CN104379717B - Preparaton, it is as or for producing purposes and its preparation of warewashing detergent - Google Patents

Preparaton, it is as or for producing purposes and its preparation of warewashing detergent Download PDF

Info

Publication number
CN104379717B
CN104379717B CN201380033256.6A CN201380033256A CN104379717B CN 104379717 B CN104379717 B CN 104379717B CN 201380033256 A CN201380033256 A CN 201380033256A CN 104379717 B CN104379717 B CN 104379717B
Authority
CN
China
Prior art keywords
preparaton
weight
acid
present
glass
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.)
Expired - Fee Related
Application number
CN201380033256.6A
Other languages
Chinese (zh)
Other versions
CN104379717A (en
Inventor
马科斯 A·加西亚
S·许弗
M·哈特曼
H·韦伯
M·埃莫鲁斯
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 CN104379717A publication Critical patent/CN104379717A/en
Application granted granted Critical
Publication of CN104379717B publication Critical patent/CN104379717B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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

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)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Washing And Drying Of Tableware (AREA)

Abstract

The present invention relates to preparaton, it is included：(A) at least one amino carboxylic acid compound, selected from MDGA compound (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetic acid compound (GLDA) and its salt and their derivative, (B) at least one alkoxylate alkylene imine polymers, there is average molecular weight Mw to be 800 25000g/mol for it, positive charge density is at least 5meq/g, and with 2 weight % to the alkylene oxide side chain for being no more than 80 weight %, the total amount meter based on alkoxylate alkylene imine polymers.

Description

Preparaton, its as or for produce warewashing detergent purposes and its Prepare
The present invention relates to preparaton, it is included：
(A) at least one amino carboxylic acid compound, selected from MDGA compound (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetic acid compound (GLDA) and its salt, and
(B) at least one alkoxylate alkylene imine polymers, there is average molecular weight Mw to be 800-25000g/ for it Mol, positive charge density is at least 5meq/g, and the alkylene oxide side chain with 2 weight % to most 80 weight %, based on alcoxyl The total amount meter of base alkylene imine polymers.
In addition, being used to prepare according to the method for the preparaton of the present invention and its conduct or for producing the present invention relates to a kind of The purposes of dish washing agent, particularly for the purposes of the dish washing agent of machine dish washing.
Dish washing agent must is fulfilled for many requirements.For example, they must be able to be sufficiently cleaned with vessel, they are in waste water There should not be harmful or potentially harmful material, they should allow water to wash away and dry from the vessel, and they should not be in device Thrown into question in the operation of ware rinsing maching.Finally, they should not cause aesthetically non-required result to the vessel to be cleaned.With regard to this In, it can especially address glass corrosion.
Glass corrosion be not only mechanical effect for example because glass rubs together or the part of glass and ware wash machine it The result of room machine contact, and it is main because chemical effect causes.For example, specific ion can be by repeating machine-washing from glass It is dissolved out in glass, this inadvertently changes optical characteristics and thus changes aesthetic.
In the case of glass corrosion, some effects can be observed.First, the formation of microcosmic microcrack can be observed, The microcrack is significantly in line form.Secondly, in many cases, can be observed it is general haze, be for example roughened, this makes The glass is obtained to seem to fall from favor.The type effect is totally subdivided into flashing color-variable, ridge formation and sheet and ring Shape hazes.
WO 2006/108857 discloses alkoxylate polyethyleneimine as the additive of detergent.For example, it is public The detergent for including zeolite or polyaminocarboxylic acid compound such as EDTA or triethylenediamine pentacetate as complexant is opened.
WO 01/96516 proposes the preparaton for including alkoxylate polyethyleneimine for cleaning of hard surfaces.Will be net Changing water is used to rinse.
WO 2010/020765 discloses the utensil washing composition comprising polyethyleneimine.The type dish washing is combined Thing can include phosphate or not phosphate-containing.They have good inhibitory action for glass corrosion.Vessel containing zinc and bismuth Detergent is not proposed.However, in many cases, not postponing fully or preventing glass corrosion, especially line corrodes With haze.
Therefore, it is used as or it is an object of the present invention to provide suitable for preparing utensil washing composition and avoiding in the prior art Known disadvantage simultaneously suppresses glass corrosion or at least reduces the preparaton of glass corrosion particularly well.Another object is to provide a kind of use It is suitable as or for preparing utensil washing composition and the method for the preparaton that avoids shortcoming known in the art in preparing.Again One purpose is to provide the purposes of preparaton.
Thus, it is found that preparaton defined in beginning, it is also abbreviated by preparaton of the present invention.
The preparaton of the present invention is free from heavy metal.In the present invention, this is understood to mean that the preparaton of the present invention not The heavy metal compound of bleaching catalyst is not played containing those, especially not iron content and the compound of bismuth.With regard to heavy metal compound For, the content that " being free of " is interpreted as not refer in the context of the present invention the heavy metal compound of bleaching catalyst effect is total It is 0-100ppm altogether, is determined according to Leach methods and based on solid content.It is preferred that the content of beary metal that preparaton of the present invention has is Less than 0.05ppm, the solid content meter based on the preparaton.
In the context of the present invention, " heavy metal " is that all proportions are at least 6g/cm3Metal.Specifically, heavy metal It is noble metal and zinc, bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.
It is preferred that preparaton of the present invention does not include the zinc and bismuth compound of measurable ratio, that is, it is, for example, less than 1ppm.
Preparaton of the present invention is included：
(A) it is at least one to be selected from MDGA compound (MGDA), iminodisuccinic acid (IDS) and glutamic acid The amino carboxylic acid compound of diethyl acidulants (GLDA) and its salt, is also abbreviated by amino carboxylic acid compound (A) in the context of the present invention Or compound (A), preferred their salt.
It is preferred that, compound (A) selection is free acid, particularly preferably in form is partially or completely neutralized, i.e., as salt.Properly Counter ion counterionsl gegenions be, for example, inorganic cation, such as ammonium, alkali metal or alkaline-earth metal, preferably Mg2+、Ca2+、Na+、K+, or it is organic Cation, the especially ammonium preferably replaced by one or more organic groups, triethanol ammonium, N, N- diethanol ammoniums, the mono--C of N-1-C4 Alkyl diethanol ammonium, such as N- methyl diethanol ammonium or N- normal-butyl diethanol ammoniums, the and-C of N, N- bis-1-C4Alkyl alcohol ammonium.
Compound (A) very particularly preferably is MDGA compound (MGDA), cinic acid (IDS) With the alkali metal salt of glutamic acid diacetic acid compound (GLDA), especially sodium salt.
Very particularly preferably, MDGA compound (MGDA), cinic acid (IDS) or glutamic acid Diethyl acidulants (GLDA) are fully neutralized.
In addition, preparaton of the present invention is included：
(B) at least one alkoxylate alkylene imine polymers, there is average molecular weight Mw to be 800-25000g/ for it Mol, positive charge density is at least 5meq/g, and the epoxy with 2 weight % to most 80 weight %, preferably 5-60 weight % Alkane side chain, the total amount meter based on alkoxylate alkylene imine polymers.
In the present invention, the alkylene imine polymers of this modification are also referred to as being modified alkylene imine polymers (B).
In the context of the present invention, alkylene imine polymers are interpreted as referring to by one or more cyclic imide homopolymerizations Or copolymerization or by using at least one cyclic imide be grafted (co) polymer obtained from those polymeric materials.Example is poly- Alkylene polyamine and the Polyamide amine for being grafted with aziridine.
In the context of the present invention, polyalkylene polyamine be preferably interpreted as referring to per molecule comprising at least six nitrogen-atoms and At least five C2-C10Alkylidene unit, preferably C2-C3Those polymer of alkylidene unit, such as penten, Yi Jiyou It is polyethyleneimine.
Alkylene imine polymers and especially polyethyleneimine can for example have at least 300g/mol mean molecule quantity (Mw)；It is preferred that, the mean molecule quantity of polyethyleneimine is 800-20000g/mol, and this is by light scattering determining.
Polyalkylene polyamine can be covalent modified in quaternary (alkylation) form in part as alkylene imine polymers.Close Suitable quaternising agents (alkylating agent) are, for example, alkyl halide, especially C1-C10Alkyl chloride, such as methyl chloride, methyl bromide, methyl iodide, second Base chlorine, bromic ether, n-butyl chloride, tertiary butyl chloride, n-hexyl chlorine, also epichlorohydrin, dimethyl suflfate, dithyl sulfate and benzyl Chlorine.If to as quaternary (alkylation) polyalkylene polyamine of alkylene imine polymers covalent modified, quaternary (alkylation) Degree is preferably 1-25 moles of %, particularly preferably at most 20 moles %, based in alkylene imine polymers can it is quaternary (can alkyl Change) N atom meters.
In addition, the Polyamide amine for being grafted with aziridine is suitable as alkylene imine polymers.Suitable polyamide Base amine for example can be by making C4-C10Dicarboxylic acids and the polyalkylene polyamine that 3-10 basic nitrogen atom is preferably comprised in molecule are anti- Answer and obtain.Suitable dicarboxylic acids is, for example, butanedioic acid, maleic acid, adipic acid, glutaric acid, suberic acid, decanedioic acid or to benzene two Formic acid.The mixture of above-mentioned dicarboxylic acids, the mixture of such as adipic acid and glutaric acid, or maleic acid and adipic acid can also be used Mixture.Adipic acid is preferably used to produce Polyamide amine.The suitable polyalkylene being condensed with above-mentioned dicarboxylic acids is more Amine be, for example, diethylenetriamines, trien, dipropylenetriamine, tri propylidene tetramine, double-hexa-methylene triamine, Aminopropyl ethylenediamine and two-aminopropyl ethylenediamine.Above-mentioned polyalkylene polyamine can also be used for polyamides as a mixture In the preparation of amido amine.The preparation of Polyamide amine is carried out preferably under no dilution, it is also possible to optionally in atent solvent Carry out.The condensation of dicarboxylic acids and polyalkylene polyamine is carried out at elevated temperatures, such as is carried out at 120-220 DEG C.Anti- The water formed during answering is evaporated off from reactant mixture.This condensation can be optionally in the carboxylic acid with 4-8 carbon atom Carried out in the presence of lactone or lactams.Per moles of dicarboxylic acids usually using 0.8-1.4mol polyalkylene polyamines.In this way To Polyamide amine there is primary and secondary NH groups and it is water-soluble in.
The Polyamide amine for being grafted with aziridine can be by Bronsted acid or lewis acid such as sulfuric acid, phosphoric acid Or aziridine is acted on above-mentioned Polyamide amine and is prepared in the presence of boron trifluoride etherate.As a result graft on aziridine In the Polyamide amine.For example, 1-10 aziridine list can be grafted on each basic nitrogen atom in Polyamide amine Member, i.e., every 100 weight parts of polyamide base amine uses about 10-500 parts by weight of ethylene imines.
It is preferred that alkylene imine polymers be polyethyleneimine.
In one embodiment of the invention, polyethyleneimine is selected from highly branched polyethyleneimine.It is highly branched Polyethyleneimine is characterised by its highly -branched degree (DB).The degree of branching can for example pass through13C-NMR spectroscopic methodologies are preferably in D2In O Determine and as defined as follows：
DB=D+T/D+T+L
Wherein D (dendroid) corresponds to the ratio of tertiary amino, (linear) ratios corresponding to secondary amino group of L, T (end) correspondences In the ratio of primary amino radical.
In the context of the present invention, highly branched polyethyleneimine is that DB is 0.1-0.95, preferably 0.25-0.90, spy Not preferred 0.30-0.80, very particularly preferably at least 0.5 polyethyleneimine.
In one embodiment of the invention, polyethyleneimine is mean molecule quantity MwFor 600-20000g/mol, excellent Select 800-15000g/mol highly branched polyethyleneimine (homopolymer).
In the context of the present invention, alkylene imine polymers use in covalent modified form and especially should be so that it have There is a 2-80 weight % altogether, preferably 5-60 weight % alkylene oxide side chain, based on alkoxylate imino group imine polymer (B) Total amount meter.For alkoxylate, epoxides, such as oxirane, expoxy propane, 1,2- epoxy butanes, 2,3- can be used Epoxy butane, styrene oxide or epichlorohydrin.It is preferred that alkoxylating agent be oxirane and expoxy propane, and epoxy second The mixture of alkane and expoxy propane.
In one embodiment, in alkoxylate imino group imine polymer (B), the primary of imino group imine polymer It is alkoxylated with 5-60 moles of % nitrogen-atoms of secondary amino group.
In one embodiment of the invention, modified alkylene imine (B) be selected from oxirane or epoxy The polyethyleneimine of propane reaction.
Modified polyalkyleneimine (B) can have the HMW or low-molecular-weight, anionic as counter ion counterionsl gegenions, It can be organically or preferably inorganic.In the context of the present invention, high molecular weight anionic has 200g/mol or more Greatly, such as at most 2500g/mol mean molecule quantity, low-molecular-weight, anionic, which has, is less than 200g/mol, such as 17-150g/ Mol molecular weight.The example of low molecule amount means organic balance ion is acetate, propionate and benzoate anion.Low molecule amount is inorganic The example of counter ion counterionsl gegenions is sulfate radical, chlorion, bromide ion, hydroxyl, carbonate, methanesulfonate and bicarbonate radical.
In one embodiment of the invention, the cationic charge density that modified polyalkyleneimine (B) has is extremely Few 5meq/g to most 25meq/g (milliequivalent/gram), preferably up to 22meq/g refers to not consider to contend with the g data represented Modification polyalkyleneimine (B) during ion.Cationic charge density can for example be obtained by titration, such as by using poly- Vinyl sulfate (polyvinyl sulfate) is titrated.
In one embodiment of the invention, modified polyalkyleneimine (B) has 1.1-10, preferably 1.5-5 point Son amount distribution Mw/Mn。
In one embodiment of the invention, preparaton of the present invention is included：
1-50 weight %, preferably 10-25 weight % amino carboxylic acid compound (A) altogether,
0.001-5 weight %, preferably 0.02-0.5 weight % modification polyalkyleneimine (B) altogether, in each case Under the solid content meter based on the preparaton.
In the modification of the present invention, preparaton of the present invention is with 1000:1 to 25:1 weight is than inclusion compound (A) With modified polyalkyleneimine (B).
In a preferred embodiment of the invention, preparaton of the present invention not phosphate-containing and Quadrafos, wherein phosphoric acid hydrogen Salt is included into this scope, such as without tertiary sodium phosphate, pentasodium triphosphate and the sodium of metaphosphoric acid six.Associated with phosphate and Quadrafos " being free of " be interpreted as referring to phosphate in the context of the present invention and the content of Quadrafos is total up to by weight analysis determining 10ppm to 0.2 weight %.
Preparaton of the present invention can be in ware washing and/or kitchen utensils comprising for example to using other favourable groups Point.
In another embodiment of the present invention, preparaton of the present invention is not wrapped in ware washing and/or kitchen utensils Containing for example to using favourable other components, but can easily be prepared with other components and therefore be suitable as raw material.
In one embodiment of the invention, preparaton of the present invention includes sodium citrate (C).Thus, term lemon Lemon acid sodium includes mono-sodium salt and preferred disodium salt.Sodium citrate can be used as anhydrous salt or as hydrate, for example, make Used for dihydrate.
In one embodiment of the invention, preparaton of the present invention is included：
(D) at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulphate, It is also referred to as in the context of the present invention " bleaching agent (D) ".
It is preferred that bleaching agent (D) be selected from anhydrous or for example as monohydrate or be used as tetrahydrate or so-called dihydrate Sodium perborate, anhydrous or for example as the SODIUM PERCARBONATE of monohydrate, and sodium peroxydisulfate, wherein term " persulfate " exists Include peracid H under each case2SO5Salt and peracetic dithionite.
Thus, alkali metal salt can also be alkali metal hydrogencarbonate, alkali metal perboric acid hydrogen salt in each case With alkali metal persulfuric acid hydrogen salt.However, preferably two alkali metal salts in each case.
In one embodiment of the invention, preparaton of the present invention is included：0-50 weight % sodium citrates (C), preferably 1-30 weight %, particularly preferred at least 5 weight % sodium citrate (C), this is used as anhydrous citric acid sodium to determine；0-15 is heavy altogether Measure % bleaching agents (D), preferably at least 0.5 weight % bleaching agents (D), selected from alkali metal percarbonate, alkali metal perborate and Alkali metal persulphate, in each case the solid content meter based on the preparaton.
In one embodiment of the invention, preparaton of the present invention is solid, such as powder or tablet at room temperature. In another embodiment of the invention, preparaton of the present invention is liquid at room temperature.In one embodiment of the invention, Preparaton of the present invention is particle, liquid preparation or gel.
In one embodiment of the invention, preparaton of the present invention includes 0.1-10 weight % water, is matched somebody with somebody based on described The all solids sum meter of preparation.
In one embodiment of the invention, preparaton of the present invention can have other compositions (E), such as a kind of or many Surfactant is planted, one or more enzymes, one or more builders, especially non-phosphorus builder, one or more are helped Lotion (cobuilder), one or more alkali metal carriers, one or more bleaching agents, one or more bleaching catalysts, one Plant or a variety of bleach activators, one or more bleaching stibilizers, one or more defoamers, one or more corrosion inhibitors, one Plant or a variety of builders, buffer, dyestuff, one or more spices, one or more organic solvents, one or more tablettings are helped Agent, one or more disintegrants, one or more thickeners, or one or more cosolvents.
The example of surfactant especially nonionic surfactant, and anion or zwitterionic surfactant With the mixture of nonionic surfactant.It is preferred that nonionic surfactant be alcohol alcoxylates and alkoxylated fats Two-and segmented copolymer of alcohol, ethylene oxide and propylene oxide, and anhydro sorbitol and ethylene oxide or propylene oxide Reaction product, alkyl glucoside and so-called amine oxide.
The preferred embodiment of alcohol alcoxylates and alkoxy fatty alcohols is, for example, the compound of logical formula (I)：
Wherein each variable as defined below：
R1It is identical or different and selected from straight chain C1-C10Alkyl is preferably identical in each case and selected from ethyl and spy Not preferred methyl,
R2Selected from C8-C22Alkyl, such as n-C8H17、n-C10H21、n-C12H25、n-C14H29、n-C16H33Or n-C18H37,
R3Selected from C1-C10Alkyl, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, N-pentyl, isopentyl, sec-amyl, neopentyl, 1,2- dimethyl propyls, isopentyl, n-hexyl, isohesyl, Sec-Hexyl, positive heptan Base, n-octyl, 2- ethylhexyls, n-nonyl, positive decyl or isodecyl,
M and n is at least 1 for 0-300, wherein n and m summation.It is preferred that m is 1-100 and n is 0-30.
The compound of logical formula (I) can be block copolymer or random copolymer, preferred block copolymer herein.
Other preferred embodiments of alcohol alcoxylates and alkoxy fatty alcohols are, for example, the compound of logical formula (II)：
Wherein each variable as defined below：
R1It is identical or different and selected from C1-C10Alkyl is preferably identical in each case and selected from ethyl and especially excellent Select methyl,
R4Selected from C6-C20Alkyl, especially n-C8H17、n-C10H21、n-C12H25、n-C14H29、n-C16H33、n-C18H37,
A is 1-6 number,
B is 4-20 number,
D is 4-25 number.
The compound of logical formula (II) can be block copolymer or random copolymer, preferred block copolymer herein.
Other suitable nonionic surfactants are selected from two-and many blocks being made up of ethylene oxide and propylene oxide and are total to Polymers.Other suitable nonionic surfactants are selected from ethoxylation or propoxylation Isosorbide Dinitrate.Amine oxide or alkane Base glucoside is equally suitable.The summary of other suitable nonionic surfactants can be in EP-A 0 851 023 and DE-A Found in 198 19 187.
There can also be the mixture of two or more different nonionic surfactants.
The example of anion surfactant is C8-C20Alkyl sulfate, C8-C20Alkylsulfonate and per molecule have 1- The C of 6 ethylene oxide units8-C20Alkyl ether sulfate.
In one embodiment of the invention, preparaton of the present invention can include 3-20 weight % surfactant.
Preparaton of the present invention can include one or more enzymes.The example of enzyme is lipase, hydrolase, amylase, albumen Enzyme, cellulase, esterase, pectase, lactase and peroxidase.
Preparaton of the present invention can for example include at most 5 weight %, preferably 0.1-3 weight % enzyme, in each case Total solid content meter based on preparaton of the present invention.
In addition to sodium citrate (C), preparaton of the present invention can be washed comprising one or more builder, especially without phosphorus help Agent.The example of suitable builder is silicate, especially sodium disilicate and sodium metasilicate, zeolite, especially sheet silicate, formula α-Na2Si2O5、β-Na2Si2O5With δ-Na2Si2O5Those, and fatty acid sulfonate, α-hydracrylate, alkali metal malonic acid Salt, fatty acid sulfonate, alkyl and alkenyl disuccinate, tartaric acid diacetin, tartaric acid Monoacetate, oxidized starch And polymer builders, such as polycarboxylate and poly-aspartate.
In one embodiment of the invention, builder be selected from polycarboxylate, for example (methyl) acrylate homopolymer or The alkali metal salt of (methyl) acrylic copolymer.
Suitable comonomer is monoethylenically unsaturated dicarboxylic acid such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and lemon Health acid.Suitable polymer especially polyacrylic acid, it preferably has 2000-40000g/mol, preferably 2000-10000g/ Mol, especially 3000-8000g/mol mean molecule quantity Mw.Also suitable is co-polymeric polycarboxylic acids' salt, especially acrylic acid with Those of methacrylic acid, and acrylic or methacrylic acid and maleic acid and/or fumaric acid those.
It can also use at least one selected from monoene category unsaturation C3-C10Monocarboxylic acid or C4-C10Dicarboxylic acids or its acid anhydrides example Monomer and at least one such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid is as follows Listed hydrophilic or hydrophobically modified monomer copolymer.
Suitable hydrophobic monomer is, for example, isobutene, diisobutylene, butylene, amylene, hexene and styrene, with 10 Or more carbon atom alkene or its mixture, such as 1- decene, 1- dodecylenes, tetradecene, cetene, 1- ten Eight carbenes, 1- eicosylenes, the dodecylenes of 1- bis-, 1- tetracosenes and 1- cerotenes, C22- alpha-olefin, C20-C24-α- Alkene and per molecule averagely have the mixture of the polyisobutene of 12-100 carbon atom.
Suitable hydrophilic monomer is the monomer with sulfonate radical or phosphonate groups, and with hydroxy functional group or ring The non-ionic monomer of oxyalkyl group.For example allyl alcohol, isoprene alcohol, methoxy poly (ethylene glycol) (methyl) third can be mentioned Olefin(e) acid ester, methoxyl group polypropylene glycol (methyl) acrylate, methoxyl group polytetramethylene glycol (methyl) acrylate, the poly- (ring of methoxyl group Ethylene Oxide-copolymerization-oxirane) (methyl) acrylate, ethyoxyl polyethylene glycol (methyl) acrylate, ethyoxyl poly- the third two Alcohol (methyl) acrylate, ethyoxyl polytetramethylene glycol (methyl) acrylate and the poly- (expoxy propane-copolymerization-epoxy second of ethyoxyl Alkane) (methyl) acrylate.PAG herein can be with per molecule comprising 3-50 is individual, particularly 5-40 is individual, especially 10-30 epoxy alkane unit.
It is particularly preferred containing sulfonic monomer herein for 1- acrylamido -1- propane sulfonic acids, 2- acrylamidos - 2- propane sulfonic acids, 2- acrylamido -2- methyl propane sulfonic acids, 2- methacryl amido -2- methyl propane sulfonic acids, 3- methyl Acrylamido -2- hydroxypropanesulfonic acids, allyl sulphonic acid, methallyl sulfonic acid, allyloxy benzene sulfonic acid, methallyl oxygen Base benzene sulfonic acid, 2- hydroxyls -3- (2- propenyloxy groups) propane sulfonic acid, 2- methyl -2- propylene -1- sulfonic acid, styrene sulfonic acid, vinyl Sulfonic acid, acrylic acid 3- sulfapropyls ester, methacrylic acid 2- sulfoethyls, methacrylic acid 3- sulfapropyls ester, sulfo group first Base acrylamide, sulfomethvl Methacrylamide, and the sour salt, such as its sodium, potassium or ammonium salt.
The monomer of the particularly preferred group of compound containing phosphonic acids is vinyl phosphonate and its salt.
Further, it is also possible to which amphipathic nature polyalcohol is used as into builder.
Preparaton of the present invention can for example include the builder of 10-50 weight %, preferably up to 20 weight % altogether.
In one embodiment of the invention, preparaton of the present invention can include one or more Auxiliary builders.
The example of Auxiliary builders is phosphonate, such as hydroxyalkanoate phosphonate and amino-alkane phosphonic acid salt.In hydroxyl chain In alkane phosphonate, 1- hydroxyl ethanes -1,1- diphosphonate (HEDP) is especially important as Auxiliary builders.It is preferably used as sodium Salt, wherein disodium salt are in neutrality, and tetrasodium salt is in alkaline (pH 9).Suitable amino-alkane phosphonic acid salt is preferably ethylenediamine tetraacetic methylene Base phosphonate (EDTMP), diethylenetriamine pentamethylenophosphonic acid salt (DTPMP), also have its higher homologue.They preferably with The sodium-salt form of neutral reaction is used, such as six sodium salts as EDTMP or seven and eight sodium salts as DTPMP are used.
Preparaton of the present invention can include one or more alkali carriers.If desired alkaline pH, alkali carrier is for example provided for example At least 9 pH.Such as alkali carbonate, alkali metal hydrogencarbonate, alkali metal hydroxide and alkali silicate are to close Suitable.It is preferred that alkali metal in each case be potassium, particularly preferred sodium.
In addition to bleaching agent (D), preparaton of the present invention can include one or more chlorine bleaches.
Suitable chlorine bleaches is, for example, chloro- 5, the 5- dimethyl hydantoins of 1,3- bis-, N- Clofenamides, toluene-sodium-sulfonchloramide, chlorine Amine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, postassium hypochlorite, DCCK and DCCNa.
Preparaton of the present invention can for example include 3-10 weight % chlorine bleaches.
Preparaton of the present invention can include one or more bleaching catalysts.Bleaching catalyst can be selected from promotion bleaching Transition metal salt and/or transient metal complex, such as manganese-, iron-, cobalt-, ruthenium-or molybdenum-salicylide ethylene diamine ligand (salen) match somebody with somebody Compound or-carbonyl-complexes.Can also use the manganese with nitrogenous three pin (tripod) part, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and Copper complex and cobalt-, iron-, copper-and ruthenium-amine complex be used as bleaching catalyst.
Preparaton of the present invention can include one or more bleach activators, such as N-methylmorpholineAcetonitrile salt (" MMA Salt "), trimethyl ammonium acetonitrile salt, N- imides such as N- nonanoylsuccinimides, 1,5- diacetyl -2,2- dioxo Hexahydro -1,3,5- triazines (" DADHT ") or nitrile quaternary salt (trimethyl ammonium acetonitrile salt).
Other examples of suitable bleach activator are tetra acetyl ethylene diamine (TAED) and tetra-acetylated hexamethylene diamine.
Preparaton of the present invention can include one or more corrosion inhibitors.In the present case, this, which is interpreted as referring to, suppresses gold Belong to those compounds of corrosion.The example of suitable corrosion inhibitor is triazole type, especially benzotriazole, dibenzo triazole Class, aminotriazole(ATA) class, alkyl amino triazole type, also phenol derivatives, such as quinhydrones, catechol, hydroxy-hydroquinone, gallate, Phloroglucin or pyrogallol.
In one embodiment of the invention, the corrosion comprising 0.1-1.5 weight % suppresses preparaton of the present invention altogether Agent.
Preparaton of the present invention can include one or more builders, such as sodium sulphate.
Preparaton of the present invention can be selected from silicone oil and paraffin oil comprising one or more defoamers.
In one embodiment of the invention, preparaton of the present invention includes 0.05-0.5 weight % defoamer altogether.
Preparaton of the present invention can include phosphonic acids or one or more phosphonate derivatives, such as hydroxyl ethane -1,1- diphosphine Acid.
Invention further provides purposes of the preparaton of the present invention in machine-washing vessel and kitchen utensils.In this hair In bright context, it should be mentioned that kitchen utensils be, for example, tank, pan, earth pot, also metal such as skimming tool, fish slice and Squeeze garlic device.
It is preferred that preparaton of the present invention machines clean have at least one can be decorated or not decorated glass control surface Article in purposes.Thus, in the context of the present invention, glass control surface is interpreted as referring to the article with least One part is as the part made by glass, and it contacts the air of surrounding and can be by dirty when using the article.Therefore, it is described Article can be those basic being made up of glass as drinking glass or glass bowl.However, they for example can also be Lid with the single component being made up of another material, such as cover with metal edge and handle.
Glass control surface can be decorated, for example, colour or impress, or can not decorated.
Term " glass " includes any required glass, such as lead glass and especially soda-lime glass, crystal glass and boron Silicate glass.
It is preferred that, machines clean is the washing (automatic utensil washing) using ware wash machine.
In one embodiment of the invention, at least one preparaton of the present invention is used for drinking glass, glass system The machines clean of vase and ovenproof glass container.
In one embodiment of the invention, by water that hardness is 1-30 ° of Deutschland hardness, preferably 2-25 ° Deutschland hardness For cleaning, wherein Deutschland hardness should be particularly understood that finger calcium hardness.
Rinsing is alsoed for, it is 1-30 ° of Deutschland hardness, the water of preferably 2-25 ° Deutschland hardness that can use hardness.
If preparaton of the present invention is used for into machines clean, even tabulated in machines clean repeatedly with least one glass During the article in face, and it is and if only if clear together with the cutter or pottery that the article with least one glass control surface and severe are stained When clean, low-down glass corrosion tendency is also only observed.In addition, preparaton of the present invention is used for glass and metal article Together, for example cleaned significantly more without harm together with tank, pan or squeezing garlic device.
Furthermore, it is possible to which it was observed that preparaton of the present invention has when for ware washing and kitchen utensils and glass surface Extraordinary bleaching effect.
The present invention further provides a kind of method for preparing preparaton of the present invention, preparation method of the present invention is also referred to as.For Carry out preparation method of the present invention, the process for example can be including in one or more steps in presence of water will be such as the following group Divide and be mutually mixed：
(A) amino carboxylic acid compound, selected from MDGA compound (MGDA), iminodisuccinic acid (IDS) and Glutamic acid diacetic acid compound (GLDA) and its salt, and
(B) at least one alkoxylate alkylene imine polymers, there is average molecular weight Mw to be 800-25000g/ for it Mol, positive charge density is at least 5meq/g, and the alkylene oxide side chain with 2 weight % to most 80 weight %, based on alcoxyl The total amount meter of base alkylene imine polymers,
And optionally
(C) sodium citrate, or
(D) at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulphate,
And optionally other components (E),
Then water is completely or partially removed.
Compound (A), modified polyalkyleneimine (B) and bleaching agent (D) are as defined above.
In one embodiment of the invention, before at least part removes water, with one for preparaton of the present invention Plant or the mixing of various other compositions (E) can for example be mixed with following material：One or more surfactants, one Plant or a variety of enzymes, one or more builders, one or more Auxiliary builders, especially non-phosphorus builder, it is one or more Alkali carrier, one or more bleaching agents, one or more bleaching catalysts, one or more bleach activators, one or more bleaching Stabilizer, one or more defoamers, one or more corrosion inhibitors, one or more builders, buffer or dyestuff.
In one embodiment, the process is included by evaporation, particularly by spray drying, mist projection granulating or compacting, So as to completely or partially remove water from preparaton of the present invention, such as it is 0.1-10 weight % to residual moisture.
In one embodiment of the invention, water is completely or partially removed under the pressure of 0.3-2 bars.
In one embodiment of the invention, water is completely or partially removed at a temperature of 60-220 DEG C.
Preparaton of the present invention can be readily derived by preparation method of the present invention.
Cleaning formulations of the present invention can be in liquid or solid form, using single-phase or multiphase, as tablet or in terms of other Measure unit form, provided with packaging or unpackaged form.The water content of liquid adjustments can change in 35-90% water.
The present invention is illustrated by working Examples.
It is general：Ensure test article according to being cleaned for the first time in family expenses ware wash machine until weighing and visually rank glass Afterwards, using only cleaning mitten processing test article, so that the weight and/or range estimation impression of test article will not be forged.
The data represented using % is weight %, unless otherwise clearly indicating.
I. preparaton of the present invention is prepared
The charge density of modified polyethyleneimine (B) is always pressed and determined as follows (referring also to Horn, Prog.Colloid＆ Polym.Sci.1978,65,251)：
Modified polyethyleneimine described in 1g (B) is dissolved in 100ml softened waters.Set up using cushioning liquid and aqueous HCl 4.0 pH, is determined by potentiometry.Add 3ml aqueous Toluidine Blue solutions (50mg/l water) and be 0.0004meq/ with concentration Ml N/400-KPVS (polyvinyl potassium sulfate) solution (Wako) titration, until color is by indigo plant change powder.Charge density is by as follows Calculate：
LA=0.4KV
Wherein
LA：The charge density of the modified polyethyleneimine (B), meq/g (milliequivalent/gram)
KV：The consumption of N/400-KPVS solution, [ml]
I.1 basic mixture is prepared
First by preparing basic mixture according to the feed material of table 1.Feed material is dry-mixed.
Table 1：The basic mixture tested with preparaton of the present invention and control formulation
All data are in terms of g.
Abbreviation：
MGDA：MDGA is used as trisodium salt
TAED：N, N, N ', N '-tetra acetyl ethylene diamine
I.2 preparaton of the present invention is prepared
I.2.1 preparaton 2-8 of the present invention and control formulation V1 is prepared
Using the modified polyethyleneimine (B) shown in table 2, it is prepared according to following general procedure：
By the polyethyleneimine arranged according to table 2 the 2nd and 3 and the KOH pellet (water based on the weight % of polyethyleneimine meter 0.7 Content is 50 weight %, and remaining is KOH) add in 2L autoclaves.Mixture is heated to 120 DEG C under decompression (10 millibars), And stirred 2 hours at 120 DEG C, water is removed during this period.Then autoclave is purged three times with nitrogen, and initially pressed in 1 bar 140 DEG C are heated under power.Then, the oxirane or expoxy propane arranged according to table 2 the 5th was added in 2 hours.When addition is completed When, mixture is stirred for 3 hours at 140 DEG C.Then, water or optionally other is removed at decompression (10 millibars) and 90 DEG C Volatile compound.This obtains the modified polyethyleneimine (B) according to table, is lurid waxy solid.
Table 2：Modified polyethyleneimine (B)
Abbreviation in table 2：
AO:Alkylene oxide
2nd row：Mw PEI represent the molecular weight of the polyethyleneimine for alkoxide, i.e., for unmodified polyethyleneimine Amine.
3rd row：PEI represents unmodified polyethyleneimine
7th row：Molar ratio represents parent material.
8th row：Alkylene oxide part by weight in all alkoxylate alkylene imine polymers (B).
Process：
20ml distilled water is introduced in 100ml beakers and modified polyethyleneimine according to table 2 and 3 is added under agitation (B)。
Then the mixture is stirred 10 minutes.Then the MGDA trisodium salts being dissolved in 30ml water are added according to table 3 (A.1).This obtains as clear as crystal solution.Then the basic mixture according to table 3 is added, the mixture is again stirring for and steamed Shampoo.
If by the basic mixture of corresponding proportion independently of (A.1), (B), (C.1) or (D.1) in the process of the test The aqueous solution is metered, then with test equal amount active component drying preparaton when obtain identical result.Therefore, metered charge Order is not problem.
II. the purposes of preparaton of the present invention and control formulation in machines clean glass
It is general：Ensure test article according to being cleaned for the first time in family expenses ware wash machine until weighing and visually rank glass Afterwards, using only cleaning mitten processing test article, so that the weight and/or range estimation impression of test article will not be forged.
The test of preparaton of the present invention and control formulation is performed as follows.
Method of testings of the II.1 for the ware wash machine with continuous operation
Ware wash machine：Miele G 1222SCL
Process：65 DEG C (band prewashing)
Vessel：3 " GILDE " champagne glasses, 3 " INTERMEZZO " brandy glasses
In order to clean, glass is placed in the top pottery basket of ware wash machine.Dish washing agent used is every kind of In the case of be that, according to the 25g preparatons of the present invention or 25g control formulations of table 3, table 3 illustrates that the present invention matches somebody with somebody in each case The active component (A.1) of preparation, basic mixture, silicate (C.1 or C.2) and compound (D) and/or (E) and (B).Washing Carried out at a temperature of 55 DEG C of clear drift.The water hardness is in each case 0-2 ° of Deutschland hardness.Washing is carried out in each case 100 wash cycles, the i.e. process are run 100 times.Gravimetric analysis and visually rank are carried out after 100 wash cycles.
Glass weight is determined after drying before first time wash cycle is started and after last time wash cycle. Weight loss is the difference of the two values.
In addition to gravimetric analysis is assessed, 1 is used in the darkroom for having light after being circulated at 100 after perforated plate (very Difference) to 5 (very good) grading system to vessel carry out visually rank.Thus, in each case determine layer corrosion/ Haze and/or line corrosion grade.
The test procedure：
For the purpose of pretreatment, test article is used into 1g tables in family expenses ware wash machine (Bosch SGS5602) first Face activating agent (n-C18H37(OCH2CH2)10) and 20g lemons acid elution is to remove any pollutant OH.Test article is dried, determined Its weight is simultaneously fastened to mesh-like base insert.
In order to assess weight abrasion, dry test article of weighing.Then the visually rank of test article is carried out.Therefore, to test article Surface evaluation line corrosion (ridge line) and corrosion of hazing (sheet hazes).
It is estimated according to following scheme.
Line corrodes：
L5：There is no visible lines
L4：Slight line, fine rule corrosion are formed in considerably less region
L3：In the wired corrosion in several regions
L2：In the wired corrosion in some regions
L1：Serious line corrosion
Glass hazes：
L5：There is no visible haze
L4：Slightly hazed in considerably less region
L3：Hazed in several regions
L2：Hazed in some regions
L1：Substantially seriously hazed on whole glass surface
Also allow intermediate grade (such as L3-4) during assessing.
If being tested instead of water with hardness for the water of 2 ° of Deutschland hardness, preparaton of the present invention is equally always rotten in glass It is better than corresponding control formulation in terms of the suppression of erosion.
II.3 results
As a result it is summarized in table 3.
All it is only unusual slight glass corrosion or even without glass corrosion in embodiments of the present invention.

Claims (14)

1. a kind of preparaton without heavy metal, it is included：
(A) 1-50 weight % at least one amino carboxylic acid compound altogether, selected from MDGA compound (MGDA), sub- Amino disuccinic acid (IDS) and glutamic acid diacetic acid compound (GLDA) and its salt,
(B) 0.001-2 weight % at least one alkoxylate alkylene imine polymers altogether, it has average molecular weight Mw For 800-25000g/mol, positive charge density is at least 5meq/g, and the alkylene oxide with 2 weight % to most 80 weight % Side chain, the total amount meter based on alkoxylate alkylene imine polymers,
Solid content meter based on the preparaton in each case.
2. preparaton according to claim 1, its not phosphate-containing and Quadrafos.
3. according to the preparaton of claim 1 or 2, wherein (B) is selected from the poly- second reacted with oxirane or expoxy propane Alkene imines.
4. according to the preparaton of claim 1 or 2, its content of beary metal having is less than 0.05ppm, based on the preparaton Solid content meter.
5. according to the preparaton of claim 1 or 2, wherein alkylene imine polymers (B) polymerize selected from wherein alkylene imine At most 30 moles % nitrogen-atoms of the primary and secondary amino of thing with expoxy propane react those.
6. according to the preparaton of claim 1 or 2, it is solid at room temperature.
7. according to the preparaton of claim 1 or 2, it includes 0.1-10 weight % water.
8. according to the preparaton of claim 1 or 2, wherein nitrogen-atoms in alkoxylate alkylene imine polymers (B) with Mol ratio between alkylen groups is at most 5.
9. purposes of the preparaton as claimed in one of claims 1-8 in ware washing and kitchen utensils, wherein washing makes Carried out with the water that hardness is 2-25 ° of Deutschland hardness.
10. preparaton as claimed in one of claims 1-8 has at least one can be decorated or not decorated in washing Purposes in the article of glass control surface.
11. purposes according to claim 9 or 10, wherein the washing is the washing using ware wash machine.
12. purposes according to claim 9 or 10, wherein by least one preparaton as claimed in one of claims 1-8 For washing drinking glass, glass flower pot and ovenproof glass container.
13. the method for preparaton as claimed in one of claims 1-8 is prepared a kind of, wherein existing in one or more steps Following component is mutually mixed in the presence of water：
(A) amino carboxylic acid compound, selected from MDGA compound (MGDA), iminodisuccinic acid (IDS) and paddy ammonia Sour diethyl acidulants (GLDA) and its salt, and
(B) at least one alkoxylate alkylene imine polymers, there is average molecular weight Mw to be 800-25000g/mol for it, just Charge density is at least 5meq/g, and the alkylene oxide side chain with 2 weight % to most 80 weight %, sub- based on alkoxylate The total amount meter of alkyl imino polymer,
And optionally other components,
Then the water is completely or partially removed.
14. method according to claim 13, wherein removing the water by spray drying or mist projection granulating.
CN201380033256.6A 2012-04-25 2013-04-23 Preparaton, it is as or for producing purposes and its preparation of warewashing detergent Expired - Fee Related CN104379717B (en)

Applications Claiming Priority (21)

Application Number Priority Date Filing Date Title
US201261637901P 2012-04-25 2012-04-25
US201261637891P 2012-04-25 2012-04-25
EP12165550 2012-04-25
EP12165545.0 2012-04-25
US61/637,891 2012-04-25
EP12165550.0 2012-04-25
US61/637,901 2012-04-25
EP12165556 2012-04-25
EP12165556.7 2012-04-25
EP12165545 2012-04-25
EP12168044.1 2012-05-15
EP12168054 2012-05-15
EP12168044 2012-05-15
EP12168038.3 2012-05-15
EP12168054.0 2012-05-15
EP12168038 2012-05-15
US201261697817P 2012-09-07 2012-09-07
EP12183437 2012-09-07
EP12183437.8 2012-09-07
US61/697,817 2012-09-07
PCT/EP2013/058391 WO2013160301A1 (en) 2012-04-25 2013-04-23 Formulations, use thereof as or for production of dishwashing detergents and production thereof

Publications (2)

Publication Number Publication Date
CN104379717A CN104379717A (en) 2015-02-25
CN104379717B true CN104379717B (en) 2017-08-11

Family

ID=49482225

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201380033256.6A Expired - Fee Related CN104379717B (en) 2012-04-25 2013-04-23 Preparaton, it is as or for producing purposes and its preparation of warewashing detergent

Country Status (11)

Country Link
EP (1) EP2841549B1 (en)
JP (1) JP6133971B2 (en)
KR (1) KR102007148B1 (en)
CN (1) CN104379717B (en)
BR (1) BR112014026565A2 (en)
CA (1) CA2871210A1 (en)
ES (2) ES2612342T3 (en)
MX (1) MX2014013009A (en)
PL (1) PL2841549T3 (en)
RU (1) RU2623440C2 (en)
WO (1) WO2013160301A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014173473A1 (en) * 2013-04-23 2014-10-30 Basf Se Formulations, use thereof as or for production of dishwashing detergents and production thereof
ES2632465T3 (en) * 2013-02-28 2017-09-13 Basf Se Formulations, their use as or for the preparation of dishwashing products and their preparation
US9994797B2 (en) * 2013-04-02 2018-06-12 Basf Se Formulations, preparation thereof, and use thereof as, or for preparing, dishwashing compositions
KR102205587B1 (en) * 2013-05-27 2021-01-20 바스프 에스이 Aqueous solutions containing a complexing agent in high concentration
JP2015086295A (en) * 2013-10-30 2015-05-07 花王株式会社 Dishwashing detergent composition
EP3224338B1 (en) * 2014-11-26 2019-04-17 Basf Se Aqueous solution containing combination of complexing agents
EP3034596B2 (en) 2014-12-17 2021-11-10 The Procter & Gamble Company Detergent composition
JP2018529788A (en) * 2015-07-09 2018-10-11 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ How to wash dishes
RU2742268C2 (en) 2016-06-20 2021-02-04 Басф Се Powders and granules and method of producing such powders and granules

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999005248A1 (en) * 1997-07-23 1999-02-04 Unilever Plc Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers
WO2009092699A1 (en) * 2008-01-24 2009-07-30 Unilever Nv Machine dishwash detergent compositions
WO2010020765A1 (en) * 2008-08-16 2010-02-25 Reckitt Benckiser N.V. Composition
CN101835883A (en) * 2007-10-25 2010-09-15 禾大国际股份公开有限公司 Laundry formulations and method of cleaning

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PE6995A1 (en) * 1994-05-25 1995-03-20 Procter & Gamble COMPOSITION INCLUDING A PROPOXYLATED POLYKYLENE OAMINE POLYKYLENE OAMINE POLYMER AS DIRT SEPARATION AGENT
US5837663A (en) 1996-12-23 1998-11-17 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing tablets containing a peracid
DE19819187A1 (en) 1998-04-30 1999-11-11 Henkel Kgaa Solid dishwasher detergent with phosphate and crystalline layered silicates
WO2001096516A1 (en) 2000-06-14 2001-12-20 The Procter & Gamble Company Process for cleaning a surface
US7138462B2 (en) * 2003-08-22 2006-11-21 Los Alamos National Security, Llc Functionalized polymers for binding to solutes in aqueous solutions
EP1877531B1 (en) 2005-04-15 2010-10-13 Basf Se Amphiphilic water-soluble alkoxylated polyalkylenimines with an internal polyethylene oxide block and an external polypropylene oxide block
JP5213091B2 (en) 2006-08-22 2013-06-19 ディバーシー株式会社 Granular detergent composition for automatic dishwasher, method for producing the same, and method for using the same
ES2412684T3 (en) * 2009-06-19 2013-07-12 The Procter & Gamble Company Liquid dishwashing detergent composition by hand
PL2392638T3 (en) * 2010-06-04 2018-03-30 Dalli-Werke Gmbh & Co. Kg Low-hygroscopic particulate composition comprising one or more aminopolycarboxylate chelating compounds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999005248A1 (en) * 1997-07-23 1999-02-04 Unilever Plc Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers
CN101835883A (en) * 2007-10-25 2010-09-15 禾大国际股份公开有限公司 Laundry formulations and method of cleaning
WO2009092699A1 (en) * 2008-01-24 2009-07-30 Unilever Nv Machine dishwash detergent compositions
WO2010020765A1 (en) * 2008-08-16 2010-02-25 Reckitt Benckiser N.V. Composition

Also Published As

Publication number Publication date
JP6133971B2 (en) 2017-05-24
ES2693772T3 (en) 2018-12-13
EP2841549A1 (en) 2015-03-04
CN104379717A (en) 2015-02-25
KR20150013593A (en) 2015-02-05
ES2612342T3 (en) 2017-05-16
KR102007148B1 (en) 2019-08-05
BR112014026565A2 (en) 2017-06-27
MX2014013009A (en) 2015-08-06
RU2623440C2 (en) 2017-06-26
PL2841549T3 (en) 2017-04-28
EP2841549B1 (en) 2016-10-26
WO2013160301A1 (en) 2013-10-31
RU2014147082A (en) 2016-06-10
CA2871210A1 (en) 2013-10-31
JP2015515531A (en) 2015-05-28

Similar Documents

Publication Publication Date Title
CN104379717B (en) Preparaton, it is as or for producing purposes and its preparation of warewashing detergent
CN103874756B (en) Preparaton, its as or for preparing purposes and its preparation of dishwasher detergent
CN104284971B (en) Preparaton, its as or production warewashing detergent purposes and its production
CN106459849B (en) Preparaton, as or production dish washing agent in purposes and its preparation
CN103890158B (en) Preparaton, preparation method and its purposes for being used as or being used to prepare dishwashing agent
CN105102602B (en) Preparaton, its as or for product dish washing detersive purposes and its preparation
US9732309B2 (en) Formulations, their use as or for producing dishwashing detergents and their production
KR101952567B1 (en) Formulations, use thereof as or to produce dishwashing detergents, and production thereof
US8846593B2 (en) Dishwashing composition comprising a covalently modified alkyleneimine polymer
JP2018529788A (en) How to wash dishes
CN105143424B9 (en) Preparaton, its as or be used to prepare the purposes and its preparation of dish washing detersive
TW201321498A (en) Formulations, their use as or for producing dishwashing detergents and their production

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20170811