JP3164854B2 - Skin hygiene sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the growth of microorganisms causing acne and unsanitary bacteria on skin by contacting a water-insoluble porous body composed of chitin or chitosan and fibrous material with the skin. The present invention relates to a sheet for skin hygiene that suppresses skin irritation and keeps the skin clean, and a method for using the sheet to prevent acne using the sheet.

[0002]

2. Description of the Related Art Acne is an inflammatory disease of the pilosebaceous system that occurs around puberty, and it is considered that internal and external factors such as age, stress, cosmetics, and diet are involved in a complex manner. The direct cause of the onset is considered to be increased secretion of sebum by hormone stimulation, clogging of pores, or abnormal proliferation of bacteria indigenous to the skin. Propionibacterium acnes (Propionibacter
ium acnes). From such a viewpoint, as a method for treating acne, a method of applying a sulfur-based drug to an affected area, a method of applying a drug applied in a seal form to an affected area, and the like have been used. On the other hand, no effective method for preventing the onset of acne has been known so far, and it has been said that frequent washing of the face and keeping the skin clean are best.

On the other hand, it is already known that an antibacterial effect is exhibited by dissolving chitin and chitosan in an acidic solution. Chitosan and its degradation products have a growth inhibitory effect against phytopathogenic fungi (Allan, C, R., LA Hadwi
ger: The fungicidal effectof chitosan on fungi of
varying cell wall composition, Exp.Micology, 3, 2
85-287 (1979)) and is widely known to have antibacterial properties such as being effective against Gram-positive and Gram-negative bacteria (Hata Uchida: Antibacterial properties of chitin and chitosan, food chemicals, 2). , 22-29 (1988)).

However, antibacterial activity as a general property,
Specific treatment, antimicrobial properties against specific microorganisms for the purpose of prevention, etc. need to be examined in a completely different dimension, considering the type of microorganisms, diversity of properties and the relationship between the microorganisms and inflammation, It is difficult to predict the specific antibacterial activity of chitin and chitosan. As an attempt to use chitosan as a cosmetic material, chitosan is sponge-shaped and acylated and used as a pack or the like (Japanese Patent Laid-Open No. 62-238209).
No.) etc. are known, but these are intended to protect the skin mainly by imparting physical functions such as water retention, and are not intended for specific treatment or prevention. .

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and uses chitosan to form a fibrous structure, exhibits extremely excellent functions in skin hygiene, and is particularly useful for acne prevention. The aim is to provide effective materials.

[0006]

This object is achieved by the following means. That is, the present invention comprises a composite porous body having a tissue obtained by dissolving chitin or chitosan in an acidic solution, mixing with a plant fiber, and integrating the same to form a porous body. A skin hygiene sheet having an antibacterial property against bacteria, and particularly a skin hygiene sheet having an antibacterial property against acne-causing bacteria. Heretofore, there have been no reports on the effects of chitin and chitosan on skin-resident bacteria, in particular, on Propionibacterium acnes, which is a pimple-causing bacterium.

As a result of intensive studies, the present inventors have found that an acidic solution of chitin and chitosan has an excellent effect of killing the bacteria. Further, a water-insoluble porous body sheet (hereinafter, abbreviated as "porous body") made by adding fibrous material to chitin and chitosan to make it porous, especially freeze-dried, is brought into contact with the skin. The inventors have found that other bacteria on the skin can be quickly killed, that the skin is kept clean, and that it leads to the prevention of acne, and the present invention has been completed. In other words, the present invention suppresses the growth of Propionibacterium acnes, which is considered to play a major role in acne inflammation, by using a porous body containing chitin or chitosan, and furthermore, has a harmful effect on the skin. The bacterium Staphylococcus epidermidis
is), Escherichia coli, Staphylococcus aureu
s), Pseudomanas aer
uginosa) can prevent the development of acne through killing or inhibiting growth. The characteristic of this porous material is that, by directly applying or sticking the material directly or immersed in an acidic solution such as water or lemon water to the skin, chitin or chitosan in the porous material gradually dissolves and is resident in the skin. It suppresses the growth of bacteria considered to be involved in the development of acne, such as acne bacteria. In addition, the effect of the porous body for preventing acne is maintained even if the porous body is washed and used many times as long as the porous body is not lost. For further disposal,
It does not pollute the environment because it is naturally degraded by microorganisms in the soil.

Hereinafter, the present invention will be described in detail. In the present invention, chitin refers to D-glucosamine whose amino group is acetylated, regardless of its property, production method, raw material, etc.
A polysaccharide consisting of straight-chain molecules having -1,4 bonds, which includes derivatives such as deacetylated products, etherified products, esterified products, and hydroxyethylated products. The deacetylated product of chitin is particularly called chitosan, but can be used irrespective of the production method and the like. Chitin is an extremely stable polysaccharide and is generally insoluble or hardly soluble in inorganic and organic solvents other than concentrated inorganic acids and formic anhydride, and may be restricted in handling.

On the other hand, chitosan forms a salt in the presence of an acid and dissolves, which is convenient in handling. The degree of polymerization and the degree of deacetylation of chitin and chitosan depend on their solubility, processability,
It affects the stability and the like, and the lower the degree of polymerization, the better the solubility and the better the processability, but there is a tendency that the shape retention, strength and the like in the case of a structure are reduced. Further, the lower the degree of deacetylation, the lower the reactivity and the lower the solubility. Since the antibacterial property is considered to be in the amino group, chitosan having a relatively high ratio of amino group in one molecule and chitosan having a higher degree of deacetylation are preferable from the viewpoint of antibacterial property. In addition, chitosan has a good fixability to a fiber described later, and generally, chitosan is preferably used. However, when chitosan is used, the water resistance and water retention of the structure may be reduced. Therefore, it is advisable to adjust the mixing ratio with the fiber, adjust the water content, and the like. The degree of polymerization of chitosan is generally 100 or more, and the degree of deacetylation is 50 to 100%.
The degree is preferred. In addition, a mixture of chitosan and chitin may be used, and the solubility and the like can be adjusted ("chitin or chitosan" means each alone or a mixture).

[0010] Next, in the present invention, the fibrous material has a function of supporting the structure of the porous body, and when the porous body is brought into contact with the skin, chitin or chitosan is appropriately applied to the skin in the presence of moisture. To elute for a certain period of time. Even in a structure without fibrous material, chitin and chitosan elute quickly even as a porous material, and the structure gradually disappears,
In addition, it is difficult to maintain a constant effect for a long period of time, which is unsuitable for use for treatment and prevention. For the first time, chitin and chitosan can exhibit their original antibacterial properties to the fullest extent by integrating and making the fiber fibrous. It is preferable that the fibrous material contains insoluble plant fiber or water-soluble plant fiber as a main component of the fiber. Here, the insoluble plant fiber often contains cellulose as a main component, but preferably has a characteristic that it has a hydrophilic active group on its surface and has a fixing property to chitin and chitosan. The shape is preferably fibrous. This is because the structure can be easily constructed.

[0011] Typically, it is a plant fiber derived from wood or grain. The wood fiber is a fiber derived from conifers such as fir and fir, a fiber derived from hardwood, and the like, and is available as, for example, pulp fiber or wood pulp. The cereal fiber is a fiber derived from the outer skin of bran such as wheat or soybean, and for example, a soybean pressed residue (okara) or the like can be used. One or more of these can be used, and crystalline cellulose can also be used.

On the other hand, when a water-soluble plant fiber is used, the structure of the porous body is reduced, and the porous body itself may partially dissolve in a long-term use. If used, it can be used satisfactorily depending on the form of use.

[0013] Here, the water-soluble plant fiber means a water-soluble indigestible component mainly composed of polysaccharide, regardless of its origin.
Plant-derived polysaccharide, seaweed-derived polysaccharide, microorganism-derived polysaccharide,
And chemically modified polysaccharides. As plant-derived polysaccharides, guar gum, locust bean gum, tara gum,
Pectin, mannan, hemicellulose, cereal gums such as β-glucan and the like are exemplified, and polysaccharides derived from seaweed include alginic acid, carrageenan, furceleran, etc., and polysaccharides derived from microorganisms include xanthan gum, pullulan, etc. Modified polysaccharides include polydextrose, carboxymethyl cellulose and the like. The above insoluble and water-soluble plant fibers can be used alone or as a mixture of two or more.

In the present invention, chitin or chitosan and fibrous material are integrated. The term “integration” refers to homogeneously mixing to form a polyion complex, but the degree and mode of formation of the polyion complex are not particularly limited,
What is necessary is just to adjust suitably according to the target porous body. That is, the final porous body is prepared so as to have a structure in which chitin and chitosan are bonded or attached to the fibrous material.

Next, a feature of the porous body of the present invention is that it is porous in addition to the above-described structure. Since it is a porous body, it is lightweight, flexible, has sufficient strength, and can have excellent reactivity because it can greatly increase the surface area. That is, the antibacterial properties of chitin and chitosan are related to the structure of the porous body, and an effective action and effect can be obtained only when the structure is optimized. The bulk specific gravity of the porous material is generally about 0.01 to 0.1 g / cc, but may be appropriately set depending on the intended use of the porous body. The hole diameter is not particularly limited, and may be designed in relation to the desired mechanical characteristics. Usually 10-50
It may be about 0 μm. If the bulk specific gravity is small and the pore size is large, the composite porous body is rich in water absorption and elasticity, but the strength and water resistance are reduced, while if the bulk specific gravity is large and the pore size is small,
Hardens, reduces water absorption and increases strength and water resistance.
The antibacterial property tends to decrease even if the bulk specific gravity is small or large, and is appropriately adjusted within the above range.

By the way, chitosan is particularly soluble in dilute acid, and is therefore affected by water in its structure. No special treatment is required for a water-soluble structure, but in the case of a water-resistant structure, an insolubilization treatment is required. In other words, the resulting porous body has excellent water retention, but when immersed in water, the chitosan and fibers forming the structure swell and dissolve in water, so the porous body retains shape. Lose sex. Therefore, if the device is used for a relatively long time, it may become lumpy. By the way, when the composite porous body is insolubilized by acetylation treatment, chitosan integrated with the fiber is acetylated, so that the tissue can be maintained and stabilized without substantially impairing the function of the fiber. The reason is that before the acetylation, the porous body is already integrated at the molecular level on the tissue, and the chitosan molecule is entangled with the fiber molecule by a polyion complex, etc., and the fiber molecule is physically or chemically
It is considered that they are electrically constrained. For example, a carboxyl group, which is a hydrophilic group of a fiber molecule, bonds with an amino group of chitosan to reduce hydrophilicity and form a crosslinked structure. In this state, further acetylation of chitosan is considered to significantly stabilize the structure at the molecular level and realize structural strength and water resistance while maintaining functions such as water absorption of the fiber.

Normally, even when chitosan having a deacetylation degree of 60% or more is used as a raw material, the final product has an acetylation degree of about 40 to 50% due to the use of an acetic acid solution or the like.
Since water resistance cannot be expected at this degree of acetylation, acetylation treatment is performed to reduce the acetylation degree to 60 to 70.
% Or more, water resistance can be achieved.

The weight ratio of chitin or chitosan to fibrous material is preferably from 1: 0.5 to 1: 5, and within this range, the binding or adhesion of chitin or chitosan is effectively exhibited, It can maintain its structure and exhibit an antibacterial effect. If the proportion of the fiber is too large, the structure becomes high, but the antibacterial action becomes insufficient. On the other hand, when the proportion of the fiber is too small, the antibacterial action is not sufficiently exhibited because the structure becomes low and the fiber becomes hard.

Next, an example of a method for preparing the porous body of the present invention will be described. First, a mixed solution composed of water, chitosan, fiber and acetic acid is prepared. In addition to acetic acid, lactic acid, citric acid, hydrochloric acid and the like may be used. Chitosan and fiber are pH 4.8
Since it dissolves in the acidity below pH 4, preferably below pH 4,
It can be dissolved and mixed in 50 to 100 times the amount of water. After neutralization, the mixed solution is placed in a mold having an arbitrary shape and thickness depending on the use form to make it porous, and then acetylated, whereby a chitosan composite porous body having fibers immobilized on chitosan is formed. In addition, the amount of fiber varies with the type of fiber used. In the above pH range, it is sufficient for dissolving chitosan, but insufficient for dissolving chitin. When chitin is used, it may be dissolved in formic anhydride or the like in advance or made into fine particles.

As a method for making the porous material, a method of mixing a pyrolytic foaming agent such as sodium hydrogencarbonate or ammonium hydrogencarbonate, or a reactive foaming agent such as baking powder to which an acidic agent is further added, or a mixer or the like. A commonly used method such as a method of mechanically mixing air can also be used, but freeze drying of the solution is most preferable for forming fine pores. In this case, a fine porous structure and an antibacterial effect are not obtained. There is also an advantage that it is possible to simultaneously make porous and dry while maintaining both. The freezing temperature is preferably about -20 to -40C, and finer pores are formed at lower temperatures.

Acetylation can be carried out, for example, by dipping in a solution of an organic anhydride such as acetic anhydride or exposing the solution to a gaseous atmosphere. The higher the degree of acetylation, the lower the solubility and the higher the stability. Usually, about 68% can be acetylated in one hour in gas. It should be noted that, even if the processing is continued overnight, a horizontal buyout occurs at about 70%. Drying of the structure can usually be carried out at 100 to 150 ° C. for about 3 to 12 hours. The water content may be about 2-4%.

The porous body described above is most preferably in the form of a sheet in use. This is because a relatively thin layer is more convenient because it is a use mode of contacting the skin. In addition, since it is a porous body even if it is thin, it has sufficient water retention, and has a large surface area that can be a reaction surface and exhibits a high antibacterial effect. Usually 2
It may be about 10 to 10 mm thick. The size is appropriately selected depending on the purpose of use. A relatively small mat may be used for spot treatment of acne or the like, or a relatively large cut may be used for hygienic applications such as cleaning the face over a wide area.

As a method for preventing acne using the skin hygiene sheet of the present invention, the skin hygiene sheet is sterilized or grown by contacting the skin as it is or by immersing it in water or an acidic solution to the skin. Methods for suppressing and preventing the onset of acne may be mentioned. Even if it comes into contact with the skin as it is, the sheet receives moisture due to the breathing of the skin, etc.,
Moisture is trapped inside the structure, and the function is gradually exerted. In addition, when acne has already been generated, a liquid material is accumulated in that part, and it has a function of directly contacting the affected part by absorbing this. In the above method, in the embodiment in which the acidic solution is impregnated, the dissolution of chitosan and chitin is positively promoted. This allows
The amount of chitosan and chitin acting on the affected area increases, and the effect can be enhanced. However, it is not suitable for long-term use due to reduced resistance. In addition, since the acid solution itself can be expected to have a small but antibacterial action to some extent, a synergistic effect is exhibited. As the acidic solution, for example, a lemon solution or the like having a pH of about 3 to 5 can be used.

Both chitin and chitosan have high biocompatibility,
There is no problem even if it comes into contact with the skin for a long time, and it is suitable for skin hygiene.

Specifically, in order to prevent and treat acne, for example, the sheet of the present invention is supported on a support such as a suitable gauze, sponge, or cotton cloth and impregnated with water or an acidic solution. Paste it on. It is effective to reapply several times a day. Or, at night, apply the same sheet before going to bed, leave it on until morning, or after every face wash, 5-10 minutes,
You may attach a sheet. In this case, no particular support is required. Since the sheet of the present invention has high water absorption, the impregnated liquid does not easily exude.

[0026]

The present invention will be described below with reference to examples.

Example 1 (Preparation of porous body) 1 g of paper pulp (manufactured by Todomatsu) and 1 g of chitosan (degree of polymerization: about 2,000, degree of deacetylation: 80) were mixed with 100 cc of water, and 1 g of acetic acid was added with stirring. (PH 3.5). Stir well until chitosan and pulp are completely dispersed, spread on a pad and freeze-dry (-20 ° C), neutralize with 10% aqueous sodium hydrogen phosphate, and add 2.5 ml of acetic anhydride Was added to acetylate the chitosan. Next, the sheet is washed with water and dried by ventilation (105 ° C., 2 hours) to form a sheet (L300 mm ×
(W300 mm x T5 mm) porous body was obtained. This had an acetylation degree of 30%, a bulk density of 0.05 g / cc, an average pore diameter of 100 μm, and a water content of 3%. In the following antibacterial activity test, the above porous body cut into a cube of about 5 mm and sterilized by an autoclave was used.

(Test for antibacterial activity) (Test 1) A culture solution of Propionibacterium acnes SBT-3380 (acne bacillus) cultured in a GAM medium at 37 ° C. for 20 hours, and a porous body cut into about 5 mm cubes Was inoculated into 20 ml of GAM medium at a concentration of about 1 × 10 ⁶ CFU / ml, and cultured at 37 ° C. with reciprocal shaking (150 rpm). The culture solution was collected at regular intervals, and the number of viable bacteria was measured. As shown in Table 1, the bactericidal action against Propionibacterium acnes was observed in the porous body.

[0029]

[Table 1] (Test 2) Staphylococcus epidamidis SBT-3078 cultured on a normal agar medium at 37 ° C. for 20 hours.
Culture medium and 100 mg of a sterilized small piece of a porous body cut into about 5 mm cubes were placed in a 20 ml ordinary agar medium at about 1 × 1.
0 ⁶ CFU / ml and then inoculated to and reciprocal shaking culture (150 rpm) at 37 ° C.. The culture solution was collected at regular intervals, and the number of viable bacteria was measured. As shown in Table 2, the bactericidal action against Staphylococcus epidamidis was observed in the porous body.

[0030]

[Table 2] (Test 3) A culture of Escherichia coli SBT-3242 cultured in a standard liquid medium at 37 ° C. for 20 hours, and about 5
100 mg sterilized small pieces of porous material cut into mm cubes
In a 20 ml ordinary agar medium at about 1 × 10 ⁶ CFU / ml
And reciprocal shaking culture at 37 ° C (150 r
pm). The culture solution was collected at regular intervals, and the number of viable bacteria was measured. As shown in Table 3, the bactericidal action against Escherichia coli was observed in the porous body.

[0031]

[Table 3] (Test 4) A culture solution of Staphylococcus aureus SBT-3266 cultured in a standard liquid medium at 37 ° C. for 20 hours, and a sterilized small piece of a porous body cut into about 5 mm cubes (100 mg) were added to a 20 ml SPC medium. 1 × 10 ⁶ C
FU / ml was inoculated and cultured at 37 ° C with reciprocal shaking (150 rpm). Collect the culture solution at regular intervals,
The viable cell count was measured. As shown in Table 4, the bactericidal action against Staphylococcus aureus was observed in the porous body.

[0032]

[Table 4] (Test 5) A culture solution of Pseudomonas aeruginosa cultured in SPC medium at 37 ° C. for 20 hours, and 100 mg of a sterilized small piece of a porous body cut into about 5 mm cubes were put in 20 pieces.
The mixture was inoculated into ml SPC medium at about 1 × 10 ⁶ CFU / ml, and cultured at 37 ° C. with reciprocal shaking (150 rpm). The culture solution was collected at regular intervals, and the number of viable bacteria was measured. As shown in Table 5, Pseudomonas
A bactericidal effect on aeruginosa was observed.

[0033]

[Table 5] (Test 6) Escherichia coli SB on a standard agar plate medium
After 1 ml of a T-3242 culture solution was smeared and sufficiently infiltrated into agar, a porous body which had been sterilized in advance was placed on a plate medium. After 10 minutes and 30 minutes, the porous body was removed, and the removed agar was hollowed out using a stainless steel pipe having an inner diameter of 6 mm. The removed agar was put into 5 ml of physiological saline, and then stirred well, and the viable cell count was measured. as a result,
As shown in Table 6, the viable cell count of Escherichia coli was reduced by directly contacting the porous body. As a control, a gauze cut out to the same size as the porous body was used.

[0034]

[Table 6] (Porous Body Sticking Test) The obtained porous body was 25 m
cut into mx 20 mm (thickness of about 2 mm when dried), immersed in lemon solution (pH 2.4), swelled sufficiently, about 2 k
Squeezed with a load of g to remove liberated liquid. Three times a day, a person with acne inflammation was stuck to the porous patch or a conventional gauze, similarly immersed and squeezed with a lemon solution, and taped. Five volunteers wearing the gauze patch (comparative product) stated that some of the lemon juice leaked out and stained the clothes, and that the inflammation did not heal faster. On the other hand, five volunteers wearing the porous patch stated that there was no outflow of lemon juice and that the porous body absorbed the liquid coming out of acne and the inflammation was cured quickly.

Example 2 The porous material (Ch-P-A) obtained in Example 1 and the non-acetylated porous material (Ch-P) obtained by the same method were used.
-O) was used to test antibacterial activity against P. acnes SBT-3380 based on: Test method: A seed culture cultured overnight at 37 ° C. was inoculated with 100 mg of a sterilized porous material (about 5 mm cubic) into a 20 ml medium (GAM medium) at about 1 × 10 ⁶ CFU / ml, and cultured. I do. Collect the culture solution at regular intervals,
The viable cell count is measured. As a result, as shown in FIG.
h-P. A bactericidal effect on acnes was observed. In particular, no detection of bacteria was observed for Ch-PO without acetylation treatment even after 5 days. For Ch-PA subjected to the acetylation treatment, the number of viable cells temporarily decreased greatly, but the number of viable cells increased thereafter. Thus, the non-acetylated Ch-P had stronger antibacterial activity in the long term, but in actual acne prevention, it was replaced several times a day, so there was no substantial difference. Was determined.

[0036]

As described above, the porous body of the present invention exerts an excellent antibacterial action against acne-causing bacteria due to its structure and antibacterial properties of chitin and chitosan, and keeps the skin clean. In particular, it is extremely effective in preventing and treating acne. In addition, there is a large degree of freedom in the form that the form can be designed as desired, and it is excellent as a skin hygiene sheet.

[Brief description of the drawings]

FIG. 1 is a graph showing the P.P. of a porous material obtained in Examples of the present invention. ac
It is a figure which shows the antibacterial property with respect to nes.

Continuation of the front page (56) References JP-A-1-207238 (JP, A) JP-A-62-238209 (JP, A) JP-A-63-290808 (JP, A) JP-A-64-16714 (JP) , A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K 31/722 A61K 9/00-9/72 A61K 47/00-47/48 C08J 9/28 C08L 5/08

Claims (4)

(57) [Claims] 1. Dissolution of chitin or chitosan in an acidic solution
And, integrally mixed with vegetable fiber, made from a composite porous body having formed by porous tissue sheet skin hygiene with antimicrobial against indigenous bacteria on the skin. 2. The resident bacterium on the skin is an acne-causing bacterium.
The sheet for skin hygiene according to claim 1. Wherein said composite porous body is treated acetylated
Consisting claim 1 or 2 Skin hygiene seat according. 4. A method in which chitosan is dissolved in the presence of moisture for a certain period of time.
The skin hygiene sheet according to claim 1, 2 or 3, which can be put out.