CA1244180A

CA1244180A - Aqueous agent for the treatment of wood

Info

Publication number: CA1244180A
Application number: CA000425826A
Authority: CA
Inventors: Hans-Dieter Zagefka; Wilfried Bartz
Original assignee: Chemische Werke Huels AG
Current assignee: Huels AG; Evonik Operations GmbH
Priority date: 1982-04-17
Filing date: 1983-04-14
Publication date: 1988-11-01
Also published as: DK166783D0; NO159001B; FI831250A0; JPS58188608A; FI831250L; NO831346L; EP0092655A1; DE3360280D1; NO159001C; ATE13834T1; FI77051B; FI77051C; EP0092655B1; DK166783A; DE3214196A1; JPH0337484B2

Abstract

A B S T R A C T
The application relates to an aqueous treatment agent for the impregnation of wood. It contains an organic bonding agent capable of drying by oxidation and rendered soluble with an acid, an organic wood-protective agent which is not water-soluble, and also possibly a water-soluble wood-protective agent and possibly an additive normally used in impregnating and painting technology.
The said bonding agent is a low-molecular, modified or unmodified, 1,3-butadiene polymer or copolymer carrying amino groups. By using the treatment agent, the bonding agent and wood-protective agent penetrate deeply into the wood and remain fixed there.

Description

~ 23443-254 The present invention relates to an aqueous treatment agent for the impregnation of wood.
The term wood is intended to mean all types of wood and wood-materials having an open-pore structure capable of impregna-tion.
The term wood-protective agent is intended to mean a wood-protecting biocide, preferably an insecticidal or fungicidal substance or a mixture of such substances.
The invention relates to wood-impregnation and related techniques, seeking to produce more effective and longer lasting protection for wood. Therefore it is regarded as important to ensure that adequate concentrations of bonding agent and wood-protective agent penetrate and remain fixed in the parts of the wood to be protected. Under certain circumstances a decorative surface may also be imparted to the wood.
The invention is not concerned with the techniques of painting wood. Pain-ting is only concerned with the surface of the wood, without any in-depth action.
German Offenlegungsschrift 30 26 300 discloses wood-protective agents for impregnation (impregnating agents) whichare, among others, mixtures of water-soluble inorganic wood-protective agents and (in practice) water-insoluble organic wood-protective agents.
Water-insoluble wood-protective agents, even when pre-viously dissolved in water-compatible organic solvents such as lower alcohols and ]cetones, are only sparingly soluble in aqueous - 1 - '~' solutions of bonding agents, such as occur during production.
l'herefore the concentration of water-insoluble wood-protective agents which penetrate the treated wood according to the above prior art, is thus also comparatively low. For these reasons, the protection cannot always meet practical requirements.
The objective was therefore to overcome this disadvan-tage and to obtain an improved treatment-agent for wood which, with conventional methods of treatment, will ensure that the bond-ing agent and wood-protective agent penetrate deeply into the wood to be protected, in adequate concentrations, and be fixed there.
According to the present invention there is provided an aqueous treatment agent for the impregnation of wood having an open-pore structure capable of impregnation, wherein said treat-ment agent has a pH value of 2 to 8, is substantially free from pore-closing additives and comprises:
[A] a water-soluble or water dispersible bonding agent which:
i) is composed of a basic polymer and an amino group attached to the basic polymer, the basic polymer being a 1,3-butadiene polymer unmodi-fied or modified by isomerization, partial cyclization or partial hydrogenation, being composed of at least 70 mole ~ of 1,3-butadiene units and not more that 30 mole % of copolymerizable other 1,3-diolefin or ~-unsaturated monoolefin units; having a number average molecular weight (Mn) of 500 to 6,000; and having a double-bond content corresponding to an iodine number of at .` . - 2 -least 100 (g of iodine per 100 g), ii) is dryable by oxidation, and iii) has a titratable amino group content, excluding quater-nary ammonium groups, of from more than 50 to 600 mg-atom per 100 g;
[B] a water-insoluble organic wood-protective agent;
and [C] an acid in an amount sufficient in relation to the amino group in the bonding agent to render the bonding agent soluble or dispersible in water.
The bonding agent [A] which as one of the essential ingredients of the aqueous treatment agent according to the invention may also be called "binder".
It would be impossible for a person skilled in the art to gather any suggestions for accomplishing the purpose of the application from the closest prior art previously mentioned, or from the more remote prior art disclosed in German Offenlegungs-schrift Nos. 30 04 319 and 30 14 194 (the bonding agents mentioned are alkyd resins adapted to be diluted in water). Although, according to the latter Offenlegungsschrift, it is possible to prepare treatment agents having a comparatively high content of water-insoluble organic wood-protective agents, the concentration of wood-protective agent in the treated wood obtainable with such treatment agents is insufficient or unreliable.
See the comparison example (treatment agent A according to German Offenlegungsschrift 30 14 194) which deals with penta-chlorophenol absorption in impregnated test pieces.

The treatment agents according to the present invention are effective and provide for long lasting wood protection. They are superior to the treatment agents disclosed in German Offenle-gungsschrift 30 26 300, in that impregnated test pieces absorb less water. It is therefore expected that they will also surpass the treatment agents of the said prior art in their ability to regulate the absorption and release of moisture from treated wood, thus preventing the formation of cracks caused by stresses therein under certain environmental conditions.
Most of the bonding agents themselves contained in the treatment agents according to the invention are known and may be produced by known methods (German patent 28 38 930,0S's 29 11 243 and 30 26 300; see also European patent 83 709 of February 20, 1985 equivalent to Canadian patent application, Serial No. 419,336 of January 12, 1983).
The basic polymers for the production of the bonding agent preferably comprise at least 90 mole % of 1,3-butadiene structural units and not more than 10 mole ~ of other copolmeriz-able 1,3-diolefins and ~-unsaturated monoolefin structural units.
Homopolymers of 1,3-butadiene are particularly preferred.
Preferred comonomers are 1,3-diolefins, for example isoprene and 1/3-pentadiene. An example of the copolymerizable ~-unsaturated monoolefins is styrene.
The basic polymers may be produced according to known methods, as described in German Patents 11 86 631, 12 12 302, 12 41 119, 12 51 537, 12 92 853, 20 29 416, 21 22 956 and German Patent 23 61 782 of May 6, 1982 equivalent to Canadian Patent ~2~8~
1,037,499 of August 29, 1978.
The number average molecular weight (Mn) which characterizes the basic polymer is determined by vapour-pressure osmometry. Preferably it is 800 to 3,000.
Preferably less than 40% of olefinic double bonds are present in trans-configuration in the homo- or copolymers. Of these polymers, those particularly preferred contain, at the same time at least 40~ of the olefinic double bonds in cis-configura-tion.
The basic polymers may be used directly, as they occur during production, for subsequent functionalization. They may, however, also be modified before- and, under certain circum-stances, after - functionalizing in known fashion, by isomeriza-tion, partial cyclization or partial hydrogenation. Special preference is given to unmodified polymers.
The amino groups may be introduced into the 1,3-buta-diene polymers by various known methods during preparation of the bonding agents.
Thus a preferred route (I) starts with the addition of an ¢-~-unsaturated dicarboxylic acid, or an anhydride thereof, and modification where required of the addition-product by partial cyclization (German Offenlegungsschrift 30 14 196) and then the addition-product is reacted with a primary/tertiary alkylenedi-amine or a mixture of such diamines, to form an aminodicarboxylic-acidimide addition product (German Patent 28 38 930, column 7, examples 1 and 2).
The initial addition product is based in general upon 16 to 25, preferably 18 to 24% by weight of maleic anhyride (MSA) and 84 to 75, preferably 82 to 76% by weight of a polybutadiene having a number average molecular weight (Mn) of between 800 and

2,000, an iodine number of at least 350 (g of iodine/100 g), and a cis-double bond con-tent of at least 70% based on the total double bond content.
The primary/tertiary alkylenediamines have the general formula:

H2N - Rl - N (I) twherein Rl is a C2-Cg alkylene residue and R2 and R3, independ-ently of each other, are Cl-C6 alkyl residues which may be sub-stituted with a Cl-C6 alkoxy group at a position excluding the ~-position adjacent the N-atom or R2 and R3 jointly form - (CH2)s-or -(CH2)2-O-(CH2)2- t i.e. part of a ring).
The total carbon atom number in residues R2 and R3 is preferably not more than 8.
The following are examples of suitable diamines of the general formula I:
N,N-Dimethylethylenediamine, N,N-Diethylethylenediamine, N,N-Dimethylpropylenediamine(1,3), N,N~Diethylpropylenediamine(1,3), N,N-Diethyltetramethylenediamine(1,4), 2,2,N,N~Tetramethylpropylenediamine(1,3), l-Diethylamino-4-methyltetramethylenediamine(1,4), N-(3-Aminopropyl)morpholine; and N-(3-Aminopropyl)piperidine. A preferred diamine is N,N-Dimethylpropylenediamine(1,3).
Some of the diamines may be replaced by NH3 or a primary C1-C6 (cyclo)alkylamine, the (cyclo)alkyl residue of which may be substituted by a C1-C4 alkoxy group (excluding the ~-position adjacent the N-atom).
The bonding agents obtained by route (I) preferably contain from 120 to 300 mg-atom of titratable amine-nitrogen/
100 g.
A preferred route (II) uses 1,3-butadiene polymers containing epoxy groups. These may be produced, for example by terminal functionalizing of polymers obtained by the liqing-poly-merization pro~ess by reaction with epichlorohydrin. Polymers of this kind, with terminal epoxy groups, are commercially avail-able.
They may also be obtained by epoxidizing 1t3-butadiene polymers (German Patent 28 38 930, column 7, line 57 to column 8, line 5); vinyl groups may also be epoxidized, if required.
The amount of titratable epoxy-oxygen contained in the polymers (DIN*16 945) is generally from 3 to 9, preferably 4 to 8%
by weight.
It is known to aminate 1,3-butadiene polymers containing epoxy groups (German Patent 28 38 930, examples 3 to 7; German Offenlegungsschrift No. 29 11 243 published October 2, 1980, and German Patent 30 26 300 of December 20, 1984 equivalent to Canadian Patent 1,174,792 of September 18, 1984; see also European Patent 83 709 of February 20, lg85 equi~alent to Canadian Patent application, Serial No. 41~,336 of January 12, 1983).
Suitable amines include diamines of general formula (II) and monoamine of general formula (III) below:

R2 ~
HN - Rl - N (II) R4 l \ R3' [wherein Rl, R2 and R3 , are as defined for general formula I, or R2 and R3 may also be, independently of each other, a Cl-C6 alkyl radical substituted with a hydroxyl group (excluding the ~-position adjacent the N-atom); and R4 is a hydrogen atom or a Cl-C6 alkyl radical which may be sub-stituted by a hydroxyl or Cl-C4 alkoxy group (excluding the ~-position adjacent the N-atom)].
Suitable diamines of the general formula (II) where R4 is H (primary/tertiary alkylene-diamine) are for example, those mentioned in connection with general formula (I) and N,N-bis(2-hydroxyethyl)propylenediamine(l,3).
Suitable diamines of the general formula (II) where R4 is other than H(secondary/tertiary alkylene-diamines) are, for example, l-methylpiperazine and l-(~-hydroxyethyl)-piperazine.
HN - R6 (III) *"DIN" is an abbreviation for Deutsche Industrie-Norm (German Industrial Standard) and is published by the German Standards Committee.

'~,.~

c~

[wherein R5 is a hydrogen atom or a Cl-C6 alkyl radical which may be substituted with a hydroxyl group or a Cl-C4 group (excluding the ~-position adjacent the N-~tom), and R6 is a Cl-C6 alkyl or up to C6 cycloalkyl radical, each of which may be substituted by a hydroxyl group or a Cl-C4 alkoxy radical (excluding the ~-position adjacent the N-atom, or R5 and R6 jointly form -(CH2)s- or -(CH2)2-O-(CH2)2-radical, i.e., part of a ring].
The total carbon atom number in residues R5 and R6 is preferably not more than ~.
Suitable monoamines of the general formula (II), are for example, where R5 is H (primary amines): methylamine, ethylamine, propylamines, butylamines, pentylamines, hexylamines, 2-amino-3-methylbutane, 2-methoxyethylamine, 3-methoxypropylamine, 3-ethoxy-propylamine, cyclohexylamine, ethanolamine, 2-hydroxypropylamine,

3-hydroxypropylamine, and isopropanolamine; and where R5 is other than H (secondary amines): dimethylamine, diethylamine, dipropyl-amine, diisopropylamine, dibutylamine, diisobutylamine, di-s-butylamine, N-methylethylamine, N-methylbutylamine, N-methyl-s-butylamine, N-ethylbutylamine, bis(2 methoxyethyl)amine, bis(3-methoxypropyl)amine, N-methylcyclohexylamine, diethanolamine, diisopropanolamine, N-methylethanolamine, l-ethylaminobutanol(2), piperidine and morpholine.
Secondary amines are preferred. Diethanolamine is particularly preferred.
The total amount of the amine may be equimolar in rela-tion to the content of epoxy groups in the epoxidized polymer. It ,. . . .

is also possible to use an excess of amine and to remove the unreacted amine after the reaction. It is further possible to employ the amine in less than equimolar amounts, so that some of the epoxy rings remain unchanged.
Bonding agents obtained by route (II) preferably contain 100 to 300 mg atom of titratable amine-nitrogen/100 g.
As the amino group content increases, so does the water solubility of the bonding agent, neutralized with acids, and the stability of the aqueous bonding agent solutions. The solubility and stability may also be improved by the introduction of amino groups carrying hydrophilic substituents, quaternary ammonium groups being excluded.
The products thus obtained containing amino groups are rendered water-soluble and water-dispersible by neutralization, or partial neutralization, with acids or mixtures of acids. The acids used may be inorganic acids, for example sulphuric, hydro-chloric and carbonic acid; and organic acids, for example formic, acetic, propionic and lactic acid.
Preference is given to the use of biocidal acids, for example hydrofluoric, hexafluorosilicic, phosphoric, boric, arsenic, benzoic, salicylic and phosphorous acid, or to biocidal acid salts, for example potassium hydrogenfluoride or, if neces-sary, to acids which form complexes with metal ions, for example tartaric acid or ethylenediaminetetraacetic acid.
In order to achieve adequate solubility or dispersibil-ity of the bonding agent in water, the amount of the acid added must be sufficiently high. The higher the concentration of the `l "i 8~

amino groups in the bonding agent, the lower the degree of neutralization required to achieve the desired effect. Generally, the minimal amount of acid is 0O3 to 0.5 equivalents of acid/
equivalent of amino groups. As the amount of acid increases, so does the stability of the aqueous bonding agent solution, and this is revealed, for example, by better compatibility with conven-tional additives such as may be contained in the treatment agent according to the invention, and by increased penetrabllity.
It may thus be desirable, under certain circumstances to use 5 or more equivalents of acid/equivalent of amino groups. In these cases, it is then desirable to use at least some biocidal acid.
The treatment agents preferably have a pH value of 3 to 7.
The following are examples of the water-insoluble wood-protective agents: 2,5-dimethylfuran-3-carboxylic acid N-methoxy-N-cyclohexylamide, tributyltin benzoate, tributyltin naphthenate, r-hexachlorocyclohexane, pentachlorophenol, 2-mercaptobenzthiadia-zole-2, methoxycarbonylaminobenzimidazole, N,N-dimethyl-N'-phenyl-N'-~fluorodichloromethylthio)sulphamide, N,N-dimethyl-N'-p-tolyl-N'-(fluorodichloromethylthio)sulphamide, carbamates, dithiocarba-mates, phosphoric acid esters, phosphonates, thiophosphoric acid esters, dithiophosphoric acid esters, thionophosphoric acid esters, o-phenylphenol, hydroxyquinoline derivatives, endosulphane and pyrethroids.
Suitable water-soluble wood-protective agents are, for example, alkali metal fluorides, silicofluorides such as MgSiF6, alkali metal arsenates, borates and salts of lead, tin, cadmium, nickel, cobalt, manganese, copper, mercury, zinc and trivalent chromium, also (C12- to -C14 alkyl)benzyldimethylammonium chloride.
For the purpose of producing the treatment agents according to the invention, it is possible to add to the acid aqueous solution or dispersion of the bonding agent, which may if necessary contain a water-soluble wood-protective agent, a water-insoluble organic wood-protective agent which may be dissolved in a water-compatible solvent. As a rule, however, it is desirable first of all to add the water-insoluble wood-protective agent to the bonding agent, to convert this into a salt by further addition of acid, and finally to complete the treatment agent with water, possibly with a further water-soluble wood-protective agent.
Other suitable additives, are those normally used in impregnating and painting compositions and include, for example pigments, anti-skinning agents, stabilizers, siccatives, surfac-tants viscosity regulators and water-compatible solvents.
Suitable water-compatible solvents include, for example:
isopropanol, butanols, diac~tone-alcohol, alkylcellosolves and dimethylethers of glycols. These solvents may be used in amounts up to 100 parts per 100 parts by weight of the bonding agent. It is preferred that no solvents are present in the composition.
Additives of the kind described may be added in amounts normally used in practice. The type and amount of such additives is governed by the particular material to be treated, -the use to which it will be put, and the processing method, and is easily ~l~ - 12 -determined by a few investigative tests.
The treatment agents should be substantially free of pore-closing additives. Among the pore-closing additives to be excluded are those which, because of their type and their concen-tration in the treatment agent, would close the pores of the wood when applied, thus substantially interfering with the desired in-depth action of the treatment agent.
Since the bonding agents used in the treatment agents according to the invention dry by oxidation, it is generally unnecessary to add to them any cross-linking agents. Of course, additional bonding agents, which act - possibly upon heat-treat-ment - as cross-linking agents, for example water-soluble and water-dispersible aminoplasts or phenolic resins, may also be used, as long as the effect sought within the meaning of the purpose of the present invention is achieved.
Generally speaking, the treatment agents according to the invention have a bonding agent content of 1 to 40, preferably 5 tO 30~ by weight and they may be applied by any known method (cf. DIN 68 800, Sheet 3). As is known to any person skilled in the art, the achievable protection is closely linked with the treatment process.
Particularly effective is an impregnating process where-by the wood is subjected to complete impregnation under pressure or vacuum.
The following examples serve to explain the invention.
Parts are intended to mean parts by weight and percentages are intended to mean percentages by weight, unless otherwise L~
indicated.
Examples A polybutadiene was used as the basic polymer to produce a treatment agent according to the invention, characterized as follows:
- Mn (determined by vapour-pressure osmometry in chloro-benzene): about 1,700.
- iodine number (g of iodine/100 g (DIN 53 241): 445.
- double bond distribution (IR analysis) in % of total double bonds: 73 cis and 25 trans(in structural units obtained by 1,4 polymerization of 1,3-butadiene);
2 vinyl (in structural units obtained by 1,2 polymerization of 1,3-butadiene).
- viscosity (pa.s) (DIN 53 214, 20C): 0.8 The polymers carrying the amino groups (amine adducts) are produced by two routes.
Route I (amine adduct 1).
Amine adduct 1 was produced in known fashion (German Patent 28 38 930, column 7, example 1) from 1,462 parts of poly-butadiene, 388 parts of maleic anhydride (about 21% o-f maleic anhydride in the polybutadiene-maleic anhydride adduct) and 485 parts of N,N-dimethylpropylenediamine-(1,33.
Acid number: < 3 mg of KOH/g.
185 mg-atom of titratable amine-nitrogen/100 g.
After the addition of 18 parts of 50% acetic acid to 100 parts of amine adduct 1, a mixture was obtained which can be freely diluted with water.

Route II. (amine adducts 2 to 4) -The polybutadiene was epoxidized in known fashion with 60% H2O2 in the presence of formic acid (German Patent 28 38 930, column 7, line 60 to column 8, line 5). The epoxidized polybuta-diene obtained is characterized as follows:
- total oxygen (%) (elementary analysis): 8Ø
- epoxy-oxygen (%) (DIN 16 945): 5.9.
- viscosity (pa.s) (DIN 53 214, 20C): 7.2.

4,708 parts of the epoxidized polybutadiene were mixed in a nitrogen atmosphere with 872 parts of diethanolamine and were heated, with stirring to 190C. The reaction was complete in 6 hours. Amine adduct 2, thus obtained, is characterized as follows:
- residual epoxy-oxygen (%): 2.5.
- 145 mg-atom of titratable amine-nitrogen/100 g.
Amine adduct 3 was obtained in the same way.
- Residual epoxy-oxygen (%): 0~7.
- 232 mg-atom of titratable amine-nitrogen/100 g.
Amine adduct 4 was obtained in the same way, but N,N-di-methyl-propylene-diamine 1,3 was used in place of diethanol-amine.
- Residual epoxy-oxygen (%): 2.6.
- 292 mg-atom of titratable amine-nitrogen/100 g.
Production of treatment agents 1 to 4 (according to the invention) and A (according to October 22, 1981 equivalent to European Patent 38 932 of December 28, 1983) l8~
(Treatment Agent 1):
32 parts of amine adduct 1, 14.6 of pentachlorophenol (PCP) and 14.5 parts of lactic acid were mixed at about 70C. The addition of 314 parts of water produced a light-brown, slightly milky solution.
- pH value: 2.5.
- solid content (%): 15.8.
- PCP content (%): 3.9 (Treatment Agent 2):
31.5 parts of amine adduct 2, 14.4 parts of PCP and 6 parts of 73% lactic acid were mixed at about 70C. The addition of 307 parts of water produced a light-grey, slightly cloudy solution.
- pH value: 3.9.
solid content (%): 14Ø
- PCP content (%~: 4Ø
(Treatment Agent 3):
36.1 parts of amine adduct 3, 17.3 parts of PCP and 7.5 parts of lactic acid were mixed at about 70C. The addition of 374 parts of water produced a light-brown, clear solution.
- pH value 3.5.
- solid content (~): 14Ø
- PCP content (%): 4Ø
(Treatment Agent 4):
32.2 parts of amine-adduct 4, 14.7 parts of PCP and 9.0 parts of 50% aqueous phosphoric acid were mixed at about 70C.
The addition of 312 parts of water produced a greyish-brown ~ -16 -emulslon.
- pH value; 3.8.
- solid content (%): 14Ø
- PCP content (%): 4.0 (Treatment Agent A):
75 parts of a water dilutable alkyd-resin (63~ in butyl-glycol), produced according to ~erman Offenlegungsschrift 30 14 194, published October 22, 1981 equivalent to European Patent 38 932 of December 28, 1983, 4 parts of triethylamine and 26 parts of 10% aqueous caustic soda were mixed (neutralized alkyd-resin). 23 parts of PCP and 10 parts of an addition-product consisting of ethylene-oxide and nonyl-phenol (molar ratio 10:1) were added to this mixture, and the mixture was then diluted with water.
- pH value: 8.3.
- solid content (~): 15.1.
- PCP content (%): 4Ø
Impregnating tests.
The impregnating tests were carried out with blocks of pine sap-wood (14 x 22 x 50 mm test pieces) according to the (DIN
52 160, pages 2 and 3) complete impregnation process. The results are set forth in the following table.

Tab1e: Impregnatln~_Tests Treatment Agent Dry Uptake (%) Relative _ _total PCP Dry Uptake (%) 1 34,9 8,5 15,6 2 31,9 9,1 14,2 3 32,1 9,1 13,8 4 31,6 9,1 14,0 A 12,2 3,6 15,5 _ Determination of dry uptake and relative dry uptake of the test-pieces is carried out according to the equations:
dry uptake (%) = W - T . 100;

relative dry uptake (~) = W - T . 100, I - T
wherein: W = the weight of the wood, impregnated, dried T = the weight of the wood, untreated, dried I = the weight oE the wood, impregnated, without drying.
For the purpose of calculating the PCP dry uptake of the test-pieces, W was determined indirectly by determining the residual amount of PCP in the treatment agent aEter impregnation.
As may be gathered from the Table, the relative dry up-take corresponds well with the solid content of the treatment agent. On the other hand, analytical investigation of the excess solution used to impregnate the test-pieces shows that the compos-ition of the treatment agent is not changed by the treatment. It : A

may be gathered from this that both the bonding agent and the wood-protective agent penetrate into the test-pieces.
If the test-pieces impregnated with treatment agents 1 to 4 according to the invention are stacked one upon the otherl the surfaces in contact do not stick together, i.e., the bonding agent displays the required penetration and is not merely precip-itated onto the surface of the test-pieces.
It may also be gathered from the Table that it is possible, with treatment agents 1 to 4 according to the invention, to introduce considerably larger amounts of PCP into the test-pieces than is possible with treatment agent A (PCP dry uptake) used for comparison purposes.
The treatment agents according to the invention also surpass the corresponding treatment agents of the closest prior art disclosed in German Offenlegungsschrift 30 26 300, since the latter do not even meet the requirement for satisfactory absorp-tion of water-insoluble wood-protective agents (attainable concen-tration thereof in aqueous treatment agents).

:-

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An aqueous treatment agent for the impregnation of wood having an open-pore structure capable of impregnation, wherein said treatment agent has a pH value of 2 to 8, is substantially free from pore-closing additives and comprises:
[A] a water-soluble or water-dispersible bonding agent which:
i) is composed of a basic polymer and an amino group attached to the basic polymer, the basic polymer being a 1,3-butadiene polymer unmodi-fied or modified by isomerization, partial cyclization or partial hydrogenation; being composed of at least 70 mole % of 1,3-butadiene units and not more that 30 mole % of copolymerizable other 1,3-diolefin or .alpha.-unsat-urated monoolefin units; having a number average molecu-lar weight (Mn) of 500 to 6,000; and having a double-bond content corresponding to an iodine number of at least 100 (g of iodine per 100 g), ii) is dryable by oxidation, and iii) has a titratable amino group content, excluding quater-nary ammonium groups, of from more than 50 to 600 mg-atom per 100 g;
[B] a water-insoluble organic wood-protective agent;
and [C] an acid in an amount sufficient in relation to the amino group in the bonding agent to render the bonding agent soluble or dispersible in water.

2. A treatment agent according to claim 1, wherein the basic polymer is a 1,3-butadiene homopolymer.

3. A treatment agent according to claim 1, which comprises 1 to 40% by weight of the bonding agent.

4. A treatment agent according to claim 1, 2 or 3, which further comprises a water-soluble wood-protective agent.

5. A treatment agent according to claim 1, 2 or 3, which further comprises an additive selected from the group consisting of a pigment, an anti-skinning agent, a stabilizer, a siccative, a surfactant, a viscosity regulator and a water-compatible solvent.

6. A treatment agent according to claim 1, 2 or 3, wherein the wood-protective agent is an insecticidal or fungicidal sub-stance or a mixture thereof.

7. A treatment agent according to claim 1, 2 or 3, wherein the basic polymer is a copolymer of 1,3-butadiene with isoprene, 1,3-pentadiene or styrene as comonomer.

8. A treatment agent according to claim 1, 2 or 3, wherein the basic 1,3-butadiene polymer has as number average molecular weight (Mn) of 800 to 3,000.

9. A treatment agent according to claim 1, 2 or 3, wherein the basic 1,3-butadiene polymer contains less than 40% of olefinic double bonds in the trans-configuration and at least 40% of ole-finic double bonds in the cis-configuration.

10. A treatment agent according to claim 1, 2 or 3, wherein the basic 1,3-butadiene polymer is unmodified.

11. A treatment agent according to claim 1, 2 or 3 wherein the bonding agent contains from 100 to 300 mg-atom of titratable amino-nitrogen/100 g.

12. A treatment agent according to claim 1, 2 or 3, wherein the acid is a biocidal acid selected from the group consisting of hydrofluoric, hexafluorosilicic, phosphoric, boric, arsenic, ben-zoic, salicylic, phosphoric, tartaric and ethylene-diamine-tetra-acetic acid.

13. A treatment agent according to claim 1, 2 or 3, which comprises 5 to 30% by weight of the bonding agent.

14. An aqueous treatment agent for the impregnation of wood having an open-pore structure capable of impregnation, wherein said treatment agent is substantially free from pore-closing addi-tives and comprises:

[A] 1 to 40 % by weight of a water-soluble or water dispersible bonding agent which:
i) is composed of a basic polymer and an amino group intro-duced into the basic polymer, the basic polymer being a 1,3-butadiene polymer unmodi-fied or modified by isomerization, partial cyclization or partial hydrogenation; being composed of at least 70 mole % of 1,3-butadiene units and not more than 30 mole % copolymerizable other 1,3-diolefin or .alpha.-unsaturated monoolefin units; having a number average molecular weight (?n) of 500 to 6,000; and having a double bond content corresponding to iodine number of at least 100 (gram of iodine per 100 gram), ii) is dryable by oxidation, and iii) has a titratable amino group content of from more than 50 to 600 milligram-atom per 100 gram, [B] a biocidally effective amount of a water-insoluble organic wood-protective biocide, and [C] an acid in an amount sufficient to neutralize the amino group in the bonding agent such that the said bonding agent is soluble or dispersible in water and the treatment agent has a pH value of 2 to 8, wherein the bonding agent is produced by:
either (a) adding an .alpha.,.beta.-unsaturated dicarboxylic acid or its anhydride to the basic 1,3-butadiene polymer and then react-ing the resulting adduct with an alkylenediamine containing both primary and tertiary amino groups of the formula:

(I) (wherein R1 is a C2-C8 alkylene radical, and R2 and R3 are independently C1-C6 alkyl radical which may be substituted with a C1-C6 alkoxy radical at a position excluding the .alpha.-position adjacent the N-atom, or R2 and R3 together form -(CH2)5- or -(CH2)2-O-(CH2)2-), or (b) reacting the basic 1,3-butadiene polymer contain-ing an epoxy group with a diamine of the formula:

(II) (wherein R1 has the same meaning as in formula (I), R2' and R3' may independently be the same as R2 and R3 defined in formula (I), or R2' and R3' may also be a C1-C6 alkyl radical substituted by a hydroxy radical at a position excluding the .alpha.-position adjacent the N-atom, and R4 is a hydrogen atom or a C1-C6 alkyl radical which may be substituted by a hydroxyl or C1-C4 alkoxy radical at a position excluding the .alpha.-position adjacent the N-atom), or a monoamine of the formula:
(III) (wherein R5 is a hydrogen atom or a C1-C6 alkyl radical which may be substituted with a hydroxyl or C1-C4 alkoxy radi-cal at a position excluding the .alpha.-position adjacent to the N-atom, and R6 is a C1-C6 alkyl or up to C6 cycloalkyl, each of which may be substituted by a hydroxyl or C1-C4 alkoxy radical at a position excluding the .alpha.-position adjacent the N-atom, or R5 and R6 jointly form -(CH2)5- or -(CH2)2-O-(CH2)2-radical).

15. A treatment agent according to claim 14, wherein the basic polymer is an unmodified 1,3-butadiene homopolymer and the amino group is introduced into the basic 1,3-butadiene polymer by the process (a).

16. A treatment agent according to claim 15, wherein in process (a), maleic anhydride is added to the basic 1,3-butadiene polymer and the resulting adduct consists of about 16 to 25 % by weight of maleic anhydride portion and 84 to 75 % by weight of polybutadiene.

17. A treatment agent according to claim 16, wherein as a first step in process (a), about 16 to 25 % by weight of maleic anhydride is added to 84 to 75 % by weight of polybutadiene having a number average molecular weight (Mn) of 800 to 2,000, an iodine number of at least 350 and a cis-double bond content of at least 70% (based on the total double bond), wherein the percent-ages of the maleic anhydride and polybutadiene are based on the total amount of these two reactants.

18. A treatment agent according to claim 17, wherein as a second step in process (a), the maleic anhydride-polybutadiene adduct is reacted with a diamine selected from the group con-sisting of N,N-dimethylethylenediamine, N,N-diethylethylenedi-amine, N,N-dimethylpropylenediamine(1,3),N,N-diethylopropylenedi-amine(1,3), N,N-diethyltetramethylenediamine(1,4), 2,2,N,N-tetra-methylpropylenediamine(1,3), 1-diethylamino-4-methyltetra-methylenediamine(1,4), N-(3-aminopropyl)morpholine and N-(3-amino-propyl)piperidine, such that the resulting bonding agent [A] has a titratable amino group content of about 120 to about 300 mg-atom per 100 g.

19. A treatment agent according to claim 17, wherein as a second step in process (a), the maleic anhydride-polybutadiene adduct is reacted with N,N-dimethylpropylenediamine(1,3) such that the resulting bonding agent [A] has a titratable amino group content of about 120 to about 300 mg-atom per 100 g.

20. A treatment agent according to claim 16, 17 or 18, wherein said water-insoluble wood-protective biocide [B] is selected from the group consisting of 2,5-dimethylfuran-3-carbox-ylic acid N-methoxy-N-cyclohexylamide, tributyltin benzoate, tri-butyltin naphthenate, .gamma.-hexachlorocyclohexane, pentachlorophenol, 2-mercaptobenzothiadiazole-2, methoxycarbonylaminobenzimidazole, N,N-dimethyl-N'-phenyl-N'(fluorodichloromethylthio)sulphamide, N,N-dimethyl-N'-p-tolyl-N'-(fluorodichloromethylthio)sulphamide, carbamates, dithiocarbamates, phosphoric acid esters, phosphon-ates, thiophosphoric acid esters, dithiophosphoric acid esters, thionophosphoric acid esters, o-phenylphenol, hydroquinone deriva-tives, endosulphane and pyrethroids.

21. A treatment agent according to claim 16, 17 or 19, wherein said water-insoluble wood-protective biocide [B] is penta-chlorophenol and is present in an amount of about 3.9 to 4.0 % by weight based on the total aqueous composition.

22. A treatment agent according to claim 14, wherein the bonding agent [A] is produced by the process (b) using an unmodi-fied polybutadiene.

23. A treatment agent according to claim 22, wherein the basic 1,3-butadiene polymer containing an epoxy group is produced by (b-1) terminal functionalization with epichlorohydrin of a polymer obtained by the living polymerization of butadiene or by (b-2) epoxidizing a 1,3-butadiene polymer.

24. A treatment agent according to claim 23 wherein the 1,3-butadiene polymer containing an epoxy group is reacted with a monoamine of formula (III) in which R5 and R6 are each up to C6 alkyl group which is substituted by a hydroxyl group at a position excluding the .alpha.-position adjacent the N-atom, such that the resulting bonding agent [A] has a titratable amino group content of about 100 to about 300 mg-atom per 100 g.

25. A treatment agent according to claim 23, wherein the 1,3-butadiene polymer containing an epoxy group is reacted with N,N-dimethylpropylenediamine(1,3) or diethanolamine such that the resulting bonding agent [A] has a titratable amino group content of about 100 to about 300 mg-atom per 100 g.

26. A treatment agent according to claim 22, 23 or 24, wherein said water-insoluble wood-protective biocide [B] is selected from the group consisting of 2,5-dimethylfuran-3-carbox-ylic acid N-methoxy-N-cyclohexylamide, tributyltin benzoate, tri-butyltin naphthenate, .gamma.-hexachlorocyclohexane, pentachlorophenol, 2-mercaptobenzothiadiazole-2, methoxycarbonylaminobenzimidazole, N,N-dimethyl-N'-phenyl-N'(fluorodichloromethylthio)sulphamide, N,N-dimethyl-N'-p-tolyl-N'-(fluorodichloromethylthio)sulphamide, carbamates, dithiocarbamates, phosphoric acid esters, phosphon-ates, thiophosphoric acid esters, dithiophosphoric acid esters, thionophosphoric acid esters, o-phenylphenol, hydroquinone deriva-tives, endosulphane and pyrethroids.

27. A treatment agent accoridng to claim 23, 24 or 25, wherein said water-insoluble wood-protective biocide [B] is penta-chlorophenol and is present in an amount of about 3.9 to 4.0 % by weight based on the total aqueous composition.

28. A method of impregnating wood which comprises treating the wood with a treatment agent as defined in claim 1, 2 or 3.

29. A method of impregnating wood which comprises treating the wood with a treatment agent as defined in claim 14, 18 or 23 by a complete impregnation under pressure or vacuum.