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EP2812421A1 - Produit de lavage ou de nettoyage contenant de la cellulose ou un dérivé de cellulose - Google Patents

Produit de lavage ou de nettoyage contenant de la cellulose ou un dérivé de cellulose

Info

Publication number
EP2812421A1
EP2812421A1 EP13700094.9A EP13700094A EP2812421A1 EP 2812421 A1 EP2812421 A1 EP 2812421A1 EP 13700094 A EP13700094 A EP 13700094A EP 2812421 A1 EP2812421 A1 EP 2812421A1
Authority
EP
European Patent Office
Prior art keywords
acid
treated
cellulose
cleaning agent
washing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP13700094.9A
Other languages
German (de)
English (en)
Other versions
EP2812421B1 (fr
Inventor
Georg Meine
Cornelius Bessler
Andrea Eutebach
Frank Sonnenschein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2812421A1 publication Critical patent/EP2812421A1/fr
Application granted granted Critical
Publication of EP2812421B1 publication Critical patent/EP2812421B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/228—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with phosphorus- or sulfur-containing groups
    • 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
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents

Definitions

  • the invention relates to a liquid washing or cleaning agent containing surfactant (s) and a cellulose or a cellulose derivative.
  • the invention also relates to processes for the preparation of the washing or cleaning agent.
  • detergents or cleaners To increase the washing or cleaning performance of detergents or cleaners they often contain one or more additives.
  • detergents in order to prevent re-release of previously released soil in finer distribution (redeposition), detergents contain so-called graying inhibitors, such as carboxymethylcellulose.
  • EP 054325 A1 describes a detergent with carboxymethyl cellulose as
  • liquid detergents or cleaners have increasingly been offered in transparent bottles. Due to the low solubility of carboxymethylcellulose in liquid detergents or cleaners, turbidity occurs when incorporating carboxymethylcellulose into liquid detergents or cleaners. This leads to an aesthetically unappealing product, especially if it is offered in a transparent bottle.
  • Another problem is that stable dispersions of cellulose or cellulose derivatives in the matrix of a detergent or cleaning agent are very difficult to obtain.
  • Detergent can be improved without the graying-inhibiting property of the cellulose or the cellulose derivative is lost.
  • the improved incorporability of aesthetically pleasing liquid detergents or cleaners are obtained with graying-inhibiting property.
  • the agent is an acid-treated cellulose derivative selected from the group consisting of acid-treated carboxymethylcellulose (CMC), an acid-treated cellulose acid sulfonic acid ester salt, cellulose acid-treated methylcellulose, acid-treated ethylcellulose, acid-treated hydroxyethylcellulose, acid-treated hydroxypropylcellulose, acid-treated
  • Hydroxypropylmethylcellulose acid-treated methylhydroxyethylcellulose, acid-treated methylcarboxymethylcellulose, acid-treated ethylhydroxyethylcellulose and a mixture of these acid-treated cellulose derivatives.
  • These acid-treated cellulose derivatives can be incorporated in a particularly stable and uniform manner in the liquid matrix of a washing or cleaning agent.
  • the acid-treated cellulose derivative is acid-treated carboxymethylcellulose (CMC) and / or acid-treated hydroxypropylmethylcellulose. Particularly preferred is the acid-treated carboxymethyl cellulose acid-treated sodium carboxymethyl cellulose.
  • Cellulose derivative 0.01 to 10 wt .-% and more preferably 0, 1 to 8 wt .-%, each based on the total liquid detergent or cleaning agent is.
  • the acid-treated cellulose or the acid-treated cellulose derivative has been treated with an alkylbenzenesulfonic acid.
  • Alkylbenzenesulfonic acid are commonly used anionic surfactants in liquid detergents or cleaners. Through the use of alkylbenzenesulfonic acid as acid in the
  • acid treatment does not require the use of an additional chemical, and the acid-treated cellulose or the acid-treated cellulose derivative can be used directly, that is to say without further work-up, in the preparation of the liquid washing or cleaning agent be used. This makes the preparation of the liquid detergent or cleaning agent particularly effective.
  • the invention relates to the use of an acid-treated cellulose or an acid-treated cellulose derivative in a liquid washing or cleaning agent for increasing the anti-graying performance of the washing or cleaning agent.
  • the invention relates to a process for the preparation of a liquid washing or cleaning agent containing 1 to 70 wt .-%, based on the total liquid detergent or cleaning agent surfactant (s) and an acid-treated cellulose or a
  • the resulting ground mixture is mixed with the surfactants and the further constituents of the washing or cleaning agent.
  • the invention relates to a process for the preparation of a liquid washing or cleaning composition containing from 1 to 70% by weight, based on the total liquid detergent or cleaning agent, of surfactant (s) and an acid-treated cellulose or a
  • a cellulose or a cellulose derivative is brought into contact with an aqueous solution of an acid with stirring
  • the mixture obtained is mixed with the surfactants and the further constituents of the washing or cleaning agent.
  • the liquid washing or cleaning agent contains an acid-treated cellulose or an acid-treated cellulose derivative.
  • the acid-treated cellulose derivative is preferably acid-treated carboxymethylcellulose (CMC), an acid-treated cellulose acid sulfonic acid salt, an acid-treated cellulose acid acid sulfate salt, acid-treated methylcellulose, acid-treated ethylcellulose, acid-treated hydroxyethylcellulose, acid-treated hydroxypropylcellulose, acid-treated hydroxypropylmethylcellulose, acid-treated methylhydroxyethylcellulose, acid-treated methylcarboxymethylcellulose, acid-treated ethylhydroxyethylcellulose or a mixture this acid-treated cellulose derivatives.
  • the cellulose derivative is acid-treated carboxymethylcellulose (CMC), an acid-treated cellulose acid sulfonic acid salt, an acid-treated cellulose acid acid acid sulfate salt, acid-treated methylcellulose, acid-treated ethylcellulose, acid-treated hydroxyethylcellulose, acid-treated
  • Carboxymethylcellulose especially acid-treated sodium carboxymethylcellulose, and / or acid-treated hydroxypropylmethylcellulose.
  • alkylbenzenesulfonic acid particularly preferred is dodecylbenzenesulfonic acid and / or Ci 0 -Ci 3 -alkylbenzenesulfonic acid to
  • the amount of acid-treated cellulose or acid-treated cellulose derivative is preferably 0.01 to 10 wt .-%, and more preferably 0.1 to 8 wt .-%, each based on the total liquid detergent or cleaning agent.
  • the acid treatment of the cellulose or the cellulose derivative is carried out by grinding with an acid. It is preferred that the
  • the amount of alkylbenzenesulfonic acid is from 0.01 to 50% by weight, and more preferably from 0.1 to 5% by weight, based on the total cellulose (derivative) / alkylbenzenesulfonic acid mixture. Accordingly, it is also advantageous if the amount of cellulose (derivative) is 50 to 99.99% by weight and more preferably 95 to 99.9% by weight, in each case based on the total cellulose (derivative) / alkylbenzenesulfonic acid mixture, is.
  • a solvent is present in addition to the cellulose or the cellulose derivative and the acid.
  • ethanol is used as the solvent. It is especially preferred
  • Carboxymethylcellulose in particular sodium carboxymethylcellulose, with a Ci 0 -Ci 3 - alkylbenzenesulfonic acid by milling in a ball mill to treat.
  • Sodium carboxymethylcellulose ground with C 10 -C 13 -alkylbenzenesulfonic acid can be stably incorporated into the matrix of a liquid detergent or cleaning agent without precipitation, creaming, deposits and / or lumps.
  • Sodium carboxymethylcellulose has high transparency and good graying-inhibiting properties.
  • the acid treatment of a cellulose or of a cellulose derivative is carried out by bringing the cellulose or the cellulose derivative into contact with an aqueous solution of an acid with stirring.
  • the amount of alkylbenzenesulfonic 0, 1 to 20 wt .-% based on the total cellulose (derivative) / alkylbenzenesulfonic acid / water mixture. It is further preferred if the amount of cellulose (derivative) is from 0.01 to 2.5% by weight, based on the total cellulose (derivative) / alkylbenzenesulfonic acid / water mixture.
  • hydroxypropylmethylcellulose It is preferred to subject hydroxypropylmethylcellulose to such acid treatment with a Ci 0 -Ci 3 - alkylbenzenesulfonic acid.
  • Liquid detergents or cleaners with a C 10 -C 13 - Alkylbenzenesulfonic acid-treated hydroxypropylmethylcellulose are clear and have good graying-inhibiting properties.
  • the liquid detergent or cleaning agent further contains a surfactant which may be, for example, an anionic surfactant, a nonionic surfactant, a zwitterionic surfactant, a cationic surfactant, or a mixture thereof.
  • a surfactant which may be, for example, an anionic surfactant, a nonionic surfactant, a zwitterionic surfactant, a cationic surfactant, or a mixture thereof.
  • the anionic surfactant used may preferably be sulfonates and / or sulfates.
  • surfactants of the sulfonate type preferably come C 9 .i 3 -Alkylbenzolsulfonate,
  • Olefinsulfonates ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from Ci 2 -i 8-monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration.
  • Alk (en) ylsulfates are the alkali metal and in particular the sodium salts of
  • Sulfuric acid semi-esters of Ci 2 -C 8 fatty alcohols for example from coconut fatty alcohol,
  • Tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Ci 0 -C 2 o-oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred.
  • the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates are also suitable anionic surfactants.
  • fatty alcohol ether sulfates such as the sulfuric acid monoesters of straight-chain or branched C 7 ethoxylated with from 1 to 6 mol of ethylene oxide.
  • 2 i-alcohols such as 2-methyl-branched C 9 .n-alcohols having an average of 3.5 moles of ethylene oxide (EO) or Ci 2 _i 8 -Fettalkohole with 1 to 4 EO, are suitable.
  • Suitable anionic surfactants are soaps.
  • Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
  • the anionic surfactants including the soaps may be in the form of their sodium, potassium, magnesium or ammonium salts. Suitable ammonium salts as counterions for the anionic surfactants are the protonated forms of choline, triethylamine, monoethanolamine, triethanolamine or methylethylamine.
  • the content of anionic surfactant including soaps is preferably from 2 to 40% by weight and more preferably from 5 to 30% by weight, based in each case on the total liquid detergent or cleaning agent.
  • Suitable nonionic surfactants include alkoxylated fatty alcohols, alkoxylated
  • Fatty acid alkyl esters Fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof.
  • the nonionic surfactant used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol are preferred.
  • Preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 7 EO or 4 EO, C. 9 i Alcohol with 7 EO, C 13 . 15 -alcohols with 5 EO, 7 EO or 8 EO, C 12 -i8-alcohols with 5 EO or 7 EO and mixtures of these.
  • Levels of ethoxylation represent statistical averages, which may be an integer or a fractional number for a particular product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention.
  • a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol such as a mixture of a C16-18 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO.
  • the washing, cleaning, post-treatment or washing aid containing a Ci-2 -i8 Fett.alkohol with 7 EO, or C-i3-i5-oxo-alcohol with 7 EO or 8 EO nonionic surfactant.
  • the content of nonionic surfactant is preferably 1 to 40 wt .-% and more preferably 2 to 30 wt .-%, each based on the total liquid detergent or cleaning agent.
  • the total amount of anionic and nonionic surfactant in the liquid washing or cleaning agent is up to 70 wt .-%, preferably up to 50 wt .-%, based on the total liquid detergent or cleaning agent.
  • the liquid detergent or cleaning agent may contain other ingredients that the performance and / or aesthetic properties of the washing or cleaning Cleaner further improve.
  • the washing or cleaning agent preferably additionally contains one or more substances from the group of builders, bleaching agents, bleach catalysts, bleach activators, enzymes, enzyme stabilizers, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils , Inlet preventer, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives,
  • Corrosion inhibitors antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, skincare active ingredients, swelling and anti-slip agents, softening components and UV absorbers.
  • Particularly preferred substances which may be present in the washing or cleaning agent are builders, foam inhibitors, enzymes, perfumes, fluorescers, dyes,
  • Enzyme stabilizers and mixtures thereof are, for example, cellulases, amylases, proteases, lipases, mannanases, pectate lyases or xyloglucanases.
  • Suitable enzymes which may be present in the washing or cleaning agent are, for example, cellulases, amylases, proteases, lipases, mannanases, pectate lyases or xyloglucanases.
  • a particularly good anti-graying performance of the washing or cleaning agent is achieved if the washing or cleaning agent contains a cellulase.
  • the detergents or cleaners are liquid and may contain water as the main solvent. Alternatively, or in addition to the water, the detergents or cleaners may contain non-aqueous solvents.
  • the washing or cleaning agents according to the invention can be used for washing and / or cleaning textile fabrics.
  • liquid detergents or cleaners with an acid-treated cellulose or an acid-treated cellulose derivative can be used in particular for increasing the anti-graying performance of the washing or cleaning agent during the washing and / or cleaning of textile fabrics.
  • One possibility for the preparation of the washing or cleaning agent involves first grinding the cellulose or the cellulose derivative with the acid. Subsequently, the resulting mixture is transferred to a stirred tank and water, non-aqueous solvents and the other surfactants, if present, added. Then, if present, the fatty acid is added and saponification of the fatty acid moiety occurs at 50 to 60 ° C. Subsequently, the other ingredients, preferably in portions added.
  • Another possibility for the preparation of the washing or cleaning agent provides that first the cellulose or the cellulose derivative is brought into contact with an aqueous solution of the acid with vigorous stirring in a stirred tank. Subsequently, the non-aqueous solvents and the other surfactants, if any, added. Then, if present, the fatty acid is added and saponification of the fatty acid moiety occurs at 50 to 60 ° C. Subsequently, the other ingredients, preferably in portions added.
  • Table 1 below shows the compositions of two detergents or cleaners E1 and E2 according to the invention and the compositions of three detergents V1 to V4 which are not according to the invention.
  • CMC3 milled in ball mill in the presence of linear Ci 0 -Ci 3 -alkylbenzenesulfonic acid
  • HPMC1 untreated hydroxypropylmethylcellulose
  • HPMC2 treated in aqueous solution with linear Ci 0 -Ci 3 -alkylbenzenesulfonic acid
  • the sodium carboxymethylcellulose used was CMC 8036 R MV 350 from MikroTechnik GmbH & Co. KG.
  • the hydroxypropyl methylcellulose used was Methocel® K 15 M from The Dow Chemical Company.
  • the acid-treated cellulose derivatives could be incorporated stably and uniformly into the liquid matrix of detergents or cleaners.
  • the resulting liquid detergents or cleaners E1 and E2 were aesthetically much more attractive than the comparison detergents or cleaners V1 to V3. Both detergents E1 and E2 had a high transparency and the liquid detergent E2 was even clear. In contrast, the washing and cleaning agents V1 to V3 showed no uniform distribution of

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

Abstract

L'invention concerne un produit de lessive ou de nettoyage liquide contenant une cellulose traitée à l'acide ou un dérivé de cellulose traité à l'acide. L'invention concerne en outre l'utilisation d'une cellulose traitée à l'acide ou d'un dérivé de cellulose traité à l'acide dans un produit de lessive ou de nettoyage liquide pour accroître son pouvoir anti-redéposition .
EP13700094.9A 2012-02-10 2013-01-09 Produit de lavage ou de nettoyage contenant de la cellulose ou un dérivé de cellulose Not-in-force EP2812421B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012202043A DE102012202043A1 (de) 2012-02-10 2012-02-10 Wasch- oder Reinigungsmittel mit Cellulose oder einem Cellulosederivat
PCT/EP2013/050285 WO2013117361A1 (fr) 2012-02-10 2013-01-09 Produit de lavage ou de nettoyage contenant de la cellulose ou un dérivé de cellulose

Publications (2)

Publication Number Publication Date
EP2812421A1 true EP2812421A1 (fr) 2014-12-17
EP2812421B1 EP2812421B1 (fr) 2018-04-11

Family

ID=47522683

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13700094.9A Not-in-force EP2812421B1 (fr) 2012-02-10 2013-01-09 Produit de lavage ou de nettoyage contenant de la cellulose ou un dérivé de cellulose

Country Status (4)

Country Link
US (1) US9169457B2 (fr)
EP (1) EP2812421B1 (fr)
DE (1) DE102012202043A1 (fr)
WO (1) WO2013117361A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013226625A1 (de) * 2013-12-19 2015-06-25 Henkel Ag & Co. Kgaa HPMC-haltige Flüssigwaschmittel
DE102014205869A1 (de) 2014-03-28 2015-10-01 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2539451A (en) * 1948-02-27 1951-01-30 Eastman Kodak Co Method of preparing sulfuric acid esters of cellulose
NL178800C (nl) * 1952-06-02 Electricity Council Werkwijze en inrichting voor het galvanoplastisch vervaardigen van ijzer.
DE3163112D1 (en) 1980-12-17 1984-05-17 Unilever Nv Detergent composition with reduced soil-redeposition effect
DE102007021793A1 (de) * 2007-05-07 2008-11-13 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel mit Polysaccharid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013117361A1 *

Also Published As

Publication number Publication date
US20140349909A1 (en) 2014-11-27
DE102012202043A1 (de) 2013-08-14
WO2013117361A1 (fr) 2013-08-15
US9169457B2 (en) 2015-10-27
EP2812421B1 (fr) 2018-04-11

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