NO824355L - PROCEDURE FOR STABILIZING FUNGICIDES. - Google Patents

Description

The invention relates to a method for stabilizing fungicides against photochemical degradation by adding light protection agents. These are light protection agents from the class UV absorbers and poly-alkyl piperidines and mixtures thereof.

The use of fungicides for the protection of natural and synthetic organic materials against microbiological destruction in the open air is widespread. All organic materials are potential carbon suppliers for biological assimilation. Fungicides are often used in land-

use, chemistry and polymer technology to protect organic materials that either grow in the open or why an extension of the applicability when used outside is desirable. If fungicides fail, this results in microbiological attack. The microorganisms decompose and destroy organic material by enzymatic attack. The fungicide's role is to provide an environment in which fungi can no longer live on.

Such a fungitoxic environment must be maintained for the organic materials in use outside to keep it free from fungal

attack.

Most organic fungicides are sensitive to

sunlight and splits upon irradiation. Many organic and "metal" organic fungicides are UV absorbers with one or more light-sensitive bonds. Such photo-decompositions of fungicides are a significant factor in the effectiveness of a fungicide in its application. When formulating fungicides today, loss due to dilution is therefore taken into account and natural climate influence The effect of a fungicide therefore depends on maintaining a minimum inhibitory concentration (MIC) over a certain period of time.

This is referred to as a system's degree of effectiveness (efficacy^.

The minimum inhibitory concentration is complemented by the concept of shaped attack points ("spaped.charge", J.G. Hors-fall, Principles of fungicidal action, Chronica Botanica Comp., 1956, 67-73).

A fungicide is only effective when its molecule"

honor structure is maintained by contact with the fungus. The concept of shaped attack points states that the fungicide molecule has at least two active centers. One of these enables passage through the fungus's cell wall. The second, the toxaphore or poison center, is responsible for the actual eradication of the fungus. Light degradation destroys these active centers and thus the concept of shaped attack points, whereby the fungicide becomes ineffective.

Photochemical cleavage not only reduces the effect of a fungicide by destroying the formed attack points, it can also produce volatile cleavage products which are not* toxic to plants or animals, and thus threaten the environment. It is therefore desirable to prevent or at least to reduce the decomposition of the fungicide by UV irradiation. Detailed information on the effect of UV light on the action of fungicides can be found in R. Enninga, W.J. Bordes "Fungicides in latex Paints", Biodeterioration of Materials,. Proceedings of 1st International Biodeterioration Symposium, Elsevier Publishing Co, 1968, 326-332.

To overcome this problem, two methods have generally been used up to now. The first consists in the formulation increasing the dose of the fungicide, thus compensating losses during application. The other consists in the physical shielding of sunlight's UV rays. The disadvantages of the first method are, on the one hand, increased costs, and on the other, an increased risk of warm-blooded animals. A high dosage of the fungicide above the MIC is therefore desired economically and ecologically. ¥;ed another method, pigments are usually added. These have the disadvantage of a lower solubility, as they tend to chalk out and break the material. In many cases, the pigment can even initiate the photocleavage. Therefore, this method is also not satisfactory.

According to the invention, this is solved! problem with the addition of one or more specific light protection agents to the fungicides or to fungicidal formulations.

The invention therefore relates to the stabilization of fungicides against light-induced decomposition by the addition of at least one 2, 2, 6, 6~tetraalkylpiperidine compound or at least one UV absorber and a mixture of at least one 2, 2, 6, 6~tetraalkyl~ piperidine compound with at least one UV~absorber. The invention further relates to the thus stabilized compositions and their use in fungicidal formulations such as in coating - paints, varnishes, glazes, wood protection coatings, water-repellent impregnations or similar coating agents.

The use of such stabilizers avoids the disadvantages of the known problem solutions. The chemistry and solubility of the stabilizers used according to the invention facilitate their incorporation into fungicidal formulations and increase their protective effect ■ against the breakdown of fungicides, and against the associated reduction of the fungicidal effect. In detail, the added UV absorbers act as shielding of fungicides from UV light, while the piperidine compounds capture free radicals, thereby preventing these from attacking the fungicide.

The combination of both stabilizer types therefore has the advantage of a double protection mechanism. The high stabilizer activity of this light protection agent enables a reduction of the fungicide dose •.• which is necessary for a satisfactory effect and thereby avoids the aforementioned ecological and economic disadvantages of previous methods.

The piperidine compounds used as stabilizers and UV absorbers as well as their mixtures are known compounds which are known as light protection agents for plastics and varnishes, as this is for example discussed in US patent no.

11 0 304.. 4 283 327, 4 34-4- 876, 4 314 933 or in EP-A 2753-

The 2/2,6,6-tetraalkylpiperidine compounds which can be used according to the invention are generally known, as are their properties as light protectants, US patent no.

3 54.2 729, 3-64-0 928, 3 840 4.94-, 4- 021 4.32, 4- 04.9 64-7, 4 06.4 102, 4086 204 and 4 265 805 are typical examples of numerous patents in which such piperidines are mentioned -light protection-

funds. Preferably, this involves compounds containing a group of formula I

wherein R means hydrogen or methyl. Preferably, R means hydrogen.

The piperidine* compounds that can be used according to the invention include in particular the following compound classes:

a) Light protection agent with formula II

where n means a number from 1 to 4, preferably 1 or 2,

R has the meaning indicated by formula I, R^ means hydrogen, oxyl, Cj-Cjg-alkyl, C-Cg-alkenyl, C^-Cg-alkynyl, Cy-C^ aralkyl, C^-Cg-alkanoyl, C^ -C^-alkenoyl, glyoidyl or a group -GH 2 CH (0H|~Z, where Z means hydrogen, methyl or phenyl, R^preferably means hydrogen, C^-C .^"alkyl, allyl, benzyl, acetyl or acryloyl , and R 2 means when n = 1, hydrogen, optionally with one or more oxygen atoms of

broken C^~C g~alkyl, cyanoethyl, benzyl, glycidyl, a monovalent residue of an aliphatic, cycloaliphatic araliphatic or aromatic carboxylic acid, carbamic acid or proportional acid, or a monovalent silyl residue, preferably a residue of an aliphatic carboxylic acid with 2 to 18 C atoms, a cycloaliphatic carboxylic acid with 7 to 15 C atoms, or an aromatic carboxylic acid with 7 to 15 C atoms, when 1=2, C -C^ 2-alkylene, c^*"c-|2 "

alkenylene, xylylene, a divalent residue of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorous acid, or a divalent silyl residue, preferably a residue of an aliphatic dicarboxylic acid with 2 to 36 C atoms, a cycloaliphatic or aromatic dicarboxylic acid with 8 to 14 C atoms, - or an aliphatic, cycloaliphatic or aromatic dicarbamic acid with 8-14 C atoms, when n=3, a trivalent residue, an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, an aromatic tri -k.ar bamic acid or a proportional acid, or a tri-

valence silyl residue and means, when n = 4, a tetravalent residue of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid e.

Means any substituents C^-C^2~alkyl, so

are they e.g. methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl'n-undecyl or n- dodecyl.

In the sense of C^"C^g=alkyl, R- or R2 can

e.g. form the above-mentioned groups and in addition for example n-tridecyl, n"" tetradecyl, n-hexadecyl or n-octadecyl.

When R^means C^-Cg-alkenyl, then it can be, for example, 1-propenyl, allyl, metal yl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2°octenyl, 4°tert i"butyl"2 "butenyl.

R 1 as C 1 -C 8 -alkynyl preferably means propargyl.

As C 1 -C 2 -aralkyl, R 2 is especially phenethyl or, above all, benzyl.

R₂ as C₁₆₆-alkanoyl means, for example, formyl, propionyl, butyryl, octanoyl, but preferably acetyl and as C₁₆C₆-alkenoyl especially α-acryloyl.

If R represents a monovalent residue a carboxylic acid, then it means, for example, an acetic acid, stearic acid salicylic acid, methacrylic acid, benzoic acid or 6^- (3» S^di^tert. "ibutyl~4. hydroxyphenyl)- propionic acid residue.

Denotes R^a divalent residue of a dicarboxylic acid,

then it means, for example, an adipic acid, suberic acid, sebacic acid, maleic acid, phthalic acid, dibutylmalonic acid, dibenzyl

malonic acid, butyl-(3,f>-di-tert.-butyl-4-hydroxybenzyl)-malonic acid or dicycloheptene carboxylic acid residue.

Is R2 a trivalent residue of a tricarboxyl-

acid, then it means e.g. a trimeylitic acid - or a nitrilotriacetic acid residue.

If R represents a tetravalent residue of a tetracarboxylic acid, then it means e.g. a tetravalent residue of butane-1,2,3»4-tetracarboxylic acid or pyromellitic acid.

Is R2 a divalent residue of a dicarbamic acid e,

then one means, for example, a hexamethylenedicarbamic acid - or a 2,4-toluyl en-dicarbamic acid residue.

Examples of tetraalkylpiperidine photoprotectors are seen - agents of this class are the following compounds:

1) 4~h<y>drox<y->2,2,6,6-tetrameth<y>l<p>iperidine,

2) 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,

3 ) 1'-benzyl-4-hydroxy-2, 2, é, 6-tetramethylpiperidine,

4) 1-(4-tert-butyl-2-butenyl)~4-hydroxy-2-2-6-6-tetra-methylpiperidine

5) 4-stearoyloxy-2-2-6-6-tetramethylpiperidine,

6 ) 1 - ethyl - 4-salicyloyloxy-2-2-6-6-tetramethylpiperidine,

7). 4-methacryloyloxy-1-2-2-6-6-p en tame tylpiperidine,

8 ) 1,2,2,6, 6-penta methylpiperidin -4-yl -3- (3»5-di-tert. -

butyl-4-hydroxyphenyl)-propionate,

9) di-(t-benzyl-2-2-6-6-tetramethylpiperidin-4-yl)-ma-1 einate,

10) di-(2,2,6,6-tetramethylpiperidin-4-yl)-adipate,

11) di-(2,2,6,6-tetramethylpiperidin-4-yl)-sebacate,

12) di-(1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl)-sebacate, 13) di-(1-allyl-2, 2, 6, 6-tetramethylpiperidin-4 -yl)-phthalate, 14) 1-propargyl-4-3-cyanoethyloxy-2-2-6-6-tetra methyl-piperidine,

15) 1~acetyl-2,2,6,6"*t etramethylpiperidin-4-yl-acetate,

16) trimellitic acid~tri* (2, 2, 6, 6-tetramethylpiperidin"4" yl)~ester, 17 ) T-acryloyl"4~benzyloxy<->2, 2, 6, 6-tetramethyl-piperidine, 18) dibutyl"malonic acid e-di"(1,2,2,6,6wpentam.ethylpiperidin"4-yl)-ester, 19) butyl-(3,5-di-tert.-butyl-4-"hydroxybenzyl) -malonic"acid-di"(,1,2,2,6,6-pentamethylpiperidin-4'-yl)-est is, 20)dibenzyl"malonic"di-(1,2,2,6,6-pentamethylpiperidin -4-yl)-ester, 21 ) di benzyl" mal on syr e-di - (1,2, 3»6-te trame tyl -2, 6"diethyl-pip er idin" 4~yl )"*ester , 22 ) hexane~1' , 6' -bis-(4-carbamoyloxy-1 -n-butyl -2, 2, 6, 6-tetramethyl -piperidine ),

23 ) toluene-2',4'-bis-(4-carbamoyloxy-1-n-propyl-

2,2,6,6-tetramethyl-piperidine),

24) dimethyl-bis-(2,2,6,6-tetramethylpiperidine-4-oxy)-silane, 25)phenyl-tris-(2,2,6,6-tetramethylpiperidin-4-oxy)-

silane',

26) tris -(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl)-phosphite, 27) tris-(1-propyl-2,2,6,6-tetramethylpiperidine-4 -yl)-phosphate, 28 ) phenyl-_/~~ bis - (1, 2,2,6, 6 .-pentam et ylp iperidine -4-yl^,7-phosphonate,

29) (di-1,2,2,6,6-pentylpiperidin-4-yl)-sebacate.

b) Light protection agent with formula III

in which n means the numbers 1 or '2, R has the meaning given for formula I, R^ has the meaning given under a), R^

means hydrogen, C 1 -C 2 -alkyl, C 3 -C 4 -hydroxyalkyl, C 3 -C 3 -cycloalkyl, C 3 -C 3 -aralkyl, C 2 -C 3 -alkanoyl, C 3 -C 4 -alkenoyl or benzoyl, and means when n = 1, hydrogen, C^-Cjg-

alkyl, C₁-C₆-alkenyl, C₁-C₂ cycloalkyl, with a hydroxy, cyano-, alkoxycarbonyl or carbamide group substituted C₁-C₂-

alkyl, glycidyl, a group of formula -CH^-CH (OH )-Z or formula -CONH-Z, where Z means hydrogen, methyl or phenyl,

when n = 2, Q,^"^^ 2~alkylene, C^-C^2~arylene, xylylene, a -CH2»CH(OH)-CH2 group or a group -CH2-CH (OH)-CH2 -0 -X-O-CH2 (OH ) - CH2-, wherein X means C2~C^^-alkylene, G^-C^-arylene, ^ S~^-\ 2~ cycloalkylene, or provided that R^ does not mean alkanoyl , alke"noyl or benzoyl, R^ also means a divalent residue of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or may also mean the group -CO- or R$ o, and R4. means together when "~n=.1, the divalent residue of an aliphatic, cycloaliphatic, or aromatic 1,2- or 1,3-dicarboxylic acid.

If some substituents mean C₁-C₁₂ or C₁-C₁₂-alkyl, then they have the meaning already stated under a).

If some substituents mean C^~Cy- cycloalkyl, then it is especially cyclohexyl.

As C 1 -C 8 aralkyl, R 1 means especially phenylethyl or, above all, benzyl.

R 2 as C 2 -C 3 g-alkanoyl means, for example, propioyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl and as C 2 -C 3 -alkenoyl, especially acryloyl.

If R means C0-C0-alkenyl, then it concerns e.g.

4 <• o

whether allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

R 4 which is substituted with a hydroxy, cyano, alkoxycarbonyl or carbamide group can be, for example, C 2 -C 4 -alkyl. be 2-hydroxyethyl. 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl.

If some substituents mean - G^~ C^ 2_alkyl one, then it concerns e.g. about ethylene, propylene, 2,2-dimethyl--propylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

If any substituent is C^-C-j^-arylene, then they mean e.g. b-, m- or p-phenylene, 1, 4-naphthylene .or. 4,4'-diphenylene.

As C 1 -C 2 -cycloalkylene, X is especially cyclohexyl one.

Examples of tetraalkylpiperidine photoprotectors of this class are the following compounds: 30) N,N'-bis-(2,2,6,6-tetramethyl iperidin-4-yl)-hexamethylene-1,6-dia min, 31 ) N, N1 -bis - (2, 2, 6, 6-t et ram et ylp.iperidin"4-yl)-hexamethylene-1, 6-diacetamide, 32) 1-acetyl-4"(N -cyclohexylacetamido)-2,2,6,6-tetramethylpiperidine,

33 ) 4'benzylamino-2, 2, 6, 6**t etramethylpiperidine,

34) N,N'-bis-(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dibutyl"adipamide, 35)N,N1"bis"(,2,2,6 , 6~t etra methyl pip eridin r 4-yl )~N, N' ™ dicyclohexyl-2-hydroxypropylene-1,3-diamine, 36) N, N'-bis" (2, 2, 6, 6"*tetramethylpiperidin" 4-yl) "p-xylylene" diamine,

37) connection with formula

38 ) -4" (bis °2 -hydroxy ethyl - amino ) -1, 2, 2, 6, 6-pen tearet yl -

piperidine,

39) 4"(3-methyl-4-hydroxy-5-tert.-butyl-benzo acid -

amido )-2, 2, 6, 6-tetramethylpiperidine,

40 ) 4-methacrylamido--1,2,2,6,6-pentamethylpiperidine.

c) Light protection agent with formula (IV)

in which n means the numbers 1 or 2, R has the meaning given for formula I, R has the meaning given under a), and Rc means when n=1, the 0o-C -alkylene or the hydroxyalkylene or the C1-C22-acyl °xyalkyl one, when n=2, means the group (-Cr^ ) £>> (^ 2 ~ ^ 2'

Means R^C^-C8-alkylene. or hydroxyalkylene means, for example, ethylene, 1-methyl-ethylene, propylene, 2-ethyl-propylene or 2-ethyl-2-hydroxymethylpropylene. - As G'^-C22" acyloxyalkylene, RK means, for example, 2-ethyl-2-acetoxymethylpropyl en.

Examples of tetraalkylpiperidine-lys protective agents of this class have the following compounds: 41 ) 9-aza-8,8,10,1O-tetramethyl-1,5-dioxaspiro/~5. 5_7

undecane,

42) 9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro/ 5.5_7undecane, 43 ) 8-aza-2, 7, 7, 8, 9, 9^hexamethyl, -1, 4-dioxaspiroJ/~~4. jp_7

dean,

44) 9-aza.-3-hydroxymethyl-3-ethyl -8, 8, 9, 1 0, 1 0-pentamethyl-1, 5-dioxaspiro/ 5. _5_7undecane, 45) 9-aza-3-ethyl-3 -acetoxymethyl-9-acetyl-8, 8, 10, 10-t etramethyl-1, 5-dioxa sp ir oJ_ 5. j>7undecane, 46 ) 2,2,6,6-tetramethylpip eridine-4-spiro~2 '- (1',3'~ dioxane ) - 5'-spiro-5"-(1,3""dioxane)- 2"-spiro-4"'~

(2!1', 2<r>", 6'" , . 6"'-tetramethylpiperidine).

å.) Light protection agent with the formulas (VA ), ( V Bl, (VC ),

in which h means the numbers 1 or 2, R has the meaning given for formula I, R^ has the meaning given under a),

R^ means hydrogen, C^~C^2" alkyl, allyl, benzyl, glycidyl or C^-C^ alkoxyalkyl, R^ means when n ='1, hydrogen, C^-C^2-alkyl, C^- C₁-alkenyl, C₁-C₁-aralkyl, C₁-C₁ cycloalkyl, C₁-C₁-hydroxyalkyl, C₁-C₁-alkoxyalkyl, C₁-C₁-aryl, glycidyl or a group of formula "(CHg)-C00-Q or formula

- (CH2; -O-CO-Q, where p means 1 or 2 and Q means C^-C^-alkyl or phenyl, when n = 2, C2-C.j 2-alkyl en, C^-C- jg-arylene, a group -CH2-CH (OH )-CH2-O-X-0-CH2-CH(OH )-CH2-, where X means C2~C^ -alkylene, C^-C^-arylene, C^ -Cj 2~cycloalkylene, or a group -CH2-CH (OZ 1 )CH2 - (OCHg-CH (OZ' )CH2 )2 in which Z' means hydrogen, Cj-C^g alkyl, allyl, benzyl, C2~C ^2alkanoyl or benzoyl, T.. and T2 mean independently of each other

Cj-Cj g-alkyl or optionally with halogen or Cj-C^alkyl substituted C^-Cjq aryl or Cj-Cj aralkyl or T- and T2 forms together with the C atom that binds it a Cfj-C-jg cycloalkane ring.

If some substituents mean C1-C12alkyl, then it means e.g. methyl, ethyl, n-propyl, n-butyl, sec, -butyl, tert-butyl, n-hexyl, n-octyl, .2-ethyl -hexyl, n-nonyl, n-decyl, n-undecyl or n -dodecyl.

Any substituents with the meaning of Cj-C. in o-alkyl, can e.g. be the groups listed above and in addition for example n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

If some substituents mean C 2 -C 6 alkoxyalkyl, then they mean, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxy-ethyl, tert.butoxyethyl, isopropoxyethyl or propoxy-propyl.

If Ry means G^-C^ alkenyl, then it means e.g. 1~propenyl, allyl, metalyl., 2-butenyl or 2-pentenyl.

As Cy~Cy aralkyl means Ry, and T2»in particular phenethyl or above all benzyl, If T.. and T2 together with Catome form a cycloalkane ring then this can e.g. be a cyclopentane, cyclohexane", cyclooctane" or cyclodedecane ring.

If Ry means C2""C^hydroxyalkyl, then an e.g. 2 ""hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

As C^"C^Q~aryl, Ry and T2" mean in particular phenyl, α- or 3-naphthyl, which is optionally substituted by halogen or -C 1 -alkyl.

If Ry means C2~C^2 alkylene, then it is about

e.g. ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene octamethylene, decamethylene or didecamethylene.

As C₁-C₂₂₂alkenylene, Ry means especially 2-butenylene, 2-pentenyl one or 3-hexenylene.

If R denotes C 1 -C arylene, then one means, for example, o-, m- or p-phenylene, 1,4-°naphthylene or 4,4'"diphenylene.

Means Z' <-'2"^12 alkanoyl, sa means, for example, propionyl, butyryl, octanoyl, dodecanoyl, but preferably acetyl.

X has the meaning given under b) as C8-C3 alkylene, ^S~3 arylene or C3-C32 cycloalkylene.

Examples of tetraalkylpiperidine photoprotectors from this class are the following compounds: 47) 3-benzyl -1, 3» 8-triaza-7, 7, 9» 9-tetramethylspiro £7decan-2, 4-dione,48) 3-n -octyl-1, 3, 8-triaza-7, 7, 9» 9-tetramethylspiro _/ 4._5_7decan-2, 4-dione,49) 3-allyl -1,3» 8-triaza-1, 7 , 7, 9»9-pen tame tyl sp iro £~5.7decan^2, 4-dione, 50) 3-glycidyl-1, 3»8-tEiaza-7, 7, 8, 9»9-pentamethyl- spiro^ 4. 5_"7decan-2, 4-dione, 5t) 2 - is o -propyl -7, 7, 9» 9-1 et ram et yl -1 -oxa-3, 8-diaza- 4-oxo-spiro-d/_ 4.5_7decane, 52) 2, 2-dibutyl-7, 7,-9» 9-tetramethyl'1-oxa-3» 8-diaza-4.-oxo-spiro-_/ 4-5_7decan, 53) 2, 2, 4, 4-tetramet<y>l-7-oxa-3, 20diaza-2 1^oxo-dispiro/ 5« 1 • 11 • 2_7-heneicosan, 54) 2'* butyl-7, 7, 9, 9~tetramethyl-1-oxa-4, 8~diaza-3-oxo- spiro-/ 4«57decane, or the compounds with the following formulas: e i) Light protection agent with formula VI. in which n means the numbers 1 or 2, and RQ means a group with formula "TT MTT " in which R has the meaning given for formula I, R^ has the meaning given under aj, Y means -0- or -NR^-, A means C^- C^ alkylene or -(CH^^-O-°§x means the numbers 0 or 1, R^ is equal to Rg or one of the groups -NR^R^» "^^-13" -NHCHgOR^ „ or -N (CH20R1 )2> R1Q means when n = 1 the group Rg or R^, and when n = 2 the group -Y-B-X-, in which B means optionally -N (R )- interrupted C^C^alkylene, R^ means C ^-C^2alkyl, cyclohexyl, benzyl or C^-C hydroxyalkyl or a gruDPe of formula... _.. _ ^ R^2means C^-C^2alkyl, cyclohexyl, benzyl, C^-C^hydroxyalkyl and R ...3 means hydrogen, C1-C12 alkyl or phenyl, or R^ and R^2 together mean C^-C^alkylene or oxaalkylene' or R^ and R^2 each mean a group of formula

If some substituents mean C₁-C₁alkyl, they mean, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n -nonyl, n-decyl, n-undecyl or n-dodecyl.

If any substituents mean C 1 -C 4 hydroxyalkyl, then they mean e.g. 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl .■

Does A mean Co-Cq Skylen, sa means, for example, ethylene, propylene, 2, 2-dimethylpropylene, tetramethylene or hexamethylene.

Means R^. and R^ together C^=C^alkylene or oxaalkylene, then these mean e.g. tetramethylene, pentamethylene or 2-oxap entamethylene.

Examples of tetraalkylpiperidine "light protectants" - agents of this class are the compounds with the following formulas:

f) Light protection agent with formula VII

wherein n means the numbers 1 or 2, R has the meaning given for formula I, and R^ means when n = 1, C^-Cjg alkyl, CyC^ aralkyl, the group -CO-R^, with -CN, -COOR^ , -OH or

-0C0R„-, substituted C.-C, alkyl or

wherein R 1 -C 12 alkyl, C 8 -C 12 alkenyl or phenyl, R 1 means C 12 C 12 alkyl, R 1 ? means C-^^g alkyl, C8-C^ alkenyl, cyclohexyl, benzyl or C^-C^q aryl, or when n = 2, R^ means C^-C12 alkylene, 2-but enylene-1,4, xylylene , the group "(CHg^-00C"R18-C00" (CH2)2- or the group -CH2"00C-Rig-C00-CH2%-i where R^g means Cg-C^Qalkylene, phenylene or cyclohexyl one and R ^ means C^-C^q alkylene, xylylene or cyclohexyl one.

If any substituents mean C^"C^2alkyl, then they are, for example, methyl, ethyl, n-propyl, n'-butyl, sec.butyl, tert.-butyl, n-hexyl, n^octyl, 2" ethyl"hexyl, n-nonyl, n"decyl, now undecyl or n"dodecyl.

Any substituents which may mean Cj~C|g

can e.g. be the above-mentioned groups and in addition, for example, show n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl. If any groups mean C8-C6-alkylene, then they mean, for example, ethylene, propylene, 2,2-dimethylpropylene, tetra " methylene, hexamethylene, octameylene or decamethylene.

R₂ means as C₁-C₂ alkyl, e.g. n-butyl, sec.-butyl, tert.-butyl, n-hexyl, n-octyl, 2-ethyl "hexyl, 1, 1.-dimethyl-2-tert.-butylethyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

If R^ means a -CN-substituted ^-C^alkyl, then it means, for example, cyanomethyl, cyanoethyl, 3-cyano-n-propyl

or 4-cyano-n-butyl.

If R. , C^-C^ alkylene, then it concerns e.g. about 2, 2-dlme tylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylen.

If R^ means Cy-C^^ aralkyl, then a particularly means phenethyl, p-methyl-benzyl or above all benzyl.

R-j^ as Cg-C^ alkenyl means, for example, vinyl, 1-propenyl, allyl, metallyl, 2-butenyl.

R^y means as Cg-Cj^alkenyl, e.g. those for R^

in the sense of alkenyl listed groups and in addition for example crotyl, 2-hexenyl, 2-octenyl or 2-decenyl. If R^y means C^-G^ aryl, then for example a possible o- or p-position with methyl, ethyl, isopropyl, n-butyl or tert-butyl substituted phenyl.

Examples for tetraalkyl pipes are id in "light protect el s es - agents of this class have the following compounds: 65) bis-/ 3-(2, 2, 6, 6-tetramethylpiperidino )~ ethyl 7-se ba eat, 66 ) a -(.2,2,6, 6-tetramethyl "piperidino ) edd ik acid "n" oetyl = ester,

67) 1,4-bis" (2,2,6,6-tetramethylpiperidino)-2-butene.

g) Light protectants with formula VIII

wherein B means "NCRg^)- or "O", E means the ^"C-^ alkylene group

~CH2~CH(,Z )-0", where Z means hydrogen, methyl ■■■or- phenyl,

the group ~ (CHg ),j "NH- or a single bond, R means hydrogen or methyl, R^ has the meaning given under a), R^^ means hydrogen or C^"C^g alkyl, R^-j means hydrogen , C^-C^g alkyl, C^-Cy cycloalkyl, Cy-C^ aralkyl, cyanoethyl, C^-C^g aryl,

the group -CHg-CH(Z)"OH, a group of formula

or a group with formula

wherein Z is hydrogen, methyl or phenyl and G is C 8 -C 3 alkylene or C 3 -C 3 arylene, or R 3 is a group

-E-C0-NH-CH2-OR2Q.

•If any substituents mean C^-Cjg alkyl, then they mean e.g. methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n~ dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Means any substituents Cy-C^2aralkyl,

then they mean, for example, phenethyl or especially benzyl.

When R 1 means C 1 -C 8 alkenyl, it can e.g.

be 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, or 4-tert.-butyl-2-butenyl.

R.j is spm C 1 -C 8 alkenyl, preferably propargyl.

As Cj-Cg alkanoyl, R- means, for example, formyl, propionyl, butyryl, octanoyl, but preferably acetyl as C-^-Cc, alkenoyl, especially acryloyl.

R 2 , as C 2 -Cr, is cycloalkyl, especially cyclohexyl.

As C₁-C₁₂ aryl, R₂ means especially phenyl, a- or B-naphthyl which is optionally substituted with halogen or C₁-C₂. alkyl. E means as C^-C^ alkylene, e.g. methylene, ethylene or

propyl en.

As Cg-C^alkylene, G means, for example, ethylene, propylene, 2,2-dimethylpropylene, tetraethylene, or hexamethylene and as C^-C^arylene o-, m- or p-phenylene, 1, 4.- na f tyl en or 4, 4' -dif enylene.

Examples of tetraalkylpiperidine~light protectants of this class are the following compounds: 68) N-hydroxymethyl-N'-2,2,6,6-tetramethylpiperidine"4"

yl-urine substance,

69 ) N-methoxymethyl -N' "2, 2, 6, 6~tetramethylpiperidin"4-yl"urea, ?0) N"methoxymethyl-N1-n"dodecyl~N'~ 2,2,6,6-tetramethyl -piperidine" 4"yl"urea. 71 ) 0" (2, 2, 6, 6-tetramethylpiperidin-4-yl )-N-methoxymethyl-urethane. h) Photoprotectant with formula IX

wherein n means a number from 1 to 4, preferably 1 or 2, R

and R^ under a) stated meaning, R 22 means hydrogen, hydroxyl or C 1 -C 8 alkoxy, and R^^ means when n = 1, ^-\"^ 2Q alkyl,

C₁-C₁ alkoxyalkyl, C₁-C₁ cycloalkyl, or C₁-C₁ aralkyl,

when n is 2, C^-C^ .alkylene, or with one or two -0- of-

broken C^-Cg alkylene, C^-C^ cycloalkylene, Cg-C^cycloalkylene-dialkylene or Cg-C^ aralkylene, when n = 3, ^ 2~^ 12 alkanetriyl,

and when n = 4»C^-C|2alkanetetrayl.

Examples of R,^ as a monovalent residue are ethyl, 2-ethylbutyl, n-octyl, n-dodecyl, n-octadecyl, -2-isopropoxyethyl, 2-dodecyloxyethyl, 2-butoxypropyl, cyclohexyl, cyclooctyl, benzyl or 2 -phenylethyl. Examples of R2^ as a divalent residue are 1,2-ethylene, tetramethylene, hexamethylene, octamethylene, dodecamethylene, 3-oxa-pentamethylene, 3»6-dioxaoctamethylene, 1»4-cyclohexylene, 1,5- cyclooctylene, 1, A -cyclohexyl en-dimethyl en, 1, 4--cyclohexyl en-diethyl en, m- or p-xylylene. Examples of Rg-j as a trivalent residue are propane-1,2,3-triyl, 1,1,1-trimethyl-enetane or 1,1,1-trimethyl enpropane. Examples for R 1 as a divalent residue are butane-1,2,3»4-tetrayl or tetramethylene-methane.

i) Polymeric compounds whose inverted structural unit contains a tetraalkylpiperidine residue of formula I, in particular polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyethers, polyamides, polyamines, polyurethanes, polyurethanes, polyaminotriazines, poly(meth ) acrylates, poly(meth)acrylamides and their copolymers, which contain such residues.

Examples of tetraalkylpiperidine*"light protection agents - agents of this class are the compounds with the following formulas where m means the numbers 2- about 200.

• j) Compounds which in their molecule contain at least one 2-(2'-hydroxyphenyl)-benztriazole group or 2-hydroxy-benzophenone group and at least one tetraalkylpiperidine group.

Examples of tetraalkylpiperidine photoprotectors of this class are compounds with the following formulas

As far as the tetraalkylpiperidine compounds are basic compounds, they can form salts with acids. This includes, for example, inorganic acids or organic carboxylic acids, sulphonic, phosphonic or phosphinic acids, such as e.g. hydrochloric acid, boric acid, phosphoric acid, acetic acid, salicylic acid, toluenesulfonic acid or benzenephosphonic acid.

Instead of the 2,2,6,6-tetraalkylpiperidines

other sterically hindered -heterocyclic amines can also be used, such as, for example, the compounds with the following formulas:

in which R 1 and R 4 L mean hydrogen, C^-C^-alkyl, C^-Cj2 hydroxyalkyl, C^ "C^-haloalkyl, Cg-C^2-cyanoalkyl, C^-C^2-aminoalkyl, C2-C ^-alkenyl, or Cy-C^-aralkyl, and R^ also means oxygen, hydroxy or alkoxy,

<R>0 and R3.means C^-C^2-alkyl or -halo-alkyl, C2-C^2 means cyanoalkyl, C^-C^2-aminoalkyl, C^-C^-cycloalkyl or -hydroxycycloalkyl, C2" C 1 -alkenyl or C 1 -C 4 -aralkyl.

R5, R<6>, R7 and R8 mean C^C^-alkyl or halo-genal<alkyl,><C>2~^12cyanoalkyl, G^-C^ aminoalkyl, Cg-C^ alke-

nyl or Cn-C., aralkyl, •

2 3 ^ 6

R and R , as well as R" and R can each time together

form C, -C/--alkylene,

R 7 and R 8 can also o be hydrogen, and R and R 8 together with the C atom to which they are bound can form a polymethylene ring with 5-6 C atoms.

The UV absorbers applicable according to the invention

is likewise generally known. This includes in particular the following connection classes:

1. 2-(2<1->hydroxyphenyl)-benztriazoles, such as e.g. 5<1->methyl-, 3', 5'-di-tert.-butyl-, .-butyl-, 5' - (1, 1, 1, 3, 3-tetramethyl butyl )-, 5-chloro-3' , 51 -di-tert. -butyl-, 5-chloro-3'-tert-butyl-5'-methyl-, 3'-sec. -but yl-5'-tert. -butyl-, 3'-a-methylbenzyl-5'-methyl-, 3'-a-methyl benzyl-5'-methyl-5-chloro-,4'-hydroxy-, 4-'-methoxy-, 4 ' -octyloxy-, 3 1 >5'-di-tert.-amyl-, 3' -methyl-5'-carbo me toc sy-ethyl-, 3' » 5' -bis (a,a-di met yl benzyl )-, 3'5'-bis(a,a -dimethylbenzyl )-5-chloro-, 3' , 51-di. -1 is t.-o ethyl-, 3'5'-di.-tert.-octyl-5-chloro- or 5-chloro-3<1>,5'-di-tert.-amyl derivative. 2. 2,4-bis-(2<1>-hydroxyphenyl)-6-alkyl-s-triazines, such as e.g. 6-ethyl-, 6-heptad ecyl - or 6-undecyl-derivatives. 3-2-hydroxybenzophenones such as e.g. 4-hydroxy-, 4--methoxy-, 4-octoxy-, 4-'"decyloxy-, 4-dsdecyloxy-, 4."benzyloxy-, 4-, 2' , 4.'-trihydroxy- or 2 1 -hydroxy-4-, 4.' "dimethoxy derivatives. 4-.1,3-bis-(2'-hydroxybenzoyl)"benzenes, e.g. 1,3-bis(2'-hydroxy-4,'-hexyloxy-benzoyl)-benzene, 1,3"bis-(2'-hydroxy-4-'-octyloxy-benzoyl)~benzene or 1,3" bis"(2'~hydroxy-4.'-dodecyloxy-benzoyl)-benzene. 5. Esters of optionally substituted benzoic acids, such as e.g. 4-tert.-butyl-phenyl salicylate, phenyl salicylate . .-butyl-phenyl ester is. 6. Acrylates such as, for example, α-cyano-3»3-diphenylacrylic acid ethyl ester or -isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester, α-cyano-3-methyl- p-Methoxy-cinnamic acid methyl ester or -butyl ester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N-(3-carbomethoxy-3-cyanovinyl)-2-methyl-indoline 7. Oxalic acid ediamides such as ejs . -tert.-butyl-oxanilide, 2, ethoxy-2'-ethyl-oxanilide, N,N'-bis-(3-dimethylaminopropyl)-oxalamide, 2, ethoxy -5-tert. -butyl-2'-ethyloxanilide, 2,ethoxy-2'-ethyl-5,4'-di-tert. - butyl oxanilide, mixtures of ortho- and para-methoxy- as well as o- and p-ethoxy-disubstituted oxanilides. Among the UV absorbers used according to the invention, those from class 1 (benztriazoles) are preferred. Such benztriazoles are e.g. disclosed in US Pat ents Nos. 3,004,896, 3,189,615, 3,320,194, 4,127,586, and 4,283,327.

The term "fungicides" as used here shall, in general terms, include all compounds with an inhibitory or exterminating effect on fungi and mould. Typical fungicide classes are carbamates such as 3-iodo-2-propynyl-N-butylcarbamate, dimethyl-dithiocarbamate; 2"sec -butylphenyl"*N-methylcarbamate, benzimidazole carbamates, 1-naphthyl-N-methylcarbamate j 3"methyl~ 4-dimethylaminophenyl-N-methyl-carbamate or 3,4"dimethyl-6-chlorophenyl "N-methylcarbamate, chlorinated phenols such as tetrachlorophenol, pentachlorophenol, or sodium pentachlorophenolate, non-phenolic chlorinated compounds such as 1" chlorine, N-trichloromethylthio-4-cyclohexene- 1,2-dicarboximide, N-trichloromethyl" thiophthalimide, tetrachloroisophthalonitrile, tetrachloropyridine-4"methyl-. sulfonate, 2,4-dichloro-6-(o~chloroanilino)-s-triazine, 2,3-dichloro-1,4-naphthoquinone, α,α-bis(p-chlorophenyl)-3-pyridyl-methanol or pentachloronitrobenzene, organotin compounds such as tri-butyltin oxide, mercury compounds such as phenylmercuric silver acetate or oleate, zinc compounds such as Zn-naphthenate or Zn-dimethyldithiocarbamate, copper compounds such as copper-chromium-arsenate or copper-naphthenate, ketones such as 2-n-octyl-4-isothiazolin-3-one or 3,3,-ethylene-bis/tetrahydro-4,6-dimethyl-2H-1,3,5-thiadiazin-2-thione;

sulfones such as e.g. 1, 2-bis-(n-propylsulfonyl)-ethane or other fungicides as they are known to those skilled in the art. For this purpose, reference should also be made to the specialist literature, e.g. Dewayne, Torgeson, "Fungicides", Vol. II, Academic Press, New York, 1969, or Ullmann's Encyclopéidie der technischen Chemie, 4th edition, Volume 12, 1-14 (1976).

The stabilizers are used according to the invention i

an amount of approx. 0.25 to 4 parts by weight, preferably 0.5 to 1.5 parts by weight per part by weight of fungicide.. If a combination of piperidine compound and UV absorber is used, their weight ratio is preferably 16:1 to 1:16, especially 3:1 to 1:3. The possible amounts used depend on the nature of the fungicide, on the desired degree and stabilization and on the nature of the substrate. To the mixture of stabilizer, to the fungicide or to the formulations of the fungicide is no problem and can be done by usual methods, at any suitable time before application.

The fungicides can be stabilized according to the invention regardless of whether they are used in solution, emulsion or other liquid form. Special forms of application are additives for coating colours, lacquers, glazes, wood protective coatings, water-repellent impregnation and similar coating formulations. Such formulations may contain binders, such as e.g. alkyl resins, acrylic resins, polyester resins, phenolic resins, polyurethanes, epoxy resins, or mixtures thereof, they may contain solvents, surfactants, foam breakers, thickeners, such as e.g. carboxymethyl cellulose, or polyacrylic acid derivatives, plasticizers, dispersants, water repellents, drying oils, pigments, fillers such as e.g. asbestos, talc or kaolin and similar components.

Insofar as these formulations are polymer compositions, the formulations may contain polymeric additives, as is usual in the technology of plastics and varnishes, especially stabilizers of various types. Such polymer additives are preferably used in an amount of 0.1-5% by weight, especially 0.5% by weight, referring to the polymer. ■ Of particular importance is the addition of antioxidants, especially those from the class of sterically hindered phenols, which include: - 1. Alkylated monophenols such as 2,6-di.-tert.-butyl-4-methylphenol, 2-tert.-butyl-4,6-dimethylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2 " (a-methyl cyclohexyl)-4, 6-dimethylphenol, 2, 6_di-octadecyl-4-methylphenol or 2,6-di-tert-butyl-4-methoxymethyl-phenol, 2. Alkylated hydroquinones, which 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone or 2,6-diphenyl-4 -octadecylcksyphenol, 3. Hydroxylated thiodiphenyl ethers such as 2,2'-thio-bis-(6-tert.-butyl-4-methylphenol), 2, 2'-thio-bis-(4-octylphenol), 4,4' -ti o-bis - (6-tert.-butyl-3-methyl.phenol ) or 4» 4' -thio-bis - (6-tert.-butyl-2-methylphenol ), 4. Alkylidene- bisphenol is as 2,^2'-methylene-bis-(6-tert-butyl-4-rnetylphenol), 2,2'-methyl en-bis (4-met yl - 6-cyclohexyl phenol), 2,2'-methyl en-bis (4» 6-di-tert. -butyl phenol ), 2,2' - ethylidene-bis - (4> 6-di-tert. -butylphenol ), 4» 4-' -methylene-bis (2, 6-di-tert. -butyl - phenol), 4» 4' -methyl en-bis (6-tert. -butyl-2-methylphenol 1 -bis-(5-tert.-butyl-4°hydroxy-2-methylphenyl) -butane or 1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane, 5. Hydroxybenzyl compounds such as 1,3»5-tri-(3, 5-di-tert .-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 3»5-di-tert.-butyl-4-hydroxy-benzyl-mercaptoacetic acid-isooctyl-ester, 1,3»5-tris - ( 3, 5-di-tert.-butyl -4-hydroxybenzyl)-isocyanurate, 1,3»5.-tris-(4"tert."butyl-3-hydroxy-2,6-dimethyl-benzyl)-isocyanurate , 3»5-di"tert-butyl-4-hydroxybenzyl-phosphonic acid dioctadecyl ester or 3»5"di-tert-butyl-4"hydroxy-benzyl-phosphonic acid monoethyl ester calcium salt, 6 Esters of 3-(3,5-di-tert.-butyl~4~hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols such as e.g. with methanol, octadecanol, 1,6"hexanediol, neopentyl glycol, thio"diethylene glycol, diethylene glycol, trietyl englycol, pentaerythritol, tris-hydroxyethyl isocyanurate or di-hydroxyethyl"oxalic" acid diamide, 7. Esters of (5-tert.-but<y >l"4-hydroxy<y->3-meth<y>l-phenyl)-propionic acid with mono- or polyhydric alcohols, such as for example with methanol, octadecanol, 1,6_hexanediol, neopentyl glycol, thiodiethylene glycol, diethyl englycol, triethyl englycol, pentaerythritol, tris-hydroxyethyl-isocyanurate or di-hydroxyethyl-oxalic acid diamide, 8. Amides of "3-jf3" 5-di-tert.-butyl-4-hydroxyphenyl) propionic acid, such as N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine, N,N'-di-(3,5-di-tert,-butyl -4-hydroxyphenylpropionyl)-trimethyl.endiamine or N,N' ~ di - (3, 5 -di -tert. -butyl -4-hy d.roxyphenyl -propionyl ) -hydraz in,

Further added polymer stabilizers can be metal deactivators such as e.g. sebacic acid-bis(phenylhydrazide), N,N'-bis(salicyloyl).-oxalic acid dihydrazide or N,N'-bis

(salicyloyl)-thiodipropionic acid dihydrazide, thiosynergists as

e.g. dilauryl thiodipropionate, aromatic and aliphatic-aromatic phosphoric acid esters, or phosphonic acid esters, PVC stabilizers such as methyl carboxylate, organotin compounds or epoxide compounds or light protectants such as

e.g. organic nickel compounds.

The fungicide formulations can be applied to different substrates. Of particular importance is application on wood, metal, plastics and masonry for protection against mold and other fungi. Also for materials such as rubber, paper or textiles, it can be advantageous to use a fungicide. The task of the stabilizer added according to the invention is here to protect the fungicide from decomposition, and from there its effect on the substrate is maximally beneficial. The following examples show different areas of application for the invention. Here, parts always mean parts by weight, and percent by weight.

The following commercial fungicides are used in the examples:

Example T

A white wood protection glaze based on linseed oil, TiOg pigments, white spirit and 2, 2, 4-trimethyl-1, 3-pentane-diol monoisobutyrate is mixed with 0.25% 0.5% > 1% > 2% and 2.5% of the fungicide I, II, and III. Each of these 15 mixes is shared

in 5 samples of which each time a sample remains unstable is pea,

a sample is mixed with 1% stabilizer A, a sample with 1% stabilizer B, a sample with 1% A, and "\% B, and a sample

with 2% A, and 1% B. The percentages therefore always refer to solvent-free glaze.

The samples are applied to pine boards of 30x20x1 cm..

The boards are cut in two halves and exposed to climatic influences in the open air. One half is thereby posted 90° to the north, the other half ^ 5° to the south.

After 4 months of climate change, they are showing courage

south-facing boards without stabilizer, as well as comparison samples without fungicide, but with stabilizer, strongly attacked by the fungus. This shows that the stabilizers themselves have no fungicidal effect. The combination of 1% fungicide I with 1% stabilizer A, and 1% stabilizer B.

A corresponding series of experiments ';,' is carried out with the same wood protection glaze, and 0.5% fungicide and different amounts of the stabilizers, of which B over a: full year's climate impact (45° south).. As a comparison, the fungicides are used in a concentration of 0.5 and 2.0% without stabilizer. Fungal growth is assessed according to ASTM D-3274--76 with 1-10, with 10 meaning a mold-free surface. Table 1 shows that the samples with 0.5% fungicide and 1 - 2% stabilizer show approximately the same effect as unstable ice pea samples with 2% fungicide.

Example 2

Films of 90 µm thickness are prepared from an unpigmented ■acrylic resin emulsion (Rohm & Haas, Acrylic Lat ex AC-64) with 60% solid s-t of f content*'. To the emulsion was added

1% fungicide I and various amounts of stabilizer A and its mixtures with B and C. The films are irradiated after drying with a fluorescent solar lamp, in a black illumination chamber for 12 hours. The resulting discoloration of the film characterizes the determination of the Yellowness index, according to ASTM D-1 925-63T before and after illumination. The discoloration occurs with yellow-colored cleavage products I. Table 2 shows the effect of the stabilizers. The specified addition quantities refer to the solid substance (resin) of the emulsion.

Example j3

75 mg of stabilizer A is added to a solution of 20 mg of fungicide IV in 1000 ml of toluene. An unstabilized solution of IV serves as a comparison. These solutions are irradiated in closed ampoules with a fluorescent sunlight lamp in a black illumination chamber. At intervals of 15 minutes, the remaining content of fungicides IV is determined by gas chromatography. The results in table 3 show a clear stabilization with the addition of A.

Example 4

A white touch-on color is prepared according to the following recipe:

Another sample is additionally mixed with % (referenced

to solids content one of the acrylic resin latexes) stabilizer A and 1% stabilizer B.

The colors are applied to strips of filter paper and the dried strips are irradiated with a fluorescent sunlight lamp in a black light chamber for 12 hours. The resulting discoloration is characterized by measuring the Yellow index (Yl) according to ASTM 1 925-:63T. " After irradiation, the Yl of the unstabilized sample is 41.1, while the stabilized sample shows a Yl of 16.22. Before the irradiation, both samples show a Yl of 3.

Example - 5

A commercial exterior paint based on an oil-modified alkyl resin (Sears, semi-Gloss Trimm) is mixed with 0.5% (referred to the solids content of the paint) of fungi-

cid V. Half of this is mixed with 1% stabilizer A and 1% stabilizer B. Both paints are applied to steel tins (Bonderite 1000) and the tins are set at an angle of 45° to the south for an external climatic influence in Florida. After 1 year, the unstabilized paint shows strong mold attack, while the stabilized paint only has ...a minimal amount of mold. When considering below

electron microscope shows that the mycelium of the mold and the stabilized paint is much less dense than on the unstabilized paint.

Example - 6

As discussed in example 3, a solution of 20 ppm fungicide VI in toluene is mixed with 80 ppm stabilizer A and irradiated together with the unstabilized solution with UV light.

At certain intervals, samples of the solution are examined for their content of fungicide VI, following that of J.Satho in Bull. Environment. Contam. Tox. 22 (1979), 590"597 mentioned method. The results are listed in table 4-.

Example 7

0.1 g of a fungicide VI and 0.075 g of stabilizer resp. stabilizer mixture. The inner wall of an ampoule is coated with an acrylic resin thus stabilized as 1 g of the formulated solution is filled into the ampoule, and by turning the ampoule the solvent evaporates in a vacuum. The ampoule is then closed and irradiated with a fluorescent sunlight lamp in a black light chamber. After illumination, the ampoules are opened, the film on the inner wall is extracted with chloroform and the extract is determined for fungicide VI according to the method given in example 6 with gas chromatographic analysis (Ec detector). The results are listed in table 5.

Example 8

As discussed in example 7, the inner side is equipped with of the ampoule with an acrylic resin cover. Various fungicides and various stabilizers are added to the resin solution which are indicated in Table 6. After illumination, the resin film is extracted with 10 ml of chloroform. The extraction solution is diluted twice, and analyzed by thin layer chromatography on silica gel plates. on their content of fungicides. The following elution agents are used to develop the chromatogram for the various fungicides:

After development of the chromatograms by means of UV-fluorescence, the spots of fungicides made visible are qualitatively compared visually.

Example 9

As discussed in example 1, the pine board is coated with a clear wood varnish on a t erpent in base and with a clear varnish on a linoleum base. Both varnishes are mixed with 1% fungicide IX, and with the following stabilizers in the indicated amounts: 2% k. in % A, 1% B, 2% B, 2% A + 1% B, 4% A +

2% B, 2% J, A % J, 2% K, K % K.

As a comparison, the unstabilized formulations are applied. The board is subjected to a five-month climate impact in the open air. After this time, the unstabilized samples show a mold attack of 3 -' 9 according to the scale of ASTM D-3274-76, while all stabilized samples are mold-free, which corresponds to the scale value 10.

Claims (8)

1. Process for stabilizing fungicides against light degradation by adding at least one 2, 2, 6, 6-tetraalkyl - piperidine compound or at least one UV absorber or a mixture of at least one 2, 2, 6, 6-tetraalkyl pipe eridine compounds .with at least one UV absorber. 2. Process according to claim 1, characterized in that the tetraalkylpiperidine compound is a compound containing a group of formula I wherein R means hydrogen or methyl. 3. Method according to claim 2, characterized in that the tetraalkylpiperidine compound is a compound of formula I, in which R means hydrogen. 4. _ Method according to claim 1, characterized in that the UV absorber is a 2-(2'-hydroxyphenyl)-benztriazole. 5. Method according to claim 1, characterized in that a mixture of a 2, 2, 6, 6-tetraalkylpiperidine compound with a UV absorber is used in a ratio of 16:1 to 1:16. 6. Method according to claim 1, characterized in that the fungicide is one from the group of carbamates, chlorinated phenols, non-phenolized chlorinated compounds, organic compounds, mercury, copper or zinc compounds, ketones or sulphones. 7. Composition containing a fungicide and a light protectant, the light protectant being either a 2, 2, 6, 6-tetraalkylpiperidine compound :: or a UV absorber or a mixture of a tetraalkylpiperidine compound and a UV absorber. 8 . Use of a composition according to claim 8 in paints, varnishes, glazes, wood protection, etc. smoke, water repellency, impregnations and similar on printing media.