JP2018043969A - Foamable external composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide foamable external compositions capable of substantially retaining a foaming situation for a fixed time after the foaming situation has been established, without requiring an alcohol component and/or a hypochlorous acid component as essential.SOLUTION: A foamable external composition containing water, a hydroxide, and a thickener at least is provided. The hydroxide is selected from alkali metal hydroxide, alkali metal earth metal hydroxide, and tetra-alkylammonium hydroxide.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an external composition having foamability. More specifically, the present invention can substantially maintain the foamed state for a certain period of time after the foamed state is formed without requiring an alcohol-based component and / or a hypochlorous acid-based component. The present invention relates to a foamable external composition.

  In the present invention, “external use” means that the composition for external use of the present invention is applied by means other than “internal use and injection” (Yodogawa Pharmaceutical University Dictionary, 5th edition, 268 pages, 2013). , See Yodogawa Shoten). As long as it is applied by means other than "internal use and injection", the subject, method and means for applying the composition for external use of the present invention are not particularly limited. The composition for external use of the present invention can be suitably applied to the surface of the skin, mucous membrane and the like by means of application, gargling, spraying, spraying, etc., for the purpose of disinfection and cleaning, for example.

  With the recent consumer trend (cleanliness orientation), there is an increasing need for antibacterial and antibacterial agents for external use on the entire skin external surface including fingers, arms and legs. In particular, since the summer of 1996, when pathogenic Escherichia coli (enteric hemorrhagic Escherichia coli) O-157 has become violent, the number and types of sanitized products have increased.

  According to data from a private research company, the scale of the deodorizing, deodorizing, and disinfecting market exceeded 100 billion yen (sales amount basis) in fiscal 2005, and then 113.9 billion yen in fiscal 2008. However, the growth rate has been steady, although the rate of growth has slowed. In 2009, when there was a flu in the new flu, the number increased, and the market has since been improving. Furthermore, according to a survey by the JPO, “Inorganic antibacterial agents and natural organic antibacterial agents are expected to grow, and when antibacterial products are applied with inorganic antibacterial agents, a huge market of about 800 billion yen market. It is.

  In addition to the above, recently there have been many news of new infectious diseases such as O-157 and avian influenza, and the cause bacteria and viruses are “invisible”, so consumers have excessive anxiety For this reason, there is a tendency that the needs for “sanitization” and “antibacterial” products are even higher.

  Furthermore, with the recent support of natural thinking, antibacterial and antifungal agents are safer and less toxic than synthetic organic antibacterial and antifungal agents, and gradually release antibacterial components to prolong antibacterial properties. There is an increasing need for inorganic antibacterial and antifungal agents with durability to maintain, as well as natural sanitizing and antibacterial agents with high safety.

  There are, of course, a very large number of sanitized products currently on the market. For example, Patent Document 1 (Japanese Patent Laid-Open No. 11-302146) describes an external composition containing an alcohol component. Patent Document 2 (Japanese Patent Application Laid-Open No. 2014-114291) describes an external composition containing a hypochlorous acid-based component. As described above, some of the products are “non-alcoholic”, but most are compositions for external use containing “alcohol” or “sodium hypochlorite” as the main component. Both “alcohol” and “sodium hypochlorite” have an excellent disinfecting effect, but there are points that should be “cautioned in use”.

(About alcohol)
Conventionally, “alcohol” is a general term for ethanol (ethyl alcohol), methanol (methyl alcohol), isopanol (isopropyl alcohol), and the like. Traditionally, the alcohols used for disinfection were ethanol and isopropanol, which are said to have relatively low toxicity to humans. Some conventional compositions for external use (from the viewpoint of taxation under the Liquor Tax Law) are those in which 2-propanol, a secondary alcohol, is added to ethanol, or in combination with 2-propanol or benzalkonium chloride. Some products were made into drugs.

The merit of using alcohol is that it is excellent in quick-drying and fast-acting properties, has high safety, and has antibacterial effects against various bacteria (excluding spores). On the other hand, the disadvantages include the following.
・ Ineffective against bacteria and noroviruses that form spores.
-Strong irritation to skin, leather and artificial leather, causing rough hands and deterioration of the leather surface.
-Since it is easy to evaporate, there is no lasting sterilization effect, and when it is used in a wet state (that is, a reduced alcohol concentration), the effect is reduced.
・ Since it is highly volatile (easily vaporized), it is flammable and has a strong alcohol odor.

(Sodium hypochlorite)
The merit of using sodium hypochlorite is that it is excellent in rapid action and has antibacterial effect against various bacteria (the effect can be expected for spores and norovirus). On the other hand, the disadvantages include the following.
-Expert elements of handling such as dilution concentration by the object are high.
・ Stimulation on skin, leather and artificial leather is strong, causing rough hands and leather surface deterioration.
-There are restrictions on the objects of use, such as deterioration of plastic and rubber products, corrosion of metals, bleaching action (use precautions for color and patterned linens).
・ Chlorine gas is generated when there is a chlorine odor and acidic substances are mixed.

(Non-alcohol disinfectant)
Regarding the needs of non-alcohol-based disinfectants (for example, disinfecting gels and foaming external compositions), there are the following possibilities.
(1) About “alcohol” allergy About half of Japanese people do not have ALDH2 (aldehyde dehydrating enzyme) or its function is weak, and they may become alcohol allergic. The route of alcohol absorption is not limited to alcohol consumption, but for example, by wiping with alcohol or touching things (sanitized sheets, wet tissue, disinfectant, detergent, makeup, etc.) without notice, May be taken from the skin.

(2) About the expanding halal market (discipline of halal and Muslim) In the Islamic norm "Islamic law", alcohol is considered to disturb the spirit, and it is prohibited to use it. Contained seasonings must also be avoided. Strict halal rules are established not only for food, but also for cosmetics and pharmaceutical manufacturing processes.

  Regarding the “halal” market, the population of the ASEAN countries is 600 million, of which 40% are Muslims. There are 500 million Muslims in South Asia, 180 million in India, 1.7 billion in Pakistan, 140 million in Bangladesh, 500 million Muslims in total. Resident. There are 300 million Muslims in West Asia, such as the Middle East, and more than 1 billion in Asia, accounting for 40% of the Asian population.

・ The halal market is 60 trillion yen. Of that, Asia is 35 trillion yen. The Muslim food market (halal market) around the world is $ 580 billion (60 trillion yen). Asia's total is 345 billion dollars (35 trillion yen), which is 60% of the world.
・ The number of Muslims in Japan is 100,000 (the maximum is about 20,000 in Indonesia), and the halal market in Japan is 54 billion yen. There are 350,000 Muslims visiting Japan. The halal food market in Japan is approximately 2.5 billion yen, and accommodation and souvenirs are 10 billion yen (12.5 billion yen in total). Moreover, with the increase in Olympics and international conferences, Muslims visiting Japan are expected to double in 1 or 2 years (Source: Brand Research Institute materials)

  As described above, there is no doubt that the need for an external composition that does not require an alcohol-based component and / or a hypochlorous acid-based component will continue to increase. The form of such a composition for external use is not particularly limited, but as a form that can be widely used as daily necessities (that is, not limited to medical use) (* in addition to use as a liquid composition itself), for example, external use Examples thereof include a composition and an external composition having foamability.

These external compositions and external compositions having foaming properties have respective characteristics. For example, the latter external composition having foamability (that is, a foam-type external composition) has the following characteristics.
-In the case of a foam type, it is easy to apply an appropriate amount of the composition.
In the case of the foam type, the total application amount can be saved relatively (for example, compared with the liquid type applied in a liquid state).
-Compared with the gel type, it is possible to reduce stickiness after application, and it is easy to improve the "use feeling".

JP-A-11-302146 JP 2014-114291 A

  The object of the present invention is to eliminate the drawbacks of the prior art described above, without making the alcohol component and / or hypochlorous acid component essential, and after forming the foamed state, the foamed state is maintained for a certain period of time. It is providing the foamable external composition which can be hold | maintained substantially.

  As a result of earnest research, the present inventor has a foaming property including at least water, calcium hydroxide, and a thickener even when the alcohol component and / or hypochlorous acid component is not used as in the prior art. It is a composition for external use; and that it is possible to substantially maintain the foamed state for a certain time after foaming the composition for external use, is extremely effective for achieving the above object. I found it.

  The foamable external composition of the present invention is based on the above findings, and more specifically has the following constitution.

A foamable external composition comprising at least water, a hydroxide and a thickener; and
The composition for external use, wherein the hydroxide is selected from an alkali metal hydroxide, an alkali metal earth metal hydroxide, and a tetraalkylammonium hydroxide.

  The present invention can include, for example, the following aspects.

[1] A foaming external composition comprising at least water, a hydroxide and a thickener; and
The composition for external use, wherein the hydroxide is selected from an alkali metal hydroxide, an alkali metal earth metal hydroxide, and a tetraalkylammonium hydroxide.

  [2] Foaming property according to Ross Miles method is Tf (the time counted immediately after the flow of the test solution is finished) = 2 minutes “bubble height”, and the foaming property according to [1] is 30 mm to 210 mm Topical composition.

  [3] The foaming topical composition according to any one of [1] or [2], which has antibacterial properties against at least one of Escherichia coli, feline calicivirus and ringworm.

  [4] The foamable external composition according to any one of [1] to [3], wherein the surface tension is 33 mN / m or more in surface tension measurement by a platinum plate suspension plate method.

  [5] The foaming external composition according to any one of [1] to [4], wherein the surface tension at Tf = 450 milliseconds is 38 mN / m or more in surface tension measurement (dynamic) by the maximum foam pressure method. object.

  [6] The foaming external composition according to any one of [1] to [5], wherein the surface tension at Tf = 30 milliseconds is 38 mN / m or more in surface tension measurement (dynamic) by the maximum foam pressure method. object.

[7] The alkali metal hydroxide is calcium hydroxide (Ca (OH) ₂ ) lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), And the composition for external use according to any one of [1] to [6], selected from cesium hydroxide (CsOH).

[8] The alkaline earth metal hydroxide is strontium hydroxide (Sr (OH) ₂ ), barium hydroxide (Ba (OH) ₂ ), europium hydroxide (II) (Eu (OH) ₂ ), And the composition for external use according to any one of [1] to [6], which is selected from thallium hydroxide (I) (TlOH).

[9] The tetraalkylammonium hydroxide is selected from tetramethylammonium hydroxide (N (CH ₃ ) ₄ OH) and tetraethyl ammonium hydroxide (N (C ₂ H 5) ₄ OH). [6] The composition for external use according to any one of [6].

  [10] In any one of [1] to [4], the calcium hydroxide is calcium hydroxide generated from a natural calcium carbonate-based material such as shell, coral, egg shell or limestone. The external composition as described.

  As described above, according to the present invention, the alcohol-based component and / or the hypochlorous acid-based component is not essential, the alcohol-based component and / or the hypochlorous acid-based component is not essential, and foaming is performed. After forming the state, a foamable external composition capable of substantially maintaining the foamed state for a certain time can be obtained.

According to this invention, the foaming external composition which has the following characteristics can be obtained further.
(1) It is easy to apply an appropriate amount of the composition.
(2) The total application amount can be saved relatively (for example, compared with a liquid type in which the liquid is applied in a liquid state).
(3) It is possible to reduce stickiness after coating, and it is easy to improve the “use feeling”.
(4) A useful foaming composition for external use can be produced even in an embodiment in which a “surfactant” that may have strong toxicity, permeability, and persistence is not substantially used (in the prior art) In order to form foam, it was common to add a surfactant).

It is a schematic diagram for demonstrating the presumed mechanism of bubble formation at the time of using the thickener (for example, Metrows) in this invention. It is a photograph which shows an example of the actual culture state in the antibacterial test (E. coli) of the composition for external use (Sherry aqueous solution) of the present invention. It is a photograph which shows an example of the actual culture state in the antibacterial test (E. coli) of the composition for external use (Sherry aqueous solution) of the present invention. It is a photograph which shows an example of the instrument etc. which were used in the pH stability test of the composition for external use of this invention. It is a photograph which shows an example of the instrument etc. which were used in the pH stability test of the composition for external use of this invention.

It is a photograph which shows an example of the instrument etc. which were used in the pH stability test of the composition for external use of this invention. It is a graph which shows an example of the surface tension measurement result at the time of using the composition for external use of this invention. It is a photograph which shows an example of the actual culture state in the feline calicivirus antibacterial property test at the time of using the external composition of this invention. It is a photograph which shows an example of the actual culture state in the antibacterial test to the trichophyton using the external composition of this invention. It is a photograph which shows an example of the actual culture state in the antibacterial test to ringworm bacteria using a control sample.

It is a photograph which shows an example of the actual culture state in the antibacterial property test (E. coli) of the composition for external use (sherry gel) of this invention. It is a photograph which shows an example of the actual culture state in the antibacterial property test (E. coli) of the composition for external use (sherry gel) of this invention. It is a photograph which shows an example of the instrument etc. which were used in the foaming power and stability test of the external composition of this invention. It is a photograph which shows an example of the sample etc. which were used in the foaming power and stability test of the external composition of this invention. It is a photograph which shows an example of the foaming state of the sample used in the foaming power and stability test of the external composition of this invention.

It is a schematic cross section which shows the instrument (Rosmiles method measuring apparatus) used in the foaming force and stability test of the external composition of this invention. It is a graph which shows an example of the measurement result obtained in the foaming power and stability test of the external composition of this invention. It is a photograph which shows an example of the instrument etc. which were used in the test of the "ease of foaming" and the "hardness of foam disappearance" of the external composition of this invention. It is a photograph which shows an example of the sample etc. which were used in the test of the "ease of foaming" and the "hardness of foam disappearance" of the external composition of this invention. It is a photograph which shows an example of the instrument etc. which were used in the test of the "ease of foaming" and the "hardness of foam disappearance" of the external composition of this invention.

It is a photograph which shows an example (immediately after sample introduction and after time passage) of the actual sample state used in the test of “hardness of disappearance of bubbles” of the composition for external use of the present invention. It is a photograph which shows an example (immediately after sample introduction and after time passage) of the actual sample state used in the test of “hardness of disappearance of bubbles” of the composition for external use of the present invention. It is a photograph which shows an example of the instrument etc. which were used for the relationship measurement of the difference of the "thickener" in the composition for external use of this invention, and foaming power. It is a photograph which shows an example of the state of the actual sample used for the relationship measurement of the difference of the "thickener" in the composition for external use of this invention, and foaming power.

  Hereinafter, the present invention will be described more specifically with reference to the drawings as necessary. In the following description, “parts” and “%” representing the quantity ratio are based on mass unless otherwise specified.

(Foaming composition for external use)
The foamable external composition of the present invention is capable of maintaining the foamed state for a certain period of time after the foamed state is formed without requiring an alcohol-based component and / or a hypochlorous acid-based component. . Here, in the present invention, “without requiring an alcohol-based component” means that the “alcohol-based component” is not essential (that is, even in an embodiment that does not contain an alcohol-based component). It means that the original effect of the composition for external use (that is, having an appropriate antibacterial property and being able to maintain the foamed state for a certain time after the foamed state is formed) can be exhibited.

(Alcohol component)
In the present invention, the “alcohol component” refers to an alcohol compound having 1 to 10 carbon atoms and 1 to 4 “OH groups”. The content of such an alcohol component can be measured, for example, by gas chromatograph mass spectrometry or GC / MS (SIM) analysis. For details of the alcohol component analysis, for example, the following URL can be referred to as necessary.
http://www.ube-ind.co.jp/usal/documents/f074_142.htm
http://www.an.shimadzu.co.jp/gcms/support/faq/fundamentals/index.htm

Regarding the details of the alcohol analysis, for example, “trimethylsilylation → GC-MS analysis method” at the following URL can be suitably used as necessary.
http://www.jsac.or.jp/bunseki/pdf/bunseki2008/200807nyumon.pdf (derivatization for GC / MS, LC / MS)

(Hypochlorous acid component)
The foamable external composition of the present invention is capable of maintaining the foamed state for a certain period of time after the foamed state is formed, without requiring a hypochlorous acid component. Here, in the present invention, “without requiring a hypochlorous acid-based component” means that the “hypochlorous acid” is not essential (that is, in a mode not containing a hypochlorous acid-based component). In addition, the foaming external composition of the present invention has the original effect (that is, having an appropriate antibacterial property and being able to maintain the foamed state for a certain time after the foamed state is formed). Say there is.

In the present invention, the “hypochlorous acid component” is sodium hypochlorite (chemical formula is NaClO) obtained through chlorine in an aqueous solution of sodium hydroxide, an aqueous solution obtained by electrolyzing a sodium chloride aqueous solution or hydrochloric acid. Says certain hypochlorous acid water. The content of such a hypochlorous acid component can be measured by, for example, gas chromatography mass spectrometry when the amount is small, and syringaldazine method when the amount is large. In addition, it can be measured by an ion chromatography and a quantitative analysis method of “sodium hypochlorite sample solution for ammonium test”. For details of the hypochlorous acid analysis, for example, the following URL can be referred to as necessary.
http://www.an.shimadzu.co.jp/hplc/ic/ic.htm
http://www.jaima.or.jp/jp/basic/chromatograph/ion-chromatography.html
Article "Hypochlorous acid" in the "11th revision Japanese Pharmacopoeia Commentary" (Yodogawa Shoten, 1986)

For trace analysis of hypochlorous acid components using the GC-MS method, for example, the following URL (quantitative determination of hypochlorous acid in foods by GC-MS) can be suitably used.
http://www.pref.okinawa.jp/site/hoken/eiken/syoho/documents/s34_12gc-ms.pdf

(Change in pH)
In the foamable external composition of the present invention, the pH before foaming (water-soluble gel) was P1, and the composition was sealed and stored at 25 ° C., and the pH after t (hr) elapsed was P2. In this case, when t = 48 hours, the pH reduction rate Pv = 100 × (P1−P2) / P1 (%) is preferably 20% or less. The value of Rv is further preferably 18% or less, more preferably 16% or less, further preferably 14% or less, and further preferably 12% or less, Further, it is preferably 10% or less, more preferably 8% or less, further preferably 7% or less, further preferably 6% or less, particularly 5% or less. It is preferable. In the case of P2 ≧ P1, these numerical values satisfy the above-described decrease rate Pv (assuming that Pv = zero).

(Thickener)
In the present invention, the thickener is not particularly limited. That is, the thickener that can be used in the present invention is not particularly limited as long as a suitable foaming state is given in combination with (water + hydroxide) which is an essential component of the foamable external composition of the present invention. Moreover, in this invention, it is also possible to use 2 or more types of thickeners by combining by mixing etc. as needed. Thus, "whether it provides suitable foaming state in combination with (water + hydroxide thereof)", the same measurement method and conditions as "Loss Miles method" described in "Example 7" described below Thus, it is preferable to measure the “foaming property”. In addition, regarding the details of the “Loss Smiles method”, for example, the following URL can be referred to as necessary.
『Http://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/7347/1/6-5-9_p189-193.pdf』

  The measurement by the “Rossmiles method” is simple but accurate. In addition, the measurement by the “Rosmiles method” can be performed “one measurement” in a time of about 5 to 10 minutes (excluding preparation of a measurement sample, data analysis after data measurement, etc.). is there. Therefore, the measurement by the “Loss Smiles method” can be suitably used as a simple screening method.

  In addition, it is preferable to select the thickener suitable in this invention from the system | strain (series; explained in full detail below) excellent in compatibility with said basic aqueous solution. Furthermore, among “thickness excellent in compatibility” thickeners, relatively “short-molecule” thickeners can be suitably used.

(Preferred thickener)
(Water-soluble cellulose thickener)
In the present invention, from the viewpoint of compatibility in the combination of (water + hydroxide), a water-soluble cellulose-based thickener can be preferably used. Examples of such water-soluble cellulose-based thickeners include the following.
CMC (carboxymethylcellulose), HEC (hydroxyethylcellulose), HPMC (hydroxypropylmethylcellulose), CVP (carboxyvinylpolymer / carbomer), decyltetradeceth-20 / HDI copolymer

In the present invention, a nonionic water-soluble cellulose ether-based thickener can be preferably used. Examples of such nonionic water-soluble cellulose ether-based thickeners include the following.
HEC (hydroxyethylcellulose), HEMC (hydroxyethylmethylcellulose), HPMC (hydroxypropylmethylcellulose), MC (methylcellulose)

In the present invention, from the viewpoint of compatibility in the combination with (water + hydroxide) as described above, a water-soluble cellulose-based thickener can be preferably used. Examples of the system thickener (for example, a water-soluble cellulose ether-based thickener) include the following.
CMC (carboxymethylcellulose), HEC (hydroxyethylcellulose), HPMC (hydroxypropylmethylcellulose), CVP (carboxyvinylpolymer / carbomer), decyltetradeceth-20 / HDI copolymer, HEMC (hydroxyethylmethylcellulose), overlapping HPMC (hydroxypropyl) Methylcellulose), MC (methylcellulose) overlap HPMC (hydroxypropylmethylcellulose).

(Especially preferred thickener)
In the present invention, as the “nonionic water-soluble cellulose ether-based thickener”, various etherifying agents (for example, after natural or synthetic cellulose is treated with an alkali (for example, sodium hydroxide)). , Methyl chloride, ethylene oxide, propylene oxide, etc.) and “methylcellulose-based” (MCE type) and “hydroxypropylmethylcellulose-based” (HPMC type) thickeners which can be suitably used.

As the MCE type, for example, a methoxy (—OCH ₃ ) group = about 25 to 33% (for example, a compound having CAS No. = 9004-67-5) can be suitably used. On the other hand, as the HPMC type, for example, the following can be preferably used.
<Methoxy group><Hydroxypropoxygroup>
(-OCH ₂ CHOHCH ₃₎
27-30% 4-7.5%
(For example, compound of CAS No. = 9004-65-3)
27-30% 7-12%
19-24% 4-12%

In the present invention, it is preferable to use a thickener that satisfies one or more of the following conditions. The thickener further preferably satisfies two or more of the following conditions, and further preferably satisfies three of the following conditions.
(A) It has a methyl group (—CH 3) or methoxy group (—OCH 3) that imparts hydrophobicity that promotes a decrease in hydrogen bonding to the hydroxyl group of cellulose, and / or a group in which a glucose residue is replaced with a hydroxypropoxy group.
(B) Nonionic properties that are not easily affected by salts and metal ions.
(C) The viscosity standard value (for example, the viscosity standard value described in the “catalog” of the product) is 03 to 15,000 mPa · s.

Regarding the above-mentioned product “catalog”, the following URL can be referred to as necessary.
<Shin-Etsu Chemical HP>
http://www.metolose.jp/index.shtml
type
http://www.metolose.jp/industrial/type.shtml
Variety
http://www.metolose.jp/industrial/grade.shtml

  Examples of the thickener that satisfies the above conditions include SH60-03, SH60-50, and SH65-4000 manufactured by Shin-Etsu Chemical Co., Ltd. Among these, SH60-06 can be particularly preferably used.

(Preferred thickener)
In the present invention, a cellulose-based thickener having a methoxy (—OCH ₃ ) group and a hydroxypropoxy group (—OCH ₂ CHOHCH ₃ ) is preferable. Here, the content of the methoxy group in the thickener is preferably 15 to 40%, more preferably 18 to 35%, and further preferably 19 to 33%. It is preferable that it is 19 to 31% (for details of the content of such a methoxy group, for example, a table of “Metroze” (trade name) described later can be referred to). On the other hand, the content of the hydroxypropoxy group is preferably 3 to 18%, more preferably 3.5 to 16%, further preferably 4 to 15%, particularly 4 to 13%. (For details of the content of such a hydroxypropoxy group, for example, the “Metroze” table described later can be referred to).

(hydroxide)
The hydroxide that can be used in the present invention is not particularly limited as long as it is selected from an alkali metal hydroxide, an alkali metal earth metal hydroxide, and a tetraalkylammonium hydroxide. That is, as long as a suitable foaming state is given in combination with (water + thickening agent) which is an essential component of the foamable external composition of the present invention, an “alkali metal hydroxide, alkali metal earth” that can be used in the present invention can be used. The “hydroxide selected from a hydroxide of a metal and a hydroxide of tetraalkylammonium” is not particularly limited. It should be noted that guanidine that exhibits strong alkalinity in water is a molecular cation that has protonated cations that are resonance-stabilized, so the above-mentioned “alkali metal hydroxides, alkali metal earth metal hydroxides, And tetraalkylammonium hydroxide "can be used in the present invention.

  In the present invention, as the hydroxide, two or more kinds of hydroxides may be used in combination by mixing or the like, if necessary.

  As described above, “whether or not it is a hydroxide that gives a suitable foaming state in combination with (water + thickener)” can be easily confirmed by the same method as the screening in Example 7 described later. can do. That is, in “Screening of Example 7”, the thickener was fixed to “specific thickener” (for example, SH60-06, manufactured by Shin-Etsu Chemical Co., Ltd.) used in “Example 1”, What is necessary is to perform screening with “thing” variable.

  Examples of the alkali metal hydroxide include calcium hydroxide (Ca (OH) 2), lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), and One or more selected from cesium hydroxide (CsOH) can be suitably used. Examples of the alkaline earth metal hydroxide include strontium hydroxide (Sr (OH) 2), barium hydroxide (Ba (OH) 2), europium hydroxide (II) (Eu (OH) 2), And one or more selected from thallium hydroxide (I) (TlOH) can be preferably used. Further, as the alkali metal hydroxide, one or more selected from alkali metal earth metal hydroxides and tetraalkylammonium hydroxides can be suitably used.

(Calcium hydroxide)
The calcium hydroxide may be added to the external composition of the present invention in the form of calcium oxide (CaO) (for example, in the form of calcined calcium). This is because this calcium oxide is neutral in powder, has a hydroxyl group, becomes calcium hydroxide and exhibits strong alkalinity. As the naturally derived calcined calcium, calcined shell calcium, coral, calcium oxide purified from chicken eggs, calcium oxide produced from limestone called lime, and the like can also be used.

(Calcium hydroxide content)
In the present invention, even when “CaO” (calcium oxide; molecular weight = 56) is added to the foamable external composition, the content is “Ca (OH) ₂ ” (calcium hydroxide; molecular weight = 74). Shall be calculated as This is because CaO usually exists in the state of Ca (OH) ₂ in a system containing water as in the foamable external composition of the present invention. One mole of “CaO” corresponds to one mole of “Ca (OH) ₂ ”. Therefore, for example, when 1 mol (56 g) of “CaO” is added to the foamable external composition of the present invention, the content is 1 mol (74 g) of “Ca (OH) ₂ ” added. Calculate as

(Optional component)
The foamable external composition of the present invention contains the above-mentioned water, hydroxide and thickener as essential components, but may contain other optional components as necessary. Examples of such “arbitrary components” include the following.
-Food additives such as sweeteners (eg glycerin), hyaluronic acid, chitosan, fragrance extract, etc. Details of such "food additives" can be confirmed, for example, at the following URL (Ministry of Health, Labor and Welfare website).
http://www.mhlw.go.jp/stf/seisakunitsuite/bunya/kenkou_iryou/shokuhin/syokuten/
-Quasi-drug additive such as chamomile extract The details of such "quasi-drug additive" can be confirmed, for example, at the following URL (Independent Administrative Institution Pharmaceuticals and Medical Devices Agency website).
http://www.pmda.go.jp/index.html

  However, from the viewpoint of suitably exerting the effect of the foamable external composition of the present invention, when the total of the essential components (that is, water + calcium hydroxide + thickening agent) is 100 parts by mass, the above “ The total of “optional components” (excluding the following “antibacterial agent” and the above-mentioned “alcohol-based component” and “hypochlorous acid-based component”) is preferably 100 parts by mass or less. The total of the “arbitrary components” is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and further preferably 40 parts by mass or less with respect to 100 parts by mass of the total of essential components. Preferably, it is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and particularly preferably 10 parts by mass or less.

(Antimicrobial agent)
The foamable external composition of the present invention does not require an antibacterial agent. That is, in the present invention, an antibacterial agent is not necessarily required. However, you may mix | blend an antibacterial agent as needed. Examples of such “antibacterial agents” include the following.

1. Low-level disinfectant 1) Quaternary ammonium salt (1) Benzalkonium chloride (2) Benzethonium chloride 2) Chlorhexidine (1) Chlorhexidine gluconate 3) Amphoteric surfactant (1) Alkyldiaminoethylglycine hydrochloride 2. Medium level disinfectant 1) Alcohol (1) Ethanol (2) Isopropanol (3) Isopropanol-added ethanol solution (4) Disinfectant based on alcohol 2) Iodohol-iodine (1) Povidone iodine (2) Iodo tincture 3 ) Hypochlorous acid (1) Sodium hypochlorite (2) Other hypochlorous acid disinfectant 4) Phenol (1) Cresol (2) Phenol High-level disinfectant 1) Aldehydic (1) Glutaral (2) Phthalal 2) Other high-level disinfectant (1) Peracetic acid (2) Hydrogen peroxide (3) Chlorine dioxide Other disinfectants 1) Acrinol hydrate 2) Oxole 3) Triclosan 4) Formalin etc.

The details of the “antibacterial agent” can be confirmed, for example, at the following URL (Yoshida Pharmaceutical homepage; disinfectant text 4th edition “from the standpoint of infection control based on evidence”).
http://www.yoshida-pharm.com/category/countermeasure/texts/

  However, from the viewpoint of suitably exerting the effect of the foamable external composition of the present invention, when the total of the essential components (that is, water + calcium hydroxide + thickening agent) is 100 parts by mass, the above “ The amount of the “antibacterial agent” is preferably 82 parts by mass or less. The amount of the “antibacterial agent” is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, further preferably 50 parts by mass or less, and further 40 parts by mass. Is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, further preferably 15 parts by mass or less, and further preferably 10 parts by mass or less. Preferably, it is preferably 8 parts by mass or less, more preferably 6 parts by mass or less, and particularly preferably 5 parts by mass or less.

(Cellulose nanofiber)
In the present invention, cellulose nanofibers can be used as necessary as the above-mentioned “thickening agent” without departing from the spirit of the present invention. This cellulose can be used as all of the above mentioned “thickeners” or as part of a “thickener” (ie cellulose nanofibers and other “non-nanofiber” thickeners described above. In combination). Moreover, it is also possible to use 2 or more types of cellulose nanofibers as a thickener by combining them by mixing or the like as necessary. Regarding the cellulose nanofibers, for example, Tetsuo Kondo, “A New World Opened by Nanofibers”, Chemistry, February 2016, pp. 33-38, (Chemical Doujin) can be referred to as necessary. . Here, the “range not inconsistent with the gist of the present invention” is as necessary as long as a suitable foaming state is given in combination with (water + hydroxide) which is an essential component of the foamable external composition of the present invention. It can be used.

(Preferable manufacturing method)
The production method of the foamable external composition of the present invention is not particularly limited. From the viewpoint of simplicity and efficiency, for example, the following “Production Method A” and / or “Production Method B” can be preferably used. When a thickener containing a carboxy group is used, when a salt (hydroxide) is added to the solution of the thickener (production method A), and when a thickener is added to the salt solution With (Manufacturing method B), there exists a tendency for those thickening effects to come out. Usually, the former method (Production Method A) tends to give an external composition having a higher viscosity.

(Production method A; thickener is added to the salt solution)
(1) Using purified water, prepare a solution of 0.1% hydroxide (for example, shellel = shell calcined calcium) powder.
(2) A hydroxide gel containing 1% thickener is prepared based on the 0.1% hydroxide solution obtained above. That is, the thickener is dissolved little by little in a 0.1% hydroxide aqueous solution and stirred for about 1 minute with a blender machine while paying attention not to “dama”. At this time, “foaming” is observed, but the produced “foam + mixture” is immediately put into a sealed container. At this time (immediately before putting in a closed container), it is confirmed that the pH of the mixture is 12 or more.

(Manufacturing method B; salt is added to the thickener dispersion solution)
(1) A 1% thickener aqueous solution is prepared by blending a thickener with purified water.
(2) A 0.1% calcium hydroxide-containing gel is prepared based on the 1% thickener aqueous solution obtained above. That is, while dissolving calcium hydroxide (for example, shellel = shell calcined calcium) powder little by little in a 1% thickener aqueous solution, it is stirred for about 1 minute with a blender machine, taking care not to cause “dama”. Bond. At this time, “foaming” is observed, but the produced “foam + mixture” is immediately put into a sealed container. At this time (immediately before putting in a closed container), it is confirmed that the pH of the mixture is 12 or more.

(Measurement of antibacterial properties)
The foamable external composition of the present invention can exhibit an appropriate antibacterial effect. More specifically, when measured under the conditions of “Example 5” described later (that is, using a viable cell solution adjusted to 1 × 10 exp (8) / mL), the pour plate In the state after the culture, when the foamable external composition of the present invention is used as a sample, a preferable range of the “viable cell count (N ₁₅ ) 15 minutes after the start of measurement” can be defined as follows. it can.

(Number of viable bacteria 15 minutes after the start of measurement)
That is, when N ₀ = the initial viable cell count and N ₁₅ = the viable cell count after 15 minutes, in the present invention, the ratio Nn = N ₀ / N ₁₅ = 100 or more (that is, 1 × 10 exp (2) Or more). The ratio Nn is further preferably 3 × 10 exp (2) or more, more preferably 6 × 10 exp (2) or more, and further preferably 8 × 10 exp (2) or more. Further, it is preferably 1 × 10 exp (3) or more, more preferably 3 × 10 exp (3) or more, further preferably 6 × 10 exp (3) or more, and further 8 × 10 exp. It is preferably (3) or more, more preferably 1 × 10 exp (4) or more, further preferably 3 × 10 exp (4) or more, further 6 × 10 exp (4) or more. Preferably, it is preferably 8 × 10 exp (4) or more, more preferably 1 × 10 exp (5) or more, and further 3 × 10 exp (5) or more. DOO preferably, more preferably at 6 × 10exp (5) or more, more preferably at 8 × 10exp (5) or more, and particularly preferably 1 × 10exp (6) above.

(Number of viable bacteria 30 minutes after the start of measurement)
That is, when N ₀ = the initial viable cell count and N ₁₅ = the viable cell count after 30 minutes, in the present invention, the ratio Nn = N ₀ / N ₃₀ = 100 or more (that is, 1 × 10exp (2) Or more). The ratio Nn is further preferably 3 × 10 exp (2) or more, more preferably 6 × 10 exp (2) or more, and further preferably 8 × 10 exp (2) or more. Further, it is preferably 1 × 10 exp (3) or more, more preferably 3 × 10 exp (3) or more, further preferably 6 × 10 exp (3) or more, and further 8 × 10 exp. It is preferably (3) or more, more preferably 1 × 10 exp (4) or more, further preferably 3 × 10 exp (4) or more, further 6 × 10 exp (4) or more. Preferably, it is preferably 8 × 10 exp (4) or more, more preferably 1 × 10 exp (5) or more, and further 3 × 10 exp (5) or more. DOO preferably, more preferably at 6 × 10exp (5) or more, more preferably at 8 × 10exp (5) or more, and particularly preferably 1 × 10exp (6) above.

(Antimicrobial properties 15 minutes after the start of measurement)
Regarding the above-mentioned antibacterial effect, under the conditions of “Example 5” described later (that is, using a living bacterial solution adjusted to 1 × 10 exp (8) / mL), the “Shelyl aqueous solution” sample according to the present invention. Nr (Nr) ratio of “viable cell count” = Naq at 15 minutes after the start of measurement, and “viable cell count” = Ng when the foaming external composition of the present invention is used as a sample. ₁₅ = Naq / Ng) is preferably 1.5 or more 15 minutes after the start of measurement. The Nr ₁₅ is preferably 1.6 or more, more preferably 1.7 or more, further preferably 1.8 or more, and further 1.9 or more. Preferably, it is preferably 2 or more, more preferably 2.1 or more, further preferably 2.2 or more, further preferably 2.3 or more, Is preferably 2.4 or more, more preferably 2.5 or more, further preferably 2.6 or more, further preferably 2.7 or more, and further 2 Is preferably 2.8 or more, more preferably 2.9 or more, further preferably 3 or more, further preferably 3.1 or more, and further on 3.2. It is preferable that there is also 3.3 or more Preferably, it is preferably 3.4 or more, more preferably 3.5 or more. The greater this ratio Nr, the greater the antibacterial effect “gelled” in the present invention.

(Antimicrobial properties 30 minutes after the start of measurement)
Regarding the antibacterial properties 30 minutes after the start of measurement, the “ratio Nr ₃₀ ” defined in the same manner as the ratio Nr ₁₅ is preferably 1.5 or more 30 minutes after the start of measurement. The Nr is preferably 1.6 or more, more preferably 1.7 or more, further preferably 1.8 or more, and further 1.9 or more. Preferably, it is preferably 2 or more, more preferably 2.1 or more, further preferably 2.2 or more, and further preferably 2.3 or more. Preferably, it is preferably 2.4 or more, more preferably 2.5 or more, further preferably 2.6 or more, and further preferably 2.7 or more, Furthermore, it is preferably 2.8 or more, more preferably 2.9 or more, further preferably 3 or more, further preferably 3.1 or more, and further 3. 2 is preferable, and further Is preferably .3 or more, more preferably 3.4 or more, and particularly preferably 3.5 or more.

In addition, regarding the “antibacterial effect” in the above-mentioned “Example 5”, the values of 15 minutes after the start of measurement and 30 minutes after the start of measurement are mentioned, but the foaming external composition of the present invention The “antibacterial effect” can be measured in the same manner as the measurement in “Application Example 5” even at a time point in the range of 5 minutes to less than 15 minutes after the start of measurement. In other words, even at the time points in these ranges, values similar to the above-described “Nn” and “Nr” (for example, the ratio Nn = N ₀ / N ₅ and Nr _{5 at} the time point 5 minutes after the start of measurement) = Naq / Ng) can be calculated, and a numerical value in the “preferred range” similar to that described above can be given.

(Aspects corresponding to “halal”)
In an embodiment that should correspond to “halal”, it is important to reduce as much as possible the content of “alcohol component” (for example, ethanol) in the foamable external composition of the present invention. Needless to say, the use of “alcohol” is strictly restricted in Islam.

(Aspect prepared at the time of use)
The foamable external composition of the present invention can also be used in a so-called “prepared before use” mode. In facilities and institutions where “sterilization” is important, such as medical institutions, beauty salons, barbers, etc., the foaming topical composition of the present invention is prepared and used “in situ” immediately before its use. This is because, for example, it may be preferable from the viewpoint of reducing the probability of preventing deterioration of the product due to the storage method and conditions as much as possible.

  In such an embodiment of the foamable external composition “prepared at the time of use” of the present invention, it is preferable that the “foamed state” can be maintained for ** 10 seconds or more. 5 minutes or more This “bubble state” holding time is preferably 15 seconds or more, more preferably 30 seconds or more, further preferably 45 minutes or more, further preferably 60 seconds or more, and further 1.5 minutes. The above is preferable, and it is particularly preferable that it is 2 minutes or more.

  On the other hand, in the embodiment of the present invention in which “moderate defoaming property” is required (for example, the embodiment of the present invention that does not require washing after foaming), the foaming time is preferably 5 minutes or less. The “bubbled state” holding time is preferably 4.5 minutes or less, more preferably 4 minutes or less, further preferably 3.5 minutes or less, and further preferably 3 minutes or less.

(Aspect used for oral care)
Since the foamable external composition of the present invention is “external use” (that is, applicable by means other than internal use and injection), it is also used in oral care of humans and animals (for example, pets such as dogs and cats). can do. Even in such an aspect, for example, from the viewpoint of facilitating application to the oral cavity, as needed (for example, changing / reducing the type and amount of thickener) than the aspect used for human fingers. The viscosity can be made slightly lower.

(Aspect used for animals)
The foamable external composition of the present invention can be suitably used for various cares such as oral care for animals other than humans (for example, pets such as dogs and cats).

(Preferable foaming measurement method)
The “foamability” measurement method that can be used in the present invention is not particularly limited. However, from the viewpoint of the balance between simplicity of measurement / accuracy / measurement cost, “loss miles” described in “Example 7” described later is used. The “foaming property” is preferably measured by the same measurement method and conditions as in “Method”. In addition, regarding the details of the “Loss Smiles method”, for example, the following URL can be referred to as necessary.
『Http://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/7347/1/6-5-9_p189-193.pdf』

(Loss Miles method; measured by Ross-Miles Method)
(1) Referring to FIG. 16, 50 ml of test solution is put into cylinder B.
(2) Place 200 ml of the same test solution into pipette A.
(3) Opening the pipette A cock, causing the test liquid to flow down, and the liquid flowing down collides with the test liquid in the cylinder B, thereby generating bubbles.
(4) The height of foam (foaming force) is measured immediately after the flow of the test solution is finished.
(5) The height of foam (foam lacquer stability) is measured and evaluated every minute.

(Suitable foaming property of the composition of the present invention)
In a preferred embodiment of the present invention, the time counted from “immediately after the flow of the test solution is finished” is represented by “Tf”. When this “immediately after the flow of the test solution is finished” is set to Tf = 0 (zero), the “foaming property” of the composition of the present invention is evaluated based on the “bubble height” at Tf = 2 minutes. To do.

(Preferred upper limit)
In a preferred embodiment of the present invention, the “bubble height” at Tf = 2 minutes is preferably 250 mm or less. The “bubble height” is preferably 240 mm or less, more preferably 230 mm or less, further preferably 220 mm or less, and further preferably 210 mm or less. Is preferably 200 mm or less, more preferably 190 mm or less, further preferably 180 mm or less, further preferably 170 mm or less, further preferably 160 mm or less, Is preferably 150 mm or less.

(Preferable lower limit)
In a preferred embodiment of the present invention, the “bubble height” at Tf = 2 minutes is preferably 30 mm or more. The “bubble height” is preferably 40 mm or more, more preferably 50 mm or more, further preferably 60 mm or more, further preferably 70 mm or more, Is preferably 80 mm or more, and more preferably 90 mm or more.

(Preferred range)
In the present invention, a “preferable range” comprising any combination of the “preferred upper limit” and “preferable lower limit” of the “bubble height” listed above can be mentioned. Typical examples of the “preferable range” are as follows. That is, the “range” of the bubble height at Tf = 2 minutes is preferably, for example, 30 to 210 mm. The “range” is further preferably 30 to 200 mm, 40 to 200 mm, more preferably 50 to 200 mm, further preferably 60 to 180 mm, further preferably 70 to 170 mm, and more preferably 80 to 200 mm. 180 mm is preferable, 90 to 170 mm is more preferable, 100 to 180 mm is more preferable, 100 to 160 mm is more preferable, 100 to 170 mm is more preferable, 100 to 160 mm is more preferable, and 100 to 150 mm is more preferable. .

  In the aspect of the present invention in which a lower “foaming power immediately after application” is preferred, the “range” of the height of the foam at Tf = 2 minutes is preferably, for example, 30 to 150 mm. The “range” of the height of the foam is preferably 30 to 140 mm, more preferably 30 to 130 mm, further preferably 30 to 120 mm, further preferably 30 to 110 mm, and further preferably 30 to 100 mm. .

  In addition, in the aspect of the present invention in which a higher “foaming power immediately after application” is preferred, the “range” of the foam height at Tf = 2 minutes is preferably, for example, 50 to 250 mm. The “range” of the height of the bubbles is preferably 80 to 250 mm, more preferably 100 to 250 mm, and particularly preferably 150 to 250 mm.

(Suitable surface tension)
The “surface tension” measurement method that can be used in the present invention is not particularly limited, but the following “surface tension” measurement method is used in terms of the balance between measurement ** simpleness / accuracy / measurement cost **. It can be used suitably.
<Measurement Condition A-Platinum Plate Suspension Plate Type>
・ Surface tension meter: CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.
Measuring method: Platinum plate suspension plate type

(Suitable lower limit)
In the “surface tension” measurement by the “platinum plate suspension plate type”, the surface tension of the composition of the present invention is preferably 25 mN / m or more from the viewpoint of providing appropriate foaming. The surface tension is preferably 26 mN / m or more, more preferably 27 mN / m or more, further preferably 28 mN / m or more, and further 29 mN / m or more. It is preferably 30 mN / m or more, more preferably 31 mN / m or more, further preferably 32 mN / m or more, and further preferably 33 mN / m or more. Further, it is preferably 34 mN / m or more, more preferably 35 mN / m or more, further preferably 36 mN / m or more, further preferably 37 mN / m or more, Is preferably 38 mN / m or more, more preferably 39 mN / m or more, and further preferably 40 mN / m or more. Further, it is preferably 41 mN / m or more, more preferably 42 mN / m or more, further preferably 43 mN / m or more, and further preferably 44 mN / m or more. Furthermore, it is preferably 45 mN / m or more, more preferably 46 mN / m or more, further preferably 47 mN / m or more, further preferably 48 mN / m or more, It is preferably 49 mN / m or more, and more preferably 50 mN / m or more.

(Suitable upper limit)
In the “surface tension” measurement by the “platinum plate suspension plate type”, the surface tension of the composition of the present invention is preferably 76 mN / m or less from the viewpoint of giving appropriate foaming. The surface tension is preferably 70 mN / m or less, more preferably 68 mN / m or less, further preferably 66 mN / m or less, and further 64 mN / m or less. It is preferably 62 mN / m or less, more preferably 60 mN / m or less, further preferably 58 mN / m or less, and further preferably 56 mN / m or less. Further, it is preferably 54 mN / m or less, more preferably 52 mN / m or less,
Furthermore, it is preferably 50 mN / m or less, more preferably 48 mN / m or less, further preferably 46 mN / m or less, further preferably 44 mN / m or less, It is preferably 42 mN / m or less, more preferably 40 mN / m or less, further preferably 38 mN / m or less, further preferably 36 mN / m or less, and further 34 mN / m or less. m or less is preferable.

(Preferred range)
In the present invention, a “preferable range” consisting of an arbitrary combination of “preferable upper limit” and “preferable lower limit” of “surface tension” by the “platinum plate suspension plate type” listed above can be mentioned. Typical examples of the “preferable range” are as follows. That is, the “surface tension” according to the “platinum plate suspension plate type” is preferably 26 to 76 mN / m. Furthermore, the “surface tension” is preferably 36 to 56 mN / m, more preferably 38 to 56 mN / m, further preferably 40 to 56 mN / m, and more preferably 42 to 56 mN / m. It is preferably 56 mN / m.

<Measurement condition B-maximum bubble pressure method (dynamic measurement)>
Test method: Measured at 25 ° C. using Cruz BP-2 (maximum foam pressure method). As the density of the sample solution, the value of water is used.

  From the viewpoint of a suitable balance of “foaming-out of foam”, in the foamable external composition of the present invention, the surface tension of the composition measured at 25 ° C. using the maximum foam pressure method is as follows. It is preferable.

(Suitable surface tension-measurement at Tf)
In the foamable external composition of the present invention, from the viewpoint of a suitable balance of “foaming-out of foam” (when the time from the start of the formation of the interface until the pressure becomes maximum is represented by “Th”) The surface tension of the composition at Tf of 450 milliseconds is preferably 33 mN / m or more. This surface tension is preferably 38 mN / m or more, more preferably 40 mN / m or more, further preferably 41 mN / m or more, and further 42 mN / m or more. It is preferably 43 mN / m or more, more preferably 44 mN / m or more, and further preferably 45 N / m or more.

(Preferred range)
In the foamable external composition of the present invention, the surface tension of the composition at a time point where Tf is 450 milliseconds is 26 to 76 mN / m from the viewpoint of a suitable balance of “foaming-out of foam”. preferable. The surface tension of the composition is preferably 36 to 56 mN / m, more preferably 38 to 56 mN / m, further preferably 40 to 56 mN / m, and further 41 It is preferably ˜56 mN / m, more preferably 42 to 56 mN / m, further preferably 42 to 54 mN / m, and further preferably 42 to 52 mN / m.

For details of measurement using this maximum bubble pressure method, for example, the following URL can be referred to.
http://www.face-kyowa.co.jp/science/theory/what_surface_tention/#id04
http://www.sanyo-kruss.com/qa/products02.html
(At these sites, the time from when the interface begins to form until the pressure reaches its maximum is called "Surface Age", and is a time parameter for evaluating dynamic surface tension measurements. ).

(Inactivation effect of feline calicivirus)
<Test conditions>
Action time: Test article: 15 minutes; Control: 0 (zero; initial), 15 minutes Test virus: Feline calicivirus F-9 (ATCC (registered trademark) VR-782 (trademark))
Test type: Virus inactivation effect test Other conditions: Same as in Example 9

In the foaming topical composition of the present invention, the inactivation effect on feline calicivirus (similar to norovirus), that is, the infectious titer logarithm decreasing value after acting for 15 minutes = log ₁₀ (initial infectious titer / infection titer after acting) The value of is preferably greater than 3.0. The infectious value logarithmic decrease value of the composition of the present invention is preferably 3.1 or more, more preferably 3.2 or more, further preferably 3.3 or more, It is preferably 3.4 or more, more preferably 3.5 or more, further preferably 3.6 or more, further preferably 3.7 or more, and further 3. It is preferably 8 or more, more preferably 3.9 or more, and further preferably 4.0 or more.

(Anti-bacterial effect against ringworm bacteria)
<Test conditions>
・ Test bacteria: Trichophyton rubrum TIMM 2659
Other conditions: Same as in Example 10

In the foamy external composition of the present invention, the inactivation effect against ringworm (ie, athlete's foot fungus), that is, the logarithmic decrease in infectivity value after acting for 15 minutes = log ₁₀ (number of initial viable cells / live cells after acting) The value of (number) is preferably greater than 1. The infectivity value logarithmic decrease value of the composition of the present invention is further preferably 2 or more, more preferably 3 or more, further preferably 3.1 or more, and further 3 .2 or more, more preferably 3.3 or more, further preferably 3.4 or more, further preferably 3.5 or more, and further 3.6. Preferably, it is preferably 3.7 or more, more preferably 3.8 or more, further preferably 3.9 or more, and further preferably 4.0 or more. Preferably there is.

(Quantitative method of surfactant)
The “surfactant” that may be contained in the composition of the present invention (with a relatively small amount, a trace amount, and / or unavoidable) is not particularly limited. For example, the analysis described in the following URL It can be quantified by a method (for example, LC-MS measurement conditions described in Table 2 on page 13 and Table 3 on page 14).
『Https://www.scas.co.jp/scas_news/news/pdf/22/frontier2_22.pdf』

  Hereinafter, the present invention will be described more specifically with reference to examples.

Example 1
(Preparation of composition for external use by production method A)
In a Pyrex (registered trademark) beaker having a capacity of 3000 ml, 999 g of “purified water” (trade name: Trusco purified water, manufactured by Trusco Nakayama Co., Ltd.) in accordance with Japanese Pharmacopoeia standards was put. Next, 1 g of calcium hydroxide (Ca (OH) 2) powder, shell calcined calcium powder; made by Shin Functional Science Co., Ltd., trade name: Cheryl powder) is put into the purified water, and a stirrer (portable type) The blender machine: manufactured by Tescom Co., Ltd., model: THM320, trade name: stick blender; rotation speed = 9000-15,000 rpm) was stirred for about 1 minute, and then allowed to stand for 12 hours.

  After the standing, the supernatant of the precipitate was collected to obtain a 0.1% calcium hydroxide aqueous solution for preparing the external composition of the present invention.

  Next, a calcium hydroxide external composition containing a 1% thickener was prepared based on the 0.1% calcium hydroxide solution obtained above. That is, in a Pyrex (registered trademark) container with a capacity of 3000 ml, the 0.1% calcium hydroxide aqueous solution (1000 g) obtained above was stirred (portable blender machine: manufactured by Tescom Corporation). , Model: THM320, trade name: stick blender; rotational speed = 9,000-15,000 rpm), “Nonionic water-soluble cellulose ether” as a thickener (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: Metroles) While adding 101 g of 65SH-4000 and 60SH-06 to the 0.1% calcium hydroxide aqueous solution little by little, taking care not to “dama”, about 5 minutes Gradually added over time. Furthermore, stirring by the blender machine was continued for about 3 minutes under the same conditions, and then allowed to stand for 24 hours.

  At this time, “foaming” is observed in the mixture for preparation of the composition for external use. The generated “foam + mixture” is immediately put into a sealed container (made of Pyrex (registered trademark) glass: capacity = about 1000 mL (milliliter). ), Manufactured by Nippon Genetics Co., Ltd. By this operation, the foamable external composition of the present invention was obtained.

As described above, it was confirmed that the pH of the mixture was 12 or more immediately before the “foam + mixture” was put in the sealed container. The measurement conditions used for pH measurement at this time are as follows.
pH measuring device: Hanna Instruments Japan Co., Ltd., Model: HI 98128, Product name: pHep5 (Pep 5)

Example 1a
(Confirmation of viscosity change over time)
In the gel composition obtained in Example 1, the presence or absence of a change in viscosity over time was confirmed.
<Storage conditions>
The gel composition in the sealed container obtained in Example 1 was stored under conditions of 25 ° C. and normal pressure.
<Confirmation method of viscosity change>
Confirmation method: The viscosity of the gel composition after each lapse of time was confirmed by a visual method.
Confirmed elapsed time: After the preparation of the gel composition, it was observed for 24 hours, 48 hours, or up to about 1 week.

<Confirmation result of viscosity change>
No change in viscosity was observed in the period of 24 to 48 hours after preparation of the gel composition. In addition, when a thickener other than the above “Metroze” was used, a phenomenon in which the viscosity increased was also observed. Even when the viscosity increased in this way, there was no substantial adverse effect on the use / effect of the external composition of the present invention.

Example 1b
The same as in Example 1 except that the thickening agent for preparing a gel composition shown in the following “Table 1” was used instead of the “Metroze 65SH-4000” as the thickening agent used in Example 1 above. Thus, a total of 11 types of gel compositions were obtained.

(Table 1)
<Thickener for preparing gel composition>
* 1: 20 ° C, 2% aqueous solution,
* 2: 25 ° C., 1% aqueous solution 30 rpm,
* 3: 25 ° C., 1% aqueous solution 60 rpm,
* 4: 1% dry weight
* 5: 1% non-neutralized dispersion

  Detailed specifications of various thickeners described in Table 1 are shown in Tables 2 to 6 below. In the “Results” section of Tables 2 to 6 below, “determining method” means “manufacturing method A”, and “after thickener dispersion” is “manufacturing method B”. ".

<Functional group of Metroze>
65SH-4000: Methoxy group = 28.1 (27-30)
Hydroxy * propoxy group * = 6.1 (4.0-7.5)
Viscosity (mPa · S): 3500-5600
65SH-1500: methoxy group = 28.2 (27-30)
Hydroxy * propoxy group * = 6.14.0-7.5
Viscosity (mPa · S): 1200 to 1800
65SH-15000: methoxy group = 28.1 (27-30)
Hydroxy * propoxy group * = 6.0 (4.0-7.5)
Viscosity (mPa · S): 12000-18000
90SH-15000: methoxy group = 23.0 (19-24)
Hydroxy * propoxy group * = 9.6 (4.0-12)
Viscosity (mPa · S): 12000-18000

<Functional group of HEC Daicel>
・ (Product name unknown): hydroxyethyl group = 1.0 to 1.3
Viscosity (mPa · S): 100 to 300
SP900: hydroxyethyl group = ** unknown **
Viscosity (mPa · S): 4000-5500
<Functional group of CMC Daicel>
CMC 2260: Carboxymethyl group Viscosity (mPa · S): 4000 to 6000
Etherification degree: 0.89 (0.8-1.0)

<Functional group of kicolate>
F-120: Carboxymethyl group Viscosity (mPa · S): 150-200
Degree of substitution: 0.56 (0-3)

<Functional group of Hibiswako>
Hibiswaco 103: Carboxy group = 59.9 (57.7-63.4%)
Viscosity (mPa · S): 17800 (13,000 to 27000)
(1% unneutralized 400)
Hibiswaco 104: Carboxy group = 59.9 (57.7-63.4%)
Viscosity (mPa · S): 25800 (22000-40000)
(1% unneutralized 2500)
Hibiswaco 105: Carboxy group = 59.9 (57.7-63.4%)
Viscosity (mPa · S): 10200 (7000-14000)
(1% unneutralized 5000)

<Functional group of EMALEX>
EMALEX 2420: hydroxyl group = 47.97%
HLB value: 12

(Table 2)

(Table 3)

(Table 4)

(Table 5)

(Table 6)

In addition, the value shown in the above “standard thickening value (mPa · s)” is obtained from the website of each manufacturer.
Shin-Etsu Chemical Co., Ltd .: http://www.metolose.jp/industrial/index.shtml; etc. Daicel Finechem Co., Ltd .: http://www.daicelfinechem.jp/products/chemical.html
Nichirin Chemical Industry Co., Ltd .: http://www.nichirin-chem.co.jp/31seihin.html
Wako Pure Chemical Industries, Ltd. :: http://www.wako-chem.co.jp/kaseihin/hiviswako/index.htm
Nippon Emulsion Co., Ltd. :: https://www.nihon-emulsion.co.jp/products/emalex

With respect to the various thickeners described above, the following results were obtained.
<Metroze>
(General) It was relatively less affected by acids and bases, and exhibited a predetermined viscosity in the range of pH 3.0 to 11.0. In addition, in the case of Metrouse use, even if it preserve | saved for one year or more, the fall of the viscosity was not seen.
Metroze 65SH-4000: Viscosity related data was generally good.
・ Metroze 65SH-1500:
(Manufacturing method A) The viscosity related data showed a value close to “Metroze 65SH-4000”.
(Manufacturing method B) The viscosity related data showed a value close to “Metroze 65SH-4000”.
・ Metroze 65SH-15000:
(Manufacturing method A) The viscosity related data was “honey-like → good after 24 hours”.
(Manufacturing method B) The viscosity related data was “honey ⇒good after 24 hours”.
・ Metroze 90SH-15000:
(Manufacturing method A) The viscosity related data was “honey-like → good after 24 hours”.
(Manufacturing method B) The viscosity related data was “honey ⇒good after 24 hours”.

<HEC Daicel>
(General) It was not easily affected by salts and metal ions, and was highly compatible with salts and other drugs.
-Unknown product name (hydroxyethyl group: 1.0 to 1.3):
(Manufacturing method A) The viscosity related data was "viscosity relaxation".
(Manufacturing method B) The viscosity-related data was “viscosity-relaxed white turbidity → transparent after 48 hours”.
・ SP900:
(Manufacturing method A) The viscosity related data was "high viscosity".
(Manufacturing method B) The viscosity related data were "viscosity strong cloudiness".

<CMC Daicel>
-CMC 2260:
(Manufacturing method A) The viscosity related data was "jelly-like".
(Manufacturing method B) The viscosity related data was "jelly-like and hard gel separation".

<Chicolate>
(General) There was a tendency to be susceptible to metal ions and salt contamination. Some divalent salt metals are good and bad. The viscosity decreases at pH 10 or higher.
・ F120:
(Manufacturing method A) The viscosity related data was "water state".
(Production method B) The viscosity-related data was “water”.

<Hibis Wako>
(General) Effective pH range (1% thickener):
Hibiswako 103: 5.5-10,
Hibiswako 104: 5 to 10.5,
Hibiswako 105: 4-11
Stability against metal ions:
Hibis Wako 103: Slightly unstable Hibis Wako 104: Slightly unstable Hibis Wako 105: Stable / Hibis Wako 103
(Manufacturing method A) The viscosity related data was “jelly-like / damaged / pH decreased”.
(Production method B) Viscosity-related data was “no viscosity / depleted white turbidity-separated sulfur-smelling pH drop”.
・ Hibiswako 104
(Manufacturing method A) The viscosity related data was “jelly-like / damaged / pH decreased”.
(Production method B) Viscosity-related data was “no viscosity / depleted white turbidity-separated sulfur-smelling pH drop”.
・ Hibiswako 105
(Manufacturing method A) The viscosity related data was “jelly-like / damaged / pH decreased”.
(Production method B) Viscosity-related data was “no viscosity / depleted white turbidity-separated sulfur-smelling pH drop”.

<EMALEX>
(General) Etherified product obtained by addition polymerization of ethylene oxide to iso-branched higher alcohol. Since the alkyl group has an iso-branch, it has a lower melting point than the straight chain type.
EMALEX 2420: “Component: Polyoxyethylene decyl tetradecyl ether (Production method A) Viscosity is very low.
(Production Method B) Lightly cloudy and very weak in viscosity

Example 1c
(Preparation of composition for external use by production method B; adding salt to thickener dispersion solution)
Pyrex (registered trademark) beaker with a capacity of 3000 ml was charged with 1000 g of “purified water” (trade name: Trusco purified water, manufactured by Trusco Nakayama Co., Ltd.) according to Japanese Pharmacopoeia standards. Next, under stirring (portable blender machine: manufactured by Tescom Co., Ltd., model: THM320, trade name: stick blender; rotation speed = 9,000 to 15,000 rpm) To avoid “dama” while 101 g of “ionic water-soluble cellulose ether” (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: Metrol's 65SH-4000) is gradually dissolved in the purified water. Carefully added over about 5 minutes. Furthermore, stirring with the blender machine was continued for about 3 minutes under the same conditions, and then allowed to stand for 12 hours.

  A 1% thickener aqueous solution was prepared by the above operation.

  Next, a 0.1% calcium hydroxide-containing gel was prepared based on the 1% thickener aqueous solution obtained above. That is, in the Pyrex (registered trademark) container with a capacity of 3000 ml, the 1% thickener aqueous solution (1000 g) obtained above [Is 1101 g better with 1000 g of purified water and 101 g of thickener? ] Under stirring (portable blender machine: manufactured by Tescom Co., Ltd., model: THM320, product name: stick blender; rotation speed = 9,000-15,000 rpm), calcium hydroxide (Ca (OH) 2) powder 1 g of body calcined shell shell calcium powder (manufactured by New Functional Science Co., Ltd., trade name: Cheryl powder) is gradually added over about 5 minutes, and then stirring is continued for about 3 minutes under the same conditions. Let stand for hours.

  When this calcium hydroxide powder is mixed, “foaming” is observed in the gel preparation mixture, but this generated “foam + mixture” is immediately sealed in a sealed container (made of Pyrex (registered trademark) glass; The volume was about 1000 mL, manufactured by Nippon Genetics, trade name: Hiroguchi Medium Bottle). By this operation, the foamable external composition of the present invention was obtained.

As described above, it was confirmed that the pH of the mixture was 12 or more immediately before the “foam + mixture” was put in the sealed container. The measurement conditions used for pH measurement at this time are as follows.
pH measuring device: Hanna Instruments Japan Co., Ltd., Model: HI 98128, Product name: pHep5 (Pep 5)

  Instead of “nonionic water-soluble cellulose ether” (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: Metroles 65SH-4000), which is a thickener used in the above operation, each “thickening” shown in Table 1 above. A foaming external composition using each “thickening agent” shown in Table 1 was obtained in the same manner as in the above operation except that “agent” was used.

  The evaluation results and the like of the various external compositions obtained above are shown in Tables 2 to 6 above and Tables 7 to 8 below.

(Table 7)

(Table 8)

(Confirmation of viscosity change over time)
Among the various gel compositions (foaming external compositions) shown in Tables 2 to 8 above, those using the following “thickening agents” are immediately after gel formation (for example, 5 minutes after gel formation). A good foaming state was exhibited, and a good foaming state was exhibited even after storage for 24 hours in a sealed container.
<Production method A>
Metroise: Hydroxypropyl methylcellulose 65SH-15000, 65SH-15000, 90SH-15000
<Production method B>
Metroise: Hydroxypropyl methylcellulose 65SH-15000, 65SH-15000, 90SH-15000

Example 2
(Viscoelasticity measurement)
Viscoelasticity was measured under the following conditions for eight specimens of “gel composition according to the present invention” obtained in Example 1 (manufacturing dates differ; storage at room temperature) (measurement date and time: January 2016) 28th (Thursday) 13: 00 to 16:00).
・ Test place: Tochigi Prefectural Industrial Technology Center (1-20-20 Yuinomori, Utsunomiya City)
-Measuring machine manufacturer: HAAKE (Haake) [Germany]; Model: Rheostress RS600
・ <Measurement sample>
-Specimen 1: Sample number 201501818 Sample after 1 year (Production date: February 18, 2015)
Specimen 2: Sample number 20150720 Sample after 6 months (manufacturing date: July 20, 2015)
Specimen 3: Sample number 20151209 Sample after 2 months (Production date: December 9, 2015)
Sample 4: Sample No. 2016160115 Sample after 2 weeks (Production date: January 15, 2016)
Specimen 5: Sample number 201601121 Sample after one week (Production date: January 21, 2016)
Specimen 6: Sample number 20160126 Sample after 1 day (Production date: evening of January 26, 2016)
Specimen 7: Sample number 20160128 Sample immediately after production (Production date: January 28, 2016)
Specimen 8: Sample number tepika — 4C10 Commercially available alcoholic gel sample (manufactured by Kenei Pharmaceutical Co., Ltd.)
-Viscoelasticity measuring apparatus The following measurement conditions were set in the rheostress RS600, a measuring instrument was mounted, and samples 1 to 8 were measured.
Sensor: C35 / 1 ° CE (sample amount 0.200 cm 3; measurement range 100 to 106 Pa · S)
* With reference to the viscosity standard, the sensor was selected within the measurement range, assuming that the viscosity was between salad oil (60-80) and shampoo (2,000-3,000).
Measurement temperature: 25 ° C
It was determined on the assumption of storage at room temperature (referring to “cosmetic evaluation method” in JP 2011-185950 A).
Shear rate: continuously increasing from 0 to 200 (1 / S) in 60 seconds, then continuously decreasing from 200 (1 / S) to 0.
dγ / dt [1 / s]: Reference was made to “Cosmetics Evaluation Method” in JP2011-185950A.

  The obtained results are shown in Table 9.

(Table 9)

Example 3
(PH measurement)
1. Implementation date January 28, 2016 (Thursday) 10: 00 to 11:30
2. Place Tochigi Industrial Technology Center (1-20-20 Yuinomori, Utsunomiya City)
3. Measuring machine Manufacturer: HORIBA Model: 6366C
4). <Sample>
Specimen 1: Sample number 201501818 Sample after one year (Production date: February 18, 2015)
Specimen 2: Sample number 20150720 Sample after 6 months (manufacturing date: July 20, 2015)
Specimen 3: Sample number 20151209 Sample after 2 months (production date: December 9, 2015)
Specimen 4: Sample number 201601115 Sample after 2 weeks (Production date: January 15, 2016)
Specimen 5: Sample number 201601121 Sample after one week (production date: January 21, 2016)
Specimen 6: Sample number 20160126 Sample after 1 day (Production date: evening of January 26, 2016)
Specimen 7: Sample No. 20160128 Sample immediately after production (Production date: January 28, 2016)
Specimen 8: Cheryl powder aqueous solution (before adding thickener)
5. Method: Wash and correct the electrode before measuring the sample with “pH standard solution 100-9” (Ph: 9) manufactured by Horiba.
-After correction, samples 1 to 8 are measured. Before each sample measurement, the electrode is washed with “pH standard solution 100-9”.
-The measurement time was 3 minutes after electrode insertion.

  The obtained results are shown in Table 10.

(Table 10)

Example 4
(Thickener screening)
In the present invention, the “thickening agent” suitable for the preparation of the external composition of the present invention can be easily screened by the following method. As is apparent from the following procedure, a significant number (eg, about 10-50 samples of different thickeners) can be screened in parallel.

Specifically, the following procedure is used.
(1) Similar to that in Example 1, a “0.1%” concentration Ca (OH) 2 aqueous solution is prepared.
(2) As in Example 1, the “thickening agent” to be screened is added to the Ca (OH) 2 aqueous solution, and the gelation state of the resulting mixture is visually checked (for example, Depending on the type of “thickener”, it may be in a solution state).
(3) Furthermore, the persistence of the gelled state is visually checked for a long time (for example, after 24 hours).
(4) Check the gelation state for a longer time (for example, about one week).

Example 5
(Measurement of antibacterial effect of composition for external use)
The antibacterial effect of the external composition of the present invention was measured by the following method.
・ Test place: Kaken Test Center (Osaka Office; Nishi-ku, Osaka City)
・ Microorganism: Escherichia coli NBRC 3972
Test method: 0.1 mL of a bacterial solution adjusted to a viable cell count of 10 ⁸ cells / mL (that is, 1 × 10 exp (8) cells / mL) is added to a sample solution of 10 mL, and a specified time (that is, 15 minutes) (30 minutes). Thereafter, 1 mL of the test solution was inactivated with 9 mL of SCDLP broth medium, and the viable cell count was measured by pour plate culture. Moreover, the same process was performed with distilled water as object.

  The results obtained above are shown in Table 11. That is, when distilled water (control) is used as a sample, the initial viable cell count is 8.3 × 10 exp (4), the viable cell count after 15 minutes is 1.1 × 10 exp (5), The number of viable bacteria after 30 minutes was 1.0 × 10exp (5).

  On the other hand, when a Sherry (Sherry ⇒ Shellyl) aqueous solution (that is, an aqueous solution of “water + hydroxide”) was used as a sample, the viable count after 6.0 minutes was 6.0 and after 30 minutes The number of viable bacteria was 3.5.

  Furthermore, when the shelly gel (that is, the gel of “water + hydroxide + thickener” obtained in Example 1) was used as a sample, the viable count after 15 minutes was less than 1.0, The viable count after 30 minutes was also less than 1.0.

(Table 11)

Example 6
(Measurement of foaming power in foaming; body sensory evaluation)
“Ease of foaming” (foaming power) and resistance to foam disappearance (stability) were measured in the facility of New Functional Chemical Co., Ltd. by the following methods. In addition, regarding such “ease of foaming” and measurement of the difficulty of foam disappearance, refer to literature (Oreo Science Vol. 1, No. 8, 863-870, 2001) as necessary. can do.

<Sample>
(1) Foaming composition for external use of the present invention (prepared product using 60SH-06 as a thickener in Examples)
Ingredients: purified water, calcium hydroxide aqueous solution, thickener (“Metrozu” 60SH-06, manufactured by Shin-Etsu Chemical Co., Ltd .; hydroxypropylmethylcellulose)
(2) Daiso Sangyo Co., Ltd. [Manufacturing: Aeolia Co., Ltd.] Medicinal foam hand soap Active ingredient: Triclosan Other ingredients: Water, lauric acid, myristic acid, hydroxylated K, coconut oil fatty acid ethanolamide, glycerin, hyaluron Acid Na-2, aloe extract (2), fragrance, ethanol, EDTA-4Na, BHT, diethylene glycol monoethyl ether, methyl paraben, lactic acid, phenoxyethanol, anhydrous sodium sulfite, sodium benzoate, DL-malic acid (3) Lion (strain) ) "Medicated beautiful clean foam hand soap"
Active ingredient: Isopropylmethylphenol Other ingredients: PG, sorbite solution, lauric acid, palm oil fatty acid acylglycine potassium solution, hydroxylated K, myristic acid, monoethanolamine, fragrance, lauryldimethylamine oxide solution, dimethyldiallyl ammonium chloride Acrylamide copolymer liquid, EDTA, polystyrene emulsion, benzoate, red 401

Inspection items: Ease of foaming (foaming power) and difficulty of foam disappearance (stability)
Inspection method: Equipment used (A) Foam foam bottle (Tokyo Light Industry, trade name: Pump Former M1) Container capacity: 50 mL

(B) Measuring cup (made by Nikko Hansen, trade name: PP disposable beaker)
Container capacity: 100 mL
(C) Foam foam bottle (manufactured by Tokyo Light Industry, trade name: pump former M1)
Container capacity: 50 mL, dispenser: 0.37 cc Midorikawa ⇒ (C) Measuring cup (Daisang Sangyo, trade name: measuring cup) Container capacity: 250 ml

<Measurement of ease of foaming (foaming power)>
“Ease of foaming” of each measurement object was confirmed by the volume of the foam by the following method.
50 ml of the solution to be measured is weighed in the measuring cup (B), filled in the shaker (A) Midorikawa⇒foam foam bottle (A), and then 10 times in the foam foam bottle (C) Midorikawa⇒measurement cup (C). The volume of the foam was confirmed. A total of three types of the above-described foamable external composition of the present invention and the above-mentioned two commercially available products were each subjected to N = 5 times, and images and the like were recorded. At this time, the images were recorded using iPhone 6s (registered trademark) (Apple).
The work of weighing, filling, and pushing the dispenser was performed by one person in charge.

(Confirmation of pH stability)
Using the “foaming composition for external use” of the present invention (prepared product using 60SH-06 as a thickener in Examples), pH stability was measured by the following method.
-Implementation date and time: 1st August 6, 2016 (Sat) 10: 00-11: 00
The second September 6, 2016 (Tuesday) 10: 00 to 11: 00
・ Location: Headquarters, New Functional Science Co., Ltd. 90-7 Sugawara, Shimono, Tochigi
Sample Sample 1A: “Foaming composition for external use” of the present invention (manufactured on July 6, 2016)
Sample 1B: “foaming composition for external use” of the present invention (produced on July 28, 2016)

Inspection method: 1 week, 1 month, 2 months after production, pH of the product is confirmed with test paper. After production, foam foam bottle (D) (manufactured by Daiso Sangyo, trade name: foam pump bottle, container capacity: 350 mL ) Save for the above period. After the storage, foam was sprayed from a dispenser (FIG. 18) on the pH test paper to check the pH.

<Result>
The result obtained by the said test is shown to FIGS.
As shown in these figures, it was confirmed that the pH value was stable even after 2 months had passed since the production.

Example 7
(Measurement of foaming power in foaming; instrumental analysis)
Based on the instrumental analysis, the “foaming power” in foaming was measured by the following method.
<Measurement method and conditions>
1. Implementation date: Thursday, August 4, 2016, 9:30 to 11:00
2. Venue: Osaka City Industrial Research Institute, Biological and Living Materials Research Department, Cosmetic Materials Laboratory (1-6-50 Morinomiya, Joto-ku, Osaka)
3. Measuring machine: Loss Mile method measuring device 4. Sample: Same as Example 6 (3 types)

This measurement was rented out from Osaka City Industrial Research Institute and was measured by in-house members (inspection method: foaming force measurement by the Ross Mile method). Regarding the details of the “apparatus” and the like used here, the following URL (Osaka City Industrial Research Institute) can be referred to as necessary.
http://www.omtri.or.jp/

FIG. 13 shows the appearance of the “measuring device based on the loss smile method” used in this example. The mode of the sample used in this example is shown in FIG. A schematic view of the apparatus is shown in FIG. The outline of the “measurement method by the Ross Mile method” used in this example is shown in the following [Table].
The measurement results from “immediately after falling” to “after 5 minutes” of the foamable external composition of the present invention are shown in FIG. The measurement results of foaming-foam stability of “three types” of samples containing the foamable external composition of the present invention are shown in the graph of FIG.

Example 7a
(Measurement of surface tension; instrumental analysis)
Inspection organization: Osaka Municipal Industrial Research Institute (http://www.omtri.or.jp/)
Inspection method: surface tension measurement suspension plate type and maximum bubble pressure method <test method>
Surface tension meter: CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.
Measuring method: Platinum plate suspension type <Measurement result>
<Sample><Surface tension (mN / m)>
Foamable external composition of the present invention (Sheryl foam) 45.8
L company medicated foam hand soap 31.7
D company medicated foam hand soap 27.7

<Change in surface tension over time>
・ Test report date: August 29, 2016 ・ Executing agency: Osaka Municipal Industrial Research Institute ・ Test method:
It measured at 25 degreeC using Cruz BP-2 (maximum bubble pressure method). As the density of the sample solution, the value of water was used.

<Result>
The results were as shown in Tables 13 to 5 below and FIG.

Example 8
<Confirmation of foaming power by difference in thickener>
1. Date and time of implementation: Saturday, August 6, 2016, 10:00 to 11:00
2. Venue: Headquarters of New Functional Science Co., Ltd. (90-7 Sugawara, Shimono City, Tochigi Prefecture)
3. Measuring instrument 4. sample:
Sample 1: Shellyl foam (thickener 60SH-06)
Sample 2: Shellyl gel (thickener 65SH-4000)
Sample 3: Shellyl gel (thickener 95SH-4000)
5. Inspection method: Ease of foaming was confirmed by the volume of foam.

<Measurement method>
50 ml of the target solution was weighed in (B), filled in (A), and then subjected to 10 pushes in (C) to confirm the foam volume.
The work of weighing, filling and pushing the dispenser was performed by one person in charge.
<Result>
It was as shown in FIG.
The thickener tends to form bubbles more easily in the low viscosity type than in the high viscosity type.

The description with reference to FIG. 1 is as follows.
-The bubble formation speed was fast in the order of 60SH-06>60SH-50> 60SH-10,000.
This is presumed to be because the low-viscosity 60SH type is more easily diffused in the solution than the high-viscosity type, so that foam formation is quick and bubbles with a small particle size are easily formed.
In 60SH-10,000, since the viscosity is high at the same concentration as 60SH-06 and 60SH-50, a force for entraining bubbles is necessary, and it is estimated that foaming becomes more difficult.
In Metroze (60SH-06, 43 mN / m (25 ° C.)) and surfactant (surface tension 32 mN / m (25 ° C.)), the surface tension is lower and bubbles are more easily formed.

Example 9
<Test conditions>
Testing organization: Kitasato University Environmental Science Center Testing period: April 26, 2016 to April 27, 2016 Duration of action: Specimen: 15 minutes; Control: 0 (zero; initial), 15 minutes Test cat Calicivirus: Feline calicivirus F-9 (ATCC (registered trademark) VR-782 (trademark))
Test type: virus inactivation effect test, effectiveness check test of action stop solution, cytotoxicity check test Other test conditions are shown in the following Tables [Table 14-1] to [Table 14-8] and FIG. As shown.

<Results of virus inactivation test>
In this study, we examined the inactivation effect of feline calicivirus (norovirus substitute) by “Sheryl Gel”.
In EN14476: 2005 (Chemical disinfectants and antiseptics Virucidal quantitative suspension test for chemical disinfectants and antiseptics used in human medicine) which is a European standard test method for antiviral agents and the like, the disinfection effect is judged from the initial infectious titer to 4.0 log ₁₀ With the above reduction in infectivity, it was determined that there was an inactivation effect.
In this test, “Sheryl Gel” was found to have an effect of reducing the infectious titer of feline calicivirus by more than 4.0 with an action of 15 minutes, and was judged to have a virus inactivating effect.

<Results of effectiveness confirmation test of action stop solution>
The results are shown in [Table 14-7] above. When the infectivity titer when the virus was allowed to act on the “test sample” was compared with the “control (PBS)”, no difference was observed. From the above results, it was determined that the action stop solution was effective for the test product.
<Results of cytotoxicity confirmation test>
The test results are shown in [Table 14-8] above. In this test, the viable cell ratio of the sample stock solution for cytotoxicity confirmation after dilution of the test product was 50% or more. From the above results, it was determined that no toxicity to CRFK cells was observed and the infectivity titration system was not affected.
Example 10
(Bacteria elimination test)
Test organization: Japan Food Research Center General test outline: After inoculating a specimen with a test bacterial solution (hereinafter referred to as “sample”), the number of viable bacteria in the sample was measured after a predetermined time. A preliminary test (confirmation of neutralization conditions) was conducted in advance to confirm the conditions under which viable cell counts could be measured without being affected by the specimen.
Test results:
The results are shown in [Table] below, and the test conditions are shown in [Table] below. Moreover, the viable count plate after culture | cultivation was shown in [FIG. 9]-[FIG. 10].
In addition, it was confirmed by a preliminary test that the number of viable bacteria can be measured without being affected by the specimen by diluting the sample 10 times with the SCDLP medium.

(Consideration of “Result” in Examples)
<Confirmation of foaming power by difference in thickener>
From this result, it was found that the thickener is more likely to form bubbles in the low viscosity type than in the high viscosity type.

<Confirmation of pH stability>
From this result, it was found that there is no problem in compatibility with a strong alkaline aqueous solution and pH stability even with a low viscosity type thickener.

<Bubbling power-speed of foaming>
From the results of the above “good foaming” and “ease of foaming” by the mouth smile method, the foamable external composition of the present invention (foamable external composition (Cheryl foam)) and a similar commercial product, It was found that there was no significant difference in foaming immediately after the inspection operation. Therefore, in normal usage, after applying the foamable external composition of the present invention, it is considered that the finger is often "familiarized", etc., so the "feeling of foam immediately after application" is a point. Is estimated. From this point of view, it has been found that it is possible to produce a “product with good foaming” even in an embodiment that does not depend on a surfactant.

<Hardness of foam disappearance (slowness of foam break-up speed)
From the data of the defoaming speed result of “ease of foaming” in the above “mouth smile method” (instrumental analysis) and in-house inspection (sensory test), it is similar to the foaming topical composition of the present invention (Sheryl foam). It was found that the foaming external composition of the present invention has a higher defoaming speed than commercial products. In the foaming external composition of the present invention in which the “rinse unnecessary after application” is preferred (that is, the foaming speed is preferred), the “feeling of the remaining foam” is rather disadvantageous. There is a fear. Therefore, in a mode in which “the speed of foaming out” is important, it is preferable to exhibit “the speed of foaming out”.

In addition, the foaming external use of the present invention does not use an antifoaming agent or the like for the purpose of speeding up the foaming, and even if only water + hydroxide + thickening agent is used, “the speed of foaming” It is possible to demonstrate.
URL: www.kansai.co.jp/rd/token/pdf/156/05.pdf

In the present invention, it is preferable to use a thickener that satisfies one or more of the following conditions. The thickener further preferably satisfies two or more of the following conditions, and further preferably satisfies three of the following conditions.
(A) methyl (--CH3) or methoxy (--OCH3) providing a hydrophobic prompting a reduction in the cellulosic hydroxyl hydrogen bonding, and / or that has a group replaced with hydroxycarboxylic propoxy group.
(B) Nonionic properties that are not easily affected by salts and metal ions.
(C) Viscosity standard value (e.g., viscosity specifications in the "Catalog" of the product) is 4.8~18000 mPa · s (20 ℃, 2% aqueous solution) it is.

Claims (12)

A foamable external composition comprising at least water, a hydroxide and a thickener; and
The composition for external use, wherein the hydroxide is selected from an alkali metal hydroxide, an alkali metal earth metal hydroxide, and a tetraalkylammonium hydroxide.   The foaming external composition according to claim 1, wherein the foaming property according to the Ross Miles method is 30 mm to 210 mm in terms of Tf (the time counted immediately after the flow of the test liquid is finished) = 2 minutes. object.   The foaming external composition according to any one of claims 1 and 2, which has antibacterial activity against at least one of Escherichia coli, feline calicivirus and ringworm.   The foaming external composition according to any one of claims 1 to 3, wherein the surface tension is 33 mN / m or more in surface tension measurement by a platinum plate hanging plate method.   The foaming external composition according to any one of claims 1 to 4, wherein the surface tension at Tf = 450 seconds is 38 mN / m or more in surface tension measurement (dynamic) by a maximum foam pressure method.   The foamable external composition according to any one of claims 1 to 5, wherein the surface tension at Tf = 30 seconds is 38 mN / m or more in surface tension measurement (dynamic) by a maximum foam pressure method. The alkali metal hydroxide includes calcium hydroxide (Ca (OH) ₂ ) lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), and hydroxide. The composition for external use according to any one of claims 1 to 6, which is selected from cesium (CsOH). The alkaline earth metal hydroxide comprises strontium hydroxide (Sr (OH) ₂ ), barium hydroxide (Ba (OH) ₂ ), europium (II) hydroxide (Eu (OH) ₂ ), and hydroxide. The composition for external use according to any one of claims 1 to 6, which is selected from thallium (I) (TlOH). Hydroxides of tetraalkyl ammonium, tetramethyl ammonium hydroxide _{(N (CH 3) 4OH)} , and any one of claims 1 to 6, selected from tetraethyl ammonium hydroxide _{(N (C 2 H5) 4} OH) Item 1. An external composition according to Item 1.   The foaming external composition according to any one of claims 1 to 9, wherein the calcium hydroxide is calcium hydroxide produced from a material containing calcium carbonate as a main component.   The foaming external composition according to claim 10, wherein the calcium hydroxide is calcium hydroxide produced from a natural material mainly composed of calcium carbonate.   The composition for external use according to claim 11, wherein the calcium hydroxide is calcium hydroxide produced from shells, corals, egg shells or limestone.