WO2007135435A2

WO2007135435A2 - Wood preservative formulations

Info

Publication number: WO2007135435A2
Application number: PCT/GB2007/001919
Authority: WO
Inventors: Paul Stuart Warburton; Andrew Stewart Hughes
Original assignee: Arch Timber Protection Ltd
Current assignee: Arch Timber Protection Ltd
Priority date: 2006-05-24
Filing date: 2007-05-24
Publication date: 2007-11-29
Anticipated expiration: 2008-11-24
Also published as: WO2007135435A3; AU2007253048A1; EP2043433A2; NZ596157A; NZ573995A; GB2438404A; GB0610336D0; AU2007253048B2

Abstract

The invention provides formulations comprising an amine oxide, an azole and a compound of formula (I): R1-A-NR2p Wherein : R1 denotes an alkyl group which contains from 6 to 24 carbon atoms, benzyl or substituted benzyl, or (CH2- CH2O)nH where n = 1-20; A is absent or denotes a linker group that may be C=O or -C=ONH (CH2) s- where s = 1-3; P = 2 or 3; and each R2, which are the same or different, denotes H, CH3, C2H5, (CH2-CH2O)nH where n = 1-20, an alkyl group which contains from 6 to 24 carbon atoms, (CH2)mCOOH, (CH2)mCOO¯, (CHX)mSO3H or (CHX)mSO3¯ where m = 1 to 3 and X denotes H or OH,; and wherein if the compound is charged it is accompanied by a counterion X¯. The formulations of the invention are surprisingly effective at protecting wood and other cellulosic substrates, in particular at providing antisapstain activity. The invention also provides methods for treating wood and other cellulosic substrates with said formulations.

Description

Wood Preservative Formulations

The present invention relates to formulations for protecting wood and other cellulosic substrates against moulds, staining and other defacing organisms, and in particular to antisapstain applications.

Antisapstain chemicals are used to protect timber, 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 (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.

'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 have also been described for use in antisapstain formulations (WO 2001/0189779, WO 2000/0071312) . However, there remains a need for alternative and improved wood preservative formulations, to address environmental concerns and customer pressure for ever more effective and competitive products. Improved azole containing formulations are of particular interest. The present inventors have found that formulations comprising an amine oxide, an azole and a compound of formula (I)

F^-A-NR² _P

(I) wherein R¹ denotes an alkyl group which contains from 6 to 24 carbon atoms, benzyl or substituted benzyl, or (CH₂- CH₂O)_nH where n = 1-20;-

A is absent or denotes a linker group that may be C=O or -C=ONH (CH₂) _s- where s = 1-3; p = 2 or 3 ; and each R², which may be the same or different, denotes H, CH₃, C₂H₅, (.CH₂-CH₂O)_nH where n = 1-20, an alkyl group which contains from 6 to 24 carbon atoms, (CH₂)_mCOOH, (CH₂J_1nCOO^", (CHX)_1nSO₃H or (CHX)_1nSO₃ ^" where m = 1 to 3 and X denotes H or OH; and wherein if the compound is charged it is 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 compound and compound of formula (I)

R^x-A-NR² _p ^' (I) wherein

R¹ denotes an alkyl group which contains from 6 to 24 carbon atoms, benzyl or substituted benzyl, or (CH₂- CH₂O)_nH where n = 1-20; A is absent or denotes a linker group that may be C=O or -C=ONH (CH₂) _s- where s = 1-3; P = 2 or 3; and each R², which may be the same or different, denotes H, CH₃, C₂H₅, (CH₂-CH₂O)_nH where n = 1-20, an alkyl group which contains from 6 to 24 carbon atoms,

(CH₂)_mCOOH, (CH₂J₁₁COO-, (CHX)_1nSO₃H or (CHX)₁₁₁SO₃ ^" where m = 1 to 3 and X 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) R²

R¹ A N—»-0

R³

(ID wherein

R¹, R² and R³ are independent and can be hydrogen, optionally substituted poly (oxyalkylene) or a linear, branched, cyclic, aromatic or any combination thereof of a saturated or unsaturated, substituted or unsubstituted C₁ to C₄₀ group, preferably C₁ to C₂₀, or alternatively R² and R³ together form a substituted or unsubstituted cyclic group; A is absent or denotes a linker group that may be -C=ONH (CH₂) _s- 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 group that forms part of R¹, R² or R³ 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 iV-alkylated cyclicamine 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 amine oxide includes at least one C₈-C₁₈ alkyl moeity.

Preferred trialiphatic substituted amine oxides are represented by the general formula (III)

(III) wherein R⁴, R⁵ and R⁶ are independent and can be linear, branched, cyclic, aromatic or any combination thereof of a saturated or unsaturated C₁ to C₄₀ group 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. R⁴, R⁵ and R⁶ independently may be alkyl, alkenyl, or alkynyl groups. More preferably, R⁴ is a linear, branched, cyclic or any combination thereof C₈ to C₂₂ 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 C₁ to C₂₂ saturated or unsaturated groups, such as coco, hydrogenated tallow, soya, decyl, and hexadecyl .

A preferred trialiphatic substituted amine oxide is dialkylmethylamine oxide having the formula R⁴R⁵CH₃N-O, where R⁴ and R⁵ are defined as above. Another preferred trialiphatic substituted amine oxide is an alkyldimethylamine oxide having the formula R⁴(CH₃)₂N-O, where R⁴ is defined as above. More preferred alkyldimethylamine oxides have the formula R²² (CH₃) ₂N--O, where R²² is a linear or branched C₈-C₁₈ alkyl or alkenyl. Preferably, R²² is a linear or branched C₈-C₁₆ alkyl. Alkyldimethylamine oxides are non-toxic and non- mutagenic surfactants . Suitable alkyldimethylamine oxides include, but are not limited to, a C₁₀ alkyldimethylamine oxide, a C₁₀-C₁₄ alkyldimethylamine oxide, a C₁₂-C₁₆ alkyldimethylamine oxide, a C₁₆-C₁₈ alkyldimethylamine oxide, and' any combination of any of the foregoing.

Preferred iV-alkylated cyclicamine oxides have the formula R⁷R⁸R⁹N-O where R⁷ is defined as R⁴ above, and R⁸ and R⁹ are linked to form a cyclic group. The cyclic group typically contains from 4 to 10 carbon atoms and may optionally contain oxygen, sulphur, nitrogen, or any combination of any of the foregoing. More preferred JW- alkylated cyclicamine oxides include, but are not limited to, an alkylmorpholine N-oxide, a dialkylpiperazine di-JV-oxide, and any combination of any of the foregoing.

Preferred alkylmorpholine JV-oxides have the general formula (IV) :

(IV) where R¹⁰ is defined as R⁴ above . According to a more preferred embodiment , R¹⁰ is a linear or branched C₈ to C₁₆ alkyl . Examples of preferred alkylmorpholine i\7-oxides include, but are not limited to , cetyl morpholine N- oxide and lauryl morpholine JV-oxide .

Preferred dialkylpiperazine di-ϊV-oxides have the general formula (V) :

(V) where R¹¹ is defined as R⁴ above and R¹² is defined as R⁵ above .

Preferred alkyldi (poly (oxyalkylene) ) amine oxides have the general formula (VI) :

(VI ) where R¹³ is defined as R⁴ above ; R¹⁴ and R¹⁵ independently are H or CH₃ ; and m and n independently are integers from about 1 to about 10 . Preferred dialkylbenzylamine oxides have the formula R¹⁶R¹⁷R¹⁸N-O, where R¹⁶ is defined as R⁴ above; R¹⁷ is defined as R⁵ above; and R¹⁸ is benzyl . More preferred dialkylbenzylamine oxides include, but are not limited to , alkylbenzylmethylamine oxides having the formula R¹⁶R¹⁷CH₃N-O where R¹⁶ and R¹⁷ are defined as above .

According to a more preferred embodiment , R¹⁶ is a linear or branched C₈-C₁₂ alkyl .

Preferred fatty amidopropyldimethylamine oxides have the general formula (VII) :

(VII) where R¹⁹ is defined as R⁴ above.

Preferred diamine oxides have the general formula (VIII) :

.(VIII) where R²⁰ is defined as R⁴ above; and n is an integer from about 1 to about 10.

Preferred triamine oxides have the general formula (IX) :

[IX) where R²¹ is defined as R⁴ above; and m and n independently are integers from about-1 to about 10. Particularly preferred amine oxides are alkyl dimethyl amine oxides such as decyl dimethyl amine oxide, lauryl dimethyl amine oxide, isoalkyl dimethyl amine oxide, myristyl dimethyl ethyl amine oxide, cetyl dimethyl amine oxide, stearyl dimethyl amine oxide and octyl dimethyl amine oxide. Particularly preferred is N-alkyl (C₁₂-C₁₆) -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 C₁₂-N,N-dimethylamine oxide and C₁₆- N,N-dimethylamine oxide being especially preferred. 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)

(X) wherein

X denotes C or N; R¹ denotes hydrogen or a linear, branched, cyclic, aromatic or any combination thereof of a saturated or unsaturated, substituted or unsubstituted C₁ to C₄₀ group wherein any of the carbon atoms other than those bound to the nitrogen atom shown in formula (X) may be replaced with an optionally substituted hetero atom;

R² denotes hydrogen, C₁-C₈ alkyl, C₂-C₈ alkenyl, C₆-C₁₀ aromatic, C₅-C₁₀ heteroaromatic or C₁-C₄ alkyl carbamate; R³ denotes hydrogen; or when X is C together with R⁴ may provide a 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 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 positions.

Preferred triazole compounds include a triazole compound selected from compounds of formula (XI) :

(XI) wherein R⁵ represents a branched or straight chain

C_1-5 alkyl group (e.g. t-butyl) and R represents a phenyl group optionally substituted by one or more substituents selected from halogen (e.g. chlorine, fluorine or bromine) atoms or C_1-3 alkyl (e.g. methyl), C_1-3 alkoxy (e.g. methoxy) , phenyl or nitro groups.

Alternatively, the triazole compound is advantageously selected from compounds of formula (XII) :

(XII) wherein R⁷ is as defined for R⁶ above and R⁸ represents a hydrogen atom or a branched or straight chain C_1-5 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, diniconazole, bitertanol, hexaconazole, azaconazole, flutriafol, epoxyconazole, tetraconazole, penconazole, and mixtures thereof.

Most preferred triazoles are propiconazole, azaconazole, hexaconazole, tebuconazole, cyproconazole, 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 R¹ group is directly bonded 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, 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 organic groups and having the general formula (XIII) :

(XIII)

Of the quaternary ammonium compounds which may be used in the compositions and methods of the present invention, suitable compounds include: 1. Monoalkyltrimethyl ammonium salts of formula (XIV):

(XIV) 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, 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 C₁₂ and C₁₄.

2. Dialkyl dimethyl ammonium salts of formula (XV) :

(XV) wherein R¹ and R² 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, 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 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 dialkyl methyl or ethyl benzyl ammonium salts of formulae (XVI) or (XVII) :

(XVI) (xvii; wherein R¹ and R² 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 compound; R³ is methyl or ethyl; R⁴, R⁵ and R⁶ are hydrogen or C_1-8 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 chloride in which the alkyl groups are predominantly C₁₂ '

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

(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, preferably from 8 to 10 carbon atoms in a dialkyl 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. 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. 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. 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- hydroxypropyl sulfobetaine) .

The betaine is, e.g. of the formula R-N⁺(CH₃) ₂-CH₂- COO^" ; or R-C (=0) N⁺ (CH_j)₂-CH₂-COO^" or a salt thereof where R is a straight chain C₆-C₂₄ alkyl group, or a C₈-C₁₈ alkyl group, or R is a straight chain C₁₂-C₁₆ alkyl group. The betaine in one embodiment is a cocamidopropylbetaine of formula: RC (=0) NH (CH₂) ₃-N⁺ (CH₃) ₂- CH₂-COO^" wherein R is a C₁₁-C₁₃ straight chain alkyl group.

The compound of formula (I) may be a dimethylalkylamine or salt thereof. A 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 dimethylalkylanaines , it is also possible to use mixtures, for example dimethyl-C₁₂-alkylamine and dimethyl-C₁₄alkylamine (dimethyl-C₁₂/C₁₄-alkylamine) .

The compositions typically comprise one or more further active ingredients . Halopropynyl compounds are particularly preferred examples of additional active ingredients . 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) :

-c-b°^Xd ^R (XX) 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 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. Preferred are compounds where in is 1 and n is 1 having the following formula (XXI) :

(XXI)

Suitable R substituents include alkyls such as methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, cycloalkyls such as cyclohexyl, aryls, alkaryls and aralkyls such as phenyl, benzyl, tolyl, cumyl, halogena.ted alkyls and aryls, such as chlorobutryl and chlorophenyl, and alkoxy aryls such as ethoxyphenyl and 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, 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 would be expected based on an additive effect.

Therefore synergy is taking place. Thus preferred compositions comprise, in synergistic proportions, an 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 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 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 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 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 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 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. Preferably C12 amine oxides are used, or alternatively a mixture of C12 and C16 amine oxides, 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 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. 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 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 formulations include benzalkonium chloride or didecyldimethylammonium chloride or carbonate or bicarbonate, IPBC, propiconazole or tebuconazole, thiabendazole or imazalil and a C₁₆ and/or^' C₁₂ dimethyl amine oxide. Each of the ingredients are also preferred 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 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. The compositions according to the invention may additionally, comprise other active ingredients such as termiticides , insecticides, bacteriocid.es 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 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 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- diamine, Dazomet, (E) -1- (2-chloro-l, 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 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, permethrin, silafluofen, deltamethrin, bifenthrin, cyfluthrin, chlorfenapyr, thiachloprid, etofenprox, chlothianidin, thiamethoxam and imidacloprid, and benzoylureas such as lufenuron, hexaflumuron and flufenoxuron and in particular, flurox. 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, latex, fluorocarbon, organic carboxylate/metals, paper • sizing agents or amine oxides, or combinations thereof; 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, 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 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 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 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. 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 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 based composite products such as oriented strandboard, medium density fibreboard, fibreboard, hardboard and particle board

Other materials which can benefit from treatment with the formulations of the invention are 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 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. 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 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 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 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, ethyl lactate and 2-ethyl hexyl lactate. 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 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 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 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 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:

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 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 Example 1. 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.

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) 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.

Figure 8 is a graph showing the performance of AT27M (AT26 plus mixed C12/C16 amine oxides) applied during the test of Example 2.

Figure 9 is a graph showing the performance of AT15M

(ATβA 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 (ATβA 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, 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.

Figure 13 is a graph showing the performance of AT6 applied at 1.03% applied during the test of Example 3. 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.

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.

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 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.

Figure 19 is a graph showing the performance of ATFl (AT7A with DDAC used in place of the BAC, and no thiabendazole) applied during the test of Example 4.

Figure 20 is a graph showing the performance of ATF2 (ATFl without the IPBC) applied during the test of Example 4.

Figure 21 is a graph showing the performance of ATF3 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. 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 (ATF5 without the imazalil and IPBC) applied during the test of Example 4.

Examples

Typically, the following formulations were made by first mixing the azoles and/or imidazoles plus the 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 added and mixed until a clear homogenous product was obtained.

Example 1

Two anti-sapstain formulations were tested in an accelerated field trial in Florida.

The formulations were as follows :

AT6 (Comparative Formulation)

Benzalkonium chloride (80% a. i.) 62.5% w/w IPBC (98% a.i. ) 5.1

Propiconazole (50% a.i.) 10.0 Defoamer 0.2

Dowanol DPM® 10.0

Water 12.2

AT7M

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 C16 amine oxide (30% a.i) ^' 4.0

C12 amine oxide (30% a.i.) 4.0 Defoamer 0.2

Dowanol DPM® 10.0

Water 3.19

Both formulations contained the same levels of IPBC, propiconazole and benzalkonium chloride, but AT7M additionally contained thiabendazole and C12 and C16 amine oxides .

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 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 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 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.

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 was assigned a grade according to the 0-4 scale given in CEN/TS 15082 'Wood Preservatives - Determination of the Preventive Effectiveness Against Sapstain Fungi on Freshly Sawn Timber - Field Test¹.

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.

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. 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 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 thiabendazole and equal amounts of C12 and C16 amine 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% failure rate as shown by only 1 of the 25 boards reaching a grade 2.

Example 2

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 modified by the addition of other biocides; alone, in combinations and with mixed C12/C16 amine oxides.

The formulations were as follows

AT6A (Comparative Formulation)

Benzalkonium chloride (80% a.i.) 62.5% w/w

IPBC (98% a.i. ) 5.1

Propiconazole (50% a.i.) 10.0 Defoamer 0.2

Dowanol DPM® 8.0

Propionic acid 3.0

Water 11.2

AT7M

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

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 Water 2.19

AT15M

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.) 2.02

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

Propionic acid 3.0

Water 0.17

AT26 (Comparative Formulation)

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

Defoamer 0.2

Dowanol DPM® 8.0

Propionic acid 3.0 Water 9.18

AT27M

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

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

Water 1.18

AT29M

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 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 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 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 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 stored in 48 cm wide stacks (5 samples were stored parallel in a single layer) . 40 samples were stored 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 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.

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 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 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 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 formulations more quickly and reliably, all data presented herein refers to this closed stacked arrangement. No data is presented for timber stored open stacked.

Figure 4 shows the data for untreated Scots pine after 4 months exposure 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.

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.

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% 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 ATβA plus thiabendazole, prochloraz and mixed C12/C16 amine oxides.

Figure 10 shows the effect of including thiabendazole, imazalil and mixed C12/C16 amine oxides. AT29M is ATβA plus thiabendazole, prochloraz and mixed C12/C16 amine oxides.

AT7M with both 1% Thiabendazole and 8% mixed amine oxides performs better than ATβA, with only 3% failure rate and 75% of the boards being completely clean (Grade 0) .

Figure 7 shows the addition of 2% Imazalil to ATβA to give formulation AT26, has a slightly detrimental effect on anti-sapstain performance with an increase in the number of failing boards from 28% to 30% combined with a reduction in the number of clean (Grade 0) boards. 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 ATβA. 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 amine oxides performs better that ATβA, ^" 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 amine oxides performs better than ATβA, with only a 5% failure rate.

Example 3

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 was labeled as AT9.

AT9

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.) 10.0

Defoamer 0.2

Dowanol DPM® 10.0 Water 2.2 The wood used in the trial was freshly sawn maritime pine (Pinus pinsaster) with moisture content in the region 40-60%.

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:

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 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 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 samples were stored without stickers (closed stacked) .

Separate stacks were formed for each product in order to prevent any unwanted interactions .

This test methodology is broadly as described in CEN/TS 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 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 amount of sapstain present on each board is shown graphically in figures 11 to 15.

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 results give validity to the trial.

Figures 12 to 15 show that at the solution strengths tested the formulations with the Clβ amine oxide gave better performance. In commercial terms, the two tests 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.

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 the AT9 treated wood are slightly lower that in the AT6 due to the added cost of the Clβ amine oxide and the desire to compare performance of the two formulations at equivalent cost in the wood.

It would be expected therefore that, if amine oxide was not having an effect on antisapstain performance, 0.62% 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 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.

Example 4

A number of anti-sapstain formulations were tested in a field trial in Polnica, North-Eastern.

The formulations were as follows :

AT7A

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 Defoamer 0.2

Dowanol DPM® 8.0

Propionic acid 3.0

Water 27.04

ATFl

Dimethyldidecylammonium chloride (80% a.i.) 30% w/w

IPBC (98% a.i. ) 2.45

Propiconazole (50% a.i.) 4.8 C12 amine oxide (30% a.i.) 6.0

Defoamer 0.2 Dowanol DPM® 8.0 Propionic acid 3.0 Water 45.55

ATF2

Dimethyldidecylairanonium chloride (80% a.i.) 30% w/w

Propiconazole (50% a.i.) 4.8

C12 amine oxide (30% a.i.) 6.0 Defoamer 0.2

Dowanol DPM® 8.0

Propionic acid 3.0

Water 48.0

ATF3

DDACarbonate* (50% a.i.) 48% w/w

IPBC (98% a.i.) 2.45

Azaconazole (98% a.i.) 2.45 C12 amine oxide (30% a.i.) 6.0

Defoamer 0.2

Dowanol DPM® 8.0

Propionic acid 3.0

Water 29.9

*DDACarbonate is didecyldimethylammonium' carbonate/bicarbonate

ATF4

DDACarbonate (50% a.i.) 48% w/w

Azaconazole (98% a.i.) 2.45

C12 amine oxide (30% a.i.) 6.0

Defoamer 0.2 Dowanol DPM® 8.0

Propionic acid 3.0 Water 32.35

ATF5

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 Defoamer 0.2

Dowanol DPM® 8.0

Propionic acid 3.0

Water 28.4

ATF6

DDACarbonate (50% a.i.) 48% w/w

Hexaconazole (75% a.i.) 3.20

C12 amine oxide (30% a.i.) 6.0 Defoamer 0.2

Dowanol DPM® 8.0

Propionic acid 3.0

Water 31.6

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 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 between 40 and 60%. For each formulation a total of 35 boards each were used, each board measuring approx. 22mm x 125mm x 1000mm.

The dipping was performed in open tanks containing 40 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 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.

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 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 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 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 presented graphically in Figures 16 to 24. 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 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.

Figure 17 shows the performance of the control benzalkonium chloride, propiconazole and IPBC formulation (AT6A) and as such establishes the criteria 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%.

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 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.

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 product in the wood are the same. The failure rate of AT7A is comparable to that of AT7M from Examples 1 and 2, demonstrating that mixed amine oxides are not requiredto provide this synergism.

Figure 19 shows the effect of changing the benzalkonium 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 ATFl.

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 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.

Figure 20 shows the effect of omitting the IPBC from ATFl to give ATF2. Omission of the IPBC from ATFl 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 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 dimethyldidecylammonium carbonate/bicarbonate. Additionally the propiconazole in AT7A has been substituted by azaconazole, and the thiabendazole has been omitted. This is formulation ATF3.

Changing the azole, quaternary ammonium compound and counter ion plus omitting thiabendazole has not resulted in a loss of synergy with only 11% failure rate versus the 25% of the base system at the same active ingredient levels .

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. 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 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 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 not required to provide excellent antisapstain activity.

Example 5

The following formulations within the scope of the invention are also described:

Formulation 1

C12 amine oxide (30% a. i.) 6.0% w/w Wocosen 50TK® (50% a.i. Propiconazole) 4.8 DDAC (80% a.i. ) 30.0 IPBC (98% a.i.) 2.45 Dowanol DPM® 15.0 Propionic acid 1.0

Water 40.75

Formulation 2

C12 amine oxide (30% a.i.) 6.0% w/w

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

Formulation 3

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

IPBC (98% a.i.) 2.45

Dowanol DPM® 15.0

40 mole ethoxylated castor oil 10.0 water 37.75

Formulation 4

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

Dowanol DPM® ^' 15.0 40 mole ethoxylated castor oil 10.0 water 40.2 Formulation 5

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

IPBC (98% a.i. ) 2.45

Thiabendazole (99% a.i.) 0.5 Dowanol DPM® 15.0

40 mole ethoxylated castor oil 10.0 water 37.25

Formulation 6

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 Thiabendazole (99% a.i.) 0.5

Dowanol DPM® 15.0

40 mole ethoxylated castor oil 10.0 water 39.7

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 IPBC (98% a.i. ) 2.45

Dowanol DPM® 15.0

Propionic acid 1.0

40 mole ethoxylated castor oil 20.0 water 0.75

Formulation 8 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 Dowanol DPM® 15.0

Propionic acid 1.0

40 mole ethoxylated castor oil 20.0 water 3.2

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 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

Formulation 10

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

Imazalil (99% a.i.) 0.75

Dowanol DPM® 15.0

Propionic acid 1.0

40 mole ethoxylated castor oil 20.0 water 2.45

Formulation 11

C12 amine oxide (30% a.i.) 6.0% w/w Azaconazole (98% a.i.) 2.45

DDACarbonate* (50% a.i.) 48.0 IPBC (98% a.i. ) 2.45

Dowanol DPM® 15.0 water 26.1

*DDACarbonate is didecyldimethylammonium carbonate/bicarbonate

Formulation 12

C12 amine oxide (30% a.i.). 6.0% w/w

Azaconazole (98% a.i.) 2.45

DDACarbonate (50% a.i.) 48.0

Dowanol DPM® 15 water 28.55

Formulation 13

C12 amine oxide (30% a.i.) 6.0% w/w

Hexaconazole (75% a.i.) 3.2 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

Formulation 14

C12 amine oxide (30% a.i.) 6.0% w/w

Hexaconazole (75% a.i) 3.2 DDACarbonate (50% a.i.) 48.0

Dowanol DPM® 15.0 water 27.8

Formulation 15

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

IPBC (98% a.i. ) 2.45

Dowanol DPM® 15.0 Propionic acid 1.0

40 mole ethoxylated castor oil 20.0 water , 0.75

Formulation 16

^' 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 Propionic acid 1.0

40 mole ethoxylated castor oil 20.0 water 3.2

Formulation 17

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 40 mole ethoxylated castor oil 20.0

Water • 30.2

Formulation 18

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 Dowanol DPM® 15.0

Propionic acid 1.0 Water 40.75

AT9M

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 Defoamer 0.2

Dowanol DPM® 10.0

Water 4.2

AT9MA

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

Defoamer 0.2

Dowanol DPM® 8.0

Propionic acid 3.0

Water 3.2

ATIlM

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.) 2.02

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 Water 1.18

AT13M

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 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 Water - 1.18

AT21M

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.) 2.02

Imazalil (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

Propionic acid 3.0

Water 0.17

AT23M

Benzalkonium chloride (80% a.i.) 62.5% w/w

IPBC (98% a.i. ) 10.2 Propiconazole ^' (50% a.i.) 10.0

C16 amine oxide (30% a.i) 4.0 C12 amine oxide (30% a.i.) 4.0

Defoamer 0.2

Dowanol DPM® 6.0

Propionic acid 3.0

Water 0.1

AT25M

Benzalkonium chloride (80% a.i.) 62.5% w/w IPBC (98% a.i. ) 5.1

Propiconazole (50% a.i.) 20.0

Cl6 amine oxide (30% a.i) 4.0

C12 amine oxide (30% a.i.) 4.0

Defoamer 0.2 Dowanol DPM® 0.0

Propionic acid 3.0

Water 1.2

The active ingredients in the above formulations are summarised in table 2:

Table 2 : Summary of formulations according to the invention.

Claims

1. A wood preservative formulation comprising an amine oxide , an azole and a compound of formula (I)

R^x-A-NR² _p

(D wherein

R¹ denotes an alkyl group which contains from 6 to 24 carbon atoms, benzyl or substituted benzyl, or (CH₂- CH₂O)_nH where n = 1-20;

A is absent or denotes a linker group that may be C=O or -C=ONH (CH₂) _s- where s = 1-3; p = 2 or 3 ; and each R², which are the same or different, denotes H, CH₃, C₂H₅, (CH₂-CH₂O)_nH where n = 1-20, an alkyl group which contains from 6 to 24 carbon atoms, (CH₂)_mC00H, (CH₂)_mCOO^~, (CHX)_1nSO₃H or (CHX) _mS0₃ ^" where m = 1 to 3 and X denotes H or OH; and wherein if the compound is charged it is accompanied by a counterion X^".

2. A formulation as defined in claim 1, wherein said amine oxide is : (i) a trialiphatic substituted amine oxide;

(ii) an iV-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.

3. A formulation as defined in claim 2, wherein said trialiphatic amine oxide has the formula R¹R²R³N-¹O, 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 .

4. A formulation as defined in claim 3, wherein R¹ is a linear, branched or any combination thereof C₃ to C₂₂ saturated or unsaturated group ; and R² and R³ independently are linear, branched, or any combination thereof C₁ to C₂₂ saturated or unsaturated groups .

5. A formulation as defined in claim 4, wherein R² and R³ are both methyl .

6. A formulation as defined in claim 4 or claim 5, wherein R¹ is a linear or branched C₈ to C₁₈ alkyl or alkenyl .

7. A formulation as defined in claim 4 or claim 5, wherein R¹ is a linear or branched C₁₂ to C₁₆ alkyl .

8. A formulation as defined in claim 7, wherein the amine oxide is a mixture of C12 and Cl6 dimethyl alkyl amine oxides.

9. A formulation as defined in any one of the above claims, wherein the azole is an imidazole, a 1,2,4- triazole, or mixtures of both.

10. A formulation as defined in claim 9, wherein the imidazole is a benzimidazole.

11. A formulation as defined in claim 9 or claim 10, wherein the imidazole is selected from thiabendazole, imazalil, carbendazim and prochloraz.

12. A formulation as defined in any one of claims 9 to 11, wherein the 1, 2, 4-triazole is selected from compounds of formula (XI) :

(XI) wherein R⁵ represents a branched or straight chain C_1-5 alkyl group (e.g. t-butyl) and R⁶ represents a phenyl group optionally substituted by one or more substituents selected from halogen (e.g. chlorine, fluorine or bromine) atoms or C_1-3 alkyl (e.g. methyl) , C_1^3 alkόxy (e.g. methoxy) , phenyl or nitro groups;

compounds of formula (XII) :

(XII) wherein R⁷ is as defined for R⁶ above and R⁸ represents a hydrogen atom or a branched or straight chain C_1-5 alkyl group (e.g. n-propyl) ; or selected from the group comprising triadimefon, triadimenol, triazbutil, cyproconazole, difenoconazole, fluquinconazole, flusilazole, uniconazole, diniconazole, bitertanol, hexaconazole, flutriafol, epoxyconazole, tetraconazole, penconazole, and mixtures thereof

13. A formulation as defined in claim 12, wherein the 1, 2, 4-triazole is selected from triadimefon, triadimenol, triazbutil, propiconazole, cyproconazole, difenoconazole, fluquinconazole, tebuconazole, flusilazole, uniconazole, diniconazole, bitertanol, hexaconazole, azaconazole, flutriafol, epoxyconazole, tetraconazole, penconazole and mixtures thereof.

14. A formulation as defined in claim 12 or 13 , wherein the 1, 2, 4-triazole is selected from propiconazole, azaconazole, hexaconazole, tebuconazole, cyproconazole, triadimefon and mixtures thereof.

15. A formulation as defined in any one of the above claims, wherein the compound of formula (I) is a quaternary ammonium compound.

16. A formulation as defined in claim 15, wherein the quarternary ammonium compound is selected from compounds of formula (XIV) :

(XIV) wherein R is an alkyl group having from 6 to 22 carbon atoms, preferably from 12 to 14 carbon atoms; compounds of formula (XV) :

(XV) wherein R¹ and R² 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;

compounds of formulae (XVI) or (XVII) :

(XVI) (XVII) wherein R¹ and R² 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 compound; R³ is methyl or ethyl; R⁴, R⁵ and R⁶ are hydrogen or C_1-8 alkyl groups;

or compounds of formulae (XVIII) or (XIX) :

(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, preferably from 8 to 10 carbon atoms in a .dialkyl 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 ;

and wherein and X^" is an anion chosen to allow ready water solubility of the quaternary ammonium salt.

17. A formulation as defined in claim 16, wherein the quaternary ammonium salt is cocotrimethyl ammonium chloride in which the alkyl group R consists of a mixture of predominantly C₁₂ and C₁₄.

18. A formulation as defined in claim 16, 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.

19. A formulation as defined in claim 16, 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.

20. A formulation as defined in claim 16, wherein the quarternary ammonium salt is benzalkonium chloride or benzalkonium hydroxide.

21. A formulation as defined in any one of claims 1 to 14, wherein the compound of formula (I) is a betaine.

22. A forumulation as defined in claim 21, 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.

23. A formulation as defined in any one of claims 1 to 14, wherein the compound of formula (I) is a C12-C14 dimethylalkylamine or salt thereof.

24. A formulation as defined in any one of the previous claims, further comprising a halopropynyl compound.

25. A formulation as defined in claim 24, wherein the halorpopynyl compound is an iodoproynyl compound of formula (XX) :

(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 .

26. A formulation as defined in claim 25, wherein the iodopropynyl compound is 3-iodo-2-propynyl butyl carbamate .

27. A formulation as defined in any preceding claim, wherein the formulation is in a liquid form.

28. A formulation as defined in claim 27, wherein the formulation is an emulsion.

29. 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 preceeding claims or applying the individual components to the substrate such that the substrate effectively receives a formulation as defined in any of the preceding claims .

30. A method as claimed in claim 29, wherein the substrate is affected by or at risk of being affected by mould and staining or defacing organisms and in particular sapstain organisms .

31. A substrate made of wood or other cellulosic material treated with a formulation as claimed in any one of claims 1 to 28.

32. A substrate of wood or other cellulosic material comprising an amine oxide , an azole and a compound of formula (I)

R'-A-NR^

(I) wherein R¹ denotes an alkyl group which contains from 6 to 24 carbon atoms, benzyl or substituted benzyl, or (CH₂- CH₂O)_nH where n = 1-20;

A is absent or denotes a linker group that may be C=O or -C=ONH (CH₂) _s- where S = 1-3;

P = 2 or 3; and each R², which are the same or different, denotes H, CH₃, C₂H₅, (CH₂-CH₂O)_nH where n = 1-20, an alkyl group which contains from 6 to 24 carbon atoms, (CH₂) _mCOOH, (CH₂J_1nCOO^", (CHX)_1nSO₃H or (CHX)_1nSO₃ ^" where m = 1 to 3 and X denotes H or OH, ; and wherein if the compound is charged it is accompanied by a counterion X^".