KR20220037046A - Acryl-modified polyurethane composition and method for preparing the same, and waterborne coating composition prepared therefrom and method for preparing the same - Google Patents

Abstract

The present invention relates to an acryl-modified polyurethane composition and a method for preparing the same, and a waterborne coating composition using the acryl-modified polyurethane composition and a method for preparing the same. Particularly, the acryl-modified polyurethane composition includes acryl-modified polyurethanes each including a polyisocyanate-derived polymerization unit and hydroxyalkyl (meth)acrylate-derived polymerization unit in combination with a polymerization unit derived from each of a mono-anhydrosugar alcohol, di-anhydrosugar alcohol, polysaccharide alcohol, polysaccharide alcohol-derived anhydrosugar alcohol, and a polymer of at least one thereof, and shows improved adhesive property (adhesiveness), cracking resistance and water resistance at the same time.

Description

Acrylic-modified polyurethane composition and method for preparing the same, and aqueous coating solution composition prepared therefrom, and method for preparing the same

The present invention relates to an acryl-modified polyurethane composition and a method for producing the same, and an aqueous coating solution composition using the same and a method for producing the same, and more particularly, from a polymer unit derived from polyisocyanate and a hydroxyalkyl (meth)acrylate. Acrylic-modified polyurethanes each comprising polymerized units derived from one or more polymers of mono-anhydrosugar alcohol, dianhydrosugar alcohol, polysaccharide alcohol, polysaccharide alcohol-derived anhydrosugar alcohol, and one or more polymers thereof, together with polymerized units derived therefrom; It relates to an acrylic-modified polyurethane composition capable of providing an aqueous coating solution composition with improved properties (adhesiveness), crack resistance and water resistance, and a method for manufacturing the same, and an aqueous coating solution composition using the same and a method for manufacturing the same.

Polyols and isocyanates, which are essential components of polyurethane, are usually manufactured from petroleum-based raw materials. In the field of , urethane, a method for partially or completely replacing polyols and isocyanates prepared from petroleum-based raw materials with environmentally friendly components has been requested.

Polyol can be produced from renewable biomass such as vegetable oil, cellulose, and lignin, and biopolyol derived from natural vegetable oil is already being produced on a commercial scale. The physical properties of the produced biopolyol depend on the type of biomass used for manufacturing. In general, castor oil, palm oil, etc. are used for the production of soft and hard polyurethanes and synthetic polyols, and soybean oil is used for the production of soft polyurethane polyols. However, the currently produced biomass-based biopolyol has a disadvantage in that it has a high viscosity.

Natural vegetable oil-based isocyanate is essentially an aliphatic compound, which has a disadvantage in that it is less reactive than petroleum-based aromatic diisocyanate. Therefore, there are not many studies on preparing diisocyanate using biomass.

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 an effect of improving the strength of these materials. useful. In addition, it is known that it can be used as an eco-friendly solvent for adhesives, eco-friendly plasticizers, biodegradable polymers, and water-soluble lacquers.

As such, anhydrosugar alcohol has attracted a lot of attention due to its various application possibilities, and its use in actual industry is gradually increasing.

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 an acryl-modified polyurethane composition and a method for manufacturing the same, and an aqueous system using the same, which can provide an aqueous coating solution composition having excellent environmental friendliness and improved adhesion (adhesion), crack resistance and water resistance To provide a coating solution composition and a method for manufacturing the same.

In order to achieve the above object, the present invention provides an acrylic-modified polyurethane composition comprising first to fifth acrylic-modified polyurethanes, wherein the first to fifth acrylic-modified polyurethanes are derived from polyisocyanate. and polymerized units derived from first to fifth polyol components, respectively, together with polymerized units and polymerized units derived from hydroxyalkyl (meth)acrylate, wherein the first polyol component is a monoanhydrosugar alcohol and , the second polyol component is a dianhydrosugar alcohol, the third polyol component is a polysaccharide alcohol represented by the following formula (1), and the fourth polyol component is a non-hydrated substance formed by removing water molecules from the polysaccharide alcohol represented by the following formula (1) Provided is an acryl-modified polyurethane composition, which is a sugar alcohol, wherein the fifth polyol component is a polymerization product of at least one selected from the first to fourth polyol components:

[Formula 1]

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

According to another aspect of the present invention, (1) reacting polyisocyanate and hydroxyalkyl (meth)acrylate to prepare an acrylic-modified isocyanate intermediate; and (2) reacting the acrylic-modified isocyanate intermediate obtained in step (1) with a polyol composition comprising first to fifth polyol components, wherein the first polyol component is monohydrated alcohol , the second polyol component is a dianhydrosugar alcohol, the third polyol component is the polysaccharide alcohol represented by Formula 1, and the fourth polyol component is formed by removing water molecules from the polysaccharide alcohol represented by Formula 1 Anhydrosugar alcohol, wherein the fifth polyol component is a polymerization product of one or more selected from the first to fourth polyol components, a method for producing an acrylic-modified polyurethane composition is provided.

According to another aspect of the present invention, the acrylic-modified polyurethane composition and a polymer composition prepared from a polymerization reaction of a hydrophilic acrylic monomer; and water; containing, a water-based coating solution composition is provided.

According to another aspect of the present invention, in the presence of water and a polymerization initiator as a solvent, there is provided a method for preparing an aqueous coating solution composition comprising the step of polymerizing the acrylic-modified polyurethane composition and a hydrophilic acrylic monomer.

The acrylic-modified polyurethane composition according to the present invention has excellent eco-friendliness, and the water-based coating solution composition of the present invention prepared by using it is eco-friendly because there is no organic solvent at all, and at the same time, adhesion (adhesion), crack resistance and water resistance are excellent. All are improved to show excellent paint performance.

In addition, since the acrylic-modified polyurethane composition according to the present invention is prepared from a polyol composition obtained by utilizing a by-product obtained in the process of producing an internal dehydrated product of hydrogenated sugar, it increases economic efficiency and improves eco-friendliness by solving the by-product treatment problem can do it

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

[Acrylic-modified polyurethane composition]

The acrylic-modified polyurethane composition of the present invention includes first to fifth acrylic-modified polyurethanes.

(1) the first acrylic-modified polyurethane

The first acrylic-modified polyurethane included in the acrylic-modified polyurethane composition of the present invention includes a polymer unit derived from monoanhydride alcohol as the first polyol component, a polymer unit derived from polyisocyanate, and a hydroxyalkyl ( polymerized units derived from meth)acrylates.

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.

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.

In one embodiment, examples of the polyisocyanate include methylenediphenyl diisocyanate (MDI) (eg, 2,4- or 4,4'-methylenediphenyl diisocyanate), xylylene diisocyanate (XDI), m- or p-tetramethylxylylene diisocyanate (TMXDI), toluene diisocyanate (TDI), di- or tetra-alkyldiphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate (TODI) ), phenylene diisocyanate (eg, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate), naphthalene diisocyanate (NDI), or 4,4'-dibenzyl diisocyanate, etc. aromatic polyisocyanates; Hydrogenated MDI (H12MDI), 1-methyl-2,4-diisocyanatocyclohexane, 1,12-diisocyanatododecane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6 -Diisocyanato-2,4,4-trimethylhexane, isophorone diisocyanate (IPDI), tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate (HDI) (eg 1,6-hexamethylene diisocyanate), dimer fatty acid diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate (eg cyclohexane-1,4-diisocyanate) or ethylene diisocyanate aliphatic polyisocyanates such as; Or it may be a combination thereof, but is not limited thereto.

In another embodiment, examples of the polyisocyanate include methylenediphenyl diisocyanate (MDI), ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1-12-dodecane di Isocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, 2,4-hexahydrotoluene diisocyanate, 2,6 -hexahydrotoluene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate (HMDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2 ,6-toluene diisocyanate, toluene diisocyanate mixed with 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (2,4-/2,6-isomer ratio = 80/20), diphenylmethane- 2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, polydiphenylmethane diisocyanate (PMDI), naphthalene-1,5-diisocyanate, or a combination thereof, but is not limited thereto .

More specifically, the polyisocyanate may be methylenediphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), or a combination thereof.

In one embodiment, examples of the hydroxyalkyl (meth)acrylate may be a linear or branched alkyl acrylate having a hydroxy group, a linear or branched alkyl methacrylate having a hydroxy group, or a combination thereof, and more Specifically, it may be a linear or branched C1-C8 alkyl acrylate having a hydroxyl group, a linear or branched C1-C8 alkyl methacrylate having a hydroxyl group, or a combination thereof, and more specifically, hydroxymethyl acrylate, Hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypentyl acrylic Late, hydroxypentyl methacrylate, 2-hydroxyethylhexyl acrylate, 2-hydroxyethylhexyl methacrylate, 2-hydroxyethylbutyl acrylate, 2-hydroxyethylbutyl methacrylate, hydroxyoctyl acrylate, hydroxyoctyl methacrylate, or a combination thereof, and more specifically, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate acrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, or a combination thereof, but is not limited thereto.

According to one embodiment, in the first acrylic-modified polyurethane, with respect to 1 equivalent of the polymerized unit derived from the first polyol component, 2 equivalents of the polymerized unit derived from polyisocyanate and hydroxyalkyl (meth) Two equivalents of polymerized units derived from acrylates may be included.

(2) second acrylic-modified polyurethane

The second acrylic-modified polyurethane included in the acrylic-modified polyurethane composition of the present invention includes a polymerized unit derived from dianhydrosugar alcohol as the second polyol component, a polymerized unit derived from polyisocyanate, and a hydroxyalkyl ( polymerized units derived from meth)acrylates.

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.

Specific examples of the polyisocyanate and hydroxyalkyl (meth)acrylate included as polymerized units in the second acryl-modified polyurethane are the same as those described in the first acryl-modified polyurethane.

According to one embodiment, in the second acrylic-modified polyurethane, with respect to 1 equivalent of the polymerization unit derived from the second polyol component, 2 equivalents of a polymerization unit derived from a polyisocyanate and hydroxyalkyl (meth) Two equivalents of polymerized units derived from acrylates may be included.

(3) a third acrylic-modified polyurethane

The third acrylic-modified polyurethane included in the acrylic-modified polyurethane composition of the present invention is a polymer unit derived from a polysaccharide alcohol represented by the following formula (1) as a third polyol component, a polymer unit derived from polyisocyanate, and polymerized units derived from hydroxyalkyl (meth)acrylates.

[Formula 1]

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

In one embodiment, the polysaccharide alcohol represented by Formula 1 may be prepared from a hydrogenation reaction of polysaccharides greater than or equal to disaccharides, including maltose.

Specific examples of polyisocyanate and hydroxyalkyl (meth)acrylate included as polymerized units in the third acryl-modified polyurethane are the same as those described in the first acryl-modified polyurethane.

According to one embodiment, in the third acrylic-modified polyurethane, 2 equivalents of polymerized units derived from polyisocyanate and hydroxyalkyl (meth) with respect to 1 equivalent of polymerized units derived from the third polyol component Two equivalents of polymerized units derived from acrylates may be included.

(4) the fourth acrylic-modified polyurethane

The fourth acrylic-modified polyurethane included in the acrylic-modified polyurethane composition of the present invention is a polymerization derived from anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1, which is the fourth polyol component. unit, a polymerized unit derived from a polyisocyanate, and a polymerized unit derived from a hydroxyalkyl (meth)acrylate.

In one embodiment, the fourth polyol component may be 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 from 0 to 4.

Specific examples of polyisocyanate and hydroxyalkyl (meth)acrylate included as polymerization units in the fourth acryl-modified polyurethane are the same as those described in the first acryl-modified polyurethane.

According to one embodiment, in the fourth acrylic-modified polyurethane, 2 equivalents of polymerized units derived from polyisocyanate and hydroxyalkyl (meth) with respect to 1 equivalent of polymerized units derived from the fourth polyol component Two equivalents of polymerized units derived from acrylates may be included.

(5) the fifth acrylic-modified polyurethane

The fifth acrylic-modified polyurethane included in the acrylic-modified polyurethane composition of the present invention is a polymerization unit derived from one or more polymerization products selected from the first to fourth polyol components, which are the fifth polyol components. , polymerized units derived from polyisocyanates, and polymerized units derived from hydroxyalkyl (meth)acrylates.

In one embodiment, the fifth polyol component may be 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.

Specific examples of polyisocyanate and hydroxyalkyl (meth)acrylate included as polymerization units in the fifth acryl-modified polyurethane are the same as those described in the first acryl-modified polyurethane.

According to one embodiment, in the fifth acrylic-modified polyurethane, 2 equivalents of polymerized units derived from polyisocyanate and hydroxyalkyl (meth) with respect to 1 equivalent of polymerized units derived from the fifth polyol component Two equivalents of polymerized units derived from acrylates may be included.

In one embodiment, the first acryl-modified polyurethane may be an acryl-modified polyurethane represented by the following Chemical Formula A; The second acryl-modified polyurethane may be an acryl-modified polyurethane represented by the following Chemical Formula B; The third acryl-modified polyurethane may be an acryl-modified polyurethane represented by the following formula (C); The fourth acryl-modified polyurethane may be an acryl-modified polyurethane represented by the following Chemical Formula D; The fifth acryl-modified polyurethane may be an acryl-modified polyurethane represented by the following formula (E), but is not limited thereto:

[Formula A]

[Formula B]

[Formula C]

[Formula D]

[Formula E]

In the above formulas A to E,

R1 is each independently an alkylene group, a cycloalkylene group, or an arylene group, more specifically, a C1-C20 linear or C2-C20 branched alkylene group, a C3-C20 cycloalkylene group, or a C6-C20 arylene group; ,

R2 is each independently each independently an alkylene group, more specifically, a C1-C8 linear or C2-C8 branched alkylene group;

R3 is each independently each independently a hydrogen atom or an alkyl group, more specifically, a hydrogen atom or a C1-C4 linear or C3-C4 branched alkyl group;

L1 is a divalent organic group derived from the first polyol component, and more specifically, 1,4-anhydrohexitol, 3,6-anhydrohexitol, 2,5-anhydrohexitol, 1,5-anhydrohexitol or a divalent organic group derived from 2,6-anhydrohexitol,

L2 is a divalent organic group derived from the second polyol component, more specifically, a divalent organic group derived from isosorbide, isomannide or isoidide, and more specifically selected from the following formula

L3 is a divalent organic group derived from the third polyol component,

L4 is a divalent organic group derived from the fourth polyol component, and more specifically, a divalent organic group derived from the compound represented by Formula 2, the compound represented by Formula 3, or a mixture thereof,

L5 is a divalent organic group derived from the fifth polyol component.

[Method for producing acrylic-modified polyurethane composition]

A method for preparing an acrylic-modified polyurethane composition provided according to another aspect of the present invention comprises the steps of (1) reacting a polyisocyanate with a hydroxyalkyl (meth)acrylate to prepare an acrylic-modified isocyanate intermediate; and (2) reacting the acrylic-modified isocyanate intermediate obtained in step (1) with a polyol composition comprising first to fifth polyol components; wherein, the first to fifth polyols The components are the same as described above for the acrylic-modified polyurethane composition.

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

In one embodiment, the number average molecular weight (Mn: unit g/mol) of the polyol composition may be 193 or more, 195 or more, 200 or more, 202 or more, 205 or more, or 208 or more. In addition, the number average molecular weight (Mn) of the polyol composition of the present invention may be 1,589 or less, 1,560 or less, 1,550 or less, 1,520 or less, 1,500 or less, 1,490 or less, or 1,480 or less.

In one embodiment, the number average molecular weight (Mn) of the polyol composition may be 193 to 1,589, specifically 195 to 1,550, more specifically 200 to 1,520, and even more specifically 202 to 1,520. It may be 1,500, and more specifically, it may be 205 to 1,490. When the number average molecular weight of the polyol composition is less than 193, an acrylic-modified polyurethane composition is prepared using the polyol composition, and when this is applied to the preparation of the aqueous coating solution composition, phase separation occurs within the aqueous coating solution composition, and thus the aqueous coating solution When the number average molecular weight exceeds 1,589, an acrylic-modified polyurethane composition is prepared using the polyol composition, and when this is applied to the preparation of the aqueous coating solution composition, the coating film formed from the aqueous coating solution composition is at room temperature. Peeling may occur in water, resulting in poor water resistance.

In one embodiment, the polyol composition may have a polydispersity index (PDI) of 1.13 or more, 1.15 or more, 1.20 or more, 1.23 or more, or 1.25 or more. In addition, the polyol composition of the present invention may have a polydispersity index (PDI) of 3.41 or less, 3.40 or less, 3.35 or less, 3.30 or less, 3.25 or less, 3.22 or less, or 3.19 or less.

In one embodiment, the polyol composition may have a polydispersity index (PDI) of 1.13 to 3.41, specifically 1.13 to 3.40, more specifically 1.15 to 3.35, and even more specifically 1.20. to 3.25, and more specifically, 1.23 to 3.22. When the polydispersity index of the polyol composition is less than 1.13 or exceeds 3.41, an acrylic-modified polyurethane composition is prepared using the polyol composition, and when this is applied to the preparation of the aqueous coating solution composition, the coating film formed from the aqueous coating solution composition is at room temperature. Peeling may occur from the inside, resulting in poor water resistance.

In one embodiment, the average number of -OH groups per molecule in the polyol 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. In addition, the average number of -OH groups per molecule in the polyol composition may be 21.36 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.

More specifically, the average number of -OH groups per molecule in the polyol composition may be 2.54 to 21.36, more specifically, 2.60 to 21.30, and even more specifically, 2.65 to 21.0. . When the average number of -OH groups per molecule in the polyol composition is less than 2.54, an acrylic-modified polyurethane composition is prepared using the polyol composition, and when this is applied to the preparation of the aqueous coating solution composition, the coating film formed from the aqueous coating solution composition is at room temperature Peeling may occur in water, resulting in poor water resistance, and when the number exceeds 21.36, an acrylic-modified polyurethane composition is prepared using the polyol composition, and when applied to the preparation of the aqueous coating solution composition, in the aqueous coating solution composition phase separation may occur, so it may be difficult to express physical properties as an aqueous coating solution.

In one embodiment, the polyol composition is prepared by hydrogenation reaction of a glucose-containing saccharide composition (eg, glucose; mannose; fructose; and a saccharide composition including polysaccharides at least disaccharides including maltose) to prepare and obtain a hydrogenated saccharide composition The hydrogenated sugar composition may be heated under an acid catalyst for a dehydration reaction, and the obtained dehydration reaction product may be prepared by thin film distillation, more specifically, after thin film distillation of the obtained dehydration reaction product is obtained by thin film distillation, It could be the remaining by-products.

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 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 saccharide composition is less than 41% by weight, the number average molecular weight (Mn) of the polyol composition is too high, and an acrylic-modified polyurethane composition is prepared using the polyol composition, and this is applied to the preparation of an aqueous coating solution composition , The coating film formed from the water-based coating solution composition may peel off in room temperature water, resulting in poor water resistance, and when it exceeds 99.5 wt%, the number average molecular weight of the polyol composition becomes too low. When preparing the composition and applying it to the preparation of the aqueous coating solution composition, phase separation occurs in the aqueous coating solution composition, so that it may be difficult to express physical properties as an aqueous coating solution.

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) may be lowered, and when it exceeds 57 wt %, there is a problem in that the distillation yield of the dianhydrosugar alcohol is significantly lowered when the result of the dehydration reaction of the hydrogenated sugar composition is thin-film distilled. In addition, when the polysaccharide alcohol content in the hydrogenated sugar composition is less than 0.8% by weight, a polyol composition is prepared using the hydrogenated sugar composition, and an acrylic-modified polyurethane composition is prepared using the polyol composition, and this is used for preparing an aqueous coating solution composition. When applied, cracks may occur in the coating film formed from the aqueous coating solution composition, and when it exceeds 57 wt%, the viscosity of the polyol composition prepared using the hydrogenated sugar composition becomes very high, so that the acrylic- When preparing the modified polyurethane composition, there may be a problem in that it is easily cured.

According to one embodiment, in the step (1) of the method for producing the acrylic-modified polyurethane composition of the present invention, 1 equivalent of polyisocyanate and 1 equivalent of hydroxyalkyl (meth)acrylate are reacted to react hydroxyalkyl ( An acrylic-modified isocyanate intermediate to which meth)acrylate is partially added is prepared.

In one embodiment, the reaction of step (1) may be carried out in the presence of a catalyst, such as an amine catalyst, an organometallic catalyst, or a mixture thereof. The reaction may be performed at room temperature (eg, 20 to 30° C.).

The type of the amine catalyst is not particularly limited, but preferably one or a mixture of two or more selected from tertiary amine catalysts may be used, and more specifically, triethylene diamine, triethylamine , N-methyl morpholine (N-Methyl morpholine), N-ethyl morpholine (N-Ethyl morpholine), or one selected from the group consisting of a combination thereof may be used.

The type of the organometallic catalyst is also not particularly limited, but for example, an organotin catalyst, more specifically, tin octylate, dibutyltin dilaurate (DBTDL), tin bis[2-ethylhexanoate], or a combination thereof. One selected from the group consisting of may be used.

According to one embodiment, in the step (2) of the method for producing the acrylic-modified polyurethane composition of the present invention, the first to fifth polyols per 100 parts by weight of the acrylic-modified isocyanate intermediate obtained from the step (1) By reacting 30 to 300 parts by weight of the polyol composition including the components, an acrylic-modified polyurethane composition can be obtained. When the content of the polyol composition per 100 parts by weight of the acryl-modified isocyanate intermediate is too less than the above level, phase separation occurs in the aqueous coating solution composition to which the prepared acrylic-modified polyurethane composition is applied, so that it is difficult to express the physical properties as an aqueous coating solution. If the content of the polyol composition is excessively greater than the above level, the coating film formed from the aqueous coating solution composition to which the prepared acrylic-modified polyurethane composition is applied may peel off in room temperature water, resulting in poor water resistance.

In one embodiment, the reaction of step (2) may also be carried out in the presence of a catalyst, such as the above-described amine catalyst, organometallic catalyst, or a mixture thereof. In addition, the reaction may be carried out for a suitable time (eg, 0.1 to 5 hours, preferably 0.5 to 2 hours) under elevated temperature (eg, at 50 to 100°C, preferably 50 to 70°C), but in this not limited

[Aqueous coating liquid composition and manufacturing method thereof]

According to another aspect of the present invention, the acrylic-modified polyurethane composition of the present invention and a polymer composition prepared from a polymerization reaction of a hydrophilic acrylic monomer; and water; containing, a water-based coating solution composition is provided.

In one embodiment, as the hydrophilic acrylic monomer, at least one selected from the group consisting of an acrylic monomer having a carboxyl group, an acrylic monomer having an amide group, an acrylic monomer having a hydroxyl group, and combinations thereof may be used.

Illustratively, as the acrylic monomer having a carboxyl group, one or more selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid and maleic acid may be used, and the acrylic monomer having an amide group may include acrylamide, N-methylolamide And one or more selected from the group consisting of diacetone acrylamide may be used, and as the acrylic monomer having a hydroxyl group, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxy At least one selected from the group consisting of hydroxypropyl methacrylate may be used, but is not limited thereto.

In one embodiment, the content of the acrylic-modified polyurethane composition in the aqueous coating solution composition may be more than 30 parts by weight and less than 85 parts by weight based on 100 parts by weight of the total of the acrylic-modified polyurethane composition, the hydrophilic acrylic monomer and water. there is. If the content of the acrylic-modified polyurethane composition in the aqueous coating solution composition is too less than the above level, the water resistance of the coating film formed from the coating solution composition may be poor. can

More specifically, the content of the acrylic-modified polyurethane composition in the aqueous coating solution composition is based on a total of 100 parts by weight of the acrylic-modified polyurethane composition, the hydrophilic acrylic monomer and water, 31 parts by weight or more, 32 parts by weight or more, 33 It may be at least 34 parts by weight, at least 35 parts by weight, at least 36 parts by weight, at least 37 parts by weight, at least 38 parts by weight, at least 39 parts by weight, or at least 40 parts by weight, and may be 84.5 parts by weight or less, 84 parts by weight or more. parts by weight or less, 83.5 parts by weight or less, 83 parts by weight or less, 82.5 parts by weight or less, 82 parts by weight or less, 81.5 parts by weight or less, 81 parts by weight or less, 80.5 parts by weight or less, or 80 parts by weight or less, but is not limited thereto.

In one embodiment, the content of the hydrophilic acrylic monomer in the aqueous coating solution composition may be 10 parts by weight to 50 parts by weight based on 100 parts by weight in total of the acrylic-modified polyurethane composition, the hydrophilic acrylic monomer and water. If the content of the hydrophilic acrylic monomer in the aqueous coating solution composition is excessively less than the above level, the amount of the acrylic-modified polyurethane composition may be relatively large and the crack resistance of the coating film formed from the coating solution composition may be poor. The amount of the acrylic-modified polyurethane composition may be relatively small, so that the water resistance of the coating film formed from the coating liquid composition may be poor.

More specifically, the content of the hydrophilic acrylic monomer in the aqueous coating solution composition is 10.5 parts by weight or more, 11 parts by weight or more, 11.5 parts by weight or more, based on 100 parts by weight of the total of the acrylic-modified polyurethane composition, the hydrophilic acrylic monomer and water. , 12 parts by weight or more, 12.5 parts by weight or more, 13 parts by weight or more, 13.5 parts by weight or more, 14 parts by weight or more, 14.5 parts by weight or more, or 15 parts by weight or more, and also 49 parts by weight or less, 48 parts by weight or less, 47 parts by weight or less, 46 parts by weight or less, 45 parts by weight or less, 44 parts by weight or less, 43 parts by weight or less, 42 parts by weight or less, 41 parts by weight or less, or 40 parts by weight or less, but is not limited thereto.

In one embodiment, the content of water in the aqueous coating solution composition may be 5 to 30 parts by weight, more specifically 5 parts by weight, based on 100 parts by weight of the total of the acrylic-modified polyurethane composition, the hydrophilic acrylic monomer and water. It may be in the range of parts by weight to 25 parts by weight, and more specifically, may be in the range of 5 parts by weight to 20 parts by weight, but is not limited thereto.

The aqueous coating solution composition of the present invention can be obtained by polymerizing the acrylic-modified polyurethane composition and a hydrophilic acrylic monomer in a water solvent in the presence of a polymerization initiator.

Accordingly, according to another aspect of the present invention, there is provided a method for preparing an aqueous coating solution composition, comprising the step of polymerizing the acrylic-modified polyurethane composition and a hydrophilic acrylic monomer in the presence of water and a polymerization initiator as a solvent. .

In the method for preparing the aqueous coating solution composition of the present invention, the specific usage amount of the acrylic-modified polyurethane composition, the specific type and usage amount of the hydrophilic acrylic monomer, and the specific usage amount of water are as exemplarily described in the aqueous coating solution composition above.

In one embodiment, as the polymerization initiator, for example, a persulfate-based catalyst such as potassium persulfate (KPS) may be used, but is not limited thereto.

In one embodiment, the amount of the polymerization initiator used may be 0.01 to 5 parts by weight, more specifically 0.1 to 1 parts by weight, based on 100 parts by weight of the total of the acrylic-modified polyurethane composition, the hydrophilic acrylic monomer and water. , but is not limited thereto.

In one embodiment, the polymerization reaction of the acrylic-modified polyurethane composition and the hydrophilic acrylic monomer is at an elevated temperature (eg, at 50 to 100° C., preferably at 60 to 90° C.) for a suitable time (eg, 0.5 to 5 hours, preferably Preferably, it may be carried out for 1 hour to 3 hours), but is not limited thereto.

The water-based coating solution composition of the present invention may additionally include additives that can be commonly used in water-based paints or coating solutions.

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 a polyol composition comprising the first to fifth polyol components>

Preparation Example 1: Preparation of a polyol composition using glucose in an amount of 97% by weight

A liquid hydrogenated sugar composition having a concentration of 55 wt% (solids basis, sorbitol 96 wt%, mannitol 0.9 Weight% and 3.1% by weight of polysaccharide alcohol greater than or equal to disaccharide) 1,819 g were obtained, which was put into a batch reactor equipped with a stirrer and concentrated by heating to 100° C., thereby obtaining 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 internal temperature of 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 concentrated under a reduced pressure of 45 mmHg for 1 hour or more to remove residual moisture and low boiling point substances to obtain 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%, and through this, the molar conversion rate from sorbitol to isosorbide was calculated to be 77.6%.

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

Preparation Example 2: Preparation of a polyol composition using a saccharide composition containing 78% by weight of glucose

Preparation Example Except for using 78% by weight of a glucose-containing saccharide composition (a total of 78% by weight of glucose and mannose, fructose and polysaccharides (sugars higher than disaccharides such as maltose) was used in place of the 97% pure glucose product) The hydrogenation reaction was performed in the same manner as in 1 to obtain 1,819 g of a liquid hydrogenated sugar composition having a concentration of 55% by weight (based on solids, 76% by weight of sorbitol, 3.6% by weight of mannitol and 20.4% by weight 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 1 for 1,000 g of the concentrated hydrogenated sugar composition, except that the content of sulfuric acid was changed from 9.6 g to 7.6 g and the content of 50% aqueous sodium hydroxide solution was changed from 15.7 g to 12.4 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 856 g, and as a result of analyzing the obtained anhydrosugar-alcohol conversion solution by gas chromatography, the conversion content to isosorbide was 54.9 wt%, through which sorbitol to isosorbate The molar conversion to beads was calculated to be 77.1%.

Thin film distillation was performed on 856 g of the obtained anhydrosugar-alcohol conversion solution in the same manner as in Preparation Example 1 to obtain about 478 g of a distillate (distillation yield: about 55.8%). 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 98.5%. After separation of the distillate, isosorbide (dianhydrosugar alcohol) 1.9% by weight, isomannide (dianhydrosugar alcohol) 2.1% by weight, sorbitan (monanhydrosugar alcohol) 0.9% by weight, polysaccharide alcohol represented by Formula 1 and 12.4% by weight of anhydrosugar alcohol derived therefrom and 82.7% by weight of a polymer thereof, wherein the composition has a number average molecular weight of 294 g/mol, a polydispersity index of 2.1, and a hydroxyl value of the composition of 714 mg KOH/ g, to obtain about 378 g of a polyol composition having an average number of -OH groups per molecule in the composition of 3.74.

<Preparation of acrylic-modified polyurethane composition>

Example A1: Acrylic-modified using 100 parts by weight of the polyol composition of Preparation Example 1 as a polyol, isophorone diisocyanate (IPDI) as a polyisocyanate, and 2-hydroxyethyl methacrylate as a hydroxyalkyl (meth)acrylate Polyurethane composition preparation

Put 222 g of isophorone diisocyanate (IPDI) and 0.1 g of dibutyltin dilaurate (DBTDL) as a reaction catalyst in a three-necked glass reactor with a stirrer, and slowly add 65 g of 2-hydroxyethyl methacrylate while mixing at room temperature. After preparing 287 g of an acryl-modified isocyanate intermediate to which hydroxyalkyl (meth)acrylate is partially added, 287 g of the polyol composition obtained in Preparation Example 1 (corresponding to 100 parts by weight relative to 100 parts by weight of the acryl-modified isocyanate intermediate) was introduced slowly. After completion of the input, the reaction product was cooled to room temperature after aging and stirring at 50° C. for 1 hour, to obtain 570 g of an acryl-modified polyurethane composition.

Example A2: Acrylic-modified poly using 30 parts by weight of the polyol composition of Preparation Example 1 as a polyol, hexamethylene diisocyanate (HDI) as a polyisocyanate, and 2-hydroxyethyl acrylate as a hydroxyalkyl (meth)acrylate Preparation of urethane composition

168 g of hexamethylene diisocyanate (HDI) was used in place of isophorone diisocyanate (IPDI) as polyisocyanate, and 2-hydroxyethyl in place of 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate The same method as in Example A1 was used except that 58 g of acrylate was used, and 67.8 g of the polyol composition obtained in Preparation Example 1 (acryl-modified isocyanate intermediate 100 parts by weight, corresponding to 30 parts by weight) was used as a polyol. 290 g of an acrylic-modified polyurethane composition was obtained.

Example A3: Acryl- using 300 parts by weight of the polyol composition of Preparation Example 1 as a polyol, methylenediphenyl diisocyanate (MDI) as a polyisocyanate, and 2-hydroxyethyl methacrylate as a hydroxyalkyl (meth)acrylate Modified polyurethane composition preparation

As polyisocyanate, 250 g of methylenediphenyl diisocyanate (MDI) was used instead of isophorone diisocyanate (IPDI), and 945 g of the polyol composition obtained in Preparation Example 1 as a polyol (acryl-modified isocyanate intermediate 100 parts by weight, relative to 100 parts by weight, 300 weight 1,220 g of an acrylic-modified polyurethane composition was obtained by performing the same method as in Example A1, except that part) was used.

Example A4: Acrylic-modified poly using 150 parts by weight of the polyol composition of Preparation Example 2 as a polyol, hexamethylene diisocyanate (HDI) as a polyisocyanate, and 2-hydroxyethyl acrylate as a hydroxyalkyl (meth)acrylate Preparation of urethane composition

168 g of hexamethylene diisocyanate (HDI) was used in place of isophorone diisocyanate (IPDI) as polyisocyanate, and 2-hydroxyethyl in place of 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate 58 g of acrylate is used, and 339 g of the polyol composition obtained in Preparation Example 2 (corresponding to 100 parts by weight of the acrylic-modified isocyanate intermediate, corresponding to 150 parts by weight) is used instead of the polyol composition wool obtained in Preparation Example 1 as a polyol Then, 550 g of an acrylic-modified polyurethane composition was obtained by performing the same method as in Example A1.

Comparative Example A1: Using polyethylene glycol (number average molecular weight: 500 g/mol) as polyol, isophorone diisocyanate (IPDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate Acrylic-modified polyurethane manufacturing

As a polyol, 500 g of polyethylene glycol (number average molecular weight: 500 g/mol) (corresponding to 174 parts by weight, relative to 100 parts by weight of the acryl-modified isocyanate intermediate) was used instead of the polyol composition obtained in Preparation Example 1, 782 g of an acrylic-modified polyurethane of the following Chemical Formula 4 was obtained by performing the same method as in Example A1.

[Formula 4]

Comparative Example A2: Using polypropylene glycol (number average molecular weight: 500 g/mol) as polyol, hexamethylene diisocyanate (HDI) as polyisocyanate, and 2-hydroxyethyl acrylate as hydroxyalkyl (meth)acrylate Acrylic-modified polyurethane manufacturing

168 g of hexamethylene diisocyanate (HDI) was used in place of isophorone diisocyanate (IPDI) as polyisocyanate, and polypropylene glycol (number average molecular weight: 500 g/mol) in place of the polyol composition obtained in Preparation Example 1 as a polyol , Kumho Petrochemical (Production)) 500 g (corresponding to 221 parts by weight relative to 100 parts by weight of the acryl-modified isocyanate intermediate), as a hydroxyalkyl (meth)acrylate, instead of 2-hydroxyethyl methacrylate 720 g of an acrylic-modified polyurethane of the following formula (5) was obtained by performing the same method as in Example A1 except that 58 g of 2-hydroxyethyl acrylate was used.

[Formula 5]

Comparative Example A3: Polytetramethylene glycol (number average molecular weight: 1,000 g/mol) as polyol, methylenediphenyl diisocyanate (MDI) as polyisocyanate, 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate Acrylic-modified polyurethane production using

As a polyisocyanate, 250 g of methylenediphenyl diisocyanate (MDI) was used in place of isophorone diisocyanate (IPDI), and as a polyol, polytetramethylene glycol (number average molecular weight: 1,000 g) in place of the polyol composition obtained in Preparation Example 1 /mol, Aldrich Corporation (manufactured by)) 1,000 g (corresponding to 317 parts by weight, relative to 100 parts by weight of the acryl-modified isocyanate intermediate), by performing the same method as in Example A1, the acryl- 1,308 g of modified polyurethane was obtained.

[Formula 6]

Comparative Example A4: Preparation of acrylic-modified polyurethane using isosorbide as polyol, isophorone diisocyanate (IPDI) as polyisocyanate, and 2-hydroxyethyl methacrylate as hydroxyalkyl (meth)acrylate

By performing the same method as in Example A1 except that 146 g of isosorbide (corresponding to 51 parts by weight, relative to 100 parts by weight of an acryl-modified isocyanate intermediate) was used instead of the polyol composition obtained in Preparation Example 1 as a polyol. 431 g of an acrylic-modified polyurethane of Formula 7 was obtained.

[Formula 7]

<Preparation of aqueous coating solution composition>

Examples B1 to B4 and Comparative Examples B1 to B4: standard preparation

Water, potassium persulfate (KPS) as a polymerization initiator, acryl-modified polyurethane, and acrylic monomer were mixed in the weight ratio shown in Table 1 below, and then sufficiently stirred using a high-speed dissolver, and then heated to 85° C. and stirred. Then, the polymerization reaction was sufficiently conducted for 3 hours to prepare aqueous coating solution compositions of Examples B1 to B4 and Comparative Examples B1 to B4.

[Table 1]

<Evaluation of physical properties of the aqueous coating solution composition>

The aqueous coating solution composition prepared in Examples B1 to B4 and Comparative B1 to B4 was coated twice on a polyvinyl chloride (PVC) film and dried to prepare a specimen comprising a polyvinyl chloride film and a coating film formed on the film and the adhesiveness, crack resistance, and water resistance of the specimens were evaluated by the following method, and the results are shown in Table 2 below.

<Method of measuring physical properties>

(1) Adhesiveness

According to ASTM D 3359, which is the standard for testing adhesion of coatings, by using a cross hatch cutter to cross a line and make a scratch on the coating film of the specimens, 100 grid pieces of size 10mm x 10mm were made, and then the tape was placed on the grid piece After attaching and rubbing with uniform force, the tape was peeled off, and the number of grid pieces that came off from the coating film of the specimens and adhered to the removed tape was counted. The degree of adhesion is expressed as a numerical value of 0B to 5B according to the number of grid pieces separated from the coating film of the specimens. (Level 4B or higher required)

(2) crack resistance

After storing the specimens in a freezer at -20°C for 1 hour and storing them in a hot-air dryer at 80°C for 1 hour, repeating 5 times, the coating film of the specimens is broken, peeled, cracks such as cracks The occurrence was visually observed.

(3) water resistance

After immersing the specimens in room temperature water for 72 hours, it was visually observed whether swelling, cracking, peeling, discoloration, etc. of the coating film occurred.

[Table 2]

As shown in Table 2 above, in the case of the aqueous coating solution compositions of Examples B1 to B4 prepared using the acrylic-modified polyurethane composition according to the present invention, all of the standard requirements of adhesion, cracking properties and water resistance were achieved.

On the other hand, in the case of the aqueous coating solution composition of Comparative Example B1 to which the acrylic-modified polyurethane prepared using polyethylene glycol, which is a general-purpose hydrophilic polyol, was applied, cracks occurred in the coating film and peeling occurred in room temperature water, resulting in poor water resistance. In addition, in the case of the aqueous coating solution compositions of Comparative Examples B2 and B3 to which the acrylic-modified polyurethane prepared using polypropylene glycol or polytetramethylene glycol, which are general-purpose polyols, is applied, phase separation occurs within the coating solution composition, and evaluation of physical properties as an aqueous coating solution was impossible.

In addition, in the case of Comparative Example B4 to which the acrylic-modified polyurethane prepared by using anhydrosugar alcohol (ISB) alone was applied, peeling occurred in room temperature water, resulting in poor water resistance.

As described above, in the case of the water-based coating solution composition prepared using the acrylic-modified polyurethane composition according to the present invention, it is an eco-friendly water-based coating solution without any organic solvent and/or surfactant, and has all of adhesion, crack resistance and water resistance. You can see that it is excellent.

Claims (12)

An acrylic-modified polyurethane composition comprising the first to fifth acrylic-modified polyurethanes,
The first to fifth acrylic-modified polyurethanes are derived from the first to fifth polyol components, respectively, together with a polymerized unit derived from polyisocyanate and a polymerized unit derived from hydroxyalkyl (meth)acrylate. polymerized units;
here,
The first polyol component is monosugar alcohol,
The second polyol component is dianhydrosugar alcohol,
The third polyol component is a polysaccharide alcohol represented by the following formula (1),
The fourth polyol component is an anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the following formula (1),
The fifth polyol component is one or more polymerization products selected from the first to fourth polyol components,
Acrylic-modified polyurethane composition:
[Formula 1]

In Formula 1, n is an integer of 0 to 4. The acrylic-modified polyurethane composition according to claim 1, wherein the first polyol component is hexitol monohydrate. The acrylic-modified polyurethane composition according to claim 1, wherein the second polyol component is hexitol dianhydride. The acrylic-modified polyurethane 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 from 0 to 4. The acrylic-modified polyurethane composition according to claim 1, wherein the fifth polyol component is 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. According to claim 1,
the first acryl-modified polyurethane is an acryl-modified polyurethane represented by the following formula (A);
the second acryl-modified polyurethane is an acryl-modified polyurethane represented by the following formula (B);
the third acryl-modified polyurethane is an acryl-modified polyurethane represented by the following formula (C);
the fourth acryl-modified polyurethane is an acryl-modified polyurethane represented by the following formula (D);
The fifth acrylic-modified polyurethane is an acrylic-modified polyurethane represented by the following formula (E),
Acrylic-modified polyurethane composition:
[Formula A]

[Formula B]

[Formula C]

[Formula D]

[Formula E]

In the above formulas A to E,
R1 is each independently an alkylene group, a cycloalkylene group, or an arylene group,
R2 is each independently each independently an alkylene group,
R3 is each independently each independently a hydrogen atom or an alkyl group,
L1 is a divalent organic group derived from the first polyol component,
L2 is a divalent organic group derived from the second polyol component,
L3 is a divalent organic group derived from the third polyol component,
L4 is a divalent organic group derived from the fourth polyol component,
L5 is a divalent organic group derived from the fifth polyol component. (1) reacting polyisocyanate and hydroxyalkyl (meth)acrylate to prepare an acrylic-modified isocyanate intermediate; and
(2) reacting the acrylic-modified isocyanate intermediate obtained in step (1) with a polyol composition comprising the first to fifth polyol components;
here,
The first polyol component is monosugar alcohol,
The second polyol component is dianhydrosugar alcohol,
The third polyol component is a polysaccharide alcohol represented by the following formula (1),
The fourth polyol component is an anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the following formula (1),
The fifth polyol component is one or more polymerization products selected from the first to fourth polyol components,
Method for preparing the acrylic-modified polyurethane composition:
[Formula 1]

In Formula 1, n is an integer of 0 to 4. The method for producing an acrylic-modified polyurethane composition according to claim 7, wherein in step (2), 30 to 300 parts by weight of the polyol composition are reacted per 100 parts by weight of the acrylic-modified isocyanate intermediate. A polymer composition prepared from the polymerization reaction of the acrylic-modified polyurethane composition of any one of claims 1 to 6 and a hydrophilic acrylic monomer; and water; containing, a water-based coating solution composition. The aqueous coating solution composition according to claim 9, wherein the hydrophilic acrylic monomer is at least one selected from the group consisting of an acrylic monomer having a carboxyl group, an acrylic monomer having an amide group, an acrylic monomer having a hydroxyl group, and combinations thereof. The aqueous coating solution composition according to claim 9, wherein the content of the acrylic-modified polyurethane composition is greater than 30 parts by weight and less than 85 parts by weight based on 100 parts by weight of the total of the acrylic-modified polyurethane composition, the hydrophilic acrylic monomer and water. In the presence of water and a polymerization initiator as a solvent, a method for preparing an aqueous coating solution composition comprising the step of polymerizing the acrylic-modified polyurethane composition of any one of claims 1 to 6 and a hydrophilic acrylic monomer.