CN111454155A - Skin penetration enhancer, preparation method thereof and application thereof in cosmetics - Google Patents
Skin penetration enhancer, preparation method thereof and application thereof in cosmetics Download PDFInfo
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Abstract
The invention provides a transdermal absorption enhancer, a preparation method thereof and application thereof in cosmetics. The transdermal absorption enhancer is prepared from the following raw materials: di-menthyl phthalate, Chinese medicinal volatile oil, and propylene glycol; the di-menthyl phthalate has a structure shown in the following formula I. The invention adopts the combination of the traditional Chinese medicine volatile oil and the di-menthyl phthalate, so that the change of the skin ultrastructure is the largest, and the synergistic effect on the transdermal absorption effect is shown.
Description
Technical Field
The invention relates to the technical field of cosmetics, in particular to a transdermal absorption enhancer, a preparation method thereof and application thereof in cosmetics.
Background
However, the skin care products are burdened by excessive nutrients which cannot be absorbed by the skin, which causes 'skin oxidation', but cannot play a role in delaying aging, and rather accelerates skin aging. Bacteria on the skin surface require a large amount of vitamins, proteins and biological cell nutrients during their growth and reproduction, which are the main components of nutritional cosmetics. If the nutrients of the cosmetic are not completely absorbed by the skin, he becomes a hotbed for the growth and propagation of parasitic bacteria, and the large amount of bacteria also causes skin infections. In addition, in the existing transdermal drug delivery preparation, macromolecular drugs and fat-soluble drugs are difficult to permeate into the skin, so that the related drugs cannot exert the due drug effects. It is thus clear that the development of a percutaneous absorption enhancer in a percutaneous preparation and a cosmetic is of great significance for the development of a percutaneous preparation and a cosmetic.
Currently, the common transdermal absorption enhancers can be divided into: (1) organic solvents: ethanol, propylene glycol, ethyl acetate, dimethyl sulfoxide, and dimethyl imide; (2) surfactants: cationic surfactants, anionic surfactants, nonionic surfactants; (3) laurocapram and its homologs; (4) organic acids, fatty acids: oleic acid, linoleic acid and lauryl alcohol; (5) cutin moisturizing and softening agent: urea, salicylic acid and pyrrolidones; (6) terpenes: di-menthyl phthalate, camphor, limonene, and the like. In addition, amino acids, as well as some water-soluble proteins, phospholipids, etc., can also increase the dermal absorption of many drugs. However, the common transdermal absorption enhancers have the defects of irritation to skin after long-term use, toxicity to body organs after systemic absorption, difficult production and high cost. In addition, the existing transdermal enhancers have the following problems: the transdermal efficiency is low, and the absorption amount of the effective substances through pores is not more than 10%; toxic and harmful components exist, and the toxicity is strong; the structure is unstable and the moisture retention is poor. The above problems are not favorable for popularization and application of the transdermal enhancer. Therefore, the obtained multifunctional transdermal absorption enhancer which is low in cost, good in transdermal absorption promoting effect, good in moisturizing effect, good in biocompatibility and biodegradable has very important significance for improving the permeability of cosmetics and transdermal drug delivery preparations and promoting the wide application of the cosmetics and the transdermal drug delivery preparations.
Disclosure of Invention
The invention aims to provide a transdermal absorption enhancer, a preparation method thereof and application thereof in cosmetics.
The technical scheme of the invention is realized as follows:
a di-menthyl phthalate having the structure shown in formula I:
the invention provides a transdermal absorption enhancer, which is prepared from the following raw materials: di-menthyl phthalate, Chinese medicinal volatile oil, and propylene glycol.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 5-10 parts of di-menthyl phthalate, 1-3 parts of traditional Chinese medicine volatile oil and 20-50 parts of propylene glycol.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 6-9 parts of di-menthyl phthalate, 2-3 parts of traditional Chinese medicine volatile oil and 35-45 parts of propylene glycol.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 7 parts of di-menthyl phthalate, 2 parts of traditional Chinese medicine volatile oil and 35 parts of propylene glycol.
As a further improvement of the invention, the Chinese medicinal volatile oil is one or a mixture of more than two of dry ginger oil, clove oil, cubeb oil, Chinese amomum oil, tsaoko oil, amomum cardamomum oil, grassleaf sweelflag rhizome volatile oil, nutmeg volatile oil, orange peel volatile oil and zanthoxylum oil.
As a further improvement of the invention, the preparation method of the di-menthyl phthalate comprises the following steps:
s1, mixing phthalic acid and thionyl chloride, heating and reacting to generate phthaloyl chloride with a structure of
S2, heating phthaloyl chloride and menthol for reaction to generate the product of the di-menthyl phthalate.
As a further improvement of the invention, the preparation method of the di-menthyl phthalate specifically comprises the following steps:
s1, mixing phthalic acid and thionyl chloride, heating to 50-70 ℃, refluxing for 1-3h, and removing excessive thionyl chloride under reduced pressure to obtain phthaloyl chloride;
the mass ratio of phthalic acid to thionyl chloride is 1: (7-10);
s2, dissolving phthaloyl chloride in dichloromethane, cooling to-5 ℃, adding anhydrous pyridine and menthol under the stirring condition, slowly heating to 30-45 ℃, stirring for reacting for 2-4h, adding 1 mol/L hydrochloric acid into the organic phase for washing, separating liquid, washing with saturated sodium chloride solution, separating liquid, and then using anhydrous Na2SO4Drying the organic phase, filtering, and removing the solvent by the organic phase under reduced pressure to obtain the di-menthyl phthalate;
the mass ratio of the phthaloyl chloride to the anhydrous pyridine to the menthol is 1: (3-7): (1.9-2.2).
The invention further provides a preparation method of the transdermal absorption enhancer, which comprises the following steps: dissolving di-menthyl phthalate in propylene glycol, adding the Chinese medicinal volatile oil while stirring, mixing, and dispersing at high speed to obtain the skin penetration enhancer.
As a further improvement of the invention, the condition of high-speed dispersion is 10000-12000r/min homogenization for 1-2 min.
The invention further protects the application of the transdermal absorption enhancer in cosmetics.
The invention has the following beneficial effects: the synthesized di-menthyl phthalate has simple preparation method, wide raw material source and high yield, and the prepared di-menthyl phthalate has better antibacterial property and good transdermal absorption effect, can cause the change of skin ultrastructure and mainly shows that keratinocytes are loose, the intercellular space is increased and the pore diameter of the hair follicle opening is widened;
the added traditional Chinese medicine volatile oil is a large category of important active ingredients, has strong pharmacological activity, has strong transdermal absorption promoting effect and small irritation to skin, also has certain treatment effect, and can generate synergistic effect with the transdermally absorbed medicines;
when the Chinese medicinal volatile oil and the di-menthyl phthalate are used together, the change of the skin ultrastructure is the largest, which shows that the Chinese medicinal volatile oil and the di-menthyl phthalate have synergistic effect on the effect of transdermal absorption.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
EXAMPLE 1 preparation of di-menthyl phthalate
The synthetic route is as follows:
the preparation method specifically comprises the following steps:
s1, mixing 1mol of phthalic acid and 7mol of thionyl chloride, heating to 50 ℃, refluxing for 1h, and removing excessive thionyl chloride under reduced pressure to obtain phthaloyl chloride;
s2, dissolving 1mol of phthaloyl chloride in 200m of L methylene chloride, cooling to-5 ℃, and stirring in a stirring barAdding 3mol of anhydrous pyridine and 1.9mol of menthol, slowly heating to 30 ℃, stirring for reaction for 2 hours, adding 1 mol/L hydrochloric acid into the organic phase for washing, separating liquid, washing with saturated sodium chloride solution, separating liquid, and then using anhydrous Na2SO4The organic phase is dried, filtered and the organic phase is decompressed to remove the solvent, so that the di-menthyl phthalate is obtained with the yield of 90 percent.
The molecular structure of the di-menthyl phthalate is characterized in that (400MHz, CDCl)3)8.01(d,2H),7.57(d,2H),3.91(td,2H),2.01(m,2H),1.91-1.92(m,2H),1.82-1.83(m,2H),1.61-1.62(m,2H),1.52-1.55(m,4H),1.27-1.29(m,4H),1.09(d,6H),1.01(d,12H)。
EXAMPLE 2 preparation of di-menthyl phthalate
The preparation method specifically comprises the following steps:
s1, mixing 1mol of phthalic acid and 10mol of thionyl chloride, heating to 70 ℃, refluxing for 3 hours, and removing excessive thionyl chloride under reduced pressure to obtain phthaloyl chloride;
s2, dissolving 1mol of phthaloyl chloride in 200m L dichloromethane, cooling to-5 ℃, adding 7mol of anhydrous pyridine and 2.2mol of menthol under stirring, slowly heating to 45 ℃, stirring for reacting for 4h, adding 1 mol/L hydrochloric acid into the organic phase for washing, separating liquid, washing with saturated sodium chloride solution, separating liquid, and then using anhydrous Na2SO4The organic phase was dried, filtered and the solvent removed under reduced pressure from the organic phase to give the di-menthyl phthalate in a yield of 93%.
EXAMPLE 3 preparation of di-menthyl phthalate
The preparation method specifically comprises the following steps:
s1, mixing 1mol of phthalic acid and 8.5mol of thionyl chloride, heating to 60 ℃, refluxing for 2 hours, and removing excessive thionyl chloride under reduced pressure to obtain phthaloyl chloride;
s2, dissolving 1mol of phthaloyl chloride in 200m L dichloromethane, cooling to-5 ℃, adding 5mol of anhydrous pyridine and 2mol of menthol under stirring, slowly heating to 37 ℃, stirring for reacting for 3h, adding 1 mol/L hydrochloric acid into the organic phase for washing, separating liquid, washing with saturated sodium chloride solution, separating liquid, and then using anhydrous Na2SO4DryingFiltering the organic phase, and removing the solvent by the organic phase under reduced pressure to obtain the di-menthyl phthalate with the yield of 95 percent.
Example 4
The raw materials comprise the following components in parts by weight: 5 parts of di-menthyl phthalate, 1 part of dried ginger oil and 20 parts of propylene glycol.
The preparation method comprises the following steps: dissolving di-menthyl phthalate in propylene glycol, adding dried ginger oil while stirring, uniformly mixing, and uniformly dispersing at high speed under the condition of 10000r/min for 1min to obtain the transdermal absorption enhancer.
Example 5
The raw materials comprise the following components in parts by weight: 10 parts of di-menthyl phthalate, 3 parts of zanthoxylum oil and 50 parts of propylene glycol.
The preparation method comprises the following steps: dissolving the di-menthyl phthalate in propylene glycol, adding the zanthoxylum oil while stirring, uniformly mixing, and then uniformly dispersing at high speed, wherein the high-speed dispersion condition is 12000r/min and homogenizing for 2min, thus obtaining the transdermal absorption enhancer.
Example 6
The raw materials comprise the following components in parts by weight: 6 parts of di-menthyl phthalate, 2 parts of nutmeg volatile oil and 35 parts of propylene glycol.
The preparation method comprises the following steps: dissolving the di-menthyl phthalate in propylene glycol, adding the nutmeg volatile oil while stirring, uniformly mixing, and uniformly dispersing at a high speed for 1min under the condition of 10500r/min to obtain the transdermal absorption enhancer.
Example 7
The raw materials comprise the following components in parts by weight: 9 parts of di-menthyl phthalate, 3 parts of orange peel volatile oil and 45 parts of propylene glycol.
The preparation method comprises the following steps: dissolving the di-menthyl phthalate in propylene glycol, adding the orange peel volatile oil while stirring, uniformly mixing, and uniformly dispersing at a high speed for 2min under the condition of 11500r/min to obtain the transdermal absorption enhancer.
Example 8
The raw materials comprise the following components in parts by weight: 7 parts of di-menthyl phthalate, 2 parts of clove oil and 35 parts of propylene glycol.
The preparation method comprises the following steps: dissolving the di-menthyl phthalate in propylene glycol, adding clove oil while stirring, uniformly mixing, and then uniformly dispersing at a high speed, wherein the condition of high-speed dispersion is 11000r/min and homogenizing for 1.5min, thus obtaining the transdermal absorption enhancer.
Comparative example 1
In comparison with example 8, the other conditions were not changed without adding the di-menthyl phthalate.
The raw materials comprise the following components in parts by weight: clove oil 9 parts and propylene glycol 35 parts.
The preparation method comprises the following steps: dissolving clove oil in propylene glycol, uniformly mixing, and then uniformly dispersing at a high speed, wherein the condition of high-speed dispersion is 11000r/min for homogenizing for 1.5min, thus obtaining the transdermal absorption enhancer.
Comparative example 2
Compared to example 8, no clove oil was added, and the other conditions were unchanged.
The raw materials comprise the following components in parts by weight: 9 parts of di-menthyl phthalate and 35 parts of propylene glycol.
The preparation method comprises the following steps: dissolving the di-menthyl phthalate in propylene glycol, uniformly mixing, and then uniformly dispersing at a high speed, wherein the condition of high-speed dispersion is 11000r/min for homogenizing for 1.5min, thus obtaining the transdermal absorption enhancer.
Test example 1
The transdermal absorption enhancers prepared in examples 4-8 and comparative examples 1-2 of the invention are added into the anti-aging skin care product in the lancome black bottle, the addition amount of the transdermal absorption enhancer is 0.2 wt% of the anti-aging skin care product, the blank control group is added with deionized water with the same amount, and the detection is carried out by a GM71-DK-SKIRn skin tester produced by Beijing technology Limited company of the Western chemical instruments.
The test method comprises measuring skin state of the subject under the test environment temperature of 25 deg.C and humidity of 50%, respectively taking 2cm × 2cm area on both sides of face of each subject, coating the anti-aging skin care product with skin penetration enhancer on the left side of the face, coating the anti-aging skin care product with herba Cardamomi small black bottle 0.5m L on the right side of the face, coating the anti-aging skin care product with the same volume of the anti-aging skin care product with the.
TABLE 1 comparative data for consumer versus skin care product usage
| Test items | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Comparative example 1 | Comparative example 2 | Blank control |
| Water content | The improvement is 54 percent | Increase by 55 percent | The improvement is 51 percent | Increase by 57 percent | Increase by 60 percent | The improvement is 20 percent | Increase by 23% | Increase by 22% |
| Texture | The improvement is 47 percent | The improvement is 45 percent | Increase by 49 percent | The improvement is 51 percent | Increase by 55 percent | The improvement is 17 percent | The improvement is 14 percent | The improvement is 15 percent |
| Skin tone | Increase by 42 percent | The improvement is 45 percent | The improvement is 44 percent | The improvement is 43 percent | Increase by 49 percent | Increase by 8 percent | Increase by 8 percent | The improvement is 7 percent |
| Pigment | Reduce by 40% | Reduce by 45 percent | Reduce by 48 percent | The reduction is 47 percent | The reduction is 51 percent | The reduction is 10 percent | The reduction is 11 percent | The reduction is 9 percent |
| Elasticity | The improvement is 58 percent | Increase by 60 percent | Increase by 56 percent | The improvement is 62 percent | The improvement is 65 percent | Increase by 25% | The improvement is 18 percent | The improvement is 20 percent |
In table 1, the indexes of the anti-aging skin care products added with the skin penetration enhancers prepared in examples 4 to 8 are all higher than those of comparative examples 1 and 2 and the blank control by using water as the blank control, and the skin condition can be improved more obviously and the state of the skin can be restored by adding the anti-aging skin care products with the skin penetration enhancers prepared by the invention.
In the comparative example 1 and the comparative example 2, the dimesna phthalate or the clove oil is not added respectively, the indexes of the dimesna phthalate or the clove oil are obviously reduced and are not much different from those of a blank control group, and the addition of the dimesna phthalate and the clove oil has a synergistic effect.
Test example 2 in vivo experiment of transdermal absorption enhancer for collagen absorption
Kunming mice, 72, weighing 18-22g, were randomly divided into three groups of 8 mice each, and were administered in groups as follows:
model control group, coated with collagen, 0.1mg/m L.
Water-soluble azone group, coating collagen (0.1mg/m L) + water-soluble azone (0.2 wt%).
Examples 4-8 groups collagen (0.1mg/m L) + transdermal absorption enhancer (0.2 wt%) prepared in examples 4-8 were applied to obtain collagen solution of example 4, collagen solution of example 5, collagen solution of example 6, collagen solution of example 7 and collagen solution of example 8 in this order.
Comparative example 1-2 group collagen (0.1mg/m L) + transdermal absorption enhancer (0.2 wt%) prepared in comparative example 1-2 were applied to obtain a collagen solution of comparative example 1 and a collagen solution of comparative example 2 in this order.
Taking a male mouse with the weight of 18-22g, breaking the neck, killing the male mouse, shaving the belly hair, taking the skin without damage, removing subcutaneous fat on a petri dish, washing the inner surface of the skin with physiological saline, refrigerating and storing at-4 ℃, using the device within 48 hours, fixing the skin between an upper chamber and a lower chamber of a Franz diffusion cell, enabling the stratum corneum to face upwards, taking a 0.9% physiological saline solution as a receiving solution, taking a sample solution of 3m L as a release solution, placing the device in a constant-temperature water bath of (32 +/-0.5) DEG C, starting stirring (200r/min), respectively taking samples of 1m L for 0.5h, 1h, 2h, 4h, 6h, 8h, 10h and 12h, simultaneously not adding an equal-volume of fresh receiving solution at the same temperature, using a 0.22 mu m microporous filter membrane for the sample, taking a sample filtrate of 1m L, diluting with a mobile phase, carrying out ultraviolet quantitative analysis, calculating the cumulative permeation quantity (Qn) of the medicine, and taking an average operation of three.
TABLE 2 Effect of different penetration enhancers on the transdermal absorption of collagen
| Group of | n | Qn(μg/cm2)(12h) |
| Model control group | 8 | 0 |
| Water-soluble azone group | 8 | 235.13±11.24 |
| EXAMPLE 4 group | 8 | 1778.35±13.21 |
| EXAMPLE 5 group | 8 | 1757.25±15.23 |
| EXAMPLE 6 group | 8 | 1799.24±21.25 |
| EXAMPLE 7 group | 8 | 1823.53±38.26 |
| EXAMPLE 8 group | 8 | 1852.67±31.56 |
| Comparative example 1 group | 8 | 324.24±10.24 |
| Comparative example 2 group | 8 | 392.56±9.15 |
As is clear from Table 2, the skin penetration enhancers prepared in examples 4 to 8 of the present invention significantly improved the skin penetration of collagen compared to collagen monomers (blank). The permeation amount was significantly higher than in comparative examples 1, 2 and the water-soluble azone group.
In comparative example 1 and comparative example 2, the dimemyl phthalate or the clove oil is not added respectively, the permeation amount is obviously reduced and is not much different from that of a blank control group, and the addition of the dimemyl phthalate and the clove oil has a synergistic effect.
Compared with the prior art, the synthesized di-menthyl phthalate has simple preparation method, wide raw material source and high yield, and the prepared di-menthyl phthalate has better antibacterial property and good transdermal absorption effect, can cause the change of the skin ultrastructure and mainly shows that the keratinocyte is loose, the intercellular space is increased, and the pore diameter of the hair follicle opening is widened;
the added traditional Chinese medicine volatile oil is a large category of important active ingredients, has strong pharmacological activity, has strong transdermal absorption promoting effect and small irritation to skin, also has certain treatment effect, and can generate synergistic effect with the transdermally absorbed medicines;
when the Chinese medicinal volatile oil and the di-menthyl phthalate are used together, the change of the skin ultrastructure is the largest, which shows that the Chinese medicinal volatile oil and the di-menthyl phthalate have synergistic effect on the effect of transdermal absorption.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A di-menthyl phthalate having the structure shown in formula I:
2. the transdermal absorption enhancer is characterized by being prepared from the following raw materials in parts by weight: the di-menthyl phthalate of claim 1, which comprises 5-10 parts of di-menthyl phthalate, 1-3 parts of traditional Chinese medicine volatile oil and 20-50 parts of propylene glycol.
3. The transdermal absorption enhancer as claimed in claim 2, which is prepared from the following raw materials in parts by weight: 6-9 parts of di-menthyl phthalate, 2-3 parts of traditional Chinese medicine volatile oil and 35-45 parts of propylene glycol according to claim 1.
4. The transdermal absorption enhancer as claimed in claim 3, which is prepared from the following raw materials in parts by weight: the di-menthyl phthalate of claim 1, 2 parts of traditional Chinese medicine volatile oil and 35 parts of propylene glycol.
5. The transdermal absorption enhancer according to any one of claims 2 to 4, wherein the volatile oil of the traditional Chinese medicine is one or a mixture of two or more selected from the group consisting of ginger oil, clove oil, cubeb oil, Chinese amomum oil, tsaoko oil, cardamon oil, grassleaf sweelflag rhizome volatile oil, nutmeg volatile oil, orange peel volatile oil and zanthoxylum oil.
6. The method of claim 1 for the preparation of a di-menthyl phthalate comprising:
s1, mixing phthalic acid and thionyl chloride, heating and reacting to generate phthaloyl chloride with a structure of
S2, heating phthaloyl chloride and menthol for reaction to generate the product of the di-menthyl phthalate.
7. The method for preparing di-menthyl phthalate according to claim 6, specifically comprising:
s1, mixing phthalic acid and thionyl chloride, heating to 50-70 ℃, refluxing for 1-3h, and removing excessive thionyl chloride under reduced pressure to obtain phthaloyl chloride;
the mass ratio of phthalic acid to thionyl chloride is 1: (7-10);
s2, dissolving phthaloyl chloride in dichloromethane, cooling to-5 ℃, adding anhydrous pyridine and menthol under the stirring condition, slowly heating to 30-45 ℃, stirring for reacting for 2-4h, adding 1 mol/L hydrochloric acid into the organic phase for washing, separating liquid, washing with saturated sodium chloride solution, separating liquid, and then using anhydrous Na2SO4Drying the organic phase, filtering, and removing the solvent by the organic phase under reduced pressure to obtain the di-menthyl phthalate;
the mass ratio of the phthaloyl chloride to the anhydrous pyridine to the menthol is 1: (3-7): (1.9-2.2).
8. A process for producing a percutaneous absorption enhancer according to any one of claims 2 to 5, which comprises the steps of: dissolving di-menthyl phthalate in propylene glycol, adding the Chinese medicinal volatile oil while stirring, mixing, and dispersing at high speed to obtain the skin penetration enhancer.
9. The method for preparing a transdermal absorption enhancer as claimed in claim 8, wherein the high speed dispersion condition is 10000-12000r/min homogenization for 1-2 min.
10. A skin penetration enhancer according to any one of claims 2 to 5 for use in cosmetics.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010342240.5A CN111454155A (en) | 2020-04-27 | 2020-04-27 | Skin penetration enhancer, preparation method thereof and application thereof in cosmetics |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010342240.5A CN111454155A (en) | 2020-04-27 | 2020-04-27 | Skin penetration enhancer, preparation method thereof and application thereof in cosmetics |
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| CN111454155A true CN111454155A (en) | 2020-07-28 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4526872Y1 (en) * | 1966-03-23 | 1970-10-19 | ||
| EP0228064A2 (en) * | 1985-12-24 | 1987-07-08 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Photographic elements with sterically hindered photographic coupler solvents |
| EP0353714A2 (en) * | 1988-08-04 | 1990-02-07 | Fuji Photo Film Co., Ltd. | Silver halide photographic photosensitive materials |
| EP0426043A2 (en) * | 1989-10-30 | 1991-05-08 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material and method for forming color image |
| CN101157612A (en) * | 2007-11-13 | 2008-04-09 | 沈阳药科大学 | Organic acid menthol derivative and transdermal drug delivery preparation having the same |
| CN103179970A (en) * | 2010-09-30 | 2013-06-26 | 富山化学工业株式会社 | Transdermal absorption preparation |
-
2020
- 2020-04-27 CN CN202010342240.5A patent/CN111454155A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4526872Y1 (en) * | 1966-03-23 | 1970-10-19 | ||
| EP0228064A2 (en) * | 1985-12-24 | 1987-07-08 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Photographic elements with sterically hindered photographic coupler solvents |
| EP0353714A2 (en) * | 1988-08-04 | 1990-02-07 | Fuji Photo Film Co., Ltd. | Silver halide photographic photosensitive materials |
| EP0426043A2 (en) * | 1989-10-30 | 1991-05-08 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material and method for forming color image |
| CN101157612A (en) * | 2007-11-13 | 2008-04-09 | 沈阳药科大学 | Organic acid menthol derivative and transdermal drug delivery preparation having the same |
| CN103179970A (en) * | 2010-09-30 | 2013-06-26 | 富山化学工业株式会社 | Transdermal absorption preparation |
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