EP0706558A1 - Detergents pour lave-vaisselle contenant des adjuvants biodegradables - Google Patents

Detergents pour lave-vaisselle contenant des adjuvants biodegradables

Info

Publication number
EP0706558A1
EP0706558A1 EP94918884A EP94918884A EP0706558A1 EP 0706558 A1 EP0706558 A1 EP 0706558A1 EP 94918884 A EP94918884 A EP 94918884A EP 94918884 A EP94918884 A EP 94918884A EP 0706558 A1 EP0706558 A1 EP 0706558A1
Authority
EP
European Patent Office
Prior art keywords
acid
weight
composition according
agents
agent
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
EP94918884A
Other languages
German (de)
English (en)
Inventor
Willi Buchmeier
Hans Andree
Peter Krings
Birgit Burg
Jürgen Härer
Peter Jeschke
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 EP0706558A1 publication Critical patent/EP0706558A1/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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C11D3/3788—Graft polymers

Definitions

  • the invention relates to alkaline dishwashing detergents for the mechanical cleaning of dishes with a biodegradable bath component.
  • the latest generation of low-alkaline agents for the automatic cleaning of dishes contain not only bleaching agents based on oxygen, surface-active substances and enzymes, but also a combination of water-soluble builders which are derived from complexing agents, e.g. Citrate, from alkali carriers, e.g. Soda, hydrogecarbonate or disilicate, and from dispersants such as e.g. Polycarboxylates exist.
  • complexing agents e.g. Citrate
  • alkali carriers e.g. Soda
  • hydrogecarbonate or disilicate e.g. Polycarboxylates
  • Other possible builder components are organophosphonic acids, aminocarboxylic acids or crystalline phyllosilicates; to the phosphates previously used, e.g. Pentanatriu tripolyphi-sphat is largely avoided today for ecological reasons.
  • the polycarboxylates used in today's dishwashing detergents e.g. maleate / acrylate copolymers, prevent limescale deposits from accumulating when the residual water hardness is too high in cleaning and clearing agents. rinse cycle; if the rinsing liquor has a high salt load, they also improve the rinse aid effect.
  • the invention relates to a low-alkaline agent for mechanical cleaning of dishes, the 1% by weight aqueous solution of which has a pH of 8 to 11.5, preferably 9 to 10.5, containing water-soluble builder components and bleaching agents Oxygen base, characterized in that it contains, as a water-soluble builder component, a copolymer which is composed at least of the monomers of an onoethylenically unsaturated C3-C8 ⁇ carboxylic acid, a 2-A1-alkylallylsulfonic acid or 2-arylallylsulfonic acid and a carbohydrate .
  • the dishwashing detergents according to the invention also include those in which the copolymers are partially or wholly by the salts of the copolymers, that is to say those copolymers in which the carboxyl group were partially or completely converted to carboxylate groups, are replaced.
  • the copolymers used according to the invention contain two carboxylic acids and / or their salts and a carbohydrate as monomers.
  • the first acidic monomer or its salt is derived from an onoethylenically unsaturated C3-Cg-monocarboxylic acid and preferably from a C3-C4-monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt is a derivative of an allylsulfonic acid which, in the 2-position, has an alkyl radical, preferably a C 1 -C 6 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives. is substituted.
  • copolymers contain 40 to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate with particular preference for acrylic acid or acrylate, 10 to 30% by weight.
  • methallylsulfonic acid or methallylsulfonate preferably 15 to 25% by weight of methallylsulfonic acid or methallylsulfonate, where methallylsulfonic acid or methallylsulfonate can also be partially replaced by a methacrylic acid-polyethylene glycol ester formed by addition of 1 to 10 ethylene oxide units on methacrylic acid, the weight ratio then being between Methacrylic acid polyethylene glycol ester and methallylsulfonic acid or sulfonate is 1:10 to 10: 1, and 15 to 40% by weight, preferably 20 to 40% by weight, of a carbohydrate.
  • This carbohydrate can, for example, be a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred.
  • predetermined breaking points are built into the polymer, which are responsible for the degradability of the polymer.
  • sucrose is preferred as the carbohydrate.
  • the copolymers used according to the invention can be prepared by any of the known and customary processes.
  • the monomeric acids are reacted with the carbohydrate, whereupon the acids are then optionally neutralized to give preferably their alkali metal salts, such as the sodium or potassium salts, or ammonium salts or alkanolamine salts, such as the monoethanolamine salt or the triethanolamine salt.
  • copolymers Analogous to the known conventional (co) polymeric polycarboxylic acids or polycarboxylates such as the homo- or copolymeric acrylic acids or acrylates, those copolymers are also preferred which are either completely or at least partially, in particular more than 50%, based on the carboxyl groups present are neutralized.
  • a completely neutralized copolymer is particularly preferred, ie it consists of the salts of the monomeric acids, in particular the sodium or potassium salts of the monomeric acids, and a carbohydrate.
  • the copolymers generally have a relative molecular mass between 1000 and 200000, preferably between 2000 and 50,000 and in particular between 3000 and 10,000. They are preferably used in powdery, spray-dried form. Particularly preferred copolymers are produced by a process which is described in the earlier German patent application P 4221 381.9.
  • Preferred dishwashing detergents according to the invention contain the copolymer in amounts of 0.5 to 30% by weight, preferably 2 to 20% by weight, furthermore 0.5 to 20% by weight, preferably 5 to 15% by weight, a bleaching agent based on oxygen, in particular alkali perborate and / or percarbonate, and nonionic surfactants in an amount of a maximum of 5% by weight, preferably a maximum of 2% by weight, the agents being free from anionic, cationic or amphoteric surfactants.
  • alkali carbonates and / or bicarbonates, in particular the sodium salts are used as alkali carriers.
  • ze in an amount of up to 60 wt .-%, preferably 5 to 50 wt .-%, contain.
  • the dishwashing detergents according to the invention can comprise further water-soluble builder components, such as synthetic polymers, which include the salts of polymerization products of unsaturated carboxylic acids and which include, for example, polyacrylates, polymethacrylates, poly alylates or copolymers of acrylic acid with maleic acid or maleic anhydride Contain amount of 0.5 to 30 wt .-%, preferably 2 to 20 wt .-%.
  • synthetic polymers which include the salts of polymerization products of unsaturated carboxylic acids and which include, for example, polyacrylates, polymethacrylates, poly alylates or copolymers of acrylic acid with maleic acid or maleic anhydride Contain amount of 0.5 to 30 wt .-%, preferably 2 to 20 wt .-%.
  • Suitable polyacrylates are, for example, Alcosperse ( R ) 102, 104, 106, 404, 406 from Alco, Acrysole ( R ) A Nl, LMW 45 N, LMW 10 N from Norsohas, Degapas ( R ) from Degussa; Suitable copolymers of polyacrylic acid and maleic acid are, for example, Sokalan ( R ) CP 5, SP 7 from BASF, Acrysol ( R ) QR 1014 from Norsohaas, Alcosperse ( R ) 175 from Alco.
  • phosphates can also be present, but the dishwashing detergents are preferably free of phosphate-containing builder components.
  • the surfactants which can be used in the agents according to the invention their foaming behavior is decisive.
  • Low-foam connections are preferred because of the mechanical mechanics.
  • a 'ilem Weg ⁇ ionic surfactants; the dishwashing agents according to the invention are therefore preferably free of anionic, cationic or amphoteric surfactants.
  • the content of nonionic surfactants is at most 5% by weight, preferably at most 2% by weight.
  • Addition products of 1 to 20 moles of ethylene oxide (E0) and / or 1 to 20 moles of propylene oxide (PO) with 1 mole of an aliphatic compound having 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, are particularly suitable as nonionic surfactants.
  • water-soluble nonionic surfactants it is also important that the water is not or not completely water-soluble glycol ethers with 2 to 7 ethylene glycol ether residues in the molecule, preferably these are used in combination with water-soluble nonionic surfactants.
  • alkyl polyglycosides of the general formula R-0- (G) x can also be used as nonionic surfactants, in which R denotes a primary, straight-chain or branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, G represents a glycose unit with 5 or 6 carbon atoms and the degree of oligomerization x is between 1 and 10.
  • Preferred dishwashing detergents according to the invention also contain complexing agents from the group of di- and honorally functional organic carboxylic acids or their salts, e.g. Nitrilotriacetic acid, but especially citric acid or its salts, in an amount of 0.5 to 60% by weight, preferably 20 to 50% by weight.
  • complexing agents from the group of di- and honorally functional organic carboxylic acids or their salts, e.g. Nitrilotriacetic acid, but especially citric acid or its salts, in an amount of 0.5 to 60% by weight, preferably 20 to 50% by weight.
  • Alkali carbonates and hydrogen carbonates used are the sodium carbonates and hydrogen carbonates, which are contained in the amounts already mentioned above.
  • the use of the highly alkaline metasilicates as alkali carriers is preferably avoided.
  • alkali silicates preferably sodium silicates with a SiO 2 Na 2 O molar ratio of 1.5: 1 to 2.5: 1, in amounts of up to 30% by weight, preferably 5 to 20% by weight, based on the entire dishwashing detergent used.
  • sodium perborate tetrahydrate (NaBÜ2 • H2O2 • 3H2O) has sodium perborate monohydrate (NaBÜ2 • H2O2) and peroxycarbonate (a2CÜ3 • 1.5 H2O2) special meaning.
  • Further bleaching agents which can be used are, for example, persic acid salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid. It preferably contains 0.5 to 20% by weight, particularly preferably 5 to 15% by weight, of an oxygen-based bleach, in particular alkali perborates and / or percarbonates.
  • the addition of small amounts of known bleach stabilizers such as borates or metaborates and metasilicates and magnesium salts, for example magnesium sulfate, can be expedient.
  • Suitable bleach activators for these oxidizing agents are in particular N-acyl and O-acyl compounds, preferably tetraacylated diamines such as N, N, N ', N'-tetraacetylethylene diamine (TAED).
  • the agents according to the invention contain such conventional bleach activators in an amount of 0.1 to 10% by weight, preferably 1 to 5% by weight.
  • the agents according to the invention are preferably free of active chlorine-releasing agents such as e.g. Trichloroisocyanuric acid.
  • Enzymes such as proteases, amylases, lipases or cellulases can be used to better remove protein or starch-containing food residues, for example proteases such as BLAP ( R ) 140 from Henkel, 0ptimase ( R ) -M-440, 0ptimase ( R ) -M-330 , 0pticlean ( R ) -M-375, Opti- clean ( R ) -M-250 from Solvay Enzymes, Maxacal ( R ) CX 450,000, Maxapem ( R ) from Ibis, Savinase ( R ) 4.0 T, 6 , 0 T, 8.0 T from Novo or Experase ( R ) T from Ibis; Amylases such as Termamyl ( R ) 60 T, 90 T from Novo, Amylase-L ⁇ ( R ) from Solvay Enzymes or Maxamyl ( R ) P 5000, CXT 5000 or CX
  • Enzymes are contained in the agents according to the invention in an amount of 0.1 to 5% by weight, preferably 0.5 to 2% by weight, based on the total dishwashing detergent.
  • optional silver protection agents as described in the older German patent application P 43 15 397.6, in particular water-soluble Mn (II) salts, can be used in an amount of up to 2% by weight, preferably 0.1 to 0.5% by weight.
  • the dishwashing detergents according to the invention are preferably in the form of pulverulent, granular or tablet-shaped preparations which can be prepared in a conventional manner, for example by mixing, granulating, roller compacting and / or by spray drying. It is also possible for the copolymers used according to the invention to be used in the form of a compound as an additive component to other granular constituents of the dishwashing detergent.
  • the procedure is preferably such that all the constituents are mixed with one another in a mixer and the mixture is produced by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressing pressures in the range from 200 • 10 ⁇ Pa to 1 500 • 10 ⁇ Pa pressed.
  • a tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with one pass ⁇ knife from 35 mm to 40 mm.
  • the manufacture of machine dishwashing detergents in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range from 800 to 900 g / 1 is characterized in that in a first stage of the process, the builder components are used with at least one portion liquid mixing com- components are mixed while increasing the bulk density of this premix and subsequently - if desired after an intermediate drying - the further components of the dishwasher detergent are combined with the premix obtained in this way.
  • the intermediate drying must be carried out in such a way that the decomposition of the sodium bicarbonate into sodium carbonate is as low as possible (or at least as constant as possible). An additional sodium carbonate portion resulting from the drying would have to be taken into account when formulating the granule formulation.
  • Low drying temperatures not only counteract the sodium bicarbonate disintegration, but also increase the solubility of the granulated cleaning agent during use. It is therefore advantageous for drying to have a supply air temperature which, on the one hand, should be as low as possible to avoid bicarbonate decomposition and, on the other hand, must be as high as necessary in order to obtain a product with good storage properties.
  • a supply air temperature of approximately 80 ° C. is preferred during drying.
  • the granules themselves should not be heated to temperatures above about 60 ° C.
  • the builder is generally mixed with at least one further component of the dishwashing detergent with the liquid components.
  • a precursor comes into consideration, in which the builder component in admixture with perborate is acted upon by the liquid nonionic surfactants and / or the solution of the fragrances and intimately mixed.
  • the remaining components are then added, and the entire mixture is worked through and homogenized in the mixing device.
  • additional amounts of liquid in particular the use of additional water, is generally not necessary here.
  • the accumulated material The mixture is then in the form of a free-flowing, dust-free powder of the desired high bulk densities, in the range from 800 to 900 g / l.
  • the pre-granules are then mixed with the missing components of the dishwashing detergent to form the finished product.
  • the mixing time is both in the preliminary stage of the compacting mixture under the influence of liquid components and in the subsequent final mixture with the other components in the range of a few minutes, for example in the range from 1 to 5 minutes.
  • Granular dishwashing detergents of the following composition were produced.
  • Agent A contained 10% by weight of the copolymer which, according to the disclosure of the older German patent application P 42 21 381.9, consists of 50% by weight of acrylic acid, 33% by weight of sucrose and 17% by weight of 2-methallylsulfonic acid was produced and then completely neutralized.
  • Comparative Example B contained 10% by weight of an acrylate maleate sold by BASF under the trade name Sokalan ( R ) CP5.
  • the agent A according to the invention had a superior cleaning performance compared to the agent B not according to the invention, especially when removing the starch, grease stick and oatmeal stains, and showed one with the other stains - apart from the tea stain comparable cleaning performance.
  • agent A according to the invention is superior to comparative agent B above all with regard to the rinse aid effect on glasses and knife blades.
  • Agent C according to the invention showed cleaning and deposit inhibition performances comparable to agent A according to the invention; due to the presence of MnSÜ4, it showed superior properties, especially with regard to the prevention of tarnishing of silverware.

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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)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des détergents peu alcalins pour lave-vaisselle qui contiennent des adjuvants présentant une bonne biodégradabilité. Ces derniers sont des copolymères constitués au moins des monomères d'un acide carboxylique C3-C8 à insaturation monoéthylénique, d'un acide 2-alkylallylsulfonique ou d'un acide arylallylsulfonique et d'un glucide, de préférence de la saccharose.
EP94918884A 1993-06-28 1994-06-20 Detergents pour lave-vaisselle contenant des adjuvants biodegradables Ceased EP0706558A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19934321429 DE4321429A1 (de) 1993-06-28 1993-06-28 Geschirrspülmittel mit biologisch abbaubarer Builderkomponente I
DE4321429 1993-06-28
PCT/EP1994/002001 WO1995000624A1 (fr) 1993-06-28 1994-06-20 Detergents pour lave-vaisselle contenant des adjuvants biodegradables

Publications (1)

Publication Number Publication Date
EP0706558A1 true EP0706558A1 (fr) 1996-04-17

Family

ID=6491391

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94918884A Ceased EP0706558A1 (fr) 1993-06-28 1994-06-20 Detergents pour lave-vaisselle contenant des adjuvants biodegradables

Country Status (7)

Country Link
EP (1) EP0706558A1 (fr)
CA (1) CA2166277A1 (fr)
CZ (1) CZ344395A3 (fr)
DE (1) DE4321429A1 (fr)
HU (1) HUT73203A (fr)
PL (1) PL312473A1 (fr)
WO (1) WO1995000624A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4417919A1 (de) * 1994-05-24 1995-11-30 Henkel Kgaa Klarspülmittel mit biologisch abbaubaren Polymeren
DE19503116A1 (de) * 1995-02-01 1996-08-08 Basf Ag Verwendung von wasserlöslichen gepfropften Naturstoffen als Additiv für Geschirrspülmittel
ATE328991T1 (de) 2000-03-29 2006-06-15 Nat Starch Chem Invest Polymere zur verhinderung von ablagerungen von calciumphosphat und calciumcarbonat in geschirrspülmaschinen
US6521576B1 (en) 2000-09-08 2003-02-18 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Polycarboxylic acid containing three-in-one dishwashing composition
US20070015674A1 (en) 2005-06-30 2007-01-18 Xinbei Song Low phosphate automatic dishwashing detergent composition
GB0522658D0 (en) 2005-11-07 2005-12-14 Reckitt Benckiser Nv Composition
KR20090048455A (ko) 2006-08-10 2009-05-13 바스프 에스이 식기 세척기용 세정 제제
DE102007006628A1 (de) 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102007042907A1 (de) * 2007-09-10 2009-03-12 Henkel Ag & Co. Kgaa Reinigungsmittel
ES2360016T5 (es) 2008-06-24 2015-05-05 Cognis Ip Management Gmbh Detergentes que contienen copolímeros de injerto

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4003172A1 (de) * 1990-02-03 1991-08-08 Basf Ag Pfropfcopolymerisate von monosacchariden, oligosacchariden, polysacchariden und modifizierten polysacchariden, verfahren zu ihrer herstellung und ihre verwendung
FR2663948B1 (fr) * 1990-07-02 1994-06-03 Rhone Poulenc Chimie Composition detergente contenant un polysaccharide greffe biodegradable.

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
EP-A- 0 441 197 *
EP-A- 0 465 287 *
See also references of WO9500624A1 *

Also Published As

Publication number Publication date
CZ344395A3 (en) 1996-07-17
WO1995000624A1 (fr) 1995-01-05
HUT73203A (en) 1996-06-28
HU9503694D0 (en) 1996-02-28
CA2166277A1 (fr) 1995-01-05
PL312473A1 (en) 1996-04-29
DE4321429A1 (de) 1995-01-05

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