DK158954B - WHITE DETERGENTS CONTAINING MONOPEROXYPHTHALIC ACID, A CHELATING COMPOUND AND AN ACTIVATOR FOR THE PEROXYGEN COMPOUND AND THE USE OF TOUCH WASH - Google Patents
WHITE DETERGENTS CONTAINING MONOPEROXYPHTHALIC ACID, A CHELATING COMPOUND AND AN ACTIVATOR FOR THE PEROXYGEN COMPOUND AND THE USE OF TOUCH WASH Download PDFInfo
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- DK158954B DK158954B DK457083A DK457083A DK158954B DK 158954 B DK158954 B DK 158954B DK 457083 A DK457083 A DK 457083A DK 457083 A DK457083 A DK 457083A DK 158954 B DK158954 B DK 158954B
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- 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
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- 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
- C11D3/3945—Organic per-compounds
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Description
iin
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Den foreliggende opfindelse angår generelt blege- og vaskemidler samt deres anvendelse til vask af tøj. Nærmere betegnet angår opfindelsen blege- og vaskemidler omfattende mono-peroxyphthalsyre og/eller et vandopløseligt salt deraf/ et 5 chelateringsmiddel, der er i stand til at danne et vandopløseligt metalkompleks i vandig opløsning, en peroxygenforbindelse og en organisk aktivator for peroxygenforbindelsen, hvilken aktivator omfatter phthalsyreanhydrid.The present invention relates generally to bleaching and washing agents as well as their use for washing clothes. More particularly, the invention relates to bleaching and detergents comprising mono-peroxyphthalic acid and / or a water-soluble salt thereof / a chelating agent capable of forming a water-soluble metal complex in aqueous solution, a peroxygen compound and an organic activator for the peroxygen compound comprising phthalic anhydride.
Blegemidler, der frigører aktivt oxygen i vaskeopløsningen, 10 er udførligt beskrevet som kendt teknik og er almindeligt benyttet til vask af tøj. Generelt indeholder sådanne blegemidler peroxygenforbindelser, såsom perborater, percarbonater, perphosphater og lignende, der fremmer den blegende virkning ved dannelse af hydrogenperoxid i vandig opløsning. En væsent-15 lig ulempe, der knytter sig til anvendelsen af sådanne peroxygenforbindelser, består i at de ikke er optimalt effektive ved de relativt lave vasketemperaturer, der benyttes i de fleste husholdningsvaskemaskiner i USA, dvs. temperaturer i intervallet fra ca. 21°C til ca. 54°C. Til sammenligning er 20 europæiske vasketemperaturer generelt betydelig højere og strækker sig over et interval, der typisk går fra ca. 32°C til ca. 93°C. Imidlertid er der også i Europa og de andre lande, der generelt for tiden benytter vasketemperaturer nær ved kogepunktet, en bevægelse mod tøjvask ved lavere tempera-2 5 tur.Bleaches that release active oxygen into the wash solution 10 are extensively described as known in the art and are commonly used for washing clothes. In general, such bleaches contain peroxygen compounds, such as perborates, percarbonates, perphosphates and the like, which promote the bleaching effect of hydrogen peroxide formation in aqueous solution. A major disadvantage associated with the use of such peroxygen compounds is that they are not optimally effective at the relatively low washing temperatures used in most household washing machines, i.e. temperatures in the range of approx. 21 ° C to approx. 54 ° C. In comparison, 20 European washing temperatures are generally significantly higher and extend over a range that typically ranges from approx. 32 ° C to approx. 93 ° C. However, in Europe and the other countries, which generally use washing temperatures near the boiling point, there is also a movement towards laundry at lower temperatures.
I et forsøg på at forøge blegevirkningen af peroxygenblege-midler har de ifølge kendt teknik benyttede materialer krævet aktivatorer i kombination med oxygenforbindelserne. Det antages generelt, at reaktionen mellem peroxygenforbindelsen 30 og aktivatoren resulterer i dannelse af en peroxysyre, som er den aktive blegeforbindelse. Talrige forbindelser har hidtil været foreslået som aktivatorer for peroxygenblege-midler, hvortil hører carboxylsyreanhydrider, såsom de 2In an attempt to increase the bleaching effect of peroxygen bleaches, the materials used in the prior art have required activators in combination with the oxygen compounds. It is generally believed that the reaction between the peroxygen compound 30 and the activator results in the formation of a peroxyacid which is the active bleaching compound. Numerous compounds have heretofore been proposed as activators for peroxygen bleaches to which carboxylic acid anhydrides, such as the 2
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i USA patentskrifterne nr. 3.928.775, 3.338.839 og 3.352.634 omhandlede, carboxylsyreestere, såsom de i USA patentskrift nr 2.995.905 omhandlede, N-acylforbindelser, såsom de i USA patentskrifterne nr. 3.916.648 og nr. 3.919.102 omhandlede, 5 cyanoaminer, såsom de i USA patentskrifterne nr. 3.916.648 og nr. 3.919.102 omhandlede, og acylsulfoamider, såsom de i USA patentskrift nr. 3.245.913 omhandlede.U.S. Patent Nos. 3,928,775, 3,338,839, and 3,352,634 to carboxylic acid esters, such as those disclosed in U.S. Patent No. 2,995,905, N-acyl compounds such as U.S. Patent Nos. 3,916,648 and 3,919. 102, 5 cyanoamines, such as U.S. Patent Nos. 3,916,648 and 3,919,102, and acylsulfoamides, such as U.S. Patent No. 3,245,913.
I forvejen fremstillede peroxysyrer har også været benyttet -til frembringelse af blegning i vaskeopløsninger til tøjvask.Pre-prepared peroxyacids have also been used to produce bleaching in laundry solutions for laundry.
10 USA patentskrifterne nr. 3.770.816, nr. 4.170.453 og 4.259.201 illustrerer kendt teknik omhandlende blegemidler omfattende en peroxysyreforbindelse.U.S. Patent Nos. 3,770,816, 4,170,453, and 4,259,201 illustrate prior art bleaching agents comprising a peroxyacid compound.
Det er generelt anerkendt indenfor den kendte teknik, at metalioner er i stand til at virke som dekomponeringskatalysatorer 15 for uorganiske peroxygenforbindelser og organiske peroxysyrer.It is generally recognized in the prior art that metal ions are capable of acting as decomposition catalysts for inorganic peroxygen compounds and organic peroxyacids.
I et forsøg på at stabilisere sådanne blegende forbindelser i vaskeopløsningen har chelaterende. midler været inkorporeret i blegende vaskemidler. USA patentskrift nr. 3.2,43.378 omhandler eksempelvis et blegemiddel indeholdende en blegende peroxy-20 genforbindelse samt et chelateringsmiddel til sekvestrering af metalkationer. Generelt falder de chelateringsmidler, som har været anvendt til dette formål, indenfor en eller to kategorier: (a) materialer, såsom heterocykliske forbindelser og ketoner, især 8-hydroxyquinolin, der binder metalkationer 25 i vaskevæsken ved udfældning af dem fra opløsningen, og (b) materialer, såsom aminopolycarboxylater og aminopolyphospho-natforbindelser, der danner vandopløselige metalkomplekser med de kationer, der findes i vaskeopløsningen. Følgelig fastslår USA patentskrift nr. 4.005.029, at udvalgte aldehyder, 30 ketoner samt forbindelser, der danner aldehyder eller ketoner i vandig opløsning (f.eks. 8-hydroxyquinolin), kan anvendes til aktivering af alifatiske peroxysyrer, såsom diperazelain-syre, diperadipinsyre og aromatiske peroxysyrer (og vandopløselige salte deraf) indbefattende monoperoxyphthalsyre og 3In an attempt to stabilize such bleaching compounds in the wash solution has chelating. agents have been incorporated into bleaching detergents. U.S. Patent No. 3,243,378, for example, discloses a bleach containing a bleaching peroxygen compound as well as a chelating agent for sequestering metal cations. Generally, the chelating agents used for this purpose fall into one or two categories: (a) materials such as heterocyclic compounds and ketones, especially 8-hydroxyquinoline, which binds metal cations 25 in the wash liquid by precipitation of them from the solution, and ( b) materials such as aminopolycarboxylates and aminopolyphosphonate compounds which form water-soluble metal complexes with the cations present in the wash solution. Accordingly, U.S. Patent No. 4,005,029 states that selected aldehydes, 30 ketones, as well as compounds that form aldehydes or ketones in aqueous solution (e.g., 8-hydroxyquinoline) can be used to activate aliphatic peroxyacids such as diperazelaic acid, diperadipic acid and aromatic peroxyacids (and water-soluble salts thereof) including monoperoxyphthalic acid and 3
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diperoxyterephthalsyre. I USA patentskrift nr. 4.170.453 omtales en blanding af 8-hydroxyquinolin, phosphorsyre og natrium-pyrophosphat som et foretrukket chelateringssystem til stabilisering af det aktive oxygen, der dannes i vaskeopløsninger 5 indeholdende diperoxydodecandisyre. USA patentskrift nr. 4.22! 452 omhandler kombinationen af angivne klasser af chelateringi midler (hvortil hører phosphonatforbindelser) med uorganiske peroxygenforbindelser og en organisk aktivator med henblik på undertrykkelse af dekomponeringen af peroxygenforbindelsen 10 i blegemidlet. Specielt siges chelateringsmidlet at inhibere den uønskede sidereaktion af peroxygenforbindelsen med den peroxysyre, der dannes ved den primære omsætning af peroxygen· forbindelsen og aktivatoren, idet virkningen af sidereaktione: består i at fjerne de blegende peroxysyreforbindelser fra 15 opløsningen. USA patentskrift nr. 4.225.452 leder imidlertid bort fra brugen af sådanne chelaterlngsmidler i opløsninger, hvori peroxysyren har en dobbeltbinding mellem carbonatomer-ne ία,α1 -stillingen i forhold til carbonylgruppen. Specielt i patentskriftets 2. spalte begyndende ved linie 63 udelukkes 20 phthalsyreanhydrid som aktivator for det omhandlede blegemiddel som følge af ustabilitet. For så vidt som den ved omsætningen mellem phthalsyreanhydrid og en uorganisk peroxygen-forbindelse dannede peroxysyre er monoperoxyphthalsyre, leder USA patentskrift nr. 5.225.452 øjesynlig bort fra brugen af 25 monoperoxyphthalsyre i de i patentskriftet omhandlede blegemidler.diperoxyterephthalsyre. U.S. Patent No. 4,170,453 discloses a mixture of 8-hydroxyquinoline, phosphoric acid, and sodium pyrophosphate as a preferred chelating system for stabilizing the active oxygen formed in wash solutions 5 containing diperoxydodecandic acid. U.S. Patent No. 4.22! 452 discloses the combination of specified classes of chelating agents (including phosphonate compounds) with inorganic peroxygen compounds and an organic activator for suppressing the decomposition of peroxygen compound 10 in the bleach. In particular, the chelating agent is said to inhibit the undesirable side reaction of the peroxygen compound with the peroxyacid formed by the primary reaction of the peroxygen compound and activator, the effect of side reactions being: removing the bleaching peroxyacid compounds from the solution. However, United States Patent No. 4,225,452 dispenses with the use of such chelating agents in solutions wherein the peroxy acid has a double bond between the carbon atoms ία, α1 position relative to the carbonyl group. Especially in the second column of the patent beginning at line 63, 20 phthalic anhydride is excluded as activator of the present bleach due to instability. In so far as the peroxyacid formed in the reaction between phthalic anhydride and an inorganic peroxygen compound is monoperoxyphthalic acid, United States Patent No. 5,225,452 is clearly disregarding the use of 25 monoperoxyphthalic acid in the bleaches disclosed in the patent.
Europæisk offentliggørelsesskrift nr. 27.693 omhandler brugen af magnesiummonoperoxyphthalat somet effektivt blegemiddel. Trykskriftet omhandler også den eventuelle kombination 30 af et blegemiddel med en "aldehyd- eller ketonperoxysyreakti-vator som beskrevet i USA patentskrift nr. 4.005.029, f.eks.European Patent Publication No. 27,693 discloses the use of magnesium monoperoxyphthalate as effective bleach. The disclosure also discloses the optional combination of a bleach with an "aldehyde or ketone peroxyacid activator as disclosed in U.S. Patent No. 4,005,029, e.g.
8-hydroxyquinolin der er en kendt peroxygenstabilisator". Trykskriftet omhandler også organiske phosphonatforbindelser tillige med en række forskellige andre forbindelser som væ-35 rende anvendelige vaskemiddel-buildere, der eventuelt kan in-8-hydroxyquinoline is a known peroxygen stabilizer. "The publication also discloses organic phosphonate compounds as well as a variety of other compounds as useful detergent builders which may be included.
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4 korporeres i de beskrevne vaskemidler. Der findes imidlertid ingen omtale vedrørende de gunstige virkninger, der ledsager anvendelsen af en ringe mængde organiske phosphonatforbindel-ser til brug som dhelateringsmidler i blegemidler og især i 5 midler indeholdende magnesiummonoperoxyphthalat.4 is incorporated in the described detergents. However, there is no mention of the beneficial effects accompanying the use of a small amount of organic phosphonate compounds for use as dhelating agents in bleaching agents and in particular in magnesium monoperoxyphthalate containing agents.
Det ovennævnte europæiske offentliggørelsesskrift omhandler også, at peroxygenforbindelser eventuelt kan inkorporeres i vaskemidler indeholdende de beskrevne peroxysyreblegemidler med henblik på opnåelse af blegning ved højere vasketempera-10 ture. Ingen antydning findes imidlertid deri vedrørende brugen af en organisk aktivator i kombination med sådanne peroxygenforbindelser, og specielt antydet om ønskeligheden af at bruge en peroxygenforbindelse i kombination med phthalsyrean-hydrid som aktivator i et blegningssystem indeholdende mono-15 peroxyphthalsyre og/eller et salt deraf samt et chelateringsmid-del af den heri beskrevne type.The above-mentioned European publication also discloses that peroxygen compounds can optionally be incorporated into detergents containing the described peroxyacid bleaches to obtain bleaching at higher washing temperatures. However, there is no indication therein of the use of an organic activator in combination with such peroxygen compounds, and in particular, of the desirability of using a peroxygen compound in combination with phthalic anhydride as activator in a bleaching system containing mono-peroxyphthalic acid and / or a salt thereof and a chelating agent of the type described herein.
Det blegende vaskemiddel ifølge opfindelsen er ejendommeligt ved, at det indeholder: (a) fra ca. 5 til ca. 50 vægt% af et middel omfattende mono-20 peroxyphthalsyre og/eller et vandopløseligt salt deraf, et chelateringsmiddel bestående i det væsentlige af en diethylen-triamin-pentamethylenphosphonsyre og/eller et vandopløseligt salt deraf, en peroxygenforbindelse, som ikke er monoperoxy-phthalsyre, og en aktivator for nævnte peroxygenforbindelse 25 bestående i det væsentlige af phthalsyreanhydrid, (b) fra ca. 5 til ca. 50 vægt% af et eller flere tensider valgt blandt anioniske, kationiske, ikke-ioniske, amfoly-tiske og zwitterioniske tensider, (c) fra ca. 5 til ca. 80 vægt% af et vaskemiddel-buildersalt 30 og (d) resten omfattende vand og eventuelt et fyldstofsalt.The bleaching detergent of the invention is peculiar in that it contains: (a) from ca. 5 to approx. 50% by weight of an agent comprising monoperoxyphthalic acid and / or a water-soluble salt thereof, a chelating agent consisting essentially of a diethylene-triamine-pentamethylene phosphonic acid and / or a water-soluble salt thereof, a non-monoperoxyphthalic acid peroxygen compound, and an activator for said peroxygen compound 25 consisting essentially of phthalic anhydride; 5 to approx. 50% by weight of one or more surfactants selected from anionic, cationic, nonionic, ampholytic and zwitterionic surfactants, (c) from ca. 5 to approx. 80% by weight of a detergent builder salt and (d) the residue comprising water and optionally a filler salt.
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Udførelsesformer for vaskemidlet ifølge opfindelsen er.angivet i de uselvstændige krav rettet på midlet. Ved fremgangsmåden ifølge opfindelsen sker blegning af det plettede og/eller forurenede materiale ved, at materialet bringes i kontakt med en 5 vandig opløsning af det omhandlede vaskemiddel.Embodiments of the detergent of the invention are set forth in the dependent claims directed to the detergent. In the process of the invention, bleaching of the stained and / or contaminated material occurs by contacting the material with an aqueous solution of the present detergent.
Med midlet og fremgangsmåden ifølge opfindelsen opnås en forøget blegevirkning.With the agent and method according to the invention, an increased bleaching effect is obtained.
10 Udtrykket "chelateringsmiddel" som heri benyttet refererer til organiske forbindelser, der i små mængder er i stand til at binde overgangsmetalkationer (f.eks. jern, nikkel og kobalt), der vides på uheldig måde at påvirke stabiliteten af peroxy-genforbindel ser og/eller peroxysyrer i vandige blegeopløsnin-15 ger. De heri benyttede chelateringsmidler indbefatter derfor ikke uorganiske forbindelser, der sædvanligvis benyttes som buildersalte i vaskemidler. De chelateringsmidler, der er anvendelige til den foreliggende opfindelses formål, hører til den type, der er i stand til at danne et i det væsentlige 20 vandopløseligt i stedet for et udfældet metalkompleks i van dige opløsninger med metalioner, især overgangsmetalkationer som de ovenfor anførte. Egnede chelateringsmidler indbefatter di ethyl entr iaminpentamethylenphosphonsyre (heri omtalt som ”DTPMP") og/eller et vandopløseligt salt deraf. Blandt saltene 25 af DTPMT foretrækkes generelt natrium-, kalium- og ammoniumsaltet som følge af deres relativt større opløselighed og lette fremstilling.The term "chelating agent" as used herein refers to organic compounds capable of binding, in small amounts, to transition metal cations (e.g., iron, nickel and cobalt) which are known to adversely affect the stability of peroxygen compounds and / or peroxyacids in aqueous bleaching solutions. Therefore, the chelating agents used herein do not include inorganic compounds usually used as builder salts in detergents. The chelating agents useful for the purposes of the present invention are of the type capable of forming a substantially water-soluble rather than a precipitated metal complex in aqueous metal ion solutions, especially transition metal cations such as those listed above. Suitable chelating agents include the di-ethylamine pentamethylene phosphonic acid (herein referred to as "DTPMP") and / or a water-soluble salt thereof. Among the salts of the DTPMT, the sodium, potassium and ammonium salts are generally preferred due to their relatively greater solubility and ease of preparation.
Generelt foreligger de i blegemidlerne ifølge opfindelsen 30 benyttede chelateringsmidler i et vægtforhold i forhold til MPPA og/eller dets salte fra ca. 1:5 til ca. 1:50 og mere foretrukket fra ca. 1:7 til ca. 1:20. I de builderholdige blegende vaskemidler ifølge opfindelsen er koncentrationen af 35 6Generally, the chelating agents used in the bleaching agents of the invention are present in a weight ratio to MPPA and / or its salts from ca. 1: 5 to approx. 1:50 and more preferably from ca. 1: 7 to approx. 1:20. In the builder-containing bleaching detergents of the invention, the concentration of 35 is 6
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chelaterings midlet generelt under ca.· 5 vægt%, fortrinsvis under ca. 2 vægt% og mest foretrukket under ca. 1 vægt% af sådanne vaskemidler.the chelating agent is generally below about 5% by weight, preferably below about 2% by weight and most preferably less than approx. 1% by weight of such detergents.
5 Monoperoxyphthalsyre og/eller et eller flere af de vandoplø selige salte deraf i kombination med en peroxygenforbindelse er blegemidlerne i midlerne ifølge opfindelsen. Selvom MPPA tilvejebringer acceptabel blegevirkning, har det den ulempe, at det har relativt dårlig stabilitet ved lagring i blanding 10 med andre komponenter, der sædvanligvis findes i husholdnings vaskemidler. Af hensyn til stabilitet anvendes magnesiumsaltet af MPPA derfor fortrinsvis i midlerne ifølge opfindelsen, nemlig magnesiummonoperoxyphthaiat. Alkalimetalsaltet, calciumeller barium-jordalkalimetalsalte og/eller ammoniumsaltet af 15 MPPA kan også anvendes i de her beskrevne blege- og vaskemid ler, selvom sådanne salte generelt er mindre foretrukne end det ovenfor nævnte magnesiumsalt ud fra et stabilitetssynspunkt .Monoperoxyphthalic acid and / or one or more of the water-soluble salts thereof in combination with a peroxygen compound are the bleaching agents of the compositions of the invention. Although MPPA provides acceptable bleaching effect, it has the disadvantage of having relatively poor stability when stored in blend 10 with other components usually found in household detergents. For reasons of stability, therefore, the magnesium salt of MPPA is preferably used in the compositions of the invention, namely magnesium monoperoxyphthalate. The alkali metal salt, calcium or barium alkaline earth metal salts and / or the ammonium salt of 15 MPPA can also be used in the bleaching and detergent compositions described herein, although such salts are generally less preferred than the above-mentioned magnesium salt from a stability point of view.
2o Fremstillingen af MPPA foretages generelt ved omsætning af hydrogenperoxid med phthalsyreanhydrid. Det resulterende MPPA kan derefter anvendes til fremstilling af magnesiummonoperoxy-phthalat ved omsætning med en magnesiumforbindelse i nærværelse af et organisk opløsningsmiddel. En detaljeret beskrivelse 25 af fremstillingen af MPPA og magnesiumsaltet deraf er anført på siderne 7 til 10 i europæisk offentliggørelsesskrift nr. 27.693, hvorhos de nævnte sider 7 til 10 medtages heri ved henvisningen dertil.The preparation of MPPA is generally carried out by reacting hydrogen peroxide with phthalic anhydride. The resulting MPPA can then be used to prepare magnesium monoperoxyphthalate by reaction with a magnesium compound in the presence of an organic solvent. A detailed description 25 of the preparation of MPPA and its magnesium salt is set forth on pages 7 to 10 of European Patent Publication No. 27,693, the pages of pages 7 to 10 of which are incorporated herein by reference.
30 De ifølge opfindelsen anvendelige peroxygenforbindelser ind befatter forbindelser, der frigører hydrogenperoxid i vandige medier, såsom alkalimetalperborater, -percarbonater, -perphos-phater og lignende. Natriumperborat er særlig foretrukket som 35 7The peroxygen compounds useful in the invention include compounds which release hydrogen peroxide in aqueous media such as alkali metal perborates, percarbonates, perphosphates and the like. Sodium perborate is particularly preferred as 7
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følge af dets kommercielle tilgængelighed.due to its commercial availability.
I blegemidlet foreligger peroxygenforbindelsen generelt i forhold til phthalsyreanhydridaktivåto'r.én.. !.·. i et molært forhold mellem peroxygenforbindelse og phthalsyreanhydrid fra ca. 1:1C 5 til ca. 10:1, idet det foretrukne forhold er fra ca. 1:2 til ca. 3:1. Det vil fremgå, at koncentrationen af phthalsyreanhydrid vil afhænge af koncentrationen af peroxygenforbindelser som på sin side styres af den ønskede blegningsgrad. Peroxyger forbindelsen foreligger typisk i blegemidlet i en mængde gåenc 10 fra ca. 1 vægt% til ca. 50 vægts, fortrinsvis fra 3 til 25 vægt% og mest foretrukket fra 5 til 20 vægt% af blegemidlet.In the bleaching agent, the peroxygen compound is generally present in relation to the phthalic anhydride active ingredient. in a molar ratio of peroxygen compound to phthalic anhydride from ca. 1: 1C 5 to approx. 10: 1, with the preferred ratio being from approx. 1: 2 to approx. 3: 1. It will be appreciated that the concentration of phthalic anhydride will depend on the concentration of peroxygen compounds which in turn is controlled by the desired degree of bleaching. The peroxygen compound is typically present in the bleach in an amount of about 10 to about 1% by weight to approx. 50 wt., Preferably from 3 to 25 wt.% And most preferably from 5 to 20 wt.% Of the bleach.
Mængden af blegemiddel, der sættes til vaskeopløsningen, vælges generelt til opnåelse af en mængde peroxygenforbindelse og peroxysyreforbindelse i intervallet svarende til ca. 3 til 15 10 dele aktiv oxygen pr. million dele af vaskeopløsnigen.The amount of bleach added to the wash solution is generally selected to obtain an amount of peroxygen compound and peroxyacid compound in the range of about 3 to 15 10 parts of active oxygen per million parts of the wash solution.
MPPA og/eller et vandopløseligt salt deraf i kombination med det valgte gelateringsmiddel, peroxygenforbindelse og phthalsyreanhydrid kan sammensættes som et separat blegeprodukt eller kan alternativt anvendes i et sammensat vaskemiddel. I 20 overensstemmelse hermed kan blegemidlet ifølge opfindelsen indbefatte konventionelle additiver, der anvendes indenfor tekstilvaskeområdet, såsom bindemidler, fyldstoffer, builder salte, proteolytiske enzymer, optiske klaringsmidler, parfumer, farvestoffer, korrosionsinhibitorer, antigenaflejrings-25 midler, skumstabilisatorer og lignende, der alle kan tilsættes i varierende mængder afhængigt af de ønskede egenskaber af blegemidlet og deres forligelighed med et sådant blegemiddel. Endvidere kan blegemidlerne ifølge opfindelsen inkorporeres i vaskemidler til tøjvask indeholdende overfladeaktive midler, 30 såsom anioniske, kationiske, ikke-ioniske, amf.olytiske og zwitterioniske detergenter og blandinger deraf.MPPA and / or a water-soluble salt thereof in combination with the selected gelling agent, peroxygen compound and phthalic anhydride may be formulated as a separate bleaching product or alternatively may be used in a composite detergent. Accordingly, the bleaching agent of the invention may include conventional additives used in the textile washing field such as binders, fillers, builder salts, proteolytic enzymes, optical cleaners, perfumes, dyes, corrosion inhibitors, antigen deposition agents, foam stabilizers, and the like. in varying amounts depending on the desired properties of the bleach and their compatibility with such bleach. Furthermore, the bleaching agents of the invention can be incorporated into laundry detergents containing surfactants such as anionic, cationic, nonionic, ampholytic and zwitterionic detergents and mixtures thereof.
Når de omhandlede blegemidler inkorporeres i et konventionelt 8When the bleaches in question are incorporated into a conventional 8
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vaskemiddel og derfor foreligger som et fuldt sammensat blegende vaskemiddel, vil sidstnævnte vaskemidler omfatte følgende: fra ca. 5 til 50 vægt% af det omhandlede blegemiddel, fra ca. 5 til ca. 50 vægt% af et detergent-overfladeaktivt middel, 5 fortrinsvis fra ca. 5 til ca. 30 vægt%, og fra ca. 5 til ca.detergent and therefore available as a fully composed bleaching detergent, the latter detergents will comprise the following: 5 to 50% by weight of the subject bleach, from approx. 5 to approx. 50% by weight of a detergent surfactant, preferably from ca. 5 to approx. 30% by weight, and from approx. 5 to approx.
80 vægt% af et detergent-buildersalt , der også kan fungerer som Puffer til opnåelse af det krævede pH-interval, når vaskemidlet sættes til vand. De vandige vaskeopløsninger vil have et pH-interval fra ca. 7 til ca. 12, fortrinsvis fra ca. 8 10 til ca. 10 og mest foretrukket fra ca. 8,5 til ca. 9. En fore-trukken mængde af buildersaltet er fra ca. 20 til 65 vægt% af midlet. Resten af midlet vil hovedsaglig omfatte vand, fyldstof salte/ såsom natriumsulfat, og eventuelt mindre additiver, såsom optiske klaringsmidler, parfumer, farvestoffer, antigen-15 aflejringsmidler og lignende.80% by weight of a detergent builder salt which can also act as Buffer to achieve the required pH range when the detergent is added to water. The aqueous wash solutions will have a pH range of approx. 7 to approx. 12, preferably from ca. 8 10 to approx. 10 and most preferably from ca. 8.5 to approx. 9. A preferred amount of the builder salt is from ca. 20 to 65% by weight of the agent. The remainder of the agent will mainly comprise water, filler salts / such as sodium sulfate, and optionally minor additives, such as optical brighteners, perfumes, dyes, antigen deposits, and the like.
Til de anioniske overfladeaktivemidler, der kan anvendes ifølge den foreliggende opfindelse, hører de overfladeaktive: forbindelser eller detergentforbindelser, der indeholder en organisk hydrofob gruppe indeholdende generelt fra ca. 8 til ca. 20 26 carbonatomer og fortrinsvis fra 10 til 18 carbonatomer i deres molekylære opbygning samt mindst én vandsolubiliserende gruppe valgt blandt sulfonat, sulfat, carboxylat, phosphonat og phosphat til dannelse af en vandopløselig detergent.Among the anionic surfactants useful in the present invention are the surfactants: compounds or detergent compounds which contain an organic hydrophobic group containing generally from ca. 8 to approx. 20 26 carbon atoms and preferably from 10 to 18 carbon atoms in their molecular structure and at least one water solubilizing group selected from sulfonate, sulfate, carboxylate, phosphonate and phosphate to form a water-soluble detergent.
Eksempler på egnede anioniske detergenter indbefatter sæber, 25 såsom de vandopløselige salte (f.eks. natrium-, kalium-, ammonium- og alkanolammoniumsaltene) af højere fedtsyrer eller harpikssalte indeholdende fra ca. 8 til ca. 20 carbonatomer og fortrinsvis 10 til 18 carbonatomer. Egnede fedtsyrer kan opnås fra olier og voksarter af animalsk eller vegetabilsk 30 oprindelse, f.eks. talg, fedt, kokosnødolie og blandinger deraf. Særlig egnede er natrium- og kaliumsaltene af fedtsyreblandinger udvundet fra kokosnødolie og talg, f.eks. kokosnød-natriumsæbe og talg-kaliumsæbe.Examples of suitable anionic detergents include soaps, such as the water-soluble salts (e.g., sodium, potassium, ammonium and alkanolammonium salts) of higher fatty acids or resin salts containing from ca. 8 to approx. 20 carbon atoms and preferably 10 to 18 carbon atoms. Suitable fatty acids can be obtained from oils and waxes of animal or vegetable origin, e.g. tallow, fat, coconut oil and mixtures thereof. Particularly suitable are the sodium and potassium salts of fatty acid mixtures extracted from coconut oil and sebum, e.g. coconut sodium soap and sebum potassium soap.
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Den anioniske detergentklasse indbefatter også de vandopløselige sulfaterede og sulfonerede detergenter med en alkylgruppe indeholdende fra ca. 8 til 26 og fortrinsvis fra ca. 12 til ca. 22 carbonatomer. Eksempler på de sulfonerede anioniske 5 detergenter er de højere alkyl-monokernearomatiske sulfonater, såsom de højere alkylbenzensulfonater indeholdende fra ca. 10 til ca. 16 carbonatomer i den højere alkylgruppe i en lige eller forgrenet kæde, såsom eksempelvis natrium-, kalium- og ammoniumsaltene af højere alkylbenzensulfonater, 10 højere alkyltoluensulfonater og alkylphenolsulfonater.The anionic detergent class also includes the water-soluble sulfated and sulfonated detergents having an alkyl group containing from ca. 8 to 26 and preferably from ca. 12 to approx. 22 carbon atoms. Examples of the sulfonated anionic detergents are the higher alkyl mono-nuclear aromatic sulfonates, such as the higher alkylbenzene sulfonates containing from ca. 10 to approx. 16 carbon atoms in the higher alkyl group in a straight or branched chain, such as, for example, the sodium, potassium and ammonium salts of higher alkylbenzenesulfonates, 10 higher alkyltoluenesulfonates and alkylphenol sulfonates.
Andre egnede anioniske detergenter er olefinsulfonaterne inkli sive langkædede alkensulfonater, langkædede hydroxyalkansul-fonater eller blandinger af alkensulfonater og hydroxyalkan-sulfonater. Olefinsulfonat-detergenterne kan fremstilles på 15 konventionel måde ved omsætning af SO^ med langkædede definer indeholdende fra ca. 8 til ca. 25 og fortrinsvis fra ca.Other suitable anionic detergents are the olefin sulfonates including long chain alkene sulfonates, long chain hydroxyalkanesulfonates or mixtures of alkene sulfonates and hydroxyalkanesulfonates. The olefin sulfonate detergents can be prepared in a conventional manner by reacting SO 2 with long-chain defines containing from ca. 8 to approx. 25 and preferably from ca.
12 til ca. 21 carbonatomer, idet sådanne olefiner har formlen RCH=CHR^ , hvori R er en højere alkylgruppe med 6 til 23 carbonatomer, og R1 er en alkylgruppe indeholdende fra ca. 1 til 2 0 ca. 17 carbonatomer eller hydrogen, til dannelse af en blandin< af sultoner og alkensulfonsyrer, som derpå behandles til omdannelse af sultonerne til sulfonater. Andre eksempler på sulfat- eller sulfonatdetergenterer paraf.finsulfonater indeholdende fra ca. 10 til ca. 20 carbonatomer og fortrinsvis 25 fra ca. 15 til ca. 20 carbonatomer. De vigtigste paraffinsulfonater fremstilles ved omsætning af langkædede a-olefiner og bisulfiter -Påraffinsulfonater med sulfonatgruppen fordelt langs paraffinkæden er vist i USA patentskrifterne nr. 2.503. 280, 2.507.088, nr. 3.260.741 og nr. 3.372.188 samt i tysk 30 patentskrift nr. 735.096. Andre anvendelige sulfat- og sulfonatdetergenter indbefatter natrium- og kaliumsulfonater af højere alkoholer indeholdende fra ca. 8 til ca. 18 carbonatomer, såsom eksempelvis natriumlaurylsulfat og natrium-talg-alkoholsulfat, natrium- og kaliumsalte af a-sulfofedtsyre-35 estere indeholdende fra ca. 10 til ca. 20 carbonatomer i 1012 to approx. 21 carbons, such olefins having the formula RCH = CHR 2, wherein R is a higher alkyl group having 6 to 23 carbon atoms and R 1 is an alkyl group containing from ca. 1 to 20 approx. 17 carbon atoms or hydrogen, to form a mixture of sultones and alkenesulfonic acids, which are then treated to convert the sultones to sulfonates. Other examples of sulfate or sulfonate detergent paraffin fin sulfonates containing from ca. 10 to approx. About 20 carbon atoms and preferably 25 from ca. 15 to approx. 20 carbon atoms. The most important paraffin sulfonates are produced by reaction of long chain α-olefins and bisulfites -Paraffin sulfonates with the sulfonate group distributed along the paraffin chain are shown in United States Patent Specification No. 2,503. 280, 2,507,088, Nos. 3,260,741 and Nos. 3,372,188, and in German 30 Patent No. 735,096. Other useful sulfate and sulfonate detergents include sodium and potassium sulfonates of higher alcohols containing from ca. 8 to approx. 18 carbon atoms, such as, for example, sodium lauryl sulfate and sodium tallow alcohol sulfate, sodium and potassium salts of α-sulfo fatty acid esters containing from ca. 10 to approx. 20 carbon atoms in 10
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asylgruppen, f.eks. methyl-a-sulfomyristat og methyl-a-sulfo-talloat, ammoniumsulfater af mono- eller di-glycerider af højere (cig“c18^ fedtsyrer, f.eks. stearinmonoglyceridmonosul-fat, natrium- og alkylolammoniumsalte af alkylpolyethenoxy-5 ethersulfater fremstillet ved kondensering af 1 til 5 mol ethylenoxid med 1 mol højere (C g”Cig) alkohol, natrium-højere alkyl (C^Q-C^g)-glycerylethersulfonater samt natrium-eller kalium-alkylphenolpolyethenoxyethersulfater med ca. 1 til 6 oxyethylengrupper pr. molekyle, og hvori alkylgrupperne 10 indeholder fra ca. 8 til ca. 12 carbonatomer.the asylum group, e.g. methyl α-sulfomyristate and methyl α-sulfo talloate, ammonium sulphates of higher mono- or di-glycerides of (cig "c18 fatty acids, for example, stearin monoglyceride monosulfate, sodium and alkylolammonium salts of alkyl polyethene oxyether sulfates prepared by condensation of 1 to 5 moles of ethylene oxide with 1 mole of higher (Cg "Cig) alcohol, sodium higher alkyl (C1-C6g) glyceryl ether sulfonates, and sodium or potassium alkylphenol polyethene oxyether sulfates having about 1 to 6 oxyethylene groups per molecule, and wherein the alkyl groups 10 contain from about 8 to about 12 carbon atoms.
De allermest foretrukne vandopløselige anioniske detergentforbindelser er ammoniumsaltene og de substituerede ammoniumsalte (såsom mono-, di- og triethanolaminsalte), alkalimetalsalte (såsom natrium-og kaliumsalte) og jordalkalimetalsalte 15 (såsøm calcium- og magnesiumsalte) af de højere alkylbenzen-sulfonater, olefinsulfonater og højere alkylsulfater. Blandt de ovenfor anførte anioniske detergentforbindelser er de mest foretrukne natrium-lineært .alkyl- benzensulfonaterne (LABS).The most preferred water-soluble anionic detergent compounds are the ammonium salts and the substituted ammonium salts (such as mono-, di- and triethanolamine salts), alkali metal salts (such as sodium and potassium salts) and alkaline earth metal salts (such as calcium and magnesium sulfate), and the higher alkyl salts, higher alkyl sulfates. Among the anionic detergent compounds listed above are the most preferred sodium linear linear alkylbenzene sulfonates (LABS).
De ikke-ioniske syntetiske organiske detergenter er karakte-20 riseret ved tilstedeværelsen af en organisk hydrofob· gruppe· og en organisk hydrofil gruppe og fremstilles typisk ved kondensation af en organisk alifatisk eller alkyl-aromatisk hydrofob .forbindelse med ethylenoxid (hydrofil af natur). Praktisk taget enhver hydrofob.forbindelse, der har en carboxy-, hydroxy-, 25 amido- eller aminogruppe med et frit hydrogenatom knyttet til nitrogenatomet,kan kondenseres med ethylenoxid eller med polyhydratationsproduktet deraf, polyethylenglycol, til dannelse af en ikke-ionisk detergent. Længden af den hydrofile kæde eller polyoxyethylenkæde kan let indstilles til opnåelse 30· af den ønskede balance mellem de hydrofobe og de hydrofile grupper.The nonionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically prepared by condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic in nature). Practically any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen atom attached to the nitrogen atom can be condensed with ethylene oxide or with its polyhydration product, polyethylene glycol, to form a nonionic detergent. The length of the hydrophilic chain or polyoxyethylene chain can be readily adjusted to achieve 30 ° of the desired balance between the hydrophobic and hydrophilic groups.
De ikke-ioniske detergenter indbefatter polyethylenoxidkon-densatet af 1 mol alkylphenol indeholdende fra ca. 6 til ca.The nonionic detergents include the polyethylene oxide condensate of 1 mole of alkylphenol containing from ca. 6 to approx.
1111
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12 i en lige eller forgrenet kædekonfiguration med ca. 5 til ca. 30 mol ethylenoxid, f.eks. nonylphenol kondenseret med 9 mol ethylenoxid, dodecylphenol kondenseret med 15 mol ethy-lenoxid og dinonylphenol kondenseret med 15 mol ethylenoxid.12 in a straight or branched chain configuration with approx. 5 to approx. 30 moles of ethylene oxide, e.g. nonylphenol condensed with 9 moles of ethylene oxide, dodecylphenol condensed with 15 moles of ethylene oxide, and dinonylphenol condensed with 15 moles of ethylene oxide.
5 Kondensationsprodukter af de tilsvarende alkylthiophenoler med 5 til 30 mol ethylenoxid er også egnede.Condensation products of the corresponding alkylthiophenols with 5 to 30 moles of ethylene oxide are also suitable.
Af ikke-ioniske overfladeaktive midler af de ovenfor beskrev-ne typer foretrækkes sådanne af den ethoxylerende alkoholtype. Særlige foretrukne ikke-ioniske overfladeaktive midler ind-10 befatter kondensationsproduktet af kokosnødfedtalkohol med ca. 6 mol ethylenoxid pr. mol kokosnødfedtalkohol, kondensationsproduktet af talgfedtalkohol med ca. 11 mol ethylenoxid pr. mol talgfedtalkohol, kondensationsproduktet af en sekundær fedtalkohol indeholdende ca. 11-15 carbonatomer med ca. 9 15 mol ethylenoxid pr. mol fedtalkohol samt kondensationsprodukter af mere eller mi ndie førgrenede primære alkoholer, hvis forgreningen er overvejende 2-methyl, med fra ca. 4 til ca.Of non-ionic surfactants of the types described above, those of the ethoxylating alcohol type are preferred. Particularly preferred nonionic surfactants include the condensation product of coconut fatty alcohol by about 6 moles of ethylene oxide per mole of coconut fat alcohol, the condensation product of sebum fat alcohol by approx. 11 moles of ethylene oxide per mole of sebum fat alcohol, the condensation product of a secondary fat alcohol containing approx. 11-15 carbon atoms with approx. 9 15 moles of ethylene oxide per moles of fatty alcohol and condensation products of more or less pre-branched primary alcohols, the branching being predominantly 2-methyl, with from approx. 4 to approx.
12 mol ethylenoxid.12 moles of ethylene oxide.
Zwitterioniske detergenter, såsom betainerne og sulfobetainer-20 ne, med følgende formel er også anvendelige: R2 R—N—R.-X==0Zwitterionic detergents, such as the betaines and sulfobetainers, of the following formula are also applicable: R2 R-N-R.-X == 0
II 4 III 4 I
R3 1-o hvori R er en alkylgruppe med fra ca. 8 til ca. 18 carbonatomer, R3 og R^ hver er en alkylen- eller hydroxyalkylengruppe indeholdende fra ca. 1 til ca. 4 carbonatomer, R4 er en alkylen- eller hydroxyalkylengruppe indeholdende 1 til 4 carbon-25 atomer og X er C eller S=0. Alkylgruppen kan indeholde en eller flere intermediere, såsom amido-, ether- eller polyethei bindinger, eller ikke-funktionelle substituenter, såsom hy- 12Wherein R is an alkyl group having from about 8 to approx. 18 carbon atoms, R 3 and R 2 each are an alkylene or hydroxyalkylene group containing from about 1 to approx. 4 carbon atoms, R4 is an alkylene or hydroxyalkylene group containing 1 to 4 carbon atoms and X is C or S = 0. The alkyl group may contain one or more intermediates, such as amido, ether or polyethyl bond, or non-functional substituents such as
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droxyl aller halogen, der ikke i væsentlig grad påvirker gruppens hydrofobe karakter. Når X er C, kaldes detergenten en betain, og når X er S=0, kaldes detergenten en sulfobetain eller sultain.droxyl all halogen which does not significantly affect the hydrophobic nature of the group. When X is C, the detergent is called a betaine and when X is S = 0, the detergent is called a sulfobetaine or sultain.
5 Kationiske overfladeaktive' midler kan også anvendes. De omfatter overfladeaktive detergentforbindelser, der indeholder en organisk hydrofobgruppe, der udgør en del af en kation, når forbindelsen opløses i vand, og en anionisk gruppe. Typiske kationiske overfladeaktive midler er aminoforbindelser 10 og kvaternære ammoniumforbindelser.Cationic surfactants may also be used. They include surfactant detergent compounds containing an organic hydrophobic group which forms part of a cation when the compound is dissolved in water, and an anionic group. Typical cationic surfactants are amino compounds 10 and quaternary ammonium compounds.
Eksempler på egnede syntetiske kationiske detergenter indbe-ter normale primære aminer med formlen RN^, hvori R er en alkylgruppe indeholdende fra ca. 12 til ca. 15 carbonatomer, diaminer med formlen RNIK^H^Ni^r hvori R er en alkylgruppe 15 indeholdende fra ca. 12 til ca. 22 carbonatomer, såsom N-2-aminoethyl-stearylamin og N-2-aminoethyl-myristylamin, amid-bundne aminer, såsom sådanne med formlen R-jCONITC^H^Ni^, hvori R^ er en alkylgruppe indeholdende fra ca. 8 til ca. 20 carbonatomer, såsom N-2-aminoethylstearylamin og N-aminoethylmyri-20 stylamid, kvaternære ammoniumforbindelser, hvori typisk en af de til nitrogenatomet knyttede grupper er en alkylgruppe indeholdende fra ca. 8 til ca. 22 carbonatomer, og tre af de til nitrogenatomet knyttede grupper er alkylgrupper, der indeholder 1 til 3 carbonatomer, inklusive alkylgrupper bærende indiffe-25 rente substituenter, såsom phenylgrupper, og indeholdende en anion, såsom halogen, acetat, methosulfat etc. Alkylgruppen kan indeholde intermediære bindinger, såsom amidbindinger, der ikke i væsentlig grad påvirker gruppens hydrofobe karakter, f.eks. stearylamidopropyl-kvaternært ammoniumchlorid. Typiske 30 kvaternært ammoniumdetergenter er ethyldimethylstearylammonium-chlorid, benzyldimethylstearylammoniumchlorid, trimethylstearyl-ammoniumchlorid, trimethylcetylammoniumbromid, dimetylethyl-laurylammoniumchlorid, dimethylpropylmyristylammoniumchlorid 13Examples of suitable synthetic cationic detergents include normal primary amines of the formula RN ^ wherein R is an alkyl group containing from ca. 12 to approx. 15 carbons, diamines of the formula RNIK ^ H ^ Ni ^ r wherein R is an alkyl group 15 containing from ca. 12 to approx. 22 carbons, such as N-2-aminoethyl-stearylamine and N-2-aminoethyl-myristylamine, amide-linked amines, such as those of the formula R 1 -CONITC 2 H 2 Ni 2, wherein R 2 is an alkyl group containing from 8 to approx. 20 carbon atoms, such as N-2-aminoethylstearylamine and N-aminoethylmyrimethyl-20-amide, quaternary ammonium compounds, wherein typically one of the nitrogen-linked groups is an alkyl group containing from ca. 8 to approx. 22 carbon atoms and three of the nitrogen atom linked groups are alkyl groups containing 1 to 3 carbon atoms, including alkyl groups bearing inert substituents such as phenyl groups and containing an anion such as halogen, acetate, methosulfate etc. The alkyl group may contain intermediates bonds such as amide bonds that do not significantly affect the hydrophobic nature of the group, e.g. stearylamidopropyl quaternary ammonium chloride. Typical quaternary ammonium detergents are ethyl dimethylstearyl ammonium chloride, benzyldimethylstearyl ammonium chloride, trimethyl stearyl ammonium chloride, trimethylcetylammonium bromide, dimethylethyl-laurylammonium chloride, dimethylpropylmyristylammonium chloride
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og de tilsvarende methosulfater cg acetater.and the corresponding methosulfates and acetates.
Amfolytiske. detergenter er også egnede til opfindelsens formål. Amfolytiske detergenter er velkendte, og mange anvendelige detergenter tilhørende denne klasse er omtalt af A. M.Ampholytic. detergents are also suitable for the purposes of the invention. Ampholytic detergents are well known and many useful detergents belonging to this class are disclosed by A.M.
5 Schwartz, J. W. Perry og J. birch i "Surface Active Agents and5 Schwartz, J. W. Perry and J. birch in "Surface Active Agents and
Detergents", Interscience Publishers, New York, 1958, bind 2. Eksempler på egnede amfotere detergenter indbefatter: alkyl-β-iminodipropionater, RN(C2H4COOM)2r alkyl-Ø-aminopro-pionater, RN (H)C2H4COOM samt langkædede imidazoIderivater 10 med den almene formel: /¾Detergents ", Interscience Publishers, New York, 1958, Volume 2. Examples of suitable amphoteric detergents include: alkyl β-iminodipropionates, RN (C2H4COOM) 2r alkyl-β-aminopropionates, RN (H) C2H4COOM, and long chain imidazole derivatives 10 the general formula: / ¾
N IN I
1212
R-C-N-CH 0CH o0CH oC00MR-C-N-CH 0CH and 0CH oC00M
Z Z zZ Z z
OH CH2COOMOH CH2COOM
hvori R i hver af ovenstående formler er en acyklisk hydrofob gruppe indeholdende fra ca. 8 til ca. 18 carbonatomer, og M er en kation til neutralisering af anionens ladning. Specifikke anvendelige amfotere detergenter indbefatter dinatrium-15 saltet af undecylcykloimidiniumethoxyethionsyre-2-ethionsyre, dodecyl-3-alanin og det indre salt af 2-trimethylaminolaurin-syre.wherein R in each of the above formulas is an acyclic hydrophobic group containing from ca. 8 to approx. 18 carbon atoms, and M is a cation for neutralizing the anion charge. Specific useful amphoteric detergents include the disodium salt of undecylcycloimidinium ethoxyethionic acid-2-ethionic acid, dodecyl-3-alanine and the inner salt of 2-trimethylaminolauric acid.
Vaskemidlet ifølge opfindelsen kan eventuelt indeholde en vaskemiddel-builder af den type, der almindeligvis anvendes i 20 vaskemidler. Egnede buildere indbefatter Æthvert af de kon ventionelle uorganiske vandopløselige buildersalte, såsom eksempelvis vandopløselige salte af phosphater, pyrophospha-ter, ortophosphater, polyphosphater, silicater, carbonater og lignende. Organiske buildere indbefatter vandopløselige 25 phosphonater, polyphosphonater, polyhydroxysulfonater, poly- acetater, carboxylater, polycarbozylater, succinater og lign.The detergent of the invention may optionally contain a detergent builder of the type commonly used in detergents. Suitable builders include any of the conventional inorganic water-soluble builder salts, such as, for example, water-soluble salts of phosphates, pyrophosphates, orthophosphates, polyphosphates, silicates, carbonates and the like. Organic builders include water-soluble phosphonates, polyphosphonates, polyhydroxy sulfonates, polyacetates, carboxylates, polycarbozylates, succinates and the like.
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Specifikke eksempler på uorganiske phosphatbuildere indbefatter natrium- og kaliumtripolyphosphater, -pyrophosphater og -hexametaphosphater. De organiske polyphosphonater indbefatter specielt eksempelvis natrium- og kaliumsaltene af ethan-1-5 hydroxy-1,1-diphosphonsyre og natrium- og kaliumsaltene af ethan-1,2-triphosphonsyre. Eksempler på disse og andre phos-phorbuilderforbindelser er anført i USA patentskrifterne nr.Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates. In particular, the organic polyphosphonates include, for example, the sodium and potassium salts of ethane-1-5 hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane-1,2-triphosphonic acid. Examples of these and other phos-phorbuilder compounds are disclosed in United States Patent Nos.
3.213.030, nr. 3.422.021, nr. 3.422.137 og 3.400.176. Penta-natriumtripolyphosphat og tetranatriumpyrophosphat er særlig 10 foretrukne vandopløselige uorganiske buildere.3,213,030, Nos. 3,422,021, Nos. 3,422,137 and 3,400,176. Penta-sodium tripolyphosphate and tetrasodium pyrophosphate are particularly preferred water-soluble inorganic builders.
Specifikke eksempler på ikke-phosphorholdige uorganiske buildere indbefatter vandopløselige uorganiske carbonat-, bicar-bonat- og silikatsalte. Alkalimetal-, f.eks. natrium og kalium, carbonaterne, bicarbonaterne og silikaterne er særlig anvende-15 lige.Specific examples of non-phosphorus-containing inorganic builders include water-soluble inorganic carbonate, bicarbonate, and silicate salts. Alkali metal, e.g. sodium and potassium, the carbonates, bicarbonates and silicates are particularly useful.
Vandopløselige organiske buildere kan også anvendes. F.eks. alkalimetal-, ammonium- og substituerede ammoniumpolyacetater, -carboxylater, -polycarboxylater og -polyhydroxysulfonater er anvendelige buildere til midlerne og fremgangsmåderne ifølge 20 opfindelsen. Specifikke eksempler på polyacetat- og polycar-boxylatbuildere indbefatter natrium-, kalium-, lithium-, ammonium- og substituerede ammoniumsalte af ethylendiamintetra-eddikesyre, nitrilotrieddikesyre, benzenpolycarboxylsyrer (dvs. penta- og tertracarboxylsyrer), carboxymethoxyravsyre 25 og citronsyre.Water-soluble organic builders can also be used. Eg. alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates are useful builders for the agents and methods of the invention. Specific examples of polyacetate and polycarboxylate builders include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, benzene polycarboxylic acid (i.e., penta and tertracarboxylic acids)
Blegemidlerne ifølge opfindelsen fremstilles ved blanding af bestanddelene som illustreret i det følgende. Ved fremstilling af vaskemidler indeholdende blegemidlet i kombination med en overfladeaktiv detergentforbindelse og/eller buildersalte, 30 kan blegemidlets komponenter blandes direkte med detergent-forbindelsen, builderen og lignende. Alternativt kan peroxy-genaktivatoren, MPPA og peroxygenforbindelsen overtrækkes med et-overtræksmateriale til forbedring af stabiliteten og/ i i 15The bleaching agents of the invention are prepared by mixing the ingredients as illustrated below. In the preparation of detergents containing the bleach in combination with a surfactant detergent compound and / or builder salts, the components of the bleach can be mixed directly with the detergent compound, builder and the like. Alternatively, the peroxy gene activator, MPPA, and peroxygen compound may be coated with one-coat material to improve stability and /
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eller hindre for tidlig aktivering af blegemidlet. Overtræknings-proccesen udføres i overensstemmelse med procedurer, der er velkendte. Egnede overtræksmaterialer indbefatter sådanne forbindelser som magnesiumphosphat, polyvinylalkohol, laurin-5 syre eller salte deraf og lignende.or prevent premature activation of the bleach. The coating process is performed in accordance with procedures well known in the art. Suitable coating materials include such compounds as magnesium phosphate, polyvinyl alcohol, lauric acid or salts thereof and the like.
EKSEMPEL 1EXAMPLE 1
AfprøvninqsprocedureAfprøvninqsprocedure
Blegningsforsøg blev udført med standardfarvede prøvetekstiler (beskrevet nedenfor) under anvendelse af de forskellige 10 blege- og vaskemidler, der er beskrevet i dette eksempels tabel 1, i en tergotometerbeholder fremstillet af US Testing Company. Tergotometeret blev holdt ved en konstant temperatur på 49°C og arbejdede ved 100 omdrejninger pr. min.Bleaching experiments were performed with standard dyed sample fabrics (described below) using the various bleach and detergents described in Table 1 of this example in a tergotometer container manufactured by the US Testing Company. The tergotometer was kept at a constant temperature of 49 ° C and operated at 100 rpm. mine.
Hvert af de i tabel 1 nævnte forsøgsmaterialer blev sat til 15 1 liter ledningsvand ved 49°C med en vandhårdhed på ca. 100 ppm, beregnet som calciumcarbonat. Forsøgsmaterialerne blev omrørt i ca. 1 min., og derefter blev en blandet tekstilpåfyldning . , bestående af to stykker tekstil, hvert af dem (7,5 cm x 10 cm) bestående af de nedenfor beskrevne plettede tekstiler, 20 sat til hver vaskebeholder. Efter en vask på 15 min.ved 49°C blev forsøgstekstilerne skyllet i ledningsvand ved 38°C og derpå tørret. Den procentiske pletfjernelse blev målt ved at tage en reflektansaflæsning for hver farvet forsøgstekstil forud for og efter vaskningen under anvendelse af 25 et Gardner Color Difference Meter, og den procentiske pletfjernelse (% S.R.) blev beregnet som følger: (Rd efter vaskning) - (Rd før vaskning) % S.R. = -1- x 100 (Rd før forurening) - (Rd før vaskning) hvori "Rd før vaskning" betegner Rd-værdien efter pletning.Each of the test materials listed in Table 1 was added to 15 L of tap water at 49 ° C with a water hardness of approx. 100 ppm, calculated as calcium carbonate. The test materials were stirred for approx. 1 min, and then a mixed textile filling. , consisting of two pieces of textile, each of them (7.5 cm x 10 cm) consisting of the spotted textiles described below, 20 set for each wash container. After a wash of 15 minutes at 49 ° C, the test fabrics were rinsed in tap water at 38 ° C and then dried. The percent stain removal was measured by taking a reflectance reading for each colored test fabric before and after washing using a Gardner Color Difference Meter, and the percent stain removal (% SR) was calculated as follows: (Rd after washing) - (Rd before washing)% SR = -1- x 100 (Rd before pollution) - (Rd before washing) where "Rd before washing" denotes the Rd value after staining.
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Størrelsen af den procentiske pletfjernelse, der blev beregnet for alle fem tekstilstykker, blev benyttet til udregning af et gennemsnit for hvert forsøgvaskemiddel. En forskel på mere end 2% i gennemsnittet for fem afprøvede 5 plettede tekstilstykker betragtes som værende signifikant.The percentage of stain removal calculated for all five textile pieces was used to calculate an average for each test detergent. A difference of more than 2% in the average of five tested 5 spotted textile pieces is considered to be significant.
Ved afslutning af hver vask blev vaskeopløsningensindhold af aktivt oxygen bestemt ved syrning med fortyndet svovlsyre efterfulgt af behandling af vaskeopløsningen med kaliumiodid og en mindre mængde ammoniummolybdat, hvorpå der blev titre-10 ret med standardiseret natriumthiosulfat under anvendelse af stivelse som indikator.At the end of each wash, the active oxygen wash solution content was determined by dilution with dilute sulfuric acid, followed by treatment of the wash solution with potassium iodide and a small amount of ammonium molybdate, then titrated with standard sodium thiosulfate using starch as indicator.
De respektive pletter og forsøgstekstiler var som følger:The respective stains and test fabrics were as follows:
Fletning med: Forsøgstektiler 1. Drue - 65 dacron - 35 bomuld 15 2. Blåbær - bomuld 3. Sulfofarve- stof - EMPA 115 (bomuld) 4. Rødvin - EMPA 114 (bomuld) 5. Kaffe/te - bomuld 20 Plettede forsøgtekstiler 1 og 2 fremstilledes ved at føre ruller af u.farvet tekstil gennem et foulard- og tørreapparat (fremstillet af Benz i Zurich, Schweiz) indeholdende enten drue- eller blåbæropløsninger ved 32°C. Efter tørring ved 121°C udskæres tekstilet i tekstilstykker på 7,5 cm x 25 io cm. 80 af disse tekstilstykker, der er imprægneret med den samme plettype, skylles i 65 liter ved 29°C i en automatisk husholdningsvaskemaskine. Derpå tørres de ved hjælp af en passage gennem en Beseler tryktørrer ved en maskintem-peraturindstilling på 6 og en hastighed på 10.Braid with: Test fabrics 1. Grape - 65 dacron - 35 cotton 15 2. Blueberries - cotton 3. Sulfur dye - EMPA 115 (cotton) 4. Red wine - EMPA 114 (cotton) 5. Coffee / tea - cotton 20 Spotted experimental fabrics 1 and 2 were prepared by passing rolls of unpainted textile through a foulard and dryer (manufactured by Benz in Zurich, Switzerland) containing either grape or blueberry solutions at 32 ° C. After drying at 121 ° C, the fabric is cut into 7.5 cm x 25 io cm textile pieces. Eighty of these textile pieces impregnated with the same stain type are rinsed in 65 liters at 29 ° C in an automatic household washing machine. They are then dried by passage through a Beseler pressure dryer at a machine temperature setting of 6 and a speed of 10.
30 Plettede tekstiler 3 og 4 købes hos Testfabrics Incorporated 1730 Spotted fabrics 3 and 4 are purchased from Testfabrics Incorporated 17
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i Middlesex, New Jersey, og skæres i tekstilstykker på 7,5 cm x 10 cm.in Middlesex, New Jersey, and cut into 7.5 cm x 10 cm textile pieces.
Det plettede tekstil 5 fremstilledes ved omrøring og gennemvæd-ning af uforurenede bomuldsstrimler (46 cm x 91 cm) i en vaske-5 maskine fyldt med en opløsning af kaffe/te (vægtforhold 8:1) ved 66°C. Maskinen får lov til at skylle- rotationstørre til fjernelse af kaffe/te-opløsningen. Det farvede · tekstil ma-skinvaskes derpå to gange med varm opløsning af pyrophosphat-overfladeaktivtmiddel efterfulgt af to komplette vaskecykler med 10 vand ved 60°C. Strimlerne tørres derpå ved hjælp af to passager gennem en "Ironrite"-maskine indstillet på 10 og skæres derpå i tekstilstykker på 7,5 cm x 10 cm.The spotted textile 5 was prepared by stirring and soaking uncontaminated cotton strips (46 cm x 91 cm) in a washing machine filled with a coffee / tea solution (weight ratio 8: 1) at 66 ° C. The machine is allowed to rinse rotation dryer to remove the coffee / tea solution. The dyed textile is then machine-washed twice with warm solution of pyrophosphate surfactant followed by two complete wash cycles of 10 water at 60 ° C. The strips are then dried by means of two passages through an "Ironrite" machine set to 10 and then cut into 7.5 cm x 10 cm textile pieces.
Et granulært vaskemiddel (her betegnet som "HDD") blev fremstillet ved hjælp af konventionel sprøjtetørring og havde 15 følgende tilnærmelsesvise sammensætning:A granular detergent (herein referred to as "HDD") was prepared by conventional spray drying and had the following approximate composition:
Sammensætning Vægt% natriumtridecylbenzensulfonat 15 ethoxyleret (^“C^-primær alkohol (7 mol EO/mol alkohol) 1 20 natriumtripolyphosphat 33 natriumcarbonat 5 natriumsilikat 7 natriumcarboxymethylcellulose 0,5 optiske klaringsmidler 0,2 25 parfume 0,2 vand 11 natriumsulfat restComposition Weight% Sodium Tridecylbenzenesulfonate 15 Ethoxylated (^ C C Primary Alcohol (7 mol EO / mol Alcohol) 1 20 Sodium Tripolyphosphate 33 Sodium Carbonate 5 Sodium Silicate 7 Sodium Carboxymethyl Cellulose 0.5 Optical Clarifiers 0.2 25 Perfume 0.2 Water 11 Sodium Sulphate
Vaskemidler A-D indeholdende HDD blev sammensat som anført i tabel 1.Detergents A-D containing HDD were composed as listed in Table 1.
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Tabel 1Table 1
Komponent SammensætningComponent Composition
A B C DA B C D
Detergent, HDD 4,50 g 4,50 g 4,50 g 4,50 g 5 H-48(1) ---- 0,25 0,25 0,25 DTPMP---- ---- 0,02 0,09Detergent, HDD 4.50 g 4.50 g 4.50 g 4.50 g 5 H-48 (1) ---- 0.25 0.25 0.25 DTPMP ---- ---- 0, 02 0.09
Natriumperborat 0,32 0,16 0,16 0,16Sodium perborate 0.32 0.16 0.16 0.16
Phathalsyreanhydrid ---- 0,125 0,125 0,125 (1) Et blegemiddel indeholdende monoperoxyphtalsyre (som mag- 10 nesiumsalt) opnået fra Interox Chemicals Houston, Texas og med et indhold af aktivt oxygen på 5,1% (2) Natriumdiethylentriaminpentamethylenphosphonat opnået fra P.A. Hunt Chemical Corporation, Lincoln, Rhode Island.Phthalic anhydride ---- 0.125 0.125 0.125 (1) A bleach containing monoperoxyphthalic acid (as magnesium salt) obtained from Interox Chemicals Houston, Texas and containing an active oxygen content of 5.1% (2) Sodium diethylenetriamine pentamethylene phosphonate obtained from P.A. Hunt Chemical Corporation, Lincoln, Rhode Island.
Midlerne A til D blev afprøvet i overensstemmelse med den 15 ovenfor beskrevne procedure, og resultatet af blegningsforsøgene er anført i tabel 2, der angiver begyndelses- og slutværdierne for aktivt oxygen (A.O.) i vaskeopløsningen (udtrykt som henholdsvis "gram til at begynde med" og "tilbageværende gram") og forureningsfjernelsen opnået for hver af de fem 20 forureninger eller pletninger.Agents A to D were tested in accordance with the procedure described above, and the results of the bleaching tests are listed in Table 2, which indicates the initial and final values of active oxygen (AO) in the wash solution (expressed as "grams to begin with", respectively). and "residual gram") and the pollution removal achieved for each of the five 20 contaminants or stains.
1919
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Tabel 2Table 2
SAMMENLIGNENDE BLEGEVIRKNINGCOMPARATIVE WHITE EFFECT
Sammensætningcomposition
Gram til at begynde med — — — — 5 (A.O. x 103) 32,8 28,7 28,7 28,’7Grams to begin with - - - - 5 (A.O. x 103) 32.8 28.7 28.7 28, '7
Tilbageværende gram (A.O. x 103) 30,4 12,4 19,5 19,9Remaining grams (A.O. x 103) 30.4 12.4 19.5 19.9
Gram forbrugt (A.O. x 103) 2,4 16,4 9,2 8,8 10 Farve- eller forureningsfjernelse: % % % %Gram Consumed (A.O. x 103) 2.4 16.4 9.2 8.8 10 Color or Pollution Removal:%%%%
Drue 61 63 67 67Grapes 61 63 67 67
Blåbær 56 65 67 68Blueberries 56 65 67 68
Sulfofarvestof (EMPA 115) 3444 15 Rødvin (EMPA 114) 41 46 49 53Sulfur Dye (EMPA 115) 3444 15 Red Wine (EMPA 114) 41 46 49 53
Kaffe/te 26 30 39 40Coffee / tea 26 30 39 40
Gennemsnit (%) 37 42 45 46Average (%) 37 42 45 46
Resultaterne i tabel 2 viser, at midlerne C og D opbruger betydelig mindre aktivt oxygen under opnåelse af forbedret 20 farve- eller forureningsfjernelse i forhold til midlet B, der er et middel svarende til midlerne C og D med den undtagelse, at det ikke indeholder chelateringsmidlet DTPMP.The results in Table 2 show that agents C and D consume significantly less active oxygen to achieve enhanced color or contaminant removal over agent B, which is an agent similar to agents C and D except that it does not contain the chelating agent. DTPMP.
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EKSEMPEL 2EXAMPLE 2
Vaskemidler E-J blev sammensat til at indeholde 0,15% detergentkoncentration som vist nedenfor i tabel 3.Detergents E-J were formulated to contain 0.15% detergent concentration as shown below in Table 3.
Tabel 3 5 Komponenter SammensætningTable 3 5 Components Composition
E F G Η I JE F G Η I J
Detergent, HDD 1,50 g 1,50 g 1,50 g 1,50 g 1,50 g 1,50 g H-48(1) 0,20 0,20 0,20 0,07 0,07 0,07 DTPMP1 ---- 0,02 ---- ---- 0,02 ---- 10 EDTA2 ---- ---- 0,02 ---- ---- 0,02Detergent, HDD 1.50 g 1.50 g 1.50 g 1.50 g 1.50 g 1.50 g H-48 (1) 0.20 0.20 0.20 0.07 0.07 0. 07 DTPMP1 ---- 0.02 ---- ---- 0.02 ---- 10 EDTA2 ---- ---- 0.02 ---- ---- 0.02
Natriumperborat (10,1% A.O.) ---- ---- ---- 0,15 0,15 0,15Sodium perborate (10.1% A.O.) ---- ---- ---- 0.15 0.15 0.15
Phthalsyreanhydrid ---- ---- ----- 0,06 0,06 0,06 (1) Et blegemiddel indeholdende monoperoxyphthalsyre (som 15 magnesiumsalt) opnået fra Interox Chemicals, Houston,Phthalic anhydride ---- ---- ----- 0.06 0.06 0.06 (1) A bleach containing monoperoxyphthalic acid (such as magnesium salt) obtained from Interox Chemicals, Houston,
Texas, og med et indhold af aktivt oxygen på 5,1%.Texas, and with an active oxygen content of 5.1%.
Natriumdiethylentriaminpentamethylenphosphonat opnået fra P.A. Hunt Chemical Corporation, Lincoln, Rhode Island.Sodium diethylenetriamine pentamethylene phosphonate obtained from P.A. Hunt Chemical Corporation, Lincoln, Rhode Island.
22
Ethylendiamintetraeddikesyre, dinatriumsalt.Ethylenediaminetetraacetic acid, disodium salt.
20 Midlerne E til J blev afprøvet i overensstemmelse med procedurerne beskrevet i eksempel 1, og resultaterne af blegningsforsøgene er opført i tabel 4. Begyndelses- og slutværdierne for aktivt oxygen i vaskeopløsningen samt plet- eller forureningsfjernelsen opnået for de 5 viste farvninger er udtrykt 25 som i tabel 2 i eksempel 1.The agents E to J were tested in accordance with the procedures described in Example 1, and the results of the bleaching experiments are listed in Table 4. The initial and final values of active oxygen in the wash solution as well as the stain or contaminant removal obtained for the 5 stains shown are expressed as 25. in Table 2 of Example 1.
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Tabel 4Table 4
SAMMENLIGNENDE BLEGEVIRKNINGCOMPARATIVE WHITE EFFECT
E F G Η I JE F G Η I J
Gram til at begynde med 5 (A.O. x 1(T) 10,2 10,2 10,2 18,6 18,6 18,6Grams to begin with 5 (A.O. x 1 (T) 10.2 10.2 10.2 18.6 18.6 18.6
Tilbageværende gram (A.O. x 10J) 3,6 5,5 3,6 9,4 13,8 10,0Remaining grams (A.O. x 10J) 3.6 5.5 3.6 9.4 13.8 10.0
Gram forbrugt (A.O. x 10 ) 6,6 4,7 6,6 9,2 4,8 8,6 10 Farvef jernelse: 111111Gram Consumed (A.O. x 10) 6.6 4.7 6.6 9.2 4.8 8.6 10 Color Iron: 111111
Drue 65 64 64 62 63 61Grapes 65 64 64 62 63 61
Blåbær 46 47 44 43 47 44Blueberries 46 47 44 43 47 44
Sulfofarvestof (EMPA 115) 344455 Rødvin (EMPA 114) 37 35 35 33 34 33 15 Kaffe/te 70 72 70 11 82 86Sulfur dye (EMPA 115) 344455 Red wine (EMPA 114) 37 35 35 33 34 33 15 Coffee / tea 70 72 70 11 82 86
Gennemsnit (%) 44 44 43 45 46 46Average (%) 44 44 43 45 46 46
Resultaterne i tabel 4 viser, at blegevirkningen opnået ved hjælp af midlet G forbedres ved anvendelse af midlerne I og J ifølge opfindelsen, der indeholder en formindsket mængde 20 af MPPA-blegekomponenten i forhold til midler med F og G,The results in Table 4 show that the bleaching effect obtained by the agent G is improved by using the means I and J according to the invention, which contain a reduced amount 20 of the MPPA bleach component compared to agents with F and G,
men som desuden indeholder perborat og phthalsyreanhydridak-tivator. Endvidere viser en sammenligning mellem virkningen af midlerne I og J, at midlet I tilvejebringer en blegeeffek-tivitet, der er ækvivalent i relation til midlet J, men under 25 forbrug af betydelig mindre aktivt oxygen, idet midlerne Ibut which additionally contains perborate and phthalic anhydride activator. Furthermore, a comparison between the effect of agents I and J shows that agent I provides a bleaching efficiency equivalent to agent J but less consumption of significantly less active oxygen, the agents I
og J er identiske med undtagelse af tilstedeværelsen af DTPMP i det førstnævnte middel og EDTA i det sidstnævnte middel.and J are identical except for the presence of DTPMP in the former and EDTA in the latter.
Claims (9)
Applications Claiming Priority (2)
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US43249082A | 1982-10-04 | 1982-10-04 | |
US43249082 | 1982-10-04 |
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DK457083D0 DK457083D0 (en) | 1983-10-04 |
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DK158954B true DK158954B (en) | 1990-08-06 |
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DK457083A DK158954B (en) | 1982-10-04 | 1983-10-04 | WHITE DETERGENTS CONTAINING MONOPEROXYPHTHALIC ACID, A CHELATING COMPOUND AND AN ACTIVATOR FOR THE PEROXYGEN COMPOUND AND THE USE OF TOUCH WASH |
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AT (1) | AT394575B (en) |
AU (1) | AU555990B2 (en) |
BE (1) | BE897905A (en) |
CA (1) | CA1216779A (en) |
CH (1) | CH656397A5 (en) |
DE (1) | DE3335011A1 (en) |
DK (1) | DK158954B (en) |
FR (1) | FR2535749B1 (en) |
GB (1) | GB2129454B (en) |
GR (1) | GR79703B (en) |
IT (1) | IT1206157B (en) |
MX (1) | MX159085A (en) |
NL (1) | NL8303403A (en) |
NO (1) | NO833581L (en) |
PT (1) | PT77435B (en) |
SE (1) | SE455792B (en) |
ZA (1) | ZA837074B (en) |
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CS249980B1 (en) * | 1984-02-29 | 1987-04-16 | Jaroslav Simunek | Laundry agent with bleaching efficiency |
SE8502752L (en) * | 1984-06-22 | 1985-12-23 | Colgate Palmolive Co | WHITE AND WASHABLE COMPOSITION, FREE FROM WATER-SOLUBLE SILICATES |
US5030380A (en) * | 1989-06-27 | 1991-07-09 | Lever Brothers Company, Division Of Conopco, Inc. | Polymeric electrolyte-hydrogen peroxide adducts |
JPH10512601A (en) * | 1994-11-18 | 1998-12-02 | ザ、プロクター、エンド、ギャンブル、カンパニー | Bleach detergent compositions containing bleach activators effective at low perhydroxyl concentrations |
CN115960292A (en) * | 2022-12-02 | 2023-04-14 | 上海昶法新材料有限公司 | Maleic anhydride-acrylic acid copolymer papermaking chelating agent and preparation method thereof |
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US3637339A (en) * | 1968-03-07 | 1972-01-25 | Frederick William Gray | Stain removal |
LU61828A1 (en) * | 1970-10-07 | 1972-06-28 | ||
EP0027693B2 (en) * | 1979-10-18 | 1988-05-11 | Interox Chemicals Limited | Magnesium salts of peroxycarboxylic acids, processes for their preparation and their use as bleaching agents in washing compositions, and processes |
CA1158129A (en) * | 1980-03-27 | 1983-12-06 | Dennis Postlethwaite | Detergent bleach compositions |
US4318647A (en) * | 1980-04-07 | 1982-03-09 | General Electric Company | Adjustable insert seat and wedge assembly for an indexable boring cutter |
NZ202252A (en) * | 1981-10-29 | 1986-04-11 | Colgate Palmolive Co | Monoperoxyphthalic acid bleaching and laundering compositions |
-
1983
- 1983-09-22 GR GR72511A patent/GR79703B/el unknown
- 1983-09-22 ZA ZA837074A patent/ZA837074B/en unknown
- 1983-09-28 AU AU19655/83A patent/AU555990B2/en not_active Ceased
- 1983-09-28 DE DE19833335011 patent/DE3335011A1/en not_active Withdrawn
- 1983-09-30 PT PT77435A patent/PT77435B/en not_active IP Right Cessation
- 1983-09-30 IT IT8349089A patent/IT1206157B/en active
- 1983-10-03 MX MX198990A patent/MX159085A/en unknown
- 1983-10-03 CA CA000438182A patent/CA1216779A/en not_active Expired
- 1983-10-03 NO NO833581A patent/NO833581L/en unknown
- 1983-10-03 FR FR8315721A patent/FR2535749B1/en not_active Expired
- 1983-10-04 AT AT0350783A patent/AT394575B/en not_active IP Right Cessation
- 1983-10-04 BE BE0/211640A patent/BE897905A/en not_active IP Right Cessation
- 1983-10-04 NL NL8303403A patent/NL8303403A/en not_active Application Discontinuation
- 1983-10-04 DK DK457083A patent/DK158954B/en not_active Application Discontinuation
- 1983-10-04 GB GB08326530A patent/GB2129454B/en not_active Expired
- 1983-10-04 CH CH5399/83A patent/CH656397A5/en not_active IP Right Cessation
- 1983-10-04 SE SE8305437A patent/SE455792B/en not_active IP Right Cessation
Also Published As
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AU1965583A (en) | 1984-04-12 |
SE455792B (en) | 1988-08-08 |
IT8349089A0 (en) | 1983-09-30 |
FR2535749A1 (en) | 1984-05-11 |
NL8303403A (en) | 1984-05-01 |
CA1216779A (en) | 1987-01-20 |
CH656397A5 (en) | 1986-06-30 |
PT77435A (en) | 1983-10-01 |
DK457083D0 (en) | 1983-10-04 |
GB2129454A (en) | 1984-05-16 |
AU555990B2 (en) | 1986-10-16 |
GR79703B (en) | 1984-10-31 |
BE897905A (en) | 1984-04-04 |
IT1206157B (en) | 1989-04-14 |
ZA837074B (en) | 1985-05-29 |
PT77435B (en) | 1986-03-18 |
AT394575B (en) | 1992-05-11 |
SE8305437L (en) | 1984-04-05 |
GB8326530D0 (en) | 1983-11-02 |
DE3335011A1 (en) | 1984-04-05 |
DK457083A (en) | 1984-04-05 |
FR2535749B1 (en) | 1987-11-06 |
GB2129454B (en) | 1986-03-05 |
MX159085A (en) | 1989-04-14 |
SE8305437D0 (en) | 1983-10-04 |
NO833581L (en) | 1984-04-05 |
ATA350783A (en) | 1991-10-15 |
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