KR102419825B1 - Paint Composition - Google Patents

Abstract

The present invention relates to a first acrylic resin emulsion comprising a unit derived from a hydroxyl group-containing acrylic monomer; and a second acrylic resin emulsion comprising a unit derived from an acrylic monomer containing an amine group or an amide group, wherein the weight ratio of the first acrylic resin emulsion to the second acrylic resin emulsion is 0.5:1 to 8:1 It relates to a phosphorus paint composition.

Description

Paint Composition {Paint Composition}

The present invention relates to a paint composition.

The decal paint applied to the container does not use a special drying device, and a uniform coating film should be formed on the outside and inside of the structure under a general environment from the winter temperature around 5℃ to the summer temperature around 40℃.

Therefore, in order to prevent stickiness of the coating film in hot and humid summer, the glass transition temperature (Tg) of the emulsion resin should be designed to be at least 20 ° C. Therefore, it was common to add more than a certain amount of volatile organic solvents (VOCs) during the manufacture of paints in order to prevent the cracking of the coating film during coating in winter when the glass transition temperature (Tg) or less.

On the other hand, on the outside of the container, there is an identification tag called a decal on the outer surface to identify each container. These decals are conventionally attached to containers by printing text on sticker-type or sheet-type paper. However, this method had a cost problem due to the inconvenience of having to reprint the print every time the decal was changed and the cost was high. In addition to the sticker or sheet type, there was also a method of directly engraving the decal on the outside of the container using an oil-based paint.

In order to solve the above problems, we want to develop a paint that can be dried at room temperature so that it can be used outside and/or inside a structure such as a container using a water-based paint without environmental pollution and has excellent water resistance, chemical resistance, appearance, and mechanical properties. Research is continuously being carried out.

The present invention is to solve the problems of the conventional coating composition as described above, and to improve the effect of moisture after drying at room temperature. An object of the present invention is to provide a coating composition with improved mechanical properties such as hardness and hardness.

The present invention relates to a first acrylic resin emulsion comprising a unit derived from a hydroxyl group-containing acrylic monomer; and a second acrylic resin emulsion comprising a unit derived from an acrylic monomer containing an amine group or an amide group;

The coating composition of the present invention is prepared by using a first acrylic resin emulsion prepared using an acrylic monomer containing a hydroxyl group and a second acrylic resin emulsion prepared using an acrylic monomer containing an amine group or an amide group in combination, so that after drying at room temperature, It is possible to improve the effect of moisture and provide a coating film with improved water resistance even under a short drying time condition, and in addition, mechanical properties such as appearance, chemical resistance, impact resistance, adhesion, and hardness of the coating film can be improved.

In addition, by using a water-based paint composition containing a water-dispersible acrylic resin emulsion, VOC is reduced and environmental problems are solved. It has the potential to be optimized.

Hereinafter, the present invention will be described in detail.

The present invention provides a coating composition.

As used herein, “weight average molecular weight” is measured by a conventional method known in the art, and may be measured by, for example, a gel permeation chromatograph (GPC) method. The “glass transition temperature” is measured by a conventional method known in the art, and may be measured, for example, by differential scanning calorimetry (DSC). Functional groups such as "hydroxyl value and "amine value" may be measured by methods well known in the art, and may represent values measured by, for example, titration.

In addition, in this specification, "(meth)acryl" means "acryl" and/or "methacrylic", and "(meth)acrylate" means "acrylate" and/or "methacrylate" .

The coating composition may include a first acrylic resin emulsion including units derived from a hydroxyl group-containing acrylic monomer; and a second acrylic resin emulsion comprising units derived from an acrylic monomer containing an amine group or an amide group.

<First acrylic resin emulsion>

The first acrylic resin emulsion included in the paint composition of the present invention is a main component in the paint and has particularly excellent chemical resistance, and when applied as a paint for decals, it contains a quick-drying, water-dispersible acrylic copolymer that dries quickly even at room temperature.

The first acrylic resin emulsion includes units derived from a hydroxyl group-containing acrylic monomer.

The first acrylic resin emulsion may further include a unit derived from an ethylenically unsaturated monomer in addition to the unit derived from the hydroxyl group-containing acrylic monomer.

The first acrylic resin emulsion may be obtained by solution polymerization (or copolymerization) of one or more monomers (monomers) selected from the hydroxyl group-containing acrylic monomer and the ethylenically unsaturated monomer in the presence of a radical polymerization initiator.

The first acrylic resin emulsion may be prepared by polymerizing a hydroxyl group-containing acrylic monomer, an ethylenically unsaturated monomer, and a radical polymerization initiator in an organic solvent, and then adding an emulsifier to emulsify it in water. It can be prepared by dispersing in water (deionized water).

The first acrylic resin emulsion may be a water-dispersible acrylic resin emulsion.

The radical polymerization initiator is potassium persulfate, peroxide, tert-butyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perfivalate, tert-amyl perbenzoate, tert-amyl Peroxyacetate, di-tert-amyl peroxide, tert-amylperoxyneodecanoate, tert-butylperoxyneodecanoate, tert-amyl-(2-ethylethyl)monoperoxycarbonate, azobis It may be isobutylnitrile, or 2.2-azobismethylbutyronitrile, but is not limited thereto.

The hydroxyl group-containing acrylic monomer may be monohydroxy alkyl (meth) acrylate, dihydroxy alkyl (meth) acrylate, lactone (meth) acrylate, or hydroxy alicyclic (meth) acrylate, but is limited thereto it's not going to be

The hydroxyl group-containing acrylic monomer is 2-hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 1,3-butanediol acrylate, 1,4- Butanediol acrylate, 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) Acrylate, 2-hydroxyethylene glycol (meth) acrylate, 2-hydroxypropylene glycol (meth) acrylate, cadura acrylate, cadura methacrylate, caprolactone acrylate, caprolactone methacrylate, 2,3 -dihydroxypropyl acrylate, 2,3-dihydroxypropyl (meth) acrylate, 4-hydroxymethylcyclohexyl (meth) acrylate, or 1,6-hexanediol di (meth) acrylate, etc. However, the present invention is not limited thereto.

The ethylenically unsaturated monomer is styrene, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, normal butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, benzyl Acrylate, isobornyl acrylate, methyl (meth) acrylate, propyl (meth) acrylate, normal butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethyl It may be hexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, or lauryl (meth) acrylate, but is not limited thereto.

The first acrylic resin emulsion has a glass transition temperature (T _g ) of 10 to 30° C., a pH of 9 to 11, an average particle size (D ₅₀ ) of 100 to 250 nm, and a solid content of 50 to 60 weight. %, and the weight average molecular weight is 200,000 to 500,000 g/mol, and the viscosity measured at 25° C. may be 300 to 1,000 cps.

The first acrylic resin emulsion may have a glass transition temperature (T _g ) of 10 to 30°C, specifically 15 to 25°C, and more specifically 15 to 20°C. If the glass transition temperature (T _g ) of the first acrylic resin emulsion is less than 10 ℃, the dryness of the paint may be reduced, and if it is more than 30 ℃, there may be a problem that an excessive solvent must be applied due to quick-drying. .

The first acrylic resin emulsion may have a pH of 9 to 11. If the pH of the first acrylic resin emulsion is less than 9, a problem of lowering resin stability may occur, and if it exceeds 11, a problem of lowering water resistance may occur.

The average particle size (D ₅₀ ) of the first acrylic resin emulsion may be 100 to 250 nm, specifically 100 to 200 nm, and more specifically 100 to 160 nm. If the average particle size of the first acrylic resin emulsion is less than 100 nm, a problem of increasing the viscosity of the resin emulsion may occur, and if it exceeds 250 nm, the storage stability of the resin emulsion may be reduced.

The average particle size (D ₅₀ ) may be defined as a particle size based on 50 wt% of the particle size distribution of the particles. The average particle size (D ₅₀ ) may be measured using, for example, a laser diffraction method.

The solid content of the first acrylic resin emulsion may be 50 to 60% by weight, specifically 50 to 56% by weight. When the solid content of the first acrylic resin emulsion is less than 50% by weight, there may be a problem in that the solid content of the coating composition is lowered, and when it is more than 60% by weight, the storage stability due to the increase in the particle size of the acrylic resin emulsion may be reduced. can

The weight average molecular weight of the first acrylic resin included in the first acrylic resin emulsion may be 200,000 to 500,000 g/mol, specifically 200,000 to 350,000 g/mol. When the weight average molecular weight of the first acrylic resin is less than 200,000 g/mol, there is a problem in that mechanical properties are deteriorated, and when it exceeds 500,000 g/mol, appearance deterioration may occur.

The viscosity measured at 25° C. of the first acrylic resin emulsion may be 300 to 1,000 cps, specifically 400 to 700 cps. The viscosity may be measured using a Brookfield viscometer (type b). If the viscosity of the first acrylic resin emulsion is less than 300 cps, storage stability may be reduced, and if it is more than 1,000 cps, the viscosity of the coating composition increases and workability becomes difficult.

The hydroxyl value (OHv) of the first acrylic resin emulsion may be 5 to 30 mgKOH/g. When the hydroxyl value of the first acrylic resin emulsion is less than 5 mgKOH/g, the synthesis stability of the first acrylic resin emulsion may be reduced, and if it exceeds 30 mgKOH/g, water resistance may be reduced.

<Second acrylic resin emulsion>

The second acrylic resin emulsion included in the paint composition of the present invention is a main component in the paint and has excellent chemical resistance and serves to strengthen mechanical properties such as impact resistance and hardness.

The second acrylic resin emulsion includes units derived from an acrylic monomer containing an amine group or an amide group.

The second acrylic resin emulsion may further include a unit derived from an ethylenically unsaturated monomer in addition to the unit derived from the acrylic monomer containing an amine group or an amide group.

The second acrylic resin emulsion may be obtained by solution polymerization (or copolymerization) of one or more monomers (monomers) selected from the amine group or amide group-containing acrylic monomer and the ethylenically unsaturated monomer in the presence of a radical polymerization initiator.

The second acrylic resin emulsion is an acrylic monomer containing an amine group or an amide group. It can also be prepared by polymerizing an ethylenically unsaturated monomer and a radical polymerization initiator in an organic solvent and then adding an emulsifier to emulsify it in water. can be manufactured.

The second acrylic resin emulsion may be a water-dispersible acrylic resin emulsion.

The radical polymerization initiator may be the same as described above in the 'first acrylic resin emulsion'. The radical polymerization initiator is potassium persulfate, benzoyl peroxide, tert-butyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perfivalate, tert-amyl perbenzoate, tert- Amyl peroxyacetate, di-tert-amyl peroxide, tert-amylperoxyneodecanoate, tert-butylperoxyneodecanoate, tert-amyl-(2-ethyl ethyl) monoperoxycarbonate, azo It may be bisisobutylnitrile, or 2.2-azobismethylbutyronitrile, but is not limited thereto.

The amine group or amide group-containing acrylic monomer may be dialkylaminoalkyl acrylate, diacetoneacrylamide, or the like, but is not limited thereto.

The amine group or amide group-containing acrylic monomer is dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminomethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, or diethylaminoethyl (meth)acrylate It may be acetone acrylamide, (meth)acrylamide, or the like, but is not limited thereto.

As for the ethylenically unsaturated monomer, the contents described above in the 'first acrylic resin emulsion' may be applied in the same manner. The ethylenically unsaturated monomer is, for example, styrene, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, normal butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl Acrylate, benzyl acrylate, isobornyl acrylate, methyl (meth) acrylate, propyl (meth) acrylate, normal butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, or lauryl (meth) acrylate, but is not limited thereto.

The second acrylic resin emulsion has a glass transition temperature of 30 to 50 ° C., a pH of 7 to 11, an average particle size (D ₅₀ ) of 100 to 200 nm, a solid content of 40 to 50 wt%, and a weight The average molecular weight may be 50,000 to 500,000 g/mol, and the viscosity at 25° C. may be 50 to 300 cps.

The second acrylic resin emulsion may have a glass transition temperature (T _g ) of 30 to 50 °C, specifically 32 to 40 °C. When the glass transition temperature (T _g ) of the second acrylic resin emulsion is less than 30 ° C, the dryness and hardness of the paint may decrease, and if it exceeds 50 ° C, excessive solvent must be applied due to quick drying. Problems can arise.

The second acrylic resin emulsion may have a pH of 7 to 11. If the pH of the second acrylic resin emulsion is less than 7, there may be a problem in storage stability, and if it is more than 11, there may be a problem in that the viscosity of the second acrylic resin emulsion increases.

The second acrylic resin emulsion may have an average particle size (D ₅₀ ) of 100 to 200 nm, specifically 120 to 170 nm. If the average particle size of the second acrylic resin emulsion is less than 100 nm, a problem of increasing the viscosity may occur, and if it is more than 200 nm, storage stability may be reduced.

The average particle size (D ₅₀ ) may be defined as a particle size based on 50 wt% of the particle size distribution of the particles. The average particle size (D ₅₀ ) may be measured using, for example, a laser diffraction method.

The content of the solid content of the second acrylic resin emulsion may be 40 to 50% by weight. If the solid content of the second acrylic resin emulsion is less than 40% by weight, there may be a problem that the solid content of the coating composition is lowered, and if it is more than 50% by weight, the synthesis stability of the second acrylic resin emulsion may be reduced. .

The weight average molecular weight of the second acrylic resin included in the second acrylic resin emulsion may be 50,000 to 500,000 g/mol, and specifically, 50,000 to 200,000. When the weight average molecular weight of the second acrylic resin is less than 50,000 g/mol, there is a problem in that mechanical properties are lowered, and when it exceeds 500,000 g/mol, there is a problem in that the appearance of the paint is deteriorated.

The viscosity measured at 25° C. of the second acrylic resin emulsion may be 50 to 300 cps, specifically 100 to 250 cps. The viscosity may be measured using a Brookfield viscometer (type b). When the viscosity of the second acrylic resin emulsion is less than 50 cps, there is a problem in that storage stability is lowered, and when it exceeds 300 cps, there is a problem in that the solid content of the paint is lowered.

The amine value (AmV) of the second acrylic resin emulsion may be 40 to 300 mgKOH/g, and specifically, the amine value may be 80 to 150 mgKOH/g. When the amine value of the second acrylic resin emulsion is less than 40 mgKOH/g, the storage stability of the paint may decrease, and if it exceeds 300 mgKOH/g, the viscosity of the paint composition may increase.

The total weight of the first acrylic resin emulsion and the second acrylic resin emulsion may be specifically included in an amount of 50 to 70% by weight, more specifically 55 to 65% by weight, based on the coating composition. If the total weight of the first acrylic resin emulsion and the second acrylic resin emulsion is less than 50% by weight, there may be a problem in that the water resistance of the coating film is lowered, and when it is more than 70% by weight, the mechanical properties of the coating film are lowered. can happen

The weight ratio of the first acrylic resin emulsion to the second acrylic resin emulsion may be 0.5:1 to 8:1, specifically 1:1 to 7:1, and 1:1 to 5:1. . When the weight ratio of the first acrylic resin emulsion to the second acrylic resin emulsion is less than 0.5:1, the storage stability of the coating composition may be reduced, and if it exceeds 8:1, water resistance may be reduced.

<Other ingredients>

The coating composition of the present invention may further include at least one selected from solvents, pigments and additives in addition to the first and second acrylic resin emulsions described above.

The solvent is included in the coating composition to improve compatibility with the first acrylic resin emulsion or the second acrylic resin emulsion, and to improve workability.

As the solvent, an alcohol-based solvent such as Texanol, Butyl Cellosolve, Butyl Carbitol, DOWANOL DPnB (DOW), or methyl acetate, ethyl acetate, n-propyl acetate , n-butyl acetate, ethyl ethoxy propionate, such as ester solvents such as water-compatible solvents (compatible solvents) may be included. In addition, the solvent may include a solvent (incompatible solvent) that is not compatible with water, such as MOP (Metal Organic Polyhedra) and mineral spirits.

The solvent may be mixed with a compatible solvent and an incompatible solvent.

The solvent may be included in an amount of 10 to 30 parts by weight, specifically, 18 to 28 parts by weight based on 100 parts by weight of the first acrylic resin emulsion and the second acrylic resin emulsion. If the content of the solvent is less than 10 parts by weight based on 100 parts by weight of the first acrylic resin emulsion and the second acrylic resin emulsion, workability may deteriorate and a problem may occur in the appearance of the coating film, and if it exceeds 30 parts by weight, The dryness of the paint may be lowered and mechanical properties may be lowered.

The pigment implements a color in a paint or serves to improve the mechanical strength of the paint film.

As the pigment, an extender pigment, red series, yellow/orange series, blue series, green series, black series, colored pigments such as white series, pearl and metallic series, etc. may be used, but is not limited thereto. For example, barium sulfate (Ba ₂ SO ₄ ) (barite, barite), barite, calcium carbonate (CaCO ₃ ), clay (clay, Al ₂ O ₃ .2SiO ₂ .2H ₂ O), bone stone powder (3MgO) • 4SiO ₂ •H ₂ 0), silicate powder (SiO ₂ ), diatomaceous earth (SiO ₂ ·nH ₂ O), silica, bentonite, talc (Talc), extender pigments such as aluminum silicate; white pigments such as titanium oxide (eg, TiO ₂ ), zinc oxide (ZnO), lithopon, zinc sulfide, lead white (2PbCO ₃ ·Pb(OH) ₂ ), and antimony oxide (Sb ₂ O ₃ ); black pigments such as carbon black, graphite, and iron black (Fe ₃ O ₄ ); Yellow such as yellow lead (PbCrO ₃ ), zinc chromate, cadmium yellow (CdS), lead cyanamide (PbCN ₂ ), titanium yellow (TiO ₂ -NiO-Sb ₂ O ₃ ), strontium yellow (SrCrO ₄ ), etc. pigment; Iron (Fe ₂ O ₃ ), lead (Pb ₃ O ₄ ), silver pearl (HgS), cadmium red (mixed crystal of CdS and HgS), molybdenum red (mixed crystal of PbCrO ₄ and PbMoO ₄ , PbSO ₄ ), red pigments such as cuprous oxide (Cu ₂ O); Royal blue (MFe[Fe(CN) ₆ ], M=K, NH ₄ , Na), ultramarine (2(Al ₂ Na ₂ Si ₃ O ₁₀ ) Na ₂ S ₄ ), cobalt blue (CoO·nAl ₂ O ₃ ) ) blue pigments such as; green pigments, such as chromium rust (a mixture of PbCrO ₄ and royal blue KFe[Fe(CN) ₆ ]), chromium oxide (Cr ₂ O ₃ ), and chromium hydroxide (Cr ₂ O ₃ .2H ₂ O); Metal powder pigments, such as silver powder (Alluminium powder), gold powder (Bronze powder); And it may be at least one selected from the group consisting of pearl pigments such as natural pearl essence and synthetic pearl pigments. In addition to the above pigment, it may further include a rust preventive pigment such as zinc phosphate for preventing rust of automobile paint.

The pigment may be included in an amount of 30 to 55 parts by weight based on 100 parts by weight of the first acrylic resin emulsion and the second acrylic resin emulsion. If the content of the pigment is less than 30 parts by weight based on 100 parts by weight of the first acrylic resin emulsion and the second acrylic resin emulsion, mechanical properties may decrease, and if it exceeds 55 parts by weight, the dispersibility becomes poor and Appearance may be degraded.

The additive may include a pH adjusting agent, a dispersing agent, an antifoaming agent, an anti-rotting agent, a wetting agent, a thickener, and the like.

The pH adjusting agent may include an amine compound, for example, aminomethylpropanol.

The dispersant serves to disperse the pigment in a uniform and stable state in the coating composition, and may include, for example, BYK-190 (BYK Corporation).

The antifoaming agent removes air bubbles during the preparation of the coating composition and serves to suppress the generation of air bubbles during coating, for example, ST2400 (BASF Company), AIREX 901W (EVONIK Company), SURFYNOL 104BC (EVONIK Company), etc. may include

The anti-corruption agent serves to prevent spoilage of the coating film, and may include, for example, Acticide MBS (THOR).

The wetting agent serves to improve the wetting properties of the paint, and may include, for example, TEGO WET 240 (EVONIK).

The thickener serves to improve the flowability and storage stability of the coating film, and may include, for example, RM8W (DOW Corporation), RM12W (DOW Corporation), Hydroxyethyl Cellulose, and the like.

The additive may be included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the first acrylic resin emulsion and the second acrylic resin emulsion.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are only for helping the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.

<Examples 1 to 14>

A coating composition was prepared by mixing the compositions shown in Tables 1 and 2 below in the following manner.

DIW, a dispersant, an antifoaming agent, and a thickener were added and stirred for 30 minutes. After adding a pH adjuster to the stirred liquid, the mixture was further stirred for 30 minutes. After the stirring was completed, a pigment was added to prepare a pre-mixing solution. After the pre-mixing solution was introduced into the disperser, dispersion was carried out for 1 hour, and when the particle size of the dispersion became 25 μm or less, it was completed.

The dispersion was stirred at low speed and stirred for 30 minutes after the acrylic resin emulsion was added. After the stirring is completed, a solvent, an antifoaming agent, a wetting agent, and an anti-corruption agent are added respectively to measure the viscosity when mixing is complete, and finally a thickener is added to adjust the viscosity to prepare a paint composition.

division ingredient Example One 2 3 4 5 6 7 acrylic emulsion Article 1-1 Acrylic Resin Emulsion 30 50 27.5 53.18 40 45 48 Part 1-2 acrylic resin emulsion - - - - - - - Article 1-3 Acrylic Resin Emulsion - - - - - - - Article 2-1 Acrylic Resin Emulsion 30 10 27.5 11.82 20 15 12 2-2 Acrylic resin emulsion - - - - - - - Section 2-3 Acrylic Resin Emulsion - - - - - - - Article 2-4 Acrylic Resin Emulsion - - - - - - - solvent DIW 10 10 11.81 9.45 10 10 10 mineral spirit
(DONGNAM YUHWA) 0.7 0.7 0.83 0.66 0.7 0.7 0.7 Texanol (Eastman) 2 2 2.36 1.89 2 2 2 pigment white pigment
(R-706, Chemours) 21.5 21.5 23.83 17.27 21.5 21.5 21.5 body pigment
(S-SIL5, SAC-materials) 3.4 3.4 3.77 2.73 3.4 3.4 3.4 pH adjuster Aminomethylpropanol 0.1 0.1 0.1 0.15 0.1 0.1 0.1 dispersant BYK-190 (BYK) 0.5 0.5 0.5 0.6 0.5 0.5 0.5 antifoam ST2400
(BASF) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 SURFYNOL 104BC
(EVONIK) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 AIREX 901w (EVONIK) 0.3 0.3 0.3 0.4 0.3 0.3 0.3 anti-corruption ACTICIDE MBS
(THOR) 0.3 0.3 0.3 0.4 0.3 0.3 0.3 wetting agent TEGO WET 240 (EVONIK) 0.1 0.1 0.1 0.15 0.1 0.1 0.1 thickener RM8W
(DOW) 0.1 0.1 0.1 0.25 0.1 0.1 0.1 Hydorxyethyl Cellolose (HEC)
(ASHLAND) 0.1 0.1 0.1 0.15 0.1 0.1 0.1 total 100 100 100 100 100 100 100

(Unit: parts by weight)

division ingredient Example 8 9 10 11 12 13 14 acrylic emulsion Article 1-1 Acrylic Resin Emulsion 52 53.3 33 28.89 - - 30 Part 1-2 acrylic resin emulsion - - - - 30 - - Article 1-3 Acrylic Resin Emulsion - - - - - 50 - Article 2-1 Acrylic Resin Emulsion 8 6.7 22 36.11 - - - 2-2 Acrylic resin emulsion - - - - 30 - - Section 2-3 Acrylic Resin Emulsion - - - - - 10 - Article 2-4 Acrylic Resin Emulsion - - - - - - 30 solvent DIW 10 10 11.81 9.45 10 10 10 mineral spirit
(DONGNAM YUHWA) 0.7 0.7 0.83 0.66 0.7 0.7 0.7 Texanol (Eastman) 2 2 2.36 1.89 2 2 2 pigment white pigment
(R-706, Chemours) 21.5 21.5 23.83 17.27 21.5 21.5 21.5 body pigment
(S-SIL5, SAC-materials) 3.4 3.4 3.77 2.73 3.4 3.4 3.4 pH adjuster Aminomethylpropanol 0.1 0.1 0.1 0.15 0.1 0.1 0.1 dispersant BYK-190 (BYK) 0.5 0.5 0.5 0.6 0.5 0.5 0.5 antifoam ST2400
(BASF) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 SURFYNOL 104BC
(EVONIK) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 AIREX 901w (EVONIK) 0.3 0.3 0.3 0.4 0.3 0.3 0.3 anti-corruption ACTICIDE MBS
(THOR) 0.3 0.3 0.3 0.4 0.3 0.3 0.3 wetting agent TEGO WET 240 (EVONIK) 0.1 0.1 0.1 0.15 0.1 0.1 0.1 thickener RM8W
(DOW) 0.1 0.1 0.1 0.25 0.1 0.1 0.1 Hydorxyethyl Cellolose (HEC)
(ASHLAND) 0.1 0.1 0.1 0.15 0.1 0.1 0.1 total 100 100 100 100 100 100 100

(Unit: parts by weight)

<Comparative Examples 1 to 4>

A coating composition was prepared by mixing with the composition shown in Table 3 below.

division ingredient comparative example One 2 3 4 acrylic emulsion Article 1-1 Acrylic Resin Emulsion 60 - 15 54 Article 2-1 Acrylic Resin Emulsion - 60 45 6 solvent DIW 10 10 10 10 mineral spirit
(DONGNAM YUHWA) 0.7 0.7 0.7 0.7 Texanol (Eastman) 2 2 2 2 pigment white pigment
(R-706, Chemours) 21.5 21.5 21.5 21.5 body pigment
(S-SIL5, SAC-materials) 3.4 3.4 3.4 3.4 pH adjuster Aminomethylpropanol 0.1 0.1 0.1 0.1 dispersant BYK-190 (BYK) 0.5 0.5 0.5 0.5 antifoam ST2400
(BASF) 0.4 0.4 0.4 0.4 SURFYNOL 104BC
(EVONIK) 0.5 0.5 0.5 0.5 AIREX 901w (EVONIK) 0.3 0.3 0.3 0.3 anti-corruption ACTICIDE MBS
(THOR) 0.3 0.3 0.3 0.3 wetting agent TEGO WET 240 (EVONIK) 0.1 0.1 0.1 0.1 thickener RM8W
(DOW) 0.1 0.1 0.1 0.1 Hydorxyethyl Cellolose (HEC)
(ASHLAND) 0.1 0.1 0.1 0.1 total 100 100 100 100

(Unit: parts by weight)

The components used in the Examples and Comparative Examples are as follows.

1-1 Acrylic resin emulsion: Tg 17°C, pH 9, D ₅₀ 130 nm, NV 52, Mw 350,000, VIS (25°C) 500 cps, OHv 20 mgKOH/g

1-2 acrylic resin emulsion: Tg 15 ℃, pH 9, D ₅₀ 100 nm, NV 50, Mw 230,000, VIS (25 ℃) 650 cps, OHv 15 mgKOH/g

1-3 Acrylic resin emulsion: Tg 30°C, pH 11, D ₅₀ 160 nm, NV 56, Mw 480,000, VIS (25°C) 430 cps, OHv 28 mgKOH/g

2-1 Acrylic resin emulsion (containing dimethylaminoethyl methacrylate): Tg 32° C., pH 8, D ₅₀ 170 nm, NV 45, Mw 50,000, VIS (25° C.) 170 cps, AmV 100 mgKOH/g

2-2 Acrylic resin emulsion (containing dimethylaminoethyl methacrylate): Tg 35° C., pH 7.5, D ₅₀ 170 nm, NV 42, Mw 100,000, VIS (25° C.) 110 cps, AmV 150 mgKOH/g

2-3 Acrylic resin emulsion (containing dimethylaminoethyl methacrylate): Tg 50° C., pH 10.8, D ₅₀ 170 nm, NV 48.5, Mw 500,000, VIS (25° C.) 200 cps, AmV 60 mgKOH/g

2-4 acrylic resin emulsion (containing diacetone acrylamide): Tg 33° C., pH 8.5, D ₅₀ 150 nm, NV 45, Mw 270,000, VIS (25° C.) 180 cps, AmV 110 mgKOH/g

<Experimental example>

The coating compositions obtained in Examples 1 to 14 and Comparative Examples 1 to 4 were dried at room temperature for 1 hour, immersed in water, and then the appearance evaluation after 48 hours had elapsed was performed by the following evaluation method, and the results are shown in Tables 4 and 5 shown in

VOC Assessment

It was evaluated as "100-non-volatile matter (wt.%)-moisture content (wt.%)".

viscosity

Using Zahn cup #3, the outflow time (seconds) until the paint composition came out was measured.

storage stability

The state in the container after storage was evaluated by visual observation and viscosity to see whether there was no significant difference in paint workability and the appearance of the coating compared to before storage.

film thickness

It was measured with a coating film gauge (ELCOMETER A456C).

Polish

Measured with a 60° gloss meter.

water resistance

Appearance after 2 days of immersion in water after drying at room temperature for 1 hour was evaluated.

adherence

After making a 2mm crosscut according to ASTM D3359, it was removed using a tape to evaluate whether there is a problem.

division Example One 2 3 4 5 6 7 8 9 10 11 12 13 14 VOC rating (wt%) 35 35 38.5 31.2 35 35 35 34 35 35.2 35 34 34 36 Viscosity (sec) 82 85 88 81 82 83 82 83 82 82 82 82 83 81 storage stability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ◎ ○ ◎ Film thickness (㎛) 40 40 40 40 40 40 40 40 40 40 40 40 40 40 Polish(%) 66 62 68 65 66 68 65 53 50 58 53 63 50 52 water resistance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ ○ ◎ ◎ ○ ◎ adherence pass pass pass pass pass pass pass pass pass pass pass pass pass pass

division comparative example One 2 3 4 VOC rating (wt%) 35 35 36 35 Viscosity (sec) 102 73 81 82 storage stability ○ X X X Film thickness (㎛) 43 31 40 40 Polish(%) 32 43 52 50 water resistance X ○ X X adherence fail fail pass pass

Claims (4)

a first acrylic resin emulsion comprising units derived from a hydroxyl group-containing acrylic monomer; and
a second acrylic resin emulsion comprising units derived from an acrylic monomer containing an amine group or an amide group;
including,
As a coating composition, the weight ratio of the first acrylic resin emulsion to the second acrylic resin emulsion is 0.5:1 to 8:1,
The first acrylic resin emulsion has a glass transition temperature (T _g ) of 10 to 30° C., an average particle size (D ₅₀ ) of 100 to 250 nm, and a weight average molecular weight of 200,000 to 500,000 g/mol. composition. delete The method according to claim 1,
The second acrylic resin emulsion,
The glass transition temperature (T _g ) is 30 to 50 ℃,
an average particle size (D ₅₀ ) of 100 to 200 nm,
Weight average molecular weight 50,000 to 500,000 g/mol
A paint composition that is The method according to claim 1,
The amine group or amide group-containing acrylic monomer is a coating composition comprising at least one selected from dialkylaminoalkyl acrylate, diacetone acrylamide, and (meth)acrylamide.