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WO2001000775A1 - Benzolactones comme activateurs de blanchiment - Google Patents

Benzolactones comme activateurs de blanchiment Download PDF

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Publication number
WO2001000775A1
WO2001000775A1 PCT/US2000/017716 US0017716W WO0100775A1 WO 2001000775 A1 WO2001000775 A1 WO 2001000775A1 US 0017716 W US0017716 W US 0017716W WO 0100775 A1 WO0100775 A1 WO 0100775A1
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WO
WIPO (PCT)
Prior art keywords
bleaching
composition according
salt
alkyl
aryl
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
PCT/US2000/017716
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English (en)
Inventor
Michael Sidney Austerberry
Stephen David Carter
Natascha Elise Morison
Roger Bolton
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.)
US Borax Inc
Original Assignee
US Borax Inc
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 US Borax Inc filed Critical US Borax Inc
Priority to AU57726/00A priority Critical patent/AU5772600A/en
Publication of WO2001000775A1 publication Critical patent/WO2001000775A1/fr
Anticipated expiration legal-status Critical
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
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3927—Quarternary ammonium 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
    • C11D3/39—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
    • C11D3/391—Oxygen-containing compounds

Definitions

  • This invention relates to novel organic bleach activators for bleaching compositions for use in laundry detergent and other cleaning applications.
  • Detergents designed for fabric cleaning applications frequently contain bleaching agents.
  • the purpose of these is primarily to oxidise chemically, and consequently remove, certain types of bleachable soils and stains but also to kill bacteria, which can otherwise lead to the spread of disease and be detrimental to human and animal health.
  • bleachable stains such as tea, coffee and fruit juices
  • an oxygen containing bleaching component such as hydrogen peroxide
  • the preferred sources of hydrogen peroxide are inorganic persalts such as sodium perborate or sodium percarbonate .
  • These bleaches work well at temperatures above 60°C, but to boost their overall effectiveness at today's relatively low washing temperatures (40-60°C) , they are most commonly employed in conjunction with bleach activator compounds at a typical level of 3-6% in the detergent.
  • An example of a bleach activator is tetraacetylethylenediamine (TAED) .
  • the bleach activator reacts stoichiometrically, with the hydrogen peroxide released from the persalt by in- ⁇ i tu perhydrolysis, to yield a stronger oxidising agent; an organic peroxyacid.
  • These stronger oxidants such as peracetic acid from TAED, are better able to bleach stains than hydrogen peroxide and also have superior biocidal activity.
  • washing temperatures continue to decline as a result of the demand for greater energy efficiency, even those presently used activated bleach systems are less attractive since their performance falls off sharply below 40°C.
  • Another drawback of these types of activators is their low rate of dissolution at low temperatures which may reduce their effectiveness and may also lead to localised fabric or dye damage.
  • phthalic anhydride as disclosed in WO 96/14383 produces perbenzoic acid
  • activators of the benzoxazin type as disclosed in EP-A-332,294 produce derivatives of perbenzoic acid.
  • these have not been commercialised which is attributable to their propensity to cause unacceptable patchy damage.
  • interfacially active bleach activators which react with persalts to produce peracids which are in turn interfacially active, has improved the performance of oxygen bleaches under certain conditions.
  • the technology has meant that lower concentrations of the bleach system in the wash liquor are needed to give equivalent performance since the bleach is effectively targeted to the stains.
  • Sodium nonanoyloxybenzene sulphonate (NOBS) as described in US-A-4 , 12, 934 is an example of this type of activator.
  • NOBS Sodium nonanoyloxybenzene sulphonate
  • this disclosure has resulted in the successful introduction of sodium perborate bleach-based detergents into the United States, where lower detergent concentrations are typically employed, and some improvement in detergent performance has been shown at temperatures below 40°C, further improvements are desired.
  • the interfacial activity of the peroxyacid has lead to reports of fabric damage.
  • further additives such as free radical scavengers as described for example, in EP-A-283 , 252.
  • Another approach considered has been the use of pre-formed peracids as bleaches.
  • Examples of these peracids include diperoxydodecanedioic acid (DPDDA) and e-N,N-phthaloylaminoperoxycarboxylic acids (PAPs) .
  • DPDDA diperoxydodecanedioic acid
  • PAPs e-N,N-phthaloylaminoperoxycarboxylic acids
  • these, and other examples of pre-formed acids can lead to better bleaching performance than TAED-activated sodium perborate
  • the peracids generally need stabilising coatings as described for example in US-A-4 , 100 , 095. Their use may also lead to pinhole damage to dyed fabrics and they are also out of favour from a cost point of view.
  • Yet another approach taken within the detergents industry has been the use of bleach catalysts which work with oxygen bleaches such as perborate or sodium percarbonate.
  • transition metal complexes usually transition metal complexes; the most commonly used metals being manganese, iron and cobalt.
  • the advantage of these over organic activators is that only minute amounts are required, which brings obvious economic advantages.
  • EP-A-458,397 and EP-A-458,398 describe manganese-based catalysts, which give considerable enhancement to persalt bleaching of stains on fabrics during washing at temperatures below 40°C. Unfortunately, they are also prone to causing dye and fabric damage.
  • Manganese ions and those of several other first row transition metals (iron, cobalt and copper) are known to catalyse the production of highly reactive radical species which can lead to the degradation of cellulosic materials.
  • Manganese (IV) oxide is an example of a staining oxide that can form in alkaline wash liquors when inadequately ligand-stabilised manganese ions (e.g. Mn 2+ ) are employed as catalysts for oxygen bleaches. Catalysts of this type can also promote the wasteful decomposition of hydrogen peroxide and the undesired reaction between hydrogen peroxide and peracids .
  • Oxidative degradation of the organic ligands in many transition metal complexes is a significant problem when these are used as oxidation or bleach catalysts. The result is that the catalyst can rapidly loose its activity. Synthetic metalloporphyrin catalysts can suffer in this respect.
  • EP-A-384,503 describes modifications made to metalloporphyrir catalysts, intended for use as bleach catalysts, which are intended to make them more stable against oxidation by the oxidant (e.g. peroxyacid) .
  • Bleach activators are required which fulfil the following requirements, that is they exhibit (I) significantly improved bleach activity below 40°C, (II) fast dispersing rate, (III) cost effectiveness, (IV) ease of processability into detergent formulations, (V) good storage stability and compatability with other detergent ingredients, (VI) a non-toxic nature, and (VII) insignificant dye and fabric damage.
  • the basic organic frameworks of the bleach activators used according to the invention are five, six or seven-membered benzolactones.
  • a bleaching composition comprising: (i) a bleaching agent, and
  • ring A represents a fused benzene ring or a fused aromatic heterocyclic ring which is unsubstituted or substituted by one or more groups chosen from hydroxy, alkoxy, alkyl, alkaryl, aryl, aralkyl, amino, alkylamino, a -N + R 3 or -(CH 2 ) n -N + R 3 (wherein each R represents alkyl or aryl and n is an integer of 1 to 6) salt, -S0 3 H or a salt thereof, or a carbonyl-containing group such as -COOH or a salt thereof or an aldehyde or ketone group; and each of R 5 to R 10 , which may be the same or different, represents H, hydroxy, alkoxy, alkyl, alkaryl, aryl, aralkyl, amino, alkylamino, a -N + R 3 (wherein R is as defined above) salt,
  • a detergent or cleaning composition containing a bleaching composition according to the present invention.
  • a method of laundering fabric in which there is used a detergent or cleaning composition according to the invention.
  • the bleach activator used is one or more benzolactones of the general formulae :
  • each of R 1 to R 4 which may be the same or different, represents H, hydroxy, alkoxy, alkyl, alkaryl, aryl, aralkyl, amino, alkylamino, a -ISTR J or - (CH 2 ) r ⁇ -N + R 3 (wherein R is as defined above) salt, -S0 3 H or a salt thereof, or a carbonyl-containing group such as -COOH or a salt thereof or an aldehyde or ketone group; and R 5 to R 10 are as defined above.
  • alkyl groups and moieties within formulae (1), (2), (3), (la), (2a) and (3a) contain 1 to 4 carbon atoms and the aryl groups and moieties are phenyl .
  • the salts of N + R 3 and (CH 2 ) n -N + R 3 are preferably halides, and n is suitably 1.
  • the preferred cations are alkali and alkaline earth metal ions, ammonium ions, or tetraalkyammonium ions (wherein the alkyl groups contain 1 to 4 carbon atoms) .
  • bleach activator a benzolactone of formula (la) , (2a) or (3a) in which each of R 1 to R 4 , which may be the same or different, represents H, alkyl, aryl or -S0 3 H or a salt thereof wherein the cation is selected from alkali, alkaline earth, ammonium or tetraalkylammonium wherein the alkyl group contains 1-4 carbon atoms; and each of R 5 to R 10 , which may be the same or different, represents H or alkyl.
  • bleaching compositions according to the present invention have good bleaching performance, particularly at low temperatures. Furthermore they fulfil requirements (I) to (VII) above.
  • Preferred bleach activators are selected from benzolactones of formula (la), for example 3 , 3-dimethyl- benzofuran-2 (3H) -one ; benzolactones of formula (2a), for example 3 , 4-dihydro-4-methyl-l-benzopyran-2 (2H) -one, 3 , 3-dimethyl-3 , 4-dihydro-l-benzopyran-2 (2H) -one, and potassium-3, 4-dihydro-l-benzopyran-2 (2H) -one-6-sulphonate, 3 , 4-dihydro-l-benzopyran-2 , 3-dione; from the benzolactones of formula (3a), for example 4 , 5-dihydro-l-benzoxepin-2 (3H) - one; and may be exemplified by the compound 3 , 4-dihydr
  • 3 , 4 -Dihydrocoumarin may be prepared by the hydrogenation of coumarin by methods known to those skilled in the art. It is also a natural product that can be extracted from, for example, tonka beans. The other benzolactones can also be prepared using methods known to those skilled in the art. 3 , 4 -Dihydrocoumarin, as with other lactones for use according to the invention, is believed to perhydrolyse to form a peroxyacid which bleaches stains on fabrics and maintains the colour of fabrics by bleaching solubilised fugitive dyes before they re-deposit onto a fabric surface. It is thought that the peroxyacid formed by perhydrolysis contains a propylphenyl chain which suggests hydrotropic characteristics. Yet another advantage of this type of activator is that after utilisation of its available oxygen, the residual component under certain conditions can revert to the original activator compound and therefore could be considered as an oxygen transfer system.
  • 3 , 4-dihydrocoumarin have been found to have beneficial properties.
  • 3 4-dihydro-l-benzopyran-2 (2H) -one-6-sulphonate anion which has the added advantage of enhancing water solubility.
  • Other derivatives prevent competing side reactions to the perhydrolysis reaction, an example of which is 3 , 3 -dimethyl-4 -hydro- l-benzopyran-2 (2H) -one (which replaces the reactive hydrogen atoms alpha to the carbonyl group) .
  • activators according to the invention have advantageous secondary properties.
  • 3 , 4 -Dihydrocoumarin is known to scavenge hydroxyl radicals with a rate constant intermediate to that measured for ethanol and dimethylsulphoxide. It is likely that the active scavenging species are phenolic groups (known to behave as radical scavengers) , formed as a result of the perhydrolysis reaction. After the oxidation of a stain the remnants of the peroxyacid will still contain a phenolic group. Any radical scavenging acts to protect the dye and the substrate to radical based damage.
  • the bleach activators are one component of the bleaching compositions of the present invention which also contain a peroxygen bleach capable of liberating hydrogen peroxide in aqueous solution, preferably sodium perborate or sodium percarbonate .
  • the bleaching composition can be formulated in any suitable form, such as a powder or as granules, by methods known to those skilled in the art.
  • Free flowing particles can be produced by any conventional technique, such as the production of a slurry into which the liquid bleach activator has been incorporated, followed by spray drying, to form a base powder to which other dry components can be added.
  • the bleaching composition according to the invention may optionally contain additional bleach activator compounds, such as tetraacetylethylenediamine, pentaacetylglucose, sodium nonanoyloxybenzene sulphonate, and other acylating activator compounds known to react with hydrogen peroxide to form a peroxyacid bleach.
  • additional bleach activator compounds such as tetraacetylethylenediamine, pentaacetylglucose, sodium nonanoyloxybenzene sulphonate, and other acylating activator compounds known to react with hydrogen peroxide to form a peroxyacid bleach.
  • additional bleach activator compounds such as tetraacetylethylenediamine, pentaacetylglucose, sodium nonanoyloxybenzene sulphonate, and other acylating activator compounds known to react with hydrogen peroxide to form a peroxyacid bleach.
  • the bleaching composition may also contain bleach catalysts
  • the bleach activators of the invention may also be used with preformed peroxyacid bleaches, examples of which include e-N,N-phthaloylaminoperoxycarboxylic acids, mono- and diperoxycarboxylic acids.
  • a particular advantage of the bleach activators of the invention is their synergistic performance with other bleach activators such as TAED.
  • the weight ratio of the bleaching agent/peroxy compound to total bleach activator in the bleaching composition will typically be between 1:1 and 150:1.
  • the weight ratio of bleaching agent/peroxy compound to an optional bleaching catalyst in the bleaching composition will be between 5:1 and 1000:1.
  • the bleaching compositions of the invention are usefully parts of detergent or cleaning compositions .
  • the detergent or cleaning compositions may contain surfactants, for example, an anionic surfactant such as an alcohol sulphate or linear alkyl benzene sulphonate or a non- ionic surfactant, such as an alcohol ethoxylate .
  • an anionic surfactant such as an alcohol sulphate or linear alkyl benzene sulphonate
  • a non- ionic surfactant such as an alcohol ethoxylate
  • the detergent or cleaning compositions will generally contain builders such as aluminosilicates (e.g. zeolite A), layered silicates, phosphates particularly sodium tripolyphosphate, trisodium citrate, sodium carbonate or sodium borate .
  • aluminosilicates e.g. zeolite A
  • layered silicates e.g. phosphates particularly sodium tripolyphosphate, trisodium citrate, sodium carbonate or sodium borate.
  • polymeric additives such as maleic/acrylic copolymers which act as co-builders, and soil release polymers such as polyethylene oxide terephthalate and carboxymethylcellulose used to prevent redeposition of soil during washing.
  • the detergent or cleaning compositions may also contain suds suppressors such as soap; enzymes such as lipase, amylase, cellulase and protease; optical brighteners such as stilbene derivatives, sequestrants and flow aids/fillers such as sodium sulphate. More detailed information on typical detergent compositions, which are known to those skilled in the art, is disclosed in, for example, WO 92/06161.
  • the bleaching composition according to the invention when it forms part of a detergent or cleaning composition may comprise between 1 and 100 wt . % of the detergent or cleaning composition (between 1 and 50%, or preferably between 1 and 35% of a main wash laundry or auto dish wash detergent, 50% or more of a bleach additive composition) .
  • the invention is further described in the following Examples :
  • the swatches were agitated at llOrpm for 31 mins in the wash liquor, (the pH was maintained at 10.0), after which the swatches were removed, rinsed in tap water and oven dried at 50°C for 1 hour.
  • 3 , 4 -dihydrocoumarin enhances the bleaching performance of the perborate-detergent system.
  • the DHC activator outperforms TAED in terms of its ability to enhance bleaching with hydrogen peroxide .
  • Swatches were prepared and tested in the manner described in Example 1 using combinations of TAED and 3 , 4-dihydrocoumarin bleach activators as indicated in Table II below.
  • the wash liquor was made up as in Example 1 except that ECE(B) Test Detergent (3.28g) was used with sodium perborate tetrahydrate (8.6mmol) in place of sodium perborate monohydrate .
  • the mixed activator systems outperform TAED as the sole activator. If the amount of activator (s) are expressed in terms of the theoretical yield of peracid formed, the enhanced bleaching performance of the combined system appears to be more evident. The synergistic increase in bleaching performance allows for the addition of lower levels of TAED. However, it is known that TAED is still biocidally active at such levels .
  • 6-sulphonate potassium-3 , 4-dihydro-l- benzopyran-2 (2H) -one- 6-sulphonate

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne une composition blanchissante comprenant: (i) un agent blanchissant, et (ii) un activateur de blanchiment, un ou plusieurs composés de formule générale (1), (2) or (3), dans laquelle le noyau A représente un noyau benzénique condensé ou un noyau hétérocyclique aromatique condensé, substitué ou non par un ou plusieurs groupes choisis parmi les groupes hydroxy, alkoxy, alkyle, alkaryle, aryle, aralkyle, amino, alkylamino, un sel -N+R3 ou -(CH2)n-N+R3 (dans lequel chaque R représente un groupe alkyle ou aryle et n est un entier prenant la valeur de 1 à 6), un groupe -SO3H ou un de ses sels, ou un groupe contenant un carbonyle, et chacun des R5 à R10, identique ou différent, représente un groupe H, hydroxy, alkoxy, alkyle, alkaryle, aryle, aralkyle, amino, alkylamino, un sel -N+R3 (dans lequel R est défini ci-dessus), un groupe -SO3H ou l'un de ses sels, ou un groupe contenant un carbonyle, et où R?5 et R6, R7 et R8¿ et/ou R?9 et R10¿, forment ensemble avec l'atome de carbone auquel ils sont liés un groupe carbonyle ou un groupe cycloalkyle. Les compositions blanchissantes de l'invention, peuvent être incorporées dans des compositions détergentes ou de nettoyage utilisées par exemple en blanchisserie. Les lactones de formules (1), (2) et (3) sont particulièrement actives comme activateurs de blanchiment dans des applications de détergents et de nettoyage, particulièrement dans celles qui demandent une mise en oeuvre à basse température.
PCT/US2000/017716 1999-06-28 2000-06-28 Benzolactones comme activateurs de blanchiment Ceased WO2001000775A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU57726/00A AU5772600A (en) 1999-06-28 2000-06-28 Benzolactones as bleach activators

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9915062.5A GB9915062D0 (en) 1999-06-28 1999-06-28 Bleaching compositions comprising bleach activators
GB9915062.5 1999-06-28

Publications (1)

Publication Number Publication Date
WO2001000775A1 true WO2001000775A1 (fr) 2001-01-04

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Application Number Title Priority Date Filing Date
PCT/US2000/017716 Ceased WO2001000775A1 (fr) 1999-06-28 2000-06-28 Benzolactones comme activateurs de blanchiment

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AU (1) AU5772600A (fr)
GB (1) GB9915062D0 (fr)
WO (1) WO2001000775A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6456798A (en) * 1987-08-28 1989-03-03 Taiyo Koryo Kk Liquid detergent bleaching agent composition having aroma
WO1996031590A1 (fr) * 1995-04-03 1996-10-10 The Procter & Gamble Company Compositions de blanchiment comportant des parfums selectionnes pour masquer l'odeur de l'agent de blanchiment

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6456798A (en) * 1987-08-28 1989-03-03 Taiyo Koryo Kk Liquid detergent bleaching agent composition having aroma
WO1996031590A1 (fr) * 1995-04-03 1996-10-10 The Procter & Gamble Company Compositions de blanchiment comportant des parfums selectionnes pour masquer l'odeur de l'agent de blanchiment

Also Published As

Publication number Publication date
AU5772600A (en) 2001-01-31
GB9915062D0 (en) 1999-08-25

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