WO2012116021A1 - Capsules et compositions comprenant celles-ci - Google Patents

Capsules et compositions comprenant celles-ci Download PDF

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Publication number
WO2012116021A1
WO2012116021A1 PCT/US2012/026043 US2012026043W WO2012116021A1 WO 2012116021 A1 WO2012116021 A1 WO 2012116021A1 US 2012026043 W US2012026043 W US 2012026043W WO 2012116021 A1 WO2012116021 A1 WO 2012116021A1
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WO
WIPO (PCT)
Prior art keywords
capsule
water
laundry care
shell layer
group
Prior art date
Application number
PCT/US2012/026043
Other languages
English (en)
Inventor
Gregory E. FERNANDES
Robert M. Macmeccan
Original Assignee
Milliken & 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
Priority claimed from US13/035,409 external-priority patent/US20120220514A1/en
Priority claimed from US13/035,445 external-priority patent/US9725684B2/en
Priority claimed from US13/400,988 external-priority patent/US20130217609A1/en
Application filed by Milliken & Company filed Critical Milliken & Company
Priority to CN201280019482.4A priority Critical patent/CN103492062A/zh
Priority to JP2013555514A priority patent/JP2014512257A/ja
Priority to EP12706418.6A priority patent/EP2678101A1/fr
Publication of WO2012116021A1 publication Critical patent/WO2012116021A1/fr

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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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0004—Coated particulate pigments or dyes
    • 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
    • C11D3/40—Dyes ; Pigments
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/12—Processes in which the treating agent is incorporated in microcapsules

Definitions

  • This application relates to capsules and encapsulated materials that are suitable for use in a variety of applications.
  • the present invention provides capsules (e.g., microcapsules).
  • the capsules generally comprise one or more encapsulated materials and a continuous shell layer surrounding the encapsulated materials.
  • these capsules are not formed by mating two preformed halves. Rather, the shell layer of the capsule is continuous and formed in such a way that it does not have a seam or joint where two halves meet or are joined.
  • the encapsulated materials can be one or more cores, or the encapsulated materials can be a number of discrete cores each surrounded by a continuous intermediate layer.
  • the capsules provided by the invention are believed to be particularly well-suited for the protection of certain components from, for example, deleterious interactions with other components in a system (e.g., cleaning composition, such as a laundry detergent).
  • the capsules are also believed to provide a convenient means by which a bluing agent can be added to a composition, such as a laundry detergent composition, without affecting the overall aesthetics of the composition.
  • a composition such as a laundry detergent composition
  • the composition can be provided with virtually any visual appearance because the composition would contain a relatively small number of colored capsules (i.e., capsules containing the bluing agent), whereas the straight addition of the same amount of bluing agent to the composition would result in a composition exhibiting the color of the bluing agent.
  • the invention provides a capsule comprising:
  • each core independently comprising at least one lipophobic material selected from the group consisting of dyes, pigments, polymeric colorants, optical brighteners, fluorescing dyes, bleaching agents, bleach activators, bleach catalysts, bleach stabilizers, textile hand modifiers, fabric softeners, fabric stiffeners, soil release agents, enzymes, oxidizing agents, antimicrobials, antifungal agents, disinfectants, antioxidants, water softening agents, detergent builders, antiredeposition agents, foam boosters, humectants, water soluble polymers, odor removers, dye-transfer inhibitors, UV absorbers, UV stabilizers, botanic extracts, urea, sequestrants, abrasives, water, and combinations thereof;
  • intermediate layer comprising a lipophilic material that is immiscible with or insoluble in aqueous media
  • a continuous shell layer surrounding the intermediate layer comprising a material selected from the group consisting of hydrogels, dehydrated hydrogels, water-soluble polymers, water-dispersible polymers, and combinations thereof.
  • the invention provides a capsule comprising:
  • a disintegration aid disposed in the shell layer the disintegration aid exhibiting an absorption of 5 grams or more of solution per gram of disintegration aid as measured in an aqueous solution having an electrical conductivity of about 5 S/cm or less.
  • the invention provides a capsule comprising:
  • intermediate layer comprising a lipophilic material that is immiscible with or insoluble in aqueous media
  • a continuous shell layer surrounding the intermediate layer comprising: (i) a material selected from the group consisting of hydrogels, dehydrated hydrogels, water-soluble polymers, water-dispersible polymers, and combinations thereof; and
  • a disintegration aid disposed in the shell layer the disintegration aid exhibiting an absorption of 5 grams or more of solution per gram of disintegration aid as measured in an aqueous solution having an electrical conductivity of about 5 S/cm or less.
  • the invention also provides compositions comprising at least one of the capsules according to the invention.
  • the invention provides a composition comprising at least one surfactant and at least one capsule according to the invention or a plurality of capsules according to the invention.
  • the invention provides a cleaning composition comprising at least one cleaning agent and at least one capsule according to the invention or a plurality of capsules according to the invention.
  • the invention provides a laundry care composition comprising at least one laundry care ingredient and at least one capsule according to the invention or a plurality of capsules according to the invention.
  • Fig. 1 is a cross-section view of a capsule according to the invention.
  • FIG. 2 is a cross-section view of another capsule according to the invention.
  • FIG. 3 is a cross-section view of another capsule according to the invention.
  • Fig. 4 is a cross-section view of a triple nozzle coextrusion apparatus suitable for use in making the capsules according to the invention.
  • the term "core” refers to a discrete body residing within the interior of a capsule.
  • the core has a distinct boundary separating it from either the surrounding intermediate layer or, in other embodiments, the shell layer.
  • the core can be a solid, a liquid, or both (e.g., a solid dispersed or suspended within a liquid).
  • the core can be a solution containing a solid or a semi-solid dissolved within a suitable solvent (e.g., water, an alcohol, or a mixture thereof).
  • lipophobic and lipophilic are generally used in a relative sense intended to convey the affinity of one component of the capsule (e.g., the core) for another component (e.g., the continuous intermediate layer). Thus, unless specifically noted in the specification, the terms are not intended to indicate that a component exhibits any particular hydrophilic-lipophilic balance value.
  • the invention provides a capsule 100, 200 comprising a relatively small number of cores 1 10, a continuous intermediate layer 120 surrounding each core 1 10, and a continuous shell layer 130 surrounding the intermediate layer 120.
  • the capsule can comprise any suitable number of cores.
  • the capsule comprises about 10 cores or less, or about 5 cores or less.
  • the capsule comprises about 1 to about 5 discrete cores.
  • the core comprises a lipophobic material.
  • lipophobic is generally used to denote a material that exhibits a sufficient aversion to the intermediate layer that at least a portion of the material can form a discrete, separate phase when the two are combined and this phase separation remains stable for a substantial period of time (e.g., about 24 hours or more).
  • the lipophobic material exhibits an octanol-water partition coefficient (log Pow) of less than 6 (e.g., about 5 or less, about 4 or less, about 3 or less, about 2 or less, or about 1 or less).
  • the lipophobic material present in the core can be any suitable lipophobic material.
  • Suitable lipophobic materials include, but are not necessarily limited to, dyes (e.g., acid dyes), pigments, polymeric colorants, optical brighteners, fluorescing dyes, bleaches, textile hand modifiers, fabric softeners, soil release agents, enzymes, oxidizing agents, antimicrobials, antioxidants, water-soluble polymers (e.g., polyethylene glycols, polyvinylpyrrolidone, and cellulose ethers), non-ionic
  • surfactants anionic surfactants, cationic surfactants, amphoteric surfactants, detergent builders, alkalis, acids, bases, complexing agents, ion-exchangers, bleaching agents, bleach activators, bleach catalysts, bleach stabilizers, enzymes, soil antiredeposition agents, soil repellant agents, soil release agents, foam
  • the lipophobic material can be a colorant, such as a dye, pigment, polymeric colorant, or a combination thereof. In certain preferred embodiments, the lipophobic material is a polymeric colorant.
  • polymeric colorant refers to a colorant comprising a chromophore and an oligomeric constituent bound to the chromophore.
  • the oligomeric constituent can be bound to the chromophore via any suitable means, such as a covalent bond, an ionic bond, or suitable electrostatic interaction.
  • the oligomeric constituent can have any suitable formula weight.
  • formula weight refers to the weight (in grams) of the oligomeric constituent per mole of the polymeric colorant.
  • the "formula weight" of the oligomeric constituent refers to the portion of the polymeric colorant's molecular weight attributable to the oligomeric constituent (the remainder being attributable to the chromophore and any other groups attached thereto).
  • the oligomeric constituent has a formula weight of about 40 or more.
  • the oligomeric constituent typically has a formula weight of about 3,000 or less. In certain possibly preferred embodiments, the oligomeric constituent has a formula weight of about 40 to about 3,000.
  • Polymeric colorants suitable for use in the invention include, but are not limited to, those colorants conforming to the structure of Formula (I) or Formula (II) below:
  • Ri or Ri— [E] a is an organic chromophore.
  • Each E is a linking moiety independently selected from the group consisting of nitrogen, oxygen, sulfur, a sulfonyl group, a sulfonate group, a sulfonamide group, and a carboxyl group.
  • Each R 2 is independently selected from the group consisting of hydrogen, alkyl groups, alkoxy groups, and aryl groups.
  • the variable a is a positive integer.
  • the variables b and c are independently selected from the group consisting of integers from 0 to 2. If E is nitrogen or a sulfonamide group, the sum of b and c is 2.
  • the polymeric colorant conforming to the structure of Formula (I) contains at least one— Z— X substituent bound to Ri through a linking moiety E.
  • the polymeric colorant contains only one liking moiety E (i.e., a is 1 )
  • at least one— Z— X substituent is bound to the linking moiety E (i.e., c is at least 1 ).
  • the polymeric colorant contains multiple linking moieties E (i.e., a is 2 or more), then at least one of the linking moieties has at least one— Z— X
  • R 4 or R 4 (G)h is an organic chromophore.
  • G is selected from the group consisting of S0 3 " and C0 2 " .
  • Each R 5 is independently selected from the group consisting of hydrogen, alkyl groups, and aryl groups; and M is selected from the group consisting of nitrogen atoms and phosphorous atoms.
  • the variable h is an integer from 1 to 4
  • the variable k is an integer from 0 to 5
  • the variable j is an integer from 1 to 6.
  • the sum of k and j is equal to 4 when M is a nitrogen atom and 6 when M is a phosphorous atom.
  • each Z is a divalent organic moiety independently selected from the group consisting of C- 1 -C 20 alkyl moieties, aryl moieties, alkoxyl moieties, and oligomeric substituents.
  • the oligomeric substituents are selected from the group consisting of (A) divalent oligomeric substituents comprising two or more divalent repeating units
  • R 2 o and R 2 i are independently selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, aryl, alkoxyalkyl, and aryloxyalkyl; (B) divalent substituents conforming to the structure of Formula (VIII)
  • R 25 and R 26 are independently selected from the group consisting of hydrogen, hydroxyl, and C-i-C-io alkyl, f is an integer from 1 to 1 2, and g is an integer from 1 to 1 00; and (C) divalent substituents comprising two or more substituents selected from (A) and (B).
  • each X is an end group independently selected from the group consisting of hydrogen, a hydroxyl group, a sulfhydryl group, thiol groups, amine groups, alkyl groups, aryl groups, alkyl ester groups, aryl ester groups, organic sulfonate groups, organic sulfate groups, and amide groups.
  • At least one— Z— X substituent of the colorant conforming to the structure of Formula (I) or Formula (II) terminates in a group selected from the group consisting of a hydroxyl group, a sulfhydryl group, thiol groups, primary amine groups, secondary amine groups, primary amide groups, and secondary amide groups.
  • at least one — Z— X substituent comprises an oligomeric substituent as defined above.
  • the cores can be the same or different.
  • each core can contain the same component(s), each core can contain different components, or some of the cores can contain the same components and other cores contain different
  • the core(s) can comprise any suitable percentage of the capsule's total volume. In certain embodiments, such as when the shell layer is hydrated (e.g., the shell contains a hydrogel), the core(s) can comprise about 5% to about 95% of the capsule's total volume. In certain other embodiments, such as when the shell layer is dehydrated, the core(s) can comprise about 5% to about 99% of the capsule's total volume. In certain possibly preferred embodiments, the core(s) can comprise about 30% to about 80% of the capsule's total volume.
  • the capsules of the first embodiment comprise a continuous, intermediate layer surrounding each core.
  • the intermediate layer can be any suitable material, but generally the intermediate layer comprises a lipophilic material that is immiscible with or insoluble in aqueous media.
  • lipophilic is used in connection with this embodiment to describe the relative affinity of the core material for the intermediate layer.
  • lipophilic is used to describe a material that exhibits a sufficient aversion to the core material that at least a portion of the core material can form a discrete, separate phase when the two are combined and this phase separation remains stable for a substantial period of time (e.g., about 24 hours or more).
  • the lipophiliic material exhibits an octanol-water partition coefficient of 6 or greater (e.g., about 7 or more, about 8 or more, about 9 or more, or about 10 or more). In certain other embodiments, the lipophilic material exhibits a water solubility of less than about one gram per 100 grams of water at 20 °C and 1 atm pressure.
  • the intermediate layer can comprise any suitable material exhibiting the properties described above.
  • the intermediate layer can be a solid, a liquid, or both (e.g., a solid dispersed or suspended within a liquid).
  • the intermediate layer can be a solution containing a solid dissolved within a suitable solvent.
  • Lipophilic materials suitable for use as the intermediate layer include, but are not limited to, vegetable oils (e.g., corn oil), vegetable fats, animal oils, animal fats, mineral oil, paraffinic oils, parrafinic waxes, silicone oils, and mixtures thereof.
  • the intermediate layer comprises a vegetable oil (e.g., corn oil) or a silicone oil.
  • the intermediate layer can comprise any suitable percentage of the capsule's total volume. In certain embodiments, the intermediate layer can comprise about 2% to about 90% of the capsule's total volume. In certain preferred
  • the intermediate layer can comprise about 4% to about 50% of the capsule's total volume or about 6% to about 30% of the capsule's total volume.
  • the lipophobic material of the core and the lipophilic material of the intermediate layer can be selected to yield capsules in which the core(s) will remain stable for an extended period of time, it may be desirable to increase the stability of the core(s) by incorporating additional components into the intermediate layer.
  • the stability of the cores can be increased by dispersing or suspending a hydrophobic, particulate material in the intermediate layer.
  • the hydrophobic, particulate material can be any suitable particulate material that can be stably dispersed or suspended in the intermediate layer.
  • Suitable hydrophobic, particulate materials include, but are not limited to,
  • hydrophobic silica e.g., hydrophobic fumed silica, hydrophobic precipitated silica, and mixtures thereof
  • hydrophobic clays hydrophobic sands, hydrophobic minerals, hydrophobic carbonaceous particles, and combinations thereof.
  • hydrophobic particles can be present in the intermediate layer in any suitable amount. Generally, the hydrophobic particles are added to the intermediate layer in an amount sufficient to appreciably increase the stability of the core(s) and the capsule.
  • the hydrophobic particulate material can be present in the intermediate layer in an amount of about 45% or less (e.g., about 25% or less, about 20% or less, about 15% or less, about 10% or less, or about 5% or less), based on the total weight of the intermediate layer.
  • the hydrophobic material can be present in the intermediate layer in an amount of about 0.1 wt.% or more (e.g., about 0.2 wt.% or more, about 0.3 wt.% or more, about 0.4 wt.% or more, about 0.5 wt.% or more, about 0.6 wt.% or more, about 0.7 wt.% or more, about 0.8 wt.% or more, about 0.9 wt.% or more, or about 1 wt.% or more).
  • about 0.1 wt.% or more e.g., about 0.2 wt.% or more, about 0.3 wt.% or more, about 0.4 wt.% or more, about 0.5 wt.% or more, about 0.6 wt.% or more, about 0.7 wt.% or more, about 0.8 wt.% or more, about 0.9 wt.% or more, or about 1 wt.% or more).
  • the intermediate layer can comprise additional lipophilic material and the hydrophobic particulate material described above.
  • the suitable additional components typically are those that can be dissolved or dispersed in the lipophilic material described above.
  • Suitable examples include, but are not limited to, hydrophobic/lipophilic colorants (e.g., pigments, dyes, polymeric colorants), hydrophobic/lipophilic perfumes, hydrophobic/lipophilic fragrances, hydrophobic/lipophilic antifoaming agents, hydrophobic/lipophilic suds depressants, opacifiers, hydrophobic/lipophilic fluorescent whitening agents, hydrophobic/lipophilic fabric softeners, hydrophobic/lipophilic antistatic agents, other oils (e.g., eucalyptus oils or pine oils), and combinations thereof.
  • hydrophobic/lipophilic colorants e.g., pigments, dyes, polymeric colorants
  • hydrophobic/lipophilic perfumes e.g., hydrophobic/lipophilic fragrances
  • hydrophobic/lipophilic antifoaming agents e.g., hydrophobic/
  • the capsule comprises a shell layer
  • the shell layer can be made from any suitable material that forms a shell of sufficient durability to encapsulate the core and intermediate layer and is stable for an extended period of time when in contact with the intermediate layer.
  • the shell layer typically is not comprised of a material that exhibits an appreciable solubility in the lipophilic material present in the intermediate layer.
  • the shell layer typically comprises a material that is water-soluble, water-dispersible, or contains a significant amount of water (e.g., a hydrogel).
  • Suitable materials for the shell layer include, but are not limited to, hydrogels, dehydrated hydrogels, water-soluble polymers, water- dispersible polymers, and combinations thereof.
  • the hydrogels can be formed using any suitable gelling agent.
  • Suitable gelling agents include, but are not necessarily limited to, polysaccharides, gelatin, alginates, agarose, carrageenans (e.g., ⁇ - carrageenan), pectin, gellan, collagen, and mixtures thereof.
  • the gelling agent is agar.
  • the water-soluble polymer and water-dispersable polymer can be selected from the group consisting of acrylates, polyhydric alcohols, polysaccharides and modified versions thereof, polyvinyl acetate, polyvinyl pyrrolidone, methyl cellulose,
  • the shell layer comprises a water-soluble polymer, and the water-soluble polymer is a polyvinyl alcohol.
  • the shell material is a water-soluble or water-dispersable polymer
  • the shell can also contain a gelling agent, such as any of the gelling agents listed above.
  • the shell layer can further comprise a crosslinking agent.
  • the function of the crosslinking agent is to cause the gelling agent to gel, thereby yielding a hydrogel that is capable of forming the shell layer of the capsule.
  • Suitable cross-linking agents include, but are not limited to, boric acid, caustic, formaldehyde, glutaraldehyde, acetaldehyde, polyaldehydes, zirconium salts (e.g., zirconium chloride, zirconium tetrachloride, zirconyl chloride), salts containing di or trivalent counter ions (e.g., calcium salts), diisocyanates, triols, epichlorohydrin, dextranaldehydes, dialdehydes, tripolyphosphates, carbodiimides, polyepoxides, isocyanates and combinations thereof.
  • the capsules of the invention are generally designed to be used in a composition (e.g., cleaning composition or laundry detergent composition) that is added to or diluted with an appreciable amount of water during use. With such addition or dilution, the water can dissolve or otherwise disintegrate the shell layer thereby releasing the contents of the capsule (e.g., core(s) and, if present, intermediate layer). While the material used in the shell layer can be selected so that it is readily soluble in water, it has been found that the disintegration of the shell layer can, under certain conditions, proceed relatively slowly leading to a delayed release of the contents of the capsule.
  • a composition e.g., cleaning composition or laundry detergent composition
  • the water can dissolve or otherwise disintegrate the shell layer thereby releasing the contents of the capsule (e.g., core(s) and, if present, intermediate layer). While the material used in the shell layer can be selected so that it is readily soluble in water, it has been found that the disintegration of the shell layer can, under certain conditions, proceed relatively slowly
  • the shell layer will not dissolve or disintegrate to release the capsule contents because, once the hydrogel shell has formed, it is stable in aqueous environments. Accordingly, in certain embodiments, it may be desirable to incorporate into the shell layer a material that promotes the disintegration of the shell layer. Such a material will be referred to herein as a "disintegration aid.”
  • the disintegration aid can be any suitable material that promotes a more rapid
  • the disintegration aid can function to promote or accelerate the disintegration of the shell layer by any suitable mechanism.
  • the disintegration aid can be a material that dissolves under certain conditions, which would leave voids or weak spots in the shell layer that allow the capsule to rupture more easily.
  • the disintegration aid can also be a material that expands or swells under certain conditions, which would exert forces on the shell layer as it expands and cause the shell layer to rupture.
  • the disintegration aid exhibits an absorption of 5 grams or more of solution per gram of disintegration aid as measured in an aqueous solution having an electrical conductivity of about 5 S/cm or less. In certain other embodiments, the disintegration aid exhibits an absorption of about 10 grams or more, about 20 grams or more, about 30 grams or more, about 40 grams or more, about 50 grams or more, about 60 grams or more, about 70 grams or more, or about 75 grams or more of solution per gram of disintegration aid as measured in an aqueous solution having an electrical conductivity of about 5 S/cm or less.
  • Suitable disintegration aids include, but are not limited to, superabsorbent polymers, swellable clays, xerogels, and combinations thereof.
  • the superabsorbent polymer can be added to the shell layer composition as particles of the final, crosslinked polymer or the superabsorbent polymer can be in situ formed in the shell by adding an polymer precursor that is then crosslinked during shell formation.
  • the disintegration aid can be present in the shell layer in any suitable amount.
  • the disintegration aid is added to the shell layer in an amount sufficient to appreciably accelerate the disintegration of the shell layer and release of the contents of the capsule.
  • the disintegration aid can be present in the shell layer in an amount of about 0.1 wt.% or more, about 0.2 wt.% or more, about 0.3 wt.% or more, 0.4 wt.% or more, or about 0.5 wt.% or more based on the total weight of the shell layer.
  • disintegration aid can be present in the shell layer in an amount of about 85 wt.% or less, about 80 wt.% or less, about 75 wt.% or less, about 70 wt.% or less, about 65 wt.% or less, about 60 wt.% or less, about 55 wt.% or less, about 50 wt.% or less, about 45 wt.% or less, about 40 wt.% or less, about 35 wt.% or less, or about 30 wt.% or less based on the total weight of the shell layer.
  • the disintegration aid is present in the shell layer in an amount of about 0.1 wt.% to about 80 wt.% based on the total weight of the shell layer. In certain other embodiments, such as when the disintegration aid is a superabsorbent polymer incorporated into the shell layer in particulate form, the disintegration aid can be present in the shell layer in an amount of about 0.5 wt.% to about 10 wt.% based on the total weight of the shell layer.
  • the shell layer can comprise additional components.
  • the capsule's shell layer may be desirable for the capsule's shell layer to be opaque or at least relatively translucent.
  • a suitable opacifier can be incorporated into the shell layer by, for example, adding the opacifier to the shell layer composition.
  • the invention provides a capsule 300 comprising at least one core 1 10 and a continuous shell layer 130 surrounding the core(s) 1 10.
  • the core can be any suitable material, including those described above for the core or the intermediate layer of the first capsule embodiment of the invention.
  • the core is a solid, semi-solid, or a lipophilic material such as those described above for the intermediate layer of the first capsule embodiment of the invention.
  • the shell layer comprises a material for forming the shell and a disintegration aid disposed in the shell layer.
  • the material for forming the shell and the disintegration aid used in such shell layer can be any suitable materials, including those described above for the first capsule embodiment of the invention.
  • the invention provides a capsule comprising at least one core, a continuous, intermediate layer surrounding the core, and a continuous shell layer surrounding the intermediate layer.
  • the core can be any suitable material, but generally the core comprises a lipophobic material such as those described above for the first capsule embodiment of the invention.
  • the intermediate layer can be any suitable material, but generally the intermediate layer comprises a lipophobic material, such as those described above for the first capsule embodiment of the invention.
  • the shell layer comprises a material for forming the shell and a disintegration aid disposed in the shell layer.
  • the material for forming the shell and the disintegration aid used in such shell layer can be any suitable materials, including those described above for the first capsule embodiment of the invention.
  • the capsules of the invention can have any suitable dimensions.
  • the capsules of the invention typically have a diameter of about 10 mm or less, about 9 mm or less, about 8 mm or less, about 7 mm or less, about 6 mm or less, or about 5 mm or less.
  • the capsules of the invention can have a diameter of about 0.05 mm to about 10 mm (e.g., about 0.05 mm to about 9 mm, about 0.05 mm to about 8 mm, about 0.05 mm to about 7 mm, about 0.05 mm to about 6 mm, about 0.05 mm to about 5 mm, about 0.06 mm to about 5 mm, about 0.07 mm to about 5 mm, about 0.08 mm to about 5 mm, about 0.09 mm to about 5 mm, or about 0.1 mm to about 5 mm).
  • the capsules of the invention can be made by any method known in the art to be suitable for producing microencapsulated materials.
  • the capsules can be made by centrifugal coextrusion encapsulation processes, jet cutting encapsulation processes, vibrating nozzle encapsulation process, and multiple nozzle coextrusion encapsulation processes.
  • the capsules of the invention are made by a triple nozzle coextrusion encapsulation process.
  • a suitable triple nozzle coextrusion process and apparatus are described, for example, in U.S. Patent No. 5,330,835 (Kikuchi et al.), the disclosure of which is hereby incorporated by reference.
  • Fig. 4 depicts a triple nozzle coextrusion apparatus suitable for use in producing capsules according to the invention.
  • the apparatus 400 comprises a first nozzle 410, a second nozzle 420, and a third nozzle 430.
  • the first nozzle 410, second nozzle 420, and third nozzle 430 are each positioned in an concentric arrangement.
  • the first nozzle 410 has a smaller diameter than the second nozzle 420 and is positioned within the second nozzle 420.
  • the second nozzle 420 has a smaller diameter than the third nozzle 420 and is positioned within the third nozzle 430.
  • the first nozzle 410 has an interior passage (not marked) that is adapted to convey the material for the core(s) to the nozzle tip 440.
  • the second nozzle 420 has an interior passage (not marked) that is adapted to convey the material for the intermediate layer to the nozzle tip 440.
  • the third nozzle 430 has an interior passage (not marked) that is adapted to convey the material for the shell layer to the nozzle tip 440.
  • the components for forming the core(s) 415, the intermediate layer 425, and the shell layer 435 are each fed to the first nozzle 410, second nozzle 420, and third nozzle 430, respectively, in a liquid state so that the components can be extruded through each nozzle to form the capsule.
  • the component(s) for forming either the core(s), the intermediate layer, or the shell layer are solid at room temperature, the component(s) can heated to a temperature sufficient to melt the component(s) and yield a flowable liquid that can be extruded through the nozzle.
  • these component(s) can be dissolved in a suitable solvent or suspended in a suitable medium.
  • the component(s) for the shell layer 435 envelops the component(s) for the intermediate layer 425
  • the component(s) for the intermediate layer 425 envelops the component(s) for the core(s) 415.
  • the result is a capsule intermediate 450 that then passes through a cooling solution 460, which cools the intermediate and allows the shell layer to solidify to the desired degree.
  • the end result is a capsule 100 having at least one core 1 10 surrounded by a continuous, intermediate layer 120 and a shell layer 130 surrounding the intermediate layer 120.
  • the cooling solution 460 can be circulated so that it flows past the nozzle tip 440 in the same direction as the emerging capsule intermediate 450.
  • the flow rates of the components for the core(s) 415, the intermediate layer 425, and the shell layer 435 can each be individually controlled to adjust the size of the capsules and the percentage of capsule mass or volume contributed by the core, intermediate layer, and shell layer.
  • the flow rates can be adjusted so as to produce capsules containing multiple cores.
  • the flow rate of the cooling solution can be varied to control the thickness of the shell layer. In general and with all other variables being the same, higher flow rates of the cooling solution will produce capsules having thinner shell layers.
  • the capsules of the invention are believed to be particularly well-suited for use in applications in which the capsules, or a composition containing the capsules, are added to or diluted with water.
  • the shell layer of the capsules disintegrates and/or dissolves, which releases the contents of the capsule (e.g., core(s) and, if present, intermediate layer).
  • the capsules of the invention are believed to be well-suited for use in a variety of compositions that are typically used in conjunction with water, such as cleaning compositions (e.g., household cleaning compositions, dish soaps, dishwashing detergent compositions, and laundry detergent compositions), personal care compositions (e.g., liquid hand soaps, liquid body washes, and shampoos), pet care compositions (e.g., liquid pet washes and liquid pet shampoos), and automotive care compositions (e.g., automotive cleaners and automotive degreasers).
  • cleaning compositions e.g., household cleaning compositions, dish soaps, dishwashing detergent compositions, and laundry detergent compositions
  • personal care compositions e.g., liquid hand soaps, liquid body washes, and shampoos
  • pet care compositions e.g., liquid pet washes and liquid pet shampoos
  • automotive care compositions e.g., automotive cleaners and automotive degreasers.
  • liquid compositions mentioned above typically contain water, it is believed that the capsules of the invention can remain stable in these
  • compositions for extended periods of time For example, it has been found that capsules of the invention having a hydrogel shell can remain stable in water for extended periods of time. Therefore, it is believed that such capsules will, under standard or normal conditions, also remain stable in the aqueous compositions mentioned above.
  • This extended stability of the capsule provides a means to protect the capsule's contents from the harsh conditions present in many of the above- mentioned compositions. Furthermore, the capsules generally will not rupture and release their contents until the capsules (or a composition containing the capsules) are exposed to a substantial change in conditions, such as high temperatures or aggressive mechanical forces (e.g., aggressive agitation).
  • compositions also typically contain relatively large amounts of ionic surfactants (e.g., anionic surfactants), and the presence of these ionic compounds produces a composition exhibiting a relatively high ionic strength.
  • ionic surfactants e.g., anionic surfactants
  • the ionic strength of the resulting mixture i.e., the composition plus water
  • the capsule can be designed so that the shell layer (e.g., a hydrogel-based shell layer) contains a disintegration aid whose swelling is inhibited in high ionic strength environments.
  • a disintegration aid would be a superabsorbent polymer.
  • the ionic strength of the resulting mixture i.e., the composition plus water
  • the ionic strength of the resulting mixture will be appreciably lower than that of the composition itself. In this lower ionic strength environment, the
  • the invention also provides compositions comprising the capsules of the invention.
  • the invention provides a composition comprising at least one surfactant and at least one capsule according to the invention or a plurality of capsules according to the invention.
  • the surfactant used in such embodiment can be any suitable surfactant, such as those typically used in cleaning compositions (e.g., liquid laundry detergents, fabric softeners, dish washing detergents), personal care compositions (e.g., liquid hand soaps, liquid body washes, and shampoos), pet care compositions, and automotive care compositions.
  • the composition can be provided in any suitable form (e.g., solid or liquid), with liquid compositions being preferred.
  • the surfactant and capsule(s) of the invention can be incorporated into any suitable liquid medium or carrier, with aqueous media or carriers being preferred.
  • the invention provides a cleaning composition comprising at least one cleaning agent and at least one capsule according to the invention or a plurality of capsules according to the invention.
  • the cleaning agent can be any suitable agent or compound typically used in cleaning compositions (e.g., household cleaning compositions). Suitable cleaning agents include, but are not limited to, surfactants (e.g., detersive surfactants), disinfectants, degreasers, bleaches, and combinations thereof.
  • capsules of the invention are believed to be particularly well-suited for use in laundry care
  • the invention provides a laundry care composition comprising at least one laundry care ingredient and at least one capsule according to the invention or a plurality of capsules according to the invention.
  • compositions and components suitable for use in the same are compositions and components suitable for use in the same.
  • the term "laundry care composition” includes, unless otherwise indicated, granular, powder, liquid, gel, paste, bar form and/or flake type washing agents and/or fabric treatment compositions.
  • fabric treatment composition includes, unless otherwise indicated, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions and combinations thereof. Such compositions can be, but need not be, rinse added compositions.
  • laundry care composition including, but not limited to, laundry detergents and fabric care compositions.
  • Such compositions comprise a plurality of said capsules and a laundry care ingredient.
  • the laundry care compositions including laundry detergents can be in solid or liquid form, including a gel form.
  • the laundry detergent composition comprises a surfactant in an amount sufficient to provide desired cleaning properties.
  • the capsules can be present in the laundry detergent composition in an amount from about 0.0001 % to about 10% by weight of the composition, more preferably from about 0.001 % to about 5% by weight of the composition, and even more preferably from about 0.01 % to about 1 % by weight of the composition.
  • the laundry detergent composition comprises a surfactant in an amount sufficient to provide desired cleaning properties.
  • the laundry detergent composition comprises, by weight, from about 5% to about 90% of the surfactant, and more specifically from about 5% to about 70% of the surfactant, and even more specifically from about 5% to about 40%.
  • the surfactant can comprise anionic, nonionic, cationic, zwitterionic and/or amphoteric surfactants.
  • the detergent composition comprises anionic surfactant, nonionic surfactant, or mixtures thereof.
  • Suitable anionic surfactants useful herein can comprise any of the conventional anionic surfactant types typically used in liquid detergent products. These include the alkyl benzene sulfonic acids and their salts as well as alkoxylated or non-alkoxylated alkyl sulfate materials.
  • Exemplary anionic surfactants are the alkali metal salts of C-
  • the alkyl group is linear and such linear alkyl benzene sulfonates are known as "LAS".
  • Alkyl benzene sulfonates, and particularly LAS are well known in the art.
  • Such surfactants and their preparation are described for example in U.S. Pat. Nos. 2,220,099 and 2,477,383.
  • sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyi group is from about 1 1 to 14.
  • Sodium C-n-C-i 4 e.g., C-
  • anionic surfactant comprises ethoxylated alkyi sulfate surfactants.
  • Such materials also known as alkyi ether sulfates or alkyi polyethoxylate sulfates, are those which correspond to the formula:
  • R— O— (C 2 H 4 0)n— S0 3 M wherein R' is a C 8 -C 2 o alkyi group, n is from about 1 to 20, and M is a salt-forming cation.
  • R' is C-I O -C-I S alkyi, n is from about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium.
  • R' is a C 2 -C 6 alkyi, n is from about 1 to 6, and M is sodium.
  • compositions of this invention and used as or in any anionic surfactant component which may be present.
  • non-alkoxylated, e.g., non-ethoxylated, alkyi ether sulfate surfactants are those produced by the sulfation of higher C 8 -C 20 fatty alcohols.
  • Conventional primary alkyi sulfate surfactants have the general formula: ROS0 3 " M + wherein R is typically a linear C 8 -C 20 hydrocarbyl group, which can be straight chain or branched chain, and M is a water-solubilizing cation.
  • R is a C-1 0 -C-15 alkyi
  • M is alkali metal, more specifically R is Ci 2 -Ci 4 and M is sodium.
  • anionic surfactants useful herein include: a) C-n-C-i 8 alkyi benzene sulfonates (LAS); b) C-
  • x is an integer of at least about 7, preferably at least about 9, and y is an integer of at least 8, preferably at least about 9;
  • MES methyl ester sulfonate
  • AOS alpha-olefin sulfonate
  • Suitable nonionic surfactants useful herein can comprise any of the conventional nonionic surfactant types typically used in liquid detergent products. These include alkoxylated fatty alcohols and amine oxide surfactants. Preferred for use in the liquid detergent products herein are those nonionic surfactants which are normally liquid.
  • Suitable nonionic surfactants for use herein include the alcohol alkoxylate nonionic surfactants.
  • Alcohol alkoxylates are materials which correspond to the general formula: R 1 (C m H 2m O) n OH wherein R 1 is a C 8 -C-
  • R 1 is an alkyl group, which can be primary or secondary, that comprises from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms.
  • the alkoxylated fatty alcohols will also be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule.
  • the alkoxylated fatty alcohol materials useful in the liquid detergent compositions herein will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. More preferably, the HLB of this material will range from about 6 to 15, most preferably from about 8 to 15.
  • HLB hydrophilic-lipophilic balance
  • Alkoxylated fatty alcohol nonionic surfactants have been marketed under the tradenames Neodol and Dobanol by the Shell Chemical Company.
  • Nonionic surfactant useful herein comprises the amine oxide surfactants.
  • Amine oxides are materials which are often referred to in the art as “semi-polar" nonionics. Amine oxides have the formula:
  • R is a relatively long-chain hydrocarbyl moiety which can be saturated or unsaturated, linear or branched, and can contain from 8 to 20, preferably from 10 to 16 carbon atoms, and is more preferably C-
  • R' is a short-chain moiety, preferably selected from hydrogen, methyl and— CH 2 OH.
  • EO is ethyleneoxy
  • PO propyleneneoxy
  • BO is butyleneoxy.
  • Amine oxide surfactants are illustrated by C-12-C-14 alkyldimethyl amine oxide.
  • Non-limiting examples of nonionic surfactants include: a) C-
  • the detersive surfactant component can comprise combinations of anionic and nonionic surfactant materials.
  • the weight ratio of anionic to nonionic will typically range from 10:90 to 90:10, more typically from 30:70 to 70:30.
  • Cationic surfactants are well known in the art and non-limiting examples of these include quaternary ammonium surfactants, which can have up to 26 carbon atoms. Additional examples include a) alkoxylate quaternary ammonium (AQA) surfactants as discussed in U.S. Pat. No. 6,136,769; b) dimethyl hydroxyethyl quaternary ammonium as discussed in U.S. Pat. No. 6,004,922; c) polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; d) cationic ester surfactants as discussed in U.S.
  • AQA alkoxylate quaternary ammonium
  • Non-limiting examples of zwitterionic surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678 to Laughlin et al., issued Dec.
  • betaine including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine, C 8 to d 8 (preferably C 12 to Ci 8 ) amine oxides and sulfo and hydroxy betaines, such as N-alkyl-N,N-dimethylammino-1 -propane sulfonate where the alkyl group can be C 8 to C-
  • Non-limiting examples of ampholytic surfactants include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain.
  • One of the aliphatic substituents comprises at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one comprises an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1 975 at column 19, lines 18-35, for examples of ampholytic surfactants.
  • the compositions can be in the form of a solid, either in tablet or particulate form, including, but not limited to, particles, flakes, or the like, or the compositions can be in the form of a liquid.
  • the liquid detergent compositions comprise an aqueous, non-surface active liquid carrier.
  • the amount of the aqueous, non-surface active liquid carrier employed in the compositions herein will be effective to solubilize, suspend or disperse the composition components.
  • the compositions can comprise, by weight, from about 5% to about 90%, more specifically from about 10% to about 70%, and even more specifically from about 20% to about 70% of the aqueous, non-surface active liquid carrier.
  • aqueous, non-surface active liquid carrier The most cost effective type of aqueous, non-surface active liquid carrier is, of course, water itself. Accordingly, the aqueous, non-surface active liquid carrier component will generally be mostly, if not completely, comprised of water. While other types of water-miscible liquids, such alkanols, diols, other polyols, ethers, amines, and the like, have been conventionally been added to liquid detergent compositions as co-solvents or stabilizers, for purposes of the present invention, the utilization of such water-miscible liquids should be minimized to hold down composition cost. Accordingly, the aqueous liquid carrier component of the liquid detergent products herein will generally comprise water present in
  • concentrations ranging from about 5% to about 90%, more preferably from about 20% to about 70%, by weight of the composition.
  • Detergent compositions can also contain bleaching agents.
  • Suitable bleaching agents include, for example, hydrogen peroxide sources, such as those described in detail in the herein incorporated Kirk Othmer's Encyclopedia of
  • the preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself.
  • perborate e.g., sodium perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide
  • sources of available oxygen such as persulfate bleach (e.g., OXONE, manufactured by DuPont).
  • percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources can also be used.
  • a suitable percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1 ,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1 ,250 micrometers.
  • the percarbonate can be coated with a silicate, borate or water-soluble surfactants.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
  • Compositions of the present invention can also comprise as the bleaching agent a chlorine-type bleaching material. Such agents are well known in the art, and include for example sodium dichloroisocyanurate ("NaDCC"). However, chlorine-type bleaches are less preferred for compositions which comprise enzymes.
  • the peroxygen bleach component in the composition is formulated with an activator (peracid precursor).
  • the activator is present at levels of from about 0.01 %, preferably from about 0.5%, more preferably from about 1 % to about 15%, preferably to about 10%, more preferably to about 8%, by weight of the composition.
  • a bleach activator as used herein is any compound which, when used in conjunction with a hydrogen peroxide, source leads to the in situ production of the peracid corresponding to the bleach activator.
  • activators are disclosed in U.S. Patent Nos. 5,576,282;
  • Preferred activators are selected from the group consisting of tetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL),
  • BOBS benzoyloxybenzenesulphonate
  • NOBS nonanoyloxybenzenesulphonate
  • PhBz phenyl benzoate
  • do-OBS decanoyloxybenzenesulphonate
  • BZVL benzoylvalerolactam
  • C 8 -OBS octanoyloxybenzenesulphonate
  • perhydrolyzable esters and mixtures thereof most preferably benzoylcaprolactam and benzoylvalerolactam.
  • Particularly preferred bleach activators in the pH range from about 8 to about 1 1 are those selected having an OBS or VL leaving group.
  • Preferred hydrophobic bleach activators include, but are not limited to, nonanoyloxybenzenesulphonate (NOBS); 4-[N-(nonanoyl) amino hexanoyloxy]- benzene sulfonate sodium salt (NACA-OBS), an example of which is described in U.S. Patent No. 5,523,434; dodecanoyloxybenzenesulphonate (LOBS or C 12 -OBS); 10-undecenoyloxybenzenesulfonate (UDOBS or Cn-OBS with unsaturation in the 10 position); and decanoyloxybenzoic acid (DOBA).
  • NOBS nonanoyloxybenzenesulphonate
  • NACA-OBS 4-[N-(nonanoyl) amino hexanoyloxy]- benzene sulfonate sodium salt
  • DOBA decanoyloxybenzoic acid
  • Preferred bleach activators are those described in U.S. Patent No. 5,998,350 to Burns et al. ; U.S. Patent No. 5,698,504 to Christie et al. ; U.S. Patent No. 5,695,679 to Christie et al. ; U.S. Patent No. 5,686,401 to Willey et al. ; U.S. Patent No. 5,686,014 to Hartshorn et al. ; U.S. Patent No. 5,405,412 to Willey et al. ; U.S. Patent No. 5,405,413 to Willey et al. ; U.S. Patent No. 5,130,045 to Mitchel et al. ; and U.S. Patent No. 4,412,934 to Chung et al., all of which are incorporated herein by reference.
  • the mole ratio of peroxygen source (as AvO) to bleach activator in the present invention generally ranges from at least 1 :1 , preferably from about 20:1 , more preferably from about 10:1 to about 1 :1 , preferably to about 3:1 .
  • Quaternary substituted bleach activators can also be included.
  • the present laundry compositions preferably comprise a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP, preferably a quaternary substituted percarboxylic acid or a quaternary substituted peroxyimidic acid); more preferably, the former.
  • QSBA structures are further described in U.S. Patent No. 5,686,015 to Willey et al. ; U.S. Patent No. 5,654,421 to Taylor et al. ; U.S. Patent No. 5,460,747 to Gosselink et al. ; U.S. Patent No. 5,584,888 to Miracle et al. ; U.S. Patent No. 5,578,136 to Taylor et al. ; all of which are incorporated herein by reference.
  • bleach activators useful herein are amide-substituted as described in U.S. Patent Nos. 5,698,504; 5,695,679; and 5,686,014, each of which are cited herein above.
  • Preferred examples of such bleach activators include: (6-octanamidocaproyl) oxybenzenesulfonate,
  • activators include benzoxazin-type activators, such as a C 6 H 4 ring to which is fused in the 1 ,2-positions a moiety
  • Nitriles such as acetonitriles and/or ammonium nitriles and other quaternary nitrogen containing nitriles, are another class of activators that are useful herein.
  • Non-limiting examples of such nitrile bleach activators are described in U.S. Patent Nos. 6,133,216; 3,986,972; 6,063,750; 6,017,464; 5,958,289; 5,877,315; 5,741 ,437; 5,739,327; 5,004,558; and in EP Nos. 790 244, 775 127, 1 017 773, 1 017 776; and in WO 99/14302, WO 99/14296, WO96/40661 , all of which are incorporated herein by reference.
  • bleaching results can be obtained from bleaching systems having an in-use pH of from about 6 to about 13, and preferably from about 9.0 to about 10.5.
  • activators with electron-withdrawing moieties are used for near-neutral or sub-neutral pH ranges.
  • Alkalis and buffering agents can be used to secure such pH.
  • compositions and methods of the present invention can also optionally include metal-containing bleach catalysts, preferably manganese and cobalt-containing bleach catalysts.
  • One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity (such as copper, iron, titanium, ruthenium tungsten, molybdenum, or manganese cations), an auxiliary metal cation having little or no bleach catalytic activity (such as zinc or aluminum cations), and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and water-soluble salts thereof.
  • a transition metal cation of defined bleach catalytic activity such as copper, iron, titanium, ruthenium tungsten, molybdenum, or manganese cations
  • an auxiliary metal cation having little or no bleach catalytic activity such as zinc or aluminum cations
  • a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid
  • the compositions herein can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Patent Nos. 5,576,282; 5,246,621 ; 5,244,594; 5,194,416; and 5,1 14,606; and European Pat. App. Pub. Nos. 549,271 A1 ; 549,272 A1 ; 544,440 A2; and 544,490 A1 .
  • Preferred examples of these catalysts include
  • Other metal-based bleach catalysts include those disclosed in U.S. Patent Nos. 4,430,243 and 5,1 14,61 1 . The use of manganese with various complex ligands to enhance bleaching is also reported in the following: U.S. Patent Nos. 4,728,455; 5,284,944; 5,246,612;
  • Cobalt Metal Complexes - Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. Patent Nos. 5,597,936; 5,595,967; and 5,703,030; and M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. inorg. Bioinorg. Mech., (1983), 2, pages 1 -94.
  • the most preferred cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula
  • Transition Metal Complexes of Macropolycyclic Rigid Ligands - Compositions herein can also suitably include as bleach catalyst a transition metal complex of a macropolycyclic rigid ligand.
  • the amount used is a catalytically effective amount, suitably about 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or more, preferably from about 0.05 ppm to about 500 ppm (wherein "ppb” denotes parts per billion by weight and "ppm” denotes parts per million by weight).
  • Transition-metal bleach catalysts of Macrocyclic Rigid Ligands which are suitable for use in the invention compositions can in general include known compounds where they conform with the definition herein, as well as, more preferably, any of a large number of novel compounds expressly designed for the present laundry or laundry uses, and are non-limitingly illustrated by any of the following:
  • compositions and methods herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the composition comprising a lipophilic fluid and a bleach system, and will preferably provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the composition comprising a lipophilic fluid and a bleach system.
  • Bleach Boosting Compounds can comprise one or more bleach boosting compounds.
  • Bleach boosting compounds provide increased bleaching effectiveness in lower temperature applications.
  • the bleach boosters act in conjunction with conventional peroxygen bleaching sources to provide increased bleaching effectiveness. This is normally accomplished through in situ formation of an active oxygen transfer agent such as a dioxirane, an oxaziridine, or an oxaziridinium. Alternatively, preformed dioxiranes, oxaziridines and
  • oxaziridiniums can be used.
  • Suitable bleach boosting compounds for use in accordance with the present invention are cationic imines, zwitterionic imines, anionic imines and/or polyionic imines having a net charge of from about +3 to about -3, and mixtures thereof.
  • These imine bleach boosting compounds of the present invention include those of the general structure:
  • R 1 - R 4 can be a hydrogen or an unsubstituted or substituted radical selected from the group consisting of phenyl, aryl, heterocyclic ring, alkyl and cycloalkyl radicals.
  • zwitterionic bleach boosters which are described in U.S. Patent Nos. 5,576,282 and 5,718,614.
  • Other bleach boosting compounds include cationic bleach boosters described in U.S. Patent Nos. 5,360,569; 5,442,066; 5,478,357; 5,370,826; 5,482,515; 5,550,256; and WO 95/13351 , WO 95/13352, and WO 95/13353.
  • Peroxygen sources are well-known in the art and the peroxygen source employed in the present invention can comprise any of these well known sources, including peroxygen compounds as well as compounds, which under consumer use conditions, provide an effective amount of peroxygen in situ.
  • the peroxygen source can include a hydrogen peroxide source, the in situ formation of a peracid anion through the reaction of a hydrogen peroxide source and a bleach activator, preformed peracid compounds or mixtures of suitable peroxygen sources.
  • the bleach boosting compounds when present, are preferably employed in conjunction with a peroxygen source in the bleaching systems of the present invention.
  • Preformed Peracids are also suitable as bleaching agents.
  • the preformed peracid compound as used herein is any convenient compound which is stable and which under consumer use conditions provides an effective amount of peracid or peracid anion.
  • the preformed peracid compound can be selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof. Examples of these compounds are described in U.S. Patent No. 5,576,282 to Miracle et al.
  • R is an alkylene or substituted alkylene group containing from 1 to about 22 carbon atoms or a phenylene or substituted phenylene group
  • Y is hydrogen, halogen, alkyl, aryl, -C(0)OH or -C(0)OOH.
  • Organic peroxyacids suitable for use in the present invention can contain either one or two peroxy groups and can be either aliphatic or aromatic.
  • the organic peroxycarboxylic acid is aliphatic, the unsubstituted peracid has the general formula:
  • Y can be, for example, H, CH 3 , CH 2 CI, C(O)OH, or C(O)OOH; and n is an integer from 0 to 20.
  • the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula:
  • Y can be, for example, hydrogen, alkyl, alkylhalogen, halogen, C(O)OH or C(O)OOH.
  • Typical monoperoxy acids useful herein include alkyl and aryl peroxyacids such as:
  • peroxybenzoic acid and ring-substituted peroxybenzoic acid e.g. peroxy-a-naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate), and o-carboxybenzamidoperoxyhexanoic acid (sodium salt);
  • aliphatic, substituted aliphatic and arylalkyl monoperoxy acids e.g. peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N,N-(3-octylsuccinoyl)aminoperoxycaproic acid (SAPA) and N,N- phthaloylaminoperoxycaproic acid (PAP);
  • amidoperoxyacids e.g. monononylamide of either peroxysuccinic acid (NAPSA) or of peroxyadipic acid (NAPAA).
  • Typical diperoxyacids useful herein include alkyl diperoxyacids and aryldiperoxyacids, such as:
  • Such bleaching agents are disclosed in U.S. Patent Nos. 4,483,781 to Hartman and 4,634,551 to Burns et al. ; European Patent Application 0,133,354 to Banks et al.; and U.S. Patent No. 4,412,934 to Chung et al.
  • Sources also include 6- nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent No. 4,634,551 to Burns et al.
  • Persulfate compounds such as for example OXONE, manufactured commercially by E.I. DuPont de Nemours of Wilmington, DE can also be employed as a suitable source of peroxymonosulfuric acid.
  • PAP is disclosed in, for example, U.S. Patent Nos. 5,487,818; 5,310,934; 5,246,620; 5,279,757 and 5,132,431 .
  • Photobleaches - Suitable photobleaches for use in the treating compositions of the present invention include, but are not limited to, the
  • Enzyme Bleaching - Enzymatic systems can be used as bleaching agents.
  • the hydrogen peroxide can also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process.
  • an enzymatic system i.e. an enzyme and a substrate therefore
  • Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991 .
  • the present invention compositions and methods can utilize alternative bleach systems such as ozone, chlorine dioxide and the like.
  • Bleaching with ozone can be accomplished by introducing ozone-containing gas having ozone content from about 20 to about 300 g/m 3 into the solution that is to contact the fabrics.
  • the gas:liquid ratio in the solution should be maintained from about 1 :2.5 to about 1 :6.
  • U.S. Patent No. 5,346, 588 describes a process for the utilization of ozone as an alternative to conventional bleach systems and is herein incorporated by reference.
  • the detergent compositions of the present invention can also include any number of additional optional ingredients.
  • laundry detergent composition components such as non-tinting dyes, detersive builders, enzymes, enzyme stabilizers (such as propylene glycol, boric acid and/or borax), suds suppressors, soil suspending agents, soil release agents, other fabric care benefit agents, pH adjusting agents, chelating agents, smectite clays, solvents, hydrotropes and phase stabilizers, structuring agents, dye transfer inhibiting agents, opacifying agents, optical brighteners, perfumes and coloring agents.
  • the various optional detergent composition ingredients if present in the compositions herein, should be utilized at concentrations conventionally employed to bring about their desired contribution to the composition or the laundering operation. Frequently, the total amount of such optional detergent composition ingredients can range from about 0.01 % to about 50%, more preferably from about 0.1 % to about 30%, by weight of the composition.
  • the liquid detergent compositions are in the form of an aqueous solution or uniform dispersion or suspension of surfactant, optical brightener, and certain optional other ingredients, some of which may normally be in solid form, that have been combined with the normally liquid components of the composition, such as the liquid alcohol ethoxylate nonionic, the aqueous liquid carrier, and any other normally liquid optional ingredients.
  • a solution, dispersion or suspension will be acceptably phase stable and will typically have a viscosity which ranges from about 100 to 600 cps, more preferably from about 150 to 400 cps. For purposes of this invention, viscosity is measured with a Brookfield LVDV-II+ viscometer apparatus using a #21 spindle.
  • liquid detergent compositions herein can be prepared by combining the components thereof in any convenient order and by mixing, e.g., agitating, the resulting component combination to form a phase stable liquid detergent composition.
  • a liquid matrix is formed containing at least a major proportion, and preferably substantially all, of the liquid components, e.g., nonionic surfactant, the non-surface active liquid carriers and other optional liquid components, with the liquid
  • any anionic surfactants and the solid form ingredients can be added. Agitation of the mixture is continued, and if necessary, can be increased at this point to form a solution or a uniform dispersion of insoluble solid phase particulates within the liquid phase. After some or all of the solid-form materials have been added to this agitated mixture, particles of any enzyme material to be included, e.g., enzyme prills, are incorporated.
  • one or more of the solid components can be added to the agitated mixture as a solution or slurry of particles premixed with a minor portion of one or more of the liquid components.
  • agitation of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity and phase stability characteristics. Frequently this will involve agitation for a period of from about 30 to 60 minutes.
  • the optical brightener is first combined with one or more liquid components to form a optical brightener premix, and this optical brightener premix is added to a composition formulation containing a substantial portion, for example more than 50% by weight, more specifically, more than 70% by weight, and yet more specifically, more than 90% by weight, of the balance of components of the laundry detergent composition.
  • a composition formulation containing a substantial portion, for example more than 50% by weight, more specifically, more than 70% by weight, and yet more specifically, more than 90% by weight, of the balance of components of the laundry detergent composition.
  • both the optical brightener premix and the enzyme component are added at a final stage of component additions.
  • the optical brightener is
  • the encapsulated optical brightener is suspended in a structured liquid, and the suspension is added to a composition formulation containing a substantial portion of the balance of
  • the detergent compositions can be in a solid form. Suitable solid forms include tablets and particulate forms, for example, granular particles or flakes. Various techniques for forming detergent compositions in such solid forms are well known in the art and can be used herein.
  • the optical brightener is provided in particulate form, optionally including additional but not all components of the laundry detergent composition.
  • the optical brightener particulate is combined with one or more additional particulates containing a balance of components of the laundry detergent composition.
  • the optical brightener optionally including additional but not all components of the laundry detergent composition, can be provided in an encapsulated form, and the optical brightener encapsulate is combined with particulates containing a substantial balance of components of the laundry detergent composition.
  • compositions of this invention prepared as hereinbefore
  • aqueous washing solutions for use in the laundering of fabrics.
  • an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing machine, to form such aqueous laundering solutions.
  • the aqueous washing solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered therewith.
  • An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering solutions can comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous washing solution. More preferably, from about 1 ,000 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing solution.
  • the optical brighteners of the present invention can be included in a fabric care composition.
  • the fabric care composition can be comprised of at least one optical brightener and a rinse added fabric softening composition ("RAFS;” also known as rinse added fabric conditioning compositions). Examples of typical rinse added softening compositions can be found in U.S. Provisional Patent Application Serial No. 60/687582 filed on October 8, 2004.
  • the rinse added fabric softening composition can comprise from about 1 % to about 90% by weight of the FSA, more preferably from about 5% to about 50% by weight of the FSA.
  • the optical brightener can be present in the rinse added fabric softening composition in an amount from about 0.5 ppb to about 50 ppm, more preferably from about 0.5 ppm to about 30 ppm. [0111] In one embodiment of the invention, the fabric softening active
  • FSA is a quaternary ammonium compound suitable for softening fabric in a rinse step.
  • the FSA is formed from a reaction product of a fatty acid and an aminoalcohol obtaining mixtures of mono-, di-, and, in one embodiment, triester compounds.
  • the FSA comprises one or more softener quaternary ammonium compounds such as, but not limited to, a monoalkyquaternary ammonium compound, a diamido quaternary compound and a diester quaternary ammonium compound, or a combination thereof.
  • the FSA comprises a diester quaternary ammonium (hereinafter "DQA") compound composition.
  • DQA compounds compositions also encompasses a description of diamido FSAs and FSAs with mixed amido and ester linkages as well as the aforementioned diester linkages, all herein referred to as DQA.
  • a first type of DQA (“DQA (1 )") suitable as a FSA in the present CFSC includes a compound comprising the formula:
  • each R substituent is either hydrogen, a short chain CrC 6 , preferably CrC 3 alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, poly (C 2 -C 3 alkoxy), preferably polyethoxy, group, benzyl, or mixtures thereof; each m is 2 or 3; each n is from 1 to about 4, preferably 2; each Y is
  • each Y is the same or different; the sum of carbons in each R 1 , plus one when Y is -0-(0)C- or -NR-C(O)-, is C 12 -C 2 2, preferably C 14 -C 20 , with each R 1 being a hydrocarbyl, or substituted hydrocarbyl group; it is acceptable for R 1 to be
  • X " can be any softener-compatible anion, preferably, chloride, bromide, methylsulfate, ethylsulfate, sulfate, phosphate, and nitrate, more preferably chloride or methyl sulfate.
  • Preferred DQA compounds are typically made by reacting alkanolamines such as MDEA (methyldiethanolamine) and TEA (triethanolamine) with fatty acids.
  • Some materials that typically result from such reactions include N,N-di(acyl-oxyethyl)-N,N-dimethylammonium chloride or N,N-di(acyl-oxyethyl)-N,N- methylhydroxyethylammonium methylsulfate wherein the acyl group is derived from animal fats, unsaturated, and polyunsaturated, fatty acids, e.g., tallow, hardended tallow, oleic acid, and/or partially hydrogenated fatty acids, derived from vegetable oils and/or partially hydrogenated vegetable oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, palm oil, etc.
  • the FSA comprises other actives in addition to DQA (1 ) or DQA.
  • the FSA comprises only DQA (1 ) or DQA and is free or essentially free of any other quaternary ammonium compounds or other actives.
  • the FSA comprises the precursor amine that is used to produce the DQA.
  • the FSA comprises a compound, identified as DTTMAC comprising the formula:
  • each R 1 is a C 6 -C 2 2, preferably C-i 4 -C 2 o, but no more than one being less than about d 2 and then the other is at least about 16, hydrocarbyl, or substituted hydrocarbyl substituent, preferably C-i 0 -C 2 o alkyi or alkenyl (unsaturated alkyi, including polyunsaturated alkyi, also referred to sometimes as "alkylene”), most preferably Ci 2 -Ci 8 alkyi or alkenyl, and branch or unbranched.
  • the Iodine Value (IV) of the FSA is from about 1 to 70; each R is H or a short chain Ci-C 6 , preferably C-
  • a " is a softener compatible anion, preferably, chloride, bromide, methylsulfate, ethylsulfate, sulfate, phosphate, or nitrate; more preferably chloride or methyl sulfate.
  • FSAs include dialkydimethylammonium salts and dialkylenedimethylammonium salts such as ditallowdimethylammonium and ditallowdimethylammonium methylsulfate.
  • dialkylenedimethylammonium salts examples include di- hydrogenated tallow dimethyl ammonium chloride and ditallowdimethyl ammonium chloride available from Degussa under the trade names Adogen® 442 and Adogen® 470 respectively.
  • the FSA comprises other actives in addition to DTTMAC.
  • the FSA comprises only compounds of the DTTMAC and is free or essentially free of any other quaternary ammonium compounds or other actives.
  • the FSA comprises an FSA described in U.S. Pat. Pub. No. 2004/0204337 A1 , published Oct. 14, 2004 to Corona et al., from
  • the FSA is one described in U.S. Pat. Pub. No. 2004/0229769 A1 , published Nov. 18, 2005, to Smith et al., on paragraphs 26 - 31 ; or U.S. Pat. No. 6,494,920, at column 1 , line 51 et seq. detailing an
  • estersquat or a quaternized fatty acid triethanolamine ester salt.
  • the FSA is chosen from at least one of the following: ditallowoyloxyethyl dimethyl ammonium chloride, dihydrogenated- tallowoyloxyethyl dimethyl ammonium chloride, ditallow dimethyl ammonium chloride, ditallowoyloxyethyl dimethyl ammonium methyl sulfate, dihydrogenated- tallowoyloxyethyl dimethyl ammonium chloride, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, or combinations thereof.
  • the FSA can also include amide containing compound compositions.
  • diamide comprising compounds include, but are not limited to, methyl-bis(tallowamidoethyl)-2-hydroxyethylammonium methyl sulfate (available from Degussa under the trade names Varisoft 1 10 and Varisoft 222).
  • An example of an amide-ester containing compound is N-[3- (stearoylamino)propyl]-N-[2-(stearoyloxy)ethoxy)ethyl)]-N-methylamine.
  • a rinse added fabric softening composition further comprising a cationic starch.
  • Cationic starches are disclosed in US 2004/0204337 A1 .
  • the rinse added fabric softening composition comprises from about 0.1 % to about 7% of cationic starch by weight of the fabric softening composition.
  • the cationic starch is HCP401 from National Starch.
  • Suitable Laundry Care Ingredients While not essential for the purposes of the present invention, the non- limiting list of laundry care ingredients illustrated hereinafter are suitable for use in the laundry care compositions and can be desirably incorporated in certain embodiments of the invention, for example to assist or enhance performance, for treatment of the substrate to be cleaned, or to modify the aesthetics of the laundry care compositions.
  • composition as is the case with perfumes, colorants, dyes or the like. It is
  • the total amount of such adjuncts can range from about 0.1 % to about 50%, or even from about 1 % to about 30%, by weight of the laundry care composition.
  • laundry care ingredients include, but are not limited to, polymers, for example cationic polymers, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfume and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments.
  • suitable examples of such other adjuncts and levels of use are found in U.S. Patent Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1 that are incorporated by reference.
  • laundry care ingredients are not essential to Applicants' laundry care compositions.
  • certain embodiments of Applicants' compositions do not contain one or more of the following adjuncts materials: bleach activators, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic metal complexes, polymeric dispersing agents, clay and soil removal/anti-redeposition agents, brighteners, suds
  • compositions according to the present invention can comprise a surfactant or surfactant system wherein the surfactant can be selected from nonionic and/or anionic and/or cationic surfactants and/or ampholytic and/or zwitterionic and/or semi-polar nonionic surfactants.
  • the surfactant is typically present at a level of from about 0.1 %, from about 1 %, or even from about 5% by weight of the cleaning compositions to about 99.9%, to about 80%, to about 35%, or even to about 30% by weight of the cleaning compositions.
  • compositions of the present invention can comprise one or more detergent builders or builder systems. When present, the compositions will typically comprise at least about 1 % builder, or from about 5% or 10% to about 80%, 50%, or even 30% by weight, of said builder.
  • Builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicate builders polycarboxylate compounds, ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1 ,3,5-trihydroxybenzene-2,4,6- trisulphonic acid, and carboxymethyl-oxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as
  • ethylenediamine tetraacetic acid and nitrilotriacetic acid as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1 ,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1 ,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • compositions herein can also optionally contain one or more copper, iron and/or manganese chelating agents. If utilized, chelating agents will generally comprise from about 0.1 % by weight of the compositions herein to about 15%, or even from about 3.0% to about 15% by weight of the compositions herein.
  • compositions of the present invention can also include one or more dye transfer inhibiting agents.
  • Suitable polymeric dye transfer inhibiting agents include, but are not limited to,
  • the dye transfer inhibiting agents are present at levels from about 0.0001 %, from about 0.01 %, from about 0.05% by weight of the cleaning compositions to about 10%, about 2%, or even about 1 % by weight of the cleaning compositions.
  • Dispersants - The compositions of the present invention can also contain dispersants.
  • Suitable water-soluble organic materials are the homo- or co- polymeric acids or their salts, in which the polycarboxylic acid can comprise at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Enzymes - The compositions can comprise one or more detergent enzymes which provide cleaning performance and/or fabric care benefits.
  • suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof.
  • a typical combination is a cocktail of conventional applicable enzymes like protease, lipase, cutinase and/or cellulase in conjunction with amylase.
  • Enzyme Stabilizers - Enzymes for use in compositions for example, detergents can be stabilized by various techniques.
  • the enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions that provide such ions to the enzymes.
  • Catalytic Metal Complexes - Applicants' compositions can include catalytic metal complexes.
  • One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methyl-enephosphonic acid) and water-soluble salts thereof.
  • Such catalysts are disclosed in U.S. patent 4,430,243.
  • compositions herein can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. patent 5,576,282.
  • Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. patents 5,597,936 and 5,595,967. Such cobalt catalysts are readily prepared by known procedures, such as taught for example in U.S. patents
  • compositions herein can also suitably include a transition metal complex of a macropolycyclic rigid ligand - abbreviated as "MRL".
  • MRL macropolycyclic rigid ligand
  • the compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the benefit agent MRL species in the aqueous washing medium, and can provide from about 0.005 ppm to about 25 ppm, from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to about 5 ppm, of the MRL in the wash liquor.
  • Preferred transition-metals in the instant transition-metal bleach catalyst include manganese, iron and chromium.
  • Preferred MRL's herein are a special type of ultra-rigid ligand that is cross-bridged such as 5,12-diethyl-1 ,5,8,12- tetraazabicyclo[6.6.2]hexa-decane.
  • Suitable transition metal MRLs are readily prepared by known procedures, such as taught for example in WO 00/32601 , and U.S. patent 6,225,464.
  • the following examples demonstrate the production of capsules according to the invention.
  • the capsules were produced using a triple nozzle coextrusion apparatus such as that depicted in Figure 4.
  • Different fluids were used to form the core(s), the intermediate layer, and the shell layer of the capsules.
  • Fluid 1 which contained the components that formed the core(s) of the capsules, was pumped through the first nozzle 410.
  • Fluid 2 which contained the components that formed the intermediate layer, was pumped through the second nozzle 420.
  • Fluid 3 which contained the components that formed the shell layer, was pumped through the third nozzle 430.
  • the compositions of the fluids used to produce the capsules in each example are described in further detail below.
  • the three fluids were simultaneously pumped through their respective nozzles so that one or more droplets of Fluid 1 emanating from nozzle 410 was encased in a droplet of Fluid 2 emanating from nozzle 420, which droplet was further encased by a droplet of Fluid 3 emanating from nozzle 430.
  • Each of the resulting "composite" droplets which would later form the capsule, was allowed to grow until it separated itself from the nozzles due to its growing weight.
  • the droplets were then collected in a bath of cold oil (e.g., corn oil or vegetable oil), in which the components of Fluid 3 solidified to form the shell layer of the capsule.
  • the resulting capsules were then collected and cleaned.
  • Fluid 1 was a 50 wt.% solution of Liquitint® Violet DD (available from Milliken & Company in Spartanburg, SC) in water.
  • Fluid 2 was a silicone oil (i.e., Dow Corning® 200 Fluid 500 cSt) containing approximately 2 wt.% hydrophobic, fumed silica particles (i.e., CAB-O-SIL® TS-720 fumed silica).
  • Fluid 3 was a 3 wt.% solution of agar in water.
  • Fluids 1 and 2 were delivered to their respective nozzles at room temperature, and Fluid 3 was heated and delivered to the nozzle at a temperature of greater than approximately 60 °C.
  • the fluids were passed through the triple nozzle coextrusion apparatus described above, and the droplets emerging from the apparatus were collected in cold corn oil maintained at a temperature of
  • the capsules contained at least one core of the polymeric colorant surrounded by an intermediate silicone layer encased in a solid hydrogel (agarose) shell layer.
  • Fluid 1 was a 50 wt.% solution of Liquitint® Violet DD (available from Milliken & Company in Spartanburg, SC) in water.
  • Fluid 2 was a silicone oil (i.e., Dow Corning® 200 Fluid 1 ,000 cSt) containing approximately 2 wt.% hydrophobic silica particles (i.e., Aerosil® 816R silica from Degussa).
  • Fluid 3 was a 3 wt.% solution of agar in water.
  • Fluids 1 and 2 were delivered to their respective nozzles at room temperature, and Fluid 3 was heated and delivered to the nozzle at a temperature of greater than approximately 60 °C.
  • the fluids were passed through the triple nozzle coextrusion apparatus described above, and the droplets emerging from the apparatus were collected in cold corn oil maintained at a temperature of
  • the capsules contained at least one core of the polymeric colorant surrounded by an intermediate silicone layer encased in a solid hydrogel (agarose) shell layer.
  • capsules Following collection and cleaning, some of the resulting capsules were placed in a liquid laundry detergent (i.e., Tide® laundry detergent from The Procter & Gamble Company). The capsules did not burst or leak upon addition to the liquid laundry detergent and remained stable (i.e., did not burst or leak) for several months.
  • a liquid laundry detergent i.e., Tide® laundry detergent from The Procter & Gamble Company.
  • Fluid 1 was a 50 wt.% solution of Liquitint® Violet DD (available from Milliken & Company in Spartanburg, SC) in water.
  • Fluid 2 was a silicone oil (i.e., Dow Corning® 200 Fluid 500 cSt) containing approximately 3 wt.% hydrophobic silica particles (i.e., Aerosil® 816R silica from Degussa).
  • Fluid 3 was a 3 wt.% solution of agar in water.
  • Fluids 1 and 2 were delivered to their respective nozzles at room temperature, and Fluid 3 was heated and delivered to the nozzle at a temperature of greater than approximately 60 °C.
  • the fluids were passed through the triple nozzle coextrusion apparatus described above, and the droplets emerging from the apparatus were collected in cold corn oil maintained at a temperature of approximately 0-10 °C.
  • the components of Fluid 3 coalesced almost instantly on contact with the cold corn oil to form capsules according to the invention.
  • the capsules contained at least one core of the polymeric colorant surrounded by an intermediate silicone layer encased in a solid hydrogel (agarose) shell layer.
  • Fluid 1 was a 50 wt.% solution of Liquitint® Violet DD (available from Milliken & Company in Spartanburg, SC) in water.
  • Fluid 2 was a silicone oil (i.e., Dow Corning® 200 Fluid 500 cSt) containing approximately 4 wt.% hydrophobic silica particles (i.e., Aerosil® 816R silica from Degussa).
  • Fluid 3 was a 3 wt.% solution of agar in water.
  • Fluids 1 and 2 were delivered to their respective nozzles at room temperature, and Fluid 3 was heated and delivered to the nozzle at a temperature of greater than approximately 60 °C.
  • the fluids were passed through the triple nozzle coextrusion apparatus described above, and the droplets emerging from the apparatus were collected in cold corn oil maintained at a temperature of
  • the capsules contained at least one core of the polymeric colorant surrounded by an intermediate silicone layer encased in a solid hydrogel (agarose) shell layer.
  • Fluid 1 was a 50 wt.% solution of Liquitint® Violet DD (available from Milliken & Company in Spartanburg, SC) in water.
  • Fluid 2 was a silicone oil (i.e., Dow Corning® 200 Fluid 1 ,000 cSt) containing approximately 2 wt.% hydrophobic silica particles (i.e., Aerosil® 816R silica from Degussa).
  • Fluid 3 was an aqueous solution containing approximately 2 wt.% agar, approximately 1 wt.% sodium polyacrylate (a
  • Fluids 1 and 2 were delivered to their respective nozzles at room temperature, and Fluid 3 was heated and delivered to the nozzle at a temperature of greater than approximately 60 °C. The fluids were passed through the triple nozzle coextrusion apparatus described above, and the droplets emerging from the apparatus were collected in cold corn oil maintained at a temperature of
  • the capsules contained at least one core of the polymeric colorant surrounded by an intermediate silicone layer encased in a solid hydrogel (agarose) shell layer.
  • the resulting capsules were placed in a liquid laundry detergent (i.e., Tide® laundry detergent from The Procter & Gamble Company).
  • a liquid laundry detergent i.e., Tide® laundry detergent from The Procter & Gamble Company.
  • Tide® laundry detergent from The Procter & Gamble Company.
  • the capsules did not burst or leak upon addition to the liquid laundry detergent.
  • the liquid laundry detergent containing the capsules was diluted with water at a level similar to that encountered in household laundering conditions, the capsules burst and released the polymeric colorant into the water.
  • Fluid 1 was a 50 wt.% solution of Liquitint® Violet DD (available from Milliken & Company in Spartanburg, SC) in water.
  • Fluid 2 was a silicone oil (i.e., Dow Corning® 200 Fluid 1 ,000 cSt) containing approximately 2 wt.% hydrophobic silica particles (i.e., Aerosil® 816R silica from Degussa).
  • Fluid 3 was an aqueous solution containing approximately 3 wt.% agar, approximately 2 wt.% sodium polyacrylate (a
  • Fluids 1 and 2 were delivered to their respective nozzles at room temperature, and Fluid 3 was heated and delivered to the nozzle at a temperature of greater than approximately 60 °C.
  • the fluids were passed through the triple nozzle coextrusion apparatus described above, and the droplets emerging from the apparatus were collected in cold corn oil maintained at a temperature of
  • the capsules contained at least one core of the polymeric colorant surrounded by an intermediate silicone layer encased in a solid hydrogel (agarose) shell layer.
  • the resulting capsules were placed in a liquid laundry detergent (i.e., Tide® laundry detergent from The Procter & Gamble Company).
  • a liquid laundry detergent i.e., Tide® laundry detergent from The Procter & Gamble Company.
  • Tide® laundry detergent from The Procter & Gamble Company.
  • the capsules did not burst or leak upon addition to the liquid laundry detergent.
  • the liquid laundry detergent containing the capsules was diluted with water at a level similar to that encountered in household laundering conditions, the capsules burst and released the polymeric colorant into the water.

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  • Oil, Petroleum & Natural Gas (AREA)
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  • Textile Engineering (AREA)
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Abstract

La présente invention concerne une capsule sans soudure qui comprend au moins un noyau et une couche d'enveloppe. La capsule peut comprendre en outre une couche intermédiaire qui entoure le(s) noyau(x) et est entourée par la couche d'enveloppe. La couche d'enveloppe comprend un matériau choisi dans le groupe constitué de polymères hydrosolubles, de polymère dispersible dans l'eau, d'hydrogels. La couche d'enveloppe peut comprendre en outre un agent délitant.
PCT/US2012/026043 2011-02-25 2012-02-22 Capsules et compositions comprenant celles-ci WO2012116021A1 (fr)

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CN201280019482.4A CN103492062A (zh) 2011-02-25 2012-02-22 胶囊及包含其的组合物
JP2013555514A JP2014512257A (ja) 2011-02-25 2012-02-22 カプセルおよびそれを含む組成物
EP12706418.6A EP2678101A1 (fr) 2011-02-25 2012-02-22 Capsules et compositions comprenant celles-ci

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US13/035,409 2011-02-25
US13/035,409 US20120220514A1 (en) 2011-02-25 2011-02-25 Capsules and compositions comprising the same
US13/035,445 US9725684B2 (en) 2011-02-25 2011-02-25 Capsules and compositions comprising the same
US13/035,445 2011-02-25
US13/400,988 2012-02-21
US13/400,988 US20130217609A1 (en) 2012-02-21 2012-02-21 Capsules and compositions comprising the same

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RU2556652C1 (ru) * 2013-12-24 2015-07-10 Александр Александрович Кролевец Способ инкапсуляции унаби
JP2016532546A (ja) * 2013-07-30 2016-10-20 ユニリーバー・ナームローゼ・ベンノートシヤープ カプセル封入有益剤に関する改良
JP2017501330A (ja) * 2013-12-05 2017-01-12 プラスチック・オムニウム・アドヴァンスド・イノベーション・アンド・リサーチ 自動車における使用のための分解ユニットを積載又は再積載する方法及びシステム

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103874758A (zh) * 2011-09-13 2014-06-18 宝洁公司 包封物
NO2719169T3 (fr) * 2014-06-17 2018-06-23
WO2016081437A1 (fr) * 2014-11-17 2016-05-26 The Procter & Gamble Company Compositions d'apport d'agent bénéfique
CN105670809A (zh) * 2016-02-24 2016-06-15 奉化市瑶琴生物科技有限公司 一种便捷式家居清洁剂及其制备和使用方法
CN107780238A (zh) * 2016-08-31 2018-03-09 江苏新瑞贝科技股份有限公司 一种用于染色工序的可溶解胶囊
CN108130742B (zh) * 2016-12-01 2020-07-10 广州蓝月亮实业有限公司 一种护理组合物、护理剂及其制备方法和应用
CN106929931B (zh) * 2017-03-24 2020-05-12 青岛邦特生态纺织科技有限公司 一种含板蓝根提取物的粘胶纤维及其制备方法
CN109137113B (zh) * 2017-03-24 2021-06-01 青岛邦特生态纺织科技有限公司 一种吸湿性好的相变调温粘胶纤维及其制备方法
AU2019321593A1 (en) * 2018-08-17 2021-03-18 The Regents Of The University Of California Particle-containing droplet systems with monodisperse fluid volumes
KR102280148B1 (ko) * 2018-12-04 2021-07-21 주식회사 케이티앤지 삼중 캡슐 및 이를 제조하는 장치 및 방법
CN111074395A (zh) * 2019-12-30 2020-04-28 江苏欧博智能纺织有限公司 一种具有芳香耐久的氨纶包覆纱线及其制备方法
CN111604013A (zh) * 2020-04-08 2020-09-01 名畔科技(镇江)有限公司 一种利用聚乙二醇长链烷基酰胺实现香精缓释的方法
CN111589388A (zh) * 2020-04-21 2020-08-28 同济大学 一种阻燃微胶囊及其制备方法
CN111589387A (zh) * 2020-04-21 2020-08-28 同济大学 一种微胶囊复合材料及其制备方法
JP7440766B2 (ja) 2020-06-17 2024-02-29 藤倉化成株式会社 水系塗料組成物及び塗装方法
CN114307983A (zh) * 2021-10-22 2022-04-12 海南大学 一种兼具分离富集、检测、催化功能的一体化智能结构体系及其制备方法
CN117358165B (zh) * 2023-12-06 2024-02-06 潍坊光华精细化工有限公司 一种核壳结构柑橘精油纳米混悬剂凝胶的制备工艺

Citations (116)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2220099A (en) 1934-01-10 1940-11-05 Gen Aniline & Flim Corp Sulphonic acids
US2477383A (en) 1946-12-26 1949-07-26 California Research Corp Sulfonated detergent and its method of preparation
DE1542260A1 (de) * 1965-03-05 1970-03-26 Keuffel & Esser Co Mit festem oder fluessigem Material gefuellte Kapseln
US3929678A (en) 1974-08-01 1975-12-30 Procter & Gamble Detergent composition having enhanced particulate soil removal performance
US3986972A (en) 1975-10-24 1976-10-19 American Cyanamid Company Acyl nitrile compounds as peroxygen bleach activators
US4217105A (en) 1977-03-28 1980-08-12 The Procter & Gamble Company Photoactivated bleach-compositions and processes
US4228042A (en) 1978-06-26 1980-10-14 The Procter & Gamble Company Biodegradable cationic surface-active agents containing ester or amide and polyalkoxy group
US4239660A (en) 1978-12-13 1980-12-16 The Procter & Gamble Company Detergent composition comprising a hydrolyzable cationic surfactant and specific alkalinity source
US4260529A (en) 1978-06-26 1981-04-07 The Procter & Gamble Company Detergent composition consisting essentially of biodegradable nonionic surfactant and cationic surfactant containing ester or amide
US4412934A (en) 1982-06-30 1983-11-01 The Procter & Gamble Company Bleaching compositions
US4430243A (en) 1981-08-08 1984-02-07 The Procter & Gamble Company Bleach catalyst compositions and use thereof in laundry bleaching and detergent compositions
US4483779A (en) 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions comprising polyglycoside and polyethoxylate surfactants and anionic fluorescer
US4483780A (en) 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions containing polyglycoside and polyethoxylate detergent surfactants
US4483781A (en) 1983-09-02 1984-11-20 The Procter & Gamble Company Magnesium salts of peroxycarboxylic acids
EP0133354A1 (fr) 1983-08-09 1985-02-20 Interox Chemicals Limited Composition de nettoyage pour prothèses dentaires
US4565647A (en) 1982-04-26 1986-01-21 The Procter & Gamble Company Foaming surfactant compositions
US4634551A (en) 1985-06-03 1987-01-06 Procter & Gamble Company Bleaching compounds and compositions comprising fatty peroxyacids salts thereof and precursors therefor having amide moieties in the fatty chain
US4728455A (en) 1986-03-07 1988-03-01 Lever Brothers Company Detergent bleach compositions, bleaching agents and bleach activators
US4810410A (en) 1986-12-13 1989-03-07 Interox Chemicals Limited Bleach activation
US4915854A (en) 1986-11-14 1990-04-10 The Procter & Gamble Company Ion-pair complex conditioning agent and compositions containing same
US4966723A (en) 1988-02-11 1990-10-30 Bp Chemicals Limited Bleach activators in detergent compositions
US5004558A (en) 1986-11-03 1991-04-02 Monsanto Company Sulfone peroxycarboxylic acids
WO1992006162A1 (fr) 1990-09-28 1992-04-16 The Procter & Gamble Company Detergent contenant des tensioactifs de sulfate d'alkyle et d'amide de l'acide gras de polyhydroxy
US5114606A (en) 1990-02-19 1992-05-19 Lever Brothers Company, Division Of Conopco, Inc. Bleaching composition comprising as a bleaching catalyst a complex of manganese with a non-carboxylate polyhydroxy ligand
US5114611A (en) 1989-04-13 1992-05-19 Lever Brothers Company, Divison Of Conopco, Inc. Bleach activation
US5130045A (en) 1987-10-30 1992-07-14 The Clorox Company Delayed onset active oxygen bleach composition
US5132431A (en) 1990-02-05 1992-07-21 Hoechst Aktiengesellschaft Process for the continuous preparation of imidoperoxycarboxylic acids
US5153161A (en) 1991-11-26 1992-10-06 Lever Brothers Company, Division Of Conopco, Inc. Synthesis of manganese oxidation catalyst
US5194416A (en) 1991-11-26 1993-03-16 Lever Brothers Company, Division Of Conopco, Inc. Manganese catalyst for activating hydrogen peroxide bleaching
EP0544490A1 (fr) 1991-11-26 1993-06-02 Unilever Plc Compositions détergentes de blanchiment
EP0544440A2 (fr) 1991-11-20 1993-06-02 Unilever Plc Composition catalytique pour le blanchiment, fabrication et utilisation dans des compositions détergentes et/ou de blanchiment
EP0549271A1 (fr) 1991-12-20 1993-06-30 Unilever Plc Activation de blanchiment
EP0549272A1 (fr) 1991-12-20 1993-06-30 Unilever Plc Activation de blanchiment
US5227084A (en) 1991-04-17 1993-07-13 Lever Brothers Company, Division Of Conopco, Inc. Concentrated detergent powder compositions
US5244594A (en) 1990-05-21 1993-09-14 Lever Brothers Company, Division Of Conopco, Inc. Bleach activation multinuclear manganese-based coordination complexes
US5246612A (en) 1991-08-23 1993-09-21 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing composition containing peroxygen bleach, manganese complex and enzymes
US5246620A (en) 1990-04-21 1993-09-21 Hoechst Aktiengesellschaft Stable peroxycarboxylic acid granules
WO1993019146A1 (fr) 1992-03-16 1993-09-30 The Procter & Gamble Company Compositions fluides renfermant des amides d'acides gras polyhydroxy
WO1993019038A1 (fr) 1992-03-26 1993-09-30 The Procter & Gamble Company Procede d'abaissement des niveaux de contaminants acides gras dans les tensioactifs a base d'amides d'acides gras polyhydroxy
US5256779A (en) 1992-06-18 1993-10-26 Lever Brothers Company, Division Of Conopco, Inc. Synthesis of manganese oxidation catalyst
US5274147A (en) 1991-07-11 1993-12-28 Lever Brothers Company, Division Of Conopco, Inc. Process for preparing manganese complexes
US5279757A (en) 1990-04-06 1994-01-18 Hoechst Aktiengesellschaft Stable peroxycarboxylic acid granule comprising an imidoperoxycarboxylic acid or salt thereof
US5280117A (en) 1992-09-09 1994-01-18 Lever Brothers Company, A Division Of Conopco, Inc. Process for the preparation of manganese bleach catalyst
US5284944A (en) 1992-06-30 1994-02-08 Lever Brothers Company, Division Of Conopco, Inc. Improved synthesis of 1,4,7-triazacyclononane
WO1994009099A1 (fr) 1992-10-13 1994-04-28 The Procter & Gamble Company Compositions fluides contenant des amides d'acides gras polyhydroxy
US5310934A (en) 1992-02-21 1994-05-10 Ausimont S.P.A. Process for purifying phthalimidoperoxycaproic acid (PAP) in order to remove chlorinated solvent impurities from it
US5330835A (en) 1991-07-31 1994-07-19 Morishita Jintan Co., Ltd. Seamless capsule and process for producing the same
US5332528A (en) 1990-09-28 1994-07-26 The Procter & Gamble Company Polyhydroxy fatty acid amides in soil release agent-containing detergent compositions
US5346588A (en) 1989-10-30 1994-09-13 Lenzing Aktiengesellschaft Process for the chlorine-free bleaching of cellulosic materials with ozone
US5360569A (en) 1993-11-12 1994-11-01 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with catalytic imine quaternary salts
US5370826A (en) 1993-11-12 1994-12-06 Lever Brothers Company, Division Of Conopco, Inc. Quaternay oxaziridinium salts as bleaching compounds
WO1994028102A1 (fr) 1993-05-20 1994-12-08 The Procter & Gamble Company Composes de blanchiment comprenant du n-acyl caprolactame, utiles dans le lavage a la main ou dans d'autres systemes de nettoyage de textiles a faible teneur en eau
US5405412A (en) 1994-04-13 1995-04-11 The Procter & Gamble Company Bleaching compounds comprising N-acyl caprolactam and alkanoyloxybenzene sulfonate bleach activators
US5405413A (en) 1993-06-24 1995-04-11 The Procter & Gamble Co. Bleaching compounds comprising acyl valerolactam bleach activators
WO1995013352A1 (fr) 1993-11-12 1995-05-18 Unilever N.V. Sels quaternaires d'imine utilises comme catalyseurs de blanchiment
WO1995013353A1 (fr) 1993-11-12 1995-05-18 Unilever N.V. Activation de precurseurs d'agents de blanchiment a l'aide de sels quaternaires d'imine
US5460747A (en) 1994-08-31 1995-10-24 The Procter & Gamble Co. Multiple-substituted bleach activators
US5482515A (en) 1993-11-12 1996-01-09 Lever Brothers Company, Division Of Conopco, Inc. Imine quaternary salts as bleach catalysts
US5487818A (en) 1992-03-10 1996-01-30 Ausimont S.P.A. Process for separating phthalimido-peroxycaproic acid from solutions in organic solvents
US5523434A (en) 1995-03-15 1996-06-04 The Procter & Gamble Company Synthesis of bleach activators
US5576282A (en) 1995-09-11 1996-11-19 The Procter & Gamble Company Color-safe bleach boosters, compositions and laundry methods employing same
US5578136A (en) 1994-08-31 1996-11-26 The Procter & Gamble Company Automatic dishwashing compositions comprising quaternary substituted bleach activators
US5584888A (en) 1994-08-31 1996-12-17 Miracle; Gregory S. Perhydrolysis-selective bleach activators
WO1996040661A1 (fr) 1995-06-07 1996-12-19 The Clorox Company Activateur de blanchiment a l'acetonitrile d'ammonium n-alkyle
US5595967A (en) 1995-02-03 1997-01-21 The Procter & Gamble Company Detergent compositions comprising multiperacid-forming bleach activators
US5597936A (en) 1995-06-16 1997-01-28 The Procter & Gamble Company Method for manufacturing cobalt catalysts
EP0790244A1 (fr) 1996-02-15 1997-08-20 Hoechst Aktiengesellschaft Activateurs de blanchiment à de nitriles d'ammonium
US5686015A (en) 1994-08-31 1997-11-11 The Procter & Gamble Company Quaternary substituted bleach activators
US5686014A (en) 1994-04-07 1997-11-11 The Procter & Gamble Company Bleach compositions comprising manganese-containing bleach catalysts
US5695679A (en) 1994-07-07 1997-12-09 The Procter & Gamble Company Detergent compositions containing an organic silver coating agent to minimize silver training in ADW washing methods
US5698504A (en) 1993-07-01 1997-12-16 The Procter & Gamble Company Machine dishwashing composition containing oxygen bleach and paraffin oil and benzotriazole compound silver tarnishing inhibitors
US5703030A (en) 1995-06-16 1997-12-30 The Procter & Gamble Company Bleach compositions comprising cobalt catalysts
US5718614A (en) 1995-08-28 1998-02-17 Electro-Matic Products Company Control apparatus for grinder
US5759990A (en) 1996-10-21 1998-06-02 The Procter & Gamble Company Concentrated fabric softening composition with good freeze/thaw recovery and highly unsaturated fabric softener compound therefor
WO1998035005A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Composition nettoyante
WO1998035002A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Compositions nettoyantes
WO1998035003A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Compose detergent
WO1998035004A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Compositions detergentes solides
WO1998035006A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Composition nettoyante liquide
WO1999005241A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Produits de nettoyage comportant des tensioactifs alkylarylsulfonate ameliores prepares a l'aide d'olefines de vinylidene et procedes de preparation desdits produits
WO1999005082A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Procedes ameliores de preparation de tensioactifs alkylbenzenesulfonate et produits contenant lesdits tensioactifs
WO1999005084A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Procede de preparation de tensioactifs alkylbenzenesulfonate a partir d'alcools et produits contenant lesdits tensioactifs
WO1999005242A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Tensio-actifs ameliores d'alkylbenzenesulfonate
WO1999005244A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Tensio-actifs ameliores d'alkylarylsulfonate
WO1999005243A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Compositions detergentes contenant des melanges de tensio-actifs a cristallinite disloquee
WO1999007656A2 (fr) 1997-08-08 1999-02-18 The Procter & Gamble Company Procedes ameliores de fabrication de tensio-actifs selon une technique de separation par adsorption et produits ainsi obtenus
WO1999014296A1 (fr) 1997-09-16 1999-03-25 Clariant Gmbh Activateurs de blanchiment a base de nitrile d'ammonium sous forme de granules enrobes
WO1999014302A1 (fr) 1997-09-16 1999-03-25 Clariant Gmbh Activateurs de blanchiment sous forme de granules
US5916481A (en) 1995-07-25 1999-06-29 The Procter & Gamble Company Low hue photobleaches
US5998350A (en) 1993-05-20 1999-12-07 The Procter & Gamble Company Bleaching compounds comprising N-acyl caprolactam and/or peroxy acid activators
US6004922A (en) 1996-05-03 1999-12-21 The Procter & Gamble Company Laundry detergent compositions comprising cationic surfactants and modified polyamine soil dispersents
US6008181A (en) 1996-04-16 1999-12-28 The Procter & Gamble Company Mid-Chain branched Alkoxylated Sulfate Surfactants
JP2000026282A (ja) * 1998-07-14 2000-01-25 Shionogi & Co Ltd 溶出性が改善された硬ゼラチンカプセル剤
US6020303A (en) 1996-04-16 2000-02-01 The Procter & Gamble Company Mid-chain branched surfactants
US6022844A (en) 1996-03-05 2000-02-08 The Procter & Gamble Company Cationic detergent compounds
WO2000023549A1 (fr) 1998-10-20 2000-04-27 The Procter & Gamble Company Detergents a lessive comprenant des alcoylbenzenesulfonates modifies
WO2000023548A1 (fr) 1998-10-20 2000-04-27 The Procter & Gamble Company Detergents a lessive comprenant des alcoylbenzenesulfonates modifies
US6060443A (en) 1996-04-16 2000-05-09 The Procter & Gamble Company Mid-chain branched alkyl sulfate surfactants
WO2000032601A2 (fr) 1998-11-30 2000-06-08 The Procter & Gamble Company Procede de preparation de tetraaza macrocycles pontes transversalement
US6093856A (en) 1996-11-26 2000-07-25 The Procter & Gamble Company Polyoxyalkylene surfactants
WO2000047708A1 (fr) 1999-02-10 2000-08-17 The Procter & Gamble Company Solides particulaires faible densite utilises dans les detergents pour lessive
US6136769A (en) 1996-05-17 2000-10-24 The Procter & Gamble Company Alkoxylated cationic detergency ingredients
US6140294A (en) 1998-11-10 2000-10-31 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Bleach and oxidation catalyst
US6150322A (en) 1998-08-12 2000-11-21 Shell Oil Company Highly branched primary alcohol compositions and biodegradable detergents made therefrom
US6221825B1 (en) 1996-12-31 2001-04-24 The Procter & Gamble Company Thickened, highly aqueous liquid detergent compositions
US6225464B1 (en) 1997-03-07 2001-05-01 The Procter & Gamble Company Methods of making cross-bridged macropolycycles
WO2001042408A2 (fr) 1999-12-08 2001-06-14 The Procter & Gamble Company Tensioactifs a base d'alcools poly(oxyalkyles) coiffes par un ether
US6287580B1 (en) 1999-08-13 2001-09-11 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Cosmetic compositions with self-warming component
US6302921B1 (en) 1999-09-01 2001-10-16 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Method of bleaching stained fabrics
US6306812B1 (en) 1997-03-07 2001-10-23 Procter & Gamble Company, The Bleach compositions containing metal bleach catalyst, and bleach activators and/or organic percarboxylic acids
US6326348B1 (en) 1996-04-16 2001-12-04 The Procter & Gamble Co. Detergent compositions containing selected mid-chain branched surfactants
US6482994B2 (en) 1997-08-02 2002-11-19 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
US6494920B1 (en) 1999-02-04 2002-12-17 Cognis Deutschland Gmbh & Co. Kg Detergent mixtures
US20040204337A1 (en) 2003-03-25 2004-10-14 The Procter & Gamble Company Fabric care compositions comprising cationic starch
US20040229769A1 (en) 2000-12-27 2004-11-18 Colgate-Palmolive Company Thickened fabric conditioners
US20080292692A1 (en) * 2007-05-21 2008-11-27 Shira Pilch Impermeable Capsules

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3015128A (en) 1960-08-18 1962-01-02 Southwest Res Inst Encapsulating apparatus
GB1096640A (en) 1964-12-07 1967-12-29 Monsanto Co Micro-fiber spinning process
US3310612A (en) 1965-03-29 1967-03-21 Southwest Res Inst Encapsulating method and apparatus
JPS5858146A (ja) * 1981-10-05 1983-04-06 Tanabe Seiyaku Co Ltd 速放性マイクロカプセル
DE59912558D1 (de) * 1999-07-02 2005-10-20 Cognis Ip Man Gmbh Mikrokapseln - IV
HUP0203565A3 (en) * 1999-12-03 2006-06-28 Procter & Gamble Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes
DE10012199A1 (de) * 2000-03-13 2001-09-20 Haarmann & Reimer Gmbh Eingekapselte Substanzen mit kontrollierter Freisetzung
WO2003043659A1 (fr) * 2001-11-16 2003-05-30 Givaudan Sa Film comestible
EP1541121B1 (fr) * 2003-12-11 2007-03-21 Rohm And Haas Company Système et procédé pour libérer des ingrédients actifs encapsulés
US7485609B2 (en) * 2005-09-29 2009-02-03 Kimberly-Clark Worldwide, Inc. Encapsulated liquid cleanser
US7662461B2 (en) * 2006-03-31 2010-02-16 Milliken & Company Synthetic leather articles and methods for producing the same
US10960077B2 (en) * 2006-05-12 2021-03-30 Intellipharmaceutics Corp. Abuse and alcohol resistant drug composition
CN1935972A (zh) * 2006-09-20 2007-03-28 王涛 洗涤胶囊及其制备方法

Patent Citations (136)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2220099A (en) 1934-01-10 1940-11-05 Gen Aniline & Flim Corp Sulphonic acids
US2477383A (en) 1946-12-26 1949-07-26 California Research Corp Sulfonated detergent and its method of preparation
DE1542260A1 (de) * 1965-03-05 1970-03-26 Keuffel & Esser Co Mit festem oder fluessigem Material gefuellte Kapseln
US3929678A (en) 1974-08-01 1975-12-30 Procter & Gamble Detergent composition having enhanced particulate soil removal performance
US3986972A (en) 1975-10-24 1976-10-19 American Cyanamid Company Acyl nitrile compounds as peroxygen bleach activators
US4217105A (en) 1977-03-28 1980-08-12 The Procter & Gamble Company Photoactivated bleach-compositions and processes
US4228042A (en) 1978-06-26 1980-10-14 The Procter & Gamble Company Biodegradable cationic surface-active agents containing ester or amide and polyalkoxy group
US4260529A (en) 1978-06-26 1981-04-07 The Procter & Gamble Company Detergent composition consisting essentially of biodegradable nonionic surfactant and cationic surfactant containing ester or amide
US4239660A (en) 1978-12-13 1980-12-16 The Procter & Gamble Company Detergent composition comprising a hydrolyzable cationic surfactant and specific alkalinity source
US4430243A (en) 1981-08-08 1984-02-07 The Procter & Gamble Company Bleach catalyst compositions and use thereof in laundry bleaching and detergent compositions
US4483779A (en) 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions comprising polyglycoside and polyethoxylate surfactants and anionic fluorescer
US4483780A (en) 1982-04-26 1984-11-20 The Procter & Gamble Company Detergent compositions containing polyglycoside and polyethoxylate detergent surfactants
US4565647B1 (en) 1982-04-26 1994-04-05 Procter & Gamble Foaming surfactant compositions
US4565647A (en) 1982-04-26 1986-01-21 The Procter & Gamble Company Foaming surfactant compositions
US4412934A (en) 1982-06-30 1983-11-01 The Procter & Gamble Company Bleaching compositions
EP0133354A1 (fr) 1983-08-09 1985-02-20 Interox Chemicals Limited Composition de nettoyage pour prothèses dentaires
US4483781A (en) 1983-09-02 1984-11-20 The Procter & Gamble Company Magnesium salts of peroxycarboxylic acids
US4634551A (en) 1985-06-03 1987-01-06 Procter & Gamble Company Bleaching compounds and compositions comprising fatty peroxyacids salts thereof and precursors therefor having amide moieties in the fatty chain
US4728455A (en) 1986-03-07 1988-03-01 Lever Brothers Company Detergent bleach compositions, bleaching agents and bleach activators
US5004558A (en) 1986-11-03 1991-04-02 Monsanto Company Sulfone peroxycarboxylic acids
US4915854A (en) 1986-11-14 1990-04-10 The Procter & Gamble Company Ion-pair complex conditioning agent and compositions containing same
US4810410A (en) 1986-12-13 1989-03-07 Interox Chemicals Limited Bleach activation
US5130045A (en) 1987-10-30 1992-07-14 The Clorox Company Delayed onset active oxygen bleach composition
US4966723A (en) 1988-02-11 1990-10-30 Bp Chemicals Limited Bleach activators in detergent compositions
US5114611A (en) 1989-04-13 1992-05-19 Lever Brothers Company, Divison Of Conopco, Inc. Bleach activation
US5346588A (en) 1989-10-30 1994-09-13 Lenzing Aktiengesellschaft Process for the chlorine-free bleaching of cellulosic materials with ozone
US5132431A (en) 1990-02-05 1992-07-21 Hoechst Aktiengesellschaft Process for the continuous preparation of imidoperoxycarboxylic acids
US5114606A (en) 1990-02-19 1992-05-19 Lever Brothers Company, Division Of Conopco, Inc. Bleaching composition comprising as a bleaching catalyst a complex of manganese with a non-carboxylate polyhydroxy ligand
US5279757A (en) 1990-04-06 1994-01-18 Hoechst Aktiengesellschaft Stable peroxycarboxylic acid granule comprising an imidoperoxycarboxylic acid or salt thereof
US5246620A (en) 1990-04-21 1993-09-21 Hoechst Aktiengesellschaft Stable peroxycarboxylic acid granules
US5246621A (en) 1990-05-21 1993-09-21 Lever Brothers Company, Division Of Conopco, Inc. Bleach activation by manganese-based coordination complexes
US5244594A (en) 1990-05-21 1993-09-14 Lever Brothers Company, Division Of Conopco, Inc. Bleach activation multinuclear manganese-based coordination complexes
US5332528A (en) 1990-09-28 1994-07-26 The Procter & Gamble Company Polyhydroxy fatty acid amides in soil release agent-containing detergent compositions
WO1992006162A1 (fr) 1990-09-28 1992-04-16 The Procter & Gamble Company Detergent contenant des tensioactifs de sulfate d'alkyle et d'amide de l'acide gras de polyhydroxy
US5227084A (en) 1991-04-17 1993-07-13 Lever Brothers Company, Division Of Conopco, Inc. Concentrated detergent powder compositions
US5274147A (en) 1991-07-11 1993-12-28 Lever Brothers Company, Division Of Conopco, Inc. Process for preparing manganese complexes
US5330835A (en) 1991-07-31 1994-07-19 Morishita Jintan Co., Ltd. Seamless capsule and process for producing the same
US5246612A (en) 1991-08-23 1993-09-21 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing composition containing peroxygen bleach, manganese complex and enzymes
EP0544440A2 (fr) 1991-11-20 1993-06-02 Unilever Plc Composition catalytique pour le blanchiment, fabrication et utilisation dans des compositions détergentes et/ou de blanchiment
US5194416A (en) 1991-11-26 1993-03-16 Lever Brothers Company, Division Of Conopco, Inc. Manganese catalyst for activating hydrogen peroxide bleaching
EP0544490A1 (fr) 1991-11-26 1993-06-02 Unilever Plc Compositions détergentes de blanchiment
US5153161A (en) 1991-11-26 1992-10-06 Lever Brothers Company, Division Of Conopco, Inc. Synthesis of manganese oxidation catalyst
EP0549271A1 (fr) 1991-12-20 1993-06-30 Unilever Plc Activation de blanchiment
EP0549272A1 (fr) 1991-12-20 1993-06-30 Unilever Plc Activation de blanchiment
US5310934A (en) 1992-02-21 1994-05-10 Ausimont S.P.A. Process for purifying phthalimidoperoxycaproic acid (PAP) in order to remove chlorinated solvent impurities from it
US5487818A (en) 1992-03-10 1996-01-30 Ausimont S.P.A. Process for separating phthalimido-peroxycaproic acid from solutions in organic solvents
WO1993019146A1 (fr) 1992-03-16 1993-09-30 The Procter & Gamble Company Compositions fluides renfermant des amides d'acides gras polyhydroxy
WO1993019038A1 (fr) 1992-03-26 1993-09-30 The Procter & Gamble Company Procede d'abaissement des niveaux de contaminants acides gras dans les tensioactifs a base d'amides d'acides gras polyhydroxy
US5256779A (en) 1992-06-18 1993-10-26 Lever Brothers Company, Division Of Conopco, Inc. Synthesis of manganese oxidation catalyst
US5284944A (en) 1992-06-30 1994-02-08 Lever Brothers Company, Division Of Conopco, Inc. Improved synthesis of 1,4,7-triazacyclononane
US5280117A (en) 1992-09-09 1994-01-18 Lever Brothers Company, A Division Of Conopco, Inc. Process for the preparation of manganese bleach catalyst
WO1994009099A1 (fr) 1992-10-13 1994-04-28 The Procter & Gamble Company Compositions fluides contenant des amides d'acides gras polyhydroxy
US5686401A (en) 1993-05-20 1997-11-11 The Procter & Gamble Company Bleaching compounds comprising N-acyl caprolactam for use in hand-wash or other low-water cleaning systems
WO1994028102A1 (fr) 1993-05-20 1994-12-08 The Procter & Gamble Company Composes de blanchiment comprenant du n-acyl caprolactame, utiles dans le lavage a la main ou dans d'autres systemes de nettoyage de textiles a faible teneur en eau
US5998350A (en) 1993-05-20 1999-12-07 The Procter & Gamble Company Bleaching compounds comprising N-acyl caprolactam and/or peroxy acid activators
US5503639A (en) 1993-06-24 1996-04-02 The Procter & Gamble Company Bleaching compounds comprising acyl valerolactam bleach activators
US5405413A (en) 1993-06-24 1995-04-11 The Procter & Gamble Co. Bleaching compounds comprising acyl valerolactam bleach activators
US5698504A (en) 1993-07-01 1997-12-16 The Procter & Gamble Company Machine dishwashing composition containing oxygen bleach and paraffin oil and benzotriazole compound silver tarnishing inhibitors
US5442066A (en) 1993-11-12 1995-08-15 Lever Brothers Company, Division Of Conopco, Inc. Quaternary oxaziridinium salts as bleaching compounds
WO1995013353A1 (fr) 1993-11-12 1995-05-18 Unilever N.V. Activation de precurseurs d'agents de blanchiment a l'aide de sels quaternaires d'imine
WO1995013352A1 (fr) 1993-11-12 1995-05-18 Unilever N.V. Sels quaternaires d'imine utilises comme catalyseurs de blanchiment
US5478357A (en) 1993-11-12 1995-12-26 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with imine quaternary salts
US5482515A (en) 1993-11-12 1996-01-09 Lever Brothers Company, Division Of Conopco, Inc. Imine quaternary salts as bleach catalysts
WO1995013351A1 (fr) 1993-11-12 1995-05-18 Unilever N.V. Sels d'oxaziridinium quarternaire utilises comme composes de blanchiment
US5370826A (en) 1993-11-12 1994-12-06 Lever Brothers Company, Division Of Conopco, Inc. Quaternay oxaziridinium salts as bleaching compounds
US5550256A (en) 1993-11-12 1996-08-27 Lever Brothers Company, Division Of Conopco, Inc. Imine quaternary salts as bleach catalysts
US5360569A (en) 1993-11-12 1994-11-01 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with catalytic imine quaternary salts
US5686014A (en) 1994-04-07 1997-11-11 The Procter & Gamble Company Bleach compositions comprising manganese-containing bleach catalysts
US5405412A (en) 1994-04-13 1995-04-11 The Procter & Gamble Company Bleaching compounds comprising N-acyl caprolactam and alkanoyloxybenzene sulfonate bleach activators
US5695679A (en) 1994-07-07 1997-12-09 The Procter & Gamble Company Detergent compositions containing an organic silver coating agent to minimize silver training in ADW washing methods
US5584888A (en) 1994-08-31 1996-12-17 Miracle; Gregory S. Perhydrolysis-selective bleach activators
US5460747A (en) 1994-08-31 1995-10-24 The Procter & Gamble Co. Multiple-substituted bleach activators
US5578136A (en) 1994-08-31 1996-11-26 The Procter & Gamble Company Automatic dishwashing compositions comprising quaternary substituted bleach activators
US5686015A (en) 1994-08-31 1997-11-11 The Procter & Gamble Company Quaternary substituted bleach activators
US5654421A (en) 1994-08-31 1997-08-05 The Procter & Gamble Company Automatic dishwashing compositions comprising quaternary substituted bleach activators
US5595967A (en) 1995-02-03 1997-01-21 The Procter & Gamble Company Detergent compositions comprising multiperacid-forming bleach activators
US5523434A (en) 1995-03-15 1996-06-04 The Procter & Gamble Company Synthesis of bleach activators
US5739327A (en) 1995-06-07 1998-04-14 The Clorox Company N-alkyl ammonium acetonitrile bleach activators
EP0775127A1 (fr) 1995-06-07 1997-05-28 The Clorox Company Activateur de blanchiment a l'acetonitrile d'ammonium n-alkyle
US6017464A (en) 1995-06-07 2000-01-25 The Clorox Company Dimeric N-alkyl ammonium acetonitrile bleach activators
WO1996040661A1 (fr) 1995-06-07 1996-12-19 The Clorox Company Activateur de blanchiment a l'acetonitrile d'ammonium n-alkyle
US5877315A (en) 1995-06-07 1999-03-02 The Clorox Company Dimeric N-Alkyl ammonium acetonitrile bleach activators
US5958289A (en) 1995-06-07 1999-09-28 The Clorox Company N-alkyl ammonium acetonitrile bleach activators
US5741437A (en) 1995-06-07 1998-04-21 The Clorox Company N-alkyl ammonium acetonitrile bleach activators
US5597936A (en) 1995-06-16 1997-01-28 The Procter & Gamble Company Method for manufacturing cobalt catalysts
US5703030A (en) 1995-06-16 1997-12-30 The Procter & Gamble Company Bleach compositions comprising cobalt catalysts
US5916481A (en) 1995-07-25 1999-06-29 The Procter & Gamble Company Low hue photobleaches
US5718614A (en) 1995-08-28 1998-02-17 Electro-Matic Products Company Control apparatus for grinder
US5576282A (en) 1995-09-11 1996-11-19 The Procter & Gamble Company Color-safe bleach boosters, compositions and laundry methods employing same
EP0790244A1 (fr) 1996-02-15 1997-08-20 Hoechst Aktiengesellschaft Activateurs de blanchiment à de nitriles d'ammonium
US6022844A (en) 1996-03-05 2000-02-08 The Procter & Gamble Company Cationic detergent compounds
US6060443A (en) 1996-04-16 2000-05-09 The Procter & Gamble Company Mid-chain branched alkyl sulfate surfactants
US6020303A (en) 1996-04-16 2000-02-01 The Procter & Gamble Company Mid-chain branched surfactants
US6008181A (en) 1996-04-16 1999-12-28 The Procter & Gamble Company Mid-Chain branched Alkoxylated Sulfate Surfactants
US6326348B1 (en) 1996-04-16 2001-12-04 The Procter & Gamble Co. Detergent compositions containing selected mid-chain branched surfactants
US6004922A (en) 1996-05-03 1999-12-21 The Procter & Gamble Company Laundry detergent compositions comprising cationic surfactants and modified polyamine soil dispersents
US6136769A (en) 1996-05-17 2000-10-24 The Procter & Gamble Company Alkoxylated cationic detergency ingredients
US5759990A (en) 1996-10-21 1998-06-02 The Procter & Gamble Company Concentrated fabric softening composition with good freeze/thaw recovery and highly unsaturated fabric softener compound therefor
US6093856A (en) 1996-11-26 2000-07-25 The Procter & Gamble Company Polyoxyalkylene surfactants
US6153577A (en) 1996-11-26 2000-11-28 The Procter & Gamble Company Polyoxyalkylene surfactants
US6221825B1 (en) 1996-12-31 2001-04-24 The Procter & Gamble Company Thickened, highly aqueous liquid detergent compositions
WO1998035002A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Compositions nettoyantes
WO1998035005A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Composition nettoyante
WO1998035003A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Compose detergent
WO1998035004A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Compositions detergentes solides
WO1998035006A1 (fr) 1997-02-11 1998-08-13 The Procter & Gamble Company Composition nettoyante liquide
US6306812B1 (en) 1997-03-07 2001-10-23 Procter & Gamble Company, The Bleach compositions containing metal bleach catalyst, and bleach activators and/or organic percarboxylic acids
US6225464B1 (en) 1997-03-07 2001-05-01 The Procter & Gamble Company Methods of making cross-bridged macropolycycles
WO1999005242A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Tensio-actifs ameliores d'alkylbenzenesulfonate
WO1999005241A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Produits de nettoyage comportant des tensioactifs alkylarylsulfonate ameliores prepares a l'aide d'olefines de vinylidene et procedes de preparation desdits produits
WO1999005082A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Procedes ameliores de preparation de tensioactifs alkylbenzenesulfonate et produits contenant lesdits tensioactifs
WO1999005243A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Compositions detergentes contenant des melanges de tensio-actifs a cristallinite disloquee
WO1999005244A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Tensio-actifs ameliores d'alkylarylsulfonate
WO1999005084A1 (fr) 1997-07-21 1999-02-04 The Procter & Gamble Company Procede de preparation de tensioactifs alkylbenzenesulfonate a partir d'alcools et produits contenant lesdits tensioactifs
US6482994B2 (en) 1997-08-02 2002-11-19 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
WO1999007656A2 (fr) 1997-08-08 1999-02-18 The Procter & Gamble Company Procedes ameliores de fabrication de tensio-actifs selon une technique de separation par adsorption et produits ainsi obtenus
US6133216A (en) 1997-09-16 2000-10-17 Clariant Gmbh Coated ammonium nitrile bleach activator granules
EP1017773A1 (fr) 1997-09-16 2000-07-12 Clariant GmbH Activateurs de blanchiment a base de nitrile d'ammonium sous forme de granules enrobes
WO1999014302A1 (fr) 1997-09-16 1999-03-25 Clariant Gmbh Activateurs de blanchiment sous forme de granules
EP1017776A1 (fr) 1997-09-16 2000-07-12 Clariant GmbH Activateurs de blanchiment sous forme de granules
US6063750A (en) 1997-09-16 2000-05-16 Clariant Gmbh Bleach activator granules
WO1999014296A1 (fr) 1997-09-16 1999-03-25 Clariant Gmbh Activateurs de blanchiment a base de nitrile d'ammonium sous forme de granules enrobes
JP2000026282A (ja) * 1998-07-14 2000-01-25 Shionogi & Co Ltd 溶出性が改善された硬ゼラチンカプセル剤
US6150322A (en) 1998-08-12 2000-11-21 Shell Oil Company Highly branched primary alcohol compositions and biodegradable detergents made therefrom
WO2000023548A1 (fr) 1998-10-20 2000-04-27 The Procter & Gamble Company Detergents a lessive comprenant des alcoylbenzenesulfonates modifies
WO2000023549A1 (fr) 1998-10-20 2000-04-27 The Procter & Gamble Company Detergents a lessive comprenant des alcoylbenzenesulfonates modifies
US6140294A (en) 1998-11-10 2000-10-31 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Bleach and oxidation catalyst
WO2000032601A2 (fr) 1998-11-30 2000-06-08 The Procter & Gamble Company Procede de preparation de tetraaza macrocycles pontes transversalement
US6494920B1 (en) 1999-02-04 2002-12-17 Cognis Deutschland Gmbh & Co. Kg Detergent mixtures
WO2000047708A1 (fr) 1999-02-10 2000-08-17 The Procter & Gamble Company Solides particulaires faible densite utilises dans les detergents pour lessive
US6287580B1 (en) 1999-08-13 2001-09-11 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Cosmetic compositions with self-warming component
US6302921B1 (en) 1999-09-01 2001-10-16 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Method of bleaching stained fabrics
WO2001042408A2 (fr) 1999-12-08 2001-06-14 The Procter & Gamble Company Tensioactifs a base d'alcools poly(oxyalkyles) coiffes par un ether
US20040229769A1 (en) 2000-12-27 2004-11-18 Colgate-Palmolive Company Thickened fabric conditioners
US20040204337A1 (en) 2003-03-25 2004-10-14 The Procter & Gamble Company Fabric care compositions comprising cationic starch
US20080292692A1 (en) * 2007-05-21 2008-11-27 Shira Pilch Impermeable Capsules

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
"Kirk Othmer's Encyclopedia of Chemical Technology", vol. 4, 1992, JOHN WILEY & SONS, pages: 271 - 300
INORG. CHEM., vol. 18, 1979, pages 1497 - 1502
INORG. CHEM., vol. 18, 1979, pages 2023 - 2025
INORG. CHEM., vol. 21, 1982, pages 2881 - 2885
INORG. SYNTHESIS, 1960, pages 173 - 176
J. CHEM. ED., vol. 66, no. 12, 1989, pages 1043 - 1045
JOURNAL OF PHYSICAL CHEMISTRY, vol. 56, 1952, pages 22 - 25
KIRK OTHMER: "Encyclopedia of Chemical Technology", vol. 17, 1982, JOHN WILEY AND SONS, pages: 27 - 90,63-72
M. L. TOBE: "Base Hydrolysis of Transition-Metal Complexes", ADV. INORG. BIOINORG. MECH., vol. 2, 1983, pages 1 - 94, XP000616123
W.L. JOLLY: "The Synthesis and Characterization of Inorganic Compounds", 1970, PRENTICE-HALL, pages: 461 - 463

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016532546A (ja) * 2013-07-30 2016-10-20 ユニリーバー・ナームローゼ・ベンノートシヤープ カプセル封入有益剤に関する改良
JP2017501330A (ja) * 2013-12-05 2017-01-12 プラスチック・オムニウム・アドヴァンスド・イノベーション・アンド・リサーチ 自動車における使用のための分解ユニットを積載又は再積載する方法及びシステム
RU2556652C1 (ru) * 2013-12-24 2015-07-10 Александр Александрович Кролевец Способ инкапсуляции унаби

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