JPS5896643A - Carbonyl group-containing copolymer aqueous dispersion composition - Google Patents

Abstract

PURPOSE:To obtain titled composition capable of forming films of markedly improved water, chemical, solvent and blocking resistance and adhesiveness to various coats, by incorporating a specific copolymer aqueous dispersion with a specific water-soluble acid hydrazide-based polymer. CONSTITUTION:The objective composition comprising (A) an aqueous dispersion of a copolymer consisting of (i) 99.5-25wt% of a monomer unit selected from acrylic acid 1-8C n-alkyl ester and methacrylic acid 2-8C n-alkyl esters, (ii) 0.1-2.0wt% of a carbonyl group-contg. monomer unit having in one molecule, at least one aldehyde or keto group and double bond, (iii) 0.5-10wt% of a third monomer unit selected from 3-5C monoolefinc unsaturated carboxylic acids, etc. and (iv) 0-74.4wt% of a fourth monomer unit selected from ethylene, acrylonitrile, etc. and (B) a water-soluble acid hydrazide-based polymer having in one molecule, at least two hydrazide groups.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous dispersion composition of a carbonyl group-containing copolymer that provides a film (coating) having excellent physical properties.

(Japanese Unexamined Patent Application Publication No. Shoj/Bar No. 111, Japanese Unexamined Patent Publication No. J Goo/Kousan No. 3). It is noteworthy that such an aqueous dispersion easily forms a coating film at a film-forming temperature of J to 2JC, and provides a coating film with excellent adhesion to adherends such as cloth and metal.

For example, in JP-A No. 8T≠-7Hiro≠≠3λ Publication KFi, a water-soluble aliphatic dihydrazine compound, a water-soluble zinc salt, and a manganese are added to an aqueous dispersion of a carbonyl group-containing copolymer having a glass transition temperature of O to jOC. An aqueous dispersion containing salt, cobalt salt or iron salt is described above, and the coating film was 2kll/j, jc in the roll-strip test.
It is described that it has an adhesion force of m. However, the water resistance, chemical resistance, and
However, there were drawbacks in that the scratch resistance and adhesive strength to various coatings were not necessarily sufficient.

The present invention provides a specific aqueous dispersion of a carbonyl group-containing copolymer containing a water-soluble acid hydrazide polyamide containing at least two hydrazide groups in the molecule! - an aqueous copolymer dispersion that provides a coating film with significantly improved properties such as water resistance, chemical resistance, solvent resistance, anti-sticking property, and adhesion to various coatings. There are some cases in which liquid compositions cannot be obtained.

That is, the present invention provides (A) (a) n-alkyl ester of acrylic acid having 7 to 1 carbon atoms, n-alkyl ester of methacrylic acid having 2 to 1 carbon atoms, saturated carboxylic acid vinyl ester, / , a monomer unit selected from 3-dienes 2! ~23 weight N, (b) carbonyl group-containing monomer unit having at least 7 aldo or keto groups and a double bond in the molecule 0, 7 to -0 weight 9, (c
) Monoolefinically unsaturated carboxylic acids having 3 to 3 carbon atoms, monoolefinically unsaturated carboxylic acid amides, he-alkyl and/or 8-alkylol derivatives of the same unsaturated carboxylic acid amides, olefinically unsaturated sulfonic acids Monomer units selected from the following reviews: 0. j~IO weight 9, sequence i
c (d) methyl methacrylate, vinyl aromatic compound,
Tertiary butyl acrylate, vinyl halide, ethylene,
CB) A water-soluble compound having at least one hydrazide group in the molecule, is added to an aqueous dispersion of a heavy type combination containing monomer units θ to 74'S44 weight 9 selected from the group consisting of acrylonitrile and methacrylonitrile. - and a dracite polymer.

The aqueous copolymer dispersion (A) of the present invention K is an n-alkyl ester of acrylic acid having carbon atoms/~j, an n-alkyl ester of methacrylic acid having 2 to g carbon atoms, and a saturated vinyl carboxylate. The monomer (a) selected from the group consisting of esters, l,3-dienes, and! Weight circle, carbonyl group-containing monomer unit Cb) having at least 47 aldo groups or L poppy groups and a double bond polymerizable in the molecule. Monoolefinically unsaturated carboxylic acids, unsaturated carboxylic acid amides, N-alkyl and/or N-alkylol derivatives of unsaturated carboxylic acid amides, monoolefins having /~20 weight 9 weight -j carbon atoms a monomer unit (c) selected from the group consisting of sexually unsaturated sulfonic acids;
o, j to IO weight 9, and a monomer unit selected from the group consisting of methyl methacrylate, vinyl aromatic compounds, tertiary butyl acrylate, vinyl halides, ethylene, acu-9a nitrile, and methacrylonitrile. (d) is θ~7
4/, 4I is a heavy gold-containing aqueous dispersion containing 9 by weight.

As the monomer forming the monomer unit (a),
For example, esters of alcohols having 2 to 2 carbon atoms, such as ethanol, isopropanol, n-propanol, n-7'tanol, isobutanol, or -monoethyl alcohol with acrylic or methacrylic acid; Examples include methyl acrylate, vinyl acetate, vinyl propionate, and butadiene. Particularly preferred monomers are coethylhexyl acrylate, n-butyl acrylate, and ethyl acrylate. Two or more types of these monomer units (a) may be contained in the copolymer.

The monomer forming the monomer unit Cb) is a monomer having at least 7 aldo groups or keto groups and a polymerizable double bond in the molecule, that is, a polymerizable sonoolefinic aldo compound. or a keto compound. Of course, compounds having only a carboxyl group (-C-OH) are not included in the monomers. Examples of the monomers include acrolein, diacetone acrylamide,
Hornrustyrol, a vinyl alkyl ketone having ~7 carbon atoms (e.g. vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), with the general formula (wherein R' is H or aCH, R"FiH or % R'' is an alkyl group having 7 to 3 carbon atoms, R is an alkyl group having 1 to 3 carbon atoms, or Examples include methacrylic) oxy-panal, diacetone acrylate, acetonitrile acrylate, diacetone acrylate, diacetone methacrylate, λ-hydroxypropyl acrylate-acetylacetate, butanediol-/, teracrylate-acetylacetate, and the like. Particularly preferred are diacetone acrylamide, acrolein and vinyl ethyl ketone. Two or more of these monomer units (b) a may be contained in the copolymer.

The monomer forming the monomer unit (c) is as follows:
Monoolefinically unsaturated carboxylic acids having 3 to j carbon atoms and the above-mentioned specific derivatives of the unsaturated carboxylic acids are used, but the unsaturated carboxylic acids may be senocarboxylic acids or dicarboxylic acids. Good too. Examples of the monoolefinically unsaturated carboxylic acids and their derivatives include acrylic acid, methacrylic acid, itaconic acid, maleic acid, amides of these acids, and N-alkyl and/or N-alkyl of amides of these acids. Roll derivative (
For example, N-methylacrylamide, N-isobutylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethodimethylacrylamide, N-n-butoxymethylacrylamide. , N-impropoxymethacrylamide), and the like. In addition, the monomer unit (C
) can also be used monoolefinically unsaturated sulfonic acids such as vinylsulfonic acid, methylacrylamidopropanesulfonic acid, etc. Two or more types of these monomer units (C) may be contained in the copolymer.

The monomer that forms the monomer unit (d) is:
Examples include methyl methacrylate, vinyl aromatic compounds (eg styrene), vinyl halides (eg vinyl chloride, vinylidene chloride), ethylene, acrylonitrile, methacrylonitrile. These/these monomer units (d)
h may not be contained in the copolymer, or two or more types thereof may be contained.

To explain the effects of each of these monomer units contained in the copolymer, the monomer unit (a) - imparts flexibility to the coating film of the aqueous dispersion composition of the present invention. However, if the monomer unit is not contained in a predetermined amount, the coating film becomes too hard, loses flexibility, and increases K and film-forming temperature, which is not preferable.

The monomer unit (b) has a carbonyl group (that is, an aldo group or a keto group) that is a water-soluble acid hydrazide poly! -CB
) to give a crosslinked structure and improve the physical properties of the coating film.

If the same monomer units are not contained in a predetermined amount, the crosslinking density of the coating film will decrease, resulting in poor water resistance, chemical resistance, blocking resistance, etc. of the coating film.

Monomer unit (e) a. Since it is a hydrophilic monomer, it improves the stability of the dispersed monomer during pentapolymerization. !
Furthermore, in the case of a monoolefinic unsaturated carboxylic acid, it acts to further improve the adhesion of the coating film to the substrate.

For example, an N-alkylol derivative of an unsaturated carboxylic acid amide acts as a crosslinking monomer within or between polymer particles and improves the physical properties of the coating film.

Monomer unit (d) #i contributes to imparting hardness to the coating film of the aqueous dispersion composition of the present invention.

To produce the copolymer dispersion used for preparing the aqueous copolymer dispersion composition of the present invention, the monomer units (a), (
b) Emulsion polymerization is carried out in an aqueous dispersion using a predetermined proportion of each of the above-mentioned monomers forming , (C) and (d).

A suitable emulsifier and polymerization initiator are used in the emulsion polymerization.

Examples of emulsifiers include higher alcohol sulfate salts, alkylbenzene sulfonates, and polyoxyethylene alkyl salts. -) Anionic surfactants such as 1% polyoxyethylene alkylphenol ether sulfate salts, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, ethylene oxide propylene oxide block copolymers, and sorbitan derivatives. used.

Examples of polymerization initiators include persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide, peroxides such as benzoyl peroxide 1, cumene hydroperoxide, and tertiary butyl hydroperoxide. Azobisisobutynitrile and the like are used. Particularly preferred are water-soluble initiators and redox initiators.

The water-soluble acid hydrazide polymer having at least one hydrazide group in the molecule used in the present invention has the following formula: Yes, A is each unit of acryland, methacrylamide, acrylic ester, methacrylic ester, or maleic anhydride, and B can be copolymerized with acryland, methacrylamide, acrylic ester, methacrylic ester, or maleic anhydride. other monomeric units. In addition, l, m, and arithmetic are each formula below. +Swearing Tokame= Indicates the number that satisfies 100 moles nine. ] The water-soluble acid hydrazide polymer having at least two hydrazide groups in the molecule, which is preferably a polymer represented by the following formula, is described, for example, in JP-A-Shojjt-1. ! Since it is described in detail in Japanese Patent Application No. 33, a detailed explanation of the polymer will be omitted.

The blending ratio of the copolymer aqueous dispersion (A) and the water-soluble acid hydrazide polymer CB) in the aqueous dispersion composition of the present invention is determined based on the aldo groups of the copolymer in the copolymer aqueous dispersion (A) and /or hydrazide group of water-soluble acid hydrazide polymer (B) is 0.02 to 7 moles of keto group
The ratio is preferably from 0 to 1 J mol.

In the aqueous dispersion composition of the present invention, a hydrazine derivative having two hydrazide groups, such as adipic acid dihydrazide and sebacic acid dihydrazide, can be used in combination with the water-soluble acid hydrazide polymer.

Aqueous dispersion composition KFi of the present invention, optionally water-soluble heavy metal salts such as zinc sulfate, manganese sulfate, cobalt sulfate, zinc acetate, manganese acetate, cobalt acetate, lead acetate, zinc nitrate, manganese nitrate, cobalt nitrate, nitric acid A small amount of lead, zinc nitrite, lead nitrite, etc. can be blended.

Additionally, the aqueous dispersion compositions of the present invention include nine pigments commonly known in the paint formulation art, calcium carbonate,
Talc, clay! Extending pigments such as squid powder and palite,
Potassium, sodium or ammonium salts of condensed phosphoric acids such as hexametaphosphoric acid, sodium or ammonium salts of polyacrylic acids, common anionic or nonionic surfactants, methylcellulose, ethylcellulose, propylcellulose, carboxymethylcellulose,
A dispersant and thickener such as polyvinyl alcohol can be added.

When the aqueous dispersion composition of the present invention is cloth-dried, the aldo group or keto group in the copolymer and the hydrazide group in the water-soluble acid hydrazide polymer easily react to form a crosslinked structure. The coating film has excellent solvent resistance, durability, blocking resistance, and yellowing resistance, and also has good adhesion to coatings such as vinyl chloride resin and alkyd resin. . Therefore, the aqueous dispersion composition of the present invention can be used for gloss paints, mastic top coat materials,
It can be used as a soft mastic top coat, a coating for slate capes, and is also useful as a repair agent for old paint coatings.

Below, production examples of acid hydrazide polymers, examples, and comparative examples will be described in more detail.

Parts and circles in these examples are by weight unless otherwise noted.

Acid hydrazide polymer production example: In a reaction vessel equipped with a temperature controller, an Ikari II stirrer, a reflux condenser thermometer, and a nitrogen inlet tube, an aqueous polyacrylic acid solution containing 300 ml of polyacrylic acid was added. (Molecular weight io, oooS Hiro 0,00
0,2096 aqueous solution) hydrazine hittride aqueous solution
600? <tO96 aqueous solution) was added and reacted at 70C for about 10 hours with stirring.

Thereafter, the above reaction product was slowly added to 10.8 methanol with stirring. The resulting precipitate is purified by reprecipitation method to produce water-soluble acid hydrazide poly! I got -. This poly! When measured by iodine titration method, the content of dracyto groups was 7j 9.

Example 1 Temperature regulator, squid p-type stirrer, reflux condenser, supply container,
The following raw materials were charged into a reaction vessel equipped with a thermometer and a nitrogen inlet tube.

water 200
3516 aqueous solution of the sodium salt of the sulfuric acid half ester of p-nonylphenol (anionic emulsifier) reacted with 20 moles of ethylene oxide; 1 part reacted with 2 j moles of ethylene oxide; 2096 aqueous solution 20 parts 1+ Separately, the following mixtures and aqueous solutions were prepared as Feed I and Feed 1.

Feed 1 Water - 00 parts Said anionic emulsifier aqueous solution C3j316 water bath liquid), 2j parts Styrene 2 parts λ Acrylic acid n-
Butyl 227 parts acrolein
//Q Acrylic acid IO part Acrylic acid 10 parts Supply - I Water 13 parts Potassium persulfate 2 parts Into the reaction vessel charged with the above raw materials, 1/10 amount of 1 feed ■ is charged and heated to OC. Then //10 of supply I
The amount was charged. Then, feed I and Feed I of the remainder) were added in small amounts at the same time for 3 to 3 hours. The mixture was fed into the reaction vessel over a period of J hours, and after the feeding was finished, it was kept at OC for another 43 hours to react. The reaction vessel is then cooled to room temperature,
Aqueous ammonia was added to adjust the PHt of the reaction product to 7-g. The concentration, total amount of copolymer, and monomer composition of the obtained aqueous copolymer dispersion are shown in the table below, and the monomer composition ratio of the copolymer is shown in the table below. Fi, almost completely matched the monomer ratio used.

To the obtained copolymer aqueous dispersion, 70 parts of the water-soluble acid hydrazide polymer obtained in Production Example 1 was added, and 1
After stirring for a period of time, the desired copolymer aqueous dispersion composition was obtained.

Comparative Example 1 An aqueous copolymer dispersion obtained by carrying out the same polymerization as in Example 1 was used as it was, ie, without adding a water-soluble acid hydrazide polymer, as an aqueous copolymer dispersion.

Comparative Example A copolymer aqueous dispersion was prepared in the same manner as in Example 1, except that no acrolein was added to the feed (1), and the water-soluble acid hydrasite obtained in Production Example 1 was added to the copolymer aqueous dispersion. 70 parts of the polymer were added and stirred, and the copolymer aqueous dispersion composition was placed in a mold.

Example 2 ~≠ The type of monomer and its usage ratio in feed #1 were changed to species A, and #1 was polymerized in the same manner as in Example 7. An aqueous copolymer dispersion was obtained.

Each of the above production examples/
70 parts of the water-soluble acid hydrazide polymer obtained in (1i! Examples λ and 3), or 1 part of the same acid hydrazide polymer and! Part λ of leic acid dihydrazide was added and stirred to obtain a copolymer aqueous dispersion composition.

Comparative Example 3 To a copolymer dispersion obtained by polymerization in the same manner as in Example 44, IO parts of 1-sepacic acid dihydrazide was added and stirred to obtain an aqueous copolymer dispersion composition.

The outline of the compositions obtained in these Examples and Comparative Examples is as shown in Table/.

Using each of the copolymer dispersion compositions obtained in Examples 7 to 3 and Comparative Examples 1 to 3 above, pigments, thickeners, wetting agents, antifoaming agents, etc. were added to these by the following method. Each paint having a pigment volume concentration of 2796 was prepared using the following methods.

That is, first, the following composition was prepared as a mill base.

Water / 0 parts Sodium polyphosphate /, 0 parts Emlan 0CC20
96) j: 0 parts titanium oxide 20
．． 0 parts antifoaming agent 20 parts (296) Natrosol 2jOHR 726 parts in total Next, each paint having the composition ratio shown below was prepared using this mill paste.

726 parts of the above mill base obtained in each example or comparative example 104! %θ parts copolymer dispersion dexanol/benzyl alcohol 73 parts cole mixture
(///) Ammonia water Co1t9)0. Part J: Antifoaming agent: 0.3 parts Polyoxyethylene Noelf: 0 parts Enol ether (20 circles) Total That's right.

The coating film physical property test method and evaluation details were as follows.

/) Water-resistant paint on the sipuru board! A test piece was prepared by applying the film to a thickness of Oμ (dry coating) and drying it at 1.20C for one week. Thereafter, it was immersed in 20C water for a week, and the appearance of the coating film and the presence or absence of blistering were evaluated.

2) Alkali resistance A test piece prepared in the same manner as 1) was immersed in saturated lime water in COOC, and evaluated in the same manner as /).

3) A test piece was prepared by applying the scratch-resistant paint to a glass plate to form a dry coating film and drying it at 20C for 7 hours.

After that, gauze was placed on the coating film, a load of 1 oor was applied, and the adhesiveness was evaluated after being treated at a predetermined temperature for 2≠ hours.

Hardness The pencil hardness of the test piece prepared in the same manner as in 3) was measured.

Solvent Resistance A line was drawn on a test piece prepared in the same manner as in 3) in marker ink or office ink, wiped off with ethyl acetate, and the state of the coating film at that time was evaluated.

6) Adhesive paint to alkyd resin coating was applied to the alkyd resin coating to a thickness of 30μ (dry coating), dried at 20C for 7 weeks, and then
A peel test was performed using Serefane tape and its adhesive strength was evaluated.

7) Adhesion to vinyl chloride resin coating The adhesive strength of p1 vinyl chloride resin coating was evaluated in the same manner as in 6).

? ) Yellowing resistance A test piece obtained by the same method as in 3) was irradiated with a germicidal ultraviolet lamp from a distance of /3 an for 7 weeks, and the degree of yellowing at that time was evaluated.

ii) The evaluation results were displayed as shown below.

◎ ...Very good○ ...Good Δ ...Average × ...As is clear from the results of the unfavorable table λ, the copolymer aqueous dispersion composition of the example The physical properties of the coating film are significantly superior to those of the comparative dispersion.

Claims (1)

[Scope of Claims] /-(A) (a) n having 7 to 1 carbon atoms in acrylic acid
- alkyl esters, n-alkyl esters of n-alkyl esters of methacrylic acid, saturated carboxylic acid vinyl esters, /, 3--)xn, weight of monomer units zj to -j 9. (b) Carbonyl group-containing monomer unit having at least 7 aldo or keto groups and a double bond in the molecule. / ~ 20 weight 9, (c) monoolefinically unsaturated carboxylic acid having j to j carbon atoms,
0.3 to 70 monomer units selected from the group consisting of unsaturated carboxylic acid amides, N-alkyl and/or N-alkylol derivatives of unsaturated carboxylic acid amides, and oligoolefinic unsaturated sulfonic acids. and (d) a monomer unit θ~711.4 selected from the group consisting of methyl methacrylate, vinyl aromatic compound, tertiary butyl acrylate, hynyl halide, ethylene, acrylonitrile, and methacrylonitrile. CB) A water-soluble acid hydrazide-based polyester having at least two hydrazide groups in the molecule! An aqueous dispersion composition of a carbonyl group-containing copolymer, characterized in that it contains -. Yu Water-soluble acid hydrazide poly! - The composition according to claim 7, wherein the ratio of hydrazide groups in the hydrazide polymer is 0.02 to 5 moles per 7 moles of aldo and/or keto groups in the copolymer. .