JP4634064B2 - Artificial carbonated spring production system - Google Patents

Description

  The present invention relates to an artificial carbonated spring having a high warm feeling after bathing and having a good skin feel, a method for producing the same, and a production system thereof.

  It has been known that a bath preparation containing a carbon dioxide gas generator in which a carbonate and an acid are combined is excellent in blood circulation promoting effect and hardly causes hot water cooling (see Patent Document 1). In addition to a warm feeling due to blood circulation promotion, a bathing agent containing an oil component in a carbon dioxide gas generator in order to improve the feeling on the skin (see Patent Document 2), an oil component in the carbon dioxide gas generator, a nonionic surfactant And a bath agent containing a cationic polymer (see Patent Document 3), a bath agent containing an oily component containing 60% or more of a fatty acid ester and a nonionic surfactant in a carbon dioxide gas generation product (see Patent Document 4), carbon dioxide gas generation A bath agent (see Patent Document 5) in which an alkyl phthalide having a specific structure and a fatty acid ester are mixed is reported.

On the other hand, means for artificially creating a carbonated spring by blowing carbon dioxide directly into bath water has been reported (see Patent Documents 6 to 9).
JP 59-70609 A JP-A 63-93711 Japanese Patent Laid-Open No. 2-115115 JP-A-2-115116 Japanese Patent Application Laid-Open No. 10-167952 Japanese Patent Laid-Open No. 3-186268 JP-A-6-78963 Japanese Patent Application Laid-Open No. 7-779 JP-A-6-174297

  However, a conventional carbonated spring in which a bathing agent or carbon dioxide gas is blown does not provide a feeling of warmth after bathing, and further, an artificial carbonated spring with a high feeling of warmth and good skin feel has been desired.

  Therefore, as a result of various studies to improve the warming feeling in a carbonated spring in which carbon dioxide gas is directly dissolved, the present inventor has conventionally thought that carbon dioxide gas dissolved in water promotes blood circulation, so that the warming feeling is improved. It was necessary to dissolve carbon dioxide gas in water at a higher concentration. However, it has been found that carbon dioxide gas can be more easily distributed in the oily component than water depending on the type of the oily component. As a result of further investigations, it was found that high-concentration carbon dioxide gas can be supplied to the skin by dispersing the oil component in the bath water and dissolving the carbon dioxide gas, thereby improving the warmth.

That is, the present invention provides the following (A) and (B):
(A) An oil component-containing composition (B) An artificial carbonated spring production system including a carbon dioxide gas dissolving device is provided.
The present invention also provides a method for producing an artificial carbonated spring in which an oil component is dispersed in bath water and carbon dioxide gas is introduced so that the carbon dioxide gas concentration in the bath water is 60 ppm or more.
Furthermore, the present invention provides an artificial carbonated spring in which the oil component concentration in the bath water is 0.1 ppm or more and the carbon dioxide concentration in the bath water is 60 ppm or more.

  According to the present invention, since a higher concentration of carbon dioxide gas dissolves in the bath water, the feeling of warmth after bathing is extremely high and the skin feel is good.

  In the present invention, the artificial carbonated spring is a bath water containing carbon dioxide in the bath water at 60 ppm or more (measurement temperature 40 ° C.), and the carbon dioxide concentration in the bath water is preferably 70 ppm or more, more preferably 80 ppm or more. . In natural water, carbon dioxide containing 1000 ppm or more of carbon dioxide is called carbonated springs, but the effect of warm bathing on the human body appears because the concentration of carbon dioxide is 60 ppm or more, and the higher this value, the higher the effect. .

  The oily component used in the present invention is not particularly limited as long as the distribution ratio of carbon dioxide oil phase / water phase is 1 or more, but an oily component of 1.1 or more is preferable. By dispersing the oil component having such a distribution ratio in the bath water, the carbon dioxide gas added thereafter is present in a higher concentration in the oil phase as well as in the bath water. This makes it possible to supply a higher concentration of carbon dioxide gas to the skin than in the past. A more preferable distribution ratio is 1.3 or more, further preferably 1.5 or more, particularly preferably 1.6 or more, and particularly preferably 1.7 or more.

  Such oily components include cetyl octanoate, cetyl isooctanoate, myristyl lactate, cetyl lactate, isopropyl myristate, myristyl myristate, isocetyl myristate, octyldodecyl myristate, isopropyl palmitate, isostearyl palmitate, adipic acid Fatty acid esters such as isopropyl, butyl stearate, isocetyl stearate, isotridecyl isononanoate, decyl oleate, cholesterol isostearate; soybean oil, nuka oil, jojoba oil, avocado oil, almond oil, olive oil, cacao butter, sesame oil, permanent Oil, castor oil, coconut oil, mink oil, beef tallow, lard, etc., hydrogenated hard oil obtained by hydrogenating these natural fats, myristic acid glyceride, 2-ethylhexanoic acid glyce Glycerides such as liquids; hydrocarbon oils such as liquid paraffin, petrolatum, paraffin, microcrystalline wax, ceresin, squalane, squalene, dioctylcyclohexane, bristan, etc .; lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid Higher fatty acids such as linoleic acid, linolenic acid, lanolinic acid, isostearic acid; higher alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, cholesterol, 2-hexyldecanol; mint oil, jasmine oil, show brain oil , Cypress oil, spruce oil, ryu oil, turpentine oil, cinnamon oil, bergamot oil, mandarin oil, ginger oil, pine oil, lavender oil, bay oil, clove oil, hiba oil, rose oil, eucalyptus oil, remo Essential oils such as oil, thyme oil, peppermint oil, rose oil, sage oil, menthol, cineole, eugenol, citral, citronellal, borneol, linalool, gellarol, camphor, thymol, spiranthol, pinene, limonene, terpene compounds; silicone oil Kind. Of these, fatty acid esters are particularly preferred. The distribution ratio is a distribution ratio of the mixed oil when two kinds of oil agents are blended. Accordingly, an oil agent having a distribution ratio of less than 1 alone can be used if it is mixed with other oil agents and the distribution ratio becomes 1 or more.

  Among these, preferable oil agents having a partition ratio of 1.7 or more alone include jojoba oil, squalene, isopropyl myristate, isocetyl myristate, isopropyl palmitate, isocetyl stearate, cetyl isooctanoate, isotridecyl isononanoate and dioctyl. And cyclohexane. Therefore, as a preferable oil component used in the present invention, an oil agent having the distribution ratio of 1.7 or more is contained, and as the oil component, the distribution ratio is 1.1 or more.

  These oily components are preferably added to the bath water in an amount of 0.1 ppm or more, further 0.1 to 500 ppm, more preferably 1 to 300 ppm, particularly 10 to 300 ppm in terms of warmth and skin feel.

In the present invention, the oil component is preferably dispersed together with the surfactant in the bath water.
Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant, and it is particularly preferable to use a nonionic surfactant.
The nonionic surfactant has an action of uniformly emulsifying the oil component in the bath water and dissolving a sufficient amount of carbon dioxide gas in the oil component or micelle when the oil component is added to the bath water. One nonionic surfactant may be used, but using two or more nonionic surfactants is preferable because the self-emulsifying property of the oil component can be sufficiently exhibited in any formulation.

  Examples of the nonionic surfactant used include glycerin fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, tetraoleic acid polyoxyethylene sorbite, polyoxyethylene alkyl ether, polyoxyethylene alkenyl. Ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkenyl ether, polyethylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyglycerin fatty acid ester Etc. One or two or more of these may be combined, and in particular, one or more nonionic surfactants selected from polyoxyethylene alkyl ether and polyoxyethylene alkenyl ether, and tetraoleic acid polyoxy It is particularly preferable to combine one or more nonionic surfactants selected from ethylene sorbit and polyoxyethylene sorbitan fatty acid ester.

  These nonionic surfactants are added to the bath water in a total amount of 0.01 to 250 ppm, particularly 0.1 to 150 ppm, especially 1 to 150 ppm from the viewpoint of self-emulsification and skin feel. Is preferred.

There is no particular restriction on the order in which the oil component and carbon dioxide are introduced into the bath water, but it is preferable to dissolve the carbon dioxide gas in the bath water in which the oil component is dispersed.
Carbon dioxide gas dissolution methods include blowing carbon dioxide gas from a carbon dioxide cylinder into bath water, introducing combustion gas and dissolving it by direct contact with hot water or water, and using carbon dioxide in combustion gas as an adsorbent. There is a method to send it to hot water or water after concentration. At this time, the carbon dioxide gas may be continuously blown or dissolved, or may be dissolved under pressure. Further, a method of dissolving carbon dioxide bubbles generated by a chemical reaction in warm water (Japanese Patent Laid-Open No. 2-270158), a static mixer in a disperser provided with warm water circulated using a conduit in the middle of the conduit, and A method of forcibly mixing carbon dioxide gas and warm water with a so-called stirrer (Japanese Patent Laid-Open No. 63-242257), a method using a multilayer composite hollow fiber membrane dissolver (manufactured by Mitsubishi Rayon Engineering Co., Ltd., “Carbonated water production apparatus” MRESPA ").

As a method of dissolving carbon dioxide gas bubbles generated by the chemical reaction in warm water, a method in which a carbon dioxide gas generation product is installed in the apparatus and the generated carbon dioxide gas is introduced into bath water is preferable. As such a carbon dioxide generator, a combination of an acid and a carbonate is preferable.
As the acid, any of organic acids and inorganic acids can be used, but those which are water-soluble and solid are preferable. Among them, succinic acid, fumaric acid, malic acid, adipic acid, tartaric acid, benzoic acid, citric acid, pyrrolidone Organic acids such as carboxylic acid and salicylic acid are particularly preferred. Examples of inorganic acids include boric acid, metasilicic acid, and silicic anhydride. Moreover, as carbonate, sodium carbonate, sodium hydrogencarbonate, magnesium carbonate, potassium carbonate, etc. are preferable. One or two or more of these acids and carbonates selected from each may be used separately as they are or as an aqueous solution. It can also be used as a mixture.

  In the present invention, the carbon dioxide concentration in the bath water is preferably 60 ppm or more by introducing carbon dioxide. The carbon dioxide gas concentration in the bath water is more preferably 70 ppm or more, and further preferably 80 ppm or more.

  In order to increase the carbon dioxide concentration in the bath water to 60 ppm or more, when carbon dioxide is used, carbon dioxide of a calculated amount or more may be blown into the hot water. On the other hand, in the case of using a composition containing a carbon dioxide gas generator, about 20 to 200 g per 150 L of hot water may be added in a composition containing 5 to 80% by mass of carbonate.

  In the present invention, the oil component may be dispersed in the bath water as it is in the liquid state, or may be incorporated into a carbonated spring production system and mixed and dispersed together with the artificial carbonated spring. In addition, when using an oily component as an oily component-containing composition containing the oily component, the oily component is stably blended in the composition to maintain a solid shape retaining property, and when put into a bath water It is preferable to blend a water-soluble polymer in the oil component-containing composition from the viewpoint of improving the dispersibility of the oil and improving the warm feeling more efficiently and further improving the skin feel. Examples of the water-soluble polymer include polyethylene glycol having a molecular weight of 200 to 20000, dextrin, alkyl glyceryl ether having a linear or branched alkyl group having 10 to 40 carbon atoms, and / or a carbon number optionally substituted with a hydroxyl group. 1-5 sulfoalkyl-modified polysaccharides, alkyl methacrylate methacrylate copolymers, and water-soluble nonionic cellulose ethers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, etc. , Ionic cellulose such as cationized cellulose, carboxymethylcellulose, cationized hydroxyethylcellulose, guar gum, hydroxyethyl guar gum, methyl guar Arm, ethyl guar gum, hydroxypropyl guar gum, hydroxyethyl guar gum, hydroxypropyl guar gum, starch, hydroxyethyl starch, methyl starch, ethyl starch, hydroxypropyl starch, and hydroxyethyl starch and hydroxypropyl starch. Of these, polyethylene glycol, dextrin, and cationized cellulose having a molecular weight of 6000 to 20000 are particularly preferable from the viewpoint of shape retention when the skin feel and the composition are solid forms such as tablets and granules. Here, examples of the cationized cellulose include quaternary ammonium group-containing cellulose. Specifically, those represented by the following general formula (1) are preferable.

[In the formula (1), A represents a residue of an anhydroglucose unit, a represents an integer of 50 to 20000, and each R ¹ represents a substituent represented by the following general formula (2). ]

[In the formula (2), R ² and R ³ are alkylene groups having 2 or 3 carbon atoms, b is an integer of 0 to 10, c is an integer of 0 to 3, d is an integer of 0 to 10, and R ⁴ is carbon. A C 1-3 alkylene or hydroxyalkylene group, R ⁵ , R ⁶ , and R ⁷ are the same or different and contain an alkyl group, aryl group, aralkyl group or a nitrogen atom in the formulas up to 10 carbon atoms, A ring may be formed. X ⁻ represents an anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfuric acid, phosphoric acid, nitric acid, etc.). ]

The degree of cation substitution of the cationized cellulose is 0.01 to 1, that is, the average value of c per anhydroglucose unit is 0.01 to 1, preferably 0.02 to 0.5. Moreover, the sum total of b + d is 1-3 on average. A degree of substitution of 0.01 or less is not sufficient, and may be 1 or more, but is preferably 1 or less from the viewpoint of reaction yield. For example R ^5, R ^6, all as R ⁷ is CH _3, or remaining one is a short-chain alkyl groups such as two CH ₃ groups is preferably those which are long-chain alkyl group having 10 to 20 carbon atoms. The molecular weight of the cationized cellulose used here is between about 100,000 and 8000000. Commercially available products include Cachicelo H-60 (manufactured by Kao), kachinar (manufactured by Toho Chemical), Leogard (manufactured by Matsumoto Kosho) and the like.

  The content of these water-soluble polymers in the oil-containing component-containing composition is 1 to 25% by mass from the viewpoint of stably blending the oily component and maintaining solid shape retention, warmth and skin feel. Further, it is preferably 2 to 20% by mass, particularly 2.5 to 20% by mass, and particularly preferably 5 to 20% by mass.

  The oil component-containing composition of the present invention may further contain known bath agent raw materials that are usually blended in bath agents, such as sodium chloride, sodium sulfate, potassium nitrate, sodium nitrate, calcium nitrate, sodium polyphosphate. Inorganic salts such as ammonium chloride, iron sulfate, sodium phosphate, sodium thiosulfate, boric acid, metasilicic acid, anhydrous silicic acid, etc .; Sojutsu, sandalwood, valerian, keigai, koboku, senkyu, orange peel, orange peel, carrot, cinnamon , Peonies, mint leaves, horned dragon, scorpion, hornbill, burdock cutlet, ginger, pineapple, pine beetle, peony, jujube, rhinoceros, saffron, duckweed extract, chimney, fennel, chimpan powder, chamomile, melissa, rosemary, maroni Herbal medicines such as Arnica; alcohols such as ethanol, stearyl alcohol, isopropyl alcohol, cetyl alcohol, hexadecyl alcohol; polyhydric alcohols such as glycerin, propylene glycol, sorbitol; titanium oxide, zinc oxide, talc, sulfur, mineral sand , Yunohana, Casein, Neutral clay, Sodium salicylate, Sodium carboxymethylcellulose, Egg yolk powder, Iri mushroom powder, Mica powder, Nonfat dry milk powder, Bactericidal preservative, Moisturizer, Metal sequestering agent, Perfume, Dye, Other necessary ingredients However, it is not limited to these.

The oily component-containing composition of the present invention can be produced according to a conventional method, and the form thereof is preferably a solid such as a powder, granule, briquette tablet, tablet or the like, and particularly a solid form such as a briquette tablet or tablet. Is preferred.
In this way, by introducing carbon dioxide into the bath water in which the oil component is dispersed, the concentration of carbon dioxide in the bath water easily becomes 60 ppm or more, so if you bathe in this bath water, you will get an excellent warm feeling. The skin feel is also good. Carbon dioxide may be bathed while blowing.

Reference Example 1 (Distribution of carbon dioxide gas to oil phase / water phase)
Carbon dioxide gas was distributed by the following method. 2 mL of oil and 8 mL of ion exchange water were placed in a 15 mL screw tube, a nozzle was inserted into the bottom of the tube, and carbon dioxide gas was continuously injected for 4 minutes. After stopping the injection, when an oil layer was formed in the upper layer, the oil layer was immediately collected and used as a carbon dioxide measurement sample. Next, a pipette was gently inserted into the bottom of the screw tube to collect an aqueous phase, which was used as a carbon dioxide measurement sample.
The ATR-IR method was used for measuring the carbon dioxide concentration. The IR spectrum of carbon dioxide gas is known to exhibit strong absorption near 2350 cm ⁻¹ , and this absorption is one vibration mode. When measured at a low setting, it is observed that it splits into two absorptions, but when carbon dioxide dissolves in the liquid, the rotation is limited, so it is observed as one absorption band. And carbon dioxide dissolved in the liquid is identified.
Measurement condition equipment: PerkinElmer SpectrumOne / Universal ATR unit Resolution: 16cm ^-1
Number of scans: 16 times (about 25 seconds)
Atmospheric correction function: OFF
Measurement sequence: Oil background measurement → Oil phase measurement → Water background measurement → Water phase measurement

  As a result, as shown in Table 1, the oil phase / water phase distribution ratio of carbon dioxide varies depending on the type of oil component. It can also be seen that depending on the type of oil component, there are those having a distribution ratio of 1 or more, and 1.1 or more. In the present invention, two or more of these oil agents can be mixed and adjusted to a distribution ratio of 1.1 or more.

  Artificial carbonated spring (Comparative Example 1) made with a carbon dioxide generator, bath water (Comparative Example 2) made with a composition containing an oily component, artificial carbonated spring made with a composition containing an oily component (Examples 1-6) ) Was evaluated for warmth and skin feel by the following evaluation methods.

〔Evaluation methods〕
(1) Evaluation of warmth feeling and skin feel after bathing Using a total of 10 panelists from 20 to 40 years old, panelists are bathed in the hot water of artificial carbonated spring created by this method, and the warmth feeling and skin after bathing The feel was evaluated according to the following criteria, and the average value of 10 people was used as the evaluation score.

<Warm feeling>
5: Warming 4: Slightly warming 3: Equivalent to hot water 2: Slightly not warm 1: Not warming

<Skin feel>
5: Moist 4: Moist 3 3: Equivalent to hot water 2: Not very moist 1: Not moist

  As a result, as shown in Table 2, in the case of the artificial carbonated spring (Comparative Example 1) created by the artificial carbonated spring generator, the feeling of warmth was not satisfactory. Further, the bath water containing only the oil component (Comparative Example 2) had a weak feeling of warming and could not satisfy the skin feeling. In contrast, the artificial carbonated spring made using a bath agent containing an oil component with a carbon dioxide oil phase / water phase distribution ratio of 1.1 or more had good warmth and skin feel. (Examples 1 to 5). In addition, the artificial carbonated spring (Example 6) prepared by combining the artificial carbonated spring and the oil / water phase distribution ratio of the carbon dioxide gas with a bath preparation containing an oil component of 1.1 or less increased the feeling of warming. However, the effect was lower than that of a bath preparation containing an oily component having a carbon dioxide gas phase / water phase distribution ratio of 1.1 or more.

Claims (4)

Below (A) and (B):
(A) a composition containing an oil component and a nonionic surfactant, wherein the distribution ratio of carbon dioxide oil phase / water phase is 1.1 or more ;
(B) An artificial carbonated spring manufacturing system including a carbon dioxide gas dissolving device that blows carbon dioxide gas into bath water, wherein the composition (A) is dispersed in bath water, and (B) carbon dioxide gas is bathed in the carbon dioxide gas dissolving device. An artificial carbonated spring production system that is used by blowing it into hot water .   The nonionic surfactant is selected from one or more nonionic surfactants selected from polyoxyethylene alkyl ethers and polyoxyethylene alkenyl ethers, tetraoleic acid polyoxyethylene sorbit and polyoxyethylene sorbitan fatty acid ester 1 The artificial carbonated spring production system according to claim 1, wherein the system comprises two or more kinds including at least one kind of nonionic surfactant.   The artificial carbonated spring production system according to claim 1 or 2, wherein (B) makes the carbon dioxide concentration in the bath water 60 ppm or more. (A) the oily component having a carbon dioxide gas phase / water phase distribution ratio of 1.1 or more is selected from fatty acid esters, glycerides, hydrogen carbonate oils, higher fatty acids, higher alcohols, essential oils and silicone oils, or The artificial carbonated spring production system according to any one of claims 1 to 3, wherein there are two or more kinds.