DK141237B - WOODEN PROTECTION AGENT ON Aqueous SOLUTION - Google Patents

Description

\ My di) PUBLICATION 141237 - ^ DENMARK <«> in., Ci.3 b 27 k 3/22 • (21) Application No. 1295/76 (22) Filed on the 24th of tnar. 1976 (23) Race day 24 Mar 1976 (44) The application submitted and the publication inscription published on 11 · f eb. 1 9δθ DIRECTORATE FOR THE PATENT AND TRADEMARKET (30 ^ PHortt the book from the

Mar 25 1975a 2515076, DE

(71) dr. WQLMAN GMBH, Id ?. Wolman-Strasse 51-55, 7575 Sinzheim, DE.

i72) Inventor: Hans-Norbert Marx, Mozarfrweg 8, 7580 Buehl-Weitenung, DE: Wolfgang Schulz, 40 Finkenweg, 7575 Sinzheim (Baden-Baden), DE: Hein = rich Poppen, 16 Weldemannsweg, 4575 Loeningen, DE.

(74) Plenipotentiary in the proceedings:

Hofman-Bang & Boutard Engineering Company.

(54) Wood preservative based on an aqueous solution.

This invention relates to a wood preservative of the kind set forth in the preamble of claim 1. This is in the form of emulsions of solutions of water-insoluble organic dyes in water-immiscible organic solvents and aqueous solutions of copper and / or zinc-containing wood preservatives.

It is known to make the impregnation of wood with colorless wood preservatives visible by adding water-soluble organic dyes to these wood preservatives. The dyes useful in this connection are water-soluble and not light-resistant. The dyeing serves the sole purpose of being able to control the treatment of wood used for indoor purposes.

To achieve, together with the impregnation, a more or less weather-resistant staining of the wood, it is known that in aqueous solutions of wood preservatives of chromates or bichromates, fluorides or bifluorides and arsenates, as well as boron compounds, dispersible insoluble organic pigment dyes can be dispersed together with an electrolyte resistant ( German Publication No. 1,642,171). In addition, to obtain an oil-shiny wood surface, paraffin, wax and oil emulsions as well as emollients can be used simultaneously.

The weather-resistant coloring of the wood is attributed to the fact that the organic, insoluble color particles are enveloped by the highly polymeric resin particles and retained on the wood fibers. This proposal, as stated, is intended to disperse insoluble solid pigment dyes in the aqueous solutions of certain inorganic wood preservatives together with water insoluble resins. However, such dispersions have weighty drawbacks.

The dispersed dye and plastic particles eventually settle, baking together. As a result, at least the container in which the dispersion is stored must be provided with a circulation pump or a stirrer. Since large solution volumes must be stored for large-scale impregnations, the process is difficult to implement in practice.

The particles are subjected to a particularly rapid sedimentation and baking when the dye and resin are dispersed in the relatively dilute wood preservative solutions (about 2 to 4% by weight solutions) impregnating wood by vacuum drying method. .

Then, by impregnation by the vacuum printing method, the dispersed, insoluble color pigments and plastic particles in the wood cells adjacent to the surface are filtered off, thereby blocking in particular the radial conduction paths of the "wood. Thereby, the volume of wood preservative solution absorbed by the wood is greatly diminished and the protective effect of the impregnation against fungi and insects is also reduced.

It is a further disadvantage that the high light and weather resistance of the color pigments is not fully utilized. As the dye particles in their plastic envelope are fixed to the wood fiber, the weather resistance depends on the coloring of the weather resistance of the plastic material.

Resin films obtained by drying dispersions, e.g., polyvinyl acetate and polyvinyl propionate films, are significantly more sensitive to light and moisture than the pigment dyes coated therewith. Due to this relationship, pigment dyes are generally leached from the surface due to the rain in the case of wooden structures constructed outdoors, giving the wood surface an unaesthetic, spotty appearance.

Copper and / or zinc-containing wood preservatives are known (GB-PS 546 256).

It is an object of the invention to provide a wood preservative based on an aqueous solution of the kind set forth in the preamble of claim 1, which does not contain any solid particles, which therefore does not contain any particles that can bake together, and which contains no particles, that can clog the wood surface, and therefore - even in the presence of chromates, bichromates or chromic acid - allows wood to be stained and impregnated in one go.

The wood preservative of the invention is peculiar to that of the characterizing part of claim 1. Surprisingly, it has been found that the wood preservative according to the invention fulfills the purpose of the invention.

Suitable dyes are those which are well soluble in organic solvents and if. light fastness type determined according to DIN 54 003 or 54 004 is between 5 and 8, preferably between 6 and 8, for example metal complexes and azo dyes.

4 141237

The dye content of the wood preservative solution according to the invention is between 0.03 and 0.5% by weight, preferably between 0.05 and 0.2% by weight, calculated in relation to the weight of the colored wood preservative solution.

The dye content at which the intensity of the dyeing of the impregnated wood becomes optimal is dependent, in addition to the coloring power of the dye, on whether the wood is impregnated with the dyed wood preservative solution using the boiler pressure or vacuum printing method or the immersion method. The color intensity generally achieves its optimum at a dye content between ca. 0.05 and 0.5%, based on the weight of the colored wood preservative solution.

In the case of higher color additions, the staining of the impregnated wood does not generally improve substantially.

It could not be foreseen that the coloring power of the wood preservative solution according to the invention is so great that a dye content of only 0.50 wt% is sufficient to achieve intensive and sustained wood staining.

To prevent the organic solvent from evaporating ahead of time from the emulsion consisting of organic dye concentrate and aqueous wood preservative solution, solvents are preferably used, the boiling point of which is at least 110 ° C and whose evaporation rate is at least 40 ( evaporation rate of diethyl ether is set equal to 1). Among the suitable solvents are e.g. higher boiling ketones, esters, alcohols, especially polyhydric alcohols with esterified or etherified hydroxy groups, e.g. ethyl glycol acetate, glycolic acid butyl ester and n-butyl glycol acetate. Pure solvents can also be replaced by mixtures of solvents, whereby e.g. the density of the dye concentrate may be affected. The amount of solvent required to dissolve the organic dye varies because it depends on the solubility of the dye in the particular solvent. Eg. 0.5 to 50, especially between 3 and 10 parts by weight, of solvent are used per part by weight of dye.

The density of the wood preservative solution of the invention may also be affected by the fact that, in addition to the dye, other organic compounds are also dissolved, suitably with fungicide or insecticidal effect. Thus, it must be taken into account that these additives do not cause precipitates in the aqueous or in the organic phase of the emulsion.

As nonionic emulsifiers, alkylphenol polyglycol ethers4 are used in fatty acid and fatty alcohol polyglycol ethers or polyethylene glyeols having molecular weights greater than 300 and mixtures thereof. These emulsifiers or solvents are both oil and water soluble and are nonionic emulsifiers of high ethoxylated organic hydroxy compounds.

It has been found that on the basis of the wood preservative solution according to the invention, stable emulsions can be formed when the degree of ethoxylation of the nonionic emulsifier is at least approx.

5 moles of ethylene oxide per and that the depth of penetration of the dye into the wood, especially by impregnation by the vacuum pressure method, depends on the content of the emulsifier in the dye concentrate. The wood preservative solution according to the invention should contain at least 0.3 to 5 parts by weight of dye at least 3 parts by weight of emulsifier. To suppress the foaming ability, antifoam agents may be added, e.g. on the basis of mineral oils or silicone oils or, in particular, water-insoluble, non-ionic anti-foaming agents (degree of oxethylation> 5) which are known to be highly active anti-foaming agents, e.g. p-nonyl-phenol-polyethylene glyco ether having an oxylation degree of approx. 1.5.

In addition, it has been found that the wood preservative solution according to the invention readily forms an emulsion which, after a short stirring or reciprocating flowing movement (between storage and impregnation container), is usable and that the speed of the emulsification can be further improved when water is added to the dye concentrate. Addition of water produces an increase in viscosity of the wood preservative solution, and this can go so far as to make the initially thin liquid solution solidify as a paste-like mass. However, with further water turnover the viscosity decreases rapidly. The water content is suitably adjusted in such a way that the viscous wood preservative solution is flowable. For example, the water content of the wood preservative solution may be up to 75% by weight.

, 141237 6

Surprisingly, the wood preservative also does not lose its emulsifiers once the emulsion has separated. This may occur in the case that the density of the organic phase of the wood preservative differs substantially from the density of the aqueous phase of the wood preservative in which it is emulsified and that the emulsion is stored for months without movement, e.g. during the winter months, in which one rarely impregnates. In these cases, it is sufficient to allow the solution to flow back and forth between the storage container and the impregnation container to again prepare the emulsion.

It could not be foreseen that on the basis of the dye concentrate and the aqueous solution containing copper and / or zinc, stable emulsions can be prepared by simple stirring despite the heavy metal content and the oxidizing effect of this solution and that the emulsifiable nature of the wood preservative is maintained.

To prepare the wood preservative according to the invention, between 0.3 and 5 parts by weight of dye or dye mixture are dissolved, optionally during heating and stirring in the organic solvent. When the dye has dissolved, stir in at least 3 parts by weight of emulsifier or emulsifier until the solution has become homogeneous. It is then cooled to room temperature. It is also possible to first dissolve the emulsifier and then the dye or both of them simultaneously in the organic solvent.

Room temperature water can be stirred into the cooled solution until the desired consistency is achieved. Instead of water one can also use the aqueous wood preservative solution in which the dye concentrate is to be emulsified. However, the addition of water or wood preservative solution is not necessary. By stirring the dye concentrate into the wood preservative solution, the wood preservative is prepared on the basis of the aqueous solution of the invention.

As a solvent for the water-insoluble dye one can also use a nonionic emulsifier with an ethoxylation degree of less than 5 moles of ethylene oxide per liter. mole of hydroxy compound. In this particular case, an additional organic solution is not needed (Application Example 6). The dye in an emulsion prepared by such an emulsifier, especially by impregnation in the boiler-vacuum-printing method, penetrates well into the wood, but it remains even after the drying of the impregnated wood. emulsifiable for a long time. However, when using organic solvents that are not emulsifiers, the dye is better and faster fixed in wood.

As water-soluble wood preservatives, the following examples were used: a CK salt based on chromium and copper, consisting of 49% by weight of crystallized copper sulfate (CuSO 4 3 "chromic anhydride (CrO4) a CKB salt based on chromium, copper and boron, consisting of

34 weight-9é CuSO ^ .SHgO

38 "K2Cr207 26" H3B03 2 "sodium hydrogen sulfate a CKF salt of chromium, copper and fluorine, consisting of 35% by weight copper silicofluoride hexahydrate (CuSiFg-SHgO) 65" ammonium bichromate (ΝΗ ^) 20γ2Ο7 of a CZ salt chromium and zinc, consisting of 62.1% by weight potassium bichromate (KgCrgO4) 37.9 "zinc sulfate monohydrate (ZnSO4 .HgO)

Water-soluble ethylenediamine complex of the copper salt of the N-nitroso-N-cyclohexylhydroxylamine (abbreviated: Cu-NCH).

OA = moles of ethylene oxide per mole of hydroxy compound.

EXAMPLE_1 In 1000 parts by weight of a 4% CK or CKB or CKF or CZ solution 8, a dye concentrate consisting of: 1.0 parts by weight of brown amine salt of "CJ Solvent Brown 37" 7.0 parts by weight of acetic acid (3-methoxy) was added. -n-butyl) ester 3.5 parts by weight alkylphenol polyethylene glycol ether, OA 9 3.5 parts by weight alkylphenol polyethylene glycol ether, OA 7 20.0 parts by weight water

A stable, brown-colored emulsion appeared, suitable for impregnating wood.

EXAMPLE 2 In the dye concentrate of Example 1, acetic acid (3-methoxy-n-butyl) ester is replaced by 7 parts by weight of glycolic acid n-butyl ester.

The other ingredients listed in Example 1 were maintained unchanged and in the same mixing ratio.

With the k% solutions of the wood preservatives listed in Example 1, this dye concentrate also gives rise to the formation of virtually spontaneously stable emulsions which are useful after short stirring.

EXAMPLE 3 I. The dye concentrate of Example 1 replaces acetic acid (3-methoxy-n-butyl) ester with the same weight amount of n-butter acid e-n-butyl ester. The other ingredients listed in Example 1 were kept unchanged and in the same mixing ratio.

To determine the influence of the protective salt concentration, the dye concentrate was stirred in 1000 parts by weight of a 10% CK or CKB or CKF or CZ solution 1000 parts by weight of a 6% CK or CKB or CKF or CZ solution 1000 parts by weight 4% CK or CKB or CKF or CZ solution 1000 parts by weight of a 3% CK or CKB or CKF or CZ solution 9 141237

These emulsions were stored without movement. After 5 to 8 weeks an enrichment of the dye concentrate was found in the parts close to the surface in the 10% solution. The emulsions were homogenized by simple reciprocating flow between two containers and then stained wood in unchanged brown color ,,

The emulsions obtained with the other solutions remained unchanged stable.

EKSEMPH ^ A

In 1000 parts by weight of a 4% CK or CKB or CKF or CZ solution, a dye concentrate consisting of 5 parts by weight of red dye "CJ Solvent Red 91" was added 15 parts by weight of n-butyric acid n-butyl ester 5 parts by weight of cyclohexanone 10 parts by weight alkylphenol polyethylene glycol ether, 05 10 10 parts by weight alkylphenol polyethylene glycol ether, 05 7 20 parts by weight water example. ^ In 1000 parts by weight of a 4% CK or CKB or CKF or CZ solution, a dye concentrate consisting of 1 part by weight of red dye CJ Solvent Red 160 was stirred. 8 parts by weight of cyclohexanone 8 parts by weight of fatty alcohol polyethylene glycol ether, 0510 parts by weight of water MSEMPEL_6

As a solvent is used a low ethoxylated, water-insoluble alkyl-phenol-polyethylene glycol ether and as an emulsifier a high-ethoxylated alkyl-phenol-polyethylene glycol ether.

In 1000 parts by weight of a 4% CK or CKB or CKF or CZ solution was added a dye concentrate consisting of 10 parts by weight of brown dye, amine salt of "CJ Solvent Brown 37" 1 part by weight of p-nonylphenol polyethylene glycol ether, 01 4 8 parts by weight of p-nonylphenol polyethylene glycol ether, 01 9 20 parts by weight of water E ^ EMPEL_7 In 1000 parts by weight of a 4% CK or CKB or CKF or CZ solution, a dye concentrate consisting of 0.5000 parts by weight of orange dye was stirred "CJ Solvent Orange 56 "0.125 parts by weight red dye" CJ Solvent Red 119 "0.125 parts by weight green dye" CJ Solvent Yellow 79 "" CJ Solvent Blue 70 »0.250 parts by weight black dye» CJ Solvent Black 27 "5.0 parts by weight n-butyric acid-n-butyl ester 2.0 parts by weight alkylphenol polyglycol ether, OS 9 2.0 Example 7 In 1000 parts by weight of a 4% CK or CKB or CKF or CZ solution, a dye concentrate consisting of 0.33 parts by weight of yellow dye "CJ Solvent Yellow 83" 0.10 parts by weight was stirred. desert color "CJ Solvent Red 91" 0.07 parts by weight blue dye »CJ Solvent Blue 44" 5.0 parts by weight n-butyric acid n-butyl ester 10.0 parts by weight of alkylphenol polyethylene glycol ether, OS. EXAMPLE 9 In 1000 parts by weight of a solution of 1.67% ethylene diamine complex of Cu-NCH, a dye concentrate consisting of 1 part by weight of blue dye "CJ Solvent Blue 70" 8 parts by weight of alkylphenol polyglycol ether, OS 9 8 parts by weight of n-butyric acid-n-butyl ester 141237 was added. 11

The foregoing examples show that the wood preservative according to the invention is composed in very different ways and that they can be emulsified in aqueous solutions of various wood preservatives.

Compared to the known dye dispersions, the wood preservative of the invention exhibits significant advantages. Since the wood preservative of the invention contains no solid particles, it is more stable and simpler to produce than the known dispersions. In addition, the impurities of the wood during impregnation are not clogged with solid particles, especially by the vacuum pressure method.

It is particularly advantageous that the dyes present in the wood preservative of the invention are not fixed to the wood fiber by a more or less weather-resistant synthetic resin. On the contrary, they penetrate the cells of the tree and into the cell walls and as a result can no longer be rinsed by rain. Thus, the weather resistance of the wood staining produced by impregnation with the wood preservative according to the invention does not depend on the more or less pronounced weather resistance of an artificial resin, but only on the light fastness of the water-insoluble dye used.