KR101031307B1 - Composition of water-dispersible polyurethane-urea/acrylate hybrid emulsion and preparing method of the same - Google Patents

Abstract

The present invention relates to a nano-acrylic hybrid water-dispersed polyurethane composition in which an acryl group is introduced into a polyurethane, and a method for preparing the same, in which dimethylol propionic acid is added to a polyurethane prepolymer synthesis step and triethylamine is used for the carboxyl group of dimeltylol propionic acid. A neutral hydrophilic group was introduced, and methyl methacrylate was added to the prepolymer to react with ethylene glycol dimethacrylate, which acts as a crosslinking agent of methyl methacrylate. After that, the nano-acrylic hybrid water-dispersed polyurethane composition having excellent physical properties can be obtained by controlling the content of the acrylic monomer and increasing the bonding strength by the crosslinking reaction by the chain extension and the emulsion-free polymerization method.

Description

Composition of water-dispersible poly (urethane-urea) / acrylate hybrid emulsion and preparing method of the same

The present invention relates to an acrylic hybrid water-dispersed polyurethane composition and a method for preparing the same, and more particularly, in the polyurethane prepolymer synthesis step, an emulsifier is not used due to the influence of the carboxyl group of dimethylol propionic acid and the hydrophilic group according to the degree of neutralization of trimethylamine. The present invention relates to an acrylic hybrid water-dispersed polyurethane composition and a method of manufacturing the same, which can be used in a coating coating of various plastics because of its excellent particle stability while having excellent nanoparticle size and excellent particle stability.

Coating paints for the coating of various plastics are growing into an important market at home and abroad. Such coating coating paints have generally used organic solvents, but in the case of using organic solvents, environmental pollution by volatile organic compounds has emerged as a serious social problem. As a result, global regulations on volatile organic compounds emission prevention, global warming prevention, and ozone depletion prevention are being followed in order to prevent environmental pollution.

According to this social trend, a lot of researches have been conducted to manufacture coating paints for eco-friendly painting, and as a part of this, various technologies for using water instead of organic solvents have been studied. Typically such aqueous paints comprise aqueous resins, pigments and other additives. Here, as an aqueous resin, an acrylic emulsion, a water dispersion polyurethane, an acrylic hybrid water dispersion polyurethane, etc. are mainly used.

Acrylic emulsion has excellent toughness, weather resistance, reactivity, compatibility with other resins, pigment miscibility, gloss, etc., and is relatively inexpensive, so it is widely used and widely used in the coating industry. Physical properties such as elongation, adhesion and hardness are insufficient. In recent years, as an aqueous coating resin, an acrylic hybrid water-dispersed polyurethane capable of exhibiting both acrylic and polyurethane properties has been gradually used.

Most acrylic hybrid water-dispersed polyurethanes are prepared in the form of swelling and polymerizing acrylic monomers using urethane as seed particles. However, most of the acrylic hybrid water-dispersed polyurethanes currently developed have poor particle dispersion stability due to their large particle size and hydrophilicity with water, and in particular, when applied to undercoat paints, they have poor coating properties such as adhesion, chemical resistance, salt water resistance, and water resistance. There is a problem.

The present invention is to solve the above-mentioned conventional problems, to provide an acrylic hybrid water-dispersible polyurethane composition in which acrylic hybrid polyurethane is dispersed in an aqueous phase in a more stable form at the size of nanoparticles without using an emulsifier. There is this.

In addition, the present invention does not use an emulsifier, the acrylic hybrid polyurethane is dispersed in the aqueous phase in a more stable form in the size of nanoparticles, and the chain extender is added to increase the molecular weight of the polyurethane acrylic hybrid to obtain excellent physical properties Another object is to provide a method of preparing a water-dispersed polyurethane.

In another aspect, the present invention is to produce a coating material for coating comprising the acrylic hybrid water-dispersed polyurethane composition.

In order to achieve the above object, the present invention is added to 5 parts by weight of dimethylol propionic acid and 20 to 60 parts by weight of an isocyanate compound to 100 parts by weight of a polyol having a number average molecular weight of 500 to 3000, and then neutralizing the pH. Polyurethane prepolymer prepared by adding until 7 to 10; Methyl methacrylate; Ethylene glycol dimethacrylate (EGDMA), which is a crosslinking agent of methyl methacrylate; Water as a solvent; Chain extenders; And an initiator, wherein the ethylene glycol dimethacrylate is 0.5 to 5 parts by weight based on 100 parts by weight of methyl methacrylate to provide a nano acrylic hybrid water-dispersed polyurethane composition.

In addition, the present invention is added by adding 5 to 10 parts by weight of dimethylol propionic acid and 20 to 60 parts by weight of isocyanate compound to 100 parts by weight of polyol having a number average molecular weight of 500 to 3000, and then neutralizing agent is added until pH 7-10. Prepolymer manufacturing step to produce a polyurethane prepolymer; Activating by adding ethylene glycol dimethacrylate (EGDMA), which is a crosslinking agent of methyl methacrylate and methyl methacrylate, to the prepolymer; A water dispersion step of dispersing the reaction solution prepared in the activation step in an aqueous phase; And a chain extender and an initiator are added to the dispersed emulsion, wherein the ethylene glycol dimethacrylate is added in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of methyl methacrylate. It provides a method for producing a water-dispersed polyurethane composition.

In another aspect, the present invention provides a method for producing a coating paint, characterized in that it comprises the acrylic hybrid water dispersion polyurethane composition.

The acrylic hybrid water-dispersed polyurethane composition according to the present invention is excellent in particle stability having nano-particle size by introducing a hydrophilic group by adding dimethylol propionic acid to the prepolymer in the synthesis step and neutralizing the carboxyl group of dimeltylol propionic acid using triethylamine. When the water dispersion process is secured and methyl methacrylate is added and reacted, ethylene glycol dimethacrylate, which acts as a crosslinking agent of methyl methacrylate, is added together and polymerized, thereby increasing the crosslinking density between methyl methacrylates. As the bonding force increases, the hardness property shows excellent physical properties.

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

Acrylic mixed water dispersion polyurethane composition according to the present invention is a polyurethane prepolymer prepared by (A) a polyol by adding dimethylol propionic acid and an isocyanate compound to react and then neutralizing agent; (B) methyl methacrylate; (C) ethylene glycol dimethacrylate (EGDMA) which is a crosslinking agent of methyl methacrylate; (D) water as a solvent; Chain extenders (E); And (F) initiators.

(A) polyurethane prepolymer

The polyurethane prepolymer according to the present invention is prepared according to a known method of adding a neutralizing agent after reacting by adding dimethylol propionic acid and an isocyanate compound to a polyol.

In the present invention, 5 to 10 parts by weight of dimethylolpropionic acid (DMPA) and 20 to 60 parts by weight of an isocyanate compound are added to 100 parts by weight of a polyol having a number average molecular weight of 500 to 3000, followed by addition of a neutralizing agent. The prepared polyurethane prepolymer was prepared.

Here, the polyol has a number average molecular weight of 500 to 3000, but if the number average molecular weight of the polyol is less than 500, there is a disadvantage in that the dispersion stability is poor, the workability is poor when applying the coating coating, the number average molecular weight exceeds 3000 When applied to the undercoat coating has a disadvantage in that the flexibility of the coating film is increased to reduce the overall physical properties. Therefore, it is preferable to use a polyol having a number average molecular weight within the above range. More preferably, the number average molecular weight is 1000 to 2500.

As the polyol, polyester polyol, carbonate polyol, caprolactone polyol and the like can be used. Preferably, polyester polyols are used.

Polyester polyols are generally commercially available and are obtained by condensation of diacids or acid anhydrides with glycols. Diacids can be used either saturated or unsaturated and alkyl or cyclic alkyl and phenyl. Examples include phthalic acid, hydrozinnate phthalic acid, isoplic acid, tellaflic acid, malonic acid, succinic acid, glutamic acid, adipic acid, pimelic acid, sublic acid, azeratic acid, sebacic acid, formic acid, succinic anhydride , Phthalic anhydride, maleic anhydride, hydrozinnate phthalic anhydride and the like. Alkyl glycols are generally used as glycols. Examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, methyl propane glycol, neopentyl glycol, butylethyl flopane glycol, butanediol, hexane diol and the like.

In the case of carbonate polyols, commercially available PCDLs from Asahi Kasai can be used.

In the case of caprolactone-based polyols, epsilon caplolactone-modified products can be used, and the commercialized lactone polyol Placcel 200 series of Daicel can be optionally used.

Dimethylolpropionic acid added to the polyol is used to introduce a hydrophilic group, and when the amount is less than 5 parts by weight with respect to 100 parts by weight of polyol, smooth water dispersion is difficult and the stability is low, and the amount of the added 10 If it exceeds the weight part, there is a disadvantage in that the chemical resistance is lowered when applied to the undercoat. Therefore, it is preferable to add 5-10 weight part of dimethylol propionic acids with respect to 100 weight part of polyols.

In this case, the dimethylol propionic acid may be added in a dissolved state in a solvent, for example, may be added by dissolving in a solvent such as N-methyl-2-pyrrolidone, methanol or ethanol, and the solvent is dimethylolpropy. 120 parts by weight or more with respect to 100 parts by weight of onic acid, preferably 120 to 200 parts by weight may be dissolved.

According to the present invention, 20 to 60 parts by weight of the isocyanate compound reacting with the polyol to form a polyurethane is added and reacted. At this time, the reaction is carried out for 3 hours or more in the state of raising the temperature of the reactor to 70 to 100 ℃, the end of the reaction can be easily confirmed through the change in the absorption band length of the isocyanate group (NCO), for example in the IR spectrum, etc. have.

At this time, when the amount of isocyanate added is less than 20 parts by weight with respect to 100 parts by weight of polyol, the resulting urethane bonds are insufficient, resulting in a lack of flexibility of the coating. This occurs, and when the amount of isocyanate added exceeds 60 parts by weight, the viscosity of the paint is increased to improve the workability and there is a problem that the overall coating properties are lowered. Therefore, it is preferable to add 20-60 weight part of addition amounts of isocyanate with respect to 100 weight part of polyols.

Isocyanates can use all of the most commonly used isocyanates, but it is preferable to use diisocyanate. As the diisocyanate, those selected from toluene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, isophorone diisocyanate, hexane diisocyanate, hexamethylene diisocyanate and the like can be used.

In order to promote the reaction, a catalyst used in preparing a conventional polyurethane may be added within a conventional addition range, and a usable catalyst is dibutyltin dilaurate (DBDTL).

Neutralization is achieved by adding the neutralizing agent to pH 7-10 with the reaction vessel cooled to 50-70 ° C.

The neutralizing agent may be ammonia, ethylamine, butylamine, dimethylamine, diisopropylamine, dimethylethylamine, benzylamine, ethanolamine, diethanolamine, triethanolamine, tributylamine, methyl diethanolamine, diethylethanolamine, Dimethylethanolamine, normal methylmorpholine, diisopropanolamine or 2-amino2-methyl1-propanol may be used, and preferably diethylethanolamine is used.

(B) Methyl methacrylate (MMA)

The nano acrylic hybrid water-dispersed polyurethane composition according to the present invention includes methyl methacrylate for imparting acrylic resin properties. As such, when methyl methacrylate is used to impart acrylic resin properties, chemical resistance is superior to that of other acrylate monomers. In particular, it is possible to prepare a composition according to the physical properties through the control of the addition amount.

It is preferable to add 10-40 weight part of said methyl methacrylates with respect to 100 weight part of polyurethane. If the added amount is less than 10 parts by weight, it is difficult to expect the improvement of chemical resistance, and if the added amount exceeds 40 parts by weight, the size of the dispersed particles increases during water dispersion, and thus there is a problem in that water dispersion stability is lowered. Therefore, methyl methacrylate is preferably added within the above range.

(C) Ethylene Glycol Dimethacrylate (EGDMA)

According to the present invention, in order to improve physical properties such as hardness and adhesion, ethylene glycol dimethacrylate, which serves as a crosslinking agent of methyl methacrylate, is added. Therefore, when ethylene glycol dimethacrylate is added together with methyl methacrylate, the crosslinking density is increased, and the ethylene glycol dimethacrylate increases the bonding strength between acrylate resins, such as hardness, adhesion, chemical resistance, etc. The characteristic can be improved.

It is preferable to add 1-5 weight part of said ethylene glycol dimethacrylates with respect to 100 weight part of methyl methacrylates. If the added amount is less than 1 part by weight, it is difficult to obtain improved hardness characteristics, and if the added amount is more than 5 parts by weight, there is a problem in that the adhesive property becomes weak. Therefore, it is preferable to add ethylene glycol dimethacrylate within the above range.

(D) water as a solvent

The solvent uses water, which is environmentally friendly compared to the use of conventional organic solvents. If necessary, some alcohol solvents may be used for the purpose of improving workability. For example, a very small amount of methanol, ethanol, isopropanol, butanol, methylcellulose, ethyl solusorb, etc. may be used.

It is not necessary to limit the addition amount of water, but 100 to 300 parts by weight may be added based on 100 parts by weight of polyurethane. If the added amount is less than 100 parts by weight, the coating property is lowered, and if it exceeds 300 parts by weight there is a disadvantage that it is difficult to form a coating of the desired thickness.

(E) chain extenders

According to the invention a chain extender for molecular weight control is added.

The chain extender may use diamines and diol compounds, specifically, a compound containing two primary or secondary amino groups and two hydroxyl groups, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexamethylenediamine , Ethylenediol, propylenediol, butylenediol, pentylenediol, hexamethylenediol can be used by mixing at least one or more.

The chain extender is preferably added 1 to 5 parts by weight based on 100 parts by weight of polyurethane. In addition, the chain extender is preferably added after dilution in a small amount of water.

(F) Initiator

The composition according to the invention comprises a polymerization initiator. As the polymerization initiator, those generally used in the art may be used.

Examples of the polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis, [2- (5 -Methyl-2-imidazolin-2-yl) propane], dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N ' Azo systems such as -dimethylene isobutyl amidine), 2,2'-azobis, [N- (2-carboxyethyl) -2-methylpropionamidine], and hydrates (made by Wako Junyaku, VA-057) Persulfates such as initiators, potassium persulfate, ammonium persulfate, di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate , t-butylperoxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3- Tetramethylbutylperoxy-2- Butylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoylperoxide, t-butylperoxyisobutylate, 1,1-di (t-hexylperoxy) cyclohexane, t-butylhydroperoxide And a peroxide-based initiator such as hydrogen peroxide, a combination of persulfate and sodium hydrogen sulfite, a peroxide-reducing initiator such as a combination of peroxide and sodium ascorbate and a reducing agent, and the like.

The said polymerization initiator may be used independently, or may mix and use 2 or more types. The total amount of use is preferably 0.05 to 0.5 parts by weight based on 100 parts by weight of polyurethane.

(G) other additives

In addition to the above components, various additives may be included within a range that does not change the characteristics of the present invention. Antioxidants, UV absorbers, light stabilizers, thermal polymerisation inhibitors, leveling agents, including, for example, antistatic agents selected from conductive polymers, quaternary ammonium salts, inorganic salts, metal particles, (meth) acrylate modified quaternary ammonium salts , Surfactants, lubricants and the like may additionally be used within the usual addition range.

The present invention provides a method for producing a nano acrylic hybrid water-dispersed polyurethane composition more effectively using the above components. The method comprises the steps of adding a dimethylol propionic acid and an isocyanate compound to the polyol to react and then adding a neutralizing agent to prepare a polyurethane prepolymer; Ethylene glycol dimethacrylate (EGDMA), which is a crosslinking agent of methyl methacrylate and methyl methacrylate, is added to the prepolymer to be activated; A dispersion step of dispersing the reaction solution prepared in the activation step in an aqueous phase; And a chain extender and an initiator in the dispersed emulsion.

Wherein the prepolymer manufacturing step is to produce a polyurethane using the process generally applied in the present invention, in the present invention in the state of increasing the temperature of the reactor to 70 to 100 ℃ number average molecular weight of 500 to 3000 in 100 parts by weight of polyol After adding 5-10 parts by weight of dimethylolpropionic acid (DMPA) and 20-60 parts by weight of isocyanate compounds, the reaction is carried out to lower the temperature of the reactor to 50-70 ° C. until the neutralizer reaches pH 7-10. Will be added.

The dimethylol propionic acid may be added by dissolving in a solvent such as N-methyl-2-pyrrolidone, methanol or ethanol. The solvent may be used in an amount of 120 to 200 parts by weight based on 100 parts by weight of dimethylol propionic acid. In addition, a reaction catalyst such as dibutyltin dilaurate (DBDTL), which is generally used in polyurethane production, may be further added to promote the reaction.

When the polyurethane is prepared through the preparation step of the prepolymer, methyl methacrylate and its crosslinking agent, ethylene glycol dimethacrylate (EGDMA), are put together to be activated. The methyl methacrylate is added 10 to 40 parts by weight based on 100 parts by weight of polyurethane, and the ethylene glycol dimethacrylate is added 1 to 5 parts by weight based on 100 parts by weight of methyl methacrylate.

Ethylene glycol dimethacrylate as a crosslinking agent in the activation step serves to improve the physical properties of the film, in particular the hardness by acting as a crosslinking agent of methyl methacrylate.

After the activation step is completed, a dispersion step of dispersing the reaction solution prepared in the activation step in the water phase. Dispersion is made by slowly adding the reaction solution passed through the activation step while putting water in a separate vessel and stirring. The content of water is not particularly limited but may be freely added within the range of 30 to 50% by weight of solids in the final product in consideration of workability. Preferably it is 150 to 250 parts by weight based on 100 parts by weight of polyurethane.

After the dispersion is completed, a chain extender and an initiator are added to the dispersed emulsion. The chain extender is used 1 to 5 parts by weight based on 100 parts by weight of polyurethane, the initiator is 0.05 to 0.5 parts by weight. The chain extender may be added by dilution in a small amount of water.

The nano acrylic hybrid water-dispersed polyurethane composition according to the present invention prepared as described above may be usefully used for coating paints, in particular, mobile phone undercoat coatings, and when applied to coating paints, chemical resistance, hardness, adhesiveness, etc. Exhibits excellent properties in physical properties.

Therefore, the present invention provides a coating material containing the acrylic hybrid water-dispersed polyurethane composition prepared as described above. Here, the coating composition in the coating composition can be adjusted in various amounts, preferably 40 parts by weight or more, more preferably 40 to 90 parts by weight based on 100 parts by weight of the total coating paint.

The coating material for coating may be a mixture of glitters, pigments and various additives such as silver powder and pearl used in the art. In addition, a polyisocyanate curing agent may be selectively used to improve physical properties of the coating material. The glitter may be coated aluminum powder, copper powder, pearl, or the like.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are only presented to aid the understanding of the present invention and the present invention is not limited thereto.

≪ Example 1 >

A polyol methylene adipate with a number average molecular weight of 2,000 g was added to a 1000 mL four-neck double jacketed reactor connected with a condenser and a stirrer, and then dissolved at 80 ° C. After dissolving the polyol, 23.795 g of isophorone diisocyanate was added together with 0.005 g of DBTL and polymerized with stirring for 140 minutes. Then, 4 g of dimethylol propionic acid (DMPA) having a hydrophilic group was dissolved in 11 g of NMP, and then stirred for 80 minutes. After the reaction, the temperature was lowered to 60 ° C. and triethylamine (TEA) 3.2 was added to neutralize the carboxyl group of DMPA for 20 minutes. 25 g of methyl methacrylate and 0.5 g of ethylene diglycol methacrylate (EDGMA) as a crosslinking agent were added together and stirred for 10 minutes.

200 g of ultrapure water was added to a separate 1000 mL reactor, and the reaction solution was slowly added thereto while stirring at 500 rpm to perform a water dispersion process at 60 ° C. 2 g of ethylenediamine (EDA) was added to 8 g of ultrapure water, and the diluted solution was added to the reaction solution in which the water dispersion step was completed, followed by stirring for 2 hours. 0.2 g of potassium peroxide as an initiator was added thereto, followed by radical polymerization for 4 hours to prepare an acrylic hybrid water-dispersed polyurethane composition.

<Examples 2 to 6 and Comparative Examples 1 to 3>

An acrylic hybrid water-dispersed polyurethane composition was prepared in the same manner as in Example 1 except that the amount of methyl methacrylate and ethylene glycol methacrylate (EGDMA) was changed as shown in Table 1 below. It was.

Experimental Example 1

Using the acrylic hybrid water-dispersed polyurethane composition prepared in Examples 1 to 6 and Comparative Examples 1 to 3, the physical properties were evaluated as shown below, and the results are shown in Table 1.

1. Grain size

The particle size of the nano acrylic hybrid water-dispersed polyurethane composition was measured by dilution with ultrapure water at 25 ° C. using capillaryhydrodynamic fractionation (CHDF2000, Matee Applied Sience, U.S.A.).

2. Tensile Strength

The prepared nano acrylic hybrid water-dispersed polyurethane composition was coated on a OPP (oriented polypropylene) film with a thickness of 0.2 mm without using a curing agent or other additives, and then dried at 80 ° C. for 24 hours. Then, the tensile strength was measured using a universal testing machine (UTM, Instron Co., U.S.A) at room temperature. At this time, the UTM had a crosshead speed of 10 mm / min, and the average of five measurements was taken as the tensile strength.

3. Chemical resistance

The prepared nano acrylic mixed water dispersion polyurethane composition was coated on a polycarbonate substrate using a spray gun without using a curing agent or other additives. The film thickness was dried at about 10 mu m at 80 deg.

Chemical resistance was measured using an eraser individual life tester (Daesung Precision) .The tester was tested at 40 reciprocating speeds per minute while placing an eraser loaded with 500g on the specimen and dampening the test area with methanol. The carbonate material side was tested until revealed. The number of round trips was determined once, and the average value was taken after five or more experiments on the same sample.

4. Adhesiveness

The prepared acrylic mixed water dispersion polyurethane composition was coated on a polycarbonate substrate using a spray gun without using a curing agent or other additives. The film thickness was dried at about 10 mu m at 80 deg.

Make 100 squares of 1mm vertical on the coated film, attach 50mm wide transparent OPP tape on it, and then scratch it with a pen tip or fingernail and press it tightly without any gaps between the scales. Peeled off. After 10 times of these desorption tests, the number of scales remaining was evaluated.

5. Cosmetic resistance

The prepared nano acrylic mixed water dispersion polyurethane composition was coated on a polycarbonate substrate using a spray gun without using a curing agent or other additives. The film thickness was dried at about 10 mu m at 80 deg.

Nivea Sun spray of SPF 20 is applied to the coated surface of the test piece by applying a cream to the brush, and left for 10 minutes at room temperature, and left flat for 24 hours at 80 ° C and 80% chamber, followed by washing with water and removing the moisture with a cloth, and standing at room temperature for 4 hours. Thereafter, a line was drawn at intervals of 2 mm on the test piece, and the eye was made to reach the film as much as the allowable area.

Experimental Example 2

The acrylic hybrid water-dispersed polyurethane composition prepared in Examples 1 to 6 and Comparative Examples 1 to 3 was also coated on the polycarbonate substrate by adding 5% of a polyisocyanate curing agent. At this time, an aqueous two-component acrylic polyurethane paint using a water-dispersible acrylic polyol and an isocyanate curing agent modified with a hydrophilic group was used as a coating for coating.

Then, the chemical resistance and adhesion evaluation in the same manner as the chemical resistance and adhesion evaluation of Experimental Example 1 and the results are shown in Table 1 below.

division MMA
Addition amount
(g) EGDMA
Addition amount
(g) Experimental Example 1 Experimental Example 2 Granularity The tensile strength Chemical resistance Adhesion Fireproof
Character Tolerance
Character Adhesion Fireproof
Character Example 1 10 3 79.1 255.9 16 100/100 65/100 250 100/100 100/100 Example 2 20 3 127.0 254.6 21 100/100 70/100 250 100/100 100/100 Example 3 30 3 198.2 167.7 30 100/100 80/100 270 100/100 100/100 Example 4 40 3 211.5 142.3 30 100/100 80/100 300 100/100 100/100 Example 5 20 One 105.5 199.2 16 100/100 40/100 230 100/100 100/100 Example 6 30 One 112.2 212.3 24 100/100 50/100 230 100/100 100/100 Comparative Example 1 10 - 88.9 81.4 2 100/100 50/100 200 100/100 100/100 Comparative Example 2 20 - 90.0 170.8 11 100/100 40/100 220 100/100 100/100 Comparative Example 3 30 - 153.2 254.0 20 100/100 40/100 220 100/100 100/100

As shown in Table 1, Examples 1 to 6 to which MMA and EGDMA were added within the preferred range of the present invention can be confirmed to have excellent physical properties compared to Comparative Examples 1 to 3 to which EGDMA was not added. When EGDMA is used in excess (range of the present invention), it is not included in the comparative example because the aggregation density is too high and aggregation occurs.

Claims (8)

Prepared by adding 5-10 parts by weight of dimethylol propionic acid and 20-60 parts by weight of isocyanate compound to 100 parts by weight of polyol having a number-average molecular weight of 500-3000, and then adding a neutralizing agent until the pH is 7-10. One polyurethane prepolymer; Methyl methacrylate; Ethylene glycol dimethacrylate (EGDMA), which is a crosslinking agent of methyl methacrylate; Water as a solvent; Chain extenders; And Including an initiator, The ethylene glycol dimethacrylate is a nano acrylic hybrid water-dispersed polyurethane composition, characterized in that by adding 0.5 to 5 parts by weight based on 100 parts by weight of methyl methacrylate. delete The method of claim 1, The methyl methacrylate is a nano acrylic hybrid water-dispersed polyurethane composition, characterized in that 10 to 40 parts by weight based on 100 parts by weight of polyurethane. Polyurethane prepolymer is added by adding 5-10 parts by weight of dimethylol propionic acid and 20-60 parts by weight of isocyanate compound to 100 parts by weight of polyol having a number-average molecular weight of 500-3000, and then adding neutralizing agent until pH 7-10. Preparing a prepolymer; Activating by adding ethylene glycol dimethacrylate (EGDMA), which is a crosslinking agent of methyl methacrylate and methyl methacrylate, to the prepolymer; A water dispersion step of dispersing the reaction solution prepared in the activation step in an aqueous phase; It comprises the step of adding a chain extender and an initiator in the dispersed emulsion, The ethylene glycol dimethacrylate is 0.5 to 5 parts by weight based on 100 parts by weight of methyl methacrylate is a method for producing a nano acrylic mixed water dispersion polyurethane composition. delete The method of claim 4, wherein The methyl methacrylate is a method for producing a nano acrylic hybrid water-dispersible polyurethane composition, characterized in that 10 to 40 parts by weight based on 100 parts by weight of polyurethane. delete A coating material for coating comprising the nanoacrylic hybrid water-dispersed polyurethane composition of claim 1.