Note: Descriptions are shown in the official language in which they were submitted.
~
~ _ 0975/00098 CA 02248031 1998-09-O1
Wood preservative for afterprotection
The present invention relates to the use of a wood preservative
for the afterprotection of wood, comprising a copper compound, a
polyamine and an inorganic fungicide, and a bandage for the af-
terprotection of wood, which contains this wood preservative.
For the aftercare of transmission-line poles in the supply
network of the post office and electricity supply companies or
similar round wood stocks, in particular in the area of the
ground-air zone, bandages containing water-soluble wood preser-
vatives are applied. It is known to employ water-soluble salts
based on inorganic fluorine compounds for this, such as, for
example, alkali metal fluorides, in some cases in combination
with alkali metal bichromate or boron compounds such as boric
acid or borax. These salts, however, are exclusively active
against wood-destroying Basidiomycetes, the soft rot activity for
installation with soil contact is absent. Proposed substances ha-
ving soft rot activity are, on the one hand, dinitrophenol (Barry
A. Richardson: Wood preservation - The Construction Press Ltd.,
Lancaster p. 181) or combinations of the abovementioned compounds
with water-soluble copper salts such as, for example, copper sul-
fate or copper acetate. Mixtures of copper sulfate, also in com-
bination with alkali bichromate, with boric acid and copper
acetate with alkali metal fluoroborates are prior art. Dinitro-
phenol has meanwhile been excluded because of its toxicity.
The water-soluble abovementioned copper compounds on their own,
but also in the abovementioned combinations, to not have good
diffusion power adequate to penetrate, for example, the sapwood
of pine poles, even on long standing, and to reach the core.
Wood preservatives based on copper and amines as complexing
agents have been proposed for large-scale impregnation, in parti-
cular boiler pressure impregnation.
EP B 211 181 relates to a wood preservative based on a copper
salt and monoethanolamine for the boiler pressure impregnation of
wood.
EP-B 270 848 describes a wood preservative based on a copper
compound, a carboxylic acid and an aliphatic polyamine for boiler
pressure impregnation.
0975/00098 CA 02248031 1998-09-O1
2
EP-A 423 674 describes a wood preservative based on a metal salt
of an N-organyldiazeniumdioxy compound and a complex-forming
polymeric amine for the boiler pressure process.
It is common to all the wood preservatives described above that
they have a high fixing power for the copper in the wood. By
means of this, the diffusion power of the copper is restricted,
which is why these systems are unsuitable for the afterprotection
of wood.
_ _
Known, currently used systems for the afterprotection of wood
contain, for example, combinations of copper naphthenate, boron
and fluorine compounds. An example of this type of product, which
1s mainly used in the USA, is CuRAP 20 (manufacturer: ISK Bio-
tech), a paste which contains 18.16 of amine-based copper
naphthenate and 40~ of sodium tetraborate decahydrate. Investiga-
tions on poles (species of wood Douglas fir or pine) which had
been treated with this product showed after a service life of
from 1 to 3 years that copper for the major part is virtually
only distributed near to the surface (0-10 mm) in the wood (with
investigated penetration depths of up to 25 mm) and these
products thus only have a very restricted diffusion power for
copper (Conserving energy by environmentally acceptable practices
1n maintaining and procuring transmission poles. 15th annual
report, September 1995, J.J. Morrell, Oregon State University,
Corvallis, Oregon.).
The subsequently published WO 96/233636 describes wood
preservatives in paste form, which comprise a fungicidal metal
compound and a fungicidal boron compound. The metal compounds
also include copper complexed with aminocarboxylic acids or
polycarboxylic acids.
The subsequently published WO 96/233635 describes a wood
preservative which comprises a metal chelate. Copper complexes
with amino acids, iminodiacetic acid, ethylenediaminotetraacetic
acid, dicarboxylic acids and polyphosphates are described.
It is an object of the present invention to make available a wood
preservative for the afterprotection of wood, which has a good
diffusion power of the copper in the wood, with good protection
at the same time against soft rot and Basidiomycetes.
CA 02248031 2005-O1-10
3
It is a further object of the present invention to make available a bandage
which
contains this wood preservative for the afterprotection of wood.
It has now been found that the above objects may be achieved by a wood
preservative based on a copper compound, a polyamine and an inorganic
fungicide, if appropriate a complex-forming organic carboxylic acid or its
ammonium of alkali metal salts, if appropriate further auxiliairies and if
appropriate water for the afterprorection of wood.
More specifically, the invention as broadly claimed relates to a process for
the
afterprotection of wood, which comprises treating the wood with an effective
wood preserving amount of a wood preservative composition comprising a
copper compound, a polyamine or alkanolamine having at least two nitrogen
atoms, and an inorganic fungicide, the treatment being effected by means of a
bandaging process, an inoculation injection process, a borehole process or a
paste process.
The invention also relates to a bandage for the afterprotection of wood,
comprising an effective wood preserving amount of a wood preservative
composition comprising a copper compound, a polyamine or alkanolamine
having at least two nitrogen atoms, and an inorganic fungicide.
These wood preservatives are particularly"suitable for the after-
protection and the aftercare of wood and are used as bandages, in
the inoculation injection process, borehole process and paste
process. They penetrate the sapwood in the presence of moisture,
e.g. soil contact, and have a good deep action.
Copper compounds which can be used are water-soluble or -insolu-
ble compounds, e.g. copper sulfate, copper acetate, copper cit-
rate, copper naphthenate, copper hydroxide, copper hydroxycarbo-
nate, copper oxychloride, copper oxide, copper borate, copper
fluoride, copper fluoroborate, bis(N-cyclohexyldiazeniumdio-
xy)copper or mixtures thereof.
CA 02248031 2005-O1-10
3a
copper hydroxycarbonate, copper hydroxide and mixtures thereof
are preferred.
Copper hydroxide, especially stabilized copper hydroxide (Nord-
deutsche Affinerie), is particularly preferably used.
The action of the wood preservative can be improved by salts of
N-cyclohexyldiazenium dioxide and other diazenium dioxides, e.g.
as the potassium salt, with copper compounds the abovementioned
bis(N-cyclohexyldiazeniumdioxy)copper generally being formed.
The mixtures contain from 0.25 to 20 % by weight of copper calcu-
fated as the element. Some of the copper can also be replaced,
for example, by a corresponding zinc compound.
Polyamines which can be used are alkyleneamines having
3-9 C atoms and 2-4 N atoms such as, for example, ethylene-
diamine, 2-diethylaminoethylamine, diethylenetriamine, triethyl-
enetetramine, tetraethylenepentamine, 1,2-diaminopropane,
1,3-diaminopropane, dipropylenetriamine, tripropylenetetramine,
3-(2-aminoethyl)aminopropylamine, N,N'-bis(3-aminopro-
~
, 0975/00098 CA 02248031 1998-09-O1
4
pyl)-1,3-propanediamine and alkanolamines such as, for example,
aminoetYiylethanolamine, and mixtures thereof.
Ethylenediamine, diethylenetriamine, 1,3-diaminopropane, dipropy-
lenetriamine, aminoethylethanolamine and mixtures thereof are
preferred.
Suitable inorganic fungicides are boron compounds such as alkali
metal borates, aminoborates, boric acid, boric acid esters and
B2~3~ fruorides such as alkali metal fluorides, alkali metal bi-
fluorides, silicon fluorides, ammonium fluorides, ammonium hydro-
gen fluorides; fluoroborates; fluorophosphates; difluorophospha-
tes and mixtures thereof.
Sodium fluoroborate, potassium fluoroborate, boric acid, sodium
fluoride and mixtures thereof are preferred.
Furthermore, complex-forming organic carboxylic acids such as
hydroxycarboxylic acids, aminocarboxylic acids, nitrogen-contai-
ning polycarboxylic acids, ammonium or alkali metal salts thereof
and mixtures thereof can additionally be used.
Suitable hydroxycarboxylic acids which can additionally be used
are, for example, glycolic acid, lactic acid, tartaric acid,
citric acid, malic acid, ammonium or alkali metal salts thereof
and mixtures thereof.
~lno acids such as, for example, glycine, sarcosine, ammonium or
alkali metal salts thereof and mixtures thereof can also be addi-
tionally used.
Suitable nitrogen-containing complex-forming polycarboxylic acids
which can additionally be used are, for example, nitrilotriacetic
acid (NTA), ethylenediaminetetraacetic acid, (EDTA), diethylene-
triaminepentaacetic acid (DPTA), propylenediaminetetraacetic acid
(PDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), ~-ala-
ninediacetic acid, ammonium or alkali metal salts thereof and
mixtures thereof.
The wood preservatives of the present invention can additionally
contain further auxiliaries such as water, binders, paste-forming
agents, organic and inorganic bases, aliphatic carboxylic acids,
ammonium or alkali metal salts thereof, plasticizers, fillers,
wetting agents, thickeners and mixtures thereof.
0975/00098 CA 02248031 1998-09-O1
The wood preservatives can additionally contain water, which
serves to adjust the viscosity and the handling.
Binders and paste-forming agents which can be used are, for exam-
s ple, acrylate resins in the form of aqueous dispersions or
powders, plastisols, aminoplastics, phenolic plastics, PVC-con-
taining plasticizers and mixtures thereof.
organic and inorganic bases which can additionally be used are
ammoi~ia, alkali metal hydroxide solution, amines or mixtures
thereof. Suitable amines are, for example, mono-, di- and
trialkylamines and also alkanolamines.
Suitable alkanolamines are, for example, monoethanolamine,
diethanolamine, triethanolamine, isopropanolamine.
To improve the flexibility of the wood preservative dried onto a
carrier material, aliphatic C5-Czo-carboxylic acids such as hexa-
noic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic
acid, 2-ethylenepentanoic acid, 2-ethylhexanoic acid, 2-ethylhep-
tanoic acid, isooctanoic acid, isononanoic acid, isodecanoic
acid, versatic acids (highly branched monocarboxylic acids),
dicarboxylic acids (C5-CZO) e.g. decanedicarboxylic acid, and se-
bacic acid, can additionally be used. Polycarboxylic acids such
as polyacrylic acids or copolymers of acrylic acid with, for
example, malefic acid and naphthenoic acids are also suitable.
Suitable wood preservatives contain, for example
2-50 $ by weight, preferably 5-40 ~ by weight, of a copper com-
pound,
2-60 $ by weight, preferably 5-50 ~ by weight, of a polyamine,
1-65 ~ by weight, preferably 2-55 ~ by weight, of an inorganic
fungicide,
0-25 ~ by weight, preferably 1-20 ~ by weight, of an alkali me-
tal salt of N-cyclohexyldiazenium dioxide,
0-35 ~ by weight, preferably 1-30 ~ by weight, of a complex-for
ming organic carboxylic acid, its ammonium salts or alka
li metal salts,
0-45 ~ by weight, preferably 1-20 $ by weight, of an auxiliary,
0-50 ~ by weight, preferably 1-40 ~ by weight, of water,
the sum of all components yielding 100 ~ by weight.
- 0975/00098 CA 02248031 1998-09-O1
6
If further components are additionally used for the three-part
combination copper compound, polyamine and inorganic fungicide,
the following wood preservatives have proven suitable:
Composition consisting of
a) 5-40 % by weight of a copper compound
5-35 % by weight of a polyamine
10-50 % by weight of an inorganic fungicide
. _5~5 % by weight of a complex-forming organic carboxylic
acid
2.5-35 % by weight of water;
or
b) 5-40 % by weight of a copper compound
5-35 % by weight of a polyamine
10-50 % by weight of an inorganic fungicide
5-25 % by weight of a complex-forming organic carboxylic
acid
2.5-20 % by weight of an aliphatic C5-C2o-carboxylic or
dicarboxylic acid
2.5-35 % by weight of water;
or especially when using binders and paste-forming agents
c) 5-40 % by weight of a copper compound
5-35 % by weight of a polyamine
5-50 % by weight of an inorganic fungicide
0-5 % by weight of an alkali metal salt of n-cyclohexyl-
diazeniumdioxide
0-20 % by weight of a complex-forming organic carboxylic acid
5-40 % by weight of an auxiliary
0-30 % by weight of water.
The wood preservatives, which can be present as concentrates or
diluted with water as viscous solutions or in the form of pastes,
if appropriate also as a solid salt, is best carried out by pre-
dissolving a polyamine and, if appropriate, complex-forming orga-
nic carboxylic acids or their ammonium or alkali metal salts and,
if appropriate, auxiliaries, especially aliphatic CS-C2o-carboxy-
lic or dicarboxylic acids, using water. The copper compounds are
then dissolved therein. The use of water can be dispensed with if
the substances employed contain sufficient water (eg. water of
crystallization). Solid salts formed from copper compounds, poly-
0975/00098 CA 02248031 1998-09-O1
7
amine and, if appropriate, complex-forming organic carboxylic
acids or their ammonium or alkali metal salts can also be used.
This premixture can even be present as a highly concentrated
paste to which the inorganic fungicides, and if appropriate
further auxiliaries, are then added with stirring.
The pH of the wood preservative in the form of the concentrates
°r pastes is in general between pH 7 and 12. Depending on the
application, the concentrates or pastes can on the one hand be
applied or introduced directly or with addition of binder on to
or into a suitable carrier material. Suitable carrier materials
are, for example, plastic films or webs, e.g. of glass fiber,
p°lypropylene, polyester or viscose fiber, foam or other porous
plastic materials. In this case, the concentrates are applied to
the carrier material, for example, by rolling (calendering).
Binders which can be used are, for example, acrylate resins in
the form of aqueous dispersions, powders; plastisols,
aminoplastics, phenolic plastics, PVC-containing plasticizers.
The system concentrate/carrier material is usually then subjected
to drying, for example air drying or, for example, in an oven at
about 100 - 180°C, the concentrate drying on in highly viscous
form and being bound to the carrier material; this binding can be
improved, if appropriate, by the abovementioned addition of
binders, at the same time the release of wood preservative can be
delayed after application by this means, if necessary, with a
high dose of binder.
The concentrates, in particular on addition of binder, can also
be pressed in the form of extrudates, dried and cut to length in
order to obtain salt cartridges for insertion into wood by means
of boreholes, e.g. in the borehole process. It is also possible
to produce cartridges made of powdered mixtures, e.g. when using
spray-dried concentrates or using powdered raw materials in the
form of pressed articles of salt.
The diffusible pastes and concentrates or cartridges can be used
in the various methods of afterprotection and aftercare when, in
the case of particularly endangered wood components, relatively
large preservative introduction amounts and penetration depths
should be achieved in certain areas.
The pastes are suitable for the bandage process, such as single
bandages or multiple bandages, the inoculation injection process,
borehole process and the paste process.
' 0975/00098 CA 02248031 1998-09-O1
8
Application takes place in the form of preventive or alternati-
vely controlling protective treatments in order
a) permanently to protect timber otherwise not treated with wood
preservatives only in specific sections, e_g. roof beam
heads;
b) to increase the amounts introduced or penetration depths
achieved in the first treatment in the danger areas;
c) in timber which has already been used in construction to
supplement or increase the preservative content from the ba-
sic protection after a relatively long standing time (period
of use);
d) in timber parts which have been used in construction also to
reach those areas, in particular in the course of a control
measure, which cannot be reached using the customary impreg-
nation process.
The invention is described with the aid of the following exam-
ples:
For the tests, the pastes/concentrates were applied in defined
amounts to foam as a carrier. The foam with the paste then went
through a drying process. The bandage obtained was applied in the
soil-air zone after preparation to round wood stocks made of pine
which had been used in underground construction. This area was
then wound with a self-adhesive PVC film and thus outwardly pro-
tected against the penetration of water.
After a standing time of 12 months, the round wood stocks were
dug out, repeatedly cut up perpendicular to the grain in the area
of the soil-air zone, the wood stock discs were removed and the
copper penetration was determined by reacting (spraying) with a
0.2 $ strength aqueous solution of 4-(2-azopyridyl)resorcinol
monosodium salt (copper reagent).
For the tests, pine round wood stocks having a diameter of at
least 20 cm and sapwood widths z 3 cm were used. In each case, an
amount of about 500 g of concentrate/salt mixture per bandage was
applied, the carrier material was incorporated with the active
compound concentrate such that it was about 10 cm above the soil
level and about 30 cm below the soil level; the covering film
0975/00098 CA 02248031 1998-09-O1
_ 9
overlapped this area by at least 10 cm in each case. The bandage
dimensions here were 40 cm x 80 cm. Per formulation, at least 2
bandages were applied to various round wood stocks and tested for
penetration power.
Example A (not according to the invention)
35 $ by weight of copper sulfate
32 $ by weight of potassium bichromate
_ _
30 ~ by weight of boric acid
3 ~ by weight of sodium hydrogen sulfate
The salt was ground, made into a paste with water, acrylate
dispersion (50 ~ strength aqueous dispersion of a copolymer of n-
butyl acrylate and styrene) as the binder (10 T concentrate/2 T
water/3 T binder), applied to the foam as carrier and dried at
120°C for at least 15 min. in a continuous flow.
The bandages obtained were applied to round wood stocks. The tim-
ber was used for construction after a standing period of 12
months, after cutting up the average copper penetration was de-
termined.
---
Copper penetration
after a standing
time of 12
months
round wood mean sapwood width: about 35 mm
stock la: _
mean copper penetration: about 9 mm
The core was not reached in any
position
round wood mean sapwood width: about 38 mm
stock 2a:
mean copper penetration: about 12 mm
The core was not reached in any
position
Example B ( not according to the invention)
50 ~ by weight of copper sulphate
~ by weight of boric acid
5 ~ by weight of sodium hydrogen sulfate
The salt was made into a paste after grinding with water,
45 acrylate dispersion (50 $ strength aqueous dispersion of a copo-
lymer of n-butyl acrylate and styrene) as the binder (10 T con-
- 0975/00098 CA 02248031 1998-09-O1
centrate/2 T water/3 T binder), applied to the foam and dried at
room temperature for at least 24 h. The bandages were applied.
Copper penetration
after a standing
time of 12
months
5 round wood mean sapwood width: about 41
stock lb: mm
mean copper pentration: about 7 mm
The core was not reached in any
position
10 _ _
round wood mean sapwood width: about 37
stock 2b: mm
mean copper penetration: about 9 mm
The core was not reached in any
position
Example C (not according to the invention)
50 ~ by weight of copper sulfate
50 ~ by weight of sodium fluoroborate
The salt is [sic] made into a paste after grinding with water,
acrylate dispersion (50 ~ strength aqueous dispersion of a copo-
lymer of n-butyl acrylate and styrene) as the binder (10 T
concentrate(2 T water/3 T binder), applied to the foam and dried
at room temperature for at least 24 h. The bandage was applied.
Copper penetration
after a standing
time of 12
months.
round wood mean sapwood width: about 32 mm
stock lc:
mean copper pentration: about 12 mm
The core was not reached in any
position
-
round wood mean sapwood width: about 43 mm
stock 2c:
mean copper penetration: about 10 mm
The core was not reached~in any
position
Example D (not according to the invention)
35 ~ by weight of copper acetate
65 ~ by weight of potassium fluoroborate
0975/00098 CA 02248031 1998-09-O1
11
The salt was made into a paste after grinding with water, acry-
late dispersion (50 ~ strength aqueous dispersion of a copolymer
of n-butyl acrylate and styrene) as the binder (10 T
concentrate(2 T water/3 T binder), applied to the foam and dried
at room temperature for at least 24 h. The bandage was applied.
Copper penetration
after a standing
time of 12
months
round wood mean sapwood width: about 37
stock ld: mm
mean copper pentration: about 7 mm
The core was not reached in any
position
round wood mean sapwood width: about 42
stock 2d: mm
mean copper penetration: about llmm
The core was not reached in any
position
Examples according to the invention
Example I
10 ~ by weight of ethanolamine
10 $ by weight of ethylenediamine
20 $ by weight of water
10 $ by weight of copper hydroxycarbonate
50 ~ by weight of boric acid
The concentrate was prepared by stirring and applied to foam and
dried at room temperature for at least 24 h. The bandage was
applied.
Copper penetration
after a standing
time of 12
months
round wood mean sapwood width: about 33 mm
stock I 1:
mean copper penetration:
virtually identical to the sapwood
area
The core is reached
round wood mean sapwood width: about 35 mm
stock I 2:
mean copper penetration:
virtually identical to the sapwood
area
The core is reached
-_ 0975/00098 CA 02248031 1998-09-O1
-- 12
Example II
25.00 $ by weight of aminoethylethanolamine
16.65 $ by weight of water
8.35 $ by weight of copper hydroxycarbonate
50.00 $ by weight of boric acid
The concentrate was prepared by stirring, applied to foam and
dried at room temperature for at least 24 h. The bandage was
applied:
Copper penetration
after a standing
time of 12
months
round wood mean sapwood width: about 41
stock II 1: ~ mm
mean copper penetration:
virtually identical to the sapwood
area
The core is reached
round wood mean sapwood width: about 31
stock II 2: mm
mean copper penetration:
virtually identical to the sapwood
area
The core is reached
Example III
32.50 ~ by weight of aminoethylethanolamine
10.00 ~ by weight of lactic acid
17.00 ~ by weight of water
25.00 ~ by weight of boric acid
15.50 ~ by weight of Cu(OH)2, commercially available,
stabilized (Manufacturer: Norddeutsche
Affinerie)
The concentrate was prepared by stirring and applied to foam and
dried at room temperature for at least 24 h. The bandage was
applied.
0975/00098 CA 02248031 1998-09-O1
- 13
Copper penetration
after a standing
time of 12 months
round wood mean sapwood width: about 38
mm
stock III 1: I
mean copper penetration: virtually
the entire
sapwood area was covered and the
core boundary
was reached.
round wood mean sapwood width: about 33
mm
stock III 2:
_ _ mean copper penetration: virtually
the entire
sapwood area was covered and the
core boundary
was reached
Example IV
7.70 $ by weight of dipropylenetriamine
9.80 ~ by weight of water
2.50 $ by weight of isooctanic acid
2.50 ~ by weight of malic acid
1.00 ~ by weight of N-cyclohexyldiazeniumdioxy-
potassium
5.50 $ by weight of copper hydroxide, commercially
available, stabilized (Manufacturer:
Norddeutsche Affinerie)
38.00 ~ by weight of sodium fluoride
33.00 ~ by weight of polyvinyl chloride powder
(Vinnolit P 4472 from Vinnolit)/
bis-(2-ethylhexyl)phthalate premixture
(mixing ratio: about 4:5)
A paste was prepared by stirring, applied to foam and dried at
130°C for at least 15 min. in a continuous flow oven. The bandage
was applied.
Copper penetration
after a standing
time of 12 months
round wood mean sapwood width: about 40
mm
stock IV 1:
mean copper penetration: virtually
the entire
sapwood area was covered and the
core boundary
was reached.
round wood mean sapwood width: about 35
mm
stock IV 2:
mean copper penetration: virtually
the entire
sapwood area was covered and the
core boundary
was reached
- 0975/00098 CA 02248031 1998-09-O1
4
.. 14
The following examples afford a correspondingly good diffusion
power . -
Example V
14.2 ~ by weight of dipropylenetriamine
8.9 $ by weight of malic acid
18.9 ~ by weight of copper hydroxide carbonate
_ _ [Cu(OH)aCuC03]
1Ø0 $ by weight of water .
35.0 ~ by weight of sodium fluoride
13.0 ~ by weight of boric acid
Deviating from the previously mentioned applications, this time
500 g of the similarly prepared paste were applied directly to
the round wood stock and covered with a plastic film. The incor-
poration conditions were identical to those described previously.
Copper penetration
after a standing
time of 12
months
Round wood mean sapwood width: about 39 mm
stock V 1:
mean copper penetration: virtually
the entire
sapwood area was covered and the
core boundary
was reached.
Round wood mean sapwood width: about 37 mm
stock V 2:
mean copper penetration: virtually
the entire
sapwood area was covered and the
core boundary
was reached.
Example VI
22.50 ~ by weight of 1,3-diaminopropane
24.00 $ by weight of water
10.00 ~'by weight of malic acid
3.50 ~ by weight of N-cyclohexyldiazeniumdioxy-
potassium
15.00 ~ by weight of copper hydroxide, commercially
available, stabilized (Manufacturer:
Norddeusche Affinerie)
25.00 ~ by weight of boric acid
0975/00098 CA 02248031 1998-09-O1
A paste was prepared by stirring, applied to foam and dried in a
continuous flow oven at 140°C.
Example VII
5
22.50 ~ by weight of 1,3-diaminopropane
21.00 ~ by weight of water
7.50 ~ by weight of nitrilotriacetic acid
4.00 ~ by weight of N-cyclohexyldiazenium-
10 _ _ dioxy-potassium
5.00 ~ by weight of glycerol
25.00 ~ by~weight of boric acid
15.00 ~ by weight of copper hydroxide,
commercially available, stabilized
15 (Manufacturer: Norddeutsche Affinerie)
A paste was prepared by stirring, applied to foam and dried for
at least 15 min in a continuous flow oven at 130°C.
Example VIII
17.00 ~ by weight of 1,3-diaminopropane
7.00 ~ by weight of monoethanolamine
26.00 $ by weight of water
8.50 ~ by weight of malic acid
2.50 ~ by weight of bis(N-cyclohexyldiazenium-
dioxy) copper
25.00 ~ by weight of boric acid
14.00 ~ by weight of copper hydroxide, commercially
available, stabilized (Manufacturer:
Norddeutsche Affinerie)
A paste was prepared by stirring, applied to foam and dried for
at least 10 minutes a.n a continuous flow oven at 130°C.
Example IX
16.70 $ by weight of dipropylenetriamine
11.80 ~ by weight of water
8.00 ~ by weight of isooctanoic acid
5.00 ~ by weight of malic acid
16.60 ~ by weight of boric acid
8.60 ~ by weight of copper hydroxide, commercially
available, stabilized Manufacturer:
Norddeutsche Affinerie)
33.30 ~ by weight of polyvinyl chloride powder
0975/00098 CA 02248031 1998-09-O1
16
(Vinnolit P 4472 from Vinnolit)/bis(2-
- ethylhexyl) phthalate premixture
(mixing ratio: about 4:5)
A paste was prepared by stirring, applied to foam and dried for
at least 15 min at 130~C in a continuous flow oven.
Example X
- 18.5 ~ by weight of dipropylenetriamine
5.3 ~ by weight of water
7.7 ~ by weight of isooctanoic acid
7.5 ~ by weight of malic acid
11.5 $ by weight of copper hydroxide, stabilized
36.5 $ by weight of sodium fluoride
13.0 $ by weight of boric acid
A paste was prepared by stirring, applied to foam and dried for
at least 15 min in a continuous flow oven at 130~C.
Example XI
15.4 ~ by weight of dipropylenetriamine
23.9 ~ by weight of water
35.7 $ by weight of copper citrate (about 35$ Cu)
(copper (II) citrate 2,5-hydrate)
25.0 ~ by weight of boric acid
A paste was prepared by stirring, applied to foam and dried for
at least 15 min in a continuous flow oven at 130~C.
Example XII
16.5 ~ by weight of diethylenetriamine
27.5 $ by weight of water
15.0 ~ by weight of malic acid
16.0 ~ by weight of copper hydroxide, stabilized
25.0 ~ by weight of boric acid
A paste was prepared by stirring, applied to foam and dried for
at least 15 min in a continuous flow oven at 130~C.
I i
CA 02248031 2005-O1-10
17
Example XIII
21.0 % by weight of dipropylenetriamine
28.0 % by weight of water
13.2 % by weight of citric acid monohydrate
16.8 % by weight of copper hydroxide (stabilized)
*.
21.0 % by weight of Polybor' (Na2Bg013 x 4 H20)
A.paste-was prepared by stirring, applied to foam and dried for
at least 15 min in a continuous flow oven at 130~C.
Example XIV
19.0 % by weight of dipropylenetriamine
11.9 % by weight of malic acid
16.9 % by weight of copper hydroxide carbonate
32.2 % by weight of water
20.0 % by weight of sodium fluoride
A paste was prepared by stirring, applied to foam and dried for
at least 15 min in a continuous flow oven at 130~C.
* Trademark
