CN110382678B - Dispersant system for automatic dishwashing formulations - Google Patents
Dispersant system for automatic dishwashing formulations Download PDFInfo
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- CN110382678B CN110382678B CN201880017116.2A CN201880017116A CN110382678B CN 110382678 B CN110382678 B CN 110382678B CN 201880017116 A CN201880017116 A CN 201880017116A CN 110382678 B CN110382678 B CN 110382678B
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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
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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
- C11D1/721—End blocked ethers
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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
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
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Abstract
An automatic dishwashing composition is provided comprising: a dispersant polymer blend comprising an acrylic acid homopolymer; and copolymers of acrylic acid with sulfonated monomers; wherein the dispersant polymer blend has a blend ratio of acrylic homopolymer to copolymer of 3: 1 to 1: 3; a surfactant; a builder; and optionally additives.
Description
The present invention relates to a dispersant system for automatic dishwashing formulations. In particular, the present invention relates to automatic dishwashing compositions incorporating such dispersant systems which reduce spotting and/or filming on dishware.
Automatic dishwashing compositions are known as a class of detergent compositions different from those used for fabric washing or water treatment. After a complete cleaning cycle, the user desires that the automatic dishwashing composition produce a non-spotting and non-filming appearance on the washed items.
Welch et al, in U.S. patent No. 5,294,365, disclose a family of hydroxy polyethers as low foaming surfactants for use as rinse aids in phosphate-containing machine dishwashing detergent formulations. Welch et al disclose compounds of the formula
Wherein R is1And R2Identical or different and are straight-chain or branched C1-18An alkyl group; n is a number from 15 to 45; and m is a number from 0 to 3.
Nonetheless, phosphate-free compositions are becoming increasingly desirable. Phosphate-free compositions rely on non-phosphate builders, such as citrate, carbonate, silicate, disilicate, bicarbonate, aminocarboxylate and others, to sequester calcium and magnesium from hard water and prevent it from leaving insoluble visible deposits on the dishware after drying. However, phosphate-free compositions tend to leave spots on glassware and other surfaces.
Compositions that exhibit improved characteristics and are phosphate free in automatic dishwashing would be a great advance in the industry. Thus, there remains a need for new surfactants having antiplaque properties. In particular, there remains a need for new surfactants with anti-spotting properties that contribute to phosphate-free and anti-spotting automatic dishwashing formulations.
The present invention provides an automatic dishwashing composition comprising: 0.5 to 15 weight percent of a dispersant polymer blend comprising: a homopolymer of acrylic acid; and copolymers of acrylic acid with sulfonated monomers; wherein the dispersant polymer blend has a mixing ratio of acrylic homopolymer to copolymer of from 3: 1 to 1: 3 on a weight basis; 0.5 to 15 wt% of a surfactant; 1 to 75 wt% of a builder; 0 to 75 wt% of additives.
The present invention provides an automatic dishwashing composition comprising: 0.5 to 15 weight percent of a dispersant polymer blend comprising: a homopolymer of acrylic acid; and copolymers of acrylic acid with sulfonated monomers; wherein the dispersant polymer blend has a mixing ratio of acrylic homopolymer to copolymer of from 3: 1 to 1: 3 on a weight basis; 0.5 to 15 wt% of a surfactant; 1 to 75 wt% of a builder; 0 to 75 wt% of an additive; wherein the automatic dishwashing composition contains less than 0.1 wt% phosphate; wherein the automatic dishwashing composition contains less than 0.1 wt% aminocarboxylate chelant; and wherein the surfactant is a glycidyl ether terminated ethoxylated alcohol of formula I:
wherein R is1Is straight-chain saturated C8-24Alkyl radical, R2Is straight-chain or branched saturated C6-20Alkyl, m has an average value of 10 to 50, and n has an average value > 1 to 2.
The present invention also provides a method of cleaning items in an automatic dishwashing machine, the method comprising: the automatic dishwashing composition of the present invention is applied to the item.
Detailed Description
When incorporated into automatic dishwashing compositions, particularly phosphate-free automatic dishwashing compositions, comprising a blend of a homopolymer of acrylic acid and a copolymer of acrylic acid and a sulfonated monomer, preferably wherein the automatic dishwashing composition further comprises the surfactants of the present invention based on the reaction of certain glycidyl ethers with the groups of ethoxylated alcohols, the dispersant formulations of the present invention significantly improve the anti-spotting and/or anti-fouling (filming) properties of the automatic dishwashing compositions.
Ratios, percentages, parts, and the like are by weight unless otherwise indicated. The weight percent (or wt%) in the composition is a percentage of the dry weight, i.e., excluding any water that may be present in the composition. The percentage of monomer units in the polymer is a percentage of the weight of solids, i.e., excluding any water present in the polymer emulsion.
As used herein, unless otherwise indicated, the terms "molecular weight" and "Mw" are used interchangeably to refer to the weight average molecular weight as measured in a conventional manner using Gel Permeation Chromatography (GPC) and conventional standards (e.g., polyethylene glycol standards). GPC techniques are described in modern Size Exclusion Chromatography (Modem Size Exclusion Chromatography), w.w.yau, j.j.kirkland, d.d.by; willi-international scientific press (Wiley-Interscience), 1979 and in the guidelines for material Characterization and Chemical Analysis (a Guide to Materials Characterization and Chemical Analysis), j.p. sibilia; german society of chemistry, Press (VCH), 1988, pages 81-84. Molecular weights reported herein are in daltons (Dalton).
The term "ethylenically unsaturated" is used to describe a molecule or moiety having one or more carbon-carbon double bonds that makes it polymerizable. The term "ethylenically unsaturated" includes both monoethylenically unsaturated (having one carbon-carbon double bond) and polyethylenically unsaturated (having two or more carbon-carbon double bonds). As used herein, the term "(meth) acrylic" refers to either acrylic or methacrylic.
As used herein and in the appended claims, the terms "ethyleneoxy" and "EO" refer to-CH2-CH2-O-。
As used herein and in the appended claims, the term "phosphate-free" means a composition containing 1 wt.% (preferably 0.5 wt.%; more preferably less than 0.2 wt.%; still more preferably less than 0.1 wt.%; still more preferably less than 0.01 wt.%; most preferably less than the detectable limit) phosphate (measured as elemental phosphorus).
The term "structural unit" as used herein and in the appended claims refers to the remainder of the indicated monomer;
thus, the structural units of acrylic acid are illustrated:
wherein the dotted line represents the point of attachment to the polymer backbone.
Preferably, the automatic dishwashing composition of the present invention comprises: from 0.5 to 15% (preferably from 0.5 to 10%, more preferably from 1 to 8%, most preferably from 2.5 to 7.5%) by weight of a dispersant polymer blend comprising: a homopolymer of acrylic acid; and copolymers of acrylic acid with sulfonated monomers; wherein the dispersant polymer blend has a mixing ratio of acrylic acid homopolymer to copolymer of from 3: 1 to 1: 3 (preferably from 2.5: 1 to 1: 2.5; more preferably from 2: 1 to 1: 2; most preferably from 1.5: 1 to 1: 1.5) on a weight basis; 0.5 to 15 wt% (preferably 0.5 to 10 wt%, more preferably 1 to 8 wt%, most preferably 2.5 to 7.5 wt%) of a surfactant (preferably wherein the surfactant is a nonionic surfactant); 1 to 75 wt% of a builder; and 0 to 75 wt% of an additive.
Preferably, the automatic dishwashing composition of the present invention comprises: from 0.5 to 15% (preferably from 0.5 to 10%, more preferably from 1 to 8%, most preferably from 2.5 to 7.5%) by weight of a dispersant polymer blend comprising: a homopolymer of acrylic acid; and copolymers of acrylic acid with sulfonated monomers; wherein the dispersant polymer blend has a mixing ratio of acrylic acid homopolymer to copolymer of from 3: 1 to 1: 3 (preferably from 2.5: 1 to 1: 2.5; more preferably from 2: 1 to 1: 2; most preferably from 1.5: 1 to 1: 1.5) on a weight basis; 0.5 to 15 wt% (preferably 0.5 to 10 wt%, more preferably 1 to 8 wt%, most preferably 2.5 to 7.5 wt%) of a surfactant (preferably wherein the surfactant is a nonionic surfactant); 1 to 75 wt% of a builder; and 0 to 75 wt% of an additive; wherein the builder is selected from the group consisting of carbonates, citrates, silicates and mixtures thereof.
Preferably, the automatic dishwashing composition of the present invention comprises: from 0.5 to 15% (preferably from 0.5 to 10%, more preferably from 1 to 8%, most preferably from 2.5 to 7.5%) by weight of a dispersant polymer blend comprising: a homopolymer of acrylic acid; and copolymers of acrylic acid with sulfonated monomers; wherein the dispersant polymer blend has a mixing ratio of acrylic acid homopolymer to copolymer of from 3: 1 to 1: 3 (preferably from 2.5: 1 to 1: 2.5; more preferably from 2: 1 to 1: 2; most preferably from 1.5: 1 to 1: 1.5) on a weight basis; 0.5 to 15 wt% (preferably 0.5 to 10 wt%, more preferably 1 to 8 wt%, most preferably 2.5 to 7.5 wt%) of a surfactant (preferably wherein the surfactant is a nonionic surfactant); 1 to 75 wt% of a builder; and 0 to 75 wt% of an additive; wherein the surfactant is a glycidyl ether terminated ethoxylated alcohol of formula I:
wherein R is1Is straight-chain saturated C8-24Alkyl (preferably straight-chain saturated C)10-14An alkyl group; more preferably straight-chain saturated C10-12An alkyl group; more preferably straight-chain saturated C10Alkyl or straight-chain saturated C12Alkyl groups); r2Is straight-chain saturated or branched saturated C6-20Alkyl (preferably branched saturated C)6-10An alkyl group; more preferably 2-ethylhexyl); m has an average value of 10 to 50 (preferably 10 to 30; more preferably 15 to 30; still more preferably 18 to 22; still more preferably 19 to 21; most preferably 20); and n has an average value > 1 to 2 (preferably 1.1 to 2; more preferably 1.2 to 1.6); and wherein the automatic dishwashing composition comprises less than 0.1 wt% (preferably < 0.05 wt%, more preferably < 0.01 wt%, still more preferably < detection limit; most preferably none) of an aminocarboxylate chelant (e.g. MGDA). The glycidyl ether capped ethoxylated alcohol surfactants of formula I may be included in R1And R2Mixtures of compounds above containing a series of alkyl groups differing in carbon number but having an average carbon number conforming to the ranges set forth above.
Preferably, the automatic dishwashing composition of the present invention comprises from 0.5 to 15 wt% of the dispersant polymer blend, based on the dry weight of the automatic dishwashing composition. More preferably, the automatic dishwashing composition of the present invention comprises from 0.5 to 10 wt% of the dispersant polymer blend, based on the dry weight of the automatic dishwashing composition. Still more preferably, the automatic dishwashing composition of the present invention comprises from 1 to 8 wt% of the dispersant polymer blend, based on the dry weight of the automatic dishwashing composition. Most preferably, the automatic dishwashing composition of the present invention comprises from 2.5 to 7.5 wt% of the dispersant polymer blend, based on the dry weight of the automatic dishwashing composition.
Preferably, the automatic dishwashing composition of the present invention comprises ≥ 1 wt% (more preferably ≥ 2 wt% >, more preferably ≥ 3 wt% >, more preferably ≥ 5 wt%) of the dispersant polymer blend, based on dry weight of the automatic dishwashing composition. Preferably, the automatic dishwashing composition of the present invention comprises, based on the dry weight of the automatic dishwashing composition: less than or equal to 10 wt% (more preferably less than or equal to 8 wt%, more preferably less than or equal to 6 wt%, more preferably less than or equal to 4 wt%) of a dispersant polymer blend.
Preferably, the dispersant polymer blend comprised in the automatic dishwashing composition of the present invention comprises a blend of an acrylic acid homopolymer and a copolymer of acrylic acid and a sulfonated monomer, wherein the mixing ratio of the acrylic acid homopolymer to the copolymer of the dispersant polymer blend is from 3: 1 to 1: 3 (preferably from 2.5: 1 to 1: 2.5; more preferably from 2: 1 to 1: 2; most preferably from 1.5: 1 to 1: 1.5) on a weight basis.
Preferably, the weight average molecular weight M of the acrylic acid homopolymer used in the automatic dishwashing composition of the present inventionWFrom 1,000 to 40,000 (preferably from 1,000 to 20,000; more preferably from 1,000 to 10,000; still more preferably from 1,000 to 5,000; most preferably from 2,000 to 4,000) daltons.
Preferably, the weight average molecular weight M of the copolymer of acrylic acid and sulfonated monomer used in the automatic dishwashing composition of the present inventionWFrom 2,000 to 100,000 (preferably from 5,000 to 60,000; more preferably from 8,000 to 25,000; more preferably from 10,000 to 20,000; most preferably from 12,500 to 17,500) daltons.
Preferably, the copolymer of acrylic acid and sulfonated monomer used in the automatic dishwashing composition of the present invention comprises structural units of at least one sulfonated monomer. More preferably, the copolymer of acrylic acid and sulfonated monomer used in the automatic dishwashing composition of the present invention comprises structural units of at least one sulfonated monomer selected from the group consisting of: 2-acrylamido-2-methylpropanesulfonic Acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic acid, 4-styrenesulfonic acid, vinylsulfonic acid, 3-allyloxysulfonic acid, 2-hydroxy-1-propanesulfonic acid (HAPS), 2-sulfoethyl (meth) acrylic acid, 2-sulfopropyl (meth) acrylic acid, 3-sulfopropyl (meth) acrylic acid, 4-sulfobutyl (meth) acrylic acid, and salts thereof.
Preferably, the copolymer of acrylic acid and sulfonated monomer used in the automatic dishwashing composition of the present invention comprises: 5-65 wt% (more preferably 15-40 wt%, most preferably 20-35 wt%) acrylic acid structural units.
Preferably, the copolymer of acrylic acid and sulfonated monomer used in the automatic dishwashing composition of the present invention comprises: 50 to 95 wt.% (preferably 70 to 93 wt.%) of acrylic acid building blocks and 5 to 50 wt.% (preferably 7 to 30 wt.%) of building blocks of 2-acrylamido-2-methylpropane sulfonic acid sodium salt. More preferably, the copolymer of acrylic acid and sulfonated monomer used in the automatic dishwashing composition of the present invention comprises: 50 to 95 wt.% (preferably 70 to 93 wt.%) of acrylic acid structural units and 5 to 50 wt.% (preferably 7 to 30 wt.%) of structural units of 2-acrylamido-2-methylpropane sulfonic acid sodium salt; wherein the weight average molecular weight Mw of the copolymer is from 2,000 to 100,000 (more preferably from 10,000 to 20,000; most preferably from 12,500 to 17,500) daltons.
The polymers comprised in the dispersant polymer blend used in the automatic dishwashing composition of the present invention may be commercially available from a variety of sources, and/or they may be prepared using literature techniques. For example, the low molecular weight polymer included in the dispersant polymer blend may be prepared by free radical polymerization. The preferred method for preparing these polymers is by homogeneous polymerization in a solvent. The solvent may be water or an alcohol solvent, such as 2-propanol or 1, 2-propanediol. Radical polymerization is initiated by the decomposition of precursor compounds, such as alkali metal persulfates or organic peracids and peresters. Activation of the precursor may be achieved by the action of an increase in reaction temperature alone (thermal activation) or by a blend of redox active agents, such as a combination of iron (II) sulfate and ascorbic acid (redox activation). In these cases, chain transfer agents are typically used to adjust the polymer molecular weight. One preferred class of chain transfer agents used in solution polymerization is alkali metal bisulfite or ammonium bisulfite. Sodium metabisulphite is particularly mentioned.
The polymer included in the dispersant polymer blend used in the automatic dishwashing composition of the present invention may be in the form of a water soluble solution polymer, a slurry, a dry powder or granules, or other solid form.
Preferably, the automatic dishwashing composition of the present invention comprises from 0.5 to 15 wt% (preferably from 0.5 to 10 wt%; more preferably from 1 to 8 wt%; most preferably from 2.5 to 7.5 wt%) surfactant. Preferably, the surfactant used in the automatic dishwashing composition of the present invention is a nonionic surfactant. More preferably, the surfactant used in the automatic dishwashing composition of the present invention is a nonionic surfactant selected from the group consisting of: ethylene oxide-propylene oxide-butylene oxide di-or tri-block copolymers, alkoxylated fatty alcohols, amine oxides, alkyl ether sulfates or alkyl polyglycosides. Preferably, the surfactant used in the automatic dishwashing composition of the present invention is a nonionic surfactant having a cloud point of less than 45 ℃. Preferably, the surfactant used in the automatic dishwashing composition of the present invention is a nonionic surfactant based on polyoxyalkylene polyether derivatives.
Preferably, the surfactant used in the automatic dishwashing composition of the present invention is a glycidyl ether capped ethoxylated alcohol of formula I:
wherein R is1Is straight-chain saturated C8-24Alkyl (preferably straight-chain saturated C)10-14An alkyl group; more preferably straight-chain saturated C10-12An alkyl group; more preferably straight-chain saturated C10Alkyl or straight-chain saturated C12Alkyl groups); r2Is straight-chain saturated or branched saturated C6-20Alkyl (preferably branched saturated C)6-10An alkyl group; more preferably 2-ethylhexyl); m isIs from 10 to 50 (preferably from 10 to 30; more preferably from 15 to 30; still more preferably from 18 to 22; still more preferably from 19 to 21; most preferably 20); and n has an average value > 1 to 2 (preferably 1.1 to 2; more preferably 1.2 to 1.6). The glycidyl ether capped ethoxylated alcohol surfactants of formula I may be included in R1And R2Mixtures of compounds above containing a series of alkyl groups differing in carbon number but having an average carbon number conforming to the ranges set forth above.
The glycidyl ether capped ethoxylated alcohol surfactants of formula I can be readily prepared using known synthetic methods. For example, a typical procedure for preparing a compound is as follows. Will conform to the formula R1OH (wherein R1Is straight-chain saturated C8-24Alkyl) alcohol is added to the reactor and heated in the presence of a base (e.g., sodium methoxide or potassium hydroxide). The mixture should be relatively free of water. To this mixture is then added the desired amount of Ethylene Oxide (EO) under pressure. After EO consumption (as indicated by a large drop in reactor pressure), the resulting ethoxylated alcohol may be separated and subjected to basic conditions to a pressure of alcohol in the range of 1: 1.1 to 1: 2: the molar ratio of the glycidyl ether is reacted with an alkyl glycidyl ether wherein the alkyl group contains from 6 to 20 carbon atoms. Alternatively, the ethoxylated alcohol may remain in the original reactor and be further reacted by the addition of an alkyl glycidyl ether. The molar ratio of catalyst to alcohol may be between 0.01: 1 and 1: 1, but is preferably between 0.02: 1 and 0.5: 1. Alternatively, Lewis acid catalysts (e.g., boron trifluoride etherate) may be employed in a molar ratio to alcohol of from 0.01: 1 to 0.25: 1. The reaction with EO and the alkyl glycidyl ether is generally carried out in the absence of a solvent and at a temperature of between 25 ℃ and 200 ℃ and preferably between 80 ℃ and 160 ℃.
Preferably, the builder used in the automatic dishwashing composition of the present invention comprises one or more of carbonate, citrate and silicate.
Preferably, the automatic dishwashing composition of the present invention comprises: 1-75 wt% of a builder. Preferably, the automatic dishwashing composition of the present invention comprises, by weight of the dry automatic dishwashing composition: not less than 1 wt% (more preferably not less than 10 wt%, still more preferably not less than 20 wt%, still more preferably not less than 25 wt%) of a builder. Preferably, the automatic dishwashing composition of the present invention comprises, by weight of the dry automatic dishwashing composition: less than or equal to 75 wt% (preferably less than or equal to 60 wt%, more preferably less than or equal to 50 wt%, most preferably less than or equal to 40 wt%) of a builder. The weight percentages of carbonate, citrate, and silicate are based on the actual weight of the salt, including the metal ion.
As used herein and in the appended claims, the term "carbonate" refers to alkali metal or ammonium carbonates, bicarbonates, percarbonates, and/or sesquicarbonates. Preferably, the carbonate salt (if any) used in the automatic dishwashing composition is selected from sodium, potassium and lithium carbonate salts (more preferably, sodium or potassium salts, most preferably sodium salts). More preferably, the carbonate salt used in the automatic dishwashing composition of the present invention is selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium percarbonate and mixtures thereof.
Preferably, the builder used in the automatic dishwashing composition of the present invention comprises carbonate. More preferably, the builder used in the automatic dishwashing composition of the present invention comprises a mixture of carbonates. Preferably, when the builder used in the automatic dishwashing composition of the present invention comprises carbonate, the automatic dishwashing composition preferably comprises 10 to 75 wt% (preferably 15 to 70 wt%; more preferably 25 to 60 wt%; most preferably 30 to 50 wt%) carbonate.
As used herein and in the appended claims, the term "citrate salt" refers to an alkali metal citrate salt. Preferably, the citrate salt (if any) used in the automatic dishwashing composition is selected from sodium, potassium and lithium citrates (more preferably sodium or potassium salts; most preferably sodium salts). More preferably, the citrate salt (if any) used in the automatic dishwashing composition is sodium citrate.
Preferably, the builder used in the automatic dishwashing composition of the present invention comprises citrate. More preferably, the builder used in the automatic dishwashing composition of the present invention comprises a mixture of carbonates. Preferably, when the builder used in the automatic dishwashing composition of the present invention comprises carbonate, the automatic dishwashing composition preferably comprises 0% to 40% (preferably 21% to 40%, more preferably 25% to 35%, most preferably 27.5% to 32.5%) by weight of citrate.
As used herein and in the appended claims, the term "silicate" refers to an alkali metal silicate. Preferably, the silicate (if any) used in the automatic dishwashing composition is selected from sodium, potassium and lithium silicates (more preferably sodium or potassium salts; most preferably sodium salts). More preferably, the silicate (if any) used in the automatic dishwashing composition is sodium disilicate. Preferably, the builder used in the automatic dishwashing composition of the present invention comprises silicate. Preferably, when the builder used in the automatic dishwashing composition of the present invention comprises silicate, the automatic dishwashing composition preferably comprises ≦ 0 to 10 wt% (preferably 0.1 to 5 wt%, more preferably 0.5 to 3 wt%, most preferably 1.5 to 2.5 wt%) silicate.
The automatic dishwashing composition of the present invention optionally further comprises: and (3) an additive. Preferably, the automatic dishwashing composition of the present invention, optionally further comprises: an additive selected from the group consisting of: an alkalinity source, a bleaching agent (e.g., sodium percarbonate, sodium perborate), and optionally a bleach activator (e.g., Tetraacetylethylenediamine (TAED)) and/or a bleach catalyst (e.g., manganese (II) acetate, cobalt (II) chloride, bis (TACN) magnesium trioxide diacetate); enzymes (e.g., proteases, amylases, lipases, or cellulases); aminocarboxylate chelants (e.g., methylglycine diacetic acid (MGDA), glutamic-N, N-diacetic acid (GLDA), iminodisuccinic acid (IDSA), 1, 2-ethylenediamine disuccinic acid (EDDS), aspartic acid diacetic acid (ASDA), or mixtures or salts thereof); phosphonates such as 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDP); defoaming agents; a colorant; a fragrance; a silicate salt; poly (ethylene glycol); an additional builder; antibacterial agents and/or fillers. The filler in the tablet or powder is an inert, water-soluble substance, typically a sodium or potassium salt, such as sodium or potassium sulphate and/or chloride, and is typically present in an amount in the range of 0 to 75 wt%. Fillers in the gel formulation may include those described above as well as water and other solvents (e.g., glycerin). Fragrances, dyes, antifoams, enzymes and antimicrobials generally do not exceed 10% by weight of the composition in total, alternatively do not exceed 5% by weight of the composition.
The automatic dishwashing composition of the present invention optionally further comprises: a source of alkalinity. Suitable alkalinity sources include, but are not limited to, alkali metal carbonates and hydroxides, such as sodium or potassium carbonate, sodium or potassium bicarbonate, sodium or potassium sesquicarbonate, sodium, lithium or potassium hydroxide, or mixtures thereof. Sodium carbonate is preferred. When present, the amount of alkalinity source in the automatic dishwashing composition of the present invention may be, for example, at least 1 wt% (preferably at least 20 wt%) and at most 80 wt% (preferably at most 60 wt%), based on the dry weight of the automatic dishwashing composition.
The automatic dishwashing composition of the present invention optionally further comprises: a bleaching agent. The preferred bleaching agent is sodium percarbonate. When present, the amount of bleach in the automatic dishwashing composition of the present invention is preferably a concentration of from 1 wt% to 25 wt% (more preferably from 1 wt% to 10 wt%) based on the dry weight of the automatic dishwashing composition.
Preferably, the automatic dishwashing composition of the present invention has a pH (1 wt% in water) of at least 9 (preferably ≧ 10). Preferably, the automatic dishwashing composition of the present invention has a pH of no greater than 13 (1 wt% in water).
Preferably, the automatic dishwashing composition of the present invention can be formulated in any typical form, e.g., in the form of tablets, powders, bars, single doses, sachets, pastes, liquids or gels. The automatic dishwashing composition of the present invention is suitable for cleaning utensils, such as tableware and cookware, dishes, in an automatic dishwashing machine.
Preferably, the automatic dishwashing compositions of the present invention can be used under typical operating conditions. For example, when used in an automatic dishwashing machine, typical water temperatures during washing are preferably 20 ℃ to 85 ℃, preferably 30 ℃ to 70 ℃. Typical concentrations of the automatic dishwashing composition, as a percentage of the total liquid in the dishwashing machine, are preferably from 0.1% to 1% by weight, preferably from 0.2% to 0.7% by weight. By selecting the appropriate product form and addition time, the automatic dishwashing composition of the present invention can be present in a pre-wash, a main wash, a penultimate rinse, a final rinse, or any combination of these cycles.
Preferably, the automatic dishwashing composition of the present invention comprises ≦ 1 wt% (preferably ≦ 0.5 wt% >, more preferably ≦ 0.2 wt% >, still more preferably ≦ 0.1 wt% >, still more preferably ≦ 0.01 wt% >, most preferably < detectable limit) of phosphate (measured as elemental phosphorus). Preferably, the automatic dishwashing composition of the present invention is phosphate-free.
Preferably, the automatic dishwashing composition of the present invention comprises < 0.1 wt.% (preferably < 0.05 wt.%; more preferably < 0.01 wt.%; most preferably < detectable limit) of an aminocarboxylate chelant (e.g. MGDA). Preferably, the automatic dishwashing composition of the present invention is free of aminocarboxylate chelants (e.g., MGDA).
Some embodiments of the present invention will now be described in detail in the following examples.
Preparation of surfactants
Materials: 1, 2-epoxyoctane, 2-ethylhexyl glycidyl ether, 1-decanol, 1-dodecanol, 2-butyl-1-octanol, sodium methoxide solution obtained from Sigma Aldrich (Sigma-Aldrich) and used without further purification. 2-ethylhexanol, first reacted with 5 equivalents of propylene oxide, then reacted with 15 equivalents of ethylene oxide, was obtained as a 90% aqueous solution from the Dow Chemical company and is hereinafter referred to as "2 EH-PO5-EO 15".
Analytical method
NMR: quantification was obtained on a Brooks (Bruker)500MHz instrument13C spectra, run generally 6144 scans, experiment zgig30, pulse length 13.25 μ s, cycle delay 5.000s, line broadening 2 Hz.
Polymer molecular weight. The weight average molecular weight can be measured by Gel Permeation Chromatography (GPC) using a known method. GPC analysis was performed by dissolving a 0.010g sample in 10mL THF, and injecting 50 μ L aliquots of this solution into two Polymer Labs PLgel 5 μm MIXED-E columns (300X 7.5mm) in series and eluting with THF (neat or containing 5% water) on an Agilent (Agilent)1100 series GPC at a flow rate of 1.0mL/min at 35 ℃ using differential refractive index detection (35 ℃). A conventional calibration curve was generated using narrow polyethylene glycol standards.
The alkoxylation reaction was carried out in a 2L 316 stainless steel conical bottom (minimum stirred volume 20mL) Parr reactor (Parr reactor) model 4530 equipped with an 1/4hp magnetically driven stirrer, 1500 watt (115V) Calrod electric heater, 1/4 inch water-filled cooling coil, 1/16 inch dip tube for sampling, internal thermowell, 1/4 inch burst disk set at 1024psig, 1/4 inch overflow valve set at 900psig, oxide addition line submerged below the liquid surface, and a 2 inch diameter blade stirrer. The bottom of the stirrer shaft had a custom made stainless steel blade shaped to the contour of the reactor to allow stirring at a very low initial volume. The oxide addition system consisted of a1 liter stainless steel addition cylinder, which was charged, weighed and attached to an oxide loading line. The reactor system was controlled by a Siemens (Siemens) SIMATIC PCS7 process control system. Reaction temperature was measured with a type K thermocouple, pressure was measured with an Ashcroft pressure sensor, ball valves were operated with a world viaroc (Swagelok) pneumatic valve actuator, cooling water flow was controlled with an ASCO motorized valve, and oxide addition rate was controlled with a mass flow control system controlled by Brooks
A Coriolis mass flow controller (model number QMBC3L1B2A1 DH1C7A1DA) and a TESCOM back pressure regulator (model number 44-1163-24-109A) that maintains a pressure differential of 100psig across the mass flow controller to provide a steady flow rate.
The reactant ratio is sometimes abbreviated as "X eq.": wherein the added reagent is considered to have an X: 1 in a molar ratio.
Practice ofExample 1: synthesis of decyl alcohol ethoxylate
A 2L parr reactor was charged with 121.3g of 1-decanol and 0.50g of powdered 85% potassium hydroxide and after pressure check and a series of nitrogen purges, the mixture was warmed to 130 ℃ to add 670.2g of ethylene oxide (about 20eq.) at an addition rate of 1 to 2 g/min. After the addition was complete and the pressure stabilized, the reaction product was cooled and unloaded to yield 785.6 g. GPC results: mW＝1220，MN1140. In DMSO-d6In (1)13C 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。
Example 2: synthesis of dodecanol ethoxylate
A2L Parr reactor was charged with 100.2g of 1-decanol and 0.56g of powdered 85% potassium hydroxide and after pressure check and a series of nitrogen purges, the mixture was warmed to 130 ℃ to add 473.0g of ethylene oxide (about 20eq.) at an addition rate of 2 g/min. After the addition was complete and the pressure stabilized, the reaction product was cooled and unloaded to yield 564.77 g. GPC results: mW＝1110，MN1045. In DMSO-d6In (1)13C 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。
Example 3: decyl alcohol ethoxylate/2-ethylhexyl glycidyl ether
To a round bottom glass flask equipped with an overhead stirrer, thermocouple, nitrogen sweep and heating mantle was added 50g of the decanol ethoxylate from example 1. Heating was continued until the decanol ethoxylate melted, stirring was then started and 2.6g of sodium methoxide solution (25% methanol solution, 25 mol% calculated as ethoxylate) were slowly added. The reactor was heated to 140 ℃ and after this temperature was reached, the addition of 13.5g of 2-ethylhexyl glycidyl ether (about 1.7eq.) was started and continued for 1 hour. After addition, the reaction was stirred at 140 ℃ for another 6 hours, then allowed to cool overnight. The next day, the reaction mixture was heated to 50 ℃ with 0.43gThe acetic acid was quenched and then poured into a vial. In DMSO-d6In (1)13C 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。
Example 4: dodecanol ethoxylate/2-ethylhexyl glycidyl ether
To a round bottom glass flask equipped with an overhead stirrer, thermocouple, nitrogen sweep and heating mantle was added 51.5g of dodecanol ethoxylate from example 2. Heating was continued until the decanol ethoxylate melted, stirring was then started and 2.6g of sodium methoxide solution (25% methanol solution, 25 mol% calculated as ethoxylate) were slowly added. The reactor was heated to 140 ℃ and after this temperature was reached, the addition of 13.5g of 2-ethylhexyl glycidyl ether (about 1.3eq.) was started and continued for 1 hour. After addition, the reaction was stirred at 140 ℃ for another 6 hours, then allowed to cool overnight. The next day, the reaction mixture was heated to 50 ℃, quenched with 0.43g of acetic acid, and then poured into a vial. In DMSO-d6In (1)13C NMR(δ，ppm)：73.3、72.9、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。
EXAMPLE 5 Synthesis of 2-Butyloctanol ethoxylate
A2L Parr reactor was charged with 85.90g of 2-butyl-1-octanol and 0.48g of powdered 85% potassium hydroxide, and after pressure check and a series of nitrogen purges, the mixture was warmed to 130 ℃ to add 406.4g of ethylene oxide (about 20eq.) at an addition rate of 2 g/min. After the addition was complete and the pressure stabilized, the reaction product was cooled and unloaded to give 493.2 g. GPC results: mW＝1390，MN1190. In DMSO-d6In (1)13C 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-epoxyoctane
To a round bottom glass flask equipped with an overhead stirrer, thermocouple, nitrogen sweep and heating mantle was added 50g of the decanol ethoxylate from example 1. Heating was continued until the decanol ethoxylate melted, stirring was then started and 2.6g of sodium methoxide solution (25% methanol solution, 25 mol% calculated as ethoxylate) were slowly added. The reactor was heated to 90 ℃ and after this temperature was reached, the addition of 9.3g of 1, 2-epoxyoctane (approx. 1.7eq.) was started and continued for 1 hour. After addition, the reaction was stirred at 140 ℃ for another 6 hours, then allowed to cool overnight. The following day, the reaction mixture was heated to 90 ℃ and heated for an additional 6 hours, then allowed to cool to 50 ℃, quenched with 0.43g of acetic acid, and then poured into a vial. In DMSO-d6In (1)13C 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-Butyloctanol ethoxylate/2-ethylhexyl glycidyl ether
To a round bottom glass flask equipped with an overhead stirrer, thermocouple, nitrogen sweep and heating mantle was added 51.5g of 2-butyloctanol ethoxylate from example 5. Heating was continued until the decanol ethoxylate melted, stirring was then started and 2.6g of sodium methoxide solution (25% methanol solution, 25 mol% calculated as ethoxylate) were slowly added. The reactor was heated to 140 ℃ and after this temperature was reached, the addition of 13.5g of 2-ethylhexyl glycidyl ether (about 1.3eq.) was started and continued for 1 hour. After addition, the reaction was stirred at 140 ℃ for another 6 hours, then allowed to cool overnight. The next day, the reaction mixture was heated to 50 ℃, quenched with 0.43g of acetic acid, and then poured into a vial. In DMSO-d6In (1)13C 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-ethylhexanol alkoxylates/2-ethylhexyl glycidyl ether
To a round bottom glass flask equipped with an overhead stirrer, thermocouple, nitrogen sweep and heating mantle was added 57.8g of 2EH-PO5-EO15 (90%). The kettle was heated to 140 ℃ for 3 hours with stirring and bubbling of active nitrogen to remove water. After cooling overnight, the temperature was raised to 70 ℃ and then 2.6g of sodium methoxide solution (25% methanol solution, 25 mol% based on ethoxylate) were slowly added. The reactor was heated to 140 ℃ and after this temperature was reached, the addition of 13.5g of 2-ethylhexyl glycidyl ether (about 1.3eq.) was started and continued for 1 hour. After addition, the reaction was stirred at 140 ℃ for another 6 hours, then allowed to cool overnight. The next day, the reaction mixture was heated to 50 ℃, quenched with 0.43g of acetic acid, and then poured into a vial. In DMSO-d6In (1)13C 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 dishwashing test
The surfactants described in examples 3-4 and comparative examples C1-C3 above were tested for anti-spotting characteristics during automatic dishwashing. The dishwashing formulations used are shown in table 1.
The food soil used in the automatic dishwashing test is shown in table 2.
| Composition (I) | Amount in 3L batch |
| Water (W) | 2L |
| Margarine | 300g |
| Potato starch | 45g |
| Quark powder | 75g |
| Benzoic acid | 3g |
| Milk | 150g |
| Egg yolk | 9 |
| Tomato sauce | 75g |
| Mustard | 75g |
Procedure for preparing food-type soils
The water was heated to 70 ℃ and potato starch, quark powder, benzoic acid and margarine were added. Stirring until the margarine is sufficiently dissolved. Milk was then added and stirred well. The mixture was allowed to cool. When the temperature is below 45 deg.C, egg yolk, ketchup and mustard are added. And (4) fully mixing.
Tableware washing test conditions
A machine: meno (Miele) SS-ADW, model G1222SC Labor. The procedure is as follows: v4, 50 ℃ wash cycle with heated wash, deactivation of fuzzy logic, heat drying. Water: 375ppm hardness (as CaCO)3Meter, confirmed by EDTA titration) Ca: Mg 3: 1, 250ppm sodium carbonate. Food-type fouling: 50g (introduced at t ═ 0, frozen in a cup).
Spot testing
After open air drying, the mottle rating was determined by trained panelists by viewing the glass from below in a light box with controlled illumination, and was in the range of 1 (no mottle) to 5 (large amount of mottle). The results are shown in tables 3 and 4.
Example 6: preparation and testing of surfactant mixtures
Prepared by one-pot (one-pot) ethoxylation and capping of dodecanol/tetradecanolPreparing a surfactant. A2L Parr reactor was charged with 79.03g of a mixture containing 68-78% dodecanol and 20-30% tetradecanol (available from Procter as CO-1270)&Gamble) and 2.85g powdered 85% potassium hydroxide, and after a pressure check and a series of nitrogen purges, the mixture was warmed to 125 ℃. A slow nitrogen purge was passed through the dip tube and 8.5g of condensate was removed from the reactor vent. The pressure was released and the vent valve was closed to add 394.0g of ethylene oxide (about 22eq.) at an addition rate of 1 to 3 g/min. The total addition time was 3 hours. The pressure stabilized about 10 minutes after the addition was complete. The mixture was held at temperature for an additional 50 minutes, then cooled to 100 ℃ and held overnight. The reactor was vented and the reaction product was cooled to 50 ℃ while slowly purging with nitrogen through the dip tube. The system was opened and a 2.6g sample was removed for analysis. To the remaining material maintained at 50 ℃ in the parr reactor, 106g of 2-ethylhexyl glycidyl ether (about 1.4 molar equivalents) were added and after sealing, pressure checking and a series of nitrogen purges, the mixture was warmed to 140 ℃ at a rate of 1 ℃/min and maintained at temperature for 6 hours, then cooled to 60 ℃ at a rate of 1 ℃/min. After opening and sampling for analysis to confirm completion of the reaction, the reaction product was unloaded to give 548.3 g. GPC results: mW＝1300，MN＝1230。
Automatic dishwashing test
The rinsing property test was performed using the above conditions. After 5 cycles, the spots and film formation grades of the glasses of the conditions comprising 1g (5% detergent) of this surfactant of example 6 were compared. The speck and film-forming grades for example 6 were 1.5 and 2.1, respectively, in contrast to the speck and film-forming grades for 1, 2-epoxydecane-terminated ethoxylated alcohol surfactant DEHYPON E-127, a product of BASF Corp., which is produced by BASF corporation, which was 2.9 and 1.9, respectively.
Comparative examples C4-C5 and example 7
Automatic dishwashing grade test
Automatic dishwashing compositions having the formulations shown in Table 5 were prepared in each of comparative examples C4-C5 and example 7.
In comparative example C4, the dispersant used was a polyacrylic acid homopolymer (Acusol) having a weight average molecular weight of about 3,600 daltonsTM420N dispersant from dow chemical). In comparative example C5, the dispersing agent used was a copolymer of acrylic acid and a sulfonated monomer (Acusol) having a weight average molecular weight of about 15,000 daltonsTM588 dispersant from dow chemical company). In example 7, the dispersant used was a dispersant blend having a 1: 1 weight polyacrylic acid homopolymer (Acusol) with a weight average molecular weight of about 3,600 daltonsTM420N dispersant from dow chemical) and a copolymer of acrylic acid and a sulfonated monomer (Acusol) having a weight average molecular weight of about 15,000 daltonsTM588 dispersant from dow chemical company).
The food soil used in the automatic dishwashing test is shown in table 6.
| Composition (I) | Amount in 3L batch |
| Water (W) | 2.1L |
| Margarine | 300g |
| Potato starch | 15g |
| Quark powder | 75g |
| Benzoic acid | 3g |
| Milk | 150g |
| Egg yolk | 9 (162 g) |
| Tomato sauce | 75g |
| Mustard | 75g |
Procedure for preparing food-type soils
The water was heated to 80 ℃ and potato starch, quark powder, benzoic acid and margarine were added. Stirring until the margarine is sufficiently dissolved. Milk was then added and stirred well. The mixture was allowed to cool. When the temperature is below 45 deg.C, egg yolk, ketchup and mustard are added. And (4) fully mixing.
Tableware washing test conditions
A machine: meno (Miele) SS-ADW, model G1222SC Labor. The procedure is as follows: the washing was carried out at 65 ℃ for 30 minutes. Water: total hardness 37 ° fH, Ca: Mg 3: 1, temporary hardness 25 ° fH. Food-type fouling: 50g (introduced at t ═ 0, frozen in a cup). Cycle number: 30.
rating test
After open-air drying, the rating was determined by a trained evaluator by observing the glass in a light box with controlled illumination from below, and ranged from 1 (no film) to 5 (high level of film formation). The results are shown in table 7.
TABLE 7
| Automatic dishwashing composition | Grade |
| Comparative example C4 | 4 |
| Comparative example C5 | 4 |
| Example 7 | 3 |
Claims (8)
1. An automatic dishwashing composition comprising:
0.5 to 15 weight percent of a dispersant polymer blend comprising:
a homopolymer of acrylic acid; and
copolymers of acrylic acid and sulfonated monomers;
wherein the dispersant polymer blend has a mixing ratio of the acrylic homopolymer to the copolymer of 3: 1 to 1: 3;
0.5 to 15 wt% of a surfactant, wherein the surfactant is a glycidyl ether terminated ethoxylated alcohol of formula I:
wherein R is1Is straight-chain saturated C8-24Alkyl radical, R2Is branched saturated C6-10Alkyl, m has an average value of 10 to 50, and n has an average value of>1 and 2 or less;
1 to 75 wt% of a builder;
0 to 75 wt% of an additive;
wherein the automatic dishwashing composition contains less than 0.1 wt% aminocarboxylate chelant.
2. The automatic dishwashing composition of claim 1 wherein said builder is selected from the group consisting of carbonates, citrates, silicates, and mixtures thereof.
3. The automatic dishwashing composition of claim 1, further comprising an additive selected from the group consisting of: bleach, bleach activator, bleach catalyst, enzyme, phosphonate, and aminocarboxylate chelant.
4. The automatic dishwashing composition of claim 1 wherein said automatic dishwashing composition is free of aminocarboxylate chelants.
5. The automatic dishwashing composition of claim 1, wherein the automatic dishwashing composition contains less than 0.5 wt% phosphate, measured as elemental phosphorus.
6. Automatic dishwashing according to claim 1Composition of which R1Is straight-chain saturated C10-14An alkyl group.
7. An automatic dishwashing composition according to claim 1 wherein R2Is 2-ethylhexyl.
8. A method of cleaning items in an automatic dishwashing machine, the method comprising:
applying the automatic dishwashing composition of claim 1 to the item.
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