CN117598932A - Sun-screening synergistic composition, water-in-oil type high-power sun-screening composition and preparation method thereof - Google Patents

Abstract

The invention belongs to the technical field of new materials, and particularly discloses a sun-proof synergistic composition which comprises the following components in percentage by weight: 20-65% of grease; 10-50% of organic silicon; 2-35% of silica; 1-10% of a first film forming agent; 1-10% of a first skin conditioning agent; the organic silicon comprises a second film forming agent and volatile organic silicon; the weight ratio of the second film forming agent to the volatile organic silicon is 1:1 to 5; the first film forming agent is acrylic acid (ester) copolymer. The sun-screening composition is suitable for a water-in-oil system, and adopts film forming agents respectively dispersed in an oil phase and a water phase for matching, so that the film forming performance of the sun-screening agent is improved; meanwhile, volatile organic silicon is adopted to improve the spreading capability of the film forming agent in the oil phase and the film forming performance; silica is adopted to improve sun-proof performance, and is also used as a skin feel modifier to reduce greasy feel of the formula, so that the formula is light and thin in body feel. Meanwhile, the invention also discloses a water-in-oil type high-power sun-screening composition and a preparation method thereof.

Description

Sun-screening synergistic composition, water-in-oil type high-power sun-screening composition and preparation method thereof

Technical Field

The invention relates to the field of new materials, in particular to a sun-proof synergistic composition, a water-in-oil type high-power sun-proof composition and a preparation method thereof.

Background

The sun protection factor, the feel of use and the applicable skin are important contributors to the choice of sun protection cosmetics for many consumers.

The sun protection factor is mainly influenced by sun protection agents, if the sun protection agents are required to achieve high-power sun protection effect, many sun protection agents are oil-soluble, and as the sun protection agents are increased, the required oil content is increased, so that the skin feel is easy to be too greasy and thick, and the use feeling is poor. The physical sunscreens are not irritating to skin, but have poor absorbability, air permeability and transparency, and the use feeling is also poor when too much physical sunscreens are added to achieve high-power sunscreens. The chemical sun-screening agent has certain irritation to skin, can possibly cause irritation and anaphylactic reaction of sensitive skin, is unfriendly to the sensitive skin and can more easily cause irritation and anaphylactic reaction by adding excessive chemical sun-screening agent to achieve high sun-screening effect.

CN116327621 a sun protection product: disclosed are sunscreen agents + film formers + skin conditioning agents formulations to increase the sun protection index. The film forming agent and the skin conditioning agent are acrylic acid (ester) copolymer (0.33%) and bisabolol (0.2%), and the SPF synergistic ratio is 21.57%.

CN 116139064A a sunscreen synergistic composition, its use and cosmetic: discloses oil control component, bisabolol, sphingomonas fermentation product extract and thiotaurine, which synergistically increase the sun-screening effect of the sun-screening agent. SPF ranges 33.3-42.4 for comparative examples 1-18 and SPF ranges 38.1-47.0 for examples 1-7 with synergistic compositions added.

The synergy of the sun protection factor is generally achieved by film formers, some polar oils and actives that act as soothing. Film formers generally spread the sunscreen cosmetic evenly over the skin; the polar grease has a structure similar to that of a sun-screening agent and acts together with the sun-screening agent; in addition, the related active substances have soothing effect on skin and inhibit the generation of skin erythema. The improvement of the film forming agent and the polar grease can lead the cosmetics to be thicker and more greasy, thereby influencing the use feeling of the cosmetics, being limited by factors such as material research and the like, and the synergy of the existing related active matters on the sun protection value is generally not obvious.

CN109820738A discloses a high-power oil-in-water type sunscreen cosmetic, which comprises the following specific scheme: phase A: the content of the organic silicon film forming agent is 4-10%; and B phase: an ultraviolet ray defending agent with a content of 18-30%; and C phase: an emollient in an amount of 10-20%; and D phase: a thickener in an amount of 0.5 to 2%; e phase: a nonionic surfactant in an amount of 3 to 6%; and F phase: polyol humectant with content of 5-10%. The polyalcohol is one or more of propylene glycol, 1,3 propylene glycol, butanediol, dipropylene glycol, glycerol and diglycerol; g phase: film forming auxiliary agent with the content of 5-15%; water, proper amount. Wherein: the organic silicon film forming agent in the phase A is one or a combination of more of trimethylsiloxysilicate, acrylic acid (ester) copolymer/polydimethylsiloxane and polymethylsilsesquioxane; the ultraviolet ray defending agent in the phase B consists of an ultraviolet ray scattering agent and an ultraviolet ray absorbing agent, wherein the mass ratio of the ultraviolet ray scattering agent to the ultraviolet ray absorbing agent is 30:70-60:40; the film forming auxiliary agent in the phase G is one or a combination of more of cyclopentadimethicone, cyclohexasiloxane, isododecane and isohexadecane.

After careful analysis of CN109820738A, the mechanism was found to be: the organic silicon film forming agent and the film forming additive are used for forming a film in an inner oil phase and are combined with the ultraviolet defending agent, so that the sun-proof cosmetic has excellent waterproof performance while the sun-proof index is improved, and particularly, the scheme can also have a refreshing skin feel and a mild formula when the ultraviolet scattering agent content in the ultraviolet defending agent is high.

The SPF value can reach 50+;

the scheme tries to develop a water-in-oil dosage form, and the starting point of the scheme is based on a water-in-oil system, wherein the water-in-oil system has better water locking capability, is thick and moist in texture, and is suitable for being used in scenes such as northern cold and plateau high ultraviolet rays.

One of the problems with water-in-oil systems is: the film forming performance of the film forming agent is lower than that of an oil-in-water system, and the oil-in-water system has stronger mobile phase, so that the film forming agent can be spread out faster; meanwhile, most of physical sunscreens such as titanium dioxide can form a surface polyhydroxy structure in water, so that the ultraviolet resistance of the sunscreen in an oil-in-water system is obviously better than the performance in a water-in-oil system.

Thus, the performance of water-in-oil dosage forms of sunscreens is far less than that of oil-in-water systems;

the technical problem that the present case solves is: how to increase SPF (short wave ultraviolet UVB) sun protection factor and PFA (long wave ultraviolet UVA) index of the sun protection agent of the water-in-oil formulation.

Disclosure of Invention

The invention aims to provide a sun-screening synergistic composition which is suitable for a water-in-oil system, adopts film forming agents respectively dispersed in an oil phase and a water phase for matching, and improves the film forming performance of the sun-screening agents; meanwhile, volatile organic silicon is adopted to improve the spreading capability of the film forming agent in the oil phase and the film forming performance; silica is adopted to improve sun-proof performance, and is also used as a skin feel modifier to reduce greasy feel of the formula, so that the formula is light and thin in body feel.

Meanwhile, the invention also discloses a water-in-oil type high-power sun-screening composition and a preparation method thereof.

In order to achieve the above purpose, the technical scheme provided by the invention is as follows: a sun-proof synergistic composition comprises the following components in percentage by weight:

20-65% of grease;

10-50% of organic silicon;

2-35% of silica;

1-10% of a first film forming agent;

1-10% of a first skin conditioning agent;

the organic silicon comprises a second film forming agent and volatile organic silicon; the weight ratio of the second film forming agent to the volatile organic silicon is 1:1 to 5;

the first film forming agent is acrylic acid (ester) copolymer.

In the sun-proof synergistic composition, the grease is one or a mixture of more than one of dibutyl adipate, butyl octanol salicylate, ethylhexyl palmitate and isononyl isononanoate.

In the sun-proof synergistic composition, the grease is a combination of dibutyl adipate and butyl octanol salicylate, and the weight ratio of the dibutyl adipate to the butyl octanol salicylate is 1-5:1-5.

In the above sunscreen synergistic composition, the first skin conditioning agent is one or more of carrageenan extract, bisabolol and panthenol.

In the sunscreen synergistic composition, the second film forming agent is a polydimethylsiloxane/vinyl trimethylsiloxysilicate cross-linked polymer;

the volatile organic silicon is one or a combination of more than one of octamethyltrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

In the sun-proof synergistic composition, the acrylic acid (ester) copolymer is a cross-linked copolymer or a linear copolymer of (methyl) acrylic acid monomer, (methyl) acrylic acid C1-C4 alkyl ester monomer and (methyl) acrylic acid C12-C22 alkyl ester monomer; the optional products are: soltex OPT Copolymer (Dow) acrylate/C12-22 alkyl methacrylate copolymer, SF-1, U-20, etc.;

or the acrylic acid (ester) copolymer is a cross-linked copolymer or a linear copolymer of (methyl) acrylic acid monomer, (methyl) acrylic acid C1-C4 alkyl ester monomer, (methyl) acrylic acid C12-C22 alkyl ester monomer and functional monomer;

the functional monomer is one or a combination of more than one of acrylamide monomer, vinyl siloxane monomer and hydroxyl alkyl acrylate.

The sun-proof synergistic composition comprises the following components in percentage by weight:

31.9-62% of grease;

16.8 to 43.2 percent of organic silicon;

silica 5.9-33.5%;

2.4-8.8% of a first film forming agent;

1.9-7.1% of first skin conditioning agent.

Meanwhile, the invention also discloses a water-in-oil type high-power sun-screening composition, which comprises the following components in percentage by weight: 5-25% of the sunscreen synergistic composition as claimed in any one of the preceding claims;

15.0-30.0% of sun-screening agent;

0.1-10.0% of emulsifying agent;

1.0 to 15.0 percent of humectant;

1.0 to 15.0 percent of emollient;

0.1-5.0% of antioxidant;

0.1-5.0% of thickener;

0-5.0% of a second skin conditioning agent;

0.1-5.0% of chelating agent;

0.1-5.0% of pH regulator;

0.1-5.0% of preservative;

water was added to 100%.

Preferably, the composition comprises the following components in percentage by weight:

12.4 to 20.4 percent of sun-proof synergistic composition;

18.5-26% of a sun-screening agent;

6-7% of emulsifying agent;

7-9% of humectant;

8-12% of an emollient;

0.1-1.0% of antioxidant;

0.1-1.0% of thickener;

0.1-1.0% of chelating agent;

0.1 to 1.0 percent of pH regulator;

0.1-1.0% of preservative;

water was added to 100%.

In the water-in-oil type high-power sun-screening composition, the sun-screening agent is a physical sun-screening agent and/or a chemical sun-screening agent;

the physical sun-screening agent is titanium dioxide and/or zinc oxide;

the chemical sun-screening agent is one or a combination of a plurality of diethyl hexyl butyramide triazone, diethyl hexyloxy phenol methoxyphenyl triazone, methoxy cinnamic acid ethylhexyl ester, diethyl amino hydroxybenzoyl benzoic acid hexyl ester, ethylhexyl triazone, salicylic acid ethylhexyl ester, phenylbenzimidazole sulfonic acid, 4-methylbenzylidene camphor, butyl methoxy dibenzoyl methane, benzophenone-4 and methylene bis-benzotriazole tetramethyl butyl phenol;

the chemical sun-screening agent at least comprises a hydrophilic chemical sun-screening agent and a lipophilic chemical sun-screening agent;

the emulsifier is one or more of cetyl PEG/PPG-10/1 polydimethylsiloxane, polyglycerol-3 diisostearate, polyglycerol-3 polyricinoleate, polyglycerol-4 isostearate and PEG-30 dimer hydroxyl stearate;

the humectant is one or more of glycerol, propylene glycol, butanediol, dipropylene glycol, 1, 2-pentanediol, 1, 2-hexanediol, sorbitol, glycerol glucoside, betaine, and trehalose;

the antioxidant is one or more of tocopherol acetate and p-hydroxyacetophenone;

the emollient is one or more of wheat germ oil, deep sea herba Capsellae seed oil, rice bran oil, BAIHUA seed oil, semen Lupini seed oil, canola oil, camellia seed oil, and butter of Butyrospermum parkii.

The second skin conditioner is one or more of Norway spruce extract, calendula extract, lime flower extract, black tea extract, herba Artemisiae Scopariae extract, and Morus alba bark extract;

the thickener is one or more of sodium chloride, magnesium sulfate, aluminum magnesium silicate and carbomer;

the chelating agent is EDTA disodium;

the pH regulator is one or a combination of more of sodium hydroxide and citric acid;

the preservative is phenoxyethanol.

Finally, the invention also discloses a preparation method of the water-in-oil type high-power sun-screening composition, which comprises the following steps:

step 1: pretreatment: preheating part of humectant and part of antioxidant to 45+ -2deg.C, mixing and dispersing uniformly;

step 2: adding grease, part of first skin conditioning agent, preservative, part of emulsifier and lipophilic sun-screening agent into a vacuum emulsifying pot, heating to 82-85 ℃, uniformly mixing and dispersing, cooling to 45+/-2 ℃, adding the rest of first skin conditioning agent and preservative, stirring until uniformly mixing and dispersing;

step 3: adding organic silicon, silica, partial thickener and emollient into a vacuum emulsifying pot, stirring until the materials are uniformly mixed and dispersed;

step 4: adding water, the rest of humectant, hydrophilic sunscreen agent, the rest of emulsifier, the rest of thickener, the rest of antioxidant, the first film forming agent and the chelating agent into a water phase pot at normal temperature, and stirring until the materials are uniformly mixed and dispersed;

step 5: adding the mixture obtained in the step 1 into a water phase pot, and stirring until the mixture is uniformly mixed and dispersed at normal temperature;

step 6: at normal temperature, the emulsifying pot starts to vacuumize, and under the vacuum state, the water phase pot raw materials are filtered and slowly pumped into the vacuum emulsifying pot, and are homogenized and stirred until being uniformly mixed and dispersed;

step 7: and (5) taking materials, checking, and filtering and discharging after the materials are qualified.

The beneficial effects of the invention are as follows:

the sun-screening composition is suitable for a water-in-oil system, adopts film forming agents respectively dispersed in an oil phase and a water phase for matching, and improves the film forming performance of the sun-screening agent; meanwhile, volatile organic silicon is adopted to improve the spreading capability of the film forming agent in the oil phase and the film forming performance; silica is used to enhance sun protection and also as a skin feel modifier to reduce the greasy feel of the formulation. The moisturizing and soothing properties of the application formulation of the composition after application to sunscreens are enhanced by the first skin conditioning agent to improve the moisturizing and soothing properties.

Detailed Description

The invention is described below in connection with specific embodiments: it is to be understood that these specific embodiments are merely illustrative of the invention and are not limiting thereof. Those skilled in the art can fully modify the specific embodiments or technical features of the present invention in the light of the present invention, but these modified or alternative technical solutions still fall within the protection scope of the present invention.

Description of the sources of the raw materials

A carrageenan extract: self-making;

the preparation process comprises the following steps:

(1) Crushing the carrageenan, namely crushing the carrageenan into 100 meshes, adding 10 times of water of the powder, extracting for 3.5 hours at the temperature of 60-65 ℃, filtering, and taking supernatant, namely a first supernatant; adding 10 times of water into the filter residue, adjusting the pH to 3.6-3.8 by using citric acid, extracting for 24 hours at 25-30 ℃, filtering, and taking the supernatant as a second supernatant; the first supernatant and the second supernatant are mixed and stirred uniformly to obtain a mixture.

(2) Adding 60% ethanol solution into the mixture obtained in the step (1), extracting at 75 ℃ for 1.5h, and filtering to obtain filter residues and supernatant; taking filter residues and drying to obtain a first extract; adding 80% ethanol solution into the supernatant, extracting at 75deg.C for 1.5 hr, filtering, collecting supernatant, concentrating, and drying to obtain second extract;

(3) Mixing: mixing the first extract and the second extract obtained in the step (2) to obtain the carrageenan extract.

Cetyl PEG/PPG-10/1 polydimethylsiloxane, pentaerythritol tetrakis (bis-t-butylhydroxyhydrocinnamate): the proportion is 99.9996wt%, 0.0004wt% (provided by winning company);

polydimethylsiloxane, polydimethylsiloxane/vinyltrimethylsiloxysilicate cross-linked polymer: the ratio of polydimethylsiloxane, polydimethylsiloxane/vinyltrimethylsiloxysilicate cross-linked polymer was 84wt%, 16wt% (supplied by Dow chemical);

acrylic copolymer 1: CARBOPOL AQUSF-1poly her (30% solids);

acrylic copolymer 2: self-making;

the preparation process comprises the following steps: under the protection of inert gas, 50g of acrylic acid, 200g of N-tert-octyl acrylamide, 50g of methyl methacrylate, 20g of n-butyl acrylate, 15g of octadecyl methacrylate, 18g of vinyl silicone oil (viscosity 100 mPa.s) and 200g of ethanol are mixed into 200g of ethanol base solution, 6g of azodiisobutyronitrile and 50g of ethanol are mixed into 2g of ethanol base solution, the mixture is dripped completely in 2h and reacted at a constant temperature for 6h, the reaction temperature is controlled to be 75+/-2 ℃ for reaction in the whole reaction process, the temperature is raised to 85 ℃ and kept at the constant temperature for 0.5h after the reaction is finished, then the temperature is reduced to room temperature, polymer precipitate is collected, crushed and dried.

Acrylic acid (ester) copolymer 3: self-making;

the preparation process comprises the following steps: under the protection of inert gas, 50g of acrylic acid, 200g of N-tert-octyl acrylamide, 50g of methyl methacrylate, 20g of n-butyl acrylate, 15g of octadecyl methacrylate, 18g of 2-hydroxyethyl (meth) acrylate and 200g of ethanol are mixed, 1, 6g of azodiisobutyronitrile and 50g of ethanol are mixed, 2, dropwise added into 200g of ethanol base solution, the mixture is reacted for 6 hours at constant temperature, the reaction temperature is controlled to be 75+/-2 ℃ for reaction, the temperature is raised to 85 ℃ and kept constant for 0.5 hours after the reaction, then the temperature is reduced to room temperature, polymer precipitate is collected, crushed and dried.

Acrylic copolymer 4: self-making;

the preparation process comprises the following steps: under the protection of inert gas, 50g of acrylic acid, 200g of N-tert-octyl acrylamide, 32g of methyl methacrylate, 20g of n-butyl acrylate, 15g of octadecyl methacrylate, 18g of 2-hydroxyethyl (methyl) acrylate, 18g of vinyl silicone oil (viscosity 100 mPa.s), 200g of ethanol forming mixed solution 1, 6g of azodiisobutyronitrile and 50g of ethanol forming mixed solution 2 are dripped into 200g of ethanol base solution, the dripping is completed in 2h, the constant temperature reaction is carried out for 6h, the reaction temperature is controlled to be 75+/-2 ℃ in the whole reaction process, the temperature is raised to 85 ℃ and the constant temperature is kept for 0.5h after the reaction is finished, then the temperature is reduced to room temperature, and polymer precipitate is collected, crushed and dried.

Preparation process of water-in-oil type sun-screening agent

The preparation processes of the examples and comparative examples of the present invention are referred to as follows:

1. pretreatment: preheating the E-phase raw material to (45+/-2) DEG C, and uniformly mixing and dispersing for later use;

2. adding the phase A raw material into a vacuum emulsifying pot, heating to 82-85 ℃ for uniformly mixing and dispersing, cooling to (45+/-2) DEG C, adding the phase B raw material, and stirring until uniformly mixing and dispersing;

3. adding the C-phase raw material into a vacuum emulsifying pot, and stirring until the C-phase raw material is uniformly mixed and dispersed;

4. adding the phase D raw material into a water phase pot at normal temperature, and stirring until the materials are uniformly mixed and dispersed;

5. adding the E-phase raw materials which are uniformly mixed in advance into a water phase pot at normal temperature, and stirring until the E-phase raw materials are uniformly mixed and dispersed;

6. at normal temperature, the emulsifying pot starts to vacuumize, and under the vacuum state, the water phase pot raw materials are filtered and slowly pumped into the vacuum emulsifying pot, and are homogenized and stirred until being uniformly mixed and dispersed;

7. and (5) taking materials, checking, and filtering and discharging after the materials are qualified.

Examples and comparative examples

Examples 1 to 3

The formulations of examples 1-3 are referenced in Table 1 below;

table 1 formulation table

Examples 4 to 6

The formulations of examples 4-6 were substantially the same as in example 1, except that:

example 4 an equal amount of acrylic copolymer 2 was used instead of acrylic copolymer 1;

example 5 an equal amount of acrylic copolymer 3 was used instead of acrylic copolymer 1;

example 6 an equal amount of acrylic copolymer 4 was used instead of acrylic copolymer 1.

Examples 7 to 9

The formulations of examples 7-9 were substantially the same as in example 1, except that:

example 7 an equivalent replacement of butyl octanol salicylate with ethylhexyl palmitate;

example 8 an equal amount of isononyl isononanoate was used instead of dibutyl adipate;

example 9 an equivalent amount of ethylhexyl palmitate was used instead of butyl octanol salicylate and isononyl isononanoate was used instead of dibutyl adipate.

Examples 10 to 12

The formulations of examples 10-12 were substantially the same as in example 1, except that:

example 10 uses octamethyltetrasiloxane in an equivalent amount to replace octamethyltrisiloxane;

example 11 uses an equivalent amount of decamethyl cyclopentasiloxane instead of octamethyl trisiloxane;

example 12 an equivalent amount of polydimethylsiloxane, polydimethylsiloxane/vinyltrimethylsiloxysilicate crosslinked polymer was replaced with polymethylsilsesquioxane (CAS number 68554-70-1).

Comparative examples 1 to 4

The formulations of comparative examples 1-4 are referenced in Table 2 below;

table 2 formulation table

Security test

Toxicology test: all three pass are marked as +, and any one fail is marked as-;

multiple skin irritation tests, skin allergy tests, and skin phototoxicity tests.

Efficacy testing

SPF value measurement of sunscreen cosmetics: the measurement method is a measurement method of sun protection factor (SPF value) of sun protection cosmetics according to the method 2 for evaluating and checking human efficacy of the eighth chapter of cosmetic safety Specification (2015 edition). The method comprises the steps of carrying out a first treatment on the surface of the

Determination of the long-wave ultraviolet protection index (PFA value) of sunscreen cosmetics: the measurement method is a method for measuring the ultraviolet protection index (PFA value) of the sun-proof cosmetic in the eighth chapter of human efficacy evaluation and test method 4 of cosmetic safety technical Specification (2015 edition).

Sensory testing

Skin feel test: a sample of 0.2mL is smeared on the skin for 10 circles, and the spreadability is felt during the smearing process. 2 minutes after use, the skin feel greasy feel and thick feel overall skin feel. The higher the evaluation score, the better the skin feel characteristics. 1 minute-very bad, 2 minutes-bad, 3 minutes-general, 4 minutes-good, 5 minutes-very good.

Test results

The test results can be referred to Table 3

TABLE 3 safety and efficacy test results

	Toxicology test	SPF	PFA
				Example 1	+	94.2	+++
Example 2	+	90.3	+++
				Example 3	+	93.7	+++
Example 4	+	93.5	+++
				Example 5	+	94.2	+++
Example 6	+	96.6	+++
				Example 7	+	89.4	+++
Example 8	+	88.7	+++
				Example 9	+	86.5	+++
Example 10	+	87.1	+++
				Example 11	+	92	+++
Example 12	+	88.3	+++
				Comparative example 1	+	77.8	+++
Comparative example 2	+	74.9	+++
				Comparative example 3	+	79.2	+++
Comparative example 4	+	65.4	+++

Table 4 sensory test results

	Spreadability of	Refreshing and non-greasy	Light, thin and thick	Integral skin feel
					Example 1	4.5	4.2	4.5	4.4
Example 2	3.9	4.2	4.4	4.2
					Example 3	4.3	4.1	4.2	4.2
Example 4	4.5	4.2	4.5	4.4
					Example 5	4.5	4.2	4.5	4.4
Example 6	4.5	4.2	4.5	4.4
					Example 7	4.4	4.2	4.5	4.4
Example 8	4.3	4.2	4.5	4.3
					Example 9	4.3	4.2	4.5	4.3
Example 10	4.4	4.2	4.5	4.4
					Example 11	4.5	4.2	4.5	4.4
Example 12	4.4	4.2	4.5	4.4
					Comparative example 1	4.2	4.2	4.3	4.2
Comparative example 2	4.3	4.2	4.3	4.3
					Comparative example 3	4.3	4.2	4.3	4.3
Comparative example 4	4.5	3.9	4.2	4.2

Analysis of results

1. As can be seen from examples 1-3, the effect of example 1 is similar to example 3 and better than example 2;

in example 3, the amount of sunscreen (chemical sunscreen + physical sunscreen) was up to 26%, and in example 1 the amount of sunscreen (chemical sunscreen + physical sunscreen) was only 18.5%; the reason for this result is that the sunscreen synergistic composition of the present invention is used in greater amounts and has a more pronounced synergy;

more specifically, there are roughly two reasons:

the first, low affinity of grease and volatile organic silicon, the four grease of the invention are subjected to affinity ranking, and the ranking result is as follows: dibutyl adipate < butyl octanol salicylate < ethylhexyl palmitate < isononyl isononanoate; under the condition that the dosage of dibutyl adipate is large, the volatile organic silicon can volatilize faster when the formula is coated on skin, so that the spreading speed and the spreading uniformity of the first film forming agent are improved.

The second, the maximum amount of volatile silicone used in example 1, which can sufficiently assist the spreading of the first film former to form a film, improves film formation uniformity.

2. It can be seen from examples 4 to 6 and example 1 that when a homemade second film former is used, the polymer containing polyhydroxy monomer units or the polymer containing polyhydroxy monomer units, silicone monomer units has a better UV resistance, which may be due to the following reasons:

the first and the second film forming agents can be regarded as a relatively uniform linear or light cross-linked polymer, so that the physical sun-screening agent can be uniformly attached near the hydroxyl of the second film forming agent.

The second, the invention uses the end olefinic bond organosilicon monomer, its main purpose is to cooperate with the hydrophobic long chain in the long-chain acrylic ester monomer, form a layer of oleophilic on the surface, easy to be close to first film forming agent, form the bilayer membrane structure nearby, on the one hand improve the sun-proof durability, on the other hand can make different kinds of sun-proof agents concentrate more near the membrane, improve the dispersing and absorbing effects to ultraviolet ray.

The reason why the ultraviolet resistance of the silicone monomer having only a terminal olefinic bond in example 4 was slightly lowered is not clear.

3. It can be seen from examples 7-9 and example 1 that the optimal grease combination is butyl octanol salicylate + dibutyl adipate, for the specific reasons explained in the first place above.

4. It can be seen from examples 10-12 and example 1 that the properties of decamethyl cyclopentasiloxane and octamethyl trisiloxane are similar, and that octamethyl cyclotetrasiloxane has slightly worse properties than octamethyl trisiloxane, the reason for this being tentatively unknown. Example 12 demonstrates that not all silicones with film-forming functionality can achieve optimal results.

5. It can be seen from comparative examples 1 to 4 and example 1 that in the case where the amount of volatile silicone is too small, the first film forming agent is absent, and the second film forming agent is absent, the ultraviolet ray-proof ability thereof is significantly reduced, and the reason therefor can be seen from the explanation of the first point and the explanation of the second point.

In comparative example 4, when the hydrophilic organic sunscreen agent was absent, the performance was significantly deteriorated, indicating that the optimum effect was not achieved by the lipophilic organic sunscreen agent and the physical sunscreen agent in the oil phase alone.

After the skin feel test was performed on the samples of the above examples and comparative examples, the difference between the examples and comparative examples was not large in the greasy feel and the light and thin feel, indicating that the silica was effective in reducing the greasy feel, and in example 2, although the amount of silica was small, the amount of grease was relatively reduced, so that the skin feel similar to that of examples 1 and 3 could be expressed. However, optimization of skin feel and the use of the moisturizer of the present invention, the rational collocation of skin conditioners, emollients are not separable; meanwhile, the applicant believes that the combination of the emulsifying agents has an important effect on reducing the thick feel of the formula, the formula overcomes the excessively obvious thick feel of the traditional water-in-oil dosage form, and the overall skin feel is good.

The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (10)

1. The sun-proof synergistic composition is characterized by comprising the following components in percentage by weight:

20-65% of grease;

10-50% of organic silicon;

2-35% of silica;

1-10% of a first film forming agent;

1-10% of a first skin conditioning agent;

the organic silicon comprises a second film forming agent and volatile organic silicon; the weight ratio of the second film forming agent to the volatile organic silicon is 1:1 to 5;

the first film forming agent is acrylic acid (ester) copolymer.

2. The synergistic sunscreen composition according to claim 1, wherein the oil or fat is one or a mixture of more than one of dibutyl adipate, butyl octanol salicylate, ethylhexyl palmitate, isononyl isononanoate.

3. The sunscreen synergistic composition of claim 2, wherein the grease is a combination of dibutyl adipate and butyl octanol salicylate in a weight ratio of 1-5:1-5.

4. The sunscreen synergistic composition of claim 1, wherein the first skin conditioning agent is a mixture of one or more of carrageenan extract, bisabolol, panthenol;

and/or, the second film former is a polydimethylsiloxane/vinyltrimethylsiloxysilicate cross-linked polymer;

the volatile organic silicon is one or a combination of more than one of octamethyltrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

5. The synergistic composition for sunscreening according to claim 1, wherein the (ester) acrylic copolymer is a crosslinked copolymer or linear copolymer of (meth) acrylic monomer, C1-C4 alkyl (meth) acrylate monomer, C12-C22 alkyl (meth) acrylate monomer; the optional products are: soltex OPT Copolymer (Dow) acrylate/C12-22 alkyl methacrylate copolymers;

or the acrylic acid (ester) copolymer is a cross-linked copolymer or a linear copolymer of (methyl) acrylic acid monomer, (methyl) acrylic acid C1-C4 alkyl ester monomer, (methyl) acrylic acid C12-C22 alkyl ester monomer and functional monomer;

the functional monomer is one or a combination of more than one of acrylamide monomer, vinyl siloxane monomer and hydroxyl alkyl acrylate.

6. The sun-protection synergistic composition according to claim 1, comprising the following components in weight percentage:

31.9-62% of grease;

16.8 to 43.2 percent of organic silicon;

silica 5.9-33.5%;

2.4-8.8% of a first film forming agent;

1.9-7.1% of first skin conditioning agent.

7. The water-in-oil type high-power sun-screening composition is characterized by comprising the following components in percentage by weight:

a sunscreen synergistic composition as claimed in any one of claims 1 to 65 to 25%;

15.0-30.0% of sun-screening agent;

0.1-10.0% of emulsifying agent;

1.0 to 15.0 percent of humectant;

1.0 to 15.0 percent of emollient;

0.1-5.0% of antioxidant;

0.1-5.0% of thickener;

0-5.0% of a second skin conditioning agent;

0.1-5.0% of chelating agent;

0.1-5.0% of pH regulator;

0.1-5.0% of preservative;

water was added to 100%.

8. The water-in-oil high power sunscreen composition according to claim 7, comprising the following components in weight percent:

12.4 to 20.4 percent of sun-proof synergistic composition;

18.5-26% of a sun-screening agent;

6-7% of emulsifying agent;

7-9% of humectant;

8-12% of an emollient;

0.1-1.0% of antioxidant;

0.1-1.0% of thickener;

0.1-1.0% of chelating agent;

0.1 to 1.0 percent of pH regulator;

0.1-1.0% of preservative;

water was added to 100%.

9. The water-in-oil high power sunscreen composition according to claim 7, wherein the synergistic sunscreen composition comprises from 12.4 to 20.4% by weight of the total weight of the water-in-oil high power sunscreen composition;

the sun-screening agent is a physical sun-screening agent and/or a chemical sun-screening agent;

the physical sun-screening agent is titanium dioxide and/or zinc oxide;

the chemical sun-screening agent is one or a combination of a plurality of diethyl hexyl butyramide triazone, diethyl hexyloxy phenol methoxyphenyl triazone, methoxy cinnamic acid ethylhexyl ester, diethyl amino hydroxybenzoyl benzoic acid hexyl ester, ethylhexyl triazone, salicylic acid ethylhexyl ester, phenylbenzimidazole sulfonic acid, 4-methylbenzylidene camphor, butyl methoxy dibenzoyl methane, benzophenone-4 and methylene bis-benzotriazole tetramethyl butyl phenol;

the chemical sun-screening agent at least comprises a hydrophilic chemical sun-screening agent and a lipophilic chemical sun-screening agent;

the emulsifier is one or more of cetyl PEG/PPG-10/1 polydimethylsiloxane, polyglycerol-3 diisostearate, polyglycerol-3 polyricinoleate, polyglycerol-4 isostearate and PEG-30 dimer hydroxyl stearate;

the humectant is one or more of glycerol, propylene glycol, butanediol, dipropylene glycol, 1, 2-pentanediol, 1, 2-hexanediol, sorbitol, glycerol glucoside, betaine, and trehalose;

the antioxidant is one or more of tocopherol acetate and p-hydroxyacetophenone;

the emollient is one or more of wheat germ oil, deep sea herba Capsellae seed oil, rice bran oil, BAIHUA seed oil, semen Lupini seed oil, canola oil, camellia seed oil, and butter of Butyrospermum parkii.

The second skin conditioner is one or more of Norway spruce extract, calendula extract, lime flower extract, black tea extract, herba Artemisiae Scopariae extract, and Morus alba bark extract;

the thickener is one or more of sodium chloride, magnesium sulfate, aluminum magnesium silicate and carbomer;

the chelating agent is EDTA disodium;

the pH regulator is one or a combination of more of sodium hydroxide and citric acid;

the preservative is phenoxyethanol.

10. A process for preparing a water-in-oil high power sunscreen composition according to claim 9, comprising the steps of:

step 1: pretreatment: preheating part of humectant and part of antioxidant to 45+ -2deg.C, mixing and dispersing uniformly;

step 2: adding grease, part of first skin conditioning agent, preservative, part of emulsifier and lipophilic sun-screening agent into a vacuum emulsifying pot, heating to 82-85 ℃, uniformly mixing and dispersing, cooling to 45+/-2 ℃, adding the rest of first skin conditioning agent and preservative, stirring until uniformly mixing and dispersing;

step 3: adding organic silicon, silica, partial thickener and emollient into a vacuum emulsifying pot, stirring until the materials are uniformly mixed and dispersed;

step 4: adding water, the rest of humectant, hydrophilic sunscreen agent, the rest of emulsifier, the rest of thickener, the rest of antioxidant, the first film forming agent and the chelating agent into a water phase pot at normal temperature, and stirring until the materials are uniformly mixed and dispersed;

step 5: adding the mixture obtained in the step 1 into a water phase pot, and stirring until the mixture is uniformly mixed and dispersed at normal temperature;

step 6: at normal temperature, the emulsifying pot starts to vacuumize, and under the vacuum state, the water phase pot raw materials are filtered and slowly pumped into the vacuum emulsifying pot, and are homogenized and stirred until being uniformly mixed and dispersed;

step 7: and (5) taking materials, checking, and filtering and discharging after the materials are qualified.