EP1513916A1 - Utilisation de copolymeres contenant des unites d'oxyde d'alkylene comme adjuvants dans des produits detergents - Google Patents

Utilisation de copolymeres contenant des unites d'oxyde d'alkylene comme adjuvants dans des produits detergents

Info

Publication number
EP1513916A1
EP1513916A1 EP03740181A EP03740181A EP1513916A1 EP 1513916 A1 EP1513916 A1 EP 1513916A1 EP 03740181 A EP03740181 A EP 03740181A EP 03740181 A EP03740181 A EP 03740181A EP 1513916 A1 EP1513916 A1 EP 1513916A1
Authority
EP
European Patent Office
Prior art keywords
copolymers
mol
component
detergents
alkylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP03740181A
Other languages
German (de)
English (en)
Other versions
EP1513916B1 (fr
Inventor
Pia Baum
Kathrin Michl
Franz Weingart
Stephan Nied
Gregor Brodt
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP1513916A1 publication Critical patent/EP1513916A1/fr
Application granted granted Critical
Publication of EP1513916B1 publication Critical patent/EP1513916B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • 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

Definitions

  • copolymers containing alkylene oxide units as additives in detergents and cleaning agents
  • the present invention relates to the use of copolymers containing alkylene oxide units which
  • R 1 is hydrogen or methyl
  • R 2 is a chemical bond or unbranched or branched Ci-C ⁇ -alkylene
  • R 3 are identical or different unbranched or branched C 2 -C alkylene radicals
  • R 4 unbranched or branched C 1 -C 6 alkyl
  • the invention relates to detergents and cleaning agents which contain these copolymers as a deposit-inhibiting additive.
  • the dishes In automatic dishwashing, the dishes should be cleaned in a residue-free state with an immaculately shiny surface, for which a cleaner, rinse aid and regeneration salt usually have to be used to soften the water.
  • the so-called "2inl" dishwashing detergents introduced on the market contain, in addition to the detergent for removing the soiling on the wash ware, integrated rinse aid surfactants, which ensure that water flows off the wash ware during the rinse and drying cycle and thus prevent limescale and water stains. Refilling a rinse aid is no longer necessary when using these products.
  • Modern machine dishwashers "3inl" cleaners, are to combine the three functions of cleaning, rinsing and water softening in a single detergent formulation, so that the refill of salt with water hardness levels of 1 to 3 is also superfluous for the consumer.
  • Sodium tripolyphosphate is usually added to these cleaners to bind the hardness-forming calcium and magnesium ions. This in turn results in calcium and magnesium phosphate deposits on the wash ware.
  • EP-A-324 568 describes water-soluble copolymers for detergents and cleaning agents which are obtained by polymerizing acrylic acid, methacrylic acid and alkoxypolyethylene glycol methacrylates, which have a long-chain alkoxy radical and / or a long-chain polyethylene glycol block, in the presence of isopropanol be preserved.
  • the alkoxypolyethylene glycol methacrylate content of these copolymers is ⁇ 1 mol%.
  • copolymers based on at least one monomer from the group of maleic acid, acrylic acid and methacrylic acid and an optionally methoxy- or ethoxylated polyethylene glycol (meth) acrylate as a further monomer which have an average molecular weight M w of 1,000 to 10,000, are used for desizing, cleaning, bleaching and dyeing natural and synthetic bevels.
  • Copolymers of acrylic acid and methoxypolyethylene glycol methacrylate are disclosed in detail.
  • JP-A-2000/24691 describes copolymers of monomers containing unsaturated carboxylic acids and polyalkylene oxide units with average molecular weights M w of> 50,000 to 3,000,000 as agents against scale based in particular on silicates in water circuits, for example cooling systems. In one only copolymers of acrylic acid and methoxypolyethylene glycol methacrylate are disclosed individually.
  • the object of the invention was to remedy the problems outlined above and to provide an additive which can also be used advantageously, in particular, in multifunctional cleaners and in particular has a deposit-inhibiting effect.
  • R 1 is hydrogen or methyl
  • R 2 is a chemical bond or unbranched or branched Ci-C ß alkylene
  • R 3 are identical or different unbranched or branched C 2 -C alkylene radicals
  • R 4 unbranched or branched Ci-C ß alkyl
  • copolymerized randomly or in blocks found as an additive to detergents and cleaning agents. Furthermore, detergents and cleaning agents have been found which contain the copolymers containing alkylene oxide units as a coating-inhibiting additive.
  • the copolymers containing alkylene oxide units contain as copolymerized components (a) and (b) acrylic acid or methacrylic acid and / or water-soluble salts of these acids, in particular the alkali metal salts, such as potassium and especially sodium salts, and ammonium salts.
  • the proportion of acrylic acid (a) in the copolymers to be used according to the invention is 50 to 93 mol%, preferably 65 to 85 mol% and particularly preferably 65 to 75 mol%.
  • Methacrylic acid (b) is present in the copolymers to be used according to the invention in an amount of 5 to 30 mol%, preferably 10 to 25 mol% and especially 15 to 25 mol%.
  • the copolymers contain, as component (c), nonionic monomers of the formula I.
  • R 1 is hydrogen or preferably methyl
  • R 2 unbranched or branched Ci-C ⁇ alkylene or preferably a chemical bond
  • R 3 same or different unbranched or branched
  • R 4 unbranched or branched Ci-C ⁇ -alkyl, preferably dC 2 alkyl;
  • n 3 to 50 preferably 5 to 40, particularly preferably 10 to 30.
  • methoxypolyethylene glycol (meth) acrylate methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and Ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, methoxypolyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate being preferred and methoxypolyethylene glycol methacrylate being particularly preferred.
  • the polyalkylene glycols contain 3 to 50, especially 5 to 40 and especially 10 to 30 alkylene oxide units.
  • the proportion of nonionic monomers (c) in the copolymers to be used according to the invention is 2 to 20 mol%, preferably 5 to 15 mol% and especially 5 to 10 mol%.
  • the copolymers to be used according to the invention generally have an average molecular weight M w of 3,000 to 50,000, preferably 10,000 to 30,000 and particularly preferably 15,000 to 25,000.
  • the K value of the copolymers is usually 15 to 40, in particular 20 to 35, especially 27 to 30 (measured in 1% by weight aqueous solution at 25 ° C., according to H. Fikentscher, Cellulose- Chemie, vol. 13, pp. 58-64 and 71-74 (1932)).
  • copolymers to be used according to the invention can be produced by radical polymerization of the monomers. All known radical polymerization processes can be used. In addition to bulk polymerization, the methods of solution polymerization and emulsion polymerization should be mentioned in particular, with solution polymerization being preferred.
  • the polymerization is preferably carried out in water as a solvent.
  • alcoholic solvents in particular C 1 -C 4 alcohols, such as methanol, ethanol and isopropanol, or mixtures of these solvents with water.
  • thermally activatable polymerization initiators include initiators with a decomposition temperature in the range from 20 to 180 ° C., in particular from 50 to 90 ° C., are preferred.
  • suitable thermal initiators are inorganic peroxo compounds, such as peroxodisulfates (ammonium and preferably sodium peroxoxdisulfate), peroxosulfates, percarbonates and hydrogen peroxide; organic peroxo compounds, such as diacetyl peroxide, di tert.-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toloyl) peroxide, succinyl peroxide, tert.-butyl peracetate, tert , tert-butyl peroctoate, tert.
  • inorganic peroxo compounds such as peroxo
  • Butyl perneodecanoate tert. -Butylperbenzoa, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2-ethylhexanoate and diisopropyl peroxidicarbamate; Azo compounds such as 2, 2 '-azobisisobutyronitrile, 2,2' -azo-bis (2-methylbutyronitrile) and azobis (2-amidopropane) dihydrochloride.
  • initiators can be used in combination with reducing compounds as starter / controller systems.
  • reducing compounds include phosphorus-containing compounds, such as phosphorous acid, hypophosphites and phosphinates, sulfur-containing compounds, such as sodium bisulfite, sodium sulfite and sodium formaldehyde sulfoxilate, and hydrazine.
  • photoinitiators examples include benzophenone, aceto-phenone, benzoin ether, benzyl dialkyl ketones and their derivatives.
  • Thermal initiators are preferably used, inorganic peroxo compounds, in particular sodium peroxodisulfate (sodium persulfate), being preferred.
  • the peroxo compounds are used particularly advantageously in combination with sulfur-containing reducing agents, in particular sodium bisulfite, as the redox initiator system.
  • sulfur-containing reducing agents in particular sodium bisulfite
  • copolymers are obtained which contain -S0 ⁇ Na + and / or -S0 ⁇ Na + as end groups and are notable for particular cleaning power and deposit-inhibiting action.
  • starter / regulator systems containing phosphorus can also be used, e.g. Hypophosphites / phosphinates.
  • the quantities of photoinitiator and starter / regulator system must be matched to the substances used. If, for example, the preferred system peroxodisulfate / hydrogen sulfite is used, 2 to 6% by weight, preferably 3 to 5% by weight, peroxodisulfate and usually 5 to 30% by weight, preferably 5 to 10% by weight, are usually used. %, Hydrogen sulfite, based in each case on the monomers (a), (b) and (c).
  • polymerization regulators can also be used.
  • the compounds known to those skilled in the art are suitable, for example sulfur compounds, such as mercaptoethanol, 2-ethylhexylthioglycolate, thioglycolic acid and dodecyl mercaptan. If polymerisa- tion controller are used, their amount is in the
  • the polymerization temperature is generally 30 to 200 ° C, preferably 50 to 150 ° C and particularly preferably 80 to
  • the polymerization can be carried out under atmospheric pressure, but is preferably carried out in a closed system under the self-developing pressure.
  • the monomers (a), (b) and (c) can be used as such in the preparation of the copolymers to be used according to the invention, but reaction mixtures which are obtained in the preparation of the monomers (c) can also be used.
  • reaction mixtures which are obtained in the preparation of the monomers (c) can also be used.
  • methoxypolyethylene glycol methacrylate the monomer mixture obtained in the esterification of polyethylene glycol monomethyl ether with an excess of methacrylic acid can be used.
  • the esterification can advantageously also be carried out in situ in the polymerization mixture by combining (1) acrylic acid, (2) a mixture of methacrylic acid and polyethylene glycol monomethyl ether and (3) radical initiators in parallel.
  • a catalyst required for the esterification such as methanesulfonic acid or p-toluenesulfonic acid, can additionally be used.
  • copolymers to be used according to the invention can also be obtained by a polymer-analogous reaction, e.g. by reacting an acrylic acid / methacrylic acid copolymer with polyalkylene glycol onoalkyl ether.
  • a polymer-analogous reaction e.g. by reacting an acrylic acid / methacrylic acid copolymer with polyalkylene glycol onoalkyl ether.
  • the radical copolymerization of the monomers is preferred.
  • the aqueous solutions obtained in the preparation of the copolymers containing carboxylic acid groups to be used according to the invention can be neutralized or partially neutralized, i.e., by adding base, in particular sodium hydroxide solution. adjusted to a pH in the range 4-8, preferably 4.5-7.5.
  • copolymers used according to the invention are outstandingly suitable as additives for detergents and cleaning agents.
  • the copolymers used according to the invention thereby also increase the cleaning power of the dishwashing detergent. In addition, they promote the drainage of the water from the wash items even in low concentrations, so that the proportion of rinse aid surfactants in the dishwashing detergent can be reduced.
  • copolymers containing sulfonic acid groups are used, in particular also when the dishwasher is operated without water regeneration salt for water softening.
  • the copolymers containing sulfonic acid groups can therefore be used advantageously not only in 2inl cleaners but also in 3inl cleaners.
  • copolymers used according to the invention can be used directly in the form of the aqueous solutions obtained in the preparation and also in dried, e.g. form obtained by spray drying, fluidized spray drying, roller drying or freeze drying. Accordingly, the detergents and cleaning agents according to the invention can be in solid or liquid form, e.g. be provided as powders, granules, extrudates, tablets, liquids or gels.
  • reaction mixture After stirring for two hours at 100 ° C., the reaction mixture was cooled to room temperature and adjusted to a pH of 7.2 by adding 190 g of 50% strength by weight sodium hydroxide solution. A slightly yellowish, clear solution of a copolymer with a solids content of 25.7% by weight and a K value of 27.2 (1% by weight aqueous solution, 25 ° C.) was obtained.
  • Dishwasher Miele G 686 SC rinses: 2 rinses 55 ° C normal (without pre-rinsing) dishes: knife (WMF table knife Berlin, monoblock) 10 and barrel-shaped glass beaker (Matador, Ruhr Kristall)
  • Dishwashing liquid 21 g copolymer: 4.2 g rinse aid temperature: 65 ° C 15 water hardness: 25 ° dH
  • the items to be washed were assessed 18 hours after cleaning by visual inspection in a black-painted light box with halogen spotlight and pinhole using a grading scale from 20 10 (very good) to 1 (very bad).
  • the highest grade 10 corresponds to surfaces free of deposits and drips, from scores ⁇ 5 deposits and drops are already recognizable with normal room lighting, so they are perceived as disturbing.

Landscapes

  • 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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
EP03740181A 2002-06-07 2003-06-04 Utilisation de copolymeres contenant des unites d'oxyde d'alkylene comme adjuvants dans des compositions pour lave-vaisselle Expired - Lifetime EP1513916B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10225594 2002-06-07
DE10225594A DE10225594A1 (de) 2002-06-07 2002-06-07 Verwendung von Alkylenoxideinheiten enthaltenden Copolymeren als Zusatz in Wasch- und Reinigungsmitteln
PCT/EP2003/005823 WO2003104373A1 (fr) 2002-06-07 2003-06-04 Utilisation de copolymeres contenant des unites d'oxyde d'alkylene comme adjuvants dans des produits detergents

Publications (2)

Publication Number Publication Date
EP1513916A1 true EP1513916A1 (fr) 2005-03-16
EP1513916B1 EP1513916B1 (fr) 2006-10-11

Family

ID=29557707

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03740181A Expired - Lifetime EP1513916B1 (fr) 2002-06-07 2003-06-04 Utilisation de copolymeres contenant des unites d'oxyde d'alkylene comme adjuvants dans des compositions pour lave-vaisselle

Country Status (11)

Country Link
US (1) US20050245427A1 (fr)
EP (1) EP1513916B1 (fr)
JP (1) JP2005531653A (fr)
CN (1) CN1273577C (fr)
AT (1) ATE342332T1 (fr)
AU (1) AU2003274115A1 (fr)
BR (1) BR0311490B1 (fr)
CA (1) CA2488032C (fr)
DE (2) DE10225594A1 (fr)
MX (1) MXPA04011456A (fr)
WO (1) WO2003104373A1 (fr)

Families Citing this family (8)

* 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
DE102005028460A1 (de) * 2005-06-17 2006-12-28 Basf Ag Verwendung von Alkylenoxideinheiten enthaltenden Copolymeren als Zusatz zu wäßrigen Systemen
DE102005041349A1 (de) * 2005-08-31 2007-03-01 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate
DE102005041347A1 (de) 2005-08-31 2007-03-01 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate
DE102008028229A1 (de) * 2008-06-16 2009-12-17 Fit Gmbh Zusammensetzung zur Herstellung von Reinigungsmitteln, Tablettiermischung, Polymerkombination, Reinigunsmittel-Formkörper und Verfahren zur deren Herstellung
US8685911B2 (en) * 2009-11-30 2014-04-01 The Procter & Gamble Company Rinse aid compositions
JP5668936B2 (ja) * 2011-09-06 2015-02-12 三浦工業株式会社 全窒素の定量方法
US20210317386A1 (en) * 2018-08-03 2021-10-14 Nippon Shokubai Co., Ltd. Polycarboxylic acid copolymer

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3719647A (en) * 1971-01-25 1973-03-06 Procter & Gamble New polymers and detergent compositions containing them
JP2901294B2 (ja) * 1989-12-12 1999-06-07 日華化学株式会社 繊維製品用洗浄性向上剤
JP2000024691A (ja) * 1998-07-09 2000-01-25 Jsr Corp 水溶性共重合体（塩）およびスケール防止剤
US6998453B2 (en) * 2001-10-03 2006-02-14 Nippon Shokubai Co., Ltd. (Meth)acrylic acid type polymer and unsaturated polyalkylene glycol type copolymer, and methods for production thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03104373A1 *

Also Published As

Publication number Publication date
MXPA04011456A (es) 2005-02-14
CA2488032A1 (fr) 2003-12-18
DE10225594A1 (de) 2003-12-18
WO2003104373A1 (fr) 2003-12-18
AU2003274115A1 (en) 2003-12-22
BR0311490B1 (pt) 2013-04-09
DE50305365D1 (de) 2006-11-23
JP2005531653A (ja) 2005-10-20
CA2488032C (fr) 2010-09-14
CN1659264A (zh) 2005-08-24
EP1513916B1 (fr) 2006-10-11
CN1273577C (zh) 2006-09-06
BR0311490A (pt) 2005-03-15
US20050245427A1 (en) 2005-11-03
ATE342332T1 (de) 2006-11-15

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