EP1767614A1 - Verfahren zur Herstellung eines sprühgetrockneten Pulvers - Google Patents

Verfahren zur Herstellung eines sprühgetrockneten Pulvers Download PDF

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Publication number
EP1767614A1
EP1767614A1 EP06121132A EP06121132A EP1767614A1 EP 1767614 A1 EP1767614 A1 EP 1767614A1 EP 06121132 A EP06121132 A EP 06121132A EP 06121132 A EP06121132 A EP 06121132A EP 1767614 A1 EP1767614 A1 EP 1767614A1
Authority
EP
European Patent Office
Prior art keywords
weight
capsules
slurry
perfume
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06121132A
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English (en)
French (fr)
Inventor
Jonathan Warr
Stuart Fraser
Emmanuel Aussant
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Takasago International Corp
Original Assignee
Takasago International Corp
Takasago Perfumery Industry Co
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Filing date
Publication date
Priority claimed from EP05291975A external-priority patent/EP1767613A1/de
Application filed by Takasago International Corp, Takasago Perfumery Industry Co filed Critical Takasago International Corp
Priority to EP06121132A priority Critical patent/EP1767614A1/de
Publication of EP1767614A1 publication Critical patent/EP1767614A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay

Definitions

  • the present invention relates to a process for spray drying an oil or waxy solid containing aminoplast core shell capsule along with inorganic salts and optionally a binding agent or one or more surfactants to form a particulate powder.
  • Adding fragrance during later stages of the laundry process is one way to provide fragrance to the laundry e.g. through rinse conditioners or drier sheets as shown in US patent 4,511,495 and ironing products but this involves the cost and inconvenience of purchasing and using an additional product.
  • Another method for delivering perfume to laundered fabric is one which increases deposition during the wash and prevents evaporation during drying for example by the use of pro-fragrances. These molecules deposit onto textiles during the wash and later react to release volatile fragrance molecules. The reaction can be triggered by a number of means: under the influence of co-deposited enzymes as in US patent 5,726,345 , of sunlight as in US patent 6,218,355 , or by bacterial or enzymatic decomposition.
  • capsules must be sufficiently robust to withstand all the processes involved in manufacture e.g. transporting, handling and packing yet still be sufficiently friable as to rupture under relatively gentle conditions whilst handling the garment.
  • certain fragrance components are sensitive to the alkalinity and/or bleach content of detergent powders.
  • any capsule intended to provide the benefits stated above could be in a form so as to mix easily and uniformly in a detergent powder and withstand processing and manipulation during manufacture and yet be capable of rupturing on handling the laundry.
  • the present invention relates to the process of manufacturing powders containing perfume capsules by spray drying.
  • the process involves (a) the preparation of a slurry which contains inorganic salts and optionally a binding agent and between 0.001% and 20% by weight based on the dried powder of the capsules and (b) spray drying the resulting slurry to form a spray dried powder.
  • the powder is a laundry detergent powder in which case the slurry may contain at least one detergent active of the type anionic, non-ionic, zwitterionic or cationic surfactant.
  • Part of the inorganic salts may function as the builder in the detergent as for example with phosphate or carbonate salts.
  • the slurry might include additional inorganic compounds such as aluminosilicate salts which function as a detergent builder.
  • Other common ingredients of detergent powders normally added to the slurry include fluorescers, polymers such as maleic anhydride acrylic acid copolymers, sequestrants, silicone antifoams, and anti redeposition agents.
  • the invention also covers any subsequent treatment of that powder necessary to prepare particles which can be incorporated directly into a laundry detergent product. So, depending on the design and operation of individual spray drying towers, granulation may be required to form particles of the appropriate size for inclusion into a detergent powder. Such granulation may be part of the same spray drying process or a separate step after the spray drying.
  • the powder of the invention could be used directly in laundry cleaning or conditioning, it could be blended with other ingredients typically post-dosed into spray dried detergents such as bleaches, bleach precursors, sequestrants, enzymes, colour protecting agents, further surfactants, inorganics, and fragrance as part of the detergent manufacturing process.
  • the capsules of the invention could be added to a detergent powder as a convenient way of adding concentrated encapsulated perfume into another pre-formed detergent powder.
  • the powder might be converted into another form of detergent product for example the powder might be compressed or coated to form a detergent tablet which is then used for fabric treatment as part of conventional laundering.
  • dispersants are often advantageous for tablets.
  • the capsules used in the invention process have an average particle size of less than about 300 microns preferably an average size of not greater than 100 microns and especially a 5-50 micron average size range.
  • the capsules used in the invention process are core shell capsules which are thermally stable at 250°C for 15 minutes.
  • Capsules based on starches or water soluble polymers are primarily intended to protect the perfume during storage and to release the perfume once mixed with water as exemplified in EP patent 1,388,585 which releases perfume during the laundering process.
  • EP patent 1,196,533 which provides an oil or waxy solid encapsulated within a starch capsule will also release it on contact with water. These capsules fail the slurry stability test described below and so are outside the scope of the present invention.
  • Capsules based on perfume incorporation into high melting waxes or polymers such as in EP patent 0,469,228 which claims a perfume solid composition having melting points over the range of 35 to 120° C are unlikely to retain perfume through the high temperatures of spray drying.
  • capsules of the present invention A specific requirement of capsules of the present invention is that a large proportion of the capsules must survive dispersal in the warm aqueous slurry without excessive leakage of the contents and then remain intact through the exposure to high temperatures encountered during spray drying.
  • suitable capsules can be defined by two tests:
  • the amount of encapsulated material released being determined by an appropriate analytical method, so for example, perfume release might be determined by trapping the released perfume and measuring it by gas chromatography.
  • Spray Dry Test (Test 2): To meet the requirements of the invention more than 30% by weight of the encapsulated material, added to a slurry at room temperature for 15 minutes, the slurry having the following composition:
  • the core shell capsules based on formaldehyde and urea, formaldehyde and melamine, or formaldehyde and urea and melamine condensation polymers are particularly well suited although this is not intended to exclude capsules made with other monomers or incorporating other monomers or other amine aldehyde condensation polymers.
  • suitable monomers for core shell capsules are for example methyl methacrylate as exemplified in International application WO 01/49817 , and urethanes as exemplified in International application WO 03/099005 . Suitable monomers are well known to those skilled in the art of polymerisation reactions.
  • International application WO 92/18601 teaches the use of aminoplast capsules for laundry application, among others, with the capsules having a core which solidifies at ambient temperature to improve the strength of the capsules.
  • International application WO 00/05951 describes an aminoplast capsule with a base cleavable ester moiety to trigger release under alkaline conditions.
  • US patent 6,849,591 teaches the use of spray drying to dry aminoplast capsules made via addition polymerization in the oil phase preferably with oil soluble initiators; however, this patent does not suggest the addition of capsules to a detergent slurry, nor the addition of any other ingredients during the drying step.
  • Particularly preferred core shell capsules suitable for the process of the invention are the core shell capsules containing in the core an oil or waxy solid, said oil or solid waxy having little or no aldehyde or amine containing raw materials. It is also preferable if more than 80% by weight of the oil or waxy solid are in the range ClogP 1.5-4.5, more preferably ClogP 2-4.
  • the appropriate core shell capsules contain in the core an oil or waxy solid, said oil or waxy solid comprising by weight:
  • the benefit agents other than perfume ingredients are preferably selected among the group consisting of malodour counteracting agents, essential oils, aromatherapeutic materials, chemaesthetic agents vitamins, insect repellents, UV absorbers, antioxidants and agents, which improve the capsule properties such as:
  • compositions and processes for manufacturing aminoplast capsules in the form of dispersion such as EP 1,246,693 A1 and US patent 6,261,483 which are incorporated herein by reference.
  • a typical condensation polymerization process for preparing a capsule dispersion would include the following steps.
  • the first step is the mixing of the above-defined emulsion with melamine-formaldehyde resin (with a melamine: formaldehyde: methanol mixture in the approximate molar ratios 1:3:2 to 1:6:4) and an emulsifier.
  • melamine-formaldehyde resin with a melamine: formaldehyde: methanol mixture in the approximate molar ratios 1:3:2 to 1:6:4
  • an emulsifier may be precondensed or the monomers may be used directly.
  • Some of the melamine can be replaced by urea.
  • the formaldehyde may be partially etherified preferably as the methyl ethers.
  • the shell is constituted of 50-100% by weight formaldehyde-melamine or formaldehyde-melamine-urea or formaldehyde-urea condensation polymers or partially corresponding etherified formaldehyde condensation polymers, preferably as the methyl ethers.
  • the shell may be also constituted of 50-100 % by weight of methacrylate or urethane.
  • the capsules are cured by heating to a temperature between 60°C to 100°C for several hours under moderate stirring.
  • urea melamine or other amines, or mixtures thereof can be made to reduce the formaldehyde concentration in the finished dispersion, and increase the wall thickness.
  • a particularly advantageous ratio is 5:1 to 1:1 melamine:urea.
  • the temperature is reduced to around 50°C, and the dispersion is neutralized before being adjusted to a pH around 9.5.
  • the final capsule dispersion as shipped should contain less than 0.1% by weight of free formaldehyde or free acetaldehyde measured by GLC or HPLC (standard methods are published by the US Environmental Protection Agency; HPLC requires derivatisation of the formaldehyde), preferably less than 100 ppm (wt/wt) and more preferably less than 10 ppm wt/wt.
  • Such materials as cationic polymers or copolymers e.g. polyvinyl imidazole, polysaccharides based on beta 1, 4 linkages such a guar gum, and polyester copolymers such as those sold commercially as soil release polymers for detergents are examples of suitable materials to improve deposition.
  • cationic polymers or copolymers e.g. polyvinyl imidazole, polysaccharides based on beta 1, 4 linkages such a guar gum, and polyester copolymers such as those sold commercially as soil release polymers for detergents are examples of suitable materials to improve deposition.
  • Capsules of the above process will generally have a particle size within the range from 5-100 ⁇ m, preferably 5-70 ⁇ m, depending on the composition of the core material and emulsifying conditions.
  • the capsule wall will have a thickness of 0.025 ⁇ m-1.0 ⁇ m. These parameters are important in the proper functioning of the capsules. If the capsule wall is too thin, the capsules will be too friable for subsequent shipping and handling, if too thick they might not break when required. If capsules are very small the wall material may become an uneconomically large proportion of the capsule. Very large capsules either require thicker walls or the addition of hardeners to the core to prevent breakage in handling both of which reduces the amount of beneficial agent delivered.
  • the dispersion of capsules may typically contain, by weight, 2.5%-80% dispersed capsules by weight in water. Preferably the dispersion contains from 5%-70% by weight of capsules and even more preferably from 30% - 70% by weight. In some forms of the process excess water can be removed to form a concentrated wet cake. Since the capsules are introduced to aqueous slurry the presence of water is not deleterious and may protect the capsules during shipping.
  • the capsules are introduced in the slurry in the form of an aqueous dispersion of capsules.
  • Suitable perfumes for the composition can be composed from a wide range of perfumery raw materials well known to those skilled in the art. Examples of suitable perfume ingredients are described in S. Arctander, Perfume Flavors and Chemicals. Vols. I and II, Aurthor, Montclair, N.J., and the Merck Index, 8th Edition, Merck & Co., Inc. Rahway, N.J., both are being incorporated herein by reference. It is preferable if the perfume has little or no aldehyde or amine containing raw materials. It is also preferable if more than 80% by weight of the perfume is in the range ClogP 1.5-4.5, more preferably ClogP 2-4.
  • Particularly preferred suitable perfume compositions are in the form of an oil or waxy solid, which contain at least two perfume ingredients, wherein:
  • perfume composition which is also named “fragrance” as defined below is an essential part of the invention.
  • the term “perfume composition” means any odoriferous material or any material which acts as a malodor counteractant.
  • a wide variety of chemicals are known for perfumery uses, including materials such as alcohols, ketones, esters, ethers, nitriles, and the like.
  • the perfume compounds will have molecular weights of less than 400 mass units to ensure sufficient volatility and will not contain strongly ionizing functional groups such as sulphonates, sulphates, or quaternary ammonium ions.
  • perfumes Naturally occurring plant and animal oils and exudates or oils and exudates identical to those found in the nature, comprising complex mixtures of various chemical components are also known for use as perfumes, and such materials can be used herein.
  • Perfume compositions of the present invention can be relatively simple in their composition with a minimum of two perfume or fragrance ingredients or can comprise highly complex mixtures of natural and synthetic chemical components, chosen to provide any desired odor.
  • aldehydes not only react to some extent during the preparation of the capsules but surprisingly they continue reacting over time on storage within the capsule itself to an extent which may make the fragrance olfactively unacceptable.
  • aldehydes are reactive species some aldehydes e.g. lilial, cyclamen aldehyde and hexyl cinnamic aldehyde are frequently used at quite high levels in fragrances for laundry products and are stable in these formulations.
  • the perfume composition of the present invention preferably restrict the level of total aldehydes including alpha beta unsaturated aldehydes to less than 20% by weight, preferably less than 10% by weight and even more preferably less than 1% by weight of the perfume composition.
  • the perfume compositions of the invention preferably contain less than 10% by weight, and more preferably less than 1% by weight of primary and secondary amines.
  • a further aspect of the invention is that the capsule should contain more than 50% by weight, and preferably more than 60% and more preferably more than 70% and even more preferably more than 80% by weight of perfumery ingredients.
  • capsules Whilst economically it would seem obvious to incorporate as much active ingredients as possible into each capsule, for many practical reasons, associated with emulsion stability, capsule integrity etc., many capsules contain other ingredients e.g. solvents, hardeners which substantially dilute the fragrance and benefit agents.
  • fragrance compositions of the invention preferably contain less than 25% by weight of perfume ingredients preferably less than 20% by weight with ClogP>4 and less than 20% by weight with ClogP ⁇ 2.
  • ClogP refers to the octanol/water partitioning coefficient (P) of fragrance ingredients.
  • the octanol/water partitioning coefficient of a perfume ingredient is the ratio between its equilibrium concentrations in octanol and in water.
  • the partitioning coefficients of perfume ingredients are more conveniently given in the form of their logarithm to the base 10, logP.
  • the perfume ingredients of this invention have logP of about 1.5 and higher preferably in the range 2.5 to 5.
  • the logP of many perfume ingredients has been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, Calif., contains many, along with citations to the original literature.
  • ClogP values reported herein are most conveniently calculated by the "CLOGP" program available within the Chemoffice Ultra Software version 9 available from CambridgeSoft Corporation, 100 CambridgePark Drive, Cambridge, MA 02140 USA or CambridgeSoft Corporation, 8 Signet Court, Swanns Road, Cambridge CB5 8LA UK.
  • the ClogP values are preferably used instead of the experimental logP values in the selection of perfume ingredients which are useful in the present invention.
  • the composition of such oils can be determined by analysis or using the compositions published in the ESO 2000 database published by BACIS (Boelens Aroma Chemical Information Service, Groen van Prinsterlaan 21, 1272 GB Huizen, The Netherlands).
  • the oil or waxy solid contains 0-1 % by weight of perfume ingredients, which are selected among:
  • the composition of the capsule core must take into account the less desirable characteristics of some fragrance materials such as persistence in the environment, accumulation in aquatic organisms, and toxic, allergenic or irritant effects with some humans.
  • the capsules will deliver fragrance more efficiently to the surface fewer capsules and hence less fragrance is needed to achieve a desired fragrance effect, so the overall environmental load is reduced.
  • the greater concentration on skin or in close proximity to the skin requires additional care to formulate the core composition using only ingredients known to be safe in such a context.
  • perfume compositions are nitro musks as exemplified by musk ambrette CAS 83-66-9, and musk ketone CAS 81-14-1, polycyclic musks typified by Galaxolide CAS 1222-05-5 and Tonalid CAS1506-02-1, cashmeran, geranyl nitrile, safrole, estragol, methyl eugenol, halogen containing perfumery materials.
  • Materials listed in Annex 1 of the Dangerous Substances Directive (67/548/EEC) or any of its amendments or ATPs (Adaptation to Technical Progress), or classified as R43 in their safety data sheet are optionally restricted to less than 1% of the core composition, preferably less than 0.1% by weight, more preferably below 0.001%, and even more preferably below the analytical detection limit.
  • any materials classified as very toxic or toxic are preferably excluded from the core composition.
  • Those fragrance ingredients alleged to be allergenic substances within the 7th amendment of the Cosmetic Directive, Directive 2003/15/EC (7th amendment to Directive 76/768/EEC) and the Detergent Regulations (2004/648/EEC) are optionally restricted to below 1% by weight, preferably below 100ppm and more preferably below 10ppm of the core composition.
  • These Directives are also amended via ATPs, for example the 26 th Commission Directive 2002/34/EC.
  • the core composition is preferably formulated so as not to require any form of classification or warning phrase, especially classification Xi or Xn due to for example the presence of amounts of raw materials classified as R43 “sensitisasion by skin contact”, R36 “irritating to eyes”, R38 "irritating to skin” or R21 “Harmful in contact with skin” under the Dangerous Preparations Directive (99/45/EEC).
  • the SCCNFP Stemific Committee on Cosmetic Products and Non Food Products for Consumers
  • SCCNFP/0392/00 SCCNFP/0392/00, final, give a number of raw materials where there is concern.
  • the oil or waxy solid has preferably a peroxide value of 0-20 millimoles peroxide / litre, preferably 0-10 millimoles peroxide / litre, and even more preferably 0-1 millimoles peroxide / litre.
  • limonene (d-, I-, and dl-), and natural products containing substantial amounts of limonene, they should have a peroxide value of less than 20 millimole peroxide per litre.
  • the methods for measuring peroxide value are well known to those skilled in the art, and a method is published by the FMA (Fragrance Material Association).
  • Typical perfume compositions herein can comprise, for example, woody/earthy notes containing as perfume ingredients synthetic materials and natural extracts such as sandalwood oil, or patchouli oil and the like.
  • the perfumes herein can be of a light, floral fragrance, e.g., rose, violet, jasmine, lily and the like.
  • the perfume compositions herein can be formulated to provide desirable fruity odors, e.g., lime, lemon, orange, berry fruits or peach and the like.
  • any chemically compatible material which exudes a pleasant or otherwise desirable odor can be used in the perfumed capsules herein to provide a desirable odor when applied to fabrics.
  • Table 1 below lists some perfume ingredients which have ClogP values, calculated using Chemoffice Ultra Version 9, between 2.0 and 5.0 and which comply with the requirements of the present invention. The values were found to be essentially identical to those obtained using Daylight ClogP (version 4.9).
  • Table 1 Name ClogP CAS n° Laevo carvone 2.01 6485-40-1 Geraniol 2.97 106-24-1 Cis Jasmone 2.64 588-10-8 Alpha Terpineol 2.63 98-55-5 Eugenol 2.34 97-53-0 Methyl cinnamate 2.46 103-26-4 Methyl dihydrojasmonate 2.91 24851-98-7 Beta methyl naphthyl ketone 2.76 93-08-3 Iso bornyl acetate 4.04 125-12-2 Carvacrol 3.35 499-75-2 Para cymene 4.07 99-87-6 Dihydromyrcenol 3.04 18479-58-8 Geranyl acetate 3.91 105-87-3 Linalyl acetate
  • Table 2 below lists examples of materials, widely used in fragrances for household products, the levels of which are restricted within the invention.
  • Table 2 Name ClogP CAS n° Hydroxycitronellal 1.54 107-75-5 Linalool 2.75 78-70-6 Phenyl ethyl alcohol 1.33 60-12-8 Coumarin 1.41 91-64-5 Vanillin 1.28 121-33-5 Citronellol 3.25 106-22-9 d-Limonene 4.35 5989-27-5 Isobutyl quinoline 3.98 93-19-6 Hexyl cinnamic aldehyde 5.00 101-86-0 Lilial 4.10 80-54-6 Galaxolide 5.74 1222-05-5 Cyclamen aldehyde 3.83 103-95-7
  • the invention also encompasses the use of odiferous materials which also act as malodor counteractants. These materials, although termed “perfume ingredients” hereinafter, may have a weak odor but can conceal or reduce any unpleasant odors. Examples of suitable malodor counteractants are disclosed in US patent. 3,102,101 and in US patent 5,554,588 .
  • Olfactively weak or neutral solvents may constitute up to 30% of the capsule core material by weight, preferably less than 20% by weight and more preferably less than 10% by weight. If present they will most likely have been introduced with one or more perfume ingredients. In the perfume industry it is quite common to dissolve solid perfume ingredients in a suitable solvent or to dilute powerful materials, used at low levels, with a solvent to facilitate manufacture.
  • Typical solvents include high ClogP materials such as benzyl benzoate, isopropyl myristate, dialkyl adipates, citrate esters such as acetyl triethyl citrate or acetyl tributyl citrate or triethyl citrate or diethyl phthalate or low ClogP materials such as propylene glycol or dipropylene glycol. While these materials could affect fragrance release or emulsion properties during capsule manufacture, at the levels described such effects will be minimal. For the purpose of this patent, when solvent is present, it is considered as an "other benefit agent".
  • high ClogP materials such as benzyl benzoate, isopropyl myristate, dialkyl adipates, citrate esters such as acetyl triethyl citrate or acetyl tributyl citrate or triethyl citrate or diethyl phthalate
  • low ClogP materials such as propylene glycol or diprop
  • other benefit agent means any material capable of being encapsulated in the way described above and which can survive storage to deliver a benefit when used in household, personal care or cosmetic products. It is preferable if the benefit agent contains little or no aldehydes, in particular alpha, beta unsaturated aldehydes or primary or secondary amines; as described previously, i.e. they should satisfy the requirements concerning aldehydes and amines given above for the perfume composition. Benefit agents do not have to conform to the ClogP requirements as outlined for the fragrance ingredients since it is not a necessary feature of the benefit agents that they vapourise to be effective.
  • Materials which when added to the emulsion improve the properties of the core emulsion before encapsulation, or the properties of the capsules themselves.
  • Materials which provide a warming or cooling effect such as described in Cosmetics and Toiletries Vol. 120 No 5 p105 by M Erman are also benefit agents.
  • Such agents include but are not limited to: cyclohexane carboxamide N-ethyl-5-methyl-2-(1-methylethyl) known as WS3 TM (CAS N° 39711-79-0); N 2,3-trimethyl-2-isopropylbutamide known as WS23 TM (CAS 51115-67-4); menthyl lactate (CAS N° 59259-38-0); (-)-menthoxypropane 1,2-diol known as cooling agent 10 TM and isopulegol.
  • antioxidants such as butylated hydroxyl toluene or butylated hydroxyanisole or pentaerythrityl tetra- di- t-butyl hydroxyhydrocinnamate, octadecyl di t-butyl-4-hydroxyhydrocinnamate (CAS N° 2082-79-3), tetrabutyl ethylidenebisphenol (CAS N° 35958-30-6) are benefit agents.
  • UV absorbers such as octyl methoxycinnamate, benzophenone 3, butylmethoxydibenzoylmethane, or benzotriazolyl dodecyl p cresol (CAS N° 6683-19-8), bis ethylhexyloxyphenolmethoxyphenyltriazine are benefit agents.
  • the materials listed above are intended to exemplify the benefit agents but are not intented to limit the benefit agents to this list. Mixtures of the above may also be considered as benefit agents of the invention.
  • vitamin E acetate can function as an antioxidant as well as a vitamin precursor.
  • the aqueous slurry used in the invention process comprises inorganic salts and at least one binding agent.
  • Inorganic salts suitable for spray drying are typically sodium, potassium, magnesium, calcium or aluminium salts of sulphate, carbonate, bicarbonate, citrate and silicate, which can be used alone or in any combination or ratio. Some are discussed below as inorganic builders, and others play roles such as:
  • Especially preferred inorganic salts are: sodium carbonate, calcium carbonate, sodium bicarbonate, sodium silicates, layered sodium silicates (especially Na SKS-6), sodium phosphates (especially sodium tripolyphosphate, sodium metaphosphate), sodium aluminosilicates (especially Zeolite 4A, Zeolite A24).
  • Binding agents suitable for spray drying include nonionic, anionic, amphoteric and cationic surfactants discussed in detail below.
  • Other suitable binding agents are organic polymers such as polycarboxylates and sodium carboxy methyl cellulose. It is particularly preferred that the binding agent has a functional benefit e.g. surfactants are also part of the cleaning system, polycarboxylate is part of the builder system etc.
  • Preferred binding organic polymers/polycarboxylates are: poly(acrylic acid), copolymers of acrylic acid (especially copolymer with maleic acid), poly(aspartic acid), poly(lactic acid), citric acid, carboxy methyl cellulose and salts/derivatives thereof, polyethyleneglycol and derivatives thereof.
  • Particularly preferred binding surfactants of the present invention are the conventional C 11 -C 18 alkyl benzene sulfonates ("LAS"), the C 10 -C 18 alkyl alkoxy sulfates (AE x Sulfates; especially EO 1-7 ethoxy sulfates), alkyl sulfates (AS), soaps and mono or di-alkyl (C 10 -C 20 ) quaternary ammonium salts.
  • LAS C 11 -C 18 alkyl benzene sulfonates
  • AE x Sulfates especially EO 1-7 ethoxy sulfates
  • AS alkyl sulfates
  • soaps and mono or di-alkyl (C 10 -C 20 ) quaternary ammonium salts.
  • the slurry is made by mixing the inorganic salts and the binding agents and the capsules with water by the methods well known by the person skilled in the art. As the slurry is very concentrated it is typically a dispersion rather than a solution (even when it contains materials which have good water solubility), and it needs to be well and continuously mixed. Any particulate matter present in the dispersion must be sufficiently small to easily pass through a spray drying nozzle without causing a blockage.
  • Spray drying as a processing technique has and continues to find widespread use as a method for producing powders. It creates relatively porous particles which dissolve easily, even at low temperatures.
  • Many patents and publications are available on spray drying.
  • An overview article for detergent powders can be found in Powdered Detergents vol 71 (Surfactant Science Series) ed M Showell, ISBN 0-8247-9988-7 , which includes a general overview of production methods and includes on page 25, a schematic of slurry preparation and spray drying (courtesy Ballestra SPA), and Formulating Detergents and Personal Care Products. Ho Tan Tai. AOCS Press ISBN 1-893997-10-3 .
  • Spray drying processes for forming detergent compositions are well known in the art and typically involve the steps of forming a detergent slurry, often warmed to 60-80°C using at least in part heat of anionic surfactant neutralization (e.g. neutralization of linear alkyl benzene sulphonic acid).
  • the slurry has typically a water content of between 30%-60% by weight and commonly comprises a builder, a neutralized or acid-form anionic surfactant, a nonionic surfactant, a neutralizing alkali such as soda ash or sodium carbonate, an inorganic salt or salts such as sodium sulphate, water, processing aids, and organic polymers in a crutcher.
  • the detergent slurry is pumped to the top of a spray drying tower, and sprayed from nozzles in the tower to form atomized droplets.
  • These compositions could also be prepared by continuous slurry making.
  • continuous slurry making is meant a process in which components are fed continuously and substantially simultaneously to a slurry making vessel while mixed slurry is removed to the spray tower at a rate which maintains an essentially constant volume in the vessel.
  • Hot air is pumped through the spray drying towers such that when the atomized droplets are sprayed into the hot air, they dry into a powder as the free moisture evaporates.
  • the spray-dried granules thus formed are then collected at the bottom of the tower.
  • Numerous patents teach specific modifications to this basic protocol in order to better produce powders with specific properties.
  • US patent 4,269,722 teaches spray drying especially porous particles to incorporate nonionic surfactant.
  • GB patent 1,473,201 teaches spray drying compositions containing zeolite.
  • EP patent 1,499,703 describes the manufacture of powders having low anionic surfactant content while US patent 4,900,466 describes the preparation of particles having defined pores by varying the ratio of inorganic salts in a composition with little or no surfactant but using a polymeric binder. However none of these detergent patents describe the incorporation of capsules within the slurry.
  • the characteristics of the powder particles will be affected.
  • conventional spray dried detergent powders have bulk densities of 200-550 kgm -3 and particle sizes concentrated around 250-700 ⁇ m. In some instances it is possible to produce much finer and denser powders. These may not disperse uniformly within a detergent powder and so it is preferable if the powder is more agglomerated. This may be achieved in the spray drying tower by adding some steam to the powder or separately in a fluid bed mixer.
  • composition of a range powders (often termed “blown powder” or “base powder”) which can be prepared by spray drying can be found in International application WO 99/65458 which is incorporated herein by reference. This patent also teaches ingredients which can be post dosed or sprayed on to the base powder.
  • the surfactant composition for a detergent powder may contain at least about 0.01% by weight of a surfactant selected from the group consisting of anionic, cationic, nonionic, and zwitterionic surface active agents.
  • a surfactant selected from the group consisting of anionic, cationic, nonionic, and zwitterionic surface active agents.
  • surfactant is present to the extent of from about 1.0% to 60%, more preferably 1.0% to about 30% by weight of the composition.
  • Non-limiting examples of surfactants useful herein typically at levels from about 1% to about 55%, by weight include the conventional C 11 -C 18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C 10 -C 20 alkyl sulfates ("AS"), the C 10 -C 18 secondary alkyl sulfates of the formula CH 3 (CH 2 ) x (CHOSO 3 - M + )CH 3 and CH 3 (CH 2 ) y (CHOSO 3 - M + )CH 2 CH 3 where x and (y+1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C 10 -C 18 alkyl alkoxy sulfates (AE x Sulfates; especially EO 1-7 ethoxy sulfates), C 10 -C 18 alkyl al
  • the conventional nonionic and amphoteric surfactants such as the C 12 -C 18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C 6 -C 12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C 12 -C 18 betaines and sulfobetaines ("sultaines"), C 10 -C 18 amine oxides, and the like, can also be included in the overall compositions.
  • the C 10 -C 18 N-alkyl polyhydroxy fatty acid amides are highly preferred, especially the C 12 -C 18 N-methylglucamides. See International application WO 92/06154 .
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10 -C 18 N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C 12 -C 18 glucamides can be used for low sudsing.
  • C 10 -C 20 conventional soaps may also be used. If high foaming is desired, the branched-chain C 10 -C 16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful.
  • Other conventional useful surfactants are described further herein and are listed in standard texts such as " Surface Active Agents and Detergents" by Schwartz, Perry & Berch incorporated herein by reference.
  • Anionic surfactants can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals.
  • alkyl is the alkyl portion of higher acyl radicals.
  • tallow or coconut alcohols and about 1 to about 10 moles of ethylene oxide
  • the reaction products of fatty acids are derived from coconut oil or waxy solid sodium or potassium salts of fatty acid amides of a methyl tauride in which the fatty acids, for example, are derived from coconut oil or waxy solid and sodium or potassium beta-acetoxy- or beta-acetamido-alkanesulfonates where the alkane has from 8 to 22 carbon atoms.
  • secondary alkyl sulfates may be used by the formulator exclusively or in conjunction with other surfactant materials and the following identifies and illustrates the differences between sulfated surfactants and otherwise conventional alkyl sulfate surfactants.
  • Non-limiting examples of such ingredients are as follows.
  • Conventional primary alkyl sulfates such as those illustrated above, have the general formula ROSO 3 - M + wherein R is typically a linear C 8 -C 22 hydrocarbyl group and M is a water solublizing cation.
  • Branched chain primary alkyl sulfate b surfactants i.e. branched-chain "PAS" having 8-20 carbon atoms are also know; see, for example, EP patent application 0,439,316 .
  • Conventional secondary alkyl sulfate surfactants are those materials which have the sulfate moiety distributed randomly along the hydrocarbyl "backbone" of the molecule. Such materials may be depicted by the structure CH 3 (CH 2 ) n (CHOSO 3 - M + )(CH 2 ) m CH 3 wherein m and n are integers of 2 of greater and the sum of m+n is typically about 9 to 17, and M is a water-solublizing cation.
  • the aforementioned secondary alkyl sulfates are those prepared by the addition of H 2 SO 4 to olefins.
  • a typical synthesis using alpha olefins and sulfuric acid is disclosed in US patent 3,234,258 , or in US patent 5,075,041 . See also US patent 5,349,101 and US patent 5,389,277 .
  • Water soluble salts of the higher fatty acids ie soaps are useful anionic surfactants in the composition herein.
  • the fatty acids may be saturated, often termed hardened, wholly or partially as required. Soaps can be made by direct saponification of fats or oil or waxy solids or by the neutralization of free fatty acids.
  • Particularly useful are the sodium and/or potassium salts of the mixtures of fatty acids derived from coconut oil, palm oil and tallow.
  • Other useful soaps are described in EP patent 1 282 678 in the section titled "fatty acids”.
  • the preferred surfactants of the present invention are anionic surfactants, however, other surfactants useful herein are described below.
  • compositions of the present invention can optionally include at least about 0.01% by weight, preferably at least 0.1% by weight, more preferably from about 1% to about 30% by weight, of a nonionic surfactant.
  • Preferred nonionic surfactants such as C 12 -C 18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C 6 -C 12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), block alkylene oxide condensate of C 6 -C 12 alkyl phenols, alkylene oxide condensates of C 8 -C 22 alkanols and ethylene oxide/propylene oxide block polymers (Pluronic.TM.-BASF Corp.), as well as semi polar nonionics (e.g., amine oxides and phosphine oxides) can be used in the present compositions.
  • AE alkyl ethoxylates
  • Alkylpolysaccharides such as disclosed in US patent 4,565,647 (incorporated herein by reference) may also be preferred nonionic surfactants in the compositions of the invention.
  • nonionic surfactants comprises alkyl polyglucosides having 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain such as disclosed in US patent 4,565,647 . These compounds usually contain from 1 to 20, preferably from 1.1 to 5, glucoside units.
  • Another class of nonionic surfactants comprises N-alkylglucamides.
  • a particularly desirable surfactant of this type for use in the compositions herein is alkyl-N-methyl glucamide.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides.
  • Another optional detersive surfactant is a cationic surfactant.
  • the cationically charged group is an ammonium group substituted by at least one, preferably only one, hydroxyalkyl group and three alkyl groups of which one is a long alkyl chain having 12 to 20 carbon atoms and the other two alkyl substituents have 1 to 4 carbon atoms.
  • the hydroxyalkyl preferably has from 1 to 4 carbon atoms, more preferably 2 or 3 carbon atoms, most preferably 2 carbon atoms.
  • Suitable quaternary ammonium compounds for use as detersive surfactants are: coconut trimethyl ammonium chloride or bromide; coconut methyl dihydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide; C 12 -C 15 dimethyl hydroxyethyl ammonium chloride or bromide; coconut dimethyl hydroxyethyl ammonium chloride or bromide; myristyl trimethyl ammonium methyl sulphate; lauryl dimethyl benzyl ammonium chloride or bromide; lauryl dimethyl (ethenoxy) ammonium chloride or bromide.
  • amphoteric surfactants include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds in which the aliphatic moieties can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group.
  • amphoteric surfactants are the betaines which have the general formula: RN + (R 1 )(R 2 )CH 2 ) n X - wherein R is a hydrophobic group selected from the group consisting of alkyl groups containing from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms, alkyl aryl and aryl alkyl groups containing a similar number of carbon atoms with a benzene ring being treated as equivalent to about 2 carbon atoms, and similar structures interrupted by amido or ether linkages; each R 1 and R 2 are alkyl groups containing from 1 to about 3 carbon atoms ; and n is from 1 to 6 and X is a carboxylate group.
  • betaines cocoamidopropyl betaine, dodecyl dimethyl betaine, cetyl dimethyl betaine, dodecyl amidopropyl dimethyl betaine, tetradecyldimethyl betaine, and tetradecylamidopropyldimethyl betaine.
  • Detergent builders can optionally be included in the slurry for spray drying. They may also be incorporated into laundry detergent compositions to assist in controlling mineral hardness. Inorganic as well as organic builders can be used separately or in admixture. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soil.
  • the level of builder can vary widely depending upon the type of builder and the end use of the composition. When present, the compositions will typically comprise at least about 1% by weight of builder. Formulations typically comprise from about 5% to about 80%, more typically about 10% to about 50%, by weight, of detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • suitable inorganic builders are aluminosilicates having ion exchange properties, such as zeolites, for example.
  • zeolites are suitable, especially zeolite A, X, B, P, MAP and HS in their Na form or in forms in which some of the Na has been replaced by other cations such as Li, K, Ca, Mg, or ammonium.
  • Suitable zeolites are described, for example, in EP-A 0 038 591 , EP-A 0 021 491 , EP-A 0 087 035 , US patent 4,604,224 , GB-A 2 013 259 , EP-A 0 522 726 , EP-A 0 384 070 and WO-A-94/24 251 .
  • amorphous or crystalline silicates such as amorphous disilicates, crystalline disilicates, such as the sheet silicate SKS-6 (manufacturer: Hoechst).
  • the silicates may be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preference is given to the use of Na, Li and Mg silicates.
  • Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates) and aluminosilicates.
  • polyphosphates exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates
  • phosphonates phosphonates
  • phytic acid e.g., silicates, carbonates (including bicarbonates and sesquicarbonates) and aluminosilicates.
  • non-phosphate builders are required in some locales.
  • silicate builders are the alkali metal silicates, particularly those having a SiO 2 :Na 2 O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in US patent 4,664,839 .
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the NaSKS-6 silicate builder does not contain aluminium. NaSKS-6 has the Na 2 SiO 5 morphology form of layered silicate. It can be prepared by methods such as those described in DE-A-3,417,649 and DE-A-3,742,043 .
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x O 2x+1 .yH 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • the ⁇ Na 2 SiO 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in DE Patent application 2,321,001 .
  • WO 2005/052105 describes formulations which are essentially zeolite free, and which are based around carbonate and co-polymer as builder system.
  • EP patent 0 267 043 describes yet another approach to the use of carbonate as a builder via the use of seeded calcite to promote suspended calcium carbonate.
  • Aluminosilicate builders are particularly useful in the present invention being of great importance in most currently marketed heavy duty granular detergent compositions.
  • Aluminosilicate builders include those having the empirical formula: [M z (zAlO 2 )y].xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in US patent 3,985,669 . Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ].
  • xH 2 O wherein x is from about 20 to about 30, especially about 27.
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • Preferred polycarboxylates are organic polymers with pendant carboxylic acid groups. Typical examples include polymers of acrylic acid and copolymers of acrylic acid and maleic acid (suitable grades of both types of polymers for laundry detergents are commercially available from BASF in the Sokalan PA and CP ranges, eg Sokalan CP5). Further interesting organic polymers are polymers which may be biodegradeable, such as poly(aspartic acid) and poly(lactic acid). These polymers can be added as acids or as salts e.g. sodium, potassium or ammonium salts, and in general, even if added as acids, will be neutralized in the slurry or when post-dosed onto the detergent powder.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in US patent 3,128,287 , US patent 3,635,830 and the "TMS/TDS" builders of US patent 4,663,071 .
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in US patents 3,923,679 ; 3,835,163 ; 4,158,635 ; 4,120,874 and 4,102,903 .
  • ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance due to their availability from renewable resources and their biodegradability. Citrates can also be used in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C 5 -C 20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in EP Patent Application 0 200 263 .
  • Fatty acids e.g., C 12 -C 18 monocarboxylic acids
  • the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
  • polycarboxylates particularly amino polycarboxylates
  • examples would be ethylene diamine tetra acetic acid (EDTA) and especially the biodegradable chelants, such as salts and derivatives of disuccinic acid, such as ethylenediamine-N,N'-disuccinic acid (EDDS); iminodisuccinate (IDS) and hydroxyiminodisuccinate (HIDS).
  • EDTA ethylene diamine tetra acetic acid
  • biodegradable chelants such as salts and derivatives of disuccinic acid, such as ethylenediamine-N,N'-disuccinic acid (EDDS); iminodisuccinate (IDS) and hydroxyiminodisuccinate (HIDS).
  • compositions herein A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, soil release polymers.
  • Inorganic salts in addition to those discussed above can also be useful ingredients, in particular sodium, potassium, magnesium, calcium or aluminium salts of sulphate, carbonate, bicarbonate, citrate, silicate, which can be used alone or in any combination or ratio.
  • Inorganic salts not used as builders can play roles such as:
  • Suitable soil release polymers and/or grayness inhibitors for laundry detergents are the following:
  • polyester soil release polymers are supplied by Rhodia under the Repel-O-Tex trade mark, and BASF under the Sokolan SR trade mark.
  • soil release polymers are amphiphilic graft polymers or copolymers of vinyl and/or acrylic esters on polyalkylene oxides (see US patents 4,746,456 and 4,846,995 , DE-A 3 711 299 , US patents 4,904,408 , 4,846,994 and 4,849,126 ) or modified celluloses, such as methylcellulose, hydroxypropylcellulose or carboxymethylcellulose, for example.
  • Cotton soil release polymers are also beneficial, and modified polyethylene imines are described in US patent 6,121,226 . Ethoxylated polyethylene imines may be particularly useful.
  • softening agents which can optionally be added to the detergent powder to formulate a softening in the wash powder are clays especially the smectite clays of US patent 4,062,647 as well as other softener clays known in the art, can optionally be used typically at levels from about 0.5% to about 10% by weight to provide fabric softening concurrent with cleaning from a detergent powder or tablet.
  • Clay softeners can be used in combination with amine and cationic softeners as disclosed for example in US patent 4,375,416 and US patent 4,291,071 . They can also be used in conjunction with flocculating agents as taught in US patent 6,881,717 . All the above are incorporated herein by reference.
  • color transfer inhibitors used are homopolymers and copolymers of vinylpyrrolidone, of vinylimidazole, of vinyloxazolidone and of 4-vinylpyridine-N-oxide, having molecular masses of from 15 000 to 100 000, and also crosslinked, finely divided polymers based on these monomers. This use of such polymers is known and disclosed for example in DE-B 2 232 353 , DE-A 2 814 287 , DE-A 2 814 329 and DE-A 4 316 023 .
  • Natural polymers which can act as deposition aids or have a restoration benefit such as guar gum, locust bean gum, and xanthan gum or their derivatives as described in EP 1 141 195 and EP 1 141 196 .
  • Suitable enzymes are proteases, lipases, amylases, and cellulases.
  • the enzyme system may be confined to a single one of the enzymes or may comprise a combination of different enzymes.
  • foam boosters such as the C 10 -C 16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels.
  • the C 10 -C 14 monoethanol and diethanol amides illustrate a typical class of such foam boosters.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 10.5. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • the present invention can be used directly in low density powders (typically below 550 kgm -3 ) but may also be incorporated into high density granular compositions in which the density of the granule is at least 550 kgm -3 up to 1200 kgm -3 more particularly from 500 to 950 kgm -3 sometimes known as concentrated detergents or compact powders and also in laundry detergent tablets.
  • a typical (heavy duty) powder or granule laundry detergent of the invention, containing perfumes and benefit agents in the capsules, may have the following exemplary composition:
  • the process of the invention may also be used to formulate detergent tablets, or tablets with a gel layer which are used in domestic laundry.
  • Tablets contain many of the same ingredients of a detergent powder but the need to form the detergent into a tablet which will be mechanically stable yet disperse and dissolve quickly in water impose certain restrictions on the formulation as taught in International application WO 99/41353 and EP application 1 123 381 .
  • Many tablets are made from spray dried detergent powder which is mixed with other ingredients then compressed into a tablet and perhaps coated with a water soluble layer as described in US patent 6,358,911 , prior to packaging.
  • Compacting powders to make tablets may cause difficulty in retaining sprayed on liquid ingredients such as nonionic surfactant or perfume or adversely affect tablet disintegration and dissolution, so the incorporation of perfume or other liquid ingredients in an encapsulated form may be especially beneficial.
  • compositions may include particular forms of smectite clays and cationic agents as described in US patent 6,627,598 and cationic or nonionic softener molecules which may be salts of long chain tertiary amines.
  • Also provided herein is a method of delivering perfume to laundry which comprises the steps of taking the spray dried powder and adding it to a powder detergent composition or incorporating the capsules in a detergent slurry which, after spray drying provides a basic detergent powder to which other ingredients may be added either by liquid spray on as for example free fragrance or as solid granules as for example bleaching agents to formulate a commercial detergent powder and then the use of this detergent powder in a domestic clothes washing machine.
  • a 2 I cylindrical stirring vessel was fitted with an infinitely adjustable disperser having a standard commercial dispersion disk with a diameter of 50 mm.
  • This charge was processed to a capsule dispersion by adjusting the stirring speed to a peripheral speed of approximately 20 ms -1 .
  • the temperature was held at about 35°C.
  • the dispersion was oil-free; a particle size of about 5 ⁇ m had been established.
  • the stirring speed of the dispersion disk was then reduced to a level sufficient for uniform circulation of the vessel contents.
  • a cure temperature of 90°C was set, and once reached by injection of hot steam, a feed of a 27% suspension of melamine-urea (ratio 2.5:1, melamine:urea) in formic acid (to adjust pH to pH 4.5) was added to the dispersion of the preformed microcapsules with a constant mass flow rate and was metered in over the course of an hour. A total of 67 g of the suspension of melamine-urea was metered in.
  • the dispersion After the dispersion had been cooled to about 55°C, it was neutralized with diethanolamine and adjusted to a pH of 9.5 using ammonia.
  • slurry compositions for a zeolite built mixed non-ionic / anionic detergent powder such as is typical of many commercial formulations sold for use in front loading automatic washing machines in Europe.
  • the slurry was prepared and continuously agitated, and warmed to 80°C then spray dried in a 7 metre tower using a spinning disk for atomisation with an air inflow temperature of 220°C and outflow temperature of 80-95°C.
  • Examples 2 to 4 contain perfume capsules of different fragrance compositions while example A is the base powder to which free fragrance or encapsulated fragrance is added after spray drying. After a suitable storage period washes were carried out with all 3 invention formulations to demonstrate the survival and performance of the spray dried capsules.
  • the average particle diameter of the capsules was respectively 16 ⁇ m, 18 ⁇ m and 14 ⁇ m (Malvern Instrument).
  • a fresh slurry was made as above example A, and 10 g mixed with 0.06 g of the capsule dispersion of perfume composition n°1.
  • the headspace above 10 g of the fragranced slurry was sampled and analysed initially (time zero), and after 60 minutes by GC/MS.
  • a fresh slurry was also made as above example A, and 10g mixed with 0.02g of free perfume composition n°1, to provide a control of the headspace measurement, and was analysed in an identical fashion.
  • the samples were mixed gently and then stored without further agitation at 70°C, and subsequently analysed at 70°C.
  • a further 10 g sample of the slurry A was mixed with a starch capsule containing a mint fragrance provided by Takasago Europe GmbH ("Micronplus” TM ).
  • the headspace of that sample is measured by GC/MS initially and after 60 min. The sample was stored and analysed at 70°C.
  • Aminoplast capsules show a minimum leakage during slurry survival test while the starch capsules fail the "slurry survival test".
  • Example Z The composition of Example Z was made into a slurry by mixing with water at ambient temperature in the ratio 3:7 Composition Example Z: Water, and then spray dried with a Buchi B-290 to give a base powder. An identical procedure was followed with the composition of Example 6.
  • Supplier Example Z Wt %
  • Example 6 Wt % Sodium sulphate Aldrich 38 38 Nonionic 7EO Shell - Neodol 23-7 1.6
  • the base powder from Example 6 had 70% by weight of encapsulated fragrance remaining after the slurry and spray drying process.
  • the base powder from Example 6 is highly suitable as an adjunct for addition to many types of detergent powders for example for addition to non tower detergent compositions or to phosphate, carbonate or aluminosilicate based detergent powders.
  • Example 7 and comparative examples B and C show the amount of perfume remaining on a line dried cotton towelling glove (bath mitt) after washing.
  • the glove is washed in a linitester at 40°C for 45 minutes at a liquor to cloth ratio of 10:1 with a detergent concentration of 6.8 g/l of wash liquor, followed by 2 ambient rinses, and line drying.
  • Example B the Free Perfume of composition n°1 was dosed onto the powder of example Z. Perfume was incorporated at 0.64% by weight on the powder.
  • Example C is identical to example B except perfume is added via direct addition of the capsule dispersion of perfume composition n°1 to the powder of example Z. Perfume was incorporated at 0.64% by weight on the powder (some unencapsulated fragrance is present in the capsule dispersion). Note that these capsules were not spray dried in a detergent base.
  • Example 7 uses the spray dried powder of example 6 comprising 0.42% by weight of fragrance (after spray drying).
  • Example C shows that the use of encapsulated fragrance results in higher fragrance delivery to fabric after the wash, relative to the use of free fragrance.
  • Example 7 shows that after preparing a slurry and spray drying, despite some fragrance loss, there is still a considerable advantage for the use of encapsulated fragrance.
  • Example 8 and comparative examples D and E show the amount of perfume remaining on a line dried cotton towelling glove (bath mitt) after washing.
  • the glove is washed in a linitester at 40°C for 45 minutes at a liquor to cloth ratio of 10:1 with a detergent concentration of 6.8 g/l of wash liquor, followed by 2 ambient rinses, and line drying.
  • the perfume composition n°1 is dosed onto the powder of example A. Perfume was incorporated at 0.2 % by weight on the powder.
  • Example E is similar to example B except perfume is added via direct addition of the capsule dispersion of perfume composition n°1 to the powder of example A. Perfume was incorporated at 0.2 % by weight on the powder (some unencapsulated fragrance is present in the capsule dispersion). Note that these capsules were not spray dried in a detergent base.
  • Example 8 uses the spray dried powder of example 3 comprising 0.2 % by weight of fragrance (after spray drying).
  • Example D Example E
  • Example 8 Perfume composition n°1 available in wash 4 mg 4 mg 4mg (as recovered after spray-drying) % by weight recovered 8 17 25
  • Example E shows that the use of encapsulated fragrance results in higher fragrance delivery to fabric after the wash, relative to the use of free fragrance.
  • Example 8 shows that after preparing a slurry and spray drying there is a considerable advantage for the use of encapsulated fragrance.
  • Examples 9 to 13 demonstrate several detergent powder formulations in which the capsules can be included in the slurry prior to spray drying.
  • Examples 9 to 11 are conventional low bulk density powders having different builders whilst example 13 is a high bulk density powder generally known as a concentrated powder.
  • a second perfume may be post dosed to the detergent powder, and this may be the same fragrance as in the capsule but it may also have a different composition and odour.
  • Example 9 Wt % Example 10 Wt % Example 11 Wt % Example 12 Wt % Example 13 Wt % Ingredients added before spray drying Sodium Linear (C 11 -C 13 ) alkyl benzene sulphonate (Na-LAS) 8.5 11 11 8 3.0 Sodium (C 12 -C 15 ) alkyl 3-ethoxy sulphate (AES) 1.5 Alcohol ethoxylate Neodol 23 7EO (Shell) 6.5 3.5 3.5 5 Cationic Praepagen HY 1.3 1.5 Dequest 2060 (Monsanto) 0.6 Sodium linear (C 12 -C 18 ) Carboxylates 2 1 1.2 0.3 Zeolite A24 19.5 Zeolite A4 22 20 15.0 Sokolan CP5 ex BASF 1.7 3 1 2.0 polyacrylate (mw 5000) 3.5 Sodium citrate/citric acid 2.5 1.5 4 2 Sodium silicate 1.5 4.0 Sodium disilicate (SKS-6) 2.5 3.5 11 Sodium carbonate 18.5 1
  • Examples 14 to 17 demonstrate a range of slurry compositions which can be spray dried into detergent powders showing different surfactant types and builder.
  • the powder was slurried to give 30-60% by weight water at 80-85°C and spray dried with an air inlet temperatures between 200C- 350°C and outflow temperatures of 90-100°C.
  • Example 14 Hand wash powder Wt %
  • Example 15 Carbonate built Zero P powder Wt %
  • Example 16 Zeolite built powder Wt %
  • Example 17 Phosphate built powder Wt %
  • Anhydrous sodium sulphate 3.0 42.0 20.3 29.74 Anhydrous sodium carbonate 45.0 33.0 10.0 8.0
  • Zeolite A4 32.0 Anhydrous sodium tripolyphosphate 22 Sodium Linear (C 11 -C 13 ) alkyl benzene sulphonate (Na-LAS) 28.0 18.0 9.0 Alcohol ethoxylate Neodol 23- 7EO ex Shell 2.6
  • Post addition 4.0 Perfume composition n°1 encapsulated as in example 1 0.26 0.26 0.26 0.26 Moisture and minors to 100% to 88% to 88% to 93% Post dosed ingredients Nil 12% 12% 7%
  • bleaches bleach precursors, enzymes, certain surfactants, builders, antifoam agents, anti-redeposition agents, fabric care polymers, fluorescers, photobleaches, and free fragrance can all be added to any of these compositions after spray drying.
  • Capsule dispersions of perfume compositions n°1 to n°3 were directly spray dried with a Buchi B-290 to give powders which was essentially 100% dry capsules. A weighed amount of these dry capsules was placed in a temperature controlled oven at 200°C and after 10 minutes the temperature was increased by 10°C. This procedure was repeated to 260°C. The samples were weighed after each temperature increment and in all case the final weight loss was less than 5%.
  • fragrance composition (perfume composition n° 4) was encapsulated as per Example 1, then a slurry prepared and spray dried as per Example 6.
  • Perfume Composition N° 4 CAS No Wt % Iso amyl alcohol* 123-51-3 10 Butyl acetate* 123-86-4 5 Phenyl ethyl alcohol* 60-12-8 35 Veltol Plus* 4940-11-8 1 Cinnamic Alcohol* 104-54-1 9

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Fats And Perfumes (AREA)
EP06121132A 2005-09-23 2006-09-22 Verfahren zur Herstellung eines sprühgetrockneten Pulvers Withdrawn EP1767614A1 (de)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2301517A1 (de) * 2006-08-01 2011-03-30 The Procter & Gamble Company Pflegemittel enthaltender Freisetzungspartikel
WO2018030431A1 (en) 2016-08-09 2018-02-15 Takasago International Corporation Solid composition comprising free and encapsulated fragrances
CN110785481A (zh) * 2017-06-20 2020-02-11 荷兰联合利华有限公司 包含香料的颗粒洗涤剂组合物
CN113631695A (zh) * 2019-04-17 2021-11-09 宝洁公司 胶囊
US11912961B2 (en) 2020-10-16 2024-02-27 The Procter & Gamble Company Liquid fabric care compositions comprising capsules
US11938349B2 (en) 2020-10-16 2024-03-26 The Procter & Gamble Company Antiperspirant and deodorant compositions comprising capsules
US12077728B2 (en) 2020-10-16 2024-09-03 The Procter & Gamble Company Laundry care additive particles

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4234627A (en) * 1977-02-04 1980-11-18 The Procter & Gamble Company Fabric conditioning compositions
WO1993013195A1 (en) * 1991-12-20 1993-07-08 The Procter & Gamble Company A process for preparing a perfume capsule composition
US6849591B1 (en) * 1999-07-09 2005-02-01 Basf Aktiengesellschaft Microcapsule preparations and detergents and cleaning agents containing microcapsules
WO2005059083A1 (en) * 2003-12-19 2005-06-30 Unilever N.V. Detergent granules and process for their manufacture

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4234627A (en) * 1977-02-04 1980-11-18 The Procter & Gamble Company Fabric conditioning compositions
WO1993013195A1 (en) * 1991-12-20 1993-07-08 The Procter & Gamble Company A process for preparing a perfume capsule composition
US6849591B1 (en) * 1999-07-09 2005-02-01 Basf Aktiengesellschaft Microcapsule preparations and detergents and cleaning agents containing microcapsules
WO2005059083A1 (en) * 2003-12-19 2005-06-30 Unilever N.V. Detergent granules and process for their manufacture

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2301517A1 (de) * 2006-08-01 2011-03-30 The Procter & Gamble Company Pflegemittel enthaltender Freisetzungspartikel
WO2018030431A1 (en) 2016-08-09 2018-02-15 Takasago International Corporation Solid composition comprising free and encapsulated fragrances
CN110785481A (zh) * 2017-06-20 2020-02-11 荷兰联合利华有限公司 包含香料的颗粒洗涤剂组合物
CN110785481B (zh) * 2017-06-20 2021-04-13 荷兰联合利华有限公司 包含香料的颗粒洗涤剂组合物
CN113631695A (zh) * 2019-04-17 2021-11-09 宝洁公司 胶囊
US11904287B2 (en) 2019-04-17 2024-02-20 The Procter & Gamble Company Capsules
US11912961B2 (en) 2020-10-16 2024-02-27 The Procter & Gamble Company Liquid fabric care compositions comprising capsules
US11938349B2 (en) 2020-10-16 2024-03-26 The Procter & Gamble Company Antiperspirant and deodorant compositions comprising capsules
US12077728B2 (en) 2020-10-16 2024-09-03 The Procter & Gamble Company Laundry care additive particles

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