Laundry gel bead with multi-effect cleaning power and preparation method thereof

Abstract

The invention relates to a laundry gel bead with multi-effect cleaning power and a preparation method thereof, the laundry gel bead with multi-effect cleaning power comprises the following components: an amphiphilic polymer, isomeric alcohol polyoxyethylene ether, ethoxylated propoxylated fatty alcohol, fatty acid, a surfactant, protease, cellulase, a neutralizer, an auxiliary agent and a solvent, the amphiphilic polymer is obtained by further carrying out condensation polymerization on a reaction product of 5-bromomethyl dimethyl isophthalate and dimethylaminoethyl methacrylate, terephthalic acid, ethylene glycol and polyethylene glycol. The components such as the amphiphilic polymer, the isomeric alcohol polyoxyethylene ether, the surfactant and the enzyme are compounded, the compatibility among the various components is good, the stability of the laundry gel beads is effectively improved, the components can form a strong synergistic effect, the cleaning capacity of the product is further improved, and the laundry gel beads have good application prospects.

Description

Technical Field

[0001] The invention relates to the technical field of detergents, and in particular to laundry beads with multi-effect cleaning power and a preparation method thereof. Background Art

[0002] With the advancement of science and technology and the accelerated pace of people's lives, more and more convenient and efficient products are appearing in our lives. In recent years, concentrated detergents have gradually attracted attention and become popular around the world. Concentrated detergents achieve higher cleaning efficiency and environmental performance by increasing the content of active ingredients in the formula, especially the concentration of surfactants. Among them, laundry beads have gradually become an important washing product for modern families and laundries with their unique advantages.

[0003] The active matter content of the Chinese laundry detergent industry standard is 15%, while the active matter content of concentrated laundry detergent can reach 25%, and that of concentrated + type can reach 45%. The active matter content of laundry beads is even as high as 80%-90%. Although the active matter content of common commercially available laundry beads is high, there is still room for improvement in the decontamination performance. Common commercially available products can only have 8 times the cleaning power for one or more of carbon black, protein and sebum stains, or only have 12 times the cleaning power for protein stains. The cleaning power of laundry beads is still a common concern of consumers. In addition, the common means of improving the decontamination power is to increase the surfactant content or increase the amount of protease added. The beads are formulated with ultra-high active matter content. If the active content is too high, the formula will be unstable or the surfactant will precipitate. Increasing the amount of protease added to the laundry beads formula only has a good effect on improving the protein detergency, but there is no obvious improvement in the removal of sebum and carbon black stains, and it may even affect the stability of the formula, increase the cost, but the decontamination performance cannot be significantly improved.

[0004] In summary, there is an urgent need to research and develop a stable laundry detergent bead product that has higher cleaning power against carbon black, protein and sebum stains to solve the problems existing in the prior art. Summary of the invention

[0005] Based on this, the present invention provides a laundry condenser bead with multi-effect cleaning power. The present invention uses amphiphilic polymers, isomeric alcohol polyoxyethylene ethers, surfactants, enzymes and other ingredients to compound, and the compatibility between the various ingredients is good, which effectively improves the stability of the laundry condenser bead, and the components can form a strong synergistic effect, further improving the cleaning ability of the product, overcoming the shortcomings of the prior art, and having good application prospects.

[0006] One object of the present invention is to provide a laundry condensate bead with multiple cleaning effects, wherein the laundry condensate bead with multiple cleaning effects comprises the following components in mass fractions:

[0007] Amphiphilic polymer 1%-5%

[0008] Isopropyl alcohol polyoxyethylene ether 1%-5%

[0009] Ethoxylated propoxylated fatty alcohol 1%-10%

[0010]

[0011] in,

[0012] The amphiphilic polymer is a reaction product of 5-bromomethyl dimethyl isophthalate and dimethylaminoethyl methacrylate, which is further obtained by polycondensation with terephthalic acid, ethylene glycol and polyethylene glycol.

[0013] Furthermore, the preparation method of the amphiphilic polymer comprises the following steps:

[0014] S1, mixing 5-bromomethyl dimethyl isophthalate, dimethylaminoethyl methacrylate and a catalyst, and heating the mixture for reaction to obtain an intermediate product;

[0015] S2. The intermediate product, terephthalic acid, ethylene glycol and a catalyst are mixed, heated under vacuum conditions for reaction, and then ethylene glycol and polyethylene glycol are added to continue the reaction to obtain an amphiphilic polymer.

[0016] Furthermore, in step S1, the temperature of the heating reaction is 30-60°C.

[0017] Furthermore, in step S1, the molar ratio of dimethyl 5-bromomethylisophthalate to dimethylaminoethyl methacrylate is 1:(10-15).

[0018] Furthermore, in step S2, the temperature of the heating reaction is 200-300°C.

[0019] Furthermore, in step S2, the molar ratio of the intermediate product, terephthalic acid, ethylene glycol and polyethylene glycol is 1:(5-10):(10-15):(0.5-2).

[0020] Furthermore, in step S1, the catalyst is cuprous bromide and N,N,N,N,N-pentamethyldiethylenetriamine; in step S2, the catalyst is antimony acetate.

[0021] Furthermore, the isomeric alcohol polyoxyethylene ether is isomeric tridecanol polyoxyethylene ether.

[0022] Furthermore, the surfactant is selected from one or more of anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants.

[0023] Preferably, the anionic surfactant is selected from at least one of linear alkylbenzene sulfonic acid and its salts, fatty acid salts, alkyl sulfates, ethoxylated fatty alcohol sulfates, α-olefin sulfonates, sulfosuccinates, fatty acid alkyl ester sulfonates, and ethoxylated fatty alcohol ether carboxylates;

[0024] The cationic surfactant is selected from at least one of a quaternary ammonium salt surfactant, a heterocyclic surfactant and a polymeric cationic surfactant;

[0025] The nonionic surfactant is selected from at least one of fatty alcohol alkoxylates, alkyl polysaccharides, fatty acid alkoxylates, fatty acid ethoxylates, fatty acid alkylolamides, and ethoxylated sorbitan esters;

[0026] The zwitterionic surfactant is selected from at least one of an amino acid-based surfactant, an amine oxide-based surfactant, a betaine-based surfactant, and an imidazoline-based surfactant.

[0027] The compounding of the components such as the ethoxylated propoxylated fatty alcohol and the nonionic surfactant of the present invention is beneficial to reducing the gel phase area of ​​the surfactant, thereby improving the solubility of the components, avoiding the precipitation and stratification of the laundry beads, and improving the overall stability of the laundry beads.

[0028] Furthermore, the protease is selected from one or more of cysteine ​​protease, metalloprotease, serine protease and aspartic acid protease.

[0029] Furthermore, the cellulase is selected from one or more of endocellulase, exocellulase, cellobiase, oxidative cellulase and cellulose phosphorylase.

[0030] Furthermore, the neutralizing agent is selected from one or more of sodium hydroxide, potassium hydroxide, monoethanolamine, and triethanolamine.

[0031] Furthermore, the auxiliary agent is selected from one or more of flavors, preservatives, pigments, and inorganic salts.

[0032] Furthermore, the solvent is selected from one or more of water, ethanol, glycerol, propylene glycol, sorbitol, polyethylene glycol, diethylene glycol butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, diethylene glycol butyl ether acetate, dipropylene glycol butyl ether and tripropylene glycol butyl ether.

[0033] Furthermore, the auxiliary agent is selected from one or more of flavors, preservatives, pigments, inorganic salts, and pH regulators.

[0034] Another object of the present invention is to provide a method for preparing the above-mentioned laundry beads with multi-effect cleaning power, comprising the following steps:

[0035] L1. Add the solvent into a container, heat it, add the fatty acid, neutralizing agent, surfactant and amphiphilic polymer, and stir until dissolved;

[0036] L2, add the remaining solvent, adjust the pH after cooling, then add the isomeric alcohol polyoxyethylene ether, ethoxylated propoxylated fatty alcohol and other components, stir and dissolve to obtain the contents;

[0037] L3. The contents are fed into a packaging machine and packaged with a PVA water-soluble film to obtain laundry beads with multi-effect cleaning power.

[0038] Furthermore, the heating temperature is 50-70°C.

[0039] Furthermore, the pH value is adjusted to 6-8.

[0040] Furthermore, the thickness of the PVA water-soluble film is 60-100 μm.

[0041] The present invention has the following beneficial effects:

[0042] The laundry beads with multi-effect cleaning power of the present invention are compounded with components such as isomeric alcohol polyoxyethylene ether, amphiphilic polymer, ethoxylated propoxylated fatty alcohol, surfactant, protease, cellulase, etc., wherein the amphiphilic polymer is firstly reacted with 5-bromomethyl isophthalic acid dimethyl ester and dimethylaminoethyl methacrylate, free radical polymerization is carried out under the action of a catalyst to obtain polydimethylaminoethyl methacrylate side chain, and then further condensed with terephthalic acid and ethylene glycol to obtain a polyester segment containing a benzene ring, and finally condensed with polyethylene glycol to obtain a hydrophilic polyether segment. The amphiphilic polymer prepared by the present invention has hydrophilic amino segments and ethoxylated polyether segments, as well as hydrophobic polyester segments, and has good interfacial activity, which can not only improve the stability of laundry beads, but also help to enhance the decontamination effect of the product. In addition, the polyester segment in the amphiphilic polymer has a similar structure to the polyester fiber in the clothing, and is easily adsorbed on the fabric surface during washing, while the hydrophilic polyether segment plays an anti-redeposition and long-lasting cleaning effect. The introduced polymer amino side chain can not only play a hydrophilic role, but also has an antibacterial effect. In addition, the various active functional groups in the amphiphilic polymer have good compatibility with other anionic and nonionic surfactants, and have a strong affinity with proteases and cellulases. The oxygen-containing active groups can also combine with the enzymes through hydrogen bonds, avoiding the possibility of inactivation of the enzyme components in the high sulfonic acid content composition. Therefore, the amphiphilic polymer can promote the removal of various stains such as grease and protein on the surface of clothing while further reducing surface tension and improving interfacial activity. The various components enhance the cleaning effect of the product through synergistic enhancement. DETAILED DESCRIPTION

[0043] In order to more clearly illustrate the technical solution of the present invention, the following examples are listed. Unless otherwise stated, the raw materials, reactions and post-treatment methods shown in the examples are common raw materials on the market and technical methods well known to those skilled in the art.

[0044] The words "preferred", "preferably", "more preferably", etc. in the present invention refer to embodiments of the present invention that can provide certain beneficial effects in certain circumstances. However, other embodiments may also be preferred under the same circumstances or other circumstances. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not applicable, nor is it intended to exclude other embodiments from the scope of the present invention.

[0045] It should be understood that, except in any operating examples, or where otherwise indicated, all numbers expressing, for example, the amounts of ingredients used in the specification and claims should be understood to be modified in all cases by the term "about". Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximate values ​​that vary depending on the desired properties to be obtained by the present invention.

[0046] The present invention uses the following raw materials:

[0047] Glycerol and propylene glycol: solvents, purchased from Guangzhou Reagent Factory.

[0048] MEA: monoethanolamine, base neutralizer, purchased from Dow.

[0049] Sulfonic acid: linear alkylbenzene sulfonic acid, carbon number 10-14, anionic surfactant, purchased from Zanyu.

[0050] Fatty acids: C16-18 fatty acids, purchased from Pacific Oils.

[0051] AES: fatty alcohol polyoxyethylene sulfate, the carbon number of the fatty alcohol is 12-14, the average degree of ethoxylation is 2, anionic surfactant, purchased from Anhui Jintong.

[0052] AEO9: fatty alcohol polyoxyethylene ether, the carbon number of the fatty alcohol is 12-14, the average degree of ethoxylation is 9, non-ionic surfactant, purchased from BASF.

[0053] Ethoxylated propoxylated C16-18 alcohol: fatty alcohol with 16-18 carbon atoms, non-ionic surfactant, Dow EcoSense series product.

[0054] Secondary alcohol polyoxyethylene ether: brand number is secondary alcohol 1209, purchased from Jiangsu Saike.

[0055] CAB: cocamidopropyl betaine, a zwitterionic surfactant, purchased from Guangzhou Tianci.

[0056] APG: Alkyl polyglycoside, nonionic surfactant.

[0057] Citric acid: pH adjuster, purchased from Guangzhou Reagent Factory.

[0058] Cellulase: purchased from Guangdong Yiduoli Biotechnology Co., Ltd.

[0059] Protease: purchased from Novozymes (China) Biotechnology Co., Ltd.

[0060] Preservatives: Methylisothiazolinone, Chloromethylisothiazolinone.

[0061] Isomeric alcohol polyoxyethylene ether: Isomeric tridecyl alcohol polyoxyethylene ether 1305.

[0062] The method for preparing the amphiphilic polymer in the embodiment of the present invention comprises the following steps:

[0063] S1. Using DMF as solvent, dimethylaminoethyl methacrylate, cuprous bromide and N,N,N,N,N-pentamethyldiethylenetriamine were mixed, and 5-bromomethyldimethylisophthalate was added under nitrogen protection. After reacting at 50° C. for 8 h, sufficient THF was added to terminate the reaction, and the solvent was removed by distillation under reduced pressure to obtain an intermediate product;

[0064] Wherein, the molar ratio of dimethylaminoethyl methacrylate, cuprous bromide, N,N,N,N,N-pentamethyldiethylenetriamine, and 5-bromomethyldimethylisophthalate is 10:1:1:1;

[0065] S2. The intermediate product, terephthalic acid and ethylene glycol in a molar ratio of 1:10:13 are mixed, stirred and melted at 250°C, a catalytic amount of antimony acetate is added, vacuum is evacuated, the reaction is carried out for 2 hours, and then the temperature is raised to 280°C for reaction for 3 hours; then ethylene glycol and polyethylene glycol PEG-4000 in a molar ratio of 1:0.5 (the molar ratio of ethylene glycol to the intermediate product is 2:1) are added, the reaction is carried out at 250°C for 1 hour, and then the reaction is continued at 280°C for 2 hours to obtain an amphiphilic polymer.

[0066] The components and corresponding mass fractions of the laundry beads with multi-effect cleaning power of Examples 1-3 of the present invention are shown in Table 1.

[0067] Table 1 Components and their mass fractions in Examples 1-3

[0068]

[0069]

[0070] The preparation method of the laundry beads with multi-effect cleaning power of Examples 1-3 comprises the following steps:

[0071] L1. Add 1 / 2 of glycerol, propylene glycol and deionized water into a container according to the above mass fractions, add fatty acids, MEA, sulfonic acid, AES, AEO9, secondary alcohol polyoxyethylene ether, CAB, APG and amphiphilic polymer at 60°C, and stir until dissolved;

[0072] L2, add the remaining solvent, add citric acid to adjust the pH to 7 after cooling, then add isomeric alcohol polyoxyethylene ether, ethoxylated propoxylated C16-18 alcohol and other components, stir and dissolve to obtain contents;

[0073] L3. The contents are fed into a packaging machine and packaged with a PVA water-soluble film to obtain laundry beads with multi-effect cleaning power.

[0074] Comparative Examples 1-2 are set based on the embodiment. The difference between the comparative examples and the embodiment is that:

[0075] The difference between Comparative Example 1 and Example 1 is that the mass of the amphiphilic polymer is replaced by isomeric alcohol polyoxyethylene ether, and the other ingredients and preparation method are the same as those of Example 1;

[0076] The difference between Comparative Example 2 and Example 1 is that the preparation method of the amphiphilic polymer is modified as follows:

[0077] Mix dimethyl terephthalate and ethylene glycol, heat to 110°C, stir for 1 hour, remove excess water, add polyethylene glycol PEG4000 and catalyst antimony acetate after the reactants are completely melted, react at 260°C for 4 hours under nitrogen protection to obtain a product, wherein the molar ratio of dimethyl terephthalate, ethylene glycol, polyethylene glycol, and antimony acetate is 1.3:1:2:0.1;

[0078] The other ingredients and preparation method are the same as those in Example 1.

[0079] Test Example 1

[0080] The laundry beads of the embodiments and comparative examples were tested for stability.

[0081] Test method:

[0082] Low temperature stability: Place the laundry beads in an environment with a temperature of 0±2℃ for 8 weeks, then take them out and observe them immediately. If there is no obvious color change, stratification or precipitation of the laundry beads, the low temperature stability is considered qualified.

[0083] Constant temperature and humidity stability: Place the laundry beads in an environment with a temperature of 37±2℃ and a humidity of 75% for 8 weeks, then take them out and observe them immediately. If there is no obvious color change, stratification or precipitation of the laundry beads, the constant temperature and humidity stability is considered qualified.

[0084] Room temperature stability: Place the laundry beads in an environment with a temperature of 25±2℃ for 8 weeks, then take them out and observe them immediately. If there is no obvious color change, stratification or precipitation of the laundry beads, the room temperature stability is considered qualified.

[0085] High temperature stability: Place the laundry beads in a 45±2℃ environment for 8 weeks, then take them out and observe them immediately. If there is no obvious discoloration, stratification or precipitation of the laundry beads, the high temperature stability is considered qualified.

[0086] Freeze-thaw cycle stability: Place the laundry beads at -15℃ for 24 hours, take them out and place them at room temperature for 24 hours, repeat this cycle 4 times, and observe the appearance after each cycle. If there is no obvious color change, stratification or precipitation of the laundry beads, the freeze-thaw cycle stability is considered qualified.

[0087] Cold and hot cycle stability: Place the laundry beads at -15℃ for 24 hours, take them out and place them at 45±1℃ for 24 hours, cycle 4 times, and observe the appearance after each cycle. If there is no obvious color change, stratification or precipitation of the laundry beads, it is judged to be qualified for freeze-thaw cycle stability.

[0088] Test results:

[0089] The results of the stability study are shown in Table 2.

[0090] Table 2 Stability test results

[0091]

[0092]

[0093] The stability test results show that the laundry beads of Examples 1-3 can maintain good stability under high and low temperature, freeze-thaw cycle, and hot and cold cycle conditions, while Comparative Examples 1-2 in which the amphiphilic polymer was replaced have defects to varying degrees under low temperature, freeze-thaw cycle, and hot and cold cycle conditions, and the stability is significantly reduced.

[0094] Test Example 2

[0095] The cleaning performance of the laundry beads of the embodiments and comparative examples was tested.

[0096] Test method:

[0097] The test was conducted according to the national standard GB / T 13174 "Determination of detergency and cyclic washing performance of detergents for clothing". The concentration of the standard laundry detergent was 0.2 wt %, and the concentration of the laundry beads prepared in Example 1 and Comparative Examples 1-2 was 0.01667 wt %.

[0098] Among them, the P value represents the decontamination ratio. Generally, the decontamination ratio of a standard laundry detergent is set to 1.00, and the higher the P value, the better the cleaning power.

[0099] Test results:

[0100] The test results are shown in Table 3.

[0101] Table 3 Cleaning performance test results

[0102]

[0103] According to Table 3, it can be concluded that the embodiment adopts an amphiphilic polymer compounded with surfactants, enzymes and other components, has excellent cleaning ability, and can effectively remove carbon black, protein and sebum dirt, while the amphiphilic polymer in Comparative Example 1 is replaced by isomeric alcohol polyoxyethylene ether, and no amino side chain is introduced into the polymer of Comparative Example 2, resulting in a decrease in the cleaning power of the ingredients and the synergistic effect between the various components. The washing effect is significantly reduced compared with the embodiment, and an ideal improvement is not achieved.

[0104] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0105] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A laundry condensate bead with multi-effect cleaning power, characterized in that: The laundry beads with multi-effect cleaning power include the following components by mass fraction: in, The amphiphilic polymer is a reaction product of 5-bromomethyl dimethyl isophthalate and dimethylaminoethyl methacrylate, which is further obtained by polycondensation with terephthalic acid, ethylene glycol and polyethylene glycol.

2. The laundry detergent beads with multi-effect cleaning power according to claim 1, characterized in that: The preparation method of the amphiphilic polymer comprises the following steps: S1, mixing 5-bromomethyl dimethyl isophthalate, dimethylaminoethyl methacrylate and a catalyst, and heating the mixture for reaction to obtain an intermediate product; S2. The intermediate product, terephthalic acid, ethylene glycol and a catalyst are mixed, heated under vacuum conditions for reaction, and then ethylene glycol and polyethylene glycol are added to continue the reaction to obtain an amphiphilic polymer.

3. The laundry detergent beads with multi-effect cleaning power according to claim 2, characterized in that: In step S1, the temperature of the heating reaction is 30-60°C.

4. The laundry detergent beads with multi-effect cleaning power according to claim 2, characterized in that: In step S1, the molar ratio of dimethyl 5-bromomethylisophthalate to dimethylaminoethyl methacrylate is 1:(10-15).

5. The laundry detergent beads with multi-effect cleaning power according to claim 2, characterized in that: In step S2, the temperature of the heating reaction is 200-300°C.

6. The laundry detergent beads with multi-effect cleaning power according to claim 2, characterized in that: In step S2, the molar ratio of the intermediate product, terephthalic acid, ethylene glycol and polyethylene glycol is 1:(5-10):(10-15):(0.5-2).

7. The laundry detergent beads with multi-effect cleaning power according to claim 1, characterized in that: The isomeric alcohol polyoxyethylene ether is isomeric tridecanol polyoxyethylene ether.

8. The laundry detergent beads with multi-effect cleaning power according to claim 1, characterized in that: The surfactant is selected from one or more of anionic surfactants, nonionic surfactants, amphoteric surfactants and cationic surfactants.

9. The laundry detergent beads with multi-effect cleaning power according to claim 1, characterized in that: The auxiliary agent is selected from one or more of flavors, preservatives, pigments, inorganic salts, and pH regulators.

10. The method for preparing the laundry beads with multi-effect cleaning power according to any one of claims 1 to 9, characterized in that: The steps include: L1. Add the solvent into a container, heat it, add the fatty acid, neutralizing agent, surfactant and amphiphilic polymer, and stir until dissolved; L2, add the remaining solvent, adjust the pH after cooling, then add the isomeric alcohol polyoxyethylene ether, ethoxylated propoxylated fatty alcohol and other components, stir and dissolve to obtain the contents; L3. The contents are fed into a packaging machine and packaged with a PVA water-soluble film to obtain laundry beads with multi-effect cleaning power.

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