CN110305742A

CN110305742A - A kind of automatic dish-washing machine detergent composition

Info

Publication number: CN110305742A
Application number: CN201910631103.0A
Authority: CN
Inventors: 周文杰; 梁智坤; 黄亮; 李作文; 沈兵; 张利萍
Original assignee: Guangzhou Liby Enterprise Group Co Ltd
Current assignee: Guangzhou Liby Enterprise Group Co Ltd
Priority date: 2019-07-12
Filing date: 2019-07-12
Publication date: 2019-10-08

Abstract

The invention discloses a kind of automatic dish-washing machine detergent compositions, are related to daily-use chemical industry technical field.The composition includes following parts by weight of component: 0.01~20 part of component A；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；0~20 part of optional member；20~85 parts of water；Wherein, the component A is a kind of and/or a variety of alkyl polyglycoside.It is acted synergistically by the compounding of each component, stability of the liquid detergent at high-temperature (50 DEG C~80 DEG C) can be improved, be allowed to be not easy split-phase and precipitation, and enhance the performance of detergent composition anti-dirt redeposition.

Description

A kind of automatic dish-washing machine 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 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.

Liquid preparation is important a member in automatic dish-washing machine detergent, and liquid preparation, which has, to be dissolved the features such as rapid, one Deeply by the favor of consumer since straight.But it needs to add non-ionic surface active due to being difficult to avoid that in automatic dish-washing machine detergent Agent, and due to containing a large amount of organic salts and inorganic salts in automatic dish-washing machine detergent, make under nonionic surfactant solubility Drop, therefore liquid automatic dishwasher detergent product is generally emulsion system on the market.Because emulsion is heterogeneous system, and it is high The problem of Wen Shi, nonionic surfactant solubility further decline, and product is easy to appear demulsification or layering.

Summary of the invention

Technical problem to be solved by the invention is to provide a kind of automatic dish-washing machine special purpose detergent compositions, this is washed automatically Bowl machine liquid detergent composition has good high-temperature stability, is mainly manifested in each component and saves for a long time in higher temperature When, it is not in split-phase or precipitation problem.

To solve the above-mentioned problems, the present invention the following technical schemes are provided:

A kind of automatic dish-washing machine detergent composition, including following parts by weight of component:

0.01~20 part of component A；

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；

0~20 part of optional member；

20~85 parts of water；

Wherein, the component A is a kind of and/or a variety of alkyl polyglycoside.

Further, the alkyl polyglycoside has 1 structure of general formula:

In general formula 1, n is 2~16, and n is positive integer；

M is 2~10, and m is positive integer；

P is 2~10, and p is positive integer.

Further, the other surfaces activating agent includes fatty alcohol alkoxy compound, fatty acid alkoxylates, fat The direct polyoxyethylene of acid alkylolamide, fatty acid methyl ester ethoxylate, polyether surfactant, natural oil and polyoxy One of allyl, heterogeneous poly alkyl alcohol oxyalkyl ether sodium sulfovinate are a variety of.

Further, the repetitive unit of the copolymer dispersant is selected from unsaturated monomer A, unsaturated monomer B, unsaturated The group that residue forms after 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 of the copolymer dispersant, which is selected from, 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, which is selected from, contains a sulfonic acid group, and contains only one not It is saturated the monomer of double bond, the sulfonic acid group of the unsaturated monomer B of the copolymer dispersant is in copolymer dispersant with salt shape Formula exists；

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, the unsaturated monomer B of the copolymer dispersant is selected from: vinyl sulfonic acid, styrene sulfonic acid, 2- Methyl -2- propylene -1- sulfonic acid, allyl sulphonic acid, this sulfonic acid of allyloxy, methyl allyloxy sulfonic acid, methyl allyloxy benzene Sulfonic acid, 2- hydroxyl -3- (2- allyloxy) propane sulfonic acid, 1- acrylamido -1- propane sulfonic acid, 2- acrylamido -2- third Alkyl sulfonic acid, 2- acrylamido -2- methyl propane sulfonic acid, 2- methacryl amido -2- methyl propane sulfonic acid, 3- metering system Amide groups -2- hydroxypropanesulfonic acid, acrylic acid -3- sulfonic group propyl ester, methacrylic acid -2- sulfonic group ethyl ester, methacrylic acid - One of 3- sulfonic group propyl ester is a variety of.

Further, the unsaturated monomer C of the copolymer dispersant includes unsaturated monomer C1, unsaturated monomer C2 and Unsaturated monomer C3；

The unsaturated monomer C1 of the copolymer dispersant, which is selected from, meets the compound such as following formula (1):

In formula (1), 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, dimethylacrylamide, dimethylaminopropyl metering system Amide；

The unsaturated monomer C3 of the copolymer dispersant is selected from the compound met such as following formula (2) and/or formula (3):

In formula (2), R₁Selected from hydrogen, the group of one or more compositions of methyl, R₂The saturated alkyl for being 2 to 8 for carbon number；

In formula (3), R₁Selected from hydrogen, the group of one or more compositions of methyl；R₃Selected from hydrogen, methyl, one kind of ethyl or more The group of kind composition；R₄Selected from hydrogen, the saturated alkyl that carbon number is 1 to 20, the positive integer that m is 1 to 30.

Further, the amino acid derivativges chelating agent includes methylglycine diacetic acid, glutamic acid diacetic acid, N, N- The one of dicarboxylic acids amino -2- hydroxy propane base sulfonic acid, 3- hydroxyl -2,2 '-iminodisuccinic acid and its alkali metal salts or ammonium salt Kind is a variety of.

Further, the enzyme preparation includes protease, alpha-amylase, cellulase, hemicellulase, phosphatidase, ester Enzyme, lipase, peroxidase/oxidizing ferment, pectase, lyases, mannase, cutinase, reductase, zytase, Amylopectase, tannase, pentosanase, maltosan, arabinase, 1,4 beta-glucanase it is one or more.

Further, the additive includes filler, alkaline agent, viscosity modifier, bleach system, ozone stabilizer, prevents Lose one of agent, preservative, colorant, colour stabilizer and essence or a variety of.

Compared with prior art, the attainable technical effect of present invention institute includes:

Automatic dish-washing machine detergent composition provided by the invention is acted synergistically by the compounding of each component, be can be improved Stability of the liquid detergent at high-temperature (50 DEG C~80 DEG C), is allowed to be not easy split-phase and precipitation, the beneficial effect is main Applied in the automatic dispensing scheme of liquid detergent, conceptual design is launched due to liquid automatically and necessarily refers to detergent composition It is designed in the storage of dish washer interior, and will necessarily have high-temperature, conventional liquid detergent composition when dishwasher into operation Phenomena such as necessarily will appear split-phase with this condition and being precipitated.Applicants have unexpectedly found that meeting alkyl described in claim Glucosides compounds synergistic effect with other each components, can play with this condition and increase detergent composition high-temperature stability Effect；In addition, the property for enhancing the redeposition of detergent composition anti-dirt can also be played by meeting alkyl glycosides described in claim Energy；Liquid detergent composition described in the invention is no viscous systems, and the state of no viscosity is more advantageous to dish-washing machine liquid Detergent embarking device carries out quantitative dispensing.

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 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.

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.

Automatic dish-washing machine detergent composition

Automatic dish-washing machine detergent composition of the invention include powdery automatic dish-washing machine detergent composition, it is liquid from The solid of dynamic dish-washing machine detergent composition, the liquid automatic dish-washing machine detergent composition of unit dose or unit dose is automatic Dish-washing machine detergent composition, is chosen in particular from the group of following composition: powdery automatic dish-washing machine detergent composition, liquid automatic The solid of dish-washing machine detergent composition, the liquid automatic dish-washing machine detergent composition of unit dose or unit dose is washed automatically Bowl machine detergent composition.

The substrate (i.e. tableware) that automatic dish-washing machine detergent composition of the invention passes through and needs to contact connects in water Touching, to achieve the purpose that the greasiness removal of substrate surface to clean substrate surface.

The automatic dish-washing machine detergent composition generally also includes surfactant system and other common washings Auxiliary agent such as enzyme preparation, fragrance etc..

Automatic dish-washing machine detergent composition of the invention, by weight, including following components:

0.01~20 part of component A；

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；

0~20 part of optional member；

20~85 parts of water；

Wherein, the component A is a kind of and/or a variety of alkyl polyglycoside.

The each component for including in composition is further described as follows:

Component A

The component A is the mixture of one or more alkyl polyglycoside.

The content of the component A is the 0.01%~20% of mixture.

The alkyl polyglycoside has 1 structure of general formula:

In general formula 1, n is 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；

P is 2~10, preferably 2~8, more preferably 2~6, and p is positive integer.

Applicants have unexpectedly found that meeting the alkyl polyglycoside of the above structure feature for other in detergent composition Component, such as fatty alcohol alkoxy compound class nonionic surfactant, copolymer dispersant etc. has good solubilization.Tool Body surface is existing: fatty alcohol alkoxy compound class nonionic surfactant and its water solubility of copolymer dispersant are poor, wash in liquid Wash be usually in agent composition emulsion dispersion state, and meet the branched alkane alkyl polyglucosides of the above structure feature to nonionic table Face activating agent and copolymer dispersant have extremely strong solubilization, the appearance of detergent composition can be made to be maintained at clarification saturating Bright state can furthermore keep liquid detergent composition under the high temperature conditions (refering in particular to 50 DEG C~65 DEG C) Clear state, and phenomena such as split-phase is with being precipitated will not occur for liquid detergent composition itself.In addition, applicant's also accident Ground has found that the alkyl polyglycoside foam levels by collateralization transformation have obtained apparent inhibiting effect, meets machine washing tableware The characteristics of detergent low foam.It is worth noting that, one of technical solution of the present invention it is a technical advantage that even if do not add silicon Oxygen alkanes defoaming agent can still rely on the alkyl polyglycoside control system foam levels of branched structure, and since type siloxane disappears Infusion is not soluble in water, and when addition is with liquid detergent composition, emulsion structure will necessarily be presented.

For the detergent composition for automatic release device, whether the assessment of high-temperature stability is in addition to occurring point Mutually and outside precipitation phenomenon, also need to consider the redissolution situation after excessive temperature storage, in general, its rinse temperature of dish-washing machine all can More than 65 DEG C, individual types are even up to 80 DEG C, and liquid detergent composition, which is difficult to avoid that, under this hot conditions will appear point Phase phenomenon, in general such noted phase separation phenomena is irreversible, but applicants have unexpectedly found that when the alkyl for adding collateralization When polysaccharide glycosides is as solubilizer, and when detergent composition restores from hot environment to normal temperature environment, it can effectively make nonionic The phenomenon that surfactant high temperature is precipitated is restored to clear, and it is automatic that this enables the liquid detergent composition to be suitable for In delivery device.

The alkyl polyglycoside is selected from following substance in one of the embodiments:

Alkyl polyglycoside 1: the alkyl polyglycoside 1 meets alkyl polyglycoside general structure, and wherein the value of n is the value of 6, m Value for 2, p is 6；

Alkyl polyglycoside 2: the alkyl polyglycoside 2 meets alkyl polyglycoside general structure, and wherein the value of n is the value of 4, m Value for 2, p is 8；

Alkyl polyglycoside 3: the alkyl polyglycoside 3 meets alkyl polyglycoside general structure, and wherein the value of n is the value of 6, m Value for 3, p is 10.

Other surfaces activating agent

Automatic dish-washing machine detergent composition of the present invention may include one or more other surfaces activating agents.

The content of the other surfaces activating agent is the 0.01%~20% of mixture.

The other surfaces activating agent can be fatty alcohol alkoxy compound class nonionic surfactant.

The fatty alcohol alkoxy compound class nonionic surfactant can have following formula 2 structure:

In general formula 2, n is 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 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.

In another embodiment, the fatty alcohol alkoxy compound class nonionic surfactant also can have following logical 3 structure of formula:

In general formula 3, n is 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.

The fatty alcohol alkoxy compound is the ring-opening polymerisation under basic catalyst effect of fatty alcohol and epoxyalkane Product.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 it is not limited to hexanol, octanol, decyl alcohol, 2-ethylhexanol, 3- propyl enanthol, laruyl alcohol, different three decyl alcohol, tridecanol, 14 Alkanol, one kind and its mixture of hexadecanol, Palmitoleyl alcohol, stearyl alcohol, isooctadecanol, oleyl alcohol, sub- oleyl alcohol, linolenyl alcohol.? It is SHELL company NEODOL series linear primary alcohol ethoxylate product, DOW company ECOSURF EH through commercialized example Serial ethoxylation and the third oxidation 2-ethylhexanol product, BASF AG's Lutensol XL series ethoxylation and the third oxidation 3- The Dehypon of propyl enanthol product, BASF AG Lutensol XP series ethoxylation 3- propyl enanthol product and BASF AG Series of products.

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.

The fatty alcohol alkoxy compound class nonionic surfactant is selected from following object in one of the embodiments, Matter:

Fatty alcohol alkoxy compound 1: the fatty alcohol alkoxy compound 1 meets 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；

Fatty alcohol alkoxy compound 2: the fatty alcohol alkoxy compound 2 meets 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；

Fatty alcohol alkoxy compound 3: the fatty alcohol alkoxy compound 3 meets fatty alcohol alkoxy compound general structure, The value that the value that the value that wherein value of n is 6, m is 3, x+z is 8, y is 0.

The other surfaces activating agent may include one or more of fatty acid alkyl alcohol amides, and the carbon number of fatty acid is 6 to 24, it can be the fatty acid of straight chain, be also possible to the fatty acid of branch, can be the fatty acid of saturation, be also possible to insatiable hunger The fatty acid of sum；Alkylol number is 0 to 2.The glycollic amide that preferred fatty acid carbon number is 8 to 18, diglycollic amide, isopropyl Alkylolamides, suitable example are coconut acid diethanolamides.

The other surfaces activating agent may include one or more of fatty acid methyl ester ethoxylates, have following logical 4 structure of formula:

In general formula 4, n is 6 to 24；X is 2 to 20, and preferably n is that 8 to 18, x is 0.5 to 30.It is preferred that x is 4 to 10.Suitable example Son is LION company MEE product.

The other surfaces activating agent may include one or more of polyether surfactants.

Wherein, the content of the polyether surfactant is the 0.01%~20% of mixture, with total weight of the mixture It calculates.

Polyether surfactant is a kind of polymer, contains ethyl oxide, oxidation propyl and oxidation butyl repetitive unit Nonionic surfactant, and the nonionic surfactant meets following general structure 5:

In general formula 5, the molecular weight of the polyether surfactant is 1000~6000, preferably 2000~6000；

In the molecule of the polyether surfactant, the content of ethyl oxide is 40%~80%, preferably 60%~ 80%；

In the molecule of the polyether surfactant, aoxidize propyl content be 5%~40%, preferably 5%~ 20%；

In the molecule of the polyether surfactant, aoxidize butyl content be 3%~20%, preferably 5%~ 15%；

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, preferably 12~18 carbon straight chain alcohols.The 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 polyether surfactant is selected from following substance in one of the embodiments:

Polyether surfactant 1: the polyether surfactant 1 meets polyether surfactant general structure, Wherein R base is laruyl alcohol, and the content of ethyl oxide is 80%, aoxidizes propyl 10%, aoxidizes butyl 10%；

Polyether surfactant 2: the polyether surfactant 2 meets polyether surfactant general structure, Wherein R base is laurel secondary alcohol, and the content of ethyl oxide is 80%, aoxidizes propyl 5%, aoxidizes butyl 15%.

The other surfaces activating agent may include the direct polyoxyethylene of one or more of natural oils and polyoxypropylene Compound.

The content of the direct polyoxyethylene of the natural oil and polyoxypropylene compound is the 0.01%~20% of mixture, institute It states the direct polyoxyethylene of natural oil and polyoxypropylene compound meets following general structure 6:

In general formula 6, R is the aliphatic hydrocarbon that carbon atom number is 10~30, preferably unsaturated hydrocarbons, the number of unsaturated bond It can be 1~7；

Wherein, m, m ' and m " can be 0~10, and m, m ' and m " be positive integer；

And m, m ' and the sum of m " be 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 " be positive integer；

And n, n ' and the sum of n " be 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 " be positive integer；

And p, p ' and the sum of p " be 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 (fatty acid of the soybean oil forms are as follows: palmitic acid content 6%~8%, oleic acid 25% with soybean oil ~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 the direct polyoxyethylene of natural oil and polyoxypropylene compound are to pass through day Prepared by the right direct ethoxylation of grease and polyoxypropyleneization, compared to traditional nonionic surfactant, it, which is omitted, is washed The pre-treating technology for washing agent alcohol greatly reduces industrial production cost and three wastes problem, and it is living directly to control surface from source Property agent production environmental pressure.In addition, natural oil is direct due to not needing the reaction such as to hydrogenate natural oil, be saponified The original hydrophobic structure characteristic of natural oil can be retained in polyoxyethylene and the fatty alcohol of polyoxypropylene compound, so that such is new It is some special that type nonionic surfactant has the function of, such as to the strong emulsification of 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) has unsaturated bond, assigns its flexible hydrophobic segment, is 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.

The other surfaces activating agent may include one or more of heterogeneous poly alkyl alcohol oxyalkyl ether sodium sulfovinates.

The content of the heterogeneous poly alkyl alcohol oxyalkyl ether sodium sulfovinate is the 0.5%~10% of mixture.

The heterogeneous poly alkyl alcohol oxyalkyl ether sodium sulfovinate has general structure 7 and/or general formula 8:

X, y, z in general formula 7 or general formula 8 only represents the ratio for meeting general formula 7 or methyl ethoxy and ethyoxyl in general formula 8 Example, does not limit the mode of methyl ethoxy and ethyoxyl polymerization, methyl ethoxy can itself continuous polymerization, also can be poly- with ethyoxyl It closes, only needs to meet (x+z): y to be 3~6, preferred (x+z): y is 3~4.

In general formula 7 or general formula 8, n is 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 0~30, preferably 1~15, more preferably 1~10；

Y is 0~10, preferably 0~5, more preferably 0~2；

Z is 0~30, preferably 1~15, more preferably 1~10；

(x+z): y is 3~6, preferably 3~4.

The heterogeneous poly alkyl alcohol oxyalkyl ether sodium sulfovinate is that fatty alcohol and epoxyalkane are made in basic catalyst The salt of sulfuric ester is generated using Sulfation with the product of lower ring-opening polymerisation, wherein fatty alcohol includes straight chain alcohol or branch Isomery alcohol, alkoxy include ethyoxyl or propoxyl group.Preferably, fatty alcohol includes hexanol, octanol, decyl alcohol, 2-ethylhexanol, 3- At least one of propyl enanthol, laruyl alcohol, different three decyl alcohol, tridecanol, tetradecanol, hexadecanol.

Commercialized fatty alcohol alkane can be used in the synthesis of the heterogeneous poly alkyl alcohol oxyalkyl ether sodium sulfovinate Oxygroup compound, such as: SHELL company NEODOL series linear primary alcohol ethoxylate product, DOW company ECOSURF EH series Ethoxylation and the third oxidation 2-ethylhexanol product, BASF AG's Lutensol XL series ethoxylation and the third oxidation 3- propyl Enanthol product and BASF AG's Lutensol XP series ethoxylation 3- propyl enanthol product.

One of preferred embodiment is the heterogeneous aliphatic alcohol polyethenoxy sodium sulphate synthesized using the XL-80 of BASF AG ST2S, embodiment will be using them as the beneficial effect of object display technique scheme.

Copolymer dispersant

The content of the copolymer dispersant is the 0.1%~30% 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:

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, comprising: 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 of the copolymer dispersant, which is selected from, contains more than one carboxylic acid group, and contains only one The monomer of a unsaturated double-bond, comprising: maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid；

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, specifically include: the vinyl monomer containing sulfonic acid group, the allyl monomer containing sulfonic acid group contain 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；

Preferably, the unsaturated monomer B of the copolymer dispersant is chosen in particular from: vinyl sulfonic acid, styrene sulfonic acid, 2- methyl -2- propylene -1- sulfonic acid, allyl sulphonic acid, this sulfonic acid of allyloxy, methyl allyloxy sulfonic acid, methyl allyloxy Benzene sulfonic 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- methyl-prop Acrylamide base -2- hydroxypropanesulfonic acid, acrylic acid -3- sulfonic group propyl ester, methacrylic acid -2- sulfonic group ethyl ester, metering system Acid -3- sulfonic group propyl ester.

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, preferably 2000~100000.

Preferably, the unsaturated monomer C of the copolymer dispersant includes unsaturated monomer C1, unsaturated monomer C2 and not It is saturated monomer C3；

In formula (3), R₁Selected from hydrogen, the group of one or more compositions of methyl, R₃Selected from hydrogen, methyl, one kind of ethyl or more The group of kind composition, R₄Selected from hydrogen, the saturated alkyl that carbon number is 1 to 20, the positive integer that m is 1 to 30.

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.

The copolymer dispersant is selected from following substance in one of the embodiments:

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: 1, inhibitor and calcium in the action principle of inhibitor 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 combined in a manner of 1:1 with calcium ion, exist 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 polycarboxylate brand-new chemical property, summarized below The type and effect of common polymer monomer.

The type and effect summary sheet of common polymer monomer

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 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 detergent composition must satisfy many requirements.They need to have various culinary art dirts outstanding Clean-up performance, including remove 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 phosphoric acid salt The automatic dish-washing machine detergent tablet of chelating agent is 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 detergent composition composition added with specific chelating agent, It is friendly to environment and to milk residue, eggs residue, starchiness class residue and pesticide residue ingredient have good Good removal effect is able to maintain after 30 DEG C or so or 35 DEG C or so or 37 DEG C or so storages a few weeks or longer time 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.

Enzyme preparation

Automatic dish-washing machine detergent composition provided by the invention may include one or more enzyme preparations, to provide cleaning Performance, fabric nursing and/or other beneficial effects.The enzyme preparation is selected from following enzyme group in groups: protease, alpha-amylase, Cellulase, hemicellulase, phosphatidase, esterase, lipase, peroxidase/oxidizing ferment, pectase, lyases, sweet dew are poly- Carbohydrase, cutinase, reductase, zytase, amylopectase, tannase, pentosanase, maltosan, arabinase, β- Dextranase.Common enzyme preparation is protease, amylase, lipase, cutinase and/or cellulase.Enzyme preparation content is The 0.1%~10% of automatic dish-washing machine detergent composition.

Automatic dish-washing machine detergent composition of the invention may include: account for the enzyme of composition weight 0.001%~10% Stabilising system.The enzyme stabilising system can be compatible with detergent composition, may include calcium ion, boric acid, borax, propylene glycol, Glycerol, one or more of mixtures of polyalcohol.The weight and dosage of enzyme stabilising system are according to the shape of detergent composition The type of formula and composition and enzyme preparation is adjusted.

Detergent enzyme preparation

Detergent enzyme preparation refers to the enzyme preparation for being commonly used in preparing detergent compositions, the enzyme preparation are as follows: all kinds of Amylase, each quasi-lipase, all kinds of protease, all kinds of cellulases and all kinds of hemicellulases.

Amylase

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 Termamyl 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.

Preferably, diastase content is the 0.2%-5% of detergent composition.Meanwhile also may include in composition Account for the enzyme stabilising system of composition weight 0.001~10%.The enzyme stabilising system can be compatible with detergent composition, can wrap At least one of calcium ions, boric acid, borax, propylene glycol, glycerol and polyalcohol.The weight and dosage of enzyme stabilising system are with root It is adjusted according to the form and composition of detergent composition and the type of enzyme preparation.

Protease

Suitable protease includes the protease of bacterium, fungi, plant, virus or animal origin, such as plant or micro- life Object source.Preferred microorganism source.Mutant or protein engineered mutant including chemical modification.It can be alkalinity Protease, such as serine protease or metalloproteinases.Serine protease can be trypsase or bacillus subtilis protein Enzyme.Metalloproteinases can be thermolysin or other metalloproteinases.It is suitble to can purchasing from commercial channel for conditions above The protease bought includes the enzyme preparation product sold with following trade name, comprising: the Alcalase from Novozymes company, 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；Maxatase from Danisco company and Dupont company, 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.

Preferably, protease preparation content is the 0.2%~5% of detergent composition.Meanwhile also may include in composition Account for the enzyme stabilising system of composition weight 0.001~10%.The enzyme stabilising system can be compatible with detergent composition, can wrap At least one of calcium ions, boric acid, borax, propylene glycol, glycerol and polyalcohol.The weight and dosage of enzyme stabilising system are with root It is adjusted according to the form and composition of detergent composition and the type of enzyme preparation.

Optional member

Automatic dish-washing machine detergent composition of the present invention includes following optional additive: filler, glues alkaline agent Spend the mixture of one or more compositions of regulator, preservative, colorant, colour stabilizer and essence.

Automatic dish-washing machine detergent composition of the present invention may include one or more alkaline agents, and alkaline agent is selected from hydrogen-oxygen Change sodium, potassium hydroxide, the sodium salt of ethylenediamine tetra-acetic acid, alkali carbonate, the silicate of alkali metal.

Automatic dish-washing machine detergent composition of the present invention may include one or more fillers, be selected from citric acid Sodium, sodium sulphate, sodium chloride, potassium chloride, water, preferably sulfuric acid sodium and sodium citrate.

Automatic dish-washing machine special purpose detergent composition of the present invention may include one or more of viscosity modifiers, To provide suitable viscosity.Suitable viscosity modifier such as salt, polysaccharide, sizing material, short chain fatty alcohol, short chain fatty alcohol alkyl ether. Suitable example is sodium chloride, ethyl alcohol, propylene glycol, sodium citrate, alkyl-hydroxyalkylcelluloswith ether, carragheen, xanthan gum, poly- third Alkenylamide derivative.

Automatic dish-washing machine special purpose detergent composition of the present invention may include one or more of bleach systems.Drift Lean type system includes hypohalite beaches, peroxide bleaches.Peroxide typically comprises hydrogen peroxide source and bleaching is lived Change system.Hydrogen peroxide source includes but is not limited to perborate, percarbonate, persulfate and their mixture.One In a little embodiments, preferred hydrogen peroxide source is SODIUM PERCARBONATE.Bleach system may include bleach-activating, and the bleaching is lived For promoting peroxide, fast decoupled generates oxygen to agent at a lower temperature, the group selected from following compound composition: four acetyl Base ethylenediamine, benzoyl caprolactam, 4- nitrobenzoylcaprolactam, 3- chlorobenzoylcaprolactam, benzoyl Oxygroup benzene sulfonate, nonanoly acyloxy benzene sulfonate, phenol benzoate, decanoyloxybenzenesulphonate, benzoyl valerolactam are pungent Acyloxybenzenesulfonic acids salt, transition metal bleach catalyst.

Automatic dish-washing machine special purpose detergent composition of the present invention can also include ozone stabilizer, and the ozone is steady Determine the speed that generation hydrogen peroxide is decomposed in agent for adjusting peroxide, the local concentration of hydrogen peroxide is made to be unlikely to excessive, closes 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 In, the content of bleach system is the 0.01%~30%, preferably 0.01%~20% of detergent composition total weight, further Preferably 0.01%~10%.

The automatic dish-washing machine special purpose detergent composition may include one or more corrosion inhibitors, these corrosion inhibitors can mention For confrontation glass and/or the benefit of metal erosion, and the term is covered for preventing or reducing non-ferrous metal (especially silver Or copper) corrosion reagent.

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.

Automatic dish-washing machine detergent composition of the present invention may include the corrosion inhibitor of any conventional amount.However, base In total weight, additive amount is preferably 0.01%~5%, and preferably 0.05%~3%, more preferably 0.1%~2.5%.

In some embodiments, automatic dish-washing machine detergent composition of the present invention preferably comprises preservative, closes Suitable example is phenoxy group alcohol, sodium benzoate；Isothiazolinone and its derivative such as methylisothiazolinone, methyl chloroisothiazole Quinoline ketone, or mixtures thereof one kind of benzoisothiazolinone.Preservative dosage be 0.001% to 5%, preferably 0.01% to 2%.

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.

Automatic dish-washing machine special purpose detergent composition of the present invention preferably comprises fragrance, and the fragrance is suitable comprising all Fragrance component for cleaning product.Fragrance used of the invention can be natural origin, be also possible to chemically synthesized product, The either mixture of the two.Suitable example such as lemon, rose, jasmine, lavender, citrus is fragrant, green fragrant, radix aucklandiae etc..

In some embodiments, automatic dish-washing machine special purpose detergent composition of the present invention contains binder.Institute Stating binder includes starch slurry, methylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, sodium carboxymethylcellulose, ethyl fibre Tie up element, povidone, gelatin, polyethylene glycol, 50%~70% sucrose solution and sodium alginate.

In some embodiments, automatic dish-washing machine special purpose detergent composition of the present invention contains disintegrating agent.Institute State disintegrating agent include dried starch, carboxyrnethyl starch sodium, low-substituted hydroxypropyl cellulose, cross-linked carboxymethyl cellulose sodium, crospovidone, Gas-producing disintegrant, the gas-producing disintegrant are preferably the mixture of citric acid and sodium bicarbonate.

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 composition of the invention is using various method preparations well-known to those skilled in the art.The composition Preparation can be carried out by conventional means, specifically should be according to the state of component in the solution and effect and the stabilization of component Property the suitable processing temperature of selection 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 in being illustrated according to the concrete operations of dish-washing machine about detergent addition description section carry out using.

Detergent composition of the invention is more suitable in the automatic release device of liquid automatic dishwasher detergent, should be certainly Dynamic delivery device refers to the detergent that can store at least 20 times washing procedure dosages, and may be implemented to determine automatically in washing process The mechanical device of amount addition detergent.

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

1) 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.

Effect application test

The method of the experimental test occurred in embodiment verifying is as follows:

1, 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.

1.1, 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.

1.2, 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.

1.3, dirt is filled

It fills dirt and is used for coated vegetable dish and small oval plate, fill the formula of dirt are as follows: 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 Lard, butter and vegetable oil are placed in a beaker by the mass ratio of 1:1:2, 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.

1.4, 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, specific evaluation method is evaluated as shown in Figure 1, to detergent Properties make scoring.

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

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, the formula of artificial dirt are as follows: 10% miscella, 15% wheat Powder, 7.5% whole milk powder, 30% fresh whole egg liquid, 4% catsup, 1% mustard, 32.5% distilled water.Wherein miscella with Lard, butter and vegetable oil are placed in a beaker by the mass ratio of 1:1:2, 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 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.

2.6, it defiles referring to 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, evaluated by the specific evaluation method of following clean effect evaluation table, to the items of detergent Performance makes scoring.When the surface being infected with visual method starch dirt is scored, it can be coloured, be made with iodine solution (KI-I2) Residue is more eye-catching.In order to facilitate comparative example performance difference, when dirt is artificial dirt, unified use justifies vegetable dish as commenting Valence object；It is unified to use rice bowl as evaluation object when dirt is oat stain；It is unified to use teacup when dirt is tea stain For evaluation object.

Clean effect evaluation table

Embodiment

Embodiment 1 and comparative example 1, comparative example 2, comparative example 3

It is formed according to the following table 1 and prepares powder detergent composition A and A ', B ', C '.

Detergent composition A and A ', the B ', C ' that 1 embodiment 1 of table and comparative example 1, comparative example 2, comparative example 3 are prepared

Embodiment 1 and comparative example 1, comparative example 2, the test result of detergent powder the composition A and A ' of comparative example 3, B ', C ' Such as table 1.As can be seen that embodiment 1 is the detergent combination that the technical solution described according to the present invention is prepared from 1 result of table Object, wherein the compounding containing alkyl polyglycoside and/or fatty alcohol alkoxy compound, and under the coordinated of other components, energy It is enough to keep that detergent is not stratified the effect of good stability under the conditions of high-temperature (50 DEG C~80 DEG C)；And alkyl glycosides can also The performance for playing enhancing detergent composition anti-dirt redeposition combines detergent by the coordinative role with other components The dirt-removing power of object is stronger；In addition, detergent composition made from the present embodiment is no viscous systems, no viscosity state more Be conducive to dish-washing machine automatic liquid detergent dispensing device and carry out quantitative dispensing.

Comparative example 1, comparative example 2 and comparative example 3 have lacked technical essential described in portion of techniques scheme.Wherein comparative example 1, comparative example 2 and comparative example 3 have lacked branched alkane alkyl polyglucosides and/or fatty alcohol alkoxy compound, and it is heavy to resist from visible its of result Product performance and high-temperature stability obviously weaken.

Embodiment 2, embodiment 3, embodiment 4

Detergent tablet composition B, C, the D prepared according to the following table 2 composition.

Detergent tablet composition B, C, D that 2 embodiment 2 of table, embodiment 3, embodiment 4 are prepared

The test result such as table 2 of detergent tablet composition B, C, D of embodiment 2, embodiment 3, embodiment 4.From 2 result of table In as can be seen that technical solutions according to the invention can be used different types of branched alkane alkyl polyglucosides, non-ionic surface is living Property agent, the components such as polymeric dispersant compounding, synergistic effect realize, make liquid detergent composition at high temperature still have compared with High stability not there is a phenomenon where layering, split-phase or is precipitated, and the performance with anti-dirt redeposition.And according to hope The effect reached can carry out the adjustment in the range of claim restriction to the additive amount of different component.

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

1. a kind of automatic dish-washing machine detergent composition, which is characterized in that including following parts by weight of component:

0.01~20 part of component A；

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；

0~20 part of optional member；

20~85 parts of water；

Wherein, the component A is a kind of and/or a variety of alkyl polyglycoside.

2. automatic dish-washing machine detergent composition as described in claim 1, which is characterized in that the alkyl polyglycoside has general formula 1 structure:

In general formula 1, n is 2~16, and n is positive integer；

M is 2~10, and m is positive integer；

P is 2~10, and p is positive integer.

3. automatic dish-washing machine detergent composition as described in claim 1, which is characterized in that the other surfaces activating agent packet Fatty alcohol alkoxylates, fatty acid alkyl alcohol amide, fatty acid methyl ester ethoxylate, gather fatty acid alkoxylates The direct polyoxyethylene of ether type surfactant, natural oil and polyoxypropylene compound, heterogeneous fatty alcohol polyoxyalkyl ether sulfuric acid One of ester sodium is a variety of.

4. automatic dish-washing machine detergent composition as described in claim 1, which is characterized in that the weight of the copolymer dispersant Multiple unit is selected from unsaturated monomer A, the group that residue forms after unsaturated monomer B, unsaturated monomer C polymerization, and meets such as ShiShimonoseki System:

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 of the copolymer dispersant, which is selected from, contains more than one carboxylic acid group, and contains only one not It is saturated the monomer of double bond；

6) the unsaturated monomer B of the copolymer dispersant, which is selected from, contains a sulfonic acid group, and contains only a unsaturation The sulfonic acid group of the monomer of double bond, the unsaturated monomer B of the copolymer dispersant is deposited 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%；

9) molecular weight of the copolymer dispersant is 1000~150000.

5. automatic dish-washing machine detergent composition as claimed in claim 4, it is characterised in that: the copolymer dispersant is not Saturation monomer B is selected from: vinyl sulfonic acid, styrene sulfonic acid, 2- methyl -2- propylene -1- sulfonic acid, allyl sulphonic acid, allyl oxygen Basic sulfonic acid, methyl allyloxy sulfonic acid, methyl allyloxy benzene sulfonic 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, one of methacrylic acid -3- sulfonic group propyl ester or a variety of.

6. automatic dish-washing machine detergent composition as claimed in claim 4, it is characterised in that: the copolymer dispersant is not Being saturated monomer C includes unsaturated monomer C1, unsaturated monomer C2 and unsaturated monomer C3；

The unsaturated monomer C2 of the copolymer dispersant is selected from acrylamide, benzyl methacrylamide, cyclohexyl methyl third Acrylamide, N-tert-butyl acrylamide, Methacrylamide, dimethylacrylamide, dimethylaminopropyl Methacrylamide；

In formula (3), R₁Selected from hydrogen, the group of one or more compositions of methyl；R₃Selected from hydrogen, methyl, one or more groups of ethyl At group；R₄Selected from hydrogen, the saturated alkyl that carbon number is 1 to 20, the positive integer that m is 1 to 30.

7. automatic dish-washing machine detergent composition as described in claim 1, which is characterized in that the amino acid derivativges chelating agent Including methylglycine diacetic acid, glutamic acid diacetic acid, N, N- dicarboxylic acids amino -2- hydroxy propane base sulfonic acid, hydroxyl -2 3-, 2 '-iminodisuccinic acids and its alkali metal salts or ammonium salt it is one or more.

8. automatic dish-washing machine detergent composition as described in claim 1, it is characterised in that: the enzyme preparation include protease, Alpha-amylase, cellulase, hemicellulase, phosphatidase, esterase, lipase, peroxidase/oxidizing ferment, pectase, cracking Enzyme, mannase, cutinase, reductase, zytase, amylopectase, tannase, pentosanase, maltosan, I Primary carbohydrase, 1,4 beta-glucanase it is one or more.

9. automatic dish-washing machine detergent composition as described in claim 1, which is characterized in that the additive includes filling Agent, alkaline agent, viscosity modifier, bleach system, ozone stabilizer, corrosion inhibitor, preservative, colorant, colour stabilizer and essence One of or it is a variety of.