CN116554975A - A high oxygen-containing detergent composition with stable viscosity and preparation method thereof - Google Patents

Abstract

The invention relates to the field of detergents, and discloses a high-oxygen-content detergent composition with stable viscosity and a preparation method thereof, wherein the detergent composition comprises the following components in percentage by mass: 3.5-8.0% of hydrogen peroxide, 1-10% of anionic surfactant, 5-14% of nonionic surfactant, 0.5-3% of thickener, 0.002-0.02% of hydrogen peroxide stabilizer, neutralizer and the balance of water; the pH of the detergent composition is 4-7. The detergent composition has higher effective oxygen content and long-term viscosity stability, and the surfactant and the hydrogen peroxide can act on stains together to remove stains quickly and recover the whiteness of clothes. The preparation method has the characteristics of simple process and contribution to long-term viscosity stabilization.

Description

A high oxygen-containing detergent composition with stable viscosity and preparation method thereof

technical field

The invention relates to the field of detergents, in particular to a high-oxygen detergent composition with stable viscosity and a preparation method thereof.

Background technique

With the improvement of people's living standards, cleaning clothes requires not only ordinary laundry detergent, but also deep cleaners to help remove stains and increase the brightness of clothes. The dyes used in most fabrics have poor chlorine fastness. The hypochlorous acid in traditional chlorine bleaches destroys the structure of stains and also the structure of dyes, which destroys the color of clothes and causes irreversible damage. And oxygen bleach has attracted people's attention in recent years, and this is because hydrogen peroxide in the oxygen bleach reacts with stains to generate oxygen and water, which will not cause chlorine residues and is more in line with green environmental protection requirements; The damage of the dye is small, and it is also suitable for bleaching and cleaning of colored fabrics.

Oxygen bleaching liquid currently used in the market has the characteristics of low viscosity, low oxygen content, and poor adhesion. It is easy to lose when it is pre-coated on clothes, and it is difficult to fix it on local stains. The stain remover with a certain viscosity can not only be added in water to soak and wash clothes, but also can be pre-coated on fabrics to fix them on local stains, reducing the amount of laundry detergent in the subsequent washing process, and the higher concentration of oxygen content is more effective. Helps remove stains.

While ensuring the stability of hydrogen peroxide, in order to increase the viscosity of the oxygen bleaching liquid, it is necessary to add a thickener for thickening while adding a hydrogen peroxide stabilizer. However, in a relatively high concentration hydrogen peroxide system, many acidic/neutral thickeners cannot achieve a good thickening effect, especially under high temperature conditions, which may be caused by the strong oxidation of hydrogen peroxide. Therefore, choosing the right thickener and surfactant is the key to thickening.

Contents of the invention

Aiming at the problems of low viscosity and low oxygen content of available oxygen in the existing oxygen bleaching solution, the invention provides a high oxygen-containing detergent composition with stable viscosity and a preparation method thereof. The detergent composition has relatively high effective oxygen content and long-term viscosity stability, and its preparation method has the characteristics of simple process and favorable long-term viscosity stability.

Concrete technical scheme of the present invention is:

In the first aspect, the present invention provides a high oxygen-containing detergent composition with stable viscosity, comprising the following components in mass percentage:

3.5-8.0% hydrogen peroxide, 1-10% anionic surfactant, 5-14% non-ionic surfactant, 0.5-3% thickener, 0.002-0.02% hydrogen peroxide stabilizer, neutralizer, water margin. The pH of the detergent composition is 4-7.

Wherein, the thickener is acryloxydimethyl ammonium taurate carboxyethyl acrylate cross-linked copolymer, polyvinylpyrrolidone, polyethylene glycol stearate, acrylate cross-linked polymer and PPG - One or more of 2 hydroxyethyl cocamides.

The team of the present invention accidentally found that compounds with C-C chain polymer structures having amide bonds, ester bonds or pyrrolidone structures have a certain thickening effect on detergent systems containing hydrogen peroxide, and when biopolymers and their modified polymers are selected When conventional thickeners such as cellulose ethers, xanthan gum, etc. and inorganic salts such as NaCl are used, there is no thickening effect on the system.

Further preferably, the thickener is acryloxydimethyl ammonium taurate carboxyethyl acrylate cross-linked copolymer or PPG-2 hydroxyethyl cocamide.

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.

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

The number of EO is preferably between 12 and 30, and the proportion of long EO chains must exceed 60%, otherwise the viscosity stability is poor. The possible reason is that the neat arrangement of longer EO increases the intermolecular force and improves the viscosity stability.

As preferably, the anionic surfactant is linear alkylbenzene sulfonate sodium, linear alkyl sodium sulfate, fatty alcohol polyoxyethylene ether sodium sulfate, alkenyl sulfonate and sodium methyl lauroyl taurate one or more of .

Further preferably, the anionic surfactant is one or more of sodium linear alkylbenzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate and alkenyl sulfonate.

Preferably, when the thickener is acryloxydimethyl taurate ammonium carboxyethyl acrylate crosslinked copolymer, the mass ratio of anionic surfactant to nonionic surfactant is ≤0.5, and the nonionic surfactant Preferably it is Lutensol TO 20 (BASF); the anionic surfactant is preferably sodium linear alkylbenzene sulfonate; the neutralizing agent is preferably triethanolamine.

As a preference, when the thickener is PPG-2 hydroxyethyl cocamide, the nonionic surfactant is C12～C14 alkyl glycoside; the anionic surfactant is sodium linear alkylbenzene sulfonate and fatty alcohol polyoxygen Sodium Vinyl Ether Sulfate.

Preferably, the hydrogen peroxide stabilizer is pyridone ethanolamine salt.

Preferably, the pH of the detergent composition is 5-6.

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

Second aspect, the present invention provides a kind of preparation method of above-mentioned detergent composition, comprises the following steps:

(1) Add the anionic surfactant and the nonionic surfactant into the water and stir evenly, and the water content in the system after adding water is 40-50wt%;

(2) adjust the pH with a neutralizing agent and stir evenly;

(3) Add a thickener, reduce the rotating speed, and stir evenly;

(4) Add hydrogen peroxide and hydrogen peroxide stabilizer and stir evenly.

The present inventors have found that different order of addition has a significant effect on the long-term viscosity as well as the oxygen content of the detergent compositions of the present invention. The method of the present invention needs to adjust the pH first and then add the thickener, and the thickener is added before the hydrogen peroxide, which is conducive to the consistency of the overall pH, the uniform dispersion of the thickener, and the long-term viscosity stability of the detergent; Hydrogen peroxide and stabilizer are added last, which reduces the decomposition of hydrogen peroxide during the preparation process.

Compared with the prior art, the present invention has the following technical effects:

(1) The present invention finds that the C-C chain polymer structure compound with amide bond, ester bond or pyrrolidone structure is selected as a thickener, which has a certain thickening effect on the detergent system containing hydrogen peroxide, and when the biopolymer is selected When it is combined with modified polymer polymers such as cellulose ethers, xanthan gum, etc. and inorganic salts such as NaCl and other conventional thickeners, there is no thickening effect on the system.

(2) In the preparation method of the present invention, it is necessary to adjust the pH first and then add the thickener, and the thickener is added before the hydrogen peroxide, which is conducive to the consistency of the overall pH, the uniform dispersion of the thickener, and the detergent Long-term viscosity stability; hydrogen peroxide and stabilizer are added last, reducing the decomposition of hydrogen peroxide during preparation.

Detailed ways

The present invention will be further described below in conjunction with embodiment.

General Example

A high oxygen-containing detergent composition with stable viscosity, comprising the following components in mass percentage:

3.5-8.0% hydrogen peroxide, 1-10% anionic surfactant, 5-14% non-ionic surfactant, 0.5-3% thickener, 0.002-0.02% hydrogen peroxide stabilizer, neutralizer, water margin. The pH of the detergent composition is 4-7 (more preferably 5-6).

Preferably, the thickener is acryloxydimethyl ammonium taurate carboxyethyl acrylate cross-linked copolymer, polyvinylpyrrolidone, polyethylene glycol stearate, acrylate cross-linked polymer and One or more of PPG-2 hydroxyethyl cocamide. More preferably, it is acryloxydimethyl ammonium taurate carboxyethyl acrylate cross-linked copolymer or PPG-2 hydroxyethyl cocamide.

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. More preferably, it is a C12-C18 isomeric alcohol polyoxyethylene ether whose EO number is 12-30.

As preferably, the anionic surfactant is linear alkylbenzene sulfonate sodium, linear alkyl sodium sulfate, fatty alcohol polyoxyethylene ether sodium sulfate, alkenyl sulfonate and sodium methyl lauroyl taurate one or more of . More preferably, it is one or more of sodium linear alkylbenzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate and alkenyl sulfonate.

Preferably, when the thickener is acryloxydimethyl taurate ammonium carboxyethyl acrylate crosslinked copolymer, the mass ratio of anionic surfactant to nonionic surfactant is ≤0.5, and the nonionic surfactant Preferably it is Lutensol TO 20 (BASF); the anionic surfactant is preferably sodium linear alkylbenzene sulfonate; the neutralizing agent is preferably triethanolamine.

As a preference, when the thickener is PPG-2 hydroxyethyl cocamide, the nonionic surfactant is C12～C14 alkyl glycoside; the anionic surfactant is sodium linear alkylbenzene sulfonate and fatty alcohol polyoxygen Sodium Vinyl Ether Sulfate.

Preferably, the hydrogen peroxide stabilizer is pyridone ethanolamine salt.

A kind of preparation method of above-mentioned detergent composition comprising hydrogen peroxide, comprises the following steps:

(1) Add the anionic surfactant and the nonionic surfactant into the water and stir evenly, and the water content in the system after adding water is 40-50wt%;

(2) adjust the pH with a neutralizing agent and stir evenly;

(3) Add a thickener, reduce the rotating speed, and stir evenly;

(4) Add hydrogen peroxide and hydrogen peroxide stabilizer and stir evenly.

specific embodiment

In the following examples, the following abbreviations will be used:

LAS: sodium linear alkylbenzene sulfonate, the number of carbon atoms in the alkyl group is 11-13;

AOS: sodium α-olefin sulfonate, the number of carbon atoms in the alkyl group is 14-16;

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

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

Tac: Clariant Aristoflex Tac, ammonium acryloyldimethyltaurate/carboxyethyl acrylate cross-linked copolymer;

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

Carbopol U20: Carbopol Ultrez20 (Lubrizol), acrylate/C10-30 alkyl acrylate cross-linked copolymer;

Lutensol TO 20 (BASF): Processed from saturated C13 isomeric alcohols, EO number is 20;

APG: alkyl glucoside, the number of carbon atoms in the alkyl group is 12-14;

AEO-9: Fatty alcohol polyoxyethylene ether, EO number is 9.

Implementation method: a method for preparing a high oxygen-containing detergent composition with stable viscosity, comprising the steps of:

(1) Anionic surfactant and nonionic surfactant are added into a certain amount of water together, the water is 40% to 50% of the whole amount, and stirred and mixed evenly;

(2) Use a neutralizer to adjust the pH to 4-7, stir and mix evenly;

(3) Add thickener in reactor, reduce rotating speed, stir and mix evenly;

(4) Add hydrogen peroxide solution and hydrogen peroxide stabilizer, stir and mix;

1. The viscosity effect of different thickeners in different systems

According to Table 1 and Table 2, various thickeners show different viscosity effects in LAS Lutensol and LAS APG systems. The addition of NaCl in Table 1 decreased the initial viscosity and increased the percent viscosity reduction. However, cellulose ether, xanthan gum and VPC all exhibited low initial viscosities in the two systems, and the percentage of viscosity reduction at 45°C for 7 days was 100%, while the initial viscosity of carbomer U20 was better than that of cellulose ether. , Xanthan Gum, and VPC, but not as much as Tac and PPG-2 Hydroxyethyl Cocamide. The best performer in the LAS Lutensol system is Tac, and the best performer in the LAS APG system is PPG-2 hydroxyethyl cocamide.

Table 1-Viscosity effect of different thickeners in LAS Lutensol system

Table 2-Viscosity effect of different thickeners in LAS APG system

Two, Tac thickener system research (embodiment 1-10 and comparative example 1-5)

Table 3-Examples 1-10 and Comparative Examples 1-5

According to Table 3, it can be seen that:

In Examples 1-3 and Comparative Example 1, the difference mainly lies in the use of different anionic surfactants LAS, AES, AOS and MES. Through data comparison, it can be seen that under the Tac thickener system, when the nonionic surfactant is LutensolTO 20, the viscosity reduction percentage of the system is the lowest when the anionic surfactant is LAS, and its viscosity stability is better.

In Comparative Examples 3, 2 and Examples 1, 5, and 4, different ratios of LAS and LutensolTO 20 were added, the ratios were 10:5, 6:9, 5:10, 4:11, 1:14, According to the percentage of viscosity reduction in 30 days, when LAS: Lutensol TO 20≤0.5, with the increase of Lutensol TO 20 content, the initial viscosity of the system increases, and the viscosity stability increases at the same time.

In addition, it can be seen from Example 1 and Example 6 that under the same pH conditions, when the neutralizing agent is selected as triethanolamine, it has a viscosity stabilizing effect on the system of the present invention relative to the NaOH neutralizing agent. Neutralize to form a stable polymer structure and increase the viscosity stability of the system. From Example 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.

3. Research on PPG-2 hydroxyethyl cocamide thickener system (Example 7 and Comparative Examples 6-12)

Table 4-Example 7 and Comparative Examples 6-12

It can be seen from Table 4 that the viscosity stability of Example 7 is good at high temperature and increases after 45°C. It shows that under the PPG-2 hydroxyethyl cocamide thickener system, when there are only LAS and APG in the system, the stability is poor, but after adding AOS, AES, LutensolTO 20 and AEO-9, only AES shows good stability. Thickening effect and subsequent viscosity stability.

Four, the impact of different preparation methods on the viscosity stability of the composition system of the present invention

The comparison method is as follows:

(1) Anionic and nonionic surfactants are added to water together;

(2) adding hydrogen peroxide solution;

(3) Add thickener and stir evenly;

(4) Add pyridone ethanolamine salt and stir;

(5) Adjust the pH and add the remainder of water.

Table 5 - Viscosity changes before and after storage at 45°C for 40 days between the implementation method and the comparison method

Recipe 1 Recipe 2 Recipe 1 Recipe 2 method Method of implementation Method of implementation comparison method comparison method Pyridone ethanolamine salt 0.01% 0.005% 0.01% 0.005% Initial viscosity (mPa.s) 2080 1880 1880 1900 Viscosity at 45°C on day 30 (mPa.s) 1840 1010 820 83 Viscosity reduction percentage (%) 11.54 46.28 44.68 95.63

Formulation 1 in Table 5 is the same as that of Example 1, and Formulation 2 is based on Formulation 1, but the amount of pyridone ethanolamine salt is reduced to 0.005%. Comparing the implementation method of formula 1 with the comparison method, and the implementation method of formula 2 with the comparison method, it can be seen that at 45°C, the viscosity retention of the implementation method is obviously better than that of the comparison method. When the added amount of pyridone ethanolamine salt is 0.005%, its viscosity reduction percentage is obviously higher than that of 0.01% pyridone ethanolamine salt.

5. The influence of different pH on the viscosity stability and effective oxygen content of the system

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

The relationship between table 6-pH and system viscosity stability

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 on day 30 (mPa.s) 0 269 1440 1720 1760 1840 1710 1660 1270 550 Viscosity reduction percentage (%) 100 87.49 30.77 15.69 14.98 11.54 8.06 13.09 11.80 46.08

Effective oxygen content test: refer to the test method of effective oxygen content in QB/T 4310-2012.

Table 7-Relationship between pH and effective oxygen content

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 (%) on the 30th day at 45°C 3.41 3.61 3.64 3.65 3.66 3.68 3.64 Percentage reduction of available oxygen (%) 7.08 1.90 1.36 0.82 0.81 1.08 1.62

According to Table 6, it can be seen that when the pH is ≤4.1 and >8.15, the viscosity of the system decreases significantly after being placed at 45°C for 30 days. According to Table 7, the relative pH=3.13, when the pH is between 3.63 and 7.23, the loss of effective oxygen content is low, the stability of oxygen content is better, combined with the percentage of viscosity reduction, the optimal pH range is 5 to 6.

6. Effect of anionic surfactant on detergency.

Decontamination performance test: Refer to GB/T 13174-2008 Detergency of Detergents for Clothing and Determination of Cycle Washing Performance, washing adjustment concentration is 0.2%, 40°C, 160rpm, 20min.

Table 8 - Stain removal performance test

Test items standard laundry detergent 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

Remarks: The data in Table 8 are decontamination ratios.

Stain removal performance test: refer to GB/T 13174-2008 Determination of Detergency and Cycle Washing Performance of Detergents for Clothing, and use specific stains to obtain stained cloth by padding and drying. With reference to the formula of Example 1, water was used instead of the hydrogen peroxide solution to obtain Comparative Example 13.

Table 9 - Stain removal performance test

Remarks: The data in Table 9 are ΔE values, the larger the ΔE value, the stronger the stain removal ability.

As can be seen from Table 8, the decontamination ability of the composition of the present invention to the three kinds of soiled cloths is stronger than that of the national standard liquid, and has good decontamination ability, and triethanolamine has no influence on the decontamination ability. According to the ΔE value in Table 9, it can be seen that for red wine stains and vegetable stains, the stain removal ability of the hydrogen peroxide component is better than that of the hydrogen peroxide component, and the stain removal of the vegetable stains in Example 1 containing hydrogen peroxide The ability is obviously better than that of Comparative Example 12 without hydrogen peroxide, so the hydrogen peroxide composition has a good stain removal effect.

Raw materials used in the present invention, equipment, if not specified, are commonly used raw materials, equipment in this area; Method used in the present invention, if not specified, are conventional methods in this area.

The above are only preferred embodiments of the present invention, and do not limit the present invention in any way. All simple modifications, changes and equivalent transformations made to the above embodiments according to the technical essence of the present invention still belong to the technical solution of the present invention. scope of protection.

Claims (10)

1. A high oxygen-containing detergent composition with stable viscosity, characterized in that: comprising the following components in mass percent: 3.5~8.0% hydrogen peroxide, 1~10% anionic surfactant, 5~14% non-ionic surfactant, 0.5~3% thickener, 0.002~0.02% hydrogen peroxide stabilizer, Neutralizer, water balance; The pH of the detergent composition is 4-7; The thickener is acryloyloxydimethyl taurate ammonium carboxyethyl acrylate cross-linked copolymer, polyvinylpyrrolidone, polyethylene glycol stearate, acrylate cross-linked polymer and PPG-2 One or more of hydroxyethyl cocamides. 2. detergent compositions as claimed in claim 1 is characterized in that: described thickener is acryloxy dimethyl taurate ammonium carboxyethyl acrylate cross-linked copolymer or PPG-2 hydroxyethyl Cocamide. 3. The detergent composition according to claim 1 or 2, characterized in that: The nonionic surfactant is one or more of C12~C18 fatty alcohol polyoxyethylene ether, C12~C18 isomerized alcohol polyoxyethylene ether and C12~C14 alkyl glycoside; The anionic surfactant is one of linear alkylbenzene sulfonate sodium, linear alkyl sodium sulfate, fatty alcohol polyoxyethylene ether sodium sulfate, alkenyl sulfonate and sodium methyl lauroyl taurate or more. 4. The detergent composition according to claim 3, characterized in that: The non-ionic surfactant is a C12-C18 isomeric alcohol polyoxyethylene ether with an EO number of 12-30; The anionic surfactant is one or more of sodium linear alkylbenzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfate and alkenyl sulfonate. 5. The detergent composition according to claim 4, characterized in that: The thickener is acryloyloxydimethyl ammonium taurate carboxyethyl acrylate cross-linked copolymer; The mass ratio of the anionic surfactant to the nonionic surfactant is ≤0.5. 6. The detergent composition according to claim 5, characterized in that: Described nonionic surfactant is Lutensol TO 20; The anionic surfactant is sodium linear alkylbenzene sulfonate; Described neutralizing agent is triethanolamine. 7. The detergent composition according to claim 3, characterized in that: Described thickener is PPG-2 hydroxyethyl cocamide; Described nonionic surfactant is C12～C14 alkyl glucoside; The anionic surfactant is sodium linear alkylbenzene sulfonate and fatty alcohol polyoxyethylene ether sodium sulfate. 8. The detergent composition according to claim 1 or 2, characterized in that: the hydrogen peroxide stabilizer is pyridone ethanolamine salt. 9. The detergent composition according to claim 1 or 2, characterized in that: the pH of the detergent composition is 5-6. 10. A preparation method of detergent composition as claimed in one of claims 1-9, characterized in that it comprises the following steps: (1) Add the anionic surfactant and the nonionic surfactant into the water and stir evenly; (2) Adjust the pH with a neutralizer and stir evenly; (3) Add thickener and stir evenly; (4) Add hydrogen peroxide and hydrogen peroxide stabilizer and stir well.