JPWO2020066188A1 - Moisture-based patch - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-containing patch whose adhesive strength is maintained even after the moisture in the adhesive layer is volatilized.
An acrylic acid alkyl ester-based copolymer which is a copolymer of a monomer mixture composed of a monomer A and a monomer B, wherein the monomer A has a glass transition temperature (Tg) when the monomer A is homopolymerized. Is a monomer that becomes a polymer of 270 K or more, and the monomer B is a monomer that becomes a polymer having a glass transition temperature (Tg) of 220 K or less when the monomer B is homopolymerized, and is based on the total mass of the monomer mixture. A water-containing patch obtained by blending an acrylic acid alkyl ester-based copolymer in a pressure-sensitive adhesive layer, wherein the proportion of the monomer A is 30% by mass or more and 50% by mass or less.
[Selection diagram] None

Description

The present invention relates to a water-containing patch, and more particularly, to a water-containing patch which maintains high adhesive strength even after the water in the pressure-sensitive adhesive layer is volatilized and has low skin irritation.

A patch using a water-containing adhesive base, which is also generally referred to as a "pap agent" (referred to as a water-containing patch in the present specification) is a plaster layer (adhesive layer) containing an active ingredient such as a drug. It is a kind of adhesive provided on a support such as a non-woven fabric. Since the poultice uses an adhesive base containing water in the plaster layer, the adhesive strength is weak although the skin irritation is low, and in particular, the adhesive strength decreases with time as the water in the plaster layer volatilizes. The problem was that it was easy to peel off from the skin.
In order to solve these problems, an emulsion (also called emulsion) base in which an acrylic acid alkyl ester copolymer known as one component constituting a non-aqueous (also referred to as hydrophobic or lipophilic) adhesive is dispersed is used. A technique of blending a water-containing patch into a plaster layer (adhesive layer) is known.

For example, Patent Document 1 contains 1% of a methyl acrylate / 2-ethylhexyl acrylate copolymer resin emulsion (trade name: Nicazole TS-620, Nippon Carbide Industries, Ltd.) in a poultice base (plaster). A patch (comparative product) is disclosed.
Patent Document 2 provides a water-containing patch that can exhibit adhesive strength and re-adhesive strength during long-term application, suppress deterioration of hardening and suppleness due to water loss, and suppress breakage of the support during peeling. For the purpose of the above, the water-dispersible surfactant was added in an amount of 0.01% by mass or more and 10.0% by mass or less, and the methyl acrylate / 2-ethylhexyl acrylate copolymer was added to the entire composition for a water-containing external patch. A water-containing external patch containing 5.0% by mass or more and 10% by mass or less is disclosed.
Patent Document 3 describes a polyacrylic acid neutralized product and 2.5 of the neutralized product, with an object of providing a poultice material having sufficient adhesive strength even when the water content of the poultice agent decreases with the passage of time. A poultice containing 10 times by mass (5 to 25% by mass on a plaster basis) methyl acrylate / 2-ethylhexyl acrylate copolymer and polyacrylic acid is disclosed.
Patent Document 4 includes poly (methyl acrylate / 2-ethylhexyl acrylate) and a surfactant such as polyethylene glycol fatty acid ester for the purpose of providing a poultice that can peel off the release liner with a smaller force. Pap agents are disclosed.
Patent Document 5 discloses that a cold sheet was obtained using an adhesive composition containing 1.5% by weight of an acrylic resin emulsion (trade name: Nicazole TS-620) and 6.2% by weight of sodium polyacrylate. ing.

Japanese Unexamined Patent Publication No. 9-208462 Japanese Patent No. 5650684 Japanese Patent No. 5921779 International Publication No. 2016/10427 JP-A-2002-104957

As described above, it is known that an acrylic acid alkyl ester copolymer such as a methyl acrylate / 2-ethylhexyl acrylate copolymer is blended in the pressure-sensitive adhesive layer in order to enhance the adhesive durability of the water-containing patch. ing. However, when the blending amount of the above-mentioned copolymer is small, for example, the patch disclosed in Patent Document 1 is shown to lack both initial tack and long-lasting adhesiveness due to the small blending amount. Even when the desired effect of improving the adhesive strength is not obtained and the blending amount is increased, it can be said that the adhesive strength particularly after the moisture in the pressure-sensitive adhesive layer is volatilized is sufficiently satisfactory as compared with the tape preparation. It wasn't a thing.

As a result of diligent research to solve the above problems, the present inventors conducted a glass transition temperature (Tg) when homopolymerized as an acrylic acid alkyl ester-based copolymer on the pressure-sensitive adhesive layer of a water-containing patch. ) Is 30 to 50% by mass of a polymer having a polymer content of 270 K or more, and a monomer having a Tg of 220 K or less when homopolymerized is blended so that the total amount of both monomers is 100% by mass. The present invention has been completed by finding that the adhesive strength is not lowered but rather improved even after the water content in the pressure-sensitive adhesive layer is volatilized, and the skin irritation is also low.

That is, the present invention is a water-containing patch composed of a support, an adhesive layer provided on the support, and a release liner.
The present invention relates to a water-containing patch in which the pressure-sensitive adhesive layer contains the following components 1) to 6) as essential components.
1) Acrylic-based hydrophilic pressure-sensitive adhesive 2) Acrylic acid alkyl ester-based copolymer which is a copolymer of a monomer mixture composed of monomer A and monomer B.
The monomer A is a polymer having a glass transition temperature (Tg) of 270 K or more when the monomer A is homopolymerized.
The monomer B is a monomer having a glass transition temperature (Tg) of 220 K or less when homopolymerized with the monomer B.
Acrylic acid alkyl ester copolymer 3) organic solvent 4) cross-linking agent 5) organic acid 6) in which the proportion of the monomer A is 30% by mass or more and 50% by mass or less with respect to the total mass of the monomer mixture. water

And according to the present invention, the following embodiments are further provided.
1. 1. The monomer A is (meth) acrylic acid alkyl ester such as methyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, vinyl acetate, acrylonitrile, acrylamide. And at least one monomer selected from the group consisting of styrene,
The monomer B is at least one monomer selected from the group consisting of butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate and isononyl acrylate.
The water-containing patch.
2. The monomer A is at least one monomer selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl methacrylate and n-butyl methacrylate.
The water-containing patch, wherein the monomer B is at least one monomer selected from the group consisting of 2-ethylhexyl acrylate and butyl acrylate.
3. 3. The water-containing patch further containing an active ingredient.

According to the present invention, a monomer mixture consisting of a monomer A having a glass transition temperature (Tg) of 270 K or more when homopolymerized and a monomer B having a Tg of 220 K or less when homopolymerized. A pressure-sensitive adhesive containing an acrylic acid alkyl ester-based copolymer, which is a polymer and in which the proportion of the monomer A is 30% by mass or more and 50% by mass or less with respect to the total mass of the monomer mixture. By blending into the layer, the adhesive strength can be maintained even after the water in the adhesive layer has volatilized, the skin irritation is low, there is no inter-polymer adhesion, and a water-containing system that can be reattached to the skin. A patch can be provided.

As described above, in order to enhance the durability of the adhesive strength of the water-containing patch, acrylics such as methyl acrylate / 2-ethylhexyl acrylate copolymer resin emulsion (trade name: Nicazole TS-620, Nippon Carbide Industries Co., Ltd.) Proposals have been made to blend an acid alkyl ester copolymer into the pressure-sensitive adhesive layer and to increase the blending amount. However, in the proposals so far, even when the blending amount of the copolymer is increased, the adhesive strength after the water in the pressure-sensitive adhesive layer is volatilized (after water volatilization) is sufficient as compared with the tape agent. I couldn't say that.
In the above-mentioned problems, the present inventors pay attention to the types of monomers constituting the acrylic acid alkyl ester-based copolymer, which have not been studied so far, and in particular, the blending ratio thereof, during water content and after drying (water volatilization). The adhesive strength of (later) was evaluated. Then, paying attention to the glass transition temperature (Tg) of the homopolymer composed of the monomer, the monomer having a Tg of 270 K or more when homopolymerized and the polymer having a Tg of 220 K or less when homopolymerized By combining with a monomer that becomes It has been found that even when the blending amount of the copolymer is small, the patch has excellent adhesive strength not only when it contains water but also when it is dried, and it is a patch having low skin irritation.
Hereinafter, the configuration of the water-containing patch of the present invention will be described.

The water-containing patch of the present invention (hereinafter, also simply referred to as “patch”) comprises a support, an adhesive layer provided on the support, and a release liner.
The shape of the patch, particularly the support, and the preparation portion composed of the pressure-sensitive adhesive layer provided on the support is not particularly limited, and is rectangular (square, rectangle, etc.), square (trapezoid, rhombus, etc.), polygonal. , Circular, oval, semi-circular, triangular, crescent-shaped, and a combination of these, and various other shapes can be selected according to the sticking location.
The area of the patch (particularly the above-mentioned pharmaceutical portion) can be appropriately determined, and can be, for example, in the range of ^{2 to 300 cm 2 in consideration of the amount of the active ingredient to be blended in the pressure-sensitive adhesive layer.}

[Adhesive layer]
The water-containing patch of the present invention has an acrylic acid alkyl ester-based adhesive that generally constitutes a non-aqueous acrylic pressure-sensitive adhesive, in addition to the hydrophilic acrylic pressure-sensitive adhesive described later, with respect to the water-containing pressure-sensitive adhesive layer. It is characterized in that a polymer is also blended.
Adhesives generally used for the pressure-sensitive adhesive layer (plaster layer) of water-containing patches include polyacrylic acid, partially neutralized polyacrylic acid, sodium polyacrylate, and N-vinylacetamide / sodium acrylate copolymer. Hydrophilic acrylic pressure-sensitive adhesives such as resins are widely used. From the viewpoint of having a high affinity with the above-mentioned hydrophilic acrylic pressure-sensitive adhesive and being able to be kneaded uniformly, the non-water-based pressure-sensitive adhesive to be blended in the water-containing pressure-sensitive adhesive layer of the water-containing patch includes acrylic and methacrylic adhesives. An emulsion-type pressure-sensitive adhesive is preferably blended.
In the present specification, the "acrylic acid alkyl ester-based copolymer" is intended to contain both an acrylic acid and an alkyl ester of methacrylic acid, and the "acrylic adhesive" is also an acrylic adhesive and a methacrylic acid. It is intended to contain both of the adhesives.

<Acrylic acid alkyl ester copolymer>
The acrylic acid alkyl ester-based copolymer (non-aqueous pressure-sensitive adhesive base) constituting the non-aqueous acrylic pressure-sensitive adhesive has an alkyl ester having 2 to 9 carbon atoms as a component that exhibits adhesive strength, and is homopolymerized. A monomer having a glass transition temperature (Tg) of -55 ° C. (218K) or less when allowed to grow, and a polymer having a Tg of 8 to 165 ° C. (281-438K) when homopolymerized as a component for improving cohesiveness. It is a copolymer composed of a monomer having a above-mentioned monomer and a monomer having a functional group such as a cross-linking point such as a carboxyl group or a hydroxy group if necessary (an example of the monomer is given in Table 1).
The acrylic acid alkyl ester-based copolymer used in the present invention contains monomer A, which is a polymer having a glass transition temperature (Tg) of 270 K or more when homopolymerized, and a glass transition temperature (Tg) of 220 K or less when homopolymerized. It is a copolymer of a monomer mixture composed of monomer B which becomes a polymer. The upper limit of the glass transition temperature Tg of the homopolymer of the monomer A is about 500 K, and the lower limit of the glass transition temperature Tg of the homopolymer of the monomer B is about 200 K.

It should be noted that homopolymers obtained by polymerizing only monomers that exhibit adhesive strength are said to have high adhesive strength but weak mechanical strength, and generally, copolymerization with a monomer that improves cohesive strength improves mechanical strength. The coalescence is used as an adhesive.
As listed as the monomer exhibiting the adhesive strength shown in Table 1 above, in the present invention, as a monomer having a higher adhesive strength, acrylic acid having a Tg of 220 K or less when the monomer is homopolymerized (homopolymer). Butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isononyl acrylate and the like are used. Of these, butyl acrylate and 2-ethylhexyl acrylate are preferable, and among them, 2-ethylhexyl acrylate, which has a proven track record as a pharmaceutical additive and has high adhesive strength (low homopolymer Tg), can be preferably used. ..
Examples of the monomers that improve the cohesiveness (the Tg of the homopolymer is 270 K or more) include the monomers listed in Table 1. Among these, methyl acrylate, methyl methacrylate, ethyl methacrylate and n-butyl methacrylate are preferable. In the present invention, methyl acrylate, which has high mechanical strength and does not significantly reduce the adhesiveness (the Tg of the homopolymer is relatively low), is particularly preferable.

As mentioned in the prior art, as a commercially available acrylic acid alkyl ester-based copolymer used for a patch, Nicazole (registered trademark) TS-620 (methyl acrylate / acrylic) manufactured by Nippon Carbide Co., Ltd. 2-Ethylhexyl acid copolymer resin emulsion). The methyl acrylate / 2-ethylhexyl acrylate copolymer resin emulsion is a product listed in the Pharmaceutical Additives Regulations.
The present inventors cannot obtain the desired adhesive strength with Nicazole TS-620 (methyl acrylate / 2-ethylhexyl acrylate copolymer resin emulsion), which has been used in conventional water-containing patches. Considering that the adhesive strength decreases after the water from the pressure-sensitive adhesive layer volatilizes, the change of the copolymerization ratio of the above-mentioned copolymer was examined.
Then, in the above copolymer, when the polymerization ratio of the monomer having a Tg of the homopolymer of 270 K or more, that is, methyl acrylate was variously changed, as shown in the results of Examples described later, the Tg of the homopolymer was 270 K or more. For the first time, it was confirmed that a system using a copolymer in which the amount of the monomer (methyl acrylate or the like) to be used is 30% by mass or more can maintain the adhesive strength even when the pressure-sensitive adhesive layer is aerated. Further, if the blending amount of the monomer (methyl acrylate, etc.) having a Tg of homopolymer of 270 K or more exceeds 50% by mass, the emulsion aggregates and precipitates, making it difficult to redisperse. Therefore, the upper limit is 50% by mass. It was as follows.

In the pressure-sensitive adhesive layer of the water-containing patch of the present invention, the blending amount of the acrylic acid alkyl ester-based copolymer (in the case of an emulsion, the amount converted into solid content) is based on the total mass of the pressure-sensitive adhesive layer of the water-containing patch. For example, it can be 0.1% by mass or more and 30% by mass or less, 1.0% by mass or more and 15% by mass or less, and 5.0% by mass or more and 10% by mass or less.
Further, the mixing ratio with the acrylic hydrophilic pressure-sensitive adhesive, which will be described later, is, for example, in terms of mass ratio, acrylic acid alkyl ester-based copolymer: acrylic-based hydrophilic pressure-sensitive adhesive = 10: 1 to 1:10, the same = 5 :. It can be 1 to 1: 5, the same = 3: 1 to 1: 2, the same = 2: 1 to 1: 1 and the like.

<Active ingredient>
The pressure-sensitive adhesive layer in the water-containing patch of the present invention optionally contains an active ingredient. When the active ingredient is not contained, the water-containing patch of the present invention can be used as a keloid-like skin covering material, a cushioning material for protecting callus, flesh blister, and the like.
When the pressure-sensitive adhesive layer contains an active ingredient, it contains a physiologically active substance. The physiologically active substance is not particularly limited as long as it has transdermal absorbability and exhibits pharmacological activity when administered into the body, and may be a water-soluble substance or a fat-soluble substance.
Physiologically active substances include, for example, non-steroidal anti-inflammatory agents such as fervinac, flurbiprofen, diclofenac, diclofenac sodium, methyl salicylate, glycol salicylate (ethylene glycol salicylate), indomethacin, ketoprofen, ibuprofen, or esters thereof; diphenhydramine. , Antihistamines such as chlorpheniramine; analgesics such as aspirin, acetaminophen, ibuprofen, sodium loxoprofen; local anesthetics such as lidocaine and diclofenac; muscle relaxants such as schisametonium chloride; antifungal agents such as clotrimazole; Anti-inflammatory agents such as; vasodilators such as nitroglycerin and isosorbide nitrate; vitamins such as vitamin A, vitamin E (tocopherol), tocopherol acetate, vitamin K, octothiacin, riboflavin butyrate, prostaglandins; Examples include extracts, nonylate vanillylamide, capsaicin, l-menthol, dl-camfur and the like. The physiologically active substance may be used alone or in combination of two or more.

The blending amount of the above active ingredient can be appropriately determined depending on the type thereof. For example, 0.1% by mass or more and 30% by mass or less, or 0.5% by mass or more and 15 based on the total mass of the pressure-sensitive adhesive layer of the water-containing patch. It can be mass% or less.

<Acrylic hydrophilic adhesive>
The pressure-sensitive adhesive layer of the water-containing patch of the present invention contains an acrylic hydrophilic pressure-sensitive adhesive.
Examples of the acrylic hydrophilic pressure-sensitive adhesive include water-soluble (meth) acrylic polymers. The water-soluble (meth) acrylic polymer is a polymer obtained by polymerizing a (meth) acryloyl group-containing monomer having a functional group (hydrophilic group) having water solubility, and is blended with water in the pressure-sensitive adhesive layer. , Demonstrates stickiness. Examples of the water-soluble (meth) acrylic polymer include homopolymers such as polyacrylic acid and neutralized products of polyacrylic acid; and copolymers such as N-vinylacetamide / sodium acrylate copolymer resin.
The above-mentioned neutralized polyacrylic acid may be a completely neutralized polyacrylic acid, a partially neutralized polyacrylic acid, or a mixture thereof. The neutralized polyacrylic acid means a polyacrylic acid salt, and for example, sodium salt, potassium salt, calcium salt, ammonium salt and the like can be used.

The blending amount of the acrylic hydrophilic pressure-sensitive adhesive may be, for example, 0.1% by mass or more and 10% by mass or less, and 1% by mass or more and 8% by mass or less, based on the total mass of the pressure-sensitive adhesive layer of the water-containing patch. can.

<Organic solvent>
The organic solvent blended in the pressure-sensitive adhesive layer of the water-containing patch of the present invention may have a role of assisting the dissolution of the active ingredient such as a drug and preventing the active ingredient from precipitating from the pressure-sensitive adhesive layer. As such an organic solvent (solubilizing agent), crotamitone; N-methyl-2-pyrrolidone; polyalkylene glycol such as macrogly 400 (polyethylene glycol) and polybutylene glycol; diethyl adipate, diisopropyl adipate, diethyl sebacate , Fatty ester such as diisopropyl sebacate, isopropyl myristate, isopropyl palmitate, oleyl oleate; sorbitan esters such as polyoxyalkylene fatty acid ester; polyhydric alcohols such as 1,3-butanediol; dimethylformamide; dimethylsulfoxide, etc. Can be mentioned. These can be used alone or in combination of two or more.

The blending amount of the organic solvent can be, for example, 0.1% by mass or more and 20% by mass or less based on the total mass of the pressure-sensitive adhesive layer of the water-containing patch.

<Crosslinking agent>
Examples of the cross-linking agent blended in the pressure-sensitive adhesive layer of the water-containing patch of the present invention include polyvalent metal salts, and among them, polyvalent metal compounds containing aluminum. As an example, hydroxides such as aluminum hydroxide and alumina magnesium hydroxide; aluminum chloride, aluminum sulfate, potassium aluminum sulfate, aluminum glycinate (dihydroxyaluminum aminoacetal), dihydroxyaluminum aminoacetate, synthetic aluminum silicate, dry hydroxide. Positive salts of inorganic or organic acids such as aluminum gel, kaolin and aluminum stearate or basic salts thereof; re-salts such as aluminum myoban; aluminate such as sodium aluminate; inorganic aluminum complex salts and organic aluminum chelate compounds. Examples thereof include polyvalent metal compounds such as synthetic hydrotalcite, magnesium aluminate aluminate, and magnesium aluminate metasilicate, and these can be used alone or in combination of two or more.

The amount of the cross-linking agent to be blended may be appropriately selected in consideration of the degree of cross-linking that may contribute to the residue of the adhesive on the skin and the adhesiveness. Based on the total mass of the pressure-sensitive adhesive layer of the water-containing patch, for example, 0.01% by mass or more and 6.0% by mass or less, 0.01% by mass or more and 4.0% by mass or less, or 0.01% by mass or more. The range of 2.0% by mass or less can be mentioned.

<Organic acid>
Examples of the organic acid blended in the pressure-sensitive adhesive layer of the water-containing patch of the present invention include citric acid, lactic acid, tartaric acid, gluconic acid, glycolic acid, malic acid, fumaric acid, metasulfonic acid, maleic acid, acetic acid and the like. , These can be used alone or in combination of two or more.
The blending amount of the organic acid can be, for example, in the range of 0.01% by mass or more and 5% by mass or less based on the total mass of the pressure-sensitive adhesive layer of the water-containing patch.

<Water>
As described above, the water-containing patch of the present invention contains water (moisture) in the pressure-sensitive adhesive layer. In the present specification, the "water" contained in the pressure-sensitive adhesive layer includes not only water separately added as water when the pressure-sensitive adhesive layer is formed, but also water contained in the form of an emulsion or an aqueous solution. The blending amount of water is not particularly limited, but based on the total mass of the pressure-sensitive adhesive layer of the water-containing patch, for example, 10% by mass or more and 90% by mass or less, 15% by mass or more and 70% by mass or less, 20% by mass or more and 50% by mass. It can be in the range of% or less. It should be noted that this water content is a value at the time of preparing the patch or before the patch is applied, and is not limited to the case where water volatilizes from the adhesive layer with the progress of the application.

<Other optional ingredients>
The pressure-sensitive adhesive layer of the water-containing patch of the present invention has, as other optional components, a water-soluble polymer compound, a surfactant, a wetting agent, a stabilizer, an antioxidant, an inorganic powder, a colorant, a fragrance, and an antiseptic. Ingredients that can be generally blended in the pressure-sensitive adhesive layer of conventional water-containing patches (pups) or non-aqueous patches (tapes), such as agents, can be blended. These optional components can be used alone or in combination of two or more.

<Water-soluble polymer compound>
Examples of the water-soluble polymer compound include gelatin, canten, polyvinyl alcohol, polyvinylpyrrolidone, propylene carbonate, carboxymethyl cellulose, carmellose sodium, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, methyl cellulose, sodium alginate, and maleic anhydride. Examples include polymers and carrageenan. These can be used alone or in combination of two or more.
The blending amount of the water-soluble polymer compound is usually 1.0% by mass or more and 30% by mass or less, 3.0% by mass or more and 20% by mass or less, based on the total mass of the pressure-sensitive adhesive layer of the water-containing patch. Alternatively, it can be in the range of 5.0% by mass or more and 20% by mass or less.

<Surfactant>
Examples of the surfactant include polyoxyethylene fatty acid esters such as polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, polyethylene glycol distearate, polyethylene glycol dilate, and polypropylene glycol dioleate. Sorbitan monocaprilate, sorbitan monolaurate, sorbitan monomillistate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monoolate, sorbitan triolate, sorbitan monosesquiolate, and Solbitan fatty acid esters such as these ethylene oxide adducts; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monoolate, Polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan triolate and polyoxyethylene sorbitan triisostearate; polyoxyethylene dodecyl ether (polyoxyethylene lauryl ether), polyoxyalkylene lauryl ether, polyoxyethylene tridecyl ether, Polyoxyalkylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene behenyl ether, polyoxyethylene-2-ethylhexyl ether, polyoxyethylene iso Polyoxyethylene alkyl ethers such as decyl ether; polyoxyethylene alkylphenol ethers such as polyoxyethylene styrene phenyl ethers, polyoxyethylene nonylphenyl ethers, polyoxyethylene distyrene phenyl ethers, and polyoxyethylene tribenzylphenyl ethers; Glycerin fatty acid esters such as glycerin stearate and glycerin monooleate; nonionic surfactants such as polyethylene glycol, polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, and lecithin can be mentioned. These can be used alone or in combination of two or more.
The blending amount of these surfactants is, for example, 0.001% by mass or more and 10% by mass or less, 0.01% by mass or more and 5% by mass or less, based on the total mass of the pressure-sensitive adhesive layer of the water-containing patch. be able to.

<Wetting agent>
A wetting agent (also referred to as a moisturizer) can be blended in the pressure-sensitive adhesive layer of the water-containing patch of the present invention in order to suppress evaporation of water over time. Examples of the wetting agent include concentrated glycerin, D-sorbitol, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, liquid paraffin, 1,3-propanediol, 1,4-butanediol, martitol, and xylitol. Valuable alcohol can be mentioned. These can be used alone or in combination of two or more.
The amount of the wetting agent is usually, for example, 1.0% by mass or more and 70% by mass or less, 5.0% by mass or more and 60% by mass or less, or 10% by mass, based on the total mass of the pressure-sensitive adhesive layer of the water-containing patch. It can be in the range of% or more and 60% by mass or less.

<Stabilizer>
A stabilizer can be added to the pressure-sensitive adhesive layer of the water-containing patch of the present invention in order to improve the storage stability of the active ingredient and the like against light (particularly ultraviolet rays), heat or oxygen.
Examples of the stabilizer include sodium edetate (ethylenediaminetetraacetic acid disodium salt); an antioxidant such as dibutylhydroxytoluene (BHT); an ultraviolet absorber such as a benzoylmethane derivative; and the like.
The blending amount of the stabilizer is usually in the range of 0.01% by mass or more and 1% by mass or less based on the total mass of the pressure-sensitive adhesive layer of the water-containing patch.

<Inorganic powder>
As the inorganic powder, calcium carbonate, magnesium carbonate, silicate, zinc oxide, titanium oxide, magnesium sulfate, calcium sulfate and the like can be blended.

[Support]
Examples of the support used for the water-containing patch of the present invention include flexible supports such as films, non-woven fabrics, Japanese paper, cotton cloths, knitted cloths, woven cloths, and laminated composites of non-woven fabrics and films. These supports are preferably made of a flexible material that can adhere to the skin and can follow the movement of the skin, and a material that can suppress the occurrence of skin irritation after long-term application. Examples of the material of these supports include polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polystyrene, nylon, cotton, acetate rayon, rayon, rayon / polyethylene terephthalate composite, polyacrylonitrile, polyvinyl alcohol, and the like. Acrylic polyurethane, ester polyurethane, ether polyurethane, styrene-isoprene-styrene copolymer, styrene-butadiene-styrene copolymer, styrene-ethylene-propylene-styrene copolymer, styrene-butadiene rubber, ethylene-vinyl acetate Examples thereof include copolymers and cellophane as essential components.

Further, by coloring the support such as cloth to a color tone such as skin color with a coloring agent, it is possible to reduce the difference from the skin color at the time of application. In addition, the form of a plastic film having excellent transparency can be adopted in that the color tone of the skin under attachment can be easily seen through.

The thickness of the support is usually about 5 μm to 1 mm. When the support is a cloth, its thickness is preferably 50 μm to 1 mm, more preferably 100 to 800 μm, and further preferably 200 to 700 μm. When the support is a plastic film, its thickness is preferably 10 to 300 μm, more preferably 12 to 200 μm, and even more preferably 15 to 150 μm. When the thickness of the support is as thin as about 5 μm to 30 μm, if a peelable carrier film layer is provided on the surface opposite to the adhesive layer formed on the support, the handleability as a patch can be improved. It is preferable because it improves. However, if the thickness of the support is smaller than 5 μm, the strength and handleability of the patch will decrease, making it difficult to stick to the skin, tearing due to contact with other members, or contact with water for bathing, etc. Contact may cause it to peel off the skin in a short time. In addition, if the thickness of the support is too large (more than 1 mm), it becomes difficult for the patch to follow the movement of the skin, and it becomes easy to form a trigger for peeling off at the edge of the patch, so that the patch can be peeled off from the skin in a short time. There is a risk of peeling or an increase in discomfort during sticking.
When the support is a film, one or both sides of the support may be sandblasted, corona-treated, or the like for the purpose of improving the anchoring property of the adhesive and the support.
Further, in order to facilitate removal from the packaging material, unevenness may be provided on one side or both sides of the support by a method other than sandblasting.

[Peeling liner]
The release liner (also referred to as release layer / release paper) used in the water-containing patch of the present invention is preferably made of a material that does not easily absorb or adsorb drugs or the like in the pressure-sensitive adhesive layer, and is commonly used in the technical field of patches. Can be used.
For example, plastic films such as polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polypropylene (non-stretched, stretched, etc.), polyethylene, polyurethane, polyvinyl chloride, polystyrene, etc .; high-quality paper, glassin paper, parchment paper, craft Paper such as paper and synthetic paper; peeling processed paper in which the plastic film, paper or synthetic paper, synthetic fiber and the like are coated with a release agent having peeling performance such as silicone resin and fluororesin; aluminum foil; various films and sheets are used. Examples thereof include colorless or colored sheets such as laminated laminated paper and laminated peeled paper obtained by coating the laminated paper with a release agent. The release liner can also be provided with irregularities so that it can be easily taken out from the packaging material.
The thickness of these release liners is not particularly limited, but is usually in the range of 10 μm to 1 mm, for example, 20 μm to 500 μm, preferably 40 μm to 200 μm.
The shape of the release liner can be a square, a rectangle, a circle, or the like, and if desired, a shape with rounded corners can be used. The size may be the same as or slightly larger than the size of the support in the pasting material. The peeling liner may be composed of one or a plurality of strips, and the cut may be formed of a straight line, a wavy line, or a sewing machine line, or a part of the peeling liners may overlap each other.

[Manufacturing method of hydrous patch]
The water-containing patch of the present invention can be produced by using a conventionally known method. For example, it can be manufactured through the following steps i) or ii).
i) A step of applying the pressure-sensitive adhesive layer forming composition on the support to form the pressure-sensitive adhesive layer, and a step of bonding the pressure-sensitive adhesive layer formed on the support and the release liner.
ii) A step of applying the pressure-sensitive adhesive layer forming composition on the release liner to form the pressure-sensitive adhesive layer, and a step of bonding the pressure-sensitive adhesive layer formed on the release liner and the support.
The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is usually 10 μm to 1000 μm, for example, about 20 μm to 800 μm.

The pressure-sensitive adhesive layer-forming composition includes various components contained in the above-mentioned pressure-sensitive adhesive layer: active ingredient, acrylic hydrophilic pressure-sensitive adhesive, acrylic acid alkyl ester-based copolymer, organic solvent, cross-linking agent, organic acid and water. It is a semi-solid composition which contains, and can further contain any other component.

The water-containing patch of the present invention is characterized in that the adhesive strength is maintained when it is water-containing and when it is dried (after water volatilization), and it is also a patch having low skin irritation.
Here, the skin irritation can be evaluated by, for example, the individual average value (average PII) of the skin primary irritation index (PII) by the Draize method, and the patch of the present invention is, for example, 1. It can be .40 or less.
The primary skin irritation index (PII) (Primary Irrationation Index) by the above-mentioned Draize method is an evaluation method using a rabbit lesion. Specifically, after the sample (test substance) is attached to the back of the rabbit and the sample is removed after a predetermined time, the reaction (the state of erythema and the size of edema) at the affixed site after the elapse of a predetermined time is 0 to 0. It is a value that is evaluated on a scale of 4 and is shown as the total value of the two evaluation values (the average value if there are multiple judgment times), and the individual average value (average P.I. I.I.) is calculated and evaluated.
In the present invention, after the sample (hydrous-based patch) is pasted for 24 hours, the patch is observed after a predetermined time has passed after the sample is removed, and the stimulus reaction is scored. 30 minutes and 24 hours after the removal. Based on the stimulus response scores in I. I. To evaluate skin irritation.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

<Preparation of patch>
The patches of Examples and Comparative Examples were produced by the following procedure.

Example 1:
1.5 parts by mass of polyvinyl alcohol was dissolved in 20 parts by mass of purified water (aqueous phase).
Next, 1.25 parts by mass of ethylene glycol salicylate and 1 part by mass of L-menthol were dissolved by adding 1 part by mass of Macrogol (registered trademark) 400 (manufactured by Sanyo Chemical Industries, Ltd.) (oil phase).
Further, 4 parts by mass of a partially neutralized polyacrylic acid, 4 parts by mass of sodium carmellose, and 0.25 parts by mass of dihydroxyaluminum aminoacetate were uniformly dispersed in 25 parts by mass of concentrated glycerin (glycerin phase).
Aqueous phase, methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion (31.1% by mass of methyl acrylate in the copolymer, trace amount of polyoxyethylene nonylphenyl ether (30EO) contained in the emulsion) in the stirrer ) 7 parts by mass, 0.20 parts by mass of sodium edetate hydrate, and 30 parts by mass of a 70% aqueous solution of D-sorbitol were added in this order, and the mixture was uniformly dispersed or dissolved. The oil phase and the glycerin phase were added in this order and kneaded uniformly. Further, 1 part by mass of lactic acid was added, and the mass was corrected with purified water so that the total mass became 100 parts by mass, and then uniformly kneaded under degassing conditions to obtain the pressure-sensitive adhesive layer forming composition of Example 1. ..
The obtained pressure-sensitive adhesive layer-forming composition was spread on the silicone surface of a liner (pete (75 μm) treated with silicone on one side) with a spreading machine adjusted to a slit width of 0.5 mm, and a knit support (made of polyester) was spread. After laminating, it was aged at 50 ° C. for 1 week. After aging, it was punched into an arbitrary shape to obtain the formulation of Example 1.

Example 2:
Example 1 except that the methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion (methyl acrylate compounding amount: 31.1% by mass) was changed to an emulsion having a methyl acrylate compounding amount of 40.8% by mass. In the same manner as above, the formulation of Example 2 was obtained.

Example 3:
Example 1 except that the methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion (methyl acrylate compounding amount: 31.1% by mass) was changed to an emulsion having a methyl acrylate compounding amount of 46.7% by mass. In the same manner as above, the formulation of Example 3 was obtained.

Example 4:
Methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion, methyl methacrylate / 2-ethylhexyl acrylate copolymer emulsion (30.0% by mass of methyl methacrylate in the copolymer) 10 parts by mass (of the copolymer) The preparation of Example 4 was obtained in the same manner as in Example 1 except that the solid content conversion value was changed to 4.34 parts by mass).

Example 5:
Methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion, ethyl methacrylate / 2-ethylhexyl acrylate copolymer emulsion (30.0% by mass of ethyl methacrylate in the copolymer), 10 parts by mass (of the copolymer) The preparation of Example 5 was obtained in the same manner as in Example 1 except that the solid content conversion value was changed to 4.14 parts by mass).

Example 6:
Methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion, n-butyl methacrylate / 2-ethylhexyl acrylate copolymer emulsion (30.0% by mass of n-butyl methacrylate in the copolymer) 10 parts by mass ( The preparation of Example 6 was obtained in the same manner as in Example 1 except that the solid content conversion value of the copolymer was changed to 4.34 parts by mass).

Example 7:
Methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion, methyl acrylate / n-butyl acrylate copolymer emulsion (30.0% by mass of methyl acrylate in the copolymer), 10 parts by mass (of the copolymer) The preparation of Example 7 was obtained in the same manner as in Example 1 except that the solid content conversion value was changed to 4.54 parts by mass).

Example 8:
The methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion (methyl acrylate compounding amount: 31.1% by mass) is changed to an emulsion having a methyl acrylate compounding amount of 46.7% by mass, and the compounding amount is changed to 5% by mass. The preparation of Example 8 was obtained in the same manner as in Example 1 except that the part (the solid content conversion value of the copolymer was 2.95 parts by mass) was changed.

Example 9:
The methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion (methyl acrylate compounding amount: 31.1% by mass) is changed to an emulsion having a methyl acrylate compounding amount of 46.7% by mass, and the compounding amount is changed to 10% by mass. The preparation of Example 9 was obtained in the same manner as in Example 1 except that the part (the solid content conversion value of the copolymer was changed to 5.9 parts by mass).

Example 10:
The methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion (methyl acrylate compounding amount: 31.1% by mass) is changed to an emulsion having a methyl acrylate compounding amount of 46.7% by mass, and the compounding amount is 12% by mass. The preparation of Example 10 was obtained in the same manner as in Example 1 except that the part (the solid content conversion value of the copolymer was 7.08 parts by mass) was changed.

Example 11:
The methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion (methyl acrylate compounding amount: 31.1% by mass) is changed to an emulsion having a methyl acrylate compounding amount of 46.7% by mass, and the compounding amount is changed to 15% by mass. The preparation of Example 11 was obtained in the same manner as in Example 1 except that the part (the solid content conversion value of the copolymer was changed to 8.85 parts by mass).

Example 12:
The methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion (methyl acrylate compounding amount: 31.1% by mass) is changed to an emulsion having a methyl acrylate compounding amount of 46.7% by mass, and the compounding amount is changed to 20% by mass. The preparation of Example 12 was obtained in the same manner as in Example 1 except that the part (the solid content conversion value of the copolymer was changed to 11.8 parts by mass).

Comparative Example 1:
Example 1 except that the methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion (methyl acrylate compounding amount: 31.1% by mass) was changed to an emulsion having a methyl acrylate compounding amount of 14.7% by mass. In the same manner as above, the formulation of Comparative Example 1 was obtained.

Comparative Example 2:
Example 1 except that the methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion (methyl acrylate compounding amount: 31.1% by mass) was changed to an emulsion having a methyl acrylate compounding amount of 27.0% by mass. In the same manner as above, the formulation of Comparative Example 2 was obtained.

Comparative Example 3:
The same as in Comparative Example 1 except that the compounding amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion (methyl acrylate compounding amount: 14.7% by mass) was changed to 10 parts by mass (10% by mass). The preparation of Comparative Example 3 was obtained.

Comparative Example 4:
The same as in Comparative Example 1 except that the compounding amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion (methyl acrylate compounding amount: 14.7% by mass) was changed to 15 parts by mass (15% by mass). The preparation of Comparative Example 4 was obtained.

Comparative Example 5:
The same as in Comparative Example 1 except that the compounding amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion (methyl acrylate compounding amount: 14.7% by mass) was changed to 20 parts by mass (20% by mass). The preparation of Comparative Example 5 was obtained.

Comparative Example 6:
The same as in Comparative Example 1 except that the compounding amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion (methyl acrylate compounding amount: 14.7% by mass) was changed to 25 parts by mass (25% by mass). The preparation of Comparative Example 6 was obtained.

In the blending amounts of the copolymerized emulsions in Examples 1 to 3, Comparative Example 1 and Comparative Example 2, the solid content conversion value of the copolymer is based on the mass of all the components constituting the pressure-sensitive adhesive layer. 4.13% by mass, Examples 4 and 6 are 4.34% by mass, Examples 5 and 7 are 4.14% by mass, Example 8 is 2.95% by mass, and Example 9 5.90% by mass, Example 10 was 7.08% by mass, Example 11 was 8.85% by mass, Example 12 was 11.80% by mass, and Comparative Example 3 was 5.90% by mass. %, Comparative Example 4 was 8.85% by mass, Comparative Example 5 was 11.80% by mass, and Comparative Example 6 was 14.75% by mass.

Reference Example 1, Reference Example 2:
A commercially available tape agent (Fatus (registered trademark) 5.0, Hisamitsu Pharmaceutical Co., Ltd., lot number: SC08T) is used as the preparation of Reference Example 1, and a commercially available poultice (Vantelin Kowa New Mini Pad,) is used as the preparation of Reference Example 2. Kowa Co., Ltd., lot number: NA640) was used for various tests described later.

Test Example 1 (Adhesive strength test)
For each of the formulations of Examples 1 to 12, Comparative Examples 1 to 6, and Reference Example 1 and Reference Example 2, the initial (hereinafter referred to as “water-containing”, the formulations of Examples and Comparative Examples are immediately after production. The preparations of the reference example are the ones immediately after opening the product packaging) and when dried overnight at 50 ° C. (hereinafter referred to as "drying"), both of which have the liner peeled off (the adhesive layer is exposed). The tilted ball tack adhesive strength (held overnight at 50 ° C.) was carried out according to the Japanese Pharmacopoeia General Test Method 6.12 Adhesive Strength Test Method 3.2 Tilt Ball Tuck Test Method.
The results obtained are shown in Tables 2 and 3.

Test Example 2 (Plastic between plasters and reattachment test)
The interplasia peelability and reattachment property were evaluated for each of the formulations of Examples 1 to 12, Comparative Examples 1 to 6, and Reference Example 1 and Reference Example 2.
The obtained results are also shown in Tables 2 and 3.
1) Peelability between plasters The liner of each formulation cut into a size of 5 cm × 5 cm was peeled off, each formulation was folded in half, the adhesive layers were firmly adhered to each other, and the mixture was allowed to stand for 30 seconds. Then, the bonded portion was peeled off and evaluated according to the following criteria (N = 3).
◯: Easily peeled Δ: Peeled but deformed ×: Not peeled 2) Reattachment The liner of each preparation (10 cm × 7 cm) was peeled off and attached to the inside of the human upper arm. After 30 seconds had passed, it was peeled off, attached again to another part of the forearm, and evaluated according to the following criteria (N = 3).
◯: With reattachment Δ: Weak reattachment ×: No reattachment

<Test results>
As shown in Table 2, among the monomers constituting the acrylic acid alkyl ester-based copolymer, the blending amount of the monomer A in which the Tg of the homopolymer of the monomer is 270 K or more, that is, methyl acrylate / acrylic acid 2- Blending amount of methyl acrylate in the ethylhexyl copolymer resin, blending amount of methyl methacrylate in the methyl methacrylate / 2-ethylhexyl acrylate copolymer resin, blending of ethyl methacrylate in the ethyl methacrylate / 2-ethylhexyl acrylate copolymer resin Amount, amount of n-butyl methacrylate in n-butyl methacrylate / 2-ethylhexyl acrylate copolymer resin, amount of methyl acrylate in methyl acrylate / n-butyl acrylate copolymer resin is 30% by mass or more In the preparations of Examples 1 to 9 using the resin emulsion, the ball tack adhesive strength immediately after production (when water is contained) is a commercially available tape agent (Reference Example 1) and a commercially available poultice agent (Reference Example 2). Although the result was slightly lower than that (see Table 3), the ball tack adhesive strength at the time of drying (drying at 50 ° C. overnight) was almost the same as that of a commercially available tape agent. Further, as shown in the results of Examples 3 and 8 to 12, the blending amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer resin (methyl acrylate blending amount: 46.7% by mass) was increased. According to this, the adhesive strength increases both after the Manufacturing Agency (when water is contained) and when it is dried. In particular, in Examples 10 to 12, even when water is contained, the adhesive strength is compared with the commercially available products shown in Reference Example 1 and Reference Example 2. The adhesive strength was equal to or higher than that of the above. Further, in any of the examples, the pressure-sensitive adhesive layers can be easily peeled off even when they are adhered to each other, and re-adhesiveness is also recognized. Was kept.

On the other hand, the preparations (Comparative Examples 1 and 2) in which the amount of the monomer A compounded, that is, the amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer resin compounded in methyl acrylate is less than 30% by mass, are balls at the time of drying. The result was that the tack adhesive strength was lower than that of Examples 1 to 12. As described above, when the blending amount of methyl acrylate exceeds 50% by mass, the emulsion aggregates and precipitates, making redispersion difficult, and the upper limit of the blending amount is 50% by mass.
Further, with respect to the methyl acrylate / 2-ethylhexyl acrylate copolymer resin in which the amount of methyl acrylate used in Comparative Example 1 was 14.7% by mass, the amount of the copolymerized resin was 7% by mass to 25% by mass. The preparations (Comparative Example 1, Comparative Example 3 to Comparative Example 6) increased in the range of (4.13% by mass to 14.75% by mass as solid content) were carried out from Examples 1 to both when they were water-containing and when they were dried. The result was that the ball tack adhesive strength was lower than that of the preparation of Example 3.
The preparations of Comparative Examples 1 to 4 were evaluated for the same interplasia peeling property and reattachment property as the preparations of Examples, but the formulations of Comparative Example 5 and Comparative Example 6 were evaluated between the plasters. Both the releasability and the reattachment property were evaluated to be less than the pharmaceutical product of the example, and there was a tendency that these performances were rather deteriorated by increasing the blending amount of the acrylic acid alkyl ester-based copolymer.

Then, the formulation of Reference Example 1, which is a commercially available formulation, was evaluated as not peeling off when the pressure-sensitive adhesive layers were adhered to each other and having no reattachability.
Further, in the formulation of Reference Example 2, after the pressure-sensitive adhesive layers were adhered to each other, the adhesive layer was peeled off but deformed, and the adhesive layer was reattached but had weak adhesiveness.

From the above results, among the monomers constituting the acrylic acid alkyl ester-based copolymer, the amount of monomer A (methyl acrylate, etc.) in which the Tg of the homopolymer of the monomer is 270 K or more is 30 to 50% by mass. By adopting a certain acrylic acid alkyl ester-based copolymer (methyl acrylate / 2-ethylhexyl acrylate copolymer resin, etc.), it is possible to obtain a formulation having excellent adhesive strength not only when it contains water but also when it is dried. It was also confirmed that the preparation is easy to peel off between the plasters and has re-adhesion.

Test Example 3 (Primary skin irritation index test)
The primary skin irritation index (PII) test based on the Draize method was performed by the following method. For details on the Draize method, see Draize JH, Woodard, G. and Calvery, HO (1944): Methods for the study of irritation and Toxicity of substances applied topically to the skin and mocous membranes, J. Pharmacol Exp. Ther., 82. : 377-390).

The preparations of Example 3 and Comparative Example 1 were punched to 15 mmφ, the release liner was peeled off, and then the hair was cut and shaved, and the white rabbit (17 weeks old, male, JW) (N = 3) was attached to the back of the white rabbit. A moisture-permeable catelype (transparent adhesive film, Nichiban Co., Ltd.) was attached over the prepared product so as to cover the entire product.
After application for 24 hours, the caterip and the preparation are peeled off, the application part of the preparation is wiped with purified water, and the skin condition of the application part 30 minutes after the peeling and after 24 hours is observed, and the drays shown in Table 4 are observed. The stimulus response was scored according to the criteria of.
In addition, based on the scoring values 30 minutes and 24 hours after the preparation was peeled off, the scoring average value after 30 minutes or 24 hours, and the individual average value from the skin primary irritation index (PI) of each individual. A mean skin primary irritation index (mean PII) was obtained.
DNBC (2,4-dinitrochloro-benzene) was used as a positive control, a commercially available poultice (Nobi Nobi Salonship (registered trademark) FH warmth, Hisamitsu Pharmaceutical Co., Ltd.) was used as the preparation of Reference Example 3, and the preparation of Reference Example 4 was used. Using a commercially available poultice (Halix (registered trademark) 55EX warmth, Lion Co., Ltd.), the same primary skin irritation index test was performed, and the average scoring value after 30 minutes or 24 hours was obtained for each individual. The skin primary irritation index (PI) and the skin primary irritation index (mean PII) were obtained.
The results obtained are shown in Table 5.

As shown in Table 5, the average primary irritation index (mean PII) in the formulations of Example 3, Comparative Example 1, Reference Example 3 and Reference Example 4 was 0.7 to 1.0, which was mild. The result was that it was a stimulus for.
On the other hand, the mean primary irritation index (mean PII) in the positive control was 2.8, which was moderate irritation.

From the results of the above examples, according to the present invention, among the monomers constituting the acrylic acid alkyl ester-based copolymer, the content of monomer A (methyl acrylate, etc.) in which the Tg of the homopolymer of the monomer is 270 K or more. By blending 30 to 50% by mass of an acrylic acid alkyl ester-based copolymer (methyl acrylate / 2-ethylhexyl acrylate copolymer resin, etc.) in the pressure-sensitive adhesive layer of the water-containing patch, when it is water-containing and when it is dried. It was confirmed that it is possible to provide a patch having low skin irritation while maintaining high adhesiveness.

Claims (4)

A water-containing patch composed of a support, an adhesive layer provided on the support, and a release liner.
A water-containing patch in which the pressure-sensitive adhesive layer contains the following components 1) to 6) as essential components.
1) Acrylic-based hydrophilic pressure-sensitive adhesive 2) Acrylic acid alkyl ester-based copolymer which is a copolymer of a monomer mixture composed of monomer A and monomer B.
The monomer A is a polymer having a glass transition temperature (Tg) of 270 K or more when the monomer A is homopolymerized.
The monomer B is a monomer having a glass transition temperature (Tg) of 220 K or less when homopolymerized with the monomer B.
Acrylic acid alkyl ester-based copolymer 3) organic solvent 4) cross-linking agent 5) organic acid 6 in which the proportion of the monomer A is 30% by mass or more and 50% by mass or less with respect to the total mass of the monomer mixture. )water The monomer A is selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, vinyl acetate, acrylonitrile, acrylamide and styrene. At least one kind of monomer,
The monomer B is at least one monomer selected from the group consisting of butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate and isononyl acrylate.
The water-containing patch according to claim 1. The monomer A is at least one monomer selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl methacrylate and n-butyl methacrylate.
The monomer B is at least one monomer selected from the group consisting of 2-ethylhexyl acrylate and butyl acrylate.
The water-containing patch according to claim 2. The water-containing patch according to any one of claims 1 to 3, further comprising an active ingredient.