JP2017178917A - Solid washing agents, mineral stains washing methods, and skin or hair cosmetic methods - Google Patents

Abstract

PURPOSE: To provide solid washing agents containing no surfactant which breaks the barrier layer of the skin, mineral stain-washing methods, and skin or hair cosmetic methods, first; and to provide solid washing agents for removing mineral stains, mineral stain-washing methods, and skin or hair cosmetic methods, secondly.CONSTITUTION: In a carbon dioxide gas generating solid washing agent which substantially contains no surfactant, a solid detergent has a solution with pH of 6.2 to 8.0 after dissolution, a mineral stain-washing method uses the solid washing agent, and a skin or hair cosmetic method uses the solid washing agent.SELECTED DRAWING: None

Description

  The present invention relates to a solid cleaning agent, a mineral stain cleaning method and a skin or hair cosmetic method, and is specifically referred to as a solid cleaning agent, and is used for face washing, bathing, showering, hair washing, aesthetics, etc. In particular, it does not contain petroleum-based surfactants and plant surfactants, and does not destroy the skin barrier layer. Especially, it is a solid cleaning agent, a mineral soil cleaning method, and skin or hair beauty that is excellent in cleaning power of mineral stains. It is about the law.

  In recent times, people's lives have been enriched, many useful chemicals have been developed and marketed, and people's lives seemed to have become very rich. There is a very high concern about our health. In particular, petroleum-based synthetic surfactants stand on the surface, products that say “no petroleum-based synthetic surfactant is used”, street corners, plant surfactants, and products such as silicon-free products, It has been developed and marketed (Patent Document 1).

However, even though it is derived from plants, there is no change in the use of surfactants, and only changing the type of surfactants.
That is, even if it is a plant-derived surfactant, it cannot suppress the destruction of the barrier layer of human skin.

  Therefore, without using a surfactant, as a cleaner for nails and limbs, tablets or powder-like nails containing carbonate, organic acid, reducing agent, titanium oxide powder, sodium carboxymethylcellulose and dextrin that generate carbon dioxide gas and The technique of a limb cleaning agent is known (Patent Document 2).

  According to this technology, since the surfactant is not substantially used, the barrier layer of the human skin is certainly not destroyed, but especially when the hair is washed, the mineral stains on the hair root cannot be removed. The inventors have determined.

JP 2014-231481 A Japanese Patent No. 4544735

  Accordingly, a first object of the present invention is to provide a solid detergent substantially free from a surfactant that destroys the barrier layer of the skin, a mineral dirt washing method, and a skin or hair cosmetic method.

  The second object of the present invention is to provide a solid cleaning agent for removing mineral dirt, a mineral dirt cleaning method, and a skin or hair cosmetic method.

Other objects of the present invention will become apparent from the following description.
In the present invention, “amount” represents “mass” unless otherwise specified, and “%” represents “mass%” unless otherwise specified.

The present invention for solving the above problems has the following configuration.

[Invention 1]
A solid detergent having a solution pH of 6.2 to 8.0 after dissolution in a carbon dioxide generating solid detergent substantially free of surfactant.
[Invention 2]
It contains at least one chosen from the following A group, The solid detergent of Claim 1 characterized by the above-mentioned.
[Group A]
Isopropylmethylphenol, salicylic acid, tricroic acid, glycyrrhizic acid, β-glycyrrhizic acid, trichlorocarbanilide, benzalkonium chloride [Invention 3]
The solid detergent according to claim 1 or 2, which contains water-soluble silicon or a water-soluble silicon compound.
[Invention 4]
It contains at least one selected from sodium n-octane sulfonate, sodium n-heptane sulfonate, sodium tetradesense sulfonate, sodium coconut oil fatty acid ethyl ester sulfonate, or any one of claims 1 to 3. The solid cleaning agent according to 1.
[Invention 5]
5. The solid detergent according to claim 1, comprising at least one organic acid and sodium bicarbonate among citric acid, succinic acid, fumaric acid and malic acid.
[Invention 6]
The solid detergent according to any one of claims 1 to 5, which has a tablet shape and has a friability of 5.0 wt% or less.
[Invention 7]
A mineral soil cleaning method using the solid cleaning agent according to any one of the present inventions 1 to 6.
[Invention 8]
A cosmetic method for skin or hair using the solid detergent according to any one of the present inventions 1 to 6.

  According to the inventions 1 to 6, the generated carbon dioxide gas quickly changes into bicarbonate ions depending on the pH of the hot water, dissolves in the hot water, suppresses escape into the air, and efficiently converts to high concentration as bicarbonate ions. When dissolved, bicarbonate ions are immediately absorbed into the blood vessels of the skin and hair roots, blood flow is increased, and a solid detergent with high health and beauty effects from the inside can be provided.

Furthermore, although conventional detergents and shampoos have a cleaning effect against oil stains on the skin and hair, mineral ions attached to the surface of keratin and proteins adhere to high concentrations and become mineral stains. Almost no cleaning effect was observed. In this regard, according to the first to eighth aspects of the present invention, the realization of a high concentration of bicarbonate ions and a solid detergent having a defined solution pH allows the bicarbonate ions to be present free, and the minerals attached to the skin and hair are free of weight. Carbonate ions are removed, body odor and hair odor caused by the mineral stains can be removed, and it is now possible to provide health and beauty solid hair cleaning agents or mineral stain cleaning methods and beauty methods. It was. That is, in the present invention, “mineral stain” has the following meaning.
Hair (body hair / hair) is said to be a mineral outlet, and unnecessary minerals (calcium, magnesium, potassium, sodium, etc.) in the body are discharged from the pores and become mineral dirt. That is, if this mineral content is left as it is, it adheres to and accumulates on the skin and coat with sebum and the like, causing a stubborn stain and odor. These minerals are positive ions that are electrostatically bound to the negatively charged hair, and if you use bicarbonate ions that are more negatively charged than the hair, this mineral stain is drawn and washed off. be able to.

  Furthermore, according to the first to eighth aspects of the invention, bicarbonate ions can be present more freely, and free hydrogen ions can also be present, and the effect of cleaning mineral stains is enhanced, resulting in higher health, beauty, and hairdressing effects. A solid bath preparation could be provided, and the effects of the present invention were remarkable.

  Furthermore, according to the said invention 1-8, cleaning agent can be made into solids, such as powder, a granule, and a tablet, and generation | occurrence | production of a carbon dioxide gas can be activated more actively by specific neutral-weak alkali pH, and the remarkable effect of invention is acquired. In particular, according to the above inventions 2 and 3, the neutralization reaction can be made active when charged in solid form, and the effect of the present invention is remarkable.

  According to the second aspect of the present invention, it is possible to efficiently continue to generate micro-sized carbon dioxide bubbles of a certain diameter or less efficiently for a long time, and the pH of the aqueous solution after dissolving the solid detergent is easily increased by bicarbonate ions. Can be made a value that can be neutralized and dissolved at a high concentration, and can maintain a sufficient carbon dioxide concentration without impairing the neutralization reactivity in the solid detergent, and in particular, according to the invention 5, citric acid, The skin affinity of succinic acid, fumaric acid, and malic acid enhances the transdermal absorption of carbon dioxide and provides a solid cleaning agent with high health and beauty effects. Especially in the case of citric acid, the effect is very high.

  Further, according to the inventions 5 and 6, the solid detergent can be made into a tablet, for example, and the acidic component in the tablet dissolves and comes into contact with a high concentration to easily cause a neutralization reaction. The fine carbon dioxide bubbles can be efficiently generated, the micro-sized bubbles can be continuously generated over a long period of time, and the concentration of the carbon dioxide component dissolved in water can be maximized. The effect of can be remarkable.

  Further, according to the invention 5, the organic acid is specified, and particularly the citric acid as the organic acid is efficiently neutralized even under the condition of a small amount of citric acid that becomes neutral after dissolution. The carbon dioxide gas component that efficiently generates micro-sized carbon dioxide bubbles efficiently and dissolves in water at a higher concentration, and has the property of making bicarbonate ions free, making the effects of the present invention remarkable. It was.

  The solid cleaning agent according to the present invention is not limited to the uses described in face washing, bathing, showering, hair washing, aesthetics and other background arts.For example, it is stored in a shower head or a mist generating facial device, etc. Depending on the combination, it may be used for shower water or aesthetic mist.

  The present inventors have found that carbon dioxide gas is present at a pH of 6.2 or more as 28% or more as bicarbonate ions, and this bicarbonate ion does not destroy the barrier layer of the skin at all and completely removes dirt including old keratin. It has been found that bicarbonate ions can also be removed by inclusion of bicarbonate ions, even after removal and removal of surfactants by the surfactant. Therefore, it was also found that mineral ions aggregate on the inner surface with the keratin surface of the skin on the negative side and the barrier layer remains to form a potentiometric battery, which has a new effect of forming a youthful skin.

  Despite the fact that bicarbonate ions are used for washing, they absorb percutaneously, improve blood flow, have parasympathetic nerves as an advantage, and can be relaxed and have an unexpected effect of getting good sleep (deep sleep). I also found out.

When the compound selected from the group A of the present invention is at least 0.03% by mass to 0.18% by mass, the effects of the present invention are excellent. Furthermore, when it was in this range, it turned out that a bactericidal action appears favorably and there exists the effect of this invention synergistically.
[Group A]
Isopropyl methylphenol, salicylic acid, trichloro acid, glycyrrhizic acid, β-glycyrrhizic acid, trichlorocarbanilide, benzalkonium chloride

  When the content of the water-soluble silicon or water-soluble silicon compound of the present invention is from 0.5% by mass to 5.0% by mass, the effects of the present invention are excellent. Furthermore, it has been newly found that hair fall is less within this range.

Furthermore, when the solid detergent is a tablet-type detergent, the tablet hardness is preferably 25 kg or more, which is effective for tablet molding stability. When tablet friability is 5.0 wt% or less, acidic components in the tablet dissolve in high concentration and come into contact with each other, so that neutralization reaction is likely to occur, and the generation of fine carbon dioxide bubbles inside the tablet is efficient. Microbubbles can be generated frequently over a long period of time, the concentration of carbon dioxide component dissolved in water can be maximized, and the effects of the present invention can be made remarkable. When the friability is 3.0 wt% or less, the generation of fine carbon dioxide bubbles of the above micro size is more efficiently caused, which is more preferable from the effect of the present invention. Most preferably, the friability is 2.0 wt% or less.
The friability of the tablet according to the present invention will be described. The friability is determined by storing the tablets in an environment of 25 ° C. and 40% RH for 1 week, and then putting 5 tablets in a tablet friability tester (manufactured by Higaki Medical Science Co., Ltd.) and rotating for 5 minutes (rotation speed) Is 25 rpm). After finishing, the powder on the surface of each tablet is used. ゙ Lashi (for example ゙ used for cleaning the chemical balance) ゙ Ask. [(Tablet weight before wear (g) sum-Tablet weight after wear (g) sum) / Tablet weight before wear (g) sum] × 100 = Table friability (wt%) Tablet friability is 5.0 wt% or less Then, micro-sized foaming in the tablet is caused slowly, and dissolution of carbon dioxide in the liquid can be controlled efficiently. Therefore, the friability is preferably 5.0 wt% or less, more preferably 3.0 wt% or less, and particularly preferably 2.0 wt% or less. The friability within the present invention is that the generation of carbon dioxide gas in the tablet occurs more efficiently, particularly after dissolution of the tablet starts, the carbon dioxide gas dissolves efficiently in water, and the bubble diameter is reduced. It becomes finer and the effects of the present invention are excellent.

  In the present invention, a tablet detergent is more preferable than a granular detergent because of its ease of handling.

  The solid cleaning agent of the present invention may be used as a cleaning liquid after hot water of about 40 ° C. is placed in a certain basin or the like and dissolved. Preferably, the solid cleaning agent is put in a shower head (FIG. 1) and showered. The effect of the present invention is excellent when used.

  The use of citric acid as the organic acid is more effective in neutralization with carbonates than in the case of using other organic acids, so that the effects of the present invention can be exhibited more remarkably.

Water-soluble silicon or water-soluble silicon compounds used in the present invention, for example, silica (SiO _3), can also be used any known public such as orthosilicic acid, under the name UMO micron powder and fine silicon powder from Inc. Links It can also be obtained. In particular, when UMO micron powder is used, the effect of the present invention can be remarkably expressed.

Hereinafter, the present invention will be described in more detail.
In the present invention, even if the pH immediately after the solid detergent is dissolved is neutral or weakly alkaline at a specific value, an environment in which the neutralization reaction occurs efficiently in the detergent appears and the reaction is continued for a certain time. The concentration of carbon dioxide dissolved in water is sufficiently high, so that the dissolved carbonic acid component can be made into high-concentration bicarbonate ions, and some can be made into free bicarbonate ions in hot water. .

  The pH immediately after dissolution of the solid detergent in the present invention is important to be in the range of pH 6.2 to 8.0 so that the dissolved carbon dioxide component is neutralized and dissolved as bicarbonate ions at a high concentration. PH is in the range of 7.0 to 8.0, where carbon dioxide generation and efficient conversion to bicarbonate occurs, especially when the composition is substantially free of bicarbonate sequestering substances. This is important in terms of enhancing the cleaning ability of mineral dirt.

  The meaning of pH immediately after dissolution means that the bicarbonate ion spontaneously volatilizes the carbon dioxide gas even if the detergent is close to neutral pH, and the pH gradually rises. Even if the pH is 7.0, the pH changes to about 7.5 after 24 hours, and further increases by blowing air in a jet bath or the like. Therefore, it is appropriate that the pH after dissolution is defined by the pH immediately after.

  Whether it's face washing, hair washing, showering, footbath, bathing, the required amount of solid detergent is 20g to 100g (0.01% to 5%) per 200 liters. The pH immediately after the agent is dissolved is a pH value necessary for the presence of bicarbonate ions at a high concentration.

  Since the solid detergent according to the present invention is adjusted to the pH value of the present invention by an acid or alkali pH adjuster as necessary, it is suitable for efficient neutralization reaction and dissolution in hot water. One feature of the present invention is that the pH of hot water or aqueous solution in which carbon dioxide gas is generated at a rate and the solid detergent is completely dissolved can be neutralized to a specific value. In particular, adjusting the pH with sodium bicarbonate is a preferred embodiment.

  In nature, neutralization reaction is unlikely to occur, but in powders, granules or tablets, bicarbonate and organic acid come into contact with high concentration, causing neutralization reaction, while adjusting the pH of a large amount of dissolved water, From neutral to weakly alkaline.

  In the present invention, the amount of the organic acid added to the bicarbonate is effective as long as the pH adjustment is within the range of the present invention, but it is desirably 1/50 to 2/3, particularly 1 / 10 to 1/3 is preferable.

  As a result, the generated carbonic acid component is neutralized to become bicarbonate ions, but even if bicarbonate is added from the beginning, for example, there is no bathing effect that warms the body, so it is the same as natural carbonated spring In addition, it has made a surprising discovery that no effect on health, beauty, aesthetics, etc. can be obtained unless it goes through a mechanism that generates carbon dioxide and becomes bicarbonate ion via that carbon dioxide. I'm proud.

  In this way, when the hot water and water are in a neutral state, the bicarbonate and the organic acid such as citric acid react slowly and finely, so that the high bathing effect of the present invention can be obtained and a product with high added value can be provided. .

  The above-mentioned effect of the present invention is that the bicarbonate and the organic acid (particularly citric acid) are granulated with polyethylene glycol, and each is mixed under the condition within a certain ratio, so that the pH of the cleaning agent is within a certain range immediately after dissolution. By designing, when water penetrates into the cleaning agent, it reacts vigorously and uniformly, and the generated carbon dioxide bubbles are generated as fine carbon dioxide gas of micro size, and the cleaning agent has many small bubbles until the end. It is generated and dissolved in water before the bubbles come into the air. The concentration of carbon dioxide in the liquid and dissolved bicarbonate ions can be increased unnecessarily, and the carbon dioxide dissolves and becomes bicarbonate ions. A cleaning agent adjusted to a pH of 6.2 to 8.0 and containing a substance of Group A of the present invention, more preferably substantially free of bicarbonate sequestering substance The effect of the present invention is There is exhibited to the maximum.

  Furthermore, in the present invention, since the mixture of bicarbonate is a granulated material prepared by coating with polyethylene glycol using a fluidized bed, the effects of the present invention such as a uniform reaction in the tablet are exhibited. Is greatly demonstrated.

  In the present invention, when the solid detergent of the present invention is used as a tablet, the neutralization reaction efficiency inside the tablet can be maximized even though the solution becomes neutral as the tablet hardness increases.

  The bicarbonate sequestration substance referred to in the present invention is an organic or inorganic compound containing mineral components such as calcium and magnesium. Specifically, calcium sulfate, calcium silicate, calcium carbonate, calcium oxide, calcium hydroxide, etc. And magnesium salts such as magnesium sulfate, magnesium silicate, magnesium carbonate, magnesium oxide, magnesium hydroxide, and magnesium stearate.

  Specific examples are as described above, but other compounds containing calcium and magnesium have the same effect of sequestering bicarbonate ions, and the present invention does not contain these bicarbonate sequestering compounds. It is indispensable to exert an effect.

  However, the present invention preferably contains water-soluble silicon. As water-soluble silicon, any publicly known and publicly available silicon may be used. In particular, water-soluble silicon can be obtained from Lynx Co., Ltd. under the names of UMO micron powder and fine silicon powder, and when UMO micron powder is used, the effects of the present invention can be remarkably expressed. Moreover, plant-derived water-soluble silicon sold by Mediations Co., Ltd. can be obtained, and this also showed a remarkable effect similar to UMO micron powder.

  As the organic acid used in the present invention, citric acid, fumaric acid, succinic acid, malic acid, and the like are used, but using an organic acid containing at least citric acid more effectively neutralizes the detergent. Sustained and fine bubbles can be generated, and the effects of the present invention can be exhibited more significantly as a preferred compound.

  In addition, when obtaining a granulated product by granulating at least one of bicarbonate or organic acid in a fluidized bed, when using a mechanical fluidized bed granulator that does not substantially use air as a stirring action, The reaction in the tablet can be enhanced efficiently. As the fluidized bed of the mechanical stirring method, since the powder is flowed using mechanical blades such as a propeller without using air for stirring, the moisture brought in from the humid air during granulation It is also possible to make a vacuum with a vacuum pump during granulation without reducing the amount of moisture in the granulation, and it is possible to granulate by lowering the amount of polyethylene glycol. It is preferably used because it can exhibit an effect that can be reduced.

  A mechanical fluidized bed granulator that does not substantially use air as an agitation action is a mixer that arranges a chamfered shovel in a horizontal drum, causes centrifugal diffusion and vortex action, and causes three-dimensional flow. For example, it is sold in the market as a product made in Germany Leedige or Matsuzaka Giken.

  More preferably, the granulator is equipped with a vacuum pump for reducing the pressure. That is, it is preferable in order to improve the effect of the present invention by reducing the pressure during cooling and operating so that even a little moisture can fly. Furthermore, it is preferable to have a chopper for preventing the granulated granules from becoming coarse particles upon cooling. That is, the effect of reducing the diameter of the carbon dioxide gas bubbles of the present invention to a micro size is exhibited by operating the chopper during cooling to adjust the particle size, which is a more preferable granulation method.

  In the present invention, the most preferable production method is that sodium bicarbonate is granulated by a fluidized bed granulator using polyethylene glycol (PEG) and a mechanical stirring system, and a certain amount of organic acid and anhydrous water are added to the granulated product. Sodium carbonate and polyethylene glycol are added, and after mixing, compression molding is performed at a high pressure to obtain a solid bath agent, whereby the effect of the present invention is greatly exerted.

  Of course, the mixture mainly composed of organic acid is also granulated with polyethylene glycol, mixed with polyethylene glycol without granulating bicarbonate, and mixed with organic acid granulated product to obtain tablets. In addition, the amount of the compound to be granulated is a relatively small production method from the viewpoint of process, but in any case, either the bicarbonate or the organic acid is used from the viewpoint of cost. It is desirable to produce by simply granulating and mixing one side. Even if this granulated product is used as a powder, the effect of the present invention is exerted greatly, but by compressing and forming a single tablet, the neutralization reaction of the present invention is maintained for a long time and dissolved carbon dioxide gas. Can be increased. However, it is also a preferable production method that both bicarbonate and organic acid are mixed or coated with polyethylene glycol.

  The PEG used in the present invention is preferably one having an average molecular weight of 1000 to 8000 in view of the effects of the present invention. PEG having an average molecular weight of about 1450 or 6000 makes the granulation result preferable from the viewpoint of improvement in molding stability, wrinkle adhesion resistance, capping and tablet molding speed by a compression molding tablet machine such as a rotary tableting machine. When the powder / granule or tablet is dissolved in hot water, the carbon dioxide component can be dissolved to the maximum in the bicarbonate ion, and the solid detergent of the present invention consisting of the powder / granule or tablet is As the hardness, thickness, and diameter increase, the effects of the present invention can be made more remarkable.

  The ratio of polyethylene glycol to 100 parts by weight of granulated product A or mixture A of bicarbonate (sodium bicarbonate or potassium bicarbonate) is 1/100 to 1/5, particularly preferably 1/100 to 1/10, When the ratio of PEG is less than the above amount, the diameter of the carbon dioxide bubble is increased and the foaming time is shortened, and the carbon dioxide component dissolved in the hot water may not be increased, while the amount of polyethylene glycol is larger than the above. As a result, the amount of bubbles generated is suppressed, and the amount of carbon dioxide gas dissolved in the same manner may be reduced.

  Further, in the present invention, after obtaining a granulated product A or PEG mixture A of bicarbonate, and adding an organic acid or organic acid granulated product B or PEG organic acid mixture, anhydrous sodium carbonate or anhydrous potassium carbonate is added. By adding an anhydride such as the above, the effect of the present invention can be exhibited more remarkably, and the amount of foaming can be increased for a long time while the bubble diameter of carbon dioxide gas is made optimally small. It turns out that it is obtained.

  Moreover, as an effect of this anhydride, it is a compound that exhibits the effect of the present invention more preferably when anhydrous sodium carbonate is added.

  Further, in the present invention, when the organic acid is not granulated, and only the polyethylene A is added to and mixed with the granulated product A and the organic acid, and the solid powder / granule or the tablet is formed by compression molding, It was found that the bubbles of size could be foamed for a long time, and the carbon dioxide component dissolved in the hot water could be increased, and a good cleaning agent could be obtained. In this case, it is a desirable manufacturing method in which the steps can be greatly omitted and the cost effect is also achieved.

  On the other hand, the micro-sized foam of the present invention is foamed for a long time and dissolved in hot water even in the case of compression molding simply by granulating organic acid with PEG and mixing bicarbonate and PEG at a constant temperature. When the carbon dioxide component to be used is maximized, the process can be largely omitted, and the cost effect is combined, it has been found that this is a desirable manufacturing method.

  The ratio of polyethylene glycol to organic acid used in this production method is preferably 5 to 15 parts by mass with respect to 100 parts by mass of organic acid.

  The amount of organic acid or organic acid mixture B or organic acid granulation B added to bicarbonate granulate A or PEG mixture A is not specified, but is preferably 1/50 to 2/3, particularly preferably 1. It is desirable that the ratio is from / 10 to 1/3 to maximize the effects of the present invention.

  Although the effect of the present invention can be obtained by adding an anhydride without any particular granulation, more preferably, the organic acid is added together with polyethylene glycol or PEG granulated B, and granulated A It is possible to prepare a solid bath agent having a preferable neutralization reactivity by mixing and tableting with a powder or compression molding.

  Furthermore, in the present invention, either the step of creating the granulated product A or the mixture A, or the step of mixing the granulated product A with the organic acid or the granulated product B, either powder, granulation or compression molding It is preferable to add an anhydride to the process.

In the present invention, it is desirable to use sodium lauryl sulfate, sodium lauroyl sarcosinate, sodium myristoyl methylalanine, sodium lauryl sulfonate, sodium n- (normal) octane sulfonate, tetradecene as compounds desirable to be used for powder mixing and tableting. Sodium sulfonate and coconut oil fatty acid ethyl ester sodium sulfonate are used. Among these, it is sodium n- (normal) octane sulfonate and sodium n-heptane sulfonate that can obtain the effects of the present invention remarkably. That is, both of these compounds not only cause micro-size foaming when the cleaning agent according to the present invention is dissolved in hot water and maintain transparency of the hot water after dissolution, but also keep the body warm by the cleaning agent. A favorable effect is also exhibited in terms of improving the effect.
The amount of sodium n- (normal) octane sulfonate, sodium n-heptane sulfonate, sodium tetradesense sulfonate, sodium palm oil fatty acid ethyl ester sulfonate of the present invention is 0 of the solid detergent according to the present invention. It may be about .0005 to 0.01% by mass.

  In the present invention, in addition to the main component, other components (additives) can be mixed as necessary. Examples of other additives include health ingredients such as hyaluronic acid, fragrances, pigments, surfactants, and the like, and if necessary, anhydrides such as sodium carbonate.

  The organic acid or organic acid mixture B and granulated product B include anhydrides such as sodium carbonate, fragrances, pigments, polyethylene glycol, and the like as desirable additives.

  For compression molding to mix powders or produce tablets, known compression molding machines can be used without any particular restrictions, such as hydraulic press machines, single-shot tablet machines, rotary tablet machines, briquetting machines, etc. Can be used. The size of the punch used in this tableting machine or the like is preferably 7 mm or more when the punch is circular, and when the punch is a triangle or square, the diameter is 7 mm or more when converted to a circular punch. Those are preferred. The same applies to the thickness of the ridge. In the case of obtaining a round tablet product, the tablet diameter is preferably 7 mm or more, more preferably 10 mm or more, and the thickness is also 7 mm or more, preferably 10 mm or more. More preferably, the diameter and thickness are each 7 mm or more.

  As described above, when a tablet is used, the shape does not necessarily have to be a circle having a flat surface, and the shape is not limited in any way as long as it is a solid body of 7 mm or more, whether it is an oval, a tablet, or a sphere.

  In the present invention, it is preferable to cause micro-size foaming slowly in a hard solid of a certain size or more, and to more efficiently dissolve carbon dioxide gas in the liquid. Therefore, the hardness is preferably 30 kg or more, and the diameter and thickness are preferred. Is more preferably 7 mm or more, the hardness is particularly preferably 60 kg or more, the higher the hardness, the more effectively the generation of carbon dioxide in the tablet and the efficient dissolution of carbon dioxide in the bath, The bubble diameter is reduced, yielding favorable results.

  Hereinafter, hardness, which is a preferable requirement when the solid detergent of the present invention is used as a tablet, will be described.

  In order to realize the present invention, the hardness as the tablet breaking strength from the diameter direction used in the examples of many patent specifications was measured.

  In this method, the breaking strength of the tablet is measured, and the hardness [kg] of the tablet is measured four times using a digital tablet hardness tester New Speed Checker TS75NL manufactured by Okada Seiko Co., Ltd. as a hardness measurement method in the diameter direction. . In this case, the hardness was reproducible and no large variation in value was observed.

  When the bubble diameter of the carbon dioxide gas generated in the liquid, which is a preferable tablet condition of the present invention, is measured visually, the tablet diameter is 7 mm or less, and the bubbles are uniformly generated, the neutralization reaction is finished, and the tablet is finished. Until the tablet is completely melted, the tablet remains sinked to the bottom, and it is possible to measure the tablet hardness using 12 kinds of samples of 7 lots of test produced tablets so that carbon dioxide can be efficiently dissolved in the liquid. If the average value is measured four times, the amplitude of the measured value can be ignored, and the tablet has an average surface hardness of 15 kg or more, preferably 18 kg or more (more preferably 25 kg or more, most preferably 30 kg or more, particularly 60 kg or more). It was confirmed that

  The present invention preferably has a constitution that does not substantially contain a bicarbonate sequestering substance. In the present invention, the bicarbonate sequestering substance is an inorganic compound and an organic compound containing mineral components such as calcium and magnesium as described above.

  In the present invention, if there is a bicarbonate sequestering substance, the bicarbonate ions generated in the hot water according to the present invention will be sequestered. For this reason, mineral stains that are ionically bonded to body and hair proteins and keratin. In some cases, the action of adhering to and dissolving the resin cannot be achieved. On the other hand, if there is no bicarbonate sequestering substance, the mineral stain adheres to the bicarbonate ions and is removed, resulting in a negative ion body / hair surface. The effect which can be returned to a state can be expected.

  In the present invention, it is desirable not to add compounds other than the compound of the present invention as much as possible. However, 1 or 2 of an acidic component, an alkali component, a scent component, a gorgeous hot spring component, etc., which do not belong to the bicarbonate sequestering substance, as necessary. The above can also be added.

  In the present invention, if the organic acid component relative to the amount of bicarbonate is larger than the preferred range of the present invention, the bubble size is large, the reaction may be intense and the reaction may be terminated in a short time, and the amount of bicarbonate relative to the amount of bicarbonate If the amount of the organic acid component is too small, the neutralization reaction does not occur efficiently, and the generated carbon dioxide gas is reduced, and the effects of the present invention may not be exhibited.

  If the amount of bicarbonate is too small, the amount of polyethylene glycol used must be increased, otherwise the neutralization reaction will be too intense and the bubble diameter will be increased, impairing the effects of the present invention. There is a case. Also, even when the amount of polyethylene glycol is large or small relative to the amount of bicarbonate or organic acid, the neutralization reaction may not occur uniformly and continuously, and the bubble diameter may not be constant. is there.

  As described above, after adding the necessary components of the present invention in the preferred amount ratio of the present invention, a pH adjusting agent capable of sufficiently exerting the effects of the present invention is added to adjust the pH of the hot water after dissolution. It is a desirable embodiment to be within the scope of the present invention.

  As the pH adjuster used in the present invention, sodium carbonate, sulfuric acid, or an organic acid is preferably used. However, any publicly known and publicly available one can be used without any particular limitation, and in particular, a pH adjuster as a food additive. It is preferable from the viewpoint of safety that the detergent may enter the eyes and mouth. For example, trisodium citrate (sodium citrate), disodium citrate, monosodium citrate, potassium gluconate , Sodium gluconate, disodium succinate, sodium acetate, DL-sodium tartrate, sodium L-tartrate, potassium carbonate, sodium bicarbonate, sodium carbonate, sodium lactate, DL-sodium malate, and the like.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to these.

[Example-1]
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to these.

1. Preparation of cleaning powder for comparison A powder cleaning agent of interest (Comparative 1) was prepared by adding to the improved model of Matsuegi Giken-made Redige Mixer VT1200 so that the total weight was 430 kg and mixing for about 10 minutes.
Ingredient (mass%) Comparison 1
Anhydrous sodium carbonate 25
Succinic acid 25
L-cysteine hydrochloride 0.4
Titanium oxide powder 0.1
Dextrin 0.1
CMC 0.6
PEG6000 6
Lactose 3
Fragrance 0.2
Hydrolyzed keratin 0.01
Carrot powder 0.01
Cha extract 0.01
Licorice flavonoid 0.01
Benzalkonium chloride 0.0005
Hydrolyzed collagen 0.015
Natural vitamin E 0.05
Granular sugar 39.4945
100
The granular saccharide used was Meiji Seika's granular saccharide containing white sugar, lactose and dextrin, and encapsulating high-pressure gas.

2. Preparation of the cleaning powder of the present invention A powder cleaning agent of the present invention (Invention 1) was prepared by adding to the improved version of the RED 1200 mixer VT1200 manufactured by Matsuzaka Giken Co., Ltd. so that the total weight was 430 kg and mixing for about 10 minutes.
Ingredient (mass%) Invention 1
Anhydrous sodium carbonate 4.0
Sodium bicarbonate 74.9
Citric anhydride 15.8
PEG6000 4.8
OSA-Na 0.5
100
OSA-Na: sodium n-octane sulfonate

3. Preparation of comparative cleaning agent and cleaning powder of the present invention In Example 1, the amounts of anhydrous sodium carbonate, sodium bicarbonate and citric acid were adjusted to the pH shown in Table 1, and Comparative Examples 2, 3, 4 and 5 and Inventions 2, 3 and 4 were prepared.

  Above 1. ~ 3. Dissolve 1.5g of the cleaning powder prepared in 4 in 4L of hot water at a temperature of 40 ° C to prepare the cleaning liquid shown in Table 1, and wash the hair to 20 people using a shower nozzle until the liquid disappears at a rate of 13ml / s. The results are summarized in Table 1.

[Evaluation criteria]
(A) Detergency Evaluation 1: Hair dirt remains sticky (less than 50% when completely removed)
Evaluation 2: A little stickiness of hair stains remains (50% or more and less than 80% when completely removed)
Evaluation 3: The hair was removed. The moisture of the hair is gone and it ’s gone. (At least 80% when fully removed and less than 50% moisture satisfaction)
Evaluation 4: The hair was removed. Slightly less moisture in the hair, slightly rustling. (80% or more when completely removed, moisture satisfaction 50% or more and less than 90%)
Evaluation 5: The hair was removed. There is moisture of hair, too and is smooth. (80% or more when fully removed and 90% to 100% satisfaction with moisture)

(B) Follicle dirt Evaluation 1: No follicle dirt is removed.
Evaluation 2: 20% or less when the follicle dirt is completely removed.
Evaluation 3: The hair fouling is 20% or more and less than 50%.
Evaluation 4: The hair fouling was 50% or more and less than 80%.
Evaluation 5: The hair fouling was 80% or more and 100% (no follicle fouling even when viewed with a magnifier).

(C) Warmness of toes after 30 minutes from hair washing Evaluation 1: Less than 10% based on Evaluation 5.
Evaluation 2: Warm of 10% or more and less than 20% based on Evaluation 5.
Evaluation 3: When evaluation 5 is used as a reference, the warmth is 20% or more and less than 50%.
Evaluation 4: When evaluation 5 is used as a reference, the warmth is 50% or more and less than 80%.
Evaluation 5: It is as warm as hot water (100% on the basis).

(D) The ratio of a good sleep time was evaluated using an OMRON sleep meter HSL-101.
Evaluation 1: A good sleep time of less than 10%.
Evaluation 2: A good sleep time of 10% or more and less than 20%.
Evaluation 3: A good sleep time of 20% or more and less than 40%.
Evaluation 4: A good sleep time of 40% or more and less than 50%.
Evaluation 5: A good sleep time of 50% or more.

[Table 1]
The solution pH is a value measured by dissolving 1.5 g of cleaning powder in 4 L of tap water and measuring at room temperature.

  As is apparent from Table 1, the present invention has excellent detergency even with no surfactant, removes hair root mineral stains, and further bicarbonate ions enter the blood vessels through the skin, increasing the bicarbonate ion concentration. The blood flow improves to send oxygen obtained from breathing to neutralize the blood flow, and even if the hair is washed in the shower, the blood flows sufficiently to the capillaries of the end foot, improving the feeling of warming Furthermore, it can be seen that the ratio of the time during which sleep was able to sleep well in the sleep time increases due to the deep body temperature rise.

[Example 2]
Preparation of the cleaning powder of the present invention (Invention 5 and 6) In addition, 0.1% by mass of isopropylmethylphenol is added to the weight ratio, and the ratio of the other components is reduced evenly by the amount added. Created in the same way.
2.0% by mass of water-soluble silicon (UMO micron powder purchased from Lynx Co., Ltd.) was added, and the amount of added water was equally lowered according to the ratio of other components to prepare Invention 6.
Evaluation was conducted in the same manner as in Example 1, and the results are summarized in Table 2.

[Table 2]

From the results shown in Table 2, it can be seen that the addition of isopropylmethylphenol and water-soluble silicon exhibits the effects of the present invention.
Furthermore, the sterilizing effect of isopropylmethylphenol itself can be exhibited, the skin of the face, which is the effect of water-soluble silicon, can be eliminated, the wrinkles can be reduced, the skin can be stretched, and the inherent properties of the material can be exhibited. understood.

[Example 3]
Operation-1
390 kg of sodium hydrogen carbonate is added to a modified model of RED1200 manufactured by Matsuzaka Giken Co., Ltd., hot water of 60 ° C. is circulated through the jacket at a rotation speed of 115 rpm, and when the product temperature reaches 55 ° C., 20 kg of PEG 6000 is granulated. When the product temperature reaches 65 ° C, chilled water is circulated through the jacket, the pressure is reduced to 10 Torr, and the product temperature is cooled to 45 ° C.
The obtained granule is called AA granule.

Operation-2
A 333 kg of AA granules, 67 kg of anhydrous citric acid, 17 kg of anhydrous sodium carbonate, 4 kg of PEG6000, and 2 kg of OSA-Na are added to a modified Leedge mixer VT1200 and stirred at 115 rpm for 10 minutes to prepare a mixture A.

Operation-3
After adding up to PEG 6000 in the same manner as in the operation-2, 0.4 kg of isopropylmethylphenol and 2 kg of OSA-Na were added and stirred at 115 rpm for 10 minutes to prepare a mixture B.

Operation-4
After adding up to PEG 6000 in the same manner as in the above operation-2, 8 kg of water-soluble silicon (Linx UMO Micron Powder Co., Ltd.) and OSA-Na were added and stirred at 115 rpm for 10 minutes to prepare a mixture C.

Operation-5
The mixture prepared by the above operation was subjected to a tough press collect 1527HU (tablet making machine) manufactured by Kikusui Seisakusho, and a weight of 7 tons was added to prepare tablets having a hardness shown in Table 3 having a diameter of 30 mm, a thickness of 15 mm, and a weight of 15 g.
Table 3 summarizes the evaluation results.

[Table 3]

  From the results shown in Table 3, when a tablet is used, the dissolution time becomes longer, and fine carbon dioxide gas is generated from the powder. As a result, the amount of carbon dioxide dissolved in the aqueous solution increases, and the carbon dioxide gas becomes bicarbonate ions. It has been found that the effect of promoting the flow increases, the blood flow to the terminal increases, the toes become warm, and the deep body temperature also rises, so that it is possible to sleep well.

  Mixtures B and C can increase tablet hardness by adding them, and thus can exert the effect of the present invention on deep sleep due to the improvement of blood flow to the end by improving blood flow and deep body temperature. found.

[Example 4]
Instead of OSA-Na in Example 2, Operation-2, Operation-3 and Operation-4, 2 kg of sodium tetradesense sulfonate was added, and the other operations were performed in the same manner as in Example 3, and the evaluation is shown in Table 4. The results are summarized.

[Table 4]

  From the results of Table 4, it can be seen that when the lubricant is changed from OSA-Na to sodium tetradesense sulfonate, depending on the type of lubricant, the effect of hair root mineral stains is affected, and OSA-Na is preferred.

[Example 5]
In place of OSA-Na in Operation-2, Operation-3 and Operation-4 in Example 3, 2 kg of coconut oil fatty acid ethyl ester sodium sulfonate was added, and the same operation as in Example 3 was performed except that Table 5 The evaluation results are summarized in.

[Table 5]

  From the results in Table 5, it can be seen that changing the lubricant from OSA-Na to coconut oil fatty acid ethyl ester sodium sulfonate affects the effect of hair root mineral stains depending on the type of lubricant, and OSA-Na is preferred. .

[Example 6]
In the mixtures A, B and C of Example 3, the weight of 7 tons and the tableting speed of operation 5 were changed as needed, and the friability was changed by changing the weighting time of the maximum tableting load especially by the tableting speed. Made different tablets. The dissolved pH was 7.0. Table 6 summarizes the evaluation results.

[Table 6]

From the results shown in Table 6, when the tablet friability is 5.0 wt% or less, micro-sized foaming in the tablet is caused slowly, and dissolution of carbon dioxide in the liquid can be efficiently controlled. Therefore, the friability is preferably 5.0 wt% or less, more preferably 3.0 wt% or less, and particularly preferably 2.0 wt% or less. The friability within the present invention is that the generation of carbon dioxide gas in the tablet occurs more efficiently, particularly after dissolution of the tablet starts, the carbon dioxide gas dissolves efficiently in water, and the bubble diameter is reduced. It turns out that the effect of this invention is show | played favorably. Further, from the mixtures B and C, it can be seen that the addition of the compound of the present invention exhibits the effects of the present invention.

Claims (8)

A solid detergent having a solution pH of 6.2 to 8.0 after dissolution in a carbon dioxide generating solid detergent substantially free of surfactant. It contains at least one chosen from the following A group, The solid detergent of Claim 1 characterized by the above-mentioned.
[Group A]
Isopropyl methylphenol, salicylic acid, trichloro acid, glycyrrhizic acid, β-glycyrrhizic acid, trichlorocarbanilide, benzalkonium chloride The solid detergent according to claim 1 or 2, which contains water-soluble silicon or a water-soluble silicon compound. The solid detergent according to any one of claims 1 to 3, comprising at least one selected from sodium n-octanesulfonate, sodium n-heptanesulfonate, and sodium tetradesensesulfonate. 5. The solid detergent according to claim 1, comprising at least one organic acid and sodium bicarbonate among citric acid, succinic acid, fumaric acid and malic acid. The solid detergent according to any one of claims 1 to 5, which has a tablet shape and has a friability of 5.0 wt% or less. A mineral dirt cleaning method using the solid cleaning agent according to claim 1. A cosmetic method for skin or hair using the solid detergent according to any one of claims 1 to 6.