CN115353936A - Detergent composition with enhanced oil stain dispersion effect and preparation method of laundry beads thereof - Google Patents

Detergent composition with enhanced oil stain dispersion effect and preparation method of laundry beads thereof Download PDF

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Publication number
CN115353936A
CN115353936A CN202210747824.XA CN202210747824A CN115353936A CN 115353936 A CN115353936 A CN 115353936A CN 202210747824 A CN202210747824 A CN 202210747824A CN 115353936 A CN115353936 A CN 115353936A
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detergent composition
surfactant
fatty acid
oil stain
polyester
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CN115353936B (en
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张少雄
汤美娟
黄平
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Guangdong Youkai Technology Co ltd
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Guangdong Youkai Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043—Liquid or thixotropic (gel) compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

The invention relates to a detergent composition with an oil stain dispersing effect enhancement effect and a preparation method of a washing bead thereof, wherein the detergent composition comprises the following components in percentage by mass: 0.2-2% of polyester-polyether copolymer, 0.5-4% of hydrophobic modified polymer, 0.1-10% of fatty acid methyl ester ethoxylate, 8-85% of surfactant, auxiliary agent and water. The invention adopts the polyester polyether copolymer with a specific structure to be matched with the hydrophobic modified polymer and the fatty acid methyl ester ethoxylate, and the three components can generate a synergistic effect and can effectively disperse oil stains and better form an oil stain isolation film, thereby reducing the adsorption amount of the oil stains on fabrics and obviously improving the oil stain dispersing capability of the detergent composition. Meanwhile, the three components also improve the stability of the product, ensure the appearance form of the product and ensure that the product can well exert the decontamination performance under any temperature condition.

Description

Detergent composition with oil stain dispersing effect enhancement and preparation method of washing condensation bead of detergent composition
Technical Field
The invention relates to the technical field of detergents, in particular to a detergent composition with an oil stain dispersing effect and a preparation method of a washing bead thereof.
Background
Along with the development of society, the environmental protection consciousness of people is gradually strengthened, in order to meet the requirements of environmental protection and green consumption of consumers, industrial manufacturers carry out a great amount of technical innovation, and actively promote detergent products to adopt green raw materials, green production, green packaging and the like so as to realize the purpose of product greening. To achieve the greening of detergent products, renewable surfactants of plant origin are currently more recommended. The natural plant-derived surfactant specifically includes the following: natural fatty alcohol-polyoxyethylene ether (C12-14 AEO series nonionic surfactant), natural sodium fatty alcohol-polyoxyethylene ether sulfate (AES), fatty acids (coconut oleic acid and oleic acid are main), fatty acid methyl ester ethoxylate (FMEE), natural alkyl glycoside (C12-14 APG), cocamidopropyl betaine (CAB), and the like.
As is well known, dodecylbenzene sulfonic acid is also a surfactant commonly used in detergents, has good oil stain removal capacity and is low in price, but a dodecylbenzene carbon chain is a petrochemical source, is still not good enough in green environmental protection compared with the surface active products listed above, and the appearance of the product is often influenced due to the deep color of the raw material. At present, more and more consumers tend to buy detergents compounded by surfactants with green plant-based sources, and due to the fact that environmental awareness is enhanced, the consumers pay more and more attention to green detergent products, and great market demands are provided for greening of the detergent products. Based on the above, the currently developed green plant-based detergent does not use or uses less components such as dodecylbenzene sulfonic acid in the product formula development.
There are many products that improve to the degreasing effect in the prior art, for example: fatty alcohol polyoxyethylene ether sodium sulfate, other sulfate surfactants and amphoteric surfactant alkyl betaine are compounded to improve the deoiling effect; the composite is compounded by adopting the lipophilic polymer, the hydrophobic polymer and the adsorption carrier material, has obvious selective adsorption on oily substances, and can improve the deoiling effect by being compounded with surface activity; the polyester polyether copolymer and the hydrophobically modified maleic acid copolymer are mixed, so that the wettability and the water absorption of the fabric can be fundamentally improved, and the fabric has a good decontamination effect. However, the technical scheme does not solve the problem of how to better improve the oil stain dispersing effect of a formula system which is never added with dodecylbenzene sulfonic acid, and the trend of product greening cannot be met.
In view of the above, there is a need to develop a detergent with no or less sulfonic acid and enhanced oil stain dispersing effect, so as to solve the problems in the prior art and meet the development requirements of the current market.
Disclosure of Invention
In view of the foregoing, there is a need for a detergent composition and method of making laundry beads thereof having enhanced oil soil spreading properties that overcome the deficiencies of the prior art.
The invention aims to provide a detergent composition with an oil stain dispersion enhancing effect, which comprises the following components in percentage by mass:
Figure BDA0003719982070000021
auxiliary agent
Water;
wherein the content of the first and second substances,
the polyester polyether copolymer has the following structural general formula:
Figure BDA0003719982070000022
wherein n ranges from 6 to 100; m ranges from 1 to 15;
the hydrophobically modified polymer has the following general structural formula:
Figure BDA0003719982070000023
wherein y ranges from 30 to 80; m is a group of + Is selected from NH 4 + 、K + 、Na + One of (1);
the fatty acid methyl ester ethoxylate has the following general structural formula:
R-COO-[-CH 2 -CH 2 -O-] x -CH 3 ；
wherein R is selected from alkyl with 12-14 carbon atoms; x ranges from 3 to 12.
Further, the weight average molecular weight of the polyester-polyether copolymer is 1000-15000; the weight average molecular weight of the hydrophobic modified polymer is 1000-8000.
Further, the weight average molecular weight of the polyester-polyether copolymer is preferably 3000 to 10000; the weight average molecular weight of the hydrophobically modified polymer is preferably 1000 to 5000; the mass fraction of the fatty acid methyl ester ethoxylate is preferably 2-8%.
Further, the mass fraction of the polyester-polyether copolymer is preferably 0.5-1%; the mass fraction of the hydrophobically modified polymer is preferably 2 to 4%.
The hydrophobic chain segment of the polyester-polyether copolymer is similar to the structure of a polyester fabric, is easy to adsorb on the surface of the fabric fiber, and increases the hydroxyl content on the surface of the polyester fiber, so that the polymer is more effectively adsorbed on the fabric to form a hydrophilic film, and the polymer is insoluble in oil and water, thereby reducing the adsorption of oil dirt on the polyester fiber.
The hydrophobic modified polymer has more hydrophobic benzene ring groups, has steric hindrance effect and prevents oil stain agglomeration.
The fatty acid methyl ester ethoxylate hydrophobic group is ester-based carbon chain which is partially similar to the structure of the oil stain, has better effects of emulsifying and compatibilization on the oil stain according to the principle of similar compatibility, and can effectively reduce the oil stain from being adsorbed on the polyester fabric again.
Further, the surfactant includes an anionic surfactant, a nonionic surfactant, and a zwitterionic surfactant.
Further, the mass fraction of the anionic surfactant is 2-25%, the mass fraction of the nonionic surfactant is 1-30%, and the mass fraction of the zwitterionic surfactant is 2-30%.
Further, the mass fraction of the anionic surfactant is preferably 5 to 25%, the mass fraction of the nonionic surfactant is preferably 2 to 20%, and the mass fraction of the zwitterionic surfactant is preferably 1 to 12%.
Further, the anionic surfactant is selected from one or more of alkyl sulfate, fatty alcohol polyoxyethylene carboxylate, alpha-olefin sulfonate and fatty acid salt; the nonionic surfactant is selected from one or more of alkyl polyglycoside, fatty alcohol-polyoxyethylene ether, alkanolamide, polyol ester and fatty acid ester ethoxylate; the zwitterionic surfactant is selected from one or more of amino acid type surfactant, amine oxide type surfactant, betaine type surfactant and imidazoline surfactant.
Further, the fatty alcohol polyoxyethylene sulfate, alkyl is C6-C24 alkyl, the alkyl is straight-chain alkyl or branched-chain alkyl, preferably C12-C14 alkyl, polyoxyethylene represents average ethoxylation degree, EO number is preferably 0.5-3; the alkyl sulfate is preferably C12 linear alkyl sodium sulfate; the fatty alcohol polyoxyethylene carboxylate, the alkyl can be C8-C14 alkyl, the alkyl is straight-chain alkyl or branched-chain alkyl, preferably C12-C14 alkyl, polyoxyethylene represents average ethoxylation degree, and EO number is preferably 2-10; the alpha-olefin sulfonate is preferably a sodium salt, wherein the carbon number of the alkyl group on the unsaturated double bond is C6-C24, preferably C8-C18.
The fatty acid salt is a metal salt of C10-C20 fatty acid, the fatty acid salt is formed by alkaline neutralization of fatty acid, and a commonly used alkaline neutralizing agent is sodium hydroxide or potassium hydroxide; the fatty acid salt is preferably one or more of lauric acid (lauric acid), myristic acid (myristic acid), palmitic acid (palmitic acid), oleic acid and stearic acid (stearic acid), and alkali metal salt of arachidonic acid; further preferred is a potassium salt of the above fatty acid.
The nonionic surfactant fatty alcohol-polyoxyethylene ether is a synthetic product of natural fatty alcohol and ethylene oxide, wherein the fatty alcohol is preferably a fatty alcohol with 8-18 carbon atoms, the fatty alcohol is a straight-chain alcohol or an isomeric alcohol, polyoxyethylene represents the average ethoxylation degree, and the EO number is preferably 3-20.
Further, the auxiliary agent is selected from one or more of preservatives, optical brighteners, solvents, enzyme preparations, photostable bleaches, anti-redeposition agents, neutralizing agents, perfumes, pigments and salts.
Further, the preservative is selected from one or more of phenoxyethanol, sodium benzoate, methylchloroisothiazolinone, benzisothiazolinone, isothiazolinone and derivatives thereof.
Further, the anti-redeposition agent is selected from one or more of sodium polyacrylate, maleic acid acrylic acid copolymer, carboxymethyl cellulose, vinyl pyrrolidone homopolymer and copolymer.
Further, the enzyme preparation is selected from one or more of protease, cellulase, lipase, amylase, mannanase and pectinase.
Further, the solvent is selected from one or more of glycerol, propylene glycol, ethanol and polyethylene glycol.
Further, the photostable bleaching agent is selected from one or more of hypochlorite bleaching agent and peroxide bleaching agent; the peroxide bleaching agent is percarbonate or perborate.
Further, the neutralizing agent is selected from one or more of sodium hydroxide, potassium hydroxide, monoethanolamine and triethanolamine
Further, the perfume is selected from perfume ingredients suitable for any detergent product, either of natural origin or of chemically synthesized products, such as perfumes of the melon, floral type.
Further, the pigment is any dye or pigment which can be suitably used in washing products.
Further, the salt is selected from one or more of sodium citrate, borax, ethylene diamine tetraacetic acid disodium salt, sodium percarbonate, sodium gluconate, sodium tartrate and sodium oxalate.
Another object of the present invention is to provide a method for preparing the above detergent composition having an enhanced oil-stain dispersion effect, the method comprising the steps of:
s1, adding water into a container, adding an anionic surfactant under a heating condition, and stirring until the water is dissolved;
s2, stopping heating, adding the nonionic surfactant and the zwitterionic surfactant, and stirring until the nonionic surfactant and the zwitterionic surfactant are dissolved;
and S3, adding the balance of water, cooling, adjusting the pH value, adding the polyester-polyether copolymer, the hydrophobic modified polymer, the fatty acid methyl ester ethoxylate and other auxiliaries, and stirring until the mixture is dissolved to obtain the detergent composition with the effect of enhancing the oil stain dispersion.
Further, in step S1, the heating temperature is 50-70 ℃.
Further, in step S3, the pH is 7 to 8.
It is another object of the present invention to provide a laundry bead comprising the above detergent composition having an enhanced oil dispersion effect.
Another object of the present invention is to provide a method for preparing the above laundry beads, comprising the steps of:
l1, adding a solvent into a container;
l2, adding a neutralizing agent and fatty acid, and stirring until the neutralizing agent and the fatty acid are completely dissolved;
l3, sequentially adding other anionic surfactants, nonionic surfactants and zwitterionic surfactants, and stirring until the anionic surfactants, the nonionic surfactants and the zwitterionic surfactants are completely dissolved;
l4, adding the polyester-polyether copolymer, the hydrophobic modified polymer, the fatty acid methyl ester ethoxylate and other auxiliaries, and stirring until the components are dissolved;
l5, adjusting the pH value to 7-8.5;
and L6, adding the balance of water, cooling, adding other auxiliary agents, stirring until the auxiliary agents are completely dissolved, and sealing the membrane to obtain the washing gel bead product.
The invention has the following beneficial effects:
1. the detergent composition with the effect of enhancing oil stain dispersion is a formula system without containing dodecylbenzene sulfonic acid, and the main component of the detergent composition is basically surface activity of a natural plant-based carbon chain, so that the detergent composition is more environment-friendly.
2. The invention adopts the polyester polyether copolymer with a specific structure to be matched with the hydrophobic modified polymer and the fatty acid methyl ester ethoxylate. The polyester polyether copolymer hydrophobic chain segment is similar to a polyester fabric structure, is easy to adsorb on the surface of fabric fibers, increases the hydroxyl content on the surface of the polyester fibers, enables the polymer to be effectively adsorbed on the fabric to form a hydrophilic film, is not compatible with oil and water, and can reduce the adsorption of oil dirt on the polyester fibers. In addition, the invention discovers that the oil stain can be dispersed very effectively by matching with the hydrophobic modified polymer through research, because the polymer has more hydrophobic benzene ring groups, has steric hindrance effect and prevents the oil stain from agglomerating. Meanwhile, the hydrophobic group of the fatty acid methyl ester ethoxylate is an ester carbon chain which is partially similar to the structure of the oil stain, and the oil stain is emulsified and compatibilized better according to the principle of similar compatibility. The polyether polyester and the oil stain are adsorbed on the polyester cloth in a competitive relationship, and due to the existence of a synergistic effect, the fabric adsorbs more polyether polyester polymers to form an oil stain isolating membrane, so that the adsorption amount of the oil stain on the fabric is greatly reduced, and the effect of enhancing the dispersion of the oil stain is achieved.
3. The polyester-polyether copolymer, the hydrophobic modified polymer and the fatty acid methyl ester ethoxylate have good compatibility with other components, and molecules of the polyester-polyether copolymer, the hydrophobic modified polymer and the fatty acid methyl ester ethoxylate can be stably combined and wound, so that a stable and uniform system is formed, the stability of a product is improved, the appearance form of the product is ensured, and the product can well exert the decontamination performance under any temperature condition.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the following examples are listed. The starting materials, reactions and work-up procedures which are described in the examples are, unless otherwise stated, those which are customary in the market and are known to the person skilled in the art.
The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may, in some instances, provide certain beneficial results. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
It should be understood that other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention.
The scores in the embodiment of the invention are mass scores.
KOH in the examples of the present invention: sodium hydroxide, base neutralizer, purchased from Guangzhou reagent works.
MEA in the examples of the present invention: monoethanolamine, alkali neutralizer, available from dow.
Citric acid in the examples of the present invention: pH adjuster, purchased from Guangzhou reagent works.
Glycerol and propylene glycol in the examples of the invention: solvent, purchased from Guangzhou reagent works.
Fatty acids and oleic acid in the examples of the invention: purchased from pacific grease.
AES in the embodiment of the present invention: the fatty alcohol polyoxyethylene sulfate has fatty alcohol carbon atom number of 12-14 and average ethoxylation degree of 2, and the anionic surfactant is purchased from Aleurites angustifolia.
The AOS in the embodiment of the invention: alpha-olefin sulfonate, anionic surfactant.
AEO9 in the embodiment of the present invention: fatty alcohol polyoxyethylene ether, the number of carbon atoms of fatty alcohol is 12-14, the average degree of ethoxylation is 9, and the nonionic surfactant is purchased from Pasteur company.
TO8 in the embodiment of the present invention: ethoxylated isomeric tridecanol, average degree of ethoxylation 8, nonionic surfactant, lutensol TO series product from BASF corporation.
PAA in the embodiments of the present invention: sodium salt of acrylic acid homopolymer, polycarboxylate, dow company Acusol 445N.
Hydrophobically modified acrylic copolymers in the examples of the invention: the Dow company, acusol845.
CAB in the embodiment of the present invention: cocamidopropyl betaine, a zwitterionic surfactant, purchased from the cantonese, guangzhou.
APG in the examples of the present invention: alkyl glycoside, nonionic surfactant.
Preservatives in the examples of the invention: a mixture of methylisothiazolinone and chloromethylisothiazolinone.
The polyester polyether copolymers of the embodiments of the present invention are available from the kraine SRN series and have the following general structural formula:
Figure BDA0003719982070000071
the hydrophobically modified polymers in the examples of the invention were purchased from noron Alcosperse series products, having the following general structural formula:
Figure BDA0003719982070000072
the fatty acid methyl ester ethoxylate in the embodiments of the present invention is FMEE, available from medium and light daily chemical technologies, having the following general structural formula:
R-COO-[-CH 2 -CH 2 -O-]x-CH 3 。
the respective ingredients and the respective mass fractions in the detergent composition having the oil stain dispersion enhancing effect in example 1 and the detergent compositions of comparative examples 1 to 5 are shown in table 1.
Table 1 ingredients and their mass fractions in detergent compositions of example 1 and comparative examples 1 to 5
Figure BDA0003719982070000073
Figure BDA0003719982070000081
The detergent composition of example 1 having an enhanced oil-stain dispersing effect was prepared by the following method:
s1, adding water into a container, heating to 60 ℃, adding fatty acid and sodium hydroxide, and stirring until the fatty acid and the sodium hydroxide are dissolved;
s2, stopping heating, adding the nonionic surfactant and the zwitterionic surfactant, and stirring until the nonionic surfactant and the zwitterionic surfactant are dissolved;
and S3, adding the balance of water, cooling, adjusting the pH value to 7, adding the polyester-polyether copolymer, the hydrophobic modified polymer, the fatty acid methyl ester ethoxylate and other auxiliaries, and stirring until the mixture is dissolved to obtain the detergent composition with the oil stain dispersion enhancing effect.
The detergent compositions of comparative examples 1 to 5 were prepared by a method different from that of example 1 in that: FMEE or hydrophobically modified polymer is replaced or deleted in the same manner as the other steps.
The individual ingredients and corresponding mass fractions of the laundry bead concentrate liquid detergents in examples 2-3 and comparative examples 6-9 are shown in table 2.
TABLE 2 ingredients and their mass fractions in the concentrated liquid detergents for washing beads of examples 2 to 3 and comparative examples 6 to 9
Figure BDA0003719982070000082
Figure BDA0003719982070000091
The methods of making the laundry bead concentrate liquid detergents of examples 2-3 and comparative examples 6-9 were all as follows:
l1, adding glycerol and propylene glycol into a container, then adding fatty acid and a neutralizing agent, and stirring until the fatty acid and the neutralizing agent are dissolved;
l2, adding other anionic surfactants, nonionic surfactants and zwitterionic surfactants, and stirring until the mixture is dissolved;
and L3, adding the balance of water, adjusting the pH to 7, cooling to 45 ℃, adding the polyester-polyether copolymer, the hydrophobic modified polymer, the fatty acid methyl ester ethoxylate and other auxiliaries, stirring until the mixture is dissolved, and sealing a membrane to obtain the washing condensed bead concentrated liquid detergent.
The detergent compositions of examples 4 to 5 having the enhanced oil stain dispersing effect and the detergent compositions of comparative examples 10 to 11 were additionally provided for stability test. The detergent compositions of examples 4 to 5 and comparative examples 10 to 11 were prepared in the same manner as in example 1.
The respective ingredients and the corresponding mass fractions in the detergent compositions of examples 4 to 5 and comparative examples 10 to 11 are shown in table 3.
TABLE 3 Components and their mass fractions in examples 4 to 5 and comparative examples 10 to 11
Figure BDA0003719982070000092
The laundry beads of examples 6-7 and comparative examples 12-13 were additionally set for stability testing. The preparation of the laundry beads of examples 6-7 and comparative examples 12-13 was the same as in examples 2-3.
The individual ingredients and the corresponding mass fractions in the laundry beads of examples 6-7, comparative examples 12-13 are shown in table 4.
TABLE 4 ingredients and their mass fractions in examples 6 to 7 and comparative examples 12 to 13
Figure BDA0003719982070000101
Test example 1
The test method comprises the following steps:
the detergent compositions prepared in examples 1 to 3 and the laundry beads prepared in comparative examples 1 to 9 were subjected to an oil-stain-dispersing effect test.
1) Polyester white cloth (GB/T7568.4): the polyester white cloth is cut into square blocks with the size of 6 x 6cm by the purchased textile industry technical supervision in Shanghai city.
2) Preparing carbon black oil stain liquid: (1) accurately weighing 20% of activated carbon powder in a beaker; (2) accurately weighing 80% of blend oil, slowly adding the blend oil into the mixture obtained in the step (1), placing the blend oil under a stirrer, and stirring for 10 minutes at the rotating speed of 300-500 revolutions per minute until carbon powder and the oil stain liquid are uniformly mixed; the stirring was maintained throughout the experiment.
3) Adopting a vertical decontamination machine of RHLQ type of the national institute of daily chemical industry; compared with the same vehicle test, the detergent composition is prepared into 2g/L aqueous solution by hard water, the concentrated liquid detergent of the washing coagulated beads is prepared into 1g/L aqueous solution with the accuracy of 0.01 g, the concentrated liquid detergent is placed in different decontamination tanks, the washing temperature is adjusted to 30 ℃, and the stirring speed is 120 r/min.
4) 10g of carbon black oil stain was added and then stirred for 2 minutes to uniformly disperse the stain. The white cloth pre-washed with the corresponding detergent was put into an aqueous detergent solution under agitation and washed for 20 minutes. After the washing of the decontamination machine is finished, the test piece is taken out by tweezers or chopsticks and is flatly laid in a 45-degree oven for drying.
5) The measurement was carried out by a fluorescence whiteness meter, and the whiteness values of the cloth before and after washing were measured. The whiteness retention was calculated.
The smaller the whiteness difference R (difference between the whiteness before washing and the whiteness after washing), the better the oil stain dispersing effect of the detergent is, and the worse the oil stain dispersing effect is. The following formula is specifically calculated:
R＝N0-N1
wherein R represents a difference in whiteness; n1 represents the whiteness after washing; n0 represents the whiteness before washing.
The test results are shown in table 5.
TABLE 5 results of measuring oil-stain dispersing effect of detergent composition
Sample (I) Composition comprising a fatty acid ester and a fatty acid ester Whiteness value before washing Whiteness value after washing Difference in whiteness R
Example 1 Composition D 85 70.8 14.19
Comparative example 1 Composition A 85 58.48 26.52
Comparative example 2 Composition B 85 60.96 24.41
Comparative example 3 Composition C 85 63.01 21.64
Comparative example 4 Composition E 85 52.31 30.25
Comparative example 5 Composition F 85 52.46 31.2
As can be seen from Table 5, the R value of the composition A obtained by adding the polyether polyester copolymer in the comparative example 1 is obviously reduced compared with that of the comparative example 5, which shows that the oil stain dispersing performance of the polyether polyester copolymer is better improved, and the oil stain dispersing performance of the composition E obtained by adding FMEE alone is not improved as seen from the comparative examples 4 and 5. Comparative example 2 it was found that composition B has improved oil spreading properties by replacing AEO9 with FMEE based on the addition of polyether polyester. Comparative example 3 composition C, which is prepared by compounding polyether polyester copolymer with hydrophobically modified copolymer, has further improved oil stain dispersing performance compared with comparative example 1, but the effect is still inferior to that of example 1. In the embodiment 1, the three raw materials are reasonably compounded, and the obtained composition D has the best oil stain dispersing performance, so that the three components have better coordination and synergism, and the single existing effect is not ideal.
TABLE 6 measurement results of oil stain dispersing effect of laundry beads
Sample (I) Composition comprising a metal oxide and a metal oxide Whiteness value before washing Whiteness value after washing Difference in whiteness R
Example 2 Composition I 85 69.82 16.23
Example 3 Composition J 85 72.6 13.11
Comparative example 6 Composition G 85 64.98 20.32
Comparative example 7 Composition H 85 67.66 19.65
Comparative example 8 Composition K 85 52.47 31.83
Comparative example 9 Composition L 85 53.16 32.34
According to the table 6, the combination of the polyether polyester copolymer and the hydrophobic modified polymer is respectively and independently introduced in the comparative examples 6 and 7, compared with the comparative example 8, the fluorescent whiteness R value is obviously reduced, and the oil stain dispersibility is good; the comparative example 9 only introduces the hydrophobic modified maleic acid copolymer, which cannot bring better improvement, because the acrylic acid ester modified acrylic acid copolymer cannot embody good oil stain dispersing performance in structure. In the embodiments 2 and 3, the polyether polyester copolymer and the hydrophobically modified polymer are compounded, so that on one hand, the polyether polyester copolymer can form an oil stain isolating membrane, and on the other hand, the hydrophobically modified polymer has a proper number of carbon chains and benzene rings, so that oil stains can be well emulsified and dispersed, and a synergistic interaction effect is further generated, thereby obviously improving the oil stain dispersing performance.
Test example 2
The test method comprises the following steps:
stability tests were conducted on the detergent compositions prepared in examples 4 to 7 and comparative examples 10 to 13, and on the laundry bead concentrated liquid detergent.
Low-temperature stability: the sample was placed in a 0 ℃ refrigerator for 4 weeks, and after returning to normal temperature, the appearance was observed.
High-temperature stability: the sample was placed in an oven at 45 ℃ for 4 weeks, and after returning to normal temperature, the appearance was observed.
Freeze-thaw cycle: placing the sample in a refrigerator at the temperature of-15 ℃ for 24 hours, and recovering the temperature for 24 hours; and circulating for 4 times, and observing the appearance after the normal temperature is recovered.
And (3) cold-hot circulation: placing the sample in an oven at 45 ℃ for 24 hours, and then placing the sample in a refrigerator at-15 ℃ for 24 hours; and circulating for 4 times, and observing the appearance after the normal temperature is recovered.
The test results are shown in table 7.
TABLE 7 stability measurement results
Sample(s) Composition comprising a fatty acid ester and a fatty acid ester Stability at Low temperature High temperature stability Freeze thaw cycle stability Stability of cold and hot circulation
Example 4 Composition M No precipitation and no delamination No precipitation and no delamination No precipitation and no delamination No precipitation and no delamination
Example 5 Composition N No precipitation and no delamination No precipitation and no delamination No precipitation and no delamination No precipitation and no delamination
Example 6 Composition Q No precipitation and no delamination No precipitation and no delamination No precipitation and no delamination No precipitation and no delamination
Example 7 Composition R No precipitation and no delamination No precipitation and no delamination No precipitation and no delamination No precipitation and no delamination
Comparative example 10 Composition O Milky appearance No precipitation and no delamination Exhibit milky white precipitate No precipitation and no delamination
Comparative example 11 Composition P Milky appearance No precipitation and no delamination Exhibit milky white precipitate No precipitation and no delamination
Comparative example 12 Composition S Opalescent turbidity No precipitation and no delamination No precipitation and no delamination No precipitation and no delamination
Comparative example 13 Composition T Milky white turbidity Precipitation of crystals No precipitation and no delamination No precipitation and no delamination
According to table 6, the detergent composition with the oil stain dispersing effect enhancement and the washing and condensing liquid detergent have good stability, which shows that the polyester-polyether copolymer, the hydrophobic modified polymer and the fatty acid methyl ester ethoxylate in the invention have good compatibility with other components, and molecules of the polyester-polyether copolymer, the hydrophobic modified polymer and the fatty acid methyl ester ethoxylate can be stably combined and wound to form a stable and uniform system, while the comparative example cannot be stably existed in the solution when the temperature changes, so that the layering, the turbidity and the precipitation of the product are caused, and the use experience and the performance of the product are influenced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (10)

1. A detergent composition with an oil stain dispersion enhancing effect is characterized by comprising the following components in percentage by mass:
Figure FDA0003719982060000011
auxiliary agent
Water;
wherein the content of the first and second substances,
the polyester polyether copolymer has the following structural general formula:
Figure FDA0003719982060000012
wherein n ranges from 6 to 100; m ranges from 1 to 15;
the hydrophobically modified polymer has the following general structural formula:
Figure FDA0003719982060000013
wherein y ranges from 30 to 80; m is a group of + Is selected from NH 4 + 、K + 、Na + One of (a) and (b);
the fatty acid methyl ester ethoxylate has the following general structural formula:
R-COO-[-CH 2 -CH 2 -O-] x -CH 3 ；
wherein R is selected from alkyl with 12-14 carbon atoms; x ranges from 3 to 12.
2. A detergent composition having an enhanced oily soil dispersing effect according to claim 1, wherein said polyester-polyether copolymer has a weight average molecular weight of 1000 to 15000; the weight average molecular weight of the hydrophobic modified polymer is 1000-8000.
3. A detergent composition having an enhanced oily soil dispersing effect according to claim 1, wherein said surfactant comprises anionic surfactant, nonionic surfactant and zwitterionic surfactant.
4. A detergent composition with an enhanced oil dispersing effect as claimed in claim 3, wherein said anionic surfactant is selected from one or more of alkyl sulfate, fatty alcohol polyoxyethylene carboxylate, alpha-olefin sulfonate, and fatty acid salt; the nonionic surfactant is selected from one or more of alkyl polyglycoside, fatty alcohol-polyoxyethylene ether, alkanolamide, polyol ester and fatty acid ester ethoxylate; the zwitterionic surfactant is selected from one or more of amino acid type surfactant, amine oxide type surfactant, betaine type surfactant and imidazoline surfactant.
5. A detergent composition with an enhanced oily soil dispersing effect according to claim 1, wherein said auxiliary agent is one or more selected from the group consisting of preservatives, optical brighteners, solvents, enzyme preparations, photostable bleaches, anti-redeposition agents, neutralizers, perfumes, pigments and salts.
6. The detergent composition having an enhanced oil stain dispersing effect according to claim 5, wherein the preservative is selected from one or more of phenoxyethanol, sodium benzoate, methylchloroisothiazolinone, benzisothiazolinone, isothiazolinone and derivatives thereof.
7. A detergent composition with an enhanced oily soil dispersing effect as claimed in claim 5, wherein said anti-redeposition agent is selected from one or more of sodium polyacrylate, maleic acid acrylic acid copolymer, carboxymethyl cellulose, homopolymer and copolymer of vinyl pyrrolidone.
8. The method for preparing a detergent composition having an enhanced oil dispersing effect according to any one of claims 1 to 7, wherein the method for preparing a detergent composition having an enhanced oil dispersing effect comprises the steps of:
s1, adding water into a container, adding an anionic surfactant under a heating condition, and stirring until the water is dissolved;
s2, stopping heating, adding the nonionic surfactant and the zwitterionic surfactant, and stirring until the nonionic surfactant and the zwitterionic surfactant are dissolved;
and S3, adding the balance of water, cooling, adjusting the pH value, adding the polyester-polyether copolymer, the hydrophobic modified polymer, the fatty acid methyl ester ethoxylate and other auxiliaries, and stirring until the mixture is dissolved to obtain the detergent composition with the effect of enhancing the oil stain dispersion.
9. A laundry bead comprising a detergent composition according to any of claims 1 to 7 having enhanced oil dispersion.
10. A method of making a laundry bead as claimed in claim 9, wherein the method of making a laundry bead comprises the steps of:
l1, adding a solvent into a container;
l2, adding a neutralizing agent and fatty acid, and stirring until the neutralizing agent and the fatty acid are completely dissolved;
l3, sequentially adding other anionic surfactants, nonionic surfactants and zwitterionic surfactants, and stirring until the anionic surfactants, the nonionic surfactants and the zwitterionic surfactants are completely dissolved;
l4, adding the polyester-polyether copolymer, the hydrophobic modified polymer, the fatty acid methyl ester ethoxylate and other auxiliaries, and stirring until the components are dissolved;
l5, adjusting the pH value to 7-8.5;
and L6, adding the balance of water, cooling, adding other auxiliary agents, stirring until the auxiliary agents are completely dissolved, and sealing the membrane to obtain the washing gel bead product.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106635497A (en) * 2016-12-12 2017-05-10 广州立白企业集团有限公司 Detergent composition
CN108676638A (en) * 2018-06-12 2018-10-19 广州立白企业集团有限公司 The liquid detergent composition of stabilization and preparation method thereof containing polyester soil release polymers
CN113667554A (en) * 2021-09-22 2021-11-19 广州立白企业集团有限公司 Liquid detergent compositions containing amphiphilic graft polymers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106635497A (en) * 2016-12-12 2017-05-10 广州立白企业集团有限公司 Detergent composition
CN108676638A (en) * 2018-06-12 2018-10-19 广州立白企业集团有限公司 The liquid detergent composition of stabilization and preparation method thereof containing polyester soil release polymers
CN113667554A (en) * 2021-09-22 2021-11-19 广州立白企业集团有限公司 Liquid detergent compositions containing amphiphilic graft polymers

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