KR102433225B1 - Polyol composition obtained by addition reaction of compatibilizer to anhydrosugar alcohol composition, thermoplastic starch composition comprising the polyol composition or anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition, and molded article comprising the starch composition - Google Patents

Abstract

The present invention relates to a polyol composition, a thermoplastic starch composition, and a molded article comprising the same, and more particularly, to a molded article having improved economical efficiency and eco-friendliness and improved tensile strength and elongation by using an anhydrosugar alcohol composition derived from biomass It relates to polyol compositions and thermoplastic starch compositions that can be provided, and to such molded articles.

Description

A polyol composition obtained by addition reaction of a compatibilizer to an anhydrosugar alcohol composition, a thermoplastic starch composition comprising the polyol composition, anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition, and a molded article including the starch composition TECHNICAL FIELD obtained by addition reaction of compatibilizer to anhydrosugar alcohol composition, thermoplastic starch composition comprising the polyol composition or anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition, and molded article comprising the starch composition}

The present invention relates to a polyol composition, a thermoplastic starch composition, and a molded article comprising the same, and more particularly, to a molded article having improved economical efficiency and eco-friendliness and improved tensile strength and elongation by using an anhydrosugar alcohol composition derived from biomass It relates to polyol compositions and thermoplastic starch compositions that can be provided, and to such molded articles.

In the conventional case, when the thermoplastic starch composition is prepared, components such as glycerol and sorbitol are added as plasticizers to plasticize the starch. However, when the conventional plasticizer component is mixed with starch and extruded to form pellets, and then mixed with a biodegradable polymer and processed into a film, the tensile strength and elongation of the film are lowered, so the range of use is limited It had to be limited to food packaging and agricultural mulching film. In addition, due to the use of the plasticizer, the processing cost and production cost of the thermoplastic starch composition are increased.

Therefore, there is a need for developing a technology for producing a thermoplastic starch composition capable of reducing the cost of producing a thermoplastic starch composition by removing a factor of cost increase due to the use of a conventional plasticizer and improving the physical properties of a molded article including the same.

Hydrogenated sugar (also referred to as “sugar alcohol”) refers to a compound obtained by adding hydrogen to a reducing end group of a saccharide, generally HOCH ₂ (CHOH) _n CH ₂ OH (where n is an integer of 2 to 5) ), and is classified into tetritol, pentitol, hexitol, and heptitol (with 4, 5, 6 and 7 carbon atoms, respectively) according to the number of carbon atoms. Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol, and the like, and sorbitol and mannitol are particularly effective substances.

Anhydrosugar alcohol is a substance formed by removing one or more water molecules from the inside of a hydrogenated sugar. When one water molecule is removed, it has a tetraol form with 4 hydroxyl groups in the molecule, and 2 When the dog is removed, it has the form of a diol having two hydroxyl groups in the molecule, and can be prepared by using hexitol derived from starch (eg, Korea Patent No. 10-1079518, Korean Patent Application Laid-Open No. 10-2012-0066904). Anhydrosugar alcohol is an eco-friendly material derived from renewable natural resources, and research on its manufacturing method has been conducted with a lot of interest from a long time ago. Among these anhydrosugar alcohols, isosorbide prepared from sorbitol has the widest industrial application range at present.

The use of anhydrosugar alcohol is very diverse, such as treatment of heart and blood vessel diseases, adhesives for patches, pharmaceuticals such as mouthwashes, solvents for compositions in the cosmetic industry, and emulsifiers in the food industry. In addition, it can raise the glass transition temperature of polymer materials such as polyester, PET, polycarbonate, polyurethane, and epoxy resin, and has an effect of improving the strength of these materials. useful. In addition, it is known that it can be used as an eco-friendly solvent for adhesives, eco-friendly plasticizers, biodegradable polymers, and water-soluble lacquers.

As such, anhydrosugar alcohol has attracted a lot of attention due to its various uses, and its use in actual industry is gradually increasing. However, in the prior art, special uses such as simply using as a binder for a by-product obtained in the process of producing anhydrosugar alcohol by dehydrating hydrogenated sugar were not considered.

Therefore, there is also a need for development of useful uses for a by-product obtained in the process of preparing hydrogenated sugar from glucose and anhydrosugar alcohol from hydrogenated sugar.

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyol composition and a thermoplastic starch composition capable of providing a molded article having improved economic efficiency and environmental friendliness and improved tensile strength and elongation, and such a molded article.

A first aspect of the present invention is a polyol composition comprising:

It is obtained by addition reaction of a compatibilizer to anhydrosugar alcohol composition,

The anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is a mono-anhydrosugar alcohol, the second polyol component is a dianhydrosugar alcohol, and the third polyol component has the following formula It is a polysaccharide alcohol represented by 1, the fourth polyol component is an anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1 below, and the fifth polyol component is the first to fourth polyol components At least one polymer selected from

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 1.13 to 3.41; and

iii) the average number of —OH groups per molecule in the anhydrosugar alcohol composition is 2.54 to 21.36;

There is provided a polyol composition, wherein the compatibilizer is added in an amount of greater than 3 parts by weight and less than 80 parts by weight per 100 parts by weight of the anhydrosugar alcohol composition:

[Formula 1]

In Formula 1, n is an integer of 0 to 4.

A second aspect of the present invention is a thermoplastic starch composition comprising:

starch; and a plasticizer; and

The plasticizer comprises: (i) the polyol composition according to the first aspect of the present invention; (ii) an anhydrosugar alcohol composition as defined in the first aspect of the present invention; or (iii) anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of an anhydrosugar alcohol composition as defined in the first aspect of the present invention with an alkylene oxide;

The anhydrosugar alcohol-alkylene glycol composition provides a thermoplastic starch composition prepared by addition reaction of an alkylene oxide in an amount of more than 5 parts by weight to less than 700 parts by weight per 100 parts by weight of the anhydrosugar alcohol composition .

A third aspect of the present invention provides a masterbatch comprising the thermoplastic starch composition according to the second aspect of the present invention.

A fourth aspect of the present invention is the masterbatch according to the third aspect of the present invention; and a thermoplastic resin; provides a molded article comprising.

According to the present invention, it is possible to obtain a molded article having improved economical efficiency and environmental friendliness and improved tensile strength and elongation, and a polyol composition and a thermoplastic starch composition capable of providing the same.

In addition, the thermoplastic starch composition according to the present invention and a molded article including the same are an anhydrosugar alcohol composition obtained by utilizing a by-product obtained in the process of preparing an internal dehydrated product of hydrogenated sugar or an anhydrosugar alcohol-alkyl derived from the anhydrosugar alcohol composition. Since it is manufactured using a ren glycol composition or a polyol composition, it is possible to increase economic efficiency and improve eco-friendliness by solving the by-product treatment problem.

Hereinafter, the present invention will be described in more detail.

[Polyol composition]

The polyol composition according to the first aspect of the present invention is obtained by addition-reacting a compatibilizer to an anhydrosugar alcohol composition.

Anhydrous sugar alcohol composition

The anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is a monoanhydrosugar alcohol, the second polyol component is a dianhydrosugar alcohol, and the third polyol component has the following formula It is a polysaccharide alcohol represented by 1, the fourth polyol component is an anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1 below, and the fifth polyol component is the first to fourth polyol components at least one polymer selected from among

[Formula 1]

In Formula 1, n is an integer of 0 to 4.

mono-anhydrosugar alcohol, which is the first polyol component included in the anhydrosugar alcohol composition of the present invention; dianhydrosugar alcohol as a second polyol component; polysaccharide alcohol as a third polyol component; anhydrosugar alcohol formed by removing water molecules from polysaccharide alcohol, which is a fourth polyol component; and at least one polymer selected from the first to fourth polyol components that are the fifth polyol component, preferably two or more, more preferably all of them, a glucose-containing saccharide composition (eg, glucose , mannose, fructose, and maltose) are subjected to a hydrogenation reaction to prepare a hydrogenated sugar composition, and the obtained hydrogenated sugar composition is heated in the presence of an acid catalyst for a dehydration reaction, and the obtained dehydration reaction product It can be obtained in the process of preparing by thin film distillation. More specifically, all of the first to fifth polyol components included in the anhydrosugar alcohol composition of the present invention may be by-products remaining after thin film distillation is obtained by thin film distillation of the obtained dehydration reaction product.

The monoanhydrosugar alcohol, which is the first polyol component, 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. In the present invention, the type of the mono-anhydrosugar alcohol is not particularly limited, but may preferably be mono-anhydrosugar hexitol, and 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.

The dianhydrosugar alcohol, which is the second polyol component, is an anhydrosugar alcohol formed by removing two water molecules from the inside of a hydrogenated sugar, and has a diol form having two hydroxyl groups in the molecule, and hexitol derived from starch It can be manufactured using Since dianhydrosugar alcohol is an eco-friendly material derived from renewable natural resources, research on its manufacturing method has been conducted with a lot of interest from a long time ago. Among these dianhydrosugar alcohols, isosorbide prepared from sorbitol currently has the widest industrial application range.

In the present invention, the type of the dianhydrosugar alcohol is not particularly limited, but may preferably be dianhydrosugar hexitol, and 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.

In one embodiment, the polysaccharide alcohol represented by Formula 1, which is the third polyol component, may be prepared by hydrogenation reaction of polysaccharides of disaccharides or higher including maltose.

In one embodiment, the anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1, which is the fourth polyol component, is a compound represented by the following Formula 2, a compound represented by the following Formula 3, or a mixture thereof can be selected from:

[Formula 2]

[Formula 3]

In Formulas 2 and 3,

n is each independently an integer from 0 to 4.

In one embodiment, the at least one polymer selected from the first to fourth polyol components, which is the fifth polyol component, includes at least one selected from the group consisting of a condensation polymer prepared from the following polycondensation reaction. can do:

- polycondensation reaction of the first polyol component,

- polycondensation reaction of the second polyol component,

- polycondensation reaction of the third polyol component,

- polycondensation reaction of the fourth polyol component,

- polycondensation reaction of the first polyol component and the second polyol component,

- polycondensation reaction of the first polyol component and the third polyol component,

- polycondensation reaction of the first polyol component and the fourth polyol component,

- polycondensation reaction of the second polyol component and the third polyol component;

- polycondensation reaction of the second polyol component and the fourth polyol component,

- polycondensation reaction of the third polyol component and the fourth polyol component,

- polycondensation reaction of the first polyol component, the second polyol component and the third polyol component;

- polycondensation reaction of the first polyol component, the second polyol component and the fourth polyol component;

- polycondensation reaction of the first polyol component, the third polyol component and the fourth polyol component;

- polycondensation reaction of the second polyol component, the third polyol component and the fourth polyol component, or

- Polycondensation reaction of the first polyol component, the second polyol component, the third polyol component and the fourth polyol component.

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 1.13 to 3.41;

iii) The average number of -OH groups per molecule in the anhydrosugar alcohol composition is 2.54 to 21.36.

When the number average molecular weight of the anhydrosugar alcohol composition is less than 193, the resin composition including the thermoplastic starch composition prepared using the same has poor processability and is not extruded into a film or the like. Conversely, when the number average molecular weight of the anhydrosugar alcohol composition exceeds 1,589, extrusion molding of the resin composition including the thermoplastic starch composition prepared using the same is possible, but the tensile strength and elongation of the molded article are poor.

In addition, when the polydispersity index of the anhydrosugar alcohol composition is less than 1.13, the resin composition including the thermoplastic starch composition prepared using the same has poor processability and is not extruded into a film or the like. Conversely, when the polydispersity index of the anhydrosugar alcohol composition exceeds 3.41, extrusion molding of the resin composition including the thermoplastic starch composition prepared using the same is possible, but the tensile strength and elongation of the molded article are poor.

In addition, when the average number of -OH groups per molecule in the anhydrosugar alcohol composition is less than 2.54, the resin composition including the thermoplastic starch composition prepared using the same has poor processability and is not extruded into a film or the like. Conversely, if the average number of -OH groups per molecule in the anhydrosugar alcohol composition exceeds 21.36, extrusion molding of the resin composition including the thermoplastic starch composition prepared using the same is possible, but the tensile strength and elongation of the molded article are lower. become bad

In one embodiment, the number average molecular weight (Mn: unit g / mol) of the anhydrosugar alcohol composition may be 193 or more, 195 or more, 200 or more, 202 or more, 205 or more, or 208 or more, and also 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. Further, in one embodiment, the number average molecular weight (Mn) of the anhydrosugar alcohol composition may be 193 to 1,589, specifically 195 to 1,550, more specifically 200 to 1,520, and more specifically As may be 202 to 1,500, more specifically, may be 205 to 1,490.

In one embodiment, the polydispersity index (PDI) of the anhydrosugar 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, and also 3.41 or less, 3.40 or less, 3.35 or less, 3.30 or less, 3.25 or less or less, 3.22 or less, or 3.19 or less. Further, in one embodiment, the polydispersity index (PDI) of the anhydrosugar alcohol composition may be 1.13 to 3.41, specifically 1.13 to 3.40, more specifically 1.15 to 3.35, and even more Specifically, it may be 1.20 to 3.25, and even more specifically, it may be 1.23 to 3.22.

In one embodiment, 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, and also, 21.36 or more. or less, 21.30 or less, 21.0, 20.5 or less, 20.0 or less, 19.95 or less, or 19.92 or less. Further, in one embodiment, the average number of -OH groups per molecule in the anhydrosugar alcohol composition may be from 2.54 to 21.36, more specifically from 2.60 to 21.30, and even more specifically from 2.65 to It can be 21.0 pieces.

In one embodiment, in the anhydrosugar alcohol composition, based on the total weight of the composition, for example, the first polyol component is 0.1 to 20% by weight, specifically 0.6 to 20% by weight, more specifically 0.7 to 15% by weight may be included, and the second polyol component may be included in an amount of 0.1 to 28% by weight, specifically 1 to 25% by weight, more specifically 3 to 20% by weight, the third polyol component and the fourth polyol The total content of the components may be 0.1 to 6.5% by weight, specifically 0.5 to 6.4% by weight, more specifically 1 to 6.3% by weight, and the fifth polyol component is 55 to 90% by weight, specifically 60 to 89.9% by weight, more specifically 70 to 89.9% by weight may be included, but is not particularly limited thereto.

In one embodiment, the anhydrosugar alcohol composition is prepared by hydrogenating a glucose-containing saccharide composition (e.g., glucose; mannose; fructose; and a saccharide composition including polysaccharides at least disaccharides including maltose) by hydrogenation reaction; , the obtained hydrogenated sugar composition is heated under an acid catalyst for dehydration reaction, and the obtained dehydration reaction product may be prepared by thin film distillation, and more specifically, thin film distillate obtained by thin film distillation of the obtained dehydration reaction product. After that, it may be the remaining by-product.

More specifically, a hydrogenation reaction of the glucose-containing saccharide composition is carried out under a hydrogen pressure condition of 30 to 80 atm and a heating condition of 110°C to 135°C to prepare a hydrogenated sugar composition, and dehydration of the obtained hydrogenated sugar composition The reaction is carried out 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 thin film distillation of the obtained dehydration reaction product is carried out under reduced pressure conditions of 2 mbar or less and 150° C. to 175° C. It may be carried out under the heating conditions of, but is not limited thereto.

In one embodiment, 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, based on the total weight of the saccharide composition, and 99.5 weight % or less, 99 wt% or less, 98.5 wt% or less, 98 wt% or less, 97.5 wt% or less or 97 wt% or less, for example 41 to 99.5 wt%, 45 to 98.5 wt% or 50 to 98 wt% It can be %.

When the glucose content in the sugar composition is less than 41% by weight, the number average molecular weight (Mn) of the anhydrosugar alcohol composition is too high, and the resin composition including the thermoplastic starch composition prepared using the same is not extruded into a film or the like due to poor processability. If it exceeds 99.5% by weight, the number average molecular weight of the anhydrosugar alcohol composition is too low, and the tensile strength and elongation of the molded article including the thermoplastic starch composition prepared using the same may be poor.

In one embodiment, the content of polysaccharide alcohol (sugar alcohol greater than or equal to disaccharide) included in the hydrogenated sugar composition is the total dry weight of the hydrogenated sugar composition (here, the dry weight means the weight of solids remaining after removing moisture from the hydrogenated sugar composition) ), may be 0.8 wt% or more, 1 wt% or more, 2 wt% or 3 wt% or more, and 57 wt% or less, 55 wt% or less, 52 wt% or less, 50 wt% or less, or 48 wt% or less It may be, for example, 0.8 to 57% by weight, 1 to 55% by weight, or 3 to 50% by weight.

When the content of the polysaccharide alcohol in the hydrogenated sugar composition is less than 0.8% by weight, the effect of increasing fluidity due to the polysaccharide alcohol and the anhydrosugar alcohol derived therefrom is insignificant, so the distillation yield of the dianhydrosugar alcohol (eg, isosorbide) This may be lowered, and when it exceeds 57 wt%, there is a problem in that the distillation yield of the dianhydrosugar alcohol is significantly lowered when the result of the dehydration reaction of the hydrogenated sugar composition is thin-film distilled.

In addition, when the polysaccharide alcohol content in the hydrogenated sugar composition is less than 0.8% by weight, an anhydrosugar alcohol composition is prepared using the hydrogenated sugar composition and the compatibility of the polyol composition prepared using the anhydrosugar alcohol composition is lowered, so that the final product is Molding may not be easy, and when it exceeds 57 wt%, an anhydrosugar alcohol composition is prepared using the hydrogenated sugar composition, and the tensile strength of a molded article including the thermoplastic starch composition to which the polyol composition prepared using the same is applied and poor elongation.

Compatibilizer and its addition reaction

The polyol composition of the present invention is prepared by addition reaction of the compatibilizer in an amount of more than 3 parts by weight to less than 80 parts by weight per 100 parts by weight of the anhydrosugar alcohol composition.

In one embodiment, the compatibilizer may be at least one selected from the group consisting of C3-C10 dicarboxylic acids or anhydrides thereof, and more specifically, at least one selected from the group consisting of maleic acid, citric acid, or anhydrides thereof. However, the present invention is not limited thereto.

In one embodiment, the amount of the addition-reacted compatibilizer per 100 parts by weight of the anhydrosugar alcohol composition may be more than 3 parts by weight, 4 parts by weight or more, or 5 parts by weight or more, and also less than 80 parts by weight, 70 parts by weight or less, 60 parts by weight or more. parts by weight or less, or 50 parts by weight or less. Specifically, the amount of the addition-reacted compatibilizer per 100 parts by weight of the anhydrosugar alcohol composition is more than 3 parts by weight to less than 80 parts by weight, 4 parts by weight to 70 parts by weight, 5 parts by weight to 60 parts by weight, or 5 parts by weight to 50 parts by weight.

When the amount of the addition-reacted compatibilizer is 3 parts by weight or less per 100 parts by weight of the anhydrosugar-alcohol composition, the tensile strength and elongation of the molded article including the thermoplastic starch composition prepared using the same deteriorates. The tensile strength and elongation of

In one embodiment, the addition reaction of the anhydrosugar alcohol composition and the compatibilizer is a catalyst, such as a base catalyst (eg, sodium hydroxide, etc.) in the presence of an elevated temperature (eg, 50 ℃ to 100 ℃, or 60° C. to 80° C.), for example, for 1 to 10 hours, or for 2 to 5 hours, but is not limited thereto.

[Thermoplastic Starch Composition]

The thermoplastic starch composition according to the second aspect of the present invention comprises: starch; and a plasticizer;

starch

In one embodiment, the starch is selected from the group consisting of corn starch, potato starch, sweet potato starch, tapioca starch, rice starch, wheat starch, sago starch, modified starches thereof, dextrins, or combinations thereof. There may be more than one.

In one embodiment, the amount of the starch included in the thermoplastic starch composition is based on 100 parts by weight of the total solid content in the thermoplastic starch composition, for example, 50 parts by weight or more, 55 parts by weight or more, 60 parts by weight or more, 65 parts by weight or more. Or it may be 70 parts by weight or more, and may be 95 parts by weight or less, 90 parts by weight or less, 85 parts by weight or less, or 80 parts by weight or less, but is not limited thereto.

plasticizer

The plasticizer included in the thermoplastic starch composition of the present invention may include (i) the polyol composition of the present invention; (ii) the anhydrosugar alcohol composition; or (iii) anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of the anhydrosugar alcohol composition and alkylene oxide;

As plasticizer components that can be included in the thermoplastic starch composition of the present invention, (i) the polyol composition of the present invention and (ii) the anhydrosugar alcohol composition are as described above.

As a plasticizer component that can be included in the thermoplastic starch composition of the present invention, (iii) the anhydrosugar alcohol-alkylene glycol composition refers to a composition obtained by addition reaction of the above-described anhydrosugar alcohol composition with an alkylene oxide, and accordingly, anhydrosugar alcohol -The alkylene glycol composition includes an adduct obtained by reacting an alkylene oxide with at least one terminal of each of the first to fifth polyol components, and specifically, the anhydrosugar alcohol-alkylene glycol composition is the first polyol component of an alkylene oxide adduct (hereinafter referred to as “the first anhydrosugar alcohol-alkylene glycol”), an alkylene oxide adduct of the second polyol component (hereinafter, “second anhydrosugar alcohol-alkylene glycol”) ), an alkylene oxide adduct of a third polyol component (hereinafter referred to as “third anhydrosugar alcohol-alkylene glycol”), an alkylene oxide adduct of a fourth polyol component (hereinafter referred to as “the third 4 anhydrosugar alcohol-alkylene glycol”) and an alkylene oxide adduct of the fifth polyol component (hereinafter referred to as “fifth anhydrosugar alcohol-alkylene glycol”).

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

As a plasticizer component that can be included in the thermoplastic starch composition of the present invention, (iii) the anhydrosugar alcohol-alkylene glycol composition comprises an alkylene oxide in an amount of more than 5 parts by weight to less than 700 parts by weight per 100 parts by weight of the anhydrosugar alcohol composition. It is prepared by addition reaction. When the added amount of the alkylene oxide per 100 parts by weight of the anhydrosugar alcohol composition is 5 parts by weight or less, the tensile strength and elongation of the molded article including the thermoplastic starch composition prepared using the same, the tensile strength and elongation of the molded article are poor. The strength and elongation are poor.

In one embodiment, the amount of the addition-reacted alkylene oxide per 100 parts by weight of the anhydrosugar alcohol composition is, for example, more than 5 parts by weight, 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more or It may be 10 parts by weight or more, and may be less than 700 parts by weight, 650 parts by weight or less, 600 parts by weight or less, 550 parts by weight or less, or 500 parts by weight or less, but is not limited thereto.

In one embodiment, the addition reaction of the anhydrosugar alcohol composition and the alkylene oxide is, for example, at a temperature of 100° C. or more, more specifically 100° C. to 140° C., for 1 hour or more, more specifically 1 hour to It may be carried out for 5 hours, but is not limited thereto.

In one embodiment, the plasticizer comprises a plasticizer component other than the (i) polyol composition, (ii) anhydrosugar alcohol composition and (iii) anhydrosugar alcohol-alkylene glycol composition (hereinafter, “additional plasticizer component”). may additionally include.

In one embodiment, the additional plasticizer component is water, glycerol, glycerin, ethylene glycol, glucose, sorbitol, maltose, sucrose, cyclodextrin, glycerin diacetate, propylene glycol, polypropylene glycol, methoxyethylene glycol, pentaerythritol or It may be one or more selected from the group consisting of combinations thereof, but is not limited thereto.

In one embodiment, the total amount of the plasticizer included in the thermoplastic starch composition is based on 100 parts by weight of the total solid content in the thermoplastic starch composition, for example, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 20 parts by weight. or more, and may be 50 parts by weight or less, 45 parts by weight or less, 40 parts by weight or less, 35 parts by weight or less, or 30 parts by weight or less, but is not limited thereto.

In one embodiment, when the additional plasticizer component is included in the thermoplastic starch composition, the amount of the additional plasticizer component is, based on 100 parts by weight of the total plasticizer, for example, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more. or more or 40 parts by weight or more, and may be 90 parts by weight or less, 80 parts by weight or less, 70 parts by weight or less, or 60 parts by weight or less, but is not limited thereto.

[Masterbatch and molded product]

According to another aspect of the present invention, there is provided a masterbatch comprising the above-described thermoplastic starch composition of the present invention.

There is no particular limitation on the method for preparing the masterbatch, and methods and apparatuses conventionally used for preparing the masterbatch in the art may be used. In one embodiment, the masterbatch comprises the starch and plasticizer described above ((i) polyol composition, (ii) anhydrosugar alcohol composition and/or (iii) anhydrosugar alcohol-alkylene glycol composition), and optionally additional After the mixture in which the plasticizer component is uniformly mixed with distilled water is added to the extruder and extruded, it may be prepared in the form of pellets cut to an appropriate size, but is not limited thereto.

According to another aspect of the present invention, the above-described masterbatch of the present invention; and a thermoplastic resin; is provided.

In one embodiment, the thermoplastic resin may be a biodegradable thermoplastic resin, and more specifically, the biodegradable thermoplastic resin is polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polylactic acid, It may be one or more selected from polyhydroxy alkanoate (PHA), polyethylene, polypropylene, polystyrene, or a combination thereof, but is not limited thereto.

In one embodiment, the molded article may be a molded article by extrusion, injection, or other processing, and more specifically, may be an extrusion-molded article (eg, a film, a sheet, etc.).

There is no particular limitation on the manufacturing method of the molded article, and methods and apparatuses conventionally used for manufacturing the resin molded article in this technical field may be used. In one embodiment, the molded article may be manufactured in the form of a film by mixing the masterbatch of the thermoplastic starch composition of the present invention described above and the above-described thermoplastic resin and then performing blow molding, but is not limited thereto. does not

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited thereto.

[Example]

<Preparation of anhydrosugar alcohol composition comprising the first to fifth polyol components>

Preparation Example A1: Preparation of anhydrosugar alcohol composition using glucose and a thin film distiller at a content of 97% by weight

A liquid hydrogenated sugar composition having a concentration of 55% by weight by hydrogenating a glucose product having a purity of 97% in the presence of a nickel catalyst and at a temperature of 125°C and a hydrogen pressure of 60 atm (Sorbitol 96% by weight, mannitol 0.9% by weight based on solid content) % and 3.1% by weight of polysaccharide alcohol more than disaccharide) 1,819 g were obtained, which was put into a batch reactor with a stirrer 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. Thereafter, the temperature inside the reactor was raised to about 135° C., and a dehydration reaction was performed under a reduced pressure of about 45 mmHg to convert to anhydrosugar alcohol. After completion of the dehydration reaction, the temperature of the reaction product was cooled to 110° C. or less, and about 15.7 g of a 50% sodium hydroxide aqueous solution was added to neutralize the reaction product. Thereafter, the temperature was cooled to 100 or less and concentrated under reduced pressure of 45 mmHg for 1 hour or more to remove residual moisture and low boiling point substances, thereby obtaining about 831 g of anhydrosugar-alcohol conversion solution. As a result of analyzing the obtained anhydrosugar-alcohol conversion solution by gas chromatography, the conversion content to isosorbide was 71.9 wt%, and the molar conversion rate from sorbitol to isosorbide was calculated to be 77.6%.

831 g of the obtained anhydrosugar-alcohol conversion solution was put into a thin film distiller (SPD) to proceed with distillation. At this time, the distillation was carried out at a temperature of 160° C. and a vacuum pressure of 1 mbar, to obtain about 589 g of a distillate (distillation yield: about 70.9%). At this time, the purity of isosorbide in the distillate was measured to be 96.8%, and the distillation yield of isosorbide calculated therefrom was 95.3%. After separation of the distillate, isosorbide (dianhydrosugar alcohol) [second polyol component] 11.5% by weight, isomannide (dianhydrosugar alcohol) [second polyol component] 0.4% by weight, sorbitan (monanhydrosugar) alcohol) [first polyol component] 7.4 wt%, polysaccharide alcohol represented by the above formula (1) [third polyol component] and anhydrosugar alcohol derived therefrom (that is, formed by removing water molecules from polysaccharide alcohol) [agent a total of 2.5% by weight of the polyol component of 4] and 78.2% by weight of a polymer thereof [the fifth polyol component], the composition has a number average molecular weight of 208 g/mol, a polydispersity index of the composition is 1.25, and the composition About 242 g of anhydrosugar alcohol composition having a hydroxyl value of 751 mg KOH/g and an average number of -OH groups per molecule in the composition of 2.78 was obtained.

Preparation A2: Preparation of a sugar composition containing 85.2 wt% of glucose and anhydrosugar alcohol composition using a thin film distiller

Preparation Example Except for using a saccharide composition containing 85.2% by weight of glucose (85.2% by weight of glucose and 14.8% by weight of mannose, fructose and polysaccharides (disaccharides or higher saccharides such as maltose) in place of the 97% pure glucose product) Hydrogenation reaction was performed in the same manner as in A1 to obtain 1,852 g of a liquid hydrogenated sugar composition having a concentration of 54 wt% (based on solid content, sorbitol 84.1 wt%, mannitol 2.8 wt%, and disaccharide or higher polysaccharide alcohol 13.1 wt%), This was put into a batch reactor equipped with a stirrer and concentrated by heating to 100° C. to obtain 1,000 g of a concentrated hydrogenated sugar composition.

The same method as in Preparation Example A1 for 1,000 g of the concentrated hydrogenated sugar composition, except that the content of sulfuric acid was changed from 9.6 g to 8.4 g and the content of 50% aqueous sodium hydroxide solution was changed from 15.7 g to 13.7 g was converted to anhydrosugar alcohol by performing a dehydration reaction. The anhydrous sugar-alcohol conversion solution obtained as a result of the dehydration reaction was about 846 g, and as a result of analyzing the obtained anhydrous sugar-alcohol conversion solution by gas chromatography, the conversion content to isosorbide was 61.7 wt%, through which sorbitol to isosorbate The molar conversion to beads was calculated to be 77.4%.

Thin film distillation was performed on 846 g of the obtained anhydrosugar-alcohol conversion solution in the same manner as in Example 1 to obtain about 528 g of a distillate (distillation yield: about 62.4%). At this time, the purity of isosorbide in the distillate was measured to be 96.5%, and the distillation yield of isosorbide calculated therefrom was 97.6%. After separation of the distillate, 4.0 wt% of isosorbide (dianhydrosugar alcohol), 1.6 wt% of isomannide (dianhydrosugar alcohol), 2.1 wt% of sorbitan (monohydrosugar alcohol), polysaccharide alcohol represented by Formula 1 and a total of 5.1% by weight of anhydrosugar alcohols derived therefrom (i.e., formed by removing water molecules from the polysaccharide alcohol) and 87.2% by weight of their polymers, wherein the composition has a number average molecular weight of 720 g/mol, and About 318 g of anhydrosugar alcohol composition having a polydispersity index of 2.54, a hydroxyl value of the composition of 754 mg KOH/g, and an average number of -OH groups per molecule in the composition of 9.68 was obtained.

Preparation A3: Preparation of a sugar composition containing 50.2 wt% of glucose and anhydrosugar alcohol composition using a thin film distiller

Except for using a saccharide composition containing 50.2% by weight of glucose (50.2% by weight of glucose and 49.8% by weight of mannose, fructose, and polysaccharides (disaccharides or higher saccharides such as maltose) in place of the 97% pure glucose product), Preparation Example Hydrogenation reaction was performed in the same manner as in A1 to obtain 1,819 g of a liquid hydrogenated sugar composition having a concentration of 55 wt% (based on solids, sorbitol 48.5 wt%, mannitol 3.6 wt%, disaccharide or higher polysaccharide alcohol 47.9 wt%), This was put into a batch reactor equipped with a stirrer and concentrated by heating to 100° C. to obtain 1,000 g of a concentrated hydrogenated sugar composition.

The concentrated hydrogenated sugar composition 1,000, except that the content of sulfuric acid was changed from 9.6 g to 4.85 g, the content of 50% aqueous sodium hydroxide solution was changed from 15.7 g to 7.9 g, and the reaction temperature was changed to 120 ° C. g was converted to anhydrosugar alcohol by performing a dehydration reaction in the same manner as in Preparation Example A1. The anhydrous sugar-alcohol conversion solution obtained as a result of the dehydration reaction was about 890 g, and as a result of analyzing the obtained anhydrous sugar-alcohol conversion solution by gas chromatography, the conversion content of isosorbide was 33.7 wt%, and through this, The molar conversion of the beads was calculated to be 77.1%.

Thin film distillation was performed on 890 g of the obtained anhydrosugar-alcohol conversion solution in the same manner as in Preparation Example A1 to obtain about 304 g of a distillate (distillation yield: about 34.2%). At this time, the purity of isosorbide in the distillate was measured to be 96.9%, and the distillation yield of isosorbide calculated therefrom was 98.3%. After separation of the distillate, isosorbide (dianhydrosugar alcohol) 0.9 wt%, isomannide (dianhydrosugar alcohol) 2.1 wt%, sorbitan (monanhydrosugar alcohol) 0.9 wt%, polysaccharide alcohol represented by Formula 1 and a total of 6.2% by weight of anhydrosugar alcohols derived therefrom (i.e., formed by removing water molecules from the polysaccharide alcohol) and 89.9% by weight of their polymers, wherein the composition has a number average molecular weight of 1,480 g/mol, and About 586 g of anhydrosugar alcohol composition having a polydispersity index of 3.19, a hydroxyl value of the composition of 755 mg KOH/g, and an average number of -OH groups per molecule in the composition of 19.92 was obtained.

Preparation A4: Preparation of anhydrosugar alcohol composition using 99.9% by weight of glucose crystals and a thin film distiller

A hydrogenation reaction was performed in the same manner as in Preparation Example A1 except for using a glucose crystal having a purity of 99.9% by weight separated in the glucose manufacturing process instead of a glucose product having a purity of 97%, and a liquid phase having a concentration of 55% by weight was used. 1,819 g of a hydrogenated sugar composition (based on solid content, sorbitol 99.1 wt%, mannitol 0.2 wt%, disaccharide or higher polysaccharide alcohol 0.7 wt%) was obtained, which was placed in a batch reactor with a stirrer and heated to 100 ° C. to concentrate, resulting in concentrated hydrogenation 1,000 g of the sugar composition was obtained.

The same method as in Preparation Example A1 for 1,000 g of the concentrated hydrogenated sugar composition, except that the content of sulfuric acid was changed from 9.6 g to 9.9 g and the content of 50% aqueous sodium hydroxide solution was changed from 15.7 g to 16.2 g was carried out to proceed with a dehydration reaction to convert to anhydrosugar alcohol. The anhydrous sugar-alcohol conversion solution obtained as a result of the dehydration reaction was about 827 g, and as a result of analyzing the obtained anhydrous sugar-alcohol conversion solution by gas chromatography, the conversion content of isosorbide was 74.2 wt%, and through this, The molar conversion of the beads was calculated to be 77.2%.

Thin film distillation was performed on 827 g of the obtained anhydrosugar-alcohol conversion solution in the same manner as in Preparation Example A1 to obtain about 555 g of a distillate (distillation yield: about 67.1%). At this time, the purity of isosorbide in the distillate was measured to be 96.7%, and the distillation yield of isosorbide calculated therefrom was 87.5%. After separation of the distillate, 28.2% by weight of isosorbide (dianhydrosugar alcohol), 17.4% by weight of sorbitan (monoanhydrosugar alcohol) and 54.4% by weight of a polymer thereof, and the number average molecular weight of the composition is 192 g/mol , the polydispersity index of the composition is 1.12, the hydroxyl value of the composition is 740 mg KOH/g, and about 272 g of anhydrosugar alcohol composition having an average number of -OH groups per molecule in the composition is 2.53.

Preparation A5: Preparation of sugar composition containing 40.1 wt% of glucose and anhydrosugar alcohol composition using a thin film distiller

Preparation Example Except that 40.1 wt% of a glucose-containing saccharide composition (40.1 wt% of glucose and 59.9 wt% of mannose, fructose and polysaccharides (disaccharides or higher saccharides such as maltose) was used in place of the 97% pure glucose product) Hydrogenation was performed in the same manner as in A1 to obtain 1,819 g of a liquid hydrogenated sugar composition having a concentration of 55 wt% (based on solid content, sorbitol 38.8 wt%, mannitol 4.1 wt%, disaccharide or higher polysaccharide alcohol 57.1 wt%), This was put into a batch reactor equipped with a stirrer and concentrated by heating to 100° C. to obtain 1,000 g of a concentrated hydrogenated sugar composition.

The same method as in Preparation Example A1 for 1,000 g of the concentrated hydrogenated sugar composition, except that the content of sulfuric acid was changed from 9.6 g to 3.9 g and the content of 50% aqueous sodium hydroxide solution was changed from 15.7 g to 6.3 g was converted to anhydrosugar alcohol by performing a dehydration reaction. The anhydrous sugar-alcohol conversion solution obtained as a result of the dehydration reaction was about 902 g, and as a result of analyzing the obtained anhydrosugar-alcohol conversion solution by gas chromatography, the conversion content of isosorbide was 26.8 wt%, and through this, The molar conversion of the beads was calculated to be 77.4%.

Thin film distillation was performed on 902 g of the obtained anhydrosugar-alcohol conversion solution in the same manner as in Preparation Example A1 to obtain about 246 g of a distillate (distillation yield: about 27.3%). At this time, the purity of isosorbide in the distillate was measured to be 96.1%, and the distillation yield of isosorbide calculated therefrom was 97.8%. After separation of the distillate, isosorbide (dianhydrosugar alcohol) 0.7% by weight, isomannide (dianhydrosugar alcohol) 2.3% by weight, sorbitan (monoanhydrosugar alcohol) 0.5% by weight, polysaccharide alcohol represented by Formula 1 and a total of 6.5% by weight of anhydrosugar alcohols derived therefrom (i.e., formed by removing water molecules from the polysaccharide alcohol) and 90.0% by weight of polymers thereof, wherein the composition has a number average molecular weight of 1,590 g/mol, and About 663 g of anhydrosugar alcohol composition having a polydispersity index of 3.42, a hydroxyl value of 754 mg KOH/g, and an average number of -OH groups per molecule in the composition of 21.37 was obtained.

Preparation A6: Preparation of a saccharide composition containing 96.8 wt% of glucose and a polyol composition using simple vacuum distillation

Except for using a saccharide composition containing 96.8% by weight of glucose (96.8% by weight of glucose and 3.2% by weight of mannose, fructose and polysaccharides (disaccharides or higher saccharides such as maltose) in place of the 97% pure glucose product), Example 1,819 g of a liquid hydrogenated sugar composition having a concentration of 55 wt% (solids basis, sorbitol 95.7 wt%, mannitol 1.1 wt%, disaccharide or higher polysaccharide alcohol 3.2 wt%) was obtained by performing a hydrogenation reaction in the same manner as in 1, This was put into a batch reactor equipped with a stirrer 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 was converted into anhydrosugar alcohol by performing a dehydration reaction in the same manner as in Example 1. The anhydrous sugar-alcohol conversion solution obtained as a result of the dehydration reaction was about 832 g, and as a result of analyzing the obtained anhydrosugar-alcohol conversion solution by gas chromatography, the conversion content of isosorbide was 71.5 wt%, and through this, The molar conversion of the beads was calculated to be 77.5%.

Simple vacuum distillation was performed on 832 g of the obtained anhydrosugar-alcohol conversion solution to obtain about 461 g of a distillate (distillation yield: about 55.4%). At this time, the purity of isosorbide in the distillate was measured to be 96.6%, and the distillation yield of isosorbide calculated therefrom was 74.8%. After separation of the distillate, isosorbide (dianhydrosugar alcohol) 40.4% by weight, isomannide (dianhydrosugar alcohol) 0.4% by weight, sorbitan (monanhydrosugar alcohol) 3.2% by weight, disaccharide or more polysaccharide alcohol and derived therefrom 2.0 wt% of anhydrosugar alcohol and 54.0 wt% of a polymer thereof, the number average molecular weight of the composition is 210 g/mol, the polydispersity index of the composition is 3.94, and the hydroxyl value of the composition is 710 mg KOH/g , about 371 g of anhydrosugar alcohol composition having an average number of -OH groups per molecule in the composition of 2.66 was obtained.

The yields for each preparation step for the anhydrosugar alcohol composition of Preparation Examples A1 to A6 are shown in Table 1 below, and the composition and physical property values of each anhydrosugar alcohol composition are shown in Table 2 below.

[Method of measuring yield]

1) Isosorbide (ISB) molar conversion

2) Isosorbide (ISB) conversion content

Through gas chromatography analysis, the content (wt%) of isosorbide in the anhydrous sugar-alcohol conversion solution was measured, and the isosorbide conversion content indicates the purity of isosorbide (ISB) in the anhydrous sugar-alcohol conversion solution.

3) distillation yield

4) Distillation yield of isosorbide (ISB)

[Method for measuring physical properties of polyol composition]

1) Number average molecular weight (Mn) and polydispersity index (PDI)

Each of the polyol compositions prepared in Examples and Comparative Examples was dissolved in 1 to 3 parts by weight in N,N-dimethylformamide, and then using a Gel Permeation Chromatography (GPC) apparatus (Agilent Corporation). Number average molecular weight (Mn) and polydispersity index (PDI) were measured. The column used at this time was PLgel 3μm MIXED-E 300x7.5mm (Agilent Co.), the column temperature was 50°C, and the developing solvent used was N,N-dimethylformamide containing 0.05 M NaBr, flowing at 0.5 mL/min. and polystyrene (Aldrich, Inc.) was used as a standard material.

2) hydroxyl value

After esterification of each polyol composition prepared in Examples and Comparative Examples with an excess of phthalic anhydride under an imidazole catalyst according to ASTM D-4274D, a hydroxyl value test standard, the residual phthalic anhydride was reduced to 0.5 By performing titration with N sodium hydroxide (NaOH), the hydroxyl value of the polyol composition was measured.

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 group value x number average molecular weight) / 56,100

<Preparation of anhydrosugar alcohol-alkylene glycol composition>

Preparation B1: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 10 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A1 and 0.2 g of potassium hydroxide (KOH) were put in a high-pressure reactor with a stirrer, and the temperature was raised to 120 ° C., and then 20 g (10 parts by weight) of ethylene oxide was put in. Then, by reacting at 120° C. for 3 hours, 217 g of anhydrosugar alcohol-alkylene glycol composition was obtained.

Preparation B2: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 100 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

Anhydrosugar alcohol-alkylene glycol composition 395 g was obtained in the same manner as in Preparation Example B1, except that the content of ethylene oxide was changed from 20 g (10 parts by weight) to 200 g (100 parts by weight).

Preparation B3: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 500 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

1,190 g of anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1, except that the content of ethylene oxide was changed from 20 g (10 parts by weight) to 1,000 g (500 parts by weight).

Preparation B4: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 10 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

Anhydrosugar alcohol-alkylene glycol composition 216 g was obtained in the same manner as in Preparation Example B1, except that 20 g (10 parts by weight) of propylene oxide was used instead of ethylene oxide.

Preparation B5: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 100 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

Anhydrosugar alcohol-alkylene glycol composition 394 g was obtained in the same manner as in Preparation Example B1, except that 200 g (100 parts by weight) of propylene oxide was used instead of ethylene oxide.

Preparation B6: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 500 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

Anhydrosugar alcohol-alkylene glycol composition 1186g was obtained in the same manner as in Preparation Example B1, except that 1,000 g (500 parts by weight) of propylene oxide was used instead of ethylene oxide.

Preparation B7: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 10 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation A2

Anhydrosugar alcohol-alkyl in the same manner as in Preparation Example B1, except that 200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1. 216 g of ren glycol composition were obtained.

Preparation B8: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 100 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A2

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of ethylene oxide was 20 g (10 parts by weight) to 200 g (100 parts by weight) ), except that it was changed to anhydrosugar alcohol-alkylene glycol composition 392g was obtained in the same manner as in Preparation Example B1.

Preparation B9: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 500 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A2

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of ethylene oxide was changed from 20 g (10 parts by weight) to 1,000 g (500 parts by weight). Part), anhydrosugar alcohol-alkylene glycol composition 1,196g was obtained in the same manner as in Preparation Example B1.

Preparation B10: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 10 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A2

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 20 g (10 parts by weight) of propylene oxide was used instead of ethylene oxide And, 214 g of anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1.

Preparation B11: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 100 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar-alcohol composition of Preparation Example A2

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 200 g (100 parts by weight) of propylene oxide was used instead of ethylene oxide Then, in the same manner as in Preparation Example B1, 392 g of anhydrosugar alcohol-alkylene glycol composition was obtained.

Preparation B12: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 500 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A2

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 1,000 g (500 parts by weight) of propylene oxide was used instead of ethylene oxide. Except that, in the same manner as in Preparation Example B1, 1,192 g of anhydrosugar alcohol-alkylene glycol composition was obtained.

Preparation B13: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 10 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A3

Anhydrosugar alcohol-alkyl in the same manner as in Preparation Example B1, except that 200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A3 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1. 212 g of a Ren glycol composition was obtained.

Preparation B14: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 100 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A3

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A3 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of ethylene oxide was changed from 20 g (10 parts by weight) to 200 g (100 parts by weight). ), except that it was changed to anhydrosugar alcohol-alkylene glycol composition 396g was obtained in the same manner as in Preparation Example B1.

Preparation B15: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 500 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A3

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A3 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of ethylene oxide was changed from 20 g (10 parts by weight) to 1,000 g (500 parts by weight). Part), the same method as in Preparation Example B1 was followed to obtain 1,190 g of anhydrosugar alcohol-alkylene glycol composition.

Preparation B16: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 10 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A3

200 g (100 parts by weight) of the anhydrosugar-alcohol composition obtained in Preparation Example A3 was used instead of the anhydrosugar-alcohol composition obtained in Preparation Example A1, and 20 g (10 parts by weight) of propylene oxide was used instead of ethylene oxide And, 216 g of anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1.

Preparation B17: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 100 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A3

200 g (100 parts by weight) of the anhydrosugar-alcohol composition obtained in Preparation Example A3 was used instead of the anhydrosugar-alcohol composition obtained in Preparation Example A1, and 200 g (100 parts by weight) of propylene oxide was used instead of ethylene oxide And, 394 g of anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1.

Preparation B18: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 500 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A3

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A3 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 1,000 g (500 parts by weight) of propylene oxide was used instead of ethylene oxide. Except that, in the same manner as in Preparation Example B1, 1,192 g of anhydrosugar alcohol-alkylene glycol composition was obtained.

Preparation B19: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 10 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A4

200 g (100 parts by weight) of the anhydrosugar-alcohol composition obtained in Preparation Example A4 was used instead of the anhydrosugar-alcohol composition obtained in Preparation Example A1, and 20 g (10 parts by weight) of propylene oxide was used instead of ethylene oxide And, 216 g of anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1.

Preparation B20: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction per 100 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A5

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A5 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of ethylene oxide was 20 g (10 parts by weight) to 200 g (100 parts by weight) ), the same method as in Preparation Example B1 was followed to obtain 394 g of anhydrosugar alcohol-alkylene glycol composition.

Preparation B21: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 500 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A6

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A6 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 1,000 g (500 parts by weight) of propylene oxide was used instead of ethylene oxide. Except that, in the same manner as in Preparation Example B1, 1,194 g of anhydrosugar alcohol-alkylene glycol composition was obtained.

Preparation B22: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 5 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

206 g of anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1, except that 10 g (5 parts by weight) of propylene oxide was used instead of ethylene oxide.

Preparation B23: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 700 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

1,590 g of anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1, except that 1,400 g (700 parts by weight) of propylene oxide was used instead of ethylene oxide.

<Polyol composition prepared from anhydrous alcohol composition and compatibilizer>

Example A1: Polyol composition prepared by addition reaction of 5 parts by weight of maleic anhydride per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A1 was put into a reactor capable of heating and stirring, heated to 70 ° C, and then 0.4 g of a 50% aqueous sodium hydroxide solution was added and stirred for 30 minutes. Then, 10 g (5 parts by weight) of maleic anhydride was put into a reactor, the reaction was allowed to proceed for 2 to 3 hours, and then the reaction product was cooled to room temperature to obtain 208 g of a polyol composition to which maleic anhydride was added.

Example A2: Polyol composition prepared by addition reaction of 10 parts by weight of maleic anhydride per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

Except that the content of maleic anhydride was changed from 10 g (5 parts by weight) to 20 g (10 parts by weight), 218 g of a polyol composition to which maleic anhydride was added was obtained in the same manner as in Example A1.

Example A3: Polyol composition prepared by addition reaction of 50 parts by weight of maleic anhydride per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

Except that the content of maleic anhydride was changed from 10 g (5 parts by weight) to 100 g (50 parts by weight), 294 g of a polyol composition to which maleic anhydride was added was obtained in the same manner as in Example A1.

Example A4: Polyol composition prepared by addition reaction of 5 parts by weight of citric acid per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

208 g of a polyol composition to which citric acid was added was obtained in the same manner as in Example A1, except that 10 g (5 parts by weight) of citric acid was used instead of maleic anhydride.

Example A5: Polyol composition prepared by addition reaction of 10 parts by weight of citric acid per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

217 g of a polyol composition to which citric acid was added was obtained in the same manner as in Example A1, except that 20 g (10 parts by weight) of citric acid was used in place of maleic anhydride.

Example A6: Polyol composition prepared by addition reaction of 50 parts by weight of citric acid per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

296 g of a polyol composition to which citric acid was added was obtained in the same manner as in Example A1, except that 100 g (50 parts by weight) of citric acid was used instead of maleic anhydride.

Example A7: Polyol composition prepared by addition reaction of 5 parts by weight of maleic anhydride per 100 parts by weight of the anhydrosugar alcohol composition of Preparation A2

Maleic anhydride was added in the same manner as in Example A1, except that 200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1. 208 g of the prepared polyol composition was obtained.

Example A8: Polyol composition prepared by addition reaction of 10 parts by weight of maleic anhydride per 100 parts by weight of the anhydrosugar alcohol composition of Preparation A2

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of maleic anhydride was adjusted from 10 g (5 parts by weight) to 20 g (10 parts by weight) Part), 216 g of a polyol composition to which maleic anhydride was added was obtained in the same manner as in Example A1.

Example A9: Polyol composition prepared by addition reaction of 50 parts by weight of maleic anhydride per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A2

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of maleic anhydride was adjusted from 10 g (5 parts by weight) to 100 g (50 parts by weight) Part), 296 g of a polyol composition to which maleic anhydride was added was obtained in the same manner as in Example A1.

Example A10: Polyol composition prepared by addition reaction of 5 parts by weight of citric acid per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A2

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 10 g (5 parts by weight) of citric acid was used instead of maleic anhydride except that Then, in the same manner as in Example A1, 208 g of a polyol composition to which citric acid was added was obtained.

Example A11: Polyol composition prepared by addition reaction of 10 parts by weight of citric acid per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A2

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 20 g (10 parts by weight) of citric acid was used instead of maleic anhydride Then, in the same manner as in Example A1, 218 g of a polyol composition to which citric acid was added was obtained.

Example A12: Polyol composition prepared by addition reaction of 50 parts by weight of citric acid per 100 parts by weight of the anhydrosugar alcohol composition of Preparation A2

200 g (100 parts by weight) of the anhydrosugar-alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar-alcohol composition obtained in Preparation Example A1, and 100 g (50 parts by weight) of citric acid was used instead of maleic anhydride Then, in the same manner as in Example A1, 298 g of a polyol composition to which citric acid was added was obtained.

Example A13: Polyol composition prepared by addition reaction of 5 parts by weight of maleic anhydride per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A3

Maleic anhydride was added in the same manner as in Example A1, except that 200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A3 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1. 208 g of the prepared polyol composition was obtained.

Example A14: Polyol composition prepared by addition reaction of 10 parts by weight of maleic anhydride per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A3

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A3 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of maleic anhydride was adjusted from 10 g (5 parts by weight) to 20 g (10 parts by weight) Part), 218 g of a polyol composition to which maleic anhydride was added was obtained in the same manner as in Example A1.

Example A15: Polyol composition prepared by addition reaction of 50 parts by weight of maleic anhydride per 100 parts by weight of the anhydrosugar alcohol composition of Preparation A3

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A3 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of maleic anhydride was adjusted from 10 g (5 parts by weight) to 100 g (50 parts by weight) Part), 298 g of a polyol composition to which maleic anhydride was added was obtained in the same manner as in Example A1.

Example A16: Polyol composition prepared by addition reaction of 5 parts by weight of citric acid per 100 parts by weight of the anhydrosugar alcohol composition of Preparation A3

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A3 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 10 g (5 parts by weight) of citric acid was used instead of maleic anhydride except that Then, in the same manner as in Example A1, 206 g of a polyol composition to which citric acid was added was obtained.

Example A17: Polyol composition prepared by addition reaction of 10 parts by weight of citric acid per 100 parts by weight of the anhydrosugar alcohol composition of Preparation A3

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A3 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 20 g (10 parts by weight) of citric acid was used instead of maleic anhydride Then, in the same manner as in Example A1, 216 g of a polyol composition to which citric acid was added was obtained.

Example A18: Polyol composition prepared by addition reaction of 50 parts by weight of citric acid per 100 parts by weight of the anhydrosugar alcohol composition of Preparation A3

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A3 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 100 g (50 parts by weight) of citric acid was used instead of maleic anhydride except that Then, in the same manner as in Example A1, 294 g of a polyol composition to which citric acid was added was obtained.

Comparative Example A1: Polyol composition prepared by addition reaction of 5 parts by weight of maleic anhydride per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A4

Maleic anhydride was added in the same manner as in Example A1, except that 200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A4 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1. 208 g of the prepared polyol composition was obtained.

Comparative Example A2: Polyol composition prepared by addition reaction of 10 parts by weight of citric acid per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A5

200 g (100 parts by weight) of the anhydrosugar-alcohol composition obtained in Preparation Example A5 was used instead of the anhydrosugar-alcohol composition obtained in Preparation Example A1, and 20 g (10 parts by weight) of citric acid was used instead of maleic anhydride Then, in the same manner as in Example A1, 216 g of a polyol composition to which citric acid was added was obtained.

Comparative Example A3: Polyol composition prepared by addition reaction of 50 parts by weight of maleic anhydride per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A6

200 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A6 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of maleic anhydride was adjusted from 10 g (5 parts by weight) to 100 g (50 parts by weight) Part), 298 g of a polyol composition to which maleic anhydride was added was obtained in the same manner as in Example A1.

Comparative Example A4: Polyol composition prepared by addition reaction of 3 parts by weight of maleic anhydride per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

Except that the content of maleic anhydride was changed from 10 g (5 parts by weight) to 6 g (3 parts by weight), 204 g of a polyol composition to which maleic anhydride was added was obtained in the same manner as in Example A1.

Comparative Example A5: Polyol composition prepared by addition reaction of 80 parts by weight of maleic anhydride per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

Except that the content of maleic anhydride was changed from 10 g (5 parts by weight) to 160 g (80 parts by weight), 358 g of a polyol composition to which maleic anhydride was added was obtained in the same manner as in Example A1.

<Thermoplastic starch composition and film production using the same>

Example B1: Preparation of thermoplastic starch composition and film thereof using the anhydrosugar alcohol composition of Preparation Example A1

210 g of the anhydrosugar alcohol composition obtained in Preparation Example A1, 189 g of glycerol (GLY) and 167 g of distilled water were added to 1,400 g of starch having a moisture content of 10% by weight, and uniformly mixed to prepare a mixture, and then the screw diameter was 40 mmØ , the mixture was injected into a single screw extruder having 5 barrels, and extrusion was performed at an extrusion speed of 130 rpm to 150 rpm. At this time, the temperature of each barrel of the extruder is shown in Table 3 below. A masterbatch in the form of pellets was prepared by cutting the thermoplastic starch composition obtained through the extrusion to an appropriate size.

After mixing 3.5 kg of polybutylene adipate terephthalate (PBAT) and 1.5 kg of the masterbatch of the obtained thermoplastic starch composition, blow molding was performed to prepare a film. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 281.3 MPa, and the average elongation was 584%. In addition, the standard deviation of the tensile strength of the film was 1.2 MPa, the standard deviation of the elongation was 0.8%, confirming that the film was uniformly formed.

Example B2: Preparation of thermoplastic starch composition and film thereof using the anhydrosugar alcohol composition of Preparation Example A2

The same as in Example B1, except that 210 g of the anhydrosugar alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of ethylene glycol (EG) was used instead of glycerol. The method was followed to prepare a masterbatch and film of the thermoplastic starch composition. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 290.3 MPa, and the average elongation was 594.7%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 1.2 MPa and a standard deviation of elongation of 0.5% of the film.

Example B3: Preparation of thermoplastic starch composition and film thereof using the anhydrosugar alcohol composition of Preparation A3

The same method as in Example B1, except that 210 g of the anhydrosugar alcohol composition obtained in Preparation Example A3 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of sorbitol (SBT) was used instead of glycerol. was performed to prepare a masterbatch and a film of the thermoplastic starch composition. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 284.3 MPa, and the average elongation was 589.7%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.5 MPa and a standard deviation of elongation of 1.2% of the film.

Example B4: Preparation of thermoplastic starch composition and film thereof using the anhydrosugar alcohol-alkylene glycol composition of Preparation B1

189 g of anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of sorbitol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g A masterbatch and a film of a thermoplastic starch composition were prepared in the same manner as in Example B1, except for the above. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 302.3 MPa, and the average elongation was 624.7%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.9 MPa and a standard deviation of elongation of 1.2% of the film.

Example B5: Preparation of thermoplastic starch composition and film thereof using anhydrosugar alcohol-alkylene glycol composition of Preparation B2

Example B1 except that 189 g of anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of distilled water was changed from 167 g to 188 g A masterbatch and a film of the thermoplastic starch composition were prepared in the same manner as described above. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 301.0 MPa, and the average elongation was 632.0%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.8 MPa and a standard deviation of elongation of 2.2% of the film.

Example B6: Preparation of thermoplastic starch composition and film thereof using anhydrosugar alcohol-alkylene glycol composition of Preparation B3

189 g of anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B3 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of ethylene glycol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and a film of a thermoplastic starch composition were prepared in the same manner as in Example B1, except that it was changed to . As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 299.3 MPa, and the average elongation was 629.3%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.5 MPa and a standard deviation of elongation of 0.5% of the film.

Example B7: Preparation of thermoplastic starch composition and film thereof using anhydrosugar alcohol-alkylene glycol composition of Preparation B4

189 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B4 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of ethylene glycol was used instead of glycerol, and the content of distilled water was 167 g to 188 g A masterbatch and a film of a thermoplastic starch composition were prepared in the same manner as in Example B1, except that it was changed to . As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 303.3 MPa, and the average elongation was 640.3%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.5 MPa and a standard deviation of elongation of 0.5% of the film.

Example B8: Preparation of thermoplastic starch composition and film thereof using anhydrosugar alcohol-alkylene glycol composition of Preparation B5

189 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B5 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of sorbitol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and film of a thermoplastic starch composition were prepared in the same manner as in Example B1, except for the changes. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 305.0 MPa, and the average elongation was 651.0%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0 MPa and a standard deviation of elongation of 0.8% of the film.

Example B9: Preparation of thermoplastic starch composition and film thereof using anhydrosugar alcohol-alkylene glycol composition of Preparation B6

Example B1 except that 189 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B6 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of distilled water was changed from 167 g to 188 g A masterbatch and a film of the thermoplastic starch composition were prepared in the same manner as described above. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 304.7 MPa, and the average elongation was 649.3%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.5 MPa and a standard deviation of elongation of 0.5% of the film.

Example B10: Preparation of thermoplastic starch composition and film thereof using anhydrosugar alcohol-alkylene glycol composition of Preparation B7

Example B1 except that 189 g of anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B7 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of distilled water was changed from 167 g to 188 g A masterbatch and a film of the thermoplastic starch composition were prepared in the same manner as described above. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 306.7 MPa, and the average elongation was 650.3%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 1.7 MPa and a standard deviation of elongation of 0.5% of the film.

Example B11: Preparation of a thermoplastic starch composition and film thereof using the anhydrosugar alcohol-alkylene glycol composition of Preparation B8

189 g of anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B8 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of ethylene glycol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and film of a thermoplastic starch composition were prepared in the same manner as in Example B1, except for the changes. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 307.0 MPa, and the average elongation was 670.7%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 2.2 MPa and a standard deviation of elongation of 0.9% of the film.

Example B12: Preparation of thermoplastic starch composition and film thereof using anhydrosugar alcohol-alkylene glycol composition of Preparation B9

189 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B9 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of sorbitol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and film of a thermoplastic starch composition were prepared in the same manner as in Example B1, except for the changes. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 307.0 MPa, and the average elongation was 659.3%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.8 MPa and a standard deviation of elongation of 1.2% of the film.

Example B13: Preparation of a thermoplastic starch composition and a film thereof using the anhydrosugar alcohol-alkylene glycol composition of Preparation B10

189 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B10 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of sorbitol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and film of a thermoplastic starch composition were prepared in the same manner as in Example B1, except for the changes. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 308.7 MPa, and the average elongation was 681.0%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.5 MPa and a standard deviation of elongation of 0.8% of the film.

Example B14: Preparation of thermoplastic starch composition and film thereof using the anhydrosugar alcohol-alkylene glycol composition of Preparation B11

Example B1, except that 189 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B11 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of distilled water was changed from 167 g to 188 g A masterbatch and a film of the thermoplastic starch composition were prepared in the same manner as described above. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 311.3 MPa, and the average elongation was 688.7%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 1.2 MPa and a standard deviation of elongation of 1.2% of the film.

Example B15: Preparation of thermoplastic starch composition and film thereof using anhydrosugar alcohol-alkylene glycol composition of Preparation B12

189 g of anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B12 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of ethylene glycol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and film preparation of a thermoplastic starch composition were prepared in the same manner as in Example B1, with the exception of changes. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 309.3 MPa, and the average elongation was 681.0%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.9 MPa and a standard deviation of elongation of 0.8% of the film.

Example B16: Preparation of thermoplastic starch composition and film thereof using anhydrosugar alcohol-alkylene glycol composition of Preparation B13

189 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B13 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of ethylene glycol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and a film of a thermoplastic starch composition were prepared in the same manner as in Example B1, except that it was changed to . As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 291.0 MPa, and the average elongation was 599.7%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.8 MPa and a standard deviation of elongation of 1.2% of the film.

Example B17: Preparation of thermoplastic starch composition and film thereof using anhydrosugar alcohol-alkylene glycol composition of Preparation B14

189 g of anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B14 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of sorbitol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g A masterbatch and a film of a thermoplastic starch composition were prepared in the same manner as in Example B1, except for the above. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 295.0 MPa, and the average elongation was 602.7%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.8 MPa and a standard deviation of elongation of 1.2% of the film.

Example B18: Preparation of thermoplastic starch composition and film thereof using anhydrosugar alcohol-alkylene glycol composition of Preparation B15

Example B1, except that 189 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B15 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of distilled water was changed from 167 g to 188 g A masterbatch and a film of the thermoplastic starch composition were prepared in the same manner as described above. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 292.3 MPa, and the average elongation was 601.3%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.9 MPa and a standard deviation of elongation of 1.2% of the film.

Example B19: Preparation of thermoplastic starch composition and film thereof using anhydrosugar alcohol-alkylene glycol composition of Preparation B16

Example B1 except that 189 g of anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B16 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of distilled water was changed from 167 g to 188 g A masterbatch and a film of the thermoplastic starch composition were prepared in the same manner as described above. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 295.7 MPa, and the average elongation was 608.3%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 2.4 MPa and a standard deviation of elongation of 0.5% of the film.

Example B20: Preparation of a thermoplastic starch composition and a film thereof using the anhydrosugar alcohol-alkylene glycol composition of Preparation B17

189 g of anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B17 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of ethylene glycol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and film of a thermoplastic starch composition were prepared in the same manner as in Example B1, except for the changes. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 300.3 MPa, and the average elongation was 613.3%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.5 MPa and a standard deviation of elongation of 1.2% of the film.

Example B21: Preparation of thermoplastic starch composition and film thereof using anhydrosugar alcohol-alkylene glycol composition of Preparation B18

189 g of anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B18 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of sorbitol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g A masterbatch and a film of a thermoplastic starch composition were prepared in the same manner as in Example B1, except for the above. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 307.0 MPa, and the average elongation was 612.3%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 1.6 MPa and a standard deviation of elongation of 1.7% of the film.

Example B22: Preparation of thermoplastic starch composition and film thereof using the polyol composition of Example A1

Using 189 g of the polyol composition obtained in Example A1 instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, using 189 g of sorbitol instead of glycerol, and changing the content of distilled water from 167 g to 188 g, A masterbatch and film of the thermoplastic starch composition were prepared in the same manner as in Example B1. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 324.0 MPa, and the average elongation was 722.3%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.8 MPa and a standard deviation of elongation of 1.2% of the film.

Example B23: Preparation of thermoplastic starch composition and film thereof using the polyol composition of Example A2

The same method as in Example B1 was performed except that 189 g of the polyol composition obtained in Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and film of the thermoplastic starch composition were prepared. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 323.7 MPa, and the average elongation was 724.3%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 1.2 MPa and a standard deviation of elongation of 0.5% of the film.

Example B24: Preparation of thermoplastic starch composition and film thereof using the polyol composition of Example A3

189 g of the polyol composition obtained in Example A3 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of ethylene glycol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. , A masterbatch and a film of a thermoplastic starch composition were prepared in the same manner as in Example B1. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 323.0 MPa, and the average elongation was 722.3%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 1.6 MPa and a standard deviation of elongation of 1.7% of the film.

Example B25: Preparation of Thermoplastic Starch Composition and Film Thereof Using Polyol Composition of Example A4

189 g of the polyol composition obtained in Example A4 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of ethylene glycol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. , A masterbatch and a film of a thermoplastic starch composition were prepared in the same manner as in Example B1. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 321.7 MPa, and the average elongation was 720.0%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 1.7 MPa and a standard deviation of elongation of 0.8% of the film.

Example B26: Preparation of a thermoplastic starch composition and film thereof using the polyol composition of Example A5

189 g of the polyol composition obtained in Example A5 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of sorbitol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. , A masterbatch and a film of a thermoplastic starch composition were prepared in the same manner as in Example B1. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 321.0 MPa, and the average elongation was 724.3%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 1.4 MPa and a standard deviation of elongation of 0.9% of the film.

Example B27: Preparation of Thermoplastic Starch Composition and Film Thereof Using Polyol Composition of Example A6

The same method as in Example B1 was performed, except that 189 g of the polyol composition obtained in Example A6 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and film of the thermoplastic starch composition were prepared. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 321.0 MPa, and the average elongation was 721.0%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.8 MPa and a standard deviation of elongation of 0% of the film.

Example B28: Preparation of thermoplastic starch composition and film thereof using polyol composition of Example A7

The same method as in Example B1 was performed, except that 189 g of the polyol composition obtained in Example A7 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and film of the thermoplastic starch composition were prepared. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 345.7 MPa, and the average elongation was 734.0%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 1.7 MPa and a standard deviation of elongation of 0.8% of the film.

Example B29: Preparation of a thermoplastic starch composition and film thereof using the polyol composition of Example A8

189 g of the polyol composition obtained in Example A8 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of ethylene glycol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. to prepare a masterbatch and a film of the thermoplastic starch composition in the same manner as in Example B1. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 363.0 MPa, and the average elongation was 751.0%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 2.2 MPa and a standard deviation of elongation of 0.8% of the film.

Example B30: Preparation of a thermoplastic starch composition and film thereof using the polyol composition of Example A9

189 g of the polyol composition obtained in Example A9 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of sorbitol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. , A masterbatch and a film of a thermoplastic starch composition were prepared in the same manner as in Example B1. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 349.7 MPa, and the average elongation was 741.0%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 1.2 MPa and a standard deviation of elongation of 0.8% of the film.

Example B31: Preparation of a thermoplastic starch composition and film thereof using the polyol composition of Example A10

189 g of the polyol composition obtained in Example A10 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of sorbitol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. , A masterbatch and a film of a thermoplastic starch composition were prepared in the same manner as in Example B1. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 326.3 MPa, and the average elongation was 724.3%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.5 MPa and a standard deviation of elongation of 0.9% of the film.

Example B32: Preparation of Thermoplastic Starch Composition and Film Thereof Using Polyol Composition of Example A11

The same method as in Example B1 was performed, except that 189 g of the polyol composition obtained in Example A11 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and film of the thermoplastic starch composition were prepared. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 327.0 MPa, and the average elongation was 727.3%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0 MPa and a standard deviation of elongation of 0.9% of the film.

Example B33: Preparation of Thermoplastic Starch Composition and Film Thereof Using Polyol Composition of Example A12

189 g of the polyol composition obtained in Example A12 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of ethylene glycol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. , A masterbatch and a film of a thermoplastic starch composition were prepared in the same manner as in Example B1. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 326.0 MPa, and the average elongation was 730.3%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.8 MPa and a standard deviation of elongation of 0.5% of the film.

Example B34: Preparation of Thermoplastic Starch Composition and Film Thereof Using Polyol Composition of Example A13

Using 189 g of the polyol composition obtained in Example A13 instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, using 189 g of sorbitol instead of glycerol, and changing the content of distilled water from 167 g to 188 g, A masterbatch and film of the thermoplastic starch composition were prepared in the same manner as in Example B1. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 318.0 MPa, and the average elongation was 718.3%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.8 MPa and a standard deviation of elongation of 0.5% of the film.

Example B35: Preparation of Thermoplastic Starch Composition and Film Thereof Using Polyol Composition of Example A14

Using 189 g of the polyol composition obtained in Example A14 instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, using 189 g of sorbitol instead of glycerol, and changing the content of distilled water from 167 g to 188 g, A masterbatch and film of the thermoplastic starch composition were prepared in the same manner as in Example B1. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 318.7 MPa, and the average elongation was 722.0%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 1.2 MPa and a standard deviation of elongation of 0.8% of the film.

Example B36: Preparation of Thermoplastic Starch Composition and Film Thereof Using Polyol Composition of Example A15

The same method as in Example B1 was performed, except that 189 g of the polyol composition obtained in Example A15 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and film of the thermoplastic starch composition were prepared. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 320.3 MPa, and the average elongation was 722.7%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.5 MPa and a standard deviation of elongation of 1.2% of the film.

Example B37: Preparation of Thermoplastic Starch Composition and Film Thereof Using Polyol Composition of Example A16

The same method as in Example B1 was performed, except that 189 g of the polyol composition obtained in Example A16 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and film of the thermoplastic starch composition were prepared. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 315.7 MPa, and the average elongation was 698.7%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 2.4 MPa and a standard deviation of elongation of 1.2% of the film.

Example B38: Preparation of Thermoplastic Starch Composition and Film Thereof Using Polyol Composition of Example A17

189 g of the polyol composition obtained in Example A17 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of ethylene glycol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. to prepare a masterbatch and a film of the thermoplastic starch composition in the same manner as in Example B1. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 314.3 MPa, and the average elongation was 710.0%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.9 MPa and a standard deviation of elongation of 0.8% of the film.

Example B39: Preparation of Thermoplastic Starch Composition and Film Thereof Using Polyol Composition of Example A18

189 g of the polyol composition obtained in Example A18 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of sorbitol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. , A masterbatch and a film of a thermoplastic starch composition were prepared in the same manner as in Example B1. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 314.7 MPa, and the average elongation was 699.0%. In addition, it was confirmed that the film was uniformly formed with a standard deviation of tensile strength of 0.5 MPa and a standard deviation of elongation of 0.8% of the film.

Comparative Example B1: Preparation of a thermoplastic starch composition and film thereof using the anhydrosugar alcohol composition of Preparation Example A4

Preparation of a masterbatch and film of a thermoplastic starch composition in the same manner as in Example B1, except that 210 g of the anhydrosugar alcohol composition obtained in Preparation Example A4 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1. was tried, but extrusion molding could not be performed due to high viscosity.

Comparative Example B2: Preparation of a thermoplastic starch composition and film thereof using the anhydrosugar alcohol composition of Preparation Example A5

The same method as in Example B1 was performed, except that 210 g of the anhydrosugar alcohol composition obtained in Preparation Example A5 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of ethylene glycol was used instead of glycerol. Thus, a masterbatch and a film of the thermoplastic starch composition were prepared. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 148.3 MPa, and the average elongation was 396.7%. In addition, the standard deviation of tensile strength of the film was 1.2 MPa, and the standard deviation of elongation was 1.2%.

Comparative Example B3: Preparation of a thermoplastic starch composition and a film thereof using the anhydrosugar alcohol composition of Preparation Example A6

The same method as in Example B1 was performed, except that 210 g of the anhydrosugar alcohol composition obtained in Preparation Example A6 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of sorbitol was used instead of glycerol. A masterbatch and film of the thermoplastic starch composition were prepared. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 153.3 MPa, and the average elongation was 401.0%. In addition, the standard deviation of tensile strength of the film was 1.2 MPa, and the standard deviation of elongation was 0.8%.

Comparative Example B4: Preparation of a thermoplastic starch composition and a film thereof using the anhydrosugar alcohol-alkylene glycol composition of Preparation B19

Example B1, except that 189 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B19 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of distilled water was changed from 167 g to 188 g A masterbatch and a film of the thermoplastic starch composition were prepared in the same manner as described above. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 169.3 MPa, and the average elongation was 436.0%. In addition, the standard deviation of tensile strength of the film was 0.5 MPa, and the standard deviation of elongation was 3.7%.

Comparative Example B5: Preparation of a thermoplastic starch composition and a film thereof using the anhydrosugar alcohol-alkylene glycol composition of Preparation B20

189 g of anhydrosugar alcohol-alkylene glycol composition obtained in Preparation B20 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of ethylene glycol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and film of a thermoplastic starch composition were prepared in the same manner as in Example B1, except for the changes. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 173.0 MPa, and the average elongation was 450.0%. In addition, the standard deviation of tensile strength of the film was 0.8 MPa and the standard deviation of elongation was 0.8%.

Comparative Example B6: Preparation of a thermoplastic starch composition and a film thereof using the anhydrosugar alcohol-alkylene glycol composition of Preparation B21

189 g of anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B21 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of sorbitol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g A masterbatch and a film of a thermoplastic starch composition were prepared in the same manner as in Example B1, except for the above. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 174.7 MPa, and the average elongation was 468.7%. In addition, the standard deviation of tensile strength of the film was 1.2 MPa, and the standard deviation of elongation was 1.9%.

Comparative Example B7: Preparation of a thermoplastic starch composition and a film thereof using the anhydrosugar alcohol-alkylene glycol composition of Preparation B22

Example B1 except that 189 g of anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B22 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of distilled water was changed from 167 g to 188 g A masterbatch and a film of the thermoplastic starch composition were prepared in the same manner as described above. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 169.7 MPa, and the average elongation was 440.7%. In addition, the standard deviation of tensile strength of the film was 26.8 MPa, and the standard deviation of elongation was 43.8%.

Comparative Example B8: Preparation of a thermoplastic starch composition and a film thereof using the anhydrosugar alcohol-alkylene glycol composition of Preparation B23

189 g of anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B23 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of ethylene glycol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and film of a thermoplastic starch composition were prepared in the same manner as in Example B1, except for the changes. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 186.3 MPa, and the average elongation was 502.3%. In addition, the standard deviation of tensile strength of the film was 1.7 MPa and the standard deviation of elongation was 1.7%.

Comparative Example B9: Preparation of a thermoplastic starch composition and film thereof using the polyol composition of Comparative Example A1

189 g of the polyol composition obtained in Comparative Example A1 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of sorbitol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. , A masterbatch and a film of a thermoplastic starch composition were prepared in the same manner as in Example B1. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 176.7 MPa, and the average elongation was 498.7%. In addition, the standard deviation of tensile strength of the film was 0.5 MPa, and the standard deviation of elongation was 1.7%.

Comparative Example B10: Preparation of a thermoplastic starch composition and a film thereof using the polyol composition of Comparative Example A2

The same method as in Example B1 was performed, except that 189 g of the polyol composition obtained in Comparative Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and film of the thermoplastic starch composition were prepared. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 174.0 MPa, and the average elongation was 491.7%. In addition, the standard deviation of tensile strength of the film was 0.8 MPa, and the standard deviation of elongation was 1.2%.

Comparative Example B11: Preparation of a thermoplastic starch composition and a film thereof using the polyol composition of Comparative Example A3

189 g of the polyol composition obtained in Comparative Example A3 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of ethylene glycol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. to prepare a masterbatch and a film of the thermoplastic starch composition in the same manner as in Example B1. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 176.3 MPa, and the average elongation was 496.0%. In addition, the standard deviation of tensile strength of the film was 1.2 MPa, and the standard deviation of elongation was 2.2%.

Comparative Example B12: Preparation of a thermoplastic starch composition and a film thereof using the polyol composition of Comparative Example A4

189 g of the polyol composition obtained in Comparative Example A4 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 189 g of sorbitol was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. , A masterbatch and a film of a thermoplastic starch composition were prepared in the same manner as in Example B1. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 176.3 MPa, and the average elongation was 467.3%. In addition, the standard deviation of tensile strength of the film was 17.2 MPa, and the standard deviation of elongation was 62.2%.

Comparative Example B13: Preparation of a thermoplastic starch composition and a film thereof using the polyol composition of Comparative Example A5

The same method as in Example B1 was performed, except that 189 g of the polyol composition obtained in Comparative Example A5 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and film of the thermoplastic starch composition were prepared. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 187.0 MPa, and the average elongation was 502.3%. In addition, the standard deviation of tensile strength of the film was 1.6 MPa, and the standard deviation of elongation was 2.6%.

Comparative Example B14: Preparation of thermoplastic starch composition and film thereof using glycerol

Without using the anhydrosugar alcohol composition obtained in Preparation Example A1, the content of glycerol was changed from 189 g to 378 g, and the content of distilled water was changed from 167 g to 188 g. The same method as in Example B1 was performed, A masterbatch and film of the thermoplastic starch composition were prepared. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 222.1 MPa, and the average elongation was 505.0%. In addition, the standard deviation of tensile strength of the film was 0.8 MPa and the standard deviation of elongation was 4.1%.

Comparative Example B15: Preparation of thermoplastic starch composition and film thereof using ethylene glycol

The same method as in Example B1 was performed, except that the anhydrosugar alcohol composition obtained in Preparation Example A1 was not used, ethylene glycol 378 g was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and film of the thermoplastic starch composition were prepared. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 212.7 MPa, and the average elongation was 504.3%. In addition, the standard deviation of tensile strength of the film was 2.1 MPa, and the standard deviation of elongation was 1.2%.

Comparative Example B16: Preparation of a thermoplastic starch composition using sorbitol and a film thereof

The same method as in Example B1 was performed, except that the anhydrosugar alcohol composition obtained in Preparation Example A1 was not used, sorbitol 378 g was used instead of glycerol, and the content of distilled water was changed from 167 g to 188 g. A masterbatch and film of the starch composition were prepared. As a result of measuring the tensile strength and elongation of the prepared film three times, the average tensile strength was 214.3 MPa, and the average elongation was 511.3%. In addition, the standard deviation of tensile strength of the film was 0.9 MPa, and the standard deviation of elongation was 1.2%.

The compositions and properties of the thermoplastic starch compositions obtained in Examples B1 to B39 and Comparative Examples B1 to B16 are shown in Table 4 below.

As shown in Table 4, as a result of measuring the average and standard deviation of tensile strength of three tensile specimens of films prepared using the thermoplastic starch compositions of Examples B1 to B39 according to the present invention, the average tensile strength of three tensile specimens Although the value was excellent at 281.3 MPa or more, the tensile strength standard deviation of the three tensile specimens was 2.4 MPa or less, and the tensile strengths of the three tensile specimens were equal to each other. It can be seen that they are uniformly dispersed.

In addition, as a result of measuring the average elongation and standard deviation of three elongation specimens of films prepared using the thermoplastic starch composition of Examples B1 to B39 according to the present invention, the average elongation value of the three elongation specimens was 584.0% or more, while excellent, The elongation standard deviation range of the three elongation specimens was 2.2% or less, and the elongation deviations of the three elongation specimens were equal to each other.

However, in the case of Comparative Example B1, the viscosity was rapidly increased and extrusion molding was not easy. In the case of the film of Comparative Example B2, the tensile strength and elongation of the film were very poor. In the case of the film of Comparative Example B3, the tensile strength of the film was also The strength and elongation were very poor.

In addition, in the case of the films of Comparative Examples B4 to B6, the tensile strength and elongation of the film were poor, and in the case of the film of Comparative Example B7, the compatibility was lowered and the tensile strength and elongation of the film were very poor, but the uniformity of the film was very decreased, and in the case of the film of Comparative Example B8, the tensile strength and elongation of the film were poor.

In addition, in the case of the films of Comparative Examples B10 and B11, the tensile strength and elongation of the films were poor, and in the case of the films of Comparative Example B12, the compatibility was lowered and the tensile strength and elongation of the films were very poor, but the uniformity of the films was very decreased, and in the case of the film of Comparative Example B13, the tensile strength and elongation of the film were poor.

In addition, the films of Comparative Examples B14 to B16 using only conventional plasticizers as plasticizers had very poor tensile strength and elongation compared to the films prepared in Examples.

Claims (17)

A polyol composition comprising:
It is obtained by addition reaction of a compatibilizer to anhydrosugar alcohol composition,
The anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is a mono-anhydrosugar alcohol, the second polyol component is a dianhydrosugar alcohol, and the third polyol component has the following formula It is a polysaccharide alcohol represented by 1, the fourth polyol component is an anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1 below, and the fifth polyol component is the first to fourth polyol components At least one polymer selected from
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 1.13 to 3.41; and
iii) the average number of —OH groups per molecule in the anhydrosugar alcohol composition is 2.54 to 21.36;
A polyol composition, wherein the compatibilizer is added in an amount of greater than 3 parts by weight to less than 80 parts by weight per 100 parts by weight of the anhydrosugar alcohol composition:
[Formula 1]

In Formula 1, n is an integer of 0 to 4. The polyol composition of claim 1, wherein the first polyol component is hexitol monohydrate. The polyol composition of claim 1, wherein the second polyol component is hexitol dianhydride. The polyol composition according to claim 1, wherein the fourth polyol component is selected from a compound represented by the following formula (2), a compound represented by the following formula (3), or a mixture thereof:
[Formula 2]

[Formula 3]

In Formulas 2 and 3, n is each independently an integer of 0 to 4. The polyol composition of claim 1 , wherein the fifth polyol component comprises at least one selected from the group consisting of a condensation polymer prepared from the following polycondensation reaction:
- polycondensation reaction of the first polyol component,
- polycondensation reaction of the second polyol component,
- polycondensation reaction of the third polyol component,
- polycondensation reaction of the fourth polyol component,
- polycondensation reaction of the first polyol component and the second polyol component,
- polycondensation reaction of the first polyol component and the third polyol component,
- polycondensation reaction of the first polyol component and the fourth polyol component,
- polycondensation reaction of the second polyol component and the third polyol component;
- polycondensation reaction of the second polyol component and the fourth polyol component,
- polycondensation reaction of the third polyol component and the fourth polyol component,
- polycondensation reaction of the first polyol component, the second polyol component and the third polyol component;
- polycondensation reaction of the first polyol component, the second polyol component and the fourth polyol component;
- polycondensation reaction of the first polyol component, the third polyol component and the fourth polyol component;
- polycondensation reaction of the second polyol component, the third polyol component and the fourth polyol component, or
- Polycondensation reaction of the first polyol component, the second polyol component, the third polyol component and the fourth polyol component. The method according to claim 1, wherein the anhydrosugar-alcohol composition is subjected to a hydrogenation reaction of a glucose-containing saccharide composition to prepare a hydrogenated sugar composition, the obtained hydrogenated sugar composition is heated under an acid catalyst to perform a dehydration reaction, and the obtained dehydration reaction product is applied to a thin film. A polyol composition prepared by distillation. 7. The polyol composition of claim 6, wherein the glucose-containing saccharide composition contains from 41% to 99.5% by weight of glucose, based on the total weight of the saccharide composition. The polyol composition according to claim 1, wherein the compatibilizer is at least one selected from the group consisting of C3-C10 dicarboxylic acids or anhydrides thereof. A thermoplastic starch composition comprising:
starch; and a plasticizer; and
The plasticizer comprises: (i) the polyol composition of any one of claims 1 to 8; (ii) an anhydrosugar alcohol composition as defined in paragraph 1; or (iii) anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of the anhydrosugar alcohol composition defined in claim 1 with an alkylene oxide;
The anhydrosugar alcohol-alkylene glycol composition is a thermoplastic starch composition prepared by addition reaction of an alkylene oxide in an amount of more than 5 parts by weight to less than 700 parts by weight per 100 parts by weight of the anhydrosugar alcohol composition. 10. The method of claim 9, wherein the starch is at least one selected from the group consisting of corn starch, potato starch, sweet potato starch, tapioca starch, rice starch, wheat starch, sago starch, modified starches thereof, dextrins, or combinations thereof. Thermoplastic Starch Composition. 10. The method of claim 9, wherein the plasticizer further comprises a plasticizer component (an additional plasticizer component) other than the (i) polyol composition, (ii) anhydrosugar alcohol composition and (iii) anhydrosugar alcohol-alkylene glycol composition. , a thermoplastic starch composition. 12. The method of claim 11 wherein said additional plasticizer component is water, glycerol, glycerin, ethylene glycol, glucose, sorbitol, maltose, sucrose, cyclodextrin, glycerin diacetate, propylene glycol, polypropylene glycol, methoxyethylene glycol, pentaerythritol Or at least one selected from the group consisting of a combination thereof, a thermoplastic starch composition. The thermoplastic starch composition of claim 11 , wherein the additional plasticizer component is included in an amount of from 10 parts by weight to 90 parts by weight, based on 100 parts by weight of the total plasticizer. A masterbatch comprising the thermoplastic starch composition of claim 9 . The masterbatch of claim 14; and a thermoplastic resin; The molded article according to claim 15, wherein the thermoplastic resin is a biodegradable thermoplastic resin. 17. The method of claim 16, wherein the biodegradable thermoplastic resin is at least one selected from polybutylene adipate terephthalate, polybutylene succinate, polylactic acid, polyhydroxy alkanoate, polyethylene, polypropylene, polystyrene, or a combination thereof. , molded products.