CA1078104A

CA1078104A - Wood preservative

Info

Publication number: CA1078104A
Application number: CA287,919A
Authority: CA
Inventors: Siegfried Cymorek; Helmut Hinterberger; Wolfgang Metzner; Hubert Koddebusch
Original assignee: Desowag Bayer Holzschutz GmbH
Current assignee: Desowag Materialschutz GmbH
Priority date: 1976-09-30
Filing date: 1977-09-29
Publication date: 1980-05-27
Also published as: JPS6224241B2; AT379541B; ATA696577A; ES462725A1; NO773254L; MY8500091A; NL7710148A; FI60807C; BR7706505A; CH634343A5; IT1086098B; FR2366110A1; NO147405C; FI60807B; FI772895A; JPS5344604A; DK147038B; DK147038C; FR2366110B1; GB1590069A

Abstract

ABSTRACT OF THE DISCLOSURE:
An agent for preserving wood and wood materials, characterized in that it consists of 0.5 to 7 % by weight of a mixture of (a) at least one insecticidal alkoxyphenyl - N -alkylcarbamate and/or alkyphenyl - N - alkylcarbamate soluble in a non readily volatilizable or oleaginous organic solvent having a vaporization factor above 35 and a flash-point above 30°C, and (b) at least one insecticidal halogenated or halogen-free, thio- or thionophosphoric acid ester or thionophosphonic acid ester, or a mixture thereof, soluble in a non readily volatilizable or oleaginous organic solvent having a vaporization factor above 35 and a flash-point above 30°C, said esters having the general formula :

Description

~C3713~0~
The present invention is concerned with an agent for preserving wood and wood materials, which agent consists o~ pre-determined amounts by weight of an insecticidal alkoxy-phenyl-~-alkylcarbamate and/or alkyl-phenyl-N-alkylcarbamate, an insecti-cidal thio- or thionophosphoric acid ester or thionophosphonic acid ester, and a fungicidal compound,as well as a non readily vola-tili zable, oily or oleaginous, organic solven-t having a vaporization factor above 35 and a flash point above 30Cu It is already known that numerous carbamates and thio-phosphoric-acid esters have effective insecticidal action. These compounds are therefore used mainly as pesticides, for the protection of plants (cf., for instance, German Patent N.
1 137 895), as sprays and the like, for the direct or indirect control of noxious insects. When these insecticides are used in plant protection, they aré frequently required to decompose after a certain length of time, to prevent them from being absorbed into foodstuffs and thus harming human beings or animals.
It is also desirable to be able to wash these insecticides from plants with water, so that fruits and vegetables treated with these insecticides can be rinsed with water, before they are eaten.
This means that many insecticides which are highly effective for plants lose their effectiveness after a certain length of time, even if they are properly applied, so that further treatment may become necessary, depending upon the individual case. As far as possible, most insecticides, in the form of solutions, emulsions, concentrated sprays, and the like, should not penetrate deeply into the plants, but should perform their function on the surface of the plant, whence they may be rinsed or removed after a certain length of time~ Systemic insecticides, -on the other hand, do penetrate into the plants, but they de-compose therein after a certain length of time, for example ~1~7~

within 3 weeks. Powdered insecticides often show little adhesion and are easily washed away.
Furthermore, most insecticides are frequently required to ~e selective in their action and must not harm beneficial creatures such as bees, birds, and the like. As a result of this requirement, many insecticides are effective only a~ains-t certain pests, e.g. against mites and the like, and may have no effect upon other insects.
Accordingly, the ~pplicant has checked numerous in-sec-ticides to determine their suitability as wood-preserving agents. During these tests it was found that many highly effective insecticides having a broad spectrum of insecticidal effectiveness, e,g~ insecticidal phosphoric-acide esters and the like, cannot be used as wood-preserving agents.
The reason for this is that the demands made upon wood-preserving agents differ considerably from those made upon insecticides used in conventional fields, for plant protection and as pesticides. Whereas plant-protecting insecticides are intended to decompose ox be washed away after a certain length of time, the effects of preserving agents are expected to be long-lasting. Moreover, wood preservatives should not merely adhere to the surface, thus immediately killing all animals coming into contact with the wood, but should penetrate as deeply as possible into the wood, in order to protect it against subsequent attack. Even weathering should cause no substantial loss of effectiveness and no substantial reduction in the preservative action of the protective agent used for wood~ Since wood, and wood materials, are not only attacked and destroyed by numerous wood pests, insects, larvae thereof, and the like, but are also threatened by vegetabLe agents of destruction (fungi and the like~, an effective wood preservative must also be an effective fungicide. It is also important that the action of the 8~

insecticidal component be not impaired by the action of the fungicidal component, or vice~versa.
It is therefore an object of the present invention to provide a highly effective wood preservative which, even after a long time, will have an adequate insecticidal and fungicidal action in preserving wood, and which will offer the wood, or wood materials, permanent protection, without impairing the quality thereof, and also provide adequate preserving action even under weathering, i.e. under the action of rain, snow, frost and sunshine. Such wood preservative agent may not only be used as a long-term fungicide and insecticide for protecting wood, but also as a wood-protecting priming coat or as a wood-protecting coloured or transparent coating, which will penetrate satisfactorily into the wood or wood materials7 In accordance with the invention, there is thus provided an agent for preserving wood and wood materials, which consists of 0.5 to 7 % by weight, preferably 2 to 5 % by weight, of a mixture of ~a) at least one insecticidal alkoxyphenyl-N-alkylcarbamate and/or alkylphenyl-N-alkylcarb~mate soluble in a non readily volatilizable or oleaginous organic solvent having a vaporization factor above 35 and a flash-point above 30C, and ~b) at least one insecticidal halogenated or halogen-free, thio-or thionophosphoric acid ester or thionophosphonic acid ester, or a mixture thereof, soluble in a non readily volatllizable or oleaginous organic solvent having a vaporization factor above 35 and a flash-point above 30C, the esters having the general formula: R10 \ I fN :
p _ 0 - N - C - R3 R~
- 30 wherein Rl represents an alkyl radical having 1 to 4 carbon atoms, R2 represents an alkyl or alkoxy radical having 1 to 4 carbon ~toms or a phenyl radical, R3 represents a phenyl - - . ~ - - . . .

~ )78~

radical or a phenyl radical substituted by 1 to 3 halogen atoms or by lower alkyl or alkoxy groups, the weight ratio of (a) to (b) varying from 3:1 to 1:3, preferably from 1:0.75 to 1:2, about 0.3 to 10% by weight of at least one fungicidal compound soluble in a non readily volatilizable or oleaginous organic solvent having a vaporization factor above 35 and a flash-point above 30C, and at least 64 % by weight, preferably at least 72% by weight, of a non readily volatilizable, oily or oleaginous organic solvent having a vaporization factor above 35 and a flash-point above 30C.
In one preferred embodiment, the insecticidal mixture contains an al]coxyphenyl-N-alkylcarbamate of the general formula:

\ OR'2 and/or an alkylphenyl-N-alkylcarbamate of the general formula: .

- 0 - C - NH - R'l :

~ R' - wherein :
R'l represents an alkyl radical having 1 - 4 C-atoms, preferably a methyl radical, and R'2 represents an alkyl radical having 1 - 5 C-atoms, preferably ~- -an alkyl radical having 3 or 4 C-atoms.
As halogenated, or halogen-free, thio- or thionophos-- 30 phoric acid esterlor thionophosphonic acid ester, use is advan-tageously made of an ester of the formula~

1(~7~0~

\ 11 0 N

and, preferably, ~diethoxy-thiophos~horyloxyimino)-phenylac~toni-trile or 0,0-diethyl-0-(alpha~cyanobenzylidene-amino~~-thiono-phosphate and/or (diethoxy-thiophosphoryloxyimino)-2-chlorophenyl-acetonitrile.
The fungicides, used i:n the given weight ratios, are fungicides known per se and soluble in non readil~ volatilizable, oily or oleaginous organic solvents, preference being give~ to a fungicidal chlorophenol, preferably penta- and/or tetrachloro-phenol, or a fungicidal organometallic compound of tetravalent tin, or a l-trityl-1,2,4-triazole of the general formula: .

N :
! ~

`R

.. .. .

wherein : :
R represents a fluorine, chlorine or bromine atom, a trifluoro- :
methyl, nitro or cyano group or an alkyl group having up to 4 . : :
. 30 carbon atoms, and n is 1 or 2, as well as the salts thereof with organic or in- ~.
organic acids, preferably trifluoromethyl-triphenylmethyl-triazole -- 5 -- :

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or a mixture of one or more of these fungicides.
According to one particularly advantageous embodiment, use is made of a mixture consisting of 2-isopropoxy-phenyl-N-methylcarbamate and/or butylphenyl-N-methylcarbamate and an insecticidal, halogenated or halogen-free, thio-or thionophos-phoric acid ester or thionophosphonic acid ester of the formula :

~ - 0 - N ~ C - ~ Hal C H 0-~"

preferably, (diethoxythiophosphoryloxyimino)-phenylacetonitrile or 0,0-diethyl 0-(alpha-cyanobenzylidene-amino)-thionophosphate and/or (diethoxy-thiophosphoryloxyimino)-2-chlorophenylacetonitri-le.
Although, in preliminary tests, numerous insecticides having a broad spectrum of effectiveness, e.g. 0,0-diethyl-0-~(2-isopropyl-4-methyl)-6-pyrimidyl/-thionophosphate, 0,0 dimethyl-0-2,2-dichlorovinyl-phosphatej diethyl-vinylphosphate, and bis(dimethylamino)-phosphorylfluoride, etc., were found to be unsuitable as wood preservatives, since much of their effectiveness lost after the test has lasted for a certain length of time, it was found, within the scope of the invention, that using a combination of insecticidal alkoxy-phenyl-N-alkylcarbamate and/or alkylphenyl-~-alkylcarbamate and at least one insecticidal, halogenated or halogan-free, thio-or thionophosphoric acid ester or thionophosphonic acid ester, produces a long-lasting wood preservative with increased effectiveness. It was also found -~
that the addition of fungicidal substances produced no reduction in the effectiveness of the insecticide~ Such wood preservative penetrates satisfactorily into the wood and wood materials and thus also produces a certain preservation and impregnation in .

~7~

depth. During tests carried out in the open, it was also found that the preservative retained its effectiveness even over a long period of weathering, retaining its protective fungicidal and insecticidal properties without in any way damaging the wood.
According to a preferred embodiment of the inven-tion, 0.5 - 20% by weight , preferably 2 - 15% by weight of the non readily volatilizable, oily or oleaginous organic solvent, or solvent mixture, having a vaporization factor above 35 and a flash-point above 30C, is replaced by the same amount of at least one organic bonding agent and/or fixing agent which can be dispersed or emulsified, but preferably cannot be dissolved, in the said oily or oleaginous solvent or solvent mixture.
According to a particularly desirable embodiment, the bonding agent used is a synthetic resin in the form of an emulsion, dispersion, or solution, preferably an alkyd resin, a modified alkyd resin, a phenolic resin and/or indene-cumarone resins.
Up to 10% by weight of bitumen or bituminous substances may also be used as bonding agents. Furthermore, known dyestuffs, pigments, water-repellants, deodorizers and inhibitors, corrosion-protection agents and the like may be used. The water-repellants used may be paraffins, waxes, lanolin and the like, in amounts of 0 2 to 5%, preferably 0 5 to 2% by weight of the wood-protective agent.
The fixing agents advant~geously used are above all compounds which also prevent volatilization, and/or crystalliza-tion and precipitatio~ of the effective ingredients. Preference is given to the following:
a) plasticizers, e.g. alkyl-, aryl- or aralkylphthalates, preferably dibutyl-, dioctyl- and benYylbutylphthalates, alkyl phosphates or phosphoric-acid esters, preferably tributyl-phosphate, adipates, preferably di-(2-ethyl-hexyl)-adipate, stearates and oleates, e.g. alkyl , -:

~7~

steara-te or alkyl oleate, preferably butyl oleate, butyl ~tearate or amyl stearatc, bis-(dimethylbenzyl)-ether, p-toluene-sulphonic-acid ethyl ester, glycerine ester, glycerine ether or high-molecular-weight glycol ether, and/or b) oils, e.g. linseed oil, castor oil, tall oil and esters thereof, and/or c) flxing agents based on ketones and/or polyvinylalkyl ethers, e.g. ketones with alkyl-, aryl- or aralkyl groups, preferably benzophenone, ethylbenzophenone, polyvinylalkyl ether, preferably polyvinylmethyl ether.
The non readily volatilizable, oily or oleaginous organic solvents, having a vaporization factor above 35 and a flash-point above 30C, preferably above 45C, are avantageously solvents which are insoluble,or scarcely soluble, in water. Such ~ -solvents may be mineral oils, arornatic fractions thereof, or solvent mixtures containing mineral oils, preferably test benzene, petroleum, gas oil and/or alkyl benzene, and the like.
Preference is given to the following mineral oils having a boiling range of 170 - 220C, test benzene having a boiling range of 170 - 220C, spindle oil having a boiling range of 250 - 350C, petroleum and aromatics having a boiling range of 160 - 280C, terpentine oil and the like.
In a preferred embodiment, use can also be made of high-boiling-point mixtures of aromatic and aliphatic hydro-carbons, having a boillng range of 180 to about 220C and/or spindle oil and/or monochloronaphthalene, preferably a-monochloro- -naphthalene.
The non readily volatilizable, oily or oleaginous organic solvents, having a vaporization factor above 35 and a ... .... .
flash-point above 30C, preferably above 45C, may be partly replaced by organic solvents which volatilize easily or relatively . ,, , - , .. . . , ~ -- ~ - . - - :- -~i7~

well, provided tha-t the mixture of solvents ~lso has a vaporiza-tion factor above 35 and a flash-point above 30C, preferably above 45C, and provided that the insecticide-fungicide mixture is soluble in this mixture of solvents. In this cas, the insec-ticide-fungicide mixture should be at least as soluble as it is in the aforesaid oily or oleaginous solvents. It was found that, depending upon the vaporization factor and flash-point of the oily or oleaginous solvent used, the non readily, oily or oleaginous organic solvent may be replaced by up to 20 %, prefer-ably up to 15 %, of its weight, by a solvent having a lowervaporization factor.
As regards the fungicidal components, it has been found that these may be used in different concentrations, depen~
ing upon the type of fungicide. ~etween 3 and 8% by weight of chlorophenol, preferably penta~ andJor tetra-chlorophenol, was found to be a particularly effective fungicide. Surprinsingly enough, it was also found that fungicidal organometallic compounds of tetravalent tin and fungicidal l-trityl-1,2-4-triazole impart a very satisfactory fungicidal action to the wood preservative, even in concentrations of between 0.3 and 2% by weight. The preferred fungicide for the wood preservative therefore comprises between 0.3 and 2% by weight of a fungicidal organometallic compound of tetravalent tin and/or l-trityl-1,2,4-triazole of the general formula:

N
~ N ~

~ ~ Rn _ g _ ~ 8~

wherein R represents a fluorine, chlorine or bromine atom, a trifluoromethyl,nitro or cyano group, or an alkyl group having up to 4 C-atoms, and n is 1 or 2, as well as the salts thereof with organic or inorganic acids, and,preferably, trifluoromethyl-triphenylmethyltriazole, or a mixture of one or more of the above-mentioned funyicides.
Fungicidal, tetravalent tin-organic compounds known per se may be used as the organometallic compounds o~ tetravalent tin.
The following fungicidal, tetravalent tin-organic compounds were found to be particularly suitable for the wood preservative according to the invention : bis-(tri-butyl tin)oxide, tri-n-butyl tin trichloracetate, tri-n-butyl tin-8-oxyquinoline, tri-n-butyl tin pentachlorophenolate, tri-n-butyl tin bis ethylene-thiocarbamate, tri-n-butyl tin benzoylcyanoacetic acid, tri-n-butyl tin dimethyl arsenic acid,tri-n-butyl tin fluoride, tri-n-butyl tin rhodanide, tributyl tin dichlorophenolate, and the adduct tri-n-butyl tin acrylate/hexachlorocyclopentadiene.
However, the a~ove-mentioned preferred fungicides, may also be replaced by other fungicides soluble in oily or oleaginousoryanic solvents having a vaporization factor above 35 and a flash point above 30C, preferably above 45C, or by mixtures of these fungicides with the previously mentioned fungicides, e.g. fungicidal, oil soluble naphthenates, preferably zinc and/or copper naphthenates: 8-oxyquinoline or the fungicidal, oil-solu-ble salts or derivatives thereof, preferably phenyl-mercury-8-oxyquinolate; fungicidal compounds and derivatives or mixtures of chlorophenols, preferably compounds or mixtures of penta- and/or tetrachlorophenol with not easily volatilized amines, e.g.

rosinamine, nitrophenols and nitrochlorsphenols and/or nitro-chlorobenzene~, especially 1,2-dinitrotetrachlorobenzene; oil-soluble, fungicidal, metal-organic compounds, e.g. of copper, ~L~378~

zinc, manganese, cobalt, chromium or mexcury, e.g. in the form of caprylates, napthenates, oleates and the like, fungicidal salts of N-nitroso-N-cyclohexylhydroxylamine, preferably of the aluminum salt of N-nitroso-~-cyclohexylhydroxylamine and/or N-trichloro-methylthiotetrahydrophthalimide . However, in using N-nitroso-N-cyclohexylhydroxylamine and/or the aluminum salt of N-nitroso-N~
cyclohexylhydroxylamine, it must be taken into account that these fungicidal compounds appear ~o be suitable only fox specific types of wood and wood ungi. Creosot~-o:il distillat~ and/or creosote oil may also be used in part in the fungicide mixtures.
According to another preferred embodiment, the non readily, volatilizable, oily or oleaginous organic solvent is also a fungicide, e.g. chloronaphthalene, preferably monochloronaph-thalene and/or dichloronaphthalene. This is an exceptional case where the concentration of the ungicide is exceeded. However, monochloronaphthalene and/or dichloronaphthalene are preferably not used as the sole fungicide, but in conjunction with other solvents and/or fungicides, within the scope of the present . inventionO
According to the active components used, it may be desirable to use additional emulsifiers and/or wetting agents.
From the point of view of effectiveness o the wood preservative and reduction of corrosion, it is desirable to use the preservative in conjunction with mandelic acid and/or benzotriazole. This combination prevents discolouration of the wood preservative in sheet-metal tanks, or when the said preserva-tive acts upon wood containing metal or metal parts, as a result of corrosion~ These corrosion preventatives are preferably used in amounts of between 0.05 and 0.2% by weight.
The preservatives are often made in the form of concentrates which may be diluted to normal strength, upon arrival at the worksite, with non readily volatilizable, oily oroleaginous .
-- 11 -- .:.

- : :

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organic solvents. This makes it possible to produce highly effective concentrates which will also reduce transportation cos~s.
In the case of the wood preservative according to the invention, the production of a concentrate is also particularly advantageous. In such a concentrate, o course, th~ amount of the insecticide mixture and fungicide is increased (preferably uniformly), so that the preservative can be d:iluted to the correct concentration, after transportation, by the addition of the oily or oleaginous solvents, i.e. -to the concentration at which it will be used.
The amount of the wood preservative according to the invention which is to be used will differ according to the field of application, the concentration of the active ingredients, and the like. It is generally between 100 and 350 g/m2, preferably ~-between 150 and 200 g/m2. The following are preferably used as wood and wood materials: dry wood, chipboard, plywood, building wood, planks, panels, wood for windows, doors, floors, ceilings shuttering, fences, walls, roofs, furniture, piles, masts and the ..... . .... .
likeO
Comparison tests.
Preservatives tested and test methods.
1% impregnating-agent solutions of (diethoxy~thiophospho- -ryloxyimino)-phenylacetonitrile (or 0,0-diethyl-0-(alpha-cyano-benzylidene-amino) thionophosphate), (diethoxy-thiophosphorylo-xyimino)-2-chlorophenylacetonitrile and 2-isopropoxyphenyl-N-methylcarbamate, in an oryanic solvent having a vaporization factor above 35 and a flash-point above 30C, with a ~oiling range of between 180 and 210C, were produced. The impregnating agent also contained tributyl phosphate, as a fixing agent~
Tests were made with the active ingredients alone and combined in-specific weight ratios.

For these tests, circular filters were impregnated with ~C97~3~LO~
the dilute impregnating agent and were dried for 8 days in the open. Thereafter, small glass tubes (diameter 2 cm, height 5 cm), filled with two moist discs of synthetic foam (polyurethane foam), were placed on the filters. 50 mg of lining wood and 30 reticuli-termes-santonensis workers were placed in each tube. The test~
lasted for 21 days.
These tests were arranged in such a manner that -the amount of active ingredient in one series wa~ 20 g/m2 and the amount in the other series was 25 g/m . The resul-t~ are reported in the following Tables I and II.
TABLE I

. _ _ Protective Agent g/m (Average Value) Damage _ 1 % (Diethoxy-thio phosphoryloxyimino) -phenylacetonitrile 20 70 Pitting (or 0,0-Diethyl-0-(alpha-cyanobenzylidene-amino~thionophosphate) . _ ~

1 ~O ~Diethoxy-thiophos-phoryloxyimino)-2- 20 70 Pitting chlorophenylacetonitrile _ _ _ _ 1 % 2-Isopropoxiphenyl- 20 84 Major N-methylcarbamate Damage . _ . _ .
0.25 % (Diethoxy-thio-phosphoryloxyimino) -phenylacetonitrile tor 0,0-Diethyl-0 (alpha-cyanobenzylidene- 20 90 Pitting amino)thionophosphate) + 0.75 % 2-Isopro-poxyphenyl-N-methyl-C~ ~tr ~ _ _ , :

8~

TABLE I (cont.) _ . I
Protective Agent Amount % Dead Damage . ~ g/m (Average Value) _. _ 0.25 % 2-Isopropoxyphe-nyl-N-methylcarbamate + 0.75 % (Diethoxy-thiophosphoryloxyimino) 20 88 Pitting -phenylacetonitrile (or 0,0-Diethyl-0-(alpha-cyanobenzylideneamino) thionophosphate) _ __ _ _ _ 0.25 % (Diethoxythio-phosphoryloxyimino)-2-chlorophenylacetonitrile 20 86 Pitting ~ 0.75 % 2-Isopropoxy-phenyl-N-methylcarbamate _ _ _ , __ _ _ . .
0.25 % 2-Isopropoxyphenyl .
N-methylcarbamate 20 85 Pitting + 0.75 % (Diethoxythio-phosphoryloxy.imino)-2- .
chlorophenylacetonitrile . . _ _ TABLE II

, _ _ _ _ Protective Agent Amount % Dead Damage g/m (Average Value) . _ _ ~ , 1 % (Diethoxy-thio-phosphoryloxyimino) -phenylacetonitrile(or 25 90 Pitting . 0,0-Diethyl-0-(alpha-.cyanobenzylidene-amino) thionophosphate , _ . . ~-"' .
1 % (Diethoxy-thiophos- .
phoryloxyimino)-2-chloro- 25 90 Pitting : :
phenylacetonitrile . :
_ .
1 % 2-Isopropoxyphenyl- . Major N-methylcarbamate 25 93 Damage ~~_ _ . . . .
.

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TABLE II tCont.) _ , _ _ _ lAmount % Dead Protectlve Agent 2 D~nage ¦ g/m ~Average Value) . _ _ _ __ 0.25 % (Diethoxy-thio-phosphoryloxyimino)-phenylacetonitrile (or 0,0-Diethyl-0- (alpha- 25 100 Pittingcyanobenzylidene-amino) thionophosphate ~ 0.~5 % 2-Isopropoxy-phenyl-N-methylcarbamate _ _ __ __ __ __ 0.25 % 2-Isopropoxy-phenyl-N-methylcarbamate ~ 0.75 % (Diethoxy-thio-phosphoryloxyimino) 25 100 Pitting -phenylacetonitrile (or 0,0-Diethyl-0-(alpha-cyanobenzylidene-amino) thionophosphate) . ,- _ 0.25 % (Diethoxy-thio-phosphoryloxyimino)-2-chlorophenylacetonitrile 25 94 Pitting ~ 0.75 % 2-Isopropoxy-phenyl-N-methylcarbamate _ _ Solvent (with no active Major ingredients. but with 25 28 Damage fixing agents) . _ ~ ~
'. '- '-' It may be gathered from these comparison tests that maintaining specific mixing ratios increases t~e effectiveness of the protective agent, and that this increase is greater than the cumulative effect of the individual substances~
The average number of termites killed in each three comparison test3 is shown under "% dead". "Major dal~lagc"
indicates substantial material destruction. "Pitting" indicates only paxtial destruction or minor damage, e.g. locations where the ~ermites had begun to work but had not produced extensive damage. During the course of the tests, it was found, surpris-ingly enough, that the combination of the ingredients kill the ' - . . -: - . ,. . - ~ - , ~.~7~

termites faster -than individual ingredients.
Example 1 Penta- and/or Tetrachlorophenol 5.0 % by weight Isopropoxyphenyl-N-Mekhylcarbamate 0.6 % by weight 0,0-Diethyl -0- (~-cyanobenzylidene-amino)-thionophosphate or (Diethoxy~ 1.8 % by weight thiophosphoryloxyimino)-phenylaceto-nitrile Alkyd resin (100%) 12.0 æ by weight Siccative solution 0.2 % by weight Aromatic and aliphatic hydrocarbons (boiling range : 180-212C~ 80.4 % by weight 100.0 % by weight This preservative is suitable for a wood-protec-ting priming agent and is effective against fungi and insects, includ-ing termites.
Example 2 Bis -phenyl- (3-trifluoromethylphenyl) -1-(1,2,4-triazolyl)-methane 1.0 % by weight -

2- sec.-Butylphenyl -N-methylcarbamate1,0 % by weight 2- Isopropoxyphenyl -N-methylcarbamate 1.0 % by weight 0,0-Diethyl -0- (a-cyanobenzylidene-amino)--thiono-phosphate or (Diethoxy-thiophosphoryloxyimino)-phenylacetonitrile 1.5 % by weight Benzotriazole 0~05 % by weight Organic phosphates (plasticisers)6,0 % by weight Aromatic and aliphatic hydrocarbons (boiling range : 180-212C) 89.45 % by weight 100.0 % by weight This wood preservative is a resistant protec-tive agent with a simultaneous inhibiting effect against insects, including termi es. It is also an effective fungicideO

i~37~3~~
Example 3 :
Pentachlorophenol 5.5 % by weight 2-sec. sutylphenyl -~-methylcarbamate 1.0 % by weight 0,0 Diethyl -0- (~-cyanobenzylidene-amino)-thionophosphate or (Diethoxy- 2.0 % by weight thiophosphoryloxyimino)-phenylaceto-nitrile Ben20triazole 0.1 % by weight Alkyd resin (100 %) 4.0 % by weight Aromatic and aliphatic solve~ts (boiling range : 180-212C) 87.4 % by weight 100.0 % by weight This mixture is a preventative wood preservative.
Ex~ le 4 :

Bis- phenyl- (3-trifluoromethylphenyl~
-1-(1,2,4 -triazolyl)methane1.5 % by weight 2- Iso-propoxyphenyl -N- methylcarbamate 1.5 % by weight 0,0 Diethyl -0- (a-cyanobenzylidene-amino)-thionophosphate or (Diethoxy- 2.0 % by weight thiophosphoryloxyimino)-phenylaceto-nitrile a- Monochloronaphthalene, techn.50.0 % by weight Linseed oil 6.0 % by weight Spindle oil(boiling range: 250-320C) 39.0 % by weight 100.0 % by weight This wood preservative has a good inhibitive action against insects, especially termites. It has excellent penetra-tion and long-lasting effectiveness, even under weatheringO
The fungicidal effect of this mixture i5 also very good~

- , . - . , -. .

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Example 5 Bis-phenyl- (3-trifluoromethylphenyl -l- 1.5 % by weight (1,2,4, -triazolyl)methane 2- Isopropoxyphenyl -~- methylcarbamate 0.75 % by weight 0,0- Diethyl -0- (~-cyanobenzylidene-amino)- thionophosphate or (Diethoxy- 1.5 % by weight thiophosphoryloxyimino) - phenylacetonitrile Alkyd resin (lO0 %)15.0 % by weighk Linseed oil varnish5~0 % by weight Benzotriazole 0.05 % by weight Siccative + Agent for preven-ting the foxmation of a skin0.3 % by weight Aromatic and aliphatic solvents72.90 % by weight Inorganic and organic pigments3.0 % by weight lO0.0 % by weight This wood preservative products a transparent coloura-tion of the wood and protects it against fungi and insects.
Exam~le 6 - -Penta-and/or Tetrachlorophenol5.0 % by weight Phenyl mercury oleate0.5 % by weight Isopropoxyphenyl-~-Methylcarbamate0.6 % by weight 0,0-Diethyl - 0- (a-cyanobenzylidene-amino)-thionophosphate or (Diethoxy- 1.8 % by weight thiophosphoryloxyimono)-phenylacetonitrile - -Alkyd resin (100 %)12.0 % by weight Siccative solution- 0.2 % by weight Aromatic and aliphatic hydroc~rbons (boiling range: 180 - 212C)79.9 % by weight lO0.0 % by weight - This preservativ~ is suitable as a wood-protecting priming agent and is effective against fungi and insects, includ-ing termites and blue moulds.

:

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. An agent for preserving wood and wood materials, characterized in that it consists of 0.5 to 7 % by weight of a mixture of (a) at least one insecticidal alkoxyphenyl-N-alkylcarbamate and/or alkyphenyl-N-alkylcarbamate soluble in a non readily volatilizable or oleaginous organic solvent having a vaporization factor above 35 and a flash-point above 30°C, and (b) at least one insecticidal halogenated or halogen-free, thio- or thionophosphoric acid ester or thionophosphonic acid ester, or a mixture thereof, soluble in a non readily volatil izable or oleaginous organic solvent having a vaporization factor above 35 and a flash-point above 30°C, said esters having the general formula:

wherein R1 represents an alkyl radical having 1 to 4 carbon atoms, R2 represents an alkyl or alkoxy radical having 1 to 4 carbon atoms or a phenyl radical, R3 represents a phenyl radical or a phenyl radical substituted by 1 to 3 halogen atoms or by lower alkyl or alkoxy groups, the weight ratio of (a) to (b) varying from 3:1 to 1:3; about 0.3 to 10% by weight of at least one fungicidal compound soluble in a non readily volatilizable or oleaginous organic solvent having a vaporization factor above 35 and a flash-point above 30°C; and at least 64 % by weight of a non readily volatilizable, oily or oleaginous organic solvent having a vaporization factor above 35 and a flash-point above 30°C.

2. A preserving agent according to claim 1, character-ized in that the weight ratio of (a) to (b) varies from 1:0.75 to 1:2.

3. A preserving agent according to claims 1 or 2, characterized in that the insecticidal mixture is present in an amount of 2 to 5 % by weight.

4. A preserving agent according to claim 1, character-ized in that the non readily,oily or oleaginous organic solvent is present in an amount of at least 72 % by weight.

5. A preserving agent according to claim 1, character-ized in that the alkoxyphenyl-N-alkylcarbamate is of the general formula :

wherein R'1 represents an alkyl radical of 1 to 4 carbon atoms and R'2 represents an alkyl radical of 1 to 5 carbon atoms.

6. A preserving agent according to claim 1, character-ized in that the alkylphenyl-N-alkylcarbamate is of the general formula :

wherein R'1 represents an alkyl radical of 1 to 4 carbon atoms and R'2 represents an alkyl radical of 1 to 5 carbon atoms.

7. A preserving agent according to claims 5 or 6, characterized in that R'1 represents a methyl radical.

8. A preserving agent according to claims 5 or 6, characterized in that R'2 represents an alkyl radical having 3 or 4 carbon atoms.

9. A preserving agent according to claim 1, character-ized in that R1 represents an ethyl radical, R2 represents an ethoxy radical and R3 represents a phenyl radical or a halogen-substituted phenyl radical.

10. A preserving agent according to claim 9, character-ized in that the insecticidal mixture includes 2-isopropoxy-phenyl-N-methylcarbamate and/or butylphenyl-N-methylcarbamate.

11. A preserving agent according to claims 9 or 10, characterized in that the insecticidal mixture includes (diethoxy-thiophosphoryloxyimino)- phenylacetonitrile or 0,0-diethyl -O-(.alpha.-cyanobenzylidene-amino)-thionophosphate and/or (diethoxy-thiophosphoryloxyimino)-2-chloro-phenylacetonitrile.

12. A preserving agent according to claim 1, charaeter-ized in that 0.5 to 20 % by weight of the non readily volatili-zable, oily or oleaginous solvent is replaced by the same amount of at least one organic bonding agent and/or fixing agent which can be dispersed or emulsified in the non readily volatilizable, oily or oleaginous solvent.

13. A preserving agent according to claim 1, character-ized in that 2 to 15 % by weight of the non readily volatilizable, oily or oleaginous solvent is replaced by the same amount of at least one organic bonding gent and/or fixing agent which can be dispersed or emulsified in the non readily volatilizable, oily or oleaginous solvent.