JP5327496B2 - Water-based paint composition for steel sheet - Google Patents

Description

  The present invention relates to an acrylic-polyurethane resin-based aqueous coating composition for steel plates.

Steel plates (stainless steel plates, etc.) and treated steel plates (galvanized steel plates, etc.) are widely used in applications such as building materials, automobile materials, household appliances, and household goods. These are protected from rust and maintain their aesthetics. For the purpose, a steel sheet coating composition is generally used. As such a steel sheet coating composition, an organic solvent-based coating composition has been often used. However, in recent years, an aqueous coating composition using water or alcohol as a solvent is considered in consideration of the load on the environment and the human body. It is becoming mainstream.

The water-based paint composition requires basic performance such as scratch resistance and stain resistance of the coating film, adhesion to the base material, etc. In addition, the product is exposed to wind and rain, mortar and concrete In consideration of contact or washing with an alkaline detergent, acid resistance and alkali resistance of the coating film are particularly required. In addition, when a water-based paint composition is pre-coated on a steel sheet for the purpose of rationalizing the painting line, the followability of the coating film (hereinafter referred to as workability) is required particularly when the coated steel sheet is formed. The

  In order to satisfy such requirements, in this field, for example, (i) a water-based coating composition obtained by mixing a polyester-based water-based polyurethane resin from which a flexible coating film is obtained and a water-based acrylic polymer from which a hard coating film is obtained, (Ii) A water-based coating composition comprising an acrylic compound grafted on such an aqueous polyurethane resin may be used.

However, such a water-based coating composition usually has a significant change in appearance and viscosity or may precipitate insoluble matter when left for a long period of time. Moreover, the coating film by these may melt | dissolve and will peel from a base material, when it puts on an acidic or alkaline environment. Furthermore, when the coated steel sheet coated with these is subjected to forming, the coating film may be cracked or peeled off.

An object of the present invention is to provide a coating composition for steel sheet that has good storage stability and that is particularly excellent in acid resistance, alkali resistance, and workability of a coating film.

The present inventor has found that the above-mentioned problems can be solved by a water-based coating composition for steel sheet having the following configuration. That is, the present invention is:

Polyols (a1) and polyisocyanates (a2) comprising 86 to 96% by weight of polycarbonate diol and 14 to 4% by weight of an anionic functional group-containing polyol, and one (meth) acryloyl group and one hydroxyl group in the molecule. The radically polymerizable monomer (a3) having a ratio (NCO / OH) of the equivalent value of the isocyanate group of the component (a2) to the equivalent value of the hydroxyl group of the component (a1) and the component (a3) is 1.05 / 1 to In the presence of water and polyurethane resin (A) obtained by further reacting the prepolymer composition (A ′) obtained by reacting in the range of 4/1 with a chain extender (a4) comprising only low molecular weight polyamines. in the general formula ^{_{(1): CH 2 = CR}} 1 COOR 2 ( wherein ^{R 1} represents a hydrogen atom or a methyl group also ^{R 2,} represents an alkyl group having 1 to 18 carbon atoms. Characterized in represented by (meth) causing polymerization reaction of acrylic acid alkyl esters (b1) consisting of only polymerization component (B), acrylic - steel for aqueous coating composition using an aqueous dispersion of polyurethane resin The manufacturing method .

The coating composition for steel sheets according to the present invention has good storage stability, such as no change in appearance and viscosity even when stored for a long period of time. In addition, the coating film by the steel sheet coating composition has excellent adhesion to the steel sheet, and the coating film does not whiten, swell, dissolve or peel even when placed in an environment such as wet, alkaline, acidic, etc. Excellent water resistance, especially alkali resistance and acid resistance. Furthermore, this coating film is excellent in workability, such as being free from cracking or peeling even when subjected to molding. Therefore, the coated steel plate using the steel sheet coating composition according to the present invention is useful in applications such as building materials, automobile materials, home appliances, and household goods.

The aqueous coating composition for steel sheet according to the present invention is an acrylic-polyurethane resin aqueous dispersion obtained by polymerizing a specific polymerization component (B) in the presence of the specific polyurethane resin (A) and water. Is used. The “water dispersion” means either or both of the acrylic-polyurethane resin in a water-soluble or water-dispersed state.

The polyurethane resin (A) is a polyol composed of polycarbonate diol 86 to 96% by weight (preferably 88 to 95% by weight) and anionic functional group-containing polyol 14 to 4% by weight (preferably 12 to 5% by weight). (A1) (hereinafter referred to as component (a1)), polyisocyanate (a2) (hereinafter referred to as component (a2)) and a radical polymerizable monomer (a3) having one (meth) acryloyl group and one hydroxyl group in the molecule. (Hereinafter referred to as component (a3)), the ratio (NCO / OH) of the equivalent value of the isocyanate group of component (a2) to the equivalent value of the hydroxyl group of component (a1) and component (a3) is 1.05 / 1 to 4/1 and comprising prepolymer composition obtained by reacting in the range (a ') (hereinafter, (a') referred to as the component) more consisting of only the low molecular polyamines in the chain extender (a ) (Hereinafter, (a4) is obtained by reacting a) of component.

In addition, this (a1) component consists only of a polycarbonate diol component and an anionic functional group containing polyol component, and the total amount of both becomes 100 weight%. When the used weight% of each component deviates from the range of the used weight%, the aqueous dispersion cannot be stably produced, and the alkali resistance and workability of the coating film are poor.

  As the polycarbonate diol in the component (a1), various known ones can be used without particular limitation. Specifically, for example, a demethanol condensation reaction product of polyhydric alcohol and dimethyl carbonate, a dephenol condensation reaction product of polyhydric alcohol and diphenyl carbonate, a deethylene glycol condensation reaction product of polyhydric alcohol and ethylene carbonate, etc. These can be used singly or in combination of two or more.

In addition, as this polyhydric alcohol, various well-known things can be especially used without a restriction | limiting. Specifically, for example, low molecular weight glycols [1,6-hexanediol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1 , 5-pentanediol, octanediol, 1,4-butynediol, dipropylene glycol, etc.], alicyclic glycols [1,4-cyclohexanediglycol, 1,4-cyclohexanedimethanol, etc.] These can be used individually by 1 type or in combination of 2 or more types.

In addition, the number average molecular weight of the polycarbonate diol (referred to polystyrene conversion value by gel permeation chromatography; hereinafter the same) is not particularly limited, but considering the strength of the coating film, adhesion to the substrate, etc. Usually, it is preferably about 500 to 3000.

In addition, as the anionic functional group-containing polyol in the component (a1), various known ones can be used without particular limitation. Specifically, for example, carboxyl group-containing polyols [2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, etc.] and neutralized salts thereof, sulfone group-containing dicarboxylic acids [5-sulfoisophthalic acid, 4 -Sulfoisophthalic acid, 4-sulfophthalic acid, sulfoterephthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5- (4-sulfophenoxy) isophthalic acid and the like] and neutralized salts thereof The polyol etc. which are made to obtain are mentioned, These can be used individually by 1 type or in combination of 2 or more type. Among these, since the solubility in a reaction system is high, the said carboxyl group containing polyol is preferable, and since especially acquisition is easy, the said 2, 2- dimethylol propionic acid and / or 2, 2- dimethylol butane are preferable. Acid is preferred.

In addition, as a basic compound for forming each said neutralization salt, various well-known things can be especially used without a restriction | limiting. Specifically, for example, alkali metal hydroxides (potassium hydroxide, sodium hydroxide, etc.), tertiary amines (trimethylamine, triethylamine, triisopropylamine, tributylamine etc.), alkanolamines (triethanolamine, triisopropanolamine) N-alkyldiethanolamine, N, N′-dialkylmonoethanolamine, N-alkyldiisopropanolamine, N, N′-dialkylmonoisopropanolamine, etc.], ammonia, etc., and these may be used alone or in combination. Two or more types can be used in combination. Among these, the tertiary amine and ammonia are preferable because the water resistance of the coating film is improved.

  As said (a2) component, various well-known things can be used without limitation. Specifically, for example, aromatic diisocyanate [1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate Tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, etc.], aliphatic diisocyanates [butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl] Hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, etc.], alicyclic diisocyanate [sic] Hexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, dimer diisocyanate, etc.], triisocyanate compounds [tri Phenylmethane triisocyanate, polymethylene polyphenylisocyanate, etc.], and the like. These can be used alone or in combination of two or more.

As the component (a3) , specifically, for example, at least one selected from the group consisting of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate is preferably used. obtain. In addition, when this (a3) component is not used, the storage stability of the acrylic-polyurethane resin aqueous dispersion becomes poor, and the acid resistance, alkali resistance, and workability of the coating film are insufficient.

(A4) The chain extender is a component, a low molecular polyamines [ethylenediamine, propylenediamine, hexamethylenediamine, isophorone diamine, dicyclohexylmethane-4,4'-diamine, 2-hydroxyethyl ethylenediamine, 2-hydroxyethyl propylene diamine, di-2-hydroxyethyl ethylenediamine, di-2-hydroxyethyl-propylenediamine, 2-hydroxypropyl ethylenediamine, di-2-hydroxypropyl ethylene diamine, triethylene tetramine, with diethylenetriamine, etc.], they alone , Or a combination of two or more.

Moreover, a chain length terminator can be used with (a4) component . Specifically, for example, monoalkylamines [monomethylamine, monoethylamine, mono-n-propylamine, monoisopropylamine, mono-n-butylamine, monoisobutylamine, etc.], dialkylamines [dimethylamine, diethylamine, Di-n-propylamine, di-n-butylamine, etc.], hydroxyl group-containing amines [monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tri (hydroxymethyl) aminomethane, 2-amino- 2-ethyl-1,3-propanediol etc.] and the like, and these can be used alone or in combination of two or more.

In the present invention, water [city water, distilled water, deionized water, etc.] is used as a solvent. In addition, the water may contain an alcohol solvent [methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, sec-amyl as necessary. Alcohol, diacetone alcohol, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, etc.) can be used in combination. In addition, although the usage-amount of water (and alcohol solvent as needed) is not restrict | limited, Usually, what is necessary is just to set it as the range from which the solid content concentration of a reaction system will be about 10 to 50 weight% normally. Moreover, when using together an alcohol solvent, what is necessary is just to set it as the range of about 0-30 weight% normally with respect to water. In the aqueous solvent, the basic compound may be appropriately present for the purpose of neutralizing the polyurethane resin (A).

The polymerization component (B) is represented by the general formula (1): CH ₂ = CR ¹ COOR ² (wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 18 carbon atoms). It contains (meth) acrylic acid alkyl esters (b1) (hereinafter referred to as component (b1)). R ² may have a branched structure. Moreover, content of this (b1) component is not specifically limited in a polymerization component (B), However, Usually, it is about 50-100 mol%. Further, the number of carbon atoms of magnitude R ^2, and acid-alkali resistance of the coating film, it is possible adjust the processability. However, the above-mentioned acrylic compound (a3) component having an active hydrogen-containing group is excluded from the component (B).

  Specific examples of the component (b1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) acrylic. Hexyl acid, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate and (meth) ) Stearyl acrylate and the like can be mentioned, and these can be used singly or in combination of two or more.

  In addition, if it is less than 50 mol% in the said polymerization component polymerization component (B), radically polymerizable monomers other than the said (b1) component can be used. Specifically, for example, alicyclic (meth) acrylates [(meth) acrylate 2-cyclohexyl, (meth) acrylate cyclopentyl, (meth) acrylate isobornyl, etc.], aromatic group-containing (meth) acrylates [Phenoxyethyl (meth) acrylate, 2-phenylethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, styrene, α-methylstyrene, etc.], halogen element-containing (meth) acrylates [Trifluoroethyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, 2-chloroethyl (meth) acrylate, etc.] and the like are included, and these are used alone or in combination of two or more. be able to.

Although the manufacturing method in particular of the said acrylic polyurethane resin dispersion is not restrict | limited, For example, the following methods can be illustrated.

(A) The component (a1), the component (a2) and the component (a3) are reacted to form a prepolymer composition (A ′), and then the prepolymer composition (A ′) and the component (a4) are combined. A method of reacting in the presence of water to produce a polyurethane resin (A) and then adding the polymerization component (B) in the same system to cause a polymerization reaction

(A) The (a1) component, the (a2) component, and the (a3) component are reacted to form a prepolymer composition (A ′) (hereinafter referred to as (A ′) component), and then the (A ′) component and (A4) A method of reacting the component in the presence of the water and the polymerization component (B) to produce a polyurethane resin (A), and then polymerizing the polymerization component (B) in the same system

(C) Prepolymer composition (A ′) (hereinafter referred to as (A ′) component) by reacting component (a1), component (a2) and component (a3) in the presence of the polymerization component (B). And then reacting the component (A ′) and the component (a4) to produce the polyurethane resin (A), and then polymerizing the polymerization component (B) in the same system.

In any of the production methods, the reaction temperature for producing the prepolymer (A ′) is usually about 50 to 150 ° C. Moreover, although the usage-amount of (a1) component, (a2) component, and (a3) component is not specifically limited, Specifically, the equivalent value of the isocyanate group of (a2) component, (a1) component, and (a3) The ratio (NCO / X) to the equivalent value of the active hydrogen-containing group of the component is usually in the range of about 1/2 to 4/1. Moreover, when using the said (a4) component, it is good to make the said ratio (NCO / OH) into the range used as about 1.05 / 1-4/1 normally. In the present invention, the “equivalent value of isocyanate group” means a value obtained by dividing the number of grams (g) of 1 mol of the component (a1) by the number of isocyanate groups of the (a1) component. In the present invention, the “equivalent value of the active hydrogen-containing group” means that in the component (a1) or the component (a3), the gram number (g) of 1 mol of each component is divided by the number of active hydrogen-containing groups of the component. It refers to the value obtained.

The component (a3) itself is preferably used in the range where the double bond equivalent value in the prepolymer (A ′) is usually about 2000 to 55000. Here, in the present invention, the “double bond equivalent value” means a prepolymer (A) per carbon-carbon double bond (derived from the component (a3)) contained in the prepolymer (A ′). ') Means the number of grams (in terms of solid content). When the double bond equivalent value is within the above numerical range, almost no insoluble matter is generated during the subsequent polymerization reaction, and the number average molecular weight of the polyurethane resin (A) is easily within the range described later.

Moreover , the temperature at the time of making prepolymer (A ') and (a4) component react is about room temperature-about 90 degreeC normally. The amount of the component (a4) itself used is the ratio (NCO ′ / X ′) of the equivalent value of the isocyanate group of the prepolymer (A ′) to the equivalent value of the active hydrogen-containing group of the component (a4). , X ′ means a hydroxyl group and / or an amino group) is preferably in the range of usually about 1/1 to 1/2.

Moreover, in any manufacturing method, the temperature at the time of the said polymerization reaction is about 60-100 degreeC normally. Moreover, it is preferable from the viewpoint of the storage stability of the acrylic-polyurethane resin aqueous dispersion that the amount of the polymerization component (B) is usually in the range of 3 to 50% by weight with respect to the polyurethane resin (A).

In the polymerization reaction, various known polymerization initiators can be used. Specifically, for example, azo compounds (azobisisobutyronitrile, azobisisobutylvaleronitrile, etc.), organic peroxides [benzoyl peroxide, isobutyryl peroxide, octanoyl peroxide, cumyl peroxyoctate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyacetate, lauryl peroxide, di-t-butyl peroxide, di-2-ethylhexyl peroxydine carbonate, etc.], inorganic peroxide compounds [persulfuric acid Potassium, ammonium persulfate, hydrogen peroxide, etc.) and the like. These may be used alone or in combination of two or more. The usage-amount of this polymerization initiator is about 0.1-5 weight part normally with respect to a polymerization component (B).

  The aqueous dispersion of the acrylic-polyurethane resin thus obtained has a solid content concentration of usually about 20 to 50% by weight and a viscosity of about 10 to 10000 mPa · s / 25 ° C. from a practical viewpoint. The pH is preferably about 6 to 10. In addition, the number average molecular weight of the acrylic-polyurethane resin is usually preferably about 1,000 to 1,000,000 from the viewpoint of storage stability.

The aqueous dispersion of the acrylic-polyurethane resin can be used as it is as a water-based coating composition for steel sheets, but various known crosslinking agents (melamine, isocyanate, phenol, etc.), colorants, A blocking agent, a silicon compound, a fluorine compound, an antifoaming agent, or the like can also be used in combination.

Examples of the steel sheet to be coated with the water-based coating composition of the present invention include ordinary steel sheets, treated steel sheets such as aluminum plated steel sheets, stainless steel sheets, zinc phosphate treated steel sheets, galvanized steel sheets, and zinc alloy plated steel sheets. Note that zinc alloy plating includes Zn—Al, Zn—Mg, Zn—Ni, and Zn—Al—Mg. Moreover, in order to improve the adhesiveness with the water-based paint composition, the chemical conversion treatment coating layer (chromate-based, phosphate chromate-based, non-chromium-based coating layer), An undercoat layer (a coating layer such as a polyester resin-based paint, an epoxy resin-based paint, or an epoxy-modified polyester resin-based paint) may be provided in advance.

The coating means is not particularly limited, and examples thereof include a natural roll coat method, a reverse roll coat method, and a curtain flow coat method. The coating composition for steel sheet may be applied when the surface-treated steel sheet is not yet formed (pre-coating method) or after the surface-treated steel sheet is formed (post-coating method). ).

  Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples.

Example 1
To a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube (product name “Kuraray polyol C2090”; 1,6-hexanediol / 3-methyl-1,5-pentanediol = 10 / 90 (molar ratio), number average molecular weight 2000; manufactured by Kuraray Co., Ltd.) 715 parts by weight, isophorone diisocyanate 333 parts by weight, 2,2-dimethylolpropionic acid 53 parts by weight, 2-hydroxyethyl acrylate 23 parts by weight And a urethanization reaction was performed at 70 ° C. for 6 hours to obtain a prepolymer having a free isocyanate group content of 5.0% by weight. Next, 1000 parts of the prepolymer was gradually added dropwise to a stirring chain extender aqueous solution (36 parts by weight of triethylamine, 161 parts by weight of isopropyl alcohol, 96 parts by weight of isophoronediamine, 2593 parts by weight of water), and the whole reaction system Were mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to complete the chain extension reaction. Next, after adding 100 parts by weight of methyl methacrylate, 2.7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours. A polymerization reaction was performed. Thus, an aqueous resin dispersion having a solid content of 30% by weight and a viscosity of 20 mPa · s / 25 ° C. was obtained. The resin water dispersion is used as an aqueous coating composition for steel plates.

Example 2
In a four-necked flask similar to Example 1, 650 parts by weight of the above-mentioned “Kuraray polyol C2090”, 48 parts by weight of 2,2-dimethylolpropionic acid, 303 parts by weight of isophorone diisocyanate, 2-hydroxyethyl acrylate 21 parts by weight were charged and a urethanization reaction was performed at 70 ° C. for 6 hours. Subsequently, 100 parts by weight of stearyl methacrylate was added and mixed to obtain a prepolymer composition having a free isocyanate group content of 4.5% by weight. Next, 1000 parts of the composition was gradually added dropwise to a stirring chain extender aqueous solution (32 parts by weight of triethylamine, 144 parts by weight of isopropyl alcohol, 85 parts by weight of isophoronediamine, 2363 parts by weight of water), and the whole reaction system Were mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to complete the chain extension reaction. Subsequently, 2.6 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to carry out a polymerization reaction. Thus, an aqueous resin dispersion having a solid content of 30% by weight and a viscosity of 25 mPa · s / 25 ° C. was obtained. The resin water dispersion is used as an aqueous coating composition for steel plates.

Example 3
In the same four-necked flask as in Example 1, 650 parts by weight of the above-mentioned “Kuraray polyol C2090”, 48 parts by weight of 2,2-dimethylolpropionic acid, 303 parts by weight of isophorone diisocyanate, 21 parts by weight of 2-hydroxyethyl acrylate And urethanization reaction was carried out at 70 ° C. for 6 hours. Subsequently, 200 parts by weight of lauryl methacrylate was added and mixed to obtain a prepolymer composition having a free isocyanate group content of 4.1% by weight. Next, 1090 parts of the prepolymer composition is gradually added dropwise to a stirring chain extender aqueous solution (32 parts by weight of triethylamine, 144 parts by weight of isopropyl alcohol, 85 parts by weight of isophorone diamine, 2565 parts by weight of water) to react. The entire system was mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to complete the chain extension reaction. Subsequently, 2.6 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to carry out a polymerization reaction. Thus, an aqueous resin dispersion having a solid content of 30% by weight and a viscosity of 30 mPa · s / 25 ° C. was obtained. The resin water dispersion is used as an aqueous coating composition for steel plates.

Example 4
To a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, polycarbonate diol (product name “Nipporan 980R”; poly-1,6-hexene carbonate diol, number average molecular weight 2000; Nippon Polyurethane Industry) 650 parts by weight, 2,2-dimethylolbutanoic acid 53 parts by weight, isophorone diisocyanate 303 parts by weight, 2-hydroxyethyl acrylate 21 parts by weight, and subjected to urethanization reaction at 70 ° C. for 6 hours. It was. Subsequently, 100 parts by weight of stearyl methacrylate was added and mixed to obtain a prepolymer composition having a free isocyanate group content of 4.5% by weight. Next, 1000 parts of the composition was gradually added dropwise to a stirring chain extender aqueous solution (32 parts by weight of triethylamine, 144 parts by weight of isopropyl alcohol, 85 parts by weight of isophoronediamine, 2363 parts by weight of water), and the whole reaction system Were mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to complete the chain extension reaction. Subsequently, 2.6 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to carry out a polymerization reaction. Thus, an aqueous resin dispersion having a solid content of 30% by weight and a viscosity of 25 mPa · s / 25 ° C. was obtained. The resin water dispersion is used as an aqueous coating composition for steel plates.

Comparative Example 1
In the same four-necked flask as in Example 1, the above-mentioned “Kuraray polyol C2090” was 439 parts by weight, 107 parts by weight of 2,2-dimethylolpropionic acid, 454 parts by weight of isophorone diisocyanate, and 20 parts by weight of 2-hydroxyethyl acrylate. And urethanization reaction was carried out at 70 ° C. for 6 hours. Subsequently, 100 parts by weight of lauryl methacrylate was added and mixed to obtain a prepolymer composition having a free isocyanate group content of 7.8% by weight. Next, 1000 parts of the composition was gradually added dropwise to a stirring chain extender aqueous solution (72 parts by weight of triethylamine, 144 parts by weight of isopropyl alcohol, 133 parts by weight of isophoronediamine, 2428 parts by weight of water), and the whole reaction system Were mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to complete the chain extension reaction. Subsequently, 2.7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to carry out a polymerization reaction. Thus, an aqueous resin dispersion having a solid content of 30% by weight and a viscosity of 40 mPa · s / 25 ° C. was obtained. The resin aqueous dispersion is used as a water-based coating composition for steel plate for comparison.

Comparative Example 2
In the same four-necked flask as in Example 1, 776 parts by weight of the “Kuraray polyol C2090”, 12 parts by weight of 2,2-dimethylolpropionic acid, 212 parts by weight of isophorone diisocyanate, and 20 parts by weight of 2-hydroxyethyl acrylate And urethanization reaction was carried out at 70 ° C. for 6 hours. Subsequently, 100 parts by weight of lauryl methacrylate was added and mixed to obtain a prepolymer composition having a free isocyanate group content of 2.9% by weight. Next, 1000 parts of the composition was gradually added dropwise to a stirring chain extender aqueous solution (8 parts by weight of triethylamine, 144 parts by weight of isopropyl alcohol, 56 parts by weight of isophoronediamine, 2312 parts by weight of water), and the whole reaction system Were mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to complete the chain extension reaction. Next, 2.7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to conduct a polymerization reaction. As a result, a stable aqueous dispersion could not be obtained.

Comparative Example 3
In the same four-necked flask as in Example 1, 650 parts by weight of the above-mentioned “Kuraray polyol C2090”, 48 parts by weight of 2,2-dimethylolpropionic acid and 303 parts by weight of isophorone diisocyanate were charged, and urethanized at 70 ° C. for 6 hours. Reaction was performed. Subsequently, 100 parts by weight of methyl methacrylate was added and mixed to obtain a prepolymer composition having a free isocyanate group content of 5.2% by weight. Next, 1000 parts of the composition was gradually added dropwise to a stirring chain extender aqueous solution (32 parts by weight of triethylamine, 144 parts by weight of isopropyl alcohol, 105 parts by weight of isophoronediamine, 2402 parts by weight of water), and the whole reaction system Were mixed. Thereafter, the reaction system was stirred and held at 60 ° C. for 2 hours to complete the chain extension reaction. Subsequently, 2.6 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and the reaction system was stirred and held at 70 ° C. for 3 hours to carry out a polymerization reaction. The resin water dispersion obtained in this way, having a solid content of 30% by weight and a viscosity of 10 mPa · s / 25 ° C., is used as a comparative aqueous coating composition for steel sheets.

[Evaluation of storage stability]
Each resin aqueous dispersion obtained in the above Examples and Comparative Examples was allowed to stand at 40 ° C. for 30 days, and then the change in appearance was evaluated according to the following criteria. The results are shown in Table 1. In Table 1, “-” means that evaluation was not performed.
○: Almost no change in appearance or viscosity.
X: Precipitation of insoluble matter is observed.

[Preparation of paint specimens]
Each resin aqueous dispersion obtained in the above Examples and Comparative Examples was applied to a galvanized steel sheet (thickness 0.8 mm, width 70 mm, length 150 mm) with a bar coater so that the dry film thickness was 2 μm. And dried at 80 ° C. for 10 minutes to obtain a test piece.

[Performance evaluation of coating film]
(Acid resistance)
The test piece was immersed in 0.1N hydrochloric acid for 3 minutes, and then the state of the coating film was visually observed and evaluated based on the following criteria. The results are shown in Table 1.
○: No significant change was observed in the coating film.
Δ: Changes such as whitening and swelling were observed in the coating film.
X: The coating film was dissolved or peeled off.

(Alkali resistance)
After immersing the test piece in a 1% NaOH aqueous solution for 3 minutes, the state of the coating film was visually observed and evaluated based on the following criteria. The results are shown in Table 1.
○: No significant change was observed in the coating film.
Δ: Changes such as whitening and swelling were observed in the coating film.
X: The coating film was dissolved or peeled off.

(Processability)
The central part of each test piece was extruded 8 mm with an Erichsen tester, the state of the coating film was visually observed, and evaluated based on the following criteria. The results are shown in Table 1.
○: No cracking or peeling was observed in the coating film.
Δ: Slight cracking or peeling was observed in the coating film.
X: A big crack and peeling were recognized by the coating film.

Claims (3)

Polyols (a1) and polyisocyanates (a2) comprising 86 to 96% by weight of polycarbonate diol and 14 to 4% by weight of an anionic functional group-containing polyol, and one (meth) acryloyl group and one hydroxyl group in the molecule. The radically polymerizable monomer (a3) having a ratio (NCO / OH) of the equivalent value of the isocyanate group of the component (a2) to the equivalent value of the hydroxyl group of the component (a1) and the component (a3) is 1.05 / 1 to In the presence of water and polyurethane resin (A) obtained by further reacting the prepolymer composition (A ′) obtained by reacting in the range of 4/1 with a chain extender (a4) comprising only low molecular weight polyamines. so,
General formula (1): CH ₂ = CR ¹ COOR ² (wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 18 carbon atoms) (meth) A polymerization component (B) consisting only of alkyl acrylates (b1) is subjected to a polymerization reaction ,
Acrylic - method of manufacturing an aqueous coating composition for steel sheets using an aqueous dispersion of a polyurethane resin. The manufacturing method of Claim 1 whose double bond equivalent value of a prepolymer composition (A ') is 2000-55000. The radical polymerizable monomer (a3) having one (meth) acryloyl group and one hydroxyl group in the molecule is composed of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate. The production method according to claim 1, wherein the production method is at least one selected from the group.