KR20130124723A - Silylated acrylic polyurethane dispersion, preparation method of the dispersion and paint including the same - Google Patents

Abstract

The present invention relates to a silylated acrylic polyurethane emulsion, a preparing method of the emulsion, and a paint including the same. The preparation method of a silylated acrylic polyurethane emulsion comprises a step of preparing a prepolymer with an NCO group at the terminal by adding a dimethyl propionic acid and a diisocyanate-based compound into polyol; a step of adding a silane coupling agent to the resultant solution through the prepolymer step and capping the NCO group on the terminal of the prepolymer with a silane coupling agent; a water dispersion step of extending the chain of the product by adding a chain extending agent into the resultant solution through the capping step, neutralizing the resultant solution to have pH 7-10 by adding a neutralizing agent and stirring and dispersing the product while water is added to the product; and a polymerization step of adding an acrylic monomer to an emulsion prepared by the water dispersion step and gradually adding an initiator for polymerization. The silylated acrylic polyurethane emulsion has excellent water resistance and chemical resistance, and can remarkably improve hardness when being used as paint.

Description

Silylated acrylic polyurethane dispersion, preparation method of the dispersion and paint including the same}

The present invention relates to a silylated acrylic polyurethane emulsion, a preparation method thereof, and a paint containing the same.

Polyurethane (PU) is a polymer compound in which a urethane bond (NHCOO) formed by addition reaction of a polyol having a chemically active hydroxyl group (OH) and a diisocyanate having an isocyanate group (NCO) is connected in series. Such PU can realize various physical properties by controlling the blending of polyol and diisocyanate, and has been widely applied to various fields such as adhesives, paints, fibers , and synthetic leathers.

Recently, waterborne polyurethane dispersions (PUDs), which use water as a solvent, have been spotlighted due to human toxicity and environmental problems of solvent-type polyurethanes using volatile organic compounds (VOCs) as solvents. I am getting it. There are two methods of preparing a PUD: a surfactant is added to the water to facilitate dispersion of the resin, and two methods of introducing a hydrophilic functional group into the resin without using a surfactant. The latter method takes much more time for the manufacturing process than the former, but is favored because physical properties such as mechanical strength are enhanced.

However, although PUD is an environmentally friendly process, water resistance, chemical resistance and mechanical properties tend to be lowered than solvent type polyurethane. Accordingly, researches to improve the problems of the PUD are actively being conducted.

In this regard, the present applicant is reacted by adding dimethylol propionic acid and isocyanate compound to polyol in Korean Patent No. 1031307 and then reacting with methyl methacrylate and crosslinking agent ethylene glycol di to the polyurethane prepolymer. A technique of preparing a water-dispersible nano-acrylic polyurethane composition has been disclosed by adding methacrylate to activate and dispersing water, and then adding a chain extender and an initiator thereto.

The water-dispersible nano acrylic polyurethane composition prepared by the applicant has the advantage that the hardness characteristics are complemented, but water resistance, chemical resistance and mechanical properties remain a problem to be complemented. Accordingly, the present applicant has continuously researched the technology to complement the water resistance, chemical resistance and mechanical properties of the water-dispersible acrylic polyurethane, and thus, when the silane coupling agent is used, excellent water resistance, chemical resistance and mechanical properties can be obtained. It was found and completed the present invention.

Therefore, an object of the present invention is to provide a method for producing an acrylic polyurethane emulsion that can ensure excellent water resistance, chemical resistance and mechanical properties when applied to paints.

In another aspect, the present invention is to provide an acrylic polyurethane emulsion having excellent water resistance, chemical resistance and mechanical properties produced by the above production method.

It is another object of the present invention to provide a paint comprising the acrylic polyurethane emulsion.

In order to achieve the above object, the present invention is a prepolymer manufacturing step of preparing a prepolymer having an NCO group at the end by adding a dimethylolpropionic acid (DMPA) and a diisocyanate compound to the polyol; A capping step of capping the terminal NCO group of the prepolymer with the silane coupling agent by adding a silane coupling agent to the reaction solution which has been subjected to the prepolymer preparation step; Adding a chain extender to the reaction solution after the capping step, extending the chain, neutralizing the neutralizing agent by adding the neutralizing agent until pH 7-10, and stirring and dispersing it while adding water thereto; And a polymerization step of adding an acrylic monomer to the emulsion prepared in the water dispersion step and then gradually adding an initiator to polymerize the emulsion.

The prepolymer manufacturing step may be added in a ratio of 0.5 to 1 mol of dimethylolpropionic acid (DMPA) and 2 to 3 mol of diisocyanate compound based on 1 mol of polyol having a molecular weight of 500 to 3000.

In the capping step, the silane coupling agent is preferably added at a ratio of 0.1 to 1 mole with respect to 1 mole of the polyol. The silane coupling agent may be aminopropyl triethoxysilane.

In the polymerization step, the acrylic monomer is preferably added 1.5 to 4 mol per 1 mol of the polyol. The acrylic monomer is preferably added 2-hydroxyethyl methacrylate and methyl methacrylate in a ratio of 2: 8 to 8: 2.

In order to achieve the above another object, the present invention provides a silylated acrylic polyurethane emulsion, characterized in that prepared by the above production method.

In order to achieve the above another object, the present invention provides a paint comprising a silylated acrylic polyurethane emulsion prepared by the above production method.

The present invention is to prepare a water-based polyurethane emulsion as a prepolymer, and then capping the terminal NCO group of the prepolymer using a silane coupling agent, and then polymerized with an acrylic monomer to prepare a silylated acrylic polyurethane emulsion. In addition to excellent chemical resistance, it is possible to obtain an effect of greatly improving hardness. Therefore, the silylated acrylic polyurethane emulsion prepared according to the present invention can be usefully used as a paint.

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

Method for producing a silylated acrylic polyurethane emulsion according to the present invention is a prepolymer manufacturing step of preparing a prepolymer having an NCO group at the end by adding dimethylol propionic acid and diisocyanate compound to the polyol; A capping step of capping a terminal NCO group of the prepolymer with a silane coupling agent by adding a silane coupling agent to the reaction solution which has been subjected to the prepolymer manufacturing step; Adding a chain extender to the reaction solution after the capping step, extending the chain, neutralizing the neutralizing agent by adding the neutralizing agent until pH 7-10, and stirring and dispersing it while adding water thereto; And a polymerization step of polymerizing by gradually adding an initiator after adding an acrylic monomer to the emulsion prepared in the water dispersion step.

Each step will be described in more detail as follows.

Prepolymer  Manufacturing stage

The prepolymer manufacturing step is a step of preparing a prepolymer having an NCO group at the terminal by adding dimethylol propionic acid and diisocyanate compound to the polyol.

In the present invention, a prepolymer having an NCO group at the terminal is prepared by adding 0.5 to 1 mole of dimethylolpropionic acid (DMPA) and 2 to 3 moles of diisocyanate compound based on 1 mole of polyol having a molecular weight of 500 to 3000. It was.

The polyol is used to have a molecular weight of 500 to 3000, when the molecular weight of the polyol is less than 500, there is a disadvantage in the dispersion stability, poor workability when applying the undercoat coating, if the molecular weight exceeds 3000 coating film when applied to the undercoat There is a disadvantage in that the flexibility of the decrease in overall physical properties. Therefore, it is preferable to use a polyol having a molecular weight within the above range. More preferably, those having a molecular weight of 1000 to 2500 may be used.

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 are 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 commercially available lactone polyols Placcel 200 series of Daicel can be optionally used.

Dimethylolpropionic acid added to the polyol is used to enable a smooth aqueous dispersion through the introduction of a hydrophilic group.

The dimethylol propionic acid is added in a ratio of 0.5 mol to 1 mol with respect to 1 mol of polyol. When the amount of the dimethylol propionic acid is less than 0.5 mole with respect to 1 mole of polyol, smooth water dispersion is difficult, and thus there is a disadvantage in stability. When the amount of the dimethylol propionic acid is added in excess of 1 mole, chemical resistance is applied to the paint. This has the disadvantage of deteriorating. Therefore, it is preferable to add dimethylol propionic acid in the ratio of 0.5-1 mol with respect to 1 mol 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 1-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.

The diisocyanate compound is a reaction with the above-described polyol to form a urethane group, and those generally used in the art can be used without limitation.

For example, the diisocyanate may be at least one selected from the group consisting of toluene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, isophorone diisocyanate, hexane diisocyanate, and hexamethylene diisocyanate.

The diisocyanate compound is added at a rate of 2 to 3 moles with respect to 1 mole of the polyol. When the amount of the diisocyanate added is less than 2 moles with respect to 1 mol of the polyol, there is a problem in that the coating property is easily peeled off due to poor workability when applying the prepared emulsion to the paint as a paint, and the amount of isocyanate added 3 When the molar excess exceeds the molecular weight of the prepared prepolymer, there is a problem in that the workability is poor when the prepared emulsion is applied as a paint and the overall coating properties are lowered.

When the dimethylol propionic acid and the diisocyanate compound are added to the polyol and reacted as described above, a prepolymer can be prepared, wherein the reaction is carried out for 3 hours or more in a state in which the temperature of the reactor is raised to 70 to 100 ° C. The reaction termination time can be easily confirmed by changing the absorption band length of the isocyanate group (NCO) in, for example, IR spectrum. That is, when there is no change in the absorption band length of the isocyanate group (NCO) it can be seen that the reaction is completed.

In order to promote the reaction, a catalyst used in preparing a conventional polyurethane may be added within a conventional addition range. For example, dibutyltin dilaurate (DBTL) may be used as the catalyst, and may be added at a ratio of 0.001 to 0.005 mol per mol of the polyol.

Capping Step

The capping step is a step of capping the terminal NCO group of the prepolymer with the silane coupling agent by adding a silane coupling agent to the reaction solution passed through the prepolymer manufacturing step.

The silane coupling agent is added to increase the water resistance and chemical resistance while enhancing the mechanical properties including hardness when the prepared emulsion is applied to the paint.

The silane coupling agent can be used without limitation so long as it has a functional group bondable with the terminal NCO of the prepolymer. It is preferable to use the silane coupling agent which has an amino group at the terminal.

For example, the silane coupling agent may be N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, and 3-aminopropyl. At least one selected from the group consisting of triethoxysilane can be used. More preferably, the silane coupling agent may use 3-aminopropyltriethoxysilane.

It is preferable to add 0.1-1 mol of the said silane coupling agents with respect to 1 mol of polyols, More preferably, 0.3-1 mol is added. When the amount of the silane coupling agent added is less than 0.1 mole with respect to 1 mole of polyol, there is a problem that the enhancement effect of mechanical properties including hardness is not sufficient. May occur.

At this time, the reaction in the capping step is added to the silane coupling agent while maintaining the temperature of the reactor at 70 to 100 ℃ and then reacted for 2 hours or more, the terminal NCO group of the prepolymer reacts with the silane coupling agent to be capped.

Dispersion stage

The water dispersion step is a step of dispersing by adding a chain extender to the reaction solution passed through the capping step and chain extension and neutralizing by adding a neutralizing agent until pH 7 ~ 10, and adding water thereto and stirring.

The chain extender is added to control the molecular weight. 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 may be selectively added to have an appropriate molecular weight range in consideration of the use of the prepared emulsion. For example, the chain extender may be added in a ratio of 0.05 to 1 mole based on 1 mole of polyol when the prepared emulsion is applied as a paint. In addition, the chain extender may be added after dilution in a small amount of water.

The chain extender may be formed under the same temperature conditions as the reaction of the capping step, and when the reaction is performed for about 2 hours, the remaining NCO group and the chain extender react to extend the chain.

When the chain extension is completed, a neutralization process is performed to neutralize the COOH group of dimethylolpropionic acid. The neutralization may be performed by lowering the temperature to 40 to 60 ° C. and then adding the neutralizing agent to a pH of 7 to 10. .

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.

When neutralization is completed, the reaction solution is added with water and stirred to disperse. 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. As such, when water is added to the reaction solution and stirred, a water-dispersible emulsion-type silylated polyurethane can be obtained.

Polymerization stage

The polymerization step is a step of polymerization by slowly adding an initiator after adding an acrylic monomer to the emulsion prepared in the water dispersion step.

The acrylic monomer is added to impart the properties of the acrylic resin to improve the chemical resistance and wear resistance, 2-hydroxyethyl methacrylate, methyl methacrylate, butyl methacrylate, 2-hydroxyethyl acrylate, It may include at least one selected from the group consisting of methyl acrylate, butyl acrylate, pentaerythritol triacrylate.

Preferably, the acrylic monomer is preferably added 2-hydroxyethyl methacrylate and methyl methacrylate, wherein the 2-hydroxyethyl methacrylate and methyl methacrylate of 2: 8 to 8: 2 It is preferable to add in a molar ratio, more preferably in a molar ratio of 4: 6 to 6: 4. Very good chemical resistance can be obtained when 2-hydroxyethyl methacrylate and methyl methacrylate are added at a molar ratio within the above range.

In the polymerization step, the acrylic monomer is preferably added 1.5 to 4 mol per 1 mol of the polyol. When the amount of the acrylic monomer added is less than 1.5 moles per 1 mole of polyol, there is a disadvantage in that the chemical resistance is lowered due to insufficient provision of acrylic resin properties, and when added in excess of 4 moles, workability is increased due to an increase in viscosity. There is a problem that the coating coating is non-uniform falling.

The initiator is added to initiate the polymerization reaction can be used without limitation, those commonly used in the art.

As the initiator, for example, 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 redox initiators such as a peroxide initiator such as hydrogen peroxide, a combination of persulfate and sodium hydrogen sulfite, a peroxide and a reducing agent such as a combination of peroxide and sodium ascorbate, and the like.

The initiators exemplified above may be used alone, or may be used by mixing two or more kinds. The initiator may be added within the range generally used in the art, for example, it is preferable to use 0.5 to 5 parts by weight based on 100 parts by weight of the acrylic monomer added for polymerization.

The reaction of the polymerization step may be made by slowly adding the initiator in the state of raising the reaction temperature to 70 to 90 ℃ after adding the acrylic monomer to the emulsion prepared in the water dispersion step.

The above steps complete the preparation of the silylated acrylic polyurethane emulsion according to the invention. In this case, various additives may be added to the silylated acrylic polyurethane emulsion 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 silylated acrylic polyurethane emulsion according to the present invention prepared as described above may not only be excellent in water resistance and chemical resistance when used as a paint, but also greatly improve the hardness. In particular, the silylated acrylic polyurethane emulsion may be usefully used in automotive paints and mobile phone coating paints, and when applied to coating paints exhibit excellent properties such as chemical resistance, hardness, adhesion.

The present invention provides a coating material for coating comprising the acrylic hybrid water-dispersed polyurethane composition prepared as described above.

In the coating paint, the silylated acrylic polyurethane emulsion may vary in its content, 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. Good to do.

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 or melamine 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. However, it should be understood that the present invention is not limited thereto.

≪ Example 1 >

Dissolve 0.0195 mole of dimethylol propionic acid (DMPA, 98%, Aldrich) in 5 g of 1-methyl-2-pyrrolidone (NMP, 99%, Aldrich), dissolve, and then dissolve 500 mL with a thermometer, cooler, temperature controller and stirrer. Put into a four-necked round flask. Here is 0.0585 mol of isophorone diisocyanate (IPDI, 98%, Aldrich) as isocyanate, 0.0255 mol of polycarbonate diol (PCD, MW: 1000, Asahi Kasei) as polyol and dibutyltin dilaurate (DBTL, 95%, Aldrich) was added 0.000045 mol and reacted for 3 hours at 75 ℃ to prepare a prepolymer having an NCO group at the end.

While keeping the temperature of the reactor at 75 ° C., 0.00386 moles of aminopropyltriethoxysilane (APS, 98.5%, Aldrich), a silane coupling agent, were added, and then reacted for 2 hours to cap the terminal NCO group of the prepolymer, and the chain 0.01157 mole of 1,4-butanediol (1,4-BD, 99%, Aldrich) as an extender was added thereto, followed by reaction for 2 hours to complete the chain extension reaction.

Thereafter, the reaction temperature was lowered to 50 ° C., and 0.0195 mole of triethylamine (TEA, 99.5%, Aldrich), a neutralizing agent, was added thereto to react for 1 hour to neutralize the COOH group of DMPA. 85 g of distilled water was slowly added thereto while stirring the reaction solution of the reactor at 1,000 rpm.

An acrylic solution containing 0.03384 mol of 2-hydroxyethyl methacrylate (HEMA, 97%, Aldrich) and 0.03384 mol of methyl methacrylate (MMA, 97%, Aldrich) was added as an acrylic monomer to the emulsion obtained by dispersing the water. After heating the reactor to 80 ° C., 0.5 mol of a water-soluble initiator, potassium persulfate (KPS, 97%, Aldrich), was dissolved in 5 g of water, and then slowly added dropwise for 3 hours, followed by stirring. Polyurethane emulsions were prepared.

≪ Examples 2 to 9 &

The silylated acrylic polyurethane was carried out in the same manner as in Example 1 except that the content of the silane coupling agent aminopropyltriethoxysilane and the chain extender 1,4-butanediol was changed as shown in Table 1 below. An emulsion was prepared.

≪ Comparative Example 1 &

Acrylic polyurethane was prepared in the same manner as in Example 1 except that the content of 1,4-butanediol as a chain extender was not changed as shown in Table 1 without adding aminopropyltriethoxysilane as a silane coupling agent. An emulsion was prepared.

<Experimental Example 1>

The viscosity of the silylated acrylic polyurethane emulsion and the acrylic polyurethane emulsion prepared in Examples and Comparative Examples were measured as follows and the results are shown in Table 1 below.

1) Viscosity

The viscosity of the prepared solution was measured using a rotary viscometer (LVDV-11 + P, BROOKFIELD, USA). At this time, the spindle was used # 62 and the viscosity was measured under the condition of 6rpm at 20 ℃.

<Experimental Example 2>

5 parts by weight of a melamine curing agent Cymel 327 (CYTEC, USA) was added to 100 parts by weight of the silylated acrylic polyurethane emulsion and the acrylic polyurethane emulsion prepared in Examples and Comparative Examples, followed by applying an applicator (coating thickness 30 μm). Coated on a glass substrate, and then thermally cured at 150 ° C. for 30 minutes in a dryer to form a coating film. Pencil hardness, adhesive force, abrasion resistance, chemical resistance of the prepared coating film was measured in the following manner and the results are shown in Table 1 below.

1) Pencil Hardness

The pencil hardness tester (CORE TECH., Korea) was inserted into the pencil hardness measuring pencil at a 45 ° angle, the load (1kg) was applied eight times to check the scratches. Mitsubishi pencil was used as a pencil, and pencils showing strengths such as H-9H, F, HB, and B-6B were used, and pencil hardness was indicated as a pencil before scratching occurred.

2) adhesion

Based on ASTM D 3359, make 100 squares with a checkered sheath of 11 × 11 in 1mm intervals on the cured coating layer, attach 3M Tape on it, and then pull it out sharply for the adhesion of the remaining number of eyes. Was evaluated.

3) Abrasion resistance

In order to measure the abrasion resistance of the coating film coated on the 2 mm thick PC sheet (Shinwha Bending, Korea), a wear tester (QM600T, Qmesys, Korea) was used to wear 100 times at a speed of 70 rpm under a load of 500 g and then UV. The loss of transmittance at 600 nm was measured using a visible spectrometer (UV-2450, Shimadzu).

4) Chemical resistance

In order to measure the chemical resistance of the coated coating film was measured under a 1kg load at a rotational speed of 40rpm using an eraser chain life tester (SPG, Korea). An industrial rubber eraser (Munbangsawoo, Korea) was used, and the chemical resistance of the coating film was measured by measuring the reciprocating frequency of the rubber eraser after ethanol was applied to the coating film until the coating film was peeled off.

division Addition amount of silane coupling agent (mol) Chain Extender Addition (mol) HEMA: MMA
Mole ratio Viscosity (cp) Pencil hardness Adhesion Abrasion resistance
(Transmittance loss%) Chemical resistance
(cycle) Example 1 0.00386 0.01157 1: 1 37 B 100/100 66.9 428 Example 2 0.00772 0.00964 1: 1 59 B 100/100 59.0 511 Example 3 0.01159 0.007705 1: 1 80 HB 100/100 50.3 550 Example 4 0.01544 0.00578 1: 1 120 HB 100/100 40.1 641 Example 5 0.0193 0.00385 1: 1 195 F 100/100 37.3 799 Example 6 0.02316 0.00192 1: 1 225 F 100/100 26.2 861 Example 7 0.0193 00385 8: 2 103 F 100/100 64.5 263 Example 8 0.0193 00385 2: 8 53 HB 100/100 53.2 415 Example 9 0.0193 00385 9: 1 118 F 100/100 66.5 153 Comparative Example 1 0 0.0135 1: 1 22 B 100/100 68.3 451

As shown in Table 1, in the embodiment of the present invention capping using a silane coupling agent and then to produce an acrylic polyurethane emulsion is applied as a paint as compared to the comparative example of preparing an acrylic polyurethane emulsion without using a silane coupling agent It can be confirmed that the physical properties such as adhesive strength and wear resistance, chemical resistance.

Claims (10)

A prepolymer preparation step of preparing a prepolymer having an NCO group at the terminal by adding dimethylolpropionic acid (DMPA) and a diisocyanate compound to the polyol;
A capping step of capping a terminal NCO group of the prepolymer with a silane coupling agent by adding a silane coupling agent to the reaction solution which has been subjected to the prepolymer manufacturing step;
Adding a chain extender to the reaction solution after the capping step, extending the chain, neutralizing the neutralizing agent by adding the neutralizing agent until pH 7-10, and stirring and dispersing it while adding water thereto; And
And a polymerization step of adding an acrylic monomer to the emulsion prepared in the water dispersion step and then gradually adding an initiator to polymerize the emulsion. The method according to claim 1,
The prepolymer production step is a silylene, characterized in that the addition of 0.5 to 1 mole of dimethylolpropionic acid (DMPA) and 2 to 3 moles of diisocyanate compound based on 1 mole of polyol having a molecular weight of 500 to 3000 Process for the preparation of a tethered acrylic polyurethane emulsion. The method according to claim 2,
The silane coupling agent in the capping step is a method for producing a silylated acrylic polyurethane emulsion, characterized in that the addition of 0.1 to 1 molar ratio per 1 mole of the polyol. The method according to claim 3,
The silane coupling agent is aminopropyl triethoxysilane. The method of producing a silylated acrylic polyurethane emulsion. The method according to claim 2,
In the polymerization step, the acrylic monomer is a method for producing a silylated acrylic polyurethane emulsion, characterized in that the addition of 1.5 to 4 moles per 1 mole of the polyol. The method according to claim 5,
The acrylic monomer is a method of producing a silylated acrylic polyurethane emulsion, characterized in that the addition of 2-hydroxyethyl methacrylate and methyl methacrylate in a ratio of 2: 8 to 8: 2. Preparation of prepolymer having NCO group at the end by adding 0.5-1 mol of dimethylolpropionic acid (DMPA) and 2-3 mol of diisocyanate compound per 1 mol of polyol having a molecular weight of 500-3000 step;
A capping step of capping a terminal NCO group of the prepolymer with a silane coupling agent by adding 0.1 to 1 mole of a silane coupling agent to the reaction solution that has passed through the prepolymer manufacturing step;
Adding a 0.05 to 1 mol chain extender to the reaction solution that passed through the capping step to extend the chain, and then neutralizing the neutralizing agent by adding the neutralizing agent until pH 7-10; And
And a polymerization step of polymerizing by slowly adding an initiator to the emulsion prepared in the water dispersing step and then adding 1.5 to 4 moles of the acrylic monomer to the emulsion. The method of claim 7,
The silane coupling agent is aminopropyl triethoxysilane, and the acrylic monomer is a silicate, wherein 2-hydroxyethyl methacrylate and methyl methacrylate are added in a ratio of 2: 8 to 8: 2. Process for the preparation of acrylic polyurethane emulsions. Silylated acrylic polyurethane emulsion, characterized in that produced by the method of any one of claims 1 to 8. A paint comprising a silylated acrylic polyurethane emulsion prepared by the process according to any one of claims 1 to 8.