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WO2010119076A1 - Nettoyage avec libération contrôlée d'acide - Google Patents

Nettoyage avec libération contrôlée d'acide Download PDF

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Publication number
WO2010119076A1
WO2010119076A1 PCT/EP2010/054907 EP2010054907W WO2010119076A1 WO 2010119076 A1 WO2010119076 A1 WO 2010119076A1 EP 2010054907 W EP2010054907 W EP 2010054907W WO 2010119076 A1 WO2010119076 A1 WO 2010119076A1
Authority
WO
WIPO (PCT)
Prior art keywords
glycolic
detergent composition
lactic acid
phase
acid oligomer
Prior art date
Application number
PCT/EP2010/054907
Other languages
English (en)
Inventor
Rudolf Eduard Nijburg
Original Assignee
Purac Biochem Bv
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US12/385,700 external-priority patent/US8343283B2/en
Priority claimed from EP20090158027 external-priority patent/EP2241612A1/fr
Application filed by Purac Biochem Bv filed Critical Purac Biochem Bv
Priority to RU2011141205/04A priority Critical patent/RU2533552C2/ru
Priority to CN2010800164586A priority patent/CN102395666A/zh
Priority to CA2757937A priority patent/CA2757937A1/fr
Publication of WO2010119076A1 publication Critical patent/WO2010119076A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0047—Other compounding ingredients characterised by their effect pH regulated 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates

Definitions

  • the present invention relates to the field of neutral to alkaline cleaning, especially in automatic washing machines.
  • the substrates e.g. dishes or laundry
  • a detergent solution is obtained by mixing a detergent in water, which detergent can contain components such as alkalinity agents, builders, bleaches, enzymes, surfactants for defoaming or cleaning, polymers, corrosion inhibitors etc.
  • Commercial ma- chine washing detergents are known to operate at alkaline pH, making them less efficient in removal of scale and soap scum.
  • a scale layer may accumulate inside the automatic washing machine.
  • scale deposits may be visible on certain substrates after washing.
  • Rinse aid compositions further typically contain components which aid the wetting of the substrates in the rinse, such as nonionic surfactants and/or hydrotropes, and sometimes other additives improving the efficacy of the rinsing process, such as polymers, silicones, etc.
  • These rinse aid compositions are not designed for the achievement of a primary soil removal purpose and may be added during the rinse cycle of the machine, separately from the de- tergent composition employed in the main cleaning cycle (s).
  • the ability to enhance rinsing, and in particular the ability to prevent spot and scale formation, are common measures of rinse aid performance.
  • dishwashing tablets containing at least a detergent and a rinse aid function in one tablet Such tablets sometimes are referred to as 2-in-l tablets or as tablets with a built-in rinse aid.
  • Some 2-in-l tablets have a wax portion which contains the rinse aid.
  • These types of tablets have disadvantages since they may only be used in a wash cycle that does not exceed 55 0 C, because the wax portion which contains the rinse aid will completely dissolve in a wash cycle that exceeds 55°C. This causes all of the rinse aid to drain out of the dishwashing machine be- fore the actual rinse cycle.
  • 2-in-l tablets are very complicated and expensive to produce.
  • pH sensitive 2-in-l tablets Other types of tablets that are well known are pH sensitive 2-in-l tablets. These types of tablets have a rinse aid portion that is contained in a pH sensitive material. The pH sensitive 2-in-l tablets may be used in wash cycles that exceed 55 0 C.
  • US 2001031714 relates to a laundry, dishwashing or cleaning detergent portion having two or more detersive components of which at least two are to be released into the liquor at different points in time in a laundering, dishwashing or cleaning process, said portion comprising at least one release controlling (physico) chemical switch which is not subject or not exclusively subject to temperature control, and also one or more substances for increasing the extent of the shift in pH.
  • Such components for release into the respective liquor at a later stage of the cleaning process may be provided with a pH shift sensitive coating, compounded into a detersive formulation using a pH shift sensitive binder, or compounded into a detersive formulation using a pH shift sensitive matrix material.
  • controlled release of acid from a glycolic and/or lactic acid oligomer with an average degree of polymerization between 1.8 and 6, preferably between 1.8 and 4, in a cleaning cycle in an automatic washing machine advantageously obviates the need to dose a separate rinse aid in the rinse cycle.
  • the present invention discloses a method for cleaning a substrate comprising contacting the substrate in a cleaning cycle with an aqueous cleaning solution comprising an aqueous diluent and an detergent composition, the detergent composition comprising a glycolic and/or lactic acid oligomer with an average degree of polymerization between 1.8 and 6.
  • the substrate then is contacted in a rinse cycle with an aqueous rinse, which aqeous rinse is substantially free of an intentionally added rinse agent.
  • the glycolic and/or lactic acid oligomer as described herein is water-insoluble and is biodegradable.
  • the oligomer is a polyester which reacts with water upon contact therewith, i.e. the water hydrolyses the ester bond. It has been found that the use of such an oligomer with a degree of polymerization in this range provides a controlled release of water-soluble glycolic acid and/or lactic acid in the cleaning solution during the cleaning cycle and thereby generates a pH gradient during the cleaning cycle.
  • the alkaline detergent component (s) can properly exert its cleaning function in the initial stage of the cleaning cycle, since use of the glycolic and/or lactic acid oligomer ensures that glycolic and/or lactic acid is slowly released such that it exerts its function predominantly in a later stage of the process.
  • Controlled release of the glycolic and/or lactic acid in the cleaning cycle advantageously obviates the need to dose a separate rinse aid in the rinse cycle after the cleaning cycle, or to dose a separate fabric softener.
  • the aqueous rinse thus is substantially free of an intentionally added rinse aid or fabric softener.
  • no rinse aid or fabric softener at all is intentionally added to the aqueous rinse.
  • Controlled release of acid in the cleaning cycle reduces or prevents the formation of hard water (calcium and magnesium salts) deposits in the washing machine and/or on the substrates to be cleaned, and thus obviates the need to use spe- cial washing machine cleaners. Controlled release of acid also contributes to soap scum removal.
  • This incrustation is essentially made up of non water-soluble calcium and magnesium salts of fatty ac- ids, carbonate and, to a lesser extent, silicate and zeolite. These deposits on garments generate a visible grayish staining and attract even more soil due to the stickiness of the mineral incrustation, leading to an unpleasant appearance and being detrimental to the "soft feel" of the garment. Controlled release of acid has a softening effect on fabrics and is beneficial in longer lasting fragrances, since it provides improved adherence of fragrances to the garment.
  • lactic acid has a sanitizing and disinfecting effect due to its antibacterial activity.
  • glycolic and/or lactic acid oligomer as described herein encompasses both straight-chain and cyclic glycolic and/or lactic acid oligomers.
  • the glycolic and/or lactic acid oligomer is glycolide and/or lactide, which are cy-hack glycolic and/or lactic acid dimers.
  • the glycolic and/or lactic acid oligomer is for at least 50 wt . % made up of glycolide and/or lactide, more in particular, the glycolic and/or lactic acid oligomer is for at least 70 wt.% made up of glycolide and/or lactide, still more in particular for at least 80%, even more in particular for at least 90%.
  • the detergent composition may comprise 5-70 wt.% of the glycolic and/or lactic acid oligomer based on total weight of the detergent composi- tion, preferably 10-60 wt.%, more preferably 20-50 wt.%. It is an option to formulate the glycolic and/or lactic acid oligomer and the alkaline detergent components in separate phases of the detergent composition, which option is preferred when applying the glycolic and/or lactic acid oligomer in the higher concen- tration ranges.
  • the detergent composition may comprise 10-95 wt.% of the glycolic and/or lactic acid oligomer based on weight of the phase containing the glycolic and/or lactic acid oligomer, preferably 25- 90 wt.%, more preferably 40-80 wt.%.
  • the detergent composition may be included in the aqueous diluent in a concentration of 200 to 5000 parts by weight of the detergent composition per each one million parts of the aqueous diluent.
  • the cleaning cycle can be performed at any desired temperature effectuating hydrolysis of the oligomer and release of the acid, e.g. from about 20 0 C to about 90 0 C.
  • An appropriate temperature is 60 0 C.
  • release of the acid occurs in about 30 minutes, whereas the other components of the detergent composition typically have a dissolution time of less than 5 minutes.
  • the detergent composition may comprise conventional ingredients, preferably selected from caustic agents, builders (i.e. deter- gency builders including the class of chelating agents/sequestering agents) , bleaching systems, anti-sealants, corrosion inhibitors, surfactants, antifoams and/or enzymes.
  • Suitable caustic agents include alkali metal hydroxides, e.g. sodium or potassium hydroxides, and alkali metal silicates, e.g. sodium metasilicate .
  • sodium silicate having a mole ratio of Si ⁇ 2 :Na 2 O of from about 1.0 to about 3.3, preferably from about 1.8 to about 2.2, normally referred to as sodium disilicate.
  • the pH of the detergent composition typically is in the neutral to alkaline region, i.e. from 6-11, preferably from 7- 10.
  • Suitable builder materials are well known in the art and many types of organic and inorganic compounds have been described in the literature. They are normally used in all sorts of cleaning compositions to provide alkalinity and buffering capacity, prevent flocculation, maintain ionic strength, extract metals from soils and/or remove alkaline earth metal ions from washing solutions .
  • the builder material usable herein can be any one or mixtures of the various known phosphate and non-phosphate builder materials.
  • suitable non-phosphate builder materials are the alkali metal citrates, carbonates and bicar- bonates; and the salts of nitrilotriacetic acid (NTA) ; methylglycine diacetic acid (MGDA) ; glutaric diacetic acid (GLDA) , EDTA, polycarboxylates such as polymaleates, polyace- tates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/polymethacrylate copolymers, as well as zeolites; layered silicas and mixtures thereof.
  • NTA nitrilotriacetic acid
  • MGDA methylglycine diacetic acid
  • GLDA glutaric diacetic acid
  • EDTA polycarboxylates such as polymaleates, polyace- tates, polyhydroxyacrylates, polyacrylate/poly
  • glycolic and/or lactic acid oligomer as described herein advantageously obviates the need to include builder materials with sequestrant function, such as nonbiodegradable builders like NTA and EDTA, since the slow release of acid will provide reaction with hard water metals such as calcium and/or magnesium.
  • Particularly preferred builders are phosphates, MGDA, GLDA, citrates, carbonates, bicarbonates, polyacry- late/polymaleate, maleic anhydride/ (meth) acrylic acid copolymers, e.g. Sokalan CP5 available from BASF.
  • Surfactants especially nonionics, may be present to enhance cleaning and/or to act as defoamer. Suitable surfactants further may include anionic, cationic or amphoteric surfactants, or mixtures thereof. Typically used nonionics are obtained by the condensation of alkylene oxide groups with an organic hydrophobic material which may be aliphatic or alkyl aromatic in nature, e.g. selected from the group consisting of a C2-C18 alcohol alkoxylate having EO, PO, BO and PEO moieties or a polyalkylene oxide block copolymer. The surfactant may be present in a concentration of about 0.1% to about 10% by weight, preferably from 0.2% to about 5% by weight, most preferably from about 0.5% to about 2% by weight .
  • Suitable bleaches for use in the detergent may be halo- gen-based bleaches or oxygen-based bleaches. More than one kind of bleach may be used.
  • alkali metal hypochlorite may be used as halogen bleach.
  • Other suitable halogen bleaches are alkali metal salts of di- and tri-chloro and di- and tri-bromo cyanuric acids.
  • Suitable oxygen-based bleaches are inorganic peroxides or organic peracids, derivatives thereof (including their salts) and mixtures thereof.
  • Especially preferred inorganic peroxides are percarbonates, perborates and persulphates with their sodium and potassium salts being most preferred.
  • Sodium percarbonate and sodium perborate are most preferred, especially sodium percarbonate.
  • Organic peracids include all organic peracids traditionally used as bleaches, including, for example, perben- zoic acid and peroxycarboxylic acids such as mono-or diperoxyphthalic acid, 2-octyldiperoxysuccinic acid, , diperoxy- dodecanedicarboxylic acid, diperoxy-azelaic acid and imido'per- oxycarboxylic acid and, optionally, the salts thereof.
  • PAP phthalimidoperhexanoic acid
  • the bleaching compound it is present in an amount of from 1 to 25wt%, especially 5 to 20wt%, based on the total weight of the composition.
  • the detergent compositions comprise a bleaching compound, they also preferably comprise one or more bleach activators and or one or more bleach catalysts. Any suitable bleach activator may be included for example TAED. Any suitable bleach catalyst may be included. Conventional amounts of both the bleach catalyst and bleach activator may be used e.g. independently for both the bleach activator and bleach catalyst, amounts of from 0.01 to 10wt%, more preferred of from 0.1 to 8wt% and most preferred of from 0.5 to 5wt% based on the weight of the total composition.
  • Amylolytic, cellulolytic, proteolytic and/or lipolytic enzymes would normally be used as an enzymatic component.
  • the enzymes usable herein can be those derived from bacteria or fungi.
  • the detergent composition may further comprise components with a rinse aid function, such as components which aid the wetting of the substrates in the rinse, such as nonionic surfactants and/or hydrotropes, and sometimes other additives improving the efficacy of the rinsing process, such as polymers and/or silicones.
  • a rinse aid function such as components which aid the wetting of the substrates in the rinse, such as nonionic surfactants and/or hydrotropes, and sometimes other additives improving the efficacy of the rinsing process, such as polymers and/or silicones.
  • Minor amounts of various other components may be present in the detergent composition. These include hydrotropes such as xylene sulfonates, flow control agents, disintegrants, enzyme stabilizing agents, anti-redeposition agents, corrosion inhibitors, fragrances and other functional additives.
  • hydrotropes such as xylene sulfonates, flow control agents, disintegrants, enzyme stabilizing agents, anti-redeposition agents, corrosion inhibitors, fragrances and other functional additives.
  • the detergent composition may be in solid form, for instance may be a (granular) powder, a tablet or a solid block.
  • a flow control agent When in powder form, a flow control agent may be in- eluded to provide good flow properties and to prevent lump formation of the powder.
  • a disintegrant When in tablet form, a disintegrant may be included to promote disintegration of the tablet.
  • Various classes of disintegrant are known, including the class in which disintegration is caused by swelling of the disintegrant .
  • Various swelling dis- integrants have been proposed in the literature, with the preference being directed predominantly towards starches, celluloses and water soluble organic polymers.
  • Inorganic swelling disintegrants such as bentonite clay have also been mentioned.
  • the detergent composition may be encased in a water- soluble pouch or sachet.
  • the detergent composition further may be in a unit dose form.
  • the detergent composition may be formed by, for in- stance, compression of powder ingredients, mixing of ingredients in a pourable melt, extrusion, or any combination thereof.
  • certain components of the solid detergent composition are formulated separately from each other.
  • certain components of the detergent composition may be present in at least two separate compartments of a water soluble pouch, or may be present in at least two separate layers or compartments of a tablet or solid block.
  • Such a detergent composition wherein certain components are formulated sepa- rately from each other, is commonly known as a multi-phase detergent composition.
  • the glycolic and/or lactic acid oligomer is in a separate phase from at least the major part of the alkaline components.
  • the present invention discloses a multi-phase detergent composition wherein, on the one hand, at least the glycolic and/or lactic acid oligomer and, on the other hand, at least a major part of the alkaline component (s) of the detergent composition are present in separate phases of the detergent composition.
  • At least a major part of the alkaline component (s) of the detergent composition is meant at least 60%, preferably at least 70%, more preferably at least 80%, most preferably at least 90% of the alkaline component (s) of the de- tergent composition.
  • the alkaline component (s) of the detergent composition may encompass components like caustic agents and alkaline builders .
  • Such a detergent composition thus comprises at least two phases.
  • One phase comprises the glycolic and/or lactic acid oligomer and a further phase comprises at least a major part of the alkaline component (s) .
  • more than one functional component may be included in more than one further phase.
  • potentially chemically sensitive and/or mutually incompatible components may be separated from each other by formulation in separate phases, in order to avoid any loss in performance caused by components reacting together and potentially becoming inactive or exhausted.
  • a barrier layer comprising a barrier layer composition may be located between the various phases of the multi-phase solid detergent composition.
  • the barrier layer composition may comprises at least one binder selected from the group consisting of organic polymers, for example granular and liquid polyethylene and/or polypropylene glycols, especially those of molecular weight 4000, 6000 and 9000, polyvinyl pyrolindone (PVP), especially PVP of molecular weight 90000, polyacrylates, sugars and sugar derivatives, starch and starch derivatives, for example hydroxy propyl methyl cellulose (HPMC) and carboxy methyl cellulose (CMC); and inorganic polymers, such as hexametaphosphate .
  • organic polymers for example granular and liquid polyethylene and/or polypropylene glycols, especially those of molecular weight 4000, 6000 and 9000
  • PVP polyvinyl pyrolindone
  • HPMC hydroxy propyl methyl cellulose
  • CMC carboxy methyl cellulose
  • the advantage of the presence of a barrier layer is to prevent or reduce migration of components from one phase to an- other phase.
  • the concentration of the glycolic and/or lactic acid oligomer in the respective phase of the multi-phase detergent composition is 10-95 wt.% based on the total weight of the respective phase, preferably 25-90 wt.%, more preferably 50-85 wt.%.
  • the multi-phase detergent composition is in a solid form, for instance is a (granular) powder, a tablet or a solid block.
  • the multi-phase detergent composition may be encased in a water-soluble pouch or sachet.
  • the multi-phase detergent composition further may be in a unit dose form.
  • Phase 2 of the prepared formulations A - I was a transparent and ho- mogenous liquid having a melting point of above 60 0 C, whereas phase 1 was a pourable melt containing solid particles.
  • phase 12.5 g were taken and poured into a mold having a dimension of 3.5 x 3.5 x 0.8 cm. Before solidification the molds containing the two respective phases were put on top of each other and further cooled down, thus forming a two layered rigid block of ⁇ 25 g having a dimension of 3.5 x 3.5 x 1.6 cm.
  • the prepared rigid blocks consist of a two-phase system, phase 1 containing the alkaline detergent component and phase 2 containing the slow release acid generating component.
  • Table 1A Compositions of lactide based machine dishwashing formulations
  • Genapol OA80 (Fatty alcohol 15 5 20 5 15 5
  • Figures IA, B, C show the development of the pH over time for each composition A to I . It can be seen that the pH gradually decreases, indicating gradual release of acid over time.
  • the neutral to alkaline detergent phase had a dissolution time of less than 5 minutes, whereas the acid release phase showed a dissolution time of about 30 minutes.
  • three commercial dish washing tablets were tested in the same way. These tablets did not show a decrease in pH (see Table 2) .

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention porte sur un procédé pour le nettoyage d'un substrat comprenant la mise en contact du substrat lors d'un cycle de nettoyage avec une solution aqueuse de nettoyage comprenant un diluant aqueux et une composition de détergent, la composition de détergent comprenant un oligomère d'acide glycolique et/ou lactique ayant un degré moyen de polymérisation compris entre 1,8 et 6. L'oligomère d'acide glycolique et/ou lactique permet une libération contrôlée d'acide glycolique et/ou lactique dans la solution de nettoyage produisant un gradient de pH acide dans la solution de nettoyage pendant le cycle de nettoyage. De préférence, le substrat est mis en contact lors d'un cycle de rinçage avec une solution aqueuse de rinçage qui est pratiquement exempte d'un agent de rinçage intentionnellement ajouté ou d'un produit assouplissant.
PCT/EP2010/054907 2009-04-16 2010-04-14 Nettoyage avec libération contrôlée d'acide WO2010119076A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
RU2011141205/04A RU2533552C2 (ru) 2009-04-16 2010-04-14 Очистка с регулируемым высвобождением кислоты
CN2010800164586A CN102395666A (zh) 2009-04-16 2010-04-14 控制酸的释放的清洁
CA2757937A CA2757937A1 (fr) 2009-04-16 2010-04-14 Nettoyage avec liberation controlee d'acide

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US12/385,700 US8343283B2 (en) 2009-04-16 2009-04-16 Cleaning with controlled release of acid
US12/385,700 2009-04-16
EP09158027.4 2009-04-16
EP20090158027 EP2241612A1 (fr) 2009-04-16 2009-04-16 Nettoyage avec une libération contrôlée d'acide

Publications (1)

Publication Number Publication Date
WO2010119076A1 true WO2010119076A1 (fr) 2010-10-21

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Application Number Title Priority Date Filing Date
PCT/EP2010/054907 WO2010119076A1 (fr) 2009-04-16 2010-04-14 Nettoyage avec libération contrôlée d'acide

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CN (1) CN102395666A (fr)
CA (1) CA2757937A1 (fr)
RU (1) RU2533552C2 (fr)
WO (1) WO2010119076A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10647945B2 (en) 2013-07-03 2020-05-12 Basf Se Use of a gel-like polymer composition which can be obtained by polymerizing an acid group-containing monomer in the presence of a polyether compound in formulations for automatic dishwashing

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160145542A1 (en) * 2014-11-25 2016-05-26 Milliken & Company Cleaning Composition
CN111867375B (zh) * 2018-03-09 2022-09-23 富士胶片株式会社 抗菌膜、抗菌组合物、带抗菌膜的基材及赋予抗菌性的方法
RU2731182C1 (ru) * 2019-11-15 2020-08-31 Владимир Николаевич Школьный Парфюмерно-косметическое сухое изделие однократного применения

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115309A (en) * 1976-04-03 1978-09-19 Henkel Kommanditgesellschaft Auf Aktien Compositions and method for activating oxygen utilizing cyclic ester-anhydrides of α-hydroxycarboxylic acids
WO1992012228A1 (fr) * 1991-01-14 1992-07-23 E.I. Du Pont De Nemours And Company Compositions biodegradables utilisees pour la liberation regulee d'agents chimiques
US20010031714A1 (en) 1999-12-13 2001-10-18 Thomas Gassenmeier Laundry, dishwashing or cleaning product detergent portions with controlled release of active substance

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5879469A (en) * 1997-01-06 1999-03-09 Deeay Technologies Ltd. Dishwashing method and detergent composition therefor
DE69908139T2 (de) * 1998-07-17 2004-04-08 The Procter & Gamble Company, Cincinnati Waschmitteltabletten und deren Herstellung

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115309A (en) * 1976-04-03 1978-09-19 Henkel Kommanditgesellschaft Auf Aktien Compositions and method for activating oxygen utilizing cyclic ester-anhydrides of α-hydroxycarboxylic acids
WO1992012228A1 (fr) * 1991-01-14 1992-07-23 E.I. Du Pont De Nemours And Company Compositions biodegradables utilisees pour la liberation regulee d'agents chimiques
US20010031714A1 (en) 1999-12-13 2001-10-18 Thomas Gassenmeier Laundry, dishwashing or cleaning product detergent portions with controlled release of active substance

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10647945B2 (en) 2013-07-03 2020-05-12 Basf Se Use of a gel-like polymer composition which can be obtained by polymerizing an acid group-containing monomer in the presence of a polyether compound in formulations for automatic dishwashing

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CN102395666A (zh) 2012-03-28
RU2011141205A (ru) 2013-05-27
RU2533552C2 (ru) 2014-11-20
CA2757937A1 (fr) 2010-10-21

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