JP5539769B2 - Hydrous gel sheet - Google Patents

Description

  The present invention relates to a water-containing gel sheet in which three kinds of specific water-soluble polymers are combined, and further relates to a water-containing gel sheet containing an oil component and a water-soluble drug. More specifically, by containing the above-mentioned components, it has a characteristic of having moisture in the gel structure, fresh and rich in flexibility and stretchability, and excellent adhesion to the skin. A water-containing gel sheet that increases flexibility and moisture content and is excellent in stability over time can be obtained.

Traditionally, hydrous gel sheets have been used to relieve patient's pain by absorbing heat and replenishing water by stretching it to the forehead during fever, in addition to medical poultices impregnated with anti-inflammatory analgesics and skin-penetrating agents. It is applied to various fields such as preparations for wounds, wound dressings that protect the wound itself from the external environment, and pack preparations that effectively penetrate cosmetic ingredients into the skin.
For example, a technique for forming a gel using a metal ion as a crosslinking agent on an acrylic acid polymer (see Patent Document 1), or a gel composition using a cellulose polymer and a polyvalent metal salt thereof (Patent Document 2) , A gel sheet for packs containing xanthan gum and locust bean gum based on agar (Patent Document 3), a patch sheet using methyl vinyl ether / maleic anhydride crosspolymer as a gelling agent (Patent Document 4), and carrageenan There is a cooling sheet (Patent Document 5).

JP-A 63-150222 JP 59-108045 A JP 2005-8613 A JP 2006-298894 A JP 2006-095200 A

However, in the technique described in Patent Document 1, the gel may become non-uniform due to the rapid formation of a cross-linked structure consisting of an acrylic polymer and metal ions during production. There has been a problem in stability that the aqueous component oozes out of the gel due to the change in the cross-linked structure over time. Moreover, in the technique of the above-mentioned Patent Document 2, the gelation reaction is fast and the handling at the time of production is very bad. Furthermore, these often have insufficient gel strength. In order to compensate for this, the usability is satisfied by applying the gel to a support made of non-woven fabric, etc., but as a result, there are problems such as loss of elasticity and flexibility inherent to the gel. It was. Moreover, the technique of the above-mentioned Patent Document 3 has a problem that the gel structure is weakened by blending a water-soluble drug such as an electrolyte, and the structure cannot be maintained during use, although a support is not required. Furthermore, in the technique of the above-mentioned patent document 4, since the adhesiveness of the sheet is too strong, there are problems such as stickiness of the after-skin after use, poor usability, and the gel itself being torn off when peeled off from the skin. Existed. Moreover, with the technique of the said patent document 5, even if intensity | strength improved, the feeling of close_contact | adherence to skin, elasticity, etc. were not enough.
Therefore, the present invention is characterized by maintaining the gel strength, fresh, rich in flexibility and elasticity, and excellent in adhesion to the skin, and increasing the flexibility and moisture content of the skin by using it. The main object of the present invention is to provide a hydrogel sheet that is excellent in stability over time.

In order to solve the above problems, the inventors of the present invention relate to a water-containing gel sheet in which three kinds of specific water-soluble polymers are combined, and further contain an oily component and a water-soluble drug to thereby increase the strength and elasticity of the gel sheet. It was found that a water-containing gel sheet having excellent properties, further usability and skin effect, and good stability over time was obtained, and the present invention was completed.
Based on the above findings, the present invention comprises at least a combination of component (a): (meth) acrylic acid, (meth) acrylic acid alkyl ester, and a compound having two or more ethylenically unsaturated groups. A water-soluble polymer that exhibits increased viscosity when an electrolyte is contained, component (b): methyl vinyl ether / maleic anhydride copolymer, component (c): agar, and component (D): A hydrogel sheet characterized in that a gel composition containing water is formed into a sheet shape.
The hydrogel sheet of the present invention preferably contains 0.5 to 10.0% by mass of the water-soluble polymer of the component (a) in the gel composition.
The component (b) methyl vinyl ether / maleic anhydride copolymer is preferably contained in the gel composition in an amount of 0.01 to 5.0% by mass, and the component (c) agar is added to the gel composition. It is preferable to contain 0.05-3.0 mass% in a gel composition.
Furthermore, it is preferable to contain 0.01-20.0 mass% of oil-based components in the said gel composition as a component (e).
Furthermore, as a component (f), it is preferable to contain 0.01-10.0 mass% of water-soluble chemical | medical agents in the said gel composition.
When the water-soluble drug of the component (f) is an electrolyte component, the electrical conductivity at 25 ° C. of an aqueous solution composed of the component (d) water is preferably 50 to 2500 mS / m.

  The hydrogel sheet of the present invention is characterized by the fact that the gel is fresh, rich in flexibility and stretchability, and excellent in adhesion to the skin, and increases the flexibility and moisture content of the skin when used, and is stable over time Excellent in properties.

Sectional drawing which shows an example of the water-containing gel sheet of this invention.

The code | symbol 10 of FIG. 1 has shown an example of the hydrogel sheet of this invention, and the hydrogel sheet 10 has the gel layer 15 which shape | molded the gel composition in the sheet form.
Although the water-containing gel sheet 10 may be composed of the gel layer 15 alone, the support film 11 and / or the release film 18 may be attached to one side or both sides of the gel layer 15.
Although the support film 11 is not specifically limited, what has flexibility, such as a nonwoven fabric and a resin film, is desirable.
The release film 18 is not particularly limited, and various materials such as a resin film can be used. However, a release film is preferably used so that the gel layer 15 is easily peeled off. Moreover, if the peeling film 18 with low water vapor permeability is affixed to the gel layer 15, moisture evaporation from the gel is prevented, and storage stability is enhanced.

Next, the gel composition constituting the gel layer 15 will be described.
The gel composition used in the present invention is roughly classified into a specific water-soluble polymer that gels and exhibits viscosity when component (a) contains an electrolyte, and component (b) methyl vinyl ether / maleic anhydride copolymer. , Component (c) agar and (d) water at least. Moreover, you may contain a component (e) oil-based component and (f) water-soluble chemical | medical agent as needed.

Hereinafter, each component will be described in detail.
<Component (a): Water-soluble polymer>
The water-soluble polymer that can be used in the gel composition is blended for the purpose of maintaining the gel structure as the basic skeleton of the gel composition, and has the effect of improving the aging stability and the skin effect of the gel sheet pack.
The water-soluble polymer of component (a) is composed of a copolymer in which (meth) acrylic acid, (meth) acrylic acid alkyl ester, and a compound having two or more ethylenically unsaturated groups are bonded to each other. It is a water-soluble polymer that exhibits thickening when it is contained.

  In the present invention, (meth) acrylic acid refers to acrylic acid and methacrylic acid, and (meth) acrylic acid alkyl ester refers to acrylic acid alkyl ester and methacrylic acid alkyl ester. Therefore, the water-soluble polymer (a) may use either one or both of acrylic acid and methacrylic acid as the raw material monomer for the copolymer. One or both may be used.

(A-1) Acrylic acid, methacrylic acid The composition ratio in the water-soluble polymer (a) of acrylic acid or methacrylic acid (hereinafter referred to as (meth) acrylic acid) impairs the properties of the water-soluble polymer (a). It is not particularly limited as long as it is not set, and can be set freely. In the present invention, 95.42 to 97.48 mass% (hereinafter, “mass%” is simply abbreviated as “%”), that is, 95.42% or more and 97.48% or less is preferable, and 95.47 to 97. .46% is more preferable, and 95.97 to 96.94% is still more preferable.
When the composition ratio of the (meth) acrylic acid in the water-soluble polymer (a) is less than 95.42%, a low-concentration aqueous solution (described later) containing the water-soluble polymer (a) is prepared. In some cases, the viscosity in the presence of the electrolyte becomes extremely high, and the rate of change in viscosity at a predetermined electrolyte concentration increases, making it difficult to use. Conversely, when the composition ratio of (meth) acrylic acid in the water-soluble polymer (a) exceeds 97.48%, when preparing a neutralized viscous aqueous solution containing the water-soluble polymer (a) described later, This is because a sufficient viscosity cannot be obtained in the presence of the electrolyte, and the rate of change in viscosity due to temperature and electrolyte concentration may be large, making it difficult to use.

(A-2) Acrylic acid alkyl ester, methacrylic acid alkyl ester Acrylic acid alkyl ester or methacrylic acid alkyl ester (hereinafter referred to as “(meth) acrylic acid alkyl ester”) is the type of water-soluble polymer (a). Although it will not specifically limit if a characteristic is not impaired, In this invention, it is preferable that carbon number of an alkyl group is 18-24 (18 or more and 24 or less). The (meth) acrylic acid alkyl ester having 18 to 24 carbon atoms in the alkyl group refers to an ester of (meth) acrylic acid and a higher alcohol having 18 to 24 carbon atoms in the alkyl group. Examples include esters of (meth) acrylic acid and stearyl alcohol, esters of (meth) acrylic acid and eicosanol, esters of (meth) acrylic acid and behenyl alcohol, and esters of (meth) acrylic acid and tetracosanol. it can. These may be used alone or in combination of two or more.

  Among these, in the present invention, considering the viscosity characteristics and texture of the neutralized viscous aqueous solution described later containing the water-soluble polymer (a) and the neutralized viscous aqueous solution in the presence of an electrolyte, stearyl methacrylate, Eicosanyl methacrylate, behenyl methacrylate, and tetracosanyl methacrylate are preferred, and (meth) acrylic acid alkyl esters containing at least 50% behenyl methacrylate are more preferred. In addition, as a (meth) acrylic-acid alkylester whose carbon number of an alkyl group is 18-24, you may use commercial items, such as brand name "Blemmer VMA70" by Nippon Oil & Fat Co., Ltd., for example.

  The composition ratio of the (meth) acrylic acid alkyl ester in the water-soluble polymer (a) is not particularly limited as long as the characteristics of the water-soluble polymer (a) are not impaired, and can be freely set. In the present invention, it is particularly preferably 2.43% to 4.3%, and more preferably 2.91% to 3.84%. When the composition ratio of the (meth) acrylic acid alkyl ester in the water-soluble polymer (a) is less than 2.43%, an electrolyte is present when a neutralized viscous aqueous solution containing the water-soluble polymer (a) described later is prepared. In some cases, sufficient viscosity cannot be obtained, and the rate of change in viscosity due to temperature and electrolyte concentration is large, making it difficult to use. Conversely, when the composition ratio of the (meth) acrylic acid alkyl ester in the water-soluble polymer (a) exceeds 4.3%, a neutralized viscous aqueous solution containing the water-soluble polymer (a) described below is prepared. This is because the viscosity in the presence of a low concentration of electrolyte becomes extremely high, and the rate of change in viscosity at a predetermined electrolyte concentration may be large, making it difficult to use.

  As a more detailed constitutional ratio in the water-soluble polymer (a) of the (meth) acrylic acid alkyl ester, the (meth) acrylic acid alkyl ester having an alkyl group having 18 to 24 carbon atoms is 2.43% to 4.3%. It is preferable to contain. More specifically, for example, one (meth) acrylic acid alkyl ester having 18 to 24 carbon atoms in the alkyl group may be contained in an amount of 2.43 to 4.3%, and the alkyl group has 18 carbon atoms. A mixture of 2 or more kinds of (meth) acrylic acid alkyl esters of 24 to 2.4% may be contained.

(A-3) Compound having two or more ethylenically unsaturated groups The type of the compound having two or more ethylenically unsaturated groups is not particularly limited as long as the properties of the water-soluble polymer (a) are not impaired. In the invention, for example, a compound in which the ethylenically unsaturated group is an allyl group can be suitably used. Specifically, pentaerythritol allyl ethers such as pentaerythritol diallyl ether, pentaerythritol triallyl ether, and pentaerythritol tetraallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, and polyallyl saccharose are particularly preferable. In addition, these compounds having two or more ethylenically unsaturated groups may be used alone or in combination of two or more.

  The composition ratio of the compound having two or more ethylenically unsaturated groups in the water-soluble polymer (a) is not particularly limited as long as the properties of the water-soluble polymer (a) are not impaired, and can be freely set. In the present invention, 0.08 to 0.29% is particularly preferable, 0.11 to 0.24% is more preferable, and 0.15 to 0.19% is still more preferable. When the composition ratio of the compound having two or more ethylenically unsaturated groups in the water-soluble polymer (a) is less than 0.08%, a later-described neutralized viscous aqueous solution containing the water-soluble polymer (a) was prepared. In some cases, a sufficient viscosity cannot be obtained in the presence of an electrolyte, and the rate of change in viscosity due to temperature and electrolyte concentration is large, making it difficult to use. Conversely, when the composition ratio of the compound having two or more ethylenically unsaturated groups in the water-soluble polymer (a) exceeds 0.29%, the neutralized viscous aqueous solution described later containing the water-soluble polymer (a). This is because the viscosity in the presence of a low concentration of electrolyte becomes high and the viscosity change rate at a predetermined electrolyte concentration is large, which may make it difficult to use.

  The water-soluble polymer (a) contained in the gel composition of the hydrogel sheet of the present invention is a compound having the above (meth) acrylic acid, (meth) acrylic acid alkyl ester, and two or more ethylenically unsaturated groups. And a copolymer in which at least are bonded. The polymerization method is not particularly limited, and can be freely selected from any known methods. For example, a usual method such as a method in which these components are stirred in a solvent in an inert gas atmosphere and polymerized using a polymerization initiator can be used.

Although the inert gas for obtaining the inert gas atmosphere used for superposition | polymerization is not specifically limited, For example, nitrogen gas, argon gas, etc. can be mentioned. Although the solvent used for the polymerization is not particularly limited, it dissolves (meth) acrylic acid, (meth) acrylic acid alkyl ester, and a compound having two or more ethylenically unsaturated groups. Is not particularly limited as long as it does not dissolve the polymerization reaction and does not inhibit the polymerization reaction. Specific examples of such a solvent include hydrocarbon solvents such as n-pentane, n-hexane, n-heptane, cyclopentane, and cyclohexane. These may be used alone or in combination of two or more. Among these, n-hexane and n-heptane can be preferably used. These hydrocarbon solvents can also be used in combination with organic solvents such as ketones, esters, ethers, and saturated alcohols. Specific examples of preferred organic solvents include methyl acetate, ethyl acetate, isopropyl acetate, propyl acetate, butyl acetate, methyl ethyl ketone, butyl propionate, cyclohexanone and the like.
The amount of the solvent used for the polymerization is 300 to 5000 parts by mass (300 parts by mass or more and 5000 parts by mass or less) with respect to 100 parts by mass of (meth) acrylic acid from the viewpoint of improving stirring operability and economy. It is preferable that

Although the polymerization initiator used for polymerization is not particularly limited, for example, a radical polymerization initiator can be preferably used. Specific examples include α, α′-azoisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobismethylisobutyrate, and the like. Among these, in order to obtain a high molecular weight water-soluble polymer (a), it is preferable to use 2,2′-azobismethylisobutyrate.
The amount of the polymerization initiator used for the polymerization is preferably 0.00003 to 0.002 mol (0.00003 mol or more and 0.002 mol or less) with respect to 1 mol of (meth) acrylic acid. When the amount of the polymerization initiator used is less than 0.00003 mol, the reaction rate becomes slow, which may not be economical. On the other hand, when the amount of the polymerization initiator used exceeds 0.002 mol, the polymerization proceeds rapidly, and it may be difficult to control the reaction.

  The reaction temperature in the polymerization is not particularly limited as long as the target water-soluble polymer (a) is obtained, but it is preferably 50 to 90 ° C. (50 to 90 ° C.), and preferably 55 to 75 ° C. More preferred. When the reaction temperature is less than 50 ° C., the viscosity of the reaction solution increases and it may be difficult to stir uniformly. Conversely, when the reaction temperature exceeds 90 ° C., the reaction proceeds rapidly, and it may be difficult to control the reaction. The reaction time can be appropriately set depending on the reaction temperature, but it is usually preferably 0.5 to 5 hours (30 minutes to 5 hours).

The water-soluble polymer (a) used for this invention can be obtained by heating the reaction solution at 80-130 degreeC after completion | finish of reaction, for example, and volatilizing and removing the said solvent. This is because if the heating temperature is less than 80 ° C., drying may take a long time, and if it exceeds 130 ° C., the solubility of the resulting water-soluble polymer (a) in water may be impaired.
When used in the present invention, the water-soluble polymer (a) usually has a pH of 6.5 to 7.5 (pH 6.5 or more and 7.5 or less) at about 1% at 25 ° C. using a neutralizing agent. Used as a neutralized viscous aqueous solution. In order to achieve the object of the present invention, this neutralized viscous aqueous solution preferably has the following properties.

The viscosity at 25 ° C. of the neutralized viscous aqueous solution containing 1% of the water-soluble polymer (a) and 1% of sodium chloride is used to obtain a fresh texture without stickiness when used in the gel composition of the hydrous gel sheet. From the viewpoint that the viscosity can be increased with a small addition amount, it is preferably 40000 mPa · s or more, and more preferably 42000 mPa · s or more.
When the viscosity at 25 ° C. of a neutralized viscous aqueous solution containing 1% of the water-soluble polymer (a) and 1% of sodium chloride is 1, the viscosity when the temperature of the neutralized viscous aqueous solution is 50 ° C. is 0. .8 to 1.2 (0.8 to 1.2), more preferably 0.9 to 1.1, when the gel composition of the hydrous gel sheet is used, it is hardly affected by temperature fluctuations. .

  A solution containing 1% water-soluble polymer (a) and 0.5% sodium chloride with respect to viscosity 1 at 25 ° C. of a neutralized viscous aqueous solution containing 1% water-soluble polymer (a) and 1% sodium chloride The viscosity of the Japanese viscous aqueous solution at 25 ° C. is preferably 0.7 to 1.2, and more preferably 0.9 to 1.0. In this case, when it is used for the gel composition of the hydrous gel sheet, it is easy to utilize for various compounding formulations having different electrolyte concentrations.

  By incorporating the water-soluble polymer (a) described above, it is possible to obtain a water-containing gel sheet that is fresh, flexible and stretchable, and has excellent temporal stability by incorporating moisture into the gel structure. . This is presumed that the alkyl group introduced into the water-soluble polymer (a) forms an aggregate by hydrophobic interaction in aqueous solution, thereby increasing the viscosity and reducing the influence of the electrolyte. The In addition, the compound having two or more ethylenically unsaturated groups introduced into the water-soluble polymer (a) acts as a cross-linking agent to increase the viscosity, and the degree of freedom of hydrophobic interaction decreases, resulting in a temperature increase. It is also presumed that the influence of this is reduced.

  The content of the water-soluble polymer (a) in the gel composition is not particularly limited as long as the object of the present invention is not impaired, and can be appropriately adjusted depending on the object and the blending of other components. 0.5 to 10.0%, more preferably 1.0 to 5.0%. In the present invention, the content in the gel composition is the content in the gel composition (gel layer 15) after being formed into a sheet, that is, after gelation.

The gel composition can contain a basic substance that can be a neutralizing agent for preparing the neutralized viscous aqueous solution containing the water-soluble polymer (a). The kind of the basic substance is not particularly limited as long as it can be adjusted so that the pH at about 1% of the water-soluble polymer (a) is 6.5 to 7.5, and a known basic substance can be freely selected. Can be used. Specific examples include alkali metal hydroxides such as sodium hydroxide and amines such as triethanolamine and diisopropanolamine. Among these, sodium hydroxide is particularly preferred in the present invention. Can be used.
The water-soluble polymer (a) exhibits thickening properties in the presence of an electrolyte and exhibits gel characteristics. The electrolyte for obtaining the gel characteristics is not particularly limited, but the following electrolytes (excluding the basic substance) can be used for evaluating the gel characteristics of the water-soluble polymer (a). Moreover, these electrolytes can also be contained in the hydrated gel sheet of the present invention, and as a result, the gel strength of the hydrated gel sheet can be further increased.

  The type of the electrolyte is not particularly limited as long as it is an electrolyte usually used for skin cosmetics. Specifically, it is a neutral inorganic salt such as sodium chloride, magnesium chloride or potassium chloride, and refers to an inorganic salt other than the component (f) described later.

<Component (b): Methyl vinyl ether / maleic anhydride copolymer>
In order to further increase the strength of the water-containing gel sheet having the water-soluble polymer (a) as a basic skeleton in the gel composition of the water-containing gel sheet, in order to improve adhesion to the skin, and further to improve stability over time And a methyl vinyl ether / maleic anhydride copolymer. The methyl vinyl ether / maleic acid copolymer is not particularly limited as long as it is within the range described in US Pat. No. 5,874,510, and the product is sold under the trade name of Stabilise from IPS Japan. There are things that have been.
The content of the component (b) methyl vinyl ether / maleic anhydride copolymer in the water-containing gel sheet is not particularly limited as long as the object of the present invention is not impaired, and is appropriately adjusted depending on the purpose and the blending of other components. However, it is more preferable that the content of the composition is 0.01 to 5.0%, more preferably 0.05 to 2.5%.

<Component (c): Agar>
Agar is a component that gels water into a solid state, and generally known agar can be used. In addition, as the agar of the component (c), so-called low-strength agar (for example, disclosed in JP-A-5-317008) obtained by cleaving the molecule by acid treatment or the like is used to adjust the jelly strength. Can do. In the present invention, when the acid-treated low-strength agar is selected as the agar of the component (c), it is fresh, rich in flexibility and stretchability, and increases the softness and moisture content of the skin when used, and A hydrous gel sheet having excellent temporal stability can be obtained.
The content of the component (c) agar in the gel composition is not particularly limited as long as the object of the present invention is not impaired, and can be appropriately adjusted depending on the object and the blending of other components. It is more preferable that it is 0.05-3.0% in a thing, More preferably, it is 0.1-2.0%.

When the agar component (c) is used, the sheet strength is higher than when other components (gelatin, xanthan gum) or the like are used. Therefore, when the water-containing gel sheet of the present invention is attached to the skin and then peeled off, the sheet is not destroyed and the gel composition does not transfer to the skin and remain.
Carrageenan is prepared from red algae as with agar, but compared with agar, the skin adhesion when combined with the components (a) and (b) is not sufficient. Therefore, agar is most suitable for the hydrogel sheet of the present invention.

<Component (d): Water>
The water of component (d) is a component that forms the outer phase of the hydrogel sheet, and is a component that embodies a fresh feeling of use. The content of the component (d) in the gel composition is not particularly limited as long as the object of the present invention is not impaired, and can be appropriately adjusted depending on the object and the composition of other components. It is more preferable that it is 65.0-99.5% in a composition, More preferably, it is 80.0-97.5%.

<Component (e): Oily component>
The oil component is a component constituting the oil phase of the gel composition of the water-containing gel sheet, and is used for obtaining a skin effect such as a feeling of use such as smoothness and an emollient feeling. Component (e) includes hydrocarbons, fats and oils, regardless of the origin of animal oils, vegetable oils, synthetic oils, etc., and solid oils, semisolid oils, liquid oils, volatile oils, etc. Waxes, hardened oils, ester oils, fatty acids, higher alcohols, fluorinated oils, lanolin derivatives, oil-based gelling agents, lipophilic surfactants, oil-soluble UV absorbers, etc. Can be blended.

  Specifically, hydrocarbons such as liquid paraffin, squalane, petrolatum, polyisobutylene, polybutene, paraffin wax, ceresin wax, microcrystalline wax, montan wax, Fischer-Tropsch wax, olive oil, castor oil, mink oil, macadamian nut Oils and fats such as owl, beeswax, carnauba wax, candelilla wax, waxes such as gay wax and jojoba oil, octyldodecyl myristate, polyglyceryl diisostearate, diglyceryl triisostearate, glyceryl tribehenate, pentaerythrodiphosphate Trit esters, cholesterol fatty acid esters, esters such as N-lauroyl-L-glutamate di (cholesteryl, behenyl, octyldodecyl), stearic acid, Higher fatty acids such as phosphoric acid, myristic acid, behenic acid, isostearic acid, oleic acid, rosin acid, higher alcohols such as stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, behenyl alcohol, perfluoropolyether , Fluorinated oils such as perfluorodecane and perfluorooctane, lanolin, lanolin acetate, lanolin fatty acid isopropyl, lanolin derivatives such as lanolin alcohol, dextrin fatty acid ester, sucrose fatty acid ester, starch fatty acid ester, 12-hydroxystearic acid, stear Oily gelling agents such as calcium phosphate, ethyl aminobenzoate, methoxycinnamic acid-2-ethylhexyl, 4-tert-butyl-4′-methoxydibenzoylme Emissions, oil-soluble ultraviolet absorbers and the like, such as oxybenzone and the like, can be used in combination alone or in combination. Furthermore, among these, fatty acid esters having two or more branches in the molecule selected from isotridecyl isononanoate, isononyl isononanoate, neopentyl glycol di-2-ethylhexanoate and glyceryl tri-2-ethylhexanoate Of these, an oily component containing at least one kind is more preferable.

  The content of the oil component of the component (e) in the gel composition is not particularly limited as long as the object of the present invention is not impaired, and can be appropriately adjusted depending on the object and the blending of other components. 0.01 to 20.0% is preferable, and 0.1 to 10.0% is more preferable.

<Component (f): Water-soluble drug>
The type of the water-soluble drug is not particularly limited as long as it is composed of an electrolyte and a non-electrolyte and can be used for a normal water-containing gel sheet or skin cosmetic. For example, electrolytes having a moisturizing effect include organic compounds such as amino acids, lactic acid, citric acid and pyrrolidone carboxylic acid, and metal salts thereof such as potassium, sodium, magnesium and calcium, L-alanine, β-alanine, L- Arginine, L-arginine hydrochloride, L-asparagine monohydrate, L-aspartic acid, polyaspartic acid, L-citrulline, L-cysteine, L-cysteine hydrochloride monohydrate, L-cystine, L-dopa L-glutamic acid, L-glutamic acid hydrochloride, L-glutamine, polyglutamic acid, glycine, trimethylglycine, L-histidine, L-histidine hydrochloride monohydrate, L-hydroxyproline, L-isoleucine, L-leucine, L-lysine, L-lysine hydrochloride, L-methionine, L-ornithine hydrochloride, L Proline, L- phenylalanine, L- serine, L- threonine, L- tryptophan, L- tyrosine, amino acids and their derivatives and salts L- valine, and the like.

Examples of the whitening electrolyte include ascorbic acid, ascorbic acid phosphate, ascorbic acid sulfate, ascorbic acid glucoside, and water-soluble ascorbic acids such as metal salts such as sodium, potassium, magnesium, and calcium. It is done. Furthermore, glycyrrhizinates, glycyrrhetinates, salicylates, tranexamates, arbutin, urea, alum, deep sea water, hot spring water, and other naturally-derived aqueous solutions containing these electrolytes are also included. These can be used alone or in combination of two or more. Among these electrolytes, electrolytes containing alkali metal salts or amines are preferable, and ascorbic acid, pyrrolidone carboxylic acid, glycyrrhizic acid, water-soluble derivatives thereof, and salts thereof are particularly preferable.
Examples of non-electrolytes having a moisturizing effect include sugars and sugar alcohols. Examples of the saccharide include monosaccharides such as glucose, fructose, galactose, xylose, maltose, sucrose, lactose, lactose, sucrose, fructose, starch and dextrin, disaccharides such as trehalose, oligosaccharides and polysaccharides. Examples of sugar alcohols include sorbitol, mannitol, maltitol and the like.
That is, the water-soluble drug of component (f) that can be used in the present invention comprises an organic acid and its salts, an amino acid and its derivatives and salts as electrolytes, and a saccharide and sugar alcohols as non-electrolytes. One type may be used alone, or two or more types may be mixed and used.

The content of the component (f) water-soluble drug in the gel composition is not particularly limited as long as the object of the present invention is not impaired, and can be appropriately adjusted depending on the object and the blending of other components. The electrical conductivity at 25 ° C. is 50 to 2500 mS / m (50 mS / m or more and 2500 mS / m or less), more preferably 80 to 2000 mS / m.
In addition, electrical conductivity is the value which measured the aqueous solution which consists of the water-soluble chemical | medical agent of a component (f) and the water of a component (d) at 25 degreeC constant temperature before adding a component (a)-(c). Here, the measurement was performed using an electric conductivity meter (trade name “CM-60G” manufactured by Toa Denpa Kogyo Co., Ltd.).

By containing the above components (a) to (f), the water-containing gel sheet according to the present invention has moisture in the gel structure, fresh, rich in flexibility and stretchability, and excellent in adhesion to the skin. By using it, it is possible to obtain a water-containing gel sheet that increases the flexibility and moisture content of the skin and is excellent in stability over time.
In addition to the above components, the hydrogel sheet of the present invention further includes components used in normal skin cosmetics, for example, surfactants, active electrolyte components other than (f), polymeric substances, moisturizing components, cosmetic components, bactericides. Preservatives, inorganic powders, organic powders, antioxidants, pigments, fragrances, and the like can be used as long as the effects of the present invention are not impaired.

  The use of the hydrogel sheet of the present invention is a medical poultice impregnated with an anti-inflammatory analgesic component or a skin-penetrating agent, a medical treatment that relieves patient pain by absorbing heat and replenishing water by stretching the forehead during fever Preparations, wound coverings that protect the wound itself from the outside environment, and sheet-like pack preparations that effectively penetrate cosmetic ingredients into the skin. The usage method includes a method of directly stretching the hydrogel sheet on the skin, a method of sticking it to a nonwoven fabric, and the like.

<Method for producing hydrous gel sheet>
Although the manufacturing method of the water-containing gel sheet of the present invention is not particularly limited, as an example, a composition (before gelation) composed of a mixture of the above components (a) to (c) and other components (water, etc.) Heat at least above the melting point of agar (70 ° C. or higher) to mix each component uniformly.
The composition is formed into a sheet shape while maintaining the temperature at which each component does not solidify or precipitate, and then cooled to a temperature lower than the freezing point of the agar (less than 40 ° C.), a gel-like composition (gel composition) is obtained. A water-containing gel sheet is obtained.
In addition, components other than components (a) to (d) may be added before heating, or may be added after heating. You may perform processes, such as defoaming and filtration, between the heating mixing and shaping | molding of a composition (before gelatinization).
The molding method is not particularly limited, and various methods such as press molding and extrusion molding can be adopted. In any method, the composition is filled and molded while the temperature of the composition is high (above the freezing point of the agar). It is desirable. In this case, since the sheet is formed only by cooling, the molding is easy and the sheet shape is also good.

Since the components (a) to (c) used in the present invention have high water retention properties, the composition before heating and the composition after gel molding (gel layer 15) are approximately equal in the blending ratio of each component. The error is negligibly small. In addition, since water or the like of the component (d) is not drained after sheet forming, freshness is maintained, and skin adhesion and storage stability are high.
Moreover, in order to improve adhesiveness more, surface treatments, such as an unevenness | corrugation, may be given to a water-containing gel sheet (gel layer 15), but this invention does not give surface treatment by the combination of component (a)-(c). In addition, practically sufficient adhesion can be obtained. Moreover, even when surface processing is performed, since the adhesiveness is originally high, it is not necessary to strictly control the shape and size of the unevenness, and the production of the hydrogel sheet is easy.

  Hereinafter, the present invention will be described in more detail based on examples. In addition, the Example demonstrated below shows an example of the typical Example of this invention, and, thereby, the range of this invention is not interpreted narrowly.

[Synthesis Example 1]
In a 500 mL four-necked flask equipped with a stirrer, a thermometer, a nitrogen blowing tube and a cooling tube, 45 g (0.625 mol) of acrylic acid and an alkyl (meth) acrylate having 18 to 24 carbon atoms in the alkyl group Blemmer VMA70 as an ester (manufactured by NOF Corporation: 10-20 parts by mass of stearyl methacrylate, 10-20 parts by mass of eicosanyl methacrylate, 59-80 parts by mass of behenyl methacrylate, and tetracosanyl methacrylate content of 1 1.58 g of a mixture of less than parts by mass), 0.07 g of pentaerythritol allyl ether, 150 g of normal hexane and 0.081 g (0.00035 mol) of 2,2′-azobismethylisobutyrate were charged.
Subsequently, after stirring and mixing uniformly, nitrogen gas was blown into the solution in order to remove oxygen present in the upper space of the reaction vessel, the raw material and the solvent. Subsequently, it was made to react for 4 hours, hold | maintaining at 60-65 degreeC under nitrogen atmosphere. After the completion of the reaction, the resulting slurry was heated to 90 ° C. to distill off normal hexane, and further dried under reduced pressure at 110 ° C. and 10 mmHg for 8 hours to obtain (meth) acrylic acid / ( 43 g of a meth) acrylic acid alkyl ester copolymer was obtained.
[Synthesis Example 2]
In Synthesis Example 1, a white fine powder was prepared in the same manner as in Example 1 except that the amount of Bremer VMA70 (manufactured by NOF Corporation) was changed to 1.10 g and the amount of pentaerythritol allyl ether was changed to 0.03 g. 44 g of a (meth) acrylic acid / (meth) acrylic acid alkyl ester copolymer was obtained.
[Synthesis Example 3]
In Synthesis Example 1, a white fine powder was obtained in the same manner as in Example 1 except that the amount of use of Blemmer VMA70 (manufactured by NOF Corporation) was changed to 2.20 g and the amount of pentaerythritol allyl ether used was changed to 0.2 g. 44 g of a (meth) acrylic acid / (meth) acrylic acid alkyl ester copolymer was obtained.
(1) Preparation of water-containing gel sheet The water-containing gel sheets according to Examples 1 to 17 and Comparative Examples 1 to 5 having the compositions shown in Tables 1 to 3 below were prepared. In this example, the water-soluble polymer (a) prepared in the above “Synthesis example” was used.

[Examples 1 to 17]
First, the water-soluble polymer (a), the components (b) and (c), sodium hydroxide as a basic substance, and purified water were uniformly mixed and dissolved at 80 ° C. Next, 1,3-butylene glycol, sodium lactate, ascorbic acid 2-glucoside and the like were uniformly mixed and dispersed. Then, defoaming was performed, the obtained gel composition was pressed into a sheet shape, and a hydrous gel sheet according to Examples 1 to 17 was prepared.

[Comparative Examples 1-5]
First, in place of the water-soluble polymer (a), an alkyl acrylate acrylate copolymer is used for Comparative Example 1, sodium acrylate and aluminum chloride are used for Comparative Example 2, and sodium carboxymethylcellulose is used for Comparative Example 3. Triethanolamine was used as the material. For Comparative Example 4, polyvinyl alcohol was used instead of component (b), and for Comparative Example 5, gelatin was used instead of component (c), and the same production as in Examples 1 to 17 with the compositions shown in Tables 1 to 3 above. The hydrogel sheet was adjusted under the conditions. The compositions of Examples and Comparative Examples are shown in Tables 1 to 3 below together with the results of evaluation tests described later.

  The unit of the numerical value of each component in the above Tables 1 to 3 is% (mass%), and the “remaining amount” of water (purified water) of component (d) is the sum of other components (% ) Minus the value. In addition, the electrical conductivity was measured for the aqueous solution by mixing the water of component (d) and the electrolyte of component (f) at the blending ratios in Tables 1 to 3 above.

(2) Evaluation of each quality characteristic Comparative evaluation was performed according to the evaluation criteria shown below about the hydrogel sheet concerning Examples 1-17 prepared above and Comparative Examples 1-5.

According to the sensory evaluation test of 20 panelists specializing in cosmetics evaluation (A) Sheet strength (B) Usability (B1) Freshness, (B2) Adhesion, (B3) Elasticity, (B4) No stickiness (C) Skin Effect Regarding eight items of (C1) skin moisture content, (C2) skin flexibility (D) stability over time, comparative evaluation was performed according to the following evaluation criteria.

(A) Sheet strength

(B) Usability

  (C) Skin effect

  The scores of the evaluation results of each item by 20 cosmetic evaluation panels were summed up and evaluated according to the evaluation criteria shown in Table 12 below. In the present invention, an evaluation of B or higher is considered suitable in the present invention.

(3) Results The results are shown in Tables 1 to 3 above. As shown in Tables 1 to 3, for the hydrogel sheets according to Examples 1 to 17, all evaluations of sheet strength, usability, skin effect, and stability over time showed results of B evaluation or more. In particular, in the pasting action, the strength of the gel sheet itself, the adhesion to the skin and the stretchability are important, and it is considered that the high adhesion contributes to the moisture content and flexibility of the skin. . From this result, the preferable content of the water-soluble polymer (a) is 0.5 to 10.0%, the preferable content of the component (b) is 0.01 to 5.0%, It was found that the preferable content of (c) was 0.05 to 3.0%. Moreover, it turned out that what mix | blended the oil-based component as a component (e) improves the softness | flexibility of skin more.

On the other hand, about the hydrogel sheet which concerns on Comparative Examples 1-5, problems, such as drainage and gelation, were confirmed compared with the thing of an Example by the point of stability with time. In particular, the stickiness of the back skin was severe in Comparative Example 2, and Comparative Example 3 was particularly poor in gel strength and freshness.
Further, even if the components (a), (c), etc. are the same, when the methyl vinyl ether / maleic acid copolymer of the component (b) is changed to another as in Comparative Example 4, there is no stickiness. Even if the flexibility is extremely deteriorated and the components (a) and (b) are the same, if the agar of the component (c) is changed to another as in Comparative Example 5, the sheet strength and stability over time are improved. It deteriorated remarkably, and as a result, the adhesion to the skin decreased, and the moisture content and flexibility of the skin decreased.
From the above, the water-soluble polymer of component (a), the methyl vinyl ether / maleic acid copolymer of component (b), and the agar of component (c) are all prepared, so that moldability, usability, skin It was demonstrated that a hydrous gel sheet excellent in all of the effects can be obtained.

Next, another specific example of the hydrogel sheet of the present invention will be described.
<Example 18: Water-containing gel sheet>
(component)
1. Water-soluble polymer (a) described in Synthesis Example 1: 3.0%
2. Sodium hydroxide: 1.25%
3. Isotridecyl isononanoate: 1.0%
4). Methyl vinyl ether / maleic acid copolymer: 0.05%
5. Agar: 1.0%
6). Citric acid: 0.5%
7). Sodium citrate: 0.1%
8). Ascorbic acid 2-glucoside: 2.0%
9.1,3-butylene glycol: 10.0%
10.1,2-pentanediol: 1.0%
11. Glycerin: 8.0%
12 L-theanine: 0.1%
13. Lauroyl glutamate lysine Na: 0.2%
14 Purified water (add 100%)
15. Preservative: appropriate amount 16. Ethanol: 5.0%
13. As the lauroylglutamate lysine Na, trade name “Perisea L-30” manufactured by Asahi Kasei Co., Ltd. was used.

<< Preparation method >>
14 purified water is added to the above components 1 to 13, the mixture is mixed and dissolved at 80 ° C, and the stirred mixture is cooled to 50 ° C. Then, 15 and 16 were added, and the mixture stirred was pressed into a sheet shape to obtain a hydrous gel sheet made of a sheet-like gel composition.
In Example 18 and Examples 19 and 20 to be described later, “add 100%” of purified water means that the total of water added is 100%, and the content of purified water ranges from 100% to other. It is a value obtained by subtracting the total (%) of the components.
The water-containing gel sheet of Example 18 is fresh, rich in flexibility / stretchability, and excellent in adhesion to the skin. By using it, the flexibility and moisture content of the skin are increased, and the stability over time. It was excellent.

<Example 19: Water-containing gel sheet>
(component)
1. Water-soluble polymer (a) described in Synthesis Example 2: 0.5%
2. Sodium hydroxide: 0.12%
3. Methyl vinyl ether / maleic acid copolymer: 1.0%
4). Agar: 3.0%
5. Trehalose: 0.5%
6.1,3-butylene glycol: 7.0%
7.1,2-Pentanediol: 1.0%
8). Glycerin: 8.0%
9. Glycylglycine: 0.2%
10. Indomethacin: 5.0%
11. Purified water (add 100%)
12 Preservative: appropriate amount 13. Ethanol: 5.0%

<< Preparation method >>
11 purified water is added to the above components 1 to 10, the mixture is mixed and dissolved at 80 ° C., and the stirred mixture is cooled to 50 ° C. Then, 12 and 13 were added, and the mixture stirred was pressed into a sheet shape to obtain a hydrous gel sheet made of a sheet-like gel composition.
The water-containing gel sheet of Example 19 is characterized by its freshness, richness in flexibility and stretchability, and excellent adhesion to the skin. By using it, the flexibility and moisture content of the skin is increased, and the stability over time. It was excellent.

<Example 20: hydrous gel sheet>
(component)
1. Water-soluble polymer (a) described in Synthesis Example 3: 5.0%
2. Sodium hydroxide: 1.25%
3. Methyl vinyl ether / maleic acid copolymer: 2.0%
4). Agar: 1.5%
5. Methyl salicylate: 2.0%
6.1,3-butylene glycol: 7.0%
7.1,2-Pentanediol: 1.0%
8). Glycerin: 8.0%
9. Glycylglycine: 0.2%
10. Purified water (add 100%)
11. Preservative: appropriate amount 12. Ethanol: 5.0%

<< Preparation method >>
10 purified water is added to the above components 1 to 9, the mixture is mixed and dissolved at 80 ° C., and the stirred one is cooled to 50 ° C. Then, 11 and 12 were added, and the mixture and stirred were pressed into a sheet shape to obtain a hydrous gel sheet made of a sheet-like gel composition.

  The water-containing gel sheet of Example 20 is characterized by its freshness, richness in flexibility and stretchability, and excellent adhesion to the skin. By using it, the flexibility and moisture content of the skin is increased, and the stability over time. It was excellent.

  The hydrogel sheet of the present invention can be widely used for medical paste materials, cosmetic pack materials, and the like that are directly attached to human or animal skin.

10: hydrous gel sheet 11 ... support film 15 ... gel layer (sheet-like gel composition)
18 …… Release film

Claims (7)

Component (a): (meth) acrylic acid 95.42 mass% to 97.48 mass% or less , (meth) acrylic acid alkyl ester 2.43 mass% to 4.3 mass%, and ethylenically unsaturated group and compound 0.08 wt% ～0.29 wt% having two or more, but by Rukoto such a copolymer has at least bonded, water-soluble polymer which exhibits a thickening when it is contained an electrolyte,
Component (b): methyl vinyl ether / maleic anhydride copolymer;
Ingredient (c): agar,
Component (d): water,
A water-containing gel sheet, characterized in that a gel composition containing is molded into a sheet shape.   The water-containing gel sheet according to claim 1, wherein the gel composition contains the water-soluble polymer of the component (a) in an amount of 0.5 to 10.0% by mass.   The water content according to any one of claims 1 and 2, wherein the gel composition contains 0.01 to 5.0% by mass of the methyl vinyl ether / maleic anhydride copolymer of the component (b). Gel sheet.   The hydrogel sheet according to any one of claims 1 to 3, wherein 0.05 to 3.0 mass% of the agar of the component (c) is contained in the gel composition.   Furthermore, the water-containing gel sheet of any one of Claims 1 thru | or 4 which contains 0.01-20.0 mass% of oily components in the said gel composition as a component (e).   Furthermore, the water-containing gel sheet of any one of Claims 1 thru | or 5 which contains 0.01-10.0 mass% of water-soluble chemical | medical agents in the said gel composition as a component (f).   The water-containing gel sheet according to claim 6, wherein the water-soluble drug of the component (f) is an electrolyte component, and the electrical conductivity at 25 ° C of an aqueous solution composed of the component (d) water is 50 to 2500 mS / m.

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