DE2155402A1 - Paints stabilized against microbial attack - Google Patents

Description

"Paints stabilized against microbial attack"

Priority: November 6, 1970, V.St.A., no.87 615

It is known that paints, such as paints or varnishes, often have insufficient resistance to attack by microorganisms. Some of these paints, like Manure paints or building paints contain resin-like binders drying oils, binders on oil-based bases or alkyd resins that are attacked by fungi. Other paints, e.g. Aqueous dispersions of water-insoluble synthetic linear polymers generally contain plasticizers and viscosity-increasing agents Additives (thickeners) based on animal or vegetable raw materials. Plier through are the paints üchirnmcl-prone. iis obvious that the partial or complete destruction of the paint or the

209820/0974

with paint films produced by microbe infestation a considerable amount Represents an obstacle to the general use of paints, especially in those areas of application where microbe infestation is to be expected.

Various biocidal agents have been proposed for use in paints. However, these biocidal agents have not proven entirely satisfactory. Some do not provide permanent protection against microbial attack, while others cause sulfide discoloration, and still others migrate from animal paint film, volatilize or leach from the paint film during use of the object to be protected.

The object of the invention was therefore to provide stabilization against microbial attack To provide paints that contain, as biocidal agents, compounds that are compatible with the conventional, Resin-like binders used in paints are very compatible, do not cause sulfide discoloration and an effective and permanent protection against the destructive attack by fungi, bacteria and other microorganisms guarantee, without the desired physical properties of the paints or the paint films produced with them, e.g. to adversely affect the viscosity or the color. This object is achieved by the invention.

The invention thus relates to microbial attack stabilized Paints, consisting of

(a) a water-insoluble resinous binder,

(b) about 0.10 to 3 percent by weight, based on the

209820/097/4

spreading agent, an N'-trichloromethylinercaptoindazole of the general formula (I)

(D

in which X denotes a halogen atom, a nitro, amino or (halobenzylidene) amino group, η denotes a Has a value of 0 to 2 and Y represents a hydrogen or halogen atom, and optionally (c) water or organic solvents, extenders, pigments, dyes, defoaming agents, drying agents, Emulsifiers, dispersants, plasticizers, corrosion inhibitors, bactericides and other common ones Additives and processing aids.

If X represents a halogen atom, this is preferably a chlorine, bromine or iodine atom. Preferred (halobenzylidene) amino groups are the (chlorobenzylidene) and (bromobenzylidene) amino groups. If Y is a halogen atom, this can be a chlorine, bromine, fluorine or iodine atom. In the paints of the invention, preference is given to using those TrMüoimethylmeicaptoindazoles of the general formula (I) in which η is 1, Y is a hydrogen or chlorine atom and X is a nitro group or a chlorine atom in the 5- or 6-position.

209820/0974

Specific examples of N ¹ -trichloromethylmercaptoindazoles of the general formula (I) are N'-trichloromethylmercapto-3-chloroindazole, N ^l -trichloromethylmercapto-5-nitroindazole, N'-trichloromethylmercapto-3-chloro-5-nitroindazole, N'-trichloromethylmercapto 5-chloroindazole, N'-trichloromethylmercapto-3,5-dichloroindazole, N ^l -trichloromethylmercapto-3-'bromo-5-aminoindazole, N'-trichloromethylmercapto ^, 5-dibromoindazole, N'-trichloromethylmercapto-3 »5- diiodindazole, N ¹ -trichloromethylmercapto-ö-nitroindazole, N'-trichloromethylmercapto-3-bromo-6-aminoindazole, N'-trichloromethylmercapt0-6- (3,4-dichlorobenzylidene) -aminoindazole, N'-chloromethylmercapto-3-chloromethylmercapto-3 6-nitroindazole, N'-trichloromethylmercapto-5,6-dinitroindazole or N * -trichloromethylmercapto-3,5 »6-trichlorindazole.

The preparation of the N'-trichloromethyl mercaptoindazoles of the general Formula (I) can be made in a number of ways. According to one process, the corresponding indazoles are made with Trichloromethylsulfenyl chloride condensed. The condensation is generally refluxed in a solvent such as benzene, toluene, xylene, ethanol, acetone or ethylene dichloride carried out. This method is described in CA-PS 853 219 and DT-OS 1,814,335.

The paints of the invention can be either solvent-free or contain water or organic solvents as solvents. The paints preferably contain an oil-based binder or a synthetic linear polymer.

In a preferred embodiment, the paints contain one or more organic solvents and a binder

209820/0974

oil-based medium. Examples of oil-based binders are drying oils such as flaxseed oil, tung oil, soybean oil, dehydrated Castor oil, safflower oil or fish oil, thickened drying oils (thick oils), mixtures of drying oils or thick oils with resins such as lime resins (rosin treated with lime), rosin esters (esterified rosin) or phenolic resins, Oleoresin varnishes made by heating one of the aforementioned resins with one or more drying oils or thick oils or alkyd resins made from polyhydric alcohols such as pentaerythritol or glycerol with dicarboxylic acids such as Phthalic anhydride, or fatty acids.

In a further preferred embodiment, the paints exist of the invention from an aqueous dispersion containing about 10 to 60 percent by weight of the oil-based binder and / or the synthetic linear polymer. The aqueous dispersions of synthetic linear polymers are generally produced by emulsion polymerization of monoethylenically unsaturated monomers, but can also be several times unsaturated monomers, such as butadiene, chlorobutadiene or isoprene, can be used to a certain extent. Specific examples for synthetic linear polymers are polyvinyl acetate, polyvinyl butyrate, Polyvinyl chloride, vinyl acetate-vinyl chloride copolymers, Vinyl acetate-acrylonitrile copolymers, vinyl chloride-acrylonitrile copolymers, Vinyl chloride-vinylidene chloride copolymers, polyethylene, polyisobutylene, polystyrene, Styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, copolymers of acrylic acid esters or methacrylic acid esters with alcohols that have 1 to 8 carbon atoms in alcohol, with vinyl acetate, vinyl chloride, acrylic

209820/097 / *

nitrile or styrene, copolymers of the aforementioned acrylic acid esters, the aforementioned methacrylic acid esters and acrylic acid or styrene-maleic anhydride copolymers.

It has been shown that a content of 0.10 percent, based on the weight of the paint, of one or several of the N'-trichloromethylmercaptoindazoles of the general Formula (i) is sufficient to provide a considerable improvement in terms of the resistance to microbial attack. It can be up to 3 percent or more of the biocidal Connection is used, however, the larger quantities cause generally no further improvement in paint properties and are therefore generally not used. The optimal amount of the biocidal compound depends inter alia on the specific compound of the general formula (I), the type of binder and the intended use of the paint away. However, the preferred content of the trichloromethyl mercaptoindazole is generally about 0.5 to 2 percent by weight, based on the weight of the paint.

The N'-trichloromethyl mercaptoindazole can be added to the paint be incorporated in any way. For example, it can be combined with the pigments or other components to form a pigment phase Mix, which is then mixed with the binder and water or an organic solvent. The N * -trichloromethyl mercaptoindazole however, it can also be added to the finished paint. The N'-trichloromethyl mercaptoindazole can either be added as such or dissolved in solvents such as alcohols, ethers or ketones.

209820/0974

The examples illustrate the invention.

example 1

The influence of the N'-trichloromethylmercaptoindazoles used according to the invention in combating a representative group of fungi, bacteria and algae is determined with the aid of the standard agar plate assay disc procedure.

For this purpose, solutions of the test compounds in dioxane are added to a solution of phenylcuric silver (II) acetate in water turns. The results are shown in Table I, with the effectiveness of the individual compounds as follows is designated:

NZO does not inhibit microbial growth ZO-X zone of inhibition in mm G growth in the zone

209820/0974

Table I.

N'-trichloro

methyl mercapto-

5-nitroindazole

N'-trichloro

methylmercapto-

6-nitroindazole

N'-trichloro

methylmercaptp-

3-chloro-6-nitroindazole

Phenyl mercury (II) acetate

no addition

salary

1.0 2.0

0.5

1.0 2.0

1.0 2.0

mushrooms

NJ
O (7 days in Incuba
tion time) G
ZO-2
NZO G
ZO-3
NZO CO
O A. niger
P. crustosum
P.pullulans Ό974 bacteria
(48 hours incuba
tion time) ZO-3
NZO
ZO-2 Z0-7
Z0-3
Z0-6 E. flavescens
S. aureus
A. aerogenes
Z.vesicstoria
3. subtilis Seaweed
(7 days of incubation
Time) ZO-4 Z0-6 G. vulgaris

Z0-4 ZO-11 ZO-11

ZO-13 Z0-6 Z0-6 Z0-6

Z0-3

ZO-10 ZO-14 ZO-11 ZO-12 NZO ZO-8 Z0-10 Z0-10 ZO-12 NZO ZO-7 ZO-12 ZO-17 ZO-21 NZO

ZO-2 ZO-2

Z0-3 ZO-16

Z0-6 ZO-8

ZO-15 Z0-16 NZO Z0-15 Z0-17 NZO Z0-11 Z0-13 NZO Z0-10 «. NZO ZO-22 ZO-25 NZO

ZO-20

NZO

Example 2

(A) A polyvinyl acetate emulsion paint becomes like
is made as follows:

Component parts by weight

Water 280

Potassium pyrophosphate 3

Calcium metasilicate 135

Titanium dioxide (rutile) 220

2 percent aqueous

Methyl cellulose solution 2CC

Diethylene glycol diethyl ether 37

aqueous polyvinyl acetate dispersion

(55 percent by weight) 350

Two samples of this paint are mixed with 2 percent by weight of an N ¹ -trichloromethyl mercaptoindazole of the general formula (I) or with 2 percent by weight of a comparison compound.

(B) An acrylic latex paint is made as follows:

Ingredient parts by weight titanium dioxide 114

Mica (wet milled) H

Calcium carbonate 57

V / aas he 70

Pigment dispersant (25 percent aqueous solution of sodium salt. zeö of a diisobutylene maleic anhydride copolymer)

209820/0974

_ ₁₀ - 2155A02

Porting recipe (B) component parts by weight

Ethylene glycol 9

Hydroxyethyl cellulose '1

aqueous ammonia (28 percent) 1

Acrylic acid ester latex 2aq

($ 4-6 solid content)

Two samples of this paint are mixed with 2 percent by weight of an N'-trihlomiethyl mercaptoindazole of the general type Formula (I) or with 2 percent by weight of a Yergleiehsverbindungen.

(C) A building exterior paint is made as follows:

Component parts by weight

basic lead carbonate 288

Zinc oxide 232

Titanium Dioxide (Rutile) 149

Talc 260

Linseed oil (refined with bases) 242

thickened linseed oil 114

White spirit 114

Anti-skin agents (Exkin 2) 2

Manganese naphthenate (6 percent) 2.27

Lead naphthenate (24 percent) 11 »3

Two samples of this paint are mixed with 2 percent by weight of an N'-trichloromethyl mercaptoindazole of the general formula (I) or with 2 percent by weight of a comparative compound.

209820/0974

Example 3

The samples of polyvinyl acetate emulsion paint prepared in Example 2 (A), the acrylic latex paint (B) and the oil-based architectural exterior paint (C) are as follows examined:

Sheets of stretched paper are dipped into the paints, dried for 24 hours and dipped again into the paints. After drying for 24 hours, the coated papers are cut into square test samples with an edge length of 32 mm. The test samples are placed in a dish containing malt and mycophilic agar inoculated with 1 ml of a suspension of the test organism. The dishes prepared in triplicate are kept at 28 ^° C. and observed weekly. The results are compiled in Table II, where ZO-X again denotes the zone of inhibition in mm.

Example 4

According to Example 3, sheets of paper coated with paints (A), (B) and (C) are produced. After drying has ended, 1 sheet is subjected to the leach test for 24 hours according to Method 5831, CCC-T-191b. The sheets of paper are then cut into test samples with an edge length of 32 mm and placed in a dish containing malt and mycophilic agar which have been inoculated with 1 ml of a suspension of the test organism. The dishes prepared in triplicate are kept at 28 ^° C. and observed weekly.

The results (mean values from the triplicate tests) are in Table III, using the following evaluation key:

ZO-X zone of inhibition in mm

0 no zone of inhibition; no growth on the paint film

1-10 increasing microbial growth on the paint film

Example 5

Cedar boards are emulsified with the polyvinyl acetate of Example 2 deleted, the 2 percent by weight of N'-trichloromethylmercapto-ö-nitroindazole, bis- (phenylmercury- (II) -) - dodecenyl succinate as a comparison compound or contains no additive. The painted boards are on issued to a weathering test rig in Florida. The boards are checked at certain time intervals, whereby in each case the extent of fungal growth is determined using a scale from 0 to 10 in which 0 is no growth and 10 signify a mushroom growth in which the board is covered with mushrooms. The results are shown in Table IV.

209820/0974

Painting-
biocidal compound color *) B.
A.
C. ■ ι pH Tabel II fungicidal effectiveness ZO-2
ZO-2
ZO-2 - ^ SL - at cn
cn
4> -
O
NJ N'-trichloromethy1-
mercapto-3-chlorine-
indazole B.
A.
σ 7.2
6.5 • Pullularia penicillium
pullulans crustosum ZO-2
ZO-3
ZO-3 Aspergillus
Niger N'-Trie hlormethy1-
mercapto-3-chlorine-
5-nitroindazole B.
A.
0 8.5
7.0 Influence on
the color ZO-3
ZO-3
ZO-2 - ZO-3
ZO-3
ZO-3 N'-trichloromethyl
mercapto-3.5-
dichloroindazole B.
A.
σ 8.1
6.9 none
Il
H ZO-5
ZO-4
ZO-6 ZO-2
ZO-7
ZO-5 ZO-2
ZO-2
ZO-1 N'-trichloromethyl
mercapto-6-nitro-
indazole B.
A.
C. 8.0
7.1 greyish-white
ti
none ZO-1
ZO-2
ZO-1 - 2098 N'-trichloromethy1-
mercapto- 6- (3,4-di-
ciilorbency lids) -
aminoindazole B.
A.
σ 8.3
6.8 dd
It
dd ZO-3 "
ZO-8
ZO-5 ZO-1
ZO-6
ZO-4 ZO-3
ZO-5 -
ZO-5 20/0 Bis ~ (phenylmercuric
ber- (II) -) - dodecenyl-
succinate
(Super Ad-It) 8.4
. 6.9 dd
It ZO-1
ZO-1
ZO-1 - (O
4P * ' A = based on] Polyvinyl acetate ti
It
dd ZO-9
ZO-17
ZO-8 ZO-10
ZO-13
ZO-10 B = based on, A.cryllatex It
dd
dd C = based on '. linseed oil

Table III

biocidal compound

H '-Trichloromethyl-

mercapto-6-nitro-

indazol N '-Triehlormet hy 1-mercapto-3-chloro-5-nitroindazole

Bis (phenyl mercury (II)) - dodecenyl succinate (Super Ad-It)

without addition

Paint '

fungicidal effectiveness

Aspergillus niger

not exhausted '

1 week

2 weeks

3 weeks

4 weeks

drained '

1 week

2 weeks

3 weeks

4 weeks

Pullularia pullulans not depleted '1
2
3
4th

Week weeks weeks weeks

drained

1 week

2 weeks

3 weeks

4 weeks

O ZO-1 O ZO-1 O ZO-1 O ZO-1 O O O O O . O O O O ZO-1 O ZO-1 O ZO-1 O ZO-1 O O O O O O O O

ZO-1
ZO-1

O
O
O
O

ZO-1
ZO-1
ZO-1
ZO-1

O
O
O
O

O O O O

O O O O

O C O

O O O O

ZO-6
ZO-6
ZO-4
ZO-2 ZO-5
ZO-5
ZO-5
ZO-5 ZO-3
ZO-3
ZO-3
ZO-3 ZO-5
ZO-5
ZO-5
ZO-5 1
1
1
2 O
O
. 1
1 O
O
1
2 O
•1
1
1

10 10 K) 10 10 cn 10 10 cn 10 10 J> 10 10 O 10 10 N) 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10

= based on acrylic latex; C = linseed oil; **) Number of weeks at 28% and 90 to 95 # relative humidity;

Number of months in the weathering test

- 15 -

Table IV

N'-trichloromethyl

mercapto-6-nitro-

indazole

Bis- (phenyl- without mercury- Zn- (II) -) - dodesatz cenylsuccj nat

13th

19th

21st

24

0 0 2 2 2 2 2 2 2 4

0 4th 2 6th 2 6th 2 8th 2 8th 2 8th 4 ' 8th 4th 8th 4th 8th 4th 8th

It can be seen from the above tables that the N ¹ -trihlomethylmereaptoindazoles used according to the invention are effective biocides both for aqueous and for solvent-based paints. This gives the paints a resistance to microbial attack that persists even after the paint films have been leached out. The N'-Triehlomethylmereaptoindazole have no influence on the pH, the color, the viscosity and the heat aging behavior of the paints or paint films. In contrast to those paints which contain bis (phenylmercuric (II) -) - dodecenyl succinate as biocide, the paints according to the invention do not show any gray or black discoloration under the influence of hydrogen sulfide.

Claims

209820/097 /,

Claims (10)

Claims 1. Paints stabilized against microbial attack, consisting of the end (a) a water-insoluble resinous binder, (b) about 0.10 to 3 percent by weight, based on the paint, of an N ¹ -trichloromethyl mercaptoindazole of the general formula (I) (D in which X is a halogen atom, a nitro, amino or (halobenzylidene) amino group, η is a value from 0 to 2 and Y represents a hydrogen or halogen atom, and optionally (c) water or organic solvents, extenders, pigments, dyes, defoaming agents, drying agents, Emulsifiers, dispersants, plasticizers, corrosion inhibitors, Bactericides and other common additives and processing aids. 2. Paint according to claim 1, characterized in that the content of N'-trichloromethyl mercaptoindazole is 0.5 to Percentage by weight, based on the paint. 2Q9820 / 0974 3. Paint according to claim 1 and 2, characterized by the content of N'-trichloromethylmercapto-lp-nitroindazole. 4. Paint according to claim 1 and 2, characterized by the content of N'-Tr-ichlormethylmercapto-o-nitroindazole. 5. Paints according to claim 1 and -2, characterized by the content of N ^l -trichloromethylmercapto-3-chloro-6-nitroindazole. 6. A paint according to claim 1 and 2, characterized by the content of ^{5 f} U ~! Erichlormethylmercapto-3-chloro-5-nitroindazole. · 7. Paint according to claim 1 and 2, characterized by the content of N'-trichloromethylmercapto-3,5-dichloroindazole. 8. Paint according to claim 1 and 2, characterized by the content of N'-trichloromethylmereapto - ^ - chlorindazole. 9. Paint according to claim 1 to 8, characterized in that the binder is polyvinyl acetate. 10. Paint according to claim 1 to 8, characterized in that the binder is an acrylic acid resin. Λ ORiGiNAt INSPECTED 209820/0974 ——-