JPH07228835A - Resin composition for water-based paint - Google Patents

Abstract

(57) [Summary] [Purpose] Each of them has excellent pigment dispersibility and water resistance under a wide range of drying conditions and various coating conditions, both for room temperature drying and baking. It is an object of the present invention to provide a resin composition for a water-based coating which is excellent in dispersibility with carbon black and has extremely high practicality. [Composition] A water-based paint in which a specific modified resin is dispersed in water, which is obtained by introducing a hydroxycarboxylic acid and a specific polyol into a hydroxyl group-containing vinyl copolymer through a diisocyanate compound. Resin composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a new and useful resin composition for water-based paint. More specifically, the present invention provides a copolymer of an ethylenically unsaturated monomer and an ethylenically unsaturated monomer having a hydroxyl group through an isocyanate compound, a hydroxycarboxylic acid, a polyoxyalkylene glycol, and a polyoxyalkylene glycol. Oxyalkylene bisphenol A
More specifically, the present invention relates to a resin composition for water-based paints, which is obtained by dispersing a modified resin in the form of addition of ether and / or polyoxyalkylene glycol monoalkyl ether in water and has excellent dispersibility of carbon black.

[0002]

2. Description of the Related Art In recent years, there has been an urgent need to switch from organic solvent-based paints to water-based paints due to ignition and explosion of organic solvents in paints, air pollution, and occupational health and safety problems.

Conventional ethylenically unsaturated monomers and α, β-
An aqueous copolymer with a monoethylenically unsaturated acid has a difficulty in dispersibility of carbon black.

[0004]

Therefore, the present inventors have diligently started research for the purpose of enhancing the dispersibility of carbon black.

Therefore, the problem to be solved by the present invention is to provide a resin composition for a water-based coating having an extremely high practicality, which can provide a coating film having excellent carbon black dispersibility. is there.

[0006]

Therefore, the present inventors have
As a result of intensive and intensive studies, focusing on the problems to be solved by the invention as described above, a copolymer (A) of an ethylenically unsaturated monomer and an ethylenically unsaturated monomer having a hydroxyl group is obtained. With a hydroxycarboxylic acid through an isocyanate compound, polyoxyalkylene glycol, polyoxyalkylene bisphenol A ether and /
Further, it has been found that the modified resin to which polyoxyalkylene glycol monoalkyl ether is added has the excellent dispersibility of carbon black, and the present invention is now completed. It was.

That is, the present invention basically comprises a copolymer (A) of an ethylenically unsaturated monomer and an ethylenically unsaturated monomer having a hydroxyl group; one or two units in one molecule. Reaction product (B-1) or (B-2) of a hydroxycarboxylic acid having a hydroxyl group with a diisocyanate compound
A reaction product of a polyoxyalkylene glycol, a monofunctional alcohol, and a diisocyanate compound (C
-1); Reaction product of polyoxyalkylene bisphenol A ether, monofunctional alcohol, diisocyanate compound (C-2) and / or polyoxyalkylene glycol monoalkyl ether, and diisocyanate compound ( C-3) is obtained by reacting with a modified resin of a specific form, which is dispersed in water to provide an extremely highly practical resin composition for water-based coatings,

Specifically, a copolymer (A) of an ethylenically unsaturated monomer and an ethylenically unsaturated monomer having a hydroxyl group, respectively; a hydroxy having one hydroxyl group in one molecule. Reaction product (B-1) of carboxylic acid (b-1) and diisocyanate compound (b-2) and / or hydroxycarboxylic acid (b-3) having two hydroxyl groups in one molecule, and diisocyanate Compound (b-2)
With a monofunctional alcohol (b-4) (B
-2) and; polyoxyalkylene glycol (c-1)
And a reaction product of a diisocyanate compound (b-2) and a monofunctional alcohol (b-4) (C-1); polyoxyalkylene bisphenol A ether (c-2)
And the reaction product (C-2) of the diisocyanate compound (b-2) and the monofunctional alcohol (b-4) and /
Alternatively, polyoxyalkylene glycol monoalkyl ether (c-3) and diisocyanate compound (b-
(2) A modified resin obtained by reacting the reaction product (C-3) with 2) is dispersed in water to provide an extremely practical resin composition for water-based paints. There

Alternatively, a copolymer (A) of an ethylenically unsaturated monomer and an ethylenically unsaturated monomer having a hydroxyl group; a hydroxycarboxylic acid having one or two hydroxyl groups in one molecule , A diisocyanate compound (b-
2) a reaction product (B-1) or (B-2); a polyoxyalkylene glycol (c-1), a monofunctional alcohol (b-4), and a diisocyanate compound (b).
-2) reaction product (C-1); polyoxyalkylene bisphenol A ether (c-2), monofunctional alcohol (b-4), and diisocyanate compound (b-
2) with the reaction product (C-2) and / or polyoxyalkylene glycol monoalkyl ether (c-
3) and a specific modified resin having a solid content acid value of 15 to 100, which is obtained by reacting a reaction product (C-3) of a diisocyanate compound (b-2), in water. The present invention is intended to provide a resin composition for water-based coatings, which has extremely high practicability,

Further, a copolymer (A) of an ethylenically unsaturated monomer and an ethylenically unsaturated monomer having a hydroxyl group; a hydroxycarboxylic acid (b) having one hydroxyl group in one molecule. -1) and a diisocyanate compound (b
-2) and a reaction product (B-1) and / or a hydroxycarboxylic acid having two hydroxyl groups in one molecule (b-
3), a reaction product (B-2) of the diisocyanate compound (b-2) and the monofunctional alcohol (b-4);
Reaction product (C-1) of polyoxyalkylene glycol (c-1), diisocyanate compound (b-2) and monofunctional alcohol (b-4); polyoxyalkylene bisphenol A ether (c-2) ), A diisocyanate compound (b-2), and a reaction product (C-2) of a monofunctional alcohol (b-4) and / or a polyoxyalkylene glycol monoalkyl ether (c-3), and a diisocyanate compound The solid content acid value obtained by reacting the reaction product (C-3) with (b-2) is 15 to 100, and the polyoxyalkylene glycol (c-1) described above is used. ),
Polyoxyalkylene bisphenol A ether (c-
2) and / or the content of the polyoxyalkylene glycol monoalkyl ether (c-3) is 0.1 to 2
It is an object of the present invention to provide a resin composition for water-based coatings, which has a very high practicality and is obtained by dispersing 5.0% by weight of a specific modified resin in water.

Here, the above-mentioned ethylenically unsaturated monomer, which is an essential component constituting the resin composition for water-based paint of the present invention, is copolymerized with an ethylenically unsaturated monomer having a hydroxyl group. The product (A) is prepared as follows.

The manufacturing method is not particularly limited, but it can be prepared by a known and commonly used method.
Of these, only representative ones will be described. To give an ethylenically unsaturated monomer at a temperature of about 60 to about 150 ° C. in various solvents such as toluene and xylene. That is, the ethylenically unsaturated monomer having a hydroxyl group and the radical polymerization initiator are appropriately adjusted over about 3 to about 4 hours.

After that, the copolymer is obtained by reacting for about 5 to about 10 hours.
During this reaction, it may be copolymerized with various copolymerizable polymers such as alkyd resin, polyester resin, epoxy ester resin, urethane resin, chlorinated polyethylene resin or chlorinated polypropylene resin. Good.

Examples of the solvent that can be used include those selected from the group consisting of solvents that do not react with isocyanate groups. Of these, only typical ones are exemplified by benzene, toluene,
Xylene, methyl acetate, ethyl acetate, n-butyl acetate,
Examples thereof include isobutyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cellosolve acetate, tetrahydrofuran, and cyclohexanone, and one or more of these can be used as necessary.

Further, the ethylenically unsaturated monomer and the hydroxyl group-containing ethylenically unsaturated monomer that can be used are not particularly limited, but of these, only typical ones will be exemplified. , Carbon number is 1
(Meth) acrylic acid esters of 18 alcohols with (meth) acrylic acid; or so-called reactive group-free monovalent compounds such as styrene, α-methylstyrene, vinyltoluene, vinylpyridine, butadiene and isoprene. Starting with the quantity,

Various unsaturated carboxylic acids such as (meth) acrylic acid, fumaric acid, maleic anhydride or itaconic acid; β-hydroxyethyl (meth) acrylate,
various hydroxyl group-containing vinylic monomers such as β-hydroxypropyl (meth) acrylate or polyethylene glycol mono (meth) acrylates; (meth) acrylamides; or methoxy polyethylene glycol (meth) acrylates, Examples thereof include so-called reactive group-containing hydrophilic monomers. If necessary, one or more of these can be used.

Further, the radical polymerization initiator which can be used is not particularly limited, but if only representative ones are exemplified, various radical polymerization initiators such as acetyl peroxide or benzoyl peroxide can be used. Diacyl peroxides; various ketone peroxides such as methyl ethyl ketone peroxide or cyclohexanone peroxide;

Various hydroperoxides such as tert-butyl hydroperoxide or cumene hydroperoxide; various dialkyl peroxides such as di-tert-butyl peroxide or dicumyl peroxide; tert-butyl peroxide Various alkyl peroxyesters such as oxyacetate or tert-butyl peroxypivalate;

Also, various azo compounds such as azobisisobutyronitrile or azobisisovaleronitrile; or various persulfates such as potassium persulfate or ammonium persulfate. If necessary, one or more of these can be used.

Next, a method for preparing a reaction product of a diisocyanate compound and a hydroxyl group-containing substance, that is, a reaction product of various hydroxycarboxylic acids and monofunctional alcohols, which will be described later, will be described. ,
In order to react any of these reaction products with the copolymer (A) of the ethylenically unsaturated monomer and the ethylenically unsaturated monomer having a hydroxyl group as described above. It is to be prepared.

When preparing the above-mentioned modified resin, which is an essential component of the resin composition for water-based paint of the present invention, a hydroxycarboxylic acid having one hydroxyl group in each molecule is prepared. The equivalent ratio with the diisocyanate compound is 1.0 to 1.1: 2.0.

Further, a hydroxycarboxylic acid having two hydroxyl groups in one molecule, a diisocyanate compound, and 1
The equivalent ratio with the functional alcohol is 2.0: 4.0: 1.
It is suitable to carry out the reaction with a ratio of 0 to 1.1.

The equivalent ratio of a hydroxycarboxylic acid having one hydroxyl group in one molecule (hereinafter also referred to as a monohydroxycarboxylic acid) to a diisocyanate compound is 1.
The equivalence ratio of 1.0 to 1.0: 2.0 is 1.0.
In the case of less than, inevitably, unreacted diisocyanate compound is likely to remain in the reaction product from these two components,

Furthermore, during the reaction of the copolymer (A) of the ethylenically unsaturated monomer and the ethylenically unsaturated monomer having a hydroxyl group, the viscosity becomes abnormally high or gelation occurs. It is not appropriate because

On the other hand, when the equivalent ratio exceeds 1.1, the reaction products from both components are inevitably mixed with the ethylenically unsaturated monomer and the ethylenically unsaturated monomer having a hydroxyl group. In any case, the reaction efficiency with the copolymer (A) is lowered, and the water dispersibility and water resistance are deteriorated.

Similarly, the equivalent ratio of hydroxycarboxylic acid having two hydroxyl groups in one molecule (hereinafter also referred to as dihydroxycarboxylic acid), diisocyanate compound and monofunctional alcohol is 2.0: 4. 0: 1.0 ~
First of all, to make 1.1, dihydroxycarboxylic acid,
The equivalent ratio to the diisocyanate compound is 2.
When the ratio is less than 0: 4.0 or exceeds this ratio, the viscosity of the reaction products of these three becomes high, the polymer is generated, and the two products in one molecule are inevitably increased. The hydroxycarboxylic acid having a hydroxyl group and the diisocyanate compound are not preferable because they may remain in the reaction product as they are,

The equivalent ratio of monofunctional alcohol is 1.0.
When it is less than 100%, the viscosity is inevitably increased during the reaction with the copolymer (A) of the ethylenically unsaturated monomer and the ethylenically unsaturated monomer having a hydroxyl group. It is not appropriate because it will gel.

On the other hand, when it exceeds 1.1, the resulting reaction products of these three components, the ethylenically unsaturated monomer and the ethylenically unsaturated monomer having a hydroxyl group are used together. In either case, the reaction efficiency with the polymer (A) is lowered, and the water dispersibility and water resistance are deteriorated.

One hydroxyl group is contained in one molecule, which is an essential component of the resin composition for water-based paints of the present invention.
Or a hydroxycarboxylic acid having two hydroxyl groups,
The reaction product with diisocyanate is generally prepared as follows.

The preparation method is not particularly limited, but it can be prepared by various known and conventional methods. Of these, only representative ones are exemplified, and the monohydroxycarboxylic acid and the diisocyanate compound are reacted in a nitrogen stream with stirring in a temperature range from room temperature to about 100 ° C. Is to do.

If the reaction heat cannot be controlled, one of the raw materials may be dropped. At this time, a reaction catalyst may or may not be used, but if only representative examples of such a reaction catalyst are given, dibutyltin dilaurate, dibutyltin dioctate, potassium acetate, stearic acid can be used. Examples thereof include metal salts such as zinc and tin octylate, and nitrogen-containing compounds such as triethylamine, triethylenediamine and morpholine.

When the viscosity of the reaction product becomes high, the following solvent may be allowed to coexist in advance to carry out the reaction. The solvent that can be used is not particularly limited, but if only representative ones among them are exemplified, benzene, toluene, xylene, methyl acetate, ethyl acetate, n-butyl acetate, The various ones mentioned above, such as isobutyl acetate, cyclohexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, cellosolve acetate, tetrahydrofuran or cyclohexanone.

To give another example, the reaction of dihydroxycarboxylic acid and diisocyanate compound is carried out in a nitrogen stream while stirring at a temperature range from room temperature to about 100 ° C. It is a thing.

The free isocyanate group content (N
When the CO%) reaches a predetermined value, monofunctional alcohol is added to continue the reaction. If the reaction heat cannot be controlled, there is also a method of dropping one of the raw materials. At this time, the reaction catalyst may or may not be used, but as such a reaction catalyst,
Various types as described above are used.

Further, when the viscosity of the reaction product becomes high, the reaction may be carried out in the state where various solvents as mentioned above are coexisted in advance.

There are no particular restrictions on the mono- or dihydroxycarboxylic acid used in these reactions, but if only representative ones are exemplified, hydroxypivalic acid, Glycolic acid, lactic acid, 3-hydroxypropionic acid, 2-
Hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyisobutyric acid, 2-hydroxy-2-
Methyl propionic acid,

3-hydroxyvaleric acid, 5-hydroxyvaleric acid, 10-hydroxyoctadecanoic acid, 2-hydroxycyclohexanecarboxylic acid, citric acid, tartaric acid, dimethylolpropionic acid, dimethylolbutanoic acid,
3-hydroxyglutaric acid, L-leucinic acid, α, β-
Examples include hydroxyhydrocinnamic acid, glyceric acid, mandelic acid or malic acid. Of course, these may be used alone or in combination of two or more kinds.

Similarly, the diisocyanate compound is not particularly limited, but if only typical ones are exemplified, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, m -Xylylene diisocyanate, p-xylylene diisocyanate, hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, lysine diisocyanate (scientific name is 2,6-diisocyanate methylcaproate),

4,4-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or -2,6) -diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate or dimer acid. Such as diisocyanate. Of course, these may be used alone or in combination of two or more kinds.

Similarly, although there is no particular limitation on monofunctional alcohols, only typical ones among them are exemplified by methyl alcohol, ethyl alcohol, n-propyl alcohol and isopropyl. Alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert
-Butyl alcohol, n-amyl alcohol, isoamyl alcohol, tert-amyl alcohol, neopentyl alcohol,

N-hexyl alcohol, cyclohexyl alcohol, n-heptyl alcohol, n-octyl alcohol, capryl alcohol, n-nonyl alcohol, n-decyl alcohol, lauryl alcohol, mystyryl alcohol, cetyl alcohol, stearyl alcohol,

Allyl alcohol, furfuryl alcohol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate. Or β
-Including hydroxypropylmethacrylate,

"UNIOX M-400, M-55
0, M-1000, M-2000 or M-400
0 "[above, product of NOF CORPORATION]," M-PEG "
CP400, CP2500 or CP5000 "[above, Dai-ichi Kogyo Seiyaku Co., Ltd. product] and the like. They are,
Of course, each may be used alone or in combination of two or more.

Further, the polyoxyalkylene glycol and / or polyoxyalkylene bisphenol A ether and the diisocyanate compound and the monofunctional alcohol are reacted at an equivalent ratio of 2.0: 4.0: 1.0 to 1.1. Is appropriate.

Polyoxyalkylene glycol and /
Alternatively, polyoxyalkylene glycol is first reacted with polyoxyalkylene bisphenol A ether, diisocyanate compound, and monofunctional alcohol at an equivalent ratio of 2.0: 4.0: 1.0 to 1.1. And / or polyoxyalkylene bisphenol A
The equivalent ratio of ether and diisocyanate compound, respectively,

When it is less than 2.0: 4.0 or exceeds this ratio, the viscosity of the reaction product is inevitably increased or polymerized,
Polyoxyalkylene glycol, polyoxyalkylene bisphenol A ether and / or diisocyanate compound are not preferable because they may remain in the reaction product as they are,

The equivalent ratio of monofunctional alcohol is 1.
When it is less than 0, the reaction product and
During the reaction with the copolymer (A) of the ethylenically unsaturated monomer and the ethylenically unsaturated monomer having a hydroxyl group, the viscosity becomes abnormally high or gelation occurs, which is appropriate. Without

On the other hand, when it exceeds 1.1, the reaction product is inevitably reacted with the copolymer (A) of the ethylenically unsaturated monomer and the ethylenically unsaturated monomer having a hydroxyl group. In both cases, the efficiency is lowered and the water dispersibility and the pigment dispersibility are deteriorated, which is not preferable.

Similarly, it is suitable to carry out the reaction at an equivalent ratio of polyoxyalkylene glycol monoalkyl ether to diisocyanate compound of 1.0 to 1.1: 2.0.

The reaction is carried out with the equivalent ratio of the polyoxyalkylene glycol monoalkyl ether and the diisocyanate compound being 1.0 to 1.1: 2.0 so that the reaction is carried out in the equivalent amount of the polyoxyalkylene glycol monoalkyl ether. When the ratio is less than 1.0, unreacted diisocyanate compound will remain in the reaction product,

Further, during the reaction between the ethylenically unsaturated monomer and the copolymer (A) of the ethylenically unsaturated monomer having a hydroxyl group, the viscosity becomes abnormally high or gelation occurs. Is not appropriate, while the equivalence ratio is 1.1.
If it exceeds, the reaction efficiency between the reaction product and the copolymer (A) of the ethylenically unsaturated monomer and the ethylenically unsaturated monomer having a hydroxyl group will inevitably decrease, and In both cases, dispersibility and water resistance are deteriorated, which is not preferable.

These reaction products are prepared as follows. The preparation method is not particularly limited, and can be carried out by various known and conventional methods. Among them, particularly representative ones are exemplified, polyoxyalkylene glycol and / Or polyoxyalkylene bisphenol A ether and diisocyanate compound in a nitrogen stream while stirring, from room temperature to about 100 ° C
The reaction is carried out within the temperature range.

Then, when the NCO% reaches a predetermined value, monofunctional alcohol is added to continue the reaction. If the reaction heat cannot be controlled, there is also a method of dropping one of the raw materials. At this time, the reaction catalyst may or may not be used, but it goes without saying that various reaction catalysts as described above can be used if necessary, and the viscosity of the reaction product In the case of high temperature, it goes without saying that the above-mentioned solvent may be allowed to coexist in advance to carry out the reaction.

To give another example, polyoxyalkylene glycol monoalkyl ether,
The reaction with the diisocyanate compound is carried out in a temperature range of about 100 ° C. from room temperature in a nitrogen stream while stirring. At that time, if the reaction heat cannot be controlled, there is of course a method of dropping either raw material.

At this time, the reaction catalyst may or may not be used, but of course, if necessary, various reaction catalysts as described above can be used, and In the case where the viscosity of the reaction product becomes high, it goes without saying that the various solvents described above may be allowed to coexist in advance to carry out the reaction.

The polyoxyalkylene glycol to be used in the reaction is not particularly limited, but if only typical ones are exemplified, "PEG 200, 300, 400,
600, 1000, 1500, 1540, 2000, 4
000, 6000, 6000P, 11000 or 2
0000 ”;“ Uniol D-400 or D-2
000 ”or“ Unisafe DC-1100 or DC-1800 [above, products of NOF CORPORATION], etc.,

Furthermore, "PEG 200, 300, 4
00, 600, 1000, 1500, 1540, 200
0, 4000, 6000, 10000 or 2000
0 ”[above, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] and the like. Of course, these may be used alone or in combination of two or more kinds.

Similarly, the polyoxyalkylene bisphenol A ether used in the reaction is not particularly limited, but only typical ones among them will be mentioned. Uniall DA-350F, DA-400, DB-400, DB
-900 or DB-2000 "[above, NOF Corporation product] and the like. Of course, these may be used alone or in combination of two or more kinds.

Furthermore, the polyoxyalkylene glycol monoalkyl ether used in the reaction is also not particularly limited, but only representative ones among them are exemplified. For example, "UNIOX M-400, M-550, M-
1000, M-2000 or M-4000 "[above, product of NOF CORPORATION]; or" M-PEG C "
P400, CP2500 or CP5000 "[above, product of Dai-ichi Kogyo Seiyaku Co., Ltd.] and the like. They are,
Of course, each may be used alone or in combination of two or more.

Similarly, the diisocyanate compound is not particularly limited, but if only representative ones of them are illustrated, as described above, 2,4
-Toluene diisocyanate, 2,6-toluene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, lysine diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), methylcyclohexane Examples thereof include -2,4 (or -2,6) -diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate and dimer acid diisocyanate. It goes without saying that these may be used alone or in combination of two or more kinds.

Similarly, as the monofunctional alcohol, as described above, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s.
ec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, t
ert-amyl alcohol,

Neopentyl alcohol, n-hexyl alcohol, cyclohexyl alcohol, n-heptyl alcohol, n-octyl alcohol, capryl alcohol, n-nonyl alcohol, n-decyl alcohol, lauryl alcohol, mystyryl alcohol, cetyl alcohol, stearyl alcohol. ,

Allyl alcohol, furfuryl alcohol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl Needless to say, various compounds such as acrylate and β-hydroxypropyl methacrylate can be used, and each of these compounds may be used alone or in combination of two or more kinds.

The above is a method for preparing a reaction product of a diisocyanate compound and a hydroxyl group-containing substance. In this way, not only the reaction is performed separately, but finally the desired reaction product is obtained. (That is, a monoisocyanate compound) is obtained,

Hydroxycarboxylic acid, polyoxyalkylene glycol, polyoxyalkylene bisphenol A ether and / or polyoxyalkylene glycol monoalkyl ether, monofunctional alcohol, and diisocyanate compound were charged at once. Of course, the reaction may be carried out in a so-called batch reaction mode.

Next, a copolymer (A) of an ethylenically unsaturated monomer and a hydroxyl group-containing ethylenically unsaturated monomer,
Let us now turn to the description of the reaction with the monoisocyanate compound described above.

As the modified resin which is the final object of the present invention, that is, a copolymer (A) of an ethylenically unsaturated monomer and a hydroxyl group-containing ethylenically unsaturated monomer; hydroxycarboxylic acid A reaction product (B-1) and / or (B-2) between the diisocyanate compounds; a reaction product (C-1) between the polyoxyalkylene glycol-diisocyanate compound; a polyoxyalkylene bisphenol A ether-diisocyanate compound As the reaction product (C-2) and / or the reaction product (C-3) between the polyoxyalkylene glycol monoalkyl ether-diisocyanate compound, the solid content acid value is in the range of about 15 to about 100. In addition, polyoxyalkylene glycol, polyoxyalkylene bisphenol Ethers and / or content of the polyoxyalkylene glycol monoalkyl ether, the use of those forms that are adjusted in a range of Taiyaku 0.1 Taiyaku 25.0% by weight, is suitable.

When the acid value of the solid content is less than about 15, it is difficult to dissolve in water, which is unsatisfactory.
If it exceeds about 100 and becomes too large, the water resistance of the coating film will inevitably decrease, and in any case, it is not preferable. Preferably, the acid value of solid content is in the range of about 20 to about 85.

Further, polyoxyalkylene glycol,
When the content of polyoxyalkylene bisphenol A ether and / or polyoxyalkylene glycol monoalkyl ether is less than about 0.1% by weight,
Inevitably, the dispersibility of carbon black deteriorates,

On the other hand, if the amount exceeds about 25% by weight and becomes too large, the water resistance is inevitably deteriorated, which is not preferable in any case. Preferably about 0.
It is in the range of 5 to about 20.0% by weight.

The preparation method is not particularly limited, and various known and conventional methods can be used. Of these, only typical ones can be used. Copolymer (A) of unsaturated monomer and hydroxyl group-containing ethylenically unsaturated monomer
When,

Reaction product between hydroxycarboxylic acid and diisocyanate compound; reaction product between polyoxyalkylene glycol and diisocyanate compound, reaction product between polyoxyalkylene bisphenol A ether and diisocyanate compound and / or polyoxyalkylene glycol The reaction product between the monoalkyl ether-diisocyanate compound,

The reaction is carried out in a temperature range from room temperature to about 100 ° C. in a nitrogen stream while stirring.

When the viscosity of these various types of reaction products is high, benzene, toluene, xylene, methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, acetone, methyl ethyl ketone, methyl are used. The above-mentioned solvent such as isobutyl ketone, methyl isobutyl ketone, cellosolve acetate, tetrahydrofuran or cyclohexanone may be allowed to react in advance in the coexisting state.

After the reaction is completed, it is important to add the following hydrophilic solvent and to keep the inside of the reaction vessel in a vacuum state with a vacuum pump to remove the non-hydrophilic solvent. is there. In this case, the boiling point of the hydrophilic solvent is
The first condition is that it is higher than the boiling point of the non-hydrophilic solvent.

The hydrophilic solvent is not particularly limited, but includes the followings.

Of these, only typical ones will be exemplified. Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether,
Propylene glycol monoisobutyl ether, propylene glycol mono-tert-butyl ether,

Examples include methyl cellosolve, ethyl cellosolve, butyl cellosolve, isobutyl cellosolve, tert-butyl cellosolve, isopropyl cellosolve, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol or tert-butyl alcohol.

The modified resin obtained as described above is not particularly limited, but if only representative ones are exemplified, potassium hydroxide, sodium hydroxide, etc. , Various inorganic alkalis (among others, alkali metal salts); or ammonia,

Monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-n-propylamine, dimethyl n-propylamine, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-amino Ethyl ethanolamine,

It is neutralized with various amines such as N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine or N, N-dimethylpropanolamine. As the neutralizing agent, one kind or two or more kinds selected from each of the above listed compounds can be used, and the pH is adjusted to the range of 7 to 11.

The resin composition for an aqueous coating composition of the present invention thus obtained can be used as it is as an aqueous coating composition after being diluted with water to an appropriate viscosity and concentration. ,

Known and commonly used coating materials,
Pigments; various extender pigments such as calcium carbonate, silica, talc; anticorrosion pigments; defoamers; plasticizers; solvents; colorants;
Add various dryers such as cobalt naphthenate and lead naphthenate,

Further, it is also possible to use it by mixing with various water-soluble or water-dispersible resins such as amino resin, acrylic resin, polyester resin, epoxy resin, polyurethane resin, emulsion and latex. Is.

For example, if it is used as it is, it can be used as a room temperature dry paint, and of course, it can be used as a baking paint by adding an amino resin or the like. Further, depending on the design of the resin, it can be used as an ultraviolet curable paint, an electron beam curable paint, or the like.

The coating composition in these various forms can be coated by various known and commonly used coating methods such as dipping, brush coating, air spraying, airless spraying, electrodeposition coating or roll coating. I can.

In this case, iron, non-ferrous metal, plastic, paper, wood, fiber, concrete, slate, and the like can be given to exemplify only representative ones.

[0088]

EXAMPLES Next, the present invention will be described with reference to Examples and Comparative Examples.
More specifically, the invention is by no means limited to these examples. In the following, all parts and% are based on weight unless otherwise specified.

Example 1 A 5 liter glass flask equipped with a nitrogen gas inlet tube and equipped with a stirrer, a thermometer and a glass tube was charged with 2,000 parts of toluene, while blowing nitrogen gas. The temperature was raised to 110 ° C.

Then, 646 parts of methyl methacrylate, 634 parts of n-butyl acrylate and β
-Hydroxyethyl methacrylate 720 parts, 40 parts of "Perbutyl Z" [tert-butyl peroxybenzoate, which is a radical polymerization initiator manufactured by NOF CORPORATION], and 40 parts of toluene. The resulting mixture was added dropwise over 4 hours.

After that, the reaction was continued at the same temperature for 6 hours to obtain a copolymer. Hereinafter, this is abbreviated as (A-1), but this has a nonvolatile content of 5
It was 0.1%.

Separately, in a 3 liter glass flask equipped with a nitrogen gas introduction tube and equipped with a stirrer, a thermometer and a cooling tube, 2,4- / 2,6- = 80 /
18 (20 parts by weight) of toluene diisocyanate
9.3 parts and 126.2 parts of hydroxypivalic acid,
Charge 10 parts of "UNIOX M-550" [polyethylene glycol monomethyl ether manufactured by NOF CORPORATION] and 325.5 parts of ethyl acetate to obtain NCO%.
Was carried out at 60 ° C. until the ratio reached 7.0%. The reaction products obtained here are (B-
It was a mixture of 1) and (C-3). Hereinafter, each of these will be described as (B-1-1) and (C-3-
Abbreviated as 1).

Next, to this reaction mixture, 1,346.1 parts of the above-mentioned copolymer (A-1) was added, and the reaction temperature was set to 60 ° C. until the NCO% became 0.1% or less. The reaction was carried out. Further, 430.0 parts of butyl cellosolve was added, and toluene and ethyl acetate were removed by a vacuum pump while maintaining the temperature from 50 ° C to the maximum temperature of 110 ° C while stirring.

After that, the temperature was lowered to 50 ° C., and 108.0 parts of triethylamine was added to neutralize. The resin thus obtained has a nonvolatile content of 65.6%.
And the acid value of the solid content was 58.8.

Next, 361.8 parts of ion-exchanged water was added to 304.9 parts of this resin, and well stirred to obtain 666.7 parts of an aqueous dispersion.

As shown below, the coating composition (A)
Alternatively, according to the blending ratio as shown in (B), first, a coating material is prepared, and the average dry film thickness is 30 microns (μ
m) Paint it to the front and back,

For the coating composition (A), 10 at 20 ° C.
One day drying, while for coating composition (B), 15
Each of the coated plates that had been baked and dried at 0 ° C for 20 minutes was subjected to a water resistance test at 40 ° C for 10 days.

Further, each paint was placed in a 0.125 liter glass bottle and allowed to stand at room temperature for 10 days, and then the degree of change (pigment dispersibility) such as sedimentation state and separation of the pigment was observed. .

<< Coating Composition A >> Water Dispersion 266.7 parts “MA-100” [Carbon manufactured by Mitsubishi Kasei Co., Ltd.] 4.0 〃 “Homocal D” [Calcium carbonate manufactured by Shiraishi Industry Co., Ltd.] 24 .7 〃 "NS # 100" [Nitto Koka Co., Ltd. calcium carbonate] 24.7 〃 "BYK-080" [Germany Beak (BYK) 0.2 〃 Chemie defoamer] " SN-373 "[Antifoam manufactured by San Nopco Ltd.] 0.4〃

<< Coating Composition B >> Water Dispersion 240.0 Parts "S-695" [Dainippon Ink and Chemicals Incorporated 12.1〃 Methyletherified Melamine Resin] * "MA-100" (same as above) 4.0〃 "Homocal D" (same as above) 24.7〃 "NS # 100" (same as above) 24.7〃 "BYK-080" (same as above) 0.2〃 "SN-373" (same as above) 0.4 〃

* "S-695" is an abbreviation for "Watersol S-695".

Example 2 A nitrogen gas introducing pipe was attached, and a stirrer, a thermometer,
In a 1 liter glass flask equipped with a dropping funnel and a cooling tube, dimethylolpropionic acid of 95.
5 parts and 165.9 parts of n-butyl acetate were charged.

On the other hand, from the dropping funnel, 239.5 parts of hexamethylene diisocyanate was dropped, and the reaction was carried out at 80 ° C., and after confirming that the NCO% was 12.0%, 53.0 parts of n-butanol was added and the reaction was allowed to continue until the NCO% reached 5.4%. Hereinafter, the reaction product obtained here was converted into (B-2-
Abbreviated as 1).

Separately, 33.6 parts of hexamethylene diisocyanate and "Uniol D-2000" were placed in a 3 liter glass flask equipped with a nitrogen gas introduction tube, and further equipped with a stirrer, a thermometer and a cooling tube.
2 of [Polypropylene glycol manufactured by Nippon Oil & Fats Co., Ltd.]
00 parts and 103 parts of n-butyl acetate were charged.

At 80 ° C., the reaction was allowed to continue and NC
After confirming that the O% became 2.5%, 7.7 parts of n-butanol was added, and the reaction was carried out until the NCO% became 1.2%. Hereinafter, the reaction product obtained here is abbreviated as (C-1-1).

In addition, the copolymer (A
-1) of 741.1 parts and the total amount of the above-mentioned (B-2-1) were added, and the reaction was carried out at a reaction temperature of 80 ° C. until the NCO% became 0.1% or less.

Then, 470 parts of butyl cellosolve was added, and while raising the temperature from 50 ° C. to a maximum temperature of 110 ° C., the inside of the reaction vessel was kept in a vacuum state by a vacuum pump to remove n-butyl acetate and toluene. I'm sorry.

After that, the temperature is lowered to 50 ° C.,
72 parts of triethylamine was added to neutralize. The resin obtained here had a nonvolatile content of 64.7% and a solid content acid value of 38.5.

Next, 357.6 parts of ion-exchanged water was added to 309.1 parts of this resin and stirred well to obtain 666.7 parts of an aqueous dispersion. After that, it was made into a paint in the same manner as in Example 1, and the water resistance test and the pigment dispersibility test were performed.

Comparative Example 1 A nitrogen gas introduction pipe was attached, and a stirrer, a thermometer,
A 3 liter glass flask equipped with a dropping funnel and a cooling tube was charged with 29.4% of hydroxypivalic acid.
Department, "UNIOX M-1000" [NOF CORPORATION]
Made of polyethylene glycol monomethyl ether]
00 parts and 88.7 parts of methyl ethyl ketone were charged.

On the other hand, from the dropping funnel, 77.5 parts of isophorone diisocyanate was appropriately added, and the reaction was carried out at 60 ° C. until the NCO% reached 5.0, and (B'-
A mixture of 1) and (C-3) was obtained. Hereinafter, these reaction products are respectively (B'-1-1) and (C-3-
2) is abbreviated.

Then, 1,878.6 parts of the copolymer resin (A-1) prepared in Example 1 was added and the NCO was again added.
The reaction was carried out at 60 ° C. until the% became 0.1% or less. Further, 260 parts of isopropyl cellosolve and 260 parts of butyl cellosolve were added, and while stirring, 110
While raising the temperature to 0 ° C., the inside of the reaction vessel was kept in a vacuum state with a vacuum pump to remove methyl ethyl ketone and toluene.

Subsequently, the temperature was lowered to 50 ° C. and 25 parts of triethylamine were added to neutralize. The resin obtained here has a nonvolatile content of 65.8%,
Moreover, the acid value of the solid content was 13.7.

Next, 362.7 parts of ion-exchanged water was added to 304.0 parts of this resin and stirred well to obtain 666.7 parts of an aqueous dispersion, which was dispersed in water. I couldn't get it after all because I didn't like it. Therefore, it was also impossible to paint.

Comparative Example 2 A nitrogen gas introducing pipe was attached, and a stirrer, a thermometer,
A 3 liter glass flask equipped with a dropping funnel and a cooling tube was charged with 220.9% of hydroxypivalic acid.
Parts, 50.0 parts of "UNIOX M-2000" [polyethylene glycol monomethyl ether manufactured by NOF CORPORATION], and 252.7 parts of n-butyl acetate were charged.

From the dropping funnel, 318.7 parts of hexamethylene diisocyanate was added, and the NCO% was 9.5%.
The reaction was carried out at 80 ° C. until it became, and a mixture of (B′-1) and (C-3) was obtained as a reaction product. Hereinafter, these reaction products are abbreviated as (B'-1-2) and (C-3-3), respectively.

819.2 parts of the copolymer resin (A-1) obtained in Example 1 was added to this reaction product, and the NCO% was 0.1% or less at the same temperature. The reaction was allowed to continue.

Further, 350 of isopropyl cellosolve was added.
． Add 0 parts and stir while stirring from 50 ° C up to 110 ° C
The temperature inside the reaction vessel was maintained in a vacuum state with a vacuum pump while the temperature was raised to 1 to remove toluene and n-butyl acetate.

Subsequently, the temperature was lowered to 50 ° C. and 189 parts of triethylamine were added to neutralize. The resin obtained here has a nonvolatile content of 64.5%,
Moreover, the acid value of the solid content was 104.5.

Then, to 310.1 parts of this resin, 356.6 parts of ion-exchanged water was added and stirred well to obtain 666.7 parts of an aqueous dispersion. After that, it was made into a paint in the same manner as in Example 1, and the water resistance test and the pigment dispersibility test were performed.

Comparative Example 3 A nitrogen gas introduction pipe was attached, and a stirrer, a thermometer,
In a 3 liter glass flask equipped with a dropping funnel and a cooling tube, 126.2 of hydroxypivalic acid was added.
Parts and 133.8 parts of ethyl acetate.

On the other hand, from the dropping funnel, 2, 4
186.2 parts of toluene diisocyanate of − / 2, 6− = 80/20 (weight part ratio) was added dropwise, and NCO% was 1
The reaction was carried out at 60 ° C. until it reached 0.1%.
Hereinafter, the reaction product obtained here is abbreviated as (B-1-2).

Then, 1,372.7 parts of the copolymer resin (A-1) obtained in Example 1 was added, and the NCO% became 0.1% or less at the same temperature. The reaction was allowed to continue.

Further, 200 parts of butyl cellosolve,
230 parts of isopropyl cellosolve was added, and while stirring, the inside of the reaction vessel was kept in a vacuum state by a vacuum pump at 50 ° C. to 110 ° C. to remove toluene and ethyl acetate.

After that, the temperature was lowered to 50 ° C., and 108.0 parts of triethylamine was added to neutralize. The resin obtained here has a nonvolatile content of 65.2%.
And the solid content acid value was 58.9.

Then, 360.0 parts of ion-exchanged water was added to 306.7 parts of this resin and well stirred to obtain 666.7 parts of an aqueous dispersion. After that, it was made into a paint in the same manner as in Example 1, and the water resistance test and the pigment dispersibility test were performed.

Comparative Example 4 A nitrogen gas introduction pipe was attached, and a stirrer, a thermometer,
In a 3 liter glass flask equipped with a dropping funnel and a cooling tube, 126.2 of hydroxypivalic acid was added.
Department, "UNIOX M-4000" [NOF CORPORATION]
Made of polyethylene glycol monomethyl ether]
60 parts and 229 parts of ethyl acetate were charged.

On the other hand, from the dropping funnel, 2, 4
-14,2 parts of toluene diisocyanate of-/ 2,6- = 80/20 (weight part ratio) was added dropwise, and reaction was carried out at 60 ° C until NCO% was 4.7%,
As a reaction product, a mixture of (B-1) and (C'-3) was obtained. Hereinafter, these reaction products are respectively (B-
It is abbreviated as 1-3) and (C'-3-1).

Subsequently, 927.9 parts of the copolymer resin (A-2) obtained in Example 1 was added, and the reaction was carried out at the same temperature until the NCO% became 0.1% or less. Allowed me to continue.

Furthermore, 43 of isopropyl cellosolve was added.
Add 0.0 parts and, with stirring, from 50 ° C to a maximum of 110
At 0 ° C., the inside of the reaction vessel was kept in a vacuum state by a vacuum pump to remove toluene and ethyl acetate.

Subsequently, the temperature was lowered to 50 ° C., and 108.0 parts of triethylamine was added for neutralization. The resin obtained here has a nonvolatile content of 64.9%.
And the acid value of the solid content was 59.1.

Next, 358.5 parts of ion-exchanged water was added to 308.2 parts of this resin and well stirred to obtain 666.7 parts of an aqueous dispersion. Thereafter, it was made into a coating material in the same manner as in Example 1, and a water resistance test and a pigment dispersion test were conducted. The results are summarized in Table 1.

[0133]

[Table 1]

<Evaluation Criteria for Water Resistance Test> ○ ………… Blanching, not observed × ………… Blanching is remarkable

<Evaluation Criteria for Pigment Dispersibility Test> ∙: No pigment settling, and strong blackness in the entire coating × ………… Significant settling of pigment, and the entire coating is whitish

[0136]

As is clear from the above results, the resin composition for water-based paints of the present invention can be dried at room temperature and baked under a wide range of drying conditions and various coating conditions. It is possible to provide an extremely useful water-based paint having excellent pigment dispersibility and water resistance.

Claims (4)

[Claims] 1. A copolymer (A) of an ethylenically unsaturated monomer and an ethylenically unsaturated monomer having a hydroxyl group via an isocyanate compound is added to a hydroxycarboxylic acid and polyoxyalkylene glycol, A resin composition for an aqueous coating composition, which is obtained by dispersing a modified resin obtained by addition reaction of polyoxyalkylene bisphenol A ether and / or polyoxyalkylene glycol monoalkyl ether in water. 2. The above modified resin is a reaction product of a hydroxycarboxylic acid (b-1) having one hydroxyl group in one molecule and a diisocyanate compound (b-2) (B-
1) and / or a reaction product of a hydroxycarboxylic acid (b-3) having two hydroxyl groups in one molecule, a diisocyanate compound (b-2) and a monofunctional alcohol (b-4) (B -2) and; polyoxyalkylene glycol (c-1) and diisocyanate compound (b-2)
With a monofunctional alcohol (b-4) (C
-1); Polyoxyalkylene bisphenol A ether (c-2) and diisocyanate compound (b-2)
With a monofunctional alcohol (b-4) (C
-2) and / or a polyoxyalkylene glycol monoalkyl ether (c-3) and a reaction product (C-3) of the diisocyanate compound (b-2); an ethylenically unsaturated monomer, and a hydroxyl group. The composition according to claim 1, which is obtained by reacting the copolymer (A) with an ethylenically unsaturated monomer contained therein. 3. The above-mentioned modified resin is a reaction product of a hydroxycarboxylic acid (b-1) having one hydroxyl group in one molecule and a diisocyanate compound (b-2) (B-
1) and / or a reaction product of a hydroxycarboxylic acid (b-3) having two hydroxyl groups in one molecule, a diisocyanate compound (b-2) and a monofunctional alcohol (b-4) (B -2) and; polyoxyalkylene glycol (c-1) and diisocyanate compound (b-2)
With a monofunctional alcohol (b-4) (C
-1); Polyoxyalkylene bisphenol A ether (c-2) and diisocyanate compound (b-2)
With a monofunctional alcohol (b-4) (C
-2) and / or a polyoxyalkylene glycol monoalkyl ether (c-3) and a reaction product (C-3) of the diisocyanate compound (b-2); an ethylenically unsaturated monomer, and a hydroxyl group. It is obtained by reacting the copolymer (A) with an ethylenically unsaturated monomer which has, and has a solid content acid value in the range of 15 to 100. The composition according to 2. 4. The reaction product (B-) of the above-mentioned modified resin, which is obtained by reacting a hydroxycarboxylic acid (b-1) having one hydroxyl group in one molecule with a diisocyanate compound (b-2).
1) and / or a reaction product of a hydroxycarboxylic acid (b-3) having two hydroxyl groups in one molecule, a diisocyanate compound (b-2) and a monofunctional alcohol (b-4) (B -2) and; polyoxyalkylene glycol (c-1) and diisocyanate compound (b-2)
With a monofunctional alcohol (b-4) (C
-1); Polyoxyalkylene bisphenol A ether (c-2) and diisocyanate compound (b-2)
With a monofunctional alcohol (b-4) (C
-2) and / or a polyoxyalkylene glycol monoalkyl ether (c-3) and a reaction product (C-3) of the diisocyanate compound (b-2); an ethylenically unsaturated monomer, and a hydroxyl group. It is obtained by reacting the copolymer (A) with an ethylenically unsaturated monomer which has, and has a solid content acid value in the range of 15 to 100, and has the above polyoxy group. The content of the alkylene glycol (c-1), the polyoxyalkylene bisphenol A ether (c-2) and / or the polyoxyalkylene glycol monoalkyl ether (c-3) is within the range of 0.1 to 25.0% by weight. The composition according to claim 1 or 2, which is