WO2000002982A2 - Procede servant a preparer des particules de produit de reaction d'amine - Google Patents

Procede servant a preparer des particules de produit de reaction d'amine Download PDF

Info

Publication number
WO2000002982A2
WO2000002982A2 PCT/US1999/015678 US9915678W WO0002982A2 WO 2000002982 A2 WO2000002982 A2 WO 2000002982A2 US 9915678 W US9915678 W US 9915678W WO 0002982 A2 WO0002982 A2 WO 0002982A2
Authority
WO
WIPO (PCT)
Prior art keywords
perfume
methyl
acid
composition
compositions
Prior art date
Application number
PCT/US1999/015678
Other languages
English (en)
Other versions
WO2000002982A3 (fr
Inventor
Jean-Luc Philippe Bettiol
Alfred Busch
Hugo Denutte
Christophe Laudamiel
Johan Smets
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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=WO2000002982(A2) "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
Priority to CA002336666A priority Critical patent/CA2336666A1/fr
Priority to DE69933230T priority patent/DE69933230T3/de
Priority to BR9912033-0A priority patent/BR9912033A/pt
Priority to EP99932388A priority patent/EP1123376B2/fr
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU48702/99A priority patent/AU4870299A/en
Priority to KR1020017000417A priority patent/KR20010053480A/ko
Priority to JP2000559205A priority patent/JP4493849B2/ja
Publication of WO2000002982A2 publication Critical patent/WO2000002982A2/fr
Publication of WO2000002982A3 publication Critical patent/WO2000002982A3/fr
Priority to US10/911,115 priority patent/US20050043205A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • 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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/507—Compounds 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 and/or secondary and/or secondary 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.
  • One solution is to use carrier mechanisms for perfume delivery, such as by encapsulation. This is taught in the prior art and described in U.S. 5,188,753.
  • 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 and/or ketone fragrance perception.
  • perfumers have formulated around the composition For example, by having a carrier or encapsulating material for such notes such as with cyclodextrin, zeolites or starch
  • 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 ammo functional polymer comprising at least one primary and/or secondary amine group and a perfume component selected from ketone, aldehyde, and mixtures thereof, characterised in that said ammo 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
  • a method of delivering residual fragrance to a surface by means of the compound or composition of the invention.
  • An essential component of the invention is a product of reaction an amino functional polymer comprising at least one primary and/or secondary 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 on-going 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.
  • Methylanthranilate 1 % (reference) 3.4 1 ,4-b ⁇ s-(3-am ⁇ nopropyl) piperazine (BNPP) 1 % 1 0
  • a general structure for the am o functional polymer containing at least one primary amine group of the present invention is as follows
  • 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 ammo functional polymer is of the following formula
  • Ammo functional polymer containing a secondary amine group have a structure similar to the above excepted that the polymer comprises one or more -NH- groups instead of -NH2 Further, the polymer structure may also have one or more of both -NH2 and -NH- groups
  • ammo functional polymer of the present invention contains at least one free, unmodified primary and/or secondary ammo 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 ammo functional polymer comprising an unmodified primary and/or secondary ammo group present on side cha ⁇ n(s)
  • the ammo functional polymers of the present invention will comprise several ammo groups, more preferably more than 10 ammo groups
  • the ammo 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
  • ammo 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 (1) (2) (3)
  • F H, - NH 2 , - COOH, COOR*, -C - CH 3 , - O-C -CH 3 ,- OH, - CN, - OR * ,
  • 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.
  • 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. This 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.
  • end groups E can be an H, NH2 groups, an aromatic, alicyclic, heteroaromatic or heterocyclic group including mono-, di-, oligo-, poly-saccharides :
  • 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 for use in the present invention are selected from the polyvinylamines, derivatives thereof, copolymer thereof, alkylene polyamine, polyaminoacid and copolymer thereof, cross-linked polyaminoacids. amino substituted polyvinylalcohol, polyoxyethylene bis amine or bis aminoalkyl, aminoalkyl piperazine and derivatives, N,N'-bis-(3- aminopropyl)-1 ,3-propanediamine linear or branched (TPTA), and mixtures thereof.
  • TPTA N,N'-bis-(3- aminopropyl)-1 ,3-propanediamine linear or branched
  • Polyamino acid is one suitable and preferred class of amino-functional polymer.
  • Polyaminoacids are compounds which are made up of amino acids or chemically modified amino acids. They can contain alanine, serine, aspartic acid, arginine, valine, threonine, glutamic acid, leucine, cysteine, histidine, lysine, isoleucine, tyrosine, asparagine, methionine, proline, tryptophan, phenylalanine, glutamine, glycine or mixtures thereof.
  • chemically modified amino acids the amine or acidic function of the amino acid has reacted with a chemical reagent.
  • Preferred polyamino acids are polylysines, polyarginine, polyglutamine, polyasparagine, polyhistidine, polytryptophane or mixtures thereof. Most preferred are polylysines or polyamino acids where more than 50% of the amino acids are lysine, since the primary amine function in the side chain of the lysine is the most reactive amine of all amino acids.
  • the preferred polyamino acid has a molecular weight of 500 to 10.000.000, more preferably between 5.000 and 750.000.
  • the polyamino acid can be cross linked.
  • the cross linking can be obtained for example by condensation of the amine group in the side chain of the amino acid like lysine with the carboxyl function on the amino acid or with protein cross linkers like PEG derivatives.
  • the cross linked polyamino acids still need to have free primary and/or secondary amino groups left for reaction with the active ingredient.
  • the preferred cross linked polyamino acid has a molecular weight of 20 000 to 10 000 000, more preferably between 200 000 and 2 000 000
  • the polyamino acid or the ammo acid can be co-polymerized with other reagents like for instance with acids, amides, acyl chlorides More specifically with aminocaproic acid, adipic acid, ethylhexanoic acid, caprolactam or mixture thereof
  • the molar ratio used in these copolymers ranges from 1 1 (reagent/ ammo acid (lysine)) to 1 20, more preferably from 1 1 to 1 10
  • the polyamino acid like polylysine can be partially ethoxylated
  • polyaminoacid can be obtained before reaction with the active ingredient, under a salt form
  • polylysine can be supplied as polylysine hydrobromide
  • Polylysine hydrobromide is commercially available from Sigma, Applichem, Bachem and Fluka
  • ammo functional polymers containing at least one primary and/or secondary amine group for the purpose of the present invention are:
  • Polyamino acid (L-lysine / lauric acid in a molar ratio of 10/1), Polyamino acid (L-lysine / aminocaproic acid / adipic acid in a molar ratio of 5/5/1 ), ), Polyamino acid (L-lysine / aminocaproic acid /ethylhexanoic acid in a molar ratio of 5/3/1) Polyamino acid (polylysme-cocaprolactam), Polylysine hydrobromide, cross- linked polylysine,
  • Preferred ammo functional polymers containing at least one primary and/or secondary amine group are
  • ammo functional polymers comprising at least one primary and/or secondary amine group and the amine reaction product provide fabric appearance benefits, in particular color care and protection against fabric wear Indeed, 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
  • compositions of the present invention can provide simultaneously fabric care and long lasting perfume benefits
  • perfume ketone or aldehyde any chain containing at least 1 carbon atom, preferably at least 5 carbon atoms
  • a typical disclosure of suitable ketone and/or aldehydes, traditionally used in perfumery, can be found in "perfume and Flavor Chemicals", Vol. I and II, S. Arctander, Allured Publishing, 1994, ISBN 0-931710-35-5.
  • 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 Ionone, Fleuramone, Dihydrojasmone, Cis-Jasmone, Iso-E-Super, Methyl- Cedrenyl-ketone or Methyl- Cedrylone, Acetophenone, Methyl-Acetophenone, Para-Methoxy-
  • 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-d ⁇ methyl-3-cyclohexen-1 -carboxaldehyde, c ⁇ s/trans-3,7-d ⁇ methyl-2,6-octad ⁇ en-1-al, heliotropm, 2,4,6-tr ⁇ methyl-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
  • Odor Detection Threshold should be lower than 1 ppm, preferably lower than 10ppb - measured at controlled Gas Chromatography (GC) conditions such as described here below
  • GC Gas Chromatography
  • 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 Since the precise concentration at the detector at any point in time is known, the mass per volume inhaled is known and hence the concentration of material.
  • solutions are delivered to the sniff port at the back-calculated concentration.
  • a panelist sniffs the GC effluent and identifies the retention time when odor is noticed. The average over all panelists determines the threshold of noticeability.
  • the necessary amount of analyte is injected onto the column to achieve a certain concentration, such as 10 ppb, at the detector.
  • Typical gas chromatograph parameters for determining odor detection thresholds are listed below.
  • perfume components are those selected from : 2- methyl-2-(para-iso-propylphenyl)-propionaldehyde, 1-(2,6,6-trimethyl-2- cyciohexan-1-yl)-2-buten-1-one and/or para-methoxy-acetophenone.
  • the following compounds having an ODT ⁇ 10ppb measured with the method described above undecylenic aldehyde, undecalactone gamma, heliotropin, dodecalactone gamma, p-anisic aldehyde, para hydroxy-phenyl- butanone, cymal, benzyl acetone, ionone alpha, p.t.bucinal, damascenone, ionone beta and methyl-nonyl ketone.
  • the level of perfume is of from 10 to 90%, preferably from 30 to 85%, more preferably from 45 to 80% by weight of the amine reaction product.
  • Preferred amine reaction products are those resulting from the reaction of polyaminoacid like Polylysine, BNPP, or TPTA with one or more of the following Alpha Damascone, Delta Damascone, Carvone, Hedione, Florhydral, Lilial, Heliotropine, Gamma-Methyl-lonone and 2,4-dimethyl-3-cyclohexen-1- carboxaldehyde, and mixture thereof.
  • Most preferred amine reaction products are those from the reaction of BNPP or TPTA with Alpha and Delta Damascone.
  • 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 preferably 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.
  • the spinned but still wet fabrics are assessed for their odors using the scale mentioned below.
  • half of the fabric pieces are hung on a line for 24 hr drying, away from any possible contaminations. Unless specified, this drying takes place indoor. Ambient conditions are at temperature between 18-25C and air moisture between 50-80%.
  • the other half is placed in a tumble drier and undergoes a full "very dry" cycle, i.e. in a Miele, Novotronic T430 set on program white-extra dry (full cycle). Tumble dry fabrics are also assessed on the next day. Fabrics are then stored in opened aluminum bags in an odor free room, and assessed again after 7 days.
  • 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 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 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 Hence, the interaction with perfume composition which may be present in fully formulated composition is avoided as well as side reaction that could occur Further, by such means of incorporation, 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 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 C11-C18 alkyl benzene sulfonates ("LAS”) and primary, branched-cham and random C10-C20 alkyl sulfates (“AS”), the C-jo-C-18 secondary (2,3) alkyl sulfates of the formula
  • x and (y + 1) are integers of at least 7, preferably at least 9, and M is a water- solubilizmg cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C10-C18 alkyl alkoxy sulfates ("AE X S", especially x up to 7 EO ethoxy sulfates), C10-C-18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C- ⁇ rj-18 glycerol ethers, the C-
  • 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
  • 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
  • detergent builder Granular formulations typically comprise from 1 % to 80%, more typically from 5% to 50% by weight, of the detergent builder
  • Inorganic or P-containmg detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripoiyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and alummosilicates
  • non-phosphate builders are required in some locales
  • the 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 S1O2 Na2 ⁇ 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-Na2S ⁇ 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 NaMS ⁇ x ⁇ 2 ⁇ + ⁇ yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1 9 to 4, preferably 2, and y is a
  • Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 , as the alpha, beta and gamma forms As noted above, the delta-Na2S ⁇ 5 (NaSKS-6 form) is most preferred for use herein
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispenmg 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
  • Alummosilicate builders are useful in the present invention Alummosilicate 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 Alummosilicate builders include those having the empirical formula z/n[(AI0 2 )z(S ⁇ 2)y] xH 2 0 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
  • alummosilicate ion exchange materials are commercially available These alummosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived A method for producing alummosilicate ion exchange materials is disclosed in U S 3,985,669 Preferred synthetic crystalline alummosilicate ion exchange materials useful herein are available under the designations Zeolite A Zeolite P (B), Zeolite MAP and Zeolite X
  • the alummosilicate 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 oxydisuccmate, 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
  • detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1 , 3, 5- t hydroxy benzene-2, 4, 6-tr ⁇ sulphon ⁇ c acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamme tetraacetic acid and nitnlotriacetic acid, as well as polycarboxylates such as mellitic acid, pyromellitic succmic acid, oxydisuccmic acid, polymaleic acid, benzene 1 ,3,5-tr ⁇ carboxyl ⁇ c 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
  • succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in EP 0,200,263.
  • Fatty acids e.g., C12-C18 monocarboxylic acids such as oleic acid and/or its salts, can also be incorporated into the compositions alone, or in combination with 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.
  • bleaching agents may be at levels of from 1 % to 30%, more typically from 5% to 20%, of the detergent composition, especially for fabric laundering. If present, 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
  • 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-tr ⁇ -methyl hexanoyl oxybenzene sulfonate
  • TAED tetraacetyl ethylene diamine
  • R1 is an alkyl group containing from 6 to 12 carbon atoms
  • R 2 is an alkylene containing from 1 to 6 carbon atoms
  • R5 IS H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon atoms
  • 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- octanam ⁇ do-caproyl)oxybenzenesulfonate, (6-nonanam ⁇ docaproyl)oxybenzene sulfonate, (6-decanam ⁇ do-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 benzoxazm-type activators disclosed by Hodge et al in U S Patent 4,966,723
  • a highly preferred activator of the benzoxazm-type is
  • Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
  • R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to 12 carbon atoms.
  • Highly preferred 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 perbor
  • 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-0) (1 ,4,7-trimethyl-1 ,4,7-triazacyclononane)2(PF6)2, Mn" ⁇ (u-0)-
  • 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.
  • hydrophilic optical brighteners useful in the present invention are those having the structural formula:
  • R ⁇ is selected from anilino, hydroxyethyl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N- methylamino, morphilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • is anilino
  • R2 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.
  • Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the rinse added compositions herein
  • Ri is anilino
  • R2 is N-2-hydroxyethyl-N-2- methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-b ⁇ s[(4- an ⁇ l ⁇ no-6-(N-2-hydroxyethyl-N-methylam ⁇ no)-s-tr ⁇ az ⁇ ne-2-yl)am ⁇ no]2,2'- stilbenedisulfonic acid disodium salt
  • Tinopal 5BM-GX® is commercially marketed by Ciba-Geigy
  • R ⁇ is anilino
  • R2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-b ⁇ s[(4-an ⁇ l ⁇ no-6-morph ⁇ l ⁇ no-s-tr ⁇ az ⁇ ne-2- yl)am ⁇ no]2,2'-st ⁇ lbened ⁇ sulfon ⁇ c acid, sodium salt
  • Tinopal AMS-GX® 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
  • a soil release agent preferably 0.2% to 5%, of a soil release agent
  • 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 polymers suitable for use in the present invention
  • U S Patent 4 702,857 Gosselink, issued October 27, 1987, U S 4,968,451 Scheibel et al issued November 6, U S 4,702,857, Gosselink, issued October 27, 1987, U S 4 711 730, Gosselink et al , issued December 8, 1987, U S 4,721 ,580 Gosselink issued January 26, 1988, U S 4,877,896 Maldonado et al , issued October 31 , 1989, U S 4,956,447, G
  • soil release agents include the METOLOSE SM100, METOLOSE SM200 manufactured by Shm-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 po ⁇ nt(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 Depending on the amount of anionic or nonionic detergent, etc , used in the wash cycle of a
  • Preferred scum dispersants are Brij 700®, Varonic U-250®, Genapol T-500®, Genapol T-800®, Plurafac A-79®, and Neodol 25-50®
  • bactencides used in the compositions of this invention include glutaraldehyde, formaldehyde, 2-bromo-2-n ⁇ tro-propane-1 ,3-d ⁇ ol sold by Inolex Chemicals, located in Philadelphia, Pennsylvania, under the trade name Bronopol®, and a mixture of 5-chloro-2-methyl-4- ⁇ soth ⁇ azol ⁇ ne-3-one and 2- methyl-4- ⁇ soth ⁇ azol ⁇ ne-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 Suitable 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
  • 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, terpmeol, 3,7-d ⁇ methyl-c/s- 2,6-octad
  • 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, tnethyl 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 Chelating Agents
  • 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, triethylenetetra- aminehexacetates, diethylenetriaminepentaacetates, and ethanoldigiycines, 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-disuifobenzene.
  • a preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
  • EDDS ethylenediamine disuccinate
  • the 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 C1-C4 diphosphonic acid, more preferably a C2 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.
  • a C1-C4 diphosphonic acid more preferably a C2 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.
  • compositions of the invention may preferably contain a clay, preferably present at a level of from 0.05% to 40%, more preferably from 0.5% to 30%, most preferably from 2% to 20% by weight of the composition.
  • clay mineral compound as used herein, excludes sodium aluminosilicate zeolite builder compounds, which however, may be included in the compositions of the invention as optional components.
  • One preferred clay may be a bentonite clay.
  • Highly preferred are smectite clays, as for example disclosed in the US Patents No.s 3,862,058 3,948,790, 3,954,632 and 4,062,647 and European Patents No.s EP-A-299,575 and EP-A- 313,146 all in the name of the Procter and Gamble Company.
  • smectite clays herein includes both the clays in which aluminium oxide is present in a silicate lattice and the clays in which magnesium oxide is present in a silicate lattice.
  • Typical smectite clay compounds include the compounds having the general formula Al2(Si2 ⁇ 5)2(OH)2.nH2 ⁇ and the compounds having the general formula Mg 3 (Si2 ⁇ 5)2(OH)2.nH2 ⁇ . Smectite clays tend to adopt an expandable three layer structure.
  • Suitable smectite clays include those selected from the classes of the montmorillonites, hectorites, volchonskoites, nontronites, saponites and sauconites, particularly those having an alkali or alkaline earth metal ion within the crystal lattice structure.
  • Sodium or calcium montmorillonite are particularly preferred.
  • Suitable smectite clays are sold by various suppliers including English China Clays, Laviosa, Georgia Kaolin and Colin Stewart Minerals. Clays for use herein preferably have a particle dimension of from 10nm to 800nm more preferably from 20nm to 500 mm, most preferably from 50nm to 200 mm.
  • Particles of the clay mineral compound may be included as components of agglomerate particles containing other detergent compounds.
  • the term "largest particle dimension" of the clay mineral compound refers to the largest dimension of the clay mineral component as such, and not to the agglomerated particle as a whole.
  • Substitution of small cations, such as protons, sodium ions, potassium ions, magnesium ions and calcium ions, and of certain organic molecules including those having positively charged functional groups can typically take place within the crystal lattice structure of the smectite clays.
  • a clay may be chosen for its ability to preferentially absorb one cation type, such ability being assessed by measurements of relative ion exchange capacity.
  • the smectite clays suitable herein typically have a cation exchange capacity of at least 50 meq/100g.
  • U.S. Patent No. 3,954,632 describes a method for measurement of cation exchange capacity.
  • the crystal lattice structure of the clay mineral compounds may have, in a preferred execution, a cationic fabric softening agent substituted therein.
  • a cationic fabric softening agent substituted therein Such substituted clays have been termed 'hydrophobically activated' clays.
  • the cationic fabric softening agents are typically present at a weight ratio, cationic fabric softening agent to clay, of from 1 :200 to 1 :10, preferably from 1 :100 to 1 :20.
  • Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP- B-0 011 340.
  • a preferred commercially available "hydrophobically activated" clay is a bentonite clay containing approximately 40% by weight of a dimethyl ditallow quaternary ammonium salt sold under the tradename Claytone EM by English China Clays International.
  • the clay is present in an intimate mixture or in a particle with a humectant and a hydrophobic compound, preferably a wax or oil, such as paraffin oil
  • humectants are organic compounds, including propylene glycol, ethylene glycol, dimers or tnmers of glycol, most preferably glycerol
  • the particle is preferably an agglomerate
  • the particle may be such that the wax or oil and optionally the humectant form an encapsulate on the clay or alternatively, the clay be a encapsulate for the wax or oil and the humectant It may be preferred that the particle comprises an organic salt or silica or silicate
  • the clay is preferably mixed with one or more surfactants and optionally builders and optionally water, in which case the mixture is preferably subsequently dried
  • a mixture is further processed in a spray-drying method to obtain a spray dried particle comprising the clay
  • the flocculating agent is also comprised in the particle or granule comprising the clay
  • the intimate mixture comprises a chelating agent
  • compositions of the invention may contain a clay flocculating agent, preferably present at a level of from 0 005% to 10%, more preferably from 0 05% to 5%, most preferably from 0 1 % to 2% by weight of the composition
  • the clay flocculating agent functions such as to bring together the particles of clay compound in the wash solution and hence to aid their deposition onto the surface of the fabrics in the wash This functional requirement is hence different from that of clay dispersant compounds which are commonly added to laundry detergent compositions to aid the removal of clay soils from fabrics and enable their dispersion within the wash solution
  • Preferred as clay flocculating agents herein are organic polymeric materials having an average weight of from 100,000 to 10,000,000, preferably from 150,000 to 5,000,000, more preferably from 200,000 to 2,000,000 Suitable organic polymeric materials comprise homopolymers or copolymers containing monomeric units selected from alkylene oxide, particularly ethylene oxide, acrylamide, acrylic acid, vinyl alcohol, vinyl pyrrolidone, and ethylene imine. Homopolymers of, on particular, ethylene oxide, but also acrylamide and acrylic acid are preferred.
  • EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe preferred organic polymeric clay flocculating agents for use herein.
  • the weight ratio of clay to the flocculating polymer is preferably from 1000:1 to 1 :1 , more preferably from 500:1 to 1 :1 , most preferably from 300:1 to 1 :1 , or even more preferably from 80:1 to 10:1 , or in certain applications even from 60:1 to 20:1.
  • Inorganic clay flocculating agents are also suitable herein, typical examples of which include lime and alum.
  • the flocculating agent is preferably present in a detergent base granule such as a detergent agglomerate, extrudate or spray-dried particle, comprising generally one or more surfactants and builders.
  • Effervescent means may also be optionally used in the compositions of the invention.
  • Effervescency as defined herein means the evolution of bubbles of gas from a liquid, as the result of a chemical reaction between a soluble acid source and an alkali metal carbonate, to produce carbon dioxide gas, i.e. C6H 8 0 7 + 3NaHC0 3 ⁇ * • Na 3 C 6 H 5 ⁇ 7 + 3C0 2 + 3H2O
  • Suitable alkali and/ or earth alkali inorganic carbonate salts herein include carbonate and hydrogen carbonate of potassium, lithium, sodium, and the like amongst which sodium and potassium carbonate are preferred.
  • Suitable bicarbonates to be used herein include any alkali metal salt of bicarbonate like lithium, sodium, potassium and the like, amongst which sodium and potassium bicarbonate are preferred.
  • the choice of carbonate or bicarbonate or mixtures thereof may be made depending on the pH desired in the aqueous medium wherein the granules are dissolved.
  • the inorganic alkali and/ or earth alkali carbonate salt of the compositions of the invention comprises preferably a potassium or more preferably a sodium salt of carbonate and/ or bicarbonate.
  • the carbonate salt comprises sodium carbonate, optionally also a sodium bicarbonate.
  • the inorganic carbonate salts herein are preferably present at a level of at least 20% by weight of the composition. Preferably they are present at a level of at least 23% or even 25% or even 30% by weight, preferably up to about 60% by weight or more preferably up to 55% or even 50% by weight.
  • detergent granules such as agglomerates or spray dried granules.
  • an effervescence source is present, preferably comprising an organic acid, such as carboxylic acids or aminoacids, and a carbonate. Then it may be preferred that part or all of the carbonate salt herein is premixed with the organic acid, and thus present in an separate granular component.
  • Preferred effervescent source are selected from compressed particles of citric acid and carbonate optionally with a binder: and particle of carbonate, bicarbonate and malic or maleic acid in weight ratios of 4:2:4.
  • the dry add form of citric acid and carbonate are preferably used.
  • the carbonate may have any particle size.
  • the carbonate salt in particular when the carbonate salt is present in a granule and not as separately added compound, the carbonate salt has preferably a volume median particle size from 5 to 375 microns, whereby preferably at least 60%, preferably at least 70% or even at least 80% or even at least 90% by volume, has a particle size of from 1 to 425 microns.
  • the carbon dioxide source has a volume median particle size of 10 to 250, whereby preferably at least 60 %, or even at least 70% or even at least 80% or even at least 90% by volume, has a particle size of from 1 to 375 microns; or even preferably a volume median particle size from 10 to 200 microns, whereby preferably at least 60 %, preferably at least 70% or even at least 80% or even at least 90% by volume, has a particle size of from 1 to 250 microns.
  • the carbonate salt when added as separate component, so to say 'dry-added' or admixed to the other detergent ingredients, the carbonate may have any particle size, including the above specified particle sizes, but preferably at least an volume average particle size of 200 microns or even 250 microns or even 300 microns.
  • the carbon dioxide source of the required particle size is obtained by grinding a larger particle size material, optionally followed by selecting the material with the required particle size by any suitable method.
  • percarbonate saits may be present in the compositions of the invention as a bleaching agent, they are not included in the carbonate salts as defined herein
  • compositions 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, anti-static agents, other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations and solid fillers for bar compositions.
  • composition of the invention may take a variety of physical form including liquid, gel, foam in either aqueous or non-aqueous form, granular and tablet forms.
  • 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 wiil 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.
  • the composition When in a liquid form, the composition may also be dispensed by a dispensing means such as a spray dispenser, or aerosol dispenser.
  • a dispensing means such as a spray dispenser, or aerosol dispenser.
  • the present invention also relates to such compositions incorporated into a spray dispenser to create an article of manufacture that can facilitate treatment of fabric articles and/or surfaces with said compositions containing the amine reaction product and other ingredients (examples are cyclodextrins, polysaccharides, polymers, surfactant, perfume, softener) at a level that is effective, yet is not discernible when dried on the surfaces.
  • the spray dispenser comprises manually activated and non-manual powered (operated) spray means and a container containing the treating composition. Typical disclosure of such spray dispenser can be found in WO 96/04940 page 19 line 21 to page 22 line 27.
  • the articles of manufacture preferably are in association with instructions for use to ensure that the consumer applies sufficient ingredient of the composition to provide the desired benefit.
  • compositions to be dispensed from a sprayer contain a level of amine reaction product of from about 0.01% to about 5%, preferably from about 0.05% to about 2%, more preferably from about 0.1% to about 1 %, by weight of the usage composition.
  • composition of the invention are suitable for use in any step of the domestic treatment, that is a pre-treatment composition, as a wash additive, as a composition suitable for use in the laundry and cleaning process.
  • a pre-treatment composition as a wash additive
  • a composition suitable for use in the laundry and cleaning process Obviously, multiple application can be made such as treating the fabric with a pre-treatment composition of the invention and thereafter with the composition suitable for use in the laundry process.
  • 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 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.
  • active component e.g perfume
  • the abbreviated component identifications have the following meanings:
  • STPP Anhydrous sodium tripolyphosphate TSPP Tetrasodium pyrophosphate Zeolite A Hydrated sodium aluminosilicate of formula Nai2(A1 ⁇ 2Si ⁇ 2)-
  • Citric acid Anhydrous citric acid Borate Sodium borate Carbonate Anydrous sodium carbonate with a particle size between 200 ⁇ m and 900 ⁇ m
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m
  • Protease Proteolytic enzyme having 3.3% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Savinase
  • Protease I Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591 , sold by
  • 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
  • NAC-OBS (6-nonamidocaproyl) oxybenzene sulfonate
  • TAED Tetraacetylethylenediamine DTPA
  • DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename
  • Photoactivated Sulfonated zinc phthlocyanine encapsulated in bleach (1) dextrin soluble polymer Photoactivated Sulfonated alumino phthlocyanine encapsulated in bleach (2) dextrin soluble polymer Brightener 1 Disodium 4,4'-bis(2-suiphostyryl)biphenyl Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5- thazin-2-yl)amino) stilbene-2:2'-disulfonate
  • PEO Polyethylene oxide with an average molecular weight of 50,000
  • PVNO Polyvinylpyridine N-oxide polymer with an average molecular weight of 50,000
  • PEI Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen
  • Opacifier Water based monostyrene latex mixture, sold by
  • Wax Paraffin wax PA30 Polyacrylic acid of average molecular weight of between about 4,500 - 8,000.
  • 3 -Ci 5 mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5.
  • Neodol 45-13 C14-C15 linear primary alcohol ethoxylate sold by Shell
  • ARP2 Amine reaction product of N,N'b ⁇ s(am ⁇ nopropyl)1 ,3- propanediamine with ⁇ -Damascone as made from
  • Flocculating agent II polyethylene oxide of average molecular weight of between 400,000 and 1 ,000,000
  • Flocculating agent III polymer of acrylamide and/ or acrylic acid of average molecular weight of 200,000 and
  • liquid detergent formulations were prepared in accord with the invention (levels are given as parts per weight).
  • liquid detergent formulations were prepared in accord with the invention (levels are given in parts per weight):
  • liquid detergent compositions were prepared in accord with the invention (levels are given in parts per weight).
  • composition in the form of a tablet, bar, extrudate or granule in accord with the invention is a composition in the form of a tablet, bar, extrudate or granule in accord with the invention
  • laundry bar detergent compositions were prepared in accord with the invention (levels are given in parts per weight).
  • Nonionic 1.2 1.0 0.7 0.8 1.9 0.7 0.6 0.3
  • 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/cnr ⁇ 2 using a standard 12 head rotary press:
  • liquid dishwashing detergent compositions of density 1.40Kg/L were prepared according to the present invention :
  • liquid rinse aid compositions were prepared according to the present invention :
  • liquid dishwashing compositions were prepared according to the present invention :
  • liquid hard surface cleaning compositions were prepared according to the present invention :
  • lavatory cleansing block compositions were prepared according to the present invention.
  • the following toilet bowl cleaning composition was prepared according to the present invention.

Abstract

L'invention concerne une composition nettoyante et détergente contenant un ingrédient détersif et un produit de réaction entre un polymère fonctionnel amino comprenant au moins un groupe amine primaire et/secondaire et un parfum. Ceci permet de libérer le parfum pendant une durée prolongée par rapport à l'utilisation du parfum lui-même.
PCT/US1999/015678 1998-07-10 1999-07-12 Procede servant a preparer des particules de produit de reaction d'amine WO2000002982A2 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
JP2000559205A JP4493849B2 (ja) 1998-10-28 1999-07-12 洗濯およびクリーニング組成物
KR1020017000417A KR20010053480A (ko) 1998-07-10 1999-07-12 세척 및 세정 조성물
DE69933230T DE69933230T3 (de) 1998-07-10 1999-07-12 Wasch- und reinigungsmittelzusammensetzungen
BR9912033-0A BR9912033A (pt) 1998-10-28 1999-07-12 Composições para lavar roupa e limpeza
EP99932388A EP1123376B2 (fr) 1998-10-28 1999-07-12 Compositions de lessive et de nettoyage
CA002336666A CA2336666A1 (fr) 1998-07-10 1999-07-12 Procede servant a preparer des particules de produit de reaction d'amine
AU48702/99A AU4870299A (en) 1998-07-10 1999-07-12 Laundry and cleaning compositions
US10/911,115 US20050043205A1 (en) 1998-07-10 2004-08-04 Laundry and cleaning compositions

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
EP98870155.3 1998-07-10
EP98870226.2 1998-10-28
EP98870226A EP0971024A1 (fr) 1998-07-10 1998-10-28 Compositions de blanchissage et de lavage
EP98870155 1998-10-28
EP99870025A EP0971026A1 (fr) 1998-07-10 1999-02-11 Compositions de lavage et de nettoyage
EP99870025.6 1999-02-11

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US09720346 A-371-Of-International 2001-02-28
US10/714,784 Continuation US20040147426A1 (en) 1998-07-10 2003-11-17 Laundry and cleaning compositions

Publications (2)

Publication Number Publication Date
WO2000002982A2 true WO2000002982A2 (fr) 2000-01-20
WO2000002982A3 WO2000002982A3 (fr) 2001-06-14

Family

ID=27239771

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/015678 WO2000002982A2 (fr) 1998-07-10 1999-07-12 Procede servant a preparer des particules de produit de reaction d'amine

Country Status (16)

Country Link
EP (2) EP0971026A1 (fr)
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)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6451751B1 (en) 1998-07-10 2002-09-17 The Procter & Gamble Company Process for producing particles of amine reaction product
WO2002092746A1 (fr) * 2001-05-11 2002-11-21 The Procter & Gamble Company Compositions de proparfum
US6699823B2 (en) 1998-07-10 2004-03-02 Procter & Gamble Company Amine reaction compounds comprising one or more active ingredient
US6790815B1 (en) 1998-07-10 2004-09-14 Procter & Gamble Company Amine reaction compounds comprising one or more active ingredient
US6858575B2 (en) 2001-11-27 2005-02-22 Procter & Gamble Company Pro-perfume compositions and substrate-treating products and methods using them
US6906012B1 (en) 1999-11-09 2005-06-14 Procter & Gamble Company Detergent compositions comprising a fragrant reaction product
US6916769B2 (en) 2001-12-03 2005-07-12 The Procter & Gamble Company Fabric treatment composition
US7036176B2 (en) 2002-02-13 2006-05-02 The Procter & Gamble Company Sequential dispensing of laundry additives during automatic machine laundering of fabrics
US7036177B2 (en) 2002-02-13 2006-05-02 The Procter & Gamble Company Dispensing of rinse additives into the rinse cycle during automatic machine laundering of fabrics
US7086110B2 (en) 2002-02-13 2006-08-08 The Procter & Gamble Company Selective dispensing of laundry additives during automatic machine laundering of fabric
US7168273B2 (en) 2002-11-07 2007-01-30 The Procter & Gamble Company Selective dispensing apparatus
US7340790B2 (en) 2002-02-13 2008-03-11 Procter & Gamble Company Universal dispenser for dispensing of laundry additives during automatic machine laundering of fabrics
US7445643B2 (en) 2003-12-03 2008-11-04 The Procter & Gamble Company Automatic machine laundering of fabrics
US7569529B2 (en) 2005-09-07 2009-08-04 The Procter & Gamble Company Method of using fabric care compositions to achieve a synergistic odor benefit
US7716956B2 (en) 2002-12-20 2010-05-18 The Procter & Gamble Company Attachment means
US7723285B2 (en) 2004-07-20 2010-05-25 Michigan Molecular Institute Beneficial agent delivery systems
US7749952B2 (en) 2006-12-05 2010-07-06 The Procter & Gamble Company Fabric care compositions for softening, static control and fragrance benefits
WO2011005816A1 (fr) 2009-07-09 2011-01-13 The Procter & Gamble Company Procédé de préparation de particules de parfum
US20110305659A1 (en) * 2009-09-18 2011-12-15 Ricky Ah-Man Woo Freshening compositions comprising malodor binding polymers and malodor control components
US8278230B2 (en) 2007-06-05 2012-10-02 The Procter & Gamble Company Perfume systems
EP1627036B2 (fr) † 2003-05-28 2015-06-17 Kao Corporation Composition de parfum
US9139799B1 (en) 2014-07-11 2015-09-22 Diversey, Inc. Scale-inhibition compositions and methods of making and using the same
US9920288B2 (en) 2014-07-11 2018-03-20 Diversey, Inc. Tablet dishwashing detergent and methods for making and using the same
US10346718B2 (en) 2014-07-11 2019-07-09 Diversey, Inc. Tablet dishwashing detergent and methods for making and using the same

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6740713B1 (en) 1999-07-08 2004-05-25 Procter & Gamble Company Process for producing particles of amine reaction products
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
EP1111034A1 (fr) 1999-12-22 2001-06-27 The Procter & Gamble Company Compositions de détergents et de nettoyants et/ou de soin des tissus
WO2006012215A1 (fr) * 2004-06-24 2006-02-02 Flexitral, Inc. Nouveaux muscs aldehydiques et leurs derives
EP2125552A2 (fr) * 2007-03-13 2009-12-02 The Procter and Gamble Company Procédé et produit de parfumage
DE102007012909A1 (de) 2007-03-19 2008-09-25 Momentive Performance Materials Gmbh Mit Duftstoffen modifizierte, reaktive Polyorganosiloxane
DE102007012910A1 (de) 2007-03-19 2008-09-25 Momentive Performance Materials Gmbh Mit Duftstoffen modifizierte, verzweigte Polyorganosiloxane
EP2270124A1 (fr) * 2009-06-30 2011-01-05 The Procter & Gamble Company Compositions de blanchiment comportant un système de livraison de parfum
KR101135069B1 (ko) * 2010-06-07 2012-04-19 씨엠에스무역(주) 환경친화형 저온용 소핑제 및 이를 이용한 소핑방법
JP5536563B2 (ja) * 2010-06-28 2014-07-02 株式会社Ａｄｅｋａ 食器洗浄機用洗浄剤組成物およびこの組成物を使用した洗浄方法
JP2012111810A (ja) * 2010-11-22 2012-06-14 Kao Corp 自動洗浄機用粉末洗浄剤組成物
JP6114072B2 (ja) * 2013-03-06 2017-04-12 花王株式会社 自動洗浄機用液体洗浄剤組成物
CN105102600A (zh) * 2013-03-28 2015-11-25 宝洁公司 包含聚醚胺、去垢性聚合物和羧甲基纤维素的清洁组合物
JP6101570B2 (ja) * 2013-05-31 2017-03-22 ライオン株式会社 洗浄剤
KR101485552B1 (ko) * 2013-07-04 2015-01-22 주식회사 잡스 살균제 조성물
US20150210964A1 (en) * 2014-01-24 2015-07-30 The Procter & Gamble Company Consumer Product Compositions
US9693675B2 (en) * 2014-12-20 2017-07-04 Medivators Inc. Cleaning composition
JP6629003B2 (ja) * 2015-08-06 2020-01-15 花王株式会社 食器用液体洗浄剤組成物
JP6591277B2 (ja) * 2015-12-15 2019-10-16 花王株式会社 食器用液体洗浄剤組成物
JP6862035B2 (ja) * 2017-01-20 2021-04-21 株式会社Adeka 中性洗浄剤組成物
EP3947620A1 (fr) * 2019-03-26 2022-02-09 Unilever Global Ip Limited Composition
JP7421920B2 (ja) 2019-12-17 2024-01-25 花王株式会社 繊維製品用洗浄剤組成物

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4853369A (en) 1987-12-18 1989-08-01 International Flavors & Fragrances Inc. Schiff base reaction product of ethyl vanillin and methyl anthranilate and organoleptic uses thereof
US5188753A (en) 1989-05-11 1993-02-23 The Procter & Gamble Company Detergent composition containing coated perfume particles
WO1995004809A1 (fr) 1993-08-09 1995-02-16 Firmenich S.A. Procede de parfumage de textiles
WO1995008976A1 (fr) 1993-09-30 1995-04-06 The Procter & Gamble Company Systeme fournissant une substance active
JPH0940687A (ja) 1995-07-31 1997-02-10 T Hasegawa Co Ltd 置換グルコサミン誘導体および持続性香料組成物
EP0841391A1 (fr) 1996-11-07 1998-05-13 The Procter & Gamble Company Compositions de parfum

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1133847B (de) † 1960-08-11 1962-07-26 Haarmann & Reimer Gmbh Verwendung der Kondensationsprodukte von Aldehyden und Ketonen mit Oxyaminen in der Parfuemerie
CA1130058A (fr) * 1978-11-17 1982-08-24 James B. Melville Formule liquide
US5008437A (en) † 1987-12-18 1991-04-16 International Flavors & Fragrances Inc. Schiff base reaction product of ethyl vanillin and methyl anthranilate and organoleptic uses thereof
GB8908199D0 (en) * 1989-04-12 1989-05-24 Unilever Plc Malodors reduction
GB8921995D0 (en) * 1989-09-29 1989-11-15 Unilever Plc Perfumed laundry detergents
USH1468H (en) * 1994-04-28 1995-08-01 Costa Jill B Detergent compositions containing cellulase enzyme and selected perfumes for improved odor and stability
EP0831143A1 (fr) * 1996-09-19 1998-03-25 The Procter & Gamble Company Composé polymérique contenant un ou plus alcools actifs

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4853369A (en) 1987-12-18 1989-08-01 International Flavors & Fragrances Inc. Schiff base reaction product of ethyl vanillin and methyl anthranilate and organoleptic uses thereof
US5188753A (en) 1989-05-11 1993-02-23 The Procter & Gamble Company Detergent composition containing coated perfume particles
WO1995004809A1 (fr) 1993-08-09 1995-02-16 Firmenich S.A. Procede de parfumage de textiles
WO1995008976A1 (fr) 1993-09-30 1995-04-06 The Procter & Gamble Company Systeme fournissant une substance active
JPH0940687A (ja) 1995-07-31 1997-02-10 T Hasegawa Co Ltd 置換グルコサミン誘導体および持続性香料組成物
EP0841391A1 (fr) 1996-11-07 1998-05-13 The Procter & Gamble Company Compositions de parfum

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KAMOGAWA ET AL., J. POLY. SET POLYM, CHEM. ED., vol. 20, 1982, pages 3121

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6451751B1 (en) 1998-07-10 2002-09-17 The Procter & Gamble Company Process for producing particles of amine reaction product
US6699823B2 (en) 1998-07-10 2004-03-02 Procter & Gamble Company Amine reaction compounds comprising one or more active ingredient
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
WO2002092746A1 (fr) * 2001-05-11 2002-11-21 The Procter & Gamble Company Compositions de proparfum
US6858575B2 (en) 2001-11-27 2005-02-22 Procter & Gamble Company Pro-perfume compositions and substrate-treating products and methods using them
US6916769B2 (en) 2001-12-03 2005-07-12 The Procter & Gamble Company Fabric treatment composition
US7036176B2 (en) 2002-02-13 2006-05-02 The Procter & Gamble Company Sequential dispensing of laundry additives during automatic machine laundering of fabrics
US7036177B2 (en) 2002-02-13 2006-05-02 The Procter & Gamble Company Dispensing of rinse additives into the rinse cycle during automatic machine laundering of fabrics
US7086110B2 (en) 2002-02-13 2006-08-08 The Procter & Gamble Company Selective dispensing of laundry additives during automatic machine laundering of fabric
US7340790B2 (en) 2002-02-13 2008-03-11 Procter & Gamble Company Universal dispenser for dispensing of laundry additives during automatic machine laundering of fabrics
US7168273B2 (en) 2002-11-07 2007-01-30 The Procter & Gamble Company Selective dispensing apparatus
US7716956B2 (en) 2002-12-20 2010-05-18 The Procter & Gamble Company Attachment means
EP1627036B2 (fr) † 2003-05-28 2015-06-17 Kao Corporation Composition de parfum
US7445643B2 (en) 2003-12-03 2008-11-04 The Procter & Gamble Company Automatic machine laundering of fabrics
US7723285B2 (en) 2004-07-20 2010-05-25 Michigan Molecular Institute Beneficial agent delivery systems
US7569529B2 (en) 2005-09-07 2009-08-04 The Procter & Gamble Company Method of using fabric care compositions to achieve a synergistic odor benefit
US7749952B2 (en) 2006-12-05 2010-07-06 The Procter & Gamble Company Fabric care compositions for softening, static control and fragrance benefits
US8278230B2 (en) 2007-06-05 2012-10-02 The Procter & Gamble Company Perfume systems
WO2011005816A1 (fr) 2009-07-09 2011-01-13 The Procter & Gamble Company Procédé de préparation de particules de parfum
US8273699B2 (en) 2009-07-09 2012-09-25 The Procter & Gamble Company Process for preparing a perfume particle
US20110305659A1 (en) * 2009-09-18 2011-12-15 Ricky Ah-Man Woo Freshening compositions comprising malodor binding polymers and malodor control components
US9139799B1 (en) 2014-07-11 2015-09-22 Diversey, Inc. Scale-inhibition compositions and methods of making and using the same
US9273269B2 (en) 2014-07-11 2016-03-01 Diversey, Inc. Scale-inhibition compositions and methods of making and using the same
US9920288B2 (en) 2014-07-11 2018-03-20 Diversey, Inc. Tablet dishwashing detergent and methods for making and using the same
US10346718B2 (en) 2014-07-11 2019-07-09 Diversey, Inc. Tablet dishwashing detergent and methods for making and using the same

Also Published As

Publication number Publication date
BR9912033A (pt) 2001-05-22
MA24922A1 (fr) 2000-04-01
TR200100002T2 (tr) 2002-09-23
CN1321187A (zh) 2001-11-07
HUP0200238A2 (hu) 2002-07-29
EP1123376B1 (fr) 2006-09-13
AU4870299A (en) 2000-02-01
DE69933230D1 (de) 2006-10-26
EP1123376A2 (fr) 2001-08-16
ID28314A (id) 2001-05-10
EP1123376B2 (fr) 2012-10-17
DE69933230T3 (de) 2013-02-07
JP2002520495A (ja) 2002-07-09
ATE339494T1 (de) 2006-10-15
EP0971026A1 (fr) 2000-01-12
CA2336666A1 (fr) 2000-01-20
ES2273504T3 (es) 2007-05-01
CZ200158A3 (cs) 2002-04-17
HUP0200238A3 (en) 2004-01-28
WO2000002982A3 (fr) 2001-06-14
KR20010053480A (ko) 2001-06-25
DE69933230T2 (de) 2007-08-30
JP4493849B2 (ja) 2010-06-30

Similar Documents

Publication Publication Date Title
EP1123376B1 (fr) Compositions de lessive et de nettoyage
EP1144566B1 (fr) Compositions de lessive et de nettoyage
US7601681B2 (en) Laundry and cleaning and/or fabric care composition
EP1144578B1 (fr) Procede servant a preparer des particules de produit de reaction d'amine
US20040147426A1 (en) Laundry and cleaning compositions
US20030228992A1 (en) Laundry and cleaning and/or fabric care compositions
US6764986B1 (en) Process for producing particles of amine reaction products
US6451751B1 (en) Process for producing particles of amine reaction product
EP1116788A1 (fr) Composition de pro-parfum
US20040018955A1 (en) Pro-perfume composition
EP1067174B1 (fr) Procédé de production de particules de produit de réaction d'amine
US6972276B1 (en) Process for making amine compounds
EP1067116A1 (fr) Procédé de préparation d'imines
EP1067173A1 (fr) Procédé de production de particules de produit de réaction d'amine
MXPA01000292A (en) Laundry and cleaning compositions
MXPA01000290A (en) Laundry and cleaning compositions
EP1067117A1 (fr) Procédé de préparation de composés imines

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 99808494.8

Country of ref document: CN

AK Designated states

Kind code of ref document: A2

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

AL Designated countries for regional patents

Kind code of ref document: A2

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

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

Ref document number: IN/PCT/2000/00331/DE

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 1200001038

Country of ref document: VN

ENP Entry into the national phase

Ref document number: 2000 559205

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2336666

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: PV2001-58

Country of ref document: CZ

WWE Wipo information: entry into national phase

Ref document number: 2001/00002

Country of ref document: TR

WWE Wipo information: entry into national phase

Ref document number: PA/a/2001/000292

Country of ref document: MX

Ref document number: 48702/99

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 1020017000417

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 1999932388

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 09720346

Country of ref document: US

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

AK Designated states

Kind code of ref document: A3

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

AL Designated countries for regional patents

Kind code of ref document: A3

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

WWP Wipo information: published in national office

Ref document number: 1020017000417

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 1999932388

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: PV2001-58

Country of ref document: CZ

WWR Wipo information: refused in national office

Ref document number: 1020017000417

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 10911115

Country of ref document: US

WWG Wipo information: grant in national office

Ref document number: 1999932388

Country of ref document: EP