CN108865480B

CN108865480B - Special detergent composition for automatic dish-washing machine

Info

Publication number: CN108865480B
Application number: CN201810901960.3A
Authority: CN
Inventors: 张龙秋; 周文杰; 梁智坤; 黄亮; 沈兵; 张利萍
Original assignee: Guangzhou Liby Enterprise Group Co Ltd
Current assignee: Guangzhou Lidi Technology Co ltd
Priority date: 2018-08-09
Filing date: 2018-08-09
Publication date: 2020-11-06
Anticipated expiration: 2038-08-09
Also published as: CN108865480A

Abstract

The invention discloses a special detergent composition for an automatic dish-washing machine, and relates to the technical field of daily chemical industry. The composition comprises: 0.01-20 parts of polyether surfactant; 0.01-20 parts of a nonionic surfactant; 0.01-20 parts of other surfactants; 0.1-30 parts of a copolymer dispersant; 0.1-40 parts of an amino acid derivative chelating agent; 0.1-10 parts of enzyme preparation and 0-80 parts of additive; wherein the nonionic surfactant at least comprises two fatty alcohol alkoxylates, namely a fast-emulsifying fatty alcohol alkoxylate and a slow-emulsifying fatty alcohol alkoxylate, and the weight ratio of the polyether surfactant to the fatty alcohol alkoxylate is 1: 0.1 to 1.5. The special detergent composition for the automatic dish washing machine has good emulsifying, dispersing and removing effects on oil stains and food stains, effectively reduces foams in the washing process, and improves the cleaning capacity of the detergent.

Description

Special detergent composition for automatic dish-washing machine

Technical Field

The invention relates to the technical field of daily chemical industry, in particular to a special detergent composition for an automatic dish-washing machine.

Background

Compared with the manual tableware washing, the automatic dish washing machine has the advantages of saving physical strength, convenience and water saving, and has multiple functions of cleaning, disinfecting, drying, storing and the like, so that the automatic dish washing machine can fully meet the requirement that people hope to be liberated from simple and repeated housework.

The dishwasher mainly utilizes the spraying effect of strong water flow generated in a three-dimensional space, the heat energy effect of heated water and the oil and stain removing effect of a cleaning agent to finish the cleaning and removal of the dirt on the tableware by mutual cooperation. The water flow which is pressurized by the pressurizing pump and then sprayed into the dish washer from the nozzle performs three-dimensional rotating motion in the dish washer, so that dead corners which cannot be cleaned do not exist in the dish washer, strong water flow energy impact effect generated by spraying can effectively remove dirt adhered to the tableware. Meanwhile, the dirt-removing power of hot water is obviously improved compared with that of cold water, and the solubility of insoluble substances such as slightly soluble salt and the like in the hot water is often greatly increased, so that the possibility of hard water salt scale formation on tableware is reduced to a certain extent, and when the temperature of oil stains such as fat and the like is higher than the melting point of the oil stains, the mutual attraction among oil drops is reduced, the adhesive force of the oil drops on the surface of the tableware is also reduced, so that the oil stains are easy to remove from the surface of the tableware and are not easy to adsorb and deposit on the tableware. Many of the components of the detergent for automatic dish washer, such as bleaching agent, etc., are characterized by higher activity at higher temperature, and these components tend to play a stronger role in the detergent for machine washing than in the detergent for hand washing.

Due to the limitations of the operating principle of a dishwasher, hand dishwashing detergents and machine dishwashing detergents cannot be mixed. In the general knowledge of the daily chemical industry, the formulations for hand washing and machine washing of detergents for washing fabrics are similar, except that the contents of the various components are different, i.e. the tendency towards certain performance indexes is different, for example, the hand washing product is required to be rich in foam, while the machine washing is required to be medium or low in foam. Or simply, there is not much problem in mixing the two. However, it is absolutely impossible to mix the detergent for washing dishes, and the manual dishwashing detergent cannot be used in an automatic dishwasher. In the case of hand dishwashing detergents, consumers often determine whether the amount of detergent added is sufficient based on the amount of suds. Therefore, hand dishwashing detergents are foamy or even have a certain foam stabilizing property, and moreover, the detergent has a high surfactant content, which plays a major role in removing dirt. Furthermore, no additional builder is required. However, in machine washing, the dishwasher-specific detergent must be low-foaming, even non-foaming, in order to protect the water pump, prevent flooding, prevent excessive foaming from affecting the rotation of the swing arm, and the like. The surfactant plays a role in wetting the surface in the special washing detergent for machine washing.

Although the surfactant selected in the dishwasher detergent is low-foam, the surfactant solution inevitably forms foam due to the impact of the dishwasher water flow, and the water-soluble polymers such as protein, starch and the like contained in the dirt also form stable foam, and the existence of the foam can influence the decontamination effect of the dishwasher, so the problem of controlling the foam of the dishwasher detergent is one of the important researches in the field.

Disclosure of Invention

The invention aims to solve the technical problem that the existing dish washing machine has too much foam to influence the oil stain removal effect of the dish washing machine.

In order to solve the above problems, the present invention provides the following technical solutions:

a special detergent composition for an automatic dishwasher comprises the following components in parts by weight:

0.01-20 parts of polyether surfactant;

0.01-20 parts of a nonionic surfactant;

0.01-20 parts of other surfactants;

0.1-30 parts of a copolymer dispersant;

0.1-40 parts of an amino acid derivative chelating agent;

0.1-10 parts of an enzyme preparation;

0-80 parts of an additive;

wherein the nonionic surfactant at least comprises two fatty alcohol alkoxylates, namely a fast-emulsifying fatty alcohol alkoxylate and a slow-emulsifying fatty alcohol alkoxylate, and the weight ratio of the polyether surfactant to the fatty alcohol alkoxylate is 1: 0.1 to 1.5.

The further technical scheme is as follows: the polyether surfactant has the following general formula (1):

in the general formula (1), the molecular weight of the polyether surfactant is 500-6000;

in the molecules of the polyether surfactant, the content of the oxidized ethyl is 40-80 percent;

in the molecules of the polyether surfactant, the content of the oxypropyl is 5-40%;

in the molecules of the polyether surfactant, the content of the butyl oxide is 3-20%;

in the molecule of the polyether surfactant, R group is selected from linear fatty alcohol and/or branched fatty alcohol with the carbon number of 6-24, and the binding site of R based on polyether group is selected from primary position, secondary position and tertiary position.

The further technical scheme is as follows: the content of the rapid emulsifier fatty alcohol alkoxylate is 0.01-10% of the composition, and the rapid emulsifier fatty alcohol alkoxylate has the following general formula (2):

wherein in the general formula (2), n is 2-16 and n is a positive integer; m is 2-10 and m is a positive integer; x is 0-10; y is 0 to 10; z is 0 to 10; (x + z): y is 0.2 to 1;

the content of the slow emulsifier fatty alcohol alkoxylate is 0.01-15% of the composition, and the slow emulsifying fatty alcohol alkoxylate can also have the following general formula (3):

wherein in the general formula (3), n is 2-16 and n is a positive integer; m is 2-10 and m is a positive integer; x is 3-30; y is 0 to 10; z is 3 to 30; (x + z): y is 3 to 10.

The further technical scheme is as follows: the other surfactant comprises at least one of alkyl polyglycoside, fatty acid alkoxylate, fatty acid alkylolamide, fatty acid methyl ester ethoxylate, natural oil direct polyoxyethylene or polyoxypropylene.

The further technical scheme is as follows: the repeating unit of the copolymer dispersant is selected from the group consisting of residues after polymerization of unsaturated monomer A, unsaturated monomer B and unsaturated monomer C, and satisfies the following relationship:

1) the residue of the unsaturated monomer A of the copolymer dispersant accounts for 60 to 90 percent of the weight of the copolymer dispersant;

2) the unsaturated monomer A of the copolymer dispersant comprises 70 to 99.99 weight percent of unsaturated monomer A1 and 0.01 to 30 weight percent of unsaturated monomer A2;

3) the unsaturated monomer A1 of the copolymer dispersant is selected from monomers containing one carboxylic acid group and only one unsaturated double bond; the carboxylic acid groups of the unsaturated monomer A1 of the copolymer dispersant are present in the copolymer dispersant in the form of a salt;

4) the unsaturated monomer A2 of the copolymer dispersant is selected from monomers containing more than one carboxylic acid group and only one unsaturated double bond;

5) the residue of the unsaturated monomer B of the copolymer dispersant accounts for 10 to 40 percent of the weight of the copolymer dispersant;

6) the unsaturated monomer B of the copolymer dispersant is selected from monomers containing one sulfonic acid group and only one unsaturated double bond, and the sulfonic acid group of the unsaturated monomer B of the copolymer dispersant exists in a salt form in the copolymer dispersant;

7) the residue of the unsaturated monomer C of the copolymer dispersant accounts for 0.1 to 20 percent of the weight of the copolymer dispersant;

8) the unsaturated monomer C of the copolymer dispersant is selected from monomers containing one unsaturated double bond;

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

The further technical scheme is as follows: the unsaturated monomer A1 of the copolymer dispersant is selected from acrylic acid, methacrylic acid, alpha-hydroxy acrylic acid, alpha-hydroxy methacrylic acid and crotonic acid;

the unsaturated monomer A2 of the copolymer dispersant is selected from maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid;

the unsaturated monomer B of the copolymer dispersant is selected from a vinyl monomer containing a sulfonic acid group, an allyl monomer containing a sulfonic acid group, acrylamide containing a sulfonic acid group, methacrylamide containing a sulfonic acid group, acrylate containing a sulfonic acid group and methacrylate containing a sulfonic acid group.

The further technical scheme is as follows: the unsaturated monomer C of the copolymer dispersant comprises unsaturated monomer C1, unsaturated monomer C2 and unsaturated monomer C3;

the unsaturated monomer C1 of the copolymeric dispersant is selected from compounds corresponding to the following general formula (4):

wherein, in the general formula (4), R₁One or more selected from hydrogen and methyl, and n is a positive integer from 2 to 8;

the unsaturated monomer C2 of the copolymer dispersant is selected from one of acrylamide, benzyl methacrylamide, cyclohexyl methacrylamide, tert-butyl acrylamide, methacrylamide, dimethylacrylamide and dimethylaminopropyl methacrylamide;

the unsaturated monomer C3 of the copolymeric dispersant is selected from compounds corresponding to the following formula (5) and/or the following formula (6):

wherein, in the general formula (5), R₁One or more selected from hydrogen and methylGroup of seeds, R₂Is a saturated alkyl group having 2 to 8 carbon atoms;

wherein, in the general formula (6), R₁One or more selected from hydrogen and methyl, R₃One or more selected from hydrogen, methyl and ethyl, R₄Selected from hydrogen, saturated alkyl with carbon number of 1-20, and m is a positive integer of 1-30.

The further technical scheme is as follows: the amino acid derivative chelating agent includes at least one of methylglycine diacetic acid (MGDA), glutamic acid diacetic acid (GLDA), N-dicarboxylic acid amino-2-hydroxypropanesulfonic acid, 3-hydroxy-2, 2' -iminodisuccinic acid, and alkali metal or ammonium salts thereof.

The further technical scheme is as follows: the enzyme preparation comprises at least one of protease, alpha-amylase, cellulase, hemicellulase, phospholipase, esterase, lipase, peroxidase/oxidase, pectinase, lyase, mannanase, cutinase, reductase, xylanase, pullulanase, tannase, pentosanase, maltosanase, arabinase and beta-glucanase.

The further technical scheme is as follows: the additive comprises at least one of filler, alkaline agent, viscosity regulator, bleaching system, active oxygen stabilizer, corrosion inhibitor, antiseptic, colorant, color stabilizer and essence.

Compared with the prior art, the invention can achieve the following technical effects:

the special detergent composition for the automatic dishwasher can greatly reduce foam in the washing process by adding the polyether surfactant and the fatty alcohol alkoxylate in a certain proportion; the components in the composition are cooperated with each other, so that the emulsifying and dispersing effects of the nonionic surfactant on oil stains can be improved, and the decontamination performance is enhanced; the water flow pressure of the nozzle of the dish washing machine is ensured, and the washing efficiency of the dish washing machine is improved.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

FIG. 1 is a schematic diagram of the action mechanism of a polyether surfactant for inhibiting foaming of a nonionic surfactant;

FIG. 2 is a schematic diagram showing the evaluation criteria of conjunctiva and plaque formation.

Detailed Description

The features, benefits and advantages of the present invention will become apparent to those skilled in the art from a reading of the present disclosure. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

All percentages, parts and ratios are based on the total weight of the composition of the present invention, unless otherwise specified. All weights as they pertain to listed ingredients are assigned to levels of active material and, therefore, do not include solvents or by-products that may be included in commercially available materials, unless otherwise specified. The term "weight content" herein may be represented by the symbol "%".

All molecular weights herein are weight average molecular weights expressed in daltons, unless otherwise indicated.

All formulations and tests herein occur at 25 ℃ environment, unless otherwise indicated.

The use of "including," "comprising," "containing," "having," or other variations thereof herein, is meant to encompass the non-exclusive inclusion, as such terms are not to be construed. The term "comprising" means that other steps and ingredients can be added that do not affect the end result. The term "comprising" also includes the terms "consisting of …" and "consisting essentially of …". The compositions and methods/processes of the present invention can comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein.

It is also to be understood that the terminology used in the description of the embodiments of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the embodiments of the invention. As used in the description of embodiments of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

Special detergent composition for automatic dish-washing machine

The detergent composition for automatic dish washing machine of the present invention includes a powder detergent composition for automatic dish washing machine, a liquid detergent composition for automatic dish washing machine, a unit dose of the liquid detergent composition for automatic dish washing machine or a unit dose of the solid detergent composition for automatic dish washing machine, and is specifically selected from the group consisting of: a powder-like automatic dishwasher specific detergent composition, a liquid-like automatic dishwasher specific detergent composition, a unit-dose liquid automatic dishwasher specific detergent composition, or a unit-dose solid automatic dishwasher specific detergent composition.

The special detergent composition for the automatic dishwasher is contacted with a substrate (namely tableware) needing to be contacted in water, so that stains on the surface of the substrate are removed, and the aim of cleaning the surface of the substrate is fulfilled.

The detergent compositions for automatic dishwashing generally also comprise a surfactant system and other customary detergency builders such as enzyme preparations, perfumes and the like.

The special detergent composition for the automatic dishwasher comprises the following components in parts by weight:

0.01-20 parts of polyether surfactant;

0.01-20 parts of a nonionic surfactant;

0.01-20 parts of other surfactants;

0.1-30 parts of a copolymer dispersant;

0.1-40 parts of an amino acid derivative chelating agent;

0.1-10 parts of an enzyme preparation;

0-80 parts of an additive;

wherein the nonionic surfactant at least comprises two fatty alcohol alkoxylates, namely a fast-emulsifying fatty alcohol alkoxylate and a slow-emulsifying fatty alcohol alkoxylate, and the weight ratio of the polyether surfactant to the fatty alcohol alkoxylate is 1: 0.1 to 1.5, preferably 1: 0.1 to 0.5.

The components included in the composition are further described below:

polyether surfactant

The content of the polyether surfactant provided by the embodiment of the invention is 0.01-20% of the special detergent composition for the automatic dishwasher, calculated by the total weight of the composition.

The polyether surfactant is a polymer, and the polymer surfactant contains repeating units of oxyethyl, oxypropyl and oxybutyl, and the polymer surfactant corresponds to the following general formula (1):

wherein, in the general formula (1), the molecular weight of the polyether surfactant is 500-6000, preferably 600-4000;

in the molecules of the polyether surfactant, the content of the oxidized ethyl is 40-80%, preferably 60-80%;

in the molecules of the polyether surfactant, the content of the oxypropyl is 5-40%, preferably 5-20%;

in the molecules of the polyether surfactant, the content of the butyl oxide is 3-20%, preferably 5-15%;

in the molecule of the polyether surfactant, R groups are selected from linear fatty alcohol and/or branched fatty alcohol with 6 to 24 carbon atoms, preferably 12-18 carbon linear alcohol, and the binding sites of R based on polyether groups are selected from primary, secondary and tertiary positions.

In addition, the preferred values of the oxyethylene group, oxypropyl group and oxybutyl group are only the proportional relationship among the oxyethylene group, oxypropyl group and oxybutyl group, and the polymerization mode is not limited, and each polymerization unit may be continuously polymerized by itself or with other polymerization units as long as the whole numerical ratio is maintained.

The applicant has found that a polyether surfactant with a proper ratio of oxypropyl group and oxybutyl group can exert the function of inhibiting the foaming of a nonionic surfactant, especially the foaming function of fatty alcohol polyoxyethylene/polyoxypropylene ether, because the polyether surfactant molecule meeting the above requirements can form a complex structure with other surfactants in washing water, effectively limits the migration of other surfactant molecules (especially fatty alcohol polyoxyethylene/polyoxypropylene ether) to a bubble interface, thereby reducing the foaming amount of the surfactant molecules and enhancing the defoaming capability, and the specific action mechanism is shown in fig. 1.

As depicted in fig. 1, the polyether surfactant meeting the above requirements does not spread in water because molecular chains have no electric charges, and its chimeric oxypropyl and oxybutyl groups are effective to form hydrophobic regions throughout the polymer molecules, while micelles composed of surfactants are adsorbed in the hydrophobic regions by hydrophobic bonding to form complexes, thereby hindering the migration of surfactant molecules to the bubble interface. In addition, the applicant also found that if the polyether surfactant contains too many hydrophobic groups in the molecule, the molecule itself is easy to migrate to the interface of the air bubbles, which greatly reduces the effect of inhibiting the air bubbles of the surfactant molecules. It must be emphasized that the fatty alcohol polyoxyethylene/polyoxypropylene ether and polyether surfactant molecules meeting the above requirements have similar structures, and the combination effect of the fatty alcohol polyoxyethylene/polyoxypropylene ether and polyether surfactant molecules into a compound is stronger than that of other surfactants, so that the low foaming effect of the detergent composition is better.

In certain embodiments, the polyether surfactant is selected from the group consisting of:

polyether surfactant 1: the polyether surfactant 1 conforms to the general structural formula (1) of the polyether surfactant, wherein the R group is lauryl alcohol, the content of the oxyethyl group is 80 percent, the content of the oxypropyl group is 10 percent, and the content of the oxybutyl group is 10 percent;

polyether surfactant 2: the polyether surfactant 2 conforms to the structural general formula (1) of the polyether surfactant, wherein R is lauryl secondary alcohol, the content of the oxidized ethyl is 80%, the content of the oxidized propyl is 5%, and the content of the oxidized butyl is 15%.

Polyether surfactant 3: the polyether surfactant 3 conforms to the general structural formula (1) of the polyether surfactant, wherein R is lauryl secondary alcohol, the content of the oxidized ethyl is 40%, the content of the oxidized propyl is 40%, and the content of the oxidized butyl is 20%; (ii) a

Polyether surfactant 4: the polyether surfactant 4 conforms to the structural general formula (1) of the polyether surfactant, wherein R is lauryl secondary alcohol, the content of the oxidized ethyl is 50%, the content of the oxidized propyl is 30%, and the content of the oxidized butyl is 20%.

Nonionic surfactant-fatty alcohol alkoxylates

The detergent composition special for the automatic dishwasher comprises 0.01-20 parts by weight of nonionic surfactant, wherein the nonionic surfactant at least comprises two fatty alcohol alkoxylates, and the fatty alcohol alkoxylates comprise a fast-emulsifying fatty alcohol alkoxylate and a slow-emulsifying fatty alcohol alkoxylate.

In some embodiments, the detergent composition for automatic dish washer comprises 0.01-10 parts by weight of fast emulsifying type fatty alcohol alkoxylate and 0.01-15 parts by weight of slow emulsifying type fatty alcohol alkoxylate.

Wherein the rapidly emulsifying fatty alcohol alkoxylate has the following general formula (2):

in some embodiments, in the general formula (2), n is 2 to 16, preferably 2 to 10, more preferably 2 to 8, and n is a positive integer;

m is 2-10, preferably 2-8, more preferably 2-4, and m is a positive integer;

x is 0 to 10, preferably 0 to 5, and more preferably 0 to 3;

y is 0 to 10, preferably 0 to 7, and more preferably 2 to 5;

z is 0 to 10, preferably 0 to 5, and more preferably 0 to 3;

(x + z): y is 0.2 to 1, preferably 0.2 to 0.5.

The slow emulsifying fatty alcohol alkoxylate has the following general formula (3):

in some embodiments, in the general formula (3), n is 2 to 16, preferably 2 to 10, more preferably 2 to 8, and n is a positive integer;

m is 2-10, preferably 2-8, more preferably 2-4, and m is a positive integer;

x is 3-30, preferably 3-15, and more preferably 3-10;

y is 0 to 10, preferably 0 to 7, and more preferably 0 to 5;

z is 3 to 30, preferably 3 to 15, and more preferably 3 to 10;

(x + z): y is 3 to 10, preferably 5 to 10.

It should be noted that the fatty alcohol alkoxylates provided in the examples of the present invention are products of ring opening polymerization of fatty alcohols and alkylene oxides under the action of alkaline catalysts. The fatty alcohol includes a straight chain alcohol or a branched chain isomeric alcohol. Alkoxy groups include ethoxy and propoxy groups. Fatty alcohols include, but are not limited to, one or more mixtures of hexanol, octanol, decanol, 2-ethylhexanol, 3-propylheptanol, lauryl alcohol, isotridecyl alcohol, tridecyl alcohol, tetradecyl alcohol, cetyl alcohol, palmitoyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol. Examples which have been commercialized are the NEODOL series of linear fatty alcohol ethoxylate products from SHELL, the ECOSURF EH series of ethoxylated and propoxylated 2-ethylhexanol products from DOW, the Lutensol XL series of ethoxylated and propoxylated 3-propylheptanol products from BASF, the Lutensol XP series of ethoxylated 3-propylheptanol products from BASF, and the Dehypon series products from BASF.

In addition, the preferred value of methylethoxy y represents only the ratio of methylethoxy to ethoxy, and is not intended to limit the manner in which it is polymerized, either by itself or with ethoxy, as long as the overall value remains desired.

The applicant has found that, during the operation of an automatic dishwasher, the filming and spotting phenomenon is not only influenced by the concentration of metal ions in the washing water, but also the filming and spotting phenomenon of the dirt in the washing process is deposited on the surface of the washed ware, that is, the filming and spotting phenomenon on the surface of the tableware in the actual washing process is often the result of the joint formation of two different kinds of dirt. Notably, applicants have also found that the more stable the soil emulsion produced during the actual wash process, the better its anti-filming and spotting effects on the detergent.

The applicant has found that the ratio of ethoxy groups to methyl ethoxy groups (hereinafter referred to as EO: PO) has a very large effect on the emulsifying properties, because the structure of the hydrophilic groups determines the adsorption speed and adsorption density of the material at the soil/water interface, and that the higher the adsorption speed and adsorption density, which indicates the faster reduction of the soil/water interfacial tension, i.e. the soil can be dispersed into an emulsion with a lower particle size, although the nonionic surfactants are different from the general nonionic surfactants (such as AEO9, which does not contain methyl ethoxy groups), the lower the micelle formation speed and the number of micelle aggregation of micelles, compared to AEO9, but the higher the adsorption speed and adsorption density at the soil/water interface (especially when the applicant claims the hydrophobic chain structure and the two ethoxy ratio ranges of the fast-emulsifying alcohol alkoxylates), which are effective in emulsifying the soil during machine washing, however, the hydrophilicity is too low, so that the emulsion is formed unstably and the emulsion breaking is easily caused. The applicant finds that the addition of the fatty alcohol alkoxylate with low adsorption speed at the dirt/water interface and strong hydrophilicity (particularly the applicant claims the hydrophobic chain structure and the two ethoxyl ratio ranges of the slow emulsifying fatty alcohol alkoxylate) can effectively enhance the stability of the dirt after emulsification. When the technology of the applicant is compounded with a proper scale inhibitor, the scale inhibitor and the scale inhibitor can play a role in synergism, and the compounding of the fast-emulsifying fatty alcohol alkoxylate and the slow-emulsifying fatty alcohol alkoxylate can reduce the dosage of the scale inhibitor and obtain a cost space on the premise of ensuring the anti-filming and anti-spotting performance of the special detergent composition for the automatic dish-washing machine.

In certain embodiments, the fast emulsifying fatty alcohol alkoxylate is selected from the following:

fast-emulsifying fatty alcohol alkoxylate 1: the fast emulsifying fatty alcohol alkoxylate 1 corresponds to the general structural formula of the fast emulsifying fatty alcohol alkoxylate, wherein n has a value of 6, m has a value of 2, x + z has a value of 2, and y has a value of 4.

Fast-emulsifying fatty alcohol alkoxylate 2: the fast emulsifying fatty alcohol alkoxylate 2 corresponds to the general structural formula of the fast emulsifying fatty alcohol alkoxylate, wherein n has a value of 4, m has a value of 2, x + z has a value of 3, and y has a value of 6.

In certain embodiments, the slow emulsifying fatty alcohol alkoxylate is selected from the group consisting of:

slow-emulsifying fatty alcohol alkoxylate 1: the slow-emulsification fatty alcohol alkoxylate 1 conforms to the general structural formula of the slow-emulsification fatty alcohol alkoxylate, wherein the value of n is 4, the value of m is 3, the value of x + z is 8, and the value of y is 0.

Slow-emulsifying fatty alcohol alkoxylate 2: the slow-emulsification fatty alcohol alkoxylate 2 conforms to the general structural formula of the slow-emulsification fatty alcohol alkoxylate, wherein the value of n is 4, the value of m is 3, the value of x + z is 8, and the value of y is 2.

Other surfactants

The special detergent composition for the automatic dishwasher comprises 0.01 to 20 weight parts of other surfactants.

In certain embodiments, the additional surfactant may comprise one or more alkylpolyglycosides having the general formula (a):

in the general formula (a), n is 6 to 24, p is 1.1 to 3, and n is preferably 8 to 16. Suitable alkyl polyglycosides are for example the products of the Glucopon series of alkyl glycosides from BASF.

In certain embodiments, the additional surfactant may comprise one or more fatty acid alkoxylates, preferably ethoxylated C8 to C18 fatty acid esters, with an average degree of ethoxylation of 2 to 10. May contain an ethoxylated alkyl sorbitan ester having an alkyl carbon number of from 6 to 18 and an average degree of ethoxylation of from 4 to 20; a suitable example is the Corda Tween series of products.

In certain embodiments, the additional surfactant may comprise one or more fatty acid alkylolamides, the fatty acid having a carbon number of from 6 to 24, and may be a linear or branched fatty acid, and may be a saturated or unsaturated fatty acid; the alkyl alcohol number is 0 to 2. Monoethanolamide, diethanolamide, isopropanolamide of fatty acids having a carbon number of 8 to 18 are preferred, a suitable example being coconut diethanolamide.

In certain embodiments, the additional surfactant may comprise one or more fatty acid methyl ester ethoxylates of the following general formula (b):

in the general formula (b), n is 6-24; x is 2-20; preferably, n is 8-18, and x is 0.5-30; preferably, x is 4 to 10. A suitable example is the LION company MEE product.

In certain embodiments, the additional surfactant may comprise one or more polyether surfactants.

In certain embodiments, the additional surfactant may comprise one or more of natural oil direct polyoxyethylene and polyoxypropylene. Wherein, the content of the natural oil direct polyoxyethylene and the polyoxypropylene compound is 0.01-20% of the composition, and the natural oil direct polyoxyethylene and the polyoxypropylene compound accord with the following structural general formula (c):

wherein, in the general formula (c), R is aliphatic hydrocarbon with 10-30 carbon atoms, preferably unsaturated hydrocarbon, and the number of unsaturated bonds can be 1-7;

m, m 'and m' can be 0-10, and m, m 'and m' are positive integers;

the sum of m, m 'and m' is 10-30, preferably 10-25, and more preferably 15-25;

(m + m "): m' is 0.2 to 3, preferably 1 to 2.

Wherein n, n 'and n' can be 0-10, and n, n 'and n' are positive integers;

the sum of n, n 'and n' is 10-30, preferably 10-25, and more preferably 15-25;

(n + n "): n' is 0.2 to 3, preferably 1 to 2.

Wherein p, p 'and p' can be 0-10, and p, p 'and p' are positive integers;

the sum of p, p 'and p' is 10-30, preferably 10-25, and more preferably 15-25;

(p + p "): p' is 0.2 to 3, preferably 1 to 2.

The natural oil direct polyoxyethylene and the polyoxypropylene compound can also be a mixture of a plurality of substances meeting the requirements;

suitable natural fats and oils meeting the above conditions are listed below as direct polyoxyethylene and polyoxypropylene,

the MOE-54 is prepared by using soybean oil (fatty acid composition of the soybean oil is 6-8% of palmitic acid, 25-36% of oleic acid, 3-5% of stearic acid, 52-65% of linoleic acid, 0.04-0.1% of arachidic acid and 2.0-3.0% of linolenic acid) as a natural oil raw material to carry out polyoxyethylene and polyoxypropylene, wherein the total number of polyoxyethylene and polyoxypropylene groups is 54, and the ratio of polyoxyethylene to polyoxypropylene is 2: 1.

The natural oil direct polyoxyethylene and the polyoxypropylene are novel ester ether type nonionic surfactants, the raw materials are taken from natural vegetable oil, the solubilizing power to the oil is strong, and the emulsifying property is good; and has the advantages of easy biodegradation, low ecological toxicity, small irritation and the like. More importantly, the tedious process for preparing the detergent alcohol from natural alcohol or synthetic alcohol has been introduced, and the direct polyoxyethylene and polyoxypropylene compound of the natural oil is prepared by directly ethoxylating and polyoxypropylenating the natural oil, so that compared with the traditional nonionic surfactant, the pretreatment process of the detergent alcohol is omitted, the industrial production cost and the three-waste problem are greatly reduced, and the environmental burden of the surfactant production is directly controlled from the source. In addition, because natural oil does not need to be subjected to hydrogenation, saponification and other reactions, the original hydrophobic structure characteristics of the natural oil can be reserved in the direct polyoxyethylene of the natural oil and the fatty alcohol of the polyoxypropylene compound, so that the novel nonionic surfactant has some special functions, such as strong emulsification effect on water-insoluble substances.

Compared with fatty acid methyl ester ethoxylate (FMEE) which has been gradually raised in recent years, natural oil direct polyoxyethylene and polyoxypropylene have the following advantages: (1) has unsaturated bonds, endows the soft hydrophobic chain segment with the hydrophobic chain segment, and is beneficial to improving the interfacial activity. (2) The glycerol backbone, making its hydrophobic segments three times as many as a typical surfactant molecule. The unique structures enable the natural oil and fat to directly complete the adsorption of polyoxyethylene and polyoxypropylene on a two-phase interface more quickly, and then a better washing and decontaminating effect is exerted.

Because the natural oil direct polyoxyethylene and polyoxypropylene compound have the advantage of natural unsaturated bonds, the surfactant is easier to intertwine and fold among molecules. In general, as the concentration of nonionic surfactant increases, the modulus of expansion will be maximized due to the simultaneous and increasing diffusion exchange process and interfacial concentration. This maxima occurs due to diffusion exchange between the interface and the bulk phase. In the research on the variation trend of the expansion modulus and the phase angle of emulsions of Tween60 and Tween80 (the difference between the two is a carbon-carbon double bond), the expansion modulus of Tween80 is greatly higher than that of Tween60, and the phase angle of Tween80 is lower than that of Tween60, which indicates that the nonionic surfactant Tween80 with unsaturated hydrophobic groups forms an interfacial film with stronger elasticity and has stronger interfacial activity than that of a nonionic surfactant with saturated carbon chains, and similarly, natural oil direct polyoxyethylene and polyoxypropylene have the advantages compared with a common nonionic surfactant.

In addition, it is also considered that the nonionic surfactant having an unsaturated bond hydrophobic structure has a stronger intermolecular interaction in the research of the interfacial discipline. In a low concentration range, both the saturated hydrophobic group and the unsaturated hydrophobic group extend into the oil phase, and the polyoxyethylene group extends into the water phase; as the interfacial concentration increases before CMC (in the intermediate concentration range), the nonionic surfactant molecules become tightly adsorbed on the interface and the oxyethylene groups form a stable sublayer, which controls the rheological behavior, resulting in increased modulus and decreased phase angle. But further increase in concentration beyond the CMC concentration (in the high concentration range), the non-ionic surfactant adsorption at the interface becomes saturated, leading to a drastic decrease in modulus with a significant increase in phase angle due to the new relaxation process, i.e., the faster exchange process contribution between the interface layer and the micelles near the interface increases. In the whole process of increasing the concentration of the surfactant molecules, the molecules B with unsaturated hydrophobic groups are more flexible and are easier to crosslink and intertwine, so that the nonionic surfactant molecules with unsaturated hydrophobic groups can form a more stable interfacial film, and the emulsifying capacity and the emulsifying stability of the nonionic surfactant molecules with unsaturated hydrophobic groups are stronger than those of the common nonionic surfactant molecules with saturated hydrophobic groups.

The natural oil direct polyoxyethylene and the polyoxypropylene product with an unsaturated bond structure are used for replacing a conventional nonionic surfactant with a saturated hydrophobic group, so that stronger interfacial activity and interfacial stability can be effectively provided, the dirt-removing capability of a detergent composition is stronger, and even a certain capability of preventing dirt from redepositing is provided to reduce the addition amount of a polymer, so that the natural oil direct polyoxyethylene and the polyoxypropylene product have great advantages compared with the conventional nonionic surfactant, especially fatty alcohol polyoxyethylene ether which is widely applied in the industry at present.

Copolymer dispersants

The content of the copolymer dispersant is 0.1-30 parts by weight of the special detergent composition for the automatic dishwasher.

The repeating unit of the copolymer dispersant is selected from the group consisting of residues after polymerization of an unsaturated monomer A, an unsaturated monomer B and an unsaturated monomer C, and satisfies the following relationship:

2) the unsaturated monomer A of the copolymer dispersant comprises 70 to 99.99 weight percent of unsaturated monomer A1, and comprises 0.01 to 30 weight percent of unsaturated monomer A2;

3) the unsaturated monomer A1 of the copolymer dispersant is selected from monomers containing one carboxylic acid group and only one unsaturated double bond, and comprises: acrylic acid, methacrylic acid, alpha-hydroxyacrylic acid, alpha-hydroxymethylacrylic acid, crotonic acid; the carboxylic acid group of the unsaturated monomer A1 of the copolymer dispersant exists in the copolymer dispersant in the form of salt, specifically monovalent metal salt, divalent metal salt and ammonium salt, and organic ammonium salt;

4) the unsaturated monomer A2 of the copolymer dispersant is selected from monomers containing more than one carboxylic acid group and only one unsaturated double bond, and comprises: maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid.

6) the unsaturated monomer B of the copolymer dispersant is selected from monomers containing one sulfonic acid group and only one unsaturated double bond, and specifically comprises the following components: the copolymer dispersant comprises a vinyl monomer containing a sulfonic acid group, an allyl monomer containing a sulfonic acid group, a (meth) acrylamide containing a sulfonic acid group, and a (meth) acrylate containing a sulfonic acid group, wherein the sulfonic acid group of an unsaturated monomer B of the copolymer dispersant exists in the form of a salt in the copolymer dispersant, specifically a monovalent metal salt, a divalent metal salt, an ammonium salt, and an organic ammonium salt;

7) the unsaturated monomer B of the copolymer dispersant is specifically selected from: vinylsulfonic acid, styrenesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, allylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-allyloxy) propanesulfonic acid, 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate;

8) the residue of the unsaturated monomer C of the copolymer dispersant accounts for 0.1 to 20 percent of the weight of the copolymer dispersant;

9) the unsaturated monomer C of the copolymer dispersant is selected from monomers containing one unsaturated double bond, and specifically comprises the following components: unsaturated monomer C1, unsaturated monomer C2, unsaturated monomer C3;

10) the unsaturated monomer C1 of the copolymeric dispersant is selected from compounds corresponding to the following general formula (4):

in the general formula (4), R₁One or more selected from hydrogen and methyl, and n is a positive integer from 2 to 8;

11) the unsaturated monomer C2 of the copolymer dispersant is selected from acrylamide, benzyl methacrylamide, cyclohexyl methacrylamide, tert-butyl acrylamide, methacrylamide, dimethylacrylamide, dimethylaminopropyl methacrylamide;

12) the unsaturated monomer C3 of the copolymeric dispersant is selected from compounds corresponding to the following formula (5) and/or the following formula (6):

r in the general formula (5)₁One or more selected from hydrogen and methyl, R₂Is a saturated alkyl group having 2 to 8 carbon atoms;

in the general formula (6), R₁One or more selected from hydrogen and methyl, R₃One or more selected from hydrogen, methyl and ethyl, R₄Selected from hydrogen, saturated alkyl with carbon number of 1-20, and m is a positive integer of 1-30.

13) The molecular weight of the copolymer dispersant is 1000-150000, preferably 2000-100000;

copolymer dispersants meeting the above requirements may use copolymer dispersants already commercialized such as: the DOW company Acusol series and the BASF company Sokalan series.

In certain embodiments, the copolymer dispersant is selected from the group consisting of:

copolymer dispersant 1: the copolymer dispersant conforms to the structural general formula of the copolymer dispersant, wherein the unsaturated unit A is 65% of acrylic acid and 5% of maleic acid, the unsaturated monomer B is 20% of 2-acrylamido-2-methylpropanesulfonic acid, the unsaturated monomer C is 10% of hydroxyethyl acrylate, and the molecular weight of the polymer is about 6500.

Copolymer dispersant 2: the copolymer dispersant conforms to the structural general formula of the copolymer dispersant, wherein the unsaturated unit A is 70 percent of acrylic acid, the unsaturated monomer B is 20 percent of 2-acrylamido-2-methylpropane sulfonic acid, the unsaturated monomer C is 10 percent of hydroxypropyl acrylate, and the molecular weight of the polymer is about 8300.

Anti-filming and anti-spotting mechanism of copolymer dispersions

A hard water film due to calcium and magnesium ions during dishwashing is an undesirable result. The insoluble scaling substance formed by sulfate, carbonate, phosphate and the like and metal ions is effectively inhibited by adding the washing assistant, so that the scaling substance is prevented from being on the surface of the objectA film and stains are formed. The content of hard water ions in water is called the hardness of water and is expressed in mg/kg (as CaCO)₃Calculated), and may also be expressed in ppm. Generally, natural water sources flowing through limestone areas have a high hardness; for example, groundwater hardness in inner Mongolia regions is 400ppm and natural water hardness in Australia is about 1000 ppm. The greater the hardness of the water, the greater the impact on the detergent composition.

In addition, some divalent metal ions are sometimes artificially added to detergent formulations from the standpoint of certain components of the detergent. For example, methylisothiazolinone derivatives are commonly used in detergent products as preservatives, and magnesium ions are sometimes used as stabilizers to increase their stability. The enzyme preparation is also a common component in the washing products, and calcium ions are sometimes added into the washing products as a stabilizing agent in order to increase the stability of the enzyme preparation. These divalent cations may also have some effect on the washing performance, even leading to precipitation and crystallization of insoluble carbonates.

Calcium carbonate is the most common of the insoluble structures. In solution, calcium carbonate is typically formed by the formation of a supersaturated solution of calcium carbonate in solution with carbonate ions and calcium ions, followed by precipitation, which proceeds through a pre-nucleation stage, a crystal nucleation stage, an early stage of crystal growth after nucleation, and a crystallization stage. Other components in the solution, pH value, temperature and ionic strength have important influence on the nucleation and crystal growth of calcium carbonate crystals.

Among the several forms of calcium carbonate, the calcite form is the most stable, but also the most difficult to remove. From the viewpoint of removing the scale, it is also of great significance to effectively control the crystal form of calcium carbonate produced in the solution to a non-calcite crystal form. When phosphate, carboxylate, anionic polyelectrolyte type is present in the solution, these substances have a significant influence on the generation of calcium carbonate nuclei and the growth of crystals. Different substances have different effects on calcium carbonate crystals, some substances such as polyaspartic acid (PAsp) can promote the calcium carbonate in a solution to be finally converted into a certain crystal form such as an aragonite type, and are called as crystal form regulators, and some substances such as polymers containing carboxyl groups can obviously inhibit the generation rate of the calcium carbonate, and are called as calcium carbonate inhibitors. There is a great deal of work being put into play around the mechanism of action of inhibitors on the production and growth of calcium carbonate crystals, and current research is inclined towards the principle of action of inhibitors including: 1. the inhibitor combines with calcium ions to produce a complex, thereby inhibiting the nucleation of calcium carbonate crystals. 2. The inhibitor stabilizes the precore cluster (precore) of calcium carbonate, thereby inhibiting the nucleation of calcium carbonate crystals. The pre-core cluster is the minimum unit of calcium carbonate stably existing in a solution, the pre-core cluster is further aggregated to form an amorphous aggregate, and the aggregate is further converted into a crystalline micro-domain and then grows into a crystal. 3. The inhibitor stabilizes the particles by binding to the surface of the precursor particles of nano-sized calcium carbonate (crystals), thereby inhibiting further growth of calcium carbonate crystals.

It is believed that the addition of a polymer containing carboxylate groups allows for a significant delay in nucleation of calcium carbonate, with the induction period increasing with increasing carboxylate content. In the early stage of the crystal growth stage (post nucleation stage) in the late nucleation stage, the hydrodynamic radius of the aggregates in the solution increases linearly with time and eventually converges to a certain saturation value. Therefore, it is considered that the inhibition of calcium carbonate nucleation by the polymer is mainly achieved by stabilization of the aggregates (pre-core clusters). Especially when the concentration of the inhibitor is much lower than that of calcium ions in the solution, even if the functional groups (carboxyl, phenolic, sulfonic) of the inhibitor are all combined with calcium ions in a 1:1 manner, the solution contains a large amount of free calcium ions, and therefore the inhibition effect mainly does not come from the complexation of the functional groups and the calcium ions. But rather, the functional groups (carboxyl, phenolic group and sulfonic group) are adsorbed on the interface of the new calcium carbonate crystal, so that the growth sites of the calcium carbonate are interrupted, and further growth of the calcium carbonate is inhibited. The difference in the adsorption capacity of the functional groups is represented by the length of the induction time and the degree of inhibition.

The polycarboxylate has strong binding effect on calcium ions in aqueous solution, the 'bridging' effect of a part of calcium ions in the solution causes the electrostatic repulsion between carboxylate radicals of the polymer to be weakened, and the conformation of the polymer is gradually changed from stretching to winding and is adopted to be more compact. Thus, although part of the calcium ions in the solution have been bound by the polycarboxylate, the polymer cannot further bind the rest of the calcium ions in the solution, and at the same time, cannot effectively stabilize aggregates (e.g., growing calcium carbonate pre-nuclear clusters) and particulates in the solution, and may even gel due to a decrease in hydrophilicity; and thus still results in the continued production and growth of calcium carbonate crystals. The polycarboxylate is too strong due to the binding of the carboxylate to the particle surface, leaving only a small amount of carboxylate ions to provide electrostatic repulsion. Less electrostatic repulsion is detrimental to the separation of particles from one another, particles and substrate surface.

Therefore, much research has focused on chemical modification of polycarboxylates. Copolymerization is the most common method of modification. The novel chemical properties of the polycarboxylates are imparted by the polymers of unsaturated monocarboxylic acids and second/third monomers, the types and roles of the common polymeric monomers are shown in Table 1 below.

Table 1 types and roles of the common Polymer monomers

Numerous patent documents, such as US3332904, US3898037, US6395185, CN102197125A, CN102197127, etc., report polymers containing both sulfonate groups and carboxylate groups. The sulfonate has only weak adsorption effect on the surface of the particle, and the exposed sulfonate is enriched on the surface of the particle to endow the particle with certain electronegativity. The introduction of sulfonate groups greatly increases electrostatic repulsion between the polymer-bound particles, thereby reducing particle agglomeration and deposition on the substrate surface. In addition, compared with the sulfonate and the carboxylate, the sulfonate has stronger polarity, can endow the polymer with stronger water solubility in a wider pH value range, and is suitable to be used as a scaling agent in the field of household washing. Thus, for polymers containing sulfonate, carboxylate groups, the weight proportion of residues containing sulfonate groups is not recommended to exceed 50%. The content of carboxylate radical in the polymer is above 50%, so that the polymer has the chelating capacity of calcium ion and good water solubility.

Japanese catalyst corporation in CN101952351A examined the relationship between the molecular weight and the performance of the copolymer. The copolymer composition comprises unsaturated monomers I comprising dicarboxylates, such as maleic acid (anhydride); monocarboxylated unsaturated monomers II, such as acrylic acid. The unsaturated monomer III containing sulfonate is 3-allyloxy-2-hydroxy-1-propanesulfonate (HAPS). Higher molecular weight has strong calcium ion capturing ability, and lower molecular weight increases the dispersing ability for hydrophilic dirt. The copolymer is ultimately used in a laundry powder composition. The patent application of a polymer containing sulfonate group in CN102197125A and CN102197127 by Procter & gamble company for washing and decontaminating high hardness water can effectively inhibit the deposition of a surfactant and resist the gelation. By surfactant deposit is meant a precipitate formed by anionic surfactant and hard water ions. CN102197127 reports copolymers comprising unsaturated monomers I containing ethylene oxide repeating units; the unsaturated monomer II containing carboxylate, such as acrylic acid, and the unsaturated monomer III containing sulfonate is 3-allyloxy-2-hydroxy-1-propanesulfonate. The polymer containing sulfonate groups was claimed by proclaim company CN102197125A to be particularly suitable for use in high hardness water environments. AA/AMPS copolymers having an average molecular weight of 150 ten thousand or more are reported in Kao corporation in patent CN 100503802C. The high molecular weight copolymer gives a smooth touch to the object to be cleaned at a usual washing concentration, and is suitable for hand washing.

The length of the molecular chain of the polycarboxylate, the number of carboxylic acid groups and the form of the molecule in the solution all influence the washing-assistant performance of the polycarboxylate. In general, polycarboxylic acid polymers are effective on suspended solid particles such as carbon black, but have relatively poor dispersibility on hydrophobic oily stains such as sebum. Some documents improve the dispersing efficiency of polycarboxylates on hydrophobic soils by introducing ester-based unsaturated monomers.

US4029577, US4499002, japanese patent publication 61-107997, 61-107992 report structures of acrylic acid and nonionic unsaturated monomers (hydroxyalkyl acrylates, acrylamides, alkoxyalkyl alcohol esters of acrylic acid) for inhibiting silicate production. The nonionic unsaturated monomer improves the binding capacity of the polymer to silica scale. Although the overall charge density of the polymer is reduced compared to the polyacrylic (sodium) homopolymer, the antiscalant performance (which is manifested as hard water film resistance) is significantly increased.

A problem often encountered in the automatic dishwasher industry relates to the formation and accumulation of solid deposits, often referred to as "scaling", on the items being washed. The daily water supply may contain alkaline earth metal cations such as calcium, magnesium, iron, copper, barium, zinc, etc., and some anions such as bicarbonate, carbonate, sulfate, phosphate, silicate, fluoride, etc. When these combinations of cations and anions are present in concentrations exceeding the solubility of their reaction products, solid precipitates form and accumulate on the items being cleaned. For example, when the ionic product of magnesium and silicate exceeds the solubility of magnesium silicate, solid magnesium silicate will form and accumulate on the surfaces of dishes, pots, flatware, plastic tableware, glass containers, pans, and silverware, resulting in unsightly films or stains on the cleaned items. Moreover, if the concentration of these substances approaches or exceeds the solubility limit, scale may form on the material. The mechanism by which the metal ions combine with the anions to form a soil on the surface of the substrate can be attributed to homogeneous nucleation and/or heterogeneous nucleation, which is common knowledge in the field of aquatic chemistry. More often, heterogeneous nucleation is encountered in the automatic dishwasher industry because the conditions required for homogeneous nucleation are harsh, whereas the soil concentration for heterogeneous nucleation is much lower than for homogeneous nucleation.

Automatic dishwasher detergents are generally considered to be a class of detergents other than fabric cleaning or water treatment agents. After a cleaning cycle is completed in an automatic dishwasher, the excellent automatic dishwasher detergent is effective in preventing metal ions and anionic deposits from forming films and/or spots on glassware, ceramic tableware, plastic tableware and containers, silverware, flatware, fine porcelain, cookware, and other common surfaces being cleaned.

It is worth noting that even though the mechanism of film and/or spot formation on the surface being cleaned by metal ions and anionic precipitates is heterogeneous nucleation, the film and spot formation factors are different. Generally, the metal ions and anion precipitates exist in the form of film or spots depending on the size of their solubility product in water, which is affected by the chelating agent and the scale inhibitor. Notably, applicants have unexpectedly found that the nonionic unsaturated monomers, chain length, and/or molecular weight distribution of the polymer can also have an effect on conjunctiva and plaque formation.

Amino acid derivative chelating agents

The content of the amino acid derivative chelating agent is 0.1-40% of the special detergent composition for the automatic dishwasher.

The amino acid derivative chelating agent may be methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA), N-dicarboxamido-2-hydroxypropanesulfonic acid, 3-hydroxy-2, 2' -iminodisuccinic acid, aspartic acid-N-monoacetic acid (ASMA), aspartic acid-N, N-diacetic acid (ASDA), aspartic acid-N-monopropionic Acid (ASMP), iminodisuccinic acid (IDA), N- (2-sulfomethyl) -aspartic acid (SMAS), N- (2-sulfoethyl) aspartic acid (SEAS), N- (2-sulfomethyl) glutamic acid (SMGL), N- (2-sulfoethyl) glutamic acid (SEGL), N-methyliminodiacetic acid (MIDA), alpha-alanine-N, n-diacetic acid (alpha-ALDA), beta-alanine-N, N-diacetic acid (beta-ALDA), serine-N, N-diacetic acid (SEDA), isoserine-N, N-diacetic acid (ISDA), phenylalanine-N, N-diacetic acid (PHDA), anthranilic acid-N, N-diacetic acid (ANDA), sulfanilic acid-N, N-diacetic acid (SLDA), taurine-N, N-diacetic acid (TUDA) and sulfomethyl-N, N-diacetic acid (SMDA) and alkali metal or ammonium salts thereof. In this document, it is also referred to as a chelating agent or green chelating agent.

The alkali metal salt of the amino acid derivative chelating agent may be selected from lithium salts, preferably potassium salts, more preferably sodium salts.

Detergent composition compositions specific for automatic dishwashers have to meet a number of requirements. They need to have excellent cleaning properties on various cooking soils, including removal of organic materials such as milk soils, oily soils, egg residues, meat residues, and the like. Automatic dishwasher detergent tablets not only need to cope with hard water of different hardness, but also have environmental-friendly characteristics, so that automatic dishwasher detergent tablets containing phosphate-based chelating agents have not been accepted by society.

It has been shown that certain chelating agents compete for the central Ca bound to the active site of the enzyme preparation²⁺Metal ions, thereby reducing the activity of the enzyme preparation and its active shelf life. Therefore, how to screen for proper chelating agents is very important for washing tablets by adding enzyme.

The present invention relates to a detergent composition for automatic dish washer added with specific chelating agent, which is environment friendly and has good removing effect on milk residue, egg residue, starchy residue and pesticide residue, and can maintain 50% of enzyme activity after storing at about 30 deg.C, or about 35 deg.C, or about 37 deg.C for several weeks or more.

The scale bodies are mostly crystalline, such as calcium carbonate, CaCO₃Having an ionic lattice of positively charged Ca²⁺With negatively charged CO₃ ^2-Combine with each other when colliding, and have hard scale strictly arranged in a certain direction. For Ca after addition of chelating agent²⁺The chelation of (2) inhibits the growth of crystal lattice in a certain direction, CaCO₃The crystal structure of the hard scale is distorted and does not grow further according to the normal rule, and larger amorphous particles are produced, wherein the larger amorphous particles are partially adsorbed on the crystal and enter the crystal lattice along with the growth of the crystal, and the larger amorphous particles are CaCO₃The crystal is dislocated, and some cavities are formed in the scale layer. Even if part of the crystal grows up, a compact scale layer is difficult to form, thereby CaCO₃The hard scale is changed into soft scale and is easy to be washed away by water flow.

Silicon and silica scale

The types of silicon in water in nature can be classified into three types, namely dissolved silicon, colloidal silicon and micro-particle silicon. Dissolved silicon is silicic acid (H) formed by silicon in water₄SiO₄) A compound; the colloidal silica is silica colloidal scale formed by hydrogen absorption condensation and dehydration condensation of silicic acid in water to form a silica gel mass space structure and then continuous dehydration; particulate silicon is the larger particles formed by the combination of silicon and the particulate suspension in water.

The content of dissolved silicon in water is usually SiO₂Is measured by mass concentration of (a). The water in nature contains about 6 to 120ppm of silicon. The solubility limit of silicon at 25 ℃ is approximately 120 ppm. When the silicon content in the water exceeds a limit value, colloid is formed or combined with other ions to form a silicate state, and then silicon scale is separated out and formed.

Silica scale commonly found in water generally exists in two states, one is silicic acid polymerization state or silica gel group amorphous state, called as colloidal silica, and its structural formula can be expressed as xHSiO₂.yH₂And O. The colloidal silica is generally composed of a single molecule of ortho-silicic acid or SiO₂Polymerized and is stable in water. It is worth noting that when the pH is about 7, the silicic acid molecules are not substantially ionized, and remain in a molecular state; when the pH is about 8.5, about one tenth of molecules in silicic acid are ionized; at a pH of about 10, about half of the silicic acid is ionized. When the silicon in the water is excessive, SiO is formed₂SiO of this kind₂Is amorphous and then suspended in the form of colloidal particles in water. This is commonly referred to as colloidal or suspended silicon. The colloidal silica exists in a molecular polymerization state or a particle attachment state in water mostly, and the diameter is generally 1-100 μm.

Another form of silica scale is silicate scale, commonly CaSiO₃、MgSiO₃And the like are hardly soluble salts. Silicate scale is generally dense in structure, and after formation, the silicate scale is tightly attached to the wall of equipment and is not easy to remove. The mechanism of scale formation is as follows: in an alkaline environment, Ca²⁺、Mg²⁺With OH^-Binding to form Ca (OH)₂And Mg (OH)₂The corresponding hydroxide is then combined with silicate ions to finally become silicate scale.

It is noted that the working environment of the automatic dishwasher is generally an alkaline environment, and the pH value is 9-13.

Enzyme preparation

The detergent compositions provided herein for use in automatic dishwashing machines may comprise one or more enzyme formulations to provide cleaning performance, fabric care and/or other benefits. The enzyme preparation is selected from the following enzyme groups: proteases, alpha-amylases, cellulases, hemicellulases, phospholipases, esterases, lipases, peroxidases/oxidases, pectinases, lyases, mannanases, cutinases, reductases, xylanases, pullulanases, tannases, pentosanases, maltosanases, arabinases, beta-glucanases. Commonly used enzyme preparations are proteases, amylases, lipases, cutinases and/or cellulases. The content of the enzyme preparation is 0.1-10% of the special detergent composition for the automatic dishwasher.

The detergent composition for automatic dish washer of the present invention may comprise: an enzyme stabilizing system accounting for 0.001-10% of the weight of the composition. The enzyme stabilizing system is compatible with detergent compositions and may comprise one or more mixtures of calcium ions, boric acid, borax, propylene glycol, glycerol, polyols. The weight and amount of the enzyme stabilizing system will vary depending on the form and composition of the detergent composition and the type of enzyme preparation.

Detergent composition-enzyme preparation special for automatic dish-washing machine

The special detergent composition for the automatic dishwasher, namely the enzyme preparation, refers to the common enzyme preparation for preparing the detergent composition, and the enzyme preparation comprises one or a mixture of more of various amylases, various lipases, various proteases, various cellulases and various hemicellulases.

In certain embodiments, the detergent compositions provided by embodiments of the present invention comprise amylase.

Examples of amylases which can be formulated according to the invention are alpha-amylases from Bacillus licheniformis (Bacillus licheniformis), Bacillus amyloliquefaciens (Bacillus amyloliquefaciens) or Bacillus stearothermophilus (Bacillus stearothermophilus) and more particularly further developed products which improve them for use in washing or cleaning compositions and dishwashing detergents. Enzymes from Bacillus licheniformis are available from the Termamyl series of enzyme preparation products from Novozymes corporation. Alpha-amylases from Bacillus amyloliquefaciens are sold by Novozymes under the name BAN, and variants of alpha-amylases from Bacillus stearothermophilus are also sold by Novozymes under the names BSG and Novamyl. In addition, particular attention should be paid to the alpha-amylase from Bacillus A7-7(DSM12368) and the cyclodextrin glucanotransferase (CGTase) from Bacillus agaradherens (DSM 9948) for this purpose. Fusion products of all the indicated molecules can likewise be used. In addition, further developments of alpha-amylases from Aspergillus niger and Aspergillus oryzae (A. oryzae) obtainable from Novozymes in the Fungamyl series are also suitable. More preferably, alpha-amylases of Amylase-LT, Stainzyme, Stainymeultra, Stainzyme plus and Achieve series available from Novozymes are used, and alpha-amylases of Preferenz series and Excellenz series available from Dupont are also suitable.

The amylase enzyme preparation is present at a level of from 0.2% to 5% of the first detergent composition. Meanwhile, the first detergent composition can also comprise an enzyme stabilizing system which accounts for 0.001-10% of the weight of the first detergent composition. The enzyme stabilizing system is compatible with detergent compositions and may comprise at least one of calcium ions, boric acid, borax, propylene glycol, glycerol, and polyols. The weight and amount of the enzyme stabilizing system will vary depending on the form and composition of the detergent composition and the type of enzyme preparation.

In certain embodiments, the detergent compositions provided by embodiments of the present invention comprise a protease.

The proteases of the invention include those of bacterial, fungal, plant, viral or animal origin, for example of plant or microbial origin. Preferably of microbial origin. Chemically modified mutants or protein engineered mutants are included. It may be an alkaline protease, such as a serine protease or a metalloprotease. The serine protease may be trypsin or subtilisin. The metalloprotease may be thermolysin or another metalloprotease. Commercially available proteases suitable for the above conditions include the enzyme preparation products sold under the following trade names, including: alcalase, Duralase, Duralym, Relass Ultra, Savinase, Savinase Ultra, Primase, Polarzyme, Kannase, Liquanase, Liquanase Ultra, Ovozyme, Coronase Ultra, Neutase, Everlase and Esperase series products from Novozymes corporation; maxase, Maxacal, Maxapem, Purafect, Purafect Prime, Purafect MA, Purafect Ox, Purafect OxP, Puramax, Properase, FN2, FN3, FN4, excelase, Eraser, Opticlean, Blaze, Progress, Excellenz and Optimase series products from Danisco and Dupont.

The protease preparation is contained in an amount of 0.2% to 5% of the first detergent composition. Meanwhile, the composition can also comprise an enzyme stabilizing system which accounts for 0.001-10% of the weight of the first detergent composition. The enzyme stabilizing system is compatible with detergent compositions and may comprise at least one of calcium ions, boric acid, borax, propylene glycol, glycerol, and polyols. The weight and amount of the enzyme stabilizing system will vary depending on the form and composition of the detergent composition and the type of enzyme preparation.

Additive agent

The detergent composition special for the automatic dishwasher comprises the following optional additives: one or more of a filler, an alkaline agent, a viscosity regulator, a preservative, a colorant, a color stabilizer and an essence.

In certain embodiments, the detergent composition provided by the present invention may comprise one or more alkaline agents selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium salts of ethylenediaminetetraacetic acid, alkali metal carbonates, alkali metal silicates.

In certain embodiments, the detergent compositions provided herein may comprise one or more fillers selected from sodium citrate, sodium sulfate, sodium chloride, potassium chloride, water, preferably sodium sulfate and sodium citrate.

In certain embodiments, the automatic dishwasher specific detergent compositions provided herein may comprise one or more viscosity modifiers to provide a suitable viscosity. Suitable viscosity modifiers are, for example, salts, polysaccharides, gums, short-chain fatty alcohols, short-chain fatty alcohol alkyl ethers. Suitable examples are sodium chloride, ethanol, propylene glycol, sodium citrate, alkyl hydroxyalkyl cellulose ethers, carrageenan, xanthan gum, polyacrylamide derivatives.

In certain embodiments, the automatic dishwasher specific detergent compositions provided herein may comprise one or more bleaching systems. The bleaching system comprises hypohalite bleach, peroxide bleach. Peroxides typically comprise a source of hydrogen peroxide and a bleach activation system. Sources of hydrogen peroxide include, but are not limited to, perborates, percarbonates, persulfates, and mixtures thereof. In some embodiments, the preferred hydrogen peroxide source is sodium percarbonate. The bleaching system may comprise a bleach activator for promoting rapid decomposition of peroxide at lower temperatures to generate oxygen selected from the group consisting of: tetraacetylethylenediamine, benzoylcaprolactam, 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate, nonanoyloxybenzenesulfonate, phenyl benzoate, decanoyloxybenzenesulfonate, benzoylvalerolactam, octanoyloxybenzenesulfonate, transition metal bleach catalysts.

In some embodiments, the detergent composition may further comprise a reactive oxygen species stabilizer for adjusting the rate of hydrogen peroxide generation by peroxide decomposition so that the local concentration of hydrogen peroxide is not too high, and examples of the suitable stabilizer are polyfunctional organic phosphoric acids such as hydroxyethylidene diphosphate and ethylenediamine tetramethylene phosphate. In some embodiments, the bleaching system is present at a level of from 0.01% to 30%, preferably from 0.01% to 20%, and more preferably from 0.01% to 10% by weight of the total detergent composition.

In certain embodiments, the automatic dishwasher specific detergent compositions provided herein may comprise one or more corrosion inhibitors which provide corrosion benefits to glass and/or metal, and the term encompasses agents used to prevent or reduce the staining of non-ferrous metals, particularly silver or copper.

It is known to include sources of multivalent ions in detergent compositions specific for automatic dishwashers for the benefit of corrosion protection. For example, multivalent ions, particularly silver, copper, zinc, bismuth, and/or manganese ions, are included for their ability to inhibit such corrosion. Suitable inorganic redox active materials may be metal salts and/or metal complexes of zinc, bismuth, manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and/or complexes, the metal being in one of the oxidation states II, III, IV, V or VI. Particularly suitable metal salts and/or metal complexes are selected from the group consisting of MnSO₄Manganese (II) citrate, manganese (II) stearate, manganese (II) acetylacetonate and [ 1-hydroxyethane-1, 1-diphosphonic acid]Manganese (II) and V₂O₅、V₂O₄、VO₂、TiOSO₄、K₂TiF₆、K₂ZrF₆、CoSO₄、Co(NO₃)₂Zinc acetate, zinc sulfate and Ce (NO)₃)₃A group of which. Any suitable source of multivalent ions may be used, preferably selected from the group consisting of sulfates, carbonates, acetates, gluconates, and metal protein compounds. Zinc salts are particularly preferred corrosion inhibitors.

Preferred silver/copper corrosion inhibitors are Benzotriazole (BTA) or dibenzotriazole and substituted derivatives thereof. Other suitable agents are organic and/or inorganic redox-active substances and paraffin oils. Benzotriazole derivatives are those compounds in which the available substitution sites on the phenyl ring are partially or fully substituted. Suitable substituents are straight or branched C1-20 alkyl and hydroxy, thio, phenyl or halogen (such as fluoro, chloro, bromo and iodo). The preferred substituted benzotriazole is methylbenzotriazole.

In certain embodiments, the automatic dishwasher specific detergent compositions of the present invention may comprise any conventional amount of corrosion inhibitors. However, the amount added is preferably 0.01 to 5%, preferably 0.05 to 3%, more preferably 0.1 to 2.5%, based on the total weight.

In some embodiments, the present invention relates to automatic dishwasher specific detergent compositions comprising a colorant comprising a dye and a pigment. The coloring agent includes all coloring agents used in washing products, and suitable examples are acid scarlet G, basic fuchsin, acid golden G, acid bright yellow G, basic egg yolk, direct fast blue B2RL, indigo, and the like.

In some embodiments, the present invention relates to detergent compositions specific for automatic dishwashers comprising a color stabilizer. Color stabilizers include all color stabilizers that can be used in laundry products.

In certain embodiments, the detergent compositions specific for automatic dishwashers to which the present invention relates preferably contain perfume, which comprises all perfume ingredients suitable for use in laundry products. The fragrances used in the present invention may be of natural origin, or may be chemically synthesized, or a mixture of both. Suitable examples are lemon, rose, jasmine, lavender, citrus, green, costus root etc.

In addition to the above optional ingredients, the detergent composition for automatic dish washer of the present invention may further comprise various general and conventional additives such as water, organic solvent, co-solvent, solubilizing agent, structuring agent, foam promoter, foam inhibitor, fabric softener, anti-wrinkle agent, etc. These additives and the associated methods of use are well known to those skilled in the art, and the particular type and amount of such additives can be selected and adjusted to the particular needs.

Methods of formulation and use

The detergent tablet compositions of the present invention are prepared by various methods well known to those skilled in the art. The formulation of the composition may be carried out by conventional means, and the appropriate processing temperature and processing time will be selected with reference to the state and effect of the components in solution, and the stability of the components.

The detergent compositions of the present invention are useful in a manner well known to those skilled in the art, and typically are used by contacting the particular detergent composition embodiment with the surface of the item to be laundered, either undiluted or diluted in water, and then rinsing the surface of the item to be laundered. Preferably, the articles to be washed are subjected to a washing step between the above-mentioned contacting step and the rinsing step. The washing step includes, but is not limited to, scrubbing and mechanical agitation. The washed objects comprise fabrics and tableware. The detergent composition has a concentration of from about 500ppm to 10000ppm in water, preferably from 5 ℃ to about 60 ℃. The ratio of water to laundry is preferably about 1:1 to about 20: 1. of course, the detergent compositions of the present invention may also be used according to the description of the specific operating instructions of the dishwasher in relation to detergent addition.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following examples are intended to further describe and demonstrate embodiments within the scope of the present invention. The examples are therefore to be understood as merely illustrative of the invention in more detail and not as limiting the content of the invention in any way. In the following examples, all amounts are by weight unless otherwise indicated, and the amounts of the listed ingredients are converted to active material amounts.

Preparation method of special detergent composition for liquid automatic dish-washing machine

) Firstly, adding process water into a batching pot;

2) slowly adding a thickening agent while stirring, and adjusting the pH to 6-9 after fully dispersing;

3) adding the chelating agent component, the polymer component, the alkaline assistant and the surfactant in sequence, and stirring uniformly;

4) adding essence into the mixing pot, and stirring uniformly;

5) adding other auxiliary agents into the batching pot, and uniformly stirring;

6) standing for a period of time, and then recovering to normal temperature.

Preparation method of special detergent composition for powder automatic dish-washing machine

1) Firstly, adding a filling agent into a proportioning pot;

2) adding the chelating agent, the scale inhibitor and the surfactant in sequence under stirring, and uniformly stirring;

3) adding a defoaming agent, an oxidant and an activating agent thereof, and uniformly stirring;

4) adding essence and enzyme preparation into the mixing pot, and stirring uniformly;

5) adding other additives into the batching pot, and uniformly stirring;

6) and (3) continuously and fully stirring the materials in the proportioning pot to ensure that no caking or agglomeration phenomenon exists, sieving the uniformly mixed materials (20-80 meshes), and packaging after the materials are qualified through inspection.

Preparation method of detergent composition special for sheet-shaped automatic dishwasher

The detergent compositions described herein may also be prepared as detergent tablets, especially multi-phase detergent tablets, comprising:

1) a first phase having a smooth upper surface, or the upper surface may be slightly convex or concave, the difference in height between the highest and lowest points of the upper surface being 1mm to 5 mm;

2) a second phase bonded to and partially covering the upper surface of the first phase.

The present invention also provides a process for preparing the above tablet comprising the step of binding said second phase to said first phase.

The tablets of the present invention retain the advantages of the commercially available tablets. The second phase can be readily formed into a shape that appears as a sphere (or other shape formed by compression) protruding from the upper surface of the tablet. Furthermore, the different phases of the tablet may still contain incompatible components, or components which are desired to be released into the wash liquor at different times. Second, if desired, the second phase can be formed into a different shape that is not easily placed into the cavity. Since the second phase does not have to be placed exactly in the cavity, a slight deviation does not hinder the implementation of the solution when it is placed on the surface of the first phase. Even a slight deviation in the placement of the second phase will not result in its separation from the first phase. If the accurate placement position of the second phase cannot be ensured, the height difference between the highest point and the lowest point of the upper surface of the first phase is reduced, and the optimal height difference is 1-3 mm.

The first phase of the multi-phase detergent tablet may be of any shape as long as it has a flat or substantially flat upper surface in combination with the second phase. The first phase may have, for example, a circular, elliptical or rectangular cross-section. Desirably the tablet is rectangular block or cylindrical. The first phase may be formed by compression, for example, by compression in a powder or granular composition tablet press. The first phase may also be shaped by casting or extrusion, for example. The first phase may contain one or more layers of different compositions if desired, and may itself contain one or more inserts of different compositions.

The second phase of the multi-phase detergent tablet may also be of any shape including, but not limited to, spherical, tablet, oval.

The upper surface of the first phase is flat or substantially flat. By "flat" we mean that the upper surface has a substantially continuous profile without any unfilled cavities. However, the upper surface may be rough, since the composition forming the first phase is granular. The upper surface may be smooth, optionally with chamfered edges, or may have a rounded surface with a natural transition.

The second phase is prepared independently of the first phase. The second phase may also be compacted, for example from a powder or granular composition, or formed by extrusion or injection moulding. The second phase may also be a non-compressible phase, for example formed by a liquid composition and a gelling agent to form a gel, or by post-melt curing of the desired components. The second phase may also contain one or more portions of different compositions. The lower surface of the second phase is flat or substantially flat and ideally matches the upper surface of the first phase to ensure that they adhere to each other. For example, both surfaces may be smooth, or the upper surface of the first phase may be convex and the lower surface of the second phase may be concave, or vice versa.

However, although the surfaces of the first and second phases may be of any shape, shapes without sharp edges or corners are preferred to avoid damage and abrasion during transportation and storage.

The first and second phases are bonded together, for example with an adhesive. The adhesive may be applied to the first phase, the second phase, or both. A suitable binder is polyethylene glycol, preferably having a molecular weight of 800 to 6000.

The amount of the first phase in the tablet is generally greater than the amount of the second phase. For example, the weight ratio of the first phase to the second phase is generally greater than 1:1, preferably greater than 10:1, more preferably greater than 15: 1.

The second phase partially covers the upper surface of the first phase. For example, the second phase covers 10 to 50%, preferably 20 to 40%, of the upper surface in terms of surface area.

The second phase of the tablet contains a component that is capable of being released first with the component of the first phase. The second phase may contain an enzyme preparation, which may also contain a bleaching agent. If desired, the second phase may be only slightly compressed, or may be made into a non-compressed form such as a gel, in order to allow the second phase to dissolve rapidly in the wash liquor. The second phase may also contain a disintegrant, for example a mixture such as a mixture of an acid and a base that foams when exposed to water. Suitable disintegrants are acids such as citric acid in combination with a carbonate or bicarbonate salt such as sodium carbonate or bicarbonate.

Each phase or phases of the tablet may be prepared by any compression method, such as tableting, tableting or extrusion, preferably tableting. Suitable equipment includes standard single stroke presses or rotary compressors.

The first phase prepared according to the invention preferably has a width or length of between 10mm and 80mm, more preferably at least 15mm and at most 25mm, and a weight of between 5 and 100 g. The aspect ratio (or aspect ratio) of the tablet is preferably greater than 1:1, more preferably greater than 3: 2. The compression force for preparing the tablet does not need to exceed 120,000kN/m²Preferably not more than 90,000kN/m²More preferably not more than 85,000kN/m²And still more preferably not more than 70,000kN/m²Most preferably not more than 50,000kN/m²。

Test for Effect

The method of experimental testing that occurs in the validation of the examples is as follows:

1. method for testing detergency based on vertical type decontamination machine

Standard artificial stains were allowed to adhere uniformly to the slides, and after washing with a dishwasher detergent solution of a prescribed concentration under prescribed conditions, the percent stain removal was measured.

1.1 reagents and materials

Anhydrous ethanol, citric acid (10g/L), deionized water, and anhydrous calcium chloride (CaCl)₂Anhydrous), magnesium sulfate (MgSO)₄.7H₂O), whole milk powder, fresh egg, wheat flour, 100ppm hard water (Ca)²⁺:Mg²⁺3: 2): weighing 1.67g of anhydrous CaCl₂And 2.47g MgSO₄.7H₂And preparing 1L of hard water with the concentration of 2500ppm by using O, and diluting 40mL of the hard water to 1L when in use, namely the hard water with the concentration of 100 ppm.

1.2 instruments and devices

An electronic balance, an analytical balance, a vertical decontamination machine, corresponding complete equipment, an oven and a thermometer, the temperature of 0-100 ℃, the electromagnetic oven and a microscope slide glass with the size of 2mm multiplied by 76mm multiplied by 26mm, 250mL beaker, a pig palm oil paint brush, a measuring cylinder, 1L, 50mL, a measuring cup and 2L.

1.3 preparation of Artificial oil stain

10% of mixed oil, 15% of wheat flour, 7.5% of whole milk powder, 30% of fresh whole egg liquid and 32.5% of distilled water. Fresh eggs are firstly shelled and placed in a clean beaker to be uniformly stirred for standby. And then, placing the mixed oil in a beaker, heating to 50-60 ℃ until the mixed oil is completely melted, pouring the uniformly mixed wheat flour and the whole milk powder into the beaker, and uniformly stirring. Then, the fresh egg liquid is added into the beaker in several times and stirred evenly. And finally adding water into the beaker in several times and stirring the mixture into fine artificial dirt.

1.4 preparation of contaminated sheets

The newly purchased slide glass is boiled in a conventional detergent solution (reference concentration: 10g/L) for 15min and then washed with tap water until no water drops are formed. Soaking in citric acid solution (reference concentration: 10g/L) for 1h, rinsing twice with tap water, rinsing twice with deionized water, ultrasonic treating in anhydrous ethanol for 20min, oven drying at 80 deg.C for 1.5h, and cooling. The slide was lined with a 10mm line to show that smear was confined below this line.

1.5, smearing

The washed slides were numbered in groups of 4 slides each, and then accurately weighed (to 1mg) on an analytical balance, the mass meter being m₀. The prepared artificial dirt and the brush are placed on an electronic balance (accurate to 0.01g), and the oil stain coating amount is controlled by a decrement method. Smearing is carried out by coating one side, drying and then coating the other side. Generally, the slide is held in the air and laid flat, the brush is used to evenly spread the artificial stain on the slide, and then the slide is laid flat on the tray. The single-side smearing quality is controlled to be 0.30 g-0.35 g. After all the glass slides are coated on one surface, the glass slides are placed in an oven at 80 ℃ to be dried for 30min, then the glass slides are taken out to be cooled, and then the other surface is coated, wherein the coating quality is also controlled to be 0.30 g-0.35 g. After coating, the coating is placed in an oven at 80 ℃ for baking for 1 h. Taking out, cooling to room temperature, and placing on analytical balance to obtain accurate mass meter (accurate to 1mg)₁。m₁-m₀Namely the quality of the dirt coated on the glass slide, the error of the dirt amount between different glass slides is controlled within 0.5 percent.

1.6 washing

(liquid product) weighing 0.5g of sample to be tested in a washing barrel of a vertical decontamination machine, correspondingly putting the known weight of dirt pieces and a washing rack into the washing barrel, filling the stirring slurry, taking 40mL of 2500ppm hard water by using a 50mL measuring cylinder, pouring 40mL of the hard water into the washing barrel along the stirring slurry, taking 960mL of 50 ℃ deionized water by using a 1L measuring cylinder, pouring the deionized water into the washing barrel along the stirring slurry, adding water into the last sample, starting the decontamination machine, and starting washing. After 30min, the machine is automatically stopped, the stirrer is quickly taken down, the washing rack is taken out, the washed glass slide and the washing rack are placed in an oven at 80 ℃ for drying for 1h, the glass slide and the washing rack are taken out for cooling, and the glass slide is weighed to be m₂。

(powder product) 0.5g of sample to be detected is weighed in a small beaker, 40mL of 2500ppm hard water is measured by a 50mL measuring cylinder and poured into a washing barrel, 960mL of 50 ℃ deionized water is measured by a 1L measuring cylinder, and the beaker filled with the sample to be detected is washed into the washing barrel. When the last one isAfter the samples are added, the washing racks are placed into the corresponding washing barrels one by one, and after the stirrer is quickly installed, the decontamination machine is started to start washing. After 30min, the machine is automatically stopped, the stirrer is quickly taken down, the washing rack is taken out, the washed glass slide and the washing rack are placed in an oven at 80 ℃ for drying for 1h, the glass slide and the washing rack are taken out for cooling, and the glass slide is weighed to be m₂。

Note: 1. each set of test should prepare three groups of dirty sheets for the competitive detergent, and three groups of dirty sheets for each sample to be tested; 2. since different smearing conditions can affect the result of the determination of the decontamination rate, parallel samples are required for comparison in each determination.

1.7, results show

Stain removal ratio (%) - (m)₁-m₂)/(m₁-m₀)×100

In the formula: m is₀-slide mass before smearing, g;

m₁-the mass of the smeared slide, g;

m₂-mass of slide after washing, g.

1.8 determination of detergency

The relative average deviation of the three results is less than or equal to 10 percent.

2. Method for testing detergency of various soils-testing actual washing effect of dish-washing machine

After a certain amount of artificial soil was applied to tableware and washed with a detergent solution for household tableware at a predetermined concentration in a dishwasher, the performance of the detergent, such as removal of soil, was referenced by visual evaluation. Non-stained tableware can also be used as a standard and compared therewith.

2.1 reagents and materials

Unless otherwise stated, only distilled or deionized water or water of comparable purity, lard, tallow, refined vegetable oil, milk powder, wheat flour, fresh eggs, tomato ketchup, mustard, tea, oatmeal, citric acid were used in the analysis.

2.2 instruments and devices

Analytical balance, tray balance, dishwasher (controllable temperature, dry, can hold 6 sets of tableware at least), thermometer, pig palm oil paint brush, electromagnetic heating agitator, beaker, stainless steel strainer (1mm mesh), rice bowl (114.3mm), vegetable dish (203.2mm, interior concave surface 140mm), glass cup (60mm 130mm), teacup (70mm 50mm), teacup tray (130mm, interior concave surface 95mm), little oval dish (230mm), condiments dish (70mm), soup basin (200mm), chopsticks, soup spoon, soup ladle, knife, fork.

2.3, Artificial fouling

The artificial dirt is used for coating the vegetable dish and the small oval dish, and the formula of the artificial dirt comprises the following components in percentage by mass: 10% of mixed oil, 15% of wheat flour, 7.5% of whole milk powder, 30% of fresh whole egg liquid, 4% of tomato sauce, 1% of mustard and 32.5% of distilled water. The lard, the beef tallow and the vegetable oil are placed in a beaker according to the mass ratio of 1:1:2, heated to be melted, and stirred uniformly for later use.

Shelling fresh eggs, placing the eggs in a beaker, and uniformly stirring the eggs for later use; mixing wheat flour and whole milk powder; the mixed oil is put in a beaker and heated to 50-60 ℃ for melting. Transferring the uniformly mixed wheat flour and the whole milk powder into a beaker of melted mixed oil for stirring; adding the fresh egg liquid into a beaker in several times and stirring uniformly; adding tomato sauce and mustard, stirring, adding distilled water into beaker, and stirring to obtain fine artificial dirt.

The dishes were first washed in a dishwasher with a 1% citric acid solution, and even new dishes, were washed in the dishwasher before each use, first with a 1% citric acid solution and then with a detergent at the concentrations recommended by the manufacturer, each of which was subjected to a conventional wash cycle. Deionized or distilled water is used in the rinsing process. When there is any stain on the glass, the drying cycle of the dishwasher is not used. No water mark on the glass indicates that the glass is rinsed well. Taking out, washing with distilled water until water drops are not hung, drying in a drying oven, and cooling for later use.

Dipping the artificial dirt with a pig palm oil paint brush, uniformly coating the artificial dirt on the concave central surface of the plate, and placing the plate at the temperature of (25 +/-1) ℃ for 8h for later use after the artificial dirt is coated.

2.4 soaking in tea

The tea stain is used for coating tea cups and tea holders. The preparation process comprises the following steps: in a suitable container, 1000mL of boiling water [ water hardness (2.5. + -. 0.2) mmol/L ] is added to 16g of tea leaves and soaked for 15min, and the tea water is poured into another container through a sieve while stirring. Adding 100mL of filtered tea water into each cup, adding 10mL into each saucer, standing at (25 + -1) ° C for 8h, and discarding the tea water for later use.

2.5 soaking oat

187mL of deionized water was mixed with 12.5g of oatmeal, and the mixture was boiled for 10min with constant stirring. Smeared with a brush onto the inner surface of the dish. The inner edge of the upper part of the dish was left 20mm free of coating. After smearing, the mixture is placed at the temperature of (25 +/-1) ℃ for 4 hours for standby.

1.6, smear see table 2 below:

TABLE 2 stain watch

2.7 test procedure

The stained dishware and other utensils were placed in the dishwasher as per the specifications of the dishwasher. The power was turned on and the program was set to a standard washing state for the test. The dish washer is taken out and aired on the bracket quickly after being automatically stopped, and after being cooled to room temperature, the evaluation is carried out according to the specific evaluation mode shown in the table 3 according to the test purpose, and the performance of the detergent is graded. When the surface of the starchy soil was marked visually, the residue was made more visible by coloring with iodine solution (KI-I2). In order to compare the performance difference of the embodiment conveniently, when the dirt is artificial dirt, the round vegetable dish is uniformly used as an evaluation object; when the dirt is oat stain, uniformly using a rice bowl as an evaluation object; when the dirt is tea stain, tea bowls are uniformly used as evaluation objects.

TABLE 3 Performance evaluation Table

3. Rapid determination of anti-caking and anti-spotting properties

After a certain amount of the filled soil was placed in a dishwasher and washed in the dishwasher with a domestic dishwashing detergent solution of a specified concentration and with wash water of a specified hardness, the detergent was evaluated for anti-filming and anti-spotting properties by visual evaluation. Non-stained tableware can also be used as a standard and compared therewith. If the test object is a tablet or other unit dose formulation with an encapsulated structure, the test is performed after the detergent is added and stirred until it is completely dissolved or uniformly dispersed.

3.1 reagents and materials

3.2 instruments and devices

Analytical balance, tray balance, dishwasher (temperature-controllable, dry, can hold 6 sets of tableware at least), thermometer, electromagnetic heating stirrer, beaker, stainless steel sieve (1mm mesh), glass (60mm 130mm), knife, fork.

3.3 filling in dirt

The dirt filling formula is used for coating the vegetable dish and the small oval dish, and comprises the following components: 10% mixed oil, 15% wheat flour, 7.5% whole milk powder, 30% fresh whole egg liquid, 4% tomato sauce, 1% mustard and 32.5% vegetable oil. The lard, the beef tallow and the vegetable oil are placed in a beaker according to the mass ratio of 1:1:2, heated to be melted, and stirred uniformly for later use.

Shelling fresh eggs, placing the eggs in a beaker, and uniformly stirring the eggs for later use; mixing wheat flour and whole milk powder; the mixed oil is put in a beaker and heated to 50-60 ℃ for melting. Transferring the uniformly mixed wheat flour and the whole milk powder into a beaker of melted mixed oil for stirring; adding the fresh egg liquid into a beaker in several times and stirring uniformly; adding tomato sauce and mustard, stirring, adding vegetable oil into beaker, and stirring to obtain fine dirt for smearing.

3.4 test procedure

The glasses were first washed in a dishwasher with a 1% citric acid solution, and even new glasses, were washed in a dishwasher before each use, first with a 1% citric acid solution and then with a detergent at the concentrations recommended by the manufacturer, each with a conventional washing cycle. Deionized or distilled water is used in the rinsing process. When there is any stain on the glass, the drying cycle of the dishwasher is not used. No water mark on the glass indicates that the glass is rinsed well. Taking out, washing with distilled water until water drops are not hung, drying in a drying oven, and cooling for later use.

The glass and the filling oil were placed in the dishwasher according to the specification of the dishwasher. The power was turned on, the washing was programmed to a standard washing state, and the test was carried out with 320ppm hard water (Ca) as the washing water²⁺:Mg²⁺3:2), the number of repeated washes can be increased by itself to increase the extent of conjunctival and plaque formation as required by the test. And after the dishwasher is automatically stopped, quickly taking out the glass cups to be aired on the bracket, cooling to room temperature, and evaluating according to the specific evaluation mode shown in the figure 2 according to the test purpose to grade various performances of the detergent. Conjunctival and plaque formation were judged.

Examples

Example 1 and comparative examples 1 and 2

Automatic dishwasher specific detergent compositions a and a ', B ', C ' formulated according to the following composition of table 4.

Table 4 detergent tablet compositions a and a ', B ' and C ' prepared in example 1 and comparative examples 1, 2 and 3 and corresponding test results

The test results of the powdery detergent compositions a and a ', B ', C ' of example 1 and comparative example 1, comparative example 2, comparative example 3 are shown in table 4. As can be seen from the results of table 4, in the above-mentioned comparative examples, comparative example 1, comparative example 2 and comparative example 3, which are incomplete examples of the technical solution according to the present invention, respectively contain a polyether type surfactant and a fatty alcohol alkoxy compound, the detergency test effect and artificial soil, oat soil and foam reducing performance of example 1 are superior to those of comparative examples 1, 2 and 3. The result shows that the polyether surfactant and the two fatty alcohol alkoxylates are compounded in the technical scheme provided by the embodiment of the invention, so that the synergistic interaction effect is achieved, and the control of the effective components on reducing foam and the emulsifying and dispersing capacity of the oil stain are fully exerted.

Example 1 and comparative example 4, comparative example 5, comparative example 6

Automatic dishwasher specific detergent compositions a and D ', E ', F ' formulated according to the following composition of table 5.

Table 5 powdery detergent compositions a and D ', E ', F ' prepared in example 1 and comparative example 4, comparative example 5, comparative example 6 and corresponding test results

The test results of the powdery detergent compositions A and D ', E ', F ' of example 1 and comparative example 4, comparative example 5, comparative example 6 are shown in Table 5. As can be seen from table 5, comparative examples 4, 5 and 6 all employ the polyether surfactant and the fatty alcohol alkoxylate compound in combination as required according to the present invention, but the polyether surfactant and the fatty alcohol alkoxylate compound are not mixed in proportion as required according to the present invention, and although the foam control effect of comparative examples 4, 5 and 6 is significant, the oil-stain emulsifying, dispersing and emulsifying soil property is greatly reduced, resulting in greatly reduced detergency and manual soil and oat soil removal effects.

Example 2, example 3, example 4, and example 5

An automatic dishwasher specific detergent composition B, C, D, E formulated according to the composition of table 6 below.

Table 6 powdered detergent composition B, C, D, E prepared according to example 2, example 3, example 4, and example 5 and corresponding test results

The test results of the powdered detergent composition B, C, D, E prepared in example 2, example 3, example 4, and example 5 are shown in table 6. It can be seen from table 6 that the above 4 examples show that the technical solution of the present invention has more implementation possibilities (formulation of different substrates, such as example 7 and example 8), and is not limited to the use of some raw materials, and the compositions mainly according to the claims of the present invention can all perform similar functions.

In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. The special detergent composition for the automatic dishwasher is characterized by comprising the following components in parts by weight:

0.01-20 parts of polyether surfactant;

0.01-20 parts of a nonionic surfactant;

0.01-20 parts of other surfactants;

0.1-30 parts of a copolymer dispersant;

0.1-40 parts of an amino acid derivative chelating agent;

0.1-10 parts of an enzyme preparation;

0-80 parts of an additive;

wherein the nonionic surfactant at least comprises two fatty alcohol alkoxylates, namely a fast-emulsifying fatty alcohol alkoxylate and a slow-emulsifying fatty alcohol alkoxylate, and the weight ratio of the polyether surfactant to the fatty alcohol alkoxylate is 1: 0.1 to 0.5;

the content of the quick-emulsifying fatty alcohol alkoxylate is 0.01-10% of the weight of the composition, and the quick-emulsifying fatty alcohol alkoxylate has the following general formula (2):

wherein in the general formula (2), n is 2-10 and n is a positive integer; m is 2-8 and m is a positive integer; x is 0-5; y is 0 to 7; z is 0 to 5; (x + z): y is 0.2 to 0.5;

the content of the slow emulsifying type fatty alcohol alkoxylate is 0.01-15% of the weight of the composition, and the slow emulsifying type fatty alcohol alkoxylate can also have the following general formula (3):

wherein in the general formula (3), n is 2-10 and n is a positive integer; m is 2-8 and m is a positive integer; x is 3-15; y is 0 to 7; z is 3-15; (x + z): y is 5-10;

the polyether surfactant has the following general formula (1):

in the general formula (1), the number average molecular weight of the polyether surfactant is 600-4000;

in the molecules of the polyether surfactant, the content of the mol percent of the oxyethyl is 60 to 80 percent;

in the molecules of the polyether surfactant, the mole percentage content of the oxypropyl is 5-20%;

in the molecules of the polyether surfactant, the mole percentage content of the butyl oxide is 5-15%;

in the molecule of the polyether surfactant, R group is selected from linear fatty alcohol and/or branched fatty alcohol with the carbon number of 12-18, and the binding site of R based on a polyether group is selected from primary, secondary and tertiary positions;

the other surfactant comprises at least one of alkyl polyglycoside, fatty acid alkoxylate, fatty acid alkylolamide, fatty acid methyl ester ethoxylate, natural grease direct polyoxyethylene or polyoxypropylene;

the additive comprises at least one of a filling agent, an alkaline agent, a viscosity regulator, a bleaching system, an active oxygen stabilizer, an anticorrosive agent, a preservative, a coloring agent, a color stabilizer and essence;

9) the number average molecular weight of the copolymer dispersant is 1000-150000;

the unsaturated monomer A1 of the copolymer dispersant is selected from acrylic acid, methacrylic acid, alpha-hydroxy acrylic acid, alpha-hydroxy methacrylic acid and crotonic acid;

the unsaturated monomer B of the copolymer dispersant is selected from a vinyl monomer containing a sulfonic acid group, an allyl monomer containing a sulfonic acid group, acrylamide containing a sulfonic acid group, methacrylamide containing a sulfonic acid group, acrylate containing a sulfonic acid group and methacrylate containing a sulfonic acid group;

the unsaturated monomer C of the copolymer dispersant comprises unsaturated monomer C1, unsaturated monomer C2 and unsaturated monomer C3;

wherein, in the general formula (5), R₁One or more selected from hydrogen and methyl, R₂Is a saturated alkyl group having 2 to 8 carbon atoms;

2. A detergent composition as claimed in claim 1, wherein said amino acid derivative chelating agent comprises at least one of methylglycinediacetic acid, glutamic acid diacetic acid, N-dicarboxylic acid amino-2-hydroxypropanesulfonic acid, 3-hydroxy-2, 2' -iminodisuccinic acid, and alkali metal or ammonium salts thereof.

3. A detergent composition as claimed in claim 1, which is especially adapted for use in an automatic dishwasher, wherein: the enzyme preparation comprises at least one of a protease, an alpha-amylase, a cellulase, a hemicellulase, a phospholipase, an esterase, a lipase, a peroxidase/oxidase, a pectinase, a lyase, a mannanase, a cutinase, a reductase, a xylanase, a pullulanase, a tannase, a pentosanase, a maltosanase, an arabinase, a beta-glucanase.