WO2001040430A1 - Systeme de liberation dote d'un support poreux encapsule charge d'additifs, notamment d'additifs detergents tels que des parfums - Google Patents

Systeme de liberation dote d'un support poreux encapsule charge d'additifs, notamment d'additifs detergents tels que des parfums Download PDF

Info

Publication number
WO2001040430A1
WO2001040430A1 PCT/IB2000/001755 IB0001755W WO0140430A1 WO 2001040430 A1 WO2001040430 A1 WO 2001040430A1 IB 0001755 W IB0001755 W IB 0001755W WO 0140430 A1 WO0140430 A1 WO 0140430A1
Authority
WO
WIPO (PCT)
Prior art keywords
perfume
additive
zeolite
particle
coating material
Prior art date
Application number
PCT/IB2000/001755
Other languages
English (en)
Inventor
Edgar Manuel Marin
Jose Maria Velazquez
Jiten Odhavji Dihora
Roberto Garciagonzalez
Gaurav Saini
Original Assignee
The Procter & Gamble Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to HU0203565A priority Critical patent/HUP0203565A3/hu
Priority to JP2001541168A priority patent/JP2003515664A/ja
Priority to AU14082/01A priority patent/AU759299B2/en
Priority to US10/148,760 priority patent/US6790814B1/en
Priority to MXPA02005445A priority patent/MXPA02005445A/es
Priority to EP00976207A priority patent/EP1234015A1/fr
Priority to BR0015971-9A priority patent/BR0015971A/pt
Priority to CA002390382A priority patent/CA2390382A1/fr
Publication of WO2001040430A1 publication Critical patent/WO2001040430A1/fr

Links

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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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 delivery particles, particularly to particles for the delivery of laundry additives, such as perfume agents, and detergent compositions including the delivery particles, especially granular detergents.
  • a detergent composition comprising a perfume which can provide a "sun-dried type" of odor has now been found.
  • Laundry and other fabric care compositions which contain perfume mixed with or sprayed onto the compositions are well known from commercial practice. Because perfumes are made of a combination of volatile compounds, perfume can be continuously emitted from simple solutions and dry mixes to which the perfume has been added. Various techniques have been developed to hinder or delay the release of perfume from compositions so that they will remain aesthetically pleasing for a longer length of time. To date, however, few of the methods deliver significant fabric odor benefits after prolonged storage of the product.
  • Another method for delivery of perfume in the wash cycle involves combining the perfume with an emulsifier and water-soluble polymer, forming the mixture into particles, and adding them to a laundry composition, as is described in U.S. Pat. 4,209,417, Whyte, issued June 24, 1980; U.S. Pat. 4,339,356, Whyte, issued July 13, 1982; and U.S. Pat. No. 3,576,760, Gould et al, issued April 27, 1971.
  • the perfume can also be adsorbed onto a porous carrier material, such as a polymeric material, as described in U.K. Pat. Pub. 2,066,839, Bares et al, published July 15, 1981.
  • a porous carrier material such as a polymeric material, as described in U.K. Pat. Pub. 2,066,839, Bares et al, published July 15, 1981.
  • Perfumes have also been adsorbed onto a clay or zeolite material which is then admixed into particulate detergent compositions.
  • the preferred zeolites have been Type A or 4A Zeolites with a nominal pore size of approximately 4 Angstrom units. It is now believed that with Zeolite A or 4A, the perfume is adsorbed onto the zeolite surface with relatively little of the perfume actually absorbing into the zeolite pores.
  • compositions are taught by WO 94/28107, published December 8, 1994 by The Procter & Gamble Company. These compositions comprise zeolites having pore size of at least 6 Angstroms (e.g., Zeolite X or Y), perfume releaseably incorporated in the pores of the zeolite, and a matrix coated on the perfumed zeolite, the matrix comprising a water-soluble (wash removable) composition comprising from 0% to about 80%, by weight, of at least one solid polyol containing more than 3 hydroxyl moieties and from about 20% to about 100%), by weight, of a fluid diol or polyol, in which the perfume is substantially insoluble and in which the solid polyol is substantially soluble.
  • zeolites having pore size of at least 6 Angstroms (e.g., Zeolite X or Y)
  • perfume releaseably incorporated in the pores of the zeolite e.g., Zeolite X or Y
  • WO 97/34982 discloses particles comprising perfume loaded zeolite and a release barrier, which is an agent derived from a wax and having a size (i.e., a cross-sectional area) larger than the size of the pore openings of the zeolite carrier.
  • WO 98/41607 discloses glassy particles comprising agents useful for laundry or cleaning compositions and a glass derived from one or more of at least partially-water-soluble hydroxylic compounds.
  • a preferred agent is a perfume in a zeolite carrier.
  • porous carriers such as zeolite particles
  • perfume loaded into porous carriers can be effectively protected from premature release of perfume by coating said loaded carrier particles with a hydrophobic oil and thereafter encapsulating the oil-coated perfume-loaded carrier particles with a water-soluble or water-dispersible, but oil-insoluble, material, such as starch or modified starch.
  • the porous carrier may be selected to be substantive to fabrics to be able to deposit enough perfume on the fabrics to deliver a noticeable odor benefit even after the fabrics are dry.
  • the present invention solves the long-standing need for a simple, effective, storage-stable perfume delivery system which provides consumer-noticeable odor benefits during and after the laundering process, and which has reduced product odor during storage of the composition.
  • fabrics treated by the present perfume delivery system have higher scent intensity and remain scented for longer periods of time after laundering and drying.
  • the present invention also provides a delivery system for other additives, which are desirably protected from release until the product comprising the additive is exposed to a wet or moist environment.
  • the present invention relates to a delivery system for additives, which are incorporated in a variety of consumer products, including detergents and cleaning compositions, room deodorizers, insecticidal compositions, carpet cleaners and deodorizers wherein the additive is protected from release until exposed to a wet or moist environment.
  • the present additive delivery system is a particle comprising a core of a porous carrier material containing an additive, such as a perfume, in its pores; a first coating of a hydrophobic oil encapsulating said core, and a second coating of a water-soluble or water-dispersible, but oil-insoluble, material, such as starch or modified starch, encapsulating the hydrophobic-oil coated core.
  • the present delivery particle can be used to deliver laundry and cleaning agents either to or through the wash cycle.
  • a laundry additive delivery particle according to the present invention effectively delivers perfume ingredients through the wash to a fabric surface.
  • the porous carrier material is typically selected from zeolites, macroporous zeolites, amorphous silicates, crystalline nonlayer silicates, layer silicates, calcium carbonates, calcium/sodium carbonate double salts, sodium carbonates, clays, sodalites, alkali metal phosphates, chitin microbeads, carboxyalkylcelluloses, carboxyalkylstarches, cyclodextrins, porous starches, and mixtures thereof.
  • the carrier material is a zeolites such as Zeolite X, Zeolite Y, and mixtures thereof.
  • Particularly preferred porous carriers are zeolite particles with a nominal pore size of at least about 6 Angstroms to effectively incorporate perfume into their pores. Without wishing to be limited by theory, it is believed that these zeolites provide a channel or cage-like structure in which the perfume molecules are trapped. Unfortunately, such perfumed zeolites are not sufficiently storage-stable for commercial use in granular fabric care products such as laundry detergents, particularly due to premature release of perfume upon moisture absorption.
  • the perfume-loaded zeolite can first be coated with a hydrophobic oil to protect the zeolite particles by forming a protective barrier to entrap and maintain the perfume within the zeolite's pores, and thereafter encapsulating the oil-coated particle with a water-soluble or water-dispersible, but oil-insoluble, material.
  • the perfume substantially remains within the pores of the zeolite particles. It is also believed that since the perfume is incorporated into the relatively large zeolite pores, it has better perfume retention through the laundry process than other smaller pore size zeolites in which the perfume is predominately adsorbed on the zeolite surface.
  • the hydrophobic oil coating can be a non-perfume oil but is preferably a perfume which can be the same as or different from the perfume oil loaded into the carrier. It is believed that when the present encapsulated particle is added to water, such as during laundering, the water-soluble or water-dispersible encapsulating material dissolves and starts to release the oil coating. When this oil coating is a perfume, the perfume notes are released from the wash solution, providing the wet odor benefit . The carrier particles loaded with perfume are released in the wash solution and deposit onto fabrics. After the fabrics are dried, perfume is released from the carrier as moisture in the atmosphere displaces the perfume contained in the pores of the carrier, providing the dry odor benefit.
  • the additive contained in the porous carrier core is preferably selected from the group consisting of perfumes, bleaches, bleach promoters, bleach activators, bleach catalysts, chelants, antiscalants, dye transfer inhibitors, photobleaches, enzymes, catalytic antibodies, brighteners, fabric-substantive dyes, antifungals, antimicrobials, insect repellents, soil release polymers, fabric softening agents, dye fixatives, pH jump systems, and mixtures thereof.
  • the preferred laundry additive to be loaded into the porous carrier material is a perfume.
  • the particle core is a perfume-loaded zeolite (PLZ).
  • the preferred encapsulating material is a starch, modified starch or starch hydrolysate while the preferred oil coating material is a perfume oil.
  • the external encapsulating material may further include an ingredient selected from the group consisting of plasticizers, anti-agglomeration agents, and mixtures thereof.
  • a laundry or cleaning detergent composition is provided.
  • the laundry or cleaning composition comprises from about 0.001% to about 50% by weight of the composition of the laundry additive particle as described above and from about 50% to about 99.999% by weight of the composition of laundry ingredients selected from the group consisting of detersive surfactants, builders, bleaching agents, enzymes, soil release polymers, dye transfer inhibitors, fillers and mixtures thereof.
  • the composition includes at least one detersive surfactant and at least one builder.
  • an additive delivery particle having a core loaded with an additive, preferably a laundry additive such as a perfume, and at least two surface coatings comprising an intermediate hydrophobic oil coating and an external encapsulating coating of a water-soluble or water-dispersible material. It is another object of the present invention to provide a laundry and cleaning composition having said laundry additive particle thereon. It is a further object of the present invention to provide a laundry additive particle which can provide improved fabric odor benefits, prolong storage life capabilities, and reduce product odor intensity.
  • Figure 1 shows a SEM of an intact average sized laundry additive particle comprising an encapsulated perfume-loaded zeolite particle according to the present invention.
  • Figure 2 shows a SEM of a cross-section of a particle according to the present invention, containing loaded zeolite particles inside a starch coating.
  • the present invention relates to a laundry additive particle and to laundry and cleaning compositions comprising the laundry additive particle, which is preferably a perfume- containing particle.
  • Laundry and cleaning compositions include traditional granular laundry detergents as well as granular bleach, automatic dishwashing, hard surface cleaning, and fabric softening compositions.
  • the laundry additive particle of the present invention provides superior through the wash perfume delivery capabilities as well as minimizes product odor due to evolving volatile perfume ingredients. While not wishing to be bound by theory, it is also believed that the specified coatings of the particle of the present invention increase the stability of the particle.
  • the preferred laundry particle of the present invention comprises a core of a porous carrier loaded with perfume, said loaded core being first coated with a hydrophobic oil material and thereafter encapsulated with an external coating of a water-soluble or water- dispersible, but oil-insoluble, material, such as starch or modified starch, to form the final particle.
  • the laundry additive particles of the present invention have a hygroscopicity value of less than about 80%.
  • the "hygroscopicity value”, as used herein, means the level of moisture uptake by the particles, as measured by the percent increase in weight of the particles under the following test method.
  • the hygroscopicity value required for the present invention particles is determined by placing 2 grams of particles in an open container petri dish under conditions of 90°F and 80% relative humidity for a period of 4 weeks. The percent increase in weight of the particles at the end of this time is the particles' hygroscopicity value as used herein.
  • Preferred particles of the present invention have a hygroscopicity value of less than about 50%, more preferably less than about 30%.
  • the laundry additive particles of the present invention typically comprise from about 5% to about 50% of the loaded central core particle which itself is about 60% to about 99% porous carrier and about 1% to about 40% perfume or other laundry additive material, from about 1% to about 40% of hydrophobic oil intermediate coating material, and from about 10% to about 94% external encapsulating material.
  • the central core of the additive particle comprises a porous carrier material and a laundry additive loaded into said carrier material.
  • the two ingredients of the central core may be mixed in a number of different ways.
  • Procedure consists of placing the carrier material particles (zeolite) in the equipment and pouring the laundry additive at the same time that mixing occurs. Mixing time is from 0.5 to 15 minutes. The loaded carrier material (zeolite) is then allowed to rest for a period from 0.5 to 48 hours before further processing. During the loading process when heating occurs, cool jacketing may be used as an option.
  • suitable equipment is a mixer of the Littleford type, which is a batch type mixer with plows and chopper blades that operate at high RPM's, to continuously mix the powder or mixture of powders while liquid perfume oil is being sprayed thereon.
  • the porous carrier material means any material capable of supporting (e.g., by adsorption into the pores) a deliverable agent such as a laundry or cleaning agent.
  • a deliverable agent such as a laundry or cleaning agent.
  • Such materials include porous solids such as zeolites.
  • zeolites are selected from zeolite X, zeolite Y and mixtures thereof.
  • zeolite used herein refers to a crystalline aluminosilicate material.
  • the structural formula of a zeolite is based on the crystal unit cell, the smallest unit of structure represented by
  • n is the valence of the cation M
  • x is the number of water molecules per unit cell
  • m and y are the total number of tetrahedra per unit cell
  • y/m is 1 to 100. Most preferably, y/m is 1 to 5.
  • the cation M can be Group IA and Group IIA elements, such as sodium, potassium, magnesium, and calcium.
  • a zeolite useful herein is a faujasite-type zeolite, including Type X Zeolite or Type Y Zeolite, both with a pore size typically in the range of from about 4 to about 10 Angstrom units, preferably about 8 Angstrom units.
  • aluminosilicate zeolite materials useful in the practice of this invention are commercially available. Methods for producing X and Y-type zeolites are well- known and available in standard texts. Preferred synthetic crystalline aluminosilicate materials useful herein are available under the designation Type X or Type Y.
  • the crystalline aluminosilicate material is Type X and is selected from the following:
  • the crystalline aluminosilicate material is Type Y and is selected from the following:
  • Zeolite MAP the class of zeolites known as, "Zeolite MAP" may also be employed in the present invention.
  • Zeolite MAP Such zeolites are disclosed and described in U.S. Patent Application Serial No. 08/716,147 filed September 16, 1996 and entitled, "Zeolite MAP and Alcalase for Improved Fabric Care.”
  • Zeolites used in the present invention are in particle form having an average particle size from about 0.5 microns to about 120 microns, preferably from about 0.5 microns to about 30 microns, as measured by standard particle size analysis technique.
  • the size of the zeolite particles allows them to be entrained in the fabrics with which they come in contact. Once established on the fabric surface (with the coatings having been washed away during the laundry process), the zeolites can begin to release their incorporated laundry agents, especially when subjected to heat or humid conditions.
  • the intermediate oil coating material forms a coating on the central core particle.
  • the intermediate coating provides a barrier to minimize release or leakage of any deliverable agent, such as a perfume, incorporated into the porous carrier.
  • the intermediate coating material comprises a hydrophobic oil such as a perfume oil which can be the same as or different from the perfume loaded into the carrier, or a non-perfume oil, such as mineral oil.
  • the hydrophobic oil can be one or a mixture of organic compounds, preferably having a weighted average ClogP lower than the weighted average ClogP of the additive material or mixture loaded in the pores of the carrier. ClogP values are typically used to characterize perfume ingredients, i.e., by their octanol/water partition coefficient P.
  • the octanol/water partition coefficient of a perfume ingredient is the ratio between its equilibrium concentration in octanol and in water.
  • the intermediate oil coating material is thus preferably less hydrophobic than the additive material contained in the porous carrier.
  • the highest ClogP of the material comprising the hydrophobic oil coating is lower than the lowest ClogP of the material comprising the additive loaded in the porous carrier. Even more preferably, there is a difference of at least one unit and most preferably, two units between the highest ClogP of the hydrophobic oil coating material and the lowest ClogP of the loaded additive material.
  • the external encapsulating material is coated on the intermediate coating material which is coated on the core particle and provides the outer layer of the final particle.
  • the external coating material provides a substantially non-tacky or non-sticky coating for the final particle.
  • the external coating provides a particle which will have a non- tacky surface in high humidity conditions such as 80% relative humidity at 90 °F.
  • the external coating is a material derived from one or more at least partially wash- soluble or dispersible compounds. That is, the external coating will either be soluble in an aqueous wash environment or be dispersible in that aqueous wash environment.
  • the compounds useful herein are preferably selected from the following classes of materials.
  • Carbohydrates which can be any or a mixture of: i) Starches including modified starches and starch hydrolysates; ii) Oligosaccharides (defined as carbohydrate chains consisting of 2-35 monosaccharide molecules); iii) Polysaccharides (defined as carbohydrate chains consisting of at least 35 monosaccharide molecules); and iv) Simple sugars (or monosaccharides); and v) hydrogenates of i), ii), iii), and iv).
  • Both linear and branched carbohydrate chains may be used.
  • chemically modified starches and poly-/oligo-saccharides may be used. Typical modifications include the addition of hydrophobic moieties of the form of alkyl, aryl, etc. identical to those found in surfactants to impart some surface activity to these compounds.
  • All natural or synthetic gums such as alginate esters, carrageenin, agar-agar, pectic acid, and natural gums such as gum arabic, gum tragacanth and gum karaya.
  • Cellulose and cellulose derivatives examples include: i) Cellulose acetate and Cellulose acetate phthalate (CAP); ii) Hydroxypropyl Methyl Cellulose (HPMC); iii)Carboxymethylcellulose (CMC); iv) all enteric/aquateric coatings and mixtures thereof.
  • CAP Cellulose acetate and Cellulose acetate phthalate
  • HPMC Hydroxypropyl Methyl Cellulose
  • CMC Carboxymethylcellulose
  • Water soluble polymers including polyacrylates, caprolactones, Polyvinyl alcohol (PVA) and Polyethylene glycol (PEG).
  • Waxes including silicone waxes, paraffinic waxes, and microcrystalline waxes.
  • Long Chain (C10-C35) fatty compounds including fatty acids, fatty alcohols and fatty esters.
  • Natural proteins including gelatin, casein and egg albumin.
  • Materials within these classes which are not at least partially wash soluble or dispersible are useful herein only when mixed in such amounts with the compounds useful herein such that the particle produced has the preferred hygroscopicity value of less than about 80%. It is also preferred that these compounds be low temperature processable, preferably within the range of from about 50 °C to about 200 °C, and more preferably within the range of from about 60 °C to about 180 °C.
  • Preferred encapsulating materials are starches or modified starches such as CAPSULTM commercially available from National Starch, cellulose and cellulose derivatives such as hydroxy propyl methyl cellulose, other carbohydrates such as sucrose and fructose, natural polymers such as gum arabic and guar gum, natural proteins, and water-soluble polymers such as polyethylene glycol.
  • CAPSULTM commercially available from National Starch
  • cellulose and cellulose derivatives such as hydroxy propyl methyl cellulose
  • other carbohydrates such as sucrose and fructose
  • natural polymers such as gum arabic and guar gum
  • natural proteins such as polyethylene glycol
  • the external encapsulation coating may include optional additive ingredients such as plasticizers, anti-agglomeration agents, and mixtures thereof.
  • the optional plasticizers include sorbitol, polyethylene glycol, propylene glycol, low molecular weight carbohydrates and the like with a mixture of sorbitol and polyethylene glycol and low molecular weight polyols being the most preferred.
  • the plasticizer is employed at levels of from about 0.01% to about 5%.
  • the anti-agglomeration agents according to the present invention are preferably surfactants and are included at low levels of less than 1% of the external coating. Suitable surfactants for use in the present invention include TWEENTM 80 commercially available from Imperial Chemicals, Inc. (ICI).
  • Laundry and cleaning additives or agents are included in the particle of the present invention.
  • the agents are contained in the porous carrier material as hereinbefore described.
  • agents which are incorporated into the particles of the present invention may be the same as or different from those agents which are typically used to formulate the remainder of the laundry and cleaning compositions containing the particle.
  • the particle may comprise a perfume agent and (the same or different) perfume may also be blended into the final composition (such as by spray-on techniques) along with the perfume-containing particle.
  • These agents are selected as desired for the type of composition being formulated, such as granular laundry detergent compositions, granular automatic dishwashing compositions, or hard surface cleaners.
  • the laundry particle of the present invention may of course be included in a composition which may contain other ingredients.
  • the compositions containing laundry additive particles can optionally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.).
  • the preferred laundry or cleaning additive according to the present invention is a perfume material.
  • perfume is used to indicate any odoriferous material which is subsequently released into the aqueous bath and/or onto fabrics or other surfaces contacted therewith.
  • the perfume will most often be liquid at ambient temperatures.
  • materials such as aldehydes, especially C 6 -C ⁇ 4 aliphatic aldehydes, C 6 -C ⁇ acyclic terpene aldehydes and mixtures thereof, ketones, alcohols and esters. More commonly, naturally occurring plant and animal oils and exudates comprising complex mixtures of various chemical components are known for use as perfumes.
  • the perfumes herein can be relatively simple in their compositions or can comprise highly sophisticated complex mixtures of natural and synthetic chemical components, all chosen to provide any desired odor.
  • Typical perfumes can comprise, for example, woody/earthy bases containing exotic materials such as sandalwood, civet and patchouli oil.
  • the perfumes can be of a light floral fragrance, e.g., rose extract, violet extract, and lilac.
  • the perfumes can also be formulated to provide desirable fruity odors, e.g., lime, lemon, and orange. Any chemically compatible material which exudes a pleasant or otherwise desirable odor can be used in the perfumed compositions herein.
  • the perfume component is selected from the group consisting of C 6 -C] 4 aliphatic aldehydes, C 6 -C ⁇ 4 acyclic terpene aldehyde and mixtures thereof.
  • the perfume component is selected from C 8 -C ⁇ 2 aliphatic aldehydes, C 8 -C ⁇ 2 acyclic terpene aldehydes and mixtures thereof.
  • the perfume component is selected from the group consisting of citral; neral; iso-citral; dihydro citral; citronellal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2- methyl decanal; methyl nonyl acetaldehyde; 2-nonen-l-al; decanal; undecenal; undecylenic aldehyde; 2, 6 dimethyl octanal; 2, 6, lO-trimethyl-9-undecen-l-al; trimethyl undecanal; dodecenal; melonal; 2-methyl octanal; 3, 5, 5, trimethyl hexanal and mixtures thereof.
  • the preferable mixtures are, for example, a mixture comprising 30% by weight of 2-nonen-l-al, 40% by weight of undecylenic aldehyde and 30% by weight of citral or a mixture comprising 20% by weight of methyl nonyl acetaldehyde, 25% by weight of lauric aldehyde, 35% by weight of decanal and 20% by weight of 2-nonen-l-al.
  • a "sun dried odor" is produced on the fabric even though the fabric is not actually dried in the sun.
  • the "sun dried” odor is formed by selecting aldehydes such that at least one of them is present naturally in cotton fabrics after the fabric is dried in the sun and thus, are a component of the sun dried odor.
  • Perfumes also include pro-fragrances such as acetal pro-fragrances, ketal pro-fragrances, ester pro-fragrances (e.g., digeranyl succinate), hydrolyzable inorganic-organic pro- fragrances, and mixtures thereof.
  • pro-fragrances may release the perfume material as a result of simple hydrolysis, or may be pH-change-triggered pro-fragrances (e.g., pH drop) or may be enzymatically releasable pro-fragrances.
  • Preferred perfume agents useful herein are defined as follows.
  • perfume agents are those which have the ability to be incorporated into the pores of the carrier, and hence their utility as components for delivery from the carrier through an aqueous environment.
  • Commonly-owned WO 98/41607 describes the characteristic physical parameters of perfume molecules which affect their ability to be incorporated into the pores of a carrier, such as a zeolite.
  • a carrier such as a zeolite.
  • perfume delivery particles the preferred perfume agents have a threshold of noticeability (measured as odor detection thresholds ("ODT") under carefully controlled GC conditions as described in detail hereinafter) less than or equal to 50 parts per billion (“ppb").
  • Laundry agent perfume mixtures useful for the present invention perfume delivery particles preferably comprise from about 0% to about 80% of deliverable agents with ODTs above 50 ppb up to 1 ppm, and from about 20% to about 100% (preferably from about 30% to about 100%; more preferably from about 50% to about 100%) of deliverable agents with ODTs less than or equal to 50 ppb.
  • perfumes carried through the laundry process and thereafter released into the air around the dried fabrics e.g., such as the space around the fabric during storage. This requires movement of the perfume out of the zeolite pores with subsequent partitioning into the air around the fabric.
  • Preferred perfume agents are therefore further identified on the basis of their volatility. Boiling point is used herein as a measure of volatility and preferred materials have a boiling point less than 300 °C.
  • Laundry agent perfume mixtures useful for the present invention laundry particles preferably comprise at least about 50% of deliverable agents with boiling point less than 300 °C (preferably at least about 60%; more preferably at least about 70%).
  • preferred perfume delivery particles herein for use in laundry detergents comprise compositions wherein at least about 80%, and more preferably at least about 90%, of the deliverable perfume agents have a weighted average ClogP value ranging from about 1.0 to 16, and more preferably from about 2.0 to about 8.0. Most preferably, the deliverable perfume agents or mixtures have a weighted average ClogP value between 3 and 4.5. While not wishing to be bound by theory, it is believed that perfume materials having the preferred ClogP values are sufficiently hydrophobic to be held inside the pores of the zeolite carrier and deposited onto fabrics during the wash, yet are able to be released from the zeolite pores at a reasonable rate from dry fabric to provide a noticeable benefit. ClogP values are obtained as follows. Calculation of ClogP:
  • perfume ingredients are characterized by their octanol/water partition coefficient P.
  • the octanol/water partition coefficient of a perfume ingredient is the ratio between its equilibrium concentration in octanol and in water. Since the partition coefficients of most perfume ingredients are large, they are more conveniently given in the form of their logarithm to the base 10, logP.
  • logP logP
  • ClogP The "calculated logP” (ClogP) is determined by the fragment approach of Hansch and Leo (cf., A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P.G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990).
  • the fragment approach is based on the chemical structure of each perfume ingredient and takes into account the numbers and types of atoms, the atom connectivity, and chemical bonding.
  • the ClogP values which are the most reliable and widely used estimates for this physicochemical property, can be used instead of the experimental logP values in the selection of perfume ingredients.
  • the gas chromatograph is characterized to determine the exact volume of material injected by the syringe, the precise split ratio, and the hydrocarbon response using a hydrocarbon standard of known concentration and chain-length distribution.
  • the air flow rate is accurately measured and, assuming the duration of a human inhalation to last 0.2 minutes, the sampled volume is calculated. Since the precise concentration at the detector at any point in time is known, the mass per volume inhaled is known and hence the concentration of material.
  • solutions are delivered to the sniff port at the back-calculated concentration. A panelist sniffs the GC effluent and identifies the retention time when odor is noticed. The average over all panelists determines the threshold of noticeability.
  • the perfume can be combined with a perfume fixative.
  • the perfume fixative materials employed herein are characterized by several criteria which make them especially suitable in the practice of this invention. Dispersible, toxicologically-acceptable, non-skin irritating, inert to the perfume, degradable and/or available from renewable resources, and relatively odorless additives are used. Perfume fixatives are believed to slow the evaporation of more volatile components of the perfume.
  • suitable fixatives include members selected from the group consisting of diethyl phthalate, musks, and mixtures thereof. If used, the perfume fixative comprises from about 10% to abut 50%, preferably from about 20% to about 40%, by weight, of the perfume.
  • the Type X or Type Y Zeolites to be used as the preferred carrier herein preferably contain less than about 15% desorbable water, more preferably less than about 8% desorbable water, and most preferably less than about 5% desorbable water.
  • Such materials may be obtained by first activating/dehydrating by heating to about 150 to 350 °C, optionally with reduced pressure (from about 0.001 to about 20 Torr). After activation, the agent is slowly and thoroughly mixed with the activated zeolite and, optionally, heated to about 60°C or up to about 2 hours to accelerate absorption equilibrium within the zeolite particles. The perfume/zeolite mixture is then cooled to room temperature and is in the form of a free-flowing powder.
  • the amount of perfume or other laundry additive incorporated into the zeolite carrier is typically from 1% to 40%, preferably at least about 10%, more preferably at least about 18.5%, by weight of the loaded particle, given the limits on the pore volume of the zeolite. It is to be recognized, however, that the present invention particles may exceed this level of laundry additive by weight of the particle, but recognizing that excess levels of laundry additives will not be incorporated into the zeolite, even if only deliverable agents are used. Therefore, the present invention particles may comprise more than 40% by weight of laundry agents. Since any excess laundry agents (as well as any non- deliverable agents present) are not incorporated into the zeolite pores, these materials are likely to be immediately released to the wash solution upon contact with the aqueous wash medium.
  • perfume-loaded zeolite particles in the form of a free-flowing powder are thoroughly coated with a hydrophobic oil such as mineral oil or perfume oil.
  • a hydrophobic oil such as mineral oil or perfume oil.
  • the hydrophobic-oil coated particles are mixed to a solution of modified starch (CAPSULTM, National Starch & Chemicals) and agitated to form an emulsion.
  • the emulsion is then spray-dried using a spray dryer having a spraying system such as co-current with a spinning disk, with vaneless disk, with vaned disk or wheel or with two-fluid mist spray nozzle.
  • Typical conditions involve an inlet temperature of from about 120 °C to about 220 °C and an outlet temperature of from about 50 °C to about 220 °C.
  • the present laundry additive delivery particles are discrete particles having particle size of from about 3 to about 100 microns as measured by standard particle size analysis technique.
  • Figure 1 shows a SEM of an intact average sized encapsulated perfume- loaded zeolite particle according to the present invention.
  • Figure 2 shows a cross-section of a particle according to the present invention, containing loaded zeolite particles inside a starch coating.
  • Samples of encapsulated perfume-loaded zeolite particles are kept in open jars at 80 °F and 70% Relative Humidity and in sealed plastic bags at 120 °F for ten days. After that period the samples are taken out and evaluated organoleptically. Particles are homogenized and dosed according to regional real washing conditions. They are mixed with odorless base granule, previously approved for this kind of test. Original particles (which are not subjected to stability testing conditions) are included as reference. Perfume intensity scores for the particles are registered in terms of Dry Fabric Odor. Particles with perfume loaded zeolite are able to provide between 5 points to 20 points of advantage, in a perfume intensity scale, compared against control with sprayed on perfume alone.
  • Adjunct ingredients useful in the laundry or cleaning compositions according to the present invention include surfactants, builders, and agents such as those which are incorporated into the present delivery particles.
  • the various types of agents useful in laundry and cleaning compositions are described hereinafter.
  • the compositions containing particulate compositions can optionally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition.
  • the granules and/or the agglomerates include surfactants at the levels stated previously.
  • the detersive surfactant can be selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants and mixtures.
  • Nonlimiting examples of surfactants useful herein include the conventional Ci j-Cjg alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C10-C20 alkyl sulfates (“AS”), the C ⁇ Q-CIS secondary (2,3) alkyl sulfates of the formula CH3(CH ) ⁇ (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 C10-C18 alkyl alkoxy sulfates (“AE X S”; especially EO 1-7 ethoxy sulfates), ClO'Cl ⁇ alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxy
  • the conventional nonionic and amphoteric surfactants such as the C ⁇ -Cjg alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C -C ⁇ 2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetaines ("sultaines"), C10-C18 amine oxides, and the like, can also be included in the overall compositions.
  • the C10-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 9,206,154.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as CIQ-CJ S N-(3-methoxypropyl) glucamide.
  • the N-propyl through N- hexyl C12-C18 glucamides can be used for low sudsing.
  • C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
  • the C1Q-C1 alkyl alkoxy sulfates (“AE X S”; especially EO 1-7 ethoxy sulfates) and C-12"C-18 alkyl ethoxylates (“AE”) are the most preferred for the cellulase-containing detergents described herein.
  • the granules and agglomerates preferably include a builder at the previously stated levels.
  • a builder at the previously stated levels.
  • inorganic as well as organic builders can be used.
  • crystalline as well as amorphous builder materials can be used.
  • Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils and to eliminate water hardness.
  • 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), sulphates, and aluminosilicates.
  • non-phosphate builders are required in some locales.
  • compositions herein function surprisingly well even in the presence of the so-called “weak” builders (as compared with phosphates) such as citrate, or in the so-called “under built” situation that may occur with zeolite or layered silicate builders.
  • silicate builders are the alkali metal silicates, particularly those having a Si ⁇ 2:Na2 ⁇ ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Hoechst commonly abbreviated herein as "SKS-6”
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na2Si ⁇ 5 morphology form of layered silicate.
  • 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 ⁇ 2 ⁇ + yH2 ⁇ 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.
  • delta-Na2SiO5 (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.
  • Aluminosilicate builders are useful builders in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
  • 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 U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. 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:
  • 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.
  • 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 Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. 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 ethyl enediamine 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 for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C5- C20 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 European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent 3,723,322.
  • Fatty acids e.g., C ⁇ -C ⁇ g monocarboxylic acids
  • the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane- 1 - hydroxy-l,l-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
  • composition of the present invention may also include enzymes, enzyme stabilizers, brighteners, polymeric dispersing agents (i.e. polyacrylates), carriers, hydrotropes, suds boosters or suppressors, soil release agents, dye transfer inhibitors, and processing aids.
  • enzymes enzyme stabilizers, brighteners, polymeric dispersing agents (i.e. polyacrylates), carriers, hydrotropes, suds boosters or suppressors, soil release agents, dye transfer inhibitors, and processing aids.
  • the laundry and cleaning compositions of the present invention can be used in both low density (below 550 grams/liter) and high density granular compositions in which the density of the granule is at least 550 grams/liter.
  • Granular compositions are typically designed to provide an in the wash pH of from about 7.5 to about 11.5, more preferably from about 9.5 to about 10.5.
  • Low density compositions can be prepared by standard spray-drying processes.
  • Various means and equipment are available to prepare high density compositions. Current commercial practice in the field employs spray-drying towers to manufacture compositions which have a density less than about 500 g/1. Accordingly, if spray-drying is used as part of the overall process, the resulting spray- dried particles must be further densified using the means and equipment described hereinafter.
  • the formulator can eliminate spray-drying by using mixing, densifying and granulating equipment that is commercially available. The following is a nonlimiting description of such equipment suitable for use herein.
  • spray-dried granules from a tower can be densified further by loading a liquid such as water or a nonionic surfactant into the pores of the granules and/or subjecting them to one or more high speed mixer/densifiers.
  • a suitable high speed mixer/densifier for this process is a device marketed under the tradename "L ⁇ dige CB 30" or "L ⁇ dige CB 30 Recycler” which comprises a static cylindrical mixing drum having a central rotating shaft with mixing/cutting blades mounted thereon.
  • the ingredients for the detergent composition are introduced into the drum and the shaft/blade assembly is rotated at speeds in the range of 100-2500 rpm to provide thorough mixing/densification.
  • the preferred residence time in the high speed mixer/densifier is from about 1 to 60 seconds.
  • Other such apparatus includes the devices marketed under the tradename “Shugi Granulator” and under the tradename “Drais K-TTP 80).
  • Another process step which can be used to density further spray-dried granules involves grinding and agglomerating or deforming the spray-dried granules in a moderate speed mixer/densifier so as to obtain particles having lower intraparticle porosity.
  • Equipment such as that marketed under the tradename "L ⁇ dige KM" (Series 300 or 600) or “L ⁇ dige Ploughshare” mixer/densifiers are suitable for this process step.
  • Such equipment is typically operated at 40-160 rpm.
  • the residence time of the detergent ingredients in the moderate speed mixer/densifier is from about 0.1 to 12 minutes.
  • Other useful equipment includes the device which is available under the tradename "Drais K-T 160".
  • This process step which employs a moderate speed mixer/densifier e.g. L ⁇ dige KM
  • L ⁇ dige CB high speed mixer/densifier
  • Other types of granules manufacturing apparatus useful herein include the apparatus disclosed in U.S. Patent 2,306,898, to G. L. Heller, December 29, 1942.
  • the reverse sequential mixer/densifier configuration is also contemplated by the invention.
  • One or a combination of various parameters including residence times in the mixer/densifiers, operating temperatures of the equipment, temperature and/or composition of the granules, the use of adjunct ingredients such as liquid binders and flow aids, can be used to optimize densification of the spray-dried granules in the process of the invention.
  • adjunct ingredients such as liquid binders and flow aids
  • Patent 4,637,891 issued January 20, 1987 (granulating spray-dried granules with a liquid binder and aluminosilicate); Kruse et al, U.S. Patent 4,726,908, issued February 23, 1988 (granulating spray-dried granules with a liquid binder and aluminosilicate); and, Bortolotti et al, U.S. Patent 5,160,657, issued November 3, 1992 (coating densified granules with a liquid binder and aluminosilicate).
  • the formulator can eliminate the spray-drying step by feeding, in either a continuous or batch mode, starting detergent ingredients directly into mixing/densifying equipment that is commercially available.
  • One particularly preferred embodiment involves charging a surfactant paste and an anhydrous builder material into a high speed mixer/densifier (e.g. L ⁇ dige CB) followed by a moderate speed mixer/densifier (e.g. L ⁇ dige KM) to form high density detergent agglomerates.
  • a high speed mixer/densifier e.g. L ⁇ dige CB
  • a moderate speed mixer/densifier e.g. L ⁇ dige KM
  • the liquid/solids ratio of the starting detergent ingredients in such a process can be selected to obtain high density agglomerates that are more free flowing and crisp.
  • the process may include one or more recycle streams of undersized particles produced by the process which are fed back to the mixer/densifiers for further agglomeration or build-up.
  • the oversized particles produced by this process can be sent to grinding apparatus and then fed back to the mixing/densifying equipment.
  • These additional recycle process steps facilitate build-up agglomeration of the starting detergent ingredients resulting in a finished composition having a uniform distribution of the desired particle size (400-700 microns) and density (> 550 g 1). See Capeci et al, U.S. Patent 5,516,448, issued May 14, 1996 and Capeci et al, U.S. Patent 5,489,392, issued February 6, 1996.
  • the high density detergent composition of the invention can be produced using a fluidized bed mixer.
  • the various ingredients of the finished composition are combined in an aqueous slurry (typically 80% solids content) and sprayed into a fluidized bed to provide the finished detergent granules.
  • this process can optionally include the step of mixing the slurry using the aforementioned L ⁇ dige CB mixer/densifier or a "Flexomix 160" mixer/densifier, available from Shugi. Fluidized bed or moving beds of the type available under the tradename "Escher Wyss" can be used in such processes.
  • Another suitable process which can be used herein involves feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic material (e.g. sodium carbonate) and optionally other detergent ingredients into a high speed mixer/densifier (residence time 5-30 seconds) so as to form agglomerates containing a partially or totally neutralized anionic surfactant salt and the other starting detergent ingredients.
  • a high speed mixer/densifier e.g. L ⁇ dige KM
  • a moderate speed mixer/densifier e.g. L ⁇ dige KM
  • high density detergent compositions according to the invention can be produced by blending conventional or densified spray-dried detergent granules with detergent agglomerates in various proportions (e.g. a 60:40 weight ratio of granules to agglomerates) produced by one or a combination of the processes discussed herein.
  • Additional adjunct ingredients such as enzymes, perfumes, brighteners and the like can be sprayed or admixed with the agglomerates, granules or mixtures thereof produced by the processes discussed herein.
  • Bleaching compositions in granular form typically limit water content, for example, to less than about 7% free water, for best storage stability.
  • the method of washing fabrics and depositing perfume thereto comprises contacting said fabrics with an aqueous wash liquor comprising at least about 100 ppm of conventional detersive ingredients described hereinabove, as well as at least about 0.1 ppm of the above-disclosed laundry additive particle.
  • said aqueous liquor comprises from about 500 ppm to about 20,000 ppm of the conventional detersive ingredients and from about 10 ppm to about 200 ppm of the laundry additive particle.
  • the laundry additive particle works under all circumstances, but is particularly useful for providing odor benefits during the laundering process and on wet and dry fabrics.
  • the method comprises contacting fabrics with an aqueous liquor containing at least about 100 ppm of conventional detersive ingredients and at least about 1 ppm of the laundry additive particle such that the perfumed zeolite particles are entrained on the fabrics, storing line-dried fabrics under ambient conditions with humidity of at least 20%, drying the fabric in a conventional automatic dryer, or applying heat to fabrics which have been line-dried or machine dried at low heat (less than about 50°C) by conventional ironing means (preferably with steam or pre-wetting).
  • Perfume-loaded zeolite (“PLZ”) is prepared by mixing Zeolite 13X and perfume at a 85/15 weight ratio.
  • the PLZ is thoroughly mixed with the intermediate coating oil (ICO) in a proportion of 1:0.5 to 1:1 PLZ:ICO.
  • the mixture is then poured into a solution about 4 fold the weight of the mixture and containing about 25% solid starch. During the entire process, this second mixture is kept with agitation using a mixer or a high-speed homogenizer such as a tissue homogenizer.
  • the mixture is then pumped into a spray dryer at 180 °C to 220 °C.
  • the process yields a fine powder, which is suitable for use as a laundry additive in a detergent composition.
  • the perfume loaded in the zeolite has following composition:
  • the particles formed unexpectedly have a superior "Neat Product Odor” ("NPO") and emit only minimal detectable odors over the base product odor as observed by a statistically significant number of panelist graders. This provides strong evidence of the lack of perfume displacement from the carrier particles.
  • NPO Neat Product Odor
  • the following detergent compositions according to the invention are suitable for machine and handwashing operations.
  • the base granule is prepared by a conventional spray drying process in which the starting ingredients are formed into a slurry and passed through a spray drying tower having a counter current stream of hot air (200-400 C) resulting in the formation of porous granules.
  • the remaining adjunct detergent ingredients are sprayed on or added dry.
  • the following detergent composition according to the invention is in the form of a laundry bar which is particularly suitable for handwashing operations.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Fats And Perfumes (AREA)

Abstract

La présente invention concerne un système de libération d'additifs qui sont incorporés dans de nombreux produits de consommation, tels que des détergents et des compositions nettoyantes, des désodorisants, des compositions insecticides, nettoyants et désodorisants de moquette, dans lequel l'additif n'est libéré que lorsqu'il est exposé à un environnement mouillé ou humide. D'une manière plus spécifique, le système de libération d'additifs de l'invention est une particule comprenant un noyau constitué d'un matériau support poreux contenant dans ses pores un additif, tel que du parfum ; un premier revêtement en huile hydrophobe enveloppant ledit noyau ; et un second revêtement constitué d'un matériau hydrosoluble ou dispersable dans l'eau mais insoluble dans l'huile, tel que l'amidon ou l'amidon modifié, qui enveloppe le noyau enrobé d'huile hydrophobe. La particule de libération de l'invention peut s'utiliser avec des agents de nettoyage ou de lessivage lors ou pendant un cycle de lavage. Au cours du lavage, une particule de libération d'un additif de lessivage de l'invention libère efficacement sur la surface d'un tissu des ingrédients parfumés.
PCT/IB2000/001755 1999-12-03 2000-11-27 Systeme de liberation dote d'un support poreux encapsule charge d'additifs, notamment d'additifs detergents tels que des parfums WO2001040430A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
HU0203565A HUP0203565A3 (en) 1999-12-03 2000-11-27 Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes
JP2001541168A JP2003515664A (ja) 1999-12-03 2000-11-27 添加剤、特に香料のような洗剤添加剤が充填された内包された多孔性キャリアを有するデリバリーシステム
AU14082/01A AU759299B2 (en) 1999-12-03 2000-11-27 Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes
US10/148,760 US6790814B1 (en) 1999-12-03 2000-11-27 Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes
MXPA02005445A MXPA02005445A (es) 1999-12-03 2000-11-27 Sistema de suministro que tiene vehiculo o poroso encapsulado cargado con aditivos, particularmente aditivos de detergentes tales como perfumes.
EP00976207A EP1234015A1 (fr) 1999-12-03 2000-11-27 Systeme de liberation dote d'un support poreux encapsule charge d'additifs, notamment d'additifs detergents tels que des parfums
BR0015971-9A BR0015971A (pt) 1999-12-03 2000-11-27 Sistema de liberação tendo veìculo poroso encapsulado carregado com aditivos, particularmente aditivos de detergente tais como perfumes
CA002390382A CA2390382A1 (fr) 1999-12-03 2000-11-27 Systeme de liberation dote d'un support poreux encapsule charge d'additifs, notamment d'additifs detergents tels que des parfums

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US16902499P 1999-12-03 1999-12-03
US60/169,024 1999-12-03
US20862900P 2000-06-01 2000-06-01
US60/208,629 2000-06-01

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US10/911,022 Continuation US20050009715A1 (en) 1999-12-03 2004-08-04 Delivery system having a encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes

Publications (1)

Publication Number Publication Date
WO2001040430A1 true WO2001040430A1 (fr) 2001-06-07

Family

ID=26864689

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2000/001755 WO2001040430A1 (fr) 1999-12-03 2000-11-27 Systeme de liberation dote d'un support poreux encapsule charge d'additifs, notamment d'additifs detergents tels que des parfums

Country Status (14)

Country Link
EP (1) EP1234015A1 (fr)
JP (1) JP2003515664A (fr)
KR (1) KR100466468B1 (fr)
CN (1) CN1237163C (fr)
AR (1) AR029197A1 (fr)
AU (1) AU759299B2 (fr)
BR (1) BR0015971A (fr)
CA (1) CA2390382A1 (fr)
CZ (1) CZ20021828A3 (fr)
EG (1) EG22678A (fr)
HU (1) HUP0203565A3 (fr)
MA (1) MA25777A1 (fr)
MX (1) MXPA02005445A (fr)
WO (1) WO2001040430A1 (fr)

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002064725A1 (fr) * 2001-02-12 2002-08-22 The Procter & Gamble Company Systeme d'administration pourvu d'un support poreux encapsule charge d'additifs
WO2003057815A1 (fr) * 2002-01-07 2003-07-17 Ciba Specialty Chemicals Holding Inc. Composition particulaire comprenant des fixatifs de colorant
EP1388585A1 (fr) * 2002-08-07 2004-02-11 The Procter & Gamble Company Composition détergente
EP1407754A1 (fr) * 2002-10-10 2004-04-14 INTERNATIONAL FLAVORS & FRAGRANCES INC. Compositions de parfum encapsulées
EP1449912A1 (fr) * 2003-02-18 2004-08-25 Cognis Iberia, S.L. Compositions aqueuses contenant des matières actives microencapsulées
EP1471137A1 (fr) * 2003-04-23 2004-10-27 The Procter & Gamble Company Composition comprenant un polymere cationique ameliorant la deposition en surface
WO2005010269A1 (fr) * 2003-07-22 2005-02-03 Deotexis Inc. Procede pour appliquer des parfums sur des textiles et matiere odoriferante
JP2005512811A (ja) * 2002-01-10 2005-05-12 フイルメニツヒ　ソシエテ　アノニム 押出し成形された送達系の製造法
EP1533364A2 (fr) * 2003-11-20 2005-05-25 INTERNATIONAL FLAVORS & FRAGRANCES INC. Matieres encapsulees
EP1541121A1 (fr) * 2003-12-11 2005-06-15 Rohm And Haas Company Système et procédé pour libérer des ingrédients actifs encapsulés
US6984617B2 (en) * 2002-04-26 2006-01-10 The Procter & Gamble Company Fragrance release
EP1632558A1 (fr) * 2004-09-06 2006-03-08 The Procter & Gamble Composition comprenant un polymère cationique favorisant le dépot superficiel
US7125835B2 (en) 2002-10-10 2006-10-24 International Flavors & Fragrances Inc Encapsulated fragrance chemicals
DE102005042053A1 (de) * 2005-09-02 2007-03-08 Henkel Kgaa Zeolith- und parfümhaltige Teilchen mit verbesserten Dufteigenschaften
US7276472B2 (en) 2004-03-18 2007-10-02 Colgate-Palmolive Company Oil containing starch granules for delivering benefit-additives to a substrate
US7279454B2 (en) 2004-03-18 2007-10-09 Colgate-Palmolive Company Oil containing starch granules for delivering benefit-additives to a substrate
CN100429345C (zh) * 2006-07-28 2008-10-29 上海应用技术学院 应用玫瑰-龙涎-檀香复合香精在纺织品上加香的方法
US7601678B2 (en) * 2001-02-07 2009-10-13 Henkel Ag & Co. Kgaa Washing and cleaning agents comprising fine microparticles with cleaning agent components
WO2010028898A1 (fr) * 2008-09-12 2010-03-18 Unilever Plc Améliorations se rapportant à des assouplisseurs de tissu
WO2010060677A1 (fr) * 2008-11-27 2010-06-03 Henkel Ag & Co. Kgaa Détergent ou nettoyant parfumé
WO2010077651A2 (fr) 2008-12-08 2010-07-08 The Procter & Gamble Company Substrat solide poreux et soluble et complexes parfum amidon situés en surface
WO2011005943A1 (fr) * 2009-07-10 2011-01-13 The Procter & Gamble Company Compositions contenant des particules délivrant un agent bénéfique
WO2011005932A1 (fr) * 2009-07-10 2011-01-13 The Procter & Gamble Company Compositions contenant des particules d'administration d'agent bénéfique
WO2011014401A2 (fr) 2009-07-30 2011-02-03 The Procter & Gamble Company Articles et procédés de soin oral
WO2011072009A1 (fr) 2009-12-08 2011-06-16 The Procter & Gamble Company Substrat solide poreux pouvant être dissous et revêtement résidant en surface comprenant des microsphères de matrice
WO2012116014A1 (fr) * 2011-02-25 2012-08-30 Milliken & Company Capsules et compositions les comprenant
WO2015169851A1 (fr) * 2014-05-09 2015-11-12 Basf Se Granulé d'acylhydrazone doté d'un revêtement à deux couches destiné à être utilisé dans des détergents pour le linge
WO2016168629A1 (fr) * 2015-04-15 2016-10-20 Aeonclad Coatings, Llc Particules enrobées pour la formation de couches polymères ou métalliques continues
US9725684B2 (en) 2011-02-25 2017-08-08 Milliken & Company Capsules and compositions comprising the same
US10385296B2 (en) 2017-03-16 2019-08-20 The Procter & Gamble Company Methods for making encapsulate-containing product compositions
US10385297B2 (en) 2017-03-16 2019-08-20 The Procter & Gamble Company Methods for making encapsulate-containing product compositions
US10611988B2 (en) 2017-03-16 2020-04-07 The Procter & Gamble Company Methods for making encapsulate-containing product compositions
EP3580320A4 (fr) * 2017-02-10 2020-12-09 Henkel IP & Holding GmbH Exhausteurs de parfum particulaires
CN114958499A (zh) * 2022-05-26 2022-08-30 深圳市汇尚科科技有限公司 留香珠及其制备方法、洗涤剂组合物

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006006003A1 (fr) * 2004-07-02 2006-01-19 Firmenich Sa Composes hydrophiles encapsules
KR100733292B1 (ko) * 2005-12-23 2007-06-29 한국생산기술연구원 친수성 왁스 조성물, 이를 함유한 가공극세사 섬유원단의제조방법 및 그로 제조된 가공극세사 섬유원단
KR101145940B1 (ko) * 2005-12-29 2012-05-15 애경산업(주) 세탁 및 세정용 첨가제 조성물
MX2009005390A (es) * 2006-11-22 2009-06-02 Procter & Gamble Particula de suministro que contiene agentes beneficos.
EP2270124A1 (fr) * 2009-06-30 2011-01-05 The Procter & Gamble Company Compositions de blanchiment comportant un système de livraison de parfum
CN107982095B (zh) * 2017-10-19 2020-03-27 珀莱雅化妆品股份有限公司 一种具有抗皱功效的缓释固体微球的制备方法
KR102019645B1 (ko) * 2019-02-21 2019-09-09 한국화학연구원 염기성오염물질 제거용 비드 및 이의 제조방법
RU2713356C1 (ru) * 2019-05-15 2020-02-04 Сергей Борисович Врублевский Шихта для композиционного отбеливателя и способ его получения (варианты)
KR102231747B1 (ko) * 2019-10-16 2021-03-24 대경대학교 산학협력단 보색샴푸 조성물 및 이의 제조방법

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997011151A1 (fr) * 1995-09-18 1997-03-27 The Procter & Gamble Company Systemes de liberation
WO1997034982A1 (fr) * 1996-03-22 1997-09-25 The Procter & Gamble Company Systeme d'emission a zeolite charge d'une barriere de liberation
WO1999055819A1 (fr) * 1998-04-23 1999-11-04 The Procter & Gamble Company Particules de parfum en inclusion et compositions detergentes contenant ces particules

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997011151A1 (fr) * 1995-09-18 1997-03-27 The Procter & Gamble Company Systemes de liberation
WO1997034982A1 (fr) * 1996-03-22 1997-09-25 The Procter & Gamble Company Systeme d'emission a zeolite charge d'une barriere de liberation
WO1999055819A1 (fr) * 1998-04-23 1999-11-04 The Procter & Gamble Company Particules de parfum en inclusion et compositions detergentes contenant ces particules

Cited By (57)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7601678B2 (en) * 2001-02-07 2009-10-13 Henkel Ag & Co. Kgaa Washing and cleaning agents comprising fine microparticles with cleaning agent components
WO2002064725A1 (fr) * 2001-02-12 2002-08-22 The Procter & Gamble Company Systeme d'administration pourvu d'un support poreux encapsule charge d'additifs
AU2002367419B2 (en) * 2002-01-07 2008-04-10 Ciba Specialty Chemicals Holding Inc. Particulate composition comprising dye fixatives
WO2003057815A1 (fr) * 2002-01-07 2003-07-17 Ciba Specialty Chemicals Holding Inc. Composition particulaire comprenant des fixatifs de colorant
JP2005512811A (ja) * 2002-01-10 2005-05-12 フイルメニツヒ　ソシエテ　アノニム 押出し成形された送達系の製造法
JP4646186B2 (ja) * 2002-01-10 2011-03-09 フイルメニツヒ ソシエテ アノニム 押出し成形された送達系の製造法
US6984617B2 (en) * 2002-04-26 2006-01-10 The Procter & Gamble Company Fragrance release
WO2004015050A1 (fr) * 2002-08-07 2004-02-19 The Procter & Gamble Company Composition detergent
JP2005533168A (ja) * 2002-08-07 2005-11-04 ザ プロクター アンド ギャンブル カンパニー 洗剤組成物
EP1388585A1 (fr) * 2002-08-07 2004-02-11 The Procter & Gamble Company Composition détergente
US7196049B2 (en) 2002-10-10 2007-03-27 International Flavors & Fragrances, Inc Encapsulated fragrance chemicals
US7294612B2 (en) 2002-10-10 2007-11-13 International Flavors & Fragrances Inc. Encapsulated fragrance chemicals
US7585824B2 (en) 2002-10-10 2009-09-08 International Flavors & Fragrances Inc. Encapsulated fragrance chemicals
US7125835B2 (en) 2002-10-10 2006-10-24 International Flavors & Fragrances Inc Encapsulated fragrance chemicals
EP1407754A1 (fr) * 2002-10-10 2004-04-14 INTERNATIONAL FLAVORS & FRAGRANCES INC. Compositions de parfum encapsulées
EP1449912A1 (fr) * 2003-02-18 2004-08-25 Cognis Iberia, S.L. Compositions aqueuses contenant des matières actives microencapsulées
EP1471137A1 (fr) * 2003-04-23 2004-10-27 The Procter & Gamble Company Composition comprenant un polymere cationique ameliorant la deposition en surface
WO2004094583A3 (fr) * 2003-04-23 2005-01-06 Procter & Gamble Composition comprenant un polymere cationique favorisant le depot superficiel
WO2004094583A2 (fr) * 2003-04-23 2004-11-04 The Procter & Gamble Company Composition comprenant un polymere cationique favorisant le depot superficiel
WO2005010269A1 (fr) * 2003-07-22 2005-02-03 Deotexis Inc. Procede pour appliquer des parfums sur des textiles et matiere odoriferante
EP1533364A3 (fr) * 2003-11-20 2005-06-08 INTERNATIONAL FLAVORS & FRAGRANCES INC. Matieres encapsulees
EP1533364A2 (fr) * 2003-11-20 2005-05-25 INTERNATIONAL FLAVORS & FRAGRANCES INC. Matieres encapsulees
AU2004233544B2 (en) * 2003-12-11 2010-08-12 Rohm And Haas Company System and process for releasing encapsulated active ingredients
EP1541121A1 (fr) * 2003-12-11 2005-06-15 Rohm And Haas Company Système et procédé pour libérer des ingrédients actifs encapsulés
US7338928B2 (en) 2003-12-11 2008-03-04 Rohm And Haas Company System for releasing encapsulated active ingredients
US7396804B2 (en) 2004-03-18 2008-07-08 Colgate-Palmolive Company Oil containing starch granules for delivering benefit-additives to a substrate
US7393815B2 (en) 2004-03-18 2008-07-01 Colgate-Palmolive Company Oil containing starch granules for delivering benefit-additives to a substrate
US7279454B2 (en) 2004-03-18 2007-10-09 Colgate-Palmolive Company Oil containing starch granules for delivering benefit-additives to a substrate
US7396805B2 (en) 2004-03-18 2008-07-08 Colgate-Palmolive Company Oil containing starch granules for delivering benefit-additives to a substrate
US7276472B2 (en) 2004-03-18 2007-10-02 Colgate-Palmolive Company Oil containing starch granules for delivering benefit-additives to a substrate
US7393816B2 (en) 2004-03-18 2008-07-01 Colgate-Palmolive Company Oil containing starch granules for delivering benefit-additives to a substrate
WO2006029066A1 (fr) * 2004-09-06 2006-03-16 The Procter & Gamble Company Composition comprenant un polymere cationique facilitant le depot en surface
EP1632558A1 (fr) * 2004-09-06 2006-03-08 The Procter & Gamble Composition comprenant un polymère cationique favorisant le dépot superficiel
DE102005042053A1 (de) * 2005-09-02 2007-03-08 Henkel Kgaa Zeolith- und parfümhaltige Teilchen mit verbesserten Dufteigenschaften
CN100429345C (zh) * 2006-07-28 2008-10-29 上海应用技术学院 应用玫瑰-龙涎-檀香复合香精在纺织品上加香的方法
WO2010028898A1 (fr) * 2008-09-12 2010-03-18 Unilever Plc Améliorations se rapportant à des assouplisseurs de tissu
CN102149803A (zh) * 2008-09-12 2011-08-10 荷兰联合利华有限公司 与织物调理剂有关的改进
WO2010060677A1 (fr) * 2008-11-27 2010-06-03 Henkel Ag & Co. Kgaa Détergent ou nettoyant parfumé
WO2010077651A2 (fr) 2008-12-08 2010-07-08 The Procter & Gamble Company Substrat solide poreux et soluble et complexes parfum amidon situés en surface
WO2011005943A1 (fr) * 2009-07-10 2011-01-13 The Procter & Gamble Company Compositions contenant des particules délivrant un agent bénéfique
WO2011005932A1 (fr) * 2009-07-10 2011-01-13 The Procter & Gamble Company Compositions contenant des particules d'administration d'agent bénéfique
EP3336164A1 (fr) 2009-07-10 2018-06-20 The Procter & Gamble Company Compositions contenant des particules délivrant un agent bénéfique
WO2011014401A2 (fr) 2009-07-30 2011-02-03 The Procter & Gamble Company Articles et procédés de soin oral
WO2011072009A1 (fr) 2009-12-08 2011-06-16 The Procter & Gamble Company Substrat solide poreux pouvant être dissous et revêtement résidant en surface comprenant des microsphères de matrice
US9725684B2 (en) 2011-02-25 2017-08-08 Milliken & Company Capsules and compositions comprising the same
WO2012116014A1 (fr) * 2011-02-25 2012-08-30 Milliken & Company Capsules et compositions les comprenant
CN103492062A (zh) * 2011-02-25 2014-01-01 美利肯公司 胶囊及包含其的组合物
WO2015169851A1 (fr) * 2014-05-09 2015-11-12 Basf Se Granulé d'acylhydrazone doté d'un revêtement à deux couches destiné à être utilisé dans des détergents pour le linge
WO2016168629A1 (fr) * 2015-04-15 2016-10-20 Aeonclad Coatings, Llc Particules enrobées pour la formation de couches polymères ou métalliques continues
US9617394B2 (en) 2015-04-15 2017-04-11 Aeonclad Coatings, Llc Coated particles for forming of continuous polymeric or metallic layers
US20160304677A1 (en) * 2015-04-15 2016-10-20 Aeonclad Coatings, Llc Coated particles for forming of continuous polymeric or metallic layers
EP3580320A4 (fr) * 2017-02-10 2020-12-09 Henkel IP & Holding GmbH Exhausteurs de parfum particulaires
US11008535B2 (en) 2017-02-10 2021-05-18 Henkel IP & Holding GmbH Particulate fragrance enhancers
US10385296B2 (en) 2017-03-16 2019-08-20 The Procter & Gamble Company Methods for making encapsulate-containing product compositions
US10385297B2 (en) 2017-03-16 2019-08-20 The Procter & Gamble Company Methods for making encapsulate-containing product compositions
US10611988B2 (en) 2017-03-16 2020-04-07 The Procter & Gamble Company Methods for making encapsulate-containing product compositions
CN114958499A (zh) * 2022-05-26 2022-08-30 深圳市汇尚科科技有限公司 留香珠及其制备方法、洗涤剂组合物

Also Published As

Publication number Publication date
KR100466468B1 (ko) 2005-01-15
HUP0203565A3 (en) 2006-06-28
MA25777A1 (fr) 2003-07-01
MXPA02005445A (es) 2002-11-29
EP1234015A1 (fr) 2002-08-28
CN1408019A (zh) 2003-04-02
HUP0203565A2 (hu) 2003-02-28
JP2003515664A (ja) 2003-05-07
EG22678A (en) 2003-06-30
AU1408201A (en) 2001-06-12
CN1237163C (zh) 2006-01-18
AU759299B2 (en) 2003-04-10
BR0015971A (pt) 2002-07-16
CA2390382A1 (fr) 2001-06-07
AR029197A1 (es) 2003-06-18
CZ20021828A3 (cs) 2002-10-16
KR20020059831A (ko) 2002-07-13

Similar Documents

Publication Publication Date Title
US6790814B1 (en) Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes
AU759299B2 (en) Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes
EP0931130B1 (fr) Particule pour additif de lessive a couches superficielles multiples
US20030045446A1 (en) Delivery system having encapsulated porous carrier loaded with additives
US6221826B1 (en) Laundry additive particle having multiple surface coatings
EP0701600B1 (fr) Systeme de diffusion de parfum comprenant des zeolites
CA2329331C (fr) Particules de parfum en inclusion et compositions detergentes contenant ces particules
EP1539913B1 (fr) Composition de parfum
JPH0319978A (ja) 香料／シクロデキストリン複合体での布帛の処理
CA2265804A1 (fr) Procede de revetement double destine a la production d'une composition particulaire de lavage contenant des additifs, destinee a liberer un parfum et presentant des proprietes physiques ameliorees
AU2002245426A1 (en) Delivery system having encapsulated porous carrier loaded with additives
MXPA99008579A (en) Laundry additive particle having multiple surface coatings
MXPA98008663A (en) Laundry additive particle having multiple surface coatings

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ CZ DE DE DK DK DM DZ EE EE ES FI FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 14082/01

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 2390382

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: IN/PCT/2002/00531/DE

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: PV2002-1828

Country of ref document: CZ

ENP Entry into the national phase

Ref document number: 2001 541168

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: PA/a/2002/005445

Country of ref document: MX

Ref document number: 1020027007005

Country of ref document: KR

Ref document number: 10148760

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 008166633

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2000976207

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1020027007005

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2000976207

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: PV2002-1828

Country of ref document: CZ

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWG Wipo information: grant in national office

Ref document number: 14082/01

Country of ref document: AU

WWG Wipo information: grant in national office

Ref document number: 1020027007005

Country of ref document: KR

WWW Wipo information: withdrawn in national office

Ref document number: 2000976207

Country of ref document: EP