FI62243C - FOERFARANDE FOER KONSERVERING AV TRAE OCH TRAEPRODUKTER GENOM BEHANDLING MED EN ORGANOTENNFOERENING - Google Patents

Description

RSSr ^ l M (11) ANNOUNCEMENT

Ma ljp 'utläggningsskrift 6224 3 c (45) Fatentti uiy preceded 10 12 1922 iSjrijM Patent meddelat ^ τ ^ (51) Kv.ik? /Int.a.3 B 27 K 3/34 ENGLISH I - Fl N LAN D (21 ) Piun «lh« k * nim —P «» * n * w * etaMf 761120 (22) Htkamlipilvl - AnaMuiInfidag 23-0U.76 (23) Alku pilvi — GIM | h «ad« | 23.0U.76 (41) Interpreters julklMluI - Victims offancNg 26.10.76

Pentti-] * registry controlled (44) NlhtmWp ™ μ heard », pv„, _

Patent · och registerstyrelsen '' Antölam utl »| d © ch utUkrifM» puMinnd 31.08.82 (32) (33) (31) Requested utuelknit-βηΜ prterttut 25 · 0U. 75

Holland-Holland (NL) 750U900 (71) M & T International B.V.,. 137, Laan van Nieuw Oost-Indie, The Hague,

Holland-Holland (NL) (72) Wilhelmus Johannes Bordes, Voorborch at Middelburg, Holland-Holland (NL) (7U) Oy Kolster Ab (5U) Method for the protection of wood and wood products by means of an organotin compound - For the protection of wood and wood products in the genome This invention relates to a method for protecting wood and wood products, such as plywood, particle board and hardboard, by treating wood or wood products with an organotin compound.

Use of organotin compounds, in particular trialkyltin compounds, as a wood preservative, i. as a substance that protects wood from decaying fungi and other such organisms, has increased in recent years. In general, the process is carried out by treating, for example impregnating, the wood or wood product with a solution or dispersion of an organotin compound in an organic solvent system. The most commonly used organotin compound for this purpose is bis- (tri-n-butyltin) oxide.

Although good results have already been obtained with organotin compounds, bis (tri-n-butyltin) oxide in particular has the disadvantage that it is relatively volatile, so that during long-term storage of the treated wood or wood product it can evaporate to a considerable extent, so that the protective effect heikke-nee.

It has now been found that long-term protection of wood and wood products can be achieved by treating wood or wood products with a solution of a compound of formula (R_Sn) H X in which R is 1 to 10 carbon atoms dissolved in an organic solvent.

«3 cl« O

an alkyl group or a cyclohexyl or phenyl group and X is an anion derived from oxosulphuric acid or oxyphosphoric acid and a is an integer and b is zero or an integer such that (a + b) corresponds to the valence of anion X, the treatment being carried out 3 , 4 kg organotin compound / m wood or wood product.

In the above formula, R is preferably a straight-chain alkyl group containing up to 6 carbon atoms, especially an n-butyl group.

The anion X is preferably a sulfate or phosphate ion.

Other suitable anions are, for example, diphosphate, phosphite, thiosulfate or sulfite anions.

Preferred wood preservatives for use in the process of this invention are bis (tri-n-butyltin) sulfate and tris (tri-n-butyltin) phosphate.

It is known from DE-2 411 016 to protect wood and wood products with triorganotin compounds. It has been mentioned that the electronegative group attached to the tin atom can be, for example, a sulphate or phosphate group, but according to the examples only bis (tri-n-butyltin) oxide has been used, i.e. there is no concrete example of organotin phosphate or sulphate and / or sulphite. . However, the most important difference compared to the process according to the invention is that, according to the known process, an aqueous solution of the organotin compound is used when an organic solvent is used in the process according to the invention. In addition, the aqueous solution used in the known process contains a quaternary ammonium compound which is not required in the process of the invention. It should also be mentioned that in the known process 0.15 to 1.5 kg, generally 0.15 to 0.5 kg of organotin compound, calculated per 1 m 3 3 62243 of treated wood or wood product, are used, while in the process according to the invention at least 0.4 kg commitment under similar conditions.

It is true that bis (tri-n-butyltin) oxide gives good results. However, this impregnating agent evaporates very easily, whereas the tin compounds used in the process according to the invention are not easily volatile and are almost odorless; in addition, they are less toxic than those used in the known method and nevertheless the new method achieves a better protective effect than the known method.

Organotin compounds useful in the process of the invention are known e.g. from Dutch Application 6,602,002 and U.S. Patent 2,630,436. However, the compounds have not previously been used as wood preservatives.

As the solvent for the wood preservative, conventional solvents can be used, which include both polar and non-polar private compounds as well as mixtures of two or more compounds. A suitable solvent for bis (tri-n-butyltin) sulphate is, for example, 2-butoxyethanol ("butylglycol") and suitable solvents for tris (tri-n-butyltin) phosphate are, for example, solvents known as turpentines or arms.

The concentration of the organotin compound in the solvent can be varied within wide limits, and is preferably 0.1 to 2.0% by weight. Optionally, the wood preservative may be stored and transported in the form of a concentrate that is diluted for on-site use.

The treatment of wood and wood products with a wood preservative can be carried out in many different ways, which are known per se in this technique. Thus, the wood or wood product to be protected can be immersed in the solution of the preservative for a time sufficient to achieve the desired saturation. Another treatment method that is often recommended due to more complete absorption of the preservative into the substrate is vacuum and / or pressure impregnation. For a detailed description of such methods, reference is made to "Wood Preservation" by G.M. Hunt and G. A. Garratt, 3rd ed., American 4 62243

Foresty Series, Me. Craw-Hill (1967).

In order to compare the wood-protective activity of the compounds used in the process according to the invention with the activity shown by bis (tri-n-butyltin) oxide, the following test method was used:

As a preservative for the wood to be examined, the samples were impregnated with test pieces of beech wood cut from so-called tongue-and-groove loaders. For each tongue loader with a normal length of 1 5 cm. two 50 x 18.8 x 1.8 mm test pieces were always cut, one for impregnation and the other for control. Prior to testing, the test pieces were dried for 16 hours at 105 ° C, cooled in a desiccator, accurately weighed and then stored for one week at 75% relative humidity.

Impregnation of the test pieces with solutions of the test preservative at different concentrations was carried out by immersing the wood in the liquid, then keeping it under reduced pressure (about 7 cm Hg) for one hour and then for another 0.5 hours at normal pressure. After wiping the test pieces superficially, they were weighed accurately as quickly as possible and then air-dried for two weeks, during which time the samples were stored separately on a non-absorbent, air-permeable medium. The specimens were then stored for another two weeks at 75% relative humidity. From each set of twelve specimens impregnated with a certain concentration of wood preservative, four samples were now subjected to a standardized four-week water extraction according to DIN 52176. The other four samples were subjected to evaporation treatment for 13 weeks, during which time the samples were stored in a circulating air heating oven. The oven temperature was maintained alternately at 40 ° C (8 hours) and 25 ° C (16 hours). After these treatments, the specimens as well as the remaining four untreated samples were sterilized.

All specimens treated as described above were then examined for the effect of the microorganism Coniophora cerebella. For this purpose, each test piece together with the corresponding control piece was pressed into the amount of soil contained in a 100 ml wide-necked can with a screw cap. The soil used was canned NVT soil / standardized at 20% humidity and screened through a 5 mm mesh screen. The cans were 75-80% filled and sterilized in a pressure vessel at 120 ° C for one hour. After inoculation, the cans were kept for 45 days at 22 ° C and 75% relative humidity. At the end of this period, the test pieces were taken out, cleaned, dried for 15 hours at 105 ° C and then accurately weighed. Each measured percentage weight loss of the specimen represents the amount of wood decay.

Example

The wood-protecting activity against Coniophora cerebella was tested according to the experimental procedure described above and protected both according to the method of the invention and with bis (tr: L-n-butyltin) oxide. For bis (tri-n-butyltin sulfate) 2-butoxyethanol was used as the solvent and for tris (tri-n-butyltin) phosphate and bis (tri-n-butyltin) oxide "Shellsol A" solvent (alkylbenzene mixture) was used. with concentrations of 0.1, 0.2, 0.4, 0.8 and 1.6% by weight The following treatments were performed on the impregnated test pieces: a) no treatment b) four-week extraction according to DIN 52176 c) 13 evaporation for one week at 40/25 ° C

The test results are shown in the following table: 6 62243 ‘i’

•B

SLn ^ fvoiHiH r ~ id id o o n h oo n k ^ ·> »^ ^ ^ ^ ^ V N N h.

_ CO r-1 CM O t '' CX \ O M * O CX ΙΟ O 00 rH

: o ¢ 1) d w3 vo ω u) in <j vo m vo m * m id m m * P Drp 3! ~ ----

-P Q CO

d 5 rro>) ό -P γΗ + j vo a) fi n n o co σ> rp r ~ - cm vd m i C 35 »d -P» · *> »» · »» »» .....

P Cu> iQJ ooorrvo o o.-I cm co, -ι, h cm .- <<x

d -X-P rP CM <- (00 CM

-C _______ § cn "" * £ co p co ε>: rc \ cm cm 0 in cm h 00 σν ov vo σν 00 h & cx τ t "co · * σ · mo id n in 00 00 10 oo Γ0 rH «·. · *.». «* · * ·» »*» »·.«. * W «k ·» *.

Ή> 1 ID CO rp O O in CO r-P O O LO CM rP O O

X

• P

d co ex id cm r- 0 co co id id \ d 10 in h 0 * P - v ^ ^ V k ^ k k k k k

M _ ID CM ID CX ip ID CO ID rp CO CO CO CM

<#> a) d π <f n 00 <m cm cm rP cm cm ip ip cm

I> rP

S -----— ic w Ο ο: π3> i -pc h + j 00 mo id o cx r ~ 0 co cm r'- 0 <x 10 0 -P -P »P -pkkkkk ^ ^ ^ ^ ^ ^ ^ s

g Sj J ^ 1 ^ OOiHrH rHtPi — I O ip iHOOOO

§H —---- 3%

-H -P CO

> m E vo 10 qo n v σι in vo vo cm cm cm r-- p ·: d \ in co id 00 • p id ex m r- ro σν σν n in ro rH ^ ^ ^ ^ «w *. * k v · * »^ ^ h, rH M VO CO .H O O inCNr-HOO - in cn © ©> 1 0 _Lii .____ x '

2 <0 VO CO IM Is P <ID tp in CM ID CO CO ID CO

'' “N jJ VS ^ V * 1 ^« k * k * k * t * · »«, * »«> d dP Η σ N VD rl CO Cv CM rp CM CO ID 00 n <ajdinmiDiDin cm ro cm cm co ro ro ro ro cm ^: 0> M__ I kx qh 4-1 in rr 0 00 0 co in 00 00 in r- · ro cm oh • p rp -p. . . . . . v s. ^. . ^. .

g Oi-I OOr-C O O O O CO O O O O CM

C/O

to> 1

P -P

r-4 coco o r ~ ro in p · m cm —1 «ρ r» 00 p · 10 m 0

Cl) rt £ σ in Is oo m · o m oo co ro r- p -P cH \ ^ * »· **» ^ «· *> n, s 1. ^ k ^« k

P P tjl lOCOi-HOO ID CO rp O O U0 CM rP O O

-2 $ r - ^ -----

• P

w

SC CO

SS ID CO P1 CM rp VO CO V N H ID 00 P * CM rP

X 0> \ ^

Q rP O O © O 1 — IOOOO rp O O O O

X <K> I a It., ____ 8 a 1! 4 1, ί

<D co e -P -P 1 -p -h C -P

35> 1 -P | 4-> 4J -H-P-P 1 -P

Ä P Ό -p -H -P H -P +> -p -P

P4-IXJ P rP d P H Id P 1 — I -H

£ S & 3 £ JS ΐ S I äss Q> iq W P H PPM CO p II) en S p o ^ to β B ^ l

Claims (3)

7 62243 These results show that the extraction resistance is very good for all three compounds. However, the evaporation coefficient is considerably lower with bis (tri-n-butyltin) oxide than with the compounds used according to the invention. To achieve good wood preservative activity after 13 weeks of evaporation treatment, the degree of saturation of this compound should be at least 1.36 to 2.87 kg / cm. In contrast, when bis (tri-n-butyltin) sulfate or tris (tri-n-butyltin) phosphate is used, a degree of saturation of 0.85 and 0.34 to 0.69, respectively, is sufficient. It should be noted that the fungal decay in the control samples is greater in the case of bis (tri-n-butyltin) sulfate than in both other cases. One explanation for this could be that "Shellsol A", which was used as a solvent in the latter two cases, contains some impurities that act to slow the growth of fungi. A method for protecting wood and wood products by treating wood or wood products with an organotin compound, characterized in that the wood or wood product is treated with a solution of a compound of formula (R_Sn) HX dissolved in an organic solvent, wherein H is 1 to 10 carbon atoms an alkyl group, or a cyclohexyl or phenyl group, and X is an anion derived from oxosulphuric acid or oxophosphoric acid, and a is an integer and b is zero or an integer such that (a + b) corresponds to the valence of the anion X, that binds at least 0.4 kg organotin compound / m wood or wood product. Process according to Claim 1, characterized in that bis, (tri-n-butyltin) sulphate or tris- (tri-n-butyltin) phosphate is used as the organotin compound. Process according to Claim 1 or 2, characterized in that the content of the organotin compound in the solution is 0.1 to 2.0% by weight.