Composition of a timber formulation comprising Cu salts and organic cyclic ingredients for the preservation of timber for decks

Abstract

This invention relates to a composition, a process for producing a composition, a timber formulation, a process for producing a timber formulation, a construction comprising the timber formulation and a use of the construction comprising the timber formulation are herein disclosed. The composition can include a Cu-salt, a first cyclic organic compound comprising a B heteroatom and at least one further B-free cyclic organic compound. The composition and timber formulation herein disclosed are designed as wood preservatives and may be used as part of a timber preserving treatment.

Claims

1. A composition comprising; i. a Cu-salt ii. at least one first cyclic organic compound comprising a B heteroatom in a cycle; iii. at least one further B free cyclic organic compound comprising a heteroatom selected from the group of O, N, S, or P, or a combination of at least two thereof in a cycle.

2. The composition according to claim 1, wherein the B heteroatom is negatively charged in the at least one first cyclic organic compound comprising a B heteroatom.

3. The composition according to claim 1, wherein the composition further comprises at least two different B free cyclic organic compounds.

4. The composition according to claim 3, wherein the at least two different B free cyclic organic compounds differ in at least one of the following structural terms: (a) the number of halogen atoms; (b) number of cycles; (c) number of heteroatoms other than halogens.

5. The composition according to claim 1, wherein the copper is present in the composition in a concentration in a range from 0.02-80 wt.-%.

6. The composition according to claim 1, wherein at least 60 wt.-% of the copper pre-sent in the composition has a particle size in the range from 1-1000 nm.

7. The composition according to claim 1, wherein the copper has a d.sub.50 value in the range from 0.5-500 nm.

8. The composition according to claim 1, wherein the copper has a d.sub.90 value in the range from 0.5-2000 nm.

9. The composition according to claim 1, wherein the copper has a d.sub.10 value in the range from 0.08-500 nm.

10. The composition according to claim 1, wherein the Cu-salt is dispersed in a solvent wherein the solvent is a polar solvent, in order to obtain a liquid phase.

11. The composition according to any of claim 10, wherein the concentration of solvent lies in a range preferably from 1-60 wt.-% based on the total weight of the composition.

12. The composition according to claim 1, wherein the first cyclic organic compound is present in the composition in a range from 0.1-60 wt.-% based on the total weight of the composition.

13. The composition according to claim 1, wherein the at least one further cyclic compound is present in the composition in a range from 0.01-70 wt.-% based on the total weight of the composition.

14. The composition according to claim 1, wherein the first cyclic organic compound is a betain or its derivative or both.

15. The composition according to claim 1, wherein the further organic compound is a triazole or its derivative or both.

16. The composition according to claim 1, wherein the first cyclic organic compound has a moiety of the general formula (I): ##STR00005## wherein in formula (I), X is selected from elements P, N, or B; Y is B; R1, R2 are independently from each other a saturated linear hydrocarbon containing from 1-20 C atoms; and m and n are independently from each other any integer value in the range from 1-20.

17. The composition according to claim 1, wherein the further cyclic organic compound has a moiety of the general formula (II): ##STR00006## wherein in formula (II), R3 is a heteroatom selected from elements C or N; R4 is a non-C heteroatom selected from elements, N, O or S; R5 is a heteroatom selected from elements C or N; R6 is a heteroatom selected from elements, C, N, O or S; and R7 is H, or comprises an organic moiety wherein the organic moiety can comprise at least one heteroatom selected from the group of C, H, O, N, halogen, or a combination of at least two thereof.

18. The composition according to claim 1, wherein the at least one further B free cyclic organic compound is selected from the group consisting of triadimefon, cyproconazol, tebuconazol, propriconazole or salts of each thereof.

19. The composition according to claim 3 wherein the at least two further B free cyclic organic compounds are tebuconazol and propriconazole or salts of each thereof.

20. A process for producing a composition, wherein the process comprises at least the following steps; i. providing a first cyclic organic compound comprising a B heteroatom; ii. providing at least one further B free cyclic organic compound comprising a heteroatom selected from the group of O, N, S, or P, or a combination of at least two thereof in a cycle; iii. providing a Cu-salt; iv. contacting the first cyclic organic compound comprising a B heteroatom with the at least one further B free cyclic organic compound in a solvent in order to obtain a solution; and v. contacting the solution of step (iv) with a Cu-salt in order to obtain the composition.

21. The process according to claim 20 wherein the Cu-salt is comprised in a liquid phase comprising a solvent.

22. The process for producing a composition according to claim 20, wherein the composition comprises at least two different further B free cyclic organic compounds.

23. The process for producing a composition according to claim 22, wherein in step iv. the contacting is performed at a temperature in the range from 30-80° C.

24. The process for producing a composition according to claim 20, wherein the first cyclic organic compound comprising a B heteroatom and the at least one further cyclic organic compound are contacted in a ratio of at least 1:25, wherein 1 is the concentration of the first cyclic organic compound and 25 is the concentration of the at least one further cyclic organic compound.

25. The process for producing a composition according to claim 20 wherein the Cu-salt liquid phase, is prepared at a temperature in the range from 5-60° C.

26. The process for producing a composition according to claim 20, wherein Cu-salt is ground.

27. The process for producing a composition according to claim 26, wherein the Cu-salt is ground until at least 50 wt.-% of the particles are less than 2000 nm in size.

28. The process for producing a composition according to claim 26, wherein the Cu-salt is ground until less than or equal to 30 wt.-% of the particles are smaller than 100 nm in size, based on the total weight of the composition.

29. The process for producing a composition according to claim 20, wherein the composition comprises: i. a Cu-salt ii. at least one first cyclic organic compound comprising a B heteroatom in a cycle; iii. at least one further B free cyclic organic compound comprising a heteroatom selected from the group of O, N, S, or P, or a combination of at least two thereof in a cycle.

30. A timber formulation comprising: a. a composition according to claim 1; and b. a timber; wherein the composition is present in the timber.

31. The timber formulation according to claim 30, wherein the timber comprises sap-wood in a range from 10-80 wt.-% of the timber.

32. A process for producing a timber formulation comprising the following process steps: a. providing a timber; b. applying an under-atmospheric pressure (vacuum); c. contacting the timber with a composition according to claim 1; d. applying an over-atmospheric pressure to the vessel in order to obtain the timber formulation.

33. The process according to claim 32, wherein the vacuum is in a range from 0.01 to 2.0 bar.

34. The process according to claim 32, wherein the water content of the timber is in a range from 5-50 wt.-% of the timber.

35. The process according to claim 32, wherein the over-atmospheric pressure is in the range from 1-15 bar.

36. The process according to claim 32, wherein the timber comprises at least 10 wt.-% sapwood.

37. The process according to claim 32, wherein the contacting in step c. is performed with a treating solution, wherein the treating solution comprises the composition being diluted by a solution solvent, wherein the concentration of the composition is in the range from 0.05-70 wt.-%, based on the treating solution.

38. A construction comprising a timber formulation according to claim 30 or obtainable by a process according to claim 32.

39. The construction according to claim 38, wherein the construction comprises an exterior surface which comprises the timber formulation, according to claim 30 or obtainable by a process according to claim 32.

40. The construction according to claim 39, wherein the exterior surface is of a sawed timber.

41. A use of a composition obtained by a process according to claim 20 to protect the exposed surface of a timber.

42. The use according to claim 41, wherein the timber is part of a wood comprising product.

43. The use according to claim 41, wherein the timber is comprised in an exterior surface.

44. A process for producing a timber formulation comprising the following process steps: a. providing a timber; b. applying an under-atmospheric pressure (vacuum); c. contacting the timber with a composition obtainable by the process according to claim 20; d. applying an over-atmospheric pressure to the vessel in order to obtain the timber formulation.

Description

DESCRIPTION OF DRAWINGS

(1) The drawings are for illustrative purposes only, they are not a scale representation of the invention and are not to be considered as limiting the scope of the invention. The figures show in:

(2) FIG. 1 a process flow diagram of the process according to the invention;

(3) FIG. 2 a schematic drawing showing the exterior of a vessel and compartment used according to the invention;

(4) FIG. 3 a schematic drawing of an open vessel with compartment comprising the composition according to the invention;

(5) FIG. 4 a schematic representation of a deck.

(6) FIG. 1 is a process flow diagram describing the process according to the invention from composition preparation through to timber testing. The steps followed are: I. contacting a first B comprising cyclic organic compound with at least one further B free cyclic organic compound in order to obtain a solution; II. preparing a liquid-phase Cu-salt; III. contacting, at ambient temperature, solution I with liquid-phase II in order to obtain the composition according to the invention; IV. timber appropriately spaced via separators, placed in a vessel; V. vacuum of 0.1 bar is applied to the vessel for 30 minutes at 25° C.; VI. composition of III. is introduced to the vessel; VII. over-atmospheric pressure of 10 bar is applied to the vessel for 90 minutes at 25° C. in order to obtain treated timber; VIII. pressure returned to ambient pressure and composition of III. is removed from the vessel; IX. the treated timber is dried at ambient temperature.

(7) FIG. 2 shows a vessel 100 closed by a door 101 situated above a compartment 112.

(8) FIG. 3 shows a vessel under working conditions 102 with an open door 103 allowing an interior view 107 of both the vessel 100 and compartment 112. Inside the vessel 107 are timbers 104, with said timbers 104 being separated horizontally by a separator 105 and vertically by separators 106. The vessel 100 is positioned above compartment 112 wherein the composition according to the invention 113 is stored during the treatment process. The composition 113 is transported into the vessel 100 via an opening 111 in the cylindrical tubing 110 positioned within the vessel 100, wherein said cylindrical tubing 110 comprises two valve mechanisms 109 and a seal 108. By adjusting the valve mechanisms 109 and the pressure applied to the interior of the vessel 107, the composition 113 is transported from the compartment 112 to the interior of the vessel 107 and the timbers 104 are treated.

(9) FIG. 4 is a representation of a deck 205 extending from the exterior wall of a construction 200, with said wall comprising both a door 206 and window 207. The deck is comprised of horizontal timbers 202 joined together at interfaces 203. Said joined timbers 202 are supported by perpendicular timbers placed underneath 201. The deck is finished by a timber railing 204 wherein said timbers share interfaces primarily at the vertices and edges of the horizontal timbers 202. It should be noted that this figure is a general representation of a deck and is for illustration purposes only. Decks of various sizes, designs and other variables are herein also included.

EXAMPLES

(10) The invention is now explained by means of examples which are intended for illustration purposes only and are not to be considered as limiting the scope of the invention. In particular the timbers prepared according to the invention and the examples herein described, are for illustration purposes only. There are numerous possible combinations of reaction conditions applicable to this invention. The selected examples are chosen to give a general, yet detailed description of results and are not to be considered as limiting the scope of the invention.

Example 1

Product A—Dissolved Copper

(11) Solution I

(12) At room temperature, 200.0 g of basic copper carbonate (CAS number 12069-69-1) was slowly dissolved in a solution of 371.0 g of monoethanol amine (commercially available from Aldrich) in 236.5 g water under vigorous stirring. Once the copper carbonate completely dissolved, the pH value of the solution was adjusted with carbon dioxide to 8.8-9.0.

(13) Solution II

(14) At 50° C., a solution of 2.0 g of propiconazol (CAS number 60207-90-1) in 2.0 g propylene glycol (commercially available from Aldrich) and 2.0 g tebuconazol (CAS number 107534-96-3) were added to 100.0 g di-decyl-poly-oxethyl-ammoninum borate (CAS number 214710-34-6) and stirred until completely dissolved.

(15) After cooling solution II to room temperature, solution II was added slowly to solution I under continuous stirring in order to obtain a homogeneous solution, hereinafter referred to as Product A. The Product A contained 33.3 wt.-% Active Ingredient (AI). The AI contained 33.3 wt.-% copper.

(16) Table 1 shows the reactants of product A and their respective amounts, whilst table 2 gives the active ingredients and their respective amounts.

(17) TABLE-US-00001 TABLE 1 Compounds Amount [g] Normalized [%] Copper carbonate 50% 200.00 21.89% MEA 371.00 40.61% Water 236.50 25.89% Propiconazol 2.00 0.22% Propylene glycol 2.00 0.22% Tebuconazol 2.00 0.22% DPAB TGAI 100.00 10.95% Product A 913.50 100.00% MEA = monoethanolamine, DPAB = Crude betain with an Al content of 59%, TGAl = Technical grade Al, Al = the active ingredient, DPAB TGAl = DPAB 59% Al - only 59% are active Al.

(18) The ratios of copper:azol, copper:betain and betain:azol were 1:25, 1:1 and 1:25 respectively, wherein the azol is the sum of propiconazol and tebuconazole. The copper content based on the amount of copper oxide is 33.3%.

(19) TABLE-US-00002 TABLE 2 Actives Amount [g] Normalized [%] Copper oxide 125.16 66.52% DPAB 59% AI 59.00 31.36% Propiconazol 2.00 1.06% Tebuconazol 2.00 1.06% Product A 188.16 100.00% DPAB = Crude betain with an Al content of 59%, TGAl = Technical grade Al, Al = the active ingredient, DPAB TGAl = DPAB 59% Al - only 59% are active Al.

Example 2

Product B—Micronized Copper

(20) Dispersion I

(21) 400.0 g of copper carbonate (CAS number 12069-69-1) was dispersed in a solution of 144.0 g of water. After stirring for 30 min the mixture was placed in a commercial grinding mill and ground until 70 wt.-% or more of the particles were less than 1000 nm in size, and 10 wt.-% or less of the particles, were smaller than 100 nm in size.

(22) Solution II

(23) At 50° C., a solution of 4.0 g of propiconazol (CAS number 60207-90-1) in 4.0 g, propylene glycol (commercially available from Aldrich) and 4.0 g tebuconazol (CAS number 107534-96-3) were added to 200.0 g di-decyl-poly-oxethyl-ammoninum borate (CAS number 214710-34-6) and stirred until the dissolving process was complete and a homogeneous solution was obtained.

(24) After cooling solution II to room temperature, solution II was added slowly to dispersion I under continuous stirring in order to obtain a homogeneous dispersion hereinafter referred to as Product B. The Product B contained 80.4 wt.-% Active Ingredient (AI). The AI contained 33.3 wt.-% copper.

(25) Table 3 shows the reactants of Product B and their respective amounts, whilst table 4 gives the active ingredients and their respective amounts.

(26) TABLE-US-00003 TABLE 3 Compounds Amount [g] Normalized [%] Copper carbonate 50% 400.00 52.91% Water 144.00 19.05% Propiconazol 4.00 0.53% Propylene glycol 4.00 0.53% Tebuconazol 4.00 0.53% DPAB TGAI 200.00 26.46% Product B 756.00 100.00% DPAB = Crude betain with an Al content of 59%, TGAl = Technical grade Al, Al = the active ingredient, DPAB TGAl = DPAB 59% Al - only 59% are active Al.

(27) MEA=monoethanolamine, DPAB=Crude betain with an AI content of 59%, TGAI=Technical grade AI, AI=the active ingredient, DPAB TGAI=DPAB 59% AI—only 59% are active AI.

(28) The ratios of copper:azol, copper:betain and betain:azol were 1:25, 1:1 and 1:25 respectively, wherein the azol is the sum of propiconazol and tebuconazole. The copper content based on the amount of copper oxide is 33.3%.

(29) TABLE-US-00004 TABLE 4 Actives Amount [g] Normalized [%] Copper oxide 250.31 66.52% DPAB 59% AI 118.00 31.36% Propiconazol 4.00 1.06% Tebuconazol 4.00 1.06% Product B 376.31 100.00% DPAB = Crude betain with an Al content of 59%, TGAl = Technical grade Al, Al = the active ingredient, DPAB TGAl = DPAB 59% Al - only 59% are active Al.

Example 3

Product C—Betain & Triadimefon

(30) At 50° C., 14.0 g of triadimefon and 36.0 g of water were added to 950.0 g di-decyl-poly-oxethyl-ammoninum borate (CAS number 214710-34-6) and stirred until completely dissolved in order to obtain a homogeneous solution, hereinafter referred to as Product C.

(31) Unlike products A and B, product C contained 0.00 wt.-% copper.

(32) Table 5 shows the reactants of product C and their respective amounts, whilst table 6 gives the active ingredients and their respective amounts.

(33) TABLE-US-00005 TABLE 5 Compounds Amount [g] Normalized [%] Water 36.00 3.60% Triadimefon 14.00 1.40% DPAB TGAI 950.00 95.00% Product C 1000.00 100.00% Triadimefon = triazole, i.e. an N-heterocycle, DPAB = Crude betain with an Al content of 59%, TGAl = Technical grade Al, Al = the active ingredient, DPAB TGAl = DPAB 59% Al - only 59% are active Al.

(34) The ratios of copper:azol, copper:betain and betain:azol were 0:0, 0:0 and 1:67.86 respectively, wherein the azol is triadimefon.

(35) TABLE-US-00006 TABLE 6 Actives Amount [g] Normalized [%] DPAB TGAI 950.00 98.55% Triadimefon 14.00 1.45% Product C 964.00 100.00% Triadimefon = triazole, i.e. an N-heterocycle, DPAB = Crude betain with an Al content of 59%, TGAl = Technical grade Al, Al = the active ingredient, DPAB TGAl = DPAB 59% Al - only 59% are active Al.

Example 4

Product D—Betain & Cyproconazol

(36) At 50° C., 3.0 g of cyproconazol and 497.0 g of water were added to 500.0 g di-decyl-poly-oxethyl-ammoninum borate (CAS number 214710-34-6) and stirred until completely dissolved in order to obtain a homogeneous solution, hereinafter referred to as Product D.

(37) As in product C, product D also contained 0.00 wt.-% copper.

(38) Table 7 shows the reactants of product D and their respective amounts, whilst table 8 gives the active ingredients and their respective amounts.

(39) TABLE-US-00007 TABLE 7 Compounds Amount [g] Normalized [%] Water 497.00 49.70% Cyproconazol 3.00 0.30% DPAB TGAI 500.00 50.00% Product D 1000.00 100.00% DPAB = Crude betain with an Al content of 59%, TGAl = Technical grade Al, Al = the active ingredient, DPAB TGAl = DPAB 59% Al - only 59% are active Al.

(40) The ratios of copper:azol, copper:betain and betain:azol were 0:0, 0:0 and 1:166.67 respectively, wherein the azol is cyproconazol.

(41) TABLE-US-00008 TABLE 8 Actives Amount [g] Normalized [%] DPAB TGAI 500.00 99.40% Cyproconazol 3.00 0.60% Product D 503.00 100.00% DPAB = Crude betain with an Al content of 59%, TGAl = Technical grade Al, Al = the active ingredient, DPAB TGAl = DPAB 59% Al - only 59% are active Al.

Comparative Example

(42) For comparison the product NatureWood-CA, commercially available from Osmose Inc., USA was employed. The NatureWood-CA contained as Active Ingredient (AI): 50 parts by weight basic copper carbonate (CAS number 12069-69-1) to 1 part by weight tebuconazole (CAS number 107534-96-3) to 1 part by weight propiconazole (CAS number 60207-90-1) and no di-decyl-poly-oxethyl-ammoninum borate (CAS number 214710-34-6). See table 9.

(43) TABLE-US-00009 TABLE 9 Compounds Amount [g] Normalized [%] Copper carbonate 50% 50.00 96.15% Propiconazol 1.00 1.92% Tebuconazol 1.00 1.92% Comparative example 52.00 100.00%

(44) The ratios of copper:azol, copper:betain and betain:azol were 1:25, 0:0 and 0:0 respectively, wherein the azol is the sum of propiconazol and tebuconazole. Table 10 gives the active ingredients and their respective amounts. The copper content based on the amount of copper oxide is 49.3%.

(45) TABLE-US-00010 TABLE 10 Actives Amount [g] Normalized [%] Copper oxide 31.29 93.99% Propiconazol 1.00 3.00% Tebuconazol 1.00 3.00% Comparative example 33.29 100.00%

(46) Preparation of Timbers Using Products A-D/Comparative

(47) Timber pieces were positioned in a treating vessel. Over a period of 30 minutes a pressure of 0.1 bar was applied. The treating solution containing a Product was sucked into the vessel. Then the pressure in the vessel was increased to 10 bar at 25° C. for 90 minutes. Afterwards the pressure was set to ambient pressure and the remainder of the treating solution was removed. The impregnated timber pieces were dried at ambient temperature. Further details are given in the tables and standards below.

(48) Test E7-9 on Product B

(49) The timber employed in the tests was Southern yellow pine. The Standards of the American Wood Protection Association were applied for the test E7-09 as amended in 2009, E18-06 as revised in 2006 and E16-09 as amended in 2009. The details are provided in table 11 below.

(50) The timber employed in the tests was Southern yellow pine. The Standards of the American Wood Protection Association were applied for the test E7-09 as amended in 2009 (tables 11A and 11B), E18-06 as revised in 2006 (tables 12A and 12B) and E16-09 as amended in 2009 table 12C). The details of all tests are provided in the tables below.

(51) TABLE-US-00011 TABLE 11A Conc. of Av. absorption of Av. AI Av. copper oxide Av. DPAB Av. propiconazol Av. tebuconazol treating solution treating solution retention retention retention retention retention Av. rating [wt.-% AI in in timber in timber in timber in timber in timber in timber test site Product water] [l/m.sup.3] [kg/m.sup.3] [kg/m.sup.3] [kg/m.sup.3] [kg/m.sup.3] [kg/m.sup.3] Hawaii Product 0.400% 641 2.56 1.71 0.80 0.03 0.03 9.40 B Comparative 0.371% 690 2.56 2.41 0 0.08 0.08 9.55 MCA-C

(52) TABLE-US-00012 TABLE 11B Av. rating Av. after rating after 2 years 3 years Av. rating after Av. rating after test site test site 5 years test site 2 years test site Product Hawaii Hawaii Hawaii North Carolina Product B 9.40 9.50 8.56 9.85 Comparative 9.55 9.60 8.75 10.00 MCA-C

(53) Tables 11A and 11B show that Product B is sufficiently active to achieve similar results to those obtained from the comparative example. Product B however, is able to retain DPAB to 0.80 kg/m.sup.3 whereas the comparative example cannot retain DPAB at all (0.00 kg/m.sup.3).

(54) Tables 11A and 11B further show that Product B, with a significantly reduced amount of copper (1.71 kg/m.sup.3) compared to the amount of copper in the comparative example (2.14 kg/m.sup.3), is capable of achieving a similar level of preservation as that of the comparative example. The E18-09 test produced even better results as can be seen in tables 12A and 12B.

(55) TABLE-US-00013 TABLE 12A Conc. of Av. absorption of Av. AI Av. copper oxide Av. DPAB Av. propiconazol Av. tebuconazol Av. rating treating solution treating solution retention retention retention retention retention test site [wt.-% AI in in timber in timber in timber in timber in timber in timber North Product water] [l/m.sup.3] [kg/m.sup.3] [kg/m.sup.3] [kg/m.sup.3] [kg/m.sup.3] [kg/m.sup.3] Carolina Product 0.167% 637 1.06 0.71 0.33 0.01 0.01 10.00 B Comparative 0.167% 647 1.08 1.02 0 0.03 0.03 9.90 MCA-C

(56) TABLE-US-00014 TABLE 12B Av. rating after Av. rating after Av. rating after 2 years test site 5 years test site 2 years test site Product Hawaii Hawaii North Carolina Product B 9.60 8.85 10.00 Comparative 9.70 9.17 9.90 MCA-C

(57) Here it can be seen that less copper and azol are required compared to the corresponding values in table 11, yet the average rating result is higher, at 10.00 compared to 9.40 in table 11.

(58) Here it can be seen that less copper and azol are required compared to the corresponding values in tables 11A and 11B, yet the average rating result is higher, at 10.00 (table 12B) compared to 9.40 in table 11B.

(59) From tables 12A and 12B, Product B, again with a significantly reduced amount of copper (0.71 kg/m.sup.3) compared to the amount of copper in the comparative example (1.02 kg/m.sup.3), is capable of achieving a similar level of preservation as that of the comparative example, and indeed outperforms the comparative example in the average rating test (after 2 years, test site in North Carolina).

(60) TABLE-US-00015 TABLE 12C Av. rating Conc. of Av. absorption of Av. AI Av. copper oxide Av. DPAB Av. propiconazol Av. tebuconazol after 2 years treating solution treating solution retention retention retention retention retention test site [wt.-% AI in in timber in timber in timber in timber in timber in timber North Product water] [l/m.sup.3] [kg/m.sup.3] [kg/m.sup.3] [kg/m.sup.3] [kg/m.sup.3] [kg/m.sup.3] Carolina Product 0.167% 573 0.96 0.64 0.30 0.01 0.01 9.50 B Comparative 0.167% 585 0.98 0.92 0 0.03 0.03 9.61 MCA-C

(61) Table 12C shows similar results, i.e., Product B is capable of achieving a similar level of preservation (9.50) as that of the comparative example (9.61). Product B achieves this, however, not only with a lower amount of copper present (0.64 kg/m.sup.3 compared to 0.92 kg/m.sup.3), but also with a lower absorption of the treating solution itself (573 l/m.sup.3 (prod. B) compared to 585 l/m.sup.3 (comparative). These are significant and unexpected findings.

(62) Test EN113 on Product C

(63) In both tables 13 and 14 the standard applied is EN113. Prior to EN113, the timber was washed according to EN84. The type of timber used was pine.

(64) Tables 13 and 14 show the average retention of the active ingredient (AI) in Product C when it is exposed to both “poria placenta” (table 13) and “coniophora puteana” (table 14). Comparisons are also made with retention values of DPAB and the azol (triadimefon) in the timber. Average AI retention values are required in order to pass the EN113 Standard.

(65) TABLE-US-00016 TABLE 13 Average a.i. retention against poria Average DPAB Average azol placenta retention in retention in Product [kg/m.sup.3] timber [kg/m.sup.3] timber [kg/m.sup.3] DPAB TGAI 4.50 azol 0.10 Product C 1.83 1.80 0.03 DPAB = Crude betain with an Al content of 59%, TGAl = Technical grade Al, Al = the active ingredient, DPAB TGAl = DPAB 59% Al - only 59% are active Al.

(66) Table 13 shows that when using Product C, an AI retention value of 1.83 can be achieved with using less DPAB (1.80 kg/m.sup.3 instead of 4.50 kg/m.sup.3) and less azol (0.03 kg/m.sup.3 instead of 0.10 kg/m.sup.3).

(67) TABLE-US-00017 TABLE 14 Average a.i. retention Average against coniophora DPAB retention Average azol puteana in timber retention in Product [kg/m.sup.3] [kg/m.sup.3] timber [kg/m.sup.3] DPAB TGAI 7.40 azol 0.10 Product C 2.89 2.85 0.04 DPAB = Crude betain with an Al content of 59%, TGAl = Technical grade Al, Al = the active ingredient, DPAB TGAl = DPAB 59% Al - only 59% are active Al.

(68) Table 14 shows similar results, with an AI retention value of 2.89 when using smaller amounts of both cyclic compounds DPAB (2.85 kg/m.sup.3 instead of 7.40 kg/m.sup.3) and azol (0.04 kg/m.sup.3 instead of 0.10 kg/m.sup.3). These findings show that by reducing the amounts of DPAB and azol by factors of 2.5 and 10 respectively; results are improved, furthermore, they are improved in the absence of copper.

(69) Test EN113 on Product D

(70) In both tables 15 and 16 the standard applied is EN113. Prior to EN113, the timber was washed according to EN84. The type of timber used was pine.

(71) As for product C, tables 15 and 16 show the average retention of the active ingredient (AI) in Product D when it is exposed to both “poria placenta” (table 15) and “coniophora puteana” (table 16). Comparisons are also made with retention values of DPAB and the azol (cyproconazol) in the timber. The average AI retention values are required in order to pass the EN113 Standard.

(72) TABLE-US-00018 TABLE 15 Average a.i. retention against poria Average DPAB Average azol placenta retention in retention in product [kg/m.sup.3] timber [kg/m.sup.3] timber [kg/m.sup.3] DPAB TGAI 4.50 azol 0.10 Product D 1.16 1.15 0.01 DPAB = Crude betain with an Al content of 59%, TGAl = Technical grade Al, Al = the active ingredient, DPAB TGAl = DPAB 59% Al - only 59% are active Al.

(73) Table 15 shows that when using product D, a higher AI retention value of 1.16 against poria placenta can be achieved, again with using less DPAB (1.15 kg/m.sup.3 instead of 4.50 kg/m.sup.3) and azol (0.01 kg/m.sup.3 instead of 0.10 kg/m.sup.3).

(74) TABLE-US-00019 TABLE 16 Average a.i. retention Average against coniophora DPAB retention Average azol puteana in timber retention in Product [kg/m.sup.3] [kg/m.sup.3] timber [kg/m.sup.3] DPAB TGAI 7.40 azol 0.10 Product D 2.41 2.40 0.01 DPAB = Crude betain with an Al content of 59%, TGAl = Technical grade Al, Al = the active ingredient, DPAB TGAl = DPAB 59% Al - only 59% are active Al.

(75) Table 16 shows similar results, with an AI retention value of 2.41 when using smaller amounts of both cyclic compounds DPAB (2.40 kg/m.sup.3 instead of 7.40 kg/m.sup.3) and azol (0.01 kg/m.sup.3 instead of 0.10 kg/m.sup.3). These findings show that by again reducing the amounts of DPAB and azol by factors of 3 and 10 respectively; results are improved, once more noting that these results are achieved in the absence of copper.

(76) From the above examples, objects of the invention have herein been fulfilled. A partial solution to at least one of the problems encountered in the state of the art in relation to a chromium-free wood preservative which can remain effective over a long period of time has been achieved. These results show that an increased performance can be achieved with a reduced amount of copper in the composition, thus indicating that the dispersion of copper particles within the composition and formulation is homogeneous, and therefore can remain effective at lower concentrations. These results show that by combining at least 2 heterocyclic B free organic compounds, both of which comprise at least one halogen atom, with a further cyclic organic compound comprising B, a synergy will be produced; and in doing so, will allow for a significant improvement in the AI retention in timber. When these compounds are further combined with copper, the results herein show that the same if not an improved performance against fungi (poria placenta/coniophora puteana) can be achieved compared to the comparative examples. Products A and B contain 66.52% (normalized) active copper compared with 93.99% (normalized) active copper used in the comparative example. This provides an additional advantage to the present invention in that less active organic ingredients are needed in order to achieve a quality timber protection. It is also clear that the invention has proven a reduced need for copper in a timber preservative. With a better performing composition, the longevity, durability and mechanical stability of timber and any construction using said timber will also be improved.

REFERENCE LIST

(77) 100 Vessel (100). 101 Sealed door (101) of vessel (100). 102 Interior view of vessel (100) and compartment (112). 103 Open door (103) of vessel (100) showing the interior (107) and layout of timbers (104) during treatment process. 104 Timbers (104) inserted into vessel (100). 105 Separators (105) used to create a horizontal gap between the stacked timbers (104). 106 Separators (106) used to create a vertical gap between the stacked timbers (104). 107 Interior of vessel (100). 108 Seal of cylindrical tubing (110) positioned within vessel (100). 109 Valve mechanism comprised in the cylindrical tubing (110) positioned within the vessel (100), which allows for transport of composition (113) from compartment (112) into the vessel. 110 Cylindrical tubing positioned within the vessel (100). 111 Opening at the end of cylindrical tubing (110) positioned within the vessel (100) to allow uptake of the composition (113) according to the invention from container (112). 112 Compartment comprising the composition (113). 113 The composition according to the invention. 200 Exterior wall (200) of a construction with exit onto a decked area (205). 201 Timber (201) preserved according to the invention, placed underneath and perpendicular to the upper layer of timbers (202) in order to give support to a deck (205). 202 Timbers (202) preserved according to the invention, connected at interfaces (203) in order to produce a deck (205). 203 Interfaces (203) of preserved timbers connected to form a deck (205). 204 Timbers (204) preserved according to invention, connected perpendicularly to horizontal timbers (202) of the deck (205) and vertical exit wall leading onto deck (200) in order to enclose the deck (205). 205 A deck (205) produced by assembling together timbers (201, 202, 204) preserved according to the invention. 206 Door of exterior wall of construction. 207 Window of exterior wall of construction.