Liquid or Solid Fabric Softener Composition Comprising Microencapsulated Fragrance Suspension and Process for Preparing Same

This invention relates to specific fragrance compositions and specific liquid or solid fabric softener compositions of matter. The liquid or solid fabric softener compositions of matter when used in their proper environments, cause the fabrics treated with same to have aromas with good initial strengths which aromas are controllably released (under the normal conditions of use of fabrics treated using solutions created from the liquid or solid fabric softening compositions of matter, at a consistently high level over an extended period of time. This invention is also specially adapted to the creation of liquid or solid fabric softener compositions of matter which give rise to "bursts" of different fragrances from a qualitative standpoint at controllable time intervals over controllable periods of time.

The prior art recognizes that perfume-containing particles of a defined melting point and size can be incorporated into compositions containing a fabric-substantive cationic surfactant. Thus, in Canadian Pat. No. 1,111,616 issued on Nov. 3, 1981 it is indicated that the cationic surfactant in the composition probably becomes associated, in the use of the composition, with the perfumed particles and assists in carrying the particles to a fabric surface where they release their perfume especially during heat treatment such as drying or ironing. It is further indicated in Canadian Pat. No. 1,111,616 that the particles have particular advantage of enhancing the impact of perfume components which are normally somewhat labile and tend to be lost during processing or use. The instant invention represents a distinct improvement over the advance in the prior art disclosed in Canadian Pat. No. 1,111,616. According to Canadian Pat. No. 1,111,616, there is provided a perfumed conditioning composition which comprises from 0.1% to 20% by weight of the composition of particles having an average particle size in the range of from 0.1 up to 2,000 microns and having a melting point in the range of from 38.degree. C. to 150.degree. C., said particles comprising, by weight of the particles (a) less than 95% in at least 25% of the carrier substance and (b) from 1% to 75% of a perfume, said particles being incorporated into a composition which contains from 0.1% to 10% of a fabric substantive cationic surfactant. The instant invention can be used in conjunction with the subject matter of the examples of Canadian Pat. No. 1,111,616 and represents a distinct improvement thereover.

Even prior to the discovery as set forth in Canadian Pat. No. 1,111,616, most domestic detergent compositions and rinse-added textile softeners have been perfumed, but in general, little of the perfume was transmitted to the fabrics except when special fabric substantive perfumes were used as described in United Kingdom Patent Specification No. 838,240.

In addition, German Offenlegungsschrift No. 2,631,129 describes textile treatment compositions containing prills of size 5 to 2,000 microns comprising 95 to 99.5% of a fabric softening (and anti-static) agent and 0.5 to 5% of a non-fabric softening fabric conditioning material, e.g. a perfume. Such prills are entrained and carried with the fabrics into a fabric drier where they melt or soften at the temperature reached in the drier. The melting of the prills allows the fabric softening agent to spread over the fabric surfaces by virtue of the tumbling action of the drier and further causes the non-fabric softening agent to deposit efficiently onto the fabrics being dried. The German Offenlegungsschrift No. 2,702,162 describes fabric conditioning particles of size from 5 to 2,000 microns comprising 20-53% castor wax, 45-80% quaternary fabric softener and optionally from 0.1 to 2% perfume. They are intended to be dispersed in detergent compositions. United Kingdom Patent Specification No. 1,204,123 describes mixtures of perfumes or other things in an extrudable solid which mixtures are formed into granules which are added to surfactant-containing powders. Fabric conditioning compositions containing perfume microcapsules are also described in U.S. Pat. No. 4,234,627 which relates to granular presoaking/washing compositions comprising:

(A) from about 3% to 20% by weight of a granular fabric treatment mixture, the granules within said mixture comprising

(i) water-insoluble, friable microcapsules varying in size from about 5 to 500 microns, each microcapsule consisting essentially of

(a) a liquid core containing fabric conditioning agent; and

(b) a solid thin polymeric shell completely surrounding said core; said shell having an average thickness ranging between 0.1 and 50 microns; and

(ii) a substantially water-insoluble, fabric substantive capsule transfer agent having a melting point between about 40.degree. C. and 150.degree. C.; said capsule transfer agent surrounding each microcapsule;

the weight ratio of microcapsules to capsule transfer agent within each granule of the fabric treatment mixture ranging between about 0.002:1 and 2000:1; and

(B) from about 5% to 90% by weight of a presoaking/washing adjuvant selected from the group consisting of water-soluble detersive surfactants, detergency builders and mixtures of water-soluble detersive surfactants and detergency builders.

In addition, United Kingdom published Patent Specification No. 2,022,609A describes a soap or detergent additive composition comprising a blend of:

(A) an essential oil

(B) a detergent composition which includes an anionic, cationic, or nonionic surfactant or mixtures thereof; and

(C) a softening agent which comprises a fixed oil derivative.

The essential oil could be, for example, a 35-40% eucalyptus oil solution as set forth in Example 4 on page 5 of said patent specification.

In addition, U.S. Pat. No. 4,284,567 issued on Aug. 18, 1981 discloses the requirement of considerable stability of perfume substances in the formulation of detergents particularly where the stability is required in alkaline surroundings. A tetrahydropyran derivative is described for use in perfuming detergents which is stable.

Furthermore, there has been considerable work performed relating to fragrance substances which have a fragrance impact both initially and over an extended period of time during the consumption of the consumable material in which the fragrance is located. Problems have arisen in attempting to create such fragrance compositions for use with hydro-alcohol compositions of matter such as colognes, wherein part of the fragrance is available for immediate results whereas another part of the fragrance provides the effect gradually over extended periods of time; and further, in different manners in different controllable periods of time. Such problems include the continuous distribution of "initial impact" and "extended release" fragrance over the entire mass of the hydro-alcohol composition of matter (e.g., cologne) as well as commercial manufacture of same.

In a somewhat analogous manner, U.S. Pat. Nos. 4,253,473, 4,259,355, 4,001,438 and 3,920,849 have presented solutions to such problems where other consumable materials are concerned, e.g. smoking tobacco, hot beverages, and chewing gums. Thus, described in U.S. Pat. No. 3,920,849, are orally utilizable compositions which may be either chewing gum compositions, chewable medicinal tablets, chewing tobacco or toothpaste having, on oral intake, a high flavor intensity release evenly and uniformly over an extended oral utilization time in the mouth cavity; the orally utilizable compositions containing a non-confined flavor oil, a flavor oil which is physically entrapped in solid particles and a suspending agent such as silica, xanthan gum, ethyl cellulose and hydroxypropyl cellulose; the non-confined flavor oil, the entrapped flavor oil and the suspension agent being premixed prior to addition to either the chewing gum base, the chewing tobacco, the chewable medicinal tablet base, the toothpaste base, the smoking tobacco or the hot beverage. Neither U.S. Pat. Nos. 4,253,473, 4,259,355, 3,920,849 nor 4,001,438 discloses the use of such material for fragrancing fabrics treated with one or more liquid or solid fabric softener compositions which are consumed during the standard use of such liquid or solid fabric softener compositions subsequent to the drying of the thus-treated fabric.

U.S. Pat. No. 1,526,039 teaches that if an essential oil or flavoring is combined with a chewing gum base in a finely divided condition, and the particles of the flavoring or oil are encased in a suitable covering so as not to contact the gum directly during manufacture, the deleterious effect of the flavoring on the gum is prevented or largely reduced. It is further stated therein that:

"When the emulsion is added to the gum base, it is thoroughly mixed therewith by the usual means employed for mixing the flavoring material with such base.

"The production of the emulsion serves to break up the essential oil into fine particles and to encase these particles in the emulsifying material, so that when the emulsion is added to the gum mass, the essential oil to a large degree is prevented from coming into direct contact with the base, and from having deleterious action thereon."

U.S. Pat. No. 2,886,440 teaches a method of preparing a chewing gum characterized by "extended flavor perception time, true flavor character, and high degree of flavor release comprising the steps of forming a spray-dried emulsion of a volatile, water-immiscible flavoring agent encapsulated within finely divided particles of gelatin, and substantially uniformly distributing said gelatin encapsulated flavoring agent within an all-enveloping mass of a chewable gum base."

The use of separate "fixed" and "unfixed" fragrance portions is also taught but there is no disclosure therein of the principle of this invention, to wit: mixing the fixed and unfixed fragrance portions with a suspension agent prior to adding to a fabric softener composition prior to use thereof.

U.S. Pat. No. 2,886,446 teaches a chewing gum comprising (i) smaller particles of gelatin characterized by faster liberation of flavor and (ii) larger particles of gelatin characterized by slower liberation of flavor, each of the gelatin particles containing dispersed therewithin, in dried emulsion form, discrete micro-droplets of a volatile water-immiscible flavoring agent, and an all-enveloping mass of a chewable gum base within which the particles are substantially uniformly distributed whereby the flavor is released substantially evenly and uniformly over the extended chewing time.

U.S. Pat. No. 2,886,445 teaches that:

"It is now possible to obtain a flavoring composition, particularly adapted for use in chewing gum which permits attainment of a product characterized by extended flavor perception time, true flavor character, and release of a large proportion of flavoring agent. This flavoring composition comprises finely divided particles of a dried hardened gelatin emulsion containing discrete micro-droplets of a volatile, water-immiscible flavoring agent. Preparation of the flavoring composition of this invention may be effected by encapsulating discrete micro-droplets of volatile, water-immiscible flavoring agent within finely divided particles of a dried emulsion of hardened gelatin."

U.S. Pat. No. 2,886,449 teaches:

"A chewing gum containing a flavoring composition characterized by an extended flavor perception time, true flavor character, controlled release of a large portion of flavoring agent, and reduction in amount of flavor oil required (which) may be prepared by the process comprising forming a gelatin-coacervated flavor, and substantially uniformly distributing said gelatin-coacervated flavor within an all-enveloping mass of a chewable gum base. The product chewing gum . . . comprises . . . finely divided particles of coacervated gelatin containing a water-immiscible flavoring agent therewithin and an all-enveloping mass of a chewing gum base within which the particles are substantially distributed."

The utilization of sustained release flavor containing capsules in such materials as chewing gum and medicinal tablets is also taught in British Pat. No. 1,205,764.

The use of sustained release flavor capsules in conjunction with polyethylene glycols (which are taught to be employed to desolventize the capsules) is set forth in British Pat. No. 1,318,799.

The use of hydroxypropyl cellulose contained in microcapsules especially for pressure sensitive copying paper is disclosed in Japanese Pat. No. J7 9000 426 claiming a priority of U.S. application Ser. No. 480,956 filed on June 19, 1974 and assigned to the Mead Corporation. In said Japanese Pat. No. J79 000 426, it is indicated that oil-containing microcapsules especially for pressure sensitive copying paper are prepared by (a) preparing an aqueous solution of hydroxypropyl cellulose containing reactive hydroxyl groups and having a decreasing water solubility as the temperature increases; (b) then preparing a solution of an oil soluble cross-linking agent for the hydroxypropyl cellulose in an oil; then emulsifying the oil solution in the aqueous solution to form an emulsion containing droplets of the oil solution; (c) then heating the emulsion to a temperature above the precipitation temperature of the hydroxypropyl cellulose so that hydroxypropyl cellulose precipitates over the droplets to form solid microcapsule walls and (d) finally maintaining the emulsion at this temperature until the microcapsule walls become insoluble in water and in the oil. Nothing in the Japanese Pat. No. J79 000 426 discloses the creation of a liquid or solid fabric softener composition wherein the fragrance thereof is controllably released during the use activity (after treatment of fabrics with said fabric softener composition) at a consistently high level over an extended period of time from the treated fabric.

In U.S. Pat. No. 3,623,489, the formation of a shredded tobacco material having intimately admixed therewith a micro-encapsulated synthetic clove flavoring material (wherein the capsules are of such a size as to create an audible crackling sound when burned) and the incorporation thereof into smoking articles such as cigarettes and cigars is disclosed. It is further disclosed that these capsules may also contain a tobacco flavor enhancer.

U.S. Pat. No. 3,753,730 issued on Aug. 21, 1973 discloses processes for altering the flavors of particulate grain products comprising applying a composition comprising a flavoring agent, an edible cold water insoluble film former and a vehicle to a particulate grain product; drying the distributed composition to form a flavor containing film on the grain product; and then optionally distributing the coated flavored grain through a large mass of uncoated grain particles.

German Offenlegungsschrift No. 2,826,042 published on Jan. 4, 1979 discloses a condiment consisting of a lemon flavored salt prepared by mixing salt and a lemon oil powder and spraying the resulting mixture with lemon oil. More particularly, the salt is admixed with (a) from 0.1 up to 0.5 weight percent of salt of a terpene-free lemon oil bonded to a powdery carrier and (b) terpene-free liquid lemon oil. The condiment is prepared by mixing the dry salt with component (a), spraying the mixture with component (b) and mixing through a screw conveyor.

Hydroxypropyl cellulose itself is described in particular in three publications:

a. Hercules/Klucel.RTM./hydroxypropyl cellulose published by Hercules Incorporated of Wilmington, Del.;

b. Klug, Vol. 24, No. 51, Food Technology, January, 1970, page 51 entitled "Functional Helpmate to Development . . . Hydroxypropyl Cellulose/a New Water Soluble Cellulose Polymer"; and

c. U.S. Pat. No. 3,278,521, issued on Oct. 11, 1966 entitled: "Hydroxypropyl Cellulose and Process"/Inventor: Klug.

However, the prior art does not set forth commercially feasible processes for creating fabric softener compositions containing an aromatizing composition which provides instantaneous, evenly distributed aroma release over extended, continuous, non-interrupted fragrance perception time periods and, at the same time, provides during the use activity (subsequent to treatment of the fabric with the fabric softener and drying of said fabric) extended constant fragrance impact which is provided by our invention.

The use of "spray dried fragrances" is not, however, new to the art. "Spray dried fragrances" are known as taught in the following prior art:

a. Miles et al, J. Soc. Cosmet. Chem., 22, 655-666 (Sept. 17, 1971) ["Encapsulated Perfumes in Aerosol Products"]

b. Brenner et al, U.S. Pat. No. 3,971,852 issued July 27, 1976 (Process of Encapsulating an Oil and Product Produced Thereby).

The Miles et al article discloses an apparently stable spray dried encapsulated fragrance which may be formulated into aerosols. It is indicated that when sprayed on a surface under both in vivo and in vitro conditions gradually release fragrance upon exposure to moisture. It is further shown by Miles et al that the release rate can be varied according to the liquid vehicle and that it varies with the individual test subject and to the stimuli to which he or she is exposed.

The Brenner et al, U.S. Pat. No. 3,971,852 discloses interalia perfume compositions, preferably in particulate form, comprising a cellular matrix having oil in the cells thereof in which the matrix comprises a polysaccharide and a polyhydroxy compound in such proportions that the oil may constitute up to 80% by volume so stably held in the cells that the extractable oil is not substantially in excess of 5%. The polysaccharides are indicated to be natural gums such as gum arabic, starch derivatives and dextrinized and hydrolyzed starches. It is further indicated that the polyhydroxy compounds may be alcohols, lactones, monoethers, plant-type sugars and acetals.

Nothing in either of the Brenner et al U.S. Pat. No. 3,971,852 or the Miles et al article infers the concept of our invention.

FIG. 1 is a photomicrograph of the fabric softener suspension produced according to Example I (200X magnification).

FIG. 2 is a photomicrograph of the fabric softener suspension produced according to Example II (200X magnification).

FIG. 3 sets forth a block diagram flow sheet indicating the preparation of a solid or liquid fabric softener of our invention as more fully described in Examples I and II.

FIG. 4 sets forth a block diagram flow sheet indicating the preparation of the fragranced solid or liquid fabric softener of our invention as more fully described in Example III.

FIG. 5 sets forth a block diagram flow sheet indicating the preparation of the fragranced solid or liquid fabric softener of our invention as more fully described in Example IV.

FIG. 6 sets forth a block diagram flow sheet indicating the preparation of another embodiment of our invention which is a fragranced fabric softener liquid which causes evolution on use from the fabrics treated therewith at controlled periods of time, different fragrances as more fully described in Example V.

FIG. 7 sets forth a graph of intensity of perceptible, desired aroma evolved from the fabric treated with the fabric softener composition of our invention vs. time for each of the individual aromas evolved as a result of the use of the fragranced liquid or solid fabric softener prepared according to Example V.

FIG. 8 sets forth a block diagram flow sheet indicating the preparation of the fragranced solid or liquid fabric softener of our invention as more fully described in Example VI wherein the use of the fragranced fabric softener causes the evolution of two different fragrances from the fabric treated therewith over two different periods of time in a controlled manner.

FIG. 9 sets forth a block diagram flow sheet indicating the preparation of the fragranced solid or liquid fabric softener of our invention as more fully described in Example VII wherein on use two different aromas are evolved at two different periods of time with high intensity and in a controlled manner.

FIG. 10 sets forth a block diagram flow sheet indicating the preparation of the fragranced solid or liquid fabric softener of our invention as more fully described in Example VIII wherein on use over two different periods of time, two different fragrances are evolved in a controlled manner for a controlled period of time.

FIG. 11 sets forth a block diagram flow sheet indicating the preparation of the fragranced solid or liquid fabric softener of our invention as more fully described in Example IX wherein on use, two different fragrances are evolved from the fabric treated with the fabric softener composition over two different periods of time in a controlled manner.

FIG. 12 sets forth a graph indicating the Klucel.RTM. brand of hydroxypropyl cellulose solids concentration (weight percent) vs. Brookfield viscosity at 25.degree. C. in centipoises for types E, L, J, G, M and H Klucel.RTM. hydroxypropyl cellulose materials. Thus, FIG. 12 indicates the effect of concentration of Klucel.RTM.-type on the viscosity of water solutions.

FIG. 13 sets forth a block diagram flow sheet indicating the preparation of the fragranced solid or liquid fabric softener of our invention as more fully described in Example X, with three distinct fragrances being evolved over a period of 24 hours commencing with the application of the fabric softener composition in liquid form to a fabric and drying of said fabric.

FIG. 14 is a graph of time (on the "X" axis) vs. intensity of aroma evolved from the fabric (scale 1-10) on the "Y" axis for the performance of the liquid fabric softener over a period of 24 hours beginning with the wearing of the dried fabric to which the fabric softener composition has been applied.

It is an object of this invention to provide a solid or liquid fabric softener composition containing a perfume composition characterized by (i) an almost instantaneous aroma perception prior to the use and on use of the fabric which has been treated with said fabric softener composition and (ii) over an extended period of time on use, controlled, constant and continuous non-interrupted, high impact fragrance release from the fabric which has been treated with said fabric softener composition.

A second object of this invention is to increase the total amount of aroma release from the fabric to which is applied the fabric softener composition of our invention.

Further objects of this invention will be apparent to those skilled in the art from the following detailed description of the invention.

This invention relates to the use of fragrance compositions in solid or liquid fabric softener compositions of matter.

The solid or liquid fabric softener compositions of matter have fragrances with good, evenly distributed initial strength and this fragrance or series of fragrances, as the case may be, is controllably released with continuous, non-interrupted, high fragrance impact over an extended period of time during the period of time starting with the wearing of the fabric which has been (a) treated with said fabric softener composition and (b) dried.

The solid or liquid fabric softener compositions of matter contain a mixture of (i) a con-confined fragrance oil (emulsified or non-emulsified or both); (ii) a fragrance oil which is physically entrapped in solid non-toxic particles and (iii) a suspending agent such as hydroxypropyl cellulose, ethyl cellulose, silica or xanthan gum; the non-confined oil, the fragrance oil which is physically entrapped in solid particles and suspending agent being premixed prior to addition to a carrier liquid for use.

Our invention thus provides for use in conjunction with solid or liquid fabric softener compositions (i) an organoleptically improved perfume product and additives therefor as well as (ii) methods of making same which overcome specific problems heretofore encountered in which improved aromatized compositions have an aroma with good initial strength and have one or more aromas which are controllably released during the use activity of the solid or liquid fabric softener compositions of matter at a consistently high level over an extended period of time prior to actual use and on utilization of the fabric softener in providing a softening effect on the fabric. The actual use period begins with the wearing of the fabric rather than on drying of the fabric.

Our invention further provides improved aromatized fabric softener additives (e.g. taken alone or further in conjunction with anti-static agents and/or detergents) and methods whereby various nuances may be imparted to the head space above the fabric treated with the fabric softener compositions particularly with the wear of said fabrics, and may be readily varied and controlled to produce the desired uniform (or uniform for discrete periods of time) characteristics wherein one or more of the aromas have good initial strength and wherein one or more of the aromas is controllably released during the use activity (commencing with the wear of the fabric) at a consistently high level over one or more extended periods of time.

Thus, it has been found that it is now possible to obtain a liquid or solid fabric softener composition of matter containing one or more fragrance compositions which provide almost (i) instantaneous fragrance release on use thereof in extended high intensity, (ii) constant fragrance perception time during "use" (commencing with the wearing of the fabric treated with the fabric softener), (iii) true fragrance character and (iv) controlled release of the major proportion of the fragrancing agent initially present in the fragrance composition. It has been further found that it now possible to obtain the impact of two, three or more different fragrances at different periods of time. The quantity of fragrance evolved and the quality of fragrance evolved over given periods of time are functions of the ratios of the particular ingredients utilized in the fabric softener compositions as explained in more detail, infra.

More specifically, various fabric softening compositions are usable in the practice of our invention. These fabric softening compositions may be divided into two categories, solid fabric softening compositions with which the perfumed pastes or powders can be mixed and (ii) liquid fabric softening compositions in which the perfumed powders or pastes or suspensions can be further suspended.

A. Examples of publications setting forth workable solid fabric softening compositions which are usable in the practice of our invention are:

1. U.S. Pat. No. 4,234,627 issued on Nov. 18, 1980 title: "Fabric Conditioning Compositions" (the disclosure of which is incorporated herein by reference);

2. U.S. Pat. No. 4,018,688 issued on Apr. 19, 1977 title: "Capsules, Process of Fabric Conditioning Composition Containing said Capsules" (the disclosure of which is incorporated herein by reference);

3. U.S. Pat. No. 4,294,710 issued on Oct. 13, 1981 title: "Detergent Softener with Amine Ingredient" (the disclosure of which is incorporated herein by reference);

4. U.S. Pat. No. 4,294,711 issued on Oct. 13, 1981 title: "Washing and Softening Compositions and Methods for their Manufacture" (the disclosure of which is incorporated herein by reference);

5. Canadian Pat. No. 1,100,262 issued on May 5, 1981 title: "Softening Composition" (particularly concerning distearyl dimethylammonium chloride) (the disclosure of which is incorporated herein by reference);

6. Canadian Pat. No. 1,102,054 issued on June 2, 1981 title: "Fabric Treatment Compositions" (the disclosure of which is incorporated herein by reference);

7. Canadian Pat. No. 1,102,510 issued on June 9, 1981 title: "Fabric Treatment Compositions Containing Polyglycerol Esters" (the disclosure of which is incorporated herein by reference);

8. Canadian Pat. No. 1,111,616 issued on Nov. 3, 1981 title: "Fabric Conditioning Composition" (the disclosure of which is incorporated herein by reference);

9. Canadian Pat. No. 1,069,260 issued on Jan. 8, 1980 title: "Fabric Treatment Compositions" (the disclosure of which is incorporated herein by reference);

10. Canadian Pat. No. 1,074,966 issued on Apr. 8, 1980 title: "Detergent-Compatible Fabric Softening and Antistatic Compositions" (the disclosure of which is incorporated herein by reference);

11. Canadian Pat. No. 1,079,459 issued on June 17, 1980 title: "Fabric Treatment Compositions" (the disclosure of which is incorporated herein by reference);

12. Canadian Pat. No. 1,080,407 issued on July 1, 1980 title: "Capsules and Fabric Conditioning Composition Containing Same" (the disclosure of which is incorporated herein by reference);

13. Canadian Pat. No. 1,104,760 issued on July 14, 1981 title: "Antistatic, Fabric-Softening Detergent Additive" (the disclosure of which is incorporated herein by reference);

14. Canadian Pat. No. 1,066,207 issued on Nov. 13, 1979 title: "Fabric Conditioning Compositions" (the disclosure of which is incorporated herein by reference);

15. U.K. Pat. No. 1,556,437 published Nov. 21, 1979 title: "Fabric Softening Agents" (the disclosure of which is incorporated herein by reference);

16. U.K. Pat. No. 1,566,506 published Apr. 30, 1980 title: "Fabric Conditioning Compositions" (the disclosure of which is incorporated herein by reference);

17. U.K. Pat. No. 1,571,526 published July 16, 1980 title: "Fabric Treatment Compositions Containing Polyglycerol Esters" (the disclosure of which is incorporated herein by reference);

18. U.K. Pat. No. 1,571,527 published July 16, 1980 title: "Fabric Treatment Compositions" (the disclosure of which is incorporated herein by reference);

19. U.K. Pat. No. 2,043,130 A filed Mar. 2, 1979 and issued on Oct. 1, 1980 title: "Fabric Care Compositions Containing Smectite Clay and Gelatinized Vegetable Starch" (the disclosure of which is incorporated herein by reference);

20. U.K. Pat. No. 2,040,989 A issued Sept. 3, 1980 title: "Antistatic, Fabric-Softening Detergent Additive" (the disclosure of which is incorporated herein by reference);

21. European published Patent Application No. 23,367 filed on June 17, 1980 title: "Detergent Composition having a Textile Softening Property and its Manufacture" (the disclosure of which is incorporated herein by reference);

22. European Patent Application No. 26,013 published Apr. 1, 1981 title: "Washing and Softening Compositions and Methods for their Manufacture" (the disclosure of which is incorporated herein by reference).

B. Liquid fabric softener compositions:

1. U.S. Pat. No. 3,664,952 issued on May 23, 1972 title: "Aqueous Textile Softening Composition" (the disclosure of which is incorporated herein by reference);

2. U.S. Pat. No. 4,173,539 issued on Nov. 6, 1979 title: "Cationic Surfactant Compositions" (the disclosure of which is incorporated herein by reference);

3. U.S. Pat. No. 4,264,457 issued on Apr. 28, 1981 title: "Cationic Liquid Laundry Detergent and Fabric Softener" (the disclosure of which is incorporated herein by reference);

4. U.S. Pat. No. 4,268,401 issued on May 19, 1981 title: "Liquid Detergent Compositions Having Washing and Softening Properties" (the disclosure of which is incorporated herein by reference);

5. U.S. Pat. No. 2,978,408 issued on Apr. 4, 1961 title: "Scorch Resistant Textile Softening Finish Composition" (the disclosure of which is incorporated by reference);

6. U.S. Pat. No. 4,292,035 issued on Sept. 29, 1981 title: "Fabric Softening Compositions" (the disclosure of which is incorporated herein by reference);

7. Canadian Pat. No. 1,074,965 issued on Apr. 8, 1980 title: "Fabric Softening Compositions" (the disclosure of which is incorporated herein by reference);

8. Canadian Pat. No. 1,102,054 issued on June 2, 1981 title: "Fabric Treatment Compositions" (the disclosure of which is incorporated herein by reference);

9. Canadian Pat. No. 1,102,510 issued on June 9, 1981 title: "Fabric Treatment Compositions Containing Polyglycerol Esters" (the disclosure of which is incorporated herein by reference);

10. Canadian Pat. No. 1,102,511 issued on June 9, 1981 title: "Textile Treating Composition" (the disclosure of which is incorporated herein by reference);

11. Canadian Pat. No. 1,100,262 issued on May 5, 1981 title: "Softening Composition" (the disclosure of which is incorporated herein by reference);

12. Canadian Pat. No. 1,105,207 issued on July 21, 1981 title: "Textile Treatment Compositions" (the disclosure of which is incorporated herein by reference);

13. Canadian Pat. No. 1,105,208 issued on July 21, 1981 title: "Textile Treatment Composition" (the disclosure of which is incorporated herein by reference);

14. Canadian Pat. No. 1,105,209 issued on July 21, 1981 title: "Textile Conditioning Compositions with Low Content of Cationic Materials" (the disclosure of which is incorporated herein by reference);

15. Canadian Pat. No. 1,106,109 issued on Aug. 4, 1981 title: "Concentrated Liquid Fabric Softener Composition" (the disclosure of which is incorporated herein by reference);

16. Canadian Pat. No. 1,110,015 issued on Oct. 6, 1981 title: "Fabric Softener Composition and Method" (the disclosure of which is incorporated herein by reference);

17. Canadian Pat. No. 1,111,617 issued on Nov. 3, 1981 title: "Textile Conditioning Compositions Containing Polymeric Cationic Materials" (the disclosure of which is incorporated herein by reference);

18. U.K. Patent Application No. 2,041,025 A filed on June 26, 1978 and issued on Sept. 3, 1980 title: "Concentrated Liquid Fabric Softener Containing Mixed Active System" (the disclosure of which is incorporated herein by reference);

19. European published Patent Application No. 21,476 filed on May 27, 1980 and published on Jan. 7, 1981 title: "Liquid Fabric Softener Containing a Quaternary Ammonium Salt and Method of Conditioning Fabrics" (the disclosure of which is incorporated herein by reference);

20. European published Application No. 18,039 filed on Apr. 10, 1980 and published on Oct. 29, 1980 title: "Fabric Softening Composition" (the disclosure of which is incorporated herein by reference).

The fragrance compositions useful with the fabric softener compositions of our invention consist essentially of one or a combination of the following suspensions of entrapped fragrance in a solid in a liquid fragrance medium whereby no settling of the entrapped fragrance occurs in the liquid medium which is also a fragrance at least compatible with the entrapped fragrance if not the same as the entrapped fragrance.

a. From about 1 part by weight up to about 10 parts by weight of a non-confined fragrance in alcoholic solution which alcoholic solution contains a surfactant;

b. From about 0.1 parts by weight up to about 10 parts by weight of a solid suspending agent which may or may not be hydrated with water, selected from the group consisting of clays, e.g., smectite clay, hydroxypropyl cellulose having a molecular weight of from about 50,000 up to about 800,000, a structure as follows: ##STR1## having a particle size such that 95% of the particles pass through 30 mesh screens and 99% of the particles pass through 20 mesh screens and having a viscosity defined according to FIG. 12; or colloidal silica, xanthan gum or ethyl cellulose having a particle size of from about 0.004 up to about 0.130 microns, a surface area of from about 100 up to about 500 m.sup.2 per gram and a density of from about 1.0 up to about 4.0 pounds per cubic foot;

c. From about 2 up to about 10 parts by weight of an entrapped fragrance oil which is releasable either (i) hydrolytically (as a result of contact with excreted sweat and the fabric treated with a fabric softener composition of our invention) or (ii) by means of the application of mechanical pressure (for example as a result of rubbing or washing and/or normal contact between the skin and clothing article treated with the fabric softener composition of our invention), physically entrapped in a solid material, said solid material having a particle size of from about 3 microns up to about 400 microns, said physically entrapped fragrance oil being organoleptically compatible with the non-confined fragrance oil of "a".

a. From about 1 up to about 10 parts by weight of a non-confined hydrophobic fragrance oil;

b. From about 0.1 up to about 10 parts by weight of a solid suspending agent selected from the group consisting of hydroxypropyl cellulose having a molecular weight of from about 50,000 up to about 800,000, a structure as follows: ##STR2## having a particle size such that 95% of particles are passed through 30 mesh screens and 99% of the particles are passed through 20% mesh screens and having a viscosity defined according to FIG. 12; or colloidal silica; or xanthan gum; or ethyl cellulose having a particle size of from about 0.004 up to about 0.130 microns, a surface area of from about 100 up to about 500 m.sup.2 per gram and a density of from about 1.0 up to about 4.0 pounds per cubic foot;

c. From about 2 up to about 10 parts by weight of an entrapped fragrance oil releasable either (i) hydrolytically (as a result of contact with excreted sweat and the fabric treated with a fabric softener composition of our invention) or (ii) by means of the application of mechanical pressure (for example, as a result of rubbing or washing and/or normal contact between the skin and clothing articles treated with the fabric softener composition of our invention), physically entrapped in a solid material, said solid material having a particle size of from about 3 microns up to about 400 microns, said physically entrapped fragrance oil being organoleptically compatible with the non-confined hydrophobic fragrance oil.

a. From about 1 part up to about 10 parts by weight of a non-confined hydrophobic first fragrance oil;

b. From about 0.1 up to about 10 parts by weight of a solid suspending agent for suspending such first fragrance oil selected from the group consisting of hydroxypropyl cellulose having a molecular weight of from about 50,000 up to about 800,000, a structure as follows: ##STR3## having a particle size such that 95% of the particles pass through 30 mesh screens and 99% of the particles pass through 20 mesh screens and having a viscosity defined according to FIG. 12; or colloidal silica; xanthan gum or ethyl cellulose having a particle size of from about 0.004 up to about 0.130 microns, a surface area of from about 100 up to about 500 square meters per gram and a density of from about 1.0 up to about 4.0 pounds per cubic foot;

c. For the non-confined hydrophobic first fragrance oil, from about 2 up to about 10 parts by weight of an entrapped fragrance oil releasable either (i) hydrolytically (as a result of contact with excreted sweat and the fabric treated with a fabric softener composition of our invention) or (ii) by means of application of mechanical pressure (for example, as a result of rubbing, or washing and/or normal contact between the skin and clothing article treated with the fabric softener composition of our invention), physically entrapped in a solid material, said solid material having a particle size of from about 3 microns up to about 400 microns, said physically entrapped fragrance oil being organoleptically compatible with the non-confined hydrophobic first fragrance oil as well as the confined and non-confined fragrance materials as set forth infra in "d", "e" and "f";

d. From about 1 part by weight up to about 10 parts by weight of a second fragrance oil, which is compatible from an organoleptic standpoint with said first fragrance oil and which is compatible with said entrapped fragrance oil, in an alcoholic solution with a surfactant material. The surfactant material may be, and is preferred to be, a nonionic surface active material such as a sucrose ester, having the generic structure: ##STR4## wherein R represents an alkyl group of a fatty acid.

e. For the non-confined second fragrance oil, from about 0.1 up to about 10 parts by weight of a solid suspending agent or a suspending agent combined with water which may be, for example, smectite clay or another type of clay defined as "Ben-A-Gel.RTM." which is a highly beneficiated smectite clay having a specific gravity of 2.5, a density of 20.9 pounds per gallon and a bulking value of 0.0479 gallons per pound; or hydroxypropyl cellulose having a molecular weight of from about 50,000 up to about 800,000, a structure as follows: ##STR5## having a particle size such that 95% of the particles are passed through 30 mesh screens and 99% of the particles are passed through 20 mesh screens and having a viscosity defined according to FIG. 12; or colloidal silica, xanthan gum or ethyl cellulose having a particle size of from about 0.004 up to about 0.130 microns, a surface area of from about 100 up to about 500 m.sup.2 per gram and a density of from about 1.0 up to about 4.0 pounds per cubic foot;

f. For the non-confined second fragrance oil, from about 2 up to about 10 parts by weight of an entrapped fragrance oil, releasable either (i) hydrolytically (as a result of contact with excreted sweat and the fabric treated with a fabric softener composition of our invention) or (ii) by means of application of mechanical pressure (for example as a result of rubbing or washing and/or normal contact between the skin and clothing articles treated with the fabric softener composition of our invention), physically entrapped in a solid material, said solid material having a particle size of from about 5 microns up to about 400 microns, said physically entrapped fragrance oil being organoleptically compatible with the fragrance oils of "a", "b", "c", "d" and "e", supra.

a. From about 2 up to about 10 parts by weight of a first non-confined hydrophobic fragrance oil;

b. From about 0.1 up to about 10 parts by weight of a solid suspending agent for the fragrance oil in "a" selected from the group consisting of finely divided clay, (e.g., attapulgite clay), hydroxypropyl cellulose having a molecular weight of from about 50,000 up to about 800,000, a structure as follows: ##STR6## having a particle size such that 95% of the particles are passed through 30 mesh screens and 99% of the particles are passed through 20 mesh screens and having a viscosity defined according to FIG. 12; or colloidal silica, xanthan gum or ethyl cellulose having particle sizes of from about 0.004 up to about 0.130 microns, a surface area of from about 100 up to about 500 m.sup.2 per gram and a density of from about 1.0 up to about 4.0 pounds per cubic foot;

c. From about 2 up to about 10 parts by weight of an entrapped fragrance oil releasable either (i) hydrolytically (as a result of contact with excreted sweat and the fabric treated with a fabric softener composition of our invention) or (ii) by means of application of mechanical pressure (for example, as a result of rubbing or washing and/or normal contact between the skin and clothing articles treated with the fabric softener composition of our invention), compatible with the fragrance oil in "a", physically entrapped in a solid material, said solid material having a particle size of from about 5 microns up to about 400 microns, said physically entrapped fragrance oil being organoleptically with the non-confined hydrophobic flavor oil of "a";

d. From about 2 up to about 10 parts by weight of a second non-confined hydrophobic fragrance oil different from that set forth in "a" herein;

e. From about 0.1 up to about 10 parts by weight of a solid suspending agent for the fragrance oil of "d" selected from the group consisting of attapulgite clay, hydroxypropyl cellulose having a molecular weight of from about 50,000 up to about 800,000, a structure as follows: ##STR7## having a particle size such that 95% of the particles are passed through 30 mesh screens and 99% of the particles are passed through 20 mesh screens and having a viscosity defined according to FIG. 12; or colloidal silica, xanthan gum or ethyl cellulose having particle sizes of from about 0.004 up to about 0.130 microns, a surface area of from about 100 up to about 500 square meters per gram and a density of from about 1.0 up to about 4.0 pounds per cubic foot;

f. From about 2 up to about 10 parts by weight of an entrapped fragrance oil releasable either (i) hydrolytically (as a result of contact with excreted sweat and the fabric treated with a fabric softener composition of our invention) or (ii) by means of application of mechanical pressure (for example, as a result of rubbing or washing and/or normal contact between the skin and clothing articles treated with the fabric softener composition of our invention), compatible with the fragrance oil of "d", physically entrapped in a solid material, said solid material having a particle size of from about 5 microns up to about 400 microns, said physically entrapped fragrance oil being organoleptically compatible with said non-confined hydrophobic fragrance oil "e" as well as "a";

g. From about 2 up to about 10 parts by weight of a third non-confined fragrance oil further mixed with an alcohol such as ethyl alcohol and a surfactant;

h. From about 0.1 up to about 10 parts by weight of a solid suspending agent for the fragrance mixture "g" selected from the group consisting of a finely divided clay e.g., attapulgite clay, or hydroxypropyl cellulose having a molecular weight of from about 50,000 up to about 800,000, a structure as follows: ##STR8## having a particle size such that 95% of the particles are passed through 30 mesh screens and 99% of the particles are passed through 20 mesh screens and having a viscosity defined according to FIG. 12; or colloidal silica; or xanthan gum; or ethyl cellulose having a particle size of from about 0.004 up to about 0.130 microns, a surface area of from about 100 up to about 500 m.sup.2 per gram and a density of from about 1.0 up to about 4.0 pounds per cubic foot;

j. From about 2 up to about 10 parts by weight of an entrapped fragrance oil releasable either (i) hydrolytically (as a result of contact with excreted sweat and the fabric treated with the fabric softener composition of our invention) or (ii) by means of application of mechanical pressure (for example, as a result of rubbing or washing and/or normal contact between the skin and clothing articles treated with the fabric softener composition of our invention), physically entrapped in a solid material, said solid material being capable of being broken down over a period of time as a result of the normal use of colognes, said solid material having a particle size of from about 5 microns up to about 400 microns, said physically entrapped fragrance oil being organoleptically compatible with the non-confined fragrance oils and fragrance oil solutions of "a", "d" and "g" as well as the confined fragrance oils of "c" and "f".

Preparation of the fragrance compositions employed in the liquid or solid fabric softener compositions of matter taken alone or further together with anti-static agents or detergents of our invention may be effected in the alternative by:

First preparing a mixture of fragrance oil, alcohol and surfactant. The range of ratios of fragrance: alcohol may vary from about 1:5 up to about 1:40 with a preferred ratio (weight:weight) of 1:10. The ratio range of fragrance:surfactant may vary from about 1:2 up to about 3:1 with a preferred ratio of 2 parts by weight of fragrance:1 part by weight of surfactant. The ratio range of alcohol:surfactant may vary from about 10:1 up to about 30:1 with a preferred ratio of alcohol:surfactant being about 20:1 (weight:weight). The type of alcohol used which is non-toxic, e.g. ethyl alcohol or isopropyl alcohol, preferably ethyl alcohol. The type of surfactant used is preferred to be a nonionic surfact active material although anionic, cationic or zwitterionic surface active materials are usable. Preferred in the group of nonionic surface active materials for the purposes of our invention are sucrose esters produced by the reaction of sucrose with tallow fatty acids having the generic structure: ##STR9## wherein R is a fatty acid alkyl group. Specific examples of such sucrose esters are "CRODESTA.RTM.F-10, F-20, F-50, F-70, F-110, F-140 and F-150" manufactured by Croda Incorporated of 51 Madison Avenue, New York, N.Y. 10010. The properties of these esters are as follows:

Additives to the fragrance:alcohol:surfactant mixture are preferred but not necessary for stabilization purposes. Such agents are, for example, methyl paraben. The resulting mixture is then admixed with from about 1.0 part by weight up to about 2 parts by weight of a suspending agent which may be a mixture of finely divided clay and water, e.g., smectite clay (Ben-A-Gel.RTM.EW manufactured by N L Industries, Inc., P.O. Box 700, Hightstown, N.J. 08520) which is described as a highly beneficiated smectite clay having a specific gravity of 2.5, a density of 20.9 pounds per gallon and a bulking value in gallons per pound of 0.0479, or hydroxypropyl cellulose having a molecular weight of from about 50,000 up to about 800,000, a structure as follows: ##STR10## having a particle size such that 95% of the particles are passed through 30 mesh screens and 99% of the particles are passed through 20 mesh screens and having a viscosity defined according to FIG. 12; or colloidal silica, e.g., Cab-O-Sil.RTM.M-5 brand of silica produced by the Cabot Corporation of 125 High Street, Boston, Mass. 02110 having a surface area of 200 m.sup.2 per gram, a nominal particle size of 0.012 microns and a density of 2.3 pounds per cubic foot; xanthan gum and ethyl cellulose, said silica, xanthan gum and ethyl cellulose having particle sizes of from about 0.004 up to about 0.130 microns, a surface area of from about 100 up to about 500 m.sup.2 per gram and a density of from about 1.0 up to about 4.0 pounds per cubic foot thereby forming a first suspension; and then:

Admixing the first suspension with from about 2 up to about 10 parts by weight of an entrapped fragrance oil releasable either (i) hydrolytically (as a result of contact with excreted sweat and the fabric treated with a fabric softener composition of our invention) or (ii) by means of application of mechanical pressure (for example as a result of rubbing or washing and/or normal contact between the skin and clothing articles treated with the fabric softener composition of our invention), physically entrapped in a solid material, said solid material having a particle size of from about 5 microns up to about 400 microns thereby forming a second suspension, said physically entrapped fragrance oil being organoleptically compatible with the non-confined fragrance oil which is in admixture with the alcohol and the surfactant whereby the physically entrapped materials may be produced by one of the following techniques:

a. particles having a cellular matrix having the fragrance oil in the cells thereof in which the matrix comprises polysaccharide and polyhydroxy compounds in such proportions that the fragrance may constitute up to 80% by volume so stably held in the cells that the extractable perfume oil is not substantially in excess of 5% accomplished according to the procedure of U.S. Pat. No. 3,971,852 issued on July 27, 1976 (the disclosure of which is incorporated herein by reference);

b. microcapsules prepared by means of coacervation according to the process of U.S. Pat. Nos. 2,800,457; 2,800,458; 3,041,289 and 3,533,958 the disclosures of which are incorporated by reference herein;

c. microcapsules prepared by inter-phase polymerization around perfume oil microdroplets according to the process of U.S. Pat. Nos. 3,615,972 (suspension-type polymerization); 3,516,941; and 3,423,489, the disclosures of which are incorporated herein by reference.

Other entrapment agents include hydrocarbon waxes, solid surfactants (e.g., "Pluronics.RTM."), KLUCEL.RTM. hydroxypropyl cellulose (also used as suspension agents) and mannitol-polyvinyl alcohol polymer.

In addition to the foregoing suspension agents, additional suspension agents, polymeric suspension agents, SGP.RTM. absorbent polymers produced by the Henkel Corporation of 4620 West 77th Street, Minneapolis, Minn. 55435 is operable. Examples of the "SGP.RTM. polymers" are SGP.RTM. polymer 502S and SGP.RTM. polymer 147. The ratio of SGP.RTM. polymer to water usable in our invention may vary from 0.2 parts polymer:50 parts water up to 0.5 parts polymer:50 parts by weight water.

Additional suspension agents are defined in "Drug and Cosmetic Industry", May 1981, pages 39-42 and "Drug and Cosmetic Industry", June 1981, pages 52, 54, 56, 102, 103, 104 and 105 (articles by Alma J. Scheer). The suspension agents set forth in the Drug and Cosmetic Industry articles are:

a. microcrystalline cellulose

b. carrageenan

c. propylene glycol alginate

d. sodium alginate

e. methyl cellulose

f. sodium carboxymethyl cellulose (e.g., Hercules cellulose gum manufactured by Hercules, Inc., 910 Market Street, Wilmington, Del.)

g. Veegum (manufactured by R. T. Vanderbilt Company of 30 Winfield Street, Norwalk, Conn.) [a natural inorganic complex colloidal magnesium aluminum silicate]

It is noteworthy that the carboxymethyl cellulose and sodium carboxymethyl cellulose also act as stabilizers thereby obviating the necessity for an additional stabilizer in the system.

Subsequent to the admixing of the first suspension with the entrapped fragrance oil which is releasable either (i) hydrolytically (as a result of contact with excreted sweat and the fabric treated with the fabric softener composition of our invention) or (ii) by means of application of mechanical pressure (for example, as a result of rubbing or washing and/or normal contact between the skin and clothing articles treated with the fabric softener composition of our invention), the resulting material is, in the alternative:

a. suspended in a liquid fabric softener composition such as those defined according to the claims of U.S. Pat. No. 3,664,952; 4,173,539; 4,264,457 and 4,268,401 the disclosures of which are incorporated by reference herein and marketed as a fragranced liquid fabric softener; or

b. intimately admixed "as is" in thixotropic paste form with a "solid" fabric softener (of the nature of that disclosed in U.S. Pat. Nos. 4,234,627 or 4,018,688 which disclosures are incorporated by reference herein) and marketed as such; or

c. dried as a powder and then intimately admixed with a "solid" fabric softener (as disclosed in U.S. Pat. Nos. 4,234,627 or 4,018,688 incorporated by reference herein) and marketed as such.

The remarkable quality of the liquid fabric softener composition of matter of our invention is that substantially no settling occurs and that the composition of matter suspensions are quite stable.

Preparation of the fragrance compositions employed in the solid or liquid fabric softener compositions of matter of this aspect of our invention may be effected by:

1. Admixing

a. From about 1 up to about 10 parts by weight of a non-confined hydrophobic fragrance oil, and

b. From about 0.1 up to about 10 parts by weight of a solid or viscous liquid suspending agent selected from the group consisting of an SGP.RTM. polymer solution (manufactured by the Henkel Corporation of Minneapolis, Minn.); a colloidal suspension of smectite clay (e.g., Ben-A-Gel.RTM. manufactured by N L Industries, Inc. of Hightstown, N.J.); hydroxypropyl cellulose having a molecular weight of from about 50,000 up to about 800,000 having the structure: ##STR11## having a particle size such that 95% of the particles are passed through 30 mesh screens and 99% of the particles are passed through 20 mesh screens; having a viscosity defined according to FIG. 12; and colloidal silica, xanthan gum and ethyl cellulose having a particle size of from about 0.004 up to about 0.130 microns, a surface area of from about 100 up to about 500 m.sup.2 per gram and a density of from about 1.0 up to about 4.0 pounds per cubic foot thereby forming a first suspension and then

2. Admixing the first suspension with from about 2 up to about 10 parts by weight of an entrapped fragrance oil which is physically in a solid material and which is releasable either (i) hydrolytically (as a result of contact with excreted sweat and the fabric treated with a fabric softener composition of our invention) or (ii) by means of application of mechanical pressure (for example, as a result of rubbing or washing and/or normal contact between the skin and worn clothing articles treated with the fabric softener composition of our invention), said solid material having a particle size of from about 3 microns up to about 400 microns thereby forming a second suspension, said physically entrapped fragrance oil being organoleptically compatible with the non-confined hydrophobic fragrance oil, said solid particles being produced according to any number of processes thusly:

a. Suspension polymerization as defined according to U.S. Pat. No. 3,615,972, the disclosure of which is incorporated herein by reference;

b. Compositions in particulate form comprising a cellular matrix having the perfume oil in the cells thereof in which the matrix comprises polysaccharide and polyhydroxy compounds in such proportions that the perfume oil may constitute up to 80% by volume so stably held in the cells that the extractable perfume oil is not substantially in excess of 5% in accordance with U.S. Pat. No. 3,971,852 issued on July 27, 1976 and incorporated herein by reference;

c. Emulsion polymerization forming capsules around microdroplets of fragrance oil according to the teachings of U.S. Pat. Nos. 3,423,489 and 3,516,941, the disclosures for which are incorporated by reference herein; or

d. Encapsulation by means of coacervation as disclosed in U.S. Pat. Nos. 2,800,457; 2,800,458; 3,041,289 and 3,533,958 the disclosures for each of which is incorporated herein to form a second suspension.

3. Substantially uniformly distributing the resulting second suspension in a liquid fabric softener composition such as those defined by the claims of U.S. Pat. Nos. 3,664,952; 4,173,539; 4,264,457 and 4,268,401 the disclosures of which are incorporated herein by reference.

In summary, in carrying out the process of our invention sustained release fragrances are prepared by combining non-confined fragrance oils with encapsulated or physically entrapped fragrance oils. These combinations are fashioned so that the free fragrance oil or fragrance oil emulsion are bound in a network of physically entrapped fragrance oil and suspending agent. The thixatropic pastes or free-flowing powders which result are products where the unconfined fragrance oil or unconfined fragrance oil emulsion, the "encapsulated" or physically entrapped fragrance oil and suspending agent are held together by physical forces.

Although the fragranced materials and fabric softener compositions of matter of our invention can be prepared from single fragrance oils, e.g. patchouli oil or vetiver oil or rose oil or synthetic vetiver oil compositons or synthetic rose oil compositions, it is possible to extend the range of properties effected by use of the fabric softener composition by use of combinations of two or more physically entrapped fragrance compositions (physically entrapped in one or more manners, e.g. spray-dried gums and encapsulation as by coacervation) and/or two or more non-confined fragrances or fragrance emulsions which may or may not be different but which are organoleptically compatible with the physically entrapped fragrances. For example, it is possible to separately prepare spray-dried fragrance compositions from gelatins of various Blooms and then to add these compositions to the first suspension of fragrance oil or fragrance oil emulsion and suspension agent (e.g. hydroxypropyl cellulose) and also add spray-dried fragrance alone to ethanol and water mixtures to form an individual fabric softener composition of matter. Thus, such a fabric softener composition of matter may, for example, contain a mixture of fragrance compositions prepared from a low Bloom gelatin (characterized by a rapid fragrance release) and a high Bloom gelatin (characterized by a longer fragrance release on use thereof and in contact with the skin and the fabric treated with the fabric softener composition of our invention) as well as non-confined fragrance oil or fragrance oil emulsion (very rapid release). The properties effected by these resultant fabric softener compositions (to the head space above the treated fabric on wearing of the fabric) will be intermediate to the properties obtained from each of the fragrance compositions when used separately. Specifically, if a fragrance composition formed from 50 Bloom gelatin is mixed with a fragrance composition formed from 200 Bloom gelatin and the mixture is both (i) added to a fragrance oil and suspension agent which composition is added to, for example, a cologne and (ii) added to the fabric softener composition of matter alone, the product may effect a fragrance release from the treated fabric into the head space thereover on wear of said fabric which is substantially more "even" over the use period than is the case when single fragrance compositions just containing the entrapped and non-confined fragrance oils or emulsions and suspensions are employed.

Similarly, it is possible to modify the properties of the perfume compositions useful with the fabric softener compositions of our invention by use of mixtures of physically entrapped fragrance compositions, e.g. spray-dried fragrance compositions characterized by different ratios of entrapment agent to fragrance oil. If, for example, a composition containing 10% fragrance agent and 90% gelatin is mixed with one containing 50% fragrance agent and 50% gelatin, the resulting blended fragrance composition after adding non-confined fragrance oil or fragrance oil emulsion and suspension agent, will yield a composition having a more even (in relation to duration of use activity time) liberation of fragrance than is obtained by use of either fragrance agent alone.

Liberation of fragrance from the perfume compositions of our invention may also be modified in a controlled manner to obtain an even, sustained fragrance level from the time that use begins (on the fabric treated with the fabric softener composition) and thereafter for a protracted period of time far in excess of that obtained today in such fabric softener compositions by using various mixtures of fragrance compositions (a) having different particle size of physically entrapped fragrance, the resulting product deriving much of its initial fragrance from the smaller particles and much of its later fragrance from the larger particles or (b) formed from gelatins of different pH (the composition formed from gelatin of higher pH (e.g. 6) giving quick release of fragrance while that formed from lower pH (e.g. 2.5) giving slower release).

A particularly desirable fragrance composition of our invention contains unfixed fragrance, spray-dried fragrance and suspension agent, hydroxypropyl cellulose, in proportions of about 1:1:0.1. This product is characterized by an interesting or pleasing fragrance level which may start at 0.25 seconds from the point of contacting the fabric to which the fabric softener composition is applied with the skin on use thereof. Over substantially the entire period of fragrance release, the fragrance level is higher than that of any fragranced fabric softener of the prior art and the fragrance is continuous, rich, full and true.

Thus, in summary, the term "encapsulate" may be used to describe the relation of the entrapment agent and the fragrance agent and may mean either (a) that the latter in the form of spray-dried emulsions of discrete microdroplets is distributed substantially uniformly within or in the interstices of finely divided particles of the former or (b) that the fragrance agent is locked within polymerized capsule walls where the polymer is a urea formaldehyde polymer or the like. Thus, for example, the fragrance agent is locked within the entrapment agent (e.g., gelatin, gum acacia, urea formaldehyde resin, dextrin, modified food starch, suspension polymerizate, wax, hydroxypropyl cellulose, or emulsion polymerizate) to the extent that the former is released substantially only as the molecules of entrapment agent are either (a) dissolved from the individual entrapment agent particles by the hydrolytic action of, for example, sweat glands or (b) eliminated from the individual entrapping particles as a result of the application of positive mechanical pressure created, for example, by rubbing or washing or the normal abrading of articles of clothing treated with the fabric softener compositions of our invention against the skin on wearing of said articles of clothing.

The following examples illustrate processes for preparing individual fragrance compositions necessary to produce the fabric softener compositions useful in our invention.

The following fragrance formula is provided:

The instant rose formulation has an intense rose aroma with great floralcy and woodyness with clary-sage and violet leaf nuances.

20 grams of the fragrance composition of Example A is emulsified in a solution containing 300 grams gum acacia and 700 grams water. The emulsion is spray-dried with a Bowen Lab Model Drier utilizing 250 c.f.m. of air with an inlet temperature of 500.degree. F., an outlet temperature of 200.degree. F. and a wheel speed of 50,000 r.p.m.

130 grams of vetiver oil redistilled is emulsified in a solution containing 300 grams of "Nadex" dextrin (manufactured by National Starch and Chemical Co. of New York, N.Y.) and 700 grams of water. The emulsion is spray-dried with a Bowen Lab Model Drier utilizing 250 c.f.m. of air with an inlet temperature of 500.degree. F., an outlet temperature of 200.degree. F., and a wheel speed of 50,000 r.p.m.

10 parts by weight of 50 Bloom pigskin gelatin is added to 90 parts by weight of water at a temperature of 150.degree. F. The mixture is agitated until the gelatin completely dissolves and the solution is cooled to 120.degree. F. 20 parts by weight of the perfume composition of Example A is added to the solution which is then homogenized to form an emulsion having a particle size typically in the range of 2-5 microns. This material is kept at 120.degree. F. under which conditions the gelatin will not jell.

Coacervation is induced by adding, slowly and uniformly, 40 parts by weight of a 20% aqueous solution of sodium sulfate. During coacervation, the gelatin molecules are deposited uniformly about each oil droplet as a nucleus.

Gelation is effected by pouring the heated coacervate mixture into 1,000 parts by weight of 7% aqueous solution of sodium sulfate at 65.degree. F. The resulting jelled coacervate is then filtered and washed with water at a temperature below the melting point of gelatin to remove the salt.

Hardening of the filter cake is effected by washing with 200 parts by weight of 37% solution of formaldehyde in water. The cake is then washed to remove residual formaldehyde.

A 40% dextrin solution is freeze-dried. This is accomplished by a conventional technique such as that described in column 4 of U.S. Pat. No. 3,404,007 the disclosure of which is incorporated by reference herein.

The freeze-dried material is then milled to a particle size of 20-40 mesh.

100 grams of this freeze-dried material are then combined with 50 grams of patchouli oil redistilled (East Indies). This is accomplished by mixing the materials in a suitable blender such as a ribbon blender. This results in a dry, free-flowing powder having the advantages heretobefore described. To ensure against atmospheric reaction or vaporization of the patchouli oil in the solid matrix, the powder is given a protective coating to seal the entrances to the interstices or cavities in the porous particulate matrix. One suitable form of coating is a dextrin solution which has the property of forming an impermeable film for preventing the escape or permeation of the fragrance oil.

2-hydroxyethyl methacrylate (100 parts) is stirred with 0.05 parts by weight t-butyl peroctoate in a nitrogen atmosphere at a temperature of 40.degree. C. for 30 minutes. The resultant mixture is cooled to 25.degree. C. and a further 0.10 parts by weight of t-butyl peroctoate is added, ethylene glcol dimethacrylate (0.1 part) being added at the same time. To this casting solution, oil of galbanum natural is added in an amount of 10 parts by weight. After curing and granulation, the fragranced powder is used as part of a fragrance releasing formulation as exemplified infra.

500 grams of water are heated to boil and 500 grams of dextrin (National Starch and Chemical Corporation, 78-1523) is added with rapid and efficient mixing using a closed turbine, high shear mixer (Barrington CONVERTI JET Model CJ-5B). Mixing is continued until a homogeneous solution is obtained.

81 grams of petitgrain oil Paraguay is emulsified in 300 grams of the shell composition solution (A) by means of a homogenizing mixer (Barrington CONVERTI JET Model CJ-5B operated as a closed turbine unit). At the start of the operation, the temperature of the matrix composition solution is 20.degree. C. and of the petitgrain oil is 15.degree. C. The mixing vessel is cooled during the operation of the mixing in order to prevent a rise in temperature and to keep the temperature below 20.degree. C.

1000 grams of polyethylene glycol having an average molecular weight of 400 (Union Carbide Corporation, Carbowax 400) and at a temperature of about 25.degree. C. is placed in a vessel equipped with homogenizing mixer (Barrington CONVERTI JET Model CJ-5B operated as an open turbine unit). 100 grams of the petitgrain oil capsule composition (B) is introduced into the polyethylene glycol in a thin stream with steady medium speed operation of the mixer (about 1,500 rpm shaft speed). By the action of the mixer, the petitgrain oil emulsion is broken up into coarse liquid particles, which in contact with the polyethylene glycol, are rapidly converted into gel particles and finally into virtually anhydrous granules.

The capsule granules are separated from the excess polyethylene glycol by means of a basket centrifuge and used in fabric softener compositions as set forth in the examples, infra.

According to the process of U.S. Pat. No. 3,971,852, Example 1 at column 12, a solution of encapsulant comprising 32 parts of glucoronolactone and 48 parts of the polysaccharide having the following units:

sorbitol

erythritol

fructose

sucrose

D-glucoronolactone

glucose

glycerine

maltose

mannitan

methyl-A-D-glycopyranoside

raffinose

ribitol

sorbitan

is prepared by dissolving them in 250 parts of water with agitation at high speed in a household type Waring blender. Sandalwood oil (EI) is slowly added to the resulting solution until 120 parts are incorporated while continuing high speed agitation for 3 minutes at which time an oil/water emulsion has formed with an average droplet diameter of 0.5 microns. The viscosity is determined with a Brookfield Model LVT Viscosimeter is 57.5 centpoises at 30.degree. C. The proportions are chosen to give a sandalwood oil loading of 60% (120 parts sandalwood oil and 80 parts encapsulant). The resulting mixture is spray-dried in a standard Anhydro laboratory drier, size No. 1, maintained at an air inlet temperature of 180.degree. C. and an air outlet temperature of 90.degree. C. at a feed rate of 3 pounds per hour of emulsion. There is collected 170 parts by weight of powdered product readily passing through a 140 mesh screen which, upon analysis by standard steam distillation technique, is shown to contain 56% by volume (V/W) or 56% by weight (W/W) of volatile oil based on the weight of the product. This represents an 85% weight recovery of product containing 93% of the theoretical load of sandalwood oil initially employed to make the emulsion. This represents a total recovery of 79% of the original oil. The extractable oil of the product is 0.2% as determined by extraction. The moisture content is 2.1% as determined by Karl Fisher procedure. In general the volatile oil content is determined by the standard steam distillation technique on product as produced. The volatile oil content as so determined includes the extractable oil.

Apparatus as illustrated in FIG. 1 of U.S. Pat. No. 3,423,489 issued on Jan. 1, 1969, the disclosure of which is incorporated herein by reference, is used to form capsules of an aqueous film material in wax shells. The nozzle is inclined at an angle of 30.degree. from the vertical. The nozzle was provided with an orifice of 0.167 mm in diameter and was immersed in the bath to a depth of 1 mm. The fill liquid has the following composition:

One liter of filtered fill solution is placed in the reservoir to which one atmosphere gauge pressure is applied. The temperature of the fill liquid is 24.degree. C. The wax temperature is 170.degree. C. and the tip winding is heated to about 400.degree. C. The needle valve is opened and the fill solution is discharged at a rate of 4.5 meters per second. The Reynolds Number (N.sub.Re) characterizing the flow of fill liquid through the nozzle is 150 (measured before immersion in wax). The wax solidifies at a distance approximately 80 cm from the orifice which is 0.4 seconds travel time of the wax in the trajectory path. The time is sufficient to permit the biliquid column formed by the discharging aqueous solution and the molten wax pulled along therewith to first form a string of capsules and then to separate into individual discrete capsules. Capsules are produced at a rate of about 60,000 per minute. The total trajectory length is about 12 feet (about 1 second total time in trajectory) after which the capsules are allowed to fall onto an inclined plane from which they proceed to a collecting trough. The capsules collected are 700 microns in average diameter and have a shell thickness of about 50 microns. The fill liquid comprises about 63% of the total capsule volume and the shell material about 37%. The capsules are useful in preparing the fabric softener compositions as set forth in the Examples I-X, infra.

The following examples are given to illustrate embodiments of our invention as it is presently preferred to practice it. It will be understood that these examples are illustrative and the invention is not to be considered as restricted thereto except as indicated in the appended claims. These examples also encompass detailed description of the drawings.

The following mixture is prepared:

A.

Perfume composition of Example A: 2.00 parts

Food grade ethanol 95%: 19.80 parts

Methyl paraben (p-hydroxymethyl benzoate): 0.20 parts

Crodesta.RTM.F-110 (a fatty acid sucrose ester having the formula: ##STR13## manufactured by Croda Inc. of 51 Madison Avenue, New York, N.Y. 10010: 1.00 parts

This mixture is mixed at room temperature using a propellant-type mixer until the mixture is uniform. The following mixture is prepared:

B.

Ben-A-Gel.RTM.EW (a specially processed smectite clay gellant having a specific gravity of 2.5; a density of 20.9 pounds per gallon and a bulking value of 0.0479 gallons per pound manufactured by N L Industires of Hightstown, N.J.): 0.48 parts

Distilled water: 72.52 parts

The resulting mixture is mixed using a propellant type mixer until a smooth gel is formed.

Using a Brookfield Model LV Viscosimeter, the following viscosity readings are made:

(Spindle No. 1)

12 rpm=200 centipoises

30 rpm=114 centipoises

60 rpm=76 centipoises

The smooth gel (B) is added to mixture (A) slowly, using a propeller-type mixer.

Microencapsulated perfume prepared according to Example J (4.00 parts) are added to the resultant mixture of B and A using a propellant type mixer until the capsules are uniformly dispersed.

Part of the resulting material is dried and admixed at levels of 4%, 6%, 8%, 10% and 12% with the detergent formulation as described in Example I of U.S. Pat. No. 4,234,627, to wit:

The second portion of the resulting material is admixed at the levels of 4%, 6%, 8%, 12% and 14% with the fabric softener composition of Example 1 of U.S. Pat. No. 4,173,539 which is produced as follows:

A mixture of cetyltrimethylammonium bromide (9 parts MW 364), a commercial sodium linear C.sub.10 -C.sub.15 alkyl benzene sulfonate (containing 91.8% of sulfonate, MW 358, 4.6% sodium sulfate, 0.4% sodium chloride and 1.9% water, 6.34 parts), isopropyl alcohol (8 parts) and water (4 parts) is heated to and maintained at 70.degree. C. until it is wholly liquid. Sufficient demineralized water at 70.degree. C. is added to bring the weight of the composition to 200 parts and the mixture is stirred for two minutes and allowed to cool to ambient temperature. 4.67 parts of behenoyl-hydroxypropyl trimethylammonium chloride is then added to this mixture with stirring.

Each of the above softener compositions; the solid composition and the liquid composition are separately added to detergents which are, in turn, added to clothes batches in washing machines. In each case, the fabrics display on wear an intense rose fragrance. After five hours, the resultant fabrics display interesting guiacwood fragrances. The wearer of the clothing treated with each of the above fabric softeners retains a pleasant guiacwood fragrance for 24 hours thereafter in each of the above cases. In addition, the use of the resulting fabric softener on the above fabrics has the effect of covering undesirable aromas on the fabric and on the wearer of the fabric.

FIG. 1 is a photomicrograph of the suspension produced according to the instant example prior to admixture with the fabric softener composition (200X magnification).

FIG. 3 is a block diagram-flow sheet of the abovedescribed process.

An experiment similar to that of the immediately preceding example is carried out except that the pH of the resultant suspension is adjusted to 5.5 using phosphoric acid.

The resultant viscosity using a Brookfield Model LV Viscosimeter, Spindle No. 1, is as follows:

6 rpm=595 centipoises

12 rpm=377.5 centipoises.

An experiment similar to that carried out above is carried out except that instead of 2 parts by weight of fragrance in mixture "A", 4 parts by weight of fragrance is used and instead of 72.52 parts by weight of Ben-A-Gel.RTM.EW, 67.0 parts is used and instead of 4.0 parts by weight of capsules prepared according to Example J, 8.0 parts by weight of capsules prepared according to Example J is used.

The resultant viscosity using a Brookfield Model LV Viscosimeter, Spindle No. 1, is as follows:

6 rpm=555 centipoises

12 rpm=355 centipoises

An experiment similar to the immediately preceding example is carried out except that the Ben-A-Gel.RTM. concentration is at 1.7 times that used in the immediately preceding concentration (1% Ben-A-Gel.RTM. in water). The resulting viscosity is as follows:

Using a Brookfield Model LV Viscosimeter, Spindle No. 2:

6 rpm=1,100 centipoises

12 rpm=650 centipoises

30 rpm=350 centipoises

The results of each of these additional experiments are identical to those set forth above.

The following mixture is prepared:

A.

Fragrance prepared according to Example A: 2.00 parts

Ethyl alcohol (food grade 95% aqueous): 19.80 parts

Methyl paraben: 0.20 parts

Crodesta.RTM.F-110: 1.00 parts

The resulting mixture is mixed at room temperature using a propellant type mixer until the mixture is uniform.

The following mixture is then prepared:

B.

SGP.RTM. polymer 502-S manufactured by the Henkel Corporation of 4620 W. 77th Street, Minneapolis, Minn. 55435, a starch based absorbent polymer produced according to the following U.S. Pat. Nos.:

3,935,099

3,981,100

3,985,616

3,997,484

the disclosure of which are incorporated by reference herein: 0.29 parts

Distilled water: 73.71 parts

This mixture is mixed using a propellant type mixer until a clear gel is formed.

Mixture B is added to mixture A slowly using a propellant type mixer.

Microcapsules prepared according to Example J (4.00 parts) are added to the mixture of B and A using a propellant type mixer until the capsules are uniformly dispersed.

The viscosity of the resultant suspension using a Brookfield model LVI viscosimeter (spindle No. 3) is as follows:

6 rpm: 6700 centipoises

12 rpm: 4300 centipoises

30 rpm: 2460 centipoises

FIG. 2 is a photomicrograph of the resulting suspension (200X magnification).

The resulting material is divided into two portions. The first portion is admixed at the rates of 4%, 6%, 8%, 10% and 12% with the following mixture:

The above composition is prepared in accordance with U.S. Pat. No. 4,234,627 at Example I, column 13, line 39.

The second portion is added at the levels of 4%, 6%, 8%, 10% and 12% to a detergent prepared in accordance with Example 1 of U.S. Pat. No. 4,173,539 at column 8 as follows:

A mixture of cetyltrimethylammonium bromide (9 parts MW 364), a commercial sodium linear C.sub.10 -C.sub.12 alkyl benzene sulfonate (containing 91.8% of sulfonate, MW 358, 4.6% sodium sulfate, 0.4% sodium chloride, 6.34 parts), isopropyl alcohol (8 parts) and water (4 parts) is heated and maintained at 70.degree. C. until it is wholly liquid. Sufficient demineralized water at 70.degree. C. is added to bring the weight of the composition to 200 parts and the mixture is stirred for two minutes and allowed to cool to ambient temperature. 4.75 parts of 3-behenoyloxy-2-hydroxypropyl trimethylammonium chloride is then added to the resulting mixture. The resulting mixture is stirred for a period of 30 minutes.

The pourable liquid fabric softening composition is prepared in accordance with U.S. Pat. No. 4,173,539 the disclosure of which is incorporated by reference herein.

When the above solid and liquid compositions are used in conjunction with fabrics to be softened, one handling the thus treated dried fabrics or wearing the thus treated dried fabrics experiences in the head space above the fabrics, the evolution, initially, of a high intensity rose aroma which last for five hours. This is followed by a pleasant lower intensity guiacwood aroma which lasts for thirty hours. In addition, there is an unexpected and surprising effect of deodorancy attached to the use of the fabric softener composition which lasts for thirty-six hours.

FIG. 3 sets forth a block diagram-flow sheet for the process of this example.

The following mixture is prepared:

The KLUCEL.RTM.EF is dispersed in the viscous liquid flavor composition of Example A with vigorous stirring, thereby resulting in a viscous liquid. 48.4 parts by weight of the powder fragrance composition of Example B is then blended into such viscous liquid with stirring at 25.degree. C. for a period of 30 minutes resulting in a thixotropic sustained release fragrance paste.

The resulting fragrance paste is admixed at levels of 6%, 8%, and 10% with the softening composition of Example II at column 5 of U.S. Pat. No. 3,664,952:

The resulting fabric softener is used to treat polyester fabrics at levels of 0.001%-0.05% based on the dry weight of the fabrics. The fabrics are then dried. On wearing of the fabrics, there is evolved from the thus treated fabric over a period of 24 hours starting with the initial wearing of the fabric, a pleasant rose fragrance at closely similar intensity levels.

FIG. 4 is a block flow diagram of the process of this example.

The following mixture is prepared:

The KLUCEL.RTM.LF is dispersed in the patchouli oil with vigorous stirring thereby resulting in a viscous liquid. 65 parts by weight of the the powder fragrance composition of Example D is then blended into the viscous liquid with stirring at 25.degree. C. for a period of 30 minutes resulting in a dry, free-flowing sustained release fragrance powder. The resulting sustained release powder is admixed with the following detergent/softener composition (of Example I at column 13 of U.S. Pat. No. 4,234,627):

The resulting fabric softener powder is admixed with a 50-50 ethanol-water mixture and is used to treat cotton fabrics at levels from 0.001% up to 0.05%. The resulting fabrics after treatment are then dried. On wearing, the fabrics evolve a pleasant patchouli fragrance initially followed by, after five hours, a pleasant rose fragrance for a period of thirty hours thereafter.

FIG. 5 sets forth a block diagram-flow sheet of the process of this example.

The following mixture is prepared:

The KLUCEL.RTM.JF is dispersed in the patchouli oil with vigorous stirring thereby resulting in a viscous liquid. 47.25 parts by weight of the powder fragrance composition of Example E is then blended into said viscous liquid with stirring at 25.degree. C. for a period of 30 minutes resulting in a thixotropic sustained release fragrance paste.

47.25 parts by weight of the powder fragrance composition of Example H (sandalwood fragrance) is then blended into said thixotropic sustained release fragrance paste with stirring at 25.degree. C. for a period of 60 minutes resulting in a sustained release fragrance powder.

The sustained release fragrance powder is admixed with the following fabric softener/detergent mixture of Example I of U.S. Pat. No. 4,234,627:

The resulting powder is added to 50:50 food grade ethanol:water at levels of 20%, 30%, 40% and 50%.

On use, nylon fabrics treated with each of the fabric softener liquids yield for times set forth in FIG. 7, first patchouli fragrances; then for a brief period of time a patchouli/sandalwood fragrance and, finally, for a period of thirty hours a sandalwood fragrance subsequent to the wearing of the fabrics. The patchouli fragrance itself lasts for a period of about eight hours. The actual intensity vs. time graph for aromas X.sub.4 and Y.sub.4 are indicative of patchouli aromas and the graph for fragrance Z.sub.4 is indicative of sandalwood aroma.

FIG. 6 sets forth the flow sheet-block diagram for the process of this example.

The following mixture is prepared:

A.

Ylang oil: 2.0 parts by weight

Ethyl alcohol (95% food grade): 19.8 parts by weight

Methyl paraben: 0.2 parts by weight

Crodesta.RTM.F-110: 1.50 parts by weight

This mixture is mixed at room temperature using a propellant type mixer until the mixture is uniform.

The following mixture is then prepared:

B.

Ben-A-Gel.RTM.EW: 0.85 parts by weight

Distilled water: 72.52 parts by weight

The resulting mixture is mixed in a propellant type mixer until a smooth gel is formed.

C. To the mixtue of "A" and "B" is added galbanum-containing polymer prepared according to Example F. The resulting mixture is mixed in a propellant type mixer until the powder is uniformly dispersed.

The following mixture is prepared:

D.

Galbanum oil: 2.0 parts by weight

Ethyl alcohol: 19.80 parts by weight

Methyl paraben: 0.20 parts by weight

Crodesta.RTM.F-110: 1.50 parts by weight

The resulting mixture is mixed using a propellant type mixer until the mixture is uniform.

The following mixture is prepared:

E.

Ben-A-Gel.RTM.EW: 0.48 parts by weight

Distilled water: 72.52 parts by weight

The resulting mixture "E" is mixed until a smooth gel is formed.

Mixture "E" is added to mixture "D" slowly using a propeller type mixer.

F. Using a propellant type mixer, the petitgrain oil capsules prepared according to Example G are added to "D" and "E" until the capsules are uniformly dispersed.

The mixtures of "A", "B", "C" and "D", "E", "F" and then intimately admixed in a propellent type mixer until a smooth blend is formed which is a solid mixture of the materials which is a solid powder.

The resulting solid powder is admixed with the following detergent/softener composition:

The resulting powder is admixed at levels of 20%, 30%, 40% and 50% with 50:50 food grade ethanol:water solution. The resulting solutions are used to treat clothing made of natural cotton fabric. The clothing treated with the above fabric softener compositions on use as a result of either (a) the hydrolytic action of body sweat or (b) the application of positive mechanical pressure to the particles which entrap the fragrances yield fragrances first for a period of twelve hours as galbanum and then for a period of thirty-five hours as petitgrain.

FIG. 8 sets forth a block flow diagram for the process of this example.

The following mixture is prepared:

A.

Sandalwood fragrance: 2.00 parts by weight

Ethyl alcohol: 19.80 parts by weight

Methyl paraben: 0.20 parts by weight

Crodesta.RTM.F-110: 1.00 parts by weight

The resulting mixture is mixed using a propellent type mixer until the mixture is uniform at 25.degree. C.

The following mixture is prepared:

B.

SGP.RTM. polymer 502-S: 0.32 parts by weight

Distilled water: 72.71 parts by weight

Mixture "B" is mixed using a propellant type mixer until a clear gel is formed at 25.degree. C.

Mixture "B" is added to mixture "A" slowly using a propellant type mixer.

C. Using a propellant type mixer, the capsules produced according to Example C (vetiver oil) are added to the mixture of "B" and "A" until the capsules are uniformly dispersed. The resulting mixture is denominated X.sub.6 +Y.sub.6. Mixture X.sub.6 +Y.sub.6 is then admixed with the following mixture in a propellant type mixer at 25.degree. C.:

Vetiver oil: 47.25 parts by weight

Propylene glycol: 0.50 parts by weight

KLUCEL.RTM.HF (brand of hydroxypropyl cellulose produced by the Hercules Corporation of Wilmington, Del. having a molecular weight of about 800,000 and a viscosity defined according to FIG. 12): 5.00 parts by weight

The KLUCEL.RTM.HF is dispersed in the vetiver oil with vigorous stirring thereby resulting in a viscous liquid. 47.25 parts by weight of the powder fragrance composition of Example C is then blended into said viscous liquid with stirring at 25.degree. C. for a period of 30 minutes resulting in a thixatropic sustained release fragrance paste denominated as "Z.sub.6 +W.sub.6 ".

Thus, after mixing Z.sub.6 +W.sub.6 with X.sub.6 +Y.sub.6, a dry cologne powder is produced denominated as "X.sub.6 +Y.sub.6 +Z.sub.6 +W.sub.6 in FIG. 9.

FIG. 9 is the block diagram for the process of this example.

The resulting product is admixed at the rate of 50% with the following detergent/fabric softener composition:

The resulting powder is admixed with a 50:50 ethanol mixture at levels of 20%, 30%, 40%, 50% and 60% yielding fabric softener solutions which on use and (a) as a result of the hydrolytic action of the sweat glands or (b) as a result of mechanical pressure applied to the particles of entrapped fragrances, yield subsequent to the wearing of the fabric treated, a very long-lasting woody fragrance having sandalwood and vetiver notes for a period of forty hours and also giving rise to a malodor deodorant effect thereby eliminating any maladors from the treated fabrics which are in contact with the wearer's body for a period of forty hours.

FIG. 9 sets forth the block flow diagram for the process of this example.

The following mixture is prepared:

A.

Guiacwood oil: 2.0 parts by weight

Ethanol: 19.8 parts by weight

Methyl paraben: 0.2 parts by weight

Crodesta.RTM.F-110: 1.00 parts by weight

The resulting mixture is mixed at room temperature using a propellant type mixer until the mixture is uniform.

The following mixture is prepared:

B.

Ben-A-Gel.RTM.EW: 0.55 parts by weight

Distilled water: 72.55 parts by weight

The resulting mixture is mixed in a propellant type mixer until a smooth gel is formed.

Mixture "B" is added to mixture "A" slowly using a propeller type mixer.

C. Capsules prepared according to Example J (guiacwood oil) are added to the mixture of "B" and "A" using a propellant type mixer (4.00 parts). The capsules are mixed until uniformly dispersed.

The following mixture is prepared:

D.

Sandalwood oil: 2.00 parts by weight

Ethanol: 19.8 parts by weight

Methyl paraben: 0.2 parts by weight

Crodesta.RTM.F-110: 1.00 parts by weight

Mixture "D" is mixed at room temperature using a propellant type mixer until the mixture is uniform.

The following mixture is prepared:

E.

SGP Polymer.RTM.502-S: 0.29 parts by weight

Distilled water: 72.71 parts by weight

The resulting mixture "E" is mixed using a propellant type mixer until a smooth gel is formed.

Mixture "E" is added slowly to mixture "D" using a propeller type mixer.

F. To the mixture of "D" and "E" using a propellant type mixture is added 4.0 parts of the capsules produced according to Example H until the capsules are uniformly dispersed (4.0 parts capsules).

The resulting mixtures of "A", "B", "C" and "D", "E", "F" are then combined to yield a dry powder.

This dry powder is intimately admixed at a 50:50 level with a "high solids cationic liquid detergent and fabric softener" composition . . . the composition of Example 6 at column 11 of U.S. Pat. No. 4,264,457 which is as follows:

The resulting fabric softener composition is used to treat polyester fabrics at the levels of from 0.001% up to 0.05%. Subsequent to treatment, the fabrics are dried. On use (a) as a result of the hydrolytic action of the sweat glands of the wearer or (b) as a result of the application of mechanical pressure to the particles of entrapped fragrances and the fabric treated with the fabric softener composition, a sandalwood/guiacwood fragrance is evolved from the thus treated fabric over a period of thirty hours.

FIG. 10 sets forth a block diagram-flow sheet for the process of this example whereby the products denoted as X.sub.7 +Y.sub.7 +Z.sub.7 +W.sub.7 and S+X.sub.7 +Y.sub.7 +Z.sub.7 +W.sub.7 (liquid fabric softener) are produced.

The following mixture is prepared:

The ethyl cellulose and hydroxypropyl cellulose are intimately admixed. The intimate mixture of ethyl cellulose and hydroxypropyl cellulose is dispersed in the liquid fragrance composition of Example A with vigorous stirring thereby resulting in a viscous liquid. 48.4 parts by weight of the powder fragrance of Example B is then blended into said viscous liquid with stirring at 25.degree. C. for a period of 30 minutes resulting in a thixatropic sustained release fragrance paste.

This fragrance paste is denoted as fragrance paste X.sub.8 +Y.sub.8.

The following mixture is prepared:

The KLUCEL.RTM.MF is dispersed in the trans,trans-delta damascone with vigorous stirring thereby resulting in a viscous liquid. 65 parts by weight of the powder fragrance composition of Example F (galbanum) is then blended into the viscous liquid with stirring at 25.degree. C. for a period of 30 minutes resulting in a dry, free-flowing sustained release fragrance powder. This fragrance powder is denoted as fragrance powder Z.sub.8 +W.sub.8. The thixathropic paste X.sub.8 +Y.sub.8 and the powder Z.sub.8 +W.sub.8 are then blended in a Banberry Mixer to yield a free-flowing powder denoted as X.sub.8 +Y.sub.8 +Z.sub.8 +W.sub.8, a dry product.

At a 50:50 level, this dry product is admixed with a high solids cationic liquid detergent and fabric softener as described in Example 6 at column 11 of U.S. Pat. No. 4,264,457:

The resulting fabric softener liquid is used at the levels of 0.001% up to 0.05% to treat nylon fabric apparel. The resulting apparel is then dried. The resulting nylon fabric on use by the wearer as a result of (a) the hydrolytic action of the body sweat glands or (b) the application of mechanical pressure to the particles of entrapped fragrance on the thus treated fabric yields a pleasant woody-type fragrance with intense floral rosy nuances over a period of thirty-six hours. The resulting fragrance also has the capability of giving rise to an excellent malodor deodorancy effect thereby eliminating malodors and yielding excellent aroma nuances over a long period of time.

FIG. 11 sets forth the block diagram-flow sheet for the process of this example.

The following mixture is prepared:

A.

Guiacwood oil: 2 parts by weight

Ethyl alcohol: 19.80 parts by weight

Methyl paraben: 0.20 parts by weight

Crodesta.RTM.F-110: 1.00 parts by weight

The resulting mixture is mixed at room temperature using a propellant type mixer until the mixture is uniform.

The following mixture is prepared:

B.

SGP.RTM. polymer 502-S (prepared according to Example 9 of U.S. Pat. No. 3,935,099 issued on Jan. 27, 1976, the disclosure for which is incorporated herein): 0.29 parts by weight

Distilled water: 72.71 parts by weight

This mixture "B" is mixed using a propellant type mixer at room temperature until a clear gel is formed.

Mixture "B" is added to mixture "A" slowly using a propellant type mixer.

The capsules formed in Example J containing guiacwood oil (4.0 parts) are added to the mixture of "B" and "A" and the resulting mixture "C" is mixed until the capsules are uniformly dispersed using a propellant type mixer at 25.degree. C.

The resulting mixture is herein denoted as mixture "X.sub.9 +Y.sub.9 ".

The following mixture Z.sub.9 +W.sub.9 is prepared:

The KLUCEL.RTM.GF is admixed with the xanthan gum and the resulting mixture is dispersed in the sandalwood oil with vigorous stirring thereby resulting in a viscous liquid. 71 parts by weight of the fragrance prepared according to Example H is then blended into the said viscous liquid with stirring at 25.degree. C. for a period of 30 minutes resulting in a dry, free-flowing sustained release fragrance powder denoted as fragrance powder Z.sub.9 +W.sub.9.

The following mixture is prepared:

The KLUCEL.RTM.HF is dispersed in the oil of rose with vigorous stirring thereby resulting in a viscous liquid. 47.25 parts by weight of the fragrance composition prepared according to Example D is then blended into the said viscous liquid with stirring at 25.degree. C. for a period of 30 minutes resulting in a thixatropic sustained release fragrance paste denoted as fragrance product "R.sub.9 +Q.sub.9 ".

Fragrance products R.sub.9 +Q.sub.9, X.sub.9 +Y.sub.9 and Z.sub.9 +W.sub.9 are then blended in a mixer at 25.degree. C. for a period of 30 minutes. The resulting product denoted as "X.sub.9 +Y.sub.9 +Z.sub.9 +W.sub.9 +R.sub.9 +Q.sub.9 " is a dry product and is admixed with the following fabric softener composition:

The foregoing composition is from Example 4 at column 10 of U.S. Pat. No. 4,264,457 the disclosure of which is incorporated by reference herein. The TROIS COTES DU FORCE!.TM. liquid fabric softener is thus created. Polyester apparel treated with this fabric softener at levels of from 0.001% up to 0.08% exhibit the intensity-time-quality pattern on wearing as set forth in FIG. 14 which is a graph of intensity (on a scale of 1-10) vs. time. The fragrance lasts for twenty-five hours at a relatively high intensity.

FIG. 13 is a block flow diagram of the process of this example.

The process of Example X is carried out wherein a solution, X.sub.9 +Y.sub.9 +Z.sub.9 +W.sub.9 +R.sub.9 +Q.sub.9 +S is produced. 0.5 parts by weight of an emulsion stabilized prepared according to European Pat. No. 28,456 having the structure: ##STR14## (wherein R represents C.sub.15 saturated straight chain hydrocarbon) is added together with 4 parts of water. The use of this material is abstracted in published European patent application No. 28,456 thusly:

Branched fatty acid cholesterol ester(s), used as emulsion stabilisers which are not irritating to the skin and can be used in cosmetic and medicinal skin compositions

KAOSOAPKK 31.10.79-JP-139788

B01 E15 (13.05.81)A61k-07/48C07j-09

30.09.80 as 303436 (34pp1401) (E) CH-669205 FR1442283 3. Jnl. Ref. E(ATCHDEFRGBLI)

(A) Branched fatty acid cholesterol esters of formula (I) are new.

(R is a satd. 11-23C aliphatic hydrocarbon gp. with at least one alkyl substit. attached to the main chain between the carboxyl bonding position and the centre of the main chain).

(B) Cosmetic compositions contg. a cosmetic oil, water, an emulsifier and (I) are also claimed.

(I) is useful as an emulsion stabiliser esp. for emulstion type cosmetics or medicinal compsns. for application to the skin. (I) is liq. at room temp. and is capable of stabilising an emulsion together with an emulsifier. (I) have very low irritation to the skin and can therefore be used in products which are applied directly to the skin. ##STR15##

The use of this material gives rise to an improved fabric softener without any adverse effects upon the length of time that the fragrance is evolved from the user during the use thereof.

In each of the foregoing examples, where SGP.RTM. polymer 502-S is used, it can be replaced at the same level with Carbopol.RTM. resin 907, 910, 941, 934, 934P or 940, acrylic acid polymers manufactured by the B. F. Goodrich Company of 6100 Oak Tree Blvd., Cleveland, Ohio 44131. The molecular weights of these Carbopol.RTM. resins are as follows:

Where used in the preceding examples, supra, Crodesta.RTM.F-110 is sucrose monostearate having the properties set forth supra.