JPS6213881B2 - - Google Patents

Abstract

In compositions for the preservation of wood and timber materials and in the preparation of these compositions composed of 1-30 % by weight of fungicide or fungicide mixture and/or 0.3-15 % by weight of insecticide or insecticide mixture and over 55 % by weight of an organic, oily or oil-type solvent or solvent mixture of low volatility which is soluble in this mixture and which can also contain one or more organic hydrophilic solvents and/or organochemical binders and/or fixatives, 0.01-0.5 % by weight of mandelic acid and/or benzotriazole are employed as corrosion inhibitors per 100 g of the wood preservative.

Description

[Detailed description of the invention]

The present invention relates to preservatives for wood or wood-based materials, the composition of which has good wood-protecting and wood-preserving properties and also low corrosive and/or anti-corrosive action. The discoloration, disintegration and also the concomitant reduction in the effectiveness of the wood preservative which occur in the presence of metals, in particular iron, are significantly reduced or prevented. Numerous wood preservatives contain pesticides and/or chlorophenols, such as penta- and/or tetrachlorophenols, along with other additives or organic solvents. Penta- and tetrachlorophenols are highly active fungicidal organic compounds, which dissolve in oily wood preservatives and exhibit more or less strong discoloration in iron containers or iron immersion containers. This discoloration is initially due to the corrosive effect of chlorphenol on iron. The iron enters the solution as iron pentachlorophenol with a brown to dark brown coloration. Depending on the type of solvent, discoloration can occur already within the first week when stored in iron containers. For solvents like alcohol, methylene glycol or aliphatic ketones,
A brown discoloration occurs within 2-3 days. In the case of drugs containing pentachlorphenol, even small amounts of dissolved pentachlorphenol can cause a strong discoloration of the solution in the presence of iron particles. A similar discoloration or corrosive effect can be caused by certain pesticides and/or oils based on oils or oily solvents.
or fungicides or other wood preservatives, such as 8-oxyquinoline, carbamates, phosphates or thiophosphates, tetravalent tin organic compounds, as well as numerous wood preservatives containing mixtures of two or more of these compounds. show. Suitable wood protection preparations cannot be used to impregnate raw wood because the wood often develops a harmful brown coloration. For users of protectants, it is extremely important that light-colored wood protectants do not exhibit discoloration by storage in iron containers or iron soaking baths. The impregnating agent is
Do not discolor the natural wood color. moreover,
The metals in contact with the wood preservative are corrosive and must be prevented from becoming corroded, resulting in a reduction in the effectiveness of the wood preservative. It is already known to add corrosion inhibitors to various water-soluble wood protection agents in order to inhibit the effects of corrosion. Thus, for example, according to German Patent Specification No. 1033401, ammonium molybdate is added to an aqueous solution of hydrogen fluoride. Furthermore, according to Canadian Patent Specification No. 913,524, morpholine or triethanolamine was used as a corrosion inhibitor for aqueous solutions of ammonium or alkaline salts of tetra- and pentachlorophenols. Generally, however, these corrosion inhibitors for water-soluble wood preservatives cannot be used in the same manner for wood preservatives based on oils or oily substances. Therefore, the aforementioned corrosion inhibitors cannot be used in oil-based wood protectants. These corrosion inhibitors are poorly soluble in oil-based wood preservatives and either crumble or have no corrosion inhibiting effect in the composition. It is also known that dibenzyl sulfoxide can be used as a corrosion inhibitor with good results for wood protectants of the salt type, such as aqueous hexafluorosilicate or hydrofluoride solutions. However, dibenzyl sulfoxide
Increases corrosion of iron in oily wood protectants containing pentachlorophenol. From this,
It is clear that corrosion inhibitors which greatly reduce corrosion in salt-containing preparations have no corrosion-inhibiting effect or increase metal corrosion in oily and chlorophenol-containing preparations. The object and problem of the present invention is therefore to find a highly active wood preservative that avoids the above-mentioned disadvantages. Another purpose is to prevent or reduce the discoloration of preservatives or to prevent the corrosive effect of wood preservatives or metals, especially iron, in contact with the wood treated with them. The object of the present invention is to find a wood preservative in combination with an oil-soluble or oil-based preparation-soluble organic insecticide or fungicide that can be inhibited or reduced. Also, since wood preservatives often additionally contain resins with high acid numbers and/or additives that also promote corrosion, such as tall oil esters, these additives, synthetic resins or fixatives are used. Even when using wood, corrosion had to be prevented or reduced in wood protectants. Finally, a method had to be found for producing this wood preservative. According to the invention, preservatives for wood or wood-based materials suitable for these tasks meet the German Industrial Standards
Volatility of 35 and above according to DIN53170
Flash point according to DIN 51758 or DIN 51755
Disinfectants or disinfectant mixtures soluble in oily or oily refractory organic solvents having a temperature of 30°C or higher, i.e. chlorinated phenols and/or N-nitroso-N-cyclohexylhydroxylamine salts 1-
30% by weight, preferably 3-8% by weight and/or a pesticide or pesticide mixture soluble in said organic solvent
0.3 to 15% by weight, preferably 1 to 5% by weight, and at least 55%, preferably at least 87% by weight of the organic solvents or organic solvent mixtures mentioned above, and as corrosion inhibitors mandelic acid and/or benztriazole 0.01 ~0.5% by weight, advantageously 0.05-0.1% by weight
Contains. Mandelic acid as well as benztriazole thus proved to be good corrosion inhibitors in oily or oily wood protectants containing insecticides and/or fungicides. Apparently, the mandelic acid used in the wood preservative is
Forms a protective thin layer against corrosion. Benztriazole likewise acts as a corrosion inhibitor in the preservative. In the present invention, the above weight range of the corrosion inhibitors mandelic acid and/or benzatriazole is critical. If the weight ratio is less than 0.01% by weight, no corrosion prevention effect will occur. The amount of corrosion inhibitor added may exceed 0.5% by weight, however, no further improvement can be obtained and the product price increases. The best effect is found in the corrosion inhibitor weight ratio
Obtained at 0.05-0.1% by weight. This is also disclosed by the examples (see 0.05% by weight of mandelic acid or benztriazole in Examples 1 and 2 and 0.1% by weight in the test and comparative tests). The weight range of the fungicide and/or insecticide is critical since below the above weight ratio the bactericidal or insecticidal effect of the wood preservative cannot be obtained. The upper limit weight ratio may be exceeded, but no further improvement is obtained and this only increases the cost of the wood preservative. However, there are no restrictions on the type of fungicides or insecticides to be used, although they must in particular be oily or soluble in oily solvents. According to a particularly preferred embodiment, an oily or oily refractory organic solvent having a volatility of 35 or higher and a flash point of 30 DEG C. or higher according to the above-mentioned German Industrial Standards is used.
10% by weight, preferably 2 to 5% by weight, is replaced by an equal amount of one or more hydrophilic organic solvents, in which case as hydrophilic organic solvents it is advantageous to be dispersible or emulsifiable in oily or oily solvents. The one that is soluble in the water is used. As hydrophilic organic solvents used are those having a flash point above 30° C. and a volatility above 35: preferably suitable aliphatic and/or aromatic alcohols, ketones, aldehydes,
Organic salts or alkyl glycol ethers as well as emulsifiers and water are used. According to another advantageous embodiment, an oily or oily refractory organic solvent having a volatility of 35 or more and a flash point of 30° C. or more according to said German Industrial Standard.
0.5-30% by weight, preferably 2-15% by weight, with an equal amount of one or more organic binders and/or
Alternatively, instead of a fixing agent, in that case an organic binder and/or fixing agent is used which is easily dispersible or emulsifiable or soluble in oily or oily solvents. Alkyd resins or linseed oil are preferably used as organic binders, but varnishes or phenolic resins can also be used. Phosphate esters or phthalate esters are used as fixing agents to prevent or reduce volatilization of additives in wood. As a phosphoric acid ester, di-2-ethylhexyl phthalate,
Tributyl phosphate, tricresyl phosphate, triphenyl phosphate or triisobutyl phosphate may also be used as phthalate esters, as well as dibutyl phthalate, diisobutyl phthalate, diphenyl octyl phthalate or di-2-ethylhexyl phthalate. I can do it. As oily or oily refractory organic solvents having a volatility above 35 and a flash point above 30° C. according to the German Industrial Standards, water-insoluble or almost water-insoluble solvents are preferably used. Preferably, suitable mineral oils or their aromatic fractions or solvent mixtures containing mineral oils are used as such solvents, preferably benzine, petroleum, paraffin oils and/or alkylbenzoles. According to a particularly advantageous embodiment, a fungicide or
Chlorinated phenols, preferably penta- and/or tetrachlorophenols, are used as a component of the disinfectant mixture. Other advantageous fungicides include salts of N-nitroso-N-cyclohexylhydroxylamine, such as Al-N-nitroso-N-cyclohexylhydroxylamine. As insecticides, oily or oily solvent-soluble insecticides known per se are used. According to a particularly preferred embodiment, one of the insecticides or insecticide mixtures
As components: Lindan = hexachlorocyclohexane, and/or phosphoric esters and/or thiophosphoric esters and/or sulfonic acid esters and/or thionophosphoric esters and/or thiol phosphoric esters: for example (a) ethyl-parathion; (Ethyl-Parathion)
=O.O-diethyl-O-(p-nitrophenyl)thionophosphate, (b) Phoxim = (diethoxy-thiophosphoryloximino)phenylacetonitrile, (c) Chlorpyrifos = O.O -diethyl-O
-(3,5,6-trichloro-2-pyridyl)phosphorthioate, or (d) Tokution = O-ethyl-O-(2,4-dichlorophenyl)-S-n-propyldithiophosphate , and/or carbamates: e.g. (a)
2-Second-butylphenyl-N-methylcarbamate [Bassa] or (b) 2-isopropoxyphenyl-N-methylcarbamate [Propoxur] are used. Particularly advantageous with regard to preservative effect and corrosion-reducing effect is the use of chlorinated phenols in combination with carbamates and/or phosphoric esters or thiophosphoric esters, together with mandelic acid and/or benztriazole. In this combination, when the wood preservative is used without the addition of mandelic acid and/or benztriazole, in sheet iron containers or when the wood preservative acts on metals or metal-containing wood,
It was found that the wood preservative caused significant discoloration. Additionally, corrosion of the iron parts in contact with the wood preservative occurred. These phenomena can be avoided when using mandelic acid and/or benztriazole together. It is particularly effective in this case if benztriazole as corrosion inhibitor is combined with these additives together with chlorinated phenols, in particular pentachlorophenol and/or tetrachlorophenol, or if chlorinated phenols, preferably This is the case when penta- or tetrachlorophenol is combined with additives together with carbamate- and/or phosphate- or thiophosphate-based insecticides which are oily or soluble in oily solvents. When combined with these additives, benztriazole has somewhat better corrosion protection than mandelic acid. Also, the addition of benztriazole in these compositions
Metals, in particular iron, are also inhibited from corrosion and at the same time protect the wood protectant from the dark discoloration that occurs when iron parts corrode or in iron containers. In the case of some other oily or oily solvent-soluble organic pesticides or fungicides and/or organic wood preservatives, on the other hand, it is more advantageous to use mandelic acid. The combination of benztriazole and mandelic acid is particularly preferably used in the preservatives for wood and wood-based materials according to the invention in a ratio of about 20:1 to about 1:4. It is advantageous to use preservatives of the above-mentioned composition together with corrosion-inhibiting additives from the beginning, without first causing discoloration or corresponding corrosion of the preservative, since it is possible to use the preservatives with corrosion-inhibiting additives in addition after corrosion has occurred. Decolorization or dissolution can be done by disinfectants that can be used,
This is because it is no longer possible in many cases depending on the duration of action, etc. According to an embodiment, chlorinated phenols, preferably penta- and/or tetrachlorophenols, can be combined in whole or in part with other disinfectants, preferably N
- a bactericidal salt of nitroso-N-cyclohexylhydroxylamine, preferably Al-N-nitroso-N
-Substitute with cyclohexylhydroxylamine.
In this case, up to 50% by weight, preferably up to 30% by weight of chlorinated phenols, preferably penta- and/or tetrachlorophenols, are added to salts of N-nitroso-N-cyclohexylhydroxylamine, preferably Al- Switch to N-nitroso-N-cyclohexylhydroxylamine. Furthermore, in producing the above-mentioned preservative for wood and wood-based materials, the present invention provides that, during or after the production of the wood preservative, it has a volatility of 35 or more according to German Industrial Standard DIN 53170 and a flammability according to DIN 51758 or DIN 51755. 1 to 30% by weight of a disinfectant or disinfectant mixture soluble in an oily or oily refractory organic solvent having a temperature of 30° C. or higher, i.e. chlorinated phenol and/or N-nitroso-N-cyclohexylhydroxylamine salt, and / or 0.3 to 15% by weight of an insecticide or insecticidal mixture soluble in the organic solvent, and the organic solvent or organic solvent mixture as described above.
The present invention relates to a method of adding or mixing 0.01 to 0.5% by weight of mandelic acid and/or benztriazole as a corrosion inhibitor to a finished wood preservative containing 55% by weight or more. In this case, mandelic acid and/or benztriazole are preferably added to the wood preservative during or after its manufacture in the form of a paste, dispersion or solution together with organic solvents and/or plasticizers. Ru. According to a particularly preferred embodiment, the mandelic acid and/or the benztriazole are dissolved in a liquid plasticizer or in one or more solvents in the form of a 0.5-10% solution, preferably a 2-6% solution. It is added in Frequently, the wood preservatives are produced in the form of concentrates which are diluted to standard strength at the point of use using oily or oily, refractory organic solvents after transport. This makes it possible to produce highly active wood protection concentrates that can be transported with reduced transport costs. When this concentrate is produced according to the invention, the preservative concentrate for wood and wood-based materials is an oily or oily refractory organic compound having a volatility of 35 or more and a flash point of 30° C. or more according to the German Industrial Standards mentioned above. It consists of 10 to 30% by weight of a fungicide or fungicide mixture soluble in a solvent, and/or 5 to 15% by weight of an insecticide or an insecticide mixture soluble in the organic solvent, and 55% by weight or more of the organic solvent. In this case, mandelic acid and/or benztriazole as corrosion inhibitors are preferably already added to the concentrate, especially if the concentrate is to be stored or transported in contact with metals, for example in sheet metal containers. Ru. Binders and/or adhesion agents can already be added to the concentrate, in which case the volatility is above 35 and the flash point is
5 to 20% by weight of an oily or oily refractory organic solvent having a temperature of 30°C or higher can be finely dispersed or emulsified in the solvent, or is soluble in the solvent.
Equivalent amounts of binder and/or adhesion agent can be substituted. In special cases, up to 30% by weight of oily or oily refractory organic solvents can also be replaced by advantageously soluble binders and/or adhesion promoters. Mandelic acid and/or benztriazole are added to the concentrate in a large weight corresponding to the dilution ratio to be applied. The present invention will be explained in detail below using examples. Example 1 Pentachlorophenol (as a fungicide)
7% by weight hexachlorocyclohexane (as an insecticide)
1% by weight dibutyl phthalate (as fixing agent) 8% by weight mandelic acid 0.05% by weight Alkyd resin (100%) (as organic binder)
4% by weight Testbenzine 79.95% by weight When this wood preservative was stored at 50° C. for 4 weeks, no discoloration of the solution occurred in the presence of iron nails. The same preservative, but without mandelic acid, changed color slightly after 1 week and turned brown after 4 weeks. Example 2 Tetrachlorophenol (as a fungicide)
6% by weight 2-sec-butylphenyl-N-methylcarbamate (as insecticide) 2% by weight (diethoxy-thiophosphoryloximino)phenyl-acetonitrile [Phoxim]
(As an insecticide) 1% by weight Linseed oil 7% by weight Benztriazole 0.05% by weight Aromatic benzine and Testobenzine
83.95% by weight This wood preservative contains benztriazole and shows no discoloration over 4 weeks at 40°C in the presence of iron nails. In the absence of benztriazole,
A strong discoloration was already observed after one week. Example 3 Pentachlorophenol/tetrachlorophenol (1:1) (as a fungicide) 6% by weight 2-ylopropoxyphenyl-N-methylcarbamate [Propoxur] (as an insecticide) 2% by weight O.O. -Diethyl-O-(3,5,6-trichloro-2-pyridyl)phosphorthioate [Chlorpyrifos] (as an insecticide)
2% by weight Alkyd resin (100%) 15% by weight Cobalt octoate (as curing agent or drying agent for alkyd resins) 0.2% by weight Testbenzine containing aromatics 74.74% by weight Benztriazole 0.03% by weight Mandelic acid 0.03% by weight This The wood preservative contained an additive mixture (benztriazole and mandelic acid) and showed no discoloration over 5 weeks at 45°C in the presence of iron nails. When using a preservative without the additive mixture, a strong discoloration of the preservative was already observed after one week. According to a preferred embodiment, a preferred mixture of penta- or tetrachlorophenols, in particular pentachlorphenol with 15 to 35% by weight of tetrachlorphenol or tetrachlor with 20 to 45% by weight of pentachlorphenol Phenol is used. Tests and Comparative Tests Tests were carried out using the wood preservative according to the invention, with and without the addition of mandelic acid and/or benztriazole, in the presence of metals to determine the corrosion or discoloration that occurs. In this case, the metal was immersed in a suitable wood preservative for the entire test period. The test mixtures used each have the following composition: (1) aromatic benzine 94.5% by weight pentachlorophenol/tetrachlorophenol (1:1) 5.5% by weight (2) aromatic benzine 92.0% by weight pentachlorophenol/ Tetrachlorophenol (1:1) 5.5% by weight O-ethyl-O-(2,4-dichlorophenyl)-S-n-propyldithiophosphate [Tokution] (as phosphate ester) 1.5% by weight 2-iso Propoxyphenyl-N-methylcarbamate [Propoxur] (as carbamate) 1.0% by weight (3) Aromatic benzine 90.0% by weight Pentachlorophenol/tetrachlorphenol (1:1) 5.5% by weight 2-Second-butylphenyl -N-Methyl carbamate [Bassa] (as carbamate) 2.0% by weight O.O-diethyl-O-(p-nitrophenyl)-thionophosphate [Ethyl-Paration] (as phosphate ester)
1.5% by weight 2-isopropoxyphenyl-N-methylcarbamate [Propoxur] (as carbamate) 1.0% by weight (4) Aromatic benzine 96.0% by weight Al-N-nitroso-N-cyclohexylhydroxylamine 4.0% by weight (5) Aromatic benzine 93.5% by weight Pentachlorophenol/tetrachlorophenol (1:1) 5.5% by weight Linden (hexachlorocyclohexane)
1.0% by weight (6) Aromatic benzine 90.5% by weight Al-N-nitroso-N-cyclohexylhydroxylamine 4.0% by weight Pentachlorophenol/tetrachlorophenol (1:1) 5.5% by weight

【table】

【table】

Claims (1)

[Scope of Claims] 1. Wood and wood based on organic fungicides and/or organic insecticides soluble in oily or oily solvents and oily or oily organic solvents or mixtures of oily or oily organic solvents as main components. As a preservative for materials, the preservative has a volatility of 35 or higher according to German Industrial Standard DIN 53170.
Flash point according to DIN 51758 or DIN 51755
1 to 30% by weight of a disinfectant or disinfectant mixture soluble in oily or oily refractory organic solvents having a temperature of 30°C or higher, i.e. chlorinated phenols and/or N-nitroso-N-cyclohexylhydroxylamine salts, and/ or 0.3 to 15% by weight of an insecticide or an insecticide mixture soluble in the organic solvent, and 55% by weight or more of the organic solvent or organic solvent mixture, and 0.01 to 10% of mandelic acid and/or benztriazole as a corrosion inhibitor. A preservative for wood or wood-based materials, characterized in that it contains 0.5% by weight. 2 Volatility 35 according to German industrial standard DIN53170
0.5 to 30% by weight of an oily or oily refractory organic solvent or organic solvent mixture having a flash point of 30°C or higher according to DIN 51758 or DIN 51755, and an equivalent amount of one or more organic bonds. In place of organic binders and/or fixing agents, in which case organic binders and/or fixing agents are dispersible or emulsifiable or soluble in oily or oily solvents or solvent mixtures, i.e. as organic binders. Preservative for wood or wood-based materials according to claim 1, characterized in that alkyd resins or linseed oil and phosphates or phthalates are used as fixatives. 3. A preservative for wood or wood-based materials according to claim 1 or 2, characterized in that the chlorinated phenol used as a disinfectant is penta- and/or tetrachlorophenol. .