CA1086006A

CA1086006A - Bleach compositions containing perfume oils

Info

Publication number: CA1086006A
Application number: CA305,097A
Authority: CA
Inventors: Robert S. Desimone
Original assignee: Hercules LLC
Current assignee: Hercules LLC
Priority date: 1977-07-26
Filing date: 1978-06-09
Publication date: 1980-09-23
Also published as: US4113645A; GB2002433A; DE2832135A1; GB2002433B; NL7807698A

Abstract

BLEACH COMPOSITIONS CONTAINING PERFUME OILS

Abstract of the Disclosure An improvement in perfumed bleach solutions which comprises employing a quaternary ammonium salt as an inert dispersing agent for the perfume oil.

Description

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:' This invention relates to the preparation of bleach solutions containing perfume oils to mask the unpleasant chlorine odor which is characteristic of such solutions.
The problem associated with the perfuming of an alkali ; 5 metal hypochlorite bleach solution is a two-part problem.
First, such bleach solutions are aqueous systems, and since most fragrance compositions are no~ soluble in aqueous sys-tems, an appropriate surfactant must be found for dispersing the perfume in the bleach to form a stable emulsion. The `10 surfactant must be one which is unaffected or substantially unaffected by the strong oxidizing and alkali action of the bleach. Second, perfume oils or perfume compositions must be used which likewise are impervious to the oxidizing action of the bleach.
`` 15 If either the surfactant or the perfume is unstable in the presence of the alkali metal hypochlorite, the effect of the perfume will be lost. A more serious problem, however, is that the alkali metal hypochlorite will be consumed by reaction with the additive and thus the strength of the solution will be ]owered, rendering it less effective for ~`? its intended use as a household bleach or disinfectant.
The concept of a perfumed bleach composition has been advanced previously. For example, V.S. patent 3,684,722 .~- teaches that an alkali hypochlorite bleach solution thick-ened wit~ a mixture of an alkali metal soap and an amine ox~de or a long chain substituted betaine can be perfumed, but that the addition of perfume leads to a reduction in stability o the thickened solution. U.S. patent 3,876,551 teaches preparation of similar compositions based on amine oxides but without the alkali metal soap. Omission of the soap is said to be desirable in order that perfume oils , ' ~. ~ ' '. '' , . , ' 6)6 ;~ _ having "clean fresh", "floral", "woody", ~musk~ or "citrusy"
odors can functio~ properly.
Neither of the cited references, however, appears to provide a solution to the problem of long term stability.
There is no suggestion that the bleach is substantially un-diminished in strength or that the fragrance characteristics of the per~ume oils are unaltered upon long term storage.
It is an object of this invention ~o provide perfumed hypo-chlorite bleach compositions which are stable over rela-tively long periods of time.
It is a further object of this invention to providestable perfumed bleach compositions having a variety of odor types.
It is yet another object of this invention to provide surfactants capable of dispersing a perfume oil in a hypo-chlorite bleach so1ution, which surfactants are inert to the oxidizing action of the bleach over long periods of storage time.
These and other objects of the invention are accom-plished by dispersing a perfume oil in an aqueous solutionof an alkali metal hypochlorite using, as a dispersant, a ` quaternary ammonium compound of the general formula R2 +
Rl- N - R4 xn or `
R3 n ¦ R - N- R --N -R6 1 [ Xn 1 whera Rl is an alkyl or aromatic group containing from about l to 20 carbon atoms, R2 thrcugh R7 are selected from the group consisting of alkyl and aromatic groups con-taining about l to 14 carbon atoms, cycloalkyl groups :' :' , . , , : . ~ : : ' containing about 5 to 18 carbon atoms, alkaryl groups ~on-taining from 7 to ln carbon atoms, and pyridyl groups, and X
is selected from the group consisting of fluoride, chloride, nitrate, sul~ate, methyl sulfate, carbonate, sulfonate, chlorate and hydroxide and n is either 1 or 2 and is equal to the valence of X.
~ ypical quaternary ammonium salts useful in the bleach compositions of this invention are hexadecyl trimethyl - ammonium chloride, dodecyl trimethyl ammonium chloride, pentadecy] triethyl ammonium chloride, dimethyl stearyl - benzyl ammonium chloride, tetradecyl trimethyl ammonium - chloride, hexadecyl trimethyl ammonium chloride, and mix-tures of these materials. Two preferred quaternary com-pounds are hexadecyl trimethyl ammonium chloride and dodecyl ~` 15 trimethyl ammonium chloride.
It wil] be apparent that the perfume oils suitable for use in this invention are those materials which are resist-ant to the oxidative effects of the bleach or to the alkali action of the alkali metal hypochlorite solution. As em-ployed herein, the term "perfume" or "perfume oil" is in--~ tended to include both individual, unblended compounds and . blended compositions comprised of a number of specific, identifiable chemical compounds. The preferred classes of fragrance ingredients meeting these requirements are such ~-~ 25 materials as aromatic heterocyclic nitrogen compounds such as quinoline~, pyridines and pyrazines, aliphatic or aromat-- ic acetals, a]iphatic or aromatic ethers, aliphatic or aromatic nitriles, tertiary alcohols, and cyclic oxides.
~ Obviously, not every compound within these classes is a use-- 30 ful perfume oil, but any which are otherwise useful and which do not contain substituent groups which are sensitive to ~lk~li metal hypochlorite or to alkali are useful. Sub-stituent groups which are sensitive and which cannot be ~resent are such groups as active methylene groups adjacent 3S to an aromatic ring, esters, C-C double bonds, ketones or aldehydes with enolizable hydrogens, primary or secondary alcohols, and free phenolic hydroxyls.
` Among specific perfume oils found stable upon long '~ , ' ; . ." ,, .
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term storage in contact with liquid alkali metal hypochlor-ite solutions are 1,8-cineole, 2-isobutyl quinoline, 2-hexyl pyridine, dihydro-8-terpineol, tetrahydrolinalool, para-cresyl methyl ether~ hepanal diethyl acetal, beta-naphthyl ethyl ether, diphenyl oxide, cedrol, diphenyl ketone, dihy-droanethole, acetaldehyde ethyl-beta-phenyl ethyl acetal, resorcinol dimethyl ether, diphenyl oxide, tertiary amyl cymene, dimethyl phenyl carbinol, 2-ethyl-3,5-dimethyl pyrazine, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl cyclopenta-gamma-2-benzopyran and methyl phenyl ethyl ether.
A typical alkali metal hypochlorite solution employed as a household bleach contains about 5% of sodium hypochlor-ite. Solutions varying from about 1 to 15% hypochlorite can be used, however. Any of the alkali metal hypochlorites can be used; so~ium hypochlorite is preferred.
The amount of quaternary ammonium salt required to dis-perse the perfume oil in the aqueous bleach solution is be-tween about 0.025 and 1% based on the weight of alkali metal hypochlorite solution. While the precise amount in any instance varies, depending upon the amount and type of per-;' fume oil used and the type of dispersion desired, as a rule of thumb, it is usual]y found that the amount of dispersant employed is no greater than about three times the weight of perfume oil employed.
~, 25 The amount of perfume oil added to the bleach solution depends upon the type of oil used and the strength or odor effect desired. Since most perfume oils are relatively ex-pensive as compared to the market price of the bleach solu-tion, the upper limit of perfume oil for economic reasons can usually not exceed about 0.5% based on the weight of the bleach solution. Normally, the amount is between about 0.02 and 0.3~ and preferably between about 0.05 and 0.15%.
The following examples illustrate the invention but are not intended to be limiting. Parts and percentages aLe ~5 by weight unless otherwise specified.
- Example 1 ` A perfume was compounded in the fol]owing proportions:

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Parts Diphenyl oxide 140 - Cedryl methyl ether 10 Tetrahydrolinalool 100 Acetaldehyde ethyl, beta-phenyl ethyl acetal 30 1,8-Cineole 200 ; Tetrahydromuguol (IFF Register) 50 - Acetaldehyde methyl ethyl acetal 10 l,l-Diethoxy heptane 10 Isobutanal diethyl acetal 220 Phenyl acetaldehyde dimethyl acetal 10 Hydrotropic aldehyde dimethyl acetal 10

2-Isobutyl quinoline 5 Dihydroterpinyl acetate 10 Resorcinol dimethyl acetal 5 This perfume was added with shaking at 0 1% concentration to commercial 5.1~ sodium hypochlorite bleach solution contain-ing 0.3% o~ a 29% aqueous solution of hexadecyl trimethyl ammonium chloride (Arquad 16 29 - Armak Industrial Chemicals Division of Akzona, Inc.). After 14 months of storage at room temperature shielded from light, the mixture still possessed a strong odor of the original perfume quality. A
sample of the original unperfumed bleach showed 3.7% hypo-- chlorite (7~.5% of original) after the 14-month storage period, while the perfumed bleach sample showed 2.7% sodium hypochlorite (53% of original).
Example 2 ~hree perfumes containing various proportions of:
Beta-naphthyl ethyl ether Tetrahydrolinalool - Paracresyl methyl ether Diphenyl oxide Acetaldehyde ethyl - beta-phenyl ethyl acetal were added, with shaking, separately at 0.05% c~ncentration to three separate portions of liquid bleach, which contained 0.05~ hexadecyl trimethyl ammonium chloride and placed in an oven at 55C. After 72 hours in the oven at 55C., all samples still retained some fragrance.

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Exam~le 3 ~ The following materials were combined (3 drops) with 50 - ml. of commercial 5.1% sodium hypochlorite sol~tion and 9 drops of 29% hexadecyl trimethyl ammonim chloride solution were added, with shaking, to give a dispersion. Periodic observations were made, as shown below, after the solution was al]owed to stand at ambient temperature shielded from light:
Compound Comments .. .. . .. _ Fragrance from Example 2 24 days, odor still strong

3 months, odor still present ~ Dihydroanethole 3 months, odor still strong - Resorcinol dimethyl ether 3 months, odor still present Phenyl acetaldehyde 3 months, odor still present dimethyl acetate - Isobutyl quinoline 3 months, odor strong Diethoxyheptane 3 months, some odor still present Isobutanal diethyl acetal 3 weeks, odor strong 3 months, little odor , Dihydroterpinyl acetate 3 weeks, odor still strong 3 months, odor somewhat diminished ! Exam~le 4 Three fragrances were made up of the following ingredients:
Fraqrance #1 _ #3 Eucalyptus oil (1,8-cineole) 800 900 930 Cedryl methyl ether 50 60 50 Dihydroanethole 10 40 19 Tetrahydrolinalool 140 0 0 Tetrabutyl quinoline 0 0 ~ Total parts 1~
- ` 35 Each fragrance was added to commercial 5.1% sodium hypo-chlorite liquid bleach at 0.1% concentration in three separ-ate 50-ml. portions, which contained 0.05%, 0.3%, and 0.15%, respectively, oP 29% hexadecyl trimethyl ammonium chloride solution. All solutions were virtually clear upon mixing o~ the ingredients. Periodic observations were made on the i samples as shown below.

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Example 5 A fragrance formulated as shown below:
1,8-Cineole 930 parts Cedryl methyl ether 50 parts Dihydroanethole 19 parts 2-Isobutyl quinoline 1 part was added at 0.05~ to 5.0% aqueous sodium hypochlorite solu-tion containing 0.2% hexadecyl trimethyl ammonium chloride and the mixture was stirred until homogeneous. After 6-1/2 months' storage at ambient temperature, shielded from light, the mixture was found somewhat turbid, while the fragrance was strong.
- Example 6 A fragrance, formulated as in Example 5, was added at - 15 0.2% to two portions of 5.1% commercial sodium hypochlorite ; solution, containing 0.2% and 0.4~, respectively, of hexa-decyl trimethyl ammonium chloride. The solution containing 0.2% quaternary was slightly turbid initially, after mixing, while the one containing 0.4% was clear. After thre months, at ambient storage conditions, the solution containing 0.2 quaternary was hazy with a strong odor of perfume still present, while the 0.4% solution was opaque, but still pos-sessing a strong fragrance aroma.
Exam~le 7 ~- 25 A mixture of 0.05% fragrance, formulated as in Example 5, and 0.2% hexadecyl trimethyl ammonium chloride in 5.1%
sodium hypochlorite solution was found clear after initial mixing. After six weeks, some gelatinous precipitate was present, with the perfume odor quite strong. AEter four months of storage, under ambient conditions, shielded from light, the solution was turbid, the odor satisfactory.
Example 8 (a) ~ solution of 3 drops of diphenyl methane and 9 drops of a 30% aqueous solution of hexadecyl trimethyl ammonium chloride in 25 ml. of 5.1% sodium hypochlorite was shaken, to aid dispersion, and stored for 4 months at ambi-ent temperature, at which point the odor of the diphenyl methane was absent.
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(b) A solution of 3 drops of a mixture of 2,6-dimethyl-2-octanol and tetrahydrolinalool (mixture known commercially as Tetrahydromuguol, IFF Register) and 9 drops of a 20%
aqueous solution of hexadecyl trimethyl ammonium chloride was stored, at ambient temperature, for 4 months, whereupon the odor of the fragrance material was still strong and the hypochlorite strength of the solution tested out at 4.35 hypochlorite. The original 5.1% hypoch]orite solution, after the same four-month period, tested at 4.85% hypo-chlorite.
In a similar manner, the following fragrance materialswere storage-tested with results as tabulated below.

Storage ~ Hypochlorite Material Period Odor Remaining 15 1,4-Cineole 4 months Nil 1,8-Cineole 4 months Strong Acetaldehyde ethyl methyl acetal 4 months Strong Beta-phenyl ethyl methyl ether 4 months Strong Cedryl methyl ether 4 months Strong4.05%
6 months Strong Diphenyl oxide 4 months Strong Perfume from Ex. l 3 months Strong4.55~
25 Perfume from Ex. 1 4 months Strong4.10%
2-Isobutyl quinoline 4 months Strong4.05%
Dihydroanethole 4 months Strong4.35%

Ortho-methoxybenzyl ether 4 months Strong ; 30 l,l-Diethoxy heptane 4 months Moderate Exam~le 9 A Eragrance formulated as in Example 5 was added at 0.05% level to 5.0% aqueous sodium hypochlorite solution containing 0.2% hexadecyl trimethyl ammonium chloride ~Varlquat E228 - Ashland Chemical Company) and the mixture stirred until homogeneous. After 6-1/2 months' storage at ambient temperature, shielded from light, the mixture was found somewhat turbid, but the fragrance persisted in strength.

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Example lO
A fragrance formulated as in Example 5 was added at 0.05% level to 5.0% aqueous sodium hypochlorite solution containing 0.6% of a mixture of 5% octyl, 6% decyl, 51~
dodecyl, 19% tetradecyl, 9% hexadecyl and 5% octadecyl tri-methyl ammonium chlorides (Arquad C-33 - Armak Industrial Chemicals Division of Akzona, Inc.) and the mixture stirred until homogeneous. After 6-1/2 months of storage at ambient temperature, shielded from light, ~he perfume in the mixture had retained its odor potency.

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Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. In an alkali metal hypochlorite bleach solution containing a perfume oil to mask the chlorine odor thereof and a dispersant for said perfume oil, the improvement which comprises said dispersant being at least one quaternary ammonium compound having the structural formula or where R1 is an alkyl or aromatic group containing from about 1 to 20 carbon atoms, R2 through R7 are selected from the group consisting of alkyl and aromatic groups con-taining about 1 to 14 carbon atoms, cycloalkyl groups con-taining about 5 to 18 carbon atoms, alkaryl groups contain-ing from 7 to 10 carbon atoms, and pyridyl groups and X is selected from the group consisting of fluoride, chloride, nitrate, sulfate, methyl sulfate, carbonate, sulfonate, chlorate and hydroxide, and n is either 1 or 2 and is equal to the valence of X.

2. The bleach solution of claim 1 wherein the perfume oil is present in an amount between about 0.02 and 0.5% and the quaternary ammonium compound is present in an amount be-tween about 0.025 and 1%.

3. The bleach solution of claim 2 wherein the alkali metal hypochlorite is sodium hypochlorite.

4. The bleach solution of claim 3 wherein the quat-ernary ammonium compound comprises hexadecyl trimethyl ammonium chloride.

5. The bleach solution of claim 3 wherein the quater-nary ammonium compound comprises dodecyl trimethyl ammonium chloride.