CA1195246A - Stabilized fungicide compositions - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Fungicides and fungicidal formulations are stabilized against the adverse effects of exposure to light by the addition thereto of effective amounts of a 2,2,6,6-tetraalkylpiperidine compound, or a UV absorber, or a blend of said piperidine compound and said UV absorber

Description

\

~5~ -~6 ~ he use of organic fungicides for the protection of natural and synthetic organic materials from microbiological attack in exterior service application is wide spread. All organic materials are potential carbon sources for biological assimilation. Fungicides are used extensively in agricultural, chemical and polymer technology to protect organics which are either indigenous to the outdoors or require an extended exterior service life. Failure of a fungicide to perform properly results in microbiological invasion. Microorganisms deface and destroy organic substances through enzymatic attack. The role of the fungicide is to create a toxic environment which is not conducive to supporting life. A toxic environment must be maintained for organic materials in exterior service situations to remain free from biota.

Most organic fungicides are sensitive to sunlight and readily decompose upon exposure. Many organic and organo metallic fungicides are strong UV absorbing chemicals with one or more photo-sensitive bonds. Photochemical decomposition of fungicides has been detailed in the literature.
Photodecomposition of a funglcide is the primary factor in reducing the effective service life of a fungicide. Fungicides are presently being formulated to take into account migration and loss of fungicide due to natural weathering. The efficiency of a fungicide therefore depends upon the maintenance of a minimum inhibitory concentration (MIC) of a fungicide for a precise period of time. This is referred to as the efficacy of a system.

The minimum inhibitor concentration is complemented by the concept of "shaped-charge" Horsfall, "Principles of Fungicidal Action" Chronica Botanica Mass. (1956) A fungicide is active only if the original molecular design of the fungicide is maintained when in contact with the invading organism. The concept of "shaped-charge" state that the fungicide molecule has at least two sites which must be maintained for effective fungicidal activity. One site facilities fungicide passage through the organism cell wall. The other site the toxaphor or poison center, delivers the actual lethal chemistry to the organism. These sites must be maintained in order for the fungicide to be effective. Photochemical decomposition destroys these important sites and thus the shape charge leaving the fungicide ineffective.

Photochemical decomposition not only reduces the fungicide's efficiency through destruction of shape charge but may also produce volatile by-products of decomposition that eventually produce even more toxic material. The latter two situations pose both an environmental as well as a health hazard. It is therefore desirable to reduce or prevent fungicides from the degradatiQn produced by exposure to ultra-violet sources. Additional background information on fungicide stabilization may be obtained from Enninga et al, "Fungicides in Latex Paints", Biodeterioration of Materials, Proceedings of 1st International Biodeterioration Symposium, Elsevier Publishing Co., New York, pp 326-332 (1968).

Two methods have generally been utili~ed to overcome this breakdown problem. A first approach involves loading high levels of fungicide into the formulation in order to compensate for the breakdown over time. This approach is further discussed in the Enninga et al paper. The second approach involves the incorporation of a screen to physically block the sun~s harmful UV radiation. The disadvantages of the first approach are two-fold. High levels of fungicide are costly. High levels are also a danger to mammalian contact. Therefore, the high loading of a fungicide beyond the MIC is economically and environmentally undesirable. The primary disadvantage of the second approach is that UV screens are usually pigments. The disadvantages of the use of pigments include poor solubility, chalking, opacity and embrittlement. Pigments also tend to initiate photodecomposition. Accordingly, this second approach is likewise deemed inadequate.

. .

The present invention relates therefore to the s-tabillz-ation of fungicides against light induced deterioration by -the incorporation in fungicide compositions of a 2,2,6,6-tetraalkyl-piperidine compound, or a mixture thereof with an ultraviolet absorber. The invention also relates to the stabilized composi-tions resulting therefrom as well as to formulated systems, such as paints, substrate treatments and protective coatings, contain-ing said stabilized fungicides.
The utilization of such stabilizer systems substa:ntially overcomes most of the difficulties encountered with prior art approaches. Thus, the chemical mechanisms and solubility charac-teristics of these compo-mds facilitates their incorporation into fungicide compositions and their ability to prevent deterioration of the fungicide and consequent reduction in fungicidal activi-ty.
More specifically, the UV absorber serves to preven-t the fungicide from "seeing" the ultraviolet light which causes its degradation.
In turn, the piperidine compound prevents the fungicide from degrading due to free radical attack on the molecule. The compound terminates these available free radi.cals. The combination of the -two therefore provides added benefits by attacking two distinct mechan.isms of degradation of the fungicide. Of primary signifi-cance, the stabilization effectiveness of these syste~s allows for a reduction in the

2 ~6 concentration levels necessary to provide a satisfactory fungi-cidal response. Accordingly, the environmental and economic dis-advanta~es noted hereinabove are now substantially eliminated.

The individual piperdine compounds and UV absorbers as well as the combination thereof are known and are recognized for their ability to combat light-induced degradation of polymeric sub-strates and various resin-based coatin~s. Representative patents disclosing the individual piperidines and UV absorbers are noted hereinbelow. Blends for stabilization of said substrates and coatings are disclosed, for example, in U~S. Patent Nos.
4,110,304 4,283,327, 4,3~4i933, 4,344,876 and European 2,753.

The use of individual UV absorbers to combat light-induced degradation of insecticides is likewise known. For example, U.S. 4,056,610 and U.S~ 4,171 355 disclose the use of W
absorbers such as benzophenones, benzotriazoles, malonates, triazines and nickel compounds to stabilize pyrethroid insecticides. Ger. Offen. 2,139,625 discloses the use of speci~ic benzotriazoles for the stabilization of ethylphenoxy-epoxy-octene insecticides. South African 71/05,370 likewise discloses the use of specific benzotriazoles to stabilize larvacides. Chem. Abstracts 77/18322 discloses the use of benzophenones for the stabilization of pyrethrin and allethrin insecticides.

The stabilization of fungicidal compositions, however, represents a special situation in view of the unique problems encountered therewith, said problems being itemized hereinabove.
Accordingly, the unexpec-ted discovery discussed and claimed herein reflects an understanding of these problems and a recognition of the elements that disting~ish the stabilization of fungicides from the stabilization of various polymeric substratesl coatings and insecticides.

The 2,2,6,6-tetraalkylpiperidine compounds to be used according to the invention are generally known and are recognized for their ability to combat light degradation. U.S. 3,542,729, U.S. 3,640,928, U.S. 3,840,494, U.S. 4,021,432, U.S. 4,049,647, U.S. 4.064,102, U.S. 4,086,204 and U.S. 4,265,805 are typical of the numerous patents that disclose such piperidine light stabilizers.

The hindered amine light stabilizers useful in the instant invention are in particular 2,2,6,6-tetraalkylpiperidine compounds which contain a group of the formula (I) ;2~6 RCH2 y ~ R

` RCH / \ H
in which R is hydrogen or methyl.
The light stabilisers to be used according to the invention include on particular the following classes of compounds:
a) Light stabilisers of the formula (II) RCH ~ ~ R

Rl- N ~ - O~ R2 (II) H2 CH3 n in which n is a number from 1 - 4 inclusive, preferably 1 or 2; R is as defined under the formula (I); Rl is hydrogen~ oxyl~ Cl Cl8 alkyl~ C3-C8 alkenyl, C3-C8 alkynyl, C7-C12 aralkyl, Cl-C8 alkanoyl, C3-C5 alkenoyl, glycidyl, a group -CH2CH(OH)-Z wherein Z is hydrogen, methyl or phenyl, with Rl preferably being hydrogen, Cl-C12 alkyl, allyl, benzyl, acetyl or acryloyl; and R2 when n is 1 is hydrogen, Cl-C18 alkyl optionally interrupted by one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a mono-valent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acid, or of carbamic acid or of a pho~phorus-containing acid, or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having 2 - 18 C atoms, of a cycloaliphatic carboxylic acid having 5 - 12 atoms or of an aromatic carboxylic acid having 7 - 15 C atoms; R2 when n is 2 is Cl-C12 alkylene, C4-C12 alkenylene, xylylene, a bivalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, of dicarbamic acid or of a phosphorus-containing acid, or a bivalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid having 2 - 36 C atoms, of a cycloaliphatic or aromatic dicarboxylic acid having 8 - 14 C atoms, or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8 - 14 C atoms; R2 when n is 3 is a trivalent radical of an aliphatic, cyclo-aliphatic or aromatic tricarboxylic acid, of an aromatic tricarbamic acid or of a phosphorus_containing acid, or a trivalent silyl radical; and R2 when n is 4 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

If any substituents are Cl-C12 alkyl, they are for example methyl, ethyl, n-propyl, n-butyl, sec-butyl, ter~-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
As Cl-C18 alkyl, R1 or R2 can be for example the groups given above, and in addition for example n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
When Rl is C3-C8 alkenyl, it can be for example l-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tert-butyl-2--butenyl.

_ g _ ~l~9~;;zi~

As C3-C8 alkynyl, Rl is preferably propargyl.
Rl as C7-C12 aralkyl is in particular phenethyl or especially benzyl.
As Cl-C8 alkanoyl, Rl is for example formyl, propionyl, butyryl, octanoyl but preferably acetyl, and as C3-C5 alkenoyl, Rl is particularly acryloyl.
If R2 is a monovalent radical of a carboxylic acid, it is for example a radical of acetic acid, stearic acid, salicylic acid, methacrylic acid, maleic acid, benzoic acid or ~-(3,5-di-tert-butyl-4-hydroxyphenyl3-propionic acid.

;~

2 ~;

If R2 is a bivalent radical of a dicarboxylic acid, it is for example a radical of adipic acid, suberic acid, sebacic acid, maleic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid or butyl-~3,5-di-tert-butyl-4-hydroxybenzyl)-malonic acid, or bicycloheptenedicarboxylic acid.

If R2 is a trivalent radical of a tricarboxylic acid, it is for example a radical of trimellitic acid or of nitrilotriacetic acid.

If ~2 is a -tetravalent radical of a tetracarboxylic acid, it is fGr example a radical of pyromellitic acid or butane-1,2,3,4-tetracarboxylic acid.

If R2 is a bivalent radical of a dicarbamic acid, it is for example a radical of hexamethylenedicarbamic acid or of 2,4-toluylenedicarbamic acid.

The following compounds are examples of polyalkylpiperidine light stabilizers of this class:

1) 4-hydroxy-2t2r6/6-tetramethylpiperidine~
2) 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,

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

4) 1-(4-tert-Dutyl-2-butenyl)-4-hydroxy-2,2,6,6-tetra-methylpiperidine,

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

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

7) 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine,

8) 1,2,2,6,6-pentamethylpiperidin-4-yl-~-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate,

9) 1-benzyl-2,2,6,6-tetramethyl-4-piperidinylmaleinate,

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-tetramethyl-piperidin-4-yl)-phthalate,

14) 1-propargyl-4-~-cyanoethyloxy-2,2,6,6-tetramethyl-piperidine,

15) 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-acetate,

16) trimellitic acid-tri~(2,2,6,6-tetramethylpiperidin-4-yl)-ester,

17) 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine,

18) dibutyl-malonic acid-di(1,2,2,6,6-pentamethvl-piperidin-4-yl)-ester,

19) butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)-malonic acid-di-(1,2,2,6,6-pentamethylpiperidin-4-yl)-ester,

20) dibenzyl-malonic acid-di-(1,2,2,6,6-pentamethyl-piperidin-4-yl)-ester,

21) dibenzyl-malonic acid-di-(1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl)-ester, ,i 2~6

22) hexane-1',6'-bis-(~-varbamoyloxy-1-n-butyl-2,2,6,6-tetramethylpiperidine),

23) toluene-2',4'-bis-(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiperidine),

24) dimethyl-bis-(2,2,6,6-tetramethylpiperidine-4-oxy)-silane,

25) phenyl-tris-(2,2,6,6-tetramethylpiperidine-4-oxy)-silane,

26) tris-(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl)-phosphite,

27) tris-(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl)-phosphate, and

28) phenyl-[bis-(1,2,2,6,6-pentamethylpiperidin-~-yl)]-phosphonate,

29) di(l,2,2,6,6-pentamethylpiperidin-4-yl)-sebacate b) Light stabilisers of the formula (III

¦ RCH2 ~ R3 1 Rl- N ~ -~ T R4 (III) RCH2 CH3 n Z~6 in which n is the number 1 or 2; R is as defined under the formula I; Rl is as defined under a); R3 is hydrogen, Cl-C12 alkyl, C5-C7 cycloalkyl, C7-C8 aralkyl, C2-C18 alkanoyl, C3-C5 alkenoyl or benzoyl; and R4, when n is 1, is hydrogen, Cl-C18 alkyl, C3-C~3 alkenyl, C5-C7 cycloalkyl, C2-C8 alkyl substituted by a cyano, carbonyl or carbamide group t or it is glycidyl, a group of the formula -CH2-CH(OH)-Z or of the formula -CONH-Z wherein Z is hydrogen, methyl or phenyl; or R4 when n is 2 is C2-C12 alkylene, C6-C12 arylene, xylylene, a -CH2-CH(OH)-CH2 group, or a group -cH2-cH(oH)-cH2-o-x-o-cH2-cH(oH)-cH
s C2 C10 alkylene, C6 C15 arylene or C -C
cycloalkylene; or, provided that R3 is not alkanoyl~
alkenoyl or benzoyl, R4 can also be a bivalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or can be the group -CO-; or R3 and R4 together when n is 1 can be the cyclic radical of an aliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.
If any substituents are Cl-C18 alkyl, they are as already defined under a).
If any substituents are C5-C7 cycloalkyl, they are in particular cyclohexane.
As C7-C8 aralkyl, R3 is particularly phenethyl or above all benzyl.

-- 1~ --,,~
.,~

S2~6 As C2-C18 alkanoyl, R3 is for example propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl but preferably acetyl; and as C3-C5 alkenoyl, R3 is in particular acryloyl.
If R4 is C2-C8 alkenyl unsubstituted or substituted by a cyano, carbonyl or carbamide group r it is for example l-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 2,2-dicyanovinyl, 1-methyl-2-cyano-2-methoxy-vinyl or 2,2-diacetylaminovinyl.
If any substituents are C2-C12 alkylene, they are for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
If any substituents are C6-C15 arylene, they are for example o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
As C6-C12 cycloalkylene, X is especially cyclohexylene.
The following compounds are examples of polyalkyl-piperidine light stabilisers of this class:

30) N,N'-bis-(2,2,6,6-tetramethylpiperidin-4-yl)hexamethyl-ene-1,6-diamine, 5~6

31) N,N'-bis-(2,2,6,6-tetramethylpiperidin-4-yl)hexamethyl-ene-1,6-diaceta~ide,

32) 1-acetyl-4-(N-cyclohexylacetamido)-2,2,6,6-tetramethylpiper-idine,

33) 4-benzylamino-2,2,6,6-tetramethylpiperidine,

34) N,N'-bis-(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dibutyl-adipamide,

35) N,N'-bis-(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dicyclo-hexyl-(2-hydroxypropylene),

36) N,N'-bi.s-(2,2,6,6-tetramethylpiperidin-4-yl)-p-xylylene-diamine,

37) the compound of the formula z~

CH CH
3 y 3 C H
CH - ~ ~ N-CH2-CH(OH~-CH2 -O

f 3 ~

CH - N ~ - N-CH2-CH(OH)-CH2- o 3 H3 C4Hg

38) 4-(bis-2-hydroxyethyl)-amino-1,2,2,6,6-pentamethyl-piperidine, ' 39) 4-(3-methyl-4-hydroxy-5-tert-butyl-benzoic-acidamido) 2,2,6,6-tetramethylpiperidine, and 40) 4-methacrylamino-1,2,2,6,6-pentamethylpiperidine.

c) Light stabi.lisers of the Eormula (IV) , ~.~

, s~

RCH2 ~ R ~
Rl- N ~ ~ ~R5 (IV) _ H2 CH3 n in which n is the number 1 or 2; R is as defined under the formula (I); Rl is as definPd under a); and R5, when n is 1 is C2-C8 alkylene or hydroxyalkylene or C4-C22 acyloxyalkylene;
and R5, when n is 2, is the group (-CH2)2C(CH2-)2.

If R5 is C2-C8 alkylene or hydroxyalkylene, it is for example ethylene, l-methyl-ethylene, propylene, 2-ethyl-propylene or 2-ethyl-2-hydroxymethylpropylene~

As C4-C22 acyloxyalkylene, R5 is for example 2-ethyl-2-acetoxymethyl-propylene.

The following compounds are examples of polyalkyl-piperidine light stabilisers of this class:

41) 9-aza-8,8,10,10-tetramethyl~1,5-dioxaspiro[5.5]undecane, 42) 9-aza-8,8,10,10 tetramethyl-3-ethyl-1,5-dioxaspiro[5.5~-undecane, .,.~`,~

43) 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro~4.5]decane, 44) 9-aza 3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1-5-dioxaspiro[5.5]undecane, 45) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetra-methyl-1,5-dioxaspiro[5.5]undecane, and 46) 2,2,6,6-tetramethylpiperidine-4-spiro-2'-(1'~3'-dioxane)-5'-spiro-5" (1"-dioxane)-2"-spiro-4"'-(2"',2"', 6"',6"'-tetramethylpiperidine).

d) Light stabilisers of the formulae (VA), (VB) and (VC) RCO~ ~ 7 ( VA ) 3 5 3 ITl ~ O~--C-T
Rl- N X I 2 ~ NH- C=0 (VB) RCH2 y CEI R T
~ ¦ ( VC ) ~ C- NH
H2 ~H3 0 in which n is the number 1 or 2; R is as defined under the formula (I); R1 is as defined under a); R6 is hydrogen, Cl-C12 alkyl, allyl, benzyl, glycidyl or C2-C6 alkoxyalkyl and R7 when n is 1, is hydrogen, Cl-C12 alkyl, C3 C5 y 7 9 aralkyl, C5-C7 cycloalkyl, C2-C4 hydroxyalkyl, C2-C6 alkoxy-alkyl, C6-C10 - 19 -. ~ , ~3~

aryl, glycidyl, a group of the formula -(CH)-COO-Q or of the formula -(CH2)m-O-CO-Q wherein m is 1 or 2, and Q is Cl-C4 alkyl or phenyl; or R7, when n is 2, is C2-C12 alkylene, C6-C12 arylene, a group -CH2-CH(OH)-CH2-O-X-O-CH2-CH(OH)-CH2- wherein X
is C2-Clo alkylene, C6-C15 arylene or C6-C12 cycloalkylene. or a group -CH2CH(O2') CH2-(OCH2-CH(OZ')CH2)2- wherein Z' is hydrogen, Cl-Cl~7 alkyl, allyl, benzyl, C2-C12 alkanoyl or benzoyl, and T
and T2 independently of another are hydrogen, Cl-Clg alkyl or C6-Clo aryl which is unsubstituted or substituted by halogen or Cl-C4 alkyl, or Cl-Cg aralkyl, or Tl and T2 together with the C
atom which bonds them form Cs-C7 cycloalkyl, pyrrolidinyl or piperidinyl, which are unsubstituted or substituted by Cl-C4 alkyl.

If any substituents are C1~C12 alkyl, they are for exa7r.ple methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, ~-ethyl-he~yl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

As for C1-Clg alkyl, they can be for example the groups stated above, and in addition for example n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

i .~

.

i2 ~
If any substituents are C2-C6 alkoxyalkyl, they are for example methoxymethyl, ethoxymethyl, propoxymethyl, tetr.-Butoxymethyl, ethoxyethyl, ethoxypropyl, n~butoxy-ethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.

If any group is C3~C5 alkenyl, it is for example l-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.

As for C7-Cg aralkyl, they are in paxticular phenethyl or above all benzyl and as C5-C7 cycloalkyl, or Tl ~ T2 the C atom, R7 is especially cyclohexyl.

If R7 is C2-C4 hydroxyalkyl, it is for example 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxy-butyl or 4-hydroxybutyl.

As for C6-C10 aryl, they are in particular phenyl, or a-or ~-naphthyl which is unsubstituted or substituted by halogen or C1-C4 alkyl.

If R7 is C2-C12 alkylene, it is for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexa-methylene, octamethylene, decamethylene or dodecamethylene.

If R7 is C6-C12 arylene r it is for example o-, m-or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

If Z' is C2-C12 alkanoyl, it is for example propionyl, butyryl, octanoyl,dodecanoyl or preferably acetyl.

As C2-C10 alkylene, C6-C15 arylene or C6-C12 cyclo-alkylene, X has the meaning given under b).

The following compounds are examples of polyalkyl-piperidine light stabilisers of this class:

47) 3-benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro [4.5]decane-2,4-dione, 48) 3-n-octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro [4.5]decane-2,4-dione, 49) 3-allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro [4.5]decane-2,4-dione, 50) 3-glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro [4.5]decane-2,4-dione, ,.. ~.

~S;~4~

50a) 2-isopropyl-7,719,9-tetramethyl-l-oxa-3,8-diaza-4-oxyspiro-[4.5]decane 50b) 2-butyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxyspiro-[4~5]decane 50c) 2-isopropyl-7,7,9,9,-tetr~methyl-1-oxa-4,8-diaza-3-oxy-spiro [ 4~5]decane, 50d) 2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxyspiro-[4,5]decane.

or the compounds of the following formulae:

Unable to recognize this page.

e) Light stabilisers of the formula (VI) ~10 in which n is the number 1 or 2, and R8 is a group of the formula R~CH2R

- Y- IA)X ~ \ - Rl CH~3 CH2R

in which R is as defined under the formula (I), ~1 is as defined under a), Y is -O- or -NR11-, A is C2-C6 alkylene; and x is the number O or l; Rg is the groups 8' 11 12~ OR13, -NHCH20R13 or -N(CH20R13)2; R
when n is 1 is the groups R8 or Rg, and Rlo when n is 2 is the group -Y-s-Y- wherein s is C2-C6 alkylene optionally interrupted by -N(R113; Rll is Cl-C12 alkyl~
cyclohexyl, benzyl or Cl~C4 hydroxyalkyl, or a group of the formula ~ CH3 N--R

CH/ \ H
R12 is Cl-C12 alkyl, cycl.ohexyl, benzyl or Cl-C~ hydroxy-alkyl; R13 is hydrogen, Cl-C12 alkyl or phenyl; or Rll and R12 together are C4-C5 alkylene or oxaalkylene, or Rll and R12 are each a group of the formula /
HN> ~ ~ot N ,N

3 ~ CH3 If any substituents are Cl-C12 alkyl, they are 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 are Cl-C4 hydroxyalkyl, they are for example 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxy-propyl, 2-hydroxybutyl or 4-hydroxybutyl~

If A is C2-C6 alkylenes, it is for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.

If Rll and R12 together are C4-C5 a:Lkylene or oxa-alkylene, this is for example tetramethylene, penta-methylene or 3-oxapentamethylene.

The compounds of the following formulae are examples of polyalkylpiperidine light stabilisers of this class:

.~

54 ~ CH3~< CH3 o ~o_l~o~>

5 5 )~ ( C4 H 9 ) 2 C 2 H 5~ ~ $--C 2 H 5 56) C~<CH3 CH --CH ~H

>~ ~ O ~<CH3 ~1~> 2 2I\N~ CH2 CH2 < ~H

3 3 1~7\ 3 Unable to recognize this page.

2 ~

u~

H17C8 - N NH(CH2)3 _ i 3 U 3 ~ 2 f) Light stabilisers of the formula (VII

R~<C H 2 R
L ~N~R14 (VII) CH3 CH2R n in which n is the number 1 or 2; R is as defined under the formula (I); and R14 when n is 1 is C4-C18 alkyl, C7-C12 aralkyl, the group -CO-R15, or C1-C4 alkyl which is substituted by -CN, -COOR16, -OH, -OCOR17 or -CH2-CH(OH)~ o wherein R15 is C~-C12 alkyl~ C -C
= ~
alkenyl or phenyl, R16 is Cl-C18 alkyl, R17 is Cl-C18 alkyl, C2-C10 alkenyl, cyclohexyl, benzyl or C6-C10 aryl;
or R14 when n is 2 is C4-C12 alkylene, 2-butenylene-1,4, xylylene, the group -(CH2)20CO-R18-COO-(CH2)2- or the group -CH2-COO-Rlg-COO-CH2- wherein R18 is C2-C10 alkylene~

-!' ~5i2~;

phenylene or cyclohexylene, and Rlg is C2-C10 alkylene, xylylene or cyclohexylene.

If any substituents are Cl-C12 alkyl, 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~ n-undecyl or n-dodecyl A

Any substituents which are Cl-C18 alkyl can be for example the groups mentioned above, and in addition for example n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

If any groups are C2-C10 alkylene, these are in particular ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene or deca-methylene.
As C4-C18 alkyl, R14 is for example n-butyl, sec-bu-tyl, ter~.butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, l,l-dimethyl-2-tert-butylethyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
If R14 is a Cl-C4 alkyl group substituted by -CN, it is for example cyanomethyl, cyanoethyl, 3-cyano-n-propyl or 4-cyano-n-butyl.
If R14 is C4-C12 alkylene, it is for example 2,2-dimethylpropylene, tetramethylene, hexamethylene, octa-methylene, decamethylene or dodecamethylene.
If R14 is C7-C12 aralkyl, it is in particular phenethyl, p-methyl-benzyl or especially benzyl.

, As C2-C4 alkenyl, R15 is for example vinyl, l-propenyl, allyl, methallyl or 2-butenyl~

As C2-C10 alkenyl, R17 is for example the groups mentioned for R15 as alkenyl, and in addition for example crotyl, 2-hexenyl, 2-octenyl or 2-decenyl.

If R17 is C6-C10 aryl, it is for example phenyl which is unsubstituted or substituted in the o- or p-position by methyl, ethyl, isopropyl, n-butyl or tert-butyl.
The following compounds are examples of polyalkyl-piperidine light stabilisers of this class:
60) bis-[~-(2,2,6,6-tetramethylpiperidine)-ethyl]-sebacate, 61) a-(2,2,6,6-tetramethylpiperidine)-aceti.c acid-n-octyl ester, and 62) 1,4-bis-(2,2,6,6-tetramethylpiperidine)-2-butene.

g) Light stabilisers of the formula (VIII) ROH2 ~ R

R -N ~ D-E-co-NH-c~2-oR2o (VIII) in which D is -N(R21)- or -0-; E is Cl-C3 alkylene, the group -CH2-CH(Z)-0- wherein Z is hydrogen, methyl or phenyl, the group -(CH2)3-N~- or a single bond; R is hydrogen or methyl; Rl is hydrogen, Cl-C18 alkyl, C3-C8 alkenyl~ C3-C8 alkynyl, C7-C12 aralkyl, Cl-C8 alkanoyl, C3-C5 alkenoyl or glycidyl; R20 is hydrogen or Cl-C18 alkyl; R21 is hydrogen, Cl-C18 alkyl, C5-C7 cycloalkyl, ~C7 ~s~

C7-C12 aralkyl, cyanoethyl, C6-C10 aryl, the group -CH2-CH(Z)-OH wherein Z has -the meaning defined above, a group of the formula RCH2,~
\

R -I

or a group of the formula -G- ~-E-co-NH-cH2-oR2o ~ R

)<
Rl wherein G can be C2-C6 alkylene or C6-C12 arylene; or R21 is a group -E-CO-NH-CH2-OR2o.
If any substituents are Cl-C18 alkyl, 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, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
If any substituents are C7-C12 aral]cyl, they are for example phenethyl or in particular benzyl.
If Rl is C3-C8 alkenyl, it can be for example 1-propenyl, allyl, methallyl, 2-bu-tenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tert-butyl-2-butenyl.

~;

~S;2~6 As C3-C8 alkynyl, Rl is preferably propargyl. As Cl-C8 alkanoyl, Rl is for example rormyl, propionyl, butyryl, octanoyl but preferably acetyl; and as C3-C5 alkenoyl, Rl is especially acryloyl.

As C5-C7 cycloalkyl, R21 is in particular cyclohexyl.
As C6-C10 aryl, R21 is particularly phenyl, or a- or ~-naphthyl which is unsubstituted or substituted with halogen or Cl-C4 alkyl. As Cl-C3 alkylene, E is for example methylene, ethylene or propylene.

As C2-C6 alkylene, G is for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene;
and as C6-C12 arylene, G is o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

The following compounds are examples of polyalkyl-piperidine light stabilisers of this class:

63) N-hydroxymethyl-N'-2,2,6,6-tetramethylpiperidin-4-yl)-urea, 64) N-methoxymethyl-N'-2,2,6,6-tetramethylpiperidin-4-yl-urea, i~¢~.

52'~i 65) N-methoxymethyl-N~ n-dodecyl-N'-2,2,6,6-tetramethyl-piperidin-4-yl-urea, and 66) 0-(2,2,6,6-tetramethylpiperidin-4-yl)-methoxy-methyl-urethane.

h) Polymeric compounds of which the recurring structural unit contains a polyalkylpiperidine radical of the formula (I), especially polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates or poly(meth)acrylamides, and copolymers thereof which contain such radicals.

The compounds o~ the following formulae, wherein m is a number from 2 to about 200 inclusive, are examples of polyalkylpiperidine light stabilisers of this class.

- 33a -"" ,~,.

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~s~

76) ~f 2 ~
O=C ~ 3 o ~ l_ CH

fH3 CH CH
O=C ~ 3 C6H13-N ~ CH3 i) Light stabilisres of the formula IX

C-~ R

2 3 n ~;

'' 5~6 in which n is a number from 1 - 4 inclusive, preferably 1 or 2; R is as defined under the formula (I); Rl is y , Cl C18 alkyl, C3-C8 alkenyl, C3-C~ alkynyl C7-C12 aralkyl, Cl-C8 alkanoyl, C3~C5 alkenoyl, glycidyl, a group -CH2CH(OH) Z wherein Z is hydrogen, methyl or phenyl, with Rl preferably being hydrogen, Cl-C12 alkyl, allyl, benzyl, acetyl or acryloyl; R22 is hydrogen, hydroxyl or Cl-C8 alkoxy; and R23, when n is 1, is Cl-C20 alkyl, C5-C12 cycloalkyl, C7-C14 aralkyl; when n is 2, R23 is C2-C12 alkylene~ C2-C12 cycloalkylene, C8-C16 cycloalkylene-di-alkylene, C8-C14 aralkylene, C4-Cg mono- or dioxaalkylene;
when n is 3, R23 is C3-C12 alkane-triyl; and when n is 4, R23 is C4-C12 alkane-tetrayl.

j) Light stabilizers of the formula (X) ~ ~ 28 ~ ~O 25 (X) _ 26 27 n in which n is a number from 4-10 inclusive; R24 is C2-C8 alkylene or C5-C6 cycloalkylene; R25 is Cl-C8 alkyl or C5-C6 cycloalkyl; R25 and R27 are Cl-C8 alkyl or together form a C5-C6 cycloalkylene ring; and R27 is hydrogen, hydroxyl, Cl-C8 alkoxy or Cl-C8 acyloxy.

, ~ .

~S2~i Compounds having one of the following formulae are likewise applicable.

R36 ~ N ~ R3 N ~ R36 ~ M`~
33 R32 31 ~ ~ 31 R33 R R31 wherein R29 and R32 independently represent hydrogen, alkyl having from 1 to 24 carbon atoms, hydroxyalkyl having from 1 to 12 carbon atoms, haloalkyl having from 1 to 12 carbon atoms, cyanoalkyl having from 2 to 12 carbon atoms, aminoalkyl having from 1 to 12 carbon atoms, alkenyl havinc~ from 2 to 4 carbon atoms, and unsubstituted hydrocarbon aralkyl having from 7 to 14 carbon atoms;
R32 optionally also represents oxygen, hydroxy or alkoxy;
R30 and R31 independently represent alkyl having from 1 to 12 carbon atoms, haloalkyl having from 1 to 12 carbon atoms, cyanoalkyl having from 2 to 12 carbon atoms, aminoalkyl having from 1 to 12 carbon atoms, cycloalkyl having from 5 to 14 carbon atoms, hydroxy cycloalkyl having from 5 to 14 carbon atoms, alkenyl having from 2 to 14 carbon atoms, and unsubstituted hydrocarbon aralkyl having from 7 to 14 carbon atoms;

- 39 -` 7' z~

R33~ R34, R35, R36 independently represent alkyl having from 1 to 12 carbon atoms, haloalkyl having from 1 to 12 carbon atoms, cyanoalkyl having from 2 to 12 carbon atoms, aminoalkyl having from 1 to 12 carbon atoms, alkenyl having from 2 to 14 carbon atoms, and unsubs-tituted hydrocarbon aralkyl having from 7 to 14 carbon atoms;
so that when R30~ R31 is cyclized having from 4 to 6 unsubstituted methylene groups, and R33, R34 is also cyclized having from 4 to 6 unsubstituted methylene groups, each cyclized substituent is different;
R35, R36 additionally also represent hydrogen; and R35, R36 may when taken together with the carbon atoms to which they are attached, form a polymethylene ring having from 5 to 6 carbon atoms.

Provided the polyalkylpiperidine derivatives are basic compounds, they can form salts with acids. Suitable acids are for example inorganic acids or organic carboxylic, sulfonic, phosphonic or phosphinic acids, such as hydro-chloric acid, boric acid, phosphoric acid, acetic acid, salicylic acid, toluenesulfonic acid or benzenephosphonic acid.

-- ~0 --~SZ'~6 Applicable U.V. absorbers are also well known to those skilled in the art. Included among such ~pplicable agents are:

1.1. 2-~2'-Hydroxy henyl)-henzotriazc)les, e.g. the 5'-methyl-, 3',5'-di-tert.-b-~tyl-, 5'-tert. butyl , ~'-(1,1,3, 3-tetramethylb~tyl)-, S-chloro-3',5'-di-terl.-butyl-, 5-chloro-3 '-t~r~.-butyl-5 '-methyl-, 3'-sec.-butyl-5'-tert.-butyl-, 3'-al~ha-methylben~yl-5'-methyl-, 3'-alpha~methyl-benzyl-5'-methyl-5-chloro-, 4'-hydroxy- t 4'-methoxy-, 4'-oct-oxy-, 3',5'-di-tert.-amyl-, 3'-methyl-5'-carboMethoxyethyl-, 3',5'-bis(alpha,alp~a-dimeth~lbenzyl),3',5'-Dis(alpha,alpha-dimethyl benzyl)-5-chloro-, 3',5'-di-ter~.-octylphenyl, 3',5'-di-tert.-ocJ~ylphenyl-5-chloro- and 5-chloro-3',5'-di-tert. amyl-derivatives.

1.~. 2,4-bis-(~'-Hydroxyphenyl)-6-al.ky1-s-triazines, e.g.
the 6-ethyl-, 6 heptadecyl~ or 6-undecyl-d~rivati~-e.

1.3. 2-Hydroxyben ophenGn~c, e.g. th~ 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4- dodecylGxy-, 4--benzylc~y-, 2',4-4'-trihydroxy- or 2'-hydroxy-4,4'-~imethoxy-dervative.

~s~

1.4. 1,3-bis-(2'-Hydroxybenzoyl)-benzenes, e.~. 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.

1.5. Esters of optionally substituted benzoic_cid, e.g.
phenylsalicylate, octylphenylsalicylate, dibenzoylresorcin, bis-(4-tert.-butylbenzoyl)-resorcin, benzoylresorcin, 3,5-di-tert.-butyl-4-hydroxybenzoic acid-2,4-di-tert.-butylphenyl ester or -octadecyl ester or -2-methyl-4,6-di-tert~-butyl ester.

1.6. Acrylates, e.g.
a-cyano-~3,~-diphenylacrylic acid-ethyl ester or isooctyl ester, a-carbomethoxy-cinnamic acid methyl ester, a-cyano-13-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester or N-(~-carbomethoxyvinyl)-2-methyl-indoline.

1.7. Oxalic acid diamides, e.~.
4,4'-di-octyloxy-oxanilide, 2,2'-di-doclecyloxy-5,5'-di-tert -butyl-oxanilide, 2-ethoxy-2'-ethyl~oxanilide, N,N'-bis-(3-dimethyl-aminopropyl)-oxalamide, 2-ethoxy-5-tert.-butyl-2'-ethyl-5,4'-di-tert.-butyl-oxanilide, or mixtures of ortho-and para-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

~..

The benzotriazole U.V. absorbers are preferred for use in the instant invention. Typical benzotriazoles are described, for example, in U.S. 3,004,896, U.S. 3,189,615, U.S. 3,320,194, U.S.
4,127,586 and U.S. 4,283,327.

The term "fungicides" as utilized herein is intended to cover compounds covering a broad range of fungicidal, mildewcidal, preservative and antifouling activities, which compounds are subject to light-induced deterioration. O~
particular interest are mildewcides and fungicides.
Typical fun~icides include carbamates such as 3-iodo-2-propynyl-butylcarbamate, dimethyldithiocarbamate, 2-sec.butyl-phenyl-N-methyl-carbamate, benzimidazol carbamates, carbamyl-(l-naphthyl-N-methylcarbamate), dithio carbaminate, (2-isopropoxy-phenyl)-N-methylcarbamate, 4-(dimethylamino)-m-tolyl methylcarba-mate, 6-chloro-3,4-xylyl methylcarbamate, zinc dimethyldithio carbamate and l-naphthyl methylcarbamate; arsenic compounds such as copper chrome arsenate; chlorinated phenols such as tetrachlorophenol, pentachlorophenol, sodium pentachlorophenate;
copper compounds such as copper naphthenate; other chlorinated compounds such as l-chloronaphthalene, N-t:richloromethyl-thio-phthalimide, tetrachloroisophthalonitrile, tetrachloro-pyridine-4-methyl-sulfonate, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, 2,3-dichloro~,4-naphthoquinone, ~,~-bis(p-chloro-phenyl)-3-pyridine-methanol and pentachloronitrobenzene; or~ano i2 ~

mercury compounds such as phenyl mercuric oleate and di(phenyl mercury) dodecenyl succinate; organo tin compounds such as tributyl tin oxide, zinc compounds such as zinc naphthenate;
ketones such as 2-n-octyl-4-isothiazolin-3-one, and 3,3'-ethylene bis [tetrahydro-4,6-dimethyl-2H-1,3,5-thiadiazine-2-thione];
sulfonyl compounds such as 1,2-bis(N-propylsulfonyl)ethane; and iodomethyl p-tolyl sultone azole compounds such as 2-(4-thiazolyl)benzimidazole and (Zn)2 mercapto benzothiazole;
and other fungicides well known to those skilled in the art.
Reference in this regard may be made to Torgeson, F n~c_ es, Vol. II r Chemistry and Physiology, Acedemic Press 9 New York (1969).

In general, each of the stabilizers of this invention is employed in concentrations of from about 0.25:1-4.0:1 and preferably 0.5:1 to 1.5:1, these ratios being determined relative to the weight of the fungicide material. Where the combined system is utilized, the piperidine compound and UV absorber are utilized in relative concentrations of from 16:1 to 1:16, and preferably 3:1 to 1:3. Specific concentrations within these ranges will depend on the nature of the fungicide, on the degree of stabilization required and on the nature of the substrate.
The stabilizers may be readily incorporated by any conventional techniques at any convenient stage prior to the application of the fungicide or ~ungicide-containing formulation.

:, The stabilized polymer compositions of the invention may optionally also contain from about 0.1 to about 5 ~, preferably from about o.5 to about 3 ~ by weight of various conventional additives, such as the following, particularly phenolic antioxidants or metal deactivators, or mixtures thereof:

1. Antioxidants 1.1 Simple 2,6-dialky~henols such as, for exa~ple, 2,6-ditert.-butyl-4-methylphenol, 2-tert.-butyl-4,6-dimethylphenol, 2,6-di-tert.-butyl-4~methoxymethylphenol and 2,6-dioctadecyl-4-methylphenol.

1.2 Derivatives of alkylated hydroquinones, such as for example 2,5-di tert.-butyl-hydroquinone, 2,5-di-tert.-amyl-hydroquinone, 2,6-di-tert,-butyl-hydroquinone, 2,5-di-tert.-butyl-4-hydroxy-anisole, 3,5-di-tert.-butyl-4-hydroxy-anisole, 3,5-di-tert.-butyl-4-hydroxyphenyl stearate and bis-(3,5-di-tert.-butyl-4-hydroxyphenyl) adipate.

1.3 Hydroxylated thiodiphenyl ethers, such as for example, 2,2'-thio-bis-(6~tert.-butyl-4-methylphenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert.-butyl-3-methylphenol), 4,4'-thio-bis-(3,6-di-sec.-amylphenol), 4,4'-thio-bis-(6-tert.-butyl-2-methylphenol) and 4,4'-bis-(2,6-dimethyl-4-hydroxy-phenyl) disulfide.

,r .. ~

z~

1.4 Alkylidene-bisphenols, such as, for example, 2,2'-methylene-bis-(6-tert.-butyl-4-methylphenol), 2,2'-methylene-bis-(6-tert.-butyl-4-ethylphenol), 4,4'-methylene-bis-t6-tert.-butyl-2-methylphenol), 4,4'-methylene-bis-(2,6-di-tert.-butyl-phenol), 2,6-di(3-tert.-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 2,2'-methylene-bis-[4-nethyl-6-(~-methylcyclo-hexyl)-phenol], l,l-bis(3,5-dimethyl-2-hydroxyphenyl)-butane, 1,1-bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propane, 1,1,3-tris-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butane, 2,2-bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercapto-butane, 1,1,5,5-tetra-(5-tert.-butyl-4-hydroxy-2-methyl-phenyl)-pentane and ethylene glycol bis [3,3-bis(3-tert.-butyl-4-hydroxyphenyl)-butyrate].

1.5 o-, N- and S-benzyl compounds, such as for example, 3,5,3',5'-tetra-tert.-butyl-4,4'-dihydroxydibenzyl ether, octa-decyl 4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate, tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-amine and bis-(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate.

1.6 Hydroxybenzylated malonates, such as for example, diocta-decyl 2,2-bis-(3,5-di-tert.-butyl-2-hydroxybenzyl)-malonate, dioctadecyl 2-(3-tetr.-butyl-4-hydroxy-5-methylbenzyl)-malonate, di-dodecylmercapto-ethyl 2,2-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonate and di-[4-(1,1,3,3-tetramethylbutyl)-phenyl] 2,2-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonate.

~ 46 -'Y~

2 ~ Eii 1.7 Hydroxybenzyl-aromatic compounds, such as, for example, 1,3,5-tri-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6-trimethyl-ben~ene, 1,4-di-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene and 2,4,6-tri-(3,5-di-tert.-butyl-4-hydroxy-benzyl)-phenol.

1.8 s-Triazine compounds, such as, for example 2,4-bis-octylmercapto-6-(3.5-di-tert.-butyl-4-hydroxy-anilino)-s-triazine, 2-octylmercapto-4,6-bis-(3,5-di-tert.-butyl-4-hydroxy anilino)-s-triazine, 2-octylmercapto-4,6-bis-(3,5-di-tertO-butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.-butyl-4-hydroxyphenoxy)-2-triazine, 2,4,6-tris-(3,5-di-tert.-butyl-4-hydroxyphenylethyl)-s-triazine and 1,3,5~tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)isocyanurate.

1.9 Amides of ~-(3l5-di~tert.-butyl-4-hydroxvphenyl)-propionic acid, such as, for exampleS 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hexahydro-s-triazine and N,N'-di-3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hexamethylenediamine, N,N'-bis-R-(3,5-di-t-butyl-4-hydroxyphenyl)-propionyl-hydrazine.

1.10 Esters of ~-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols, such as for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, l,9-nonane-diol, ethylene glycol, 1,2-propanediol, diethylene glycol, thio-diethylene glycol, neopentylglycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethylhexenediol, trimethylel-ethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2.2.2]octane.

i _ 5Z~

1.11 Esters of ~-(5-tert.-butyl-4=hyd oxy-3-m thylphenyl-propionic_acid with monohydric or polyhydric alcohols, such as for example, with methanol, ethanol, octadecanol, 1,6-hexene-diol, l,9-nonanediol, ethylene glycol, 1,2-propanediol, di-ethylene glycol, thioethylene glycol, neopentylglycol, penta-erythritol, 3-thia-undecanol, 3-thia-pentanedecanol, trimethyl-hexanediol, trimethylolethane. trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxakicyclo[2.2.2]octane.

1.12 Esters of 3,5-di-tert.-butyl-4-hydroxy~henylacetic acid with monohydric or polyhydric alcohols, such as for example, with methanol, ethanol, octadecanol, 1,6-hexandiol, 1,9-nonanediol, ethylene glycol, 1,2-propenediol, diethylene glycol, thio-diethylene glycol, neopentylglycol, pentaerythrit-ol, 3-thiaundecanol, 3-thia-pen-tadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl iso-cyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2.2.2]-octane especially the tetrakis ester of pentarythri-tol.

1.13 Benzylphosphonates, such as, for example, dimethyl 3,5-di-tert.-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert.-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert.~butyl-~-hydroxybenzylphosphonate and dioctadecyl 5-tert.-butyl-4-hydroxy-3-methylbenzylphosphonate.

i.~

~s~

2. Metal deactivators, e.g.. oxanilide, isophthalic acid di-hydrazide, sebacic acid-bis-phenylhydrazide, bis-benzylidene-oxalic acid dihydrazide, N,N'~diacetal-adipic acid dihydra-zide, N,N'-bis-alicyloyl-oxalic acid dihydrazide, N,N1-bis-salicyloylhydrazine, N,N'-bis-(3,5-di-tert.-butyl-4~hydroxy-phenylpropionyl)-hydrazine, N-salicyloyl-N'-salicylalhydrazine, 3-salicyloyl-amino-1,2,4-triazole or N,N'-bis-salicyloyl-thio-propionic acid dihydrazide.

Other additives that can be incorporated in the stabilized compositions are thiosynergists such as dilauryl thiodi-propionate, basic co-stabilizers, nucleation agents, phosphites, phosphonites, lubricants such as stearyl alcohol, fillers, asbestos, kaolin~ talc, glass fibres, pigments, optical brighteners, flameproofing agents and antistatic agents.
Among this group, phosphites in combination with a blend of UV
absorbers and piperidine compound are of particular interest.

As previously noted, the fungicides can be effectively stabilized whether they are applied in solution, emulsion or some other liquid form, or whether they are formulated into finished formulations such as paints, ]acquers, stains, enamels, substrate treatments such as wood preservatives and water repellent ., .

systems, or other coating formulations. Ingredients present in such formulations are well known to those skilled in the art. A
number of these ingredients have been listed hereinabove.
Additional ingredients include resin systems such as alkyd resins, acrylic resins, polyesters, phenolics, polyurethanes, epoxies and blends thereof; solvents; surfactants; defoamers;
thickeners such as carboxymethyl cellulose, polyacrylic or polymethacrylic acids; plasticizers, dispersants; binders, water repellents; oxidizable oils such as vegetable oils; and the like. Pigments and fillers in these formulations function as UV
screening agents.

The fungicidal compositions can be applied to a large variety of substrates. Of particular importance is the application of the stabilized fungicide systems to wood, metal or natural or synthetic polymeric substrates for the prevention of mildew and other fungus formations. Textile and paper substrates are likewise applicable. In this manner, the stabilizers prevent the decomposition of the fungicide, thereby facilitating the desired fungicidal activity and providing maximum protection to the substrate.

The following examples further illustrate the embodiments of this invention. In these examples, all parts given are by weight unless otherwise specified.

s~

The following stabilizers are utilized in these examples.

A - 2-(2-hydroxy-3,5-di-tert.amylphenyl)-2H-benzotriazole B - bis(l,2,2,6,6-pentamethyl-4-piperidyl) decanedioate C - polyester oligomer of 1-(2-hydroxyethyl)-2,2,5,5-tetra-methyl 4-hydroxy piperidine and 2,2-diethylmalonic acid D - 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole E - bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate F - bis(l,2,2,6,6-pentamethyl-4-piperidyl)C[3,5-bis(l,l-dimethyl-ethyl-4-hydroxyphenyl)methyl]butyl] propanedioate G - mixture of 3-(5-chloro-2H-benzotriazole-2-yl)-4-hydroxy-5-(l,l-dimethyl-ethyl phenyl propionic acid)-octyl and -2-ethyl-hexyl esters H - 8-acetyl-3-dodecyl-7,7~9,9-tetramethyl-1,3,8-triazaspiro-[4.5]decane-2,4-dione I - 2-dodecyl-2'-ethoxy-oxanilide J - 2-hydroxy-4-n-octoxybenzophenone K - 2,2l-dihydroxy-4-methoxybenzophenone L - 2,4-dihydroxybenzophenone Example 1 This example illustrates the fungicidal stabilizing capability of the stabilizing system of this inventlo.n. In each instance, the effectiveness of light stabilization of the fungi-cide was determined as the ability to prevent mildew defacement of the coating surface as a function of time.
Outdoor exposure tests were conducted utilizing a linseed oil white stain and wood perservative based on mineral spirits, titanium dioxide pigment, linseed oil and coalescing solvent (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate).
Samples were prepared u-tilizing 0.25%, 0.5%, 1.0%, 2.0% and 2.5%, by weight of the stain, of the following fungicides:
3-iodo-2-propynyl butyl carbamate (Polyphase* from Troy Chemical Co.) 1,2-bis(n-propylsulfonyl)ethane (Vancide PA* from Vanderbilt Co . ) * Trademark ~5.2~

N-trichloromethylthio-phthalimide (Fungitrol 11* from Tenneco).
In turn, the samples were left unstabilized or stabili-zed wi-th 1.0% stabilizer A, 1.0% stabilizer B, 1.0% stabilizer A plus 1.0% stabilizer B, and 2.0% stabilizer A plus 1.0%
stabilizer B, the percentages being based on the weight of resin solids.
Each formulation was coated onto l"x8"x12" white pine boards. The boards were cut in half, with one panel being posed outdoors at a position angle of 90N and the mate thereof being exposed at a position angle of 45S.
Within four months of exposure, all of the controls exposed at 45S were severely mildewedO The controls were the stain formulations without fungicide and the stain formulations without fungicide, but with light stabilizers. The failure of the latter control group was significant inasmuch as it demonstra-ted the lack of fungicidal activity on the part of the stabilizer system. Accordingly, increased fungicidal activity can be attributed solely to the stabilizing effect on the fungicide.
Other resul-ts of this testing procedure indicated that a 1% Polyphase formulation stabilized with 1% stabi]izer A and 1%

* Trademark ~S2i~

stabilizer B decidedly outperformed the unstabilized 1~ Polyphase formulation and was equal to or slightly better than the unstabilized 2~o Polyphase formulation.

The following test data reflect on certain of these results. Mildew ratings were noted according to ASTM D-3274-76 on a scale of 1-10, with a rating of 10 indicating a mildew-free surface.

Fungicide Conc. (~) Stabilizer Conc. Mildew Rating (at 45S) _ _ _ _ ._ ___ _ __ _____ _ . _ _ncide PA 4 mos. 6 mos. 12 mos 0.5 - 8 4 5 0O5 1.0% stab. B 9 9 g 0.5 1.0% stab. A 9 8 6 0.5 2.0~ stab.A/1.0% stab.B 8.5 9 9 0.5 1.0% stab.A/l.0~ stab.B 9 8 9 2.0 ~ 9.5 9 7 Polyphase 0.5 1.0% stab. B 8.5 7 7 0.5 1.0% stab. A 8 8 8 0.5 2.0% stab.A/1.0% stab.B 8 8 8 0.5 1.0~ stab.A/l.0~ stab.B 8 6 6 2.0 - 9 8 8 ~a9~ 6 _n~l - 11 0.5 - 8 8 0.5 l.0~ stab. B 9 8 9 0.5 1.0% stab. A 8 6 0.5 2.0~ stab.A~1.0% stab.B 9 9 g 0.5 1.0~ stab.A~l.0~ stab. B 9 9 g 2.0 ~ 9 9 9 The stabilizing effectiveness of the instant stabilizing systems is thus clearly indicated.

Example 2 This example further illustrates the fungicidal stabilizing capability of the stabilizing systems of this invention.

The active material utilized in this example was 3-iodo-2-propynyl butyl carbamate (Polyphase), a material utilized as a mildewcide and fungicide. The carbamate was formulated into a clear acrylic emulsion of 60% solids (Rohm &
Haas acrylic latex AC-64) at a l.0~, by weight, active carbamate concentration and appropriate amounts of stabilizer were blended into the emulsion. Films of 90 micron thickness were prepared from the unstabilized emulsion as well as from the various stabilized emulsions. The resulting dry films were then exposed 5~

to a fluorescent sunlight/black light chamber for a period of 12 hours and the yellowness index determined by means of ASTM
D-1525-63-T.

The stabilizer concentrations (% by weight of resin solids) and the test results are noted in the following table.

Stabilizer System % Yellowne_s Index A B C
Control 38.87 1.5 1.5 - 19.76 1.5 1.0 - 19.32 1.5 0.5 - 19.00 0.5 1.0 - 27.98 0.5 0.5 - 28.35 0.5 1.5 - 30.82 0 5 ~ ~ 31.11 1.0 - - 24.77 1.5 - - 23.21 - 0.5 - ~1.19 - 1.0 - 45.63 - 1.5 - 45.59 1.0 1.0 - 25.00 1.0 1.5 - 23.33 1.0 0.5 - 24.53 1.0 - 1.0 27.05 - - 1.0 19.00 Slnce the breakdown products of Polyphase are yellow. these results clearly indicate the biocide stabilization characteristics of the instant systems. In reviewing this data, it should be recognized that accelerated weathering devices employing UV energy may not be the preferred vehicle for determining the stabilization activity of stabilization systems containing only the piperidine compounds. Rather, such results should be considered in combination with other test data to obtain a true performance profile Example 3 The photodecomposition characteristics of the carbamate of Example 1 were furthered studied by means of thin layer chromatography Thus the carbamate 1 part of the carbamate combined with 2 parts of stabilizer D, 1 part of the carbamate with 2 parts of stabi.lizer E and 1 part of the carbamate combined with a blend of 2 parts stabilizer D and 2 parts stabilizer E were subjected to a low pressure mer~ury vapor lamp for a period of 15 minutes and then tested by chromatography in methylene chloride solvent to determine the existence of decomposition product. The chromatographic study indicated that the stabilized carbamate after exposure exhibited the same pattern as the unexposed car-bamate, with the unstabilized, exposed carbamate showing distinct evidence of decomposition.
Example 4 The following solution study under W irradiation was conducted in order to determine -the amount of residual Nopcocide N96* (tetrachloro isophthalonitrile - a broad spectrum mildewcide from Diamond Shamrock Corp.) in solution after periods of UV
exposure. A control sample was prepared containing 20 mg. of Nopcocide in 1000 ml. of toluene. The stabilized samples contained 20 m~. of Nopcocide and 75 mg. of stabilizer in 1000 ml. of toluene. The control and stabilized samples were exposed in a fluorescent sunlight/black light chamber in sealed vials for a period in excess of 105 minutes. The residual Nopcocide was determined by gas chromatography. The results are noted below:

Sample % Residual Fungicide after Conc. (mg) 0 min.15 min.30 min.45 min. 60 min.

Control - 100 30.0 7.0 4.0 0.5 Stab. A 75 100 97.0100.0 85.5 86.0 Stab. C 75 100 44.518.0 4.5 2.5 Stab. A 75 100 94.086.5 84.0 84~0 -~ Stab. C 75 * Trademark 5~

These data clearly establish the stabilizing effectiveness of the stabilizers of this example in terms of maintaining the active ingredient.

Example 5 Films of 120 micron thickness were prepared from (1) AC-64 acrylic latex (60% solids); (2) AC-64 and 1% by weight of Nopcocide N96; and (3) AC-64, 1% of N96, 1% of stabilizer A and 1% of stabilizer B, the latter percentages being based on resin solids. Each of the films was subjected to UV irradiation. Film 1 was seen to be UV transparent, i.e. limited visibility. Film 2 was highligh-ted due to the fluorescent effect on the N96. This fluorescent effect suggests that the N96 is absorbing UV light energy. Since the mildewcide in the fluorescent state is in an excited state, decomposition can be anticipated.

In contrast, the stabilized film was dar~. due to the absorption of the ultraviolet light by the stabilizer system.
Decomposition would not be anticipated in the latter instance.

Example 6 This example illustrates the stabilizing effectiveness of the instant system when incorporated into a fungicide containing, standard latex white house paint.

The following paint formulation was utilized.

Parts water 100.0 defoamer 0.5 ethylene glycol 14.0 hydroxyethyl cellulose1.0 surfactant 6.75 titanium dioxide 125.0 talc 100.0 acrylic latex (AC-64)182.0 defoamer 0.5 fungicide(Polyphase) 6.0 coalescing solvent* 58.0 water 10.0 *2,2,4-trimethyl-1,3~pentanediol monoisobutyrate A second sample of the paint was prepared in identical fashion with the exception tha-t the acrylic latex was blended with 1% stabilizer A and 1% stabilizer B (each based on weiyht of solids) prior to its addition to the formulation.
Each paint was then applied to strips of cellulosic filter paper, dried and exposed in the fluorescent sunlight/black light chamber for a period of 12 hours. The change in yellowness index (YI) was then determined by ASTM D-1925-63-T, with the samples before exposure exhibiting a YI of 3, the exposed control exhibiting a YI of 41.1 and the exposed stabilized system exhibiting a YI of 16.22. Accordingly, it was noted that -the stabilized paint layer was far more attractive than the yellowed unstabilized system.
Example 7 A commercial exterior oil-based alkyd paint (Sears Semi-Gloss Trim) containing 0.5% 2,3,5,6-tetrachloro-4-(methyl-sulfonyl)-pyridine mildewcide (Dowicil S13* from Dow Chemical Corp.) and a similar paint containing 1% of stabilizer A and 1%
of stabilizer B (based on resin solids) were applied to Bonderite 1000 cold rolled steel panels and the panels exposed at an angle of 45S for one year in southern Florida. An inspection of the panels revealed a substantial amount of mildew growth on the control panel as contrasted with a minimal amount of mildew * Trademark ~35iZ ~6 formation of the panel painted with the stabilized formulation.
It is clear. thererore, that the light stabilizers have maintained the effectiveness of the mildewcide by protecting it from UV induced decomposition.

Scanning electron micrographs of the respective coatings revealed that the stabilized coating had a less extensive and less dense growth of hyphae ~mildew fungi) than the unstabilized coating. These observations further confirm the retention of a toxic environment in the stabilized system.

5~

Example 8 . _ _ A procedure similar to that of Example 4 was utilized to determine the amount of residual pentachlorophenol, a widely recognized fungicide and mildewcide, after periods of UV
exposure.

Solutions of 20 ppm pentachlorophenol in toluene were prepared. Control samples were retained while other samples were formulated containing 80 ppm stabilizer A, 80 ppm stabilizer F and a blend of 80 ppm stabilizer A and 80 ppm stabilizer F, respectively. The control and stabilized samples were exposed in the fluorescent sunlight/black light chamber for varying intervals of time.

The basic method utilized for analysis of pentachlorophenol IS described in Satoh, "Photochemical Reaction of Chlorothalonil in Organic Solvents, "Bull.
Environ. Contam. Tox. 22, 590-597 (1979). This procedure __ required derivitization of the pentachlorophenol by the procedure described on page 179 of the 1982-83 Pierce Products Catalog [Kawahara, Anal. Chem., 40, No. 6, 1009 (1968)]. The ., _ results of these evaluations are noted in the following table.

Exposure Time(min) Residual Pentachlarophenol (~) Control Stab.A Stab F Stab A+

67 100 69.82 100 56.18 100 5~.88 97. oa 30.77 98.7 34.04 96.08 16.04 91.5 20.96 94.94 5.9 93~33 12.26 85.14 This data further confirms the stabilizing effectiveness of the instant systems in terms of preventing decomposition of active material.

Example 9 A 15%, by weight, toluene solution of a thermoplastic acrylic ester resin (Acryloid B 66* from Rohm & Haas) was prepared and 10 grams thereof were blended with 0.1 gram of pentachloro-phenol and approximately 0.5 grams of total stabilizer. There-after, 1.0 gram of the formulation was roll coated into a thin film on the interior wall of a vial and dried by evaporation.
The vial was capped and exposed in the fluorescent sunlight/
black light chamber for the indicated exposure time. Following exposure, each sample was extracted and analyzed for residual pentachlorophenol by the procedure of Example 8 utilizing gas chromatographic analysis with an electron capture detector.
The results are noted in the following table.

StabilizerConc. (%) % Retention after 0 hrs. 24 hrs. _5 hrs.
Control - 100.016.0 5.0 F 5 100.0100.0100.0 G 5 100.0100.0100.0 ~1 5 100.034.021.0 F + G 2.5 + 2.5 100.0100.0100.0 G + H 2.5 + 2.5 100.0100.0100.0 (G + H 1.6 -t 1.6 100.0100.0100.0 (+ Antioxidant** + 1.6 **Thiodiethylene bis-(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate *Trademark , The test procedure thus further demonstrated the abili-ty of the instant stabilizer systems to maintain the integrity of fungicides.
Example 10 The procedure of Example 9 was repeated to prepare the films in the capped vials. Following exposure, 10 mls. o~ chloro-form were introduced into each vial to extract the film. A 5 ml.
aliquot of the extract was further diluted in 10.0 ml. of chloro-form and a thin layer chromatograph performed on pre-coated silica gel plates utilizing ultraviolet fluorescence as the detecting mechanism. The solvent systems utilized for the different fungi-cides for TLC development were as follows.

Fungicide _olvent Nopcocide N-96 methylene chloride Fungitrol-ll 70:30 benzene/n-hexane pentachlorophenol methylene chloride Amical 48* methylene chloride Skane M-8** 90:10 methylene chloride/methanol * trade mark for diiodomethyl paratolyl sulfone from Abbott Laboratories.

** trade mark for 2-n-octyl-4-isothiazolin-3-one from Rohm &
Haas Corp.

5~ ~

The results are noted in the following table :
ungicide _ystemExposure Rf _alue* Comment Time (hrs.
Nopcocide N-96 control 0 .58 standard Rf control r_200 .58 decreased spot inter~sity + 5% Stab. A,v 200 .58 standard Rf + 5% Stab. H ~ 200 .58 slightly decreased spot intensity Fungitrol _ 11 control 0 .15 standard Rf control ~v200 - spot not observed + 5% Stab.B ~200 - spot not observed + 5% Stab.G ~200 .15 standard Rf (+ 5% Stab.B ~200 - spot not observed (+ 5~ Stab.G
Amical 48 _ __ control 0 .40 standard Rf control 64.0 - spot not observed + 5% Stab.F 64.0 .40 standard R~
+ 5~ Stab.I 64.0 .40 standard Rf Skane M8 control 0 .6 standard Rf control 64.0 - spot not observed + 5~ Stab.J 64.0 .6 standard Rf (+ 5% Stab.J 64.0 .6 standard Rf (+ 5% Stab.C
~entachl_rophenol control 0 0.30 standard R~
control 64.3 - spot not observed + 5~ Stab.E 64.3 - spot not observed (+ 5% Stab.H 64.3 0.30 standard Rf ~+ 5~ Stab.G
* Rf value indicates the differential between the chromatographic distance travelled by the solvent and the distance traveled by the active ingredient.

J5~ ~

This test model also demonstrates the ability of UV
absorbers and piperidine compounds to protect fungicides from photo-oxidation.

~_ample 11 The procedure of Example l was repeated utilizing a terpene clear wood finish and a linseed oil clear wood finish, each containing 1%, by weight of phenyl mercuric oleate mildewcide.
The panels which contained both stabilized and unstabilized areas, were exposed outdoors at a position angle of 45S. Mildew ratings were again noted according to ASTM D-3274-76 on a scale of 1-lO, with a rating of 10 reflecting a mildew-free surface.

Thè following stabilizer systems were utilized Stabilizer Conc. (%) B

A + B 2 + l A + B 4 + 2 52'~

All panels exhibited a mildew free surface at the initiation of the test procedure. After a five month exposure period, virtually all of the unstabilized areas showed mildew formation.
Mildew ratings for the latter areas ranged from 3-9. In contrast, each of the stabilized areas had a mildew rating oE 10 after the five month period indicating a mildew-free surface and effective stabilization of the mildewcide.

In summary, this invention provides novel stabilized fungicide systems which exhibit excellent performance characteristics. Variations may be made in procedures, proportions and materials without departing from the scope of the invention as defined by the following claims.

Claims (28)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A composition of matter comprising a fungicide subject to light-induced deterioration stabilized with an effective stabilizing amount of a 2,2,6,6-tetraalkylpiperidine compound, or a mixture thereof with an ultraviolet absorber.

2. The composition of matter of claim 1, wherein said piperidine compound contains a group of the formula wherein R is hydrogen or methyl.

3. The composition of claim 2, wherein R is hydrogen.

4. The composition of claim 1, wherein said piperidine compound and said UV absorber being present in relative concen-trations of 16:1 to 1:16.

5. The composition of claim 1, wherein said 2,2,6,6-tetra-alkylpiperidine compound corresponds to the formula (II) (II) in which n is a number from 1 - 4 inclusive; R is hydrogen or methyl; R1 is hydrogen, oxyl, C1-C18 alkyl, C3-C8 alkenyl, C1-C8 alkynyl, C7-C12 aralkyl, C1-C8 alkanoyl, C3-C5 alkenoyl, glycidyl or a group -CH2-CH(OH)-Z wherein Z is hydrogen, methyl or phenyl;
and R2,when n is 1,is hydrogen, C1-C18 alkyl optionally interrup-ted by one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acid, or of carbamic acid or of a phospho-rus-containing acid, or a monovalent silyl radical; R2, when n is 2, is C2-C12 alkylene, C4-C12 alkenylene, xylylene, a bivalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, of dicarbamic acid or of a phosphorus-containing acid, or a bivalent silyl radical; R2, when n is 3, is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, of an aromatic tricarbamic acid or of a phosphorus-containing acid, or a trivalent silyl radical; and R2, when n is 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

6. A composition according to Claim 5, wherein in the stabilizer of formula (II) (II) n is the number 1 or 2; R is hydrogen or methyl; R1 is hydrogen, C1-C12 alkyl, allyl, benzyl, acetyl or acryloyl; and R2, when n is 1, is a radical of an aliphatic carboxylic acid having 2-18 C atoms, of a cycloaliphatic carboxylic acid having 5-12 C a-toms or of an aromatic carboxylic acid having 7-15 C atoms; and R2, when n is 2, is a radical of an aliphatic dicarboxylic acid having 2-36 C atoms, of a cycloaliphatic or aromatic dicarboxylic acid having 8-14 C atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 C atoms.

7. A composition according to Claim 1, wherein said piperidine compound corresponds to the formula (III) (III) in which n is the number 1 or 2; R is hydrogen or methyl; R1 is hydrogen, oxyl, C1-C18 alkyl, C3-C8 alkenyl, C3-C8 alkynyl, C7-C12 aralkyl, C1-C8 alkanoyl or C3-C5 alkenoyl; R3 is hydrogen, C1-C12 alkyl, C5-C7 cycloalkyl, C7-C8 aralkyl, C2-C18 alkanoyl, C3-C5 alkenoyl or benzoyl; and R4, when n is 1, is hydrogen, C1-C18 alkyl, C3-C8 alkenyl, C5-C7 cycloalkyl, C2-C8 alkyl sub-stituted by a cyano, carbonyl or carbamide group, or it is glycidyl, a group of the formula -CH2-CH(OH)-Z or of the formula -CONH-Z wherein Z is hydrogen, methyl or phenyl; or R4, when n is 2, is C2-C12 alkylene, C6 C12 arylene, xylylene, a -CH2-CH(OH)-CH2-group or a group -CH2-CH(OH)-CH2-O-X-O-CH2-CH(OH)-CH2-wherein X is C2-C10 alkylene, C6-C15 arylene or C6-C12 cyclo-alkylene; or, provided that R3 is not alkanoyl, alkenoyl or ben-zoyl, R4 can also be a bivalent radical of an aliphatic, cycloaliphatic, or aromatic dicarboxylic acid or dicarbamic acid, or can also be the group -CO-; or R3 and R4 together, when n is 1, can be the cyclic radical of an aliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

8. A composition according to Claim 1, wherein said piper-idine compound corresponds to the formula (IV) (IV) in which n is the number 1 or 2; R is hydrogen or methyl; R1 is hydrogen, oxyl, C1-C18 alkyl, C3-C8 alkenyl, C3-C8 alkynyl, C7-C12 aralkyl, C1-C8 alkanoyl or C3-C5 alkenoyl; and R5, when n is 1, is C2-C8 alkylene or hydroxyalkylene or C4-C22 acyloxyalkylene;
and R5, when n is 2, is the group (-CH2)2C(CH2-)2.

9. A composition according to Claim 1, wherein said piperidine compound corresponds to the formula (VA), (VB), or (VC).

(VA) (VB) (VC) in which n is the number 1 or 2; R is hydrogen or methyl; R1 is hydrogen, oxyl, C1 C18 alkyl, C3-C8 alkenyl, C3-C8 alkynyl C7-C12 aralkyl, C1-C8 alkanoyl, C3-C5 alkenoyl, glycidyl, a group -CH2CH(OH)-Z wherein Z is hydrogen, methyl or phenyl;

R6 is hydroge, C1-C12 alkyl, allyl, benzyl, glycidyl or C2-C6 alkoxyalkyl; and R7, when n is 1, is hydrogen, C1-C12 alkyl, C3-C5 alkenyl, C7-C9 aralkyl, C5-C7 cycloalkyl, C2-C4 hydroxyalkyl, C2-C6 alkoxyalkyl, C6-C10 aryl, glycidyl, a group of the formula -(CH)-COO-Q or of the formula -(CH2)m-O-CO-Q wherein m is 1 or 2, and Q is C1-C4 alkyl or phenyl; or R7, when n is 2, is C2-C12 alkylene, C6-C12 arylene, a group -CH2-CH(OH)-CH2-O-X-O-CH2-CH(OH)-CH2- wherein X is C2-C10 alkylene, C6-C15 arylene or C6-C12 cyclo-alkylene, or a group -CH2CH(OZ')CH2-(OCH2-CH(OZ')CH2)2- wherein Z' is hydrogen, C1-C18 alkyl, allyl, benzyl, C2-C12 alkanoyl or benzoyl, and T1 and T2 independently of one another are hydrogen, C1-C18 alkyl or C6-C10 aryl which is unsubstituted or substituted by halogen or C1-C4 alkyl, or C7-C9 aralkyl, or T1 or T2 together with the C atom which bonds them form C5-C7 cycloalkyl, pyrroli-dinyl or piperidinyl, which are unsubstituted or substituted by C1-C4 alkyl.

10. A composition according to Claim 1, wherein said piperi-dine compound corresponds to the formula (VI) (VI) in which n is the number 1 or 2; and R8 is a group of the formula in which R is hydrogen or methyl; R1 is hydrogen, oxyl, C1 C18 alkyl, C3-C8 alkenyl, C3-C8 alkynyl C7-C12 aralkyl, C1-C8 alkanoyl, C3-C5 alkenoyl, glycidyl, a group -CH2CH(OH)-Z wherein Z is hydrogen, methyl or phenyl; Y is -O- or -NR11-, A is C2-C8 alkylene; and X is the number 0 or 1; R9 is the group R8, NRllR12, -OR13, -NHCH2OR13 or -N(CH2OR13)2; R10, when n is 1, is the group R8 or R9; and R10, when n is 2, is the group -Y-B-Y- wherein B is C2-C6 alkylene optionally interrupted by -N(R11)-; R11 is C1-C12 alkyl, cyclohexyl, benzyl or C1-C4 hydroxyalkyl, or a group of the formula R12 is C1-C12 alkyl, cyclohexyl, benzyl, C1-C4 hydroxyalkyl; R13 is hydrogen, C1-C12 alkyl or phenyl; or R1l and R12 together are C4-C5 alkylene or oxaalkylene, or R11 and R12 are each a group of the formula

11. A composition according to Claim 1, wherein said piper-idine compound corresponds to the formula (VII) (VII) in which n is the number 1 or 2; R is hydrogen or methyl; and R14, when n is 1, is C4-C18 alkyl, C7 C12 aralkyl, the group -CO-R15, or C1-C4 alkyl which is substituted by -CN, -COOR16, -OH, -OCOR17 or wherein R15 is C1-C12 alkyl, C2-C4 alkenyl or phenyl, R16 is C1-C18 alkyl, R17 is C1-18 alkyl, C2-C10 alkenyl, cyclohexyl, benzyl or C6-C10 aryl; or R14, when n is 2, is C4-C12 alkylene, 2-butenylene-1,4, xylylene, the group -(CH2)2-COC-R18-COO-(CH2)2-or the group -CH2-OOC-R19-COO-CH2-wherein R18 is C2-C10 alkylene, phenylene or cyclohexylene, and R19 is C2-C10 alkylene, xylylene or cyclohexylene.

12. A composition according to Claim 1, wherein said piperidine compound corresponds to the formula (VIII) (VIII) in which D is -N(R21)- or -O-; E is C1-C3 alkylene, the group -CH2-CH(Z)-O- wherein Z is hydrogen, methyl or phenyl; the group -(CH2)3-NH- or a single bond; R is hydrogen or methyl; R1 is hydrogen, C1-C18 alkyl, C3-C8 alkenyl, C3-C8 alkynyl, C7-C12 aralkyl, C1-C8 alkanoyl, C3-C5 alkenoyl or glycidyl; R20 is hydrogen or C1-C18 alkyl; R21 is hydrogen, C1-C18 alkyl, C5-C7 cycloalkyl, C7-C12 aralkyl, cyanoethyl, C6-C10 aryl, the group -CH2-CH(Z)-OH wherein Z has the meaning defined above; a group of the formula or a group of the formula wherein G is C2-C6 alkylene or C6-C12 arylene; or R21 is a group -E-CO-NH-CH2-OR20.

13. A composition according to claim 1, wherein said piperidine compound is a polymeric compound in which the recurring structural unit contains a 2,2,6,6 tetraalkylpiperidine radical selected from the group consisting of polyester, polyether, polyamide, polyamine, polyurethane, polyurea, polyaminotriazine, poly(meth)acrylate, poly(meth)acrylamide and copolymers thereof which contain such a radical.

14. A composition according to Claim 1, wherein said piperidine compound corresponds to the formula (IX) (IX) in which n is a number from 1-4 inclusive; R is hydrogen or methyl;
R1 is hydrogen, oxyl, C1-C18 alkyl, C3-C8 alkenyl, C3-C8 alkynyl, C7-C12 aralkyl, C1-C8 alkanoyl, C3-C5 alkenoyl, glycidyl, a group -CH2CH(OH)-Z wherein Z is hydrogen, methyl or phenyl;
R22 is hydrogen, hydroxyl or C1-C8 alkoxy; and R23, when n is 1, is C1-C20 alkyl, C5-C12 cycloalkyl, C1-C14 aralkyl, when n is 2, R23 is C2-C12 alkylene, C6-C12 cycloalkylene, C8-C16 cycloalkyl-enene-dialkylene, C8-C14 aralkylene, C4-C9 mono- or dioxaalkylene;
when n is 3, R23 is C3-C12 alkane-triyl, and when n is 4, R23 is C4-C12 alkane-tetrayl.

15. A composition according to Claim 13, wherein said piperidine compound corresponds to the formula (X) (X) in which n is a number from 4-10 inclusive; R24 is C2-C8 alkylene or C5-C6 cycloalkylene; R25 is C1-C8 alkyl or C5-C6 cycloalkyl;
R26 and R27 are C1-C8 alkyl or together form a C5-C6 cycloalkyl-ene ring; and R28 is hydrogen hydroxyl, C1-C8 alkoxy or C1-C8 acyloxy.

16. A composition according to Claim 1, wherein said piperidine compound is bis-(2,2,6,6-tetramethyl-4-piperidyl) sebacate.

17. A composition according to Claim 1, wherein said piperidine compound is bis(1,2,2,6,6-pentamethyl-4-piperidyl) decanedioate.

18. The composition according to claim 1, wherein said piperidine compound is the polyester oligomer of 1-(2-hydroxy-ethyl)-2,2,6,6,-tetramethyl-4-hydroxypiperidine and 2,2-diethyl-malonic acid; bis(1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis(1,1-di-methylethyl-4-hydroxyphenyl)methyl]butyl]-propanedioate or the mixture of 3-(5-chloro-2H-benzotriazole-2-yl)-4-hydroxy-5-(1,1-dimethylethyl-phenylpropionic acid)-octyl-and -2-ethylhexyl esters.

19. The composition of claim 1, wherein said U.V. absorber is selected from the group consisting of 2-(2-hydroxyphenyl)-2H-benzotriazoles, 2,4-bis(2-hydroxyphenyl)-6-alkyl-s-triazines, 2-hydroxybenzophenones, 1,3-bis(2-hydroxybenzoyl)-benzenes, esters of benzoic acids, acrylates and oxalic acid diamides.

20. The composition of claim 19, wherein said U.V. absorber is a benzotriazole.

21. The composition of Claim 20, wherein said benzotriazole is 2-(2-hydroxy-4-methylphenyl)-2H-benzotriazole or 2-(2-hydroxy-3,5-di-tert.amylphenyl)-2H-benzotriazole.

22. The composition of Claim 20, wherein said benzotriazole is 2-(2-hydroxy-4-methylphenyl)-2H-benzotriazole or 2-(2-hydroxy-3,5-di-tert.amylphenyl)-2H-benzotriazole.

23. The composition of Claim 19, wherein said U.V. absorber is 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]
decane-2 4-dione; 2-dodecyl-2'-ethoxy-oxanilide; 2-hydroxy-4-n-octoxybenzophenone; 2,2'-dihydroxy-4-methoxybenzophenone or 2,4-dihydroxybenzophenone.

24. The composition of Claim 1, wherein said stabilizer is a blend of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) decanedioate and 2-(2-hydroxy-3,5-di-tert.amylphenyl)-2H-benzotriazole.

25. The composition of Claim 1, wherein said fungicide is selected from the group consisting of carbamates, arsenic comp-ounds, chlorinated phenols, copper compounds, chlorinated comp-ounds other than chlorinated phenols; organo mercury compounds, organic tin compounds, zinc compounds, ketones, sulfonyl compounds and azole compounds.

26. The composition of Claim 5 where said fungicide is selected from the group consisting of carbamates, arsenic com-pounds, chlorinated phenols, copper compounds, chlorinated compounds other than chlorinated phenols, organo mercury com-pounds, organic tin compounds, zinc compounds, ketones, sulfonyl compounds and azole compounds.

27. The composition of Claim 1, which is present in a paint, lacquer, stain, enamel, substrate treatment or other coating formulation.

28. A method of stabilizing fungicides against light-induced deterioration which comprises adding to said fungicide an effective stabilizing amount of a stabilizing composition according to Claim 1.