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
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
• • 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
  • C11D17/0078—Multilayered 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/06—Phosphates, including polyphosphates
• • 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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/08—Silicates
• • 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
  • C11D3/3796—Amphoteric polymers or zwitterionic polymers
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds

Definitions

• the subject of the present invention is the use, in a “two in one” or “three in one” washing and rinsing composition of tableware in a machine, of a water-soluble or water-dispersible amphoteric copolymer as an anti-redeposition agent for soiling (“ soil repellent agent ”).
• a solid preformulation in particular in the form of granules, comprising said amphoteric copolymer adsorbed and / or absorbed on a water-soluble solid inorganic support, as well as the use, in a composition “two in one ”or“ three in one ”washing and rinsing dishes in the machine, of said preformulation as an anti-redeposition agent for soiling (“ soil repellent agent ”).
• compositions for the treatment of hard surfaces water-soluble or water-dispersible amphoteric copolymers derived from at least one cationic monomer from the family of diallyldimethylammonium chloride (DADMAC for diallyldimethylammonium chloride), at least one anionic monomer (especially acrylic acid) and optionally at least one nonionic monomer, to give the treated surface hydrophilization properties.
• DMDMAC diallyldimethylammonium chloride
• anionic monomer especially acrylic acid
• nonionic monomer optionally at least one nonionic monomer
• compositions confer in particular on the treated surfaces anti-flow, anti-fogging, anti-stain or anti-stain properties; the term “anti-trace” or “anti-staining” properties means that the treated surface retains these properties over time, including after subsequent contact with water, whether it is rain water, distribution network water or rinse water with or without rinse aid. It is therefore a question here of essentially avoiding stains or traces of water and limescale.
• a first object of the invention consists in the use, in a washing and rinsing composition “two in one” (“two in one”) or “three in one” (“three in one”) for cleaning the dishes.
• a washing and rinsing composition “two in one” (“two in one”) or “three in one” (“three in one”) for cleaning the dishes.
• a machine of a water-soluble or water-dispersible amphoteric copolymer comprising, in the form of polymerized units:
• - Ri and R 4 independently of one another represent a hydrogen atom or a linear or branched C ⁇ -C 6 alkyl group;
• - R 2 and R 3 independently of one another represent an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl group is a C ⁇ -C 6 chain, linear or branched, preferably a methyl group;
• - n and m are whole numbers between 1 and 3;
• - X represents a counterion compatible with the water-soluble or water-dispersible nature of the polymer
• (c) optionally at least one hydrophilic monomer compound with ethylenic unsaturation of neutral charge carrying one or more hydrophilic groups, copolymerizable with (a) and (b), in which the molar ratio a / b is between 15/85 and less 50/50, preferably between 25/75 and 45/55, as an anti-redeposition agent for soiling (“soil repellent agent”).
• soil repellent agent an anti-redeposition agent for soiling
• R 4 represents hydrogen
• ion X " is advantageously chosen from the halide ions (chloride,
• the copolymer according to the invention advantageously has a molecular mass of at least 1,000, advantageously of at least 10,000; it can preferably range from 50,000 to 500,000. Unless otherwise indicated, when we speak of molecular mass, it will be the molecular mass by weight, expressed in g / mol.
• the copolymer is preferably random.
• the monomer (a) has the following structure:
• X " being is as defined above.
• a particularly preferred monomer is that of the above formula in which X " represents CI " , called DADMAC.
• the monomers (b) are advantageously C 3 -C 8 carboxylic, sulfonic, sulfuric, phosphonic or phosphoric acids with water-soluble monoethylenic unsaturation, their anhydrides and their water-soluble salts.
• carboxylic acids such as acrylic acid, methacrylic acid, ⁇ -ethacrylic acid, ⁇ , ⁇ -dimethylacrylic acid, methylenemalonic acid, vinylacetic acid , allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-methacroyl -alanine, N-acryloyl-hydroxy-glycine. and the alkali metal and ammonium salts thereof.
• carboxylic acids such as acrylic acid, methacrylic acid, ⁇ -ethacrylic acid, ⁇ , ⁇ -dimethylacrylic acid, methylenemalonic acid, vinylacetic acid , allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic
• the monomers (c) there may be mentioned acrylamide, vinyl alcohol, dC 4 alkyl esters of acrylic acid and methacrylic acid, dC hydroxyalkyl esters of acrylic acid and methacrylic acid, in particular ethylene glycol and propylene glycol methacrylate and methacrylate, polyalkoxylated esters of acrylic acid and methacrylic acid, in particular esters polyethylene glycol and polypropylene glycol.
• the level of monomers (c) is advantageously between 0 and 50%, preferably 0 to 30 mol%.
• copolymers are very particularly preferred:
• DADMAC / maleic acid copolymers - DADMAC / itaconic acid copolymers; the DADMAC / acid monomer molar ratio being between 15/85 and less than 50/50, preferably between 25/75 and 45/55.
• the most preferred copolymers are the DADMAC / acrylic acid copolymers whose molar ratio is between 15/85 and less than 50/50, preferably between 25/75 and 45/55.
• the washing and rinsing composition “two in one” or “three in one” according to the invention comprises at least one copolymer as described above at a content of between 0.01% and 10%, preferably between 0.02 % and 0.5% by weight relative to the total weight of the composition.
• the composition according to the invention generally comprises at least one surfactant. This is advantageously non-ionic and / or anionic and / or amphoteric; preferably it is a nonionic surfactant.
• nonionic surfactants there may be mentioned in particular the condensates of alkylene oxide, in particular of ethylene oxide and optionally of propylene with alcohols, polyols, alkylphenols, fatty acid esters, fatty acid amides and fatty amines; amine oxides, sugar derivatives such as alkylpolyglycosides or esters of fatty acids and sugars, in particular sucrose monopalmitate; long chain tertiary phosphine oxides; dialkylsulfoxides; polyoxyethylene and polyoxypropylene block copolymers; polyalkoxylated sorbitan esters; fatty esters of sorbitan, poly (ethylene oxide) and fatty acid amides modified so as to give them a hydrophobic character (for example, mono- and diethanolamides of fatty acids containing from 10 to 18 carbon atoms ).
• alcohols polyols, alkylphenols, fatty acid esters, fatty acid amides and fatty amine
• amphoteric surfactants mention may be made of sodium alkyl iminopropionates or iminodipropionates, such as Mirataine H2C HA and Mirataine JC HA from Rhodia.
• Surfactants can be present in an amount of 0.1 to 20%, preferably 0.2 to 10% by weight.
• the copolymer weight ratio of general formula (I) / surfactant is between 1/2 and 1/100, advantageously 1/5 and 1/50.
• the proportions are given by weight.
• organic "builders” or “cobuilders” detergency builders improving the surface properties of surfactants
• organic phosphonates and water-soluble aminophosphonates such as. ethane 1-hydroxy-1, 1-diphosphonates,. aminotri (methylene diphosphonate). vinyldiphosphonates
• cotelomer salts of vinylphosphonic or vinyldiphosphonic acid and acrylic acid such as those of the BRIQUEST® or MIRAPOL A300 or 400 range from RHODIA (at a rate of 0 to 2% of the total weight of detergent composition expressed as dry matter); • polycarboxylic acids or their water-soluble salts and the water-soluble salts of carboxylic polymers or copolymers such as. polycarboxylate or hydroxypolycarboxylate ethers.
• polyacetic acids or their salts nitriloacetic acid, N acid, N-dicarboxymethyl-2-aminopentane dioic, ethylenediamine-tetraacetic acid, diethylenetriamine pentaacetic acid, ethylenediamine-tetraacetates, nitrilotriacetates, N- (2 hydroxyethyl) -nitrilod 0 to 10% of the total weight of detergent composition expressed as dry matter); . salts of succinic C 5 -C 2 o acids
• polyacetal carboxylic esters salts of polyaspartic or polyglutamic acids. citric acid, gluconic acid or tartaric acid or their salts (at a rate of 0 to 10% of the total weight of detergent composition expressed as dry matter in the case of a composition for dishwasher);
• polyphosphates of alkali metals, ammonium or alkanolamines such as RHODIAPHOS HD7 sold by the company RHODIA, (at a rate of 0 to 70% of the total weight of detergent composition expressed as dry matter);
• alkali metal silicates with a Si ⁇ 2 / M 2 0 ratio which can range from 1 to 4, preferably from 1.5 to 3.5, most particularly from 1.7 to 2.8; they may be amorphous silicates or lamellar silicates such as the ⁇ -, ⁇ -, ⁇ - and ⁇ - phases of Na 2 Si 2 0 5 , sold under the references
• borates, carbonates, bicarbonates, alkali or alkaline earth sesquicarbonates in an amount which can range up to approximately 50% of the total weight of said detergent composition expressed as dry matter
• cogranules of hydrated alkali metal silicates with Si ⁇ 2 / M 2 0 ratio which can range from 1.5 to 3.5, and alkali metal carbonates (sodium or potassium) Mention may in particular be made of cogranules in which the weight content of water associated with the silicate relative to the dry silicate is at least 33/100, the weight ratio of silicate to carbonate possibly ranging from 5/95 to 45/55, preferably from 15/85 to 35/65, as described in EP-A-488 868 and EP-A-561,656, such as NABION 15 sold by the company RHODIA; (the total quantity of organic and / or mineral "builders", which can represent up to 90% of the total weight of said detergent composition expressed as dry matter); ⁇ bleaches of the perborate type, percarbonates associated or not with
• a washing and rinsing composition "3 in 1" differs from a washing and rinsing composition "2 in 1” in particular by a higher concentration of organic builders and sodium tripolyphosphate.
• a “3 in 1” washing and rinsing composition comprises
• the “two-in-one” or “three-in-one” washing and rinsing composition can be in the form of a liquid, gel, compacted powder or no ; preferably, it is in the form of a monolayer or multilayer tablet.
• a particularly advantageous embodiment consists in the use, according to the invention, of said water-soluble or water-dispersible amphoteric copolymers in the form of a solid preformulation, in particular in the form of granules, comprising said amphoteric copolymer adsorbed and / or absorbed on a solid, water-soluble inorganic support. .
• a second object of the invention consists, as a new industrial product, in a dry solid preformulation intended for a “two in one” or “three in one” washing and rinsing composition for an automatic dishwashing machine, said preformulation consisting essentially of a solution or a dispersion of said amphoteric copolymer adsorbed and / or absorbed on a particulate solid support in at least one water-soluble inorganic material.
• the water-soluble inorganic supports there may be mentioned sulfates, tripolyphosphates, carbonates, bicarbonates, sesquicarbonates of alkali metals, preferably sodium.
• said support is sodium tripolyphosphate, preferably in the anhydride form obtained by atomization.
• the weight ratio, expressed in dry terms, of amphoteric copolymer / inorganic support is from 5/95 to 50/50, preferably from 10/90 to 30 70.
• said preformulation is presented under co-granules having a median diameter of 250 to 1000 ⁇ m (measurement by sieve size).
• Said preformulation can be obtained by granulation of the support material in particulate form using an aqueous solution or dispersion of amphoteric copolymer, said solution or dispersion having a dry extract of 10 to 40%, preferably 15 to 35%.
• the support material in particulate form can have a median diameter of 150 to 700 ⁇ m.
• the granulation operation can be carried out in a known manner using a granulation device such as a drum, plate, fluidized bed, etc.
• a third object of the invention consists in a process for improving the anti-redeposition properties of soiling of a washing and rinsing composition “two in one” or “three in one” for cleaning dishes in a machine, by adding to said composition of an effective amount of at least one water-soluble or water-dispersible amphoteric copolymer described above or of a preformulation as described above.
• Another object of the invention consists, as a new industrial product, in a washing and rinsing formulation “2 in 1” or “3 in 1” for washing dishes in a particularly efficient dish washing machine, including:
• nonionic surfactant from 0.1 to 20%, preferably from 0.2 to 10%, very particularly from 0.2 to 5% by weight of nonionic surfactant.
• the sodium silicate is a cogranulate of hydrated sodium silicate of Si ⁇ 2 / Na 2 0 ratio which can range from 1.5 to 3.5, and of sodium carbonate, the weight ratio of silicate to carbonate which can range from 5/95 to 45/55, preferably from 15/85 to 35/65, like the NABION 15 marketed by Rhodia.
• Said “2 in 1” or “3 in 1” formulation may also comprise the usual additives present in compositions for dishwashers, such as those described above and in amounts already mentioned above.
• the washing and rinsing formulation is implemented in the dishwashing machine, by introduction into the machine compartment provided for this purpose. 20 g of conventional washing powder containing 0.1% or 0.2% of polymer to be tested are thus used.
• the test is carried out on 10 soda glasses regularly placed in the machine.
• control 0 conventional powder without polymer (control): white veil and traces of dirt clearly visible
• Example 1 Powder or tablet formula "3 in 1" The test is carried out in hard water (40 ° TH), without rinsing salts or regenerating salt.
• NABION 15 (builder, co-granulate Carbonate / Sodium silicate) 25%
• Antarox B12 DF non-ionic surfactant, defoamer 0.9%
• Antarox B79R non-ionic surfactant 0.9%
• Rhodoline DP 226 35 (polymer builder) 2%
• the formulation is in powder form or else in the form of a tablet 44 mm in diameter and 1 cm thick, obtained by compacting 20 g of powder under a pressure of 2 Mpa.
• the test is carried out in fresh water ( ⁇ 5 ° TH), without rinsing salt.
• NABION 15 (builder, co-granulate Carbonate / Sodium silicate) 34%
• Antarox B12 DF nonionic surfactant, defoamer 0.8%
• Antarox B79R non-ionic surfactant 0.8%
• Rhodoline DP 22635 polymer builder
• the formulation is in powder form or else in the form of a tablet 44 mm in diameter and 1 cm thick, obtained by compacting 20 g of powder under a pressure of 4 Mpa.
• Example 1 The operation described in Example 1 is carried out by implementing the formulations given in the following table:
• Example 1 The operation described in Example 1 is carried out by implementing the formulations given in the following table:

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• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 2002
  • 2002-05-27 FR FR0206434A patent/FR2839977B1/fr not_active Expired - Fee Related
• 2003
  • 2003-05-26 BR BRPI0304924-8A patent/BR0304924B1/pt active IP Right Grant
  • 2003-05-26 EP EP03755203A patent/EP1507844B1/fr not_active Expired - Lifetime
  • 2003-05-26 CN CN2012103489699A patent/CN102936540A/zh active Pending
  • 2003-05-26 AT AT03755203T patent/ATE509089T1/de not_active IP Right Cessation
  • 2003-05-26 AU AU2003255604A patent/AU2003255604A1/en not_active Abandoned
  • 2003-05-26 WO PCT/FR2003/001582 patent/WO2003099980A1/fr not_active Ceased
  • 2003-05-26 JP JP2004508222A patent/JP4672364B2/ja not_active Expired - Fee Related
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  • 2003-05-26 ES ES03755203T patent/ES2362181T3/es not_active Expired - Lifetime
  • 2003-05-27 US US10/445,481 patent/US20040005990A1/en not_active Abandoned
• 2006
  • 2006-08-04 US US11/499,211 patent/US20060270579A1/en not_active Abandoned
• 2007
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