CN110382678A - Dispersant system for automatic tableware detergent compositions - Google Patents
Dispersant system for automatic tableware detergent compositions Download PDFInfo
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- CN110382678A CN110382678A CN201880017116.2A CN201880017116A CN110382678A CN 110382678 A CN110382678 A CN 110382678A CN 201880017116 A CN201880017116 A CN 201880017116A CN 110382678 A CN110382678 A CN 110382678A
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- Prior art keywords
- cleaning compositions
- automatic tableware
- tableware cleaning
- weight
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Classifications
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
-
- 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
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
Abstract
A kind of the automatic tableware cleaning compositions are provided, it includes: polymer dispersant blend, it includes acrylate homopolymers；With the copolymer of acrylic acid and sulfonated monomer；Wherein the mixing ratio of the acrylate homopolymer of polymer dispersant blend and copolymer is 3: 1 to 1: 3；Surfactant；Builder；With optional additive.
Description
The present invention relates to the dispersant systems for automatic tableware detergent compositions.Specifically, the present invention relates to incorporate
The automatic tableware cleaning compositions of this kind of dispersant system reduce spot and/or film forming on tableware.
The automatic tableware cleaning compositions are known as and one kind different for those of fabric washing or water process detergent
Detergent composition.After complete cleaning circulation, user it is expected the automatic tableware cleaning compositions on washed article
The sum without spot is generated without film outward appearance.
Welch et al. discloses the hydroxy polyethers as low foaming surfactant in U.S. Patent No. 5,294,365
Family, the rinse aid being used as in phosphate-containing machine dishwashing detergent detergent formulation.Welch et al. discloses following formula
Close object
Wherein R1With R2It is identical or different, and be linear chain or branched chain C1-18Alkyl；N is 15 to 45 number；And m is 0
To 3 number.
Nevertheless, phosphate free composition increasingly caters to the need.Phosphate free composition dependence nonphosphate, which helps, to be washed
Agent is come such as citrate, carbonate, silicate, dislicata, bicarbonate, aminocarboxylate and other builders with chelating
From the calcium of hard water and magnesium and prevent to leave insoluble visible deposition object on its tableware after the drying.However, phosphate free combines
Object is easier to leave spot in glassware and other surfaces.
Presented in automatic tableware washing the composition of improved characteristic and phosphate free by be industry a much progress.
Therefore, there is still a need for the novel surfactant with antiplaque dot characteristics.Specifically, it is still desirable to antiplaque dot characteristics
Novel surfactant facilitates the automatic tableware of phosphate free and antiplaque point to wash formulation.
The present invention provides the automatic tableware cleaning compositions, it includes: the polymer dispersant blending of 0.5 to 15 weight %
Object comprising: acrylate homopolymer；With the copolymer of acrylic acid and sulfonated monomer；Wherein the third of polymer dispersant blend
It is 3: 1 to 1: 3 that the mixing ratio of olefin(e) acid homopolymer and copolymer, which is based on weight,；The surfactant of 0.5 to 15 weight %；1 to 75
The builder of weight %；The additive of 0 to 75 weight %.
The present invention provides the automatic tableware cleaning compositions, it includes: the polymer dispersant blending of 0.5 to 15 weight %
Object comprising: acrylate homopolymer；With the copolymer of acrylic acid and sulfonated monomer；Wherein the third of polymer dispersant blend
It is 3: 1 to 1: 3 that the mixing ratio of olefin(e) acid homopolymer and copolymer, which is based on weight,；The surfactant of 0.5 to 15 weight %；1 to 75
The builder of weight %；The additive of 0 to 75 weight %；Wherein the automatic tableware cleaning compositions contain less than 0.1wt%
Phosphate；Wherein the automatic tableware cleaning compositions contain the aminocarboxylate chelators less than 0.1wt%；Wherein institute
State the ether capped ethoxylated alcohol of glycidyl that surfactant is Formulas I:
Wherein R1It is linear saturation C8-24Alkyl, R2It is linear chain or branched chain saturation C6-20Alkyl, the average value of m are 10 to 50,
And the average value > 1 to 2 of n.
The present invention also provides a kind of methods of clean article in automatic tableware rinsing maching, and the method includes: incite somebody to action this
The automatic tableware cleaning compositions of invention are applied to the article.
Specific embodiment
When being incorporated in the automatic tableware cleaning compositions (especially not phosphatic the automatic tableware cleaning compositions), this
The blend for dispersing the copolymer that agent formulation includes acrylate homopolymer and acrylic acid and sulfonated monomer of invention is (preferably,
Described in the automatic tableware cleaning compositions further comprise the base of the invention based on certain glycidol ethers and ethoxylated alcohol
The surfactant of group's reaction), which significantly improves the antiplaque point of the automatic tableware cleaning compositions
And/or fouling (film forming) performance.
Unless otherwise instructed, otherwise ratio, percentage, number and its analog are by weight.Weight in the composition
Amount percentage (or weight %) is the percentage of dry weight, that is, excludes any water that may be present in composition.Monomer in polymer
The percentage of unit is the percentage of solid weight, i.e., does not include any water present in polymer emulsion.
As used herein, unless otherwise instructed, otherwise term " molecular weight " and " Mw " are used interchangeably to refer to as used
The Weight-average molecular that gel permeation chromatography (GPC) and conventional criteria object (such as polyethylene glycol reference substance) measure in a usual manner
Amount.GPC technology is " modern size exclusion chromatography (Modem Size Exclusion Chromatography) ", W.W.Yau,
J.J.Kirkland, D.D.Bly；Willie-International Science Press (Wiley-Interscience), in 1979 and in " material
Material characterization and chemical analysis guide (A Guide to Materials Characterization and Chemical
Analysis) ", J.P.Sibilia；Publishing house, German chemical association (VCH), 1988, it is discussed in detail in the 81-84 pages.Herein
Middle reported molecular weight is with dalton (Dalton) for unit.
Term " alkene system is unsaturated " is for describing molecule or the portion of one or more carbon-to-carbon double bonds with keeping its polymerizable
Point.Term " alkene system unsaturated " includes that monoene belongs to unsaturated (having a carbon-to-carbon double bond) and polyenoid belongs to unsaturation (there are two tools
Or more carbon-to-carbon double bond).As used herein, term " (methyl) acrylic acid " refers to acrylic or methacrylic acid.
As used herein and in the appended claims, term " ethyleneoxy " and " EO " refer to-CH2-CH2-O-。
As used herein and in the appended claims, term " phosphate free " mean containing≤1wt% (preferably≤
0.5wt%；More preferably less than≤0.2wt%；Still more preferably less than≤0.1wt%；Even more preferably less than≤0.01wt%；It is optimal
Choosing is less than detectable limit) phosphate (with element phosphorus measurement) composition.
Refer to the remainder of shown monomer with term " structural unit " used in appended claims herein；
Therefore, the structural unit of acrylic acid is illustrated:
Its dotted line indicates the tie point with main polymer chain.
Preferably, the automatic tableware cleaning compositions of the invention include: 0.5 to 15 weight % (preferably 0.5 to 10 weight
Measure %；More preferable 1 to 8 weight %；Most preferably 2.5 to 7.5 weight %) polymer dispersant blend, it includes acrylic acid
Homopolymer；With the copolymer of acrylic acid and sulfonated monomer；The wherein acrylate homopolymer of polymer dispersant blend and copolymerization
It is 3: 1 to 1: 3 (preferably 2.5: 1 to 1: 2.5 that the mixing ratio of object, which is based on weight,；More preferable 2: 1 to 1: 2；Most preferably, 1.5: 1 to 1:
1.5)；0.5 to 15 weight % (preferably 0.5 to 10 weight %；More preferable 1 to 8 weight %；Most preferably 2.5 to 7.5 weight %)
Surfactant (preferably, wherein glass or plastic containers)；The builder of 1 to 75 weight %；With 0 to
The additive of 75wt%.
Preferably, the automatic tableware cleaning compositions of the invention include: 0.5 to 15 weight % (preferably 0.5 to 10 weight
Measure %；More preferable 1 to 8 weight %；Most preferably 2.5 to 7.5 weight %) polymer dispersant blend, it includes acrylic acid
Homopolymer；With the copolymer of acrylic acid and sulfonated monomer；The wherein acrylate homopolymer of polymer dispersant blend and copolymerization
It is 3: 1 to 1: 3 (preferably 2.5: 1 to 1: 2.5 that the mixing ratio of object, which is based on weight,；More preferable 2: 1 to 1: 2；Most preferably, 1.5: 1 to 1:
1.5)；0.5 to 15 weight % (preferably 0.5 to 10 weight %；More preferable 1 to 8 weight %；Most preferably 2.5 to 7.5 weight %)
Surfactant (preferably, wherein glass or plastic containers)；The builder of 1 to 75 weight %；With 0 to
The additive of 75wt%；Wherein the builder is selected from carbonate, citrate, silicate and its mixture.
Preferably, the automatic tableware cleaning compositions of the invention include: 0.5 to 15 weight % (preferably 0.5 to 10 weight
Measure %；More preferable 1 to 8 weight %；Most preferably 2.5 to 7.5 weight %) polymer dispersant blend, it includes acrylic acid
Homopolymer；With the copolymer of acrylic acid and sulfonated monomer；The wherein acrylate homopolymer of polymer dispersant blend and copolymerization
It is 3: 1 to 1: 3 (preferably 2.5: 1 to 1: 2.5 that the mixing ratio of object, which is based on weight,；More preferable 2: 1 to 1: 2；Most preferably, 1.5: 1 to 1:
1.5)；0.5 to 15 weight % (preferably 0.5 to 10 weight %；More preferable 1 to 8 weight %；Most preferably 2.5 to 7.5 weight %)
Surfactant (preferably, wherein glass or plastic containers)；The builder of 1 to 75 weight %；With 0 to
The additive of 75wt%；Wherein surfactant is the ether capped ethoxylated alcohol of glycidol of Formulas I:
Wherein R1It is linear saturation C8-24Alkyl (preferably linear saturation C10-14Alkyl；More preferable linear saturation C10-12Alkyl；
More preferable linear saturation C10Alkyl or linear saturation C12Alkyl)；R2It is linear saturation or branch saturation C6-20Alkyl (preferably branch
It is saturated C6-10Alkyl；More preferable 2- ethylhexyl)；The average value of m is 10 to 50 (preferably 10 to 30；More preferable 15 to 30；Also more
It is preferred that 18 to 22；Again even more preferably from 19 to 21；Most preferably 20)；And the average value > 1 to 2 (preferably 1.1 to 2 of n；More preferably
1.2 to 1.6)；And wherein the automatic tableware cleaning compositions include to be less than 0.1wt% (preferably < 0.05wt%；It is more excellent
Selection of land < 0.01wt%；Still more preferably < detection limit；Do not have most preferably) aminocarboxylate chelators (such as MGDA).Formulas I
The ether capped ethoxylated alcohol surfactant of glycidol may include in R1And R2A series of upper compound containing alkyl
Mixture, the alkyl carbon number is different, but has the average carbon number for meeting range described above.
It is preferably based on the dry weight of the automatic tableware cleaning compositions, the automatic tableware cleaning compositions packet of the invention
Include the polymer dispersant blend of 0.5 to 15 weight %.It is highly preferred that dry based on the automatic tableware cleaning compositions
Weight, the automatic tableware cleaning compositions of the invention include the polymer dispersant blend of 0.5 to 10 weight %.Still more preferably
Ground, based on the dry weight of the automatic tableware cleaning compositions, the automatic tableware cleaning compositions of the invention include 1 to 8 weight %
Polymer dispersant blend.Most preferably, the dry weight based on the automatic tableware cleaning compositions, buffet meal of the invention
Tool cleaning compositions include the polymer dispersant blend of 2.5 to 7.5 weight %.
Preferably, in terms of the dry weight of the automatic tableware cleaning compositions, the automatic tableware cleaning compositions of the invention include >=
1wt% (more preferably >=2wt%；More preferably >=3wt%；More preferably >=5wt%) polymer dispersant blend.Preferably,
In terms of the dry weight of the automatic tableware cleaning compositions, the automatic tableware cleaning compositions of the invention include :≤10wt% (more preferably≤
8wt%；More preferably≤6wt%；More preferably≤4wt%) polymer dispersant blend.
It preferably, include polymer dispersant blend in the automatic tableware cleaning compositions of the invention include propylene
The blend of the copolymer of sour homopolymer and acrylic acid and sulfonated monomer, wherein the acrylic acid homopolymerization of polymer dispersant blend
It is 3: 1 to 1: 3 (preferably 2.5: 1 to 1: 2.5 that the mixing ratio of object and copolymer, which is based on weight,；More preferable 2: 1 to 1: 2；Most preferably
1.5: 1 to 1: 1.5).
Preferably, for the weight average molecular weight M of the acrylate homopolymer in the automatic tableware cleaning compositions of the inventionWFor
1,000 to 40,000 (preferably 1,000 to 20,000；More preferable 1,000 to 10,000；Even more preferably from 1,000 to 5,000；It is optimal
Select 2,000 to 4,000) dalton.
Preferably, for acrylic acid and sulfonated monomer in the automatic tableware cleaning compositions of the invention copolymer weight
Average molecular weight MWIt is 2,000 to 100,000 (preferably 5,000 to 60,000；More preferable 8,000 to 25,000；More preferable 10,000
To 20,000；Most preferably 12,500 to 17,500) dalton.
Preferably, the copolymer for acrylic acid and sulfonated monomer in the automatic tableware cleaning compositions of the invention includes
The structural unit of at least one sulfonated monomer.It is highly preferred that the propylene used in the automatic tableware cleaning compositions of the invention
The copolymer of acid and sulfonated monomer includes the structural unit of at least one sulfonated monomer selected from the following: 2- acrylamido -2-
Methyl propane sulfonic acid (AMPS), 2- methacryl amido -2- methyl propane sulfonic acid, 4- styrene sulfonic acid, vinyl sulfonic acid, 3- alkene
Propoxyl group sulfonic acid, 2- hydroxyl -1- propane sulfonic acid (HAPS), 2- sulfoethvl (methyl) acrylic acid, 2- sulfapropyl (methyl) third
Olefin(e) acid, 3- sulfapropyl (methyl) acrylic acid, 4- sulfobutyl group (methyl) acrylic acid and its salt.
Preferably, the copolymer packet for acrylic acid and sulfonated monomer in the automatic tableware cleaning compositions of the invention
Contain: 5-65wt% (more preferable 15-40wt%；Most preferably 20-35wt%) acryllic acid structural unit.
Preferably, the copolymer packet for acrylic acid and sulfonated monomer in the automatic tableware cleaning compositions of the invention
Contain: 50 to 95wt% (preferably 70 to 93wt%) acrylic acid structure unit and 5 to 50wt% (preferably 7 to 30wt%) 2- third
The structural unit of acrylamide base -2- methyl propane sulfonic acid sodium salt.It is highly preferred that being used for the automatic tableware cleaning compositions of the invention
In acrylic acid and the copolymer of sulfonated monomer include: 50 to 95wt% (preferably 70 to 93wt%) acrylic acid structure unit and
5 to the 50wt% (structural units of preferably 7 to 30wt%) 2- acrylamido -2- methyl propane sulfonic acid sodium salt；It is wherein described
The weight average molecular weight Mw of copolymer is 2,000 to 100,000 (more preferably 10,000 to 20,000；Most preferably 12,500 to
17,500) dalton.
The polymer for including in polymer dispersant blend used in the automatic tableware cleaning compositions of the invention can
With commercially available from various sources and/or its can be used technical literature preparation.For example, being included in polymer dispersant blend
Low-molecular weight polymer can be prepared by free radical polymerization.The preferred method for being used to prepare these polymer is by molten
The homogeneous polymerization carried out in agent.Solvent can be water or alcoholic solvent, such as 2- propyl alcohol or 1,2-PD.Free radical polymerization is by forerunner
Compound, such as alkali metal persulphate or organic peracid and perester decompose and cause.The activation of predecessor can pass through list
Only raised effect (thermal activation) or admixture by redox active agent of reaction temperature, such as ferric sulfate (II) and anti-bad
The combination (redox activation) of hematic acid is realized.In these cases, typically using chain-transferring agent to adjust polymer molecule
Amount.The preferred chain-transferring agent of one kind used in polymerisation in solution is alkali metal bisulfite or ammonium bisulfite.It is specifically mentioned
Be sodium metabisulfite.
The polymer for including in polymer dispersant blend used in the automatic tableware cleaning compositions of the invention can
In the form of water-soluble solution polymer, slurries, dried powder or particle or other solid forms.
Preferably, the automatic tableware cleaning compositions of the invention include 0.5 to 15 weight % (preferably 0.5 to 10 weight %；
More preferable 1 to 8 weight %；Most preferably 2.5 to 7.5 weight %) surfactant.Preferably, in automatic tableware of the invention
Surfactant used in cleaning compositions is nonionic surface active agent.It is highly preferred that automatic tableware of the invention is washed
Washing surfactant used in composition is nonionic surfactant selected from the following: epoxy ethane-epoxy propane-epoxy
Butane two or triblock copolymer, alkoxy fatty alcohols, amine oxide, alkyl ether sulfate or alkyl polyglycoside.Preferably, exist
Surfactant used in the automatic tableware cleaning compositions of the invention is the non-ionic table with the cloud point lower than 45 DEG C
Face activating agent.Preferably, the surfactant used in the automatic tableware cleaning compositions of the invention is based on polyoxyalkylene
The nonionic surface active agent of polyether derivative.
Preferably, the surfactant used in the automatic tableware cleaning compositions of the invention is the glycidol of Formulas I
Ether capped ethoxylated alcohol:
Wherein R1It is linear saturation C8-24Alkyl (preferably linear saturation C10-14Alkyl；More preferable linear saturation C10-12Alkyl；
More preferable linear saturation C10Alkyl or linear saturation C12Alkyl)；R2It is linear saturation or branch saturation C6-20Alkyl (preferably branch
It is saturated C6-10Alkyl；More preferable 2- ethylhexyl)；The average value of m is 10 to 50 (preferably 10 to 30；More preferable 15 to 30；Also more
It is preferred that 18 to 22；Again even more preferably from 19 to 21；Most preferably 20)；And the average value > 1 to 2 (preferably 1.1 to 2 of n；More preferably
1.2 to 1.6).The ether capped ethoxylated alcohol surfactant of the glycidol of Formulas I may include in R1And R2Above containing a series of
The mixture of the compound of alkyl, the alkyl carbon number is different, but has the average carbon number for meeting range described above.
Known synthetic method can be used easily in the ether capped ethoxylated alcohol surfactant of the glycidol of Formulas I
Preparation.For example, the exemplary program for being used to prepare compound is as follows.By meeting formula R1OH (wherein R1It is linear saturation C8-24Alkane
Base) alcohol be added in reactor, and heated in the presence of alkali (such as sodium methoxide or potassium hydroxide).Mixture should be opposite
It is not aqueous.The desired amount of ethylene oxide (EO) is then added into this mixture under stress.(such as by anti-after EO consumption
Device pressure is answered to decline to a great extent instruction), can be with separating obtained ethoxylated alcohol, and make it under alkaline condition 1: 1.1 to 1
: the alcohol in 2 ranges: the molar ratio of glycidol ether and alkyl glycidyl ether (wherein alkyl contains 6 to 20 carbon atoms) into
Row reaction.Alternatively, ethoxylated alcohol can be retained in original reaction apparatus and by add alkyl glycidyl ether carry out into
Single step reaction.The molar ratio of catalyst and alcohol can between 0.01: 1 and 1: 1, but preferably 0.02: 1 to 0.5: 1.Alternatively,
Lewis acid catalyst (such as boron triflouride etherate) can be with 0.01: 1 to 0.25: the 1 molar ratio use with alcohol.Generally
In the presence of solvent-free and between 25 DEG C to 200 DEG C, and preferably at a temperature of between 80 DEG C to 160 DEG C carry out with EO and
The reaction of alkyl glycidyl ether.
Preferably, builder used in the automatic tableware cleaning compositions of the invention include one or more carbonate,
Citrate and silicate.
Preferably, the automatic tableware cleaning compositions of the invention include: the builder of 1-75wt%.Preferably, with drying
The poidometer of the automatic tableware cleaning compositions, the automatic tableware cleaning compositions of the invention include: >=1wt% (more preferably >=
10wt%；More preferably >=20wt%；More preferably >=25wt%) builder.Preferably, to dry the automatic tableware cleaning compositions
Poidometer, the automatic tableware cleaning compositions of the invention include :≤75wt% (preferably≤60wt%；More preferably≤50wt%；
Most preferably≤40wt%) builder.Actual weight of the weight percent of carbonate, citrate and silicate based on salt,
Including metal ion.
As used herein and in the appended claims, term " carbonate " refers to the carbonate of alkali metal or ammonium, carbonic acid
Hydrogen salt, percarbonate and/or sesquicarbonate.Preferably, in the automatic tableware cleaning compositions carbonate (if there is
Words) carbonate (it is highly preferred that the salt of sodium or potassium, most preferably sodium salt) selected from sodium, potassium and lithium.It is highly preferred that of the invention
Carbonate used in the automatic tableware cleaning compositions is selected from sodium carbonate, sodium bicarbonate, SODIUM PERCARBONATE and its mixture.
Preferably, builder used in the automatic tableware cleaning compositions of the invention includes carbonate.It is highly preferred that with
Builder in the automatic tableware cleaning compositions of the invention includes the mixture of carbonate.Preferably, when it is of the invention from
When builder used in dynamic dish washing compositions includes carbonate, the automatic tableware cleaning compositions preferably include 10 to 75
Weight % (preferably 15 to 70 weight %；More preferable 25 to 60 weight %；Most preferably 30 to 50 weight %) carbonate.
As used herein and in the appended claims, term " citrate " refers to alkali-metal citrate.Preferably,
The citrate that the citrate used in the automatic tableware cleaning compositions (if any) is selected from sodium, potassium and lithium is (more excellent
Select the salt of sodium or potassium；Most preferably, the salt of sodium).It is highly preferred that for the automatic tableware cleaning compositions citrate (if
If) it is sodium citrate.
Preferably, builder used in the automatic tableware cleaning compositions of the invention includes citrate.It is highly preferred that
It include the mixture of carbonate for the builder in the automatic tableware cleaning compositions of the invention.Preferably, when for this hair
When builder in bright the automatic tableware cleaning compositions includes carbonate, the automatic tableware cleaning compositions preferably comprise >=0-40
Weight % (preferably 21-40 weight %；More preferable 25-35 weight %；Most preferably 27.5 to 32.5 weight %) citrate.
As used herein and in the appended claims, term " silicate " refers to alkali silicate.Preferably, certainly
Silicate (if any) used in dynamic dish washing compositions is selected from silicate (more preferable sodium or the potassium of sodium, potassium and lithium
Salt；Most preferably, the salt of sodium).It is highly preferred that silicate used in the automatic tableware cleaning compositions (if any) is
Sodium disilicate.Preferably, builder used in the automatic tableware cleaning compositions of the invention includes silicate.Preferably, when
When including silicate for the builder in the automatic tableware cleaning compositions of the invention, the automatic tableware cleaning compositions are preferably wrapped
Containing≤0 to 10wt% (preferably 0.1 to 5wt%；More preferable 0.5 to 3wt%；Most preferably 1.5 to 2.5 weight %) silicate.
The automatic tableware cleaning compositions of the invention optionally further include: additive.Preferably, of the invention automatic
Dish washing compositions optionally further include: additive, selected from the group being made up of: alkaline source, bleaching agent
(such as SODIUM PERCARBONATE, sodium perborate) and optionally bleach-activating (such as tetra acetyl ethylene diamine (TAED)) and/or bleaching
Catalyst (such as bis- (TACN) three magnesia of manganese acetate (II), cobalt chloride (II), oxalic acid)；Enzyme is (for example, protease, starch
Enzyme, lipase or cellulase)；Aminocarboxylate chelators (such as methylglycine diacetic acid (MGDA), glutamic acid-N, N-
Oxalic acid (GLDA), iminodisuccinic acid (IDSA), 1,2- ethylenediamine disuccinic acid (EDDS), aspartic acid oxalic acid
Or mixtures thereof (ASDA) or salt)；Phosphonate such as 1-Hydroxy ethylene-1,1-diphosphonic acid (HEDP)；Defoaming agent；Colorant；Fragrance
Agent；Silicate；Poly(ethylene glycol)；Additional builder；Antibacterial agent and/or filler.Filler in tablet or powder is lazy
Property, water-soluble substances, typically sodium salt or sylvite, such as sodium sulphate or potassium sulfate and/or sodium chloride or potassium chloride, and deposit
Amount typically in 0wt% to 75wt% range.Filler in gel preparation may include those described above and water and other
Solvent (such as glycerol).Aromatic, dyestuff, defoaming agent, enzyme and antibacterial agent are usually no more than the 10wt% of composition, substitution in total
Ground is no more than the 5wt% of composition.
The automatic tableware cleaning compositions of the invention optionally further include: alkaline source.Suitable alkaline source include but
It is not limited to alkali carbonate and alkali metal hydroxide, such as sodium carbonate or potassium carbonate, sodium bicarbonate or saleratus, sesquialter carbon
Sour sodium or sesquialter potassium carbonate, sodium hydroxide, lithium hydroxide or potassium hydroxide or above mixture.Sodium carbonate is preferred.When
In the presence of, in terms of the dry weight of the automatic tableware cleaning compositions, the amount of the alkaline source in the automatic tableware cleaning compositions of the invention
It can be for example, at least 1 weight % (preferably at least 20 weight %) and at most 80 weight % (preferably up to 60 weight %).
The automatic tableware cleaning compositions of the invention optionally further include: bleaching agent.Preferred bleaching agent was carbon
Sour sodium.When it is present, in terms of the dry weight of the automatic tableware cleaning compositions, bleaching agent in the automatic tableware cleaning compositions of the invention
Amount be preferably the concentration of 1wt% to 25wt% (more preferable 1wt% to 10wt%).
Preferably, the automatic tableware cleaning compositions of the invention have the pH of at least 9 (preferably >=10) (in water
1wt%).Preferably, the automatic tableware cleaning compositions of the invention have the pH (1wt% in water) no more than 13.
Preferably, the automatic tableware cleaning compositions of the invention can be with any canonical form, for example, being in tablet, powder, block
Shape object, single dose, pouch, lotion, liquid or gel form are prepared.The automatic tableware cleaning compositions of the invention are suitable for automatic
Cleaning appliance in table-ware washing machine, such as tableware and cooker, dish.
Preferably, the automatic tableware cleaning compositions of the invention can use under typical operating conditions.For example,
When, in use, the typical water temperature in washing process is preferably 20 DEG C to 85 DEG C, preferably 30 DEG C are arrived in automatic tableware rinsing maching
70℃.0.1 is preferably by the typical concentration of the automatic tableware cleaning compositions of percentages of total liquid in table-ware washing machine
Weight % to 1 weight %, preferably 0.2 weight % are to 0.7 weight %.By selecting product form appropriate and addition time,
The automatic tableware cleaning compositions of the invention can reside in prewashing, master washes, rinse for second from the bottom time, finally rinse or these are followed
In any combination of ring.
Preferably, the automatic tableware cleaning compositions of the invention include≤1 weight % (preferably≤0.5 weight %；More preferably
≤ 0.2 weight %；Even more preferably from≤0.1 weight %；Even more preferably from≤0.01 weight %；The detectable limit of most preferably <) phosphoric acid
Salt (with element phosphorus measurement).Preferably, the automatic tableware cleaning compositions of the invention not phosphate-containing.
Preferably, the automatic tableware cleaning compositions of the invention include 0.1 weight % of < (preferably 0.05 weight % of <；More
It is preferred that 0.01 weight % of <；The detectable limit of most preferably <) aminocarboxylate chelators (such as MGDA).Preferably, of the invention
The automatic tableware cleaning compositions be free of aminocarboxylate chelators (such as MGDA).
It now will some embodiments of detailed description of the present invention in the examples below.
The preparation of surfactant
Material: 1,2- octylene oxide, 2- hexyl glycidyl ether, 1- decyl alcohol, DODECANOL, 1-, 2- butyl -1- are pungent
Alcohol, sodium methoxide solution are obtained from Sigma-Aldrich (Sigma-Aldrich) and are used without further purification.First
Reacted with 5 equivalent propylene oxide, then with the 2-Ethylhexyl Alcohol of 15 equivalent reacting ethylene oxides in the form of 90% aqueous solution from pottery
Family name chemical company (Dow Chemical) obtains and hereinafter is referred to as " 2EH-PO5-EO15 ".
Analysis method
NMR: it is quantified on Brooker (Bruker) 500MHz instrument13C spectrum, 6144 scanning of general operation are real
Test zgig30, pulse length 13.25 μ s, circulation delay 5.000s, spectral line broadening 2Hz.
Polymer molecular weight.Weight average molecular weight can be used known method and be measured by gel permeation chromatography (GPC).
Concatenated two Polymer are injected by the way that 0.010g sample to be dissolved in 10mL THF, and by this solution of 50 μ L equal parts
5 μm of MIXED-E columns (300 × 7.5mm) of Labs PLgel and using differential refractive index detection (35 DEG C) at 35 DEG C with
It is enterprising that the flow rate of 1.0mL/min with THF (pure or contain 5% water) is eluted in 1100 series GPC of Agilent (Agilent)
Row gpc analysis.Normal calibration curve is generated using narrow polyethylene glycol reference substance.
Alkoxylation is in 2L 316 stainless steel conical lower portion (minimum stirred volume 20mL) Paar reactor (Parr
Reactor it) is carried out in model 4530, equipped with 1/4hp magnetic drive blender, 1500 watts of (115V) Calrod electric heating
Device, 1/4 inch of the filling cooling coil of water, 1/16 inch diptube pipe for sampling, internal thermowell, setting exist
1/4 inch of rupture pressure disc of 1024psig, 1/4 inch of overflow valve that 900psig is arranged in are immersed in subsurface oxide addition
The blade mixer of line and 2 inch diameters.The stainless steel of the customization for the profile for being configured to reactor is arranged at the bottom of blender axis
Blade is to allow to stir under low-down initial volume.Oxide add-on system is made of 1 liter of stainless steel addition cylinder, through filling
Expect, weigh and is attached on oxide Load Line.Reactor assembly is by Siemens (Siemens) SIMATIC PCS7 process
Control system control.With K-type thermocouple measurement reaction temperature, pressure is measured with Ya Sike (Ashcroft) pressure sensor, is used
The big Lip river gram of generation (Swagelok) operated pneumatic valve actuator operates ball valve, with ASCO electric valve control cooling water flow, and uses matter
Flow control system control oxide adding rate is measured, the mass flow control system is by Brooks
Coriolis mass flow controller (model QMBC3L1B2A1A1A1DH1C7A1DA) and TESCOM back pressure regulator (model
44-1163-24-109A) form, the back pressure regulator kept on the mass flow controller pressure difference of 100psig with
Stable flow rate is provided.
Ratio of reactants is sometimes referred to simply as " X eq. ": reagent added by wherein is considered relative to primitive reaction object tool
There is the molar ratio of X:1.
Embodiment 1: the synthesis of decyl alcohol ethoxylate
121.3g 1- decyl alcohol and powdered 85% potassium hydroxide of 0.50g are packed into 2L Paar reactor, and in pressure
It checks with after a series of nitrogen purging, mixture is warming up to 130 DEG C to add with 1 to 2g/min adding rate
670.2g ethylene oxide (about 20eq.).After addition completion and pressure are stablized, by reaction product cooling and unloads, obtain
785.6g.GPC result: MW=1220, MN=1140.In DMSO-d6In13C NMR (δ, ppm): 72.4,70.3,69.7,
69.8、69.6、60.2、31.4、29.3、29.1、29.1、29.0、28.8、25.7、22.1、13.8。
Embodiment 2: the synthesis of docyl alcohol ethoxylates
100.2g 1- decyl alcohol and powdered 85% potassium hydroxide of 0.56g are packed into 2L Paar reactor, and in pressure
It checks with after a series of nitrogen purging, mixture is warming up to 130 DEG C to add 473.0g with the adding rate of 2g/min
Ethylene oxide (about 20eq.).After addition completion and pressure are stablized, by reaction product cooling and unloads, obtain 564.77g.
GPC result: MW=1110, MN=1045.In DMSO-d6In13C NMR (δ, ppm): 72.4,70.4,59.9,69.6,60.1,
31.4、29.3、29.1、29.1、29.0、28.8、25.7、22.1、13.8。
Embodiment 3: decyl alcohol ethoxylate/2- hexyl glycidyl ether
Into the glass round bottom flask equipped with overhead type stirrer, thermocouple, nitrogen purging and heating mantle, addition 50g comes
From the decyl alcohol ethoxylate of embodiment 1.Heating is melted until decyl alcohol ethoxylate, is then begun to stir and is slowly added
2.6g sodium methoxide solution (25% methanol solution, the 25mol% in terms of ethoxylate).Reactor is heated to 140 DEG C, is reached
After this temperature, starts to add 13.5g 2- hexyl glycidyl ether (about 1.7eq.) and continue 1 hour.After addition,
Reactant is stirred for 6 hours at 140 DEG C, is then allowed to cool overnight.Second day, reaction mixture is heated to 50 DEG C,
It is quenched, and is then poured into bottle with 0.43g acetic acid.In DMSO-d6In13C NMR (δ, ppm): 73.3,72.8,72.4,
70.3、70.2、69.9、69.6、68.5、60.2、31.4、30.1、29.3、29.1、29.0、28.6、25.7、23.4、22.6、
22.2、13.8、10.7。
Embodiment 4: docyl alcohol ethoxylates/2- hexyl glycidyl ether
51.5g is added into the glass round bottom flask equipped with overhead type stirrer, thermocouple, nitrogen purging and heating mantle
Docyl alcohol ethoxylates from example 2.Heating until decyl alcohol ethoxylate melt, then begin to stirring and slowly
It adds 2.6g sodium methoxide solution (25% methanol solution, the 25mol% in terms of ethoxylate).Reactor is heated to 140 DEG C,
After reaching this temperature, starts to add 13.5g 2- hexyl glycidyl ether (about 1.3eq.) and continue 1 hour.Addition
Afterwards, reactant is stirred for 6 hours at 140 DEG C, is then allowed to cool overnight.Second day, reaction mixture is heated to 50
DEG C, it is quenched with 0.43g acetic acid, and be then poured into bottle.In DMSO-d6In1372.9 C NMR (δ, ppm): 73.3,
72.5、70.4、70.1、69.9、69.6、68.4、60.1、31.4、30.1、29.2、28.8、28.6、25.7、23.4、22.6、
22.1、13.8、10.7。
The synthesis of 5: 2- butyl octyl alcohol ethoxylate of embodiment
85.90g 2- butyl -1- octanol and powdered 85% potassium hydroxide of 0.48g are packed into 2L Paar reactor, and
And after pressure inspection and a series of nitrogen purging, mixture is warming up to 130 DEG C so as to the addition of the adding rate of 2g/min
406.4g ethylene oxide (about 20eq.).After addition completion and pressure are stablized, by reaction product cooling and unloads, obtain
493.2g.GPC result: MW=1390, MN=1190.In DMSO-d6In13C NMR (δ, ppm): 73.4,72.4,70.2,
69.9、60.2、58.0、31.3、30.9、39.6、29.2、28.5、26.2、22.6、22.1、13.8。
Comparative example C1: decyl alcohol ethoxylate/1,2- octylene oxide
Into the glass round bottom flask equipped with overhead type stirrer, thermocouple, nitrogen purging and heating mantle, addition 50g comes
From the decyl alcohol ethoxylate of example 1.Heating is melted until decyl alcohol ethoxylate, is then begun to stir and is slowly added
2.6g sodium methoxide solution (25% methanol solution, the 25mol% in terms of ethoxylate).Reactor is heated to 90 DEG C, is reached
After this temperature, starts to add 9.3g 1,2- octylene oxide (about 1.7eq.) and continue 1 hour.After addition, reactant is existed
It is stirred at 140 DEG C 6 hours, is then allowed to cool overnight.Second day, reaction mixture is heated to 90 DEG C and reheats 6
Hour, 50 DEG C are then allowed to cool to, is quenched with 0.43g acetic acid, and be then poured into bottle.In DMSO-d6In13C
NMR (δ, ppm): 75.6,72.4,70.4,70.0,69.9,69.6,68.8,68.6,60.2,33.7,31.4,29.3,29.1,
29.1、29.0、28.9、25.7、25.0、22.1、13.8、13.8。
Comparative example C2:2- butyl octyl alcohol ethoxylate/2- ethylhexyl glycidol ether
51.5g is added into the glass round bottom flask equipped with overhead type stirrer, thermocouple, nitrogen purging and heating mantle
2- butyl octyl alcohol ethoxylate from example 5.Heating is melted until decyl alcohol ethoxylate, is then begun to stir and be delayed
Slow addition 2.6g sodium methoxide solution (25% methanol solution, the 25mol% in terms of ethoxylate).Reactor is heated to 140
DEG C, after reaching this temperature, starts to add 13.5g 2- hexyl glycidyl ether (about 1.3eq.) and continue 1 hour.
After addition, reactant is stirred for 6 hours at 140 DEG C, is then allowed to cool overnight.Second day, reaction mixture is heated
To 50 DEG C, it is quenched with 0.43g acetic acid, and be then poured into bottle.In DMSO-d6In13C NMR (δ, ppm): 73.5,
73.3、72.7、72.4、70.5、70.1、69.9、68.5、60.2、58.3、37.6、31.3、30.9、30.6、30.1、29.2、
28.5、26.2、23.4、22.6、22.1、13.8、10.8。
Comparative example C3:2- ethyl hexanol alcoxylates/2- hexyl glycidyl ether
57.8g is added into the glass round bottom flask equipped with overhead type stirrer, thermocouple, nitrogen purging and heating mantle
2EH-PO5-EO15 (90%).Continue 3 hours stirring and kettle being heated to 140 DEG C under active nitrogen bubbling to remove water.It is cooling
After overnight, temperature is increased to 70 DEG C and is then slowly added 2.6g sodium methoxide solution (25% methanol solution, with ethyoxyl
Compound meter 25mol%).Reactor is heated to 140 DEG C, after reaching this temperature, starts to add the contracting of 13.5g 2- ethylhexyl
Water glycerin ether (about 1.3eq.) and continue 1 hour.After addition, reactant is stirred for 6 hours at 140 DEG C, then makes it
Cool overnight.Second day, reaction mixture is heated to 50 DEG C, is quenched with 0.43g acetic acid, and be then poured into bottle.?
DMSO-d6In13C NMR (δ, ppm): 74.6,74.6,74.4,74.3,74.2,73.3,73.2,72.9,72.5,72.4,
72.2、70.6、70.1、69.8、68.4、67.9、30.1、28.5、23.4、22.5、17.2、13.9、10.9。
Automatic tableware washing test
The surface-active described in above embodiments 3-4 and comparative example C1-C3 is tested during automatic tableware washing
The antiplaque dot characteristics of agent.Dishwashing detergent formulation used is shown in table 1.
Food soil used in automatic tableware washing test is shown in table 2.
| Ingredient | Quantity in 3L batch of material |
| Water | 2L |
| Margarine | 300g |
| Potato starch | 45g |
| Quark powder | 75g |
| Benzoic acid | 3g |
| Milk | 150g |
| Yolk | 9 |
| Tomato catsup | 75g |
| Mustard | 75g |
Prepare the program of food soil
It heats the water to 70 DEG C and adds potato starch, quark powder, benzoic acid and margarine.Stirring is until artificial
Cream sufficiently dissolves.It then adds milk and is sufficiently stirred.Keep mixture cooling.When temperature is lower than 45 DEG C, addition yolk,
Tomato catsup and mustard.It is sufficiently mixed.
Dishwashing detergent test condition
Machine: Mei Nuo (Miele) SS-ADW, model G1222SC Labor.Program: there are V4 50 DEG C of heating washing to wash
Circulation is washed, fuzzy logic, heat drying are deactivated.Water: 375ppm hardness is (with CaCO3Meter is titrated by EDTA and is confirmed), Ca: Mg
=3: 1,250ppm sodium carbonate.Food soil: 50g (is introduced, be frozen in cup) in t=0.
Spot test
After open air drying, the glass observed from below in the lamp box with controlled illumination is passed through by housebroken appraiser
Glass cup determines speck grade, and speck grade is in 1 (immaculate) to 5 (a large amount of spots) range.As a result it is showed in 3 He of table
In table 4.
Spot tests A
Spot test b
Embodiment 6: the preparation and test of surfactant mixture
Surfactant is prepared by one pot of (one-pot) ethoxylation of dodecanol/tetradecanol and sealing end.To
Loading 79.03g contains 68-78% dodecanol in 2L Paar reactor and the mixture of 20-30% tetradecanol (can be with CO-
1270 buy from P&G (Procter&Gamble)) and powdered 85% potassium hydroxide of 2.85g, and in pressure inspection and a system
After column nitrogen purging, mixture is warming up to 125 DEG C.Slow nitrogen is purged through dip-tube and from reactor exhaust outlet
Remove 8.5g condensate.It releases stress and closes exhaust valve to add 394.0g epoxy with 1 to 3g/min adding rate
Ethane (about 22eq.).Total addition time is 3 hours.About 10 minutes after the addition was complete, pressure was stablized.By mixture in temperature
It keeps 50 minutes, be subsequently cooled to 100 DEG C and keep overnight again under degree.Reactor is vented and is cooled to reaction product
50 DEG C, while slowly being purged with nitrogen by dipping tube.Opening system and 2.6g sample is removed for analyzing.To anti-in Paar
The surplus material for being maintained at 50 DEG C in device is answered to add 106g 2- hexyl glycidyl ether (about 1.4 molar equivalent), and
After sealing, pressure inspection and a series of nitrogen purging, by mixture be warming up to the rate of 1 DEG C/min at 140 DEG C and
At a temperature of kept for 6 hours, be then cooled to 60 DEG C with the rate of 1 DEG C/min.It opens and sampling analysis is to confirm that reaction is completed
Afterwards, reaction product is unloaded, 548.3g is obtained.GPC result: MW=1300, MN=1230.
Automatic tableware washing test
Rinsing characteristic test is carried out using above-mentioned condition.After 5 circulations, compare including 1g (5% detergent) this implementation
The spot and film forming grade of the glass of the condition of the surfactant of example 6.The spot and film forming grade of embodiment 6 are 1.5 respectively
With 2.1, in contrast, the ethoxylated alcohol surface of the product 1 of BASF AG (BASF Corp.), 2- decamethylene sealing end is living
Property agent DEHYPON E-127 spot and film forming grade be 2.9 and 1.9 respectively.
Comparative example C4-C5 and embodiment 7
Automatic tableware washs level estimate
The automatic tableware cleaning compositions are prepared in each comparative example C4-C5 and embodiment 7, with formula shown in table 5.
In comparative example C4, dispersing agent used is that weight average molecular weight is about 3, the polyacrylic acid homopolymer of 600 dalton
(AcusolTM420N dispersing agent derives from Dow Chemical).In comparative example C5, dispersing agent used is acrylic acid and sulfonation list
The weight average molecular weight of body is the copolymer (Acusol of about 15,000 daltonTM588 dispersing agents derive from Dow Chemical).?
In embodiment 7, dispersing agent used is dispersant blend, and the weight average molecular weight with 1: 1 weight is about 3,600 dalton
Polyacrylic acid homopolymer (AcusolTM420N dispersing agent derives from Dow Chemical) and acrylic acid and sulfonated monomer divide equally again
Son amount is the copolymer (Acusol of about 15,000 daltonTM588 dispersing agents, derive from Dow Chemical) blend.
Food soil used in automatic tableware washing test is shown in table 6.
| Ingredient | Quantity in 3L batch of material |
| Water | 2.1L |
| Margarine | 300g |
| Potato starch | 15g |
| Quark powder | 75g |
| Benzoic acid | 3g |
| Milk | 150g |
| Yolk | 9 (~162 grams) |
| Catsup | 75g |
| Mustard | 75g |
Prepare the program of food soil
It heats the water to 80 DEG C and adds potato starch, quark powder, benzoic acid and margarine.Stirring is until artificial
Cream sufficiently dissolves.It then adds milk and is sufficiently stirred.Keep mixture cooling.When temperature is lower than 45 DEG C, addition yolk,
Tomato catsup and mustard.It is sufficiently mixed.
Dishwashing detergent test condition
Machine: Mei Nuo (Miele) SS-ADW, model G1222SC Labor.Program: it is washed 30 minutes at 65 DEG C.Water:
37 ° of fH total hardnesss, Ca: Mg=3: 1,25 ° of fH of temporary hardness.Food soil: 50g (is introduced, be frozen in cup) in t=0.
Cycle-index: 30.
Level estimate
After open air drying, the glass observed from below in the lamp box with controlled illumination is passed through by housebroken appraiser
Glass cup determines grade, and in 1 (no film) to 5 (high level film forming) range.As a result it is shown in table 7.
Table 7
| The automatic tableware cleaning compositions | Grade |
| Comparative example C4 | 4 |
| Comparative example C5 | 4 |
| Embodiment 7 | 3 |
Claims (10)
1. a kind of the automatic tableware cleaning compositions, it includes:
The polymer dispersant blend of 0.5 to 15 weight %, it includes:
Acrylate homopolymer；With
The copolymer of acrylic acid and sulfonated monomer；
Wherein the mixing ratio of the acrylate homopolymer of the polymer dispersant blend and the copolymer is 3: 1 to 1:
3；
The surfactant of 0.5 to 15 weight %；
The builder of 1 to 75 weight %；
The additive of 0 to 75 weight %.
2. the automatic tableware cleaning compositions according to claim 1, wherein the builder is selected from carbonate, citric acid
Salt, silicate and its mixture.
3. the automatic tableware cleaning compositions according to claim 1 further include additive selected from the following: bleaching
Agent, bleach-activating, bleaching catalyst, enzyme, phosphonate and aminocarboxylate chelators.
4. the automatic tableware cleaning compositions according to claim 1, wherein the automatic tableware cleaning compositions are free of ammonia
Yl carboxylic acid salt chelating agent.
5. the automatic tableware cleaning compositions according to claim 1, wherein the automatic tableware cleaning compositions contain it is small
In the phosphate of 0.5wt% (with element phosphorus measurement).
6. the automatic tableware cleaning compositions according to claim 5, wherein the automatic tableware cleaning compositions contain less
In the aminocarboxylate chelators of 0.1wt%.
7. the automatic tableware cleaning compositions according to claim 6, wherein the surfactant is the glycidol of Formulas I
Ether capped ethoxylated alcohol:
Wherein R1It is linear saturation C8-24Alkyl, R2It is linear chain or branched chain saturation C6-20Alkyl, the average value of m is 10 to 50, and n
Average value > 1 to 2.
8. the automatic tableware cleaning compositions according to claim 7, wherein R1It is linear saturation C10-14Alkyl.
9. the automatic tableware cleaning compositions according to claim 7, wherein R2It is branch saturation C6-10Alkyl.
10. a kind of method of the clean article in automatic tableware rinsing maching, the method includes:
The automatic tableware cleaning compositions according to claim 1 are applied to the article.
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| PCT/US2018/023089 WO2018183010A1 (en) | 2017-03-30 | 2018-03-19 | Dispersant system for automatic dish washing formulations |
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| WO2020247199A1 (en) * | 2019-06-05 | 2020-12-10 | Dow Global Technologies Llc | Automatic dishwashing compositions and method of cleaning articles |
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