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CN103987831A - Use of formulations for machine dishwashing - Google Patents

Use of formulations for machine dishwashing Download PDF

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Publication number
CN103987831A
CN103987831A CN201280060636.4A CN201280060636A CN103987831A CN 103987831 A CN103987831 A CN 103987831A CN 201280060636 A CN201280060636 A CN 201280060636A CN 103987831 A CN103987831 A CN 103987831A
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CN
China
Prior art keywords
weight
multipolymer
purposes
preparaton
alcoxylates
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Inventor
S·费舍尔
J·特罗皮施
H·韦伯
R·埃特尔
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BASF SE
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BASF SE
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    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • 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
    • C11D3/3788—Graft polymers

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)
  • Washing And Drying Of Tableware (AREA)

Abstract

The use of formulations comprising (a1) at least one copolymer obtainable through copolymerization of (a1.1) at least one N-vinylamide, (a1.2) vinyl acetate, (a1.3) at least one polyether, (a1.4) optionally at least one further comonomer, (a2) at least one alkoxylate of the general formula (I) R1-(OCH2CHR2)mOR3 where the variables are each defined as follows: R1 is C8-C24-alkyl, linear or branched, R2 is C1-C10-alkyl, in each case the same or different, linear or branched, or hydrogen, R3 is hydrogen or C1-C4-alkyl, linear or branched, m is 1 to 100, in formulations for machine dishwashing.

Description

The purposes of preparaton in mechanical dishwashing detergent
The purposes of the preparation that the present invention relates to comprise following component in automatic tableware wash formulations:
(a1) at least one multipolymer that can obtain by following monomer copolymerization:
(a1.1) at least one N-vinylamide,
(a1.2) vinyl-acetic ester,
(a1.3) at least one polyethers,
(a1.4) optional at least one other comonomer,
(a2) alcoxylates of at least one general formula (I):
R 1-(OCH 2CHR 2) mOR 3 (I)
Wherein variable-definition is as follows:
R 1for linearity or branching C 8-C 24alkyl,
R 2identical or different in every kind of situation, be linearity or branching C 1-C 10alkyl or hydrogen,
R 3for hydrogen or linearity or branching C 1-C 4alkyl
M is the number of 1-100.
The invention further relates to the purposes of specific copolymer.
There is the harsh requirement about machine dishwashing detergent preparaton.Except actual noresidue is cleaned, it is desirable to obtain vessel, metal object and the glass of perfect light.Until about calendar year 2001, in many cases, therefore washing composition, rinse aid and so-called regenerant salt are metered into respectively in dishwasher, wherein regenerant salt has the task in conjunction with calcium ion and magnesium ion, and rinse aid has and guarantees water diffluence prevent lime mark and the formation of water gauge note from the whole area of goods.
" three-in-one " dish washing detergent of introducing from that time combines the function of washing composition, rinse aid and regenerant salt in a kind of product.Therefore, human consumer need to not supplement rinse aid and salt in dishwasher.Other function (for example protecting with protection against corrosion and protection in case the corrosion of silver) be incorporated to the exploitation that causes x unification (wherein for example x=6 or 9) or " integrated " product.
The combination that WO2008/132131 discloses at least one alcohol alkoxylate, at least one short chain alcohol ethoxylate, at least one polymkeric substance containing sulfonate groups and/or at least one hydrophilic modifying polycarboxylate and optional polycarboxylate is improving the purposes in the cleaning-rinsing performance in phosphorous and without phosphorus machine dish washing detergent together with other component of common routine.
DE 102 33 834 A disclose the alkoxylate with 8-18 carbon atom and the average every mol of alcohol of 1-12 mole ethylene oxide (EO), and preferably ethoxylation primary alconol is as the nonionogenic tenside in machine dish washing compositions.The natural origin alcohol that preferably has 12-18 carbon atom and have the average 2-8 mole of every mol of alcohol of EO is as the alcohol ethoxylate of lauric alcohol, palmityl alcohol, tallow alcohol or oleyl alcohol.
Many " X unifications " or " integrated " dish washing detergent are not still realized good cleaning-rinsing result that can use the rinse aid time limit separately, be water from vessel without the ground diffluence of striped and dripless, make them not with shinny and obtain without dry water droplet (stain).Also find especially at harder a little water, while washing in 10 ° of water more than Deutschland hardness, can to improve film forming.On this point, film forming is to be understood that meaning undesired settling on an area forms.Therefore, the value of film forming is better, and the settling occurring on the surface of object to be washed is more even and less.
Therefore, object is to provide the preparaton can be used in " X unification " or " integrated " dish washing detergent rinse aid can for example be added by tablet dose in main wash(ing)cycle, but only observes good effect in cleaning-rinse cycle.
Therefore, find to start the purposes of the preparation defining in machine dishwashing detergent preparaton, also referred to as the present invention's preparation used.
The present invention's preparation used comprises:
(a1) at least one multipolymer, also referred to as multipolymer (a1).Multipolymer (a1) can obtain by following monomer copolymerization:
(a1.1) at least one N-vinylamide, for example N-vinyl formamide or N-vinyl acetamide, preferably at least one N-vinyl lactam, for example NVP and N-caprolactam,
(a1.2) vinyl-acetic ester,
(a1.3) at least one polyethers,
(a1.4) optionally at least one other comonomer, for example (methyl) vinylformic acid, (methyl) vinyl cyanide and (methyl) vinylformic acid C 1-C 4alkyl ester.
The example of suitable polyethers (a1.3) is the polytetramethylene glycol that can obtain by 2,3-dimethyl ethylene oxide or 2-ethyl ethylene oxide polymerization.Preferred polyethers (a1.3) is selected from polyoxyethylene glycol, polypropylene glycol and polytetrahydrofuran, and is selected from the mixed polymer of ethylene oxide and propylene oxide and/or 2,3-dimethyl ethylene oxide or 2-ethyl oxyethane.The mixed polymer of above-mentioned ethylene oxide and propylene oxide and/or 2,3-dimethyl ethylene oxide or 2-ethyl oxyethane can be random copolymers or segmented copolymer, and those of for example ethylene oxide and propylene oxide can be AB type or ABA type.
Can be by C identical or different in every kind of situation for polyethers (a1.3) 1-C 20alkanol or alkylating agent, preferably use C 1-C 18alkanol, for example, use the unidirectional or two-way etherificate of methyl alcohol, ethanol, propyl carbinol, Virahol, n-propyl alcohol, isopropylcarbinol, Pentyl alcohol, n-hexyl alcohol, n-Octanol, nonanol-, nonylcarbinol, n-dodecane alcohol, n-tridecane alcohol, cetyl alcohol or Octadecane alcohol.
In another embodiment of the present invention, polyethers (a1.3) is glycol.
In one embodiment of the invention, polyethers (a1.3) has 1000-100000g/mol, preferably 1500-35000g/mol, particularly preferably the molecular-weight average M of 10000g/mol w.Molecular-weight average M woriginate in the OH value of measuring according to DIN53240 or measure by gel permeation chromatography (GPC).
In a preferred embodiment of the present invention, multipolymer (a1) is graft copolymer, wherein at least one polyethers (a1.3) is as grafting basis, and N-vinylamide (a1.1), vinyl-acetic ester (a1.2) and optional at least one other comonomer (a1.4) are for example by free-radical polymerized grafting thereon.
In one embodiment of the invention, being in those multipolymers (a1) of graft copolymer, N-vinylamide (a1.1), vinyl-acetic ester (a1.2) and optional at least one other comonomer (a1.4) are irregularly grafted in side chain.In another embodiment of the present invention, in the every kind of situation of side chain for this analog copolymer (a1) of graft copolymer, only comprise the N-vinylamide (a1.1) of polymerization or only comprise vinyl-acetic ester (a1.2) or optionally only comprise other comonomer (a1.4).
The example of suitable other comonomer (a1.4) is (methyl) vinylformic acid, (methyl) vinyl cyanide and (methyl) vinylformic acid C 1-C 4alkyl ester, preferably vinylformic acid, methyl acrylate, ethyl propenoate and n-butyl acrylate.
In one embodiment of the invention, multipolymer (a1) has the molecular-weight average M that measures 90000-140000g/mol by GPC w.
In one embodiment of the invention, multipolymer (a1) has at room temperature and in 1 % by weight ethanolic soln, is measured as 10-60 according to Fikentscher, preferably the K value of 15-40.
In one embodiment of the invention, multipolymer (a1) comprises polymerized form:
Amount to 30-80 % by weight, preferably 40-70 % by weight, the particularly preferably N-vinylamide (a1.1) of 50-60 % by weight,
Amount to 10-50 % by weight, preferably 15-35 % by weight, the particularly preferably vinyl-acetic ester of 25-35 % by weight (a1.2),
Amount to 10-50 % by weight, preferably 30 % by weight at the most, particularly preferably 25 % by weight at the most, the very particularly preferably polyethers of 20 % by weight (a1.3) at the most,
Amount to 0-10 % by weight comonomer (a1.4),
Quality based on whole multipolymer (a1) in every kind of situation.
In addition, the present invention's preparation used comprises:
(a2) alcoxylates of at least one general formula (I):
R 1-(OCH 2CHR 2) mOR 3 (I)
Also referred to as alcoxylates (a2), wherein variable is:
R 1for branching or preferred linear C 8-C 24alkyl, for example n-octyl, positive decyl, dodecyl, n-tetradecane base, n-hexadecyl, Octadecane base, NSC 62789 base,
R 2for linearity identical or different in every kind of situation or branching C 1-C 10alkyl, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, isopentyl; N-hexyl, isohexyl, Sec-Hexyl, n-octyl, positive decyl, isodecyl, particularly preferably methyl, or preferred hydrogen,
R 3for hydrogen or branching or preferred linear C 1-C 4alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, particularly preferably methyl or normal-butyl, the number that m is 1-100.Number m refers to mean value, and can be integer, but may not be integer.
If select m for being greater than 1 and at least two R 2differ from one another, the alcoxylates of formula (I) can be random copolymers or segmented copolymer; They are preferably segmented copolymer.Radicals R therein 2be different and select m for being greater than 3, be preferably greater than in 5 embodiment, different alkoxide unit can be with random distribution or block fashion, and preferred block fashion is arranged in alcoxylates (a2).
Preferred alcoxylates (a2) is for having the alkoxylate of 8-18 carbon atom and average every mole of alkanol of 1-12 mole ethylene oxide (EO), preferably ethoxylation primary alkanol.Particularly preferably use every mole of C of average 2-8 mole EO 8-C 18the natural origin alcohol with 12-18 carbon atom of alkanol ethoxylation is as the alcoxylates of lauric alcohol, palmityl alcohol, tallow alcohol or oleyl alcohol.As an example, can especially mention the C with every mole of alkanol ethoxylation of average 3 or 4 moles of EO 12-C 14alkanol, with the C of every mole of alkanol ethoxylation of average 7 moles of EO 9-C 11alkanol, with the C of every mole of alkanol ethoxylation of average 3,5,7 or 8 moles of EO 13-C 15alcohol, and with the C of every mole of alkanol ethoxylation of average 5 moles of EO 12-C 18alcohol.
In addition especially can mention:
-with the C of 9 mole ethylene oxides and 2 moles of every mole of alkoxy of oxybutylene 13-C 15the mixture of oxo alcohol,
-with 10 mole ethylene oxides and average 1.5 mole 1, the oxyalkylated iso-C of 2-oxidation amylene 10alkanol,
-with 9 mole ethylene oxides and the oxyalkylated C of 5 mole propylene oxide 10-C 12fatty alcohol,
-with average 4.46 mole ethylene oxide+0.86 mole oxybutylene alkoxylate and on single position by the C of methyl blocking 13-C 15oxo alcohol,
-with 4.5 mole ethylene oxides and the oxyalkylated 2-propyl enanthol of average 0.9 mole propylene oxide, and the mixture of at least two kinds in above-mentioned alkoxide (a2).
In the alcoxylates of formula (I), the ethoxylate of preferred formula (II):
R 1-(OCH 2CH 2) x–OR 3 (II)
Wherein:
R 1for linear C 16-C 18alkyl,
R 3for linearity or branching C 1-C 6alkyl or preferably hydrogen,
X is 8-10, preferably 8,9 or 10.
Particularly preferred formula (II) ethoxylate is based on tallow alcohol (C 16-C 18alcohol) and there are those of every mole of tallow alcohol of average 9 mole ethylene oxides.
Preferred linear C 16-C 18alkanol is cetyl alcohol and Octadecane alcohol.These can obtain by the hydrogenation of natural tallow.But suitable also have linear C 17alkanol.
The linear C of natural origin 16and C 18the mixture of alkanol is also referred to as tallow alcohol.Tallow alcohol has unsaturated part, particularly cholesterol or the how unsaturated C of small proportion 16and C 18alcohol moiety.But based on the amount of alcohol, these are generally 5 % by weight at the most, preferably 0.1-2 % by weight.In the context of the invention, owing to only slightly being polluted by unsaturated chain alkanol, tallow alcohol should be preferably included in C 16-C 18under alkanol.
In one embodiment of the invention, the present invention's preparation used comprises 1-60 % by weight multipolymer (a1) and 40-99 % by weight alcoxylates (a2), preferably 1-50 % by weight multipolymer (a1) and 50-99 % by weight alcoxylates (a2).
In one embodiment of the invention, multipolymer (a1) and alcoxylates (a2) are present in the present invention's preparation used as sosoloid.On this point, term " sosoloid " is intended to refer to the micro-discrete distribution of multipolymer (a1), or molecular dispersion is distributed in the state in the solid substrate of alcoxylates (a2) ideally, as for example by as shown in microscope.
In one embodiment of the invention, the present invention's preparation used (a) is pourable and form that can flowing water water-soluble pulverulent.
In one embodiment of the invention, the present invention's preparation used (a) for mean diameter be the form of the powder of 100-1500 μ m.In another embodiment of the present invention, the form that the present invention's preparation used (a) is particle.
In another embodiment of the present invention, the present invention's preparation used (a) is the form of intimate mixture or layer, for example, for dishwasher tablet, as ball or hemisphere, or be whole dishwasher tablet coating form or for example, as the part of dishwasher tablet, the independent surface of dishwasher tablet or the coating of surperficial fragment.
Use the present invention preparation used as or obtain fabulous cleaning and there are especially the vessel of a little lime mark for the preparation of dish washing compositions.In addition,, in the time using above-mentioned preparaton, the vessel of washing demonstrate extraordinary film forming properties.
The present invention further provides the purposes of the present invention's preparation used in machine dishwashing detergent preparaton, also referred to as purposes of the present invention.The present invention further provides the machine dishware washing method that uses at least one the present invention preparaton used.The present invention further provides the machine dishwashing detergent preparaton that comprises at least one the present invention preparaton used based on for example 0.1-20 % by weight of the present invention's preparaton used.
In one embodiment of the invention, the present invention's preparaton used comprises:
(a) amount to 0.1-20 % by weight, preferably 0.5-15 % by weight, particularly preferably at least one the present invention preparation used of 1-10 % by weight,
(b) nonionogenic tenside that is different from multipolymer (a1) and alcoxylates (a2) of total 0-10 % by weight, also referred to as tensio-active agent (b),
(c) one or more polycarboxylates of total 0-20 % by weight, also referred to as polycarboxylate (c),
(d) the title complex forming agent that is different from inorganic phosphate of total 0-50 % by weight, also referred to as title complex forming agent (d),
(e) one or more inorganic phosphates of total 0-70 % by weight, also referred to as phosphoric acid salt (e),
(f) amount in every kind of situation of 0-60 % by weight and be different from other buider of title complex forming agent (d) and help buider, also referred to as buider (f) or help buider (f),
(g) SYNTHETIC OPTICAL WHITNER of total 0-30 % by weight, also referred to as SYNTHETIC OPTICAL WHITNER (g), and optional bleach-activating agent or bleaching catalyst,
(h) enzyme of total 0-8 % by weight,
(i) one or more other additives of total 0-50 % by weight, and optional water.
Herein, the total solids level of the data that represent with % by weight based on the present invention's preparaton used.
In one embodiment of the invention, preparaton of the present invention has 5-14, preferably the pH of 8-13.
In one embodiment of the invention, preparaton of the present invention can have the water-content of the total solids level 0.1-10 % by weight based on the present invention's preparaton used.
Tensio-active agent (b) also can be described as component (b) hereinafter.Polycarboxylate (c) also can be described as component (c) hereinafter.Title complex forming agent (d) also can be described as component (d) etc. hereinafter.Preferred preparaton of the present invention comprises at least one and is selected from the material of component (b) to component (i), and wherein component (i) is different from water.
In one embodiment of the invention, additive (i) is selected from negatively charged ion or zwitterionics, basic supports, corrosion inhibitor, defoamer, dyestuff, perfume compound, filler, organic solvent, film-making auxiliary, disintegrating agent (disintegrant), thickening material and solubility promoter.
Component (b)-(i) is below described in more detail for example.
Except being present in the nonionogenic tenside of the component (a) in preparation of the present invention (a), preparaton of the present invention can comprise 10 % by weight tensio-active agents (b) at the most, for example weak or low bubble nonionogenic tenside.
Preferably preparaton of the present invention comprises total 0.1-10 % by weight, the preferably tensio-active agent (b) of 0.25-5 % by weight.
In one embodiment of the invention, tensio-active agent (b) selects free C 1-C 20two of alkanol, ethylene oxide and propylene oxide composition-and segmented copolymer.
In another embodiment of the present invention, tensio-active agent (b) is selected from the reaction product of sorbitan ester and ethylene oxide and/or propylene oxide.Other suitable tensio-active agent (b) is selected from ethoxylation or propoxylation sorbitan ester.Amine oxide or alkyl glycoside are also suitable.The general introduction of other suitable nonionogenic tenside can be found in EP-A 0 851 023 and DE-A 198 19 187.
In one embodiment of the invention, the mixture that preparaton of the present invention comprises two or more tensio-active agents (b).
In one embodiment of the invention, the present invention's preparation used comprises at least one polycarboxylate (c), an alkali metal salt of for example (methyl) acrylate homopolymer or (methyl) acrylic copolymer.Preferably preparaton of the present invention comprises total 0.1-20 % by weight polycarboxylate (c).
Suitable comonomer for (methyl) acrylic copolymer is monoethylenically unsaturated dicarboxylic acid, for example toxilic acid, fumaric acid, maleic anhydride, methylene-succinic acid and citraconic acid.Suitable acrylate copolymer particularly preferably has 2000-40000g/mol, preferably the molecular-weight average M of 2000-10000g/mol, particularly 3000-8000g/mol wpolyacrylic acid.Those of suitable copolymerization polycarboxylate (c), particularly vinylformic acid in addition and methacrylic acid and acrylic or methacrylic acid and toxilic acid and/or fumaric acid.
Also can use at least one to be selected from monoene and belong to unsaturated C 3-C 10single-or dicarboxylic acid or its acid anhydride, for example monomer of toxilic acid, maleic anhydride, vinylformic acid, methacrylic acid, fumaric acid, methylene-succinic acid and citraconic acid and at least one are as the multipolymer of listed hydrophilic or hydrophobically modified monomer below.
Suitable hydrophobic monomer for example for iso-butylene, diisobutylene, butylene, amylene, hexene and vinylbenzene, there is alkene or its mixture of 10 or more carbon atoms, for example 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene, 1-bis-dodecylenes, 1-tetracosene and 1-cerotene, C 22alpha-olefin, C 20-C 24the mixture of alpha-olefin and the polyisobutene with an average 12-100 carbon atom.
Suitable hydrophilic monomer is the monomer with sulfonate or phosphate group, and has the non-ionic monomer of hydroxyl-functional or oxyalkylene group.As an example, can mention: vinyl carbinol, isoprene alcohol, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, methoxyl group polytetramethylene glycol (methyl) acrylate, methoxyl group gathers (propylene oxide-copolymerization-ethylene oxide) (methyl) acrylate, oxyethyl group polyoxyethylene glycol (methyl) acrylate, oxyethyl group polypropylene glycol (methyl) acrylate, oxyethyl group polytetramethylene glycol (methyl) acrylate and oxyethyl group gather (propylene oxide-copolymerization-ethylene oxide) (methyl) acrylate.Herein, polyalkylene glycol comprises 3-50, particularly 5-40, an especially 10-30 oxyalkylene units.
Herein, particularly preferred is 1-acrylamido-1-propane sulfonic acid containing sulfonic acid group monomer, 2-acrylamido-2-propane sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid, 2-methacrylamido-2-methyl propane sulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allyl sulphonic acid, methallylsulfonic acid, allyloxy Phenylsulfonic acid, methyl allyloxy Phenylsulfonic acid, 2-hydroxyl-3-(2-propenyloxy group) propane sulfonic acid, 2-methyl-2-propylene-1-sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, vinylformic acid 2-sulfo group propyl ester, methacrylic acid 2-sulfo group ethyl ester, methacrylic acid 2-sulfo group propyl ester, sulfo group Methacrylamide, sulfo group methyl acrylamide, salt with described acid, for example its sodium, potassium or ammonium salt.
Particularly preferred is vinyl phosphonate and salt thereof containing phosphonate groups monomer.
In one embodiment of the invention, preparaton of the present invention comprises 50 % by weight at the most, for example at least 0.1 % by weight, preferably 1-45 % by weight, particularly preferably 1-40 % by weight title complex forming agent (d).
Preferred title complex forming agent (d) is selected from aminocarboxylic acid ester and polyaminocarboxylic acid ester and salt thereof, particularly an alkali metal salt and derivative thereof, for example methyl ester.
In the context of the invention, aminocarboxylic acid ester be to be understood that mean nitrilotriacetic acid(NTA) and-as mentioned above-can partially or completely neutralize-have a tertiary group, described tertiary group has one or two CH 2those organic compound of-COOH group.In the context of the invention, polyaminocarboxylic acid ester is to be understood that and means-as mentioned above-and can partially or completely neutralize-have those organic compound of at least two tertiary amino, described tertiary amino has one or two CH independently of each other separately 2-COOH group.
In another embodiment of the present invention, aminocarboxylic acid ester is selected from-as mentioned above-and can partially or completely neutralize-have those organic compound of a secondary amino group, described secondary amino group has one or two CH (COOH) CH 2-COOH group.In another embodiment of the present invention, polyaminocarboxylic acid ester is selected from-as mentioned above-and can partially or completely neutralize-have those organic compound of at least two secondary amino groups, described secondary amino group has a CH (COOH) CH separately 2-COOH group.
Particularly preferred aminocarboxylic acid ester and polyaminocarboxylic acid ester are selected from nitrilotriacetic acid(NTA) (NTA), ethylenediamine tetraacetic acid (EDTA) (EDTA), diethylene triaminepentaacetic acid(DTPA), hydroxyethylethylene diamine tri-acetic acid and MDGA (MGDA), L-glutamic acid oxalic acid, iminodisuccinic acid, oxyimino disuccinic acid, ethylenediamine disuccinic acid, aspartic acid oxalic acid and salt thereof, for example its an alkali metal salt, particularly its potassium and sodium salt.Particularly preferred title complex forming agent (d) is MDGA and salt thereof.
As component (e), the present invention's preparaton used can comprise 70 % by weight at the most, for example 5-60 % by weight, particularly preferably 20-55 % by weight phosphoric acid salt (e).
The example of phosphoric acid salt (e) is alkali metal phosphate and polymerization alkali metal phosphate particularly, and it can be selected from their alkalescence, neutrality or acidic sodium or sylvite.The example of this class phosphoric acid salt (e) is tertiary sodium phosphate, tetra-na diphosphate, disodium diacid diphosphate, pentasodium triphosphate, so-called Sodium hexametaphosphate 99, there is 5-1000, the preferably oligomeric phosphoric acid trisodium of the oligomeric degree of 5-50, with corresponding sylvite, or the mixture of Sodium hexametaphosphate 99 and corresponding sylvite, or the mixture of sodium and sylvite.Preferred phosphoric acid salt (e) is alkali metal phosphate, particularly Thermphos SPR or triphosphoric acid five potassium (tripoly phosphate sodium STPP or Potassium tripolyphosphate), also has sodium-metaphosphate.
In a preferred embodiment of the present invention, the present invention's preparaton used does not comprise phosphoric acid salt (e); In the context of the invention, there is the preparaton that solids content based on the present invention's specific preparaton used is less than 100 ppm by weight phosphoric acid salt (e) and be considered to without phosphorus.
As component (f), the present invention's preparaton used can comprise 60 % by weight at the most, for example 0.1-60 % by weight buider (f) or help buider (f).In the context of the invention, buider (f) and help buider (f) to be to be understood that to mean to be different from inorganic phosphate and title complex forming agent (d) and its main purpose and be the water-soluble or water-insoluble substance in conjunction with calcium ion and magnesium ion.
Buider (f) can be selected from low molecular weight carboxylic acid and salt thereof, for example citric acid and an alkali metal salt thereof, particularly anhydrous sodium citrate or citrate trisodium dihydrate.Other suitable buider (f) also has suitable succsinic acid and an alkali metal salt thereof, fatty acid sulfonate, alpha-hydroxypropionic acid, basic metal malonate, fatty acid sulfonate, C 1-C 20alkyl or C 2-C 20alkenyl disuccinate, tartrate diacetin, tartrate Monoacetate, Sumstar 190, oxygen base disuccinate, glyconic acid, oxa-diacetin, carboxymethyl oxygen base succinate, tartrate monosuccinic acid salt, tartrate disuccinate, tartrate Monoacetate, tartrate diacetin and alpha-hydroxypropionic acid.
Other example of suitable buider (f) is silicate, particularly sodium disilicate and Starso, zeolite, sheet silicate, particularly formula α-Na 2si 2o 5, β-Na 2si 2o 5and δ-Na 2si 2o 5those.
The example that helps buider (f) is phosphonate, for example hydroxyl paraffinic hydrocarbons phosphonate and amino-alkane hydrocarbon phosphonate.In alkyl chain alkane phosphonate, 1-hydroxyl ethane-1,1-diphosphonate (HEDP) is preferably as helping buider (f).It preferably as sodium salt, give the disodium salt of neutralization reaction and give alkali reaction (pH9) tetra-na salt use.Suitable amino-alkane hydrocarbon phosphonate is preferably ethylenediamine tetramethylene phosphonic acid salt (EDTMP), diethylenetriamine pentamethylenophosphonic acid(DTPP) salt (DTPMP) and higher homologue thereof.They are preferably with the form of neutral reaction sodium salt, for example as six sodium salts of EDTMP or as seven of DTPMP-and eight sodium salts use.
In addition, use carbonate and supercarbonate, wherein preferred as alkali salt, particularly sodium salt, for example sodium carbonate and sodium bicarbonate.
In one embodiment of the invention, preparaton of the present invention comprises at the most 30 % by weight SYNTHETIC OPTICAL WHITNER (g) and chooses any one kind of them or multiple bleach-activating agent or bleaching catalyst.
In one embodiment of the invention, preparaton of the present invention comprises one or more oxygen bleaching agents or one or more chlorine bleaching agents.The example of suitable oxygen bleaching agent is Sodium peroxoborate; anhydrous or for example as monohydrate or as the SPC-D of tetrahydrate or so-called dihydrate; anhydrous or for example as the hydrogen peroxide of monohydrate; persulphate; organic peracid; for example peroxide lauric acid, peroxide stearic acid, peroxide-α-naphthoic acid, 1; 12-diperoxy dodecanedioic acid, peroxybenzoic acid, 1; 9-diperoxyazelaic acid, diperoxy m-phthalic acid; in its every kind situation as free acid or as an alkali metal salt; particularly, as sodium salt, also have alkylsulfonyl peroxy acid and positively charged ion peroxy acid.
Preparaton of the present invention can comprise 0.5-15 % by weight oxygen bleaching agent.
Suitable chlorine bleaching agent is for example 1,3 dichloro 5,5 dimethyl hydantoin, N-chlorine sulphamide, chloramine-T, chloramine B, clorox, Losantin, magnesium hypophosphite, potassium hypophosphite, potassium dichloroisocyanurate and Surchlor GR 60.
Preparaton of the present invention can comprise for example 3-10 % by weight chlorine bleaching agent.
Preparaton of the present invention can comprise one or more bleaching catalysts.Bleaching catalyst can be selected from bleaching and promote transition metal salt or transition metal complex, for example manganese-, iron-, cobalt-, ruthenium-or molybdenum-selenium complexes, or manganese-, iron-, cobalt-, ruthenium-or molybdenum-carbonyl-complexes.With manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and the copper complex of nitrogenous triangle part, and cobalt-, iron-, copper-and ruthenium-amine complex also can be used as bleaching catalyst.
Preparaton of the present invention can comprise one or more bleach-activating agents, for example N-methylmorpholine-acetonitrile salt (" MMA salt "), trimethyl ammonium acetonitrile salt, N-imide, for example N-nonanoyl succinimide, 1,5-diacetyl-2,2-dioxo six hydrogen-1,3,5-triazine (" DADHT ") or nitrile quaternary ammonium salt, i.e. trimethyl ammonium acetonitrile salt.
In one embodiment of the invention, the present invention's preparaton used comprises the % by weight based on total the present invention preparaton 0.1-10 used, preferably 1-9 % by weight, particularly preferably 1.5-8 % by weight bleach-activating agent.
Preparaton of the present invention can comprise for example total 8 % by weight at the most, preferably 0.1-3 % by weight enzyme (h), the total solids level based on the present invention's preparaton used in every kind of situation.The example of enzyme (h) is lipase, lytic enzyme, amylase, proteolytic enzyme, cellulase, esterase, polygalacturonase, Sumylact L and peroxidase.
In one embodiment of the invention, preparaton of the present invention can comprise total 0.1-50 one or more additives of % by weight (i).The example of additive (i) is negatively charged ion or zwitterionics, alkali carrier, corrosion inhibitor, defoamer, dyestuff, perfume compound, filler, organic solvent, film-making auxiliary, disintegrating agent, thickening material and solubility promoter.
Disintegrating agent is also referred to as tablet disintegrant.Example is cross-linking polyethylene pyrrolidone.
The example of film-making auxiliary is for example to have at least molecular weight M of 1500g/mol wpolyoxyethylene glycol.The example of film-making auxiliary is for example to have to be greater than 1500 to the molecular weight M of 8000g/mol at the most wpolyoxyethylene glycol.
The example of anion surfactant is C 8-C 20alkyl-sulphate, C 8-C 20alkylsulfonate and the C with every mole of 1-6 ethylene oxide unit 8-C 20sulfated alkyl ether.
The example of zwitterionics be season aliphatic series ammonium salt or the derivative of salt or tertiary sulfonium salt, wherein aliphatic group can for non-branching or branching and wherein in aliphatic substituting group there is C 6-C 20alkylidene group, preferably C 8-C 18alkylidene group, it is with anionic group, for example carboxyl, sulfate group, bound phosphate groups or phosphonyl group.
The specific examples of zwitterionics is trimethyl-glycine, for example cocoamidopropyl.
Preparaton of the present invention can comprise one or more alkali carriers.If need alkaline pH, alkali carrier is guaranteed for example at least 9 pH.Suitable is for example alkaline carbonate, alkali metal hydrocarbonate, alkali metal hydroxide and alkali metal silicate.In every kind of situation, preferred basic metal is potassium, particularly preferably sodium.
Preparaton of the present invention can comprise one or more corrosion inhibitors.In this case, these are to be understood that those compounds that mean to suppress metallic corrosion.The example of suitable corrosion inhibitor is triazole, particularly benzotriazole, two benzotriazole, aminotriazole, alkylamino triazole, also has phenol derivatives, for example quinhydrones, pyrocatechol, hydroxy-hydroquinone, gallic acid, Phloroglucinol or metagallic acid.
In one embodiment of the invention, preparaton of the present invention comprises total 0.1-1.5 % by weight corrosion inhibitor.
In one embodiment of the invention, preparaton of the present invention comprises glass corrosion inhibitor.Glass corrosion can be learned by the clouding on glass surface, iris, striped and line.Preferred glass corrosion inhibitor is selected from the coordination compound of magnesium, zinc and bismuth salt and zinc, magnesium or bismuth.
Preparaton of the present invention can comprise one or more defoamers, and described defoamer is selected from for example silicone oil and paraffin oil.
In one embodiment of the invention, preparaton of the present invention comprises total 0.05-0.5 % by weight defoamer.
In one embodiment of the invention, preparaton of the present invention can comprise one or more acid, for example methanesulfonic or its salt.
In one embodiment of the invention, preparaton of the present invention can have one or more dyestuffs.The example of suitable dye is patent blue.
In one embodiment of the invention, preparaton of the present invention can comprise one or more perfume compound, for example spices.
In one embodiment of the invention, preparaton of the present invention can comprise one or more sanitass, for example 2-methyl-2H-isothiazole-3-ketone (Kathon (CG).
Suitable filler is for example sodium sulfate.
The example of suitable organic solvent is ethanol, Virahol and propylene glycol.
Cleaning formulations of the present invention can be liquid, gel single-phase or heterogeneous solid form, the form of tablet or the form of other dose unit.
If preparaton of the present invention for ware washing, obtains fabulous cleaning and has especially the vessel of considerably less lime mark.In addition, use the vessel of preparaton washing of the present invention to demonstrate extraordinary film forming properties.
The present invention further provides the purposes of preparaton of the present invention in machine dishwashing detergent.The present invention further provides the machine dishware washing method that uses at least one above-mentioned preparaton.
On this point, the statement " vessel " relevant with dishwashing detergent is to be understood that and not only means porcelain, pottery and vinyl disc, and mean tableware, for example silverware or plastic tableware, and pot, pan, kitchen utensils be as lemon juicer or garlic squeezer or amount kettle, and glass and Glass Containers for cooking.
Preferably machine dishwashing detergent is the washing (automatic tableware washing) that uses dishwasher.
In one embodiment of the invention, use hardness is 1-30 ° of Deutschland hardness, the preferably water of 2-25 ° of Deutschland hardness, and Deutschland hardness is to be understood that especially and means calcium hardness.
Due to washing methods of the present invention, obtain fabulous cleaning and there are especially the vessel of considerably less lime mark.In addition, use the vessel of preparaton washing of the present invention to demonstrate extraordinary film forming properties.
The present invention further provides the purposes of the multipolymer (a1) obtaining by following monomer copolymerization in machine dishwashing detergent preparaton:
(a1.1) at least one N-vinylamide,
(a1.2) vinyl-acetic ester,
(a1.3) at least one polyethers,
(a1.4) optional at least one other comonomer.
In a preferred variant, wherein multipolymer (a1) can obtain by following monomer copolymerization:
Amount to 30-80 % by weight N-vinylamide (a1.1),
Amount to 10-50 % by weight vinyl-acetic ester (a1.2),
Amount to 10-50 % by weight a polyethers (a1.3),
Amount to 0-10 % by weight comonomer (a1.4),
Quality based on whole multipolymer (a1) in every kind of situation.
Other performance specification of multipolymer (a1) is in above.
The present invention further provides the method for preparing the present invention's preparation used, wherein at least one multipolymer (a1) and at least one alcoxylates (a2) are mixed.
In a preferred variant, program relates at least one multipolymer (a1) or at least one alcoxylates (a2) melting, it is mixed with multipolymer (a1) or alcoxylates (a2), then make it cooling.
In another preferred variant, program relates at least one multipolymer (a1) and at least one alcoxylates (a2) is mixed with molten state separately, then makes them cooling.
In one embodiment, multipolymer (a1) and alcoxylates (a2) is for example without dilution or mix under the existence of water, then optional except anhydrating.Water can for example be removed by evaporating.
In a preferred embodiment of the present invention, by multipolymer (a1) for example stirred vessel, can heating tube or forcing machine in melting, then mix with the alcoxylates (a2) of solid or melting form.Then can make it cooling.In another embodiment of the present invention, by alcoxylates (a2) for example stirred vessel, can heating tube or forcing machine in melting, then mix with the multipolymer (a1) of solid or melting form.Then can make it cooling.
In a preferred embodiment of the present invention, multipolymer (a1) and alcoxylates (a2) are mixed with the form of solid separately, then by gained mixture for example stirred vessel, can heating tube or forcing machine in melting, then can make it cooling.
In another preferred embodiment of the present invention, multipolymer (a1) can be mixed to therefore alcoxylates (a2) melting with solid alcoxylates (a2) with melting form.During this period or subsequently, mix, then make mixture cooling.
In another preferred embodiment of the present invention, by multipolymer (a1) and alcoxylates (a2) melting, by two kinds of melt-mixing, then make it cooling respectively.
Therefore, for example can in another step, further process melt-liquid copolymer (a1) of producing after the purification operations after its preparation.For example, melt-liquid copolymer (a1) can be incorporated in suitable hybrid element and with at least one alcoxylates (a2) and mix.Suitable hybrid element is for example the second forcing machine, kneader, dynamic and static mixer and combination thereof.
Suitable embodiment is to mix by multipolymer (a1) melting and with alcoxylates (a2).Herein, program can relate to using multipolymer (a1) and alcoxylates (a2) separately or be metered in one or more entrances of forcing machine as mixture, by these meltings, mix simultaneously, and then cooling and granulate.Or only by multipolymer (a1) melting, and alcoxylates (a2) is metered in the melts of multipolymer (a1) at one or more somes place via side dosage (side travelling belt).In this embodiment, extruder screw should have suitable hybrid element.Suitable hybrid element can be for example for transmit and non-transmission kneading block, have tooth hybrid element, have perforated bars element, turbine hybrid element, have the hybrid element of saving, have tooth section etc.
According to an embodiment, dry copolymer (a1) obtains under the existence of alcoxylates (a2).For this reason, alcoxylates (a2) can be added in the solution or dispersion of multipolymer (a1), or add in molten copolymer (a1), and can make gained mixture enter in forcing machine, or dividually alcoxylates (a2) is introduced in forcing machine.For example, nonionogenic tenside (a2) can be used as initial charge and introduces in cold forcing machine with solid or liquid form, can pump into polymers soln, and by the two degasification together, or polymers soln can be used as initial charge and introduces, pump in the forcing machine of heating, and first evaporate the solvent (for example 50-95%) of specific part, then in later phases, add using nonionogenic tenside (a2) as solid or as suspension (slurry), and solvent is evaporated together.
After the mixture of multipolymer (a1) and alcoxylates (a2) is cooling, can make its cooling and optionally pulverize.What be suitable for pulverizing is all routine techniquess that become known for this object in principle, for example heat or cold beating.Make its cooling and pulverize can carry out with any desired sequence.Therefore, for example, the extrudate of multipolymer (a1) and alcoxylates (a2) can be patted with rotating blade or with airstream, then by it with air or cooling under shielding gas.In another change programme; can be laid on using the extrudate of multipolymer (a1) and alcoxylates (a2) as melt thigh cooling zone (stainless steel, teflon, chain band) upper, after solidifying, it is granulated or it is ground.
Other breaking method as spray solidification be also possible.
The compound of general formula (I) can pass through corresponding C 8-C 24alkanol obtains by oxyalkylene alkoxylate.Herein, can be etherificate after alkoxylate, for example, with suitable alcohol or use other alkylating agent, particularly use methyl-sulfate etherificate, or use carboxylic esterification.
Preferably R 2for hydrogen.
Alkoxylate can for example be used basic catalyst, for example alkali metal hydroxide or alkali metal alcoholates, or for example, with an acidic catalyst, BF 3h 3pO 4, BF 32 (C 2h 5) 2o, BF 3, SbCl 5, SnCl 42H 2o or hydrotalcite, or carry out with the agent of bimetal hydride catalytic.
The method of preparing multipolymer (a1) is that itself is known, for example, referring to WO2007/051743.Preparation can be preferably by free radical polymerization, preferably in solution, carry out in non-aqueous organic solvent or in the mixture of water and non-aqueous organic solvent.Suitable non-aqueous organic solvent is for example alcohol, for example methyl alcohol, ethanol, n-propyl alcohol and Virahol, and glycol, for example ethylene glycol and glycerine.Be suitable for ester, for example ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate or butylacetate, the wherein ethyl acetate in addition of making solvent.Free-radical polymerized for carrying out, preferably polyethers (a1.3) is introduced as initial charge, and together or dividually, simultaneously or add continuously N-vinylamide (a1.1), vinyl-acetic ester (a1.2) and optional other comonomer (a1.4).
Free-radical polymerizedly preferably at the temperature of 60-100 DEG C, carry out.Suitable pressure is for example barometric point, but also can select higher or lower pressure.
Below by work, embodiment sets forth the present invention in more detail.
Work embodiment
I. material used
I.1 the preparation of multipolymer (a1)
I.1.1 the preparation of multipolymer (a1-1)
Charging 1:240g vinyl-acetic ester (a1.2)
Charging 2: be dissolved in the 456g caprolactam (a1.1-1) in 240g ethyl acetate
Charging 3: cross the PIVALIC ACID CRUDE (25) tert-butyl ester (75 % by weight in aliphatic mixture) with the 10.44g of 67.90g ethyl acetate dilution
By the 104.0g polyoxyethylene glycol (M being dissolved in 25g ethyl acetate w: 6000g/mol) (a1.3-1) introduce in whipping device and at N as initial charge 2under atmosphere, be heated to 77 DEG C.In the time reaching the internal temperature of 77 DEG C, add 1g charging 3, and make polymerization of mixtures 15 minutes.Then start being metered into of charging 1, charging 2 and charging 3 simultaneously.Charging 1 and charging 2 were metered into through 5 hours, and charging 3 was metered into through 2 hours.After all chargings are metered into, reaction mixture is stirred at 77 DEG C other 3 hours.Then by 500ml water dilution for reaction mixture.Then remove volatile constituent by vapor distillation.By the aqueous solution freeze-drying of available like this multipolymer (a1-1).After grinding, obtain as the unusual multipolymer of free-flowing powder (a1-1).M w：44000g/mol
I.1.2 the preparation of multipolymer (a1-2)
Charging 1: be dissolved in 500g caprolactam (a1.1-1) and 180g vinyl-acetic ester (a1.2) in 100g ethyl acetate
Charging 2: cross the thylhexoic acid tert-butyl ester (98 % by weight) with the 10.50g of 94.50g ethyl acetate dilution
By the 100.0g polyoxyethylene glycol (M being dissolved in 165g ethyl acetate w: 6000g/mol) (a1.3-1) introduce in whipping device and at N as initial charge with 20g vinyl-acetic ester (a1.2) 2under atmosphere, be heated to 77 DEG C.In the time reaching the internal temperature of 77 DEG C, add 10.5g charging 2, and make mixture partially polymerized 15 minutes.Then start being metered into of charging 1 and charging 23 simultaneously.Charging 1 was metered into through 5 hours, and charging 2 was metered into through 2 hours.After all chargings are metered into, reaction mixture is stirred at 77 DEG C other 3 hours.Then by 500ml water dilution for reaction mixture.Then remove volatile constituent by vapor distillation.By the aqueous solution freeze-drying of available like this multipolymer (a1-1).After grinding, obtain as the unusual multipolymer of free-flowing powder (a1-2).
I.1.3 the preparation of other multipolymer (a1-3) to (a1-5)
Program as embodiment I.1.2 as described in, but in every kind of situation, select the difference composition of charging 1 and charging 2.
This obtains the following multipolymer according to table 1.
Table 1: the composition of multipolymer (a1-1) to (a1-5)
Alcoxylates used (a2-1) is n-C 18h 37-(OCH 2cH 2) 9-OH:
II. the preparation of preparaton of the present invention and control formulation
The preparation of II.1 basic mixture
Polycarboxylate used (c-1) is: the random copolymers of vinylformic acid/AMPS (2-acrylamido-2-methyl propane sulfonic acid), weight ratio 7:3, with the neutralization of NaOH part, M w: 20000g/mol, K value 40, pH5 (in distilled water 1%).
For preparing basic mixture, in every kind of situation, material as described in Table 2 dry blending in kitchen utensils is separated together and by sample spliter.
Table 2: the composition of basic mixture
HEDP: the disodium salt of hydroxyl ethane-(1,1-di 2 ethylhexyl phosphonic acid)
All amount data represent with g.
The preparation of II.2 the present invention preparation used and Comparative formulation
The preparation of preparation EZ-1 of the present invention
Mix by (a2-1) melting of 10g alcoxylates and with 5g solid copolymer (a1-1).First this produce the heterogeneous mixture of turbid solution form.Be cooled to room temperature and again after melting, obtaining the uniform mixture of clear solution form.Make this mixture be cooled to room temperature, obtain preparation EZ-1.EZ-1 is at room temperature solid.
The preparation of II.3 the present invention without phosphorus preparaton EF-1 used
19.95g basic mixture is introduced as initial charge without BP-P.Then EZ-1 melting is also added the 1.6gEZ-1 that comprises 1.05g (a2-1) and 0.55g (a1-1) without in BP-P.Available like this preparaton EF-1 is solidified.
The preparation of II.4 the present invention phosphorous preparaton used and control formulation
The preparation of II.4.1 the present invention preparaton EF-1P used
20.4g basic mixture is introduced as initial charge containing BP-P.Then 0.9gEZ-1 melting is also dropwise added containing in BP-P.Available like this preparaton EF-1P is solidified.
The preparation of II.4.2 control formulation V-F-2P
20.4g basic mixture is introduced as initial charge containing BP-P.Then 0.6g alcoxylates (a2-1) melting is also dropwise added containing in BP-P.Available like this control formulation V-F-2P is solidified.
III. test preparaton of the present invention and control formulation
For the test of machine dishwashing detergent, select following experiment condition:
Dishwasher: Miele G1222SCL
Program: 50 DEG C, R-time2 (8 minutes) (without pre-rinsing)
Goods: 3 cuttves (WMF Tafelmesser Berlin, Monoblock)
3 Amsterdam0.2 rise glass cylinder
3 " OCEAN BLUE " BREAKFAST PLATES (being formed by melamine resin)
3 porcelain dish RIMMED PLATES FLAT19CM
Arrange: cutter is in plate-rack, and glass is in the basket of top, and dish is in nethermost basket
Dish washing detergent: 21g
Dirt adds: 100g cleaning-rinsing dirt (comprising egg, starch and grease) is metered into frozen state
Cleaning-rinsing temperature: 65 DEG C
The water hardness: 21 ° of Deutschland hardnesss (Ca/Mg): HCO 3(3:1): 1.35
Wash(ing)cycle: 6; Every kind of situation disconnects (open dish washing machine door 10 minutes, close dish washing machine door 50 minutes) between lower 1 hour
Assessment: after 6 wash(ing)cycles in darkroom visual assessment under the light after orifice plate
After 6 wash(ing)cycles, use the level evaluation goods of 10 (very good) to 1 (non-constant).Give the grade (very many strong stain=1 are to inviolateness=10) of 1-10 for stain, and for film forming, give grade 1-10 (settling of 1=highly significant, 10=deposit-free).
The result of without phosphorus preparaton for IV.1
Test-results is summarized in table 3 (referring to nextpage).
The result of phosphorous preparaton for IV.2
Test-results is summarized in table 4 (referring to nextpage).

Claims (14)

1. the purposes of the preparation that comprises following component in machine dishwashing detergent preparaton:
(a1) at least one can be by the multipolymer that following monomer copolymerization is obtained:
(a1.1) at least one N-vinylamide,
(a1.2) vinyl-acetic ester,
(a1.3) at least one polyethers,
(a1.4) optional at least one other comonomer,
(a2) alcoxylates of at least one general formula (I):
R 1-(OCH 2CHR 2) mOR 3 (I)
Wherein variable-definition is as follows:
R 1for linearity or branching C 8-C 24alkyl,
R 2identical or different in every kind of situation, be linearity or branching C 1-C 10alkyl or hydrogen,
R 3for hydrogen or linearity or branching C 1-C 4alkyl,
M is the number of 1-100.
2. according to the purposes of claim 1, it comprises 1-50 % by weight multipolymer (a1) and 50-99 % by weight alcoxylates (a2).
3. according to the purposes of claim 1 or 2, wherein multipolymer (a1) can obtain by following monomer copolymerization:
Amount to 30-80 % by weight N-vinylamide (a1.1),
Amount to 10-50 % by weight vinyl-acetic ester (a1.2),
Amount to 10-50 % by weight polyethers (a1.3),
Amount to 0-10 % by weight comonomer (a1.4),
Quality based on whole multipolymer (a1) in every kind of situation.
4. according to the purposes of any one in claim 1-3, wherein multipolymer (a1) is graft copolymer.
5. according to the purposes of any one in claim 1-4, wherein N-vinylamide (a1.1) is selected from N-vinyl lactam.
6. according to the purposes of any one in claim 1-4, wherein N-vinylamide (a1.1) is selected from NVP and N-caprolactam.
7. according to the purposes of any one in claim 1-6, wherein polyethers (a1.3) is selected from the molecular-weight average M with 1000-100000g/mol wpolyoxyethylene glycol.
8. according to the purposes of any one in claim 1-7, wherein alcoxylates (a.2) is selected from and has every mole of linear C of average 8.5-9.5 mole ethylene oxide 16-C 18the linear C of alkanol 16-C 18the ethoxylate of alkanol.
9. according to the purposes of any one in claim 1-8, the linear C of at least one formula (I) that wherein alcoxylates (a2) comprises at least 80 % by weight 16-C 18the ethoxylate of alcohol, wherein m is selected from 8,9 and 10.
10. according to the purposes of any one in claim 1-9, wherein multipolymer (a1) and alcoxylates (a2) exist as sosoloid.
11. use the machine dishware washing method of at least one preparaton, and described preparaton comprises:
(a) at least one that amounts to 0.1-20 % by weight be according to the preparation of any one in claim 1-9,
(b) nonionogenic tenside that is different from multipolymer (a1) and alcoxylates (a2) of total 0-10 % by weight,
(c) one or more polycarboxylates of total 0-20 % by weight,
(d) the title complex forming agent that is different from inorganic phosphate of total 0-50 % by weight,
(e) one or more inorganic phosphates of total 0-70 % by weight,
(f) amount to other the without phosphorus buider and help buider particularly that is different from title complex forming agent (d) in every kind of situation of 0-60%,
(g) SYNTHETIC OPTICAL WHITNER of total 0-30 % by weight and optional bleach-activating agent or bleaching catalyst,
(h) enzyme of total 0-8 % by weight,
(k) one or more other additives of total 0-50 % by weight, and optional water.
12. according to the method for claim 11, and wherein additive is selected from negatively charged ion or zwitterionics, alkali carrier, corrosion inhibitor, defoamer, dyestuff, perfume compound, sanitas, filler, organic solvent, film-making auxiliary, disintegrating agent, thickening material and solubility promoter.
The purposes of 13. multipolymers (a1) that can obtain by following monomer copolymerization in machine dishwashing detergent preparaton:
(a1.1) at least one N-vinylamide,
(a1.2) vinyl-acetic ester,
(a1.3) at least one polyethers,
(a1.4) optional at least one other comonomer.
14. according to the method for claim 13, and wherein multipolymer (a1) can obtain by following monomer copolymerization:
Amount to 30-80 % by weight N-vinylamide (a1.1),
Amount to 10-50 % by weight vinyl-acetic ester (a1.2),
Amount to 10-50 % by weight polyethers (a1.3),
Amount to 0-10 % by weight comonomer (a1.4),
Quality based on whole multipolymer (a1) in every kind of situation.
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