阅读说明：本技术 承载尿素或其衍生物的稳定组合物 (Stable compositions carrying urea or derivatives thereof ) 是由 黄诚赟 丛远华 郭奕光 贾海东 于 2021-08-19 设计创作，主要内容包括：本发明提供了一种承载尿素或其衍生物的稳定组合物,所述组合物包含：(a)油脂；(b)阳离子乳化剂,所述阳离子乳化剂是二硬脂基二甲基氯化铵；(c)长链脂肪醇,所述长链脂肪醇的碳链长度为16-22；(d)水相；其中,所述尿素衍生物是尿素的碳原子数为1-6的羟烷基化物,其中,所述阳离子乳化剂与长链脂肪醇的重量比为10:1至1:4,所述阳离子乳化剂与承载的尿素或其衍生物的重量比为1:10至50:1。(The present invention provides a stable composition carrying urea or a derivative thereof, said composition comprising: (a) grease; (b) a cationic emulsifier which is distearyldimethylammonium chloride; (c) the long-chain fatty alcohol has a carbon chain length of 16-22; (d) an aqueous phase; wherein the urea derivative is a hydroxyalkyl compound of urea with 1-6 carbon atoms, the weight ratio of the cationic emulsifier to the long-chain fatty alcohol is 10: 1-1: 4, and the weight ratio of the cationic emulsifier to the supported urea or the derivative thereof is 1: 10-50: 1.)

1. A stable composition carrying urea or a derivative thereof, the composition comprising:

(a) grease;

(b) a cationic emulsifier which is distearyldimethylammonium chloride;

(c) the long-chain fatty alcohol has a carbon chain length of 16-22;

(d) an aqueous phase;

wherein the urea derivative is a hydroxyalkylated product of urea having 1 to 6 carbon atoms,

wherein the weight ratio of the cationic emulsifier to the long-chain fatty alcohol is 10:1 to 1:4, and the weight ratio of the cationic emulsifier to the supported urea or the derivative thereof is 1:10 to 50: 1.

2. The composition of claim 1, wherein the oil is selected from the group consisting of: a non-polar solid oil; a non-polar liquid oil; polar liquid oils; polar solid oils; a silicone oil; or mixtures thereof.

3. The composition of claim 1, wherein the composition comprises 0.1 to 20 wt.% of the oil.

4. The composition of claim 1, wherein the composition comprises 2.5 to 10 wt% of the cationic surfactant.

5. The composition of claim 1, wherein the long chain fatty alcohol is selected from the group consisting of: cetyl alcohol, cetearyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol or mixtures thereof.

6. The composition of claim 1, wherein the composition comprises 0.1 to 10% by weight of the long chain fatty alcohol.

7. The composition of claim 1, wherein the composition comprises 1% by weight or more of urea or a derivative thereof.

8. The composition of claim 1, wherein the composition comprises 50% by weight or more of the aqueous phase.

9. The composition of any one of claims 1 to 8, wherein the weight ratio of the cationic emulsifier to the long chain fatty alcohol is from 10:1 to 1:2 and the weight ratio of the cationic emulsifier to the supported urea or derivative thereof is from 1:2 to 10: 1.

10. An external preparation for skin comprising the composition according to any one of claims 1 to 9.

Technical Field

The invention relates to the field of cosmetics, in particular to a stable composition carrying urea or derivatives thereof and application thereof in cosmetics.

Background

Urea is one of natural moisturizing factors of skin, and the effects of moisturizing, softening skin, promoting percutaneous penetration and the like of urea are widely reported in documents. In the literature, "instruments and dermatologists evaluate the effect of glycerol and urea on the dry skin of atopic dermatitis patients", skin research and technology, Lod en M. et al report that the mean value of the skin capacitance of 35 subjects increased from 35A.U. to 42A.U (the higher the moisture content of the skin surface, the higher the capacitance), and the mean value of the epidermal water loss of about 11 g/(m) after 30 days of use of a moisturizer containing 4% urea²H) to 8.5 g/month/(m)²H), the average value of the total dryness fraction is reduced from 3.2 to 0.8, the experimental results are obviously superior to those of a control group without urea, and the statistical difference proves that the urea has the effects of moisturizing, softening and strengthening the skin barrier. In the literature, "influence of urea on human epidermis and skin", Hellgren et al report that the water absorption capacity of epidermis after the dry epidermis is immersed in 10% urea solution is approximately 300% of the initial mass after 90 hours, and the water absorption capacity is about 3 times of that of the sample immersed in distilled water after the epidermis is almost balanced. The increase of water absorption of dry skin comes from the fact that the urea aqueous solution increases the permeability of the epidermis. Literature "new effects of transdermal penetration enhancers on the transdermal penetration of two zinc salts", Science Technology and Engineering, 2016; 16:1671-²Rises to 388.04 mu g/cm²The cumulative osmotic quantity per unit time of the zinc gluconate is 682.26 mu g/cm²Rises to 1020.49 mu g/cm²And the permeation rate is still further improved with the increase of the urea content.

Recent research shows that the urea has more intensive disclosure on the skin care efficacy. For example, in the literature, "urea uptake enhances human barrier function and antibacterial defense by regulating epidermal gene expression", the journal of dermatology research susannen g. -b., (2012)132, 1561-1572 reports that urea can improve the expression of skin barrier-related genes AMP, LL-37 and β -defensin-2, and the action mechanisms of urea regulation gene expression, skin barrier improvement and antibacterial activity are studied in detail. According to the results of the study, the authors concluded that urea is not just a product of body metabolism, but rather has the effect of modifying the expression of genes associated with the skin barrier as a small molecule modulator. Further, urea and skin: one famous molecular revisit summarizes the application of urea as a medicine for treating skin diseases such as psoriasis, allergic dermatitis, eczema, seborrheic dermatitis and the like.

However, the practical application of urea having a potent skin care effect to cosmetics or dermatology medical products has faced many challenges. One of them is that the hydrolysis of urea can generate stronger alkalinity and ionicity, and puts a very high demand on the bearing capacity of the cosmetic formula matrix. For example, 12 kinds of commercially available emulsion formulations (viscosity of 1000mPa · s to 20000mPa · s, each formulation using an emulsifier and a thickener) from shanghai home-based co-products co.ltd. were tested, and 11 formulations were formulated with urea and a combination of urea + glycine + triethyl citrate, and the viscosity was significantly reduced in the stability test at high temperature over time, and stability problems such as delamination and emulsion breaking occurred, which failed to satisfy the requirements of national regulations on the stability of cosmetics. After further testing of the 12 formulations above with respect to emulsifiers and thickeners, it was found that most of the samples did not remain stable during high temperature testing after compounding with urea (test example 1).

The urea has strict requirement on the bearing capacity of a formula system, and the bearing capacity of most commercially available formulas of cosmetics cannot meet the requirement of compound urea, so that the urea has strong efficacy, good safety and low price, and the urea is used in the current cosmetics and commercial products at low rate (according to the search result of Mintel based on the global market in 2020, the proportion of the cosmetics containing the urea is only 2.8%). In addition, most of the current urea cosmetics are added only in a trace amount to stabilize the pH value of the formula, and the addition amount is far lower than the urea efficacy addition amount reported in the above documents.

Therefore, the development of a formulation base capable of stably supporting urea or its derivatives, or a composition comprising urea or its derivatives, is of great significance for facilitating the use of urea and its derivatives in cosmetics.

Disclosure of Invention

In one aspect, the present invention provides a stable composition carrying urea or a derivative thereof, the composition comprising:

(a) grease;

(b) a cationic emulsifier which is distearyldimethylammonium chloride;

(c) the long-chain fatty alcohol has a carbon chain length of 16-22;

(d) an aqueous phase;

wherein the urea derivative is a hydroxyalkylated product of urea having 1 to 6 carbon atoms,

wherein the weight ratio of the cationic emulsifier to the long-chain fatty alcohol is 10:1 to 1:4, and the weight ratio of the cationic emulsifier to the supported urea or the derivative thereof is 1:10 to 50: 1.

In a preferred embodiment, the fat or oil in the composition is selected from: a non-polar solid oil; a non-polar liquid oil; polar liquid oils; polar solid oils; a silicone oil; or mixtures thereof. In a preferred embodiment, the composition comprises from 0.1 to 20% by weight of the oil.

In a preferred embodiment, the composition comprises from 2.5 to 10 wt% of a cationic surfactant.

In a preferred embodiment, the long chain fatty alcohol in the composition is selected from: cetyl alcohol, cetearyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol or mixtures thereof. In a preferred embodiment, the composition comprises 0.1 to 10 wt.% of the long chain fatty alcohol.

In a preferred embodiment, the composition comprises 1% by weight or more of urea or a derivative thereof.

In a preferred embodiment, the composition comprises more than 50% by weight of an aqueous phase.

In a preferred embodiment, the weight ratio of cationic emulsifier to long chain fatty alcohol in the composition is from 10:1 to 1:2 and the weight ratio of cationic emulsifier to supported urea or derivative thereof is from 1:2 to 10: 1.

In another aspect, the present invention also provides an external preparation for skin comprising the stable composition of the present invention.

Detailed Description

The present invention has surprisingly found that a stable composition can support urea or a derivative thereof and that the composition exhibits an abnormal thickening behaviour when tested at elevated temperatures over time at suitable ratios. Therefore, the emulsification technology of the invention has high practical value in the practical application of future cosmetics and skin medical products.

To provide a more concise description, some of the quantitative representations presented herein are not modified by the term "about". It is understood that each quantity given herein is intended to refer to the actual given value, regardless of whether the term "about" is explicitly used, and also to refer to the approximation to such given value that would reasonably be inferred by one of ordinary skill in the art, including approximations due to experimental and/or measurement conditions for such given value.

To provide a more concise description, some quantitative expressions are recited herein as a range from about an X amount to about a Y amount. It should be understood that when a range is recited, the range is not limited to the upper and lower limits recited, but includes the entire range from about the X amount to about the Y amount or any amount therebetween.

Urea

Urea is one of natural moisturizing factors of skin, and the effects of moisturizing, softening skin, promoting percutaneous penetration and the like of urea are widely reported in documents. However, the practical application of urea having a potent skin care effect to cosmetics or dermatology medical products has faced many challenges. The urea has strict requirements on the bearing capacity of a formula system, and the bearing capacity of most commercially available formulas of cosmetics cannot meet the requirements of compound urea.

The present invention innovatively provides a stable composition capable of supporting urea or its derivatives.

In some embodiments, the urea supported by the stabilizing composition of the present invention is in the form of a urea formulation. For example, the urea formulation is urea: glycine: triethyl citrate is a compound formed by the weight ratio of 10:10: 1. In a specific embodiment, the urea formulation is a formulation of 5% urea, 5% glycine and 0.5% triethyl citrate.

In some embodiments, the urea carried by the stabilizing composition of the present invention is a urea derivative. For example, the urea derivative is a hydroxyalkylated derivative of urea. In a particular embodiment, the urea derivative is a hydroxyalkylated derivative having 1 to 6 carbon atoms. In a particular embodiment, the urea derivative is hydroxyethyl urea.

In some embodiments of the invention, the stabilizing composition comprises 0.1 to 20 wt.% urea or a derivative thereof. In some embodiments of the invention, the stabilizing composition comprises 0.1 to 10 wt.% urea or a derivative thereof.

In some embodiments of the invention, the stabilizing composition comprises 1% by weight or more of urea or a derivative thereof. In some embodiments of the invention, the stabilizing composition comprises 2% by weight or more of urea or a derivative thereof. In some embodiments of the invention, the stabilizing composition comprises 3% by weight or more of urea or a derivative thereof. In some embodiments of the invention, the stabilizing composition comprises 4% by weight or more of urea or a derivative thereof. In some embodiments of the invention, the stabilizing composition comprises 5% by weight or more of urea or a derivative thereof.

Oil and fat

The stabilized compositions of the invention carrying urea or its derivatives comprise a lipid. In some embodiments, the stabilizing composition of the present invention comprises a lipid selected from the group consisting of: (1) a non-polar solid oil; (2) a non-polar liquid oil; (3) polar liquid oils; (4) polar solid oils; (5) a silicone oil; or any mixture thereof.

In some embodiments, the stabilizing compositions of the present invention comprise white petrolatum. In some embodiments, the stabilizing composition of the present invention comprises # 10 white oil. In some embodiments, the stabilizing compositions of the present invention comprise isooctyl palmitate. In some embodiments, the stabilizing composition of the present invention comprises cetyl palmitate. For example, in some particular embodiments, the stabilizing compositions of the present invention comprise cetyl palmitate ACP available from Croda (singapore). In some embodiments, the stabilizing composition of the present invention comprises dimethicone. For example, in some embodiments, the stabilizing compositions of the present invention comprise dimethicone (100cst) available from dow (zhang) investment limited.

In some embodiments of the invention, the stabilizing composition comprises 0.1 to 20 wt.% of the oil. In some embodiments of the invention, the stabilizing composition comprises 1 to 20 wt.% of the oil. In some embodiments of the invention, the stabilizing composition comprises 1-10 wt.% of the oil. In some embodiments of the invention, the stabilizing composition comprises 5 to 10 wt.% of the oil.

Cationic surfactant

The cationic surfactant refers to an emulsifier with cationic groups, and the molecular structure of the emulsifier comprises cationic groups and alkyl chains. The cationic groups mainly comprise alkyl quaternary ammonium salt, alkyl pyridinium and alkyl amine salt, and generally have good heat resistance, light resistance, acid-base tolerance, surface activity, stability and biodegradability. The cationic surfactant can form a film on the surface of skin or hair due to the unique charge property, so that the cationic surfactant has unique product use feeling and is widely applied to hair products in particular.

The cationic surfactant is compounded in the hair product, an alkyl chain of the cationic surfactant is attached to a cutin surface to form a cationic membrane, and the charge repulsion of the cationic membrane enables the substrate to have a lubricating effect, particularly the hair is smooth and soft after the product is used, and the force required for combing the hair is reduced. In contrast, cationic surfactants are used relatively rarely in skin care products due to the widespread use of anionic thickeners. However, the cationic surfactant has strong absorption feeling and film-forming property, can remarkably shield the sticky feeling of grease, can enable the product to have unique use feeling, and can have unique competitiveness in the cosmetic market if being applied to a proper product.

The stabilizing composition of the present invention comprises a cationic surfactant. In a particular embodiment, the cationic surfactant employed in the stabilizing compositions of the present invention is distearyldimethylammonium chloride. In a particular embodiment, the cationic surfactant employed in the stabilizing compositions of the present invention is TA-100 available from Evonik Operations GmbH.

It has now been surprisingly found that the use of distearyldimethylammonium chloride results in a stable composition capable of carrying urea or a derivative thereof. It was also unexpected that some samples, after compounding with urea, showed significant viscosity increase in the high temperature stability over time test, while the samples without urea were not similarly abnormal. The abnormal phenomenon has higher application value in the practical production of cosmetics and skin medical products: (1) the distearyl dimethyl ammonium chloride is compounded with other emulsifiers, so that the phenomenon that the viscosity of the material body is obviously reduced after the distearyl dimethyl ammonium chloride is compounded with urea can be improved or avoided; (2) the material body is aged at high temperature in the preparation process, and then the viscosity of a sample is regulated and controlled; (3) this property can be used to make hard creams and remain stable during the strengthening test. It is also necessary to point out that the efficacy of urea is suitable for the care of dry skin, and the addition amount of grease of cosmetics designed for the skin is generally higher, so that the skin feel is greasy and the absorption is poor. The distearyl dimethyl ammonium chloride has strong absorption and covering properties when being applied to cosmetics due to the cationic property, can effectively improve the greasy feeling of a formula with high oil addition, improves the absorptivity, and enables consumers to obtain better use experience while meeting the efficacy of the cosmetics.

In some embodiments of the invention, the stabilizing composition comprises from 0.5 to 20 wt% of a cationic surfactant. In some embodiments of the invention, the stabilizing composition comprises from 1 to 20 wt% of a cationic surfactant. In some embodiments of the invention, the stabilizing composition comprises 1 to 10 wt% of a cationic surfactant. In some embodiments of the invention, the stabilizing composition comprises 2.5 to 10 wt% of a cationic surfactant. In some embodiments of the invention, the stabilizing composition comprises 5 to 10 wt% of a cationic surfactant.

In some embodiments of the invention, the weight ratio of the cationic emulsifier to the supported urea or derivative thereof is from 1:10 to 50: 1. In some embodiments of the invention, the weight ratio of the cationic emulsifier to the supported urea or derivative thereof is from 1:10 to 10: 1. In some embodiments of the invention, the weight ratio of the cationic emulsifier to the supported urea or derivative thereof is from 1:2 to 10: 1. In one embodiment of the invention, the weight ratio of cationic emulsifier to supported urea or derivative thereof is 1: 1.

Long chain fatty alcohols

The stabilizing composition of the present invention, which carries urea or a derivative thereof, comprises a long chain fatty alcohol. In some embodiments, the long chain fatty alcohol included in the stabilizing composition of the present invention is a long chain fatty alcohol having from 16 to 22 carbon atoms.

In some embodiments, the stabilizing composition of the present invention comprises a long chain fatty alcohol selected from the group consisting of: cetyl alcohol, cetearyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol or mixtures thereof.

In some embodiments of the invention, the stabilizing composition comprises 0.1 to 10 wt.% of the long chain fatty alcohol. In some embodiments of the invention, the stabilizing composition comprises 0.5 to 10 wt.% of the long chain fatty alcohol. In some embodiments of the invention, the stabilizing composition comprises 1 to 10 wt.% of the long chain fatty alcohol. In some embodiments of the invention, the stabilizing composition comprises 1 to 5 wt.% of the long chain fatty alcohol. In some embodiments of the invention, the stabilizing composition comprises 3 to 5 wt.% of the long chain fatty alcohol.

In some embodiments of the invention, the weight ratio of the cationic emulsifier to the long chain fatty alcohol is from 10:1 to 1: 4. In some embodiments of the invention, the weight ratio of the cationic emulsifier to the long chain fatty alcohol is from 10:1 to 1: 2. In some embodiments of the invention, the weight ratio of the cationic emulsifier to the long chain fatty alcohol is from 10:1 to 1: 1. In one embodiment of the invention, the weight ratio of cationic emulsifier to long chain fatty alcohol is 5: 2.

Aqueous phase

The stabilising composition of the invention also comprises an aqueous phase. In some embodiments, the aqueous phase may be water or other aqueous carrier.

In some embodiments of the invention, the stabilizing composition comprises 50% by weight or more of the aqueous phase. In some embodiments of the invention, the stabilizing composition comprises 60% by weight or more of the aqueous phase. In some embodiments of the invention, the stabilizing composition comprises 70% by weight or more of the aqueous phase. In some embodiments of the invention, the stabilizing composition comprises 80% by weight or more of the aqueous phase.

External preparation for skin

The composition of the present invention can be applied to a skin external preparation as an efficacy additive. In some embodiments, the external skin agent is selected from: face cleaning lotion, cosmetic water, lotion, cream, jelly and facial mask. Different amounts are added according to different types of preparations.

The external preparation for skin is a general concept of all ingredients generally used for the external part of skin, and may be, for example, a cosmetic composition. The cosmetic composition can be basic cosmetics, face makeup cosmetics, body makeup cosmetics, hair care cosmetics and the like, and the dosage form of the cosmetic composition is not particularly limited and can be reasonably selected according to different purposes. The cosmetic composition also contains different cosmetically acceptable media or matrix excipients according to different dosage forms and purposes.

The stable compositions of the invention form emulsified systems, are particularly suitable for skin care of dry and moderately dry skin, and have particular advantages in the cosmetics of hand, foot, body care.

For example, based on the results of a 14-day consumer leave-on test, it was concluded that the stable compositions of the present invention were suitable for use on the hands in proportions of 98%, 96%, 94%, 96% and 98% in order to moisturize, soften, fine, increase skin luster, prevent chapping, relieve dryness, relieve tightness, smooth skin, and support laboratory objective index measurements (skin moisture content, skin moisture loss, skin elasticity, skin scaling, skin smoothness improved both immediately and after 4 weeks of use, and were statistically different from the control). In addition, 94% of consumers agree that the product is easy to absorb and not sticky after absorption, and 98% agree that the product has a protective film feel. Therefore, when the technology reported by the invention is applied to a proper product, the product can be endowed with good use feeling and efficacy, and the product has strong product competitiveness.

The invention will be further illustrated by the following specific examples. It should be noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art in light of the above teachings. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the manufacturer. All percentages and parts are by weight unless otherwise indicated.

Experimental materials:

distearyldimethylammonium chloride (TA-100): purchased from Evonik Operations GmbH;

cetostearyl alcohol (H-MY): sdn Bhd from Emery Oleochemicals (M);

white vaseline: purchased from hansheng chemical (smoothy) ltd;

urea: purchased from national drug group chemical agents, ltd;

hydroxyethyl urea (50%): purchased from Guangzhou Western general Fine chemical technology, Inc.;

triethyl citrate: purchased from purje perfumery, shanghai;

glycine: purchased from Hebei Huayang Biotech limited;

cetyl alcohol (cetyl alcohol): from BASF;

behenyl alcohol (behenyl alcohol): from BASF;

cationic conditioner ECON-100: purchased from Chongqing Haimai Biochemical technology, Inc.;

potassium lauryl phosphate (HR-S1): purchased from Liaoning Dandong Ankang chemical works;

polyglycerol pentastearate and sodium stearoyl lactylate: purchased from NIKKOL CHEMICAL co.ltd;

glycerol laurate: from BASF;

polyglycerol-10 myristate (polyglycerol myristate): purchased from NIKKOL CHEMICAL co.ltd;

PEG-20 methyl glucose sesquistearate (MSE-20): lublorun specialty chemical (shanghai) limited;

ceteareth-30: from BASF;

alatong 2121: purchased from CRODA;

polyquaternary ammonium salt-37 (PQ-37): from BASF;

grafted corn starch 25: purchased from Daito KaseiKogyo co, ltd.;

xanthan gum: purchased from Jungbunzlauer Austria AG;

sodium polyacrylate: purchased from saint japan;

acryloyldimethyl ammonium taurate/VP copolymer (AVC): purchased from Clariant;

10# white oil: purchased from Zhejiang Zhengxin Petroleum science and technology Co., Ltd;

isooctyl palmitate: purchased from PALM-oleo (klang) SDN BHD;

cetyl palmitate ACP: purchased from Croda (singapore);

dimethicone (100 cst): purchased from dow (zhang) investment limited.

An experimental instrument:

weighing a balance: METTLER TOLEDO, PB 4002-N;

a constant-temperature water bath kettle: Shanghai-Heng scientific instruments Inc., HWS-28;

a desk-top homogenizer: POLYTRON, PT 3100D;

a desk type stirrer: IKA EUROSTAR, power control-visc;

oven constant temperature at 25 ℃: friocell707, MMM, Germany;

oven constant temperature of 48 ℃: friocell707, MMM, Germany;

a pH meter: METTLER TOLEDO, SevenMulti;

viscometer: BROOKFIELD, DV-S digital display viscometer.

Examples 1 to 18: an emulsifying system containing different surfactants and preparation of corresponding urea-containing samples.

Appropriate amounts of phase A, phase B and phase C were weighed in three beakers as shown in Table 1 and heated in a 90 ℃ water bath for 30min, respectively. Homogenizing phase A with a desk type homogenizer at 5000rpm for 2min to disperse uniformly; then keeping 5000rpm for homogenization, adding phase B while the mixture is hot, and continuing to homogenize for 2min after the addition is finished; continuing to keep 5000rpm for homogenization, adding the C phase into the mixed sample while the mixed sample is hot, and keeping the mixed sample for homogenization for 5min after the C phase is added. After which the beaker was sealed using PE film and the sample was allowed to stand overnight at room temperature. Adding phase D the next day, homogenizing again at room temperature with a desk homogenizer at 5000rpm for 3min to mix the sample uniformly, sealing the beaker with PE film, and keeping the sample for use.

Table 1 shows the surfactant types and the amounts of the respective raw materials contained in examples 1 to 18.

TABLE 1

Examples 1-18 were prepared with 9 multiple emulsification systems containing different surfactants, each surfactant formulated separately for the base and one for each of the examples containing urea. The preparation amount of each sample is 200g, the preparation process is unified by a concentrated aqueous phase method, the concentrated aqueous phase method is compounded with 2% of cetearyl alcohol and 6% of white vaseline, and the addition amount of the urea in the embodiment containing the urea is 5%.

Examples 19 to 33: preparing hydrosols of various polymer thickeners and corresponding samples containing urea.

Weighing a proper amount of deionized water in a beaker according to the table 2, stirring at room temperature at 500rpm, slowly adding the polymer powder into the beaker, and after the polymer is soaked and dispersed, increasing the stirring speed to 1000rpm and keeping the stirring speed for 60min to completely and uniformly disperse the polymer. Thereafter, add phase B into the beaker and continue stirring at 1000rpm for 30min to completely dissolve and disperse the solid uniformly.

Table 2 shows the types of the polymeric thickeners and the amounts of the respective raw materials used in examples 19 to 33.

TABLE 2

Examples 19-33 were prepared with 5 composite emulsification systems containing different polymeric thickeners, each having a molecular weight adjusted to 0.4% or 0.5% depending on its aqueous viscosity. Three samples, namely a base material sample, a urea-containing sample and a urea-containing composition sample, are respectively prepared from each macromolecular thickening agent. The preparation amount of each sample is 200g, the urea addition amount of each urea-containing sample is 5%, and 5% of urea, 5% of glycine and 0.5% of triethyl citrate are added to each urea-containing composition sample.

Test example 1: stability testing of examples 1-33

After the pH and viscosity measurements of the samples of the fresh examples 1 to 33, each sample was divided equally into 2150 ml transparent PET bottles, which were placed in a 25 ℃ incubator and a 48 ℃ incubator, respectively, after the caps were tightened. And taking the sample out of the incubator regularly, standing for 6h, cooling to room temperature, measuring the pH and viscosity of the sample, observing the properties of the sample, and returning the sample to the incubator after the measurement is finished.

Table 3 shows the pH and viscosity of examples 1-33 at each test time point.

TABLE 3

Table 3 summarizes the pH and viscosity of examples 1-33 at each test time point. Examples 1-18 are built emulsification systems prepared with 9 different commercially available surfactants, and corresponding urea addition samples. Wherein, 2 cationic surfactants (TA-100, examples 1-2; ECON-100, examples 3-4), 1 anionic surfactant (HR-S1, examples 5-6), 1 anionic compound nonionic surfactant (polyglycerol pentastearate and sodium stearoyl lactylate, examples 7-8) and 5 nonionic surfactants are selected. The 5 nonionic surfactants can be further subdivided into: (1) monoglycerides (glyceryl laurate, examples 9-10); (2) polyglycerol-based surfactants (polyglycerol monomyristate, examples 11-12); (3) polyethylene glycol surfactants (ceteareth-30, examples 13-14); (4) carbohydrate surfactants (MSE-20, examples 15-16; Alaton 2121, examples 17-18).

After a one month standing at room temperature for the TA-100 based built emulsification system (example 1), the sample pH dropped slightly from 4.99 to 4.96; the sample viscosity was 4780 mPas, which was higher than that of the fresh sample 3170 mPas. After standing at 48 ℃ for 1 month, the pH of the sample was 4.79, which was slightly lower than the initial value, while the viscosity was 2380 mPas, which was slightly lower than the freshly prepared sample. After the sample formulated with 5% urea (example 2) had been left at room temperature for 1 month, the pH of the sample rose from 5.45 to 7.66 and the viscosity dropped substantially from 2180 mPas to 680 mPas. The viscosity of the sample increased significantly after being left at 48 ℃ for 1 month. The viscosity of the sample after standing at 48 ℃ for 1 week and 2 weeks, i.e., 1 month, was 11530 mPas, 11100 mPas and 9720 mPas, respectively, compared with 3570 mPas of the fresh sample. At the same time, the sample pH also rose from 5.45 to 9.24. The above experimental results show that the TA-100 complex system can stably bear urea, and in addition, in the high-temperature stability test of the embodiment 2, the viscosity of the sample is obviously improved.

After a one month storage at room temperature of the formulated emulsification system based on the cationic conditioner ECON-100 (example 3), the pH of the sample slightly dropped from 3.89 to 3.86; the sample viscosity is too low, the suspension force is insufficient and cannot be kept stable, and the layering phenomenon can occur after the sample is kept static for a short time. After the sample is placed at 48 ℃ for 1 month, the sample is layered at each time point, and the pH value of the sample after the stability test is 3.67 which is slightly reduced compared with the initial value. After the 5% urea formulated sample (example 4) was allowed to stand at room temperature for 1 month, the pH of the sample slightly increased from 4.06 to 4.16, and the sample also delaminated at each time point. After the sample was allowed to stand at 48 ℃ for 1 month, the pH rose dramatically from 4.06 to 7.58, with delamination also occurring at each test time point. The experimental results show that the cationic conditioner ECON-100 compound system cannot stably bear urea, and two samples have the problem of layering under various test conditions. Furthermore, despite being a cationic surfactant, the formulated urea sample (example 4) did not observe the thickening properties similar to those exhibited by example 2 in the high temperature time test.

After a formulated emulsification system (example 5) based on potassium lauryl phosphate (HR-S1) was allowed to sit at room temperature for one month, the pH of the sample dropped slightly from 7.57 to 7.45; the sample viscosity was 725 mPas, which was higher than 117 mPas of the fresh sample. After standing at 48 ℃ for 1 month, the pH of the sample was 7.72, which slightly increased from the initial value, but the sample delaminated at each time point due to too low a viscosity. The pH of the sample (example 6) containing 5% urea was slightly increased from 7.43 to 7.62 after the sample was left at room temperature for 1 month, and the viscosities of the samples at room temperature for 1 week, 2 weeks, and 1 month were 392 mPas, 1658 mPas, and 2358 mPas, respectively, which were significantly increased from the initial value of 125 mPas. After the sample is placed at 48 ℃ for 1 month, the pH value of the sample is greatly increased from 7.43 to 8.93, and the samples are also layered due to insufficient suspension force caused by low viscosity in each test. The experimental results show that the lauryl alcohol phosphate potassium salt (HR-S1) compound emulsification system can only stably bear urea at room temperature, and the material body is layered due to insufficient suspension force at high temperature.

After a compound emulsification system based on polyglycerol pentastearate and sodium stearoyl lactylate (example 7) is placed at room temperature for one month, the pH value of the sample is slightly reduced from 4.74 to 4.33; the sample viscosity was 18580 mPas, which was significantly higher than 4950 mPas of the freshly prepared sample. After standing at 48 ℃ for 1 month, the pH of the sample was 4.46, which is a small decrease from the initial value, while the viscosity was 14920 mPas, which is a similar small decrease from the freshly prepared sample. After the sample formulated with 5% urea (example 8) was allowed to stand at room temperature for 1 month, the pH of the sample rose from 4.80 to 5.87 and the viscosity rose significantly from 6250 mPas to 25250 mPas. The viscosity of the sample also increased significantly after standing at 48 ℃ for 1 month. The viscosities of the samples left standing at 48 ℃ for 1 week, 2 weeks and 1 month were 35580 mPas, 23830 mPas and 28500 mPas, respectively, compared with the viscosity of 6250 mPas of the fresh sample. At the same time, the pH of the sample also increased from 4.80 to 8.08. The experiment results show that the compound system based on the polyglycerol pentastearate and the sodium stearoyl lactylate can stably bear urea.

After one month of storage at room temperature for the dilaurin-based built emulsification system (example 9), the pH of the sample dropped from 4.77 to 4.07; but the viscosity of the sample is too low, the suspension force is insufficient, a stable emulsification system cannot be maintained, and the sample can be layered after standing for a short time. After being placed at 48 ℃ for 1 month, the materials are also layered due to the low viscosity of the materials; the pH of the sample after the stability test was 4.74, which was substantially the same compared to the initial value. The pH of the compounded 5% urea sample (example 10) increased slightly from 6.32 to 7.21 after being allowed to stand at room temperature for 1 month, and the viscosities of the samples after being allowed to stand at room temperature for 1 week, 2 weeks, and 1 month were 992 mPas, 3680 mPas, and 7830 mPas, respectively, which were significantly higher than the initial values (< 150 mPas). However, after the sample was allowed to stand at 48 ℃ for 1 month, the pH of the sample rose from 6.32 to 7.37, delamination occurred in each test due to insufficient suspending force due to too low a viscosity, and demulsification was evident from 2 weeks of standing, forming an oil cake on top of the body. The experimental results show that the compound emulsification system based on the lauroyl glyceride can only stably bear urea at room temperature, the viscosity of a micelle reconstituted material body is increased, but the micelle reconstituted material body is layered due to insufficient suspension force in a high-temperature stability test, and the micelle reconstitution can cause the emulsion breaking because the emulsifying capacity of the surfactant is reduced.

After one month at room temperature the compounded emulsifying system based on polyglycerol monomyristate (example 11) slightly dropped the sample pH from 7.99 to 6.67; the stable emulsifying system can not be maintained due to the insufficient suspending force caused by the excessively low viscosity of the sample, and the layering can be realized after the short-time standing. After being placed at 48 ℃ for 1 month, the material body still delaminates due to too low viscosity; the pH of the sample after the stability test was 7.19, which was reduced from the initial value. After the 5% urea formulated sample (example 12) was allowed to sit at room temperature for 1 month, the pH of the sample dropped slightly from 8.16 to 7.98, with delamination at each time point. After the sample was allowed to sit at 48 ℃ for 1 month, the pH of the sample rose from 8.16 to 8.83 and the samples were similarly stratified at each time tested. The experimental results show that the polyglycerol monomyristate compound emulsifying system cannot stably bear urea, and two samples have the problem of layering under various testing conditions.

The built emulsification system based on ceteareth-30 (example 13) showed a small increase in the pH of the sample from 6.30 to 6.45 after a month at room temperature; the viscosity of the sample is too low, the suspension force is insufficient, a stable emulsification system cannot be maintained, and the sample can be layered after standing for a short time. After being placed at 48 ℃ for 1 month, the material body is also layered due to too low viscosity; the pH value drops to 4.13, which is significantly lower than the initial value. After the 5% urea formulated sample (example 14) was left at room temperature for 1 month, the pH rose from 7.52 to 8.14 and the sample stratified at each time point. After the sample was allowed to sit at 48 ℃ for 1 month, the pH of the sample rose from 7.52 to 9.06 and the samples stratified at each time tested. The experimental results show that the ceteareth-30 complex system cannot stably bear urea, and two samples have the problem of layering under various test conditions.

After a compound emulsification system based on MSE-20 (example 15) was left at room temperature for one month, the pH of the sample dropped slightly from 7.08 to 6.67; the sample viscosity was 167 mPas, which was slightly lower than that of the fresh sample 183 mPas. After the sample is placed at 48 ℃ for 1 month, the pH value of the sample is 3.86, and is obviously reduced compared with the initial value; the viscosity of the samples was 1700 mPas, 2600 mPas and 15670 mPas in this order after standing for 1 week, 2 weeks and 1 month, which was significantly higher than that of the freshly prepared samples. After a sample of the compounded 5% urea (example 16) had been left at room temperature for 1 month, the pH rose from 7.13 to 7.93 and the viscosity slightly dropped from 167 to 142 mPas. The viscosity of the sample also increased after standing at 48 ℃ for 1 month. The viscosity of the samples left at 48 ℃ for 1 week, 2 weeks and 1 month was 1400 mPas, 2200 mPas and 1833 mPas, respectively, compared to the viscosity of the freshly prepared sample of 167 mPas, but the rise was significantly smaller than that of the non-formulated urea sample. At the same time, the sample pH also rose from 7.13 to 8.92. The experimental results show that the compound system based on MSE-20 can stably bear urea, but the compound of urea obviously influences the micelle reconstruction of the surface active at high temperature, so that the rising amplitude of the viscosity of a material body of a compound urea sample is obviously lower than that of an un-compound urea sample in a high-temperature stability test.

After the alaton 2121-based built-up emulsification system (example 17) was left at room temperature for one month, the pH of the sample dropped slightly from 7.01 to 6.82; the sample viscosity was 46330 mPas, which was slightly lower than that of 47500 mPas in the fresh sample. After the sample is placed at 48 ℃ for 1 month, the pH value of the sample is 6.52, which is reduced compared with the initial value; the viscosity of the samples was 50170 mPas, 51000 mPas and 52500 mPas in this order, after standing for 1 week, 2 weeks and 1 month, which were slightly higher than those of the freshly prepared samples. After a sample of the compounded 5% urea (example 18) had been left at room temperature for 1 month, the pH rose from 6.95 to 7.19 and the viscosity slightly dropped from 48750 to 43170 mPas. The viscosity of this sample after leaving at 48 ℃ for 1 month was remarkably lowered, and the viscosities of the samples after leaving at 48 ℃ for 1 week, 2 weeks and 1 month were 44080 mPas, 32250 mPas and 23000 mPas, respectively, as compared with 48750 mPas of the fresh sample. At the same time, the sample pH also rose from 6.95 to 7.92. The experimental results show that the compound system based on the alaton 2121 can stably bear urea, but the compound urea obviously influences the high-temperature stability of the emulsifying system, and the viscosity of the sample is less than half of the initial value after 1-month stability test.

The above experimental data show that of the 9 emulsion systems tested, only 4 emulsion systems can carry urea, wherein the emulsion systems based on MSE-20 and alaton 2121 have shown a more pronounced impact of urea formulation on the stability of the respective emulsion system at high temperatures. It can be seen that for most surfactants, carrying urea presents a significant challenge to formulation stability. It is important to note that the TA-100 based formulated emulsion system (example 2) has good stability and also exhibits high temperature thickening properties after urea formulation that the uncomplexed urea sample (example 1) does not have, and therefore further studies on the properties of the formulated emulsion system are described below.

In addition to surfactants, polymeric thickeners are often used in cosmetics to provide viscosity to the formulation, which in turn improves formulation stability. Examples 19-33 investigated the stability of five different commercially available polymeric thickener hydrosols after compounding urea, and the investigated polymers can be classified into three categories according to the structure of the polymer chain: (1) cationic polymeric thickeners (PQ-37, examples 19-21); (2) nonionic polymeric thickeners (M25, examples 22-24; xanthan gum, examples 25-27); (3) anionic polymeric thickeners (sodium polyacrylate, examples 28-30; AVC, examples 31-33). Each macromolecule was prepared separately in triplicate, one without urea, the second with 5% urea, the third with 5% urea, 5% glycine and 0.5% triethyl citrate.

The 0.5% PQ-37 hydrosol (example 19) was found to be very stable. After the sample is placed at room temperature for 1 month, the viscosity slightly rises from 16430 mPas to 18370 mPas; after standing at 48 ℃ for one month, the viscosity was 15130 mPas, which was not significantly changed from 16430 mPas of the fresh sample. After compounding PQ-37 with 5% urea (example 20), the sample stability significantly deteriorated, with the pH increasing from 4.43 to 7.84 and the viscosity decreasing from 18030mPa · s to 5280mPa · s after example 20 had been left to stand at room temperature for 1 month; on the other hand, after leaving at 48 ℃ for only one week, the viscosity greatly decreased to 183 mPas as the pH increased to 8.88. After compounding PQ-37 with 5% urea, 5% glycine and 0.5% triethyl citrate (example 21), the stability of the sample also becomes significantly worse, and after example 21 is left at room temperature for 1 month, the pH value rises slightly from 5.23 to 5.77, while the viscosity drops from 13230 mPa.s to 5430 mPa.s; after standing at 48 ℃ for one week, the pH was slightly increased to 5.70, and the viscosity was greatly decreased to 333 mPas. The experimental results show that the PQ-37 hydrosol cannot stably bear urea. And the results of example 21 show that the increase in pH caused by urea decomposition is not the only cause of the viscosity loss of the material.

The 0.4% M25 hydrosol (example 22) was found to be more stable. After the sample was left at room temperature for 1 month, the viscosity increased slightly from 15420 mPas to 18270 mPas; after standing at 48 ℃ for one month, the viscosity was 8270 mPas, which was lower than that of 15420 mPas of the fresh sample. After compounding M25 with 5% urea (example 23), the sample stability became poor, and after example 20 was left at room temperature for 1 month, the pH rose from 7.13 to 7.48, while the viscosity decreased from 16080mPa · s to 15220mPa · s; after standing at 48 ℃ for one month, the viscosity dropped to 2230 mPas greatly as the pH increased to 8.90. After compounding PQ-37 with 5% urea, 5% glycine and 0.5% triethyl citrate (example 24), the sample stability also deteriorated, and after example 24 was left to stand at room temperature for 1 month, the pH decreased slightly from 6.76 to 6.62, while the viscosity decreased from 15830 mPa.s to 8700 mPa.s; after standing at 48 ℃ for one month, the pH dropped to 6.31 and the viscosity dropped considerably to 1170 mPas. The results of the above experiments show that the M25 hydrosol cannot stably carry urea.

The 0.5% xanthan hydrosol (example 25) is very stable. After the sample is placed at room temperature for 1 month, the viscosity slightly rises from 1242 mPas to 1317 mPas; after standing at 48 ℃ for one month, the viscosity was 970 mPas, which was slightly lower than that of the fresh sample. After compounding xanthan gum with 5% urea (example 26), the sample still maintained good stability, and after example 20 was left to stand at room temperature for 1 month, the pH rose from 7.04 to 7.38, while the viscosity rose slightly from 1383mPa · s to 1425mPa · s; after standing at 48 ℃ for one month, the pH of the sample increased to 8.65 and the viscosity decreased to 867 mPas. After compounding PQ-37 with 5% urea, 5% glycine and 0.5% triethyl citrate (example 27), there was no significant change in sample stability, and after example 21 was left at room temperature for 1 month, the pH increased slightly from 5.55 to 7.21, while the viscosity increased slightly from 1442 mPa.s to 1575 mPa.s; after one month at 48 ℃ the pH increased slightly to 6.04 and the viscosity of the sample decreased slightly to 1270 mPas. The above experimental results show that the xanthan gum hydrosol can stably carry urea and the composition thereof.

The 0.4% sodium polyacrylate hydrosol (example 28) is very stable. After the sample is placed at room temperature for 1 month, the viscosity slightly rises from 2667 mPas to 2625 mPas; after standing at 48 ℃ for one month, the viscosity was 2845 mPas, which was not much changed from the freshly prepared sample. The sample stability was significantly worse after compounding sodium polyacrylate with 5% urea (example 29), with example 29 standing at room temperature for 1 month with pH rising from 6.89 to 7.26 and viscosity decreasing from 3392mPa · s to 833mPa · s; after leaving at 48 ℃ for only one week, the viscosity dropped to 142 mPas with a pH increase to 7.99. After compounding sodium polyacrylate with 5% urea, 5% glycine and 0.5% triethyl citrate (example 30), the stability of the sample also became significantly worse. Example 30 after standing at room temperature for 1 month, the pH dropped from 6.51 to 6.32 slightly, while the viscosity dropped from 2000 mPas to 358 mPas greatly; after one week at 48 ℃ the pH dropped to 5.80 and the viscosity of the sample dropped to 117 mPas. The above experimental results show that the sodium polyacrylate hydrosol can not stably carry the urea and the urea composition.

The 0.4% AVC hydrosol (example 31) is very stable. After the sample is placed at room temperature for 1 month, the viscosity slightly rises from 5250 mPas to 7400 mPas; after one month at 48 ℃, the viscosity is 13570mPa · s, which is significantly improved compared to the freshly prepared sample, probably because the high temperature promotes the rearrangement of the micelle structure. The stability of the sample was significantly worse after compounding AVC with 5% urea (example 32), with the pH increasing from 6.46 to 7.64 and the viscosity decreasing from 6092mPa · s to 608mPa · s after 1 month of standing at room temperature for example 32; on the other hand, after leaving at 48 ℃ for only one week, the viscosity dropped to 142 mPas greatly as the pH increased to 8.61. After compounding AVC with 5% urea, 5% glycine and 0.5% triethyl citrate (example 33), the sample stability also became significantly worse. Example 21 after standing at room temperature for 1 month, the pH increased slightly from 5.64 to 5.73, while the viscosity decreased from 3180 mPas to 508 mPas; after one week at 48 ℃ the pH increased slightly to 5.73 and the viscosity of the sample decreased greatly to 117 mPas. The experimental results show that the AVC hydrosol cannot stably bear the urea and the composition thereof.

The experimental results show that four of the five tested macromolecular thickening agents can not stably bear urea. However, the xanthan gum only carrying urea has many limitations in practical cosmetic applications, such as the lower thickening efficiency can not be used for preparing higher viscosity dosage forms, and the use feeling of the product is affected by the sticky skin feeling. It should be noted that, in addition, the four macromolecules with significantly reduced viscosity in the stability test, after the composition of urea + glycine + triethyl citrate is compounded, although the pH value is basically kept stable, the phenomenon of significant viscosity reduction still occurs in the stability test, which indicates that the increase of the pH value caused by the decomposition of urea is not the only reason for the viscosity loss of the sample. The strong ionic properties of the urea decomposition products also place high demands on the formulation stability. Most of the macromolecular thickeners form a gel structure by virtue of repulsive force among the same charges, and the enhancement of the ionic property can weaken an electric double layer, so that the repulsive force of the charges among the molecules of the thickeners is reduced and the thickeners lose viscosity, and therefore, the selection space of the macromolecular thickeners which still have good stability after urea is compounded is extremely limited.

Therefore, most of the surfactants and the macromolecular thickeners do not have the ability of stably carrying urea, thereby greatly limiting the practical application of the urea with strong skin care effect in cosmetics. Furthermore, after examining 12 kinds of commercially available emulsion formulations (viscosity of 1000 mPas to 20000 mPas, each formulation using an emulsifier different) from Shanghai's Co., Ltd, it was found that some and only cationic formulations using the same emulsifiers as those used in examples 1-2 could satisfy the requirements of national regulations on cosmetic stability after formulating urea. The other 11 surfactants based on anions, saccharides, polyethylene glycol and polyglycerol esters are compounded with various high-molecular thickeners, so that the problems of obvious viscosity reduction, layering and even emulsion breaking stability are caused. It can be seen that the cationic emulsion formulations based on TA-100 show good stability and interesting high temperature viscosifying properties after being compounded with urea, and more intensive investigations on the compounding of TA-100 with urea are carried out below.

Examples 34 to 53: preparing a compound emulsification system containing different grease types and grease amounts and a corresponding urea-containing sample.

Appropriate amounts of phase A, phase B and phase C were weighed in three beakers as shown in Table 4 and heated in a 90 ℃ water bath for 30min, respectively. Homogenizing phase A with a desk type homogenizer at 5000rpm for 2min to disperse uniformly; then keeping 5000rpm for homogenization, adding phase B while the solution is hot, and keeping the homogenization for 2min after the addition is finished; continuing to keep 5000rpm for homogenization, adding the C phase into the mixed sample while the mixed sample is hot, and keeping the mixed sample for homogenization for 5min after the C phase is added. After which the beaker was sealed using PE film and the sample was allowed to stand overnight at room temperature. Adding phase D the next day, homogenizing again at room temperature with a desk homogenizer at 5000rpm for 3min to mix the sample uniformly, sealing the beaker with PE film, and keeping the sample for use.

Table 4 shows the types of fats and oils and the amounts of the respective raw materials in examples 34 to 53.

TABLE 4

The emulsification systems of examples 34-53 were the same as examples 1-2, fixed at 5% TA-100 with 2% cetearyl alcohol. The amount of each sample was 200g, and the sample preparation process used the concentrated aqueous phase method in accordance with example 1-2. On the basis, the influence of the type and the amount of the oil and fat on the properties of the sample was examined. In examples 34 to 43, the amount of the fixed oil added was 6%, and samples were prepared using various types of oils; in examples 44 to 53, the amount of the oil was fixed to white petrolatum to examine the influence of the amount of the oil added on the properties of the samples. Each sample was prepared with a base and one urea containing example, each with 5% urea.

Test example 2: stability testing of examples 34-53

After the pH and viscosity measurements of the samples of fresh examples 34-53, each sample was divided equally into 2150 ml transparent PET bottles, which were placed in an incubator at 25 ℃ and an incubator at 48 ℃ after the caps were tightened. And taking the sample out of the incubator regularly, standing for 6h, cooling to room temperature, measuring the pH and viscosity of the sample, observing the properties of the sample, and returning the sample to the incubator after the measurement is finished.

Table 5 shows the pH and viscosity of examples 34-53 at each test time point (shown as a comparison between example 1 and example 2).

TABLE 5

Table 5 summarizes the pH and viscosity of examples 34-53 at each test time point and includes the corresponding data for examples 1-2 for comparison. Wherein, examples 1-2 and examples 34-41 investigate the influence of 5 different oils on the properties of a built emulsifying system, and the five oils include: (1) non-polar solid oils (white petrolatum, examples 1-2); (2) nonpolar liquid oils (10# white oil, examples 34-35); (3) polar liquid oils (isooctyl palmitate, examples 36-37); (4) polar solid oils (cetyl palmitate ACP, examples 38-39); (5) silicone oils (Dimethicone (100cst), examples 40-41). In addition, examples 42 to 43 use the above oils and fats in combination.

The pH of the sample emulsified # 10 white oil (example 34) after 1 month at room temperature was 4.94, which was almost unchanged from the initial value of 4.93; the viscosity of the sample was 5700 mPas, which was slightly higher than that of the freshly prepared sample 5450 mPas. After standing at 48 ℃ for 1 month, the pH of the sample dropped from 4.93 to 4.64, while the viscosity was 4200 mPas, which was a small drop compared to the freshly prepared sample. After a sample of the compounded 5% urea (example 35) had been left at room temperature for 1 month, the pH increased from 5.47 to 7.80 and the viscosity decreased from 8130 mPas to 5570 mPas. The viscosity of the sample increased after standing at 48 ℃ for 1 month. The viscosities of the samples left standing at 48 ℃ for 1 week, 2 weeks and 1 month were 9500 mPas, 8840 mPas and 8450 mPas, respectively, compared with the viscosity of 1092 mPas of the fresh sample. At the same time, the pH of the sample also increased from 5.47 to 9.21. The experimental results show that the TA-100 compound system can stably bear urea after emulsifying No. 10 white oil, and the viscosity of a sample tends to rise in a high-temperature stability test.

The pH of the sample of emulsified isooctyl palmitate (example 36) after 1 month at room temperature was 4.24, which increased slightly from the initial value of 4.09; the sample viscosity was 7930 mPas, which was higher than that of the fresh sample 6170 mPas. After standing at 48 ℃ for 1 month, the pH of the sample was 4.09, which corresponds to the initial value, while the viscosity was 4930 mPas, which is a small drop compared to the freshly prepared sample. After a sample of the compound 5% urea (example 37) had been left at room temperature for 1 month, the pH increased from 4.30 to 6.79 and the viscosity dropped considerably from 3570 mPas to 1100 mPas. The viscosity of the sample increased significantly after being left at 48 ℃ for 1 month. The viscosity of the samples left standing at 48 ℃ for 1 week, 2 weeks and 1 month was 5000 mPas, 9630 mPas and 8280 mPas, respectively, as compared with 3570 mPas of the fresh sample. At the same time, the pH of the sample also increased from 4.30 to 9.16. The experimental results show that urea can be stably supported after the isooctyl palmitate is emulsified by the TA-100 compound system, and the viscosity of a sample tends to rise in a high-temperature stability test.

The sample of emulsified cetyl ACP palmitate (example 38) after 1 month at room temperature had a pH of 4.59, slightly elevated from the initial value of 4.47; the sample viscosity was 7480 mPas, which was slightly higher than that of the fresh sample 6100 mPas. After standing at 48 ℃ for 1 month, the pH of the sample was 4.46, which was almost unchanged from that of the freshly prepared sample, while the viscosity was 6300 mPas, which was slightly increased from that of the freshly prepared sample. After a sample of the compounded 5% urea (example 39) had been left at room temperature for 1 month, the pH rose from 4.87 to 7.40 and the viscosity rose from 3570 mPas to 4570 mPas. The viscosity of the sample increased significantly after being left at 48 ℃ for 1 month. The viscosity of the samples after standing at 48 ℃ for 1 week, 2 weeks and 1 month was 12380 mPas, 17330 mPas and 15330 mPas, respectively, compared with the viscosity of 3570 mPas of the fresh sample. At the same time, the sample pH also increased from 4.87 to 8.98. The experimental results show that urea can be stably supported after the hexadecanoic acid ACP is emulsified by the TA-100 compound system, and the viscosity of a sample shows a remarkable rising trend in a high-temperature stability test.

The pH of the sample of simethicone (100cst) (example 40) after 1 month at room temperature was 5.04, which was slightly lower than the initial value of 5.08; the sample viscosity was 9630 mPas, which was significantly higher than 3250 mPas of the fresh sample. After standing at 48 ℃ for 1 month, the pH of the sample was also 5.04, while the viscosity was 11230 mPas, which was a significant increase over that of the freshly prepared sample. After the 5% urea-reconstituted sample (example 41) had been left to stand at room temperature for 1 month, the pH of the sample rose from 5.55 to 7.70 and the viscosity dropped from 4820 mPas to 2330 mPas. After the sample was left at 48 ℃ for 1 month, the viscosity of the sample was 8380 mPas, 16650 mPas and 17000 mPas, respectively. At the same time, the pH of the sample also increased from 5.55 to 9.21. The experimental results show that the TA-100 compound system emulsified dimethyl silicone oil (100cst) can stably bear urea, and the sample viscosity shows an obvious rising trend in a high-temperature stability test.

The sample emulsified with various oils (example 42) was allowed to stand at room temperature for 1 month, and the pH was slightly lowered from 6.10 to 5.86, while the viscosity was 1280 mPas, which was slightly increased as compared with the freshly prepared sample 858 mPas. After standing at 48 ℃ for 1 month, the pH of the sample dropped from 6.10 to 5.46, whereas the viscosity was 880 mPas, which was not significantly changed from the freshly prepared sample. After a sample of 5% urea was allowed to stand at room temperature for 1 month (example 43), the pH rose from 6.21 to 7.98, and the viscosity rose slightly from 858 mPas to 1380 mPas. The viscosity of the sample increased significantly after being left at 48 ℃ for 1 month. The viscosities of the samples left standing at 48 ℃ for 1 week, 2 weeks and 1 month were 5025 mPas, 20170 mPas and 11530 mPas, respectively, compared with the viscosity of 1092 mPas of the fresh sample. At the same time, the pH of the sample also increased from 6.21 to 9.02. The experimental results show that the TA-100 compound system can still stably bear urea after emulsifying the compound grease, and the sample viscosity also shows a remarkable rising trend in a high-temperature stability test.

The following conclusions can be drawn by combining the above experimental results: although the samples of examples 34-43 differ slightly in their properties due to differences in grease properties. But overall, all samples showed the following commonalities consistent with examples 1-2: all examples were able to stably carry urea, and the viscosity of the samples rose in the high temperature stability test after urea compounding. The TA-100 compound emulsifying system has wide grease selection space after being compounded with urea, and is beneficial to the practical application of the technology reported by the invention in cosmetics.

Examples 44-53 the fixed oil was white petrolatum and the effect of the oil addition on the properties of the TA-100 built emulsification system was examined. The amounts of the oils and fats added in examples 44 to 45, 46 to 47, 48 to 49, 1 to 2, 50 to 51 and 52 to 53 were 0%, 1%, 3%, 6%, 10% and 20% in this order.

After the sample without compounded grease (example 44) was left at room temperature for 1 month, the pH was 4.97, which was slightly lower than the initial value of 5.29; the sample viscosity was 2150 mPas, which was slightly higher than that of the freshly prepared sample 1700 mPas. After standing at 48 ℃ for 1 month, the pH of the sample was 4.88 and the viscosity was 1280 mPas, which was lower than that of the freshly prepared sample. After a sample of the compounded 5% urea (example 45) had been left at room temperature for 1 month, the pH rose from 5.27 to 7.14 and the viscosity fell from 1270 mPas to 258 mPas. The viscosity of the sample increased significantly after being left at 48 ℃ for 1 month. The viscosity of the samples at 48 ℃ for 1 week, 2 weeks and 1 month was 4250 mPas, 14500 mPas and 14750 mPas, respectively, compared to the viscosity of the freshly prepared sample of 1270 mPas. At the same time, the pH of the sample also increased from 5.27 to 9.24. The experimental results show that the TA-100 compound emulsion system has good urea bearing performance under the condition of not compounding grease, and the properties of related samples have no obvious difference compared with those of the examples 1-2.

After a compounded 1% white petrolatum sample (example 46) was left at room temperature for 1 month, the pH was 5.01, which was slightly lower than the initial value by 5.25; the sample viscosity was 1980 mPas, which was slightly higher than 1720 mPas of the fresh sample. After standing at 48 ℃ for 1 month, the pH of the sample was 4.84 and the viscosity was 1330 mPas, which was lower than that of the freshly prepared sample. After a sample of the compounded 5% urea (example 47) had been left at room temperature for 1 month, the pH increased from 5.75 to 7.27 and the viscosity decreased from 1320 to 300 mPas. The viscosity of the sample increased significantly after being left at 48 ℃ for 1 month. The viscosities of the samples at 48 ℃ for 1 week, 2 weeks and 1 month were 3450 mPas, 13670 mPas and 14830 mPas, respectively, compared to the viscosity of the freshly prepared sample of 1320 mPas. At the same time, the sample pH also rose from 5.75 to 9.23. The above experimental results show that the TA-100 complex emulsion system has good urea bearing capacity when 1% white vaseline is compounded, and the properties of the related samples are not obviously different from those of the samples in examples 1-2.

After a compounded 3% white vaseline sample (example 48) is placed at room temperature for 1 month, the pH value is 4.97, which is slightly reduced compared with the initial value of 5.29; the sample viscosity was 2120 mPas, which was slightly higher than 1900 mPas of the fresh sample. After standing at 48 ℃ for 1 month, the pH of the sample was 4.88 and the viscosity was 1330 mPas, which was reduced compared to the viscosity of the freshly prepared sample. After a sample formulated with 5% urea (example 49) had been left at room temperature for 1 month, the pH rose from 5.76 to 7.41 and the viscosity fell from 1530 to 333 mPas. The viscosity of the sample increased significantly after being left at 48 ℃ for 1 month. The viscosities of the samples left standing at 48 ℃ for 1 week, 2 weeks and 1 month were 5800 mPas, 16080 mPas and 1650 mPas, respectively, compared with the viscosity of the fresh sample of 1530 mPas. At the same time, the pH of the sample also increased from 5.76 to 9.26. The above experimental results show that the TA-100 complex emulsion system has good urea bearing capacity when 3% white vaseline is compounded, and the properties of the related samples are not obviously different from those of the samples in examples 1-2.

After a compounded 10% white vaseline sample (example 50) is placed at room temperature for 1 month, the pH value is 5.09, which is slightly reduced compared with the initial value of 5.29; the sample viscosity was 2670 mPas, which was slightly higher than 2200 mPas of the fresh sample. After standing at 48 ℃ for 1 month, the pH of the sample was 5.20 and the viscosity was 1620 mPas, which was lower than that of the freshly prepared sample. After a sample of 5% urea formulated (example 51) had been left at room temperature for 1 month, the pH of the sample rose from 5.78 to 7.43 and the viscosity dropped from 1770 mPas to 392 mPas. The viscosity of the sample increased significantly after being left at 48 ℃ for 1 month. The viscosity of the sample after standing at 48 ℃ for 1 week, 2 weeks and 1 month was 8680 mPas, 18750 mPas and 21500 mPas, respectively, compared with the viscosity of 1770 mPas of the fresh sample. At the same time, the sample pH also rose from 5.78 to 9.28. The above experimental results show that the TA-100 complex emulsion system has good urea bearing capacity when 10% white vaseline is compounded, and the properties of the related samples are not obviously different from those of the samples in examples 1-2.

The pH of the 20% white petrolatum-compounded sample (example 52) was 5.00, which was reduced from the initial value of 5.40 after being left at room temperature for 1 month; the viscosity of the sample was 10630 mPas, which was slightly higher than that of the freshly prepared sample 7020 mPas. After standing at 48 ℃ for 1 month, the pH of the sample was 4.95 and the viscosity was 4820 mPas, which is lower than that of the freshly prepared sample. After a sample of the compounded 5% urea (example 53) had been left at room temperature for 1 month, the pH rose from 5.76 to 7.55 and the viscosity dropped from 2380 mPas to 800 mPas. The viscosity of the sample increased significantly after being left at 48 ℃ for 1 month. The viscosities of the samples left standing at 48 ℃ for 1 week, 2 weeks and 1 month were 14230 mPas, 18170 mPas and 19500 mPas, respectively, compared with the viscosity of the fresh sample of 2380 mPas. At the same time, the pH of the sample also increased from 5.76 to 9.23. The above experimental results show that the TA-100 complex emulsion system has good urea bearing capacity when 20% white vaseline is compounded, and the properties of the related samples are not obviously different from those of the samples in examples 1-2.

Combining the results of the experiments of examples 44-53, we found that the viscosity of the TA-100 built emulsion system increased gradually as the amount of white petrolatum was increased. Within the range of 0-20% of the white vaseline compound amount, the TA-100 compound emulsifying system can stably bear urea, and the properties of the sample are basically consistent compared with those of the samples in examples 1-2. The experimental results of examples 34-53 demonstrate that the TA-100 complex emulsification system has good urea bearing capacity under all the above-mentioned test conditions, has a wide adjustment space for grease addition and complex species, and is beneficial to the practical application of the technology reported in the present invention in the cosmetic industry.

Examples 54 to 62: and (3) preparing TA-100 compound emulsification system samples of different urea adding amounts and urea compositions or derivatives.

Appropriate amounts of phase A, phase B and phase C were weighed in three beakers as shown in Table 6 and heated in a 90 ℃ water bath for 30min, respectively. Homogenizing phase A with a desk type homogenizer at 5000rpm for 2min to disperse uniformly; then keeping 5000rpm for homogenization, adding phase B while the solution is hot, and keeping the homogenization for 2min after the addition is finished; continuing to keep 5000rpm for homogenization, adding the C phase into the mixed sample while the mixed sample is hot, and keeping the mixed sample for homogenization for 5min after the C phase is added. After which the beaker was sealed using PE film and the sample was allowed to stand overnight at room temperature. Adding phase D the next day, homogenizing again at room temperature with a desk homogenizer at 5000rpm for 3min to mix the sample uniformly, sealing the beaker with PE film, and keeping the sample for use.

Table 6 shows the charge of each of the feedstocks of examples 54-62.

TABLE 6

The emulsification systems of examples 54-62 were the same as examples 1-2, fixed at 5% TA-100 with 2% H-MY. The amount of each sample was 200g, and the sample preparation process used the concentrated aqueous phase method in accordance with example 1-2. In examples 54 to 61, 6% white vaseline was formulated, and on the basis of this, the influence of the amount of urea added, urea derivatives and urea compositions on the properties of the samples was examined. Example 625 kinds of oils and fats were emulsified (oil and fat ratio same as in example 42) and formulated with a urea composition.

Test example 3: stability testing of examples 54-62

After the pH and viscosity measurements of the samples of fresh examples 54-62, each sample was divided equally into 2150 ml transparent PET bottles, which were placed in an incubator at 25 ℃ and an incubator at 48 ℃ after the caps were tightened. And taking the sample out of the incubator regularly, standing for 6h, cooling to room temperature, measuring the pH and viscosity of the sample, observing the properties of the sample, and returning the sample to the incubator after the measurement is finished.

Table 7 shows the pH and viscosity of examples 54-62 at each test time point (shown as a comparison of examples 1-2 and examples 42-43).

TABLE 7

Table 7 summarizes the pH and viscosity of examples 54-62 at various test time points and includes the data for examples 1-2 and examples 42-43 for comparison. Wherein, the examples 1-2 and 54-59 investigate the influence of 8 different urea addition amounts on the properties of the compound emulsification system, and the urea addition amounts are as follows in sequence according to the sequence of the urea addition amounts: 0% (example 1), 0.1% (example 54), 0.2% (example 55), 0.5% (example 56), 1% (example 57), 2% (example 58), 5% (example 2) and 10% (example 59). Example 60 and example 61 were the same as the above example base material but were formulated with a urea composition (5% urea + 5% glycine + 0.5% triethyl citrate) and a urea derivative (5% hydroxyethyl urea), respectively. Example 62 multiple oils were compounded (emulsified oils as in example 42) and urea compositions were compounded to simulate a complex system that approximates the actual formulation of a cosmetic.

The pH of the 0.1% urea-compounded sample (example 54) rose slightly from 4.92 to 6.19 after 1 month at room temperature, with a viscosity of 2730 mPas, which is a small increase compared to 1750 mPas of the freshly prepared sample. After standing at 48 ℃ for 1 month, the pH of the sample rose from 4.92 to 7.98. The viscosity of the samples left at 48 ℃ for 1 week, 2 weeks and 1 month was 1020 mPas, 850 mPas and 608 mPas, respectively, and was gradually decreased from 1750 mPas of the fresh samples.

The pH of the 0.2% urea-compounded sample (example 55) rose slightly from 5.09 to 5.20 after 1 month at room temperature, and the viscosity of the sample was 2630 mPas, which was higher than 1780 mPas of the freshly prepared sample. After standing at 48 ℃ for 1 month, the pH of the sample rose from 5.09 to 8.50. The viscosity of the samples left at 48 ℃ for 1 week, 2 weeks and 1 month was 780 mPas, 580 mPas and 408 mPas, respectively, and was gradually decreased from 1750 mPas of the fresh samples.

The pH of the 0.5% urea-compounded sample (example 56) rose from 5.04 to 5.66 after being left at room temperature for 1 month, with a sample viscosity of 2170 mPas, which was slightly higher than 1950 mPas of the freshly prepared sample. After standing at 48 ℃ for 1 month, the pH of the sample rose from 5.04 to 8.82. The viscosity of the samples left at 48 ℃ for 1 week, 2 weeks and 1 month was 530 mPas, 750 mPas and 2142 mPas, respectively, and tended to decrease and then increase compared with 1950 mPas of the fresh sample.

The sample formulated with 1% urea (example 57) had a pH increase from 5.09 to 6.20 after being left at room temperature for 1 month, and the viscosity of the sample was 1620 mPas, which was slightly lower than 1900 mPas of the freshly prepared sample. After standing at 48 ℃ for 1 month, the pH of the sample rose from 5.09 to 8.97. The viscosity of the samples left at 48 ℃ for 1 week, 2 weeks and 1 month was 520 mPas, 1050 mPas and 10830 mPas, respectively, and tended to decrease and then increase significantly compared with 1900 mPas of the freshly prepared samples.

The pH of the 2% urea reconstituted sample (example 58) rose from 5.13 to 6.71 after 1 month at room temperature, the viscosity of the sample was 1030 mPas and it decreased slightly compared to the freshly prepared sample 1180 mPas. After standing at 48 ℃ for 1 month, the pH of the sample rose from 5.13 to 9.08. The viscosity of the samples left at 48 ℃ for 1 week, 2 weeks and 1 month was 1270 mPas, 6920 mPas and 16250 mPas, respectively, and tended to increase gradually compared with 1180 mPas of the fresh samples.

After the sample formulated with 10% urea (example 59) had been left at room temperature for 1 month, the pH increased from 5.64 to 7.62, and the viscosity of the sample was 600 mPas, which was significantly lower than 1780 mPas of the freshly prepared sample. After standing at 48 ℃ for 1 month, the pH of the sample rose from 5.64 to 9.15. The viscosity of the samples left at 48 ℃ for 1 week, 2 weeks and 1 month was 15630 mPas, 10050 mPas and 11750 mPas, respectively, and was significantly increased and substantially stabilized as compared with 1780 mPas of the freshly prepared samples.

After a sample of the formulated urea composition (example 60) had been left at room temperature for 1 month, the pH slightly dropped from 5.59 to 5.58, and the viscosity of the sample was 500 mPas, which was lower than 820 mPas of the freshly prepared sample. After standing at 48 ℃ for 1 month, the pH of the sample rose slightly from 5.59 to 5.89. The viscosity of the samples left at 48 ℃ for 1 week, 2 weeks and 1 month was 4330 mPas, 8200 mPas and 13580 mPas, respectively, and was gradually increased compared with 820 mPas of the freshly prepared samples.

After the sample formulated with 5% hydroxyethyl urea (example 61) had been left at room temperature for 1 month, the pH dropped slightly from 8.42 to 8.16, and the sample viscosity was 6820 mPas, which was a small drop compared to the freshly prepared sample 8330 mPas. After standing at 48 ℃ for 1 month, the pH of the sample rose slightly from 8.42 to 8.92. The viscosity of the samples left at 48 ℃ for 1 week, 2 weeks and 1 month were 8200 mPas, 10000 mPas and 8120 mPas, respectively, which were slightly higher than that of 8330 mPas of the fresh samples.

After a sample (example 62) of the compounded composition of various oils and ureas was left at room temperature for 1 month, the pH dropped slightly from 6.76 to 6.19, and the viscosity of the sample was 620 mPas, which was slightly higher than 458 mPas of the freshly prepared sample. After standing at 48 ℃ for 1 month, the pH of the sample decreased from 6.76 to 5.93. The viscosity of the samples left at 48 ℃ for 1 week, 2 weeks and 1 month was 5025 mPas, 20170 mPas and 11530 mPas, respectively, and was significantly increased as compared with 458 mPas of the fresh samples.

The above experimental results can be summarized as follows:

(1) the TA-100 compound emulsification system can bear urea, urea derivatives and urea compositions with different addition amounts, and all samples have no layering and demulsification problems.

(2) Samples with low urea compound (0.1% -0.2%, examples 54-55) showed a tendency to decrease in viscosity in the high temperature time-dependent strengthening test; samples with lower urea loadings (0.5% -1%, examples 56-57) showed a viscosity increase followed by a viscosity decrease in the high temperature time-dependent stress test; samples with higher urea formulations (2% -10%, examples 2 and 58-59) showed a tendency to increase in viscosity during the high temperature time-dependent strengthening test. This phenomenon may result from the fact that the reconstitution of TA-100 micelles is promoted by water-soluble anionic small molecules produced by urea decomposition. Under the conditions of low urea amount and few decomposition products, the method mainly breaks the existing micelle structure to reduce the viscosity of the material body; however, when the amount of urea is high and the amount of decomposition products is large, the formation of new micelles having a larger polymerization degree is promoted, and the viscosity of the material is significantly increased. The experimental results show that the TA-100 compound emulsifying system is easier to show the unique property when higher-content urea is compounded, and has practical value in the formula of the urea with effective addition amount.

(3) Example 60 and example 61 urea compositions and urea derivatives were formulated based on example 1, both of which were stable to carry urea and had properties similar to other formulated urea samples. It is noted that the pH of the two samples did not rise significantly, indicating that the urea-promoted reconstitution of the TA-100 micelles did not occur only under strongly alkaline conditions. The TA-100 compound emulsifying system reported by the invention can show unique properties on the premise of meeting the regulatory standard of national cosmetic regulations on sample pH.

(4) Example 62 based on example 60, a variety of greases were formulated and the samples performed in the stability test substantially the same as the latter. For a complex system close to the actual formula of cosmetics, the emulsion system reported by the invention still has good bearing property and unique tackifying performance, and the complex emulsion system is proved to have wide oil and additive placement adjustment space and be beneficial to the application of the complex emulsion system in cosmetics.

Examples 63 to 88: adjusting the addition amount of TA-100, the addition type of long-chain fatty alcohol and the addition amount of the TA-100 composite emulsifying system sample, and preparing a corresponding urea-containing sample.

Appropriate amounts of phase A, phase B and phase C were weighed in three beakers as shown in Table 8 and heated in a 90 ℃ water bath for 30min, respectively. Homogenizing phase A with a desk type homogenizer at 5000rpm for 2min to disperse uniformly; then keeping 5000rpm for homogenization, adding phase B while the mixture is hot, and continuing to homogenize for 2min after the addition is finished; continuing to keep 5000rpm for homogenization, adding the C phase into the mixed sample while the mixed sample is hot, and keeping the mixed sample for homogenization for 5min after the C phase is added. After which the beaker was sealed using PE film and the sample was allowed to stand overnight at room temperature. Adding phase D the next day, homogenizing again at room temperature with a desk homogenizer at 5000rpm for 3min to mix the sample uniformly, sealing the beaker with PE film, and keeping the sample for use.

Table 8 shows the types of the long-chain fatty alcohols added in examples 63 to 88 and the amounts of the respective raw materials charged.

TABLE 8

Examples 63-88 the fixation process was a concentrated aqueous phase process, the amount of oil added was 6% white petrolatum, and the amount of each sample was 200 g. In examples 63 to 78, the amount of TA-100 added was 5%, and the influence of the amount and type of the added long-chain fatty alcohol on the properties of the material was examined. Examples 79-88 fixed long chain fatty alcohols were 2% H-MY, and the effect of TA-100 addition on the properties of the materials was examined. Each sample was prepared with a base stock and a urea-containing example, each added at 5%.

Test example 4: stability testing of examples 63-88

After measuring the pH and viscosity of the samples of fresh examples 63-88, each sample was divided equally into 2150 ml transparent PET bottles, which were placed in an incubator at 25 ℃ and an incubator at 48 ℃ after the caps were tightly screwed. And taking the sample out of the incubator regularly, standing for 6h, cooling to room temperature, measuring the pH and viscosity of the sample, observing the properties of the sample, and returning the sample to the incubator after the measurement is finished.

Table 9 shows the pH and viscosity of examples 63-88 at each test time point (as listed in examples 1-2).

TABLE 9

Table 9 summarizes the pH and viscosity at each test time point for examples 63-88 and includes the data for examples 1-2 for comparison. Wherein, examples 1-2 and examples 63-74 examined the influence of 7 different H-MY addition amounts, and the addition amounts of the H-MY are sequentially as follows: 0% (examples 63 to 64), 0.5% (examples 65 to 66, 1% (examples 67 to 68), 2% (examples 1 to 2), 3% (examples 69 to 70), 4% (examples 71 to 72) and 5% (examples 73 to 74). examples 75 to 76 and examples 77 to 78 were each formulated with 2% of behenyl alcohol and 2% of cetyl alcohol.

After a sample (example 63) which is not compounded with the long-chain fatty alcohol is placed at room temperature for 1 month, the pH value is 6.06, and is slightly increased compared with the initial value of 5.61; the sample viscosity was 1042 mPas, which was higher than 620 mPas of the fresh sample. After standing at 48 ℃ for 1 month, the pH of the sample was 5.35, which was slightly lower than the initial value, and the viscosity was 617 mPas, which was substantially the same as that of the freshly prepared sample. After a sample of the compounded 5% urea (example 64) had been left at room temperature for 1 month, the pH rose from 5.90 to 7.38 and the viscosity dropped slightly from 1030 to 783 mPas. The viscosity of the sample decreased significantly after being left at 48 ℃ for 1 month. The viscosity of the sample left at 48 ℃ for 1 week, 2 weeks and 1 month was 280 mPas, 280 mPas and 280 mPas, respectively, compared with the viscosity of the fresh sample of 1030 mPas. At the same time, the sample pH also rose from 5.90 to 8.98. It is necessary to point out that all the above samples show solid lumps, resulting from insufficient stability of the emulsified system, which in turn leads to the precipitation and agglomeration of the grease. The experimental results show that the TA-100 emulsifying system without long-chain fatty alcohol can not stably emulsify grease, and the phenomenon that the viscosity is obviously increased in a high-temperature aging stability test after urea compounding is also not observed, and the experimental results can prove that the long-chain fatty alcohol plays a key role in the compounding emulsifying system.

The sample (example 65) with 0.5% cetearyl alcohol (H-MY) combination, after 1 month at room temperature, had a pH of 5.68, which rose slightly from the initial value of 5.31; the sample viscosity was 400 mPas, which was slightly higher than 380 mPas of the fresh sample. After standing at 48 ℃ for 1 month, the pH of the sample was 4.97, which was slightly lower than the initial value, while the viscosity was 725 mPas, which was higher than that of the freshly prepared sample. After a sample of the compounded 5% urea (example 66) had been left at room temperature for 1 month, the pH rose from 5.62 to 7.41 and the viscosity dropped slightly from 420 mPas to 250 mPas. The viscosity of the sample decreased after being left at 48 ℃ for 1 month. The viscosity of the samples left at 48 ℃ for 1 week, 2 weeks and 1 month was 270 mPas, 280 mPas and 208 mPas, respectively, compared with the viscosity of 420 mPas of the fresh samples. At the same time, the sample pH also rose from 5.62 to 9.00. The above experimental results show that a TA-100 emulsifying system formulated with 0.5% cetearyl alcohol can carry urea, but no significant increase in viscosity in high temperature stability over time tests was observed after formulating urea. It can be seen that the properties of the low-long-chain fatty alcohol compound sample are significantly different from those of the sample in example 2.

The sample (example 67) with a 1% compound of cetearyl alcohol (H-MY) has a pH of 5.49, which rises slightly compared to the initial value of 5.31, after being left for 1 month at room temperature; the sample viscosity was 358 mPas, which was slightly lower than 430 mPas of the freshly prepared sample. After standing at 48 ℃ for 1 month, the pH of the sample was 4.81, which was lower than the initial value, while the viscosity was 575 mPas, which was slightly higher than that of the freshly prepared sample. After a sample of the compounded 5% urea (example 68) had been left at room temperature for 1 month, the pH increased from 5.65 to 7.46 and the viscosity decreased from 670 mPas to 267 mPas. The viscosity of the sample showed a marked increase after standing at 48 ℃ for 1 month. The viscosity of the samples left at 48 ℃ for 1 week, 2 weeks and 1 month was 2880 mPas, 5330 mPas and 7920 mPas, respectively, compared with the viscosity of the freshly prepared samples of 670 mPas. At the same time, the sample pH also rose from 5.65 to 9.00. The above experimental results show that the TA-100 emulsion system compounded with 1% cetearyl alcohol can carry urea, and the properties are substantially consistent compared with those of example 2.

The sample (example 69) with 3% of the cetearyl alcohol (H-MY) compound has a pH of 5.62, which rises slightly from the initial value of 5.32, after 1 month at room temperature; the sample viscosity was 9630 mPas, which was slightly higher than that of 7780 mPas of the fresh sample. After standing at 48 ℃ for 1 month, the pH of the sample was 4.79, which was lower than the initial value, while the viscosity was 8450 mPas, which was slightly higher than the freshly prepared sample. After a sample of the compounded 5% urea (example 70) had been left at room temperature for 1 month, the pH rose from 5.76 to 7.63 and the viscosity dropped slightly from 36420 mPas to 31580 mPas. The viscosity of the sample after being left at 48 ℃ for 1 month shows a small decrease. The viscosities of the samples left standing at 48 ℃ for 1 week, 2 weeks and 1 month were 23580 mPas, 23000 mPas and 21670 mPas, respectively, compared with the viscosity of the freshly prepared sample of 36420 mPas. At the same time, the sample pH also rose from 5.76 to 9.06. The above experiment results show that the TA-100 emulsifying system compounded with 3% of cetearyl alcohol can bear urea, and different from the example 2, the instant viscosity of the sample is obviously increased after the urea is compounded, and the viscosity of the urea-containing sample is slightly reduced in a high-temperature time test, which shows that the TA-100 compounding emulsifying system can show unique properties due to the higher adding amount of the cetearyl alcohol.

The sample (example 71) with a 4% compound of cetostearyl alcohol (H-MY) had a pH of 5.62, which increased slightly from the initial value of 5.16, after 1 month at room temperature; the sample viscosity was 32580 mPas, which was slightly lower than 36830 mPas of the freshly prepared sample. After standing at 48 ℃ for 1 month, the pH of the sample was 5.79, which was higher than the initial value, while the viscosity was 35330 mPas, which was slightly lower than the freshly prepared sample. The sample formulated with 5% urea (example 72) had a pH rise from 5.79 to 7.83 and a viscosity of 53420 mPas consistent with the freshly prepared sample after 1 month at room temperature. The viscosity of the sample showed a small increase after standing at 48 ℃ for 1 month. The viscosity of the samples left standing at 48 ℃ for 1 week, 2 weeks and 1 month was 48420 mPas, 59920 mPas and 65170 mPas, respectively, compared with the viscosity of 53420 mPas of the fresh samples. At the same time, the sample pH also rose from 5.79 to 8.94. The above experimental results show that the TA-100 emulsifying system compounded with 4% cetostearyl alcohol can bear urea, and the urea-containing sample shows a small rising trend in high-temperature stability tests. In contrast to example 2, a significant increase in the immediate viscosity of the sample occurred after urea was compounded.

The sample (example 73) with 5% of the cetearyl alcohol (H-MY) compound has a pH of 5.57, which rises slightly from the initial value of 5.05, after being left for 1 month at room temperature; the sample viscosity was 32580 mPas, which was lower than 45250 mPas of the freshly prepared sample. After standing at 48 ℃ for 1 month, the pH of the sample was 5.90, which was higher than the initial value, and the viscosity was 35000 mPas, which was lower than that of the freshly prepared sample. After a sample of 5% urea (example 74) had been left at room temperature for 1 month, the pH increased from 5.79 to 7.99 and the viscosity increased from 53420 mPas to 66250 mPas. The viscosity of the sample increased after being left at 48 ℃ for 1 month. The viscosity of the samples left at 48 ℃ for 1 week, 2 weeks and 1 month was 48420 mPas, 61630 mPas and 73080 mPas, respectively, compared to the viscosity of 53420 mPas of the fresh sample. At the same time, the sample pH also rose from 5.79 to 8.96. The above experimental results show that the TA-100 emulsion system formulated with 5% cetostearyl alcohol can carry urea, and consistent with example 2, the urea-containing sample showed an upward trend in the high temperature stability over time test.

After a sample (example 75) formulated with 2% behenyl alcohol (i.e., behenyl alcohol) was left at room temperature for 1 month, its pH was 5.28, which increased slightly from the initial value of 4.88; the sample viscosity was 8250 mPas, which was lower than that of 13580 mPas, which was the fresh sample. After standing at 48 ℃ for 1 month, the pH of the sample was 5.12, which was higher than the initial value, and the viscosity was 10500 mPas, which was slightly lower than that of the freshly prepared sample. After compounding the sample of 5% urea (example 76) and standing at room temperature for 1 month, the pH increased from 5.54 to 7.67 and the viscosity decreased from 14170 mPas to 7500 mPas. The viscosity of the sample increased after being left at 48 ℃ for 1 month. The viscosities of the samples left standing at 48 ℃ for 1 week, 2 weeks and 1 month were 15670 mPas, 26080 mPas and 27250 mPas, respectively, compared with the viscosity of the fresh sample 14170 mPas. At the same time, the sample pH also rose from 5.54 to 9.06. The experimental results show that the TA-100 emulsifying system compounded with 2% of behenyl alcohol can bear urea, and a urea-containing sample has an ascending trend in a high-temperature aging stability test. The initial viscosity of the corresponding sample was however higher compared to examples 1 and 2, indicating that the longer carbon chain of behenyl alcohol contributed to the formulation viscosity development.

After a sample (example 77) compounded with 2% cetyl alcohol was left at room temperature for 1 month, its pH was 5.68, which increased slightly from the initial value of 5.42; the sample viscosity was 2325 mPas, which was higher than that of the freshly prepared sample 1700 mPas. After standing at 48 ℃ for 1 month, the pH of the sample was 6.70, which was higher than the initial value, while the viscosity was 750 mPas, which was significantly lower than that of the freshly prepared sample. After a sample formulated with 5% urea (example 78) had been left at room temperature for 1 month, the pH increased from 5.92 to 7.27 and the viscosity increased from 2920 mPas to 5258 mPas. The viscosity of the sample increased after being left at 48 ℃ for 1 month. The viscosities of the samples at 48 ℃ for 1 week, 2 weeks and 1 month were 10880 mPas, 16170 mPas and 15670 mPas, respectively, compared to 2920 mPas of the fresh sample. At the same time, the sample pH also rose from 5.92 to 9.26. The above experimental results show that the TA-100 emulsification system compounded with 2% cetyl alcohol can carry urea, and the properties of the related samples are basically consistent with those of the examples 1-2.

The experimental results show that after TA-100 is compounded with proper types and addition amounts of long-chain fatty alcohol, the prepared sample can stably bear urea. However, with varying amounts and types of fatty alcohol compounds, the following properties were found in the experiments:

(1) the sample emulsified system without long-chain fatty alcohol is poor in stable star, and oil blocks are generated due to oil phase aggregation caused by demulsification in a stability test.

(2) After compounding a long-chain fatty alcohol sample with low content (0.5%, examples 65 to 67) with urea, no significant viscosity increase tendency occurred during the high-temperature stability test.

(3) After compounding a long-chain fatty alcohol sample with high content (more than 3 percent) and compounding urea, the instant viscosity is obviously increased in examples 69-74.

(4) The viscosity of the sample formulated with behenyl alcohol (examples 76 to 77) was significantly higher than that of the sample formulated with the same amount of cetearyl alcohol and cetyl alcohol.

The experiments show that the TA-100 compound emulsifying system has wide space in the selection of the type and the compound amount of the long-chain fatty alcohol. The viscosity of the body can be adjusted by adjusting the addition type and the addition amount of the long-chain fatty alcohol so as to adapt to the requirements of the formula viscosity of cosmetics of different types, and the method is favorable for the practical application of the invention in the cosmetic industry. In addition, when the compound amount of the long-chain fatty alcohol is higher, the viscosity of a sample after urea is added is obviously increased, and the compound emulsifying system disclosed by the invention has more advantages in application of cream or high-viscosity emulsion.

Examples 1-2 and 79-88 examined the effect of 6 different amounts of TA-100 added, in order of TA-100 addition: 0% (examples 79 to 80), 0.5% (examples 81 to 82), 2.5% (examples 83 to 84), 5% (examples 1 to 2), 7.5% (examples 85 to 86) and 10% (examples 87 to 88).

After leaving the sample without TA-100 added (example 79) at room temperature for one month, the pH dropped slightly from 4.88 to 4.62; in addition, due to the excessively low emulsifying capacity and suspending power of the formula, material body layering and demulsification are found at each test time point. After the sample is placed at 48 ℃ for 1 month, the sample is also layered and demulsified at each time point, and the pH value of the sample is 4.57 after the stability test, which is slightly reduced compared with the initial value. After the 5% urea formulated sample (example 80) was allowed to stand at room temperature for 1 month, the pH rose from 6.13 to 8.29 and the sample at each time point exhibited delamination and demulsification. After the sample was allowed to stand at 48 ℃ for 1 month, the pH of the sample rose from 9.17, and the samples were also allowed to stratify and break emulsions at various times during the test. The experimental results show that the sample without TA-100 complex does not have the capability of emulsifying and supporting a material body, and can not stably bear urea, and the core effect of TA-100 in a complex emulsifying system is proved.

After a one month standing at room temperature for a built-up emulsification system with a TA-100 0.5% formulation (example 81), the pH of the sample dropped slightly from 5.38 to 4.87; the samples stratified at each time point. After the sample is placed at 48 ℃ for 1 month, the sample still delaminates at each time point due to the excessively low viscosity, and the pH value of the sample after the stability test is 4.85, which is slightly reduced compared with the initial value. After the 5% urea formulated sample (example 82) was allowed to stand at room temperature for 1 month, the pH rose from 6.18 to 8.23 and the sample still delaminated at each time point. However, example 82 exhibited unique properties in the high temperature aging test at 48 ℃, and the viscosity of the samples left at 48 ℃ for 1 week, 2 weeks and 1 month were 1350mPa · s, 4458mPa · s and 18250mPa · s, respectively, showing a tendency to rise significantly compared to the initial values. The experimental results show that the compound emulsification system with the TA-100 compound amount of 0.5 percent shows the phenomenon that the viscosity is obviously increased in a high-temperature time test. The discovery means that TA-100 with lower concentration can be used to be compounded with other surfactants, so that the urea bearing capacity of the latter can be improved, the formula which cannot stably bear urea originally can meet the regulatory requirement of national regulations on the stability of cosmetics, and the urea bearing agent has high value in the practical application of the cosmetic industry.

The sample (example 83) with 2.5% of the TA-100 compound amount had a pH of 4.97 after being left at room temperature for 1 month, which was decreased from the initial value of 5.60; the sample viscosity was 383 mPas, which was slightly higher than 370 mPas of the fresh sample. After standing at 48 ℃ for 1 month, the pH of the sample was 4.85, which was lower than the initial value, and the viscosity was 542 mPas, which was higher than that of the freshly prepared sample. After a sample of the compounded 5% urea (example 84) had been left at room temperature for 1 month, the pH rose from 6.13 to 8.17 and the viscosity slightly dropped from 420 to 383 mPas. The viscosity of the sample showed a significant tendency to increase after standing at 48 ℃ for 1 month. The viscosities of the samples left standing at 48 ℃ for 1 week, 2 weeks and 1 month were 24200 mPas, 23500 mPas and 63920 mPas, respectively, compared with the viscosity of the fresh sample of 420 mPas. At the same time, the sample pH also rose from 6.13 to 9.24. The above experimental results show that the compound emulsification system with the TA-100 addition of 2.5% can bear urea, and the properties of the related samples are basically consistent with those of the examples 1-2.

The sample (example 85) with a TA-100 dose of 7.5% had a pH of 4.89 after being left at room temperature for 1 month, which was slightly lower than the initial value of 5.23; the sample viscosity was 28170 mPas, which was slightly higher than that of 27000 mPas, which was a fresh sample. After standing at 48 ℃ for 1 month, the pH of the sample was 4.79, which was slightly lower than the initial value, and the viscosity was 23670 mPas, which was also slightly lower than the freshly prepared sample. After a sample of 5% urea formulated (example 86) had been left to stand at room temperature for 1 month, the pH increased from 6.15 to 7.67 and the viscosity decreased from 41420 mPas to 25500 mPas. The viscosity of the sample after standing at 48 ℃ for 1 month showed a tendency to decrease and then increase. The viscosities of the samples left at 48 ℃ for 1 week, 2 weeks and 1 month were 12930 mPas, 25670 mPas and 55300 mPas, respectively, compared to the viscosity of the fresh sample of 41420 mPas. At the same time, the sample pH also rose from 6.15 to 9.14. The above experimental results show that the compound emulsification system with the TA-100 addition of 7.5% can bear urea, and the properties of the related samples are basically consistent with those of the examples 1-2.

The sample (example 87) with 10% of TA-100 loading was at pH 4.97 after 1 month at room temperature, slightly lower than the initial value of 5.08; the sample viscosity was 30420 mPas, which was slightly higher than 29080 mPas of the fresh sample. After standing at 48 ℃ for 1 month, the pH of the sample was 4.90, which is a small drop from the initial value, while the viscosity was 28330 mPas, which is a slight drop from the freshly prepared sample. After a sample of the compounded 5% urea (example 88) had been left at room temperature for 1 month, the pH rose from 5.58 to 7.47 and the viscosity dropped from 49180 mPas to 23920 mPas. The viscosity of the sample after standing at 48 ℃ for 1 month showed a tendency to decrease and then increase. The viscosities of the samples left at 48 ℃ for 1 week, 2 weeks and 1 month were 16270 mPas, 45500 mPas and 85700 mPas, respectively, compared with the viscosity of 49180 mPas of the fresh sample. At the same time, the sample pH also rose from 5.58 to 9.24. The above experimental results show that the compound emulsification system with the TA-100 addition of 10% can bear urea, and the properties of the related samples are basically consistent with those of the examples 1-2.

The experimental results show that after the dosage and the variety of the long-chain fatty alcohol are fixed, the prepared compound emulsifying system can stably bear urea within a wider TA-100 compound range. However, depending on the TA-100 formulation, the following characteristics were found in the experiments:

(1) samples not formulated with TA-100 (examples 79-80) did not have grease emulsification and structural support capability and showed problems of delamination and demulsification under all conditions tested. And the phenomenon of tackifying the compounded urea in a high-temperature time test is not shown, and the key effect of the TA-100 in a compounding system is proved.

(2) The sample compounded with low TA-100 (0.5%, example 81) delaminated due to insufficient suspension force; however, after urea is compounded (example 82), the viscosity of the material body is remarkably improved in a high-temperature stability test, and the fact that a sample with a low TA-100 addition amount has the characteristic of high-temperature tackifying after urea is compounded is proved. The discovery explains a brand-new formula design idea, and the compound use of a small amount of TA-100 and other emulsification systems is beneficial to improving the urea bearing capacity of the latter, so that the urea bearing capacity meets the requirement of national law on the stability of cosmetics.

(3) When the sample with high TA-100 content (more than 5 percent, examples 85-88) is compounded, the viscosity immediately rises after the urea is compounded, and the viscosity first drops and then rises in the stability test at high temperature, which may be because the urea decomposition product mentioned above promotes the micelle reconstruction of the TA-100.

In conclusion, the compound emulsifying system reported by the invention has the capability of stably bearing urea within a wider TA-100 compound amount range. The viscosity of the material body can be changed by adjusting the addition amount of TA-100, which is beneficial to applying the technology reported by the invention to various cosmetic formulations.

The following are examples of specific applications of the complex system in external preparations for skin, and the formulation and preparation methods of these preparations. In the tables, "-" indicates no addition.

Application example 1: preparation of face cream

Application example 2: preparation of the emulsion

Application example 3: preparation of essence

Application example 4: preparation of facial mask

Application example 5: preparation of eye cream

Application example 6: preparation of the spray