US3671630A - Halogenated phenolic germicidal compositions containing terpene color stabilizers - Google Patents

Abstract

Aqueous solutions containing halogenated phenolic germicidal compositions are stabilized against color change on exposure to light by providing in the solutions an effective amount of a discoloration inhibitor selected from the group consisting of alpha-phellandrene, allo ocimene, ocimene, terpinolene, myrcene, isoprene, rosin, tall oil, myrcene hydrate, and abietic acid. The solutions may also contain up to 35 percent of a detergent and other conventional detergent adjuvants.

Description

United States Patent Carroll et al.

1 51 June 20, 1972 HALOGENATED PHENOLIC GERMICIDAL COMPOSITIONS CONTAINING TERPENE COLOR STABILIZERS Francis Emery Carroll, Wyckofi; Walter Charles Seebold, Westwood, both of NJ.

Lever Brothers Company, New York, N.Y.

Filed: Aug. 17, 1970 Appl. No.: 64,623

Inventors:

Assignee:

Related US. Application Data Continuation-in-part of Ser. No. 673,264, Oct. 6, 1967, abandoned.

US. Cl ..424/174, 252/106, 252/107, 424/195, 424/230, 424/317, 424/347, 424/355, 424/356 Int. Cl ..A01n 9/30, C1 1d 3/48, Cl 1d 9/50 Field of Search ..424/174, 195, 59, 60, 230, 424/317, 347, 355, 356; 252/106, 107; 260/489, 652.5

Primary E.\'aminerAlbert T. Meyers Assistant Examiner-Leonard Schenkman Attorney-Brumbaugh, Graves, Donohue & Raymond [57] ABSTRACT Aqueous solutions containing halogenated phenolic germicidal compositions are stabilized against color change on exposure to light by providing in the solutions an effective amount of a discoloration inhibitor selected from the group consisting of alpha-phellandrene, allo ocimene, ocimene. terpinolene, myrcene, isoprene, rosin, tall oil, myrcene hydrate, and abietic acid. The solutions may also contain up to 35 percent of a detergent and other conventional detergent adjuvants.

22 Claims, N0 Drawings I HALOGENATED PIIENOLIC GERMICIDAL COMPOSITIONS CONTAINING TERPENE COLOR S'IABILIZERS This application is a continuation-in-part of application, Ser. No. 673,264, filed Oct. 6, I967, now abandoned.

The present invention relates to aqueous solutions containing halogenated phenolic germicidal compositions which have improved stability against discoloration by light.

Aqueous solutions containing halogenated phenolic germicidal compositions, such as tribromosalicylanilide (TBS), dibromosalicylanilide (DB8), and hexachlorophene, change color on exposure to sunlight, actinic light and even artificial light for prolonged periods of time. The freshly made aqueous compositions are colorless or slightly yellowish, but change to a dark amber within a very few hours of exposure to light. Special precautions are thus necessary in the manufacture, packaging and distribution of these germicidal solutions to insure that they do not become exposed to light and undergo undesirable color change.

One prior art attempt to improve the color stability of germicidal compositions is by the incorporation therein of an inorganic sulfite. While such compositions have improved stability against discoloration, the inorganic sulfite imparts an undesirable sour odor which consumers dislike. More importantly, where these germicidal liquid compositions containing sulfite are packaged and sold in resilient containers, it has been noted that the containers are subject to significant collapse or paneling of their resilient walls. This is thought to be occasioned by the removal of oxygenfrom the head space of the resilient container due to the presence of the inorganic sulfite reducing agent.

It is accordingly an object of the present invention to provide an aqueous germicidal composition based on halogenated phenolic germicides, which solutions have improved stability to discoloration by light and which, at the same time, are free of the disadvantages of the prior art set forth above. It is a further object to provide aqueous germicidal detergent compositions having the same advantages.

It has now been found that aqueous solutions of halogenated phenolic germicides can be significantly stabilized against color change in the presence of light by incorporating in such compositions, as stabilizers, a compound selected from the group consisting of alpha-phellandrene, allo ocimene, ocimene, terpinolene, myrcene, isoprene, rosin, tall oil, myrcene hydrate and abietic acid. Of these materials, the most effective are alpha-phellandrene, allo ocimene, ocimene, terpinolene and myrcene. The isoprene and abietic acid are somewhat less effective but, nevertheless, retard color development to a significant extent.

These compositions are terpenes and are generally representative of many of the classes of known terpenes. For

' example, the ocimene and myrcene are acyclic monoterpeand provides results similar to those obtained with abietic acid itself. An analysis of a typical wood rosin is as follows:

Fraction Sinpine, a commercially available mixture of terpenes, provides excellent results. The approximate composition of Sinpine is as follows:

Terpinolene 10% oz pinene 15% a terpinene 20% Dipentene 20% Cineol 10% Camphene 15% 'y terpinene 5% Unidentified 5% Total: [00% Mugol and Myrcenol are trade names for mixtures of terpene alcohols which have been found to provide stabilizing activity' equivalent to that obtained with isoprene and abietic acid. The structure of Myrcenol is given in U.S. Pat. No. 3,075,003; it is called myrcene hydrate in line 43, column 2. Mugol is the compound shown in U.S. Pat. No. 2,867,688, top of column 3, as a mixture of 3 isomers: viz., cis and trans at the indicated double bond in the structure in line 15, the other double bond being trans, and in the structure in line 19 the double bond being trans. The mixture consists of about 50 percent of the cis-trans mixture in ratio of 1:2 and the balance being the structure in line 19.

Tall oil, a distilled product containing a high percentage of rosin acids also provides results approximating those obtained by abietic acid. Tall oil has the following analysis:

tain phytosterols, lignins,

mercaptans and higher alcohols 0n the other hand, many terpenes and related compounds have been found to be completely ineffective. The following compounds gave no color stabilizing effect: linalyl acetate, geranyl acetate, limonene, alpha pinene, beta pinene, terpinyl acetate, neryl acetate, alpha-terpineol, quinone, methyl eugenol, camphene, amyl cinnamic aldehyde, laevo carvone, pipertone, colchicine, beta ionone and menthanyl acetate terpenes.

The aqueous germicidal solutions of the present invention usually contain a solubilizer. The brominated salicylanilides are highly insoluble in water. The potassium salt of tribromosalicylanilide is slightly soluble in water at room temperature. A solvent for the germicides is required which is also miscible in water. Water admixed with a lower aliphatic monohydric or polyhydric alcohol, such as methanol, ethanol, propanol or glycol is useful. Solvents of this nature also include acetone, xylene sulfonate and n-propyl alcohol. In compositions containing mixed detergent active materials, the germicides may be dissolved in one of these materials. For example, in compositions containing lauric diethanolamide as a suds booster, the germicide can be dissolved in the amide prior to formulating the balance of the composition. 7

The halogenated phenolic germicides used to make the color stabilized compositions of this invention should be present in germicidal effective amounts. The appropriate amount will vary, depending upon the nature of the solution, and generally will range from 0.1 percent to about 4 percent by weight. A preferred amount is about 0.4 percent by weight of the total composition.

The halogenated phenolic germicides are well known conventional materials, representative examples of which include the normal and alkali metal salt forms of 4'-monobromosalicylanilide, 5-monobromosalicylanilide, 4',5-dibromosalicylanilide, 3,5-dibromosalicylanilide, 3,4',5-tribromosalicylanilide, 3,4',S-trichlorosalicylanilide, 3',4,5-trichlorosalicylanilide, 3,3',4',5-tetrachlorosalicylanilide, trichlorocarbanilide, and hexachlorophene or 2,2-dihydroxy, 3,5,6,3',5' ,6'-hexachlorodiphenyl methane. Of these the preferred halogenated phenolic germicides are hexachlorophene and the normal and equivalent alkali metal salt forms of 3,4',5- tribromosalicylanilide and 4',5-dibromosalicylanilide as well as mixtures thereof containing at least about 50 percent by weight of 3,4',5-tribromosalicylanilide. Other halogenated phenolic germicides which discolor on exposure to light and which may be stabilized by the addition of terpene compositions according to this invention include 2,4,6- trichlorophenol, tetrachlorophenol, 4-chloro-2-cyclopentylphenol, sodium pentachlorophenate, p-chloro-m-cresol, bithionol or 2,2'-thiobis (4,6-dichlorophenol), 3-[2-hydroxy- 3,5-dichlorophenyl1-5,7-dichlorocoumaran, o-benzyl-pchlorophenol and 4,6-dibromocresol.

In accordance with one preferred embodiment of the invention, the aqueous halogenated germicide solution contains a detergent.fAmmonium alkyl aryl sulfonate is an example of a suitable detergent and may be used alone or in combination with an ammonium C -C alcohol 3E0 sulfate and lauric diethanolamide. Other compatible detergents generally known in the art may be employed. Typical of such detergents are anionic, cationic or nonionic non-soap detergents and water-soluble fatty acid soaps. Furthermore, other detergent adjuvants, such as inorganic-detergents, inorganic builder salts, sequestering agents, hydrotropes, opacifiers, perfumes, soilsuspending agents, optical brighteners, colorants, and abrasive particles maybe used. Such materials are conventional materials for the formulation of aqueous detergent compositions and have been fully described in the technical and patent literature, for example, in Soaps and Detergents" by Thomssen and McCutcheon and Encyclopedia of Chemical Technology by Kirk and Othmer.

The stabilizers of this invention are used in an amount sufficient to retard or prevent discoloration of the aqueous germicidal compositions. Generally speaking, amounts ranging from 0.25'to 1 percent have been effective with germicide levels of 0.4 percent. In addition, stabilizer levels ranging from 1 to 5 percent have been useful with a 4 percent level of germicide. Reverting to specific examples, an aqueous solution containing TBS as the germicide at a level of 0.4 percent is completely stabilized for 72 hours exposure to light by the use of alpha-phellandrene at a level ranging from 0.25 to 1 percent.

With an aqueous solution containing 0.4 percent TBS, a level of myrcene ranging from 0.5 to 1 percent was an effective stabilizer, while with the same TBS solution, ocimene was effective over a range of 0.25 to 1 percent, and abietic acid was partially effective over a range of 0.1 to 0.5 percent.

The following examples serve to illustrate the invention previously disclosed and are not intended to limit it in any way. All percentages are by weight unless otherwise indicated.

EXAMPLE 1 Ingredients by Weight TBS 0.4 Acetone 93.6 Water misc. 5.0 Stabilizer 1.0 Total: 100.0

After preparation, samples of the various liquids containing the various color stabilizers were stored in glass bottles on a roof so as to provide constant exposure to light during the daytime hours. The color of the liquids was graded at the time the liquids were made and at various intervals thereafter. The following legend was used to evaluate the compositions in conducting the visual color grading tests:

0 Colorless to slight yellow tint l Very slightly yellow 2 Slightly yellow to slightly amber 3 Yellow to medium amber 4 Amber Table 1 below gives the values assigned to the compound initially and after 2 hours, 15 hours, and 106 hours of exposure to daylight. Liquids having a color grading of 3 or more are considered unsatisfactory with respect to color stability.

TABLE 1 Visual Color Gradings of Liquids After Exposure to Daylight for Stabilizer 0 Hrs. 2 Hrs. 15 Hrs. 106 Hrs.

Terpinolene 0 l 2 l Alpha-phellandrene 0 0 0 0 Allo ocimene 0 0 0 0 Sinpine' 0 1-2 3 1-2 Sinpine (redistilled) 0 1-2 2 l Ocimene 0 0 0 0 Myrcene 0 0 2 l-2 "Sinpine is a mixture of terpenes supplied by Givaudan-Delawanna lnc.

Abietic acid l 1-2 2 2 Rosin WW 0 1-2 2 1-2 None 0 2 4 4 "About rosin acids and 10% nonacids.

EXAMPLE 11 A liquid composition was prepared according to the invention to contain 0.4 percent TBS in acetone and water with no adjustment of the pH taking place after the addition of the color stabilizers. These liquids had a pH within the range of 3-3.5. Their composition was as follows:

Ingredients by Weight TBS 0.4 Acetone 79.6 Stabilizer 1.0 Water and Misc. 19.0 Total: 100.0

The effect of light on the color of the above liquid containing various stabilizers is given in Table 2 below. After 72 hours, the initially colorless liquids without stabilizers had changed to a yellow color. The other compounds prevented a color change.

TABLE 2 Visual Color Gradings of Liquids After Exposure to Light for 0 Hrs. 72 Hrs.

Stabilizer Allo ocimene Abietic acid Rosin WW Myrcene Ocimene Alpha-phellandrene Mugol Sinpine None U OOOOOOO Described in Example I A terpene alcohol, supplied by International Flavors and Fragrances, lnc.

EXAMPLE in Aqueous germicidal compositions were prepared containing 0.4 percent TBS in alcohol and water and adjusted to a pH of I03 with potassium hydroxide. The composition of the germicidal liquid was as follows:

ingredients by Weight TBS 0.4

N-propyl alcohol 50.0

KOH (50%) 0.125

Stabilizer 1.0

Water and misc. 48.475 100.000

Total:

Table 3 below gives the visual color gradings made when the solutions were initially prepared, and after 72 hours of exposure to light.

TABLE 3 Visual Color Gradings of Liquids After Exposure to Light for Stabilizer Hrs. 72 Hrs.

Abietic acid 0 0 Rosin WW 0 0 Allo ocimene 0 0 Sinpine 0 0 Pipertone 0 4 None 0 4 Legend 0 colorless to slight yellow tint 4 amber The control liquid containing no stabilizer and the liquid containing pipertone were amber. The remaining liquids ranged from colorless to a slight yellow tint.

EXAMPLE lV Gcrmicidal liquid formulations containing 4 percent TBS and various levels of alpha-phellandrene were tested for light stability. The composition of the liquids were as follows:

ingredients I: by Weight TBS 4.0 Acetone 86-9l Stabilizer 0-5 Water 5.0

The compositions had a pH within the range of 2.3-2.7.

Table 4 gives the visual color gradings obtained. A reading of 0 indicates a colorless liquid, whereas a reading of 3 designates a yellow to medium amber liquid.

A germicidal liquid formulation containing 1 percent TBS and 1 percent of various color stabilizers was tested for light stability. The composition of the liquid was as follows:

Ingredients b by Weight TBS l.O Acetone 93.0 Water 5.0 Stabilizer l.0

Total: 100.0 Pb 6.6

Table 5 below shows the results of the tests. In the visual color gradings, 0 is colorless, 2 is slightly yellow to slightly amber, and 4 is amber.

TABLE 5 Visual Color Gradings of Liquids After Exposure to Daylight for Stabilizer 0 Hrs. 106 Hrs.

Allo ocimene 0 2 Alpha-phellandrene 0 2 None 0 4 The above demonstrates that a germicidal liquid containing 1 percent TBS changes from a colorless liquid to an amber liquid when exposed to daylight. The color began to develop almost immediately on exposure to light and the liquid was noticeably colored in about 2 hours. Liquids containing the stabilizers were stabilized as a slight yellow liquid as compared to the amber or reddish brown color with the control liquid.

EXAMPLE VI Germicidal liquids containing hexachlorophene, both with and without color stabilizers, were tested for light stability. The composition of the germicidal liquids was as follows:

ingredients 1: by Weight Hexachlorophene 0.4 Aeetoae 54.0 Water 44.6 Stabilizer l .0 Total 100.0

Table 6 below gives the visual color gradings obtained by using various stabilizers in the above germicidal liquid compositions. In the gradings, 0 indicates a colorless solution, 3 a yellow to medium amber and 4 designates amber.

TABLE6 3 Visual Color Gradings of Liquids After Exposure to Daylight for S Stabilizer Hrs. 336 Hrs.

Alpha-phellandrene 0 0 Allo oeimene 0 0 Benzene .0 4 l0 Laevo carvone 0 3 None 0 4 The liquids containing hexachlorophene changed from colorless to amber on exposure to light. Alpha-phellandrene and allo oeimene prevented discoloration of the liquid. Benzene and laevo carvone were ineffective as color stabilizers.

EXAMPLE Vll Germicidal-liquid detergent formulations containing 0.4 percent hexachlorophene and l0 percent dodecylbenzene sulfonate, together with various color stabilizers were prepared. The compositions had the following formula, with a pH of 6-7.5:

Ingredients I: by Weight NH Ucane l2 sulfonate l0.0 Hexachlorophene 0.4 Acetone 46.0 Water 42.6 Stabilizer l .0 Total: 100.0

Color gradings of the solutions were made on the following basis: 0 colorless to a slightly yellow tint; l slightly yellow, 40 and 4 amber.

Table 7 below summarizes the results obtained.

TABLE 7 Visual Color Gradings of Liquids After Exposure to Daylight for Stabilizer 0 Hrs. 336 Hrs.

Alpha-phellandrene 0-l 0 Allo ocimene O-l 0 Benzene 0-l 4 Laevo carvone 0-1 4 None 0-] 4 The detergent formulations containing hexachlorophene changed from a colorless liquid to an amber liquid on exposure to daylight. Alpha-phellandrene and allo ocimene The liquids were prepared by dissolving the detergent and TBS in acetone and water. The color stabilizer was added last and the pH of the liquid was adjusted to within the range of 6-7.5 with either sodium or ammonium hydroxide or sulfuric acid. The acetone was used to dissolve the TBS which is insoluble in water. Samples of the liquid containing various organic components undergoing evaluation as stabilizers were stored on a roof in glass bottles for exposure to light.

Table 8 below gives the visual color gradings for these substances after various periods of exposure to daylight. 0 is colorless to a slightly yellow tinted solution. 1 indicates very slightly yellow. 2 indicates slightly yellow to slightly amber, and 3 is yellow to medium amber.

' TABLE 8 Visual Color Gradings of Liquids After Exposure to Daylight for Stabilizer 0 Hrs. 2 Hrs. 35 Hrs. 336 Hrs.

Linalyl acetate Terpinyl Neryl acetate Terpinolene Beta pinene Beta ionone Methyl eugenol Mugol Myrcenol Methanyl acetate terpenes Alpha-phellandrene Allo oeimene Sinpine Sinpine (redistilled) Ocimene Myrcene Abietic acid Rosin WW Tall oil fatty acid lsomerized linoleic acid None CG OO-OOO QOOO OOOOOOOOO BIN NONOOO OOON -ONNNONNN The liquid detergent containing no additive changed from a colorless liquid to a yellow or slightly amber liquid in 2 hours and to a yellow to medium amber liquid in 35 hours. The liquids containing terpinolene, Mugol, alpha-phellandrene, allo oeimene, Sinpine, oeimene, myrcene and Rosin WW were graded 0 after 336 hours of exposure to light.

EXAMPLE [X Germicidal aqueous detergent compositions were prepared containing 0.4 percent TBS, 10 percent ammonium dodecylbenzene sulfonate and 1 percent of various organic compounds as color stabilizers. After storing these solutions for a period of time, they were graded according to the following visual evaluations:

Mugol 2 l-2 2 Myrcenol 0 2 1-2 2 Alpha-phellandrene 0 0 0 0 Allo ocimene 0 0 0 0 Sinpine 0 2 1-2 1 Ocimene 0 2 1-2 1 Myrcene 0 2 0 l Abietic acid 1 2 2 2 Rosin WW 0 1 1-2 1 None 0 2 3 4 The data show that the liquid containing no stabilizer changed from a colorless liquid to one having a slight yellow to a slight amber tint in 2 hours, and to an amber liquid after 280 hours exposure to light. The liquids containing alpha-phellandrene and allo ocimene were colorless liquids after 280 hours of exposure to light. The other stabilizers were effective but to a lesser extent.

EXAMPLE X Germicidal liquid detergents containing 0.4 percent TBS, percent lauric diethanolamide and 1 percent of various organic compounds as color inhibitors were prepared and were visually evaluated according to the following table:

0 Colorless to light yellow tint l very slightly yellow 2 slightly yellow to slightly amber 3 yellow to medium amber Table 10 below gives the results of these experiments.

TABLE 10 Visual Color Gradings of Liquids After Exposure to Daylight for Additive 0 Hrs. 2 Hrs. 35 Hrs. 336 Hrs.

Terpinolene Beta pinene Mugol Myrcenol Alpha-phellandrene Allo ocimene Sinpine Sinpine (redistilled) Ocimene Myrcene Abietic acid Rosin WW Tall oil fatty acid None OOO-OOOOOOOOOO WwNNNONNOONNNN U NNNCQOMOONUNN --OOOOOOO The liquids containing terpinolene, alpha-phellandrene, allo ocimene, sinpine, ocimene, and myrcene were colorless liquids after 336 hours of exposure to light, whereas the control changed to a yellow to a medium amber liquid after 2 hours.

EXAMPLE XI A germicidal liquid detergent composition was prepared to have the following formula:

Ingredients by Weight NH. dodecylbenzene sulfonate (Ucane 12) NH, Alfol 1412 SEC sulfate Lauric diethariolamide NH. xylene sulfonate TABS Water and misc.

Stabilizer Total:

The liquids were prepared by dissolving the TBS in lauric diethanolamide and then adding this mixture to an aqueous solution of the two sulfonates and the sulfate. The color stabilizer was then added and the pH of the material adjusted to 6-7 by the addition of sulfuric acid. The liquids were stored for varying periods of time and then evaluated according to the following:

0 colorless to slightly yellow tint l very slightly yellow to very slightly amber 2 slightly yellow to slightly amber 3 yellow to medium amber 4 amber 5 dark amber Table 11 below gives the results of these experiments.

The control liquid containing no additive changed to a medium amber color in 2 hours and to a dark amber after 30 hours of exposure to light. The liquids containing allo ocimene, redistilled Sinpine, terpinolene and ocimene maintained a very slight yellow to a slight amber color after 194 hours of exposure to light.

EXAMPLE X" A number of germicidal liquid detergents having the composition given in Example Xl were prepared containing 0.4 percent TBS and varying levels of alpha-phellandrene. Table 12 below summarizes the results of the visual color evaluations of this series of tests, using the grading system of Example X1.

TABLE 12 Visual Color Grade of Liquids Exposed to Light for I: Alpha-phellandrene 0 Hrs. 72 Hrs.

EXAMPLE XII! The effect of varying the levels of myrcene in the composition of Example X1 is given in the following table. The visual color grading system of Example X1 was used.

TABLE 13 Visual Color Grade of Liquids Exposed to Light for I: Myrcene 0 Hrs. 72 Hrs.

.1. 12 0.5 1 l TABLE l7 1.0 l l EXAMPLE XIV Visual Color Grading After Exposure to Light for The effect of varying the oclmene levels in the germicidal Germicidal Composition composition of Example Xi is given in the following table. The A visual color grading system of Example Xl was used.

0 0 0 TABLE l4 36 l 0 60 2 0 84 3 0 120 4 0 Visual Color Grade of Liquids I44 4 0 Exposed to Light for I68 4 0 Ocimene 0 Hrs. 72 Hrs. 5 204 5 0 g l l g 7 EXAMPLE XVlll I l 015 1 1 Two germicidal solutions containing l percent 1 i tetrachlorophenol and 75 percent ethanol were prepared. The first solution, B, simply contained a balance of water while the second solution, B, contained in addition 1.0 percent allo EXAM LE XV ocimene. Thetwo solutions were visually color graded after The effect of varying the Rosin WW levels in the germicidal exposure m ham accordm to the following legend:

0 colorless composition of Example XI is given in the following table. The visual color grading system of EXam le XI was used 1 very light p 2 light violet TABLE 15 3 medium violet 4 --dark violet 5 very dark violet visual Color Grade of Liquid. The results of this experiment are reported below in Table Exposed to Light for l8. k Rosin WW 0 Hrs. 72 Hrs.

TABLE 18 0.1 l 5 0.15 l 5 Visual Color Grading After 0.20 l l-2 Exposure to Light for 0.25 l l-2 Germicidal Composition 0.5 l l-Z Hours B B 1.0 l l-2 4 26 0 0 l 0 EXAMPLE XVI 6o 2 o The effect of varying the abietic acid levels in the germicidal n i g composition of Example Xl is given in the following table. The 5 1 g 0 visual color grading system of Example XI was used. 3 5 0 i 204 5 0 TABLE 16 so EXAMPLE XIX Visual Solor Gaadfe of Liquids Two gennicidal solutions containing LOpercent 4-chloro- W l l Z-cycIopentylphenol and 75 percent ethanol were prepared. ADM": 0 72 The first solution, C, simply contained a balance of water while the second solution, C, contained in addition 1.0 per- 0 l 5 5 5 cent allo ocimene. The two solutions were visually color 3 graded after exposure to light according to the following 0125 1 1-2 0.5 l [-2 0 trace yellow 1 slight yellow 0 2 light amber EXAMPLE Table 19 gives the results of this experiment: Two gennicidal solutions containing 1.0 percent 2,4,6- TABLE 9 trichlorophenol and 75 percent ethanol were prepared. The first solution, A, simply contained a balance of water while the second solution, A, contained in addition 1.0 percent allo ocimene. The two solutions were visually color graded after gi t sg gg'fi'al exposure to light according to the following legend: Po Gcmicidfl composition 0 colorless Hours C C' l light pinkish violet 2 medium pinkish violet o o 0 v 3 medium reddish violet 35 o o 4 dark reddish violet 60 l l 5 very dark reddish violet g 8 The results of this experiment are reported below .in Table 9 I 0 17: m z o EXAMPLE XX Two germicidal solutions containing 1.0 percent sodium pentachlorophenate and 75 percent ethanol were prepared. The first solution, D, simply contained a balance of water while the second solution, D, contained in addition 1 percent allo ocimene. The two solutions were visually color graded after exposure to light according to the following legend:

0 slight yellow 1 medium brown 2 dark brown 3 very dark brown 4 very dark reddish brown The results of this experiment are reported in Table TABLE 20 Visual Color Grading After Exposure to Light for Germicidal Composition Hours D EXAMPLE XXI Two germicidal solutions containing 1.0 percent p-chlorom-cresol and 75 percent ethanol were prepared. The first solution, E, simply contained a balance of water while the second solution, B, contained in addition 1.0 percent allo ocimene. The two solutions were visually color graded after exposure to light according to the following legend:

0 colorless l slightly pink 2 medium pink The results of this experiment are reported in Table 2 l:

Two germicidal solutions containing 1.0 percent 2,2- thiobis(4,6-dichlorophenol) and 75 percent ethanol were prepared. The first solution, F, simply contained a balance of water while the second solution, F, contained in addition 1 percent allo ocimene. The two solutions were visually colored graded after exposure to light according to the following legend:

0 colorless l medium yellow 2 medium amber 3 reddish amber 4 medium reddish amber 5 dark amber The results of this experiment are reported in Table 22:

TABLE 22 Visual Color GradingAfter Exposure to Light for Germicidal Composition Hours F EXAMPLE XXlll Two germicidal solutions containing 1.0 percent 3',4',5- trichlorosalicylanilide, to percent lauric diethanolamide and 75 percent ethanol were prepared. The first solution, G, simply contained a balance of water while the second solution, G, contained in addition 1 percent allo ocimene. The two solutions were visually color graded after exposure to light ac-' cording to the following legend:

0 colorless I l dark yellow 2 dark amber 3 very'dark amber 4 dark reddish orange 5 very dark orange The results of this experiment are reported in Table 23:

TABLE 23 Visual Color Grading After Exposure to Light for Germicidal Composition Hours G G Ln b oa-0 OOOOQOOO EXAMPLE XXIV Two germicidal solutions containing 1.0 percent 3-[2- hydroxy-3,S-dichlorophenyl]-5,7-dichlorocoumaran and 75 percent ethanol were prepared. The first solution, H, simply contained a balance of water while the second solution, H, contained in addition 1.0 percent allo ocimene. The two solutions were visually color graded after exposure to light according to the following legend:

0 slight lemon yellow 1 medium amber 2 brownish amber 3 medium brown 4 medium greenish brown The results of this experiment are reported in Table 24:

TABLE 24 Visual Color Grading After Exposure to Light For I Germicidal Composition Hours H H EXAMPLE XXV Two germicidal solutions containing 1.0 percent o-benzyl-pchlorophenol and 75 percent ethanol were prepared. The first solution, I, simply contained a balance of water while the second solution, 1', contained in addition 1.0 percent allo ocimene. The two solutions were visually color graded after 2,4,6-trichloroplienol .0 5 .0 5 .0 5.0 Ethanol 75.0 75.0 75.0 75.0 Allo ocimene L0 3.0 5.0 Water 20.0 19.0 l7.0 l5.0

These solutions were visually color graded at varying time intervals during a 228 hour light exposure period according to the following legend:

0 colorless l slightly yellow 2 light reddish purple 3 dark reddish purple exposure to light according to the following legend: 4 medium pinkish red 0 colorless 5 medium crimson 1 very light pink 6 d k 2 dark p very ar crimson I The results of this experiment are reported in Table 27: 3 orange pink 4 medium orange pink TABLE 27 5 light amber 6 medium amber Table gives the results of this experiment: visual color Gndin Aft" Exposure to Light for TABLE 25 25 Germicidal Composition Hours M i Visual Color Grading After 0 0 0 0 0 Exposure to Light for 35 2 0 0 0 Germicidal Composition 34 3 0 0 0 Hours l l' 144 4 i l 0 I68 5 l l 0 I92 5 l l 0 0 0 0 228 6 l l 0 36 l 0 60 2 0 84 3 0 120 4 0 EXAMPLE XXVI]! g 8 Four germicidal solutions having the following composi- 204 6 o tions were prepared:

40 Germicidal Composition: N% N'% N'% N'% EXAMPLE XXVI Two germicidal solutions containing 1.0 percent 4,6- 2,4,6-trichlorophenol 1.0 1.0 1.0 1.0 dibromocresol and 75 percent ethanol were prepared. The 750 751) 75 first solution, .I, simply contained a balance of water while the a 0J0 ater 24.0 23.9 23.75 23.50 second solution, J contained in addition 1 percent allo ocimene. Two solutions were visually color graded after exposure to light according to the following legend:

0 colorless l medium pink 2 medium red 3 medium orange red 4 medium orange Table 26 shows the results of this experiment:

TABLE 26 5 5 Visual Color Grading After Exposure to Light for Germicidal Composition Hours J .I'

0 0 0 36 l l 60 2 0 a4 3 0 l 20 3 0 I44 3 0 l 68 4 0 204 4 0 70 EXAMPLE XXVll Four germicidal solutions having the following compositions were prepared:

Germicidal Composition MIi MW) M% M'% These solutions were visually color graded at varying time intervals during a 228 hour light exposure period according to the following legend:

0 colorless l very light pinkish violet 2 medium reddish violet 3 light reddish violet 4 dark reddish violet 5 very dark reddish violet The results of this experiment are reported in Table 28:

1. An aqueous germicidal Composition having improved stability against discoloration by light which comprises an aqueous solution containing from about 0.1 percent to about 4 percent by weight of a halogenated phenolic germicide susceptible to discoloration by light, and a discoloration retarding amount of a discoloration inhibitor selected from the group consisting of alpha-phellandrene, allo ocimene, ocimene, terpinolene, myrcene, myrcene hydrate, rosin, tall oil, isoprene and abietic acid.

2. An aqueous germicidal composition having improved stability against discoloration by light which comprises an aqueous solution containing from about 0.1 percent to about 4 percent by weight of a halogenated phenolic germicide selected from the group consisting of 3,4',5-tribromosalicylanilide, 4,S-dibromosalicylanilide, and hexachlorophene, and a discoloration retarding amount of a discoloration inhibitor selected from the group consisting of alpha-phellandrene, allo acimene, ocimene, terpinolene, myrcene, myrcene hydrate, rosin, tall oil, isoprene and abietic acid.

3. The composition according to claim 1 wherein the discoloration inhibitor is selected from the group consisting of alpha-phellandrene, allo ocimene, ocimene, terpinolene, and myrcene.

4. The composition according to claim 1 wherein the inhibitor is present at a level of at least about 0.25 percent by weight.

5. The composition according to claim 1 wherein a solubilizer is also present, said solubilizer being miscible in water and also a solvent for the germicide.

6. The composition according to claim 1 which additionally contains from 1 to 35 percent of a detergent.

7. The composition according to claim 1 wherein the halogenated phenolic germicide is selected from the group consisting of tetrachlorophenol, 4-chloro-2-cyclopentylphenol, sodium pentachlorophenate, p-chloro-m-cresol, 2,2'-thiobis(4,6-dichlorophenol), 3',4,5-trichlorosalicylanilide, 3-[2-hydroxy-3,S-dichlorophenyl]-$,7-dichlorocoumaran, o-benzyl-p-chlorophenol, 4,6-dibromocresol, and 2,4,6-trichlorophenol.

8. The composition according to claim 7 wherein the inhibitor is 1 percent allo ocimene and the germicide is 1 percent tetrachlorophenol.

9. The composition according to claim 7 wherein the inhibitor is 1 percent allo ocimene and the germicide is 1 percent 4- chloro-2-cyclopentylphenol.

10. The composition according to claim 7 wherein the inhibitor is 1 percent allo ocimene and the germicide is 1 percent sodium pentachlorophenate.

11. The composition according to claim 7 wherein the inhibitor is l percent allo ocimene and the gennicide is l percent p-chloro-m-cresol.

12. The composition according to claim 7 wherein the inhibitor is 1 percent allo ocimene and the germicide is 1 percent 2,2'-thiobis(4,6-dichlorophenol).

13. The composition according to claim 7 wherein the inhibitor is 1 percent allo ocimene and the germicide is 1 percent 3-[2-hydroxy-3,5-dichlorophenyl]-5,7-dich|orocoumaran.

14. The composition according to claim 7 wherein the inhibitor is 1 percent allo ocimene and the germicide is 1 percent o-benzyl-p-chlorophenol.

15. The composition according to claim 7 wherein the inhibitor is 1 percent allo ocimene and the germicide is l percent 4,6-dibromocresol.

16. The composition according to claim 7 wherein the inhibitor is 1 percent allo ocimene and the germicide is 0.10 to 5 percent 2,4,6-trichlorophenol.

17. An aqueous germicidal composition having improved stability against discoloration by light which comprises from about 0.1 percent to about 4 percent by weight of a halogenated phenolic germicide susceptible to discoloration by light, water, a solubilizer which is miscible in water and is also a solvent for the germicide, from about 1 percent to about 35 percent of deter em, and a discoloration retarding amount of a discoloration lll lbitor selected from the group consisting of alpha-phellandrene, allo ocimene, ocimene, terpinolene, myrcene, myrcene hydrate, tall oil, isoprene and abietic acid.

18. An aqueous germicidal composition having improved stability against discoloration by light which comprises from about 0.1 percent to about 4 percent by weight of a halogenated phenolic germicide selected from the group consisting of 3,4,S-tribromosalicylanilide, 4,5-dibromosalicylanilide, and hexachlorophene, water, a solubilizer which is miscible in water and is also a solvent for the germicide, from about 1 percent to about 35 percent of a detergent, and a discoloration retarding amount of a discoloration inhibitor selected from the group consisting of alpha-phellandrene, allo ocimene, ocimene, terpinolene, myrcene, myrcene hydrate, rosin, tall oil, isoprene and abietic acid.

19. The composition according to claim 17 wherein the inhibitor is alpha-phellandrene, and is present at a level of 0.25 to 1 percent and the germicide is 3,4',5-tribromosalicylanilide, present at a level of about 0.4 percent.

20. A composition according to claim 17 wherein the germicide is 3,4,5-tribromosalicylanilide, present at a level of 0.4 percent and the inhibitor is myrcene, present at a level of 0.5 to 1 percent.

21. The composition according to claim 17 wherein the germicide is 3,4',S-tribromosalicylanilide, present at a level of 0.4 percent and the inhibitor is ocimene at a level of 0.25 to 1.0 percent.

22. The composition according to claim 17 wherein the germicide is 3,4',S-tribromosalicylanilide, present at a level of 0.4 percent and the inhibitor is abietic acid, present at a level of 0.1 to 0.5 percent.

' 0 i i i i STATES PATENT @IEUFEQIE QE'HFKQATE CETN Patent No. 3,6715% Dated June 20, 1972 Inventor(s) Francis Emery Carroll et al.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 1, line 68, "53" is misplaced; Col. 2, line 19, change "2,867,688" to 2,867,668 Col. 3, line change "a" to as -5 Col. line 3, change "allo ocimene, and" to allo ocimene, ocimene, and g. 001. 5, line 8, change "Sinpine 0" to Sinpine 0 0 Col. 6, line 29, change "Ph" to pH Col. 7 line' 70, change"Nhu" to NH Col. 8, line 26, change "Terpinyl" to Terpinyl acetate 5 Col. 9, line 67, change "TABS" to TBS Col.' 10,, line 19, under 60 hrs "0 hrs" unaligned; Col. 10, lines 26-29, 30, 2 2" unaligned;

Col. 10 line 29, under 30 hrs unaligned; Col. 11, line 18, change "10.25" to 0 .25 --g Col. 12, line 72, under 0 Y change "1" to 0 Col. 13, line 32, "0 .204" is unaligned and should be 20 Col. 15, line 63, under .1 change "1" to 0 --5 Col. 16, line M, "0.10 0.25 0.50" unaligned; Col. 16, line 70, "0" is unaligned; C01. 17 line 18, change "acimene" to ocimene Signed and sealed this 10th day of April 1973 (SEAL) Attest:

EDWARD M.PLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents

Claims (21)

1. 2. An aqueous germicidal composition having improved stability against discoloration by light which comprises an aqueous solution containing from about 0.1 percent to about 4 percent by weight of a halogenated phenolic germicide selected from the group consisting of 3,4'',5-tribromosalicylanilide, 4,5-dibromosalicylanilide, and hexachlorophene, and a discoloration retarding amount of a discoloration inhibitor selected from the group consisting of alpha-phellandrene, allo acimene, ocimene, terpinolene, myrcene, myrcene hydrate, rosin, tall oil, isoprene and abietic acid.
2. 3. The composition according to claim 1 wherein the discoloration inhibitor is selected from the group consisting of alpha-phellandrene, allo ocimene, ocimene, terpinolene, and myrcene.
3. 4. The composition according to claim 1 wherein the inhibitor is present at a level of at least about 0.25 percent by weight.
4. 5. The composition according to claim 1 wherein a solubilizer is also present, said solubilizer being miscible in water and also a solvent for the germicide.
5. 6. The composition according to claim 1 which additionally contains from 1 to 35 percent of a detergent.
6. 7. The composition according to claim 1 wherein the halogenated phenolic germicide is selected from the group consisting of tetrachlorophenol, 4-chloro-2-cyclopentylphenol, sodium pentachlorophenate, p-chloro-m-cresol, 2,2''-thiobis(4,6-dichlorophenol), 3'',4'',5-trichlorosalicylanilide, 3-(2-hydroxy-3, 5-dichlorophenyl)-5,7-dichlorocoumaran, o-benzyl-p-chlorophenol, 4,6-dibromocresol, and 2,4,6-trichlorophenol.
7. 8. The composition according to claim 7 wherein the inhibitor is 1 percent allo ocimene and the germicide is 1 percent tetrachlorophenol.
8. 9. The composition according to claim 7 wherein the inhibitor is 1 percent allo ocimene and the germicide is 1 percent 4-chloro-2-cyclopentylphenol.
9. 10. The composition according to claim 7 wherein the inhibitor is 1 percent allo ocimene and the germicide is 1 percent sodium pentachlorophenate.
10. 11. The composition according to claim 7 wherein the inhibitor is 1 percent allo ocimene and the germicide is 1 percent p-chloro-m-cresol.
11. 12. The composition according to claim 7 wherein the inhibitor is 1 percent allo ocimene and the germicide is 1 percent 2,2''-thiobis(4,6-dichlorophenol).
12. 13. The composition according to claim 7 wherein the inhibitor is 1 percent allo ocimene and the germicide is 1 percent 3-(2-hydroxy-3,5-dichlorophenyl) -5,7-dichlorocoumaran.
13. 14. The composition according to claim 7 wherein the inhibitor is 1 percent allo ocimene and the germicide is 1 percent o-benzyl-p-chlorophenol.
14. 15. The composition according to claim 7 wherein the inhibitor is 1 percent allo ocimene and the germicide is 1 percent 4,6-dibromocresol.
15. 16. The composition according to claim 7 wherein the inhibitor is 1 percent allo ocimene and the germicide is 0.10 to 5 percent 2,4,6-trichlorophenol.
16. 17. An aqueous germicidal composition having improved stability against discoloration by light which comprises from about 0.1 percent to about 4 percent by weight of a halogenated phenolic germicide susceptible to discoloration by light, water, a solubilizer which is miscible in water and is also a solvent for the germicide, from about 1 percent to about 35 percent of detergent, and a discoloration retarding amount of a discoloration inhibitor selected from the group consisting of alpha-phellandrene, allo ocimene, ocimene, terpinolene, myrcene, myrcene hydrate, tall oil, isoprene and abietic acid.
17. 18. An aqueous germicidal composition having improved stability against discoloration by light which comprises from about 0.1 percent to about 4 percent by weight of a halogenated phenolic germicide selected from the group consisting of 3,4'',5-tribromosalicylanilide, 4,5-dibromosalicylanilide, and hexachlorophene, water, a solubilizer which is miscible in water and is also a solvent for the germicide, from about 1 percent to about 35 percent of a detergent, and a discoloration retarding amount of a discoloration inhibitor selected from the group consisting of alpha-phellandrene, allo ocimene, ocimene, terpinolene, myrcene, myrcene hydrate, rosin, tall oil, isoprene and abietic acid.
18. 19. The composition according to claim 17 wherein the inhibitor is alpha-phellandrene, and is present at a level of 0.25 to 1 percent and the germicide is 3,4'',5-tribromosalicylanilide, present at a level of about 0.4 percent.
19. 20. A composition according to claim 17 wherein the germicide is 3,4'',5-tribromosalicylanilide, present at a level of 0.4 percent and the inhibitor is myrcene, present at a level of 0.5 to 1 percent.
20. 21. The composition according to claim 17 wherein the germicide is 3,4'',5-tribromosalicylanilide, present at a level of 0.4 percent and the inhibitor is ocimene at a level of 0.25 to 1.0 percent.
21. 22. The composition according to claim 17 wherein the germicide is 3,4'',5-tribromosalicylanilide, present at a level of 0.4 percent and the inhibitor is abietic acid, present at a level of 0.1 to 0.5 percent.