CN105647678B - Lift method and detergent composition of the cleaning compositions to albumen soil removal capabilities - Google Patents
Lift method and detergent composition of the cleaning compositions to albumen soil removal capabilities Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38618—Protease or amylase in liquid compositions only
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
- C11D3/3953—Inorganic bleaching agents
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
- C11D1/721—End blocked ethers
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Abstract
Method of the cleaning compositions to albumen soil removal capabilities is lifted the invention discloses a kind of.This method is to use 2 methyl-propane sulfonic acid copolymer sodium salt derivative of acrylic acid and 2 acrylamide, and the sodium salt derivative of the copolymer meets the following conditions：1) quality of 2 acrylamide, 2 methyl-propane sulfonic acid construction unit accounts for the 40% to 70% of 2 methyl-propane sulfonic acid construction unit gross mass of acrylic acid and 2 acrylamide in copolymer；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.Detergent composition provided by the invention containing 2 methyl-propane sulfonic acid copolymer sodium salt derivative of acrylic acid and 2 acrylamide, said composition have good albumen soil removal capabilities in high-hardness water.
Description
Technical field
The present invention relates to polymer is used as method of the cleaning compositions to the removal ability of albumen dirt is improved, specifically
It is related to the polymer containing sulfonate radical and carboxylate group, and the wash environment of high rigidity.
Background technology
Protein dirt is the most commonly seen one kind washed in dirt；Its source includes the protein such as egg white of food,
Milk stain, and bloodstain, careless stain etc..Protein dirt is easily adhered in fabric face, is difficult to dissolve in water, also more difficult to wash
Wash the lower surface that is scattered and departing from fabric of agent effect.
In the past 30 years, detergent manufacturers mix enzyme preparation in their product, to obtain the good cleaning to dirt
Power.Protease is the most common type enzyme preparation added in current fabric detergent.Due to the structural particularity of enzyme preparation, because
This composition to each component in formula, the storage condition of enzyme preparation, and the storage condition of the preparation process of detergent and product
The influence that the vigor of enzyme preparation will be produced.Due to being limited to formulation composition, even if addition protease in some detergent
It is likely difficult to obtain preferable clean effect.(the prosperous Xu Qing detergent enzymes application manual of brilliant work, China Light Industry Press, 2001,
Beijing)
Therefore, washing Industry bound pair is not in adding enzyme preparation, while has the detergent group of enhancing albumen soil removal capabilities
Compound still remains urgent demand.
In common washing process, detergent with tap water by being mixed to form cleaning solution, for cleaning with dirt
The substrate of stain.The hard water ions being present in water can reduce the washing efficiency of detergent.These ions are mainly calcium ion and magnesium
Ion, the total concentration of all hard water ions is commonly referred to as the hardness of the total hardness of water quality, referred to as water in tap water, and unit is
Mg/kg is (with CaCO3Calculate), also referred to as ppm.According to GB5749-2006《Standards for drinking water quality》, life drinks
The hardness of water should be less than 450ppm.According to GB/T 13174-2008《The survey of dress material detergent detergency and circulation scourability
It is fixed》Described in, using the hardness of water it is 250ppm when evaluating the washing efficiency of detergent.In fact, many cities and cities and towns
The tap water hardness standard in area is higher than 250ppm, such as the tap water factory calibration of Beijing is not higher than 380ppm.Taking
Underground water is more common as the city at water source and this regional phenomenon.And in some mountain areas and rural area, the slurry of resident
Directly be surface water such as river or underground water such as well water, the hardness at these water sources it could even be possible to one times of 250ppm with
On.Therefore, according to 250ppm water hardness prepare detergent and be not suitable with the washing requirement in high-hardness water area.Having must
Develop the detergent used under the hardness aquatic environment of higher.Optimal situation is, do not increase surfactant and
While washing assisant dosage, detergent can maintain suitable scourability in the aquatic environment of different hardness.
In order to reduce influence of the hard water to washing effect, must contain in detergent can combine the hard water ions such as calcium, magnesium, suppression
The washing assisant of precipitation of calcium carbonate crystallization and growth processed.Polycarboxylate and 4A zeolites are presently the most common phosphorus-free adjuvant.It is poly-
Carboxylate is except having the function that bind metal ion；Also the micro crystal of calcium carbonate can effectively be disperseed, make it be difficult to grow,
The surface of deposition pollution substrate；Also there is spot in stable dispersion cleaning solution.Polycarboxylate higher concentration calcium,
In the aquatic environment of magnesium ion content, solubility property is decreased obviously, hence it is evident that influences detergency ability, this phenomenon referred to as " is gelled ".
As the increase of polycarboxylate molecular weight, gelling phenomenon are particularly evident.Polycarboxylate is due to the combination of carboxylate radical and microparticle surfaces
Effect is too strong, and only remaining a small amount of carboxylic acid ion provides electrostatic repulsion.Less electrostatic repulsion is unfavorable for particulate
Between, particulate and substrate surface be separated.Polycarboxylate is in the relatively low system of pH value in application, carboxylate radical can be due to knot
Close proton and be changed into the carboxylic acid that hydrophily greatly declines, may result in the hydrophily of polycarboxylate, calcium ion capture ability with
And dispersion performance all substantially reduces.When polycarboxylate molecular weight is larger, in some instances it may even be possible to the heavy phenomenon of acid occurs.
Polymer containing carboxylic acid group and sulfonic acid group is due to containing strong anionic property functional group in molecular structure, at the same time
Weak anionic functional group containing strong sequestering power, makes it have excellent water solubility, antiacid antigelation stability and good
Dispersibility, complexing power and antifouling capability.This kind of polymer is widely used to synthetic fibers, oilfield chemistry, water process,
The fields such as printing and dyeing, papermaking, daily use chemicals coating.Acryloyl class sulfonate monomer above all 2- acrylamido-methyls propane sulfonic acid
(AMPS) and methylic 2- methacryls amido-methyl propane sulfonic acid.Their manufacturing process are simple, moderate.
2- acrylamide -2- methyl-propane sulfonic acids (2-Acrylamide-2-Methyl Propane Sulfonic
Acid, AMPS) structure is as follows.
AMPS is a kind of common unsaturated monomer containing sulfonate radical.AMPS is more to be come into operation in the form of comonomer,
Binary or ter-polymers are prepared with the Third monomer such as acrylic acid (AA) and maleic acid (MA), vinyl acetate.
There is no the copolymer of document report unsaturated carboxylic acid and 2- acrylamide -2- methyl-propane sulfonic acids for albumen dirt
The positive effect of removal.There is no document report under the aquatic environment higher than 250ppm hardness, the detergent containing the polymer
Composition has the albumen detergency ability of enhancing, does not also refer to unsaturated carboxylic acid and 2- acrylamide -2- methyl-propane sulfonic acids
Copolymer structural parameters such as molecular size range and distribution it can be caused to help the difference for the ability of washing.
The content of the invention
Present invention aims at provide a kind of enhancing detergent composition albumen detergency ability in the water quality of high rigidity
The sodium salt derivative of the copolymer of method, acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acids for lifting detergent for
The removal ability of albumen dirt has positive facilitation, under the aquatic environment higher than 250ppm hardness, and traditional poly- third
Olefin(e) acid sodium contrasts, the detergent of the sodium salt derivative of the copolymer containing acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acids
With preferably for the removal ability of albumen dirt.
It is a further object of the present invention to provide the detergent composition with enhancing albumen dirt removal capacity, wherein using
The copolymer of acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acids.
The present invention provides a kind of method of lifting cleaning compositions to albumen soil removal capabilities, and this method is to use third
Olefin(e) acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium salt derivatives, the sodium salt derivative of the copolymer meet with
Lower condition：
1) quality of 2- acrylamides -2- methyl-propane sulfonic acid construction units accounts for acrylic acid and 2- acryloyls in copolymer
The 40% to 70% of amine -2- methyl-propane sulfonic acid construction unit gross masses；
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.
Acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid the copolymers sodium salt derivative is in detergent compositions
Weight content is 0.01% to 5%, is preferably 0.3% to 3%, more preferably 0.5% to 2%.The albumen dirt removes
Ability be water hardness be 250ppm, 350ppm and 500ppm wash environment under measure.
In addition, the invention further relates to a kind of removal ability detergent composition for the albumen dirt for having and strengthening, it is wrapped
Contain：Weight content is 0.01% to 40% anion surfactant, and weight content is 40% to 0.01% nonionic table
Face activating agent, the zwitterionic surfactant of 0~30% (preferred content be 0.01~25%), 0~30% (preferred content is
0.01~25%) group of cationic surface active agent composition, washing assisant, 0.01% to 5% acrylic acid and 2- propylene
Acid amides -2- methyl-propane sulfonic acid copolymer sodium salt derivatives, the sodium salt derivative of the copolymer meet the following conditions：
1) quality of 2- acrylamides -2- methyl-propane sulfonic acid construction units accounts for acrylic acid and 2- acryloyls in copolymer
The 40% to 70% of amine -2- methyl-propane sulfonic acid construction unit gross masses；
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.
The anion surfactant is selected from sulfonate surfactant, carboxylate surfactant, sulfate
One or more mixtures of type surfactant；Optimizing alkyl benzene sulfonate, the alkyl sulfate of C8 to C18, C8 to C18
Ethoxylated fatty alcohol sulfate, alpha-alkene sulfonate, fatty acid alkyl esters sulfonated ester, the soap of C8 to C18, second
One or more in epoxide Fatty Alcohol Ether Carboxylate.
The nonionic surfactant is selected from fatty alcohol alkoxy compound, alkyl polyglycoside, fatty acid alkoxylates,
Fatty acid ethoxylate, fatty acid alkyl alcohol amide, one kind or their mixture of ethoxylated sorbitan acid alcohol ester.
The present invention relates to detergent composition to be substantially free of polycarboxylate, and the polycarboxylate is number-average molecular weight 2000
More than, only include following structure formula (I), the polymer of any one or more of (II) in its constitutional repeating unit；
Wherein A is COOH or COO-M+, M+For cation；B is H or CH3.M therein+Can be potassium ion, sodium ion, ammonium
Ion etc..
The detergent composition of the present invention can be any form, including following form：Liquid form, solid form, such as
Powder, particle, tablet etc.；Gel, bar, wet tissue etc., and other uniform or multiphase consumer cleaning product's forms.
In some embodiments, detergent composition of the invention is liquid or fabric detergent compositions.
By above-mentioned technical proposal, the present invention has the advantage that is with beneficial effect：
1st, it is an unexpected discovery of the invention that by using acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium
Salt derivative, can effectively improve albumen soil removal capabilities of the detergent under higher hardness aquatic environment.
2nd, on the premise of surfactant and other scrubbed component contents is not increased, the detergent combination of invention
Thing has good albumen soil removal capabilities in extensive firmness change scope.
Embodiment
For those skilled in the art, it is feature of the invention, beneficial by reading the disclosure of the specification
Effect and advantage will become obvious.
Except as otherwise noted, all percentages, fraction and ratio are calculated by the gross weight of the present composition.Remove
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 accessory substance that may be included in the material of acquisition.This paper terms " weight content " available symbols " % " represent.
Except as otherwise noted, all molecular weight herein are all relative molecular mass, are represented with g/mol units
Number-average molecular weight.
Except as otherwise noted, it is all herein to prepare and test the environment occurred at 25 DEG C.
Herein " comprising ", "comprising", " containing ", " containing ", " having " or other variations be intended to it is non-enclosed including,
Do not distinguished between these terms.Term "comprising" refers to that the other steps for not influencing final result and component can be added.Term
"comprising" further includes term " Consists of " and "consisting essentially of ...".The compositions and methods of the invention/technique includes, by
It forms and substantially by essential elements described herein and limit entry and described herein any additional or optional
Component, component, step or limit entry composition.
Hardness
" hardness " of the present invention refers to what is calculated in Unit Weight water by weight of calcium carbonate, and calcium ions and magnesium ions is total in water
Amount, unit ppm.For example, when containing 0.0005 mole of calcium ion and 0.0005 mole of magnesium ion in 1000 grams of water, its hardness is
100ppm。
The hardness that " extensive hardness " refers to water quality is 250ppm, 350ppm, 500ppm.
The hardness that " high rigidity " refers to water quality is higher than 250ppm.
Detergent composition
The term " detergent composition " of the present invention refers to fabric detergent compositions, is chosen in particular from consisting of the following
Group：Fabric detergent compositions, solid fabric detergent composition, the fabric detergent compositions of tablet/unit dosage forms.
The detergent composition of the present invention is in contact in water by the substrate (i.e. textile article) contacted with needs, so that
By the greasiness removal of substrate surface, achieve the purpose that to clean substrate surface.
Acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium salt derivatives
The present invention represents the copolymer of acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acids with AA-AMPS polymer.
The sodium salt derivative of AA-AMPS polymer represents acrylic acid and the copolymer sodium salt of 2- acrylamide -2- methyl-propane sulfonic acids spreads out
Biology.The sodium salt derivative of AA-AMPS polymer contains sulfonate group and carboxylate group at the same time, both groups are all parents
Water-based good group.
This polymer containing two kinds of hydrophilic radicals is referred to as double-hydrophilic polymer (Double Hydrophilic
Polymer).The shortcomings that this kind of polymer can be solved in some performances of polycarboxylic acids.Double-hydrophilic polymer refers to containing two
The polymer of the different types of hydrophilic radical of kind.On the one hand, in molecule a kind of hydrophilic structure unit can and stromal surface
Strong interaction occurs, copolymer is anchored on to the surface of matrix；On the other hand, another hydrophilic structure in molecule
Unit will not substantially be acted on stromal surface, so as to ensure the sufficient hydrophilicity of polymer, can also be reduced to a certain extent
It is changed into deflation from stretching, extension with polymer conformation is suppressed, to ensure that polymer can play complexing, dispersion performance to large extent.
For to a certain degree, the surfactant of the somewhat similar similar traditional sense of double-hydrophilic polymer, can play stabilization, disperse
The effect of complex compound, particulate in aqueous solution.
At present, commercially available parents' aqueous polymer is summarized as follows：Dow companies Acusol 587,588 be solid content 30 to
40% copolymer containing carboxylate radical and sulfonate radical, molecular weight is 12000 to 13000.It is recommended that the use of field is washing powder, especially
There is significantly inhibitory action for the crystal growth of insoluble calcium polyphosphate and silicate.In addition, the carboxylic acid of Acusol series
Salt and co-polymer of sulfonate may be also used in dish washing detergent compositions, for reducing glass and crust object drying process
The formation of middle surface moisture film has facilitation.Dow companies Acumer series is that solid content 35 to 45% contains carboxylate radical and sulfonic acid
The copolymer of root, for water treatment field.There are several trades mark such as Acumer2000, Acumer2100, Acumer3100.
Acumer2000 is the bipolymer of carboxylate and sulfonate, and Acumer3100 is carboxylate and sulfonate, non-ionic list
The terpolymer of body.Major function is the precipitation of the metallic compounds such as effectively scattered phosphate, zinc salt, iron oxide, for carbon
The scattered of sour calcium also has certain positive effect.
It has been found that composition, the molecular weight of acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium salt derivatives
Size and distribution help it and wash detergency ability and have obvious influence.Found based on more than, the sodium salt of present invention selection copolymer spreads out
Biological gratification the following conditions：
1) quality of 2- acrylamides -2- methyl-propane sulfonic acid construction units accounts for acrylic acid and 2- acryloyls in copolymer
The 40% to 70% of amine -2- methyl-propane sulfonic acid construction unit gross masses,
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.
Inventor has found that acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium salt derivatives can be effectively
Strengthen removal ability of the detergent composition to albumen dirt.Acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymers
The additive amount of sodium salt derivative can be 0.01% to 5%, be calculated with composition weight.Based on cost and reach washing for expected degree
Wash the consideration of performance, its dosage be no more than 10%, be 0.01% to 5%, be preferably 0.3% to 3%, more preferably 0.5% to
2%.
The molecular weight and its molecular weight of acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium salt derivatives point
Cloth
Polymer is that a series of molecular size ranges differ, and has the mixture that the homologue of identical construction unit forms.
The average molecular weight of polymer is a statistic.The equal molecule of number is known as with the molecular weight of the average polymer of molecule amount
Amount, is represented with Mn.Weight average molecular weight is known as with the molecular weight of the average polymer of quality, is represented with Mw.
Acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium salt derivatives are as a kind of polymer, equally
There are a series of homologue that molecular size ranges differ, its average molecular weight is a statistic.
The mutual difference of homologue molecular weight is characterized with molecular weight distribution (D) in polymer.D values calculate as follows：
The D values of polymer are generally more than 1.0.D values are smaller, illustrate the mutual molecular weight differences of homologue in polymer
It is different closer；D values are bigger, and the explanation mutual molecular weight difference of homologue is bigger.
The acrylic acid and the equal molecule of 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium salt derivative numbers that the present invention selects
Amount is between 5000 to 10000, and molecular weight distribution (D values) is 1.60 to 1.85.
The survey of the molecular weight and its distribution of acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium salt derivatives
Method for testing
Present invention selection gel exclusion chromatography (GPC) measure acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acids are total to
The molecular mass and distribution of polymers sodium salt derivative.Molecular weight determination is specifically carried out using water phase GPC.
Water mutually refers to GPC tests using water as mobile phase.Detected using differential refraction detector (RID).
The present invention uses the polyacrylic acid molecular weight of PSS companies of Germany (Polymer Standard Service GmbH)
Standard items, the number-average molecular weight of standard items is between 1000 to 20000.
Surfactant system
Detergent composition of the present invention is except acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium
Outside salt derivative, also comprising surfactant system.Suitable surfactant system includes, but is not restricted to：Anion table
Face activating agent, nonionic surfactant, cationic surfactant, zwitterionic surfactant, double type surface-active
One kind of agent and its a variety of mixtures.Preferable surfactant system includes anion surfactant and non-ionic surface
The mixture of activating agent.
Anion surfactant
The content of anion surfactant is the 0.01% to 30% of detergent composition, with detergent composition gross weight
Amount calculates.
Anion surfactant is selected from sulfonate surfactant, carboxylate surfactant, sulfate type table
One or more mixtures of face activating agent；Alkylbenzenesulfonate preferably is selected from, the alkyl sulfate of C8 to C18, C8 is to C18's
Ethoxylated fatty alcohol sulfate, alpha-alkene sulfonate, fatty acid alkyl ester sulfonate, the soap of C8 to C18, ethyoxyl
Change one kind of Fatty Alcohol Ether Carboxylate, and their mixture.
In some embodiments, the mixture of anion surfactant preferably comprises alkylbenzenesulfonate and its derivative
Thing.The alkylbenzenesulfonate meets below formula：
Wherein R1 be carbon number be 6 to 24 alkyl, M+For cation, such as potassium ion, sodium ion, ammonium ion etc..R1 can
To be the alkyl of straight chain or the alkyl of side chain；It can be the alkyl of saturation or contain one or more insatiable hungers
With the alkyl of double bond.Further preferred R1 is the straight chained alkyl that carbon number is 8 to 18.Suitable example is dodecyl benzene sulfonic acid
Sodium.
In some embodiments, the mixture of anion surfactant contains the aliphatic alcohol sulfate of ethoxylation.
Ethoxylated fatty alcohol sulfate is the derivative of ethoxylate fatty alcohol, has below formula：
Wherein R1 is the alkyl that carbon number is 6 to 24；X is 0.5 to 30；Wherein M+For cation, for example, potassium ion, sodium from
Son, ammonium ion etc..R1 can be the alkyl of the alkyl of straight chain or side chain；It can be the alkyl of saturation or contain
There is the alkyl of one or more unsaturated double-bonds.It is preferred that R1 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 preferably 0.5 to 3.Suitable example is the Texapon N70 of BASF AG.
In some embodiments, containing alkyl sulfate, alkyl segment can be straight chain, or side chain, can
To be the alkyl of saturation or contain the alkyl of one or more unsaturated double-bonds.Optimizing alkyl carbon number is 6 to 24 alkane
Base sulfate, further preferred carbon number are 8 to 18 alkyl sulfate.Suitable example is lauryl sodium sulfate.
In some embodiments, containing alpha-alkene sulfonate, there is below formula：
Wherein a is 0 to 2, R1Be carbon number be 6 to 24 alkyl, preferably R1It is the alkyl that carbon number is 8 to 18.
In some embodiments, the mixture of anion surfactant contains soap, preferably carbon number for 8 extremely
The soap of 18.The alkyl segment of aliphatic acid can be straight chain, or side chain, can be the alkyl of saturation,
It can be the alkyl containing one or more unsaturated double-bonds.Soap can be single composition or a variety of fat
The mixture of acid composition.Suitable example is enuatrol, sodium laurate.The soap also includes ethoxylized fatty alcohol ether
Carboxylate, the carbon number of fatty alcohol preferably 8 to 18, average ethoxylation degree is preferably 2.0 to 10.
The anionic surfactant mixture can also include one kind of alkyl sodium disulfonate or derivatives thereof and more
Kind mixture, optimizing alkyl diphenyl oxide disulfonate, suitable example is disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate salt, DOW companies
Dowfax series of products.Fatty acid alkyl esters sulfate can also be contained, be preferably fatty acid methyl ester sulfate (MES), it is fatty
Sour carbon number preferably 8 to 18.Sulfosuccinate can also be included, is preferably fatty alcohol polyoxyethylene ether sulfosuccinic acid monoesters
Disodium salt, fatty alcohol carbon number preferably 8 to 18, average ethoxylation degree is preferably 2.0.
Nonionic surfactant
The content of nonionic surfactant is the 0.01% to 30% of detergent composition, with detergent composition gross weight
Amount calculates.
Nonionic surfactant is selected from fatty alcohol alkoxy compound, alkyl polyglycoside, fatty acid alkoxylates, fat
Sour ethoxylate, fatty acid alkyl alcohol amide, one kind and their mixture of ethoxylated sorbitan acid alcohol ester.
In some embodiments, non-ionic surfactant mixture preferably comprises fatty alcohol alkoxy compound, described
Fatty alcohol alkoxy compound has below general formula：
Wherein, n is 6 to 24；X is that 0.5 to 30, y is 0 to 10.
The fatty alcohol alkoxy compound is the ring-opening polymerisation under basic catalyst effect of fatty alcohol and epoxyalkane
Product, substantially mixture.Fatty alcohol includes the isomery alcohol of straight chain alcohol or side chain.Alkoxy grp includes ethoxy group and the third oxygen
Group.The preferred carbon number of fatty alcohol is 8 to 18 fatty alcohol, and preferable alcohol includes but is not limited to hexanol, octanol, decyl alcohol, 2- second
Base alcohol, 3- propyl enanthols, laruyl alcohol, different three decyl alcohol, tridecanol, tetradecanol, hexadecanol, Palmitoleyl alcohol, stearyl alcohol,
Isooctadecanol, oleyl alcohol, sub- oleyl alcohol, one kind and its mixture of linolenyl alcohol.Average ethoxylation degree x preferably 2 to 12.Preference
Son is SHELL companies NEODOL series linear primary alcohol ethoxylate products, the ECOSURF EH series ethoxylations of DOW companies
With the third oxidation 2-ethylhexanol product, BASF AG's Lutensol XL series ethoxylations and the third oxidation 3- propyl enanthol products
With BASF AG's Lutensol XP series ethoxylation 3- propyl enanthol products.
In some embodiments, non-ionic surfactant mixture preferably comprises alkyl polyglycoside, has following logical
Formula：
Wherein, n is that 6 to 24, p is 1.1 to 3.It is preferred that n is 8 to 16.Suitable alkyl polyglycoside such as BASF AG
Glucopon series alkyl glycosides products.
Non-ionic surfactant mixture can contain fatty acid alkoxylates, preferably be selected from ethoxylation C8 to C18
Fatty acid ester, average ethoxylation degree are 2 to 10.Ethoxylated sorbitan acid alcohol Arrcostab, alkyl carbon number can be contained
For 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, can
Can be the aliphatic acid of saturation or undersaturated fat to be the aliphatic acid of straight chain or the aliphatic acid of side chain
Acid；Alkylol number is 0 to 2.Preferred fatty acid carbon number be 8 to 18 a glycollic amide, 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.It is preferred that it is 0.5 to 30 that n, which is 8 to 18, x,.It is preferred that x is 4 to 10.Suitable example
It is LION companies MEE products.
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% amphion
Surfactant, the group of 0~30% cationic surface active agent composition.Zwitterionic surfactant includes betaine type table
Face activating agent, Imidazoline Surfactants, amino acid type surfactant, amine oxide type surfactant；Including but it is unlimited
It is formed on：Alkyl betaine, fatty acid amide glycine betaine, fattyamidopropyl betaine, fatty amide propyl hydroxypropyl sulfonation beet
Alkali, including acetate alkyl sodium form imidazoline, fatty acid type imidazoline, sulfonic acid type imidazoline；Alanine derivatives, glycine spread out
Biology；Alkyl dimethyl amine oxide, fatty acyl amido dimethylamine oxide etc..Cationic surfactant includes quaternary ammonium salt
Class surfactant, heterocyclic class surfactant, polymer-type cationic surfactant.Including：Single long linear quaternary ammonium salt,
Double long linear quaternary ammonium salts, benzyl quaternary ammonium salt, hydroxyalkyl quaternary ammonium salt, fatty amide propyl hydroxyalkyl quaternary ammonium salt, there is vinyl pyrrole
The multi-quaternary ammonium salt that alkanone and unsaturated amides or unsaturated quaternary ammonium salt are copolymerized.
Polycarboxylate
Detergent composition of the present invention is substantially free of polycarboxylic acids.Term " being substantially free of " refers to preparing the present invention
Polycarboxylate is not artificially added in the detergent composition being related to.Specifically, detergent composition of the polycarboxylate in the present invention
In weight content be not higher than 0.0001%.
Term " polycarboxylate " number average molecular only includes following structural formula more than 2000 in its constitutional repeating unit
(I), the polymer of any one or more of (II)；
Wherein A is COOH or COO-M+, M+Can be potassium ion, sodium ion, ammonium ion etc. for cation.B is H or CH3。
Washing assisant
Detergent composition of the present invention can include washing assisant, the washing assisant be selected from fluorescent whitening agent,
The group of enzyme preparation, bleach system composition.
Fluorescent whitening agent
Detergent composition of the present invention preferably comprises fluorescent whitening agent.Fluorescent whitening agent is in detergent compositions
Application be technology known in the art, and have many commercially available fluorescent whitening agent commodity.The use of usual fluorescent whitening agent
Measure as the 0.01% to 2wt% of total composition, preferably 0.01% to 0.1%.Fluorescent whitening agent (is mostly with its alkali metal salt
Sodium salt) form presence.Preferable fluorescent whitening agent including but not limited to：Diphenylethyllene connects benzene compound.Suitable example
It is double (the 2- sodium sulfonates styryl) biphenyl of 4,4'-, such as the product of BASF AG's CBS-X trades mark.Diamines stilbene two-
Sulfoacid compound.Suitable example is 4,4 '-bis- { [(4- phenylamino 6- morpholinoes -1,3,5-, triazine -2- bases)] amino } equal two
Benzene is for ethene -2,2 '-disulfonate.
The group selected from following compound composition can be included：2- (4- styryl -3- sulfo groups phenyl) -2H- naphtho-s [1,2-
D] 1-Sodium-1,2,4-Triazole, 4,4 '-bis- { [(4- phenylaminos 6- (N- methyl-N-2- ethoxys) amino -1,3,5-, triazine -2- bases)] amino }
Stilbene -2,2 '-disulfonate, 4,4 '-bis- { [(4- phenylamino 6- morpholinoes -1,3,5-, triazine -2- bases)] ammonia
Base } stilbene -2,2 '-disulfonate, 4,4 '-bis- (2- sulfostyryls) biphenyl disodiums.
Enzyme preparation
Detergent composition of the present invention can include one or more of enzyme preparations, to provide clean-up performance, knit
Thing is nursed 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 gathers
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, is preferably 0.01% to 2%.
The detergent composition of the present invention can include the enzyme stabilising system for accounting for composition weight 0.001% to 10%.Institute
Stating enzyme stabilising system can be compatible with detergent composition, can include calcium ion, boric acid, borax, propane diols, glycerine, polyalcohol
One kind and its mixture.The weight and dosage of enzyme stabilising system are in the form of according to detergent composition and composition and enzyme system
The type of agent is adjusted.
Bleach system
Detergent composition of the present invention can include bleach system.Bleach system includes hypohalite beaches,
Peroxide bleaches.Peroxide bleaches typically comprises hydrogen peroxide source and bleach activating system.Hydrogen peroxide source bag
Include but be not limited to perborate, percarbonate, persulfate, and their mixture.In some embodiments it is preferred that
Hydrogen peroxide source is SODIUM PERCARBONATE.Bleach system can include bleach-activating, and the bleach-activating is used to promote peroxidating
Fast decoupled produces oxygen to thing at a lower temperature, the group selected from following compound composition：Tetra acetyl ethylene diamine, benzoyl oneself
Lactams, 4- nitrobenzoylcaprolactams, 3- chlorobenzoylcaprolactams, benzoyl oxybenzene sulfonates, nonanoyl oxygen
Base benzene sulfonate, phenol benzoate, decanoyloxybenzenesulphonate, benzoyl valerolactam, octanoyloxy benzene sulfonate, transition
Metal bleach catalyst.
Detergent composition of the present invention can also include ozone stabilizer, and the ozone stabilizer is used to adjust
Peroxide breaks down produces the speed of hydrogen peroxide, the local concentration of hydrogen peroxide is unlikely to excessive, suitable example is hydroxyl
The organic phosphoric acid of the polyfunctionality such as ethylidene diphosphonic acid, ethylenediamine tetraacetic methene phosphoric acid.
Anti redeposition agent
From the viewpoint of washing effect is effectively improved, it can include to resist in detergent composition of the present invention and sink again
Product agent.The anti redeposition agent includes but is not limited to the group of following compound composition：Cellulose derivative, such as carboxymethyl are fine
Dimension element, ethylhydroxyethylcellulose, methylcellulose；The homopolymer and copolymer of vinyl pyrrolidone, such as the poly- second of straight chain
The copolymer of vinyl pyrrolidone, n-vinyl pyrrolidone and vinyl acetate, n-vinyl pyrrolidone and N- vinyl
The copolymer of imidazoles, polyvinyl oxazolidone.
Optional member
Detergent composition of the present invention includes following optional additive：Alkaline agent, inorganic salts, viscosity modifier,
Preservative, colouring agent, essence.
Detergent composition of the present invention can include one or more alkaline agents, and alkaline agent is selected from sodium hydroxide, hydrogen-oxygen
Change potassium, alkali carbonate, the silicate of alkali metal.In some embodiments, detergent composition of the present invention can
With comprising one or more salts, the salt can be inorganic salts or organic salt.Detergent composition of the present invention
One or more of viscosity modifiers can be included, to provide suitable viscosity.Suitable viscosity modifier such as inorganic salts are more
Sugar, sizing material, short chain fatty alcohol, short chain fatty alcohol alkyl ether.Suitable example is sodium chloride, ethanol, propane diols, sodium citrate,
Alkyl-hydroxyalkylcelluloswith ether, carragheen, xanthans, polyacrylamide derivative.
In some embodiments, detergent composition of the present invention preferably comprises preservative, and suitable example is
Phenoxy group alcohol, sodium benzoate；Isothiazolinone and its derivative such as methylisothiazolinone, methylchloroisothiazandnone, benzo
One kind of isothiazolinone or its mixture.Preservative dosage is 0.001% to 5%, is preferably 0.01% to 2%.
In some embodiments, detergent composition of the present invention contains colouring agent, and the colouring agent includes dye
Material and pigment.Colouring agent can include the colouring agent for being used in and being applied in cleaning product, suitable example such as acid red G, alkali
Property pinkish red, Methanil Yellow G, Acid Light Yellow G, alkaline yolk, direct fast blue B2RL, indigo-blue etc..
Detergent composition of the present invention preferably comprises spices, and the spices includes all and is suitable for cleaning product
Fragrance component.The spices used of the present invention can be natural origin or the product of chemical synthesis, or the two is mixed
Compound.Suitable example such as lemon, rose, jasmine, lavender, citrus is fragrant, blue or green fragrant, banksia rose etc..
Except above-mentioned optional member, detergent composition of the invention can also include water, organic solvent, cosolvent, solubilising
Agent, structural agent, promotees the various common and conventional additives such as infusion, foam inhibitor, fabric softener, anti wrinkling agent.These add
It is all well-known to those skilled in the art to add agent and associated method of use, and the selection of its specific type and dosage can basis
Actual needs is adjusted.
Preparation and application method
The detergent composition of the present invention can be formulated into various suitable object forms and use those skilled in the art
It is prepared by known various methods.Suitable object form includes but is not limited to liquid-type, solid particle type, tablet form.Liquid
The preparation of build composition can be carried out by conventional means, specifically should according to the state of component in the solution and effect, and
The stability and heat endurance of component are selected from suitable processing temperature and process time.The preparing process of solid particle type composition
It can be first to prepare the aqueous slurry containing constituent part, then be spray-dried slurry, finally by dry gained particle and in addition
Partial component mixing.
The application method of the detergent composition of the present invention is well-known to those skilled in the art, typical application method
It is by specific detergent composition embodiment in a manner of undiluted or in the way of dilution in water, and washed object
Surface contacts, and then rinses the surface of washed object.Preferably, be washed object above-mentioned contact procedure and rinse step it
Between carry out washing step.Washing step includes but not limited to clean and mechanical agitation.Washed object includes fabric and tableware.Institute
Stating detergent composition, concentration is about 500ppm to 10000ppm in water, and water temperature is preferably 5 DEG C to about 60 DEG C.Water is with being washed
The ratio of object is preferably from about 1：1 to about 20：1.
Without being further described, it is believed that those skilled in the art can use this to greatest extent using the above
Invention.The following examples purpose is to be further described and shows specific embodiment within the scope of the present invention.Therefore, it is real
Apply example to be interpreted as being only used for showing the present invention in more detail, without the content limiting the invention in any way.
In following embodiments, except as otherwise noted, all contents are weight percentages, and related ingredients listed contains
Amount is the content of the active material by conversion.
In the described embodiment, the following trade mark and abbreviation will be used.
PAA：The sodium salt derivative of acrylate homopolymer, belongs to polycarboxylate.Dow Chemical Products
Acusol445N。
LAS：C10-C13 sodium n-alkylbenzenesulfonates.
AOS：Alpha-alkene sulfonate, anion surfactant.
AES：Ethoxylated fatty alcohol sulfate, the main carbon number of fatty alcohol are C12-C14, and average ethoxyquin degree is 2, cloudy
Ionic surface active agent.
K12：Lauryl sodium sulfate, anion surfactant.
AEO7：Ethoxylized fatty alcohol, average ethoxyquin degree is 7, nonionic surfactant.
AEO9：Ethoxylized fatty alcohol, average ethoxyquin degree is 9, nonionic surfactant.
TO-7：Ethoxylation isomerous tridecanol, average ethoxyquin degree is 7, nonionic surfactant, BASF AG's production
Product, the trade mark are Lutensol TO-7.
XP-80：Ethoxylation 2- propyl enanthols, average ethoxyquin degree is 8, nonionic surfactant, BASF AG
Product, the trade mark are Lutensol XP-80.
XL-80：Ethoxylation and propoxyl group 2- propyl enanthols, average ethoxyquin degree is 8, nonionic surfactant,
BASF AG's product, the trade mark are Lutensol XL-80.
MEE：Fatty acid methyl ester ethoxylate, nonionic surfactant, LION Products.
APG：C8-C14 alkyl glycosides, nonionic surfactant, BASF AG's product, trade mark Glucopon650EC.
LAO：Dodecanamide propyl amine oxide, nonionic surfactant.
CAB：Cocoamidopropyl betaine, zwitterionic surfactant.
LAB：Lauroylamidopropyl betaine, zwitterionic surfactant.
Protease：Alkali protease, Novozymes Products, the trade mark are Savinase Ultra 16XL.
Viscosity modifier：Sodium citrate.
Brightening agent：4,4'- double (2- sodium sulfonates styryl) biphenyl, fluorescent whitening agent, BASF AG's product, the trade mark are
CBS-X。
Preservative：Methylisothiazolinone and chlormethylisothiazo,ine alcohol/ketone mixtures.
Peroxide bleaches：SODIUM PERCARBONATE.
The preparation process embodiment of acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium salt derivatives
By the composition of 1 polymerization system of table, prepare acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium salts spread out
Biology, technique are as follows：
1) 2- acrylamide-2-methylpro panesulfonic acids, acrylic acid, RAFT reagents are added in the reactor, add 60 grams go from
Sub- water, stirring is to being completely dissolved；
2) 60 DEG C are warming up to, initiator is dissolved in dissolving in 5 grams of deionized waters obtains the aqueous solution of initiator；
3) initiator solution is added dropwise into reactor, time for adding is controlled at 10 minutes to 15 minutes, is added dropwise follow-up
Continuous stirring reaction, temperature are kept for 60 DEG C.React 6 it is small when postcooling to room temperature；
4) 10%NaOH aqueous solutions are added into reactor, adjust pH to 8.5；
5) 100 DEG C of vacuum rotary steams are warming up to, removal solvent obtains acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acids are total to
Polymers sodium salt derivative.
The name of 1 acrylic acid of table and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium salt derivatives
The molecular mass and distribution of acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium salt derivatives is surveyed
Examination
It is big that molecular weight is carried out to acrylic acid of the present invention and 2- acrylamide -2- methyl-propane sulfonic acid copolymers sodium salt derivative
Small and distribution test, step are as follows：
1) molecular weight tests are carried out using 30,8 μm of gel chromatographic columns of Aglilent PL aquagel-OH, using showing difference
Refraction detector (RID) is used as detection part, and interpretation of result is carried out using Agilent GPC softwares.
2) mobile phase is the trisodium phosphate aqueous solution of 0.02mol/L, and flow velocity 1mL/min, column temperature is 35 DEG C.Molecular weight mark
Quasi- product be PSS companies of Germany (Polymer Standard Service GmbH) polyacrylic acid standard items, its number-average molecular weight
Between 1000 to 20000.30 milligrams of different molecular weight polyacrylic acid standard items are weighed in 10 milliliters of volumetric flasks, are added ultrapure
Water is settled to scale, and series standard solution is made.
3) 30 milligrams of AA-AMPS copolymer sodium salt derivatives sample is weighed in 10 milliliters of volumetric flasks, is added ultra-pure water and is determined
Hold to scale, sample solution is made.
4) the test result such as institute of table 2 of acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium salt derivatives
Show.It is 5200 to 10000 that copolymer A, B, C, which are satisfied by 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 process embodiment 1-3 and comparative example 1-3 of detergent composition
Formed according to table 3 below and prepare fabric detergent compositions A-F, preparation process is as follows：
1) deionized water is added into preparing tank；
2) start stirring, add above-mentioned various surfactants, be warming up to 60 DEG C, stirring is to being completely dissolved；
3) withdraw heat source, add viscosity modifier, AA-AMPS copolymers sodium salt derivative of the present invention or as pair
The component of ratio, stirring is to being completely dissolved；
4) it is less than 45 DEG C in temperature, adds fluorescent whitening agent brightening agent, essence, pigment, preservative, is stirred to completely molten
Solution.
3 liquid detergent composition A-F of table is formed
Following washing detergency ability is carried out to the liquid detergent composition A-F prepared in embodiment 1-3 and comparative example 1-3
Test.
Decontamination performance test methods under 250ppm hardness
Detergency ability test is carried out with reference to GB/T 13174-2008.Using sebum, albumen, three kinds of soiled cottons of carbon black, use north
Jing Kang light optical instrument Co., Ltd WSD-3U fluorescent whiteness meter measures whiteness W before three kinds of soiled cottons are washed1.By GB/T 13174-
2008 prepare the slurry that hardness is 250ppm, and wherein calcium ions and magnesium ions ratio is 3：2.
The liquid detergent composition A-F slurries of 250ppm prepared in embodiment 1-3 and comparative example 1-3 are matched somebody with somebody
0.2% solution is made, 1 washing, wash time are completed with China Daily-use Chemical Industry Institute RHLQ types Terg-O-Tometer
20min, wash temperature are 30 DEG C, and 120 revs/min of mixing speed, three kinds of soiled cottons are rinsed, dry, with WSD-3U fluorescent whiteness
Meter three kinds of soiled cottons of measurement wash rear whiteness W2.Whiteness difference △ W calculate as follows：
△ W=W2-W1。
W2：Soiled cotton washes rear whiteness,
W1：Soiled cotton washes preceding whiteness.
△ W values are smaller, illustrate that soiled cotton washes that rear whiteness difference is smaller before washing, the washing efficiency of composition is poorer.
On the basis of comparative example 1, the decontamination ratio P calculating for calculating each surveyed composition is as follows：
P=△ Wi/△WI,
△Wi：The whiteness difference of surveyed composition,
△WI：The whiteness difference of comparative example 1.
Wherein P values are less than 1, illustrate that the dirt-removing power of surveyed composition is less than comparative example 1, P values are more than 1, illustrate institute's survey group
The dirt-removing power of compound is more than comparative example 1.P values are bigger, illustrate that the dirt-removing power of surveyed composition is stronger.
Table 4 is the decontamination result of liquid detergent composition A-F.
4 liquid detergent composition decontamination result of table
By table 4 as it can be seen that the synthesis detergency ability of comparative example 3 is worst, illustrate acrylic acid and 2- acrylamide -2- methyl-propyls
Sulfonic acid copolymer sodium salt derivative (embodiment 1-3, comparative example 2), acrylate homopolymer sodium salt derivative (comparative example 1) have just
Efficiency is washed in helping for face.Compared with comparative example 1 with 2, using three implementations for meeting AA-AMPS copolymers sodium salt of the present invention
Example is respectively provided with obvious preferably albumen soil removal capabilities.Compared with comparative example 1 with 2, three embodiments for carbon black dirt and
The removal ability of sebum dirt is similar.Illustrate under the aquatic environment of 250ppm hardness, 1-3 of the embodiment of the present invention has
It is substantially better than the albumen soil removal capabilities of comparative example 1-3, and more preferably comprehensive clean effect.
Following anti-dirt deposition properties are carried out to liquid detergent composition A-F prepared by embodiment 1-3 and comparative example 1-3
Test.
Anti-dirt deposition properties test method
Using the polyester textile and cotton fabric for meeting GB/T 7568.2-2008.Use the limited public affairs of Beijing Kang Guang optical instruments
Department's WSD-3U fluorescent whiteness meter two kinds of fabrics of measurement wash preceding whiteness W '1。
Dirt is parrot coal dirt, and preparation steps are as follows：
1) by 20g carbon black dispersions in 70g deionized waters, 7.5g vegetable oil, 2.5g mineral oil, with IKA companies IKA are added
T25 homogenizers (band S25N-18G homogeneous cutter) homogeneous 20 minutes, obtains 100g parrot coal dirts.
2) slurry that hardness is 250ppm is prepared by GB/T 13174-2008, wherein calcium ions and magnesium ions ratio is 3:2.
3) in the case where being kept stirring, by 10g parrot coal soil dispersion in 1L slurries, 2g embodiments are rapidly added
2 liquid detergent compositions prepared, add fabric to be washed.
With China Daily-use Chemical Industry Institute RHLQ type Terg-O-Tometers, wash time 20min, wash temperature 30
DEG C, mixing speed 120r/min is dry by two kinds of fabric rinsings, is measured with WSD-3U fluorescent whiteness meter, is white after record fabric washing
Spend W '2.Whiteness difference △ W ' calculate as follows：
△ W '=W '2-W’1。
W’2：Fabric washes rear whiteness,
W’1：Fabric washes preceding whiteness.
△ W ' values are bigger, illustrate that fabric is subject to the pollution of greasy filth dirt more serious in washing process, the anti-dirt of composition
It is poorer to deposit efficiency.
On the basis of comparative example 1, it is as follows to calculate each surveyed composition anti-pollution deposition ratio R calculating：
R=△ W 'i/△W’I,
△W’i：The whiteness difference of surveyed composition,
△W’I：The whiteness difference of comparative example 1.
Wherein R values are more than 1, illustrate that the anti-dirt deposition capability of surveyed composition is less than comparative example 1, R values are less than 1, explanation
The anti-dirt deposition capability of surveyed composition is more than comparative example 1.P values are bigger, illustrate that fabric is more polluted, then survey combination
The anti-dirt deposition capability of thing is weaker.
Table 5 is the anti-dirt deposition results of liquid detergent composition A-F.
5 liquid detergent composition A-F anti-dirt deposition results of table
By table 5 as it can be seen that being entirely free of polycarboxylate and acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium
The 5 anti-dirt deposition capability of comparative example of salt derivative is worst.Illustrate polycarboxylate and acrylic acid and 2- acrylamide -2- methyl-props
Base sulfonic acid copolymer sodium salt derivative is all to have positive help to wash efficiency.
Either cotton fabric or polyester textile, the embodiment of the present invention have the anti-pollution dirt deposition significantly better than comparative example
Efficiency.Compared with polyester textile, acrylic acid is with 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium salt derivatives for cotton
The inhibition of dirt deposition becomes apparent from fabric.
It can be seen from the above that use the acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium that meet patent requirements
The embodiment 1-3 of salt derivative has the anti-pollution dirt deposition effect for being substantially better than comparative example under the conditions of the washing water quality of 250ppm
Energy.
Albumen dirt removal capacity test under different quality hardness
1-3 of the embodiment of the present invention and comparative example 1 liquid detergent composition prepared are carried out under different quality hardness
Albumen dirt is removed and can tested.Washing detergency ability test method under different quality hardness is identical with above description, simply
The hardness of slurry is changed to 350ppm, 500ppm.The slurry of different hardness is prepared by GB/T 13174-2008, wherein
Calcium ions and magnesium ions ratio is 3：2.Table 6 is the decontamination result table of liquid detergent composition under different quality hardness.6 different quality of table
The decontamination result of liquid detergent composition under hardness
By table 6 as it can be seen that in 250ppm, the washing aquatic environment of 350ppm, 500ppm, compared with comparative example, three realities
Apply example and be respectively provided with obvious preferably albumen soil removal capabilities.Compared with comparative example, three embodiments are for carbon black dirt and skin
The removal ability of fat dirt is similar.Illustrate under the aquatic environment of 250ppm to 500ppm hardness, it is of the present invention
Acrylic acid assigns detergent composition with 2- acrylamide -2- methyl-propane sulfonic acid copolymers sodium salt derivative has the egg of enhancing
White soil removal capabilities, and more preferably comprehensive clean effect.
The preparation process embodiment 4 of detergent composition
The step of preparation process that preparation fabric detergent compositions are formed according to table 7 below is as follows：
1) deionized water is added into preparing tank；
2) start stirring, add above-mentioned various surfactants, be warming up to 60 DEG C, stirring is to being completely dissolved；
3) heat source is withdrawn, adds viscosity modifier, acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium salts
Derivative, stirring is to being completely dissolved；
4) it is less than 45 DEG C in temperature, sequentially adds brightening agent, preservative, enzyme preparation, enzyme stabilizers, essence, pigment, stirring
To being completely dissolved.
7 fabric detergent compositions of table form
| Component | Content (%) |
| LAS | 3 |
| Odium stearate | 2 |
| 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 |
| Preservative | 0.1 |
| Water | Surplus |
The preparation process embodiment 5 of detergent composition
Formed according to table 8 below and prepare dish washing detergent compositions.Preparation process is as follows：
1) deionized water is added into preparing tank；
2) start stirring, add above-mentioned various surfactants, be warming up to 60 DEG C, stirring is to being completely dissolved；
3) heat source is withdrawn, adds viscosity modifier, acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium salts
Derivative, stirring is to being completely dissolved；
4) it is less than 45 DEG C in temperature, sequentially adds preservative, essence, pigment is stirred to being completely dissolved.
8 liquid dishwashing detergent compositions of table form
| 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 |
| Preservative | 0.05 |
| Water | Surplus |
The preparation process embodiment 6 of detergent composition
The step of preparation process that granular pattern fabric detergent compositions are prepared according to table 9 below composition is as follows：
1) as shown in table 7, deionized water, LAS, AOS, acrylic acid and 2- acrylamide -2- methyl are added in preparing tank
Propyl sulfonic acid copolymer sodium salt derivative, sodium sulphate, sodium carbonate, zeolite, sodium silicate, brightening agent, starts stirring, obtains solid content
For 65% to 75% aqueous slurry, and it is 65 to 75 DEG C temperature control；
2) aqueous slurry is pumped by spray drying tower, spray drying obtains granule type solid；
3) granule type solid is transported to rear match system, in preparing tank and AEO9, peroxide bleaches, bleach activating
Agent, ozone stabilizer, protease, pigment, essence are uniformly mixed, and obtain granular pattern fabric detergent compositions.
9 granular pattern fabric detergent compositions of table form
Dimension disclosed herein and numerical value should not be construed as the stringent limitation of the exact value.Unless otherwise stated, often
A such dimension is intended to indicate that described value and the functionally equivalent scope around the value.For example, it is disclosed as the amount of " 40mm "
Guiding principle is intended to indicate that " about 40mm ".
The All Files quoted in the content of the invention is included herein by reference all in relevant portion.For any
The reference of file is not construed as recognizing that it is the prior art for the present invention.
Although specific embodiments of the present invention have had been illustrated and described, for those skilled in the art
For it is readily apparent that a number of other modification and change can be made in the case of without departing substantially from spirit and scope of the present invention
Type.These modifications and variations are included within protection scope of the present invention.
The above described is only a preferred embodiment of the present invention, not make limitation in any form to the present invention, therefore
It is every without departing from technical solution of the present invention content, what the technical spirit according to the present invention made above example any simply repaiies
Change, equivalent variations and modification, in the range of still falling within technical solution of the present invention.
Claims (11)
1. a kind of lifting cleaning compositions are in the water quality of high rigidity to the method for albumen soil removal capabilities, it is characterised in that：
This method is to use acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium salt derivatives, the copolymer
Sodium salt derivative meets the following conditions：
1) in copolymer, the quality of 2- acrylamide -2- methyl-propane sulfonic acid construction units accounts for acrylic acid and 2- acrylamides -2-
The 40% to 70% of methyl-propane 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.
2. according to the method described in claim 1, it is characterized in that：Acrylic acid and 2- the acrylamide -2- methyl-propyl sulphurs
The weight content of acid copolymer sodium salt derivative in detergent compositions is 0.01% to 5%.
3. according to the method described in claim 1, it is characterized in that：The hardness of the high hardness value water quality is higher than 250pm.
A kind of 4. detergent composition with enhancing albumen soil removal capabilities, it is characterised in that it includes：
In terms of weight content, 0.01% to 40% anion surfactant, 0.01% to 40% non-ionic surface is lived
Property agent, 0~30% zwitterionic surfactant, the group of 0~30% cationic surface active agent composition, washing helps
Agent, 0.01% to 5% acrylic acid and 2- acrylamide -2- methyl-propane sulfonic acid copolymer sodium salt derivatives, the copolymer
Sodium salt derivative meet the following conditions：
1) quality of 2- acrylamides -2- methyl-propane sulfonic acid construction units accounts for acrylic acid and 2- third in copolymer sodium salt derivative
The 40% to 70% of acrylamide -2- methyl-propane sulfonic acid construction unit gross masses；
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.
5. detergent composition according to claim 4, it is characterised in that：The anion surfactant is selected from sulfonic acid
Salt form surfactant, carboxylate surfactant, one or more mixtures in sulfated surfactant.
6. detergent composition according to claim 4, it is characterised in that：The nonionic surfactant is selected from fat
Alcohol alkoxylates, alkyl polyglycoside, fatty acid alkoxylates, fatty acid alkyl alcohol amide, ethoxylated sorbitan acid
One kind or their mixture in alcohol ester.
7. detergent composition according to claim 4, it is characterised in that：The 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, antiredeposition
One or more mixtures in agent；The bleach system includes peroxide bleaches, and bleach-activating and ozone are stablized
Agent.
8. detergent composition according to claim 7, it is characterised in that：Further comprise following optional addition
Agent：Alkaline agent, inorganic salts, viscosity modifier, preservative, colouring agent, one or more mixtures in essence.
9. detergent composition according to claim 4, it is characterised in that：The detergent composition can be any shape
Formula, including liquid form or solid form.
10. the preparation method of the detergent composition any one of claim 4-7, it is characterised in that including following step
Suddenly：
1) deionized water is added into preparing tank；
2) stirring is started, adds the surfactant, is warming up to 60 DEG C, stirring is to being completely dissolved；
3) heat source is withdrawn, adds acrylic acid and 2- acrylamide -2- the methyl-propane sulfonic acid copolymer sodium salt derivatives, is stirred
To being completely dissolved；
4) it is less than 45 DEG C in temperature, adds the washing assisant, stirs to being completely dissolved, up to detergent composition.
11. the preparation method of detergent composition according to claim 8, it is characterised in that comprise the following steps：
1) deionized water, anion surfactant, acrylic acid and 2- acrylamide -2- methyl-propyl sulphurs are added in preparing tank
Acid copolymer sodium salt derivative, inorganic salts, zeolite, brightening agent, starts stirring, obtains the aqueous slurry that solid content is 65% to 75%
Material, and temperature control at 65 to 75 DEG C；
2) by the aqueous slurry by being pumped by spray drying tower, spray drying obtains granule type solid；
3) granule type solid is transported to rear match system, is floated in preparing tank with nonionic surfactant, peroxide
White agent, bleach-activating, ozone stabilizer, enzyme preparation, colouring agent, essence are uniformly mixed, and obtain granular pattern fabric detergent group
Compound.
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| CA3151786A1 (en) * | 2019-10-11 | 2021-04-15 | Laura BUENO ROMO | A method of laundering fabric |
| CN111269760B (en) * | 2020-03-31 | 2021-07-02 | 广州立白企业集团有限公司 | Detergent composition for endowing washed fabrics with long-acting antibacterial and odor inhibition effects and odor evaluation method |
| CN111304023A (en) * | 2020-04-28 | 2020-06-19 | 上海华翰生物科技股份有限公司 | Cleaning agent composition |
| CN111363637A (en) * | 2020-04-28 | 2020-07-03 | 上海华翰生物科技股份有限公司 | Preparation process of cleaning agent composition |
| CN112725098B (en) * | 2020-12-28 | 2022-04-08 | 厦门琥珀日化科技股份有限公司 | Microcapsule essence laundry detergent and preparation method thereof |
| CN116440013A (en) * | 2023-04-13 | 2023-07-18 | 上海东利大健康研究院有限公司 | High-liquid-content cleaning wet tissue and two-step spray preparation method thereof |
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| CN101617034A (en) * | 2007-02-21 | 2009-12-30 | Lg生活健康株式会社 | Contain powder detergent of acidic water-soluble polymer and preparation method thereof |
| CN103459442A (en) * | 2010-11-23 | 2013-12-18 | 巴斯夫欧洲公司 | Copolymers containing carboxylic acid groups, sulfonic acid groups, and polyalkylene oxide groups, used as scale-inhibiting additives to detergents and cleaning agents |
| CN103890022A (en) * | 2011-08-10 | 2014-06-25 | 巴斯夫欧洲公司 | Copolymers made of isoprenol, monoethylenically unsaturated monocarboxylic acids and sulphonic acids, process for producing same and use of same as deposit inhibitors in systems conveying water |
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| DE10225794A1 (en) * | 2002-06-10 | 2003-12-18 | Basf Ag | Composition comprising sulfonic acid group containing copolymers, monoethylenically unsaturated carboxylic acid and nonionic monomer useful as a coating inhibiting additive in dishwashers |
| CN102197127A (en) * | 2008-09-01 | 2011-09-21 | 宝洁公司 | Sulfonate group-containing copolymers and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101617034A (en) * | 2007-02-21 | 2009-12-30 | Lg生活健康株式会社 | Contain powder detergent of acidic water-soluble polymer and preparation method thereof |
| CN103459442A (en) * | 2010-11-23 | 2013-12-18 | 巴斯夫欧洲公司 | Copolymers containing carboxylic acid groups, sulfonic acid groups, and polyalkylene oxide groups, used as scale-inhibiting additives to detergents and cleaning agents |
| CN103890022A (en) * | 2011-08-10 | 2014-06-25 | 巴斯夫欧洲公司 | Copolymers made of isoprenol, monoethylenically unsaturated monocarboxylic acids and sulphonic acids, process for producing same and use of same as deposit inhibitors in systems conveying water |
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