CN108865480A - A kind of automatic dish-washing machine special purpose detergent composition - Google Patents

A kind of automatic dish-washing machine special purpose detergent composition Download PDF

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Publication number
CN108865480A
CN108865480A CN201810901960.3A CN201810901960A CN108865480A CN 108865480 A CN108865480 A CN 108865480A CN 201810901960 A CN201810901960 A CN 201810901960A CN 108865480 A CN108865480 A CN 108865480A
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China
Prior art keywords
unsaturated monomer
acid
copolymer dispersant
washing machine
special purpose
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CN201810901960.3A
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CN108865480B (en
Inventor
张龙秋
周文杰
梁智坤
黄亮
沈兵
张利萍
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Guangzhou Lidi Technology Co ltd
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Guangzhou Liby Enterprise Group Co Ltd
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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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3738—Alkoxylated silicones
    • 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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • 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
    • 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
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D3/38636—Preparations containing enzymes, e.g. protease or amylase containing enzymes other than protease, amylase, lipase, cellulase, oxidase or reductase
    • 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
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • 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
    • C11D3/38654—Preparations containing enzymes, e.g. protease or amylase containing oxidase or reductase
    • 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
    • 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
    • C11D1/008—Polymeric surface-active agents
    • 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
    • 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
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • C11D2111/14—

Abstract

The invention discloses a kind of automatic dish-washing machine special purpose detergent compositions, are related to daily-use chemical industry technical field.The composition includes：0.01~20 part of polyether surfactant；0.01~20 part of nonionic surfactant；0.01~20 part of other surfaces activating agent；0.1~30 part of copolymer dispersant；0.1~40 part of amino acid derivativges chelating agent；0.1~10 part of enzyme preparation and 0~80 part of additive；Wherein, the nonionic surfactant includes at least two kinds of fatty alcohol alkoxy compounds, for quick emulsification type fatty alcohol alkoxy compound and at a slow speed emulsifying fatty alcohol alkoxy compound, and the weight ratio of the polyether surfactant and the fatty alcohol alkoxy compound is 1：0.1~1.5.Automatic dish-washing machine special purpose detergent composition provided by the invention all has good emulsion dispersion removal to greasy dirt, food dirt and acts on, and the foam in washing process is effectively reduced, improves the cleaning capacity of detergent.

Description

A kind of automatic dish-washing machine special purpose detergent composition
Technical field
The present invention relates to daily-use chemical industry technical field more particularly to a kind of automatic dish-washing machine special purpose detergent compositions.
Background technique
Compared with washing by hand tableware, automatic dish-washing machine have the advantages that save physical strength, conveniently, it is water-saving, and have cleaning, The multiple functions such as disinfection, drying and storage, therefore can sufficiently meet that it is desirable to conform to the principle of simplicity to solve abjection in single duplicate housework The needs come.
Dirt on dishwasher removal tableware is mainly that the injection for relying on powerful water flow to generate in three-dimensional space is made With the thermal energy effect of, warm water and the deoiling effect of cleaning agent, these three effects mutually collaboration is completed.By force (forcing) pump It is ejected into the rotary motion that the water flow in dish-washing machine carries out three-dimensional space in machine from nozzle after pressurization, is not present in machine The dead angle of less cleaning sprays the strong current kinetic energy impact effect of generation, can be effectively removed the dirt adhered on tableware. Meanwhile the dirt-removing power of hot water is significantly improved than cold water, the solubility of the indissolubles object such as slightly soluble salt often greatly increases in the hot water, So hard water salt crust obtains a degree of reduction a possibility that being formed on tableware, and the greasy dirts such as fat are higher than its in temperature When fusing point, the attractive interaction between oil droplet is reduced, and adhesive force of the oil droplet on tableware surface also reduces, therefore is easy to from tableware table Face is removed, and is not easy to adsorb again and be deposited on tableware.And many ingredients in automatic dish-washing machine special purpose detergent are as bleached Agent etc., have at relatively high temperatures more have the characteristics that it is higher active, these ingredients often machine washing special purpose detergent in can send out It waves than effect stronger in detergent for washing dishware with hand.
Due to the limitation of dishwasher into operation principle, detergent for washing dishware with hand cannot be mixed with machine washing detergent.In daily use chemicals In industry wisdom, for the detergent of laundering of textile fabrics, hand-washing with the formula of machine washing is that comparison is similar, only various components Content is different, i.e., different to the tendency of certain performance indicators, for example requires handwashing products foaming abundancy, and machine-washes and then require Middle bubble or low bubble.Or briefly, the two is mixed in fact also without too big problem.But absolutely can not when dishwashing detergent Mixed, detergent for washing dishware with hand cannot be used for automatic dish-washing machine.In detergent for washing dishware with hand, consumer is mostly according to foam volume Number judge whether detergent additive amount enough.Therefore, detergent for washing dishware with hand will steep more or even to have certain foam stabilizing Performance plays a major role to decontamination moreover, surface-active contents are high.Furthermore, it is not necessary that additionally using builder.But In machine washing, in order to protect water pump, overflow is prevented, prevents excessive foam from influencing the rotation etc. that pendulum washes arm, dish-washing machine personal cleansing Agent must be it is low foaming, it is even still.Surfactant is more to play moistened surface to make in machine washing special purpose detergent With.
Although selected surfactant is low bubble in dish-washing machine detergent, since the impact of dish-washing machine water flow is made With so that surfactant solution inevitably will form foam, in addition the water solubilitys such as the protein contained in dirt, starch Macromolecule can also form stable foam, and the presence of these foams can all influence the clean effect of dish-washing machine, therefore, how control The bubble-related issues of dish-washing machine special purpose detergent are always one of emphasis of the area research.
Summary of the invention
The technical problem to be solved by the present invention is to existing dish-washing machine detergent foam is excessive, deoiling for dish-washing machine is influenced Dirty effect.
To solve the above-mentioned problems, the present invention provides following technical scheme：
A kind of automatic dish-washing machine special purpose detergent composition, including following parts by weight of component：
0.01~20 part of polyether surfactant；
0.01~20 part of nonionic surfactant；
0.01~20 part of other surfaces activating agent；
0.1~30 part of copolymer dispersant；
0.1~40 part of amino acid derivativges chelating agent；
0.1~10 part of enzyme preparation；
0~80 part of additive；
Wherein, the nonionic surfactant includes at least two kinds of fatty alcohol alkoxy compounds, is quick emulsification type rouge Fat alcohol alkoxylates and at a slow speed emulsifying fatty alcohol alkoxy compound, and the polyether surfactant and the fat The weight ratio of alcohol alkoxylates is 1：0.1~1.5.
Further technical solution is for it：Polyether surfactant has following general formula (1)：
Wherein, in general formula (1), the molecular weight of the polyether surfactant is 500~6000；
In the molecule of the polyether surfactant, the content of ethyl oxide is 40%~80%；
In the molecule of the polyether surfactant, the content for aoxidizing propyl is 5%~40%；
In the molecule of the polyether surfactant, the content for aoxidizing butyl is 3%~20%；
In the molecule of the polyether surfactant, R base is selected from the straight-chain fatty alcohol and/or branch that carbon number is 6 to 24 Fatty alcohol, and R is selected from uncle position, secondary position and uncle position based on the binding site of polyether group.
Further technical solution is for it：The content of quick emulsification agent fatty alcohol alkoxy compound is the 0.01% of composition ~10%, and the quick emulsification agent fatty alcohol alkoxy compound has following general formula (2)：
Wherein, in general formula (2), n is 2~16 and n is positive integer；M is 2~10 and m is positive integer；X is 0~10；Y is 0 ~10；Z is 0~10；(x+z)：Y is 0.2~1；
The content of the fatty alcohol alkoxy compound of emulsifier at a slow speed be composition 0.01%~15%, and it is described at a slow speed Emulsifying fatty alcohol alkoxy compound can also have following general formula (3)：
Wherein, in general formula (3), n is 2~16 and n is positive integer；M is 2~10 and m is positive integer；X is 3~30；Y is 0 ~10；Z is 3~30；(x+z)：Y is 3~10.
Further technical solution is for it：The other surfaces activating agent includes alkyl polyglycoside, fatty acid alkoxylate The direct polyoxyethylene of object, fatty acid alkyl alcohol amide, fatty acid methyl ester ethoxylate, natural oil or polyoxypropylene compound It is at least one.
Further technical solution is for it：The repetitive unit of copolymer dispersant is selected from unsaturated monomer A, unsaturated monomer The group that residue forms after B, unsaturated monomer C polymerization, and meet following relationship：
1) residue of the unsaturated monomer A of the copolymer dispersant in copolymer dispersant weight accounting be 60% to 90%；
2) the unsaturated monomer A of the copolymer dispersant includes the unsaturated monomer A1 of weight ratio 70% to 99.99% With the unsaturated monomer A2 of weight ratio 0.01% to 30%；
3) the unsaturated monomer A1 of the copolymer dispersant, which is selected from, contains a carboxylic acid group, and contains only one not It is saturated the monomer of double bond；The carboxylic acid group of the unsaturated monomer A1 of the copolymer dispersant is in copolymer dispersant with salt shape Formula exists；
4) the unsaturated monomer A2 selection of the copolymer dispersant contains more than one carboxylic acid group, and contains only one The monomer of a unsaturated double-bond；
5) residue of the unsaturated monomer B of the copolymer dispersant in copolymer dispersant weight accounting be 10% to 40%；
6) the unsaturated monomer B of the copolymer dispersant is selected from containing a sulfonic acid group and contains only an insatiable hunger With the monomer of double bond, the sulfonic acid group of the unsaturated monomer B of the copolymer dispersant in copolymer dispersant in the form of salts In the presence of；
7) residue of the unsaturated monomer C of copolymer dispersant weight accounting in copolymer dispersant is 0.1% To 20%；
8) the unsaturated monomer C of the copolymer dispersant is selected from the monomer containing a unsaturated double-bond；
9) molecular weight of the copolymer dispersant is 1000~150000.
Further technical solution is for it：The unsaturated monomer A1 of copolymer dispersant be selected from acrylic acid, methacrylic acid, Alpha-hydroxy acrylic acid, Alpha-hydroxy methacrylic acid, butenoic acid；
The unsaturated monomer A2 of the copolymer dispersant is selected from maleic acid, fumaric acid, maleic anhydride, itaconic acid, lemon health Acid；
The unsaturated monomer B of the copolymer dispersant is selected from the vinyl monomer containing sulfonic acid group, contains sulfonic group The allyl monomer of group, the acrylamide containing sulfonic acid group, the Methacrylamide containing sulfonic acid group contain sulfonic acid group Acrylate, the methacrylate containing sulfonic acid group.
Further technical solution is for it：The unsaturated monomer C of copolymer dispersant includes unsaturated monomer C1, unsaturation Monomer C2 and unsaturated monomer C3；
The unsaturated monomer C1 of the copolymer dispersant is selected from the compound for meeting following general formula (4)：
Wherein, in general formula (4), R1Selected from hydrogen, the group of one or more compositions of methyl, the positive integer that n is 2 to 8；
The unsaturated monomer C2 of the copolymer dispersant is selected from acrylamide, benzyl methacrylamide, cyclohexyl first Base acrylamide, N-tert-butyl acrylamide, Methacrylamide, dimethacrylamide, dimethylaminopropyl metering system One of amide；
The unsaturated monomer C3 of the copolymer dispersant is selected from the change for meeting following general formula (5) and/or following general formula (6) Close object：
Wherein, in general formula (5), R1Selected from hydrogen, the group of one or more compositions of methyl, R2The saturation for being 2 to 8 for carbon number Alkyl；
Wherein, in general formula (6), R1Selected from hydrogen, the group of one or more compositions of methyl, R3Selected from hydrogen, methyl, ethyl The group of one or more compositions, R4Selected from hydrogen, the saturated alkyl that carbon number is 1 to 20, the positive integer that m is 1 to 30.
Further technical solution is for it：The amino acid derivativges chelating agent includes methylglycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA), N, N- dicarboxylic acids amino -2- hydroxy propane base sulfonic acid, 3- hydroxyl -2,2 '-imino group At least one of disuccinic acid and its alkali metal salts or ammonium salt.
Further technical solution is for it：Enzyme preparation includes protease, alpha-amylase, cellulase, hemicellulase, phosphorus Lipase, esterase, lipase, peroxidase/oxidizing ferment, pectase, lyases, mannase, cutinase, reductase, wood Dextranase, amylopectase, tannase, pentosanase, maltosan, arabinase, at least one of 1,4 beta-glucanase.
Further technical solution is for it：Additive includes that filler, alkaline agent, viscosity modifier, bleach system, ozone are steady Determine at least one of agent, corrosion inhibitor, preservative, colorant, colour stabilizer and essence.
Compared with prior art, the attainable technical effect of present invention institute includes：
Automatic dish-washing machine special purpose detergent composition proposed by the present invention, by the way that a certain proportion of polyether-type surface is being added Activating agent and fatty alcohol alkoxy compound can greatly reduce the foam in washing process；A component cooperates with mutually in composition Cooperation, can promote nonionic surfactant to the emulsion dispersion effect of greasy dirt, the detergency ability of enhancing；Guarantee Nozzle of bowl washer Water flow pressure, promote the detersive efficiency of dish-washing machine.
Detailed description of the invention
Technical solution in order to illustrate the embodiments of the present invention more clearly, below will be to needed in embodiment description Attached drawing is briefly described, it should be apparent that, drawings in the following description are some embodiments of the invention, general for this field For logical technical staff, without creative efforts, it is also possible to obtain other drawings based on these drawings.
Fig. 1 is the mechanism of action schematic diagram that polyether surfactant inhibits nonionic surfactant blistering；
Fig. 2 is the evaluation criterion schematic diagram of conjunctiva and spotting.
Specific embodiment
For those skilled in the art, feature of the invention, beneficial by reading the content of this disclosure Effect and advantage will become obvious.Based on the embodiments of the present invention, those of ordinary skill in the art are not making wound Every other embodiment obtained under the premise of the property made labour, shall fall within the protection scope of the present invention.
Unless otherwise specified, all percentages, score and ratio are calculated by the total weight of the present composition.It removes Non- otherwise indicated, all wt in relation to ingredients listed gives the content of active material, thus they be not included in it is commercially available The solvent or by-product that may include in the material of acquisition.This paper term " weight content " available symbols " % " indicate.
Unless otherwise specified, all molecular weight herein are all the weight average molecular weight indicated as unit of dalton.
Unless otherwise specified, the environment at 25 DEG C occurs for all preparations and test herein.
Herein "include", "comprise", " containing ", " containing ", " having " or other variants be intended to it is non-enclosed include, It is not distinguished between these terms.Term "comprising", which refers to, can be added not the other steps for influencing final result and ingredient.Term "comprising" further includes term " Consists of " and "consisting essentially of ...".The compositions and methods of the invention/technique may include, It is made from it and substantially by essential elements described herein and limit entry and described herein any additional or optional Ingredient, component, step or limit entry composition.
It is also understood that in this embodiment of the present invention term used in the description merely for the sake of description particular implementation Example purpose and be not intended to limit the embodiment of the present invention.Such as the institute in specification and appended book of the embodiment of the present invention As use, other situations unless the context is clearly specified, otherwise " one " of singular, "one" and "the" are intended to wrap Include plural form.
Automatic dish-washing machine special purpose detergent composition
Automatic dish-washing machine special purpose detergent composition of the invention include powdery automatic dish-washing machine special purpose detergent composition, The liquid automatic dish-washing machine special purpose detergent composition or list of liquid automatic dish-washing machine special purpose detergent composition, unit dose The solid automatic dish-washing machine special purpose detergent composition of position dosage, is chosen in particular from the group of following composition：Powdery automatic dish-washing machine is special It is dedicated with detergent composition, liquid automatic dish-washing machine special purpose detergent composition, the liquid automatic dish-washing machine of unit dose The solid automatic dish-washing machine special purpose detergent composition of detergent composition or unit dose.
Automatic dish-washing machine special purpose detergent composition of the invention pass through and the substrate (i.e. tableware) that needs to contact in water It is in contact, to achieve the purpose that the greasiness removal of substrate surface to clean substrate surface.
The automatic dish-washing machine special purpose detergent composition is generally also comprising surfactant system and other common Washing assisant such as enzyme preparation, fragrance etc..
Automatic dish-washing machine special purpose detergent composition of the invention, by weight, including following components：
0.01~20 part of polyether surfactant；
0.01~20 part of nonionic surfactant；
0.01~20 part of other surfaces activating agent；
0.1~30 part of copolymer dispersant；
0.1~40 part of amino acid derivativges chelating agent；
0.1~10 part of enzyme preparation；
0~80 part of additive；
Wherein, the nonionic surfactant includes at least two kinds of fatty alcohol alkoxy compounds, is quick emulsification type rouge Fat alcohol alkoxylates and at a slow speed emulsifying fatty alcohol alkoxy compound, and the polyether surfactant and the fat The weight ratio of alcohol alkoxylates is 1：0.1~1.5, preferably 1：0.1~0.5.
The each component for including in composition is further described as follows：
Polyether surfactant
The content of polyether surfactant provided by the embodiment of the present invention is the combination of automatic dish-washing machine special purpose detergent The 0.01%~20% of object, is calculated with composition total weight.
Polyether surfactant is a kind of polymer, contains ethyl oxide, oxidation propyl and oxidation butyl repetitive unit Polymeric surfactant, and the polymeric surfactant meets following general formula (1)：
Wherein, in general formula (1), the molecular weight of polyether surfactant is 500~6000, preferably 600~4000；
In the molecule of polyether surfactant, the content of ethyl oxide is 40%~80%, preferably 60%~80%；
In the molecule of polyether surfactant, the content for aoxidizing propyl is 5%~40%, preferably 5%~20%；
In the molecule of polyether surfactant, the content for aoxidizing butyl is 3%~20%, preferably 5%~15%；
In the molecule of polyether surfactant, R base is selected from the straight-chain fatty alcohol and/or Branched fatty that carbon number is 6 to 24 Alcohol, preferably 12~18 carbon straight chain alcohols, and R is selected from uncle position, secondary position and uncle position based on the binding site of polyether group.
In addition ethyl oxide, oxidation propyl and aoxidize butyl preferred value only represent ethyl oxide, oxidation propyl and The mutual proportionate relationship between butyl is aoxidized, the mode of its polymerization can not be limited, each polymerized unit both can be continuous with itself Polymerization, can also polymerize with other polymerized units, as long as whole number ratios keep requiring.
It has been found that the polyether surfactant of oxidation propyl and oxidation butyl with proper ratio, Neng Goufa The effect for inhibiting nonionic surfactant blistering is waved, especially inhibition aliphatic alcohol polyethenoxy/polyethenoxy ether blistering is made With, this is because meet above-mentioned requirements polyether surfactant molecule can in washing water with other surfaces activity dosage form At composite construction, other surfaces active agent molecule (especially aliphatic alcohol polyethenoxy/polyethenoxy ether) is effectively limited to bubble Interfacial migration, to reduce the foam number and enhancing defoaming capacity of surfactant molecule, the specific mechanism of action such as Fig. 1 institute Show.
It describes as shown in figure 1, meets the polyether surfactant of above-mentioned requirements since strand is without charge, in water It not will do it and sprawl, chimeric oxidation propyl and oxidation butyl effectively can form hydrophobic region in entire polymer molecule Domain, and the micella of surfactant composition is adsorbed in hydrophobic region by hydrophobic binding and forms compound, to hinder surface Migration of the active agent molecule to bubble interface.In addition, applicant further found that if contained in polyether surfactant molecule dredge Water base group is excessive, its molecule itself is easy to cause to be easy to migrate to bubble interface, this will will be greatly reduced it and inhibit surface-active The effect of agent molecule bubble.It must be stressed that due to aliphatic alcohol polyethenoxy/polyethenoxy ether for meeting above-mentioned requirements and poly- Ether type surfactant molecule has similar structure, and the effect for being combined into compound can be better than other kinds of surface and live Property agent, so that the low bubble effect of detergent composition is more preferable.
In certain embodiments, polyether surfactant is selected from following substance：
Polyether surfactant 1：Polyether surfactant 1 meets polyether surfactant general structure (1), Middle R base is laruyl alcohol, and the content of ethyl oxide is 80%, aoxidizes propyl 10%, aoxidizes butyl 10%；
Polyether surfactant 2：Polyether surfactant 2 meets polyether surfactant general structure (1), Middle R base is laurel secondary alcohol, and the content of ethyl oxide is 80%, aoxidizes propyl 5%, aoxidizes butyl 15%.
Polyether surfactant 3：Polyether surfactant 3 meets polyether surfactant general structure (1), Middle R base is laurel secondary alcohol, and the content of ethyl oxide is 40%, aoxidizes propyl 40%, aoxidizes butyl 20%；；
Polyether surfactant 4：Polyether surfactant 4 meets polyether surfactant general structure (1), Middle R base is laurel secondary alcohol, and the content of ethyl oxide is 50%, aoxidizes propyl 30%, aoxidizes butyl 20%.
Nonionic surfactant-fatty alcohol alkoxy compound
Automatic dish-washing machine special purpose detergent composition provided in an embodiment of the present invention include 0.01-20 parts by weight it is non-from Sub- surfactant, the nonionic surfactant include at least two kinds of fatty alcohol alkoxy compounds, fatty alcohol alkoxylates Object includes quick emulsification type fatty alcohol alkoxy compound and emulsifying fatty alcohol alkoxy compound at a slow speed.
In certain embodiments, automatic dish-washing machine special purpose detergent composition includes the quick emulsification of 0.01~10 parts by weight The emulsifying fatty alcohol alkoxy compound at a slow speed of type fatty alcohol alkoxy compound and 0.01~15 parts by weight.
Wherein, quick emulsification type fatty alcohol alkoxy compound has following general formula (2)：
In certain embodiments, in general formula (2), n be 2~16, preferably 2~10, more preferably 2~8, and n be positive it is whole Number；
M is 2~10, preferably 2~8, more preferably 2~4, and m is positive integer；
X is 0~10, preferably 0~5, more preferably 0~3；
Y is 0~10, preferably 0~7, more preferably 2~5；
Z is 0~10, preferably 0~5, more preferably 0~3；
(x+z)：Y is 0.2~1, preferably 0.2~0.5.
Emulsifying fatty alcohol alkoxy compound has following general formula (3) at a slow speed：
In certain embodiments, general formula (3), n are 2~16, preferably 2~10, more preferably 2~8, and n is positive integer；
M is 2~10, preferably 2~8, more preferably 2~4, and m is positive integer；
X is 3~30, preferably 3~15, more preferably 3~10；
Y is 0~10, preferably 0~7, more preferably 0~5；
Z is 3~30, preferably 3~15, more preferably 3~10；
(x+z)：Y is 3~10, preferably 5~10.
It should be noted that fatty alcohol alkoxy compound provided in an embodiment of the present invention is fatty alcohol and epoxyalkane in alkali The product of ring-opening polymerisation under property catalyst action.Fatty alcohol includes the isomery alcohol of straight chain alcohol or branch.Alkoxy grp includes ethoxy Group and propoxyl group group.Fatty alcohol includes but is not limited to hexanol, octanol, decyl alcohol, 2-ethylhexanol, 3- propyl enanthol, laurel Alcohol, different three decyl alcohol, tridecanol, tetradecanol, hexadecanol, Palmitoleyl alcohol, stearyl alcohol, isooctadecanol, oleyl alcohol, sub- oleyl alcohol, One or more mixtures of linolenyl alcohol.Commercialized example is SHELL company NEODOL series straight-chain fatty alcohol ethoxy Glycolylate product, the ECOSURF EH series ethoxylation of DOW company and the third oxidation 2-ethylhexanol product, BASF AG Lutensol XL series ethoxylation and the third oxidation 3- propyl enanthol product, BASF AG's Lutensol XP series ethoxylation The Dehypon series of products of 3- propyl enanthol product and BASF AG.
In addition the preferred value of methyl ethoxy y only represents the ratio of its methyl ethoxy and ethyoxyl, can not limit Its mode polymerizeing, methyl ethoxy can also both be polymerize with itself continuous polymerization with ethyoxyl, as long as whole numerical value is kept It is required that.
It is found by the applicant that influencing the not just slurry of conjunctiva and spotting phenomenon in the automatic dish-washing machine course of work In concentration of metal ions, the surface that the dirt in washing process can equally be deposited on washed utensil forms conjunctiva and spotting is existing As the conjunctiva and spotting phenomenon of the tableware surface occurred during, that is to say, that Actual laundering, often two different dirts The result being collectively formed.It is worth noting that, applicant further found that the dirt lotion of generation is more steady during Actual laundering It is fixed, it is better for the resistive connection film and spotting effect of detergent.
It is found by the applicant that ratio (the hereinafter referred to as EO of ethyoxyl and methyl ethoxy：PO) very to the influence of emulsifiability Greatly, because the structure of hydrophilic radical determines the substance in dirt/water termination adsorption rate and adsorption density, adsorption rate Illustrating that dirt/water interfacial tension decline is faster more greatly with adsorption density, i.e., dirt can be dispersed into the lower emulsion of partial size, Although such nonionic surfactant is different from general nonionic surfactant (such as AEO9, wherein not containing methyl second Oxygroup), speed and the aggregation number of micelle for forming micelle are all low compared with AEO9, but in dirt/water termination adsorption rate and suction Attached density is very high (to refer in particular to quick emulsification type fatty alcohol alkoxy compound is claimed in applicant hydrophobic chain structure and two kinds of second Oxygroup proportional region), such fatty alcohol alkoxy compound can effectively emulsify dirt in machine washing process, but due to it is hydrophilic Property is too low, results in lotion not quietly, is easy to cause demulsification.It is found by the applicant that on this basis plus in dirt/hydrosphere The fatty alcohol alkoxy compound that the adsorption rate in face is low but hydrophily is strong (refers in particular to the claimed emulsifying fatty alcohol at a slow speed of applicant The hydrophobic chain structure of alcoxylates and two kinds of ethyoxyl proportional regions) can effectively reinforce emulsification after dirt stability.And When the compounding of the technology described in the above applicant is with suitable antisludging agent, the two can play synergistic effect, and quick emulsification type fat Being used in compounding for alcohol alkoxylates and at a slow speed type fatty alcohol alkoxy compound can guarantee automatic dish-washing machine special purpose detergent Under the premise of the resistive connection film and spotting performance of composition, the dosage of antisludging agent is reduced, obtains cost space.
In certain embodiments, quick emulsification type fatty alcohol alkoxy compound is selected from following substance：
Quick emulsification type fatty alcohol alkoxy compound 1：Quick emulsification type fatty alcohol alkoxy compound 1 meets quick emulsification agent Fatty alcohol alkoxy compound general structure, the value that the value that the value that wherein value of n is 6, m is 2, x+z is 2, y is 4.
Quick emulsification type fatty alcohol alkoxy compound 2：Quick emulsification type fatty alcohol alkoxy compound 2 meets quick emulsification agent Fatty alcohol alkoxy compound general structure, the value that the value that the value that wherein value of n is 4, m is 2, x+z is 3, y is 6.
In certain embodiments, emulsifying fatty alcohol alkoxy compound is selected from following substance at a slow speed：
Emulsifying fatty alcohol alkoxy compound 1 at a slow speed：Emulsifying fatty alcohol alkoxy compound 1 meets emulsifying at a slow speed at a slow speed Fatty alcohol alkoxy compound general structure, the value that the value that the value that wherein value of n is 4, m is 3, x+z is 8, y is 0.
Emulsifying fatty alcohol alkoxy compound 2 at a slow speed：Emulsifying fatty alcohol alkoxy compound 2 meets emulsifying at a slow speed at a slow speed Fatty alcohol alkoxy compound general structure, the value that the value that the value that wherein value of n is 4, m is 3, x+z is 8, y is 2.
Other surfaces activating agent
Automatic dish-washing machine special purpose detergent composition provided by the invention includes that the other surfaces of 0.01-20 parts by weight are living Property agent.
In certain embodiments, other surfaces activating agent may include a kind of or alkyl polyglycoside, the alkyl polyglycoside With following general formula (a)：
In general formula (a), n is that 6~24, p is 1.1~3, and preferably n is 8~16.Suitable alkyl polyglycoside such as BASF AG Glucopon series alkyl glycosides product.
In certain embodiments, other surfaces activating agent may include one or more fatty acid alkoxylates, preferably For ethoxylation C8 to C18 aliphatic ester, average ethoxylation degree is 2 to 10.Ethoxylated sorbitan acid alcohol can be contained Arrcostab, alkyl carbon number are 6 to 18, and average ethoxyquin degree is 4 to 20；Suitable example is that Corda company's T ween series produces Product.
In certain embodiments, other surfaces activating agent may include one or more fatty acid alkyl alcohol amides, fat The carbon number of acid is 6 to 24, can be the fatty acid of straight chain, is also possible to the fatty acid of branch, can be the fatty acid of saturation, It can be unsaturated fatty acid；Alkylol number is 0 to 2.The glycollic amide that preferred fatty acid carbon number is 8 to 18, diethyl Alkylolamides, isopropanol amide, suitable example are coconut acid diethanolamides.
In certain embodiments, other surfaces activating agent may include one or more fatty acid methyl ester ethoxylates, The following general formula (b) of fatty acid methyl ester ethoxylate：
In general formula (b), n is 6~24；X is 2~20；It is preferred that it is 0.5~30 that n, which is 8~18, x,；It is preferred that x is 4~10.Properly Example is LION company MEE product.
In certain embodiments, other surfaces activating agent may include one or more polyether surfactants.
In certain embodiments, other surfaces activating agent may include the direct polyoxyethylene of one or more natural oils and Polyoxypropylene compound.Wherein, the content of the direct polyoxyethylene of natural oil and polyoxypropylene compound be composition 0.01%~ 20%, the direct polyoxyethylene of the natural oil and polyoxypropylene compound meet following general structure (c)：
Wherein, in general formula (c), R is the aliphatic hydrocarbon that carbon atom number is 10~30, preferably unsaturated hydrocarbons, unsaturation The number of key can be 1~7；
M, m' and m " can be 0~10, and m, m' and m " are positive integer；
And the sum of m, m' and m " are 10~30, preferably 10~25, more preferably 15~25；
(m+m″)：M' is 0.2~3, preferably 1~2.
Wherein, n, n' and n " can be 0~10, and n, n' and n " are positive integer；
And the sum of n, n' and n " are 10~30, preferably 10~25, more preferably 15~25；
(n+n″)：N' is 0.2~3, preferably 1~2.
Wherein, p, p' and p " can be 0~10, and p, p' and p " are positive integer；
And the sum of p, p' and p " are 10~30, preferably 10~25, more preferably 15~25；
(p+p″)：P' is 0.2~3, preferably 1~2.
And the direct polyoxyethylene of the natural oil and polyoxypropylene compound may be a variety of objects for meeting above-mentioned requirements The mixture of matter；
It is exemplified below out the direct polyoxyethylene of suitable natural oil and polyoxypropylene compound for meeting conditions above,
MOE-54 is that (the fatty acid group of the soybean oil becomes with soybean oil：Palmitic acid content 6%~8%, oleic acid 25% ~36%, stearic acid 3%~5%, linoleic acid 52%~65%, arachidic acid 0.04%~0.1% and linolenic acid 2.0%~ 3.0%) polyoxyethylene is carried out for natural oil raw material and polyoxypropylene, polyoxyethylene and polyoxypropylene group total quantity are 54, the ratio between polyoxyethylene groups and polyoxypropylene base are 2:1.
The direct polyoxyethylene of natural oil and polyoxypropylene compound are a kind of novel ester-ether type nonionic surfactants, Raw material is derived from natural plant grease, strong to grease solubilizing power, has good emulsifiability；And there is easily biological-degradable, ecology The advantages that toxicity is low, and irritation is small.It is more importantly that by the agency of is crossed from natural alcohol or synthol and prepares detergent above The cumbersome technique of alcohol, and the direct polyoxyethylene of natural oil and polyoxypropylene compound be by the direct ethoxylation of natural oil and Polyoxypropyleneization preparation, compared to traditional nonionic surfactant, the pre-treating technology of detergent alcohol is omitted in it, greatly The earth reduces industrial production cost and three wastes problem, directly controls the environmental pressure that surfactant produces from source.Separately Outside, due to not needing reaction, the direct polyoxyethylene of natural oil and the polyoxypropylene compound such as to hydrogenate natural oil, be saponified Fatty alcohol in can retain the original hydrophobic structure characteristic of natural oil so that such new non-ionic surfactants has Some special functions, such as the strong emulsification to non-water soluble substance.
Compared with the fatty acid methyl ester b-oxide (FMEE) gradually risen in recent years, the direct polyoxyethylene of natural oil and poly- Oxypropylene compound has the advantage that：(1) there is unsaturated bond, assign its flexible hydrophobic segment, be conducive to promote interfacial activity. (2) glycerol backbone, so that its hydrophobic segment is three times of general surfactant molecule.These unique structures allow natural oil Directly polyoxyethylene and polyoxypropylene compound are more quickly completed absorption in two-phase interface, then play more preferably washing decontamination effect Fruit.
Since the direct polyoxyethylene of natural oil and polyoxypropylene compound have the advantage of natural unsaturated bond, table It is easier to wind between the active agent molecule of face and fold.In general, with the increase of nonionic surfactant concentration, due to diffusion Constantly maximum will occur in enhancing, expansion modulus simultaneously for exchange process and interfacial concentration.The appearance of this maximum is due to boundary Caused by the diffusion exchange interaction alternate with body of face.Study that (difference of them is a carbon in Tween60 and Tween80 Carbon double bond) lotion the discussion with the variation tendency of concentration of expansion modulus and phase angle in, it was found that the expansion modulus pole of Tween80 Big value is significantly greater than Tween60, and the angle values of Tween80 are lower than Tween60, show with unsaturated hydrophobic grouping it is non-from Sub- surfactant Tween80 form the stronger interfacial film of elasticity and have than saturated carbon chains nonionic surfactant more Strong interfacial activity, similarly, the direct polyoxyethylene of natural oil and polyoxypropylene compound compare general non-ionic surface and live Property agent also has such advantage.
In addition, also thinking to have the nonionic surfactant of unsaturated bond hydrophobic structure to have in the research of interface subject There is stronger intermolecular interaction.In the low concentration range, saturation hydrophobic grouping and unsaturated hydrophobic grouping protrude into oily phase, Polyoxyethylene group protrudes into water phase；With increasing to before CMC (within the scope of intermediate concentration) for interfacial concentration, non-ionic surface is living Property agent molecule becomes closely in adsorbed on interfaces, and ethylene oxide group forms stable sub-layer, this controls rheological behaviour, causes Modulus increases and phase angle reduces.But concentration is further increased to more than CMC concentration (in high concentration range), the nonionic on interface SURFACTANT ADSORPTION saturation, it is due to new relaxation process, i.e., exchanged faster between the micella near boundary layer and interface Cheng Gongxian increases, and drastically reduces modulus, while phase angle significantly increases.In the increased whole process of surfactant molecule concentration In, have the molecule B flexibility of unsaturated hydrophobic grouping stronger, it is intermolecular to be easier to be crosslinked and wind, therefore there is unsaturation The nonionic surfactant molecule of hydrophobic grouping can form more stable interfacial film, and emulsifying capacity and emulsion stability are equal It is stronger than the general nonionic surfactant molecule with saturation hydrophobic grouping.
Use the direct polyoxyethylene of natural oil and polyoxypropylene compound product substitution routine with unsaturated bond structure Have saturation hydrophobic grouping nonionic surfactant, stronger interfacial activity and interface stability can be effectively provided, Keep the dirt-removing power of detergent composition stronger, or even providing certain prevents the ability of soil redeposition to reduce polymer Additive amount, therefore the direct polyoxyethylene of natural oil and polyoxypropylene compound product compare conventional nonionic surfactant, especially It is the fatty alcohol polyoxyethylene ether industrially widely applied at present, there is big advantage.
Copolymer dispersant
The content of the copolymer dispersant is 0.1~30 part of parts by weight of automatic dish-washing machine special purpose detergent composition.
The repetitive unit of the copolymer dispersant is selected from unsaturated monomer A, unsaturated monomer B, unsaturated monomer C polymerization The group of residue composition afterwards, and meet following relationship：
1) residue of the unsaturated monomer A of the copolymer dispersant in copolymer dispersant weight accounting be 60% to 90%；
2) the unsaturated monomer A of the copolymer dispersant includes the unsaturated monomer A1 of weight ratio 70% to 99.99%, Unsaturated monomer A2 comprising weight ratio 0.01% to 30%；
3) the unsaturated monomer A1 of the copolymer dispersant, which is selected from, contains a carboxylic acid group, and contains only one not It is saturated the monomer of double bond, including：Acrylic acid, methacrylic acid, Alpha-hydroxy acrylic acid, Alpha-hydroxy methacrylic acid, butenoic acid；Institute The carboxylic acid group for stating the unsaturated monomer A1 of copolymer dispersant exists, in particular to one in the form of salts in copolymer dispersant Valence metal salt, divalent metal salt and ammonium salt and organic ammonium salt；
4) the unsaturated monomer A2 selection of the copolymer dispersant contains more than one carboxylic acid group, and contains only one The monomer of a unsaturated double-bond, including：Maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid.
5) residue of the unsaturated monomer B of the copolymer dispersant in copolymer dispersant weight accounting be 10% to 40%；
6) the unsaturated monomer B of the copolymer dispersant, which is selected from, contains a sulfonic acid group, and contains only one not It is saturated the monomer of double bond, is specifically included：Vinyl monomer containing sulfonic acid group, the allyl monomer containing sulfonic acid group, contains There is (methyl) acrylamide of sulfonic acid group, and (methyl) acrylate containing sulfonic acid group, the copolymer dispersant The sulfonic acid group of unsaturated monomer B exists in the form of salts in copolymer dispersant, in particular to univalent metal salt, divalent metal Salt and ammonium salt and organic ammonium salt；
7) the unsaturated monomer B of the copolymer dispersant is chosen in particular from：Vinyl sulfonic acid, styrene sulfonic acid, 2- first Base -2- propylene -1- sulfonic acid, allyl sulphonic acid, this sulfonic acid of allyloxy, methyl allyloxy sulfonic acid, methyl allyloxy benzene sulphur Acid, 2- hydroxyl -3- (2- allyloxy) propane sulfonic acid, 1- acrylamido -1- propane sulfonic acid, 2- acrylamido -2- propane Sulfonic acid, 2- acrylamido -2- methyl propane sulfonic acid, 2- methacryl amido -2- methyl propane sulfonic acid, 3- methacryl Amido -2- hydroxypropanesulfonic acid, acrylic acid -3- sulfonic group propyl ester, methacrylic acid -2- sulfonic group ethyl ester, methacrylic acid -3- Sulfonic group propyl ester；
8) residue of the unsaturated monomer C of copolymer dispersant weight accounting in copolymer dispersant is 0.1% To 20%；
9) the unsaturated monomer C of the copolymer dispersant is selected from the monomer containing a unsaturated double-bond, specifically includes： The group of one or more compositions of unsaturated monomer C1, unsaturated monomer C2, unsaturated monomer C3；
10) the unsaturated monomer C1 of the copolymer dispersant is selected from the compound for meeting following general formula (4)：
In general formula (4), R1Selected from hydrogen, the group of one or more compositions of methyl, the positive integer that n is 2 to 8；
11) the unsaturated monomer C2 of the copolymer dispersant is selected from acrylamide, benzyl methacrylamide, cyclohexyl Methacrylamide, N-tert-butyl acrylamide, Methacrylamide, dimethacrylamide, dimethylaminopropyl methyl-prop Acrylamide；
12) the unsaturated monomer C3 of the copolymer dispersant, which is selected from, meets following general formula (5) and/or following general formula (6) Compound：
R in general formula (5)1Selected from hydrogen, the group of one or more compositions of methyl, R2The saturated alkyl for being 2 to 8 for carbon number；
In general formula (6), R1Selected from hydrogen, the group of one or more compositions of methyl, R3Selected from hydrogen, methyl, one kind of ethyl or The group of a variety of compositions, R4Selected from hydrogen, the saturated alkyl that carbon number is 1 to 20, the positive integer that m is 1 to 30.
13) molecular weight of the copolymer dispersant is 1000~150000, preferably 2000~100000；
Commercialized copolymer dispersant can be used in the copolymer dispersant for meeting above-mentioned requirements, such as：DOW company Acusol series and BASF AG's Sokalan series of products.
In certain embodiments, the copolymer dispersant is selected from following substance：
Copolymer dispersant 1：The copolymer dispersant meets copolymer dispersant general structure, wherein unsaturated single First A is 65% acrylic acid and 5% maleic acid, the 2- acrylamido -2- methylpropane sulphur that unsaturated monomer B is 20% Acid, unsaturated monomer C are 10% hydroxy-ethyl acrylate, and polymer molecular weight is about 6500.
Copolymer dispersant 2：The copolymer dispersant meets copolymer dispersant general structure, wherein unsaturated single The acrylic acid that first A is 70%, the 2- acrylamido -2- methyl propane sulfonic acid that unsaturated monomer B is 20%, unsaturated monomer C For 10% hydroxypropyl acrylate, polymer molecular weight is about 8300.
The resistive connection film and anti-spotting mechanism of copolymer dispersant
Hard water film is caused to be the result that people are not intended to see due to calcium ions and magnesium ions during dish washing.By adding Washing assisant is added to effectively inhibit the insoluble foulant that sulfate, carbonate and phosphate etc. and metal ion are formed, thus Prevent foulant from forming film and stain in object surface.The content of hard water ions is known as the hardness of water, unit mg/kg in water (with CaCO3Calculate), also referred to as ppm.In general, the open water supply for flowing through In Limestone Area has higher hardness； Such as the ground water hardness in Inner Mongol area is 400ppm, the Australian natural water hardness is about 1000ppm.The hardness of water is bigger Also detergent composition is influenced bigger.
In addition, also can artificially be added in detergent compositions sometimes from the point of view of the certain components of detergent The metal ion of divalent.For example, the derivative of methylisothiazolinone is generally used in cleaning product as preservative, in order to increase Add its stability, sometimes using magnesium ion as stabilizer.Enzyme preparation is also component common in cleaning product, in order to increase The stability of enzyme preparation can also add calcium ion as stabilizer in cleaning product sometimes.These bivalent cations also can be to washing It washs effect and generates some influences, even result in the precipitating and crystallization of insoluble carbonate.
Calcium carbonate is one kind most commonly seen in insoluble structure object.In the solution, the common forming process of calcium carbonate is, Carbanion and calcium ion first form the supersaturated solution of calcium carbonate in the solution, then start to precipitate, precipitation process experience Pronucleus stage, crystal nucleation stage, the early stage of crystal growth, crystallization stage after nucleation.At this moment the other components in solution, PH value and temperature, ionic strength all have a major impact the nucleation of calcium carbonate crystal and crystal growth.
Inside several crystal forms of calcium carbonate, calcite crystal form is the most stable, but is also to be most difficult to removal.From going From the perspective of dirt, the crystal form of the calcium carbonate generated in solution is efficiently controlled, is controlled in non-calcite crystal form Have great importance.When there are phosphate, carboxylate, when anionic polyelectrolyte type, these substances are to carbonic acid in solution The generation of calcium nucleus and the growth of crystal generate significant impact.Influence of the different substances to calcium carbonate crystal is had nothing in common with each other, Some substances such as poly-aspartic-acid (polyaspartic acid, PAsp) can promote the calcium carbonate in solution finally to turn Certain crystal form such as aragonite type, the referred to as adjusting control agent of crystal form are turned to, some substances such as polymer containing carboxyl can obviously press down The rate of the generation of calcium carbonate processed, the referred to as inhibitor of calcium carbonate.There is a large amount of work around inhibitor to calcium carbonate crystal Generate and growth the mechanism of action and be unfolded, current research trend includes in the action principle of inhibitor：1, inhibitor and calcium Ions binding generates complex compound, to inhibit the nucleation of calcium carbonate crystal.2, inhibitor stablizes the pronucleus cluster of calcium carbonate (prenuleation cluster), to inhibit the nucleation of calcium carbonate crystal.Pronucleus cluster be calcium carbonate in the solution The minimum unit being stabilized, pronucleus cluster, which is further assembled, forms unformed aggregation, and aggregation is further transformed to tie Brilliant microdomain, is then grown to crystal.3, inhibitor is by being incorporated in the precursor particles surface of the calcium carbonate (crystal) of Nano grade, Stablize particle, to inhibit calcium carbonate crystal further growth.
It is generally believed that the polymer addition containing carboxylate group allows calcium carbonate nucleus to have obvious postpone, induction period Increase as carboxylic acid radical content increases.The morning of the crystal growth phase (post nucleation stage) of phase after nucleation Phase, the hydrodynamic radius of aggregation linearly increases as the time increases in solution, finally converges on a certain saturation value.Cause This, it is believed that the inhibiting effect that polymer is nucleated calcium carbonate mainly by the stabilisation to aggregation (pronucleus cluster) come It realizes.Especially when the concentration of inhibitor is well below the calcium ion in solution, even if inhibitor functional group (carboxyl, phenolic group, sulphur Acidic group) all with calcium ion with 1:1 mode combines, and exists in solution containing a large amount of free calcium ions, therefore inhibiting effect master It is not originating from the complexing of functional group and calcium ion.And it is derived from functional group's (carboxyl, phenolic group, sulfonic group) and is adsorbed in The interface of Speleothem crystal, so that the growth site of calcium carbonate has been interrupted, to inhibit the further growth of calcium carbonate. The difference of functional group's adsorption capacity is presented as the length of induction time and the height of inhibiting rate.
Polycarboxylate has strong combination to calcium ion in aqueous solution, " bridging " of a part of calcium ion in solution The electrostatic repulsion that effect causes the carboxylate radical of polymer mutual weakens, and the conformation of polymer is gradually changed into from stretching, extension to twine Around taking the conformation more tightened.Therefore, although the calcium ion of part is bound by polycarboxylate in solution, polymerization Object can not further combined with remaining calcium ion in solution, while can not effectively the aggregation in stablizing solution (as gradually The calcium carbonate pronucleus cluster of growth) and particle, it could even be possible to the gelatine due to hydrophilic decline；Therefore it still results in Calcium carbonate crystal continues generation and growth.Polycarboxylate is only remaining since the combination of carboxylate radical and microparticle surfaces is too strong A small amount of carboxylic acid ion provides electrostatic repulsion.Less electrostatic repulsion is unfavorable between particle, particle and substrate Surface is separated.
Therefore, numerous studies concentrate on the chemical modification of polycarboxylate.Copolymerization is most commonly seen method of modifying.By not Saturated monocarboxylic acid and second comonomer/Third monomer polymer assign the brand-new chemical property of polycarboxylate, common polymerization The type of object monomer and effect see the table below 1.
The type and effect of the common polymer monomer of table 1
A large amount of patent documents such as US3332904, US3898037, US6395185, CN102197125A, CN102197127 It reports and contains sulfonate group simultaneously, the polymer of carboxylate group.Wherein, sulfonate radical only has faint suction to microparticle surfaces Attached effect, exposed sulfonate radical are enriched in microparticle surfaces, assign particle certain elecrtonegativity.The introducing of sulfonate radical is added significantly to The electrostatic repulsion between particle that polymer combines, to reduce the reunion of particle, and in the deposition of substrate surface.Separately Outside, sulfonate radical is compared with carboxylate radical, has stronger polarity, it is stronger in more extensive pH value range to assign polymer Water solubility is useful in household washing field as fouling agent.Therefore, for containing sulfonate group, the polymerization of carboxylate group For object, the weight accounting of the residue containing sulfonate group is it is not recommended that more than 50%.And carboxylate group contains in polymer Amount then should could ensure the sequestering power for polymerizeing existing calcium ion, and have preferable water solubility 50% or more in this way.
Nippon Shokubai Co., Ltd has investigated the molecular weight of copolymer and the relationship of performance in patent CN101952351A.Altogether Unsaturated monomer I of the polymers composition comprising double carboxylate radicals, such as maleic acid (acid anhydride)；The unsaturated monomer II of monocarboxylic acid root, such as propylene Acid.Unsaturated monomer III containing sulfonate radical is 3- allyloxy -2- hydroxyl -1- propane sulfonic acid salt (HAPS).Molecular weight is higher right Calcium ion capture ability is strong, and molecular weight is lower then to increase the dispersibility of hydrophilic stains.Copolymer final application is being done washing In compound powder.Procter & Gamble reports that a kind of polymer containing sulfonate radical is used for height in CN102197125A, CN102197127 The washing decontamination of hardness water quality, can effectively inhibit surfactant deposition and antigelation.So-called surfactant deposition refers to yin The precipitating that ionic surfactant and hard water ions are formed.The copolymer of CN102197127 report contains ethylene oxide The unsaturated monomer I of repetitive unit；Unsaturated monomer II containing carboxylate radical, such as acrylic acid, the unsaturation containing sulfonate radical are single Body III is 3- allyloxy -2- hydroxyl -1- propane sulfonic acid salt.Procter & Gamble declares in CN102197125A containing sulfonate radical Polymer is especially suitable for applying in high-hardness water environment.Kao Corp reports AA/ in patent CN100503802C The copolymer of AMPS, 1,500,000 or more average molecular weight of copolymer.The copolymer of this high molecular weight is in common wash concentration Under, the smooth touch of cleaned material is assigned, hand washing washing is suitable for.
The length of the strand of polycarboxylate, form all can be right in the solution for the number and molecule of carboxylic acid group number Its washing aid performance has an impact.In general, polycarboxylate polymer is more effective for suspended solid particle spot such as carbon black, And it is relatively weak to the dispersibility of hydrophobic oil-dirt such as sebum.Some documents are gathered by introducing esters unsaturated monomer and being promoted Dispersion efficiency of the carboxylate to hydrophobic soil.
US4029577, US4499002, Japanese Patent Publication 61-107997,61-107992 report acrylic acid and it is non-from Subtype unsaturated monomer (hydroxy alkyl acrylate, acrylamide, the alkoxyalkyl alcohol ester of acrylic acid) is for inhibiting silicic acid The structure that salt generates.Nonionic unsaturated monomer improves polymer to the binding ability of silicon dirt.Although the electricity of polymer entirety Lotus density is declined compared with polyacrylic acid (sodium) homopolymer, but anti-tartar efficiency (ability for showing as hard water resistance film) has obvious increasing Add.
Frequently problem is related to formation of the solid sediment on institute's article-cleaning and tired in automatic dish-washing machine industry Product, frequently referred to " fouling ".Daily water supply may be containing alkaline earth metal cation such as calcium, magnesium, iron, copper, barium, zinc etc. and some Anion such as bicarbonate radical, carbonate, sulfate radical, phosphate radical, silicate, fluorine ion etc..When these cations and anion Combination be more than its reaction product solubility concentration in the presence of, will form solid and precipitate and accumulate in the article cleaned On.For example, when the ionic product of magnesium and silicate be more than magnesium silicate solubility when, will be formed solid phase magnesium silicate and be accumulated in disk, Tank, flatware, plastic tableware, glass container, pan and silverware surface on, cause to generate on clean article ugly Film or stain.Moreover, if the concentration of these substances may form knot near or above solubility limit in material Dirt.Metal ion and anion binding can be attributed to homogeneous nucleation and/or non-in the mechanism that cleaned material surface forms dirt Homogeneous nucleation, this is the common sense in Water Environmental Chemistry field.The case where more situation, automatic dish-washing machine industry encounters is non-equal It is mutually nucleated, because condition needed for homogeneous nucleation is harsher, and dirt concentration when nonhomogen-ous nucleation is well below homogeneous nucleation The dirt concentration for being.
It is generally acknowledged that automatic dish-washing machine detergent is a kind of detergent for being different from fabric cleaning or water treatment agent.Automatic After completing the cleaning frequency in dish-washing machine, excellent automatic dish-washing machine detergent can effectively prevent metal ion and anion from precipitating Object is on glassware, crockery, plastic tableware and container, silverware, flatware, fine porcelain, cooker and other normal The surface to be cleaned seen forms film and/or spot.
It is worth noting that, even if metal ion and anion sediment form film and/or spot in surface to be cleaned Its mechanism belongs to nonhomogen-ous nucleation, but the formative element of film and spot is discrepant.In general, metal ion and yin It is size depending on its solubility product in water that ion precipitation object, which exists in the form of a film or exists in the form of spot, and The size of the solubility product will receive the influence of chelating agent, antisludging agent again.It is worth noting that, applicants have unexpectedly found that polymer Nonionic unsaturated monomer, chain length and/or molecular weight distribution conjunctiva and spotting can also be had an impact.
Amino acid derivativges chelating agent
The amino acid derivativges chelator is the 0.1~40% of automatic dish-washing machine special purpose detergent composition.
The amino acid derivativges chelating agent can be methylglycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA), N, N- dicarboxylic acids amino -2- hydroxy propane base sulfonic acid, 3- hydroxyl -2,2 '-iminodisuccinic acid, aspartic acid-N- One acetic acid (ASMA), aspartic acid-N, N- oxalic acid (ASDA), one propionic acid of aspartic acid-N- (ASMP), iminodisuccinic acid (IDA), N- (2- sulphur methyl)-aspartic acid (SMAS), N- (2- sulfoethyl) aspartic acid (SEAS), N- (2- sulphur methyl) paddy ammonia Acid (SMGL), N- (2- sulfoethyl) glutamic acid (SEGL), N- methyliminodiacetic acid (MIDA), α-alanine-N, N- diethyl Acid (α-ALDA), Beta-alanine-N, N- oxalic acid (β-ALDA), serine-N, N- oxalic acid (SEDA), isoerine-N, N- Oxalic acid (ISDA), phenylalanine-N, N- oxalic acid (PHDA), ortho-aminobenzoic acid-N, N- oxalic acid (ANDA), sulfanilic acid- N, N- oxalic acid (SLDA), taurine-N, N- oxalic acid (TUDA) and sulphur methyl-N, N- oxalic acid (SMDA) and its alkali metal salt Or ammonium salt.In file of the present invention, also referred to as chelating agent or green chelating agent.
The alkali metal salt of the amino acid derivativges chelating agent can be selected from lithium salts, preferably sylvite, more preferably sodium salt.
Automatic dish-washing machine special purpose detergent combination of compositions object must satisfy many requirements.They need dirty to various culinary arts Dirt has outstanding clean-up performance, including removes organic substance such as milk dirt, greasy dirt, eggs residue, meat residue etc.. Automatic dish-washing machine detergent tablet not only needs to cope with the hard water of different hardness, it is necessary to have the characteristics that environmental-friendly, therefore contain There is the automatic dish-washing machine detergent tablet of phosphoric acid salt chelating agent not received by society.
Some researches show that the center Ca of the active site of certain chelating agents meeting competitive binding enzyme preparations2+Metal ion, thus Reduce activity and its vital preservation time of the enzyme preparation.Therefore suitable chelating agent how is screened, to enzymatic detergent tablet It is very important.
And the present invention describes a kind of automatic dish-washing machine special purpose detergent combination of compositions added with specific chelating agent Object is friendly to environment and has to milk residue, eggs residue, starchiness class residue and pesticide residue ingredient Good removal effect, the energy after 30 DEG C or so or 35 DEG C or so or 37 DEG C or so storages a few weeks or longer times Keep 50% or more enzyme activity.
Dirty body is mostly crystalline solid, by taking calcium carbonate as an example, CaCO3It is by positively charged Ca with ionic lattice2+With band The CO of negative electrical charge3 2-It is bonded to each other when colliding, and there is the hard scale strictly arranged by certain direction.After chelating agent is added To Ca2+Chelation, it is suppressed that lattice to certain orientation grow up, CaCO3The crystal structure of hard scale is distorted, and is no longer pressed Normal rule continues to increase, and generation is some biggish noncrystalline particles, and part is adsorbed on crystal, and generation is one A little biggish noncrystalline particles, part are adsorbed on crystal, are entered in lattice with the growth of crystal, are CaCO3It is brilliant Body misplaces, and some cavities are formed in dirty layer.Even if still there is partial crystals growing up, it is also difficult to closely dirty layer is formed, To make CaCO3Hard scale is changed into soft dirt, is easily washed away by water flow.
Silicon and silicon dirt
The type of silicon can be attributed to three kinds in nature water, be dissolution silicon, colloidal silicon and particle silicon respectively.Dissolving silicon is silicon Silicic acid (the H formed in water4SiO4) compound；Colloidal silicon is usually that the silicic acid in water passes through the condensation of suction hydrogen and dehydrating condensation, shape Space structure is rolled into a ball at silica gel, then proceedes to the silicon dioxide colloid dirt that dehydration is formed；Particle silicon is then the graininess in silicon and water The larger particles that suspended matter is formed after combining.
The content of silicon is dissolved in water usually with SiO2Mass concentration measure.The silicon contained in the water of nature is about 6 ~120ppm.At 25 DEG C, the solubility limit of silicon is about 120ppm.Silicone content in water goes beyond the limit after value, will form glue Body forms silicate state with other ions bindings, is then precipitated and forms silicon dirt.
And silicon dirt common in water generally exists with two states, a kind of form is that silicic acid polymerization state or silica gel group are unformed State, referred to as colloidal silicon, general structure are represented by xHSiO2.yH2O.Colloidal silicon is generally by monomolecular positive silicic acid or SiO2It is poly- It closes, it is more stable in water.It is worth noting that, silicic acid molecule will not ionize substantially as pH=7 or so, protect Hold the form of molecular state；There are about 1/10th molecules to ionize as pH=8.5 or so, in silicic acid；PH=10 or so When, then there are about the silicic acid of half can generate ionization.When the silicon excess in water, SiO will form2, this SiO2Be it is unsetting, Then it is suspended in water in the form of colloidal particle.Here it is commonly called colloidal silicon or suspension silicon.Colloidal silicon is in water It is to exist in the form of molecule aggregation state or in the form of particle attached state mostly, diameter is generally 1~100 μm.
Another existence form of silicon dirt is silicate scale, it can be common that CaSiO3、MgSiO3Equal difficulty soluble salts.Silicate scale Structure it is usually all finer and close, formed after can closely be attached on appts wall, removal be extremely not easy.Its scaling mechanisms is substantially It is as follows：In alkaline environment, Ca2+、Mg2+With OH-In conjunction with generation Ca (OH)2With Mg (OH)2Etc. corresponding hydroxide, then with Silicate ion combines, and finally becomes silicate scale.
It is worth noting that the working environment of automatic dish-washing machine is generally alkaline environment, pH value is 9~13.
Enzyme preparation
Automatic dish-washing machine special purpose detergent composition provided by the invention may include one or more enzyme preparations, to provide Clean-up performance, fabric nursing and/or other beneficial effects.The enzyme preparation is selected from following enzyme group in groups：Protease, alphalise starch Enzyme, cellulase, hemicellulase, phosphatidase, esterase, lipase, peroxidase/oxidizing ferment, pectase, lyases are sweet Reveal dextranase, cutinase, reductase, zytase, amylopectase, tannase, pentosanase, maltosan, arabinose Enzyme, 1,4 beta-glucanase.Common enzyme preparation is protease, amylase, lipase, cutinase and/or cellulase.Enzyme preparation contains Amount is the 0.1%~10% of automatic dish-washing machine special purpose detergent composition.
Automatic dish-washing machine special purpose detergent composition of the invention may include：Account for composition weight 0.001%~10% Enzyme stabilising system.The enzyme stabilising system can be compatible with detergent composition, may include calcium ion, boric acid, borax, and the third two Alcohol, glycerol, one or more of mixtures of polyalcohol.The weight and dosage of enzyme stabilising system are according to detergent composition The type of form and composition and enzyme preparation is adjusted.
Automatic dish-washing machine special purpose detergent composition-enzyme preparation
Automatic dish-washing machine special purpose detergent composition-enzyme preparation refers to the enzyme system for being commonly used in preparing detergent compositions Agent, the enzyme preparation include all kinds of amylase, each quasi-lipase, all kinds of protease, all kinds of cellulases and all kinds of hemicelluloses One or more mixtures of enzyme.
In certain embodiments, automatic dish-washing machine special purpose detergent composition provided in an embodiment of the present invention includes starch Enzyme.
The example for the amylase that can be prepared according to the present invention is from bacillus licheniformis (Bacillus Licheniformis), from bacillus amyloliquefaciens (Bacillus amyloliquefaciens) or from stearothermophilus bud The alpha-amylase of spore bacillus (Bacillus stearothermophilus), and more specifically, further include improve they with In washing or the further development of cleaning compositions and dish washing detergent.Enzyme from bacillus licheniformis can be from The Termamy l series enzyme preparation product of Novozymes company obtains.Alpha-amylase from bacillus amyloliquefaciens be by Novozymes sale, entitled BAN, the variant of the alpha-amylase from bacillus stearothermophilus are equally sold by Novozymes It sells, entitled BSG and Novamyl.In addition, for this purpose, should also further pay special attention to come from bacillus A7-7 (DSM12368) alpha-amylase and the ring for carrying out self-adhesion agar bacillus (Bacillus agaradherens) (DSM 9948) Dextrin glucan based transferase (CGTase).It can also use the fusion product of all specified molecules.In addition, be available from Novozymes in Fungamyl series of products from aspergillus niger (Aspergillus niger) and aspergillus oryzae (A.oryzae) the further exploitation product of alpha-amylase are also suitable.The more preferably Amylase-LT of Novozymes company, Alpha-amylase in Stainzyme, Stainsymeultra, Stainzymeplus and Achieve series, in addition Dupont is public Alpha-amylase in Preferenz series and the Excellenz series of department is also suitable.
Diastase content is the 0.2%-5% of the first detergent composition.Meanwhile first in detergent composition also It may include the enzyme stabilising system for accounting for the first detergent composition weight 0.001~10%.The enzyme stabilising system can and wash Agent composition is compatible, may include at least one of calcium ion, boric acid, borax, propylene glycol, glycerol and polyalcohol.Enzyme liptinite The weight and dosage of system are in the form of according to detergent composition and form and the type of enzyme preparation is adjusted.
In certain embodiments, automatic dish-washing machine special purpose detergent composition provided in an embodiment of the present invention includes albumen Enzyme.
Protease of the present invention includes the protease of bacterium, fungi, plant, virus or animal origin, such as plant Or it is microbe-derived.Preferred microorganism source.Mutant or protein engineered mutant including chemical modification.It can be with It is alkali protease, such as serine protease or metalloproteinases.Serine protease can be trypsase or withered grass bar Mycoproteinase.Metalloproteinases can be thermolysin or other metalloproteinases.Be suitble to conditions above can from business The protease of channel purchase includes the enzyme preparation product sold with following trade name, including：From Novozymes company Alcalase, Duralase, Durazym, Relase, Relase Ultra, Savinase, Savinase Ultra, Primase, Polarzyme, Kannase, Liquanase, Liquanase Ultra, Ovozyme, Coronase, Coronase Ultra, Neutrase, Everlase and Esperase series of products；From Danisco company and Dupont company Maxatase, Maxacal, Maxapem, Purafect, Purafect Prime, Purafect MA, Purafect Ox, Purafect OxP, Puramax, Properase, FN2, FN3, FN4, Excellase, Eraser, Opticlean, Blaze, Progress, Excellenz and Optimase series of products.
Protease preparation content is the 0.2%~5% of the first detergent composition.It meanwhile also may include accounting in composition The enzyme stabilising system of first detergent composition weight 0.001~10%.The enzyme stabilising system can and detergent composition It is compatible, it may include at least one of calcium ion, boric acid, borax, propylene glycol, glycerol and polyalcohol.The weight of enzyme stabilising system It in the form of according to detergent composition and is formed and the type of enzyme preparation is adjusted with dosage.
Additive
Include following optional additive in automatic dish-washing machine special purpose detergent composition provided by the invention：Filler, Alkaline agent, viscosity modifier, preservative, colorant, colour stabilizer and essence one or more compositions mixture.
In certain embodiments, automatic dish-washing machine special purpose detergent composition provided by the invention may include a kind of or more Kind alkaline agent, alkaline agent are selected from sodium hydroxide, potassium hydroxide, the sodium salt of ethylenediamine tetra-acetic acid, alkali carbonate, the silicic acid of alkali metal Salt.
In certain embodiments, automatic dish-washing machine special purpose detergent composition provided by the invention may include a kind of or more Kind filler, is selected from sodium citrate, sodium sulphate, sodium chloride, potassium chloride, water, preferably sulfuric acid sodium and sodium citrate.
In certain embodiments, automatic dish-washing machine special purpose detergent composition provided by the invention may include a kind of or more A variety of viscosity modifiers, to provide suitable viscosity.Suitable viscosity modifier such as salt, polysaccharide, sizing material, short chain fatty alcohol are short Chain fatty alcohol alkyl ether.Suitable example is sodium chloride, ethyl alcohol, propylene glycol, sodium citrate, alkyl-hydroxyalkylcelluloswith ether, card Draw glue, xanthan gum, polyacrylamide derivative.
In certain embodiments, automatic dish-washing machine special purpose detergent composition provided by the invention may include a kind of or more A variety of bleach systems.Bleach system includes hypohalite beaches, peroxide bleaches.Peroxide typically comprises peroxide Change hydrogen source and bleach activating system.Hydrogen peroxide source includes but is not limited to perborate, percarbonate, persulfate and it Mixture.In some embodiments it is preferred that hydrogen peroxide source be SODIUM PERCARBONATE.Bleach system may include bleaching and live Agent, for promoting peroxide, fast decoupled generates oxygen to the bleach-activating at a lower temperature, is selected from following compound The group of composition：Tetra acetyl ethylene diamine, benzoyl caprolactam, 4- nitrobenzoylcaprolactam, 3- chlorobenzene formacyl Caprolactam, benzoyl oxybenzene sulfonates, nonanoly acyloxy benzene sulfonate, phenol benzoate, decanoyloxybenzenesulphonate, benzene first Acyl-valerolactams, octanoyloxy benzene sulfonate, transition metal bleach catalyst.
In certain embodiments, automatic dish-washing machine special purpose detergent composition provided by the invention can also be steady comprising ozone Determine agent, the ozone stabilizer is used to adjust peroxide and decomposes the speed for generating hydrogen peroxide, makes the localized rich of hydrogen peroxide Degree is unlikely to excessive, and suitable example is 1-hydroxy ethylidene-1,1-diphosphonic acid, the organic phosphoric acid of the polyfunctionalities such as ethylenediamine tetraacetic methene phosphoric acid. In some embodiments, the content of bleach system is the 0.01%~30% of detergent composition total weight, preferably 0.01%~20%, further preferably 0.01%~10%.
In certain embodiments, automatic dish-washing machine special purpose detergent composition provided by the invention may include a kind of or more Kind corrosion inhibitor, these corrosion inhibitors can provide the benefit of confrontation glass and/or metal erosion, and the term is covered for preventing Or reduce the reagent of the corrosion of non-ferrous metal (especially silver or copper).
It include multivalent ion source in automatic dish-washing machine special purpose detergent composition is known for the benefit of corrosion protection 's.For example, multivalent ion, especially silver, copper, zinc, bismuth and/or manganese ion for it inhibit the ability of such corrosion and by comprising Inside.Suitable inorganic oxide reduction activation substance can be zinc, bismuth, manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salt and/or compound Metal salt and/or metal composite, the metal is one of oxidation state II, III, IV, V or VI.Particularly suitable metal Salt and/or metal composite are selected from by MnSO4, manganese citrate (II), manganese stearate (II), manganese acetylacetonate (II), [1- hydroxyl Base ethane -1,1- di 2 ethylhexyl phosphonic acid] close manganese (II), V2O5、V2O4、VO2、TiOSO4、K2TiF6、K2ZrF6、CoSO4、Co(NO3)2, acetic acid Zinc, zinc sulfate and Ce (NO3)3The group of composition.Any suitable multivalent ion source can use, and the multivalent ion source is preferred From sulfate, carbonate, acetate, gluconate and metalloprotein compound.Zinc salt is particularly preferred corrosion inhibitor.
Preferred silver/copper corrosion inhibitor is benzotriazole (BTA) or dibenzo triazole and its derivative with substituent group.Its The reagent that he is suitble to is organic and/or inorganic oxide reduction activation substance and paraffin oil.Benzotriazole derivatives are can on phenyl ring Substitution site is by partially or completely those of substitution compound.Suitable substituent group be the alkyl of linear chain or branched chain C1~20 and Hydroxyl, sulfenyl, phenyl or halogen (such as fluorine, chlorine, bromine and iodine).The preferred benzotriazole with substituent group is methyl benzo three Azoles.
In certain embodiments, automatic dish-washing machine special purpose detergent composition of the present invention may include any conventional The corrosion inhibitor of amount.However, being based on total weight, additive amount is preferably 0.01%~5%, preferably 0.05%~3%, more preferably 0.1%~2.5%.
In some embodiments, automatic dish-washing machine special purpose detergent composition of the present invention contains colorant, institute Stating colorant includes dyestuff and pigment.Colorant includes all colorants applied in cleaning product, suitable example such as acid The bright red G of property, basic fuchsin, Methanil Yellow G, Acid Light Yellow G, alkaline yolk, direct fast blue B2RL are indigo-blue etc..
In some embodiments, automatic dish-washing machine special purpose detergent composition of the present invention contains colour stable Agent.Colour stabilizer includes all colour stabilizers that can be applied in cleaning product.
In certain embodiments, automatic dish-washing machine special purpose detergent composition of the present invention preferably comprises fragrance, institute Stating fragrance includes the fragrance component that all are suitable for cleaning product.Fragrance used of the invention can be natural origin, can also be with It is chemical synthesis the mixture of product or the two.Suitable example such as lemon, rose, jasmine, lavender, citrus is fragrant, It is green fragrant, radix aucklandiae etc..
In addition to above-mentioned optional member, automatic dish-washing machine special purpose detergent composition of the invention also may include water, You Jirong Agent, cosolvent, solubilizer, structural agent, to promote infusion, foam inhibitor, fabric softener, anti wrinkling agent etc. various common and conventional Additive.These additives and associated method of use are all well-known to those skilled in the art, specific type and dosage Selection can be adjusted according to actual needs.
Preparation and application method
Detergent tablet composition of the invention is using various method preparations well-known to those skilled in the art.The combination The preparation of object can be carried out by conventional means, specifically should be according to the steady of the state of component in the solution and effect and component It is qualitative to select suitable processing temperature and process time.
The application method of detergent composition of the invention is well-known to those skilled in the art, typical application method Be by specific detergent composition embodiment in a manner of undiluted or dilution in water in the way of and washed object Then surface contact 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 is not limited to scouring and mechanical stirring.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 and washed The ratio of object is preferably from about 1：1 to about 20：1.Certainly, detergent composition of the invention can also be according to the specific of dish-washing machine In operating instruction about detergent addition description section carry out using.
Without being further described, it is believed that those skilled in the art can use this using the above to the maximum extent Invention.The following examples purpose is to be further described and show specific embodiment within the scope of the present invention.Therefore, real It applies 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.Implement below In example, unless otherwise specified, all contents are weight percentages, and the content in relation to ingredients listed is the work by conversion The content of property substance.
Liquid automatic dish-washing machine special purpose detergent preparation method of composition
) process water is first put into ingredients pot；
2) under stirring, it is slowly added to thickener, after fully dispersed, adjusts pH to 6~9；
3) chelator component, polymers compositions, alkaline assistant, surfactant are sequentially added, is stirred evenly；
4) essence is put into ingredients pot, is stirred evenly；
5) other auxiliary agents are added into ingredients pot, stir evenly；
6) stand a period of time after, restore to room temperature is sufficient.
Powdery automatic dish-washing machine special purpose detergent preparation method of composition
1) filler is first put into ingredients pot；
2) under stirring, chelating agent, antisludging agent, surfactant is sequentially added, is stirred evenly；
3) defoaming agent, oxidant and its activator are put into, is stirred evenly；
4) essence and enzyme preparation are put into ingredients pot, are stirred evenly；
5) other additives are added into ingredients pot, stir evenly；
6) continue adequately to stir the material in ingredients pot, guarantee to be uniformly mixed without agglomeration and clustering phenomena Material be sieved (20 mesh~80 mesh), packed after the assay was approved.
Sheet automatic dish-washing machine special purpose detergent preparation method of composition
Automatic dish-washing machine special purpose detergent composition described in the invention can also be prepared into detergent tablet, especially Multi-phase detergent tablet, the multi-phase detergent tablet include：
1) the first phase, with smooth upper surface or the upper surface can be it is slightly convex or recess, it is described The difference in height of the highs and lows of upper surface is 1mm~5mm；
2) the second phase, and part bonding with the upper surface of first phase cover the upper surface of first phase.
The present invention also provides the method for preparing above-mentioned tablet, this method includes gluing second phase and first phase The step of conjunction.
The advantages of tablet of the invention remains marketed tablet.Second phase can be readily formed seem sphere (or Suppress formed other shapes) slave tablet upper surface shape outstanding.In addition, tablet it is different mutually can still contain it is incompatible Component, or containing the component for being hopeful to be discharged into different time in cleaning solution.Secondly, if it is desired, can be by second phase Form the different shape for being not easy to be put into cavity.Since second phase is not necessarily accurately placed in cavity, so will When on its surface for being placed in first phase, slightly deviation will not hinder the implementation of technical solution.Even if second phase Placement location, which slightly has deviation, will not cause it to separate with the first phase.If not can guarantee the accurate placement location of the second phase, only need The highs and lows difference in height of first phase upper surface is reduced, preferably 1mm~3mm.
First phase of the multi-phase detergent tablet can be any shape, as long as it is flat with combining with described second Smooth or substantially flat upper surface.First phase can have such as annular, ellipse or rectangular section.Wish the tablet It is rectangular block or cylinder.First phase repressed can shape, for example, by pressing in powder or granular composition tablet press machine Contracting.First phase can also be by for example casting or extrusion molding.If desired, first phase containing one or more layers not Same composition, and itself contain the insert of one or more different components.
Second phase of the multi-phase detergent tablet also can be any shape, and including but not limited to spherical, sheet is oval Shape.
The upper surface of first phase is flat or substantially flat.So-called " flat ", we refer to that the upper surface has There is substantially continuous profile and does not contain any cavity not being filled.But the upper surface can be it is coarse because formed The composition of first phase is granular.The upper surface can be smooth, selectively has chamfered edge, or can have nature The circular surface of transition.
Preparation of the preparation of second phase independently of first phase.Second phase can also be repressed for example by powder Or granular composition compression moulding, or by extrusion or casting.Second phase can be also uncompressed phase, such as by liquid group It closes object and gelling agent forms gel, or solidify after making the hot melt of required component.Second phase can also contain one or more The part of a different components.The lower surface of second phase is flat or substantially flat, and ideally with described first The upper surface of phase matches, to guarantee that they can be bonded to each other.For example, this two surfaces can be smooth or described The upper surface of one phase can be protrusion, and the lower surface of second phase can be recess, and vice versa.
It should be preferably the shape of no sharp edge or acute angle but although the surface of the first phase and the second phase can have any shape Shape, to avoid damaging and denuding when transporting and storing.
First phase is mutually bonded together with second, such as uses adhesive bonding.Adhesive can be coated in the first phase, On second phase or both.Adhesive appropriate is polyethylene glycol, and preferred molecular weight is 800~6000.
The amount of the first phase is typically larger than the amount of the second phase in the tablet.Such as the weight of first phase and second phase Amount is than being typically larger than 1:1, preferably greater than 10:1, more preferably greater than 15:1.
Second phase partly covers the upper surface of first phase.For example, second phase is covered for surface area Cover the 10~50% of the upper surface, preferably 20%~40%.
Second phase of the tablet contains component that can first with the release of the component of first phase.Second phase can be with Containing enzyme preparation, it can also contain bleaching agent.If necessary, in order to make second phase quickly be dissolved in cleaning solution, Second phase can be only slightly compressed, or can be made into uncompressed form such as gel.Second phase can also contain disintegrating agent, example Such as certain mixture, the mixture being such as made of the bronsted lowry acids and bases bronsted lowry that can be blistered when chance water.Disintegrating agent appropriate is certain acid such as citron Acid is formed with carbonate or bicarbonate such as sodium carbonate or sodium bicarbonate.
Any compression method preparation, such as tabletting, cake of press or crowded can be used in each phase of the tablet or the phase of multilayer Out, preferred tabletting method.Equipment appropriate includes standard single stroke press machine or rotary compressor.
Preferably it is wide or grows between 10mm to 80mm for the first prepared phase according to the present invention, more preferably at least 15mm is at most 25mm, and its weight is 5-100g.The ratio of height to diameter (or depth-width ratio) of the tablet is preferably greater than 1:1, more there is choosing big In 3:2.It prepares compressing force used in the tablet and does not require more than 120,000kN/m2, preferably more than 90,000kN/m2, more preferably No more than 85,000kN/m2, further preferably it is no more than 70,000kN/m2, most preferably not more than 50,000kN/m2。
Effect application test
The method of the experimental test occurred in embodiment verifying is as follows：
1, it is based on Terg-O-Tometer detergency test method
It is evenly affixed to standard intraocular's dirt on glass slide, with the dish-washing machine detergent solution of normal concentration in regulation item After washing under part, the removal percentage of dirt is measured.
1.1, reagent and material
Dehydrated alcohol, citric acid (10g/L), deionized water, anhydrous calcium chloride (CaCl2It is anhydrous), magnesium sulfate (MgSO4.7H2O), whole milk powder, Fresh Egg, wheat flour, 100ppm hard water (Ca2+:Mg2+=3:2)：It is anhydrous to weigh 1.67g CaCl2With 2.47g MgSO4.7H2O prepares 1L, is 2500ppm hard water, it is 100ppm hard that when use, which takes 40mL to be diluted to 1L, Water.
1.2, instrument and equipment
Electronic balance, assay balance, Terg-O-Tometer and corresponding a complete set of equipment, baking oven, thermometer, 0 DEG C~100 DEG C, electricity Magnetic furnace, microscope slide 2mm × 76mm × 26mm, 250mL beaker, pig palm fibre paintbrush, graduated cylinder, 1L, 50ml, measuring cup, 2L.
1.3, artificial greasy dirt preparation
10% miscella, 15% wheat flour, 7.5% whole milk powder, 30% fresh whole egg liquid, 32.5% distilled water.First Fresh Egg decladding is placed in clean beaker, is stirred evenly spare.Then, miscella is placed in a beaker 50~60 DEG C of heating Until melting completely, then uniformly mixed wheat flour and whole milk powder are poured into, and stirs evenly.Then, then by fresh egg liquid divide It is added in the beaker, and stirs evenly for several times.It finally adds water in several times and stirs into fine and smooth artificial dirt in beaker.
1.4, dirty piece preparation
New purchase glass slide need to be in conventional dish washing liquid solution (reference concentration：After 10g/L) boiling 15min, first with originally washing It washs to not hanging droplet.It is placed in citric acid solution (reference concentration again：10g/L) in impregnate 1h, then first with tap water rinse twice, It is rinsed twice, is finally placed in dehydrated alcohol after ultrasound 20min with deionized water again, it is cooling after being placed in 80 DEG C of baking ovens baking 1.5h It is spare., along 10mm line is drawn, limitation will be defiled below this line to show on glass slide.
1.5, it defiles
Every 4 one group of glass slide after cleaning is numbered, then is placed in assay balance and is precisely weighed and (is accurate to 1mg), The quality is calculated as m0.Prepared artificial dirt and hairbrush are placed on electronic balance (being accurate to 0.01g), controlled with Subtraction method The coated amount of greasy dirt.It defiles using one side is first applied, after drying, then applies another side.Generally, it holds slide vacantly to lay flat, uses hairbrush Artificial spot is evenly coated on slide, then slide is lain against into pallet.Single side defiles quality control in 0.30g~0.35g.It is single After face is painted with all slides, after being placed in 80 DEG C of baking ovens baking 30min, after taking out cooling, then another side is applied, quality of defiling also controls 0.30g~0.35g.After being painted with, then it is placed in after 80 DEG C of baking ovens dry 1h.Taking-up is cooled to room temperature, then to set assay balance accurate (accurate To 1mg), which is calculated as m1。m1-m0As the be coated with dirt quality of the slide should control the dirt amount error between different slides Within 0.5%.
1.6, it washs
(liquid product) weighs 0.5g sample to be tested in the washing tube of Terg-O-Tometer, the dirty piece of known weight together with Wash stand is correspondingly put into washing tube, and stirring slurry is installed, and is measured 2500ppm hard water 40mL with 50mL graduated cylinder and is fallen along agitating paddle Enter in washing tube, then measure 50 DEG C of deionized water 960mL with the graduated cylinder of 1L, is poured into washing tube along agitating paddle, the last one After water is added in sample, starts spotter, start to wash.After 30min, machine autostop rapidly removes blender, and taking-up is washed Wash frame, be placed on after 80 DEG C of baking ovens dry 1h rear glass slide is washed together with washing, take out it is cooling after to weigh be m2。
(powder product) weighs 0.5g sample to be tested in small beaker, measures 2500ppm hard water 40mL with 50mL graduated cylinder and falls Enter in washing tube, then measure 50 DEG C of deionized water 960mL with the graduated cylinder of 1L, beaker is equipped with sample wash to be measured into washing In bucket.It is put into corresponding washing tube one by one after the last one sample is added, then wash stand, after blender is installed rapidly, Start spotter, starts to wash.After 30min, machine autostop rapidly removes blender, wash stand is taken out, washing rear bearing After slide is placed on 80 DEG C of baking ovens baking 1h together with washing, weigh after taking out cooling as m2。
Note：1, every group of test should be three groups of dirt pieces of competing product detergent preparation, also prepare three groups of dirts for each sample to be tested Piece；2, since condition difference of defiling can affect soil removal efficiency measurement result, therefore measurement needs parallel sample to be subject to pair every time According to.
1.7, result indicates
Soil removal efficiency (%)=(m1-m2)/(m1-m0)×100
In formula：m0- defile before glass slide quality, g；
m1- defile after glass slide quality, g；
m2Glass slide quality after-washing, g.
1.8, detergency judges
Relative average debiation≤10% of three groups of results.
2, to all kinds of dirt detergency dependence tests-dish-washing machine Actual laundering measure of merit method
A certain amount of artificial dirt is applied on tableware, family's dishware detergent of normal concentration is used in dish-washing machine After solution washing, judge by visual observation to refer to detergent to performances such as the removals of dirt.Also the tableware that will can not defile is as mark Standard is compared with it.
2.1, reagent and material
Unless otherwise indicated, distilled water or deionized water or the water of suitable purity, lard, butter, essence is used only in analysis Vegetable oil processed, milk powder, wheat flour, Fresh Egg, catsup, mustard, tealeaves, oatmeal, citric acid.
2.2, instrument and equipment
Assay balance, counter balance, dish-washing machine (controllable temperature, drying can at least accommodate 6 sets of tablewares), thermometer, pig palm fibre oil Painting brush, electromagnetic heating blender, beaker, stainless steel leakage sieve (1mm mesh), rice bowl (114.3mm), vegetable dish (203.2mm, indent Face 140mm), glass (60mm*130mm), teacup (70mm*50mm), teacup tray (130mm, inner concave 95mm), small ellipse Disk (230mm), condiments disc (70mm), soup pot (200mm), chopsticks, soupspoon, soup ladle, knife, fork.
2.3, artificial dirt
Artificial dirt is used for coated vegetable dish and small oval plate, and the formula of artificial dirt is (mass fraction)：10% miscella, 15% wheat flour, 7.5% whole milk powder, 30% fresh whole egg liquid, 4% catsup, 1% mustard, 32.5% distilled water.Wherein Miscella is with 1:1:Lard, butter and vegetable oil are placed in a beaker by 2 mass ratio, and heating makes its thawing, are stirred evenly, to With.
Fresh Egg decladding is set in beaker, is stirred evenly spare；Wheat flour and whole milk powder are uniformly mixed；Miscella is set 50 DEG C~60 DEG C thawings are heated in beaker.Uniformly mixed wheat flour and whole milk powder are transferred to the miscella of thawing by several times It is stirred in beaker；Fresh Egg liquid is added in beaker by several times and is stirred evenly；Catsup is added and mustard stirs evenly, finally divides Secondary distilled water is added in beaker stirs into fine and smooth artificial dirt, defiles spare.
Tableware is first washed in dish-washing machine with 1% citric acid solution, even new tableware, also to be washed using preceding every time It is cleaned in bowl machine, is washed, then washed under the concentration that manufacturer recommends with detergent again, often with 1% citric acid solution first It is a to carry out conventional wash cycle.Deionized water or distilled water during rinsing.When on glass also When spot, the drying cycles of dish-washing machine are not used.There is no washmarking to illustrate rinsed clean on glass.Distilled water is used after taking-up It rinses to droplet is not hung, sets spare after dry, cooling in drying box.
It is uniformly applied on median plane concave in plate with artificial dirt on the pig palm fibre paintbrush libation at an ancient wedding ceremony, in (25 ± 1) after defiling DEG C place 8h it is spare.
2.4, tea stain
Tea stain is used for coated teacup and saucer.Its preparation process is as follows：In suitable container, by 1000mL boiling water [water Hardness be (2.5 ± 0.2) mmol/L] be added in 16g tealeaves and impregnate 15min, by leak sieve tea is poured into while stirring In another container.The tea of 100mL filtering is added in each teacup, 10mL is added in each saucer, is placed in (25 ± 1) DEG C 8h discards Aqua Folium Camelliae sinensis, spare.
2.5, oat stain
It is mixed with 187mL deionized water with 12.5g oatmeal, 10min is boiled after mixture boiled is risen and is stirred continuously.With Brush is defiled to service plate inner surface.The inward flange on tableware top stays 20mm not be coated with.In (25 ± 1), DEG C placement 4h is standby after defiling With.
1.6, it defiles referring to such as the following table 2：
2 spot table of table
2.7, test procedure
According to the specification requirement of dish-washing machine, the tableware for coating spot and other vessel are put in dish-washing machine.Connect electricity Source, setting program are standard wash state, are tested.It takes out rapidly and is dried in the air on bracket after dish-washing machine autostop, is cooled to After room temperature, according to test purpose, is evaluated by specific evaluation method shown in table 3, the properties of detergent are made and are commented Point.When the surface being infected with visual method starch dirt is scored, it can be coloured with iodine solution (KI-I2), keep residue more eye-catching. It is unified to use circle vegetable dish as evaluation object when dirt is artificial dirt in order to facilitate comparative example performance difference；Work as dirt It is unified to use rice bowl as evaluation object when dirt is oat stain；It is unified to use teacup for evaluation object when dirt is tea stain.
3 performance evaluation table of table
3, the quick measurement of resistive connection film properties and anti-spotting performance
A certain amount of filling dirt is placed in dish-washing machine, is washed in dish-washing machine with family's dishware of normal concentration After the slurry washing of agent solution and regulation hardness, judged by visual observation to evaluate the resistive connection film and anti-spotting of detergent Energy.Also tableware will can not be defiled as standard, be compared with it.If test object be tablet or other with encapsulating structure Unit dose formulations, then stirring is tested after being completely dissolved or be uniformly dispersed to it after putting into detergent.
3.1, reagent and material
Unless otherwise indicated, distilled water or deionized water or the water of suitable purity, lard, butter, essence is used only in analysis Vegetable oil processed, milk powder, wheat flour, Fresh Egg, catsup, mustard, tealeaves, oatmeal, citric acid.
3.2, instrument and equipment
Assay balance, counter balance, dish-washing machine (controllable temperature, drying can at least accommodate 6 sets of tablewares), thermometer, electromagnetism add Thermal agitation device, beaker, stainless steel leakage sieve (1mm mesh), glass (60mm*130mm), knife, fork.
3.3, dirt is filled
It fills dirt and is used for coated vegetable dish and small oval plate, the formula for filling dirt is：10% miscella, 15% wheat Powder, 7.5% whole milk powder, 30% fresh whole egg liquid, 4% catsup, 1% mustard, 32.5% vegetable oil.Wherein miscella with 1:1:Lard, butter and vegetable oil are placed in a beaker by 2 mass ratio, and heating makes its thawing, are stirred evenly, for use.
Fresh Egg decladding is set in beaker, is stirred evenly spare；Wheat flour and whole milk powder are uniformly mixed；Miscella is set 50 DEG C~60 DEG C thawings are heated in beaker.Uniformly mixed wheat flour and whole milk powder are transferred to the miscella of thawing by several times It is stirred in beaker；Fresh Egg liquid is added in beaker by several times and is stirred evenly；Catsup is added and mustard stirs evenly, finally divides Secondary vegetable oil is added in beaker stirs into fine and smooth filling dirt, defiles spare.
3.4, test procedure
Glass is first washed in dish-washing machine with 1% citric acid solution, even new glass, is also wanted using preceding every time It is cleaned in dish-washing machine, is washed with 1% citric acid solution, then washed under the concentration that manufacturer recommends with detergent again first It washs, each will carry out conventional wash cycle.Deionized water or distilled water during rinsing.When on glass There are also when spot, the drying cycles of dish-washing machine are not used.There is no washmarking to illustrate rinsed clean on glass.With steaming after taking-up Distilled water is rinsed to droplet is not hung, and is set spare after dry, cooling in drying box.
According to the specification requirement of dish-washing machine, glass and filling greasy dirt are put in dish-washing machine.Power on, journey is set Sequence is standard wash state, is tested, and slurry is 320ppm hard water (Ca2+:Mg2+=3:2), being needed according to test can To increase the number of repeated washing voluntarily to increase the degree of conjunctiva and spotting.Glass is taken rapidly after dish-washing machine autostop It is dried in the air out on bracket, after being cooled to room temperature, according to test purpose, is evaluated by the specific evaluation method of Fig. 2, to each of detergent Item performance makes scoring.Judge conjunctiva and spotting.
Embodiment
Embodiment 1 and comparative example 1, comparative example 2
Automatic dish-washing machine special purpose detergent composition A and A ', the B ', C ' prepared according to the following table 4 composition.
Detergent tablet composition A and A ' that 4 embodiment 1 of table and comparative example 1, comparative example 2 and comparative example 3 are prepared, B ' and C ' and corresponding test result
Embodiment 1 and comparative example 1, comparative example 2, the powder detergent composition A and A ' of comparative example 3, B ', C ' test knot Fruit such as table 4.From 4 result of table as can be seen that in above-mentioned comparative example, comparative example 1, comparative example 2 and comparative example 3 are institute of the present invention The incomplete embodiment for the technical solution stated, contains polyether surfactant and fat alcohol alkoxy compound respectively, real Apply the detergency test effect and artificial dirt of example 1, oat dirt and reduction foaming properties are superior to comparative example 1,2,3.It is tied Fruit shows that technical solution provided by the embodiment of the present invention answers polyether surfactant and two kinds of fatty alcohol alkoxy compounds With use, synergistic function is played, has given full play to active principle to the control for reducing foam and the emulsification point for enhancing greasy dirt The ability of dissipating.
Embodiment 1 and comparative example 4, comparative example 5, comparative example 6
Automatic dish-washing machine special purpose detergent composition A and D ', the E ', F ' prepared according to the following table 5 composition.
Powder detergent composition A and D ' that 5 embodiment 1 of table and comparative example 4, comparative example 5, comparative example 6 are prepared, E ', F ' and corresponding test result
Embodiment 1 and comparative example 4, comparative example 5, the powder detergent composition A and D ' of comparative example 6, E ', F ' test knot Fruit such as table 5.As can be seen from Table 5, comparative example 4,5 and 6 all uses the polyether surfactant required according to the present invention Be used in compounding with fat alcohol alkoxy compound, but not according to the present invention claims polyether surfactant and fatty alcohol The ratio of alkoxide compound mixes, although comparative example 4,5 and 6 controls, foam effect is obvious, the emulsion dispersion cream of greasy dirt Change fouling performance to substantially reduce, leads to its detergency and manually dirt, oat dirt removal effect is gone to be greatly reduced.
Embodiment 2, embodiment 3, embodiment 4, embodiment 5
Automatic dish-washing machine special purpose detergent composition B, C, D, the E prepared according to the following table 6 composition.
Powder detergent composition B, C, D, E prepared by 6 embodiment 2 of table, embodiment 3, embodiment 4, embodiment 5 and corresponding Test result
The test knot of powder detergent composition B, C, D, E prepared by embodiment 2, embodiment 3, embodiment 4, embodiment 5 Fruit such as table 6.As can be seen from Table 6, it is more real to may indicate that technical solutions according to the invention have for above 4 embodiments Existing possible (formula of different matrix, such as embodiment 7 and embodiment 8), is not limiting upon the use of several raw materials of Mr. Yu, main to accord with The composition for closing invention claim can play similar effect.
In the above-described embodiments, it all emphasizes particularly on different fields to the description of each embodiment, is not described in some embodiment Part, reference can be made to the related descriptions of other embodiments.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality It applies 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, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (10)

1. a kind of automatic dish-washing machine special purpose detergent composition, which is characterized in that including following parts by weight of component：
0.01~20 part of polyether surfactant；
0.01~20 part of nonionic surfactant；
0.01~20 part of other surfaces activating agent；
0.1~30 part of copolymer dispersant；
0.1~40 part of amino acid derivativges chelating agent；
0.1~10 part of enzyme preparation；
0~80 part of additive；
Wherein, the nonionic surfactant includes at least two kinds of fatty alcohol alkoxy compounds, is quick emulsification type fatty alcohol Alcoxylates and at a slow speed emulsifying fatty alcohol alkoxy compound, and the polyether surfactant and the fatty alcohol alkane The weight ratio of oxygroup compound is 1：0.1~1.5.
2. automatic dish-washing machine special purpose detergent composition as described in claim 1, which is characterized in that the polyether-type surface-active Agent has following general formula (1)：
Wherein, in general formula (1), the molecular weight of the polyether surfactant is 500~6000；
In the molecule of the polyether surfactant, the content of ethyl oxide is 40%~80%；
In the molecule of the polyether surfactant, the content for aoxidizing propyl is 5%~40%；
In the molecule of the polyether surfactant, the content for aoxidizing butyl is 3%~20%；
In the molecule of the polyether surfactant, R base is selected from the straight-chain fatty alcohol and/or Branched fatty that carbon number is 6 to 24 Alcohol, and R is selected from uncle position, secondary position and uncle position based on the binding site of polyether group.
3. automatic dish-washing machine special purpose detergent composition as described in claim 1, which is characterized in that the quick emulsification agent fat The content of alcohol alkoxylates is the 0.01%~10% of composition, and the quick emulsification agent fatty alcohol alkoxy compound has Following general formula (2)：
Wherein, in general formula (2), n is 2~16 and n is positive integer；M is 2~10 and m is positive integer；X is 0~10；Y is 0~10； Z is 0~10；(x+z)：Y is 0.2~1；
The content of the fatty alcohol alkoxy compound of emulsifier at a slow speed is the 0.01%~15% of composition, and described is emulsified at a slow speed Type fatty alcohol alkoxy compound can also have following general formula (3)：
Wherein, in general formula (3), n is 2~16 and n is positive integer；M is 2~10 and m is positive integer；X is 3~30；Y is 0~10； Z is 3~30；(x+z)：Y is 3~10.
4. automatic dish-washing machine special purpose detergent composition as described in claim 1, which is characterized in that the other surfaces activating agent Including alkyl polyglycoside, fatty acid alkoxylates, fatty acid alkyl alcohol amide, fatty acid methyl ester ethoxylate, natural oil At least one of the direct polyoxyethylene of rouge or polyoxypropylene compound.
5. automatic dish-washing machine special purpose detergent composition as described in claim 1, which is characterized in that the copolymer dispersant Repetitive unit is selected from unsaturated monomer A, the group that residue forms after unsaturated monomer B, unsaturated monomer C polymerization, and meets as follows Relationship：
1) residue of the unsaturated monomer A of the copolymer dispersant in copolymer dispersant weight accounting be 60% to 90%；
2) the unsaturated monomer A of the copolymer dispersant includes the unsaturated monomer A1 and again of weight ratio 70% to 99.99% Measure the unsaturated monomer A2 than 0.01% to 30%；
3) the unsaturated monomer A1 of the copolymer dispersant, which is selected from, contains a carboxylic acid group, and contains only a unsaturation The monomer of double bond；The carboxylic acid group of the unsaturated monomer A1 of the copolymer dispersant is deposited in the form of salts in copolymer dispersant ?；
4) the unsaturated monomer A2 selection of the copolymer dispersant contains more than one carboxylic acid group, and contains only one not It is saturated the monomer of double bond；
5) residue of the unsaturated monomer B of the copolymer dispersant in copolymer dispersant weight accounting be 10% to 40%；
6) the unsaturated monomer B of the copolymer dispersant is selected from containing a sulfonic acid group and contains only unsaturation pair The sulfonic acid group of the monomer of key, the unsaturated monomer B of the copolymer dispersant exists in the form of salts in copolymer dispersant；
7) residue of the unsaturated monomer C of the copolymer dispersant in copolymer dispersant weight accounting be 0.1% to 20%；
8) the unsaturated monomer C of the copolymer dispersant is selected from the monomer containing a unsaturated double-bond；
9) molecular weight of the copolymer dispersant is 1000~150000.
6. automatic dish-washing machine special purpose detergent composition as claimed in claim 5, it is characterised in that：The copolymer dispersant Unsaturated monomer A1 be selected from acrylic acid, methacrylic acid, Alpha-hydroxy acrylic acid, Alpha-hydroxy methacrylic acid, butenoic acid；
The unsaturated monomer A2 of the copolymer dispersant is selected from maleic acid, fumaric acid, maleic anhydride, itaconic acid, citraconic acid；
The unsaturated monomer B of the copolymer dispersant is selected from the vinyl monomer containing sulfonic acid group, contains sulfonic acid group Allyl monomer, the acrylamide containing sulfonic acid group, the Methacrylamide containing sulfonic acid group, third containing sulfonic acid group Olefin(e) acid ester, the methacrylate containing sulfonic acid group.
7. automatic dish-washing machine special purpose detergent composition as claimed in claim 5, it is characterised in that：The copolymer dispersant Unsaturated monomer C include unsaturated monomer C1, unsaturated monomer C2 and unsaturated monomer C3；
The unsaturated monomer C1 of the copolymer dispersant is selected from the compound for meeting following general formula (4)：
Wherein, in general formula (4), R1Selected from hydrogen, the group of one or more compositions of methyl, the positive integer that n is 2 to 8；
The unsaturated monomer C2 of the copolymer dispersant is selected from acrylamide, benzyl methacrylamide, cyclohexyl methyl third Acrylamide, N-tert-butyl acrylamide, Methacrylamide, dimethacrylamide, dimethylaminopropyl Methacrylamide One of；
The unsaturated monomer C3 of the copolymer dispersant is selected from the chemical combination for meeting following general formula (5) and/or following general formula (6) Object：
Wherein, in general formula (5), R1Selected from hydrogen, the group of one or more compositions of methyl, R2The saturated alkyl for being 2 to 8 for carbon number；
Wherein, in general formula (6), R1Selected from hydrogen, the group of one or more compositions of methyl, R3Selected from hydrogen, methyl, one kind of ethyl Or the group of a variety of compositions, R4Selected from hydrogen, the saturated alkyl that carbon number is 1 to 20, the positive integer that m is 1 to 30.
8. automatic dish-washing machine special purpose detergent composition as described in claim 1, which is characterized in that the amino acid derivativges chela Mixture includes methylglycine diacetic acid, glutamic acid diacetic acid, N, N- dicarboxylic acids amino -2- hydroxy propane base sulfonic acid, 3- hydroxyl - At least one of 2,2 '-iminodisuccinic acids and its alkali metal salts or ammonium salt.
9. automatic dish-washing machine special purpose detergent composition as described in claim 1, it is characterised in that：The enzyme preparation includes albumen Enzyme, alpha-amylase, cellulase, hemicellulase, phosphatidase, esterase, lipase, peroxidase/oxidizing ferment, pectase, Lyases, mannase, cutinase, reductase, zytase, amylopectase, tannase, pentosanase, maltosan, Arabinase, at least one of 1,4 beta-glucanase.
10. as described in claim 1 with the automatic dish-washing machine special purpose detergent composition of strong dirt emulsifying effectiveness, feature Be, the additive include filler, alkaline agent, viscosity modifier, bleach system, ozone stabilizer, corrosion inhibitor, preservative, At least one of colorant, colour stabilizer and essence.
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CN110331051A (en) * 2019-07-12 2019-10-15 广州立白企业集团有限公司 A kind of automatic dish-washing machine detergent composition
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CN110305742A (en) * 2019-07-12 2019-10-08 广州立白企业集团有限公司 A kind of automatic dish-washing machine detergent composition
CN110331051A (en) * 2019-07-12 2019-10-15 广州立白企业集团有限公司 A kind of automatic dish-washing machine detergent composition
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CN111518631A (en) * 2020-05-15 2020-08-11 广州立白企业集团有限公司 Detergent composition with enhanced emulsifying function and easy rinsing
CN114149868A (en) * 2021-12-03 2022-03-08 广州立白企业集团有限公司 Tablet detergent composition with hardness and solubility and preparation method thereof
CN114058450A (en) * 2021-12-03 2022-02-18 广州立白企业集团有限公司 Stable granular detergent composition and preparation method thereof
CN114058450B (en) * 2021-12-03 2024-01-26 广州立白企业集团有限公司 Stable granular detergent composition and preparation method thereof
CN114149868B (en) * 2021-12-03 2024-01-30 广州立白企业集团有限公司 Tablet detergent composition with hardness and dissolution performance and preparation method thereof
CN114276879A (en) * 2021-12-27 2022-04-05 广东红日星实业有限公司 Burn mark cleaning agent composition and preparation method and application thereof
CN114276879B (en) * 2021-12-27 2024-03-26 广东红日星实业有限公司 Burn cleaning agent composition and preparation method and application thereof
CN114854503A (en) * 2022-05-16 2022-08-05 佛山市顺德区美的洗涤电器制造有限公司 Detergent composition for removing stubborn stains special for dish washing machine
CN114854503B (en) * 2022-05-16 2024-02-23 佛山市顺德区美的洗涤电器制造有限公司 Special detergent composition for dish washing machine for removing stubborn stains
CN114958493A (en) * 2022-06-09 2022-08-30 广州立涤科技有限公司 Automatic dishwasher detergent composition for improving tableware quick-drying performance

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