CN112315820A

CN112315820A - Oil-in-water sunscreen emulsion and preparation method thereof

Info

Publication number: CN112315820A
Application number: CN202011406371.1A
Authority: CN
Inventors: 邱镇国; 张毅; 梁达锋; 李怡殊
Original assignee: Guangdong Gadetin Daily Necessities Co ltd
Current assignee: Guangdong Gadetin Daily Necessities Co ltd
Priority date: 2020-12-02
Filing date: 2020-12-02
Publication date: 2021-02-05

Abstract

The invention belongs to the field of cosmetics, and particularly relates to an oil-in-water sunscreen emulsion and a preparation method thereof. The oil-in-water sunscreen emulsion comprises, by weight, 45-60 parts of a group A water phase component, 35-45 parts of a group B oil phase component, 0.5-0.8 part of a group C component, 0.5-1.5 parts of a group D component and 15-20 parts of a group E component; the group B oil phase component is selected from one or more of organic sunscreen agent, grease, skin feel regulator, emulsifier and antioxidant; the emulsifier comprises an O/W type emulsifier with pH value of 5.5-7.5 and an O/W nonionic emulsifier with HLB value of 10-13 of 5 wt% aqueous solution. The oil-in-water sun-blocking emulsion provided by the invention has strong sun-blocking capability, no stimulation to human bodies, excellent compatibility to silicon oil substances, difficult crystallization and precipitation, easy film formation, safe use, good touch and fresh skin feel.

Description

Oil-in-water sunscreen emulsion and preparation method thereof

Technical Field

The invention belongs to the field of cosmetics, and particularly relates to an oil-in-water sunscreen emulsion and a preparation method thereof.

Background

Sunlight is a well-established cause of photodamage, photoaging and skin cancer, and consists of Ultraviolet (UV) (290-400nm), visible (400-700nm) and infrared (> 700nm), with 5% reaching the earth's surface being UV radiation and a lesser proportion penetrating the atmosphere onto human skin. The effects of ultraviolet light on the skin include erythema, tanning, drug induced phototoxicity, photoaging, and non-melanotic skin cancers, among others. In recent years, the more the air pollution, the more the ozone layer thinning cavity causes the damage of ultraviolet rays to the skin. It is therefore desirable to protect our skin with sunscreen products.

For emulsion type sunscreen products, two general types of emulsion systems can be distinguished: oil-in-water type, water-in-oil type. The oil-in-water sunscreen product usually has heavy skin feel and is sticky due to high-content oil and large-molecular-weight main emulsifier in the external phase, and the experience of consumers is not good when the sunscreen product is used in summer. The oil-in-water type emulsion has a great advantage in summer due to its water-moist feeling. However, many oil-in-water emulsion cosmetics have poor water resistance as compared with oil-in-water emulsion products. Particularly in summer, people easily sweat or frequently soak in water for swimming, and the sun-proof product has more chance of being exposed to water. Oil-in-water type cosmetics are more likely to cause the loss of the ultraviolet ray protection agent due to poor water resistance, thereby reducing the ultraviolet ray protection function of sunscreen products. In the research and development of oil-in-water emulsion cosmetics, most of researches are focused on improving the water resistance, and the researches on simultaneously improving the water resistance and the sun protection index are less.

Therefore, it is very important to develop an oil-in-water sunscreen having good touch, high sun protection index and strong water resistance.

Disclosure of Invention

In order to solve the defects and deficiencies of the prior art, the invention provides in a first aspect an oil-in-water sunscreen emulsion, which comprises, by weight, 45-60 parts of a group A water phase component, 35-45 parts of a group B oil phase component, 0.5-0.8 part of a group C component, 0.5-1.5 parts of a group D component and 15-20 parts of a group E component; the group B oil phase component is selected from one or more of organic sunscreen agent, grease, skin feel regulator, emulsifier and antioxidant; the emulsifier comprises an O/W nonionic emulsifier with HLB value of 10-13.

In a preferable technical scheme, in the group B oil phase component, the mass ratio of the organic sunscreen agent, the grease, the skin feel conditioning agent, the emulsifier and the antioxidant is (20-26): (8-12): (0.01-0.1): (3-5): (0.05-0.15).

As a preferable technical scheme, the organic sunscreen agent is selected from one or more of ethylhexyl methoxycinnamate, homosalate, octocrylene, ethylhexyl salicylate, diethyl amino hydroxybenzoyl hexyl formate and bis-ethyl hexyloxy phenol methoxyphenyl triazine.

As a preferred embodiment, the emulsifier further comprises cetearyl glucoside and cetearyl alcohol.

As a preferable technical scheme, the O/W nonionic emulsifier with the HLB value of 10-13 is glycerol stearate and PEG-100 stearate.

As a preferable technical scheme, the grease comprises one or more of cyclopentadimethyl siloxane, isononyl isononanoate, C12-15 alcohol benzoate and hydrogenated polyisobutene.

As a preferred technical scheme, the group a water phase component comprises water, glycerol, butanediol, carbomer, xanthan gum and sodium hyaluronate; the mass ratio of the water, the glycerin, the butanediol, the carbomer, the xanthan gum and the sodium hyaluronate is (30-40): (2-4): (1-3): (0.1-0.2): (0.1-0.3): (0.01-0.03).

As a preferable technical scheme, the component E is one or more selected from phenoxyethanol, dipotassium glycyrrhizinate, silica and methylene bis-benzotriazole tetramethyl butyl phenol.

As a preferable technical scheme, the mass ratio of the phenoxyethanol to the dipotassium glycyrrhizinate to the silica to the methylene bis-benzotriazole tetramethyl butylphenol is (0.2-0.4): (0.05-0.15): (2-4): (4-6).

The second aspect of the invention provides a preparation method of the oil-in-water sunscreen emulsion, which comprises the following steps:

s1: adding the water phase components of group A into an emulsifying pot, heating to 80-85 deg.C, stirring and homogenizing to completely dissolve;

s2: adding the group B oil phase components into an oil phase pot, heating to 80-85 ℃, and stirring to completely dissolve the group B oil phase components;

s3: adding the group B oil phase component treated by the S2 into the group A water phase component treated by the S2, homogenizing and emulsifying uniformly, stirring and cooling to 55-65 ℃ to obtain a mixture 1;

s4: adding the component C into the mixture 1 obtained in the step S3, stirring and homogenizing until the component C is completely dissolved, and continuously cooling to 40-50 ℃ to obtain a mixture 2;

s5: mixing and dissolving the component D completely, then adding the component D into the mixture 2 obtained in the step S4, and stirring and mixing the component D until the component D is completely dissolved to obtain a mixture 3;

s6: pre-dispersing methylene bis-benzotriazole tetramethyl butyl phenol by water according to a ratio of 1:2, adding the component E into the mixture 3 obtained in the step S5, and stirring and mixing until the component E is completely dissolved to obtain the oil-in-water sun-block emulsion.

Has the advantages that: the oil-in-water sun-screen emulsion provided by the invention can achieve full-wavelength protection and protection of skin by absorbing and blocking the wavelengths in UVA and UVB ranges, has strong sun-screen capability, has no stimulation to human body, has excellent compatibility with silicon oil substances, is not easy to crystallize and separate out, is easy to form a film, is safe to use, and has good and refreshing skin feel.

Detailed Description

The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 to 5" is disclosed, the described range should be construed as including the ranges "1 to 4", "1 to 3", "1 to 2", "2 to 3" and "3 to 4", "4 to 5" and "3 to 5", etc. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

In order to solve the technical problems, the invention provides an oil-in-water sunscreen emulsion which comprises, by weight, 45-60 parts of a group A water phase component, 35-45 parts of a group B oil phase component, 0.5-0.8 part of a group C component, 0.5-1.5 parts of a group D component and 15-20 parts of a group E component; the group B oil phase component is selected from one or more of organic sunscreen agent, grease, skin feel regulator, emulsifier and antioxidant; the emulsifier comprises an O/W nonionic emulsifier with HLB value of 10-13.

In one embodiment, the oil-in-water sunscreen emulsion comprises 52 parts of a group A water phase component, 40 parts of a group B oil phase component, 0.6 part of a group C component, 1 part of a group D component and 17 parts of a group E component in parts by weight.

Group A aqueous phase component

In one embodiment, the group a aqueous phase components include water, glycerin, butylene glycol, carbomer, xanthan gum, sodium hyaluronate; the mass ratio of the water, the glycerin, the butanediol, the carbomer, the xanthan gum and the sodium hyaluronate is (30-40): (2-4): (1-3): (0.1-0.2): (0.1-0.3): (0.01-0.03); preferably, the mass ratio of the water to the glycerin to the butanediol to the carbomer to the xanthan gum to the sodium hyaluronate is 34: 3: 4: 0.15: 0.2: 0.02.

(Water)

In the invention, the water is deionized water.

(Glycerol)

In the invention, the glycerin is colorless, transparent, odorless and viscous liquid, tastes sweet and has hygroscopicity. Mixing with water and alcohols, amines and phenols in any ratio, and making the aqueous solution neutral.

(butanediol)

In the invention, the butanediol is 1, 2-butanediol.

(Carbonic acid)

In the invention, the carbomer is TR-1 and is purchased from Lumbo corporation.

TR-1 is a multifunctional polymer that emulsifies 30% oil by weight at a pH ranging from 4 to 5.5 and 20% oil at a pH ranging from 3 to 11.

(Xanthan gum)

In the present invention, the xanthan gum, also known as xanthan gum, is an extracellular acidic heteropolysaccharide produced by fermentation of xanthomonas sp. Is prepared from D-glucose, D-mannose and D-glucuronic acid in a weight ratio of 2: 2: 1, the relative molecular mass of the polysaccharide polymer compound is more than 100 ten thousand. The secondary structure of xanthan gum is that the side chain winds around the main chain skeleton reversely, and a rodlike double-spiral structure is formed through a hydrogen bond system. It has unique rheological property, good water solubility, good stability to heat and acid and alkali, and good compatibility with various salts, and can be used as thickener, suspending agent, emulsifier, and stabilizer.

The xanthan gum is reversely wound around the main chain skeleton due to the side chain, forms a rod-shaped double-spiral structure through a hydrogen bond system, can be used as a thickening agent, a suspending agent and an emulsifying agent, has synergistic effect with carbomer, sodium hyaluronate and the like, provides a consistency with less pH influence for a system, has good skin feel and is beneficial to improving the stability of the system.

In the invention, the xanthan gum is given by the brand number

XGN, purchased from New chemical industries, Inc.

(sodium hyaluronate)

In the invention, the sodium hyaluronate has the chemical formula of (C)₁₄H₂₀NO₁₁Na) n, an inherent component in human body, is a glucan aldehyde acid, has no species specificity, and is widely present in tissues such as placenta, amniotic fluid, crystalline lens, articular cartilage, skin dermis and the like; it is distributed in the cytoplasm and the intercellular substance of the organ, and plays a role in lubricating and nourishing the cells and the organelles contained therein. Sodium hyaluronate belongs to high molecular polymer and has strong lubricating feeling and film forming property. The skin care product containing sodium hyaluronate has obvious lubrication feeling and good hand feeling when being smeared. After being applied to the skin, a layer of film can be formed on the surface of the skin, so that the skin can generate good smooth feeling and moist feeling, and the protective effect on the skin is achieved.

In one embodiment, the sodium hyaluronate is available under the trade designation Hybloom sodium hyaluronate (HA-T) and purchased from Huaxi Biotech.

Group B oil phase component

In one embodiment, the group B oil phase component is a mixture of organic sunscreens, oils, skin feel modifiers, emulsifiers, antioxidants.

In a preferred embodiment, in the group B oil phase component, the mass ratio of the organic sunscreen agent, the grease, the skin-feel modifier, the emulsifier and the antioxidant is (20-26): (8-12): (0.01-0.1): (3-5): (0.05-0.15); more preferably, in the group B oil phase component, the mass ratio of the organic sunscreen agent, the grease, the skin feel modifier, the emulsifier and the antioxidant is 25.5: 10: 0.05: 4: 0.1.

(organic sunscreen agent)

In one embodiment, the organic sunscreen agent is selected from one or more of ethylhexyl methoxycinnamate, homosalate, octocrylene, ethylhexyl salicylate, hexyl diethylaminobenzoyl formate, bis-ethylhexyloxyphenol methoxyphenyl triazine; preferably, the organic sunscreen agent is a mixture of ethylhexyl methoxycinnamate, homosalate, octocrylene, ethylhexyl salicylate, hexyl diethylamino hydroxybenzoyl formate, bis-ethylhexyloxyphenol methoxyphenyl triazine.

In a preferred embodiment, the mass ratio of the ethylhexyl methoxycinnamate, homosalate, octocrylene, ethylhexyl salicylate, hexyl diethylamino hydroxybenzoyl formate, bis-ethylhexyloxyphenol methoxyphenyl triazine is 9: 2: 5: 5: 3: 1.5.

the invention adopts ethylhexyl methoxycinnamate, homosalate, octocrylene, ethylhexyl salicylate, diethyl-amino-hydroxybenzoyl hexyl formate and bis-ethylhexyloxyphenol methoxyphenyl triazine as organic sun-screening agents, and the mass ratio is controlled to be 9: 2: 5: 5: 3: 1.5, can reduce the damage to the skin, has no irritation, and does not produce toxic metabolites. The sunscreen lotion has strong sunscreen capacity, is applied to oil-in-water sunscreen lotion, has good oil compatibility, is not greasy, is quick in film forming and is not easy to crystallize and separate out.

In the invention, the ethylhexyl methoxycinnamate is colorless to light yellow viscous liquid, is insoluble in water, is soluble in organic solvents such as ethanol and the like, has good oil solubility, and is suitable for being stored in a closed place in the shade. Ethylhexyl methoxycinnamate is a good absorber in the ultraviolet UVB region and is effective in preventing280-310nm ultraviolet rays and high absorptivity. Has no stimulation to skin and good safety, and is almost an ideal sunscreen emulsion. CAS number 5466-77-3, chemical formula C₁₈H₂₆O₃The structural formula is as follows:

the invention adopts ethylhexyl methoxycinnamate which can be used as a penetration enhancer and can be easily absorbed by skin. The maximum addition level, which is defined by national and european union regulations, is 10 wt%.

In the invention, the homosalate is represented by the chemical formula C₁₆H₂₂O₃CAS number: 118-56-9, is a colorless transparent liquid chemical substance, is insoluble in water, can absorb ultraviolet rays in the UVB 295-315 wave band, and is mainly used for ultraviolet UVB sun-screening milk in industry. The amount should not exceed 10 wt%.

In the invention, the molecular formula of the ethylhexyl salicylate is C₁₅H₂₂O₃CAS number 118-60-5.

In the present invention, the octocrylene, the oil-soluble ultraviolet absorber, is insoluble in water. It can help other oil soluble solid sunscreen emulsion to dissolve. The emulsion has the advantages of high absorptivity, no toxicity, no teratogenic action, good stability to light and heat and the like, can absorb UVB and a small amount of UVA, is a I-class sun block approved by the FDA in the United states, and has high use rate in the United states and Europe. CAS number 6197-30-4, molecular formula C₂₄H₂₇NO₂。

In the present invention, the diethylaminohydroxybenzoylbenzoic acid hexyl ester (Diethylaminohydroxybenzoyl hexyl benzoate), also referred to as 4-tolylthiourea or p-methylphenylthiourea, is an ester compound having a relative molecular mass of 397.5072. CAS number 302776-68-7, formula C₂₄H₃₁NO₄。

In the invention, the CAS number of the bis-ethylhexyloxyphenol methoxyphenyl triazine is 187393-00-6, and the molecular formula is C₃₈H₄₉N₃O₅Structural formula is

(oil and fat)

In a preferred embodiment, the grease comprises one or more of cyclopentadimethylsiloxane, isononyl isononanoate, C12-15 alcohol benzoate and hydrogenated polyisobutene.

In a preferred embodiment, the grease is a mixture of cyclopentadimethylsiloxane, isononyl isononanoate, C12-15 alcohol benzoate and hydrogenated polyisobutene; more preferably, the weight ratio of the cyclopentadimethylsiloxane, the isononyl isononanoate, the C12-15 alcohol benzoate and the hydrogenated polyisobutene is 3: 3: 2: 2.

the invention adopts the combination of cyclopentadimethyl siloxane, isononyl isononanoate, C12-15 alcohol benzoate and hydrogenated polyisobutene as grease, and the grease and the emulsifiers of cetearyl glucoside, cetearyl alcohol, glycerol stearate and PEG-100 stearate have the same effect, so that good touch feeling can be kept. And C12-15 alcohol benzoate, liquid grease have strong polarity, can effectively dissolve organic sunscreen agent, effectively reduce the possibility of crystallization, isononyl isononanoate is nonpolar grease containing multi-methyl branched chain structure, has excellent compatibility to silicon oil substances, and thus solves the problem that cyclopenta dimethyl silicone polymer and sunscreen emulsion are mutually insoluble.

In the invention, the cyclopentasiloxane has the name of: decamethylcyclopentasiloxane, cyclopentasiloxane, decamethylcyclopentasiloxane (D5). CAS number 541-02-6, molecular formula C₁₀H₃₀O₅Si₅. Under the designation SF1202, purchased from mayonnaise corp.

In the invention, the isononyl isononanoate has a molecular formula of C₁₈H₃₆O₂CAS number: 42131-25-9. Commonly known as synthetic silk oil.

The invention adopts isononyl isononanoate, unique multi-methyl branched chain structure, silky feeling, dry and comfortable and extremely soft hand feeling, and excellent emollient. The silicon oil stabilizer and the coupling agent have good compatibility with silicon oil, can solve the problem of low-temperature precipitation of the silicon oil. Has good dispersion ability for pigment, low viscosity, refreshing skin feeling, and no greasy feeling. Odd-numbered mid-chain branched alcohols are colorless, odorless, liquid monoesters with odd-numbered mid-chain branched fatty acids and have low viscosities.

In the invention, the C12-15 alcohol benzoate is available from New-Ann chemical trade company of Foshan under the CAS number of 68411-27-8 and AB 25.

The invention adopts C12-15 alcohol benzoate, has good dissolving capacity and toner dispersing capacity, has fresh skin feel, and is particularly suitable for being used as a sunscreen product. The oil-soluble sun-screening emulsion pigment, the poly-C siloxane and other components are easy to dissolve in C12-15 alcohol benzoate and easy to emulsify, and the greasy feeling can be obviously overcome by adding a small amount of the ester.

In the invention, the hydrogenated polyisobutene is a synthetic polymer and is mainly used as a film forming agent, a softening agent and a viscosity control agent in cosmetics. Hydrogenated polyisobutenes have the cosmetic properties of squalane and are therefore referred to as synthetic squalane. The isomeric straight chain alkane can be used as oil phase component of cosmetics and medicines, has moistening, moisturizing and lubricating effects, and has properties similar to natural squalane; the hydrogenated polyisobutene is purchased from cypress picture chemical technology ltd, guangzhou.

(skin-feel modifier)

In one embodiment, the skin feel modifier is selected from one or more of dextran, hyaluronic acid/sodium hyaluronate, pullulan, sodium alginate, xanthan gum, glucose, trehalose, fructose, maltose, bisabolol; preferably, the skin feel modifier is bisabolol.

In the invention, the bisabolol is a component existing in the chamomile, and the anti-inflammatory effect of the chamomile is mainly derived from the bisabolol. Bisabolol is colorless to glutinous liquid of rice straw yellow, and is soluble in lower alcohol (ethanol, isopropanol), fatty alcohol, glyceride and vinegar, and hardly soluble in water and glycerol.

In one embodiment, the bisabolol is α -bisabolol.

In the present invention, the α -bisabolol has a chemical formula C₁₅H₂₆O, CAS number515-69-5, structural formula:

the invention adopts alpha-bisabolol as a skin feel regulator, has good stability and excellent skin compatibility, and not only has anti-inflammatory performance, but also is proved to have bacteriostatic activity. The alpha-bisabolol does not change color after long-term storage.

(emulsifiers)

In one embodiment, the emulsifier further comprises cetearyl glucoside and cetearyl alcohol.

In one embodiment, the cetearyl glucoside and cetearyl alcohol are available under the brand name M68, available from behabo corporation.

In the invention, the cetearyl glucoside and the cetearyl alcohol are O/W type emulsifiers with self-emulsifying and self-thickening functions, oleophylic fat groups and hydrophilic glucose groups of the O/W type emulsifiers are both plant sources, and the O/W type emulsifiers do not contain solvents and irritant by-products, have excellent emulsifying performance, promote the formation of liquid crystals in a formula system, and can endow the product with excellent smooth and plump skin feeling, and unique use effects of moisturizing and slow-release functional components. In the cooling process after emulsification, the liquid crystal of the system is gradually formed, and strong stirring is avoided so as not to damage the ordered structure of the liquid crystal.

In one embodiment, the O/W nonionic emulsifier having an HLB value of 10 to 13 is glyceryl stearate and PEG-100 stearate, available from Daiichi corporation under the trademark ARLACEL 170-PA- (SG).

In a preferred embodiment, the mass ratio of cetearyl glucoside to cetearyl alcohol, glyceryl stearate and PEG-100 stearate is 2: 2.

in the present invention, the HLB value: the surfactant is an amphiphilic molecule with a hydrophilic group and a lipophilic group, and the amount of the size and the force balance degree between the hydrophilic group and the lipophilic group in the surfactant molecule is defined as the hydrophilic-lipophilic balance value of the surfactant.

In the invention, the HLB value of the glycerol stearate and the PEG-100 stearate is 11.2, the acid value (mg KOH/g) is less than or equal to 3.0, and the saponification value (mg KOH/g) is 80-100. Can be used alone or as auxiliary emulsifier, has strong emulsifying ability, excellent stability in weakly acidic and electrolyte-containing formulas, and good compatibility with most cosmetic components and medicinal components. Has good emulsifying capacity to polar and non-polar grease, and the emulsified paste has fine and bright appearance, good spreadability and easy application.

In the present invention, the acid value represents the number of milligrams of potassium hydroxide (KOH) required to neutralize 1 gram of chemical substance.

In the present invention, the saponification value represents the number of milligrams of potassium hydroxide consumed by alkaline hydrolysis of 1g of fats and oils.

(antioxidant)

In one embodiment, the antioxidant is selected from one or more of tocopheryl acetate, dibutyl hydroxy toluene, butyl hydroxy anisole; preferably, the antioxidant is tocopherol acetate.

In the invention, the tocopherol acetate is easily soluble in chloroform, diethyl ether, acetone and vegetable oil, is soluble in alcohol and is insoluble in water. Has good heat resistance, can be oxidized when being exposed to light, has dark color and belongs to vitamin E derivatives. Tocopherol acetate is not only skin regulator, but also antioxidant, and has protective effect of preventing skin injury due to sunlight and ultraviolet when used in cosmetic. Signs of aging, such as skin aging and damage, are often associated with free radical damage, as this can result in a loss of balance in native sebum and collagen production.

Component C

In one embodiment, the C component includes a thickener and a pH adjuster; the mass ratio of the thickening agent to the pH regulator is 5: 1.

in one embodiment, the thickener is ethylhexyl olivate, sodium acrylate copolymer, polyglycerol-4 oleate sold under the trademark Olivem 2020G, available from Ronghai Biotech, Inc.

According to the invention, the olive oil acid ethylhexyl ester, the acrylic acid (ester) copolymer sodium and the polyglycerol-4 oleate are colorless to light yellow viscous liquid, contain 65% of natural components, can be suspended in a stable system, are clear in skin feel, are not sticky, are bright and white in paste body, and have moisturizing performance.

In one embodiment, the pH adjusting agent is triethanolamine.

In the invention, the triethanolamine, namely the tri (2-hydroxyethyl) amine, is an organic compound which can be regarded as a trihydroxy substituent of triethylamine and has a chemical formula of C₆H₁₅NO₃. Similar to other amine compounds, because of the lone pair of electrons on the nitrogen atom, triethanolamine has weak alkalinity and can react with inorganic acid or organic acid to generate salt.

According to the invention, triethanolamine is adopted to achieve the application effects of thickening and moisturizing, the triethanolamine interacts with carbomer TR-1 in the group A water phase component to form a stable high molecular structure, so that the stability of the oil-in-water sunscreen emulsion is improved, and the triethanolamine interacts with an emulsifier, ethylhexyl olivate, sodium acrylate copolymer and polyglycerol-4 oleate to realize 2-week circulation and low-temperature demulsification-free phenomenon of the oil-in-water sunscreen emulsion, so that the triethanolamine is centrifuged without layering, the in-vitro sunscreen index is further improved, the greasy feeling is reduced, and the spreadability is improved.

Component of group D

In one embodiment, the group D component is a preservative combination; the preservative composition comprises a preservative and pentanediol, and the mass ratio of the preservative to the pentanediol is 0.4: 0.6.

in one embodiment, the preservative is selected from one or more of methylparaben, propylparaben, and p-hydroxyacetophenone; preferably, the preservative is p-hydroxyacetophenone.

In the invention, the p-Hydroxyacetophenone is also named 4-Hydroxyacetophenone (4-hydroxy acetophenone), 4-Acetylphenol (4-Acetylphenol), p-Acetylphenol (p-Acetylphenol), 4-hydroxyphenylmethyl ketone (4-hydroxyphenyl methyl ketone), commonly called conicol (picenol), is white needle-shaped crystal at normal temperature, is combustible, can be easily dissolved in hot water, methanol, ethanol, diethyl ether, acetone and benzene, and can be hardly dissolved in petroleumAnd (c) an ether. Is naturally present in stems and leaves of Artemisia scoparia of Compositae, and roots of Artemisia capillaris, Heteropappus japonica of Asclepiadaceae, etc. CAS number 99-93-4, molecular formula C₈H₈O₂Chemical structural formula is

In the invention, the pentanediol is 1, 2-pentanediol, colorless transparent liquid with a chemical formula of C₅H₁₂O₂Can be dissolved in organic solvents such as alcohol, ether and ethyl acetate, and is often applied to cosmetic solvents.

The invention adopts 1, 2-pentanediol, the pH regulator with excellent performance, and simultaneously has the function of antisepsis, reduces the allergy caused by p-hydroxyacetophenone, but has the special smell of alcohol, and can improve the water resistance of the oil-in-water sun-proof emulsion.

Component E

In one embodiment, the E component is selected from one or more of phenoxyethanol, dipotassium glycyrrhizinate, silica, methylene bis-benzotriazole tetramethylbutylphenol; preferably, the component E is a mixture of phenoxyethanol, dipotassium glycyrrhizinate, silica and methylene bis-benzotriazole tetramethyl butylphenol.

In a preferred embodiment, the mass ratio of the phenoxyethanol to the dipotassium glycyrrhizinate to the silica to the methylene bis-benzotriazole tetramethylbutylphenol is (0.2-0.4): (0.05-0.15): (2-4): (4-6); more preferably, the mass ratio of the phenoxyethanol to the dipotassium glycyrrhizinate to the silica to the methylene bis-benzotriazole tetramethylbutylphenol is 0.3: 0.1: 3: 5.

(Phenoxyethanol)

In the invention, the molecular formula of the phenoxyethanol is C₈H₁₀O₂CAS number 122-99-6, structural formula

The colorless slightly viscous liquid has aromatic odor, is slightly soluble in water, is easily soluble in ethanol and sodium hydroxide, and has antibacterial and antiseptic effects.

(dipotassium glycyrrhizinate)

In the invention, the dipotassium glycyrrhizinate is white or off-white fine powder, has the purity of 98 percent, has special sweet taste, good water solubility and pure mouthfeel. The dipotassium glycyrrhizinate has multiple effects of bacteriostasis, inflammation diminishing, detoxification, anti-allergy, deodorization and the like. Has wide application in the industries of medicine, cosmetics, daily chemicals, food and the like. CAS number: 68797-35-3, formula: c₄₂H₆₀K₂O₁₆。

(silica)

In the present invention, the silica is also called silicon dioxide or quartz sand.

In one embodiment, the silica has an oil absorption of 0.9 to 1.3cc/g, an average pore size of 1 to 3 μm, and is available under the trade name Sunsil-20W from Guangzhou HuaTu cosmetics science and technology, Inc.

(methylenebis-benzotriazoltetramethylbutylphenol)

In the present invention, the methylenebis-benzotriazoltetramethylbutylphenol, CAS No.: 103597-45-1, chemical sun-screening lotion. The Tinosorb M test has the same UV-shielding wavelength as Tinosorb S at 280-400nm, but the maximum protective efficacy occurs at both wavelengths 303nm and 358nm, thus having protective effects against both UV-A and UV-B.

In one embodiment, the method for preparing the oil-in-water sunscreen emulsion comprises the following steps:

s3: adding the group B oil phase component treated by the S2 into the group A water phase component treated by the S2, homogenizing and emulsifying uniformly, stirring and cooling to 60 ℃ to obtain a mixture 1;

s4: adding the component C into the mixture 1 obtained in the step S3, stirring and homogenizing until the component C is completely dissolved, and continuously cooling to 45 ℃ to obtain a mixture 2;

The oil-in-water sunscreen emulsion prepared by the preparation method can effectively prevent emulsion breaking and oil yielding caused by adding the organic sunscreen agent into the water phase component, so that the stability of the oil-in-water sunscreen emulsion is improved strongly, the oil-in-water sunscreen emulsion cannot be layered under a centrifugal condition, and the water resistance of the oil-in-water sunscreen emulsion is greatly improved.

The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.

In addition, the starting materials used are all commercially available, unless otherwise specified.

Examples

Example 1

Example 1 provides an oil-in-water sunscreen comprising, by weight, 45 parts of a group a water phase component, 35 parts of a group B oil phase component, 0.5 part of a group C component, 0.5 part of a group D component, 15 parts of a group E component;

the group A water phase component comprises water, glycerol, butanediol, carbomer, xanthan gum and sodium hyaluronate; the mass ratio of the water, the glycerin, the butanediol, the carbomer, the xanthan gum and the sodium hyaluronate is 30: 4: 3: 0.1: 0.1: 0.01; the butanediol is 1, 2-butanediol; carbomer is TR-1 and is purchased from Lumbo corporation; the xanthan gum is of the grade

XGN, purchased from New chemical industries, Inc.; the sodium hyaluronate is Hybloom sodium hyaluronate (HA-T) and purchased from Huaxi Biotech company;

the group B oil phase component is a mixture of an organic sunscreen agent, grease, a skin feel regulator, an emulsifier and an antioxidant; in the group B oil phase component, the mass ratio of the organic sunscreen agent, the grease, the skin feel regulator, the emulsifier and the antioxidant is 25.5: 10: 0.05: 4: 0.1; the organic sunscreen agent is a mixture of ethylhexyl methoxycinnamate, homosalate, ethylhexyl salicylate, octocrylene, diethyl aminooxybenzoyl hexyl formate, and bis-ethylhexyloxyphenol methoxyphenyl triazine; the mass ratio of the ethylhexyl methoxycinnamate, the homosalate, the ethylhexyl salicylate, the octocrylene, the diethyl amino hydroxybenzoyl hexyl formate to the bis-ethylhexyloxyphenol methoxyphenyl triazine is 9: 2: 5: 5.: 3: 1.5; the ethylhexyl methoxycinnamate CAS number 5466-77-3; the homosalate CAS number 118-56-9; the CAS number of the ethylhexyl salicylate is 118-60-5; the Okrill CAS number 6197-30-4; the CAS number of the diethylamino hydroxybenzoyl hexyl benzoate is 302776-68-7; the CAS number of the bis-ethylhexyloxyphenol methoxyphenyl triazine is 187393-00-6; the grease is a mixture of cyclopentadimethylsiloxane, isononyl isononanoate, C12-15 alcohol benzoate and hydrogenated polyisobutene; the mass ratio of the cyclopentadimethylsiloxane, isononyl isononanoate, C12-15 alcohol benzoate and hydrogenated polyisobutene is 3: 3: 2: 2; the cyclopentasiloxane, designated SF1202, was purchased from Mitigo, Inc.; the isononyl isononanoate CAS number 42131-25-9; the C12-15 alcohol benzoate with the brand number of AB25 is purchased from Xinan chemical trade company of Foshan; the hydrogenated polyisobutene is purchased from cypress diagram chemical technology, ltd, guangzhou; the skin feel modifier is alpha-bisabolol with CAS number 515-69-5; the emulsifier is a mixture of cetearyl glucoside and cetearyl alcohol, glyceryl stearate and PEG-100 stearate; the mass ratio of the cetearyl glucoside to the cetearyl alcohol, the glyceryl stearate to the PEG-100 stearate is 2: 2; the antioxidant is tocopherol acetate;

the component C comprises a thickening agent and a pH regulator; the mass ratio of the thickening agent to the pH regulator is 5: 1; the thickening agent is ethylhexyl olive oleate, sodium acrylate copolymer and polyglycerol-4 oleate, the mark is Olivem 2020G, and the thickening agent is purchased from Yonghai Biotech limited; the pH regulator is triethanolamine;

the component D is a preservative combination; the preservative composition comprises a preservative and pentanediol; the mass ratio of the preservative to the pentanediol is 0.4: 0.6; the preservative is p-hydroxyacetophenone with CAS number 99-93-4; the pentanediol is 1, 2-pentanediol;

the component E is a mixture of phenoxyethanol, dipotassium glycyrrhizinate, silica and methylene bis-benzotriazole tetramethyl butyl phenol; the mass ratio of the phenoxyethanol to the dipotassium glycyrrhizinate to the silica to the methylene bis-benzotriazole tetramethyl butylphenol is 0.2: 0.05: 2: 4; the CAS number of the phenoxyethanol is 122-99-6; the glycyrrhizic acid dipotassium CAS number 68797-35-3; the silica has an oil absorption of 0.9-1.3cc/g, an average pore diameter of 1-3 μm, a trade name of Sunsil-20W, and is available from Guangzhou Huatu cosmetics science and technology Limited; the methylene bis-benzotriazole tetramethylbutylphenol has CAS number 103597-45-1.

The preparation method of the oil-in-water sunscreen emulsion comprises the following steps:

Example 2

Embodiment 2 provides an oil-in-water sunscreen emulsion comprising, by weight, 60 parts of a group a water phase component, 45 parts of a group B oil phase component, 0.8 part of a group C component, 1.5 parts of a group D component, and 20 parts of a group E component;

the aqueous phase components of group a were the same as in example 1, except that the mass ratio of water, glycerin, butylene glycol, carbomer, xanthan gum, and sodium hyaluronate was 40: 4: 5: 0.2: 0.3: 0.03;

the component of the group B oil phase is the same as that of the group B oil phase in example 1, except that the mass ratio of the organic sunscreen agent to the grease to the skin-feel modifier to the emulsifier to the antioxidant is 26: 12: 0.1: 5: 0.15;

the component C is the same as the component in the example 1;

the component D is the same as in example 1;

the component E is the same as the component in example 1, except that the mass ratio of the phenoxyethanol to the dipotassium glycyrrhizinate to the silica to the methylene bis-benzotriazole tetramethyl butylphenol is 0.4: 0.15: 4: 6.

the oil-in-water sunscreen was prepared as in example 1.

Example 3

Example 3 provides an oil-in-water sunscreen comprising, by weight, 52 parts of a group a water phase component, 40 parts of a group B oil phase component, 0.6 part of a group C component, 1 part of a group D component, 17 parts of a group E component;

the aqueous phase components of group a were the same as in example 1, except that the mass ratio of water, glycerin, butylene glycol, carbomer, xanthan gum, and sodium hyaluronate was 34: 3: 4: 0.15: 0.2: 0.02;

the component of the oil phase in the group B is the same as that in example 1, except that the mass ratio of the organic sunscreen agent to the grease to the skin-feel modifier to the emulsifier to the antioxidant is 25.5: 10: 0.05: 4: 0.1;

the component C is the same as the component in the example 1;

the component D is the same as in example 1;

the component E is the same as the component in example 1, except that the mass ratio of the phenoxyethanol to the dipotassium glycyrrhizinate to the silica to the methylene bis-benzotriazole tetramethyl butylphenol is 0.3: 0.1: 3: 5.

the oil-in-water sunscreen was prepared as in example 1.

Example 4

Example 4 provides an oil-in-water sunscreen as in example 3, except that the cetearyl glucoside and cetearyl alcohol are replaced with caprylic/capric triglyceride, which is purchased from oxsnow.

The oil-in-water sunscreen was prepared as in example 1.

Example 5

Example 5 provides an oil-in-water sunscreen as in example 3, except that the cetearyl glucoside and cetearyl alcohol, glyceryl stearate and PEG-100 stearate are present in half the original amount.

The oil-in-water sunscreen was prepared as in example 1.

Example 6

Example 6 provides an oil-in-water sunscreen similar to example 3, except that glyceryl stearate and PEG-100 stearate were replaced with cetyl PEG/PPG-10/1 dimethicone, which was purchased from New chemical company.

The oil-in-water sunscreen was prepared as in example 1.

Example 7

Example 7 provides an oil-in-water sunscreen as in example 3, except that triethanolamine is replaced with glycerol.

The oil-in-water sunscreen was prepared as in example 1.

Example 8

Example 8 provides an oil-in-water sunscreen as in example 3.

s4: and simultaneously adding the component C, the component D and the component E into the mixture 1 obtained in the step S3, stirring and homogenizing until the components are completely dissolved, and continuously cooling to 45 ℃ to obtain the oil-in-water sun block.

Performance testing

1. And (3) stability testing: the oil-in-water sunscreen emulsions described in examples 1-8 were subjected to stability tests in cycles of normal temperature, 5 deg.C, -18 deg.C and 48 deg.C and high and low temperatures, and stability was observed after taking out every week and returning to normal temperature, and the test results are shown in Table 1.

2. And (3) centrifugal test: the sunscreen emulsions described in examples 1 to 8 were placed in a centrifuge and operated at 3000 rpm for 30min, and then the separation and stratification were observed, and the test results are shown in Table 1.

TABLE 1

	Stability test	Centrifugal test
			Example 1	Stabilization	Stabilization
Example 2	Stabilization	Stabilization
			Example 3	Stabilization	Stabilization
Example 4	Oil production at high and low temperatures of 2 weeks	Layering
			Example 5	2 weeks high and Low temperatureOil appearance	Layering
Example 6	Oil production at high and low temperatures of 2 weeks	Layering
			Example 7	Oil production at high and low temperatures of 2 weeks	Layering
Example 8	Stabilization	Stabilization

3. In vitro sun protection index: the oil-in-water sunscreen emulsions described in examples 1-8 were tested for in vitro Sun Protection Factor (SPF) according to the COLIPA Method (2011) standard, and the results are shown in table 3.

4. Evaluation of the degree of freshness: 36 volunteers with healthy skin, regardless of male and female, were randomly selected from a group of 6 individuals to try the oil-in-water sunscreen emulsions described in examples 1-8, and the refreshing degree was evaluated according to the evaluation criteria in Table 2, with the score ranging from 1 to 5, the larger the value, the deeper the degree, and the test results are shown in Table 3.

5. Evaluation of spreadability: 36 volunteers with healthy skin, regardless of male and female, are selected from the oil-in-water sun block described in examples 1-8, a group of 6 persons is randomly selected for trial use, the spreadability evaluation is carried out according to the evaluation standard of table 2, the score ranges from 1 to 5, the larger the value is, the deeper the degree is, and the test result is shown in table 3.

TABLE 2

TABLE 3

	SPF value	Degree of freshness	Spreadability
				Example 1	157.64	3.2	3.5
Example 2	171.47	3.4	3.4
				Example 3	148.14	3.7	3.8
Example 4	47.80	3.0	3.0
				Example 5	58.63	2.7	2.8
Example 6	56.91	2.5	2.4
				Example 7	87.19	2.8	2.5
Example 8	170.79	3.4	3.2

The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims

1. The oil-in-water sunscreen emulsion is characterized by comprising, by weight, 45-60 parts of a group A water phase component, 35-45 parts of a group B oil phase component, 0.5-0.8 part of a group C component, 0.5-1.5 parts of a group D component and 15-20 parts of a group E component; the group B oil phase component is selected from one or more of organic sunscreen agent, grease, skin feel regulator, emulsifier and antioxidant; the emulsifier comprises an O/W nonionic emulsifier with HLB value of 10-13.

2. The oil-in-water sunscreen emulsion according to claim 1, wherein in the component of the oil phase in the group B, the mass ratio of the organic sunscreen agent, the grease, the skin feel modifier, the emulsifier and the antioxidant is (20-26): (8-12): (0.01-0.1): (3-5): (0.05-0.15).

3. The oil-in-water sunscreen according to claim 2 wherein the organic sunscreen is selected from one or more of ethylhexyl methoxycinnamate, homosalate, octocrylene, ethylhexyl salicylate, hexyl diethylaminobenzoyl formate, bis-ethylhexyloxyphenol methoxyphenyl triazine.

4. The oil-in-water sunscreen according to claim 1 wherein the emulsifier further comprises cetearyl glucoside and cetearyl alcohol.

5. The oil-in-water sunscreen according to claim 1 wherein the O/W nonionic emulsifier having an HLB value of 10-13 is glyceryl stearate and PEG-100 stearate.

6. The oil-in-water sunscreen as claimed in claim 1 wherein the oil comprises one or more of cyclopentadimethylsiloxane, isononyl isononanoate, C12-15 alcohol benzoate, hydrogenated polyisobutene.

7. The oil-in-water sunscreen according to claim 1 wherein the group a aqueous phase components comprise water, glycerin, butylene glycol, carbomer, xanthan gum, sodium hyaluronate; the mass ratio of the water, the glycerin, the butanediol, the carbomer, the xanthan gum and the sodium hyaluronate is (30-40): (2-4): (1-3): (0.1-0.2): (0.1-0.3): (0.01-0.03).

8. The oil-in-water sunscreen emulsion according to any of claims 1 to 7 wherein the E component is selected from one or more of phenoxyethanol, dipotassium glycyrrhizinate, silica, methylene bis-benzotriazole tetramethylbutylphenol.

9. The oil-in-water sunscreen emulsion according to claim 8, wherein the mass ratio of phenoxyethanol to dipotassium glycyrrhizinate to silica to methylene bis-benzotriazole tetramethylbutylphenol is (0.2-0.4): (0.05-0.15): (2-4): (4-6).

10. A method for preparing the oil-in-water sunscreen according to claim 8, comprising the steps of: