AU2007253048B2 - Wood preservative formulations - Google Patents

Abstract

The invention provides formulations comprising an amine oxide, an azole and a compound of formula (I): R

Description

- 1 WOOD PRESERVATIVE FORMULATIONS Field of the Invention The present invention relates to formulations for 5 protecting wood and other cellulosic substrates against moulds, staining and other defacing organisms, and in particular to antisapstain applications. Background of the Invention 10 Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field. Antisapstain chemicals are used to protect timber, 15 in particular freshly felled or sawn timber, from attack by moulds, sapstain and decay fungi which would otherwise discolour the timber and so reduce its value. Commonly used chemicals in antisapstain formulations include 3-iodo-2-propynyl-butyl-carbamate 20 (IPBC), quaternary ammonium compounds such as didecyldimethylammonium chloride (DDAC) and benzalkonium chloride (BAC), borates (such as Borax), triazoles, copper 8-hydroxyquinoline, alkyl amines and their salts, and fenpropimorph. 25 Combinations of IPBC, triazoles and quaternary ammonium compounds have been used commercially. Formulations containing boron, for example Antiblu Select (Arch Timber Protection, Ltd.) which contains BAC, IPBC and boric acid are also known. Amine oxides 30 have also been described for use in antisapstain formulations (WO 2001/0189779, WO 2000/0071312). It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative. 35 It is an object of an especially preferred form of the present invention to provide for alternative and improved wood preservative formulations, to address -2 environmental concerns and customer pressure for ever more effective and competitive products. Improved azole containing formulations are of particular interest. Unless the context clearly requires otherwise, 5 throughout the description and the claims, the words "comprise", "comprising", and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of "including, but not limited to". 10 Although the invention will be described with reference to specific examples it will be appreciated by those skilled in the art that the invention may be embodied in many other forms. 15 Summary of the Invention According to a first aspect of the present invention there is provided a wood preservative formulation comprising a synergistic combination of an amine oxide, an azole and a compound of formula (I) 20 R--A-NR 2P (I) wherein Ri denotes an alkyl group which contains from 25 6 to 24 carbon atoms, benzyl or substituted benzyl, or (CH 2

-CH

2 0)nH where n = 1-20; A is absent or denotes a linker group that may be C=O or -C=ONH(CH 2 )s- where s = 1-3; p = 2 or 3; 2 30 and each R , which are the same or different, denotes H, CH 3 , C 2

H

5 , (CH 2

-CH

2 0)nH where n = 1-20, an alkyl group which contains from 6 to 24 carbon atoms, (CH 2 )mCOOH, (CH 2 )mCOO , (CHR 9 )mSO 3 H or

(CHR

9 )mSO 3 where m = 1 to 3 and R 9 denotes H or OH; 35 and wherein if the compound is charged it is accompanied by a counterion X-; wherein said amine oxide is: - 2a (i) a trialiphatic substituted amine oxide; (ii) an N-alkylated cyclic amine oxide; (iii) a dialkylpiperazine di-N-oxide; (iv) an alkyldi(poly(oxyalkylene))amine oxide; 5 (v) a dialkylbenzylamine oxide; (vi) a fatty amidopropyldimethyl amine oxide; (vii) a diamine oxide; (viii) a triamine oxide; or (ix) any combination of any of the foregoing; and 10 wherein the azole is: an imidizole selected from the group consisting of: benzimidazole, thiabendazole, imazalil, carbendazim, prochloraz; a 1,2,4-triazole selected from compounds of 15 formula (XI): OH

H

2 H 2

R

6 -C -C

R

5

CH

2 N (XI) wherein R 5 represents a branched or straight chain C 1

-

5 alkyl group and R6 represents a phenyl 20 group optionally substituted by one or more substituents selected from halogen atoms or C1-3 alkyl, C1-3 alkoxy, phenyl or nitro groups; compounds of formula (XII): 0 R7

R

8 0,O

CH

2 N

(XII)

- 2b wherein R 7 is as defined for R 6 above and R 8 represents a hydrogen atom or a branched or straight chain C 1

-

5 alkyl group; or selected from the group comprising 5 triadimefon, triadimenol, triazbutil, cyproconazole, difenoconazole, fluquinconazole, flusilazole, uniconazole, diniconazole, bitertanol, hexaconazole, flutriafol, epoxyconazole, tetraconazole, penconazole, and mixtures thereof 10 or mixtures of both said imidizole and said 1,2,4-triazole. According to a second aspect of the present invention there is provided a method of protecting a 15 substrate of wood or other cellulosic material which comprises applying to the substrate a formulation as claimed in the first aspect of the present invention or applying the individual components to the substrate such that the substrate effectively receives a formulation 20 according to the first aspect of the present invention. According to a third aspect of the present invention there is provided a substrate made of wood or other cellulosic material treated with a formulation as 25 defined in the first aspect of the present invention. According to a fourth aspect of the present invention there is provided a substrate of wood or other cellulosic material comprising a synergistic combination 30 of an amine oxide, an azole and a compound of formula (I)

R

1

-A-NR

2 P (I) 35 wherein - 2c R' denotes an alkyl group which contains from 6 to 24 carbon atoms, benzyl or substituted benzyl, or (CH 2

-CH

2 0)nH where n = 1-20; A is absent or denotes a linker group that may 5 be C=O or -C=ONH (CH 2 ) - where s = 1-3; p = 2 or 3; 2 and each R , which are the same or different, denotes H, CH 3 , C 2

H

5 , (CH 2

-CH

2 0)nH where n = 1-20, an alkyl group which contains from 6 to 24 carbon 10 atoms, (CH 2 )mCOOH, (CH 2 )mCOO , (CHR 9 )mSO 3 H or

(CHR

9 )mSO3 where m = 1 to 3 and R 9 denotes H or OH,; and wherein if the compound is charged it is accompanied by a counterion X~; wherein said amine oxide is: 15 (i) a trialiphatic substituted amine oxide; (ii) an N-alkylated cyclic amine oxide; (iii) a dialkylpiperazine di-N-oxide; (iv) an alkyldi(poly(oxyalkylene))amine oxide; (v) a dialkylbenzylamine oxide; 20 (vi) a fatty amidopropyldimethyl amine oxide; (vii) a diamine oxide; (viii) a triamine oxide; or (ix) any combination of any of the foregoing; and wherein the azole is: 25 an imidizole selected from the group consisting of: benzimidazole, thiabendazole, imazalil, carbendazim, prochloraz; a 1,2,4-triazole selected from compounds of formula (XI): 30 (XI) OH

H

2 H 2

R

6 -C -C R 5

CH

2 N ""N

N

- 2d wherein R 5 represents a branched or straight chain C1-5 alkyl group and R 6 represents a phenyl group optionally substituted by one or more substituents selected from halogen atoms or C1-3 5 alkyl, C1-3 alkoxy, phenyl or nitro groups; compounds of formula (XII): 0 R 7

CH

2 N N- / (XII) wherein R7 is as defined for R 6 above and R 8 10 represents a hydrogen atom or a branched or straight chain Ci-s alkyl group; or selected from the group comprising triadimefon, triadimenol, triazbutil, cyproconazole, difenoconazole, fluquinconazole, 15 flusilazole, uniconazole, diniconazole, bitertanol, hexaconazole, flutriafol, epoxyconazole, tetraconazole, penconazole, and mixtures thereof or mixtures of both said imidizole and said 1,2, 4-triazole. 20 The present inventors have found that formulations comprising an amine oxide, an azole and a compound of formula (I) 25 R -A-NR 2P (I) wherein R' denotes an alkyl group which contains from 6 to 24 carbon atoms, benzyl or substituted benzyl, or (CH 2 30 CH 2 0)nH where n = 1-20; - 2e A is absent or denotes a linker group that may be C=0 or -C=ONH(CH 2 )s- where s = 1-3; p = 2 or 3; and each R 2 , which may be the same or different, 5 denotes H, CH 3 , C 2

H

5 , (CH 2

-CH

2 0)nH where n = 1-20, an alkyl group which contains from 6 to 24 carbon atoms,

(CH

2 )mCOOH, (CH 2 )mCOO , (CHR')mSO 3 H or (CHR')mSO3 where m = 1 to 3 and R 9 denotes H or OH; and wherein if the compound is charged it is 10 accompanied by a suitable counterion X are surprisingly effective at protecting wood, in particular at providing antisapstain activity. Thus the present invention provides an antisapstain composition comprising an amine oxide compound, an azole 15 compound and compound of formula (I)

RI-A-NR

2 P (I) wherein 20 R 1 denotes an alkyl group which contains from 6 to 24 carbon atoms, benzyl or substituted benzyl, or (CH 2 CH 2 0)nH where n = 1-20; A is absent or denotes a linker group that may be C=0 or -C=ONH(CH2)s- where s = 1-3; 25 P = 2 or 3; 2 and each R , which may be the same or different, denotes H, CH 3 , C 2

H

5 , (CH 2

-CH

2 0)nH where n = 1-20, an alkyl group which contains from 6 to 24 carbon atoms,

(CH

2 )mCOOH, (CH 2 )mCOO , (CHR')mSO 3 H or (CHR 9 )mS0 3 where m = 30 1 to 3 and R 9 denotes H or OH; and wherein if the compound is charged it is accompanied by a suitable counterion X-. Preferably, the amine oxide is represented by the general formula (II) 35 WO 2007/135435 PCT/GB2007/001919 -3 R2 R--A--+O

R

3 (II) wherein R, R 2 and R 3 are independent and can be hydrogen, optionally substituted poly(oxyalkylene) or a linear, 5 branched, cyclic, aromatic or any combination thereof of a saturated or unsaturated, substituted or unsubstituted

C

1 to C,, group, preferably C, to C, 20 or alternatively R 2 and R 3 together form a substituted or unsubstituted cyclic group; 10 A is absent or denotes a linker group that may be -C=ONH(CH2)9- where s = 1-3; wherein any of the carbon atoms other than those bound to the nitrogen atom shown in formula (II) may be replaced with a hetero atom, or alternatively any methyl 15 group that forms part of R1, R 2 or R 3 other than one which is bound directly to the nitrogen atom shown in formula (II) may be replaced with a dimethyl amine oxide. The amine oxide compound may be a trialiphatic substitured amine oxide, an N-alkylated cyclicamine 20 oxide, .a dialkylpiperazine di-N-oxide, an alkyldi(poly(oxyalkylene) )amine oxide, a dialkylbenzylamine oxide, a fatty amidopropyldimethyl amine oxide, a diamine oxide, a triamine oxide, or any combination of any of the foregoing. Preferably, the 25 amine oxide includes at least one C 8

-C

8 alkyl moeity. Preferred trialiphatic substituted amine oxides are represented by the general formula (III) R4 R 5--N+ R6 WO 2007/135435 PCT/GB2007/001919 -4 (III) wherein R 4 , R' and R 6 are independent and can be linear, branched, cyclic, aromatic or any combination thereof of a saturated or unsaturated C 1 to C 40 group 5 wherein any of the carbon atoms other than those bound to the nitrogen atom shown in formula (III) may be replaced with a hetero atom, particularly oxygen, sulphur or nitrogen. R 4 , R5 and R' independently may be alkyl, alkenyl, or alkynyl groups. More preferably, R 4 10 is a linear, branched, cyclic or any combination thereof

C

8 to C 22 saturated or unsaturated group, such as coco, hydrogenated tallow, soya, decyl, hexadecyl, and oleyl; and R5 and R6 independently are linear, branched, or any combination thereof C 1 to C 22 saturated or unsaturated 15 groups, such as coco, hydrogenated tallow, soya, decyl, and hexadecyl. A preferred trialiphatic substituted amine oxide is dialkylmethylamine oxide having the formula R 4

RCH

3 N-0, where R 4 and R' are defined as above. Another preferred 20 trialiphatic substituted amine oxide' is an alkyldimethylamine oxide having the formula R 4

(CH

3

)

2 N-0, where R 4 is defined as above. More preferred alkyldimethylamine oxides have the formula R 22

(CH

3

)

2 N-0, where R 2 is a linear or branched C 8

-C

1 8 alkyl or alkenyl. 25 Preferably, R" is a linear or branched C.-C 1 alkyl. Alkyldimethylamine oxides are non-toxic and non mutagenic surfactants. Suitable alkyldimethylamine oxides include, but are not limited to, a C 10 alkyldimethylamine oxide, a C-C 14 alkyldimethylamine 30 oxide, a C 12

-C

16 alkyldimethylamine oxide, a C 26

-C

18 alkyldimethylamine oxide, and any combination of any of the foregoing. Preferred N-alkylated cyclicamine oxides have the formula R 7

RR

9 N-0 where R! is defined as R 4 above. and R 8 35 and R 9 are linked to form a cyclic group. The cyclic group typically contains from 4 to 10 carbon atoms and WO 2007/135435 PCT/GB2007/001919 -5 may optionally contain oxygen, sulphur, nitrogen, or any combination of any of the foregoing. More preferred N alkylated cyclicamine oxides include, but are not limited to, an alkylmorpholine N-oxide, a 5 dialkylpiperazine di-N-oxide, and any combination of any of the foregoing. Preferred alkylmorpholine N-oxides have the general formula (IV): RIO N O 0 \ -/ 10 (IV) where R10 is defined as R4 above. According to a more preferred embodiment, R 0 is a linear or branched C 8 to C 1 alkyl. Examples of preferred alkylmorpholine N-oxides include, but are not limited to, cetyl morpholine N 15 oxide and lauryl morpholine N-oxide. Preferred dialkylpiperazine di-N-oxides have the general formula (V): R R1 N N 0 0 (V) 20 where R 1 1 is defined as R' above and R1 2 is defined as R above. Preferred alkyldi(poly(oxyalkylene) )amine oxides have the general formula (VI): WO 2007/135435 PCT/GB2007/001919 -6

CH

2 CHR140 )mH

R

1 3 --- +O0 R(-I H 1

CH

2 CHR"O) H (VI) where Rl' is defined as R 4 above; R 1 4 and R independently are H or CH,; and m and n independently are integers from about 1 to about 10. 5 Preferred dialkylbenzylamine oxides have the formula R 1 'R"R1N-0, where R1 6 is defined as R 4 above; R 7 is defined as R' above; and R is benzyl. More preferred dialkylbenzylamine oxides include, but are not limited to, alkylbenzylmethylamine oxides having the formula 10 R R CH 3 N-O where R" 'and R1 7 are defined as above. According to a more preferred embodiment, R6 is a linear or branched C8-C 1 alkyl. Preferred fatty amidopropyldimethylamine oxides have the general formula (VII): 15 0

CH

3 R1 N H

H

3 C (VII) where R" is defined as R 4 above. Preferred diamine oxides have the general formula (VIII):

CH

3 R20- -- +jO (H2C N CH

H

3 C 20

(VIII)

WO 2007/135435 PCT/GB2007/001919 -7 where R 20 is defined as R 4 above; and n is an integer from about 1 to about 10. Preferred triamine oxides have the general formula (IX):

H

3 C0

H

2 C N(C_ m _CH3 H2C N CH n / O.4

H

3 C 5 (IX) where R 2 1 is defined as R' above; and m and n independently are -integers from about-1 to about 10. Particularly preferred amine oxides are alkyl 10 dimethyl amine oxides such as decyl dimethyl amine oxide, lauryl dimethyl amine oxide, isoalkyl dimethyl amine oxide, myristyl dimethyl ethyl amine oxide, cetyl diinethyl amine oxide, stearyl dimethyl amine oxide and octyl dimethyl amine oxide. Particularly preferred is 15 N-alkyl (C 2 -C,) -N,N-dimethylamine oxide (ADO). In addition a mixture of two or more amine oxides may be used, with a mixture, e.g. an equimolar mixture of C ,-N,N-dimethylamine oxide and C 16 - N,N-dimethylamine oxide being especially preferred. 20 The formulations of the present invention comprise one or more azole compounds, i.e. a compound comprising an azole group. The azole compound may be an imidazole or a 1,2,4-triazole and is preferably represented by the general formula (X) 25 WO 2007/135435 PCT/GB2007/001919 -8 R1 R4 N N /> R2 R3) (X) wherein X denotes C or N; 5 R 1 denotes hydrogen or a linear, branched, cyclic, aromatic or any combination thereof of a saturated or unsaturated, substituted or unsubstituted C1 to C,, group wherein any of the carbon atoms other than those bound to the nitrogen atom shown in formula (X) may be 10 replaced with an optionally substituted hetero atom;

R

2 denotes hydrogen, Cl-Ca alkyl, C 2

C

8 alkenyl, C.-C. aromatic, C 5

-C

1 , heteroaromatic or C 1

-C

4 alkyl carbamate; R' denotes hydrogen; or when X is C together with R may provide a 15 benzimidazole group. The imidazole compound incorporates a five-membered diunsaturated ring composed of three carbon atoms and two nitrogen atoms at non-adjacent positions. The imidazole compound may be a benzimidazole. Preferred 20 compounds include thiabendazole, imazalil, carbendazim and prochloraz. The 1,2,4-triazole compound incorporates a five-membered diunsaturated ring composed of three nitrogen atoms and two carbon atoms at non-adjacent 25 positions. Preferred triazole compounds include a triazole compound selected from compounds of formula (XI): WO 2007/135435 PCT/GB2007/001919 -9 OH

H

2 H 2

R

6 -C -C R5

CH

2 N N (XI) wherein R 5 represents a branched or straight chain

C

15 alkyl group (e.g. t-butyl) and R 6 represents a phenyl 5 group optionally substituted by one or more substituents selected from halogen (e.g. chlorine, fluorine or bromine) atoms or C13 alkyl (e.g. methyl), C, 3 alkoxy (e.g. methoxy), phenyl or nitro groups. Alternatively, the triazole compound is 10 advantageously selected from compounds of formula (XII): 0 R7

CH

2 N N-/ (XII) wherein R" is as defined for R above and R" represents a hydrogen atom or a branched or straight 15 chain C1 5 alkyl group (e.g. n-propyl). Particularly preferred triazoles include but are not limited to, triadimefon, triadimenol, triazbutil, propiconazole, cyproconazole, difenoconazole, fluquinconazole, tebuconazole, flusilazole, uniconazole, 20 diniconazole, bitertanol, hexaconazole, azaconazole, WO 2007/135435 PCT/GB2007/001919 - 10 flutriafol, epoxyconazole, tetraconazole, penconazole, and mixtures thereof. Most preferred triazoles are propiconazole, azaconazole, hexaconazole, tebuconazole, cyproconazole, 5 triadimefon and mixtures thereof. The compound of formula (I) may optionally be a quaternary ammonium compound, an amine or amine salt, a betaine or an amphoteric betaine compound. When the linker group A is absent, the R 1 group is directly bonded 10 to the nitrogen. Where the compound of formula (I) is positively charged, it is accompanied by an anion X which is chosen to allow ready water solubility. Examples of suitable anions include chloride, bromide, sulphate, acetate, 15 propionate, lactate, citrate, methosulphate, hydroxide, carbonate and bicarbonate.

The compound of formula (I) may preferably be a quaternary ammonium compound, i.e. a compound derived from ammonium with all four hydrogen atoms replaced by 20 organic groups and having the general formula (XIII): R 1 2 (XIII) Of the quaternary ammonium compounds which may be used in the compositions and methods of the present invention, suitable compounds include: 25 1. Monoalkyltrimethyl ammonium salts of formula (XIV): CH3

R-N-CH

3 - X

CH

3

(XIV)

WO 2007/135435 PCT/GB2007/001919 - 11 wherein R is an alkyl group having from 6 to 22 carbon atoms, preferably from 12 to 14 carbon atoms, and X is an anion chosen to allow ready water solubility of the quaternary ammonium salt. Examples being : chloride, 5 bromide, sulphate, acetate, propionate, lactate, citrate, methosulphate, carbonate and bicarbonate. Preferred examples include Cocotrimethyl ammonium chloride in which the alkyl group R consists of a mixture of predominantly C.2 and C1. 10 2. Dialkyl dimethyl ammonium salts of formula (XV): YH3 R'-N' CH3. X~ R2 (XV) wherein R- and R2 are alkyl groups which may be the same or different and which contain from 6 to 22 carbon 15 atoms, preferably from 8 to 10 carbon atoms, and X is an anion of the type previously described. Preferred examples include Didecyl dimethyl ammonium chloride, didecyl dimethyl ammonium carbonate, didecyl dimethyl ammonium bicarbonate, dioctyl dimethyl 20 ammonium chloride and octyl decyl dimethyl ammonium chloride either individually or as a mixture containing two or three of these. 3. Alkyl dimethyl or diethyl benzyl ammonium salts and 25 dialkyl methyl or ethyl benzyl ammonium salts of formulae (XVI) or (XVII): R 4 R 4

R

3

R

3 R1 3 R H-N- . X and R-N- C -X H22 H R3 R R 2

R

5 RS R 6 (XVI)

(XVII)

WO 2007/135435 PCT/GB2007/001919 - 12 wherein R 1 and R 2 are alkyl groups which can be the same or different and which contain from 6 to 22 carbon atoms, preferably from 8 to 10 carbon atoms in a dialkyl compound and from 10 to 14 carbon atoms in a monoalkyl 5 compound; R 3 is methyl or ethyl; R 4 , R 5 and R' are hydrogen or Ci-, alkyl groups; and X~ is an anion of the type previously described. Preferred examples include Coco benzyl dimethyl ammonium chloride and dicoco benzyl methyl ammonium 10 chloride in which the alkyl groups are predominantly C,, and

C

1 . 4. Alkyl and dialkyl oxyethylene methyl ammonium salts of formulae (XVIII) or (XIX): 15

CH

3 CH3 R- N-CH 3 - X R N R X ( C-CH2O) H ( C-CH20) H H2 mH2m (XVIII) (XIX) wherein R' and R 2 are alkyl groups which may be the same or different and which contain from 6 to 22 carbon atoms, preferably from 8 to 10 carbon atoms in a dialkyl 20 compound and from 10 to 14 carbon atoms in a monoalkyl compound, most preferably 10 carbon atoms. .m is a number from 1 to 20 typically from 1 to 8, preferably from 3 to 5. X~ is an anion of the type previously described, preferably propionate or lactate. 25 Preferred examples include N,N-didecyl-N-methyl poly(oxyethyl) ammonium propionate (Bardap 26) or N,N didecyl-N-methyl-poly(oxyethyl) ammonium lactate. ,Benzalkonium chloride and benzalkonium hydroxide are especially preferred.

WO 2007/135435 PCT/GB2007/001919 - 13 Alternatively, the compound of formula (I) may preferably be a betaine. Betaines are advantageous as they are amphoteric and hence remove the need to have a potentially corrosive counterion. 5 Preferably, the betaine is selected from the group consisting of coco amido propyl dimethyl betaine; cetyl betaine( (carboxylatomethyl) hexadecyldimethylammonium); C12 amine dipropionate; and coco amido propyl dimethyl sultaine (cocoamidopropyl-N, N-dimethyl-N-2 10 hydroxypropyl sulfobetaine). The betaine is, e.g. of the formula R-N'(CH 3 ) 2

-CH

2 COO ; or R-C(=O)N(CH 3

)

2

-CH

2 -COO or a salt thereof where R is a straight chain C 6

-C

24 alkyl group, or a C,-C, alkyl group, or R is a straight chain C1 2 -C16 alkyl group. 15 The betaine in one embodiment is a cocamidopropylbetaine of formula: RC(=O)NH(CH 2

)

3 -N+ (CH 3

)

2 CH 2 -COO~ wherein R is a C,,-C_ straight chain alkyl group. The compound of formula (I) may be a dimethylalkylamine or salt thereof. A 20 dimethylalkylamine is an N,N-dimethyl-N-alkylamine where alkyl represents an alkyl chain with 6 to 20 carbon atoms, preferably 12 to 14 carbon atoms. In addition to pure dimethylalkylamines, it is also possible to use mixtures, for example dimethyl-C 12 -alkylamine and 25 dimethyl-C.

4 alkylamine (dimethyl-C.

2

/C

14 -alkylamine). The compositions typically comprise one or more further active ingredients. Halopropynyl compounds are particularly preferred examples of additional active ingredients. 30 Preferred halopropynyl compounds are iodopropynyl carbamate compounds. The iodopropylnyl carbamate compound is an ester or salt of carbamic acid. This class of compounds includes compounds of the general formula (XX): 0 [I -- Nn R (XX) H2H WO 2007/135435 PCT/GB2007/001919 - 14 wherein R is selected from the group consisting of hydrogen, substituted and unsubstituted alkyl groups having from 1 to 20 carbon atoms, substituted and unsubstituted aryl, alkyl aryl, and aralkyl groups 5 having from 6 to 20 carbon atoms and from substituted and unsubstituted cycloalkyl and cycloalkenyl groups of 3 to 10 carbon atoms, and m and n are independently integers from 1 to 3, i.e., m and n are not necessarily the same. 10 Preferred are compounds where m is 1 and n is 1 having the following formula (XXI): 0 I - C 0 N-R

H

2 H (XXI) Suitable R substituents include alkyls such as methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, hexyl, 15 heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, cycloalkyls such as cyclohexyl, aryls, alkaryls and aralkyls such as phenyl, benzyl, tolyl, cumyl, halogenated alkyls and aryls, such as chlorobutryl and chlorophenyl, and alkoxy aryls such as ethoxyphenyl and 20 the like. Compounds of this formula include iodopropargyl carbamates such as 3-iodo-2-propynyl propyl carbamate, 3-iodo-2-propynyl butyl carbamate, 3-iodo-2-propynyl hexyl carbamate, 3-iodo-2-propynyl cyclohexyl carbamate, 25 3-iodo-2-propynyl phenyl carbamate, and mixtures thereof. Most preferred is 3-iodo-2-propynyl butyl carbamate (IPBC). The inventors have shown that the efficacy of the formulations described is surprisingly greater than 30 would be expected based on an additive effect. Therefore synergy is taking place. Thus preferred compositions comprise, in synergistic proportions, an WO 2007/135435 PCT/GB2007/001919 - 15 azole compound, an amine oxide compound and a compound of formula (I). Particularly effective ratios of the azole to amine oxide have been identified and include amine oxide:azole 5 ratios of 4:1 to 1:20, preferably 4:1 to 1:10, preferably 2:1 to 1:5, more preferably 1.5:1 to 1:2. Particularly effective ratios of compound (I) to amine oxide have been identified and include compound (I):amine oxide ratios of greater than 2:1, preferably 10 greater than 4:1, more preferably greater than 5:1 or 6:1 e.g. greater than 8:1 or 10:1, such as 2:1 to 100:1, or 2:1 to 50:1, or 4:1 to 30:1 preferably 10:1 to 25:1, preferably 15:1 to 25:1. Particularly preferred formulations are those in 15 which the compound of formula (I) is a quaternary ammonium compound. Typically these formulations will have a quaternary ammonium compound:amine oxide ratio of greater than 2:1, preferably greater than 4:1, more preferably greater than 5:1 or 6:1 e.g. greater than 8:1 20 or 10:1, such as 2:1 to 50:1, or 4:1 to 30:1 preferably 10:1 to 25:1, preferably 15:1 to 25:1. Particularly effective ratios of compound (I) to azole have been identified and include compound (I): azole ratios of greater than 2:1, preferably greater 25 than 4:1, such as 2:1 to 20:1, or 3:1 to 15:1, or 4:1 to 12:1, preferably 5:1 to 10:1. Preferred formulations contain a mixture of azoles, preferably a mixture of 1,2,4-triazoles and imidazoles. Typically these formulations will have a 30 triazole:imidazole ratio of 10:1 to 1:10, preferably 10:1 to 1:2, more preferably 10:1 to 1:1, most prefered is 10:1 to 2:1. Alternatively, the triazole:imidazole ratio is preferably 2:1 to 1:10, more preferably 1:1 to 1:10, most preferred being 1:2 to 1:10. 35 Preferably C12 amine oxides are used, or alternatively a mixture of C12 and C16 amine oxides, WO 2007/135435 PCT/GB2007/001919 - 16 preferably with a ratio of 3:1 to 1:3, preferably 2:1 to 1:2, most preferred is about 1:1. Further preferred formulations contain a halopropynyl compound. Typically these formulations 5 will have a halopropynyl:amine oxide ratio of 4:1 to 1:10, preferably 2:1 to 1:5, more preferably 1.5:1 to 1:2. Thus, the formulations have a preferred compound (I) to halopropynl compound ratio of 20:1 to 4:1, preferably 15:1 to 5:1, most preferably about 10:1. 10 All of the above ratios refer to weight percent as a percentage of the total weight of the composition. Thus, a ratio of 1:1 will refer to two components being present in equal weight percents in a composition. Thus, especially preferred formulations according 15 to the present invention comprise, an imidazole compound, an amine oxide compound, a triazole compound, a quaternary ammonium compound and a halopropylnyl compound, all as defined above and preferably at the ratios specified above . Suitable examples of such 20 formulations include benzalkonium chloride or didecyldimethylammonium chloride or carbonate or bicarbonate, IPBC, propiconazole or tebuconazole, thiabendazole or imazalil and a C.

6 and/or-C 1 dimethyl amine oxide. Each of the ingredients are also preferred 25 in their own right and may be combined with other ingredients to form further preferred formulations according to the invention. The concentration of the formulation required for preservative treatment depends on the ratio of 30 particular active agents selected, the method of treatment employed, the timber species, the level of protection required and the nature and quantity of any other biocides present. The amounts necessary can be determined readily by one skilled in the art. 35 The compositions according to the invention may additionally, comprise other active ingredients such as WO 2007/135435 PCT/GB2007/001919 - 17 termiticides, insecticides, bacteriocides and other fungicides. Suitable additional fungicides would be apparent to one skilled in the art and will vary according to the application. In particular, additional 5 fungicides which extend the spectrum of activity of the formulation may be chosen, such as fungicides active against bluestain fungi, white rots, brown rots, dry rots and moulds. Suitable additional fungicides include for example, dichlofluanid, acypetacs, including copper 10 and zinc salts, isothiazolones, tolyfluanid, chlorothanonil, fenpropimorph, sorbic acid and salts thereof, borates, guazatine and salts thereof, benzoic acid and its salts, oxathiazines, TCMTB, MBT, PCP and its salts, N-(3-aminopropyl)-N-dodecylpropane-1,3 15 diamine, Dazomet, (E)-l-(2-chloro-1,3-thiazol-5 ylmethyl-2-nitroguanadine, as well as metal compounds such as copper, Cu-oxide, copper naphthenate, copper carbonate, copper oxine, copper hydroxide, copper dihydroxide, Cu-HDO, potassium-HDO, also iron and zinc 20 and salts, compounds and soaps thereof. Suitable insecticides would also be apparent to the skilled man depending upon the intended application, and include, for example, chlorpyrifos, cypermethrin, fenvalerate, fipronil, farox, tetramethrin, isofenphos, 25 permethrin, silafluofen, deltamethrin, bifenthrin, cyfluthrin, chlorfenapyr, thiachloprid, etofenprox, chlothianidin, thiamethoxam and imidacloprid, and benzoylureas such as lufenuron, hexaflumuron and flufenoxuron and in particular, flurox. 30 The compositions according to the invention may additionally comprise other components which may act to improve the characteristics of the wood treated with these biocides. Such compounds could include water repellents based on waxes, silicones and polysiloxanes, 35 latex, fluorocarbon, organic carboxylate/metals, paper sizing agents or amine oxides, or combinations thereof; WO 2007/135435 PCT/GB2007/001919 - 18 resins or crosslinking agents based on-alkyds, acrylics, polyurethanes, formaldehydes, dimethylol, and epichlorohydrin or combinations thereof. Oils may also be used as may UV absorbers, corrosion inhibitors, 5 penetrating aids including glycols, bactericides eg PHMB, colouring agents, antioxidants, metal chelators especially iron chelators, optical brightening agents, defoamers, pH buffers or other stabilisers. In concentrate form the wood treatment composition will 10 typically comprise as active ingredients 1-20%, preferably 1-10%, e.g. 1-5% w/w amine oxide, 0.5-20%, preferably 1-12%, e.g. 2-10% w/w of azole and 5-70%, preferably 10-60% w/w compound (I). When compound (I) is a quaternary ammonium compound, the wood treatment 15 will typically comprise as active ingredient 10-70%, preferably 20-60% w/w quarternary ammonium compound. Typically these concentrates will be diluted prior to application to the wood. Dilution will preferably be with water, e.g. at a ratio, water:concentrate v/v of 20 15:1 to 250:1 e.g. 75:1 to 150:1. The appropriate dilution level can be determined by one skilled in the art dependent upon cost, the type of wood to be treated, environmental conditions and the length of time protection is required. 25 In a further aspect, the invention provides a method of preserving wood or other cellulosic substrates which comprises applying to the wood or other cellulosic substrate a formulation of the invention as described above or applying the individual components to the 30 wood/substrate such that the wood/substrate effectively receives a formulation as described. Types of wood which can benefit from treatment with the formulations of the invention include sawn timber, logs, glulam, plywood, laminated veneer lumber, wood 35 based composite products such as oriented strandboard, WO 2007/135435 PCT/GB2007/001919 - 19 medium density fibreboard, fibreboard, hardboard and particle board Other materials which can benefit from treatment with the formulations of the invention are 5 lignocellulosic substrates, wood plastic composites, cardboard and cardboard faced building products such'as plasterboard, and cellulosic material such as cotton. Also, leather, textile materials and even synthetic fibres, hessian, rope and cordage as well as composite 10 wood materials. For convenience, the invention is described with reference to the treatment of wood but it will be appreciated that other materials may be treated analogously. Preferably, though not exclusively, the formulations are applied to unseasoned timber. 15 Conveniently, the compositions of the present invention are applied as a liquid composition. They may also be applied as a solid implant or paste. Preferably, the compositions are applied as a liquid composition, e.g. in the form of an emulsion made up of 20 solubilised liquid droplets. These emulsions do not contain any biocides in a solid, particulate form. Preferably, the emulsions are in the form of a micro emulsion. The person skilled in the art of making emulsions knows how to make an emulsion according to the 25 invention by the use of suitable solvents and emulsifying agents. Preferably, when applied in liquid form, this is in an aqueous solution, but one or more organic solvents or a mixture of water and an organic solvent could also be 30 used. Suitable organic solvents include both aromatic . and aliphatic hydrocarbon solvents such as white spirit, petroleum distillate, kerosene, diesel oils and naphthas. Also, benzyl alcohol, 2-phenoxy ethanol, methyl carbitol, propylene carbonate, benzyl benzoate, 35 ethyl lactate and 2-ethyl hexyl lactate.

WO 2007/135435 PCT/GB2007/001919 - 20 The application of these compositions may be by one or more of dipping, deluging, spraying, brushing or other surface coating means or by impregnation methods, e.g. high pressure or double vacuum impregnation into 5 the body of the wood or other material, all being techniques well known to the man skilled in the art. Impregnation under pressure is particularly advantageous when the substrate is wood or a wood composite material which is made to become wet during its life, for 10 example, wood for window frames, timber used above ground in exposed environments such as decking and timber used in ground contact or fresh water or salt water environments. Substrates made of wood or cellulosic material 15 which have been treated with a composition or by a method according to the invention as described herein, comprise further aspects of the present invention. Preferably, the compositions are applied to timber components before they are used but they can also be 20 used remedially as a curative action in preventing continued wood defacement. The invention will be further described with reference to the following non-limiting Examples and Figures in which: 25 Figure 1 is a graph showing the extent of sapstain present on the untreated boards used in Example 1. Figure 2 is a graph showing the performance of AT6 30 applied at 1.35% v/v during the test of Example 1. Figure 3 is a graph showing the performance of AT7M (AT6 plus thiabendazole and equal amounts of C12 and C16 amine oxides) applied at 1.15% v/v during the test of 35 Example 1.

WO 2007/135435 PCT/GB2007/001919 - 21 Figure 4 is a graph showing the extent of sapstain present on the untreated Scots pine after 4 months' exposure, as described in Example 2. 5 Figure 5 is a graph showing the performance of AT6A applied at 1.02% v/v during the test of Example 2. Figure 6 is a graph showing the performance of AT7M (AT6A plus thiabendazole and mixed C12/C16 amine oxides) 10 applied during the test of Example 2. Figure 7 is a graph showing the performance of AT26 (AT6A plus Imazalil) applied during the test of Example 2. 15 Figure 8 is a graph showing the performance of AT27M (AT26 plus mixed C12/C16 amine oxides) applied during the test of Example 2. 20 Figure 9 is a graph showing the performance of AT15M (AT6A plus thiabendazole, prochloraz and mixed C12/C16 amine oxides) applied during the test of Example 2. Figure 10 is a graph showing the performance of AT29M 25 (AT6A plus thiabendazole, imazalil and mixed C12/C16 amine oxides) applied during the test of Example 2. Figure 11 is a graph showing the extent of sapstain present on the untreated boards after 4 months exposure, 30 as described in Example 3. Figure 12 is a graph showing the performance of AT6 applied at 0.69% applied during the test of Example 3. 35 Figure 13 is a graph showing the performance of AT6 applied at 1.03% applied during the test of Example 3.

WO 2007/135435 PCT/GB2007/001919 - 22 Figure 14 is a graph showing the performance of AT9 (AT6 plus C16 amine oxide) applied at 0.62% applied during the test of Example 3. 5 Figure 15 is a graph showing the performance of AT9 (AT6 plus C16 amine oxide) applied at 0.93% applied during the test of Example 3. 10 Figure 16-is a graph showing the extent of sapstain present on the untreated boards after 2 months' exposure, as described in Example 4. Figure 17 is a graph showing the performance of AT6A 15 applied during the test of Example 4 Figure 18 is a graph showing the performance of AT7A (a diluted form of AT6A plus thiabendazole and C12 Amine oxide) applied during the test of Example 4. 20 Figure 19 is a graph showing the performance of ATF1 (AT7A with DDAC used in place of the BAC, and no thiabendazole) applied during the test of Example 4. 25 Figure 20 is a graph showing the performance of ATF2 (ATFI without the IPBC) applied during the test of Example 4. Figure 21 is a graph showing the performance of ATF3 30 applied during the test of Example 4. Figure 22 is a graph showing the performance of ATF4 (ATF3 without the IPBC) applied during the test of Example 4. 35 WO 2007/135435 PCT/GB2007/001919 - 23 Figure 23 is a graph showing the performance of ATF5 applied during the test of Example 4. Figure 24 is a graph showing the performance of ATF6 5 (ATF5 without the imazalil and IPBC) applied during the test of Example 4.

WO 2007/135435 PCT/GB2007/001919 - 24 Examples Typically, the following formulations were made by first mixing the azoles and/or imidazoles plus the 5 halopropynyl compound (if present) with the Dowanol DPM@ solvent for 30 minutes. After this time; the compound of formula (I) (and ethoxylated caster oil if required) was added and the formulation mixed until all the solids dissolved. Water, amine oxides and defoamer were then 10 added and mixed until a clear homogenous product was obtained. Example 1 15 Two anti-sapstain formulations were tested in an accelerated field trial in Florida. The formulations were as follows: 20 AT6 (Comparative Formulation) Benzalkonium chloride (80% a.i.) 62.5% w/w IPBC (98% a.i.) 5.1 Propiconazole (50% a.i.) 10.0 25 Defoamer 0.2 Dowanol DPM@ 10.0 Water 12.2 AT7M 30 Benzalkonium chloride (80% a.i.) 62.5% w/w IPBC (98% a.i.) 5.1 Propiconazole (50% a.i.) 10.0 Thiabendazole (99% a.i.) 1.01 35 C16 amine oxide (30% a.i) 4.0 C12 amine oxide (30% a.i.) 4.0 WO 2007/135435 PCT/GB2007/001919 - 25 Defoamer 0.2 Dowanol DPM@ 10.0 Water 3.19 5 Both formulations contained the same levels of IPBC, propiconazole and benzalkonium chloride, but AT7M additionally contained thiabendazole and C12 and C16 amine oxides. 10 The formulations were tested at solution strengths (diluted with water) chosen -such that the cost of product in the treated wood was the same AT6 1.35% v/v 15 AT7M 1.15% The wood used for the trial was freshly sawn Southern Yellow Pine obtained locally in Florida. For each formulation a total of 25 boards each measuring 25mm x 20 100mm x 600mm were tested. An accelerated field test method was used. After dipping boards for 1 minute in treatment solution and allowing excess liquid to run off, the boards were 25 stacked in blocks of 25, five boards wide by five boards high with no separation between layers or rows. Finally each stack was covered in polythene to maintain the moisture content at a high level. 30 The stacks were stored for the duration of the trial in the open sawmill yard. After three weeks the boards were inspected for visual colonisation by sapstain and mould fungi. Each board 35 was assigned a grade according to the 0-4 scale given in CEN/TS 15082 'Wood Preservatives - Determination of the WO 2007/135435 PCT/GB2007/001919 - 26 Preventive Effectiveness Against Sapstain Fungi on Freshly Sawn Timber - Field Test'. Grade Description 0 "clean" timber with 0% surface stain coverage 1 "slight" staining with less than 10% surface stain coverage 2 "medium" staining with 10%-25% surface stain coverage 3 "heavy" staining with 26%-50% surface stain coverage 4 "severe" staining with >50% surface stain coverage 5 Table 1: Scale for estimation of sapstain coverage The sapstain ratings (grades) for each board and each product as well as untreated control boards are presented graphically in Figures 1 to 3. 10 Figure 1 shows the extent of sapstain present on the untreated boards. All 25 boards have achieved either Grade 3 (heavy staining) or Grade 4 (severe staining) indicating a very high fungal activity during the test. 15 Grade 2 or higher is generally accepted as representing a failure to sapstain in commercial terms, hence a 100% failure rate has been achieved. Figure 2 shows how AT6 performed at 1.35% v/v during the 20 test. Performance is rather poor in this test as 5 boards have reached a-Grade 2 or higher. Hence 25% of the boards treated with AT6 have failed the test. Figure 3 shows the effect of incorporating both 25 thiabendazole and equal amounts of C12 and C16 amine WO 2007/135435 PCT/GB2007/001919 - 27 oxides into AT6 to give a formulation called AT7M, applied at 1.15% v/v such that the cost in the wood is the same as 1.35% AT6. It is immediately clear that the performance is now much improved over AT6 with only a 4% 5 failure rate as shown by only 1 of the 25 boards reaching a grade 2. Example 2 10 A number of anti-sapstain formulations were tested in a field trial in Polnica, North-Eastern Poland. All formulations contained the same levels of IPBC, propiconazole and benzalkonium ,chloride but were 15 modified by the addition of other biocides; alone, in combinations and with mixed C12/C16 amine oxides. The formulations were as follows 20 AT6A (Comparative Formulation) Benzalkonium chloride (80% a.i.) 62.5% w/w IPBC (98% a.i.) 5.1 Propiconazole (50% a.i.) 10.0 25 Defoamer 0.2 Dowanol DPM@ 8.0 Propionic acid 3.0 Water 11.2 30 AT7M Benzalkonium chloride (80% a.i.) 62.5% w/w IPBC (98% a.i.) 5.1 Propiconazole (50% a.i.) 10.0 35 Thiabendazole (99% a.i.) 1.01 C16 amine oxide (30% a.i) 4.0 WO 2007/135435 PCT/GB2007/001919 - 28 C12 amine oxide (30% a.i.) 4.0 Defoamer 0.2 Dowanol DPM@ 8.0 Propionic acid 3.0 5 Water 2.19 AT15M Benzalkonium chloride (80% a.i.) 62.5% w/w 10 IPBC (98% a.i.) 5.1 Propiconazole (50% a.i.) 10.0 Prochloraz (99% a.i.) 2.02 Thiabendazole.(99% a.i.) 1.01 C16 amine oxide (30% a.i) 4.0 15 C12 amine oxide (30% a.i.) 4.0 Defoamer 0.2 Dowanol DPM@ 8.0 Propionic acid 3.0 Water 0.17 20 AT26 (Comparative Formulation) Benzalkonium chloride (80% a.i.) 62.5% w/w IPBC (98% a.i.) 5.1 25 Propiconazole (50% a.i.) 10.0 Imazalil (99% a.i.) 2.02 Defoamer 0.2 Dowanol DPM® 8.0 Propionic acid 3.0 30 Water 9.18 AT27M Benzalkonium chloride (80% a.i.) 62.5% w/w 35 IPBC (98% a.i.) 5.1 Propiconazole (50% a.i.) 10.0 WO 2007/135435 PCT/GB2007/001919 - 29 Imazalil (99% a.i.) 2.02 C16 amine oxide, (30% a.i) 4.0 C12 amine oxide (30% a.i.) 4.0 Defoamer 0.2 5 Dowanol DPM@ 8.0 Propionic acid 3.0 Water 1.18 AT29M 10 Benzalkonium chloride (80% a.i.) 62.5% w/w IPBC (98% a.i.) 5.1 Propiconazole (50% a.i.) 10.0 Imazalil (99% a.i.) 2.02 15 Thiabendazole (99% a.i.) 1.01 C16 amine oxide (30% a.i) 4.0 C12 amine oxide (30% a.i.) 4.0 Defoamer 0.2 Dowanol DPM@ 8.0 20 Propionic acid 3.0 Water 0.17 The wood used for the trial was freshly sawn Scots pine obtained locally in Poland with moisture contents 25 between 40 and 60%. For each formulation a total of 60 boards each were used, each board measuring 22mm x 125mm x 1000mm. The boards were treated by dipping in open tanks 30 containing 40 liters of solution. The samples were immersed in the bath for 1 min. Next the treated wood was stored for 10 min in a special stand in order to allow draining of excess product. 60 samples were dipped for each product and concentration. The wood was 35 stored in 48 cm wide stacks (5 samples were stored parallel in a single layer). 40 samples were stored WO 2007/135435 PCT/GB2007/001919 - 30 without stickers (close stacked) while the other 20 pieces were stored with stickers (open stacked) to reflect common commercial practices. The stickers used were 8mm thick and were dipped in the same product as 5 the stack to which they were allocated. Separate stacks were formed for each product in order to prevent any unwanted interactions. A control stack of untreated timber was also included. 10 All the stacks were covered by a layer of untreated boards and were stored for the duration of the trial in the open yard exposed to the weather. This test methodology is broadly as described in CEN/TS 15 15082 "Wood Preservatives-Determination of the Preventive Effectiveness Against Sapstain Fungi on Freshly Sawn Timber-Field Test". The stacks of treated boards were inspected after 4 20 months. Each individual board was assigned a visual grade according to the 0-4 scale also given in CEN/TS 15082 and described in Table 1 of Example 1. The sapstain ratings (grades) for each board and each 25 product as well as untreated control boards are presented graphically in Figures 4 to 8. Since a closed stack configuration represents the more severe hazard and shows up differences between 30 formulations more quickly and reliably, all data presented herein refers to this closed stacked arrangement. No data is presented for timber stored open stacked. 35 Figure 4 shows the data for untreated Scots pine after 4 months exposure WO 2007/135435 PCT/GB2007/001919 - 31 Figure 5 shows how AT6A performed at 1.02% v/v during the test. The performance is poor, with 28% of the boards having grade 2 or above. 5 Figure 6 shows the effect of including thiabendazole and mixed C12/C16 amine oxides. AT7M is AT6A plus both 1% Thiabendazole and 8% mixed amine oxides. 10 Figure 7 shows the data for including Imazalil in AT6A. AT26 is AT6A plus 2% Imazalil. Figure 8 shows the effect of including Imazalil and mixed C12/C16 amine oxides. AT27M is AT6A plus both 2% 15 imazalil and 8% mixed C12/C16 amine oxides. Figure 9 shows the effect of including thiabendazole, prochloraz and mixed C12/C16 amine oxides. AT15M is AT6A plus thiabendazole, prochloraz and mixed C12/C16 20 amine oxides. Figure 10 shows the effect of including thiabendazole, imazalil and mixed C12/C16 amine oxides. AT29M is AT6A plus thiabendazole, prochloraz and mixed C12/C16 amine 25 oxides. AT7M with both 1% Thiabendazole and 8% mixed amine oxides performs better than AT6A, with only 3% failure rate and 75% of the boards being completely clean (Grade 30 0). Figure 7 shows the addition of 2% Imazalil to AT6A to give formulation AT26, has a slightly detrimental effect on anti-sapstain performance with an increase in the 35 number of failing boards from 28% to 30% combined with a reduction in the number of clean (Grade 0) boards.

WO 2007/135435 PCT/GB2007/001919 - 32 However the combined addition of 2% Imazalil and 8% mixed C12/C16 amine oxides to give formulation AT27M, gives markedly improved anti-sapstain performance over 5 AT6A. As shown in Figure 8, the number of failures is reduced to 13% although the number of clean boards is rather similar. AT15M with 2% prochloraz, 1% thiabendazole and 8% mixed 10 amine oxides performs better that AT6A,' with only a 3% failure rate and 58% of the boards being completely clean (Grade 0). AT29M with 2% imazalil, 1% thiabendazole and 8% mixed 15 amine oxides performs better than AT6A, with only a 5% failure rate. Example 3 20 This example shows the results of a field trial conducted in Portugal. In this example, C16 amine oxide was used and incorporated in to the base formulation AT6 as used in Example 1 at 10% such that the add-on cost to the formulation was also around 10%. The formulation 25 was labeled as AT9. AT9 Benzalkonium chloride (80% a.i.) 62.5% w/w 30 IPBC (98% a.i.) 5.1 Propiconazole (50% a.i.) 10.0 C16 amine oxide (30% a.i.) 10.0 Defoamer 0.2 Dowanol DPM@ 10.0 35 Water 2.2 WO 2007/135435 PCT/GB2007/001919 - 33 The wood used in the trial was freshly sawn maritime pine (Pinus pinsaster) with moisture content in the region 40-60%. 5 Each board used in the trial was 1000mm x 95mm x 18mm and composed predominantly of.sapwood. AT6 and AT9 were used at two concentrations each: 10 AT6: 1.03% and 0.69% v/v AT9: 0.93% and 0.62% v/v The solution strengths used were confirmed as correct by laboratory analysis. The strengths were chosen to match 15 the costs of the solutions as the same for each comparative test. The dipping was performed in open tanks containing 40 liters of solution. The samples were immersed in the 20 bath for 1 min. Next, wood was stored fro 10 min in a special stand in order to allow draining of excess product. 30 samples were dipped for each product and concentration. The wood was stored in 48cm wide stacks (5 samples were stored parallel in a single layer) . The 25 samples were stored without stickers (closed stacked). Separate stacks were formed for each product in order to prevent any unwanted interactions. All the stacks were covered by a layer of untreated 30 boards and were stored for the duration of the trial in the open yard exposed to the weather. This test methodology is broadly as described in CEN/TS 15082 "Wood Preservatives-Determination of the 35 Preventive Effectiveness Against Sapstain Fungi on Freshly Sawn Timber-Field Test".

WO 2007/135435 PCT/GB2007/001919 - 34 The stacks of treated boards were inspected after 4 months. Each individual board was assigned a visual grade according to the 0-4 scale also given in CEN/TS 5 15082 and described in Table 1 of Example 1. The amount of sapstain present on each board is shown graphically in figures 11 to 15. 10 The extent of staining on the untreated boards after 4 months is shown in Figure 11. Boards showing sapstain grades of 2 or higher are generally taken to indicate failures to sapstain in commercial terms, hence all 30 boards (i.e. 100% of the boards) have failed. The 15 results give validity to the trial. Figures 12 to 15 show that at the solution strengths tested the formulations with the C16 amine oxide gave better performance. In commercial terms, the two tests 20 of AT9 show a 0% failure rate as there were no boards with a sapstain grade of 2 or above. In contrast, the AT6 formulations show a commercial failure rating of 13% and 40% for 1.03% and 0.69% v/v respectively. 25 The levels of active ingredients (BAC, propiconazole and IPBC) in the wood are very close for each product at the two solution strengths tested. That is to say that 1.03% AT6 treated timber has rather similar levels of actives to 0.93% AT9 and so on. In fact the levels in 30 the AT9 treated wood are slightly lower that in the AT6 due to the added cost of the C16 amine oxide and the desire to compare performance of the two formulations at equivalent cost in the wood. 35 It would be expected therefore that, if amine oxide was not having an effect on antisapstain performance, 0.62% WO 2007/135435 PCT/GB2007/001919 - 35 AT9 would perform very similarly or slightly worse than 0.69% AT6. In fact, comparison of figures 12 to 15 and the failure rates quoted above shows the reverse with the amine oxide-containing variant far out-performing 5 the base product despite the slightly lower active ingredient levels in the wood. These two results suggest C16 amine oxide is enhancing the performance of the formulation. 10 Example 4 A number of anti-sapstain formulations were tested in a field trial in Polnica, North-Eastern. 15 The formulations were as follows: AT7A 20 Benzalkonium chloride (50% a.i.) 48% w/w IPBC (98% a.i.) 2.45 Propiconazole (50% a.i.) 4.8 Thiabendazole (99% a.i.) 0.51 C12 amine oxide (30% a.i) 6.0 25 Defoamer 0.2 Dowanol DPM@ 8.0 Propionic acid 3.0 Water 27.04 30 ATF1 Dimethyldidecylammonium chloride (80% a.i.) 30% w/w IPBC (98% a.i.) 2.45 Propiconazole (50% a.i.) 4.8 35 C12 amine oxide (30% a.i.) 6.0 Defoamer 0.2 WO 2007/135435 PCT/GB2007/001919 - 36 Dowanol DPM@ 8.0 Propionic acid 3.0 Water 45.55 5 ATF2 Dimethyldidecylammonium chloride (80% a.i.) 30% w/w Propiconazole (50% a.i.) 4.8 C12 amine oxide (30% a.i.) 6.0 10 Defoamer 0.2 Dowanol DPM@ 8.0 Propionic acid 3.0 Water 48.0 15 ATF3 DDACarbonate* (50% a.i.) 48% w/w IPBC (98% a.i.) 2.45 Azaconazole (98% a.i.) 2.45 20 C12 amine oxide (30% a.i.) 6.0 D6foamer 0.2 Dowanol DPM@ 8.0 Propionic acid 3.0 Water 29.9 25 *DDACarbonate is didecyldimethylammonium' carbonate/bicarbonate ATF4 30 DDACarbonate (50% a.i.) 48% w/w Azaconazole (98% a.i.) 2.45 C12 amine oxide (30% a.i.) 6.0 Defoamer 0.2 35 Dowanol DPM@ 8.0 Propionic acid 3.0 WO 2007/135435 PCT/GB2007/001919 - 37 Water 32.35 ATF5 5 DDACarbonate (50% a.i.) 48% w/w IPBC (98% a.i.) 2.45 Hexaconazole (75% a.i.) 3.20 Imazalil (99% a.i.) 0.75 C12 amine oxide (30% a.i.) 6.0 10 Defoamer 0.2 Dowanol DPM@ 8.0 Propionic acid 3.0 Water 28.4 15 ATF6 DDACarbonate (50% a.i.) 48% w/w Hexaconazole (75% a.i.) 3.20 C12 amine oxide (30% a.i.) 6.0 20 Defoamer 0.2 Dowanol DPM@ 8.0 Propionic acid 3.0 Water 31.6 25 The formulations were tested at solution strengths (diluted with water) chosen such that the cost of product and amount of active components (namely the amine oxide, azole and compound of formula (I)) in the treated wood was approximately the same. Thus, AT6A was 30 diluted to 0.58 % v/v, while the other compositions were diluted to 1.2 % v/v. The wood used for the trial was freshly sawn Scots pine obtained locally in Poland with moisture contents 35 between 40 and 60%. For each formulation a total of 35 WO 2007/135435 PCT/GB2007/001919 - 38 boards each were used, each board measuring approx. 22mm x 125mm x 1000mm. The dipping was performed in open tanks containing 40 5 liters of solution. The samples were immersed in the bath for 1 minute and then the treated wood stored for 10 min in a special stand in order to allow draining of excess product. 35 samples were dipped for each product at the required concentration. The wood was stored in 63 10 cm wide stacks (5 samples were stored in parallel in a single layer). All 35 samples were stored in a five by seven board stack without stickers (close stacked) to reflect common commercial practice. 15 Separate stacks were formed for each product in order to prevent any unwanted interactions. A control stack of untreated timber was also included. All the stacks were covered by a layer of untreated 20 boards and were stored for the duration of the trial in the open yard exposed to the weather This test methodology is broadly as described in CEN TS 15082 "Wood Preservatives-Determination of the 25 Preventive Effectiveness Against Sapstain Fungi on Freshly Sawn Timber-Field Test''. The stacks of treated boards were inspected after 2 months. Each individual board was assigned a visual 30 grade according to the 0-4 scale also given in CEN TS 15082, as described in Table 1 of Example 1. The sapstain ratings (grades) for boards treated with each product as well as untreated control boards are 35 presented graphically in Figures 16 to 24.

WO 2007/135435 PCT/GB2007/001919 - 39 Figure 16 shows the data for untreated Scots pine after 2 months' exposure. All 35 of the 35'boards have achieved at least a Grade 2 (medium staining), with 34 reaching Grade 4 (severe staining) indicating a very 5 high fungal activity during the test. Grade 2 or higher is generally accepted as representing a failure to sapstain in commercial terms, hence a 100% failure rate has been achieved for the untreated control boards. This result establishes the validity of the trial. 10 Figure 17 shows the performance of the control benzalkonium chloride, propiconazole and IPBC formulation (AT6A) and as such establishes the criteria 15 by which the alternatives are judged. Details of this formulation are given in Example 2. 7 boards out of 35 have reached Grade 2 or above, hence the failure rate is 20%. 20 Figure 18 shows the performance of AT7A, which has the same combination of actives as AT6A but includes thiabendazole and C12 amine oxide. This formulation is similar to AT7M used in -Examples 1 and 2, but does not contain a mixture of amine oxides. Furthermore, the A 25 suffix in AT7A denotes a less concentrated version of the formulation, for ease of handling. This less concentrated material is used at a lesser dilution but active levels in the timber are the same. 30 The addition of thiabendazole and C12 amine oxide to AT6A reduces the failure rate to less than 3% with only one board reaching Grade 2. This gives clear confirmation of the synergism of this combination as demonstrated in Examples 1 and 2 as the costs of the 35 product in the wood are the same. The failure rate of AT7A is comparable to that of AT7M from Examples 1 and WO 2007/135435 PCT/GB2007/001919 - 40 2, demonstrating that mixed amine oxides are not requiredto provide this synergism. Figure 19 shows the effect of changing the benzalkonium 5 chloride in AT7A for an equivalent amount of an alternative quaternary ammonium chloride, in this case dimethyldidecylammonium chloride (DDAC). Additionally the thiabendazole is omitted. This is referred to as formulation ATFI. 10 4 out of the 25 boards have reached Grade 2 ('medium' staining) and hence are classed as failures. However this represents only 11%, compared to 25% for AT6A, demonstrating that the improvement in performance from 15 amine oxide inclusion is maintained when an alternative quaternary ammonium compound is used. Furthermore, the presence of both a triazole and an imidazole is not a requirement for synergism. 20 Figure 20 shows the effect of omitting the IPBC from ATF1 to give ATF2. Omission of the IPBC from ATF1 has not resulted in an increase in failures over AT6A, in fact a 0% failure rate is observed. This result demonstrates that IPBC is not a required co-formulant of 25 the synergistic mixture. Figure 21 shows the effect of changing the benzalkonium chloride in AT7A for an equivalent amount of an alternative quaternary ammonium compound, in this case 30 dimethyldidecylammonium carbonate/bicarbonate. Additionally the propiconazole in AT7A has been substituted by azaconazole, and the thiabendazole has been omitted. This is formulation ATF3. 35 Changing the azole, quaternary ammonium compound and counter ion plus omitting thiabendazole has not resulted WO 2007/135435 PCT/GB2007/001919 - 41 in a loss of synergy with only 11% failure rate versus the 25% of the base system at the same active ingredient levels. 5 Figure 22 shows the effect of omitting the IPBC from ATF3 to give ATF4. The failure rate of only 9% clearly shows that omitting the IPBC from ATF3 is not detrimental to the synergistic improvement in performance of the amine oxide containing combination. 10 This result demonstrates that IPBC is not.a required co formulant of the synergistic mixture. Figure 23 shows the performance of a composition wherein the quaternary ammonium compound, triazole and imidazole 15 of AT7A have been replaced with dimethyldidecylammonium carbonate/bicarbonate, hexaconazole and imazalil respectively. This is example ATF5. 'The lack of failures to sapstain clearly shows the suitability of this azole, imidazole and quaternary ammonium compound 20 for the synergistic mixture. Figure 24 shows the effect of omitting both the IPBC and imazalil from ATF5 to give formulation ATF6. The lack of failures in this example demonstrates that IPBC is 25 not required to provide excellent antisapstain activity. ExamPle 5 The following formulations within the scope of the 30 invention are also described: Formulation 1 C12 amine oxide (30% a.i.) 6.0% w/w 35 Wocosen 50TK@ (50% a.i. Propiconazole) 4.8 DDAC (80% a.i.) 30.0 WO 2007/135435 PCT/GB2007/001919 - 42 IPBC (98% a.i.) 2.45 Dowanol DPM@ 15.0 Propionic acid 1.0 Water 40.75 5 Formulation 2 C12 amine oxide (30% a.i.) 6.0% w/w 10 Wocosen 50TK@ (50% a.i. Propiconazole) 4.8 DDAC (80% a.i.) 30.0 Dowanol DPM@ 15.0 Propionic acid 1.0 water 43.2 15 Formulation 3 C12 amine oxide (30% a.i.) 6.0% w/w Wocosen 50TK@ (50% a.i. Propiconazole) 4.8 20 C12 dimethylamine 17.75 Propionic acid 6.25 IPBC (98% a.i.) 2.45 Dowanol DPM@ 15.0 40 mole ethoxylated castor oil 10.0 25 water 37.75 Formulation 4 30 C12 amine oxide (30% a.i.) 6.0% w/w Wocoseno 50TK(50% a.i. Propiconazole) 4.8 C12 dimethylamine 17.75 Propionic acid 6.25 Dowanol DPM@ 15.0 35 40 mole ethoxylated castor oi'l 10.0 water 40.2 WO 2007/135435 PCT/GB2007/001919 - 43 Formulation 5 C12 amine oxide (30% a.i.) 6.0% w/w 5 Wocosen 50TK@ (50% a.i. Propiconazole) 4.8 C12 dimethylamine 17.75 Propionic acid 6.25 IPBC (98% a.i.) 2.45 Thiabendazole (99% a.i.) 0.5 10 Dowanol DPM@ 15.0 40 mole ethoxylated castor oil 10.0 water 37.25 Formulation 6 15 C12 amine oxide (30% a.i.) 6.0% w/w Wocosen 50TK@ (50% a.i. Propiconazole)- 4.8 C12 dimethylamine 17.75 Propionic acid 6.25 20 Thiabendazole (99% a.i.) 0.5 Dowanol DPM@ 15.0 40 mole ethoxylated castor oil 10.0 water 39.7 25 Formulation 7 C12 amine oxide (30% a.i.) 6.0% w/w Wocosen@ 50TK(50% a.i. Propiconazole) 4.8 C12 amine dipropionate (30% a.i.) 50.0 30 IPBC (98% a.i.) 2.45 Dowanol DPM@ 15.0 Propionic acid 1.0 40 mole ethoxylated castor oil 20.0 water 0.75 35 Formulation 8 WO 2007/135435 PCT/GB2007/001919 - 44 C12 amine oxide (30% a.i.) 6.0% w/w Wocosen 50TK@ 50% a.i. Propiconazole) 4.8 C12 amine dipropionate (30% a.i.) 50.0 5 Dowanol DPM@ 15.0 Propionic acid 1.0 40 mole ethoxylated castor oil 20.0 water 3.2 10 Formulation 9 C12 amine oxide (30% a.i.) 6.0% w/w Wocosen 50TK@ (50% a.i. Propiconazole) 4.8 C12 amine dipropionate (30% a.i.) 50.0 15 IPBC (98% a.i.) 2.45 Imazalil(99% a.i.) 0.75 Dowanol DPM@ 15.0 Propionic acid 1.0 40 mole ethoxylated castor oil 20.0 20 Formulation 10 C12 amine oxide (30% a.i.) 6.0% w/w Wocosen 50TK@ (50% a.i. Propiconazole) 4.8 25 C12 amine dipropionate (30% a.i.) 50.0 Imazalil (99% a.i.) 0.75 Dowanol DPM@ 15.0 Propionic acid 1.0 40 mole ethoxylated castor oil 20.0 30 water 2.45 Formulation 11 C12 amine oxide (30% a.i.) 6.0% w/w 35 Azaconazole (98% a.i.) 2.45 DDACarbonate* (50% a.i.) 48.0 WO 2007/135435 PCT/GB2007/001919 - 45 IPBC (98% a.i.) 2.45 Dowanol DPM@ 15.0 water 26.1 5 *DDACarbonate is didecyldimethylammonium carbonate/bicarbonate Formulation 12 10 C12 amine oxide (30% a.i.) 6.0% w/w Azaconazole (98% a.i.j 2.45 DDACarbonate (50% a.i.) 48.0 Dowanol DPM@ 15 water 28.55 15 Formulation 13 C12 amine oxide (30% a.i.) 6.0% w/w Hexaconazole (75% a.i.) 3.2 20 DDACarbonate (50% a.i.) 48.0 IPBC (98% a.i.) 2.45 Imazalil(99% a.i.) 0.75 Dowanol DPM@ 15.0 water 24.6 25 Formulation 14 C12 amine oxide (30% a.i.) 6.0% w/w Hexaconazole (75% a.i) 3.2 30 DDACarbonate (50% a.i.) 48.0 Dowanol DPM@ 15.0 water 27.8 Formulation 15 35 C12 amine oxide (30% a.i.) 6.0% w/w WO 2007/135435 PCT/GB2007/001919 - 46 Wocosen 50TK@ (50% a.i. propiconazole) 4.8 Cocoamidopropyl betaine (30% a.i.) 50.0 IPBC (98% a.i.) 2.45 Dowanol DPM@ 15.0 5 Propionic acid 1.0 40 mole ethoxylated castor oil 20.0 water 0.75 Formulation 16 10 C12 amine oxide (30% a.i.) 6.0% w/w Wocosen 50TK@ (50% a.i. propiconazole) 4.8 Cocoamidopropyl betaine (30% a.i.) 50.0 Dowanol DPM@ 15.0 15 Propionic acid 1.0 40 mole ethoxylated castor oil 20.0 water 3.2 Formulation 17 20 C12 amine oxide (30% a.i.) 6.0% w/w Wocosen 50TK@ (50% a.i. propiconazole) 4.8 C12 dimethylamine 24.0 Dowanol DPM@ 15.0 25 40 mole ethoxylated castor oil 20.0 Water 30.2 Formulation 18 30 C12 amine oxide (30% a.i.) 6.0% w/w Wocosen 50TK@ (50% a.i. Propiconazole) 4.8 Methyl C12 bis(glycol ether) quarternary ammonium chloride 30.0 IPBC (98% a.i.) 2.45 35 Dowanol DPM@ 15.0 Propionic acid 1.0 WO 2007/135435 PCT/GB2007/001919 - 47 Water 40.75 AT9M 5 Benzalkonium chloride (80% a.i.) 62.5% w/w IPBC (98% a.i.) 5.1 Propiconazole (50% a.i.) 10.0 C16 amine oxide (30% a.i) 4.0 C12 amine oxide (30% a.i.) 4.0 10 Defoamer 0.2 Dowanol DPM@ 10.0 Water 4.2 AT9MA 15 Benzalkonium chloride (80% a.i.) 62.5% w/w IPBC (98% a.i.) 5.1 Propiconazole (50% a.i.) 10.0 C16 amine oxide (30% a.i) 4.0 20 C12 amine oxide (30% a.i.) 4.0 Defoamer 0.2 Dowanol DPM@ 8.0 Propionic acid 3.0 Water 3.2 25 AT11M Benzalkonium chloride (80% a.i.) 62.5% w/w IPBC (98% a.i.) 5.1 30 Propiconazole (50% a.i.) 10.0 Prochloraz (99% a.i.) 2.02 C16 amine oxide (30% a.i) 4.0 C12 amine oxide (30% a.i.) 4.0 Defoamer 0.2 35 Dowanol DPM@ 8.0 Propionic acid 3.0 WO 2007/135435 PCT/GB2007/001919 - 48 Water 1.18 AT13M 5 Benzalkonium chloride (80% a.i.) 62.5% w/w IPBC (98% a.i.) 5.1 Propiconazole (50% a.i.) 10.0 Prochloraz (99% a.i.) 1.01 Thiabendazole (99% a.i.) 1.01 10 C16 amine oxide (30% a.i) 4.0 C12 amine oxide (30% a.i.) 4.0 Defoamer 0.2 Dowanol DPM@ 8.0 Propionic acid 3.0 15 Water 1.18 AT21M Benzalkonium chloride (80% a.i.) 62.5% w/w 20 IPBC (98% a.i.) 5.1 Propiconazole (50% a.i.) 10.0 Prochloraz (99% a.i.) 2.02 Imazalil (99% a.i.) 1.01 C16 amine oxide (30% a.i) 4.0 25 C12 amine oxide (30% a.i.) 4.0 Defoamer 0.2 Dowanol DPM@ 8.0 Propionic acid 3.0 Water 0.17 30 AT23M Benzalkonium chloride (80% a.i.) 62.5% w/w IPBC (98% a.i.) 10.2 35 Propiconazole '(50% a.i.) 10.0 C16 amine oxide (30% a.i) 4.0 WO 2007/135435 PCT/GB2007/001919 - 49 C12 amine oxide (30% a.i.) 4.0 Defoamer 0.2 Dowanol DPM@ 6.0 Propionic acid 3.0 5 Water 0.1 AT25M Benzalkonium chloride (80% a.i.) 62.5% w/w 10 IPBC (98% a.i.) 5.1 Propiconazole (50% a.i.) 20.0 C16 amine oxide (30% a.i) 4.0 C12 amine oxide (30% a.i.) 4.0 Defoamer 0.2 15 Dowanol DPM@ 0.0 Propionic acid 3.0 Water 1.2 The active ingredients in the above formulations are 20 summarised in table 2: Form. Amine Azole 1 Azole 2/3 Compound(I) Add. Oxide 1 C12 Propiconazole DDAChloride IPBC dimethyl amine oxide 2 C12 Propiconazole DDAChloride dimethyl amine oxide 3 C12 Propiconazole C12 IPBC dimethyl dimethyl amine amine oxide 4 C12 Propiconazole C12 dimethyl dimethyl amine amine oxide 5 C12 Propiconazole Thiabendazole C12 IPBC dimethyl dimethyl amine amine oxide 6 C12 Propiconazole Thiabendazole C12 dimethyl dimethyl-- WO 2007/135435 PCT/GB2007/001919 - 50 amine amine oxide 7 Cl2 Propiconazole C12 Amine IPBC dimethyl dipropionate amine oxide 8 C12 Propiconazole C12 Amine dimethyl dipropionate amine oxide 9 C12 Propiconazole Imazalil C12 Amine IPBC dimethyl dipropionate amine oxide 10 C12 Propiconazole Imazalil C12 Amine dimethyl dipropionate amine oxide 11 C12 Azaconazole DDACarbonate dimethyl /bicarbonate IPBC amine oxide 12 C12 Azaconazole DDACarbonate dimethyl /bicarbonate amine oxide 13 C12 Hexaconazole Imazalil DDACarbonate dimethyl /bicarbonate IPBC amine oxide 14 C12 Hexaconazole DDACarbonate dimethyl /bicarbonate amine oxide 15 C12 Prochloraz C12 IPBC dimethyl amidopropyl amine betaine oxide 16 C12 Prochloraz C12 dimethyl amidopropyl amine betaine oxide 17 C12 Propiconazole C12 dimethyl dimethyl amine amine oxide 18 Cl2 Propiconazole Methyl C12 IPBC dimethyl bis(glycol amine ether) quat. oxide chloride AT9M C12/C16 Propiconazole Benzalkonium IPBC mixed chloride dimethyl amine oxide AT9MA C12/C16 Propiconazole Benzalkonium IPBC mixed chloride dimethyl _ amine WO 2007/135435 PCT/GB2007/001919 - 51 oxide AT11M C12/C16 Propiconazole Prochloraz Benzalkonium IPBC mixed chloride dimethyl amine oxide AT13M Cl2/C16 Propiconazole Prochloraz/ Benzalkonium IPBC mixed Thiabendazole chloride dimethyl amine oxide AT21M C12/C16 Propiconazole Prochloraz/ Benzalkonium IPBC mixed Imazalil chloride dimethyl amine oxide AT23M C12/C16 Propiconazole Benzalkonium IPBC mixed chloride dimethyl amine oxide AT25M C12/C16 Propiconazole Benzalkonium IPBC mixed chloride dimethyl amine oxide , Table 2: Summary of formulations according to the invention.

Claims (33)

1. A wood preservative formulation comprising a synergistic combination of an amine oxide, an azole and a compound of formula (I) RI-A-NR 2P (I) wherein Ri denotes an alkyl group which contains from 6 to 24 carbon atoms, benzyl or substituted benzyl, or (CH 2 -CH 2 0)nH where n = 1-20; A is absent or denotes a linker group that may be C=O or -C=ONH(CH 2 )s- where s = 1-3; p = 2 or 3; 2 and each R , which are the same or different, denotes H, CH 3 , C 2 H 5 , (CH 2 -CH 2 0),H where n = 1-20, an alkyl group which contains from 6 to 24 carbon atoms, (CH 2 )mCOOH, (CH 2 )mCOO , (CHR 9 )mSO 3 H or (CHR 9 )mSO3 where m = 1 to 3 and R 9 denotes H or OH; and wherein if the compound is charged it is accompanied by a counterion X-; wherein said amine oxide is: (i) a trialiphatic substituted amine oxide; (ii) an N-alkylated cyclic amine oxide; (iii) a dialkylpiperazine di-N-oxide; (iv) an alkyldi(poly(oxyalkylene))amine oxide; (v) a dialkylbenzylamine oxide; (vi) a fatty amidopropyldimethyl amine oxide; (vii) a diamine oxide; (viii) a triamine oxide; or (ix) any combination of any of the foregoing; and wherein the azole is: an imidizole selected from the group consisting of: benzimidazole, thiabendazole, imazalil, carbendazim, prochloraz; - 53 a 1,2,4-triazole selected from compounds of formula (XI): OH H 2 H 2 R 6 -C -C R 5 CH 2 N N (XI) wherein R 5 represents a branched or straight chain C 1 -5 alkyl group and R represents a phenyl group optionally substituted by one or more substituents selected from halogen atoms or C1-3 alkyl, C1-3 alkoxy, phenyl or nitro groups; compounds of formula (XII): O R7 CH2 N N N-/ (XII) wherein R 7 is as defined for R 6 above and R 8 represents a hydrogen atom or a branched or straight chain C 1 - 5 alkyl group; or selected from the group comprising triadimefon, triadimenol, triazbutil, cyproconazole, difenoconazole, fluquinconazole, flusilazole, uniconazole, diniconazole, bitertanol, - 54 hexaconazole, flutriafol, epoxyconazole, tetraconazole, penconazole, and mixtures thereof or mixtures of both said imidizole and said 1,2,4-triazole.

2. A formulation according to claim 1, wherein said trialiphatic amine oxide has the formula R 1 R 2 R 3 N-0, wherein R1, is a linear, branched, cyclic or any combination thereof of saturated or unsaturated C8 to C40 group; and R2 and R3 independently are linear, branched, or any combination thereof C1 to C40 saturated or unsaturated groups.

3. A formulation according to claim 2, wherein R' is a linear, branched or any combination thereof C8 to C22 saturated or unsaturated group; and R2 and R3 independently are linear, branched, or any combination thereof Ci to C22 saturated or unsaturated groups.

4. A formulation according to claim 3, wherein R2 and R 3 are both methyl.

5. A formulation according to claim 3 or claim 4, wherein R 1 is a linear or branched C8 to C18 alkyl or alkenyl.

6. A formulation according to claim 3 or claim 4, wherein R 1 is a linear or branched C12 to C16 alkyl.

7. A formulation according to claim 6, wherein the amine oxide is a mixture of C12 and C16 dimethyl alkyl amine oxides.

8. A formulation according to any one of the preceding claims, wherein the 1,2,4-triazole is selected from triadimefon, triadimenol, triazbutil, - 55 propiconazole, cyproconazole, difenoconazole, fluquinconazole, tebuconazole, flusilazole, uniconazole, diniconazole, bitertanol, hexaconazole, azaconazole, flutriafol, epoxyconazole, tetraconazole, penconazole and mixtures thereof.

9. A formulation according to any one of the preceding claims, wherein the 1,2,4-triazole is selected from propiconazole, azaconazole, hexaconazole, tebuconazole, cyproconazole, triadimefon and mixtures thereof.

10.A formulation according to any one of the preceding claims, wherein the compound of formula (I) is a quaternary ammonium compound. ll.A formulation according to claim 10, wherein the quarternary ammonium compound is selected from compounds of formula (XIV): TH3 R-N-CH 3 - X CH 3 (XIV) wherein R is an alkyl group having from 6 to 22 carbon atoms; compounds of formula (XV): (XV) H 3 1 2fH RN-CH 3 . X - 56 wherein R' and R 2 are alkyl groups which may be the same or different and which contain from 6 to 22 carbon atoms; compounds of formulae (XVI) or (XVII): R 3 R 3 RI-N CRNC - X H 2 2 H 2 R3 Ra R2 R5 RR R 5 (XVI) (XVII) wherein R 1 and R 2 are alkyl groups which can be the same or different and which contain from 6 to 22 carbon atoms in a dialkyl compound and from 10 to 14 carbon atoms in a monoalkyl compound; R 3 is methyl or ethyl; R 4 , R 5 and R 6 are hydrogen or C 1 . 8 alkyl groups; or compounds of formulae (XVIII) or (XIX): H3 TH3 R N+-CH 3 - X R-N+-R2 - X C-CH2O) H (C-CH20) H H2 H2 (XVIII) (XIX) wherein R1 and R2 are alkyl groups which may be the same or different and which contain from 6 to 22 carbon atoms in a dialkyl compound and from 10 to 14 carbon atoms in a monoalkyl compound; m is a number from 1 to 20; - 57 and wherein and X is an anion chosen to allow ready water solubility of the quaternary ammonium salt.

12. A formulation according to claim 11, wherein R is an alkyl group having from 12 to 14 carbon atoms.

13. A formulation according to claim 11, wherein R1 and R2 are alkyl groups which may be the same or different and which contain from 8 to 10 carbon atoms.

14. A formulation according to claim 11, wherein for compounds of formulae (XVI) or (XVII), Ri and R2 contain from 8 to 10 carbon atoms in a dialkyl compound and from 10 to 14 carbon atoms in a monoalkyl compound.

15. A formulation according to claim 11, wherein for compounds of formulae (XVIII) or (XIX), R1 and R 2 contain from 8 to 10 carbon atoms in a dialkyl compound and from 10 to 14 carbon atoms in a monoalkyl compound.

16. A formulation according to claim 11, wherein for compounds of formulae (XVIII) or (XIX), R' and R 2 contain 10 carbon atoms in a dialkyl compound and 10 carbon atoms in a monoalkyl compound.

17. A formulation according to claim 11, wherein for compounds of formulae (XVIII) or (XIX), m is from 1 to 8.

18. A formulation according to claim 17, wherein the quaternary ammonium salt is cocotrimethyl ammonium chloride in which the alkyl group R consists of a mixture of predominantly C 1 2 and C 1 4 . - 58 19. A formulation according to claim 17, wherein the quarternary ammonium salt is seleteced from didecyl dimethyl ammonium chloride, didecyldimethylammonium carbonate, didecyldimethylammonium bicarbonate, dioctyl dimethyl ammonium chloride and octyl decyl dimethyl ammonium chloride either individually or as a mixture containing two or three of these.

20. A formulation according to claim 17, wherein the quarternary ammonium salt is selected from coco benzyl dimethyl ammonium chloride and dicoco benzyl methyl ammonium chloride in which the alkyl groups are predominantly C12 and C14.

21. A formulation according to claim 17, wherein the quarternary ammonium salt is benzalkonium chloride or benzalkonium hydroxide.

22. A formulation according to any one of claims 1 to 9, wherein the compound of formula (I) is a betaine.

23. A forumulation according to claim 22, wherein the betaine is selected from the group consisting of coco amido propyl dimethyl betaine; cetyl betaine( (carboxylatomethyl) hexadecyldimethylammonium); C12 amine dipropionate; and coco amido propyl dimethyl sultaine (cocoamidopropyl-N, N-dimethyl-N-2 hydroxypropyl sulfobetaine.

24. A formulation according to any one of claims 1 to 9, wherein the compound of formula (I) is a C12-C14 dimethylalkylamine or salt thereof.

25. A formulation according to any one of the preceding claims, further comprising a halopropynyl compound. - 59 26. A formulation according to claim 25, wherein the halorpopynyl compound is an iodoproynyl compound of formula (XX): 0 I C O -N-R H 2 H (XX) wherein R is selected from methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, cyclohexyl, phenyl, benzyl, tolyl, cumyl, chlorobutryl, chlorophenyl, and ethoxyphenyl.

27. A formulation according to claim 26, wherein the iodopropynyl compound is 3-iodo-2-propynyl butyl carbamate.

28. A formulation according to any one of the preceding claims, wherein the formulation is in a liquid form.

29. A formulation according to claim 28, wherein the formulation is an emulsion.

30. A method of protecting a substrate of wood or other cellulosic material which comprises applying to the substrate a formulation as claimed in any one of the preceding claims or applying the individual components to the substrate such that the substrate effectively receives a formulation according to any one of the preceding claims.

31. A method according to claim 30, wherein the substrate is affected by or at risk of being affected by mould and staining or defacing organisms and in particular sapstain organisms. - 60 32. A substrate made of wood or other cellulosic material treated with a formulation as claimed in any one of claims 1 to 29.

33. A substrate of wood or other cellulosic material comprising a synergistic combination of an amine oxide, an azole and a compound of formula (I) R -A-NR 2P (I) wherein R' denotes an alkyl group which contains from 6 to 24 carbon atoms, benzyl or substituted benzyl, or (CH 2 -CH 2 0)nH where n = 1-20; A is absent or denotes a linker group that may be C=O or -C=ONH (CH 2 )s- where s = 1-3; p = 2 or 3; and each R 2 , which are the same or different, denotes H, CH 3 , C 2 H 5 , (CH 2 -CH 2 0)nH where n = 1-20, an alkyl group which contains from 6 to 24 carbon atoms, (CH 2 )mCOOH, (CH 2 )mCOO , (CHR 9 )mSO 3 H or (CHR 9 )mSO3 where m = 1 to 3 and R 9 denotes H or OH; and wherein if the compound is charged it is accompanied by a counterion X-; wherein said amine oxide is: (i) a trialiphatic substituted amine oxide; (ii) an N-alkylated cyclic amine oxide; (iii) a dialkylpiperazine di-N-oxide; (iv) an alkyldi(poly(oxyalkylene))amine oxide; (v) a dialkylbenzylamine oxide; (vi) a fatty amidopropyldimethyl amine oxide; (vii) a diamine oxide; (viii) a triamine oxide; or (ix) any combination of any of the foregoing; and wherein the azole is: - 61 an imidizole selected from the group consisting of: benzimidazole, thiabendazole, imazalil, carbendazim, prochloraz; a 1,2,4-triazole selected from compounds of formula (XI): OH H 2 H 2 R 6 -- C--C RS CH2 N N (XI) wherein R5 represents a branched or straight chain Ci-5 alkyl group and R 6 represents a phenyl group optionally substituted by one or more substituents selected from halogen atoms or C1- 3 alkyl, C 1 -3 alkoxy, phenyl or nitro groups; compounds of formula (XII): -0 R 7 CH 2 N N / (XII) wherein R 7 is as defined for R 6 above and R 8 represents a hydrogen atom or a branched or straight chain C 1 - 5 alkyl group; or selected from the group comprising triadimefon, triadimenol, triazbutil, cyproconazole, difenoconazole, fluquinconazole, - 62 flusilazole, uniconazole, diniconazole, bitertanol, hexaconazole, flutriafol, epoxyconazole, tetraconazole, penconazole, and mixtures thereof or mixtures of both said imidizole and said 1,2,4-triazole.

34. A wood preservative formulation according to claim 1, said formulation substantially as herein described with reference to any one of the embodiments of the invention illustrated in the accompanying drawings and/or examples.

35. A method according to claim 30, said method substantially as herein described with reference to any one of the embodiments of the invention illustrated in the accompanying drawings and/or examples.

36. A substrate according to claim 32, said substrate substantially as herein described with reference to any one of the embodiments of the invention illustrated in the accompanying drawings and/or examples.

37. A substrate according to claim 33, said substrate substantially as herein described with reference to any one of the embodiments of the invention illustrated in the accompanying drawings and/or examples. Dated this 2 nd day of August 2012 Shelston IP Attorneys for: Arch Timber Protection Limited