DD291332A5 - ANTIMICROBELICALLY ADJUSTED WAFERRED ART RESIN DISPERSIONS - Google Patents

Abstract

The invention relates to antimicrobially treated, aqueous synthetic resin dispersions based on polyvinyl acetate or polyacrylate. In addition to auxiliaries and additives known per se, the dispersions contain thiadiazoles substituted as antimicrobial active components, which ensure preservation of the dispersions or of the paints formulated therewith during storage as well as protection of the resulting paint films from microbial attack. microbial infestation; Paints and varnishes; Lagerstabilitaet; Film preservation; polyvinyl acetate; polyacrylate; Auxiliaries and additives; antimicrobial active component; substituted thiadiazoles}

Description

contain.

2. antimicrobially treated aqueous synthetic resin dispersions according to claim 1, characterized in that the antimicrobial active component is contained in concentrations of 0.01-3 parts by weight in%.

Field of application of the invention

The invention relates to antimicrobially treated aqueous synthetic resin dispersions based on polyacrylate or polyvinyl acetate and paints prepared therefrom. It can be used both for preserving the dispersions themselves and for protecting the resulting paint films from microbial attack.

Characteristic of the known technical solutions

Aqueous dispersions of synthetic resins, which have great economic importance as dispersion paints, both to ensure the stability during storage to application and to avoid microbial, especially fungal attacks on the paint films produced the addition of suitable antimicrobial agents. This concerns during storage mainly a bactericidal effect in the aqueous phase and then predominantly a fungicidal action in the paint-plastic film. These requirements meet only a few substances.

It is known to use benzisthiazolone- (3) as antimicrobial additive for these purposes. This substance is very effective, but technically difficult to access and unokonomisch.

Also known is the use of dithiocarbamates and thiuram. However, they are only sufficiently effective at high concentrations and have a negative influence on the paintability with drying oils or alkyd resins.

Volatile substances such as aldehydes are not permanent, phenols are too toxic or odor intensive and organic tin compounds are not suitable for indoor use because of their high toxicity.

Also known are attempts to counteract these deficiencies by combinations of active ingredients. (DD-PS 107848 and DD-PS 233941). However, one achieves only sufficient storage stability, but no sufficient film stability.

Furthermore, it is known that a part of the active substances on which the antimicrobial additives according to the invention are based has been proposed as pesticides because of their fungicidal action against phytopathogenic fungi (for example DD-PS 222770). In this case, an effect is specifically demonstrated against harmful fungi from the group of Oomycetes, in particular against Phytophthora infestans.

Object of the invention

It is an object of the invention to find a suitable antimicrobially active and inertly toxic additive to aqueous synthetic resin dispersions and paints formulated therewith by which both good preservation of the dispersions and reliable protection of the resulting paint films from microbial attack are to be achieved.

Explanation of the essence of the invention

The object of the invention is to develop new antimicrobially treated aqueous synthetic resin dispersions. This object is achieved according to the invention by the fact that aqueous synthetic resin dispersions based on polyvinyl acetate or polyacrylate and paints prepared therefrom containing known additives (ζ, Pigment pigments) have thiadiazoles of the general formula ## STR2 ## substituted as antimicrobial active component

_{χ Ν}

Il

^N "~S (O) _n OH ₂ R,

in the X m Br or Eq

η a 1 or 2 and R c is phenyl or χ -, ι-N, added

ύ Ο "*

become.

The active compounds can be prepared by literature ancestors by halogenation and subsequent oxidation of the corresponding cyanimidodithiocarbonic acid monoester salts (e.g., U.S. Patent 3,736,328, Z. Chem., 20,11980, 370). Sio are added to the synthetic resin dispersions and are already effective in concentrations of 0.01% by weight in%. For practical purposes of preservation and equipment, concentrations of 0.05-0.5 mass% in%, depending on the load on the paint, are recommended.

0.05-0.1 mass% in% are sufficient to ensure storage stability, while 0.1-0.5 mass% are used for film stabilization, depending on the desired duration of action and germ load.

To achieve optimal distribution in the medium, the active ingredients can be powdered, z. B. wet-ground, pasted with water and combined with surfactants.

The active ingredients are stable, low-toxic and do not negatively affect the ecosphere under the conditions of use.

embodiments

Example 1 Testing of the Aqueous Synthetic Resin Dispersion for Sterility

test description

The technical dispersion is mixed with the specified concentration of the active ingredients to be tested. Subsequently, a sample (1 ml) is removed and placed in a flamed test tube filled with Sabourand nutrient medium (I) and parallel with thioglycolate nutrient medium (II).

The samples with the culture medium I are incubated for 10 days at 22-24 ° Cund with the culture medium II for 10 days at 30-32 ⁰ C in the incubator. Subsequently, the review takes place. The results are summarized in Table 1. It means + without microwave infestation

+/- hardly any microbial infestation

- microbial infestation

Table 1: Evaluation of the synthetic resin dispersion for sterility

Active substance concentration Evaluation in the nutrient medium

% I Il

without - (known) Benzisothiazolone (3) 0.1 0.05 thiuram 1.0 0.5 tributyltin 0.2 formaldehyde 0.3 0.05 (Invention) 3-chloro-5-benzylsulfonyl 0.1 1,2,4-thiadiazol 0.05 (3-bromo-1,2,4-thiadiazol-5-yl) - 0.05 (3'-bromo-1 ', 2', 4'-thiadiazole) 0.01 5'-ylthiomethyl) sulfoxide

-J- -,

Example 2 Storage test of the aqueous synthetic resin dispersion

test description

1 kg of synthetic resin dispersion is mixed with the specified concentration of the active substances to be tested and stored in a test tube at room temperature.

The assessment for microbial infestation takes place monthly according to the following rating scheme

1 = no infestation

2 = weak infestation

3 = heavy infestation

The results are included in Table 2.

concentration 0.1 1 month storage time -3- 291,332 % 0.03 3 2 months _ 0.05 3 Table 2: Microbial infestation of stored aqueous synthetic resin dispersions 0.1 1 3 months active substance 0.3 1 1 3 0.5 1 1 without 0.3 1 1 2 (known) 0.5 1 1 1 Combination according to DD-PS107848 0.05 1 2 2 0.1 1 1 1 Combination according to DD-PS 233941 0.1 1 1 3 0.2 1 1 Benzisothiazolone (3) 1 3 0.03 1 2 2 thiuram 1 ', 2', 4'-thiadiazol-5'-ylthiomethyl) sulfoxide 0.05 1 1 1 1 3 (Invention) 3-chloro-5-benzylsulfonyl-1,2,4-thiadiazol 1 2 2 (3-bromo-1,2,4-thiadiazol-5-yl) - (3'-bromo- 1 1 1 1 3 2 1

Example 3 Testing the film stability of the paint film

test description

The dried films are placed in petri dishes on mineral salt or nutrient agar and each sprayed with spore suspension of Penicillium funicuiosum (A) -Pultularia pullulans (B) and Aspergillus niger (C) sprayed. This is followed by a 6-week incubation in the incubator at 25 ° C with

weekly assessment for growth according to the following rating scheme

1 = overgrown

2 = medium growth

3 = weak growth

4 = no vegetation

The test results are summarized in Table 3.

Table 3: Fungus growth of the paint film

active substance

Concentration%

Rating (week) 1 2

(known)

thiuram

Tri-butyl-tin oxide

(Invention)

(3-Bromo-1,2,4-thiadiazol-5-yl) - (3'-bromo-1 ', 2', 4'-thiadiazol-5'-ylthiomethyl) sulfoxide 3-chloro-5-benzylsulfonyl-1 , 2,4-thiadiazol

0.5 0.2 0.2 0.1

0.2 0.1 0.2 0.1

ABC ABC ABC ABC 322 121 111 111 444 433 333 222 444 322 222 121 444 444 332 121 444 343 232 111 444  '44 444 444 444 443 333 332 444 444 444 444 444 334 223 222

Claims (1)

1. Antimicrobially treated aqueous synthetic resin dispersions and thus formulated paints based on polyvinyl acetate or polyacrylate, characterized in that they are in addition to conventional auxiliaries and additives as antimicrobial active component substituted thiadiazoles of the general formula ¹ ^ S * ¹¹ - S (O) _n CH ₂ R, in the X ο Br or Ul η β 1 or 2
and R β is phenyl or X - n N,