Wood preservative formulations comprising isothtazolones which provide protection against surface staining

Abstract

The present invention provides a wood preservative formulation comprising an isothiazolone, an organic fungicidal timber decay preservative and an unsaturated carboxylic or sulphonic acid, salt or anhydride thereof. The formulations of the invention are surprisingly effective at protecting wood and other cellulosic substrates, in particular at providing prolonged protection against in-service surface staining. The invention also provides methods for treating wood and other cellulosic substrates with said formulations.

Claims

1. A method of protecting a substrate of wood or other cellulosic material which comprises applying to the substrate or treating the substrate with an effective amount of a formulation comprising: an isothiazolone in an amount from 10 ppm but less than 500 ppm, the isothiazolone selected from the group consisting of methylisothiazol-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, octylisothiazol-3-one, 1,2-benzisothiazol-3(2H)-one, N-methyl-1,2-benzisothiazol-3-one, N-(n-butyl)-1,2-benzisothiazol-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, and combinations thereof; an organic fungicidal timber decay preservative, wherein the organic fungicidal timber decay preservative selected from the group consisting of a quaternary ammonium compound, an azole, a fungicidal heterocyclic compound, or mixtures thereof in an amount from 100 ppm to 300 ppm, wherein the organic fungicidal timber decay preservative is free of thiabendazole; and an unsaturated carboxylic or sulphonic acid, a salt, ester or anhydride thereof in an amount from 1000 to 10000 ppm, the unsaturated carboxylic or sulphonic acid being selected from the group consisting of (i) abietic acid, pimaric acid, benzoic acid, salicylic acid, a dodecyl benzene sulfonic acid, a dehydroacetic acid, or a salt, ester or anhydride thereof, (ii) a linear unsaturated carboxylic acid having from 4 carbons to 22 carbons, a salt, ester or anhydride thereof, and (iii) an aromatic acid is of formula (I): ##STR00006## wherein Y denotes CO.sub.2M or SO.sub.3M; each R independently denotes C.sub.1-C.sub.12 alkyl, OH, OMe, OEt, NH.sub.2, NMe.sub.2, CO.sub.2M or halogen, wherein two R groups may optionally form naphthyl; M denotes H, K or Na; and m denotes 0 to 2, or a salt, ester or anhydride of formula (I); and wherein the formulation inhibits surface staining for at least 24 weeks; and wherein the formulation is free of haloalkynyl compounds and biocidal metal ions.

2. The method as defined in claim 1, wherein the salt is an alkali metal salt.

3. The method as defined in claim 1, wherein the aromatic acid or salt thereof is selected from the group consisting of benzoic acid and sodium benzoate.

4. The method as defined in claim 1, wherein the unsaturated carboxylic or sulphonic acid is selected from the group consisting of abietic acid, sodium abietate, pimaric acid and sodium pimarate.

5. The method as defined in claim 1, wherein the unsaturated carboxylic acid, salt, ester or anhydride thereof is selected from the group consisting of oleic acid, sodium oleate or potassium oleate.

6. The method as defined in claim 1, wherein the isothiazolone is 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one.

7. The method as defined in claim 1, wherein the organic fungicidal timber decay preservative is an azole.

8. The method as defined in claim 7, wherein the azole compound is an imidazole, a 1,2,4-triazole, or mixtures of both.

9. The method as defined in claim 8, wherein the imidazole is a benzimidazole.

10. The method as defined in claim 8, wherein the 1,2,4-triazole is selected from the group consisting of compounds of formula (IV): ##STR00007## wherein R.sup.5 represents a branched or straight chain C.sub.1-5 alkyl group; and R.sup.6 represents a phenyl group optionally substituted by one or more substituents selected from halogen, C.sub.1-3 alkyl, C.sub.1-3 alkoxy, phenyl or nitro; and compounds of formula (V): ##STR00008## wherein R.sup.7 is as defined for R.sup.6 above; and R.sup.8 represents a hydrogen atom or a branched or straight chain C.sub.1-5 alkyl group; or selected from the group consisting of triadimefon, triadimenol, triazbutil, cyproconazole, difenoconazole, fluquinconazole, flusilazole, tebuconazole, uniconazole, diniconazole, bitertanol, hexaconazole, flutriafol, epoxyconazole, tetraconazole, penconazole, ipconazole, prothiazole and mixtures thereof.

11. The method as defined in claim 10, wherein the 1,2,4-triazole is selected from the group consisting of triadimefon, triadimenol, triazbutil, propiconazole, cyproconazole, difenoconazole, fluquinconazole, tebuconazole, flusilazole, uniconazole, diniconazole, bitertanol, hexaconazole, azaconazole, flutriafol, epoxyconazole, tetraconazole, penconazole, ipconazole, prothiazole and mixtures thereof.

12. The method as defined in claim 10, wherein the 1,2,4-triazole is selected from the group consisting of propiconazole, tebuconazole, and mixtures thereof.

13. The method as defined in claim 1, wherein the formulation is in a liquid form.

14. The method as defined in claim 13, wherein the ratio of azole to isothiazolone is 10:1 to 2:1 w/w.

15. The method as defined in claim 13, wherein the formulation is an emulsion.

16. The method as defined in claim 1, wherein the organic fungicidal timber decay preservative is an azole, and wherein the ratio of azole to isothiazolone is at least 3:2.

17. The method as defined in claim 1, wherein the total amount of isothiazolone in the solution is at least 30 ppm to 300 ppm.

18. The method as defined in claim 1, wherein the formulation is free of biocidal metal ions.

19. A method of protecting a substrate of wood or other cellulosic material which comprises applying to the substrate or treating the substrate with an effective amount of a formulation in the form of an emulsion, comprising: an isothiazolone in an amount from 10 ppm but less than 500 ppm, the isothiazolone selected from the group consisting of methylisothiazol-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, octylisothiazol-3-one, 1,2-benzisothiazol-3(2H)-one, N-methyl-1,2-benzisothiazol-3-one, N-(n-butyl)-1,2-benzisothiazol-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, and combinations thereof; an organic fungicidal timber decay preservative, wherein the organic fungicidal timber decay preservative is free of thiabendazole, wherein the organic fungicidal timber decay preservative selected from the group consisting of a quaternary ammonium compound, an azole, a fungicidal heterocyclic compound, or mixtures thereof in an amount from 100 ppm to 300 ppm, wherein the organic fungicidal timber decay preservative is free of thiabendazole; and an unsaturated carboxylic or sulphonic acid, a salt, ester or anhydride thereof, the unsaturated carboxylic or sulphonic acid being selected from the group consisting of (i) an unsaturated cyclic carboxylic or sulphonic acid being a resin acid, a salt, ester or anhydride thereof, (ii) a linear unsaturated carboxylic acid having from 4 carbons to 22 carbons, a salt, ester or anhydride thereof, and (iii) an aromatic acid is of formula (I): ##STR00009## wherein Y denotes CO.sub.2M or SO.sub.3M; each R independently denotes C.sub.1-C.sub.12 alkyl, OH, OMe, OEt, NH.sub.2, NMe.sub.2, CO.sub.2M or halogen, wherein two R groups may optionally form naphthyl; M denotes H, K or Na; and m denotes 0 to 5, or a salt, ester or anhydride of formula (I); and wherein the formulation is free of haloalkynyl compounds and biocidal metal ions.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a photograph of untreated wood after exposure for 25 weeks, according to Example 1.

(2) FIG. 2 is a photograph of wood treated with formulation I-1 after exposure for 25 weeks.

(3) FIG. 3 is a photograph of wood treated with formulation I-2 after exposure for 25 weeks.

(4) FIG. 4 is a photograph of wood treated with formulation I-3 after exposure for 25 weeks.

(5) FIG. 5 is a photograph of wood treated with formulation I-4 after exposure for 25 weeks.

(6) FIG. 6 is a photograph of wood treated with formulation I-5 after exposure for 25 weeks.

(7) FIG. 7 is a photograph of wood treated with formulation I-6 after exposure for 25 weeks.

(8) FIG. 8a is a photograph of wood treated with formulation I-7 after exposure for 25 weeks.

(9) FIG. 8b is a photograph of wood treated with formulation I-8 after exposure for 25 weeks.

(10) FIG. 8c is a photograph of wood treated with formulation I-9 after exposure for 25 weeks.

(11) FIG. 8d is a photograph of wood treated with formulation I-10 after exposure for 25 weeks.

(12) FIG. 9a is a photograph of wood treated with formulation I-11 after exposure for 25 weeks.

(13) FIG. 9b is a photograph of wood treated with formulation I-12 after exposure for 25 weeks.

(14) FIG. 9c is a photograph of wood treated with formulation I-13 after exposure for 25 weeks.

(15) FIG. 9d is a photograph of wood treated with formulation I-14 after exposure for 25 weeks.

(16) FIG. 10a is a photograph of wood treated with formulation I-15 after exposure for 25 weeks.

(17) FIG. 10b is a photograph of wood treated with formulation I-16 after exposure for 25 weeks.

(18) FIG. 11a is a photograph of wood treated with formulation I-17 after exposure for 25 weeks.

(19) FIG. 11b is a photograph of wood treated with formulation I-18 after exposure for 25 weeks.

(20) FIG. 12a is a photograph of wood treated with formulation I-19 after exposure for 25 weeks.

(21) FIG. 12b is a photograph of wood treated with formulation I-20 after exposure for 25 weeks.

(22) FIG. 13 is a photograph of wood treated with formulation II-1 after exposure for 25 weeks.

(23) FIG. 14 is a photograph of wood treated with formulation II-2 after exposure for 25 weeks.

(24) FIG. 15 is a photograph of wood treated with formulation II-3 after exposure for 25 weeks.

(25) FIG. 16 is a photograph of wood treated with formulation II-4 after exposure for 25 weeks.

(26) FIG. 17 is a photograph of wood treated with formulation II-5 after exposure for 25 weeks.

(27) FIG. 18 is a photograph of wood treated with formulation II-6 after exposure for 25 weeks.

(28) FIG. 19 is a photograph of wood treated with formulation III-1-13 after exposure for 24 weeks.

(29) FIG. 20a is a photograph of wood treated with formulation III-2-28 after exposure for 24 weeks.

(30) FIG. 20b is a photograph of wood treated with formulation III-3-40 after exposure for 24 weeks.

(31) FIG. 21a is a photograph of wood treated with formulation III-2-25 after exposure for 24 weeks.

(32) FIG. 21b is a photograph of wood treated with formulation III-3-37 after exposure for 24 weeks.

(33) FIG. 22a is a photograph of wood treated with formulation IV-1 after exposure for 24 weeks.

(34) FIG. 22b is a photograph of wood treated with formulation IV-2 after exposure for 24 weeks.

(35) FIG. 22c is a photograph of wood treated with formulation IV-3 after exposure for 24 weeks.

(36) FIG. 22d is a photograph of wood treated with formulation IV-4 after exposure for 24 weeks.

(37) FIG. 23a is a photograph of untreated Scottish Larch as used in Example 5 prior to exposure for 16 months.

(38) FIG. 23b is a photograph of Scottish Larch treated with the formulation of Example 5 prior to exposure for 16 months.

(39) FIG. 24a is a photograph of untreated Scottish Larch as used in Example 5 after exposure for 16 months.

(40) FIG. 24b is a photograph of Scottish Larch treated with the formulation of Example 5 after exposure for 16 months.

EXAMPLES

Example 1

(41) A field trial was initiated in which a number of formulations were tested for their ability to prolong the period which timber could be maintained in a stain and mould free condition.

(42) The formulations were prepared by adding all of the water insoluble ingredients (e.g. azoles, isothiazolone, any insoluble acids etc.) to the solvent (Dowanol DPM®) and stirring until fully dissolved. The surfactant was then stirred in and water added. Any water soluble additives (e.g. sodium benzoate) were added last.

(43) “a.i.” as used in these examples is active ingredient.

(44) The following products were used for each of the active ingredients:

(45) TABLE-US-00001 Preventol A8 ® (95% a.i. tebuconazole) Wocosen 50TK ® (50% a.i. propiconazole) Vanquish 100 ® (99% a.i. BBIT) Acticide 45 ® (45% a.i. OIT) Acticide B20 ® (20% a.i. BIT)

(46) The formulations used in the test were as follows (all values are given in % w/w):

(47) Formulation I-1 (Comparative)

(48) TABLE-US-00002 Tebuconazole (95% a.i.) 1.5 Surfactant 11.25 Solvent 8.8 Water 78.45
Formulation I-2 (Comparative)

(49) TABLE-US-00003 Propiconazole (50% a.i.) 3 Surfactant 11.25 Solvent 8.8 Water 76.95
Formulation I-3 (Comparative)

(50) TABLE-US-00004 Tebuconazole (95% a.i.) 1 Propiconazole (50% a.i.) 1 Surfactant 11.25 Solvent 8.8 Water 77.95
Formulation I-4 (Comparative)

(51) TABLE-US-00005 Tebuconazole (95% a.i.) 1.5 Surfactant 11.25 Solvent 8.8 Sodium benzoate 22.5 Water 55.95
Formulation I-5 (Comparative)

(52) TABLE-US-00006 Propiconazole (50% a.i.) 3 Surfactant 11.25 Solvent 8.8 Sodium Benzoate 22.5 Water 54.45
Formulation I-6 (Comparative)

(53) TABLE-US-00007 Tebuconazole (95% a.i.) 1 Propiconazole (50% a.i.) 1 Surfactant 11.25 Solvent 8.8 Sodium benzoate 22.5 Water 55.45
Formulation I-7 (Comparative)

(54) TABLE-US-00008 BBIT (99% a.i.) 1.25 Dowanol DPM ® 8.99 Dehscofix CO120F ® 11.23 Water 77.04 EDTA 1.5

(55) Diluted to be equivalent to 100 ppm BBIT when applied to wood.

(56) Formulation I-8 (Comparative)

(57) TABLE-US-00009 BBIT (99% a.i.) 1.21 Tebuconazole (95% a.i.) 0.97 Propiconazole (50% a.i.) 1.01 Dowanol DPM ® 8.69 Dehscofix CO120F ® 10.86 Water 75.81 EDTA 1.45

(58) Diluted to be equivalent to 100 ppm BBIT when applied to wood.

(59) Formulation I-9 (Comparative)

(60) TABLE-US-00010 BBIT (99% a.i.) 1.19 Dowanol DPM ® 8.97 Dehscofix CO120F ® 11.21 Water 54.56 Sodium Benzoate 22.57 EDTA 1.5

(61) Diluted to be equivalent to 100 ppm BBIT when applied to wood.

(62) Formulation I-10

(63) TABLE-US-00011 BBIT (99% a.i.) 1.19 Tebuconazole (95% a.i.) 1 Propiconazole (50% a.i.) 1 Dowanol DPM ® 8.69 Dehscofix CO120F ® 12.64 Water 50.8 Sodium Benzoate 22.94 EDTA 1.49

(64) Diluted to be equivalent to 100 ppm BBIT when applied to wood.

(65) Formulation I-11 (Comparative)

(66) TABLE-US-00012 BIT (20% a.i.) 5.99 Dowanol DPM ® 8.99 Dehscofix CO120F ® 11.29 Water 72.23 EDTA 1.5

(67) Diluted to be equivalent to 100 ppm BIT when applied to wood.

(68) Formulation I-12 (Comparative)

(69) TABLE-US-00013 BIT (20% a.i.) 5.86 Tebuconazole (95% a.i.) 0.98 Propiconazole (50% a.i.) 0.98 Dowanol DPM ® 8.79 Dehscofix CO120F ® 10.98 Water 70.81 EDTA 1.61

(70) Diluted to be equivalent to 100 ppm BIT when applied to wood.

(71) Formulation I-13 (Comparative)

(72) TABLE-US-00014 BIT (20% a.i.) 5.98 Dowanol DPM ® 9.07 Dehscofix CO120F ® 11.22 Sodium benzoate 22.57 Water 49.61 EDTA 1.5

(73) Diluted to be equivalent to 100 ppm BIT when applied to wood.

(74) Formulation I-14

(75) TABLE-US-00015 BIT (20% a.i.) 5.97 Tebuconazole (95% a.i.) 0.99 Propiconazole (50% a.i.) 1.01 Dowanol DPM ® 8.97 Dehscofix CO120F ® 11.22 Sodium benzoate 7.46 Water 47.55 EDTA 1.56

(76) Diluted to be equivalent to 100 ppm BIT when applied to wood.

(77) Formulation I-15 (Comparative)

(78) TABLE-US-00016 OIT (45% a.i.) 0.79 Dowanol DPM ® 8.84 Dehscofix CO120F ® 11.05 Water 77.65 EDTA 1.67

(79) Diluted to be equivalent to 30 ppm OIT when applied to wood.

(80) Formulation I-16

(81) TABLE-US-00017 OIT (45% a.i.) 0.80 Tebuconazole (95% a.i.) 1 Propiconazole (50% a.i.) 1 Dowanol DPW ® 9.04 Dehscofix CO120F ® 11.24 Water 52.94 Sodium benzonate 22.48 EDTA 1.5

(82) Diluted to be equivalent to 30 ppm OIT when applied to wood.

(83) Formulation I-17 (Comparative)

(84) TABLE-US-00018 BBIT (99% a.i.) 3.6 Dowanol DPM ® 9.01 Dehscofix CO120F ® 11.24 Water 74.63 EDTA 1.52

(85) Diluted to be equivalent to 300 ppm BBIT when applied to wood.

(86) Formulation I-18

(87) TABLE-US-00019 BBIT (99% a.i.) 3.59 Tebuconazole (95% a.i.) 1.02 Propiconazole (50% a.i.) 1.02 Dowanol DPM ® 9.05 Dehscofix CO120F ® 11.22 Sodium benzoate 22.45 Water 50.14 EDTA 1.50

(88) Diluted to be equivalent to 300 ppm BBIT when applied to wood.

(89) Formulation I-19 (Comparative)

(90) TABLE-US-00020 BIT (20% a.i.) 17.98 Dowanol DPM ® 8.99 Dehscofix CO120F ® 11.24 Water 60.24 EDTA 1.55

(91) Equivalent to 300 ppm BIT when applied to wood

(92) Formulation I-20

(93) TABLE-US-00021 BIT (20% a.i.) 18.18 Tebuconazole (95% a.i.) 1.01 Dowanol DPM ® 9.16 Dehscofix CO120F ® 11.38 Sodium benzoate 22.71 Water 36.05 EDTA 1.51

(94) Equivalent to 300 ppm BIT when applied to wood

(95) The test formulations were evaluated using planed timber blocks of dimension 135×70×25 mm which were machined from Scots Pine (Pinus sylvestris). The upper face of each block consisted entirely of sapwood. Five duplicate blocks were treated with each of the formulations.

(96) For exposure, the blocks were mounted horizontally on untreated pine racks at ground lavel on a gravel surface for natural weathering conditions.

(97) After 25 weeks exposure, the samples were inspected to determine the extent of surface staining and mould growth.

(98) For comparison, a further set of five untreated timber blocks were also subjected to 25 weeks exposure. The untreated blocks showed considerable mould growth and surface staining, as shown in FIG. 1.

(99) The blocks treated with formulations 1, 2 and 3 are shown in FIGS. 2, 3 and 4 respectively. As can be seen, the inclusion of azoles has little effect on the amount of surface staining. Furthermore, the combination of tebuconazole and propiconazole showed no discernable improvement over the use of either azole alone.

(100) The blocks treated with formulations 4, 5 and 6 are shown in FIGS. 5, 6 and 7 respectively. These Figures show that the combination of sodium benzoate with an azole does show significantly improved protection against surface staining. Moreover, the difference between propiconazole and tebuconazole either alone or in combination is more evident. However, each of formulations 4, 5 and 6 fail to provide acceptable protection against surface staining.

(101) The blocks treated with formulations 7, 8, 9 and 10 are shown in FIGS. 8a, 8b, 8c and 8d respectively. FIGS. 8a and 8b demonstrate that blocks treated with a formulation containing only an isothiazolone (BBIT) show similar surface staining to blocks treated with a formulation comprising an isothiazolone and an azole. Therefore, the azole does not markedly improve the performance of the isothiazolone. FIG. 8c shows that the combination of BBIT and sodium benzoate does show significant improvement in protection against surface staining. However, the blocks in FIG. 8c are beginning to show the first signs of significant surface staining. In contrast, the blocks treated with the three way combination of BBIT, sodium benzoate and an azole according to the invention show no visible surface staining (see FIG. 8d).

(102) The blocks treated with formulations 11, 12, 13 and 14 are shown in FIGS. 9a, 9b, 9c and 9d respectively. These Figures show a similar trend to FIGS. 8a, 8b, 8c and 8d, in that the azole/BIT combination shows little improvement over BIT alone, while BIT/sodium benzoate does show an improvement. However, the most effective formulation is clearly the three way combination of BIT, sodium benzoate and an azole, as shown in FIG. 9d.

(103) The blocks treated with formulations 15, 16, 17, 18, 19 and 20 are shown in FIGS. 10a, 10b, 11a, 11b, 12a and 12b respectively. These figures clearly show that the combination of isothiazolone with azole and sodium benzoate display significantly better protection against surface stain than the use of either isothiazolone alone, or sodium benzoate and azole in combination (see FIGS. 5 and 7).

Example 2

(104) The following formulations were formulated and tested using the same protocols as described in Example 1.

(105) Formulation II-1

(106) TABLE-US-00022 OIT (45% a.i.) 2.65 Tebuconazole (95% a.i.) 1.49 Dowanol DPM ® 9.10 Dehscofix CO120F ® 11.17 Water 51.28 Sodium benzonate 22.59 EDTA 1.72

(107) Diluted to be equivalent to 100 ppm OIT when applied to wood.

(108) Formulation II-2

(109) TABLE-US-00023 OIT (45% a.i.) 2.65 Propiconazole (50% a.i.) 3.13 Dowanol DPM ® 8.98 Dehscofix CO120F ® 11.23 Water 49.97 Sodium benzonate 22.47 EDTA 1.56

(110) Diluted to be equivalent to 100 ppm OIT when applied to wood.

(111) Formulation II-3

(112) TABLE-US-00024 OIT (45% a.i.) 2.67 Triadimefon 1.50 Dowanol DPM ® 17.99 Dehscofix CO120F ® 17.46 Water 36.44 Sodium benzonate 22.43 EDTA 1.52

(113) Diluted to be equivalent to 100 ppm OIT when applied to wood.

(114) Formulation II-4

(115) TABLE-US-00025 OIT (45% a.i.) 2.66 Tebuconazole (95% a.i.) 1 Propiconazole (50% a.i.) 1 Dowanol DPM ® 8.99 Dehscofix CO120F ® 11.24 Water 73.53 EDTA 1.58

(116) Diluted to be equivalent to 100 ppm OIT, then combined with 0.03 w/w abietic acid and applied to wood.

(117) Formulation II-5

(118) TABLE-US-00026 OIT (45% a.i.) 2.66 Tebuconazole (95% a.i.) 1 Propiconazole (50% a.i.) 1 Dowanol DPW ® 8.99 Dehscofix CO120F ® 11.24 Water 73.53 EDTA 1.58

(119) Diluted to be equivalent to 100 ppm OIT, then combined with 0.03 w/w sodium salicyclate and applied to wood.

(120) Formulation II-6

(121) TABLE-US-00027 OIT (45% a.i.) 2.66 Tebuconazole (95% a.i.) 1 Propiconazole (50% a.i.) 1 Dowanol DPM ® 8.99 Dehscofix CO120F ® 11.24 Water 73.53 EDTA 1.58

(122) Diluted to be equivalent to 100 ppm OIT, then combined with 0.03 w/w oleic acid and applied to wood.

(123) Photographs of wood treated with formulations II-1 to II-6 after 25 weeks' exposure are shown in FIGS. 13 to 18 respectively. From these figures, it is clear that each of the formulations displays excellent protection against surface staining.

Example 3

(124) Sections of pine sideboard were cut into 134×68×20 mm blocks which were then treated with wood preservative treatment solutions. The formulations were applied to the blocks by 45 minute wet vacuum in the treatment solution at 80 kPa (600 mmHg) followed by an hour at 1.2 MPa (12 bar) pressure. The blocks were treated with an average retention target of 650 kg/m.sup.3,

(125) The following products were used for each of the active ingredients:

(126) TABLE-US-00028 Acticide DT ® (10-25% a.i. DCOIT) Acticide RS ® (10-25% a.i. CMIT) Acticide 45 ® (45% a.i. OIT) Preventol A8 ® (95% a.i. tebuconazole) Wocosen 50TK ® (50 a.i propiconazole) Evipol ® (94% a.i. cyproconazole) Corbel ® (79.5% a.i. fenpropimorph) Carboquat 250T ® (50% a.i. didecyldimethyl ammonium chloride)

(127) The formulations used in the test were as follows (all values are given in % w/w):

(128) Formulation III-1-1 (Comparative)

(129) TABLE-US-00029 Oleic acid 15.00 30% NaOH solution 7.08 Dowanol DPM 9.00 Dehscofix CO130F 11.25 Dissolvine E39 1.50 Foamban 2901 0.08 Water 56.10

(130) This concentrate was then diluted down to 0.45% with water.

(131) Formulation III-1-2 (Comparative)

(132) TABLE-US-00030 Sodium salicylate 10.00 30% NaOH solution 8.33 Dowanol DPM 9.00 Dehscofix CO130F 11.25 Dissolvine E39 1.50 Foamban 2901 0.08 Water 59.84

(133) This concentrate was then diluted down to 0.45% with water.

(134) Formulation III-1-3 (Comparative)

(135) TABLE-US-00031 Sodium dodecyl benzene sulfonate 20.00 Dowanol DPM 9.00 Dehscofix CO130F 11.25 Dissolvine E39 1.50 Foamban 2901 0.08 Water 58.18

(136) This concentrate was then diluted down to 0.45% with water.

(137) Formulation III-1-4 (Comparative)

(138) TABLE-US-00032 Abietic acid 10.00 30% NaOH solution 4.41 Dowanol DPM 9.00 Dehscofix CO130F 11.25 Dissolvine E39 1.50 Foamban 2901 0.08 Water 63.76

(139) This concentrate was then diluted down to 0.45% with water.

(140) Formulation III-1-5 (Comparative)

(141) TABLE-US-00033 Sodium benzoate 20.00 Dowanol DPM 9.00 Dehscofix CO130F 11.25 Dissolvine E39 1.50 Foamban 2901 0.075 Water 58.18

(142) This concentrate was then diluted down to 0.45% with water.

(143) Formulation III-1-6 (Comparative)

(144) TABLE-US-00034 Sodium acetate 11.38 Dowanol DPM 9.00 Dehscofix CO130F 11.25 Dissolvine E39 1.50 Foamban 2901 0.08 Water 66.79

(145) This concentrate was then diluted down to 0.45% with water.

(146) Formulation III-1-7 (Comparative)

(147) TABLE-US-00035 Methyl benzoate 18.90 30% NaOH solution 18.51 Dowanol DPM 9.00 Dehscofix CO130F 11.25 Dissolvine E39 1.50 Foamban 2901 0.08 Water 40.76

(148) This concentrate was then diluted down to 0.45% with water.

(149) Formulation III-1-8 (Comparative)

(150) TABLE-US-00036 Dehydroacetic acid 5.00 Dowanol DPM 9.00 Dehscofix CO130F 11.25 Dissolvine E39 1.50 Foamban 2901 0.08 Water 73.17

(151) This concentrate was then diluted down to 0.45% with water.

(152) Formulation III-1-9 (Comparative)

(153) TABLE-US-00037 Preventol A8 (Teb) 0.79 Wocosen 50TK (Prop) 1.50 Dowanol DPM 9.00 Dehscofix CO130F 11.25 Dissolvine E39 1.50 Foamban 2901 0.08 Water 75.89

(154) This concentrate was then diluted down to 0.95% with water.

(155) Formulation III-1-10 (Comparative)

(156) TABLE-US-00038 Evipol (Cyp) 1.554 Dowanol DPM 9.00 Dehscofix CO130F 11.25 Dissolvine E39 1.50 Foamban 2901 0.08 Water 76.62

(157) This concentrate was then diluted down to 0.95% with water.

(158) Formulation III-1-11 (Comparative)

(159) TABLE-US-00039 DDAC 3.00 Dowanol DPM 9.00 Dehscofix CO130F 11.25 Dissolvine E39 1.50 Foamban 2901 0.08 Water 75.18

(160) This concentrate was then diluted down to 28.6% with water.

(161) Formulation III-1-12 (Comparative)

(162) TABLE-US-00040 Fenpropimorph 1.89 Dowanol DPM 9.00 Dehscofix CO130F 11.25 Dissolvine E39 1.50 Foamban 2901 0.08 Water 76.29

(163) This concentrate was then diluted down to 0.95% with water.

(164) Formulation III-1-13 (Comparative)

(165) TABLE-US-00041 Acticide RS (CMIT) 26.68 Propylene glycol 30.00 Caflon TD1010 11.11 Water 32.21

(166) This concentrate was then diluted down to 1.5% with water (60 ppm CMIT).

(167) Formulation III-1-14 (Comparative)

(168) TABLE-US-00042 Acticide 45 (OIT) 13.34 Propylene glycol 30.00 Caflon TD 1010 11.11 Water 45.55

(169) This concentrate was then diluted down to 0.1% with water (60 ppm OIT).

(170) Formulation III-1-15 (Comparative)

(171) TABLE-US-00043 Acticide DT (DCOIT) 13.34 Propylene glycol 30.00 Caflon TD1010 22.22 Water 34.44

(172) This concentrate was then diluted down to 0.1% with water (60 ppm DCOIT).

(173) Formulation III-2-16 (Comparative)

(174) This formulation was formed from 0.95% of the concentrate in III-1-9 and 0.1% of the concentrate in III-1-14 in water.

(175) Formulation III-2-17 (Comparative)

(176) This formulation was formed from 0.95% of the concentrate in III-1-9 and 0.45% of the concentrate in III-1-7 in water.

(177) Formulation III-2-18 (Comparative)

(178) This formulation was formed from 0.45% of the concentrate in III-1-7 and 0.1% of the concentrate in III-1-14 in water.

(179) Formulation III-2-19 (Comparative)

(180) This formulation was formed from 28.6% of the concentrate in III-1-11 and 0.1% of the concentrate in III-1-14 in water.

(181) Formulation III-2-20 (Comparative)

(182) This formulation was formed from 28.6% of the concentrate in III-1-11 and 0.45% of the concentrate in III-1-5 in water.

(183) Formulation III-2-21 (Comparative)

(184) This formulation was formed from 0.45% of the concentrate in III-1-5 and 0.1% of the concentrate in III-1-14 in water.

(185) Formulation III-2-22 (Comparative)

(186) This formulation was formed from 0.95% of the concentrate in III-1-9 and 0.45% of the concentrate in III-1-8 in water.

(187) Formulation III-2-23 (Comparative)

(188) This formulation was formed from 0.45% of the concentrate in III-1-8 and 0.1% of the concentrate in III-1-14 in water.

(189) Formulation III-2-24 (Comparative)

(190) This formulation was formed from 1.5% of the concentrate in III-1-13 and 0.95% of the concentrate in III-1-10 in water.

(191) Formulation III-2-25 (Comparative)

(192) This formulation was formed from 0.95% of the concentrate in III-1-10 and 0.45% of the concentrate in III-1-1 in water.

(193) Formulation III-2-26 (Comparative)

(194) This formulation was formed from 1.5% of the concentrate in III-1-13 and 0.45% of the concentrate in III-1-1 in water.

(195) Formulation III-2-27 (Comparative)

(196) This formulation was formed from 1.5% of the concentrate in III-1-13 and 0.45% of the concentrate in III-1-4 in water.

(197) Formulation III-2-28 (Comparative)

(198) This formulation was formed from 0.95% of the concentrate in III-1-12 and 0.45% of the concentrate in III-1-4 in water.

(199) Formulation III-3-29

(200) This formulation was formed from 1.5% of the concentrate in III-1-13, 0.95% of the concentrate in III-1-12 and 0.45% of the concentrate in III-1-4 in water.

(201) Formulation III-3-30

(202) This formulation was formed from 0.95% of the concentrate in III-1-9, 0.1% of the concentrate in III-1-14 and 0.45% of the concentrate in III-1-8 in water.

(203) Formulation III-3-31

(204) This formulation was formed from 0.95% of the concentrate in III-1-9, 0.1% of the concentrate in III-1-14 and 0.45% of the concentrate in III-1-1 in water.

(205) Formulation III-3-32

(206) This formulation was formed from 0.95% of the concentrate in III-1-9, 0.1% of the concentrate in III-1-14 and 0.45% of the concentrate in III-1-7 in water.

(207) Formulation III-3-33

(208) This formulation was formed from 0.95% of the concentrate in III-1-10, 0.1% of the concentrate in III-1-14 and 0.45% of the concentrate in III-1-5 in water.

(209) Formulation III-3-34

(210) This formulation was formed from 28.6% of the concentrate in III-1-11, 0.1% of the concentrate in III-1-14 and 0.45% of the concentrate in III-1-4 in water.

(211) Formulation III-3-35

(212) This formulation was formed from 28.6% of the concentrate in III-1-11, 0.1% of the concentrate in III-1-14 and 0.45% of the concentrate in III-1-5 in water.

(213) Formulation III-3-36

(214) This formulation was formed from 0.95% of the concentrate in III-1-9, 0.1% of the concentrate in III-1-14 and 0.45% of the concentrate in III-1-3 in water.

(215) Formulation III-3-37

(216) This formulation was formed from 0.95% of the concentrate in III-1-10, 1.5% of the concentrate in III-1-13 and 0.45% of the concentrate in III-1-1 in water.

(217) Formulation III-3-38

(218) This formulation was formed from 0.95% of the concentrate in III-1-10, 1.5% of the concentrate in III-1-13 and 0.45% of the concentrate in III-1-5 in water.

(219) Formulation III-3-39

(220) This formulation was formed from 28.6% of the concentrate in III-1-11, 1.5% of the concentrate in III-1-13 and 0.45% of the concentrate in III-1-2 in water.

(221) Formulation III-3-40

(222) This formulation was formed from 0.95% of the concentrate in III-1-12, 1.5% of the concentrate in III-1-13 and 0.45% of the concentrate in III-1-4 in water.

(223) Formulation III-3-41 (Comparative)

(224) This formulation was formed from 0.95% of the concentrate in III-1-9, 0.1% of the concentrate in III-1-15 and 0.45% of the concentrate in III-1-6 in water.

(225) After drying, the blocks were left outside exposed to the weather on horizontal racks for a total of twenty four weeks, running from September though to March. The tests were carried out in northern England, meaning that the blocks were left exposed through autumn and winter. The blocks were monitored over time to assess the level of any staining. The following scores were attributed to the blocks, depending on the level of observable staining:

(226) TABLE-US-00044 Score Level of Staining 0 No staining visible 1 Insignificantly blue stained. The surface exhibits only individual small blue stained spots with a largest diameter of 2 mm. 2 Blue stained: the surface is continuously blue stained up to a maximum of one third of the surface area, or partially stained in up to half of the area. 3 Strongly blue stained. More than half the surface area is continuously stained or more than half the surface area is partially blue stained.

(227) The tables below summarises the results obtained after 24 weeks' exposure:

(228) TABLE-US-00045 Iso- Decay Formulation thiazolone Preservative Acid Score Untreated — — — 3 III-1-1* — — Oleic acid 3 III-1-2* — — Sodium salicylate 3 III-1-3* — — Sodium dodecyl 3 benzene sulfonate III-1-4* — — Abietic acid 3 III-1-5* — — Sodium benzoate 3 III-1-6* — — Sodium acetate 3 III-1-7* — — Methyl benzoate + 3 NaOH III-1-8* — — Dehydroacetic 3 acid III-1-9* — Tebuconazole/ — 3 Propiconazole III-1-10* — Cyproconazole — 3 III-1-11* — DDAC — 2 III-1-12* — Fenpropimorph — 3 III-1-13* CMIT — — 1 III-1-14* OIT — — 2 III-1-15* DCOIT — — 3 III-2-16* OIT Tebuconazole/ — 2 Propiconazole III-2-17* — Tebuconazole/ Methyl benzoate + 3 Propiconazole NaOH III-2-18* OIT — Methyl benzoate + 1 NaOH III-2-19* OIT DDAC — 1 III-2-20* — DDAC Sodium benzoate 2 III-2-21* OIT — Sodium benzoate 1 III-2-22* — Tebuconazole/ Dehydroacetic 3 Propiconazole acid III-2-23* OIT — Dehydroacetic 2 acid III-2-24* CMIT Cyproconazole — 1 III-2-25* — Cyproconazole Oleic acid 3 III-2-26* CMIT — Oleic acid 1 III-2-27* CMIT — Abietic acid 1 III-2-28* — Fenpropimorph Abietic acid 3 III-3-29 CMIT Fenpropimorph Abietic acid 1 III-3-30 OIT Tebuconazole/ Dehydroacetic 1 Propiconazole acid III-3-31 OIT Tebuconazole/ Oleic acid 1 Propiconazole III-3-32 OIT Tebuconazole/ Methyl benzoate + 1 Propiconazole NaOH III-3-33 OIT Cyproconazole Sodium benzoate 1 III-3-34 OIT DDAC Abietic acid 1 III-3-35 OIT DDAC Sodium benzoate 1 III-3-36 OIT Tebuconazole/ Sodium dodecyl 1 Propiconazole benzene sulfonate III-3-37 CMIT Cyproconazole Oleic acid 1 III-3-38 CMIT Cyproconazole Sodium benzoate 1 III-3-39 CMIT DDAC Sodium salicylate 1 III-3-40 CMIT Fenpropimorph Abietic acid 1 III-3-41* DCOIT Tebuconazole/ Sodium acetate 3 Propiconazole *denotes Comparative Example OIT and CMIT were used at 60 ppm, while DCOIT was used at 30 ppm.

(229) The data in the above tables show that each of the wood treated with a composition of the invention achieve a score of 1 after 24 weeks' exposure, meaning that only insignificant levels of surface staining are observed. In contrast, the comparative composition containing a saturated acid (formulation III-3-66) only achieves a score of 2, meaning that significant levels of surface staining are observed.

(230) In addition, the data show that the use of the combination of three components in accordance with the in accordance with the invention achieves better results that the individual ingredients when used on their own or in combination with only one other component. For example, formulations III-1-8, III-1-9, III-1-14, III-2-22 and III-2-23 each give scores of 2 or 3, whereas formulation III-3-30 achieves a score of 1. Thus, the combination of OIT, tebuconazole/propiconazole and dehydroacetic acid is achieving much better results than could have been expected based on the results of only one or two of these ingredients being used in combination, i.e. three way synergy is present.

(231) The data also show that some of the two-way combinations are also very effective even without the third ingredient. Thus, combinations of OIT and sodium benzoate or methyl benzoate/NaOH achieve a score of 1 even without the organic fungicidal timber decay preservative.

(232) The result obtained for formulation III-1-13 shows that CMIT is very effective even when used alone at 60 ppm, achieving a score of 1. However, the addition of an unsaturated acid and organic fungicidal timber decay preservative still leads to a visible improvement in the treated wood, even if the improvement is not shown in the score that the wood achieves.

(233) Thus, FIG. 19 shows blocks treated with CMIT on its own (formulation III-1-13), while FIGS. 20a and 20b show blocks treated with fenpropimorph and abietic acid (formulation III-2-28) and together with CMIT (formulation III-3-40). FIG. 20a clearly shows that formulation III-2-28 is ineffective at preventing surface staining, yet when used in combination with CMIT provides blocks that are even less stained that when using CMIT alone (compare FIG. 20b and FIG. 19). Thus, abietic acid and fenpropimorph enhance the efficacy of CMIT at preventing surface staining even though these compounds have no significant activity at preventing surface staining when used alone.

(234) The same result is seen with cyproconazole and oleic acid, as shown in FIG. 21a (cyproconazole and oleic acid, formulation III-2-25) and 21b (CMIT, cyproconazole and oleic acid, formulation III-3-37).

Example 4

(235) Using the same protocol as Example 3, the following formulations were tested:

(236) Formulation IV-1

(237) This formulation was formed from 0.95% of the concentrate in III-1-9, 0.008% of the concentrate in III-1-14 and 0.45% of the concentrate in III-1-5 in water.

(238) Formulation IV-2

(239) This formulation was formed from 0.95% of the concentrate in III-1-9, 0.016% of the concentrate in III-1-14 and 0.45% of the concentrate in III-1-5 in water.

(240) Formulation IV-3

(241) This formulation was formed from 0.95% of the concentrate in III-1-9, 0.05% of the concentrate in III-1-14 and 0.45% of the concentrate in III-1-5 in water.

(242) Formulation IV-4

(243) This formulation was formed from 0.95% of the concentrate in III-1-9, 0.1% of the concentrate in III-1-14 and 0.45% of the concentrate in III-1-5 in water.

(244) Formulation IV-5

(245) This formulation was formed from 0.95% of the concentrate in III-1-9, 0.17% of the concentrate in III-1-14 and 0.45% of the concentrate in III-1-5 in water.

(246) Each of the formulations therefore contained sodium benzoate, tebuconazole, propiconazole and OIT, but with the level of OIT varied from 5 ppm to 100 ppm. The results obtained after 24 weeks exposure are shown in the following table:

(247) TABLE-US-00046 Formulation OIT level (ppm) Score IV-1 5 2 IV-2 10 2 IV-3 30 1 IV-4 60 1 IV-5 100 1

(248) The data in the table show that best scores are obtained by using OIT levels above 10 ppm. However, even at 10 ppm the performance of this composition is surprisingly good. Photographs of the blocks treated with formulations IV-1 to IV-4 are shown in FIGS. 22a-22d, from which it can clearly be seen that even at 10 ppm OIT the composition provides excellent protection against surface staining.

Example 5

(249) A treatment solution was formed from the following formulation:

(250) TABLE-US-00047 Ingredient % w/w Preventol A8 (96.5% a.i Tebuconazole) 0.389 Permethrin 75:25 cis:trans (93.7% a.i.) 0.130 Wocosen 15TK (15.6% Propiconazole) 7.21 Foamban HV810G 0.35 Dowanol DPM 7.0 Ethoduomeen T25 2.0 Propionic acid 1.72 Dissolvine E39 1.5 Dehscofix CO130F 4.75 Sodium benzoate 22.5 Water 52.451

(251) The formulation was diluted to working strength (2.0% w/w) with water and combined with OIT at levels of 60 ppm.

(252) The solution was applied to Scottish Larch decks which were left exposed to the atmosphere for 16 months. FIGS. 23a and 23b show the untreated (control) and treated decking prior to exposure, while FIGS. 24a and 24b show the untreated (control) and treated decking after 16 months. These Figures clearly show that the untreated wood developed significant surface staining, while the treated wood remained relatively stain free for the entire period. The formulation of the invention therefore provides excellent protection against surface staining for a significant period of time, well in excess of 12 months.