KR101477890B1 - Water dispersible 2 component acrylic polyol resin composition - Google Patents

Abstract

The present invention relates to a water-dispersible two-component type acrylic polyol resin composition, which comprises 1 to 30 parts by weight of an epoxy-based reactive diluent monomer; 1 to 15 parts by weight of a carboxyl group-containing monomer; 1 to 50 parts by weight of a hydroxyl group-containing monomer; 1 to 20 parts by weight of a nonionic type acrylate monomer; 1 to 20 parts by weight of an unsaturated monomer; 0.1 to 5 parts by weight of reactive silane; And 1 to 10 parts by weight of a neutralized basic amine capable of reacting with an isocyanate compound, wherein the nonionic acrylate is at least one compound selected from the group consisting of polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate (Meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, polyethylene glycol polytetramethylene glycol mono (meth) acrylate, polypropylene glycol polytetramethylene glycol mono And the like.
As a result, the content of the organic solvent which is excellent in gloss and appearance, exhibits excellent physical properties such as water resistance, solvent resistance, weather resistance and adhesion, excellent storage stability after water dispersion, It is possible to provide a low water dispersible two-pack type acrylic polyol resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a water-dispersible two-component type acrylic polyol resin composition,

The present invention relates to a water-dispersible, two-pack type acrylic polyol resin composition.

Recently, in order to develop environmentally friendly paint in domestic and overseas, we are developing various uses and properties.

Particularly, since the content of the organic solvent can be reduced as compared with the conventional solvent type acrylic resin, the water-based type paint is an environment-responsive type resin and is used for ships, automobiles, trains, plastic molded articles, household appliances, large- It is used for various purposes such as for building, construction, woodworking and so on.

Among these fields, in the fields of marine, railway, automotive coatings, and the like, there is a demand for coating properties excellent in gloss, appearance, solvent resistance and water resistance similar to oily paints, As regulations for environmental problems become more severe, there is a desperate need for a technique capable of sufficiently reducing the content of organic solvents in order to further realize low VOC (Volatile Organic Compound) while having good storage stability.

Korean Patent Laid-Open Publication No. 10-2012-0048061 discloses a prior art, but the conventional art has a problem in that it does not meet recent environmental problems because it contains organic solvents in a certain amount or more.

In addition, an emulsifier is added in order to improve the storage stability and the complexity of the reaction process in the process of dispersing the resin having a high viscosity in the production of the water dispersion system, and the problem that the weatherability of the coating film is deteriorated by the emulsifier is also a concern.

As a result, researches have been actively carried out to sufficiently cope with recent environmental problems while sufficiently improving the physical properties of the coating film, such as gloss, solvent resistance, water resistance, and weather resistance, which are excellent in stable water dispersion and storage stability of the acrylic resin of the water dispersion system .

It is an object of the present invention to provide an organic solvent which is excellent in gloss and appearance, exhibits excellent physical properties such as water resistance, solvent resistance, weather resistance, and adhesion, is excellent in storage stability after water dispersion, Water-soluble two-component acrylic polyol resin composition.

According to the present invention, the above-mentioned object is achieved by a composition comprising 1 to 30 parts by weight of an epoxy-based reactive diluent monomer; 1 to 15 parts by weight of a carboxyl group-containing monomer; 1 to 50 parts by weight of a hydroxyl group-containing monomer; 1 to 20 parts by weight of a nonionic type acrylate monomer; 1 to 20 parts by weight of an unsaturated monomer; 0.1 to 5 parts by weight of reactive silane; And 1 to 10 parts by weight of a neutralized basic amine capable of reacting with an isocyanate compound, wherein the nonionic acrylate is at least one compound selected from the group consisting of polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate (Meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, polyethylene glycol polytetramethylene glycol mono (meth) acrylate, polypropylene glycol polytetramethylene glycol mono Wherein the water-soluble two-component acrylic polyol resin composition is at least one selected from the group consisting of water-soluble two-component acrylic polyol resin compositions.
Here, the epoxy-based reactive diluent monomer has the following chemical formula.

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(Wherein R1 and R2 are alkyl groups having 1 to 6 carbon atoms)

The carboxyl group-containing monomer may be at least one selected from the group consisting of (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and maleic anhydride.

Also, the hydroxyl group-containing monomer may be at least one selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- hydroxybutyl (meth) acrylate, ) Acrylate, caprolactone-modified hydroxy (meth) acrylate, and the like.

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On the other hand, the reactive silane is preferably selected from the group consisting of glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxy But are not limited to, ethoxysilane, ethoxysilane, vinylmethyldimethoxysilane, methacryloxypropyltrimethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, aminneohexyltrimethoxysilane , Aminneohexylmethyldimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, and the like.

According to the present invention, it is possible to provide an organic solvent which is excellent in gloss and appearance, exhibits excellent physical properties such as water resistance, solvent resistance, weather resistance, adhesion and the like, and is excellent in storage stability after water dispersion, It is possible to provide a water-dispersible, two-pack type acrylic polyol resin composition having a low content.

The present invention relates to a water-dispersible, two-component acrylic polyol resin composition obtained by neutralizing an acrylic polymer containing a carboxyl group-containing monomer, a hydroxyl group-containing monomer and a non-ionic acrylate monomer as essential components with a specific amine compound as a neutralizing base, And curing with an isocyanate compound, so that the action and effect of the present invention can be sufficiently exhibited. The hydrophilic property is improved by neutralizing the carboxyl group-containing monomer so that the dispersion stability after the water dispersion is sufficient, and at the same time, the nonionic type acrylate monomer is used to complement the hydrophilic property. As the curing agent, a hydrophilic group-containing isocyanate compound excellent in compatibility with an acrylic polyol resin in an aqueous dispersion form may be used, or an isocyanate compound diluted with an organic solvent And the acid value is designed to be low in order to increase the pot life when mixed with the curing agent. After the film formation, the isocyanate compound as a curing agent reacts with the hydroxyl group in the resin and also with the amine compound used for neutralizing the carboxyl group, It is possible to prevent deterioration of the water resistance caused by the base and to exert excellent appearance and physical properties of the coating film when used for various purposes. In addition, for the purpose of improving the weather resistance, reactive silane which improves adhesion and cross-linking density was introduced to exhibit solvent resistance, high weatherability and excellent scratch resistance.

In order to exhibit excellent water resistance, it is necessary to increase the molecular weight of the resin composition. In this case, a high viscosity is required and a large amount of solvent must be used, and dispersion stability may not be sufficient. Among monomer components constituting the acrylic resin, Rate is used to complement the neutralized portion of the carboxyl group with a base to improve the dispersion stability and to minimize the content of the organic solvent by using an epoxy-based reactive dilution monomer when synthesizing an acrylic resin, and at the same time, It is possible to produce a polymer with little use of a small amount of solvent or with little use of the solvent, and water dispersion is facilitated, so that it becomes possible to exhibit sufficient dispersion stability while preventing deterioration of water resistance .

That is, the present invention relates to a process for producing an acrylic resin composition comprising an epoxy-based reactive diluent monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer and a non-ionic acrylate monomer as essential components and optionally an acrylic resin containing an unsaturated monomer and a reactive silane, 2-part type acrylic polyol resin composition containing a neutralized basic amine capable of reacting with water.

Hereinafter, the present invention will be described in detail.

The present invention relates to a water-dispersible two-component type acrylic polyol resin composition, which comprises an epoxy-based reactive diluent monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer and a non-ionic acrylate monomer as essential components, An acrylic resin containing silane and a neutralized basic amine capable of reacting with an isocyanate compound.

It is preferable that the acrylic polymer is obtained by a solution polymerization using an epoxy-based reactive diluent monomer and dispersing the acrylic polymer in water in the presence of an amine compound in order to use little or no organic solvent in early acrylic polymerization.

The content of the organic solvent in the resin composition is preferably 30 parts by weight or less based on 100 parts by weight of the solid content and more preferably no organic solvent at all.

As described above, the water-dispersible, two-pack type acrylic polyol resin composition of the present invention sufficiently exhibits the desired performance without adding an organic solvent. However, in order to further improve the performance of the coating film, It is also possible to add an organic solvent separately.

The method for solution polymerization in the organic solvent using the monomer component is not particularly limited, but examples of the organic solvent to be used include methanol, ethanol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, methyl cellosolve, Alcohols such as sorb, propylcellosolve, butyl cellosolve, methylcarbitol and ethylcarbitol; Ethylene glycols such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monobutyl ether; Ether esters such as methyl cellosolve acetate, ethyl cellosolve acetate and propylene glycol monomethyl ether acetate; Aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-heptane; Ketones such as acetone, methyl ethyl ketone methyl isobutyl ketone, diisobutyl ketone, and the like can be used.

Of these organic solvents, those having a high boiling point are preferred for the reaction between the epoxy-reactive type diluent monomer and the carboxyl group during the synthesis, and for example, propylene glycol monobutyl ether is preferable.

It is preferable that the polymerization reaction is carried out by maintaining the content of the organic solvent at 50 parts by weight or less with respect to 100 parts by weight of the total solvent amount in order to sufficiently improve the polymerizability of the monomer component and lower the content of the solvent. More preferably 30 parts by weight or less.

In the above water-dispersible two-component type acrylic polyol resin composition, the acrylic resin is preferably a water-dispersible acrylic resin, a carboxyl group-containing monomer for reacting with the epoxy-based reactive diluent monomer, a hydroxyl group- An acrylic resin containing an anionic acrylate as an essential component which facilitates water dispersion is prepared by neutralizing an acrylic polymer containing a small amount of a solvent in the presence of an amine compound and then dispersing it in water or in a mixed solvent of water and an organic solvent A two-part type acrylic polyol resin is obtained by a method in which an acrylic polymer is subjected to solution polymerization using an epoxy-based reactive dilution monomer to disperse an acrylic polymer in water in the presence of an amine compound .

A small amount of solvent is required in the reaction vessel in the synthesis of the acrylic polymer. It is possible to cause sufficient polymerization and to replace the solvent necessary for forming the low viscosity type polymer with the epoxy reactive dilution monomer or to use the initial solvent or the minimum solvent in combination. The reactive diluent monomer thus used is allowed to polymerize with the carboxyl group-containing monomer in the acrylic monomer using an epoxy type reactive diluent monomer capable of polymerization with the acrylic monomer.

Here, the epoxy type reactive diluent monomer compound is represented by the following formula.

[Chemical Formula]

(Wherein R1 and R2 are alkyl groups having 1 to 6 carbon atoms).

Examples of the acrylic resin include a carboxyl group-containing monomer for allowing water dispersion and reaction with an epoxy-based reactive diluent monomer, a hydroxyl group-containing monomer for reacting with a curing agent, and a nonionic acrylic Rate as an essential component.

More preferably, a monomer component comprising an epoxy reactive type diluent monomer, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, and a non-ionic acrylate monomer as essential components and optionally containing an unsaturated monomer and a reactive silane is used .

When the water-dispersible, two-pack type acrylic polyol resin composition of the present invention is used as a cured coating or the like by reacting with the curing agent by using the hydroxyl group-containing monomer, it is possible to sufficiently improve the isocyanate and crosslinking density and to improve the water resistance, weather resistance, , Chemical resistance, and coating film hardness.

In the monomer component, the content of the epoxy-reactive diluent monomer in the component is preferably 1 part by weight or more based on the total amount of the monomers. Preferably 5 to 30 parts by weight, more preferably 5 to 20 parts by weight. When the amount is less than 5 parts by weight, the polymer does not form a polymer having a low viscosity. When the amount is more than 20 parts by weight, physical properties such as hardness of the dried coating film become insufficient.

In the monomer component, as the carboxyl group-containing monomer, one or more of (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and maleic anhydride may be used. Among these, (meth) acrylic acid is preferable.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, caprolactone-modified hydroxy (meth) acrylate, and the like. Of these, 2-hydroxyethyl (meth) acrylate is preferred.

The carboxyl group-containing monomer is neutralized with an amine and used for water dispersion. However, when the content is large, the viscosity is high due to excessive hydrophilization, adversely affecting the water resistance, and shorten the pot life time when mixed with isocyanate as a curing agent. When the content of carboxyl groups is small, water dispersion is not smooth and storage stability is also unstable. Therefore, non-ionic acrylate monomers which increase the stability of water dispersion and facilitate water dispersion while using a minimum carboxyl group-containing monomer are used. Examples of nonionic acrylate monomers include polyethylene glycol mono (meth) acrylate, polypropylene (Meth) acrylate, methacryloxypropyleneglycol mono (meth) acrylate, glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, polyethylene glycol polytetramethylene glycol mono (Meth) acrylate, and the like can be used. Of these, methoxypolyethylene glycol (meth) acrylate is preferred.

The content of the methoxypolyethylene glycol (meth) acrylate in the monomer component is preferably 1 part by weight or more based on the total amount of the monomers. Preferably 3 to 30 parts by weight, more preferably 5 to 20 parts by weight. If the amount is less than 5 parts by weight, stability of water dispersion may be increased, water dispersion may not be easy, and storage stability after water dispersion becomes insufficient. If it exceeds 20 parts by weight, the viscosity increases during synthesis, and a large amount of solvent is required, and the physical properties such as water resistance and smoothness are insufficient in the cured coating film.

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Among these, cyclohexyl (meth) acrylate and isobonyl (meth) acrylate are preferable for improving weather resistance. When isobornyl (meth) acrylate is used, the content of isobonyl (meth) acrylate in the monomer component is preferably 5 equivalents or more based on the total amount of the monomers. Preferably 10 to 80 equivalents, and more preferably 10 to 70 equivalents. If the amount is less than 5 equivalents, the performance such as hardness and weather resistance of the coating film becomes insufficient. On the other hand, if it exceeds 80 equivalent parts, the content of the hydroxyl group-containing monomer to which the curing agent reacts becomes small, so that the reaction with the curing agent becomes insufficient and the physical properties of the cured coating film become insufficient.

In addition, reactive silane is introduced to improve weatherability and adhesion and increase cross-linking density, so that solvent resistance, high weatherability and excellent scratch resistance can be exhibited.

Examples of the reactive silane include epoxy silane such as glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, and epoxycyclohexylethyltrimethoxysilane; Vinyl silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxyethoxysilane and vinylmethyldimethoxysilane; Acrylsilanes such as methacryloxypropyltrimethoxysilane; Aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, aminneohexyltrimethoxysilane, aminneohexylmethyldimethoxysilane, and aminoethylaminopropylmethyldimethoxysilane. Aminosilane; One or two or more kinds of silanes may be used. Among these, glycidoxypropyltrimethoxysilane is preferably used.

When the reactive silane is used, the content of the reactive silane in the monomer component is preferably 5 parts by weight or less based on the total amount of the monomers. Preferably 0.1 to 3 parts by weight. When the amount is less than 0.1 parts by weight, the performance of solvent resistance, weather resistance, and scratch resistance becomes insufficient. If the amount is more than 5 parts by weight, the cross-linking reaction is excessively caused in the course of the synthesis, resulting in an increase in viscosity or a gel-like state, making synthesis impossible.

The silane may be added to the reaction vessel together with the solvent and the reactive diluent monomer, or may be mixed with the acrylic monomer and the polymerization initiator.

In the polymerization method, examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis- (2-methylbutyronitrile); and azo compounds such as benzoyl peroxide, Oxides, cumene hydroperoxide, t-butylperoxy-2-ethylhexanoate, and t-amylperoxy-2-ethylhexanoate, and the like can be used. Of these, it is preferable to incorporate t-amyl peroxy-2-ethylhexanoate.

In order to lower the viscosity in the polymerization method, a chain transfer system can be used as needed. Examples of the chain transfer agent include, but are not limited to, butane thiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexylmercaptan, thiophenol, octyl thioglycolate, mercaptopropionic acid Octyl, 2-ethylhexyl mercaptopropionic acid ester, 2-mercaptoethyl ethyl octanoate, 1,8-dimercapto-3,6-dioxaoctane, decanetrithiol, dodecyl mercaptan mercaptoethanol, thioglycerol , Thiol chain transfer agents such as thioglycolic acid, mercaptopropionic acid and 2-mercaptoethanesulfonic acid; unsaturated hydrocarbon compounds such as? -methylstyrene dimer,? -terpinene,? -terpinene, dipentene, and tapinolene, and the like can be used. Among them, it is preferable to include an alpha -methylstyrene dimer chain transfer agent.

The method of adding the chain transfer agent to the reaction vessel may be introduced into the reaction vessel together with the solvent and the reactive diluting monomer, or may be mixed with the acrylic monomer and the polymerization initiator.

In the above polymerization method, the method of adding the monomer component or polymerization initiator to the reaction vessel is not particularly limited, but from the viewpoint of reducing the work stability against heat generation in the reaction and the molecular weight distribution of the acrylic resin, It is preferable to polymerize by a solution polymerization method using a method of dropping an initiator into a reaction vessel.

In the polymerization method, the polymerization conditions such as the polymerization temperature are appropriately determined by a solvent, a polymerization initiator, a chain transfer agent and the like, but the polymerization temperature is usually 0 ° C or higher, preferably 180 ° C or lower. More preferably, it is not lower than 120 ° C but not higher than 170 ° C.

In the dispersing step of the water-dispersible two-component type acrylic polyol resin, the acrylic resin obtained as described above is dispersed in water or a mixed solvent of water and an organic solvent in the presence of an amine compound. However, There is a preferred method in which an amine compound is added to an acrylic resin polymer polymerized in a small amount of solvent to neutralize the acrylic resin and then ion-exchanged water is added dropwise to the neutralized product to disperse it. Alternatively, the neutralized product is subjected to ion exchange It is possible to disperse by using a method of dropping and dispersing in water.

As the water-dispersible two-component type acrylic polyol resin composition of the present invention, secondary and tertiary amines having a boiling point of not higher than 280 ° C are used which can react with an isocyanate compound containing a hydroxyl group as a neutralizing base and being a curing agent.

As the amine compound, it is preferable to use one or more of, for example, dimethylethanolamine, N-methyldiethanolamine, diethanolamine, triethanolamine, and the like. Among them, triethanolamine is more preferable.

The amount of the amine compound to be used is preferably such that the acrylic polyol resin is neutralized to sufficiently maintain the resin dispersion stability and is not particularly limited. For example, when triethanolamine is used, the degree of neutralization of the carboxyl group in the acrylic resin In an amount of 30 to 150 mol%.

As the water-dispersible, two-pack type acrylic polyol resin obtained by the above process, the acid value based on the solid content is preferably 50 mgKOH / g or less. If it exceeds 50 mgKOH / g, the hydrophilicity of the obtained resin becomes excessively high. Therefore, when it is used for various purposes, it is poor in water resistance, and the viscosity of the resin becomes high while being water-soluble, have. And more preferably 30 mgKOH / g or less. Also, it is preferably 5 mgKOH / g or more. If it is less than 5 mgKOH / g, the dispersion stability of the resin is lowered, and there is a possibility that preparation of a stable aqueous dispersion type acrylic resin composition becomes impossible. More preferably 10 mgKOH / g or more.

The hydroxyl group is preferably 50 mgKOH / g or more and 300 mgKOH / g or less based on the solid content. If the amount is less than 50 mgKOH / g, the degree of crosslinking with the curing agent is insufficient in forming a coating film, and excellent coating performance can not be obtained. When the amount exceeds 300 mgKOH / g, the effect of the present invention can not be sufficiently exhibited. More preferably not less than 100 mgKOH / g and not more than 200 mgKOH / g.

The acrylic resin having an aqueous dispersion preferably has a weight average molecular weight of 1,000 or more and 50,000 or less. If the weight average molecular weight is less than 1,000, water resistance may not be sufficient. If the weight average molecular weight is more than 50,000, there is a possibility that the leveling property may not be excellent and a good appearance may not be given. The weight average molecular weight is more preferably 2,000 to 30,000.

In the water-dispersible, two-component acrylic polyol resin composition of the present invention, the polyisocyanate compound as the curing agent may be a polyisocyanate compound having a hydrophilic group or a polyisocyanate compound having a hydrophobic state diluted with an organic solvent. Blocked polyisocyanates may also be used if very long pot life is required.

If necessary, a crosslinking agent capable of reacting with a carboxyl group and a silane group may be used in combination. Examples of the crosslinking agent include oxazoline, carbodiimide, aziridinyl, epoxy, alkoxysilane, A compound having a functional group such as a methylol group, a methylol alkyl group or a vinyl ether group, or a polymer, may be used.

In the water-dispersible, two-component acrylic polyol resin composition of the present invention, the content of the polyisocyanate as a curing agent may be suitably set according to the use and the like, and is not particularly limited. For example, the isocyanate It is preferable to use from 0.5 equivalents to 3.0 equivalents of the group. If it is outside this range, there is a possibility that sufficient water resistance and weather resistance can not be obtained. More preferably 1.0 equivalents to 2.5 equivalents.

As the water-dispersible, two-pack type acrylic polyol resin composition, additives may also be used if necessary.

Examples of the additive include additives such as antioxidants, ultraviolet absorbers, ultraviolet stabilizers, polymerization inhibitors, leveling agents, wetting agents, defoamers, coupling agents, antibacterial agents, surfactants, plasticizers, lubricants, antiseptics, pigment dispersants, A flame retardant, a slip agent, a metal chelating agent, an anti-blocking agent, a heat stabilizer, a processing stabilizer, a colorant, and the like.

In the present invention, by coating the above-mentioned water-dispersible two-component type acrylic polyol resin composition on a substrate and curing it, it is possible to form a cured film preferable for various uses.

Examples of the substrate include a metal plate such as glass, aluminum, iron and zinc, a metal substrate, polyethylene, polyvinyl chloride, EVIE, a fiber reinforced plastic, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polystyrene, Plastic materials such as polypropylene, polyester, polyolefin, acrylic resin, epoxy resin and nylon resin, synthetic leather, wood, fiber, and paper.

The coating method and the method of curing the coating film when forming the coating film using the water-dispersible two-component type acrylic polyol resin composition may be suitably set according to the application to be used. Examples of the coating method include immersion coating, Application by a roll brush, spray coating, roll coating, dip coating, bar coating, float coating and the like are preferable.

The curing method can be carried out by room temperature curing, heat curing, or the like, and curing conditions and the like may be appropriately set according to the intended use.

Production Example 1 (Water-dispersible, two-pack type acrylic polyol resin A)

10 parts by weight of propylene glycol monobutyl ether and 10 parts by weight of an epoxy reactive diluent monomer were added in a four-necked flask equipped with a stirrer, a thermometer, a condenser and a fractional nude, and the mixture was heated to 150 ° C. Then, 17.2 parts by weight of styrene, 10 parts by weight of isobornyl methacrylate, 30 parts by weight of 2-hydroxyethyl methacrylate, 10 parts by weight of polyethylene glycol acrylate, 7.3 parts by weight of methacrylic acid, 2,2'-azobis- (2- Methylbutyronitrile) (5 parts by weight) were separately added dropwise over 3 hours. After completion of the dropwise addition, the mixture was maintained at 150 for 4 hours, cooled, and added with 5.5 parts by weight of triethanolamine at 100 or less and neutralized for 30 minutes. Then, 135 parts by weight of deionized water was added dropwise at 70 to obtain a water- A polyol resin A was obtained.

Production Example 2 (Water-dispersible, two-pack type acrylic polyol resin B)

A water-dispersible, two-pack type acrylic polyol resin B having a solid content of about 40 parts by weight was prepared in the same manner as in Preparation Example 1, except that the contents shown in the following Table 1 were applied.

Production Example 3 (Water-dispersible, two-pack type acrylic polyol resin C)

A water-dispersible, two-pack type acrylic polyol resin C having a solid content of about 40 parts by weight was prepared in the same manner as in Preparation Example 1, except that the contents shown in the following Table 1 were used.

Production Example 4 (Water-dispersible, two-pack type acrylic polyol resin D)

A water-dispersible, two-pack type acrylic polyol resin D having a solid content of about 40 parts by weight was prepared in the same manner as in Preparation Example 1, except that the contents shown in Table 1 were applied.

Production Example 5 (Water-dispersible, two-pack type acrylic polyol resin E)

A water-dispersible two-pack type acrylic polyol resin E having a solid content of about 40 parts by weight was prepared in the same manner as in Preparation Example 1, except that the contents shown in Table 1 were applied.

Production Example 6 (Water-dispersible, two-pack type acrylic polyol resin F)

A water-dispersible two-pack type acrylic polyol resin F having a solid content of about 40 parts by weight was prepared in the same manner as in Preparation Example 1, except that the contents shown in Table 1 were applied.

Production Example 7 (Water-dispersible, two-pack type acrylic polyol resin G)

A water-dispersible two-pack type acrylic polyol resin G having a solid content of about 40 parts by weight was prepared in the same manner as in Preparation Example 1, except that the contents shown in Table 1 were applied.

Production Example 8 (Water-dispersible, two-pack type acrylic polyol resin H)

A water-dispersible, two-pack type acrylic polyol resin H having a solid content of about 40 parts by weight was prepared in the same manner as in Preparation Example 1, except that the contents shown in the following Table 1 were used.

Production Example 9 (Water-dispersible, two-pack type acrylic polyol resin I)

A water-dispersible two-pack type acrylic polyol resin I having a solid content of about 40 parts by weight was prepared in the same manner as in Preparation Example 1, except that the contents shown in Table 1 were applied.

Production Example 10 (Water-dispersible, two-pack type acrylic polyol resin J)

A water-dispersible two-pack type acrylic polyol resin J having a solid content of about 40 parts by weight was prepared in the same manner as in Preparation Example 1, except that the contents shown in Table 2 were applied.

Production Example 11 (Water-dispersible, two-pack type acrylic polyol resin K)

A water-dispersible two-pack type acrylic polyol resin K having a solid content of about 40 parts by weight was prepared in the same manner as in Preparation Example 1, except that the contents shown in Table 2 were applied.

Production Example 12 (Water-dispersible, two-pack type acrylic polyol resin L)

A water-dispersible, two-pack type acrylic polyol resin L having a solid content of about 40 parts by weight was prepared in the same manner as in Preparation Example 1, except that the contents shown in Table 2 were applied.

Comparative Example 1 (Water-dispersible, two-pack type acrylic polyol resin M)

A water-dispersible, two-pack type acrylic polyol resin M having a solid content of about 40 parts by weight was prepared in the same manner as in Preparation Example 1, except that the contents shown in Table 2 were applied.

Comparative Example 2 (Water-dispersible, two-pack type acrylic polyol resin N)

A water-dispersible, two-pack type acrylic polyol resin N having a solid content of about 40 parts by weight was prepared in the same manner as in Preparation Example 1, except that the contents shown in Table 2 were applied.

[Measurement method and evaluation result 1]

The properties of the water-dispersible two-component acrylic polyol resin compositions prepared in Preparation Examples 1 to 12 and Comparative Examples 1 and 2 were evaluated by the following methods. The results are shown in Tables 1 and 2 below.

1. Determination of solid content (non-volatile matter)

Each resin composition prepared above was taken in a flat dish having an inner diameter of about 80 mm and the bottom was flatly kneaded so as to be well dried, then placed in a thermostat (105 ± 2 ° C), dried for 3 hours and then measured for solid content Respectively.

2. Molecular weight measurement

Molecular weight and molecular weight distribution were measured by GPC (Gel Permeation Chromatography, Waters R-410, USA). The detector was RI, and the columns were connected with four of Shodex KF-802, KF-803, KF-804 and KF-805. And THF was used as a solvent.

3. Viscosity measurement

The viscosity was measured by spindle No. 4, 30 RPM using a Brookfield viscometer LVF as a non-Newtonian rotational viscometer test method of ASTM D 2196 after maintaining the resin composition in a constant temperature water bath at 25 ° C for 30 minutes. The unit was cps (mPa.s ) Units were used.

4. Storage Stability after Moisture

The resin composition thus prepared was then dissolved in a transparent glass bottle and stored in a thermostatic chamber (25 ± 2 ° C.) for 20 days. The state of each resin composition was visually observed, and according to the degree of layer separation and degree of viscosity change, As a reference.

- No layer separation of the resin composition, little or no change in viscosity: Good (O)

- No layer separation of the resin composition and a lot of viscosity change: Normal (△)

- With layer separation: Bad (X)

Configuration Production Example 1 Production Example 2 Production Example 3 Production Example 4 Production Example 5 Production Example 6 Production Example 7 Production Example 8 Production Example 9 Propylene glycol monobutyl ether 10 10 10 10 10 - 10 10 10 Epoxy type reactive diluent monomer 10 10 10 15 20 20 10 10 10 Styrene 17.2 17.2 17.2 10.5 3.8 3.8 17.2 7.2 22.2 Methyl methacrylate 10 10 10 10 10 10 10 10 10 Isobornyl methacrylate 10 10 10 10 10 10 - 20 10 2-hydroxyethyl methacrylate 30 30 30 30 30 30 40 30 30 Polyethylene glycol acrylate 10 - - - - - - - - Polypropylene glycol acrylate - 10 - - - - - - - Methoxypolyethylene glycol methacrylate - - 10 10 10 10 10 10 5 Methacrylic acid 7.3 7.3 7.3 9 10.7 10.7 7.3 7.3 7.3 AIBN 5 5 5 5 5 5 5 5 5 Triethanolamine 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 Ion-exchange water 135 135 135 135 135 145 135 135 135 Sum 250 250 250 250 250 250 250 250 250 Non-volatile matter (%) 40.1 40.3 40.1 40.2 40.3 39.8 40.2 40.3 40.4 Molecular weight (Mw) 14000 14000 14200 14900 14300 14800 15100 14700 14700 Viscosity (cps) 5000 3400 2800 2600 2200 2500 4300 2700 2100 Storage stability △ △ ○ ○ ○ ○ ○ ○ △

Configuration Production Example 10 Production Example 11 Production Example 12 Comparative Example 1 Comparative Example 2 Propylene glycol monobutyl ether 10 10 10 20 10 Epoxy type reactive diluent monomer 10 10 10 - 10 Styrene 15.2 15.2 15.2 25.66 22.2 Methyl methacrylate 10 10 10 15 15 Isobornyl methacrylate 10 10 10 10 10 2-hydroxyethyl methacrylate 30 30 30 30 30 Methoxypolyethylene glycol methacrylate 10 10 10 10 - Methacrylic acid 7.3 7.3 7.3 3.84 7.3 Vinyltriethoxysilane 2 - - - - Glycidoxypropyltrimethoxysilane - 2 - - - Aminopropyltriethoxysilane - - 2 - - AIBN 5 5 5 5 5 Triethanolamine 5.5 5.5 5.5 5.5 5.5 Ion-exchange water 135 135 135 125 135 Sum 250 250 250 250 250 Non-volatile matter (%) 40.8 40.6 40.7 40.6 40.3 Molecular weight (Mw) 15200 15400 15100 15300 14100 Viscosity (cps) 3500 3400 3400 14300 11200 Storage stability ○ ○ ○ X X

As can be seen from Tables 1 and 2, in the case of the resin compositions (Production Examples 1 to 12) prepared by the present invention, the epoxy type reactive diluent monomer compound and the non-ionic acrylate were used, And the weight average molecular weight was high, but the viscosity was low and the storage stability was good. It was confirmed that the resin compositions prepared in Comparative Examples 1 and 2 had similar weight average molecular weights but higher viscosity and poor storage stability.

≪ Example 1 >

Titanium oxide (TiO2), calcium carbonate (CaCO3) and additives were mixed in the contents shown in the following Table 3 in 45.0 parts by weight of water-dispersible two-component type acrylic polyol resin A (solid content 40%, acid value 25 mgKOH / g, hydroxyl value 130 mgKOH / g) . A thickener and water were added to the dispersion thus prepared, followed by stirring and mixing to prepare a water dispersible acrylic paint composition. The following evaluation was made by using polyisocyanate (Baidu Dewar 3100, manufactured by Bayer AG) as a curing agent in an amount equivalent to 1 (resin composition): 1.5 (polyisocyanate). The results are shown in Table 3.

[Measurement method and evaluation result 2]

(Appearance of coating film)

The zinc phosphate treated steel sheet was coated with the resin composition so that the dry film thickness was 50 microns and cured at 80 DEG C for 30 minutes, and then the appearance was visually observed.

Good: Appearance good, Partial: Bad part, X: Cracked

(Water resistance)

The test piece used in the evaluation of the appearance of the coating film was immersed in warm water at 40 ° C for 24 hours to visually observe the appearance change.

?: No change,?: Some blisters exist, X: All blisters exist

(Solvent resistance)

The test specimens used in the evaluation of coating appearance were cured at room temperature for 24 hours, then xylene was dropped on the coating film and left for 30 seconds, and the appearance changes were visually observed.

?: No change,?: Partial dissolution and swelling, X: Dissolution or swelling

≪ Example 2 >

Except that the water-dispersible, two-part type acrylic polyol resin B (solid content 40%, acid value 25 mg KOH / g, hydroxyl value 130 mg KOH / g) and the blending components used in Example 1 were used in the formulation ratios shown in Table 3 To obtain an aqueous acrylic paint composition. Various tests were carried out in the same manner as in Example 1 using the obtained coating composition. The results are shown in Table 3.

≪ Example 3 >

Except that the water-dispersible two-component type acrylic polyol resin C (solid content 40%, acid value 25 mg KOH / g, hydroxyl value 130 mg KOH / g) and the blending components used in Example 1 were used in the formulation ratios shown in Table 3 To obtain an aqueous acrylic paint composition. Various tests were carried out in the same manner as in Example 1 using the obtained coating composition. The results are shown in Table 3.

<Example 4>

Except that the water-dispersible, two-part type acrylic polyol resin D (solid content 40%, acid value 25 mg KOH / g, hydroxyl value 130 mg KOH / g) and the blending components used in Example 1 were used in the formulation ratios shown in Table 3 To obtain an aqueous acrylic paint composition. Various tests were carried out in the same manner as in Example 1 using the obtained coating composition. The results are shown in Table 3.

&Lt; Example 5 >

Except that the water-dispersible, two-part type acrylic polyol resin E (solid content 40%, acid value 25 mgKOH / g, hydroxyl value 130 mgKOH / g) and the compounding ingredients used in Example 1 were used in the formulation ratios shown in Table 3 To obtain an aqueous acrylic paint composition. Various tests were carried out in the same manner as in Example 1 using the obtained coating composition. The results are shown in Table 3.

Example 1 Example 2 Example 3 Example 4 Example 5 The water-dispersible two-component type acrylic polyol resin A 45 Water-dispersible two-component type acrylic polyol resin B 45 Water-dispersible two-component acrylic polyol resin C 45 Water-dispersible two-component type acrylic polyol resin D 45 Water-dispersible two-component acrylic polyol resin E 45 Dispersant One Thickener 2 Defoamer 0.2 TiO2 29 CaCO3 10 H2O 12.8 Sum 100 100 100 100 100 Exterior ○ ○ ○ ○ ○ Water resistance △ △ △ △ △ Solvent resistance △ △ ○ ○ ○

&Lt; Example 6 >

Except that the water-dispersible two-component type acrylic polyol resin F (solid content 40%, acid value 25 mg KOH / g, hydroxyl value 130 mg KOH / g) and the compounding ingredients used in Example 1 were used in the formulation ratios shown in Table 4 To obtain an aqueous acrylic paint composition. Various tests were carried out in the same manner as in Example 1 using the obtained coating composition. The results are shown in Table 4.

&Lt; Example 7 >

Except that the water-dispersible two-component type acrylic polyol resin G (solid content 40%, acid value 25 mg KOH / g, hydroxyl value 170 mg KOH / g) and the blending components used in Example 1 were used in the formulation ratios shown in Table 4 To obtain an aqueous acrylic paint composition. Various tests were carried out in the same manner as in Example 1 using the obtained coating composition. The results are shown in Table 4.

&Lt; Example 8 >

Except that the water-dispersible, two-part type acrylic polyol resin H (solid content 40%, acid value 25 mg KOH / g, hydroxyl value 130 mg KOH / g) and the compounding ingredients used in Example 1 were used in the formulation ratios shown in Table 4 To obtain an aqueous acrylic paint composition. Various tests were carried out in the same manner as in Example 1 using the obtained coating composition. The results are shown in Table 4.

&Lt; Example 9 >

Except that the water-dispersible two-component type acrylic polyol resin I (solid content 40%, acid value 25 mg KOH / g, hydroxyl value 130 mg KOH / g) and the compounding ingredients used in Example 1 were used in the formulation ratios shown in Table 4 To obtain an aqueous acrylic paint composition. Various tests were carried out in the same manner as in Example 1 using the obtained coating composition. The results are shown in Table 4.

&Lt; Example 10 >

Except that the water-dispersible two-component type acrylic polyol resin J (solid content 40%, acid value 25 mg KOH / g, hydroxyl value 130 mg KOH / g) and the compounding ingredients used in Example 1 were used in the formulation ratios shown in Table 4 To obtain an aqueous acrylic paint composition. Various tests were carried out in the same manner as in Example 1 using the obtained coating composition. The results are shown in Table 4.

Example 6 Example 7 Example 8 Example 9 Example 10 Water-dispersible two-component type acrylic polyol resin F 45 Water-dispersible two-component acrylic polyol resin G 45 Water-dispersible two-component type acrylic polyol resin H 45 Water-dispersible two-component acrylic polyol resin I 45 Water-dispersible two-component acrylic polyol resin J 45 Dispersant One Thickener 2 Defoamer 0.2 TiO2 29 CaCO3 10 H2O 12.8 Sum 100 100 100 100 100 Coat appearance X ○ ○ ○ ○ Water resistance △ ○ △ △ ○ Solvent resistance ○ ○ ○ ○ ○

&Lt; Example 11 >

Except that the water-dispersible, two-part type acrylic polyol resin K (solid content 40%, acid value 25 mg KOH / g, hydroxyl value 130 mg KOH / g) and the blending components used in Example 1 were used in the formulation ratios shown in Table 5 To obtain an aqueous acrylic paint composition. Various tests were carried out in the same manner as in Example 1 using the obtained coating composition. The results are shown in Table 5.

&Lt; Example 12 >

Except that the water-dispersible two-component type acrylic polyol resin L (solid content 40%, acid value 25 mg KOH / g, hydroxyl value 130 mg KOH / g) and the compounding ingredients used in Example 1 were used in the formulation ratios shown in Table 5 To obtain an aqueous acrylic paint composition. Various tests were carried out in the same manner as in Example 1 using the obtained coating composition. The results are shown in Table 5.

&Lt; Comparative Example 1 &

Except that the water-dispersible two-component type acrylic polyol resin M (solid content 40%, acid value 25 mg KOH / g, hydroxyl value 130 mg KOH / g) and the blending components used in Example 1 were used in the blending ratios shown in Table 5 To obtain an aqueous acrylic paint composition. Various tests were carried out in the same manner as in Example 1 using the obtained coating composition. The results are shown in Table 5.

&Lt; Comparative Example 2 &

Except that the water-dispersible, two-part type acrylic polyol resin N (solid content 40%, acid value 25 mg KOH / g, hydroxyl value 130 mg KOH / g) and the compounding ingredients used in Example 1 were used in the formulation ratios shown in Table 5 To obtain an aqueous acrylic paint composition. Various tests were carried out in the same manner as in Example 1 using the obtained coating composition. The results are shown in Table 5.

Example 11 Example 12 Comparative Example 1 Comparative Example 2 Water-dispersible two-component acrylic polyol resin K 45 Water-dispersible two-component acrylic polyol resin L 45 Water-dispersible two-component acrylic polyol resin M 45 Water-dispersible two-component acrylic polyol resin N 45 Dispersant One Thickener 2 Defoamer 0.2 TiO2 29 CaCO3 10 H2O 12.8 Sum 100 100 100 100 Coat appearance ○ ○ ○ X Water resistance ○ ○ X X Solvent resistance ○ ○ X X

As can be seen from Tables 3 to 5, in the case of the coating compositions (Examples 1 to 12) prepared using the resin composition according to the present invention, due to the influence of the epoxy reactive diluent monomer compound and nonionic acrylate, It was found that the coating film had good appearance, water resistance, and solvent resistance due to its stability. In particular, it was confirmed that Examples 10 to 12, which are silane crosslinking type, have improved water resistance and solvent resistance.

The coating compositions prepared in Comparative Examples 1 and 2 had a high viscosity and a poor storage stability, so that the viscosity of the coating composition was still high, resulting in cracks on the outer appearance of the coating film, and thus, the coating composition lacked water resistance and solvent resistance.

INDUSTRIAL APPLICABILITY As described above, the water-dispersible, two-pack type acrylic polyol resin composition according to the present invention is excellent in gloss and appearance, exhibits excellent physical properties such as water resistance, solvent resistance, weather resistance and adhesion, And the content of organic solvents that can cope with demands for environmental regulation is low.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the scope of the present invention is not limited to the disclosed exemplary embodiments. Various modifications and variations may be made without departing from the scope of the appended claims.

Claims (6)

1 to 30 parts by weight of an epoxy-based reactive diluent monomer;
1 to 15 parts by weight of a carboxyl group-containing monomer;
1 to 50 parts by weight of a hydroxyl group-containing monomer;
1 to 20 parts by weight of a nonionic type acrylate monomer;
1 to 20 parts by weight of an unsaturated monomer;
0.1 to 5 parts by weight of reactive silane; And 1 to 10 parts by weight of a neutralized basic amine capable of reacting with an isocyanate compound,
The non-ionic acrylate is a non-
(Meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, polyethylene glycol polytetramethylene glycol mono (meth) acrylate, polypropylene glycol polytetramethylene glycol Wherein the water-dispersible acrylic polyol resin is at least one selected from the group consisting of mono (meth) acrylate, methoxypolyethylene glycol (meth) acrylate. The method according to claim 1,
Wherein the epoxy-based reactive diluent monomer has the following chemical formula.

(Wherein R1 and R2 are alkyl groups having 1 to 6 carbon atoms)
The method according to claim 1,
The carboxyl group-
(Meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, and mixtures thereof.
The method according to claim 1,
The hydroxyl group-
(Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate. The water-dispersible two-component acrylic polyol resin composition according to claim 1,
delete The method according to claim 1,
The reactive silane,
Glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxyethoxysilane, vinylmethyldimethoxysilane, vinyltrimethoxysilane, Aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, aminneohexyltrimethoxysilane, aminonohexylmethyldimethoxysilane, aminobutyltrimethoxysilane, Silane, and aminoethylaminopropylmethyldimethoxysilane. 2. The water-dispersible acrylic polyol resin composition according to claim 1,