CN109512682B

CN109512682B - Multiple emulsion with function of protecting natural water-soluble pigment, preparation method and application thereof

Info

Publication number: CN109512682B
Application number: CN201811654304.4A
Authority: CN
Inventors: 余嘉敏; 杨锦杰; 曾永权
Original assignee: Huanan Industrial Technology Research Institute of Zhejiang University
Current assignee: Huanan Industrial Technology Research Institute of Zhejiang University
Priority date: 2018-12-29
Filing date: 2018-12-29
Publication date: 2022-03-25
Anticipated expiration: 2038-12-29
Also published as: CN109512682A

Abstract

The invention relates to a multiple emulsion with a function of protecting natural water-soluble pigment, a preparation method and application thereof. The multiple emulsion consists of a W/O type primary phase and an external water phase, wherein the W/O type primary phase comprises a natural water-soluble pigment solution, a W/O type emulsifier and an oil phase thickener, and the external water phase comprises an O/W type emulsifier and a water phase thickener. The multiple emulsion of the invention wraps the natural water-soluble pigment in the inner water phase, can avoid the damage of external factors to the natural water-soluble pigment, improve the stability of the natural water-soluble pigment, and simultaneously, the system can also have good stability. The preparation method of the multiple emulsion is simple, and has good application prospect in the field of cosmetics.

Description

Multiple emulsion with function of protecting natural water-soluble pigment, preparation method and application thereof

Technical Field

The invention belongs to the field of cosmetics, and relates to a multiple emulsion with a function of protecting natural water-soluble pigments, and a preparation method and application thereof.

Background

The natural water-soluble pigment is derived from roots, stems, leaves, flowers, fruits and other parts of natural plants, mostly anthocyanins, carotenoids and flavonoids, is a substance with biological activity, and has high safety. According to the reports of the literature, the natural water-soluble pigment not only can provide a dyeing effect, but also has the effects of resisting oxidation, improving eyesight, resisting cancer, resisting mutation, losing weight, resisting aging and the like. Therefore, the natural water-soluble pigment has wide application prospect in the industries of food, medicine and cosmetics.

The natural water-soluble pigments come from various parts of natural plants, the natural plants are various in types and complex in properties, most of the natural plant pigments are sensitive to light, heat, oxygen, microorganisms, metals and pH value changes, and the stability is poor, so that the application of the natural water-soluble pigments is limited. At present, natural water-soluble pigments are mostly applied in the forms of microcapsules, liposomes, nano-particles and the like, but the preparation process is complex and is not beneficial to production and application in cosmetics. Therefore, an ideal system is needed, which not only can protect the natural water-soluble pigment well, but also has a simpler preparation method, and in addition, the system itself needs to have better stability so as to facilitate the application and popularization.

Disclosure of Invention

In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a multiple emulsion with the function of protecting natural water-soluble pigments, a preparation method and application thereof.

The purpose of the invention is realized by the following technical scheme:

a multiple emulsion with the function of protecting natural water-soluble pigment is characterized in that: the multiple emulsion consists of a W/O type initial phase and an external water phase, and the mass ratio of the W/O type initial phase to the external water phase is 10-80: 20-90;

the W/O type primary phase comprises 0.1-80% of natural water-soluble pigment, 0.1-20% of W/O type emulsifier, 5-60% of grease, 0.1-5% of oil phase thickener and the balance of water by mass percent;

the external aqueous phase comprises 0.1-20% by mass of an O/W emulsifier, 0.1-5% by mass of an aqueous phase thickener and the balance water, the O/W emulsifier being a mixture of dimethicone copolymer and caprylic/capric triglyceride, a mixture of cetearyl olive oil ester and sorbitan olive oil ester, a mixture of cetearyl glucoside and cetearyl alcohol, a mixture of lauryl glucoside, polyglyceryl-2 dipolyhydroxystearate and glycerol, a mixture of cetearyl glucoside and cetearyl alcohol, PEG-20 methyl glucoside sesquistearate, steareth-21, ceteareth-21, behenyl ether-25, PEG-7 sodium olive oil carboxylate, ceteareth-6 olive oleate, cetearyl glucoside, cetyl phosphate DEA salt, cetyl phosphate, potassium cetyl phosphate, ceteareth-20, glyceryl stearate, tris (laureth-4) phosphate, PEG-20 glyceryl stearate, sodium cetearyl sulfonate, or a mixture of at least one of these with Tween, preferably a mixture of steareth-21 and Tween 60. The multiple emulsion has multiple structures, can effectively wrap natural water-soluble pigments in an internal water phase, avoids the damage of external factors to the natural water-soluble pigments, has good illumination stability, smoothness, spreadability and lightness and thinness, and can easily form a more regular multiple structure when an O/W type emulsifier is a mixture of steareth-21 and tween 60, thereby being more beneficial to the protection of the natural water-soluble pigments.

Preferably, the mass ratio of the W/O type initial phase to the external water phase is 30-70: 30-70;

the W/O type primary phase comprises 0.1-80% of natural water-soluble pigment, 2-8% of W/O type emulsifier, 10-60% of grease, 0.1-0.5% of oil phase thickener and the balance of water by mass percent;

the external water phase comprises 1-8% of O/W type emulsifier, 0.1-1% of water phase thickener and the balance of water by mass percent. Under the condition, the multiple structure quantity of the multiple emulsion is more, the particle size ratio is smaller, and the natural water-soluble pigment can be better wrapped, so that the natural water-soluble pigment can be better protected.

Preferably, the W/O type emulsifier is a mixture of cyclopentadimethylsiloxane and PEG/PPG-20/15 polydimethylsiloxane, a mixture of cyclopentadimethylsiloxane and PEG/PPG-18/18 polydimethylsiloxane, a mixture of cyclopentadimethylsiloxane and PEG-12 polydimethylsiloxane cross-linked polymer, isosteareth-2, a mixture of sorbitan sesquioleate and cetyl PEG/PPG-10/1 polydimethylsiloxane, span, polyglycerol-2 dipolyhydroxystearate, polyglycerol-3 diisostearate, polyglycerol-3 polyricinoleate, PEG-10 polydimethylsiloxane, lauryl PEG-10 tris (trimethylsiloxy) silaethyl polymethylsiloxane, sorbitan tristearate, PEG-12 dimethicone, sorbitan monostearate, dimethicone, and mixtures thereof, Sorbitan oleate, a mixture of sorbitan sesquioleate and sorbitan trioleate, PEG-8 polydimethylsiloxane, bis-isobutyl PEG/PPG-10/7/polydimethylsiloxane copolymer, polydimethylsiloxane PEG-10/15 crosspolymer, polyglycerol-2 sesquioleate, PEG-30 dipolyhydroxystearate, sorbitan olivil oleate, PEG-9 polydimethylsiloxane, lauryl PEG/PPG-18/18 polydimethylsiloxane, cetyl PEG/PPG-10/1 polydimethylsiloxane, preferably cetyl PEG/PPG-10/1 polydimethylsiloxane. When the substances are used as the W/O type emulsifier, the multiple emulsion not only has good light stability, but also has good heat resistance and cold resistance, the formed multiple emulsion has a more regular structure, and particularly when cetyl PEG/PPG-10/1 polydimethylsiloxane is used as the W/O type emulsifier, the multiple emulsion is easy to form a regular multiple structure, so that natural water-soluble pigments can be better protected.

Preferably, the oil phase thickener is at least one of trihydroxy stearate, aluminum/magnesium hydroxide stearic acid complex and modified montmorillonite, and is preferably modified montmorillonite. The substances are used as the oil phase thickening agent, the collision among particles in the W/O type initial phase can be properly slowed down, so that the multiple emulsion has better stability, and particularly, the modified montmorillonite is used as the oil phase thickening agent, so that the multiple emulsion has better stability.

Preferably, the oil is at least one of caprylic/capric triglyceride, isopropyl myristate, squalane, triglyceride and isononyl isononanoate, and is preferably a mixture of caprylic/capric triglyceride and isopropyl myristate. When the grease is the substances, the grease does not need to be heated and melted, the natural water-soluble pigment can be prevented from being damaged by high temperature when being added into the grease, and when the grease is the mixture of caprylic/capric triglyceride and isopropyl myristate, the formation of multiple structures of multiple emulsions is facilitated.

Preferably, the aqueous phase thickener is at least one of polyacrylic acid polymer, hydroxyethyl cellulose, guar gum, xanthan gum, gelatin, hydroxypropyl starch phosphate, guar gum hydroxypropyl trimethyl ammonium chloride, hectorite, magnesium aluminum silicate, soluble starch, gum arabic, sodium alginate, carboxymethyl cellulose and carboxypropyl cellulose, and is preferably xanthan gum. These materials are used as water phase thickening agents, which are beneficial to the stability of multiple emulsions and the formation of multiple structures.

Preferably, the natural water-soluble pigment is at least one of tetrapyrrole derivatives, isoprene derivatives, anthocyanin derivatives, ketone derivatives, quinone derivatives and caramel pigment, the tetrapyrrole derivatives are at least one of chlorophyll, sodium copper chlorophyllin and heme, the isoprene derivatives are at least one of capsanthin, gardenia yellow and beta-carotene, the anthocyanin derivatives are at least one of red orange, grape skin red, roselle red, radish red, beet red, sweet potato red, black bean red and mulberry red, the ketone derivatives are at least one of curcumin, monascus pigment, safflower yellow and cocoa shell pigment, and the quinone derivatives are at least one of shellac red and cochineal red.

Preferably, the mass ratio of the W/O type initial phase to the external water phase is 30: 70;

the W/O type initial phase comprises 5 percent of cetyl PEG/PPG-10/1 polydimethylsiloxane, 10 percent of caprylic/capric triglyceride, 10 percent of isopropyl myristate and 0.3 percent of modified montmorillonite in percentage by mass;

the external water phase comprises 0.5 percent of xanthan gum, 1 percent of steareth-21 and 1 percent of Tween 60 in percentage by mass. Under the condition, the multiple structure of the multiple emulsion is regular round, the average grain diameter is about 10 mu m, the system stability is good, and the natural water-soluble color can be well protected.

The invention also provides a preparation method of the multiple emulsion, which comprises the following steps:

(1) homogenizing the W/O type emulsifier, the grease and the oil phase thickener for 2-4min at 3000-;

(2) slowly dripping the natural water-soluble pigment solution into the oil phase while homogenizing, and homogenizing for 3-7min under the conditions of 4000-6000rpm after dripping to form a stable W/O emulsion to obtain a W/O type initial phase;

(3) uniformly mixing the initial water phase at 40-50 ℃ and 200-600rpm, dropwise adding the W/O type initial phase into the initial water phase, and stirring for 20-30min after dropwise adding to obtain the multiple emulsion.

The invention also provides the use of said multiple emulsions, which can be used for the preparation of cosmetics, including but not limited to masks, essences, lotions, creams or lipsticks.

Compared with the prior art, the invention has the following advantages and beneficial effects:

(1) the multiple emulsion with the function of protecting the natural water-soluble pigment can wrap the natural water-soluble pigment in the internal water phase, can avoid the damage of external factors to the natural water-soluble pigment, improves the stability of the natural water-soluble pigment, has good stability and is easy to popularize and apply.

(2) The preparation method of the multiple emulsion with the function of protecting the natural water-soluble pigment is simple to operate, controllable in conditions and easy to produce.

(3) The multiple emulsion with the function of protecting the natural water-soluble pigment is smooth, has good spreadability, does not feel greasy when being used, and has good application prospect in the field of cosmetics.

Drawings

FIG. 1 is a view showing a structure of a microscope of a multiple emulsion in example 2;

FIG. 2 is a view showing a structure of a microscope of a multiple emulsion in comparative example 3;

FIG. 3 is a view showing a structure of a microscope of an emulsion in comparative example 4.

Detailed Description

To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.

Example 1

A multiple emulsion with natural water soluble pigment protecting effect has components shown in Table 1.

TABLE 1 ingredients and contents/% of multiple emulsions of examples 1-7 having the function of protecting natural water-soluble pigments

The preparation method of the multiple emulsion comprises the following steps:

(1) homogenizing cetyl PEG/PPG-10/1 polydimethylsiloxane, caprylic/capric triglyceride, isopropyl myristate and modified montmorillonite at 3000rpm for 4min to obtain oil phase;

(2) uniformly mixing the anthocyanin extract water solution with water, slowly dripping into the oil phase while homogenizing, and homogenizing at 4000rpm for 7min after dripping to form a stable W/O emulsion to obtain a W/O type primary phase;

(3) uniformly mixing glycerol, xanthan gum, tween 60, steareth-21, phenoxyethanol and water at 40 ℃ and a stirring speed of 400rpm to obtain a primary water phase, dropwise adding the W/O type primary phase into the primary water phase, and stirring for 30min after dropwise adding to obtain the multiple emulsion.

The multiple emulsion can be used for preparing cosmetics such as facial mask, essence, lotion, cream, lipstick, etc.

Example 2

The preparation method of the multiple emulsion comprises the following steps:

(1) homogenizing cetyl PEG/PPG-10/1 polydimethylsiloxane, caprylic/capric triglyceride, isopropyl myristate and modified montmorillonite at 4000rpm for 3min to obtain an oil phase;

(2) uniformly mixing the anthocyanin extract water solution with water, slowly dripping into the oil phase while homogenizing, and homogenizing at 5000rpm for 5min after dripping to form a stable W/O emulsion to obtain a W/O type initial phase;

(3) uniformly mixing glycerol, xanthan gum, tween 60, steareth-21, phenoxyethanol and water at the temperature of 45 ℃ and the stirring speed of 400rpm to obtain a primary water phase, dropwise adding the W/O type primary phase into the primary water phase, and stirring for 25min after dropwise adding to obtain the multiple emulsion.

Example 3

The preparation method of the multiple emulsion comprises the following steps:

(1) homogenizing cetyl PEG/PPG-10/1 polydimethylsiloxane, caprylic/capric triglyceride, isopropyl myristate and modified montmorillonite at 5000rpm for 2min to obtain oil phase;

(2) uniformly mixing the anthocyanin extract water solution with water, slowly dripping into the oil phase while homogenizing, and homogenizing at 6000rpm for 3min after dripping to form a stable W/O emulsion to obtain a W/O type primary phase;

(3) uniformly mixing glycerol, xanthan gum, steareth-21, phenoxyethanol and water at the temperature of 50 ℃ and the stirring speed of 400rpm to obtain a primary water phase, dropwise adding the W/O type primary phase into the primary water phase, and stirring for 20min after dropwise adding to obtain the multiple emulsion.

Examples 4 to 15

All of them are multiple emulsions having a function of protecting natural water-soluble pigments, in which the components of examples 4-7 are shown in Table 1, and the components of examples 8-15 are shown in Table 2.

TABLE 2 ingredients and contents/% of multiple emulsions of examples 8-15 having the function of protecting natural water-soluble pigments

Example 16

A multiple emulsion having a function of protecting a natural water-soluble pigment, the composition and content of which are the same as those in example 1; the preparation method was the same as in example 1 except that the stirring speed in step (3) was 200 rpm.

Example 17

A multiple emulsion having a function of protecting a natural water-soluble pigment, the composition and content of which are the same as those in example 1; the preparation method was the same as in example 1 except that the stirring speed in step (3) was 600 rpm.

Comparative example 1

An emulsion was prepared in the same manner as in example 1 except that the aqueous phase contained no steareth-21 in the same amounts and components as in example 1.

Comparative example 2

An emulsion, which is the same as the emulsion of the embodiment 1 except that the W/O type primary phase does not contain cetyl PEG/PPG-10/1 polydimethylsiloxane, and contains 5 percent of span 60 by mass percent; the emulsion was prepared as in example 1 except that span 60 was used in place of cetyl PEG/PPG-10/1 dimethicone in step (1).

Comparative example 3

An emulsion, which comprises 5% by weight of PEG-30 dipolyhydroxystearate and does not contain cetyl PEG/PPG-10/1 polydimethylsiloxane in the W/O type primary phase, and the other components and contents are the same as those in example 1; the emulsion was prepared in the same manner as in example 1 except that PEG-30 dipolyhydroxystearate was used in step (1).

Comparative example 4

An emulsion having the same composition and content as in example 1; the preparation method was the same as example 1 except that the stirring in step (3) was changed to homogenization at a speed of 600 rpm.

Comparative example 5

An O/W type emulsion is prepared by the following steps: uniformly mixing 10g of cetyl PEG/PPG-10/1 polydimethylsiloxane, 10g of caprylic/capric triglyceride and 10g of isopropyl myristate to obtain an oil phase; then 0.5g of xanthan gum, 1g of steareth-21, 0.5g of tween 60, 2g of glycerol, g of pigment and g of water are uniformly mixed to obtain a water phase; and (3) dripping the oil phase into the water phase while homogenizing at 4000rpm, and homogenizing at 5000rpm for 5min to obtain the O/W type emulsion.

The structure of the emulsions of examples 1 to 17 and comparative examples 1 to 3 was observed by a microscope, and the emulsions of examples 1 to 17 and comparative examples 1 to 6 were subjected to a stability test in which the emulsions were exposed to 50 deg.C, 18 deg.C and natural light for 1 month, respectively, to observe changes in the emulsions, and the results of the structure and stability tests are shown in Table 3.

TABLE 3 test results

As can be seen from Table 3, examples 1 to 17 did not change color at high temperature, low temperature and light conditions as compared with comparative example 5, which indicates that the multiple emulsion structure of the present invention is superior in protecting natural water-soluble pigments; compared with comparative example 1, examples 1-17 can form multiple structures and are stable under light conditions, which shows that the multiple structures of multiple emulsions are formed and the stability of the system is related to the type of W/O type emulsifier; the multiple structures of the multiple emulsions of examples 1-12 and 15 have a larger number than that of the multiple emulsions of example 13 and example 1-12 and example 15 have a smaller particle size than that of the multiple emulsions of example 14, which indicates that when the W/O type primary phase and the external aqueous phase have a mass ratio of 25-70:30-75, the W/O type primary phase comprises 2-8% W/O type emulsifier and 0.1-0.5% oil phase thickener, and the external aqueous phase comprises 1-8% O/W type emulsifier and 0.1-1% aqueous phase thickener, the multiple emulsions have a better protective effect on natural water-soluble pigments, and the mass ratio of the W/O type primary phase and the external aqueous phase is 30-70:30-70, and the W/O type primary phase comprises 2-8% W/O type emulsifier, 0.1-1% aqueous phase thickener 10-60% of grease and 0.1-0.5% of oil phase thickening agent, and when the external water phase comprises 1-8% of O/W type emulsifier and 0.1-1% of water phase thickening agent in percentage by mass, the forming effect of the multiple structure is better; examples 1-17 are more stable at high and low temperatures than comparative examples 2 and 3, which illustrates that the use of suitable O/W emulsifiers is beneficial to system stability; compared with comparative example 4, the multiple structures can be formed in examples 1 and 16-17, which shows that when the W/O type primary phase is mixed with the water phase, the stirring is more favorable for the formation of the multiple structures than the homogenization, and in addition, compared with examples 16-17, example 1 can form the multiple structures with more regular and smaller particle size, which shows that when the W/O type primary phase is mixed with the water phase, the stirring speed is too high or too low to be favorable for the formation of the multiple structures.

The multiple emulsion of example 1-2 was centrifuged at 3000rpm for 30min to delaminate example 1, but not example 2, indicating that the stability of the system was very good.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. A multiple emulsion with the function of protecting natural water-soluble pigment is characterized in that: the multiple emulsion consists of a W/O type initial phase and an external water phase, wherein the mass ratio of the W/O type initial phase to the external water phase is 30: 70;

the W/O type primary phase comprises 10% of natural water-soluble pigment, 5% of W/O type emulsifier, 20% of grease, 0.3% of oil phase thickener and the balance of water by mass percent;

the W/O type emulsifier is cetyl PEG/PPG-10/1 polydimethylsiloxane; the grease is a mixture of caprylic/capric triglyceride and isopropyl myristate; the oil phase thickener is modified montmorillonite;

the external water phase comprises 2% of O/W type emulsifier, 0.5% of water phase thickener and the balance of water by mass percent;

the O/W type emulsifier is a mixture formed by steareth-21 and tween 60; the water phase thickener is xanthan gum;

the preparation method of the multiple emulsion comprises the following steps:

(3) uniformly mixing the external water phase at 40-50 ℃ and 200-600rpm, dropwise adding the W/O type primary phase into the external water phase, and stirring for 20-30min after dropwise adding to obtain the multiple emulsion.

2. Multiple emulsion according to claim 1, characterized in that: the natural water-soluble pigment is at least one of tetrapyrrole derivatives, isoprene derivatives, anthocyanin derivatives, ketone derivatives, quinone derivatives and caramel pigment, the tetrapyrrole derivatives are at least one of chlorophyll, sodium copper chlorophyllin and heme, the isoprene derivatives are at least one of capsanthin, gardenia yellow and beta-carotene, the anthocyanin derivatives are at least one of lingonberry red, grape skin red, roselle red, radish red, beet red, sweet potato red, black bean red and mulberry red, the ketone derivatives are at least one of curcumin, monascus pigment, safflower yellow and cocoa shell pigment, and the quinone derivatives are at least one of shellac red and cochineal red.

3. Multiple emulsion according to claim 1, characterized in that: the W/O type initial phase comprises 10% of caprylic/capric triglyceride and 10% of isopropyl myristate in percentage by mass.

4. Use of a multiple emulsion according to any one of claims 1 to 3, wherein: the multiple emulsion is used for preparing cosmetics, including facial masks, essences, lotions, creams or lipsticks.