WO2022064608A1 - Hydrous adhesive patch for non-medical product - Google Patents

Hydrous adhesive patch for non-medical product Download PDF

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Publication number
WO2022064608A1
WO2022064608A1 PCT/JP2020/036081 JP2020036081W WO2022064608A1 WO 2022064608 A1 WO2022064608 A1 WO 2022064608A1 JP 2020036081 W JP2020036081 W JP 2020036081W WO 2022064608 A1 WO2022064608 A1 WO 2022064608A1
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WO
WIPO (PCT)
Prior art keywords
water
mass
pressure
sensitive adhesive
adhesive layer
Prior art date
Application number
PCT/JP2020/036081
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French (fr)
Japanese (ja)
Inventor
眞 金箱
Original Assignee
ニチバン株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ニチバン株式会社 filed Critical ニチバン株式会社
Priority to JP2022551502A priority Critical patent/JPWO2022064608A1/ja
Priority to PCT/JP2020/036081 priority patent/WO2022064608A1/en
Publication of WO2022064608A1 publication Critical patent/WO2022064608A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60Sugars; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/24Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/58Adhesives

Definitions

  • the present invention relates to a non-pharmaceutical water-containing patch, and more specifically, a water-containing patch that maintains high adhesive strength even after the water in the pressure-sensitive adhesive layer is volatilized and has low skin irritation.
  • a water-containing patch that 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 adhesive in the present specification), has a plaster layer (adhesive layer) as a woven fabric, knitted fabric, non-woven fabric, or the like. It is a kind of patch to be provided on the support of. 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 the adhesive strength decreases with time, especially with the volatilization of water in the plaster layer. The problem was that it was easy to peel off from the skin.
  • an emulsion (also called emulsion) base in which an acrylic acid alkyl ester copolymer known as one component constituting a non-aqueous (hydrophobic or lipophilic) adhesive is dispersed is used.
  • a technique of blending a water-containing patch into a plaster layer (adhesive layer) is known.
  • Patent Document 1 aims to provide a water-containing patch having excellent adhesive force and re-sticking force even after long-term sticking, and suppressing hardening and suppleness due to loss of water. 5.0% by mass or more and 10% by mass or less of the methyl acrylate / 2-ethylhexyl acrylate copolymer and 0.01% by mass or more of the water-dispersible surfactant with respect to the entire composition for a water-containing external patch. A patch containing 10.0% by mass or less is disclosed. Further, in Patent Document 2, a polyacrylic acid neutralized product and the neutralized product 2.
  • Patent Document 3 contains poly (methyl acrylate / 2-ethylhexyl acrylate) and a monofatty acid ester of polyethylene glycol as a surfactant for the purpose of providing a poultice that can peel off a peeling liner with a smaller force.
  • Pap agents are disclosed.
  • Patent No. 5650684 Patent No. 5921779 Patent No. 6469136
  • 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.
  • the adhesive strength after the moisture in the adhesive layer is volatilized is not sufficiently satisfactory as compared with the tape agent.
  • hydrophilic acrylic pressure-sensitive adhesives polyacrylic acid partially neutralized products (manufactured by Showa Denko Corporation, Viscomate (registered trademark) NP-800, etc.), etc.
  • stickiness constituting the pressure-sensitive adhesive layer of water-containing patches have been used.
  • the thickening agent sodium carmellose, etc.
  • the thickening agent sodium carmellose, etc.
  • a cross-linking agent dihydroxyaluminum aminoacetate (manufactured by Kyowa Chemical Industry Co., Ltd., glycinal, etc.) so as not to dissolve in water and lose its function).
  • a method of dispersing these components in a wetting agent containing almost no water and adding the components to a composition forming a pressure-sensitive adhesive layer is generally practiced in the production of a poultice.
  • the present invention has been completed by finding that the polymer does not decrease, but rather improves significantly, and that the skin irritation is also low.
  • the present invention is: [1] A non-pharmaceutical water-containing patch comprising a support, an adhesive layer provided on the support, and a release liner.
  • the pressure-sensitive adhesive layer 1) Acrylic hydrophilic adhesive, 2) Acrylic acid alkyl ester-based copolymer emulsion, 3) Crosslinking agent, 4) Condensing agent, 5) Wetting agents containing little water, and 6) water, Contains,
  • the acrylic acid alkyl ester copolymer 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 higher when the monomer A is homopolymerized.
  • the monomer B is a polymer having a glass transition temperature (Tg) of 220 K or less when the monomer B is homopolymerized.
  • Tg glass transition temperature
  • the acrylic acid alkyl ester-based copolymer emulsion is contained in a proportion of 20% by mass or more and less than 70% by mass with respect to the total mass of the pressure-sensitive adhesive layer. Water-containing patch for non-pharmaceutical products.
  • the acrylic acid alkyl ester-based copolymer is an acrylic acid alkyl ester-based copolymer 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. .. b)
  • the pressure-sensitive adhesive layer has a pH of 2 to 4.
  • the non-pharmaceutical water-containing patch according to [1] or [2], which is selected from the group consisting of, and xylitol.
  • the pressure-sensitive adhesive layer is It has a peel adhesive strength of 1N / 15 mm or more after storage at 50 ° C. for 16 hours from the date of manufacture of the patch. Immediately after the patch is manufactured, it has a probe tack of 0.7 N / mm ⁇ or more and has a probe tack.
  • the probe tack value of the pressure-sensitive adhesive layer immediately after the production of the patch is 1.8 times or more the probe tack value of the pressure-sensitive adhesive layer after storage at 50 ° C. for 16 hours from the date of manufacture of the patch.
  • the non-pharmaceutical water-containing patch according to any one of [1] to [3].
  • the pressure-sensitive adhesive layer is further 7) a cooling agent 8) an organic solvent, 9) pH regulator, 10) Chelating agent, The non-pharmaceutical water-containing patch according to any one of [1] to [4].
  • a monomer mixture consisting of a monomer A having a glass transition temperature (Tg) of 270 K or more at the time of homopolymerization and a monomer B having a Tg of 220 K or less at the time of homopolymerization.
  • Tg glass transition temperature
  • a monomer B having a Tg of 220 K or less at the time of homopolymerization.
  • acrylics such as methyl acrylate / 2-ethylhexyl acrylate copolymer resin emulsion (trade name: Nicazole TS-620, Nippon Carbide Industries Co., Ltd.), etc.
  • Proposals have been made to blend an acid alkyl ester copolymer emulsion into the pressure-sensitive adhesive layer and to increase the blending amount.
  • the adhesive strength after the water in the pressure-sensitive adhesive layer is volatilized is sufficiently sufficient as compared with the tape agent. I could't say that.
  • the present inventors have encountered the above-mentioned problems in an amount of 20% by mass or more and less than 70% by mass, which exceeds the amount previously proposed, and is an emulsion of a copolymerized resin emulsion of methyl acrylate and 2-ethylhexyl acrylate (hereinafter, co-weight).
  • co-weight an emulsion of a copolymerized resin emulsion of methyl acrylate and 2-ethylhexyl acrylate
  • co-weight emulsion of a copolymerized resin emulsion of methyl acrylate and 2-ethylhexyl acrylate
  • the non-pharmaceutical water-containing patch of the present invention (hereinafter, also simply referred to as “patch”) comprises a support, a pressure-sensitive adhesive layer provided on the support, and a release liner.
  • the shape of the patch, particularly the support, and the preparation portion consisting of the pressure-sensitive adhesive layer provided on the support is not particularly limited, and is rectangular (square, rectangle, etc.), quadrangular (trapezoid, rhombus, etc.), polygonal. , Circular, oval, semi-circular, triangular, crescent-shaped, and a combination of these, etc., various shapes can be selected according to the attachment location.
  • the area of the patch (particularly the above-mentioned pharmaceutical product portion) can be appropriately determined, and can be, for example, in the range of 2 to 300 cm 2 in consideration of the purpose of use of the patch.
  • the non-pharmaceutical water-containing patch of the present invention generally constitutes a non-aqueous acrylic pressure-sensitive adhesive in addition to the hydrophilic acrylic pressure-sensitive adhesive described later for the water-containing pressure-sensitive adhesive layer. It is characterized by blending an emulsion of an ester-based copolymer.
  • the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer (plaster layer) of a water-containing patch includes 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.
  • 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.
  • the "acrylic acid alkyl ester-based copolymer” is intended to contain both acrylic acid and methacrylic acid alkyl esters, and the "acrylic adhesive” is also an acrylic pressure-sensitive adhesive and methacrylic acid. It is intended to contain both of the adhesives.
  • 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.
  • the acrylic acid alkyl ester-based copolymer used in the present invention has a 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 a monomer B as a polymer.
  • the upper limit of the glass transition temperature Tg of the homopolymer of the monomer A is about 500 K
  • the lower limit of the glass transition temperature Tg of the homopolymer of the monomer B is about 200 K.
  • homopolymers obtained by polymerizing only a monomer that exhibits adhesive strength are said to have high adhesive strength but weak mechanical strength, and in general, copolymerization with a monomer that improves cohesive strength improves mechanical strength.
  • the coalescence is used as an adhesive.
  • 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.
  • butyl acrylate and 2-ethylhexyl acrylate are preferable, and 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. ..
  • the monomers that improve the aggregating power include the monomers listed in Table 1.
  • methyl acrylate, methyl methacrylate, ethyl methacrylate and n-butyl methacrylate are preferable.
  • 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.
  • Nikazole registered trademark
  • TS-620 methyl acrylate
  • the methyl acrylate / 2-ethylhexyl acrylate copolymer resin emulsion is listed in the pharmaceutical additive standard. According to the Pharmaceutical Additives Standard (2018), when Nikazole TS-620 is evaporated to dryness on a water bath and then dried at 105 ° C.
  • the amount of evaporation residue is 57 to 61%.
  • the proportion of the monomer A in which the Tg of the homopolymer is 270 K or more to 30% by mass or more and 50% by mass or less, improvement in the adhesive strength of the pressure-sensitive adhesive layer at the time of water dispersal can be expected. ..
  • the blending amount of the acrylic acid alkyl ester-based copolymer emulsion is 20% by mass based on the total mass of the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch. It can be more than 70% by mass and 20% by mass or more and 60% by mass or less.
  • the blending amount (solid content equivalent amount) of the acrylic acid alkyl ester-based copolymer is, for example, 0.1% by mass or more and 40% by mass or less, based on the total mass of the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch. It can be 10% by mass or more and 37% by mass or less.
  • the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention contains an acrylic hydrophilic pressure-sensitive adhesive.
  • 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 can be blended with water in the pressure-sensitive adhesive layer. , Demonstrates adhesiveness.
  • water-soluble (meth) acrylic polymer examples include homopolymers such as polyacrylic acid and a neutralized product of polyacrylic acid; and copolymers such as N-vinylacetamide / sodium acrylate copolymer resin.
  • the polyacrylic acid neutralized product may be a completely neutralized product of polyacrylic acid, a partially neutralized product of 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 is, 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 non-pharmaceutical water-containing patch. can do.
  • the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention further contains a cross-linking agent.
  • the cross-linking agent include polyvalent metal salts, and examples thereof include polyvalent metal compounds containing aluminum.
  • 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 aluminate; inorganic aluminum complex salts and organic aluminum chelate compounds.
  • examples thereof include polyvalent metal compounds such as synthetic hydrotalcite, magnesium aluminate silicate, 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 residual adhesive on the skin and the adhesiveness.
  • the blending amount is, 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, based on the total mass of the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch.
  • the range of 0.01% by mass or more and 2.0% by mass or less can be mentioned.
  • the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention contains a thickening agent, which is expected to function as improving the shape retention and the tackiness of the pressure-sensitive adhesive.
  • the thickening agent include celluloses such as ethyl cellulose, sodium carmerol, hydroxyethyl cellulose, hydroxypropyl cellulose, hypromellose and methyl cellulose, polysaccharides such as sodium alginate, carrageenan, xanthan gum and sodium hyaluronate, gelatin and urea. Can be mentioned. Of these, carmellose sodium, which has thixotopy properties and improves ductility, is preferable.
  • the blending amount of the thickening agent is usually, for example, 0.1% by mass or more and 10% by mass or less, 0.5% by mass or more and 20% by mass, based on the total mass of the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch. Below, or in the range of 1.0% by mass or more and 10% by mass or less.
  • the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention contains a wetting agent (also referred to as a moisturizing agent).
  • the wetting agent has a function of suppressing evaporation of water over time, and can be directly mixed with water such as a water-soluble polymer such as a hydrophilic acrylic pressure-sensitive adhesive, a thickening agent such as carmellose sodium, and a cross-linking agent. It is expected to have a function of suppressing thickening due to lump generation and cross-linking. For the reason of avoiding the latter direct addition to water, it is desirable to use a wetting agent that contains almost no water.
  • the hydrophilic acrylic pressure-sensitive adhesive the thickening agent, etc.
  • a cross-linking agent or the like By blending a cross-linking agent or the like to prepare a pre-formation and then mixing it with other components constituting the pressure-sensitive adhesive layer, lump generation and thickening can be suppressed.
  • wetting agents include concentrated glycerin, glycerin, D-sorbitol, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, liquid paraffin, 1,3-propanediol, 1,4-butanediol, and martitol.
  • Polyhydric alcohols such as xylitol.
  • a wetting agent containing water can be preferably blended.
  • the D-sorbitol solution which is usually used as a 70% aqueous solution, contains water, so that it is difficult to use it for suppressing the generation of lumps and thickening (preparation of the above-mentioned preform), but it is mixed with other components thereafter. It is possible to mix them together.
  • the blending amount of the wetting agent (the total amount of the wetting agent containing almost no water and the wetting agent containing water) is usually set based on, for example, the total mass of the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch. It can be in the range of 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 or more and 60% by mass or less.
  • the non-pharmaceutical water-containing patch of the present invention contains water (moisture) in the pressure-sensitive adhesive layer.
  • the "water” contained in the pressure-sensitive adhesive layer includes not only water separately added as water at the time of forming the pressure-sensitive adhesive layer, 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 non-pharmaceutical 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. It can be in the range of 50% by mass 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.
  • a cooling agent can be added to the pressure-sensitive adhesive layer.
  • the refreshing agent include l-menthol, dl-camphor, kehi oil, geraniol, peppermint oil, bergamot oil, d-borneol, eucalyptus oil and the like, and these may be used alone or in combination of two or more. can.
  • the blending amount may be appropriately selected in consideration of developing a refreshing sensation at the time of application.
  • the blending amount of l-menthol as a refreshing agent is, for example, 0.01% by mass or more and 4.0% by mass or less, 0.01% by mass, based on the total mass of the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch.
  • the range of% or more and 3.0% by mass or less can be mentioned.
  • the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention may further contain an organic solvent.
  • the organic solvent blended in the pressure-sensitive adhesive layer may have a role of assisting the dissolution of each compounding component and preventing the precipitation of each compounding component from the pressure-sensitive adhesive layer.
  • organic solvent such as crotamitone; N-methyl-2-pyrrolidone; polyalkylene glycol such as macrogol 400 (polyethylene glycol) and polybutylene glycol; diethyl adipate, diisopropyl adipate, diethyl sebacate , Fatty esters such as diisopropyl sebacate, isopropyl myristate, isopropyl palmitate, oleyl oleate; sorbitan esters such as polyoxyalkylene fatty acid esters; 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 is, for example, 0.1% by mass or more and 20% by mass or less, 0.5% by mass or more and 10% by mass or less, or 1 based on the total mass of the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch. It can be in the range of 0.0% by mass or more and 5% by mass or less.
  • the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention may further contain a pH adjuster.
  • a pH adjuster either an organic acid or an inorganic acid can be used, and these may be used in combination.
  • the organic acid include citric acid, lactic acid, tartrate acid, gluconic acid, glycolic acid, malic acid, fumaric acid, metasulfonic acid, maleic acid, acetic acid and the like, and these may be used alone or in combination of two or more. Can be done.
  • hydroxy acids such as lactic acid also have the effect of improving the solubility of the sparingly soluble aluminum compound (crosslinking agent).
  • the inorganic acid examples include hydrochloric acid, boric acid, phosphoric acid, sulfuric acid and the like, and 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 non-pharmaceutical water-containing patch.
  • the blending amount of the inorganic acid can be, for example, in the range of 0.1% by mass or more and 1.2% by mass or less based on the total mass of the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch.
  • a chelating agent can be added to the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention in order to control the dissolution rate of the poorly soluble aluminum compound (crosslinking agent).
  • the chelating agent include sodium edetate (ethylenediaminetetraacetic acid disodium salt).
  • the blending amount of the chelating agent 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 non-pharmaceutical water-containing patch.
  • a water-soluble polymer compound a surfactant, a stabilizer (antioxidant, an ultraviolet absorber, etc.), an inorganic substance, etc.
  • These optional components can be used alone or in combination of two or more.
  • water-soluble polymer compound examples include polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, sucrose fatty acid ester and the like. 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 and 3.0% by mass or more and 20% by mass based on the total mass of the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch. It can be in the range of% or less, or 5.0% by mass or more and 20% by mass or less.
  • surfactant examples include polyoxyethylene fatty acid esters such as polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, polyethylene glycol distearate, polyethylene glycol dilate, and polypropylene glycol dioleate.
  • 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 non-pharmaceutical water-containing patch. Can be a range.
  • a stabilizer can be added to the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention in order to improve the storage stability of the ingredients against light (particularly ultraviolet rays), heat or oxygen. ..
  • the stabilizer include an antioxidant such as dibutylhydroxytoluene (BHT); an ultraviolet absorber such as a benzoylmethane derivative; and the like.
  • BHT dibutylhydroxytoluene
  • 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 non-pharmaceutical 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.
  • Examples of the support used for the non-pharmaceutical water-containing patch of the present invention include flexible supports such as films, non-woven fabrics, Japanese papers, cotton cloths, knitted fabrics, woven fabrics, 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.
  • the support such as cloth can be colored with a colorant to a color tone such as skin color to reduce the difference from the skin color at the time of application. Further, in that the color tone of the skin under the application can be easily seen through, the form of a plastic film having excellent transparency can be adopted.
  • the thickness of the support is usually about 5 ⁇ m to 1 mm.
  • its thickness is preferably 50 ⁇ m to 1 mm, more preferably 100 to 800 ⁇ m, and further preferably 200 to 700 ⁇ m.
  • the support is a plastic film, its thickness is preferably 10 to 300 ⁇ m, more preferably 12 to 200 ⁇ m, and even more preferably 15 to 150 ⁇ m.
  • the thickness of the support is as thin as about 5 ⁇ m to 30 ⁇ m, if a peelable carrier film layer is provided on the surface opposite to the pressure-sensitive adhesive layer formed on the support, the handleability as a patch can be improved. It is preferable because it improves.
  • the thickness of the support is smaller than 5 ⁇ m, 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 with water for bathing, etc. It may peel off from the skin in a short time due to contact.
  • 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 application.
  • 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.
  • the release liner (also referred to as release layer / release paper) used in the non-pharmaceutical 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. Conventional ones can be used in the field.
  • 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 ⁇ m to 1 mm, for example, 20 ⁇ m to 500 ⁇ m, preferably 40 ⁇ m to 200 ⁇ m.
  • 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 patch.
  • 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.
  • the non-pharmaceutical water-containing patch of the present invention can be produced by 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 ⁇ m to 1000 ⁇ m, for example, about 20 ⁇ m to 800 ⁇ m.
  • the pressure-sensitive adhesive layer-forming composition includes various components contained in the above-mentioned pressure-sensitive adhesive layer: acrylic hydrophilic pressure-sensitive adhesive, acrylic acid alkyl ester-based copolymer, cross-linking agent, thickening agent, wetting agent, and water. It is a semi-solid composition which may contain a cooling agent, an organic solvent, a pH adjuster and a chelating agent, and may further contain any other component. It is preferable to set the pH of the pressure-sensitive adhesive layer forming composition to 2 to 4 because good crosslinkability and shape retention can be expected.
  • the non-pharmaceutical water-containing patch of the present invention is characterized in that the adhesive strength is maintained when it contains water (immediately after application) and when it does not contain water (after the water volatilizes after application), and it also has skin irritation. It is a low patch.
  • the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention has i) a peel adhesive strength of 1 N / 15 mm or more after storage at 50 ° C. for 16 hours from the date of manufacture of the patch, and ii) the patch.
  • the adhesive Immediately after the manufacture of the adhesive, it has a probe tack of 0.7 N / mm ⁇ or more, and iii) the probe tack value of the pressure-sensitive adhesive layer immediately after the manufacture of the patch is 50 ° C. for 16 hours from the date of manufacture of the patch. It is preferable that the pressure-sensitive adhesive layer has an adhesive strength such that the probe tack value after storage is 1.8 times or more.
  • Example 1 1 part by mass of polyvinyl alcohol was dissolved in 10 parts by mass of purified water by heating at 70 ° C., and then cooled to room temperature (preliminary preparation 1). Next, 3 parts by mass of Macrogol (registered trademark) 400 and 1 part by mass of lactic acid were added to 1 part by mass of l-menthol, dissolved at 40 ° C., and then cooled to room temperature (preliminary preparation 2). Further, 4 parts by mass of the partially neutralized polyacrylic acid, 3 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 (preliminary preparation 3).
  • preform 1 methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion (solid content 60%, polyoxyethylene nonylphenyl ether (30EO) trace amount contained in the emulsion), 20 parts by mass, sodium edetate water. 0.2 parts by mass of Japanese product, 25 parts by mass of D-sorbitol 70% aqueous solution and 0.4 parts by mass of hydrochloric acid were added in this order, and the mixture was uniformly dispersed or dissolved under degassing conditions. The pre-formal product 2 was added thereto and kneaded uniformly under degassing conditions.
  • the preform 3 is added, the mass is corrected with purified water so as to have a total of 100 parts by mass, and then the mixture is uniformly kneaded under degassing conditions to obtain the pressure-sensitive adhesive layer forming composition (plaster) of Example 1. Obtained.
  • the obtained pressure-sensitive adhesive layer-forming composition is spread on the silicone surface of a liner (pete (75 ⁇ m) 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) is formed. After laminating, it was punched into an arbitrary shape, sealed in an aluminum bag, and aged at 40 ° C. for 1 week to obtain the formulation of Example 1.
  • Example 2 Same as Example 1 except that the amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion was changed to 30 parts by mass (solid content 60%) and the amount of the D-sorbitol 70% aqueous solution was changed to 20 parts by mass. The preparation of Example 2 was obtained.
  • Example 3 Same as Example 1 except that the compounding amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion was changed to 40 parts by mass (solid content 60%) and the compounding amount of the 70% aqueous solution of D-sorbitol was changed to 15 parts by mass. The preparation of Example 3 was obtained.
  • Example 4 The amount of methyl acrylate / 2-ethylhexyl acrylate copolymer compounded emulsion is 50 parts by mass (solid content 60%), the amount of D-sorbitol 70% aqueous solution is 10 parts by mass, and the amount of concentrated glycerin is 20 parts by mass.
  • the pharmaceutical product of Example 4 was obtained in the same manner as in Example 1 except that it was changed.
  • Example 5 The amount of methyl acrylate / 2-ethylhexyl acrylate copolymer compounded emulsion is 60 parts by mass (solid content 60%), the amount of D-sorbitol 70% aqueous solution is 0 parts by mass, and the amount of concentrated glycerin is 20 parts by mass.
  • the pharmaceutical product of Example 5 was obtained in the same manner as in Example 1 except that it was changed.
  • Comparative Example 1 A pharmaceutical product of Comparative Example 1 was obtained in the same manner as in Example 1 except that the blending amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion was changed to 7 parts by mass (solid content 60%).
  • Comparative Example 2 A pharmaceutical product of Comparative Example 2 was obtained in the same manner as in Example 1 except that the blending amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion was changed to 10 parts by mass (solid content 60%).
  • Comparative Example 3 The amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion was changed to 70 parts by mass (solid content 60%), the amount of the D-sorbitol solution was changed to 0 parts by mass, and the amount of concentrated glycerin was changed to 10 parts by mass. Except for the above, an attempt was made to obtain a pressure-sensitive adhesive layer-forming composition in the same manner as in Example 1, but a large amount of lumps were generated in the obtained pressure-sensitive adhesive layer-forming composition, and the subsequent spread to the liner was not achieved. The formulation could not be obtained.
  • Test Example 1 Adhesive layer (adhesive layer forming composition (plaster)) With respect to the formulations of Examples 1 to 5 and Comparative Examples 1 and 2 when they contained water (after aging) and when they did not contain water (after aging, the liner was peeled off to expose the pressure-sensitive adhesive layer). After drying at 50 ° C. for 16 hours), the color of the pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer forming composition) was visually evaluated. The results obtained are shown in Table 2.
  • Test Example 2 Cross-linked state of adhesive layer (adhesive layer forming composition (plaster))
  • the formulations (after aging) of Examples 1 to 5 and Comparative Examples 1 to 3 were cut into 1 cm ⁇ 5 cm and immersed in 50 mL of purified water at room temperature (23 ° C. ⁇ 5 ° C.). After 16 hours from the immersion, the swelling state of the pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer forming composition) was visually evaluated, and the cross-linked state of the pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer forming composition) was evaluated according to the following evaluation criteria. The results obtained are shown in Table 2.
  • ⁇ Evaluation criteria> No cross-linking (adhesive layer (adhesive layer forming composition) dissolved) +: Cross-linked (adhesive layer (adhesive layer forming composition) does not dissolve and swells greatly) ++: Strong cross-linking (adhesive layer (adhesive layer forming composition) does not dissolve and swells moderately) +++: Very strong cross-linking (adhesive layer (adhesive layer forming composition) does not dissolve and swells small)
  • the pressure-sensitive adhesive layer-forming composition evaluated as “-” may dissolve a polymer compound such as a hydrophilic acrylic pressure-sensitive adhesive, and as the dissolution progresses, it may be deposited on the bottom of the immersed container. On the other hand, as the evaluation changes from "+" to "+++", the swelling of the polymer compound decreases, and it can be confirmed that the pressure-sensitive adhesive layer-forming composition is in
  • Test Example 3 Adhesive strength test
  • ⁇ Test product> For the formulations of Examples 1 to 5, Comparative Example 1 and Comparative Example 2, water-containing (after aging) and water-free (after aging, the liner was removed to expose the pressure-sensitive adhesive layer, and the temperature was 50 ° C. for 16 hours. After drying in storage), the two types were set as the initial stage.
  • the "moisture-containing" preparations (after aging and in an aluminum bag) of Examples 1 to 5, Comparative Example 1 and Comparative Example 2 were stored at 60 ° C. for 1 week.
  • the following tests 1) to 3) were carried out for the "initial" (moisture-containing, moisture-free) and "60 ° C. for 1 week storage" (moisture-containing) of all the above-mentioned preparations.
  • the white turbidity of the pressure-sensitive adhesive layer-forming composition disappears due to the volatilization of water, and in all the formulations prepared in the range of 7% by mass to 60% by mass of the 2-ethylhexyl acrylate copolymer resin emulsion, after drying.
  • the color of the pressure-sensitive adhesive layer-forming composition became transparent.
  • the pressure-sensitive adhesive layer-forming composition of Comparative Example 3 in which the blending amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer resin emulsion was increased to 70% by mass caused a large amount of lumps to be generated in the formulation. It was impossible to manufacture.
  • the pressure-sensitive adhesive layer-forming composition in which the amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer resin emulsion was 7% by mass to 60% by mass was crosslinked, and the amount of the emulsion was increased. As a result, the cross-linked state tended to become stronger.
  • the formulations of Examples 1 to 5 were No. 1 in terms of water content (initial stage). The number was 21 or more, and no decrease with time was observed. In addition, the ball tack adhesive strength after the water volatilized tended to increase from the time when the water volatilized. On the other hand, the formulations of Comparative Examples 1 and 2 decreased with time when they contained water, and at 60 ° C. and 1 W, No. It was 17 or less.
  • the formulations of Examples 1 to 5 showed 1 N / 15 mm or more after the water volatilization, and depended on the blending amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer resin emulsion. Therefore, the value of peel adhesive strength increased.
  • the peel adhesive strength was less than 1N / 15 mm even after the water volatilized.
  • the formulations of Examples 1 to 5 showed 1 N / 5 mm ⁇ or more after the water volatilization, and depended on the blending amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer resin emulsion. As a result, the value of probe tack adhesive strength increased. In the formulations of Comparative Example 1 to Comparative Example 2, the probe tack adhesive strength after water volatilization exceeded 1 N / 5 mm ⁇ , but the value was lower than that of the examples.
  • the formulations of Examples 1 to 5 are higher in both water-containing and water-free (after water volatilization) in the ball tack and probe tack than the formulations of Comparative Examples 1 and 2.
  • the value was shown, and the peel adhesive strength was significantly higher than that after the water volatilization.
  • the blending amount of the acrylic acid alkyl ester-based copolymer emulsion is 20% by mass or more and less than 70% by mass with respect to the total mass of the pressure-sensitive adhesive layer, thereby containing water. It was confirmed that it is possible to provide a non-pharmaceutical water-containing patch having low skin irritation while maintaining high adhesiveness during time and drying.

Abstract

[Problem] To provide a hydrous adhesive patch which retains adhesive force even after the water contained in the pressure-sensitive adhesive layer has volatilized off. [Solution] A hydrous adhesive patch for non-medical products which includes a pressure-sensitive adhesive layer including an emulsion of an alkyl acrylate copolymer in a proportion of 20 mass% or higher but less than 70 mass%, the alkyl acrylate copolymer being a copolymer of a monomer mixture comprising monomer A and monomer B. The monomer A is a monomer which, when homopolymerized, forms a polymer having a glass transition temperature (Tg) of 270K or higher, and the monomer B is a monomer which, when homopolymerized, forms a polymer having a glass transition temperature (Tg) of 220K or lower.

Description

非医薬品用含水系貼付剤Non-pharmaceutical water-containing patch
 本発明は非医薬品用含水系貼付剤に関するものであり、詳細には、粘着剤層中の水分が揮散された後においても高い粘着力が維持され、且つ、皮膚刺激性の低い、含水系貼付剤に関する。 The present invention relates to a non-pharmaceutical water-containing patch, and more specifically, a water-containing patch that maintains high adhesive strength even after the water in the pressure-sensitive adhesive layer is volatilized and has low skin irritation. Regarding the agent.
 一般に「パップ剤」とも称される水を含む粘着基剤を用いる貼付剤(本明細書において含水系貼付剤と称する)は、膏体層(粘着剤層)を織布、編布、不織布等の支持体上に備える貼付剤の一種である。パップ剤は、膏体層に水を含む粘着基剤を用いているため、皮膚刺激性は低いものの粘着力が弱く、特に膏体層中の水分の揮散とともに粘着力が経時的に低下し、皮膚から剥離し易いことが問題であった。
 こうした問題を解決するために、非水系(疎水性、親油性とも称する)の粘着剤を構成する一成分として知られるアクリル酸アルキルエステル共重合体を分散させたエマルション(エマルジョンとも)基剤を、含水系貼付剤の膏体層(粘着剤層)に配合する技術が知られている。
A patch using a water-containing adhesive base, which is also generally referred to as a "pap agent" (referred to as a water-containing adhesive in the present specification), has a plaster layer (adhesive layer) as a woven fabric, knitted fabric, non-woven fabric, or the like. It is a kind of patch to be provided on the support of. 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 the adhesive strength decreases with time, especially with the volatilization of water in the plaster layer. 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 (hydrophobic or lipophilic) adhesive is dispersed is used. A technique of blending a water-containing patch into a plaster layer (adhesive layer) is known.
 例えば、特許文献1には、長時間の貼付でも優れた粘着力と再貼着力を有し、水分の喪失に伴う硬化及びしなやかさの抑制を図った含水系の貼付剤の提供を目的として、含水系外用貼付剤用組成物全体に対して、アクリル酸メチル・アクリル酸2-エチルヘキシル共重合体を5.0質量%以上10質量%以下、水分散性界面活性剤を0.01質量%以上10.0質量%以下配合した貼付剤が開示されている。
 また特許文献2には、時間経過によるパップ剤の水含有量が減少した場合においても十分な付着力を有するパップ剤の提供を課題として、ポリアクリル酸中和物と該中和物の2.5~10倍質量(膏体基準で5~25質量%)のアクリル酸メチル・アクリル酸2-エチルヘキシル共重合体とポリアクリル酸とを含有するパップ剤が開示されている。
 特許文献3には、より小さな力で剥離ライナーを剥離可能なパップ剤の提供を目的として、ポリ(アクリル酸メチル/アクリル酸2-エチルヘキシル)と界面活性剤としてポリエチレングリコールのモノ脂肪酸エステル等を含むパップ剤が開示されている。
For example, Patent Document 1 aims to provide a water-containing patch having excellent adhesive force and re-sticking force even after long-term sticking, and suppressing hardening and suppleness due to loss of water. 5.0% by mass or more and 10% by mass or less of the methyl acrylate / 2-ethylhexyl acrylate copolymer and 0.01% by mass or more of the water-dispersible surfactant with respect to the entire composition for a water-containing external patch. A patch containing 10.0% by mass or less is disclosed.
Further, in Patent Document 2, a polyacrylic acid neutralized product and the neutralized product 2. A poultice containing 5 to 10 times by mass (5 to 25% by mass based on a plaster) of a methyl acrylate / 2-ethylhexyl acrylate copolymer and polyacrylic acid is disclosed.
Patent Document 3 contains poly (methyl acrylate / 2-ethylhexyl acrylate) and a monofatty acid ester of polyethylene glycol as a surfactant for the purpose of providing a poultice that can peel off a peeling liner with a smaller force. Pap agents are disclosed.
特許第5650684号Patent No. 5650684 特許第5921779号Patent No. 5921779 特許第6469136号Patent No. 6469136
 上述のように、含水系貼付剤の粘着持続性を高めるために、アクリル酸メチル・アクリル酸2-エチルヘキシル共重合体等のアクリル酸アルキルエステル共重合体を粘着剤層に配合することが知られている。
 しかしこれまで提案された含水系貼付剤において、特に粘着剤層中の水分が揮散した後における粘着力は、テープ剤と比較すると十分に満足できるといえるものではなかった。
 また従来、含水系貼付剤の粘着剤層を構成する親水性アクリル系粘着剤(ポリアクリル酸部分中和物(昭和電工(株)製、ビスコメート(登録商標)NP-800等)など)や粘稠化剤(カルメロースナトリウム等)は、通常親水性の高い高分子化合物であるため、直接水に投入するとダマが発生し得る。加えて架橋剤(ジヒドロキシアルミニウムアミノアセテート(協和化学工業〈株〉製、グリシナール等)など)は、水に溶解してその機能を失うことがないよう、その溶解を抑制することが必要となる場合がある。こうした理由から、水をほとんど含まない湿潤剤にこれら成分を分散させ、粘着剤層を形成する組成物にこれを投入する方法が、パップ剤の製造で一般に実施されている。しかし前記エマルションを20質量%以上の割合で配合した場合、前述の親水性アクリル系粘着剤、粘稠化剤及び架橋剤を粘着剤層に分散させる役割を担う、水を含まない湿潤剤(濃グリセリン等)の配合量が相対的に少なくなる。そのため、これら成分を粘着剤層に十分に分散させることができず、結果として粘着剤中にダマが発生する問題があった。
 また、アクリル酸メチル・アクリル酸2-エチルヘキシル共重合体等のアクリル酸アルキルエステル共重合体を20%以上配合すると、他の成分の配合量が少なくなり、架橋反応がしにくくなったり、保形性が保てない問題があった。
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, in the water-containing adhesives proposed so far, the adhesive strength after the moisture in the adhesive layer is volatilized is not sufficiently satisfactory as compared with the tape agent.
In addition, conventionally, hydrophilic acrylic pressure-sensitive adhesives (polyacrylic acid partially neutralized products (manufactured by Showa Denko Corporation, Viscomate (registered trademark) NP-800, etc.), etc.) and stickiness constituting the pressure-sensitive adhesive layer of water-containing patches have been used. Since the thickening agent (sodium carmellose, etc.) is usually a highly hydrophilic high molecular compound, lumps may occur when it is directly put into water. In addition, when it is necessary to suppress the dissolution of a cross-linking agent (dihydroxyaluminum aminoacetate (manufactured by Kyowa Chemical Industry Co., Ltd., glycinal, etc.) so as not to dissolve in water and lose its function). There is. For this reason, a method of dispersing these components in a wetting agent containing almost no water and adding the components to a composition forming a pressure-sensitive adhesive layer is generally practiced in the production of a poultice. However, when the emulsion is blended in a proportion of 20% by mass or more, a water-free wetting agent (concentrated) that plays a role of dispersing the above-mentioned hydrophilic acrylic pressure-sensitive adhesive, thickening agent and cross-linking agent in the pressure-sensitive adhesive layer. The amount of glycerin, etc.) is relatively small. Therefore, these components cannot be sufficiently dispersed in the pressure-sensitive adhesive layer, and as a result, there is a problem that lumps are generated in the pressure-sensitive adhesive.
Further, when an acrylic acid alkyl ester copolymer such as a methyl acrylate / 2-ethylhexyl acrylate copolymer is blended in an amount of 20% or more, the blending amount of other components is reduced, the cross-linking reaction becomes difficult, and the shape is retained. There was a problem that I couldn't keep my sex.
 本発明者らは、前記課題を解決するために鋭意研究を行った結果、非医薬品用含水系貼付剤の粘着剤層に、アクリル酸アルキルエステル系共重合体として、ホモ重合したときのガラス転移温度(Tg)が270K以上のポリマーとなるモノマーと、ホモ重合したときのTgが220K以下のポリマーとなるモノマーを共重合した共重合体のエマルションを、従来量を遥かに上回る20質量%以上70質量%未満の割合にて配合することにより、粘着剤層形成時におけるダマ発生を抑制し、架橋性や保形性を損なうことなく、また粘着剤層中の水分が揮散した後においても粘着力が低下せずにむしろ著しく向上すること、かつ、皮膚刺激性も低いことを見出し、本発明を完成した。 As a result of diligent research to solve the above problems, the present inventors have made a glass transition when homopolymerized as an acrylic acid alkyl ester-based copolymer on the pressure-sensitive adhesive layer of a non-pharmaceutical water-containing patch. A copolymer emulsion obtained by copolymerizing a monomer having a temperature (Tg) of 270 K or more and a polymer having a Tg of 220 K or less when homopolymerized is 20% by mass or more 70, which far exceeds the conventional amount. By blending in a proportion of less than mass%, the generation of lumps during the formation of the pressure-sensitive adhesive layer is suppressed, the crosslinkability and shape retention are not impaired, and the adhesive strength even after the moisture in the pressure-sensitive adhesive layer is volatilized. The present invention has been completed by finding that the polymer does not decrease, but rather improves significantly, and that the skin irritation is also low.
 すなわち本発明は:
[1]
支持体と、該支持体上に設けられた粘着剤層及び剥離ライナーからなる非医薬品用含水系貼付剤であって、
前記粘着剤層が、
1)アクリル系親水性粘着剤、
2)アクリル酸アルキルエステル系共重合体エマルション、
3)架橋剤、
4)粘稠化剤、
5)水をほとんど含まない湿潤剤を含む、湿潤剤、及び
6)水、
を含有し、
前記アクリル酸アルキルエステル共重合体は、モノマーAとモノマーBからなるモノマー混合物の共重合体であって、
前記モノマーAは、該モノマーAをホモ重合したときガラス転移温度(Tg)が270K以上のポリマーとなるモノマーであり、
前記モノマーBは、該モノマーBをホモ重合したときガラス転移温度(Tg)が220K以下のポリマーとなるモノマーであり、
該粘着剤層の全質量に対して20質量%以上70質量%未満の割合にてアクリル酸アルキルエステル系共重合体エマルジョンを含有する、
非医薬品用含水系貼付剤。
That is, the present invention is:
[1]
A non-pharmaceutical water-containing patch comprising a support, an adhesive layer provided on the support, and a release liner.
The pressure-sensitive adhesive layer
1) Acrylic hydrophilic adhesive,
2) Acrylic acid alkyl ester-based copolymer emulsion,
3) Crosslinking agent,
4) Condensing agent,
5) Wetting agents containing little water, and 6) water,
Contains,
The acrylic acid alkyl ester copolymer 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 higher when the monomer A is homopolymerized.
The monomer B is a polymer having a glass transition temperature (Tg) of 220 K or less when the monomer B is homopolymerized.
The acrylic acid alkyl ester-based copolymer emulsion is contained in a proportion of 20% by mass or more and less than 70% by mass with respect to the total mass of the pressure-sensitive adhesive layer.
Water-containing patch for non-pharmaceutical products.
 そして本発明によれば、さらに以下の実施態様が提供される。
[2]
下記(a)乃至c)のうち1項もしくは2項以上を備えることを特徴とする、[1]に記載の非医薬品用含水系貼付剤。
a)前記アクリル酸アルキルエステル系共重合体は、前記モノマー混合物の全質量に対して、前記モノマーAの割合が30質量%以上50質量%以下である、アクリル酸アルキルエステル系共重合体である。
b)前記粘着剤層は、pH2~4である。
c)前記水をほとんど含まない湿潤剤(水分16%以下)の配合量に対する、前記親水性アクリル系粘着剤、前記粘稠化剤、及び前記架橋剤の合計配合量の質量比率が、(合計配合量)/(前記湿潤剤)=7.25/25~7.25/10である。
[3]
前記水をほとんど含まない湿潤剤が、濃グリセリン、グリセリン、D-ソルビトール、エチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、流動パラフィン、1,3-プロパンジオール、1,4-ブタンジオール、マルチトール、及びキシリトールからなる群から選択される、[1]又は[2]に記載の非医薬品用含水系貼付剤。
[4]
前記粘着剤層は、
貼付剤の製造日から50℃、16時間保管後において、1N/15mm以上のピール粘着力を有し、
貼付剤の製造直後において、0.7N/mmφ以上のプローブタックを有し、かつ、
貼付剤の製造直後の粘着剤層のプローブタック値に対して、貼付剤の製造日から50℃、16時間保管後の粘着剤層のプローブタック値が1.8倍以上である、
[1]乃至[3]のうち何れか一項に記載の非医薬品用含水系貼付剤。
[5]
前記粘着剤層が、さらに
7)清涼化剤
8)有機溶媒、
9)pH調節剤、
10)キレート剤、
を含有する、[1]乃至請求項[4]のうち何れか一項に記載の非医薬品用含水系貼付剤。
Further, according to the present invention, the following embodiments are further provided.
[2]
The non-pharmaceutical water-containing patch according to [1], which comprises one or more of the following (a) to (c).
a) The acrylic acid alkyl ester-based copolymer is an acrylic acid alkyl ester-based copolymer 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. ..
b) The pressure-sensitive adhesive layer has a pH of 2 to 4.
c) The mass ratio of the total amount of the hydrophilic acrylic pressure-sensitive adhesive, the thickening agent, and the cross-linking agent to the amount of the wetting agent (moisture 16% or less) containing almost no water is (total). Blending amount) / (the wetting agent) = 7.25 / 25 to 7.25 / 10.
[3]
The wetting agent containing almost no water is concentrated glycerin, glycerin, D-sorbitol, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, liquid paraffin, 1,3-propanediol, 1,4-butanediol, and martitol. The non-pharmaceutical water-containing patch according to [1] or [2], which is selected from the group consisting of, and xylitol.
[4]
The pressure-sensitive adhesive layer is
It has a peel adhesive strength of 1N / 15 mm or more after storage at 50 ° C. for 16 hours from the date of manufacture of the patch.
Immediately after the patch is manufactured, it has a probe tack of 0.7 N / mmφ or more and has a probe tack.
The probe tack value of the pressure-sensitive adhesive layer immediately after the production of the patch is 1.8 times or more the probe tack value of the pressure-sensitive adhesive layer after storage at 50 ° C. for 16 hours from the date of manufacture of the patch.
The non-pharmaceutical water-containing patch according to any one of [1] to [3].
[5]
The pressure-sensitive adhesive layer is further 7) a cooling agent 8) an organic solvent,
9) pH regulator,
10) Chelating agent,
The non-pharmaceutical water-containing patch according to any one of [1] to [4].
 本発明によれば、ホモ重合したときのガラス転移温度(Tg)が270K以上のポリマーとなるモノマーAと、ホモ重合したときのTgが220K以下のポリマーとなるモノマーBとからなるモノマー混合物の共重合体であるアクリル酸アルキルエステル系共重合体のエマルジョンを、非医薬品用含水系貼付剤の粘着剤層に20質量%以上70質量%未満にて配合することにより、そして好ましい態様においては、a)前記モノマー混合物の全質量に対して、前記モノマーAの割合を30質量%以上50質量%以下であるアクリル酸アルキルエステル系共重合体を採用するか、b)前記粘着剤層がpH2~4であるか、又は、c)親水性高分子(親水性アクリル系粘着剤及び粘稠化剤)並びに架橋剤の合計配合量/水をほとんど含まない湿潤剤(濃グリセリン等)の配合量の質量比率を7.25/25~7.25/10とすることにより、粘着剤層形成時におけるダマ発生を抑制し、また粘着剤層中の水分が揮散した後においても粘着力を維持でき、かつ、皮膚刺激性が低い非医薬品用含水系貼付剤を提供できる。 According to the present invention, a monomer mixture consisting of a monomer A having a glass transition temperature (Tg) of 270 K or more at the time of homopolymerization and a monomer B having a Tg of 220 K or less at the time of homopolymerization. By blending the emulsion of the acrylic acid alkyl ester-based copolymer as the polymer in the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch in an amount of 20% by mass or more and less than 70% by mass, and in a preferred embodiment, a. ) Adopt an acrylic acid alkyl ester-based copolymer 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, or b) the pressure-sensitive adhesive layer has a pH of 2 to 4. Or c) Total amount of hydrophilic polymer (hydrophilic acrylic pressure-sensitive adhesive and thickening agent) and cross-linking agent / mass of amount of wetting agent containing almost no water (concentrated glycerin, etc.) By setting the ratio to 7.25 / 25 to 7.25 / 10, the generation of lumps during the formation of the pressure-sensitive adhesive layer can be suppressed, and the adhesive strength can be maintained even after the water content in the pressure-sensitive adhesive layer is volatilized. , A non-pharmaceutical water-containing patch having low skin irritation can be provided.
 上述したように、含水系貼付剤の粘着力の持続性を高めるべく、アクリル酸メチル・アクリル酸2-エチルヘキシル共重合樹脂エマルジョン(商品名 ニカゾールTS-620、日本カーバイド工業(株))等のアクリル酸アルキルエステル共重合体エマルションを粘着剤層に配合する提案や、この配合量を増量する提案がなされている。しかしこれまでの提案では、共重合体の配合量を増加させた場合においても、特に粘着剤層中の水分が揮散した後(水揮散後)の粘着力はテープ剤と比べて十分なものとはいえるものではなかった。
 本発明者らは、上記の課題に際し、従来提案された配合量を超える、20質量%以上70質量%未満の量にてアクリル酸メチル・アクリル酸2-エチルヘキシル共重合樹脂エマルジョン(以下、共重合体エマルションともいう)を粘着剤層に配合することにより、粘着剤層中の水分が揮散した後においても粘着力を維持でき、かつ、皮膚刺激性が低い非医薬品用含水系貼付剤を提供できることを見出した。
 以下、本発明の非医薬品用含水系貼付剤の構成について説明する。
As described above, acrylics such as methyl acrylate / 2-ethylhexyl acrylate copolymer resin emulsion (trade name: Nicazole TS-620, Nippon Carbide Industries Co., Ltd.), etc., in order to enhance the durability of the adhesive strength of the water-containing patch. Proposals have been made to blend an acid alkyl ester copolymer emulsion 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 sufficiently sufficient as compared with the tape agent. I couldn't say that.
The present inventors have encountered the above-mentioned problems in an amount of 20% by mass or more and less than 70% by mass, which exceeds the amount previously proposed, and is an emulsion of a copolymerized resin emulsion of methyl acrylate and 2-ethylhexyl acrylate (hereinafter, co-weight). By blending (also referred to as a coalesced emulsion) in the pressure-sensitive adhesive layer, it is possible to provide a non-pharmaceutical water-containing patch which can maintain the adhesive strength even after the water in the pressure-sensitive adhesive layer is volatilized and has low skin irritation. I found.
Hereinafter, the configuration of the non-pharmaceutical water-containing patch of the present invention will be described.
 本発明の非医薬品用含水系貼付剤(以下、単に「貼付剤」とも称する)は、支持体と、該支持体上に設けられた粘着剤層及び剥離ライナーからなる。
 上記貼付剤、特に支持体と、該支持体上に設けられた粘着剤層からなる製剤部分の形状は特に限定されず、方形(正方形、長方形等)、四角形(台形、菱形等)、多角形、円形、楕円形、半円形、三角形、三日月形、並びにこれらを組み合わせた形状等、貼付箇所に合わせて種々の形状を選択できる。
 なお貼付剤(特に上記の製剤部分)の面積は適宜決定することができ、例えば貼付剤の使用目的などを考慮し、例えば2~300cmの範囲とすることができる。
The non-pharmaceutical water-containing patch of the present invention (hereinafter, also simply referred to as “patch”) comprises a support, a pressure-sensitive adhesive layer provided on the support, and a release liner.
The shape of the patch, particularly the support, and the preparation portion consisting of the pressure-sensitive adhesive layer provided on the support is not particularly limited, and is rectangular (square, rectangle, etc.), quadrangular (trapezoid, rhombus, etc.), polygonal. , Circular, oval, semi-circular, triangular, crescent-shaped, and a combination of these, etc., various shapes can be selected according to the attachment location.
The area of the patch (particularly the above-mentioned pharmaceutical product portion) can be appropriately determined, and can be, for example, in the range of 2 to 300 cm 2 in consideration of the purpose of use of the patch.
[粘着剤層]
 本発明の非医薬品用含水系貼付剤は、その含水系の粘着剤層に対して、後述する親水性のアクリル系粘着剤に加えて、一般に非水系のアクリル系粘着剤を構成するアクリル酸アルキルエステル系共重合体のエマルジョンも配合することを特徴とする。
 一般に含水系貼付剤の粘着剤層(膏体層)に使用される粘着剤としては、ポリアクリル酸、ポリアクリル酸部分中和物、ポリアクリル酸ナトリウム、N-ビニルアセトアミド・アクリル酸ナトリウム共重合樹脂等の親水性のアクリル系粘着剤が広く用いられている。上記の親水性のアクリル系粘着剤と親和性が高く、均一に練合できる観点から、含水系貼付剤の含水系の粘着剤層に配合する非水系粘着剤としては、アクリル系及びメタクリル系のエマルション型の粘着剤が好ましく配合される。
 なお、本明細書において「アクリル酸アルキルエステル系共重合体」とは、アクリル酸及びメタクリル酸のアルキルエステルの双方を含むことを意図し、また「アクリル系粘着剤」もアクリル系粘着剤とメタクリル系粘着剤の双方を含むことを意図してなる。
[Adhesive layer]
The non-pharmaceutical water-containing patch of the present invention generally constitutes a non-aqueous acrylic pressure-sensitive adhesive in addition to the hydrophilic acrylic pressure-sensitive adhesive described later for the water-containing pressure-sensitive adhesive layer. It is characterized by blending an emulsion of an ester-based copolymer.
Generally, the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer (plaster layer) of a water-containing patch includes 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 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 acrylic acid and methacrylic acid alkyl esters, and the "acrylic adhesive" is also an acrylic pressure-sensitive adhesive and methacrylic acid. It is intended to contain both of the adhesives.
<アクリル酸アルキルエステル系共重合体>
 非水系のアクリル系粘着剤を構成するアクリル酸アルキルエステル系共重合体(非水系粘着基剤)は、粘着力を発現する成分として、アルキルエステルの炭素原子数が2~9であり、ホモ重合させたときガラス転移温度(Tg)が-55℃(218K)以下のポリマーとなるモノマーと、凝集力を向上させる成分として、ホモ重合させたときTgが8~165℃(281~438K)のポリマーとなるモノマーと、さらに必要によってはカルボキシル基やヒドロキシ基といった架橋点となるなどの官能基を有するモノマーで構成される共重合体である(モノマーの一例を表1に挙げた)。
 本発明において使用するアクリル酸アルキルエステル系共重合体は、ホモ重合したときガラス転移温度(Tg)が270K以上のポリマーとなるモノマーAと、ホモ重合したときガラス転移温度(Tg)が220K以下のポリマーとなるモノマーBからなるモノマー混合物の共重合体である。上記モノマーAのホモポリマーのガラス転移温度Tgの上限値はおよそ500Kであり、また、上記モノマーBのホモポリマーのガラス転移温度Tgの下限値はおよそ200Kである。
<Acrylic acid alkyl ester-based 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 to 438K) when homopolymerized as a component for improving aggregation power. 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 has a 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 a monomer B as 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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 なお、粘着力を発現するモノマーのみを重合したホモポリマーは、粘着力は高いものの機械的強度が弱いとされ、一般に凝集力を向上させるモノマーとの共重合により機械的強度を向上させた共重合体が粘着剤として用いられる。
 上記の表1に示す粘着力を発現するモノマーとして挙げたように、本発明では、より粘着力の高いモノマーとして、該モノマーをホモ重合させたとき(ホモポリマー)のTgが220K以下であるアクリル酸ブチル、アクリル酸2-エチルヘキシル、アクリル酸オクチル、アクリル酸イソノニル等が用いられる。これらのうち、アクリル酸ブチル、アクリル酸2-エチルヘキシルが好ましく、なかでも医薬品添加物として使用実績があり、粘着力の高い(ホモポリマーのTgが低い)アクリル酸2-エチルヘキシルを好ましく用いることができる。
 また凝集力を向上させるモノマー(ホモポリマーのTgが270K以上)としては表1に挙げたモノマーが挙げられ、これらの中でもアクリル酸メチル、メタクリル酸メチル、メタクリル酸エチル及びメタクリル酸n-ブチルが好ましく、本発明では、機械的強度が高く、粘着性を著しく低下させない(ホモポリマーのTgが比較的低い)アクリル酸メチルが特に好ましい。
It should be noted that homopolymers obtained by polymerizing only a monomer that exhibits adhesive strength are said to have high adhesive strength but weak mechanical strength, and in general, copolymerization with a monomer that improves cohesive strength improves mechanical strength. The coalescence is used as an adhesive.
As mentioned 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 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 aggregating power (the homopolymer Tg 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.
 なお、従来技術において挙げたように、貼付剤に使用される市販のアクリル酸アルキルエステル系共重合体のエマルションとして、日本カーバイド(株)製の、ニカゾール(登録商標)TS-620(アクリル酸メチル・アクリル酸2-エチルヘキシル共重合樹脂エマルジョン)がある。アクリル酸メチル・アクリル酸2-エチルヘキシル共重合樹脂エマルジョンは、医薬品添加物規格の収載品である。医薬品添加物規格(2018年)によれば、ニカゾールTS-620を水浴上で蒸発乾固した後、105℃で3時間乾燥するとき、蒸発残留物の量は57~61%である。
 なお、上記共重合体において、ホモポリマーのTgが270K以上となるモノマーAの割合を30質量%以上50質量%以下とすることにより、粘着剤層の水気散時における粘着力の向上が期待できる。
As mentioned in the prior art, as an emulsion of a commercially available acrylic acid alkyl ester-based copolymer used for a patch, Nikazole (registered trademark) TS-620 (methyl acrylate) manufactured by Nippon Carbide Co., Ltd. -There is a 2-ethylhexyl acrylate copolymer resin emulsion). The methyl acrylate / 2-ethylhexyl acrylate copolymer resin emulsion is listed in the pharmaceutical additive standard. According to the Pharmaceutical Additives Standard (2018), when Nikazole TS-620 is evaporated to dryness on a water bath and then dried at 105 ° C. for 3 hours, the amount of evaporation residue is 57 to 61%.
In the above copolymer, by setting the proportion of the monomer A in which the Tg of the homopolymer is 270 K or more to 30% by mass or more and 50% by mass or less, improvement in the adhesive strength of the pressure-sensitive adhesive layer at the time of water dispersal can be expected. ..
 本発明の非医薬品用含水系貼付剤の粘着剤層において、アクリル酸アルキルエステル系共重合体エマルションの配合量は、非医薬品用含水系貼付剤の粘着剤層の全質量を基準として20質量%以上70質量%未満、また20質量%以上60質量%以下とすることができる。後述するアクリル系親水性粘着剤との配合割合は、例えば、質量比で、アクリル酸アルキルエステル系共重合体エマルション:アクリル系親水性粘着剤=5:1~15:1などとすることができる。
 またアクリル酸アルキルエステル系共重合体の配合量(固形分換算量)は、非医薬品用含水系貼付剤の粘着剤層の全質量を基準として例えば0.1質量%以上40質量%以下、また10質量%以上37質量%以下とすることができる。後述するアクリル系親水性粘着剤との配合割合は、例えば、質量比で、アクリル酸アルキルエステル系共重合体(固形分換算量):アクリル系親水性粘着剤=10:1~1:10、同=5:1~1:5、同=3:1~1:2、同=2:1~1:1などとすることができる。
In the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention, the blending amount of the acrylic acid alkyl ester-based copolymer emulsion is 20% by mass based on the total mass of the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch. It can be more than 70% by mass and 20% by mass or more and 60% by mass or less. The mixing ratio with the acrylic hydrophilic pressure-sensitive adhesive, which will be described later, can be, for example, an acrylic acid alkyl ester-based copolymer emulsion: acrylic-based hydrophilic pressure-sensitive adhesive = 5: 1 to 15: 1 in terms of mass ratio. ..
The blending amount (solid content equivalent amount) of the acrylic acid alkyl ester-based copolymer is, for example, 0.1% by mass or more and 40% by mass or less, based on the total mass of the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch. It can be 10% by mass or more and 37% by mass or less. The mixing ratio with the acrylic hydrophilic pressure-sensitive adhesive described later is, for example, in terms of mass ratio, acrylic acid alkyl ester-based copolymer (solid content equivalent amount): acrylic hydrophilic pressure-sensitive adhesive = 10: 1 to 1:10, The same = 5: 1 to 1: 5, the same = 3: 1 to 1: 2, the same = 2: 1 to 1: 1 and the like.
<アクリル系親水性粘着剤>
 本発明の非医薬品用含水系貼付剤の粘着剤層は、アクリル系親水性粘着剤を含有する。
 上記アクリル系親水性粘着剤としては、水溶性の(メタ)アクリル系ポリマーが挙げられる。水溶性(メタ)アクリル系ポリマーは、水溶性を有する官能基(親水性基)を有する(メタ)アクリロイル基含有モノマーを重合して得られるポリマーであり、粘着剤層に水とともに配合することで、粘着性を発揮する。水溶性(メタ)アクリル系ポリマーは、例えばポリアクリル酸、ポリアクリル酸の中和物等のホモポリマー;N-ビニルアセトアミド・アクリル酸ナトリウム共重合樹脂等のコポリマーが挙げられる。
 上記ポリアクリル酸中和物は、ポリアクリル酸完全中和物であっても、ポリアクリル酸部分中和物であっても、これらの混合物であってもよい。ポリアクリル酸中和物とは、ポリアクリル酸塩を意味し、例えば、ナトリウム塩、カリウム塩、カルシウム塩、アンモニウム塩等を用いることができる。
<Acrylic hydrophilic adhesive>
The pressure-sensitive adhesive layer of the non-pharmaceutical 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 can be blended with water in the pressure-sensitive adhesive layer. , Demonstrates adhesiveness. Examples of the water-soluble (meth) acrylic polymer include homopolymers such as polyacrylic acid and a neutralized product of polyacrylic acid; and copolymers such as N-vinylacetamide / sodium acrylate copolymer resin.
The polyacrylic acid neutralized product may be a completely neutralized product of polyacrylic acid, a partially neutralized product of 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.
 アクリル系親水性粘着剤の配合量は、非医薬品用含水系貼付剤の粘着剤層の全質量を基準として、例えば0.1質量%以上10質量%以下、1質量%以上8質量%以下とすることができる。 The blending amount of the acrylic hydrophilic pressure-sensitive adhesive is, 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 non-pharmaceutical water-containing patch. can do.
<架橋剤>
 本発明の非医薬品用含水系貼付剤の粘着剤層は、更に架橋剤を含有する。該架橋剤としては、多価金属塩が挙げられ、中でもアルミニウムを含む多価金属化合物が挙げられる。一例として、水酸化アルミニウム、水酸化アルミナマグネシウム等の水酸化物;塩化アルミニウム、硫酸アルミニウム、硫酸アルミニウムカリウム、アルミニウムグリシネート(ジヒドロキシアルミニウムアミノアセタール)、ジヒドロキシアルミニウムアミノアセテート、合成ケイ酸アルミニウム、乾燥水酸化アルミニウムゲル、カオリン、ステアリン酸アルミニウム等の無機又は有機酸の正塩又はそれらの塩基性塩;アルミニウムミョウバン等の復塩;アルミン酸ナトリウム等のアルミン酸塩;無機性アルミニウム錯塩及び有機性アルミニウムキレート化合物;合成ヒドロタルサイト、ケイ酸アルミン酸マグネシウム、メタケイ酸アルミン酸マグネシウム等の多価金属化合物が挙げられ、これらを単独又は2種以上の組み合わせで用いることができる。
<Crosslinking agent>
The pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention further contains a cross-linking agent. Examples of the cross-linking agent include polyvalent metal salts, and examples thereof include 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 aluminate; inorganic aluminum complex salts and organic aluminum chelate compounds. Examples thereof include polyvalent metal compounds such as synthetic hydrotalcite, magnesium aluminate silicate, and magnesium aluminate metasilicate, and these can be used alone or in combination of two or more.
 架橋剤の配合量は、粘着剤の皮膚への残留や貼着性の一因となり得る架橋度を考慮して適宜選択すればよい。例えばその配合量は、非医薬品用含水系貼付剤の粘着剤層の全質量を基準として、例えば0.01質量%以上6.0質量%以下、0.01質量%以上4.0質量%以下、あるいは、0.01質量%以上2.0質量%以下の範囲を挙げることができる。 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 residual adhesive on the skin and the adhesiveness. For example, the blending amount is, 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, based on the total mass of the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch. Alternatively, the range of 0.01% by mass or more and 2.0% by mass or less can be mentioned.
<粘稠化剤>
 本発明の非医薬品用含水系貼付剤の粘着剤層は粘稠化剤を含有し、これは粘着剤の保形性向上や粘着性向上としての機能が期待される。該粘稠化剤としては、例えば、エチルセルロース、カルメロールナトリウム、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒプロメロース、メチルセルロース等のセルロース類、アルギン酸ナトリウム、カラギーナン、キサンタンガム、ヒアルロン酸ナトリウム等の多糖類、ゼラチン、尿素等が挙げられる。このうち、チキソトピー性があり展延性が向上するカルメロースナトリウムが好適である。これらは1種単独で、又は2種以上を適宜組み合わせて、使用できる。
 粘稠化剤の配合量は、通常、非医薬品用含水系貼付剤の粘着剤層の全質量を基準として、例えば0.1質量%以上10質量%以下、0.5質量%以上20質量%以下、あるいは1.0質量%以上10質量%以下の範囲とすることができる。
<Thickening agent>
The pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention contains a thickening agent, which is expected to function as improving the shape retention and the tackiness of the pressure-sensitive adhesive. Examples of the thickening agent include celluloses such as ethyl cellulose, sodium carmerol, hydroxyethyl cellulose, hydroxypropyl cellulose, hypromellose and methyl cellulose, polysaccharides such as sodium alginate, carrageenan, xanthan gum and sodium hyaluronate, gelatin and urea. Can be mentioned. Of these, carmellose sodium, which has thixotopy properties and improves ductility, is preferable. These can be used alone or in combination of two or more.
The blending amount of the thickening agent is usually, for example, 0.1% by mass or more and 10% by mass or less, 0.5% by mass or more and 20% by mass, based on the total mass of the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch. Below, or in the range of 1.0% by mass or more and 10% by mass or less.
<湿潤剤>
 本発明の非医薬品用含水系貼付剤の粘着剤層は、湿潤剤(保湿剤とも)を含有する。該湿潤剤には、経時的な水分の蒸発を抑制する機能とともに、親水性アクリル系粘着剤等の水溶性高分子、カルメロースナトリウム等の粘稠化剤、架橋剤等、直接水に配合するとダマ発生や架橋により増粘することを抑制する機能が期待される。後者の直接水に配合することを避けるという理由においては、水をほとんど含まない湿潤剤を使用することが望ましい。すなわち粘着剤層形成時において、無水の湿潤剤であるか、水を含んでいたとしてもごく少量(例えば16%以下)である湿潤剤に、前記親水性アクリル系粘着剤、粘稠化剤、架橋剤等を配合して予製剤とした後、粘着剤層を構成する他成分と混合することにより、ダマ発生や増粘を抑制できる。そのような湿潤剤としては、例えば、濃グリセリン、グリセリン、D-ソルビトール、エチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、流動パラフィン、1,3-プロパンジオール、1,4-ブタンジオール、マルチトール、キシリトール等の多価アルコールが挙げられる。これらは、1種単独で、又は2種類以上を適宜組み合わせて、使用できる。
 なお、前者の経時的な水分の蒸発を抑制するという理由においては、水を含む湿潤剤を好適に配合できる。例えば通常70%水溶液として用いられるD-ソルビトール液は、水分を含むため、ダマ発生や増粘の抑制(前述の予製剤の調製)に用いることは困難であるが、その後の他成分と混合する際に一緒に配合することが可能である。
 湿潤剤の配合量(水をほとんど含まない湿潤剤と、水を含む湿潤剤との合計量)は、通常、非医薬品用含水系貼付剤の粘着剤層の全質量を基準として、例えば1.0質量%以上70質量%以下、5.0質量%以上60質量%以下、あるいは10質量%以上60質量%以下の範囲とすることができる。
 なお、前述した親水性アクリル系粘着剤と粘稠化剤、及び架橋剤の合計配合量<A>と、水をほとんど含まない湿潤剤(例えば濃グリセリン)の配合量<B>質量比率を、<A>/<B>=7.25/25~7.25/10としてこれらを配合することにより、ダマが発生せず、均一に練合できることが期待できるため好適である。
<Wetting agent>
The pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention contains a wetting agent (also referred to as a moisturizing agent). The wetting agent has a function of suppressing evaporation of water over time, and can be directly mixed with water such as a water-soluble polymer such as a hydrophilic acrylic pressure-sensitive adhesive, a thickening agent such as carmellose sodium, and a cross-linking agent. It is expected to have a function of suppressing thickening due to lump generation and cross-linking. For the reason of avoiding the latter direct addition to water, it is desirable to use a wetting agent that contains almost no water. That is, at the time of forming the pressure-sensitive adhesive layer, the hydrophilic acrylic pressure-sensitive adhesive, the thickening agent, etc. By blending a cross-linking agent or the like to prepare a pre-formation and then mixing it with other components constituting the pressure-sensitive adhesive layer, lump generation and thickening can be suppressed. Examples of such wetting agents include concentrated glycerin, glycerin, D-sorbitol, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, liquid paraffin, 1,3-propanediol, 1,4-butanediol, and martitol. , Polyhydric alcohols such as xylitol. These can be used alone or in combination of two or more.
In addition, for the reason of suppressing the evaporation of water over time of the former, a wetting agent containing water can be preferably blended. For example, the D-sorbitol solution, which is usually used as a 70% aqueous solution, contains water, so that it is difficult to use it for suppressing the generation of lumps and thickening (preparation of the above-mentioned preform), but it is mixed with other components thereafter. It is possible to mix them together.
The blending amount of the wetting agent (the total amount of the wetting agent containing almost no water and the wetting agent containing water) is usually set based on, for example, the total mass of the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch. It can be in the range of 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 or more and 60% by mass or less.
In addition, the total amount <A> of the above-mentioned hydrophilic acrylic pressure-sensitive adhesive, the thickening agent, and the cross-linking agent and the amount <B> mass ratio of the wetting agent containing almost no water (for example, concentrated glycerin) are set. By blending these as <A> / <B> = 7.25 / 25 to 7.25 / 10, it is preferable because it can be expected that lumps do not occur and uniform kneading can be performed.
<水>
 上述した通り、本発明の非医薬品用含水系貼付剤は、粘着剤層中に水(水分)を含有するものである。本明細書において、粘着剤層に含まれる「水」とは、粘着剤層を形成時に、水として別に添加したものだけでなく、エマルションや水溶液などの形態として含まれる水も含む。
 水の配合量は特に限定されないが、非医薬品用含水系貼付剤の粘着剤層の全質量を基準として、例えば10質量%以上90質量%以下、15質量%以上70質量%以下、20質量%以上50質量%以下の範囲とすることができる。なおこの水分配合量は、貼付剤調製時、あるいは、貼付剤の貼付前の値であり、貼付の経過とともに粘着剤層から水が揮散した場合にはこの限りでない。
<Water>
As described above, the non-pharmaceutical 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 at the time of forming the pressure-sensitive adhesive layer, 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 non-pharmaceutical 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. It can be in the range of 50% by mass 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.
<清涼化剤>
 本発明の非医薬品用含水系貼付剤において、粘着剤層には清涼化剤を配合することができる。該清涼化剤としては、l-メントール、dl-カンフル、ケイヒ油、ゲラニオール、ハッカ油、ベルガモット油、d-ボルネオール、ユーカリ油等が挙げられ、これらを単独又は2種以上の組み合わせで用いることができる。
 清涼化剤を配合する場合、その配合量は、貼付時に清涼感を発現することを考慮して適宜選択すればよい。例えば清涼化剤としてのl-メントールの配合量は、非医薬品用含水系貼付剤の粘着剤層の全質量を基準として、例えば0.01質量%以上4.0質量%以下、0.01質量%以上3.0質量%以下の範囲を挙げることができる。
<Refreshing agent>
In the non-pharmaceutical water-containing patch of the present invention, a cooling agent can be added to the pressure-sensitive adhesive layer. Examples of the refreshing agent include l-menthol, dl-camphor, kehi oil, geraniol, peppermint oil, bergamot oil, d-borneol, eucalyptus oil and the like, and these may be used alone or in combination of two or more. can.
When a refreshing agent is blended, the blending amount may be appropriately selected in consideration of developing a refreshing sensation at the time of application. For example, the blending amount of l-menthol as a refreshing agent is, for example, 0.01% by mass or more and 4.0% by mass or less, 0.01% by mass, based on the total mass of the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch. The range of% or more and 3.0% by mass or less can be mentioned.
<有機溶媒>
 本発明の非医薬品用含水系貼付剤の粘着剤層は、更に有機溶媒を配合し得る。該粘着剤層に配合される有機溶媒は、各配合成分の溶解を補助し、また粘着剤層から各配合成分が析出することを防ぐ役割を有し得る。このような有機溶媒(溶解補助剤)として、クロタミトン;N-メチル-2-ピロリドン;マクロゴール400(ポリエチレングリコール)、ポリブチレングリコール等のポリアルキレングリコール;アジピン酸ジエチル、アジピン酸ジイソプロピル、セバシン酸ジエチル、セバシン酸ジイソプロピル、ミリスチン酸イソプロピル、パルミチン酸イソプロピル、オレイン酸オレイル等の脂肪酸エステル;ポリオキシアルキレン脂肪酸エステル等のソルビタンエステル類;1,3-ブタンジオール等の多価アルコール;ジメチルホルムアミド;ジメチルスルホキシド等が挙げられる。これらは一種単独で、あるいは2種以上を組合せて用いることができる。
<Organic solvent>
The pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention may further contain an organic solvent. The organic solvent blended in the pressure-sensitive adhesive layer may have a role of assisting the dissolution of each compounding component and preventing the precipitation of each compounding component from the pressure-sensitive adhesive layer. As such an organic solvent (solubilizing agent), crotamitone; N-methyl-2-pyrrolidone; polyalkylene glycol such as macrogol 400 (polyethylene glycol) and polybutylene glycol; diethyl adipate, diisopropyl adipate, diethyl sebacate , Fatty esters such as diisopropyl sebacate, isopropyl myristate, isopropyl palmitate, oleyl oleate; sorbitan esters such as polyoxyalkylene fatty acid esters; 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.
 有機溶媒の配合量は、非医薬品用含水系貼付剤の粘着剤層の全質量を基準として、例えば0.1質量%以上20質量%以下、0.5質量%以上10質量%以下、あるいは1.0質量%以上5質量%以下の範囲とすることができる。 The blending amount of the organic solvent is, for example, 0.1% by mass or more and 20% by mass or less, 0.5% by mass or more and 10% by mass or less, or 1 based on the total mass of the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch. It can be in the range of 0.0% by mass or more and 5% by mass or less.
<pH調節剤>
 本発明の非医薬品用含水系貼付剤の粘着剤層は、更にpH調節剤を配合し得る。pH調整剤としては、有機酸、無機酸の何れも使用することができ、これらを併用してもよい。
 該有機酸としては、例えばクエン酸、乳酸、酒石酸、グルコン酸、グリコール酸、リンゴ酸、フマル酸、メタスルホン酸、マレイン酸、酢酸等が挙げられ、これらを単独又は2種以上の組み合わせで用いることができる。有機酸のうち、乳酸等のヒドロキシ酸は難溶性アルミニウム化合物(架橋剤)の溶解性を向上させる効果も有する。
 また該無機酸としては、例えば、塩酸、ホウ酸、リン酸、硫酸等が挙げられ、これらを単独又は2種以上の組み合わせで用いることができる。
 有機酸の配合量は、非医薬品用含水系貼付剤の粘着剤層の全質量を基準として、例えば0.01質量%以上5質量%以下の範囲とすることができる。
 無機酸の配合量は、非医薬品用含水系貼付剤の粘着剤層の全質量を基準として、例えば0.1質量%以上1.2質量%以下の範囲とすることができる。
<pH regulator>
The pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention may further contain a pH adjuster. As the pH adjuster, either an organic acid or an inorganic acid can be used, and these may be used in combination.
Examples of the organic acid include citric acid, lactic acid, tartrate acid, gluconic acid, glycolic acid, malic acid, fumaric acid, metasulfonic acid, maleic acid, acetic acid and the like, and these may be used alone or in combination of two or more. Can be done. Of the organic acids, hydroxy acids such as lactic acid also have the effect of improving the solubility of the sparingly soluble aluminum compound (crosslinking agent).
Examples of the inorganic acid include hydrochloric acid, boric acid, phosphoric acid, sulfuric acid and the like, and 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 non-pharmaceutical water-containing patch.
The blending amount of the inorganic acid can be, for example, in the range of 0.1% by mass or more and 1.2% by mass or less based on the total mass of the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch.
<キレート剤>
 本発明の非医薬品用含水系貼付剤の粘着剤層には、難溶性アルミニウム化合物(架橋剤)の溶解速度を制御させるためにキレート剤を配合することができる。
 キレート剤としては、例えば、エデト酸ナトリウム(エチレンジアミン四酢酸2ナトリウム塩)が挙げられる。
 キレート剤の配合量は、通常、非医薬品用含水系貼付剤の粘着剤層の全質量を基準として、例えば0.01質量%以上1質量%以下の範囲とすることができる。
<Chelating agent>
A chelating agent can be added to the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention in order to control the dissolution rate of the poorly soluble aluminum compound (crosslinking agent).
Examples of the chelating agent include sodium edetate (ethylenediaminetetraacetic acid disodium salt).
The blending amount of the chelating agent 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 non-pharmaceutical water-containing patch.
<その他の任意成分>
 本発明の非医薬品用含水系貼付剤の粘着剤層には、上記以外のその他の任意成分として、水溶性高分子化合物、界面活性剤、安定剤(抗酸化剤、紫外線吸収剤等)、無機粉体、着色剤、香料、防腐剤等の、従来の含水系貼付剤(パップ剤)やあるいは非水系貼付剤(テープ剤)における粘着剤層に一般に配合され得る成分を配合することができる。これらの任意成分は、それぞれ単独で、または2種以上を組み合わせて使用することができる。
<Other optional ingredients>
In the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention, as other optional components other than the above, a water-soluble polymer compound, a surfactant, a stabilizer (antioxidant, an ultraviolet absorber, etc.), an inorganic substance, etc. 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 powders, colorants, fragrances, and preservatives, can be blended. These optional components can be used alone or in combination of two or more.
〈水溶性高分子化合物〉
 水溶性高分子化合物としては、例えば、ポリビニルアルコール、ポリビニルピロリドン、カルボキシビニルポリマー、ショ糖脂肪酸エステル等が挙げられる。これらは1種単独で、又は2種以上を適宜組み合わせて、使用できる。
 水溶性高分子化合物の配合量は、通常、非医薬品用含水系貼付剤の粘着剤層の全質量を基準として、例えば1.0質量%以上30質量%以下、3.0質量%以上20質量%以下、あるいは5.0質量%以上20質量%以下の範囲とすることができる。
<Water-soluble polymer compound>
Examples of the water-soluble polymer compound include polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, sucrose fatty acid ester and the like. 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 and 3.0% by mass or more and 20% by mass based on the total mass of the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch. It can be in the range of% or less, or 5.0% by mass or more and 20% by mass or less.
〈界面活性剤〉
 界面活性剤としては、例えば、ポリオキシエチレンモノラウレート、ポリオキシエチレンモノステアレート、ポリオキシエチレンモノオレート、ポリエチレングリコールジステアレート、ポリエチレングリコールジオレート、ポリプロピレングリコールジオレート等のポリオキシエチレン脂肪酸エステル;ソルビタンモノカプリレート、ソルビタンモノラウレート、ソルビタンモノミリステート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンジステアレート、ソルビタントリステアレート、ソルビタンモノオレート、ソルビタントリオレート、ソルビタンモノセスキオレート、及びこれらのエチレンオキシド付加物等のソルビタン脂肪酸エステル;ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリステアレート、ポリオキシエチレンソルビタンモノオレート、ポリオキシエチレンソルビタントリオレート、ポリオキシエチレンソルビタントリイソステアレート等のポリオキシエチレンソルビタン脂肪酸エステル;ポリオキシエチレンドデシルエーテル(ポリオキシエチレンラウリルエーテル)、ポリオキシアルキレンラウリルエーテル、ポリオキシエチレントリデシルエーテル、ポリオキシアルキレントリデシルエーテル、ポリオキシエチレンミリスチルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンベヘニルエーテル、ポリオキシエチレン-2-エチルヘキシルエーテル、ポリオキシエチレンイソデシルエーテル等のポリオキシエチレンアルキルエーテル;ポリオキシエチレンスチレン化フェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンジスチレン化フェニルエーテル、ポリオキシエチレントリベンジルフェニルエーテル等のポリオキシエチレンアルキルフェノールエーテル;モノステアリン酸グリセリン、モノオレイン酸グリセリン等のグリセリン脂肪酸エステル;ポリエチレングリコール、ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレンヒマシ油、レシチン等の非イオン性界面活性剤が挙げられる。これらは、1種単独で、又は2種以上を適宜組み合わせて、使用できる。
 これら界面活性剤の配合量は、非医薬品用含水系貼付剤の粘着剤層の全質量を基準として、例えば0.001質量%以上10質量%以下、0.01質量%以上5質量%以下の範囲とすることができる。
<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 monocaprylate, 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 polyethylene oxide adducts; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, 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 ether, polyoxyethylene nonylphenyl ether, polyoxyethylene disstyrene phenyl ether, and polyoxyethylene tribenzylphenyl ether; 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 non-pharmaceutical water-containing patch. Can be a range.
〈安定剤〉
 本発明の非医薬品用含水系貼付剤の粘着剤層には、光(特に、紫外線)、熱又は酸素に対して、配合成分の保存安定性を向上させるために安定剤を配合することができる。
 安定剤としては、例えば、ジブチルヒドロキシトルエン(BHT)等の抗酸化剤;ベンゾイルメタン誘導体等の紫外線吸収剤;等が挙げられる。
 安定剤の配合量は、通常、非医薬品用含水系貼付剤の粘着剤層の全質量を基準として、例えば0.01質量%以上1質量%以下の範囲とすることができる。
<Stabilizer>
A stabilizer can be added to the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention in order to improve the storage stability of the ingredients against light (particularly ultraviolet rays), heat or oxygen. ..
Examples of the stabilizer include 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 non-pharmaceutical water-containing patch.
〈無機粉体〉
 無機粉体としては、炭酸カルシウム、炭酸マグネシウム、珪酸塩、酸化亜鉛、酸化チタン、硫酸マグネシウム、硫酸カルシウム等を配合することができる。
<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.
[支持体]
 本発明の非医薬品用含水系貼付剤に用いる支持体としては、フィルム、不織布、和紙、綿布、編布、織布、不織布とフィルムのラミネート複合体等の柔軟性を有する支持体が挙げられる。これらの支持体は、皮膚に密着することができ、かつ、皮膚の動きに追随することができる程度の柔軟な材質、そして長時間貼付後において皮膚のかぶれ等の発生を抑制できる材質が好ましい。これらの支持体の材質としては、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリスチレン、ナイロン、コットン、アセテートレーヨン、レーヨン、レーヨン/ポリエチレンテレフタレート複合体、ポリアクリロニトリル、ポリビニルアルコール、アクリル系ポリウレタン、エステル系ポリウレタン、エーテル系ポリウレタン、スチレン-イソプレン-スチレン共重合体、スチレン-ブタジエン-スチレン共重合体、スチレン-エチレン-プロピレン-スチレン共重合体、スチレン-ブタジエンゴム、エチレン-酢酸ビニル共重合体、セロハン等を必須成分とするものが挙げられる。
[Support]
Examples of the support used for the non-pharmaceutical water-containing patch of the present invention include flexible supports such as films, non-woven fabrics, Japanese papers, cotton cloths, knitted fabrics, woven fabrics, 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, cellophane and the like as essential components.
 また、布類などの支持体は、着色剤により肌色などの色調に着色することにより、貼付時に肌の色との相違を少なくできる。また貼付下の皮膚の色調を透けて出しやすいという点では、透明性に優れたプラスチックフィルムの形態を採用することができる。 In addition, the support such as cloth can be colored with a colorant to a color tone such as skin color to reduce the difference from the skin color at the time of application. Further, in that the color tone of the skin under the application can be easily seen through, the form of a plastic film having excellent transparency can be adopted.
 支持体の厚みは、通常5μmから1mm程度である。支持体が布類である場合、その厚みは、好ましくは50μm~1mm、より好ましくは100~800μm、更に好ましくは200~700μmである。支持体がプラスチックフィルムである場合、その厚みは、好ましくは10~300μm、より好ましくは12~200μm、更に好ましくは15~150μmである。支持体の厚みが5μm~30μm程度とごく薄い場合は、支持体上に形成された粘着剤層とは反対の面上に、剥離可能なキャリアフィルム層を設けると、貼付剤としての取り扱い性が向上するので好ましい。但し5μmよりも支持体の厚みが小さいと、貼付剤の強度や取り扱い性が低下して、皮膚への貼付が困難になり、他の部材等との接触によって破れたり、入浴等の水との接触によって短時間で皮膚から剥離したりすることがある。また、支持体の厚みが大きすぎる(1mmより超える)と、貼付剤が、皮膚の動きに追随しにくくなり、貼付剤の辺縁部に剥がれるきっかけを形成しやすくなるため、短時間で皮膚から剥離したり、貼付中の違和感が増えたりする虞がある。
 なお支持体がフィルムである場合は、粘着剤と支持体の投錨性を向上することを目的に、支持体の片面又は両面にサンドブラスト処理、コロナ処理等の処理を行なってもよい。
 また、包材から取り出しやすくするために支持体の片面又は両面にサンドブラスト以外の方法で凹凸を設けてもよい。
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 pressure-sensitive 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 with water for bathing, etc. It may peel off from the skin in a short time due to contact. 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 application.
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.
[剥離ライナー]
 本発明の非医薬品用含水系貼付剤に用いる剥離ライナー(剥離層・剥離紙ともいう)としては、粘着剤層中の薬物等が吸収・吸着しにくい材質であることが好ましく、貼付剤の技術分野において慣用のものを使用することができる。
 例えば、ポリエステル(ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等)、ポリプロピレン(無延伸、延伸等)、ポリエチレン、ポリウレタン、ポリ塩化ビニル、ポリスチレン等のプラスチックフィルム;上質紙、グラシン紙、パーチメント紙、クラフト紙等の紙や合成紙;前記プラスチックフィルム、紙又は合成紙、合成繊維等にシリコーン樹脂やフッ素樹脂等の剥離性能を有する剥離剤をコーティングした剥離加工紙;アルミ箔;これらフィルム・シートを種々積層したラミネート加工紙、及び該ラミネート加工紙に剥離剤をコーティングしたラミネート剥離加工紙などの、無色又は着色したシートを挙げることができる。なお剥離ライナーは、包材から取り出しやすいように凹凸を設けることも可能である。
 これら剥離ライナーの厚さは特に限定されないが、通常10μm~1mm、例えば20μm~500μm、好ましくは40μm~200μmの範囲である。
 剥離ライナーの形状は方形、矩形、円形等とすることができ、所望により角を丸くした形状とすることができる。その大きさは、前記貼付剤における支持体の大きさと同形状か、やや大きめとすることができる。剥離ライナーは1枚または分割されて複数枚から構成されてもよく、その切れ目は直線、波線、ミシン線状で構成されてもよく、剥離ライナー同士の一部が重なる状態としてもよい。
[Peeling liner]
The release liner (also referred to as release layer / release paper) used in the non-pharmaceutical 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. Conventional ones can be used in the field.
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 patch. 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.
[非医薬品用含水系貼付剤の製造方法]
 本発明の非医薬品用含水系貼付剤は、従来公知の方法を用いて製造され得る。例えば一例として、以下のi)又はii)の工程を経て製造可能である。
i)支持体上に、粘着剤層形成組成物を塗工し、粘着剤層を形成する工程、及び、支持体上に形成された粘着剤層と、剥離ライナーとを貼り合わせる工程。
ii)剥離ライナー上に、粘着剤層形成組成物を塗工し、粘着剤層を形成する工程、及び、剥離ライナー上に形成された粘着剤層と、支持体とを貼り合わせる工程。
 なお、上記粘着剤層の厚みは特に限定されないが、通常10μm乃至1000μm、例えば20μm乃至800μm程度とすることができる。
[Manufacturing method of non-pharmaceutical water-containing patch]
The non-pharmaceutical water-containing patch of the present invention can be produced by 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.
 前記粘着剤層形成組成物とは、前述した粘着剤層に含まれる各種成分:アクリル系親水性粘着剤、アクリル酸アルキルエステル系共重合体、架橋剤、粘稠化剤、湿潤剤及び水を含有し、清涼化剤、有機溶媒、pH調節剤及びキレート剤を含有し得、さらに、その他の任意の成分を含有し得る半固形状の組成物である。
 なお、粘着剤層形成組成物のpHを2~4とすることにより、良好な架橋性及び保形性を期待できるため好ましい。
The pressure-sensitive adhesive layer-forming composition includes various components contained in the above-mentioned pressure-sensitive adhesive layer: acrylic hydrophilic pressure-sensitive adhesive, acrylic acid alkyl ester-based copolymer, cross-linking agent, thickening agent, wetting agent, and water. It is a semi-solid composition which may contain a cooling agent, an organic solvent, a pH adjuster and a chelating agent, and may further contain any other component.
It is preferable to set the pH of the pressure-sensitive adhesive layer forming composition to 2 to 4 because good crosslinkability and shape retention can be expected.
 なお本発明の非医薬品用含水系貼付剤は、水分含有時(貼付直後)並びに水分非含有時(貼付後水分が揮散後)における粘着力が維持されることを特徴とし、また皮膚刺激性も低い貼付剤である。
 例えば本発明の非医薬品用含水系貼付剤の粘着剤層は、i)貼付剤の製造日から50℃、16時間保管後において、1N/15mm以上のピール粘着力を有し、ii)貼付剤の製造直後において、0.7N/mmφ以上のプローブタックを有し、かつ、iii)貼付剤の製造直後の粘着剤層のプローブタック値に対して、貼付剤の製造日から50℃、16時間保管後の粘着剤層のプローブタック値が1.8倍以上である、といった粘着力を有してなることが好ましい。
The non-pharmaceutical water-containing patch of the present invention is characterized in that the adhesive strength is maintained when it contains water (immediately after application) and when it does not contain water (after the water volatilizes after application), and it also has skin irritation. It is a low patch.
For example, the pressure-sensitive adhesive layer of the non-pharmaceutical water-containing patch of the present invention has i) a peel adhesive strength of 1 N / 15 mm or more after storage at 50 ° C. for 16 hours from the date of manufacture of the patch, and ii) the patch. Immediately after the manufacture of the adhesive, it has a probe tack of 0.7 N / mmφ or more, and iii) the probe tack value of the pressure-sensitive adhesive layer immediately after the manufacture of the patch is 50 ° C. for 16 hours from the date of manufacture of the patch. It is preferable that the pressure-sensitive adhesive layer has an adhesive strength such that the probe tack value after storage is 1.8 times or more.
 以下に実施例を挙げて、本発明をさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。 The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
<貼付剤の作製>
 以下の手順にて、実施例及び比較例の貼付剤を製造した。
<Making a patch>
The patches of Examples and Comparative Examples were manufactured by the following procedure.
実施例1:
 ポリビニルアルコール1質量部を、精製水10質量部に70℃に加熱して溶解させた後、室温まで冷却した(予製剤1)。
 次に、l-メントール1質量部に、マクロゴール(登録商標)400 3質量部並びに乳酸1質量部を加えて40℃で溶解させた後、室温まで冷却した(予製剤2)。
 更に、ポリアクリル酸部分中和物4質量部、カルメロースナトリウム3質量部、ジヒドロキシアルミニウムアミノアセテート0.25質量部を、濃グリセリン25質量部中で均一に分散させた(予製剤3)。
 撹拌機中に、予製剤1、アクリル酸メチル・アクリル酸2-エチルヘキシル共重合エマルジョン(固形分60%、エマルジョン中にポリオキシエチレンノニルフェニルエーテル(30EO)微量含有)20質量部、エデト酸ナトリウム水和物0.2質量部、D-ソルビトール70%水溶液 25質量部及び塩酸0.4質量部の順に投入し、脱気条件下、均一に分散又は溶解させた。ここに、予製剤2を投入し、脱気条件下、均一に練合した。更に、予製剤3を投入し、精製水で全100質量部となるように質量補正した後、脱気条件下、均一に練合し実施例1の粘着剤層形成組成物(膏体)を得た。
 得られた粘着剤層形成組成物をスリット幅0.5mmに調整した展延機でライナー(片面シリコーン処理したPET(75μm))のシリコーン面上に展延し、ニット支持体(ポリエステル製)をラミネートした後、任意の形状に打ち抜き、これをアルミ袋に密封し、40℃で1週間熟成させ、実施例1の製剤を得た。
Example 1:
1 part by mass of polyvinyl alcohol was dissolved in 10 parts by mass of purified water by heating at 70 ° C., and then cooled to room temperature (preliminary preparation 1).
Next, 3 parts by mass of Macrogol (registered trademark) 400 and 1 part by mass of lactic acid were added to 1 part by mass of l-menthol, dissolved at 40 ° C., and then cooled to room temperature (preliminary preparation 2).
Further, 4 parts by mass of the partially neutralized polyacrylic acid, 3 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 (preliminary preparation 3).
In a stirrer, preform 1, methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion (solid content 60%, polyoxyethylene nonylphenyl ether (30EO) trace amount contained in the emulsion), 20 parts by mass, sodium edetate water. 0.2 parts by mass of Japanese product, 25 parts by mass of D-sorbitol 70% aqueous solution and 0.4 parts by mass of hydrochloric acid were added in this order, and the mixture was uniformly dispersed or dissolved under degassing conditions. The pre-formal product 2 was added thereto and kneaded uniformly under degassing conditions. Further, the preform 3 is added, the mass is corrected with purified water so as to have a total of 100 parts by mass, and then the mixture is uniformly kneaded under degassing conditions to obtain the pressure-sensitive adhesive layer forming composition (plaster) of Example 1. Obtained.
The obtained pressure-sensitive adhesive layer-forming composition is 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) is formed. After laminating, it was punched into an arbitrary shape, sealed in an aluminum bag, and aged at 40 ° C. for 1 week to obtain the formulation of Example 1.
実施例2:
 アクリル酸メチル・アクリル酸2-エチルヘキシル共重合エマルジョンの配合量を30質量部(固形分60%)及びD-ソルビトール70%水溶液の配合量を20質量部に変えた以外は、実施例1と同様にして、実施例2の製剤を得た。
Example 2:
Same as Example 1 except that the amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion was changed to 30 parts by mass (solid content 60%) and the amount of the D-sorbitol 70% aqueous solution was changed to 20 parts by mass. The preparation of Example 2 was obtained.
実施例3:
 アクリル酸メチル・アクリル酸2-エチルヘキシル共重合エマルジョンの配合量を40質量部(固形分60%)及びD-ソルビトール70%水溶液の配合量を15質量部に変えた以外は、実施例1と同様にして、実施例3の製剤を得た。
Example 3:
Same as Example 1 except that the compounding amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion was changed to 40 parts by mass (solid content 60%) and the compounding amount of the 70% aqueous solution of D-sorbitol was changed to 15 parts by mass. The preparation of Example 3 was obtained.
実施例4:
 アクリル酸メチル・アクリル酸2-エチルヘキシル共重合エマルジョンの配合量を50質量部(固形分60%)、D-ソルビトール70%水溶液の配合量を10質量部及び濃グリセリンの配合量を20質量部に変えた以外は、実施例1と同様にして、実施例4の製剤を得た。
Example 4:
The amount of methyl acrylate / 2-ethylhexyl acrylate copolymer compounded emulsion is 50 parts by mass (solid content 60%), the amount of D-sorbitol 70% aqueous solution is 10 parts by mass, and the amount of concentrated glycerin is 20 parts by mass. The pharmaceutical product of Example 4 was obtained in the same manner as in Example 1 except that it was changed.
実施例5:
 アクリル酸メチル・アクリル酸2-エチルヘキシル共重合エマルジョンの配合量を60質量部(固形分60%)、D-ソルビトール70%水溶液の配合量を0質量部及び濃グリセリンの配合量を20質量部に変えた以外は、実施例1と同様にして、実施例5の製剤を得た。
Example 5:
The amount of methyl acrylate / 2-ethylhexyl acrylate copolymer compounded emulsion is 60 parts by mass (solid content 60%), the amount of D-sorbitol 70% aqueous solution is 0 parts by mass, and the amount of concentrated glycerin is 20 parts by mass. The pharmaceutical product of Example 5 was obtained in the same manner as in Example 1 except that it was changed.
比較例1:
アクリル酸メチル・アクリル酸2-エチルヘキシル共重合エマルジョンの配合量を7質量部(固形分60%)に変えた以外は、実施例1と同様にして、比較例1の製剤を得た。
Comparative Example 1:
A pharmaceutical product of Comparative Example 1 was obtained in the same manner as in Example 1 except that the blending amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion was changed to 7 parts by mass (solid content 60%).
比較例2:
 アクリル酸メチル・アクリル酸2-エチルヘキシル共重合エマルジョンの配合量を10質量部(固形分60%)に変えた以外は、実施例1と同様にして、比較例2の製剤を得た。
Comparative Example 2:
A pharmaceutical product of Comparative Example 2 was obtained in the same manner as in Example 1 except that the blending amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion was changed to 10 parts by mass (solid content 60%).
比較例3:
 アクリル酸メチル・アクリル酸2-エチルヘキシル共重合エマルジョンの配合量を70質量部(固形分60%)、D-ソルビトール液の配合量を0質量部及び濃グリセリンの配合量を10質量部に変えた以外は、実施例1と同様にして粘着剤層形成組成物を得ようとしたが、得られた粘着剤層形成組成物にダマが多数発生し、その後のライナーへの展延に至らず、製剤を得ることはできなかった。
Comparative Example 3:
The amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer emulsion was changed to 70 parts by mass (solid content 60%), the amount of the D-sorbitol solution was changed to 0 parts by mass, and the amount of concentrated glycerin was changed to 10 parts by mass. Except for the above, an attempt was made to obtain a pressure-sensitive adhesive layer-forming composition in the same manner as in Example 1, but a large amount of lumps were generated in the obtained pressure-sensitive adhesive layer-forming composition, and the subsequent spread to the liner was not achieved. The formulation could not be obtained.
試験例1(粘着剤層(粘着剤層形成組成物(膏体))
 実施例1乃至実施例5及び比較例1及び比較例2の製剤について、水分含有時(熟成後)、並びに水分非含有時(熟成後、ライナーを剥離して粘着剤層を露出させた状態で、50℃にて16時間保管にて乾燥させた後)に、粘着剤層(粘着剤層形成組成物)の色を目視で評価した。得られた結果を表2に示す。
Test Example 1 (Adhesive layer (adhesive layer forming composition (plaster))
With respect to the formulations of Examples 1 to 5 and Comparative Examples 1 and 2 when they contained water (after aging) and when they did not contain water (after aging, the liner was peeled off to expose the pressure-sensitive adhesive layer). After drying at 50 ° C. for 16 hours), the color of the pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer forming composition) was visually evaluated. The results obtained are shown in Table 2.
試験例2(粘着剤層(粘着剤層形成組成物(膏体))の架橋状態)
 実施例1乃至実施例5及び比較例1乃至実施例3の製剤(熟成後)を1cm×5cmに裁断し、室温(23℃±5℃)下、精製水50mLに浸漬させた。浸漬から16時間経過後、粘着剤層(粘着剤層形成組成物)の膨潤状態を目視で評価し、下記評価基準により粘着剤層(粘着剤層形成組成物)の架橋状態を評価した。得られた結果を表2に示す。
 <評価基準>
  -  :架橋なし(粘着剤層(粘着剤層形成組成物)が溶解)
  +  :架橋あり(粘着剤層(粘着剤層形成組成物)が溶解せずに、大きく膨潤)
  ++ :強い架橋あり(粘着剤層(粘着剤層形成組成物)が溶解せずに、中等度に膨潤)
  +++:非常に強い架橋あり(粘着剤層(粘着剤層形成組成物)が溶解せずに、小さく膨潤)
 なお、“-”評価(架橋なし)の粘着剤層形成組成物は、親水性アクリル系粘着剤等の高分子化合物が溶解し、溶解が進むと浸漬させた容器の底に堆積する事態にもなり得、一方、評価が“+”から“+++”となるに従い、高分子化合物の膨潤が少なくなり、該粘着剤層形成組成物は強い架橋状態にあることが確認できる。
Test Example 2 (Cross-linked state of adhesive layer (adhesive layer forming composition (plaster)))
The formulations (after aging) of Examples 1 to 5 and Comparative Examples 1 to 3 were cut into 1 cm × 5 cm and immersed in 50 mL of purified water at room temperature (23 ° C. ± 5 ° C.). After 16 hours from the immersion, the swelling state of the pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer forming composition) was visually evaluated, and the cross-linked state of the pressure-sensitive adhesive layer (the pressure-sensitive adhesive layer forming composition) was evaluated according to the following evaluation criteria. The results obtained are shown in Table 2.
<Evaluation criteria>
-: No cross-linking (adhesive layer (adhesive layer forming composition) dissolved)
+: Cross-linked (adhesive layer (adhesive layer forming composition) does not dissolve and swells greatly)
++: Strong cross-linking (adhesive layer (adhesive layer forming composition) does not dissolve and swells moderately)
+++: Very strong cross-linking (adhesive layer (adhesive layer forming composition) does not dissolve and swells small)
In addition, the pressure-sensitive adhesive layer-forming composition evaluated as “-” (without cross-linking) may dissolve a polymer compound such as a hydrophilic acrylic pressure-sensitive adhesive, and as the dissolution progresses, it may be deposited on the bottom of the immersed container. On the other hand, as the evaluation changes from "+" to "+++", the swelling of the polymer compound decreases, and it can be confirmed that the pressure-sensitive adhesive layer-forming composition is in a strong crosslinked state.
試験例3(粘着力試験)
<試験製剤>
 実施例1~実施例5、比較例1及び比較例2の製剤について、水分含有(熟成後)と水分非含有(熟成後、ライナーを取って粘着剤層を露出し、50℃にて16時間保管にて乾燥させた後)の2種類を初期とした。
 また、実施例1~実施例5、比較例1及び比較例2の「水分含有」製剤(熟成後、アルミ袋入り)を、60℃で1週間保存した。
 前述のすべての製剤の「初期」(水分含有、水分非含有)及び「60℃、1週間保存時」(水分含有)について、下記1)~3)の試験を実施した。
Test Example 3 (Adhesive strength test)
<Test product>
For the formulations of Examples 1 to 5, Comparative Example 1 and Comparative Example 2, water-containing (after aging) and water-free (after aging, the liner was removed to expose the pressure-sensitive adhesive layer, and the temperature was 50 ° C. for 16 hours. After drying in storage), the two types were set as the initial stage.
In addition, the "moisture-containing" preparations (after aging and in an aluminum bag) of Examples 1 to 5, Comparative Example 1 and Comparative Example 2 were stored at 60 ° C. for 1 week.
The following tests 1) to 3) were carried out for the "initial" (moisture-containing, moisture-free) and "60 ° C. for 1 week storage" (moisture-containing) of all the above-mentioned preparations.
<粘着力試験>
1)ボールタック粘着力試験:日局一般試験法 6.12粘着力試験法 3.2傾斜式ボールタック試験法に従い実施した。
2)ピール粘着力試験:日局一般試験法 6.12粘着力試験法 3.1ピール粘着力試験法に従い実施した。
3)プローブタック粘着力試験:日局一般試験法 6.12粘着力試験法 3.4プローブタック試験法に従い実施した。
 得られた結果を表3に示す。
<Adhesive strength test>
1) Ball tack adhesive strength test: Japan-wide general test method 6.12 Adhesive strength test method 3.2 The ball tack test method was carried out according to the tilted ball tack test method.
2) Peel adhesive strength test: Japan-wide general test method 6.12 Adhesive strength test method 3.1 The peel adhesive strength test method was carried out.
3) Probe tack adhesive strength test: Japan-wide general test method 6.12 Adhesive strength test method 3.4 The probe tack test method was carried out.
The results obtained are shown in Table 3.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
<試験結果(表2)>
 表2に示すように、アクリル酸メチル・アクリル酸2-エチルヘキシル共重合樹脂エマルジョン(ニカゾール)を7質量%~60質量%まで配合した粘着剤層形成組成物(実施例1~5、比較例1~2)は、製造時にダマを生じず、製剤の製造が可能であった。また、アクリル酸メチル・アクリル酸2-エチルヘキシル共重合樹脂エマルジョンの配合量が増えるに従い、粘着剤層形成組成物の色が白濁化した。粘着剤層形成組成物の白濁化は水分揮散により消失し、アクリル酸2-エチルヘキシル共重合樹脂エマルジョンの配合量が7質量%~60質量%の範囲にて調製した製剤のすべてにおいて、乾燥後の粘着剤層形成組成物の色は透明となった。
 一方、前述したように、アクリル酸メチル・アクリル酸2-エチルヘキシル共重合樹脂エマルジョンの配合量を70質量%に引き上げた比較例3の粘着剤層形成組成物は、ダマが多数発生し、製剤の製造が不可能であった。
<Test results (Table 2)>
As shown in Table 2, a pressure-sensitive adhesive layer-forming composition containing 7% by mass to 60% by mass of a methyl acrylate / 2-ethylhexyl acrylate copolymer resin emulsion (Nicazole) (Examples 1 to 5, Comparative Example 1). In (2), the preparation could be produced without causing lumps during production. Further, as the blending amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer resin emulsion increased, the color of the pressure-sensitive adhesive layer forming composition became cloudy. The white turbidity of the pressure-sensitive adhesive layer-forming composition disappears due to the volatilization of water, and in all the formulations prepared in the range of 7% by mass to 60% by mass of the 2-ethylhexyl acrylate copolymer resin emulsion, after drying. The color of the pressure-sensitive adhesive layer-forming composition became transparent.
On the other hand, as described above, the pressure-sensitive adhesive layer-forming composition of Comparative Example 3 in which the blending amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer resin emulsion was increased to 70% by mass caused a large amount of lumps to be generated in the formulation. It was impossible to manufacture.
 また、アクリル酸メチル・アクリル酸2-エチルヘキシル共重合樹脂エマルジョンの配合量が7質量%~60質量%の粘着剤層形成組成物は架橋していることが確認され、該エマルジョンの配合量の増加に伴い、架橋状態が強くなる傾向がみられた。 Further, it was confirmed that the pressure-sensitive adhesive layer-forming composition in which the amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer resin emulsion was 7% by mass to 60% by mass was crosslinked, and the amount of the emulsion was increased. As a result, the cross-linked state tended to become stronger.
 表3に示すように、ボールタック粘着力の結果において、実施例1~実施例5の製剤は、水分含有(初期)ではNo.21以上となり、経時による低下はみられなかった。また、水分揮散後のボールタック粘着力は水分揮散時より増加傾向であった。
 一方、比較例1~比較例2の製剤は、水分を含有している場合、経時的に低下して60℃1Wでは、No.17以下であった。
As shown in Table 3, in the results of ball tack adhesive strength, the formulations of Examples 1 to 5 were No. 1 in terms of water content (initial stage). The number was 21 or more, and no decrease with time was observed. In addition, the ball tack adhesive strength after the water volatilized tended to increase from the time when the water volatilized.
On the other hand, the formulations of Comparative Examples 1 and 2 decreased with time when they contained water, and at 60 ° C. and 1 W, No. It was 17 or less.
 また、ピール粘着力の結果において、実施例1~実施例5の製剤は、水分揮散後において1N/15mm以上を示し、アクリル酸メチル・アクリル酸2-エチルヘキシル共重合樹脂エマルジョンの配合量に依存して、ピール粘着力の値は増加した。
 一方、比較例1~比較例2の製剤では水分揮散後においてもピール粘着力は1N/15mm未満を示した。
In addition, as a result of the peel adhesive strength, the formulations of Examples 1 to 5 showed 1 N / 15 mm or more after the water volatilization, and depended on the blending amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer resin emulsion. Therefore, the value of peel adhesive strength increased.
On the other hand, in the formulations of Comparative Example 1 to Comparative Example 2, the peel adhesive strength was less than 1N / 15 mm even after the water volatilized.
 さらに、プローブタック粘着力の結果において、実施例1~実施例5の製剤は、水分揮散後において1N/5mmφ以上を示し、アクリル酸メチル・アクリル酸2-エチルヘキシル共重合樹脂エマルジョンの配合量に依存して、プローブタック粘着力の値は増加した。
 比較例1~比較例2の製剤では水分揮散後のプローブタック粘着力は1N/5mmφを超えたものの、実施例に及ばない値であった。
Further, as a result of the probe tack adhesive strength, the formulations of Examples 1 to 5 showed 1 N / 5 mmφ or more after the water volatilization, and depended on the blending amount of the methyl acrylate / 2-ethylhexyl acrylate copolymer resin emulsion. As a result, the value of probe tack adhesive strength increased.
In the formulations of Comparative Example 1 to Comparative Example 2, the probe tack adhesive strength after water volatilization exceeded 1 N / 5 mmφ, but the value was lower than that of the examples.
 以上の結果より、実施例1~実施例5の製剤は、比較例1~比較例2の製剤と比べ、ボールタック及びプローブタックにおいては水分含有及び水分非含有(水分揮散後)のいずれも高い値を示し、ピール粘着力に関しても水分揮散後では大きく上回る結果となった。
 以上、実施例の結果より、本発明によれば、アクリル酸アルキルエステル系共重合体エマルジョンの配合量を粘着剤層の全質量に対して20質量%以上70質量%未満とすることにより、含水時及び乾燥時の高い粘着性を維持しつつ、皮膚刺激性の低い非医薬品用含水系貼付剤を提供できることが確認された。
From the above results, the formulations of Examples 1 to 5 are higher in both water-containing and water-free (after water volatilization) in the ball tack and probe tack than the formulations of Comparative Examples 1 and 2. The value was shown, and the peel adhesive strength was significantly higher than that after the water volatilization.
As described above, based on the results of Examples, according to the present invention, the blending amount of the acrylic acid alkyl ester-based copolymer emulsion is 20% by mass or more and less than 70% by mass with respect to the total mass of the pressure-sensitive adhesive layer, thereby containing water. It was confirmed that it is possible to provide a non-pharmaceutical water-containing patch having low skin irritation while maintaining high adhesiveness during time and drying.

Claims (5)

  1. 支持体と、該支持体上に設けられた粘着剤層及び剥離ライナーからなる非医薬品用含水系貼付剤であって、
    前記粘着剤層が、
    1)アクリル系親水性粘着剤、
    2)アクリル酸アルキルエステル系共重合体エマルション、
    3)架橋剤、
    4)粘稠化剤、
    5)水をほとんど含まない湿潤剤を含む、湿潤剤、及び
    6)水
    を含有し、
    前記アクリル酸アルキルエステル共重合体は、モノマーAとモノマーBからなるモノマー混合物の共重合体であって、
    前記モノマーAは、該モノマーAをホモ重合したときガラス転移温度(Tg)が270K以上のポリマーとなるモノマーであり、
    前記モノマーBは、該モノマーBをホモ重合したときガラス転移温度(Tg)が220K以下のポリマーとなるモノマーであり、
    該粘着剤層の全質量に対して20質量%以上70質量%未満の割合にてアクリル酸アルキルエステル系共重合体エマルションを含有する、
    非医薬品用含水系貼付剤。
    A non-pharmaceutical water-containing patch comprising a support, an adhesive layer provided on the support, and a release liner.
    The pressure-sensitive adhesive layer
    1) Acrylic hydrophilic adhesive,
    2) Acrylic acid alkyl ester-based copolymer emulsion,
    3) Crosslinking agent,
    4) Condensing agent,
    5) a wetting agent containing a wetting agent containing almost no water, and 6) a wetting agent containing water,
    The acrylic acid alkyl ester copolymer 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 higher when the monomer A is homopolymerized.
    The monomer B is a polymer having a glass transition temperature (Tg) of 220 K or less when the monomer B is homopolymerized.
    The acrylic acid alkyl ester-based copolymer emulsion is contained in a proportion of 20% by mass or more and less than 70% by mass with respect to the total mass of the pressure-sensitive adhesive layer.
    Water-containing patch for non-pharmaceutical products.
  2. 下記(a)乃至c)のうち1項もしくは2項以上を備えることを特徴とする、請求項1に記載の非医薬品用含水系貼付剤。
    a)前記アクリル酸アルキルエステル系共重合体は、前記モノマー混合物の全質量に対して、前記モノマーAの割合が30質量%以上50質量%以下である、アクリル酸アルキルエステル系共重合体である。
    b)前記粘着剤層は、pH2~4である。
    c)前記水をほとんど含まない湿潤剤の配合量に対する、前記親水性アクリル系粘着剤、前記粘稠化剤、及び前記架橋剤の合計配合量の質量比率が、(合計配合量)/(前記湿潤剤)=7.25/25~7.25/10である。
    The water-containing patch for non-pharmaceutical products according to claim 1, which comprises one or more of the following (a) to (c).
    a) The acrylic acid alkyl ester-based copolymer is an acrylic acid alkyl ester-based copolymer 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. ..
    b) The pressure-sensitive adhesive layer has a pH of 2 to 4.
    c) The mass ratio of the total amount of the hydrophilic acrylic pressure-sensitive adhesive, the thickening agent, and the cross-linking agent to the amount of the wetting agent containing almost no water is (total amount) / (the above). Wetting agent) = 7.25 / 25 to 7.25 / 10.
  3. 前記水をほとんど含まない湿潤剤が、濃グリセリン、グリセリン、D-ソルビトール、エチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、流動パラフィン、1,3-プロパンジオール、1,4-ブタンジオール、マルチトール、及びキシリトールからなる群から選択される、請求項1又は請求項2に記載の非医薬品用含水系貼付剤。 The wetting agent containing almost no water is concentrated glycerin, glycerin, D-sorbitol, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, liquid paraffin, 1,3-propanediol, 1,4-butanediol, and martitol. , And the non-pharmaceutical water-containing patch according to claim 1 or 2, selected from the group consisting of xylitol.
  4. 前記粘着剤層は、
    貼付剤の製造日から50℃、16時間保管後において、1N/15mm以上のピール粘着力を有し、
    貼付剤の製造直後において、0.7N/mmφ以上のプローブタックを有し、かつ、
    貼付剤の製造直後の粘着剤層のプローブタック値に対して、貼付剤の製造日から50℃、16時間保管後の粘着剤層のプローブタック値が1.8倍以上である、
    請求項1乃至請求項3のうち何れか一項に記載の非医薬品用含水系貼付剤。
    The pressure-sensitive adhesive layer is
    It has a peel adhesive strength of 1N / 15 mm or more after storage at 50 ° C. for 16 hours from the date of manufacture of the patch.
    Immediately after the patch is manufactured, it has a probe tack of 0.7 N / mmφ or more and has a probe tack.
    The probe tack value of the pressure-sensitive adhesive layer immediately after the production of the patch is 1.8 times or more the probe tack value of the pressure-sensitive adhesive layer after storage at 50 ° C. for 16 hours from the date of manufacture of the patch.
    The water-containing patch for non-pharmaceutical products according to any one of claims 1 to 3.
  5. 前記粘着剤層が、さらに
    7)清涼化剤
    8)有機溶媒、
    9)pH調節剤、
    10)キレート剤、
    を含有する、請求項1乃至請求項4のうち何れか一項に記載の含水系貼付剤。
     
    The pressure-sensitive adhesive layer is further 7) a cooling agent 8) an organic solvent,
    9) pH regulator,
    10) Chelating agent,
    The water-containing patch according to any one of claims 1 to 4, which comprises.
PCT/JP2020/036081 2020-09-24 2020-09-24 Hydrous adhesive patch for non-medical product WO2022064608A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006090782A1 (en) * 2005-02-23 2006-08-31 Saitama Daiichi Pharmaceutical Co., Ltd. Composition for hydrous adhesive patch for external use and adhesive patch comprising the composition
WO2015025935A1 (en) * 2013-08-23 2015-02-26 久光製薬株式会社 Cataplasm and method for producing same
WO2020066188A1 (en) * 2018-09-26 2020-04-02 ニチバン株式会社 Water-containing transdermal patch

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006090782A1 (en) * 2005-02-23 2006-08-31 Saitama Daiichi Pharmaceutical Co., Ltd. Composition for hydrous adhesive patch for external use and adhesive patch comprising the composition
WO2015025935A1 (en) * 2013-08-23 2015-02-26 久光製薬株式会社 Cataplasm and method for producing same
WO2020066188A1 (en) * 2018-09-26 2020-04-02 ニチバン株式会社 Water-containing transdermal patch

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