EP0971026A1 - Compositions de lavage et de nettoyage - Google Patents

Compositions de lavage et de nettoyage Download PDF

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Publication number
EP0971026A1
EP0971026A1 EP99870025A EP99870025A EP0971026A1 EP 0971026 A1 EP0971026 A1 EP 0971026A1 EP 99870025 A EP99870025 A EP 99870025A EP 99870025 A EP99870025 A EP 99870025A EP 0971026 A1 EP0971026 A1 EP 0971026A1
Authority
EP
European Patent Office
Prior art keywords
perfume
acid
methyl
bis
aldehyde
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99870025A
Other languages
German (de)
English (en)
Inventor
Jean-Luc Philippe Bettiol
Alfred Busch
Hugo Denutte
Christophe Laudamiel
Johan Smets
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27239771&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0971026(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from EP98870226A external-priority patent/EP0971024A1/fr
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP99870025A priority Critical patent/EP0971026A1/fr
Priority to EP99870029A priority patent/EP0971021A1/fr
Priority to BR9912033-0A priority patent/BR9912033A/pt
Priority to DE69923227T priority patent/DE69923227T2/de
Priority to CNB998085081A priority patent/CN1167780C/zh
Priority to MA25671A priority patent/MA24922A1/fr
Priority to CA002336666A priority patent/CA2336666A1/fr
Priority to HU0200238A priority patent/HUP0200238A3/hu
Priority to CN99808494A priority patent/CN1321187A/zh
Priority to AU48703/99A priority patent/AU4870399A/en
Priority to ES99932388T priority patent/ES2273504T3/es
Priority to JP2000559205A priority patent/JP4493849B2/ja
Priority to BRPI9912023-2A priority patent/BR9912023B1/pt
Priority to CA002335576A priority patent/CA2335576C/fr
Priority to PCT/US1999/015678 priority patent/WO2000002982A2/fr
Priority to PCT/US1999/015679 priority patent/WO2000002986A2/fr
Priority to KR1020017000417A priority patent/KR20010053480A/ko
Priority to DE69933230T priority patent/DE69933230T3/de
Priority to US09/720,401 priority patent/US6451751B1/en
Priority to AT99932389T priority patent/ATE286962T1/de
Priority to TR2001/00002T priority patent/TR200100002T2/xx
Priority to CZ200158A priority patent/CZ200158A3/cs
Priority to IDW20010074A priority patent/ID28314A/id
Priority to ES99932389T priority patent/ES2237123T3/es
Priority to JP2000559208A priority patent/JP2002524573A/ja
Priority to EP99932388A priority patent/EP1123376B2/fr
Priority to EP99932389A priority patent/EP1144578B1/fr
Priority to ARP990103369A priority patent/AR019367A1/es
Priority to AU48702/99A priority patent/AU4870299A/en
Priority to AT99932388T priority patent/ATE339494T1/de
Publication of EP0971026A1 publication Critical patent/EP0971026A1/fr
Priority to US10/714,784 priority patent/US20040147426A1/en
Priority to US10/911,115 priority patent/US20050043205A1/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50Perfumes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06Powder; Flakes; Free-flowing mixtures; Sheets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039Coated compositions or coated components in the compositions, (micro)capsules
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719Polyamides or polyimides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723Polyamines or polyalkyleneimines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50Perfumes
    • C11D3/502Protected perfumes
    • C11D3/507Compounds releasing perfumes by thermal or chemical activation
    • C11D2111/12
    • C11D2111/14

Definitions

  • the present invention relates to laundry and cleaning compositions comprising a product of reaction between an amino functional polymer comprising at least one primary amine group, and a perfume component, in particular aldehyde or ketone perfumes.
  • Laundry and cleaning products are well-known in the art. However, consumer acceptance of laundry and cleaning products is determined not only by the performance achieved with these products but also by the aesthetics associated therewith.
  • the perfume components are therefore an important aspect of the successful formulation of such commercial products.
  • perfume additives make laundry compositions more aesthetically pleasing to the consumer, and in some cases the perfume imparts a pleasant fragrance to fabrics treated therewith.
  • the amount of perfume carried-over from an aqueous laundry bath onto fabrics is often marginal and does not last long on the fabric.
  • fragrance materials are often very costly and their inefficient use in laundry and cleaning compositions and ineffective delivery to fabrics results in a very high cost to both consumers and laundry and cleaning manufacturers. Industry, therefore, continues to seek with urgency for more efficient and effective fragrance delivery in laundry and cleaning products, especially for improvement in the provision of long-lasting fragrance to the fabrics.
  • Still another solution is to formulate compounds which provide a delayed release of the perfume over a longer period of time than by the use of the perfume itself. Disclosure of such compounds may be found in WO 95/04809, WO 95/08976 and co-pending application EP 95303762.9.
  • perfume ingredients which are characteristic of the fresh notes, namely the aldehydes and ketones perfume ingredients. Indeed, whilst these provide a fresh fragrance, these perfumes are also very volatile and have a low substantivity on the surface to be treated like fabrics.
  • a laundry and cleaning composition comprising a perfume component which provides a fresh fragrance and is substantive to the treated surface.
  • Imine compounds are known in the art under the name of Schiff bases which is the condensation of an aldehyde perfume ingredient with an anthranilate. A typical description can be found in US 4853369. By means of this compound, the aldehyde perfume is made substantive to the fabrics. However, a problem encountered with these schiff bases is that the methylanthranilate compound also exhibits a strong scent, which as a result produces a mixture of fragrances, thereby reducing or even inhibiting the aldehyde fragrance perception.
  • perfumers have formulated around the composition.
  • a carrier or encapsulating material for such notes such as with cyclodextrin, zeolites or starch.
  • Another advantage of the compounds of the invention is their ease of manufacture rendering their use most desirable.
  • the present invention relates to a laundry and cleaning composition
  • a laundry and cleaning composition comprising a detersive ingredient and a product of reaction between an amino functional polymer comprising at least one primary amine group and a perfume component selected from ketone, aldehyde, and mixtures thereof, characterised in that said amino functional polymer has an Odour Intensity Index of less than that of a 1% solution of methylanthranilate in dipropylene glycol, and the product of reaction a Dry Surface Odour Index of more than 5.
  • An essential component of the invention is a product of reaction an amino functional polymer comprising at least one primary amine group and a perfume component, so called hereinafter "amine reaction product”.
  • the amino functional polymer is characterized by an Odour Intensity Index of less than that of a 1 % solution of methylanthranilate in dipropylene glycol.
  • Odour Intensity Index it meant that the pure chemicals were diluted at 1% in Dipropylene Glycol, odor-free solvent used in perfumery. This percentage is more representative of usage levels.
  • Smelling strips, or so called “blotters” were dipped and presented to the expert panellist for evaluation. Expert panellists are assessors trained for at least six months in odor grading and whose gradings are checked for accuracy and reproducibility versus a reference on an ongoing basis. For each an amino functional polymer, the panellist was presented two blotters: one reference (Me Anthranilate, unknown from the panellist) and the sample. The panellist was asked to rank both smelling strips on the 0-5 odor intensity scale, 0 being no odor detected, 5 being very strong odor present.
  • a general structure for the amino functional polymer containing at least one primary amine group of the present invention is as follows: (NH2)n - [B] wherein n is an index of at least 1 and B is the polymer backbone. B can optionally comprise a branching group, C and hence the amino functional polymer is of the following formula: (NH2)n - [B] - [C]x wherein x ⁇ 0.
  • the amino functional polymer of the present invention contains at least one free, unmodified primary amino group attached to the main chain by hydrogen substitution, or by other suitable insertion or substitution by groups referred to as R*. Also suitable is the amino functional polymer comprising an unmodified primary amino group present on side chain(s).
  • the amino functional polymers of the present invention will comprise several amino groups, more preferably more than 10 amino groups.
  • the amino functional polymers of the present invention will preferably present a molecular weight (MW) ranging from 150 to 2.10E6; more preferably from 400-50,000; most preferably from 600 to 40,000.
  • the amino functional polymer can be a linear homo-, co-polymer and optionally branched, grafted and/or cross-linked.
  • Suitable polymer backbone B for the purpose of the present invention have the following polymer units :
  • Suitable branching units C for the polymer backbone B are :
  • the polymer backbone B can also comprise insertion groups I such as :
  • the backbone (B) can also contain several insertion groups linked together: e.g. wherein x ⁇ 1.
  • the aminofunctional polymers of the present invention can further comprise substituents R* in the main chain or in the side chain(s). Typically, R* replaces an hydrogen atom.
  • R* group can either be linked directly or via a linker group L to the main or side chain.
  • Suitable linker groups L are the above mentioned insertion groups I.
  • R* groups are C1 to C22 alkyl, alkenyl, alkylbenzene chain and/or their corresponding substituted derivatives.
  • corresponding substituted derivatives include alicyclic, aromatic, heteroaromatic or heterocyclic systems, either inserted in the main chain or incorporated by a substitution of an H atom in the main chain; an insertion group I in the main chain, as defined herein above and/or an end group E as defined below.
  • R* group can also be modified via substitution of one or more H atoms. Said substitution can either be an end group E or an insertion group I as defined above, where the insertion group is terminated by a H, E or R* group .
  • Suitable amino functional polymers containing at least one primary amine group for the purpose of the present invention are :
  • Preferred amino functional polymers containing at least one primary amine group are :
  • such amino functional polymers comprising at least one primary amine group and the amine reaction product provide fabric appearance benefits, in particular color care and protection against fabric wear.
  • the appearance of fabrics e.g., clothing, bedding, household fabrics like table linens is one of the area of concern to consumers. Indeed, upon typical consumer's uses of the fabrics such as wearing, washing, rinsing and/or tumble-drying of fabrics, a loss in the fabric appearance; which can be at least partly due to loss of color fidelity and color definition, is observed. Such a problem of color loss is even more acute after multiwash cycles. It has been found that the compositions of the present invention provide improved fabric appearance and protection against fabric wear and improved color care to laundered fabrics, especially after multiwash cycles.
  • the softening compositions of the present invention can provide simultaneously fabric care and long lasting perfume benefits.
  • perfume ketone or aldehyde it is meant any chain containing at least 1 carbon atom, preferably at least 5 carbon atoms.
  • Perfume ketones components include components having odoriferous properties.
  • the perfume ketone is selected for its odor character from buccoxime; iso jasmone; methyl beta naphthyl ketone; musk indanone; tonalid/musk plus; Alpha-Damascone, Beta-Damascone, Delta-Damascone, Iso-Damascone, Damascenone, Damarose, Methyl-Dihydrojasmonate, Menthone, Carvone, Camphor, Fenchone, Alpha-lonone, Beta-lonone, Gamma-Methyl so-called lonone, Fleuramone, Dihydrojasmone, Cis-Jasmone, Iso-E-Super, Methyl- Cedrenyl-ketone or Methyl- Cedrylone, Acetophenone, Methyl-Acetophenone, Para-Methoxy-Acetophenone, Methyl-Beta
  • the more preferred ketones are selected for its odor character from Alpha Damascone, Delta Damascone, Iso Damascone, Carvone, Gamma-Methyl-lonone, Iso-E-Super, 2,4,4,7-Tetramethyl-oct-6-en-3-one, Benzyl Acetone, Beta Damascone, Damascenone, methyl dihydrojasmonate, methyl cedrylone, and mixtures thereof.
  • Perfume aldehyde components include components having odoriferous properties.
  • the perfume aldehyde is selected for its odor character from adoxal; anisic aldehyde; cymal; ethyl vanillin; florhydral; helional; heliotropin; hydroxycitronellal; koavone; lauric aldehyde; lyral; methyl nonyl acetaldehyde; P. T.
  • More preferred aldehydes are selected for its odor character from 1-decanal, benzaldehyde, florhydral, 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde; cis/trans-3,7-dimethyl-2,6-octadien-1-al; heliotropin; 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde; 2,6-nonadienal; alpha-n-amyl cinnamic aldehyde, alpha-n-hexyl cinnamic aldehyde, P.T. Bucinal, lyral, cymal, methyl nonyl acetaldehyde, hexanal, trans-2-hexenal, and mixture thereof.
  • perfume ingredients some are commercial names conventionally known to one skilled in the art, and also includes isomers. Such isomers are also suitable for use in the present invention.
  • the perfume compounds preferably the perfume ketones or aldehydes, characterized by having a low Odor Detection Threshold.
  • Odor Detection Threshold ODT
  • GC Gas Chromatography
  • This parameter refers to the value commonly used in the perfumery arts and which is the lowest concentration at which significant detection takes place that some odorous material is present. Please refer for example in “Compilation of Odor and Taste Threshold Value Data (ASTM DS 48 A)", edited by F. A.
  • the Odor Detection Threshold is measured according to the following method : The gas chromatograph is characterized to determine the exact volume of material injected by the syringe, the precise split ratio, and the hydrocarbon response using a hydrocarbon standard of known concentration and chain-length distribution. The air flow rate is accurately measured and, assuming the duration of a human inhalation to last 0.02 minutes, the sampled volume is calculated.
  • perfume components are those selected from : 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde, 1-(2,6,6-trimethyl-2-cyclohexan-1-yl)-2-buten-1-one and/or para-methoxy-acetophenone.
  • a typical reaction profile is as follows: ⁇ , ⁇ -Unsaturated ketones do not only condense with amines to form imines, but can also undergo a competitive 1,4-addition to form ⁇ -aminoketones.
  • the perfume ingredient needs to be present in equimolar amount to the amine function so as to enable the reaction to take place and provide the resulting amine reaction product.
  • higher amount are not excluded and even preferred when the amine compound comprises more than one amine function.
  • the perfume components are released upon breaking down of the imine bond, leading to the release of the perfume component and of the primary amine compound. This can be achieved by either hydrolysis, photochemical cleavage, oxidative cleavage, or enzymatic cleavage.
  • Still other means of release for imine as well as ⁇ -aminoketone compounds can be considered such as by the steaming step of ironing the treated fabric, tumble-drying, and/or wearing.
  • the present invention include both laundry and cleaning compositions which are typically used for laundering fabrics and cleaning hard surfaces such as dishware, floors, bathrooms, toilet, kitchen and other surfaces in need of a delayed release of perfume ketone and/or aldehyde. Accordingly, by laundry and cleaning compositions, these are to be understood to include not only detergent compositions which provide fabric cleaning benefits, but also compositions such as hard surface cleaning which provide hard surface cleaning benefit.
  • the amine reaction product(s) which is incorporated into such laundry and cleaning compositions provides a dry surface Odour Index of more than 5 preferably at least 10.
  • Dry Surface Odour Index it is meant that the amine reaction product(s) provides a Delta of more than 5, wherein Delta is the difference between the Odour Index of the dry surface treated with amine reaction product(s) and the Odour Index of the dry surface treated with only the perfume raw material.
  • the amine reaction product suitable for use in the present invention needs to fulfill at least one of the following two tests.
  • Preferred amine reaction product suitable for use in the present invention fulfill both test.
  • the amine reaction product is added to the unperfumed product base.
  • Levels of amine reaction product are selected so as to obtain an odour grade on the dry fabric of at least 20. After careful mixing, by shaking the container in case of a liquid, with a spatula in case of a powder, the product is allowed to sit for 24 hrs.
  • the resulting product is added into the washing machine in the dosage and in the dispenser appropriate for its category.
  • the quantity corresponds to recommended dosages made for the corresponding market products: typically between 70 and 150 g for a detergent powder or liquid via current dosing device like granulette, or ariellette.
  • the load is composed of four bath towels (170g) using a Miele W830 washing machine at 40°C short cycle, water input :15°Hardness at a temperature of 10-18°C, and full spin of 1200rpm.
  • Odor is assessed by expert panellist smelling the fabrics.
  • a 0-100 scale is used for all fabric odor gradings.
  • the grading scale is as follows :
  • a difference of more than 5 grades after one day and/or 7 days between the amine reaction product and the perfume raw material is statistically significant.
  • a difference of 10 grades or more after one day and/or 7 days represents a step-change.
  • the amine reaction product is suitable for use in the present invention, provided that the amine compound fulfill the Odour Intensity Index.
  • the perfume raw material or blend thereof is added and carefully mixed at 0.255% in the unperfumed Hard Surface Cleaner base. After mixing and standing for 24 hrs, the homogeneity of the product is checked. In case of phase separation due to poor solubility of the perfume ingredient(s) an appropriate amount of Sodium p. Cymene Sulfonate or another solubilising agent is added till a homogeneous solution is obtained.
  • the tile is placed in a clean and aerated perspex box (38 x 40 x 32 cm) with a removable cover that has a sliding-lid (10 x 10 cm) to allow expert evaluators to smell the interior phase of the box.
  • the odor in the box is evaluated just after placing the tile in it (fresh reading) and after 1, 2 and 6 hours.
  • the grading scale is as follows :
  • Every test includes a blanc (unperfumed Hard Surface Cleaner) and in the case of testing perfume precursor, so-called amine reaction product the corresponding free perfume ingredient is also included so that the effect of the carrier is adequately measured.
  • a difference of more than 5 grades after 1 day and/or 7 days between the amine reaction product and the perfume raw material is statistically significant.
  • a difference of 10 grades or more after 1 day and/or 7 days represents a step-change.
  • the amine reaction product is suitable for use in the present, provided that the amine compound fulfill the Odour Intensity Index.
  • the amine reaction product as defined herein before is typically comprised from 0.0001% to 10%, preferably from 0.001% to 5%, and more preferably from 0.01% to 2%, by weight of the composition. Mixtures of the compounds may also be used herein.
  • incorporation of the amine reaction product in the laundry and cleaning compositions can conveniently be carried out, if necessary, by conventional incorporation means, such as by spray-on, encapsulation like starch encapsulation, e.g. as described in GB1464616, dry addition, or by encapsulation in cyclodextrin.
  • the amine reaction product is preformed before incorporation into the laundry and cleaning compositions.
  • the perfume component and the amino functional polymer of the present invention are first reacted together to obtain the resulting amine reaction product as defined in the present invention and only once formed incorporated into the laundry and cleaning compositions.
  • a better control of the compound being made is obtained.
  • the interaction with perfume composition which may be present in fully formulated composition is avoided as well as side reaction that could occur.
  • efficient control of the yield and purity of the compound is obtained.
  • the amine reaction product is incorporated in the composition separately from the perfume.
  • the amine reaction product and its subsequent perfume release is more controlled.
  • the laundry and cleaning composition comprises a detersive ingredient and further optional ingredients as described hereinafter as optional ingredients.
  • Non-limiting examples of surfactants useful herein typically at levels from 1 % to 55%, by weight include the conventional C 11 -C 18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C 10 -C 20 alkyl sulfates (“AS”), the C 10 -C 18 secondary (2,3) alkyl sulfates of the formula CH 3 (CH 2 ) x (CHOSO 3 - M + ) CH 3 and CH 3 (CH 2 ) y (CHOSO 3 - M + ) CH 2 CH 3 where x and (y + 1) are integers of at least 7, preferably at least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C 10 -C 18 alkyl alkoxy sulfates ("AE x S"; especially x up to 7 EO ethoxy sulfates), C 10 -C 18 alkyl
  • the conventional nonionic and amphoteric surfactants such as the C 12 -C 18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C 6 -C 12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C 12 -C 18 betaines and sulfobetaines ("sultaines"), C 10 -C 18 amine oxides, cationic surfactants and the like, can also be included in the overall compositions.
  • the C 10 -C 18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C 12 -C 18 N-methylglucamides.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10 -C 18 N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C 12 -C 18 glucamides can be used for low sudsing.
  • C 10 -C 20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C 10 -C 16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
  • Fully formulated laundry and cleaning compositions preferably contain, in addition to the hereinbefore described components, one or more of the following ingredients.
  • Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form.
  • the compositions will typically comprise at least 1% builder, preferably from 1% to 80%.
  • Liquid formulations typically comprise from 5% to 50%, more typically 5% to 30%, by weight, of detergent builder.
  • Granular formulations typically comprise from 1 % to 80%, more typically from 5% to 50% by weight, of the detergent builder.
  • Lower or higher levels of builder are not meant to be excluded.
  • Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • non-phosphate builders are required in some locales.
  • compositions herein function surprisingly well even in the presence of the so-called “weak” builders (as compared with phosphates) such as citrate, or in the so-called “underbuilt” situation that may occur with zeolite or layered silicate builders.
  • silicate builders are the alkali metal silicates, particularly those having a SiO 2 :Na 2 O ratio in the range 1.0:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. 4,664,839.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na 2 SiO 5 morphology form of layered silicate. It can be prepared by methods such as those described in DE-A-3,417,649 and DE-A-3,742,043.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x O 2x+1 ⁇ yH 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na 2 SiO 5 (NaSKS-6 form) is most preferred for use herein.
  • silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in DE 2,321,001.
  • Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula: M z/n [(AlO 2 ) z (SiO 2 ) y ] ⁇ xH 2 O wherein z and y are integers usually of at least 6, the molar ratio of z to y is in the range from 1.0 to 0, and x is an integer from 0 to 264, and M is a Group IA or IIA element, e.g., Na, K, Mg, Ca with valence n.
  • M is a Group IA or IIA element, e.g., Na, K, Mg, Ca with valence n.
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula: Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ] ⁇ xH 2 O wherein x is from 20 to 30, especially 27.
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of 0.1-10 microns in diameter.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. 3,128,287, U.S. 3,635,830. See also "TMS/TDS" builders of U.S. 4,663,071.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, pyromellitic, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C 5 -C 20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in EP 0,200,263.
  • Fatty acids e.g., C 12 -C 18 monocarboxylic acids such as oleic acid and/or its salts
  • C 12 -C 18 monocarboxylic acids such as oleic acid and/or its salts
  • the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
  • the detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators.
  • bleaching agents will typically be at levels of from 1% to 30%, more typically from 5% to 20%, of the detergent composition, especially for fabric laundering.
  • the amount of bleach activators will typically be from 0.1% to 60%, more typically from 0.5% to 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents like hypochlorite bleaching agents.
  • Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
  • hypochlorite a highly preferred hypochlorite bleaching component is an alkali metal hypochlorite.
  • alkali metal hypochlorites are preferred, other hypochlorite compounds may also be used herein and can be selected from calcium and magnesium hypochlorite.
  • a preferred alkali metal hypochlorite for use herein is sodium hypochlorite.
  • bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S 4,483,781, U.S 740,446, EP 0,133,354, and U.S 4,412,934.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S 4,634,551.
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate” bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
  • a preferred percarbonate bleach comprises dry particles having an average particle size in the range from 500 micrometers to 1,000 micrometers, not more than 10% by weight of said particles being smaller than 200 micrometers and not more than 10% by weight of said particles being larger than 1,250 micrometers.
  • the percarbonate can be coated with silicate, borate or water-soluble surfactants.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
  • Mixtures of bleaching agents can also be used.
  • Peroxygen bleaching agents, the perborates, the percarbonates, etc. are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
  • bleach activators Various non-limiting examples of activators are disclosed in U.S 4,915,854, and U.S 4,412,934.
  • NOBS nonanoyloxybenzene sulfonate
  • ISONOBS 3,5,5-tri-methyl hexanoyl oxybenzene sulfonate
  • TAED tetraacetyl ethylene diamine
  • amido-derived bleach activators are those of the formulae: R 1 N(R 5 )C(O)R 2 C(O)L or R 1 C(O)N(R 5 )R 2 C(O)L wherein R 1 is an alkyl group containing from 6 to 12 carbon atoms, R 2 is an alkylene containing from 1 to 6 carbon atoms, R 5 is H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon atoms, and L is any suitable leaving group.
  • a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion.
  • a preferred leaving group is phenyl sulfonate.
  • bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzene sulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551, incorporated herein by reference.
  • Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723.
  • a highly preferred activator of the benzoxazin-type is:
  • Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae: wherein R 6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to 12 carbon atoms.
  • lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. 4,033,718. If used, detergent compositions will typically contain from 0.025% to 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • the bleaching compounds can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds are well-known in the art and include, for example, the manganese-based catalysts disclosed in U.S. 5,246,621, U.S. 5,244,594; U.S. 5,194,416; U.S.
  • catalysts include Mn IV 2 (u-O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF 6 ) 2 , Mn III 2 (u-O) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 -(ClO 4 ) 2 , Mn IV 4 (u-O) 6 (1,4,7-triazacyclononane) 4 (ClO 4 ) 4 , Mn III Mn IV 4 (u-O) 1 (u-OAc) 2- (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO 4 ) 3 , Mn IV (1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH 3 ) 3 (PF 6 ),
  • metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. 5,114,611.
  • the use of manganese with various complex ligands to enhance bleaching is also reported in the following US Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.
  • compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from 0.1 ppm to 700 ppm, more preferably from 1 ppm to 500 ppm, of the catalyst species in the laundry liquor.
  • compositions herein can also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from 0.001% to 1 % by weight of such optical brighteners.
  • the hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein R 1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
  • R 1 is anilino
  • R 2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX® by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the rinse added compositions herein.
  • R 1 is anilino
  • R 2 is N-2-hydroxyethyl-N-2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX® by Ciba-Geigy Corporation.
  • R 1 is anilino
  • R 2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX® by Ciba Geigy Corporation.
  • an optional soil release agent can be added.
  • Typical levels of incorporation in the composition are from 0% to 10%, preferably from 0.2% to 5%, of a soil release agent.
  • a soil release agent is a polymer.
  • Soil Release agents are desirably used in fabric softening compositions of the instant invention. Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions of this invention. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
  • soil release agents include the METOLOSE SM100, METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo K.K., SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (Germany), ZELCON 5126 (from Dupont) and MILEASE T (from ICI).
  • the premix can be combined with an optional scum dispersant, other than the soil release agent, and heated to a temperature at or above the melting point(s) of the components.
  • the preferred scum dispersants herein are formed by highly ethoxylating hydrophobic materials.
  • the hydrophobic material can be a fatty alcohol, fatty acid, fatty amine, fatty acid amide, amine oxide, quaternary ammonium compound, or the hydrophobic moieties used to form soil release polymers.
  • the preferred scum dispersants are highly ethoxylated, e.g., more than 17, preferably more than 25, more preferably more than 40, moles of ethylene oxide per molecule on the average, with the polyethylene oxide portion being from 76% to 97%, preferably from 81% to 94%, of the total molecular weight.
  • the level of scum dispersant is sufficient to keep the scum at an acceptable, preferably unnoticeable to the consumer, level under the conditions of use, but not enough to adversely affect softening. For some purposes it is desirable that the scum is nonexistent.
  • the amount of anionic or nonionic detergent surfactant and detergency builder (especially phosphates and zeolites) entrapped in the fabric (laundry) will vary.
  • the minimum amount of scum dispersant should be used to avoid adversely affecting softening properties.
  • scum dispersion requires at least 2%, preferably at least 4% (at least 6% and preferably at least 10% for maximum scum avoidance) based upon the level of softener active.
  • Preferred scum dispersants are: Brij 700®; Varonic U-250®; Genapol T-500®, Genapol T-800®; Plurafac A-79®; and Neodol 25-50®.
  • bactericides used in the compositions of this invention include glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1,3-diol sold by Inolex Chemicals, located in Philadelphia, Pennsylvania, under the trade name Bronopol®, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-one and 2-methyl-4-isothiazoline-3-one sold by Rohm and Haas Company under the trade name Kathon 1 to 1,000 ppm by weight of the agent.
  • the present invention can contain any detergent compatible perfume.
  • perfumes are disclosed in U.S. Pat. 5,500,138, said patent being incorporated herein by reference.
  • perfume includes fragrant substance or mixture of substances including natural (i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants), artificial (i.e., a mixture of different nature oils or oil constituents) and synthetic (i.e., synthetically produced) odoriferous substances.
  • natural i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants
  • artificial i.e., a mixture of different nature oils or oil constituents
  • synthetic i.e., synthetically produced odoriferous substances.
  • Such materials are often accompanied by auxiliary materials, such as fixatives, extenders, stabilizers and solvents. These auxiliaries are also included within the meaning of "perfume", as used herein.
  • perfumes are complex mixtures of a plurality of organic compounds.
  • perfume ingredients useful in the perfumes of the present invention compositions include, but are not limited to, hexyl cinnamic aldehyde; amyl cinnamic aldehyde; amyl salicylate; hexyl salicylate; terpineol; 3,7-dimethyl-cis-2,6-octadien-1-ol; 2,6-dimethyl-2-octanol; 2,6-dimethyl-7-octen-2-ol; 3,7-dimethyl-3-octanol; 3,7-dimethyl- trans -2,6-octadien-1-ol; 3,7-dimethyl-6-octen-1-ol; 3,7-dimethyl-1-octanol; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxalde
  • fragrance materials include, but are not limited to, orange oil; lemon oil; grapefruit oil; bergamot oil; clove oil; dodecalactone gamma; methyl-2-(2-pentyl-3-oxo-cyclopentyl) acetate; beta-naphthol methylether; methyl-beta-naphthylketone; coumarin; decylaldehyde; benzaldehyde; 4-tert-butylcyclohexyl acetate; alpha,alpha-dimethylphenethyl acetate; methylphenylcarbinyl acetate; Schiff's base of 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde and methyl anthranilate; cyclic ethyleneglycol diester of tridecandioic acid; 3,7-dimethyl-2,6-octadiene-1-nitrile; i
  • perfume components are geraniol; geranyl acetate; linalool; linalyl acetate; tetrahydrolinalool; citronellol; citronellyl acetate; dihydromyrcenol; dihydromyrcenyl acetate; tetrahydromyrcenol; terpinyl acetate; nopol; nopyl acetate; 2-phenylethanol; 2-phenylethyl acetate; benzyl alcohol; benzyl acetate; benzyl salicylate; benzyl benzoate; styrallyl acetate; dimethylbenzylcarbinol; trichloromethylphenylcarbinyl methylphenylcarbinyl acetate; isononyl acetate; vetiveryl acetate; vetiverol; 2-methyl-3-(p-tert-butylphenyl)-propanal; 2-methyl-3-(
  • the perfumes useful in the present invention compositions are substantially free of halogenated materials and nitromusks.
  • Suitable solvents, diluents or carriers for perfumes ingredients mentioned above are for examples, ethanol, isopropanol, diethylene glycol, monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate, etc.
  • the amount of such solvents, diluents or carriers incorporated in the perfumes is preferably kept to the minimum needed to provide a homogeneous perfume solution.
  • Perfume can be present at a level of from 0% to 10%, preferably from 0.1% to 5%, and more preferably from 0.2% to 3%, by weight of the finished composition.
  • Fabric softener compositions of the present invention provide improved fabric perfume deposition.
  • compositions and processes herein can optionally employ one or more copper and/or nickel chelating agents ("chelators").
  • chelators can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof, all as hereinafter defined.
  • the whiteness and/or brightness of fabrics are substantially improved or restored by such chelating agents and the stability of the materials in the compositions are improved. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
  • EDDS ethylenediamine disuccinate
  • [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
  • compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates and the like.
  • MGDA water-soluble methyl glycine diacetic acid
  • Preferred chelating agents include DETMP, DETPA, NTA, EDDS and mixtures thereof.
  • these chelating agents will generally comprise from about 0.1% to about 15% by weight of the fabric care compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.
  • compositions of the present invention can further contain a crystal growth inhibitor component, preferably an organodiphosphonic acid component, incorporated preferably at a level of from 0.01% to 5%, more preferably from 0.1% to 2% by weight of the compositions.
  • a crystal growth inhibitor component preferably an organodiphosphonic acid component
  • organo diphosphonic acid it is meant herein an organo diphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the organo aminophosphonates, which however may be included in compositions of the invention as heavy metal ion sequestrant components.
  • the organo diphosphonic acid is preferably a C 1 -C 4 diphosphonic acid, more preferably a C 2 diphosphonic acid, such as ethylene diphosphonic acid, or most preferably ethane 1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present in partially or fully ionized form, particularly as a salt or complex.
  • HEDP ethane 1-hydroxy-1,1-diphosphonic acid
  • crystal growth inhibitor are the organic monophosphonic acid Organo monophosphonic acid or one of its salts or complexes is also suitable for use herein as a CGI.
  • organo monophosphonic acid it is meant herein an organo monophosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the organo aminophosphonates, which however may be included in compositions of the invention as heavy metal ion sequestrants.
  • the organo monophosphonic acid component may be present in its acid form or in the form of one of its salts or complexes with a suitable counter cation.
  • any salts/complexes are water soluble, with the alkali metal and alkaline earth metal salts/complexes being especially preferred.
  • a preferred organo monophosphonic acid is 2-phosphonobutane-1,2,4-tricarboxylic acid commercially available from Bayer under the tradename of Bayhibit.
  • compositions and processes herein can optionally employ one or more enzymes such as lipases, proteases, cellulase, amylases and peroxidases.
  • a preferred enzyme for use herein is a cellulase enzyme. Indeed, this type of enzyme will further provide a color care benefit to the treated fabric.
  • Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 9.5. U.S.
  • 4,435,307 discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME® and CELLUZYME® (Novo) are especially useful.
  • compositions herein will typically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation.
  • activity units are preferred (e.g. CEVU or cellulase Equivalent Viscosity Units).
  • compositions of the present invention can contain cellulase enzymes at a level equivalent to an activity from 0.5 to 1000 CEVU/gram of composition.
  • Cellulase enzyme preparations used for the purpose of formulating the compositions of this invention typically have an activity comprised between 1,000 and 10,000 CEVU/gram in liquid form, around 1,000 CEVU/gram in solid form.
  • Other preferred optional ingredients include enzyme stabilisers, polymeric soil release agents, materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process (i.e., dye transfer inhibiting agents), polymeric dispersing agents, suds suppressors, optical brighteners or other brightening or whitening agents, chelating agents, fabric softening clay, anti-static agents, other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations and solid fillers for bar compositions.
  • enzyme stabilisers materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process (i.e., dye transfer inhibiting agents), polymeric dispersing agents, suds suppressors, optical brighteners or other brightening or whitening agents, chelating agents, fabric softening clay, anti-static agents, other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations and solid fillers for bar compositions.
  • Liquid detergent compositions can contain water and other solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used.
  • the compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.
  • Granular detergents can be prepared, for example, by spray-drying (final product density 520 g/l) or agglomerating (final product density above 600 g/l) the Base Granule.
  • the remaining dry ingredients can then be admixed in granular or powder form with the Base Granule, for example in a rotary mixing drum, and the liquid ingredients (e.g., nonionic surfactant and perfume) can be sprayed on.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well-known to those skilled in the art.
  • Also provided herein is a method for providing a delayed release of an active ketone or aldehyde which comprises the step of contacting the surface to be treated with a a compound or composition of the invention, and thereafter contacting the treated surface with a material, preferably an aqueous medium like moisture or any other means susceptible of releasing the perfume from the amine reaction product.
  • surface it is meant any surface onto which the compound can deposit. Typical examples of such material are fabrics, hard surfaces such as dishware, floors, bathrooms, toilet, kitchen and other surfaces in need of a delayed release of a perfume ketone and/or aldehyde such as that with litter like animal litter.
  • the surface is selected from a fabric, a tile, a ceramic; more preferably is a fabric.
  • delayed release is meant release of the active component (e.g perfume) over a longer period of time than by the use of the active (e.g., perfume) itself.
  • Alcalase Proteolytic enzyme having 5.3% by weight of active enzyme, sold by NOVO Industries A/S Cellulase Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Carezyme Amylase Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T Lipase Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Lipase (1) Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Ultra Endolase Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries A/S PB4 Sodium perborate tetrahydrate of nominal formula NaBO 2 .3H 2 O.H 2 O 2 PB1 Anhydrous sodium perborate bleach of nominal formula NaBO 2 .H 2 O 2 Percarbonate Sodium
  • Photoactivated bleach (1) Sulfonated zinc phthlocyanine encapsulated in dextrin soluble polymer
  • Photoactivated bleach (2) Sulfonated alumino phthlocyanine encapsulated in dextrin soluble polymer
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl )biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2'-disulfonate
  • PEGx Polyethylene glycol, with a molecular weight of x (typically 4,000)
  • PEO Polyethylene oxide with an average molecular weight of 50,000
  • PVI Polyvinyl imidosole with an average molecular weight of 20,000
  • PAAC Pentaamine acetate cobalt(lll) salt Paraffin Paraffin oil sold under the tradename Winog 70 by Wintershall. NaBz Sodium benzoate. BzP Benzoyl Peroxide. SCS Sodium cumene sulphonate. BTA Benzotriazole. pH Measured as a 1% solution in distilled water at 20°C.
  • the following detergent compositions were prepared: GG HH II Blown Powder Zeolite A 15.0 15.0 15.0 Sulfate 0.0 5.0 0.0 LAS 3.0 3.0 3.0 QAS - 1.5 1.5 DTPMP 0.4 0.2 0.4 EDDS - 0.4 0.2 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Agglomerates LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray On Perfume 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 - - ARP2 0.02(s) - - Dry additives Citrate 5.0 - 2.0 Bicarbonate - 3.0 - Carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 PB1 14.0 7.0 10.0 PEO - - 0.2 ARP1 0.1 0.2 0.08(ec) Bentonite clay - - 10.0 Protease 1.0 1.0 1.0 1.0
  • liquid detergent formulations were prepared in accord with the invention (levels are given in parts per weight): SS TT UU VV WW XX YY ZZ LAS 10.0 13.0 9.0 - 25.0 - - - C25AS 4.0 1.0 2.0 10.0 - 13.0 18.0 15.0 C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0 C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0 TFAA - - - 4.5 - 6.0 8.0 APA - 1.4 - - 3.0 1.0 2.0 - TPKFA 2.0 - 13.0 7.0 - 15.0 11.0 11.0 Citric acid 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0 1.0 1.0 Dodecenyl/tetradecenyl succinic acid 12.0 10.0 - - 15.0 - - - Rape seed fatty acid 4.0 2.0 1.0 - 1.0 - - 3.5 - Ethanol 4.0 4.0 7.0 2.0
  • the following detergent additive compositions were prepared according to the present invention : AL AM AN LAS - 5.0 5.0 STPP 30.0 - 20.0 Zeolite A - 35.0 20.0 PB1 20.0 15.0 - TAED 10.0 8.0 - ARP1 0.3 - 0.1 ARP2 - 0.04 0.02 Protease - 0.3 0.3 Amylase - 0.06 0.06 Minors, water and miscellaneous Up to 100%
  • the following tablet detergent compositions were prepared according to the present invention by compression of a granular dishwashing detergent composition at a pressure of 13KN/cm 2 using a standard 12 head rotary press: BF BJ BK BL BM BN STPP - 48.8 49.2 38.0 - 46.8 Citrate 26.4 - - - 31.1 - Carbonate - 5.0 14.0 15.4 14.4 23.0 Silicate 26.4 14.8 15.0 12.6 17.7 2.4 ARP1 0.3 - - - 0.06 - ARP2 - 0.04 - - - 0.08 ARP3 - - 0.3 0.1(ec) - - Protease 0.058 0.072 0.041 0.033 0.052 0.013 Amylase 0.01 0.03 0.012 0.007 0.016 0.002 Lipase 0.005 - - - - - PB1 1.6 7.7 12.2 10.6 15.7 - PB4 6.9 - - - - 14.
  • liquid dishwashing detergent compositions of density 1.40Kg/L were prepared according to the present invention : BO BP BQ BR STPP 17.5 17.5 17.2 16.0 Carbonate 2.0 - 2.4 - Silicate 5.3 6.1 14.6 15.7 NaOCI 1.15 1.15 1.15 1.25 Polygen/carbopol 1.1 1.0 1.1 1.25 Nonionic - - 0.1 - NaBz 0.75 0.75 - - ARP3 0.3 0.5 0.05 0.1 NaOH - 1.9 - 3.5 KOH 2.8 3.5 3.0 - pH 11.0 11.7 10.9 11.0 Sulphate, miscellaneous and water up to 100%
  • liquid rinse aid compositions were prepared according to the present invention : BS BT BU Nonionic 12.0 - 14.5 Nonionic blend - 64.0 - Citric 3.2 - 6.5 HEDP 0.5 - - PEG - 5.0 - SCS 4.8 - 7.0 Ethanol 6.0 8.0 - ARP1 0.3 - 0.1 ARP2 - 0.04 0.01 pH of the liquid 2.0 7.5 / Miscellaneous and water Up to 100%
  • liquid dishwashing compositions were prepared according to the present invention : BV BW BX BY BZ C17ES 28.5 27.4 19.2 34.1 34.1 Amine oxide 2.6 5.0 2.0 3.0 3.0 C12 glucose amide - - 6.0 - - Betaine 0.9 - - 2.0 2.0 Xylene sulfonate 2.0 4.0 - 2.0 - Neodol C11E9 - - 5.0 - - Polyhydroxy fatty acid amide - - - 6.5 6.5 Sodium diethylene penta acetate - - 0.03 - - (40%) TAED - - - 0.06 0.06 Sucrose - - - 1.5 1.5 Ethanol 4.0 5.5 5.5 9.1 9.1 Alkyl diphenyl oxide disulfonate - - - - 2.3 Ca formate - - - - 0.5 1.1 Ammonium citrate 0.06 0.1 - - - Na chloride - 1.0 - -
  • liquid hard surface cleaning compositions were prepared according to the present invention : CA CB CD CE CF ARP2 0.04 - 0.08 - 0.01 ARP3 - 0.3 - 0.125 0.1 Amylase 0.01 0.002 0.005 - - Protease 0.05 0.01 0.02 - - Hydrogen peroxide - - - 6.0 6.8 Acetyl triethyl citrate - - - 2.5 - DTPA - - - 0.2 - Butyl hydroxy toluene - - - 0.05 - EDTA 0.05 0.05 0.05 - - Citric / Citrate 2.9 2.9 2.9 2.9 1.0 - LAS 0.5 0.5 0.5 0.5 - - C12 AS 0.5 0.5 0.5 0.5 - - C10AS - - - - 1.7 C12(E)S 0.5 0.5 0.5 - - C12,13 E6.5 nonionic 7.0 7.0 7.0 - - Neodo
  • the following spray composition for cleaning of hard surfaces and removing household mildew was prepared according to the present invention : ARP2 0.04 Amylase 0.01 Protease 0.01 Na octyl sulfate 2.0 Na dodecyl sulfate 4.0 Na hydroxide 0.8 Silicate 0.04 Butyl carbitol 4.0 Perfume 0.35 Water/minors up to 100%
  • lavatory cleansing block compositions were prepared according to the present invention.
  • the following toilet bowl cleaning composition was prepared according to the present invention.
EP99870025A 1998-07-10 1999-02-11 Compositions de lavage et de nettoyage Withdrawn EP0971026A1 (fr)

Priority Applications (32)

Application Number Priority Date Filing Date Title
EP99870025A EP0971026A1 (fr) 1998-07-10 1999-02-11 Compositions de lavage et de nettoyage
EP99870029A EP0971021A1 (fr) 1998-07-10 1999-02-15 Procédé de production de particules de produit de réaction aminé
AU48702/99A AU4870299A (en) 1998-07-10 1999-07-12 Laundry and cleaning compositions
AT99932388T ATE339494T1 (de) 1998-10-28 1999-07-12 Wasch- und reinigungsmittelzusammensetzungen
PCT/US1999/015679 WO2000002986A2 (fr) 1998-07-10 1999-07-12 Procede servant a preparer des particules de produit de reaction d'amine
DE69933230T DE69933230T3 (de) 1998-07-10 1999-07-12 Wasch- und reinigungsmittelzusammensetzungen
CNB998085081A CN1167780C (zh) 1998-07-10 1999-07-12 制备胺反应产物颗粒的方法
MA25671A MA24922A1 (fr) 1998-10-28 1999-07-12 Compositions de lavage de linge et de nettoyage
CA002336666A CA2336666A1 (fr) 1998-07-10 1999-07-12 Procede servant a preparer des particules de produit de reaction d'amine
HU0200238A HUP0200238A3 (en) 1998-10-28 1999-07-12 Laundry and cleaning composition and its use
CN99808494A CN1321187A (zh) 1998-07-10 1999-07-12 洗衣和清洁组合物
AU48703/99A AU4870399A (en) 1998-07-10 1999-07-12 Process for producing particles of amine reaction product
ES99932388T ES2273504T3 (es) 1998-07-10 1999-07-12 Composiciones para el lavado de ropa y limpiadoras.
JP2000559205A JP4493849B2 (ja) 1998-10-28 1999-07-12 洗濯およびクリーニング組成物
BRPI9912023-2A BR9912023B1 (pt) 1998-07-10 1999-07-12 processo para a fabricaÇço de partÍculas de produto de reaÇço de amina, produto de reaÇço de amina processada, mÉtodo de incorporaÇço da mesma, composiÇço final, mÉtodo para distribuiÇço de fragrÂncia residual a uma superfÍcie, uso de produto e composiÇço acondicionada.
CA002335576A CA2335576C (fr) 1998-07-10 1999-07-12 Procede servant a preparer des particules de produit de reaction d'amine
PCT/US1999/015678 WO2000002982A2 (fr) 1998-07-10 1999-07-12 Procede servant a preparer des particules de produit de reaction d'amine
BR9912033-0A BR9912033A (pt) 1998-10-28 1999-07-12 Composições para lavar roupa e limpeza
KR1020017000417A KR20010053480A (ko) 1998-07-10 1999-07-12 세척 및 세정 조성물
DE69923227T DE69923227T2 (de) 1998-07-10 1999-07-12 Verfahren zur Herstellung von Aminierungsprodukt-Teilchen
US09/720,401 US6451751B1 (en) 1998-07-10 1999-07-12 Process for producing particles of amine reaction product
AT99932389T ATE286962T1 (de) 1998-07-10 1999-07-12 Verfahren zur herstellung von aminierungsprodukte-teilchen
TR2001/00002T TR200100002T2 (tr) 1998-10-28 1999-07-12 Çamaşır ve temizlik terkipleri.
CZ200158A CZ200158A3 (cs) 1998-10-28 1999-07-12 Prací a čistící prostředky
IDW20010074A ID28314A (id) 1998-10-28 1999-07-12 Komposisi-komposisi pencuci dan pembersih
ES99932389T ES2237123T3 (es) 1998-07-10 1999-07-12 Proceso para fabricar particulas de producto de reaccion de amina.
JP2000559208A JP2002524573A (ja) 1998-07-10 1999-07-12 アミン反応生成物の粒子の製造方法
EP99932388A EP1123376B2 (fr) 1998-10-28 1999-07-12 Compositions de lessive et de nettoyage
EP99932389A EP1144578B1 (fr) 1998-07-10 1999-07-12 Procede servant a preparer des particules de produit de reaction d'amine
ARP990103369A AR019367A1 (es) 1998-07-10 1999-07-12 Composicion de lavar ropa y limpiadora que comprende un ingrediente detersivo y un producto de reaccion entre un compuesto de amina primaria y/o secundariay un componente de perfume, metodo de suministrar una fragancia residual a una superficie con la misma, uso de dicho compuesto para la fabricacio
US10/714,784 US20040147426A1 (en) 1998-07-10 2003-11-17 Laundry and cleaning compositions
US10/911,115 US20050043205A1 (en) 1998-07-10 2004-08-04 Laundry and cleaning compositions

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP98870226 1998-07-10
EP98870155 1998-10-28
EP98870155 1998-10-28
EP98870226A EP0971024A1 (fr) 1998-07-10 1998-10-28 Compositions de blanchissage et de lavage
EP99870025A EP0971026A1 (fr) 1998-07-10 1999-02-11 Compositions de lavage et de nettoyage

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EP0971026A1 true EP0971026A1 (fr) 2000-01-12

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EP99870025A Withdrawn EP0971026A1 (fr) 1998-07-10 1999-02-11 Compositions de lavage et de nettoyage
EP99932388A Expired - Lifetime EP1123376B2 (fr) 1998-07-10 1999-07-12 Compositions de lessive et de nettoyage

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JP (1) JP4493849B2 (fr)
KR (1) KR20010053480A (fr)
CN (1) CN1321187A (fr)
AT (1) ATE339494T1 (fr)
AU (1) AU4870299A (fr)
BR (1) BR9912033A (fr)
CA (1) CA2336666A1 (fr)
CZ (1) CZ200158A3 (fr)
DE (1) DE69933230T3 (fr)
ES (1) ES2273504T3 (fr)
HU (1) HUP0200238A3 (fr)
ID (1) ID28314A (fr)
MA (1) MA24922A1 (fr)
TR (1) TR200100002T2 (fr)
WO (1) WO2000002982A2 (fr)

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US6790815B1 (en) 1998-07-10 2004-09-14 Procter & Gamble Company Amine reaction compounds comprising one or more active ingredient
US6906012B1 (en) 1999-11-09 2005-06-14 Procter & Gamble Company Detergent compositions comprising a fragrant reaction product
US6972276B1 (en) 1999-07-09 2005-12-06 Procter & Gamble Company Process for making amine compounds
US7012047B2 (en) 1998-07-10 2006-03-14 Procter & Gamble Company Amine reaction compounds comprising one or more active ingredient
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US7012047B2 (en) 1998-07-10 2006-03-14 Procter & Gamble Company Amine reaction compounds comprising one or more active ingredient
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US6764986B1 (en) 1999-07-08 2004-07-20 Procter & Gamble Company Process for producing particles of amine reaction products
US6972276B1 (en) 1999-07-09 2005-12-06 Procter & Gamble Company Process for making amine compounds
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US7601681B2 (en) 1999-12-22 2009-10-13 The Procter & Gamble Company Laundry and cleaning and/or fabric care composition
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JP2002520495A (ja) 2002-07-09
CN1321187A (zh) 2001-11-07
HUP0200238A3 (en) 2004-01-28
HUP0200238A2 (hu) 2002-07-29
EP1123376A2 (fr) 2001-08-16
JP4493849B2 (ja) 2010-06-30
KR20010053480A (ko) 2001-06-25
MA24922A1 (fr) 2000-04-01
ES2273504T3 (es) 2007-05-01
CA2336666A1 (fr) 2000-01-20
DE69933230T2 (de) 2007-08-30
EP1123376B1 (fr) 2006-09-13
WO2000002982A2 (fr) 2000-01-20
EP1123376B2 (fr) 2012-10-17
AU4870299A (en) 2000-02-01
CZ200158A3 (cs) 2002-04-17
DE69933230T3 (de) 2013-02-07
BR9912033A (pt) 2001-05-22
DE69933230D1 (de) 2006-10-26
WO2000002982A3 (fr) 2001-06-14
TR200100002T2 (tr) 2002-09-23

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