CN1027082C - Coated Spice Granules - Google Patents

Abstract

Perfume particles comprise perfume dispersed in some water-insoluble polymeric carrier material and encapsulated in a protective shell by coating with a friable coating material. The coated particles allow the preservation and protection of perfumes which are susceptible to degradation or loss under storage and harsh washing conditions. In use, the surface coating is broken to allow the carrier/perfume particles contained therein to effectively deliver multiple types of perfumes to fabrics or other surfaces.

Description

The present invention relates to perfume particles comprising perfume dispersed in a water-insoluble, low molecular weight polymeric carrier material and enclosed by a frangible coating. These coated particles are useful, for example, in laundry and fabric conditioning mixtures.

The present invention is based on the concept of controlled fragrance release, i.e. release of fragrance at a certain time and under conditions to obtain the desired fragrance effect, generally speaking, this is a very old idea and efforts have been made to achieve this result From the simple idea of putting fragrance in a candle to the complex technique of micro-encapsulation.

One aspect of the concept of controlled release of fragrance is to maintain a slow release of fragrance throughout a sustained period of time. This is generally achieved by mixing the perfume with a substance that essentially traps the perfume so that a small amount of the perfume is released throughout. This high molecular weight polymeric material mixed with the perfume is used to provide a delayed release of the perfume. controlled release is known. See, for example, U.S. Patent 4,184,099 to Lindauer et al., issued January 15, 1980; European Patent Application 0,028,118 to Leonard, published May 6, 1981; U.S. Patent 4,110,261 to Newland, which teaches combining perfume with a controlled release medium and forming the mixture into a solid product for air purification.

Fabric washing has also been associated with controlled release of fragrances. Using this concept it is possible to slow down or prevent the release of spices during long-term storage on racks. This concept also makes it possible to use relatively low levels of fragrances in products, since the consumption of fragrances is considerably less.

Spices can be preserved in a number of ways during storage. Spices can be made as part of the blend package. As described in U.S. Patent 4,540,721, Staller, issued September 10, 1985, fragrances can be combined with plastics used to make bottles, or mixed with polymers and products used to coat paperboard packaging compositions. Either way, the fragrance is released from the polymer matrix throughout.

The perfume/controlled release medium may also be in the form of granules which are incorporated into the wash mixture. One way it has been stated to achieve this result is to combine perfumes with water soluble polymers. Form it into granules and add to the wash mixture, as in U.S. Patent 4,209,417 to Whyte issued June 24, 1980; U.S. Patent 4,339,356 to Whyte issued July 13, 1982; Described in U.S. Patent 3,576,760 issued April 27 to Gould et al.

Fragrances may also be adsorbed onto porous carrier materials, which may be polymeric materials. See British Patent Publication 2,066,839 (applied in the name of Vysoka Skola Chemicko Technologika), Bares et al., published Jul. 15, 1981. These methods can also be used to mask unpleasant odors in admixtures or to protect perfumes from degradation by irritating components in wash admixtures. This type of approach achieves these advantages only for dry powder or granular mixtures because the fragrance is released as soon as the polymer is hydrated. Thus, these methods guarantee the fragrance benefits of the perfume as soon as the product is unpacked and loaded into the washing machine. Notwithstanding these desirable advantages, it would be more desirable to have a method of delivering undiluted, unlost and unaltered fragrance to fabrics and releasing the fragrance at the end of the wash cycle so that the desired fragrance smells on the fabrics.

Of course, one way to achieve this result is to put the fragrance in the product that goes directly to the dryer. In this way, the perfume is delivered to the fabric during the operation of the dryer. This method is U.S. Patent 4,511,495 issued to Melville on April 16, 1985 and U.S. Patent 4,511,495 to Melville on January 13, 1987. 4,636,330 are explained. Both patents propose granulating the perfume with a carrier and then formulating these granules into a mixture which is applied to the fabric before it is placed in a dryer or dried on a clothesline.

A more desirable method of delivering perfume to laundered fabrics is to ensure that the perfume is protected during the wash and then delivered to the fabric substantially in its original state.

This method must facilitate preventing dilution, degradation or loss of fragrance during the wash cycle of the laundry process. This can be achieved by using a perfume delivery system during the drying process or after delivering the perfume to the fabric. Preventing fragrance loss during the wash involves very different and more difficult techniques. Such protection must be stable not only under heated wash conditions but also against degradation by water and other harsh chemicals of the wash process such as bleaches, enzymes, surfactants, and the like.

One method that has been proposed to achieve these advantages is the microencapsulation of fragrances. Here the fragrance comprises an encapsulating core completely covered by what may be a polymeric substance. U.S. Patent 4,145,184 to Brain et al., issued March 20, 1979, and U.S. Patent 4,234,627 to Schilling, issued November 18, 1980, indicate the use of a Tight encapsulating substances, fragrances are microencapsulated to the fabric and then lost due to possible rupture of the microcapsules when the fabric is processed.

Another method of fragrance delivery involves ensuring fragrance protection during the wash cycle while releasing fragrance in a heated drying machine. U.S. Patent 4,096,072 issued June 20, 1978 to Brock et al. Perfume can be incorporated into the wash and dry cycle by delivering fabric conditioner to fabrics through the granules containing hydrogenated castor oil and fatty quaternary ammonium salts. However, when the granules are fluffy, it is not clear whether the perfume so incorporated is released during the wash cycle or is ideally carried in the granules into the dryer where it is released.

U.S. Patent No. 4,402,856 to Schnoring et al., issued September 6, 1983, describes a microencapsulation technology that includes a shell material that allows the fragrance from the capsule to diffuse only at a specific temperature composition. This facilitates preservation of the fragrance particles during storage and further washing. The particles are attached to the fabric and carried into the dryer, so that the diffusion of the fragrance from the capsules only occurs with the heating of the dryer. These granules are made of gelatin, an anionic polymer and a hardener,

U.S. Patent No. 4,152,272 to Young, issued May 1, 1979, teaches the incorporation of perfumes into wax particles to facilitate storage in dry mixes and to protect perfumes during washing, so that the perfumes are not exposed to heat under the elevated temperature conditions of the dryer. Spreads through the wax matrix of the particles onto the fabric.

It is desirable to form a mixture containing perfume particles which can be incorporated in liquid as well as dry granular or powder mixtures and which maintains storage stability over long periods of time.

It would be desirable to provide a method of delivering a wide range of perfume materials to fabrics or other surfaces during laundering and fabric or fiber conditioning.

It would be especially desirable to have a scented washing or conditioning mixture which ensures improved product odor, improved scent release of perfume during washing and improved scent and intensity of perfume delivered to surfaces being washed.

It is particularly desirable to provide fragrance-containing particles which are stable in fluid mixtures but release fragrance upon use.

The present invention includes perfume particles having a coated average particle size of less than about 350 microns (preferably not greater than 150 microns, with an optimum particle size range of 40-150 microns) containing from about 5% to about 70% perfume dispersed in from about 30% to about 95% of a water-insoluble polymeric carrier material having a molecular weight of from about 100 to about 30,000, a melting point of from about 37°C to about 190°C and a hardness value of from about 0.1 to about 15, The particles have a friable coating on their outer surfaces (where "particle size" means the average particle diameter for particles as large as spherical and the largest diameter or size for non-spherical particles). Particle sizes larger than this result in more loss from their deposition surfaces and do not ensure a relatively large enough surface area to release fragrance at the desired rate. In addition, particles larger than the above given particle size will be readily detectable on the surface being treated, which is undesirable, and particles at the lower end of the above range tend to adhere well to the surface being treated but tend to disintegrate very quickly. Release the spice.

The granules herein are typically characterized by a coating comprising from 1% to 20% by weight of the perfume-containing granules. For general use in fabric laundering and conditioning mixtures, the coating will generally contain from 1% to 10% by weight of the perfume-containing particles.

Preferred particles herein are those wherein the friable coating is substantially water insoluble. Suitable coatings of this type can be prepared from aminoplast polymers such as the reaction products of amines and aldehydes. Typical frangible coatings include, for example, reaction products of amines selected from urea and melamine with aldehydes selected from formaldehyde, acetaldehyde and glutaraldehyde and mixtures of these amines with these aldehydes. Such frangible coatings will be described later.

Such coated perfume particles are useful in situations where the particle coating is broken or worn away (such as in an automatic washing machine or washer dryer) causing the particle to be released, which in turn releases its perfume. Thus, the coated particles can be used in typical wash mixtures containing detersive surfactants, optional builders, and the like. particles again Can be used in conditioning mixes containing fiber and fabric conditioners.

All percentages herein are by weight unless otherwise indicated.

The present invention allows for the preservation, protection and release of fragrances contained in wash and conditioning mixtures during long-term storage and harsh wash conditions. This can be achieved by isolating the perfume in a carrier material in the form of small particles, the various parts of which will now be discussed in detail.

Fragranced Granules

The perfume-containing particles of the present invention comprise perfume dispersed in a specific carrier material. The fragrance-containing particles are coated with a friable coating material which, in use, ruptures to release the fragrance-containing particles which in turn release their fragrance.

In the context of this document, the term "perfume" refers to any scented substance or any substance which acts as a malodor counteractant. In general, these substances are characterized by vapor pressures greater than ambient pressure at room temperature. The fragrance or deodorant materials used herein are generally liquid at room temperature, but may also be solid such as the various camphor fragrances known in the art. A wide variety of chemicals are known to be useful as fragrances, including substances such as aldehydes, ketones, esters, and the like. More generally, natural vegetable and animal oils and exudates containing complex mixtures of various chemical components are known to be useful as fragrances, and these materials are also useful in the present invention, where the fragrances can be relatively simple in composition, or Can contain highly adulterated complex mixtures of natural and synthetic chemical components. These are chosen to obtain the desired scent.

Typical fragrances therein may contain, for example, a woody/earthy base with foreign substances such as sandalwood oil, civet incense, green leaf oil, and the like. The fragrance here can be a faint floral fragrance, such as rose extract, violet extract and so on. The flavors herein can be formulated to provide a desired fruity aroma, such as lime, lemon, yuzu, and the like. Suitable fragrances include sunflower musk, ketone musk, Tibetan musk, mixed xylene musk, nerolitin, ethyl vanillin, and mixtures thereof.

Such fragrance substances are described in detail in Perfume Flavors and Chemicals, Vols. I and II, Aurthor, Montclair, N.J., by S. Arctander, and Merck Index, 8th Edition, Merck Co., Inc. Rahway, N.J., Both references are hereby incorporated by reference.

Briefly, any chemically compatible material that emits a pleasant or other desired odor can be used in the fragrance-containing particles herein such that it imparts the desired odor when applied to fabrics.

Perfumes, generally in solid form, are also useful in the present invention. They can be mixed with a liquefier such as a solvent prior to incorporation into the granules, or they can simply be melted and incorporated so long as the flavor does not sublimate or decompose when heated.

The invention also includes the use of substances as malodor counteractants. These substances, although hereinafter referred to as "fragrances", may not have a discernible fragrance per se but may mask or attenuate any unpleasant odors. Examples of suitable malodor counteractants are disclosed in U.S. Patent 3,102,101, Hawley et al., issued August 27,1963.

The perfume-containing particles of the present invention even include perfumes not normally used to impart fragrance to fabric surfaces such as during laundering. Fragrance materials that are very volatile, labile or soluble in the particular mixture used to deliver the fragrance are useful in the present invention because the fragrance can be separated from the mixture of particles. Perfume materials that do not persist on the fabric during the laundering process are also useful in the present invention because the particles deliver the perfume to the surface of the fabric where it is released. Thus, delivery of fragrances to surfaces using the present invention expands the variety of fragrance materials that can be used.

Generally, the perfume-containing granules of the present invention contain from about 5% to about 70%, preferably from about 5% to about 50%, perfume. The exact amount of fragrance used in the granules will vary widely, depending on the strength of the particular fragrance used and the desired fragrance effect.

Carrier materials containing perfume particles must meet certain criteria in order to be useful in the present invention. First, the carrier substance must be a water-insoluble polymeric substance. In addition, the molecular weight of the material must be between about 100 and about 30,000, preferably between about 500 and about 5,000. The molecular weight of the carrier material can be determined by any standard method. The melting point of the substance must be between about 37°C and about 190°C, typically 37°C to 130°C. This prevents melting of the particles in storage or in a washing machine for laundry use. (The most ideal carrier material is not completely melted in the automatic dryer to avoid clogging of the lint mesh and excessive heat accumulation in the dryer). The melting point of the carrier substance should also not be higher than the temperature at which the fragrance associated therewith decomposes. The melting point of the carrier substances is determined by the so-called drop melting point method. American Society for Testing and Materials (ASTM) Test Method D127-63 (reapproved 1982, listed here by reference). Briefly, this method includes the following steps. The sample to be tested is attached to the thermometer bulb by inserting the cooled thermometer into the molten sample. The thermometer with the sample is then placed in the test tube and heated in a water bath until the sample melts and the first drop falls from the thermometer bulb. The average temperature at which the sample drops is the drop melting point of the sample.

The polymer must also have a specific hardness. Hardness values can be measured using the Standard Test Method for Petroleum Wax Needle Penetration. ASTM Test Method D 1321-86 (herein incorporated by reference). Briefly, the method involves first melting and burning the sample to be tested and then heating it to 17°C (30°F) above its freezing point. The sample is then poured into a container and cooled with air under controlled conditions. The samples were then conditioned in a water bath at the test temperature. Then the needle penetration is measured with a prickly meter, that is, a standard needle is applied to the sample for 5 seconds under a load of 100 grams. The penetration or hardness value is the depth, expressed in tenths of a millimeter, of the penetration of a standard needle into the wax under these defined conditions. For use in the present invention, the hardness value of the carrier substance must be between about 0.1 and about 15, Preferably it is between 0.1 and 8. This ensures a certain hardness of the particles and optimizes the protection/preservation of the fragrance in the carrier.

The carrier material must also be non-reactive with the perfume and be relatively odorless, and the material must allow the perfume to diffuse through it. The carrier substance must also melt without decomposing.

Non-limiting examples of carrier materials that can be used include polyethylenes, polyamides, polystyrenes, polyisoprenes, polycarbonates, polyesters, polyacrylates, vinyl polymers and polyurethanes and mixtures thereof, which meet the above-mentioned criteria, for example, they are water-insoluble, have a molecular weight of between about 100 and about 30,000, a melting point of between about 37°C and 190°C and a hardness value of 0.1 to 15 between.

The most preferred supports have a hardness value of 0.1 to 8, typically 0.5; a molecular weight of 500 to 5,000 (typically 2,000); and a melting point of about 126°C - typically polyethylene.

One carrier material meeting all these qualifying criteria is sold under the tradename POLYWAX 2000 by the Petrolite Specialty Polymers Group. This material is a polyethylene having a molecular weight of about 2,000, a melting point of about 259°F (126°C) and a hardness value (measured as above) of about 0.5 at 77°F (25°C). Another substance that meets these criteria is POLYWAX1000 (also sold by Petrolite Specialty Polymers Group). This material is also a polyethylene having a molecular weight of about 1,000, a melting point of about 237°F (114°C), and a hardness number of about 1.0 at 77°F (25°C). Another such substance is POLYWAX500.

It is desirable to use mixtures of different carrier materials in the perfume granules of the present invention, for example mixtures of polymers with small amounts of waxy materials. Examples of wax materials that can be used include those sold under the tradenames BOLER 1014, STARWAX 100 and VICTORY, all of which are available from the Boler Petroleum Company. This mixture has better adhesion properties because the particles formed from it have a "stickier" surface. Provided that the final mixture of carrier substances meets the above mentioned criteria. Numerous combinations of materials are possible and contemplated to be encompassed by the present invention.

The choice of carrier material for use in the perfume-containing particles of the present invention will depend to some extent on the particular perfume employed. Some fragrances require a higher degree of protection than others, so the carrier material used with them can be chosen accordingly.

Generally, the perfume-containing granules useful herein will contain from about 30% to about 95%, preferably from about 50% to about 95%, carrier material, and this will vary with the type and amount of the particular perfume employed.

In a typical process, perfume-containing granules can be prepared as follows. The carrier substance is first heated slowly to its melting point. The material is heated to just the temperature required for melting without further heating. The perfume, usually in the form of an oil or liquid, is then rapidly added to the molten carrier material at room temperature. The two are quickly mixed into a homogeneous mixture and then rapidly cooled with liquid nitrogen (or dry ice or whatever will quickly cool the mixture) until completely solidified. The finely divided solid material is then usually crushed or ground to produce particles of the desired average particle size. Other methods such as spray cooling or extrusion can also be used to subdivide the particles.

To further stabilize particularly volatile or delicate fragrances, it may be desirable to pre-add the fragrance (eg, mixed fragrance) to the silica gel or clay prior to mixing the fragrance with the carrier material. Certain less volatile fragrances do not require this special treatment as their release from the carrier material is greatly inhibited. The goal is to optimize the rate of release of the perfume from the carrier, and this optional additional step allows for better rate control of some of the more volatile perfumes.

cladding

The above-mentioned fragrance-containing particles are sealed to form a frangible coating. This coating prevents the fragrance from freely diffusing from the granules during long-term storage. Furthermore, this coating helps to preserve the original "character" of the fragrance which has a particularly volatile main character. In addition, the coating helps to protect the perfume-containing particle from incorporation of other components of the perfumed composition.

The coating material used here is friable and is intended to break apart when using a fragrance-infused formulation, thereby releasing the fragrance-containing particles.

The particles may be coated with more than one friable coating material to produce particles with more than one coating. As long as one of the coating layers (usually the outermost layer) is fragile, different coating materials can be selected according to needs to achieve different fragrance protection effects.

Individual perfume-containing particles can also be coalesced with the coating material to obtain larger particles containing many individual perfume-containing particles. This encapsulating particle agglomeration mass presents an additional barrier to perfume diffusion from the particle. This approach also minimizes the free particle surface area available for perfume diffusion. The ratio of perfume particles to agglomerating material will vary widely depending on the degree of additional protection desired. This method of coalescence is extremely useful for very volatile fragrances or those that are particularly prone to degradation. Furthermore, the aggregated association of very small perfume particles provides additional protection against premature diffusion of the perfume.

This form of particle agglomeration is useful to prevent separation of small perfume particles from larger detergent particles, eg in dry granular detergent products.

Preparation

For frangible coatings, the preparation method is based on applying the coating as a "shell" for the fragrance-containing particles. For perfume-containing particles whose carrier substance has a melting point lower than the boiling point of the flux used in the process, the process involves melting the carrier and perfume together and adding the molten mixture to a solution or a suitable precursor of the "shell" substance , maintained above the melting temperature of the carrier, the system is stirred sufficiently to form a carrier/perfume emulsion in the shell solution with the desired droplet size. The conditions necessary for the deposition of the encapsulating substance are thereby established. The bulk of the emulsion is cooled to obtain encapsulated solid particles with the desired friable "shell". The water insolubility of the shell is either formed during the deposition stage or by appropriate treatment of the particles prior to isolation or use.

Although the method described here is a one-step melt drop forming/sealing process, it will be apparent to one of ordinary skill in the art that sealing of pre-formed flavor particles can also be accomplished in a similar manner. Preformed granules can be prepared in a variety of ways including, for example, P.B. Deasy ("Microencapsulation & Related Drug Processes", Dakker, N.Y., 1986) and A. Kondo ("Microcapsule Processing and Processing Technology", Dekker, N.Y., 1979) in their books Cryogenic milling as described, spray drying. Spray coagulation and meltable dispersion technologies. These techniques are required for carrier substances that have a melting point higher than the boiling point of the solvent.

Various suitable sealing techniques may be used, such as described in the above-mentioned book by Deasy and Kondo. Depending on the substance used, the shell can render the particle hydrophilic or hydrophobic. Non-limiting examples of sealing materials and methods include, for a hydrophilic shell, gelatin arabic-gum concentrate deposited by a complex coacervation process, such as U.S. Patent 2,800,457, and for a hydrophobic shell, urea formaldehyde deposited by polycondensation. , such as U.S. Patent 3,516,941.

The water insolubility of the shell material may result from cross-linking of the gelatin-gum arabic coacervates with suitable aldehydes or other known gelatin hardeners after deposition. Polymerization of the urea-formaldehyde precondensate during the sealing process can result in water insolubility.

The slurry containing the perfume particles can be used directly, for example spray dried with the other ingredients of the formulation, or the particles can be washed and separated and dried if desired.

Example I

Perfume particles containing a hydrophilic coating deposited by complex coacervation were prepared as follows.

132 grams of POLYWAX 500 (500 molecular weight polyethylene) was heated in a beaker on a hot plate at approximately 100°C until just melted. 44 grams of fragrance was added to the molten POLYWAX 500 at room temperature and heating was maintained to return the cored mixture to 100°C.

The molten core-containing mass was added to 400 g of a 5% aqueous gelatin solution (Sanafi Type A, 275 Bloom strength), kept in a 1 liter steel beaker at 15-20°C above the melting point of the core, and emulsified with stirring to obtain Approximately 100μ droplet size is required. Then add 200 grams of hot 11% arabic gelatin solution and keep stirring for about 30 minutes.

The pH was lowered to about 4.2 by the dropwise addition of glacial acetic acid, and the contents of the beaker were poured into 1 liter of water stirred at room temperature. This causes the core-containing mixture to set with the deposition of the gelatin-gum arabic coacervate.

The coating was formed by cooling the slurry to about 5°C through ice water. A slurry can be used here, or the particles can be freed of any undeposited coacervate in the slurry by adding approximately an equal volume of 10% sodium chloride and removing the coating with a separatory funnel. This step can be repeated if necessary to completely remove the free coacervate. The particles were dried by filtration, washing the filter cake with water followed by inopiopanol, and then air drying at 25°C overnight.

The particles can then be sieved to achieve the desired size range.

Example II

Perfume particles with a poorly water-soluble hydrophilic coating can be prepared as follows.

A slurry of perfume granules containing a gelatin-gum arabic coating was prepared as in Example I. After cooling, the slurry was allowed to warm to room temperature and 8.0 ml of 25% aqueous glutaraldehyde solution was added with stirring. The pH was raised to 5.0 by adding 2.5% aqueous sodium hydroxide and the slurry was stirred overnight.

The slurry can be used here, or isolated as in Example I.

The coating treated with glutaraldehyde can withstand water at 60°C After soaking for a long time, the untreated coating will fall off when heated to 50°C.

Example III

Perfume particles containing a hydrophobic, water-insoluble coating deposited by polycondensation were prepared as follows.

A mixture of 162 g of 37% aqueous formaldehyde and 60-65 g of urea was adjusted to pH 8.0 with 0.53 g of sodium tetraborate, heated at 70°C for 1 hour, and then 276.85 g of water were added to first form a urea-formaldehyde precondensate.

Then 429 ml of this precondensate and 142 ml of water were stirred in a 1 liter steel reactor and 57.14 g of sodium chloride and 0.57 g of sodium carboxymethylcellulose were added. A core component containing 161.3 grams of POLYWAX 500 carrier and 60.7 ml of fragrance was then added and the reactor was heated to about 10°C above the melting point of the core. Agitation was adjusted to emulsify and maintain the molten core at the desired droplet size, and the pH was adjusted to about 5.0 with dilute hydrochloric acid.

The reactor was then allowed to cool to room temperature while the pH gradually dropped to 2.2 over 2 hours. The reactor was then raised to about 50°C over an additional 2 hours, then cooled to room temperature, after which the pH was adjusted to 7.0 with 10% sodium hydroxide solution.

The product slurry containing solid core particles encapsulated with urea formaldehyde polymer can be used directly or isolated by sorting, washing and air drying as required.

Coated fragrance-containing particles prepared in the foregoing manner may be used in any product type where it is desired to attach a fragrance to the surface being treated and to apply sufficient agitation and pressure to break the frangible coating. Typical examples of these products are laundry detergents and fabric softeners. The use of the mixtures of the invention in these products is illustrated below.

Laundry washing products include: detersive surfactants; usually one or more detergency builders; optional various enzymes, bleaches, carriers, etc. Dosage formulators are very familiar. Surfactants include soaps, alkylbenzene sulfonates, ethoxylated alcohols, alkyl sulfates, and the like. Builders include various phosphates, zeolites, polycarboxylates, and the like. Typical of these components are given by reference in U.S. Patents 3,985,669; 4,379,080 and 4,605,609.

Today's fabric softeners mainly include one or more quaternary ammonium salts, or imidazolines or imidazoline compounds. Softeners (and antistatic agents) generally contain one, or more preferably two C ₁₂ -C ₁₈ alkyl substituents and two or three short chain alkyl groups. Furthermore, these materials are common and well known to softener formulators.

Example IV

Granular laundry detergents are as follows:

Component Weight %

Sodium C ₁₃ alkylbenzene sulfonate 7.5

Sodium C ₁₄ -C ₁₅ Alkyl Sulfate 7.5

_C12-13 removal of non-ethoxylated alcohols and lower ethoxylates

Alkyl polyethoxylate (6.5) 2.0

C ₁₂ Alkyltrimethylammonium Chloride 1.0

Sodium tripolyphosphate 32.0

Sodium carbonate 10.0

Sodium perborate-hydrate 5.3

Sodium octanoyloxybenzenesulfonate 5.8

Sodium diethylenetriaminepentaacetate 0.5

Sodium sulfate, H ₂ O and balance of minor components

The above mixture is prepared using conventional methods. This mixture was combined with the perfume granules of Example 1 as follows. The perfume particles of Example 1 are combined with the detergent mix in such an amount that the detergent mix contains about 0.3% perfume.

The granules can be simply mixed with detergent granules. In order to prevent the separation of fragrance particles during packaging and transportation (due to their small particle size compared to detergent particles), the particles can be coated with a coating method or water-soluble coating material (in fragile packaging) before being combined with detergent particles. over the cladding) to coalesce. This can be done in a Schugi mixer (Flexomix 160), in which a sufficient amount of dextrin glue (2% dextrin, 3% water) is sprayed on the granules to form the same particle size as other detergent granules. range of perfume particle agglomerates.

The perfume is protected in the granule from degradation by the bleach in the detergent mixture when subjected to long-term storage. When used in the wash cycle of an automatic washing machine, such a detergent mixture will provide the perfume odor substantially in its original form from the product through the wash cycle to the fabric.

A large number of perfumes can be used in the present mixtures which on the other hand are not suitable for use in such laundry detergent mixtures.

Example V

A liquid fabric softener for use in an aqueous laundry rinse bath is as follows:

Component Weight %

Softener A ^* 3.00

Softener B ^** 5.00

HCl 0.29

Polydimethylsiloxane 0.15

Polyethylene glycol (4000) 0.30

Bronopol (sterilized) 100ppm

Calcium chloride 30ppm

Dye 30ppm

Coated Spice Granules ^**** 4.0

water balance

^＊ Softener A is

wherein each R group is in the range of C ₁₅ -C ₁₈ alkyl.

wherein each R group is in the C ₁₅ -C ₁₈ alkyl range

^*** Granules prepared as in Example II. 100 micron particle size; 5% coating weight.

When used in the rinse bath of an automatic washing machine, the coating of the perfume particles of Example V ruptures and the particles provide fragrance to the treated fabrics.

Example VI

A liquid laundry detergent mixture is as follows:

Component Weight %

C ₁₃ linear alkylbenzene sulfonic acid 7.2

C _14-15 alkyl polyethoxy (2.25) sulfuric acid 10.8

_C12-13 alcohol polyethoxylate (6.5) ^* 6.5

C ₁₂ alkyltrimethylammonium chloride 1.2

C _12-14 fatty acids 13.0

Oleic acid 2.0

Citric acid (anhydrous) 4.0

Diethylenetriaminepentaacetic acid 0.23

Protease (2.0AU/g) 0.75

Amylase (375Am.U/g) 0.16

TEPA-E _15-18 ^＊＊ 1.5

Monoethanolamine 2.0

(moles of alkanolamine) (0.033)

Sodium ion 1.66

Potassium ion 2.65

(molar ratio K ⁺ : Na ⁺ ) (0.94)

Propylene glycol 6.8

Ethanol 7.8

Formic acid 0.66

Calcium ion 0.03

Secondary components and water % balance

pH 8.65 at 10% concentration in water at 68°F (20°C)

^* Removal of alcohol and monoethoxylated alcohol.

^** Tetraethylenepentamine ethoxylated with 15-18 moles (average) of ethylene oxide per hydrogen position.

Detergents may be prepared by adding the components in the following order under continuous agitation: a slurry premix of alkylbenzenesulfonic acid, sodium hydroxide, propylene glycol, and ethanol; a slurry of alkylpolyethoxylated sulfuric acid, sodium hydroxide, and ethanol Premixes; Pentaacetic acid; Alcohol polyethoxylates; Premixes of water, brighteners, alkanolamines and alcohol polyethoxylates; Ethanol; Sodium and potassium hydroxides; Fatty acids; Citric acid; Formic acid and calcium; alkyltrimethylammonium chloride; TEPA-E _15-18 ; adjust the pH to about 8.1; and balance components.

The above mixture was combined with the perfume-containing granules prepared according to Example II as follows. The perfume particles of Example II (average particle size range 40-150 microns; 5% coating) are thoroughly mixed into the liquid detergent mixture in an amount such that the detergent mixture contains about 0.3% perfume (about 1% detergent Mixture contains spice granules).

Example VII

A fiber and fabric softener mixture is as follows.

Component Weight %

Softener C ^* 3.7

TAMET ^＊＊ 0.3

GMS ^＊＊＊ 1.20

Phosphoric acid 0.023

Polydimethylsiloxane (350) 0.10

Glutaraldehyde 550ppm

Blue dye 10ppm

Encapsulated Spice Granules ^****** 3.0

^* (R ¹ ) ₂ (CH ₃ ) ₂ N ⁺ , Br ^- , where R ¹ is a mixed C ₁₂ -C ₁₈ alkyl group (i.e. "tallow alkyl").

^** TAMET is tallow alkyl N(CH ₂ CH ₂ OH) ₂ .

^*** GMS is glyceryl monostearate.

^*** The coated perfume granules prepared in Example III were sieved to an average particle size of less than 150 microns. The cladding weighs 3%.

Those of ordinary skill in the art will recognize that the anionic X used herein with any cationic fabric softener is the usual material of choice, such X being, for example, chloride bromide, methyl sulfate, and the like. Blends of fabric softeners are available such as anionic Mixtures are used as well.

Example VIII

Example VI using perfumed granules with a friable coating (melamine/urea/formaldehyde; 0.1/1/1.1 molar ratio; 300 micron particle size) with a coating weight of 1% and 20% respectively Detergent mixtures are degenerated separately.

Example IX

2% by weight of the coated perfume granules of Example I (7% coating; all granules passed through a 150 micron screen) were slowly (so as not to break the coating) mixed into the 99.44% tallow soap mixture ( Na salt) and form sticks in a bar mold.

The mixtures herein can also be combined with abrasives. As we all know, scrubbing agents mainly include 10% to 90+% abrasives, such as pumice, silicon dioxide, calcium carbonate, and the like. The coated fragrance particles used in these scrubs rupture upon use to release the fragrance.

Example X

One scrub is as follows.

Component Weight %

Sodium tallow sulfate 1.0

Calcium carbonate 40.0

Pumice (through 60 micron sieve) 45.0

Sodium sulfate 10.0

Encapsulated Spice Granules ^* 3.0

Trisodium Phosphate Chloride 1.0

^* As in Example III; 10% coating; particles passed through a 100 micron sieve.

The mixture of Example X was prepared by slowly dry mixing the ingredients.

The formulator knows that the weight (or thickness) of the utility frangible coating can be adjusted according to the intended use. For example, even fairly thick coatings can break and release their fragrance particles under European machine wash conditions, which can include multi-minute wash times with high heat and vigorous agitation. Relatively speaking, machine wash conditions in the US are relatively short and gentle so smaller cover materials should be used. For fabric softeners, agitation and agitation times are usually reduced compared to washes.

Claims (5)

1, the perfume particle that comprises, its mean particle size is 40 microns to 350 microns, the spices that contains 5% to 70% (weight), it is characterized in that it is 100 to 30 that this spices is scattered in 30% to 95% (weight) molecular weight, 000, fusing point is that 37 ℃ to 100 ℃ and hardness value are in 0.1 to 15 the water-insoluble polymeric carrier material, described particle has the water-insoluble basically frangible coating layer of 1% to 20% (weight) on its outer surface, and described coating layer comprises the aminoplastics polymkeric substance.

2, the particle of claim 1, wherein said particulate mean particle size are 40 microns to 150 microns.

3, according to the particle of claim 1 or 2, wherein coating layer contains amine that is selected from urea and melamine and the aldehyde that is selected from formaldehyde, acetaldehyde, glutaraldehyde and the reaction product of the mixture of described amine and described aldehyde.

4, the particle of claim 3, wherein carrier substance is selected from polyethylene kind, polyamide-based, polystyrene type, polyisoprene class, polycarbonate-based, polyester, polyacrylate(s), vinyl polymer class, polyurethanes and composition thereof.

5, the particle of claim 3, wherein carrier substance contains polyethylene.