KR102259013B1 - Water-soluble primer composition - Google Patents

Abstract

The present invention relates to an aqueous primer composition comprising an acrylic resin, a polyurethane polyol resin, a polyurethane resin and a chlorinated modified polyolefin resin.

Description

Aqueous primer composition {WATER-SOLUBLE PRIMER COMPOSITION}

The present invention relates to a water-based primer composition that has excellent adhesion to polyamide-based materials such as nylon and is environmentally friendly as a water-based paint.

Automotive plastic parts are generally used after being painted in order to improve the appearance characteristics and protect the surface from the external environment. At this time, the painting treatment is usually a pretreatment to improve the surface tension between the plastic part and the paint through flame or corona discharge treatment, a primer treatment to increase the adhesion between the plastic part and the base coating film, and improve the appearance characteristics of the plastic part and protect the appearance It consists of a base coating film for

Meanwhile, polyamide-based materials such as nylon are applied to automotive exterior parts such as roof rack bars, bumpers, side moldings, door handles, wiper arms, and bezels. In this case, since the polyamide-based material has very poor adhesion to other materials, for example, a base paint, primer treatment is essential.

In this regard, Japanese Patent No. 5,171,261 (Patent Document 1) discloses at least one water-based resin (B) selected from water-based polyolefin-based resins (A), water-based polyurethane resins and water-based acrylic resins, and polyester resins (C). ) and an aqueous primer coating composition comprising a crosslinking agent (D) is disclosed. However, the primer coating composition of Patent Document 1 has a problem in that the adhesion and other physical properties to the polypropylene (PP) material are satisfactory, but the adhesion to the polyamide (nylon) material and other physical properties are not satisfactory.

Therefore, there is a need for research and development on a water-based primer composition having excellent adhesion to polyamide-based materials such as nylon and excellent in various physical properties such as water resistance, chemical resistance, impact resistance, and weather resistance of the prepared coating film.

Japanese Patent Registration No. 5,171,261 (published on June 14, 2007)

Accordingly, the present invention provides an aqueous primer composition having excellent adhesion to a polyamide-based material such as nylon, and having excellent various physical properties such as water resistance, chemical resistance, impact resistance, and weather resistance of the prepared coating film.

The present invention provides an aqueous primer composition comprising an acrylic resin, a polyurethane polyol resin, a polyurethane resin, and a chlorinated-modified polyolefin resin.

The aqueous primer composition according to the present invention has excellent paint workability and excellent adhesion to polyamide-based materials such as nylon. In addition, the water-based primer composition is environmentally friendly due to its low volatile organic compound (VOC) content due to the organic solvent in the paint due to its water solubility.

Furthermore, the coating film prepared from the aqueous primer composition has excellent physical properties such as appearance characteristics, water resistance, weather resistance, chemical resistance, and heat resistance. In particular, the coating film is remarkably excellent in water resistance because peeling of the coating film produced under water resistance conditions does not occur.

Hereinafter, the present invention will be described in detail.

As used herein, "weight average molecular weight" is measured by a conventional method known in the art, for example, it can be measured by a GPC (gel permeation chromatograph) method. Further, 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). In addition, functional groups such as "acid value" and "hydroxyl value" may be measured by a method well known in the art, for example, may represent a value measured by a method of titration.

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

The aqueous primer composition according to the present invention includes an acrylic resin, a polyurethane polyol resin, a polyurethane resin, and a chlorinated-modified polyolefin resin.

In the aqueous primer composition, the weight ratio of the acrylic resin to the chlorinated-modified polyolefin resin may be 2 to 3:1. When the weight ratio of the acrylic resin and the chlorinated-modified polyolefin resin is within the above range, the water resistance and adhesion of the prepared coating film may be further improved.

acrylic resin

Acrylic resins serve to improve adhesion to materials and appearance characteristics.

The acrylic resin may be directly synthesized according to a known method, or a commercially available product may be used. In this case, the acrylic resin may be prepared by, for example, polymerizing at least one of a vinyl monomer and a (meth)acrylate monomer.

The type of the vinyl monomer is not particularly limited, but for example, styrene, methylstyrene, dimethylstyrene, fluorostyrene, ethoxystyrene, methoxystyrene, phenylene vinyl ketone, vinyl t-butyl benzoate, vinyl cyclohexano At least one selected from the group consisting of ester, vinyl acetate, vinyl pyrrolidone, vinyl chloride, vinyl alcohol, acetoxystyrene, t-butylstyrene and vinyltoluene may be used.

Examples of the (meth)acrylate monomer include N-methylolacrylamide, 2-hydroxypropyl methacrylate, propyl methacrylate, t-butylaminoethyl methacrylate, dicyclopentenyl oxyethyl methacryl. Late, acrylic acid dimer, hexanediol diacrylate, t-butyl acrylate, triisopropylsilyl acrylate, benzyl methacrylate, hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane triacrylic Late, tripropylene glycol diacrylate, ethyl methacrylate, isobutyl methacrylate, hydroxyisopropyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, triisopropyl silyl methacrylate, iso Bornyl acrylate, t-butylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, methyl methacrylate, acrylic acid, t-butyl methacrylate, isobornyl methacrylate, methacrylonitrile, methacrylic acid, You can use one or more selected from

In addition, the acrylic resin may have a pH of 7 to 9, or 7.5 to 8.5. When the pH of the acrylic resin is within the above range, there is an effect of improving storage properties and improving adhesion to materials.

Furthermore, the acrylic resin may have a minimum film formation temperature (MFFT) of 10 to 30 °C, or 13 to 22 °C. When the minimum film formation temperature of the acrylic resin is within the above range, there is an effect that the adhesion to the material is improved.

In addition, the acrylic resin may be in the form of an emulsion dispersed in water. For example, the acrylic resin may be in the form of an emulsion dispersed in water and having a solid content of 30 to 60% by weight, or 40 to 50% by weight, based on the total weight of the resin. When the acrylic resin is in the form of an emulsion, there is an effect of excellent storability after painting, and when the solid content of the acrylic resin is within the above range, there is an effect of excellent storability and paint workability.

In addition, the acrylic resin may have a weight average molecular weight (Mw) of 10,000 to 20,000 g/mol, or 13,000 to 18,000 g/mol. When the weight average molecular weight of the acrylic resin is within the above range, the chemical resistance to the material, the adhesion, and the degree of atomization of the paint are excellent.

Furthermore, the acrylic resin may be included in the composition in an amount of 15 to 30 parts by weight, or 20 to 25 parts by weight based on 5 to 15 parts by weight of the polyurethane polyol resin. When the content of the acrylic resin is within the above range, the problem of deterioration of the appearance of the prepared coating film and deterioration of various physical properties of the coating film, such as chemical resistance, can be prevented.

polyurethane polyol resin

The polyurethane polyol resin serves to improve the water resistance of the prepared coating film. In this case, the polyurethane polyol resin refers to a resin including a hydroxyl group at the terminal of the polyurethane resin. For example, the polyurethane polyol resin may be prepared by reacting a polyol resin and a diisocyanate. In addition, the polyol resin and diisocyanate are the same as described for the polyurethane polyol resin.

Meanwhile, the polyurethane polyol resin may be a water-soluble polyurethane polyol in which the polyurethane polyol resin is dispersed in water. For example, the polyurethane polyol resin may be a water-soluble polyurethane polyol in which the solid content is 20 to 40 wt%, or 25 to 35 wt%, based on the total weight of the resin, and the polyurethane polyol resin is dispersed in water. When the polyurethane polyol resin is water-soluble as described above, compatibility with a water-soluble paint is excellent, and when the solid content is within the above range, there is an effect of excellent coating workability and storage of the resin itself.

Furthermore, the polyurethane polyol resin may have a glass transition temperature (Tg) of 80 to 200 °C, or 100 to 150 °C. When the glass transition temperature of the polyurethane polyol resin is within the above range, there is an effect of excellent heat resistance.

In addition, the polyurethane polyol resin may have a hydroxyl value (OHv) of 80 to 180 mgKOH/g, or 100 to 150 mgKOH/g. When the hydroxyl value of the polyurethane polyol resin is within the above range, there is an effect excellent in material adhesion and water resistance.

In addition, the polyurethane polyol resin may have a pH of 8 to 10, or 8.9 to 9.5. When the pH of the polyurethane polyol resin is within the above range, the resin itself has an excellent storage property.

In addition, the polyurethane polyol resin may be included in the composition in an amount of 5 to 15 parts by weight, or 6 to 10 parts by weight based on 15 to 30 parts by weight of the acrylic resin. When the content of the polyurethane polyol resin is within the above range, it is possible to prevent the problem of deterioration of adhesion and water resistance of the prepared coating film.

polyurethane resin

The polyurethane resin serves to improve the weather resistance and appearance characteristics of the coating film.

The polyurethane resin may be prepared by reacting a polyol resin and diisocyanate. In this case, the polyol resin may be at least one selected from the group consisting of polyester polyol, polyethylene polyol, polypropylene polyol, polybutylene polyol, and acrylic polyol.

In addition, the diisocyanate is isophorone diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylene diisocyanate, 2,3-dimethylethylene diisocyanate, 1- Methyl trimethylene diisocyanate, 1,3-cyclopentene diisocyanate, 1,4-cyclopentene diisocyanate, 1,2-cyclopentene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2 ,4-toluene diisocyanate, 2,6-toluene diisocyanate, oligomeric isocyanate, isophorone diisocyanate, 4,4-diphenylpropane diisocyanate, xylene diisocyanate, and 1,1,6,6-tetramethylhexamethylene It may be at least one selected from the group consisting of diisocyanate.

In addition, the polyurethane resin is polyether polyurethane, polyester polyurethane, polycarbonate polyurethane, polyether ester polyurethane, polyether carbonate polyurethane, polycaprolactone polyurethane, aliphatic hydrocarbon polyurethane, aromatic hydrocarbon polyurethane and It may include one or more selected from mixtures thereof.

Furthermore, the polyurethane resin may be a water-dispersible polyurethane dispersion in which the polyurethane resin is dispersed in water. For example, the polyurethane resin may be a water dispersion type polyurethane dispersion dispersed in water and having a solid content of 30 to 50% by weight, or 35 to 45% by weight, based on the total weight of the resin. When the polyurethane resin is a water-dispersible polyurethane dispersion as described above, there is an effect excellent in compatibility with a water-soluble paint, and when the solid content is within the above range, the resin itself has an excellent storage property.

In addition, the polyurethane resin may have a glass transition temperature (Tg) of -60 to -30 °C, or -50 to -40 °C. When the glass transition temperature of the polyurethane resin is within the above range, there is an effect of excellent adhesion to the material and weather resistance.

In addition, the polyurethane resin may have a pH of 7 to 9, or 7 to 8. When the pH of the polyurethane resin is within the above range, there is an excellent effect of coating workability and storage properties of the resin itself.

Furthermore, the polyurethane resin may be included in the composition in an amount of 5 to 15 parts by weight, or 6 to 10 parts by weight based on 15 to 30 parts by weight of the acrylic resin. When the content of the polyurethane resin is less than 5 parts by weight, a problem of insufficient appearance characteristics and physical properties of the prepared coating film may occur, and when included in an amount of more than 15 parts by weight, the problem of insufficient appearance and weather resistance of the prepared coating film may occur.

Chlorinated-modified polyolefin resin

The chlorinated-modified polyolefin resin serves to improve the chemical resistance to be produced, the adhesion properties of the coating film, and the appearance characteristics. In this case, the chlorinated-modified polyolefin resin means a polyolefin resin modified with chlorine (Cl).

In addition, the polyolefin resin may include at least one selected from the group consisting of polyethylene, polypropylene, polyisopropylene, polybutylene, and copolymers thereof.

Further, the polyolefin resin may have a weight average molecular weight (Mw) of 30,000 to 100,000 g/mol, or 50,000 to 70,000 g/mol. When the weight average molecular weight of the polyolefin resin is within the above range, there is an effect of excellent heat resistance to the material.

In addition, the polyolefin resin may have a pH of 7 to 9, or 7.5 to 8.5. When the pH of the polyolefin resin is within the above range, there is an effect excellent in appearance and storage properties of the resin itself.

In addition, the content of chlorine in the polyolefin resin may be 10 to 30% by weight or 13 to 20% by weight based on the total weight of the resin. When the chlorine content of the polyolefin resin is within the above range, there is an excellent effect in water resistance and chemical resistance.

Furthermore, the polyolefin resin may be in the form of an emulsion dispersed in a solvent. For example, the polyolefin resin may be in the form of an emulsion dispersed in a solvent, and the solid content may be 20 to 40 wt%, or 25 to 35 wt%, based on the total weight of the resin. When the polyolefin resin is in the form of an emulsion as described above, there is an effect excellent in compatibility with a water-soluble paint, and when the solid content is within the above range, there is an effect that the resin viscosity can be easily adjusted.

In addition, the polyolefin resin may be included in the composition in an amount of 5 to 15 parts by weight, or 6 to 12 parts by weight based on 15 to 30 parts by weight of the acrylic resin. When the content of the polyolefin resin is within the above range, problems of deterioration in water resistance, adhesion properties of the coating film and appearance may be prevented.

The composition may further include at least one selected from the group consisting of an acryl-epoxy emulsion and a polyester resin.

Acrylic-Epoxy Emulsion

The acryl-epoxy emulsion serves to improve heat resistance, adhesion of a coating film, curing density, moisture resistance, impact resistance and appearance characteristics.

In this case, the acryl-epoxy emulsion may be an emulsion in which a resin including an acryl unit and an epoxy unit is dispersed in water. Specifically, the acrylic-epoxy emulsion is in the form of an emulsion in which a resin including an acrylic unit and an epoxy unit is dispersed in water, and the solid content may be 35 to 55% by weight, or 40 to 53% by weight based on the total weight of the resin. have. When the acrylic-epoxy emulsion is in the form of an emulsion as described above, there is an effect of excellent compatibility with water-soluble paints, and when the solid content is within the above range, the resin itself has an excellent storability.

In addition, the acrylic-epoxy emulsion may have a glass transition temperature (Tg) of 50 to 70 °C, or 55 to 65 °C. When the glass transition temperature of the acryl-epoxy emulsion is within the above range, there is an effect of excellent adhesion to the material.

In addition, the acrylic-epoxy emulsion may have a pH of 8 to 10, or 8.5 to 9.5. When the pH of the acryl-epoxy emulsion is within the above range, the resin itself has an excellent storage property.

Further, the acrylic-epoxy emulsion may be included in the composition in an amount of 0.05 to 8 parts by weight, or 1 to 3.5 parts by weight based on 15 to 30 parts by weight of the acrylic resin. When the content of the acryl-epoxy emulsion is within the above content range, it is possible to prevent the problem of deterioration of the water resistance of the coating film and the storability of the composition.

polyester resin

The polyester resin serves to improve weather resistance, adhesion of the coating film, and water resistance.

In addition, the polyester resin may be directly synthesized according to a known method, or a commercially available product may be used. For example, the polyester resin may be prepared by reacting a carboxylic acid and a hydroxyl group-containing monomer. In this case, the carboxylic acid is adipic acid (AA), isophthalic acid (IPA), trimmaletic anhydride (TMA), cycloaliphatic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, fumaric acid, maleic anhydride, It may be at least one selected from the group consisting of tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and derivatives thereof. In addition, the hydroxyl group-containing monomer is methoxy polyethylene glycol, 1,6-hexanediol (1,6-HD), neopentyl glycol (NPG), trimethylol propane (TMP), ethylene glycol, propylene glycol, diethylene glycol, It may be at least one selected from the group consisting of butanediol 1,4-hexanediol and 3-methylpentanediol.

Furthermore, the polyester resin may have a weight average molecular weight (Mw) of 10,000 to 40,000 g/mol, or 20,000 to 30,000 g/mol. When the weight average molecular weight of the polyester resin is within the above range, there is an effect of excellent coating workability.

In addition, the polyester resin may have a glass transition temperature (Tg) of -30 to -10 °C, or -25 to -15 °C. When the glass transition temperature of the polyester resin is within the above range, there is an excellent effect of interlayer adhesion between the primer and the base.

In addition, the polyester resin may have an acid value (Av) of 1 to 10 mgKOH/g, or 3 to 5 mgKOH/g. When the acid value of the polyester resin is within the above range, there is an effect of excellent adhesion to the material.

Furthermore, the polyester resin may be included in the composition in an amount of 5 to 15 parts by weight, or 6 to 10 parts by weight based on 15 to 30 parts by weight of the acrylic resin. When the content of the polyester resin is within the above range, it is possible to prevent the problem of insufficient water resistance of the prepared coating film and the deterioration of the workability of the composition.

solvent

The aqueous primer composition may further include a solvent. In this case, the solvent may be a mixture of an alcohol-based solvent and water.

The alcohol-based solvent maintains the thickness of the prepared coating film and serves to improve the workability of the composition. In addition, the alcohol-based solvent may include at least one selected from ethanol, methanol, isopropanol, n-propanol, and mixtures thereof.

In addition, the alcohol-based solvent may have a specific gravity of 0.75 to 0.90 g/cc, or 0.80 to 0.85 g/cc. In addition, the solvent may have a boiling point of 90 to 110 °C, or 95 to 99 °C. When the specific gravity of the solvent is within the above range, there is an effect of excellent storability after painting, and when the boiling point is within the above range, there is an effect of excellent painting workability and easy control of the drying rate of the painted surface.

Furthermore, the water controls the viscosity of the composition and serves to reduce the content of volatile organic compounds (VOCs) in the composition. For example, the water may include deionized water, pure water, ultrapure water, distilled water, and the like.

In addition, the solvent may be included in the composition in an amount of 13 to 40 parts by weight, or 20 to 30 parts by weight based on 15 to 30 parts by weight of the acrylic resin. For example, the solvent may include 1 to 10 parts by weight, or 2 to 6 parts by weight of an alcohol-based solvent, and 10 to 30 parts by weight, or 10 to 25 parts by weight of water, based on 15 to 30 parts by weight of the acrylic resin. . When the content of the alcohol-based solvent in the composition is within the above range, the problem of deterioration of the appearance characteristics of the prepared coating film or insufficient dryness of the composition can be prevented. In addition, when the content of water in the composition is within the above range, it is possible to prevent a problem in that the viscosity of the composition increases and the smoothness of the prepared coating film decreases, and the problem that flow occurs during coating due to increased fluidity due to the low viscosity of the composition. .

Pigment

The aqueous primer composition may further include a pigment. The pigment serves to impart color to the prepared coating film. In this case, the pigment may include, for example, talc, calcium carbonate, titanium dioxide, iron oxide, sulfur oxide, and the like.

In addition, the pigment may be included in the composition in an amount of 1 to 10 parts by weight, or 4 to 10 parts by weight based on 15 to 30 parts by weight of the acrylic resin. When the pigment content in the primer composition is within the above range, it is possible to prevent a problem of insufficient hiding power of the prepared film, and a problem of lowering the adhesion of the coating film.

additive

The aqueous primer composition may further include at least one additive selected from the group consisting of a wax, a thickener, an antifoaming agent, a UV stabilizer, a surface adjusting agent, a pH adjusting agent, and a dispersing agent.

In this case, the additive may be included in the composition in an amount of 1 to 20 parts by weight, or 5 to 15 parts by weight based on 15 to 30 parts by weight of the acrylic resin.

In addition, the wax serves to improve the abrasion resistance of the coating film. The wax is not particularly limited as long as it is a conventional wax that can be used in the coating composition, and for example, a polyolefin wax, a fluorine wax, and a paraffin wax may be used.

Furthermore, the thickener serves to improve the flowability of the composition. The thickener is not particularly limited as long as it is a conventional one that can be used in the coating composition, and for example, a urethane-based thickener or an acrylic-based thickener may be used.

In addition, the antifoaming agent serves to suppress the generation of bubbles during the formation of the coating film. In this case, the antifoaming agent may be used without any particular limitation as long as it is a conventional antifoaming agent that can be used in the paint composition.

In addition, the UV stabilizer serves to improve the weather resistance of the final coating film by blocking the ultraviolet rays reaching the prepared coating film. For example, the ultraviolet absorber may be a benzotriazole-based ultraviolet absorber.

Furthermore, the surface conditioning agent serves to control the surface tension of the prepared coating film. The surface modifier may be used without any particular limitation as long as it is a conventional material that can be used in the coating composition, and for example, a polysiloxane-based or non-silicone-based compound may be used.

In addition, the surface conditioning agent serves to improve the smoothness of the coating film. In this case, the surface modifier may be used without any particular limitation as long as it is a conventional material that can be used in the coating composition, for example, a polyacrylate copolymer or a polyether siloxane-based compound may be used.

In addition, the dispersant serves to improve the dispersibility of the pigment and other additives. In this case, the dispersant may be used without any particular limitation as long as it is a conventional dispersant that can be used in the coating composition, for example, an acrylic or polyester-based dispersant may be used.

The aqueous primer composition has a podcup viscosity of from 20 to 40 seconds, or from 25 to 35 seconds, based on Podcup No. 4 at 25°C, and from 20 to 35% by weight, or from 25 to 30% by weight, based on the total weight of the composition. It may contain solids.

As described above, the aqueous primer composition according to the present invention has excellent paint workability and excellent adhesion to polyamide-based materials such as nylon. In addition, the water-based primer composition is environmentally friendly due to its low VOC content due to the organic solvent in the paint due to its water solubility. Furthermore, the coating film prepared from the aqueous primer composition has excellent physical properties such as appearance characteristics, water resistance, weather resistance, chemical resistance, and heat resistance. In particular, the coating film is remarkably excellent in water resistance because peeling of the coating film produced under water resistance conditions does not occur.

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.

[Example]

Examples 1 to 11 and Comparative Examples 1 to 5. Preparation of aqueous primer composition

An aqueous primer composition was prepared using each component in the composition as shown in Tables 1 and 2 below.

Specifically, water, a solvent, and a pH adjuster are placed in a container, mixed at a low speed of 80 rpm using a stirrer, and then stirred at low speed while stirring at a low speed while stirring the resin part (acrylic dispersion, acrylic-epoxy emulsion, polyester, polyurethane polyol, polyurethane resin and chlorinated polyolefin resin) was placed in a container. Then, while stirring at 150 rpm for 15 minutes at medium speed, antifoaming agent, pigment, surface conditioner and wax were added, and medium speed stirring was performed for 30 minutes. Thereafter, the viscosity of the No. 4 Podcup at 25° C. was adjusted to 25 to 35 seconds by additionally using water or a thickener.

ingredient
(Part by weight) Example One 2 3 4 5 6 7 8 9 10 11 Water-soluble acrylic dispersion 1 22.7 24.8 20.7 25 22.7 23.7 - 22.7 23.58 23.96 24.5 Water-soluble acrylic dispersion 2 - - - - - - 22.7 - - - - Water-soluble polyurethane polyol 1 8.11 9.8 8.5 9.51 8.11 - 8.11 8.11 8 6.2 9.8 Water-soluble polyurethane polyol 2 - - - - - 9.89 - - - - - Water-dispersible polyurethane resin1 8.11 9.5 8.5 10 6.4 10 8.11 - 8 8.11 9.5 Water-dispersible polyurethane resin2 - - - - - - - 8.11 - - - Water-soluble chlorinated polyolefin resin1 8.11 9.5 9.5 6.5 8.11 9.96 - - 11.72 6.85 9.5 Water-soluble chlorinated polyolefin resin2 - - - - - - 8.11 8.11 - - - Water-soluble acrylic-epoxy emulsion 1.62 - 1.45 - - 3.2 1.62 1.62 1.5 1.83 - Water-dispersible polyester 8.11 - 8.11 - 9.73 - 8.11 8.11 9 9.9 - solvent 3.73 5 3.73 5.49 4.41 3.74 3.73 3.73 3.5 3.72 5.2 water 21.9 22.5 21.9 23 22.5 21.9 21.9 21.9 21 21.8 23 Pigment 7.7 8 7.7 9.2 7.7 7.7 7.7 7.7 4.5 7.72 8 Antifoam 0.97 One 0.97 One One 0.97 0.97 0.97 0.9 0.97 1.29 surface conditioning agent 0.24 0.5 0.24 0.3 0.24 0.24 0.24 0.24 0.2 0.24 0.37 wax 1.6 1.9 1.6 2 1.6 1.6 1.6 1.6 1.5 1.6 1.64 pH adjuster 3.1 3.5 3.1 4 3.5 3.1 3.1 3.1 2.8 3.1 3.2 thickener 4 4 4 4 4 4 4 4 3.8 4 4 total 100 100 100 100 100 100 100 100 100 100 100

Comparative example Ingredients (parts by weight) One 2 3 4 5 Water-soluble acrylic dispersion 1 24.93 10.14 51.76 - - Water-soluble acrylic dispersion 3 - - - - 22.7 Water-soluble polyurethane polyol 1 15.92 23.31 - 18.92 - Water-soluble polyurethane polyol 3 - - - - 8.11 Water-dispersible polyurethane resin1 15.92 - 2.5 18.92 - Water-dispersible polyurethane resin3 - - - - 8.11 Water-soluble chlorinated polyolefin resin1 - 23.31 2.5 18.92 Water-soluble chlorinated polyolefin resin3 - - - - 8.11 Water-soluble acrylic-epoxy emulsion - - - - 1.62 Water-dispersible polyester - - - - 8.11 solvent 3.72 3.73 3.73 3.73 3.73 water 21.9 21.9 21.9 21.9 21.9 Pigment 7.7 7.7 7.7 7.7 7.7 Antifoam 0.97 0.97 0.97 0.97 0.97 surface conditioning agent 0.24 0.24 0.24 0.24 0.24 wax 1.6 1.6 1.6 1.6 1.6 pH adjuster 3.1 3.1 3.1 3.1 3.1 thickener 4 4 4 4 4 total 100 100 100 100 100

Hereinafter, manufacturers and product names of each component used in Examples and Comparative Examples are shown in Table 3 below.

ingredient Remark Water-soluble acrylic dispersion 1 Solids: 47% by weight, pH 7.5, MFFT: 20°C Mw: 18,000 Water-soluble acrylic dispersion 2 Solids: 50% by weight, pH 8.5, MFFT: 13°C Mw: 13,000 Water-soluble acrylic dispersion 3 Solids: 45% by weight, pH 6, MFFT: 7°C Mw: 8,000 Water-soluble polyurethane polyol 1 Solids: 33% by weight, pH 9, Tg: 140°C, OHv: 120 mgKOH/g Water-soluble polyurethane polyol 2 Solids: 35% by weight, pH 9, Tg: 100°C, OHv: 105 mgKOH/g Water-soluble polyurethane polyol 3 Solids: 15% by weight, pH 9, Tg: 70°C, OHv: 78 mgKOH/g Water-dispersible polyurethane resin1 Solids: 40% by weight, pH 7, Tg: -46°C Water-dispersible polyurethane resin2 Solids: 43% by weight, pH 7.5, Tg: -41°C Water-dispersible polyurethane resin3 Solids: 40% by weight, pH 10, Tg: -25°C Water-soluble chlorinated polyolefin resin1 Solids: 30% by weight, pH 8, Mw: 60,000 g/mol,
Chlorine content (total weight of resin): 20% by weight Water-soluble chlorinated polyolefin resin2 Solids: 30% by weight, pH 7.5, Mw: 50,000 g/mol,
Chlorine content (total weight of resin): 13% by weight Water-soluble chlorinated polyolefin resin3 Solids: 30% by weight, pH 6.5, Mw: 25,000 g/mol,
Chlorine content (total weight of resin): 5% by weight Water-soluble acrylic-epoxy emulsion Solids: 47.5% by weight, pH 9, Tg: 59°C Water-dispersible polyester Solids: 27% by weight, pH 5.5, Tg: -20°C, Mw: 25,000 g/mol,
Av: 4mgKOH/g solvent n-propanol water Deionized water (DIW) Pigment Mixture of talc, titanium dioxide and carbon black Antifoam 2,4,7,9-tetramethyl-5-decyne-4,7-diol surface conditioning agent polysiloxane compound wax Ethylene-vinyl-acetate (EVA) copolymer wax
(Solid content: 20% by weight, pH 5.5) pH adjuster Manufacturer: KCC, Product name: CVC00479 thickener modified acrylic polymer

Test Example: Characteristic evaluation of the prepared coating film

The aqueous primer compositions of Examples 1 to 11 and Comparative Examples 1 to 5 were coated on a nylon material to a dry film thickness of 12 μm, and left at room temperature for 3 minutes. After drying by blowing hot air at 80°C for 5 minutes, apply an oil-soluble clear paint (manufacturer: KCC, product name: UT5787F-A-9000(G-25)) so that the dry film thickness is 33㎛, and at 80°C for 30 minutes During the curing process by blowing hot air to form a final coating film. The appearance characteristics and physical properties of the final coating film were measured in the following manner, and the results are shown in Table 3.

(1) Painting workability

The water-based primer composition of Examples 1 11 and Comparative Examples 1 to 5 was coated twice reciprocally on a 30cm×40cm (width×length) tin plate using 61 IWATA guns, and the degree of atomization of the paint, the degree of smoothness and the thickness of the film The ascending properties were compared.

Specifically, visually good skin spreadability on the surface and excellent spreadability is excellent (◎), visually good riseability but insufficient coating spreadability is good (○), and visual rise and spreadability is insufficient. And, if there were less than 3 points of coating foreign matter, it was evaluated as normal (Δ), and if there was more than 3 points of coating foreign matter and cratering occurred, it was evaluated as bad (×).

(2) Appearance

Gloss (LU), sharpness (SH), and orange peel (OP) were measured using Wave Scan DOI (BYK Gardner), a vehicle exterior measuring instrument for the final coating film, and the overall appearance evaluation value (CF) using the measured physical properties ) was calculated by Equation 1 below.

[Equation 1]

CF = LU×0.15 + SH×0.35 + OP×0.5

At this time, it was determined that the higher the CF value, the better the appearance characteristics of the coating film. Specifically, when the CF value was 60 or more, it was evaluated as excellent (◎), when it was 50 or more and less than 60, it was good (○), when it was 40 or more and less than 50, it was evaluated as normal (Δ), and when it was less than 40, it was evaluated as bad (×).

(3) Adhesiveness

According to the ASTM D3359 tape adhesion test method, the adhesiveness of the final coating film was drawn in 100 squares (width 1mm × length 1mm) with a blade and peeled off using a tape to measure the adhesion.

At this time, if 100 squares are 100% completely attached, excellent (◎), if the remaining squares are 95% or more and less than 100%, good (○), if 90% or more and less than 95%, normal (△), 85% or more and less than 90% case was evaluated as bad (×).

(4) water resistance

After immersing the final coating film in a 40℃ thermostat for 10 days, the adhesion and appearance characteristics of the coating film were evaluated. The evaluation criteria are excellent (◎) when 100% of 100 squares are completely attached, and 95% or more and less than 100% are attached. In the case of good (○), when 90% or more and less than 95% were attached, it was evaluated as normal (△), and when less than 90% was attached, it was evaluated as bad (x).

(5) Weather resistance

After exposing the final coating film with energy of 2,500 kJ in a xenon weatherometer tester environment, the appearance, color difference and adhesion properties of the coating film before and after energy exposure were compared. Excellent (◎) in case of grade or higher, color difference ΔE greater than 3.0, adhesion M 1.0 to 2.5, and gray scale grade 3 or higher, good (○), If the color difference is greater than ΔE 3.0 and adhesion is M 1.0 to 2.5 and less than Gray Scale 3, it is evaluated as normal (Δ), and if the color difference is ΔE 3.0 and adhesive is greater than M 2.5 and less than Gray Scale 3, it is evaluated as poor (×). did.

(6) Chemical resistance

Chemical resistance was evaluated by applying isobutanol, ethanol and methanol respectively to the cloth and rubbing the final coating film with a load of 500 g 10 times. As a result of the test, when the film does not peel off and the color does not change, excellent (◎), when the film does not peel off and only discolors, good (○), when the film is peeled but does not change color Normal (△), when the film is peeled or discolored It was evaluated as bad (x).

(7) heat resistance

After leaving the final coating film in an oven at 80°C for 300 hours, the adhesion and appearance of the coating film were compared before and after leaving it at high temperature. Excellent (◎) when the adhesion is M 1.0 to 2.5, color difference ΔE 2.0 or less, and Gray Scale 3 or higher , Good (○) when the adhesion is M 1.0 to 2.5, color difference ΔE 2.0 or higher, Gray Scale Grade 3 or higher, Normal (Δ) when adhesion M 1.0 to 2.5, color difference ΔE 2.0 or less and Gray Scale Grade 3 or higher , If the adhesion is M 3.0 or more, the color difference ΔE is greater than 2.0, and the gray scale is less than 3rd grade, it was evaluated as defective (×).

Paint workability Exterior adherence Water resistance Weather resistance Chemical resistance heat resistance Example 1 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 2 ◎ ○ ○ ○ ○ ◎ ◎ Example 3 ◎ ○ ◎ ◎ ◎ ○ ◎ Example 4 ◎ ○ ○ ○ ○ ◎ ◎ Example 5 ◎ ○ ○ ◎ ◎ ◎ ◎ Example 6 ○ ◎ ○ ○ ◎ ◎ ◎ Example 7 ○ ○ ○ ◎ ◎ ○ ○ Example 8 ◎ ◎ ◎ ◎ ○ ○ ○ Example 9 ◎ ○ ◎ ○ ◎ ◎ ◎ Example 10 ◎ ◎ ○ ○ ◎ ◎ ○ Example 11 ◎ ◎ ○ ○ ◎ ◎ ◎ Comparative Example 1 ○ ○ X ○ ○ X △ Comparative Example 2 ○ X △ △ X ○ ○ Comparative Example 3 ○ X ○ X ○ △ ○ Comparative Example 4 ○ X X ○ ○ ○ ○ Comparative Example 5 ○ ○ △ △ △ △ △

As shown in Table 4, the aqueous primer compositions of Examples 1 to 11 had excellent coating workability, and the coating film prepared therefrom had excellent appearance characteristics, adhesion, water resistance, weather resistance, chemical resistance, and heat resistance.

On the other hand, the coating films prepared from the primer compositions of Comparative Examples 1 to 5 lacked water resistance, weather resistance, chemical resistance and heat resistance. In particular, Comparative Example 2, in which the content of the acrylic dispersion was insufficient, was remarkably lacking in all physical properties.

Claims (7)

Acrylic resins, polyurethane polyol resins, polyurethane resins and chlorinated modified polyolefin resins,
The minimum film forming temperature (MFFT) of the acrylic resin is 13 to 22 ℃,
The glass transition temperature of the polyurethane polyol resin is 100 to 150 ℃,
The glass transition temperature of the polyurethane resin is -50 to -40 ℃, the aqueous primer composition. The method according to claim 1,
The acrylic resin has a solid content of 30 to 60% by weight based on the total weight of the resin, and an acrylic dispersion having a weight average molecular weight (Mw) of 10,000 to 20,000 g/mol, an aqueous primer composition. The method according to claim 1,
The polyurethane polyol resin has a hydroxyl value of 80 to 180 mgKOH/g, and a solid content of 20 to 40% by weight based on the total weight of the resin, an aqueous primer composition. The method according to claim 1,
The polyurethane resin is a water-dispersible polyurethane having a solid content of 30 to 50% by weight based on the total weight of the resin, an aqueous primer composition. The method according to claim 1,
The chlorinated-modified polyolefin resin has a weight average molecular weight of 30,000 to 100,000 g/mol, a solid content of 20 to 40% by weight based on the total weight of the resin, and a chlorine content of 10 to 30% by weight based on the total weight of the resin, Aqueous primer composition. The method according to claim 1,
The composition comprises 15 to 30 parts by weight of an acrylic resin, 5 to 15 parts by weight of a polyurethane polyol resin, 5 to 15 parts by weight of a polyurethane resin, and 5 to 15 parts by weight of a chlorinated-modified polyolefin resin. The method according to claim 1,
The composition further comprises at least one selected from the group consisting of an acrylic-epoxy emulsion and a polyester resin, an aqueous primer composition.