WO1995000623A1 - Detergent pour lave-vaisselle contenant des adjuvants - Google Patents

Detergent pour lave-vaisselle contenant des adjuvants Download PDF

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Publication number
WO1995000623A1
WO1995000623A1 PCT/EP1994/002000 EP9402000W WO9500623A1 WO 1995000623 A1 WO1995000623 A1 WO 1995000623A1 EP 9402000 W EP9402000 W EP 9402000W WO 9500623 A1 WO9500623 A1 WO 9500623A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
composition according
meth
agent
salts
Prior art date
Application number
PCT/EP1994/002000
Other languages
German (de)
English (en)
Inventor
Willi Buchmeier
Hans Andree
Peter Krings
Birgit Burg
Jürgen Härer
Peter Jeschke
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP94918883A priority Critical patent/EP0706557A1/fr
Publication of WO1995000623A1 publication Critical patent/WO1995000623A1/fr

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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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid 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
    • 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

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 mechanical cleaning of dishes contain, in addition to bleaching agents based on oxygen, surface-active substances and enzymes, a combination of water-soluble builders which are derived from complexing agents, e.g. Citrate, from alkali carriers, e.g. Soda, bicarbonate or disilicate, and from dispersants such as e.g. Polycarboxylates exist.
  • complexing agents e.g. Citrate
  • alkali carriers e.g. Soda, bicarbonate or disilicate
  • dispersants such as e.g. Polycarboxylates
  • Other possible binder components are organophosphonic acids, aminocarboxylic acids or crystalline layered silicates; on the phosphates previously used, e.g. Pentasodium tripolyphosphate is largely dispensed with today for ecological reasons.
  • the polycarboxylates used in today's dishwashing detergents e.g. Maleinat / Acrylat-Copoly ere, prevent limescale deposits when the residual water hardness is too high in the cleaning and rinse cycle; with a high salt load in the washing liquor, they also improve the rinse aid effect.
  • US Pat. No. 3,887,480 discloses dishwashing and textile cleaning agents which contain a polymer which consists of 35-70 mol% maleic acid, 20-45 mol% vinyl acetate and 2-40 mol% acrylic acid.
  • the European patent EP 0 193 360 B1 describes zeolite-containing textile detergents, the polycarboxylate poly ere composed of a C3-Cio-onocarboxylic acid, a C ⁇ -Cß-dicarboxylic acid and a nonionic spacer, for. B. vinyl alcohol included.
  • the US Pat. No. 3,755,264 discloses copolymers which, for. B.
  • EP 0 076 992 AI discloses u. a. the use of polymers composed of 50-95% by weight of acrylic acid, 0.5 to 5% by weight of vinyl acetate and up to 49% by weight of maleic acid as incrustation inhibitors in washing and cleaning agents.
  • the invention relates to a low-alkaline agent for machine 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 based on oxygen, characterized in that it contains a copoly as water-soluble builder component, the copolymer comprising 60-95% by weight, preferably 70-90% by weight, of (meth) acrylic acid or (meth) acrylate , preferably acrylic acid or acrylate, and maleic acid or maleate and 5-40% by weight, preferably 10-25% by weight, of vinyl alcohol and / or vinyl acetate, the weight ratio being (meth) acrylic acid or (meth) acrylate to maleic acid or Maleate is between 1.5: 1 and 4: 1, preferably between 2: 1 and 2.5: 1, both the amounts and the weight ratios are based on the acids, and a copolymer of the salts of the acids and vinyl alcohol is preferred are moving.
  • the copolymers used according to the invention can be prepared by any of the known and customary processes.
  • (meth) acrylic acid, preferably acrylic acid, and maleic acid are reacted with vinyl alcohol and / or vinyl acetate, whereupon the acids may then be neutralized to preferably their alkali metal salts, such as the sodium or potassium salts or ammonium salts or alkanolamine salts, such as the monoethanol insole the triethanolamine salt, and optionally a partial or complete cleavage of the vinyl acetate to the vinyl alcohol is carried out.
  • alkali metal salts such as the sodium or potassium salts or ammonium salts or alkanolamine salts, such as the monoethanol insole the triethanolamine salt
  • copolymers which are either completely or at least partially, in particular to more than 50%, based on the existing carboxyl groups are neutralized.
  • a completely neutralized copolymer is particularly preferred, ie it consists of the salts of (meth) acrylic acid, preferably acrylic acid, and maleic acid, in particular the sodium or potassium salts, and vinyl alcohol.
  • 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 powder-sprayed form. Particularly preferred copolymers are produced by a process which is described in the earlier German patent application P 43 00 772.4.
  • 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, of a bleaching agent based on oxygen, in particular alkali perborate and / or percarbonate, and nonionic surfactants in an amount of at most 5% by weight, preferably at most 2% by weight, the agents being free from anionic, cationic or amphoteric surfactants.
  • a bleaching agent based on oxygen in particular alkali perborate and / or percarbonate
  • nonionic surfactants in an amount of at most 5% by weight, preferably at most 2% by weight, the agents being free from anionic, cationic or amphoteric surfactants.
  • alkali metal carbonates and / or hydrogen carbonates, in particular the sodium salts are present as alkali carriers in an amount of up to 60% by weight, preferably 5 to 50% by weight.
  • the dishwashing detergents according to the invention can contain 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, polymaleinates or copolymers of acrylic acid with maleic acid or maleic anhydride, in an amount of 0.5 Contain up 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, polymaleinates or copolymers of acrylic acid with maleic acid or maleic anhydride, in an amount of 0.5 Contain up 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 Norsohaas, Degapas ( R ) from Degussa; Suitable copolymers of polyacrylic acid and maleic acid are, for example, Sokalan ( R ) CP 5, CP 7 from BASF, Acrysol ( R ) QR 1014 from Norsohaas, Alcosperse ( R ) 175 from Alco.
  • phosphates or zeolites can also be present, but the dishwashing detergents are preferably free from zeolites and from phosphate-containing bath components.
  • nonionic surfactants In the case of 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 machine mechanics. Above all, these are nonionic surfactants;
  • the dishwashing detergents 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 with 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines and carboxamides are the nonionic surfactants and alkanesulfonamides of interest.
  • polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule, which are not or not completely water-soluble are also important, preferably in combination with water-soluble nonionic ones Surfactants used.
  • 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 C atoms, G for a glyco - Se 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 the di- and honorically 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 the di- and honorically 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.
  • M alkali metal
  • 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.
  • bleaching agents that can be used are, for example, peracidic 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.
  • bleach stabilizers such as borates or metaborates and metasilicates and magnesium salts, for example magnesium sulfate.
  • 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 in (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 from agents that release active chlorine, e.g. Trichloroisocyanuric acid.
  • Enzymes such as proteases, aylases, lipases or cellulases can be used to better remove protein or starch-containing food residues, for example proteases such as BLAP () 140 from Henkel, 0ptimase ( R ) -M-440, 0ptimase ( R ) -M -330, 0pticlean ( R ) -M-375, 0pticlean ( R ) -M-250 from Solvay Enzy es, 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, A ylase-LT ( R ) from Solvay Enzymes or Maxamyl ( R ) P 5000, CXT 5000 or C
  • silver protection agents as described in the older German patent application P 43 15 397.6, in particular water-soluble Mn (II) salts, in an amount of up to 2% by weight, preferably 0. 1 to 0.5 wt .-%, may be included.
  • the dishwashing detergents according to the invention are preferably in the form of powdery, granular or tablet-like 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 polymers used according to the invention to be in the form of a compound can be used as an additive component to other granular components of the dishwashing detergent.
  • the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture is used by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200 ⁇ 10 ⁇ Pa to 1 500 • 10 ⁇ Pa pressed.
  • a tablet produced in this way has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter from 35 m to 40 mm.
  • the production 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 process stage, the builder components are at least partially liquid Mixing 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 so that the decomposition of the sodium bicarbonate to 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 ⁇ granulate recipe.
  • Low drying temperatures not only counteract sodium bicarbonate decay, but also increase the solubility of the granulated detergent 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. When drying, a supply air is preferred. te temperature of approx. 80 ° C. The granules themselves should not be heated to temperatures above about 60 ° C.
  • the builder is generally acted upon with at least one further component of the dishwashing agent with the liquid components.
  • a precursor may be considered in which the builder component, mixed with perborate, is acted upon by the liquid nonionic surfactants and / or the solution of the fragrances and mixed intimately.
  • 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 mixture of substances obtained is then in the form of a free-flowing, dust-free powder of the desired high bulk densities, approximately in the range from 800 to 900 g / l.
  • the pre-granules are then mixed with the still 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 of 1 to 5 minutes.
  • Granular dishwashing detergents with the following composition were produced.
  • Agent A contained 10% by weight of the copolymer which, according to the disclosure of the earlier German patent application P 43 00 772.4, was prepared from 80% by weight of acrylic acid and maleic acid in a weight ratio of 7: 3 and from 20% by weight of vinyl acetate and then completely neutralized had been.
  • Comparative Example B contained 10% by weight of an acrylate-maleate copolymer sold by BASF under the trade name Sokalan ( R ) CP5.
  • Agent A according to the invention had a superior cleaning performance compared to agent B not according to the invention, particularly when removing the starch, minced meat, fat stick and oatmeal stains, but in particular when staining tea.
  • agents A and B were carried out in a Miele G 590 dishwasher (Universal 65 ° C program) at doses of 20 g each in 7.0 l of water at 16 ° dH with the addition of 50 g of pumpable soiling (mixture of ketchup, gravy , Mustard, potato starch, egg yolk, milk, margarine) in the presence of 3.0 ml of a commercial rinse aid tested over 10 rinse cycles.
  • 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 MnSÜ, it showed superior properties especially in preventing silver tarnishing from tarnishing.

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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 d'acide (méth)acrylique ou de (méth)acrylate, d'acide maléique ou de maléate et d'alcool vinylique et/ou d'acétate vinylique.
PCT/EP1994/002000 1993-06-28 1994-06-20 Detergent pour lave-vaisselle contenant des adjuvants WO1995000623A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP94918883A EP0706557A1 (fr) 1993-06-28 1994-06-20 Detergent pour lave-vaisselle contenant des adjuvants

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4321430.4 1993-06-28
DE19934321430 DE4321430A1 (de) 1993-06-28 1993-06-28 Geschirrspülmittel mit biologisch abbaubarer Builderkomponente II

Publications (1)

Publication Number Publication Date
WO1995000623A1 true WO1995000623A1 (fr) 1995-01-05

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/002000 WO1995000623A1 (fr) 1993-06-28 1994-06-20 Detergent pour lave-vaisselle contenant des adjuvants

Country Status (7)

Country Link
EP (1) EP0706557A1 (fr)
CA (1) CA2166186A1 (fr)
CZ (1) CZ342395A3 (fr)
DE (1) DE4321430A1 (fr)
HU (1) HUT73202A (fr)
PL (1) PL312472A1 (fr)
WO (1) WO1995000623A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130050056A1 (en) * 2011-08-31 2013-02-28 Qualcomm Incorporated Wireless device with 3-d antenna system
CN107083287A (zh) * 2017-04-20 2017-08-22 合肥酷睿网络科技有限公司 一种新型机械加工用清洁剂及其生产工艺
WO2020086257A1 (fr) * 2018-10-22 2020-04-30 Dow Global Technologies Llc Composition pour lave-vaisselle automatique contenant un polymère dispersant

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10350420A1 (de) * 2003-10-28 2005-06-02 Basf Ag Verwendung von Alkylenoxideinheiten enthaltenden Copolymeren als belagsinhibierende Additive im Klarspülgang des maschinellen Geschirrspülers
BR112019011182B1 (pt) 2016-12-16 2022-12-13 Dow Global Technologies Llc Composição detergente de lavagem automática de louça

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0497611A1 (fr) * 1991-02-01 1992-08-05 Rohm And Haas Company Polymères biodégradables, procédé pour la préparation de tels polymères, et compositions contenant de tels polymères
EP0504091A1 (fr) * 1991-03-15 1992-09-16 Cleantabs A/S Composition pour le lavage machinal de la vaisselle sans phosphate
WO1992017565A1 (fr) * 1991-03-30 1992-10-15 Henkel Kommanditgesellschaft Auf Aktien Produit a laver la vaisselle en machine faiblement alcalin, sans chlore et sans phosphates, sous forme de poudres et de granules denses

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0497611A1 (fr) * 1991-02-01 1992-08-05 Rohm And Haas Company Polymères biodégradables, procédé pour la préparation de tels polymères, et compositions contenant de tels polymères
EP0504091A1 (fr) * 1991-03-15 1992-09-16 Cleantabs A/S Composition pour le lavage machinal de la vaisselle sans phosphate
WO1992017565A1 (fr) * 1991-03-30 1992-10-15 Henkel Kommanditgesellschaft Auf Aktien Produit a laver la vaisselle en machine faiblement alcalin, sans chlore et sans phosphates, sous forme de poudres et de granules denses

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130050056A1 (en) * 2011-08-31 2013-02-28 Qualcomm Incorporated Wireless device with 3-d antenna system
CN107083287A (zh) * 2017-04-20 2017-08-22 合肥酷睿网络科技有限公司 一种新型机械加工用清洁剂及其生产工艺
WO2020086257A1 (fr) * 2018-10-22 2020-04-30 Dow Global Technologies Llc Composition pour lave-vaisselle automatique contenant un polymère dispersant
CN112739806A (zh) * 2018-10-22 2021-04-30 陶氏环球技术有限责任公司 具有分散剂聚合物的自动餐具洗涤组合物
CN112739806B (zh) * 2018-10-22 2024-01-02 陶氏环球技术有限责任公司 具有分散剂聚合物的自动餐具洗涤组合物
US11920110B2 (en) 2018-10-22 2024-03-05 Dow Global Technologies Llc Automatic dishwashing composition with dispersant polymer

Also Published As

Publication number Publication date
CZ342395A3 (en) 1996-06-12
PL312472A1 (en) 1996-04-29
DE4321430A1 (de) 1995-01-05
CA2166186A1 (fr) 1995-01-05
HU9503693D0 (en) 1996-02-28
HUT73202A (en) 1996-06-28
EP0706557A1 (fr) 1996-04-17

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