WO2016006127A1 - Composition for preparing carbon dioxide formulation for external use, method for producing same, method for evaluating same, and carbon dioxide formulation for external use - Google Patents

Composition for preparing carbon dioxide formulation for external use, method for producing same, method for evaluating same, and carbon dioxide formulation for external use Download PDF

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Publication number
WO2016006127A1
WO2016006127A1 PCT/JP2014/077043 JP2014077043W WO2016006127A1 WO 2016006127 A1 WO2016006127 A1 WO 2016006127A1 JP 2014077043 W JP2014077043 W JP 2014077043W WO 2016006127 A1 WO2016006127 A1 WO 2016006127A1
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carbon dioxide
composition
external preparation
dioxide external
water
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PCT/JP2014/077043
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French (fr)
Japanese (ja)
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朱美 大和谷
更家 勝
亮介 西
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株式会社アイビーティジェイ
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Application filed by 株式会社アイビーティジェイ filed Critical 株式会社アイビーティジェイ
Priority to SG11201610558PA priority Critical patent/SG11201610558PA/en
Priority to KR1020177003471A priority patent/KR20170030583A/en
Priority to CN201480080524.4A priority patent/CN106535864B/en
Priority to KR1020187023249A priority patent/KR101958158B1/en
Publication of WO2016006127A1 publication Critical patent/WO2016006127A1/en
Priority to HK17104906.6A priority patent/HK1231368A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00Medicinal preparations containing inorganic active ingredients
    • A61K33/06Aluminium, calcium or magnesium; Compounds thereof, e.g. clay
    • A61K33/10Carbonates; Bicarbonates
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/08Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
    • A61K47/10Alcohols; Phenols; Salts thereof, e.g. glycerol; Polyethylene glycols [PEG]; Poloxamers; PEG/POE alkyl ethers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0212Face masks
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin

Definitions

  • This invention relates to the composition used for preparation of the carbon dioxide external preparation which mixes two or more agents at the time of use.
  • Patent Literature a technology for generating a carbon dioxide gas by mixing a basic composition containing a carbonate and an acidic composition such as a water-soluble acid in the presence of water is known (Patent Literature). 1 etc.).
  • carbon dioxide can be sustained by using substances that hydrolyze to produce acids, carbonates, thickeners, water, gelling agents that gel with calcium ions, and water-insoluble or poorly water-soluble calcium salts as essential ingredients.
  • a carbon dioxide external preparation that can be percutaneously / transmucosally absorbed and has a stronger beauty and medical effect can be easily prepared (see Patent Document 2, etc.).
  • the composition for preparing a carbon dioxide external preparation is one in which two or more agents are mixed and reacted at the time of use to generate carbon dioxide. Furthermore, when using a composition for preparing a carbon dioxide external preparation as a cosmetic pack, a gelling agent that gels with calcium ions and a water-insoluble or poorly water-soluble calcium salt are added to the composition for preparing a carbon dioxide external preparation. By doing so, it is known that the composition for preparing a carbon dioxide external preparation can be hardened.
  • the gelation speed and the gel hardness of the composition for preparing a carbon dioxide external preparation are not appropriate depending on the types and blending ratios of the gelling agent and the water-insoluble or poorly water-soluble calcium salt. That is, if the gelation is too fast, the composition for preparing a carbon dioxide external preparation has a problem that the elongation is poor when applied to the skin and the like, and sufficient carbon dioxide cannot be generated. On the other hand, if the gelation is too slow, the composition for preparing a carbon dioxide external preparation cannot be peeled cleanly from the skin surface by hand, and there is a problem that it is difficult to use as a pack agent.
  • the present invention has good elongation at the time of application to the skin or the like immediately after mixing of two or more agents, and from the amount of membrane-permeable carbon dioxide generated from a composition for preparing a carbon dioxide external preparation comprising conventionally known components.
  • Another object of the present invention is to provide a novel composition for preparing a carbon dioxide external preparation that generates a large amount of membrane-permeable carbon dioxide and hardens by the time of use.
  • Another object of the present invention is to provide a carbon dioxide external preparation and a cosmetic pack obtained from the novel composition for preparing carbon dioxide external preparation.
  • the present invention by containing a magnesium salt, a water-soluble calcium salt, a gelling agent that gels with magnesium ions or calcium ions, a carbonate, a substance that is hydrolyzed to generate an acid, a polyhydric alcohol, and water,
  • a magnesium salt a water-soluble calcium salt, a gelling agent that gels with magnesium ions or calcium ions, a carbonate, a substance that is hydrolyzed to generate an acid, a polyhydric alcohol, and water
  • the composition for preparing an external preparation for carbon dioxide divided into two or more agents is applied to the skin after mixing so that at least the carbonate and the substance that generates acid by hydrolysis are separately mixed, the mixture is applied from the mixing to the application.
  • the coating surface does not harden in such a state that the composition for preparing a carbon dioxide external preparation does not adhere to the hand that has touched the coating surface before, and the composition for preparing a carbon dioxide external preparation does not touch the skin by the end of use.
  • composition for preparing a carbon dioxide external preparation that gels so as not to be peeled off. That is, it is possible to provide a composition for preparing a carbon dioxide external preparation, which has good elongation when applied to the skin or the like, and is solidified to the extent that it can be peeled off by hand after the use time has elapsed.
  • a magnesium salt, a water-soluble calcium salt, a gelling agent that gels with magnesium ions or calcium ions, a carbonate, a substance that is hydrolyzed to generate an acid By containing a polyhydric alcohol and water, the amount of membrane-permeable carbon dioxide exceeding the amount of membrane-permeable carbon dioxide generated from the composition for preparing a carbon dioxide external preparation comprising components known in Patent Document 2 and the like Can be generated.
  • the composition for preparing a carbon dioxide external preparation of the present invention is for preparing a carbon dioxide external preparation in which two or more agents are mixed at the time of use, and gels with a magnesium salt, a water-soluble calcium salt, magnesium ion or calcium ion. It contains at least a gelling agent, a carbonate, a substance that is hydrolyzed to generate an acid, a polyhydric alcohol, and water, and may further contain other components as necessary.
  • the magnesium salt is not particularly limited as long as it has magnesium in its chemical structural formula and generates magnesium ions in water, and can be appropriately selected depending on the purpose.
  • magnesium may be used individually by 1 type, may use 2 or more types together, and may serve as other essential components, such as carbonate.
  • magnesium carbonate and magnesium oxide are preferable, and magnesium carbonate which also serves as a carbonate essential as a component of the composition for preparing carbon dioxide external preparation is more preferable.
  • the content of the magnesium salt with respect to the total amount of the composition for preparing carbon dioxide external preparation is not particularly limited and can be appropriately selected depending on the purpose.
  • the content exceeds 12% by mass, the time when the coated surface starts to harden and the time when the entire gel hardens to the extent that it can be peeled off without leaving the skin may be too short.
  • the content is less than 0.3% by mass, the time for the coating surface to start to solidify and the time for the gel to harden to the extent that it can be peeled without remaining on the skin become too long.
  • the water-soluble calcium salt is not particularly limited as long as it has calcium in its chemical structural formula and has water solubility and generates calcium ions in water, and can be appropriately selected depending on the purpose.
  • examples thereof include calcium chloride and calcium lactate. These may be used individually by 1 type, may use 2 or more types together, and may serve as another essential component.
  • a calcium salt that gels so that the composition for preparing a carbon dioxide external preparation by hand can be peeled off by the end of use is preferable, and calcium chloride is more preferable in terms of solubility in water.
  • the content of the water-soluble calcium salt (excluding water in the water-soluble calcium salt) with respect to the total amount of the composition for preparing carbon dioxide external preparation is not particularly limited and can be appropriately selected depending on the purpose.
  • the content is less than 0.003% by mass, the composition for preparing a carbon dioxide external preparation is not sufficiently gelled by the end of use and is difficult to peel off.
  • the content exceeds 0.05% by mass, the coating surface tends to harden from mixing to coating, and therefore it is preferably 0.003% by mass or more and 0.05% by mass or less. More preferably, it is at least 0.03% by mass.
  • the gelling agent that gels with magnesium ions or calcium ions is not particularly limited as long as it gels with magnesium ions generated from the magnesium salt or calcium ions generated from the water-soluble calcium salt, and is appropriately selected depending on the purpose. can do.
  • carrageenan, xanthan gum, tara gum, sodium alginate and the like can be mentioned. These may be used alone or in combination of two or more. Among these, sodium alginate and xanthan gum are preferable from the viewpoint of smoothness in application state and ease of use.
  • the content of the gelling agent that gels with magnesium ions or calcium ions with respect to the total amount of the composition for preparing a carbon dioxide external preparation is not particularly limited and can be appropriately selected depending on the purpose.
  • the content is less than 1.0% by mass, the composition for preparing a carbon dioxide external preparation is not sufficiently gelled, and it is difficult to obtain an effect as a skin external preparation.
  • it exceeds 7% by mass the coated surface tends to harden in a state where the composition for preparing a carbon dioxide external preparation does not adhere to the hand that touched the coated surface from mixing to coating.
  • the carbonate is not particularly limited as long as it is a carbonate that reacts with a substance that is hydrolyzed to generate an acid contained in the composition for preparing an external preparation for carbon dioxide, and is appropriately selected depending on the purpose. be able to.
  • ammonium carbonate, ammonium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, magnesium carbonate, magnesium hydrogen carbonate, calcium carbonate, calcium hydrogen carbonate, barium carbonate and the like can be mentioned. These may be used individually by 1 type, may use 2 or more types together, and may serve as other essential components, such as a magnesium salt and a calcium salt. Of these, magnesium carbonate, which also serves to generate magnesium ions, is more preferable.
  • the content of the carbonate with respect to the total amount of the composition for preparing a carbon dioxide external preparation is not particularly limited and can be appropriately selected depending on the purpose.
  • the content is less than 0.3% by mass, the generated amount of carbon dioxide is reduced, and the effect as an external preparation obtained by the generation of carbon dioxide is not sufficiently exhibited.
  • the content exceeds 12% by mass, the pH of the composition for preparing a carbon dioxide external preparation is high, and the generated carbon dioxide tends to exist as carbonate ions, so the amount of generated membrane-permeable carbon dioxide decreases. It is preferably 0.3% by mass or more and 12% by mass or less, and more preferably 0.5% by mass or more and 11% by mass or less.
  • the substance that generates an acid by hydrolysis is not particularly limited as long as it has one or more cyclic ester bonds in its molecular structure, and can be appropriately selected depending on the purpose.
  • glucono delta lactone and D, L-lactide are preferable, and glucono delta lactone is more preferable from the viewpoints of hydrolysis rate, acid generation rate that reacts with carbonate, and availability of compounds.
  • the content of the substance that is hydrolyzed to generate an acid with respect to the total amount of the composition for preparing a carbon dioxide external preparation is not particularly limited and can be appropriately selected depending on the purpose.
  • the content is less than 10% by mass, the amount of carbon dioxide generated by the reaction between the hydrolyzed acid and the carbonate decreases, and the effect as an external preparation obtained by carbon dioxide generation is not sufficiently exhibited.
  • the content exceeds 20% by mass, it is difficult to stir and mix with other components. Therefore, the content is preferably 10% by mass or more and 20% by mass or less, and more preferably 13% by mass or more and 18% by mass.
  • the polyhydric alcohol is not particularly limited as long as it has two or more hydroxyl groups in its molecular structure, and can be appropriately selected depending on the purpose.
  • examples include ethylene glycol, propylene glycol, 1,3-butylene glycol, polyethylene glycol, glycerin, 1,8-octanediol, glycerin that is a sugar alcohol, sorbitol, and trehalose that is also a sugar. These may be used alone or in combination of two or more. Among them, 1,3-butylene glycol is preferable from the viewpoint of shortening the gelation time and moisturizing.
  • the content of the polyhydric alcohol with respect to the total amount of the composition for preparing a carbon dioxide external preparation is not particularly limited and can be appropriately selected depending on the purpose.
  • the content is less than 5% by mass, the composition for preparing a carbon dioxide external preparation has a longer time for gelation after mixing two or more agents, and the composition for preparing a carbon dioxide external preparation by the end of use. Cannot be gelled so that it can be peeled off by hand.
  • the content exceeds 25% by mass, the coated surface hardens in such a state that the carbon dioxide external preparation preparation composition does not adhere to the hand that touched the coated surface from mixing to coating.
  • the mass is preferably from 25% by mass to 25% by mass, and more preferably from 5% by mass to 20% by mass.
  • the water contained in the composition for preparing a carbon dioxide external preparation is not particularly limited as long as it is water used for normal cosmetics, pharmaceuticals, and the like, and can be appropriately selected depending on the purpose.
  • distilled water, membrane permeated water, and ion exchange water can be mentioned. These may be used individually by 1 type, may use 2 or more types together, and may be contained as aqueous solution of other components, such as calcium chloride aqueous solution.
  • the content of the water with respect to the total amount of the composition for preparing a carbon dioxide external preparation is not particularly limited and can be appropriately selected depending on the purpose.
  • the content is a total of water and water contained in other components such as the water-soluble calcium salt, and is prepared so that the total amount of the carbon dioxide external preparation preparation composition is 100% by mass. Is done. Further, when the content is less than 55% by mass, the viscosity becomes high and fluidity, flexibility, and solubility of other components are lacking. Therefore, the content is preferably 55% by mass or more.
  • components of the carbon dioxide external preparation preparation composition are not particularly limited as long as they are components used in cosmetics and skin external preparations, and can be appropriately selected depending on the purpose.
  • surfactants for example, surfactants, pH adjusters, humectants, preservatives, antioxidants, fragrances, dispersants, ultraviolet absorbers, dyes and the like can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
  • the usage form of the carbon dioxide external preparation is not particularly limited and can be appropriately selected depending on the purpose.
  • a form used by mixing two or more gel-like agents when applied to the skin, etc. a form used by mixing two or more gel-like and granular agents when applied to the skin, granules, etc.
  • examples include a form in which a gel-like agent is mixed with water after being dissolved in water and then mixed at the time of application to the skin.
  • the method for evaluating the goodness of elongation of the carbon dioxide external preparation preparation composition when applied to the skin or the like is not particularly limited as long as it can show the goodness of elongation of the applied gel, and is selected according to the purpose. can do. For example, after mixing two or more agents and applying to the skin etc., the “time until the gel does not adhere to the finger when the application surface is touched” is defined as “the time when the application surface starts to solidify”, There is a method of evaluating the goodness of elongation by the length of the “time when the coated surface starts to harden”.
  • the evaluation method of the ease of peeling at the end of use can be any method that can show the ease of peeling and the tendency of the applied gel to be solidified.
  • the “time until the gel does not remain on the skin when peeled” is defined as “the time to peel off”, and the “time to peel off”
  • the method for evaluating the amount of carbon-permeable carbon dioxide generated in the composition for preparing a carbon dioxide external preparation is particularly limited as long as it can measure the amount of carbon dioxide that permeates through a membrane simulating a human skin environment. It can be appropriately selected depending on the purpose. For example, a method of immersing a porous polymer membrane in oil and fat and measuring the amount of carbon dioxide that permeates the membrane can be mentioned. In order to approach the human skin environment, a microporous film (manufactured by Sumitomo 3M, 3M microporous film, pore size of 0.3 ⁇ m or less) is used for the porous polymer film, and olive squalane (Kishimoto Special) is used for the fats and oils. A method using a carbon dioxide concentration meter (manufactured by Toa DKK Co., Ltd., model number CGP-31) is particularly preferable for measuring the amount of carbon dioxide permeated through a liver oil industry plant, plant squalane.
  • evaluation of the amount of membrane-permeable carbon dioxide generated in the composition for preparing a carbon dioxide external preparation was carried out by putting 1 g of a gel in which two or more agents were stirred and mixed into a container dedicated to a carbon dioxide concentration meter. Then, a microporous film coated with 0.1 g of olive squalane is covered, and a detector of a carbon dioxide concentration meter is attached to the dedicated container. A predetermined amount of water is added using a syringe so as to fill the space between the container and the detector, and the amount of membrane-permeable carbon dioxide generated is measured and recorded for 60 minutes every minute immediately after.
  • the carbon dioxide generated from the composition for preparing a carbon dioxide external preparation is further measured by further measuring the pH of the composition for preparing a carbon dioxide external preparation when membrane-permeable carbon dioxide is generated.
  • the state of carbon can be confirmed.
  • the method for measuring the pH is not particularly limited as long as it is a method capable of measuring the change over time of the pH of the composition for preparing an external preparation for carbon dioxide, and can be appropriately selected depending on the purpose. For example, a method of stirring and mixing two or more agents and measuring the pH of the composition for preparing a carbon dioxide external preparation over time using an everyday waterproof pH meter (manufactured by HANNA instruments, pHep4 HI98127) can be mentioned.
  • Examples 1 to 9 and Comparative Examples 1 to 3 According to the composition described in Table 1, a composition for preparing a carbon dioxide external preparation was prepared. In the examples in which magnesium carbonate that also serves as a magnesium salt and carbonate was blended, a composition for preparing a carbon dioxide external preparation was prepared with the blending amount of magnesium carbonate described in the table. And 0035 and the like, it was considered that the same amount of magnesium salt and carbonate was mixed. According to the blending amount described in Table 2, the agent divided into two was stirred and mixed until it became uniform visually before use.
  • the composition for preparing carbon dioxide external preparations was mixed according to the following evaluation method. Evaluation of good elongation at the time of application and ease of peeling at the end of use. After mixing two or more agents on the skin or the like, the “time until the gel does not adhere to the finger when the application surface is touched” is defined as the “time when the application surface starts to solidify”, and the “application surface is The time to start setting was measured. Next, after mixing two or more agents and applying to the skin, etc., the “time until the gel does not remain on the skin when peeled” was defined as the “time to remove”, and the “time to remove” was measured. .
  • the time for applying two or more agents of the composition for preparing a carbon dioxide external preparation to the skin after mixing was within 5 minutes, the time for the appropriate application surface to start to solidify was It was defined as 5-10 minutes.
  • the use time of the composition for preparing a carbon dioxide external preparation was 10 to 15 minutes, so the appropriate peeling time was defined as 10 to 15 minutes.
  • Table 3 shows the evaluation results of good elongation at the time of application to the skin after mixing and ease of peeling at the end of use.
  • Comparative Example 2 which does not contain a water-soluble calcium salt does not peel off after use, and is a water-soluble calcium salt.
  • Examples 3 and 4 where the compounding amount of calcium chloride is large, it was found that the time when the coating surface started to solidify was short and the elongation during coating was not good.
  • Comparative Example 1 in which magnesium carbonate is changed to sodium hydrogen carbonate, neither the coating surface nor the inside is hardened, and in Examples 7 and 8 in which the blending amount of magnesium carbonate is further increased, the time at which the coating surface begins to harden and the time to peel off are short. I found out that
  • Example 1 and Comparative Example 3 the amount of membrane-permeable carbon dioxide generation was evaluated by the following method.
  • 1 g of gel mixed with the two agents listed in Table 2 was put in a container dedicated to a carbon dioxide concentration meter, and a microporous film coated with 0.1 g of olive squalane was placed thereon, and the dedicated container Attach a carbon dioxide concentration meter detector.
  • a predetermined amount of water was added using a syringe so as to fill the space between the container and the detector, and the amount of carbon dioxide permeated through the membrane was measured and recorded every minute for 60 minutes.
  • Table 4 shows the test results of the amount of generated carbon permeable carbon dioxide.
  • Example 1 Based on Table 4, the time-dependent change of the membrane-permeable carbon dioxide generation amount of Example 1 and Comparative Example 3 is shown in FIG. From Table 4 and FIG. 1, when Example 1 was compared with Comparative Example 3 not containing magnesium ions and water-soluble calcium salt, the membrane-permeable dioxide up to 15 minutes, which was the assumed usage time of Example 1 after mixing, It can be seen that the carbon generation amount is about 1.2 times the membrane-permeable carbon dioxide generation amount of Comparative Example 3.
  • the pH was measured by the following method. The two agents described in Example 1 and Comparative Example 3 were stirred and mixed, and the pH of the composition for preparing a carbon dioxide external preparation was measured over time using an everyday waterproof pH meter (manufactured by HANNA instruments, pHep4 HI98127). . The measurement results of pH are shown in Table 5 and FIG.
  • Example 1 From Table 5 and FIG. 2, in Example 1, the pH drops immediately after mixing the two agents, and is maintained at pH 4.0 to 6.5 where membrane-permeable carbon dioxide is likely to be generated until 60 minutes have passed. I understood that.
  • composition for preparing carbon dioxide external preparations divided into two or more agents when the composition for preparing carbon dioxide external preparations divided into two or more agents is applied on the skin after mixing, it is applied to the hand touching the application surface from mixing to application.
  • the coating surface does not harden in such a state that the composition for preparing a carbon dioxide external preparation does not adhere, and the carbon dioxide external preparation composition is gelled so that the composition for preparing a carbon dioxide external preparation can be peeled off by the end of use.
  • the composition for carbon external preparation preparation can be provided. That is, it was found that when the composition for preparing an external preparation for carbon dioxide was applied to the skin or the like, the elongation was good, and it solidified to the extent that it could be peeled by hand after the use time.
  • the composition for preparing a carbon dioxide external preparation of the present invention comprises a magnesium salt, a water-soluble calcium salt, a gelling agent that gels with magnesium ions or calcium ions, a carbonate, a substance that is hydrolyzed to produce an acid, a polyvalent
  • a carbon dioxide external preparation comprising a component that is maintained at a pH of 4 to 6.5 and is known in Patent Document 2 in the period from the start of use to the end of use It has been found that membrane permeable carbon dioxide is generated in an amount exceeding the amount of membrane permeable carbon dioxide generated from the composition for use.
  • the effect is that by blending a component that generates magnesium ions such as magnesium carbonate, the ionic crosslinking of gelling agents such as sodium alginate and xanthan gum is made more gradual than when a component that generates calcium ions is blended. based on.
  • the blending of magnesium ions improves the elongation of the composition for preparing a carbon dioxide external preparation immediately after mixing, and contributes to hardening the entire gel.
  • the effect is that by adding calcium chloride, which is a water-soluble calcium salt, as a component that generates calcium ions, a gelling agent such as sodium alginate or xanthan gum is more effective than when water-insoluble or poorly water-soluble calcium carbonate is added.
  • the said effect adjusts the time which a coating surface begins to solidify, and the time to peel off by mix
  • the appropriate amount of the component that generates magnesium ions and the water-soluble calcium salt is selected from the conventionally known components that are mixed in an appropriate amount of water-insoluble or poorly water-soluble calcium salt as the component that generates calcium ions and do not include the component that generates magnesium ions. More membrane-permeable carbon dioxide can be generated than the amount of membrane-permeable carbon dioxide generated from the composition for preparing a carbon dioxide external preparation.
  • composition for preparing an external preparation for carbon dioxide of the present invention is easy to mix and prepare two or more agents, has a good elongation without being hardened by the time of application on the skin immediately after mixing, and the use time is over. It can be peeled off so as not to remain on the skin, and a sufficient amount of membrane-permeable carbon dioxide can be generated within the use time. Therefore, in a cosmetic pack that can continue moderate irritation to the skin, it stretches well at the time of application, peels off cleanly at the end, and has an effect as a so-called carbon dioxide gas pack. It can be suitably used for cosmetics such as agents, external preparations for skin, quasi-drugs such as hair preparations, pharmaceuticals, and pet products.
  • composition for preparing a carbon dioxide external preparation of the present invention has a characteristic that it is well stretched at the time of application and can be peeled off at the end of use, which is said to be incompatible with a so-called carbon dioxide gas pack in the beauty industry. For this reason, until now it was necessary to wipe off the lump of gel that could not be peeled off at the end of use with a towel, and there was a secondary problem in the washing process of towels that had been wiped off lump of gel. Solves such secondary problems.

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Abstract

The present invention addresses the problem of providing a novel composition for preparing carbon dioxide formulation for external use, said composition being highly spreadable on the skin immediately after mixing two or more agents until applying to the skin while preventing the surface of the applied composition from beginning to solidify, being capable of gelling so that the composition can be separated from the skin without remaining on the skin at the end of the use, and, during use period, generating membrane permeable carbon dioxide in an amount greater than the amount of membrane permeable carbon dioxide generated by a conventional composition for preparing carbon dioxide formulation for external use that comprises known components. Also, the present invention addresses the problem of providing a carbon dioxide formulation for external use and a cosmetic pack that are obtained from the novel composition for preparing carbon dioxide formulation. The composition for preparing carbon dioxide formulation at least comprises, as essential components, a gelling agent that gels in the presence of a magnesium salt, a water-soluble calcium salt, magnesium ion or calcium ion, a carbonic acid salt, a substance that generates an acid when hydrolyzed, a polyhydric alcohol and water.

Description

二酸化炭素外用剤調製用組成物、その製造方法及び評価方法、並びに二酸化炭素外用剤Composition for preparing carbon dioxide external preparation, production method and evaluation method thereof, and carbon dioxide external preparation
 本発明は、2以上の剤を使用時に混合する、二酸化炭素外用剤の調製に用いられる組成物に関する。 This invention relates to the composition used for preparation of the carbon dioxide external preparation which mixes two or more agents at the time of use.
 美容や医療効果を目的として、炭酸塩を含有する塩基性組成物と水溶性酸等の酸性組成物とを水の存在下において混合し、炭酸ガスを発生させる技術が知られている(特許文献1等参照)。
 また、加水分解されて酸を生じる物質、炭酸塩、増粘剤、水、カルシウムイオンによってゲル化するゲル化剤及び水不溶性又は水難溶性カルシウム塩を必須成分にすることにより、二酸化炭素が持続的に経皮・経粘膜吸収され、美容及び医療効果がより強力な二酸化炭素外用剤を容易に調製できることも知られている(特許文献2等参照)。
For the purpose of beauty and medical effects, a technology for generating a carbon dioxide gas by mixing a basic composition containing a carbonate and an acidic composition such as a water-soluble acid in the presence of water is known (Patent Literature). 1 etc.).
In addition, carbon dioxide can be sustained by using substances that hydrolyze to produce acids, carbonates, thickeners, water, gelling agents that gel with calcium ions, and water-insoluble or poorly water-soluble calcium salts as essential ingredients. It is also known that a carbon dioxide external preparation that can be percutaneously / transmucosally absorbed and has a stronger beauty and medical effect can be easily prepared (see Patent Document 2, etc.).
 二酸化炭素外用剤調製用組成物は、2以上の剤を使用時に混合し反応させて二酸化炭素を発生させるものである。
 さらに、二酸化炭素外用剤調製用組成物を化粧用パック剤に使用する場合は、二酸化炭素外用剤調製用組成物にカルシウムイオンによってゲル化するゲル化剤と、水不溶性又は水難溶性カルシウム塩を添加することで、二酸化炭素外用剤調製用組成物を固めることが可能であることが知られている。
The composition for preparing a carbon dioxide external preparation is one in which two or more agents are mixed and reacted at the time of use to generate carbon dioxide.
Furthermore, when using a composition for preparing a carbon dioxide external preparation as a cosmetic pack, a gelling agent that gels with calcium ions and a water-insoluble or poorly water-soluble calcium salt are added to the composition for preparing a carbon dioxide external preparation. By doing so, it is known that the composition for preparing a carbon dioxide external preparation can be hardened.
 しかしながら、前記ゲル化剤と前記水不溶性又は水難溶性カルシウム塩の種類や配合比により、二酸化炭素外用剤調製用組成物のゲル化の速度やゲルの硬さが適度にならない問題があった。すなわち、ゲル化が速すぎると、二酸化炭素外用剤調製用組成物は皮膚等に対する塗布時に伸びが悪くなり、かつ、十分な二酸化炭素を発生させることができないという問題があった。逆に、ゲル化が遅すぎると、二酸化炭素外用剤調製用組成物は皮膚表面から手できれいに剥がすことができず、パック剤として使用しにくいという問題があった。 However, there is a problem that the gelation speed and the gel hardness of the composition for preparing a carbon dioxide external preparation are not appropriate depending on the types and blending ratios of the gelling agent and the water-insoluble or poorly water-soluble calcium salt. That is, if the gelation is too fast, the composition for preparing a carbon dioxide external preparation has a problem that the elongation is poor when applied to the skin and the like, and sufficient carbon dioxide cannot be generated. On the other hand, if the gelation is too slow, the composition for preparing a carbon dioxide external preparation cannot be peeled cleanly from the skin surface by hand, and there is a problem that it is difficult to use as a pack agent.
特許第4248878号公報Japanese Patent No. 4248878 特許第4595058号公報Japanese Patent No. 4595058
 本発明は、2以上の剤の混合直後である皮膚等への塗布時には伸びがよく、従来より知られている成分からなる二酸化炭素外用剤調製用組成物から発生する膜透過性二酸化炭素量よりも多くの膜透過性二酸化炭素を発生させ、かつ、使用時間経過までに固まる新規な二酸化炭素外用剤調製用組成物を提供することを課題とする。また、本発明は、この新規な二酸化炭素外用剤調製用組成物から得られる二酸化炭素外用剤及び化粧用パックを提供することを課題とする。 The present invention has good elongation at the time of application to the skin or the like immediately after mixing of two or more agents, and from the amount of membrane-permeable carbon dioxide generated from a composition for preparing a carbon dioxide external preparation comprising conventionally known components. Another object of the present invention is to provide a novel composition for preparing a carbon dioxide external preparation that generates a large amount of membrane-permeable carbon dioxide and hardens by the time of use. Another object of the present invention is to provide a carbon dioxide external preparation and a cosmetic pack obtained from the novel composition for preparing carbon dioxide external preparation.
 本発明者らは、上記事情に鑑みて鋭意検討した結果、マグネシウム塩、水溶性カルシウム塩、マグネシウムイオン又はカルシウムイオンによってゲル化するゲル化剤、炭酸塩、加水分解されて酸を生じる物質、多価アルコール及び水を必須成分とする、二酸化炭素外用剤調製用組成物を見出した。 As a result of intensive studies in view of the above circumstances, the present inventors have found that magnesium salts, water-soluble calcium salts, gelling agents that gel with magnesium ions or calcium ions, carbonates, substances that are hydrolyzed to produce acids, many The composition for carbon dioxide external preparation preparation which used a monohydric alcohol and water as an essential component was discovered.
 本発明によれば、マグネシウム塩、水溶性カルシウム塩、マグネシウムイオン又はカルシウムイオンによってゲル化するゲル化剤、炭酸塩、加水分解されて酸を生じる物質、多価アルコール及び水を含有させることで、少なくとも前記炭酸塩及び前記加水分解されて酸を生じる物質を別に配合するように2以上の剤に分けた前記二酸化炭素外用剤調製用組成物を混合後に皮膚上に塗布した場合、混合から塗布時までに塗布表面を触れた手に二酸化炭素外用剤調製用組成物が付着しなくなるような状態に該塗布表面が固まらず、かつ、使用終了時までに二酸化炭素外用剤調製用組成物が肌に残らず剥離可能なようにゲル化する二酸化炭素外用剤調製用組成物を提供することができる。すなわち、二酸化炭素外用剤調製用組成物の皮膚等への塗布時には伸びが良く、使用時間経過後には手で剥離可能な程度に固まる、二酸化炭素外用剤調製用組成物を提供することができる。
 また、本発明の二酸化炭素外用剤調製用組成物によれば、マグネシウム塩、水溶性カルシウム塩、マグネシウムイオン又はカルシウムイオンによってゲル化するゲル化剤、炭酸塩、加水分解されて酸を生じる物質、多価アルコール及び水を含有させることで、特許文献2等で知られている成分からなる二酸化炭素外用剤調製用組成物から発生する膜透過性二酸化炭素量を超える量の膜透過性二酸化炭素を発生することができる。
According to the present invention, by containing a magnesium salt, a water-soluble calcium salt, a gelling agent that gels with magnesium ions or calcium ions, a carbonate, a substance that is hydrolyzed to generate an acid, a polyhydric alcohol, and water, When the composition for preparing an external preparation for carbon dioxide divided into two or more agents is applied to the skin after mixing so that at least the carbonate and the substance that generates acid by hydrolysis are separately mixed, the mixture is applied from the mixing to the application. The coating surface does not harden in such a state that the composition for preparing a carbon dioxide external preparation does not adhere to the hand that has touched the coating surface before, and the composition for preparing a carbon dioxide external preparation does not touch the skin by the end of use. It is possible to provide a composition for preparing a carbon dioxide external preparation that gels so as not to be peeled off. That is, it is possible to provide a composition for preparing a carbon dioxide external preparation, which has good elongation when applied to the skin or the like, and is solidified to the extent that it can be peeled off by hand after the use time has elapsed.
Further, according to the composition for preparing a carbon dioxide external preparation of the present invention, a magnesium salt, a water-soluble calcium salt, a gelling agent that gels with magnesium ions or calcium ions, a carbonate, a substance that is hydrolyzed to generate an acid, By containing a polyhydric alcohol and water, the amount of membrane-permeable carbon dioxide exceeding the amount of membrane-permeable carbon dioxide generated from the composition for preparing a carbon dioxide external preparation comprising components known in Patent Document 2 and the like Can be generated.
実施例1及び比較例3における膜透過性二酸化炭素発生量の経時変化を示すグラフ。The graph which shows the time-dependent change of the membrane-permeable carbon dioxide generation amount in Example 1 and Comparative Example 3. 実施例1及び比較例3におけるpH値の経時変化を示すグラフ。The graph which shows the time-dependent change of the pH value in Example 1 and Comparative Example 3.
 本発明の二酸化炭素外用剤調製用組成物は、2以上の剤を使用時に混合する二酸化炭素外用剤を調製するものであり、マグネシウム塩、水溶性カルシウム塩、マグネシウムイオン又はカルシウムイオンによってゲル化するゲル化剤、炭酸塩、加水分解されて酸を生じる物質、多価アルコール及び水を少なくとも含有し、必要に応じてその他の成分をさらに含有させてもよい。 The composition for preparing a carbon dioxide external preparation of the present invention is for preparing a carbon dioxide external preparation in which two or more agents are mixed at the time of use, and gels with a magnesium salt, a water-soluble calcium salt, magnesium ion or calcium ion. It contains at least a gelling agent, a carbonate, a substance that is hydrolyzed to generate an acid, a polyhydric alcohol, and water, and may further contain other components as necessary.
 前記マグネシウム塩は、その化学構造式中にマグネシウムを有するものであって水中でマグネシウムイオンを生成するものであれば特に制限はなく、目的により適宜選択することができる。例えば、酸化マグネシウム、炭酸マグネシウム、硫酸マグネシウム、ケイ酸アルミン酸マグネシウム、L-アスコルビン酸-2-リン酸エステルマグネシウム、ケイ酸マグネシウム、ステアリン酸マグネシウム、水酸化マグネシウム、酢酸マグネシウム、リンゴ酸マグネシウム、クエン酸マグネシウムなどが挙げられる。これらは1種で単独使用してもよいし、2種以上を併用してもよく、炭酸塩などの他の必須成分と兼ねてもよい。中でも炭酸マグネシウムや酸化マグネシウムなどが好ましく、二酸化炭素外用剤調製用組成物の成分として必須である炭酸塩を兼ねる炭酸マグネシウムがさらに好ましい。 The magnesium salt is not particularly limited as long as it has magnesium in its chemical structural formula and generates magnesium ions in water, and can be appropriately selected depending on the purpose. For example, magnesium oxide, magnesium carbonate, magnesium sulfate, magnesium aluminate silicate, magnesium L-ascorbate-2-phosphate, magnesium silicate, magnesium stearate, magnesium hydroxide, magnesium acetate, magnesium malate, citric acid Examples include magnesium. These may be used individually by 1 type, may use 2 or more types together, and may serve as other essential components, such as carbonate. Among these, magnesium carbonate and magnesium oxide are preferable, and magnesium carbonate which also serves as a carbonate essential as a component of the composition for preparing carbon dioxide external preparation is more preferable.
 前記マグネシウム塩の前記二酸化炭素外用剤調製用組成物全量に対する含有量は、特に制限はなく、目的により適宜選択することができる。前記含有量が12質量%を超えると、塗布表面が固まり始める時間もゲル全体が肌に残らず剥がせる程度に固まる時間も短くなりすぎることがある。一方、前記含有量が0.3質量%未満であると、塗布表面が固まり始める時間もゲル全体が肌に残らず剥がせる程度に固まる時間も長くなりすぎるため、0.3質量%以上12質量%未満であることが好ましく、0.5質量%以上11質量%以下であるとさらに好ましい。 The content of the magnesium salt with respect to the total amount of the composition for preparing carbon dioxide external preparation is not particularly limited and can be appropriately selected depending on the purpose. When the content exceeds 12% by mass, the time when the coated surface starts to harden and the time when the entire gel hardens to the extent that it can be peeled off without leaving the skin may be too short. On the other hand, when the content is less than 0.3% by mass, the time for the coating surface to start to solidify and the time for the gel to harden to the extent that it can be peeled without remaining on the skin become too long. % Is preferably less than 0.5%, more preferably 0.5% by mass or more and 11% by mass or less.
 前記水溶性カルシウム塩は、その化学構造式中にカルシウムを有するものであって水溶性を有し水中でカルシウムイオンを生成するものであれば特に制限はなく、目的により適宜選択することができる。例えば、塩化カルシウム、乳酸カルシウムなどが挙げられる。これらは1種で単独使用してもよいし、2種以上を併用してもよく、他の必須成分と兼ねてもよい。中でも使用終了時までに二酸化炭素外用剤調製用組成物が手で剥離可能なようにゲル化するカルシウム塩が好ましく、水への溶解度の面から塩化カルシウムがさらに好ましい。 The water-soluble calcium salt is not particularly limited as long as it has calcium in its chemical structural formula and has water solubility and generates calcium ions in water, and can be appropriately selected depending on the purpose. Examples thereof include calcium chloride and calcium lactate. These may be used individually by 1 type, may use 2 or more types together, and may serve as another essential component. Among them, a calcium salt that gels so that the composition for preparing a carbon dioxide external preparation by hand can be peeled off by the end of use is preferable, and calcium chloride is more preferable in terms of solubility in water.
 前記水溶性カルシウム塩(該水溶性カルシウム塩中の水を除く)の前記二酸化炭素外用剤調製用組成物全量に対する含有量は、特に制限はなく、目的により適宜選択することができる。前記含有量が0.003質量%未満であると、使用終了時間までに二酸化炭素外用剤調製用組成物が十分にゲル化せず剥離しづらくなる。一方、前記含有量が0.05質量%を超えると、混合から塗布時までに塗布表面が固まりやすくなるため、0.003質量%以上0.05質量%以下であることが好ましく、0.003質量%以上0.03質量%以下であるとさらに好ましい。 The content of the water-soluble calcium salt (excluding water in the water-soluble calcium salt) with respect to the total amount of the composition for preparing carbon dioxide external preparation is not particularly limited and can be appropriately selected depending on the purpose. When the content is less than 0.003% by mass, the composition for preparing a carbon dioxide external preparation is not sufficiently gelled by the end of use and is difficult to peel off. On the other hand, if the content exceeds 0.05% by mass, the coating surface tends to harden from mixing to coating, and therefore it is preferably 0.003% by mass or more and 0.05% by mass or less. More preferably, it is at least 0.03% by mass.
 前記マグネシウムイオン又はカルシウムイオンによってゲル化するゲル化剤は、前記マグネシウム塩から生じるマグネシウムイオンや前記水溶性カルシウム塩から生じるカルシウムイオンなどによってゲル化するものであれば特に制限はなく、目的により適宜選択することができる。例えば、カラギーナン、キサンタンガム、タラガム、アルギン酸ナトリウムなどが挙げられる。これらは1種で単独使用してもよいし、2種以上を併用してもよい。中でも塗布状態のなめらかさや使用しやすさの面から、アルギン酸ナトリウムやキサンタンガムが好ましい。 The gelling agent that gels with magnesium ions or calcium ions is not particularly limited as long as it gels with magnesium ions generated from the magnesium salt or calcium ions generated from the water-soluble calcium salt, and is appropriately selected depending on the purpose. can do. For example, carrageenan, xanthan gum, tara gum, sodium alginate and the like can be mentioned. These may be used alone or in combination of two or more. Among these, sodium alginate and xanthan gum are preferable from the viewpoint of smoothness in application state and ease of use.
 前記マグネシウムイオン又はカルシウムイオンによってゲル化するゲル化剤の前記二酸化炭素外用剤調製用組成物全量に対する含有量は、特に制限はなく、目的により適宜選択することができる。前記含有量が1.0質量%未満であると、前記二酸化炭素外用剤調製用組成物のゲル化が十分でなく、皮膚外用剤としての効果が得にくくなる。一方、7質量%を超えると混合から塗布時までに塗布表面を触れた手に二酸化炭素外用剤調製用組成物が付着しなくなるような状態に該塗布表面が固まりやすくなるため、1.0質量%以上7質量%以下であることが好ましく、2質量%以上5質量%以下であることがさらに好ましい。 The content of the gelling agent that gels with magnesium ions or calcium ions with respect to the total amount of the composition for preparing a carbon dioxide external preparation is not particularly limited and can be appropriately selected depending on the purpose. When the content is less than 1.0% by mass, the composition for preparing a carbon dioxide external preparation is not sufficiently gelled, and it is difficult to obtain an effect as a skin external preparation. On the other hand, if it exceeds 7% by mass, the coated surface tends to harden in a state where the composition for preparing a carbon dioxide external preparation does not adhere to the hand that touched the coated surface from mixing to coating. % To 7% by mass, more preferably 2% to 5% by mass.
 前記炭酸塩は、前記二酸化炭素外用剤調製用組成物に含まれる加水分解されて酸を生じる物質と反応して二酸化炭素を発生する炭酸塩であれば、特に制限はなく、目的により適宜選択することができる。例えば、炭酸アンモニウム、炭酸水素アンモニウム、炭酸カリウム、炭酸水素カリウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸マグネシウム、炭酸水素マグネシウム、炭酸カルシウム、炭酸水素カルシウム、炭酸バリウムなどが挙げられる。これらは1種で単独使用してもよいし、2種以上を併用してもよく、マグネシウム塩やカルシウム塩などの他の必須成分と兼ねてもよい。中でもマグネシウムイオンの生成を兼ねる炭酸マグネシウムがより好ましい。 The carbonate is not particularly limited as long as it is a carbonate that reacts with a substance that is hydrolyzed to generate an acid contained in the composition for preparing an external preparation for carbon dioxide, and is appropriately selected depending on the purpose. be able to. For example, ammonium carbonate, ammonium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, magnesium carbonate, magnesium hydrogen carbonate, calcium carbonate, calcium hydrogen carbonate, barium carbonate and the like can be mentioned. These may be used individually by 1 type, may use 2 or more types together, and may serve as other essential components, such as a magnesium salt and a calcium salt. Of these, magnesium carbonate, which also serves to generate magnesium ions, is more preferable.
 前記炭酸塩の前記二酸化炭素外用剤調製用組成物全量に対する含有量は、特に制限はなく、目的により適宜選択することができる。前記含有量が0.3質量%未満であると、二酸化炭素の発生量が少なくなり二酸化炭素発生により得られる外用剤としての効果が十分に発揮されにくくなる。一方、前記含有量が12質量%を超えると、前記二酸化炭素外用剤調製用組成物のpHが高くなり発生した二酸化炭素が炭酸イオンとして存在しやすく膜透過性二酸化炭素発生量が少なくなるため、0.3質量%以上12質量%以下であることが好ましく、0.5質量%以上11質量%以下であることがさらに好ましい。 The content of the carbonate with respect to the total amount of the composition for preparing a carbon dioxide external preparation is not particularly limited and can be appropriately selected depending on the purpose. When the content is less than 0.3% by mass, the generated amount of carbon dioxide is reduced, and the effect as an external preparation obtained by the generation of carbon dioxide is not sufficiently exhibited. On the other hand, if the content exceeds 12% by mass, the pH of the composition for preparing a carbon dioxide external preparation is high, and the generated carbon dioxide tends to exist as carbonate ions, so the amount of generated membrane-permeable carbon dioxide decreases. It is preferably 0.3% by mass or more and 12% by mass or less, and more preferably 0.5% by mass or more and 11% by mass or less.
 前記加水分解されて酸を生じる物質は、その分子構造内に環状エステル結合を1以上有するものであれば特に制限はなく、目的により適宜選択することができる。例えば、グルコノデルタラクトン、パントラクトン、D,L―又はL―ラクチド(3,6―ジメチル―1,4-ジオキサン―2,5―ジオン)、D,L―又はL―グリコリド、無水フタル酸、無水マレイン酸、無水コハク酸などが挙げられる。これらは1種で単独使用してもよいし、2種以上を併用してもよい。中でもグルコノデルタラクトンやD,L―ラクチドなどが好ましく、加水分解速度及び炭酸塩と反応する酸の生成速度の面や化合物の入手しやすさの面からもグルコノデルタラクトンがさらに好ましい。 The substance that generates an acid by hydrolysis is not particularly limited as long as it has one or more cyclic ester bonds in its molecular structure, and can be appropriately selected depending on the purpose. For example, glucono delta lactone, pantolactone, D, L- or L-lactide (3,6-dimethyl-1,4-dioxane-2,5-dione), D, L- or L-glycolide, phthalic anhydride , Maleic anhydride, succinic anhydride and the like. These may be used alone or in combination of two or more. Of these, glucono delta lactone and D, L-lactide are preferable, and glucono delta lactone is more preferable from the viewpoints of hydrolysis rate, acid generation rate that reacts with carbonate, and availability of compounds.
 前記加水分解されて酸を生じる物質の前記二酸化炭素外用剤調製用組成物全量に対する含有量は、特に制限はなく、目的により適宜選択することができる。前記含有量が10質量%未満であると、加水分解した酸と炭酸塩との反応による二酸化炭素の発生量が少なくなり、二酸化炭素発生により得られる外用剤としての効果が十分に発揮されにくくなる。一方、前記含有量が20質量%を超えると、他成分と撹拌混合しにくくなるため、10質量%以上20質量%以下であることが好ましく、13質量%以上18質量%であるとさらに好ましい。 The content of the substance that is hydrolyzed to generate an acid with respect to the total amount of the composition for preparing a carbon dioxide external preparation is not particularly limited and can be appropriately selected depending on the purpose. When the content is less than 10% by mass, the amount of carbon dioxide generated by the reaction between the hydrolyzed acid and the carbonate decreases, and the effect as an external preparation obtained by carbon dioxide generation is not sufficiently exhibited. . On the other hand, when the content exceeds 20% by mass, it is difficult to stir and mix with other components. Therefore, the content is preferably 10% by mass or more and 20% by mass or less, and more preferably 13% by mass or more and 18% by mass.
 前記多価アルコールは、その分子構造内に水酸基を2以上有するアルコールであれば特に制限はなく、目的により適宜選択することができる。例えば、エチレングリコール、プロピレングリコール、1,3-ブチレングリコール、ポリエチレングリコール、グリセリン、1,8-オクタンジオールや、糖アルコールでもあるグリセリン、ソルビトール、糖でもあるトレハロースなどが挙げられる。これらは1種で単独使用してもよいし、2種以上を併用してもよい。中でもゲル化時間を短縮する効果や保湿の面から、1,3-ブチレングリコールが好ましい。 The polyhydric alcohol is not particularly limited as long as it has two or more hydroxyl groups in its molecular structure, and can be appropriately selected depending on the purpose. Examples include ethylene glycol, propylene glycol, 1,3-butylene glycol, polyethylene glycol, glycerin, 1,8-octanediol, glycerin that is a sugar alcohol, sorbitol, and trehalose that is also a sugar. These may be used alone or in combination of two or more. Among them, 1,3-butylene glycol is preferable from the viewpoint of shortening the gelation time and moisturizing.
 前記多価アルコールの前記二酸化炭素外用剤調製用組成物全量に対する含有量は、特に制限はなく、目的により適宜選択することができる。前記含有量が5質量%未満であると、前記二酸化炭素外用剤調製用組成物は2以上の剤を混合後にゲル化する時間が長くなり、使用終了時間までに二酸化炭素外用剤調製用組成物が手で剥離可能なようにゲル化することができなくなる。一方、前記含有量が25質量%を超えると、混合から塗布時までに塗布表面を触れた手に二酸化炭素外用剤調製用組成物が付着しなくなるような状態に該塗布表面が固まるため、5質量%以上25質量%以下であることが好ましく、5質量%以上20質量%以下であるとさらに好ましい。 The content of the polyhydric alcohol with respect to the total amount of the composition for preparing a carbon dioxide external preparation is not particularly limited and can be appropriately selected depending on the purpose. When the content is less than 5% by mass, the composition for preparing a carbon dioxide external preparation has a longer time for gelation after mixing two or more agents, and the composition for preparing a carbon dioxide external preparation by the end of use. Cannot be gelled so that it can be peeled off by hand. On the other hand, when the content exceeds 25% by mass, the coated surface hardens in such a state that the carbon dioxide external preparation preparation composition does not adhere to the hand that touched the coated surface from mixing to coating. The mass is preferably from 25% by mass to 25% by mass, and more preferably from 5% by mass to 20% by mass.
 前記二酸化炭素外用剤調製用組成物に含まれる水は、通常の化粧品、医薬品等に用いられる水であれば、特に制限はなく、目的により適宜選択することができる。例えば、蒸留水、膜透過水、イオン交換水が挙げられる。これらは1種で単独使用してもよいし、2種以上を併用してもよく、塩化カルシウム水溶液など他の成分の水溶液として含まれていてもよい。 The water contained in the composition for preparing a carbon dioxide external preparation is not particularly limited as long as it is water used for normal cosmetics, pharmaceuticals, and the like, and can be appropriately selected depending on the purpose. For example, distilled water, membrane permeated water, and ion exchange water can be mentioned. These may be used individually by 1 type, may use 2 or more types together, and may be contained as aqueous solution of other components, such as calcium chloride aqueous solution.
 前記水の前記二酸化炭素外用剤調製用組成物全量に対する含有量は、特に制限はなく、目的により適宜選択することができる。また、前記含有量は、前記水及び前記水溶性カルシウム塩などの他の成分に含まれる水を合計したものであり、前記二酸化炭素外用剤調製用組成物全量が100質量%となるように調製される。また、前記含有量が55質量%未満であると粘性が高くなり流動性、柔軟性、さらには他の成分の溶解性等に欠けるため、前記含有量は55質量%以上であることが好ましい。 The content of the water with respect to the total amount of the composition for preparing a carbon dioxide external preparation is not particularly limited and can be appropriately selected depending on the purpose. The content is a total of water and water contained in other components such as the water-soluble calcium salt, and is prepared so that the total amount of the carbon dioxide external preparation preparation composition is 100% by mass. Is done. Further, when the content is less than 55% by mass, the viscosity becomes high and fluidity, flexibility, and solubility of other components are lacking. Therefore, the content is preferably 55% by mass or more.
 前記二酸化炭素外用剤調製用組成物のその他の成分は、化粧品や皮膚外用剤に用いられる成分であれば特に制限はなく、目的により適宜選択することができる。例えば、界面活性剤、pH調整剤、保湿剤、防腐剤、酸化防止剤、香料、分散剤、紫外線吸収剤、色素などが挙げられる。これらは1種を単独使用してもよいし、2種以上を併用してもよい。 Other components of the carbon dioxide external preparation preparation composition are not particularly limited as long as they are components used in cosmetics and skin external preparations, and can be appropriately selected depending on the purpose. For example, surfactants, pH adjusters, humectants, preservatives, antioxidants, fragrances, dispersants, ultraviolet absorbers, dyes and the like can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
 前記二酸化炭素外用剤の使用形態は、特に制限はなく、目的により適宜選択することができる。例えば、ジェル状の2以上の剤を皮膚等への塗布時に混合することにより使用する形態、ジェル状及び顆粒状の2以上の剤を皮膚等への塗布時に混合することによる使用する形態、顆粒状の剤を水で溶解後にジェル状の剤を皮膚等への塗布時に混合することによる使用する形態などが挙げられる。 The usage form of the carbon dioxide external preparation is not particularly limited and can be appropriately selected depending on the purpose. For example, a form used by mixing two or more gel-like agents when applied to the skin, etc., a form used by mixing two or more gel-like and granular agents when applied to the skin, granules, etc. Examples include a form in which a gel-like agent is mixed with water after being dissolved in water and then mixed at the time of application to the skin.
 前記二酸化炭素外用剤調製用組成物の皮膚等への塗布時の伸びの良さの評価方法は、塗布したジェルの伸びの良さを示すことができる方法であれば、特に制限はなく、目的により選択することができる。例えば、2以上の剤を混合後皮膚等へ塗布してから「塗布表面を触った時にジェルが手指に付着しないようになるまでの時間」を「塗布表面が固まり始める時間」と定義し、該「塗布表面が固まり始める時間」の長短で伸びの良さを評価する方法が挙げられる。 The method for evaluating the goodness of elongation of the carbon dioxide external preparation preparation composition when applied to the skin or the like is not particularly limited as long as it can show the goodness of elongation of the applied gel, and is selected according to the purpose. can do. For example, after mixing two or more agents and applying to the skin etc., the “time until the gel does not adhere to the finger when the application surface is touched” is defined as “the time when the application surface starts to solidify”, There is a method of evaluating the goodness of elongation by the length of the “time when the coated surface starts to harden”.
 前記二酸化炭素外用剤調製用組成物の皮膚等への塗布後、使用終了時点での剥がしやすさの評価方法は、塗布したジェルの剥がしやすさ、固まりやすさを示すことができる方法であれば、特に制限はなく、目的により選択することができる。例えば、2以上の剤を混合後皮膚等へ塗布してから「剥がした時にジェルが肌に残らないようになるまでの時間」を「剥がせる時間」と定義し、該「剥がせる時間」の長短を使用時間と対比して評価する方法が挙げられる。 After the application of the composition for preparing a carbon dioxide external preparation to the skin or the like, the evaluation method of the ease of peeling at the end of use can be any method that can show the ease of peeling and the tendency of the applied gel to be solidified. There is no particular limitation, and it can be selected according to the purpose. For example, after mixing two or more agents and applying to the skin etc., the “time until the gel does not remain on the skin when peeled” is defined as “the time to peel off”, and the “time to peel off” There is a method of evaluating long and short in comparison with use time.
 前記二酸化炭素外用剤調製用組成物の膜透過性二酸化炭素の発生量の評価方法は、人の皮膚環境を模した膜を透過する二酸化炭素量を計測することができる方法であれば、特に制限はなく、目的により適宜選択することができる。例えば、多孔性高分子膜を油脂に浸し、該膜を透過する二酸化炭素量を計測する方法が挙げられる。人の皮膚の環境に近づけるため、前記多孔性高分子膜にはマイクロポーラスフィルム(住友スリーエム社製、3Mマイクロポーラスフィルム、孔径0.3μm以下)を使用し、前記油脂にはオリーブスクワラン(岸本特殊肝油工業所製、植物スクワラン)を使用し、前記膜透過二酸化炭素量計測には炭酸ガス濃度計(東亜ディーケーケー(株)製、型番CGP-31)を用いる方法が特に好ましい。 The method for evaluating the amount of carbon-permeable carbon dioxide generated in the composition for preparing a carbon dioxide external preparation is particularly limited as long as it can measure the amount of carbon dioxide that permeates through a membrane simulating a human skin environment. It can be appropriately selected depending on the purpose. For example, a method of immersing a porous polymer membrane in oil and fat and measuring the amount of carbon dioxide that permeates the membrane can be mentioned. In order to approach the human skin environment, a microporous film (manufactured by Sumitomo 3M, 3M microporous film, pore size of 0.3 μm or less) is used for the porous polymer film, and olive squalane (Kishimoto Special) is used for the fats and oils. A method using a carbon dioxide concentration meter (manufactured by Toa DKK Co., Ltd., model number CGP-31) is particularly preferable for measuring the amount of carbon dioxide permeated through a liver oil industry plant, plant squalane.
 前記二酸化炭素外用剤調製用組成物の膜透過性二酸化炭素の発生量の評価は、具体的には、2以上の剤を撹拌混合したジェル1gを炭酸ガス濃度計専用の容器に入れ、その上からオリーブスクワラン0.1gを塗布したマイクロポーラスフィルムを被せ、該専用容器に炭酸ガス濃度計の検出器を取り付ける。前記容器と検出器の間を満たすように注射器を用いて所定量の水を加え、直後から1分ごとに60分間、膜透過性二酸化炭素発生量を測定し記録して行う。 Specifically, evaluation of the amount of membrane-permeable carbon dioxide generated in the composition for preparing a carbon dioxide external preparation was carried out by putting 1 g of a gel in which two or more agents were stirred and mixed into a container dedicated to a carbon dioxide concentration meter. Then, a microporous film coated with 0.1 g of olive squalane is covered, and a detector of a carbon dioxide concentration meter is attached to the dedicated container. A predetermined amount of water is added using a syringe so as to fill the space between the container and the detector, and the amount of membrane-permeable carbon dioxide generated is measured and recorded for 60 minutes every minute immediately after.
 前記二酸化炭素外用剤調製用組成物の評価方法として、膜透過性二酸化炭素発生時に二酸化炭素外用剤調製用組成物のpHをさらに測定することにより、二酸化炭素外用剤調製用組成物から発生する二酸化炭素の状態を確認することができる。
 前記pHの測定方法は、前記二酸化炭素外用剤調製用組成物のpHの経時変化を測定できる方法であれば、特に制限はなく、目的により適宜選択することができる。例えば、2以上の剤を撹拌混合し、日常防水型pH計(HANNA instruments製、pHep4 HI98127)を使用して二酸化炭素外用剤調製用組成物のpHを経時的に測定する方法が挙げられる。
As a method for evaluating the composition for preparing a carbon dioxide external preparation, the carbon dioxide generated from the composition for preparing a carbon dioxide external preparation is further measured by further measuring the pH of the composition for preparing a carbon dioxide external preparation when membrane-permeable carbon dioxide is generated. The state of carbon can be confirmed.
The method for measuring the pH is not particularly limited as long as it is a method capable of measuring the change over time of the pH of the composition for preparing an external preparation for carbon dioxide, and can be appropriately selected depending on the purpose. For example, a method of stirring and mixing two or more agents and measuring the pH of the composition for preparing a carbon dioxide external preparation over time using an everyday waterproof pH meter (manufactured by HANNA instruments, pHep4 HI98127) can be mentioned.
 以下に実施例及び比較例を挙げて本発明を具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
 (実施例1~9及び比較例1~3)
 表1に記載した組成に従い、二酸化炭素外用剤調製用組成物を調製した。なお、マグネシウム塩及び炭酸塩を兼ねる炭酸マグネシウムを配合した実施例においては、表中に記載された炭酸マグネシウムの配合量で二酸化炭素外用剤調製用組成物を調製したが、請求項4、段落0034及び0035等の必須成分の配合条件においては、マグネシウム塩及び炭酸塩がそれぞれ同量配合されているものとみなした。
 表2に記載した配合量に従い、2つに分かれた剤を、使用直前に目視で均一になるまで撹拌混合した。
(Examples 1 to 9 and Comparative Examples 1 to 3)
According to the composition described in Table 1, a composition for preparing a carbon dioxide external preparation was prepared. In the examples in which magnesium carbonate that also serves as a magnesium salt and carbonate was blended, a composition for preparing a carbon dioxide external preparation was prepared with the blending amount of magnesium carbonate described in the table. And 0035 and the like, it was considered that the same amount of magnesium salt and carbonate was mixed.
According to the blending amount described in Table 2, the agent divided into two was stirred and mixed until it became uniform visually before use.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 実施例1~9及び比較例1~3で調製して得られた二酸化炭素外用剤調製用組成物について、以下に示す評価方法により、該二酸化炭素外用剤調製用組成物の、混合後皮膚等への塗布時の伸びの良さ及び使用終了時点での剥がしやすさの評価を行った。
 2以上の剤を混合後皮膚等へ塗布してから「塗布表面を触った時にジェルが手指に付着しないようになるまでの時間」を「塗布表面が固まり始める時間」とし、該「塗布表面が固まり始める時間」を計測した。次に2以上の剤を混合後皮膚等へ塗布してから「剥がした時にジェルが肌に残らないようになるまでの時間」を「剥がせる時間」とし、該「剥がせる時間」を計測した。そして、2以上の剤を混合後皮膚等へ塗布する時間をもとに適切な「塗布表面が固まり始める時間」を規定し、また、使用時間をもとに適切な「剥がせる時間」を規定した。「塗布表面が固まり始める時間」及び「剥がせる時間」の両方が規定時間内にある場合には「良い(◎)」と評価し、両方とも規定時間内にない場合は「悪い(△)」と評価し、一方が規定時間内にありもう一方が規定時間にない場合は「ふつう(○)」と評価し、混合後60分経過しても固まらないあるいは剥がせない場合は「使用不可(×)」と評価した。
 記載の実施例及び比較例において、二酸化炭素外用剤調製用組成物の2以上の剤を混合後皮膚等へ塗布する時間は5分以内であったので、前記適切な塗布表面が固まり始める時間は5~10分と規定した。また、記載の実施例及び比較例において二酸化炭素外用剤調製用組成物の使用時間は10~15分であったので、前記適切な剥がせる時間は10~15分と規定した。
 混合後皮膚等への塗布時の伸びの良さ及び使用終了時点での剥がしやすさの評価結果を表3に示す。
About the composition for preparing carbon dioxide external preparations prepared in Examples 1 to 9 and Comparative Examples 1 to 3, the composition for preparing carbon dioxide external preparations was mixed according to the following evaluation method. Evaluation of good elongation at the time of application and ease of peeling at the end of use.
After mixing two or more agents on the skin or the like, the “time until the gel does not adhere to the finger when the application surface is touched” is defined as the “time when the application surface starts to solidify”, and the “application surface is The time to start setting was measured. Next, after mixing two or more agents and applying to the skin, etc., the “time until the gel does not remain on the skin when peeled” was defined as the “time to remove”, and the “time to remove” was measured. . Then, specify the appropriate “time for the coated surface to start to solidify” based on the time to apply two or more agents to the skin, etc., and specify the appropriate “time to peel off” based on the usage time. did. If both “time when the coated surface starts to solidify” and “time to peel off” are within the specified time, it is evaluated as “good (◎)”, and if both are not within the specified time, “bad (△)”. If one is within the specified time and the other is not within the specified time, it is evaluated as “Normal (○)”. If it does not solidify or peel off after 60 minutes after mixing, X) ".
In the examples and comparative examples described, since the time for applying two or more agents of the composition for preparing a carbon dioxide external preparation to the skin after mixing was within 5 minutes, the time for the appropriate application surface to start to solidify was It was defined as 5-10 minutes. Further, in the examples and comparative examples described, the use time of the composition for preparing a carbon dioxide external preparation was 10 to 15 minutes, so the appropriate peeling time was defined as 10 to 15 minutes.
Table 3 shows the evaluation results of good elongation at the time of application to the skin after mixing and ease of peeling at the end of use.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 表3より、良い(◎)評価であった実施例1、2及び6と比較し、水溶性カルシウム塩の含まれない比較例2では使用終了後に剥がせず、又、水溶性カルシウム塩である塩化カルシウムの配合量が多くなる実施例3及び4では塗布表面が固まり始める時間が短く塗布時の伸びがよくないことが分かった。また、炭酸マグネシウムを炭酸水素ナトリウムに変更した比較例1では塗布表面も内部も固まらず、さらに炭酸マグネシウムの配合量を増やした実施例7及び8では塗布表面が固まり始める時間も剥がせる時間も短くなることが分かった。 From Table 3, compared with Examples 1, 2 and 6 which were good (◎) evaluation, Comparative Example 2 which does not contain a water-soluble calcium salt does not peel off after use, and is a water-soluble calcium salt. In Examples 3 and 4 where the compounding amount of calcium chloride is large, it was found that the time when the coating surface started to solidify was short and the elongation during coating was not good. Further, in Comparative Example 1 in which magnesium carbonate is changed to sodium hydrogen carbonate, neither the coating surface nor the inside is hardened, and in Examples 7 and 8 in which the blending amount of magnesium carbonate is further increased, the time at which the coating surface begins to harden and the time to peel off are short. I found out that
 実施例1及び比較例3で調製して得られた二酸化炭素外用剤調製用組成物について、膜透過性二酸化炭素発生量の評価は、以下の方法により行った。
 実施例及び比較例について、表2に記載の2剤を混合したジェル1gを炭酸ガス濃度計専用の容器に入れ、その上からオリーブスクワラン0.1gを塗布したマイクロポーラスフィルムを被せ、該専用容器に炭酸ガス濃度計の検出器を取り付ける。前記容器と検出器の間を満たすように注射器を用いて所定量の水を加え、直後から1分ごとに60分間、膜透過二酸化炭素発生量を測定し記録した。
 膜透過性二酸化炭素発生量の試験結果を表4に示す。
About the composition for carbon dioxide external preparation preparation obtained by preparing in Example 1 and Comparative Example 3, the amount of membrane-permeable carbon dioxide generation was evaluated by the following method.
For Examples and Comparative Examples, 1 g of gel mixed with the two agents listed in Table 2 was put in a container dedicated to a carbon dioxide concentration meter, and a microporous film coated with 0.1 g of olive squalane was placed thereon, and the dedicated container Attach a carbon dioxide concentration meter detector. A predetermined amount of water was added using a syringe so as to fill the space between the container and the detector, and the amount of carbon dioxide permeated through the membrane was measured and recorded every minute for 60 minutes.
Table 4 shows the test results of the amount of generated carbon permeable carbon dioxide.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
 表4に基づき、実施例1及び比較例3の膜透過性二酸化炭素発生量の経時変化を図1に示す。
 表4及び図1より、実施例1と、マグネシウムイオン及び水溶性カルシウム塩を含まない比較例3とを比較した場合、混合後実施例1の想定使用時間である15分までにおける膜透過性二酸化炭素発生量は比較例3の膜透過性二酸化炭素発生量の約1.2倍になっていることが分かる。
Based on Table 4, the time-dependent change of the membrane-permeable carbon dioxide generation amount of Example 1 and Comparative Example 3 is shown in FIG.
From Table 4 and FIG. 1, when Example 1 was compared with Comparative Example 3 not containing magnesium ions and water-soluble calcium salt, the membrane-permeable dioxide up to 15 minutes, which was the assumed usage time of Example 1 after mixing, It can be seen that the carbon generation amount is about 1.2 times the membrane-permeable carbon dioxide generation amount of Comparative Example 3.
 前記pHの測定は、以下の方法により行った。実施例1及び比較例3に記載の2剤を撹拌混合し、日常防水型pH計(HANNA instruments製、pHep4 HI98127)を使用して二酸化炭素外用剤調製用組成物のpHを経時的に測定した。
 pHの測定結果を表5及び図2に示す。
The pH was measured by the following method. The two agents described in Example 1 and Comparative Example 3 were stirred and mixed, and the pH of the composition for preparing a carbon dioxide external preparation was measured over time using an everyday waterproof pH meter (manufactured by HANNA instruments, pHep4 HI98127). .
The measurement results of pH are shown in Table 5 and FIG.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
 表5及び図2より、実施例1においては2剤の混合後直後にpHが下がり、60分経過するまで、膜透過性二酸化炭素が発生しやすいpH4.0~6.5に保持されていることが分かった。 From Table 5 and FIG. 2, in Example 1, the pH drops immediately after mixing the two agents, and is maintained at pH 4.0 to 6.5 where membrane-permeable carbon dioxide is likely to be generated until 60 minutes have passed. I understood that.
 表3~5及び図1~2より、2以上の剤に分けた前記二酸化炭素外用剤調製用組成物を混合後に皮膚上に塗布した場合、混合から塗布時までに塗布表面を触れた手に二酸化炭素外用剤調製用組成物が付着しなくなるような状態に該塗布表面が固まらず、かつ、使用終了時までに二酸化炭素外用剤調製用組成物が手で剥離可能なようにゲル化する二酸化炭素外用剤調製用組成物を提供できることが分かった。すなわち、二酸化炭素外用剤調製用組成物の皮膚等への塗布時には伸びが良く、使用時間経過後には手で剥離可能な程度に固まることが分かった。
 また、本発明の二酸化炭素外用剤調製用組成物は、マグネシウム塩、水溶性カルシウム塩、マグネシウムイオン又はカルシウムイオンによってゲル化するゲル化剤、炭酸塩、加水分解されて酸を生じる物質、多価アルコール及び水を含有させることで、使用開始直後から使用終了までの期間において、pHが4~6.5に維持され、かつ、特許文献2等で知られている成分からなる二酸化炭素外用剤調製用組成物から発生する膜透過性二酸化炭素量を超える量の膜透過性二酸化炭素を発生させることが分かった。
From Tables 3 to 5 and FIGS. 1 and 2, when the composition for preparing carbon dioxide external preparations divided into two or more agents is applied on the skin after mixing, it is applied to the hand touching the application surface from mixing to application. The coating surface does not harden in such a state that the composition for preparing a carbon dioxide external preparation does not adhere, and the carbon dioxide external preparation composition is gelled so that the composition for preparing a carbon dioxide external preparation can be peeled off by the end of use. It turned out that the composition for carbon external preparation preparation can be provided. That is, it was found that when the composition for preparing an external preparation for carbon dioxide was applied to the skin or the like, the elongation was good, and it solidified to the extent that it could be peeled by hand after the use time.
Further, the composition for preparing a carbon dioxide external preparation of the present invention comprises a magnesium salt, a water-soluble calcium salt, a gelling agent that gels with magnesium ions or calcium ions, a carbonate, a substance that is hydrolyzed to produce an acid, a polyvalent By containing alcohol and water, the preparation of a carbon dioxide external preparation comprising a component that is maintained at a pH of 4 to 6.5 and is known in Patent Document 2 in the period from the start of use to the end of use It has been found that membrane permeable carbon dioxide is generated in an amount exceeding the amount of membrane permeable carbon dioxide generated from the composition for use.
 以上の効果はいくつかの要因に基づく。まず、前記効果は、炭酸マグネシウムなどのマグネシウムイオンを生じる成分を配合することで、カルシウムイオンを生じる成分を配合した場合よりも、アルギン酸ナトリウムやキサンタンガムなどのゲル化剤のイオン架橋を緩やかにすることに基づく。マグネシウムイオンの配合は、混合直後の二酸化炭素外用剤調製用組成物の伸びをよくし、又、ジェル全体を固めることに寄与する。さらに、前記効果は、カルシウムイオンを生じる成分として水溶性カルシウム塩である塩化カルシウムを配合することで、水不溶性又は水難溶性の炭酸カルシウムを配合した場合よりも、アルギン酸ナトリウムやキサンタンガムなどのゲル化剤のイオン架橋を早めることに基づく。水溶性カルシウムイオンの配合は、混合直後より二酸化炭素外用剤調製用組成物の塗布表面を固めることに寄与する。また、前記効果は、多価アルコールであるブチレングリコールの配合量を多くすることで、ゲル化剤のイオン架橋を早めることができることに基づく。ブチレングリコールの配合は、混合直後の二酸化炭素外用剤調製用組成物の伸びの良さや剥がせる時間の調節に寄与する。
 そして、前記効果は、炭酸マグネシウムなどのマグネシウムイオンを生じる成分及び水溶性カルシウム塩を適量配合することで、塗布表面が固まり始める時間や剥がせる時間を調節し、二酸化炭素外用剤調製用組成物から発生する膜透過性二酸化炭素を二酸化炭素外用剤調製用組成物の外へ放出できることに基づく。マグネシウムイオンを生じる成分及び水溶性カルシウム塩の適量な配合は、カルシウムイオンを生じる成分として水不溶性又は水難溶性カルシウム塩の適量に配合しマグネシウムイオンを生じる成分を配合しない従来より知られている成分からなる二酸化炭素外用剤調製用組成物から発生する膜透過性二酸化炭素量よりも多くの膜透過性二酸化炭素を発生させることができる。
These effects are based on several factors. First, the effect is that by blending a component that generates magnesium ions such as magnesium carbonate, the ionic crosslinking of gelling agents such as sodium alginate and xanthan gum is made more gradual than when a component that generates calcium ions is blended. based on. The blending of magnesium ions improves the elongation of the composition for preparing a carbon dioxide external preparation immediately after mixing, and contributes to hardening the entire gel. Further, the effect is that by adding calcium chloride, which is a water-soluble calcium salt, as a component that generates calcium ions, a gelling agent such as sodium alginate or xanthan gum is more effective than when water-insoluble or poorly water-soluble calcium carbonate is added. Based on accelerating ionic crosslinking of The formulation of water-soluble calcium ions contributes to hardening the coating surface of the carbon dioxide external preparation preparation composition immediately after mixing. Moreover, the said effect is based on the fact that the ionic crosslinking of the gelling agent can be accelerated by increasing the blending amount of butylene glycol which is a polyhydric alcohol. The blend of butylene glycol contributes to the good elongation of the composition for preparing a carbon dioxide external preparation immediately after mixing and the adjustment of the peeling time.
And the said effect adjusts the time which a coating surface begins to solidify, and the time to peel off by mix | blending an appropriate quantity of the component which produces magnesium ions, such as magnesium carbonate, and a water-soluble calcium salt, From the composition for carbon dioxide external preparation preparation This is based on the fact that the generated membrane-permeable carbon dioxide can be released out of the composition for preparing a carbon dioxide external preparation. The appropriate amount of the component that generates magnesium ions and the water-soluble calcium salt is selected from the conventionally known components that are mixed in an appropriate amount of water-insoluble or poorly water-soluble calcium salt as the component that generates calcium ions and do not include the component that generates magnesium ions. More membrane-permeable carbon dioxide can be generated than the amount of membrane-permeable carbon dioxide generated from the composition for preparing a carbon dioxide external preparation.
 本発明の二酸化炭素外用剤調製用組成物は、2以上の剤の混合調製が容易な上、混合直後皮膚上への塗布時までに塗布表面が固まることなく伸びがよく、かつ、使用時間終了までに肌に残らないように剥がせ、そして、使用時間内には十分な量の膜透過性二酸化炭素の発生を持続することができるものである。したがって、肌への適度な刺激を継続できる化粧用パックにおいては、塗布時には伸びがよく、終了時にはきれいに剥がせ、かつ、いわゆる炭酸ガスパックとしての効果を有するが、化粧用パックのみならず、ピーリング剤などの化粧品、皮膚用外用剤、毛髪用剤等の医薬部外品、医薬品、ペット用品のいずれにも好適に使用することができる。 The composition for preparing an external preparation for carbon dioxide of the present invention is easy to mix and prepare two or more agents, has a good elongation without being hardened by the time of application on the skin immediately after mixing, and the use time is over. It can be peeled off so as not to remain on the skin, and a sufficient amount of membrane-permeable carbon dioxide can be generated within the use time. Therefore, in a cosmetic pack that can continue moderate irritation to the skin, it stretches well at the time of application, peels off cleanly at the end, and has an effect as a so-called carbon dioxide gas pack. It can be suitably used for cosmetics such as agents, external preparations for skin, quasi-drugs such as hair preparations, pharmaceuticals, and pet products.
 本発明の二酸化炭素外用剤調製用組成物は、特に、美容業界におけるジェル状のいわゆる炭酸ガスパックでは両立しないといわれた、塗布時に伸びがよく使用終了時に剥がせる特徴を有する。このため、今までは使用終了時に剥がしきれない固まりかけのジェルをタオルで拭き取る必要があり、固まりかけのジェルを拭き取ったタオルの洗濯処理にも副次的な課題が生じていたが、本発明はそのような副次的課題も解決するものでもある。 The composition for preparing a carbon dioxide external preparation of the present invention has a characteristic that it is well stretched at the time of application and can be peeled off at the end of use, which is said to be incompatible with a so-called carbon dioxide gas pack in the beauty industry. For this reason, until now it was necessary to wipe off the lump of gel that could not be peeled off at the end of use with a towel, and there was a secondary problem in the washing process of towels that had been wiped off lump of gel. Solves such secondary problems.

Claims (7)

  1.  少なくともマグネシウム塩、水溶性カルシウム塩、マグネシウムイオン又はカルシウムイオンによってゲル化するゲル化剤、炭酸塩、加水分解されて酸を生じる物質、多価アルコール及び水を必須成分とする、二酸化炭素外用剤調製用組成物。 Preparation of topical carbon dioxide preparation containing at least magnesium salt, water-soluble calcium salt, gelling agent that gels with magnesium ion or calcium ion, carbonate, substance that generates acid upon hydrolysis, polyhydric alcohol and water Composition.
  2.  少なくとも前記炭酸塩及び前記加水分解されて酸を生じる物質を別に配合するように、2以上に分けた前記二酸化炭素外用剤調製用組成物を混合後に皮膚上に塗布した場合、混合から塗布時までに塗布表面が固まらず、かつ、使用終了時までに二酸化炭素外用剤調製用組成物が皮膚から剥離可能なようにゲル化する、請求項1に記載の二酸化炭素外用剤調製用組成物。 When the carbon dioxide external preparation preparation composition divided into two or more is applied on the skin after mixing so that at least the carbonate and the substance that generates acid upon hydrolysis are separately mixed, from mixing to application The composition for preparing a carbon dioxide external preparation according to claim 1, wherein the coating surface does not solidify and gels so that the composition for preparing a carbon dioxide external preparation can be peeled from the skin by the end of use.
  3.  膜透過性二酸化炭素発生量が、マグネシウム塩を除き水溶性カルシウム塩を水不溶性又は水難溶性カルシウム塩に変更してなる前記二酸化炭素外用剤調製用組成物を混合する場合の膜透過性二酸化炭素発生量を超える期間を備えるように、マグネシウム塩及び水溶性カルシウム塩を配合した、請求項1又は2に記載の二酸化炭素外用剤調製用組成物。 Membrane-permeable carbon dioxide generation when the amount of carbon-permeable carbon dioxide generated is mixed with the composition for preparation of carbon dioxide external preparation prepared by changing the water-soluble calcium salt to a water-insoluble or poorly water-soluble calcium salt except for the magnesium salt The composition for preparing a carbon dioxide external preparation according to claim 1 or 2, wherein a magnesium salt and a water-soluble calcium salt are blended so as to have a period exceeding the amount.
  4.  前記二酸化炭素外用剤調製用組成物全量に対する前記マグネシウム塩の含有量は0.3質量%以上12質量%以下であり、前記二酸化炭素外用剤調製用組成物全量に対する前記水溶性カルシウム塩の含有量は0.003質量%以上0.05質量%以下であり、前記二酸化炭素外用剤調製用組成物全量に対する前記マグネシウムイオン又はカルシウムイオンによってゲル化するゲル化剤の含有量は1.0質量%以上7質量%以下であり、前記二酸化炭素外用剤調製用組成物全量に対する前記炭酸塩の含有量は0.3質量%以上12質量%以下であり、前記二酸化炭素外用剤調製用組成物全量に対する前記加水分解されて酸を生じる物質の含有量は10質量%以上20質量%以下であり、前記二酸化炭素外用剤調製用組成物全量に対する前記多価アルコールの含有量は5質量%以上25質量%以下である、請求項1から3のいずれかに記載の二酸化炭素外用剤調製用組成物。 Content of the said magnesium salt with respect to the said composition for carbon dioxide external preparation preparation is 0.3 mass% or more and 12 mass% or less, Content of the said water-soluble calcium salt with respect to the said total composition for carbon dioxide external preparation preparation Is 0.003% by mass or more and 0.05% by mass or less, and the content of the gelling agent gelled by the magnesium ions or calcium ions with respect to the total amount of the composition for preparing a carbon dioxide external preparation is 1.0% by mass or more. 7% by mass or less, and the content of the carbonate with respect to the total amount of the carbon dioxide external preparation preparation composition is 0.3% by mass or more and 12% by mass or less, and the carbon dioxide external preparation preparation total amount The content of the substance that is hydrolyzed to generate an acid is 10% by mass or more and 20% by mass or less. The alcohol content is 25 mass% or more 5 wt%, carbon dioxide external preparation prepared composition according to any one of claims 1 to 3.
  5.  少なくともマグネシウム塩、水溶性カルシウム塩、マグネシウムイオン又はカルシウムイオンによってゲル化するゲル化剤、炭酸塩、加水分解されて酸を生じる物質、多価アルコール及び水を必須成分とする、請求項1から4のいずれかに記載の二酸化炭素外用剤調製用組成物の製造方法。 The essential components are at least a magnesium salt, a water-soluble calcium salt, a gelling agent that gels with magnesium ions or calcium ions, a carbonate, a substance that is hydrolyzed to generate an acid, a polyhydric alcohol, and water. The manufacturing method of the composition for carbon dioxide external preparation preparation in any one of these.
  6.  請求項1から4のいずれかに記載の、二酸化炭素外用剤調製用組成物を用いた二酸化炭素外用剤。 A carbon dioxide external preparation using the composition for preparing carbon dioxide external preparation according to any one of claims 1 to 4.
  7.  請求項1から4のいずれかに記載の、二酸化炭素外用剤調製用組成物を用いた化粧用パック。 A cosmetic pack using the carbon dioxide external preparation preparation composition according to any one of claims 1 to 4.
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