JP2000212074A - Multilayer gel structural self-adhesive sheet for living body and cosmetic and quasi-drug using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a self-adhesive sheet for living body which has good operativity, shows an excellent follow-up property to skin movement and storage durability and gives no visual feeling of physical disorder. SOLUTION: This multilayer gel structural self-adhesive sheet 1 for living body includes a self-adhesive layer and a base layer which are composed of the gel of a synthetic polymer containing at least water as a solvent and having a network structure and have mutually different gel compositions and the both layers are laminated in the direction of the thickness of the self-adhesive sheet 1. Further, cosmetic and quasi-drugs on this invention are made of the self-adhesive sheet 1 and include therapeutic ingredients or the like correspondent to the cosmetics or the quasi-drugs.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biological adhesive sheet having a multilayer gel structure used in the fields of pharmaceuticals, quasi-drugs, cosmetics, sanitary materials, miscellaneous goods, and the like. The present invention relates to a multi-layer, gel-structured pressure-sensitive adhesive sheet for a living body, which has excellent flexibility and does not cause visual discomfort even when attached to the skin.

[0002]

2. Description of the Related Art Conventionally, packs and patches used for the treatment of beauty, beauty and skin, and the like, or pressure-sensitive adhesive sheets for living bodies such as transdermal absorbents, pressure-sensitive adhesive tapes for wounds, wound dressings, anti-inflammatory analgesics and the like have been used. From the viewpoint of ease of handling and the effect of blocking the skin surface, etc., a sheet-shaped material such as a nonwoven fabric, a woven fabric, or a plastic film was used as a support substrate, and various active ingredients were contained on the support substrate. What adhere | attached the hydrophilic adhesive gel is used. However, in order to prevent the adhesive gel from slipping through the nonwoven fabric or woven fabric,
Since the opaque one with little porosity is used,
There was a problem that the visual unpleasant sensation when attached to the skin surface was large, and the time and place were greatly restricted when using the bioadhesive sheet.

On the other hand, if a plastic film is used as a supporting base material, the whole pressure-sensitive adhesive sheet for living body can be made transparent, so that there is provided a pressure-sensitive adhesive sheet which is not conspicuous at the time of use and does not give a sense of visual discomfort. However, the adhesion between the hydrophilic pressure-sensitive adhesive gel and the plastic film is poor, and both are easily peeled off, which causes a problem in use. Furthermore, since the plastic film lacks flexibility, the pressure-sensitive adhesive sheet for a living body cannot follow the movement of the skin surface sufficiently, and it is easy to peel off from the skin surface, and there is a problem that the skin becomes uncomfortable when used. .

[0004]

SUMMARY OF THE INVENTION In order to solve the above problems, Japanese Patent Laid-Open Publication No. 3-86806 and Japanese Patent Laid-Open Publication No.
No. 117 discloses that gelatin is a polyvalent metal ion compound,
A sheet using a gel obtained by reacting aldehydes, polyhydric alcohols or saccharides as a support substrate, and using a hydrogel obtained by reacting a polyacrylic acid-based polymer with a polyvalent metal ion compound as an adhesive layer Packs or patches are disclosed.

[0005] If the pack agent disclosed in the above publication is used,
Since both the gelatin as the support substrate and the hydrogel used for the adhesive layer are transparent or translucent, there is no visual discomfort when applied to the skin surface. In addition, since both the support base material and the adhesive layer are made of gel, there is no problem that both peel off at the time of use, and since the followability to the movement of the skin surface becomes better, it is easy to peel off from the skin surface. Problems can also be solved.

However, gels containing gelatin as a main component have another problem of poor stability to heat. When stored at a high temperature, the shape of the product itself is impaired. When transporting, the problem that the product is deteriorated remarkably occurs. Further, since gelatin is a natural product, the gel tends to rot, and even if a large amount of a preservative is added to prevent the decay of the gel, the gel is not suitable for use in direct contact with the human body. In addition, there is a problem from the viewpoint of quality stability, for example, since gelatin is a natural product, the quality varies.

[0007] Therefore, an object of the present invention is to solve the above-mentioned problems, to have a degree of transparency that does not cause visual discomfort, to prevent peeling or destruction during use, and to follow the movement of the skin. An object of the present invention is to provide a biological pressure-sensitive adhesive sheet which is excellent in heat resistance and rot resistance (that is, excellent in storage durability).

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, as a pressure-sensitive adhesive layer and a supporting substrate of a pressure-sensitive adhesive sheet for living body, a synthetic polymer having different compositions from each other has been used. The present inventors have found a new fact that when a gel body is used and these are laminated in the thickness direction, it is possible to obtain a multi-layered gel-structured pressure-sensitive adhesive sheet for a living body that has solved the above-mentioned problems, and has completed the present invention.

That is, the multi-layered gel-structured pressure-sensitive adhesive sheet for living body of the present invention comprises a pressure-sensitive adhesive layer comprising a synthetic polymer gel having a network structure and containing at least water as a solvent, and having a gel composition different from each other, and a support layer. The adhesive layer and the support layer are laminated in the thickness direction. According to the multi-layered gel structure living body pressure-sensitive adhesive sheet of the present invention, since the pressure-sensitive adhesive layer and the support layer each consist of a gel body,
The feeling of adhesion to the skin and the followability to the movement of the skin are excellent, and the adhesiveness between the adhesive layer and the support layer is good, so that peeling between the two layers does not occur during use.

The adhesive properties of the two layers are also different due to the difference in the gel composition of the adhesive layer and the support layer. Therefore, according to the pressure-sensitive adhesive sheet of the present invention, the pressure-sensitive adhesive layer is set so that the pressure-sensitive adhesive layer has sufficient pressure-sensitive adhesiveness to the skin, and the support layer is set to have a lower pressure-sensitive adhesiveness than the pressure-sensitive adhesive layer. Thereby, the operability at the time of sticking to or peeling from the skin can be improved.

The degree of adhesion between the pressure-sensitive adhesive layer and the support layer in the multi-layered gel-structured pressure-sensitive adhesive sheet for living body of the present invention is determined in accordance with JIS Z 0237-1991 "Testing method for pressure-sensitive adhesive tape / pressure-sensitive adhesive sheet" from the above viewpoint. When measured with a ball tacking device (inclination angle: 20 degrees), the difference in ball number between the adhesive layer and the support layer becomes 1 or more,
And it is preferable that the ball number of the adhesive layer is adjusted to be in the range of 2 to 50.

The gel constituting the pressure-sensitive adhesive layer and the support layer in the pressure-sensitive adhesive sheet of the present invention is described in JP-A-3-86.
It is transparent or translucent like the gelatin or the hydrogel that constitutes the supporting substrate and the adhesive layer in JP-A-806 and JP-A-3-167117. Therefore, the external appearance of the pressure-sensitive adhesive sheet of the present invention is also transparent or translucent, and when applied to the skin, there is no visual discomfort.

Further, the gels constituting the adhesive layer and the support layer are not natural polymer gels such as gelatin, but are synthetic polymer gels.
The pressure-sensitive adhesive sheet of the present invention has excellent storage durability and quality stability. In the multi-layered gel-structured bioadhesive sheet of the present invention, the synthetic polymer having a network structure constituting the gel body includes (a) one or more polymerizable unsaturated monomers and a crosslinkable unsaturated monomer. Copolymer with monomer, or (b)
Hydrophilicity obtained by polymerizing one or more polymerizable unsaturated monomers having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group on a side chain A crosslinked structure obtained by reacting a synthetic polymer with at least one crosslinking agent selected from the group consisting of a polyvalent metal ion compound, a polyvalent carboxylic acid, a polyhydric alcohol, a polyfunctional epoxide and a dialdehyde. It is preferably a body.

The polymerizable unsaturated monomers include:
It is preferably at least one selected from the group consisting of (meth) acrylamide and its derivatives, vinylpyrrolidone, (meth) acrylic acid and its salts. From the viewpoint of improving the strength and handleability, the multilayer gel structure living body pressure-sensitive adhesive sheet of the present invention has a sufficient opening ratio inside or on the surface of the pressure-sensitive adhesive sheet as long as the transparency of the pressure-sensitive adhesive sheet is not impaired. Large woven or non-woven fabrics may be laminated.

On the other hand, cosmetics and quasi-drugs of the present invention are characterized by being formed from the above-mentioned multi-layered gel-structured pressure-sensitive adhesive sheet for living body of the present invention. Incidentally, in the present invention, the "adhesive sheet for a living body" refers to a pack fee, a patch, a transdermal absorbent, an adhesive tape for a living body, a wound covering agent, an anti-inflammatory analgesic, and the like.
It refers to an adhesive sheet that is used by attaching it to the skin for the purpose of treating beauty, facial beauty, skin, and the like.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the multi-layered gel structure bioadhesive sheet of the present invention, the gel body constituting the pressure-sensitive adhesive layer and the support layer is composed of at least a synthetic polymer having a network structure and a solvent containing water, and is preferably colorless or colored. It is characterized by being transparent or translucent and having shape retention.

(Solvent) The proportion of water in the gel constituting the adhesive layer and the support layer is preferably 1 to 99% by weight. If the proportion of water in the gel body is less than 1%, it may not be possible to easily dissolve various additives such as medicinal ingredients and the like incorporated in the gel. Conversely, if the proportion of water in the gel body exceeds 99% by weight, the stiffness of the gel body becomes weak, and it is difficult to stably maintain additives such as solvents and medicinal components contained in the gel body. Could be.
The proportion of water in the gel body is preferably 5 to 5 in the above range.
It is preferably 95% by weight, more preferably 10-85% by weight.

Solvents constituting the above-mentioned gel body are those which do not cause phase separation with water in addition to water, and have conventionally been used for transdermal applications in the fields of cosmetics, pharmaceuticals, quasi-drugs, sanitary materials, sundries and the like. As long as the solvent is used, it can be used after being mixed with water. Such solvents include, for example, monoalcohols such as ethyl alcohol,
Examples thereof include glycols such as 1,3-butylene glycol, and polyhydric alcohols such as glycerin, and these can be used alone or in combination of two or more.

The proportion of the solvent other than water in the gel body is 98
Preferably it is less than or equal to% by weight. If the ratio exceeds 98% by weight, there is a possibility that various additives and the like blended in the gel body cannot be easily dissolved. Furthermore, the stiffness of the gel body may be weakened, and it may be difficult to stably maintain additives such as a solvent and a medicinal component contained in the gel body.

(Synthetic polymer having a network structure) As the synthetic polymer having a network structure, which constitutes the gel body,
It has affinity for water and retains its gel structure even after it has been stored at least at 60 ° C. for one month, and has been conventionally used for transdermal applications in the fields of cosmetics, pharmaceuticals, quasi-drugs, sanitary materials, sundries, etc. There is no particular limitation except that
Various synthetic polymers can be used.

Among them, from the viewpoint of easy manufacture,
(a) a copolymer of one or more polymerizable unsaturated monomers and a crosslinkable unsaturated monomer, or (b) a hydroxyl group on a side chain,
A hydrophilic synthetic polymer obtained by polymerizing one or more polymerizable unsaturated monomers having at least one functional group selected from the group consisting of a carboxyl group, an amide group and an amino group; A crosslinked structure obtained by reacting at least one type of crosslinkable factor selected from the group consisting of a polyvalent metal ion compound, a polyvalent carboxylic acid, a polyhydric alcohol, a polyfunctional epoxide and a dialdehyde is preferably used. Can be

Examples of the hydrophilic synthetic polymer having a hydroxyl group in a side chain include polyvinyl alcohol obtained by polymerizing and hydrolyzing a vinyl acetate monomer. Examples of the hydrophilic synthetic polymer having a carboxyl group in the side chain include poly (meth) acrylic acid and those obtained by neutralizing a part or all of the carboxyl group with an alkali such as sodium hydroxide. Examples of hydrophilic synthetic polymers having an amide group in a side chain include poly (meth) acrylamide, polyN,
N'-dimethyl (meth) acrylamide, polyvinylpyrrolidone, poly N-vinylacetamide, and the like. Examples of the hydrophilic synthetic polymer having an amino group in the side chain include polyallylamine, one in which some or all of the amino groups are neutralized with an acid such as hydrochloric acid, and polymethacryloyltrimethyloxyethylammonium chloride.

The monomer constituting the above-mentioned hydrophilic synthetic polymer may have, in addition to a hydroxyl group, a carboxyl group, an amide group and an amino group, a functional group obtained by modifying these groups. For example, a treatment for esterifying about 40% of the hydroxyl groups or carboxyl groups in the hydrophilic synthetic polymer to make it lipophilic may be performed for the purpose of improving the adhesion to the skin. Also,
When there is a long saturated hydrocarbon moiety in the side chain, for the purpose of imparting hydrophilicity to the moiety, a hydroxyl group,
Introducing carboxyl group, amide group, amino group, etc.
You may introduce | transduce ionic functional groups, such as a sulfonic acid group and a phosphoric acid group, and may process with reagents, such as an acid and an alkali.
These treatments may be performed before the polymerization of the monomer or after the polymerization.

Examples of the polymerizable unsaturated monomer include (meth) acrylamide; (meth) acrylamide such as t-butylacrylamide sulfonic acid (and a salt thereof), N, N′-dimethylacrylamide and dimethylaminopropyl methacrylamide. Derivatives of vinyl pyrrolidone;
(Meth) acrylic acid (and salts thereof) are preferably used from the viewpoint of easy production. The polymerizable unsaturated monomers may be used alone or as a mixture of two or more.

Examples of the crosslinking unsaturated monomer include N,
N'-methylenebisacrylamide, N, N'-methylenebismethacrylamide, N, N'-ethylenebisacrylamide, N, N'-ethylenebismethacrylamide, 1,2-diacrylamideethylene glycol, and the like. As described above, as the crosslinking factor, a polyvalent metal ion compound, a polyvalent carboxylic acid, a polyhydric alcohol,
Examples include polyfunctional epoxides and dialdehydes.

Among them, polyvalent metal ion compounds include:
For example, aluminum compounds, calcium compounds, magnesium compounds and the like can be mentioned. Among them, from the viewpoint of crosslinking efficiency, aluminum hydroxide and salts thereof, synthetic aluminum silicate, magnesium aluminate metasilicate, magnesium aluminum oxide, aluminum oxide, dihydroxyaluminum amino acetate, magnesium aluminum hydroxide carbonate hydrate, hydroxide Compounds containing trivalent aluminum ions, such as aluminum sodium carbonate coprecipitate, are preferred, and those having an amorphous structure are more preferred.
As polyvalent carboxylic acids, for example, succinic acid, fumaric acid,
Examples include phthalic acid, citric acid, malic acid and the like. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, butanediol, glycerin, diethylene glycol, diglycerin and the like. Examples of the polyfunctional epoxide include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether,
Polytetramethylene glycol diglycidyl ether,
Glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, resorcin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6- Hexanediol diglycidyl ether and the like. Examples of dialdehydes include glyoxal, terephthalaldehyde, glutaraldehyde and the like.

In the gel body constituting the multi-layered gel structure bioadhesive sheet of the present invention, ie, the adhesive layer gel and the support layer gel, the amount of the synthetic polymer having a network structure, which constitutes the gel body, is as follows. 1 to 5 based on the total amount of the gel body
It is preferably 0% by weight. If the compounding amount of the synthetic polymer is less than 1% by weight, the stiffness of the gel body is weakened, and it may be difficult to stably maintain additives such as a solvent and a medicinal component contained in the gel body. . Conversely, 50% by weight
If it exceeds, the gel strength is increased, but the polymer structure of the gel body becomes too dense, and the amount of the solvent, the medicinal component and the like that can be retained in the gel body may be too small. The compounding amount of the synthetic polymer is particularly preferably from 3 to 30% by weight, more preferably from 5 to 25% by weight in the above range.

As the synthetic polymer having a network structure,
When the copolymer (a) is used, the amount of the crosslinkable unsaturated monomer is preferably 0.005 to 0.5% by weight based on the total amount of each gel. If the compounding amount is less than 0.005% by weight, it is difficult to obtain a gel having sufficient waist strength, and it may be difficult to stably maintain additives such as a solvent and a medicinal component contained in the gel. is there. Conversely, if the compounding amount exceeds 0.5% by weight, the brittleness of the obtained gel body increases, and there is a possibility that the gel body may be easily cut or broken by tensile stress or compressive stress.

On the other hand, as a synthetic polymer having a network structure, the cross-linking factor is a polyvalent metal ion compound (b).
When the crosslinked structure of (1) is used, the compounding amount of the polyvalent metal ion compound is preferably 0.1 to 10% by weight based on the total amount of each gel body. When the crosslinking factor is a polycarboxylic acid or a polyhydric alcohol, the blending amount of the polycarboxylic acid or the polyhydric alcohol is preferably 0.1 to 5% by weight based on the total amount of each gel. . When the crosslinking factor is a polyfunctional epoxide or dialdehyde, the amount of the polyfunctional epoxide or dialdehyde is 0.01 to 3% by weight based on the total amount of each gel. Is preferred.

If the amount of the crosslinking factor such as a polyvalent metal ion compound is less than the above range, the resultant synthetic polymer gel has a low stiffness, and the addition of a solvent, a medicinal component and the like encapsulated in the gel. It may be difficult to keep the agent stable. Conversely, if the amount exceeds the above range, the brittleness of the gel body increases, and there is a possibility that cutting or destruction may easily occur due to tensile stress or compressive stress.

In the present invention, the gel constituting the multi-layered gel-structured pressure-sensitive adhesive sheet for a living body, that is, the method of forming the pressure-sensitive adhesive layer gel and the support layer gel, may be a conventionally known method. [Layer Structure of Multilayer Gel Structure Biological Adhesive Sheet] The multilayer gel structure biological adhesive sheet of the present invention is obtained by laminating at least two types of gel bodies having different gel compositions in the thickness direction.

In the present invention, “different gel composition” means that at least the types of synthetic polymers having a network structure are different, and as a result, the strength, elasticity, adhesive properties, affinity with other solvents, It means that physical and chemical properties such as drying property are different. Therefore, not only when the types of the polymerizable unsaturated monomer, the crosslinkable unsaturated monomer or the crosslinkable factor constituting the synthetic polymer having a network structure are different, but also (1) the polymerizable unsaturated monomer. Although the kind of the crosslinkable unsaturated monomer or the crosslinkable factor is completely the same, but the mixing ratio of each is different, or (2) polymerizable unsaturated monomer, crosslinkable unsaturated monomer or Even if the type of the crosslinking factor and the mixing ratio thereof are completely the same, the condition of "different gel composition" is satisfied even when the polymerization reaction conditions and the crosslinking reaction conditions are different.

In the multi-layer, gel-structured pressure-sensitive adhesive sheet of the present invention, the state of lamination of the respective gel bodies constituting the whole pressure-sensitive adhesive sheet for a living body, such as the pressure-sensitive adhesive layer and the support layer, is not particularly limited. In addition to the state where is completely laminated with exactly the same shape, the state where a specific layer is different in shape from other layers, the shape of the face and body parts on a specific gel body layer,
The gel body layer having a pattern conforming to the contour may be laminated.

The thickness of the layer of each gel body may be appropriately set according to the use condition of the pressure-sensitive adhesive sheet, but is preferably 0.05 mm or more from the viewpoint of ease of production. Regarding the thickness of the entire pressure-sensitive adhesive sheet, it may be uniform throughout or partially different in thickness.
It is preferably in the range of 1 to 3 mm. If the thickness of the entire pressure-sensitive adhesive sheet is less than 0.1 mm, the strength of the pressure-sensitive adhesive sheet may be reduced. On the other hand, if it exceeds 3 mm, the self-weight of the sheet becomes too large, and there is a possibility that an uncomfortable feeling may be caused when the sheet is attached to the skin. If the entire pressure-sensitive adhesive sheet is not thick, it is possible to partially increase the thickness of the sheet to about 6 mm.

[Adhesive Properties and the Like of Adhesive Layer and Support Layer] The adhesive sheet for a living body having a multilayer gel structure of the present invention includes an adhesive layer and a support layer. Among these, the pressure-sensitive adhesive layer constitutes one surface layer of the multilayer gel-structured pressure-sensitive adhesive sheet for living body of the present invention, and the support layer constitutes the other surface layer. The adhesive layer is a surface layer for attaching the adhesive sheet to the skin. Such an adhesive layer is formed of a gel body having a chemical property that does not easily peel off when attached to the skin and that can sufficiently adhere to the skin.

On the other hand, the support layer is a surface layer located on the side opposite to the skin surface when the adhesive sheet is attached to the skin.
Such a support layer is a gel body in which the degree of adhesion to the skin is made weaker than that of the adhesive layer, or the adhesion to the skin is removed, in order to smoothly perform the operation when attaching the adhesive sheet to the skin. It is formed. In the present invention, the degree of adhesion is measured by an inclined ball tacking device (inclination angle: 20 degrees) described in JIS Z 0237-1991 “Testing method of adhesive tape / adhesive sheet”.

According to the above-mentioned JIS, all areas where the degree of adhesion indicated by the ball number is larger than 32 (ie, when the degree of adhesion is extremely large) are expressed as "ball number 32". The degree of adhesion in the region cannot be properly evaluated. Therefore, in the present invention, in order to properly evaluate the degree of adhesion even in a region where the degree of adhesion is very large,
It was decided to use a ball having a larger nominal diameter than "1" in the ball specification (Appendix Table 1, second column) specified in JIS B 1501-1988. In this case, the ball number was set to 32 times the number of calls as in the case where the number of balls (the second column) was 1 or less. Even when the ball number exceeded 32, the degree of adhesion was measured in the same manner as described above.

In order to improve the operability of the multi-layered gel-structured pressure-sensitive adhesive sheet for living body of the present invention, that is, to smoothly perform the operation of attaching the pressure-sensitive adhesive sheet to the skin, the inclined ball tack test is used. The difference in the degree of adhesion between the adhesive layer and the support layer is preferably 1 or more, and more preferably 3 or more in ball number. The adhesive properties required for each of the adhesive layer and the support layer are set according to the purpose of use and the application site of the adhesive sheet, and are not particularly limited. However, in general, the ball number of the adhesive layer is preferably from 2 to 40, and more preferably from 3 to 30, when the main purpose is to apply to the face. Further, when it is intended to be applied to each part of the body other than the face, it is preferably 4 to 50, and 5 to 32.
Is more preferable. When the ball number of the pressure-sensitive adhesive layer is larger than the upper limit value shown in these ranges, after the pressure-sensitive adhesive sheet is attached to the skin, when the pressure-sensitive adhesive sheet is removed, pain or discomfort may be felt. In addition, when the value is below the lower limit, the adhesive sheet may lack adhesiveness when attached to the skin, and may be easily peeled off.

When the ball number on the pressure-sensitive adhesive layer side is 2, the result of the ball tack test on the support layer becomes smaller than 2, and no measured value can be obtained according to the above-mentioned JIS regulations. Therefore, in the present invention, a case where the measured value of the adhesion degree of the support layer is so small that the measured value of the adhesion degree of the support layer does not appear is defined as “the difference between the ball number of the adhesive layer and the support layer is 1 or more” in the above-mentioned JIS. .

In the present invention, the viscosity of the gel is controlled by, for example, adjusting the amount of the polymerizable unsaturated monomer relative to the total amount of the gel and the type and amount of the polymerization initiator. Conventionally known means such as controlling the degree of polymerization or adjusting the amount of the crosslinkable unsaturated monomer or crosslinkable factor relative to the total amount of the gel body may be used. That is,
Increasing the degree of polymerization or increasing the amount of the crosslinkable unsaturated monomer or crosslinkable factor can reduce the degree of adhesion of the obtained gel. In order to increase the degree of adhesion of the gel body, the reverse operation may be performed. Further, the degree of adhesion of the gel body can be increased by adding a tackifier.

In the multi-layered gel-structured pressure-sensitive adhesive sheet of the present invention, the transparency of the pressure-sensitive adhesive sheet is not impaired.
For the purpose of improving the tear strength of the pressure-sensitive adhesive sheet and the handleability of the movement of the skin surface when the pressure-sensitive adhesive sheet is attached to the skin, a woven or nonwoven fabric having a sufficiently large porosity, for example, a pressure-sensitive adhesive layer and It can be laminated on the interface with the support layer, the inside of each of the layers, the surface of any one of the layers, or the like.

The woven fabric or nonwoven fabric having a large aperture ratio is a material having a wide aperture ratio (transparency is maintained) such that a 10-point type can be read even through a woven fabric or nonwoven fabric. Say. The place where such a woven or nonwoven fabric is laminated may be inside the single gel layer of each gel layer constituting the pressure-sensitive adhesive sheet, or at the interface of different gel layers or the surface of the pressure-sensitive adhesive sheet. It is preferably inside the gel body constituting the body layer.

The multi-layered gel-structured pressure-sensitive adhesive sheet for living body of the present invention comprises one of the surface layers as the pressure-sensitive adhesive layer and the other as the support layer. Depending on the application (for example, a buffer layer or the like), one or two or more different layers (inner layers) having a different gel composition from these layers may be included. The multi-layered gel-structured pressure-sensitive adhesive sheet of the present invention has a structure in which each layer including the inner layer is integrally formed.

[Additives] In addition to a synthetic polymer having a network structure and a solvent containing at least water, each of the gels constituting the multi-layered gel-structured bioadhesive sheet of the present invention contains Various additives are blended according to the purpose of use. Such additives include, for example, medicinal ingredients for the purpose of treating beauty, facial treatment and skin, etc., as well as humectants,
Examples include a thickener, a fragrance, a coloring agent, a stabilizer, an antioxidant, an ultraviolet absorber, a tackifier, a pH adjuster, a chelating agent, a surfactant, a preservative, and an antibacterial agent.

The above-mentioned medicinal components are not particularly limited as long as they are conventionally used in pharmaceuticals, quasi-drugs, cosmetics, sanitary materials, miscellaneous goods, etc., and include, for example, ashitaba extract, avocado extract, Amacha extract, Altea extract, Arnica extract, Aloe extract, Apricot extract, Apricot kernel extract, Ginkgo extract, Fennel extract, Turmeric extract, Oolong tea extract, Age extract, Echinashi leaf extract, Ohgon extract, Obaaku extract, Ouren extract, Barley extract, St. John's wort extract, Spicewort extract, Dutch mustard extract, orange extract, seawater dried product, seaweed extract, hydrolyzed elastin, hydrolyzed wheat powder, hydrolyzed silk, chamomile extract, carrot extract, sagebrush extract, licorice extract, calcadae Vinegar, song extract, kiwi extract, cinchona, cucumber extract, guanosine,
Gardenia extract, Kumazasa extract, Clara extract, Walnut extract, Grapefruit extract, Clematis extract, Chlorella extract, Mulberry extract, Gentian extract,
Black tea extract, yeast extract, burdock extract, rice bran extract, rice germ oil, comfrey extract, collagen,
Cowberry extract, Saishin extract, Psychoextract, Saitai extract, Salvia extract, Sabonso extract, Sasa extract, Hawthorn extract, Sansho extract, Shiitake extract, Jio extract, Shikon extract, Perilla extract, Shinanoki extract, Shimotsukeiso extract, Peony extract, Shobu root extract , Birch extract, horsetail extract, vegetative extract, hawthorn extract,
Western elderberry extract, Achillea millefolium extract, Common mint extract, Sage extract, Genus mallow extract, Senkyu extract, Assembly extract, Soybean extract, Tissou extract, Thyme extract, Tea extract, Clove extract, Chigaya extract, Chimpanzee extract, Touki extract, Calendula extract, Tonin extract , Spruce extract, dokudami extract, tomato extract, natto extract, carrot extract, garlic extract, nobara extract, hibiscus extract, bakkumondou extract, parsley extract, honey, hamamelis extract, Parietaria extract, chickpea extract, bisabolol, loquat extract, coltsfoot extract , Fukinotou extract, kukuroyou extract, butcher bloom extract, grape extract, propolis, loofah extract, safflower Vinegar, peppermint extract, lime extract, button extract, hops extract, pine extract, horse chestnut extract, skunk cabbage extract, Sapindus extract, Melissa extract, peach, cornflower extract, eucalyptus extract, saxifrage extract, Yuzuekisu,
Yokuinin extract, mugwort extract, lavender extract,
Examples include apple extract, lettuce extract, lemon extract, astragalus extract, rose extract, rosemary extract, Roman chamomile extract, royal jelly extract and the like.

Also, biopolymers such as deoxyribonucleic acid, mucopolysaccharide, sodium hyaluronate, sodium chondroitin sulfate, collagen, elastin, chitin, chitosan, hydrolyzed eggshell membranes; amino acids, sodium lactate, urea, sodium pyrrolidonecarboxylate; Moisturizing components such as betaine, whey and trimethylglycine; oily components such as sphingolipids, ceramides, cholesterol, cholesterol derivatives, and phospholipids; Inflammatory agent; vitamins A, B2, B6, C, D, E, vitamins such as calcium pantothenate, biotin, nicotinamide, and vitamin C ester; allantoin, diisopropylamine dichloroacete Active ingredients such as tocophenol and 4-aminomethylcyclohexanecarboxylic acid; antioxidants such as tocophenol, carotenoid, flavonoid, tannin, lignan, saponin; cell activators such as α-hydroxy acid and β-hydroxy acid; γ- Blood circulation promoters such as oryzanol and vitamin E derivatives; wound healing agents such as retinol and retinol derivatives; whitening agents such as arbutin, kojic acid, placenta extract, sulfur, ellagic acid, linoleic acid, tranexamic acid and glutathione; cepharanthin and licorice extraction Products, pepper tincture, hinokitiol, garlic iodide extract, pyridoxine hydrochloride, dl-α-tocopherol acetate, dl-α-tocopherol acetate, nicotinic acid, nicotinic acid derivatives, calcium pantothenate, D-
Pantothenyl alcohol, acetyl pantothenyl ethyl ether, biotin, allantoin, isopropylmethylphenol, estradiol, ethinylesteradiol, capronium chloride, benzalkonium chloride, diphenhydramine hydrochloride, tacanal, camphor, salicylic acid, nonylate vanillylamide, nonanoyl vanillylamide, pyro Cuton olamine, glyceryl pentadecanoate,
1-menthol, mononitroguaiacol, resorcinol, γ-aminobutyric acid, benzethionium chloride, mexiletine hydrochloride, auxin, female sex hormone, cantaristinctin, cyclosporine, hydrocortisone, polyoxyethylene sorbitan monostearate, peppermint oil, analgesic, mental stability Agents, antihypertensives, antibiotics, antihistamines, antibacterials, plant-derived components, seaweed-derived components, and the like.

The compounding amount of the medicinal component cannot be specified unconditionally because the amount of the active component varies depending on the material.
And more preferably 0.05 to 10% by weight. Examples of the humectant include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, glycerin, diglycerin, sorbitol, malbitol, trehalose, raffinose, xylitol, mannitol, hyaluronic acid and salts thereof, polyethylene glycol, polyglycerin and the like. Glycols, polyhydric alcohols and polysaccharides. These can be used alone or in combination of two or more.

The moisturizing agent has the following effects in addition to providing a moisturizing effect to the skin to which the adhesive sheet is attached. That is, when the amount of water contained in one of the gel bodies constituting the pressure-sensitive adhesive sheet is considerably larger than that of the other gel bodies adjacent to the gel body, the gel body having a higher water content Water moves from one side to another adjacent gel body having a relatively small amount of water, and as a result, the latter gel body expands, and the whole adhesive sheet may be warped. Such a warpage can be prevented by adding a considerable amount of a humectant to the former gel having a large amount of water. The amount of the humectant to be blended in such a case cannot be specified unconditionally because it is related to the difference in the water retention capacity between adjacent different gel bodies and the water retention capacity of the humectant itself, but generally the amount of the humectant in the gel body having a large amount of water 0.1 to 8 with respect to the total amount of the gel body.
It is preferably 0% by weight, more preferably 1 to 30% by weight.

The thickener is preferably a relatively small amount, and the mixed liquid before gelation has a certain degree of viscosity, and examples thereof include water-soluble polymers such as polyethylene oxide and hydroxyethyl cellulose. The amount of the thickener is
It is preferably 0.01 to 20% by weight, more preferably 0.05 to 10% by weight, based on the total amount of the gel body.

The above-mentioned additives may be used, depending on the purpose and application of the multi-layered gel-structured pressure-sensitive adhesive sheet of the present invention, for each of the gels constituting the pressure-sensitive adhesive sheet. Alternatively, it is added to all gel bodies. For example,
In the case where the medicinal component is intended to be immediately and transdermally absorbed, the medicinal component may be added to the adhesive layer closest to the skin. In addition, in order to obtain a certain degree of delayed or sustained effect, rather than rapidly percutaneously absorb the medicinal ingredient, add an appropriate medicinal ingredient to the surface adhesive layer and add the medicinal ingredient to other gel bodies. What is necessary is just to add.

Each gel constituting the multi-layered gel-structured pressure-sensitive adhesive sheet for living body of the present invention may be composed of a type of synthetic polymer having a network structure, a type of solvent containing water, The composition and the like can be selected. For example,
When the adhesive sheet for a living body is stuck to the face or the like to exert a skin tightening effect, the ratio of water in the solvent constituting the adhesive layer should be 70% by weight or more of the gel body constituting the adhesive layer. The synthetic polymer having a network structure constituting the gel body may be a synthetic polymer mainly composed of a polymerizable unsaturated monomer having a carboxyl group such as (meth) acrylic acid or a salt thereof. Thereby, evaporation of water existing inside the pressure-sensitive adhesive sheet can be promoted, and the above-mentioned object can be achieved.

Conversely, when the evaporation of water is not preferred, the ratio of water in each gel body may be set to 20% by weight or less based on the gel body. Among the various additives to be added to the gel body, there are those which react with the functional groups of the synthetic polymer having a network structure constituting the gel body and impair the role of the original additive. When such an additive is used, a synthetic polymer having a network structure consisting of only functional groups that do not react with the additive may be used. For example, a cationic additive reacts with a synthetic polymer composed of a polymerizable unsaturated monomer having a carboxyl group such as anionic (meth) acrylic acid or a salt thereof, but reacts with acrylamide and N, N ′ −. Since it does not react with a synthetic polymer composed of a copolymer of a nonionic polymerizable unsaturated monomer and a crosslinkable unsaturated monomer such as methylenebisacrylamide, by using such a synthetic polymer, The additive can fulfill its original role.

[Production Method of Multilayer Gel Structure Biological Adhesive Sheet] Next, a method of producing the multilayer gel structure biological adhesive sheet of the present invention will be described. As described above, each gel body constituting the multi-layered gel-structured bioadhesive sheet of the present invention comprises, as described above, a synthetic polymer having a network structure constituting the gel body, (a) 1
A copolymer of one or more polymerizable unsaturated monomers and a crosslinkable unsaturated monomer, or (b) selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group in the side chain A hydrophilic synthetic polymer obtained by polymerizing one or more polymerizable unsaturated monomers having at least one functional group, a polyvalent metal ion compound, a polyvalent carboxylic acid,
It is preferably a crosslinked structure obtained by reacting with at least one crosslinking factor selected from the group consisting of polyhydric alcohols, polyfunctional epoxides and dialdehydes.

When the copolymer of the polymerizable unsaturated monomer and the crosslinkable unsaturated monomer (a) is used as a synthetic polymer having a network structure, a method for producing a gel is as follows. For example, there is a method in which a polymerizable unsaturated monomer, a crosslinkable unsaturated monomer, and a polymerization initiator are added to a solvent constituting a gel to carry out polymerization. For the polymerization, a system in which the polymerization is started by heating or light irradiation or by adding a polymerization initiator may be selected.

On the other hand, when the crosslinked structure formed by reacting the hydrophilic synthetic polymer of (b) with a crosslinkable factor is used as a synthetic polymer having a network structure, a method for producing a gel body includes: For example, there is a method in which a hydrophilic synthetic polymer polymerized in advance in the same manner as described above is dissolved, and a crosslinking reaction is performed by adding a crosslinking factor to the solution. The cross-linking reaction may be started by heating or may be started by adding a reaction initiator. Alternatively, a system in which a crosslinking reaction starts immediately upon addition of a crosslinking factor may be selected.

In the case where a gel is obtained by polymerizing the unsaturated monomer of the above (a), azobiscyanovaleric acid or An azo polymerization initiator such as azobisaminopropane dihydrochloride, or a reducing agent such as ferrous sulfate, dithionite, pyrosulfite and the like, hydrogen peroxide, t-butyl hydroperoxide, peroxodisulfate, etc. The polymerization can be carried out by adding a redox polymerization initiator consisting of These azo-based polymerization initiators and redox-based initiators may be used alone or as a mixture as necessary. When using a redox initiator,
A system in which polymerization is initiated only by adding without heating may be used. In the case of photopolymerization, a photoradical polymerization initiator such as acetophenone, benzoin ether, phosphorus, benzophenone, thioxanthone, and azo, and a photocation such as diazonium salt, diallyliodonium salt, and triarylsulfonium salt. Polymerization can be carried out by adding a polymerization initiator or the like.

The adhesive sheet for a living body having a multilayer gel structure according to the present invention is characterized in that gel bodies having different compositions depending on the purpose of use and application are laminated and formed integrally so as not to peel off each layer. For this reason, as a method of manufacturing the pressure-sensitive adhesive sheet of the present invention, after the gelation of one of the adjacent gel bodies is completed, the other gel body is brought into a state where gelation does not start or a stage where gelation is in progress. In this case, a method is adopted in which the layers are laminated in a state where the fluidity remains, and both layers are integrally formed when the gelation of the other gel body is terminated.

If adjacent gel bodies are laminated after both gellings have been completed, delamination may occur. In particular, delamination tends to occur when the pressure-sensitive adhesive sheet is expanded or contracted for application or peeled off from the skin after use. In addition, when adjacent gel bodies are stacked in a state where both gelation processes have not started, or when both gelation stages are in the middle and fluidity remains, gel bodies are stacked. There is a possibility that the interface between the gel bodies is lost, and in some cases, the two compounds before gelation are completely mixed, so that the respective gel bodies cannot be distinguished.

The term "end of gelation" in the present invention means that the composition before gelation has undergone a gelling reaction and has a shape-retaining property. In the present invention, the adjustment of the thickness of each gel body layer is performed by spreading using an extruder, a doctor blade, or the like, or by filling a container having a predetermined thickness. In the above-described manufacturing method, as a lamination method after at least one of the gel bodies constituting the pressure-sensitive adhesive sheet has finished gelling, the extruder or a doctor blade or the like is used on the gelated layer to leave One of the gel bodies is laminated in a state where the gelation does not start, or in a state where the progress of the gelation is in the middle and the fluidity remains, and the gelation of such a layer is terminated (if necessary) hand,
It is more preferable to adopt a method of integrally forming each gel body layer by repeating the above operation) from the viewpoint of simplifying the manufacturing equipment.

Further, one of the gel bodies constituting the adhesive sheet
In a state where the gelation does not start, or in the state where the progress of the gelation is in the middle and the fluidity remains, the container is filled and then the remaining gel which has already finished the gelation from above By laminating the body (or a layer in which the remaining plurality of gel bodies are integrated) and further terminating the gelation of the former gel-forming compound in which fluidity remains,
It is more preferable to adopt a method of integrally forming each layer from the viewpoint of facilitating the manufacturing process. In this case, if the shape of the container to be filled is formed according to the shape of the pressure-sensitive adhesive sheet for living body at the time of use, the in-line manufacturing process is facilitated and more preferable in the manufacturing process.

The bioadhesive sheet of the present invention has a plastic film of polyethylene, polypropylene, polyethylene terephthalate or the like as it is on at least the surface layer on the side of the adhesive layer, or has a surface such as a silicone resin or the like, until it is used. It is preferable for hygiene that the mold is applied as a release paper in a state of being applied. Further, from the viewpoint of preventing drying of the pressure-sensitive adhesive sheet and hygiene considerations, it is preferable that the above-mentioned release paper is also attached to the surface layer on the support layer side.

It is necessary to peel off the pasted release paper since it is not flexible enough to follow the movement of the skin surface because of its poor flexibility. If the release paper is used with the release paper adhered to the surface of the support layer, the release paper will be peeled off from the adhesive sheet during use, making it difficult to handle. The release paper may be used as an underlay or a surface material during the gel production process of the pressure-sensitive adhesive sheet, or may be affixed after the production of the pressure-sensitive adhesive sheet is completed.

The shape of the multi-layered gel-structured pressure-sensitive adhesive sheet for living body of the present invention is not particularly limited, but may be elliptical, circular, heart-shaped, semi-circular, semi-elliptical, square, rectangular, trapezoidal, triangular, or along the application site. The shape or a combination thereof may be used, and a shape that can be most appropriately stuck to a use site may be appropriately designed. In addition, if a convex portion or a concave portion is provided at the center portion or the peripheral portion of the adhesive sheet for the purpose of alignment or the like, or a notch or a hollow portion is provided according to the shape of the used portion, the handleability of the adhesive sheet is improved. Can be.

The application site of the pressure-sensitive adhesive sheet for living body of the present invention includes a face (lips, cheeks, eyes, upper and lower eyes, nose, forehead), arms, legs, chest, abdomen, back, Neck and the like. The shape, area, and thickness of the pressure-sensitive adhesive sheet for a living body, the pressure-sensitive adhesive properties of the pressure-sensitive adhesive layer, and the like may be appropriately adjusted according to the application site.
For example, when forming a pressure-sensitive adhesive sheet in which the application site is the entire face, as shown in FIG. 1, a portion corresponding to the position of the eyes and the mouth was cut out, and a cut was made in the portion corresponding to the position of the nose. It is preferable to make adjustments such as increasing the adhesive strength of the pressure-sensitive adhesive layer or reducing the thickness of the pressure-sensitive adhesive layer because the pressure-sensitive adhesive layer has a shape and a large bonding area.

[0065]

[Production of biological adhesive sheet]

Example 1 A biological adhesive sheet having a two-layer gel structure composed of an adhesive layer and a support layer was produced by the following production method. Table 1 shows the composition of the composition for forming the adhesive layer gel and the support layer gel.

[0066]

[Table 1]

The components excluding the crosslinking factor (synthetic aluminum silicate) among the formulations for forming the adhesive layer gel shown in Table 1 were mixed and kneaded at 50 ° C. for about 30 minutes to make uniform. Was further added and kneaded at 60 ° C. for about 10 minutes to obtain a uniform mixture. The composition for forming an adhesive layer gel thus obtained was uniformly spread on a 100 μm-thick polypropylene sheet to a thickness of 0.8 mm using a doctor blade. This was left at room temperature for about 2 hours to terminate the gelation, thereby forming an adhesive layer gel.

The composition for forming a support layer gel shown in Table 1 was uniformly spread on the above-mentioned adhesive layer gel to a thickness of 0.5 mm in the same manner as in the above-mentioned adhesive layer gel. The gelation was terminated by allowing to stand for 2 hours to form a support layer gel. Further, on this support layer gel, a thickness of 50
A polypropylene sheet of μm was placed thereon and punched into the shape shown in FIG. 1 (length x = 180 mm, width y = 220 mm) to obtain a desired final product.

Example 2 An adhesive sheet for a living body having a two-layer gel structure comprising an adhesive layer and a support layer was produced by the following production method. Table 2 shows the composition of the composition for forming the adhesive layer gel and the support layer gel.

[0070]

[Table 2]

The polymerization initiator (4% aqueous solution of ammonium persulfate and 2%
% Potassium pyrosulfite aqueous solution), dissolved and mixed with purified water and glycerin (humectant) as a solvent, and then the polymerization initiator was added and stirred well to obtain a support layer gel-forming composition. . Next, a spacer having a thickness of 0.4 mm is placed on a polyethylene terephthalate sheet (thickness: 50 μm) having a surface coated with a silicone resin (a release agent), and the support layer gel is formed in an area surrounded by the spacer. The formulation was poured. Further, the surface of the compound is coated on a polyethylene terephthalate sheet (thickness: 100 μm) coated with a silicone resin (release agent).
, And the mixture was heated at 70 ° C. for 5 minutes to perform polymerization, thereby terminating the gelation and forming a support layer gel.

A 100 μm-thick polyethylene terephthalate sheet was peeled off from the support layer gel thus obtained, and a spacer having a thickness of 0.7 mm was provided around the polyethylene terephthalate sheet. The adhesive layer gel-forming composition shown in Table 2 was poured in the same manner as in the gel formation. In addition, silicone resin (release agent) on the surface
Was covered with a polyethylene terephthalate sheet (thickness: 38 μm) and irradiated with ultraviolet rays having an intensity of 50 mW / cm ² for 60 seconds to perform polymerization, thereby terminating the gelation and forming an adhesive layer gel.

The obtained gel sheet was punched into the same shape as in Example 1 to obtain a desired final product. Example 3 An adhesive sheet for living body having a two-layer gel structure composed of an adhesive layer and a support layer was produced by the following production method. Table 3 shows the composition of the composition for forming the adhesive layer gel and the support layer gel.

[0074]

[Table 3]

The components excluding the polymerization initiator (trade name “Irgacure 184”, manufactured by Ciba-Geigy Co., Ltd.) in the gel composition for forming the support layer shown in Table 3 were dissolved and mixed with purified water and glycerin (humectant) as solvents. After that, the polymerization initiator was added, and the mixture was sufficiently stirred to obtain a support layer gel-forming composition. Next, a spacer having a thickness of 0.5 mm is provided on a polypropylene sheet (thickness: 100 μm) having a surface coated with a silicone resin (release agent), and the support layer gel is formed in a range surrounded by the spacer. After pouring the formulation, a woven fabric of 15 denier nylon tulle was immersed in the formulation. Further, the surface of the gel composition for forming a support layer containing the woven fabric was covered with a polyethylene terephthalate sheet (thickness: 38 μm) coated with a silicone resin (release agent) on the surface, and the strength was 50 mW / cm.
Irradiation of ultraviolet light of No. ² was carried out for 60 seconds to carry out polymerization to terminate gelation.

Next, the components excluding the crosslinking factor (magnesium aluminate metasilicate) among the compounds for forming the adhesive layer gel shown in Table 3 were mixed and kneaded at 50 ° C. for about 30 minutes to obtain a uniform mixture. , The crosslinking factor is added, and
The mixture was kneaded at a temperature of about 10 minutes for homogenization. The thus obtained composition for forming an adhesive layer gel is poured into a polypropylene container (depth: 1 mm) molded in a size smaller than the shape shown in FIG. 1 (about 2 mm), and the container is filled with a doctor blade. Were filled evenly so that no gap was formed.

Immediately after the filling of the composition for forming an adhesive layer gel, the gel of the support layer after gelation was overlaid on a container filled with the composition. At this time, the polypropylene sheet (thickness: 100 μm) used as an underlay during the production of the support layer gel was peeled off, and the support layer gel and the adhesive layer were stacked on top of each other with the surface of the support layer gel exposed facing downward. The formulation for gel formation was crimped.

Further, a container filled with the composition for forming an adhesive layer gel, a support layer gel, and a polyethylene terephthalate sheet (thickness: 38) adhered to the support layer gel.
.mu.m) were punched out in accordance with a shape slightly larger than the shape of the container (the shape shown in FIG. 1 as in Example 1). Thereafter, the gelation of the adhesive layer gel-forming composition in the container was completed at room temperature for about 2 hours to obtain a desired final product.

Example 4 An adhesive sheet for living body having a two-layer gel structure comprising an adhesive layer and a support layer was produced by the following production method. Table 4 shows the compositions of the adhesive layer gel and the support layer gel forming composition.

[0080]

[Table 4]

A gel for a support layer was prepared in the same manner as in Example 2 except that the formulation for forming a support layer gel shown in Table 4 was used. Next, a thickness of 100 μm was obtained from the obtained support layer gel.
The polyethylene terephthalate sheet was peeled off, a spacer having a thickness of 0.7 mm was set around the polyethylene terephthalate sheet, and the composition for forming an adhesive layer gel shown in Table 4 was poured. Formed.

The gel sheet thus obtained was punched into the same shape as in Example 1 to obtain a desired final product. Comparative Example 1 A biological adhesive sheet having a two-layer gel structure composed of an adhesive layer and a support layer was produced by the following production method. Table 5 shows the compositions of the composition for forming the adhesive layer gel and the support layer gel. The composition for forming the adhesive layer gel is the same as that used in Example 1.

[0083]

[Table 5]

An adhesive layer gel was formed in the same manner as in Example 1 except that the formulation for forming an adhesive layer gel shown in Table 5 was used. After mixing components other than the crosslinking factor (potassium aluminum sulfate) in the support layer gel forming composition shown in Table 5, the mixture was heated to 30 ° C. to dissolve the gelatin, and then the crosslinking factor was added. Kneaded for 5 minutes. The support layer gel-forming composition thus obtained was applied to the surface of the gel after completion of gelation with a doctor blade to a thickness of 0.5%.
mm, and left standing at room temperature for about 2 hours to terminate the gelation to form a support layer gel.

Further, the support layer gel was coated on the gel with a thickness of 50 μm.
m was placed on the polypropylene sheet and punched into the same shape as in Example 1 to obtain a desired final product. Comparative Example 2 A composition for forming an adhesive layer gel having the same composition as that used in Example 1 was uniformly spread to a thickness of 0.8 mm by the same method as in Example 1, and immediately thereafter, a support was formed on the surface thereof. A nonwoven fabric made of polypropylene having a basis weight of 100 g / m ² was pressed and left at room temperature for about 2 hours to complete gelation.

Next, this was punched out in the same shape as in Example 1 to obtain a biological adhesive sheet as a final product. Comparative Example 3 A composition for forming an adhesive layer gel having the same composition as that used in Example 1 was uniformly spread to a thickness of 0.8 mm by the same method as in Example 1, and immediately thereafter, a support was provided on the surface thereof. The gelation was terminated by pressing an ethylene-vinyl acetate copolymer sheet (100 μm thick) as above and leaving it at room temperature for about 2 hours.

Next, this was punched out into the same shape as in Example 1 to obtain an adhesive sheet for living body as a final product. Comparative Example 4 A gel composition for forming an adhesive layer having the same composition as that used in Example 1 was uniformly spread to a thickness of 0.8 mm by the same method as in Example 1, and then left at room temperature for about 2 hours. The gelation was thereby terminated. The upper surface of the adhesive layer gel thus obtained was covered with a polyethylene terephthalate sheet (thickness: 100 μm) coated with a silicone resin (release agent) on the surface, and punched into the same shape as in Example 1.

Next, the plastic film covering both surfaces of the adhesive layer was peeled off to obtain a single-layer gel-structured biological adhesive sheet. [Performance Test] Various tests were performed to evaluate the performance of the pressure-sensitive adhesive sheets obtained in the above Examples and Comparative Examples.

(Evaluation of Adhesiveness) First, the adhesiveness of the adhesive layer gel and the support layer gel in each adhesive sheet was measured according to JIS.
It was measured according to the method described in Z 0237-1991 “Testing method for pressure-sensitive adhesive tape / pressure-sensitive adhesive sheet 12. Tilted ball tack”. The inclination angle at the time of measurement was set to 20 degrees. However, the ball to be used is JISB
Call of the ball prescribed in 1501-1988 (column 2)
By using a material larger than 1 in the above, it was made to correspond to a gel sheet having high adhesiveness. Table 6 shows the measurement results.

[0090]

[Table 6]

(Evaluation of Sensory Characteristics) (1) Transparency Each of the pressure-sensitive adhesive sheets obtained in the above Examples and Comparative Examples was placed on a white paper, and 10-point characters (Mincho style) printed with black ink on the paper were used. Read). The transparency was evaluated as ○ when the characters on the paper could be read, and as × when the characters could not be read.

(2) Operability The operability of the pressure-sensitive adhesive sheet was evaluated after attaching to the face so that the surface layer of the pressure-sensitive adhesive layer was in contact with the skin. That is, when the pressure-sensitive adhesive sheet was stuck to the face, it did not cling to the finger at all, and could be easily pasted as 5, and if it could not be stuck at all to the finger, as 0,
The determination was made in six stages from 0 to 5. In Examples and Comparative Example 1, the plastic sheet stuck to the support layer was peeled off at the time of use and then stuck to the face.

(3) Followability In the case where the adhesive sheet adhered in the same manner as in the evaluation of the “operability” in the above (2) expands and contracts completely following the movement of the face, it is set to 5 0 if no follow-up is seen
The evaluation was made in six stages from 0 to 5. (4) Feeling of adhesion In the case where the pressure-sensitive adhesive sheet adhered in the same manner as in the evaluation of the “operability” of the above (2) adheres along the face surface, it is set to 5,
In the case where wrinkles were formed in each part of the adhesive sheet and a large number of floating occurred, it was judged as 0 and judged in 6 stages from 0 to 5.

(5) Feeling at the time of peeling When peeling the adhered adhesive sheet from the face in the same manner as in the evaluation of “operability” in (2) above, the case where no discomfort was felt on the skin was set to 5, In the case of feeling unpleasant or unpleasant, it was judged as 0 and judged in 6 steps from 0 to 5. (6) Cool sensation A cooling sensation was felt when attaching the adhesive sheet,
0 to 5) when the cooling sensation was sufficiently maintained for 5 minutes, and 0 when the cooling sensation was not felt at the time of application, and 0 to 5
It was judged at the stage.

(7) Delamination between layers When each pressure-sensitive adhesive sheet is used and when it is peeled off from the face after use, a case where no peeling occurs between the laminated layers is indicated by “○”.
The case where peeling occurred was evaluated as x. The result of the above evaluation was the average of the evaluations by 10 specialized panelists. Above (2) ~
In the evaluation of (6), if the evaluation result (average value) is 4 or more, it is determined that the evaluation is good for the item.

Table 7 shows the evaluation items.

[0097]

[Table 7]

From the results shown in Table 7, Comparative Examples 2 and 3
Since the adhesive sheet uses an existing plastic sheet or nonwoven fabric instead of a gel as a support, it may have serious drawbacks in terms of delamination, opacity, or the ability to follow the movement of the skin. understood. Further, it was found that the single-layer gel structure pressure-sensitive adhesive sheet obtained in Comparative Example 4 had a serious drawback in operability. In addition, the pressure-sensitive adhesive sheet of Example 4 had an extremely good feeling of adhesion to the skin, but the evaluation of the feeling when peeled from the face was slightly low because the pressure-sensitive adhesive layer had too high a pressure-sensitive adhesive property. However, the degree of tackiness in Example 4 was such that there was no problem when applied to skin other than the face.

(Heat Stability Test) The pressure-sensitive adhesive sheets obtained in Examples and Comparative Example 1 were placed in an aluminum bag with a plastic sheet covering the pressure-sensitive adhesive layer and the support layer attached thereto, and sealed. Stored at 60 ° C. for months. After a lapse of one month, the adhesive sheet was taken out of the aluminum bag, and the appearance was inspected to determine whether the shape shown in FIG. 1 was maintained and whether liquid dripping had occurred.

Table 8 shows the test results. In addition, when the shape of the adhesive sheet was held, it was evaluated as ○, and when it was not held, it was evaluated as ×.

[0101]

[Table 8]

From the results shown in Table 8, it was found that the adhesive sheet for living body with a two-layer gel structure of Comparative Example 1 had no thermal stability because gelatin gel was used for the support layer. (Rust test) After exposing the pressure-sensitive adhesive sheets obtained in Examples and Comparative Example 1 to the outside for one week in a state where the plastic sheet covering the pressure-sensitive adhesive layer and the support layer was peeled off, the temperature was set to 38 ° C. It was left in a petri dish for 2 weeks at a humidity of 40 to 80%. After standing, it was inspected whether or not decay had occurred in the adhesive layer or the support layer.

Table 9 shows the test results. In addition, the case where rot did not occur was evaluated as O, and the case where rot occurred was evaluated as X.

[0104]

[Table 9]

From the results in Table 9, it can be seen that in the double-layered gel-structured pressure-sensitive adhesive sheet for living body of Comparative Example 1, since gelatin gel was used for the support layer, spoilage occurred even though an antiseptic was added. I understood.

[0106]

As described in detail above, according to the present invention,
Each layer adopts a multilayer gel structure consisting of a synthetic polymer gel body, so the entire adhesive sheet is transparent, excellent in operability, feeling of close contact or following the movement of the skin, and excellent in storage durability Thus, a multi-layer gel-structured pressure-sensitive adhesive sheet for living body can be obtained.

Such a pressure-sensitive adhesive sheet for a living body is suitably used in the fields of pharmaceuticals, quasi-drugs, cosmetics, sanitary materials, sundries, and the like.

[Brief description of the drawings]

FIG. 1 is a front view showing one embodiment of a multi-layered gel structure living body pressure-sensitive adhesive sheet according to the present invention.

[Explanation of symbols]

 1 Multilayer gel structure bioadhesive sheet

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasushi Yasushi 7-1-33, Oanji, Nara City, Nara Prefecture (72) Inventor Kozo Sakai 8-1-1407, Hakuhoji-cho, Nara City, Nara Prefecture (72) Inventor Akihiro Kuroda, Kanagawa 5-28, Kotobukicho, Odawara-shi, Kanebo Cosmetics Research Laboratory (72) Inventor Saori Ishihata 5-28, Kotobukicho, Odawara-shi, Kanagawa Kanebo Cosmetics Research Laboratory F-term (reference) 4C076 AA77 BB31 CC03 CC24 DD27 DD29 DD30 DD38 DD39 DD40 DD42 DD60 EE03 EE09 EE11 EE13 EE16 EE24 EE27 EE47 EE48 FF35 FF36 FF39 FF70 4C083 AB052 AB352 AB372 AB412 AC102 AC122 AC252 AC432 AC851 AD071AD07 AD071 AD071 AK21A AK21K AK25A AK25K AK26A AK26K AR00A AR00B BA02 BA03 BA07 BA10B BA10C DG15C GB66 JK07 JL00 JL13A JM01B JM10A JN01 4J002 BG011 BG 131 BJ001 DE146 DJ036 EC046 EF066 EF116 EP026 FD146 GB00 GF00 GJ00 HA04 4J004 AA06 AA10 AB01 CA03 CC02 CC08 DA02 DA03 DA04 DB02 FA09

Claims (8)

[Claims] 1. An adhesive layer comprising a gel of a synthetic polymer having at least water as a solvent and having a network structure, and having a gel composition different from each other, and a support layer, wherein the adhesive layer and the support layer are in a thickness direction. An adhesive sheet for a living body having a multilayer gel structure, wherein the adhesive sheet is laminated on a substrate. 2. The degree of adhesion between an adhesive layer and a support layer is determined according to JIS.
Z 0237-1991 “Testing method of pressure-sensitive adhesive tape / pressure-sensitive adhesive sheet”
2. The pressure-sensitive adhesive sheet according to claim 1, wherein the difference between the ball numbers of the two layers is 1 or more, and the ball number of the pressure-sensitive adhesive layer is in the range of 2 to 50, when measured in degrees. 3. The pressure-sensitive adhesive sheet according to claim 1, which has a transparent or translucent appearance. 4. A synthetic polymer having a network structure constituting the gel body, comprising: (a) a copolymer of one or more polymerizable unsaturated monomers and a crosslinkable unsaturated monomer; Or (b) a hydroxyl group on the side chain,
A hydrophilic synthetic polymer obtained by polymerizing one or more polymerizable unsaturated monomers having at least one functional group selected from the group consisting of a carboxyl group, an amide group and an amino group; A crosslinked structure obtained by reacting at least one type of crosslinking factor selected from the group consisting of a polyvalent metal ion compound, a polyvalent carboxylic acid, a polyhydric alcohol, a polyfunctional epoxide and a dialdehyde. 4. The pressure-sensitive adhesive sheet for a living body having a multilayer gel structure according to any one of 1 to 3. 5. The polymerizable unsaturated monomer comprises (meth) acrylamide and a derivative thereof, vinylpyrrolidone, (meth)
The pressure-sensitive adhesive sheet according to claim 4, which is at least one selected from the group consisting of acrylic acid and a salt thereof. 6. A woven or non-woven fabric having a sufficiently large aperture ratio is laminated on the inside or the surface of the pressure-sensitive adhesive sheet.
6. The pressure-sensitive adhesive sheet for a living body having a multilayer gel structure according to any one of items 5 to 5. 7. A cosmetic product formed from the multi-layer gel structure bioadhesive sheet according to claim 1. 8. A quasi-drug, which is formed from the multi-layer gel structure bioadhesive sheet according to claim 1. Description: