A high fatty acid content liquid detergent composition comprising a dye fixative and a process for its preparation

Abstract

The present application relates to the field of detergent, and discloses a high fatty acid content liquid detergent composition containing a dye fixing agent and a preparation method thereof.The liquid detergent composition comprises: 0.1-5% of the dye fixing agent, 1-15% of non-ionic surfactant, 1-15% of anionic surfactant, and water; wherein: the dye fixing agent is the reactant of amine and epichlorohydrin; the anionic surfactant contains 2-7% of fatty acid surfactant in all raw materials; and the weight ratio of the non-ionic surfactant to the anionic surfactant is at least 0.4:1.The present application optimizes the proportion and type of raw materials in the liquid detergent composition, so that the cationic dye fixing agent can still maintain good low-temperature stability in the high content anionic surfactant for a long time.In the above formula framework, the addition of the dye fixing agent can even improve the low-temperature stability of the system to a certain extent.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of detergents, in particular to a high fatty acid content liquid detergent composition comprising a dye fixative and a preparation method thereof. BACKGROUND

[0002] With the improvement of people's living standards, consumers pay more attention to the use of different color systems in daily clothing, home fabrics and other clothing. However, during the cleaning process, the dye on the fabric often releases into the water, causing discoloration, or transferring to different colored fabrics, causing different colored fabrics to stain each other. In today's fast-paced life, people are no longer satisfied with the method of washing fabrics separately to avoid color bleeding. Instead, they hope that detergents can not only meet the general cleaning needs, but also have anti-fading or bleeding effects.

[0003] Currently, to solve the problem of fading or bleeding, additives with color protection function are mainly added. The color protection additives for liquid detergents are generally non-ionic and cationic. Non-ionic color protection additives mainly form a film on the surface of the fabric to reduce the loss of dye molecules on the colored fabric and reduce the amount of free dye staining white fabric, thereby achieving the effect of color protection and anti-color bleeding. However, the color fixing and anti-color bleeding effect of such color protection agents is limited. Cationic color protection additives, on the other hand, can fix dyes by adsorbing to the surface of the fabric, and can prevent color bleeding by combining with free dye molecules. However, such dye fixing agents are strong cations, and require high detergent formulations. Strong anionic and cationic surfactant interactions can easily make the formulation system turbid or even precipitate. Patent CN114644963A discloses that adding a small amount of hydrogenated castor oil or microcrystalline cellulose to a laundry detergent composition containing a dye fixing agent can improve its stability. Compared to additional additives, if the formulation system itself is compatible with such dye fixing agents and can be stored stably for a long time, it is also an economical and effective solution. SUMMARY

[0004] To solve the above technical problems, the present application provides a high fatty acid content liquid detergent composition comprising a dye fixing agent and a preparation method thereof. By optimizing the proportion and type of raw materials in the liquid detergent composition, the cationic dye fixing agent has good compatibility in the high content of anionic surfactant, thereby effectively playing the color protection and anti-color bleeding performance. In the above formulation framework, the addition of dye fixing agent can even improve the low temperature stability of the system to a certain extent.

[0005] The specific technical solutions of the present application are as follows:

[0006] In a first aspect, the present application provides a high fatty acid content liquid detergent composition comprising a dye fixative, comprising the following ingredients in mass percentages: 0.1-5% of a dye fixative, 1-15% of a nonionic surfactant, 1-15% of an anionic surfactant, and water.

[0007] wherein: the dye fixative is a reaction product of an amine and epichlorohydrin; the anionic surfactant comprises 2-7% of a fatty acid surfactant based on the total ingredients; and the weight ratio of the nonionic surfactant to the anionic surfactant is at least 0.4:1.

[0008] Preferably, the dye fixative is 0.5-2%.

[0009] As described in the background section, the dye fixative is strongly cationic and is sensitive to the formulation system. Too much anionic surfactant can cause instability in the formulation. The present application has found that the addition of a certain amount of fatty acid to the anionic surfactant can improve the compatibility of the dye fixative in the system. The present application has also found that in a system with a low ratio of nonionic surfactant to anionic surfactant, the replacement of only a portion of the anionic surfactant with fatty acid can also improve the low temperature stability of the system.

[0010] Preferably, the amine is a primary amine, a secondary amine, or a tertiary amine.

[0011] Further preferably, the dye fixative is a reaction product of dimethylamine and epichlorohydrin, i.e. poly(2-hydroxypropyldimethylammonium chloride).

[0012] Preferably, the weight ratio of the nonionic surfactant to the anionic surfactant is 0.4-4:1.

[0013] Preferably, the fatty acid surfactant accounts for 30-60% of the anionic surfactant (further preferably 45-55%), and the fatty acid surfactant is a straight chain saturated fatty acid or a straight chain unsaturated fatty acid having a carbon chain length of 10-20, or a mixture of the two.

[0014] Further preferably, the fatty acid surfactant is one or more of lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid.

[0015] Preferably, the anionic surfactant, in addition to the fatty acid surfactant, comprises one or more of a fatty alcohol polyoxyethylene ether sulfate, a fatty alcohol polyoxyethylene ether carboxylate, and does not comprise any of an alkyl sulfonate, an alkyl chain sulfate, an alkyl chain benzene sulfonate, and an alpha-alkenyl sulfonate.

[0016] The present application finds that when the anionic surfactant structure does not carry an ethoxy block, the addition of a dye fixative will cause the formulation system to become hazy or turbid, and the low temperature stability is poor.

[0017] As preferred, the nonionic surfactant comprises one or more of alkyl glycoside, fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, fatty acid methyl ester ethoxylate, and amine oxide type surfactant.

[0018] As preferred, the content of the anionic surfactant is 4-15%; the content of the nonionic surfactant is 2-15%.

[0019] As preferred, the pH of the liquid detergent composition is 8.50-9.50.

[0020] As preferred, the liquid detergent composition specifically comprises the following components in mass percentage:

[0021] A) dye fixative 0.1-5.0% (as 0.5-2%),

[0022] B) fatty acid surfactant 2-7%,

[0023] C) nonionic surfactant 2-15%,

[0024] D) anionic surfactant other than B) 2-8%,

[0025] E) chelating agent 0-0.5%,

[0026] F) enzyme preparation 0-0.2%,

[0027] G) thickening agent 0-2%,

[0028] H) preservative 0-0.2%,

[0029] I) pH adjuster,

[0030] J) fragrance 0-1%,

[0031] H) water balance.

[0032] In a second aspect, the present application provides a preparation method of the above liquid detergent composition, comprising the following steps:

[0033] 1) add part of the pH adjuster in water, then add the fatty acid surfactant, and stir uniformly at 40-60°C.

[0034] 2) sequentially add the nonionic surfactant, the remaining anionic surfactant, and stir uniformly.

[0035] 3) cooling to 30-40℃, adjusting pH to 8.5-9.5, adding the rest of the components, stirring uniformly, finally adding dye fixative, and supplementing water to 100%.

[0036] Compared with the prior art, the present application has the following technical effects:

[0037] (1) The present application optimizes the formula system, so that the strong cationic dye fixative can be stored stably for a long time in a low temperature environment, and the addition of the dye fixative can further enhance the low temperature stability of the above formula system.

[0038] (2) The present application ensures good low temperature stability of the dye fixative without affecting the color protection effect and the anti-bleeding effect. DETAILED DESCRIPTION

[0039] The present application will be further described below in combination with examples.

[0040] General examples

[0041] A high fatty acid content liquid detergent composition containing a dye fixative includes the following raw materials by mass percentage: 0.1-5% (preferably 0.5-2%) of dye fixative, 1-15% of nonionic surfactant (preferably 2-15%), 1-15% of anionic surfactant (preferably 4-15%), and water. The pH of the system is controlled to be 8.50-9.50.

[0042] The dye fixative is the reaction product of an amine and epichlorohydrin; the amine is a primary amine, a secondary amine or a tertiary amine, and the dye fixative is most preferably the reaction product of dimethylamine and epichlorohydrin, i.e. poly(2-hydroxypropyldimethylammonium chloride).

[0043] The anionic surfactant contains 2-7% of fatty acid surfactant based on all raw materials; the fatty acid surfactant accounts for 30-60% (further preferably 45-55%) of the anionic surfactant, and the fatty acid surfactant is a straight-chain saturated fatty acid or a straight-chain unsaturated fatty acid with a carbon chain length of 10-20 or a mixture of the two. Further preferably, it is one or more of lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid.

[0044] The anionic surfactant, in addition to the fatty acid surfactant, also includes one or more of fatty alcohol polyoxyethylene ether sulfate and fatty alcohol polyoxyethylene ether carboxylate, and does not contain any of alkyl sulfonate, alkyl chain sulfate, alkyl chain benzene sulfonate and α-alkenyl sulfonate. Further preferably, the nonionic surfactant includes one or more of alkyl glycoside, fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, fatty acid methyl ester ethoxylate and amine oxide type surfactant.

[0045] The weight ratio of nonionic surfactant to anionic surfactant is at least 0.4:1, and further preferably 0.4-4:1.

[0046] As preferred, the liquid detergent composition specifically comprises the following components in mass percentage:

[0047] A) dye fixative 0.1-5.0% (preferably 0.5-2%),

[0048] B) fatty acid surfactant 2-7%,

[0049] C) nonionic surfactant 2-15%,

[0050] D) anionic surfactant other than B) 2-8%,

[0051] E) chelating agent 0-0.5%,

[0052] F) enzyme preparation 0-0.2%,

[0053] G) thickening agent 0-2%,

[0054] H) preservative 0-0.2%,

[0055] I) pH adjuster,

[0056] J) perfume 0-1%,

[0057] H) water balance.

[0058] The pH adjuster is one or more of sodium hydroxide, potassium hydroxide. The thickening agent includes one or more of sodium chloride, sodium citrate, sodium formate, sodium sulfate, polyacrylic polymer and polysaccharide polymer. The enzyme preparation includes one or more of protease, amylase, cellulase, lipase and mannanase. The preservative includes one or more of methylisothiazolinone, methylchloroisothiazolinone, benzisothiazolinone, phenoxyethanol and nipagin.

[0059] A method for preparing a liquid detergent composition, comprising the following steps:

[0060] 1) adding part of the pH adjuster in water, and then adding the fatty acid surfactant, and stirring uniformly at 40-60°C.

[0061] 2) sequentially adding the nonionic surfactant, the rest of the anionic surfactant, and stirring uniformly.

[0062] 3) cooling to 30-40°C, adjusting the pH to 8.5-9.5, then adding the rest of the components, stirring uniformly, and finally adding the dye fixative and making up to 100% with water. Specific embodiments

[0064] A process for preparing a liquid detergent, comprising the following steps:

[0065] 1) adding part of potassium hydroxide into deionized water first, then adding fatty acid, and stirring uniformly at 40-60°C;

[0066] 2) adding nonionic surfactant, the rest of anionic surfactant successively, and stirring uniformly;

[0067] 3) cooling to 30-40°C, adjusting pH to the range of 8.5-9.5 with potassium hydroxide, then adding the rest of components, stirring uniformly, finally adding dye fixing agent, and supplementing water to 100%.

[0068] The raw materials or reagents used in the following examples are all ordinary commercially available products unless otherwise specified.

[0069] The trade names or abbreviations of some components used in the examples and comparative examples are as follows:

[0070] AES: sodium fatty alcohol polyoxyethylene ether sulfate, the carbon chain length of fatty alcohol is 12-14, and the average ethoxylation degree is 2;

[0071] AEO-9: fatty alcohol polyoxyethylene ether, the carbon chain length of fatty alcohol is 12-14, and the average ethoxylation degree is 9;

[0072] AEO-7: fatty alcohol polyoxyethylene ether, the carbon chain length of fatty alcohol is 12-14, and the average ethoxylation degree is 7; K12: sodium fatty alcohol sulfate;

[0073] MES: sodium fatty acid methyl ester sulfonate;

[0074] AOS: sodium α-olefin sulfonate;

[0075] LAS: sodium dodecyl benzene sulfonate;

[0076] AEC-9H: fatty alcohol polyoxyethylene ether carboxylic acid;

[0077] EDTA-2Na: disodium ethylenediaminetetraacetate, chelating agent;

[0078] KF-88: kathon, preservative.

[0079] The stability test is carried out by visual inspection as follows: after the prepared liquid detergent sample is stored at low temperature (-5°C) for a period of time (1 week, 2 weeks, 4 weeks or 8 weeks), it is taken out for observation, and the phenomenon is recorded.

[0080] The color protection and color transfer prevention test of the prepared liquid detergent composition is carried out according to the following method:

[0081] 1. Cut 6cm*6cm size of red, yellow, navy blue color cloth with reactive dye, three pieces for each cloth base, and determine the L* / a* / b* value of the cloth sample before washing with Color.

[0082] 2. Prepare 250 ppm (Ca 2+ : Mg 2+ = 3:2) hard water, dissolve 1.5 g of the prepared detergent composition in 750 mL of hard water, stir until fully dissolved, and preheat to 30°C in advance.

[0083] 3. Put in 3 pieces of cloth base, and wash in a vertical decontamination machine (RHLQ III type, manufactured by China Daily Chemical Industry Research Institute) for 20 minutes (180 rpm).

[0084] 4. Take out the cloth pieces in order, rinse the cloth pieces twice, thereby completing one washing, and dry after 3 cycles of washing. Determine the L* / a* / b* value after washing.

[0085] And calculate ΔE based on the measurement results before and after washing, the lower the ΔE, the better the color protection effect.

[0086] Among them, the cloth used in the color protection experiment is direct yellow, direct green and direct black, and each color cloth is washed with an additional three pieces of 40 double-sided white knitted cotton cloth. The washing steps are the same as the color protection test steps. And by testing the color difference of white cotton cloth before and after washing, it is determined whether the composition has color protection effect.

[0087] According to GBT 13174-2008 "Determination of Detergency and Performance of Detergent for Fabrics", the prepared detergent composition is evaluated for its detergency effect.

[0088] Table 1: Formulation of Examples 1-7 and Comparative Example 1

[0089]

[0090] Note: Dye fixing agent 1 is poly(2-hydroxypropyl dimethyl ammonium chloride), TEXCARE DFC 6, purchased from Clariant.

[0091] Table 2: Performance test results of Examples 1-7 and Comparative Example 1

[0092]

[0093] √: clear and transparent; o: hazy, turbid; x: precipitated and layered.

[0094] From the data in Table 1 and Table 2, it can be seen that the addition of fatty acid to the anionic surfactant system of the composition can improve the low temperature stability of the formulation; further, comparing the formulation system without the addition of fatty acid but with the addition of dye fixative (Comparative Example 1) and the formulation system without the addition of dye fixative but with the addition of fatty acid (Example 2), the low temperature stability of the formulation system with the addition of both fatty acid and dye fixative (Example 1) is obviously improved due to the addition of dye fixative, which indicates that the addition of dye fixative has little effect on the improvement of the low temperature stability of the system when the formulation does not contain fatty acid. Comparing Examples 4, 5, 6 and 7, it can be seen that the addition of dye fixative can significantly improve the low temperature stability of the composition only when the proportion of fatty acid in the total anionic surfactant is within a certain range (30-60%, further preferably 45-55%).

[0095] Table 3: Formulations of Examples 8-13 and Comparative Example 2

[0096] Component Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Control 2 Dye fixative 1 ]] 0.1 0.5 0.9 1.5 2.0 2.5 0 AES 5.5 5.5 5.5 5.5 5.5 5.5 5.5 AEO-9 4 4 4 4 4 4 4 Cocoate 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Oleate 3 3 3 3 3 3 3 AEO-7 2 2 2 2 2 2 2 EDTA-2Na 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Sodium citrate dihydrate 1 1 1 1 1 1 1 NaCl 1.5 1.5 1.5 1.5 1.5 1.5 1.5 KOH to 9.1 to 9.1 to 9.1 to 9.1 to 9.1 to 9.1 to 9.1 KF-88 0.1 0.1 0.1 0.1 0.1 0.1 0.1

[0097] Table 4: Performance test results of Examples 8-13 and Comparative Example 2

[0098]

[0099] From the data in Table 3 and Table 4, it can be seen that when the content of dye fixative is too low (Example 8), it cannot improve the low temperature stability of the composition, and when the amount of dye fixative is further increased, the improvement of the low temperature stability of the composition is more obvious (Examples 9-12). However, it is not desirable to add too much, which is not economical and does not have beneficial effects on color protection and low temperature stability.

[0100] Table 5: Formulations of Examples 14-18 and Comparative Example 3

[0101]

[0102]

[0103] Table 6: Performance test results of Examples 14-18 and Comparative Example 3

[0104] Example 14 Example 15 Example 16 Example 17 Example 18 Control 3 Compatibility Hazy Hazy Hazy Hazy Clear Clear

[0105] From Table 5 and Table 6, it can be seen that when the anionic surfactant structure does not contain an ethoxy block within the aforementioned limited range, the addition of dye fixative can make the formulation system become not clear or turbid (Examples 14-17). The precipitate is separated out after Examples 16 and 17 are placed at low temperature for 48 hours, and the low temperature stability is poor.

[0106] Table 7: Formulation of Examples 19-20 and Control Example 4

[0107] Component Example 19 Example 20 Control 4 Dye fixative 1 ]] 0.3 1.0 0 AES 5.5 5.5 5.5 AEO-9 4 4 4 Cocoate 2.5 2.5 2.5 Oleate 3 3 3 AEO-7 2 2 2 EDTA-2Na 0.2 0.2 0.2 Sodium citrate dihydrate 1 1 1 NaCl 1.5 1.5 1.5 KOH to 9.1 to 9.1 to 9.1 KF-88 0.1 0.1 0.1

[0108] Table 8: Performance test results of Examples 19-20 and Control Example 4

[0109]

[0110] From Table 7 and Table 8, it can be seen that the addition of the dye fixing agent in the composition framework can have certain color protection effects on reactive dye yellow cloth and red cloth; in the results of pure cotton white cloth mixed with direct dye yellow cloth and navy blue cloth, the dye fixing agent also has certain anti-bleeding effects. Finally, the addition of the dye fixing agent in the composition framework has less negative impact on the three national standard stained cloths, and even has a slight improvement effect on the removal of carbon black stained cloth.

[0111] The raw materials and equipment used in the present application are conventional raw materials and equipment in the art unless otherwise specified; the methods used in the present application are conventional methods in the art unless otherwise specified.

[0112] The above is only a preferred embodiment of the present application, and does not limit the present application in any way, and any simple modification, change and equivalent transformation of the above embodiment according to the technical essence of the present application still belongs to the protection scope of the technical solution of the present application.

[0113] The scope of protection.

Claims

1. A method for simultaneously improving the low temperature stability of a liquid detergent composition and the compatibility of a dye fixative in the system, characterized in that: The liquid detergent composition comprises the following raw materials by mass percentage: 0.5-2% of amines and reactants of epichlorohydrin as dye fixatives, 2-15% of nonionic surfactants, 2-7% of fatty acid surfactants, 2-8% of fatty alcohol polyoxyethylene ether sulfate and / or fatty alcohol polyoxyethylene ether carboxylate, water; pH is 8.5-9.5; The liquid detergent composition does not contain any of alkyl sulfonate, alkyl chain sulfate, alkyl chain benzene sulfonate and α-alkyl sulfonate; The fatty acid surfactant is one or more of lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid; The fatty acid surfactant accounts for 45-60% of the total amount of fatty alcohol polyoxyethylene ether sulfate, fatty alcohol polyoxyethylene ether carboxylate and fatty acid surfactant; The weight ratio of nonionic surfactant to the sum of fatty alcohol polyoxyethylene ether sulfate, fatty alcohol polyoxyethylene ether carboxylate and fatty acid surfactant is 0.4-0.545:

1.

2. The method of claim 1, wherein: The amine is a primary amine, a secondary amine or a tertiary amine.

3. The method of claim 2, wherein: The dye fixative is the reaction product of dimethylamine and epichlorohydrin, i.e. poly(2-hydroxypropyl dimethyl ammonium chloride).

4. The method of claim 1, wherein: The nonionic surfactant includes one or more of alkyl glycoside, fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, fatty acid methyl ester ethoxylate and amine oxide type surfactant.

5. The method of claim 1, wherein: The total content of the fatty alcohol polyoxyethylene ether sulfate, the fatty alcohol polyoxyethylene ether carboxylate and the fatty acid surfactant is 4-15%.

6. The method of claim 1, wherein: The liquid detergent composition comprises the following components by mass percentage: A) 0.5-2% of dye fixatives, B) 2-7% of fatty acid surfactants, C) 2-15% of nonionic surfactants, D) 2-8% of fatty alcohol polyoxyethylene ether sulfate and / or fatty alcohol polyoxyethylene ether carboxylate, E) 0-0.5% of chelating agents, F) 0-0.2% of enzyme preparations, G) 0-2% of thickening agents, H) 0-0.2% of preservatives, I) pH adjusters, J) 0-1% of fragrances, H) water in balance.

7. The method of claim 6, wherein: The preparation method of the liquid detergent composition comprises the following steps: 1) Add part of the pH adjuster in water, then add the fatty acid surfactant, and stir uniformly at 40-60°C; 2) Add the nonionic surfactant, the fatty alcohol polyoxyethylene ether sulfate and / or the fatty alcohol polyoxyethylene ether carboxylate in sequence, and stir uniformly; 3) Cool to 30-40°C, adjust the pH to 8.5-9.5, add the remaining components except the dye fixatives, stir uniformly, add the dye fixatives, and supplement water to 100%.

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