WO1994007461A1

WO1994007461A1 - Perfume compositions

Info

Publication number: WO1994007461A1
Application number: PCT/EP1993/002555
Authority: WO
Inventors: Brian O'rourke; John Norman Short
Original assignee: Givaudan-Roure (International) S.A.
Priority date: 1992-09-29
Filing date: 1993-09-21
Publication date: 1994-04-14

Abstract

The invention concerns non-sticky, non-ethanolic fragrance formulations containing conventional odoriferous material at a level of ca. 2 %, preferably ca. 5 % to ca. 30 % which is solubilised by a combination of (a) a solubiliser and (b) a cosolubiliser in water.

Description

Perfume compositions

The invention concerns non-sticky, non-ethanolic fragrance formulations containing conventional odoriferous material at a level of ca. 2%, preferably ca. 5% to ca. 30% which is solubilised by a combination of (a) a solubiliser and

(b) a cosolubiliser in water.

These fragrance formulations are clear, transparent or at least translucent or opaque formulations, generally solutions, or at the utmost micro-emulsions.

Suitable solubilizers (a) are in particular non-ionic surface active agents (class ai).

A further class (class a2) of suitable solubilizers are Ci-β-alkanol propylene oxide and ethylene oxide polymers (oligomers) - and mixtures of such compounds with the non-ionic surfactants (ai).

The suitable classes are defined in detail below.

The fragrance ingredients may be of any natural and/or synthetic origin. In the foreground of the interest are (fat) soluble perfume oils.

(Fat) soluble perfume oils are natural or synthetic essential oils, such as orange oil, pine oil, peppermint oil, eucalyptus oil, lemon oil, clove leaf oil, cedarwood oil, bergamot oil, rosmary oil, patchouli oil, lavandin oil, spike oil, rose oil, vetiver oil, fennel oil, anise oil, thyme oil, geranium oil, lavender oil, menthol and synthetic, oil soluble perfume oils, preferably selected from the usual group consisting of alcohols, ketones, aldehydes, esters and polyenic compounds, etc. Naturally the term also encompasses any mixtures of perfume oils as defined herein. Furthermore, the term also encompasses perfume concentrates in non-ethanolic diluents as well as perfume bases in, preferably, non-ethanolic diluents. The final fragrance formulations, i.e. the consumer products to which the novel formulations are diluted to with water may be in particular

a) water-based colognes, containing up to ca. 6 % of perfume material, b) aqueous extrait perfumes, containing up to ca. 25%, in particular ca. 18 to 25 % perfume material,

c) aqueous Eau de Toilette containing up to ca. 18%, particularly ca. 6 to 18% perfume material.

It is to be noted that all figures and brackets of figures given are approximate figures.

The co-solubilizer, whose function is to promote the solubilization in a given solubilizer, is in particular a water-soluble glycol, e.g. an aliphatic glycol, such as ethylene glycol, propylene glycol, e.g. 1,2- propylene glycol, dipropylene glycol, hexylene glycol etc., or a poly¬ ethylene glycol, or a (volatile) silicone or a (volatile) silicone copolymer. The number n in the unit (OCH₂CH2)_n of the polyethylene glycol is conveniently ca. 4 to ca. 40, e.g. 6 or 12, etc. The alkyl group of the chain can contain ether linkages.

At the same time, the co-solubilizer functions as an anti-sticking agent, in as far as by its use, the concentration of the solubilizer - which very frequently causes stickiness - can be lowered, e.g. to levels less than would otherwise be possible, and in particular to equal or less than 25%. Additionally the co-solubilisers (b) and in particular the silicones can by themselves improve the cosmetic touch of the formulation and reduce the stickiness.

Convenient products a) are:

Cremophor RH40, RH60, Tween 20, 80 (Polysorbate 20, 80), Triton X-100 (Octoxynol-9), Lamacit 877 (Nonoxynol-14) LRI (mixture of PPG 26-buteth 26 and PEG hydrogenated castor oil), Triton X 102

(Octoxynol-13) etc.

Convenient products b) are:

Dimethicone (a linear polyalkyl, i.e. a polydimethyl siloxane), Cyclomethicone (a cyclic dimethyl polysiloxane), Phenyl Dimethicone (a polyalkylaryl siloxane), Dimethicone Copolyol (a polymer of dimethyl siloxane with polyethylene and/or polyoxypropylene side chains), Dimethiconol (a dimethyl silicone terminated with hydroxyl groups), etc.

and, in general, the entire classes to which the above commercial products belong to.

The volatile silicones such as the cyclic polysiloxanes are preferred, although also non-volatile silicones such as those polyalkyl siloxanes, polyalkylaryl siloxanes and polyether siloxane copolymers and mixtures thereof which do not exhibit an appreciable vapor pressure at ambient temperatures can be used. The preferred non¬ volatile silicones would be linear polyalkyl siloxanes, especially linear polydimethyl siloxanes (i.e. dimethicone).

The nature of the non-ionic surfactant (a) is not critical and practically all these surfactants may be used for the purpose of the present invention. Preferred are those surfactants with a HLB-value of 12 or greater.

As non-ionic surfactants there are, however, preferably used ethoxylated or propoxylated or propoxylated/ethoxylated derivatives of:

aliphatic alcohols, in particular C 12-20 aliphatic alcohols, alkylphenols, aliphatic carboxylic acid (fatty acid) esters, fatty acid esters of anhydrosorbitol, natural fats, oils and waxes.

All the various suitable types of non-ionic surfactants are well- known in the art, see e.g. the respective entries in the appropriate encyclopediae of, e.g. Ullmann, Kirk-Othmer and Rompp, as well as the appropriate cosmetic standard works, such as those from Janistyn, Nowak, Balsam/Sagarin, Shinoda, or, in particular, the

CFTA International Cosmetic Ingredient Dictionary 4th ed. (The Cosmetic, Toiletry, and Fragrance Association, Washington D.C. 1991) and the various leaflets provided by the suppliers listed in the literature. The term (Ci₂-₂₀-)aliphatic alcohols should embrace saturated and ethylenically unsaturated straight and branched, native and synthetic fatty alcohols. Examples are: cetyl, (iso) stearyl, cocoyl (i.e. fatty alcohols resulting from the hydrogenation of coconut oil), lauryl, oleyl, myristyl, capryl, tridecyl, eicosyl, alcohols.

The preferred alcohols are the Ciβ-iβ-aliphatic alcohols, e.g. cetyl, stearyl and oleyl alcohol.

The term alkylphenol should particularly embrace mono-, di- and tri-C_δ-i_δ-alkyl-phenols, whereby the alkyl radicals can be straight or branched. Examples are octyl, nonyl, dodecyl; octyl and nonyl are preferred.

The term aliphatic carboxylic acid (fatty acid) esters should embrace monoesters, diesters, sesquiesters of the fatty acids, e.g. of Ci2-i8-acids, particularly Cιβ-18-acids; examples of such acids are lauric, (iso) stearic, myristic, palmitic, stearic (preferred), linolenic linoleic, oleic, coco (i.e. fatty acids derived from coconut oil), ricinoleic, castor, etc. and hydrogenated castor oil fatty acids (preferred).

The term relates primarily to the respective polyoxyethylene (preferred) and polyoxypropylene/polyoxyethylene esters of the fatty acids enumerated above.

The term should, however, also embrace esters with polyhydroxy compounds, e.g. ethylene glycol, polyethylene glycol, glycerol, diglycerol, polyglycerol, propylene glycol, sorbitol, etc.

The term fatty acid esters of anhydrosorbitol relates to mono-, di- and triesters of sorbitan and fatty acids, e.g. to the oleates (preferred), to the laurates, to the palmitates, the stearates, etc.

The term natural fats, oils and waxes relates preferably to such compounds as castor oil (triglyceride high in ricinoleic esters), to lanolin, to beeswax, etc.

The average number of ethylene oxide units (degree of ethoxylation, EO) in the propoxylated and ethoxylated component (a2) is suitably between 10 and 40, preferably between 25 and 35; the respective number of propylene oxide units (degree of propoxylation, PO) is also suitably between 10 and 40, also preferably between 25 and 35.

The terms "ethoxylated" and "propoxylated-ethoxylated" relate to the condensation products of ethylene oxide and/or propylene oxide with substrates having acid (movable) protons, i.e. those enumerated above for component (ai).

In an analogous manner, the term "propylene oxide and ethylene oxide polymer" relates to the respective condensation products of the group of compounds outlined above for a) with ethylene oxide and propylene oxide.

e.g. Ci.β-alkanol +

condense reaction product with

C_l2-20-aliphatic alcohol +

, or

e.g. Ci2-20-aliphatic alcohol +

condense reaction product

The reaction involved is genetically an alkylation (i.e. an oxalkylation, a hydroxethylation), the products resulting from this reaction are thus usually termed ethoxlates or oxethylates and propoxylates or oxpropylates.

The respective figures for EO in the components ai) are suitably between 8 and 200, preferably between 30 and 50, PO is suitably 0 to 20, preferably 0 to 6, most preferably 2 to 4.

A preferred class of Cι-6-alkanol derivatives are butanol derivatives, e.g. as represented by formula C₄H₉(O-C₃H₆)aO(C₂H₄)_bOH

wherein a = 20 to 40, preferably 20 to 30 and b = 20 to 40, preferably 25 to 35.

If a = b = 26, the product involved is Witconol APEB (Witco Chemical, Organics Div.).

In all cases where a number of ethylene oxide or propylene oxide groups is given (example: butyl alcohol 26 PO 26 EO), this is an average number or molecules added. It is well-known that this number represents a statistical average, and in a given composition, the proportion of molecules present with the number shown will very often not be greater than 30 to 40% of the total number of molecules.

The preparation of the novel formulations is conveniently effected y a) mixing the ethanol-free perfume concentrate and the solubilizer, preferably at room temperature until a homogeneous mixture results, and then adding the co-solubilizer, again until the mixture is homogeneous, then adding the water to such premix, slowly at first under vigorous stirring, then more quickly towards the end.

The premix contains conveniently from ca. 12.5% to ca. 75% fragrance material.

The solubilizer is generally more expensive then the co- solubilizer, it is thus generally indicated to work with a the minimum amount of solubilizer.

The novel solubilized perfume oil solutions may be used in cosmetic formulations, i.e. in aqueous solutions, in sprays, gels, etc. Suitable and preferred approximate parameters are as follows:

convenient preferred amount of perfume oil in fragrance solution 2% to 30% 5% to 20%

(a) 1% to 25% 5% to 18%

(b) 8% to 50% 10% to 30%

amount of a) + bVperfume oil l to lO l to 6

amount of (a) + (b) in final fragrance 2% to 50% 15% to 40% solution

[H2O] in consumer product 20% to 95% 40% to 80%

If (b) is a (volatile) silicone, a convenient amount is ca. 0.6 - 2% and a prefered εunount is ca. 0.8 to 1.5%.

In the context of this invention, all percentages are given on the weight basis.

γaτn lP 1

a) Water - LRI - Propylene glycol - 15% Perfume E

A = Cosmetically acceptable touch C = Sticky

S = Stable, see also Example 2 U = Unstable

Sticky is defined as the skin having excessive drag when stroked with a finger after the fragrance formulation has been applied in normal conventional doses and allowed to dry.

Cosmetically acceptable is defined as the skin having an agreeable touch and is not sticky after the formulation has been applied as above.

Stable; the formulation is stable when it remains clear without separation into 2 or more phases when stored for a period of 1 month at temperatures in the range of ca. 5 - 45°C.

Unstable; the formulation becomes milky or separates into 2 or more phases when stored for a period of 1 month at temperatures in the range of ca. 5 - 45°C.

Aspect; aspect is the physical appearance at normal room temperature, either clear (transparent) or opaque (milky). b) Water - LRI - Propylene glycol - 20% Perfume G

A = Cosmetically acceptable touch

C = Sticky

S = Stable

U = Unstable (2-phases), see Example 1

c) Water - LRI - Dimethicone - 5% Perfume M

A = Acceptable, non-sticky

S a Stable

U = Unstable, see Example 1

d) Water - Lamacit 877-DGP - 10% Perfume S

A,C : see Example 1

U unstable

* S2, S4, S8: increase of the percentage of Lamacit : increase of the solution stability.

* S8, S9, S12: increase of the percentage of DPG : decrease of the percentage of Lamacit.

* Sll, S12: increase of the percentage of Lamacit : change from a cloudy solution to a clear one.

In the above Examples Perfume E, G, M and S are conventional fragrance bases consisting of natural and synthetic ingredients, whereby these bases contain at the outmost 10% - non ethanolic - ingredients.

The examples show that the use of (glycol) co-solubilisers allow a reduction of the amount of solubiliser required to obtain a clear solution and improve the stability of the clear solution.

Thus, the solubilisers (a) used in the examples 2 are :

(a) - LRI (mixture of PPG26 - buteth 26 and PEG hydrogenated castor oil).

(a) - Octoxynol 13 (eg. Triton X102.)

(a) - Polysorbate 20 (eg. Tween 20), Montanox 20

The co-solubilisers (b) used in the examples 2 are

(b) - Propylene glycol,

(b) - Dipropylene glycol,

(b) - PEG 12.

a)

b)

c)

d)

The preferred Couples of (a) and (b) consist of those chemicals made use of in the Examples 1 a) to d) and 2 a) to d); hexylene glycol as a still further compound (b), must also be mentioned here. Practical selection of solubiliser and co-solubiliser:

A suitable formulation can expediently be made as follows:

1 - A convenient solubiliser and co-solubiliser are selected, eg (a) solubiliser LRI and (b) dipropylene glycol.

2- The amount of solubiliser needed to approach reasonable solubiUzation for the required amount of fragrance oil in water is determined in the absence of co-solubiliser (b).

3 - The amount of solubiliser determined in # 2 is reduced by adding the co-solubiliser in the range as indicated.

4 - The levels of solubiliser (a) and co-solubiliser (b) are optimised by empirical methods so as to give a fragrance solution with the optimum aspect, stability and touch.

EP A 261 351 discloses, inter alia, stable, aqueous solutions of fat soluble perfume oils, containing

a) a Ci to C_- alkanol propylene oxide and ethylene oxide polyme oligomer) and

b) a non -ionic emulsifier.

The fragrance solutions in this reference require more solubiliser and are sticky and in general more expensive than an equivalent solution made according to the present invention, because the above mentioned component (a) does not correspond to any one of the co-solubilisers (b) of the current invention.

Claims

1. A non-sticky, non ethanolic fragrance formulation containing conventional odoriferous material at a level of ca. 2, preferably 5% to ca. 30% which is solubilised by a combination of (a) a solubiliser and

(b) a cosolubiliser in water.

2. A fragrance formulation as claimed in Claim 1, wherein the water is present at levels between ca. 20% and ca. 95%, preferably between ca. 40% and ca. 80%.

3. A fragrance formulation as claimed in Claim 1 or 2, in which the odoriferous material is present at levels between ca. 5% and ca. 20%.

4. A fragrance formulation as claimed in any one of Claims 1 to 3, wherein the solubiliser is present at levels between ca. 1% and ca.

25%, preferably between ca. 5% and ca. 25%, most preferably between ca. 5 and ca. 18 %.

5. A fragrance formulation as claimed in any one of Claims 1 to

4, in which the cosolubilizer is present at levels between ca. 8% and ca. 50%, preferably between ca. 10% and ca. 40%, most preferably between ca. 10 and ca. 30 %.

6. A fragrance formulation as claimed in any one of Claims 1 to

5, in which the solubilizer is an ethoxylated derivative of a natural fat, oil or wax or an ethoxylated derivative of an phenol.

7. A fragrance formulation as claimed in any one of Claims 1 to

6, in which the cosolubilizer is a glycol or a volatile or non-volatile silicone fluid or silicone copolymer.

8. A premix formulation useful for preparing the fragrance formulations according to any one of Claims 1 to 7, containing conventional odoriferous material and the components (a) and (b) of Claim 1.