CN107523428A - Detergent composition and its application - Google Patents
Detergent composition and its application Download PDFInfo
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- CN107523428A CN107523428A CN201710630646.1A CN201710630646A CN107523428A CN 107523428 A CN107523428 A CN 107523428A CN 201710630646 A CN201710630646 A CN 201710630646A CN 107523428 A CN107523428 A CN 107523428A
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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
-
- 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
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/32—Amides; Substituted amides
-
- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- 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
-
- 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
Abstract
The present invention relates to a kind of detergent composition and its application.Detergent composition pH is 5~9；By weight percentage, comprising：(i) 0.1%~60% component A；(ii) 0.1%~10% component B；(iii) 0.01%~10.00% surfactant；(iv) 0.01%~40.00% oxidant；(v) 0.01%~10% enzyme preparation；(vi) 0~50% additive.Described detergent composition pH is neutral, and prolonged application does not produce significant incrustation scale in dish-washing machine yet, dish-washing machine is not caused significantly to damage, nor affects on the brightness of dishwashing detergent, while cleaning force is good.
Description
Technical field
The present invention relates to daily chemical product technical field, more particularly to detergent composition and its application.
Background technology
The appearance of dish-washing machine, consumer can be met to life health and the high level need in enjoyment time in leisure, it is more suitable
Answer the life of the high rhythm of Modern Family.In operation principle, dish-washing machine mainly produces by powerful current in three-dimensional space
Raw jet-action, the heat energy effect of warm water and the deoiling effect of detergent cleans decontamination to tableware.
The heating work mode of strong basicity detergent and dish-washing machine causes the serious fouling of dish-washing machine.For commercial dish-washing machine
Its washing water temperature is typically at 70 DEG C~90 DEG C, and household automatic dishwasher slurry water temperature is relatively low, typically 40 DEG C~
70℃.High water temperature can effectively improve cleaning capacity of the dish-washing machine to tableware, but under the higher use environment of the water hardness,
Heating hard water can cause heating tube to condense incrustation scale, so as to influence clean result.In addition, incrustation scale spot also can be in tableware surface shape
Into having a strong impact on the finish of tableware.Meanwhile to improve the cleaning force of dish-washing machine, it is also necessary to the use of detergent.It is different from
Detergent for washing dishware with hand, dish-washing machine special purpose detergent in use, without having skin contact with cleaning solution, therefore are typically washed
Wash agent product and all use higher alkalescence, add substantial amounts of soda ash, caustic alkali etc..High alkalinity condition, which is advantageous to greatly improve, to wash the dishes
Cleaning strength of the machine to various spots especially oil stain.But it is clear that the alkali source such as soda ash and caustic alkali will seriously increase in detergent
The speed and incrustation scale firmness that incrustation scale condenses.Moreover, also the silicate substrate to tableware and muffle painting etc. have strong basicity auxiliary agent
Extremely strong corrosiveness, therefore, detergent are also required to add corrosion inhibitor, the group as described in patent publication No. CN103180426A
Compound.Finally, strong basicity product also has certain risk safe to use, is easily touched and eats by mistake by mistake by consumer, causes the damage of body
Wound.
Sodium tripolyphosphate (STPP) is a kind of good antitartar agents, but due to causing the eutrophication of water body, it is each in the world
State is strictly limited.Sodium tripolyphosphate can be complexed the calcium ions and magnesium ions in water, softening of water, moreover it is possible to scattered calcium carbonate granule, from
And play and suppress the purpose that incrustation scale is formed.It with dislicata, sodium metasilicate, soda ash etc. together with share, ensure in dish-washing machine
When cleaning solution is buffered to pH higher than 9, still formed without notable incrustation scale.But due to the eutrophication problem of Phos, it is necessary to find
New method makes up the calcium ions and magnesium ions in cleaning agent and is complexed and disperse energy with calcium carbonate to replace the sodium tripolyphosphate in detergent
The missing of power.
Antiscaling type dishware detergent disclosed in patent CN1884462A and CN1421518A, wherein containing phosphate
Antisludging agent and water-soluble additive, this may cause a certain degree of pollution to water body；The use of chelating agent is ethylenediamine in invention
Tetrem acid sodium-salt and nitrilotriacetic acid, both chelating agents have all had confirmed that environmental hazard and biological carcinogenicity, are to forbid eating
Used in tool detergent.In addition, also add 3%-4% in dish-washing machine special-purpose tableware detergent disclosed in patent CN104031782A
Disodium ethylene diamine tetraacetate.In addition, three above patent does not add enzyme preparation, wash temperature is actually only applicable to
Commercial dish-washing machine high, wash time is short, and it is not suitable for domestic bowl-washing.Patent CN101528907A is disclosed for meal of machine-washing
Tool washes clean formulation, and it discloses the compounding of polymer and chelating agent to lift cleaning strength, a large amount of due to containing in embodiment
Sodium carbonate, therefore its cleaning strength and anti-fouling performance be not high.
The content of the invention
Based on this, it is necessary to provide that a kind of anti-fouling performance is excellent, and the detergent composition that cleaning force is good.
A kind of non-phosphate detergent composition, detergent composition pH are 5~9；By weight percentage, comprising：
(i) 0.1%~60% component A；
(ii) 0.1%~10% component B；
(iii) 0.01%~10% surfactant；
(iv) 0.01%~40% oxidant；
(v) 0.01%~10% enzyme preparation；
(vi) 0~50% additive；
Wherein, the component A be selected from the compound and its salt based on amino acid, the compound based on butanedioic acid and its salt,
One or more mixtures in multi-carboxy compound and its salt；
The component B is selected from anionic polymer and its salt.
The salt, which includes the part salt neutralized of the anionic polymer or the salt neutralized completely, polymer, to be included equal
Polymers or copolymer.
In one of the embodiments, the component A be selected from dicarboxyl methylalanine and its salt, two carboxymethyl glutamic acid and
One or more mixtures in its salt；
The component B is selected from the polymer and its salt, the list of anionic monomer containing sulfonic group of the monomeric unit containing carboxyl anion
In the polymer and its salt of member, the polymer and its salt of monomeric unit containing the carboxyl anion and anionic monomer unit containing sulfonic group
One or more mixing.
In one of the embodiments, the component A is selected from dicarboxyl methylalanine and its salt；The component B, which is selected from, to be contained
The polymer and its salt of acrylic monomer units.
In one of the embodiments, the detergent composition, by weight percentage, comprising：
(i) 5%~50% component A；
(ii) 1%~5% component B；
(iii) 0.01%~10% surfactant；
(iv) 0.01%~40% oxidant；
(v) 0.01%~10% enzyme preparation；
(vi) 0~50% additive.
In one of the embodiments, the detergent composition, by weight percentage, comprising：
(i) 5%~40% component A；
(ii) 1%~2% component B；
(iii) 0.5%~10% surfactant；
(iv) 1%~30% oxidant；
(v) 0.1%~10% enzyme preparation；
(vi) 8%~50% additive.
In one of the embodiments, the salt in the component A or component B is selected from ammonium salt and/or alkali metal salt.Alkali metal
Salt is lithium salts, sodium salt and sylvite.Particularly preferred salt is sodium salt.
In one of the embodiments, the enzyme preparation be selected from protease, lipase, cellulase, peroxidase and
One or more mixtures in amylase.
In one of the embodiments, the surfactant is nonionic surfactant, preferably is selected from fatty alcohol polyoxy
One or more mixture in vinethene -9, AEO -7, Pluronic PE 6800.
In one of the embodiments, the oxidant is in Inorganic perhydrate, organic peracid and its salt
One or more mixtures.It preferably is selected from Inorganic perhydrate, more preferably SODIUM PERCARBONATE.
In one of the embodiments, the activator also containing 0.1%~10% oxidant, the activator are tetrem
Acyl ethylenediamine.
In one of the embodiments, detergent composition pH is controlled for 5~9 by adding acid-base modifier, institute
Stating acid-base modifier includes acidity regulator and alkalinity regulator.Wherein, acidity regulator is selected from daily chemical product industry institute
Well known organic acid, inorganic acid and strong acid weak base salt, citric acid, butanedioic acid, benzoic acid, gallic acid, boric acid preferably are selected from, more
It preferably is selected from citric acid.Alkalinity regulator, selected from the organic base known to daily chemical product industry, inorganic base and strong base weak acid
Salt, the carbonate of organic amine, the hydroxide of alkali metal and alkali metal preferably is selected from, more preferably from sodium hydroxide.
The present invention also provides application of the described detergent composition in dish-washing machine special purpose detergent is prepared.
Compared with prior art, the invention has the advantages that：
Detergent composition of the present invention, on the basis of controlling pH to be 5~9, collaboration, which uses to be selected from, is based on amino acid
Compound and its salt, the compound based on butanedioic acid and its salt, multi-carboxy compound and its salt in it is one or more mixed
The component A of the compound and component B selected from anionic polymer and its salt.Wherein, based on amino acid, butanedioic acid or more carboxyls
In component A, especially dicarboxyl methylalanine or its salt are typical four teeth chelating agents, can effectively chelate the metals such as calcium and magnesium
Ion, it is set not produce insoluble matter, i.e. calcium carbonate, magnesium hydroxide etc., the basic component of calcium dirt.And component B it is poly- cloudy from
Sub- polymer or its salt, especially containing acrylic monomer units polymer or its salt, can effectively with the calcium ion in water
With reference to so that calcium carbonate lattice distortion produces defect, causes calcium carbonate granule to form loose spheric granules, and can not be attached to
In heating tube.
Thus make detergent composition of the present invention, under the conditions of non-strong basicity pH, remain able to obtain preferably
Cleaning force, and pH is 5~9, can effectively reduce the deposition of incrustation scale, have excellent anti-fouling performance, the family expenses that are particularly suitable for use in are washed
The washing of bowl machine, realize that detergent composition does not produce serious incrustation scale in dish-washing machine washs use and adheres to this purpose, no
Dish-washing machine is caused significantly to damage, nor affects on the brightness of dishwashing detergent.
Further, by rationally controlling component A and component B percentage by weight in detergent composition, it is possible to increase
The anti-tartar of the detergent composition and oil cut rate is gone, optimize the washing aid performance of detergent.
In detergent composition of the present invention, do not add using phosphide is contained, water body will not be polluted, environment
It is friendly.
Embodiment
The detergent composition of the present invention and its application are described in further detail below in conjunction with specific embodiment.It is right
For those skilled in the art, by reading the content of this disclosure, feature of the invention, beneficial effect and advantage
It 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 about 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, the environment at 25 DEG C occurs for all preparations and test herein.
Herein " comprising ", "comprising", " containing ", " containing ", " having " or other variants be intended to it is non-enclosed including,
Do not distinguished between these terms.Term "comprising" refers to that the other steps for not influenceing final result and composition can be added.Term
"comprising" also includes term " Consists of " and "consisting essentially of ...".The compositions and methods of the invention/technique can include,
It is made from it and substantially by essential elements described herein and limit entry and described herein any additional or optional
Composition, component, step or limit entry composition.
Dimension disclosed herein and numerical value should not be construed as the strict limitation of the exact value.Unless otherwise indicated, often
Individual 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 prior art for the present invention.
PH is neutral：
For liquid form composition, pH value is referred to the composition liquid at 25 DEG C and directly measured using conventional pH meter.For
On-liquid form families thing or high viscosity liquid composition, pH value refer at 25 DEG C, with 1:100 (composition weights：Water weight
Amount) dissolve in deionized water, measured using conventional pH meter.
PH neutrality is defined as measuring pH value range in pH5~pH9, preferably pH6~pH8, optimal selection pH7~pH8.
Strong basicity pH is defined as pH higher than 10.
The pH neutrality of detergent composition of the present invention is controlled by adding acid-base modifier.The acid-base accommodation
Agent includes：Acidity regulator and alkalinity regulator.Wherein acidity regulator is selected from organic known to daily chemical product industry
Acid, inorganic acid and strong acid weak base salt, preferably are selected from citric acid, butanedioic acid, benzoic acid, gallic acid, boric acid, more preferably from lemon
Acid.Alkalinity regulator, selected from the organic base known to daily chemical product industry, inorganic base and strong base-weak acid salt, it preferably is selected from
The carbonate of organic amine, the hydroxide of alkali metal and alkali metal, more preferably from sodium hydroxide.
Incrustation scale is formed：
Water containing mineral matters such as more calcium (Ca), magnesium (Mg) salts is called " hard water ".Under normal temperature condition, these calcium and magnesium salt
All it is dissolved in water.But after water is boiled, the less calcium sulfate of solubility can precipitate because declining heated solubility.It is solvable
Property calcium bicarbonate and magnesium bicarbonate heat endurance it is poor, decomposed with the heating of dampening these calcium and magnesium salt auxiliary agents and become indissoluble
The calcium carbonate and magnesium hydroxide of solution also precipitate.And with heating for multiple times hard water, these insoluble calcium magnesium salts can also add
Grown on hot wall, it is increasingly thicker, finally it is formed macroscopic incrustation scale.
Incrustation scale is generally cemented in heater surfaces, causes the reduction of heating surface heat transfer situation efficiency, so as to waste fuel or electricity
Power.Can also be because expanding with heat and contract with cold and unbalance stress, increase water heater the explosion even danger of blast.When finally incrustation scale is cementing,
Plurality of heavy metal ion can usually be adhered to, if for heating drinking water, have the risk that heavy metal ion is excessively dissolved in drinking-water.
Component A：
Contain substantial amounts of inorganic salts, especially calcium, magnesium salts etc. in domestic running.Usually, by calcium, magnesium ion in water
Content with " water hardness " represent.Because calcium, magnesium ion can be combined with the swill on service plate in water, influence these dirts from
Service plate surface is removed, so as to reduce the dirt-removing power of detergent.In addition, when the water higher to the water hardness heats, easily production
Raw tosca forms incrustation scale in heating tube and service plate.Incrustation scale is formed in heating tube will influence the efficiency of heating surface；On tableware
The glossiness of tableware can be influenceed by forming scale particles.
In detergent composition of the present invention, component A is selected from compound based on amino acid and its salt, based on amber
One or more mixtures in the compound and its salt, multi-carboxylic acid compounds and its salt of acid.Component A is in the detergent group
Weight percent content in compound is 0.1%~70%, preferably 5%~40%.Wherein the compound based on amino acid is selected from
MGDA (dicarboxyl methylalanine) or GLDA (two carboxymethyl glutamic acid).Compound based on butanedioic acid is selected from imino-diacetic amber
Acid.Multi-carboxylic acid compounds are selected from aliphatic carboxylic acid, alicyclic carboxylic acid, heterocyclic carboxylic acid or aromatic carboxylic acid, the polycarboxylic acid chemical combination
Thing includes at least two carboxyls, and these carboxyls are preferably to be separated by no more than two carbon atoms.Wherein include two carboxylics
The polycarboxylic acid of base such as butanedioic acid, malonic acid, oxalic acid, maleic acid, diglycolic acid, tartaric acid, hydroxymalonic acid, fumaric acid etc..
In the present invention in the combination of involved detergent, the compound and its salt of the component A preferred amino acids, selected from two
One or more mixtures in carboxymethyl alanine and its salt, two carboxymethyl glutamic acid and its salt.Said components A preferably should
The salt of compound.Preferable salt is ammonium salt and/or alkali metal salt, i.e. lithium salts, sodium salt and sylvite, and particularly preferred salt is sodium salt.
Component B：
During heating, the calcium ions and magnesium ions in hard water can form calcium carbonate and magnesium hydroxide crystallite, and be deposited in heating tube,
And constantly growth, and form the incrustation scale cladding heating tube for being difficult to remove.Some polyanion homopolymers or copolymer can be effective
And calcium binding so that calcium carbonate lattice distortion produce defect, cause calcium carbonate granule to form loose spheric granules, and
It can not be attached in heating tube.So as to realize that suppressing incrustation scale forms, protection heating tube, the purpose of bright tableware.
In detergent composition of the present invention, component B is selected from the polymer of polyanion, including homopolymer or common
Polymers, and its part salt neutralized or the salt neutralized completely.Wherein anion is selected from carboxyl anion or sulfonic group anion.
The monomeric unit containing carboxyl anion of the polymer includes acrylic acid, fumaric acid, maleic acid, itaconic acid, aconitic acid, methyl and prolonged
Fumarate, citraconic acid, maleic anhydride.Sulfonated monomer unit containing sulfonic group anion includes 2- acrylamido -2- methyl
Propane sulfonic acid, 2- methacryl amido -2- methyl propane sulfonic acids, 3- methacryl amido -2- hydroxy-propanesulfonic acids, pi-allyl sulphur
Acid, methylpropenyl sulfonic acid, vinyl sulfonic acid, 3- allyloxy -2- hydroxyl -1- propane sulfonic acid, 2- methyl -2- acrylic -1- sulphurs
Acid, styrene sulfonic acid, acrylic acid -3- sulfo group propylene base ester, methacrylic acid 3- sulphopropyls, 2- acrylamide -2- methyl-props
Sulfonic acid, sulfomethvl acrylamido.And the suitable non-anion monomeric unit that can be selected, including acrylamide, alkane
Base vinyl ethers, methyl vinyl ether, styrene.
In the present invention in the combination of involved detergent, the component B preferably is selected from the poly- of the monomeric unit containing carboxyl anion
One or more in compound, more preferably from one kind or more in the polymer of acrylic monomer units and maleic acid monomer units
Kind.The salt that said components B preferably polymer moieties are neutralized or neutralized completely.Preferable salt is ammonium salt and/or alkali metal salt,
That is lithium salts, sodium salt and sylvite, particularly preferred salt are sodium salts.
Weight percent contents of the said components B in the detergent composition be 0.1%~10%, preferably 1%~
5%.
Surfactant：
In detergent composition of the present invention, the surfactant is nonionic surfactant, preferably fat
Mixing more than one or both of fat alcohol APEO -9, AEO -7, Pluronic PE 6800
Thing.Wherein preferred Pluronic PE 6800, it has excellent emulsification clean effect, and foam volume is low, will not be in automatic bowl
A large amount of foams are produced in machine running, cause washing to bear to machine, preferably addition is 0.01%~10.0%.
Oxidant and its activator：
Oxidant is allowed to point mainly for some coloured stains, such as coffee stain, such as tea stain, coffee stain, tea stain, red wine
Solution is removed, and has the effect of sterilizing concurrently.
The oxidant can select Inorganic perhydrate or organic peracid and its salt.
Hydrogen peroxide can add and be formed compound with some inorganic matters, so as to ensure that peroxide can be in solid form
It is steady in a long-term to exist.The inorganic salts of adduct can be formed with hydrogen peroxide includes carbonate, borax, sulfate etc., i.e., carbon
Hydrochlorate, perborate, persulfate etc..It is preferred that percarbonate.The Inorganic perhydrate is typically lithium salts, sodium salt or potassium
The alkali metal salts such as salt, particularly sodium salt.
Organic peracid includes all organic peracids for being commonly used for bleaching agent, including phthalimido peroxy caproic acid, mistake
Benzoic acid, list cross neck phthalic acid or diperoxy phthalic acid, 2- octyl group diperoxies butanedioic acid, diperoxy dodecyl two
Peroxycarboxylic acid and its salt such as acid, diperoxyazelaic acid and imido peroxycarboxylic.Wherein preferred phthalimido peroxide
Caproic acid.
Weight percent content of the above-mentioned oxidant in the detergent composition is 0.01%~40%, preferably 1%
~20%.
The activator of more than one oxidant is also included in detergent composition of the present invention, to improve relatively low
Coloured stains under wash temperature aoxidize cleaning speed, realize the purpose that low temperature expresses.Wherein selectable activator has N- acyls
Based compound and O- acyl compounds, such as acylated amine, acylated glycolurils or acylated sugar compounds.It is preferred that tetraacetyl ethylene diamine.
Weight percent content of the above-mentioned activator in the detergent composition is 0.1%~10%, preferably 0.1%
~4%.
Enzyme preparation：
In detergent composition of the present invention, enzyme preparation is selected from protease, lipase, cellulase, peroxide
One or more of mixtures in enzyme and amylase.Weight percent content in the detergent composition is 0.01%
~10%, preferably 0.1%~4%.
The detergent composition of the present invention can also include：Account for the enzyme stabilising system of composition weight 0.001% to 10%.
The enzyme stabilising system can be compatible with detergent composition, can include calcium ion, boric acid, borax, propane diols, glycerine, polynary
One or more of mixtures of alcohol.
It is without phosphorus：
It is this phosphorous to help to improve the cleaning strength of detergent it is well known that some phosphorous assistants are often added in detergent
Agent is divided into Phos and organic phosphine.Sodium tripolyphosphate is known inorganic phosphate builder, it to calcium ions and magnesium ions and heavy metal ion all
There is prominent chelation, the water hardness can be significantly reduced；And be alkaline assistant, alkaline washing ring can be provided for detergent
Border；Also there is significantly scattered suspension effect to some graininess dirts.Organic phosphine auxiliary agent is mainly the chelating containing phosphate group
Agent, such as ATMP (ATMP), hydroxy ethylene diphosphonic acid (HEDP), ethylenediamine tetramethylene phosphonic acid
(EDTMPS), diethylenetriamine penta (DTPMPA) etc..These organic phosphine auxiliary agents can significantly reduce the water hardness, and
By distorting calcium carbonate lattice and divergent function, suppress the deposition of calcium carbonate.But due to the discharge of a large amount of phosphorous domestic waters,
The eutrophication of water body, adverse condition, therefore countries in the world are caused progressively to limit phosphorus, prohibited phosphorus.
The detergent composition of the present invention is without phosphorus composition, without phosphorus to refer to not add the auxiliary agent containing P elements, or
The content of P elements is less than the 1% of composition weight in composition.
Optional member：
Detergent composition of the present invention can also include following optional additive：Filler, alkaline agent, foam control
Preparation, pH adjusting agent, preservative, colouring agent, colour stabilizer and essence one or more compositions mixtures.
Detergent composition of the present invention can include one or more fillers, selected from sodium citrate, sodium sulphate,
Sodium chloride, potassium chloride, water, preferably sulfuric acid sodium.
Detergent composition of the present invention can include one or more alkaline agents, selected from sodium hydroxide, potassium hydroxide,
The silicate of alkali carbonate, alkali metal.Detergent composition of the present invention can include one or more of foams
Controlling agent, to reduce caused foam in washing process.Suitable foam controller is all foam controls that this area uses
Preparation, such as organosilicon and paraffin oil.Weight percent content of the foam controller in the detergent composition is less than
5%.
In some embodiments, detergent composition of the present invention preferably comprises preservative, and suitable example is
Phenoxy group alcohol, sodium benzoate；OIT and its derivative, such as methylisothiazolinone, methylchloroisothiazandnone, benzo
One kind or its mixture in OIT.Preservative dosage is 0.001% to 5%, preferably 0.01% to 2%.
Compound method：
The detergent composition of the present invention is prepared using various methods well-known to those skilled in the art.The composition
Preparation can be carried out by conventional meanses, specifically should be according to the stabilization of the state of component in the solution and effect, and component
The suitable processing temperature of Sexual behavior mode and process time.
Without being further described, it is believed that those skilled in the art can use this to greatest extent using described 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 examples, except as otherwise noted, all contents are weight percentages, and relevant ingredients listed contains
Amount is the content of the active material by conversion.
The preparation method of detergent composition, comprises the following steps：
1) filler is first put into ingredients pot；
2) under stirring, component A, component B, surfactant is sequentially added, is stirred；
3) defoamer, oxidant and its activator are put into, is stirred；
4) essence and enzyme preparation are put into ingredients pot, is stirred；
5) other additives are added into ingredients pot, are stirred；
6) continue sufficiently to stir the material in ingredients pot, ensure no skinning clustering phenomena, by what is be well mixed
Material sieves (20-80 mesh), through examining qualified and being packed.
The detergent composition of the present invention can be processed into any desired form.According to the determination of further composition,
Liquid or solid can be manufactured into immediately.Fluid composition can be made liquid dishwasher agent of the viscosity less than 100 centistokes (cSt) and wash
Agent, the gel form more than 1000 centistokes, even semisolid pasty state can also be made.Solid composite can be made into particle
Shape, such as powder, particulate, fragment, or solid solid forms, as block or piece, consumer are higher to the acceptance level of the latter.
Experiment is prepared with 250ppm hard water according to GB 9985-2000 B1.2 method.
Anti-fouling performance determines：
Measuring principle：The fouling condition of different sample products is heated in hard water using electrical bar.
In beaker, add 1.0L 250ppm hard water, and 8g samples, after stirring and dissolving, be put into electrical bar, be powered plus
Heat.Treat that water is boiled, keep boiling 30 seconds, stop heating.Electrical bar is taken out, the water in beaker is outwelled, is calculated as once testing.Again
After adding hard water and sample, heat again.After completing 20 heating tests time, by heating rod and beaker ultrapure water three
It is secondary, carry out calcium dirt deposition amount (instrumental method) and range estimation calcium dirt grade (ocular estimate) measure.
Calcium dirt deposition amount (instrumental method)：
The heating rod being completed is put into 1.0L beakers, and adds 1.0L ultra-pure waters and 10g citric acids, heats and protects
80 DEG C are held until all incrustation scales are completely dissolved.The pure water vapored away is supplemented, it is 1.0L to ensure each liquor capacity, then profit
Calcium ion mass percentage content (X) in the spectrophotometer solution is inhaled with atom.
Calcium dirt deposition amount is expressed as：(100/40)×X×106Mg (with calcium carbonate quality representation)
The anti-fouling performance of sample represents that calcium dirt deposition amount is lower with calcium dirt deposition amount, shows that fouling is fewer, i.e. anti-fouling performance
Better.Usually, when calcium dirt deposition amount is less than 10mg, almost there is no incrustation scale on heating rod；In 10mg~50mg scopes, heating
There is the visible incrustation scale of a small amount of naked eyes on rod；And calcium ion content, when being more than 200mg, incrustation scale is very thick.
Estimate calcium dirt grade (ocular estimate)：
Ocular estimate is scored using different testers according to unified standard, takes the resultful average value of institute to be after scoring
The range estimation calcium dirt grade of the sample.
Standards of grading：10 points, complete Non-scale, heating tube is the silvery white of metal；
9 points, there is very small amount of incrustation scale, heating tube is the silvery white of metal；
8~7 points, there is a small amount of incrustation scale, heating tube is low and deep metal silvery white；
6~5 points, there is more incrustation scale, heating tube is canescence；
<5 points, there are a large amount of incrustation scales, heating tube is almost milky；
Score value is higher, i.e., calcium dirt lower grade, shows that the calcium dirt for being deposited in heating tube is fewer.
PH assay methods：
PH refers at 25 DEG C, with 1:100 (composition weights：Water weight) dissolve in deionized water, using conventional pH meter
Measure.
Go the measure of oil cut rate：
Measuring principle：Standard intraocular's dirt is set to be evenly affixed on slide, with the dishwashing detergent agent solution of normal concentration
After washing under the conditions of defined, the removal percentage of dirt is determined.
Artificial dirt carries out dirt preparation according to GB 9985-2000 B2.4 method.
The preparation of experiment glass slides：On slide, along 10mm lines are drawn, limitation will be defiled below this line to show；And carrying
Mark is carried out to distinguish each slide in edge on slide.It is one group by the slide of cleaning with four to be placed on weighing frame with analysis
It is M0 that balance, which is precisely weighed (accurately to 1mg),.Clamped with experiment clip along part on slide mark line, as what is be already prepared to
In dirt, dirt needs to submerge mark line with lower part, then takes out and is placed on drying frame, overnight to be dried.Claiming within second day
It is precisely weighed on amount frame with assay balance as M1.
Test procedure：
By the slide insertion of the known amount of defiling to preparing to wash in deserved wash stand.
Agitator is switched on power, wash temperature is controlled in room temperature, rotating speed 700rpm.
Weighing 4.8 grams (hand washing liquid detergent takes 4.8 grams, and automatic dish-washing machine detergent takes 2.4 grams) treats test sample in 1200ml's
In 250mg/L hard water, turn on agitator, start to wash, (hand washing liquid detergent wash time 4min, automatic dish-washing machine rear in 4min
Detergent wash time 2min30s), agitator is closed, wash stand is taken out from cleaning solution, is stood overnight, second day to washing
Slide accurate weighing afterwards is M2.
Note：
1st, every batch of experiment should be contrast dish washing detergent two groups of dirt pieces of preparation, dirty for two groups of each sample to be tested preparation
Piece.
2nd, due to defile condition difference can on going oil cut rate measurement result to bring influence, Gu the same slide defiled no matter can
How many testing sample are enough set, it is necessary to which the dish washing detergent of two groups of measure contrasts of band is compareed.
Oil cut rate is gone to calculate：Remove oil cut rate=(M1-M2)/(M1-M0)
In formula：Slide weight, g before M0- defiles；Slide weight, g after M1- defiles；Slide weight after M2- washings,
g。
Enzyme stability is tested：
After composition is stored in into 45 DEG C of constant temperature oven four weekss, the enzyme activity force value and its initial energy value of composition after heat storage
Ratio, be expressed as a percentage.The enzyme activity conservation rate of the residual protein enzyme of every kind of formula with reference to E.Dunn and
Magazine (Analyst, 1971 (96) that R.Brotherton is published:159-163) method determines.
Embodiment
Comparative example 1-3 and embodiment 1-6 detergent composition is prepared according to table 1.
The comparative example 1-3 of table 1 and embodiment 1-6 automatic dish-washing machine detergent compositions composition
1. it is purchased from BASF.
Table 2 goes oil cut rate result of the test
A, commercially available brand are alkalescent dishwashing liquid
The enzyme stability of table 3 is tested
Commercially available brand 1aWashed the dishes powder for alkalescence containing enzyme；Commercially available brand 2aFor the dishwashing liquid of alkalescent containing enzyme
In the comparative example 1 of table 1, comparative example 2 and comparative example 3, added with substantial amounts of sodium carbonate, and pH adjusting agent is not added with,
Cause the pH of its composition aqueous solution higher, be strong basicity.This can cause obvious corrosiveness to tableware.And anti-tartar
Energy test result shows that its calcium dirt deposition amount is higher, respectively 726.3mg, 126.6mg and 501.4mg, and range estimation rule shows
The formation of incrustation scale can be clearly visible.Therefore long-term use of service life for influencing whether dish-washing machine and tableware and washing are imitated
Fruit.
Embodiment 1 to embodiment 6 has been separately added into the component A, component B, pH adjusting agent of different weight percentage, its calcium dirt
Deposition significantly reduces, and ocular estimate is without unobvious incrustation scale spot, i.e., with excellent anti-fouling performance.
Table 2 shows that embodiment 1 has to embodiment 6 and preferably goes oil cut rate, can remove the spot of the overwhelming majority.It deoils
Rate performance is suitable with commercially available brand, but the pH value of composition solution is lower, i.e., gentleer.
Table 3 shows that embodiment 1 to the enzyme preparation of embodiment 6 has preferable stability, stores up by prolonged heat, does not almost have
There is an enzyme inactivation, and commercially available brand 1aEnzyme have partial inactivation, commercially available brand 2aThen complete deactivation.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that come for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of detergent composition, it is characterised in that detergent composition pH is 5~9；By weight percentage, comprising：
(i) 0.1%~60% component A；
(ii) 0.1%~10% component B；
(iii) 0.01%~10% surfactant；
(iv) 0.01%~40% oxidant；
(v) 0.01%~10% enzyme preparation；
(vi) 0~50% additive；
Wherein, the component A is selected from the compound and its salt based on amino acid, the compound based on butanedioic acid and its salt, more carboxylics
One or more mixtures in based compound and its salt；
The component B is selected from anionic polymer and its salt.
2. detergent composition according to claim 1, it is characterised in that the component A is selected from dicarboxyl methylalanine
And its one or more mixtures in salt, two carboxymethyl glutamic acid and its salt；
The component B is selected from the polymer and its salt, the anionic monomer unit containing sulfonic group of the monomeric unit containing carboxyl anion
Polymer and its salt, monomeric unit containing the carboxyl anion and anionic monomer unit containing sulfonic group polymer and its salt in one
Kind or a variety of mixtures.
3. detergent composition according to claim 2, it is characterised in that the component A is selected from dicarboxyl methylalanine
And its salt；The component B is selected from polymer and its salt containing acrylic monomer units.
4. according to the detergent composition described in claim any one of 1-3, it is characterised in that by weight percentage, comprising：
(i) 5%~50% component A；
(ii) 1%~5% component B；
(iii) 0.01%~10% surfactant；
(iv) 0.01%~40% oxidant；
(v) 0.01%~10% enzyme preparation；
(vi) 0~50% additive.
5. detergent composition according to claim 4, it is characterised in that by weight percentage, comprising：
(i) 5%~40% component A；
(ii) 1%~2% component B；
(iii) 0.5%~10% surfactant；
(iv) 1%~30% oxidant；
(v) 0.1%~10% enzyme preparation；
(vi) 8%~50% additive.
6. according to the detergent composition described in claim any one of 1-3, it is characterised in that the enzyme preparation is selected from albumen
One or more mixtures in enzyme, lipase, cellulase, peroxidase and amylase.
7. according to the detergent composition described in claim any one of 1-3, it is characterised in that the surfactant is selected from fat
One or more mixture in fat alcohol APEO -9, AEO -7, Pluronic PE 6800.
8. according to the detergent composition described in claim any one of 1-3, it is characterised in that the oxidant is selected from inorganic mistake
Aoxidize one or more mixtures in hydrogen peroxide adduct, organic peracid and its salt.
9. detergent composition according to claim 8, it is characterised in that also containing 0.1%~10% oxidant
Activator, the activator are tetraacetyl ethylene diamine.
10. application of the detergent composition described in claim any one of 1-9 in dish-washing machine special purpose detergent is prepared.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110916586A (en) * | 2019-12-19 | 2020-03-27 | 广东康宝电器股份有限公司 | Control method of steam dish-washing machine |
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| CN101018849A (en) * | 2004-09-14 | 2007-08-15 | 巴斯福股份公司 | Cleaning formulations for dishcleaning machine containing hydrophobically modified polycarboxylate |
| CN101300332A (en) * | 2005-11-07 | 2008-11-05 | 雷克特本克斯尔荷兰有限公司 | Composition |
| CN101528907A (en) * | 2006-08-10 | 2009-09-09 | 巴斯夫欧洲公司 | Cleaning formulation for a dish washer |
| CN101688155A (en) * | 2007-04-25 | 2010-03-31 | 巴斯夫欧洲公司 | Not phosphatic dishwasher detergent with excellent rinsing power |
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