JP3419043B2 - Aqueous curable resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel and useful aqueous curable resin composition. More specifically, the present invention is based on a polymer having a specific group called an N-acyl cyclic urea group, and in particular, forms a cured product excellent in chemical resistance, water resistance, corrosion resistance and appearance, The present invention relates to a highly curable aqueous curable resin composition.

The curable resin composition of the present invention is used in various fields for paints, adhesives, and sealing agents.

[0003]

2. Description of the Related Art In recent years, aqueous curable resin compositions have been actively developed mainly in the field of paints for the purpose of resource saving, energy saving and environmental measures. As one of them, for example, a vinyl-based polymer water-dispersed product or water-solubilized product having both a so-called active hydrogen-containing functional group such as a hydroxyl group and an amide group and an acid group or a neutralized acid group is cured. As the agent, a composition in which an amino resin or a blocked isocyanate compound is mixed has been studied and has been put to practical use.

However, the cured product obtained from such a compound, in the case where the amino resin is used as the curing agent, is
It is inferior in water resistance, chemical resistance, corrosion resistance, etc., and when it is applied thickly, it has the drawbacks that it is easy to generate pinholes and inferior in appearance. However, since the blocking agent is volatilized during heating, when thickly coated, there is a problem that pinholes are likely to occur and the appearance is inferior, and moreover, "burning" occurs in the baking furnace. .

[0005]

SUMMARY OF THE INVENTION However, in view of the present circumstances, the inventors of the present invention, in view of the various drawbacks and difficulties in the prior art as described above,
Research has been earnestly started in search of a curable resin composition having extremely high practicality that can form a cured product having excellent chemical resistance, water resistance, corrosion resistance and appearance.

[0006] Therefore, the problem to be solved by the present invention is based on one and in particular, a highly practical water-based curability of forming a cured product excellent in chemical resistance, water resistance, corrosion resistance and appearance, among others. There is an attempt to provide a resin composition.

[0007]

Therefore, the present inventors have
As a result of earnestly and intensively focusing on the problem to be solved by the invention as described above, a polymer having a specific group called N-acyl cyclic urea group as a functional group for crosslinking is used as a base. It was found that a curable material is excellent in curability, and further, it gives a cured product excellent in chemical resistance, water resistance, corrosion resistance and appearance, etc., and in solving the above problems brilliantly. The present invention has been completed here.

<Structure> That is, according to the present invention, basically, each of at least two N-acyl cyclic urea groups in one molecule, especially the general formula [I], is used.

[0009]

[Chemical 2] [However, X in the formula represents an alkylene group having 1 to 5 carbon atoms. ] The specific N-acyl cyclic urea group shown, and an acid group and / or a neutralized acid group,
Selected from the group consisting of an amino group, a hydroxyl group and an acetoacetyl group, a vinyl polymer (C) having at least one functional group together, and a group consisting of an amino group, a carboxyl group, a hydroxyl group and an acetoacetyl group. And a compound (B) having a molecular weight of 60 to 472 having at least one functional group as an essential component.

It has excellent curability and, above all, chemical resistance,
It is intended to provide an aqueous curable resin composition which gives a cured product having excellent water resistance, corrosion resistance and appearance.

Further, by adding a curing catalyst (D) to each of the above-mentioned compositions, it is intended to provide an aqueous curable resin composition in a form in which the curability is further improved. It is a thing.

Here, first, at least one kind selected from the group consisting of the above-mentioned N-acyl cyclic urea group, an acid group and / or a neutralized acid group, an amino group, a hydroxyl group and an acetoacetyl group. The vinyl-based polymer (C) having both the functional group of N and the N-acyl cyclic urea group reacts with the N-acyl cyclic urea group and the acid group and / or the neutralized acid group. As a functional group having active hydrogen that can be, for example, an amino group, a hydroxyl group,
It refers to a vinyl polymer having a carboxyl group and / or an acetoacetyl group.

As typical examples of the polymer (C), an acrylic polymer, an aromatic vinyl polymer,
Various vinyl polymers such as vinyl ester polymers or fluoroolefin polymers.

Here, in order to prepare the polymer (C), for example, (1) various vinyl monomers having an N-acyl cyclic urea group and various vinyl monomers having an acid group are used. Body, and a method of copolymerizing monomers having an amino group, a hydroxyl group, an acetoacetyl group, or the like, or (2) various vinyl-based compounds having both an N-acyl cyclic urea group and an acid group Examples thereof include a method of copolymerizing monomers with monomers having an amino group, a hydroxyl group, an acetoacetyl group, or the like.

Here, first, according to the above-mentioned method (1), the polymer (C) is used to obtain the polymer (C).
As typical N-acyl cyclic urea group-containing vinyl-based monomers, various compounds represented by the following general formula [II] or [III] are listed. Can be done.

R ₁ R ₂ C = CR ₃ -Y [II]

[However, in the formula, R ₁ , R ₂ and R ₃
Are respectively the same or different, a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group,
It represents a group selected from the group consisting of an acyloxyl group and an alkoxycarbonyl group, and Y represents an N-acyl cyclic urea group as represented by the above general formula [I]. ]

CH ₂ ═CH—OCO— (CH ₂ ) _n— Y [III]

[Wherein Y represents an N-acyl cyclic urea group represented by the above general formula [I], and n is an integer of 1 to 12. To do. ]

First, in specifically exemplifying the compound represented by the general formula [II], N- (meth) acryloylethylene urea and N- (meth) are particularly representative as the compound. ) Acryloyl propylene urea, N- (meth) acryloyl tetramethylene urea, N- (meth) acryloyl pentamethylene urea, N
-(Meth) acryloylhexamethylene urea, N- (meth) acryloyl heptamethylene urea, etc.,

2- (ethylene ureidocarbamido) ethyl (meth) acrylate, 2- (propyleneureidocarbamido) ethyl (meth) acrylate, 2- (tetramethyleneureidocarbamido) ethyl (meth) acrylate, methyl 3- (N-ethylene) Ureido carbonyl)
Acrylate, butyl 3- (N-ethylene ureidocarbonyl) acrylate, isobutyl 3- (N-propylene ureidocarbonyl) methacrylate and the like.

Next, in specifically exemplifying the compound represented by the above-mentioned general formula [III], N- (2-vinyloxycarbonylacetyl) ethyleneurea, N- (2-vinyloxycarbonylacetyl) ethyleneurea, N -(3-Vinyloxycarbonylpropanoyl) propyleneurea, N
Various N-, such as-(4-vinyloxycarbonylbutanoyl) tetramethyleneurea, N- (5-vinyloxycarbonylpentanoyl) tetramethyleneurea and the like.
(Ω-vinyloxycarbonylalkanoyl) alkylene ureas and the like.

Among the vinyl monomers having an acid group used for preparing the polymer (C) by the above-mentioned method (1), the carboxyl group-containing monomer is particularly representative. Examples thereof include various unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid;

Alternatively, monoesters of various unsaturated dicarboxylic acids and saturated monohydric alcohols such as monomethyl itaconate, monobutyl itaconate, monomethyl maleate, monobutyl maleate, monomethyl fumarate or monobutyl fumarate (half (Esters),

Further, various saturated dicarboxylic acids such as monovinyl adipate or monovinyl succinate; or various saturated polycarboxylic acid anhydrides such as succinic anhydride or glutaric anhydride or phthalic anhydride or trimellitic anhydride. And the like and various hydroxyl group-containing vinyl-based monomers as described below.

Particularly preferable examples of the acid group-containing vinyl monomer used for introducing an acid group other than the carboxyl group are 2-sulfonooxyethyl (meth) acrylate and 2-acrylamido-2. -Various sulfonic acid group- or phosphoric acid group-containing vinyl monomers such as methylpropane sulfonic acid or 2-phosphonooxyethyl (meth) acrylate.

Further, as the vinyl-based monomer having both an N-acyl cyclic urea group and an acid group, which is used for preparing the polymer (C) by the above-mentioned method (2), Examples include compounds represented by the following general formula [IV].

R ₄ R ₅ C = CR ₆ -Y [IV]

[However, in the formula, R ₄ , R ₅ or R ₆
Are respectively the same or different, a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group,
It represents an atomic group or group selected from the group consisting of an acyloxyl group, an alkoxycarbonyl group, a carboxyl group and a carboxyalkyl group.
It is assumed that any one of ₄ , R _{5 and} R ₆ is a carboxyl group or a carboxyalkyl group, and Y is as described above. ]

As typical vinyl monomers such as these, various alkylene urea compounds such as ethylene urea, propylene urea or tetramethylene urea, and maleic anhydride or itaconic anhydride,
1: 1 addition reaction products with various unsaturated dicarboxylic acids.

Furthermore, to prepare a polymer (C) having both a neutralized acid group as the polymer (C), for example, (3) various polymers having an N-acyl cyclic urea group are used. In addition to vinyl monomers and various vinyl monomers having a neutralized acid group, a method of copolymerizing monomers having an amino group, a hydroxyl group or an acetoacetyl group, etc. , Or (4) beforehand, (1)
Alternatively, there may be mentioned a method in which the carboxyl group in the acid group-containing vinyl polymer prepared by the method (2) is neutralized with a basic compound.

Here, first, as a particularly typical basic compound used for neutralizing the acid group in the polymer (C) according to the method (4), sodium hydroxide or water is used. Like potassium oxide,
Various alkali metal salts; carbonates or hydrogen carbonates of various alkali metals such as lithium carbonate, sodium or potassium carbonate or sodium hydrogen carbonate or potassium hydrogen carbonate;

Various quaternary ammonium hydroxides such as tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide or trimethylbenzylammonium hydroxide; or methylamine, ethylamine, n-propylamine or n. -Including various primary amines such as butylamine,

Dimethylamine, diethylamine, di-n
Various secondary amines such as propylamine; various tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine, dimethylcyclohexylamine, dimethylbenzylamine, dimethylaminoethanol or 1-dimethylamino-2-propanol. Examples include primary amines; or ammonium hydroxide.

Next, according to the above-mentioned method (3), a typical representative of the neutralized acid group-containing vinyl monomer used for the purpose of introducing the neutralized acid group into the polymer (C). Specific examples include sodium (meth) acrylate, potassium (meth) acrylate or (meth)
As described above, sodium salts, potassium salts, amine salts and the like of various carboxyl group-containing vinyl-based monomers typified by acrylic acid triethylamine salts and the like are mentioned.

Particularly representative amino group-containing monomers used for preparing the polymer (C) are tert-butylaminoethyl (meth) acrylate, 2-aminoethyl crotonate, and 2- ( N-methylamino) -ethyl crotonate, 2-aminoethyl vinyl ether, 4-aminobutyl vinyl ether,

Allylamine, N-methylallylamine,
(Meth) acrylamide, N-methyl (meth) acrylamide, Nn-butyl (meth) acrylamide, diacetone acrylamide, etc., and further,
Primary, as typified by various hydrazine residue-containing monomers obtained by reacting various isocyanate group-containing monomers such as 2-isocyanate ethyl acrylate with hydrazine To secondary amino group-containing monomers.

Further, typical examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate,
Or an addition reaction product of 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 2-hydroxyethyl allyl ether, allyl alcohol and the like, and further, these various hydroxyl group-containing monomers with ε-caprolactone And so on.

Further, as typical representatives of acetoacetyl group-containing monomers, 2-acetoacetoxyethyl (meth) acrylate, 4-acetoacetoxybutyl (meth) acrylate, 2-acetoacetoxyethyl vinyl ether or 4 -Acetoacetoxybutyl vinyl ether and the like.

As mentioned above, (1), (2),
When the polymer (C) is prepared by each method such as (3) or (4), in addition to the various vinyl monomers listed above as those used in each of these methods, Of course, other monomers that can be copolymerized with the vinyl-based monomer can also be used, but as particularly typical ones as the other monomer that can be copolymerized,

Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-
Including various alkyl (meth) acrylates such as C1 to C22 such as ethylhexyl (meth) acrylate or lauryl (meth) acrylate,

Various alicyclic alkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate or isobornyl (meth) acrylate; various such as benzyl (meth) acrylate or phenethyl (meth) acrylate Aralkyl (meth) acrylates of

Various alkyl esters of crotonic acid such as methyl crotonic acid or ethyl crotonic acid; various alkyl esters such as dimethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, dimethyl itaconate or dibutyl itaconate. Dialkyl esters of unsaturated dicarboxylic acids;

Various aromatic vinyl monomers such as styrene, p-tert-butylstyrene, α-methylstyrene or vinyltoluene; various N, N-such as N, N-dimethyl (meth) acrylamide. Disubstituted (meth) acrylamides; various cyano group-containing monomers such as (meth) acrylonitrile or crotononitrile;

Various haloolefins such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, vinyl chloride or vinylidene chloride; ethylene, propylene, isobutylene or 1-butene, Various α-olefins;

Or vinyl acetate, vinyl propionate,
Various carboxylic acid vinyl esters such as vinyl pivalate or vinyl versatate, and further various alkyl- or cycloalkyl vinyl ethers such as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether or cyclohexyl vinyl ether. Is.

To prepare each of the vinyl polymers (C) used in the present invention using the various monomers as listed above, a solution polymerization method or a bulk polymerization method, etc. Various known and commonly used polymerization methods can be applied, and among them, the solution radical polymerization method in an organic solvent is the most convenient.

At this time, various known and commonly used compounds can be used as the polymerization initiator. Of these, only typical ones will be exemplified.
2,2'-azobis (isobutyronitrile), 2,2 '
Various azo compounds such as azobis (2,4-dimethylvaleronitrile) or 2,2′-azobis (2-methylbutyronitrile);

Tert-butyl peroxypivalate,
tert-butyl peroxybenzoate, tert-
Butyl peroxy-2-ethyl hexanoate, benzoyl peroxide, lauroyl peroxide, di-
including tert-butyl peroxide or dicumyl peroxide,

Various organic peroxides such as tert-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide or diisopropyl peroxycarbonate;
It goes without saying that these may be used alone or in combination of two or more kinds.

As the organic solvent, of course, known and commonly used ones can be used, and among them, typical ones are propanol, i-propanol,
n-butanol, i-butanol, tert-butanol, amyl alcohol, i-amyl alcohol, ter
Various alcohols such as t-amyl alcohol;

Or various glycol ethers such as ethyl cellosolve and butyl cellosolve; ethyl cellosolve acetate and butyl cellosolve acetate,
Various ether esters; or N-methylpyrrolidone, dimethylformamide, dimethylacetamide, ethylene carbonate, etc., but these may be used alone or in combination of two or more. is there.

Using such a polymerization initiator and an organic solvent, the polymer (C) can be obtained by a conventional method according to a solution radical polymerization method. The amount of the organic solvent or the like used is within a known and commonly used range, for example, in the case of the polymerization initiator, about 0.1 to 5% by weight is suitable with respect to the total amount of the vinyl monomer used. Is.

The number average molecular weight of the polymer (C) thus obtained is in the range of 250 to 50,000,
More preferably, the range of 300 to 30,000 is suitable.

In this case, if it is less than 250, the curability of the finally obtained composition of the present invention tends to be insufficient, while if it exceeds 50,000 and becomes too high. In any case, it becomes difficult to disperse or solubilize water, which is not preferable.

The amount of the acid groups and / or the neutralized acid groups to be introduced into the polymer (C) is 0.1 to 3. per 100 g of the solid content of the polymer (C). The range of 0 mol is more preferable, and the range of 0.2 to 2.5 mol is more preferable.

If the amount is less than 0.1 mol,
It is difficult to obtain a stable aqueous solution or dispersion of each of these polymers. On the other hand, when it is used in excess of 3.0 mol, the water resistance of the resulting coating film is inevitably reduced. In any case, it is not preferable.

Further, N which should be introduced into this polymer (C)
-The amount of the acyl cyclic urea group is such that the polymer (C)
In the range of 0.2 to 6 mol, more preferably 0.3 to 5 mol, per 1,000 g of the solid content.

When the amount is less than 0.2 mol,
The curability tends to be inferior. On the other hand, if the amount exceeds 6 mol and is used in an excessively large amount, the water resistance of the resulting coating film is inevitably deteriorated.

Further, the amount of functional group such as amino group, hydroxyl group or acetoacetyl group, that is, a group containing so-called active hydrogen, which should be introduced into the polymer (C), is the above-mentioned polymer (C). Depending on the amount of the acid group and / or the neutralized acid group and the N-acyl cyclic urea group to be introduced therein, each can be appropriately selected, but in general,
0.2 per 100 g of solid content of the polymer (C)
It may be about 6 mol.

Then, as described above, the polymer (C)
To obtain an aqueous dispersion or aqueous solution of, for example,
(I) A method in which water is added to an organic solvent solution of the polymer (C) to disperse it in water or to make it water-soluble, and the organic solvent is removed if necessary.

(Ii) A method in which an organic solvent solution of the polymer (C) is added to water containing a protective colloid, an emulsifying agent and the like to disperse it in water or to make it water-soluble and, if necessary, to remove the solvent, iii) A method in which water is added to the organic solvent solution of the polymer (C), and then the solvent is removed and the phase inversion emulsification is performed.

Alternatively, there are various methods such as (iv) a method in which water containing a protective colloid, an emulsifier, etc. is added to a solution of the polymer (C) in an organic solvent, followed by desolvation-phase inversion emulsification. , Can be applied as it is.

Next, in the present invention, this polymer (C) is used.
A compound (B) having at least one functional group selected from the group consisting of an amino group, a carboxyl group, a hydroxyl group and an acetoacetyl group, that is, a compound containing so-called active hydrogen ( Hereinafter referred to as active hydrogen functional group-containing compound) (B) is a group consisting of various active hydrogen functional groups such as hydroxyl group, carboxyl group, amino group or acetoacetyl group, excluding N-acyl cyclic urea group. Chosen from,
A compound having at least two functional groups in one molecule and having a relatively low molecular weight of 60 to 472 excluding so-called high molecular weight polymers. Is.

The carboxyl group may be neutralized with various volatile amines or ammonium hydroxide, or the amino group may be neutralized. It may be in a form neutralized with various volatile carboxylic acids.

As typical examples of such compound (B), polyhydric alcohols, polyhydric carboxylic acids or their amine neutralized products, polyamine compounds or their acid neutralized products, polyamide compounds, polyhydric compounds Including acetoacetic acid esters of alcohols, aminocarboxylic acids, hydroxycarboxylic acids or their neutralized amines, polyhydrazide compounds, etc.,

Alternatively, a polyisocyanate compound,
A compound having a relatively low molecular weight such as a compound having a hydrazine residue, which is obtained by reacting with hydrazine.

Of these, particularly typical examples of the above polyhydric alcohols are ethylene glycol, neopentyl glycol, propylene glycol and 1,4-
Diols such as butanediol, 1,6-hexanediol, cyclohexane-1,4-dimethanol, hydrogenated bisphenol A, diethylene glycol or sorbitol;

Alternatively, various triols such as glycerin, trimethylolethane or trimethylolpropane; and various low-molecular-weight compounds having a valence of 4 or more such as pentaerythritol or sorbitol.

As typical examples of the above-mentioned polycarboxylic acids, succinic acid, glutaric acid, adipic acid or sebacic acid or phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid or methylhexahydrophthalic acid. Various dicarboxylic acids such as acids; or various low molecular weight compounds having a valence of 3 or more such as trimellitic acid, pyromellitic acid or butanetetracarboxylic acid.

Further, as typical examples of the above polyamines, ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, xylylenediamine, isophoronediamine,
Various low molecular weight compounds such as 1,3-diaminomethylcyclohexane or diethylenetriamine.

Further, as typical examples of the above-mentioned polyamides, various low molecular weight compounds such as adipic acid diamide, succinic acid diamide or sebacic acid diamide, and the like can be given.

Next, as typical examples of the acetoacetic acid esters of polyhydric alcohols mentioned above, various kinds of relatively polyhydric alcohols such as those mentioned above can be obtained by reaction with diketene. And low molecular weight compounds.

Next, as typical examples of the aminocarboxylic acid, various low molecular weight compounds such as glycine or aminocaproic acid are listed.

Next, as a particularly representative one of the above-mentioned hydroxycarboxylic acids, glycolic acid,
It is various low molecular weight compounds such as lactic acid, malic acid, 3-hydroxypyropionic acid or 12-hydroxystearic acid. As the above-mentioned polyhydrazide compound, adipic acid hydrazide or sebacine is particularly representative. These include various low molecular weight compounds such as acid hydrazide.

Further, the water-based curable resin composition of the present invention contains the above-mentioned N-acyl cyclic urea group, respectively.
The curability of the composition of the present invention can be improved by incorporating a catalyst (curing catalyst) used for the reaction with so-called various active hydrogen functional groups such as amino group, carboxyl group, hydroxyl group or acetoacetyl group. Can be further improved.

Among these curing catalysts (D), particularly representative ones are various strongly basic tertiary amines such as diazabicyclooctane, diazabicycloundecene or diazabicyclononene; dibutyl. Various organotin compounds such as tin diacetate, dibutyltin dioctoate, dibutyltin dilaurate or tributyltin-2,2-dimethylpentanoate;

Tetramethylammonium fluoride,
Various quaternary ammonium salts such as tetrabutylammonium chloride, trimethylbenzylammonium acetate, triethylbenzylammonium octoate or trimethylbenzylammonium-2,2-dimethylpentanoate;

Such as various phosphonium salts such as triphenylbenzylphosphonium fluoride, triphenylbenzylphosphonium chloride, tetrabutylphosphonium acetate or tetrabutylphosphonium-2,2-dimethylpentanoate.

Further, a special polymer such as a vinyl polymer containing a group having a catalytic activity (ability) such as a strongly basic tertiary amino group, tin carboxylate group, quaternary ammonium group or phosphonium group. Polymers of can also be used.

Among these various catalysts, it is particularly preferable to use a strongly basic tertiary amine or quaternary ammonium salt from the viewpoint of curability.

In order to prepare the water-based curable resin composition of the present invention from the components (C) and (B) described above, the N-acyl cyclic urea group in the component (C) is prepared. And the equivalent ratio of the total amount of active hydrogen functional groups in the components (C) and (B) is 0.1: 1 to 1: 0.1, preferably 0. 2: 1 to 1: 0.
These two components may be mixed in a ratio such that the ratio becomes 2.

Further, in order to prepare the water-based curable resin composition of the present invention by blending the curing catalyst (D) with the mixture of the component (C) and the component (B), each of these components can be prepared. The amount of the group or atomic group having catalytic activity is 2 to 400 mmol, preferably 4 to 200 mmol, based on 1,000 g of the solid content of the mixture. Then, the component (D) may be blended.

The water-based curable resin composition of the present invention may be used as it is or in addition to the resin composition of this form,
In addition to a solvent, a pigment, a filler, and the like, further, various known additives such as a leveling agent, an ultraviolet absorber, an antioxidant, a pigment dispersant, and the like are blended in a form in which they are mixed. , Can be used.

Further, in the composition of the present invention, the urea resin may be added within the range that does not deviate from the object of the present invention, and within the range that does not impair the features of the present invention. Various amino resins such as melamine resin and benzoguanamine resin, and various known and commonly used curing agents such as blocked isocyanate can also be added and used.

The water-based curable resin composition of the present invention thus obtained is applied to a substrate or the like, and then 100 to 25
By carrying out heat curing at about 0 ° C. for about 1 minute to about 2 hours, a cured product excellent in chemical resistance, water resistance, corrosion resistance and appearance, among others, is formed.

The curable resin composition of the present invention is used for various inorganic ceramic base materials such as cement-based materials, and for various metal base materials such as iron and aluminum alloys. Can be used for paints, but more specific uses include paints for the inside or outside of cans, paints for precoat metal, base coat paints or top coat paints for automotive topcoats, etc. Can be used for various paints such as

Further, it is effectively used in various fields other than so-called paints such as adhesives and sealing agents.
It can be used.

[0089]

EXAMPLES Next, the present invention will be explained more specifically with reference to Reference Examples, Examples and Comparative Examples. In the following, all parts and percentages are by weight unless otherwise specified. There is.

Reference Example 1 [Preparation Example of Vinyl Polymer (C) Containing N-Acyl Cyclic Urea Group / Carboxyl Group / Hydroxyl Group] A thermometer, a reflux condenser, a stirrer, a dropping funnel and a nitrogen gas introducing tube were provided. A reaction vessel was charged with 1,000 parts of propylene glycol monomethyl ether, 164 parts of N-methacryloyl propylene urea and 3 parts of tert-butyl peroxyoctoate (TBO), and while stirring, in a nitrogen gas stream, The temperature was raised to 80 ° C.

Then, at the same temperature, 2 parts of styrene (St) were added.
00 parts, n-butyl methacrylate (BMA) 526
Part, 60 parts of acrylic acid (AA) and 50 parts of 2-hydroxyethyl methacrylate, and 25 parts of TBO were added dropwise over 5 hours.

After completion of the dropping, the number average molecular weight (Mn) was 8,400 and the nonvolatile content (NV) was 5 by keeping the same temperature for 15 hours to continue the reaction.
A target polymer having an acid value of 47% and a solid content of 4% was obtained. Hereinafter, this is abbreviated as a polymer (C-1).

Reference Example 2 [Preparation Example of Vinyl Polymer (C) Containing N-Acyl Cyclic Urea Group / Carboxyl Group / Acetoacetyl Group] In a reaction vessel similar to that of Reference Example 1, 1 of ethyl cellosolve was added.
000 parts were charged and the temperature was raised to 80 ° C. in a nitrogen gas stream while stirring. Then, at the same temperature, 260 parts of St, 430 parts of BMA, 200 parts of N-methacryloyltetramethylene urea, 50 parts of 2-acetoacetoxyethyl methacrylate and methacrylic acid (MA
A mixture of 60 parts of A) and 28 parts of TBO,
It was added dropwise over 5 hours.

After completion of dropping, the reaction was continued at the same temperature for 15 hours to continue the reaction, whereby Mn was 9,800, NV was 52%, and the solid content acid value was 3%.
The target polymer No. 9 was obtained. Hereinafter, the polymer (C-
2) is abbreviated.

Reference Example 3 [Preparation Example of Vinyl Polymer (C) Containing N-Acyl Cyclic Urea Group / Carboxyl Group / Amino Group] In a reaction vessel similar to that of Reference Example 1, 80% of ethyl cellosolve was added.
Charge 0 parts and stir in a nitrogen gas stream for 8 hours.
The temperature was raised to 0 ° C. Then, at the same temperature, St of 300
Parts, 320 parts of BMA, n-butyl acrylate (B
A) consisting of 100 parts, 50 parts of AA and 200 parts of N-methacryloylethylene urea, 28 parts of TBO, 30 parts of N-methylacrylamide and 200 parts of isopropyl alcohol (isopropanol). The mixture and the mixture were separately added dropwise over 5 hours.

After the dropping, the reaction was continued at the same temperature for 15 hours to continue the reaction, whereby Mn was 9,500, NV was 51%, and the solid acid value was 3%.
The target polymer No. 9 was obtained. Hereinafter, the polymer (C-
It is abbreviated as 3).

Reference Example 4 (Preparation example of a vinyl polymer having both a hydroxyl group and a carboxyl group as a control) In a reaction vessel similar to that of Reference Example 1, ethyl cellosolve 1
000 parts were charged and the temperature was raised to 80 ° C. in a nitrogen gas stream while stirring. Then, at the same temperature, a mixture of 200 parts of St, 418 parts of BMA, 232 parts of 2-hydroxyethylmethacrylate, 100 parts of BA and 50 parts of AA and 28 parts of TBO was added for 5 hours. Was dropped.

After the dropping, the reaction was continued at the same temperature for 15 hours to continue the reaction, whereby Mn was 8,700, NV was 51%, and solid acid value was 3%.
A control polymer of 9 was obtained. Hereinafter, the polymer (R
-1) is abbreviated.

Examples 1 to 4 Triethylamine was added to the component (C) at a ratio as shown in Table 1 to neutralize the carboxyl group, and then ion-exchanged water was added to the component (C). Various aqueous resins were obtained.

Then, the component (B) or the component (D) is added in a ratio as shown in the same table, and the mixture is sufficiently stirred to give the desired various aqueous curable resin compositions. Prepared.

Thereafter, each composition was separately applied onto a zinc phosphate-treated steel sheet having a thickness of 0.8 mm so as to give a dry film thickness of 50 μm by using an applicator. After that, various cured coating films were obtained by heating and curing under the conditions shown in the table.

Subsequently, the respective cured coating films thus obtained were subjected to tests for evaluation and examination of chemical resistance, water resistance, corrosion resistance and appearance. The results are shown together in the same table.

The above chemical resistances, respectively,
"Acid resistance" and "alkali resistance" are performed as follows. "Acid resistance" ............ Keeping the cured coating film at 40 ℃, 1
The condition of the coated surface after being immersed in a 0% aqueous solution of sulfuric acid for 24 hours was visually determined.

"Alkali resistance" ... The cured coating film was immersed in a 10% aqueous sodium hydroxide solution kept at 40 ° C. for 24 hours, and the state of the coated surface was visually evaluated.

The above "water resistance" means that the cured coating film is
The condition of the coated surface after being immersed in warm water of 0 ° C. for 14 days was visually determined. Furthermore, the above "corrosion resistance" is 2 for a cured coating film with a cross cut.
The state of the coated surface after the salt spray test for 40 hours was visually evaluated.

Furthermore, the above-mentioned "appearance" is based on the smoothness, sharpness and gloss of the coated surface.
This is a comprehensive judgment.

Comparative Example 1 Control vinyl polymer (R-1) obtained in Reference Example 4
After 3.5 parts of triethylamine was added to 100 parts of the above and sufficiently stirred, 50 parts of ion-exchanged water was added to obtain a control aqueous resin.

Next, 18.9 of "Watersol S-695" [methyl etherified melamine resin manufactured by Dainippon Ink and Chemicals, Inc .; NV = 66%] was added to this resin.
A control aqueous curable resin composition was prepared by adding parts.

Then, the thus obtained control composition was coated on a zinc phosphate-treated steel sheet in the same manner as in Examples 1 to 4 so as to give a dry film thickness of 50 μm, and then 160 ° C. After baking for 30 minutes, a cured coating film for control was obtained.

Subsequently, this cured coating film was also subjected to the same evaluation test as in each example. The results are also shown in Table 2.

[0111]

[Table 1]

<< Footnotes in Table 1 >> The numbers of each component in the table are as follows:
All represent "parts by weight".

In the component (B), and are as follows. ………………… Trimethylolpropane …………………… Adipic acid dihydrazide ……………… Trimethylolpropane / trisacetoacetate

Further, "C-1", "C-2" and "C"
-3 "is an abbreviation for" polymer (C-1) "," polymer (C-2) "and" polymer (C-3) ", respectively, as a component of the vinyl polymer (C). is there.

Each of and in the component (D) is as follows. ………………… Benzyltrimethylammonium acetate …………………… Tetrabutylammonium acetate

[0116] “TEA” ………… Triethylamine

[0117]

[Table 2]

<< Footnote in Table 2 >> Abbreviation of "alkaline resistance" ... "Alkali resistance""curingcondition" .... Unit is "° C x min",
For example, "140 x 30" means "at a temperature of 220 ° C,
For 30 minutes ”. The same applies below.

[0119]

Industrial Applicability The water-based curable resin composition of the present invention is extremely highly practical in that it forms a cured product having excellent chemical resistance, water resistance, corrosion resistance and appearance.

Claims (5)

(57) [Claims] 1. A molecule is selected from the group consisting of at least two N-acyl cyclic urea groups, an acid group and / or a neutralized acid group, an amino group, a hydroxyl group and an acetoacetyl group. Selected from the group consisting of a vinyl polymer (C) having at least one kind of functional group, an amino group, a carboxyl group, a hydroxyl group and an acetoacetyl group,
The molecular weight having at least one functional group is 60 to 472.
An aqueous curable resin composition, which comprises the compound (B) as defined above as an essential film-forming component. 2. A molecule is selected from the group consisting of at least two N-acyl cyclic urea groups, an acid group and / or a neutralized acid group, an amino group, a hydroxyl group and an acetoacetyl group. Selected from the group consisting of a vinyl polymer (C) having at least one kind of functional group, an amino group, a carboxyl group, a hydroxyl group and an acetoacetyl group,
The molecular weight having at least one functional group is 60 to 472.
An aqueous curable resin composition, which comprises the compound (B) and the curing catalyst (D) as essential film-forming components. 3. The vinyl-based copolymer (C) is N
The aqueous curable resin composition according to claim 1 or 2, which is obtained by a radical polymerization method of a vinyl monomer containing an acyl cyclic urea group. 4. The water-curable resin composition according to any one of claims 1 to 3, wherein the N-acyl cyclic urea group is represented by the general formula [I]. [Chemical 1] [However, X in the formula represents an alkylene group having 1 to 5 carbon atoms. ] 5. The acid group in the vinyl polymer (C) is a carboxyl group, and the neutralized acid group in the polymer (C) is a carboxylate.
The water-based curable resin composition described.