JP2003095929A - Plaster - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a plaster having a wrinkle-free supporter film. SOLUTION: This plaster is produced by laminating a primer layer and a water-containing adhesive layer serially on one side of the supporter film. The water-containing adhesive layer contains a hardly water soluble crosslinking agent and has a pH value of 3-7.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a patch, and more specifically, a patch having improved adhesiveness between a film-shaped support and a water-containing pressure-sensitive adhesive layer and having no wrinkles on the film-shaped support. Regarding

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
As a primer layer for adhering a film-shaped support and a hydrous pressure-sensitive adhesive layer, JP-A-7-97316 and JP-A-7-2
67851, JP-A-7-316043, JP-A-8-
A primer layer described in Japanese Patent Publication No. 1119856 has been proposed, and it is known that the adhesion between the two is improved by laminating the primer layer between the two.

However, the water-containing pressure-sensitive adhesive layers described therein use a fast-dissolving compound such as aluminum chloride or alum as a cross-linking agent, and since the cross-linking speed is high, wrinkles are formed on the film immediately after production. There was a cosmetic problem of entering.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a patch without wrinkles on a film-shaped support.

[0005]

Means for Solving the Problems and Embodiments of the Invention As a result of intensive investigations by the present inventors to solve the above problems,
It came to the attention that the rate of cross-linking can be slowed by adding a poorly water-soluble compound as a cross-linking agent to the hydrous pressure-sensitive adhesive layer, and as a result of further diligent studies, when the pH of the hydrous pressure-sensitive adhesive layer exceeds 7, the cross-linking rate becomes slow. Therefore, the primer layer swells with water in the water-containing pressure-sensitive adhesive layer, and wrinkles are formed in the film immediately after production. Therefore, by adjusting the pH of the pressure-sensitive adhesive layer to 3 to 7, the film-like support is wrinkled. The inventors have found that a patch free from the above can be obtained, and completed the present invention.

That is, according to the present invention, a primer layer and a water-containing pressure-sensitive adhesive layer are sequentially laminated on one surface of a film-like support, and the water-containing pressure-sensitive adhesive layer contains a poorly water-soluble crosslinking agent, and A patch having a pH value of 3 to 7 is provided.

Here, the sparingly water-soluble crosslinking agent is synthetic hydrotalcite, dihydroxyaluminum aminoacetate (aluminum glycinate), magnesium aluminate silicate, magnesium aluminometasilicate, synthetic aluminum silicate, dry aluminum hydroxide gel. ,
Magnesium oxide, aluminum oxide, calcium oxide, copper oxide, iron oxide, titanium oxide, magnesium silicate, magnesium carbonate, magnesium hydroxide, alumina hydroxide / magnesium, magnesium hydroxide / potassium aluminum sulfate coprecipitation product, hydroxylation aluminum·
More preferably, it is one or more selected from sodium hydrogencarbonate coprecipitate, calcium hydrogenphosphate, anhydrous calcium phosphate, a cationic polymer compound or salts thereof.

The present invention will be described in more detail below. In the patch of the present invention, a primer layer is laminated on one side of a film-like support, and a hydrous pressure-sensitive adhesive layer is further laminated on the primer layer. It is a thing. Here, the type of the film-shaped support of the present invention is not particularly limited, but usually a resin film is used as the support of the patch, and the support of the present invention is The type of the resin film is not particularly limited as long as it is a resin film that is usually used for the agent.

Examples of such a resin film include olefin films such as polyethylene (hereinafter PE) and polypropylene (hereinafter PP), ester films such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), Urethane films such as polyester polyurethane and polyether polyurethane, amide films such as nylon 12, polyether block amide copolymer, styrene films such as polystyrene, polyvinyl chloride film, ethylene-vinyl acetate copolymer Examples thereof include films and polyfluorocarbon films. These may be used alone or in a blend of two or more. The degree of polymerization of the above resin is not particularly limited, and those usually used as a support film for patches can be used.

The thickness of the film-like support of the present invention is not particularly limited, but it is usually 5 to 100 μm, preferably 10 to 75 μm. If the film is too thin, it may not be easy to handle as a patch, and if it is too thick, the desired transparency and stretchability may not be obtained.

The primer layer-laminated surface of the film-shaped support of the present invention may be subjected to corona discharge treatment, ozone
UV irradiation, plasma treatment, chromic acid treatment, flame treatment,
Hot air treatment, surface unevenness treatment, or the like may be performed.

The type of the primer layer laminated on one side of the film-like support of the present invention is not particularly limited, and examples thereof include a layer made of a hydrophilic polymer resin, more specifically. Is, for example, Japanese Patent Laid-Open No. 7-97316.
And a pressure-sensitive adhesive layer (primer layer) made of a (meth) acrylic acid alkyl ester-based polymer described in JP-A-7-267851, and a monoethylenically unsaturated radical-polymerizable mono- or dicarboxylic acid described in JP-A-7-267851. Primer layer composed of copolymer with alkyl (meth) acrylate, amino group-containing monoethylenically unsaturated radically polymerizable mono- or dicarboxylic acid and (meth) acrylic described in JP-A-7-316043 Primer layer composed of copolymer with acid alkyl ester
Of the water-dispersible modified saturated polyester resin obtained by polymerizing 55 to 20 mass% of a vinyl monomer in the presence of 45 to 80 mass% of the water dispersible saturated polyester resin described in JP-A-119856. It is preferable to use a primer layer made of an aqueous dispersion or a primer layer made of a copolymer of (meth) acrylic acid ester containing an amino group and styrene.

The layer thickness of the primer layer is not particularly limited, but is usually 0.1 to 30 μm, preferably 0.4 to 15 μm, more preferably 0.8 to 10 μm.
It is preferable that it is m. If the layer thickness is too thin, the adhesiveness between the film-shaped support and the hydrous pressure-sensitive adhesive layer may be reduced, and if it is too thick, the stretchability of the film may be significantly reduced.

In the present invention, the method for laminating the primer layer on the film-like support is not particularly limited, but for example, a liquid primer layer dissolved in a solvent is applied to the surface of the film-like support. The primer layer can be laminated by volatilizing the solvent.

In the patch of the present invention, the hydrous pressure-sensitive adhesive layer laminated on the primer layer contains a poorly water-soluble crosslinking agent. In the present invention, the poorly water-soluble crosslinking agent means 1 g of a sample in 100 ml of purified water. Was added, and the mixture was shaken at 25 ° C. for 30 minutes, centrifuged (10 minutes, 1500 rpm), and the supernatant was measured by atomic absorption.
Refers to compounds that are 0 (mg / 100 ml) or less.

Specific examples of the sparingly water-soluble cross-linking agent include:
Synthetic hydrotalcite, dihydroxyaluminum aminoacetate (aluminum glycinate), magnesium aluminate silicate, magnesium aluminometasilicate, synthetic aluminum silicate, dry aluminum hydroxide gel, magnesium oxide, aluminum oxide, calcium oxide, copper oxide, Iron oxide, titanium oxide, magnesium silicate, magnesium carbonate, magnesium hydroxide, alumina hydroxide / magnesium, magnesium hydroxide / potassium aluminum sulfate coprecipitate product, aluminum hydroxide / sodium hydrogencarbonate coprecipitate, hydrogen phosphate Examples thereof include calcium, anhydrous calcium phosphate, a cationic polymer compound or a salt thereof, and these can be used alone or in combination of two or more kinds as appropriate. Among these, synthetic hydrotalcite, dihydroxyaluminum aminoacetate and the like are particularly preferable.

Here, the above-mentioned cationic polymer compound or a salt thereof has a function of acting on an anion group of a gel-forming polymer compound having an anion group to form a crosslinked structure. Polymer compounds having at least two cationic groups such as ⁺ and S ⁺ in the molecule or salts thereof, which are water-soluble. Among these,
The cation group is preferably an N ⁺ group, and more preferably the cation group is a trimethylammonium group or a polydimethyldiallylammonium group. Further, it is preferable that the main chain is a polysaccharide-based polymer compound.

Specific examples of the above-mentioned cationic polymer compound or salt thereof include vinyl-based cationized polymer compounds and cationized polysaccharides, and more specifically, poly-4 (2)-. Vinyl pyridine, ionene polymer (manufactured by Aldrich), N-trialkylaminomethyl polystyrene, aminoacetalized polyvinyl alcohol, poly-4 (5) -vinylimidazole, linear polyethyleneimine, polyethyleneimine, polydialkyldiallylammonium salt, Dialkyldiallylammonium salt-SO ₂ copolymer, cationized dextran,
Cationized starch, cationized PVP, trimethylammonium type cationized cellulose, polydimethyl diallyl ammonium type cationized cellulose (hydroxyethyl cellulose dimethyl allyl ammonium chloride, etc.), cationized PVA, dimethyl diallyl ammonium salt-acrylamide copolymer, dimethyl lauryl ammonium Examples include cationized cellulose, cationized guar gum, chitosan, gelatin, and salts thereof such as fluoride, chloride, bromide, iodide and the like. These may be used alone or in combination of two or more. The molecular weight of the cationic polymer compound is not particularly limited, but it is preferable that the weight average molecular weight is 1,000 to 100,000,000, for example. In order to obtain particularly good elasticity and shape retention for good gel formation, preferably 10,000 to
10,000,000, more preferably 50,000
It is about 10,000,000.

The amount of the sparingly water-soluble crosslinking agent in the hydrous pressure-sensitive adhesive composition of the present invention (the composition forming the hydrous pressure-sensitive adhesive layer) is not particularly limited, but the hydrous pressure-sensitive adhesive composition is not limited. 0.001 to 10 mass% of the whole, especially 0.01
-5% by mass, more preferably 0.05 to 1% by mass, and if it is less than 0.001% by mass, the cohesive force of the composition may be weakened. It may decrease.

The hydrous pressure-sensitive adhesive composition used in the present invention is formed from polyacrylic acid as its main component.
Further, other components may be optionally blended if necessary. For example, other water-soluble polymer compounds, medicinal components, emulsifiers, moisturizing components (polyhydric alcohols), cooling agents,
Inorganic powders, preservatives, fragrances, pigments and the like can be added.

Any of the above polyacrylic acids can be used, and the molecular weight and linear or branched shape are not particularly limited, but those having a molecular weight of 10,000 to 10,000,000 are preferably used. In particular, the weight average molecular weight is 10,000 to less than 500,000, 500,000 to less than 2,000,000, and 2 to 70.
It is preferable to combine two or more kinds of polyacrylic acid having an average molecular weight of 0,000 and a salt thereof, since the feeling of use is improved. In addition to a polymer obtained by polymerizing ordinary acrylic acid, a partially crosslinked acrylic acid polymer such as carboxyvinyl polymer, for example, Carbopol (trade name: manufactured by Goodrich, USA) is also suitable. Can be used.

It is also preferable to add a polyacrylic acid salt in place of the polyacrylic acid or together with the polyacrylic acid. Examples of the polyacrylic acid salt include sodium polyacrylate and potassium polyacrylate. One or more of polyacrylic acid monovalent metal salts, polyacrylic acid monoethanolamine, polyacrylic acid diethanolamine, polyacrylic acid triethanolamine and other polyacrylic acid amine salts, and polyacrylic acid ammonium salts. Can be preferably used.

The content of polyacrylic acid and / or polyacrylic acid salt is preferably 1 to 20% by weight, and more preferably 3 to 15% by weight, based on the whole hydrous pressure-sensitive adhesive composition. The anchoring force may be insufficient, and if it is too large, the viscosity of the water-containing gel may increase, which may cause a problem in workability during production, or may cause pain when the patch is peeled off.

Further, when other water-soluble polymer compound is blended, the kind thereof is not particularly limited, and those conventionally used can be used, for example, gelatin,
Agar, polyvinyl alcohol, polyvinylpyrrolidone polyethylene oxide, carboxymethyl cellulose, sodium carboxymethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose,
Examples thereof include methyl cellulose, sodium alginate, xanthan gum, gum arabic, tragacanth gum, karaya gum, maleic anhydride copolymer, propylene glycol, sodium carboxymethyl starch, and carrageenan. These can be used alone or in combination of two or more, but in the case of the present invention, especially sodium carboxymethyl cellulose is mixed with the above polyacrylic acid and / or polyacrylic acid salt, and further, if necessary. Accordingly, it is desirable to mix and use other polymer compounds. The blending amount of these other water-soluble polymer compounds can be appropriately selected within a range that does not impair the transparency of the hydrous pressure-sensitive adhesive layer of the present invention.

Examples of the medicinal component include indomethacin, glycol salicylate, methyl salicylate, ketoprofen, flurbiprofen, ibuprofen, suprofen, loxoprofen, zaltoprofen, piroxicam, felbinac, diphenhydramine, dibucaine, procaine, lidocaine, vitamin E derivative, glycyrrhetinic acid. Or these derivatives etc. are mentioned,
These may be used alone or in appropriate combination of two or more.

Examples of the above-mentioned ingredients for imparting warmth include capsaicinoids, capsaicin, dihydroxycapsaicin, capsaicin analogs such as capsanthin, capsicoside, capsicum extract, capsicum tincture, capsicum-derived substances such as capsicum, benzyl nicotinate, β-butoxy nicotinate. Ethyl, N-acyl vanilamide, nonyl acid vanilamide, and vanillyl alcohol alkyl ether represented by the following general formula (1), which can be used alone or in combination of two or more kinds. .

[0027]

[Chemical 1] (In the formula, R is an alkyl group having 1 to 6 carbon atoms)

The blending amount (the total blending amount in the case of using two or more kinds in combination) of the above-mentioned warming sensation substance with respect to the hydrous pressure-sensitive adhesive composition of the present invention is 0.0001 to 5 mass% of the whole hydrous pressure-sensitive adhesive composition. Is preferable, more preferably 0.001 to 3% by mass, further preferably 0.005 to 1% by mass. If the blending amount of the warming sensation-imparting substance is too small, sufficient warmth may not be imparted, and if it is too large, skin irritation may occur.

Examples of the emulsifier include polyglycerin fatty acid ester such as diglycerin monostearate, polyoxyethylene (POE) (10) polyoxyethylene glycerin fatty acid ester such as glyceryl monooleate, polyoxyethylene fatty acid ester, POE ( Two
5) Polyoxyethylene alkyl ether such as lauryl ether, polyoxyalkylene alkyl ether such as polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl ether sulfuric acid (ester) salt, fatty acid soap, sorbitan fatty acid ester, glycerin fatty acid ester, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, alkyl sulfate, N-acylmethyl taurine salt,
Examples thereof include alkylammonium salt, betaine acetate, propylene glycol fatty acid ester, vitamin derivative, glycyrrhizic acid, glycyrrhetinic acid and derivatives thereof, and specifically, sorbitan monooleate, glyceryl monooleate, decaglyceryl monooleate, diglyceryl dioleate. , Hexaglyceryl monolaurate, propylene glycol monostearate, POE (20)
Sorbitan monooleate, POE (60) sorbit tetraoleate, POE (40) monostearate, PO
E (10) oleyl ether, POE (10) nonylphenyl ether, POE (50) hydrogenated castor oil, POE
(5) Oleic acid amide, sodium lauryl sulfate, P
Sodium OE alkyl ether sulfate, Sodium POE alkyl ether acetate, Tri-POE (10) alkyl ether phosphate, Stearyl trimethyl ammonium chloride, Benzalkonium chloride, Betaine lauryl dimethylaminoacetate, Egg yolk, Lecithin, Imidazolinium betaine, Diethyl sebacate Etc.

As the moisturizing component (polyhydric alcohol), glycerin, sorbitol, ethylene glycol,
Propylene glycol, polyethylene glycol, polypropylene glycol, 1,3-propanediol,
1,4-butanediol, maltitol, xylitol and the like can be mentioned, and these can be used alone or in an appropriate combination of two or more kinds.

As the above-mentioned cooling agent, menthol derivatives such as camphor, thymol, menthol, N-ethyl-p-menthane-carboxamide, p-menthane-3,8-diol, l-isopulegol and l-menthylglyceryl ether are used. And the like. These can be used alone or in combination of two or more kinds as appropriate.

Examples of the above-mentioned inorganic powder include smectite, kaolin, zinc oxide, titanium oxide, silicic acid anhydride, etc. These can be used alone or in combination of two or more kinds.

Examples of the above preservatives include methylparaben, propylparaben, thymol and the like, and these can be used alone or in combination of two or more kinds.

As the fragrance, for example, fennel oil, castor oil, peppermint oil, peppermint oil, daisy leaf oil, cinnamon oil, clove oil, thymian oil, turpentine oil, henoposite oil, yamazine oil, eucalyptus oil, lavender oil, lemon oil, Orange oil, toka oil, bergamot oil, rose oil, citronella oil, lemongrass oil, camphor oil, geranium oil and the like can be mentioned. Further, as the plant extract, for example, aloe, anise, angelica, benzoin, immortelle, chamomile, chamomile, garlic, cardamom,
Galvanum, caraway, carrot seed, guaiac wood, grapefruit, cypress, sandalwood, cedarwood, juniper, star anise, sage, geranium, celery, thyme, tarragon, turpentine, frankincense, violet, pine, parsley, birch, patchouli, rose , Hyssop, Fennel, Black pepper, Bodaiju flower, Myrrh, Yarrow, Lemon, Lemongrass, Rosemary, Laurel, Spiraea, Spiraea, Cornflower, Almond, Thistle, Arnica, Cypress, Fennel, Enishida, Erica, Oguruma, mustard, calocon , Kanzui, yellow clover, ginkgo biloba, calendula, celandine, watercress, genka, gentian, sari ambo, sycamore, birch,
Fern, shirushi, camphor, chopsticks, syringa, plum, pear, halibut, taiso, takusha, dandelion, chimo, chervil, chorei, tenmondou, capsicum, neura, norangin, hagomogusa, mint, sycamore, sycamore, sycamore, sycamore. Extracts from bukuro, borigi, magwort, mayorana, melissa, mokutou, peach, mistletoe, eucalyptus, yokuinin, lavender, forsythia, wasabi radish and the like can be mentioned, but among these, especially chamomile, sage, parsley, rose. Extracts from marie, syringa, syringa, cornflower, anise, laurel, angelica, fennel, peppermint (peppermint, lemon balm), lavender, thyme, etc. are suitable. As specific components of such extract, for example, monoterpene hydrocarbon, cineole, borneol, camphor (camphor), linanol, berbenol, flavonoids, choline, amino acid, tannin, vegetable acid, fatty acid, hydrocyanic acid Glycoside, salicylic acid derivative, salvin, condensed tannin, phenolic acid, carnosic acid, triterpene acid, thujong, salben, pinene, apiol, apioline, myristicin, coumarin, kamaazulen, farnesene, bisabolol, geraniol, eugenol, terpene, ferrandrin,
Examples thereof include anethole, menthol, menthone, limonene, citral, citronellal and eugenol acetate.

The type of the dye is not particularly limited, and dyes described in the legal dye handbook can be blended.

The water-containing pressure-sensitive adhesive layer of the present invention is a water-containing system, and the water content of the water-containing pressure-sensitive adhesive composition is not particularly limited, but the water content per 100 parts by mass of the final composition. Is 30 to 98 parts by mass, more preferably 40 to 95.
Parts by mass are desirable. If the water content is too low, the anchorability between the support and the water-containing pressure-sensitive adhesive layer may be poor, and if it is too high, the properties as a water-containing pressure-sensitive adhesive may not be obtained.

The patch of the present invention is obtained by spreading the above-mentioned water-containing pressure-sensitive adhesive composition on the surface of the primer layer laminated on the above-mentioned support, and the water-containing pressure-sensitive adhesive composition to be spread (amount of paste).
Is not particularly limited, but is usually 1 to 40.
(G / 10 × 14 cm), preferably 1 to 30 (g / 1
0 × 14 cm) is desirable. If the spread amount is too large, it may be difficult to ensure transparency.

The method for producing the patch of the present invention is not particularly limited, and for example, the composition components of the hydrous pressure-sensitive adhesive composition are kneaded by a known method to prepare a hydrous pressure-sensitive adhesive composition, A water-containing pressure-sensitive adhesive layer is obtained by uniformly spreading this water-containing pressure-sensitive adhesive composition on the surface of the primer layer laminated on the above-mentioned support, and further, if necessary, the surface of the water-containing pressure-sensitive adhesive layer (plastic) with a plastic film. The patch can be prepared by covering the body surface) and cutting into a suitable size.

[0039]

EFFECTS OF THE INVENTION According to the present invention, a patch having a wrinkle on a film-shaped support can be obtained.

[0040]

EXAMPLES The present invention will be described in more detail below by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Example 1] 65 mol% (302.0 g) of 2-ethylhexyl acrylate (EHA) and 35 mol% (98.0 g) of vinylpyrrolidone (VP) were charged in a separable flask, and the monomer concentration at the initial stage of polymerization was 8%.
70.6 g of ethyl acetate was added so that it might be 5 mass%.
This solution was heated to 60 ° C. under a nitrogen atmosphere and polymerized for 32 hours. After the polymer was taken out, ethyl acetate was further added so that the polymer concentration was 25% by mass, and the mixture was uniformly mixed with a dissolver to prepare a primer layer solution. This solution was applied onto a silicone-treated release material having a thickness of 40 μm of polyethylene terephthalate (PET) so that the dried thickness would be 40 μm, and heated at 60 ° C. for 30 minutes. The primer layer on the release material was transferred to a polyurethane film having a thickness of 40 μm to prepare a film in which the primer layer was laminated on one side of the polyurethane film. The hydrous plaster shown in Example 1 of Table 1 was spread on the primer layer surface of this film to obtain a patch.

Example 2 A methacrylic acid-methyl methacrylate (mass ratio 1: 1) copolymer (Rohm Ph) was formed on an ethylene-vinyl acetate copolymer film having a thickness of 50 μm.
"EUDRAGIT L-100-5" manufactured by ARMA
5 ") 10 mass% methanol solution was applied so that the thickness after drying would be 1 µm, and dried at 60 ° C for 3 minutes to form a primer layer. The hydrous plaster shown in Example 2 of Table 1 was spread on the primer layer side of this film to obtain a patch.

Example 3 Aqueous dispersion of water-dispersible saturated polyester resin having sulfonic acid group (Pethresin A-1)
20, solid content 25%, Takamatsu Yushi Co., Ltd. 540 parts by mass, ion exchanged water 295 parts by mass, lauroyl peroxide 2 parts by mass and nonionic surfactant (POE (20) sorbitan monooleate) 3 parts by mass. Was added and dispersed uniformly.
Nitrogen gas was blown into the resulting mixture for 20 minutes for sufficient deoxidation, and then the temperature was gradually raised, and when the liquid temperature reached 72 ° C, 15 parts by mass of methyl methacrylate and 50 parts of acrylamide were added to the mixture. 1 part by mass was added dropwise at 70 to 80 ° C. Then, the liquid temperature was kept at 75 to 80 ° C. and the reaction was continued for 3 hours. After the reaction, solid content 20%,
A stable water-dispersible modified saturated polyethylene resin aqueous solution having a pH of 5.0 and a viscosity of 120 centipoise was obtained. This is gravure coated on a polyester / polyether film having a thickness of 30 μm to a dry thickness of 5 μm.
It was heated and dried at 00 ° C for 1 minute to form a primer layer.
The hydrous plaster shown in Example 3 of Table 1 was spread on the primer layer side of this film to obtain a patch.

Example 4 65 mol% (302.0 g) of 2-ethylhexyl acrylate (EHA) and 35 mol% (98.0 g) of vinylpyrrolidone (VP) were charged in a separable flask, and the monomer concentration at the initial stage of polymerization was 8%.
70.6 g of ethyl acetate was added so that it might be 5 mass%.
This solution was heated to 60 ° C. under a nitrogen atmosphere and polymerized for 32 hours. After the polymer was taken out, ethyl acetate was further added so that the polymer concentration was 25% by mass, and the mixture was uniformly mixed with a dissolver to prepare a primer layer solution. This solution was applied onto a silicone-treated release material having a thickness of 40 μm of polyethylene terephthalate (PET) so that the dried thickness would be 40 μm, and heated at 60 ° C. for 30 minutes. The primer layer on the release material was transferred to a polyether block amide copolymer film having a thickness of 30 μm to prepare a film in which the primer layers were laminated. The hydrous plaster shown in Example 4 of Table 1 was spread on the primer layer surface of this film to obtain a patch.

Example 5 A methacrylic acid-methyl methacrylate (mass ratio 1: 1) copolymer ("E" manufactured by Rohm Pharma Co., Ltd.) was formed on a polyethylene film having a thickness of 30 μm.
UDRAGITL-100-55 ") was applied in a 10 mass% methanol solution so that the thickness after drying would be 1 µm, and dried at 60 ° C for 3 minutes to form a primer layer.
The hydrous plaster shown in Example 5 of Table 1 was spread on the primer layer surface of this film to obtain a patch.

Example 6 Aqueous dispersion of water-dispersible saturated polyester resin having sulfonic acid group (Pethresin A-1)
20, solid content 25%, Takamatsu Yushi Co., Ltd. 540 parts by mass, ion exchanged water 295 parts by mass, lauroyl peroxide 2 parts by mass and nonionic surfactant (POE (20) sorbitan monooleate) 3 parts by mass. Was added and dispersed uniformly.
Nitrogen gas was blown into the resulting mixture for 20 minutes for sufficient deoxidation, and then the temperature was gradually raised, and when the liquid temperature reached 72 ° C, 15 parts by mass of methyl methacrylate and 50 parts of acrylamide were added to the mixture. 1 part by mass was added dropwise at 70 to 80 ° C. Then, the liquid temperature was kept at 75 to 80 ° C. and the reaction was continued for 3 hours. After the reaction, solid content 20%,
A stable water-dispersible modified saturated polyethylene resin aqueous solution having a pH of 5.0 and a viscosity of 120 centipoise was obtained. This was gravure coated onto a polyethylene terephthalate film having a thickness of 30 μm so that the dry thickness was 5 μm.
The primer layer was formed by heating and drying at 0 ° C. for 1 minute. The hydrous plaster shown in Example 6 of Table 1 was spread on the primer layer surface of this film to obtain a patch.

Comparative Example 1 65 mol% (302.0 g) of 2-ethylhexyl acrylate (EHA) and 35 mol% (98.0 g) of vinylpyrrolidone (VP) were charged in a separable flask, and the monomer concentration at the initial stage of polymerization was 8%.
70.6 g of ethyl acetate was added so that it might be 5 mass%.
This solution was heated to 60 ° C. under a nitrogen atmosphere and polymerized for 32 hours. After the polymer was taken out, ethyl acetate was further added so that the polymer concentration was 25% by mass, and the mixture was uniformly mixed with a dissolver to prepare a primer layer solution. This solution was applied onto a silicone-treated release material having a thickness of 40 μm of polyethylene terephthalate (PET) so that the dried thickness would be 40 μm, and heated at 60 ° C. for 30 minutes. The primer layer on the release material was transferred to a polyurethane film having a thickness of 40 μm to prepare a film in which the primer layers were laminated. The hydrous plaster shown in Comparative Example 1 in Table 1 was spread on the primer layer surface of this film to obtain a patch.

[Comparative Example 2] 65 mol% (302.0 g) of 2-ethylhexyl acrylate (EHA) and 35 mol% (98.0 g) of vinylpyrrolidone (VP) were charged in a separable flask, and the monomer concentration at the initial stage of polymerization was 8%.
70.6 g of ethyl acetate was added so that it might be 5 mass%.
This solution was heated to 60 ° C. under a nitrogen atmosphere and polymerized for 32 hours. After the polymer was taken out, ethyl acetate was further added so that the polymer concentration was 25% by mass, and the mixture was uniformly mixed with a dissolver to prepare a primer layer solution. This solution was applied onto a silicone-treated release material having a thickness of 40 μm of polyethylene terephthalate (PET) so that the dried thickness would be 40 μm, and heated at 60 ° C. for 30 minutes. The primer layer on the release material was transferred to a polyurethane film having a thickness of 40 μm to prepare a film in which the primer layers were laminated. The hydrous plaster shown in Comparative Example 2 in Table 1 was spread on the primer layer surface of this film to obtain a patch.

For each of the films of Examples 1 to 6 and Comparative Examples 1 and 2, the film surface immediately after production was visually observed and the wrinkles were evaluated based on the following wrinkle evaluation criteria. The results are also shown in Table 1.

<Evaluation Criteria for Wrinkle of Film> No wrinkles at all: 6 Almost no wrinkles: 5 No wrinkles: 4 There are some wrinkles: 3 Wrinkled: 2 Very wrinkled: 1

[0051]

[Table 1]

* 1: Polyacrylic acid (Jurimer 10SH) * 2: Sodium polyacrylate (Aronbis S) * 3: Sodium carboxymethyl cellulose (CMC
1380) * 4: Sodium alginate (duck algin) * 5: Cross-linked polyacrylic acid (Carbopol 940) * 6: Polyvinyl alcohol (Gothenol EG05)

Continued front page    (72) Inventor Norio Iida             1-3-7 Honjo, Sumida-ku, Tokyo Rio             Within the corporation F term (reference) 4C076 AA75 BB31 EE10A EE16A                       EE45 FF36

Claims (2)

[Claims] 1. A primer layer and a hydrous pressure-sensitive adhesive layer are sequentially laminated on one surface of a film-like support, and the hydrous pressure-sensitive adhesive layer contains a sparingly water-soluble crosslinking agent and has a pH of 3 or less. The patch is characterized in that it is ~ 7. 2. The sparingly water-soluble crosslinking agent is synthetic hydrotalcite, dihydroxyaluminum aminoacetate (aluminum glycinate), magnesium aluminate silicate, magnesium aluminometasilicate, synthetic aluminum silicate, dry aluminum hydroxide gel, Magnesium oxide, aluminum oxide, calcium oxide, copper oxide, iron oxide, titanium oxide, magnesium silicate, magnesium carbonate, magnesium hydroxide, alumina hydroxide.
One or two selected from magnesium, a coprecipitation product of magnesium hydroxide / potassium aluminum sulfate, an aluminum hydroxide / sodium hydrogencarbonate coprecipitation, calcium hydrogenphosphate, anhydrous calcium phosphate, a cationic polymer compound or a salt thereof. The patch according to claim 1, which comprises more than one kind.