CS207354B2 - Means for protection of wood - Google Patents

Abstract

1531868 Dyeing and preserving wood DR WOLMAN GmbH 24 March 1976 [25 March 1975] 11799/76 Heading D1B A composition for dyeing and preserving wood comprises an aqueous solution of a wood preservative which contains copper and/or zinc and also an emulsified dye concentrate which comprises a solution of up to 5 parts by weight of a water-insoluble organic dye and at least 3 parts by weight of a non-ionic emulsifier in an organic solvent which is immiscible or partially miscible with water, the dye content being from 0.03 to 0.5 percent by weight based on the total weight of the wood preservative solution. The preferred dyes are metal complex dyes or azo dyes which are soluble in the organic solvents which preferably have a boiling point of at least 110‹C and an evaporation index of at least 40, e.g. higher boiling ketones, esters and alcohols. The compositions are applied to the wood by cylinder/pressure process or vacuum/pressure process or by differing. Copper and zinc sulphates are used as wood preservatives.

Description

The present invention relates to emulsions prepared from solutions of organic water-insoluble dyes, water-immiscible organic solvent and aqueous solutions, wood preservatives containing copper or zinc.

It is known to impregnate. wood with colorless preservatives must thus ensure that water-soluble organic dyes must be added to these wood preservatives. The dyes under consideration are water-soluble and not light-stable. The coloring serves only to control the treatment of wood under the roof.

In order to achieve, with impregnation, more or less stable wood coloring, it is known to disperse in aqueous solutions of wood preservatives consisting of chromates, dichromates, fluorides and bifluorides and arsenic as well as boron compounds.

insoluble organic pigments together with an electrolytically stable plastic dispersion (DAS 1 642 1 → 1.) In order to obtain an oily shiny wood surface, paraffinic, waxy and oily emulsions can also be used, as well as softening. e ^ c ^].

The weather-resistant color of the wood results from the coating of the organic insoluble dye particles with the particles of a high-polymer plastic and thus adhering firmly to the surface of the wood. This design is accomplished by dispersing the insoluble solid pigment particles in an aqueous solution of a certain inorganic wood preservative together with water-insoluble plastics. However, these dispersions have considerable disadvantages. i '

Dispersed dye and plastic particles gradually settle while being packaged. Therefore, the container in which the dispersion is stored must be provided with at least a circulation pump or stirrer. Since large volumes of solution must be stored for large scale impregnation, efficient mixing entails considerable costs. Particle settling and packing takes place particularly quickly when the dye and plastic are dispersed in relatively dilute solutions of the wood preservative (about 2-4% solutions) which impregnate the wood in a vacuum and blasting manner. solutions of wood preservatives containing copper and zinc.

Furthermore, when impregnated by a vacuum and pressure process, the dispersed insoluble pigments and plastic particles are filtered off on the surface of the wood cells, in particular the radial channels of the wood become clogged. This reduces the volume of the wood preservative which soaks the wood and the protective effect of mold and insect impregnation is also reduced.

The disadvantage is that the high color fastness to light and weather conditions is not fully utilized, the plastic coated dye particles are fixed to the wood surface and the color fastness depends on the weather fastness of the plastic. The dispersed dried plastics films, such as polyvinyl acetate and polyvinyl propionate, are considerably more sensitive to light and moisture than the pigments coated therewith. As a result, pigment pigments are normally washed away from the surface of the loosely incorporated wood by rain, and the wood surface acquires an unsightly stained appearance.

It is therefore an object of the present invention to provide a dye concentrate which is mixed with aqueous solutions in wood-based wood preservatives containing me (1a / or zinc, especially also in the presence of chromates, dichromates or chromic acid so that the wood is impregnated Wood preservatives containing clay and / or zinc are known (British Patent Specification No. 546,256).

It has now been found that an aqueous solution in a wood-fixing wood preservative comprising a and / or zinc and a colorant has these advantages when it contains an emulsified colorant concentrate consisting of a solution of 0.3 to 5 parts by weight. a water-insoluble organic dye and at least 3 parts by weight of a non-ionic emulsifier in an organic solvent that is water-limited or only milky in water, the colorant content being 0.03 to 0.5% by weight based on the total weight of the wood preservative solution ,

Suitable colorants are colorants which are readily soluble in organic solvents and whose light fastness according to DIN 54 003 and 54 004, respectively, lie between 5 and 8, preferably between 6 and 8, for example, soluble organic dyes, such as ophthalmic complex dyes and azo dyes.

The colorant content of the wood preservative stained according to the present invention is between 0.03 and 0.5 weight percent, preferably between 0.05 and 0.2 weight percent, based on the weight of the dyed wood preservative solution.

The dye content at which the dyeing intensity of the impregnated wood is optimal depends on the dye color of the dye and on whether the wood with the dyed wood preservative solution is impregnated under pressure in a pressure, vacuum, pressure or dipping process. The dyeing intensity normally reaches an optimum if the colorant content is between 0.05 and 0.5% _t, based on the weight of the dyed wood preservative solution. By using a greater amount of dye, the coloring of the impregnated wood is generally not substantially improved. It could not be assumed that the color of the wood preservative solutions dyed according to the process of the present invention is so high that even a colorant content of 0.05% by weight achieves intensive and durable coloring of the wood.

In order to prevent evaporation of the organic solvent consisting of an organic dye concentrate and an aqueous wood preservative, solvents which preferably have a boiling point of at least < RTI ID = 0.0 > 110 C < / RTI > Evaporation is the volatility number of liquids that is important for determining the launch coefficient of solvents and diluents and is the quotient of the evaporation time of the test liquid to diethyl ether, which serves as the reference liquid. The measurement is carried out at a temperature of 293 ± 2 K and a relative air humidity of 65% ± 5. The following liquids have the following liquids for diethyl ether having a volatility: acetone 2,1, dichloromethane 1,8, methanol 2,2, chloroform 2,5 , ethyl acetate 2.9, benzene 3, trichlorethylene 3.8, carbon tetrachloride 4, 2-butanone 6, methanol 6.3, dioxane 7.3, ethanol 8.3, 2-prsajnol 11, perchlorethylene 11, xylene 13.5 , acetic acid 24, butanol 33-, pyridine 36, ethyl glycol 43, pentanol 65, water-80, decalin 95, butylglycol 163, tetralin 190,? -ethyl-hexanol · 600, ethylene glycol-600, dimethylsulfoxiP ~ 700, benzyl alcohol ~ 1 800.

The parallel between boiling point and evaporation point is not obvious. Such suitable solvents include, for example, the higher-boiling ketones, esters, alcohols, in particular polyhydric alcohols with esterified and / or esterified, e.g. ether-linked hydroxyl groups, such as, for example, ethyl glycol acetate, butyl glycol ester and n-butyl glycoacetate. Pure solvents may also be replaced by solvent mixtures, for example, the density of the dye concentrate may be affected. The number of solvents necessary for dissolving the organic dye may be varied, since the solubility of the dye is dependent on the solvent in use. For example, 0.5 to 50, in particular 3 to 10, parts of the solvent can be used per 1 parts by weight of dye.

The dye endenate density can also be influenced by the fact that other organic compounds, preferably with a fungicidal or insecticidal effect, can be dissolved in the organic solvent in addition to the colorant. At the same time, care must be taken not to cause the emulsion to precipitate in the organic phase or in the aqueous phase.

Emulsifiers or solubilizers which are soluble in both oil and water are particularly suitable as emulsifiers. These include nonionic emulators of high-ethoxylated organic hydro-compounds, namely alkylphenols, glycol ether and polysyl ether of a fatty alcohol and a fatty acid or polyethylene glycols having a molarectonic weight greater than 300 and mixtures thereof.

It has been shown that a dye concentrate and an aqueous solution of a wood preservative containing a currency or zinc form a stable emitter if the degree of ethoxylation of the non-ionic emulsifiers is at least 5 moles of ethylene oxide per mole of hydrosolvent. the pressure process is dependent on the emulsifier content of the dye concentrate. The dye concentrate of the present invention should contain at least about 3 parts by weight of emulsifiers in addition to 0.3 to 5 parts by weight of the dye. To reduce foaming, anti-foaming agents can be used, for example based on mineral oils or silioon oils or in particular water-insoluble non-ionic emulsifiers (degree of oxethylation <5), which are known to be highly effective anti-foaming agents, e.g. A phenol polyolefin polyethylene glycol ether having an oxenhylation degree of approx

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Furthermore, it has been shown that the dye concentrate easily forms an emulsion with a wood preservative solution containing a currency and / or zinc, which after brief mixing or spillage (between the container and the container) is ready for use and that the emulsification rate can still improve if water is added to the dye concentrate. The addition of water causes the viscosity of the dye concentrate to increase so that the initially liquid solution is pasty. However, the viscosity weakens rapidly when water is added. The water content is preferably adjusted such that the viscous dye concentrate is liquid. The water content of the dye concentrate may, for example, be up to 75% by weight.

The stability of the dye concentrate is not affected by the addition of water.

Surprisingly, it has been found that the dye concentrate does not lose emulsifiability even if the emulsion is emitted. This can happen if the dense oreanean phase of the concentrate concentrate is substantially separated from the aqueous solution of the wood preservative in which it has been emulsified and the emulsion is dispersed for several months. it is not used, for example in winter months, when wood is rarely impregnated. In such cases, it is sufficient if the solution is poured between the storage tank and the impregnation tank and the emulsion is renewed.

It could not be assumed that the dye concentrate of the present invention with an aqueous solution of said wood preservative, despite having heavy metals and oxidizing properties, was prepared by simply mixing a stable emulsion and that the emulsifiable dye concentrate was retained.

In the preparation of the dye concentrate of the present invention, 0.3 to 5 parts by weight of the dye or dye mixture are dissolved, optionally with heating and stirring in an organic solvent. As soon as the dye has spread, at least 3 parts by weight of the emulsifier or the emulsifier are added. of the emulsifier mixture and the mixture is stirred until a homogeneous solution is obtained. The reaction mixture is then cooled to room temperature. It is also possible to proceed by first dissolving the emulsifier and then the dye in the solvent, or by dissolving both substances in the solvent simultaneously. Water may be added to the cooled solution at room temperature until the desired consistency is obtained. Instead of water, however, an aqueous solution of the wood preservative can also be used in which the dyes are then emulsified. Addition of water, resp. wood preservative is not but necessary. By mixing the dye concentrate into the wood preservative solution, an aqueous solution according to the present invention is prepared.

As the solvent for the water-insoluble dye, a non-ionic emulsifier with an ethoxylation degree of less than 5 moles of ethylene oxide per mole of hydroxy compound can be used. In these special cases, it is not necessary to use an additional organic solvent. The dye emilse prepared with the use of an emulsifier of this type penetrates very well into the wood, especially in a vacuum and pressure process, but remains relable for a long time after drying the impregnated wood. When using organic rotpoulters, which are not codifiers, the dye in the wood fixes better and faster.

The following examples are used as wood preservatives:

The chromium-copper-based C1-C6 salts consist of weights. % crystalline copper sulfate (CuSO ₄ .5H ₂ O) % of potassium dichromate (gCgO O) and weight%. % chromium oxide (CrO ^)

Cl — B-chromium, copper and boron based scales. % CuSO ₄ .5H ₂ O weight. % K ₂ Cr ₂ O7 wt. % H3BO3 wt. % sodium sulphate

CKF — chromium, copper and fluorine based scales consisting of scales. % hexane / wire of fluorocarbon (mm < / RTI &gt; % ammonium dichromate (NH4gCrgO2).

CZ — chromium and zinc based sulphate consisting of

62.1 weight. % of potassium dichromate (KgCrgO?)

37.9 weight. % zinc sulphate (ZnSO4 · H2O)

For water soluble ethylenediamine copper salt of N-nitroso-N-cyclohexyllyroxylamine, the abbreviation Cu-NCH is used.

Abbreviations:

OE = degree of oxethylation

CJ = Color Index, Volume I.

Example 1

A dye concentrate consisting of 1% by weight of a 4% CK- or CKB- or CKF- or CZ-solution is admixed.

1.0 parts by weight of ammonium salt of brown dye, CJ Solvent Brown 37

7.0 pbw of acetic acid 3-methyl-n-butyl ester

3.5 parts of alkyleeooPooletOУyeenglkkoetOeruu OE 9

3.5 spare parts alУyleeooPoolytOУyeenglkkoetOeruu OE. 7

20.0 parts by weight of water.

A stable brown colored emuUse is formed which is well suited for wood impregnation.

P4kla d 2

In the dye concentrate of Example 1, 3-methoxy-sterile acetic acid is replaced with 7 parts by weight of glycolic acid n-butyl ester. The other components mentioned in Example 1 remain unchanged and are present in the same proportions in the mixture.

With the 4% wood preservative solution mentioned in Example 1, the dye concentrate provides a practically spontaneously stable emulsion which is usable after short mixing.

EXAMPLE 3 At the end of the dye of Example 1, 3-methoxybutyl acetic acid is replaced with the same amount of n-butyl butyric acid. The proportions mentioned in Example 1 remain unchanged and are used in the same proportions in the mixture.

In order to determine the effect of the concen- tration of the salts of the wood preservative, the dye concentrate is admixed into the

Of parts by weight of a 10% CK- or CKB- or CKF- or C-solution

Of parts by weight of 6% CK- or CKB- or 'CKF- or CZ-solution

Of parts by weight of 4% CK- or CKB- or CKF- or CZ-solution

3% by weight of CK- or CKB- or CKF- or CZ-solution

These emulsions were allowed to stand. After 5-8 weeks, a 10% solution was observed at the top of the dye contamination separation. Emmlse is simply restored by simply spilling between two containers and then staining the wood unchanged to brown.

Ossatile solutions containing emulsions will remain unchanged.

Example 4

In 1000 parts by weight of a 4% CK- or CK2- or CZ-solution, the ends of the colorant consisting of parts by weight of red coloring agent CJ solvent Red are mixed with 91 parts by weight of n-butyl ester of butane of cyclohexanone.

10. parts by weight of alkylphenolpolyethylene glycol ether OE 10 parts by weight of alkylphenolpolyethylene glycol ether OE 7 parts by weight of water.

Example 5.

A concentrate consisting of 1 part by weight of CJ Solvent Red 160 parts by weight of cyclohexanone by weight by weight of polyethylene glycol ether of fatty alcohol OE 10 parts by weight of water is mixed in 1000 parts by weight of a 4% CK- or CKB- or CD ¹ * or C ² solution.

PíkLadó

The solvent used Low-water-insoluble ^one, alkylphenol and alkylphenol vysokoethoxylovaný as emulsifier. V. 1000 parts by weight are mixed with a 4% CK- or CKB- or CKF- or CZ-dye concentrate solution consisting of a part by weight of the ammonium salt of CJ Solvent Brown 37 by weight. part of p-tortlfenolpolyet) hyϊetglyko0etheru OE 4 parts by weight of p-torn ^г lfenolpolyethylnnglykoletheгu OE 9 parts by weight water.

Example 7

In 1000 parts by weight of a 4% CK- or CKB- or CIK- or CZ-solution, a dye concentrate consisting of

0.500 parts by weight of CJ Solvent Orange 56

0.125 parts by weight of CJ Solvent Red 119

0.125 parts by weight of green dye CJ Solvent Yellow 79 and CJ Solvent Blue 70

0.250 parts by weight of CJ Solvent Black 27

5.0 pbw of butyric acid n-butyl ester 2.0 pbw of alkylphenol polyglycoline. OE -9 2.0 pbw of alkylphenol polyglycoline OE 7.

Example 8

In 1000 parts by weight of 4% CK- or CKB- or CK- or CZ-solution, the dye concentrate consisting of

0.33 parts by weight of the dye CJ Solvent Yellow 83

0.10 parts by weight of CJ Solvent Red 9 '

0.07 parts by weight of CJ Solvent Blue 44 5.0 parts by weight of t-butyl stearic acid

10.0 parts by weight of alkylphtholpolynthylntglycolthrine 9.

Example 9

In 1000 parts by weight of a solution of 1.67% Cu-NCH ethylenedamine complex, a dye contaminant consisting of

Dílu weight part of blue dye CJ Solvent Blue 70 weight parts of alkylphenol polyglycol ether OE 9 weight parts of butyric acid n-butyl ester.

The present examples show that the dye concentrates of the present invention of very different compositions can be incorporated into aqueous solutions of various wood preservatives. . __

Compared with known dye dispersions, the present invention has considerable advantages. Since the emulsions of the present invention do not contain any solid particles, they are more stable and easier to prepare than known dispersions. Furthermore, during the impregnation, especially in the vacuum and pressure process, the wood channels do not clog with solid particles.

In particular, it is preferred that the dyes contained in the emulsions prepared according to the present invention are not fixed to the wood by means of more or less weather-resistant artificial resins. They penetrate more into the cells of the wood and into the cell walls and thus cannot be washed away by the rain. Thus, the color fastness of the wood under weather conditions does not depend on whether the synthetic resin is more or less weather stable but the light-fast color of the water-soluble dye used.

Claims (4)

SUBJECT OF THE INVENTION Wood-preservative composition, wood-stable, comprising an aqueous solution of copper and / or zinc and a dye, characterized in that it comprises an emulsified colorant which is a solution of 0.3 to 5 µmol of sunscreen parts of a water-soluble dye and at least 3 parts by weight of a non-ionic emulsifier in an organic solvent containing only partially or only partially miscible water, the colorant content being 0.03 to 0.5 µmol%, based on the total wood preservative solution content. Wood preservative according to claim 1, characterized in that the organic solvent is a boiling solvent of at least 110 ° C and a volatility of at least 40, the evaporation being defined as the quotient of the vaporization time of the liquid relative to the liquid. , its retardancy is 1. 3. Wood preservative according to claim 1, characterized in that the organic dye is a metal-composite dye or an azo dye soluble in an organic solvent. 4. A wood preservative according to claim 1, wherein the non-ionic emulsifier is a polyol glycol ether or a polyglycol ether of a fatty acid or fatty alcohol, wherein the degree of redoxification is at least 5 moles of ethylene oxide per mole of hydroxy compound.