Preparation of hydrophobic deep-eutectic solvent taking tea saponin and tea polyphenol as hydrogen bond donors and application of hydrophobic deep-eutectic solvent in wash supplies

Abstract

The invention provides a hydrophobic deep-eutectic solvent taking tea saponin and tea polyphenol as hydrogen bond donors and application of the hydrophobic deep-eutectic solvent in a camellia oil washing and caring product. According to the invention, coco fatty acid diethanolamide and lauryl betaine are respectively used as hydrogen bond acceptors, tea saponin and tea polyphenol are used as hydrogen bond donors, and the hydrophobic deep-eutectic solvent type detergent with a cleaning function is prepared according to different substance amount ratios of the hydrogen bond donors and the hydrogen bond acceptors. The characteristics of detergency, foaming power and the like of the hydrophobic deep-eutectic solvent type detergent are detected, the ratio of tea polyphenol to tea saponin in a hydrogen bond donor is explored, natural, pollution-free and mild bath oil and massage oil are further prepared, and in the cleaning process, massage can be performed according to skin conditions, so that the utilization effect of active ingredients in the product is improved, and the skin care effect is improved. The development of the novel bath oil provides a new thought for the research of infant care products.

Description

Technical Field

[0001] The invention belongs to the field of preparation of cleaning products, and particularly relates to a hydrophobic low eutectic solvent with tea saponin and tea polyphenols as hydrogen bond donors and application thereof in camellia oil cleaning products. Background Art

[0002] Infants and young children are in a critical period of development. my country has nearly 10 million newborns every year, and the market demand for infant products is relatively large. Infants' skin is very delicate. On the one hand, the barrier function of infant skin is relatively poor, and the resistance to external stimuli and diseases is weak, which can easily cause skin infections and other problems. On the other hand, infants and young children's nervous system and intestinal control are immature, and they often have uncontrolled urination and defecation, causing redness and swelling of the buttocks and skin inflammation. Therefore, they need special care that is gentle, non-irritating, moisturizing and soothing.

[0003] Consumers are no longer satisfied with the cleaning function of soap and shower gel in their pursuit of bath products, but are more pursuing safe and natural care functions. Bath oils usually use natural oil ingredients, such as grape seed oil, olive oil, camellia oil and other plant oils. These ingredients have better biodegradability than the chemical synthetic agents that may be contained in shower gels. More importantly, the oil ingredients in bath oils can form a protective layer, lock in moisture, make the skin soft and delicate, moisturized and shiny, and provide deep moisturizing and nourishing for the skin. Since infants and young children's skin has not yet fully formed the dermis, the skin is prone to dryness and dehydration. Using bath oil can reduce water loss, form a protective film on the skin, protect the natural oil of the newborn's skin, and effectively prevent hard water from damaging the skin. Camellia oil, also known as tea seed oil, has been widely used in skin care products. Camellia oil is rich in unsaturated fatty acids and vitamin E and other ingredients. These substances help improve the skin barrier function, can penetrate deeply into the skin, provide long-lasting moisturizing, and help maintain the skin's hydration. In the oil-tea-producing areas, there is a folk remedy for treating infantile diaper rash, especially small-fruit camellia seed oil, which is more effective. At present, most young parents born in the 1980s prefer to buy natural, pollution-free and safe bath oil products for their babies and young children.

[0004] Deep Eutectic Solvents (DES) were first reported by Abbott et al. in 2003. They refer to two-component or three-component eutectic mixtures composed of hydrogen bond acceptors and hydrogen bond donors in a certain stoichiometric ratio. Their freezing point is significantly lower than the melting point of each component pure substance. This solvent can also be called "deep eutectic solvent" or "eutectic solvent". In 2015, the concept of hydrophobic deep eutectic solvent (HDES) was first proposed by Kroon's research group. Hydrophobic deep eutectic solvent is a type of low eutectic solvent with low polarity and hydrophobicity. This solvent has the characteristics of simple preparation and cheap and easy-to-obtain raw materials. It has broad application prospects in the fields of extraction separation, metal recovery, organic synthesis, etc. If a hydrophobic low eutectic solvent is explored, it can be miscible with oils and fats before meeting water as a massage care product, and can be dissolved in water after meeting water as a skin cleansing product, giving full play to the common characteristics of hydrophobic low eutectic solvents to achieve a two-in-one washing and care effect.

[0005] This invention applies the concept of hydrophobic low eutectic solvent to daily chemical cleaning products for the first time. Tea saponin molecules contain hydroxyl groups of various monosaccharides and hydrogen atoms in hydroxyl or carboxyl groups of organic acids, which can serve as hydrogen bond donors for hydrophobic low eutectic solvents. Tea polyphenols are complex compounds containing phenolic hydroxyl groups of multiple monomer components. These phenolic hydroxyl groups can also assist as hydrogen bond donors and are often used as anti-inflammatory, antioxidant, and antibacterial in skin care products. The hydrogen bond acceptors of hydrophobic low eutectic solvents can be provided by hydroxyl oxygen atoms in nonionic surfactants (coconut oil diethanolamide). Cationic surfactants (lauryl betaine) contain a long-chain alkyl group and a betaine group, which contains a nitrogen atom, two oxygen atoms, and three methyl groups, and have strong hydrophobic properties. The present invention uses coconut acid diethanolamide and lauryl betaine as hydrogen bond acceptors, tea saponin and tea polyphenols as hydrogen bond donors, and prepares a hydrophobic low eutectic solvent type detergent with cleaning function according to the amount ratio of different hydrogen bond donors and acceptors. The detergency and foaming power of the hydrophobic low eutectic solvent type detergent are tested, the ratio of tea polyphenols and tea saponin in the hydrogen bond donor is explored, and natural, pollution-free, mild bath oil and massage oil are further prepared. During the cleaning process, massage can be performed according to the skin condition to improve the utilization effect of the active ingredients in the product. The development of this new bath oil will provide new ideas for the research of infant care products. Summary of the invention

[0006] The invention aims to provide a hydrophobic low eutectic solvent with tea saponin and tea polyphenols as hydrogen bond donors and application thereof in camellia oil washing and care products.

[0007] To achieve the above object, the present invention adopts the following technical solution: The invention discloses a hydrophobic low eutectic solvent with tea saponin and tea polyphenols as hydrogen bond donors. The hydrophobic low eutectic solvent has tea saponin and tea polyphenols as hydrogen bond donors and coconut oil diethanolamide (6501) or lauryl betaine (BS-12) as hydrogen bond acceptor.

[0008] Furthermore, in the hydrophobic low eutectic solvent, the molar ratio of coconut oil diethanolamide (6501) to tea saponin is 40:3, and the mass proportion of tea polyphenols in hydrogen bond donors is 23.3%.

[0009] Furthermore, in the hydrophobic low eutectic solvent, the molar ratio of lauryl betaine (BS-12) to tea saponin is 40:7, and the mass proportion of tea polyphenols in hydrogen bond donors is 12.8%.

[0010] Furthermore, the preparation method of the hydrophobic low eutectic solvent comprises the following steps: mixing coconut oil diethanolamide (6501) or lauryl betaine (BS-12) with tea saponin and tea polyphenols, and stirring magnetically for 30 to 50 minutes at 50°C until the mixture is mixed into a clear and transparent liquid.

[0011] Furthermore, the application of the hydrophobic low eutectic solvent in camellia oil washing and care products: a hydrophobic low eutectic solvent bath oil prepared with coconut oil diethanolamide (6501) as a hydrogen bond acceptor, and the addition amount of camellia oil is 3.7%~16.1%. The specific preparation method includes: mixing the hydrogen bond acceptor coconut oil diethanolamide (6501) and camellia oil, stirring magnetically for 30 minutes at 50°C, adding tea saponin and tea polyphenols after complete mixing, and continuing to stir at 50°C for 1 hour to obtain a hydrophobic low eutectic solvent bath oil I.

[0012] Furthermore, the application of the hydrophobic low eutectic solvent in camellia oil washing and care products: a hydrophobic low eutectic solvent massage washing and care oil prepared with lauryl betaine (BS-12) as a hydrogen bond acceptor, and the amount of camellia oil added is 5.6%~12.8%. The specific preparation method includes: mixing the hydrogen bond acceptor lauryl betaine (BS-12) with tea saponin and tea polyphenols, stirring magnetically for 30-50 minutes at 50°C, and obtaining a clear and transparent liquid hydrophobic low eutectic solvent; slowly adding camellia oil at 50°C, stirring for 1 hour, and obtaining a hydrophobic low eutectic solvent type massage oil.

[0013] Further, the application of the hydrophobic low eutectic solvent in camellia oil washing and care products: the diluent isododecane is also added to the hydrophobic low eutectic solvent bath oil, and the mass ratio of the bath oil to the diluent isododecane is 7:3 to 3:7. The specific preparation method includes: mixing the hydrogen bond acceptor coconut oil diethanolamide (6501) and camellia oil, stirring magnetically for 30 minutes at 50°C, adding tea saponin and tea polyphenols after complete mixing, adding isododecane at 50°C, stirring for 1 hour, and preparing the hydrophobic low eutectic solvent bath oil II.

[0014] The advantages of the present invention are: The present invention uses tea saponin, tea polyphenols and other characteristic active ingredients of camellia oil as hydrogen bond donors, and other different types of surfactants as hydrogen bond acceptors to prepare a hydrophobic low eutectic solvent, which has good contact with the skin sebum membrane, and can exert the known physiological activities of the two during the massage and cleaning process, thereby enhancing the nursing effect similar to that of camellia oil. In addition, the present invention finds that the hydrophobic low eutectic solvent can be miscible with camellia oil, thus improving the more comprehensive two-in-one washing and care effect. Finally, the present invention realizes that the hydrophobic low eutectic solvent can be diluted and used by other moisturizers, etc., which can reduce production costs, expand the universality of washing and care products, and thus expand the scope of application. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 2.1 Flow chart of preparation of hydrophobic deep eutectic solvent; Figure 2.2 Decontamination results of the hydrophobic deep eutectic solvents; Figure 2.3 The results of bubble height determination of hydrophobic deep eutectic solvents; Figure 2.4 Results of determination of the foam stabilizing power of hydrophobic deep eutectic solvents; Figure 2.5 The results of the determination of the decontamination ability of the hydrophobic deep eutectic solvent of tea saponin and tea polyphenols; Figure 2.6 The foaming height measurement results of tea saponin and tea polyphenols hydrophobic deep eutectic solvent; Figure 2.7 The foam stabilizing ability test results of tea saponin and tea polyphenols hydrophobic deep eutectic solvent; Figure 3.1 Flow chart of preparation of hydrophobic deep eutectic solvent bath oil; Figure 3.2 Determination results of the detergency of bath oil and massage oil using hydrophobic deep eutectic solvents; Figure 3.3 The results of the foaming ability test of hydrophobic deep eutectic solvent bath oil and massage oil; Figure 3.4 Results of foam stabilization test of hydrophobic low eutectic solvent bath oil and massage oil. DETAILED DESCRIPTION

[0016] In order to make the above features and advantages of the present invention more clearly understood, the following embodiments are given for detailed description. The methods of the present invention are all conventional methods in the art unless otherwise specified.

[0017] 2 Exploration of configuration of tea saponin and tea polyphenols as hydrogen bond donors in hydrophobic deep eutectic solvents 2.1 Introduction Tea saponin is a compound of pentacyclic triterpenoid saponin, containing multiple functional groups such as hydroxyl (-OH). The hydrogen atoms in these functional groups can easily form hydrogen bonds with atoms with strong electronegativity (such as oxygen, nitrogen, etc.). Tea polyphenols are a natural antioxidant with a special phenolic hydroxyl group in its molecular structure. The hydrogen atoms in the phenolic hydroxyl group can also provide hydrogen bond donors. Coconut oil diethanolamide (6501) is a non-ionic surfactant. It has moisturizing, cleaning, emulsifying and dispersing effects in skin care products. Its molecular structure contains a hydrophobic group coconut oil acyl and multiple hydrophilic groups (such as hydroxyl). This structure makes it both hydrophilic and hydrophobic, and it is well miscible with a small amount of oil. Lauryl betaine (BS-12) is a mild surfactant with low irritation to the skin. It is suitable for all kinds of people, especially those with sensitive skin and infants. The oxygen atom and nitrogen atom in the carboxyl group (or carboxylate form) in its molecular structure have lone pairs of electrons, which enables it to act as a hydrogen bond acceptor and receive hydrogen atoms from hydrogen bond donors.

[0018] The purpose of this experiment is to explore a hydrophobic low eutectic solvent with tea saponin and tea polyphenols as hydrogen bond donors, optimize the ratio of hydrogen bond donors and acceptors, and test the properties, stability and washing efficacy of the hydrophobic low eutectic solvent.

[0019] 2.2 Experimental Materials and Instruments 2.2.1 Experimental Materials Table 2.1 Experimental materials 2.2.2 Experimental instruments Table 2.2 Experimental instruments 2.3 Experimental methods 2.3.1 Preparation of hydrophobic deep eutectic solvent Hydrophobic low eutectic solvents are synthesized by a simple one-step method. In addition to vacuum evaporation, grinding and freeze-drying, heating is the most commonly used method for preparing hydrophobic low eutectic solvents. The heating method refers to mixing the hydrogen bond acceptor (HBA) and the hydrogen bond donor (HBD) evenly, and then heating and stirring until the two phases form a transparent and uniform liquid.

[0020] This experiment adopts the heating method to prepare. According to the ratio of the amount of hydrogen bond donor and acceptor, a certain amount of hydrogen bond acceptor, such as cocoyl diethanolamide (6501) and lauryl betaine (BS-12), is placed in a beaker, and a certain amount of tea saponin and tea polyphenols are weighed and added to the beaker. At 50°C, the mixture is stirred in a magnetic stirrer for 30-50 minutes until it is mixed into a clear and transparent liquid. The specific preparation process is as follows: Figure 2.1 shown.

[0021] 2.3.2 Hydrophobicity test of hydrophobic deep eutectic solvents The stability of the hydrophobic low eutectic solvent mainly depends on the hydrogen bonding force in its composition structure. The stability and hydrophobicity of the hydrophobic low eutectic solvent composed of different types and proportions of HBA (hydrogen bond acceptor) and HBD (hydrogen bond donor) are different. The hydrophobic low eutectic solvent prepared in this experiment will be mainly used in washing products in the future. The prepared solvent needs to have a certain hydrophilicity and be able to dissolve in the water phase, and a certain hydrophobicity so that the oil phase can be added to prepare a natural and mild bath oil and massage oil. The specific method for testing the hydrophobicity in this experiment is: take 5g of the prepared hydrophobic low eutectic solvent, add 1g of oil while stirring at 50°C, mix for 30 minutes, and observe the stability of the solvent after standing at room temperature for 24 hours. Observe whether there is stratification and whether there is oil phase precipitation with the naked eye.

[0022] 2.3.3 Foaming Power Test of Hydrophobic Deep Eutectic Solvents This experiment refers to the Waring Blender method and is modified to adapt to existing conditions to test the foaming performance of the product. This method has the advantages of requiring less reagents and being less restricted by the environment. Dilute the sample to be tested to 0.2%, keep the temperature at 40°C, add 20mL to a 100mL measuring cylinder, hold both ends of the measuring cylinder with both hands, turn it upside down 8 times, observe the corresponding scale of the foam concave part, and observe the readings after 5min, 10min, 15min, and 20min to estimate its foaming ability and foam stabilization ability.

[0023] 2.3.4 Decontamination of Hydrophobic Deep Eutectic Solvents Detergent ability is an important indicator for evaluating cleaning products. This experiment was conducted based on the detergent ability test method in Appendix B of GB9985-2000 "Hand-washing Dishwashing Detergents" and modified according to actual conditions.

[0024] (1) Material preparation a. Samples to be tested: 1-Tea saponin hydrophobic low eutectic solvent, etc.; prepared into 1:20 concentration sample solution with tap water.

[0025] b. Artificial dirt: lard: butter: soybean oil = 1:1:2 ratio preparation, and add 5% of its mass of polyglycerol fatty acid to prepare artificial dirt.

[0026] c. Preparation of oil stain slides: Place the slide to be used in distilled water and boil for 15 minutes, then soak it in an acid solution for 1 hour, rinse the acid liquid attached to the slide with clean water, and then rinse it with distilled water. After drying, mark the slide and draw a line 1 cm from the top, where the oil stain is attached.

[0027] (2) Smearing method Weigh the treated slide (c) with an analytical balance (accurate to 0.001g), and the weight is m0. Fix it with a clip above the 1cm scale line, maintain the temperature of the artificial dirt (b) at 45~80℃ (determined by the room temperature, keep it at 80℃ when the room temperature is 25℃, and keep it at 45℃ when the room temperature is 20℃), immerse the lower end of the scale line of the slide into the oil for 1~2s and slowly remove it. After placing the oil-immersed slide at room temperature for 4h, weigh it with an analytical balance (accurate to 0.001g), and the weight is m1. The weight difference of the same batch of slides is kept at ±0.05g.

[0028] (3) Determination of dirt removal rate The sample to be tested (a) is heated and stirred in a constant temperature magnetic stirrer, and the temperature is maintained at 40°C. The glass slide is fixed above the sample with a clip, and the oil-immersed area below the scale line of the glass slide is immersed in the sample to be tested. Keep it for 1 minute, then set the speed of the magnetic stirrer to the same speed, and stir the sample to be tested to clean the glass slide for 2.5 minutes. After cleaning, place the glass slide at room temperature until it is completely dry, and weigh it again with an analytical balance (accurate to 0.001g) to obtain m2. Prepare three sets of glass slides for each set of samples to be tested, and the same batch of experiments are controlled at the same room temperature, water temperature and speed.

[0029] (4) Calculation of results Where: C——decontamination rate, % m0——mass of the slide before smearing, g m1——mass of the slide after smearing, g m2——The mass of the slide after sample liquid treatment, g 2.3.5 Design of hydrogen bond donor-acceptor ratio in hydrophobic deep eutectic solvents The hydrophobic low eutectic solvent is divided into two parts: hydrogen proton acceptor and hydrogen proton donor. In this experiment, 6501 and BS-12 were selected as hydrogen acceptors and tea saponin as hydrogen donors. The designed molar ratio of 6501 and tea saponin was (40:1, 40:3, 40:5, 40:7, 40:9), and the mass ratio was (10:1, 10:3, 10:5, 10:7, 10:9); the molar ratio of BS-12 and tea saponin was (40:1, 40:3, 40:5, 40:7, 40:9), and the mass ratio was (10:1, 10:3, 10:5, 10:7, 10:9). The tea saponin hydrophobic low eutectic solvents of different concentrations were prepared according to the preparation process of 2.3.1. The prepared tea saponin low eutectic solvent was left to stand for 24 hours for observation, and its decontamination, foaming and foam stabilization abilities were measured after stabilization.

[0030] Note: Tea saponin is a mixture, with a molecular weight of 1200, 6501 molecular weight of 287.16, BS-12 molecular weight of 271.44. In this experiment, 6501 and BS-12 are calculated based on a molecular weight of 300, so the ratio of the amount of substance is an approximate ratio, but the mass ratio is definite.

[0031] 2.3.6 Design of the ratio of hydrophobic deep eutectic solvents with tea polyphenols as auxiliary tea saponin as hydrogen bond donor Tea polyphenols, as natural antioxidants, are widely used in skin care products. Due to the presence of phenolic hydroxyl groups in their molecular structure, they can be used as hydrogen bond donors. The tea saponin hydrophobic low eutectic solvent with the best comprehensive ability in decontamination, foaming and foam stabilization in the results of 2.3.5 was selected as a fixed hydrogen bond donor acceptor mass ratio, and the ratio of tea polyphenols and tea saponin in the hydrogen bond donor was changed. With 6501 as the hydrogen bond acceptor, a tea polyphenol gradient (0.1g, 0.3g, 0.5g, 0.7g, 0.9g) was designed. With BS-12 as the hydrogen bond acceptor, a tea polyphenol gradient (0.3g, 0.5g, 0.7g, 0.9g, 1.1g) was designed. According to the preparation process of 2.3.1, tea polyphenol tea saponin hydrophobic low eutectic solvents with different ratios were prepared. The prepared tea polyphenol tea saponin hydrophobic low eutectic solvent was left to stand for 24h for observation, and its decontamination, foaming and foam stabilization abilities were measured after stabilization.

[0032] 2.4 Results and Analysis 2.4.1 Hydrophobic force detection of hydrophobic deep eutectic solvents According to the method of 2.3.2, the hydrophobicity of the hydrophobic deep eutectic solvents prepared with different ratios of hydrogen bond donors and acceptors was measured. The results are shown in the following table: Table 2.3 Hydrophobicity of hydrophobic deep eutectic solvents prepared with different ratios of hydrogen bond donors and acceptors 2.4.2 Foaming and Decontamination Performance of Hydrophobic Deep Eutectic Solvents with Different Ratios of Hydrogen Bond Donors and Acceptors The ratio of hydrogen bond donors and acceptors of the hydrophobic deep eutectic solvent was explored. 6501 and BS-12 were used as hydrogen bond acceptors, tea saponin was used as hydrogen bond donor, the molar ratio of hydrogen bond acceptor to donor was 40:1, 40:3, 40:5, 40:7, 40:9, and the mass ratio was 10:1, 10:3, 10:5, 10:7, 10:9. The prepared hydrophobic deep eutectic solvent was subjected to decontamination and foaming experiments. The results are as follows: like Figure 2.2 As shown in the figure, 6501 acts as a hydrogen bond acceptor and tea saponin acts as a hydrogen bond donor. In terms of detergency performance, as the molar ratio of the hydrogen bond acceptor to the donor increases, its detergency is enhanced. The detergency of the prepared hydrophobic low eutectic solvents is above 90%, and it has an excellent washing effect. When the molar ratio of the hydrogen bond acceptor to the donor is 40:7, the tea saponin content has the best detergency, but the high proportion of tea saponin causes the prepared solvent to have a larger viscosity and poor fluidity.

[0033] BS-12 acts as a hydrogen bond acceptor and tea saponin acts as a hydrogen bond donor. In terms of detergency performance, the detergency at the five ratios is over 90%. With the increase of the tea saponin ratio, the detergency decreases slightly. When the ratio of hydrogen bond acceptor to hydrogen bond donor is 40:9, the detergency decreases significantly. It is speculated that this is because BS-12 has a strong detergency as a surfactant alone, while tea saponin itself has a weak detergency. When its proportion in the solvent is high, the detergency decreases.

[0034] like Figure 2.3 , 2.4 As shown in the figure, the foam height of the hydrophobic low eutectic solvent prepared with 6501 as the hydrogen bond acceptor and tea saponin as the hydrogen bond donor is between 29 and 38 ml. As the proportion of tea saponin increases, the foam height gradually increases. When the molar ratio of 6501 to tea saponin is 40:7, the foam stability is poor. When the amount of tea saponin added is 1g and 3g, the foam stabilizing ability of the low eutectic solvent is better. The foam height of the hydrophobic low eutectic solvent prepared with BS-12 as the hydrogen bond acceptor and tea saponin as the hydrogen bond donor is between 42 and 59 ml. The foam height of the solvent increases first and then decreases with the increase of the proportion of tea saponin. When the molar ratio of the hydrogen bond acceptor to the donor is 40:7, the foam height reaches the best 59 ml and the foam stabilizing ability is the best.

[0035] 2.4.3 Foaming and Decontamination Performance of Hydrophobic Deep Eutectic Solvents with Tea Polyphenols as Assistance and Tea Saponin as Hydrogen Bond Donor Tea polyphenols contain phenolic hydroxyl groups in their molecular structure, which can be used as hydrogen bond donors in hydrophobic low eutectic solvents to play an antioxidant role in washing and care products. According to the state of the prepared solvent and the results of 2.4.1, the optimal ratio of foam and decontamination performance of the prepared hydrophobic low eutectic solvent was selected, and tea saponin was replaced with part of tea polyphenols as hydrogen bond donors. The mass ratio of 6501 to tea saponin was fixed at 10:3, and the ratio of tea polyphenols to tea saponin in the hydrogen bond donor was changed. The tea polyphenol gradient was (0.1g, 0.3g, 0.5g, 0.7g, 0.9g). The mass ratio of BS-12 to tea saponin was fixed at 10:7, and the tea polyphenol gradient was (0.3g, 0.5g, 0.7g, 0.9g, 1.1g). Decontamination and foaming experiments were carried out on the prepared tea saponin tea polyphenol hydrophobic low eutectic solvent. The results are as follows: like Figure 2.5 As shown, 6501 is used as a hydrogen bond acceptor, tea polyphenols assist tea saponin as a hydrogen bond donor, and the mass proportion of tea polyphenols in the hydrogen bond donor is 3.3%, 10%, 16.7%, 23.3%, and 30%. When the mass proportion of tea polyphenols is between 3.3% and 23.3%, the detergency of the prepared solvent is above 90%. When the mass proportion of tea polyphenols reaches 30%, the detergency decreases. BS-12 is used as a hydrogen bond acceptor, tea polyphenols assist tea saponin as a hydrogen bond donor, and the mass proportion of tea polyphenols in the hydrogen bond donor is 4.3%, 7.1%, 10%, 12.8%, and 15.7%. When the mass proportion of tea polyphenols is between 4.3% and 12.8%, the detergency of the prepared solvent is above 94%, which has a good washing effect. When the mass proportion of tea polyphenols reaches more than 15%, the detergency decreases.

[0036] The decrease in detergency is presumably because tea polyphenols themselves do not have detergency, and when added as a trace ingredient at a high amount, the decontamination capacity of the hydrophobic low eutectic solvent prepared with tea saponin as a hydrogen bond donor decreases.

[0037] like Figure 2.6 , 2.7 As shown, in terms of foaming, tea polyphenols assist tea saponin as a hydrogen bond donor. As the proportion of tea polyphenols increases, the foaming power of the prepared hydrophobic low eutectic solvent gradually decreases. When 6501 is used as a hydrogen bond acceptor, when the mass proportion of tea polyphenols is 10%, the hydrophobic low eutectic solvent has the strongest foaming ability, but the bubble height decreases significantly, and the foam stabilization power is poor. When the mass proportion of tea polyphenols is 23.3%, the solvent has a better foam stabilization ability. In order to ensure that the amount of tea polyphenols added is 5% of the total mass, tea polyphenols accounting for 23.3% of the mass are selected to assist tea saponin as a hydrogen bond donor to prepare a hydrophobic low eutectic solvent. When BS-12 was used as the hydrogen bond acceptor, the foam stability of the solvent was better when the mass proportion of tea polyphenols was 7.1% and 12.8%. Combined with the comprehensive determination of decontamination and foam performance, tea polyphenols with a mass proportion of 12.8% were selected as auxiliary tea saponin as the hydrogen bond donor to prepare a hydrophobic low eutectic solvent for subsequent experiments.

[0038] 2.5 Summary of this chapter This chapter studies the effects of monomeric tea saponin and tea polyphenols assisted tea saponin as hydrogen bond donors on the foaming and decontamination ability of hydrophobic low eutectic solvents, and tests the decontamination ability, foaming ability and foam stabilization ability of hydrophobic low eutectic solvents respectively. Finally, the optimal hydrogen bond donor ratio formula of tea saponin hydrophobic low eutectic solvent was determined; the molar ratio of 6501 to tea saponin was 40:3, and the molar ratio of BS-12 to tea saponin was 40:7. When 6501 was used as a hydrogen bond acceptor, tea polyphenols assisted tea saponin as a hydrogen bond donor, and the mass proportion of tea polyphenols in the hydrogen bond donor was 23.3%; when BS-12 was used as a hydrogen bond acceptor, tea polyphenols assisted tea saponin as a hydrogen bond donor, and the mass proportion of tea polyphenols in the hydrogen bond donor was 12.8%. At present, the prepared reagent has the disadvantages of high viscosity and poor fluidity. As a cleansing product, its moisturizing performance is poor. It is necessary to further explore the addition of other oily ingredients to improve the fluidity and moisturizing power of the product.

[0039] 3 Tea polyphenols assisted tea saponin as a hydrogen bond donor hydrophobic low eutectic solvent and camellia oil to develop human body washing oil formula exploration 3.1 Introduction In recent years, with the prevalence of the concept of "using oil to nourish the skin", it has gradually attracted the attention of consumers. Bath oil is the embodiment of this concept in human body care products, which uses oily ingredients to nourish and protect the skin. As consumers' demand for personal care products becomes increasingly refined, bath oil, as a product that can meet the dual functions of cleaning and nourishing, is growing in market demand, especially in winter. Camellia oil is rich in tea saponins, tea polyphenols and other antioxidants, which can remove free radicals, reduce oxidative stress, delay cell aging, help the skin resist the damage of the external environment, and keep the skin young.

[0040] The purpose of this experiment is to further optimize the formula by compounding the hydrophobic low eutectic solvent of tea saponin and tea polyphenols with camellia oil, and at the same time add isododecane as a diluent to prepare moisturizing, anti-inflammatory and repairing bath oil and massage oil, enhance the contact between the effective active ingredients and the skin, and exert better care functions. The foaming performance and detergency performance of the bath oil and massage oil were measured.

[0041] 3.2 Experimental Materials and Instruments 3.2.1 Experimental Materials Table 3.1 Experimental materials 3.2.2 Experimental instruments Table 3.2 Experimental instruments 3.3 Experimental methods 3.3.1 Preparation of Hydrophobic Deep Eutectic Solvent Cleaning Oil Products Based on the exploration of the ratio of hydrogen bond donors and acceptors in hydrophobic low eutectic solvents, the amount of camellia oil added to bath oil was explored. The preparation process of hydrophobic bath oil and massage oil was prepared by using 6501 and BS-12 as hydrogen bond acceptors. Figure 3.1 shown.

[0042] 3.3.2 Testing of Hydrophobic Deep Eutectic Solvent Cleaning Oil Products According to the relevant standards of GB / 1994-2013 "Bath Agent", the prepared hydrophobic low eutectic solvent cleaning oil product was evaluated: (1) Appearance evaluation: Evaluation based on sensory indicators such as color, shape, and odor as well as physical and chemical indicators.

[0043] (2) Formula stability test: ①Hot and cold stability test: Store in a 40ºC oven and a -5ºC refrigerator for 3 days, cycle three times, and observe whether stratification, flocculation, etc. occur.

[0044] ② High-speed centrifugal test: After the hot and cold stability test, a centrifugal test is also conducted to test the stability of the formula system to confirm that the formula can also ensure no deformation, no demulsification, and no stratification in a relatively harsh environment. The test method is to centrifuge at 3000r / min for 30min and 8000r / min for 10min to observe its stability.

[0045] 3.3.3 Testing the Foaming Power of Hydrophobic Deep Eutectic Solvent Cleaning Oil Products The foaming test of bath oil and massage oil shall be carried out according to the method in 2.3.3.

[0046] 3.3.4 Detergency testing of hydrophobic low eutectic solvent cleaning oil products The bath oil and massage oil decontamination test was carried out according to the method in 2.3.4.

[0047] 3.4 Results and Analysis 3.4.1 Physical and chemical indicators of hydrophobic deep eutectic solvent cleaning oil products Table 3.3 Evaluation results of physical and chemical indicators of cleaning oil products The color, shape and smell of the prepared hydrophobic low eutectic solvent bath oil and massage oil all meet the relevant standards, and have passed three stability tests: cold storage, hot storage and high-speed centrifugation test.

[0048] 3.4.2 Foaming and Decontamination Performance of Hydrophobic Deep Eutectic Solvent Cleaning Oil Products According to the method of 3.3.1, a hydrophobic low eutectic solvent bath oil was prepared using 6501 as a hydrogen bond acceptor, the mass of the hydrophobic low eutectic solvent was fixed at 13g, and camellia oil of different gradients (0.5g, 1g, 1.5g, 2.0g, 2.5g) was added to measure its foam and detergency performance. A hydrophobic low eutectic solvent massage oil was prepared using BS-12 as a hydrogen bond acceptor, the mass of the hydrophobic low eutectic solvent was fixed at 17g, and camellia oil of different gradients (1g, 1.5g, 2.0g, 2.5g, 3g) was added to measure its foam and detergency performance. The results are as follows: like Figure 3.2 As shown in the figure, the hydrophobic low eutectic solvent bath oil prepared with 6501 as the hydrogen bond acceptor has a cleaning rate of more than 92% when the addition amount of camellia oil is between 3.7% and 13.3%, and has an excellent washing effect. When the proportion of camellia oil is 16%, the cleaning ability decreases significantly. Therefore, it is recommended that the addition amount of camellia oil be between 3.7% and 13.3%.

[0049] The hydrophobic low eutectic solvent massage oil prepared with BS-12 as the hydrogen bond acceptor has a camellia oil addition amount between 5.6% and 15%, and the detergency reaches more than 92%. However, as the camellia oil addition amount is too high (15%), the detergency of the massage oil decreases. It is recommended that the camellia oil addition amount be between 5.6% and 12.8%. After adding the oil phase to the hydrophobic low eutectic solvent, a tiny micelle structure is formed, which can disperse the oil in the water and convert it into fine particles, thereby achieving a better cleaning effect. After adding the oil phase, the oil can be prevented from re-attaching to the surface of the cleaned object, forming a stable emulsified system to prevent the oil from re-condensing and depositing, thereby improving the cleaning effect. like Figure 3.3 , 3.4 As shown, for the hydrophobic low eutectic solvent bath oil prepared with 6501 as the hydrogen bond acceptor, the camellia oil addition amount is between 3.7% and 16.1%, which has little effect on the foaming height of the bath oil, and overall decreases with the increase of camellia oil addition amount. When the camellia oil addition amount is 16.1%, the foam stability is poor.

[0050] The hydrophobic low eutectic solvent massage oil prepared with BS-12 as the hydrogen bond acceptor has a significant decrease in foam height with the increase of camellia oil addition, indicating that the amount of camellia oil added has a great influence on the foam performance of the system, but the foam stability is slightly improved with the increase of camellia oil addition. The increase of camellia oil reduces the viscosity of the system, improves the fluidity of the product, and makes the hand feel smoother. Considering the decontamination, foaming and foam stabilization capabilities, the recommended camellia oil addition is 5.6%~12.8%.

[0051] 3.4.3 Foaming and Decontamination Performance of Isododecane Hydrophobic Bath Oil Products Isododecane is a colorless, odorless and transparent liquid that nourishes, refreshes and is not greasy to the skin. Adding a certain proportion of isododecane to washing and care products can improve the spreadability and skin feel of the products. Taking 6501 as the hydrogen bond acceptor, bath oil type I with 13.3% tea oil was selected. The specific formula was (10g 6501, 0.7g tea polyphenols, 2.3g tea saponin and 2g camellia oil). The mass ratio of bath oil I and diluent isododecane was set to 7:3, 5:5, and 3:7 to prepare hydrophobic bath oil II. Sensory evaluation, decontamination, foaming and other properties were tested according to 3.3.2, 2.3.3, and 2.3.4. The results are as follows: Table 3.4 Evaluation results of physical and chemical indicators of hydrophobic bath oil II As shown in Table 3.4, the color, appearance, stability and other aspects of hydrophobic shower oil II meet the relevant standards of GB / 1994-2013 "Bath Agent". It is a translucent reddish-brown liquid with strong fluidity and stable properties.

[0052] Table 3.5 Foaming and detergency results of hydrophobic bath oil II As shown in Table 3.5, the foaming power of hydrophobic bath oil II gradually decreases with the increase of diluent isododecane, but it has almost no effect on the decontamination. Compared with the bath oil Burt's Bees sold on the market, the decontamination effect is basically the same and the foaming power is higher than the bath oil on the market. Isododecane has excellent solubility and can quickly and thoroughly clean most oily products. As the main solvent for oil-soluble cleaning products, it can provide oil-free and refreshing skin feeling after cleaning. At the same time, it is a safe and environmentally friendly solvent, harmless to the human body, and easily biodegradable, which meets consumers' pursuit of safe and environmentally friendly ingredients.

[0053] 3.5 Summary of this chapter The camellia oil addition amount of bath oil type I and massage oil was screened out, which was 3.7%~16.1% and 5.6%~12.8% respectively. The suitable diluent isododecane was screened out, and bath oil II was further prepared. According to the national standard, the prepared hydrophobic low eutectic solvent bath oil I, bath oil II and massage oil were tested for decontamination, foaming, foam stabilization, appearance and stability, which basically met the national standard requirements for products, and opened up the market for the development of human body cleansing oil based on camellia oil.

[0054] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made according to the scope of the patent application of the present invention should fall within the scope of the present invention.

Claims

1. A hydrophobic deep eutectic solvent in which tea saponin and tea polyphenols are hydrogen bond donors, characterized in that: The hydrophobic low eutectic solvent uses tea saponin and tea polyphenols as hydrogen bond donors and uses coconut oil diethanolamide or lauryl betaine as hydrogen bond acceptors.

2. The hydrophobic deep eutectic solvent according to claim 1, characterized in that In the hydrophobic low eutectic solvent, the molar ratio of coconut oil diethanolamide to tea saponin is 40:3, and the mass proportion of tea polyphenols in hydrogen bond donors is 23.3%.

3. The hydrophobic deep eutectic solvent according to claim 1, characterized in that In the hydrophobic low eutectic solvent, the molar ratio of lauryl betaine to tea saponin is 40:7, and the mass proportion of tea polyphenols in hydrogen bond donors is 12.8%.

4. The method for preparing a hydrophobic deep eutectic solvent according to any one of claims 1 to 3, characterized in that: The following steps are involved: Mix coconut oil diethanolamide or lauryl betaine with tea saponin and tea polyphenols, and stir magnetically for 30 to 50 minutes at 50°C until the mixture becomes a clear liquid.

5. The use of the hydrophobic deep eutectic solvent according to claim 2 in camellia oil cleaning products, characterized in that: A hydrophobic deep eutectic solvent bath oil was prepared using coconut oil diethanolamide as a hydrogen bond acceptor, and the addition amount of camellia oil was 16.1%.

6. The use of the hydrophobic deep eutectic solvent according to claim 3 in camellia oil cleaning products, characterized in that: A hydrophobic low eutectic solvent massage and conditioning oil was prepared using lauryl betaine as a hydrogen bond acceptor, and the camellia oil addition amount was 12.8%.

7. The use of the hydrophobic deep eutectic solvent according to claim 5 in camellia oil cleaning products, characterized in that: A diluent isododecane is also added to the hydrophobic low eutectic solvent bath oil, and the mass ratio of the bath oil to the diluent isododecane is 7:3 to 3:7.

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