HU205160B - Process for producing water- dilutable coating material composition having fungicidal and/or bactericidal activity - Google Patents

Abstract

Water dilutable coating compsn. of 40-60 wt.% solids with fungicide and biocide action contains 5-30 wt.% of a poly-acrylate or methacrylate binder. The compsn. also consists of (all wt.%-s); 10-65 fillers and fragments, 0.3-15 polyurethane:microbiocide adduct in a ratio: 2:1-4:1; 0.05-1 thickener, 0.3-3 organic solvent pref. petrol, or petrol rich in aromatic cpds. 0.5-10 other additives as surfactants, antifoams, transient plasticizer and water vol. 100%.

Description

FIELD OF THE INVENTION The present invention relates to a process for preparing a coating composition comprising a water-dilutable acrylic acid or methacrylic acid ester polymer having a durable fungicidal and / or bactericidal action.

A. varnishes, paints, various coatings often contain pesticide, usually fungicide or bactericide as an additive.

However, the biologically active compositions, the pesticidal compositions, may also contain polymers as additives.

In these compositions, the polymers act as binders, adhesives, or protective colloids.

Their function is, if appropriate, to act as a binder in the formation of the wall of the microcapsule containing the pesticide, and, on the other hand, to improve the rain resistance of the pesticide and the stability of the aqueous dispersion containing the pesticide.

German Patent Publication No. 3,239,809 discloses a pesticidal composition wherein the fungicidal active ingredient is polyoxyacrylic acid sodium salt.

German Patent Publication No. 2 952 239 describes a liquid fungicidal composition in which a mixture of polyvinylpyrrolidone and polyvinyl acetate is added as a stabilizing agent.

However, fungicides and bactericides play an additive role in polymer-based paints and coatings.

Their task is both to preserve the liquid coatings during storage and to protect the painted surfaces against fungi and bacteria. (Varnish and Paint Pocket Book, Technical Publication, Bp. 1982 335338.0.)

The addition of fungicides and bactericides as preservatives is necessary because the thickeners in the aqueous dispersion coatings and paints, especially the cellulose or starch derivatives, are attacked by bacteria and molds during storage. Without preservatives, the shelf life of these formulations would be significantly reduced.

In places with high humidity (industrial facilities, baths, apartment kitchens, etc.), the humidity condenses on the wall and the mildew on the damp painted surface begins to mold. This can be countered by the addition of fungicides or bactericides to the coating composition.

As a preservative, a fungicide or bactericide which is highly soluble in water must be used.

In the case of coatings, however, the water-soluble fungicide or the condensing vapor or, when applied outdoors, precipitate readily to dissolve from the applied layer and therefore not long-lasting.

When an organic solvent is used as a diluent in the coating system, the above problem is overcome by using only a very water-soluble fungicide, bactericide.

However, in the case of aqueous systems, only a microbicidal additive which is highly soluble in the solvent of the system, water, should be used, as this is the only way to ensure a homogeneous distribution of the biologically active substance.

In this case, however, the fungicidal, bactericidal effect cannot be sustained due to dissolution from the surface.

The permanent fungicidal, bactericidal action of the coating material cannot be ensured even if the microbicide is too volatile, since evenly distributed microbicide molecules on the surface will fade away in less time than desired.

The high volatility of the microbicide is particularly dangerous when used indoors, as it can be harmful to human health if it is released into a confined space.

It is an object of the present invention to provide an aqueous dispersion coating system containing an additive having a fungicidal or bactericidal action, which has a very long lasting effect and is well suited for both indoor and outdoor use without harming human health.

It has been found that a fungicide, bactericidal compound containing active hydrogen - hydroxy, amino, imino, amide, imide, carboxyl, sulfonamide, sulfonimide - can be combined with an aqueous dispersion of a polyurethane polymer and the adduct thus prepared is a useful coating additive. because the chemical can also be attached to the binder.

When the adduct is formed, the active hydrogen of the fungicidal and / or bactericidal compound is attached to the free isocyanate groups of the polyurethane chain to form the adduct. However, the adduct retains a free hydroxyl group which can be attached to the free carboxyl groups of the polymeric binder.

The adduct has the particular advantage of being readily miscible with the coating material, easy to mix with and chemically incorporated therein.

The environmentally friendly coating material of the present invention is suitable for use in a high humidity environment and exhibits a long-lasting microbicidal action. It can also be used indoors without harming human health.

The advantage of the coating material is its long shelf life,

The weight ratio of the polyurethane polymer - adduct to polyurethane fungicide and / or bactericide - between 2: 1 and 4: 1 on a dry matter basis, i.e. 2 to 4 parts by weight on a dry basis, 30-60% by weight in water forming the adduct from a polyurethane dispersion.

The urethane polymers are used in an aqueous dispersion having a viscosity of 100 to 1000 mPa.s.

The polyurethane dispersion is prepared from compounds containing hydroxyl groups and a mixture of polyoxyalkylene / β-glycols of molecular weight 20050000 with aliphatic or aromatic polyisocyanates.

EN 205 160 Β.

The hydroxyl-containing compounds may be aliphatic glycols or aromatic hydroxyl-containing compounds such as bisphenol-A, fatty acid polyesters and the like. \ 5

A [poly (oxyalkylene)] - group in the polyurethane obtained can be diluted with water to the polyurethane chain through the incorporation of macromolecules into ^v.

A process for the preparation of a polyurethane dispersion is disclosed in German Patent Publication No. 2,048,956 and in U.S. Patent No. 4,016,121.

Preferred fungicidal and / or bactericidal compounds containing active hydrogen are those which contain the active hydrogen as hydroxy, amino, imino, amide, imide, carboxyl, sulfonamide, sulfonamide.

3-iodo-2-propynyl butyl carbamate;

N-methyl-chloroacetamide;

5- (n-butyl) -2- (ethylamino-6-hydroxy-4-methylpyrimidine);

alpha- (2-chlorophenyl) -a- (4'-chlorophenyl) -5 'pyrimidyl-methanol;

propionsav.stb.

Preferably, the binder used in the coating composition is an aqueous dispersion of polymers of acrylic acid or methacrylic acid (methyl butyl) ester. These may be homo or copolymers.

Preferably, an aqueous dispersion of styrene (butyl acrylate), vinyl acetate (vinyl vinegarate, vinyl propionate) butyl acrylate, methacrylic acid ethyl ester (vinyl propionate copolymer) is used.

The binder polymer always contains from 0.5 to 1.5% by weight of the free carboxyl group which can be attached to the free hydroxyl group of the adduct. 35

The filler is preferably mixed with micronized dolomite or calcite, talc, chalk, quartz flour, aluminum silicate, kaolin, barium sulphate.

The pigment used is titanium dioxide, rutile, zinc white, 40 lithopone.

Preferred thickeners are methyl hydroxypropyl cellulose, methyl hydroxyethyl cellulose, cellulose methyl ether, carboxymethyl cellulose, polyvinyl alcohol, starch esters. 45

Preferably, the organic solvent is benzene, aromatic rich gasoline, butyl glycol, butyldiglycol, butyldiglycol acetate.

Other additives include surfactants, aliphatic alcohols such as anti-freeze additives, plasticizers, etc. added to the composition.

The coating composition obtainable by the process of the present invention may be used as a paint, a noble plaster, or a coating kit.

The composition can be applied to plastered masonry, concrete, 55 asbestos cement and wood.

The coating material produced by the process of the invention has the following advantages:

unchanged fungicidal or bactericidal activity, even after prolonged storage,

- use in humid indoor environments - without adverse effects on the human body.

The coating material of the present invention is characterized in that 10-30 parts by weight of a known meth (acrylic acid) ester polymer binder in the form of 35-60% by weight aqueous dispersion, 30-70.3 parts by weight filler and pigment, 0.5-15% adduct of a part by weight of a fungicide and / or bactericide by reaction of 30-60% by weight of an aqueous dispersion of polyurethane at 3060 ° C, wherein the constituents have a weight ratio of 0.01- (2-4), based on dry matter. It contains 0.5 parts by weight of a thickener, 0.3 to 6 parts by weight of an organic solvent, preferably gasoline, and 0.5 to 10 parts by weight of other known additives, preferably a surfactant, antifoam, plasticizer and 100 parts by weight of water.

The following examples illustrate the process of the invention.

Example 7 Preparation of adduct A

In a stirrer, 1 part by weight of the fungicidal and bactericidal 3-iodo-2-propylbutyl carbamate is added and mixed with 1 part by weight of N, N-dimethylacetamide.

To the mixture was added 4.5 parts by weight of a 50% w / w dry polyurethane aqueous dispersion (NeRoz R-960, manufactured by Polyvinyl Chemie; a: pH of dispersion at 25 ° C: 8.5, viscosity at 25 ° C 200). mPa.s, acid number: 30).

The mixture was stirred at 35 ° C for 1.5 hours and then cooled to room temperature. The adduct thus obtained is used in paint coating compositions.

Example 2 Preparation of adduct B

1 part by weight of the fungicidal and bactericidal 3-iodo-2-propynyl butyl carbamate is weighed into a stirred apparatus. The active ingredient is mixed with 1 part by weight of butyl acetate.

13 parts by weight of a 30 wt.% Dry polyurethane aqueous dispersion (Neorez R-1001) made by Polyviny Chemie; pH of dispersion at 25 ° C 8.0, acid number 20, viscosity 25 'Con: 700 mPa.s).

The mixture was stirred at 30 ° C for 1 hour.

The adduct thus obtained is used in plaster coating compositions.

Example 3 Preparation of a C ⁿ adduct

To the stirring apparatus was added 1 part by weight of fungicidal N-methylol chloroacetamide and 1 part by weight of N, N-dimethylacetamide solvent.

7.5 parts by weight of an aqueous polyurethane dispersion containing 40% by weight of dry matter are added.

(NeoRez R-974, manufactured by Polyvinyl Chemie; dispersion pH: 25 'C: 7.5, viscosity at 25' C:

HU 205 160 Β

400 mPa.s, acid number: 18).

The mixture was stirred at 45 ° C for 0.9 hours and then cooled to room temperature. .

The adduct thus obtained is used in paint coating compositions. 5

Example 4.

The adduct prepared in Example 1 (Experiment A) was a NeoRez960 dispersion of polyurethane (Experiment B) and N- (fluorodichloromethylthio) phthalimide in 50% by weight of N, N-dimethylacetamide. dispersion (Experiment 'C') was examined by UV spectroscopy.

The results of the measurements are as follows.

Experiment 'A' showed an extended peak at 370 nm. Experiment 'B' showed no definite 15 peaks. Experiment 'C' showed a compound peak at 270 nm.

Comparison of the results shows that the polyurethane polymer formed a new high molecular weight adduct with the biologically active compound. 20

Example 5

The adduct prepared according to Example 1 and the 16% w / w dispersion of the fungicidal and bactericidal active ingredient (3-iodo-2-propynyl-butylcarbamate) in Ν, Ν-dimethylacetamide were stored in a closed container for 1 year.

Thereafter, 30 to 30 parts by weight of the 'F' adduct and the drug dispersion are added to 100 parts by weight of an aqueous solvent-solvent dispersion of methyl methacrylate ester. The 30 compositions are stored for an additional 3 months in a sealed container.

A 0.2 mm layer of coating material was applied to a wooden substrate and the specimens were individually stored in a 25 ° C indoor climate cabinet with 75% relative humidity for up to a day.

No mold was observed on the specimen treated with the adduct produced according to the invention.

On the control specimen treated with the active compound-only coating, mold spots appeared.

Example 6

Wall paint production

The composition of the colors is as follows:

1) Water 132.00 parts by weight

2) Pigment wetting surfactant (Pigmentverteiler A; manufactured by BASF) 1.00 parts by weight

3) Sodium tripolyphosphate 1.00 parts by weight

4) Antifoam silicone polymer (Nop co 8034, manufactured by NopcoMinzing)

GmbH, DE) 1.50 parts by weight

5) Methylhydroxypropyl cellulose (3% solution, viscosity:

22000 mPa.s) 1.50 parts by weight

6) 0.44 parts by weight of ammonium hydroxide

7) Ethylene glycol 13.00 parts by weight

8), A 'adduct (Example 1) 45.00 parts by weight

9) Zinc white 12.50 parts by weight

10) Titanium dioxide

11) Kaolin

12) Crete

13) Aromatic Rich Petrol 0p: 25 'C)

83.60 parts by weight 40.00 parts by weight 24.00 parts by weight 8.00 parts by weight

14) Pine oil 0.10 parts by weight

15) Acrylic Acid Ethyl Ester Methacrylic Acid Butyl Ester Copolymer Weight% Aqueous dispersion 82.00 parts by weight (Acronal 290 D, manufactured by BASF / DE)

445.64 parts by weight

The coating composition is prepared by adding component I (-5) to a mixing apparatus, adding the ammonium hydroxide component (6), and mixing until the cellulose thickener is completely swollen. Component 8) is added and the mixture is homogenized.

Components 7) and 9 (-12) are then added to the mixture in the above order and the mixture is dispersed. Once homogeneous, component 13 (-15) is added and the mixture is homogenized.

The resulting coating material is then mounted in sealable plastic boxes.

Example 7

Manufacture of plaster l) Water 7.0 parts by weight 2) Tetrakotassium pyrophosphate (50 wt% aqueous solution) 4.6 parts by weight 3) Petrol (lp23'C) 4) Methyl cellulose (cellulose methyl ether 5% by weight 60.0 parts by weight in aqueous solution) 21.0 parts by weight 5) Titanium dioxide 32.0 parts by weight 6) Micronized dolomite 420.0 parts by weight 7) Quartz flour 8) Antifoam silicone copolymer (Nopco 8034), manufactured by Nopco Mün- 230.0 parts by weight zing GmbH, DE) 4.0 parts by weight 9) Talkum 10) Slirol (ethyl acrylate copolymer) 90.0 parts by weight (Pliolite AC-80 H, manufactured by goodyear, USA) 130.0 parts by weight 11) Adduct B (Example 2) 150.0 parts by weight

1148.6 parts by weight

The composition is prepared by adding components 1), 2) and 4) to a mixing device.

After swelling of the cellulose ether thickener, 20 parts by weight of component 10) are added. The mixture is homogenized and then components 5 (-7) and 9 are added. After dispersing these, add the components 3), 8), 11) and then the remainder of the component 10). The mixture is stirred until complete homogeneity and then placed in sealable containers.

A long-lasting, permanently microbicidal spreading plaster is obtained.

HU 205 160 Β

Example 8

Production of Fakitt

1) Water. 12.0 parts by weight

2) Pigment wetting surfactant 0.5 parts by weight (Pigmentverteiler A, manufactured by BASF / DE)

5.3 parts by weight

3) Sodium polyphosphate (10% w / w aqueous solution)

4) Adduct C (Example 3)

5) Ammonium hydroxide

6) Methyl cellulose ether (4% aqueous solution)

7) Petrol

8) Butyl glycol

9) Crete

10) Micronized Dolomite lljLitopon

12) Micronized barium sulfate

13) ethyl acrylic acid / methacrylic butyl ester 50% by weight in water.

dispersion 174.00 parts by weight (Acronal 290.0 by BASF / DE)

14) Lacquer linseed oil 9.00 parts by weight

992.85 parts by weight * ϊ

12.0 parts by weight 0.5 parts by weight

70.0 parts 5.25 parts 2.80 parts 262.00 parts 262.00 parts 87.00 parts 87.00 parts

Example 9

A 10 cm by 10 cm 2 cm high wood specimen was coated with the composition of Example 10 to a thickness of 0.1 mm. As a control, another wood specimen was coated with a formulation having a thickness of 0.1 mm, the composition of which was identical to that of the kit of Example 8, but did not contain adduct but 25% by weight of Ν, Ν-dimethyl N-methylol chloroacetamide. acetamide solution was added in 12 parts by weight.

The specimens were placed into a beaker containing 500 cm ³ of distilled water and soaked for 180 days. The N-methylol chloroacetamide content of the aqueous phase was measured by UV spectroscopy.

Examination of the spectrum showed that the distilled water containing the composition of the invention did not contain any N-methylchloroacetamide, even trace amounts.

Claims (1)

(meth) acrylic acid ester from polymeric binder, filler, pigment, thickener, fungicide, 15 and / or bactericides, solvents and other additives, characterized in that 10-30 parts by weight of a known (meth) acrylic ester polymeric binder are mixed with 3070.3 parts by weight of filler and pigment in the form of an aqueous dispersion of 35-60% by weight. Containing from 0.5 to 15 parts by weight of active hydrogen - hydroxyl, amino, imino, amide, imide, carboxyl, sulfonamide, sulfonimide, phosphoramide, phosphorimide - polyurethane 30-60% by weight % adduct by reaction with 30% -60 ° C of aqueous dis25 in which the ratio by weight of the fungicidal and / or bactericidal active ingredient to the polyurethane - dry matter is 1. (2-4) and then mixed with 0.01 -0.5% by weight of a thickener, 0.3-6 to 30 parts by weight of an organic solvent, preferably gasoline, and 0.510 parts by weight of other known additives, preferably surfactant, antifoam, soft water and 100 parts by weight are added to the mixture and mixed until complete homogeneity is achieved.