SK72493A3 - Detergent compositions containing lipase and water-soluble quaternary ammonium compounds - Google Patents

Detergent compositions containing lipase and water-soluble quaternary ammonium compounds Download PDF

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SK72493A3
SK72493A3 SK724-93A SK72493A SK72493A3 SK 72493 A3 SK72493 A3 SK 72493A3 SK 72493 A SK72493 A SK 72493A SK 72493 A3 SK72493 A3 SK 72493A3
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alkyl
water
surfactant
surfactants
composition
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SK724-93A
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English (en)
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Alastair Pretty
Robin S Hargrove
Andre C Baeck
Alfred Bush
Andre C Convents
Jean-Paul Boutique
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Procter & Gamble
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Priority claimed from EP91870006.3A external-priority patent/EP0495344A1/en
Application filed by Procter & Gamble filed Critical Procter & Gamble
Publication of SK72493A3 publication Critical patent/SK72493A3/sk

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14—Hydrolases (3)
    • C12N9/24—Hydrolases (3) acting on glycosyl compounds (3.2)
    • C12N9/2402—Hydrolases (3) acting on glycosyl compounds (3.2) hydrolysing O- and S- glycosyl compounds (3.2.1)
    • C12N9/2405—Glucanases
    • C12N9/2434—Glucanases acting on beta-1,4-glucosidic bonds
    • C12N9/2437—Cellulases (3.2.1.4; 3.2.1.74; 3.2.1.91; 3.2.1.150)
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y302/00—Hydrolases acting on glycosyl compounds, i.e. glycosylases (3.2)
    • C12Y302/01—Glycosidases, i.e. enzymes hydrolysing O- and S-glycosyl compounds (3.2.1)
    • C12Y302/01004—Cellulase (3.2.1.4), i.e. endo-1,4-beta-glucanase
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Genetics & Genomics (AREA)
  • Zoology (AREA)
  • General Health & Medical Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Molecular Biology (AREA)
  • Biomedical Technology (AREA)
  • Biotechnology (AREA)
  • Microbiology (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Description

Povrchovo sktivne prostrit---ky obsahujúce IfpdzU a vo vy’e rozpustné kvárterné 'asóniové zlúčeniny
Oblasť techniky — · ·;·Γ E .!.,? '.*?!?
7ei;to vynález se týka povrckovo-fiktívnych prostriedkov, sajúcich zlepčené vlastnosti voči odstraňovaniu znečistenks, nsjsa potom takého znečistenia, ktoré oosr.huýe tr iglycer L-ž · roteraŕčí stav techniky &y, vo hovo a’ktívTse prostriedky techniky. Hlavne- sú p-oton r-re -povrchovo aktívne □bre
S L.
ηγΌ k-.I ’-z
n.
popiscn-2 striedky, ríklad tO tách j reprezentuje
011 15 J, popisujúci použitie lipés p-racle prostriedky, ako aj 2?-A-23> 1P-A-341 939» vzťahujúcich sa vždy ne íviií prostriedky, obsahujúce lipasu ako prostriedok sa t r eno v sr. i e znečistenia.
Produkcia 11pasy z určitých mikroorganizmov je popísaná napríklad v EP-A-214 761 a EP-A-258 O6ä.
ť·*· e bo gkt oc s
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*- - 4»
«.Ô»·. t príprave ad i
El—ä-23c 33 tív ňupvce zlúč i o v á zlúčení n,v, v továrňach -„-rl
Teraz bolo zistené, že pri kombinácii niektorými určitými vo vode ro zlúčenínasi, vaní nečistôt obsahujúcich trlglycerid z látok, s č vané efekty vo vzťahu protLpdsobonis ns opätovné zs neboli z.at i&ľ dosahovaná pri žiadnom z vysále uvedených pr í päenzýmov 1 i pas? z pu s tn.ýs i kvár t e rnýs i dochádza k neočakávanému zlepšeniu pri ocstranoe po3kyto~ špiňovanie, äov.
Podstata vynálezu
Podstata vynálezu bude Šalej popísané postupne po nasledujúcich častiach?
Vo vode rozpustné kvarterné amóniové zlúčeniny
V tomto vynáleze používané vo vode rozpustné kvarterné amóniové zlúčeniny majú všeobecný vzorec:
/1/ X“ kde R^ je Cg až C^g alkyl alebo je P^-T-C-Rg, kde T je
O, NH alebo alkyl, R^ je divá- © lentný C^ až C-j alkylénová skupina alebo , kde m je číslo od 1 do 8, kde každý z R2, ^3 a ^4 sú navzájom nezávislé a znamenajú až alkyl alebo hydroxyl alkyl, benzyl, alebo - /C^^O/^H ^de x je číslo s hodnotou od 2 do 5, nie viac ako jeden z R2, R^ alebo R^ znamenajú benzyl a X” je anión; alebo /ii/ /CH2/ / X n-r2 +
kde n je 2, 3 alebo 4, s výhodou 2, Q je CH, CHg alebo N,a R^ a R2 sú rovnaké ako vo všeobecnom vzorci uvedenom v bode /i/ a X“ znamená anión.
Výhodné dĺžky reťazcov pre R^ sú C^2 až C^ najme ak je alkylová skupina zmesou reťazcov dĺžok, odvodených od tukov z jadier kokosových alebo palmových, alebo sú odvodené od synteticky získaných látok z olefínov alebo 0X0 alkoholov. Výhodnými skupinami pre R2, R^ a R^ sú metylové a hydroxyetylové skupiny a anión X môže byť vybraný zo skupiny, ktorú tvorí halogenid, metosulfát, acetát a fosfát a to vo forme ich iónov.
Vhodnými kvarternýml amóniovými zlúčeninami s všeobecným vzorcom ' /1/ na tu uvedené použitie môžu byť napríklad:
kokosový trimetylamóniumchlorid alebo bromid kokosový metyldihydroxyetylamóniumchlorid alebo bromid d e cy 1 trie tyl amóniumchl or id decyldimetylhydroxyetylamóniumchlorid alebo bromid ci2 ež cir
KOKOSOVý dl issty1hyd roxy a ty1saÓniurach 1 or 1 d net?;lhydroxye t.vl aísóniuÄchlorid rayris tyl tr irae tylamónlumas ty lsul f d t
1euryla imety1benzyl wzónluschlor td alc bo brómíd leurylóImetyl/etériox.y/^íí^iónlumehlorL ' al-bo broiaid cholinové estery /zlúčeninv vSeobeetiého vzorce /1/ kde R,
-C!t2-O-C-C^2-14 alkyl 6 znamenajú laetyl/ d i-alkyllmldazolíny / zlúčeniny e všeobecným vzorcom. /1/ /.
Tieto vyč.Šie uvedené vo vode rozpustná kat tónové komponenty v prostriedkoch podľa tohto vynálezu,, stí schopné existencie v katiónovej forme v 0,1 Xnam vodnom roztoku pri hodnote pH 10.
Uvedené vo vode rozpustné katiónová zlúčeniny sú prítomné v množstve od 9,1 .6 hraotnostných do 10 £ haotnostnýeh, vzhľedos ne celkovú hmotnosť uvedených povrchovo aktívnych prostriedkov.
ľnzým lipasn
Tu uvedené prostriedky obsahujú enzý® llpesu, je možné zvoliť z širokej oblasti lipés; lipesy sú popísané najme pr© takéto prípady napríklad v nesledujúcich patentových prihláškach: EP 0 214 761, S? 0 256 066, Er 9 205 208, EP 0 206 390. Vhodné sú nojmš tisto komerčne dostupné 11pasové preparáty; Novo Lipolesé^, Ameno lipases CE, F, B, ÄP, ä-AP, AML e CES, a i^eito lipases yi-30, OF, a PL, taktiež esterase MM, Lipozya, 5P225, SP285, Saiken lípese, Enzeco 11pase, Toyo Jožo llpase a Piosynth llpese /továrne značky/,
V genetickom inžinierstve se u enzýmov môže dosiahnuť pomocou extrakcie vhodných génov lipasy, tj. génu pre lipasu z Husticole lanyglnosa alebo z ich mutantov, a zavedením a expres iou génu elebo jeho derivátu do vhodného produkčného organizmu ako je Aspergillus. Je možné aplikovať a adaptovať spôsoby, popísané v WO 88/02775 /Kovo/, EP 0 243 33^ /Labofina/ a EP 0 268 452 /Genencor/·
V uvedenom prostriedku je dená llpasa prítomné v množstve od 10 LU do 590? LU/g prostriedku. 1 UJ je lipolytická aktivite, ktorá sa vzťahuje na 1 mikroad t í. trova telí;·? 3 kyseliny butyrovej r· e Jednu minútu 33 nasledujúcich potíš U-n o k:
teplota 30 °C p - j· i y ú substrát tributyrín /Podrobnosti boli publikované v iiOVO publikácii Aľ 95,4/1/.
Pokiaľ jt 1 i pašou Lipolaaŕ^ 100 kLU, pohybuje sa jej úroveň typicky v rozmedzí oô 0,01 do 5 * hmotnostných, vzhľadom r.ô celkovú hmotnosť uvedeného prostriedku.
Povrchovo aktívne činidlo ¥ povrchovo aktívnych prostriedkoch sť’íu byť použité povrchovo aktívne látky z veľmi širokého rozmedzia. Typický zoznam anténových, ne iónových, asfolytlckých s tried obojakých iónov a látok, patriacich k týmto povrchovo aktívnym látkam, je uvedený v poteňte US 3, 664,961, podanom Sorrlsom dňa
23. mája 1972.
Tvlásť vhodná sú zmesi anténových povrchovo aktívnych látok, najme aulfonátových a sulfátových povrchovo aktívnych látok,v hffiotnostnoa pomere od 5 : 1 do 1 : 2, s výhodou od 3:1 do 2 : 3, výhodnejšie oô 3 : 1 do 1 : 1. Medzi výhodné sulfonéty patrí alkyl benzén suIfoná ty majúce od 9 do 15, najme od 11 do 13 atómov uhlíka v alkylovos radikále, a alfs-su.lfonátované aetvi mastné kyseliny e to estéry týchto kyselín, V/ktorých sú aestné kyseliny odvodené oô C12 - C1£ mastných zdrojových látok, s výhodou potom od Cj- mefttných zdrojových látok. V každom prípade je katiónom alkalický kov, vybraný zo sodného sono- alebo polyetanolemínu, alebo amónneho nono- elebo polyetanolamínu. Výhodné sulfátové povrchovo aktívne látky sú alkyl sulfáty sajúce od 12 do 18 ató mov uhlíka v elkylovoEi radikále, poprípade v príaesi s etoxvsulfátml sajúcimi od 10 do 20, s výhodou od 10 do 15 atómov uhlíka v alkylovo® radikále a priemerný stupeň etoxylácie od 1 do 6. Kedzi príklady vhodných alkyl sulfátov patria alkyl sulfát loje, alkyl sulfét kokosového oleje a ^14-1- sľicyľ sulfáty. 2a t iónom je v kešdom prípade vždy alkalický kov.
Jednu triedu neiónových povrchovo aktívnych látok podľa tohto vynálezu tvoria kondenzáty etylénoxidu s hydrofóbnou časťou na poskytnutie povrchovo aktívnych látok majúcich priemernú rovnováhu hydrofilnú - lipofilnú /hydrophilic - lipophilic balance = HLB/ v rozmedzí od 8 do 17, s výhodou od 9,5 do
13,5, výhodnejšie od 10 do 12,5. Hydrofóbna /lipofilná/ Časť môže byť alifatickej alebo aromatickej povahy a dĺžka danej polyoxyetylénovej skupiny, ktorá je kondenzovaná so zvláštnou hydrofóbnou skupinou, môže byť ľahko upravená pomocou vo vode rozpustnej zlúčeniny majúcej požadovaný stupeň rovnováhy medzi hydrofiInými a hydrofóbnymi elementárni.
Mimoriadne výhodnými typmi neiónových povrchovo aktívnych látok sú primárny alkohol etoxyláty obsahujúce tri až osem molov etylénoxidu na mol alkoholu, hlavne - Cprimárnych alkoholov obsahujúcich 6-8 molov etylénoxidu na mol alkoholu a - C-^ primárnych alkoholov obsahujúcich
3-5 molov etylénoxidu na mol alkoholu.
Inú triedu neiónových povrchovo aktívnych látok tvoria alkyl polyglukosidy s všeobecným vzorcom:
kde Z je časť odvodená od glukózy; R je nasýtená hydrofóbna alkylová skupina obsahujúca od 12 do 18 atómov uhlíka; t je od 0 do 10 a n je 2 alebo 3; x je od 1, 3 do 4, zlúčeniny zahŕ- j ňajú menej ako 10 % nezreagovaného mastného alkoholu a menej ako 50 % polyglukosidov s krátkym alkýlovým reťazcom. Zlúčeniny tohto typu a ich použitie v povrchovo aktívnych látkach je popísané v EP-B 0 070 077, 0 075 996 a 0 094 118.
Takisto sú ako neiónové povrchovo aktívne látky vhodné poly hydroxy mastné kyseliny a to ich smidy, s všeobecným 2 ί vzorcom R -C-N-Z kde R je H, C, . hydrokarbyl, 2-hyaroxyetyl, o i1 o
2-hydroxypropyl alebo ich zmes, Rz je hydrokarbyl, a Z je polyhydrokarbyl majúci lineárny hydrokarbylový reťazec s aspoň 3 hydroxylmi priamo pripojenými na tento reťazec, alebo ich zmes, a to zmes ich alkoxylovaných derivátov. Výhodné je, keč je R^· metyl, R^ je alkylový alebo alkenylový reťazec ako je alkyl kokosového oleja alebo iúh zmes © Z je odvodené od redukujúceho cukru ako je glukóza, fruktóza, maltóza, laktóza, v rcduktívnej amínačncj reakcii.
Šalviu triedu povrchovo aktívnych látok tvoria semipolárne povrchovo aktívne látky ako sú aEinooxtdy. Vhodnými aminooxldmi sú také, ktoré sú vybrané zo skupiny, tvorenej mon C& - C^, s výhodou N-alkyl alebo alkenyl aminooxidml s propylén— 1,3-dlemíndloxidmi, kde sú v polohe N substituované metylom, hydroxyetylos alebo hydroxypropylo©.
Inou triedou uvedených povrchovo aktívnych látok sú amfoterná povrchovo aktívne látky ako sú látky, založená na polyamíne.
Výhodné sú zmesi typov povrchovo aktívnych látok, viac výhodné sú potom zmesi aniónové a ne iónové. Uvedené povrchovo aktívne prostriedky sjčžu obsahovať od 1 do 70 A hmotnostných, vzhľadom na celkovú hmotnosť povrchovo aktívnej látky, als zvyčajne je povrchovo aktívne látka prítomná v danom prostriedku v množstve od 1 % do 30 £ hmotnostných, výhodnejšie potom v množstve od 10 % do 25 3 hmotnostných.
Výhodné je, ak je solárny pomer vo vode rozpustnej kverterr.ej amóniovej zlúčeniny ku aniónovej povrchovo aktívnej látke aenäí ako 1:1a žiadúce je, aby bol menší ako 1 : 1,5. Vo výhodnom uskutočnení podľa tohto vynálezu je vhodné, aby bol ©oltárny pomer menší ako 1:2.
Optimálne zložky
Tu uvedený prostriedok bude typicky tvorený tak, aby w sebe zahŕňal také časti, ktoré normálne tvoria povrchovo aktívne prostriedky. Pre prostriedok podľa tohto vynálezu je typické, Že obsahuje detergentné/povrchovo aktívne/ plnivo.
Na uvedené použitie je vhodný akýkoľvek systém plnív, ktorý sa konvenčné používa, vrátane aluminosllLkátových materiálov, silikátov, polykarboxylátov a mastných kyselín, materiálov ako je etyléndiemín tetraacetát, maskovacie činidlá kovových iónov ako aminopolyfosfonáty, a hlavne etyléntetrametylénfosfonitá kyselina a dietyléntrisaínpentaEietylénfosfonitá kyselina. Hoci ©Mu byť použité menej výhodné, a to z hľadiska prostredia, systémy fosfátové.
Vhodnými plnivami môžu byť anorganické látky na výmenu iónov, spoločne s anorganickými hydrétovanými alwainosiliká- 7 tovými materiálmi, výhodnejšie potom hydrátované syntetické zeolity, ako je hydrátovený zeolit A, X, B alebo HS.
Inou výhodnou látkou na plnenie je vrstevnatý siltkát, napríklad SKS-6 /Hoechst/. SKS-6 je kryštalický vrstevnatý
Medzi vhodné polykarboxylátové plnivá na použitie podľa tohto vynálezu patrí kyselina citrónová, s vývode rozpustnej soli, deriváty kyseliny jantárovej s všeobecným vzorcom FCH/COOH/CHg/COOH/ kde P znamená alkyl alebo alkenyl, s výhodou C^2-16» kde P môže byť substituovaný hydroxy! o vým, sulfónovým, sulfoxylovým alebo sulfo substituentom. Špecifickými príkladmi sú lauryljantáran, myristyljantáran, palmityljantáran, 2-dodecc-nyl jantéran, 2-tetradecenyljantáran. Jantárové plnivá sa s výhodou používajú vo forme svojich vo vode rozpustných solí, vrátane solí sodných, draselných, amónnych a alkanolamónnych.
Inými vhodnými polykarboxylátmi sú oxodijantáreny a zmesi tartaratmonojantárovéj a tartaratdijantárovéj kyseliny ako je popísané v patente US 4,663,071.
Najma pre kvapalnú modifikáciu sú vhodnými plnivami mastné kyseliny,na použitie tu uvedené sú potom vhodné nasýtené alebo nenasýtené mastné kyseliny ako aj korešpondujúce mydlá. Na tento účel výhodné nasýtené látky majú od 12 do 16 atómov uhlíka v alkylovom reťazci. Výhodnou nenasýtenou mastnou kyselinou je kyselina olejová.
Medzi výhodné systémy plnív na použitie v granulovaných prostriedkoch patrí zmes vo vode nerozpustných aluminosillkátových plnív, ako je zeolit A, a vo vode rozpustných karboxylátových cheletačných Činidiel ako je kyselina citrónová.
Iné materiály ako plnivá, ktoré môžu tvoriť časť uvedených systémov pre plnivá na použitie podľa tohto vynálezu, sú anorganické materiály ako sú uhličitany alkalických kovov, hydrogénuhličitany alkalických kovov, silikáty alkalických kovov a anorganické materiály ako sú organické fosfonáty a aminopolykarboxyláty.
Inými vo vode rozpustnými organickými sólami sú homoa ko-polymérne kyseliny alebo ich soli, pričom tieto polykarboxylové kyseliny obsahujú aspoň dva karboxylové radikály, oddelené od seba navzájom nie viac ako dvoma atómami uhlíka.
Polyméry tohto typu sú popísaná v patente Gď-A-l,59o,75c. lisdzi príklady takýchto solí patria polyokryléty 2030 e ž 5000/tj.majúca relatívnu molekulovú hmotnosť od 2030 do 5000/ a ich kopolyméry a Qaleínanhydridom, ako sú kopolyméry majúca relatívnu molekulovú hmotnosť od 20 000 do ?0 000, najms však 40 000.
V danom prostriedku sú povrchovo aktívne plnivové solt obsiahnuté bežne v množstvách od 10 % hmotnostných do 80 £ hmotnostných na celkovú hmotnosť daného prostriedku, s výhodou potom od 20 do 70 $ hmotnostných a najvýhodnejšie od 30 X hmotnostných áo 60 » hmotnostných, vždy vzhľadom ne celkovú hmotnosť daného prostriedku.
Medzi iné optimálne zložky patria Činidlá mekčiace tkaniny ako je smektlcká hlinka /kaolín/, prídavné polyméry ako polyetylénoxidy, polyvinylpyrrolldóny, polyvinylalkoholy, bieliace činidlá, bieliace aktlvátory, supresory aj iná enzýmy, vybrané zo skupiny, do ktorej patria proteasy, a®yla3»ové celulasy, peroxidasy, oxtdasy.
Forma prostriedku
Uvedený prostriedok môže byť v granulovanej forse a hlavne v kompaktnej forme, tj. aôže mať relatívne vysokú hustotu, teda konvenčné grsnulovené povrchovo aktívne prostriedky podľa tohto vynálezu môžu obsahovať menšie množstvo anorganických plniacich solí, v porovnaní s konvenčnými granulovanými povrchovo aktívnymi látkami; typickými plniacimi sólami sú soli kovov alkalických zemín a to sírany alebo chloridy, typicky potom síran sodný; kompaktné detergenty typicky obsahujúce nie viac ako 10 ž plniacich solí.
Uvedený prostriedok raôžo byť taktiež v kvapalnej forme, e potom obsahuje typické zložky pre takéto prostriedky, ako sú organické rozpúšťadlá, hlavne etanol.
Ďalej budú uvedené prípady uskutočnenia tohto vynálezu ako Príklady uskutočnenia, ktoré však majú llustratívny charakter a nijeko neobmedzujú obsah ani rozsah tohto vynálezu.
-9 Príklady uskutočnenie vynálezu
Príklad 1
Pripravia sa nasledujúce povrchovo aktívne prostriedky:
ž h m o t n o s t n é 1 1
Zložky i i Zložka A Zložka B Zložka C Príklad |
1 Sodná soľ lineárneho dodecylben- i zénsulfonátu 6,5 6,5 6,5 6,5 J Ϊ J
> Sodná soľ lojového alkoholsulfá- • tu 2,5 2,5 2,5 2 ;
j Mastný alkohol /C,?-C, _/ etoxy: lovaný /7 EO/ 9 5,5 5,5 5,5 5,5 *
í Sodná forma Zeolitu 4A 25,0 25,0 25,0 25,0
í Perborát 4Ho0 í á ·' j Tetraacetyletyléndiamín / 20,0 20,0 20,0 20,0
3,5 3,5 3,5 3,5
j Sodná soľ uhličitanu 10,0 10,0 10,0 10,0
; Bielidlo 0,2 0,2 0,2 0,2 :
« Karboxymetylcelulóza 0,5 0,5 0,5 0,5
Etyléndiamíntetraacetát 0,3 0,3 0,3 0,3 í
1 Kopolymér kyseliny akrylovej a i kyseliny maleínovej 2,5 2,5 2,5 2,5. J
j Kokosový dimetylhydroxyetyl- | amónium chlorid A — 1,5 — ľ,5 i
] Lipasa /Lipolasé^ s 100 kLU/ - - 0,36* 0;362 :
j Sodná soľ sulfátu h 9,3 9,3 9,3 9,3 j
\ Menšina + voda doplnenie bilancie na 100 ;
Vyššie uvedené prostriedky sa porovnávajú podľa % odstránenia zašpinenia a podľa efektu udržania bielosti.
% odstránenia zašpinenia sa vyhodnocuje porovnávaním meranej reflektancie látky, zašpinenej olivovým olejom, pričom je táto látka sfarbená farbou Sudan red, a to porovnaním uvedenej reflektancie pred a po vypraní; spôsob je nasledujúci:
Aby bolo lepšie viditeľné, nakoľko sa odstráni znečistenie olivovým olejom, je skúmaná vzorka ofarbená farbivom Sudan red /v oleji rozpustné farbivo/. Potom sa meria % odstránenia zašpinenia určením hodnôt reflektancie.
i
V
Na overenie takto získaných hodnôt reflektancíe /koncentrácie Sudan red/ sa prevádza korelácie s aktuálnym odstránením olivového oleja, ktorý sa odstraňuje extrakciou pred a po vypraní, čerenie extraktov sa prevádza dvoma spôsobmi: gravimetrický a pomocou infračervenej spektroskopie /1735 cm”x/. Výsledky sú nesledujúce:
ΐ Peflektancie t
μ----------ΐ 21
I-> j ίέ odstránenia zašpinenia i Γ s 1 Gravimetrický Infračervenou | f spektroskopiou | J--í-------------------------------í P ‘ Ϊ 19,4 21,6 í
Efekt udržania bielosti korešponduje s opakovaným vystavovaním zašpinenia ako percenta odstránenie zašpinenia. Počíta sa podľa vzťahu:
á opakovaného zašpiňovania x 100 % odstránenia zašpinenia
Tento efekt sa pre daný účel monitoruje, stanovuje sa reflektancia u neznečistených vzoriek.
Podmienky testu sú nasledujúce:
Zariadenie - Launderometer
Zohrievanie počas cyklu — 40 °C ,
Koncentrácia povrchovo aktívnej látky - 6 g/l
Tvrdosť vody - 2,5 mmol/1
Premývacia kvapaline - 200 ml
Zaťaženie - 6 polyesterových vzoriek tkaniny 7 x 7 cm /3 g/ z ktorých vzorky tkaniny se znečistia 50 ml olivového oleja vzorky tkaniny sa neznečistia
Počet cyklov - 2
Výsledky sú nesledujúce:
r~— .....-....... 1 Prostriedok í... 56 odstránenie znečistenia efekt udržania bielosti j
í A 57 26 !
B 62 23
c 71 31 !
j Príklad 1 j 78 18
- 11 Diskusia výsledkov
Výsledky jasne dokázali výborné vlastnosti prostriedku podľa tohto vynálezu /Príklad 1/ podľa hodnoty veličiny % odstránenia znečistenia /znečistenie obsahovalo triglyceridy/ a veličiny efektu udržania bielosti.
Synergický efekt í % odstránenia znečistenia a efekt udržania bielosti sa porovnáva s Príkladom 1 a s celkovými výsledkami prostriedkov B a C:
% odstránenia znečistenia efekt udržania bielosti
e í L /diferencia v porovnaní so spracovaním A/ j 3
p .... -1 j Príkled 1 | B + C . + 21 - 8 j
+ 19 + 2
Vyššie uvedené výsledky dokazujú, že výsledok podľa Príkladu 1 vykazuje vyšší účinok ako len prídavný a tým dokazuje existenciu synergie.
/Uvedené % odstránenia znečistenia sa zvyšujú a % opátovného zašpiňovania. sa znižujú /W//· fialej boli tiež pripravené nasledujúce povrchovo aktívne prostriedky: /v stĺpcoch na ľavej strane sa uvádza prostriedok, % hmotnostné/
Zložky
Prostriedok /¾ hmotnostné/ Príkl.2 Príkl.3 Príkl.4 * Cn-^al^lbenzé^ulfonát
I Alkoholsulfát /N®/ loja
Ci^^alkylsulfát /Na/ Alkoholetoxylét /EO^/ Mas tn^alkohol/C12-1^/e toxyΟ, οι imetyl/hy droxye tyl / amonlum chlorid
Kokosový dimetyl/hydroxyetyl/ emoniWA chlorid
Zeolit A j granulo- kompaktné kvapalný J vaný granule j
A
V
I i
J
I j
š vaný
0,5
1,5 ’C I í i' I í
J t
i
Ϊ
- 12 !
Citrát sodný 5 6 —
Mastná kyselina olejová - - 1
Kyselina citrónová - - 2
Ci^igalkyl jantáran - - 10
1,2-Propándiol - - 3
Etanol - - 7
Metaborátoktahydrát sodný - i - 1
Polyetyléhoxid, relatívna moleku- 0,3
lová hmotnosť 0,3MM · · · ' Síran sodný 2
Uhličitan sodný 11 -
Silikét sodný j 4 3 -
Natriumperborát /1 aq/ j 18 12 -
N , N, N , N—Te tra a c e tyl énd i amí n - 3 -
CMC ' 0.3 0,3 -
Polyakrylét /MW 4000 - 5000/ 3 — -
Kopolymér maleín-akrylový - 4 4»
Lipasa /LipolaseS 100 kLU/ 0,4 0.5 1
Smektická/montmorillonitová hlinka 10,5 12 4
Prímes a spojovanie /parfémy,prote- híí a n ? n é
asa a/alebo amylasa, cellulasa, pero- d xidasa, tlmivý roztok, aupreaor, rôznorodé prímesi, vlhkosť a menšinové látky/ o p 1 n e n d o 100 i e
xPriemyslová využiteľnosť
Povrchovo aktívne prostriedky podľa tohto vynálezu, majúce zlepšené vlastnosti voči odstraňovaniu znečistenia, sú veľmi zaujímavé takisto z hľadiska možnosti priemyslového využitia0 najma v textilnej výrobe.

Claims (5)

  1. t ý s, pustnú že obsahuje povrchovo fiktívne Činidlo, ,:· r> ». . . r Λ - .· 1 a r- ·. s. * » ' kvarternú soopióvif 'zlúčeninu vSeobeenéh vo vode rozo vzorca;
    /1/ f i kde R^ j© Cg — C^6 slkyVelabo 3β * &áô T je 0,
    NH ©lebo Ν-€χ-4 alkyl, 2^ je divalentná alkylénová skupina alebo /CgM^O/^, m ** číslo od 1 do ô, kde každý z P?> 7½ a sú navzájom nezávislá a znamenajú alkyl alebo hydroxyl alkyl, benzyl, alebo kde x je číslo o hodnote od 2 do 5, nie viac ako jeden z Rg, F j ©lebo znamenajú benzyl a X je anión, alebo kde n j© 2, 3, alebo 4, s výhodou 2, Q je CH, C?T2 alebo N e a 8g sú rovnaké sko vo vzorci uvedenoa /1/ a X“ znesené anión·
  2. 2. Povrchovo aktívny prostriedok podľa nároku 1, vyznačujúci s a t ý n, že uvedená svár tern é ssiónlové soli sú vybrané z látok, v ktorých R^ je C^,. - C^- alkyl a R^, R^ s sú s výhodou vybrané z aetylových e hyôroxyetylových skupín.
  3. 3· Povrchovo aktívny prostriedok podľa nároku 1 a 2, vyznačujúci g a t ý a, že úroveň uvedenej vo vode rozpustnej katiónov©j zlúčeniny je od 0,1 do 10 ž hmotnostných a úroveň uvedeného enzýsu lipasy je od 10 LC do 500 LU.
  4. 4· Povrchovo aktívny prostriedok podľa nároku 1 až 3> v y značujúcl sa t ý a, že povrch aktívneho Činidle obsahuje en iónové povrchovo aktívne látky, pričom aolárny pomer aniónovej povrchovo aktívnej látky ku vo vode rozpustnej kvartemej asóniovej zlúčäpine ja váčží ako 1:1·
  5. 5· Povrchovo ektívny prostriedok podľa ciroku 1 ež 4, vyznačujúci se t ý a, že je v granulovanej for:sc, vo forme kompaktných granúl alebo v kvapalnej forme.
SK724-93A 1991-01-16 1992-01-16 Detergent compositions containing lipase and water-soluble quaternary ammonium compounds SK72493A3 (en)

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