EP0808358A1 - Compositions de blanchiment parfumees - Google Patents

Compositions de blanchiment parfumees

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Publication number
EP0808358A1
EP0808358A1 EP95943787A EP95943787A EP0808358A1 EP 0808358 A1 EP0808358 A1 EP 0808358A1 EP 95943787 A EP95943787 A EP 95943787A EP 95943787 A EP95943787 A EP 95943787A EP 0808358 A1 EP0808358 A1 EP 0808358A1
Authority
EP
European Patent Office
Prior art keywords
weight
perfume
bleaching composition
composition according
methyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP95943787A
Other languages
German (de)
English (en)
Other versions
EP0808358A4 (fr
Inventor
Allan Campbell Mcritchie
Michael Green
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0808358A1 publication Critical patent/EP0808358A1/fr
Publication of EP0808358A4 publication Critical patent/EP0808358A4/fr
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • 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

Definitions

  • the invention relates to perfumed bleaching compositions. More specifically, it relates to bleaching compositions comprising a bleach system and a stabilised perfume composition.
  • Perfumes are an important and desirable part of detergent compositions. They are used to cover up the chemical odours of the cleaning ingredients and provide an aesthetic benefit to the wash process and, preferably the cleaned fabrics.
  • EP 430315 which discloses the use of a laundry detergent composition containing a lipase and a perfume having specific fragrance materials, exemplifies such use. In said patent, the perfume composition is said to counteract the problem of the residual malodour of lipase treated laundry.
  • perfumes generally are volatile and many perfume ingredients can be destroyed or damaged by contact with cleaning ingredients, especially alkali and bleaches.
  • bleaches are sometimes admixed after perfume spray-on. Even this does not avoid oxidation of perfumes by bleaches, especially bleach activator/bleaching agent combinations, at least partly because of perfume mobility in the compositions.
  • EP 332259 teaches the use of a liquid detergent composition containing peroxyacid bleach and perfumed silica particles which protect the perfume from oxidation by the bleach.
  • a perfume composition comprising aroma chemicals selected from primary and secondary alcohols, aliphatic aldehydes, hydrocinnamic aldehydes, esters excluding salicylates and unsaturated ketones in a bleaching composition containing a bleaching system, selected from a perhydrate in combination with a bleach activator and a preformed peracid wherein said perhydrate and/or said preformed peracid are coated, which gives an excellent perfume fragrance on fabrics as well as an excellent perfume stability in presence of the bleaching ingredient in the wash liquor and in the product during storage.
  • a perfumed bleaching composition consists of a bleaching composition and a perfume composition, both as defined hereinafter, wherein said perfume is incorporated by any means in a composition selected from: i)-the bleaching composition as a finished product, ii)-the bleaching composition during its making process, or any mixtures thereof.
  • Processes for incorporating the perfume in the bleaching composition are not critical to the present invention. This can be done by spray-on, admixture with one or more component of the bleaching composition or other means known to the man skilled in the art. A preferred process, for cost and practibility reasons, is a spray-on process.
  • the present invention relates to a perfumed bleaching composition containing:
  • a-a bleaching system selected from i)-a perhydrate in amount of from 0.1 % to 60% by weight and combined with a bleach activator in amount of from 0.1 % to 60% by weight, ii)-a preformed peracid in amount of from 0.1 % to 60% by weight, and any mixtures thereof, wherein said perhydrate and/or said preformed peracid are coated; and
  • b-a perfume in amount from 0.05% to 2% by weight which comprises aroma chemicals selected from: primary and secondary alcohols, aliphatic aldehydes, hydrocinnamic aldehydes, esters excluding salicylates, unsaturated ketones and mixtures thereof, wherein the total sum of the weight of said aroma chemicals in the perfume is at least 30% by weight of the perfume.
  • aroma chemicals selected from: primary and secondary alcohols, aliphatic aldehydes, hydrocinnamic aldehydes, esters excluding salicylates, unsaturated ketones and mixtures thereof, wherein the total sum of the weight of said aroma chemicals in the perfume is at least 30% by weight of the perfume.
  • the bleaching composition may comprise a coated bleach activator and/or a chelant such as EDDS which further enhances the storage stability of the perfume.
  • the present invention contemplates bleaching compositions having an excellent perfume fragrance as well as an excellent perfume stability.
  • a-a bleaching system selected from i)-a perhydrate in amount of from 0.1 % to 60% by weight and combined with a bleach activator in amount of from 0.1 % to 60% by weight, ii)-a preformed peracid in amount of from 0.1 % to 60% by weight, and any mixtures thereof, wherein said perhydrate and/or said preformed peracid are coated; and
  • b-a perfume in amount from 0.05% to 2% by weight which comprises aroma chemicals selected from: primary and secondary alcohols, aliphatic aldehydes, hydrocinnamic aldehydes, esters excluding salicylates, unsaturated ketones and mixtures thereof, wherein the total sum of the weight of said aroma chemicals in the perfume is at least 30% by weight of the perfume.
  • aroma chemicals selected from: primary and secondary alcohols, aliphatic aldehydes, hydrocinnamic aldehydes, esters excluding salicylates, unsaturated ketones and mixtures thereof, wherein the total sum of the weight of said aroma chemicals in the perfume is at least 30% by weight of the perfume.
  • compositions according to the present invention herein contain bleaching agents or bleaching compositions containing a bleaching system, selected from a perhydrate in combination with one or more bleach activators and one or more preformed peracids wherein said perhydrate and/or said preformed peracid are coated.
  • bleaching agents will typically be at levels of from 0.1 % to 60%, more typically from 1 % to 30%, and more preferably from 5% to 20% of the bleaching composition, especially for fabric laundering.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known.
  • the bleaching agent, source of alkaline hydrogen peroxide in the wash liquor is an inorganic perhydrate bleach or a preformed peracid.
  • the perhydrate may be any of the alkali inorganic salts such as perborate monohydrate or tetrahydrate, percarbonate, perphosphate and persilicate salts, but is conventionally an alkali metal perborate or percarbonate.
  • Sodium percarbonate which is the preferred perhydrate, is an addition compound having a formula corresponding to 2Na2C ⁇ 3-3H2 ⁇ 2 and is available commercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequestrant such as EDTA, 1 -hydroxyethylene 1 ,1 -diphosphonic acid (HEDP) or an aminophosphonate, that is incorporated during the manufacture process.
  • a heavy metal sequestrant such as EDTA, 1 -hydroxyethylene 1 ,1 -diphosphonic acid (HEDP) or an aminophosphonate
  • Another category of bleaching agent that can be used in place of or in combination with the mixture of a coated perhydrate and a bleach activator encompasses the preformed peracid bleaching agents and salts thereof.
  • Suitable examples of this class of agents include (6-octylamino)-6-oxo-caproic acid, (6-nonylamino)- 6-oxo-caproic acid, (6-decylamino)-6-oxo-caproic acid, 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. Patent 4,483,781 , U.S. Patent 4,634,551 , EP 0,133,354, U.S. Patent 4,412,934 and EP 0,170,386.
  • Mixtures of bleaching agents can also be used.
  • An essential component of the invention is a coating for the bleaching agent which prevents the source of damage (hydrogen peroxide (H2O2) and/or peroxide anion ) from diffusion such that less than 5% of the peroxide source is diffused upon storage.
  • the present invention provides an enhancement in the perfume stability after a minimum of 24 hours storage of at least 1 panel grade, preferably 2 panel grades, after grading conducted by an expert panel.
  • the stability grade is given versus a laboratory prepared standard product (grade 10.0) on a 1 to 10 scale.
  • the bleach agent coating material can be selected from mixtures of alkali metal sulphate and carbonate, sodium silicate, borate and water-soluble surfactant.
  • the bleaching agent is preferably percarbonate.
  • the most preferred coating material comprises mixed salt of an alkali and/or alkaline earth metal sulphate and carbonate.
  • the weight ratio of the mixed salt coating material to the bleaching agent lies in the range from 1 : 200 to 1 : 4, more preferably from 1 : 99 to 1 : 9, and most preferably from 1 : 49 to 1 :19.
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2S ⁇ 4.n.Na2C ⁇ 3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1 .0 and most preferably n is from 0.2 to 0.5.
  • Another suitable coating material is sodium silicate of Si ⁇ 2 • Na2 ⁇ ratio from 1 .6 : 1 to 3.4 : 1 , preferably 2.8 : 1 , applied as an aqueous solution to give a level of from 2% to 10%, (normally from 3% to 5%) of silicate solids by weight of the bleaching agent.
  • Magnesium silicate can also be included in the coating.
  • Also useful as bleaching agent coating materials are sodium citrate, borate or water-soluble surfactants such as linear alkyl benzene sulphonate and alkyl ether sulphate.
  • a useful coating material for the percarbonate bleaching agent is a solid inorganic coating material consisting of a mixture of sodium carbonate and sodium chloride disclosed in EP-A-592969.
  • Preferred peroxygen bleaching agents selected from alkali metal perborates tetrahydrates and monohydrates and percarbonates, etc., are 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.
  • the amount of bleach activator will typically be from 0.1 % to 60%, more typically from 0.5% to 40% by weight of the bleaching composition.
  • activators preferably contain one or more N- or O-acyl groups and may be selected from a wide range of classes.
  • Various nonlimiting examples of activators are disclosed in U.S. Patent 4,91 5,854 and U.S. Patent 4,412,934.
  • the nonanoyloxybenzene sulfonate (NOBS), isononanoyloxybenzene sulfonate (ISONOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used.
  • a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion.
  • a preferred leaving group is phenyl sulfonate.
  • bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6- nonanamidocaproyDoxybenzenesulfonate, (6-decanamido- caproyDoxybenzene- sulfonate, and mixtures thereof as described in U.S. Patent 4,634,551 .
  • Another class of bleach activators comprises the benzoxazin-type activators disclosed in U.S. Patent 4,966,723.
  • a highly preferred activator of the benzoxazin-type is:
  • Still another class o ⁇ f pr Q eferred- ⁇ bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae: wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to 12 carbon atoms.
  • lactam activators include benzoyl caprolactam, octano ⁇ l caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octano ⁇ l valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5- trimethylhexanoyl valerolactam and mixtures thereof. See also U.S.
  • Patent 4,545,784 which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
  • Another class of preferred bleach activators include the cationic bleach activators, derived from the valerolactam and acyl caprolactam compounds, of formula:
  • the bleach activator component is in a coated form.
  • the coating material is selected from a mixture of alkali metal C8-C22 fatty acid salts in admixture with the corresponding fatty acids (disclosed in GB 1 50731 2), a coating of C14-C18 fatty acid mixtures (disclosed in GB 1381 121 ), a mixture of C *
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can optionally be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminium phthalocyanines. See U.S. Patent 4,033,718. If used, bleaching compositions will typically contain from 0.025% to 1 .25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • the bleaching compounds can be catalysed 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. Pat. 5,246,621 , U.S. Pat. 5,244,594; U.S. Pat. 5,194,41 6; U.S. Pat. 5,1 14,606; and EP 549,271 A1 , 549,272A1 , 544,440A2, and 544,490A1 ; Preferred examples of these catalysts include Mn * V2(u-0)3(1 ,4,7-trimethyl-1 ,4,7- triazacyclononane)2(PF6)2.
  • the other essential component of the invention is a perfume composition comprising aroma chemicals selected from primary and secondary alcohols, aliphatic aldehydes, hydrocinnamic aldehydes, esters excluding salicylates, unsaturated ketones and mixtures thereof.
  • Primary alcohols suitable for the purpose of the invention are 3,7-dimethyl-6-octen-1 -ol, 3,7-dimethyl-2,6-octadien-1 -ol, phenyl ethyl alcohol, 1 -pentanol, 3-methyl-5-phenyl and cyclohexyl ethyl alcohol.
  • Preferred primary alcohols are 3,7- dimethyl-6-octen-1 -ol, 3,7-dimethyl-2,6-octadien-1 -ol and phenyl ethyl alcohol.
  • Secondary alcohols suitable for use in the perfume composition are cyclohexanol, 2-tertiary butyl, 4-methyl-3-decen-5-ol, cyclohexanol,4-tertiary butyl and 4-iso propyl cyclohexanol.
  • Preferred secondary alcohols are cyclohexanol ,2-tertiary butyl and 4-methyl-3-decen-5-ol.
  • When used such alcohols compounds will be at a level of from 1 % to 50%, preferably at a level of from 20% to 45% and more preferably from 25% to 35% by weight of the perfume composition.
  • Aliphatic aldehydes suitable for the purpose of the invention are octanal, nonanal, decanal, undecanal, dodecanal, 10- undecenal, 2-meth ⁇ l undecanal and 2-methyl decanal.
  • Hydrocinnamic aldehydes suitable for the purpose of the invention are 2-methyl-3-(4-tertiary butyl phenyl) propanal and 2- methyl-3-(4-iso propyl phenyl) propanal.
  • When used such aliphatic and hydrocinnamic aldehydes will be at a level of up to 30%, preferably at a level of up to 20% and more preferably up to 10% by weight of the perfume composition.
  • Esters, excluding salicylates, suitable for the purpose of the invention are benzyl acetate, benzyl propionate, phenyl ethyl acetate, citronellyl acetate, geranyl acetate, 2-methyl-3-phenyl- propan-2-yl acetate, 4-tertiary butyl cyclohexyl acetate, 2-tertiary butyl cyclohexyl acetate, hexahydro-4,7-methano-inden-5-yl acetate, hexahydro-4,7-methano-inden-6-yl acetate, hexahydro- 4,7-methano-inden-5-yl propionate, hexahydro-4,7-methano- inden-6-yl propionate and methyl benzoate.
  • esters excluding salicylates
  • Preferred esters are 2-methyl-3-phenyl-propan-2-yl acetate, 2-tertiary butyl cyclohexyl acetate, hexahydro-4,7-methano- inden-5-yl acetate, hexahydro-4,7-methano-inden-6-yl acetate, hexahydro-4,7-methano-inden-5-yl propionate, hexahydro-4,7- methano-inden-6-yl propinate and methyl benzoate.
  • esters excluding salicylates will be at a level of from 5% to 50%, preferably at a level of from 10% to 40% and more preferably from 25% to 35% by weight of the perfume composition.
  • Unsaturated ketones suitable for the purpose of the invention are 7-acetyl 1 ,2,3,4,5,6,7,8-octanhydro 1 ,1 ,6,7 tetra methyl naphtalene, 3-buten-2-one 3-methyl-4-(2,6,6, trimethyl-2- cyclohexen-1 -yl), 3-buten-2-one 4-(2,6,6-trimethyl-1 -cyclohexen- 1 -yl), 3-buten-2-one 4-(2,6,6-trimethyl-2-cyclohexen-1 -yl) and ketone cedr-8-enyl methyl.
  • Such unsaturated ketones When used such unsaturated ketones will be at a level of from up to 30%, preferably at a level of up to 25% by weight of the perfume composition.
  • the total sum of the weight of said aroma chemicals, described herein before, present in the perfume composition is at least 30%, preferably at least 50% and more preferably at least 80% by weight of the perfume.
  • the perfume composition is incorporated in the bleaching composition of the invention at a level of from 0.05% to 2% by weight, preferably from 0.01 % to 1 % of the bleaching composition.
  • the bleaching composition may comprise one or more iron and/or manganese chelating agents which further enhances the storage stability of the perfume.
  • Chelating A ⁇ ents - Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. 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 carbox ⁇ lates useful as optional chelating agents include ethylenediaminetetracetates, N- hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraamine- hexacetates, diethylenetriaminepentaacetates, and ethanoldi- glycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Preferred biodegradable non-phosphorus chelants for use herein are ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, ethylenediamine- N,N'-diglutamate (EDDG) and 2-hydroxypropylene-diamine-N,N'- disuccinate (HPDDS) compounds.
  • EDDS ethylenediamine disuccinate
  • EDDG ethylenediamine- N,N'-diglutamate
  • HPDDS 2-hydroxypropylene-diamine-N,N'- disuccinate
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) available under the trademark DEQUEST from Monsanto. Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy-3,5- disulfobenzene.
  • these chelating agents will generally comprise from 0.1 % to 10% by weight of the bleaching compositions herein. More preferably, if utilized, the chelating agents will comprise from 0.1 % to 3.0% by weight of such compositions.
  • the bleaching compositions of the invention may also contain additional detergent components.
  • additional detergent components The precise nature of these additional components and levels of incorporation thereof will depend on the physical form of the composition, and the nature of the cleaning operation for which it is to be used.
  • the compositions of the invention may, for example, be formulated as hand and machine laundry detergent compositions, including laundry additive compositions and compositions suitable for use in the pretreatment of stained fabrics and machine dishwashing compositions.
  • compositions suitable for use in a machine washing method eg: machine laundry and machine dishwashing methods
  • the compositions of the invention preferably contain one or more additional detersive components.
  • bleaching composition comprises additional detergent components, as described herein after, the terms 'bleaching composition' and 'detergent composition' will be used herein after as synonymous.
  • Nonlimiting examples of surfactants useful herein typically at levels from 1 % to 55%, by weight, include the conventional C-] 1 -C-
  • AE X S
  • the conventional nonionic and amphoteric surfactants such as the C12-CI 8 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and CQ- C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy /propoxy), C12-C18 betaines and sulfobetaines ("sultaines"), C10-CI 8 amine oxides, and the like, can also be included in the overall compositions.
  • the C10-CI 8 N" a *M polyhydroxy fatty acid amides can also be used. Typical examples include the Ci 2-C18 N-methylglucamides. See WO 9,206,1 54.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N (3- methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C12- C * i 8 glucamides can be used for low sudsing.
  • C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C1 6 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
  • compositions herein can optionally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., colorants, dyes, etc.).
  • other detergent adjunct materials e.g., colorants, dyes, etc.
  • the following are illustrative examples of such adjunct materials.
  • Builders - 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 paniculate soils.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least 1 % builder. Granular formulations typically comprise from 10% to 80%, more typically from 15% to 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • Inorganic or phosphate-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta- phosphates).
  • Non-phosphate builders may also be used. These can include, but are not restricted to phytic acid, silicates, alkali metal carbonates (including bicarbonates and sesquicarbonates), sulphates. aluminosilicates, monomeric polycarboxylates, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two carbon atoms, organic phosphonates and aminoalkylene poly (alkylene phosphonates).
  • compositions herein also function 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 so called 'amorphous' alkali metal silicates, particularly those having a Si ⁇ 2-Na2 ⁇ ratio in the range 1 .6:1 to 3.2:1 and crystalline layered silicates, such as the layered sodium silicates described in U.S. Patent 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-Na2Si2 ⁇ 5 morphology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 ⁇ + 1 -yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1 .9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-1 1 , as the alpha, beta and gamma forms.
  • delta-Na2Si2 ⁇ 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilising agent for oxygen bleaches, and as a component of suds control systems.
  • Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
  • Nai 2I(AI02)12(Si ⁇ 2)l 2l-xH2 ⁇ wherein x is from 20 to 30, especially 27.
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of 0.1 -10 microns in diameter.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • poly- carboxylate 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 neutralised 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 polycarboxy- lates, including ox ⁇ disuccinate, as disclosed in U.S. Patent 3,128,287 and U.S. Patent 3,635,830. See also "TMS/TDS" builders of U.S. Patent 4,663,071 .
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • ether hydroxypolycarboxylates include the ether hydroxypolycarboxylates, copoiymers of maleic anhydride with ethylene or vinyl methyl ether, or acrylic acid, 1 , 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxy- disuccinic acid, polymaleic acid, benzene 1 ,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid,
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristyisuccinate, 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.
  • Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226 and in U.S. Patent 3,308,067. See also U.S. Pat. 3,723,322.
  • Fatty acids e.g., C1 2-C18 monocarboxylic acids
  • the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • the various alkali metal phosphates such as the well- known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane-1 -hydroxy-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.
  • Enzvmes - Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride- based stains, for example, and for the prevention of fugitive dye transfer, and for fabric restoration.
  • the enzymes to be incorporated include proteases, amylases, upases, cellulases, and peroxidases, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability and stability versus active detergents and builders. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • Enzymes are normally incorporated at levels sufficient to provide up to 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from 0.001 % to 5%, preferably 0.01 %-1 % by weight of a commercial enzyme preparation.
  • proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in GB 1 ,243,784 of Novo.
  • proteases suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands).
  • Other proteases include Protease A (see EP 130,756) and Protease B (see EP257189).
  • Amylases include, for example, ⁇ -amylases described in GB 1 ,296,839 (Novo), RAPIDASE, Intemational Bio-Synthetics, Inc. and TERMAMYL, Novo Industries. Fungamyl (Novo) is especially useful.
  • the cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM 1800 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. ENDO A, CAREZYME both from Novo Industries A/S are especially useful.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1 ,372,034. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P.” Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • the LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use herein.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.
  • a wide range of enzyme materials and means for their incorporation into synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139. Enzymes are further disclosed in U.S. Patent 4,101 ,457 and in U.S. Patent 4,507,219. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. Patent 4,261 ,868. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S. Patent 3,600,319 and EP 0 199 405. Enzyme stabilisation systems are also described, for example, in U.S. Patent 3,519,570.
  • Enzvme Stabilisers The enzymes employed herein are stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. (Calcium ions are generally somewhat more effective than magnesium ions and are preferred herein if only one type of cation is being used.) Additional stability can be provided by the presence of various other art- disclosed stabilisers, especially borate species: see Severson, U.S. 4,537,706. Typical detergents, especially liquids, will comprise from 1 to 30, preferably from 2 to 20, more preferably from 5 to 15, and most preferably from 8 to 12, millimoles of calcium ion per liter of finished composition.
  • the level of calcium or magnesium ions should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, fatty acids, etc., in the composition.
  • Any water-soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the corresponding magnesium salts.
  • a small amount of calcium ion generally from 0.05 to 0.4 millimoles per liter, is often also present in the composition due to calcium in the enzyme slurry and formula water.
  • the formulation may include a sufficient quantity of a water-soluble calcium ion source to provide such amounts in the laundry liquor. In the alternative, natural water hardness may suffice.
  • compositions herein will typically comprise from 0.05% to 2% by weight of a water-soluble source of calcium or magnesium ions, or both.
  • the amount can vary, of course, with the amount and type of enzyme employed in the composition.
  • compositions herein may also optionally, but preferably, contain various additional stabilizers, especially borate-type stabilizers.
  • additional stabilizers especially borate-type stabilizers.
  • such stabilizers will be used at levels in the compositions from 0.25% to 10%, preferably from 0.5% to 5%, more preferably from 0.75% to 3%, by weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid).
  • Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable.
  • Substituted boric acids e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid
  • compositions according to the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties.
  • Granular detergent compositions which contain these compounds typically contain from 0.01 % to 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain 0.01 % to 5%.
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethyienepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1 , 1986.
  • Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in EP 1 1 1 ,965.
  • Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in EP 1 1 1 ,984; the zwitterionic polymers disclosed in EP 1 12,592; and the amine oxides disclosed in U.S. Patent 4,548,744.
  • Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein.
  • Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
  • Polymeric Soil Release Aoent Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes 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 characterized by poly(vinyl ester) hydrophobe segments include graft copoiymers of poly(vinyl ester), e.g., C ⁇ -CQ vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones (see EP 0 219 048).
  • Commercially available soil release agents of this kind include the SO K ALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from 25,000 to 55,000. See U.S. Patent 3,959,230 to Hays and U.S. Patent 3,893,929.
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10- 15% by weight of ethylene terephthalate units together with 90- 80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene giycol of average molecular weight 300- 5,000.
  • this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857.
  • Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • These soil release agents are described fully in U.S. Patent 4,968,451 .
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,71 1 ,730, the anionic end-capped oligomeric esters of U.S. Patent 4,721 ,580 and the block polyester oligomeric compounds of U.S. Patent 4,702,857.
  • Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
  • soil release agents will generally comprise from 0.01 % to 10.0%, by weight, of the compositions herein, typically from 0.1 % to 5%, preferably from 0.2% to 3.0%.
  • Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1 ,2-propylene units.
  • the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps.
  • a particularly preferred soil release agent of this type comprises one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1 ,2-propyleneoxy units in a ratio of from 1 .7 to 1 .8, and two end-cap units of sodium 2-(2-hydroxyethox ⁇ )-ethanesulfonate.
  • Said soil release agent also comprises from 0.5% to 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • a crystalline-reducing stabilizer preferably selected from xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • compositions according to the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
  • dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copoiymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from 0.01 % to 10% by weight of the composition, preferably from 0.01 % to 5%, and more preferably from 0.05% to 2%.
  • Preferred polyamine N- oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the N-0 group can be represented by the following general structures:
  • R-] , R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1 ; and the nitrogen of the N-0 group can be attached or form part of any of the aforementioned groups.
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copoiymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1 :1 ,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1 ,000,000; more preferred 1 ,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
  • poly(4-vinylpyridine-N-oxide) which as an average molecular weight of 50,000 and an amine to amine N- oxide ratio of 1 :4.
  • Copoiymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferred for use herein.
  • the PVPVI has an average molecular weight range from 5,000 to 1 ,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis. Vol 1 13.
  • the PVPVI copoiymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 :1 to 0.2:1 , more preferably from 0.8:1 to 0.3:1 , most preferably from 0.6:1 to 0.4:1 .
  • These copoiymers can be either linear or branched.
  • compositions also may employ a poly- vinylpyrrolidone (“PVP”) having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to 200,000, and more preferably from 5,000 to 50,000.
  • PVP's are known to persons skilled in the detergent field; see, for example, EP-A- 262,897 and EP-A-256,696.
  • Compositions containing PVP can also contain polyethylene giycol (“PEG”) having an average molecular weight from 500 to 100,000, preferably from 1 ,000 to 10,000.
  • PEG polyethylene giycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from 2:1 to 50:1 , and more preferably from 3:1 to 10:1 .
  • the detergent compositions herein may 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 0.01 % to 1 % by weight of such optical brighteners.
  • hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein R-j is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N- 2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]- 2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the compositions herein.
  • the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N- methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • the brightener is 4,4'-bis[(4- anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • optical brightener species which may be used in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described.
  • selected polymeric materials e.g., PVNO and/or PVPVI
  • selected optical brighteners e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS- GX
  • Tinopal UNPA-GX Tinopal UNPA-GX
  • Tinopal 5BM-GX Tinopal 5BM-GX
  • Tinopal AMS- GX Tinopal AMS- GX
  • the extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient".
  • the exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor.
  • Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
  • other, conventional optical brightener types of compounds can optionally be used in the present compositions to provide conventional fabric "brightness" benefits, rather than a true dye transfer inhibiting effect. Such usage is conventional and well-known to detergent formulations.
  • optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from 0.05% to 1 .2%, by weight, into the detergent compositions herein.
  • Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6- membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
  • optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artie White CC and Artie White CWD, available from Hilton-Davis, located in Italy; the 2-(4-stryl- phenyl)-2H-napthol[1 ,2-d]triazoles; 4,4'-bis- (1 ,2,3-triazol-2-yl)- stil- benes; 4,4'-bis(stryl)bisphenyls; and the aminocoumarins.
  • these brighteners include 4-methyl-7- diethyl- amino coumarin; 1 ,2-bis(-venzimidazol-2-yl)ethylene; 1 ,3- diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl- napth-[1 ,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [1 ,2- dltriazole. See also U.S. Patent 3,646,01 5.
  • Anionic brighteners are preferred herein.
  • Suds Su p pressors - Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" and in front-loading European-style washing machines.
  • suds suppressors A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
  • One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347.
  • the monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • the bleaching compositions herein may also contain non- surfactant suds suppressors.
  • non- surfactant suds suppressors include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C*
  • suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of -40°C and 50°C and a minimum boiling point not less than 1 10°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below 100°C.
  • the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779.
  • the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from 12 to 70 carbon atoms.
  • the term "paraffin,” as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Non-surfactant suds suppressors comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethyl- siloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
  • Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779 and EP 354016.
  • silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526.
  • Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672 and in U.S. Patent 4,652,392.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
  • polydimethylsiloxane fluid having a viscosity of from 20 cs. to 1 ,500 cs. at 25°C;
  • the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene giycol copoiymers or mixtures thereof (preferred), or polypropylene giycol.
  • the primary silicone suds suppressor is branched/crosslinked and preferably not linear.
  • typical liquid laundry detergent compositions with controlled suds will optionally comprise from 0.001 to 1 , preferably from 0.01 to 0.7, most preferably from 0.05 to 0.5, weight % of said silicone suds suppressor, which comprises (1 ) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin- producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene giycol or a copolymer of polyethylene-polypropylene giycol having a solubility in water at room temperature of more than 2 weight %; and without polypropylene giycol.
  • a primary antifoam agent which is a mixture of (a)
  • the silicone suds suppressor herein preferably comprises polyethylene giycol and a copolymer of polyethylene gl ⁇ col/polypropylene giycol, all having an average molecular weight of less than 1 ,000, preferably between 100 and 800.
  • the polyethylene giycol and polyethylene/polypropylene copoiymers herein have a solubility in water at room temperature of more than 2 weight %, preferably more than 5 weight %.
  • the preferred solvent herein is polyethylene giycol having an average molecular weight of less than 1 ,000, more preferably between 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene giycol, preferably PPG 200/PEG 300.
  • Preferred is a weight ratio of between 1 :1 and 1 :10, most preferably between 1 :3 and 1 :6, of polyethylene giycol :copolymer of polyethylene-polypropylene giycol.
  • the preferred silicone suds suppressors used herein do not contain polypropylene giycol, particularly of 4,000 molecular weight. They also preferably do not contain block copoiymers of ethylene oxide and propylene oxide, like PLURONIC L101 .
  • suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,1 18 and EP 150,872.
  • the secondary alcohols include the C ⁇ -C*i 6 alkyl alcohols having a C1 -C16 chain.
  • a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
  • Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
  • Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1 :5 to 5:1 .
  • suds should not form to the extent that they overflow the washing machine.
  • Suds suppressors when utilized, are preferably present in a "suds suppressing amount.
  • Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
  • the compositions herein will generally comprise from 0% to 5% of suds suppressor. When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to 5%, by weight, of the detergent composition.
  • fatty monocarboxylate suds suppressor is utilized.
  • Silicone suds suppressors are typically utilized in amounts up to 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
  • from 0.01 % to 1 % of silicone suds suppressor is used, more preferably from 0.25% to 0.5%.
  • these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
  • Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from 0.1 % to 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically utilized in amounts ranging from 0.01 % to 5.0%, although higher levels can be used. The alcohol suds suppressors are typically used at 0.2% -3% by weight of the finished compositions.
  • Fabric Softeners Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, as well as other softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning.
  • Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416 and U.S. Patent 4,291 ,071 .
  • compositions herein A wide variety of other functional ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc.
  • suds boosters such as the C10-CI 6 alkanolamides can be incorporated into the compositions, typically at 1 %-10% levels.
  • the C ⁇ o _ Cl 4 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • soluble magnesium salts such as MgCl2, MgS04, and the like, can be added at levels of, typically, 0.1 %-2%, to provide additional suds and to enhance grease removal performance.
  • detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
  • the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C*
  • the enzyme/surfactant solution is 2.5 X the weight of silica.
  • the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used).
  • silicone oil dispersion is emulsified or otherwise added to the final detergent matrix.
  • ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and 1 1 , preferably between 7.5 and 10.5. Laundry products are typically at pH 9-1 1 . 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 bulk density of granular bleaching compositions is typically at least 450 g/litre, more usually at least 600 g/litre and more preferably from 650 g/litre to 1000 g/litre.
  • Silicate Amo hous sodium silicate (Si ⁇ 2:Na2 ⁇ ratio normally follows)
  • Citric acid Anhydrous Citric Acid
  • Percarbonate Anhydrous sodium percarbonate bleach of empirical formula 2Na2C ⁇ 3.3H2 ⁇ 2 coated with a mixed salt of formula Na2S ⁇ 4.n.Na2C ⁇ 3 where n is 0.29 and where the weight ratio of percarbonate to mixed salt is 39:1
  • DETPMP Diethylenetriamine penta (Methylene phosphonic acid) marketed by Monsanto under the Trade name Dequest 2060.
  • Perfume samples are at least 24 hours old. The samples are coded to preserve anonymity and the results are recorded on individual sheets. The panel is held in an odour-free room. The detergent is poured into a clean plastic cup and covered immediately with a plastic lid. 1 % solutions are then made by adding hot water (50°C) to a beaker along with the product. This is covered immediately with a watch glass.
  • Panel odour grading is carried out by a minimum of three expert judges. In this instance, expert is defined as a person having at least 6 months training with demonstrated evidence of olfactive sensitivity. All grades for this work were given versus a laboratory prepared standard product (grade 10.0) on a 1 -10 scale. The individual grades are only averaged when the highest and lowest grades do not differ by more than 2 panel grades. Where differences are greater, that product is repanelled as soon as possible on a subsequent panel.
  • compositions A, B, C, D are in accordance with the present invention, wherein the perfume is selected from one of those defined in Example 1 and sprayed onto the finished detergent product.
  • compositions in accordance with the invention were all seen having an enhanced perfume stability of at least 1 grade.

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

Abstract

L'invention concerne une composition de blanchiment parfumée contenant: a-un système de blanchiment sélectionné dans i)-un perhydrate, à raison de 0,1 % à 60 % en poids et combiné à un activateur de blanchiment, à raison de 0,1 % à 60 % en poids, ii)-un peracide préformé, à raison de 0,1 % à 60 % en poids, et des mélanges de ceux-ci. Ce perhydrate et/ou ce peracide préformés sont enrobés; et b-un parfum, à raison de 0,05 % à 2 % en poids, comprenant des produits chimiques aromatiques sélectionnés parmi: des alcools primaires et secondaires, des aldéhydes aliphatiques, des aldéhydes hydrocinnamiques, des esters à l'exclusion des salicylates, des cétones insaturées et des mélanges de ceux-ci, la somme totale en poids de ces produits chimiques aromatiques représentant au moins 30 % en poids du parfum. Ladite composition de blanchiment parfumée comprend également de préférence, un chélateur qui augmente encore la durée de conservation du parfum.
EP95943787A 1994-12-21 1995-12-08 Compositions de blanchiment parfumees Ceased EP0808358A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9425876.1A GB9425876D0 (en) 1994-12-21 1994-12-21 Perfumed bleaching compositions
GB9425876 1994-12-21
PCT/US1995/016249 WO1996019560A1 (fr) 1994-12-21 1995-12-08 Compositions de blanchiment parfumees

Publications (2)

Publication Number Publication Date
EP0808358A1 true EP0808358A1 (fr) 1997-11-26
EP0808358A4 EP0808358A4 (fr) 1999-08-11

Family

ID=10766339

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95943787A Ceased EP0808358A4 (fr) 1994-12-21 1995-12-08 Compositions de blanchiment parfumees

Country Status (8)

Country Link
EP (1) EP0808358A4 (fr)
JP (1) JPH10512307A (fr)
CN (1) CN1175278A (fr)
AR (1) AR000422A1 (fr)
BR (1) BR9510309A (fr)
CA (1) CA2206458A1 (fr)
GB (1) GB9425876D0 (fr)
WO (1) WO1996019560A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69838130T2 (de) 1998-06-15 2008-04-10 The Procter & Gamble Company, Cincinnati Riechstoffzusammensetzungen
JP4112310B2 (ja) * 2002-08-14 2008-07-02 花王株式会社 液体洗浄剤組成物
EP1556522A1 (fr) 2002-10-21 2005-07-27 Basf Aktiengesellschaft Procede permettant d'eliminer les substances de corne de la peau des animaux
DE102005054565A1 (de) * 2005-11-14 2007-05-16 Henkel Kgaa Oxidationsmittel enthaltende,wohlriechende Verbrauchsprodukte
US20070123440A1 (en) * 2005-11-28 2007-05-31 Loughnane Brian J Stable odorant systems
EP2270124A1 (fr) * 2009-06-30 2011-01-05 The Procter & Gamble Company Compositions de blanchiment comportant un système de livraison de parfum
JP6184830B2 (ja) * 2013-06-14 2017-08-23 花王株式会社 漂白洗浄剤組成物

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5219549A (en) * 1990-05-25 1993-06-15 Mitsubishi Gas Chemical Company, Inc. Bleaching detergent composition
EP0657527A1 (fr) * 1993-12-10 1995-06-14 The Procter & Gamble Company Stabilisation de substances sensibles à l'oxidation dans de compositions détergentes contenant un percarbonate

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3762630D1 (de) * 1986-05-28 1990-06-13 Akzo Nv Verfahren zur herstellung von diperoxidodecandionsaeure enthaltenden agglomeraten und die verwendung derselben in bleichmitteln.
GB9021761D0 (en) * 1990-10-06 1990-11-21 Procter & Gamble Detergent compositions
US5411673A (en) * 1991-02-06 1995-05-02 The Procter & Gamble Company Peroxyacid bleach precursor compositions
GB9126296D0 (en) * 1991-12-11 1992-02-12 Unilever Plc Sodium percarbonate
US5332518A (en) * 1992-04-23 1994-07-26 Kao Corporation Stable slurry-coated sodium percarbonate, process for producing the same and bleach detergent composition containing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5219549A (en) * 1990-05-25 1993-06-15 Mitsubishi Gas Chemical Company, Inc. Bleaching detergent composition
EP0657527A1 (fr) * 1993-12-10 1995-06-14 The Procter & Gamble Company Stabilisation de substances sensibles à l'oxidation dans de compositions détergentes contenant un percarbonate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9619560A1 *

Also Published As

Publication number Publication date
WO1996019560A1 (fr) 1996-06-27
AR000422A1 (es) 1997-06-18
CA2206458A1 (fr) 1996-06-27
EP0808358A4 (fr) 1999-08-11
CN1175278A (zh) 1998-03-04
JPH10512307A (ja) 1998-11-24
BR9510309A (pt) 1997-11-11
MX9704670A (es) 1997-09-30
GB9425876D0 (en) 1995-02-22

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