CN105647678A

CN105647678A - Method for improving protein dirt removing capability of washing agent composition and washing agent composition

Info

Publication number: CN105647678A
Application number: CN201610025430.8A
Authority: CN
Inventors: 黄亮; 钱程; 洪银旋; 吴萍萍; 陈玉娥; 张利萍
Original assignee: Guangzhou Liby Enterprise Group Co Ltd
Current assignee: Guangzhou Liby Enterprise Group Co Ltd
Priority date: 2016-01-14
Filing date: 2016-01-14
Publication date: 2016-06-08
Anticipated expiration: 2036-01-14
Also published as: CN105647678B

Abstract

The invention discloses a method for improving the protein dirt removing capability of a washing agent composition. The method is characterized in that a sodium salt derivative of an acrylic acid and 2-acrylamido-2-methylpropane sulfonic acid copolymer is used, wherein the sodium salt derivative of the copolymer meets the conditions that the 2-acrylamido-2-methylpropane sulfonic acid constitutional unit in the copolymer accounts for 40%-70% of the total mass of the acrylic acid and 2-acrylamido-2-methylpropane sulfonic acid constitutional unit, the number-average molecular weight of the sodium salt derivative of the copolymer is 5200-10000, and the molecular weight distribution of the sodium salt derivative of the copolymer is 1.60-1.85. The washing agent composition containing the sodium salt derivative of the acrylic acid and 2-acrylamido-2-methylpropane sulfonic acid copolymer has high protein dirt removing capability in high-hardness water.

Description

Promote method and the composition of detergent of cleaning compositions to albumen soil removal capabilities

Technical field

The present invention relates to use polymer as the method that improves the removal ability of cleaning compositions to albumen dirt, concreteRelate to the polymer that contains sulfonate radical and carboxylate group, and the wash environment of high rigidity.

Background technology

Protein dirt is the most common one in washing dirt; Its source comprises that the protein of food is as egg white,Milk stain, and bloodstain, grass stain etc. Protein dirt easily sticks to fabric face, is difficult to dissolve also more difficult washing in waterWash the surface that disperses and depart from fabric under agent effect.

Over nearly 30 years, detergent manufacturers is mixed enzyme preparation in their product, to obtain, the good of dirt is cleanedPower. Protease is modal a kind of enzyme preparation of adding in current fabric detergent. Due to the structure particularity of enzyme preparation, because ofThis composition to each composition in formula, the storage condition of enzyme preparation, and the preparation technology of washing agent and the storage condition of productThe impact that capital produces the vigor of enzyme preparation. Owing to being limited to formulation composition, even add protease also in some washing agentMay be difficult to obtain desirable clean effect. (the prosperous Xu Qing detergent enzyme of brilliant work application manual, China Light Industry Press, 2001,Beijing)

Therefore, washing Industry bound pair, in not adding enzyme preparation, has the washing agent group of Enhancin soil removal capabilities simultaneouslyStill there is urgent demand in compound.

In common washing process, washing agent is by being mixed to form cleaning solution with running water, for cleaning with dirtThe substrate of stain. Be present in the washing usefulness that hard water ions in water can reduce washing agent. These ions are mainly calcium ion and magnesiumIon, in running water, the total concentration of all hard water ions is commonly referred to as the total hardness of water quality, and referred to as hardness of water, unit isMg/kg is (with CaCO₃Calculate), also can be expressed as ppm. According to GB5749-2006 " standards for drinking water quality ", life is drunkHardness of water should be lower than 450ppm. According to the GB/T13174-2008 " survey of washing agent detergency and circulation cleaning performance for dress materialFixed " in describe, while evaluating the washing usefulness of washing agent, adopting hardness of water is 250ppm. In fact, many cities and ground, cities and townsThe running water hardness standard in district is higher than 250ppm, and the running water of for example Beijing dispatches from the factory standard for not higher than 380ppm. TakingUnderground water is more common as city and this phenomenon of area at water source. And in some mountain area and rural area, resident's slurryDirectly surface water if river or underground water are as well water, the hardness at these water sources even likely one times of 250ppm withOn. Therefore, according to the washing agent of the water hardness preparation of 250ppm and be not suitable with the washing requirement in high-hardness water area. Having mustDevelop the washing agent using under higher hardness water quality environment. Optimal situation is, do not increase surfactant andWhen washing assisant consumption, washing agent can maintain suitable scourability in the water quality environment of different hardness.

In order to reduce the impact of hard water on clean result, in washing agent, must contain and can, in conjunction with the hard water ions such as calcium, magnesium, press downThe washing assisant of precipitation of calcium carbonate crystallization processed and growth. Polycarboxylate and 4A zeolite are current the most common phosphorus-free adjuvants. Poly-Carboxylate is except having the effect of bind metal ion; Also can effectively disperse the micro crystal of calcium carbonate, make its be difficult to growth,Deposition is polluted the surface of substrate; Also there is the effect of spot in stable dispersion cleaning solution. Polycarboxylate the calcium of higher concentration,In the water quality environment of magnesium ion content, solubility property obviously declines, and obviously affects detergency ability, and this phenomenon is called " gelling ".Along with the increase of polycarboxylate molecular weight, gelling phenomenon is particularly evident. Polycarboxylate is due to the combination of carboxylate radical and microparticle surfacesAct on too by force, only remain a small amount of carboxylic acid ion electrostatic repulsion is provided. Less electrostatic repulsion is unfavorable for particulateBetween, particulate and substrate surface separate. When polycarboxylate is applied in the lower system of pH value, carboxylate radical can be due to knotClose proton and change the carboxylic acid that hydrophily greatly declines into, may cause the hydrophily of polycarboxylate, calcium ion capture ability withAnd dispersive property all obviously reduces. When polycarboxylate molecular weight is larger, even may there is the heavy phenomenon of acid.

The polymer that contains hydroxy-acid group and sulfonic acid group is owing to containing strong anionic property functional group, simultaneously in molecular structureThe weak anionic functional group of containing strong sequestering power, makes it have the water-soluble of excellence, antiacid antigelation stability and goodDispersibility, complexing power and antifouling capability. This base polymer has been widely used in synthetic fibers, oilfield chemistry, and water treatment,Printing and dyeing, papermaking, the fields such as daily use chemicals coating. Acryloyl class sulfonate monomer the most important thing is 2-acrylamido-methyl propane sulfonic acidAnd methylic 2-methacryl amido-methyl propane sulfonic acid (AMPS). Their manufacturing process are simple, moderate cost.

2-acrylamide-2-methyl-propyl sulfonic acid (2-Acrylamide-2-MethylPropaneSulfonicAcid, AMPS) structure is as follows.

AMPS is a kind of conventional unsaturated monomer containing sulfonate radical. AMPS comes into operation mainly with the form of comonomer,And acrylic acid (AA) and maleic acid (MA), vinyl acetate grade in an imperial examination three monomers are prepared binary or ter-polymers.

There is no the copolymer of bibliographical information unsaturated carboxylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid for albumen dirtThe positive effect of removing. There is no bibliographical information under the water quality environment higher than 250ppm hardness, the washing agent that contains this polymerComposition has the albumen detergency ability of enhancing, does not also mention unsaturated carboxylic acid and 2-acrylamide-2-methyl-propyl sulfonic acidThe structural parameters of copolymer can cause it to help the difference of the ability of washing as molecular size range and distribution.

Summary of the invention

The object of the invention is to provide a kind of composition of detergent albumen detergency ability in the water quality of high rigidity that strengthensMethod, the sodium salt derivative of the copolymer of acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid for promote washing agent forThe removal ability of albumen dirt has positive facilitation, under the water quality environment higher than 250ppm hardness, and traditional poly-thirdThe contrast of olefin(e) acid sodium, the washing agent of the sodium salt derivative of the copolymer that contains acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acidThere is the better removal ability for albumen dirt.

Another object of the present invention is to provide the composition of detergent with Enhancin dirt removal capacity, wherein adoptsThe copolymer of acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid.

The invention provides a kind of method of cleaning compositions to albumen soil removal capabilities that promote, the method is to use thirdOlefin(e) acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt derivative, the sodium salt derivative of described copolymer meet withLower condition:

1) in copolymer, the quality of 2-acrylamide-2-methyl-propyl sulfonic acid construction unit accounts for acrylic acid and 2-acryloyl40% to 70% of amine-2-methyl-propyl sulfonic acid construction unit gross mass;

2) number-average molecular weight of copolymer sodium salt derivative is 5200 to 10000;

3) molecular weight distribution of copolymer sodium salt derivative is 1.60 to 1.85.

Described acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt derivative are in composition of detergentWeight content is 0.01% to 5%, is preferably 0.3% to 3%, more preferably 0.5% to 2%. Described albumen dirt is removedAbility is to measure under hardness of water is the wash environment of 250ppm, 350ppm and 500ppm.

In addition, the invention still further relates to a kind of albumen dirt with enhancing removal ability composition of detergent, its bagContain: weight content is 0.01% to 40% anion surfactant, weight content is 40% to 0.01% nonionic tableSurface-active agent, the zwitterionic surfactant of 0～30% (preferred content is 0.01～25%), 0～30% (preferred content is0.01～25%) group, washing assisant, 0.01% to 5% acrylic acid and the 2-propylene of cationic surface active agent compositionAcid amides-2-methyl-propyl sulfonic acid copolymer sodium salt derivative, the sodium salt derivative of described copolymer meets the following conditions:

Described anion surfactant is selected from sulfonate surfactant, carboxylate surfactant, sulfateThe mixture of one or more of type surfactant; Preferred alkyl benzene sulfonate, the alkyl sulfate of C8 to C18, C8 to C18Ethoxylated fatty alcohol sulfate, alpha-alkene sulfonate, fatty acid alkyl esters sulfonated ester, the soap of C8 to C18, secondOne or more in oxygen base Fatty Alcohol Ether Carboxylate.

Described non-ionic surface active agent is selected from fatty alcohol alkoxy compound, APG, and fatty acid alkoxylates,Fatty acid ethoxylate, fatty acid alkyl alcohol amide, ethoxylation dehydration sorbic acid alcohol ester a kind of or their mixture.

The present invention relates to composition of detergent substantially not containing polycarboxylate, described polycarboxylate is that number-average molecular weight is 2000Above, in its constitutional repeating unit, only comprise following structural formula (I), (II) any one or multiple polymer;

Wherein A is COOH or COO^-M⁺，M⁺For cation; B is H or CH₃. M wherein⁺Can be potassium ion, sodium ion, ammoniumIon etc.

Composition of detergent of the present invention can be any form, comprises following form: liquid form, and solid form, for examplePowder, particle, tablet etc.; Gel, bar, wet tissue etc., and other even or heterogeneous consumer's cleaning products form.

In some embodiments, composition of detergent of the present invention is liquid or fabric detergent composition.

By technique scheme, advantage and beneficial effect that the present invention has are:

1, the present invention is surprised to find that, by using acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodiumSalt derivative, can improve the albumen soil removal capabilities of washing agent under higher hardness water quality environment effectively.

2, do not increasing under the prerequisite of surfactant and other scrubbed component content the washing agent combination of this patent inventionThing is having good albumen soil removal capabilities in firmness change scope widely.

Detailed description of the invention

For a person skilled in the art, by reading the disclosure of the specification, feature of the present invention, usefulEffect and advantage will become apparent.

Except as otherwise noted, all percentage, mark and ratio are all by the total weight of the present composition. RemoveNon-ly indicate in addition, about all wt of ingredients listed all gives the content of active material, therefore they are not included in commercially availableSolvent or the accessory substance that in the material obtaining, may comprise. Term " weight content " available symbols " % " represents herein.

Except as otherwise noted, all molecular weight are all relative molecular mass in this article, are all with g/mol unit representationNumber-average molecular weight.

Except as otherwise noted, all preparations and test occur in the environment of 25 DEG C in this article.

" comprise " herein, " comprising ", " containing ", " containing ", " having " or other variant be intended to contain non-enclosed comprising,Between these terms, do not distinguish. Term " comprises " and refers to and can add other step and the composition that do not affect final result. Term" comprise " also comprise term " by ... composition " and " substantially by ... form ". The compositions and methods of the invention/technique comprises, byIts composition and substantially by essential elements described herein and limit entry and described herein arbitrary additional or optionalComposition, component, step or limit entry composition.

Hardness

" hardness " the present invention relates to refers in unit weight water gaging to calculate by weight of calcium carbonate, and in water, calcium ions and magnesium ions is totalAmount, unit is ppm. For example, while containing 0.0005 mole of calcium ion and 0.0005 mole of magnesium ion in 1000 grams of water, its hardness is100ppm。

" extensively hardness " refers to that the hardness of water quality is 250ppm, 350ppm, 500ppm.

" high rigidity " refers to that the hardness of water quality is higher than 250ppm.

Composition of detergent

Term of the present invention " composition of detergent " refers to fabric detergent composition, the free following composition of concrete choosingGroup: fabric detergent compositions, solid fabric composition of detergent, the fabric detergent composition of tablet/unit dosage forms.

Composition of detergent of the present invention contacts in water by the substrate (being textile article) that contact with needs, therebyBy the greasiness removal of substrate surface, reach the object of clean substrate surface.

Acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt derivative

The present invention represents the copolymer of acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid with AA-AMPS polymer.The sodium salt derivative of AA-AMPS polymer represents that the copolymer sodium salt of acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid spreads outBiological. The sodium salt derivative of AA-AMPS polymer contains sulfonate group and carboxylate group simultaneously, and these two kinds of groups are all parentsThe group that water-based is good.

This polymer that contains two kinds of hydrophilic radicals is called as double-hydrophilic polymer (DoubleHydrophilicPolymer). This base polymer can solve the shortcoming in some performance of polycarboxylic acids. Double-hydrophilic polymer refers to and contains twoPlant the polymer of dissimilar hydrophilic radical. On the one hand, in molecule a kind of hydrophilic structure unit can and stromal surfaceThere is strong interaction, copolymer is anchored on to the surface of matrix; On the other hand, another hydrophilic structure in moleculeUnit substantially not can with stromal surface effect, thereby ensure polymer sufficient hydrophilicity, also can reduce to a certain extentWith suppress polymer conformation and change deflation into from stretching, to ensure that polymer can bring into play complexing, dispersive property to large extent.To a certain degree, the surfactant of the somewhat similar similar traditional sense of double-hydrophilic polymer, can play stablely, dispersesComplex compound in the aqueous solution, the effect of particulate.

At present, commercially available parents' aqueous polymer is summarized as follows: the Acusol587 of Dow company, the 588th, solid content 30 to40% the copolymer containing carboxylate radical and sulfonate radical, molecular weight is 12000 to 13000. Suggestion use field is washing powder, especiallyCrystal growth for insoluble calcium polyphosphate and silicate has inhibitory action significantly. In addition the carboxylic acid of Acusol series,Salt and co-polymer of sulfonate can also be used in dish washing detergent compositions, for reducing glass and crust object dry runMiddle surperficial moisture film be formed with facilitation. The Acumer of Dow company series be solid content 35 to 45% containing carboxylate radical and sulfonic acidThe copolymer of root, for water treatment field. There is Acumer2000, Acumer2100, several trades mark such as Acumer3100.Acumer2000 is the bipolymer of carboxylate and sulfonate, and Acumer3100 is carboxylate and sulfonate, nonionic listThe terpolymer of body. Major function is the precipitation of effectively dividing the metallic compounds such as dispersion phosphate, zinc salt, iron oxide, for carbonThe dispersion of acid calcium also has certain positive effect.

Find composition, the molecular weight of acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt derivativeSize and distribute it is helped and washes detergency ability and have obvious impact. Based on above discovery, the present invention selects the sodium salt of copolymer to spread outThe following condition of biological gratification:

1) in copolymer, the quality of 2-acrylamide-2-methyl-propyl sulfonic acid construction unit accounts for acrylic acid and 2-acryloyl40% to 70% of amine-2-methyl-propyl sulfonic acid construction unit gross mass,

2) number-average molecular weight of copolymer sodium salt derivative is 5200 to 10000,

Inventor finds that acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt derivative can be effectivelyStrengthen the removal ability of composition of detergent to albumen dirt. Acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymerThe addition of sodium salt derivative can be 0.01% to 5%, calculates with composition weight. Based on cost with reach washing of expected degreeWash the consideration of performance, its consumption is no more than 10%, is 0.01% to 5%, is preferably 0.3% to 3%, more preferably 0.5% to2％。

Molecular weight and the molecular weight thereof of acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt derivative divide Cloth

Polymer is that a series of molecular size ranges differ, and has the mixture of the homologue composition of same structure unit.The mean molecule quantity of polymer is a statistic. Be called several equal molecules with the molecular weight of the average polymer of molecule numberAmount, represents with Mn. Molecular weight with the average polymer of quality is called weight average molecular weight, represents with Mw.

Acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt derivative are as a kind of polymer, sameThe homologue that exists a series of molecular size ranges to differ, its mean molecule quantity is a statistic.

In polymer, homologue molecular weight molecular weight distribution for difference (D) each other characterizes. D value is calculated as follows:

D = \frac{M_{W}}{M_{n}}

The D value of polymer is generally all greater than 1.0. D value is less, and the homologue molecular weight differences each other in polymer is describedDifferent more approaching; Molecular weight difference is larger each other for the larger explanation homologue of D value.

Acrylic acid and the equal molecule of 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt derivative number that the present invention selectsAmount is between 5000 to 10000, and molecular weight distribution (D value) is 1.60 to 1.85.

The molecular weight of acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt derivative and the survey of distribution thereof Method for testing

The present invention selects gel exclusion chromatography (GPC) to measure acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid is total toThe molecular mass and distribution of polymers sodium salt derivative. Specifically adopt water GPC to carry out molecular weight determination.

Water refers to that GPC test adopts water as mobile phase. Adopt differential refraction detector (RID) to detect.

The present invention adopts the polyacrylic acid molecular weight of German PSS company (PolymerStandardServiceGmbH)Standard items, the number-average molecular weight of standard items is between 1000 to 20000.

Surfactant system

The composition of detergent the present invention relates to is except acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodiumOutside salt derivative, also comprises surfactant system. Suitable surfactant system comprises, but is not restricted to: anion formSurface-active agent, non-ionic surface active agent, cationic surfactant, zwitterionic surfactant, double type surface-activeA kind of and the multiple mixture of agent. Preferred surfactant system comprises anion surfactant and non-ionic surfaceThe mixture of activating agent.

Anion surfactant

The content of anion surfactant is 0.01% to 30% of composition of detergent, with composition of detergent gross weightAmount is calculated.

Anion surfactant is selected from sulfonate surfactant, carboxylate surfactant, sulfate type tableThe mixture of one or more of surface-active agent; Preferably from alkylbenzenesulfonate, the alkyl sulfate of C8 to C18, C8's to C18Ethoxylated fatty alcohol sulfate, alpha-alkene sulfonate, fatty acid alkyl ester sulfonate, the soap of C8 to C18, ethyoxylChange the one of Fatty Alcohol Ether Carboxylate, and their mixture.

In some embodiments, the mixture of anion surfactant preferably contains alkylbenzenesulfonate and derivativeThing. Described alkylbenzenesulfonate meets following general formula:

Wherein R1 is that carbon number is 6 to 24 alkyl, M⁺For cation, such as potassium ion, sodium ion, ammonium ion etc. R1 canTo be the alkyl of straight chain, it can be also the alkyl of side chain; Can be saturated alkyl, can be also to contain one or more insatiable hungersAlkyl with two keys. Further preferably R1 is that carbon number is 8 to 18 straight chained alkyl. Suitable example is DBSASodium.

In some embodiments, the aliphatic alcohol sulfate that the mixture of anion surfactant contains ethoxylation.Ethoxylated fatty alcohol sulfate is the derivative of ethoxylate fatty alcohol, has following general formula:

Wherein R1 is that carbon number is 6 to 24 alkyl; X is 0.5 to 30; Wherein M⁺For cation, for example potassium ion, sodium fromSon, ammonium ion etc. R1 can be the alkyl of straight chain, can be also the alkyl of side chain; Can be saturated alkyl, can be also to containThere is the alkyl of one or more unsaturated double-bonds. Preferably R1 is that carbon number is 8 to 18 straight chained alkyl. X represents average ethoxylationDegree, is 0.5 to 30, preferably 0.5 to 10, more preferably 0.5 to 3. Suitable example is the TexaponN70 of BASF AG.

In some embodiments, contain alkyl sulfate, alkyl segment can be straight chain, can be also side chain, canTo be saturated alkyl, it can be also the alkyl that contains one or more unsaturated double-bonds. Preferred alkyl carbon number is 6 to 24 alkaneBase sulfate, further preferred carbon number is 8 to 18 alkyl sulfate. Suitable example is lauryl sodium sulfate.

In some embodiments, contain alpha-alkene sulfonate, there is following general formula:

Wherein a is 0 to 2, R₁That carbon number is 6 to 24 alkyl, preferably R₁That carbon number is 8 to 18 alkyl.

In some embodiments, the mixture of anion surfactant contains soap, preferably carbon number be 8 extremelyThe soap of 18. The alkyl segment of aliphatic acid can be straight chain, can be also side chain, can be saturated alkyl, alsoIt can be the alkyl that contains one or more unsaturated double-bonds. Soap can be single composition, can be also multiple fatThe mixture of acid composition. Suitable example is enuatrol, sodium laurate. Described soap also comprises ethoxylized fatty alcohol etherCarboxylate, preferably 8 to 18 of the carbon numbers of fatty alcohol, average degree of ethoxylation is preferably 2.0 to 10.

Described anionic surfactant mixture can also comprise a kind of and many of alkyl sodium disulfonate or derivatives thereofPlant mixture, preferred alkyl diphenyl ether sodium disulfonate, suitable example is disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate salt, DOW companyDowfax series of products. Can also contain fatty acid alkyl esters sulfate, be preferably fatty acid methyl ester sulfate (MES), fatPreferably 8 to 18 of acid carbon numbers. Can also comprise sulfosuccinate, be preferably AEO sulfosuccinic acid monoestersDisodium salt, preferably 8 to 18 of fatty alcohol carbon numbers, average degree of ethoxylation is preferably 2.0.

Non-ionic surface active agent

The content of non-ionic surface active agent is 0.01% to 30% of composition of detergent, with composition of detergent gross weightAmount is calculated.

Non-ionic surface active agent is selected from fatty alcohol alkoxy compound, APG, fatty acid alkoxylates, fatAcid ethoxylate, fatty acid alkyl alcohol amide, ethoxylation dehydration sorbic acid alcohol ester a kind of and their mixture.

In some embodiments, non-ionic surfactant mixture preferably contains fatty alcohol alkoxy compound, described inFatty alcohol alkoxy compound has following general formula:

Wherein, n is 6 to 24; X is 0.5 to 30, y to be 0 to 10.

Described fatty alcohol alkoxy compound is fatty alcohol and epoxyalkane ring-opening polymerisation under base catalyst effectProduct is mixture substantially. Fatty alcohol comprises the isomery alcohol of straight chain alcohol or side chain. Alkoxy grp comprises ethoxy group and the third oxygenGroup. The preferred carbon number of fatty alcohol is 8 to 18 fatty alcohol, and preferred alcohol includes, but are not limited to hexanol, octanol, decyl alcohol, 2-secondBase is alcohol, 3-propyl enanthol, and laruyl alcohol, different three decyl alcohol, tridecanol, tetradecanol, hexadecanol, Palmitoleyl alcohol, stearyl alcohol,One of isooctadecanol, oleyl alcohol, sub-oleyl alcohol, linolenyl alcohol and composition thereof. Average degree of ethoxylation x preferably 2 to 12. PreferenceThe Zi Shi SHELL NEODOL of company series linear primary alcohol ethoxylate product, the ethoxylation of the ECOSURFEH of DOW company seriesWith the third oxidation 2-ethylhexanol product, the LutensolXL of BASF AG series ethoxylation and the third oxidation 3-propyl enanthol productWith the LutensolXP of BASF AG series ethoxylation 3-propyl enanthol product.

In some embodiments, non-ionic surfactant mixture preferably contains APG, has following logicalFormula:

Wherein, n is 6 to 24, p to be 1.1 to 3. Preferably n is 8 to 16. Suitable APG is as BASF AGGlucopon series APG product.

Non-ionic surfactant mixture can contain fatty acid alkoxylates, preferably from ethoxylation C8 to C18Fatty acid ester, average degree of ethoxylation is 2 to 10. Can contain ethoxylation dehydration sorbitol Arrcostab, alkyl carbon numberBe 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 aliphatic acid is 6 to 24, canTo be the aliphatic acid of straight chain, can be also the aliphatic acid of side chain, can be saturated aliphatic acid, can be also undersaturated fatAcid; Alkylol number is 0 to 2. Preferred fatty acid carbon number is a glycollic amide of 8 to 18, diglycollic amide, and 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. Preferably n is 8 to 18, x to be 0.5 to 30. Preferably x is 4 to 10. Suitable exampleIt is the MEE of LION company product.

Non-ionic surfactant mixture can contain polyether surfactant. Polyether surfactant is a kind ofPolymer, the non-ionic surface active agent that contains oxidation ethylene and/or oxidation trimethylene repetitive, suitable example is as BASF public affairsThe Pluronic of department series of products.

Other surfactant

The surfactant system the present invention relates to can contain other surfactants, is selected from: 0～30% amphionSurfactant, the group of 0～30% cationic surface active agent composition. Zwitterionic surfactant comprises betaine type tableSurface-active agent, Imidazoline Surfactants, amino acid type surfactant, amine oxide type surfactant; Comprise but do not limitBe formed on: alkyl betaine, fatty acid amide betaine, fattyamidopropyl betaine, fatty amide propyl hydroxypropyl sulfonation beetAlkali, comprises acetate alkyl sodium type imidazoline, fatty acid type imidazoline, sulfonic acid type imidazoline; Alanine derivatives, glycine spreads outBiological; Alkyl dimethyl amine oxide, fatty acyl amido propyl-dimethyl amine oxide etc. Cationic surfactant comprises quaternary ammonium saltClass surfactant, heterocyclic class surfactant, polymer-type cationic surfactant. Comprise: single long linear quaternary ammonium salt,Two long linear quaternary ammonium salts, benzyl quaternary ammonium salt, hydroxyalkyl quaternary ammonium salt, fatty amide propyl hydroxyalkyl quaternary ammonium salt, has vinyl pyrroleThe multi-quaternary ammonium salt that alkane ketone and unsaturated amides or unsaturated quaternary ammonium salt copolymerization obtain.

Polycarboxylate

The composition of detergent the present invention relates to is not substantially containing polycarboxylic acids. Term " substantially not containing " refers in preparation the present inventionIn the composition of detergent relating to, artificially do not add polycarboxylate. Particularly, polycarboxylate is at composition of detergent of the present inventionIn weight content not higher than 0.0001%.

Term " polycarboxylate " index average molecular weight, more than 2000, only comprises following structural formula in its constitutional repeating unit(I), any one or multiple polymer (II);

Wherein A is COOH or COO^-M⁺，M⁺For cation, can be potassium ion, sodium ion, ammonium ion etc. B is H or CH₃。

Washing assisant

The composition of detergent the present invention relates to can comprise washing assisant, described washing assisant be selected from fluorescent whitening agent,The group of enzyme preparation, bleach system composition.

Fluorescent whitening agent

The composition of detergent the present invention relates to preferably contains fluorescent whitening agent. Fluorescent whitening agent is in composition of detergentApplication be technology known in the art, and have a lot of commercially available fluorescent whitening agent commodity. Conventionally the use of fluorescent whitening agentAmount, for 0.01% to 2wt% of total composition, is preferably 0.01% to 0.1%. Fluorescent whitening agent (mostly is with its alkali metal saltSodium salt) form existence. Preferred fluorescent whitening agent including but not limited to: diphenylethyllene connects benzene compound. Suitable exampleTwo (the 2-sodium sulfonate styryl) biphenyl of 4,4'-, as the product of the CBS-X of BASF AG trade mark. Diamines stilbene two-Sulfoacid compound. Suitable example is 4,4 '-bis-{ [(4-phenylamino 6-morpholino-1,3,5-, triazine-2-yl)] amino } equal twoBenzene is for ethene-2,2 '-disulfonic acid disodium.

Can comprise the group that is selected from following compound composition: 2-(4-styryl-3-sulfo group phenyl)-2H-naphtho-[1,2-D] 1-Sodium-1,2,4-Triazole, 4,4 '-bis-{ [(4-phenylamino 6-(N-methyl-N-2-ethoxy) amino-1,3,5-, triazine-2-yl)] amino }Stilbene-2,2 '-disulfonic acid disodium, 4,4 '-bis-{ [(4-phenylamino 6-morpholino-1,3,5-, triazine-2-yl)] ammoniaBase } stilbene-2,2 '-disulfonic acid disodium, 4,4 '-bis-(2-sulphophenyl vinyl) biphenyl disodium.

Enzyme preparation

The composition of detergent the present invention relates to can comprise one or more of enzyme preparations, so that clean-up performance to be provided, knitsThing nursing and/or other beneficial effect. Described enzyme preparation is selected from the group of following enzyme composition: protease, AMS, celluloseEnzyme, hemicellulase, phosphatidase, esterase, lipase, peroxidase/oxidizing ferment, pectase, lyases, mannase,Cutinase, reductase, zytase, amylopectase, tannase, pentosanase, maltosan, arabinase, β-Portugal is poly-Carbohydrase. Conventional enzyme preparation is protease, amylase, lipase, cutinase and/or cellulase. Enzyme preparation content is washing0.001% to 5% of agent composition, is preferably 0.01% to 2%.

Composition of detergent of the present invention can comprise the enzyme stabilising system that accounts for composition weight 0.001% to 10%. InstituteStating enzyme stabilising system can be compatible with composition of detergent, can comprise calcium ion, boric acid, borax, propane diols, glycerine, polyalcoholOne and composition thereof. The weight of enzyme stabilising system and consumption are with according to the form of composition of detergent and composition and enzyme systemThe type of agent is adjusted.

Bleach system

The composition of detergent the present invention relates to can comprise bleach system. Bleach system comprises hypohalite bleaching agent,Peroxide bleaches. Peroxide bleaches typically comprises hydrogen peroxide source and bleach activating system. Hydrogen peroxide source bagDraw together but be not limited to perborate, percarbonate, persulfate, and their mixture. In some embodiments, preferredHydrogen peroxide source is SODIUM PERCARBONATE. Bleach system can comprise bleach-activating, and described bleach-activating is used for promoting peroxidatingThing at a lower temperature fast decoupled produces oxygen, is selected from the group of following compound composition: tetra acetyl ethylene diamine, benzoyl is ownLactams, 4-nitro benzoyl caprolactam, 3-chlorobenzene formacyl caprolactam, benzoyloxy benzene sulfonate, nonanoyl oxygenBase benzene sulfonate, phenol benzoate, the last of the ten Heavenly stems acyloxy benzene sulfonate, benzoyl valerolactam, pungent acyloxy benzene sulfonate, transitionMetal bleach catalyst.

The composition of detergent the present invention relates to can also comprise oxygen stabilizer alive, and described oxygen stabilizer alive is used for adjustingOxide decomposes the speed that produces hydrogen peroxide, makes the local concentration of hydrogen peroxide be unlikely to excessive, and suitable example is hydroxylEthylidene diphosphonic acid, the organic phosphoric acid of the polyfunctionalities such as ethylenediamine tetraacetic methene phosphoric acid.

Anti redeposition agent

From the viewpoint of effective raising clean result, it is anti-heavy again to comprise at the composition of detergent the present invention relates toLong-pending agent. Described anti redeposition agent includes, but are not limited to the group of following compound composition: cellulose derivative, for example carboxymethyl fibreDimension element, ethylhydroxyethylcellulose, methylcellulose; The homopolymers of vinyl pyrrolidone and copolymer, the poly-second of for example straight chainThiazolinyl pyrrolidones, the copolymer of NVP and vinyl acetate, NVP and N-vinylThe copolymer of imidazoles, polyvinyl oxazolidone.

Optional member

The composition of detergent the present invention relates to comprises following optional additive: alkaline agent, and inorganic salts, viscosity modifier,Anticorrisive agent, colouring agent, essence.

The composition of detergent the present invention relates to can comprise one or more alkaline agents, and alkaline agent is selected from NaOH, hydrogen-oxygenChange potassium, alkali carbonate, alkali-metal silicate. In some embodiments, the composition of detergent the present invention relates to canTo comprise one or more salts, described salt can be inorganic salts or organic salt. The composition of detergent the present invention relates toCan comprise one or more of viscosity modifiers, so that suitable viscosity to be provided. Suitable viscosity modifier is as inorganic salts, manySugar, sizing material, short chain fatty alcohol, short chain fatty alcohol alkyl ether. Suitable example is sodium chloride, ethanol, and propane diols, natrium citricum,Alkyl-hydroxyalkylcelluloswith ether, carragheen, xanthans, polyacrylamide derivative.

In some embodiments, the composition of detergent the present invention relates to preferably comprises anticorrisive agent, and suitable example isPhenoxy group alcohol, Sodium Benzoate; OIT and derivative thereof be as methylisothiazolinone, methylchloroisothiazandnone, benzoA kind of or its mixture of OIT. Anticorrisive agent consumption is 0.001% to 5%, is preferably 0.01% to 2%.

In some embodiments, the composition of detergent the present invention relates to contains colouring agent, and described colouring agent comprises and dyesMaterial and pigment. Colouring agent can comprise the colouring agent of applying in be used in cleaning product, and suitable example is as acid scarlet G, alkaliProperty magenta, Methanil Yellow G, Acid Light Yellow G, alkaline yolk, direct fast blue B₂RL, indigo-blue etc.

The composition of detergent the present invention relates to preferably contains spices, and described spices comprises all and is applicable to cleaning productFragrance component. Spices used of the present invention can be natural origin, can be also the goods of chemical synthesis, or the two is mixedCompound. Suitable example is as lemon, rose, and jasmine, lavender, oranges and tangerines perfume (or spice), blue or green fragrant, the banksia rose etc.

Except above-mentioned optional member, composition of detergent of the present invention also can comprise water, organic solvent, cosolvent, solubilisingAgent, structural agent, short infusion, foam inhibitor, fabric softener, various common and the conventional additives such as anti wrinkling agent. These addIt is all well-known to those skilled in the art adding agent and associated method of use, and the type that it is concrete and the selection of consumption can basesActual needs is adjusted.

Preparation and using method

Composition of detergent of the present invention can be formulated into various suitable goods forms and adopt those skilled in the artKnown the whole bag of tricks preparation. Suitable goods form includes, but are not limited to liquid-type, solid particle type, tablet form. LiquidThe preparation of build composition can be undertaken by conventional means, specifically should the state in solution and effect according to component, andThe stability of component and heat endurance are selected from suitable processing temperature and process time. The preparing process of solid particle type compositionCan be the aqueous slurry that first preparation contains part component, then that slurry spraying is dry, finally will be dried gained particle with in additionThe component of part is mixed.

The using method of composition of detergent of the present invention is well-known to those skilled in the art, typical using methodBe by concrete composition of detergent embodiment in undiluted mode or be diluted in the mode in water, and be washed objectSurface Contact, then rinsing is washed the surface of object. Preferably, be washed object above-mentioned contact procedure and rinse step itBetween carry out washing step. Washing step includes but not limited to clean and mechanical agitation. Be washed object and comprise fabric and tableware. InstituteState composition of detergent concentration in water and be about 500ppm to 10000ppm, water temperature is preferably 5 DEG C to approximately 60 DEG C. Water be washedThe ratio of object is preferably about 1:1 to about 20:1.

Without further description, believe that those skilled in the art use the above can use to greatest extent thisInvention. The following examples object is further to introduce and show specific embodiments within the scope of the present invention. Therefore, realExecute example and be only interpreted as for showing in more detail the present invention, and the content not limiting the present invention in any way.

In following examples, except as otherwise noted, all content is all weight percentages, about containing of ingredients listedAmount is the content of the active material through converting.

In described embodiment, by the trade mark and the abbreviation that use below.

PAA: the sodium salt derivative of acrylate homopolymer, belongs to polycarboxylate. DowChemical company productAcusol445N。

LAS:C10-C13 sodium n-alkylbenzenesulfonate.

AOS: alpha-alkene sulfonate, anion surfactant.

AES: ethoxylated fatty alcohol sulfate, the main carbon number of fatty alcohol is C12-C14, average ethoxyquin degree is 2, the moonIonic surface active agent.

K12: lauryl sodium sulfate, anion surfactant.

AEO7: ethoxylized fatty alcohol, average ethoxyquin degree is 7, non-ionic surface active agent.

AEO9: ethoxylized fatty alcohol, average ethoxyquin degree is 9, non-ionic surface active agent.

TO-7: ethoxylation isomerous tridecanol, average ethoxyquin degree is 7, non-ionic surface active agent, BASF AG producesProduct, the trade mark is LutensolTO-7.

XP-80: ethoxylation 2-propyl enanthol, average ethoxyquin degree is 8, non-ionic surface active agent, BASF AGProduct, the trade mark is LutensolXP-80.

XL-80: ethoxylation and propoxyl group 2-propyl enanthol, average ethoxyquin degree is 8, non-ionic surface active agent,BASF AG's product, the trade mark is LutensolXL-80.

MEE: fatty acid methyl ester ethoxylate, non-ionic surface active agent, LION company product.

APG:C8-C14 APG, non-ionic surface active agent, BASF AG's product, the trade mark is Glucopon650EC.

LAO: dodecanamide propyl amine oxide, non-ionic surface active agent.

CAB: cocoamidopropyl betaine, zwitterionic surfactant.

LAB: lauroylamidopropyl betaine, zwitterionic surfactant.

Protease: alkali protease, Novozymes company product, the trade mark is SavinaseUltra16XL.

Viscosity modifier: natrium citricum.

Two (the 2-sodium sulfonate styryl) biphenyl of brightening agent: 4,4'-, fluorescent whitening agent, BASF AG's product, the trade mark isCBS-X。

Anticorrisive agent: methylisothiazolinone and chlormethylisothiazo,ine alcohol/ketone mixtures.

Peroxide bleaches: SODIUM PERCARBONATE.

The preparation technology embodiment of acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt derivative

Press the composition of table 1 polymerization system, prepare acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt spreads outBiology, technique is as follows:

1) in reactor, add 2-acrylamide-2-methylpro panesulfonic acid, acrylic acid, RAFT reagent, add 60 grams go fromSub-water, is stirred to completely and dissolves;

2) be warming up to 60 DEG C, initator is dissolved in 5 grams of deionized waters and dissolves the aqueous solution that obtains initator;

3) in reactor, drip initiator solution, time for adding is controlled at 10 minutes to 15 minutes, dropwises follow-upContinuous stirring reaction, temperature keeps 60 DEG C. React and be cooled to room temperature after 6 hours;

4) in reactor, add the 10%NaOH aqueous solution, regulate pH to 8.5;

5) be warming up to 100 DEG C of vacuum rotary steams, removal solvent obtains acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid is total toPolymers sodium salt derivative.

The name of table 1 acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt derivative

The molecular mass and distribution of acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt derivative is surveyed Examination

Acrylic acid of the present invention and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt derivative are carried out to molecular weight largeLittle and distribute test, step is as follows:

1) adopt AglilentPLaquagel-OH30,8 μ m gel chromatographic columnses carry out molecular weight test, adopt differentialRefraction detector (RID), as detection part, adopts AgilentGPC software to carry out interpretation of result.

2) trisodium phosphate aqueous solution that mobile phase is 0.02mol/L, flow velocity is 1mL/min, column temperature is 35 DEG C. Molecular weight markAccurate product are the polyacrylic acid standard items of German PSS company (PolymerStandardServiceGmbH), its number-average molecular weightBetween 1000 to 20000. Take 30 milligrams of different molecular weight polyacrylic acid standard items in 10 milliliters of volumetric flasks, add ultrapureWater is settled to scale, makes series standard solution.

3) take 30 milligrams, AA-AMPS copolymer sodium salt derivative sample in 10 milliliters of volumetric flasks, add ultra-pure water fixedHold to scale, make sample solution.

4) test result of acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt derivative is as table 2Show. It is 5200 to 10000 that copolymer A, B, C all meet number-average molecular weight, and molecular weight distribution is 1.60 to 1.85.

The molecule measuring test result of table 2 embodiment 1-6 and comparative example 1-3

The preparation technology embodiment 1-3 of composition of detergent and comparative example 1-3

According to following table 3 composition preparation fabric detergent composition A-F, preparation process is as follows:

1) in preparing tank, add deionized water;

2) start stirring, add above-mentioned various surfactant, be warming up to 60 DEG C, be stirred to completely and dissolve;

3) withdraw thermal source, add viscosity modifier, AA-AMPS copolymer sodium salt derivative of the present invention or with opposingThe component of ratio, is stirred to completely and dissolves;

4) in temperature lower than 45 DEG C, add fluorescent whitening agent brightening agent, essence, pigment, anticorrisive agent, is stirred to completely moltenSeparate.

Table 3 liquid detergent composition A-F composition

The liquid detergent composition A-F preparing in embodiment 1-3 and comparative example 1-3 is washed to detergency ability as followsTest.

Decontamination performance test methods under 250ppm hardness

Detergency ability test is carried out with reference to GB/T13174-2008. Adopt sebum, albumen, three kinds of soiled cottons of carbon black, use northThe Jing Kang light optical instrument WSD-3U of Co., Ltd fluorescence leucometer is measured three kinds of soiled cottons and is washed front whiteness W₁. Press GB/T13174-The slurry that 2008 preparation hardness are 250ppm, wherein calcium ions and magnesium ions ratio is 3:2.

The slurry of the liquid detergent composition A-F 250ppm preparing in embodiment 1-3 and comparative example 1-3 is joinedMake 0.2% solution, complete 1 washing, wash time with the RHLQ of China Daily-use Chemical Industry Institute type Terg-O-Tometer20min, wash temperature is 30 DEG C, 120 revs/min of mixing speeds are by three kinds of soiled cotton rinsings, dry, by WSD-3U fluorescence whitenessThree kinds of soiled cottons of instrumentation amount are washed rear whiteness W₂. Whiteness difference △ W is calculated as follows:

△W＝W₂-W₁。

W₂: soiled cotton wash rear whiteness,

W₁: soiled cotton wash front whiteness.

△ W value is less, illustrates that before soiled cotton is washed, to wash rear whiteness difference less, and the washing usefulness of composition is poorer.

Taking comparative example 1 as benchmark, the decontamination ratio P that calculates each composition of surveying is calculated as follows:

P＝△W_i/△W_I，

△W_i: the whiteness difference of the composition of surveying,

△W_I: the whiteness difference of comparative example 1.

Wherein P value is less than 1, illustrates that the dirt-removing power of surveyed composition is less than comparative example 1, and P value is greater than 1, and institute's survey group is describedThe dirt-removing power of compound is greater than comparative example 1. P value is larger, illustrates that the dirt-removing power of surveyed composition is stronger.

Table 4 is decontamination results of liquid detergent composition A-F.

Table 4 liquid detergent composition decontamination result

From table 4, the comprehensive detergency ability of comparative example 3 is the poorest, and acrylic acid and 2-acrylamide-2-methyl-propyl are describedSulfonic acid copolymer sodium salt derivative (embodiment 1-3, comparative example 2), acrylate homopolymer sodium salt derivative (comparative example 1) is just all havingUsefulness is washed in helping of face. Compare with 2 with comparative example 1, adopt three enforcements that meet AA-AMPS copolymer sodium salt of the present inventionExample all has obviously better albumen soil removal capabilities. Compare with 2 with comparative example 1, three embodiment for carbon black dirt andThe removal ability of sebum dirt is close. Illustrate that embodiment of the present invention 1-3 has under the water quality environment of 250ppm hardnessObviously be better than the albumen soil removal capabilities of comparative example 1-3, and better comprehensive clean effect.

Liquid detergent composition A-F prepared by embodiment 1-3 and comparative example 1-3 carries out following anti-dirt deposition propertiesTest.

Anti-dirt deposition properties method of testing

Employing meets polyester textile and the bafta of GB/T7568.2-2008. Use the limited public affairs of Beijing Kang Guang optical instrumentThe WSD-3U of department fluorescence leucometer is measured the front whiteness W ' that washes of two kinds of fabrics₁。

Dirt is parrot coal dirt, and preparation steps is as follows:

1) by 20g carbon black dispersion in 70g deionized water, add 7.5g vegetable oil, 2.5g mineral oil, with the IKA of IKA companyT25 homogenizer (band S25N-18G homogeneous cutter) homogeneous 20 minutes, obtains 100g parrot coal dirt.

2) slurry that is 250ppm by GB/T13174-2008 preparation hardness, wherein calcium ions and magnesium ions ratio is 3:2.

3) in the situation that keeping stirring, 10g parrot coal soil dispersion, in 1L slurry, is added rapidly to 2g embodimentThe liquid detergent composition of 2 preparations, adds fabric to be washed.

With the RHLQ of China Daily-use Chemical Industry Institute type Terg-O-Tometer, wash time 20min, wash temperature is 30DEG C, mixing speed 120r/min, by two kinds of fabric rinsings, dry, measure, record after fabric washing in vain with WSD-3U fluorescence leucometerDegree W '₂. Whiteness difference △ W ' is calculated as follows:

△W’＝W’₂-W’₁。

W’₂: fabric wash rear whiteness,

W’₁: fabric wash front whiteness.

△ W ' value is larger, illustrates that the pollution that fabric is subject to greasy filth dirt at washing process is more serious, the anti-dirt of compositionDeposition usefulness is poorer.

Taking comparative example 1 as benchmark, calculate each and survey composition anti-soil deposition ratio R and be calculated as follows:

R＝△W’_i/△W’_I，

△W’_i: the whiteness difference of the composition of surveying,

△W’_I: the whiteness difference of comparative example 1.

Wherein R value is greater than 1, illustrates that the anti-dirt deposition capability of surveyed composition is less than comparative example 1, and R value is less than 1, explanationThe anti-dirt deposition capability of the composition of surveying is greater than comparative example 1. P value is larger, illustrates that fabric is subject to more pollutions, surveys combinationThe anti-dirt deposition capability of thing is more weak.

Table 5 is anti-dirt deposition results of liquid detergent composition A-F.

Table 5 liquid detergent composition A-F anti-dirt deposition results

From table 5, completely not containing polycarboxylate and acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodiumThe comparative example 5 anti-dirt deposition capabilities of salt derivative are the poorest. Polycarboxylate and acrylic acid and 2-acrylamide-2-methyl-prop are describedBase sulfonic acid copolymer sodium salt derivative is all to have positive helping to wash usefulness.

No matter be cotton fabric or polyester textile, the embodiment of the present invention all has the anti-dirt deposition significantly better than comparative exampleUsefulness. Compare with polyester textile, acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt derivative are for cottonOn fabric, the inhibition of dirt deposition is more obvious.

As can be seen here, use and meet acrylic acid and the 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium that patent requiresThe embodiment 1-3 of salt derivative has the anti-dirt deposition effect that is obviously better than comparative example under the washing condition of water quality of 250ppmEnergy.

Albumen dirt removal capacity test under different quality hardness

Liquid detergent composition prepared by embodiment of the present invention 1-3 and comparative example 1 carries out under different quality hardnessAlbumen dirt is removed and can be tested. Washing detergency ability method of testing under different quality hardness is identical with description above, justThe hardness of slurry changes 350ppm into, 500ppm. The slurry of different hardness is pressed GB/T13174-2008 preparation, whereinCalcium ions and magnesium ions ratio is 3:2. Table 6 is decontamination result tables of liquid detergent composition under different quality hardness. Table 6 different qualityThe decontamination result of liquid detergent composition under hardness

From table 6, at 250ppm, 350ppm, in the washing water quality environment of 500ppm, compares with comparative example, three realitiesExecute example and all there is obviously better albumen soil removal capabilities. Compare with comparative example, three embodiment are for carbon black dirt and skinThe removal ability of fat dirt is close. Illustrate under the water quality environment of 250ppm to 500ppm hardness, of the present inventionAcrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt derivative are given composition of detergent and have the egg of enhancingWhite soil removal capabilities, and better comprehensive clean effect.

The preparation technology embodiment 4 of composition of detergent

Step of preparation process according to following table 7 composition preparation fabric detergent compositions is as follows:

1) in preparing tank, add deionized water;

3) withdraw thermal source, add viscosity modifier, acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium saltDerivative, is stirred to completely and dissolves;

4) in temperature lower than 45 DEG C, add successively brightening agent, anticorrisive agent, enzyme preparation, enzyme stabilizers, essence, pigment, stirTo dissolving completely.

Table 7 fabric detergent compositions composition

Component	Content (%)
		LAS	3
Odium stearate	2 17 -->
		Enuatrol	2
AES	5
		AEO9	4
TO-7	1
		XP-80	1
XL-80	1
		MEE	1
Copolymer A	1.5
		Viscosity modifier	2
Protease	0.2
		Enzyme stabilizers	3
Brightening agent	0.03
		Pigment	0.1
Essence	0.1
		Anticorrisive agent	0.1
Water	Surplus

The preparation technology embodiment 5 of composition of detergent

According to following table 8 composition preparation dish washing detergent compositions. Preparation process is as follows:

1) in preparing tank, add deionized water;

4) in temperature lower than 45 DEG C, add successively anticorrisive agent, essence, pigment is stirred to completely and dissolves.

Table 8 liquid dishwashing detergent compositions composition

Component	Content (%)
		K12	3
LAS	2
		AEO7	2
CAB	2
		LAB	2
APG	3
		LAO	2
Copolymer C	1
		Viscosity modifier	1.5
Pigment	0.05
		Essence	0.1
Anticorrisive agent	0.05
		Water	Surplus

The preparation technology embodiment 6 of composition of detergent

The step of preparation process of preparing granular pattern fabric detergent composition according to following table 9 compositions is as follows:

1) press shown in table 7, in preparing tank, add deionized water, LAS, AOS, acrylic acid and 2-acrylamide-2-methylPropyl sulfonic acid copolymer sodium salt derivative, sodium sulphate, sodium carbonate, zeolite, flower bulb alkali, brightening agent, starts stirring, obtains solid contentBe 65% to 75% aqueous slurry, and be 65 to 75 DEG C temperature control;

2) aqueous slurry high-pressure pump is delivered in spray drying tower to the dry granule type solid that obtains of spraying;

3) granule type solid is transported to rear match system, in preparing tank and AEO9, peroxide bleaches, bleach activatingAgent, the oxygen stabilizer of living, protease, pigment, essence mixes, and obtains granular pattern fabric detergent composition.

Table 9 granular pattern fabric detergent composition composition

Dimension disclosed herein and numerical value should not be construed as the strict restriction of described exact value. Unless otherwise indicated, everyIndividual such dimension is intended to represent described value and around the scope being equal in the function of this value. For example, be disclosed as the amount of " 40mm "Guiding principle is intended to represent " about 40mm ".

The All Files of quoting in summary of the invention is all included in herein with way of reference in relevant portion. For anyQuoting of file should not be interpreted as admitting that it is relevant prior art of the present invention.

Although illustrated and described specific embodiment of the invention scheme, for those skilled in the artIt is evident that, in the situation that not deviating from essence of the present invention and scope, can make multiple other amendment and changesType. Within these amendments and modification are all included protection scope of the present invention in.

The above, be only preferred embodiment of the present invention, not the present invention done to any pro forma restriction, thereforeEvery technical solution of the present invention content that do not depart from, that according to technical spirit of the present invention, above embodiment is done anyly simply repaiiesChange, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.

Claims

1. promote the method for cleaning compositions to albumen soil removal capabilities, it is characterized in that: the method is to use thirdOlefin(e) acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt derivative, the sodium salt derivative of described copolymer meet withLower condition:

1), in copolymer, the quality of 2-acrylamide-2-methyl-propyl sulfonic acid construction unit accounts for acrylic acid and 2-acrylamide-2-40% to 70% of methyl-propyl sulfonic acid construction unit gross mass;

2. method according to claim 1, is characterized in that: described acrylic acid and 2-acrylamide-2-methyl-propyl sulphurAcid copolymer sodium salt derivative weight content in composition of detergent is 0.01% to 5%, is preferably 0.3% to 3%, more excellentElect 0.5% to 2% as.

3. there is a composition of detergent for Enhancin soil removal capabilities, it is characterized in that it comprises:

Weight content is 0.01% to 40% anion surfactant, and weight content is 40% to 0.01% nonionic tableSurface-active agent, 0～30% zwitterionic surfactant, the group of 0～30% cationic surface active agent composition, washingAuxiliary agent, 0.01% to 5% acrylic acid and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodium salt derivative, described copolymerizationThe sodium salt derivative of thing meets the following conditions:

1) in copolymer, the quality of 2-acrylamide-2-methyl-propyl sulfonic acid construction unit accounts for acrylic acid and 2-acrylamide-2-40% to 70% of methyl-propyl sulfonic acid construction unit gross mass;

4. composition of detergent according to claim 3, is characterized in that: described anion surfactant is selected from sulfonic acidSalt type surfactant, carboxylate surfactant, the mixture of one or more of sulfated surfactant; PreferablyFrom alkylbenzenesulfonate, the alkyl sulfate of C8 to C18, the ethoxylated fatty alcohol sulfate of C8 to C18, alpha-olefin sulfonic acidSalt, fatty acid alkyl esters sulfonated ester, the soap of C8 to C18, ethoxylized fatty alcohol ether carboxylate.

5. composition of detergent according to claim 3, is characterized in that: described non-ionic surface active agent is selected from fatAlcohol alkoxylates, APG, fatty acid alkoxylates, fatty acid ethoxylate, fatty acid alkyl alcohol amide, secondOxygen base dehydration sorbic acid alcohol ester a kind of and their mixture.

6. composition of detergent according to claim 3, is characterized in that: described washing assisant is selected from 0.01% to 2%Fluorescent whitening agent, 0.001% to 5% enzyme preparation, 0.001% to 10% enzyme stabilising system, bleach system, antiredepositionThe mixture of one or more of agent.

7. composition of detergent according to claim 3, is characterized in that: also further comprise following optional interpolationAgent: alkaline agent, inorganic salts, viscosity modifier, anticorrisive agent, colouring agent, one or more mixture of essence.

8. composition of detergent according to claim 3, is characterized in that: described composition of detergent can be any shapeFormula, comprises following form: liquid form, solid form, for example powder, particle, tablet; Gel, bar, wet tissue etc., andConsumer's cleaning products form that other is even or heterogeneous.

9. the preparation method of the composition of detergent described in any one in claim 3-8, is characterized in that comprising the following steps:

1) in preparing tank, add deionized water;

3) withdraw thermal source, add acrylic acid as claimed in claim 3 and 2-acrylamide-2-methyl-propyl sulfonic acid copolymer sodiumSalt derivative, is stirred to completely and dissolves;

4) in temperature lower than 45 DEG C, add washing assisant as claimed in claim 6, be stirred to completely and dissolve.

10. the preparation method of the composition of detergent described in any one in claim 3-8, is characterized in that comprising following stepRapid:

1) in preparing tank, add deionized water, anion surfactant, acrylic acid and 2-acrylamide-2-methyl-propyl sulphurAcid copolymer sodium salt derivative, inorganic salts, zeolite, brightening agent, starts stirring, obtains solid content and be 65% to 75% aqueous slurryMaterial, and be 65 to 75 DEG C temperature control;

3) granule type solid is transported to rear match system, in preparing tank and non-ionic surface active agent, peroxide bleaches,Bleach-activating, the oxygen stabilizer of living, protease, pigment, essence mixes, and obtains granular pattern fabric detergent composition.