Summary of the invention
The object of the present invention is to provide a kind of composition of external structurant system, the composition has higher structuring
That is, under the same conditions performance has better suspending power.
It is a further object to provide the method for preparing external structurant system, this method can guarantee 12- hydroxyl
Base-stearic acid triglycerides crystal habit, i.e. the offer higher suspending power of detergent composition.
It is also another object of the present invention to provide the detergent and preparation method thereof containing said external structuring system, should
Method, which prepares composition, has higher stability that is, after addition insoluble particulates with higher suspending power.
The present invention relates to a kind of external structurant system combination for liquid detergent, by accounting for total composition
Weight percent meter, the external structurant system combination is to be made of the following components:
A) 0.01%~5% 12- hydroxyl-stearic acid triglycerides;
B) 0.01%~5% alkyl aryl sulphonic acid solubilizer, each alkane chain in the alkyl aryl sulphonic acid solubilizer
Carbon atom number is less than 5;
C) 5%~60% surfactant, the surfactant is anionic surfactant, non-ionic surface is living
Property agent, one kind of zwitterionic surfactant or its a variety of mixture;
D) 0.01%~5% pH stabilizer;
E) water of surplus.
External structurant system combination of the present invention, the alkyl aryl sulphonic acid solubilizer are p-methyl benzenesulfonic acid
One of sodium, sodium xylene sulfonate, cumene sodium sulfonate or a variety of mixtures, more preferably 2,4- sodium xylene sulfonate.
External structurant system combination of the present invention, the anionic surfactant are the external structurant
At least the 80% of surfactant total weight in system.
External structurant system combination of the present invention, the anionic surfactant are linear alkyl benzene sulfonic acid
Sodium, alkyl contain 11~14 carbon atoms.
External structurant system combination of the present invention, preparation method are as follows:
Under stirring, water, alkyl aryl sulphonic acid solubilizer, surfactant, pH stabilizer are successively put into reaction kettle;To
After material is completely dissolved, the pH of material is adjusted to 6.0~9.5 with pH adjusting agent;80 DEG C~95 DEG C are again heated to, and under this
Condition stirring is until all 12- hydroxyl-stearic acid triglycerides emulsify completely;Then the mixture is quickly cooled to 60 again
DEG C~80 DEG C, and be kept at this temperature 5 minutes~300 minutes;Finally again slow cooling to room temperature,
The alkyl aryl sulphonic acid solubilizer feeds intake prior to 12- hydroxyl-stearic acid triglycerides, and molten in reaction kettle
Solution.
The liquid detergent of the system combination of the present invention containing external structurant, by the weight hundred for accounting for total composition
Divide than meter, the liquid detergent composition includes:
A) 0.5%~80% external structurant system combination;
B) 0.1%~80.0% surfactant, the surfactant are anionic surfactant, nonionic table
Face activating agent, one kind of zwitterionic surfactant or its a variety of mixture;
C) washing assisant of 0.01%-20%;
D) additive of 0.01%-20%;
E) solvent of surplus.
Furthermore, based on the weight percent for accounting for liquid detergent total amount, the liquid detergent includes:
A) 1%~50% external structurant system combination, uses of any of claims 1-5 be used for
The external structurant system combination of liquid detergent;
B) 5%~60.0% surfactant, the surfactant are anionic surfactant, non-ionic surface
Activating agent, one kind of zwitterionic surfactant or its a variety of mixture;
C) washing assisant of 0.1%-20.0%;
D) additive of 0.1%-20%;
D) solvent of surplus.
Furthermore, the washing assisant is selected from enzyme preparation and its stabilizer, pH stabilizer, pH adjusting agent, resists and sink again
Product agent, functional polymer, chelating agent and fluorescent whitening agent composition;
The additive be selected from alkaline agent, viscosity modifier, preservative, colorant, colour stabilizer and essence one kind or
The mixture of a variety of compositions;
The solvent is selected from one of water, glycerol, propylene glycol, ethyl alcohol or a variety of mixtures.
The liquid detergent of the system combination of the present invention containing external structurant, preparation process are as follows:
1) solvent, alkaline agent and surfactant are added into main preparing tank, stirring is complete to dissolving;
2) addition pH adjusting agent adjusts pH to 7~9;
3) external structurant system combination is added, stirring is until dispersion is complete;
4) washing assisant, additive, and supplementing solvent is added, stirs to being completely dissolved, appearance is uniform;
5) product quality parameters are adjusted, are stirred uniform to appearance.
The liquid detergent of the system combination of the present invention containing external structurant includes: fabric detergent compositions, hard
The detergent composition of surfactant detergent composition, personal care composition and other cleaning purposes.
By means of there is above-mentioned technical proposal, the present invention has the advantage that is with beneficial effect:
1) present invention provides a kind of liquid detergent containing external structurant system combination, which has
That is, under the same conditions higher structuring performance has better suspending power.
2) the present invention also provides the preparation method of the external structurant system for liquid detergent composition, this method
In, alkyl aryl sulphonic acid solubilizer feeds intake prior to 12- hydroxyl-stearic acid triglycerides, and has more preferably surfactant
Proportion, to guarantee 12- hydroxyl-stearic acid triglycerides crystal habit, i.e., offer detergent composition has higher outstanding
Floating capacity.
3) the present invention also provides the liquid detergent and preparation method thereof containing external structurant system combination, this method
There is the liquid detergent of preparation higher suspending power to have higher stability that is, after addition insoluble particulates.
Specific embodiment
For those skilled in the art, feature of the invention, beneficial by reading the content of this disclosure
Effect and advantage will become obvious.
Unless otherwise specified, all percentages, score and ratio are calculated by the total weight of the present composition.It removes
Non- otherwise indicated, all wt in relation to ingredients listed gives the content of active material, thus they be not included in it is commercially available
The solvent or by-product that may include in the material of acquisition.This paper term " weight content " available symbols " % " indicate.
Unless otherwise specified, the environment at 25 DEG C occurs for all preparations and test herein.
Herein "include", "comprise", " containing ", " containing ", " having " or other variants be intended to it is non-enclosed include,
It is not distinguished between these terms.Term "comprising", which refers to, can be added not the other steps for influencing final result and ingredient.Term
"comprising" further includes term " Consists of " and "consisting essentially of ...".The compositions and methods of the invention/technique may include,
Be made from it and substantially by essential elements described herein and limit entry and it is described herein any additional or optionally at
Divide, component, step or limit entry form.
Think that respectively constituting external structurant system of the present invention and the group of liquid detergent composition is grouped as introduction:
12- hydroxyl-stearic acid triglycerides
12- hydroxyl-stearic acid triglycerides of the present invention is the main component of rilanit special.
Castor oil is the glyceryl ester of fatty acid, and castor oil is present in the seed of castor-oil plant, and content is 35%~57%,
Using squeeze or solvent extraction be made.90% is ricinoleic acid (the cis- octadecylene of 12- hydroxyl -9- in the fatty acid chain of castor oil
Acid), ricinoleic acid three ester of the castor oil containing about 70%.It being controlled by hydrogenation process condition, castor oil can be completely hydrogenated,
Form rilanit special.Therefore about 70% (i.e. 12- hydroxyl-stearic acid is sweet for 12- hydroxy octadecadienoic acid triglycerides in rilanit special
Oily three esters).
The invention discloses a kind of external structurant system combinations for liquid detergent, wherein total by composition
The weight percent meter of amount, it includes:
A) 0.01%~5% 12- hydroxyl-stearic acid triglycerides, preferably 0.1%~2%;
B) 0.01%~5% alkyl aryl sulphonic acid solubilizer, each alkane chain carbon in the alkyl aryl sulphonic acid solubilizer
Atomicity is less than 5, and preferably 0.1%~2%;
C) 5%~60% surfactant, the surfactant is anionic surfactant, non-ionic surface is living
Property agent, one kind of zwitterionic surfactant or its a variety of mixture;
D) the pH stabilizer of 0.01%-0.5%, the pH stabilizer are selected from citric acid, succinic acid, benzoic acid, galla turcica
One of sour, boric acid and its alkali metal salt, organic amine salt or a variety of mixtures;
E) water of 90%-95.0%.
Preparation method can be expressed as follows:
External structurant system preparation process of the present invention is four steps:
A surfactant, alkali and alkyl aryl sulphonic acid solubilizer are successively put under) stirring, into reaction kettle, and with pH tune
It saves agent and the pH of the mixture in reaction kettle is adjusted to 6.0~10, preferably 7~8.5;
B) it is then heated to 80 DEG C~95 DEG C, preferably 90 DEG C~95 DEG C, then 12- hydroxyl-stearic acid triglycerides is put into, and
At such a temperature, stirring is until all 12- hydroxyl-stearic acid triglycerides emulsify completely;
C the mixture then) is quickly cooled to 55 DEG C~80 DEG C again, and is kept at this temperature holding 5 minutes~300
Minute, preferably 60 minutes~120 minutes;
D) last slow cooling again is to being lower than 40 DEG C, preferably room temperature.
Step A) it is to prepare suitable surfactant emulsifiers solution.Well known in the industry, anionic surfactant pair
Grease has excellent emulsifying ability, and therefore, the anion table work of high level can be realized 12- hydroxyl-stearic acid triglycerides
It is fully emulsified.Since 12- hydroxyl-stearic acid triglycerides fusing point is at 85 DEG C or more;
The step B) mainly realize the thawing of 12- hydroxyl-stearic acid triglycerides, and it is newborn under Action of Surfactant
Change.When temperature is down to fusing point or less such as lower than 80 DEG C, 12- hydroxyl-stearic acid triglycerides will be precipitated again.
Under the conditions of step C) is described, 12- hydroxyl-stearic acid triglycerides will be crystallized with filamentous form, and length exists
Several microns are to tens microns, and diameter is generally tens nanometers.
Rheological yield stress
When composition is when external force is less than certain critical value, the opposing stationary behavior of class solid can be shown as, and big in external force
The behavior of class I liquid I flowing is then shown as when Mr. Yu's critical value, which is the rheological yield stress of composition.The present invention
The composition rheological yield stress being related to passes through Herschel-Bulkle using rheometeryMethod is fitted reckoning and obtains, tool
Stable suspersion can be carried out to suspended matter in system by having the composition of certain rheological yield stress, and the system that can avoid occurs layering, hangs
The phenomenon that floating object is settled or is floated downward.
Stability test
Well known in the industry, liquid detergent stability is very important index, including storage appearance stability, freezes
Melt circulation intrinsic stability.
Firstly, for a long time under the constantly violent situation of change of high temperature or low temperature storage and storage temperature, in composition
Generate split-phase, layering, precipitating, flocculation, suspended particulate phenomena such as such as surfactant, fatty acid, auxiliary agent and salt, or even produce
Raw uncertain chemical change, so that composition can not restore reset condition recovery to storage at room temperature, to generate
Because of composition wild effect caused by storage condition, that is, store appearance stability.
Generally, cause to have the reason of storing appearance stability problem:
1. composition matches improper, easy gelation;2. there are easy decomposed substances in composition;3. existing in composition with anti-
Substance is answered, anion and cationic surfactant or polymer are such as existed simultaneously.Generally, appearance stability test bag is stored
Include: high-temperature stability, low-temperature stability, Frozen-thawed cycled stability, ordinary temperature stability etc. are several.
PH adjusting agent
Alkaline environment is conducive to the detergency of the detergent composition based on promotion anionic surfactant, while again can
Cause the hydrolysis of ester group in polyester soil release polymers.Therefore, external structurant system of the present invention and its liquid detergent
PH be pH5.0~pH10.0, preferably pH6.0~pH9.0, optimal selection pH7.0~pH9.0.
The pH value of liquid detergent composition of the present invention is controlled by addition pH adjusting agent.The acid-base accommodation
Agent includes: acidity regulator and alkalinity regulator.Wherein acidity regulator selects organic acid, inorganic acid and strong acid weak base salt, excellent
Selected from citric acid, succinic acid, benzoic acid, gallic acid, boric acid, more preferably from citric acid.Alkalinity regulator, selected from selected from organic
The carbonate of amine, the hydroxide of alkali metal and alkali metal, preferably is selected from sodium hydroxide.
Surfactant
External structurant system of the present invention and its liquid detergent also include surface-active other than fatty acid salt
Agent system.Suitable surfactant system includes, but is not limited to: anionic surfactant, nonionic surfactant,
One kind of zwitterionic surfactant and its a variety of mixtures.Preferred surfactant system is living comprising anionic surface
The mixture of property agent and nonionic surfactant.
Its weight of surfactant total amount in the detergent composition of external structurant system of the present invention
Percentage composition is 5%~30%, preferably is selected from 10%~20%.
The surfactant total amount of the liquid detergent of system containing external structurant of the present invention is in the detergent group
The weight percentage 0.1%~80.0% in object is closed, preferably is selected from 5%~70%.
Fatty acid salt
Fatty acid refers to that the organic matter of a carboxyl and aliphatic hydrocarbon chain is contained in one end, including Salt of saturated fatty acid and
Unsaturated fatty acid salt.Fatty acid salt is that fatty acid is formed after alkali saponified.Usually used alkaline agent be sodium hydroxide and
Potassium hydroxide.Salt of saturated fatty acid be the fatty acid salt without containing carbon-carbon double bond, selected from octanoic acid, capric acid, lauric acid, myristic acid,
Palmitic acid, stearic acid, arachidic acid one or more mixtures.Unsaturated fatty acid salt is containing one or more carbon-carbon double bonds
Fatty acid salt.According to the difference of double bond number, and the monounsaturated fatty acids containing double bond can be divided into and containing multiple
The polyunsaturated fatty acid of double bond.Monounsaturated fatty acids has oleic acid, and polyunsaturated fatty acid has linoleic acid, linolenic acid, peanut
Tetraenoic acid etc..
In external structurant system combination of the present invention, weight of the fatty acid salt in the external structurant system
Measuring percentage composition is 0%~30%, preferably is selected from 1%~5%.
The fatty acid salt of the liquid detergent of the system of the present invention containing external structurant, the weight in the detergent
Measuring percentage composition is 0~10.0%, 0.1~5.0% preferably is selected from, more preferably from 0.5~2.0%.
In liquid detergent of the present invention, the fatty acid salt is the fatty acid for being 10 to 20 selected from carbon atom
Alkali metal salt one or more mixtures.
Anionic surfactant
In external structurant system of the present invention, anionic surfactant is in the external structurant system
Weight percentage is 5%~30%, preferably is selected from 10%~20%.And the anionic surfactant accounts for the external structurant
At least the 80% of surfactant total weight in system.The anionic surfactant be selected from sulfonate surfactant,
Carboxylate surfactant, sulfated surfactant one or more mixtures, preferably be selected from containing ethoxylation
Aliphatic alcohol sulfate sodium n-alkylbenzenesulfonate, alkyl contains 11~14 carbon atoms.
The anionic surfactant of the liquid detergent of the system of the present invention containing external structurant, in the washing
Weight percentage in agent composition is 1%~50%, preferably is selected from 1%~30%.The anionic surfactant is selected from
Sulfonate surfactant, carboxylate surfactant, sulfated surfactant one or more mixtures,
It preferably is selected from alkylbenzene sulfonate, the alkyl sulfate of C8 to C18, the ethoxylated fatty alcohol sulfate of C8 to C18, alpha-olefin sulphur
The mixtures of the one or more of hydrochlorate, fatty acid alkyl ester sulfonate, ethoxylized fatty alcohol ether carboxylate.
In some embodiments, the mixture of anionic surfactant preferably comprises alkylbenzene sulfonate and its derivative
Object.The alkylbenzene sulfonate meets following general formula:
Wherein R1It is the alkyl that carbon number is 6 to 24, M+For cation.R1The alkyl that can be straight chain, is also possible to branch
Alkyl;The alkyl that can be saturation is also possible to the alkyl containing one or more unsaturated double-bonds.More preferable R1It is that carbon number is
8 to 18 straight chained alkyl.
In some embodiments, the mixture of anionic surfactant contains the aliphatic alcohol sulfate of ethoxylation.
Ethoxylated fatty alcohol sulfate is the derivative of ethoxylate fatty alcohol, has following general formula:
Wherein R1It is the alkyl that carbon number is 6 to 24;X is 0.5 to 30;Wherein M+For cation.R1It can be the alkane of straight chain
Base is also possible to the alkyl of branch;The alkyl that can be saturation is also possible to the alkane containing one or more unsaturated double-bonds
Base.It is preferred that R1It is the straight chained alkyl that carbon number is 8 to 18.X represents average ethoxylation degree, is 0.5 to 30, preferably 0.5 to 10,
More preferable 0.5 to 3.
In some embodiments, containing alpha-alkene sulfonate, there is following general formula:
Wherein a is 0 to 2, wherein M+For cation, R1It is the alkyl that carbon number is 6 to 24, preferably R1Be carbon number be 8 to 18
Alkyl.
The anionic surfactant can also include one kind and a variety of mixing of alkyl sodium disulfonate or derivatives thereof
Object, optimizing alkyl diphenyl oxide disulfonate, suitable example are disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate salt.Fatty acid can also be contained
Alkyl sulfate, preferably fatty acid methyl ester sulfate (MES), fatty acid carbon number preferably 8 to 18.It can also include sulfo group
Succinate, preferably disodium alkyl polyoxyethylene sulfosuccinate, are put down by fatty alcohol carbon number preferably 8 to 18
Equal degree of ethoxylation is preferably 2.0.
In some embodiments, the mixture of anionic surfactant contains fatty acid salt.Fatty acid salt is fat
What acid was formed after alkaline good fortune.Usually used alkaline agent is sodium hydroxide and/or potassium hydroxide.Liquid of the present invention is washed
It washs in agent composition, the fatty acid salt is selected from the metal salt for the fatty acid that carbon atom is 10 to 20, and preferably carbon atom is
10 to 16 linear alkyl fatty acids.
Its cation of anionic surfactant described above can make alkali metal ion or alkaline-earth metal ions, preferably
Sodium ion.
Nonionic surfactant
In external structurant system of the present invention, nonionic surfactant is in the external structurant system
Weight percentage is 0%~10%, preferably is selected from 1%~5%.
The nonionic surfactant of the liquid detergent of the system combination of the present invention containing external structurant, in institute
Stating the weight percentage in detergent is 1%~50%, preferably is selected from 1%~30%.
Nonionic surfactant is selected from fatty alcohol alkoxy compound, alkyl polyglycoside, fatty acid alkoxylates, fat
Sour ethoxylate, fatty acid alkyl alcohol amide, ethoxylated sorbitan acid alcohol ester one or more mixtures.
In some embodiments, non-ionic surfactant mixture preferably comprises fatty alcohol alkoxy compound, described
Fatty alcohol alkoxy compound has following general formula:
Wherein, n is 6 to 24;X is 0.5 to 30,yIt is 0 to 10.
The fatty alcohol alkoxy compound is the ring-opening polymerisation under basic catalyst effect of fatty alcohol and epoxyalkane
Product, therefore be mixture.Fatty alcohol includes the isomery alcohol of straight chain alcohol or branch.Alkoxy grp includes ethoxy group and the third oxygen
Group.The fatty alcohol that the preferred carbon number of fatty alcohol is 8 to 18, preferred alcohol includes but is not limited to hexanol, octanol, decyl alcohol, 2- second
Base alcohol, 3- propyl enanthol, laruyl alcohol, different three decyl alcohol, tridecanol, tetradecanol, hexadecanol, Palmitoleyl alcohol, stearyl alcohol,
One kind and its mixture of isooctadecanol, oleyl alcohol, sub- oleyl alcohol, linolenyl alcohol.Average ethoxylation degree x preferably 2 to 12.Preference
Son is SHELL company NEODOL series linear primary alcohol ethoxylate product, DOW company ECOSURFEH series ethoxylation
With third oxidation 2-ethylhexanol product, the ethoxylation of BASF AG LutensolXL series and third oxidation 3- propyl enanthol product and
BASF AG LutensolXP series ethoxylation 3- propyl enanthol product.
In some embodiments, non-ionic surfactant mixture preferably comprises alkyl polyglycoside, has following logical
Formula:
Wherein, it is 1.1 to 3 that n, which is 6 to 24, p, and preferably n is 8 to 16.Suitable alkyl polyglycoside such as BASF AG
Glucopon series alkyl glycosides product.
Non-ionic surfactant mixture can contain fatty acid alkoxylates, preferably be selected from ethoxylation C8 to C18
Aliphatic ester, average ethoxylation degree are 2 to 10.Ethoxylated sorbitan acid alcohol Arrcostab, alkyl carbon number can be contained
It is 6 to 18, average ethoxyquin degree is 4 to 20;Suitable example is Corda company's T ween series of products.
Non-ionic surfactant mixture can contain fatty acid alkyl alcohol amide, and the carbon number of fatty acid is 6 to 24, can
To be the fatty acid of straight chain, it is also possible to the fatty acid of branch, can be the fatty acid of saturation, be also possible to unsaturated fat
Acid;Alkylol number is 0 to 2.The glycollic amide that preferred fatty acid carbon number is 8 to 18, diglycollic amide, isopropanol amide,
Suitable example is coconut acid diethanolamide.
Non-ionic surfactant mixture can contain fatty acid methyl ester ethoxylate, and general formula is as follows:
Wherein, n is 6 to 24;X is 2 to 20, and preferably n is that 8 to 18, x is 0.5 to 30.It is preferred that x is 4 to 10.
Non-ionic surfactant mixture can contain polyether surfactant.Polyether surfactant is a kind of
Polymer, the nonionic surfactant containing oxidation ethylene and/or oxidation trimethylene repetitive unit, suitable example such as BASF are public
Take charge of Pluronic series of products.
Other surfactants
Surfactant system of the present invention can contain other surfaces activating agent, be selected from: 0%~30% both sexes from
Sub- surfactant, the group of 0~30% cationic surface active agent composition.Zwitterionic surfactant is selected from amino acid pattern
Surfactant, amine oxide type surfactant, betaine type amphoteric surfactant, one kind of Imidazoline Surfactants or more
Kind mixture;Including but not limited to: alkyl betaine, fatty acid amide glycine betaine, fattyamidopropyl betaine, fatty acid amide
Propyl hydroxypropyl sulfonated betaine, including acetate alkyl sodium form imidazoline, fatty acid type imidazoline, sulfonic acid type imidazoline;Amino
Propanoic derivatives, glycine derivative;Alkyl dimethyl amine oxide, fatty acyl amido dimethylamine oxide etc..Cation
Surfactant includes quaternary ammonium salt surface active agent, heterocyclic surfactant, polymer-type cationic surfactant.Packet
It includes: single long linear quaternary ammonium salt, double long linear quaternary ammonium salts, benzyl quaternary ammonium salt, hydroxyalkyl quaternary ammonium salt, fatty amide propyl hydroxyalkyl season
Ammonium salt, the multi-quaternary ammonium salt for thering is vinyl pyrrolidone and unsaturated amides or unsaturated quaternary ammonium salt to be copolymerized.
Washing assisant
External structurant system combination of the present invention and the liquid detergent containing the external structurant system
It may include washing assisant, the washing assisant is selected from enzyme preparation and its stabilizer, pH stabilizer, pH adjusting agent, antiredeposition
Agent, functional polymer, chelating agent and fluorescent whitening agent composition.
Enzyme preparation and its stabilizer
Detergent composition of the present invention may include one or more of enzyme preparations, to provide clean-up performance, knit
Object nursing and/or other beneficial effects.The enzyme preparation is selected from the group of following enzyme composition: protease, alpha-amylase, cellulose
Enzyme, hemicellulase, phosphatidase, esterase, lipase, peroxidase/oxidizing ferment, pectase, lyases, mannase,
Cutinase, reductase, zytase, amylopectase, tannase, pentosanase, maltosan, arabinase, β-Portugal are poly-
Carbohydrase.Common enzyme preparation is protease, amylase, lipase, cutinase and/or cellulase.Enzyme preparation content is washing
The 0.001% to 5% of agent composition, preferably 0.01% to 2%.
Liquid detergent of the invention may include the enzyme stabilising system for accounting for composition weight 0.001% to 10%.It is described
Enzyme stabilising system can be compatible with liquid detergent, may include calcium ion, boric acid, borax, propylene glycol, glycerol, and the one of polyalcohol
Kind and its mixture.The weight and dosage of enzyme stabilising system is in the form of according to detergent composition and forms and enzyme preparation
Type is adjusted.
Anti redeposition agent
From the viewpoint of effectively improving washing effect, antiredeposition may include in liquid detergent of the present invention
Agent.The anti redeposition agent includes but is not limited to the group of following compound composition:
Cellulose derivative, such as carboxymethyl cellulose, ethylhydroxyethylcellulose, methylcellulose;Vinyl pyrrole
The homopolymer and copolymer of alkanone, such as straight linear polyethylene base pyrrolidones, vinyl pyrrolidone and vinyl acetate are total to
The copolymer of polymers, vinyl pyrrolidone and vinyl imidazole;Polycarboxylate, such as the poly- horse of polyacrylate, polyacrylic acid
Come acid copolymer, acrylic acid-acrylic ester-co-polymer of sulfonate.Anti redeposition agent content in liquid detergent composition is
0.01% to 5%, preferably 0.01% to 2%.
Functional polymer
Detergent composition of the present invention includes one or more functional polymers comprising amphipathic alkoxy
Change grease cleaning polymer, carboxylate polymer and/or modified carboxylic acid ester polymer, polycarboxylate and/or modified polycarboxylic acid salt.
Detergent composition of the present invention may include amphipathic alkoxylate grease cleaning polymer, have balance
Hydrophilicity and hydrophobic performance so that they remove fat particles from fabric surface or hard surface.The amphipathic alkoxylate
A kind of embodiment of grease cleaning polymer is comprising one or more cored structures and multiple alcoxyls for being connected to the cored structure
Base group, cored structure can with but be not limited to the molecular formula such as ethylenediamine, trien, tetren as H2N
(C2H4NH)nThe linear amine structure of H or star-like polyethyleneimine, Alkoxylated groups can with but be not limited to polyoxyethylene
Base, polyoxypropylene base and/or their block and/or random copolymerizable group.
In liquid detergent of the present invention, amphipathic alkoxylate grease cleaning polymer is in the liquid detergent
Weight percentage in composition is 0~10.0%, preferably 0.1~5.0%, more preferably 0.5~2.0%.
Liquid detergent of the present invention may include carboxylate polymer and/or modified carboxylic acid ester polymer, with enhancing
Scavenging activity of the composition to grease.It can be polyacrylate homopolymers or maleate/the third including carboxylate polymer
The Random copolymer RCP of olefin(e) acid ester and alkoxylated polycarboxylates are the polyacrylate containing polyoxyethylene base side chain.Its
Molecular weight is usually between about 2000 to about 50000.In liquid detergent of the present invention, carboxylate polymer and/or change
Property weight percentage of the carboxylate polymer in the liquid detergent composition be 0~10.0%, preferably 0.1~
5.0%, more preferably 0.5~2.0%.
Liquid detergent of the present invention may include polycarboxylate and/or modified polycarboxylic acid salt, to enhance composition pair
The Scavenging activity and inhibition calcium scale of graininess dirt are formed.It is polymerize including one or more double bond containing aliphatic carboxylic acid monomers
Made of homopolymer and copolymer water soluble salt, double bond containing aliphatic carboxylic acid monomer used includes but is not limited to acrylic acid, first
Base acrylic acid, maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylene propylmalonic acid.Modified polycarboxylic acid salt
Side chain on contain polyoxyethylene groups or alkyl.Its molecular weight is usually between about 2000 to about 10000.It is of the present invention
In liquid detergent composition, the weight hundred of polycarboxylate and/or modified polycarboxylic acid salt in the liquid detergent composition
Dividing content is 0~10.0%, preferably 0.1~5.0%, more preferably 0.5~2.0%.
Chelating agent
Liquid detergent of the present invention may include one or more metal ion chelation agents, including copper, iron and/or manganese chela
Mixture and their mixture.These chelating agents can reduce the concentration of the metal ion to dissociate in liquid detergent, thus
Reduce deactivation of these metal ions to enzyme preparation, catalyticing decomposition action to other components etc..It can be used as chelating agent
Including aminocarboxylate, amino phosphonates etc., including but not limited to edetate (EDTA), nitrilotriacetic acid salt (NTA),
Diethylentriamine pentacetate (DTPA), alanine diacetin (MGDA), glutamic acid diacetic acid salt (GLDA) and/or second two
Amine four (methylene phosphate salt) (EDTMPA), ammonia three (methylene phosphate salt) (ATMP), five (methylene phosphate of diethylenetriamines
Salt) (DTPMP), hydroxy-ethane diphosphonate (HEDP) and ethylenediamine disuccinate (EDDS) and their mixtures.This
It invents in the liquid detergent composition that is related to, weight percentage of the chelating agent in the liquid detergent be 0~
20.0%, preferably 0.1~5.0%, more preferably 0.5~2.0%.
Fluorescent whitening agent
The technology that application of the fluorescent whitening agent in liquid detergent is well-known in the art, and Commercial optical brightens
Agent commodity are abundant.Fluorescent whitening agent exists in the form of its alkali metal salt (mostly sodium salt).Preferred fluorescent whitening agent include but
It is unlimited with distyryl biphenyl compound.Suitable example is 4,4'- bis- (2- sodium sulfonate styryl) biphenyl, such as BASF
The product of company's CBS-X trade mark.The dosage of fluorescent whitening agent is the 0.01% to 2wt% of total composition, preferably 0.01%
To 0.1%.
In liquid detergent of the present invention, weight percent of the fluorescent whitening agent in the liquid detergent composition
Content is 0.01~2.00%, preferably 0.05~1.00%, more preferably 0.05~0.50%.
Solvent
Due to easily gelation after the surfactant mixture chance water of high concentration, to become to be very difficult to dissolve, just
The effect of cannot achieve decontamination.Namely in actual use, after the surfactant mixture of high concentration meets water, semisolid is formed
Shape gel, it is insoluble for a long time, expected cleaning force is on the one hand not achieved, on the other hand meeting soiled laundry, causes significantly to wash
Wash agent residual.Furthermore to meet technique production requirement, improving production efficiency, a certain amount of solvent can generally be added, to guarantee group
Closing object can quickly mix.Well known in the industry, most common solvent, that is, water can choose miscible with water organic in addition to this
Solvent.Such organic solvent includes lower alcohol, polyalcohol, ether, polyethers, alkylamine, fatty amine, alkyl (or ester group) amide, list
Replace or disubstituted N- alkyl-substituted derivative, alkyl (or ester group) carboxylic acid, lower alkyl esters, ketone, aldehyde, polyalcohol and sweet
Grease.
In liquid detergent of the present invention, solvent is selected from one of water, polyol solvent, alcohol ether solvents or a variety of
Mixture, preferably be selected from the excessively a variety of mixture of one of water, glycerol, propylene glycol, ethyl alcohol.
Optional member
Liquid detergent of the present invention includes following optional additive: alkaline agent, viscosity modifier, preservative,
The mixture of one or more compositions of toner, colour stabilizer and essence.
Liquid detergent of the present invention may include one or more alkaline agents, and alkaline agent is selected from sodium hydroxide, hydroxide
Potassium, alkali carbonate, the silicate of alkali metal.Weight percentage of the alkaline agent in the liquid detergent composition be
0.01~30.0%, preferably 0.05~10.0%, more preferably 0.05~5.0%.
Liquid detergent of the present invention may include one or more of viscosity modifiers, suitable viscous to provide
Degree.Suitable viscosity modifier such as salt, polysaccharide, sizing material, short chain fatty alcohol, short chain fatty alcohol alkyl ether.Suitable example is chlorine
Change sodium, sodium formate, sodium acetate, ethyl alcohol, propylene glycol, sodium citrate, alkyl-hydroxyalkylcelluloswith ether, carragheen, xanthan gum, poly- third
Alkenylamide derivative.Weight percentage of the viscosity modifier in the liquid detergent composition is 0.01~30.0%,
Preferably 0.05~10.0%, more preferably 0.05~5.0%.
In some embodiments, liquid detergent of the present invention preferably comprises preservative, and suitable example is benzene
Keto-alcohol, sodium benzoate;Isothiazolinone and its derivative, such as methylisothiazolinone, methylchloroisothiazandnone, benzisoxa
Or mixtures thereof one kind of thiazolinone.Preservative dosage is 0.001% to 5%, preferably 0.01% to 2%.
Material component introduction in embodiment:
In lower embodiment, unless otherwise specified, all contents are weight percentages, the content in relation to ingredients listed
It is the content of the active material by conversion.
In the described embodiment, following abbreviations will be used, and have the function of being indicated.
KOH: potassium hydroxide neutralizes fatty acid saponification and prepares fatty acid salt, alkaline agent.
Liquid alkaline: the sodium hydrate aqueous solution that mass percent containing sodium hydroxide is 32% neutralizes fatty acid saponification and prepares rouge
Fat hydrochlorate and/or neutralization LAS, alkaline agent.
LAS: sodium n-alkylbenzenesulfonate, carbon atom number are 10~13, anionic surfactant.
AOS: alpha-alkene sulfonate, anionic surfactant.
AES: ethoxylated fatty alcohol sulfate, fatty alcohol carbon atom number are 12~14, and average ethoxyquin degree is 2, yin
Ionic surface active agent.
K12: lauryl sodium sulfate, anionic surfactant.
MES: fatty acid methyl ester sulfate, fatty acid carbon atoms number are 8~18, anionic surfactant.
AEO9: ethoxylized fatty alcohol, average ethoxyquin degree are 9, nonionic surfactant.
TO-7: ethoxylation isomerous tridecanol, average ethoxyquin degree are 7, nonionic surfactant.
MEE: fatty acid methyl ester ethoxylate, fatty acid carbon atoms number are 6~24, average ethoxyquin degree is 0.5~
30, nonionic surfactant.
APG:C8-C14 alkyl glycosides, nonionic surfactant.
LAO: dodecanamide propyl amine oxide.Nonionic surfactant.
CAB: cocoamidopropyl betaine, zwitterionic surfactant.
LAB: lauroylamidopropyl betaine, zwitterionic surfactant.
1227: dodecyl benzyl dimethyl ammonium chloride, cationic surfactant.
1631: hexadecyltrimethylammonium chloride, cationic surfactant.
DTM-8:N, N '-bis- caprylyl ethylenediamine diethyl sodium sulfonates, gemini surfactant.
DTM-10:N, N '-bis- capryl ethylenediamine diethyl sodium sulfonates, gemini surfactant.
PAA: the sodium salt of acrylate homopolymer, polycarboxylate.
CPA: the sodium salt of the polymer of the constitutional repeating unit containing acrylic acid, polycarboxylate.
CMC- sodium salt: sanlose, anti redeposition agent.
EPEI: polyethyleneimine (MW=600), each-NH have 20 ethoxylate groups, polyester soil release polymerization
Object.
Protease: alkali protease, Novozymes Products, the trade mark are Savinase Ultra 16XL.
Enzyme stabilizers: the borax by accounting for enzyme stabilizers weight containing 20%, 50%, which accounts for the glycerol of enzyme stabilizers weight and 30%, accounts for enzyme
The citric acid of stabilizer weight collectively constitutes.
Brightening agent: 4,4'- bis- (2- sodium sulfonate styryl) biphenyl, Optical Bleaching Agent, BASF AG's product, the trade mark are
CBS-X。
Preservative: methylisothiazolinone and chlormethylisothiazo,ine alcohol/ketone mixtures.
Effete test embodiment 1: rheological yield stress test
Liquid detergent composition rheological property is tested by the rheometer of Anton Paar MCR-302 model, test temperature
Degree is 25~45 DEG C, and range of shear rate is 0.1~100S-1, pass through Herschel-Bulkley:y=a+bxpEquation carries out
Fitting calculates composition rheological yield stress, requires Correlation Ratio (R^2) to be greater than 0.99 when fitting.
The base fluid of 1 liquid detergent of table forms (weight percent %)
A, " appropriate " for that can add or not add the component according to demand, additive amount is that ordinary people can perceive its function
Effect.
The base fluid preparation method of the liquid detergent of above-mentioned table 1 is:
1) solvent (water, ethyl alcohol, propylene glycol), alkaline agent (potassium hydroxide, liquid alkaline) and surface-active are added into main preparing tank
Agent (fatty acid, LAS, AEO9, AES, XL-80), stirring are complete to dissolving;
2) addition pH adjusting agent (citric acid) adjusts pH to 7~9;
3) external structurant system combination (as shown in table 2 and table 4) is added, stirring is until dispersion is complete;
4) washing assisant, additive, and supplementing solvent is added, stirs to being completely dissolved, appearance is uniform;
5) product quality parameters are adjusted, are stirred uniform to appearance.
Combination formula (embodiment 1-6 and comparative example 1) of the table 2 for the external structurant system combination of liquid detergent
A, " liquid detergent yield stress " are that 6 parts of external structurant systems are mixed and stirred for uniformly with 94 parts " 1# base fluid "
To after without obvious particulate matter, according to surrender force test method, yield stress is tested.
B, " liquid detergent yield stress " are that 6 parts of external structurant systems are mixed and stirred for uniformly with 94 parts " 2# base fluid "
To after without obvious particulate matter, according to surrender force test method, yield stress is tested.
The external structurant system combination embodiment 1-6 of above-mentioned table 2, preparation method is:
A under) stirring, surfactant (LAS), alkaline agent (liquid alkaline), pH stabilizer (citric acid are successively put into reaction kettle
Sodium) and alkyl aryl sulphonic acid solubilizer (2,4- sodium xylene sulfonates, paratoluenesulfonic acid sodium salt or cumene sodium sulfonate), and with pH tune
It saves agent (citric acid) and the pH of the mixture in reaction kettle is adjusted to 6.0~10, preferably 7~8.5;
B) it is then heated to 80 DEG C~95 DEG C, preferably 90 DEG C~95 DEG C, then 12- hydroxyl-stearic acid triglycerides is put into, and
At such a temperature, stirring is until all 12- hydroxyl-stearic acid triglycerides emulsify completely;
C the mixture) is quickly cooled to 55 DEG C~80 DEG C again, and is kept at this temperature 5 minutes~300 points of holding
Clock, preferably 60 minutes~120 minutes;
D) last slow cooling again is to being lower than 40 DEG C, preferably room temperature.The external structurant system group of comparative example 1 in table 2
It closes and does not contain alkyl aryl sulphonic acid solubilizer in object A, after remaining liquid detergent base fluid (1# base fluid) is sufficiently mixed, surrender
Power is 0.13Pa.
And 1~embodiment of embodiment 6 is added with alkyl aryl sulphonic acid solubilizer, contains embodiment external structurant system group
The liquid detergent yield force for closing object is all obviously improved.
Effete test embodiment 2: the influence of process structure performance
(2,4- sodium xylene sulfonate is not contained in the composition) according to " external structurant based on composition A in table 2
The preparation method of system combination " prepares external structurant system combination, and mixed with " 1# base fluid " (" 1# base fluid " is free of 2,
4- sodium xylene sulfonate).
In preparation process, 2,4- sodium xylene sulfonate is added in different location.Specific preparation process is as follows:
Comparative example 1: not adding 2,4- sodium xylene sulfonate in preparation process, and external structurant system prepared by 6 parts with
93 parts " 1# base fluids " and 1 part of pure water mixing;
Comparative example 2: not adding 2,4- sodium xylene sulfonate in preparation process, and external structurant system prepared by 6 parts with
93 parts " 1# base fluid " mixing and 0.1 part of 2,4- sodium xylene sulfonate, 0.9 part of pure water mixing;
Comparative example 3: not adding 2,4- sodium xylene sulfonate in preparation process, and external structurant system prepared by 6 parts with
93 parts " 1# base fluid " mixing and 0.5 part of 2,4- sodium xylene sulfonate, 0.5 part of pure water mixing;
Comparative example 4: not adding 2,4- sodium xylene sulfonate in preparation process, and external structurant system prepared by 6 parts with
93 parts " 1# base fluid " mixing and 1 part of 2,4- sodium xylene sulfonate mixing;
Comparative example 5: step D adds 2,4- sodium xylene sulfonate (additive amount 0.5%), and external structure prepared by 6 parts
Change system is mixed with 93 parts " 1# base fluids " and 1 part of pure water;
Comparative example 6: step D adds 2,4- sodium xylene sulfonate (additive amount 0.5%), and external structure prepared by 6 parts
Change system is mixed with 93 parts " 2# base fluids " and 1 part of pure water;