CN109010101A - A kind of phosphoramidite chemical sun-screening agent and wide spectrum suncream and preparation method thereof - Google Patents

Abstract

A broad-spectrum chemical sunscreen, broad-spectrum sunscreen and preparation method thereof, the invention discloses a broad-spectrum sunscreen, which comprises 3-methoxycinnamic acid (2-ethyl) hexyl ester and 3, (2-ethyl)hexyl 5‑dimethoxy‑4 hydroxycinnamate, the mass ratio of the two is 0.5:5～5:0.5; this broad-spectrum chemical sunscreen can strongly absorb ultraviolet rays UVB and UVA regions The ratio of the absorbance of light in the ultraviolet UVB region and UVA region is 0.5:5 to 5:0.5. The broad-spectrum sunscreen agent prepared by the present invention includes 3-methoxycinnamic acid (2-ethyl) hexyl ester, 3,5-dimethoxy-4 hydroxycinnamic acid (2-ethyl) hexyl ester, marigold Extract, Tea Polyphenols, Tween 80, Zinc Oxide, Vaseline, Glycerin and Distilled Water. The sunscreen prepared by applying the sunscreen of the invention to an effective amount of a cosmetically acceptable carrier not only has the characteristics of broad-spectrum sunscreen, but also has no irritation to the skin, no toxic and side effects, and has high safety in use.

Description

A kind of broad-spectrum chemical sunscreen agent and broad-spectrum sunscreen and preparation method thereof

technical field

The invention relates to a daily chemical skin care product and a preparation method thereof, in particular to a sunscreen, a sunscreen containing the sunscreen and a preparation method thereof.

Background technique

For humans, if the skin is exposed to the hot sun for a long time, due to the direct contact of strong ultraviolet light with the skin, it will cause redness or tanning, which will cause skin damage, spots, sagging skin or wrinkles. In severe cases It can cause cancer such as melanoma, so effective sun protection is very necessary. Although there are many kinds of sunscreens on the market, they have shortcomings such as short duration, narrow range of effective sun protection, and unknown adverse effects caused by long-term use of artificial molecules.

Contents of the invention

Aiming at the prior art, the present invention fully makes up for the shortcomings of existing similar products, and provides a broad-spectrum sunscreen with an extremely ideal broad-spectrum sunscreen effect by integrating the advantages of various products. The broad-spectrum sunscreen of the present invention mainly protects the skin effectively through the reflection and absorption of ultraviolet rays, and the use effect is good.

In order to solve the above-mentioned technical problems, a kind of broad-spectrum chemical sunscreen that the present invention proposes, the component that comprises and weight ratio are: 3-methoxycinnamic acid (2-ethyl) hexyl ester and 3,5-dimethoxy The weight ratio of 4-hydroxycinnamic acid (2-ethyl)hexyl ester is 0.5:5～5:0.5; 3-methoxycinnamic acid (2-ethyl)hexyl ester and 3,5-dimethoxy The general formula of -4 hydroxycinnamic acid (2-ethyl) hexyl ester is as follows:

Among them, when expressed as 3-methoxycinnamic acid (2-ethyl) hexyl ester, the substituent R is the acid of R1, expressed as 3,5-dimethoxy-4 hydroxycinnamic acid (2-ethyl) When hexyl ester, substituent R is the acid of R2;

The broad-spectrum chemical sunscreen absorbs light in the ultraviolet UVB region and UVA region, and the absorbance ratio of the light in the ultraviolet UVB region to the light in the ultraviolet UVA region is 0.5:5-5:0.5.

The preferred weight ratio of the 3-methoxycinnamic acid (2-ethyl) hexyl ester and 3,5-dimethoxy-4 hydroxycinnamic acid (2-ethyl) hexyl ester is 1:1, absorbing ultraviolet rays The ratio of absorbance of light in the UVB region to light in the UVA region is 1:1.

A kind of preparation method of preparing above-mentioned broad-spectrum chemical sunscreen agent proposed in the present invention, comprises the following steps:

Preparation of (2-ethyl)hexyl 3-methoxycinnamate: 1.0 equivalents of the acid of R1 and 1.2 equivalents of 2-ethylhexan-1-ol were dissolved in 10 equivalents of tetrahydrofuran and 3 equivalents of N,N-di Methylformamide, and then dropwise added 1.2 equivalents of thionyl chloride therein to obtain a mixture; the mixture was heated to 70 °C for at least 2 days, until TLC showed that the acid of R1 of 1.0 equivalents of the raw material was completely consumed, and the mixture was washed with water ; the organic phase was concentrated and purified by thin layer chromatography with Elution gives 3-methoxycinnamic acid (2-ethyl) hexyl ester;

Preparation of (2-ethyl)hexyl 3,5-dimethoxy-4-hydroxycinnamate: 1.0 equivalents of the acid of R2 and 1.2 equivalents of 2-ethylhexan-1-ol were dissolved in 10 equivalents of tetrahydrofuran and 3 1.2 equivalents of thionyl chloride was added dropwise to an equivalent amount of N,N-dimethylformamide to obtain a mixture; the mixture was heated to 70°C for at least 2 days until TLC showed that 1.0 equivalents of the raw material R2 acid was completely consumed Afterwards, the mixture was washed with water; the organic phase was concentrated and purified by thin layer chromatography with Elution gave (2-ethyl)hexyl 3,5-dimethoxy-4-hydroxycinnamate.

A kind of broad-spectrum sunscreen proposed in the present invention, the component that comprises and percentage by weight thereof are:

The preparation method of above-mentioned broad-spectrum sunscreen comprises the following steps:

Step 1, adding zinc oxide to glycerin and stirring evenly to obtain mixture A;

Step 2, adding Tween 80, calendula flower extract and tea polyphenols into distilled water, stirring evenly to obtain mixture B;

Step 3. Add mixture B to mixture A, then add vaseline, 3-methoxycinnamic acid (2-ethyl) hexyl ester and 3,5-dimethoxy-4 hydroxycinnamic acid (2-ethyl) ) hexyl ester, stirred evenly to obtain mixture C;

Step 4, emulsifying the mixture C in step 3, which is the obtained;

The above steps are carried out at normal temperature and pressure.

Compared with prior art, the beneficial effect of the present invention is:

Has an extremely ideal broad-spectrum sunscreen effect. This product mainly protects the skin effectively through the reflection and absorption of ultraviolet rays, and the use effect is good. The main raw materials of this product are less irritating to the skin, will not cause skin allergies, have no toxic and side effects, and are relatively safe to use.

Description of drawings

Fig. 1 is the ultraviolet spectrogram when the concentration of two main chemical sunscreens in the broad-spectrum sunscreen prepared by the present invention is 0.045mmol/L in methylene chloride.

Detailed ways

The technical solution of the present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments, and the described specific embodiments are only for explaining the present invention, and are not intended to limit the present invention.

A kind of broad-spectrum chemical sunscreen that the present invention proposes, the component that comprises and weight ratio are: 3-methoxycinnamic acid (2-ethyl) hexyl ester and 3,5-dimethoxyl-4 hydroxyl cinnamon (2-Ethyl)hexyl acid is formulated according to the mass ratio of 0.5:5 to 5:0.5,

Wherein, the general formula of (2-ethyl) hexyl 3-methoxycinnamate and (2-ethyl) hexyl 3,5-dimethoxy-4 hydroxycinnamate is as follows:

The broad-spectrum chemical sunscreen absorbs light in the ultraviolet UVB region and UVA region, and the absorbance ratio of the light in the ultraviolet UVB region to the light in the ultraviolet UVA region is 0.5:5-5:0.5. When the mass ratio is 1:1, the ratio of absorbance is 1:1.

The preparation of the above-mentioned broad-spectrum chemical sunscreen includes the preparation of (2-ethyl) hexyl 3-methoxycinnamate and (2-ethyl) hexyl 3,5-dimethoxy-4 hydroxycinnamate, wherein, When preparing (2-ethyl)hexyl 3-methoxycinnamate, use the acid whose substituent R is R1, and when preparing (2-ethyl)hexyl 3,5-dimethoxy-4 hydroxycinnamate, use The acid whose substituent R is R2, the preparation process is basically the same: the corresponding acid (1.0 equivalent) and 2-ethylhexan-1-ol (1.2 equivalent) are dissolved in 10mL THF and 3mL DMF, and SOCl ₂ (1.2 equivalent). The mixture was heated to 70° C. for 2 days or more. After TLC showed complete consumption of starting material, the mixture was washed with water. The organic phase was concentrated and purified by thin layer chromatography with elute. Promptly obtain (2-ethyl) hexyl 3-methoxycinnamate and (2-ethyl) hexyl 3,5-dimethoxy-4 hydroxycinnamate respectively, and output is

The components of the broad-spectrum sunscreen prepared by using the broad-spectrum chemical sunscreen of the present invention in sunscreens and their weight percentages are: 3-methoxycinnamic acid (2-ethyl)hexyl ester is 0.5-5.0, 3 , 5-dimethoxy-4-hydroxycinnamic acid (2-ethyl) hexyl ester is 0.5-5.0, calendula extract is 5.0-10.0, tea polyphenols is 5.0-10.0, Tween 80 is 10.0-20.0 , zinc oxide is 3.0-5.0, vaseline is 3.0-10.0, glycerin is 3.0-10.0, and the balance is distilled water.

The preparation method of the above-mentioned broad-spectrum sunscreen comprises the following steps: firstly, adding zinc oxide into glycerin and stirring uniformly to obtain mixture A, which is set aside; adding Tween 80, calendula flower extract and tea polyphenols into distilled water, and stirring Obtain mixture B, standby; The above-mentioned mixture B is joined in the mixture A, then add petrolatum, 3-methoxycinnamic acid (2-ethyl) hexyl ester and 3,5-dimethoxy-4 hydroxycinnamic acid ( 2-Ethyl)hexyl ester, stirred evenly to obtain mixture C; finally, emulsifying mixture C to obtain.

Example 1:

Under normal temperature and pressure, according to the components and contents specified in Table 1 below, zinc oxide is added to glycerin and stirred evenly to obtain mixture A, which is set aside; Tween 80, calendula extract and tea polyphenols Add distilled water, stir evenly to obtain mixture B, and set aside; add the above mixture B to mixture A, then add petrolatum, 3-methoxycinnamic acid (2-ethyl)hexyl ester and 3,5-dimethoxy -(2-Ethyl)hexyl 4-hydroxycinnamate, stirred evenly to obtain a mixture C; finally, the mixture C was emulsified to obtain the obtained.

Example 2-24:

The method of Example 1 was repeated according to each component and content specified in Table 1 below.

Table 1

Sunscreen effectiveness test:

Randomly select 500 volunteers, 20 users of each embodiment, apply sunscreen on one arm, and not apply sunscreen on the other, expose to the sun for 1 hour every day, compare the tanning degree of the two arms and evaluate whether the sunscreen is allergic , used continuously for 25 days, the results are shown in Table 2, the sunscreen effect is divided into three grades:

Obvious: The contrast between the arm with sunscreen and the arm without sunscreen is obvious. The arm with sunscreen has fair skin without irritation, and the arm without sunscreen has obvious tan and sunburn.

More obvious: the arm with sunscreen is more obvious than the arm without sunscreen, the skin color of the arm with sunscreen is darker, without irritation; the arm without sunscreen is more tanned.

Inconspicuous: There was no significant contrast between sunscreen-applied arms and non-sunscreen-applied arms, and there was no significant difference in skin color between sunscreen-applied arms and non-sunscreen-applied arms.

There are two levels of irritation in sunscreens:

Irritant: Allergic reaction to sunscreen-applied arm.

Non-irritating: No allergic reaction to the arm where the sunscreen was applied.

Table 2

In the broad-spectrum sunscreen prepared by the present invention, when 3-methoxycinnamic acid (2-ethyl) hexyl ester and 3,5-dimethoxy-4 hydroxycinnamic acid (2-ethyl) hexyl ester are When the percentage content is 1; 1, the effect is the best, and the effective rate for skin tanning and sunburn can be as high as 100%, and the effective rate is lower than 100% when the ratio is reduced or increased. When 3-methoxycinnamic acid (2-ethyl) hexyl ester and 3,5-dimethoxyl-4 hydroxycinnamic acid (2-ethyl) hexyl ester percentage content exceeded 5%, by embodiment 6 results It can be seen that sunscreen can cause certain irritation to the skin, so 3-methoxycinnamic acid (2-ethyl) hexyl ester and 3,5-dimethoxy-4 hydroxycinnamic acid (2-ethyl) ) hexyl ester. However, changing the percentage content of other components in the sunscreen will affect the physical properties of this product, but has no obvious impact on the sunscreen effectiveness of this product. It can be seen from the above use effects that the use of the sunscreen provided by the present invention can effectively prevent sunburn and tanning of the skin.

From the test results in Table 2, 3-methoxycinnamic acid (2-ethyl) hexyl ester and 3,5-dimethoxy-4 hydroxycinnamic acid (2-ethyl) hexyl ester are about The 1:1 composition can strongly absorb the light in the ultraviolet B region (UVB, 285-320nm) and A region (UVA, 320-400nm) (the ultraviolet C region (UVC, <285nm) is completely absorbed by the ozone layer, so sunscreen does not have to be This design), has the characteristics of broad-spectrum sun protection. As shown in Figure 1. A good sunscreen should be able to strongly absorb the light of ultraviolet B interval (UVB, 285-320nm) and A interval (UVA, 320-400nm), and Fig. 1 is two main chemical sunscreens in the broad-spectrum sunscreen prepared by the present invention The ultraviolet spectrogram when concentration is 0.045mmol/L in dichloromethane. As shown in Figure 1, the two main chemical sunscreens can cover the entire UVA and UVB bands very well, and experiments have proved that they are very ideal sunscreens.

Although the present invention has been described above in conjunction with the accompanying drawings, the present invention is not limited to the above-mentioned specific embodiments, and the above-mentioned specific embodiments are only illustrative, rather than restrictive. Under the enlightenment of the present invention, many modifications can be made without departing from the gist of the present invention, and these all belong to the protection of the present invention.

Claims (5)

1. a kind of phosphoramidite chemical sun-screening agent, which is characterized in that the component and weight ratio for including are: 3- methoxy cinnamic acid (2- second Base) weight ratio of own ester and 3,5- dimethoxy-4 ' hydroxycinnamic acid (2- ethyl) own ester is 0.5:5~5:0.5；

The general formula of the own ester of 3- methoxy cinnamic acid (2- ethyl) and 3,5- dimethoxy-4 ' hydroxycinnamic acid (2- ethyl) own ester is such as Under:

Wherein, when being expressed as 3- methoxy cinnamic acid (2- ethyl) own ester, substituent R is the acid of R1, is expressed as 3,5- dimethoxy When -4 hydroxycinnamic acid of base (2- ethyl) own ester, substituent R is the acid of R2；

The phosphoramidite chemical sun-screening agent absorbs the light in the area ultraviolet (UV) B and the area UVA, absorbs ultraviolet (UV) B area's light and absorbs ultraviolet light The ratio of the absorbance of the area UVA light is 0.5:5~5:0.5.

2. phosphoramidite chemical sun-screening agent according to claim 1, which is characterized in that the 3- methoxy cinnamic acid (2- ethyl) oneself Ester and 3, the mass ratio of 5- dimethoxy-4 ' hydroxycinnamic acid (2- ethyl) own ester are 1:1, absorb ultraviolet (UV) B area's light and absorb The ratio of the absorbance of the area ultraviolet (UV) A light is 1:1.

3. a kind of preparation method for preparing phosphoramidite chemical sun-screening agent as claimed in claim 1 or 2, comprising the following steps:

Prepare 3- methoxy cinnamic acid (2- ethyl) own ester: by the acid of the R1 of 1.0 equivalents and the 2- ethyl hex- 1- alcohol of 1.2 equivalents It is dissolved in 10 equivalent tetrahydrofurans and 3 equivalent n,N-Dimethylformamide, the thionyl chloride of 1.2 equivalents is then added dropwise thereto, Obtain mixture；It heats the mixture to 70 DEG C to react at least 2 days, until the acid of the R1 for 1.0 equivalent of raw material that TLC is shown disappears completely After consumption, mixture is washed with water；Organic phase is concentrated to and is used thin layer chromatography, is used Elution, obtains To 3- methoxy cinnamic acid (2- ethyl) own ester；

Prepare 3,5- dimethoxy-4 ' hydroxycinnamic acid (2- ethyl) own ester: by the acid of the R2 of 1.0 equivalents and the 2- second of 1.2 equivalents Base hex- 1- alcohol is dissolved in 10 equivalent tetrahydrofurans and 3 equivalent n,N-Dimethylformamide, and 1.2 equivalents are then added dropwise thereto Thionyl chloride obtains mixture；It heats the mixture to 70 DEG C to react at least 2 days, until TLC shows the R2 of 1.0 equivalent of raw material Acid completely consume after, mixture is washed with water；Organic phase is concentrated to and is used thin layer chromatography, uses PE:EA=5:1-1:1 Elution, obtains 3,5- dimethoxy-4 ' hydroxycinnamic acid (2- ethyl) own ester.

4. a kind of wide spectrum suncream, which is characterized in that including component and its weight percent are as follows:

5. a kind of preparation method for preparing wide spectrum suncream as claimed in claim 4, which comprises the following steps:

Zinc oxide is added in glycerol and is uniformly mixing to obtain mixture A by step 1；

Tween 80, pot marigold extracting solution and tea polyphenols are added in distilled water step 2, are uniformly mixing to obtain mixture B；

Mixture B is added in mixture A by step 3, add vaseline, 3- methoxy cinnamic acid (2- ethyl) own ester and 3,5- dimethoxy-4 ' hydroxycinnamic acids (2- ethyl) own ester, stirs evenly, obtains mixture C；

Step 4 emulsifies the mixture C of step 3, as gained；

Above steps carries out at ambient temperature and pressure.