WO2021213028A1 - 一种可产氢发热保温的夹心面膜 - Google Patents

一种可产氢发热保温的夹心面膜 Download PDF

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Publication number
WO2021213028A1
WO2021213028A1 PCT/CN2021/079620 CN2021079620W WO2021213028A1 WO 2021213028 A1 WO2021213028 A1 WO 2021213028A1 CN 2021079620 W CN2021079620 W CN 2021079620W WO 2021213028 A1 WO2021213028 A1 WO 2021213028A1
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WIPO (PCT)
Prior art keywords
substrate layer
sandwich
hydrogen production
mask
water
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PCT/CN2021/079620
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English (en)
French (fr)
Inventor
周平乐
钟明伟
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杭州氢源素生物科技有限公司
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Publication of WO2021213028A1 publication Critical patent/WO2021213028A1/zh

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0212—Face masks
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M37/00—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/08—Anti-ageing preparations
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M37/00—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin
    • A61M2037/0007—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin having means for enhancing the permeation of substances through the epidermis, e.g. using suction or depression, electric or magnetic fields, sound waves or chemical agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to the technical field of facial masks, in particular to a sandwich facial mask capable of producing hydrogen, heating and heat preservation.
  • the facial masks currently on the market are mainly formed by sealing and packaging the mask cloth soaked in a large amount of nutrient solution.
  • the pores of the facial skin of the user will shrink, which not only fails to achieve the purpose of absorbing the nutrient solution, but also increases the user's discomfort.
  • the purpose of the present invention is to provide a sandwich mask that can produce hydrogen, heat The process generates heat, has good stability when placed in the air, and has high thermal insulation.
  • a sandwich mask capable of producing hydrogen, heating and heat preservation comprising a surface substrate layer, a water-permeable bottom substrate layer, and a hydrolyzable hydrogen production material arranged between the surface substrate layer and the bottom substrate layer;
  • An insulation layer is also provided on the outer surface of the surface substrate layer
  • the hydrolyzable hydrogen production material is a solid powder, and includes 10 to 90 parts by weight of at least one of sodium borohydride and metal hydride, 5 to 60 parts of a neutralizer, and 5 to 50 parts of an adsorbent.
  • the facial mask of the present invention is provided with a surface substrate layer, a water-permeable bottom substrate layer, and a hydrolyzable hydrogen production material is arranged between the surface substrate layer and the bottom substrate layer.
  • the outer side of the layer is provided with a thermal insulation layer.
  • the hydrolyzable hydrogen production material can react with water or alcohol to generate hydrogen and generate heat. When using it, moisten the bottom substrate layer of the mask or infiltrate the face after coating water to provide the required reaction water.
  • the hydrolyzable hydrogen production material needs to react with water or alcohol, which improves the stability of the mask in the air, thereby reducing the sealing process requirements, and the hydrolyzable hydrogen production material is located in the middle, and the heat dissipation to the air is slow, the heat loss is low, and the heat preservation The layer further reduces the heat loss of the heat generated by the reaction of the hydrolyzable hydrogen production material.
  • the metal hydride is at least one of calcium hydride, lithium hydride, and sodium hydride with a particle size of 0.5 to 500 ⁇ m.
  • the powdered metal hydride has a large specific surface area in contact with water, which can improve the efficiency of hydrogen production by hydrolysis.
  • the neutralizer is at least one of citric acid, oxalic acid, and phosphoric acid solid powder with a particle size of 1 to 500 ⁇ m;
  • the adsorbent is diatomaceous earth, molecular sieve, and zeolite with a particle size of 1 to 500 ⁇ m , At least one of activated carbon and foamed carbon solid powder.
  • Citric acid can neutralize the alkaline substances generated by the reaction of metal hydride or sodium borohydride, maintain the neutral environment of the mask, and reduce the irritation of the mask.
  • the adsorption material not only provides a reaction place, but also adsorbs and removes the smell of hydrogen.
  • the hydrolyzable hydrogen production material further includes 2 to 5 parts of hydrophilic fumed silica with a particle size of 20-100 nm.
  • Hydrophilic nano-silica has strong hydrophilic properties, which can assist in water trapping, enhance the water trapping and wetting ability of the hydrolyzable hydrogen production material, and improve the reaction efficiency.
  • the activity of the hydroxyl groups on the surface of the hydrophilic nano-silica is low, which is not enough to react with sodium borohydride or metal hydride, ensuring the stability of the hydrolyzable hydrogen production material.
  • the metal hydride or sodium borohydride is used after being treated by the following process: adding a hydrophilic gas phase with a particle size of 20-100nm to an acetone solution with a polyethylene glycol concentration of 10-40g/L The silica is uniformly dispersed, with a dispersion concentration of 10-25g/L, and then the metal hydride or sodium borohydride is dispersed in an acetone solution with a dispersion concentration of 50-450g/L. After standing, it is evaporated and dissolved, dried, and crushed for processing. The latter metal hydride or sodium borohydride.
  • polyethylene glycol has low reactivity and will not react with sodium borohydride or metal hydride, but polyethylene glycol has good hydrophilic properties, which helps to enhance the water-trapping capacity of hydrolyzable hydrogen production materials .
  • the inventor found that the stability of the hydrolyzable hydrogen production material after the above-mentioned process treatment is also significantly enhanced over a period of time. This may be because polyethylene glycol has a long-chain structure and is fully dissolved in acetone.
  • the long-chain structure of alcohol wraps around hydrophilic nano-silica and hydrogen-containing compounds, and has a synergistic effect with the three-dimensional network structure of hydrophilic nano-silica, which improves the hydrophilic fumed silica and metal hydride or
  • the binding strength of sodium borohydride at the same time, it has the effect of accumulating and accumulating water (forming a lake) in the presence of a large amount of water, and promotes the hydrogen production reaction; in a dry air environment, it works together with hydrophilic nano silica to bind water Function to prevent metal hydride or sodium borohydride from contacting with water to react.
  • the storage time increases, the accumulation of water and accumulation of water increase. When the water absorption reaches a certain level, the chance of contact between metal hydride or sodium borohydride and water is increased, resulting in a decrease in stability after a suitable storage time and a decrease in hydrogen production effect. .
  • the surface substrate layer is one of non-woven fabric, plastic film, and cotton cloth; the bottom substrate layer is one of water-permeable non-woven fabric, cotton cloth, and water-permeable film;
  • the thermal insulation layer is made of aluminum powder or silver powder coated on the outer side of the surface substrate layer.
  • the heat preservation layer is made of aluminum powder or silver powder coating, which will not be consumed with the reaction, and the heat preservation ability is stable.
  • the bottom substrate layer and the surface substrate layer are respectively correspondingly joined at the outer edge, the edge of the eye hole, the edge of the nostril, and the edge of the mouth hole; the bottom substrate The layer and the surface substrate layer have a number of joints evenly distributed at their respective non-edges; the corresponding joints of the bottom substrate layer and the surface substrate layer are pressed together to form a pressed line and/or pressed surface. Pattern.
  • a method for preparing the above sandwich mask includes the following steps:
  • step (4) Cut the sandwich film obtained in step (4) to obtain a sandwich mask.
  • the thickness of the obtained sandwich mask is 0.6-10 mm.
  • the sandwich facial mask of the present invention reacts with the moisture or moisturizing moisture provided by other facial masks, provides heat and generates hydrogen gas, and can be directly rinsed with clean water after use.
  • the sandwich mask of the present invention can produce hydrogen reaction after contacting with water, release heat, has low heat loss, and has high storage stability in the air, and the hydrogen production material is separately arranged between the bottom substrate layer and the surface substrate layer. It can prevent contamination of other nutrients and prevent contamination.
  • Figure 1 is a schematic diagram of the structure of the sandwich mask of the present invention.
  • Fig. 2 is a front view of the male face mask of the sandwich mask of the present invention.
  • Fig. 3 is a front view of the female face mask of the sandwich mask of the present invention.
  • Fig. 4 is a hydrogen production curve diagram of the hydrolyzable hydrogen production material in Example 1 in contact with different reaction systems.
  • Fig. 5 is a graph showing hydrogen production curves of the hydrolyzable hydrogen production material in Example 1 after being exposed to air for different periods of time.
  • the raw materials used in the present invention can be purchased from the market or commonly used in the field.
  • the methods in the following examples are conventional methods in the field.
  • the structure of the sandwich mask of the present invention is as follows:
  • a sandwich mask capable of generating hydrogen, heating and heat preservation includes a surface base material layer 1, a water-permeable bottom base material layer 3, and a hydrolyzable preparation set between the surface base material layer and the bottom base material layer.
  • Hydrogen material layer 2 the hydrolyzable hydrogen production material layer is formed by filling and laying solid powdery hydrolyzable hydrogen production material between the surface substrate layer and the bottom substrate layer, and is formed by pressing on the outer surface of the surface substrate layer.
  • Layer 4
  • the surface substrate layer is a non-woven fabric layer, which of course can also be replaced with a plastic film layer or a cotton cloth layer; when the surface substrate layer is a plastic film layer, the plastic film is preferably food-grade PP plastic.
  • the bottom substrate layer is a water-permeable film layer, of course, it can also be replaced with a water-permeable non-woven fabric layer or a cotton cloth layer; the thermal insulation layer is made of aluminum powder coated on the outer surface of the surface substrate layer, of course, it can also be replaced by coating Silver powder.
  • the bottom substrate layer and the surface substrate layer of the sandwich mask are correspondingly joined at the respective outer edges, the edges of the eye holes, the edges of the nostrils, and the edges of the mouth holes.
  • the preparation method of the sandwich mask of the present invention is as follows:
  • the bottom substrate layer on the hydrolyzable hydrogen production material, so that the bottom substrate layer and the surface substrate layer are at their respective outer edges, the edges of the eye holes, and the edges of the nostrils.
  • the edges of the mouth holes are respectively joined correspondingly to obtain a three-layer sandwich structure.
  • the thickness of the bottom substrate layer is 0.15mm;
  • the three-layer sandwich structure obtained in the pressing treatment step (3) obtains a one-piece sandwich film with a pressing pattern with a total thickness of 0.9mm, so that the bottom substrate layer and the surface substrate layer are on the non-edge
  • the joints are evenly joined to form evenly distributed joints, and a pattern composed of pressing lines and pressing surfaces is produced.
  • the thickness of the mask at the pressing lines is 0.6mm;
  • step (4) Cut the sandwich film obtained in step (4) to obtain a sandwich mask.
  • the thickness of the sandwich mask is determined by the thickness of the bottom substrate layer, the surface substrate layer, the thermal insulation layer, and the laid hydrolyzable hydrogen production materials, and the proper thickness range for the whole after lamination is 0.6-1mm.
  • composition of the hydrolyzable hydrogen production material of the sandwich mask of the present invention is as shown in the following embodiments, but is not limited to the solutions of the following embodiments.
  • Hydrolyzable hydrogen production material 1 including 5g from a mixture of 20g calcium hydride powder with a particle size of 70 ⁇ m, 45g of citric acid with a particle size of 200 ⁇ m, and 35g of diatomaceous earth with a particle size of 100 ⁇ m;
  • the mixture is pulverized and mixed uniformly with citric acid and diatomaceous earth, dried at 60°C, cooled and then mixed and pulverized with calcium hydride, and then mixed in a mixer at a speed of 500 rpm for 10 minutes.
  • the hydrolyzable hydrogen production material can react with the water mist formed by the mixed solution of water, water and glycerol and propylene glycol, and the time to reach the maximum hydrogen production is rapid. At the same time, it can be seen that the reaction capacity of the water mist formed by the hydrolyzable hydrogen production material and water is stronger than the water mist formed by the alcohol-containing solution, the reaction is rapid and the maximum hydrogen production is high.
  • the hydrolyzable hydrogen production material of Example 1 was exposed for a period of time in a clean environment at 25°C and a relative humidity of 45%, and then 0.1g of the hydrolyzable hydrogen production material and 20 mL of 50% water at a temperature of 20°C were taken.
  • the water mist reaction formed by 30% glycerol + 20% propylene glycol draw the hydrogen production curve under different storage time: exposure to air for 0 days (- ⁇ -:), exposure to air for 2 months (- ⁇ -: ), exposed to the air for 4 months (- ⁇ -), exposed to the air for 6 months (- ⁇ -), and exposed to the air for 8 months (- ⁇ -).
  • the results are shown in Figure 5.
  • the second hydrolyzable hydrogen production material is different from Example 1 in that the adsorbent material used is molecular sieve Na 2 O•3(Al 2 O 3 )•5(SiO 2 )•8(H 2 O).
  • the third hydrolyzable hydrogen production material is different from Example 1 in that the neutralizing agent used is oxalic acid.
  • Hydrolyzable hydrogen production material 4 including 5g from a mixture of 30g calcium hydride powder with a particle size of 70 ⁇ m, 55g of citric acid with a particle size of 200 ⁇ m, and 15g of diatomaceous earth with a particle size of 100 ⁇ m.
  • Hydrolyzable hydrogen production material 5 including 5g from a mixture of 20g sodium borohydride powder with a particle size of 70 ⁇ m, 45g of citric acid with a particle size of 200 ⁇ m and 35g of diatomaceous earth with a particle size of 100 ⁇ m.
  • the storage stability of the hydrolyzable hydrogen production material prepared in this example is equivalent to that of Example 1.
  • the hydrogen production rate at the beginning of the reaction is relatively lower than that of Example 1, but the hydrogen production capacity can reach a longer reaction time. And exceed Example 1.
  • Hydrolyzable hydrogen production material 6 compared with Example 1, the difference is that the mass of calcium hydride powder in the mixture is 35g and the particle size is 100 ⁇ m; the mass of citric acid powder is 30g and the particle size is 20 ⁇ m; the mass of diatomite powder is 45g and the particle size is 200 ⁇ m.
  • Hydrolyzable hydrogen production material No. 7 differs from Example 1 in that the mixture also includes 2 g of hydrophilic fumed nano silica with a particle size of 20 nm.
  • the mixture is prepared by the following process: Weigh the formula amount of calcium hydride, citric acid and diatomaceous earth, first pulverize and mix the citric acid and diatomaceous earth, then dry at 60°C, and then combine the calcium hydride powder and hydrophilicity. The fumed nano-silica is evenly mixed. After cooling the two materials, they are mixed and crushed, and then mixed in a mixer at a speed of 500 rpm for 10 minutes.
  • Example 1 Compared with Example 1, the hydrogen production rate of the hydrogen production material prepared in this example is equivalent, the maximum hydrogen production is increased by 2%, and the hydrogen production capacity after being exposed to the air for 8 months is reduced by 13.5%.
  • Hydrolyzable hydrogen production material 8 The mixture includes 20g calcium hydride powder with a particle size of 70 ⁇ m, 45g citric acid with a particle size of 200 ⁇ m, and 35g of diatomaceous earth with a particle size of 100 ⁇ m;
  • the calcium hydride powder is used after the following process: Disperse hydrophilic fumed nano silica with a particle size of 20nm in an acetone solution with a polyethylene glycol concentration of 10g/L, a dispersion concentration of 12.5g/L, ultrasonic dispersion Uniform, the ultrasonic power is 45w, the ultrasonic time is 90 minutes, and then the calcium hydride powder is uniformly dispersed in the acetone solution with a dispersion concentration of 50g/L. After standing at room temperature for 24 hours, the solvent is evaporated, dried, broken and processed After the calcium hydride.
  • the mixture is prepared by the following process: weighing the formula amount of calcium hydride, citric acid and diatomaceous earth, pulverizing and mixing the citric acid and diatomaceous earth uniformly, drying at 60°C, cooling and then mixing with the treated calcium hydride Mix and pulverize, and then mix for 10 minutes in the mixer at 500 rpm.
  • the hydrogen production rate of the hydrolyzable hydrogen production material obtained in this example is equivalent to that of Example 1.
  • the maximum hydrogen production is increased by 3.5%, and the hydrogen production capacity after 8 months of storage is reduced by 9.3%.
  • Hydrolyzable hydrogen production material 9 is different from Example 8 in that the concentration of polyethylene glycol in acetone solution during the treatment of calcium hydride powder is 40g/L, the dispersion concentration of calcium hydride powder is 25g/L, and the hydrogenation The dispersion concentration of calcium powder is 100 g/L.
  • the hydrogen production rate of the hydrolyzable hydrogen production material of this example is equivalent to that of Example 1.
  • the maximum hydrogen production is increased by 3.7%, and the hydrogen production capacity after 8 months of storage is reduced by 8.8%.
  • Hydrolyzable hydrogen production material ten The difference from Example 8 is that the mass of calcium hydride powder used in the mixture is 25g, the concentration of polyethylene glycol acetone solution in the calcium hydride powder treatment is 20g/L, calcium hydride powder The dispersion concentration of calcium hydride powder is 10g/L, and the dispersion concentration of calcium hydride powder is 40g/L.
  • the hydrogen production rate of the hydrolyzable hydrogen production material of this example is equivalent to that of Example 1.
  • the maximum hydrogen production is increased by 3.8%, and the hydrogen production capacity after 8 months of storage is reduced by 8.5%.
  • Example 8 The difference from Example 8 is that the adsorbent material used is molecular sieve Na 2 O•3(Al 2 O 3 )•5(SiO 2 )•8(H 2 O).
  • the hydrogen production rate of the hydrolyzable hydrogen production material prepared in this example is equivalent to that of Example 1, the maximum hydrogen production is increased by 3.0%, and the hydrogen production capacity after 8 months of storage is reduced by 11.3%.
  • This embodiment uses molecular sieve as the adsorption material to improve the stability of storage compared with diatomaceous earth.
  • the inventor speculates that the possible reason is that the surface of diatomaceous earth also contains hydroxyl groups, and the treated calcium hydride has the affinity
  • the hydroxyl groups of the aqueous gas phase nano-silica and polyethylene glycol form hydrogen bonds with the hydroxyl groups on the surface of diatomaceous earth, which improves the stability of the entire hydrolyzable hydrogen production material system.
  • the inventors further used activated carbon, zeolite, foamed carbon, etc. as the adsorption material to improve the storage stability of the hydrolyzable hydrogen production material under the same conditions, which is also weaker than that of Example 8.
  • the above method of use can also have other modifications, such as spraying water-containing emulsion or nutrient solution on the bottom substrate layer, or spraying a mixed solution of water and glycerol; or sticking other water-containing or nutrient solution masks on the bottom substrate
  • step (1) water or alcohol that can be hydrolyzed to produce hydrogen is provided.
  • the sandwich mask containing the hydrolyzable hydrogen-producing material of the above-mentioned embodiment was applied to 55 female volunteer testers aged 28-33 according to the above-mentioned spraying water application method. They were randomly divided into 11 groups and used continuously for 4 weeks and 6 weeks. The anti-wrinkle efficacy is evaluated after 8 weeks, and it is used every Monday, Wednesday, and Saturday, combined with visual inspection of eye wrinkles and photo display for judgment. In addition, 5 female testers with the same conditions were randomly searched as a control group to use a mask test without a layer of hydrolyzable hydrogen production material.
  • the criteria for judging the smoothness of skin fine lines are divided into 7 grades, namely: 0 no wrinkles; 1 slightly visible and inconspicuous shallow wrinkles; 2 slightly visible and obvious shallow wrinkles; 3 slightly visible and obvious shallow wrinkles; 4 slightly visible and obvious shallow wrinkles There are slightly deep wrinkles in the wrinkles; 5 slightly deep wrinkles can be seen; 6 obvious deep wrinkles can be seen; 7 very obvious deep wrinkles can be seen.
  • the testers in the experimental group and the control group were in the 5th level before the experiment. This verification test mainly observes that the smoothness of fine lines can be reduced by several grades after the user uses the mask of the above-mentioned embodiment and the control mask for a period of time. Generally speaking, the lower the number of grades, the better. The results are shown in Table 1.
  • the smoothness of fine lines can basically be reduced by 1 level, but with continued use to 6 weeks or even longer, the mask of the present invention can achieve fine lines
  • the effect of reducing the smoothness by 2 levels is even higher, while the ordinary water mask can not keep the reduction more.
  • the inventor believes that this should be because the moisture absorbed by the control group floats on the skin surface, and really absorbs very little; and the facial mask of the present invention can absorb more moisture and nutrients by the skin due to the effect of heating and hydrogen production. Improve the reduction of the smoothness of skin fine lines.

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Abstract

一种可产氢发热保温的夹心面膜，包括表面基材层、透水性的底面基材层和设置在表面基材层与底面基材层之间的可水解制氢材料；在表面基材层的外表面还设有保温层；所述可水解制氢材料为固体粉末状，包括重量份的硼氢化钠和金属氢化物中的至少一种10～90份、中和剂5～60份和吸附材料5～50份。

Description

一种可产氢发热保温的夹心面膜 技术领域
本发明涉及面膜技术领域，具体涉及一种可产氢发热保温的夹心面膜。
 背景技术
市场上的面膜目前主要是由浸润于大量营养液中的面膜布经密封包装形成。但是冷冰冰的面膜在天气寒冷的季节使用时，会让使用者面部皮肤毛孔收缩，不仅达不到吸收营养液的目的，还会造成使用者的不舒适感增强。
中国专利CN201810358280.1，专利名称“自发热面膜及其制备方法”公开了一种由营养层、导热层和发热层组成的可自发热面膜，发热层朝向空气，利用发热层的发热活性材料与空气接触氧化反应产热来达到加热目的。但是这种发热面膜要求发热层需要隔绝空气保存，对面膜的真空密封性能要求比较高；且发热层暴露在空气中设置，热量流失大。同时面膜的营养层中通常含有各种精华液，包含保湿剂、抗氧化剂、抗衰保湿剂、消炎剂等，由于发热层与营养层集成在一张面膜基材上，容易导致营养成分以及水等液体成分渗透到发热层，使得发热活性材料变质、逐渐失去活性，降低发热效果；同时发热层中的活性材料会污染精华液，容易造成皮肤过敏或其他皮肤疾病，给使用者带来不好的体验。
现有研究表明氢气能够消除活性自由基，并对氧自由基及能量代谢层面进行改善，所以对于体内发生的多种疾病如心脑血管、糖尿病、尿酸高等均有很好的改善控制作用。同时氢气分子体积小，可以非常容易的进入细胞内如细胞核和线粒体等部位，穿透性极强，因此给药途径很广，可以通过呼吸、饮用、经皮肤和注射等方式直接摄入人体，因此医疗用氢需求前景广阔。目前市场上的产氢面膜主要是将制氢材料混合成膏状后涂覆在面部，这样使用时会对面部皮肤产生灼烧感，引起皮肤刺激性，而且氢气吸收效率低。因此通过将产氢与面膜结构结合，利用产氢反应的反应热满足面膜的发热性能，并通过面膜结构改善氢气的吸收具有积极意义。
 技术问题
针对现有发热面膜利用发热材料与空气反应导致面膜密封性能要求比较高，而且发热材料暴露在空气中热量散失快，本发明的目的在于提供一种可产氢发热保温的夹心面膜，利用制氢过程发热，在空气中放置的稳定性好，同时保温性高。
 技术解决方案
本发明提供如下的技术方案：
一种可产氢发热保温的夹心面膜，所述夹心面膜包括表面基材层、透水性的底面基材层和设置在表面基材层与底面基材层之间的可水解制氢材料；
在表面基材层的外表面还设有保温层；
所述可水解制氢材料为固体粉末状，包括重量份的硼氢化钠和金属氢化物中的至少一种10~90份、中和剂5~60份和吸附材料5~50份。
与现有技术相比，本发明的面膜设有表面基材层、透水性的底面基材层，并在表面基材层和底面基材层之间设置可水解制氢材料，在表面基材层的外侧设置保温层，可水解制氢材料可与水或醇接触反应产生氢气并发热，使用时将面膜的底面基材层一侧润湿或者在脸部涂覆水后浸润提供反应所需的水。这样可水解制氢材料需与水或醇反应，提高了面膜在空气中的稳定性高，因此降低了密封工艺要求，而且可水解制氢材料位于中间，向空气散热慢，热量流失低，保温层则进一步降低了可水解制氢材料反应产生的热的热量流失。
作为本发明的改进，所述金属氢化物为粒径0.5~500μm的氢化钙、氢化锂、氢化钠中的至少一种。粉末状的金属氢化物与水接触的比表面积大，能够提高水解制氢的效率。
作为本发明的改进，所述中和剂为粒径1~500μm的柠檬酸、草酸、磷酸固体粉末中的至少一种；所述吸附材料为粒径1~500μm的硅藻土、分子筛、沸石、活性炭和泡沫碳固体粉末中的至少一种。柠檬酸等可以中和金属氢化物或硼氢化钠反应生成的碱性物质，保持面膜的中性环境，降低面膜的反应刺激性。吸附材料既提供反应场所，同时可以吸附去除氢气中的味道。
作为本发明的改进，所述可水解制氢材料中还包括粒径为20～100nm的亲水性气相二氧化硅2～5份。亲水性纳米二氧化硅具有极强的亲水性能，可以辅助捕水，增强可水解制氢材料的捕水和润湿能力，提高反应效率。同时亲水性纳米二氧化硅表面的羟基的活性低，不足以与硼氢化钠或金属氢化物反应，保证了可水解制氢材料的稳定性。
作为本发明的改进，所述金属氢化物或硼氢化钠经以下过程处理后使用：在聚乙二醇浓度为10～40g/L的丙酮溶液中加入粒径为20～100nm的亲水性气相二氧化硅分散均匀，分散浓度为10～25g/L，然后将金属氢化物或硼氢化钠分散在丙酮溶液中，分散浓度为50～450g/L，静置后蒸发溶解并干燥、破碎得到处理后的金属氢化物或硼氢化钠。聚乙二醇中含有的羟基反应活性低不会与硼氢化钠或金属氢化物发生反应，但是聚乙二醇具有很好的亲水性能，有助于增强可水解制氢材料的捕水能力。同时发明人发现，经过上述过程处理后的可水解制氢材料放置一段时间内的稳定性也有明显的增强，这可能是因为聚乙二醇具有长链结构并在丙酮中充分溶解，聚乙二醇的长链结构缠绕亲水性纳米二氧化硅和含氢化合物，并与亲水性纳米二氧化硅的三维网状结构发生协同作用，提高了亲水型气相二氧化硅与金属氢化物或者硼氢化钠的结合强度，同时在大量水存在下起到聚水、积水（成湖）效果，促进制氢反应；在干燥空气环境中则与亲水性纳米二氧化硅共同起到缚水作用，阻止金属氢化物或硼氢化钠与水接触反应。但是随放置时间增加，聚水、积水增多，当吸水达到一定程度后增加了金属氢化物或硼氢化钠与水的接触机会，导致超过适宜的放置时间后的稳定性降低，制氢效果下降。
作为本发明的改进，所述表面基材层为无纺布、塑料薄膜、棉布中的一种；所述底面基材层为透水性的无纺布、棉布、透水薄膜中的一种；所述保温层由铝粉或银粉涂覆在表面基材层的外侧面制成。保温层由铝粉或银粉涂覆制成，不会随反应消耗，保温能力稳定。
作为本发明的改进，所述底面基材层与表面基材层在各自的外边缘处、眼部孔边缘处、鼻部孔边缘处、口部孔边缘处分别对应接合；所述底面基材层与表面基材层在各自的非边缘处均匀分布有若干接合处；所述底面基材层与表面基材层相互对应接合处经压合形成由压合线条和/或压合面组成的图纹。
一种制备上述夹心面膜的方法，包括以下步骤：
（1）在表面基材层的一侧面上涂覆铝粉或银粉形成保温层；
（2）在表面基材层的另一侧面上按设定厚度均匀铺设可水解制氢材料；
（3）将底面基材层铺设在平铺开的可水解制氢材料上得到三层夹心结构；
（4）压合处理步骤（3）得到的三层夹心结构，得到一片式的带压合图纹的夹心膜片；
（5）裁剪步骤（4）得到的夹心膜片得到夹心面膜。
作为本发明方法的改进，所得夹心面膜的厚度为0.6～10mm。
一种使用上述夹心面膜的方法，其特征在于，包括以下步骤：
（1）将含有纯水或者水与丙三醇的其他面膜贴在温夹心面膜的底面基材层的外侧面或者在底面基材层的外侧面均匀喷洒一定量的水或以水为主要成份的溶液或乳液；
（2）将上述步骤（1）处理后的夹心面膜的底面基材层的外侧面贴附在脸上；
（3）贴附保持10～15分钟后取下夹心面膜，然后清水冲洗面部。
本发明的夹心面膜配合其他面膜提供的水分或者润湿的水分发生反应，提供热量并产生氢气，使用后直接清水冲洗即可。
 有益效果
本发明的有益效果如下：
本发明的夹心面膜具有可以在与水接触后发生制氢反应，释放热量，热量流失低，并且在空气中存放稳定性高，而且制氢材料单独设置在底面基材层与表面基材层之间，可以防止污染其他营养成分，并防止被污染。
 附图说明
图1是本发明的夹心面膜的结构示意图。
图2是本发明的夹心面膜的男款面膜的正面视图。
图3是本发明的夹心面膜的女款面膜的正面视图。
图中，1、表面基材层，2、可水解制氢材料层，3、底面基材层，4、保温层，5、压合线，6、压合面。
图4是实施例1中的可水解制氢材料与不同反应体系接触的制氢曲线图。
图5是实施例1中的可水解制氢材料暴露在空气不同时间后的制氢曲线图。
图4中：
-▲-：与水形成的水雾反应；
-●-：与50wt%水+30wt%丙三醇+20wt%丙二醇形成的水雾反应；
-■-：与20wt%水+50wt%丙三醇+30wt%丙二醇形成的水雾反应。
图5中：
-■-：暴露在空气中0天；
-●-：暴露在空气中2个月；
-▲-：暴露在空气中4个月；
-◄-：暴露在空气中6个月；
-♦-：暴露在空气中8个月。
 本发明的实施方式
下面就本发明的具体实施方式作进一步说明。
如无特别说明，本发明中所采用的原料均可从市场上购得或是本领域常用的，如无特别说明，下述实施例中的方法均为本领域的常规方法。
本发明的夹心面膜的结构如下：
一种可产氢发热保温的夹心面膜，如图1所示，包括表面基材层1、透水性的底面基材层3和设置在表面基材层与底面基材层之间的可水解制氢材料层2，可水解制氢材料层由固体粉末状的可水解制氢材料填充铺设在表面基材层和底面基材层之间压合形成，在表面基材层的外表面设有保温层4。
其中，表面基材层为无纺布层，当然也可以替换为塑料薄膜层或棉布层；当表面基材层为塑料薄膜层使，塑料薄膜优选食品级的PP塑料。底面基材层为透水薄膜层，当然也可以替换为透水性的无纺布层、棉布层；保温层由在表面基材层的外表面涂覆铝粉制成，当然也可以替换为涂覆银粉。
如图2和图3所示，夹心面膜的底面基材层与表面基材层在各自的外边缘处、眼部孔边缘处、鼻部孔边缘处、口部孔边缘处分别对应接合，在各自的非边缘处均匀分布有若干接合处；底面基材层与表面基材层在相互对应接合处经压合形成由压合线条5和压合面6组成的图纹。
本发明的夹心面膜的制备方法如下：
（1）在表面基材层的一侧面上涂覆铝粉或银粉形成厚度为0.2mm的保温层；
（2）在表面基材层的另一侧面上按设定厚度均匀铺设可水解制氢材料，形成可水解制氢材料层，厚度为0.3mm；
（3）将底面基材层铺设在平铺开的可水解制氢材料上，使底面基材层与表面基材层在各自的外边缘处、眼部孔边缘处、鼻部孔边缘处、口部孔边缘处分别对应接合，得到三层夹心结构。底面基材层厚度为0.15mm；
（4）压合处理步骤（3）得到的三层夹心结构，得到一片式的带压合图纹的夹心膜片，总厚度为0.9mm，使底面基材层和表面基材层在非边缘处均匀的接合，形成均匀分布的接合处，并产生由压合线条、压合面组成的图纹，压合纹处面膜厚度0.6mm；
（5）裁剪步骤（4）得到的夹心膜片得到夹心面膜。
当然需要说明的是，夹心面膜的厚度由底面基材层、表面基材层、保温层以及铺设的可水解制氢材料的厚度决定，压合后的整体的合适的厚度范围为0.6～1mm。
本发明的夹心面膜的可水解制氢材料的组成如下面实施例所示，但不局限于下述实施例的方案。
实施例1
可水解制氢材料一，包括从粒径为70μm的氢化钙粉末20g、粒径为200μm的柠檬酸45g和粒径为100μm的硅藻土35g的混合料中取5g；
该混合料将柠檬酸和硅藻土粉碎混匀后60℃烘干，冷却后再与氢化钙混合粉碎，然后500rpm的转速在混料机中混匀10min即可。
（1）制氢能力测试
将实施例1的可水解制氢材料0.10g分别与20mL的纯水、50wt%水+30wt%丙三醇+20wt%丙二醇、20wt%水+50wt%丙三醇+30wt%丙二醇形成的水雾发生接触反应，先测量产生氢气的体积，计算产氢量，然后绘制产氢量-时间的产氢曲线，得到与水形成的水雾反应的产氢曲线（-▲-）、与50wt%水+30wt%丙三醇+20wt%丙二醇形成的水雾反应的产氢曲线（-●-）、与20wt%水+50wt%丙三醇+30wt%丙二醇形成的水雾反应的产氢曲线（-■-），如图4所示。
从图4中可以看出，可水解制氢材料可以与水、水和丙三醇、丙二醇的混合溶液形成的水雾发生反应，而且达到最大产氢量的时间迅速。同时可以看出，可水解制氢材料与水形成的水雾的反应能力强于含醇的溶液形成的水雾，反应迅速且最大产氢量高。
（2）放置稳定性测试
将实施例1的可水解制氢材料在25℃、相对湿度为45%的清洁环境中暴露放置一段时间，然后取0.1g的可水解制氢材料与20mL、温度为20℃的50%水+30%丙三醇+20%丙二醇形成的水雾反应，绘制不同放置时间下的产氢曲线：暴露在空气中0天（-■-：）、暴露在空气中2个月（-●-：）、暴露在空气中4个月（-▲-）、暴露在空气中6个月（-◄-）、暴露在空气中8个月（-♦-），结果见图5所示。
从图中可以看出，随放置时间的增加，最大的产氢量逐渐降低，暴露2个月、4个月、6个月和8个月的最大的产氢量相对下降约2.6%、8.5%、12.0%和15.4%，因此暴露在空气中放置8个月后的制氢能力仍保持八成以上，具有较高的水解制氢效率。
实施例2
可水解制氢材料二，与实施例1的不同之处在于，所用吸附材料为分子筛Na 2O•3(Al 2O 3)•5(SiO 2)•8(H 2O)。
该实施例制备的可水解制氢材料的制氢能力和放置稳定性与实施例1相当。
实施例3
可水解制氢材料三，与实施例1的不同之处在于，所用中和剂为草酸。
实施例4
可水解制氢材料四，包括从粒径为70μm的氢化钙粉末30g、粒径在200μm的柠檬酸55g和粒径在100μm的硅藻土15g的混合料中取5g。
该实施例制备的可水解制氢材料的制氢能力和放置稳定性与实施例1相当。
实施例5
可水解制氢材料五，包括从粒径为70μm的硼氢化钠粉末20g、粒径在200μm的柠檬酸45g和粒径在100μm的硅藻土35g的混合料中取5g。
该实施例制备的可水解制氢材料的放置稳定性与实施例1相当，开始反应的制氢速率与实施例1相比相对有所降低，但是在更长反应时间内的制氢能力可以达到并超过实施例1。
实施例6
可水解制氢材料六，与实施例1相比不同之处在于，混合料中氢化钙粉末质量35g、粒径100μm；柠檬酸粉末质量30g、粒径20μm；硅藻土粉末质量45g、粒径200μm。
该实施例制备的可水解制氢材料的制氢能力和放置稳定性与实施例1相当。
实施例7
可水解制氢材料七，与实施例1的不同之处在于，混合料中还包括粒径为20nm的亲水性气相纳米二氧化硅2g。
该混合料经以下过程制得：称取配方量的氢化钙、柠檬酸和硅藻土，先将柠檬酸和硅藻土粉碎混匀后60℃烘干，然后将氢化钙粉末和亲水性气相纳米二氧化硅混合均匀，将两次物料冷却后混合粉碎，然后500rpm的转速在混料机中混匀10min即可。
该实施例制备的制氢材料与实施例1相比，制氢速率相当，最大的产氢量提高2%，暴露在空气中放置8个月后的制氢能力下降13.5%。
实施例8
可水解制氢材料八，该混合料包括粒径为70μm的氢化钙粉末20g、粒径为200μm的柠檬酸45g和粒径为100μm的硅藻土35g；
其中氢化钙粉末经以下过程处理后使用：将粒径为20nm的亲水性气相纳米二氧化硅分散在聚乙二醇浓度为10g/L的丙酮溶液中，分散浓度12.5g/L，超声分散均匀，超声功率为45w，超声时间90分钟，然后将氢化钙粉末超声均匀分散在该丙酮溶液中，分散浓度为50g/L，在室温下静置24小时后蒸发溶剂，并干燥、破碎得到处理后的氢化钙。
该混合料经以下过程制得：称取配方量的氢化钙、柠檬酸和硅藻土，先将柠檬酸和硅藻土粉碎混匀后60℃烘干，冷却后再与处理后的氢化钙混合粉碎，然后500rpm的转速在混料机中混匀10min即可。
该实施例所得可水解制氢材料的产氢速率与实施例1相当，最大的产氢量提升3.5%，放置8个月后的产氢能力下降9.3%。
实施例9
可水解制氢材料九，与实施例8的不同之处在于，氢化钙粉末处理过程中的聚乙二醇的丙酮溶液的浓度为40g/L、氢化钙粉末的分散浓度为25g/L、氢化钙粉末的分散浓度为100g/L。
该实施例的可水解制氢材料的产氢速率与实施例1相当，最大的产氢量提升3.7%，放置8个月后的产氢能力下降8.8%。
实施例10
可水解制氢材料十，与实施例8的不同之处在于，混合料中所用氢化钙粉末质量为25g，氢化钙粉末处理中聚乙二醇的丙酮溶液的浓度为20g/L、氢化钙粉末的分散浓度为10g/L、氢化钙粉末的分散浓度为40g/L。
该实施例的可水解制氢材料的产氢速率与实施例1相当，最大的产氢量提升3.8%，放置8个月后的产氢能力下降8.5%。
实施例11
与实施例8的不同之处在于，所用吸附材料为分子筛Na 2O•3(Al 2O 3)•5(SiO 2)•8(H 2O)。
该实施例制备的可水解制氢材料的产氢速率与实施例1相当，最大产氢量提升3.0%，放置8个月后的产氢能力下降11.3%。
该实施例以分子筛作为吸附材料后的放置稳定性提升能力与以硅藻土相比有所减弱，发明人推测可能原因是硅藻土的表面也含有羟基，处理后的氢化钙所具备的亲水性气相纳米二氧化硅和聚乙二醇的羟基与硅藻土的表面的羟基形成氢键，提高了整个可水解制氢材料体系的稳定性。同时发明人进一步的同样条件下以活性炭、沸石、泡沫碳等作为吸附材料后的可水解制氢材料的放置稳定性的提升效果亦弱于实施例8。
含有上述实施例的可水解制氢材料的夹心面膜的使用效果测试。
（一）含有上述实施例的可水解制氢材料的夹心面膜的方法如下：
（1）在上述夹心面膜的底面基材层的外侧均匀喷洒一层水，
（2）将上述喷洒水后的夹心面膜的底面基材层的外侧面贴附在脸上；
（3）贴附保持10～15分钟后取下夹心面膜，然后清水冲洗面部。
当然，上述使用方法也可有其他的变形，比如在底面基材层喷洒含水的乳液或营养液、或者喷洒水和丙三醇的混合溶液；或者将其他含水或营养液的面膜贴在底面基材层的外侧，以替代步骤（1）提供可水解制氢反应的水或醇。
（二）使用效果
将含上述实施例的可水解制氢材料的夹心面膜按照上述喷洒水的使用方法用于55名年龄为28～33岁的女性志愿测试者，随机分为11组，连续使用4周、6周和8周后对抗皱功效进行评价，每周的周一、三、六使用，结合眼角皱纹目测和照片显示给予评判。另随机寻找5名相同条件的女性测试者作为对照组使用无可水解制氢材料层的面膜测试。皮肤细纹光滑度的评判依据分为7级，分别是：0 无皱纹；1 微微可见不明显的浅皱纹；2 微微可见明显的浅皱纹；3 可见明显的浅皱纹；4 微微可见明显的浅皱纹中有稍深皱纹；5 可见稍深皱纹；6 可见明显的深皱纹；7 可见非常明显的深皱纹。实验组和对照组的测试者在实验前均处于第5等级状态。本验证试验主要观察使用者在使用一段时间上述实施例的面膜和对照组面膜后，其细纹光滑度可以降低几个等级数，一般而言，等级数降低的越多越好。其结果列于表1中。
从下表中可以看出，在使用4周基本上能达到细纹光滑度降低1个等级的效果，但随着继续使用至6周后甚至更长时间后，本发明的面膜可以实现细纹光滑度降低2个等级的效果甚至更高，而普通的水面膜则不能保持降低更多。发明人认为这应该是对照组被吸收的水分多浮于皮肤表面，真正吸收的非常少；而本发明的面膜由于加热和产氢的效果，使得皮肤能吸收更多水分和营养物质，能够进一步改善皮肤细纹光滑度的降低。
表1 使用效果表
Figure 948219dest_path_image001

Claims (10)

  1. 一种可产氢发热保温的夹心面膜，其特征在于，所述夹心面膜包括表面基材层、透水性的底面基材层和设置在表面基材层与底面基材层之间的可水解制氢材料；
    在表面基材层的外表面还设有保温层；
    所述可水解制氢材料为固体粉末状，包括重量份的硼氢化钠和金属氢化物中的至少一种10~90份、中和剂5~60份和吸附材料5~50份。
  2. 根据权利要求1所述的可产氢发热保温的夹心面膜，其特征在于，所述金属氢化物为氢化钙、氢化锂、氢化钠中的至少一种，粒径为0.5~500μm。
  3. 根据权利要求1或2所述的可产氢发热保温的夹心面膜，其特征在于，所述中和剂为粒径1~500μm的柠檬酸、草酸、磷酸固体粉末中的至少一种；所述吸附材料为粒径1~500μm的硅藻土、分子筛、沸石、活性炭和泡沫碳固体粉末中的至少一种。
  4. 根据权利要求1或2所述的可产氢发热保温的夹心面膜，其特征在于，所述可水解制氢材料中还包括粒径为20～100nm的亲水性气相二氧化硅2～5份。
  5. 根据权利要求1或2所述的可产氢发热保温的夹心面膜，其特征在于，所述金属氢化物或硼氢化钠经以下过程处理后使用：在聚乙二醇浓度为10～40g/L的丙酮溶液中加入粒径为20～100nm的亲水性气相二氧化硅分散均匀，分散浓度为10～25g/L，然后将金属氢化物或硼氢化钠分散在丙酮溶液中，分散浓度为50～450g/L，静置后蒸发溶解并干燥、破碎得到处理后的金属氢化物或硼氢化钠。
  6. 根据权利要求1所述的可产氢发热保温的夹心面膜，其特征在于，所述表面基材层为无纺布、塑料薄膜、棉布中的一种；所述底面基材层为透水性的无纺布、棉布、透水薄膜中的一种；所述保温层由铝粉或银粉涂覆在表面基材层的外侧面制成。
  7. 根据权利要求1或6所述的可产氢发热保温的夹心面膜，其特征在于，所述底面基材层与表面基材层在各自的外边缘处、眼部孔边缘处、鼻部孔边缘处、口部孔边缘处分别对应接合；所述底面基材层与表面基材层在各自的非边缘处均匀分布有若干接合处；所述底面基材层与表面基材层相互对应接合处经压合形成由压合线条和/或压合面组成的图纹。
  8. 一种制备如权利要求1至7任一所述的夹心面膜的方法，其特征在于，包括以下步骤：
    （1）在表面基材层的一侧面上涂覆铝粉或银粉形成保温层；
    （2）在表面基材层的另一侧面上按设定厚度均匀铺设可水解制氢材料；
    （3）将底面基材层铺设在平铺开的可水解制氢材料上得到三层夹心结构；
    （4）压合处理步骤（3）得到的三层夹心结构，得到一片式的带压合图纹的夹心膜片；
    （5）裁剪步骤（4）得到的夹心膜片得到夹心面膜。
  9. 根据权利要求8所述的制备方法，其特征在于，所得夹心面膜的厚度为0.6～1mm。
  10. 一种使用如权利要求1至7任一所述的夹心面膜的方法，其特征在于，包括以下步骤：
    （1）将含有纯水或者水与丙三醇的其他面膜贴在温夹心面膜的底面基材层的外侧面或者在底面基材层的外侧面均匀喷洒一定量的水或以水为主要成份的溶液或乳液；
    （2）将上述步骤（1）处理后的夹心面膜的底面基材层的外侧面贴附在脸上；
    （3）贴附保持10～15分钟后取下夹心面膜，然后清水冲洗面部。
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