WO1996000564A1

WO1996000564A1 - Four-component aerosol composition

Info

Publication number: WO1996000564A1
Application number: PCT/US1994/007426
Authority: WO
Inventors: Fred Presant; Agnes Terraforte
Original assignee: Precision Valve Corporation
Priority date: 1994-06-30
Filing date: 1994-06-30
Publication date: 1996-01-11
Also published as: AU7320694A

Abstract

A homogeneous four-component composition useful in an aerosol dispensing system is provided, comprising: a) alcohol selected from the group consisting of alcohols containing 2 or 3 carbon atoms and mixtures thereof from about 5-50 % by weight and dimethyl ether from about 5-50 % by weight wherein said alcohol and dimethyl ether together comprise no greater than about 55 % by weight of the composition; b) about 10-45 % by weight of a fluorocarbon material such as difluoroethane and 1,1,1,2-tetrafluoroethane; and c) water from about 1-50 % by weight. Total propellant is 15-95 % by weight. The composition allows for easy and fine atomization using high levels of propellant, and quick drying time where needed. The composition solubilizes all manner of active ingredients which may be present up to about 15 % by weight or more, varying with the type of product desired. The composition is useful in hairsprays, disinfectants, deodorants and air fresheners.

Description

FOUR-COMPONENT AEROSOL COMPOSITION

The present invention relates to compositions useful in aerosol, i.e. pressurized, dispensing systems. 5 The invention relates in particular to the field of aerosol compositions which exhibit environmental responsibility while retaining desirable properties associated with aerosol dispensing systems.

There are numerous difficulties associated with formulating an environmentally responsible propellant for use with an aerosol dispensing system, including but not limited to achieving a single phase, soluble composition which will retain desirable spray characteristics and product performance characteristics

IK

^of aerosols currently marketed. Flammability is also a consideration. Also problematic in the formulation of personal care products is obtaining a composition useful in dispensing active ingredient from an aerosol dispensing system absent toxic side effects.

20 Aerosol products are generally preferred over products dispensed by pumps or other systems. Many advantages of aerosols stem from the fact that air is not drawn into the aerosol container to replace ingredients dispensed. Thus the product is not exposed

-*to deteriorating or oxidizing effects of air, the product maintains its sterility, and preservatives need not be included in the product composition. Consumers prefer aerosols for their convenience, ease of use and cleanliness. Broadly speaking, the characteristics of

3°the spray dispensed from aerosol systems are superior to those of other systems. The product composition is

35 generally applied with a finer, more even spray than when applied with pump sprays. Pump-type dispensers tend to over-concentrate the product in one spot because of inability to maintain uniformity of product dispersal throughout the target area. This is important, for ^■^example, in a hairspray product where it is desirable that the spray retain manageability and hold of the hair style yet not weigh the hair down, give an unnatural hold or feel sticky to touch.

Various compounds have previously been

¹⁰suggested for use as aerosol propellants, singly or in certain combinations, such as dimethyl ether and various chlorofluorocarbons, but none have exhibited the unigue combination presented by the present invention of beneficial properties coupled with freedom from

-^drawbacks.

It is therefore desirable to develop a homogeneous, soluble and nontoxic composition with limited flammability, useful in an aerosol dispensing system for personal care as well as other products,

^°which retains advantageous spray characteristics and other properties of an aerosol, while achieving environmental responsibility.

Accordingly, it is a principle object of the present invention to provide a composition useful in an

^5aerosol dispensing system which achieves the advantageous properties of an aerosol.

A further object of the invention is to provide a sealed container with an aerosol dispensing system and a composition which attains the objectives

30described herein.

35 The foregoing objectives are achieved in a homogeneous, one-phase, 4-component composition useful in an aerosol dispensing system comprising: a) alcohol selected from the group consisting of alcohols containing 2 or 3 carbon atoms and mixtures thereof from

^about 5-50% by weight, and dimethyl ether from about 5- 50% by weight, wherein alcohol and dimethyl ether together comprise no greater than about 55% by weight of the composition; b) about 10-45% by weight of a non- chlorinated fluorocarbon such as difluoroethane, 1,1,1,2-tetrafluoroethane, or other equivalent; and c) water from about 1-50% by weight. The composition may be formulated with active ingredient from about 1-15% by weight, or more. Total propellant may vary from 15-95%. The invention also contemplates an aerosol

-'dispensing system comprising a sealed container equipped with an aerosol dispensing valve and containing therein the composition and active ingredient as above.

The present invention encompasses non-toxic compositions useful in an aerosol dispensing system.

PΩ The compositions comprise four-component systems made by mixing alcohol, dimethyl ether, non-chlorinated fluorocarbon and water in the proportions indicated.

The total of the alcohol and the ether does not exceed

55%, while the total propellant can vary from 15-95% of

^^the composition. Optional active ingredients and additives may be included in the formulation in order to prepare different forms of end products by numerous methods known to those skilled in the art. Methods for

30

35 preparing different forms of products are fully described and illustrated hereinafter.

It has been discovered that a homogeneous composition useful in an aerosol dispensing system which achieves these objectives is obtained by mixing alcohol, 5dimethyl ether ("DME") , difluoroethane or 1,1,1,2- tetrafluoroethane, and water, in a particular range of percentages by weight. The percentage range of compositions contemplated is as follows: a) alcohol selected from the group consisting of alcohols

-¹-⁰containing 2 or 3 carbon atoms and mixtures thereof from about 5-50%, preferably 10-50% and most preferably 15-50% by weight, and dimethyl ether from about 5-50%, preferably 5-45% and most preferably 5-40% by weight wherein said alcohol and dimethyl ether together

^■*-5comprise no greater than about 55% by weight of the composition; b) about 10-45%, preferably 10-40% and most preferably 20-35% by weight of a non-chlorinated fluorocarbon material selected from the group consisting of difluoroethane and 1,1,1,2-tetrafluoroethane and

2 equivalents; and c) water from about 1-50%, preferably 1-30% and most preferably 1-25% by weight. The total propellant which includes DME and the fluorocarbon ranges from 15-95%, preferably 15-85% and most preferably 25-75% of the composition provided the

25combined amount of alcohol and ether is maintained at 55% or less.

The preferred alcohol of the present invention is ethanol, which is effective with the range of constituent ingredients listed above in contributing to

3 the formulation of a homogeneous, soluble composition.

35 Isopropanol may also be used, but with a narrower range ^•■ of the other constituent ingredients.

The preferred fluorocarbon is FC-152a available from DuPont but others such as FC-134a and equivalents may be used. 5 it has further been discovered that an active ingredient or mixture of active ingredients may be added up to about 15%, preferably 1-10% by weight. Active ingredient may be added in order to render the composition useful in various applications including

-¹-⁰personal care products. Such applications include the dispensing of hairspray, air freshener, anti-perspirant and/or deodorant, disinfectant/deodorant, perfume, paint, insecticide, wax cleaner, solid lubricant, industrial cleaner/lubricant, surface cleaner,

-^^■5insecticide, and the like. In particular, the present invention is effective in dispensing a hairspray when formulated with hair fixative resin as active ingredient. Other active ingredients known by those skilled in the art to be useful in the formulation of a

2 hairspray to impart hair-holding or style retention properties to hair are also contemplated, such as film forming polymeric substances, or substances which make the hair hydrophobic. Examples of active ingredients of hairspray include any one of or a mixture thereof of

25acrylamide copolymers, adipic acid mixtures, acrylate esters and various polyguaternium compounds and vinyl acetate mixtures as listed in the CTFA Cosmetic Ingredient Handbook, 73-74 (J. Nikitakis, ed. 1988), which list is incorporated by reference herein. Active

30ingredients contemplated by the present invention are not limited thereby and include all those within the

35 knowledge of one of ordinary skill in the art which can ^■^ be dispensed by aerosols. Particularly preferred are several available from National Starch and Chemical Corporation such as Amphomer which is an octylacrylamide/acrylates/a inoethylmethacrylate polymer 5and Resyn 28-2930 vinyl aσetate/crotonic acid/vinyl neodecanoate copolymer.

The composition of the present invention is inert to a variety of active ingredients and acts as a solubilizing agent for all manner of hydrophobic and

^•-°hydrophilic active ingredients and additives. Although dimethyl ether and difluoroethane are by themselves flammable, the composition of the present total formula exhibits reduced flammability. Furthermore, the constituent components of the composition are nontoxic,

^ thereby rendering the composition safe in personal care product formulations. Safety of the composition extends to use as a hairspray, where the product composition is sprayed near the face and might possibly be inhaled. The composition of the present invention provides a

20concentration of propellant, comprising dimethyl ether and fluorocarbon, which allows for easy and fine atomization. Furthermore, the novel four component system of the present invention is formulated such that a soluble composition is achieved which provides quick 5drying time and a non-heavy feel to the hair when applied. These characteristics are desirable in many applications, including as a hairspray. The present invention provides these advantages in an aerosol dispensing system with a low content of alcohol and

30ether.

35 It has been discovered that a preferred homogeneous, non-toxic composition of the present invention is produced by the components mixed in the following range by weight percent: a) alcohol selected from the group consisting of alcohols containing 2 or 3 carbon atoms and mixtures thereof from about 10-50%, and dimethyl ether from about 5-45% wherein said alcohol and dimethyl ether together comprise no greater than about 55% by weight of the composition; b) about 10-40% by weight of a material selected from the group consisting of difluoroethane and 1,1,1,2-tetrafluoroethane; and c) water from about 1-30% by weight. The preferred alcohol of the composition is ethanol. Active ingredient may be present from about 1-15% by weight, or more. Total propellents consisting of dimethyl ether and fluorocarbon are 15-95% by weight.

It has been discovered that the most preferred homogeneous, non-toxic composition of the present invention comprises the following percentages of components measured by weight: a) ethanol, n-propanol or isopropanol at about 15-50% or even 40-50%, dimethyl ether at about 5-40% or even 5-15%; b) difluoroethane or 1,1,1,2-tetrafluoroethane at about 20-35% or even 25-30%; and c) water at about 1-25% or even 5-15%. The preferred amount of active ingredient is about 5%. The preferred amount of propellant is about 25-65%.

A total aerosol dispensing system consisting of container, valve and formula has also been discovered in accordance with the present invention. The system comprises a conventional sealed container which contains the novel composition according to the present invention, and which is provided with a conventional aerosol dispensing valve and actuator. The system is useful in storing and then dispensing active ingredient contained therein whenever desired. The composition includes the homogeneous 4-component system of the present invention in addition to active ingredient. ^J Each of the components of this composition is commercially available from chemical supply houses.

The invention will be described further in the following examples, which are intended for purposes of illustration and not limitation.

¹⁰ EXAMPLE 1

Two samples of a preferred composition of the present invention were mixed with active ingredient and other additives and designated B and C, formulated as shown in Table 1. The presence of additives such as

¹-^>fragrance, preservatives, and other additives commonly used by those skilled in the art is contemplated. Upon mixing these ingredients, the composition immediately became clear and formed a soluble, single-phase solution. The composition remained clear and

P^tO^whomogeneous both after one week at room temperature at after one week at 40° F.

The homogeneous mixture achieved with the preferred composition contrasts with the result achieved with composition A formulated as shown in Table 1.

25composition A contained alcohol at about 24%, dimethyl ether at about 30%, difluoroethane at about 34% and water at about 6% as well as active ingredient and other additives as indicated. Upon mixing these ingredients, the composition immediately became cloudy and separated

30into two layers.

35 It has further been discovered that when the composition of the present invention is formulated with active ingredient, for instance in the amounts of 1-10 wt. % and more preferably about 5 wt.%, the resulting composition is a homogeneous composition useful in 5dispensing the active ingredient from an aerosol dispensing system. Furthermore, the components of the composition useful as a propellant are non-toxic and useful in formulations for personal care products. A further advantage of the present invention is that given higher propellant content allowing for easier atomization, the valve and actuator selections and dimensions are less critical.

The composition of the present invention can be formulated following normal commercial practice, in

15which the alcohol and water are mixed with the active ingredient, and the mixture is added to a container which would be pressurized with a propellant mixture of the ether and the fluorocarbon. The final pressure is obtained by the specific mixture of all four components

20which are present with the active ingredient.

Implementation of aerosol dispensing parameters within the range of the composition set forth is deemed to be within the knowledge and skill of an ordinarily skilled artisan.

25 The following examples set forth formulations which are useful embodiments of the present invention.

30

35 TABLE 1 4 Component System

Hairspray Composition

Component A B C

Ethanol 23.98 48.98 48.9 (SD HO-Anhyd. )

A ino-2-methyl- 0.92 0.92 1.0 1-propanol containing 5% water (AMP 95%)

Distilled H₂0 6.30 10.0 10.0

Ampho er* 5.0 5.0 —

A phomer* LV-71 — -- 5.0

Fragrance 0.10 0.10 0.10 Dimethyl ether 30.0 5.0 5.0

Difluoroethane 33.70 30.0 30.0

Appearance of cloudy clear clear Finished Product (separates (& shake) Immediately into two layers)

Appearance of N/A clear clear Finished Product after 1 wk @ room temperature

Appearance of N/A clear clear Finished Product after 1 wk ? 40°F

* Octyl acrylamide/acrylates/butyl aminoethyl methacrylate polymer available from National Starch and Chemical Corp. EXAMPLE 2 Studies were performed whereby the composition of the present invention was tested in dispensing a hairspray from an aerosol dispensing system. Homogeneous compositions B and C were made with about 5% active ingredient and additives. The particular formulation of each composition is disclosed in Table 1. Study participants tested the homogeneous hair spray compositions B and C dispensed from a sealed container having an aerosol dispensing system equipped with an aerosol dispensing valve. Whole-head evaluations were performed on study participants, 2 or 3 per formulation, in order to observe overall performance of the hair sprays with compositions B and C. The results obtained are as follows: Composition B

Drying time for composition B was determined to be about 20 seconds and no stickiness or tackiness was present. The hold was rated as excellent, and the curl retention and manageability was rated as very good. The participant rated overall performance as very good.

Composition C Drying time for composition C was determined to be about 40 seconds. The product displayed a good hold when sprayed for 10-15 seconds, which was slightly longer than the participant usually sprays her hair. Manageability and curl retention was rated as very good as was overall performance.

When the composition is formulated in the amounts indicated, a homogeneous, one-phase composition of matter is achieved which is useful in an aerosol dispensing system and which has been shown to be effective.

EXAMPLE 3

4 Component Hairspray System

Component A B C

Ethanol 40.0 50.0 30.0

(anhydrous) Amino-2-methyl- 0.92 0.92 0.92 1-propanol containing 5% water

Amphomer 5.0 5.0 5.0 Distilled H₂0 8.98 11.48 6.48

Fragrance 0.10 0.10 0.10

Dimethyl ether 15.0 5.0 25.0

Difluoroethane 30.0 27.5 32.5 Appearance clear clear clear Immediately

Appearance clear clear clear after 1 wk 6 room temperature Appearance clear clear clear after 1 wk @ 40°F

% Propellant 45 32.5 57.5

Studies were performed whereby the compositions of the present invention as set forth in Example 3 were tested by dispensing from an aerosol container. Half-head tests were carried out comparing two of the compositions set forth in the table in Example 3 to a conventional aerosol hairspray formula¬ tion. Compositions A and B each exhibited longer drying times compared to the conventional product. Composition A exhibited little or no stickiness/tackiness, and exhibited superior hold and crust, manageability, and l°curl retention. Composition B displayed slight stickiness/tackiness and superior hold and crust.

15

20

25

30

35 EXAMPLE 4 4 Component Surface Disinfectant Spray Component Parts by Weight

Ethanol 40.0

_Water 39.8

5

Difluoroethane 10.0

Dimethyl ether 10.0

Hya ine 1622 0.2

(benzethonium chloride) 0

Solubility - clear

Room Temp. 3 days

% Total Propellant 20.0

5

0

5

0

5 EXAMPLE 5

1

4 Component Surface Insecticide

Component Parts by Weight

Isopropanol 40.0

5 Water 39.0

Difluoroethane 10.0

Dimethyl ether 10.0

Insecticide nominal °concentrate MJK No. 1830

Solubility - clear

Room Temp. 3 days

5

0

5

0

5 EXAMPLE 6

Personal Deodorant

Composition Parts by Weight Ethanol anhydrous 25.0 Water distilled 24.9 Hyamine 1622 0.10 Difluoroethane 25.0 Dimethyl ether 25.0 Solubility clear

EXAMPLE 7

Quick Drying Personal Deodorant

Composition Parts by Weight

Ethanol anhydrous 15.0 Hyamine 1622 0.2

Water distilled 9.6

Fragrance 0.2

Dimethyl ether 40.0

Difluoroethane 35.0

% Total Propellant 75.0

Solubility Room Temp. clear 40°F 14 days clear

Room Temp. 8 weeks clear

EXAMPLE 8

Wall Mounted Air Freshener

Composition Sample - Parts by Weight

A B C

Water 25.0 10.0 2.0

Ethanol anhydrous 25.0 15.0 8.0

Dimethyl ether 25.0 40.0 47.0

Difluoroethane 25.0 35.0 43.0

Fragrance trace trace trace

% Total Propellant 50.0 75.0 90.0

EXAMPLE 9

Disinfectant Deodorant

Composition Parts by Weight

Water 25.0

Ethanol 24.8

1,1,1,2-Tetrafluoroethane 25.0

Dimethyl ether 25.0

Orthophenyl phenol 0.1

Fragrance 0.1

Claims

WHAT IS CLAIMED IS: 1. A homogeneous composition useful in an aerosol dispensing system comprising: a. alcohol selected from the group consisting of alcohols containing 2-3 carbon atoms and mixtures thereof from about 5-50% by weight, and dimethyl ether from about 5-50% by weight, wherein said alcohol and dimethyl ether together comprise no greater than about 55% by weight of the composition; b. about 10-45% by weight of a non- chlorinated fluorocarbon material; and c. water from about 1-50% by weight.

2. A homogeneous composition as claimed in Claim 1 wherein alcohol is present at about 10-50% by weight.

3. A homogeneous composition as claimed in Claim 1 wherein dimethyl ether is present at about 5-45% by weight.

4. A homogeneous composition as claimed in Claim 1 wherein the non-chlorinated fluorocarbon is selected from the group consisting of difluoroethane and 1,1,1,2-tetrafluoroethane and mixtures thereof and is present at about 10-40% by weight.

5. A homogeneous composition as claimed in Claim 1 wherein 1,1,1,2-tetrafluoroethane is present at about 10-35% by weight.

6. A homogeneous composition as claimed in Claim 1 wherein water is present at about 1-30% by weight.

7. A homogeneous composition as claimed in claim 1 wherein said alcohol is ethanol.

8. A homogeneous composition as claimed in Claim 1 wherein said alcohol is isopropanol.

9. A homogeneous composition in accordance with Claim 1 comprising: a. alcohol selected from the group consisting of alcohols containing 2 or 3 carbon atoms and mixtures thereof from about 10-50% by weight, and dimethyl ether from about 5-45% by weight, wherein said alcohol and dimethyl ether together comprise no greater than about 55% by weight of the composition; ° b. about 10-40% by weight of a fluorocarbon material selected from the group consisting of difluoroethane and 1,1,1,2-tetrafluoroethane? and c. water from about 1-50% by weight.

10. A homogeneous composition in accordance 5with Claim 9 comprising ethanol at about 15-50% by weight, dimethyl ether at about 5-40% by weight, difluoroethane at about 20-35% by weight, and water at about 1-25% by weight.

11. A homogeneous composition in accordance 0_with Claim 9 comprising ethanol at about 15-50% by weight, dimethyl ether at about 5-40% by weight, 1,1,1,2-tetrafluoroethane at about 20-35% by weight and water at about 1-25% by weight.

12. A composition as claimed in Claim 1 5further comprising an active ingredient.

13. A composition as claimed in Claim 12 wherein said active ingredient is present in an amount up to about 15% by weight.

14. A homogeneous composition as claimed in 0ciaim 12 wherein said active ingredient is at least one

5 aterial selected from the group consisting of film formers and hair conditioning agents.

15. A homogeneous composition as claimed in Claim 12 wherein said alcohol is ethanol.

16. A homogeneous composition as claimed in 5Claim 12 wherein said alcohol is isopropanol.

17. A homogeneous composition in accordance with Claim 9 comprising ethanol at about 40-50% by weight, dimethyl ether at about 5-15% by weight, difluoroethane at about 25-30% by weight, water at about 1°5-15% by weight and active ingredient at about 5-15% by weight.

18. A homogeneous composition in accordance with Claim 9 comprising ethanol at about 40-50% by weight, dimethyl ether at about 5-15% by weight,

151,1,1,2-tetrafluoroethane at about 25-30% by weight, water at about 1-10% by weight and active ingredient at about 5-15% by weight.

19. An aerosol dispensing system comprising a sealed container equipped with an aerosol dispensing

20valve and containing therein a composition in accordance with Claim 12.

20. An aerosol dispensing system comprising a sealed container equipped with an aerosol dispensing valve and containing therein a composition in accordance

25_with Claim 13.

30

35