JP2009108006A - Method for producing gel sheet, gel sheet and sheet-like cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a gel sheet, which efficiently produces a gel sheet having high syneresis. <P>SOLUTION: The method for producing a gel sheet that comprises a liquid-permeable substrate and hydrogel layers formed on both sides of the substrate comprises (a) a process for adjusting a hydrogel-forming mixed liquid having a gelation temperature of 10-60°C and applying the mixed liquid to the liquid-permeable substrate or (b) a process for casting a hydrogel-forming mixed liquid having a gelation temperature of 10-60°C, which is adjusted to a temperature to the gelation temperature or above, into a molding flask, inserting the liquid-permeable substrate in the molding flask and impregnating the substrate with the hydrogel-forming mixed liquid and a process for gelling the hydrogel-forming mixed liquid in an atmosphere of 0°C to the gelation temperature to form a hydrogel layer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a gel sheet used in the fields of pharmaceuticals, quasi drugs, cosmetics, hygiene materials, sundries, etc., a method for producing the same, and a sheet-like cosmetic using the gel sheet.

  Conventionally, gel sheets have been used for packs and patches used for beauty, facial treatment and skin treatment, carriers for active ingredients such as skin permeation components and anti-inflammatory analgesic components, wound protection and drug immobilization, etc. It is used for living body adhesive tapes, wound dressings and the like. These gel sheets exhibit functions such as increasing the moisture content (water retention) of the skin surface, controlling the temperature of the skin, and supplying the active ingredients in the gel sheet to the skin by sticking to the skin. be able to. In particular, when the physiology of the skin is increased by improving the temperature and water content by aging the gel sheet in close contact with the skin, the increase of the physiological action causes the active ingredient in the gel sheet to be applied to the skin. It is also possible to increase the penetration of.

As a gel sheet having such an action, it is known that a polysaccharide such as collagen, chitin, chitosan, alginic acid, or cellulose is used as a constituent component as a gel base material in consideration of use in a living body (for example, , See Patent Document 1).
In addition, for the purpose of improving the moisture retention of the skin, a technique for promoting a bleeding effect from a gel base material with a specific alkylene oxide derivative (see, for example, Patent Document 2), or a solution leaching effect by adding polyethylene glycol or an electrolyte A technique (for example, see Patent Document 3) that promotes the above is known. Furthermore, a technique for efficiently producing a hydrogel having an exudation effect by a crosslinking reaction between an anionic synthetic polymer compound and a polyvalent cation compound is also known (see, for example, Patent Document 4).
However, in the above-described technique, the separation property such as effectively supplying the components retained in the hydrogel to the adjacent adherend is still insufficient, and for example, sodium polyacrylate is used. When producing a gel sheet by using it, there has been a problem that the progress of the crosslinking reaction is slow and the production efficiency is low.
Japanese Patent Laid-Open No. 3-81213 JP 2005-225837 A JP 2003-183147 A International Publication No. 2002/032405 Pamphlet

  In view of the above circumstances, an object of the present invention is to provide a gel sheet production method capable of efficiently producing a gel sheet that can have high release properties, a gel sheet obtained by the production method, and a sheet form using the gel sheet. It is to provide cosmetics.

The present invention relates to a method for producing a gel sheet comprising a liquid-permeable support and hydrogel layers formed on both sides of the support, and the liquid penetration is achieved by using the following method. This is a method for efficiently producing a gel sheet in which a hydrogel layer enters a porous support and the liquid-permeable support and the hydrogel layers on both sides of the support are integrated.
That is, the manufacturing method of the 1st gel sheet of this invention is comprised from the liquid-permeable support body and the hydrogel layer formed in both surfaces of this support body,
A step of coating a hydrogel-forming liquid mixture having a gelation temperature of 10 ° C. to 60 ° C. on a liquid-permeable support after adjusting the temperature to be equal to or higher than the gelation temperature;
Forming a hydrogel layer by gelling the hydrogel-forming compounded liquid under an atmosphere of 0 ° C. to gelation temperature;
It is characterized by having.

Further, the second method for producing a gel sheet of the present invention comprises a liquid-permeable support and hydrogel layers formed on both sides of the support,
A hydrogel-forming liquid mixture having a gelling temperature of 10 ° C. to 60 ° C., which has been adjusted to a temperature equal to or higher than the gelling temperature, is cast into a mold, and then liquid permeable into the mold. Inserting a support and impregnating the support with the hydrogel-forming compound liquid; and
Forming a hydrogel layer by gelling the hydrogel-forming compounded liquid under an atmosphere of 0 ° C. to gelation temperature;
It is characterized by having.

In the manufacturing method of the gel sheet of this invention, it is preferable that it is the following aspects (1)-(8). Two or more aspects of the following (1) to (8) may be combined.
(1) The step of forming a hydrogel layer is a step of holding the hydrogel layer in an atmosphere of 0 ° C. to gelation temperature for 1 minute to 120 minutes to gel the hydrogel-forming liquid mixture to form a hydrogel layer. Some aspects.
(2) The aspect whose viscosity at 60 degreeC of the compounding liquid for hydrogel formation is 100 mPa * s-1,000,000 mPa * s.
(3) A mode in which the liquid-permeable support is a porous film, a woven fabric, or a non-woven fabric.
(4) The aspect in which the liquid mixture for hydrogel formation contains collagen or a collagen degradation product.
(5) The aspect in which the liquid mixture for hydrogel formation contains polysaccharide.
(6) The aspect in which the liquid mixture for hydrogel formation contains O / W type | mold emulsion.
(7) The aspect in which the compounding liquid for hydrogel formation contains polyether.
(8) A mode in which the thickness is 0.4 mm to 2 mm.

The gel sheet of the present invention is obtained by the method for producing the first or second gel sheet of the present invention.
Furthermore, the sheet cosmetic of the present invention uses the gel sheet of the present invention.

  In the present invention, the term “gel sheet” is used for packs and patches used for beauty treatment, facial treatment, skin treatment, etc., carriers for active ingredients such as skin permeation ingredients and anti-inflammatory analgesic ingredients, wound protection and drug immobilization, etc. It includes adhesive tapes for living bodies, wound dressings, etc., and is used in direct contact with the adherend for the purpose of retaining moisture and active ingredients, and further infiltrating the ingredients into the skin. A sheet. This gel sheet is useful as a cosmetic such as a pack that gives moisture or an active ingredient to the skin by contacting (attaching) the skin.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the gel sheet which can manufacture efficiently the gel sheet which can have high release property, the gel sheet obtained by this manufacturing method, and the sheet-like cosmetics using this gel sheet are provided. be able to.

Hereinafter, the present invention will be described in detail.
[Method for producing gel sheet]
The method for producing the gel sheet of the present invention includes the following two aspects.
That is, the first method for producing a gel sheet of the present invention (hereinafter referred to as “gel sheet production method (1)”) includes a liquid-permeable support and hydrogel layers formed on both sides of the support. The hydrogel-forming liquid mixture having a gelation temperature of 10 ° C. to 60 ° C. is adjusted to a temperature equal to or higher than the gelation temperature, and then coated on a liquid-permeable support (hereinafter referred to as “the gel”). And a process of forming a hydrogel layer by gelling the hydrogel-forming compounded liquid in an atmosphere of 0 ° C. to gelation temperature (hereinafter referred to as “gelation process”). And the like.).

The second gel sheet manufacturing method of the present invention (hereinafter referred to as “gel sheet manufacturing method (2)”) includes a liquid-permeable support and hydrogel layers formed on both surfaces of the support. A hydrogel-forming liquid mixture having a gelation temperature of 10 ° C. to 60 ° C. adjusted to a temperature equal to or higher than the gelation temperature is cast into a mold, and then into the mold A step of inserting a liquid-permeable support and impregnating the support with the hydrogel-forming compound liquid (hereinafter referred to as “impregnation step”), and an atmosphere of 0 ° C. to gelation temperature And a step of forming a hydrogel layer by gelling the gel-forming liquid mixture (hereinafter referred to as “gelation step”).
Hereinafter, each process of the manufacturing method (1) and (2) of the gel sheet of this invention is demonstrated.

[Coating process]
In the method (1) for producing a gel sheet of the present invention, first, a hydrogel-forming liquid mixture having a gelation temperature of 10 ° C to 60 ° C is adjusted to a temperature equal to or higher than the gelation temperature, and then a liquid-permeable support. Having a step of coating on top.
Here, the “gelling temperature” is a temperature at which gelation starts when the sol-form hydrogel-forming compounded liquid is cooled at a high temperature. The gelation temperature can be measured with a viscometer as the temperature at which the viscosity suddenly increases, or as the temperature at which tan δ = 1 by dynamic viscoelasticity measurement using a rheometer.
In this invention, it is required that the gelling temperature of the hydrogel-forming liquid mixture is 10 to 60 ° C, more preferably 15 to 55 ° C, and particularly preferably 20 to 50 ° C. By having the gelation temperature within this range, the hydrogel-forming compound liquid not only diffuses and penetrates into the liquid-permeable support, but also stabilizes the physical properties of the hydrogel layer after molding, Manufacturing efficiency is increased. Here, in order to bring the gelation temperature of the hydrogel-forming liquid mixture into the above range, a method of appropriately adjusting the types and content ratios of the components constituting the hydrogel-forming liquid mixture is used.

In this invention, it is preferable that the viscosity of the liquid mixture for hydrogel formation at 60 degreeC is 100 mPa * s-1,000,000 mPa * s. When the viscosity at 60 ° C. is in this range, the gelation proceeds while the hydrogel-forming liquid mixture penetrates into the support, and interface adhesion can be imparted. As a viscosity at 60 degreeC of the compounding liquid for hydrogel formation, 120 mPa * s-500,000 mPa * s are more preferable, and 150 mPa * s-100,000 mPa * s are especially preferable. Here, in order to bring the viscosity of the hydrogel-forming liquid mixture into the above range, a method of appropriately adjusting the types and content ratios of the components constituting the hydrogel-forming liquid mixture is used.
In order to integrate the support and the hydrogel, a hydrogel-forming liquid mixture having a viscosity of 100 mPa · s to 1,000,000 mPa · s heated to 60 ° C. in the coating step. In the gelation step to be described later, it is particularly preferable to stand for 1 minute to 120 minutes in an atmosphere of 0 to 30 ° C.

  In the coating step in the present invention, the hydrogel-forming liquid mixture is adjusted to a temperature equal to or higher than its gelation temperature. This temperature is determined by the penetration of the hydrogel-forming liquid mixture into the support and in a short time. 60 to 100 degreeC is preferable from the point of hardening, and it is especially preferable that it is 60 to 85 degreeC.

The liquid-permeable support suitably used in the present invention is not particularly limited as long as the hydrogel-forming compounding liquid to be used can penetrate, and is woven, non-woven, porous film, gel, sponge-like. Examples include structures and paper. There are no particular restrictions on the materials constituting these materials, and natural fibers and regenerated fibers such as cellulose, rayon, fibroin, chitosan, carrageenan, gellan gum, nylon, polyester, polyethylene, polypropylene, acrylic resin, polylactic acid, polyurethane, etc. Synthetic fibers are used.
Of these, woven fabrics, nonwoven fabrics, and porous films are preferred, and nylon, polyester, or polyurethane woven fabrics or nonwoven fabrics are particularly preferred from the viewpoint of affinity with the hydrogel layer.

Still woven fabric of the present invention or a nonwoven fabric, is preferably basis weight is ^{3g / m 2 ~100g / m 2} , more preferably ^{5g / m 2 ~70g / m 2} , 5g / m 2 ~ Particularly preferred is 50 g / m ² . If the basis weight is less than 3 g / m ² , the strength may be insufficient and handling may be difficult, and if the basis weight is greater than 100 g / m ² , the flexibility of the hydrogel layer is reduced. Adhesion when applied to the body may be reduced.

A known coating method is applied to the coating step in the present invention, for example, blade coater, air knife, roll coater, brush coater, bar coater, lip coater, gravure coater, curtain coater, slot die coater, slide coater, etc. A coating method using is used.
As a coating method, the hydrogel-forming compounded liquid may be uniformly coated on a liquid-permeable support with a blade coater, and the penetration into the support may be enhanced by pressing after coating. Moreover, you may apply | coat the liquid mixture for hydrogel formation further on the liquid-permeable support body which has a hydrogel layer beforehand on the back surface. Furthermore, you may apply | coat the liquid mixture for hydrogel formation to the clearance gap between a cover film and a liquid-permeable support body using a roll coater.

[Impregnation process]
In the method (2) for producing a gel sheet of the present invention, first, a hydrogel-forming liquid mixture having a gelation temperature of 10 ° C. to 60 ° C. adjusted to a temperature equal to or higher than the gelation temperature is cast into a mold. Then, a step of inserting a liquid-permeable support into the mold and impregnating the support with the hydrogel-forming liquid mixture is provided.
In addition, about the details of the liquid mixture for hydrogel formation which is used in this impregnation step, the gelling temperature is 10 ° C. to 60 ° C. and its adjustment temperature, and the liquid-permeable support, This is the same as that described in the coating step of the manufacturing method (1).

In the impregnation step in the present invention, the hydrogel-forming compound liquid is cast into a mold, but the mold used here may be appropriately determined according to the shape according to the intended use, For example, a square, a rectangle, a trapezoid, a circle, an ellipse, a semicircle, a semi-ellipse, and the like can be mentioned, but there is no particular limitation. Moreover, the shape which has a recessed part and a convex part in the thickness direction may be sufficient.
Moreover, what is necessary is just to determine suitably about the quantity which casts the liquid mixture for hydrogel formation in a formwork according to the preferable thickness of a gel sheet which is mentioned later.

  By inserting a liquid-permeable support into the mold in which the hydrogel-forming liquid mixture is cast, the hydrogel-forming liquid mixture penetrates and diffuses into the support body, and is spread on both sides of the support body. It is possible to form a state in which the hydrogel-forming liquid mixture is arranged. As a result, when a hydrogel layer is formed in the below-described gelation step, a gel sheet in which the support and the hydrogel layer are integrated can be formed.

[Gelling process]
In the gel sheet manufacturing method (1) of the present invention, after the coating step, and in the gel sheet manufacturing method (2) of the present invention, after the impregnation step, a hydrogel-forming liquid mixture in an atmosphere of 0 ° C. to gelation temperature. And forming a hydrogel layer.
The temperature atmosphere in the gelation step is preferably in the range of 0 ° C. to the gelation temperature of the used hydrogel-forming liquid mixture, but 4 ° C. to 50 ° C. from the viewpoint of penetration of the hydrogel layer into the support. Is preferable, and 10 to 40 ° C is more preferable.

  In addition, the retention time in the gelation step may be appropriately determined depending on the type of the hydrogel-forming compounding solution, and the shorter the better the production efficiency. Specifically, it is preferably 1 minute to 120 minutes, more preferably 5 minutes to 110 minutes, and particularly preferably 15 minutes to 100 minutes.

The gel sheet of this invention is obtained by passing through each process as mentioned above.
According to the first method for producing a gel sheet of the present invention, a large number of gel sheets are efficiently produced by using a support wound in the form of a tape and continuously coating the support. can do.
Moreover, according to the manufacturing method of the 2nd gel sheet of this invention, the gel sheet of the various shape according to a use can be efficiently manufactured by using the formwork according to a various use.

The gel sheet of the present invention obtained by the production method of the present invention has a form in which a hydrogel layer is formed on both sides of a support, and the support and the hydrogel layer are integrated, and its shape stability Therefore, it has high handleability. Moreover, by having a hydrogel layer on both surfaces of the support, it is possible to make contact with the adherend on both surfaces of the gel sheet.
Such gel sheets are useful for electrode pads for massage machines, medical adhesive tapes, cooling sheets, wound dressings, and cosmetics such as packs.

  The thickness of the gel sheet of the present invention may be determined according to its use, but is generally preferably 0.4 mm to 2 mm, and preferably 0.5 mm to 1.5 mm from the viewpoint of shape retention and handleability. It is particularly preferred.

Next, the preferable composition of the liquid mixture for hydrogel formation used for the manufacturing method (1) and (2) of the gel sheet of this invention is demonstrated. The composition shown below is for obtaining a gel sheet excellent in release properties.
In the present invention, the release property refers to a function in which components retained in the hydrogel layer exude from the hydrogel and move to a living body or an absorbent body that are adjacent adherends. The component that exudes from the gel sheet in the present invention is referred to as a separating solution, not only the aqueous component in the hydrogel layer and the aqueous component in the emulsion, but also the oily component in the O / W emulsion and other oily components, Furthermore, microparticles are also included.
If it is a gel sheet with high release property, the various components in the hydrogel layer of a gel sheet can be effectively supplied to an adjacent adherend by contacting the adherend.

  In the present invention, “excellent in separating properties” and “high separating properties” are preferably as follows: the separation rate determined as follows is preferably 40% by mass to 90% by mass, and more preferably 45% by mass. It means that the content is 85% by mass or less and particularly preferably 50% by mass or more and 80% by mass or less.

In the present invention, the separation rate is determined by cutting a gel sheet into 3 cm × 3 cm, and filtering this sample with a filter paper No. 9 manufactured by Advantech Toyo Co., Ltd. having a diameter of 9 cm. 2 (two kinds of qualitative filter papers defined in JIS P3801 (1995 edition): 125 g / m ² , thickness 0.26 mm, drainage time 80 seconds, water absorption 80 cm) are sandwiched between the upper and lower two sheets, 25 The change in filter paper mass is measured after standing for 10 minutes in an environment of 50 ° C. and 10% relative humidity. Using the obtained measured value, the separation rate is calculated by the following formula (1). Let the average value of the value obtained by repeating said measurement test 5 times be a separation rate.
Separation rate (mass%) = (filter paper absorbed mass / gel initial mass ^* ) × 100 (1)
* Here, the gel initial mass is a value obtained by excluding the mass of the support from the mass of the test piece of the gel sheet.

  In addition, about the measuring method of a separation rate, the method described in the "fragrance journal" June 2007 pages 95-102 can also be referred, for example.

As described above, by evaluating the separation rate as the amount of liquid absorbed by the filter paper, an indicator of whether water or an active ingredient can penetrate efficiently when contacting the epidermis, which is one of the adherends It can be.
When the separation rate is less than 40%, the supply of moisture or the like may be insufficient to the adherend, and when it exceeds 90%, the stability of the gel sheet during storage may be reduced. That is, since the gel sheet excellent in release property can hold an active ingredient at a high concentration, the active ingredient can be efficiently supplied to the adherend.

The hydrogel-forming compounded liquid used in the present invention is collagen or collagen degradation products, polysaccharides, O / W type, in order to enhance the release properties of the gel sheet and to be suitably used as a cosmetic. It is preferable to contain an emulsion or a polyether. Two or more of these components may be contained.
In addition, by combining the components shown below, it is possible to obtain a gel sheet that is flexible, easily deformed by stress, and has a wet surface. Such a gel sheet can improve adhesiveness with an adherend.
Hereinafter, each component will be described.

<Polyether>
The hydrogel-forming compounded liquid in the present invention preferably contains a polyether for the purpose of promoting release properties.
Examples of the polyether include polyethylene oxide, polypropylene oxide, polyethylene oxide / polypropylene oxide block copolymer, polyethylene oxide / polypropylene oxide / polyethylene oxide block copolymer, and block polymers containing polyethylene oxide and polypropylene oxide are particularly preferable. Specifically, a polyethylene oxide / polypropylene oxide block copolymer (hereinafter sometimes abbreviated as “PEO-PPO block polymer”) or a polyethylene oxide / polypropylene oxide / polyethylene oxide block copolymer (hereinafter referred to as “PEO-PPO-PEO”). Particularly preferred is “block polymer”. These polyethers are known as poloxamers, “Pluronic”, “Lutrol” (all manufactured by BASF), New Pole (manufactured by Sanyo Chemical Industries), Epan (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) ), Pronon (manufactured by Nippon Oil & Fats Co., Ltd.), etc., can be easily obtained as commercial products.
The weight average molecular weight (Mw) of the polyether used in the present invention is preferably 1,000 to 1,000,000, and more preferably 5,000 to 500,000.

  Moreover, 0.05 mass%-20 mass% are preferable, as for content of the polyether which occupies in the compounding liquid for hydrogel formation used for this invention, 0.1 mass%-10 mass% are more preferable. 2 mass%-5 mass% are especially preferable. If the content of the polyether is 0.05% by mass or more, the release property is increased, and the active ingredient contained in the hydrogel layer is likely to exude, for example, an effect of improving skin permeability is obtained, If it is 20 mass% or less, it can prevent that the storage stability of a gel sheet falls remarkably.

<Polysaccharides>
In order to improve the handleability, the hydrogel-forming liquid mixture in the present invention preferably contains a polysaccharide.
Examples of polysaccharides that can be used in the present invention include neutral polysaccharides (eg, cellulose, amylose, amylopectin, dextran, pullulan, inulin, galactan, mannan, xylan, arabinan, glucomannan, galactomannan, agarose, methylcellulose. , Hydroxypropylcellulose, curdlan, xyloglucan, etc.), anionic polysaccharides (pectinic acid, alginic acid, agar, carrageenan, fucoidan, hyaluronic acid, chondroitin sulfate, heparin, gellan gum, native gellan gum, xanthan gum, carboxymethylcellulose, carboxymethyl starch , Carboxymethyldextran, etc.), cationic polysaccharides (chitin, chitosan, cationized cellulose, cationized starch, cationization) Dextran, etc.) and the like.
Among these, polysaccharides having a high thickening gelling action are more preferable, and glucomannan, galactomannan, agar, carrageenan, gellan gum, native gellan gum, and xanthan gum are particularly preferable. Further, two or more of these polysaccharides may be used in combination in order to improve the gelation property.

  0.01 mass%-5 mass% are preferable, as for content of the polysaccharide in the liquid mixture for hydrogel formation in this invention, 0.1 mass%-4 mass% are more preferable, 0.2 mass%-2 Mass% is particularly preferred. If the content of the polysaccharide is 0.01% by mass or more, the hydrogel layer can be prevented from lacking in strength, so that the handleability is improved, and if it is 5% by mass or less, the release property is increased. The active ingredient contained in the hydrogel layer is likely to exude, and for example, a decrease in skin permeability can be prevented.

<O / W emulsion>
It is preferable that the liquid mixture for hydrogel formation used by this invention contains O / W type | mold emulsion. In particular, an O / W emulsion containing an oil-soluble active ingredient or medicinal ingredient is preferable. By setting it as such a form, the component in O / W type | mold emulsion can be supplied to a to-be-adhered body, for example, the effect derived from each component, for example, the skin beautifying effect, can be heightened by skin penetration. .
Examples of oil-soluble active ingredients include fat-soluble vitamins and analogs thereof (tocopherol, tocotrienol, retinol, retinal, calciferol, etc.), sterols (cholesterol, phytosterol, etc.), ubiquinone (CoQ10, etc.), sphingolipid, Ceramide, oryzanol, squalene, squalane, carotenoid and the like and derivatives thereof are preferable, and in the present invention, carotenoid is particularly preferable.

Carotenoids include actinioerythrol, astaxanthin, bixin, canthaxanthin, capsanthin, β-8′-apo-carotenal, β-12′-apo′-carotenal, α-carotene, β-carotene, γ-carotene, β -Cryptoxanthine, lutein, lycopene, biolerithrin, zeaxanthin, fucoxanthin and their derivatives.
Of these, astaxanthin, lutein, zeaxanthin, and β-cryptoxanthin are preferable, and particularly astaxanthin that is recognized to have an antioxidant effect, an anti-inflammatory effect, an anti-skin aging effect, and a whitening effect is preferable.
In addition, in this O / W type | mold emulsion, you may contain other components, such as an emulsifier which can generally be contained in each phase of an emulsion composition, in the quantity generally used. Such other components also include other components described herein such as polyhydric alcohols.

The volume average particle size of the emulsified particles of the O / W emulsion is preferably 1 nm to 200 nm, more preferably 1 nm to 150 nm, and particularly preferably 1 nm to 100 nm.
The volume average particle diameter can be measured with a commercially available particle size distribution meter or the like. Emulsion particle size measurement methods include optical microscopy, confocal laser microscopy, electron microscopy, atomic force microscopy, static light scattering, laser diffraction, dynamic light scattering, centrifugal sedimentation, electricity A pulse measurement method, a chromatography method, an ultrasonic attenuation method, and the like are known, and apparatuses corresponding to the respective principles are commercially available.
In view of the volume average particle size range and ease of measurement in the present invention, it is preferable to use a dynamic light scattering method in measuring the volume average particle size of the emulsion in the present invention. As a commercially available measuring device using dynamic light scattering, Nanotrac UPA (Nikkiso Co., Ltd.), dynamic light scattering type particle size distribution measuring device LB-550 (Horiba, Ltd.), a concentrated particle size analyzer FPAR-1000 (Otsuka Electronics Co., Ltd.) etc. are mentioned.

In the present invention, the volume average particle size of the O / W emulsion employs a value measured at 25 ° C. using a concentrated particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).
The volume average particle diameter is measured by using a measuring glass tube after diluting with pure water so that the concentration of the oil phase component falls within the range of 0.1% by mass to 1% by mass. The volume average particle diameter is obtained as a cumulative (50%) value when measured by setting the dispersion medium refractive index to 1.3313 (pure water) and the dispersion medium viscosity to 0.8846 mPa · S (pure water). Can do.

The manufacturing method of an O / W type emulsion is not specifically limited, For example, the method described in Unexamined-Japanese-Patent No. 2005-75817 can be used. Alternatively, a) a water-soluble emulsifier is dissolved in an aqueous medium to obtain an aqueous phase, b) carotenoid, tocopherol, lecithin, and other oils and fats as necessary are mixed and dissolved to obtain an oil phase, and c) stirring It is preferable to manufacture by the method of mixing an aqueous phase and an oil phase below, emulsifying and dispersing, and obtaining an emulsion composition.
When emulsifying and dispersing, for example, after emulsification using a normal emulsifier using a shearing action such as stirring with a stirrer, impeller, homomixer, continuous flow type shearing device, etc., two methods are used such as passing through a high-pressure homogenizer. It is particularly preferable to use the above emulsifying apparatus in combination. By using a high-pressure homogenizer, it is possible to align the emulsion into more uniform droplets of fine particles.

The content of the O / W emulsion relative to the hydrogel in the present invention is preferably 0.001% by mass to 10% by mass, and 0.05% by mass to 1% in terms of the effectiveness of the active ingredient and the skin permeability. More preferably, it is mass%.
In addition, the content of the oil-soluble active ingredient in the hydrogel-forming liquid mixture in the present invention varies depending on the type of the active ingredient, but is preferably 0.0001% by mass to 10% by mass, and 0.005% by mass to 5% by mass. % Is more preferable.
When the oil-soluble active ingredient is a carotenoid, 0.0001% by mass to 0.5% by mass is preferable, and 0.0005% by mass to 0.1% by mass is more preferable with respect to the hydrogel-forming liquid mixture. 0.001 mass% to 0.05 mass% is particularly preferable. If the carotenoid content is 0.0001% by mass or more, the effect (skin-beautifying effect, etc.) after applying the gel sheet of the present invention to the skin can be felt, and if it is 0.5% by mass or less, Coloring can be suppressed and discomfort is less likely to occur.

<Collagen or its degradation products>
In order to obtain a gel sheet that can improve the moisture retention of an adherend such as the epidermis, the hydrogel-forming liquid mixture used in the present invention preferably contains at least one selected from collagen and its decomposition products.
Collagen here is not particularly limited, and various collagen extracts are targeted. Extraction can be performed by a known method such as acid solubilization, alkali solubilization, neutral salt solubilization, enzyme solubilization using collagen-containing raw materials. As the collagen-containing material, any material containing collagen can be used, and examples include vertebrate (eg, cow, pig, sardine, shark, etc.) skin or scales, bones, cartilage, tendons, and organs. However, since the collagen content is high, bone, cartilage, skin or scale, tendon, placenta, etc. are preferably used. Among these, water-soluble collagen is preferable as the collagen suitably used in the present invention.

Further, the degradation product of collagen used in the present invention can be obtained by hydrolyzing collagen with a proteolytic enzyme such as collagenase, trypsin or chymotrypsin, acid or alkali, or by heat denaturation.
Examples of the collagen degradation product include acid-treated gelatin, alkali-treated gelatin, enzyme-degraded gelatin, collagen tripeptide, collagen dipeptide, and amino acid (glycine, proline, hydroxyproline, acetylhydroxyproline, etc.).

  The content of collagen or collagen degradation product in the hydrogel-forming compound liquid in the present invention is preferably 0.05% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass, and 2 mass%-5 mass% are especially preferable. If the content is 0.05% by mass or more, an effect of improving water retention by contact with an adherend such as the epidermis is obtained, and if it is 20% by mass or less, the handleability of the gel sheet is improved.

<Polyhydric alcohol compound>
The hydrogel-forming liquid mixture used in the present invention preferably contains a polyhydric alcohol compound from the viewpoint of the penetration of the active ingredient into the adherend and the storage stability of the gel sheet.
Specific examples of the polyhydric alcohol compound include glycerins (glycerin, diglycerin, etc.), glycols (for example, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3 -Propanediol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, etc.), sugars (glucose, fructose) , Mannose, galactose, xylose, arabinose, glucosamine, N-acetylglucosamine, sucrose, lactose, maltose, isomaltose, trehalose, cellobiose, cordobiose, sophorose, maltotriose, la Inosu, etc. stachyose), sugar alcohols (glycerol, tray roll, erythritol, arabinitol, xylitol, ribitol, mannitol, sorbitol, galactitol, inositol, etc.). The said polyhydric alcohol compound can be used individually or in mixture of 2 or more types.

  Among these, it is preferable to use glycerins or glycols from the viewpoint of permeability of the active ingredient to the adherend, and among them, glycerin and 1,2-propanediol are particularly preferred as the hydrogel-forming liquid mixture in the present invention. 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, and 1,3-butanediol are more preferable. Furthermore, it is particularly preferable to use glycerin, 1,2-propanediol, 1,3-butanediol, or 1,2-hexanediol.

  In the present invention, the proportion of the polyhydric alcohol compound in the hydrogel-forming compound liquid is preferably 50% by mass or less, and particularly preferably 1% by mass to 20% by mass. By making the ratio of a polyhydric alcohol compound 50 mass% or less, the fall of gel strength can be prevented and the handleability of a gel sheet can be improved.

<Water-soluble divalent metal salt>
It is preferable that the hydrogel-forming liquid mixture used in the present invention contains a water-soluble divalent metal salt.
Here, the water-soluble in the present invention refers to a substance that can be dissolved in pure water at 25 ° C. by at least 0.1 mass%.
Examples of the divalent metal forming the water-soluble divalent metal salt used in the present invention include Group II magnesium, calcium, strontium, barium, and transition metals such as Cu ²⁺ , Fe ²⁺ , Zn ²⁺ , and Mn ^2+. A water-soluble salt of magnesium or calcium is preferable. The water-soluble salt may be any of an inorganic salt, an organic acid salt, and an organic / inorganic composite salt, and is not particularly limited. For example, hydrochloride, nitrate, sulfate, phosphate, carbonate, citrate, lactate, malate, succinate, ascorbate, ascorbate phosphate, gluconate, etc. .
Among these, magnesium chloride, calcium chloride, magnesium lactate, magnesium malate, magnesium citrate, calcium citrate, magnesium ascorbate, calcium ascorbate, magnesium ascorbate phosphate, magnesium gluconate, and calcium gluconate are more preferable. Magnesium chloride and magnesium ascorbate phosphate are particularly preferred.

  The proportion of the water-soluble divalent metal salt in the hydrogel-forming compounded liquid in the present invention is preferably 0.01% by mass to 5% by mass, more preferably 0.1% by mass to 4% by mass, and 0.2% Mass% to 2 mass% is particularly preferable.

Further, the blending amount of the water-soluble divalent metal salt is preferably 50 parts by mass or more with respect to 100 parts by mass of the anionic polymer compound used in combination in the hydrogel-forming compound liquid. From the viewpoint of the addition effect of the salt, 50 parts by mass to 1000 parts by mass is more preferable, 70 parts by mass to 500 parts by mass is further preferable, and 80 parts by mass to 300 parts by mass is particularly preferable.
Thus, by using an anionic polymer compound and a divalent metal water-soluble salt in combination, a three-dimensional network structure having a weak cross-linked structure is formed in the formed hydrogel, and sufficient liquid component retention is achieved. It is considered that good release properties are developed.

Here, the anionic polymer compound is selected from a carboxyl group, a sulfo group, a phospho group, and the like as a hydrophilic group in the anionic polysaccharide in the above-mentioned polysaccharide and the hydrophilic polymer compound described later. A high molecular compound having an anionic group in the molecule.
Specifically, for example, anionic synthetic polymer compounds include acrylic acid (co) polymer, methacrylic acid (co) polymer, maleic acid (co) polymer, itaconic acid (co) polymer, p- Examples thereof include vinyl benzoic acid (co) polymer, 2-acrylamido-2-methyl-1-propanesulfonic acid (co) polymer, and styrenesulfonic acid (co) polymer.
The anionic natural polymer compounds include pectic acid, alginic acid, agar, carrageenan, fucoidan, hyaluronic acid, chondroitin sulfate, heparin, gellan gum, native gellan gum, xanthan gum, carboxymethylcellulose, carboxymethyl starch, carboxymethyldextran, polyglutamic acid. Furthermore, DNA, RNA and the like can also be used as the anionic polymer compound in the present invention.

Of these, acrylic acid (co) polymer, alginic acid, agar, carrageenan, hyaluronic acid, gellan gum, native gellan gum, xanthan gum, and carboxymethylcellulose are preferred from the viewpoints of water retention, gel strength and release properties. Carrageenan, gellan gum, native gellan gum and xanthan gum are particularly preferred.
From the viewpoint of improving gel strength, these anionic polymer compounds preferably have a molecular weight in the range of 10,000 to 5,000,000, and 20,000 to 2,000,000. More preferably, it is in the range of 000.

  As described above, when the water-soluble divalent metal salt and the anionic polymer compound are used in combination, the content of the anionic polymer compound in the hydrogel-forming compound solution is 0.01% by mass to 10% by mass. % By mass is preferable, 0.1% by mass to 8% by mass is more preferable, and 0.2% by mass to 4% by mass is particularly preferable. When the content is in this range, a gel sheet having a gel strength with good handleability can be obtained, and a gel sheet having sufficient release properties can be obtained.

The anionic polymer compound and the water-soluble divalent metal salt can be appropriately combined depending on the purpose, but from the viewpoint of achieving both gel strength and release properties, the water-soluble 2 as shown below. Although the combination of a valent metal salt / anionic polymer compound is mentioned as a suitable thing, it is not restrict | limited to these.
Ascorbic acid phosphate magnesium / carrageenan,
Magnesium ascorbate phosphate / gellan gum,
Ascorbic acid phosphate magnesium / agar,
Ascorbic acid phosphate magnesium / xanthan gum,
Ascorbic acid phosphate magnesium / acrylic acid (co) polymer,
Ascorbic acid phosphate magnesium / carboxymethylcellulose,
Magnesium chloride / carrageenan,
Magnesium chloride / gellan gum,
Magnesium chloride / acrylic acid (co) polymer,
Magnesium lactate / carrageenan,
Magnesium lactate / agar calcium lactate / gellan gum calcium ascorbate / carrageenan calcium gluconate / gellan gum

<Other ingredients>
In addition to the above-mentioned components, the hydrogel-forming compounded liquid used in the present invention has other components such as hydrophilic polymer compounds, excipients, preservatives, and fragrances in order to impart various effects to the gel sheet. It is preferable to contain.

-Hydrophilic polymer compounds-
In order to obtain a gel sheet that improves the moisture retention of the adherend, the hydrogel-forming liquid mixture used in the present invention is known as long as the solubility at the time of contact with the adherend such as the skin is not impaired. A hydrophilic polymer compound can be added. The hydrophilic polymer compound can also be used for improving the shape stability of the gel sheet.
The hydrophilic polymer compound that can be used in the present invention is a polymer compound other than the polyether and the polysaccharide, and has a hydrophilic functional group (for example, hydroxyl group, carboxyl group, sulfo group, phospho group, carbamoyl). Group, amino group, ammonio group, ethyleneoxy group, etc.) may be a synthetic polymer compound or a natural polymer compound. These may be used alone or in admixture of two or more.

  Suitable synthetic polymer compounds having a hydrophilic group for the present invention include, for example, vinyl alcohol (co) polymer, 2-hydroxyethyl acrylate (co) polymer, acrylic acid (co) polymer, methacrylic acid ( Co) polymer, maleic acid (co) polymer, itaconic acid (co) polymer, p-vinylbenzoic acid (co) polymer, 2-acrylamido-2-methyl-1-propanesulfonic acid (co) polymer Styrene sulfonic acid (co) polymer, acrylamide (co) polymer, acryloylmorpholine (co) polymer, N-vinylpyrrolidone (co) polymer, vinylamine (co) polymer, N, N-dimethyldiallylammonium chloride (Co) polymer, 2-methacryloyloxyethylammonium chloride (co) polymer, polyethylene glycol methacrylate (co) polymer Polyethyleneimine, and the like.

  The hydrophilic polymer compound in the present invention preferably has a weight average molecular weight of 1,000 to 500,000, preferably 5,000 to 100,000, from the viewpoint of improving the moisture retention of the adherend. More preferred.

  In the present invention, the content of the hydrogel-forming compounding liquid is preferably 0.05% by mass to 5% by mass from the viewpoint of improving the moisture retention of the adherend and handling of the gel sheet, and 0.1% by mass. More preferably, it is -3 mass%.

-Excipient-
In order to improve the shape stability of the gel sheet, it is preferable to add an excipient to the hydrogel-forming liquid mixture used in the present invention.
As the excipient, organic or inorganic fine particles can be preferably used. As the organic fine particles, known polystyrene particles, polymethacrylate particles, and microcrystalline cellulose are preferable. Further, as the inorganic fine particles, titanium oxide, silica, alumina, calcium carbonate, kaolin, clay mineral and the like are preferable. Of these, silica or clay minerals are preferable, and gas phase method silica having an average particle diameter of 200 nm or less and synthetic smectite are particularly preferable.
In the present invention, the proportion of the excipient in the hydrogel-forming liquid mixture is preferably 10% by mass or less, and particularly preferably 1% by mass to 5% by mass.

-Preservative-
The liquid mixture for forming a hydrogel used in the present invention preferably contains a preservative as a countermeasure against the deterioration of the gel sheet by microorganisms.
Examples of the preservative include phenol, benzoic acid and its salt, salicylic acid and its salt, paraoxybenzoic acid esters (methylparaben, ethylparaben, propylparaben, butylparaben), 2-phenoxyethanol, dehydroacetic acid and its salt, sorbic acid And salts thereof, alkylaminoethylglycine chloride, triclosan, benzalkonium chloride, ethanol, propanol, butanol and the like. These may be used alone or more preferably in combination. Of these, p-hydroxybenzoates and phenoxyethanol are particularly preferred.
As content of the preservative in this invention, 0.01 mass%-0.5 mass% are preferable in the compounding liquid for hydrogel formation, 0.02 mass%-0.3 mass% are more preferable, 0.03 Mass% to 0.2 mass% is particularly preferable.

-Fragrance-
In order to obtain a gel sheet that can enhance the relaxation effect, a fragrance may be added to the hydrogel-forming liquid mixture used in the present invention.
Examples of the fragrances include alcohol-based fragrances, phenol-based fragrances, carboxylic acid-based fragrances, and amine-based fragrances. Alcohol-based fragrances include green leaf alcohol, 3-octenol, 9-decenol, linalool, geraniol, nerol, citronellol, rosinol, dimethyloctanol, hydroxycitronellol, tetrahydrolinalool, lavandol, mugol, misenol, terpineol, 1-menthol ( L-menthol), borneol, isobregol, tetrahydromegol, bornylmethoxycyclohexanol, nobol, farnesol, nerolidol, santalol, sandalol, cedrol, vetiverol, patchoulial alcohol, benzyl alcohol, β-phenylethyl alcohol, γ- Phenylpropyl alcohol, cinnamic alcohol, anise alcohol, α-amyl cinnamic alcohol, dimethyl Benzyl carbinol, methyl phenyl carbinol, dimethyl phenyl carbinol, beta-phenylethyl dimethyl carbinol, beta-phenylethyl methyl ethyl carbinol, phenoxyethyl alcohol, phenyl glycol, tertiary butyl cyclohexanol, and the like. Further, eugenol, vanillin, hinokitiol, etc. as phenolic fragrances, cinnamic acid, phenylacetic acid, hydrocinnamic acid, etc. as carboxylic acid fragrances, indole, skatole, 2-methyltetrahydroquinoline as amine-based fragrances , 6-methylquinoline and the like.
These fragrance | flavors are added in the range which does not impair the effect of this invention.

-Organic acid-
The hydrogel-forming liquid mixture used in the present invention may contain an organic acid from the viewpoint of pH adjustment.
Specific examples of the organic acid include acetic acid, α-hydroxy acid (for example, citric acid, lactic acid, gluconic acid, malic acid, succinic acid, etc.), ascorbic acid, pyrrolidone carboxylic acid and the like. These can be used alone or in admixture of two or more.
The content of the organic acid in the hydrogel-forming liquid mixture is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 2% by mass.

-Other additives-
Depending on the intended use of the gel sheet of the present invention, various active ingredients and additives can be further blended into the hydrogel-forming liquid mixture or the formed hydrogel layer. Examples of such active ingredients and additives include those shown below.
Antioxidants (tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters, etc.),
UV absorbers (p-methoxycinnamic acid, octyl p-methoxycinnamic acid, 2-methoxy-2-hydroxybenzophenone, p-dimethylaminobenzoic acid-2-ethylhexyl, etc.),
pH adjusting agents (buffering agents such as lactic acid-sodium lactate, citric acid-sodium citrate, succinic acid-sodium succinate),
Chelating agents (phytic acid, ethylenediaminetetraacetic acid, etc.),
Surfactant (polyglycerin fatty acid ester, sucrose fatty acid ester, lecithin, etc.),

Vitamins (vitamins A, B1, B2, B6, C, D, E and their derivatives),
Amino acids (glycine, trimethylglycine, pyrrolidone carboxylic acid, serine, carnitine, γ-aminobutyric acid, taurine, threonine, asparagine, glutamine, tyrosine, lysine, histidine, arginine, aspartic acid, glutamic acid, ornithine, valine, leucine, etc.)

Anti-inflammatory agents (glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.),
Moisturizer (urea, casein, soybean peptide, lactic acid bacteria fermentation metabolite, yeast fermentation metabolite, honey, lactoferrin, albumin, hydrolyzed elastin, hydrolyzed keratin, hydrolyzed silk),
Whitening agents (ascorbic acid glucoside, 3-O-ethylascorbic acid, arbutin, hydroquinone, kojic acid, lucinol, tranexamic acid, sodium adenosine-1-phosphate, magnolignan, ellagic acid, retinoid, rutin, resorcinol, cysteine, glutathione etc),

  Various extracts (for example, Ashitaba extract, Avocado extract, Achacha extract, Altea extract, Arnica extract, Aloe extract, Apricot extract, Apricot kernel extract, Ginkgo biloba extract, Fennel extract, Turmeric extract, Oolong tea extract, Ages extract, Echinashi leaf extract, Ougon extract, Oat extract, Oen extract, Barley extract, Hypericum extract, Oyster extract, Dutch mustard extract, Orange extract, Seawater dried product, Seaweed extract, Hydrolyzed elastin, Hydrolyzed wheat powder, Hydrolyzed silk, Chamomile extract, Carrot extract , Kawara mugwort extract, licorice extract, calcade extract, oyster extract, kiwi extract, kina extract, cucumber extract, guanosine, gardenia extract, kumazasa extract, clara extract, Lumi extract, grapefruit extract, clematis extract, chlorella extract, mulberry extract, gentian extract, tea extract, yeast extract, burdock extract, rice bran ferment extract, rice germ oil, comfrey extract, bilberry extract, saicin extract, psycho extract, saitai extract, Salvia extract, Soybean extract, Sasa extract, Hawthorn extract, Salamander extract, Shiitake extract, Giant extract, Shikon extract, Perilla extract, Shinobi extract, Shimotake extract, Peonies extract, Shobu root extract, Birch extract, Japanese horse chestnut extract, Papaver extract, Hawthorn Extract, elderberry extract, yarrow extract, mint extract, sage extract, mallow extract, nematode extract, sen Re-extract, Soybean extract, Taiso extract, Thyme extract, Tea extract, Clove extract, Chigaya extract, Chimpi extract, Toki extract, Tokinsenka extract, Tonin extract, Spruce extract, Dokudami extract, Tomato extract, Natto extract, Carrot extract, Garlic extract, Novara extract, Hibiscus Extract, Bacmond Extract, Parsley Extract, Honey, Clamellis Extract, Parietalia Extract, Buttercup Extract, Bisabolol, Biwa Extract, Bukit Dandelion Extract, Fukinotou Extract, Bukkuri Extract, Butcher Bloom Extract, Grape Extract, Propolis, Loofah Extract, Safflower Extract, Peppermint extract, body sage extract, button extract, hop extract, pine extract, marronnier extract, honeysuckle extract, mukurojie Kiss, Melissa extract, Peach extract, Cornflower extract, Eucalyptus extract, Yukinoshita extract, Yuzu extract, Yokuinin extract, Artemisia extract, Lavender extract, Apple extract, Lettuce extract, Lemon extract, Lotus root extract, Rose extract, Rosemary extract, Roman chamomile extract, Royal jelly extract, birch extract, iris extract, grape extract, lily extract, saffron extract, pepper extract, pepper extract, toki extract, seaweed extract, placenta extract, placenta extract, chamomile extract, pearl seed extract, coconut seed extract, grape seed Extract, watercress extract, moon beauty extract, white lupine extract, ginger extract, chicken crown extract, etc.),

Activator (for example, royal jelly, photosensitizer, cholesterol derivative, etc.)
Blood circulation promoters (for example, nonyl acid valenylamide, nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, gingerone, cantalis tincture, ictamol, tannic acid, α-borneol, nicotinic acid tocopherol, inositol hexanicotinate, cyclamate Randelate, cinnarizine, tolazoline, acetylcholine, verapamil, cephalanthin, γ-oryzanol, etc.),
Antiseborrheic agents (eg, sulfur, thianthol, etc.),
Anti-inflammatory agents (eg, tranexamic acid, thiotaurine, hypotaurine, etc.).
These active ingredients can be used alone or in combination of two or more according to the purpose of use of the gel sheet.
In addition to these, medicinal components other than those described above can be added as long as they can be administered into the living body through skin penetration.

  The various active ingredients described above can be introduced into the hydrogel layer by impregnating the gel sheet in a solution containing the active ingredient for about 1 to 3 days after the gel sheet is produced.

Moreover, it is preferable that the gel sheet of the present invention has high transparency from the viewpoint of reducing an unpleasant appearance when it is attached to the skin as an adherend.
Transparency in the present invention can be evaluated by the character discrimination size through a gel sheet using a spectrophotometer. In the gel sheet of the present invention, it is preferable to be able to discriminate a 12-point size character in the Mincho style, and it is more preferable to be able to discriminate a 10-point size character. By being in this range, it becomes easy to confirm the state of the skin at the time of application. However, it is not always necessary to be transparent when applied to a use site where the appearance is not considered.

  Moreover, it is preferable that the hydrogel layer in the gel sheet of this invention is 70 to 95 mass% in water content. When the moisture content is in this range, not only the release efficiency of the active ingredient from the hydrogel layer is improved, but also the irritation when being brought into contact with the epidermis as the adherend can be reduced. Moreover, as a moisture content of a hydrogel layer, 70 mass% or more and 95 mass% or less are preferable, 75 mass% or more and 95 mass% or less are more preferable, and 80 mass% or more and 90 mass% or less are especially preferable. When the water content is less than 70% by mass, the separating property may be deteriorated, and when it exceeds 95% by mass, the strength of the hydrogel layer is reduced and the handleability may be deteriorated.

Here, the water content of the hydrogel layer in the present invention can be measured from the mass reduction rate accompanying heat drying or vacuum drying. Specifically, 1 g of hydrogel is taken out and dried under reduced pressure at 25 ° C. until no change in mass of the sample is observed, and the value calculated by the following equation (2) is taken as the water content. In the present invention, an average value of values obtained by repeating this measurement test five times is defined as a moisture content.
Water content (mass%) = (initial mass−mass after drying) / initial mass × 100 Formula (2)

  The water content of the hydrogel layer can also be measured with a Karl Fischer, infrared, or electrical resistance moisture meter. In addition, when the hydrogel-forming liquid mixture is gelled, the water content can be set to the moisture content of the gel.

Although there is no restriction | limiting in particular as a shape of the gel sheet of this invention, The shape wound in tape shape and the roll shape may be sufficient, and the separate sheet | seat which became independent one by one may be sufficient. In the case of individual sheets, the shape is arbitrary, and examples thereof include an ellipse, a circle, a heart shape, a semicircle, a semielliptical shape, a square, a rectangle, a trapezoid, a triangle, or a combination of these, etc. You may design suitably the shape which can be affixed most appropriately with the shape along an application site | part, and a use site | part.
In addition, the gel sheet of the shape wound by roll shape can be manufactured with the manufacturing method (1) of the gel sheet of the above-mentioned this invention. Moreover, when it is an individual sheet | seat which became independent one by one, it can manufacture with the manufacturing method (2) of the gel sheet of the above-mentioned this invention by making the shape of a formwork into a desired shape.

  In addition, the gel sheet of the present invention is provided with a convex part or a concave part for the purpose of alignment or the like in the center part or the peripheral part, or provided with a cut or cut-out part according to the shape of the use site, thereby making the gel sheet easy to handle. It may be improved or the adhesion to the adherend may be improved.

The gel sheet of the present invention is preferably provided with a protective sheet on the surface applied to the living body of the hydrogel layer for the purpose of maintaining retention of active ingredients and moisture until use.
As the protective sheet, it is preferable to use a polyethylene film, a polypropylene film, a PET film or the like. Among them, it is preferable to use a polyethylene film having a thickness of 500 μm or less, more preferably 20 μm to 400 μm.

Moreover, in order to prevent that a water | moisture content and an active ingredient reduce with time, the gel sheet of this invention may be sealed one by one in the packaging material which consists of a non-breathable raw material.
For example, in the case of a gel sheet continuous in a tape shape, it can be stored in an openable / closable sealed container, such as a packaging bag made of a non-breathable sheet with a chuck, a lidded container formed of a non-breathable resin, or the like. In the case of individual sheets that are independent of each other, they may be sealed in an openable individual bag made of a non-breathable sheet. By storing and distributing in such a state, moisture and active ingredients can be maintained in an appropriate state until use.

The application site when the gel sheet of the present invention is applied to a living body includes the face (lips, cheeks, eyes, upper and lower parts of the eyes, nose, forehead, entire face), arms, legs, chest, and abdomen. , Back, neck and the like.
When the gel sheet of the present invention is applied to a living body, not only the shape described above, but also the area, thickness, adhesive property of the outermost surface of the hydrogel layer, and the like may be appropriately adjusted according to the application site. Moreover, the kind and content of the active ingredient to contain can also be adjusted suitably.
For example, when forming a gel sheet where the application site is the entire face, the shape corresponding to the position of the eyes and mouth is cut out, and the portion corresponding to the position of the nose is cut, and the pasting area is large. Therefore, it is preferable to make adjustments such as increasing the adhesive strength of the hydrogel layer or reducing the thickness. Further, the face shape may be divided into two parts, and divided into an upper part applied around the forehead, eyes and nose, and a lower part applied around the mouth to the chin part.

Since the gel sheet of the present invention formed using the hydrogel-forming liquid mixture as described above has good release and handling properties, the type and amount of components to be contained in the hydrogel layer, the hydrogel layer By selecting the thickness and the shape of the gel sheet, the gel sheet of the present invention is a pack used as a carrier for a transdermally absorbable medicine for administering a drug into a living body, for a beauty treatment, a beauty treatment, a skin treatment, etc. It is useful for sheet-like cosmetics such as skin care materials, carriers for active ingredients such as skin penetration components and anti-inflammatory analgesic components, bioadhesive tapes for wound protection and drug immobilization, wound dressings and the like.
In particular, the gel sheet of the present invention formed using the hydrogel-forming liquid mixture as described above can efficiently impart moisture and active ingredients to the adherend when contacted, so that moisture can be continuously maintained. Although it can be suitably used for any application that needs to be supplied and infiltrated, it has excellent biocompatibility and safety, so its effect is particularly remarkable in applications that efficiently apply moisture and active ingredients when applied to a living body. The active ingredient can be suitably used as a sustained release carrier or a cosmetic.

[Sheet cosmetic]
The sheet cosmetic of the present invention is constituted by the gel sheet of the present invention.
That is, the gel sheet of the present invention can be made into a cosmetic by holding a moisturizing component, a whitening component, an astringent component and the like as active ingredients. This sheet-shaped cosmetic is used with the surface of the hydrogel layer in close contact with the skin.
Since the gel sheet of the present invention is excellent in skin penetration and handling of active ingredients and the like, the sheet-like cosmetic of the present invention is applied to the face as described above to give moisture and medicinal ingredients to the skin. It is particularly useful as a sheet cosmetic.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” and “mass%” represent “parts by mass” and “mass%”, respectively.

<Preparation of O / W type emulsion>
The following aqueous phase components were dissolved for 1 hour while heating at 70 ° C. to obtain an aqueous phase composition.
(Water phase component)
・ Sucrose oleate ・ ・ ・ 15g
・ Decaglyceryl monooleate ・ ・ ・ 23g
・ Glycerin ... 500g
・ Pure water ... 322g

Moreover, the following oil phase component was melt | dissolved for 1 hour, heating at 70 degreeC, and the oil phase composition was obtained.
(Oil phase component)
・ Hematococcus alga extract (astaxanthin content 20% by mass) ... 40 g
・ Mixed tocopherol ・ ・ ・ 10g
・ Lecithin (derived from soybean) ... 90g

The aqueous phase composition was stirred with a homogenizer while maintaining the temperature at 70 ° C. (10000 rpm), and the oil phase composition was added thereto to obtain an emulsion. The obtained emulsion was high-pressure emulsified at 200 MPa using an optimizer HJP-25005 (manufactured by Sugino Machine Co., Ltd.).
The volume average particle size of the obtained emulsion was measured at 25 ° C. using a concentrated particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), and found to be 90 nm.

<Preparation of hydrogel forming liquid>
Among the components shown in Table 1, the components excluding the O / W type emulsion obtained as described above were sequentially added to water, and heated and kneaded at 80 ° C. to obtain a sol.
After cooling this sol-like material to 60 ° C., the O / W emulsion is added and stirred uniformly to prepare hydrogel-forming liquids G1 and G2 for examples, and hydro for comparative examples. A gel-forming compound solution G3 was obtained.
Here, the unit of the blending amount of each component in Table 1 is “mass%”.

(1) Gelation temperature The gelation temperatures of the obtained hydrogel-forming compound solutions G1 to G3 were measured as follows.
That is, using a Bohlin rheometer Gemini 150 (manufactured by Malvern), dynamic viscoelasticity measurement was performed under the conditions of 1 Hz and strain of 0.03. In the measurement, the sample was cooled from 60 ° C. to 25 ° C. at a rate of 3 ° C./min, and the temperature at which tan δ = 1 was determined as the gelation temperature.
The measurement results are shown in Table 1.

(2) Viscosity The viscosities at 60 ° C. of the obtained hydrogel-forming compound solutions G1 to G3 were measured as follows.
That is, the viscosity at 60 ° C. and strain rate 1 (s ⁻¹ ) was measured using a Bohlin rheometer Gemini 150 (manufactured by Malvern).
The measurement results are shown in Table 1.

<Manufacture of gel sheet-1>
A nylon knitted fabric with a basis weight of 20 g / m ² is uniformly placed on a polypropylene film having a thickness of 40 μm. After spreading one of the hydrogel-forming compounding liquids G1 to G3 using a doctor blade, immediately cover with a 40 μm-thick polypropylene film, and using a roller, uniformly spread the compounding liquid to a thickness of 0.8 mm. Extended. Then, the gel sheet of Examples 1-6 and Comparative Examples 1-3 was obtained by leaving still at 25 degreeC for 10 minutes, 100 minutes, and 24 hours, respectively.
In addition, the thickness of the obtained gel sheet was 0.8 mm, the compounded solution penetrated to the back surface of the nylon knitted fabric, and gel was formed on both surfaces of the knitted fabric.
The used hydrogel-forming liquid mixture is shown in Table 2 below.

<Manufacture of gel sheet-2>
A polypropylene case press-molded like a candy ball is used, and the hydrogel-forming compounded liquid is cast so as to have a thickness of 0.8 mm. Immediately after that, a polyester nonwoven fabric having a basis weight of 15 g / m ² was uniformly placed on the mixture of the case, and further covered with a polypropylene film of 40 μm, and then allowed to stand at 25 ° C. for 10 minutes, 100 minutes, and 24 hours, respectively. Thus, gel sheets of Examples 7 to 9 and Comparative Examples 4 to 6 were obtained.
In addition, the thickness of the obtained gel sheet was 0.8 mm. Furthermore, in Examples 7 to 9, hydrogel layers were formed on both surfaces of the nonwoven fabric, but in Comparative Examples 4 to 6, the compounded liquid could not penetrate into the nonwoven fabric, and the hydrogel layer was formed only on one surface.
The used hydrogel-forming liquid mixture is shown in Table 3 below.

(Evaluation of gel sheet)
The obtained gel sheets of Examples 1 to 9 and Comparative Examples 1 to 6 were evaluated as follows, and the evaluation results are shown in Tables 2 and 3.
In addition, each sensory evaluation of moisturizing property, skin barrier property, and skin beautifying effect was obtained by using the gel sheets of Examples 1 to 9 and Comparative Examples 1 to 6 on 10 monitors, respectively, and averaging the evaluations. Values are shown in Tables 2 and 3.

(1) Surface Curability As described above, the surface curability of the gel sheet obtained by setting the gelation time in the gelation step to 10 minutes, 100 minutes, and 24 hours was evaluated by a tack test.
Evaluation was made as AA when the surface was not sticky, A when the surface was slightly sticky but problematic in use, B when sticking operation was difficult due to stickiness on the surface, and C when not hardened.

(2) Separation rate The gel sheets of Examples 1 to 9 and Comparative Examples 1 to 6 were cut into 3 cm x 3 cm, and this sample was filtered with No. 9 filter paper No. manufactured by Advantech Toyo Corporation. 2 (two kinds of qualitative filter papers defined in JIS P3801 (1995 edition): 125 g / m ² , thickness 0.26 mm, drainage time 80 seconds, water absorption 80 cm) are sandwiched between the upper and lower two sheets, 25 The change in filter paper mass is measured after standing for 10 minutes in an environment of 50 ° C. and 10% relative humidity. Using the obtained measured value, the separation rate is calculated by the following formula (1). Let the average value of the value obtained by repeating said measurement test 5 times be a separation rate.
Separation rate (mass%) = (filter paper absorbed mass / gel initial mass ^* ) × 100 (1)
* Here, the gel initial mass is a value obtained by excluding the mass of the support from the mass of the test piece of the gel sheet.

(3) Moisturizing property The moisture content of each layer at the test site (the corner of the corner of the eye) before 10 gel sheets were attached to the monitor was evaluated by the conductance value in a stratum corneum moisture meter (manufactured by Asahi Biomed).
Thereafter, the gel sheets of Examples 1 to 9 and Comparative Examples 1 to 6 were applied to the test site for 15 minutes, and after 30 minutes after peeling, the stratum corneum water content of the test site was measured in the same manner. . When both were compared, the conductance increased by 15% or more in the average of 10 people, AA increased by 10% to 15%, A increased by 2% to 10% was observed The case was evaluated as B when the change was less than 2%.

(4) Skin barrier property In order to evaluate the rough skin improvement function, transepidermal water transpiration (TEWL) was measured by the following method.
That is, 15 minutes a day was continuously applied for 3 days, and the transepidermal water evaporation (TEWL) immediately after the gel sheet was peeled off on the 3rd day was measured with a water evaporation meter (manufactured by Asahi Biomed).
The case where TEWL decreased by 5% by mass or more as compared to before the test was evaluated as A, the case of 1% by mass to 4% by mass as B, and the case where no change was observed as C.

(5) Sensory evaluation Evaluation was performed based on the impression of the appearance of the skin immediately after the gel sheet was peeled off on the third day when 15 minutes of pasting was continued for 3 days. The case where the texture was clearly felt was indicated as A, the case where the texture was slightly felt was assumed as B, and the case where no change was observed was assumed as C.

表２および表３の結果から、実施例１〜９のゲルシートは、短時間でゲル化が進行し、生産効率が高いことが明らかとなった。さらに、実施例１〜９のゲルシートは、高い離しょう性を有し、保湿性や皮膚のバリア性の改善効果に優れ、またキメを調える美肌効果を有することが明らかとなった。
一方、比較例１〜６のゲルシートでは、ゲル化に長時間を要するために製造効率が低いことが分かる。特に、比較例１、２、４、５では、ゲル化時間が不十分であり、離しょう性を評価しようとしてもハイドロゲル層が濾紙に付着してしまい、評価不能となっていた。また、比較例１では、ゲル化時間が著しく不十分であり、保湿性や皮膚バリア性を評価しようとしても、ハイドロゲル層が表皮に残存してしまい、評価不能となっていた。さらには、比較例３および６のゲルシートのように、ゲル化時間を２４時間とした場合であっても、離しょう性、保湿性、皮膚バリア性のいずれもが実施例１〜９のゲルシートよりも劣っていることが分かる。

From the results of Table 2 and Table 3, it was revealed that the gel sheets of Examples 1 to 9 were gelled in a short time and had high production efficiency. Furthermore, it was revealed that the gel sheets of Examples 1 to 9 have high release properties, are excellent in moisturizing properties and skin barrier properties, and have a skin-beautifying effect that adjusts the texture.
On the other hand, in the gel sheets of Comparative Examples 1 to 6, it can be seen that the production efficiency is low because gelation takes a long time. In particular, in Comparative Examples 1, 2, 4, and 5, the gelation time was insufficient, and even when trying to evaluate the separation property, the hydrogel layer adhered to the filter paper, making evaluation impossible. Further, in Comparative Example 1, the gelation time was remarkably insufficient, and even when trying to evaluate the moisture retention and skin barrier properties, the hydrogel layer remained on the epidermis, making evaluation impossible. Furthermore, as in the gel sheets of Comparative Examples 3 and 6, even when the gelation time was 24 hours, all of the release properties, moisture retention, and skin barrier properties were from the gel sheets of Examples 1-9. It turns out that it is inferior.

Claims (12)

It is composed of a liquid-permeable support and hydrogel layers formed on both sides of the support,
A step of coating a hydrogel-forming liquid mixture having a gelation temperature of 10 ° C. to 60 ° C. on a liquid-permeable support after adjusting the temperature to be equal to or higher than the gelation temperature;
Forming a hydrogel layer by gelling the hydrogel-forming compounded liquid under an atmosphere of 0 ° C. to gelation temperature;
A method for producing a gel sheet, comprising: It is composed of a liquid-permeable support and hydrogel layers formed on both sides of the support,
A hydrogel-forming liquid mixture having a gelling temperature of 10 ° C. to 60 ° C., which has been adjusted to a temperature equal to or higher than the gelling temperature, is cast into a mold, and then liquid permeable into the mold. Inserting a support and impregnating the support with the hydrogel-forming compound liquid; and
Forming a hydrogel layer by gelling the hydrogel-forming compounded liquid under an atmosphere of 0 ° C. to gelation temperature;
A method for producing a gel sheet, comprising:   The step of forming the hydrogel layer is a step of forming the hydrogel layer by holding the mixture for hydrogel formation in an atmosphere of 0 ° C. to gelation temperature for 1 minute to 120 minutes and gelling the liquid mixture for forming the hydrogel. The manufacturing method of the gel sheet of Claim 1 or Claim 2 characterized by these.   4. The method for producing a gel sheet according to claim 1, wherein the hydrogel-forming liquid mixture has a viscosity at 60 ° C. of 100 mPa · s to 1,000,000 mPa · s. 5.   The said liquid-permeable support body is a porous film, a woven fabric, or a nonwoven fabric, The manufacturing method of the gel sheet of any one of Claims 1-4 characterized by the above-mentioned.   The method for producing a gel sheet according to any one of claims 1 to 5, wherein the liquid mixture for forming a hydrogel contains collagen or a collagen degradation product.   The method for producing a gel sheet according to any one of claims 1 to 6, wherein the liquid mixture for forming a hydrogel contains a polysaccharide.   The method for producing a gel sheet according to any one of claims 1 to 7, wherein the liquid mixture for forming a hydrogel contains an O / W emulsion.   The method for producing a gel sheet according to any one of claims 1 to 8, wherein the liquid mixture for forming a hydrogel contains a polyether.   The thickness is 0.4 mm-2 mm, The manufacturing method of the gel sheet of any one of Claims 1-9 characterized by the above-mentioned.   The gel sheet obtained by the manufacturing method of the gel sheet of any one of Claims 1-10.   A sheet-like cosmetic using the gel sheet according to claim 11.