KR20220080552A - Crosslinked polyol composition obtained by crosslinking anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition with epoxy compound, polyseter resin prepared by using the polyol composition and method for preparing the same, and powder coating composition comprising the resin - Google Patents

Abstract

The present invention relates to a crosslinked polyol composition, a polyester resin and a method for producing the same, and a powder coating composition comprising the resin, and more particularly, an anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol derived from biomass. A cross-linked polyol composition obtained by cross-linking the composition with an epoxy compound, and a polyester resin with improved eco-friendliness and improved physical properties such as appearance, hardness, and storage stability produced using the same, a method for producing the same, and the resin It relates to a powder coating composition.

Description

A crosslinked polyol composition obtained by crosslinking an anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition with an epoxy compound, a polyester resin prepared using the polyol composition and a method for manufacturing the same, and a powder coating composition comprising the resin {Crosslinked polyol composition obtained by crosslinking anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition with epoxy compound, polyseter resin prepared by using the polyol composition and method for preparing the same, and powder coating composition comprising the resin}

The present invention relates to a crosslinked polyol composition, a polyester resin and a method for producing the same, and a powder coating composition comprising the resin, and more particularly, an anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol derived from biomass. A cross-linked polyol composition obtained by cross-linking the composition with an epoxy compound, and a polyester resin with improved eco-friendliness and improved physical properties such as appearance, hardness, and storage stability produced using the same, a method for producing the same, and the resin It relates to a powder coating composition.

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 has the form of a diol having two hydroxyl groups in the molecule, and can be prepared by utilizing hexitol derived from starch (eg, Korean 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.

The use of anhydrosugar alcohol is very diverse, such as treatment of heart and blood vessel diseases, adhesives for patches, pharmaceuticals such as mouth fresheners, 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 the 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 application possibilities, and its use in actual industry is gradually increasing.

Korean Patent Laid-Open No. 10-2012-0113883 discloses a polyester resin for liquid paint having an alcohol functional group, obtained by copolymerizing a diacid component, a diol component including isosorbide, and lactic acid or a derivative thereof together in a single step. has been However, since lactic acid has both an alcohol and an acid functional group, a selective competitive reaction proceeds. Therefore, in the method for preparing a polyester resin disclosed in the above document, the reactivity is lowered during the preparation of the resin, and the reaction time is long, and the reaction time is short. As the length increases, the color of the prepared resin deteriorates, and there is a problem in that dispersion workability and heat resistance are deteriorated.

On the other hand, 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 a demand 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.

An object of the present invention is to provide a polyol composition capable of providing a polyester resin that is environmentally friendly and exhibits excellent adhesion, impact resistance and chemical resistance, and improved appearance, hardness, bending resistance and storage stability at the same time, and a polyol prepared using the same An ester resin and a powder coating composition comprising the resin are provided.

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

It is obtained by crosslinking an anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition with an epoxy compound,

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

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;

The anhydrosugar alcohol-alkylene glycol composition is prepared by addition reaction of the anhydrosugar alcohol composition with an alkylene oxide,

More than 3 parts by weight to less than 60 parts by weight of the epoxy compound per 100 parts by weight of the anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition is cross-linked,

A crosslinked polyol composition is provided:

[Formula 1]

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

A second aspect of the present invention is a method for preparing a crosslinked polyol composition,

Comprising a crosslinking reaction of an anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition and an epoxy compound,

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 is the 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, 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;

The anhydrosugar alcohol-alkylene glycol composition is prepared by addition reaction of the anhydrosugar alcohol composition with an alkylene oxide,

More than 3 parts by weight to less than 60 parts by weight of the epoxy compound per 100 parts by weight of the anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition is cross-linked,

A method for preparing a crosslinked polyol composition is provided.

A third aspect of the present invention provides a prepolymer block prepared from a monomer mixture comprising a polyol component and a polyacid component comprising the crosslinked polyol composition according to the first aspect of the present invention; and a polyacid component; as a repeating unit, it provides a polyester resin.

A fourth aspect of the present invention comprises the steps of: (1) reacting a polyol component comprising the crosslinked polyol composition according to the first aspect of the present invention with a polyhydric acid component to prepare a prepolymer; and (2) preparing a polyester resin by reacting the prepolymer prepared in step (1) with a polyacid component.

A fifth aspect of the present invention, the polyester resin according to the third aspect of the present invention; And it provides a powder coating composition comprising a curing agent.

According to the present invention, it is possible to obtain a polyester resin and a powder coating composition comprising the same, which are environmentally friendly and exhibit excellent adhesion, impact resistance and chemical resistance, and improved appearance, hardness, bending resistance and storage stability at the same time.

In addition, the polyester resin according to the present invention is a polyol composition derived from an anhydrosugar alcohol composition obtained by utilizing a by-product obtained in the process of preparing an internal dehydrated product of hydrogenated sugar or a composition obtained by adding an alkylene glycol to the anhydrous sugar alcohol composition Since it is manufactured using

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

[Crosslinked polyol composition and manufacturing method thereof]

The crosslinked polyol composition of the present invention is obtained by crosslinking an anhydrosugar alcohol composition or an anhydrosugar alcohol-alkylene glycol composition with an epoxy compound.

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; dianhydride 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 among the first to fourth polyol components, which is a fifth polyol component, preferably at least two, more preferably all of which comprises 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 the form of a tetraol having four hydroxyl groups in the molecule. In the present invention, the type of 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 with 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 in progress 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 preferably 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 greater than or equal to disaccharides, 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 appearance of the powder coating film including the polyester resin prepared using the same is poor, and the hardness and storage stability are deteriorated. Conversely, when the number average molecular weight of the anhydrosugar alcohol composition exceeds 1,589, the appearance of the powder coating film including the polyester resin prepared using the same is poor, and the hardness, bending resistance and storage stability are deteriorated.

In addition, when the polydispersity index of the anhydrosugar alcohol composition is less than 1.13, the appearance of the powder coating film including the polyester resin prepared using the same is poor, and the hardness and storage stability are deteriorated. Conversely, when the polydispersity index of the anhydrosugar alcohol composition exceeds 3.41, the appearance of the powder coating film including the polyester resin prepared using the same is poor, and the hardness, bending resistance and storage stability are deteriorated.

In addition, if the average number of -OH groups per molecule in the anhydrosugar alcohol composition is less than 2.54, the appearance of the powder coating film including the polyester resin prepared using the same is poor, and the hardness and storage stability are deteriorated. Conversely, when the average number of -OH groups per molecule in the anhydrosugar alcohol composition exceeds 21.36, the appearance of the powder coating film including the polyester resin prepared using the same is poor, and the hardness, bending resistance and storage stability are poor. it gets worse

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 more 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 (for example, glucose; mannose; fructose; and a saccharide composition including polysaccharides containing disaccharides or more including maltose), and , the obtained hydrogenated sugar composition is heated under an acid catalyst for a 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, the 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, 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 appearance of the powder coating film including the polyester resin prepared using the same is poor, hardness, resistance Flexibility and storage stability may deteriorate, and when it exceeds 99.5% by weight, the number average molecular weight of the anhydrosugar alcohol composition becomes too low, and the appearance of the powder coating film containing the polyester resin prepared using the same becomes poor, hardness and Storage stability may deteriorate.

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 wt%, an anhydrosugar alcohol composition is prepared using the hydrogenated sugar composition, and the polyester resin prepared using the anhydrosugar alcohol composition is used in a powder coating. Adhesive properties such as decreased adhesion to the adherend and surface peeling may occur, and when it exceeds 57 wt%, an anhydrosugar alcohol composition is prepared using this hydrogenated sugar composition, and poly In the process of preparing the ester resin, there may be a problem in that the composition is cured or gelled.

Anhydrosugar alcohol-alkylene glycol composition

In the present invention, the anhydrosugar alcohol-alkylene glycol composition refers to a composition obtained by an addition reaction of the above-described anhydrosugar alcohol composition with an alkylene oxide, and accordingly, the anhydrosugar alcohol-alkylene glycol composition comprises the first to the first 5, including an adduct obtained by reacting at least one hydroxyl group with an alkylene oxide at one end of each polyol component, specifically, the anhydrosugar alcohol-alkylene glycol composition is an alkylene oxide adduct of the first polyol component (hereinafter referred to as “the second 1 anhydrosugar alcohol-alkylene glycol), an alkylene oxide adduct of the second polyol component (hereinafter referred to as “second anhydrosugar alcohol-alkylene glycol”), the third polyol component Alkylene oxide adduct (hereinafter referred to as “the third anhydrosugar alcohol-alkylene glycol”), an alkylene oxide adduct of the fourth polyol component (hereinafter “the fourth anhydrosugar alcohol-alkylene glycol”) ) and an alkylene oxide adduct of the fifth polyol component (hereinafter referred to as “the 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.

In one embodiment, the amount of the addition-reacted alkylene oxide per 100 parts by weight of the anhydrosugar alcohol composition may be more than 30 parts by weight to less than 700 parts by weight. If the added amount of alkylene oxide per 100 parts by weight of the anhydrosugar alcohol composition is too less than the above level, the appearance of the powder coating film including the polyester resin prepared using the prepared anhydrosugar alcohol-alkylene glycol composition will be poor. and may deteriorate hardness, flex resistance and storage stability. Conversely, if the added amount of alkylene oxide is excessively greater than the above level, the appearance of the powder coating film including the polyester resin prepared using the prepared anhydrosugar alcohol-alkylene glycol composition may deteriorate, and hardness and storage stability may deteriorate. can

In one embodiment, the amount of the addition-reacted alkylene oxide per 100 parts by weight of the anhydrosugar alcohol composition may be, for example, more than 30 parts by weight, 35 parts by weight or more, 40 parts by weight or more, 45 parts by weight or more, or 50 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 performed for 5 hours, but is not limited thereto.

Epoxy compound and crosslinking reaction thereof

The crosslinked polyol composition of the present invention is prepared by crosslinking the epoxy compound in an amount of more than 3 parts by weight to less than 60 parts by weight per 100 parts by weight of the anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition.

In one embodiment, the epoxy compound is bisphenol A-epichlorohydrin resin, diglycidyl ether resin of bisphenol A, novolak-type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, bi-cyclic epoxy resin, glycy It may be selected from the group consisting of a dill ester type epoxy resin, a brominated epoxy resin, a bio-derived epoxy resin, an epoxidized soybean oil, a rubber-modified epoxy compound, or a combination thereof, but is not limited thereto.

In another embodiment, the epoxy compound is a natural rubber-modified epoxy compound, a carboxyl-terminated butadiene acrylonitrile-modified epoxy compound, a core-shell rubber-modified epoxy compound, a polybutadiene-modified epoxy compound, an acrylonitrile-butadiene-modified epoxy compound, styrene -A rubber selected from the group consisting of butadiene-modified epoxy compound, epoxy-terminated butadiene acrylonitrile-modified epoxy compound, amine-terminated butadiene acrylonitrile-modified epoxy compound, hydroxy-terminated butadiene acrylonitrile-modified epoxy compound, or a combination thereof It may be a modified epoxy compound, but is not limited thereto.

When the amount of the epoxy compound used per 100 parts by weight of the anhydrosugar alcohol composition or the anhydrosugar alcohol-alkylene glycol composition is 3 parts by weight or less, the hardness and appearance of the powder coating film including the polyester resin prepared using the same is poor. becomes Conversely, when the amount of the epoxy compound used per 100 parts by weight of the anhydrosugar alcohol composition or the anhydrosugar alcohol-alkylene glycol composition is 60 parts by weight or more, the hardness and appearance of the powder coating film including the polyester resin prepared using the same This deteriorates, and storage stability deteriorates.

Accordingly, according to another aspect of the present invention, there is provided a method for preparing a cross-linked polyol composition, comprising the step of cross-linking the anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition and the epoxy compound.

In one embodiment, the crosslinking reaction of the anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition and the epoxy compound is a catalyst, such as an organic tin-based catalyst (eg, dibutyltin dilaurate, etc.) In the presence, it may be carried out at an elevated temperature (eg, 110° C. to 180° C., or 120° C. to 160° C.), for example, for 1 to 10 hours, or for 1 to 8 hours, but is not limited thereto.

[Polyester resin and its manufacturing method]

According to another aspect of the present invention, a prepolymer block prepared from a monomer mixture comprising a polyol component and a polyacid component comprising the cross-linked polyol composition of the present invention as described above; and a polyacid component; as a repeating unit, it provides a polyester resin.

In one embodiment, the amount of the polyol composition of the present invention included as a repeating unit in the polyester resin of the present invention may be more than 0.3 parts by weight to less than 27.3 parts by weight, based on 100 parts by weight of the total polyester resin. If the content of the repeating unit derived from the polyol composition of the present invention in the polyester resin is out of the above range, it may be difficult to apply to a powder coating material due to problems such as lowering of physical properties such as leveling, hardness, and storage stability.

More specifically, the amount of the polyol composition of the present invention included as a repeating unit in the polyester resin of the present invention is 0.4 parts by weight or more, 0.5 parts by weight or more, 1 part by weight or more, based on 100 parts by weight of the total polyester resin, It may be 1.5 parts by weight or more or 1.8 parts by weight or more, and may be 25 parts by weight or less, 23 parts by weight or less, 20 parts by weight or less, 18 parts by weight or less, or 15.7 parts by weight or less, but is not limited thereto.

any additional diol component

In one embodiment, the polyol component used for preparing the polyester resin of the present invention may further include a diol component (hereinafter, “additional diol component”) other than the cross-linked polyol composition of the present invention.

In one embodiment, the additional diol component may further include a diol compound other than anhydrosugar alcohol, for example, an aliphatic diol, an alicyclic diol, an aromatic diol, or a combination thereof, and preferably further include an aliphatic diol. have. In addition, some or all of these diol components may be biomass-derived diols.

As the aliphatic diol, for example, a linear or branched aliphatic diol having 2 to 8 carbon atoms can be used, and specifically, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol (propylene glycol), 1,2-propanediol, 1,4-butanediol (1,4-butylene glycol), 1,3-butanediol, 1,2-butanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol) ), pentanediol (eg, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,2-pentanediol, etc.), hexanediol (eg, 1,6- hexanediol, 1,5-hexanediol, 1,4-hexanediol, 1,3-hexanediol, 1,2-hexanediol, etc.), heptanediol (eg, 1,7-heptanediol, 1,6 -heptanediol, 1,5-heptanediol, 1,4-heptanediol, 1,3-heptanediol, 1,2-heptanediol, etc.) and combinations thereof may be used.

As the alicyclic diol, for example, an alicyclic diol having 5 to 20 carbon atoms including 1 to 4 5-membered ring structures or 6-membered ring structures can be used, and specifically, 1,4-cyclohexane Diol, 1,3-cyclohexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, tetramethylcyclobutanediol, One selected from the group consisting of tricyclodecanedimethanol, adamantanediol, and combinations thereof may be used.

As the aromatic diol, for example, an aromatic diol having 6 to 20 carbon atoms and including 1 to 4 aromatic ring structures can be used, and specifically, bisphenol A, 4,4'-dihydroxy-diphenyl Sulfone, 4,4'-biphenol, hydroquinone, 4,4'-dihydroxy-diphenyl ether, 3-(4-hydroxyphenoxy)phenol, bis(4-hydroxyphenyl)sulfide and these One selected from the group consisting of a combination of may be used.

In one embodiment, when the polyol component used for preparing the polyester resin of the present invention includes such an additional diol component, the polyol component is 1 weight of the crosslinked polyol composition of the present invention based on 100 parts by weight of the total polyol component parts by weight to 50 parts by weight (more specifically 1 part by weight to 40 parts by weight, even more specifically 1.1 parts by weight to 32.4 parts by weight), and 50 parts by weight to 99 parts by weight (more specifically 60 parts by weight) of an additional diol component parts by weight to 99 parts by weight, more specifically 67.6 parts by weight to 98.9 parts by weight), but is not limited thereto.

polyacid component

In the present invention, as the polyhydric acid component used in the preparation of the polyester resin, diacid, triacid, or a mixture thereof may be used, and specifically, aromatic dicarboxylic acid having 8 to 14 carbon atoms as diacid (eg, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, etc.), aliphatic dicarboxylic acid having 4 to 12 carbon atoms (eg, (1,4- or 1,3-, etc.) cyclo hexanedicarboxylic acid, phthalic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, adipic acid, glutaric acid, etc.) and combinations thereof may be used, and as the trivalent acid, trimellitic acid or anhydride thereof can be used

In the present invention, there is no particular limitation on the usage ratio of the polyol component and the polyacid component used in the production of the polyester resin, for example, the amount of the polyol component is 80 to 120 moles based on 100 moles of the total polyol components. may be, or may be 90 moles to 110 moles. If the amount of the polyacid component is less than the above level compared to the total polyol component used in the production of the polyester resin, the content of the curing agent is lowered during the production of the powder coating, so there may be a problem in that chemical resistance, impact resistance, and hardness are lowered, and vice versa. If it is higher than the above level, there may be a problem in that the appearance of the coating film and leveling are deteriorated when applied to a powder coating.

In one embodiment, the polyester resin of the present invention may have, for example, an acid value of 40 to 70 mgKOH/g, and a viscosity (measured with a Brookfield viscometer at 200° C.) of 2,000 to 6,000 cPs, preferably 2,000 to It may be 5,000 cPs, more preferably 3000 to 5000 cPs, and a glass transition temperature of 55 to 100° C., preferably 55 to 75° C., more preferably 55 to 70° C., and a number average molecular weight of 2,500 to It may be 5,000, preferably 3,000 to 4,500, but is not limited thereto.

Method for producing polyester resin

According to another aspect of the present invention, (1) preparing a prepolymer by reacting a polyol component comprising the crosslinked polyol composition of the present invention with a polyacid component; and (2) reacting the prepolymer prepared in step (1) with a polyacid component to prepare a polyester resin; including, a method for producing a polyester resin is provided.

In the method for producing the polyester resin of the present invention, the cross-linked polyol composition of the present invention and the polyhydric acid component are as described above.

In one embodiment, the polyol component may further include a diol component other than the cross-linked polyol composition of the present invention, and the additional diol component is as described above.

In one embodiment, in the step (1), the reaction of the polyol component and the polyacid component (preferably the diacid component) is a catalyst, such as an organic tin-based catalyst (e.g., monobutyltin oxide, etc.), In the presence of an organic titanium-based catalyst (tetra-n-butyl titanate, etc.), or a strong acid catalyst, etc., at an elevated temperature (eg, 110° C. to 280° C., or 120° C. to 250° C.), for example, 1 to 3 hours. It may be carried out for a period of time, or 2 to 3 hours, but is not limited thereto. In one embodiment, the prepolymer obtained as a result of step (1) may have, for example, an acid value of 15 to 30 mgKOH/g, and a viscosity of 1,500 to 4,000 cPs (measured with a Brookfield viscometer at 200° C.) , but is not limited thereto.

In one embodiment, in the step (2), the reaction of the prepolymer and the polyacid component (preferably a triacid, or a mixture of triacid and diacid) is optionally a catalyst (e.g., a tin-based catalyst, for example, In the presence of monobutyltin oxide), it may be carried out at an elevated temperature (eg, 165 ° C. to 230 ° C., or 175 ° C. to 230 ° C.), but is not limited thereto. In one embodiment, the polyester resin obtained as a result of step (2) may have, for example, an acid value of 40 to 70 mgKOH/g, and a viscosity (measured with a Brookfield viscometer at 200° C.) of 2,000 to 6,000 cPs, Preferably it may be 2,000 ~ 5,000 cPs, more preferably 3000 ~ 5000 cPs, the glass transition temperature may be 55 ~ 100 ℃, preferably 55 ~ 75 ℃, more preferably 55 ~ 70 ℃, The average molecular weight may be 2,500 to 5,000, preferably 3,000 to 4,500, but is not limited thereto.

In addition, when the polyester resin is subjected to a curing reaction with an epoxy curing agent, an additive that increases the reaction rate, for example, ethyltriphenylphosphonium bromide may be additionally used in step (2).

[Powder coating composition]

According to another aspect of the present invention, there is provided a powder coating composition comprising the polyester resin of the present invention and a curing agent.

As the curing agent, a curing agent commonly used in powder coating compositions may be used without limitation, for example, an epoxy resin curing agent may be used, and as the epoxy resin curing agent, a phenol compound (eg, bisphenol A, bisphenol F, or a mixture thereof) ) and a reaction of an epoxy resin may be used, but the present invention is not limited thereto.

The amount of the polyester resin and curing agent included in the powder coating composition of the present invention is not particularly limited. For example, based on 100 parts by weight of the total of the polyester resin and the curing agent, 40 to 80 parts by weight of the polyester resin and 20 to 20 parts by weight of the curing agent 60 parts by weight, or 50 to 70 parts by weight of the polyester resin and 30 to 50 parts by weight of the curing agent may be included, but is not limited thereto.

The powder coating composition of the present invention may further include one or more additives commonly used in the powder coating composition. Such additives include, for example, 1 selected from pinhole inhibitors (eg benzoin), flowability enhancers, wax components (eg polyethylene wax), white pigments (eg titanium dioxide) and extender pigments (eg barium sulfate) More than one species may be used, but is not limited thereto. There is no particular limitation on the amount of these additives used, for example, based on 100 parts by weight of the total of the polyester resin and the curing agent, 1 to 70 parts by weight of the pigment component may be used, and 0.1 to 10 parts by weight of other additive components may be used. , but is not limited thereto.

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 A1: Preparation of anhydrosugar alcohol composition using glucose in an amount 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 greater than or equal to disaccharide) to obtain 1,819 g, put it in 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 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% aqueous sodium hydroxide solution was added to neutralize the reaction product. Thereafter, the temperature was cooled to 100° C. or less, and the resultant solution was 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% by weight, 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 under 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 wt%, isomannide (dianhydrosugar alcohol) [second polyol component] 0.4 wt%, sorbitan (monoanhydride) alcohol) [first polyol component] 7.4% by weight, 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 number average molecular weight of the composition is 208 g/mol, the 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 anhydrosugar alcohol composition using a saccharide composition containing 85.2 wt% of glucose

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) The 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 solids, 84.1 wt% of sorbitol, 2.8 wt% of mannitol, and 13.1 wt% of a polysaccharide alcohol greater than or equal to disaccharide) with a stirrer Concentrated by heating to 100 ℃ in a batch reactor with attached, to obtain a concentrated hydrogenated sugar composition 1,000g.

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 gas chromatography analysis of the obtained anhydrosugar-alcohol conversion solution, 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, isosorbide (dianhydrosugar alcohol) 4.0% by weight, isomannide (dianhydrosugar alcohol) 1.6% by weight, sorbitan (monoanhydrosugar alcohol) 2.1% by weight, 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 anhydrosugar alcohol composition using a saccharide composition containing 50.2 wt% of glucose

Preparation Example 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) 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 solid content, sorbitol 48.5 wt%, mannitol 3.6 wt%, disaccharide or higher polysaccharide alcohol 47.9 wt%), and this was stirred Concentrated by heating to 100 ℃ in a batch reactor with attached, to obtain a concentrated hydrogenated sugar composition 1,000g.

The concentrated hydrogenated sugar composition, 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. With respect to 1,000 g, a dehydration reaction was performed in the same manner as in Preparation Example A1 to convert to anhydrosugar alcohol. 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 separating the distillate, isosorbide (dianhydrosugar alcohol) 0.9% by weight, isomannide (dianhydrosugar alcohol) 2.1% by weight, sorbitan (monoanhydrosugar alcohol) 0.9% by weight, 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 755 mg KOH/g of the composition, 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

A liquid hydrogenated sugar having a concentration of 55% by weight by performing a hydrogenation reaction in the same manner as in Preparation Example A1, except that 99.9% by weight of purified glucose crystals separated in the glucose manufacturing process were used in place of the 97% pure glucose product. 1,819 g of a composition (based on solid content, sorbitol 99.1 wt%, mannitol 0.2 wt%, disaccharide or higher polysaccharide alcohol 0.7 wt%) was obtained, put into a batch reactor equipped with a stirrer, and concentrated by heating to 100 ° C. 1,000 g were 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 It 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 827 g, and as a result of analyzing the obtained anhydrosugar-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 , and the composition had a polydispersity index of 1.12, a hydroxyl value of 740 mg KOH/g, and an average number of -OH groups per molecule in the composition of about 272 g of a polyol composition of 2.53.

Preparation A5: Preparation of anhydrosugar alcohol composition using saccharide composition containing 40.1 wt% of glucose

Preparation Example Except for using 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) in place of the 97% pure glucose product) The 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% (solids basis, sorbitol 38.8 wt%, mannitol 4.1 wt%, disaccharide or higher polysaccharide alcohol 57.1 wt%), and this was stirred Concentrated by heating to 100 ℃ in a batch reactor with attached, to obtain a concentrated hydrogenated sugar composition 1,000g.

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 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 wt%, isomannide (dianhydrosugar alcohol) 2.3 wt%, sorbitan (monanhydrosugar alcohol) 0.5 wt%, 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 a polyol composition having a polydispersity index of 3.42, a hydroxyl value of 754 mg KOH/g of the composition, and an average number of -OH groups per molecule in the composition of 21.37 was obtained.

<Preparation of anhydrous sugar alcohol-alkylene glycol composition>

Preparation B1: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 50 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

240 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A1 and 0.4 g of KOH were placed in a pressure reactor, and the pressurization and exhaust process with nitrogen were repeated three times. Thereafter, the temperature inside the reactor was raised to 100° C. to remove moisture, and after all the moisture was removed, 120 g (50 parts by weight) of ethylene oxide was slowly injected and reacted at 100° C. to 140° C. After that, 4 g of a metal adsorbent (Ambosol MP20) is added to remove metal and by-products, the temperature inside the reactor is raised again, and the residual metal content is monitored while stirring at 100° C. to 120° C. for 1 hour to 5 hours, and then the metal is completely removed If it is not detected, the temperature inside the reactor is cooled to 60° C. to 90° C. and filtered to obtain 344 g of anhydrosugar alcohol-alkylene glycol composition.

Preparation B2: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 200 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

The same as in Preparation Example B1, except that the content of the anhydrosugar alcohol composition obtained in Preparation Example A1 was changed from 240 g to 140 g (100 parts by weight), and 280 g (200 parts by weight) of propylene oxide was used instead of ethylene oxide. The method was carried out to obtain 415 g of anhydrosugar alcohol-alkylene glycol composition.

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 A2

Using 70 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A2 instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and changing the content of ethylene oxide from 120 g to 350 g (500 parts by weight) Except that, in the same manner as in Preparation Example B1, 416 g of anhydrosugar alcohol-alkylene glycol composition was obtained.

Preparation B4: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 50 parts by weight of propylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A2

280 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 140 g (50 parts by weight) of propylene oxide was used instead of ethylene oxide except that And, 416 g of anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1.

Preparation B5: 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

70 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 350 g (500 parts by weight) of propylene oxide was used instead of ethylene oxide except that and 417 g of anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1.

Preparation B6: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 200 parts by weight of ethylene oxide per 100 parts by weight of the anhydrosugar alcohol composition of Preparation A3

In place of the anhydrosugar alcohol composition obtained in Preparation Example A1, 140 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A3 was used, and the content of ethylene oxide was 120 g to 280 g (200 parts by weight) except that it was used and 413 g of anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1.

<Preparation of polyol composition crosslinked with epoxy compound>

Example A1: Crosslinked polyol composition prepared by crosslinking 5 parts by weight of bisphenol A diglycidyl ether (DGEBA) per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

240 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A1 in a three-necked glass reactor with a stirrer, 12 g (5 parts by weight) of bisphenol A diglycidyl ether (YD-128, Kukdo Chemical Co., Ltd.) And 0.5 g of dibutyltin dilaurate (Aldrich Co., Ltd.) as a reaction catalyst was added, the temperature inside the reactor was raised to 150° C., and the crosslinking reaction was carried out while stirring for 2 hours. By cooling the reaction product to room temperature after completion of the crosslinking reaction, 244 g of a crosslinked polyol composition based on anhydrosugar alcohol composition was obtained.

Example A2: Crosslinked polyol composition prepared by crosslinking 25 parts by weight of bisphenol A diglycidyl ether per 100 parts by weight of anhydrosugar alcohol-alkylene glycol composition of Preparation B1

340 g (100 parts by weight) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of bisphenol A diglycidyl ether was 12 g to 85 g (25 parts by weight), the same method as in Example A1 was followed to obtain 410 g of a crosslinked polyol composition based on anhydrosugar alcohol-alkylene glycol composition.

Example A3: Crosslinked polyol composition prepared by crosslinking 50 parts by weight of bisphenol A diglycidyl ether per 100 parts by weight of anhydrosugar alcohol-alkylene glycol composition of Preparation B2

330 g (100 parts by weight) of the 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 bisphenol A diglycidyl ether was adjusted from 12 g to 165 g. Except for changing to (50 parts by weight), 487 g of a crosslinked polyol composition based on anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Example A1.

Example A4: Crosslinked polyol composition prepared by crosslinking 5 parts by weight of a CSR-modified epoxy compound per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A2

300 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 CSR (Core-Shell Rubber) was used instead of bisphenol A diglycidyl ether. 297 g of a crosslinked polyol composition based on anhydrosugar alcohol composition was obtained in the same manner as in Example A1, except that 15 g (5 parts by weight) of a modified epoxy compound (MX-154, KANEKA Co., Ltd.) was used. .

Example A5: Crosslinked polyol composition prepared by crosslinking 25 parts by weight of a CSR-modified epoxy compound per 100 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B3

Use 400 g (100 parts by weight) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B3 instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and replace the bisphenol A diglycidyl ether with CSR modified epoxy Except that 100 g (25 parts by weight) of the compound was used, 494 g of a crosslinked polyol composition based on anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Example A1.

Example A6: Crosslinked polyol composition prepared by crosslinking 50 parts by weight of CSR-modified epoxy compound per 100 parts by weight of anhydrosugar alcohol-alkylene glycol composition of Preparation Example B4

In place of the anhydrosugar alcohol composition obtained in Preparation Example A1, 330 g (100 parts by weight) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B4 was used, and in place of bisphenol A diglycidyl ether, CSR-modified epoxy 480 g of a crosslinked polyol composition based on anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Example A1, except that 165 g (50 parts by weight) of the compound was used.

Example A7: Cross-linked polyol composition prepared by crosslinking 50 parts by weight of a natural rubber-modified epoxy compound per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A3

330 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 a natural rubber-modified epoxy compound (KR) in place of bisphenol A diglycidyl ether -909, Kukdo Chemical (manufactured by)) 490 g of a crosslinked polyol composition based on anhydrosugar alcohol composition was obtained in the same manner as in Example A1, except that 165 g (50 parts by weight) was used.

Example A8: Polyol composition prepared by crosslinking 25 parts by weight of a natural rubber-modified epoxy compound per 100 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B5

400 g (100 parts by weight) 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 natural rubber was modified in place of bisphenol A diglycidyl ether. Except for using 100 g (25 parts by weight) of the epoxy compound, 489 g of a crosslinked polyol composition based on anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Example A1.

Example A9: Cross-linked polyol composition prepared by crosslinking 5 parts by weight of natural rubber-modified epoxy compound per 100 parts by weight of anhydrosugar alcohol-alkylene glycol composition of Preparation Example B6

400 g (100 parts by weight) 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 natural rubber was modified in place of bisphenol A diglycidyl ether. Except that 20 g (5 parts by weight) of the epoxy compound was used, 418 g of a crosslinked polyol composition based on anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Example A1.

Comparative Example A1: Crosslinked polyol composition prepared by crosslinking 3 parts by weight of bisphenol A diglycidyl ether per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A1

241 g of a polyol composition based on anhydrosugar alcohol composition was obtained in the same manner as in Example A1, except that the content of bisphenol A diglycidyl ether was changed from 12 g to 7.2 g (3 parts by weight).

Comparative Example A2: Polyol composition prepared by crosslinking 60 parts by weight of bisphenol A diglycidyl ether per 100 parts by weight of anhydrosugar alcohol-alkylene glycol composition of Preparation B2

Instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, 310 g (100 parts by weight) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B2 was used, and the content of bisphenol A diglycidyl ether was 12 g to 186 g. (60 parts by weight), 490 g of a crosslinked polyol composition based on anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Example A1.

Comparative Example A3: Crosslinked polyol composition prepared by crosslinking 3 parts by weight of a CSR-modified epoxy compound per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A2

300 g (100 parts by weight) of the anhydrosugar alcohol composition obtained in Preparation Example A2 was used in place of the anhydrosugar alcohol composition obtained in Preparation Example A1, and 9 g (3 g) of the CSR modified epoxy compound in place of the bisphenol A diglycidyl ether. 297 g of a crosslinked polyol composition based on anhydrosugar alcohol composition was obtained in the same manner as in Example A1, except that parts by weight) were used.

Comparative Example A4: Crosslinked polyol composition prepared by crosslinking 60 parts by weight of a CSR-modified epoxy compound per 100 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation Example B2

In place of the anhydrosugar alcohol composition obtained in Preparation Example A1, 310 g (100 parts by weight) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B2 was used, and bisphenol A diglycidyl ether was replaced with CSR modified epoxy. 486 g of a crosslinked polyol composition based on anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Example A1, except that 186 g (60 parts by weight) of the compound was used.

Comparative Example A5: Cross-linked polyol composition prepared by crosslinking 60 parts by weight of a natural rubber-modified epoxy compound per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A3

310 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 186 g of a natural rubber-modified epoxy compound instead of bisphenol A diglycidyl ether ( 60 parts by weight), 492 g of a crosslinked polyol composition based on anhydrosugar alcohol composition was obtained in the same manner as in Example A1.

Comparative Example A6: Crosslinked polyol composition prepared by crosslinking 3 parts by weight of a natural rubber-modified epoxy compound per 100 parts by weight of the anhydrosugar alcohol-alkylene glycol composition of Preparation B6

410 g (100 parts by weight) 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 natural rubber was modified in place of bisphenol A diglycidyl ether. Except that 12.3 g (3 parts by weight) of the epoxy compound was used, 409 g of a crosslinked polyol composition based on anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Example A1.

Comparative Example A7: Cross-linked polyol composition prepared by crosslinking 10 parts by weight of bisphenol A diglycidyl ether per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A4

270 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 the content of bisphenol A diglycidyl ether was changed from 12 g to 27 g (10 parts by weight). ), to obtain 286 g of a crosslinked polyol composition based on anhydrosugar alcohol composition in the same manner as in Example A1.

Comparative Example A8: Crosslinked polyol composition prepared by crosslinking 10 parts by weight of a CSR-modified epoxy compound per 100 parts by weight of the anhydrosugar alcohol composition of Preparation Example A5

300 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 30 g (10 g) of the CSR-modified epoxy compound instead of the bisphenol A diglycidyl ether. 311 g of a crosslinked polyol composition based on anhydrosugar alcohol composition was obtained in the same manner as in Example A1, except that parts by weight) were used.

<Production of polyester resin>

Example B1: Preparation of a polyester resin using the crosslinked polyol composition of Example A1

Step 1: Preparation of prepolymer

300.9 g of neopentyl glycol, 358.7 g of ethylene glycol, 75.7 g of the crosslinked polyol composition of Example A1, 800 g of terephthalic acid, and 2.7 g of monobutyltin oxide (BT-300, Songwon Industrial Co., Ltd.) as a catalyst were mixed with a nitrogen gas pipe and a cooling device. was placed in a five-neck flask containing a column, stirrer, thermometer and heater, and the temperature was gradually raised. When the temperature of 120 ° C to 160 ° C is reached, the condensed water is drained, and the temperature is raised to about 240 ° C to 250 ° C while managing the glycol in the condensed water, and then 1.4 g of tributyl phosphite is added to prepare a prepolymer.

Step 2: Preparation of polyester resin

1,200 g of the prepolymer prepared in the first step, 270 g of trimellitic anhydride, and 33 g of succinic acid prepared in the first step were placed in a 5-neck flask equipped with a column, stirrer, thermometer and heater equipped with a nitrogen gas pipe and cooling device, and heated at 220°C to 230°C. Then, the reaction was carried out while maintaining the temperature of the reactant at 220 °C to 230 °C and removing the condensed water. And finally, in order to increase the degree of polymerization of the polyester resin, excess nitrogen or reduced pressure (50 to 200 mmHg) is used to remove unextracted condensed water and unreacted substances in the polyester resin, and 4.1 g of ethyltriphenylphosphonium bromide was added to prepare a polyester resin. In this case, the prepared polyester resin exhibited an acid value of 60.1 mgKOH/g, a viscosity of 5,610 cPs (measured by Brookfield viscosity at 200°C), and a glass transition temperature of 66.8°C, and the results are shown in Table 1 below.

Example B2: Preparation of a polyester resin using the crosslinked polyol composition of Example A2

Step 1: Preparation of prepolymer

1 of Example B1, except that the neopentyl glycol content was changed from 300.9 g to 250.8 g, and 135.2 g of the cross-linked polyol composition of Example A2 was used instead of 75.7 g of the cross-linked polyol composition of Example A1 A prepolymer of a polyester resin was prepared by performing the same method as the step.

Step 2: Preparation of polyester resin

A polyester resin was prepared in the same manner as in the second step of Example B1, except that 1,200 g of the prepolymer prepared in the first step was used instead of the prepolymer obtained in the first step of Example B1. . The polyester resin prepared at this time exhibited an acid value of 54.8 mgKOH/g, a viscosity of 4,990 cPs (measured by Brookfield viscosity at 200°C), and a glass transition temperature of 62.5°C, and the results are shown in Table 1 below.

Example B3: Preparation of a polyester resin using the crosslinked polyol composition of Example A3

Step 1: Preparation of prepolymer

The first step of Example B1, except that the neopentyl glycol content was changed from 300.9 g to 336 g, and 44.7 g of the cross-linked polyol composition of Example A3 was used instead of 75.7 g of the cross-linked polyol composition of Example A1 A prepolymer of a polyester resin was prepared in the same manner as described above.

Step 2: Preparation of polyester resin

A polyester resin was prepared in the same manner as in the second step of Example B1, except that 1,200 g of the prepolymer prepared in the first step was used instead of the prepolymer obtained in the first step of Example B1. . At this time, the prepared polyester resin exhibited an acid value of 67.2 mgKOH/g, a viscosity of 5,300 cPs (measured by Brookfield viscosity at 200°C), and a glass transition temperature of 64.3°C, and the results are shown in Table 1 below.

Example B4: Preparation of a polyester resin using the crosslinked polyol composition of Example A4

Step 1: Preparation of prepolymer

1 of Example B1, except that the neopentyl glycol content was changed from 300.9 g to 346.1 g, and 7.5 g of the cross-linked polyol composition of Example A4 was used instead of 75.7 g of the cross-linked polyol composition of Example A1 A prepolymer of a polyester resin was prepared by performing the same method as the step.

Step 2: Preparation of polyester resin

A polyester resin was prepared in the same manner as in the second step of Example B1, except that 1,200 g of the prepolymer prepared in the first step was used instead of the prepolymer obtained in the first step of Example B1. . At this time, the prepared polyester resin exhibited an acid value of 64.7 mgKOH/g, a viscosity of 3,950 cPs (measured by Brookfield viscosity at 200°C), and a glass transition temperature of 62.0°C, and the results are shown in Table 1 below.

Example B5: Preparation of a polyester resin using the crosslinked polyol composition of Example A5

Step 1: Preparation of prepolymer

The neopentyl glycol content was changed from 300.9 g to 263.3 g, the ethylene glycol content was changed from 358.7 g to 313.8 g, the terephthalic acid content was changed from 800 g to 700 g, and instead of 75.7 g of the crosslinked polyol composition of Example A1, A prepolymer of a polyester resin was prepared in the same manner as in the first step of Example B1, except that 276.2 g of the crosslinked polyol composition of Example A5 was used.

Step 2: Preparation of polyester resin

A polyester resin was prepared in the same manner as in the second step of Example B1, except that 1,200 g of the prepolymer prepared in the first step was used instead of the prepolymer obtained in the first step of Example B1. . In this case, the prepared polyester resin exhibited an acid value of 49.3 mgKOH/g, a viscosity of 2,820 cPs (measured by Brookfield viscosity at 200°C), and a glass transition temperature of 53.1°C, and the results are shown in Table 1 below.

Example B6: Preparation of a polyester resin using the crosslinked polyol composition of Example A6

Step 1: Preparation of prepolymer

The neopentyl glycol content was changed from 300.9 g to 305.6 g, the ethylene glycol content was changed from 358.7 g to 336.3 g, the terephthalic acid content was changed from 800 g to 750 g, and instead of 75.7 g of the crosslinked polyol composition of Example A1, A prepolymer of a polyester resin was prepared in the same manner as in the first step of Example B1, except that 119.3 g of the crosslinked polyol composition of Example A6 was used.

Step 2: Preparation of polyester resin

A polyester resin was prepared in the same manner as in the second step of Example B1, except that 1,200 g of the prepolymer prepared in the first step was used instead of the prepolymer obtained in the first step of Example B1. . In this case, the prepared polyester resin exhibited an acid value of 54.5 mgKOH/g, a viscosity of 3,390 cPs (measured by Brookfield viscosity at 200°C), and a glass transition temperature of 57.6°C, and the results are shown in Table 1 below.

Example B7: Preparation of a polyester resin using the crosslinked polyol composition of Example A7

Step 1: Preparation of prepolymer

The neopentyl glycol content was changed from 300.9 g to 211.6 g, the ethylene glycol content was changed from 358.7 g to 336.3 g, the terephthalic acid content was changed from 800 g to 750 g, and instead of 75.7 g of the crosslinked polyol composition of Example A1, A prepolymer of a polyester resin was prepared in the same manner as in the first step of Example B1, except that 251.7 g of the crosslinked polyol composition of Example A7 was used.

Step 2: Preparation of polyester resin

A polyester resin was prepared in the same manner as in the second step of Example B1, except that 1,200 g of the prepolymer prepared in the first step was used instead of the prepolymer obtained in the first step of Example B1. . In this case, the prepared polyester resin exhibited an acid value of 51.1 mgKOH/g, a viscosity of 3,510 cPs (measured by Brookfield viscosity at 200°C), and a glass transition temperature of 56.9°C, and the results are shown in Table 1 below.

Example B8: Preparation of a polyester resin using the crosslinked polyol composition of Example A8

Step 1: Preparation of prepolymer

The neopentyl glycol content was changed from 300.9 g to 305.6 g, the ethylene glycol content was changed from 358.7 g to 336.3 g, the terephthalic acid content was changed from 800 g to 750 g, and instead of 75.7 g of the crosslinked polyol composition of Example A1, A prepolymer of a polyester resin was prepared in the same manner as in the first step of Example B1, except that 176.9 g of the crosslinked polyol composition of Example A8 was used.

Step 2: Preparation of polyester resin

A polyester resin was prepared in the same manner as in the second step of Example B1, except that 1,200 g of the prepolymer prepared in the first step was used instead of the prepolymer obtained in the first step of Example B1. . At this time, the prepared polyester resin exhibited an acid value of 53.8 mgKOH/g, a viscosity of 3,240 cPs (measured by Brookfield viscosity at 200°C), and a glass transition temperature of 57.6°C, and the results are shown in Table 1 below.

Example B9: Preparation of a polyester resin using the crosslinked polyol composition of Example A9

Step 1: Preparation of prepolymer

1 of Example B1, except that the neopentyl glycol content was changed from 300.9 g to 348.6 g, and 7.8 g of the cross-linked polyol composition of Example A9 was used instead of 75.7 g of the cross-linked polyol composition of Example A1 A prepolymer of a polyester resin was prepared by performing the same method as the step.

Step 2: Preparation of polyester resin

A polyester resin was prepared in the same manner as in the second step of Example B1, except that 1,200 g of the prepolymer prepared in the first step was used instead of the prepolymer obtained in the first step of Example B1. . At this time, the prepared polyester resin exhibited an acid value of 67.7 mgKOH/g, a viscosity of 3,940 cPs (measured by Brookfield viscosity at 200°C), and a glass transition temperature of 60.2°C, and the results are shown in Table 1 below.

Comparative Example B1: Preparation of a polyester resin using the crosslinked polyol composition of Comparative Example A1

Step 1: Preparation of prepolymer

1 of Example B1, except that the neopentyl glycol content was changed from 300.9 g to 331.0 g, and 29.7 g of the cross-linked polyol composition of Comparative Example A1 was used instead of 75.7 g of the cross-linked polyol composition of Example A1 A prepolymer of a polyester resin was prepared by performing the same method as the step.

Step 2: Preparation of polyester resin

A polyester resin was prepared in the same manner as in the second step of Example B1, except that 1,200 g of the prepolymer prepared in the first step was used instead of the prepolymer obtained in the first step of Example B1. . At this time, the prepared polyester resin exhibited an acid value of 62.3 mgKOH/g, a viscosity of 4,720 cPs (measured by Brookfield viscosity at 200°C), and a glass transition temperature of 62.5°C, and the results are shown in Table 1 below.

Comparative Example B2: Preparation of a polyester resin using the crosslinked polyol composition of Comparative Example A2

Step 1: Preparation of prepolymer

1 of Example B1, except that the neopentyl glycol content was changed from 300.9 g to 326.0 g, and 79.5 g of the cross-linked polyol composition of Comparative Example A2 was used instead of 75.7 g of the cross-linked polyol composition of Example A1 A prepolymer of a polyester resin was prepared by performing the same method as the step.

Step 2: Preparation of polyester resin

A polyester resin was prepared in the same manner as in the second step of Example B1, except that 1,200 g of the prepolymer prepared in the first step was used instead of the prepolymer obtained in the first step of Example B1. . In this case, the prepared polyester resin exhibited an acid value of 60.0 mgKOH/g, a viscosity of 5,810 cPs (measured by Brookfield viscosity at 200°C), and a glass transition temperature of 67.2°C, and the results are shown in Table 1 below.

Comparative Example B3: Preparation of a polyester resin using the crosslinked polyol composition of Comparative Example A3

Step 1: Preparation of prepolymer

A polyester resin prepolymer was prepared in the same manner as in the first step of Example B1, except that 73.8 g of the cross-linked polyol composition of Comparative Example A3 was used instead of 75.7 g of the cross-linked polyol composition of Example A1. did

Step 2: Preparation of polyester resin

A polyester resin was prepared in the same manner as in the second step of Example B1, except that 1,200 g of the prepolymer prepared in the first step was used instead of the prepolymer obtained in the first step of Example B1. . At this time, the prepared polyester resin exhibited an acid value of 58.8 mgKOH/g, a viscosity of 3,460 cPs (measured by Brookfield viscosity at 200°C), and a glass transition temperature of 56.3°C, and the results are shown in Table 1 below.

Comparative Example B4: Preparation of a polyester resin using the crosslinked polyol composition of Comparative Example A4

Step 1: Preparation of prepolymer

1 of Example B1, except that the neopentyl glycol content was changed from 263.3 g to 341.0 g, and 27.1 g of the cross-linked polyol composition of Comparative Example A4 was used instead of 75.7 g of the cross-linked polyol composition of Example A1 A prepolymer of a polyester resin was prepared by performing the same method as the step.

Step 2: Preparation of polyester resin

A polyester resin was prepared in the same manner as in the second step of Example B1, except that 1,200 g of the prepolymer prepared in the first step was used instead of the prepolymer obtained in the first step of Example B1. . In this case, the prepared polyester resin exhibited an acid value of 66.3 mgKOH/g, a viscosity of 3,920 cPs (measured by Brookfield viscosity at 200°C), and a glass transition temperature of 59.5°C, and the results are shown in Table 1 below.

Comparative Example B5: Preparation of a polyester resin using the crosslinked polyol composition of Comparative Example A5

Step 1: Preparation of prepolymer

The neopentyl glycol content was changed from 300.9 g to 258.6 g, the ethylene glycol content was changed from 358.7 g to 336.3 g, the terephthalic acid content was changed from 800 g to 750 g, and instead of 75.7 g of the crosslinked polyol composition of Example A1, A prepolymer of a polyester resin was prepared in the same manner as in the first step of Example B1, except that 161.0 g of the crosslinked polyol composition of Comparative Example A5 was used.

Step 2: Preparation of polyester resin

A polyester resin was prepared in the same manner as in the second step of Example B1, except that 1,200 g of the prepolymer prepared in the first step was used instead of the prepolymer obtained in the first step of Example B1. . In this case, the prepared polyester resin exhibited an acid value of 56.1 mgKOH/g, a viscosity of 3,330 cPs (measured by Brookfield viscosity at 200°C), and a glass transition temperature of 58.0°C, and the results are shown in Table 1 below.

Comparative Example B6: Preparation of a polyester resin using the crosslinked polyol composition of Comparative Example A6

Step 1: Preparation of prepolymer

The neopentyl glycol content was changed from 300.9 g to 258.6 g, the ethylene glycol content was changed from 358.7 g to 336.3 g, the terephthalic acid content was changed from 800 g to 750 g, and instead of 75.7 g of the crosslinked polyol composition of Example A1, A prepolymer of a polyester resin was prepared in the same manner as in the first step of Example B1, except that 214.4 g of the crosslinked polyol composition of Comparative Example A6 was used.

Step 2: Preparation of polyester resin

A polyester resin was prepared in the same manner as in the second step of Example B1, except that 1,200 g of the prepolymer prepared in the first step was used instead of the prepolymer obtained in the first step of Example B1. . In this case, the prepared polyester resin exhibited an acid value of 50.1 mgKOH/g, a viscosity of 2,850 cPs (measured by Brookfield viscosity at 200°C), and a glass transition temperature of 53.8°C, and the results are shown in Table 1 below.

Comparative Example B7: Preparation of polyester resin without cross-linked polyol composition

Step 1: Preparation of prepolymer

A prepolymer of a polyester resin was prepared in the same manner as in the first step of Example B1, except that the neopentyl glycol content was changed from 300.9 g to 351.1 g, and the cross-linked polyol composition of Example A1 was not used. prepared.

Step 2: Preparation of polyester resin

A polyester resin was prepared in the same manner as in the second step of Example B1, except that 1,200 g of the prepolymer prepared in the first step was used instead of the prepolymer obtained in the first step of Example B1. . In this case, the prepared polyester resin exhibited an acid value of 65.3 mgKOH/g, a viscosity of 4,400 cPs (measured by Brookfield viscosity at 200°C), and a glass transition temperature of 62.8°C, and the results are shown in Table 1 below.

Comparative Example B8: Preparation of a polyester resin using the crosslinked polyol composition of Comparative Example A7

Step 1: Preparation of prepolymer

A polyester resin prepolymer was prepared in the same manner as in the first step of Example B1, except that 80.3 g of the cross-linked polyol composition of Comparative Example A7 was used instead of 75.7 g of the cross-linked polyol composition of Example A1. did

Step 2: Preparation of polyester resin

A polyester resin was prepared in the same manner as in the second step of Example B1, except that 1,200 g of the prepolymer prepared in the first step was used instead of the prepolymer obtained in the first step of Example B1. . In this case, the prepared polyester resin exhibited an acid value of 55.9 mgKOH/g, a viscosity of 5,000 cPs (measured by Brookfield viscosity at 200°C), and a glass transition temperature of 54.7°C, and the results are shown in Table 1 below.

Comparative Example B9: Preparation of a polyester resin using the crosslinked polyol composition of Comparative Example A8

Step 1: Preparation of prepolymer

The first step of Example B1, except that the neopentyl glycol content was changed from 300.9 g to 326 g, and 39.4 g of the cross-linked polyol composition of Comparative Example A8 was used instead of 75.7 g of the cross-linked polyol composition of Example A1 A prepolymer of a polyester resin was prepared in the same manner as described above.

Step 2: Preparation of polyester resin

A polyester resin was prepared in the same manner as in the second step of Example B1, except that 1,200 g of the prepolymer prepared in the first step was used instead of the prepolymer obtained in the first step of Example B1. . At this time, the prepared polyester resin exhibited an acid value of 61.8 mgKOH/g, a viscosity of 6,320 cPs (measured by Brookfield viscosity at 200°C), and a glass transition temperature of 60.6°C, and the results are shown in Table 1 below.

<Method of measuring physical properties>

(1) Acid value (unit: mgKOH/g): The acid value of the polyester resin was measured using a 0.1N-KOH methanol solution.

(2) Viscosity (unit: cPs): The viscosity of the polyester resin was measured at 200°C using a Brookfield viscometer (Brookfield CAP2000+ Viscosmeter).

(3) Glass transition temperature (Tg, unit: °C): The glass transition temperature of the polyester resin was measured using a differential scanning calorimeter (DSC Q100, TA Instrument). Specifically, the temperature was raised from 20 °C to 300 °C at a temperature increase rate of 10 °C/min, and then rapidly cooled to 20 °C, and then heated to 300 °C again to measure the glass transition temperature.

<Manufacture of powder coating material>

Example C1

60 parts by weight of the bio-polyester resin prepared in Example B1, 40 parts by weight of an epoxy resin (YD-013K, equivalent 800, Kukdo Chemical Co., Ltd.) as a curing agent, 0.5 parts by weight of an anti-pinhole agent (Benzoin, Samchun (manufactured)) , 1.5 parts by weight of flowability improver (PV-5, manufactured by Worlee Co.), 0.5 parts by weight of polyethylene wax (PE 1544), 50 parts by weight of titanium dioxide (R-902+, Dupont-Titan (manufactured)) as a white pigment As a part and an extender pigment, 10 parts by weight of barium sulfate (BSN-OF, Gemme Co., Ltd.) was uniformly mixed and then pulverized. Thereafter, it was dispersed through a high-temperature extruder, the solidified particles were pulverized again through a mixer, and then a powder coating having a particle size of 120 μm or less was prepared through a sieve.

Examples C2 to C9 and Comparative Examples C1 to C9

A powder coating was prepared in the same manner as in Example C1, except that the type of bio-polyester resin was changed to the polyester resins prepared in Examples B2 to B9 and Comparative Examples B1 to B9, respectively.

Table 2 below shows the component mixing weight ratios of the powder coatings of Examples C1 to C9 and Comparative Examples C1 to C9.

<Preparation of coating film specimen>

Example D1

The powder coating prepared in Example C1 was applied to a 0.6 mm thick horse steel plate pretreated with zinc phosphate, and then cured under curing conditions for 15 minutes at 160° C. and 10 minutes at 170° C. to obtain a coating film thickness of 90±10 μm A phosphor coating film specimen was prepared.

Examples D2 to D9 and Comparative Examples D1 to D9

A coating film specimen was prepared in the same manner as in Example D1, except that the powder coating material was changed to the powder coating material prepared in Examples C2 to C9 and Comparative Examples C1 to C9, respectively.

The physical properties of the prepared coating film specimens were measured as follows.

<Measurement of physical properties of coating film specimens>

1. Leveling evaluation method: The coating film specimen was visually observed, and the less the curvature of the visually observed coating film specimen, the better the leveling was.

2. Pinhole evaluation method: The coating film specimen was visually observed, and the thickness of the visually observed pinhole was measured using a thickness gauge. The larger the pinhole thickness, the better.

3. Impact resistance evaluation method: In accordance with KSM ISO 6272-1, a 1 kg weight was dropped from a 50 cm and 20 cm high fixture to visually check whether or not cracks occurred in the coating film specimen. It indicates that the higher the drop height, the better the impact resistance.

4. Adhesion evaluation method: In accordance with KSM ISO 2409, 100 grooves are drawn at 1mm x 1mm intervals on the coating film specimen with a constant force and attached with glass tape. After a certain period of time, the glass tape is removed and the attached The number was measured.

5. Flexural resistance evaluation method: In accordance with KSM ISO 6860, when the coating film specimen was folded within 3/8 inch using a bending device, it was visually checked whether cracks occurred in the coating film specimen.

○: When cracks do not occur

X: When cracks occur

6. Hardness evaluation method: According to ASTM D3363, the hardness was measured by scratching the surface of the coating film specimen using a pencil (Mitsubishi Co., Ltd.), and the hardness was indicated according to the degree of scratching. The hardness value was expressed as 9H to 1H, F, HB, and 1B to 6B according to the hardness and concentration of the black lead of the pencil, 9H is the highest hardness value, and the hardness is sequentially lowered, and 6B is the lowest hardness value.

7. Alkali resistance and acid resistance evaluation method: According to ASTM D 1308-2, the coating film specimen was precipitated in 5% NaOH solvent or CH COOH for 48 hours, and then the coating film peeling and glossiness were checked after a certain period of time.

8. Storage stability evaluation method: The degree of agglomeration or aggregation of the powder coating was visually checked while the powder coating was stored in a high temperature environment of 40° C. for 6 hours. The less the agglomeration or aggregation of the powder coating, the better the storage stability .

◎: Almost no agglomeration or agglomeration of powder paint

○: There is some agglomeration or agglomeration of the powder coating material

X: There is a lot of agglomeration or agglomeration of the powder coating

The measured physical properties of the coating film specimens are shown in Table 3 below.

As shown in Table 3, the powder coatings of Examples C1 to C9 and Comparative Examples C1 to C9 were prepared using the polyester resins prepared in Examples B1 to B9 and Comparative Examples B1 to B9, respectively, and under the same curing conditions As a result of comparing the physical properties of the coating film specimens of Examples D1 to D9 and Comparative Examples D1 to D9 prepared by curing with

However, the coating film specimens to which the polyester resin of Examples B1 to B9 according to the present invention was applied were excellent in appearance (leveling and pinhole), flexibility, and storage stability, but the polyester resin of Comparative Examples B1 to B9 was applied. It was confirmed that at least one of silver appearance (leveling and pinhole), flexibility, and storage stability became poor.

In particular, the coating film specimen to which the polyester resin of Examples B1 to B9 according to the present invention was applied had a hardness of F or more, but the coating film specimen to which the polyester resin of Comparative Examples B1 to B9 was applied had a hardness of HB or less. .

As described above, when a powder coating material is prepared using the polyester resin according to the present invention, and a coating film specimen is prepared using the same, it can be confirmed that it is excellent in appearance, mechanical properties, chemical resistance and storage stability.

Claims (25)

A crosslinked polyol composition comprising:
It is obtained by crosslinking an anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition with an epoxy compound,
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 the following Chemical Formula 1, 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;
The anhydrosugar alcohol-alkylene glycol composition is prepared by addition reaction of the anhydrosugar alcohol composition with an alkylene oxide,
More than 3 parts by weight to less than 60 parts by weight of the epoxy compound per 100 parts by weight of the anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition is cross-linked,
Cross-linked polyol compositions:
[Formula 1]

In Formula 1, n is an integer of 0 to 4. The crosslinked polyol composition of claim 1 , wherein the first polyol component is hexitol monohydrate. The crosslinked polyol composition of claim 1 , wherein the second polyol component is hexitol dianhydrosugar. The crosslinked 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 crosslinked 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 for a dehydration reaction, and the obtained dehydration reaction product is applied to a thin film. A crosslinked polyol composition prepared by distillation. 7. The crosslinked 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 crosslinked polyol composition according to claim 1, wherein the anhydrosugar alcohol-alkylene glycol composition is prepared by addition reaction of more than 30 parts by weight to less than 700 parts by weight of an alkylene oxide per 100 parts by weight of the anhydrosugar alcohol composition. The epoxy compound according to claim 1, wherein the epoxy compound is a bisphenol A-epichlorohydrin resin, a diglycidyl ether resin of bisphenol A, a novolak type epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, a bicyclic epoxy resin, a glycy A crosslinked polyol composition selected from the group consisting of a dill ester type epoxy resin, a brominated epoxy resin, a bio-derived epoxy resin, an epoxidized soybean oil, a rubber-modified epoxy compound, or a combination thereof. The epoxy compound according to claim 1, wherein the epoxy compound is a natural rubber-modified epoxy compound, a carboxyl-terminated butadiene acrylonitrile-modified epoxy compound, a core-shell rubber-modified epoxy compound, a polybutadiene-modified epoxy compound, an acrylonitrile-butadiene-modified epoxy compound, and styrene. -A rubber selected from the group consisting of butadiene-modified epoxy compound, epoxy-terminated butadiene acrylonitrile-modified epoxy compound, amine-terminated butadiene acrylonitrile-modified epoxy compound, hydroxy-terminated butadiene acrylonitrile-modified epoxy compound, or a combination thereof A crosslinked polyol composition which is a modified epoxy compound. A method for preparing a crosslinked polyol composition, comprising:
Comprising a crosslinking reaction of an anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition and an epoxy compound,
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 the following Chemical Formula 1, 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;
The anhydrosugar alcohol-alkylene glycol composition is prepared by addition reaction of the anhydrosugar alcohol composition with an alkylene oxide,
More than 3 parts by weight to less than 60 parts by weight of the epoxy compound per 100 parts by weight of the anhydrosugar alcohol composition or anhydrosugar alcohol-alkylene glycol composition is cross-linked,
Method for preparing the crosslinked polyol composition:
[Formula 1]

In Formula 1, n is an integer of 0 to 4. A prepolymer block prepared from a monomer mixture comprising a polyol component comprising the crosslinked polyol composition of any one of claims 1 to 10 and a polyacid component; and a polyacid component; as a repeating unit, the polyester resin. The polyester resin according to claim 12, wherein the content of the crosslinked polyol composition included as a repeating unit is greater than 0.3 parts by weight and less than 27.3 parts by weight, based on 100 parts by weight of the polyester resin. The polyester resin according to claim 12, wherein the polyol component further comprises a diol component other than the crosslinked polyol composition. The polyester resin according to claim 14, wherein the diol component other than the crosslinked polyol composition is an aliphatic diol, an cycloaliphatic diol, an aromatic diol, or a combination thereof. 16. The method according to claim 15, wherein the aliphatic diol is a linear or branched aliphatic diol having 2 to 8 carbon atoms; the alicyclic diol is an alicyclic diol having 5 to 20 carbon atoms and containing 1 to 4 5-membered ring structures or 6-membered ring structures; The polyester resin, wherein the aromatic diol is an aromatic diol having 6 to 20 carbon atoms and containing 1 to 4 aromatic ring structures. 16. The method of claim 15,
The aliphatic diol is ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,2- dimethyl-1,3-propanediol, neopentylglycol, pentanediol, hexanediol, heptanediol, and combinations thereof;
The alicyclic diol is 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2- selected from the group consisting of cyclohexanedimethanol, tetramethylcyclobutanediol, tricyclodecanedimethanol, adamantanediol, and combinations thereof;
Aromatic diol is bisphenol A, 4,4'-dihydroxy-diphenyl sulfone, 4,4'-biphenol, hydroquinone, 4,4'-dihydroxy-diphenyl ether, 3-(4-hydroxyl phenoxy) phenol, bis (4-hydroxyphenyl) sulfide, and combinations thereof,
polyester resin. 15. The polyol according to claim 14, wherein the polyol component comprises 1 to 50 parts by weight of the crosslinked polyol composition and 50 to 99 parts by weight of a diol component other than the crosslinked polyol composition, based on 100 parts by weight of the total polyol component. ester resin. The polyester resin according to claim 12, wherein the polyacid component is a diacid, a triacid, or a mixture thereof. The polyester resin according to claim 19, wherein the diacid is selected from the group consisting of aromatic dicarboxylic acids having 8 to 14 carbon atoms, aliphatic dicarboxylic acids having 4 to 12 carbon atoms, and combinations thereof. 20. The method of claim 19, wherein the diacid is terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, cyclohexanedicarboxylic acid, phthalic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, adipic acid, glue A polyester resin selected from the group consisting of taric acid and combinations thereof, wherein the trivalent acid is trimellitic acid or anhydride thereof. 13. The method according to claim 12, wherein the polyester resin has an acid value of 40 to 70 mgKOH/g, a viscosity of 2,000 to 6,000 cPs (measured with a Brookfield viscometer at 200 °C), and a glass transition temperature of 55 to 100 °C, polyester resin. (1) preparing a prepolymer by reacting a polyol component comprising the crosslinked polyol composition of any one of claims 1 to 10 with a polyhydric acid component; and
(2) preparing a polyester resin by reacting the prepolymer prepared in step (1) with a polyacid component;
A method for producing a polyester resin. The polyester resin of claim 12; and a curing agent; and a powder coating composition comprising a. The powder coating composition according to claim 24, wherein the curing agent is an epoxy resin curing agent.