U.S. patent number RE28,778 [Application Number 05/564,316] was granted by the patent office on 1976-04-20 for phenolic synthetic detergent-disinfectant.
This patent grant is currently assigned to West Laboratories, Inc.. Invention is credited to William Schmidt, Murray W. Winicov.
United States Patent |
RE28,778 |
Winicov , et al. |
April 20, 1976 |
Phenolic synthetic detergent-disinfectant
Abstract
Unique and novel phenolic synthetic detergent-disinfectant
compositions are provided wherein the detergent component is an
anionic detergent and the phenolic components thereof consist
essentially of ortho phenylphenol in admixture with high activity
and intermediate activity phenolics, the ratio of ortho
phenylphenol to the high and intermediate activity phenolics being
from about 4:1-1.1:1. When prepared as a use dilution, the ortho
phenylphenol is present in an amount of at least about 450 p.p.m.
When the ortho phenylphenol is employed only with the high activity
phenolics, the preferred minimum amount of ortho phenylphenol
should be at least about 600 p.p.m. and the ratio of the ortho
phenylphenol to the high activity phenolics can then be from about
2.5:1-1.5:1 and, when used with intermediate activity phenolics at
the same preferred minimum level, the ratio of the ortho
phenylphenol to the intermediate activity phenolics can be from
about 2.1:1-1.25:1. The novel phenolic synthetic
detergent-disinfectant compositions of the invention are effective
not only against Staphylococcus and Salmonella but also against the
troublesome Pseudomonas species in hard water.
Inventors: |
Winicov; Murray W. (Flushing,
NY), Schmidt; William (Sea Cliff, NY) |
Assignee: |
West Laboratories, Inc. (Long
Island City, NY)
|
Family
ID: |
27498567 |
Appl.
No.: |
05/564,316 |
Filed: |
April 2, 1975 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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205346 |
Dec 6, 1971 |
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887748 |
Dec 23, 1969 |
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Reissue of: |
348112 |
Apr 5, 1973 |
03824190 |
Jul 16, 1974 |
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Current U.S.
Class: |
514/736; 510/386;
510/505 |
Current CPC
Class: |
A01N
31/08 (20130101); C11D 3/48 (20130101); A01N
31/08 (20130101); A01N 2300/00 (20130101) |
Current International
Class: |
A01N
31/08 (20060101); A01N 31/00 (20060101); C11D
3/48 (20060101); C11D 003/48 () |
Field of
Search: |
;252/106,107
;424/346,347 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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789,713 |
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Jan 1958 |
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UK |
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872,900 |
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Jul 1961 |
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UK |
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927,255 |
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May 1963 |
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UK |
|
Primary Examiner: Willis, Jr.; P. E.
Attorney, Agent or Firm: Thompson, Jr.; Howard E.
Parent Case Text
.Iadd.
This is an application for reissue of U.S. Pat. No. 3,824,190
issued July 16, 1974, which .Iaddend..[.This application.]. is a
continuation-in-part of application Ser. No. 205,346, filed Dec. 6,
1971, now abandoned, which in turn is a continuation of application
Ser. No. 887,748, filed Dec. 23, 1969, now abandoned.
Claims
What is claimed is:
1. A phenolic synthetic detergent-disinfectant composition
comprising an aqueous alkaline solution having a pH of about 10 to
13 and containing a mixture of phenolics and at least 0.2 parts,
per part by weight of said phenolic mixture, of anionic synthetic
surface active agent, said phenolic mixture consisting essentially
of ortho phenylphenol in the amount of at least about 5% by weight
of said composition and the balance of the other phenolics in said
mixture being a member selected from the group consisting of
.Iadd.the high activity phenolics .Iaddend.
4-chloro-2-cyclopentylphenol, .Iadd.and .Iaddend.
4-chloro-2-benzylphenol, .Iadd.the intermediate activity phenolics
.Iaddend. 4-chloro-2-phenylphenol .[.y.]., 6-chloro-2-phenylphenol,
4-.[.5.]. .Iadd.t.Iaddend.-amylphenol, 4-n-amylphenol,
2,4-dichloro-3,5-dimethylphenol, 4-chloro-3,5-dimethylphenol,
5-methyl-2-isopropylphenol, .Iadd.and .Iaddend.ortho
chloro-p-phenylphenol, and mixtures thereof, the weight ratio of
ortho phenylphenol to said other phenolics being from about .[.4:1
to 1.1:1.]. .Iadd.2.5:1 to 1.5:1 when said other phenolics include
only high activity phenolics, from about 2:1 to 1.25:1 when said
other phenolics include only intermediate activity phenolics, and
being proportioned between these limits when said other phenolics
are mixtures of high and intermediate activity phenolics according
to the relative amounts of each. .Iaddend.
2. The phenolic synthetic detergent-disinfectant composition of
claim 1 wherein the balance of said phenolic mixture is
4-chloro-2-cyclopentylphenol.
3. The phenolic synthetic detergent-disinfectant composition of
claim 1 wherein the balance of said phenolic mixture is
4-chloro-2-benzylphenol.
4. The phenolic synthetic detergent-disinfectant composition of
claim 1 wherein the balance of said phenolic mixture is a mixture
of 4-chloro-2-phenylphenol and 6-chloro-2-phenylphenol.
5. The phenolic synthetic detergent-disinfectant composition of
claim 1 wherein the balance of said phenolic mixture is
4-t-amylphenol. .[.6. The phenolic synthetic detergent-disinfectant
composition of claim 1 wherein the ratio of ortho phenylphenol to
the other phenolics is from about
2.5:1.5:1..]. 7. The phenolic synthetic detergent-disinfectant
composition
of claim 1 wherein the phenolic mixture is in powdered form. 8. The
phenolic synthetic detergent-disinfectant composition of claim 1
wherein the anionic synthetic surface active agent is selected from
the group consisting of aliphatic sulfonates, sulfonates of
aliphatic-aromatic hydrocarbons, ester sulfonates, amide
sulfonates, and sulfonates containing ether, amino, keto and
sulfone groups, as well as those obtained from sulfated fatty
alcohols, sulfated fatty condensation products such as sulfated
ethoxylated primary or secondary alcohols, and sulfated fatty
glycerides, acids, esters, phosphates, and modified
carboxylates, and mixtures thereof. 9. A germicidal use solution
comprising a mixture of phenolics and at least 0.2 parts, per part
by weight of said phenolic mixture, of anionic surface active
agent, diluted with water, including water having a hardness as
high as about 1,000 p.p.m., in an amount to provide in said use
solution at least about 750 p.p.m. of said mixture of phenolics,
said phenolic mixture consisting essentially of ortho phenylphenol
and the balance of the other phenolics in said mixture being a
member selected from the group consisting of .Iadd.the high
activity phenolics .Iaddend.4-chloro-2-cyclopentylphenol, .Iadd.and
.Iaddend.4-chloro-2-benzylphenol, .Iadd.the intermediate activity
phenolics .Iaddend.4-chloro-2-phenylphenol,
6-chloro-2-phenylphenol, 4-.[.5.]..Iadd.t.Iaddend.-amylphenol,
4-n-amylphenol, 2,4-dichloro-3,5-dimethylphenol,
4-chloro-3,5-dimethylphenol, 5-methyl-2-isopropylphenol, .Iadd.and
.Iaddend.ortho chloro-p-phenylphenol, and mixtures thereof, the
weight ratio of ortho phenylphenol to said other phenolics being
from about 4:1 to 1.1:1 .Iadd.when said other phenolics include
high activity phenolics, and being from about 2:1 to 1.25:1 when
said other phenolics include only intermediate activity phenolics,
.Iaddend.and said use solution containing
at least about 450 p.p.m. of ortho phenylphenol. 10. A germicidal
use solution as defined in claim 9 wherein the balance of said
phenolic
mixture is 4-chloro-2-cyclopentylphenol. 11. A germicidal use
solution as defined in claim 9 wherein the balance of said phenolic
misture is
4-chloro-2-benzylphenol. 12. A germicidal use solution as defined
in claim 9 wherein the balance of said phenolic mixture is a
mixture of
4-chloro-2-phenylphenol and 6-chloro-2-phenylphenol. 13. A
germicidal use solution as defined in claim 9 wherein the balance
of said phenolic
mixture is 4-t-amylphenol. 14. A germicidal use solution as defined
in claim 9 wherein the ortho phenylphenol is present in an amount
of at least
about 600 p.p.m. 15. A germicidal use solution as defined in claim
9 wherein .Iadd.the other phenolic is a high activity phenolic, and
.Iaddend.the ratio of ortho phenylphenol to the other phenolics is
from
about 2.5:1 to 1.5:1. 16. A germicidal use solution as defined in
claim 9 wherein said synthetic anionic surface active agent is
selected from the group consisting of aliphatic sulfonates,
sulfonates of aliphatic-aromatic hydrocarbons, ester sulfonates,
amide sulfonates, and sulfonates containing ether, amino, keto and
sulfone groups, as well as those obtained from sulfated fatty
alcohols, sulfated fatty condensation products such as sulfated
ethyoxylated primary or secondary alcohols, and sulfated fatty
glycerides, acids, esters, phosphates, and modified
carboxylates, and mixtures thereof. 17. The process of disinfecting
surfaces contaminated with Pseudomonas, Staphylococcus and
Salmonella organisms and combinations thereof, that comprises
applying to such contaminated surfaces a germicidal use solution as
defined in claim 9, the disinfecting activity of such use solution,
whether prepared in distilled or hard water, being adequate to free
stainless steel rings contaminated with said organisms within a 10
minute contact period when tested in conformance with the AOAC "Use
Dilution Confirmation Method."
Description
This invention relates to novel phenolic synthetic
detergent-disinfectant compositions which contain anionic detergent
and a mixture of phenolics, the phenolic mixture consisting
essentially of ortho phenylphenol, and the other phenolics in the
mixture being members selected from the class consisting of high
activity and intermediate activity phenolics. This invention
further relates to novel phenolic synthetic detergent-disinfectant
compositions which are effective not only against Staphylococcus
and Salmonella but also against the troublesome pseudomonas species
in hard water.
BACKGROUND OF THE INVENTION
The use of phenolics as disinfectants is well established in the
art, such as is represented by U.S. Pats. 1,980,966 to Blocke;
2,572,855 to Guy; 2,802,881 to Rickert; 3,002,883 to Butt et al.;
3,215,596 to Moyle et al.; and 3,257,273 to Shambough et al., as
well as by British Pats. 789,713 to Schuelke and Mayr; 872,900 to
pearson et al.; 927,255 to Wright; and 1,150,966 to Bondy et al. As
can be seen from this representative sampling of the prior art,
phenolic disinfectants are generally comprised of mixtures of
substituted phenols solubilized with alkali, anionic detergents,
soaps and the like and, in addition, frequently contain alkaline
phosphates, small amounts of a chelating agent, solvents, perfumes
and the like. For example, the British Patent to Wright (927,255)
discloses utilizing ortho phenylphenol with other phenols in
compositions which contain soap as the detergent, the detergent
being derived from the saponification of castor oil with potassium
hydroxide to obtain potassium ricinoleate. This patent also
discloses the use of oleic acid to react with excess alkali.
British Pat. 1,150,966 to Bondy et al. also reveals the use of
ortho phenylphenol in admixture with other phenolics to provide a
solid composition in tablet form which is intended for use, after
being dissolved in water, as a household detergent, such as for
dishes.
The above two British prior art references have been singled out as
they ostensibly appear to reflect the concepts of this invention.
It is important to bear these references in mind for it will be
seen, as revealed in more detail hereinafter, that the presence of
soap is detrimental to the function of the disinfectant of the
invention and that unless one employs only particular types of
phenols with ortho phenylphenol and these types only at the proper
levels, the effectiveness of the phenolic disinfectant of the
invention against Staphylococcus, Salmonella and particularly the
troublesome Pseudomonas species in hard waters will not be
achieved.
It is also well known to those skilled in the art that the
inclusion of small amounts of an anionic detergent will aid in the
performance of these phenolic disinfectants but that higher ratios
of the detergent to the phenolics interferes with their
effectiveness. It is further known that the alkali content of these
phenolic disinfectant compositions has to be controlled so that the
pH of the use dilutions prepared therefrom is not significantly
higher than the pK of the phenolics employed in the disinfectant
composition.
More recently, phenolic disinfectant compositions have been
comprised of high activity phenolics alone or of mixtures of high
activity phenolics with intermediate or low activity phenolics.
A good general survey of phenolic compounds has been presented by
R. F. Prindle and E. S. Wright in Disinfection, Sterilization and
Preservation by Lawrence and Block, Lee and Febiger, Philadelphia,
1968.
For purposes of this invention, the term "phenol coefficient," as
employed throughout the application and in the appended claims,
should be understood as being based upon the following definitions:
a high activity phenolic is one having a phenol coefficient of
about 150 or higher at temperatures of from about 20.degree. C. to
37.degree. C. against S. aureus. Similarly, an intermediate
activity phenolic is one having a phenol coefficient of from about
25 to 150, and a low activity phenolic is one having a phenol
coefficient of less than 25; the phenol coefficient being
obtainable by the methods set forth in the Methods of Analysis of
the Association of Official Agricultural Chemists (AOAC), 10th
Edition.
The disinfectant activity of disinfectants is determined and
measured by the official USDA test as described on pages 82-84 of
the AOAC, 10th edition, hereinafter referred to and identified as
the Use Dilution Confirmation (UDC) test, and is employed to test
disinfectants which are miscible with water to confirm phenol
coefficent results, and to determine maximum dilutions that are
effective for practical disinfection. In general, the test involves
providing an organism to be tested, such as S. aureus, S.
choleraesuis, Pseudomonas aeruginosa and the like, and preparing
sterilized ring carriers. The ring carriers are placed into contact
with the organism to be tested and are then placed on a petri dish
to allow the organism to dry as a film on the ring. The
contaminated carriers are then placed in a solution of the
germicide to be tested for a 10 minute exposure interval and the
results are reported in groups of 10 rings.
The disinfectant activities are reported at the recommended
dilution of the germicides being tested against S. aureus, S.
choleraesuis, and Pseudomonas aeruginosa; distilled water is
specified to dilute the germicidal products. However, hard water
can be used as the diluting medium in addition to distilled water,
and if pass results are obtained, additional efficacy claims can be
made for the product.
Generally, commercially available phenolic disinfectant
compositions fail against Pseudomonas organisms in waters
containing as little as 100 p.p.m. AOAC hardness and even fail in
city water that is ordinarily considered to be "soft"; that is,
having an AOAC hardness of as little as about 50 p.p.m.
Consequently, the claimed activity of these phenolic disinfectant
products against Pseudomonas organisms cannot be completely relied
upon to actually disinfect against Pseudomonas organisms under
actual use conditions unless they are specifically guaranteed for
use in water other than distilled water.
It is known that ortho phenylphenol has a relatively low phenol
coefficient and is, therefore, relatively ineffective against S.
aureus and S. choleraesuis. However, ortho phenylphenol is about as
effective, on a weight basis, against Pseudomonas organisms as are
the high activity phenolics. Since the solubility characteristic of
a phenolic in a use dilution limits the amount of any one phenolic
that can be incorporated in a product, it has been the practice to
include some ortho phenylphenol in product formulations in order to
enhance the performance of these products against Pseudomonas.
However, the ortho phenylphenol content is usually kept below the
total amount of other phenolics present in the product and, rarely
has it been increased to a level approximately equal to that of the
other phenolics present. It has been possible, therefore, to
provide compositions containing, in use dilution, about 500 p.p.m.
or more of combined high activity phenolics and ortho phenylphenol,
plus a small amount of a chelating agent, which are effective
against Pseudomonas in distilled water.
In attempting to formulate products that would pass against
Pseudomonas in hard water, however, a different problem has been
encountered. Attempts to increase the amount of high activity
phenolic or decrease the recommended dilution were not effective
since the solubility limit of the phenolic was reached before
enough high activity or intermediate activity phenolics could be
added to accomplish the desired result. Increasing the amount of
ortho phenylphenol at the expense of the other phenolics was also
found to be ineffective since the amount needed to disinfect
against Pseudomonas would still be inadequate against other test
organisms such as Staphylococcus and Salmonella.
THE INVENTION
In the phenolic synthetic detergent-disinfectant compositions of
the present invention, it has been found that ortho phenylphenol
can be combined with high activity and/or intermediate activity
phenols to provide effective disinfectant action against
Pseudomonas as well as against Staphylococcus and Salmonella
organisms. When provided in a use dilution, the level at which the
phenolic disinfectant of the invention becomes effective is when
there is present therein at least about 750 p.p.m. total phenolics
of which ortho phenylphenol comprises at least about 450 p.p.m.
When provided as a composition to be diluted for use, for example,
in the ratio of one ounce of composition in one gallon of water,
the amount of total phenolics that should be present, based upon
the total weight of the composition, should be at least about 9.6%
by weight of which at least about 5.75% by weight is ortho
phenylphenol. Whether in the form of a use dilution or composition,
the weight ratio of ortho phenylphenol to the high activity and/or
intermediate activity phenolics present can range from about
4:1-1.1:1. At these levels of high activity and/or intermediate
activity phenolics and minimum amounts of ortho phenylphenol, there
is established a "threshold of effectiveness" above which added
amounts of intermediate activity or high activity phenolics will
aid in their performance against Pseudomonas in hard water, but
below which the same phenolics will not contribute significantly to
their effectiveness against Pseudomonas in hard water. On the other
hand, there is no comparable threshold of effectiveness for ortho
phenylphenol against Pseudomonas in distilled water. In distilled
water there is essentially an additive effect which governs the
efficacy of a combination of phenolics whether or not the phenolics
contain ortho phenylphenol at any level.
When employed in distilled water containing a trace of a chelating
agent, as little as 500 p.p.m. ortho phenylphenol could give
consistent pass results against Pseudomonas aeruginosa. However,
when the same level of ortho phenylphenol is used in hard waters
containing from 50 p.p.m. to 500 p.p.m. hardness, consistent
failures are encountered. Even when the ortho phenylphenol level is
raised to about 600 p.p.m., generally unsatisfactory results are
obtained in hard water.
The results discussed and described hereinabove were determined
according to the previously identified UDC test. While these
results were determined according to the same test, it should be
appreciated that the conditions of this test are not exactly
reproducible from one laboratory to another, even over long runs,
since the average of positive tubes for a given test dilution may
vary slightly. Taking this into account, the UDC test results
reported hereinafter are based upon the following assigned
valuations:
ASSIGNED VALUATIONS
(a) "0"--denotes no more than one (1) positive tube in sixty
(60).
(b) "0-1"--denotes a long term average of less than one (1)
positive tube out of ten (10).
(c) "1-10"--denotes a long term average of more than one (1)
positive tube out of ten (10).
Although the official AOAC procedure identified earlier states that
no more than 1 positive tube in 60 will give the prescribed kill
with a confidence limit of 95%, variations in individual laboratory
test procedures and consequent results can give rise to conditions
wherein a "b"type result can occasionally be reflected as an "a"
result. In view of this, those compositions which support a "b"type
result are considered as being acceptable. With these
considerations in mind, the results discussed and described
hereinabove are tabulated below wherein the use dilution contained
the indicated levels of ortho phenylphenol and, as a celating
agent, a small amount (25 p.p.m.) of ethylenediamine tetraacetic
acid (EDTA), and wherein the term "Positive tubes/10 tubes" denotes
the results obtained in distilled water and hard water against
Pseudomonas aeruginosa, the hard water results being typical for
waters varying from about 100 p.p.m.-1,000 p.p.m. AOAC
hardness:
______________________________________ TABULATION OF RESULTS
______________________________________ Positive tubes/10 tubes
Distilled Hard Use dilution level of ortho phenylphenol H.sub.2 O
H.sub.2 O ______________________________________ 400 p.p.m. and
less 1-10 1-10 450 p.p.m. 0-1 1-10 500 p.p.m. 0 1-10 600 p.p.m. 0
1-10 700 p.p.m. and more 0 0
______________________________________
The foregoing relationships can be summarized as follows:
In distilled water, the effect of the phenolics is essentially
additive whether or not they contain ortho phenyl phenol;
In hard water at an ortho phenylphenol level of less than 450
p.p.m., the addition of other phenolics has little or no effect in
improving performance;
In hard water having an ortho phenylphenol level above 450 p.p.m.,
the addition of other phenolics improves performance.
The last stated relationship is extremely important. The addition
of intermediate activity or high activity phenolics to a product is
generally customary since ortho phenylphenol, in itself, exhibits
poor performance against Staphylococcus and Salmonella organisms.
In formulating compositions containing ortho phenylphenol in
combination with a high activity phenolic, it has been found to be
economical to utilize a ratio of ortho phenylphenol to high
activity phenolics within the above indicated range of 4:1-1.1:1
but preferably from about 2.5:1-1.5:1 so that a use dilution
containing, for example, 600 p.p.m. ortho phenylphenol would also
preferably contain from about 200-400 p.p.m. of the high activity
phenolics and still provide the desired efficacy. Under ordinary
conditions, a high activity phenolic present in a use dilution at a
level from about 200-300 p.p.m. has been found to be sufficient in
combination with ortho phenylphenol, to disinfect against other
organisms in addition to Pseudomonas.
For reasons of economy or solubility, the additional phenolics can
be selected entirely or partly from the intermediate activity
phenolics wherein the weight ratio of ortho phenylphenol to the
intermediate phenolics can be from about 2:1-1.25:1.
Representative of the high activity phenolics which can be employed
in the present invention are such compounds as
4-chloro-cyclopentylphenol available under the Trademark "Dowicide
9," and 4-chloro-2-benzylphenol available under the Trademark
"Santophen-1."
Illustrative of the intermediate activity phenolics which can be
employed are such compounds as 4-chloro-2-phenylphenol and
6-chloro-2-phenylphenol which are provided as a mixture available
under the Trademark "Dowicide 32," 4-t-amylphenol, 4-n-amylphenol,
2,4-dichloro-3,5-dimethylphenol (DCMX), 4
-chloro-3,5-dimethylphenol (PCMX), 5-methyl-2-isopropylphenol and,
ortho chloro-p-phenylphenol, available under the Trademark
"Dowicide 4."
The phenolic synthetic detergent-disinfectant compositions of the
present invention can be formulated to include other conventionally
employed components such as solvents, "builders," and the like as
is well known to those skilled in the art.
The amount of anionic synthetic detergent which can be incorporated
can vary over wide limits from as little as about 0.2 parts per
each part of total phenolic to as high as 2 or 3 parts detergent
per part of total phenolic.
It is understood that the terms "detergent" and "surfactant," are
synonymous and generally refer to materials which have a cleansing
action like soap but which are not derived from fatty acids. When
the prefix "synthetic" is used with these terms, it is understood
to refer to surface active agents which contain structurally
unsymmetrical molecules having both a hydrophilic, or
water-soluble, group and a hydrophobic, or oil-soluble portion, in
which the hydrophilic and/or hydrophobic group was formed by a
chemical reaction other than simple saponification.
Similarly, use of the term "anionic" throughout the application and
in the appended claims is understood as referring to those
detergent, surfactants and surface active agents, such as the
aliphatic sulfonates, sulfonates of aliphatic-aromatic
hydrocarbons, ester sulfonates, amide sulfonates, and sulfonates
containing ether, amino, keto and sulfone groups, as well as those
obtained from sulfated fatty alcohols, sulfated fatty condensation
products such as sulfated ethoxylated primary or secondary
alcohols, and sulfated fatty glycerides, acids, esters, phosphates,
and modified carboxylates.
"Builders" can also be incorporated in the phenolic synthetic
detergent-disinfectant compositions in order to improve detergency.
Examples of such builders are such compounds as tetrapotassium
pyrophosphate (TKPP), sodium tripolyphosphate (STP), trisodium or
potassium phosphate, sodium carbonate, and the like.
Similarly, solvents such as alcohols, glycols, or low molecular
weight glycol ethers can be utilized to improve solubility,
freeze-thaw stabilty and like characteristics.
In the present invention, the alkali content of the phenolic
synthetic detergent-disinfectant compositions and the pH of the use
dilutions are not critical and those skilled in the art will
recognize that they can utilize the well-known relationships
between the pK values of the phenolics employed and the desirable
pH range of the use dilutions. The balance needed to aid in
solubilizing the phenolics and the pH efficacy requirements of the
use dilution are well known to those skilled in the art. Some pH
values or ranges are indicated herein to aid in a clearer
understanding of the invention as illustrated in the examples set
forth hereinbelow. In general, liquid concentrates which are
suitable commercial products will have a pH within the range of
about 10 to 13, and will characterically provide at use dilution a
pH within the range of about 9 to 10.5.
In addition to the components listed above, the phenolic synthetic
detergent-disinfectant compositions of the invention can also have
incorporated therein small amounts of dye, perfume, or reducing
agents which serve to color, perfume and prevent oxidation of the
phenolic composition, the uses of which are well known to those
skilled in the art.
As is also well known to those skilled in the art, small amounts of
chelating agents can be utilized for their special effect in
promoting pseudomonacidal properties of germicidal phenolics in
distilled water. For this reason, in some of the examples that
follow, small amounts of EDTA are employed as representative of
conditions known to the art. EDTA complexes less than its own
weight of calcium and magnesium so that, for example, 25 p.p.m.
EDTA in use dilution may insure effectiveness in distilled water
where only traces of heavy metal cations are found, these cations
originating mainly from the bacteria culture itself. However, 25
p.p.m. EDTA has no such demonstrable effect in 100 p.p.m. hard
water, and good kills are obtained only when the phenolic synthetic
detergent-disinfectant compositions contain the amounts and ratios
of phenolics in accordance with the present invention. That is,
compositions of this invention are effective in distilled water and
in hard waters with or without small amounts of EDTA or other
chelating agents.
A clearer understanding of the phenolic synthetic
detergent-disinfectant compositions of the present invention will
be obtained when considered together with the following examples
which are set forth as being merely illustrative of the invention
and are not intended, in any way, to be limitative thereof.
The use dilutions of EXamples I-VI were prepared from the phenolics
of the invention by diluting them in water. The terms "OPP" denotes
ortho phenylphenol, "p.p.m." refers to parts per million, "%"
refers to the weight percent of the particular component based upon
total weight of the composition prior to dilution, and "HW" refers
to AOAC hard water. Other than employing small amounts of an alkali
to adjust pH and 25 p.p.m. EDTA in Examples I-III, no other
components or agents were added to the use dilutions so that the
results were obtained on an equal comparative basis. The letters in
parenthesis identify the use dilution systems in each of the
Examples.
EXAMPLE I
UDC test results against Pseudomonas aeruginosa for a use dilution
having a pH of from about 9.0 to 10.5 and containing 300 p.p.m. OPP
and the indicated amount of additional high activity phenolics or
intermediate activity phenolics in 100 p.p.m. and 400 p.p.m. AOAC
hard water were determined and are set forth below in Table 1. In
Table 1, the high activity phenolics, Dowicide 9, and Santophen-1,
are identified as H-1 and H-2, respectively, and the intermediate
activity phenolics, 4-t-amylphenol, Dowicide 32 and DCMX, are
identified as I-1, I-2 and I-3, respectively.
TABLE 1 ______________________________________ Positive tubes per
10 tubes Amount Ratio phenolic OPP to 100 p.p.m. 400 p.p.m.
Phenolic (p.p.m.) phenolic HW HW
______________________________________ (a) H-1 600 0.5:1 1-10 1-10
(b) H-2 600 0.5:1 1-10 1-10 (c) I-1 600 0.5:1 1-10 1-10 (d) I-2 600
0.5:1 1-10 1-10 (e) I-3 600 0.5:1 1-10 1-10
______________________________________
From the results set forth in Table 1 above, it can be seen that
when as much as 600 p.p.m. of intermediate activity or high
activity phenolics are employed, they do not suffice to get pass
results when only 300 p.p.m. OPP is employed.
EXAMPLE II
In this example, the pH of the use dilution was again from about
9.0-10.5, but the OPP level was raised to 400 p.p.m. and combined
with the indicated amounts of high activity or intermediate
activity phenolics which are identified in the same manner as in
Example I above. The results are tabulated below.
TABLE 2 ______________________________________ Positive tubes per
10 tubes Amount Ratio phenolic OPP to 100 p.p.m. 400 p.p.m.
Phenolic (p.p.m.) phenolic HW HW
______________________________________ (a) H-4 300 1.33:1 1-10 1-10
(b) H-1 500 0.8:1 1-10 1-10 (c) H-2 300 1.33:1 1-10 1-10 (d) H-2
600 0.655:1 1-10 1-10 (e) I-1 500 0.8:1 1-10 1-10 (f) I-2 300
1.33:1 1-10 1-10 (g) I-2 500 0.8:1 1-10 1-10 (h) I-3 500 0.8:1 1-10
1-10 ______________________________________
As can be seen from the results in Table 2, at an OPP level of 400
p.p.m., poor results were obtained even at concentrations of high
activity and intermediate activity phenolics which approach the
solubility limits of these phenolics.
EXAMPLE III
The results obtained when the level of OPP in the use dilution was
raised to 450 p.p.m. and combined with the indicated amounts of
high activity or intermediate activity phenolics are set forth
below in Table 3 wherein the pH of the use dilution was the same as
in Examples I and II and wherein the high activity and intermediate
activity phenolics are identified in the same manner as in Example
I.
TABLE 3 ______________________________________ Positive tubes per
10 tubes Amount Ratio phenolic OPP to 100 p.p.m. 400 p.p.m.
Phenolic (p.p.m.) phenolic HW HW
______________________________________ (a) H-1 200 2.25:1 1-10 1-10
(b) H-1 300 1.5:1 0-1 0-1 (c) H-1 400 1.13:1 0 0 (d) H-2 300 1.5:1
0-1 0-1 (e) I-1 400 1.13:1 0-1 0-1 (f) I-2 400 1.13:1 0-1 0-1 (g)
I-2 300 1.5:1 0-1 0-1 ______________________________________
The results in Table 3 above indicate that good results are
obtained only when the level of OPP is raised to 450 p.p.m. and the
added phenolics, whether high activity or intermediate activity,
are at a level of at least about 300 p.p.m. It is at these minimum
levels of OPP and high activity and intermediate activity phenolics
that the threshold of effectiveness is reached and it is
significant to note that at these levels, the effective weight
ratio range of OPP to either the high activity phenolic or the
intermediate activity phenolic is the same; that is, 1.13:1-1.5:1.
It should be noted that in system (a), wherein the level of high
active phenolic and the level of OPP were at their accepted minimum
amounts, pass results were not obtained since the use dilution
contained less than the minimum level of the sum of the phenolics,
but that when the level of high activity phenolic was increased, as
shown in system (b) pass results were obtained. Pass results were
also obtained when the intermediate activity phenolic was at its
minimum level as seen in system (g).
The results set forth in Table 3 were further found to be
essentially the same for waters having as little as 50 p.p.m. or as
high as 1,000 p.p.m. AOAC hardness.
EXAMPLE IV
In this example, the level of OPP in the use dilution was raised to
500 p.p.m. and combined with the indicated levels of high activity
phenolics or intermediate activity phenolics which are identified
as in Example I above. The results obtained are shown in Table
4.
TABLE 4 ______________________________________ Positive tubes per
10 tubes Amount Ratio phenolic OPP to 100 p.p.m. 400 p.p.m.
Phenolic (p.p.m.) phenolic HW HW
______________________________________ (a) H-1 200 2.5:1 1-10 1-10
(b) H-1 250 2:1 0-1 0-1 (c) H-1 300 1.67:1 0-1 0-1 (d) H-1 400
1.25:1 0 0 (e) H-2 400 1.25:1 0 0 (f) I-2 300 1.67:1 0-1 0-1 (g)
I-2 400 1.25:1 0-1 0-1 (h) I-1 450 1.11:1 0-1 0-1 (i) I-3 450
1.11:1 0-1 0-1 ______________________________________
The results in Table 4 reveal that it was only when the level of
the high activity phenolic was increased so that the total
phenolics was at 750 p.p.m. that pass results were obtained. It is
of interest to note that the effective weight ratio of OPP to high
activity phenolics ranged from about 1.25:1-1.67:1 in Table 4 and
that the effective weight ratio of OPP to intermediate activity
phenolics ranged from about 1.67:1-1.11:1.
EXAMPLE V
The OPP level in this example was raised to 600 p.p.m. and combined
with the similarly identified high activity or intermediate
activity phenolics as indicated in Table 5.
TABLE 5 ______________________________________ Positive tubes per
10 tubes Amount Ratio phenolic OPP to 100 p.p.m. 400 p.p.m.
Phenolic (p.p.m.) phenolic HW HW
______________________________________ (a) H-1 100 6:1 1-10 1-10
(b) H-1 150 4:1 0-1 0-1 (c) H-1 200 3:1 0-1 0-1 (d) H-1 300 2:1 0 0
(e) H-2 300 2:1 0 0 (f) H-1 300 2:1 0-1 0-1 (g) I-2 200 3:1 0-1 0-1
(h) I-2 300 2:1 0 0 (i) I-3 300 2:1 0-1 0-1
______________________________________
As seen from the results in Table 5 above, when the OPP is at a
level of 600 p.p.m. and the high activity phenolics are at a level
less than 150 p.p.m., as shown in system (a), the results obtained
are poor. However, when the level of high activity phenolics is
raised to at least 150 p.p.m., good results are obtained as can be
seen in system (b). Hence, it appears as though a secondary
threshold of effectiveness is reached when the use dilution
contains a minimum of 600 p.p.m. OPP and 150 p.p.m. high activity
phenolics. A corresponding relationship is also obtained with the
intermediate activity phenolics.
In a further test, a use dilution containing 550 p.p.m. OPP and 200
p.p.m. H-1 was found to yield pass results equivalent to systems
(b) and (c) above.
EXAMPLE VI
In this example, the level of OPP was raised to 700 p.p.m. and
combined with high activity phenolics and a combination of high
activity and intermediate activity phenolics as identified above,
producing the results shown below in Table 6. The pH of the use
dilutions was from about 9.0-10.5.
TABLE 6 ______________________________________ Positive tubes per
10 tubes Amount Ratio phenolic OPP to 100 p.p.m. 400 p.p.m.
Phenolic (p.p.m.) phenolic HW HW
______________________________________ (a) H-1 250 2.8:1 0 0 (b)
H-2 250 2.8:1 0 0 (c) I-1 200 1.75:1 0 0 H-1 200
______________________________________
As described earlier, selection of a proper type of surface active
agent is important when it is desired to include a surface active
agent in a use dilution formulation containing the phenolics of the
invention. Example VII is set forth below to demonstrate the
different results that are obtained when a soap is employed as the
only surface active agent as opposed to the use of a synthetic
detergent as the only surface active agent.
As is known to those skilled in the art and as employed herein, the
term "soap" refers to any salt of a fatty acid usually, obtained by
saponification of a vegetable oil with caustic soda, such as
sodium, potassium and ammonium salts of lauric, myristic, palmitic,
stearic, oleic, linoleic and ricinoleic acids.
EXAMPLE VII
Two use dilution formulations were prepared containing equal
amounts of OPP, intermediate activity phenolic and solvent. In one
formulation, a soap was employed as the surface active agent while
the other formulation contained a synthetic detergent. Each
formulation was diluted with distilled water and with hard water
and then tested for activity against Pseudomonas aeruginosa
according to the UDC test. The formulations and the results
obtained from the UDC test are set forth below in Table 7. In Table
7, the phenolics employed are identified as in Example I, the
"soap" employed was potassium ricinoleate, the term "Dowfax 2A1" is
the trademark designation for an anionic synthetic detergent
consisting essentially of disodium dodecyldiphenyloxide
disulfonate, the amounts of the components are given in percent by
weight based upon the total weight of the formulations, the term
"dilution factor" denotes the ratio of dilution based upon one part
of the total components per parts of water, and the terms "A" and
"B" identify the formulations. Sufficient water was added to each
formulation to bring the total weight of the formulations to 100%
and a trace of alkali was added to formulation B to aid in
solubilizing the phenolics.
TABLE 7 ______________________________________ Formulation A B
______________________________________ Components: OPP (ortho
phenylphenol) 15.0 15.0 1-4(4-t-amylphenol) 6.3 6.3 Soap (potassium
ricinoleate) 44.0 Dowfax 2Al (45% active) 15.0 Solvent (isopropyl
alcohol) 4.7 4.7 Dilution factor 200 200 pH: Distilled H.sup.2 O
9.0 10.1 100 p.p.m. HW 8.9 10.0 Positive tubes/10 tubes: Distilled
H.sup.2 O 0 0 100 p.p.m. HW 1-10 0
______________________________________
The results set forth in Table 7 above reveal that both
formulations gave good results when diluted with distilled water.
However, when 100 p.p.m. AOAC hard water was employed as the
dilution medium, formulation A failed while formulation B exhibited
pass results. In other tests utilizing mixtures of soap and
synthetic detergent as the surface active agents, it was found that
as long as the formulation contained a predominance of anionic
synthetic detergent, some soap could be tolerated Preferably,
however, the formulation should be substantially free of soap.
In all of the systems set forth in Examples III-VI above, it is of
paramount significance to note that when the minimum levels of OPP
and high activity and/or intermediate activity phenolics is
established, the systems were indifferent to the level of hardness
in the water.
As indicated above, the phenolics of the invention can be utilized
to obtain use dilutions having the concentrations desired or
required by the user. Typical formulations are illustrated below in
Table 8 wherein the pH of the use dilutions did not exceed 10.5 and
the amounts of the components are given in percent by weight based
upon the total weight of the formulations. The terms employed in
Table 8 are identified as follows: "Dowfax 2A1" denotes a
commercially available anionic surface active agent as previously
identified in Example VII; "NTA, NA.sub.3 " denotes
nitrilotriacetic acid, trisodium salt; "SLS" denotes sodium lauryl
sulfate; "DBS" denotes dodecylbenzene sulfonate; "dilution factor"
denotes the recommended dilution of the phenolic composition; and,
"OPP," "H-1" "H-2", "I-1", and "I-2" are as identified hereinabove.
In each formulation, sufficient water was added to bring the total
weight of the formulations to 100%.
TABLE 8 - [Typical formulations]
__________________________________________________________________________
Percent by weight/formulations Component 1 2 3 4 5 6 7 8 9 10 11
__________________________________________________________________________
Phenolics: OPP 15 18 18 15 15 15 7.5 14 14 14 5 H-1 6 7 5.9 6 2.9
H-2 7 6.3 7.5 8.5 I-1 2.5 2.5 1.25 2.0 2.0 0.8 I-2 12 4.7 Surface
active agents: Dowfax 2Al 7 8.5 8.5 4.5 6.5 4.5 4.5 8.1 6.8 6.8 4.5
SLS 3 3.5 4.0 1.0 2.1 DBS 1.5 1.5 2.0 2.0 Chelating agents: NTA,
Na.sub.3 1.0 EDTA 3.3 3.3 3.3 3.3 2.5 0.8 0.4 1.0 1.0 1.0 Alkali:
NaOH 3.0 3.5 3.7 3.6 3.3 3.2 1.4 3.0 2.6 2.8 1.4 Solvents:
Isopropanol 10 10 10 5 10 10 10 5 Hexylene glycol 5.0 10 Other
additives: Sodium sulfite 0.5 0.5 0.5 0.5 0.5 0.25 0.6 0.6 0.5 0.5
Sodium xylene sulfonate 4 Perfume 0.3 0.4 0.3 0.3 0.3 0.2 0.2 Dye
.002 .002 .001 .001 .001 .001 .001 Dilution factor 256 256 256 256
256 256 128 256 256 256 100
__________________________________________________________________________
All of the formulations listed in Table 8 above were found to give
pass results against S. aureus, S. choleraesuis and Pseudomonas
aeruginosa.
As indicated by the typical formulations in Table 8 above, phenolic
compositions are almost always recommended for dilution with water
when intended for use as disinfectants and some of the more common
dilution factors are shown in Table 8. In addition to these,
dilution factors of 1:64 and 1:200 are also recommended. These
dilution factors derive from the ratio of phenolic composition to
water, usually expressed in terms of an ounce of phenolic
composition per multiple of ounces in a gallon of water. Of the
above dilution factors, those of 1:64, 1:128 and 1:256 are
generally recommended with greater frequency than the others.
When these dilution factors are considered together with the ratio
range of ortho phenylphenol to high and/or intermediate activity
phenolics; that is, from about 4:1 to 1.11:1, the phenolic
compositions of the invention can then be expressed in terms of
percent by weight in resultant products. This is illustrated in
Table 9 below wherein representative phenolic composition contents
for typical use dilution products at the indicated ratios and
dilutions factors are shown. In Table 9, the total of high activity
and/or intermediate activity phenolics employed are not
specifically identified but are generally referred to by the term
"HAP," as acronym for the expression "higher active phenolics."
TABLE 9 - [Representative phenolic contents at typical dilution
factors] ______________________________________ Concentra- Percent
by weight phenolic tion of content at recommended Ratio of
phenolics in use dilution factors Phenolic OPP to use dilution
content HAP (p.p.m.) 1:64 1:128 1:256
______________________________________ OPP 1.11 450 2.88 5.76 11.52
HAP 1 410 2.64 5.28 10.56 OPP 2 500 3.2 6.4 12.8 HAP 1 250 1.6 3.2
6.4 OPP 4 800 5.12 10.24 29.48 HAP 1 200 1.28 2.56 5.12
______________________________________
From the data shown in Table 9, it will be seen that the lower
ratio limit of ortho phenylphenol to high and/or intermediate
activity phenolics of 1.11:1 falls well within the minimum amount
needed in a use dilution product to obtain pass results (see
Example III above). It may be possible to enhance the strength of
the product by increasing the total content of high and/or
intermediate activity phenolics while maintaining the same level of
ortho phenylphenol. However, this should be undertaken after
considering the following factors:
High and intermediate activity phenolics are characteristically
less soluble in water than ortho phenylphenol. Therefore,
increasing the content of high and/or intermediate activity
phenolics would result in corresponding difficulty to obtain a use
dilution product in which the entire phenolic composition is
dissolved.
Water solubility of increased amounts of high and/or intermediate
activity phenolics can be enhanced by utilizing greater amounts of
detergent and/or alkali in the use dilution product. However, it is
known that large amounts of detergent and/or alkali in phenolic
products are detrimental to the germicidal activity of the
phenolics.
Increasing the content of high and/or intermediate activity
phenolics also increases the toxicity of the phenolic composition
as well as the resultant use dilution products and also
unnecessarily adds to the product cost.
In view of the above facts and since the lower ratio limit of OPP
to HAP of 1.11:1 provides pass results in a use dilution product at
minimum phenolic levels, this lower ratio limit is recommended.
The upper ratio of OPP to HAP of 4:1 is also based on similar,
practical considerations. Increasing the OPP to HAP ratio above 4:1
does not enhance germicidal performance but serves to only increase
costs and the toxicity of the phenolic compositions and use
dilution products. Furthermore, Table 9 above reveals that use
dilution products having a dilution factor 1:256 require an active
total phenolic content of about 25% by weight at the upper ratio
limit of 4:1 in the phenolic composition. In effect, this upper
ratio limit represents the upper limit of practicability for
formulating use dilution products. Increasing the phenolic content
of use dilutions at the 1:256 dilution factor level is not
recommended since the corresponding amount of detergent needed to
entirely solubilize the phenolics cannot be added to the use
dilution. When the amount of detergent necessary to solubilize
increased amounts of phenolics was added to the use dilution part
of the phenolic composition was found to settle out of solution
after storage within a portion of the normal storage temperature
range of from about 15.degree. to 120.degree. F.
The median ratio of OPP to HAP of 2:1 has been included in Table 9
as representative of the most usual ratio that will most probably
be employed to provide commercial products.
EXAMPLE VIII
To further illustrate the representative data shown in Table 9
above, additional phenolic compositions were prepared and use
dilutions formulated with them which were then subjected to the UDC
test. In order to further illustrate that it is the phenolic
content that is effective in the UDC test and not other ingredients
which can be added as desired by a formulator, such as chelating
agents, solvents, builders, reducing agents and the like, a
simplified formulation was used. In addition to the phenolic
compositions of the invention, therefore, the formulated use
dilution products also contained the following ingredients:
(1) As an anionic surface active agent, "Dowfax 2A1," as identified
in Example VII, in an amount equal to the total weight of the
phenolics employed.
(2) Isopropyl alcohol in an amount of 15% by weight based upon the
total weight of the composition.
(3) Sodium hydroxide in an amount sufficient to provide a pH of
from about pH 9.5 to pH 10.3 in the use dilution.
Despite the simplicity of the above-described formulation, it will
be appreciated by those skilled in the art that the amount and type
of surface active agent can be varied as well as utilizing
combinations of different surface active agents. Similarly the type
and amount of alcohol employed is also not critical and can be
eliminated or augmented as desired. This is equally true of the
alkali utilized to provide a desired or required pH level in the
use dilution.
The phenolic compositions employed to obtain use dilutions from the
above formulation are set forth in Table 10 wherein the high
activity and intermediate activity phenolics employed are
identified a in Examples I-VII above. Additional intermediate
activity phenolics were also used and these are identified as
"I-4," "I-5," "I-6," and "I-7" for 4-n-amylphenol,
4-chloro-3,5-dimethylphenol, 5-methyl-2-isopropylphenol, and ortho
chloro-p-phenylphenol, respectively.
In Table 10 there is also shown the weight percent of ortho
phenylphenol and the weight percent of the total high and/or
intermediate activity phenolics present in each use dilution, the
dilution factor of each use dilution, and the UDC test results
obtained in the same manner as in Example I-VII above.
TABLE 10 - [UDC test results at typical use dilution factor levels]
______________________________________ Positive Tubes Per Phenolic
in Dilution 10 Tubes Phenolic use Dilution Factor of (400 ppm
Content (% by weight) Use Dilution HW)
______________________________________ (1) OPP 11.52 1:256 0 H-1
10.56 (2) OPP 11.52 1:256 0 H-2 10.56 (3) OPP 11.52 1:256 0-1 I-2
10.56 (4) OPP 11.52 1:256 0-1 I-1 10.56 (5) OPP 11.52 1:256 0-1 I-4
10.56 (6) OPP 11.52 1:256 0-1 I-3 10.56 (7) OPP 11.52 1:256 0-1 I-5
10.56 (8) OPP 11.52 1:256 0-1 I-6 10.56 OPP 11.52 (9) H-2 5.28
1:256 0 I-1 5.28 OPP 11.52 (10) I-2 3.52 1:256 0-1 I-1 3.52 I-3
3.52 (11) OPP 6.4 1:128 0 H-1 3.2 (12) OPP 6.4 1:128 0 H-2 3.2 (13)
OPP 6.4 1:128 0-1 I-2 3.2 (14) OPP 6.4 1:128 0-1 I-1 3.2 (15) OPP
6.4 1:128 0-1 I-4 3.2 (16) OPP 6.4 1:128 0-1 I-3 3.2 (17) OPP 6.4
1:128 0-1 I-5 3.2 (18) OPP 6.4 1:128 0-1 I-6 3.2 (19) OPP 6.4 1:128
0-1 I-7 3.2 OPP 6.4 (20) H-1 1.6 1:128 0 I-2 1.6 (21) OPP 5.12 1.64
0 H-1 1.28 (22) OPP 5.12 1:64 0 H-2 1.28 (23) OPP 5.12 1:64 0 I-2
1.28 (24) OPP 5.12 1:64 0 I-1 1.28 (25) OPP 5.12 1:64 0 I-4 1.28
(26) OPP 5.12 1:64 0 I-3 1.28 (27) OPP 5.12 1:64 0 I-5 1.28 (28)
OPP 5.12 1:64 0 I-6 1.28 OPP 5.12 (29) H-1 0.64 1:64 0 H-2 0.64
______________________________________
As can be seen from the results tabulated in Table 10 above,
satisfactory results were obtained in each instance.
It should be understood, and will be recognized by those skilled in
the art, that the phenolics of the invention can be prepared in
powdered form wherein the amounts of ortho phenylphenol and total
phenolics as well as the weight ratios of ortho phenylphenol to
high activity and intermediate activity phenolics will be the same.
When prepared in powdered form, the diluents employed will be salts
rather than water. Powdered phenolic compositions of the invention
can be obtained from liquid preparations by spray-drying the liquid
preparation or by spray-drying selected components of a liquid
preparation and then blending them with appropriate salts. The
powdered products obtained can then be packaged as pre-determined
units in dissolvable plastic bags, such as polyvinyl-alcohol bags,
and the bag and its contents added to the desired or required
amount of water, whereupon the bag and its contents will dissolve.
Alternatively, the individual dry components can be blended to give
the desired amounts and ratios of phenolics.
* * * * *