EP2929008A1 - Portion unique, de dimensions stables, contenant du produit de lavage de vaisselle - Google Patents

Portion unique, de dimensions stables, contenant du produit de lavage de vaisselle

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Publication number
EP2929008A1
EP2929008A1 EP13732933.0A EP13732933A EP2929008A1 EP 2929008 A1 EP2929008 A1 EP 2929008A1 EP 13732933 A EP13732933 A EP 13732933A EP 2929008 A1 EP2929008 A1 EP 2929008A1
Authority
EP
European Patent Office
Prior art keywords
acid
weight
dimensionally stable
dishwashing
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP13732933.0A
Other languages
German (de)
English (en)
Inventor
Konstantin Benda
Thomas Eiting
Nina Mussmann
Volker Blank
Noelle Wrubbel
Thorsten Bastigkeit
Peter Schmiedel
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
Priority claimed from DE201210222268 external-priority patent/DE102012222268A1/de
Priority claimed from DE201210222267 external-priority patent/DE102012222267A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2929008A1 publication Critical patent/EP2929008A1/fr
Ceased legal-status Critical Current

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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043—Liquid or thixotropic (gel) compositions

Definitions

  • the present invention relates to dimensionally stable disposable portions which contain liquid dishwashing detergents, in particular automatic dishwasher detergents, to the use of the dimensionally stable disposable portions as dishwashing compositions, in particular as machine dishwashing agents, and to a machine dishwashing process in which the dimensionally stable disposable portions are used.
  • Dishwashing detergents in particular also automatic dishwashing detergents, are available to the consumer in a multiplicity of supply forms.
  • traditional solid detergents increasingly flowable and, in particular, liquid to gelatinous dishwashing detergents have recently gained in importance.
  • the consumer particularly appreciates the rapid solubility and the associated rapid availability of the ingredients in the cleaning liquor, especially in short-dishwashing programs and at low temperatures.
  • the bags lose their attractive appearance, which may be caused, for example, by the fact that ingredients in the course of the usual storage time of the bags in the household, especially if the bags are kept in an unlocked packaging, from the bags diffuse out. As a result, the bags are no longer bulging, lose their shape and give a shriveled impression.
  • the outdiffusion of water and other solvents is accompanied by thickening of the composition, which can lead to phase separations, to a poorer solubility of the products and thus even to a poorer dishwashing result up to residues in the dishwasher.
  • the object of the invention therefore consisted of disposable portions in the form of a water-soluble To provide sachets for dishwashing, in particular for automatic dishwashing, which are characterized by dimensional stability.
  • the invention is therefore directed to a dimensionally stable disposable portion containing a liquid dishwashing detergent, in particular automatic dishwashing detergent, which when stored under purge gas (air, 3 l / h) at an isothermal temperature of 40 ° C after 2 hours a weight loss of not more than 15% by weight.
  • Another object of the invention is the use of such a dimensionally stable disposable portion as a dishwashing detergent, in particular as machine dishwashing detergent.
  • Another aspect of the invention relates to a machine dishwashing process in which a dimensionally stable disposable portion is used.
  • Liquid as used herein with respect to the dishwashing composition of the present invention includes all flowable compositions, and more particularly encompasses gels and pasty compositions.
  • the dimensionally stable disposable portions according to the invention are in the form of water-soluble pouches.
  • the water-soluble packaging allows the portioning of the liquid dishwashing detergent.
  • the amount of preferred liquid automatic dishwashing detergent in the disposable portion is in particular 10 to 30 g, especially 15 to 25 g.
  • the water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends.
  • the wrapper may be formed of one or two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.
  • the water-soluble casing contain polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer exhibit good stability with sufficiently high water solubility, in particular cold water solubility.
  • Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 ⁇ mol " , preferably from 20,000 to 500,000 ⁇ mol " , in particular ders preferably from 30,000 to 100,000 gmol " and in particular from 40,000 to 80,000 gmol.
  • polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
  • polyvinyl alcohol copolymers which are prepared in accordance with polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • a polymer selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath is selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath
  • (Meth) acrylic acid-containing (co) polymers polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added.
  • a preferred additional polymer is polylactic acids.
  • Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers.
  • Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
  • polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters.
  • Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylic esters or mixtures thereof.
  • the film material contains further additives.
  • the film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof.
  • Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-sticking agents or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble casings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, C8400 or M8900.
  • Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
  • the bag dimensions should be designed so that the bags fit into the cavity of the dosing device of a machine dishwasher and can be used via the dosing device of automatic dishwashers, without them when closing the
  • Dosing device burst.
  • the bags should be sized so that children can not swallow it.
  • the standard gull test is used based on the European Standard 71-1 standard (modified version of the ISO 8124.1 standard).
  • the standard gullet is a test cylinder, which has the size of a Kinderschlundes.
  • the Standard Maw is usually used to test whether toys or small parts can be swallowed on toys of infants under the age of 3 years.
  • parts with a width of 31, 7 mm and a length of at least 31, 7 mm must have a height (thickness) of 25.4 mm in order to pass the standard gullet test. With a larger width, the height (thickness) can also be slightly smaller.
  • disposable portions are provided in the form of water-soluble bags having a width of at least 32 mm, in particular from 32 to 40 mm and more preferably from 33 to 38 mm and a height (thickness) of at least 25 to 30 mm and in particular from 25 to 27 mm have.
  • the length of the disposable portions can be flexibly designed; By definition (and for safety reasons) the length should be at least equal to the width.
  • the maximum length is determined by the size of the dosing chambers in automatic dishwashers and should therefore not exceed 50 mm.
  • the dimensional stability ensures that the height (thickness) of the bags does not fall below 25 mm during storage.
  • the dimensional stability of the disposable portion can be defined by the weight constancy during storage of the dishwashing agent contained in the water-soluble bag.
  • the greatest possible weight stability during storage of the dishwashing detergent contained in the water-soluble bag is given when the pure dishwashing detergent (without the bag packaging) has the highest possible weight constancy in the test described below: 50 mg of the pure dishwashing detergent (without bag packaging) are in one open aluminum crucible under isothermal conditions (40 ° C) for several hours under purge gas (air, 3 l / h) kept. At intervals of 30 minutes, the weight of the filled crucible is checked and the residue of the dishwashing detergent or the weight loss of dishwashing detergent is determined.
  • weight loss is highest in the first two hours of the given test.
  • dimensional stability of the disposable portions in the form of water-soluble pouches is understood to mean that the pure dishwashing detergent has a weight loss of not more than 15% by weight in the specified test after 2 hours, preferably after 4 hours.
  • the weight loss after one hour is not above 10% by weight. It is even more advantageous if the weight loss after 2 hours is not above 10% by weight.
  • Such a dimensional stability of disposable portions in the form of water-soluble pouches is present, for example, when the water content of the dishwashing agent is from 1 to 25% by weight, preferably from 10 to 20% by weight and in particular from 10 to less than 20% by weight and the content of organic solvents having a volatility (also called volatility or evaporation number) of at least 10 simultaneously 20 to 60 wt .-% and preferably 30 to 45 wt .-% is.
  • the volatility is given as the ratio of the vapor pressure of the substance under consideration to the vapor pressure of the volatile reference substance diethyl ether at 20 ° C and a relative humidity of 65 ⁇ 5%.
  • the water content as defined herein refers to the water content determined by Karl Fischer titration.
  • the preferred organic solvents having a volatility of at least 10 and in particular more than 35 include polyhydric alcohols such as polyethylene glycols, for example PEG 200 or PEG 400, but also 2-methyl-1, 3-propanediol, 1, 3-propanediol, 1, 2-propylene glycol and glycerin.
  • polyhydric alcohols such as polyethylene glycols, for example PEG 200 or PEG 400, but also 2-methyl-1, 3-propanediol, 1, 3-propanediol, 1, 2-propylene glycol and glycerin.
  • those organic solvents and polyhydric alcohols which have a volatility of more than 50 are preferred.
  • organic solvents which have a volatility of less than 10 are completely dispensed with.
  • the total amount of polyhydric alcohol or mixtures of alcohols used is preferably at least 20% by weight, in particular at least 25% by weight, more preferably at least 28% by weight, especially at least 30% by weight.
  • Preferred amount ranges here are 20 to 50 wt .-%, in particular 25 to 45 wt .-%, especially 30 to 45 wt .-%.
  • glycerol is preferably used here in an amount of from 0.1 to 50% by weight, in particular in an amount of from 15 to 45% by weight, particularly preferably in an amount of from 20 to 40% by weight.
  • the 1, 2-propylene glycol is in this case preferably in an amount of 1 to 20 wt .-%, in particular in an amount of 5 to 15 wt .-%, particularly preferably in an amount of 8 to 14% by weight, respectively to the total mass of the dishwashing detergent, wherein the total amount of glycerol and 1, 2-propylene glycol preferably at least 20 wt .-%, in particular at least 25 wt .-%, especially at least 30 wt .-%, particularly preferably 25 to 45 wt .-%, in particular 30 to 42 wt .-%, especially 35 to 40 wt .-% in each case based on the total mass of the dishwashing detergent is.
  • the dishwashing detergents are distinguished by the fact that the mass ratio of glycerol to 1,2-propylene glycol is at least 1: 1, in particular greater than 2: 1. In further embodiments, it may be preferred that the ratio is even greater than 3: 1, more preferably greater than 4: 1, most preferably 5: 1 to 1: 0.
  • the water activity is a w , which is a measure of freely available water in a material and is defined as the quotient of the water vapor pressure over a material to the water vapor pressure over pure water at room temperature (23 ° C), maximum 0.6 and preferably 0.3 to 0.6.
  • the liquid, in particular automatic dishwashing detergents contained in the dimensionally stable disposable portions in the form of water-soluble sachets preferably contain potassium and sodium ions, the mass ratio of potassium to sodium ions in the dishwashing agent being 0.5: 1 to 85: 1, preferably 1: 1 to 30: 1, more preferably 2: 1 to 15: 1, most preferably 3: 1 to 10: 1 or about 5: 1.
  • the mass ratio of potassium ions to sodium ions is either (a) 2: 1 or more or (b) 1, 5: 1 or less, preferably (a) 3: 1 or more or (b) 1: 1 or less.
  • the mass ratio of potassium to sodium ions in the dishwashing detergent is chosen not to fall in the range of 1.5: 1 to 2: 1, preferably not in the range of 1.1: 1 to 2.9: 1 ,
  • the mass ratio of potassium to sodium ions in the dishwashing detergent is either (1) 3: 1 to 85: 1, preferably 4: 1 to 30: 1, more preferably about 5: 1; or (2) 1, 5: 1 to 0.25: 1, preferably 1, 25: 1 to 0.5: 1, more preferably about 1: 1 to 0.7: 1.
  • the sodium and potassium ions may be from the various ingredients of the dishwashing detergent, in particular from builder components and / or anionic surfactants, but also from other optional ingredients, in particular those which are described below.
  • Preferred ingredients in liquid automatic dishwashing detergents include builders which may be phosphate-containing but also phosphate-free.
  • dishwashing detergents typically contain phosphates in the form of polyphosphates.
  • Useful polyphosphates are, for example, tripolyphosphates, pyrophosphates and metaphosphates and in particular their sodium or potassium salts. Preference is given to using tripolyphosphates.
  • tripolyphosphates are condensation products of ortho-phosphoric acid (H 3 P0 4 ) with the empirical formula P3O10 5 " , which are usually used in the form of their salts, preferably the alkali metal or alkaline earth metal, more preferably in the form of their alkali metal salts.
  • Tripolyphosphate salts are generally hygroscopic, white, odorless, nonflammable solids which are readily soluble in water, According to the invention, especially the potassium salt of tripolyphosphate (K 5 P 3 Oi 0 ) or a mixture of the potassium salt of Tnpolyphosphats and the sodium salt of Tnpolyphosphats ( Na 5 P 3 O 10 ) Most preferably, only the potassium salt of the Tnpolyphosphats is used.
  • the proportion by weight of the polyphosphates, in particular of the tnpolyphosphate, in the total weight of the liquid, in particular automatic dishwashing agent is preferably from 0.1 to 30% by weight, in particular from 1 to 28% by weight, particularly preferably from 5 to 25% by weight. even more preferably from 10 to 23% by weight.
  • the liquid, in particular automatic dishwashing detergents may contain various builders, in particular carbonates, citrates, phosphonates, MGDA (methylglycinediacetic acid) or salts thereof, GLDA (glutamic acid-N, N-). diacetic acid) or salts thereof, EDDS (ethylenediamine-N, N'-disuccinic acid) or salts thereof, IDS (iminodisuccinic acid) or salts thereof, and organic cobuilders and silicates.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of the dishwashing detergent.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • dishwashing detergents contain as sole builder or in combination with phosphates, MGDA, GLDA and / or EDDS citrate, for example sodium or potassium citrate.
  • the citrate may be a source of the potassium and / or sodium ions contained in the dishwashing detergent.
  • Dishwashing compositions containing 1 to 10% by weight, preferably 2 to 5% by weight, of citrate are preferred according to the invention.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • the dishwashing detergents can in particular also contain phosphonates as further builders.
  • the phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance.
  • Preferred aminoalkane phosphonates are ethylene diaminedetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs.
  • Phosphonates are preferably present in the compositions in amounts from 0.1 to 10 wt .-%, in particular in amounts of 0.5 to 8 wt .-%, each based on the total weight of the dishwashing detergent.
  • non-phosphate-containing builder crystalline layered silicates of the general formula NaMSi x 0 2x + i ⁇ y H 2 0, wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1, 9 to 4 where particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20, are used.
  • the content of silicates is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.
  • Particularly preferred dishwashing detergents are silicate-free.
  • Builders are usually offered commercially in both solid and liquid form. In view of the desired low amounts of water in the liquid and in particular automatic dishwashing detergent, it is advantageous if at least a part of the builders is introduced into the production process in solid form. Preferably, all the builders and co-builders mentioned above are used in solid form.
  • sulfopolymers Another frequently used ingredient in particular dishwasher detergents are so-called sulfopolymers.
  • the proportion by weight of the sulfopolymer in the total weight of the preferably liquid automatic dishwashing agent is advantageously from 0.1 to 20% by weight, in particular from 0.5 to 18% by weight, particularly preferably from 0.1 to 15% by weight, in particular of 4 to 14 wt .-%, especially from 6 to 12 wt .-%.
  • the sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70 wt .-%, in particular 30 to 50 wt .-%, preferably about 35 to 40 wt .-% sulfopolymer (s).
  • the sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.
  • the copolymers may have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain, in addition to sulfonic acid-containing monomers, at least one monomer selected from the group consisting of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • unsaturated dicarboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • unsaturated dicarboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methyl Thallyloxybenzolsulfonkla, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid group-containing copolymers is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are hereby preferably selected from the aforementioned.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred dishwashing detergents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol.sup.- 1 , preferably from 4000 to 25,000 gmol.sup.- 1 and in particular from 5000 to 15,000 gmol.sup.- 1 .
  • the copolymers in addition to the carboxyl group-containing monomer and the monomer containing sulfonic acid groups, furthermore comprise at least one nonionic, preferably hydrophobic monomer.
  • the use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.
  • Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention.
  • nonionic monomers are preferably monomers of the general formula
  • R (R 2 ) C C (R 3 ) -XR 4 used, in which R to R 3 are independently -H, -CH 3 or -C 2 H 5 , X is an optional spacer group selected is composed of -CH 2 -, -C (O) O- and -C (O) -NH-, and R 4 is a straight-chain or branched saturated alkyl radical having 2 to 22 Carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C
  • the monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably in each case from 5 to 80% by weight, with respect to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, the proportion of the sulfonic acid group-containing monomer and of the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid group-containing monomer 60 to 80 wt .-%, the monomers are in this case preferably selected from the aforementioned.
  • the sulfopolymers can usually be purchased commercially in both liquid and solid form.
  • sulfopolymers in solid form in the preparation of liquid and especially automatic dishwashing detergents.
  • Further ingredients of in particular dishwasher detergents are in particular selected from the group consisting of anionic, nonionic, cationic and amphoteric surfactants, bleaches, bleach activators, bleach catalysts, enzymes, thickeners, sequestering agents, electrolytes, alkali metal hydroxides, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, Fragrances, bitter substances, and antimicrobial agents.
  • Alkali metal hydroxides are preferred in dishwashing detergents only in small amounts, preferably in amounts below 10 wt.%, Preferably below 6 wt. half 5 wt .-%, more preferably between 0, 1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the dishwashing detergent used.
  • the dishwashing agents are free of alkali metal hydroxides.
  • the liquid, in particular automatic dishwasher detergents preferably further comprise at least one nonionic surfactant.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
  • Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants.
  • the automatic dishwashing detergents contain nonionic surfactants from the group of the alkoxylated alcohols.
  • Nonionic surfactants which have a melting point above room temperature.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • nonionic surfactants have been low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • R is a straight-chain or branched, saturated or mono- or polyunsaturated C 6 .
  • 2 is 4-alkyl or alkenyl;
  • R 2 and each group R 3 is independently selected from -CH 3, -CH 2 CH 3, -CH2CH2-CH3, CH (CH3) 2 and the indices w, x, y, z are each independently integers from 1 to 6 stand.
  • nonionic surfactants are particularly preferred that have a C thylenoxidtechniken 9 .i 5 alkyl radical having 1 to 4 E, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.
  • Preferred nonionic surfactants here are those of the general formula R -CH (OH) CH 2 O-
  • R stands for a straight-chain or branched, saturated or mono- or polyunsaturated C6 -24 alkyl or alkenyl group
  • R 2 is H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • A, ⁇ ', A "and A'” independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 "CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, - CH 2 -CH (CH 2 -CH 3 ),
  • w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
  • the cleaning performance of the preparations according to the invention can be significantly improved both in comparison to surfactant-free system as well as in comparison to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.
  • surfactants of the formula R 0 [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 Cl-1 (OI-l) R 2 , in which R is a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x represents values between 0.5 and 1, 5 and y represents a value of at least 15.
  • nonionic surfactants include, for example, the C 2 -26 fatty alcohol (PO) i (EO) i 5 . 4o-2-hydroxyalkyl ethers, in particular also the C 8 -io-fatty alcohol (PO) i (EO) 22 -2-hydroxydecyl ethers.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R and R 2 R 1 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2 Butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 may be different.
  • R and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x> 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 0 [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 simplified.
  • R, R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R and R 2 Have 9 to 14 carbon atoms, R 3 is H and x assumes values of 6 to 15.
  • nonionic surfactants of the general formula R -CH (OH) CH 2 O- (AO) wR 2 have proven to be particularly effective, in which
  • R is a linear or branched, saturated or mono- or polyunsaturated C 6 - 2 4 represents alkyl or alkenyl radical;
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
  • A is a radical from the group CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH (CH 3 ), preferably CH 2 CH 2 , and
  • w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40
  • the group of these nonionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) i 0 -8o-2-hydroxyalkyl ethers, in particular also the C 8 -12 fatty alcohol (EO) 2 2-2-hydroxydecyl ethers and the C 4 . 22 fatty alcohol (EO) 40 -8o-2-hydroxyalkyl ethers.
  • Preferred liquid dishwashing detergents in particular automatic dishwasher detergents, are characterized in that the agent contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the nonionic surfactant in the total weight of the dishwashing agent is preferably 0.1 to 10% by weight. %, preferably 0.5 to 8.0 wt .-% and in particular 1, 0 to 4.0 wt .-% is.
  • Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefinsulfonates, alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates.
  • the anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example potassium or magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form of their corresponding acid, eg Dodecylbenzenesulfonic.
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R '") (R IV ) (R v ) N + CH 2 COO " , in which R'"is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R IV and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 18 -alkyl dimethylcarboxymethylbetain and Cn-Ci7-alkylamidopropyl-dimethylcarboxymethylbetain.
  • Suitable cationic surfactants are i.a. the quaternary ammonium compounds of the formula
  • R VI (R VI ) (R vii ) (R viii ) (R ix ) N + X "
  • R vi to R ix for four identical or different, in particular two long and two short-chain, alkyl radicals and X " for an anion , in particular a halide ion, for example didecyl-dimethyl-ammonium chloride, alkylbenzyl-didecyl-ammonium chloride and ren mixtures.
  • Further suitable cationic surfactants are the quaternary surface-active compounds, in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
  • the enzymes include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Based on the natural molecules, improved variants are available for use in dishwashing detergents, which are preferably used accordingly.
  • the liquid, in particular automatic dishwasher detergents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein.
  • the protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the electron flow at greatly varying redox potentials between the oxidizing enzymes and the soils (mediators).
  • a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Dishwashing agents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations.
  • These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in the case of liquid or gelated agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • a preferably natural polymer or in the form of capsules for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein.
  • dishwashing detergents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight, of enzyme preparations.
  • the group of bleaching agents includes, for example, the compounds H 2 O 2 which supply water in sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate.
  • Further bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • organic bleaching agents are the peroxy acids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-a-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaliminoperoxyhexanoic acid (PAP )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-
  • PAP phthaliminoperoxyhexanoic acid
  • Nonenylamidopersuccinate and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-Diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronate).
  • PAP is particularly preferred.
  • the pH of the liquid dishwashing detergent can be adjusted by means of customary pH regulators, the pH value being chosen depending on the desired application.
  • the pH is in a range of 5.5 to 10.5, preferably 5.5 to 9.5, more preferably 7 to 9, especially greater than 7, especially in the range 7.5 to 8.5
  • the pH adjusting agents are acids and / or alkalis, preferably alkalis.
  • Suitable acids are, in particular, organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid.
  • Suitable bases are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred.
  • volatile alkali for example in the form of ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule.
  • the alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.
  • the alkanolamine is preferably contained in agents according to the invention in an amount of from 0.5 to 10% by weight, in particular in an amount of from 1 to 6% by weight.
  • the composition according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of from 0.001 to 5% by weight. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (chelating agents, INCI chelating agents).
  • buffers are citric acid or citrates, in particular the sodium and Kaliumeitrate, for example, tri- sodium citrate 2H 2 0 and H 2 tripotassium 0th
  • the liquid dishwashing composition has a viscosity above 2000 mPas directly after preparation (Brookfield Viscometer DV-II + Pro, spindle 25, 30 rpm, 20 ° C.), in particular between 2000 and 10000 mPas. After storage, the viscosity may be higher, for example greater than 10,000 mPas, for example in the range 10000-50000 mPas, preferably around 35000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 5 rpm, 20 ° C).
  • the glass corrosion inhibitors used are preferably zinc salts, in particular zinc acetate. Glass corrosion inhibitors are preferably present in compositions according to the invention in an amount of from 0.05 to 5% by weight, in particular in an amount of from 0.1 to 2% by weight.
  • Another object of the present invention is the use of the dimensionally stable disposable portion in the form of water-soluble bags as dishwashing detergent and in particular as machine dishwashing detergent.
  • a further subject of the present invention is also a machine dishwashing process in which a dimensionally stable disposable portion according to the invention in the form of a water-soluble bag is used.
  • the dimensionally stable disposable portion can be deposited at any suitable point in the interior of the dishwasher, preferably in the cutlery basket.
  • the dimensionally stable disposable portion is metered in the form of a water-soluble bag via the metering chamber provided in the dishwasher.
  • the dimensionally stable disposable portions in the form of water-soluble bags can be prepared by any method known to the person skilled in the art.
  • the liquid constituents such as water, aqueous solutions and organic solvents are initially introduced, and the solid constituents are subsequently dissolved in the liquid submitted, step by step. Should it come at intermediate steps to warming, so it may be advantageous to first decay the heat before the next solid ingredient is added. Alternatively, a cooling of the reactor can be done from the outside.
  • the outer packaging of the market products were opened at the same time, single-use portions to be tested removed, the height (thickness) of the disposable portions in the form of water-soluble bags Market products and measured by M1 and recorded as value before storage. All samples were stored for 3 months on a heating ventilation flap (change climate 20 ° C to 30 ° C, 40-60% humidity), then the height (thickness) measured again and noted as values after storage.
  • Measuring stick Aluminum crucible, open

Abstract

L'invention concerne des portions uniques, de dimensions stables, contenant du produit de lavage de vaisselle sous forme de sachets solubles dans l'eau, qui contiennent un produit de lavage de vaisselle liquide, en particulier destiné à être utilisé comme produit de lavage de vaisselle en machine et à être employé dans des processus de lavage de vaisselle en machine. Selon l'invention, les portions sont de dimensions stables lorsque la perte de poids du produit de lavage de vaisselle dans des analyses thermogravimétriques est d'au maximum 15% en poids en 2 heures.
EP13732933.0A 2012-12-05 2013-07-01 Portion unique, de dimensions stables, contenant du produit de lavage de vaisselle Ceased EP2929008A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE201210222268 DE102012222268A1 (de) 2012-12-05 2012-12-05 Wasserarme bis wasserfreie flüssige Reinigungsmittel
DE201210222267 DE102012222267A1 (de) 2012-12-05 2012-12-05 Wasserarme bis wasserfreie flüssige Reinigungsmittel
PCT/EP2013/063776 WO2014086507A1 (fr) 2012-12-05 2013-07-01 Portion unique, de dimensions stables, contenant du produit de lavage de vaisselle

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Citations (5)

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US20120135910A1 (en) * 2010-10-15 2012-05-31 Cognis Ip Management Gmbh Aqueous Laundry Liquid Suitable for Packaging in Polyvinyl Alcohol Pouches
US20120175797A1 (en) * 2011-01-12 2012-07-12 Labeque Regine Method for controlling the plasticization of a water soluble film
WO2013074589A1 (fr) * 2011-11-15 2013-05-23 Stepan Company Compositions de sels d'amine et d'alkyl éther sulfate concentrées
WO2013120550A1 (fr) * 2012-02-14 2013-08-22 Henkel Ag & Co. Kgaa Produit de nettoyage liquide contenant un polymère sulfonique et présentant une faible teneur en eau
WO2013135512A1 (fr) * 2012-03-14 2013-09-19 Henkel Ag & Co. Kgaa Emballage soluble dans l'eau avec saupoudrage

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CA1112534A (fr) * 1976-11-03 1981-11-17 John Pardo Detergent pour lave-vaisselle automatique
US20020142931A1 (en) * 2000-07-19 2002-10-03 The Procter & Gamble Company Gel form automatic dishwashing compositions, methods of preparation and use thereof
US6228825B1 (en) * 2000-10-13 2001-05-08 Colgate Palmolive Company Automatic dishwashing cleaning system
US20040067861A1 (en) * 2002-08-20 2004-04-08 The Procter & Gamble Company Liquid gel automatic dishwashing detergent composition comprising anhydrous solvent

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Publication number Priority date Publication date Assignee Title
US20120135910A1 (en) * 2010-10-15 2012-05-31 Cognis Ip Management Gmbh Aqueous Laundry Liquid Suitable for Packaging in Polyvinyl Alcohol Pouches
US20120175797A1 (en) * 2011-01-12 2012-07-12 Labeque Regine Method for controlling the plasticization of a water soluble film
WO2013074589A1 (fr) * 2011-11-15 2013-05-23 Stepan Company Compositions de sels d'amine et d'alkyl éther sulfate concentrées
WO2013120550A1 (fr) * 2012-02-14 2013-08-22 Henkel Ag & Co. Kgaa Produit de nettoyage liquide contenant un polymère sulfonique et présentant une faible teneur en eau
WO2013135512A1 (fr) * 2012-03-14 2013-09-19 Henkel Ag & Co. Kgaa Emballage soluble dans l'eau avec saupoudrage

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