FI57893B - ANVAENDNING AV EN TRAESKYDDSAKTIV BLANDNING SAOSOM FUNGICID I ALKALISKT HAERDANDE PHENOL-FORMALDEHYDKONDENSATTRAELIM - Google Patents

Abstract

1461956 Wood protectant BASF AG 4 June 1974 [5 June 1973] 24604/74 Heading A5E An antifungal composition for protecting wood comprises an aqueous solution of an alkali metal salt of N-nitroso-N-cyclohexylhydroxylamine and a short-chain diol or aqueous formaldehyde solution. The preferred diol is ethylene glycol and the composition is suitable for incorporation in phenolic resin wood glues.

Description

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Patent · och regiateretyralaen Anuekan uthgd «di utUkiKtun pubikurud 31.07.60 (32) (33) (31) Fjryduttjr« tueHmn — tuglrd prtortMC 05.06.73

Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) P 2328 ^ 2.¾.

(71) BASF Aktiengesellschaft, 6700 Ludvigshafen, Federal Republic of Germany-Federal Republic of Germany (DE) (72) Manfred Siegler, Frankenthal, Wolfgang Eisele, Ludvigshafen,

Wolfgang Reuther, Ziegelhausen, Paul Raff, Ludvigshafen,

Federal Republic of Germany, Förbundsrepubliken Tyskland (DE) (7U) Oy Kolster Ab (5U)

The invention relates to the use of an aqueous mixture of wood preservative active for the preparation of an alkali-curable phenol-formaldehyde condensate wood adhesive, which mixture contains the alkali salt of N-nitroso-N-cyclohexylhydroxyl * amine and formaldehyde as a fungicide.

It is known to protect wood against the effects of wood-destroying microorganisms and insects with the help of preservatives. This method is also important in connection with woodworking materials (particle board, cross plywood).

SE patent publication 352 561 discloses the use of N-nitroso-N-cycloalkylhydroxylamine in combination with pentachlorophenol as a wood preservative fungicide. However, it is not a use in wood glue as in the present invention. In addition, the disclosed compositions are anhydrous and contain a cyclic ether such as trioxane as a solubilizing agent.

Although SE patent publication 352 271 also mentions in the examples the possible use of N-nitroso-N-cycloalkylhydroxylamine in wood glue, the compositions disclosed in this publication must also contain a cyclic ether, namely dioxolane.

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There are various possibilities for applying a wood preservative to my woodworking materials. One very advantageous method is to mix the wood preservative with a binder solution. It ensures an even distribution of the wood preservative.

It is known that N-nitroso-N-cyclohexyl-hydroxylamine (NOH) and its salts have a good fungicidal effect. The salts are mixed in aqueous solution with binder solutions, which in the case of acidic solutions (in acid-curable amino plastics) does not cause any difficulties.

However, in the case of alkaline binder solutions (alkali-curable phenolic grouts), decomposition of the mixture can occur. This is particularly the case for concentrated soda-alkali phenolic resins, since the sodium salt of NCH is sparingly soluble in such binder solutions.

This fact limits the use of said wood preservative, since on the one hand practically all phenolic resins used for gluing woodworking materials are condensed with soda liquor, on the other hand, phenolic resin glued woodworking materials intended for more demanding outdoor use are equipped with a fungicide.

Therefore, phenolic resins have been prepared which are condensed with Kali lye and in the solutions of which the K-salt of NCH is highly soluble. However, for economic and technical reasons (shorter shelf life), these resins could not be successful.

The use of adhesive solutions more strongly diluted with water also does not work, as the pressing times of the chipboards become too long as a result.

By means of the mixture used according to the invention, an aqueous solution of the alkali salt of N-nitroso-N-cyclohexyl-hydroxylamine is obtained as a stable solution in technically useful alkali-condensed phenolic resin adhesives. According to the invention, the addition of an aqueous solution of formalin provides a decisive improvement in solubility. The addition can take place in a wood preservative or glue.

The addition is preferably to a wood preservative.

In addition, small amounts, e.g. 2-3% ethylene glycol, based on the amount of binder used, can also be used. Formalin (aqueous solution of formaldehyde in UO) is preferably added in an amount of 10-20% based on an aqueous solution of NCH salts (usually about 30-7 *). In this case, stable solutions of NCH salts are obtained in the adhesive joint, whereby only small amounts of additional formaldehyde enter the adhesive charge. These are exposed to the macromolecule formed as a building block under the curing conditions of the adhesive resin.

One advantage of this procedure is that the solubilizing formalin is removed from solution due to the curing event and the NCH salt adheres firmly to the wood.

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Aqueous, alkali-condensed phenolic resins within the meaning of the invention are understood to mean, for example, condensates of phenol and formaldehyde in a molar ratio of about 1: 1, U to 1: 2.2, which condensates are in a 30-60 overnight aqueous solution and contain 0.2 to 2 phenols per mole. moles of alkali hydroxide. They are ordinary commercial products and can be prepared by conventional and known methods.

The use of a wood preservative active mixture does not in any way adversely affect the technological properties of wood working materials made with such binder adhesives.

In the following examples, oaa and percentages are parts by weight and percentages by weight.

Example 1 100 parts by weight of phenolic resin (solids content kQ%) are mixed well with 3 parts by weight of ethylene glycol and then stirred into 5 parts by weight of an aqueous solution of the NCH salt. This mixture does not show any decomposition after a few weeks of storage.

Particleboards are made using the mixture. In order to demonstrate unchanged technical properties, a plate glued with ordinary phenolic resin works. It is an Id mm thick 1-layer board made of spruce chips; it contains 9% solid resin and 1% paraffin by weight (dry weight). The compression temperature was 165 ° C, the compression time 8 minutes.

Testing of sheets according to DIN 52 368 - 65 without protective agent with protective agent density (kg / m ^) 6U3 6U6 bending strength (w / w) 313 306 2 transverse tensile strength (w / w) V 20 8.3 8.2 V 100 3.8 3.1 * swelling after storage for 2 hours in water (£) 13.2 13.0

Comparison: when a similar amount of NCH salt 30 Rit aqueous solution is mixed with a U8 i2 phenolic resin solution without the addition of ethylene glycol, the protective agent precipitates immediately.

Example 2 10 parts by weight of a 30% aqueous solution of the NCH salt are mixed with 2 parts by weight of an aqueous solution of formaldehyde (about Uo Utista). From this mixture, 6 parts by weight of 100 parts by weight of an aqueous solution of phenolic resin (dry resin content kd%) are mixed. The preservative is then not separated.

Particleboards are made using this mixture. The unprotected phenolic resin-bonded sheet does not technically show any comparable advantages: 11 57893 18 mm thick three-layer boards made of spruce chips Dosage In the middle layer In the cover layer, solid resin / abs.

dry chips 8 3 »11% solid wax / abs.

dry chips 1 ί 1 3 »compression temperature l65 ° C, compression time: 6 minutes Testing of boards according to DIN 52 360 - 65 without protective agent with protective agent density (kg / m ^) 639 6U2 flexural strength (kp / cm ^) 331 3 ^ 0 transverse tensile strength (kp / cm ^) V 20 7.9 6.3 V 100 3.3 3.2 swelling in 2k hours after storage in water {%) lU, 7 13, k

Comparison: if 10 parts by weight of the aqueous solution of the NCH salt 30 are mixed with a further U part by weight of water and 7 parts by weight of phenol resin are added, the NCH salt precipitates after about 10 minutes. Even gluing is not possible.

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