JP2979437B2 - Aqueous curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel and useful aqueous curable resin composition. More specifically, it includes an aqueous dispersion or an aqueous solution of a polymer containing a carboxyl group and / or a carboxylate group, and a compound containing two or more 1,3-dioxolan-2-one groups in one molecule. More particularly, the present invention relates to an aqueous curable resin composition which forms a cured product excellent in chemical resistance and water resistance.

[0002] The composition of the present invention is very useful for applications such as paints, adhesives, sealing agents and fiber treatment agents.

[0003]

2. Description of the Related Art Conventionally, as an aqueous curable resin composition for paints and adhesives, a vinyl polymer having both a hydroxyl group and a carboxyl group is neutralized with a basic substance and then dispersed or dispersed in water. An aqueous resin obtained by dissolving an amino resin or a block isocyanate as a curing agent has been put into practical use.

[0004] However, the cured coating film obtained from such a composition has drawbacks such as so-called chemical resistance and water resistance, such as alkali resistance and acid resistance, and its use has naturally been limited.

[0005]

SUMMARY OF THE INVENTION However, in view of the above-mentioned various disadvantages in the prior art, the present inventors have considered that one of them has excellent curability and the other has two kinds of resistance. With the aim of obtaining an aqueous resin with excellent chemical properties and water resistance, the research has been started earnestly.

[0006] Accordingly, the problem to be solved by the present invention is to provide a cured product which is extremely practical and has excellent curability and also excellent water resistance and chemical resistance. To provide innovative technology.

[0007]

Means for Solving the Problems Accordingly, the present inventors have:
An aqueous dispersion or an aqueous solution of a polymer having a carboxyl group and / or a carboxylate group contains 2 per molecule.
By blending a compound having one or more 1,3-dioxolan-2-one groups, it can be quickly cured by heating to obtain a cured product having excellent water resistance and chemical resistance. Thus, the present invention has been completed.

[0008] That is, the present invention, as an essential component,
An aqueous dispersion or an aqueous solution of the polymer (A) having a carboxyl group and / or a carboxylate group in a molecule thereof, and two or more 1,3-dioxolane-2-molecules in a molecule;
And (B) having an on group as an essential component.

[0009] Alternatively, an aqueous dispersion or aqueous solution of the polymer (A) containing a carboxyl group and / or a carboxylate group, and two or more 1,3-dioxolan-2-one groups per molecule. Comprising, as essential components, a compound (B) to be reacted and a curing agent (C) that reacts with a hydroxyl group.

Further, each of the above-mentioned compounds has
Furthermore, an extremely practical aqueous curable resin composition, which is further blended with a curing catalyst (D) and which gives a cured product having excellent curability and excellent chemical resistance and water resistance. It is something to offer.

Hereinafter, the configuration of the present invention will be described in detail.
Here, first, the carboxyl group and / or
Or the polymer having a carboxylate group (A)
At least one, preferably at least 2 per molecule
A polymer having two carboxyl groups and / or carboxylate groups (—COO—).

As typical examples of the polymer (A), only typical ones are exemplified, and examples thereof include vinyl polymers, polyester resins, alkyd resins, polyether resins, polyurethane resins, polyamide resins, and the like. And a block or graft polymer of the vinyl polymer and a polymer other than the vinyl polymer.

[0013] Particularly typical examples of the vinyl polymer include an acrylic polymer, a vinyl ester polymer, a fluoroolefin polymer, an α-olefin polymer and a chlorinated olefin polymer. Is mentioned.

In order to obtain the above-mentioned carboxyl group-containing vinyl polymer, a carboxyl group-containing vinyl monomer is homopolymerized or copolymerized, or a dibasic acid anhydride is added to a previously prepared hydroxyl group-containing vinyl polymer. A known and commonly used method, such as adding, can be applied.

In order to obtain a carboxyl group-containing vinyl polymer, a carboxylate group-containing vinyl monomer is homopolymerized or copolymerized, or a carboxyl group-containing vinyl polymer is neutralized with a basic substance. A known and commonly used method such as squeezing can be applied.

In order to obtain a vinyl polymer having both a carboxyl group and a carboxylate group, it is convenient to partially neutralize the carboxyl group in the carboxyl group-containing polymer with a basic substance.

In the case of preparing such a vinyl polymer, only typical examples of the carboxyl group-containing vinyl monomer to be used are as follows.
Various unsaturated carboxylic acids such as acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid; or

Monomethyl itaconate, monobutyl itaconate, monomethyl maleate, monobutyl maleate,
Monoesters (half esters) of various unsaturated dicarboxylic acids such as monomethyl fumarate or monobutyl fumarate with saturated aliphatic monohydric alcohols; or various saturated dicarboxylic acids such as monobutyl adipate or monobutyl succinate And monovinyl esters of acids.

In addition, only typical examples of the carboxylate group-containing vinyl-based monomer are given below, and sodium (meth) acrylate, potassium (meth) acrylate or (meth) acrylic acid may be used. Examples thereof include sodium salts, potassium salts and amine salts of the above-mentioned carboxyl group-containing vinyl monomers such as triethylamine salts.

In this case, only other typical copolymerizable monomers that can be used are methyl (meth) acrylate, ethyl (meth) acrylate, and n-butyl (meth) acrylate. Acrylate,
iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth)
C ₁ -C ₂₂ , such as acrylate, lauryl (meth) acrylate or stearyl (meth) acrylate
Alkyl (meth) acrylates having an alkyl group of

Various cycloalkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, or isobornyl (meth) acrylate; aralkyl (such as benzyl (meth) acrylate and phenethyl (meth) acrylate) Meth) acrylates;

Crotonic acid esters of methyl crotonate, ethyl crotonate or n-butyl crotonate; various vinyl carboxylate such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl pivalate or vinyl versatate Esters; dialkyl esters of various unsaturated dibasic acids, such as dimethyl malate, dibutyl malate, dimethyl fumarate, dibutyl fumarate, dimethyl itaconate or dibutyl itaconate;

Various aromatic vinyl monomers such as styrene, p-tert-butylstyrene, α-methylstyrene or vinyltoluene; various alkyl-vinyl monomers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether or cyclohexyl vinyl ether. Or cycloalkyl vinyl ethers;
Various α-olefins, such as ethylene, propylene or 1-butene;

Various fluoroolefins such as tetrafluoroethylene, vinylidene fluoride, hexafluoropropylene or chlorotrifluoroethylene;
-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethoxy allyl ether, allyl alcohol, 2-hydroxyethyl vinyl ether or 4-hydroxybutyl vinyl ether, Various hydroxyl-containing monomers;

Various silyloxyalkyl group-containing monomers such as 2-trimethylsilyloxyethyl (meth) acrylate, 2-trimethylsilyloxypropyl (meth) acrylate, 4-trimethylsilyloxybutyl (meth) acrylate or 4-trimethylsilyloxybutyl vinyl ether Various hydroxymethylamino group-containing monomers such as N-methylol (meth) acrylamide or N-methylolcrotonamide;

Various N-alkoxymethylamino group-containing monomers such as N-methoxymethyl (meth) acrylamide or N-butoxymethyl (meth) acrylamide; various kinds of monomers such as (meth) acrylonitrile or crotononitrile Cyano group-containing monomers; various amide group-containing monomers such as (meth) acrylamide or crotonic amide; or N, N-dimethylaminoethyl (meth) acrylate or N, N-diethylaminoethyl (meth) ) Various tertiary amino group-containing monomers such as acrylate.

The polyester resin or alkyd resin having a carboxyl group can be prepared by condensing a polycarboxylic acid component, a polyhydric alcohol component and / or an oil component by a known and commonly used method.

The carboxyl group in the carboxyl group-containing polyester resin or alkyd resin is partially or completely neutralized with a basic substance, whereby a resin having both a carboxyl group and a carboxylate group, or A resin having only a carboxylate group can be obtained.

The carboxyl group-containing polyether resin is
It is prepared by adding a dibasic acid anhydride to various polyether resins such as polyethylene glycol, polypropylene glycol, polyteramethylene glycol or polyether having a bisphenol-A skeleton or bisphenol F skeleton having a hydroxyl group. It is possible,

The carboxyl group in the carboxyl group-containing polyether resin is partially or completely neutralized with a basic substance, so that a resin having both a carboxyl group and a carboxylate group, or only a carboxylate group, is obtained. Can be obtained.

The carboxyl group-containing polyurethane resin is
It can be prepared by adding a polybasic acid anhydride to a hydroxyl group-containing polyurethane resin, or by using a compound having both a hydroxyl group and a carboxyl group such as dimethylolpropionic acid as a polyhydric alcohol component.

The carboxyl group in such a carboxyl group-containing polyurethane resin is partially or completely neutralized with a basic substance, so that a resin having both a carboxyl group and a carboxylate group, or only a carboxylate group is used. Can be obtained.

By introducing a hydroxyl group as a reactive functional group into the polymer (A), the coating performance of the cured product can be further improved. To obtain an aqueous dispersion or aqueous solution of the polymer (A) as described above,
A method in which an organic solvent solution of the polymer (A) is added to water to disperse or make water soluble, and, if necessary, to remove the organic solvent;

A method in which an organic solvent solution of the polymer (A) is added to water containing a protective colloid, an emulsifier, etc. to disperse or make water soluble, and, if necessary, to remove the organic solvent.

A method of adding water to a solution of the polymer (A) in an organic solvent, followed by desolvation and phase inversion emulsification,

Various methods such as a method of adding water containing a protective colloid or an emulsifier to a solution of the polymer (A) in an organic solvent, followed by desolvation-phase inversion emulsification can be applied. In order to obtain an aqueous dispersion or an aqueous solution of a vinyl polymer, in addition to the various methods described above, a carboxyl group and / or a carboxylate are each used as an essential monomer component in a medium containing water. A method in which a monomer (mixture) containing a vinyl monomer having a group is emulsion-polymerized or solution-polymerized, or

After a monomer (mixture) containing a carboxyl group vinyl monomer as an essential component is subjected to emulsion polymerization or solution polymerization, the carboxyl group is neutralized with a basic substance and converted into a carboxylate group. Still other methods, such as methods, can be employed.

In dispersing the above-mentioned various polymers (A) in water, it is also effective to introduce a hydrophilic polyether segment such as a polyethylene glycol segment into the polymer in advance. Is the way.

When the carboxyl group is converted to a carboxylate group, only the above-mentioned basic substances which are particularly representative are exemplified, such as sodium hydroxide, lithium hydroxide or potassium hydroxide. ,
Various alkali metal salts;

Various alkali metal carbonates or bicarbonates such as lithium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate or kalim bicarbonate;

Various quaternary ammonium hydroxides, such as tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide or trimethylbenzylammonium hydroxide;

Various primary amines such as methylamine, ethylamine, n-propylamine or n-butylamine;

Dimethylamine, diethylamine, di-n
Various secondary amines, such as -propylamine or di-n-butylamine;

Various tertiary amines such as trimethylamine, triethylamine, tri-n-butylamine, tri-n-propylamine, dimethylcyclohexylamine, dimethylbenzylamine, dimethylaminoethanol or 1-dimethylamino-2-propanol;
Or ammonium hydroxide.

The amount of the carboxyl group and / or carboxylate group introduced into the various polymers (A) as described above is 0.15 to 13 mol per 1,000 g of the solid content of the resin (A). Preferably, 0.3
Suitably, it is in the range of １１11 mol.

Next, two or more 1, 1 in one molecule described above.
The compound (B) having a 3-dioxolan-2-one group refers to a low molecular weight compound or a high molecular weight compound having a 1,3-dioxolan-2-one group, and a carboxyl group in the same molecule. Are not included.

If only typical examples of such 1,3-dioxolan-2-one groups are given as examples, they are represented by the following general formulas [I] or [II].

[0048]

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(Wherein R ¹ , R ² and R ³
Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different. )

[0050]

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(Wherein R ⁴ and R ⁵ in the formula are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different, and R ⁶ is a carbon atom having 1 to 4 carbon atoms) An alkylene group having 3 to 10 carbon atoms having a substituent such as a halogen atom or an alkosyl group;
An oxyalkylene group having 3 to 10 carbon atoms. ) And 1,3
Specific examples of the dioxolan-2-one group include:
1,3-dioxolan-2-one-4-yl group, 4-methyl-1,3-dioxolan-2-one-4-yl group,
5-methyl-1,3-dioxolan-2-one-4-yl group, 4,5-dimethyl-1,3-dioxolan-2-
On-4-yl group, 4,5,5-trimethyl-1,3-
Dioxolan-2-one-4-yl group, 4-ethyl-
1,3-dioxolan-2-one-4-yl group, 5-ethyl-1,3-dioxolan-2-one-4-yl group,
4-n-propyl-1,3-dioxolan-2-one-
4-yl group, 5-n-propyl-1,3-dioxolan-2-one-4-yl group, 4-n-butyl-1,3-dioxolan-2-one-4-yl group or 5-n -Butyl-1,3-dioxolan-2-one-4-yl group and the like;

4,5-di-n-butyl-1,3-dioxolan-2-one-4-yl group, 3,4-carbonatocyclohexyl group, 1,2-carbonatocyclohexyl Group, 2,3-carbonate cyclohexyl group, 3-methyl-3,4-carbonate cyclohexyl group, 1-methyl-3,4-carbonate cyclohexyl group, 6-methyl-3,4-carbonate cyclohexyl group, 1,2-carbonate cyclopentyl group, 2,3-carbonate cyclopentyl group, 3,4-carbonate cyclopentyl group, 4,5-carbonate cyclooctyl group or 4,
And a 5-carbonate cyclododecyl group.

Among the 1,3-dioxolan-2-one group-containing compounds, particularly typical ones are acrylic polymers, vinyl ester polymers, fluoroolefin polymers, α-olefin polymers. Or various vinyl polymers such as chlorinated olefin polymers;
Alternatively, in addition to various polymers such as polyester resin, alkyd resin, polyether resin, polyurethane resin or polyamide resin,

A low molecular weight polyisocyanate compound,
A reaction product of a compound having both a hydroxyl group and a 1,3-dioxolan-2-one group as described above in one molecule,

Further, poly (methyl) glycidyl ether of polyhydric alcohol, poly (methyl) glycidyl ether of polyhydric carboxylic acid, di (methyl) glycidyl ether type epoxy resin of bisphenol A or bisphenol F or alicyclic polyepoxide Various polyepoxy compounds such as

[0056]

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(Where R ¹ , R ² and R ^{3 in the} formula are
Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different. )

[0058]

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(However, R ⁴ and R ⁵ in the formula are each the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁶ represents a carbon atom. An alkylene group having 3 to 10 carbon atoms having a substituent such as a halogen atom or an alkosyl group;
An oxyalkylene group having 3 to 10 carbon atoms. ), Low molecular weight compounds such as those obtained by reacting with carbon dioxide in the presence of a catalyst.

When the component (B) is itself water-soluble, it can be used as it is to obtain the composition of the present invention. It can also be used by forcibly dispersing it in water using a dispersant or the like.

The curability of the composition of the present invention can be further improved by blending the above-mentioned curing agent (C) which reacts with a hydroxyl group. If only typical examples of such a hydroxyl-reactive curing agent (C) are given as examples, various amino resins such as melamine resin, benzoguanamine resin or acetoguanamine resin, and various commonly used polyisocyanate compounds Is blocked with an active hydrogen-containing compound to obtain a blocked isocyanate.

The curing catalyst (D) referred to in the present invention is a catalyst effective for ring-opening a 1,3-dioxolan-2-one group, or the 1,3-dioxolan-2-one. A compound that is effective in promoting the reaction between a group and a carboxyl group.

Among the catalysts, only typical ones are exemplified, and tetramethylammonium fluoride, tetrabutylammonium fluoride,
Tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium acetate, tetrabutylammonium-2,2-dimethylpentanoate, trimethylbenzylammonium
Various quaternary ammonium salts, such as 2,2-dimethylpentanoate or trimethylbenzylammonium propionate;

Various strongly basic tertiary amines such as diazabicyclooctane, diazabicycloundecene or diazabicyclononene; triphenylphosphine;
Various phosphines, such as tri-n-butylphosphine or tri-n-octylphosphine;

Or various phosphonium salts such as triphenylbenzylphosphonium fluoride, triphenylbenzylphosphonium chloride, tri-n-butylbenzylphosphonium fluoride or tri-n-butylbenzylphosphonium chloride.

In order to prepare the composition of the present invention from both the aqueous dispersion or the aqueous solution of the polymer (A) and the compound (B), the solid content ratio by weight of (A):
(B) = 2: 98 to 98: 2, more preferably 5:
What is necessary is just to mix both components so that it may be in the range of 95-95: 5.

The composition of the present invention is prepared from three components of the aqueous dispersion or aqueous solution of the polymer (A), the compound (B), and the curing agent (C). First, after mixing both components such that the weight ratio of the solid content of (A) and (B) is within the above range,
Total amount of solid content of (A) and (B) (total weight of solid content) 1
The solid content of the component (C) is preferably 100 parts by weight or less with respect to 00 parts by weight, more preferably 50 parts by weight.
Component (C) may be blended so as to be not more than parts by weight.

From the aqueous dispersion / water solution of the polymer (A), the compound (B), and the curing catalyst (D),
In order to obtain the composition of the present invention, the solid content weight ratio of (A) and (B) is adjusted so that the weight ratio of these solids is within the above-mentioned range.
After mixing the components, the amount of the component (D) is preferably 60 mmol or less, more preferably 40 mmol or less, based on 100 g of the total amount of the solid content (total solid content) of the components (A) and (B). The component (D) may be blended at an appropriate ratio, and the aqueous dispersion / water solution of the polymer (A) may be mixed with the compounds (B), (C) and (D). In order to obtain the composition of the present invention from the four components
After mixing these three components such that the weight ratio of the solid content of (A), (B) and (C) is within the range described above, (A), (B) and (C) The component (D) is blended at a ratio such that the component (D) is 60 mmol or less, more preferably 40 mmol or less, per 100 g of the total amount of the solid content (total solid content). Good.

The aqueous curable resin composition of the present invention thus obtained can be used as a clear composition as it is, or can be used as a colored composition by adding various pigments.

Further, if necessary, the composition of the present invention may contain, in addition to various known and commonly used additives such as an ultraviolet absorber, an antioxidant, a pigment dispersant or a leveling agent,
Water-soluble organic solvents can also be blended.

The aqueous curable resin composition of the present invention comprises a metal,
For various coatings such as plastics, coatings for general coatings such as inorganic base materials, and various coatings such as electrodeposition coatings, as well as for fiber treatment, sealing agents and adhesives. Can be widely applied.

The composition of the present invention is prepared by, for example, applying the composition to a substrate or impregnating the composition with
By heating at 00 to 250 ° C. for about 30 seconds to 1 hour, a practically cured product can be obtained.

[0073]

Next, the present invention will be described more specifically with reference examples, examples and comparative examples. In the following, all parts and percentages are by weight unless otherwise specified.

Reference Example 1 [Preparation Example of Aqueous Dispersion of Carboxyl Group-Containing Polymer (A)] In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube and a thermometer, 300 ion-exchanged water was added. And heated to 85 ° C. under a nitrogen atmosphere.
In a solution of 2.5 parts of sodium dodecylbenzenesulfonate in 0 parts, 30 parts of methyl methacrylate,
A solution in which 40 parts of n-butyl methacrylate, 20 parts of n-butyl acrylate and 10 parts of methacrylic acid were added and emulsified, and a solution obtained by dissolving 1 part of ammonium persulfate in 50 parts of ion-exchanged water were added. It was added dropwise over time.

After completion of the dropwise addition, the carboxyl group-containing acrylic polymer (A) is maintained at the same temperature for 1 hour to complete the polymerization and has a non-volatile content (hereinafter abbreviated as NV) of 20.0%. A water dispersion (emulsion) was obtained. Hereinafter, this is abbreviated as aqueous resin (W-1).

Reference Example 2 [Preparation example of aqueous dispersion of polymer (A) having both carboxyl group and hydroxyl group] As a polymerizable monomer, 30 parts of methyl methacrylate was used.
NV was changed in the same manner as in Reference Example 1 except that 40 parts of n-butyl methacrylate, 15 parts of n-butyl acrylate, 5 parts of 2-hydroxyethyl methacrylate and 10 parts of methacrylic acid were used. 20.0
% Of an aqueous dispersion of the carboxyl-hydroxyl co-polymer (A). Hereinafter, this is abbreviated as aqueous resin (W-2).

Reference Example 3 [Preparation Example of Aqueous Solution of Carboxylate Group-Containing Polymer (A)] In a reaction vessel similar to that of Reference Example 1, 66 parts of isopropyl alcohol was charged and heated to 80 ° C. in a nitrogen atmosphere. .

Then, 10 parts of styrene, 20 parts of methyl methacrylate, and 35 parts of n-butyl methacrylate
, 20 parts of n-butyl acrylate, 15 parts of acrylic acid, and 4 parts of tert-butyl peroxy-2-ethylhexanoate were added dropwise over 3 hours.

After completion of the dropping, the carboxyl group-containing acrylic resin having the NV of 60.0% and the number average molecular weight (hereinafter abbreviated as Mn) of 14,000 is maintained at the same temperature for 10 hours. A solution of the polymer (A-1) was obtained.

To the polymer solution thus obtained, 21 parts of triethylamine and 100 parts of isopropyl alcohol were added, and the mixture was sufficiently stirred.
00% was neutralized to obtain a solution of the polymer converted to carboxylate groups.

Next, 150 g of this solution was added while stirring.
A portion of ion-exchanged water was added to obtain a uniform solution. Thereafter, a portion of isopropyl alcohol and water was distilled off from this solution under reduced pressure to obtain a water-isopropyl alcohol solution of a carboxylate group-containing acrylic polymer having a nonvolatile content of 40%. Hereinafter, this is abbreviated as aqueous resin (W-3).

Reference Example 4 [Preparation Example of Aqueous Dispersion of Polymer (A) Having Both Carboxyl Group and Carboxylate Group] In 170 parts of the solution of the polymer (A-1) obtained in Reference Example 3 , 7 parts of triethylamine and 100 parts of isopropyl alcohol were added, and the mixture was sufficiently stirred to obtain a solution of a polymer in which 33% of carboxyl groups were neutralized and converted to carboxylate groups.

Next, 150 parts of ion-exchanged water was added to this solution with stirring to form a uniform solution. Thereafter, the entire amount of isopropyloxy alcohol and a part of water were distilled off from the solution under reduced pressure to obtain an aqueous dispersion of a carboxylate group-containing acrylic polymer having a nonvolatile content of 40%. Hereinafter, this is abbreviated as aqueous resin (W-4).

REFERENCE EXAMPLE 5 (Same as above) In a 1-liter stainless steel autoclave sufficiently substituted with nitrogen, 70 parts of ethyl vinyl ether, 86 parts of monovinyl adipate, "Veoba 9" (C Shell, Netherlands) ₉ branched fatty acid vinyl esters)
119 parts of methyl ethyl ketone and 233 parts of 2,
2-azobis (2,4-dimethylvaleronitrile) 1
After charging 225 parts of liquefied and collected chlorotrifluoroethylene under pressure and reacting for 15 hours with stirring, unreacted chlorotrifluoroethylene was purged, and NV Is 57% and M
A solution of a carboxyl group-containing fluoroolefin polymer having n of 14,000 was obtained.

Next, dimethylaminoethanol 2
Add 2.3 parts, stir well, and add 5 parts of carboxyl group.
0% was neutralized to obtain a solution of the polymer converted to carboxylate groups.

Thereafter, the whole amount of the polymer was added to a mixture consisting of 800 parts of ion-exchanged water and 50 parts of ethylene glycol monomethyl ether with sufficient stirring to form a dispersion. Then, methyl ethyl ketone was distilled off to obtain a water-acid solution of a fluoroolefin polymer (A) having a carboxyl group / carboxylate group having an NV of 38.1%. Hereinafter, this is referred to as an aqueous resin (W
Abbreviated as -5).

Reference Example 6 (same as above) In the same reaction vessel as in Reference Example 1, the molar ratio of 2,2-diethylpropylene glycol to ε-caprolactone was 1 /
1,134 parts of adduct 2, 672 parts of hexamethylene diisocyanate, 26 of dimethylolpropionic acid
8 parts, 3,411 parts of methyl ethyl ketone and 2 parts of dibutyltin dilaurate were charged under a nitrogen atmosphere.
C., and the reaction was carried out at the same temperature for 15 hours to obtain a solution of a polyurethane resin having hydroxyl groups at both ends.

Then, at the same temperature, 200 parts of succinic anhydride and 10 parts of diazabicyclooctane were added to the solution and reacted for 10 hours. After the temperature was lowered, 50% of the carboxyl groups became medium. Then, 202 parts of triethylamine was added thereto, and the mixture was sufficiently stirred to obtain a solution of the polymer (A) having both a carboxyl group and a carboxylate group.

Thereafter, 3,026 parts of ion-exchanged water was added to this resin solution with sufficient stirring to disperse the mixture, and then methyl ethyl ketone was distilled off under reduced pressure to obtain a polyurethane having an NV of 45%. A resin dispersion was obtained. Hereinafter, this is abbreviated as aqueous resin (W-6).

Reference Example 7 [Preparation Example of Aqueous Dispersion of Polymer (A) Having Carboxyl Group, Carboxylate Group and Hydroxyl Group] Stirrer, dropping funnel, rectification tube (produced by reaction to prevent glycol from volatilizing Is used to remove only water from the reaction system), 148.7 parts of isophthalic acid, 11.0 parts of trimethylolpropane and 211 parts of neopentyl glycol in a reaction vessel equipped with a nitrogen inlet tube and a thermometer. .
7 parts and 66.0 parts of p-tert-butylbenzoic acid were charged and the temperature was raised to 170 ° C., and after the temperature reached the temperature, it took 4 hours to gradually raise the temperature to 220 ° C.

Further, the reaction was continued while maintaining the temperature at 220 ° C. for 1 hour, and then the temperature was lowered to 180 ° C. to obtain 65.5 parts of adipic acid and 1 part of hexahydrophthalic anhydride.
38.0 parts and 13.2 parts of maleic anhydride were charged and maintained at 155 ° C. for 1 hour, and gradually heated to 220 ° C. over 4 hours.

After continuing the reaction at the same temperature for 3 hours,
Replace the rectification tube with a reflux condenser, while gradually lowering the temperature,
174 parts of methyl ethyl ketone were charged to obtain 1,174 parts of a solution of a polyester resin having an acid value of 70 and a hydroxyl value of 3 per resin solid content.

Then, 180 parts of styrene, 100 parts of n-butyl methacrylate, 50 parts of n-butyl acrylate, 50 parts of 2-hydroxyethyl methacrylate
, A mixture consisting of 20 parts of acrylic acid and 20 parts of tert-butyl peroxyoctoate was added dropwise at 80 ° C over 4 hours, and after completion of the addition, the mixture was kept at the same temperature for 12 hours. The reaction is continued, and the solid content has an acid value of 57.6, a hydroxyl value of 23.4, and
A solution of a graft polymer having a NV of 64.0% and a weight ratio of a polyester resin component having a carboxyl group / hydroxyl group and an acrylic resin component of 60/40 was obtained.

Thereafter, this graft polymer solution was added to
104 parts of triethylamine was added so that the degree of neutralization of the carboxyl group became 100%, and the mixture was sufficiently stirred to obtain a solution of a graft polymer having a carboxylate group and a hydroxyl group.

Next, 1,654 parts of ion-exchanged water was added to and dispersed in the total amount of the solution with sufficient stirring, and methyl ethyl ketone was distilled off under reduced pressure to obtain an NV of 40%. An aqueous dispersion of a graft polymer of a polyester resin-acrylic resin was obtained. Hereinafter, this is abbreviated as aqueous resin (W-7).

REFERENCE EXAMPLE 8 [Preparation Example of Hydroxyl-Reactive Curing Agent (C)] In a reaction vessel similar to that of Reference Example 1, "Varnock DN-9" was added.
80S "(aliphatic polyisocyanate resin manufactured by Dainippon Ink and Chemicals, Ltd .; NV = 100%, NCO content = 20%), 1,000 parts, 331 parts of methyl ethyl ketoxime, and 1.000 parts of dibutyltin dilaurate. 4 parts and 1,473 parts of methyl ethyl ketone were charged, the temperature was raised to 80 ° C. under a nitrogen atmosphere, and the temperature was maintained for 10 hours.

Next, 16 parts of 2-hydroxymethyl-2-methoxymethylpropionic acid was added, and the reaction was carried out for 10 hours to obtain a solution of a carboxyl group-containing blocked isocyanate resin having an NV of 50%.

Thereafter, 96.2 parts of triethylamine were added and the mixture was sufficiently stirred so that 100% of the thus introduced carboxyl groups were neutralized. Water was added with sufficient stirring to obtain a dispersion.

Further, methyl ethyl ketone was distilled off from this dispersion under reduced pressure to obtain an aqueous dispersion of a blocked isocyanate resin having an NV of 50%. Hereinafter, this is abbreviated as curing agent (C-1).

Examples 1 to 8 and Comparative Examples 1 and 2 Various components were blended at the ratios shown in Table 1 to obtain clear compositions.

Next, each of the compositions was separately applied to a 0.8 mm thick zinc phosphate steel sheet using an applicator so as to have a dry film thickness of 30 μm, and the results are shown in the table. By curing under heat under the above conditions, a cured coating film was obtained.

Thereafter, each of the cured coating films thus obtained was evaluated for chemical resistance, water resistance, and gel fraction. The results are summarized in the same table.

The compound (B) having two or more 1,3-dioxolan-2-one groups in one molecule, which is used only in Examples, was as follows.

[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

[Table 1]

[0110]

[Table 2]

[0111]

The water-based curable resin composition of the present invention provides a cured product having excellent chemical resistance and water resistance, and is extremely practical, and is particularly useful for paints, adhesives, sealing agents and the like. It is used as a fiber treatment agent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 75/04 C08L 75/04 // C09D 201/06 C09D 201/06 C09J 201/06 C09J 201/06 (58) Fields surveyed (Int.Cl. ⁶ , DB name) C08L 1/00-101/14 C09D 201/06 C09J 201/06 CA (STN)

Claims (7)

(57) [Claims] An aqueous dispersion or aqueous solution of a polymer (A) having a carboxyl group and / or a carboxylate group in a molecule, and two or more 1,3-dioxolan-2-one groups in a molecule. An aqueous curable resin composition comprising the compound (B) as an essential component. 2. An aqueous dispersion or aqueous solution of a polymer (A) having a carboxyl group and / or a carboxylate group in a molecule, and two or more 1,3-dioxolan-2-one groups in one molecule. Compound (B) and curing agent (C) and / or curing catalyst (D) that react with hydroxyl groups
, As an essential component. 3. The polymer (A) is a vinyl-based polymer
Body, polyester resin, polyurethane resin and vinyl
Graft copolymerization between a vinyl polymer and a polymer other than a vinyl polymer
At least one polymer selected from the group consisting of polymers
The aqueous curable resin composition according to claim 1, wherein 4. The method according to claim 1, wherein the polymer (A) is an acrylic polymer.
It is a coalesced or fluoroolefin polymer,
3. The aqueous curable resin composition according to 1 or 2 . 5. The aqueous curable resin composition according to claim 1, wherein the polymer (A) also has a hydroxyl group. 6. The aqueous curable resin composition according to claim 2, wherein the curing agent (C) is an amino resin and / or a blocked polyisocyanate. 7. The above 1,3-dioxolan-2-one group is represented by the general formula [I]: (Wherein R ¹ , R ² and R ³ are each
It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different. Again
Is of the general formula [II] (However, R ⁴ and R ⁵ in the formula are each the same.
A hydrogen atom or carbon number which may or may not be
R ⁶ is an alkyl group having 1 to 4 carbon atoms and 3 to 1 carbon atoms.
0 alkylene group; halogen atom or alkosyl
Having 3 to 10 carbon atoms having a substituent as a substituent
Group or an oxyalkylene group having 3 to 10 carbon atoms
Shall be represented. )
The aqueous curable resin composition according to claim 1 .