PT96791B - Process for the preparation of a detersive or amorphous composition and fabrics comprising of coated particle compositions - Google Patents

Abstract

A process is described for the preparation of a detergent composition or fabric softener characterized in that there are incorporated in the composition coated perfume particles having an average size after coating of less than 350 microns, and preferably not more than 150 microns, the said particles containing between 5% and 50% by weight of a perfume dispersed in 50% to 95% by weight of a supporting material comprising a fatty alcohol or a non-polymeric solid fatty ester or their mixtures having a molecular weight between 100 and 500 and a melting point between 37 degree C and 80 degree C, the said alcohol or ester being substantially insoluble in water, and the said particles having a friable coating which is substantially insoluble in water on their outer surfaces. The perfume particles comprise perfume dispersed in certain non-polymeric supporting materials which are insoluble in water and encapsulated in a protective coat of coating of a friable coating material. The coated particles preserve and protect perfumes which are subject to degradation or loss on storage and in cleaning compounds. In use break-up of the surface coating and the perfume/underlying support particles efficiently delivers a large quantity of types of perfume to fabrics or other surfaces.

Description

PROCESS FOR THE PREPARATION OF A DETERGENT OR SOFTENING TISSUE COMPOSITION UNDERSTANDING PARTICLES OF

COATED PERFUME

A process for the preparation of a detergent or fabric softener composition is described, characterized in that coated perfume particles are incorporated in the composition, having an average size, after coated, less than 350 mierons, preferably not more than 150 mierons , said particles comprising between 5% θ 5θ ^by weight of a perfume dispersed in 50 to 95% by weight of a support material consisting of a fatty alcohol or a solid non-polymeric fatty ester or mixtures thereof having a molecular weight included, between 100 and 500 and a melting point between 37 ° C and 80 ° C, said alcohol or ester being substantially insoluble in water, said particles having a friable coating substantially insoluble in water on their outer surfaces.

The perfume particles comprise perfume dispersed within certain water-insoluble non-polymeric support materials and encapsulated in a protective coating layer with a friable coating material. The coated particles allow the preservation and protection of perfumes that are susceptible to degradation or loss of storage and in cleaning compositions. In use, the fracture of the surface coating and the perfume particles / bottom support efficiently provides a large number of types of perfume to fabrics or other surfaces.

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Technical Field

The present invention relates to perfume particles containing perfume dispersed within a relatively low molecular weight non-polymeric support material and encapsulated with a friable coating. These coated particles are useful, for example, in tissue cleaning and conditioning compositions.

General Framework of the Invention

This invention is based on the concept of controlled perfume release, that is, release of perfume at a time and under conditions where the desired effect for the perfume is achieved. In general, this is a very old idea and several processes have been developed to achieve this purpose, from the simple idea of putting perfume on wax candles to the complex micro-encapsulation technology.

One aspect of the controlled perfume release concept is to achieve a slow release of perfume over an extended period of time. This is usually achieved by mixing perfume with a substance that essentially contains the perfume, in such a way that only small amounts of perfume are released over time. The use of high molecular weight polymeric substances which have incorporated perfume to provide controlled release of perfume over time is already known. See, for example, U.S. Patent No. 4,184,099, issued to Lindauer et al, published on January 15, 19θ0; European patent application O 028 118, Leonard, published on May 6, 1981; and U.S. Patent No. 4 110 261, Newland, issued August 29, 1971, which relate to combining perfume with a means of controlling release and combining a solid product to cool air.

The textile laundry industry is also related to the controlled release of per1

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- • 1 • - .'I smoke. The application of this concept allows to delay or prevent the release of perfume during long periods of storage. This concept also allows to use much lower perfume levels in the product since less perfume is lost.

The preservation of perfume during the storage period can be achieved in several ways. The perfume can be made from a part of the packaging for the composition. The perfume can be combined with the plastic used to make the packaging bottle, or the perfume can be mixed with a polymeric substance and the product used to coat a carton composition as described in U.S. Patent No. 4 54o 721, Staller, published September 10, 1985. Either way, the perfume is released from the polymeric matrix.

controlled perfume release agents can also be found in the form of mixed particles in the wash composition. One method designed to achieve this is to combine the perfume with a water-soluble polymer, transform it into particles and add it to the washing composition, as described in U.S. Patent No. 4,209,417, Whyte, published on 24 June 198O; U.S. Patent No. 4,339,356, Whyte, published July 13, 19θ2; and U.S. Patent No. 3,576,776, Gould et al., published April 27, 1971.

perfume can also be absorbed into a porous support material, which can be a polymeric material. See, for example, the publication of British patent number 2 066 839 »by Bares et al. (filed in the name of Vysoka Skola Chemicko Technologika), published on July 15, 1981. These methods can also be used to mask unpleasant odors in a composition or to protect perfume from degradation

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by astringent components present in powder compositions. Such methods provide these benefits only for dry powder or granular type compositions because as soon as the polymer is hydrated, the perfume is released. Thus, these methods provide benefits to the fragrance of the perfume after opening the product packaging and unloading it for washing. Although such benefits are desirable, it is even more desirable to have a method that allows the supply of undiluted, undissolved and unchanged perfume and the release of the perfume at the end of the washing process, so that the fabric has the desirable perfume odor.

Of course, a method for achieving this is to place the perfume in a product that is discharged directly into the dryer. Proceeding in this way the perfume is supplied to the fabric in the drying cycle. This method is described in the two US patents number 4 511 495, Melville, published on April 16, 19θ5 and number 4 636 330, Melville, published on January 13, 1987. Both refer to the transformation of perfume into particles with a support. These particles are then formulated in order to obtain a composition that is applied to textiles before placing them in the dryer or before drying on the laundry line.

An even more desirable method of providing perfume to washed fabric would be one that would provide perfume protection throughout the washing process, and then the perfume is delivered to the fabric essentially in its original state.

This method should allow the prevention of dilution, degradation or loss of perfume during the washing cycle in the laundry washing process. This is done using a system that releases the perfume in the drying process or after the perfume has been supplied to the fabric. Avoiding the release of perfume during the washing process involves very different and more difficult technology.

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This protection must be stable not only in conditions of high washing temperature, but must also be stable against degradation by water and other chemicals astringent in the washing process, such as washing compositions, enzymes, surfactants, etc.

One method that has been developed to provide these benefits is perfume microencapsulation. In this case, the perfume comprises a core of the capsule that is completely coated with a material that can be polymeric. US patent number 4 145 184 Brain et al. and published on March 20, 1979 and US patent number 4 234 627, Schilling, published on November 18, 1980, refer to the use of a ductile coating material that essentially prevents the diffusion of the perfume out . The perfume is supplied to the tissue by means of microcapsules and is then released by rupture of the microcapsules as can happen with the manipulation of the tissue.

Another method of perfume delivery involves providing perfume protection through the wash cycle, with perfume release under the high temperature conditions of the dryer. U.S. patent number 4,096,072, Brock et al., Published on June 20, 1978, relates to a method for providing fabric conditioning agents to textile products through the washing and drying cycle through of particles containing hydrogenated castor oil and a quaternary ammonium salt of fatty acid. The perfume can be incorporated into these particles. However, it is not clear whether the perfume thus incorporated is released in the washing cycle or carried in the particles to the dryer and released there when the particles soften.

U.S. Patent 4,402,856, Schnoring et al. and published on September 6, 1983, refers to a microencapsule technique4 =

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tion that involves the formulation of a coating material that allows the perfume to diffuse out of the capsule only at certain temperatures. This allows for the preservation of the perfume particles during storage and, additionally, during the washing cycle. The particles adhere to the fabric and are transported to the dryer. The diffusion of the perfume out of the capsules then occurs only under conditions of high temperature of the dryer. These particles are made of gelatin, an anionic polymer and a hardening agent

U.S. Patent No. 4,152,272, Young, published on May 1, 1979, refers to the incorporation of perfume into wax particles to protect the perfume during storage in dry compositions and through the process of washing. The perfume then diffuses through the wax matrix of the particles to the fabric under the high temperature conditions of the dryer.

It is desirable to provide compositions comprising perfume particles that can be incorporated in liquid, as well as dry granular or powder compositions and to provide stability during long-term storage.

It is desirable to provide a method for providing a wide range of perfume materials to fabrics or other surfaces during a fabric and fiber conditioning and cleaning process.

It is highly desirable to have a perfumed cleaning or conditioning composition that provides an improved odor to the product, an improved perfume odor released during the cleaning process and an improved odor and the intensity of the perfume delivered to the surface being cleaned.

It is particularly desirable to provide perfumed particles which are stable in fluid compositions but which release their perfume during use.

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Summary of the Invention

In addition to being especially effective in obtaining their intended benefit of prolonged perfume release, the coated perfumed particles of the present invention are designed to provide several important advantages over the various known encapsulated perfumes. First, the preferred coatings used here are stable not only in solid or granular washing compositions but also in liquid compositions. Second, the coated perfumed particles used herein do not require any additional treatment, such as applying additional cationic coatings to obtain the desired fiber and fabric substantivity result. Third, using solid carrier materials as the particle cores used herein, the particles become less fragile than the perfume particles that have liquid cores. Ijs not only simplifies manufacturing but also means that the particles are more robust under conditions of storage and shipping in the lavageurb than in other types of compositions. The non-polymeric support materials used here have the added advantage over many carriers of polymeric perfumes in that they are unpleasant in the environment or in sewage treatment facilities and / or because they are available from renewable sources, such as such as animal and vegetable fats and oils. In addition, the particles mentioned herein allow the formulation of condensed detergents with desirable perfume levels but without the undesirably high odor levels of the product packaging that are associated with the use of raw perfume.

However, in order to achieve the benefits described above and still function according to the intended way as a perfume delivery vehicle, it is important that the materials that carry the perfume employed here are carefully chosen from among the various

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'' ΐ'ηι) · 'ι classes of perspective perfume support materials widely known in the art. For example, the support may be slightly polar so that it incorporates a considerable amount of variety of perfume ingredients. Fatty alcohols and esters satisfy this requirement, but fatty acids tend to be too polar to imbue the desired high levels of many perfume ingredients. The support must be solid at room temperature so that stable particles can be produced and stored, although slightly softened in use, to help release the perfume. Likewise, fatty alcohols and esters satisfy these requirements. In addition, the substrates must be substantially insoluble in water (as defined in more detail below) under the conditions of use, since, otherwise, they would completely dissipate the perfume into the aqueous medium, for example, washing liquids, in that are used. Fatty alcohols and esters also meet these requirements. It is also important that the core material is chosen to be compatible with the material used to make the coating friable. This fact is especially important to provide particles coated with a good integrity of the friable aminoplast polymer coatings preferred here. Although it is not intended to be bound by any theory, it appears that the polarity of alcohols and esters makes them especially useful with these coatings.

In addition, it has been determined that the most preferred perfume particles of the present invention have optimal size requirements that are slightly tighter than the various encapsulated perfumes known in the literature, in order to optimally obtain the washing products of the type described here .

The present invention relates to part = 7 =

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Mod. 71 · 20,000 and * .- 90/08 perfume bowls that have an average size, when coated, less than about 350 micrometers (preferably an average size not exceeding 150 micrometers; more preferably, a range of sizes of 100 to 150 micrometers), which comprises from about 5% to about 50% (preferably at least about 10%) of a perfume dispersed in them between about 50% and about 95% of a fatty alcohol or a fatty ester of non-polymeric acid or mixtures thereof, support material having a molecular weight between about 100 and about 500 and a melting point between about 37 ° C and about 80 ° C, said esters or alcohols essentially insoluble in water and said particles having a friable coating substantially insoluble in water on their outer surfaces. (By size, the mean particle diameter in the case of substantially spherical particles or the size of the largest diameter or the largest dimension in the case of non-spherical particles). Particles of sizes larger than these values can be lost from the surface on which they are deposited and do not provide a relatively large surface area sufficient to release the perfume at the desired speed. Also, particles larger than specified may be undesirably noticeable on the surface being treated. Particles with sizes at the lower end of the range tend to stick well to the surface being treated but tend to release the scent very quickly. Extremely small particles outside the lower end of the range tend to be carried out of the tissues during washing operations.

Typically, the particles are characterized by a coating that comprises up to about 30% by weight of perfumed particles. For general use in fabric washing and conditioning compositions, the coating typically comprises between 1% to 20%, preferably 8 =

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Mod. 71 · 20,000 ex. - 90/08, 10% to 20% by weight of perfumed particles.

Preferred particles are those in which the friable coating is substantially insoluble in water. Suitable coatings of this type can be prepared from aminoplast polymers, for example, the reaction products of an amine with an aldehyde. Typical friable coatings comprise, for example, the reaction products of an amine chosen from urea and melamine and an aldehyde chosen from formaldehyde, acetaldehyde and glutaraldehyde and mixtures of said amines and said aldehydes. These friable coatings are described below.

Coated perfume particles are useful in situations where the particle coating is broken or worn (for example, in automatic washing machines or in laundry dryers) to release particles that, in turn, release your perfume. Thus, the coated particles are useful in typical cleaning compositions comprising detergent surfactants, optional bulking agents and the like. The particles are also useful in conditioning compositions that comprise fiber and tissue conditioning agents.

As can be concluded from what has been said above and from what is referred to below, the present invention comprises not only new and useful perfumed particles and compositions containing them, but also encompasses a method for providing particles that release perfume on the surface of fabrics that undergo a washing or softening process in washing machines, which comprises adding to said washing machine a detergent composition or a fabric softening composition containing particles comprising the friable coating / perfume / core, as detailed here and making operate the aforementioned machine with = 9 =

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In order to agitate the liquid of the machine and the fabrics, the agitation associated with said operation breaks the coating of said particles or fractures the particles themselves in an amount sufficient to allow the release of the perfume when the said particles are deposited on said fabrics during the said washing or softening process.

Especially preferably, the process employs particles comprising 55 to 65% by weight of core material, such as a C ^-CCC alcohol, especially straight chain alcohols or mixtures thereof; between 20 to 30% by weight of perfume; and the remainder comprising the friable coating, especially a water-insoluble polymeric coating made of an amine such as urea, melamine or mixtures thereof plus an aldehyde chosen from formaldehyde, glutaraldehyde or mixtures thereof.

It is understood that the method referred to herein is similarly useful in fabric bleaching operations which are carried out under conditions of agitation sufficient to fracture the friable coatings or which break the particles themselves. Similarly, the method is suitable for releasing perfume particles of bar soap and / or shampoos and the like, provided that these compositions are used, for example, rubbed with sufficient vigor to fracture the coating of said particles or the particles themselves .

All percentages given are by weight, unless otherwise specified.

Detailed Description of the Invention

The present invention allows the preservation, protection and supply of perfumes contained in cleaning and conditioning compositions through prolonged storage and astringent cleaning conditions. This is achieved by isolating the perfume from a material of suppositories 10 =

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in the form of small particles. The individual components of the invention will be studied in detail.

The Scented Particles

The perfumed particles of the present invention comprise perfume dispersed in certain support materials. The perfumed particles are coated with a friable coating material, which breaks down in use to release the perfumed particles, which in turn release their perfume.

In the present context, the term perfume * means any odorous material or any material that acts as a counter to bad smells. In general, these materials are characterized by having a vapor pressure lower than the atmospheric pressure at ambient temperatures. The perfume or deodorant materials used are, for the most part, liquid at room temperatures, but they can also be solid, such as the various camphor perfumes known in the art. A wide variety of chemicals are known for use in perfumery, including materials such as aldehydes, acetones, esters and the like. Most commonly, naturally occurring vegetable and animal oils and exudates comprising complex mixtures of various chemical components are known for use as perfumes and such materials can be used here. Perfumes can be relatively simple in their composition or they can comprise highly sophisticated complex mixtures of natural and synthetic chemical components, all chosen to provide any desired odor.

Typical perfumes may comprise, for example, wood / earth bases that contain exotic materials, such as sandalwood oil, civet, patchouli oil and the like. Perfumes can be of light flower scents, for example, rose extract, violet extract and the like. Perfumes can be for—

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Mod. 71 - 20,000 ex. - 70 (08 blended to provide desirable fruit odors, for example, lime, lemon, orange and the like. Suitable perfumes include musk ambret, musk acetone, musk tibetine, musk xylene, aurantiol, ethyl vanilla and mixtures thereof.

Perfume materials such as these are described in more detail by S. Arctander in Perfume Flavors and Chemicals. Vol. I and II, Aurthor, Montclair, NJ and the Merck Index, 8 »Edition. Merck & Co., Inc., Rahway, NJ, both of which are incorporated herein by reference.

In summary, any chemically compatible material that gives off a pleasant or otherwise desirable odor can be used in the perfumed particles to provide a desirable odor when applied to fabrics.

Perfumes that are normally solid can also be employed in the present invention. These perfumes can be mixed with a liquefying agent, such as a solvent, before incorporation into the particles, or they can simply be melted and incorporated as long as the perfume does not sublimate or decompose under heating.

The invention also comprises the use of materials that act as counter-actuators for bad smells. These materials, although designated as perfumes, may not have a discernible odor in themselves, but they can destroy or reduce any unpleasant odors. Examples of suitable bad odor counteractants are referred to in U.S. Patent No. 3,102,101, issued August 27, 1963 and issued to Hauley et al.

The perfumed particles of the present invention may even comprise perfumes that are not typically used to provide an aroma to a surface, such as a fabric during the washing process. The

63.138 Case Ul0U8 perfume materials that are very volatile, unstable or soluble in the particular compositions that are used to provide the perfume can be used in the present invention because the perfume is isolated from the composition in the particles. Perfume materials that are not substantive to fabrics in the washing process can also be used in the present invention since the particles deliver the perfume to the surface of the fabric where it is released. Thus, the use of the present invention to provide a perfume to a surface extends the class of perfume materials that can be used.

Generally, the perfumed particles of the present invention comprise between about 5% θ about 50%, preferably between about 20% and about 30% of perfume. The exact amount of perfume used in the particles varies greatly depending on the intensity of the particular aroma used and the desired odor effect.

The support materials used are characterized by several criteria that make them especially suitable in the practice of this invention. Of course, toxicologically acceptable materials are used that do not irritate the skin. As noted above, degradable materials and / or materials that are available from renewable sources are the most used. In general, the materials are solid at room temperature and have a melting point within the aforementioned desification. This prevents the particles from melting during storage. (It is more desirable to have a support material that does not completely melt in an automatic dryer, to avoid blocking the fiber network and excessive heat accumulation in the dryer). The melting point of the support material must also not be higher than the value at which the perfume to be combined with it decomposes. The melting point of the support material is measured by the so-called drip melting method. American Society for D127-63 test method = 13 =

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Testing and Materials (ASTM) (re-approved in 1982), incorporated herein by reference). Briefly, this method consists of the following. The sample to be measured is deposited in a thermometer bulb by immersing a cooled thermometer in the molten sample. The thermometer holding the sample is then placed in a test tube and heated in a water bath until the sample melts and the first drop falls from the bulb of the thermometer. The average of the temperatures at which the sample drops fall is the sample's drop melting point.

Support material must also be inert to the perfume and relatively odorless. The material must allow the perfume to diffuse through itself. The support material must be such that it melts without undergoing decomposition.

Having thus described the support materials useful in relation to their physicochemical properties, the following part refers to various non-polymeric compounds that can be used as support materials.

A class of support materials that is highly preferred comprises fatty alcohols. Fatty alcohols with a chain length equal to at least are substantially insoluble in water. The substantial insolubility in water is an important characteristic of the support materials in use, since, if the particle dissolves, for example, in the washing liquid, it releases its perfume immediately and thus it does not deposit on the fabric to provide the intended prolonged release of said perfume. Consequently, by the expression substantially insoluble in water, it is meant that the support materials do not dissolve in water in a proportion greater than about 10%, preferably not more than 5% by weight, at the temperatures of the aqueous media in question. that are used.

In addition, fatty alcohols are ti14 =

63,138 Case 41048 which are particularly solid at room temperature, that is, they have a melting point greater than about 30 ° C and typically melt in the range of about 37 ° C to about 75 ° C.

The most preferred support materials in this class are chosen from molecules that do not interact undesirably with the perfumes they are supporting or have a substantial amount of undesirable odor characteristics in themselves. For example, the preferred alcohol supports described below will generally not preferably be contaminated with lower molecular weight alcohols or lower molecular weight fatty acids, which can result in unpleasant or rancid smells, unless, of course, these odors are a desired complement to the perfume that is being served. In particular, straight chain fatty alcohols are preferred as they are available from natural sources. However, branched and some unsaturated alcohols can also be used.

Among the class of fatty alcohol supports, the most preferred are those of chain length between C C-C ^g. For reasons of possible foul odor, as noted above, it is generally preferred that the alcohols are substantially free of alcohols with a chain length and their oxidation products in the form of fatty acids. More specifically, nC 1 _U ° H (mirlstyl alcohol / tetradecanol) is preferred under low-temperature washing conditions in the United States of America, while alcohols in C ^ gC ^ g can be used under slightly washing conditions higher than in some European countries. Higher alcohols are also desirable when you want the benefit of a long-lasting perfume. Alcohols can also be present in the nuclei. However, it is appreciated that nuclei containing substantial amounts of alcohols may liquefy under certain storage conditions15 =

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'nm • - / I gem and the resulting liquid / coated core particles are more fragile than the solid / coated core particles and are fractured when the product is shipped. The alcohols ^ 20 '^ 24 ^ ° ^are useful under some conditions, even though these latter materials are more difficult to fill than the material in C₁-C₄ and, consequently, more expensive ones. Mixtures of fatty alcohols may also be used, provided they meet the above criteria.

In addition to the alcohols mentioned above, the following are representative, non-limiting examples of alcohols that can be used as core materials: n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol, n-docosanol, n-hyenanolanol, 16-methyl-heptadecanol, 26-methyl-hyicosanol, 22-methyl-pentacosanol and D-18-methyl-icosanol.

Other non-limiting examples of useful non-polymeric support materials include various esters having melting points equal to at least about 30 ° C, preferably between about 37 ° C and about 75 ° θ. The same considerations regarding substantial insolubility in water, acceptable odor characteristics, etc., indicated for alcohols are also important factors to consider with the support materials for esters-based perfumes.

In general, esters comprise at least about eighteen carbon atoms. Suitable esters include, for example, low alkyl esters (typically, C1 -C4) fatty acids that chemically comprise fatty acid esters of low monofunctional alcohols. Likewise, several fatty acid esters of polyfunctional alcohols can be used as long as the water insolubility parameter is satisfied. Fatty acid triglycerides, for example, fats that meet the above parameters are also suitable

63,138 Case Ul0U8 suitable for use here, as long as they give rise to the appropriate de-deconstruction.

The following examples of support materials consisting of suitable esters are given by way of illustration and not by way of limitation. It is appreciated by experts in the field that these esters are commercially available from various sources. Such esters include methyl stearate; ethyl stearate; methyl nonadecylate; ethyl nonadecylate; methyl arachidate; methyl beenate; mono-stearyl and monopalmityl esters of ethylene glycol; propylene glycol mono-stearyl and monopalmityl esters; rayon-stearyl and trimethylene glycol monopalmityl esters. Various diesters of the aforementioned polyols can also be used based on melting points and solubility characteristics.

In a typical process, particles containing perfume can be prepared as follows. The support material is first slowly heated to its melting point. The material is not heated more than necessary to melt the substance. The perfume is then added quickly, usually in the form of oil or liquid, at room temperature, to melt the support substance. The two substances are quickly mixed to form a homogeneous mixture which is then quickly cooled with liquid nitrogen (or with dry ice or any other means that allow the mixture to cool quickly) until it has completely solidified. The solid material is then germinated by spraying or grinding to produce particles of the desired average size. Other methods, such as spray cooling or extrusion, can also be used to subdivide the particles.

To stabilize particularly volatile or delicate perfumes, it may be desirable to preload = 17 =

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the perfume (that is, mix the perfume) with silica gel or clay before combining it with the support substance. Some perfumes that are not very volatile do not require this special treatment because this would excessively inhibit their release of the support substance. Optimizing the speed at which the perfume is released from the support is the intended purpose and this optional additional phase allows for better speed control with some of the most volatile perfumes.

Coating

The perfume-containing particles, referred to above, are encapsulated to obtain a friable coating. This coating prevents the perfume from diffusing out of the particles easily during long periods of storage. In addition, the coating helps to preserve the original character of perfumes that have particularly volatile characteristics. In addition, the coating helps to protect the scented particle from the action of the other ingredients in the scented formulation.

The coating materials used here are friable and designed to break when the scented formulation is used, thus releasing the scented particle.

The particles can be coated with more than one friable coating material to produce a particle having more than one coating layer. Different coating materials can be chosen to provide different perfume protection when necessary, provided that one of the coatings, usually the exterior, is friable.

The individual perfume-containing particles can also be agglomerated with the coating material to provide larger particles comprising a number of individual perfume-containing particles.

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This agglomerated material surrounding the particles provides an additional barrier to the diffusion of the perfume out of the particles. This process also minimizes the surface area of free particles capable of diffusing perfume. The proportion of perfume particles to agglomerated material varies greatly depending on the extent of the desired additional protection. This agglomeration process can be particularly useful with very volatile perfumes or with perfumes that are especially susceptible to degradation. The agglomeration of very small perfume particles also provides additional protection against premature perfume diffusion.

Agglomerating the particles in this way is useful to prevent the segregation of small particles of perfume from the larger detergent granules, for example, in a dry granular detergent product.

Manufacturing Process

For friable coatings, the manufacturing process is based on applying the coating as if it were a kind of shell to the perfumed particles. For perfumed particles whose support material has a melting point below the boiling point of the solvent used in the process, the process comprises adding the support substance and perfume to a solution of the shell material solvent or an appropriate precursor , maintained above the melting temperatures of the substrate. The system is sufficiently agitated to form a perfume / carrier emulsion with the desired liquid droplet size in the shell solution. The necessary conditions for depositing the encapsulated material are then established and the assembly is cooled to give solid encapsulated particles that have the desired friable shell.

The insolubility in water of the shell is then established either in the deposition operation or by appropriate treatment =

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Mod. 71 · 20,000 ex. - 90 (06 before isolation or use of particles.

Although the process described herein is a way of proceeding to encapsulate / melt drops in a single operation, it is easily apparent to those skilled in the art that encapsulation of preformed perfume particles can be carried out in a similar manner. The preformed particles can be prepared in a variety of ways, including cryoprotection, spray drying, spray freezing and melt dispersion techniques as described in the book of Ρ. B. Deasy Microencapsulation and Related Drug Processes, Dekker, New York, 1986 and by A. Kondo in Microcapsule Processing and Technology, Dekker, New York, 1979 «These techniques are necessary for support materials with melting points above the boiling point of the solvent.

A wide variety of encapsulation processes can be used, such as those indicated in the books by Deasy and Kondo, referred to above. Depending on the materials used, the shell may impart hydrophilicity or hydrophobicity to the particles. For examples of encapsulated materials and processes that include gum arabic / gelatin concentrate deposited by complex coacervation processes, see, for example, U.S. Patent Number 2 800 457 »θ deposited urea / formaldehyde resin by a polycondensation process, see, for example, US patent number 3 516 941. Water insolubility of shell materials can be achieved, for example, by crosslinking the gelatin / arabic gum coacervate with aldehydes appropriate or other known gelatin-hardened after deposition. The polymerization of the urea / formaldehyde pre-condensate during the encapsulation process inherently causes insolubility in water.

The suspension containing the particles

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of perfume can be used directly, for example, mixed and dried with other components of the granular detergent formulations or the particles can be washed and separated and dried, if desired.

EXAMPLES

Example I

Perfume particles are prepared containing a friable hydrophobic coating, insoluble in water, deposited by polycondensation, proceeding as described below.

First, a urea / formaldehyde pre-condensate is formed by heating the mixture of 1662 grams to 37% aqueous formaldehyde and 60 to 65 grams of urea, adjusted to pH 8.0 with 0.53 grams of sodium tetraborate, for one hour at 70 ° C and then 276.85 grams of water are added.

429 ml of this pre-condensate and 142 ml of water are stirred in a 1 liter steel reactor and 57.14 grams of sodium chloride and 0.57 grams of sodium salt of carboxymethylcellulose are added. Then, the core components which comprise 166.2 grams of support substance C ^^ OH and 55.8 grams of perfume are added and the reactor is heated to about 9θ ° θ · The stirring is adjusted to emulsify and keeping the core fused to the desired droplet size and adjusting the pH of the content to about 5.0 with dilute hydrochloric acid.

The reactor is then allowed to cool to room temperature with a gradual reduction in pH to 2.2 over a period of two hours. The reactor is then heated to about 50 ° C for a further two hours, then cooled to room temperature, after which the pH is adjusted to 7.0 with 15% ammonium hydroxide solution.

The resulting suspension containing the encapsulated solid core particles can be used directly

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with urea / formaldehyde polymer or can be isolated by separation, washing and air drying as needed.

The coated scented particles prepared in the manner mentioned above can be used in all types of products in which it is desirable to deposit fragrances on treated surfaces and in which sufficient agitation or pressure is exerted to break the friable coating. Typical examples of such products are washing detergents and fabric softeners. Next, the use of the compositions according to this invention in such products is illustrated.

Cleaning and washing products comprise: a detergent surfactant (typically, between 5 ® 30% by weight); optionally but typically, one or more disinfecting agents (10 to 55% ^by weight); optionally, 3 to 20% by weight of various enzymes, bleaching agents, support agents and the like, all of which are well known in the art and very familiar to detergent formulators. Surfactants include soap, alkyl benzene sulfonates, ethoxylated alcohols, alkyl sulfates, alpha sulfonated fatty acids and the like. Bulking agents include various phosphates, zeolites, polycarboxylates and the like. US patents number 3 9θ5 669, 4,379 θθθ ^and

6O5 609 can be referred to for typical listings of these ingredients.

Modern fabric softeners typically comprise about 3% to 35% by weight of one or more quaternary ammonium salts, for example, tallow dimethylammonium or imidazoline or imidazolinium chloride. Softening agents (and antistatic agents) generally have one or, preferably, two alkyl substituents θ ^ 2 "θΐ8 ^{and or} three lower alkyl groups. Also, these materials are conventional and well known to formulators of softening agents.

63,138 Case 41048

It is understandable that one of the greatest advantages of the scented coated particles of this invention is their ability to be formulated stably (typically 0.1% to 10% by weight) in combination with conventional detergents, bleaching agents and compositions for treating fabrics without any difficulty .

Example II

A granular washing detergent has the following composition

Components Percent by Weight

Sodium C4-benzene sulfonate 7.5

C ^^alkyl - Cquiloalkyl - sodium sulfate 7.5

Alkylated in ^ jl2 ”° 13 P ° H ^ oxylated (6.5) with vaporized non-ethoxylated alcohol and lower ethoxylate 2.0

Alkyl chloride in methylammonium 1.0

Sodium tripolyphosphate 32.0

Sodium carbonate 10.0

Sodium perborate monohydrate 5.3

Octanoyloxy-benzene sulfonate 5.8

0.5 diethylene triamine-pentacetate sodium

Sodium sulfate, H2 O ^and other constituents remaining.

The above composition is prepared using conventional means. Combine the composition with as =

63,138 Case 41048

«T f’ ’··

- · - / I perfume particles of Example I, proceeding as follows. An amount of the perfume particles of Example I is combined with the detergent composition so that the detergent composition comprises about 0.3% perfume.

The particles can simply be mixed with the granular detergent. To avoid the segregation of the perfume particles during packaging and shipping (due to their small size in relation to the detergent granules), the particles can optionally be coated or agglomerated with a water-soluble coating material (over the friable coating) ) before combining with the detergent granules. This can be done with a Schugi mixer (Flexomix ΐ6θ) in which a sufficient amount of dextrin gum solution (2% dextrin, 3% water) is sprayed onto the particles, in order to result in agglomerates of perfume particles from the same size as the detergent granules.

perfume is protected in the particles against degradation caused by the bleaching product present in the detergent composition during long periods of storage. When used in the automatic washing machine washing process, this detergent composition releases the grams of perfume in its substantially original state to the fabric through the washing process.

In the present composition, a large number of perfumes can be used which would not otherwise be suitable for use in such washing detergent compositions.

Example III

A liquid fabric softening agent is prepared for use in a water wash, with the following composition:

=

63.138 Case 4l0U8 i

Components Percentage by weight X Softening agent A 3.00 XX Softening Agent B 5.00 HCl 0.29 Polydimethylsiloxane 0.15 Polyethylene glycol 0.30 Bronopol (antimicrobial agent) 100 ppm Calcium chloride 30 ppm Dye 30 ppm Perfume coated particles 4, the

Remaining Water * The softening agent A is

II

RCOCH ₂ CH ₂ N + R (CH ₃ ) ₂ Where each R symbol represents an alkyl radical en »

5-5 ^{to C} 18 · softening agent B is _ 0

N-CH_CH_O-CR ^{2 2}

I

R in which, each R symbol represents a C ₁₅ to C ₄ alkyl radical.

xxx

Particles prepared according to Example I; granulometry = 80 to 100 micrometers; 20% by weight of coating.

=

63,138 Case 4ΐθ48

' ⁿ 31

When used in the rinsing bath of the automatic washing machine, the coating of the perfume particles of Example III breaks and the particles provide the aroma to the fabrics being treated.

Example IV

A liquid detergent composition has the following composition.

Components Percent by Weight

Linear benzenesulfonic 7 »2 alkyl acid

Alkyl acid in 10.8 polyethoxylated sulfuric acid (2.25)

Á1 cool in C ^ ₂ polyetho- 6.5 xylated (6.5) *

Alkyl chloride at C ^ - 1,2 trimethylammonium

Fatty acid at C ^ ₂ 13.0

Oleic acid 2.0

Citric acid (anhydrous) 4.0

0.23 pentacotic diethylenetriamine acid

Enzyme protease (2.0 AU / g) 0.75

Enzyme amylase (375 Am. U / g) 0.16 tepa-e ₁₅ _ _i8 «* 1.5

Monoethanolamine 2.0 (moles of alkanolamine) (0.033)

Sodium ion 1.66

Potassium ion 2.65

63,138 Case 410 78

(continued)

Components (K +: Na + molar)

Propylene glycol

Ethanol (calcium ion formic cycle

Smaller components and water pH at a concentration of 10% in water 6 ° F (20 ° C)

Percentage by weight (0.94)

6.8 ”8 t

0.66

0.03

Up to 100

8.65 xx.

alcohol and mono-ethoxylated alcohol are removed.

Ethoxylated tetra-ethylene-pentimine with 15 to 18 moles (in average) of ethylene oxide at each hydrogen site.

The detergent is prepared by adding the components, with continuous mixing, in the following order: pre-mixture of alkyl-benzene-sulfonic acid paste, sodium hydroxide, propylene glycol and ethanol; a pre-mix paste of alkyl sulfuric acid, polyethoxylaclo, sodium hydroxide and ethanol is prepared; pentacetic acid; polyethoxylated alcohol, water premix, bleaching agents, alkanolamine and polyethoxylated alcohol; ethanol; sodium hydroxide and potassium hydroxide; fatty acid; Citric acid; formic acid and calcium salt; alkyl trimethylammonium chloride; TEPA-E ^ g;

in order to be equal to about 8.1; remaining parts of the components.

The above-mentioned composition is combined with the perfume-containing particles prepared according to Example I, proceeding as indicated below. Carefully mix an amount of particles, adjust the pH and add to =

63,138 Case 41048

/ of perfume of Example I (average size = 40 to 150 micrometers; 5% of coating) in the liquid detergent composition, so that the detergent composition contains about 0.37% of perfume (about 1% of the detergent composition comprises the perfume particles).

Example V

The composition of a fiber and fabric softener has the following components.

Components

Percentage by weight

C TAMET softening agent * **

GMS

Phosphoric acid (353) Po lidime til siloxane

Glutaraldehyde

Blue dye

Perfume coated particles

3.7 o, 3

1.20

0.023

0.10

550 ppm 10 ppm

3.0 * (r!) ₂ (CH3) ₂ N +, Br ", where R ^ is mixed C ^ -C ^ g alkyl (i.e. tallow alkyl").

** T / M, ET is tallow alkyl N (Cl2 CH3 OH) ₂ .

KXIK »

GMS is glyceryl monostearate

Perfume particles coated according to Example I, sieved to have an average size less than 100 micrometers. Coating weight 20 $.

63,183

Case ΑΐθΑ8

It is advisable, as all those skilled in the art know, that X anions used with any of the fabric softening agents be chosen as usual and X may be, for example, chloride, bromide, methyl-sulfate and the like. Mixtures of fabric softening agents may also be used, as well as mixtures of anions.

Example VI

The fabric softener composition is modified according to Example III using perfumed particles with friable coatings (melamine / urea / formaldehyde; molar ratio = 0.1 / l / l, l; particle size = = 80 micrometers) with weights of coating of about 20% respectively. It should be noted that it refers to the replacement of melamine by about 15% aminoplast for use in fabric softeners. It should also be noted that the above-mentioned particles of 80 micrometers are visible in the softener products.

Example VII

A detergent bar composition is prepared by gently mixing (so as not to fracture the coating) 2% by weight of the scented coated particles of Example I (7% coating; all particles pass through a 150 micron sieve) in a mixture of 99.4% suet soap (sodium salt) and is transformed into a bar by passing through an appropriate stamp.

The compositions discussed herein can also be used in combination with abrasive agents. As is known, abrasive cleaning agents typically comprise 10% to 90% or more of abrasive materials, such as pumice, silica, calcium carbonate and the like. The coated perfume particles used in these cleaning agents are broken when used to release =

63,138 Case 41048

your perfume.

Example VIII

An abrasive cleaning composition has the following components.

Percentage

Components by weight_

Tallow sulfate alkyl sodium 1.0 Calcium carbonate 4th, the Pumice stone (passes through 60 mesh sieve) 45.0 Sodium sulphate 10.0 Perfume particles 3.0 coated * Chlorinated trisodium phosphate 1.0

X

According to Example I; coating 10 particles passed through the 100 micrometer sieve.

It is appreciated by formulators that the weight (or thickness) of the operable friable coatings can be adjusted according to the intended use. For example, even relatively thick coatings break and release perfume particles under the conditions existing in European washing machines, which can comprise washing times of many minutes at high temperatures and considerable agitation. On the contrary, the washing conditions of North American machines are much shorter and smoother washing times, so less coating material should be used. For fabric softening agents, agitation and stirring times are generally shorter than for washing.

63.138 Case 4ΐθ48 • Π-ΙΙ

Example IX

A bleaching composition comprises about 6% aqueous hypochlorite / H2O containing 10% by weight of the particles of Example I. The product is agitated before being used as a fabric bleach or in the toilet bowl as a dehydrator to suspend the particles .

Example X

A granular detergent composition for washing is prepared as follows.

Percentage

Components - by weight

C ^-alkylenesulfonate alkyl 5.64 Tallow-sulfate alcohol 2.42 Sodium sulphate 22.00 Sodium silicate 8.00 Sodium sulphate 0.40 Carboxymethyl cellulose 0.29 EDTA 0.29 Bleach 47 0.15 Sodium tripolyphosphate 21.34 Surfactant E07 * 5.00 Sodium perborate 4H ₂ O 13.23 Sodium perborate 1H ₂ O 1.96 Sodium carbonate 7.00 Proteolytic enzyme 0.79 KX TAED 3.03 Perfume particles *** 1.00

63,138

Case 41048

<ηηι

.. ✓ I (continued)

Percentage by weight

Remaining **

Components

Water / secondary components

Dobanol 45-7

Tetracetyl.ethylenediamine

Prepared according to Example 1;

size 100-150 micrometers; 20% coating

Example XI

A granular detergent concentrate is prepared from the following components:

Percentage in

Components weight

Linear sodium alkylbenzene ssulfonate with an average chain size of 12.4 13.9

Sodium alkyl sulfate 5.9 with an average chain length of 14.5

Aluminosilicate (Zeolite A; 25.36 1-10 micrometers

Polyacrylate 4500 4.47 Polyethylene glycol 8000 1.46 Sodium carbonate 17.82 Sodium sulphate 11.06 Silicate solids 2.05 = 32 =

63,138 Case 4io48 ./1 (Continued)

Percentage in

Components Weight Whitener 15 0.2Q Humidity 7.70 several 0.57 Enzyme 0.78 ^C 12-13 ^EO 6.5 ⁿ ° - ^ionic 1.07 Citric acid 6.57 Perfume particles * 1.00

X

According to Example I; size 100-150 micrometer

Claims (11)

= CLAIMS = 1 * - Process for the preparation of a detergent or fabric softener composition, characterized in that coated perfume particles having an average size, after being coated, are less than 350 microns, preferably not greater than 150 microns, comprising said particles between 5% ® 5% $ by weight of a perfume dispersed in 50% to 95% by weight of a support material consisting of a fatty alcohol or a solid non-polymeric fatty ester or mixtures thereof having a molecular weight between 100 and 500 and a melting point between 37 ° C and 80 ° C, said alcohol or ester being substantially insoluble in water, said particles having a friable coating substantially insoluble in water on their outer surfaces. 2 * - Process according to claim33 63.1 ^ 3 Case 4ΐθ48 cation 1, characterized in that the coating comprises an aminoplast polymer. 3 ^a - Process according to claim 2, characterized in that the coating comprises the reaction product of an amine with an aldehyde, preferably an amine selected from urea and melamine, and a selected aldehyde formaldehyde, acetaldehyde and glutaraldehyde and mixtures of said amines and said aldehydes. ^ 4 - Process according to claim 3, wherein said support material comprises one selected alcohol alcohols _{(η 1Ο} ID 10 0 ', 0. 5 ^a - Process according to the previous claims, characterized in that the detergent composition comprise one or more detergent surfactants and optionally one or more bulking agents and perfume contain coated particles according to claim 1. 6. A process according to claim 5, characterized in that the said perfume particles comprise a fatty alcohol (C ^-C ^ g) coated with a friable aminoplast polymer comprising the reaction product of an amine chosen from urea, melamine or their mixtures and an aldehyde chosen from formaldehyde, acetaldehyde, glutaraldehyde or their mixtures. 7. ^A process according to claim 5, characterized in that said composition is in granular or bar form and additionally contains an abrasive agent. Process according to the preceding claims, characterized in that the fabric softening composition comprises one or more anti-static or fiber or fabric softening agents, and con = 34 = 63,138 Case 4108 having perfume particles coated according to claim 1. Process according to claim 8, characterized in that the said perfume particles comprise an alcohol ^θ ° said friable coating is the product of the reaction of an amine chosen from urea and melamine or mixtures thereof with an aldehyde chosen from formaldehyde, acetaldehyde, glutaraldehyde or their mixtures. 10. The process of claim 9 wherein the softened composition comprises said perfume particles and an anti-static or fabric or fiber softening agent chosen from compounds of the general formula R-COH ₂ CH ₂ N ⁺ R (CH ₃ ) ₂ , X; N N-CH-CH-O-C-R Y 'in which each of the symbols R represents an alkyl radical and of the general formula (R ¹ ) ₂ (CH ₃ ) ₂ N ⁺ X, in which each of the symbols R ^ represents an alkyl radical and ^ ^C 12 “ ^C l8 ^ 'and their mixtures; and 63,138 Case 4lOU8 I the symbol X represents an anion. Process according to the preceding claims, characterized in that the coating of said particles breaks or fractures sufficiently to allow the release of the perfume when said particles are deposited on said fabrics during a washing or softening process.