FI59945C - CONTAINING SYNERGISTIC BLANDING INNEHOLLAND AND TRIORGANOTENNFOERENING OCH ETT KVATERNAERT AMMONIUMSALT FOER SKYDDANDE AV CELLULOSAHALTIGT MATERIAL - Google Patents

Description

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Patent- och regitterctyrelaen '7 AmMcm ucta «4 ocfc utMfcrMtan publkmrf 3i.07.8l (32) (33) (31) ho *« «y • tuofkm» —e «g« rd priority 09.03.73 15.06.73 English-England (GB) 11 ^ 19/73, • 285UU / 73 (71) Albright & Wilson Limited, P.0. Box No. 3, Oldbury, Warley, Worcestershire, England-England (GB) (72) John Leslie Bennett, Wolverhampton, Glyn Miller, Warley, Worcestershire, Barry Arthur Richardson, Winchester, Hampshire, England-England (GB) (7U) Oy Kolster Ab (5U) Use of a synergistic mixture comprising a triorganotin compound and a quaternary ammonium salt for the protection of a cellulosic material such as plywood, particle board and hardboard.

The use of trialkyltin compounds, especially tributyltin oxide, as a wood preservative has increased in recent years. However, the use of such compounds has been possible only if an organic solvent has been used for them. This has severely limited their use in protecting wood and performing certain remedial treatments (i.e., treatment of wood and wood products after wood-destroying fungi have damaged and partially destroyed the wood) in which organic solvents are commonly used to prevent wood swelling during treatment.

Previous FI patent application 31U8 / 73 describes the treatment of wood with mono-organotin compounds such as butyltin trichloride. These compounds are used in organic solution (examples) or e.g. in the form of an emulsion containing 2,59945 salts of quaternary anpqnium. The mono-organotin compounds can be used alone (examples) or mixed with organotin biocides such as tributyltin oxide. It has been noticed that the compositions of the application are not reproducible in terms of protective effect. It has now been found that wood can be protected by a combination of a triorganotin compound and a monoquat ammonium compound used to dissolve it in an aqueous system. This combination provides a better protective effect than the triorgano compound in the organic solvent system or by replacing the quaternary compound with other surfactants in the aqueous system.

An aqueous system containing an organotin compound, similar to systems previously used in masonry cleaning or as a biocide in a cooling water system, has surprisingly good performance as a wood preservative, i. to pre-treat the wood before the wood-destroying fungi have been able to act on it. In addition, it has been found that the preparation used for wood has the total amount of organotin compound required to achieve a certain degree of protection, i. the prescribed load of the organotin compound on the wood, considerably less than that required in the case where the orgasmic tin compound is used in the form of a conventional naphtha-based preparation.

The present invention relates to the use of a synergistic composition for protecting a cellulosic material which is wood or a product made therefrom and which is substantially not contaminated with wood-destroying fungi, wherein the composition treating the cellulosic material comprises an aqueous system containing 0.01-0 - an organotin compound of the formula R 1 SnX or R 2 SnYSnR 2 in which R is an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group or a phenyl group, X is an inorganic atom or group and Y is a sulfur or oxygen atom, and a monoquatium ammonium salt, of the formula - - f (I) R * - N - R '"Z" R "" 3 59945 where R', R ", R, n and R" ", which may be the same or different, mean straight-chain or branched , a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkaryl group having γ to 19 carbon atoms, an aralkyl group having 7 to 27 carbon atoms, or an aryl group having 6 to 20 carbon atoms or the like alkylene oxycondensate, or two or three of said substituents may form together with a quaternary nitrogen atom or together with a quaternary and at least one additional heteroatom a saturated or unsaturated 5-> 6- or 7-membered heterocyclic ring, and Z is a water-soluble anion, in a sufficient amount to disperse the organic compound under the processing conditions to obtain a load of 0.15 to 1.5 kg of tmaorgasmic compound per m of wood or wood product.

As used herein, the term "load" in a cellulosic material is used in its conventional sense, namely, the absorption of a preservative (here an organotin compound) per unit volume of material, defined as a mass of impregnating liquid of known concentration absorbed by a cellulosic material of known volume. Useful organotin compounds include: bis (tri-n-butyltin) oxide bis (tri-n-butyltin) sulfide tri-n-butyltin acetate tri-n-butyltin acrylate tri-n-butyltin methacrylate tri-n-butyltin phosphate tri-n -butyylitinakloridi

The corresponding trihexyltin, tricyclohexyltin and triphenyltin compounds are also particularly useful. Tri-n-butyltin oxide is particularly preferred.

Particularly useful quaternary ammonium compounds are benzalkonium chlorides of formula f, * _ CÄH_CH „- n - R Cl 052 | CH3 where R is a mixture of alkyl groups having 8 to 18 carbon atoms but mainly C12 ', ·. · ·' · Benzethonium chloride u 59945 Γ3 / = \ (CH3) 3 C CH2 C - 0 - £> - ° (Ch2) 2 o (ch2) 2h - ch2c6h5 Cl ch3 ch3 and methylbenzetonium chloride; heks adekyy1 i -pyrri di ni um um or ori di / = \ Γ.

215 3 and hexadecylpyridinium bromide; hexadecyl trimethylammonium bromine di CH_ * I 3 C / -H__ - N - CH_ Br lb I 5 ch3 N- (acylaminoformylmethyl) pyridinium chloride; phenoxy ethyl dimethyl dodecyl ammonium bromide di / VoC2H-N212H25 Br "CH3 di-n-octyldimethyl ammonium bromide CH- + I 3 C8H1T -» - C8H1T Er CH3 and n-dodecylbenzyltrimethylammonium chloride. * · 5 59945 CH3 ^> -CH2 - [- CH3 C1 "ch3 _

The compositions of matter useful in the invention are suitably stored and transported in the form of a concentrate. Such concentrates generally contain from 1 to 20% by weight, preferably from 5 to 15% by weight, of an organotin compound and from 20 to 90% by weight, preferably from 35 to 50% by weight, of a quaternary compound, the remainder being mainly water. It is desirable that the quaternary compound and the organotin compound be present in a weight ratio of between 2: 1 and 6: 1, preferably about U: 1. For use, the concentrate is diluted with a sufficient amount of water to obtain an aqueous system of suitable concentration (i.e., 0.01-0.1; wt%, preferably 0.01-0.25 wt.% Of organotin compound). This dilution generally means one part concentrate per 10-100 parts, preferably 50-500 parts water depending on the percentage of tin in the original concentrate, e.g. a concentrate containing 10 # organotin compound can be diluted 1 + 0-1000-fold , preferably about 100-fold. According to the present invention, the preservatives can be applied to wood and similar products either alone or in combination with other preservatives, for example conventional poisons. Preferred quaternary ammonium salts themselves have biological, e.g. insecticidal, activity. Additives that can be used are those commonly used in aqueous mixtures. Such additives include, for example, water-soluble salts of chlorinated phenols such as sodium pentachlorophenate. They may also contain insecticidal agents. If desired, the preservatives can also be used in combination with other protective compositions, such as inorganic chromates or mixtures of dichromates. Preservatives are applied to wood or similar products in varying amounts depending on the nature of the substrate and its intended use. It has been found that a treatment which provides a load of 0.15 to 0.5 kg (per cubic meter of wood or a product made from it) of an organotin compound provides useful protection against common wood-destroying Vasido mycetes. A load of about 0.25 kg / m is generally sufficient to protect the normal material used in buildings.

There are many ways to apply a preservative to wood or wood products. It can be accomplished by soaking the wood to be protected in a solution containing a preservative until sufficient absorption of 6,59945 has occurred. However, the preservative is preferably added by means of vacuum and / or pressure impregnation methods designed to ensure that the preservative is completely absorbed into the substrate. In this case, the cellulosic material can be contacted with the aqueous system, the pressure is raised above atmospheric pressure while the material is in constant contact with the system, and the pressure is returned to atmospheric pressure so that the pressures and the amount of time maintained are sufficient to achieve the desired load. The material is preferably subjected to a pressure below atmospheric pressure before being contacted with the aqueous system. For example, the substrate may be placed in a chamber, the pressure in the chamber is reduced, the protective agent mixture is added, usually at room temperature, to cover the substrate, the pressure is raised and maintained above atmospheric pressure and then reduced to atmospheric pressure, possibly briefly maintained. Alternatively, the pressure reduction may initially be omitted. These methods, which use or do not use pressure reduction as a source, are known as Full cell technique and ihipty cell technique and are described in W.P.K. In Findley's book "The Preservation of Timber," Pub. Black 1962, pages 36 — U1 and G.M. Hunt and G.A. In Garrat's book "Wood Preservation," 3rd ed. American Forestry.Series, McGraw-Hill, 1967.

The concentration of the organotin compound in the aqueous system, the magnitudes of the pressures, the maintenance times of the overpressure and underpressure, and the nature of the cellulosic material affect the loading of the material. In this case, increasing the concentration or overpressure, maintaining the overpressure or underpressure, or decreasing the underpressure causes an increase in the load on the material. Changing the material to one with higher absorbency results in an increase in load. A similar effect is the treatment of a cellulosic material with a smaller cross-section. Generally, vacuum treatment times ranging from five minutes to two hours, usually from 10 minutes to 10 minutes, with a vacuum of less than 100 2 2 mm Hg are used. Overpressures in the range 2-20 kg / cm, e.g. 8-15 kg / cm are suitable with treatment times of 5 hours to 20 minutes, e.g. 2 hours to 30 minutes, with longer times being used at lower pressures.

These conditions are generally suitable for use with aqueous systems containing 0.05-0.25% organotin compound.

The aqueous systems used according to the invention are very useful for the protection of wood (or a solid product made from it) against the destruction of wood-destroying Basidomycetes such as Coniophora cerebella, Polystictus versicolor, Lenzites trabea and in particular Poria monticola. the latter is resistant to ordinary copper chromium arsenate preservatives.

The invention is illustrated in the following Examples 3-6, while Examples 1 and 2 illustrate the preparation of suitable concentrates.

Example 1

An aqueous preparation containing 10% bis (tri-n-methyltin) oxide and 10% alkylbenzyldimethylammonium chloride was prepared by stirring

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1 part bis (tri-n-butyltin) oxide with 8 parts Benzalkonium Cloride B.P. (a commercial aqueous preparation containing 50% by weight of alkylbenzyldimethylammonium chloride in which the alkyl groups contain from 8 to 18 carbon atoms) and by adding 1 part of water, all concentrations and parts being by weight.

Example 2

An aqueous preparation containing 10% bis (tri-n-butyltin) oxide and 1 * 0% (n-higher alkylbenzyl) trimethylammonium chloride was prepared by mixing 1 part bis (tri-n-butyltin) oxide with 8 parts Gloquat (a commercial aqueous preparation containing 50% (n-higher alkyl) trimethylammonium chloride) and by adding 1 part water, all concentrations and parts being by weight. The n-higher alkyl group substituted as a substituent on the benzyl group is assumed to be an n-dodecyl group.

Example 3

The wood preservative activity of bis (tri-n-butyltin) oxide (TBTO) in the preparations derived from the mixtures described in Examples 1 and 2 was compared using a mycological test with the activity of the same compound prepared using a petroleum ether solvent. In this experiment, pieces of pine, Pinus sylves-tris, 15 mm long and 10 x 7 mm in cross-section, were treated by vacuum impregnation with dilutions of three preparations to give different retentions of bis (tri-n-butyltin) oxide. After drying, the halves of the pieces treated with aqueous preparations were extracted by vacuum impregnation by impregnation with deionized water and then soaking in deionized water for 5 days, during which the water was changed daily. The extracted pieces were then dried and all pieces were exposed to the brownish-causing species Coniophora cerebella of the genus Basidiomycetes by placing the pieces of wood for 6 weeks in cultures with active soil and equipped with irrigation equipment. The weight losses caused by the fungus are shown in the following table: bis (tri-n-butyltin) oxide in light petroleum solvent e 59945 TBTO concentration TBTO load Decomposition in solution% volume / wood kg / m3 weight loss% volume unextracted 0.25 1 * 15 0 0.16 0.7¾ 1.1 0.10 0.1 + 5 6.5 0.063 0.27 18.6 0.01 + 0 0.18 15.8 hi s (tri-n-butyltin) oxy dia and benzyl alkyl dimethyl ammonium chloride dia containing aqueous preparation from Example 1.

TBT0 concentration TBT0 load Decomposition in solution% volume / wood kg / m3 weight loss% volume unextracted 0.063 0.1 + U 0 0.0l + 0 0.28 0 0.025 0.18 6.0 0.016 0.11 2 .0 0.010 0.07 12.5 extracted 0.063 0.1 + 3 0 0.01 + 0 0.28 1+ .0 0.025 0.18 3.7 0.016 0.11 28.3 0.010 0.07 19.6 an aqueous preparation of bis (tri-n-butyltin) oxide and alkylbenzyltrimethylammonium chloride from Example 2.

TBT0 concentration TBT0 load Decomposition in solution% volume / wood kg / m3 weight loss% volume unextracted 0.063 0.1 + 6 0 0.0l + 0 0.27 o 0.025 0.17 10.0 '0.016 o, n 17.8 0.010 0.07 18.1+ g Aqueous preparation of Example 2 containing 59945 bis (tri-n-butyltin) oxide and alkylbenzyltrimethylammonium chloride.

TBTO concentration TBTO load Decomposition in solution $ volume / tree kg / m ^ weight loss i »volume extracted 0.063 0.43 0 0.040 0.27 0 0.025 0.17 0.5 0.016 0.11 15.0 0.010 0.07 29.1 Untreated 0 0 47.6 These results show the following range bis (tri-n- butyltin) oxide loads, comprising those retentlot, in which the weight loss first becomes negligible:

0.74 to 1.15 kg / m 2 in petroleum solvent aqueous quaternary non-extracted 0.18 to 0.28 kg / m 2 ammonium preparation (Example 1) extracted 0.26 to 0.45 kg / m 2 "" w unextracted 0.17 to 0.27 kg / m 5 (Example 2) extracted 0.17 to 0.27 kg / m 2 These results show that the activity of bis (tri-n-butyltin) oxide when used in aqueous the quaternary in ammonium preparations, for example as in Examples 1 and 2, is about 5 times higher than when used conventionally in a petroleum ether solvent.

Example 4

The wood was treated with the preparations described in Examples 1 and 2 using the usual Bethell full impregnation method. After the timber was enclosed in the cylinder, an initial vacuum was applied to the cylinder. The cylinder was flooded with preservative while maintaining a vacuum And after the preservative completely covered the timber, the effect of the vacuum was stopped and the contents of the cylinder were pressurized. Finally, the pressure was lowered, the protective agent was pumped out, and finally a vacuum was applied to the cylinder before the cylinder was placed under atmospheric pressure, and the timber was removed. The preservative was diluted with water to obtain the specified concentration depending on the final retention required. In addition to the impregnation pressure, the amounts of time during which this pressure and initial vacuum were applied varied according to the type and cross-section of the timber to be treated. For example, an initial vacuum time of 20 minutes was suitable for normal frame or log lumber timber used in buildings. If a pressure of about 10 kg / cm 2 was applied for 90 minutes or a pressure of about 12.5 kg / cm 2 for 60 minutes, a net absorption of more than 200 kg of diluted preparation per m 2 was achieved in the surface wood of the diaper. Longer times were required to treat resistant species such as Douglas spruce, hemlock, and spruce} for example, a pressure of 10 kg / cm for 120 minutes or a pressure of 12.5 kg / cm for 90 minutes. If the preparations of Examples 1 and 2 were diluted to $ 1.25 from their initial concentration with water, i.e. 0.125 bis (tri-n-butyltin) oxide, this net absorption of 200 kg per diluted preparation gave a net retention of the preservative of at least 2.5 kg per m 2 of concentrated preparation (corresponding to 0.25 kg ( tri-n-butyltin) oxide per m 2 of wood) throughout the surface wood; this is a suitable retention for the protective effect required in normal construction use.

Example 5

The wood was treated with the preparations described in Examples 1 and 2 using the standard Lovry full impregnation method. The method was the same as the Bethell's wood impregnation method described in Example 4, except that the initial vacuum was omitted and the net absorption was reduced by about 40. The pressures described in Example 4 then gave net absorbances in the Lovry method of more than 120 kg diluted formulation per m the preparations described in Examples 1 and 2 were diluted to 2.1 μl of the original preparation with water, i.e. 0.21 g of bis (tri-n-butyltin) oxide, this net absorption gave a net retention of the safener of at least 2.5 kg of concentrated preparation per m 2, corresponding to 0.25 kg of bis (tri-n-butyltin) oxide m towards the tree through the whole surface wood in the case of pine, Pinus sylvestris. This was the same retention as that achieved in the Bethell impregnation process in Example 4 »others resulted in a 40 n reduction in net absorption in the wood, which was substantially drier after treatment.

Example 6

The aqueous preparation of Example 2 diluted with water was tested as a wood preservative for its activity against various Basido-mycetes fungal species according to British Standard Method 83Θ (1961). The pieces of wood used in the experiment were kept under a vacuum of less than 10 mm Hg for 10 minutes, the diluted preparation was added and the pieces were allowed to soak for 2 hours. The pieces were weighed to determine the absorption of the preparation. Toxic limits for different fungal species are expressed as the weight of the preparation (containing 10 io TBTO) per tree. The results are shown below and are compared with the corresponding results obtained with a standard copper-chromium arsenate preparation prepared from $ 27.6 CuSO 2 .H 2 O, 35 → 4 $ J8ta KgCrgOy and 37 »0 $ * NagHAsO H 2 O and adding HgSO 4 to adjust the pH to $ 2} The toxicological limits of the latter preparation are shown as BS-4072 type 2in expressed as dry matter.

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Fosia Lenzites Folystictus monticola trabea versicolos 1. Organic tin preparation according to Example 2 unextracted <0.74 0.75-1.20 0.97-1.59 extracted <0.74 1.19-1.85 2.52- 3.90 2. Copper chromium arsenate preparation not extracted 2.93-4.85 3.09-4.86 1.61-2.64 extracted> 7.55 2.95-4.88 3.78-5.47

The results show that the diluted aqueous preparation according to Example 2 is better as a preservative than the usual inorganic preparation, especially in the case where the main wood-destroying fungus present is Foria Monticola.

Claims (8)

12,59945 Patent for suction to: Use of a synergistic mixture for the protection of a cellulosic material which is wood or a product thereof and which is not substantially contaminated with wood-destroying fungi, characterized in that the mixture for treating the cellulosic material comprises an aqueous system containing 0.01 to 0.1 * a weighted organotin compound represented by the formula R 1 SnX or R 2 SaYSnR 2 in which R is an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group or a phenyl group, X is an inorganic atom or group and Y is a sulfur or oxygen atom, and a monoquaternary an ammonium salt of the formula R "Ί + I (I) R * - N-R '" ZR "" wherein R', R ", R '" and R "", which may be the same or different, denote straight-chain or branched , a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkaryl group having 7 to 19 carbon atoms, an aralkyl group having 7 to 27 carbon atoms, or an aryl group having 6 to 20 carbon atoms, or a corresponding alkylene oxy group denate, or two or three of said substituents may be taken together with a quaternary nitrogen atom or together with a quaternary and at least one additional heteroatom to form a saturated or unsaturated 5-, 6- or 7-membered heterocyclic ring, and Z is a water-soluble anion, in an amount sufficient to disperse the organotin compound under the processing conditions to obtain a load of 0.15-1.5 kg of organostannic compound per m of wood or wood product. Use according to Claim 1, characterized in that the synergistic aqueous system contains 0.02 to 5% by weight of quaternary ammonium salt. Use according to Claim 1 or 2, characterized in that the organotin compound is tri-n-butyltin oxide. Use according to Claim 1, characterized in that the monoquaternary ammonium compound of the formula I is a compound in which R "and R "'denotes a methyl group and either R' is a benzyl group and R" "is an alkyl group having 8 to 18 carbon atoms or R 'is an alkylbenzyl group having one ring alkyl group having 8 to 18 carbon atoms and R'1' is a methyl group. Use according to Claim U, characterized in that when R 'is an alkylbenzyl group and R "" is an alkyl group, the alkyl contains 12 carbon atoms. '' K 13 5994 5 Use according to one of the preceding claims, characterized in that the weight ratio of organotin compound to quaternary ammonium compound is between 1: 2 and 1: 6. Use according to any one of the preceding claims, characterized in that the cellulosic material or product thereof is subjected to a pressure below one atmosphere, the material is then contacted with a synergistic aqueous system, the pressure is increased to an atmospheric pressure while the material is still in contact with the aqueous system. finally, the pressure is reduced to a single atmosphere, whereby the pressures and pressure maintenance times are sufficient to obtain the desired load on the cellulosic material. Use according to one of the preceding claims, characterized in that the cellulosic material or product made from it is contacted with a synergistic aqueous system, the pressure is increased to a pressure above atmospheric while the material is still in contact with the aqueous system and finally reduced to one atmosphere, which pressures are maintained are sufficient to obtain the desired load on the cellulosic material. 59945 1U