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
• • 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
  • C11D1/72—Ethers of polyoxyalkylene glycols
  • C11D1/721—End blocked ethers
• • A—HUMAN NECESSITIES
  • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
  • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
  • A47L15/00—Washing or rinsing machines for crockery or tableware
  • A47L15/0002—Washing processes, i.e. machine working principles characterised by phases or operational steps
  • A47L15/0007—Washing phases
• • 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
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2082—Polycarboxylic acids-salts thereof
• • 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
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2086—Hydroxy carboxylic acids-salts thereof
• • 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
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids
• • 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
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces

Definitions

• the present invention is directed towards a process for cleaning dishware soiled with fatty residue, characterized in that said process is carried out at a temperature in the range of from 45 to 65°C and using at least one formulation, comprising
• R 1 being selected from C4-C3o-alkyl, straight-chain or branched, and from C4-C3o-alkenyl, straight-chain or branched, with at least one C-C double bond,
• R 2 being selected from Ci-C3o-alkyl, straight-chain or branched, and from C2-C3o-alkenyl, straight-chain or branched, with at least one C-C double bond, x being selected from one to 100,
• AO being identical or different alkylene oxides, selected from CH2-CH2-O, (CH2)3-0, (Chb O, CH 2 CH(CH 3 )-0, CH(CH 3 )-CH 2 -0- and CH 2 CH(n-C 3 H 7 )-0, percentages being based on the total solids content of said formulation.
• the present invention is directed towards formulations that are useful for cleaning dishware, and towards a process for making such formulations.
• Detergent formulations especially detergent formulations for automatic dishwashing, have to meet various requirements.
• such detergent formulations need to enable a complete cleaning of china, polymer, metal, clay, and glassware and to remove all sorts of soil, like fat, proteins, starch, dyes, and more.
• the soils need to be dispersed in water during the cleaning and the water removal process, and the various soils should not deposit in the dishwashing machine in case of automatic dishwashing.
• the cleaned good should exhibit a good drying behavior, without spotting.
• Mixed hydroxy ethers are particularly efficient non-ionic surfactants, especially when combined with certain polymers, see, e. g., WO 2008/095563.
• WO 2008/095563 especially the use of mixed hydroxy ethers in formulations disclosed in WO 2008/095563 in automatic dishwashers can lead to rather high amounts of surfactant and fat residues in the filters or sieves.
• the inventive process is a process for cleaning dishware.
• the inventive process can be carried out either manually (hand-dish-wash) or preferably with the help of a machine (machine dish- wash or automatic dish-wash).
• Dishes in the context of the present invention shall not only refer to plates from china but also to any kitchenware from china, metal, glass, clay or polymer, such as - but not limited to - cups, bowls and plates from china, flatware, drinking glasses such as wine glasses, champagne flutes, beer glasses and the like, and plastic kitchenware, furthermore pots, frying pans and Dutch ovens from metal such as iron, aluminum or stainless steel.
• Dish-ware is provided in soiled form, among other soiled with fatty residue, also referred to as fat, that may stem from food itself or - for example in the case of frying pans - fat that stems from cooking or frying or baking food.
• fat may also include lard or oil, especially oil like sunflower oil, olive oil or other oil that is used for cooking purposes.
• Said fatty residue may be the sole soiling of dishware to be cleaned according to the inventive process.
• dish-ware to be cleaned according to inventive process may be soiled with a combination of fat and at least one substance other than fat, for example pigment(s), protein, carbohydrates such as starch or sugar, caramel, further- more lecithin, or dyestuff(s).
• the inventive process is being carried out at temperatures in the range of from 45 to 65°C, preferably 50 to 60°C. Said temperature refers to the temperature of the water being used in the inventive process. The inventive process is being described in more detail below.
• the inventive process is being carried out using water.
• the amount of water is influenced by the type of machine used and by the choice of the program.
• Formulations used in the inventive process comprise
• complexing agent (A) in the range of from 1 to 50 % by weight, preferably 10 to 40 % by weight of at least one complexing agent, hereinafter also being referred to as complexing agent (A), said com- plexing agent being selected from the alkali metal salts of citric acid, from the alkali metal salts of aminocarboxylic acids and from sodium tripolyphosphate.
• alkali metal salts in the context of complexing agent (A) are the potassium salts and in particular the sodium salts.
• Preferred alkali metal salts of citric acid are the sodium salts, especially the trisodium salt.
• aminocarboxylic acids are methylglycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and iminodisuccinic acid (IDS).
• Preferred alkali metal salts of aminocarboxylic acids are the trisodium salt of MGDA, the tetrasodium salt of GLDA and the tetra- sodium salt of IDS.
• Sodium tripolyphosphate preferably refers to the respective pentasodium salt.
• said formulation may contain a combination of at least two complexing agents (A), such as, for example, a combination of alkali metal salts of citric acid and MGDA, or of citric acid and GLDA, or combinations of alkali metal salts of citric acid and sodium tripolyphosphate.
• A complexing agents
• Preferred are combinations of the respective sodium salts, in particular combinations of the trisodium salts of citric acid and MGDA.
• formulations used in the inventive process are phosphate-free.
• the term phosphate-free refers to a combined phosphate and polyphosphate content of 0.01 or less up to 0.5% by weight of phosphate.
• Formulations used in the inventive process further comprise
• surfactant (B) in the range of from 2 to 8 % by weight, preferably up to 6 % by weight of at least one non- ionic surfactant of general formula (I) R 1 -CH(OH)-CH 2 -0-(AO)x-R 2 (I), hereinafter also being referred to as "surfactant (B)", the integers being defined as follows:
• R 1 is selected from C4-C3o-alkyl, straight-chain or branched, and from C4-C3o-alkenyl, straight- chain or branched, with at least one C-C double bond, preferred is C4-C3o-alkyl, straight- chain or branched, more preferred is straight-chain C4-C3o-alkyl and even more preferred is n-Cio-Ci2-alkyl.
• R 2 is selected from Ci-C3o-alkyl, straight-chain or branched, and from C2-C3o-alkenyl, straight- chain or branched, with at least one C-C double bond, preferred is C6-C2o-alkyl, more preferred is Cs-Cn-alkyl, x is selected from one to 100, preferably from 5 to 60, more preferably 10 to 50, and even more preferably 20 to 40,
• AO is selected from identical or different alkylene oxides, selected from CH2-CH2-O, (CH2)3-0, (CH 2 )4-0, CH 2 CH(CH 3 )-0, CH(CH 3 )-CH 2 -0- and CH 2 CH(n-C 3 H 7 )-0.
• (AO) x is selected from (ChbChbOJxi, x1 being selected from one to 50.
• (AO) x is selected from
• x or x1 or x2 and x3 or x4 are to be understood as average values, the number average being preferred. Therefore, each x or x1 or x2 or x3 or x4 - if applicable - can refer to a fraction although a specific molecule can only carry a whole number of alkylene oxide units.
• Formulations used in the inventive process further comprise
• copolymer (C) in the range of from 0.25 to less than 4 %, preferably 0.5 to 3.5% by weight of a copolymer, hereinafter also being referred to as copolymer (C), being obtained from copolymerizing the following comonomers (a) at least one comonomer, also being referred to as "comonomer (a)", selected from eth- ylenically unsaturated C3-C4-carboxylic acids, for example crotonic acid and preferably (meth)acrylic acid, (E)-crotonic acid, (Z)-crotonic acid, preferred is methacrylic acid and even more preferred is acrylic acid, and from ethylenically unsaturated C4-C8- dicarboxylic acids and their respective anhydrides, for example maleic acid, maleic an- hydride, itaconic acid, itaconic anhydride, citraconic acid, metaconic anhydride and fu- maric acid, preferred is maleic
• comonomer (b) at least one comonomer, also referred to as “comonomer (b)", being selected from isobutene, diisobutene,
• CisH37-ester (meth)acrylic acid n-C2oH4i-ester, (meth)acrylic acid n-C22H45-ester and (meth)acrylic acid n-C24H49-ester.
• (c) optionally, at least one further comonomer, also being referred to as "comonomer (c)", such comonomer (c) being selected from non-ionic comonomers and being different from both comonomer (a) and comonomer (b) and not being selected from either group of comonomers (a) and (b).
• comonomer (c) being selected from non-ionic comonomers and being different from both comonomer (a) and comonomer (b) and not being selected from either group of comonomers (a) and (b).
• Percentages of complexing agent (A), surfactant (B) and copolymer (C) are percentages by weight and refer to the total solids content of the respective formulation.
• copolymer (C) can be obtained by free radical co- polymerization.
• comonomer (c) is selected from omethyl styrene, para-methyl styrene and preferably from styrene.
• AO is being defined as above.
• y and y1 and y2 are to be understood as average values, the number average being preferred. Therefore, each y or y1 or y2 - if applicable - can refer to a fraction although a specific molecule can only carry a whole number of alkylene oxide units.
• copolymer (C) has an average molecular weight Mw in the range of from 1 ,000 to 30,000 g/mol, preferably 2,000 to 10,000 g/mol, determined, for example, by gel permeation chromatography (GPC) or size exclusion chromatography, and referring to the acid/salt.
• Mw average molecular weight
• copolymer (C) exhibits a polydispersity M w /M n in the range of from 1 .5 to 10, preferably 2 to 5.
• copolymer (C) is used as its alkali metal salt, its carboxyl groups being partially or preferably fully neutralized with alkali, preferably with sodium.
• copolymer (C) is selected from random copolymers, alternating copolymers, block copolymers and multiblock copolymers.
• comonomer (a) is selected from maleic acid and maleic anhydride and comonomer (b) is selected from isobutene, diisobutene and C2-C28-0 olefins, preferably from straight-chain C2-C28-a-olefins.
• Such copolymers (C) are preferably alternating copolymers.
• comonomer (a) is selected from (meth)acrylic acid and comonomer (b) is selected from Ci2-C24-alkyl esters of (meth)acrylic acid.
• Such copol- ymers (C) are preferably random copolymers.
• copolymer (C) is made from
• comonomer(s) (b) selected from isobutene, diisobutene, and C2-C28-a-olefins, and, optionally
• copolymer (C) is made from
• comonomer(s) (b) selected from Ci2-C24-alkyl esters of (meth)acrylic acid, and, optionally
• Percentages are referring to the total respective copolymer (C) as free acid.
• formulations used in the inventive process may have a total solids content in the range of from 90 to 99.9%, preferably 95 to 99 % by weight.
• inventive formulations are, e. g., in the form of powder or tablets.
• formulations used in the inventive process may have a total solids content in the range of from 15 to 40% by weight.
• inventive formulations are, e. g., in the form of gels.
• the inventive process comprises several steps, one of the steps being contacting the soiled dishware with a formulation as disclosed above, and also comprising at least one rinsing step and at least one drying step.
• the formulation used in the inventive process can be used as 2-in-1 or 3-in-1 formulation, and no separate rinse agent is necessary.
• the ion exchange does not need to be treated with regenerating salt.
• the formulation used in the inventive process can be used as 2-in-1 or 3-in-1 formulation, and neither a separate rinse agent nor a regenerating salt is necessary.
• formulations used in the inventive process may contain at least one further ingredient, also being referred to as ingredient (D).
• Ingredient (D) may be selected from one or more surfactants other than surfactant (B), one or more enzymes, one or more builders other than complexing agent (A), in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more bleaching agents, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more antifoams, one or more corrosion inhibitors, one or more buffer or one or more dyes.
• surfactants other than surfactant (B) are in particular nonionic surfactants other than surfactant (B) as well as mixtures of anionic or zwitterionic surfactants with nonionic surfactants other than surfactant (B).
• Preferred nonionic surfactants other than surfactant (B) are alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl glycosides and so-called amine oxides.
• alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (II)
• R 5 is selected from Cs-C22-alkyl, for example n-CsH , n-doHb-i , n-Ci2H25, n-C-uHbsi, n-Ci6H33
• n and n are in the range from zero to 300, where the sum of n and m is at least one.
• m is in the range from 1 to 100 and n is in the range from 0 to 30.
• Compounds of the general formula (II) may be block copolymers or random copolymers, preference being given to block copolymers.
• alkoxylated alcohols and alkoxylated fatty alcohols are, for exam- pie, compounds of the general formula (III)
• R 6 is selected from C6-C2o-alkyl, in particular n-CsH , n-doHb-i , n-Ci2H25, n-C-uFbs), n-Ci6H33,
• a is a number in the range from 1 to 6
• b is a number in the range from 4 to 20
• d is a number in the range from 4 to 25.
• Compounds of the general formula (III) may be block copolymers or random copolymers, preference being given to block copolymers.
• nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide. Further suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl glycosides are likewise suitable. An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and in DE-A 198 19 187.
• Mixtures of two or more different nonionic surfactants other than surfactant (B) may also be present.
• anionic surfactants are Cs-C2o-alkyl sulfates, C8-C20-alkylsulfonat.es and C8-C20- alkyl ether sulfates with one to 6 ethylene oxide units per molecule.
• formulations used in the inventive process can comprise in the range from 3 to 20% by weight of surfactant other than surfactant (B).
• Formulations used in the inventive process can comprise one or more enzymes. Examples of enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.
• Formulations used in the inventive process can comprise, for example, up to 5% by weight of enzyme, preference being given to 0.1 to 3% by weight, in each case based on the total solids content of the formulation according to the invention.
• formulations used according to the invention can com- prise one or more builders, in particular phosphate-free builders.
• suitable builders are fatty acid sulfonates, ohydroxypropionic acid, alkali metal malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders, for example polycarboxylates and polyaspartic acid.
• builders are selected from polycarboxylates, for example alkali metal salts of (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers.
• Suitable comonomers of polycarboxylates are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid.
• a suitable (meth)acrylic acid homopolymer is in particular polyacrylic acid, which preferably has an average molecular weight M w in the range from 2,000 to 40,000 g/mol, preferably 2,000 to 10,000 g/mol, in particular 3,000 to 8,000 g/mol.
• copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and/or fumaric acid.
• Formulations used according to the invention can comprise, for example, in the range from in total 2.5 to 20% by weight, preferably up to 10% by weight, of builders other than complexing agent (A).
• formulations used according to the invention can comprise one or more cobuilders.
• cobuilders are phosphonates, for example hydroxyalkanephosphonates and ami- noalkanephosphonates.
• hydroxyalkanephosphonates 1 -hydroxyethane-1 ,1 - diphosphonate (HEDP) is of particular importance as a cobuilder.
• HEDP 1 -hydroxyethane-1 ,1 - diphosphonate
• HEDP ethylenediaminetetra- methylenephosphonate
• DTPMP diethylenetriaminepentamethylenephosphonate
• amphoteric polymers can also be used as cobuilders.
• Formulations used in the inventive process can comprise one or more alkali carriers.
• Alkali carriers ensure, for example, a pH of at least 9 if an alkaline pH is desired.
• alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal hydroxides and alkali metal metasilicates are particularly preferred.
• a preferred alkali metal is in each case potassium, particular preference being given to sodium.
• Formulations used in the inventive process can comprise one or more bleach catalysts.
• Bleach catalysts can be selected from bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes.
• Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and also cobalt-, iron-, copper- and ruthenium-amine complexes can also be used as bleach catalysts.
• Formulations used in the inventive process can comprise, for example, 0.5 to 15% by weight of bleaching agents, hereinafter also referred to as bleach (D).
• Bleach (D) can be selected from oxygen bleaches and chlorine-containing bleaches.
• oxygen bleaches are sodium perborate, anhydrous or for example as monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as monohydrate, hydrogen peroxide, persulfates, organic peracids such as peroxylauric acid, peroxystearic acid, peroxy-a-naphthoic acid, 1 ,12-diperoxydodecanedioic acid, per- benzoic acid, peroxylauric acid, 1 ,9-diperoxyazelaic acid, diperoxyisophthalic acid, in each case as free acid or as alkali metal salt, in particular as sodium salt, also sulfonylperoxy acids and cationic peroxy acids.
• Formulations used in the inventive process can comprise, for example, in the range from 0.5 to 15% by weight of oxygen bleach.
• Suitable chlorine-containing bleaches are, for example, 1 ,3-dichloro-5,5-dimethylhydantoin, N- N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.
• Formulations used in the inventive process can preferably comprise, for example, in the range from 3 to 10% by weight of chlorine-containing bleach.
• Formulations used in the inventive process can comprise one or more bleach activators, for example N-methylmorpholinium-acetonitrile salts ("MMA salts”), trimethylammonium acetonitrile salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1 ,5-diacetyl-2,2- dioxohexahydro-1 ,3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
• suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.
• Formulations used in the inventive process can comprise one or more corrosion inhibitors.
• corrosion inhibitors include triazoles, in particular benzotria- zoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, also phenol derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.
• formulations used in the inventive process comprise in total in the range from 0.1 to 1.5% by weight of corrosion inhibitor.
• Formulations used in the inventive process can comprise one or more fillers, for example sodi- urn sulfate.
• Formulations used in the inventive process can comprise one or more antifoams, selected for example from silicone oils and paraffin oils.
• formulations used in the inventive process comprise in total in the range from 0.05 to 0.5% by weight of antifoam.
• Dishware cleaned according to the inventive process exhibits excellent properties, such as very good removal of soiling, especially of fat. Furthermore, dishware cleaned according to the in- ventive process show excellent values for spotting, filming and residues. In addition, when modern dishwashing machines are used, the filter(s) and/or sieves will contain only very low amounts of surfactant and fat after operation.
• inventive formulations may be unit doses, such as tablets, or as gel or powder, as granules or compactate. In a preferred embodiment, such a unit dose comprises 10 to 30 g of inventive formulation.
• inventive formulations may be solid, and in such embodiments they may contain some residual humidity, such as 0.01 to 10 % by weight, water. In other embodiments, inventive formulations may be liquids or gels.
• Inventive formulations comprise
• (A) in the range of from 1 to 50 % by weight, preferably 10 to 40 % by weight of at least one complexing agent (A), said complexing agent being selected from the alkali metal salts of citric acid, from the alkali metal salts of aminocarboxylic acids and from sodium tripolyphosphate.
• alkali metal salts in the context of complexing agent (A) are the potassium salts and in particular the sodium salts.
• Preferred alkali metal salts of citric acid are the sodium salts, especially the trisodium salt.
• aminocarboxylic acids are methylglycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and iminodisuccinic acid (IDS).
• Preferred alkali metal salts of aminocarboxylic acids are the trisodium salt of MGDA, the tetrasodium salt of GLDA and the tetra- sodium salt of IDS.
• Sodium tripolyphosphate preferably refers to the respective pentasodium salt.
• inventive formulations may contain a combination of at least two complexing agents (A), such as, for example, a combination of alkali metal salts of citric acid and MGDA, or of citric acid and GLDA, or combinations of alkali metal salts of citric acid and sodium tripolyphosphate.
• A complexing agents
• Preferred are combinations of the respective sodium salts, in particular combinations of the trisodium salts of citric acid and MGDA.
• inventive formulations are phosphate-free.
• phosphate-free refers to a combined phosphate and polyphosphate content of 0.01 or less up to 0.5% by weight of phosphate.
• Inventive formulations further comprise
• R 1 is selected from C4-C3o-alkyl, straight-chain or branched, and from C4-C3o-alkenyl, straight- chain or branched, with at least one C-C double bond, preferred is C4-C3o-alkyl, straight- chain or branched, more preferred is straight-chain C4-C3o-alkyl and even more preferred is n-Cio-Ci2-alkyl.
• x is selected from one to 100, preferably from 5 to 60, more preferably 10 to 50, and even more preferably 20 to 40,
• AO is selected from identical or different alkylene oxides, selected from CH2-CH2-O, (CH2)3-0, (CH 2 )4-0, CH 2 CH(CH 3 )-0, CH(CH 3 )-CH 2 -0- and CH 2 CH(n-C 3 H 7 )-0.
• CH2-CH2-O alkylene oxides
• (AO) x is selected from , x1 being selected from one to 50.
• (AO) x is selected from -(ChbCI-bO ⁇ - (CH2CH(CH3)-0)x3, x2 and x3 being identical or different and selected from 1 to 30.
• Inventive formulations further comprise (C) in the range of from 0.25 to less than 4 %, preferably 0.5 to 3.5% by weight of copolymer (C), being obtained from copolymerizing the following comonomers
• comonomer (c) being different from both comonomer (a) and comonomer (b) and not being selected from either group of comonomers (a) and (b).
• Percentages of complexing agent (A), surfactant (B) and copolymer (C) are percentages by weight and refer to the total solids content of the respective formulation.
• Comonomers (a), (b) and (c) have been defined above.
• inventive formulations are phosphate-free.
• copolymer (C) has an average molecular weight Mw in the range of from 1 ,000 to 30,000 g/mol, preferably up to 10,000 g/mol, determined by GPC. In one embodiment of the present invention, copolymer (C) exhibits a polydispersity M w /M n in the range of from 1.5 to 10, preferably 2 to 5.
• copolymer (C) is used as its alkali metal salt, its carboxyl groups being partially or preferably fully neutralized with alkali, preferably with sodium.
• copolymer (C) is selected from random copolymers, alternating copolymers, block copolymers and multiblock copolymers.
• comonomer (a) is selected from maleic acid and maleic anhydride and comonomer (b) is selected from isobutene, diisobutene and C2-C28-0 olefins, preferably from straight-chain C2-C28-a-olefins.
• Such copolymers (C) are preferably alternating copolymers.
• comonomer (a) is selected from (meth)acrylic acid and comonomer (b) is selected from Ci2-C24-alkyl esters of (meth)acrylic acid.
• Such copolymers (C) are preferably random copolymers.
• inventive formulations have a total solids content in the range of from 90 to 99.9%, preferably 95 to 99 % by weight. Such inventive formulations are, e. g., in the form of powder or tablets. In one embodiment of the present invention, inventive formulations have a total solids content in the range of from 15 to 40% by weight. Such inventive formulations are, e. g., in the form of gels. In one embodiment of the present invention, inventive formulations may contain at least one further ingredient, also being referred to as ingredient (D).
• Ingredient (D) may be selected from one or more surfactants other than surfactant (B), one or more enzymes, one or more builders other than complexing agent (A), in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more bleaching agents, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more antifoams, one or more corrosion inhibitors, one or more buffer or one or more dyes. Ingredients (D) have been explained in more detail above.
• Inventive formulations are excellently suitable for carrying out the inventive process.
• a further aspect of the present invention is a process for making inventive formulations, hereinafter also being referred to as inventive manufacturing process.
• the inventive manufacturing process comprises mixing complexing agent (A), surfactant (B) and copolymer (C) and, if applicable, one or more further ingredient (D), in one or more steps.
• Such mixing can be performed in the absence or presence of water, preferably mixing is being performed in the absence of water.
• at least one of the components complexing agent (A), surfactant (B) and copolymer (C) or, if applicable, one or more further ingredient (D) is added as aqueous solution to other components that are powdery or in the form of granules, and the water is being removed during or after mixing.
• Mixing can be performed at a temperature in the range of from 5 to 100°C, preferably 20 to 70°C or at ambient temperature.
• the inventive manufacturing process is being carried out in the presence of water, and such water is at least partially removed at the end of the inventive manufacturing process, for example by spray-drying or by making compactates of granules of different components or of premixed components.
• Copolymer (C.1 ): fully neutralized sodium salt of random copolymer from maleic acid anhydride (a.1 ), CH 2 CH-n-Ci 6 H 3 3 (b.1 )/isobutene (b.2); 65 % by weight of (a.1 ), 9 % by weight of (b.1 ), 26 % by weight of (b.2), percentages referring to the respective free acid of (C.1 ) Synthesis of copolymer (C.1 ):
• O-Xylene (363 g) and maleic acid anhydride (a.1 ) (196 g) were placed in an autoclave equipped with metering and distillation devices and a stirrer.
• the autoclave was purged with 3 bar of nitrogen three times.
• the pressure was then reduced to 91 mbar and the mixture of (a.1 ) and o- xylene was heated to 120°C.
• the following feeds were added simultaneously at 120°C, each with constant rate , starting at the same time:
• Copolymer (C.2) fully neutralized sodium salt of random copolymer from acrylic acid
• a polymerization vessel equipped with an anchor stirrer and metering devices was charged with a solution of 5 g od acrylic acid (a.2) in 175 g of isopropanol. The mixture was heated to 80°C under an atmosphere of nitrogen. The following feeds were added simultaneously at 80°C, each with constant rate, starting at the same time:
• the pH value of aqueous mix- ture so obtained was adjusted to 7.0 with aqueous sodium hydroxide solution to yield a clear aqueous polymer solution with a solid content of 23.2 wt.%. M w : 5180 g/mol.
• the weight-average molecular weight (M w ) of copolymer (C.2) was determined by GPC (gel permeation chromatography) at 23 °C, using a PSS Suprema column (PSS, Mainz, Germany).
• the eluent employed was an aqueous tris(hydroxymethyl)amino methane (TRIS) buffer solution (0.02 M), containing 0.2 M sodium chloride.
• TIS tris(hydroxymethyl)amino methane
• base mixtures were prepared from the feed materials according to table 1.
• the feed materials as well as copolymer (C.1 ), copolymer (C.2) and/or polymer (D.3) were mixed in dry state apart from (B.1 ) and (B.2), which were finally added in molten form.
• “Sieves (grade)” refers to an average grade. The sieves and filters only contained very little fat and detergent when TF.2 was used. When C-TF.1 was used, soiling of the sieve could be ob- served after the 6 th cycle.
• “Sieves (grade)” refers to an average grade. The sieves and filters only contained very little fat and detergent when TF.4 or TF.5 was used. When C-TF.3 was used, strong soiling of the sieve could be observed after the 30 th cycle.
• copolymer (C.2) was used instead of copolymer (C.1 ) the same trend was observed.

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• 2014
  • 2014-06-24 WO PCT/EP2014/063279 patent/WO2015000744A1/en not_active Ceased
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