High oxygen-containing detergent composition having stable viscosity and method of making same

Abstract

The present application relates to the field of detergent, and discloses a high-oxygen-containing detergent composition with stable viscosity and a preparation method thereof, the detergent composition comprises the following components by mass percentage: 3.5-8.0% hydrogen peroxide, 1-10% anionic surfactant, 5-14% nonionic surfactant, 0.5-3% thickening agent, 0.002-0.02% hydrogen peroxide stabilizer, neutralizer, and water in remainder; the pH of the detergent composition is 4-7. The detergent composition has high effective oxygen content and long-term viscosity stability, the surfactant and hydrogen peroxide can jointly act on stains to quickly remove stains and restore the whiteness of clothes. Moreover, the preparation method has the characteristics of simple process and being conducive to long-term viscosity stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of detergents, in particular to a high-oxygen detergent composition with stable viscosity and a preparation method thereof. BACKGROUND

[0002] With the improvement of people's living standards, not only ordinary laundry liquid but also deep cleaning agent is needed to help remove stains and increase the brightness of clothes. The dyes used in most fabrics have poor chlorine color fastness, and the hypochlorous acid in traditional chlorine bleaching agents not only destroys the structure of stains but also damages the structure of dyes, which causes damage to the color of clothes and irreversible damage. Oxygen bleaching agent has attracted attention in recent years because hydrogen peroxide in oxygen bleaching agent reacts with stains to generate oxygen and water, which does not cause chlorine residue and is more in line with the demand for green and environmental protection; at the same time, hydrogen peroxide has little damage to fabrics and dyes, and is also suitable for bleaching and washing of colored fabrics.

[0003] The oxygen bleaching liquid used in the domestic market at present has the characteristics of low viscosity, low oxygen content, and poor adhesion, and it is easy to flow off when pre-coated on clothes, and it is difficult to fix on local stains. The stain remover with certain viscosity can not only be added to water to soak and wash clothes, but also can be pre-coated on fabrics to fix on local stains, reduce the amount of laundry liquid in the subsequent washing process, and the high concentration of oxygen content is more conducive to the removal of stains.

[0004] In order to increase the viscosity of oxygen bleaching liquid while ensuring the stability of hydrogen peroxide, a thickening agent needs to be added to thicken while adding a hydrogen peroxide stabilizer. However, in a relatively high concentration of hydrogen peroxide system, many acidic / neutral thickening agents cannot achieve good thickening effect, especially under high temperature conditions, which may be caused by the strong oxidizing property of hydrogen peroxide. Therefore, selecting appropriate thickening agent and surfactant is the key to thickening. SUMMARY

[0005] In view of the problems of small viscosity and low effective oxygen content of the existing oxygen bleaching liquid, the present application provides a high-oxygen detergent composition with stable viscosity and a preparation method thereof. The detergent composition has high effective oxygen content and long-term viscosity stability, and the preparation method has the characteristics of simple process and long-term viscosity stability.

[0006] The specific technical scheme of the present application is as follows:

[0007] In the first aspect, the present application provides a high-oxygen detergent composition with stable viscosity, which comprises the following components by mass percentage:

[0008] 3.5-8.0% hydrogen peroxide, 1-10% anionic surfactant, 5-14% nonionic surfactant, 0.5-3% thickening agent, 0.002-0.02% hydrogen peroxide stabilizer, neutralizing agent, and water in balance. The pH of the detergent composition is 4-7.

[0009] The thickening agent is one or more of acryloyl oxydimethyl ammonium taurate carboxyethyl acrylate cross-linked copolymer, polyvinyl pyrrolidone, polyethylene glycol stearate, acrylate cross-linked polymer, and PPG-2 hydroxyethyl cocamide.

[0010] The present inventors have found that a compound having an amide bond, an ester bond, or a C-C chain polymer structure of a pyrrolidone has a certain thickening effect on a detergent system containing hydrogen peroxide, while conventional thickening agents such as cellulose ethers, xanthan gum, and inorganic salts such as NaCl have no thickening effect on the system.

[0011] Further preferably, the thickening agent is acryloyl oxydimethyl ammonium taurate carboxyethyl acrylate cross-linked copolymer or PPG-2 hydroxyethyl cocamide.

[0012] Preferably, the nonionic surfactant is one or more of C12-C18 fatty alcohol polyoxyethylene ether, C12-C18 isomeric alcohol polyoxyethylene ether, and C12-C14 alkyl glycoside.

[0013] Further preferably, when the nonionic surfactant is C12-C18 isomeric alcohol polyoxyethylene ether, the number of EO is 12-30.

[0014] The number of EO is preferably between 12 and 30, and the proportion of long EO chains needs to be more than 60%, otherwise the viscosity stability is poor. The possible reason is that the orderly arrangement of longer EO increases the intermolecular force, improving the viscosity stability.

[0015] Preferably, the anionic surfactant is one or more of sodium linear alkyl benzene sulfonate, sodium linear alkyl sulfate, sodium fatty alcohol polyoxyethylene ether sulfate, alkenyl sulfonate, and sodium methyl lauroyl taurate.

[0016] Further preferably, the anionic surfactant is one or more of sodium linear alkyl benzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate, and alkenyl sulfonate.

[0017] Preferably, when the thickening agent is acryloyl oxydimethyl ammonium taurate carboxyethyl acrylate cross-linked copolymer, the mass ratio of anionic surfactant to nonionic surfactant is ≤0.5, the nonionic surfactant is preferably Lutensol TO 20 (BASF), the anionic surfactant is preferably sodium linear alkyl benzene sulfonate, and the neutralizing agent is preferably triethanolamine.

[0018] As a preference, when the thickening agent is PPG-2 hydroxyethyl cocoamide, the nonionic surfactant is C12-C14 alkyl glycoside; the anionic surfactant is sodium linear alkyl benzene sulfonate and sodium fatty alcohol polyoxyethylene ether sulfate.

[0019] As a preference, the hydrogen peroxide stabilizer is pyridinone ethanolamine salt.

[0020] As a preference, the pH of the detergent composition is 5-6.

[0021] The team of the present application found that the above-mentioned preferred pH can obviously further benefit the viscosity stability and effective oxygen content stability of the system.

[0022] In a second aspect, the present application provides a preparation method of the above-mentioned detergent composition, comprising the following steps:

[0023] (1) adding the anionic surfactant together with the nonionic surfactant into water and stirring until uniform, and adding water to make the water content in the system 40-50 wt% after water addition;

[0024] (2) adjusting the pH with a neutralizing agent and stirring until uniform;

[0025] (3) adding the thickening agent, reducing the stirring speed, and stirring until uniform;

[0026] (4) adding the hydrogen peroxide and the hydrogen peroxide stabilizer and stirring until uniform.

[0027] The present application found that different feeding sequences have obvious effects on the long-term viscosity and oxygen content of the detergent composition of the present application. The method of the present application needs to adjust the pH first and then add the thickening agent, and the thickening agent is added before the hydrogen peroxide, which is beneficial to the uniformity of the overall pH, the uniform dispersion of the thickening agent, and the long-term viscosity stability of the detergent; the hydrogen peroxide and the stabilizer are added last, which reduces the decomposition of the hydrogen peroxide during the preparation process.

[0028] Compared with the prior art, the present application has the following technical effects:

[0029] (1) The present application found that selecting a C-C chain polymer structured compound with an amide bond, an ester bond or a pyrrolidone structure as a thickening agent has certain thickening effect on the detergent system containing hydrogen peroxide, while selecting a conventional thickening agent such as a biopolymer and a modified polymer such as a cellulose ether, xanthan gum and an inorganic salt such as NaCl has no thickening effect on the system.

[0030] (2) The preparation method of the present application needs to adjust pH first, then add thickening agent, and the thickening agent is added before hydrogen peroxide, which is beneficial to the consistency of the whole pH, the uniform dispersion of the thickening agent, and the long-term viscosity stability of the detergent. DETAILED DESCRIPTION

[0031] The present application will be further described below with reference to examples.

[0032] General examples

[0033] A high-oxygen-containing detergent composition with stable viscosity comprises the following components by mass percentage:

[0034] 3.5-8.0% hydrogen peroxide, 1-10% anionic surfactant, 5-14% nonionic surfactant, 0.5-3% thickening agent, 0.002-0.02% hydrogen peroxide stabilizer, neutralizer, and water in balance. The pH of the detergent composition is 4-7 (further preferably 5-6).

[0035] As a preference, the thickening agent is one or more of acryloyl oxydimethyl ammonium taurate carboxyethyl acrylate cross-linked copolymer, polyvinyl pyrrolidone, polyethylene glycol stearate, acrylate cross-linked polymer, and PPG-2 hydroxyethyl cocamide. Further preferably, it is acryloyl oxydimethyl ammonium taurate carboxyethyl acrylate cross-linked copolymer or PPG-2 hydroxyethyl cocamide.

[0036] As a preference, the nonionic surfactant is one or more of C12-C18 fatty alcohol polyoxyethylene ether, C12-C18 isomeric alcohol polyoxyethylene ether, and C12-C14 alkyl glycoside. Further preferably, it is C12-C18 isomeric alcohol polyoxyethylene ether with an EO number of 12-30.

[0037] As a preference, the anionic surfactant is one or more of sodium linear alkyl benzene sulfonate, sodium linear alkyl sulfate, sodium fatty alcohol polyoxyethylene ether sulfate, alkenyl sulfonate, and sodium methyl lauroyl taurate. Further preferably, it is one or more of sodium linear alkyl benzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate, and alkenyl sulfonate.

[0038] As a preference, when the thickening agent is acryloyl oxydimethyl ammonium taurate carboxyethyl acrylate cross-linked copolymer, the mass ratio of anionic surfactant to nonionic surfactant is ≤0.5, the nonionic surfactant is preferably Lutensol TO 20 (BASF), the anionic surfactant is preferably sodium linear alkyl benzene sulfonate, and the neutralizer is preferably triethanolamine.

[0039] As a preference, when the thickening agent is PPG-2 hydroxyethyl cocoamide, the nonionic surfactant is C12-C14 alkyl glycoside; the anionic surfactant is sodium linear alkyl benzene sulfonate and sodium fatty alcohol polyoxyethylene ether sulfate.

[0040] As a preference, the hydrogen peroxide stabilizer is pyridinone ethanolamine salt.

[0041] A preparation method of the above-mentioned detergent composition containing hydrogen peroxide, comprising the following steps:

[0042] (1) The anionic surfactant is added to water together with the nonionic surfactant and stirred uniformly, and after adding water, the water content in the system is 40-50 wt%;

[0043] (2) The pH is adjusted with a neutralizing agent and stirred uniformly;

[0044] (3) The thickening agent is added, the rotation speed is reduced, and stirred uniformly;

[0045] (4) The hydrogen peroxide and the hydrogen peroxide stabilizer are added and stirred uniformly. Specific embodiments

[0047] In the following examples, the following abbreviations will be used:

[0048] LAS: sodium linear alkyl benzene sulfonate, the number of carbon atoms of the alkyl group is 11-13;

[0049] AOS: sodium a-olefin sulfonate, the number of carbon atoms of the alkyl group is 14-16;

[0050] AES: sodium fatty alcohol polyoxyethylene ether sulfate, the carbon chain length of the fatty alcohol is 12-14, and the average degree of ethoxylation is 3;

[0051] MES: sodium fatty acid methyl ester sulfonate, the number of carbon atoms of the alkyl group is 12-14;

[0052] Tac: Clariant Aristoflex Tac, acryloyl dimethyl ammonium taurate / carboxyethyl acrylate cross-linked copolymer;

[0053] VPC: ARLYPON VPC (BASF), ethoxylated fatty alcohol / ethoxylated fatty amine;

[0054] Carbopol U20: Carbopol Ultrez 20 (Lubrizol), acrylate / C10-30 alkyl acrylate cross-linked copolymer;

[0055] Lutensol TO 20 (BASF): processed from saturated C13 isomeric alcohol, the number of EOs is 20;

[0056] APG: alkylglucoside, alkyl group having 12-14 carbon atoms;

[0057] AEO-9: fatty alcohol polyoxyethylene ether, EO number 9.

[0058] Method of implementation: a method for preparing a high-oxygen-containing detergent composition with stable viscosity, comprising the following steps:

[0059] (1) Anionic surfactant is added to a certain amount of water together with nonionic surfactant, water is 40-50% of the total amount, and stirred and mixed uniformly;

[0060] (2) Adjust the pH to 4-7 using a neutralizing agent, and stir and mix uniformly;

[0061] (3) Add thickening agent to the reactor, reduce the rotation speed, and stir and mix uniformly;

[0062] (4) Add hydrogen peroxide solution and hydrogen peroxide stabilizer, and stir and mix uniformly;

[0063] I. Viscosity effect of different thickening agents in different systems

[0064] According to Table 1 and Table 2, a variety of thickening agents show different viscosity effects in LAS Lutensol and LAS APG systems. The addition of NaCl in Table 1 reduces the initial viscosity and increases the viscosity reduction percentage. Cellulose ether, xanthan gum and VPC all show low initial viscosity in both systems, and the viscosity reduction percentage after 7 days at 45℃ is 100%. Although Carbomer U20 has better initial viscosity than cellulose ether, xanthan gum and VPC, it is still not as good as Tac and PPG-2 hydroxyethyl cocamide. The best performance in LAS Lutensol system is Tac, and the best performance in LAS APG system is PPG-2 hydroxyethyl cocamide.

[0065] Table 1 - Viscosity effect of different thickening agents in LAS Lutensol system

[0066]

[0067] Table 2 - Viscosity effect of different thickening agents in LAS APG system

[0068]

[0069] II. Study of Tac thickening agent system (Examples 1-10 and Comparative Examples 1-5)

[0070] Table 3 - Examples 1-10 and Comparative Examples 1-5

[0071]

[0072]

[0073] According to Table 3, it can be seen that:

[0074] In Examples 1-3 and Comparative Example 1, the main difference is that different anionic surfactants LAS, AES, AOS and MES are used. By comparing the data, it can be seen that in the Tac thickener system, when the nonionic surfactant is Lutensol TO 20, the viscosity reduction percentage of the system with anionic surfactant LAS is the lowest, and the viscosity stability is better.

[0075] In Comparative Examples 3 and 2 and Examples 1, 5 and 4, different proportions of LAS and Lutensol TO 20 are added, the proportions are 10:5, 6:9, 5:10, 4:11 and 1:14 respectively. According to the viscosity reduction percentage in 30 days, when LAS:Lutensol TO 20≤0.5, with the increase of the content of Lutensol TO 20, the initial viscosity of the system increases, and the viscosity stability also increases.

[0076] In addition, from Examples 1 and 6, it can be seen that when the neutralizing agent is selected as triethanolamine under the same pH, compared with NaOH neutralizing agent, the viscosity stability of the system is better. The reason may be that it neutralizes the carboxyl group in the system to form a stable polymer structure and increase the viscosity stability of the system. From Examples 6 and Comparative Examples 4 and 5, it can be seen that when the amount of triethanolamine added is low, the viscosity stability of the system decreases significantly.

[0077] III. Study on PPG-2 Hydroxyethyl Cocoamide Thickener System (Example 7 and Comparative Examples 6-12)

[0078] Table 4-Example 7 and Comparative Examples 6-12

[0079]

[0080]

[0081] From Table 4, it can be seen that the viscosity stability of Example 7 is good at high temperature, and it increases after 45°C. It shows that in the PPG-2 hydroxyethyl cocoamide thickener system, when there is only LAS and APG in the system, the stability is poor, and after adding AOS, AES, Lutensol TO 20 and AEO-9, only AES shows good thickening effect and subsequent viscosity stability.

[0082] IV. Effect of Different Preparation Methods on Viscosity Stability of the Composition System of the Invention

[0083] The comparison method is shown as follows:

[0084] (1) Add anionic and nonionic surfactants to water;

[0085] (2) Add hydrogen peroxide solution;

[0086] (3) Add thickening agent and stir well;

[0087] (4) Add pyridinone ethanolamine salt and stir well;

[0088] (5) Adjust pH and add the remaining water.

[0089] Table 5 - Viscosity change before and after 40 days at 45°C for the implementation method and the comparative method

[0090] Formulation 1 Formulation 2 Formulation 1 Formulation 2 Method Method Method Comparative Method Comparative Method Pyridone ethanolamine salt 0.01％ 0.005％ 0.01％ 0.005％ Initial viscosity (mPa.s) 2080 1880 1880 1900 Viscosity at 45°C, day 30 (mPa.s) 1840 1010 820 83 Percent viscosity reduction (%) 11.54 46.28 44.68 95.63

[0091] Formulation 1 in Table 5 is the same as the formulation of Example 1, and formulation 2 is based on formulation 1, with the amount of pyridinone ethanolamine salt reduced to 0.005%. Comparing the implementation method of formulation 1 with the comparative method, and the implementation method of formulation 2 with the comparative method, it can be seen that at 45°C, the viscosity retention of the implementation method is significantly better than that of the comparative method. When the amount of pyridinone ethanolamine salt added is 0.005%, the viscosity reduction percentage is significantly higher than that of 0.01% pyridinone ethanolamine salt.

[0092] V. Effect of different pH on viscosity stability and effective oxygen content of the system

[0093] According to the formulation of Example 1, the amount of NaOH was adjusted to obtain the following relationship between pH and viscosity, as shown in Table 6.

[0094] Table 6 - Relationship between pH and viscosity stability of the system

[0095] pH 3.13 3.63 4.1 4.5 4.7 5.15 5.62 6.2 7.23 8.15 Initial viscosity (mPa.s) 2360 2150 2080 2040 2070 2080 1860 1910 1440 1020 Viscosity at 45°C, day 30 (mPa.s) 0 269 1440 1720 1760 1840 1710 1660 1270 550 Percent viscosity reduction (%) 100 87.49 30.77 15.69 14.98 11.54 8.06 13.09 11.80 46.08

[0096] Effective oxygen content test: refer to the test method for effective oxygen content in QB / T 4310-2012.

[0097] Table 7 - Relationship between pH and effective oxygen content

[0098] pH 3.13 3.63 4.5 5.62 6.2 7.23 8.15 Initial available oxygen (%) 3.67 3.68 3.69 3.68 3.69 3.72 3.70 Available oxygen at 45°C, day 30 (%) 3.41 3.61 3.64 3.65 3.66 3.68 3.64 Percent available oxygen reduction (%) 7.08 1.90 1.36 0.82 0.81 1.08 1.62

[0099] According to Table 6, when pH ≤ 4.1 and > 8.15, the viscosity of the system is significantly reduced after 30 days at 45°C. According to Table 7, when pH is between 3.63 and 7.23, the loss of effective oxygen content is lower, and the oxygen content stability is better, and in combination with the viscosity reduction percentage, the optimal pH range is 5-6.

[0100] VI. Effect of anionic surfactant on detergency

[0101] Stain removal test: refer to GB / T 13174-2008 Determination of detergency and cyclic washing performance of laundry detergents, washing adjustment concentration 0.2%, 40℃, 160rpm, 20min.

[0102] Table 8 - Stain removal test

[0103] Test item Standard laundry liquid Example 1 Example 2 Example 3 Example 7 Carbon black 1.00 1.04 1.15 1.24 1.02 Protein 1.00 1.09 1.33 1.21 1.02 Sebum 1.00 1.40 1.18 1.18 1.43

[0104] Note: Table 8 data is the stain removal ratio.

[0105] Stain removal test: refer to GB / T 13174-2008 Determination of detergency and cyclic washing performance of laundry detergents, washing adjustment concentration 0.2%, 40℃, 160rpm, 20min.

[0106] Table 9 - Stain removal test

[0107]

[0108] Note: Table 9 data is ΔE value, the larger the ΔE value, the stronger the stain removal ability.

[0109] From Table 8, it can be seen that the stain removal ability of the composition of the present application on three kinds of stained cloth is stronger than that of the national standard liquid, and has good stain removal ability, and triethanolamine has no effect on the stain removal ability. According to the ΔE value of Table 9, for red wine stains and vegetable stains, the stain removal ability of the composition containing hydrogen peroxide component is better than that without hydrogen peroxide component, and the stain removal ability of Example 1 containing hydrogen peroxide on vegetable stains is obviously better than that of Comparative Example 12 without hydrogen peroxide, so the hydrogen peroxide composition has good stain removal effect.

[0110] 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.

[0111] The above is only the 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.

Claims

1. A process for the preparation of a high oxygenated detergent composition having stable viscosity, characterized by The method comprises: 1) adding anionic surfactant and nonionic surfactant into water and stirring; 2) adjusting pH with neutralizer and stirring; 3) adding thickening agent and stirring; 4) adding hydrogen peroxide and hydrogen peroxide stabilizer and stirring; The mass percentage of each component is: 7.7-8.0% hydrogen peroxide, 1-10% anionic surfactant, 5-14% nonionic surfactant, 2-3% thickening agent, 0.01-0.02% hydrogen peroxide stabilizer, neutralizer triethanolamine, and water in balance; The pH of the detergent composition is 5-6; The thickening agent is acryloyloxydimethylammonium taurate propyl acrylate carboxyethyl cross-linked copolymer; The nonionic surfactant is Lutensol TO 20; The anionic surfactant is one or more of sodium linear alkyl benzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate, and alkenyl sulfonate; The mass ratio of anionic surfactant to nonionic surfactant is ≤0.

5.

2. A process for preparing a high oxygenated detergent composition having stable viscosity as claimed in claim 1 wherein: The anionic surfactant is sodium linear alkyl benzene sulfonate.

3. The process for preparing high oxygenated detergent composition having stable viscosity as claimed in claim 1 wherein: The hydrogen peroxide stabilizer is pyridinone ethanolamine salt.

4. The process for preparing high oxygenated detergent composition having stable viscosity as claimed in claim 1 wherein: After adding water in step 1), the water content in the system is 40-50wt%.

5. The process for preparing high oxygenated detergent composition having stable viscosity as claimed in claim 2 wherein: The mass percentage of sodium linear alkyl benzene sulfonate in the high-oxygen-containing detergent composition is 5%.

6. The process for preparing high oxygenated detergent composition having stable viscosity as claimed in claim 1 wherein: The mass percentage of Lutensol TO 20 in the high-oxygen-containing detergent composition is 10%.

7. The method of making a high oxygenated detergent composition having stable viscosity as claimed in claim 1 wherein: The mass percentage of hydrogen peroxide in the high-oxygen-containing detergent composition is 7.7%.

8. The process for preparing high oxygenated detergent composition having stable viscosity as claimed in claim 1 wherein: The mass percentage of thickening agent in the high-oxygen-containing detergent composition is 2%.

9. A process for making a high oxygenated detergent composition having stable viscosity as claimed in claim 3 wherein: The mass percentage of hydrogen peroxide stabilizer in the high-oxygen-containing detergent composition is 0.01%.

10. The process for preparing a high oxygenated detergent composition having stable viscosity as claimed in claim 9 wherein: The pH of the high-oxygen-containing detergent composition is 5.1±0.1.

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