CN108949394B - Concentrated liquid detergent composition substantially free of solubilizer - Google Patents
Concentrated liquid detergent composition substantially free of solubilizer Download PDFInfo
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- CN108949394B CN108949394B CN201810923813.6A CN201810923813A CN108949394B CN 108949394 B CN108949394 B CN 108949394B CN 201810923813 A CN201810923813 A CN 201810923813A CN 108949394 B CN108949394 B CN 108949394B
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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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
Abstract
The invention disclosesA concentrated liquid detergent composition substantially free of solubilizer. The composite material comprises the following components in percentage by weight:
Description
Technical Field
The invention belongs to the technical field of daily chemical industry, and particularly relates to a concentrated liquid detergent composition basically free of a solubilizer.
Background
At present, concentrated liquid detergent compositions have the advantages of convenient use, suitability for mechanical washing processes and the like, and have flexible formula, simple process, energy conservation and environmental protection, and can effectively control and reduce the storage, packaging and transportation costs, so the concentrated liquid detergent compositions are more and more paid attention by consumers, manufacturers and retailers.
It is known that surfactants in aqueous solvents change phase with increasing concentration, resulting in liquid crystalline phases with high viscosity and difficult dispersion. Furthermore, concentrated liquid detergent compositions have a high content of surfactant active and are prone to gelling problems, resulting in difficulty in dispersing into a uniform product during production, and the product is prone to instability due to delamination during storage, and is also prone to high viscosity, difficult to pour, and slow in dissolution rate, which seriously affects the ease of use, and therefore the problem to be solved by concentrated detergents is to prevent the formation of surfactant gels. It is known in the art to prevent gelation by adding solubilizers to the product to change the morphology of the surfactant micelles, which leads to the formation of more fluid, more soluble spherical or rod-like micelles from the liquid crystalline phase.
Typical solubilizers include organic solvents such as ethanol, propylene glycol, dipropylene glycol n-butyl ether, ethoxylated benzyl alcohol, etc., as well as co-solvents; the cosolvent is short-chain alkylbenzene sulfonate, such as sodium p-toluenesulfonate and sodium cumene sulfonate. The solubilization effect of the small-molecule alcohol solvent is the most remarkable, but the potential safety hazard is large due to the low flash point of the small-molecule alcohol solvent. For example, chinese patent CN103275829A discloses a super-concentrated laundry detergent without solvent, which uses sodium xylene sulfonate or sodium cumene sulfonate as solubilizer to obtain a concentrated product with high stability; in a compact liquid laundry detergent composition disclosed in chinese patent CN107667165A, the solubilizer is 5-40% alcohol; in the detergent composition disclosed in chinese patent CN102549133B, not only a large amount of alcohol solvent is used, but also 1-6% of amino alcohol gel breaker is included.
However, the above-mentioned solubilizing agents cannot provide other efficacy points to the composition in addition to being able to inhibit the formation of gel states. As is known, the solubilizing agents themselves have small direct decontamination effect, cannot improve the washing efficiency, have no remarkable effect on inhibiting foams, color care, fabric care and the like, but have high dosage and cost, remarkably increase the formula cost and reduce the cost performance of products.
Therefore, in concentrated liquid detergent products, there is an urgent need to solve the technical problem that the auxiliary not only can destroy and inhibit the formation of the surfactant gel state, but also can provide other beneficial efficacy points, thereby ensuring that the composition has higher storage stability and excellent washing function.
Disclosure of Invention
It is an object of the present invention to provide a concentrated liquid detergent composition substantially free of solubilising agents which effectively overcomes the disadvantages of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a concentrated liquid detergent composition substantially free of solubiliser and consisting of, in weight percent:
wherein the number average molecular weight of the polyetheramine is less than 3000; the number average molecular weight of the aryl polymer is 1000-20000; the mass ratio of the polyether amine to the aryl polymer is 10: 1-1: 4.
Preferably, the mass ratio of the polyether amine to the aryl polymer is 8: 1-1: 1.8.
Preferably, the sum of the weight percentages of the polyether amine and the aryl polymer is 0.2-5%.
Preferably, the number average molecular weight of the polyether amine is 200 to 1500.
Preferably, the aryl polymer is an aryl polymer having an aryl group in a main chain and/or a side chain; the aryl group includes phenyl.
Preferably, the aryl polymer having an aryl group in the main chain is a polyester polymer and has the following general formula: A-B-C, wherein: a and C are residues of polyethylene glycol, polypropylene glycol or ethylene glycol/propylene glycol copolymer, and the molecular weight ranges of A and C are 400-10000; b is a polyester polymer residue formed by terephthalic acid, 5-sulfonyl-isophthalic acid or both and ethylene glycol or propylene glycol, and the molecular weight range of B is 400-10000; the B and the A are connected with the B and the C through ester groups; the aryl polymer with the side chain containing aryl is a modified styrene polymer.
Preferably, the surfactant system comprises at least one surfactant selected from the group consisting of: fatty acid salts, anionic surfactants, cationic surfactants, nonionic surfactants, and zwitterionic surfactants.
Preferably, the weight percentage of the surfactant system in the composition is 30-50%; the surfactant is composed of 0-10% of fatty acid salt, 1-30% of anionic surfactant, 1-40% of nonionic surfactant, 0-30% of zwitterionic surfactant and 0-30% of cationic surfactant.
Preferably, the detergency builders and additives comprise at least one material selected from the group consisting of: enzyme preparation, alkaline agent, pH regulator, viscosity regulator, preservative, colorant, fluorescent whitening agent, color stabilizer and essence.
Preferably, the viscosity of the composition is in the range of 100-5000 cst, and the pH is in the range of 7.5-10.0.
According to the invention, by adding a compound system of the polyether amine and the aryl polymer in the product formula, the product has excellent storage stability, no gelation and delamination phenomena occur even if the product is stored for a long time, and the product also has excellent decontamination synergism.
Detailed Description
The technical features and advantages of the present invention will become apparent to those skilled in the art from a reading of the present disclosure.
All percentages, parts and ratios are based on the total weight of the composition of the present invention, unless otherwise specified. All weights as they pertain to listed ingredients are assigned to levels of active material and, therefore, do not include solvents or by-products that may be included in commercially available materials, unless otherwise specified. The term "weight content" herein may be represented by the symbol "%".
All formulations and tests herein occur at 25 ℃ environment, unless otherwise indicated.
The use of "including," "comprising," "containing," "having," or other variations thereof herein, is meant to encompass non-inclusive inclusions, as well as non-exclusive distinctions between the terms. The term "comprising" means that other steps and ingredients can be added that do not affect the end result. The term "comprising" also includes the terms "consisting of …" and "consisting essentially of …". The compositions and methods/processes of the present invention can comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein.
The detergent compositions of the present invention are substantially free of a solubilizer. The term "substantially free" means that no solubilizing agent is artificially added to the formulated detergent compositions of the present invention or that the solubilizing agent content of the compositions is less than 1%. It is well known in the art that certain materials of detergent compositions contain certain amounts of solvents or residual monomers, such as propylene glycol, ethylene glycol, ethanol, etc., which may be introduced into the composition when formulated. The term "substantially free" means that the solubilizer content of the composition is less than 1%.
The concentrated liquid detergent composition which is basically free of solubilizer comprises the following components in percentage by weight:
wherein:
1. polyether amine (PEA)
In the invention, the polyether amine is a polymer with a main chain of a polyether structure and active functional groups at the tail ends of all or part of amine groups. Polyetheramines are generally obtained by ammoniation of polyethers, such as polyethylene glycol, polypropylene glycol or ethylene glycol/propylene glycol copolymers, glycerol/propylene glycol copolymers, etc., at elevated temperatures and pressures. It is well known in the art that linear polyetheramines (e.g., D-230) can stabilize fragrances in laundry detergents and provide longer lasting fragrances. And high molecular weight (higher than 1000), branched chain type, trifunctional polyether amine (T-5000) can inhibit foaming of liquid detergent in use. The polyetheramines currently commercially available include mono-, di-and tri-amino polyetheramines, a range of products having a molecular weight of 230 to 5000, such as those produced by Huntsman corporation, usa
M-2070, D-230, D-400, T-403 and the like which are commercial products.
In the concentrated liquid detergent composition, the polyether amine accounts for 0.1-10 wt% of the detergent composition, and the number average molecular weight of the polyether amine is less than 3000, and more preferably 200-1500.
2. Aryl polymers
In the invention, the aryl polymer refers to a polymer which contains aryl in a main chain and/or a side chain, and the number average molecular weight of the aryl polymer is 1000-20000, wherein the aryl is preferably phenyl. Wherein the polymer having an aromatic group in the main chain is mainly a polyester polymer, and the polymer having an aromatic group in the side chain is mainly a modified styrene polymer.
1) Polyester polymer
Polyester polymer refers to a compound having a structure represented by the following general formula: A-B-C.
Wherein: a and C are residues of polyethylene glycol, polypropylene glycol or ethylene glycol/propylene glycol copolymer, and the molecular weight ranges of A and C are 400-10000; b is a polyester polymer residue formed by terephthalic acid, 5-sulfonyl-isophthalic acid or both and ethylene glycol or propylene glycol, and the molecular weight range of B is 400-10000; and B and A as well as B and C are connected by ester groups.
It is well known in the art that polyester polymers, such as the above-mentioned polyester polyether block copolymers, adsorb on oily or particulate soils through hydrophobic polyester blocks during washing, and that hydrophilic blocks extend into water, thereby rendering the soils hydrophilic, achieving improved detergency of the detergent, and preventing soil redeposition. Detergent compositions built with polyester polymers generally have excellent soil release from oily and particulate soils, with soil release significantly better than detergent compositions with higher levels of surfactant. Suitable polyester polymers include the Rebel-o-tex series of polymers from Rhodia, such as SF-2, and/or the Texcare series of polymers from Clariant, such as SRA300, SRA 100.
2) Modified styrene polymer
Modified styrene polymers are polymers obtained by copolymerizing styrene with monomers containing hydrophilic groups, to improve the water solubility of the styrene polymers, for example under the trade name
Series 725, 747, etc. It is well known in the art that acrylic modified styrene polymers can also inhibit metal corrosion, inhibit soap scum deposition, provide protection of dishware, prevent yellowing and whitening of fabricsThe beneficial effect of degree maintenance.
In the concentrated liquid detergent composition, the aryl polymer accounts for 0.1-10 wt% of the detergent composition, and the mass ratio of the polyether amine to the aryl polymer in the detergent composition is 10: 1-1: 4, preferably 8: 1-1: 1.8. In the present invention, the sum of the weight percentages of the polyether amine and the aryl polymer is preferably 0.2 to 5%.
3. Surfactant system
The surfactant system comprises at least one surfactant selected from the group consisting of: fatty acid salts, anionic surfactants, cationic surfactants, nonionic surfactants, and zwitterionic surfactants. The weight percentage of the surfactant system in the composition is preferably 30-50%. Further, the surfactant is preferably composed of 0-10% of fatty acid salt, 1-30% of anionic surfactant, 1-40% of nonionic surfactant, 0-30% of zwitterionic surfactant and 0-30% of cationic surfactant.
1) Fatty acid salts
Fatty acid, which refers to an organic substance having a carboxyl group at one end and an aliphatic hydrocarbon chain, includes saturated fatty acid salts and unsaturated fatty acid salts. The fatty acid salt is formed by alkaline saponification of fatty acid. Commonly used alkaline agents are sodium hydroxide and potassium hydroxide. The saturated fatty acid salt is a fatty acid salt containing no carbon-carbon double bond. One or more selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and arachidic acid. The unsaturated fatty acid salt is a fatty acid salt containing one or more carbon-carbon double bonds. Depending on the number of double bonds, they can be classified into monounsaturated fatty acids having one double bond and polyunsaturated fatty acids having a plurality of double bonds. The monounsaturated fatty acid is oleic acid, and the polyunsaturated fatty acid is linoleic acid, linolenic acid, arachidonic acid, etc.
In the liquid detergent composition according to the present invention, the fatty acid salt is preferably contained in an amount of 0.1 to 10% by weight, more preferably 0.5 to 5.0% by weight, based on the weight of the detergent composition.
In the liquid detergent composition of the present invention, the fatty acid salt is one or more selected from alkali metal salts of fatty acids having 10 to 20 carbon atoms.
2) Anionic surfactants
In the present invention, the total weight of the mixture of anionic surfactants is 1% to 30%, preferably 1% to 10% of the total weight of the liquid detergent composition.
The anionic surfactant is selected from one or more of sulfonate surfactant, carboxylate surfactant and sulfate surfactant; preferably one or more of alkyl benzene sulfonate, alkyl sulfate of C8-C18, ethoxylated fatty alcohol sulfate of C8-C18, alpha-olefin sulfonate, fatty acid alkyl ester sulfonate and ethoxylated fatty alcohol ether carboxylate.
In some embodiments, the mixture of anionic surfactants preferably contains alkyl benzene sulfonates and derivatives thereof. The alkylbenzene sulfonate satisfies the following general formula:
wherein R is1Is an alkyl group having 6 to 24 carbon atoms, M+Is a cation. R1May be a straight-chain alkyl group or a branched-chain alkyl group; it may be a saturated alkyl group or an alkyl group having one or more unsaturated double bonds. More preferably R1Is a straight chain alkyl group having a carbon number of 8 to 18.
In some embodiments, the mixture of anionic surfactants contains ethoxylated fatty alcohol sulfates. Ethoxylated fatty alcohol sulfates are derivatives of ethoxylated fatty alcohols having the general formula:
wherein R is1Is an alkyl group having 6 to 24 carbon atoms; x is 0.5 to 30; wherein M is+Is a cation.R1May be a straight-chain alkyl group or a branched-chain alkyl group; it may be a saturated alkyl group or an alkyl group having one or more unsaturated double bonds. Preferably R1Is a straight chain alkyl group having a carbon number of 8 to 18. x represents an average degree of ethoxylation of from 0.5 to 30, preferably from 0.5 to 10, more preferably from 0.5 to 3.
In some embodiments, the alpha olefin sulfonate is present having the general formula:
wherein a is 0 to 2, wherein M+Is a cation, R1Is an alkyl group having 6 to 24 carbon atoms, preferably R1Is an alkyl group having 8 to 18 carbon atoms.
The anionic surfactant may also comprise one or more mixtures of sodium alkyldisulfonates or derivatives thereof, preferably sodium alkyldiphenyloxide disulfonates, a suitable example being the sodium salt of dodecyl diphenyloxide disulfonate. Fatty acid alkyl ester sulfate, preferably fatty acid Methyl Ester Sulfate (MES), preferably fatty acid having 8 to 18 carbon atoms, may also be contained. Sulfosuccinates, preferably fatty alcohol polyoxyethylene ether sulfosuccinic acid monoester disodium salt, preferably having a fatty alcohol carbon number of from 8 to 18, preferably having an average degree of ethoxylation of 2.0, may also be included.
In some embodiments, the mixture of anionic surfactants contains a fatty acid salt. The fatty acid salt is formed by alkaline structuring of fatty acid. The alkaline agent usually used is sodium hydroxide and/or potassium hydroxide. In the liquid detergent composition according to the present invention, the fatty acid salt is selected from metal salts of fatty acids having 10 to 20 carbon atoms, preferably linear alkyl fatty acids having 10 to 16 carbon atoms.
The cation of the above-mentioned anionic surfactant may be an alkali metal ion or an alkaline earth metal ion, and preferably a sodium ion.
3) Nonionic surfactant
In the present invention, the total weight of the mixture of nonionic surfactants is 1% to 40%, preferably from 1% to 20% of the total weight of the liquid detergent composition.
The nonionic surfactant is selected from one or more of fatty alcohol alkoxylates, alkyl polyglycosides, fatty acid alkoxylates, fatty acid ethoxylates, fatty acid alkylolamides and ethoxylated sorbitan esters.
In some embodiments, the nonionic surfactant mixture preferably contains a fatty alcohol alkoxylate having the general formula:
wherein n is 6 to 24; x is 0.5 to 30 and y is 0 to 10.
The fatty alcohol alkoxylate is a product of ring opening polymerization of fatty alcohol and alkylene oxide under the action of an alkaline catalyst, and therefore the fatty alcohol alkoxylate is a mixture. The fatty alcohol includes a straight chain alcohol or a branched chain isomeric alcohol. Alkoxy groups include ethoxy and propoxy groups. The fatty alcohol is preferably a fatty alcohol having a carbon number of 8 to 18, and the preferred alcohols include, but are not limited to, one of hexanol, octanol, decanol, 2-ethylhexanol, 3-propylheptanol, lauryl alcohol, isotridecyl alcohol, tridecyl alcohol, tetradecyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, and mixtures thereof. The average degree of ethoxylation x is preferably from 2 to 12. Preferred examples are the NEODOL series of linear fatty alcohol ethoxylates products from SHELL, the ECOSURFEH series of ethoxylated and propoxylated 2-ethylhexanols products from DOW, the Lutensol XL series of ethoxylated and propoxylated 3-propylheptanols products from BASF and the Lutensol XP series of ethoxylated 3-propylheptanols from BASF.
In some embodiments, the nonionic surfactant mixture preferably comprises an alkyl polyglycoside having the general formula:
wherein n is 6 to 24, p is 1.1 to 3, preferably n is 8 to 16. Suitable alkyl polyglycosides are for example the products of the Glucopon series of alkyl glycosides from BASF.
The nonionic surfactant mixture may contain fatty acid alkoxylates, preferably from ethoxylated C8 to C18 fatty acid esters, with an average degree of ethoxylation of from 2 to 10. May contain an ethoxylated alkyl sorbitan ester having an alkyl carbon number of from 6 to 18 and an average degree of ethoxylation of from 4 to 20; a suitable example is the Corda Tween series of products.
The nonionic surfactant mixture may contain fatty acid alkylolamides, the fatty acid having 6 to 24 carbon atoms, may be a linear fatty acid, may be a branched fatty acid, may be a saturated fatty acid, and may be an unsaturated fatty acid; the alkyl alcohol number is 0 to 2. Monoethanolamide, diethanolamide, isopropanolamide of fatty acids having a carbon number of 8 to 18 are preferred, a suitable example being coconut diethanolamide.
The nonionic surfactant mixture may contain fatty acid methyl ester ethoxylates of the general formula:
wherein n is 6 to 24; x is 2 to 20, preferably n is 8 to 18, x is 0.5 to 30. Preferably x is 4 to 10.
The nonionic surfactant mixture may contain a polyether surfactant. The polyether surfactant is a polymer, a nonionic surfactant containing ethylene oxide and/or propylene oxide repeating units, suitable examples being the Pluronic series from BASF.
4) Zwitterionic surfactants
The zwitterionic surfactant is selected from one or more of amino acid type surfactant, amine oxide type surfactant, betaine type surfactant and imidazoline type surfactant; including but not limited to: alkyl betaines, fatty amidobetaines, fatty amidopropyl betaines, fatty amidopropyl hydroxypropyl sulfobetaines, including sodium alkyl acetate type imidazolines, fatty acid type imidazolines, sulfonic acid type imidazolines; aminopropionic acid derivatives, glycine derivatives; alkyl dimethyl amine oxide, fatty amidopropyl dimethyl amine oxide, and the like.
5) Cationic surfactant
The cationic surfactant comprises quaternary ammonium salt surfactant, heterocyclic surfactant and polymer cationic surfactant. The method comprises the following steps: mono-long linear quaternary ammonium salts, bi-long linear quaternary ammonium salts, benzyl quaternary ammonium salts, hydroxyalkyl quaternary ammonium salts, fatty amidopropyl hydroxyalkyl quaternary ammonium salts, and polyquaternary ammonium salts obtained by copolymerizing vinyl pyrrolidone and unsaturated amides or unsaturated quaternary ammonium salts.
4. Detergent builders and additives
4.1 detergent builder
The liquid detergent compositions to which the present invention relates may comprise detergency builders selected from the group consisting of enzyme preparations and stabilisers therefor, bleaching systems, anti-redeposition agents, functional polymers, chelants and optical brighteners.
4.1.1 enzyme formulations and stabilizers therefor
The detergent compositions to which the present invention relates may comprise one or more enzyme preparations to provide cleaning performance, fabric care and/or other benefits. The enzyme preparation is selected from the group consisting of: proteases, alpha-amylases, cellulases, hemicellulases, phospholipases, esterases, lipases, peroxidases/oxidases, pectinases, lyases, mannanases, cutinases, reductases, xylanases, pullulanases, tannases, pentosanases, maltoglucanases, arabinases, beta-glucanases. Commonly used enzyme preparations are proteases, amylases, lipases, cutinases and/or cellulases. The enzyme preparation is present at a level of from 0.001% to 5%, preferably from 0.01% to 2% of the detergent composition.
The detergent compositions of the present invention may comprise from 0.001% to 10% by weight of the composition of an enzyme stabilising system. The enzyme stabilizing system is compatible with detergent compositions and may comprise one of calcium ions, boric acid, borax, propylene glycol, glycerol, polyols and mixtures thereof. The weight and amount of the enzyme stabilizing system will vary depending on the form and composition of the detergent composition and the type of enzyme preparation.
4.1.2 bleaching System
The liquid detergent compositions to which the present invention relates may comprise a bleach system. The bleaching system comprises hypohalite bleaching agent, peroxide bleaching agent. Peroxides typically comprise a source of hydrogen peroxide and a bleach activation system. Sources of hydrogen peroxide include, but are not limited to, perborates, persulfates, and mixtures thereof. The bleaching system may comprise a bleach activator for promoting rapid decomposition of peroxide at lower temperatures to generate oxygen selected from the group consisting of: tetraacetylethylenediamine, benzoyl caprolactam, 4-nitrobenzoyl caprolactam, 3-chlorobenzoyl caprolactam, benzoyloxybenzene sulfonate, nonanoyloxybenzene sulfonate, phenyl benzoate, decanoyloxybenzene sulfonate, benzoyl valerolactam, octanoyloxybenzene sulfonate and transition metal bleaching catalysts.
The liquid detergent composition of the present invention may further contain a reactive oxygen species stabilizer for adjusting the rate of generation of hydrogen peroxide by decomposition of the peroxide so that the local concentration of hydrogen peroxide is not too high, and examples thereof include polyfunctional organic phosphoric acids such as hydroxyethylidene diphosphate and ethylenediaminetermethylene phosphate. In some embodiments, the bleaching system is present at a level of from 0.01% to 30%, preferably from 0.01% to 20%, more preferably from 0.01% to 10% by weight of the total liquid detergent composition.
4.1.3 anti-redeposition Agents
The liquid detergent composition according to the present invention may contain an antiredeposition agent from the viewpoint of effectively improving the washing effect. The anti-redeposition agent includes, but is not limited to, the group consisting of: cellulose derivatives such as carboxymethyl cellulose, ethyl hydroxyethyl cellulose, methyl cellulose; homopolymers and copolymers of vinylpyrrolidone, such as linear polyvinylpyrrolidone, copolymers of vinylpyrrolidone and vinyl acetate, copolymers of vinylpyrrolidone and vinylimidazole; polycarboxylates, for example polyacrylates, polyacrylic polymaleic acid copolymers, acrylic acid-acrylate-sulfonate copolymers. The antiredeposition agent is present in the liquid detergent composition at a level of from 0.01% to 5%, preferably from 0.01% to 2%.
4.1.4 functional polymers
The detergent compositions to which the present invention relates may comprise amphiphilic alkoxylated grease cleaning polymers having balanced hydrophilic and hydrophobic properties such that they remove grease particles from fabric surfaces or hard surfaces. One class of embodiments of the amphiphilic alkoxylated grease cleaning polymers is that they contain one or more core structures, which may be, but are not limited to, ethylenediamine, triethylenetetramine, tetraethylenepentamine, etc., having a molecular formula H, and a plurality of alkoxylated groups attached to the core structure2N(C2H4NH)nH, linear polyamine structures or star-shaped polyethyleneimines, the alkoxylated groups of which can be, but are not limited to, polyoxyethylene groups, polyoxypropylene groups and/or their block and/or random copolymeric groups.
In the liquid detergent composition, the content of the amphiphilic alkoxylated grease cleaning polymer in the liquid detergent composition is 0-10.0 wt%, preferably 0.1-5.0 wt%, and more preferably 0.5-2.0 wt%.
The detergent compositions of the present invention may comprise carboxylate polymers and/or modified carboxylate polymers to enhance the grease removal capacity of the compositions. Including carboxylate polymers which may be polyacrylate homopolymers or random copolymers of maleates/acrylates, and alkoxylated polycarboxylates, i.e., polyacrylates containing polyoxyethylene side chains. The molecular weight is typically between about 2000 and about 50000. In the liquid detergent composition, the weight percentage content of the carboxylate polymer and/or the modified carboxylate polymer in the liquid detergent composition is 0-10.0%, preferably 0.1-5.0%, and more preferably 0.5-2.0%.
The detergent compositions of the present invention may comprise polycarboxylates and/or modified polycarboxylates to enhance the cleaning of particulate soils and to inhibit the formation of limescale in the compositions. Including water-soluble salts of homopolymers and copolymers polymerized from one or more double bond-containing aliphatic carboxylic acid monomers including, but not limited to, acrylic acid, methacrylic acid, maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid, and methylenemalonic acid. The modified polycarboxylate has a polyoxyethylene group or an alkyl group in a side chain. The molecular weight is typically between about 2000 and about 10000. In the liquid detergent composition, the weight percentage of the polycarboxylate and/or the modified polycarboxylate in the liquid detergent composition is 0-10.0%, preferably 0.1-5.0%, and more preferably 0.5-2.0%.
4.1.5 chelating agents
The liquid detergent compositions of the present invention may comprise one or more metal ion sequestrants including copper, iron and/or manganese sequestrants and mixtures thereof. These chelating agents can reduce the concentration of free metal ions in the liquid detergent, thereby reducing the inactivation of enzyme preparations by these metal ions, the catalytic decomposition of other components, and the like. Useful chelating agents include aminocarboxylates, aminophosphonates, and the like, including but not limited to Ethylenediaminetetraacetate (EDTA), Nitrilotriacetate (NTA), Diethylenetriaminepentaacetate (DTPA), alanine diacetate (MGDA), glutamic acid diacetate (GLDA), and/or ethylenediaminetetra (methylene phosphate) (EDTMPA), aminotri (methylene phosphate) (ATMP), diethylenetriaminepenta (methylene phosphate) (DTPMP), hydroxy-ethane diphosphonate (HEDP), and ethylenediamine disuccinate (EDDS), and mixtures thereof. In the liquid detergent composition, the content of the chelating agent in the liquid detergent composition is 0-20.0 wt%, preferably 0.1-5.0 wt%, and more preferably 0.5-2.0 wt%.
4.1.6 fluorescent whitening agents
The use of optical brighteners in liquid detergent compositions is well known in the art and commercially available optical brighteners are abundant. Optical brighteners are present in the form of their alkali metal salts (mostly sodium salts). Preferred optical brighteners include, but are not limited to: distyrylbiphenyl compounds. A suitable example is 4,4' -bis (2-sodium sulfonate styryl) biphenyl, such as the product of the BASF company under the CBS-X brand. The fluorescent whitening agents are used in amounts of 0.01% to 2% by weight, preferably 0.01% to 0.1% of the total composition.
In the liquid detergent composition, the fluorescent whitening agent is 0.01-2.00 wt%, preferably 0.05-1.00 wt%, and more preferably 0.05-0.50 wt% of the liquid detergent composition.
4.2 additives
The present invention relates to liquid detergent compositions comprising the following optional additives: one or more of alkaline agent, viscosity regulator, preservative, colorant, color stabilizer and essence.
The liquid detergent compositions to which the present invention relates may comprise one or more alkaline agents selected from the group consisting of sodium hydroxide, potassium hydroxide, alkali metal carbonates, alkali metal silicates. The content of the alkaline agent in the liquid detergent composition is 0.01-30.0 wt%, preferably 0.05-10.0 wt%, and more preferably 0.05-5.0 wt%.
The liquid detergent compositions to which the present invention relates may comprise one or more viscosity modifiers to provide suitable viscosity. Suitable viscosity modifiers are, for example, salts, polysaccharides, gums, short-chain fatty alcohols, short-chain fatty alcohol alkyl ethers. Suitable examples are sodium chloride, sodium formate, sodium acetate, ethanol, propylene glycol, sodium citrate, alkyl hydroxyalkyl cellulose ethers, carrageenan, xanthan gum, polyacrylamide derivatives. The weight percentage content of the viscosity regulator in the liquid detergent composition is 0.01-30.0%, preferably 0.05-10.0%, and more preferably 0.05-5.0%.
In some embodiments, the liquid detergent compositions contemplated by the present invention preferably comprise preservatives, suitable examples being phenoxyalcohols, sodium benzoate; isothiazolinone and its derivatives, such as methyl isothiazolinone, methyl chloro isothiazolinone, benzisothiazolinone or their mixture. The amount of the preservative is 0.001% to 5%, preferably 0.01% to 2%.
The liquid detergent compositions of the present invention have a dynamic viscosity in the range of from 10cst to 15000cst, more preferably from 50cst to 5000cst, and even more preferably from 200cst to 5000 cst. The pH of the liquid detergent composition of the present invention is 7.5 to 10.0, and is preferably selected from the range of pH8.0 to 9.0.
A concentrated liquid detergent composition substantially free of solubilizer as described herein can be prepared by a variety of methods well known to those skilled in the art. The formulation of the composition may be carried out by conventional means, and the appropriate processing temperature and processing time will be selected with reference to the state and effect of the components in solution, and the stability of the components.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following examples are intended to further describe and demonstrate embodiments within the scope of the present invention. The examples are therefore to be understood as merely illustrative of the invention in more detail and not as limiting the content of the invention in any way.
In the following examples, the preparation process of the present invention comprises the following steps:
1) adding a part of deionized water and alkali into the preparation tank;
2) starting stirring, heating to 60 ℃, heating and saponifying fatty acid into fatty acid salt under an alkaline condition, and stirring until the fatty acid salt is completely dissolved;
3) sequentially adding an anionic surfactant, a nonionic surfactant and an amphoteric surfactant, and stirring until the anionic surfactant, the nonionic surfactant and the amphoteric surfactant are completely dissolved;
4) stopping heating, adding the rest deionized water into the preparation tank, and cooling to below 40 ℃;
5) adding polyether amine and/or aryl polymer, and stirring uniformly;
6) adjusting the pH value;
7) adding additives such as antiseptic, stirring to dissolve completely;
8) the viscosity is adjusted.
In the following examples, all amounts are by weight unless otherwise indicated, and the amounts of the listed ingredients are converted to active material amounts.
In the examples, the following abbreviations will be used and have the indicated functions.
KOH: neutralizing fatty acid with potassium hydroxide, saponifying to obtain fatty acid salt and alkali agent.
NaOH: sodium hydroxide, neutralizing fatty acid, saponifying to obtain fatty acid salt and alkali agent.
Liquid caustic soda: sodium hydroxide water solution containing 32% of sodium hydroxide by mass, neutralizing fatty acid and saponifying to prepare fatty acid salt and/or neutralizing LAS, alkali agent.
And (3) LAS: the linear alkyl benzene sulfonic acid sodium salt contains 10-13 carbon atoms and an anionic surfactant.
AOS: alpha-olefin sulfonate, anionic surfactant.
AES: ethoxylated fatty alcohol sulfate, wherein the number of carbon atoms of fatty alcohol is 12-14, the average ethoxylation degree is 2, and the anionic surfactant is used as the surfactant.
K12: sodium lauryl sulfate, anionic surfactant.
MES: fatty acid methyl ester sulfate, wherein the carbon atom number of the fatty acid is 8-18, and an anionic surfactant.
AEO 7: ethoxylated fatty alcohol, average degree of ethoxylation 7, nonionic surfactant.
AEO 9: ethoxylated fatty alcohol, average degree of ethoxylation 9, nonionic surfactant.
TO-7: ethoxylated isomeric tridecanol, average degree of ethoxylation of 7, nonionic surfactant.
XP-80: ethoxylated 2-propylheptanol, average degree of ethoxylation of 8, nonionic surfactant.
XL-80: ethoxylated and propoxylated 2-propylheptanol, average degree of ethoxylation of 8, a non-ionic surfactant.
MEE: fatty acid methyl ester ethoxylate, wherein the number of carbon atoms of fatty acid is 6-24, the average ethoxylation degree is 0.5-30, and the nonionic surfactant is used.
EPEI: polyethyleneimine (MW 600) with 20 ethoxylate groups per NH, polyester soil release polymer.
PE 3100: polyethylene glycol anda polypropylene glycol-segmented copolymer having a polypropylene glycol block molecular weight of 950 and a polyethylene glycol monomer molecule number of 10% of the total polymer monomer molecule number, produced by BASF corporation
PE3100。
Polyether amine: amino-terminated propylene oxide, produced by Huntsman corporation, usa
M-2070, D-230, D-400, T-403, T5000 and the like which are commercial products, wherein M2070 is monoamino end capping and has the molecular weight of 2000; d230 is a diamine end-capping, molecular weight 230; d400 is a diamine end-capping, molecular weight 430; t403 is triamino terminated and has a molecular weight of 440; t5000 is triamino-terminated and has a molecular weight of 5000.
Protease: alkaline protease, a product of Novozymes corporation under the trademark Savinase Ultra 16 XL.
Enzyme stabilizer: consists of 20 percent of borax, 50 percent of glycerin and 30 percent of citric acid which account for the weight of the enzyme stabilizer.
Whitening agent: 4,4' -bis (2-sodium sulfonate styryl) biphenyl, an optical brightener, a product of BASF corporation, under the designation CBS-X.
Preservative: a mixture of methylisothiazolinone and chloromethylisothiazolinone.
Storage stability test
High-temperature stability: after the composition is bottled and sealed, the composition is placed in an environment with the temperature of 45 +/-1 ℃, and after the composition is placed at a constant temperature for 1 month, the temperature is restored to 25 +/-5 ℃ at room temperature, the composition does not delaminate or precipitate, and the high-temperature stability is qualified.
Low-temperature stability: the composition is bottled, sealed, placed in an environment of-0 + -2 deg.C, placed at constant temperature for 1 month, taken out and immediately observed. The composition has no demixing or precipitation separation, and is qualified in low-temperature stability.
Freeze-thaw cycle stability: placing the mixture in an environment with the temperature of between 15 ℃ below zero and 20 ℃ below zero, taking the mixture out after placing the mixture for 24 hours at constant temperature, and placing the mixture in an environment with the temperature of 25 +/-5 ℃ for 24 hours as a cycle for one time and for four times continuously, wherein the state of the composition is observed every time. The composition has no demixing or precipitation separation, and the freeze-thaw cycle stability of the composition is qualified at the temperature of 25 +/-5 ℃ before and after storage.
And (3) normal temperature stability: after the composition is bottled and sealed, the composition is placed in a room temperature environment, and after the composition is placed for 1 month, the composition has no layering or precipitation, and is qualified in stability at normal temperature.
Generally, if the four stability test results are all qualified, the stability test result is qualified; any one or more of which are failures, the stability test result is considered to be "failed".
Viscosity measurement
The viscosity is determined with a Brookfield model LVDV-II + Pro digital viscometer. After placing the sample in a 250mL beaker, the sample was placed in a thermostatic bath, and the temperature of the sample was controlled to a prescribed temperature (25 ℃ C. + -0.5 ℃ C.) and thermostated for 30 minutes. And selecting a rotor with a proper model to measure the viscosity of the sample according to the operation requirement of the instrument.
Table 1 detergent compositions examples 1-4
And (3) analysis:
first, composition I of comparative example 5 did not inhibit gel generation by any method, and thus the composition was not only high in viscosity but also opaque in appearance and poor in storage stability. In each of examples 1 to 4, an aryl polymer (polyester polymer, SRA100) was added and a polyether amine (composition A: D230; composition B: T403; composition C: M2070; composition D: D400) was formulated, and the pH of the compositions was 8.0 to 8.5. The results show that the polyetheramines of the examples all reduce the viscosity of the compositions and ensure their storage stability and also their clear and transparent appearance.
Comparative examples 1 to 3, however, use aryl polymers compounded with high molecular weight polyetheramines (T5000, composition E), polyethers (EOPO block copolymer, PE3100, composition F) or alcohol ether solvents (dipropylene glycol n-butyl ether, DPnB, composition G) in higher amounts than the polyether amines of the examples. Although the polyether amine, polyether and alcohol ether solvents of the comparative examples can also reduce the viscosity of the composition, the storage stability of the composition cannot be guaranteed and the composition may delaminate upon standing at normal temperature. The composition H of the comparative example 4 also has better stability, transparent appearance and lower viscosity, but the cost is higher due to the adoption of a method of compounding the alcohol solvent (propylene glycol) and the benzene sulfonic acid solubilizer (sodium p-toluenesulfonate).
Table 2 detergent compositions examples 5-8
And (3) analysis:
the results in table 2 show that composition N without the addition of an aryl polymer and a polyetheramine, composition O with the addition of only a polyetheramine (D400), and composition P with the addition of only an aryl polymer do not ensure the storage stability of the compositions, and that the compositions are significantly delaminated upon storage at room temperature. After the aryl polymer (modified styrene polymer) and the polyether amine (D400) are compounded, a stable and transparent composition can be obtained, and the viscosity of the composition is gradually reduced along with the increase of the addition amount of the aryl polymer and the polyether amine.
Dissolution Rate test
In 150ml baked cake, B620 type magneton is put in, 20g sample is weighed, 80g deionized water is slowly injected, stirring is started at 300r/min by an electric stirrer, and simultaneously a timer is started to record the time required for complete dissolution (namely, the solution is clear and transparent).
TABLE 3 detergent compositions examples 9-10
And (3) analysis:
from the results in Table 3, it is shown that the dissolution rates of composition Q of example 9 and composition S of example 10, both formulated with polyetheramine and an aryl polymer, are significantly improved, and the dissolution rate of composition S is comparable to that of composition U, but composition U is added with a large amount of solubilizer, relative to composition R of comparative example 9 and composition T of comparative example 10.
Actual stain detergency test
1) Testing cloth: the polyester white cloth (GB/T7568.4, purchased by technical supervision of textile industry in Shanghai) was cut into square test cloths of 6X 6 cm.
2)250ppm of washing water: the washing water with the hardness of 250ppm is prepared according to the requirements of GB/T13174-2008, wherein the ratio of calcium ions to magnesium ions is 3: 2.
3) Testing cloth pollution: common actual stains are represented by oil stains of chili oil of Laoganma and oil stains of mixed oil of goldfish, and are used as experimental stains. 0.2g of oil stain is taken and smeared on test cloth and aged for 4 hours at room temperature.
Greasy dirt of capsicum oil of Laoganma: only the upper layer of greasy dirt liquid is taken from the oil pepper of the Tao Huabi Laoganma sold in the market.
Oil stain of the goldfish blend oil: 200g of blend oil and 0.02g of Sudan red pigment are accurately weighed and placed in a water bath at 45 ℃ to ensure that the Sudan red is completely dissolved in the blend oil, thereby preparing colored stains.
4) And (3) testing the decontamination performance: the washing test was performed with reference to GB/T13174-2008. And (3) firstly, washing the eight pieces of test cloth by using a detergent, and airing at room temperature after washing. And then, the four pieces of the dried test cloth are polluted by oil pollution of the aged autumnal chili oil, and the four pieces of the test cloth are polluted by oil pollution of the goldfish blend oil. After staining, the stained cloth was aged at room temperature for 4 hours and tested for whiteness W1 before washing with a WSD-3U fluorescent whiteness meter. Eight soiled test cloths were then washed with detergent. After washing, the fabric was dried at room temperature and tested for whiteness W2 after washing.
Cleaning ability (whiteness after washing test cloth (W2) — whiteness before washing test cloth (W1))/number of test cloths
It is clear that the greater the difference in whiteness, the higher the detergency.
The washing conditions were: 250ppm of washing water and 2g of detergent are added into each cylinder, the washing time is 20 minutes, the washing temperature is 30 ℃, and the stirring speed is 60 r/min.
Table 4 detergent compositions examples 11-13
TABLE 5 detergency of detergent compositions V to Y against actual stains
The results in the table show that in the detergency of two actual stains, examples 11 to 13 show more excellent detergency, and that the complex formulation of the aryl polymer and the polyether amine can have more remarkable detergency improving capability.
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Unless otherwise stated, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".
All documents cited in the summary of the invention are incorporated herein by reference in the relevant part. The citation of any document is not to be construed as an admission that it is prior art with respect to the present invention.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, so that any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (7)
1. A concentrated liquid detergent composition substantially free of solubilising agents, characterised in that it comprises, in weight%:
wherein the number average molecular weight of the polyetheramine is less than 3000; the number average molecular weight of the aryl polymer is 1000-20000; the mass ratio of the polyether amine to the aryl polymer is 10: 1-1: 4;
the solubilizer comprises an organic solvent and a cosolvent, wherein the cosolvent is short-chain alkyl benzene sulfonate;
by "substantially free" is meant that no solubilizing agent is added by man or that the level of solubilizing agent in the detergent composition is less than 1%.
2. A concentrated liquid detergent composition substantially free of solubilizer as claimed in claim 1 wherein the mass ratio of polyether amine to aryl polymer is 8:1 to 1: 1.8.
3. A concentrated liquid detergent composition substantially free of solubilizer as claimed in claim 2 wherein the sum of the weight percentages of the polyetheramine and the aryl polymer is 0.2-5%.
4. A concentrated liquid detergent composition substantially free of solubilizer as claimed in claims 1 to 3 wherein the polyether amine has a number average molecular weight of 200 to 1500.
5. A concentrated liquid detergent composition substantially free of solubilizer as set forth in claim 1,
the weight percentage of the surfactant system in the composition is 30-50%;
the surfactant is composed of 0-10% of fatty acid salt, 1-30% of anionic surfactant, 1-40% of nonionic surfactant, 0-30% of zwitterionic surfactant and 0-30% of cationic surfactant.
6. A concentrated liquid detergent composition substantially free of solubilizer as claimed in claim 1 wherein the detergency builder and additive comprise at least one member selected from the group consisting of: enzyme preparation, alkaline agent, pH regulator, viscosity regulator, preservative, colorant, fluorescent whitening agent, color stabilizer and essence.
7. A concentrated liquid detergent composition substantially free of solubilizer as claimed in claim 1, wherein the viscosity of the composition is in the range of 100 to 5000cst and the pH is in the range of 7.5 to 10.0.
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