Arsenical creosote wood preservatives

20 Pages·2013·2.69 MB·English

1051-3151115 SR
4/7/87 m 416569060
United States Patent [191 [11] Patent Number: 4,656,060
Krzyzewski [45] Date of Patent: Apr. 7, 1987
[54] ARSENICAL CREOSOTE WOOD [56] References Cited
PRESERVATIVES us. PATENT DOCUMENTS
[76] Invenwn J°hn Krzyzewski'“ Ashbum Drive, 3,376,144 4/1968 Stutz ............................... ..106/15.05
Nepean, Ontario, K2E 6N3, Canada
FOREIGN PATENT DOCUMENTS
[21] Appl. No.: 744,900
1058353 7/1979 Canada .
[22] Filed: Jun. 17, 1985
Primary Examiner-Lorenzo B. Hayes
Attorney, Agent, or Firm-Millen & White
Related US. Application Data
[63] Continuation of Ser. No. 502,378, Jun. 8, 1983, aban [57] ABSTRACT
doned. A novel stable, homogeneous aqueous solution for ap
[30] Foreign Application Priority Data plication to wood surfaces is provided herein. The aque- - '
ous solution consists essentially of creosote, a conven
Sep. 28, 1982 [CA] Canada ................................. .. 412325
tional inorganic wood preservative component, ammo
[51] Int. Cl.4 ......... ..'. ............ .. C09D 5/14; B05D 3/02 nia and an oil. The oil and the creosote are present in
[52] US. Cl. ............................... .. 427/397; 106/ 15.05; speci?ed proportions in the aqueous solution. When the
106/16; 106/17; 106/18; 106/1832; 106/1836;
solution is applied to wood, and the wood dried, a creo
427/441; 428/541; 514/493; 514/494; 514/499;
sote-treated wood surface which may be painted is
514/504
provided.
[58] Field of Search 3 ............... .. 106/1505, 16, 17, 18,
106/1832, 18.36; 427/397, 441; 428/541;
514/493, 494, 499, 504 11 Claims, No Drawings
+------» -"
4,656,060
1 2
to provide relatively long term durability when applied
by pressure impregnation techniques. While such sys
ARSENICAL CREOSOTE WOOD
PRESERVATIVES tems are effective in preventing biological deterioration
of wood and provide clean and paintable surfaces, they,
This application is a continuation of application Ser. 5 however, suffer from several disadvantages. CCA pre
servatives have low stability under storage and process
No. 502,378, ?led June 8, 1983, now abandoned.
ing conditions and penetration into wood is limited.
BACKGROUND OF THE INVENTION ACC preservatives cannot penetrate refractory species
but water repellency of wood treated by ACC is good.
(i) Field of the Invention
Ammoniacal copper salts provide extremely stable
This invention relates to a system and method for the
treating solutions and produce a treated wood product
preservation of timber. In particular, it relates to com
positions for preserving wooden poles, thereby pro which is clean, in which the preservative penetrates
longing the service life of wooden poles partially buried deeply into the wood substance (particularly in the case
of refractory species), but which provides only partial
in the ground by treatment either before or after they
protection to the products against weathering. All sys
are so partially buried and whether the poles are wet or 15
dry. tems provide products which are more or less colored;
(ii) Description of the Prior Art thus the natural appearance of wood is changed or
The wood products with which the present invention covered by the colored preservative and so is unsuitable
for aesthetrially pleasing materials. Furthermore, none
is concerned are materials which are to have low aes
of these systems provides protection against glowing
thetic considerations, (e.g. foundation piles, poles, posts 20
and fences, ties, marina structures, high-way and bridge combustion. The CCA systems are believed to become
construction, laminated systems for exterior use, and ?xed in the wood by oxidation-reduction reactions asso
cooling towers. Such compositions and treatment pro ciated with the chromic acid in the compositions and it
cedures are designed to provide protection not only is these same reactions which are believed adversely to
during the storage and the handling of the timber but 25 affect stability and processing characteristics. More
also to provide protection during the ?nal use of the over, while providing a high level of protection against
fungal attact, they provide only partial protection
timber. It also relates to the treated wood products so
against weathering.
formed.
A piece of timber, due to the manner of its formation, In addition, two main preserving systems are also
possesses anisotropic structure which in?uence its prop 30 used, namely, (1) creosote, and (2) pentachlorophenol in
pole oil. These preserving systems are effective in (1)
erties and behaviour. To overcome and minimize these
disadvantages a number of speci?c problems exist: the preventing fungal and insect attack on the wood sub- '
wood must be protected against degrading environmen stance; and (2) in preventing weathering of the timber.
tal factors (namely, moisture cycling, photodegradation Both of these requirements are important where long
and biological attack; the dimensional stability with 35 life is required in wood exposed to the weather. How- I
respect to moisture cycling must be improved; photo ever, these treatments suffer from several disadvan
degradation due to sunlight might be minimized; the tages. The most important of these is low cleanliness.
resistance to biological attack (fungus) must be im Oil in these systems exudes to the surface making the
proved; and extractives which adversely affect the pro wood unpleasant (dangerous) to handle, impossible to
tective properties of coatings must be sealed within the 40 paint, and provides a surface which readily accumulates
wood. dirt.
Protective systems should impart not only protection Preservative systems which provide clean systems
against biological degradation, but also considerable available at the present time are the oil-free pentachlo
weather resistance. The system_ should provide weather rophenol systmes using liqui?ed gas or highly chlori
resistance with enhanced ?re resistance. 45 nated aliphatic hydrocarbons as a solvent and vehicle
for pentachlorophenol. Data indicates that products
Four classes of treatments are currently used in an
attempt to meet these requirements. The ?rst class is produced by these processes are inferior in weather
that of clear or pigmented penetrating systems which resistance to wood products impregnated by oil-borne
contain fungicides and water-repellent additives, e.g. preservatives. Moreover, neither of the above-men
tioned systems protects the wood against glowing com
polyethylene waxes and metal stearates in a non~aque
ous solvent media. These treatments are de?cient in that bustion.
they must be repeated at regular intervals of about 1 to Thus, each of the preserving systems mentioned
2 years to provide a desired level of protection. above has disadvantages and these can be summarised
The second class is that of stains and sealers. These as follows: The major disadvantage of the use of creo
are normally synthetic resin solutions, usually pig 55 sote and pentachlorophenol oil treatment is their low
mented and designed to penetrate the surface of the cleanliness and their lack of paintability. The major
disadvantage of the use of copper-chrome-arsenate sys
wood. These treatments as well are de?cient, and
tem is limited stability of the treating solution under
should be repeated every one or two years in order to
provide the required degree of protection. processing conditions. The major disadvantage of the
The third class is that of paint systems. Such ‘paint use of ammonical copper compounds is the lack of
systems would normally consist of a primer and top weathering resistance of the treated wood product. The
coats. When well applied, these will provide protection major disadvantages of the use of oil-borne pentachlo—
rophenol treatments is the lack of weathering properties
from two to ?ve years.
The fourth class is that of salt treatments. A number relative to the creosote and pentachlorophenol-oil sys
of salt treatments have been suggested, the most com 65 tems. '
In the past, timbers, e.g. mooring piles were impreg
mon of which are known as copper-chrome arsenate
(CCA), acid-copper-chromate (ACC) and ammoniacal nated ?rst with the water-borne inorganic mixed salts.
copper salts. Presently systems of this type are effective Then, they were seasoned by kiln-drying, air seasoning,
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or some other method. They were then retreated with replace the old poles with new impregnated ones. Poles
creosote. This procedure may take from several months which are given such remedial treatment with presently
to over a year. In Germany, it has been reported that available preservatives are expected to last from about 5
the creosote treatment preceeds and the salt impregna to 15 years longer than if they had been left untreated.
tion follows immediately or soon after. However, this Hence, the groundline treatment must be repeated at
introduces a problem of sludge formation, and disposal about 5 to about 15 year intervals.
of contaminants which introduces yet another problem. The need for prolonging the service life of existing
The main drawback of such double impregnation poles is most urgent. Because many users of such poles
procedure is that processing is expensive because of the cannot meet the demand for new pole requirements,
labour intensive operations of moving timbers to and existing poles must consequently be so improved that
from storage locations in a seasoning yard, and the they will not require early replacement. This, in turn,
delay in processing limited by the rate of moisture lost means that the need for an improved form of groundline
during seasoning. Also the creosote and water-borne preservative is therefore urgently required.
solutions must be stored separately to avoid sludging A number of preservative mastics, or paste-type
problems. In any case, a certain amount of sludge does 5 chemical formulations for groundline treatment exist.
form because the solutions are used in tandem during Most of these formulations contain pentachlorophenol
processing. in a suitable solvent, and non-leach resistant additives
It is frequently necessary to preserve timber products e.g., sodium ?uoride and borax. Such formulations are
(against fungal attack, and marine borers) with two generally applied to the groundline areas of utility poles
immiscible preservatives, i.e. creosote and inorganic 20 in the form of bandages. However, since pentachloro
salts. The reason is that neither creosote nor the inor phenol has been in short supply for the past few years
ganic salts (e.g. copper arsenate) are adequate to protect and since the shortage may continue in the future, an
the timber when used alone. alternative preservative is desirable. On the other hand,
Contemporary systems for heavy duty preservation the non-leach resistant chemicals, when used alone,
of timber (e. g. as utility poles, piles, posts, bridge beams, 25 have a short life, and have been found not to be eco
lumber, etc.) frequently employed pentachlorophenol nomically favourable.
(PCP) as a reliable heavy duty preservative. Applica While pentachlorophenol is very leach resistant, the
tion to leave a clean surface involves processes like rate of penetration of these systems is very slow, often
CELLON (trademark) LPG impregnation or the meth requiring more than about 5 years for the toxic penta
ylene chloride solvent treatment to drive the PCP into chlorophenol system to penetrate to about 1% inch
the wood providing a reasonably clean surface requir depth, It is believed that the pentachlorophenol ban
ing no seasoning. However material treated with PCP dages lose some of their effectiveness after about 10 to
by these processes, suffers from certain disadvantages, about 15 years following treatments, and that retreat
e.g. loss of PCP from wood sublimination and low ments may be necessary at a maximum of about 15 year
water repellency and weather resistance. Both disad 35 intervals. On the other hand, while sodium ?uoride
vantages result in lowering of service life when com penetrates rapidly, the levels of retention are very often
pared with wood treated by the older conventional too low to be effective.
PCP-oil-borne systems. This also results in limitations Pentachlorophenol, the main component of the
to use of the treated wood in closed poorly ventilated above-described groundline preservatives, is oil soluble
areas e.g. basements. The PCP-oil-borne systems have and is carried in solvents, e. g. grease, thickened oil base,
the major disadvantages of wood discoloration, oily etc. Consequently, the system is not essentially compati
unpaintible surfaces, stickiness and dirt retention. ble with wet wood, i.e. wood which has water which is
These disadvantages (using the so-called clean pro considerably above the ?bre saturation point. A very
cesses) can be partially solved by raising the amount of high percentage of poles are wet at the butt ends where
preservative incorporated into the wood thus retaining 45 effective treatment is required. It has also been found
the concentration level above or close to the effective that the toxic components in many of the commercial
threshold value enven after loss of some preservative, formulations of groundline bandage preservatives do
resulting in an acceptable service life. Adequate water not penetrate the entire sapwood depth in poles. Conse
repellency and PCP retention, and elimination of the quently, it is believed that suitable groundline treatment
health hazard due to vapours of PCP, can be realized by of poles may extend their service life by about 2 to 5
additional painting or top-coating of the wood surface. years.
Such additional treatments (use of excess PCP and/or A soluble borate, namely, sodium tetraborate in water
top-coating) considerably increase the cost of the has been used in “pressure-diffusion” treatments in Aus
treated wood and in some places are not economical. tralia. Such process consists of impregnating round
Telephone communication poles, and wooden power 55 material with a high concentration of the borate in an
transmission poles will decay in line service (particu abbreviated schedule (in the retort) and then stacking
larly at the ground/a ir interface) unless protected with the material to allow deeper penetration by diffusion.
wood preservatives. Generally, for a long service life However, this technique suffers the disadvantage that
(about 50 years or more), the poles are pressure impreg an expensive pressure system is necessary.
nated with wood preservatives. These preservatives 60 For maximum protection of timber from biodegrada
often lose effectiveness over a period of about 25 to tion, or marine organisms, it has been suggested that
about 35 years, generally in the groundline region (i.e. wood be treated in two stages. First it should be treated
the ground/ air interface) where conditions for leaching with an arsenical preservative, and subsequently (after a
microbial activity and slow movement of preservative seasoning period) with creosote, or other suitable oil
to the surrounding soil deplete the preservatives to 65 borne preservative. These water-soluble arsenical salts,
ineffective levels. It is much more economical to apply and either creosote, or an oil soluble preservative are
a remedial form of preservative treatment to replenish deposited (impregnated) in the wood to be protected. It
the toxicity required at the groundline region than to is also common practice to preserve timbers for use in
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marine structures for coastal locations by a two step creosote was a heterogeneous mixture, not well suited
operation. Arsenic salts are impregnated ?rst, and after for uniform treatment of timber.
a period of seasoning (usually several months outdoors), A paper in the Forest Products Journal, Vol. 20, No.
11, November 1970 by M. P. Levi et al entitled “Distri
the creosote is impregnated. Deposits of both creosote
bution and Effectiveness in Pinus Sp. of a Water Repel
and arsenic salts are speci?ed at high retentions, i.e.
lent Additive for Water-Borne Wood Preservatives”
creosote at about 20 pounds per cubic foot (pcf), and
discusses the development of a water repellent additive
arsenic at about 1.0 pcf. This labour intensive move
for use with water-borne CCA preservatives to over
ment of timber into the yard for double periods of sea
come the de?ciency of prevention of weathering degra
soning is obviously disadvantageous.
dation.
The present limitation is the requirement for the sea
Ammonical copper arsenite compositions are pres
soning which may be conducted either by stacking in a
ently being used as preservatives. Zinc arsenite compo
storage yard, and» atmospheric evaporation of the mois
sitions are also presently being used as preservatives.
ture, or by arti?cial seasoning in the treating retort. The
Zinc arsenate, zinc arsenite, and zinc phosphate can all
arti?cial seasoning process can be completed within
be applied from an acetic acid solution and, on drying,
about 18 to about 30 hours by steaming or boiling under
the salt is insoluble and ?xed in the wood. However, in
vacuum procedure carried out in the treating retort.
all of these cases, the weather resistance of the treated
In the treating of timber it is self evident that the
wood is not signi?cantly improved.
greater the penetration of the treating agent into the
U.S. Pat. No. 1,145,186 patented July 6, 1915 by Eb
wood, the better the preservation. It has generally been
erhard provided an anticorrosive paint which was based
the practice to treat the timber in two stages—?rst with
on the fact that certain compounds of chromium soluble
water borne salts and, following a seasoning period
in oil or fat respectively, possess very valuable qualities I
(usually several months), then with an oil-borne compo for prevention of rust. These compounds have the same
nent, or creosote. degree of oxidation as chromic acid, or an ethereal
In the area of “oil-borne preservatives” a break 25 solution of chromic acid as well as of perchromic acid
through was made when new preservative carriers and also chromium phosphate dissolved in oil or fat. If
were developed which dissolved lipophilic preserva linseed oil or varnish is acted upon in a suitable manner
tives adequately. Commonly, two solvents are used in by chromyl chloride, and if a violent reaction is pre
North America, methylene dichloride and so-called vented, a clear viscid greenish purple oil, or a varnish
lique?ed petroleum gases. They penetrate into wood respectively is obtained which proves to be highly valu
well and are recoverable from wood after treatment. able as a rust preventing means. To prevent an excessive
Methylene dichloride is used in Canada also for treat action of chromyl chloride upon oils, varnishes, and the
ment of spruce which it penetrates satisfactorily. like, toluene, nitro-benzene, chloroform, aniline or simi
In the ?eld of water-borne preservatives there was a lar hydrocarbons as well as bisulphide of carbon may be
similar need: to ?nd a suitable solvent for spruce with used.
good penetration characteristics. U.S. Pat. No. 1,456,509 issued to A. Mai on May 29,
It has been found that ponding or continuous spray 1923, taught that arsenic acids, sul?des of arsenic,‘
ing for a few months increases preservative penetrabil Schweinfurt or Paris green and other arsenical com
ity of spruce so that a full sapwood penetration can be pounds or mixtures may be brought in to solution to a
obtained by a standard pressure process. White spruce large extent by the action of halogen inorganic sub
poles may be penetrated deeply and uniformly with stances or compounds with easily detachable halogen
creosote throughout the lk-inch sapwood by standard atoms, as, bromine or tribromide of arsenic, or with
impregnation processes when conditioned by fresh organic halogenical compounds or aliphatic or aromatic
water ponding. Ponding now is carried out by ?oating bodies containing several substituted halogen atoms, as
debarked logs in fresh water for about 12 weeks at a 45 phthalyl chloride, tribromacetic acid, tetrachloronaph
mean temperature of about 65° F. thalene or mixtures thereof, in most of the organic sol
When creosote, or petroleum oils are mixed with vents, e.g., acetone, ether, alcohol, amylacetate, ethy
ammonium hydroxide solution and agitated for thor lacetate, benzine, benzol, tar-oils, petroleum, etc., or in
ough blending, almost immediate separation takes place mixtures of any of these substances. Solutions of this
upon storage of the mixture. 50 kind have been said to have the advantage that they
Water soluble phases and oil phases when mixed completely penetrate the wood in one single process,
together are not miscible, generally separate rapidly, that they are not washed out and that according to the
and frequently tend to produce sludges (which could solvent selected they unite in themselves insecticidal
not be used in wood preservation). and fungicidal qualities. Moreover, they have been said
Arsenical creosote (AC) is well known. R. Johnson in 55 to permit the solution of inorganic preservatives, for
the publication in a paper entitled “THE INCORPO example, naphthalene, anthracene, phenols, nitro-com
RATION OF ARSENIC IN CREOSOTE, PART 3* pounds, alkaloid salts, resins and the like, with the sole
STABILITY OF ARSENICAL CREOSOTE IN exception of the free bases; they are also solvents of
THE PRESENCE OF WATER IN WOOD that equal sulfur.
amounts of arsenic can be incorporated with dry creo 60 It has still further been proposed (see U.S. Pat. No.
sote or with creosote saturated with water. Heating of 1,942,977 issued Jan. 9, 1934 to E. E. M. Payne) to treat
As2O3 with creosote at about 90° C., for about 4 hr. wood products with a solution of one or more ammo
produces an arsenical creosote (AC) with a maximum nium phosphates and then with a solution containing
arsenic content of about 0.5 percent As2O3. Higher acid phosphates of magnesium and zinc, in order to
temperatures increase the incorporation of AS203 to a 65 precipitate an insoluble phosphate within the cell struc
maximum of about 0.75 percent at about 200° C. and ture of the material, thereby to improve the color of the
about 0.94 percent at about 220° C., but prelonged re materials and to render the treated material resistant to
?uxing reduces the arsenical contents. The arsenical ?re.
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Copper and zinc-containing fungicides which have liquid and an alkaline inorganic alkali metal salt. This
been proposed (see U.S. Pat. No. 2,414,661 issued Jan. composition suffers the disadvantage of a low level of
21, 1947 to A. A. Nikitin), where prepared by precipita retention.
tion of a zinc salt and a copper salt from an aqueous U.S. Pat. No. 3,390,951 issued July 2, 1968 to J. H.
solution with an alkali solution containing soya bean Finger et a1 provides a method of strengthening, pre
protein, or soaps of fatty acids. serving and extending the life of wooden poles by ap
Fungicides, which have been proposed for cellulosic plying a metal band to the pole surrounding the zone of
materials, (see U.S. Pat. No. 2,423,619 issued July 8, weakness with a ?brous resin impregnated material, and
1947 to L. Roon) comprise copper soaps formed in situ connecting tension means to the pole above the upper
from an aqueous solution of copper salts and aqueous band means and below the lower band means and ex
ammonia by reaction with fatty acids. tending therebetween. This procedure suffers the disad
It has also been proposed to provide water and ?re vantage of being too labour intensive and provides a
resistant coatings on wood, (see U.S. Pat. No. 2,530,453 separate heterogenous addition to the pole.
issued Nov. 21, 1950 to H. R. Frisch) by the use of zinc U.S. Pat. No. 3,409,388 issued Nov. 5, 1968 to R. F.
orthophosphate or zinc orthoarsenate compositions Nelson provides a method for preserving wooden poles
applied as a concentrated solution in aqueous ammonia. by applying a bandage which is an elongated tube of
It has been proposed, (see U.S. Pat. No. 2,722,263 preservative impermeable water soluble material, to
issued Nov. 27, 1956 to C. C. Yeager) to use a com spaced areas of the pole and dissolving the protective
pound having a high fungicidal activity in wood, which ?lm to permit direct contact between the preservative
compound is a metal resin ammonium phenoxide-com 20 and the pole. This suffers the disadvantage of low level
plex metal carboxylic acid soap compound, prepared by of retention and of not providing optimum times of
reacting a resin ammonium phenoxide with a water-sol contact of the wrapped preservative with the wood.
uble salt of a metal capable of forming a complex with U.S. Pat. No. 3,764,377 patented Oct. 9, 1973 by W.
ammonia. E. Keys provided a wood treating composition contain
It has been further proposed, (see U.S. Pat. No. 25 ing a novel arsenic compound that is compatible with
2,768,910 issued Oct. 30, 1956 to J. Krzikalla and O. creosote, and includes the toxic qualities of arsenic com
Lissner) to improve the hardness, compressive strength, pounds as well as those of creosote. The novel organic
hydroscopicity and liability to swelling of wood by arsenic compound is formed by the reaction of arsenous
impregnating the wood with an aqueous ammoniacal oxide (AS203) with N,N,N’,N’-tetrakis(2-hydroxy
solution of polycarboxylic acid containing at least six 30 propyl)ethylene diamine, and has the general structure
carbon atoms.
U.S. Pat. No. 2,875,020 issued Feb. 24, 1959 to R. G.
Ring provides a wood preservative method and pack OH CH3
age including a porous ?brous oil and water permeable Cl?-(IZH-CI-h CH3—CH'-O
sheet, e. g. a porous ?brous material for example, ?brics 35
and felted mats of vegetable ?bres or glass ?bre; a layer N—-CH3—CH3—N A3 0
on one side only of the sheet of an inert, oil base carrier CH3—CH—CH3 CH3-CH—O
of grease-like consistency containing at least 2% penta (IJH (EH3
chlorophenol, and a synthetic reservoir oil and water 2
impervious ?lm completely enclosing the sheet and
layer, e.g. a sleeve of polyethylene, polyvinyl com It has also been proposed, [see British Patent No.
pounds, etc. Such procedure is labour intensive and 1,220,281 published Jan. 27, 1971 in the name of Hick
undesirable. son’s Timber Impregnation Co. (6.3.) Ltd.] to treat
U.S. Pat. No. 2,939,704 issued June 7, 1960 to C. E. wood with an aqueous emulsion containing an aqueous
Wilkinson provides a composition including a suitable 45 solution of a wood preservative composition based on
asphalt base, cut back with a volatile diluent, as well as hexavalent chromium, a water-insoluble insecticide in a
an inorganic ?ller consisting essentially of ?ne asbestos liquid hydrocarbon solvent, and a non-ionic surface
?bres, ?ne mica, ?ne vermiculate or ?ne alkali metal active agent. The emulsion is used by impregnation of
tetraborate. This suffers the disadvantage of lack of the wood by means of a pressure process, to provide
compatibility of the organic component (the asphalt), 50 protection against fungal attack and against a variety of
i.e. the most effective preservative constituent, with wet insects.
wood. Canadian Patent No. 515,610 provides a wood treat
It has also been proposed, (see U.S. Pat. No. ing composition consisting essentially of a material se
3,007,844 issued Nov. 7, 1961 to W. O. Schuly) to use a lected from the group consisting of:
composition comprising a heavy metal ion, borate ions 55 water miscible polyhydric alcohols having from 2 to
and chromate ions as an impregnating agent for the 6 hydroxyl groups; solutions of boric acid in water
preservation of wood. miscible polyhydric alcohols having from 2 to 6
It has further been proposed, (see U.S. Pat. No. hydroxyl groups; solutions of an alkali metal borate
3,105,773 issued Oct. 1, 1963 to S. Frank and D. C. in water miscible polyhydric alcohols having from
Wehner) to preserve wood by imparting pesticidal and 2 to 6 hydroxyl groups; boric acid esters of water
anti-thallophytic properties thereby by ?rst impregnat miscible polyhydric alcohols having from 2 to 6
ing the wood with a water-soluble heavy metal salt, and hydroxyl groups; and mixtures thereof contained in
with an acrylic polymer solution. an impregnant selected from the group consisting
U.S. Pat. No. 3,376,144 issued Apr. 2, 1968 to R. E. of the tars and creosotes.
Strutz provides a wood preservative composition thick 65 Canadian Patent No. 568,393 issued Jan. 6, 1959 to
ened with a combination of a microcrystalline wax, Bror O. H'ager proposed to provide an agent for the
water soluble non-ionic surfactant, and water, com preservation of wood including an aqueous ammoniacal
bined with a mixture of an organic wood preservative solution of an amine-forming metal of the group consist
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mastic of (a) a petroleum fraction selected from oils and
ing of copper, zinc, nickel, cobalt, cadmium and silver,
greases with one of (b) asbestos screenings; (0) natural
and dissolved carbon dioxide of a content of at least
serpentine ?brous fragments; (d) mica ?akes; (e) adipic
two-thirds of the metal content. This composition is far
acid plus asbestos screenings; (f) adipic acid plus natural
too dilute to be used for groundline treatment. The same
serpentine ?brous fragments; or (g) adipic acid plus
patentee, in Canadian Patent No. 960,959 issued Jan. 14,
1975, provided a composition consisting essentially of mica flakes; and (viii) a metallic soap selected from an
(l) a metal compound selected from the group consist insoluble soap of naphthenic acid , octoic acid, 2-ethyl
ing of the oxides, hydroxides, and carbonates of copper, hexoid acid, rosin acids or tall oil acids, with aluminum,
zinc, nickel, cadmium and cobalt, and (2) a fatty acid calcium, cadmium, cobalt, copper, iron, lead, manga
having from 6 to 12 carbon atoms per molecule, dis nese, nickel, tin or zinc; to provide a thickened composi
solved in (3) an annomiacal water solution. Both these tion having a viscosity of at least 30 poises, and desir
compositions suffer the disadvantage that they do not ably to provide one composition of about 30 to about
have optimum high water repellency, optimum low 120 poises, and another composition of about 250 to
water uptake, optimum fast and high preservative pene about 300 poises, the viscosity in poises being measured
tration, and optimum resistance to arsenic leaching. 15 by a Brookfield Viscometer at 25° C.
Canadian Patent No, 978,474 issued Nov. 25, 1975
SUMMARY OF THE INVENTION
naming Michael R. Clarke and Jaromir R. Rak as inven
tors, provides a dilute aqueous composition comprising (i) Aims of the Invention
a normally water-insoluble compound selected from While the use of the compositions outlined above has
zinc arsenate, zinc arsenite, copper arsenate, copper 20 tended to provide a considerable level of protection
arsenite or mixtures thereof, a water repellent compo against speci?c degrading agencies, none of them pro
nent, including a carbonate or bicarbonate and suf? vides a suitable balance of properties for example, excel
cient ammonia to dissolve the normally water-insoluble lent stability, high weather resistance, paintability, good
compound. This composition, while it is very useful, is wood penetration and good water repellency. Addi
too dilute to be used to preserve wooden poles at the 25 tionally some of the compositions outlined provide in
groundline in the form of bandages. Also, the composi
the one system not only the protective properties men
tion is not sufficiently compatible with wet poles.
tioned above, but also a measure of protection against
Canadian Patent NO. 1,001,948 issued Dec. 21, 1976
fire and do not adversely affect the natural appearance
naming J aromir Rak as inventor provides a wood pre
of the treated wood.
servative composition imparting a clean surface and 30
Therefore, objects of this invention are to provide
good service life to the wood substrate, comprising (a)
aqueous wood-treating solutions in which a suitable
an organic wood preservative agent, i.e. pentachloro
balanced improvement is provided in the following
phenol (as primary preservative); (b) a hydrophobic
properties, namely: a good level of weather resistance;
agent selected from fatty acids and their esters, fatty
low mammalian toxicity; resistance to biological and
alcohols and various waxes, suitably having at least ten
fungal attack; resistance to water penetration; resistance
carbon atoms in the longest chain in the molecule; (c) an
to extractive staining; substantially no adverse effect on
amorphous polymer; and (d) an organic solvent for (a),
protection against glowing combustion, good adhesion
(b) and (0).
properties between the wood and a coating, e. g. paint or
Canadian Patent No. 1,058,353 issued July 17, 1979
glue, etc. later to be applied thereto; and no substantial
naming John Krzyzewski, as inventor provides a thick 40
adverse effect on lumber surfaces.
ened ammonia-base wood treating composition for ap
Another object of this invention is to provide a wood
plication as a covered layer to a wood surface, the com
treating aqueous solution which may be used for treat
position comprising: (A) a preservative component
ing wet poles.
which is one of (i) a normally water-insoluble salt se
Yet another object of this invention is to provide a
lected from the group consisting of zinc arsenate, zinc
wood treating aqueous solution having high levels of
arsenite, copper arsenate, copper arsenite and mixtures
thereof; (ii) an ammonia-soluble salt selected from the retention. .
group consisting of copper borate, zinc borate or mix (ii) Statements of Invention
tures thereof, and copper chromate, zinc chromate or
By this invention, an homogeneous creosote-contain
mixtures thereof; or (iii) an ammonia dispersible organo
ing aqueous ammonical composition is provided for
metallic compound selected from the group consisting
application to a wood surface, the composition compris
of copper naphthenate, zinc naphthenate or mixtures
ing (A) creosote in an amount of from about 21% to
thereof, copper-8-quinolinolate, zirrc-S-quinolinelate or
about 70% by weight; (B) a preservative component
mixtures thereof, or tributyltin oxide; and (iv) suf?cient
which is selected from the group consisting of (i) a
aqueous ammonia, in a concentration of about 1 to 55
normally water-insoluble salt selected from the group
about 28% by weight NH3 to solubilize the normally
consisting of zinc arsenate, zinc arsenite, copper arse
water-insoluble salt (i), or the ammonia-soluble salt (ii),
or to disperse the organometallic compound (iii); and nate and copper arsenite and mixtures thereof; (ii) an
ammonia-soluble salt selected from the group consisting
(B) a suf?cient amount of thickener component selected
from the ‘group consisting of: (v) (a) a saturated fatty of copper borate, zinc borate, or mixtures thereof, and
copper chromate, zinc chromate, or mixtures thereof;
acid of 12 to 22 carbon atoms; (b) an unsaturated fatty
(iii) an ammonia-dispersible organometallic compound
acid of 12 to 22 carbon atoms; (0) a copper, zinc, so
selected from the group consisting of copper naphthen
dium, potash, or amine salt of a saturated fatty acid of 12
ate, zinc naphthenate or mixtures thereof, copper-8-'
to 22 carbon atoms; or (e) mixtures thereof; (vi) (a)
asbestos screenings; (b) natural serpentine ?brous frag quinolinolate, zinc-8-quinolinolate or mixtures thereof,
ments; (0) mica flakes; (d) adipic acid plus asbestos or tributyltin oxide, (iv) suf?cient aqueous ammonia, in
screenings; (e) adipic acid plus natural serpentine ? a concentration of about 1 to about 28% by weight
NH; to provide about 10% to about 60% by weight of
brous fragments; or (f) adipic plus mica ?akes; (vii) a
4,656,060
11 12
water, thereby to solubilize the salt (i) or to solubilize By yet another feature, the aqueous solution includes
the salt (ii) or to disperse the compound (iii), and a about 0.1-about 4% by weight of at least one of cop
stable homogeneous, aqueous solution for application to per arsenate, zinc arsenate, copper arsenite and zinc
wood surfaces, such stable, aqueous solution consisting arsenite (as Zn or Cu or Zn+Cu metal) of the total
essentially of: (A) creosote; (B) a preservative compo aqueous solution; about 0.15 to about 10% by weight of
nent which is selected from the group consisting of (i) a the total aqueous solution of a carbonate or bicarbonate;
normally water-insoluble salt selected from the group and from about l5—about 26% ammonia.
consisting of zinc arsenate, zinc arsenite, copper arse By a further feature, the ratio of active preser
nate and copper arsenite and mixtures thereof; (ii) an vative/ammonia/water in the preservative component
ammonia-soluble salt selected from the group consisting (B) is about 20-40/15-25/65-35.
of copper borate, zinc borate, or mixtures thereof, and By another feature, component (B) comprises (a) a
copper chromate, zinc chromate, or mixtures thereof; normally water-insoluble compound selected from the
(iii) an ammonia-dispersible organometallic compound group consisting of zinc arsenate, zinc arsenite, copper
selected from the group consisting of copper naphthen arsenate, and copper arsenite and minerals thereof in an
ate, zinc naphthenate or mixtures thereof, copper-8 amount of about 0.1 to about 4% by weight (as Zn or
quinolinolate, zinc-8-quinolinolate or mixtures thereof, Cu metal) of the total aqueous solution; (b) about 0.5 to
or tributyltin oxide, and, with ether (i), (ii) or (iii), (iv) about 10% by weight of the total aqueous solution of a
suf?cient aqueous ammonia, in a concentration of about water-repellent component comprising one of (i) a wa
1 to about 28% by weight NH3 to solubilize the salt (ii) ter-insoluble organic acidic compound having a
20
or to dissolve the salt (ii) or to disperse the compound solubility§0.2% and in concentrated aqueous ammo
(iii); and (C) a solvent for the compounds (A) and (B), nia, the water-insoluble organic acidic compound being
the solvent being selected from the group consisting of selected from the group consisting of a substantially
fuel oil, pole treating oil, kerosene, tie-treating oil, water-insoluble saturated or unsaturated monocarbox
waste crank oil, and a petroleum distillate; the solvent ylic acid having between 8 and 15 carbon atoms in the
(C) being present in a sufficient amount, of about 13% carboxylic acid; a substantially water-insoluble satu
to 80% by volume of the total aqueous solution, and the rated or unsaturated monocarboxylic acid having be
creosote (A) being present in an amount of from 7% to tween 8 and 15 carbon atoms in the carboxylic acid
about 70% by volume of the total aqueous solution, substituted with a hydrocarbon radical; a substantially
thereby to provide the stable, homogeneous aqueous water-insoluble saturated or unsaturated monocarbox
solution; wood, when such solution, is applied thereto, ylic acid having between 8 and 15 carbon atoms in the
and when the wood is thereby providing a creosote carboxylic acid substituted with a hydroxyl radical; a
treated wood surface which may be painted. substantially water-insoluble saturated or unsaturated
By this invention a procedure is provided which monocarboxylic acid having between 8 and 15 carbon
comprises applying, to the surface of wood, the above atoms in the carboxylic acid substituted with a halogen;
35
described stable, homogeneous aqueous solutions, maleinized unsaturated fatty acids from animal or vege
thereby impregnating such wood, and then drying such table sources, and having an acid value of about 200 to
surfaces with a resulting loss of ammonia, thereby pro about 500; maleinized unsaturated fatty acid esters from
viding a creosote-treated wood surface which may be animal or vegetable sources and having an acid value of
painted. Accordingly, the invention also provides a about 200 to about 500; maleinized unsaturated fatty
method which includes the step of painting the creo acids, formed by the reaction of maleic acid with fatty
sote-treated wood. polycarboxylic acids and having an acid value between
about 200 and about 500; maleinized unsaturated fatty
(iii) Other Features of the Invention
acids formed by the reaction of maleic alkyds with fatty
By other features, the preservative component (B) polycarboxylic acids, and having an acid value between
45
may comprise one of the following: (A) (i) a normally about 200 and about 500; maleinized unsaturated fatty
water insoluble salt selected from the group consisting acid resins formed by the reaction of maleic acid with
of zinc arsenate, zinc arsenite, copper arsenate, copper fatty polycarboxylic acids, and having an acid value
arsenite and mixtures thereof, and (ii) suf?cient aqueous between about 200 and about 500; maleinized unsatu
ammonia, in a concentration of about 1 to 28% by rated fatty acid resins formed by the reaction of maleic
weight NH3 to solubilize the salt (i); (b) (ii) an ammonia alkyds with fatty polycarboxylic acids, and having an
soluble salt selected from the group consisting of cop acid value between about 200 and about 500; aromatic
per borate, zinc borate or mixtures thereof, and copper carboxylic acids having an acid value between about
chromate, zinc chromate or mixtures thereof; and (iv) 200 and about 500; acid esters of phosphoric acid with
suf?cient aqueous ammonia, in a concentration of about 55 monohydric alcohols and having an acid value between
1 to about 28% by weight NH3 to solubilize the salt (ii); about 200 and about 500; acid esters of phosphoric acid
or (C) (iii) an ammonia dispersible organometallic com with fatty alcohols and having an acid value between
pound selected from the group consisting of copper about 200 and about 500; synthetic polycarboxylic acids
naphthenate, zinc naphthenate or mixtures thereof; cop= having an acid value between about 200 and about 500,
per-8-quinolinolate, zinc-P8~quiloinolate or mixtures 60 and mixtures thereof, in an amount of up to about 200%
thereof; or tributyltin oxide; and (iv) suf?cient aqueous of the zinc or copper, or (ii) or (iii) a combination of the
ammonia, in a concentration of about 1 to about 28% by selected organic acidic compound and a carbonate or
weight NH3 to disperse the compound (iii). bicarbonate ion selected from the group consisting of
By another feature, the aqueous solution includes an zinc carbonate, zinc bicarbonate, copper carbonate and
acrylic resin as a water repellency improving agent. 65 copper bicarbonate in an amount of up to about 150% of
By a further feature, the aqueous solution includes the zinc or copper; and (c) ammonia, in an amount of
zinc thiocyanate, copper-thiocyanate or mixtures about 1 to about 28% by weight of the total aqueous
thereof to increase toxicity. solution; the ammonia being suf?cient to solubilize the
4,65 6,060
14
. 13
arsenate, zinc oxide, ammonium carbonate, dibutyl
normally water-insoluble salt of zinc or copper and the
normally water-insoluble water-repellent compound. phosphate, and an aqueous ammonia solution (about
By a feature thereof, the organic acidic compound is 10% by weight); (e) zinc metaborate, zinc carbonate,
selected from: monocarboxylic acids having between 8 docanoic acid and an aqueous solution (about 5% by
weight); (f) copper carbonate, copper arsenate, lauric
and 15 carbon atoms; hydroxy substituted monocarbox
ylic acids having between 8 and 15 carbon atoms; alk acid, and an aqueous ammonia solution (about 5% by
oxy substituted monocarboxylic acids having between 8 weight; (g) copper arsenate, decanoic acid, and aqueous
ammonia solution (about 7% by weight); (h) copper
and 15 carbon atoms; halogen substituted monocarbox
ylic acids having between 8 and 15 carbon atoms; satu carbonate, copper arsenite, dihexyl phosphate, and an
aqueous ammonia solution (about 7% by weight); (i)
rated fatty acids having between 8 and 15 carbon atoms;
unsaturated fatty acids having between 8 and 15 carbon copper carbonate, copper arsenate, decanoic acid and
atoms; polycarboxylic acids of acid value between an aqueous ammonia solution (about 7% by weight) and
about 200 and about 500; aromatic carboxylic acids of (i) copper arsenate, copper carbonate, decanoic acid
and an aqueous ammonia solution, (about 5% by
acid value between about 200 and about 500; acid esters
of phosphoric acid with saturated monohydric alcohols weight). .
By a further variant, the preservative (B) comprises
having between 8 and 15 carbon atoms; and acid esters
of phosphoric acid with unsaturated fatty alcohols hav (a) a soluble component adapted to form a normally
water-insoluble compound of zinc or zinc and copper
ing between 8 and 15 carbon atoms.
By another feature, the water repellent component with arsenic acid or arsenious acid in an amount of
has a solubility of about 0.5% in concentrated aqueous 20 about 0.1——about 4% by weight (as Zn or Zn+Cu
ammonia and comprise a substantially water-insoluble metal) of the total aqueous solution, the weight ratio of
monocarboxylic acid having between 8 and 15 carbon zinc or zinc and copper (as oxides) to arsenic (as oxides)
atoms in the carboxylic acid and being selected from the being about 1.5 or more; (b) about O.l5-—about 10% by
group consisting of octanoic, nonanoic (pelargonic, weight of the total aqueous solution of a water repellent
capric (decanoic), lauric (dodecanoic) and myristic 25 component comprising at least one of carbonate and
(tetradecanoic); and unsaturated fatty acids selected bicarbonate ions, in an amount of up to about 150% of
from the group consisting of A9ylo-decylenic, and A940 the zinc or copper; and (c) ammonia, in an amount of
dodecylenic. about l—about’ 28% by weight of the total aqueous
By yet a further feature, the aqueous solution has a solution.
pH of about 9 or more and comprises an aqueous solu 30 By yet another feature the ratio of CO2/NH3/Zn/As
tion containing: at least one of (a) copper ammonium or CO7/NH3/Zn+Cu/As is about 1.7-2.3/5.9-6.7/1
arsenate, (b) copper ammonium arsenite, (c) zinc ammo .9-2.9/0.9; and the ammonia is suf?cient to solubilize
nium arsenate, and (d) zinc ammonium arsenite, and (e) the normally water-insoluble salts of zinc or zinc and
anions of the selected organic acidic component. copper and the normally water-insoluble water repel
.By another feature, the unsaturated fatty acids from 35 lent compound.
By other features, the preservative component (B)
animal or vegetable sources which are maleinized are
may comprise one of the following: (a) zinc ammonium
derived from sardine oil, lard, coconut oil, sesame oil,
soybean oil, tung oil or corn oil. cations, arsenic or arsenious anions, and anions of a
By a still further feature, the aqueous solution has a carbonate or a bicarbonate; (b) zinc ammonium cations
pH of about 9 or more and comprises an aqueous solu 40 and copper ammonium cations, arsenic or arsenious
tion containing: (i) at least one of (a) copper ammonium anions; and anions of a carbonate or a bicarbonate; (c)
arsenate, (b) copper ammonium arsenite, (c) zinc ammo zinc ammonium cations, arsenic or arsenious anions,
nium arsenate, (*d) zinc ammonium arsenite, and (ii) and (c) anions of a carbonate or a bicarbonate; or (d)
anions of both (e) an organic acidic component and (f) zinc ammonium cations and copper ammonium cations,
a carbonate or bicarbonate. 45 arsenic and arsenious anions, and anions of a carbonate
By yet a further feature, the aqueous solution con and a bicarbonate.
tains: saturated monocarboxylic acids having between 8 By a further feature, the aqueous solution contains
to 15 carbon atoms, alkoxy substituted monocarboxylic carbonates of zinc or zinc and copper.
By another feature, the aqueous solution contains
acids having 8 to 15 carbon atoms and halogen substi
tuted monocarboxylic acids having between 8 and 15 50 zinc arsenate or zinc arsenite.
carbon atoms; unsaturated fatty acids having between 8 By a still further feature, the aqueous solution con
and 15 carbon atoms; mixed higher fatty acids, derived tains zinc arsenate and copper arsenate or zinc arsenite
from animal or vegetable sources, maleinized with ma and copper arsenite.
By yet other features, component (B) in the aqueous
leic acid or maleic anhydride and an inorganic carbon
ate. 55 solution may comprise (A) from about 1 to about 4 parts
By another feature the aqueous solution contains acid by volume of a composition comprising (a) copper am
esters of phosphoric acids with monohydric alcohols or monium cations, (b) arsenic or arsenious anions, and (c)
fatty alcohols, and zinc carbonate or copper carbonate. anions of a carbonate or a bicarbonate; and (B) from
By another feature, the aqueous solution contains about 1 to about 3 parts by volume of a composition
comprising (a) zinc ammonium cations, (b) arsenic or
copper arsenate and zinc arsenate.
By another feature, the aqueous solution may contain, arsenious anions and (c) anions of a carbonate or a bicar
as the preservative component one of the following (a) bonate, the Cu being present in from about 19 to about
75% by weight based on total metal or (C) about 3 parts
zinc arsenate, nonanoic acid, zinc carbonate, and an
aqueous ammonia solution (about 7% by weight); (b) by volume of a composition comprising (a) copper am
zinc arsenate, zinc carbonate, monododecyl phosphate, 65 monium cations, (b) arsenic or arsenious anions, and (c)
and an aqueous ammonia solution (about 7% by anions of a carbonate or a bicarbonate; and (D) 1 part by
weight); (0) zinc arsenate, decanoic acid, zinc carbonate volume of a composition comprising (a) zinc ammo
and an aqueous solution (about 10% by weight); ((1) zinc nium cations, (b) arsenic or arsenious anions and (c)
4,656,060
15 16
anions of a carbonate or a bicarbonate, the Cu being By a feature thereof, the preservative component (B)
present in about 60% by weight, based on total metal; or includes zinc thiocyanate, copper thiocyanate or mix
(E) 1 part by volume of a composition comprising (a) tures thereof to increase toxicity.
copper ammonium cations, (b) arsenic or arsenious an By a feature thereof, the preservative component (B)
ions, and (c) anions of a carbonate or a bicarbonate, and includes about 0.1 to about 4% by weight copper arse
(P) 1 part by volume of a composition comprising (a) nate, copper arsenite, zinc arsenate or zinc arsenite or
zinc ammonium cations, (b) arsenic or arsenious anions, mixtures thereof (as Zn and/or Cu metal) of the total
and (c) anions of a carbonate or a bicarbonate, the Cu aqueous solution; about 0.15 to about 10% by weight of
being present in 40% by weight of total metal; or (G) 1 the total aqueous solution of a carbonate or a bicarbon
part by volume of a composition comprising (a) copper ate; and from about l5—about 26% ammonia.
ammonium cations, (b) arsenic or arsenious anions, and
(c) anions of a carbonate or a bicarbonate, the Cu being GENERALIZED DESCRIPTION OF THE
present in about 19% by weight of a total metal; or INVENTION
(I) Thus, completely unexpected results have been pro
arsenic oxide (Asm): 1.2 parts by weight 15 vided by mixing any of the wood preservative composi
zinc oxide: 3.6 parts by weight tions used and described heretofore with ammonium
NH4HCO3: 4.0 parts by weight aqueous ammonia
hydroxide in the presence of a small amount of an oil
solution (28% NH3, 20 ml in 100 ml H2O): 91.0
type solvent, e.g. a petroleum oil. This was found to be
parts by weight
true for various oils, e.g. fuel oil (no. 2), pole treating
(I) 20 oil, kerosene, tie treating oil, waste crank oil and the
arsenic oxide (Asv): 1.4 parts by weight
petroleum distillate known by the trade name VAR
zinc oxide: 3.6 parts by weight
SOL. Stable, uniform, single phase solutions were pro
HN4I-ICO3: 4.1 parts by weight
duced in a wide range of concentrations. Also, unex
aqueous ammonia solution (28% NH3, 20 ml in 100
pected results are obtained when ammonium hydroxide
ml H2O): 91.9 parts by weight 25
was blended with a large volume of the oil, in the pres
(K)
ence of even a small quantity of creosote. Once again,
arsenic oxide (Asv): 1.4 parts by weight
stable single phase solutions are obtained. Another un
copper oxide: 18 parts by weight
expected result which was observed was that, in a par
zinc oxide: 1.0 parts by weight
ticular blend in a range which was on the verge or
annonium bicarbonate: 2.4 parts by weight 30
instability, the addition of a small quantity of copper
aqueous ammonia solution (28% NH3, 23.7 ml in 100 ml
naphthenate, resulted in stability being restored.
H2O): 93.5 parts by weight
The essence of this invention is the stabilization of
(L)
arsenic oxide (Asv): 1.4 parts by weight creosote with a conventional wood preservative com
position using ammonia and a speci?ed oil-like homoge
copper oxide: 1.2 parts by weight 35
nizing solvent, e.g. an oil. Thus, many types of wood
zinc oxide: 1.8 parts by weight
preservative compositions may be used. One variant of
aqueous ammonia solution (28% NH3, 22.5 ml in 100
wood preservative component comprises an aqueous
ml H2O): 95.6 parts by weight
solution containing (a) a normally water-insoluble com
or (M)
arsenic oxide (Asv): 1.4 parts by weight pound of zinc or zinc and copper with arsenic acid or
copper oxide: 0.6 parts by weight arsenious acid in an amount of about 0.1-about 4% by
zinc oxide: 2.7 parts by weight weight (as Zn or Zn+Cu metal) of the total aqueous
NH4HCO3: 3.5 parts by weight solution, the weight ratio of zinc or zinc and copper (as
aqueous ammonia solution (28% NH3, 21.2 ml in 100 oxides) to arsenic (as oxides) being about 1.5 or more;
ml H2O): 91.8 parts by weight 45 (b) about 0.15-about 10% by weight of the total aque
By a feature of the aqueous solution, the preservative ous solution of carbonate and/or bicarbonate ions in an
component (B) may comprise: (i) a normally water amount of up to about 150% of the zinc or the zinc and
insoluble salt selected from the group consisting of zinc copper; and (c) ammonia, in an amount of about l-
about 28% by weight of the total aqueous solution; and
arsenate, zinc arsenite, copper arsenate, copper arsenite
and mixtures thereof; and (iv) sufficient aqueous ammo 50 the ratio of COZ/NH3/Zn/AC or CO2/NH3/Zn
nia, in a concentration of about 1 to about 28% by +Cu/As being about 1.7—2.3/5.9—6.7/l.9—2.9/0.9, the
weight NH3 to solubilize the salt (i); or it may comprise: ammonia being suf?cient to solubilize the normally
(A) (II) an ammonia-soluble salt selected from the water-insoluble salt of zinc or zinc and copper, and the
group consisting of copper borate, zinc borate or mix carbonate and/or bicarbonate.
tures thereof, and copper chromate, zinc chromate or 55 The constituents of the preservative component of
mixtures thereof; and (iv) suf?cient aqueous ammonia, this composition may range in concentration (expressed
in a concentration of about 1 to about 28% by weight as percentage by weight of the total) as follows: 1. Zinc
NH; to solubilize the salt (ii); or it may comprise (A) (iii) or zinc and copper arsenic compound, present as the
an ammonia dispersible organometallic compound se= arsenate or the arsenite with the weight ratio of zinc or
lected from the group consisting of copper naphthenate, 60 zinc and copper (as oxides) to arsenic (as oxides) being
zinc naphthenate or mixtures thereof, copper=8= about 1.5 or more, in an amount of about 0.1-4 (as Zn or
quinolinolate, zinc-8=quinolinolate or mixtures thereof, Zn+Cu metal); 2. Carbonate and/or bicarbonate ions
or tributyltin oxide; and (iv) suf?cient aqueous ammo present in proportions ranging up to about 150% of the
nia, in a concentration of about 1 to about 28% by zinc and copper, in an amount of about 0.l5-—about 10;
weight NH3 to disperse the compound (iii). 65 and 3. Ammonia, in an amount of about 1—about 28 and
By a feature thereof, the preservative component (B) the banance, to 100%, water, and preferably with the
includes: an acrylic resin as a water repellency improv ratio of CO2/NH3/Zn/As or CO2/NH3/Zn+Cu/As
ing agent. being about l.7—2.3/5.9-6.7/1.9—2.9/0.9.
4,656,060
18
acid with fatty polycarboxylic acids, and having an acid
> There are three classes of preservative components
value between about 200 and about 500; maleinized
useful in this invention. One class comprises water
unsaturated fatty acid resins formed by the reaction of
’ insoluble but ammonia-soluble zinc arsenate, zinc arsen
maleic alkyds with fatty polycarboxylic acids, and hav
ite, copper arsenate or copper arsenite or mixtures
ing an acid value between about 200 and about 500;
thereof.
aromatic carboxylic acids having an acid value between
Another class includes water-soluble, ammonia-solu
about 200 and about 500; acid esters of phosphoric acid
ble salts, namely, copper metaborate or zinc metaborate
with monohydric alcohols and having an acid value
or mixtures thereof or copper chromate or zinc chro
between about 200 and about 500; acid esters of phos
mate or mixtures thereof.
phoric acid with fatty alcohols and having an acid value
Another class includes water-soluble, ammonia-solu
between about 200 and about 500; synthetic polycarbox
ble salts, namely, copper metaborate or zinc metaborate
ylic acids having an acid value between about 200 and
or mixtures thereof or copper chromate or zinc chro
about 500, and mixtures thereof, in an amount of up to
mate or mixtures thereof.
A third class includes water-insoluble, ammonia dis about 200% of the zinc or copper, or (ii) or (iii) a combi
persible organometallics, e.g., copper naphthenate or 15 nation of the selected organic acidic compound and a
zinc naphthenate or mixtures thereof, copper-8 carbonate or bicarbonate ion selected from the group
consisting of zinc carbonate, zinc bicarbonate, copper
quinolinolate or zinc-8-quinolinolate or mixtures
carbonate and copper bicarbonate in an amount of up to
thereof, or tributyltin oxide.
An especially preferred preservative component in about 150% of the zinc or copper; and (c) ammonia, in
the aqueous solution of this invention is based on copper 20 an amount of about 1 to about 28% by weight of the
and/or zinc ammonium complexes containing arsenic total aqueous solution; the ammonia being sufficient to
solubilize the normally water-insoluble salt of zinc or
anions (AS111 or As") and other additives, all compo
copper and the normally water-insoluble water-repel
nents being soluble in one common aqueous ammonia
lent compound.
cal solution. In the above-noted composition, the pre
The constituents of the preservative component in
servative components, in the form of water-in-soluble 25
the aqueous solution of this invention may range in
salts of zinc or copper or mixture of these, are solubi
concentration (expressed as percentage by weight of the
lized in admixture with certain speci?ed water repellent
compounds in the ammoniacal solution. total) as follows: 1. Zinc and/or copper arsenic com
The preservative component in the aqueous solution pound, present as the arsenate or the arsenite, in an
of this invention comprises an aqueous solution contain 30 amount of about 0.1-about 4 (as Zn or Cu metal); 2.
ing: (a) a normally water-insoluble compound selected Water repellent compound being a water-insoluble or
ganic acidic compound having a solubility 50.2, the
from the group consisting of zinc arsenate, zinc arsenite,
compound being present in proportions ranging be
copper arsenate, and copper arsenite and mixtures
thereof in an amount of about 0.1 to about 4% by tween 0% and about 200% of the zinc or copper; or
weight (as Zn or Cu metal) of the total aqueous solu 35 carbonate or bicarbonate ions present in proportions
tion; (b) about 0.15 to about 10% by weight of the total ranging between 0% and about 150% of the zinc or
copper; or both the water-insoluble organic acid com
aqueous solution of a water repellent component com
prising one of (i) a water insoluble organic acidic com pound and the carbonate or bicarbonate in an amount of
pound having a solubility of 20.2% and in concentra about 0.15-about 10; and 3. Ammonia, in an amount of
tion aqueous ammonia, the water insoluble organic acid 40 about 1-about 28.
compound being selected from the group consisting of a Whether copper and/or zinc is used, the organic
substantially water-insoluble saturated or unsaturated acidic component may generally be de?ned as an acidic
monocarboxylic acid having between 8 and 15 carbon compound which is insoluble in water but which is
capable of forming compounds with the metal ammonia
atoms in the carboxylic acid; a substantially water
insoluble saturated or unsaturated monocarboxylic acid 45 complex which are soluble in aqueous ammoniacal solu
tions. The organic acidic component has a solubility of
having between 8 and 15 carbon atoms in the carboxylic
50.5%, preferably about 3% in concentrated aqueous
acid substituted with a hydrocarbon radical; a substan
ammonia (about 28%). Such component may be a sub
tially water-insoluble saturated or unsaturated mono
stantially water-insoluble monocarboxylic acid having
carboxylic acid having between 8 and 15 carbon atoms
in the carboxylic acid substituted with a hydroxyl radi 50 between 8 and 15 carbon atoms in the carboxylic acid
and being either unsubstituted or substituted with hy
cal; a substantially water-insoluble saturated or unsatu
rated monocarboxylic acid having between 8 and 15 drocarbon radicals, hydroxyl radicals or halogens. Ex
amples include capric (decanoic), lauric (dodecanoic),
carbon atoms in the carboxylic acid substituted with a
myristic (tetradecanoic); unsaturated fatty acids, for
halogen; maleinized unsaturated fatty acids from animal
example A9’lo-decylenic, A9Jo-dodecylenic. The pre
or vegetable sources, and having an acid value of 200 to 55
500; maleinized unsaturated fatty acid esters from ani ferred materials are those saturated and unsaturated
higher aliphatic acids containing from nine to ?fteen
mal or vegetable sources and having an acid value of
carbon atoms. Other organic acidic compounds which
about 200 to about 500; maleinized unsaturated fatty
acids, formed by the reaction of maleic acid with fatty may be used are maleinized unsaturated fatty acids or
polycarboxylic acids and having an acid value between 60 esters from animal or vegetable sources such as, for
about 200 and about 500; maleinized unsaturated fatty example, sardine and other ?sh oils, lard, coconut oil,
acids formed by the reaction of maleic alkyds with fatty sesame oil, soybean oil, tung oil, corn oil, and having an
polycarboxylic acids, and having an acid value between acid value of about 200-about 500; maleinized unsatu
rated fatty acids; oils and resins formed by the reaction
about 200 and about 500; maleinized unsaturated fatty
acid resins formed by the reaction of maleic acid with 65 of maleic acid or maleic alkyds with the fatty polycar
fatty polycarboxylic acids, and having an acid value boxylic acids having an acid value between about 200
and about 500; aromatic carboxylic acids and deriva
between about 200 and about 500; maleinized unsatu
rated fatty acid resins formed by the reaction of maleic tives thereof having an acid value between about 200