WO2020261609A1 - Medical patch material - Google Patents

Medical patch material Download PDF

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Publication number
WO2020261609A1
WO2020261609A1 PCT/JP2019/049904 JP2019049904W WO2020261609A1 WO 2020261609 A1 WO2020261609 A1 WO 2020261609A1 JP 2019049904 W JP2019049904 W JP 2019049904W WO 2020261609 A1 WO2020261609 A1 WO 2020261609A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
less
fatty acid
sensitive adhesive
pressure
Prior art date
Application number
PCT/JP2019/049904
Other languages
French (fr)
Japanese (ja)
Inventor
泰輝 辻
つばさ 宮下
藤澤 博充
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 CN201980096526.5A priority Critical patent/CN113853414B/en
Priority to KR1020217037657A priority patent/KR20220027057A/en
Publication of WO2020261609A1 publication Critical patent/WO2020261609A1/en

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/02Adhesive bandages or dressings
    • A61F13/0246Adhesive bandages or dressings characterised by the skin-adhering layer
    • A61F13/0253Adhesive bandages or dressings characterised by the skin-adhering layer characterized by the adhesive material
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/02Adhesive bandages or dressings
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/02Adhesive bandages or dressings
    • A61F13/0246Adhesive bandages or dressings characterised by the skin-adhering layer
    • A61F13/0256Adhesive bandages or dressings characterised by the skin-adhering layer characterized by the parametric properties of the adhesive
    • 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
    • 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
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61MDEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M25/00Catheters; Hollow probes
    • A61M25/01Introducing, guiding, advancing, emplacing or holding catheters
    • A61M25/02Holding devices, e.g. on the body
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F2013/00361Plasters
    • A61F2013/00365Plasters use
    • A61F2013/00412Plasters use for use with needles, tubes or catheters
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F2013/00361Plasters
    • A61F2013/00655Plasters adhesive
    • A61F2013/00659Plasters adhesive polymeric base
    • A61F2013/00663Plasters adhesive polymeric base acrylic
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61MDEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M25/00Catheters; Hollow probes
    • A61M25/01Introducing, guiding, advancing, emplacing or holding catheters
    • A61M25/02Holding devices, e.g. on the body
    • A61M2025/0266Holding devices, e.g. on the body using pads, patches, tapes or the like

Definitions

  • the present invention relates to a medical patch to be attached to the skin surface such as an adhesive bandage or an adhesive plaster, and an adhesive composition suitable for forming an adhesive layer thereof.
  • a medical patch to be attached to the skin surface such as an adhesive bandage or an adhesive plaster, and an adhesive composition suitable for forming an adhesive layer thereof.
  • the present application claims priority based on Japanese Patent Application No. 2019-12202 filed in Japan on June 28, 2019, the contents of which are incorporated herein by reference.
  • Medical patches such as adhesive bandages and adhesive plasters are also used to fix tubes such as catheters to the skin surface.
  • the medical patch used tends to give priority to high adhesive strength.
  • the catheter or the like may need to be fixed for a long time, or may be repeatedly fixed to the same part of the skin. For this reason, medical patches used for fixing catheters and the like are required to have little effect on the skin when continuously or repeatedly applied.
  • analgesic and anti-inflammatory agents may be repeatedly fixed to the same part of the skin, and are used for medical attachments. It is desirable that the material also has little effect on the skin when it is continuously applied or repeatedly applied.
  • a fatty acid ester compatible with an acrylic acid ester polymer having a weight average molecular weight of 2.5 million or more is liquid-plasticized.
  • a medical patch using an adhesive composition contained as an agent is described.
  • Patent Document 2 describes from a copolymer obtained by emulsion polymerization of a (meth) acrylic acid alkyl ester.
  • a patch material in which a pressure-sensitive adhesive layer obtained by adding a liquid plasticizer such as a fatty acid ester to the acrylic pressure-sensitive adhesive is formed on a support is disclosed.
  • An object of the present invention is to provide a medical patch having sufficient adhesive strength and having a small effect on the skin when repeatedly stuck on the same part of the skin.
  • the present inventors have a weight average molecular weight of 350 or more and 550 or less with respect to 100 parts by mass of an acrylic copolymer in an acrylic pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer of a medical patch, and are liquid at room temperature.
  • fatty ester is contained more than 25 parts by 5 parts by mass or more, further by moisture permeability of the support medical adhesive material to the support is 500g / m 2 ⁇ 24h or more, a high adhesion to human skin
  • the present invention has been completed by finding that a medical patch with a reduced keratin exfoliation area ratio can be obtained while maintaining the above.
  • a medical patch provided with a laminate of a support and an adhesive layer.
  • the pressure-sensitive adhesive layer comprises a pressure-sensitive adhesive composition containing a copolymer containing a (meth) acrylic acid alkyl ester as a main component and a fatty acid ester compatible with the copolymer which is liquid at room temperature.
  • the weight average molecular weight of the fatty acid ester contained in the pressure-sensitive adhesive composition is 350 or more and 550 or less.
  • the pressure-sensitive adhesive composition contains 5 parts by mass or more and 25 parts by mass or less of the fatty acid ester with respect to 100 parts by mass of the copolymer.
  • the moisture permeability of the support is 500g / m 2 ⁇ 24h or more, Medical patch material.
  • the copolymer contains 65% by mass or more and 90% by mass or less of acrylic acid alkyl ester having an alkyl group having 8 or more and 12 or less carbon atoms, 2% by mass or more and 15% by mass or less of acrylic acid, and acetic acid.
  • a copolymer obtained by polymerizing 5% by mass or more and 25% by mass or less of vinyl and 0% by mass or more and 10% by mass or less of other vinyl monomers by a solution polymerization method is crosslinked with a cross-linking agent.
  • a medical patch material in which a pressure-sensitive adhesive layer is formed by a pressure-sensitive adhesive composition that is less irritating to the skin even when continuously or repeatedly applied to the same part of the skin while maintaining high adhesive strength. can do.
  • the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer of the medical patch according to the present invention is liquid at room temperature (1 ° C. or higher and 30 ° C. or lower) with a copolymer containing (meth) acrylic acid alkyl ester as a main component.
  • a copolymer containing (meth) acrylic acid alkyl ester as a main component.
  • the fatty acid ester is a liquid plasticizer that is compatible with a copolymer containing a (meth) acrylic acid alkyl ester as a main component and imparts plasticity.
  • a copolymer containing (meth) acrylic acid alkyl ester as a main component (hereinafter, may be referred to as "acrylic copolymer”) is 50 mol% or more (50 mol% or more) of all the constituent units constituting the copolymer (hereinafter, may be referred to as "acrylic copolymer").
  • acrylic copolymer is 50 mol% or more (50 mol% or more) of all the constituent units constituting the copolymer (hereinafter, may be referred to as "acrylic copolymer”).
  • Meta It means a copolymer which is a constituent unit derived from an acrylic acid alkyl ester.
  • (meth) acrylic acid alkyl ester means "acrylic acid alkyl ester and / or methacrylic acid alkyl ester”.
  • a (meth) acrylic acid alkyl ester having an alkyl group portion having 1 or more and 18 or less carbon atoms is preferable. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n (meth) acrylate.
  • a (meth) acrylic acid alkyl ester having an alkyl group having 4 or more and 18 or less carbon atoms is preferable.
  • a (meth) acrylic acid alkyl ester having an alkyl group of 4 or more and 12 or less is more preferable, and a (meth) acrylic acid alkyl ester having an alkyl group of 6 or more and 12 or less has a carbon number of 8 or more and 12 or more.
  • (meth) acrylic acid alkyl esters having the following alkyl groups are 2-ethylhexyl (meth) acrylic acid, n-octyl (meth) acrylic acid, isooctyl (meth) acrylic acid, or isononyl (meth) acrylic acid. Is particularly preferable.
  • the acrylic copolymer used in the present invention is derived from a (meth) acrylic acid alkyl ester having an alkyl group portion having 4 or more and 18 or less carbon atoms as a constituent unit derived from the (meth) acrylic acid alkyl ester.
  • Those containing at least one type of structural unit are preferable.
  • the acrylic copolymer used in the present invention may be a copolymer consisting of only structural units derived from (meth) acrylic acid alkyl ester, or a copolymer containing structural units derived from other polymerizable compounds. It may be a polymer. Examples of other polymerizable compounds include compounds having a vinyl group (vinyl monomer).
  • the vinyl monomer has a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride group, an amide group, an amino group, an epoxy group, an alkoxy group, an acyl group, a cyano group, an aryl group or a heterocyclic group.
  • a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride group, an amide group, an amino group, an epoxy group, an alkoxy group, an acyl group, a cyano group, an aryl group or a heterocyclic group.
  • Examples include vinyl monomers.
  • Examples of the vinyl monomer having a hydroxyl group include a (meth) acrylic acid ester having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. And so on.
  • Examples of the vinyl monomer having a carboxyl group or an acid anhydride group include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, monobutyl maleate and the like.
  • Examples of the vinyl monomer having an amide group include acrylamide, dimethylacrylamide, diethylacrylamide, methacrylamide, N-methylolacrylamide and the like.
  • Examples of the vinyl monomer having an amino group include dimethylaminoethyl acrylate and the like.
  • Examples of the vinyl monomer having an epoxy group include glycidyl acrylate and glycidyl methacrylate.
  • Examples of the vinyl monomer having an alkoxy group include acrylic acid alkoxyalkyl esters such as 2-methoxyethyl acrylate and ethoxyethyl acrylate.
  • Examples of the vinyl monomer having an acyl group include vinyl esters such as vinyl acetate.
  • Examples of the vinyl monomer having a cyano group include unsaturated nitriles such as acrylonitrile and methacrylonitrile.
  • Examples of the vinyl monomer having an aryl group include vinyl aromatic compounds such as styrene.
  • Examples of the vinyl monomer having a heterocyclic group include a vinyl monomer having a pyrrolidone ring such as N-vinylpyrrolidone. These vinyl monomers can be used alone or in combination of two or more.
  • the acrylic copolymer used in the present invention is preferably a copolymer of a (meth) acrylic acid alkyl ester and another vinyl monomer, and the other vinyl monomer has a hydroxyl group and a hydroxyl group.
  • a vinyl monomer having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amide group, an amino group, an epoxy group, and an alkoxy group hereinafter, "vinyl monomer (A)"
  • the copolymer contains at least one kind of vinyl monomer (hereinafter, referred to as “vinyl monomer (B)”) which does not have a functional group. )
  • the acrylic copolymer used in the present invention is an acrylic acid having an alkyl group having 4 or more and 18 or less carbon atoms, preferably 8 or more and 12 or less carbon atoms with respect to the total mass of the monomers used in the copolymerization reaction.
  • the alkyl ester is 55% by mass or more and 95% by mass or less, preferably 60% by mass or more and 95% by mass or less, more preferably 65% by mass or more and 90% by mass or less, still more preferably 80% by mass or more and 90% by mass or less, particularly preferably.
  • vinyl monomer other than vinyl monomer (A) Is 0% by mass or more and 40% by mass or less, preferably 0% by mass or more and 30% by mass or less, more preferably 0% by mass or more and 25% by mass or less, still more preferably 5% by mass or more and 15% by mass or less, and particularly preferably 9% by mass.
  • the acrylic acid alkyl ester having an alkyl group of 8 or more and 12 or less is preferably 55% by mass or more and 95% by mass or less, preferably 60% by mass or more and 95% by mass or less, more preferably 65% by mass or more and 90% by mass or less, further preferably. Is 80% by mass or more and 90% by mass or less, particularly preferably 83% by mass or more and 87% by mass or less, most preferably 85% by mass; vinyl monomer (A) is 1% by mass or more and 25% by mass or less, preferably 1% by mass.
  • the vinyl monomer (B) is 0% by mass or more and 40% by mass or less, preferably 3% by mass or more and 30% by mass or less, more preferably 5% by mass or more and 25% by mass or less, and further preferably 5% by mass or more and 15% by mass or less.
  • the copolymer is particularly preferably 9% by mass or more and 13% by mass or less, most preferably 11% by mass; and 0% by mass or more and 10% by mass or less of other vinyl monomers.
  • the vinyl monomer (A) is acrylic acid and the vinyl monomer (B) is vinyl acetate, and carbon is relative to the total mass of the monomers used in the copolymerization reaction.
  • the number of acrylic acid alkyl esters having an alkyl group of 4 or more and 18 or less, preferably 8 or more and 12 or less is 55% by mass or more and 95% by mass or less, preferably 60% by mass or more and 95% by mass or less, and more preferably 65% by mass or more.
  • acrylic acid is 1% by mass or more and 25% by mass or less, preferably. 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, further preferably 2% by mass or more and 10% by mass or less, particularly preferably 2% by mass or more and 6% by mass or less, particularly preferably 4% by mass.
  • Vinyl acetate is 0% by mass or more and 40% by mass or less, preferably 3% by mass or more and 30% by mass or less, more preferably 5% by mass or more and 25% by mass or less, still more preferably 5% by mass or more and 15% by mass or less, particularly. It is more preferable that the copolymer is 9% by mass or more and 13% by mass or less, most preferably 11% by mass; and 0% by mass or more and 10% by mass or less of other vinyl monomers.
  • an acrylic copolymer having such a copolymer composition as a pressure-sensitive adhesive, it is possible to form a pressure-sensitive adhesive layer that exhibits appropriate adhesiveness even if the pressure-sensitive adhesive layer is thin and has excellent other properties. It will be easy.
  • the weight average molecular weight of the acrylic copolymer used in the present invention is preferably 300,000 or more and 1,000,000 or less, and more preferably 450,000 or more and 650,000 or less.
  • the weight average molecular weight of the acrylic copolymer is a value obtained as a standard polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
  • the acrylic copolymer used in the present invention can generally be synthesized by radical polymerization.
  • the acrylic copolymer can be produced by a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method, but the solution polymerization method is preferable in that good adhesive properties can be easily obtained.
  • the polymerization initiator include organic peroxides such as benzoyl peroxide and lauroyl peroxide; and azo-based initiators such as azobisisobutyronitrile.
  • a radical polymerization initiator is added at a ratio of 0.1% by mass or more and 3% by mass or less to all the monomers, and the temperature is 40 ° C. or more and 90 ° C.
  • the pressure-sensitive adhesive composition used in the present invention may contain a cross-linking agent.
  • the pressure-sensitive adhesive composition contains a cross-linking agent, the cohesive force of the pressure-sensitive adhesive layer is improved by cross-linking the acrylic copolymer in the pressure-sensitive adhesive composition to form a pressure-sensitive adhesive layer. be able to.
  • cross-linking agent examples include polyfunctional isocyanate compounds [tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalenedisocyanate, and hydrogenation.
  • TDI polyethylene diisocyanate
  • MDI 4,4'-diphenylmethane diisocyanate
  • hexamethylene diisocyanate xylylene diisocyanate
  • metaxylylene diisocyanate 1,5-naphthalenedisocyanate
  • hydrogenation Diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydride xylylene diisocyanate, isophorone diisocyanate, etc.
  • polyfunctional epoxy compounds acetylacetone metal salts, etc.
  • Coronate (registered trademark) HL, Coronate L, Coronate EH manufactured by Nippon Polyurethane Industry Co., Ltd.
  • TETRAD-X (registered trademark), TETRAD-C (registered trademark), Nasem (registered trademark) manufactured by Mitsubishi Gas Chemical Company, Inc.
  • a commercially available product such as aluminum (registered trademark) can be used as a cross-linking agent.
  • the cross-linking agent may be used alone or in combination of two or more.
  • the content of the cross-linking agent is preferably 0.01 part by mass or more and 1 part by mass or less with respect to 100 parts by mass of the acrylic copolymer. It is preferably 0.03 parts by mass or more and 0.5 parts by mass or less, more preferably 0.04 parts by mass or more and 0.1 parts by mass or less, and particularly preferably 0.04 parts by mass or more and 0.08 parts by mass or less, most preferably. It is 0.06 parts by mass.
  • the cross-linking agent may be contained in the pressure-sensitive adhesive composition in advance, immediately before or when the pressure-sensitive adhesive composition is applied to a support. It may be added to the pressure-sensitive adhesive composition under construction.
  • the liquid plasticizer contained in the pressure-sensitive adhesive layer of the medical patch according to the present invention plasticizes the pressure-sensitive adhesive layer to give a soft feeling, thereby reducing skin irritation.
  • the liquid plasticizer contained in the pressure-sensitive adhesive composition used in the present invention is liquid at room temperature and is compatible with the acrylic copolymer contained in the pressure-sensitive adhesive composition, and has a weight average molecular weight of 350 or more and 550 or less. Fatty acid ester. In the following, when simply referred to as "molecular weight", it means a weight average molecular weight.
  • the (weight average) molecular weight of the fatty acid ester includes the weight average molecular weight of the single type fatty acid ester (in this case, there is almost no molecular weight distribution, and the molecular weight is substantially unique to the single type) and multiple types of fatty acids.
  • the weight average molecular weight of the ester is included.
  • the fatty acid ester contained in the pressure-sensitive adhesive composition that is liquid at room temperature is compatible with the acrylic copolymer contained in the pressure-sensitive adhesive composition, and has a molecular weight of 350 or more and 550 or less. It may be only, or may contain two or more kinds of fatty acid esters.
  • the weight average molecular weight of these fatty acid esters is 350 or more and 550 or less. It should be within the range.
  • a fatty acid ester that is liquid at room temperature has a specific size, and is compatible with the acrylic copolymer, the acrylic copolymer and the fatty acid ester are uniformly mixed, and humans.
  • a pressure-sensitive adhesive layer is formed in which the residue on the skin is sufficiently suppressed when peeled off from the skin while maintaining high adhesive strength to the skin.
  • Fatty acid esters having a molecular weight in the range of 350 or more and 550 or less and having high compatibility with acrylic copolymers can impart sufficient plasticity, and further, a drying step after coating the pressure-sensitive adhesive composition. There is no volatilization in the heating process such as. Therefore, by using a fatty acid ester having a molecular weight in the range of 350 or more and 550 or less as a liquid plasticizer, it is possible to impart appropriate skin adhesiveness when a pressure-sensitive adhesive layer is formed, and keratin that is peeled off at the time of peeling. A pressure-sensitive adhesive composition capable of reducing the area of the above can be obtained.
  • the pressure-sensitive adhesive composition used in the present invention has at least one fatty acid residue (residue derived from fatty acid, specifically, a hydroxyl group from a fatty acid) among fatty acid esters having a molecular weight in the range of 350 or more and 550 or less. It is preferable that the removed group) contains an oleic acid ester which is an oleic acid residue (a group obtained by removing a fatty acid from oleic acid).
  • an oleic acid ester fatty acid ester having at least one oleic acid residue
  • the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition used in the present invention can be continuously applied (long-term application). The effect on the skin is further reduced when it is applied repeatedly.
  • the oleic acid ester may be an ester of a monohydric alcohol and an oleic acid, or an ester of a polyhydric alcohol and an oleic acid.
  • the monohydric alcohol include alkyl alcohols such as capryl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol and oleyl alcohol.
  • the polyhydric alcohol include glycerin, sorbitol, glycol and the like.
  • an ester of a polyhydric alcohol and an oleic acid only one hydroxyl group in the polyhydric alcohol may be ester-bonded to a fatty acid, or two or more hydroxyl groups may be ester-bonded to a fatty acid.
  • an oleic acid ester in which two or more hydroxyl groups are ester-bonded to a fatty acid, only a part of the fatty acid residues in the ester may be oleic acid residues, and all the fatty acid residues in the ester are oleic acid residues. It may be an ester.
  • oleic acid ester contained in the pressure-sensitive adhesive composition used in the present invention in the range of 350 or more and 550 or less include octyl oleate, lauryl oleate, myristyl oleate, cetyl oleate, and olein.
  • examples thereof include stearyl acid, isostearyl oleate, oleyl oleate, glyceryl monooleate, sorbitan monooleate, and castor oil fatty acid ester.
  • These oleic acid esters may be used alone or in combination of two or more.
  • oleic acid ester contained in the pressure-sensitive adhesive composition used in the present invention examples include glyceryl monooleate (molecular weight: 356.5), sorbitan monooleate (molecular weight: 428.6), and oleic oleate (molecular weight: 531). Is preferable, and oleyl oleate is particularly preferable.
  • the content of the oleic acid ester in the pressure-sensitive adhesive composition used in the present invention in the range of 350 to 550 parts by mass is preferably 1 part by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the acrylic copolymer. , More preferably 5 parts by mass or more and 25 parts by mass or less, and further preferably 10 parts by mass or more and 20 parts by mass or less. If this content is less than 1 part by mass, the plasticizer layer may be insufficiently plasticized and skin irritation may not be reduced. Conversely, if it exceeds 35 parts by mass, the pressure-sensitive adhesive may aggregate. The force may be reduced, leaving adhesive residue on the skin during peeling.
  • fatty acid esters other than oleic acid esters in the pressure-sensitive adhesive composition used in the present invention which have a molecular weight in the range of 350 or more and 550 or less, include isostearyl isostearate (molecular weight: about 537).
  • the pressure-sensitive adhesive composition used in the present invention may contain other liquid plasticizers other than fatty acid esters having a molecular weight in the range of 350 or more and 550 or less as long as the effects of the present invention are not impaired.
  • the other liquid plasticizer is not particularly limited as long as it is a plasticizer that is liquid at room temperature and is compatible with the acrylic copolymer. Examples thereof include oleic acid esters having a molecular weight of less than 350, oleic acid esters having a molecular weight of more than 550, fatty acid esters other than oleic acid esters, and liquid plasticizers other than fatty acid esters.
  • liquid plasticizers other than fatty acid esters include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol and polypropylene glycol; fats and oils such as olive oil, castor oil, squalane and lanolin; and hydrocarbons such as liquid paraffin. Hydrogens; etc.
  • an organic solvent or a surfactant that is liquid at room temperature can also be used.
  • the fatty acid ester contained in the pressure-sensitive adhesive composition may be compatible with the acrylic copolymer constituting the pressure-sensitive adhesive composition as a whole, and the fatty acid ester incompatible with the acrylic copolymer may be used. It may be contained.
  • the liquid plasticizer contained in the pressure-sensitive adhesive composition used in the present invention is only a fatty acid ester having a molecular weight in the range of 350 or more and 550 or less and compatible with an acrylic copolymer.
  • the content of the fatty acid ester having a molecular weight in the range of 350 or more and 550 parts or less in the pressure-sensitive adhesive composition used is preferably 1 part by mass or more and 35 parts by mass or less, more preferably 1 part by mass or less, based on 100 parts by mass of the acrylic copolymer. It is 5 parts by mass or more and 25 parts by mass or less, more preferably 10 parts by mass or more and 20 parts by mass or less.
  • the plasticizer layer may be insufficiently plasticized and skin irritation may not be reduced. Conversely, if it exceeds 35 parts by mass, the pressure-sensitive adhesive may aggregate. The force may be reduced, leaving adhesive residue on the skin during peeling.
  • the molecular weight contained in the acrylic copolymer is in the range of 350 or more and 550 or less and the number of fatty acid esters compatible with the acrylic copolymer is two or more, "molecular weight in the pressure-sensitive adhesive composition".
  • composition of fatty acid ester in the range of 350 or more and 550 or less is the total amount of fatty acid ester corresponding to the fatty acid ester having a molecular weight in the range of 350 or more and 550 or less and compatible with the acrylic copolymer. means.
  • the present invention contains a fatty acid ester having a molecular weight in the range of 350 or more and 550 or less and compatible with an acrylic copolymer, and other liquid plasticizers
  • the content of the fatty acid ester having a molecular weight in the range of 350 or more and 550 or less is preferably 50% by mass or more, preferably 60% by mass or more, based on the total amount of the liquid plasticizer contained in the pressure-sensitive adhesive composition used in the present invention. Is more preferable, 80% by mass or more is further preferable, and 90% by mass or more is particularly preferable.
  • the weight average molecular weight of the entire liquid plasticizer contained in the pressure-sensitive adhesive composition particularly, the weight average molecular weight of the entire fatty acid ester liquid at room temperature is preferably in the range of 350 or more and 550 or less.
  • the pressure-sensitive adhesive composition used in the present invention may contain various additives in addition to the cross-linking agent, if necessary.
  • additive it is commonly used in adhesives that form an adhesive layer provided in a patch, such as drugs, fillers, antioxidants (antioxidants, preservatives), colorants, fragrances, and tackifiers.
  • Additives can be included.
  • a tackifier can be added to adjust the adhesive properties of the pressure-sensitive adhesive. Examples of the tackifier include terpene-based, terpene phenol-based, kumaron inden-based, styrene-based, rosin-based, xylene-based, phenol-based, and petroleum-based tackifier resins.
  • the medical patch according to the present invention includes a laminate of a support and an adhesive layer.
  • the medical patch according to the present invention preferably has a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition used in the present invention on at least one side of the support. Since the pressure-sensitive adhesive layer is formed by the pressure-sensitive adhesive composition, it is possible to suppress the peeling area of the keratin at the time of peeling while maintaining sufficient adhesive strength to human skin, and it can be continuously applied to the same part of the skin surface or A medical patch material that has little effect on skin irritation even when repeatedly applied can be obtained.
  • the medical patch according to the present invention is a patch that is repeatedly stuck to the same part of the skin such as for fixing a tube such as a catheter, or a specific skin such as a magnetic therapy device adhesive plaster or taping tape. It is suitable for a sticking material that is continuously or repeatedly stuck to a part.
  • moisture permeability is more than 500g / m 2 ⁇ 24h.
  • a support having sufficient moisture permeability it becomes a medical patch material having sufficiently high moisture permeability, less stuffiness when applied to the skin, and less likely to cause skin irritation or itching during application.
  • the moisture permeability of the support preferably at least 500g / m 2 ⁇ 24h, more preferably 700g / m 2 ⁇ 24h or more, still more preferably 1,000g / m 2 ⁇ 24h or more, 1, more preferably more is at 500g / m 2 ⁇ 24h or more, particularly preferably at 5,000g / m 2 ⁇ 24h or more, and most preferably 20,000g / m 2 ⁇ 24h or more.
  • the support examples include impregnated paper, coated paper, high-quality paper, kraft paper, Japanese paper, glassin paper, and other papers; polyester films such as polyethylene terephthalate and polybutylene terephthalate, polyolefin films such as polyethylene and polypropylene, and polyvinyl chloride.
  • Plastic films such as films, polypropylene films, polyurethane films, cellophane films; foams; fabrics such as non-woven fabrics, woven fabrics, knitted fabrics; laminates of two or more of these; and the like.
  • natural materials such as cotton, synthetic resin materials, recycled resin materials and various materials in which these are appropriately combined can be used.
  • Non-woven fabrics, woven fabrics, knitted fabrics, etc. made of cotton or the like can be used.
  • Moisture permeability of the support of the medical adhesive material according to the present invention is 500g / m 2 ⁇ 24h or more. Therefore, as the support, fabrics such as non-woven fabric, woven fabric, and knitted fabric are preferable. Among them, a material that is flexible enough to 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 are preferable, and the skin under application is preferable.
  • the woven fabric is preferable in that it has excellent followability to the movement of the surface, and further, it is easy to maintain the strength and the self-back surface adhesive force becomes stronger.
  • the thickness of the support can be appropriately selected in consideration of physical properties such as elongation, tensile strength, workability, feel at the time of application, and airtightness of the affected area, but is usually about 5 ⁇ m to 1 mm.
  • the carrier is placed on a surface opposite to one surface of the support provided with the adhesive layer (hereinafter referred to as the other surface). Layers may be provided.
  • the support is a woven fabric
  • its thickness is preferably 50 ⁇ m or more and 1 mm or less, more preferably 100 ⁇ m or more and 800 ⁇ m or less, and further preferably 200 ⁇ m or more and 700 ⁇ m or less.
  • the basis weight is preferably 400 g / m 2 or less, more preferably 300 g / m 2 or less, and further preferably 250 g / m 2 or less from the viewpoint of followability to the skin.
  • the support is a plastic film
  • its thickness is preferably 10 ⁇ m or more and 300 ⁇ m or less, more preferably 12 ⁇ m or more and 200 ⁇ m or less, and further preferably 15 ⁇ m or more and 150 ⁇ m or less.
  • sandblasting or corona treatment is performed on one side or the other side of the support, or both sides thereof, for the purpose of improving the anchoring property of the adhesive layer and the support. Etc. may be performed.
  • the thickness of the support is less than 5 ⁇ m, the strength and handleability of the adhesive tape will decrease, making it difficult to attach it to the skin, tearing it due to contact with other members, or using it 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 adhesive tape to follow the movement of the skin, and it becomes easy to form a trigger for peeling at the edge of the adhesive tape, so that the adhesive tape peels off from the skin in a short time. There is a risk that the feeling of discomfort during pasting will increase.
  • the pressure-sensitive adhesive layer is formed by applying the pressure-sensitive adhesive composition used in the present invention to the surface of the support to a desired thickness and drying it.
  • the pressure-sensitive adhesive composition contains a cross-linking agent, a cross-linking treatment according to the type of the cross-linking agent such as an ultraviolet irradiation treatment is performed after coating.
  • the thickness of the pressure-sensitive adhesive layer in the medical patch according to the present invention is not particularly limited, and is preferably 1 ⁇ m or more and 200 ⁇ m or less, more preferably 10 ⁇ m or more and 100 ⁇ m or less, and further preferably 20 ⁇ m or more and 80 ⁇ m or less.
  • the adhesive strength depends on the thickness of the adhesive layer. If the thickness of the adhesive layer is too thick, the adhesive strength becomes too high, and if the thickness of the adhesive layer is too thin, the adhesive strength becomes weak.
  • the thickness of the pressure-sensitive adhesive layer within the above range, in addition to being able to adhere to the skin with sufficient adhesive strength, the adhesive material can be adhered along the surface of the adherend having fine irregularities such as the skin. Furthermore, skin irritation can be suppressed low when peeled off after use.
  • the medical patch according to the present invention may be temporarily attached to a support to form a carrier layer.
  • a support for example, it can be a patch having a laminated structure of "carrier layer / support / adhesive layer / separator layer".
  • the carrier layer can improve the film-forming property of the support, the handleability of the sticking material, and the stickability to the adherend when the thickness of the support is thin. Since the carrier layer is provided to improve the handleability of the sticking material, it may cover the entire surface of the sticking material, only the edge of the sticking material, or a pattern such as a grid pattern. It may be covered in a shape.
  • the carrier layer for example, a film made of various thermoplastic resins such as polyurethane, polyethylene, polypropylene, ionomer, polyamide, polyvinyl chloride, polyvinylidene chloride, ethylene vinyl acetate copolymer, thermoplastic polyester, and polytetrafluoroethylene is used. It is preferable to form it.
  • various thermoplastic resins such as polyurethane, polyethylene, polypropylene, ionomer, polyamide, polyvinyl chloride, polyvinylidene chloride, ethylene vinyl acetate copolymer, thermoplastic polyester, and polytetrafluoroethylene is used. It is preferable to form it.
  • the various films may be laminated on paper. It is preferable that these carrier layers are thicker or stiffer than the support (for example, polyurethane elastomer film).
  • the thickness of the carrier layer can be appropriately set, but is usually 10 ⁇ m or more, preferably 20 ⁇ m or more, and the upper limit thereof is about 500 ⁇ m.
  • the medical patch according to the present invention is usually adjacent to the pressure-sensitive adhesive layer in order to protect the pressure-sensitive adhesive layer until the time when the pressure-sensitive adhesive layer is attached to the skin.
  • a separator layer is provided.
  • the separator layer in the present invention is not particularly limited, and in the technical field of affixing materials, those generally used as release paper, release film, release paper, release film, release liner and the like can be used. .. Specific examples thereof include a polyethylene terephthalate film whose surface is treated with silicone, a laminate of polyethylene whose surface is treated with silicone, and paper. Further, the separator layer may be provided with a cut in order to improve handleability (that is, releasability from the pressure-sensitive adhesive layer), may be formed in a larger area than the sticking material, and a grip portion may be provided on the peripheral edge portion. Good. Further, the separator layer may be provided with irregularities by sandblasting or the like on the surface of the separator layer facing the adhesive layer or the surface opposite to the adhesive layer for the purpose of improving handleability and printability. Good.
  • the thickness of the separator layer can be appropriately set and is not particularly limited, but is usually 20 ⁇ m or more, preferably 40 ⁇ m or more, and the upper limit thereof is about 500 ⁇ m.
  • moisture permeability is at 500g / m 2 ⁇ 24h or more.
  • the patch is, moisture permeability that is 500g / m 2 ⁇ 24h or more, less stuffiness when applied to the skin, hardly occurs itchy skin irritation or sticking in.
  • Moisture permeability of the patch it is more preferably 700g / m 2 ⁇ 24h or more, more preferably 1,000g / m 2 ⁇ 24h or more, 1,500g / m 2 ⁇ 24h or more There still more preferably, particularly preferably at 5,000g / m 2 ⁇ 24h or more, and most preferably 20,000g / m 2 ⁇ 24h or more.
  • the moisture permeability is measured at a temperature of 40 ° C. and a relative humidity of 90% according to the B condition of JIS Z0208. That is, the temperature on one side of the patch is adjusted to 40 ° C. and the relative humidity is 90%, and a moisture absorbent such as calcium chloride is placed on the other side to absorb the moisture that has passed through the patch, and the amount of change in the weight of the moisture absorbent. Is calculated by converting to 24 hours per 1 m 2 .
  • the adhesive strength of the medical patch according to the present invention is preferably 0.5 N / 25 mm or more and 12.0 N / 25 mm or less, more preferably 2.0 N / 25 mm or more and 8.0 N as the adhesive force (peeling force) against bakelite. It is preferably within the range of / 25 mm or less. Since the adhesive strength of the medical patch is within this range, when the medical patch according to the present invention is stuck on the skin surface, it has sufficient sticking performance, does not cause misalignment during sticking, and is said to be relevant. When peeling off the patch, there is no risk of peeling off the skin surface or causing a rash.
  • the method for measuring the adhesive strength of the medical patch is as follows. That is, the sticking material is cut into a predetermined length of 25 mm in width ⁇ 15 mm in length or more, preferably 100 mm to obtain a test piece. The test piece is pressed against a Bakelite test panel to be attached, and then attached with a 2 kg roller at a crimping speed of 300 mm / min and one reciprocating crimping frequency to prepare a test piece. After 20 minutes have passed since the application, the adhesive strength is applied under the conditions of a peeling angle of 180 ° and a peeling speed of 300 mm / minute in accordance with the peeling adhesive strength test method of ISO29862 method 1 (corresponding JIS: JIS Z0237). Measure.
  • the method for producing the medical patch according to the present invention is not particularly limited.
  • a method for continuously forming the pressure-sensitive adhesive layer a method in which the pressure-sensitive adhesive solution is applied onto the separator layer while running in one direction and dried is preferable.
  • a method of melting the adhesive and applying it on the separator layer may be adopted. It can also be a repeating pattern coating of a specific shape.
  • Lamination of "support / adhesive layer / separator layer” by adhering a laminate having an adhesive layer formed on one side of the separator layer and a support so that the adhesive layer and the surface of the support are in close contact with each other.
  • a patch having a structure can be produced.
  • the adhesive layer and the surface of the support of the laminated body are bonded so as to be in close contact with each other to form a “carrier layer (arbitrary layer)”.
  • a patch material having a laminated structure of "/ support / adhesive layer / separator layer” can be produced.
  • Examples 1 to 4, Comparative Examples 1 to 7 A pressure-sensitive adhesive composition containing various liquid plasticizers was prepared, and the adhesive strength and the effect on human skin of the adhesive material on which the pressure-sensitive adhesive layer was formed were investigated.
  • the liquid plasticizer methyl oleate (molecular weight: 296.5), isopropyl myristate (molecular weight: 268.0), glyceryl monooleate (molecular weight: 356.0), sorbitan monooleate (molecular weight: 428.6).
  • Oleyl oleate (molecular weight: 531.0), isostearyl isostearate (molecular weight: 537.0), soybean oil (molecular weight: about 880, SR soybean-LQ- (JP), manufactured by Claude Japan), triolein Polysorbate acid (molecular weight: 935.0), castor oil fatty acid ester (molecular weight: about 500, Ricksizer C-101, manufactured by Ito Oil Co., Ltd.), decyl oleate (molecular weight: 422.4), special castor oil-based condensed fatty acid (molecular weight: 422.4) Molecular weight: 800, Minerazole, manufactured by Ito Oil Co., Ltd.) was used.
  • woven warp: corespun, weft: cotton, moisture permeability: 21,060g / m 2 ⁇ 24h, basis weight 155 g / m 2)
  • urethane nonwoven fiber diameter: 15 [mu] m, moisture permeability: 21, 590g / m 2 ⁇ 24h, basis weight 65g / m 2)
  • polyethylene film thickness: 50 [mu] m, moisture permeability: 60g / m 2 ⁇ 24h
  • the liquid plastic agents shown in Tables 1 to 3 were mixed with 100 parts by mass of the acrylic copolymer in the solution of the above so as to have the parts by mass shown in Table 1, and Tetrad-X (Mitsubishi Gas) was further used as a cross-linking agent.
  • a uniform solution of the pressure-sensitive adhesive composition was prepared by mixing 0.06 parts by mass (manufactured by Kagaku Co., Ltd.).
  • This pressure-sensitive adhesive composition was applied to the peel-treated surface of the separator (silicone-treated polylami release paper) so that the thickness after drying was 38 ⁇ m, and dried to form a pressure-sensitive adhesive layer.
  • This pressure-sensitive adhesive layer was bonded to the supports shown in Tables 1 to 3 to prepare a patch.
  • the adhesive strength of each test sample to human skin is 10 parts by mass of the fatty acid ester with respect to 100 parts by mass of the acrylic copolymer.
  • the numerical value was higher than that of the test sample not containing the fatty acid ester (Comparative Example 1). Yes, the adhesive strength could be enhanced by blending the fatty acid ester.
  • the test sample (Comparative Example 4) in which 30 parts by mass of the fatty acid ester was mixed with 100 parts by mass of the acrylic copolymer, adhesive residue was generated at the time of peeling.
  • test sample (Comparative Example 7) in which decyl oleate, which is inferior in compatibility with the acrylic copolymer, was selected, had adhesive residue in the adhesive residue test, which caused a problem as a medical patch. It was something.
  • the exfoliation area ratio of each test sample was compared with Comparative Example 1 in the test samples (Examples 1 to 6) containing a fatty acid ester having a molecular weight in the range of 350 or more and 550 or less and having good compatibility with the acrylic copolymer.
  • the keratin exfoliation area ratio was about 40%, which was sufficiently low.
  • Comparative Example 2 Comparative Examples 5, 6 and 8 containing fatty acid esters having a molecular weight outside the range, the keratin exfoliation area ratio is 50% or more, and the reduction effect is small. I was able to confirm that.
  • test samples (Examples 1 to 6) containing a fatty acid ester having a molecular weight in the range of 350 or more and 550 or less and having good compatibility with the acrylic copolymer were almost in a skin state over time. It was confirmed that the amount was maintained without decreasing. In addition, it was confirmed that few subjects remained reddish even 24 hours after the peeling on the end date of the test.
  • Example 3 Comparative Example 9
  • Example moisture permeability Comparative example 500 g / m 2 ⁇ but 24h the at is woven more was example 3 and comparable without evaluation result of the support
  • the moisture permeability was polyethylene film is 60 g / m 2 ⁇ 24h and the support
  • the keratin thin area ratio was low, the human skin adhesive strength was significantly reduced and the skin reaction was also strong.
  • moisture permeability of the woven or nonwoven fabric is 500g / m 2 ⁇ 24h or more as a support for the pressure-sensitive adhesive layer including the acrylic copolymer, the compatibility with the acrylic copolymer
  • a pressure-sensitive adhesive layer with low skin irritation is formed even when continuously or repeatedly applied to the same part of the skin while maintaining high adhesive strength. It is clear that it can be done.

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Abstract

This medical patch material comprises a laminate of a support and an adhesive layer, wherein the adhesive layer comprises an adhesive composition containing a copolymer in which a (meth)acrylic acid alkyl ester is the main component and a fatty acid ester compatible with the copolymer when the copolymer is liquid at room temperature, the fatty acid ester contained in the adhesive composition has a weight-average molecular weight of 350-550, the adhesive composition contains 5-25 parts by mass of the fatty acid ester with respect to 100 parts by mass of the copolymer, and the support has a moisture permeability of 500 g/m2·24 h or more.

Description

医療用貼付材Medical patch
 本発明は、粘着包帯や絆創膏等の皮膚表面に貼付される医療用貼付材、及びその粘着剤層の形成に好適な粘着剤組成物に関する。本願は、2019年6月28日に、日本に出願された特願2019-122202号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a medical patch to be attached to the skin surface such as an adhesive bandage or an adhesive plaster, and an adhesive composition suitable for forming an adhesive layer thereof. The present application claims priority based on Japanese Patent Application No. 2019-12202 filed in Japan on June 28, 2019, the contents of which are incorporated herein by reference.
 粘着包帯や絆創膏等の医療用貼付材は、カテーテル等のチューブ等を皮膚表面に固定する際にも用いられる。カテーテル等の固定においては、誤って剥がれることのないように安定して固定することが必要であり、このため、用いられる医療用貼付材には、高い粘着力が優先される傾向にある。一方で、カテーテル等は、長時間の固定が必要とされる場合や、皮膚の同じ部位に繰り返し固定される場合がある。このため、カテーテル等の固定に使用される医療用貼付材には、連続貼付や繰り返し貼付された場合に、皮膚への影響が少ないことが求められている。また、肩や腰といった特定の部位に貼付される鎮痛消炎剤や、磁気治療器絆創膏、テーピングテープ等も、皮膚の同じ部位に繰り返し固定される場合があり、これ等に使用される医療用貼付材も、連続貼付や繰り返し貼付された場合の皮膚への影響が少ないことが望ましい。 Medical patches such as adhesive bandages and adhesive plasters are also used to fix tubes such as catheters to the skin surface. When fixing a catheter or the like, it is necessary to stably fix the catheter or the like so that it will not be accidentally peeled off. Therefore, the medical patch used tends to give priority to high adhesive strength. On the other hand, the catheter or the like may need to be fixed for a long time, or may be repeatedly fixed to the same part of the skin. For this reason, medical patches used for fixing catheters and the like are required to have little effect on the skin when continuously or repeatedly applied. In addition, analgesic and anti-inflammatory agents, magnetic therapy device adhesive plasters, taping tapes, etc., which are attached to specific parts such as shoulders and hips, may be repeatedly fixed to the same part of the skin, and are used for medical attachments. It is desirable that the material also has little effect on the skin when it is continuously applied or repeatedly applied.
 皮膚への刺激が抑えられた医療用貼付材としては、例えば特許文献1には、粘着剤として、重量平均分子量250万以上のアクリル酸エステル系ポリマーに、これに相溶する脂肪酸エステルを液状可塑剤として含有させた粘着剤組成物を用いた医療用貼付材が記載されている。接着性が良好なアクリル酸エステル系ポリマーを粘着剤層とし、これに相溶する脂肪酸エステルを液状可塑剤として含有させることにより、粘着剤層が可塑化されて柔らかくなり、皮膚刺激性が低減される。 As a medical patch material that suppresses irritation to the skin, for example, in Patent Document 1, as an adhesive, a fatty acid ester compatible with an acrylic acid ester polymer having a weight average molecular weight of 2.5 million or more is liquid-plasticized. A medical patch using an adhesive composition contained as an agent is described. By using an acrylic acid ester polymer with good adhesiveness as the pressure-sensitive adhesive layer and containing a fatty acid ester compatible with the pressure-sensitive adhesive layer as a liquid plasticizer, the pressure-sensitive adhesive layer is plasticized and softened, and skin irritation is reduced. To.
 また、粘着剤層に液状可塑剤を配合した粘着剤層を備える医療用貼付材としては、例えば特許文献2には、(メタ)アクリル酸アルキルエステルを乳化重合して得られた共重合体からなるアクリル系粘着剤に、脂肪酸エステル等の液状可塑剤を添加した粘着剤層を支持体に形成した貼付材が開示されている。 Further, as a medical patch material provided with a pressure-sensitive adhesive layer in which a liquid plasticizer is mixed in the pressure-sensitive adhesive layer, for example, Patent Document 2 describes from a copolymer obtained by emulsion polymerization of a (meth) acrylic acid alkyl ester. A patch material in which a pressure-sensitive adhesive layer obtained by adding a liquid plasticizer such as a fatty acid ester to the acrylic pressure-sensitive adhesive is formed on a support is disclosed.
日本国特開平11-76392号公報Japanese Patent Application Laid-Open No. 11-76392 日本国特開2009-155306号公報Japanese Patent Application Laid-Open No. 2009-155306
 本発明は、充分な粘着力を有しつつ、皮膚の同じ部位に繰り返し貼付された場合に皮膚への影響が小さい医療用貼付材を提供することを目的とする。 An object of the present invention is to provide a medical patch having sufficient adhesive strength and having a small effect on the skin when repeatedly stuck on the same part of the skin.
 本発明者らは、医療用貼付材の粘着剤層を構成するアクリル系粘着剤に、アクリル系共重合体100質量部に対して、重量平均分子量が350以上550以下であり、室温で液状の脂肪酸エステルを5質量部以上25質量部以下含有させ、さらに、医療用貼付材の支持体を透湿度が500g/m・24h以上である支持体とすることにより、ヒト皮膚への高い粘着力を維持しつつ、角質剥離面積率が低減された医療用貼付材が得られることを見出し、本発明を完成させた。 The present inventors have a weight average molecular weight of 350 or more and 550 or less with respect to 100 parts by mass of an acrylic copolymer in an acrylic pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer of a medical patch, and are liquid at room temperature. fatty ester is contained more than 25 parts by 5 parts by mass or more, further by moisture permeability of the support medical adhesive material to the support is 500g / m 2 · 24h or more, a high adhesion to human skin The present invention has been completed by finding that a medical patch with a reduced keratin exfoliation area ratio can be obtained while maintaining the above.
 すなわち、本発明は、以下の医療用貼付材を提供するものである。
[1] 支持体と粘着剤層の積層体を備える医療用貼付材であって、
 前記粘着剤層が、(メタ)アクリル酸アルキルエステルを主成分とした共重合体と、室温で液状の前記共重合体と相溶する脂肪酸エステルとを含有する粘着剤組成物からなり、
 前記粘着剤組成物に含有されている前記脂肪酸エステルの重量平均分子量が350以上550以下であり、
 前記粘着剤組成物は、前記共重合体100質量部に対して、前記脂肪酸エステルを5質量部以上25質量部以下含有しており、
 前記支持体の透湿度が500g/m・24h以上である、
 医療用貼付材。
[2] 前記脂肪酸エステルが、重量平均分子量350以上550以下である単一種の脂肪酸エステルを含有する、前記[1]の医療用貼付材。
[3] 前記共重合体が、炭素数が8以上12以下のアルキル基を有するアクリル酸アルキルエステルが65質量%以上90質量%以下と、アクリル酸が2質量%以上15質量%以下と、酢酸ビニルが5質量%以上25質量%以下と、その他のビニル単量体が0質量%以上10質量%以下とが溶液重合法により重合した共重合体を、架橋剤にて架橋させたものである、前記[1]又は[2]の医療用貼付材。
[4] 前記脂肪酸エステルが、少なくとも1個のオレイン酸残基を有する、前記[1]~[3]のいずれかの医療用貼付材。
[5] 前記脂肪酸エステル中の脂肪酸残基が、全てオレイン酸残基である、前記[4]の医療用貼付材。
[6] さらに、前記粘着剤層の前記支持体と接している面とは逆の面にセパレーター層を備える、前記[1]~[5]のいずれかの医療用貼付材。
[7] 皮膚の同じ部位に繰り返し貼付される、前記[1]~[6]のいずれかの医療用貼付材。
[8] チューブ固定用である、前記[1]~[7]のいずれかの医療用貼付材。
That is, the present invention provides the following medical patches.
[1] A medical patch provided with a laminate of a support and an adhesive layer.
The pressure-sensitive adhesive layer comprises a pressure-sensitive adhesive composition containing a copolymer containing a (meth) acrylic acid alkyl ester as a main component and a fatty acid ester compatible with the copolymer which is liquid at room temperature.
The weight average molecular weight of the fatty acid ester contained in the pressure-sensitive adhesive composition is 350 or more and 550 or less.
The pressure-sensitive adhesive composition contains 5 parts by mass or more and 25 parts by mass or less of the fatty acid ester with respect to 100 parts by mass of the copolymer.
The moisture permeability of the support is 500g / m 2 · 24h or more,
Medical patch material.
[2] The medical patch according to the above [1], wherein the fatty acid ester contains a single type of fatty acid ester having a weight average molecular weight of 350 or more and 550 or less.
[3] The copolymer contains 65% by mass or more and 90% by mass or less of acrylic acid alkyl ester having an alkyl group having 8 or more and 12 or less carbon atoms, 2% by mass or more and 15% by mass or less of acrylic acid, and acetic acid. A copolymer obtained by polymerizing 5% by mass or more and 25% by mass or less of vinyl and 0% by mass or more and 10% by mass or less of other vinyl monomers by a solution polymerization method is crosslinked with a cross-linking agent. , The medical patch material of the above [1] or [2].
[4] The medical patch according to any one of [1] to [3] above, wherein the fatty acid ester has at least one oleic acid residue.
[5] The medical patch according to the above [4], wherein all the fatty acid residues in the fatty acid ester are oleic acid residues.
[6] The medical patch according to any one of [1] to [5], further comprising a separator layer on a surface of the pressure-sensitive adhesive layer opposite to the surface in contact with the support.
[7] The medical patch according to any one of [1] to [6] above, which is repeatedly stuck to the same part of the skin.
[8] The medical patch according to any one of [1] to [7] above, which is used for fixing a tube.
 本発明によれば、高い粘着力を維持しつつ、皮膚の同じ部位に連続貼付又は繰り返し貼付した際にも皮膚刺激が低い粘着剤組成物により粘着剤層が形成された医療用貼付材を提供することができる。 According to the present invention, there is provided a medical patch material in which a pressure-sensitive adhesive layer is formed by a pressure-sensitive adhesive composition that is less irritating to the skin even when continuously or repeatedly applied to the same part of the skin while maintaining high adhesive strength. can do.
<粘着剤組成物>
 本発明に係る医療用貼付材の粘着剤層を構成する粘着剤組成物は、(メタ)アクリル酸アルキルエステルを主成分とした共重合体と、室温(1℃以上30℃以下)で液状の脂肪酸エステルとを含有する。当該脂肪酸エステルは、粘着剤である(メタ)アクリル酸アルキルエステルを主成分とした共重合体に対して相溶であり、可塑性を付与する液状可塑剤である。
<Adhesive composition>
The pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer of the medical patch according to the present invention is liquid at room temperature (1 ° C. or higher and 30 ° C. or lower) with a copolymer containing (meth) acrylic acid alkyl ester as a main component. Contains fatty acid ester. The fatty acid ester is a liquid plasticizer that is compatible with a copolymer containing a (meth) acrylic acid alkyl ester as a main component and imparts plasticity.
((メタ)アクリル酸アルキルエステルを主成分とした共重合体)
 (メタ)アクリル酸アルキルエステルを主成分とした共重合体(以下、「アクリル系共重合体」ということがある。)とは、共重合体を構成する全構成単位に対する50モル%以上が(メタ)アクリル酸アルキルエステルに由来する構成単位である共重合体を意味する。なお、本発明及び本願明細書において、(メタ)アクリル酸アルキルエステルとは、「アクリル酸アルキルエステル及び/又はメタクリル酸アルキルエステル」を表す。
(Copolymer containing (meth) acrylic acid alkyl ester as the main component)
A copolymer containing (meth) acrylic acid alkyl ester as a main component (hereinafter, may be referred to as "acrylic copolymer") is 50 mol% or more (50 mol% or more) of all the constituent units constituting the copolymer (hereinafter, may be referred to as "acrylic copolymer"). Meta) It means a copolymer which is a constituent unit derived from an acrylic acid alkyl ester. In addition, in this invention and this specification, (meth) acrylic acid alkyl ester means "acrylic acid alkyl ester and / or methacrylic acid alkyl ester".
 当該共重合体の構成単位が由来する(メタ)アクリル酸アルキルエステルとしては、アルキル基部分の炭素数が1以上18以下である(メタ)アクリル酸アルキルエステルが好ましい。具体的には、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸n-ヘキシル、(メタ)アクリル酸n-オクチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸n-デシル、(メタ)アクリル酸イソデシル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸ステアリル等が挙げられる。これらの(メタ)アクリル酸アルキルエステルは、それぞれ単独で、又は2種以上を組み合わせて用いることができる。 As the (meth) acrylic acid alkyl ester from which the constituent unit of the copolymer is derived, a (meth) acrylic acid alkyl ester having an alkyl group portion having 1 or more and 18 or less carbon atoms is preferable. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n (meth) acrylate. -Hexyl, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate , (Meta) lauryl acrylate, stearyl (meth) acrylate and the like. These (meth) acrylic acid alkyl esters can be used alone or in combination of two or more.
 本発明において用いられるアクリル系共重合体の構成単位が由来する(メタ)アクリル酸アルキルエステルとしては、炭素数が4以上18以下のアルキル基を有する(メタ)アクリル酸アルキルエステルが好ましく、炭素数が4以上12以下のアルキル基を有する(メタ)アクリル酸アルキルエステルがより好ましく、炭素数が6以上12以下のアルキル基を有する(メタ)アクリル酸アルキルエステルがさらに好ましく、炭素数が8以上12以下のアルキル基を有する(メタ)アクリル酸アルキルエステルがよりさらに好ましく、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸n-オクチル、(メタ)アクリル酸イソオクチル、又は(メタ)アクリル酸イソノニルが特に好ましい。 As the (meth) acrylic acid alkyl ester from which the structural unit of the acrylic copolymer used in the present invention is derived, a (meth) acrylic acid alkyl ester having an alkyl group having 4 or more and 18 or less carbon atoms is preferable. A (meth) acrylic acid alkyl ester having an alkyl group of 4 or more and 12 or less is more preferable, and a (meth) acrylic acid alkyl ester having an alkyl group of 6 or more and 12 or less has a carbon number of 8 or more and 12 or more. More preferably, (meth) acrylic acid alkyl esters having the following alkyl groups are 2-ethylhexyl (meth) acrylic acid, n-octyl (meth) acrylic acid, isooctyl (meth) acrylic acid, or isononyl (meth) acrylic acid. Is particularly preferable.
 本発明において用いられるアクリル系共重合体としては、(メタ)アクリル酸アルキルエステルに由来する構成単位として、アルキル基部分の炭素数が4以上18以下である(メタ)アクリル酸アルキルエステルに由来する構成単位を少なくとも1種類含むものが好ましい。例えば、(メタ)アクリル酸アルキルエステルに由来する構成単位として、アルキル基部分の炭素数が4以上18以下である(メタ)アクリル酸アルキルエステルに由来する構成単位のみを有している共重合体であってもよく、アルキル基部分の炭素数が4以上18以下である(メタ)アクリル酸アルキルエステルに由来する構成単位と、これ以外の(メタ)アクリル酸アルキルエステルに由来する構成単位との両方を含む共重合体であってもよい。 The acrylic copolymer used in the present invention is derived from a (meth) acrylic acid alkyl ester having an alkyl group portion having 4 or more and 18 or less carbon atoms as a constituent unit derived from the (meth) acrylic acid alkyl ester. Those containing at least one type of structural unit are preferable. For example, a copolymer having only a structural unit derived from a (meth) acrylic acid alkyl ester having an alkyl group portion having 4 or more and 18 or less carbon atoms as a structural unit derived from the (meth) acrylic acid alkyl ester. It may be, and the structural unit derived from the (meth) acrylic acid alkyl ester having 4 or more and 18 or less carbon atoms in the alkyl group portion and the other structural unit derived from the (meth) acrylic acid alkyl ester. It may be a copolymer containing both.
 本発明において用いられるアクリル系共重合体としては、(メタ)アクリル酸アルキルエステルに由来する構成単位のみからなる共重合体であってもよく、その他の重合性化合物に由来する構成単位を含む共重合体であってもよい。その他の重合性化合物としては、ビニル基を有する化合物(ビニル単量体)が挙げられる。 The acrylic copolymer used in the present invention may be a copolymer consisting of only structural units derived from (meth) acrylic acid alkyl ester, or a copolymer containing structural units derived from other polymerizable compounds. It may be a polymer. Examples of other polymerizable compounds include compounds having a vinyl group (vinyl monomer).
 当該ビニル単量体としては、例えば、水酸基、カルボキシル基、酸無水物基、アミド基、アミノ基、エポキシ基、アルコキシ基、アシル基、シアノ基、アリール基、複素環基等の官能基を有するビニル単量体が挙げられる。水酸基を有するビニル単量体としては、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸3-ヒドロキシプロピル、(メタ)アクリル酸4-ヒドロキシブチル等の水酸基を有する(メタ)アクリル酸エステル等が挙げられる。カルボキシル基又は酸無水物基を有するビニル単量体としては、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸、マレイン酸モノブチル等が挙げられる。アミド基を有するビニル単量体としては、アクリルアミド、ジメチルアクリルアミド、ジエチルアクリルアミド、メタクリルアミド、N-メチロールアクリルアミド等が挙げられる。アミノ基を有するビニル単量体としては、ジメチルアミノエチルアクリレート等が挙げられる。エポキシ基を有するビニル単量体としては、アクリル酸グリシジル、メタクリル酸グリシジル等が挙げられる。アルコキシ基を有するビニル単量体としては、アクリル酸2-メトキシエチル、アクリル酸エトキシエチル等のアクリル酸アルコキシアルキルエステル等が挙げられる。アシル基を有するビニル単量体としては、酢酸ビニル等のビニルエステル等が挙げられる。シアノ基を有するビニル単量体としては、アクリロニトリル、メタクリロニトリル等の不飽和ニトリル等が挙げられる。アリール基を有するビニル単量体としては、スチレン等のビニル芳香族化合物等が挙げられる。複素環基を有するビニル単量体としては、N-ビニルピロリドン等のピロリドン環を有するビニル単量体等が挙げられる。これらのビニル単量体は、それぞれ単独で、又は2種以上を組み合わせて使用することができる。 The vinyl monomer has a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride group, an amide group, an amino group, an epoxy group, an alkoxy group, an acyl group, a cyano group, an aryl group or a heterocyclic group. Examples include vinyl monomers. Examples of the vinyl monomer having a hydroxyl group include a (meth) acrylic acid ester having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. And so on. Examples of the vinyl monomer having a carboxyl group or an acid anhydride group include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, monobutyl maleate and the like. Examples of the vinyl monomer having an amide group include acrylamide, dimethylacrylamide, diethylacrylamide, methacrylamide, N-methylolacrylamide and the like. Examples of the vinyl monomer having an amino group include dimethylaminoethyl acrylate and the like. Examples of the vinyl monomer having an epoxy group include glycidyl acrylate and glycidyl methacrylate. Examples of the vinyl monomer having an alkoxy group include acrylic acid alkoxyalkyl esters such as 2-methoxyethyl acrylate and ethoxyethyl acrylate. Examples of the vinyl monomer having an acyl group include vinyl esters such as vinyl acetate. Examples of the vinyl monomer having a cyano group include unsaturated nitriles such as acrylonitrile and methacrylonitrile. Examples of the vinyl monomer having an aryl group include vinyl aromatic compounds such as styrene. Examples of the vinyl monomer having a heterocyclic group include a vinyl monomer having a pyrrolidone ring such as N-vinylpyrrolidone. These vinyl monomers can be used alone or in combination of two or more.
 本発明において用いられるアクリル系共重合体としては、(メタ)アクリル酸アルキルエステルと、その他のビニル単量体との共重合体であることが好ましく、当該その他のビニル単量体に、水酸基、カルボキシル基、酸無水物基、アミド基、アミノ基、エポキシ基、及びアルコキシ基からなる群より選ばれる少なくとも1種の官能基を有するビニル単量体(以下、「ビニル単量体(A)」ということがある。)が少なくとも1種含まれている共重合体であることがより好ましく、さらに、官能基を有さないビニル単量体(以下、「ビニル単量体(B)」ということがある。)が少なくとも1種含まれている共重合体であることが好ましい。 The acrylic copolymer used in the present invention is preferably a copolymer of a (meth) acrylic acid alkyl ester and another vinyl monomer, and the other vinyl monomer has a hydroxyl group and a hydroxyl group. A vinyl monomer having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amide group, an amino group, an epoxy group, and an alkoxy group (hereinafter, "vinyl monomer (A)"). It is more preferable that the copolymer contains at least one kind of vinyl monomer (hereinafter, referred to as “vinyl monomer (B)”) which does not have a functional group. ) Is preferably a copolymer containing at least one kind.
 本発明において用いられるアクリル系共重合体としては、共重合反応に用いられる単量体の総質量に対して、炭素数が4以上18以下、好ましくは8以上12以下のアルキル基を有するアクリル酸アルキルエステルが55質量%以上95質量%以下、好ましくは60質量%以上95質量%以下、より好ましくは65質量%以上90質量%以下、さらに好ましくは80質量%以上90質量%以下、特に好ましくは83質量%以上87質量%以下、最も好ましくは85質量%;ビニル単量体(A)が1質量%以上25質量%以下、好ましくは1質量%以上20質量%以下、より好ましくは2質量%以上15質量%以下、さらに好ましくは2質量%以上10質量%以下、特に好ましくは2質量%以上6質量%以下、特に好ましくは4質量%;ビニル単量体(A)以外のビニル単量体が0質量%以上40質量%以下、好ましくは0質量%以上30質量%以下、より好ましくは0質量%以上25質量%以下、さらに好ましくは5質量%以上15質量%以下、特に好ましくは9質量%以上13質量%以下、最も好ましくは11質量%;及び、その他のビニル単量体が0質量%以上10質量%以下;の共重合体であることが好ましく、炭素数が4以上18以下、好ましくは8以上12以下のアルキル基を有するアクリル酸アルキルエステルが55質量%以上95質量%以下、好ましくは60質量%以上95質量%以下、より好ましくは65質量%以上90質量%以下、さらに好ましくは80質量%以上90質量%以下、特に好ましくは83質量%以上87質量%以下、最も好ましくは85質量%;ビニル単量体(A)が1質量%以上25質量%以下、好ましくは1質量%以上20質量%以下、より好ましくは2質量%以上15質量%以下、さらに好ましくは2質量%以上10質量%以下、特に好ましくは2質量%以上6質量%以下、特に好ましくは4質量%;ビニル単量体(B)が0質量%以上40質量%以下、好ましくは3質量%以上30質量%以下、より好ましくは5質量%以上25質量%以下、さらに好ましくは5質量%以上15質量%以下、特に好ましくは9質量%以上13質量%以下、最も好ましくは11質量%;及び、その他のビニル単量体が0質量%以上10質量%以下;の共重合体であることがより好ましい。なかでも、ビニル単量体(A)がアクリル酸であり、ビニル単量体(B)が酢酸ビニルであることが特に好ましく、共重合反応に用いられる単量体の総質量に対して、炭素数が4以上18以下、好ましくは8以上12以下のアルキル基を有するアクリル酸アルキルエステルが55質量%以上95質量%以下、好ましくは60質量%以上95質量%以下、より好ましくは65質量%以上90質量%以下、さらに好ましくは80質量%以上90質量%以下、特に好ましくは83質量%以上87質量%以下、最も好ましくは85質量%;アクリル酸が1質量%以上25質量%以下、好ましくは1質量%以上20質量%以下、より好ましくは2質量%以上15質量%以下、さらに好ましくは2質量%以上10質量%以下、特に好ましくは2質量%以上6質量%以下、特に好ましくは4質量%;酢酸ビニルが0質量%以上40質量%以下、好ましくは3質量%以上30質量%以下、より好ましくは5質量%以上25質量%以下、さらに好ましくは5質量%以上15質量%以下、特に好ましくは9質量%以上13質量%以下、最も好ましくは11質量%;及び、その他のビニル単量体が0質量%以上10質量%以下;の共重合体であることがより好ましい。このような共重合組成を有するアクリル系共重合体を粘着剤として用いることにより、粘着剤層が薄くても適度の粘着性を示し、その他の特性にも優れた粘着剤層を形成することが容易となる。 The acrylic copolymer used in the present invention is an acrylic acid having an alkyl group having 4 or more and 18 or less carbon atoms, preferably 8 or more and 12 or less carbon atoms with respect to the total mass of the monomers used in the copolymerization reaction. The alkyl ester is 55% by mass or more and 95% by mass or less, preferably 60% by mass or more and 95% by mass or less, more preferably 65% by mass or more and 90% by mass or less, still more preferably 80% by mass or more and 90% by mass or less, particularly preferably. 83% by mass or more and 87% by mass or less, most preferably 85% by mass; 1% by mass or more and 25% by mass or less of the vinyl monomer (A), preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass. 15% by mass or less, more preferably 2% by mass or more and 10% by mass or less, particularly preferably 2% by mass or more and 6% by mass or less, particularly preferably 4% by mass; vinyl monomer other than vinyl monomer (A) Is 0% by mass or more and 40% by mass or less, preferably 0% by mass or more and 30% by mass or less, more preferably 0% by mass or more and 25% by mass or less, still more preferably 5% by mass or more and 15% by mass or less, and particularly preferably 9% by mass. % Or more and 13% by mass or less, most preferably 11% by mass; and other vinyl monomers of 0% by mass or more and 10% by mass or less; preferably a copolymer having 4 or more and 18% or less carbon atoms. The acrylic acid alkyl ester having an alkyl group of 8 or more and 12 or less is preferably 55% by mass or more and 95% by mass or less, preferably 60% by mass or more and 95% by mass or less, more preferably 65% by mass or more and 90% by mass or less, further preferably. Is 80% by mass or more and 90% by mass or less, particularly preferably 83% by mass or more and 87% by mass or less, most preferably 85% by mass; vinyl monomer (A) is 1% by mass or more and 25% by mass or less, preferably 1% by mass. % Or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, further preferably 2% by mass or more and 10% by mass or less, particularly preferably 2% by mass or more and 6% by mass or less, and particularly preferably 4% by mass; The vinyl monomer (B) is 0% by mass or more and 40% by mass or less, preferably 3% by mass or more and 30% by mass or less, more preferably 5% by mass or more and 25% by mass or less, and further preferably 5% by mass or more and 15% by mass or less. Hereinafter, it is more preferable that the copolymer is particularly preferably 9% by mass or more and 13% by mass or less, most preferably 11% by mass; and 0% by mass or more and 10% by mass or less of other vinyl monomers. Among them, it is particularly preferable that the vinyl monomer (A) is acrylic acid and the vinyl monomer (B) is vinyl acetate, and carbon is relative to the total mass of the monomers used in the copolymerization reaction. The number of acrylic acid alkyl esters having an alkyl group of 4 or more and 18 or less, preferably 8 or more and 12 or less is 55% by mass or more and 95% by mass or less, preferably 60% by mass or more and 95% by mass or less, and more preferably 65% by mass or more. 90% by mass or less, more preferably 80% by mass or more and 90% by mass or less, particularly preferably 83% by mass or more and 87% by mass or less, most preferably 85% by mass; acrylic acid is 1% by mass or more and 25% by mass or less, preferably. 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, further preferably 2% by mass or more and 10% by mass or less, particularly preferably 2% by mass or more and 6% by mass or less, particularly preferably 4% by mass. %; Vinyl acetate is 0% by mass or more and 40% by mass or less, preferably 3% by mass or more and 30% by mass or less, more preferably 5% by mass or more and 25% by mass or less, still more preferably 5% by mass or more and 15% by mass or less, particularly. It is more preferable that the copolymer is 9% by mass or more and 13% by mass or less, most preferably 11% by mass; and 0% by mass or more and 10% by mass or less of other vinyl monomers. By using an acrylic copolymer having such a copolymer composition as a pressure-sensitive adhesive, it is possible to form a pressure-sensitive adhesive layer that exhibits appropriate adhesiveness even if the pressure-sensitive adhesive layer is thin and has excellent other properties. It will be easy.
 本発明において用いられるアクリル系共重合体の重量平均分子量は、好ましくは300,000以上1,000,000以下、より好ましくは450,000以上650,000以下である。アクリル系共重合体の重量平均分子量を上記範囲内とすることによって、凝集性、粘着力、他成分との混合作業性、他成分との親和性等をバランスさせることができる。分子量が300,000を下回ると凝集性が低下するため、剥離時に皮膚への糊残りを生ずる恐れがある。重量平均分子量が1,000,000を上回ると、製造時の取り扱い性に劣る。アクリル系共重合体の重量平均分子量は、ゲルパーミエーションクロマトグラフィ(GPC)法により、標準ポリスチレン換算値として求めた値である。 The weight average molecular weight of the acrylic copolymer used in the present invention is preferably 300,000 or more and 1,000,000 or less, and more preferably 450,000 or more and 650,000 or less. By setting the weight average molecular weight of the acrylic copolymer within the above range, it is possible to balance cohesiveness, adhesive strength, workability of mixing with other components, affinity with other components, and the like. If the molecular weight is less than 300,000, the cohesiveness is lowered, which may cause adhesive residue on the skin at the time of peeling. If the weight average molecular weight exceeds 1,000,000, the handleability at the time of manufacture is inferior. The weight average molecular weight of the acrylic copolymer is a value obtained as a standard polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
 本発明において用いられるアクリル系共重合体は、一般に、ラジカル重合させることにより合成することができる。当該アクリル系共重合体は、溶液重合法、懸濁重合法、又は乳化重合法により製造することができるが、良好な粘着特性が得られ易い点で、溶液重合法が好ましい。重合開始剤としては、ベンゾイルパーオキサイド、ラウロイルパーオキサイド等の有機過酸化物;アゾビスイソブチロニトリル等のアゾ系開始剤;等が挙げられる。全単量体に対して、0.1質量%以上3質量%以下程度の割合でラジカル重合開始剤を加え、窒素気流下、40℃以上90℃以下程度の温度で、数時間から数十時間撹拌して共重合させる。溶液重合法では、溶媒として、酢酸エチル、アセトン、トルエン、これらの混合物等が汎用されている。 The acrylic copolymer used in the present invention can generally be synthesized by radical polymerization. The acrylic copolymer can be produced by a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method, but the solution polymerization method is preferable in that good adhesive properties can be easily obtained. Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide and lauroyl peroxide; and azo-based initiators such as azobisisobutyronitrile. A radical polymerization initiator is added at a ratio of 0.1% by mass or more and 3% by mass or less to all the monomers, and the temperature is 40 ° C. or more and 90 ° C. or less under a nitrogen stream for several hours to several tens of hours. Stir to copolymerize. In the solution polymerization method, ethyl acetate, acetone, toluene, a mixture thereof and the like are widely used as the solvent.
(架橋及び架橋剤)
 本発明において用いられる粘着剤組成物は、架橋剤を含有していてもよい。当該粘着剤組成物が架橋剤を含有する場合には、当該粘着剤組成物中のアクリル系共重合体を架橋処理して粘着剤層を形成することによって、粘着剤層の凝集力を向上させることができる。
(Crosslinks and crosslinkers)
The pressure-sensitive adhesive composition used in the present invention may contain a cross-linking agent. When the pressure-sensitive adhesive composition contains a cross-linking agent, the cohesive force of the pressure-sensitive adhesive layer is improved by cross-linking the acrylic copolymer in the pressure-sensitive adhesive composition to form a pressure-sensitive adhesive layer. be able to.
 架橋剤としては、多官能イソシアネート化合物〔トリレンジイソシアネート(TDI)、4,4’-ジフェニルメタンジイソシアネート(MDI)、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、メタキシリレンジイソシアネート、1,5-ナフタレンジイソシアネート、水素化ジフェニルメタンジイソシアネート、水素化トリレンジイソシアネート、水素化キシリレンジイソシアネート、イソホロンジイソシアネート等〕や多官能エポキシ化合物、アセチルアセトン金属塩等が挙げられる。また、例えば、日本ポリウレタン工業株式会社製のコロネート(登録商標)HL、コロネートL、コロネートEH、三菱ガス化学株式会社製のTETRAD-X、(登録商標)、TETRAD-C(登録商標)、ナーセム(登録商標)アルミニウム等の市販品を架橋剤とすることができる。架橋剤は、単独で、又は2種類以上を用いてもよい。 Examples of the cross-linking agent include polyfunctional isocyanate compounds [tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalenedisocyanate, and hydrogenation. Diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydride xylylene diisocyanate, isophorone diisocyanate, etc.], polyfunctional epoxy compounds, acetylacetone metal salts, etc. may be mentioned. Further, for example, Coronate (registered trademark) HL, Coronate L, Coronate EH manufactured by Nippon Polyurethane Industry Co., Ltd., TETRAD-X, (registered trademark), TETRAD-C (registered trademark), Nasem (registered trademark) manufactured by Mitsubishi Gas Chemical Company, Inc. A commercially available product such as aluminum (registered trademark) can be used as a cross-linking agent. The cross-linking agent may be used alone or in combination of two or more.
 本発明において用いられる粘着剤組成物が架橋剤を含有する場合、架橋剤の含有量は、アクリル系共重合体100質量部に対して、好ましくは0.01質量部以上1質量部以下、より好ましくは0.03質量部以上0.5質量部以下、さらに好ましくは0.04質量部以上0.1質量部以下、特に好ましくは0.04質量部以上0.08質量部以下、最も好ましくは0.06質量部である。 When the pressure-sensitive adhesive composition used in the present invention contains a cross-linking agent, the content of the cross-linking agent is preferably 0.01 part by mass or more and 1 part by mass or less with respect to 100 parts by mass of the acrylic copolymer. It is preferably 0.03 parts by mass or more and 0.5 parts by mass or less, more preferably 0.04 parts by mass or more and 0.1 parts by mass or less, and particularly preferably 0.04 parts by mass or more and 0.08 parts by mass or less, most preferably. It is 0.06 parts by mass.
 本発明において用いられる粘着剤組成物に架橋剤を含有させる場合、架橋剤は、当該粘着剤組成物に予め含有させていてもよく、当該粘着剤組成物を支持体に塗工する直前又は塗工中の粘着剤組成物に添加してもよい。 When the pressure-sensitive adhesive composition used in the present invention contains a cross-linking agent, the cross-linking agent may be contained in the pressure-sensitive adhesive composition in advance, immediately before or when the pressure-sensitive adhesive composition is applied to a support. It may be added to the pressure-sensitive adhesive composition under construction.
(液状可塑剤)
 本発明に係る医療用貼付材の粘着剤層に含有される液状可塑剤は、粘着剤層を可塑化してソフト感を付与するものであり、これにより皮膚刺激性が低減される。本発明において用いられる粘着剤組成物が含有する液状可塑剤は、室温で液状であり、当該粘着剤組成物が含有するアクリル系共重合体と相溶である、重量平均分子量が350以上550以下の脂肪酸エステルである。なお、以下、単に「分子量」と称する場合には、重量平均分子量を意味する。また、脂肪酸エステルの(重量平均)分子量には、単一種の脂肪酸エステルの重量平均分子量(この場合、分子量分布はほとんどなく、実質的には単一種固有の分子量となる)や、複数種類の脂肪酸エステルの重量平均分子量が包含される。当該粘着剤組成物に含有されている室温で液状の脂肪酸エステルが、当該粘着剤組成物が含有するアクリル系共重合体と相溶であり、かつ分子量350以上550以下である単一種の脂肪酸エステルのみであってもよく、2種類以上の脂肪酸エステルを含有していてもよい。室温で液状であり、当該粘着剤組成物が含有するアクリル系共重合体と相溶である脂肪酸エステルが2種類以上含有されている場合、これらの脂肪酸エステルの重量平均分子量が350以上550以下の範囲内にあればよい。室温で液状であり、大きさが特定の範囲であって、アクリル系共重合体と相溶である脂肪酸エステルを用いることにより、アクリル系共重合体と脂肪酸エステルが均一に混じりあっており、ヒト皮膚への高い粘着力を維持しつつ、皮膚から剥離した際に皮膚への残留が充分に抑えられた粘着剤層が形成される。
(Liquid plasticizer)
The liquid plasticizer contained in the pressure-sensitive adhesive layer of the medical patch according to the present invention plasticizes the pressure-sensitive adhesive layer to give a soft feeling, thereby reducing skin irritation. The liquid plasticizer contained in the pressure-sensitive adhesive composition used in the present invention is liquid at room temperature and is compatible with the acrylic copolymer contained in the pressure-sensitive adhesive composition, and has a weight average molecular weight of 350 or more and 550 or less. Fatty acid ester. In the following, when simply referred to as "molecular weight", it means a weight average molecular weight. In addition, the (weight average) molecular weight of the fatty acid ester includes the weight average molecular weight of the single type fatty acid ester (in this case, there is almost no molecular weight distribution, and the molecular weight is substantially unique to the single type) and multiple types of fatty acids. The weight average molecular weight of the ester is included. The fatty acid ester contained in the pressure-sensitive adhesive composition that is liquid at room temperature is compatible with the acrylic copolymer contained in the pressure-sensitive adhesive composition, and has a molecular weight of 350 or more and 550 or less. It may be only, or may contain two or more kinds of fatty acid esters. When two or more types of fatty acid esters that are liquid at room temperature and compatible with the acrylic copolymer contained in the pressure-sensitive adhesive composition are contained, the weight average molecular weight of these fatty acid esters is 350 or more and 550 or less. It should be within the range. By using a fatty acid ester that is liquid at room temperature, has a specific size, and is compatible with the acrylic copolymer, the acrylic copolymer and the fatty acid ester are uniformly mixed, and humans. A pressure-sensitive adhesive layer is formed in which the residue on the skin is sufficiently suppressed when peeled off from the skin while maintaining high adhesive strength to the skin.
 分子量が350以上550以下の範囲内である脂肪酸エステルであって、アクリル系共重合体との相溶性が高いものは、充分な可塑性を付与でき、さらに、粘着剤組成物塗工後の乾燥工程等の加熱工程での揮散が無い。このため、分子量が350以上550以下の範囲内の脂肪酸エステルを液状可塑剤として用いることにより、粘着剤層を形成した場合に適度な皮膚接着性を付与可能であり、かつ剥離時に剥離される角質の面積を抑えることが可能な粘着剤組成物が得られる。 Fatty acid esters having a molecular weight in the range of 350 or more and 550 or less and having high compatibility with acrylic copolymers can impart sufficient plasticity, and further, a drying step after coating the pressure-sensitive adhesive composition. There is no volatilization in the heating process such as. Therefore, by using a fatty acid ester having a molecular weight in the range of 350 or more and 550 or less as a liquid plasticizer, it is possible to impart appropriate skin adhesiveness when a pressure-sensitive adhesive layer is formed, and keratin that is peeled off at the time of peeling. A pressure-sensitive adhesive composition capable of reducing the area of the above can be obtained.
 本発明において用いられる粘着剤組成物は、分子量が350以上550以下の範囲内の脂肪酸エステルの中でも、少なくとも1個の脂肪酸残基(脂肪酸に由来する残基。具体的には、脂肪酸から水酸基を除いた基)がオレイン酸残基(オレイン酸から水酸基を除いた基)であるオレイン酸エステルを含有することが好ましい。液状可塑剤としてオレイン酸エステル(少なくとも1個のオレイン酸残基を有する脂肪酸エステル)を用いると、本発明において用いられる粘着剤組成物から形成された粘着剤層は、連続貼付時(長期間貼付時)や繰り返し貼付時に皮膚への影響がより低減される。 The pressure-sensitive adhesive composition used in the present invention has at least one fatty acid residue (residue derived from fatty acid, specifically, a hydroxyl group from a fatty acid) among fatty acid esters having a molecular weight in the range of 350 or more and 550 or less. It is preferable that the removed group) contains an oleic acid ester which is an oleic acid residue (a group obtained by removing a fatty acid from oleic acid). When an oleic acid ester (fatty acid ester having at least one oleic acid residue) is used as the liquid plasticizer, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition used in the present invention can be continuously applied (long-term application). The effect on the skin is further reduced when it is applied repeatedly.
 オレイン酸エステルとしては、1価アルコールとオレイン酸のエステルであってもよく、多価アルコールとオレイン酸のエステルであってもよい。1価アルコールとしては、カプリルアルコール、ラウリルアルコール、ミリスチルアルコール、セチルアルコール、ステアリルアルコール、イソステアリルアルコール、オレイルアルコール等のアルキルアルコールが挙げられる。多価アルコールとしては、グルセリン、ソルビトール、グリコール等が挙げられる。 The oleic acid ester may be an ester of a monohydric alcohol and an oleic acid, or an ester of a polyhydric alcohol and an oleic acid. Examples of the monohydric alcohol include alkyl alcohols such as capryl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol and oleyl alcohol. Examples of the polyhydric alcohol include glycerin, sorbitol, glycol and the like.
 多価アルコールとオレイン酸のエステルの場合、多価アルコール中の1個の水酸基のみが脂肪酸とエステル結合していてもよく、2個以上の水酸基が脂肪酸とエステル結合していてもよい。2個以上の水酸基が脂肪酸とエステル結合したオレイン酸エステルの場合、エステル中の脂肪酸残基の一部のみがオレイン酸残基であってもよく、エステル中の全ての脂肪酸残基がオレイン酸残基であってもよい。 In the case of an ester of a polyhydric alcohol and an oleic acid, only one hydroxyl group in the polyhydric alcohol may be ester-bonded to a fatty acid, or two or more hydroxyl groups may be ester-bonded to a fatty acid. In the case of an oleic acid ester in which two or more hydroxyl groups are ester-bonded to a fatty acid, only a part of the fatty acid residues in the ester may be oleic acid residues, and all the fatty acid residues in the ester are oleic acid residues. It may be an ester.
 本発明において用いられる粘着剤組成物が含有する分子量が350以上550以下の範囲内のオレイン酸エステルとしては、具体的には、オレイン酸オクチル、オレイン酸ラウリル、オレイン酸ミリスチル、オレイン酸セチル、オレイン酸ステアリル、オレイン酸イソステアリル、オレイン酸オレイル、モノオレイン酸グリセリル、モノオレイン酸ソルビタン、ヒマシ油脂肪酸エステル等が挙げられる。これらのオレイン酸エステルは、単独で又は2種以上組み合わせて使用してもよい。本発明において用いられる粘着剤組成物が含有するオレイン酸エステルとしては、モノオレイン酸グリセリル(分子量:356.5)、モノオレイン酸ソルビタン(分子量:428.6)、オレイン酸オレイル(分子量:531)が好ましく、特に、オレイン酸オレイルが特に好ましい。 Specific examples of the oleic acid ester contained in the pressure-sensitive adhesive composition used in the present invention in the range of 350 or more and 550 or less include octyl oleate, lauryl oleate, myristyl oleate, cetyl oleate, and olein. Examples thereof include stearyl acid, isostearyl oleate, oleyl oleate, glyceryl monooleate, sorbitan monooleate, and castor oil fatty acid ester. These oleic acid esters may be used alone or in combination of two or more. Examples of the oleic acid ester contained in the pressure-sensitive adhesive composition used in the present invention include glyceryl monooleate (molecular weight: 356.5), sorbitan monooleate (molecular weight: 428.6), and oleic oleate (molecular weight: 531). Is preferable, and oleyl oleate is particularly preferable.
 本発明において用いられる粘着剤組成物における分子量が350以上550以下の範囲内のオレイン酸エステルの含有量は、アクリル系共重合体100質量部に対して、好ましくは1質量部以上35質量部以下、より好ましくは5質量部以上25質量部以下、さらに好ましくは10質量部以上20質量部以下である。この含有量が1質量部未満の場合、粘着剤層の可塑化が不充分となって皮膚刺激性を低減することができない場合があり、逆に35質量部を超える場合、粘着剤が有する凝集力が低下し、剥離時に皮膚への糊残りを生ずる恐れがある。 The content of the oleic acid ester in the pressure-sensitive adhesive composition used in the present invention in the range of 350 to 550 parts by mass is preferably 1 part by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the acrylic copolymer. , More preferably 5 parts by mass or more and 25 parts by mass or less, and further preferably 10 parts by mass or more and 20 parts by mass or less. If this content is less than 1 part by mass, the plasticizer layer may be insufficiently plasticized and skin irritation may not be reduced. Conversely, if it exceeds 35 parts by mass, the pressure-sensitive adhesive may aggregate. The force may be reduced, leaving adhesive residue on the skin during peeling.
 本発明において用いられる粘着剤組成物におけるオレイン酸エステル以外の脂肪酸エステルであって、分子量が350以上550以下の範囲内のものとしては、イソステアリン酸イソステアリル(分子量:約537)等が挙げられる。 Examples of fatty acid esters other than oleic acid esters in the pressure-sensitive adhesive composition used in the present invention, which have a molecular weight in the range of 350 or more and 550 or less, include isostearyl isostearate (molecular weight: about 537).
 本発明において用いられる粘着剤組成物は、本発明の効果を損なわない限度において、分子量が350以上550以下の範囲内の脂肪酸エステル以外のその他の液状可塑剤を含有していてもよい。その他の液状可塑剤としては、室温で液状であり、かつアクリル系共重合体と相溶性のある可塑剤であれば特に限定されるものではない。例えば、分子量が350未満のオレイン酸エステル、分子量が550超のオレイン酸エステル、オレイン酸エステル以外の脂肪酸エステル、脂肪酸エステル以外の液状可塑剤等が挙げられる。脂肪酸エステル以外の液状可塑剤としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ポリプロピレングリコール等のグリコール;オリーブ油、ヒマシ油、スクアレン、ラノリン等の油脂;流動パラフィン等の炭化水素類;等が挙げられる。その他、室温で液状の有機溶剤や界面活性剤を用いることもできる。また、粘着剤組成物に含有されている脂肪酸エステル全体として当該粘着剤組成物を構成するアクリル系共重合体と相溶であればよく、当該アクリル系共重合体と不相溶の脂肪酸エステルを含有していてもよい。 The pressure-sensitive adhesive composition used in the present invention may contain other liquid plasticizers other than fatty acid esters having a molecular weight in the range of 350 or more and 550 or less as long as the effects of the present invention are not impaired. The other liquid plasticizer is not particularly limited as long as it is a plasticizer that is liquid at room temperature and is compatible with the acrylic copolymer. Examples thereof include oleic acid esters having a molecular weight of less than 350, oleic acid esters having a molecular weight of more than 550, fatty acid esters other than oleic acid esters, and liquid plasticizers other than fatty acid esters. Examples of liquid plasticizers other than fatty acid esters include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol and polypropylene glycol; fats and oils such as olive oil, castor oil, squalane and lanolin; and hydrocarbons such as liquid paraffin. Hydrogens; etc. In addition, an organic solvent or a surfactant that is liquid at room temperature can also be used. Further, the fatty acid ester contained in the pressure-sensitive adhesive composition may be compatible with the acrylic copolymer constituting the pressure-sensitive adhesive composition as a whole, and the fatty acid ester incompatible with the acrylic copolymer may be used. It may be contained.
 本発明において用いられる粘着剤組成物が含有する液状可塑剤が、分子量が350以上550以下の範囲内であり、かつアクリル系共重合体と相溶である脂肪酸エステルのみである場合、本発明において用いられる粘着剤組成物における分子量が350以上550以下の範囲内の脂肪酸エステルの含有量は、アクリル系共重合体100質量部に対して、好ましくは1質量部以上35質量部以下、より好ましくは5質量部以上25質量部以下、さらに好ましくは10質量部以上20質量部以下である。この含有量が1質量部未満の場合、粘着剤層の可塑化が不充分となって皮膚刺激性を低減することができない場合があり、逆に35質量部を超える場合、粘着剤が有する凝集力が低下し、剥離時に皮膚への糊残りを生ずる恐れがある。なお、アクリル系共重合体が含有する分子量が350以上550以下の範囲内であり、かつアクリル系共重合体と相溶である脂肪酸エステルが2種類以上である場合、「粘着剤組成物における分子量が350以上550以下の範囲内の脂肪酸エステルの含有量」は、分子量が350以上550以下の範囲内であり、かつアクリル系共重合体と相溶である脂肪酸エステルに該当する脂肪酸エステルの総量を意味する。 In the present invention, when the liquid plasticizer contained in the pressure-sensitive adhesive composition used in the present invention is only a fatty acid ester having a molecular weight in the range of 350 or more and 550 or less and compatible with an acrylic copolymer. The content of the fatty acid ester having a molecular weight in the range of 350 or more and 550 parts or less in the pressure-sensitive adhesive composition used is preferably 1 part by mass or more and 35 parts by mass or less, more preferably 1 part by mass or less, based on 100 parts by mass of the acrylic copolymer. It is 5 parts by mass or more and 25 parts by mass or less, more preferably 10 parts by mass or more and 20 parts by mass or less. If this content is less than 1 part by mass, the plasticizer layer may be insufficiently plasticized and skin irritation may not be reduced. Conversely, if it exceeds 35 parts by mass, the pressure-sensitive adhesive may aggregate. The force may be reduced, leaving adhesive residue on the skin during peeling. When the molecular weight contained in the acrylic copolymer is in the range of 350 or more and 550 or less and the number of fatty acid esters compatible with the acrylic copolymer is two or more, "molecular weight in the pressure-sensitive adhesive composition". "Content of fatty acid ester in the range of 350 or more and 550 or less" is the total amount of fatty acid ester corresponding to the fatty acid ester having a molecular weight in the range of 350 or more and 550 or less and compatible with the acrylic copolymer. means.
 本発明において用いられる粘着剤組成物に、分子量が350以上550以下の範囲内であり、かつアクリル系共重合体と相溶である脂肪酸エステルと、その他の液状可塑剤とを含有する場合、本発明において用いられる粘着剤組成物に含まれている液状可塑剤全量に対する、分子量が350以上550以下の範囲内の脂肪酸エステルの含有量は、50質量%以上であることが好ましく、60質量%以上であることがより好ましく、80質量%以上であることがさらに好ましく、90質量%以上であることが特に好ましい。また、粘着剤組成物に含まれている液状可塑剤全体の重量平均分子量、特に、室温で液状の脂肪酸エステル全体の重量平均分子量が、350以上550以下の範囲であることが好ましい。 When the pressure-sensitive adhesive composition used in the present invention contains a fatty acid ester having a molecular weight in the range of 350 or more and 550 or less and compatible with an acrylic copolymer, and other liquid plasticizers, the present invention The content of the fatty acid ester having a molecular weight in the range of 350 or more and 550 or less is preferably 50% by mass or more, preferably 60% by mass or more, based on the total amount of the liquid plasticizer contained in the pressure-sensitive adhesive composition used in the present invention. Is more preferable, 80% by mass or more is further preferable, and 90% by mass or more is particularly preferable. Further, the weight average molecular weight of the entire liquid plasticizer contained in the pressure-sensitive adhesive composition, particularly, the weight average molecular weight of the entire fatty acid ester liquid at room temperature is preferably in the range of 350 or more and 550 or less.
(添加剤)
 本発明において用いられる粘着剤組成物は、前記架橋剤の他に、必要に応じて、各種添加剤を含有することができる。当該添加剤としては、薬物、充填剤、酸化防止剤(抗酸化剤、防腐剤)、着色剤、香料、粘着付与剤等、貼付材が備える粘着剤層を形成する粘着剤において慣用されている添加剤を含有することができる。例えば、粘着剤の粘着特性を調整するために、粘着付与剤を配合することができる。粘着付与剤としては、例えば、テルペン系、テルペンフェノール系、クマロンインデン系、スチレン系、ロジン系、キシレン系、フェノール系、石油系等の粘着付与樹脂を挙げることができる。
(Additive)
The pressure-sensitive adhesive composition used in the present invention may contain various additives in addition to the cross-linking agent, if necessary. As the additive, it is commonly used in adhesives that form an adhesive layer provided in a patch, such as drugs, fillers, antioxidants (antioxidants, preservatives), colorants, fragrances, and tackifiers. Additives can be included. For example, a tackifier can be added to adjust the adhesive properties of the pressure-sensitive adhesive. Examples of the tackifier include terpene-based, terpene phenol-based, kumaron inden-based, styrene-based, rosin-based, xylene-based, phenol-based, and petroleum-based tackifier resins.
<医療用貼付材>
 本発明に係る医療用貼付材は、支持体と粘着剤層の積層体を備える。本発明に係る医療用貼付材は、支持体の少なくとも片面に、本発明において用いられる粘着剤組成物からなる粘着剤層を備えることが好ましい。粘着剤層が前記粘着剤組成物により形成されるため、ヒト皮膚への充分な粘着力を維持しつつ、剥離時の角質の剥離面積を抑えることができ、皮膚表面の同じ部位に連続貼付又は繰り返し貼付した際にも皮膚刺激への影響が少ない医療用貼付材が得られる。このため、本発明に係る医療用貼付材は、カテーテル等のチューブ固定用のように皮膚の同じ部位に繰り返し貼付される貼付材や、磁気治療器絆創膏、テーピングテープ等のような皮膚の特定の部位に連続貼付や繰り返し貼付される貼付材に好適である。
<Medical patch>
The medical patch according to the present invention includes a laminate of a support and an adhesive layer. The medical patch according to the present invention preferably has a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition used in the present invention on at least one side of the support. Since the pressure-sensitive adhesive layer is formed by the pressure-sensitive adhesive composition, it is possible to suppress the peeling area of the keratin at the time of peeling while maintaining sufficient adhesive strength to human skin, and it can be continuously applied to the same part of the skin surface or A medical patch material that has little effect on skin irritation even when repeatedly applied can be obtained. Therefore, the medical patch according to the present invention is a patch that is repeatedly stuck to the same part of the skin such as for fixing a tube such as a catheter, or a specific skin such as a magnetic therapy device adhesive plaster or taping tape. It is suitable for a sticking material that is continuously or repeatedly stuck to a part.
(支持体)
 本発明に係る医療用貼付材を構成する支持体は、透湿度が500g/m・24h以上のものである。充分な透湿度である支持体を用いることにより、透湿度が充分に高く、皮膚に貼付した際の蒸れが少なく、皮膚刺激や貼付中のかゆみが生じにくい医療用貼付材となる。支持体の透湿度としては、500g/m・24h以上が好ましく、700g/m・24h以上であることがより好ましく、1,000g/m・24h以上であることがさらに好ましく、1,500g/m・24h以上であることがよりさらに好ましく、5,000g/m・24h以上であることが特に好ましく、20,000g/m・24h以上であることが最も好ましい。
(Support)
Support constituting the medical adhesive material according to the present invention, moisture permeability is more than 500g / m 2 · 24h. By using a support having sufficient moisture permeability, it becomes a medical patch material having sufficiently high moisture permeability, less stuffiness when applied to the skin, and less likely to cause skin irritation or itching during application. The moisture permeability of the support, preferably at least 500g / m 2 · 24h, more preferably 700g / m 2 · 24h or more, still more preferably 1,000g / m 2 · 24h or more, 1, more preferably more is at 500g / m 2 · 24h or more, particularly preferably at 5,000g / m 2 · 24h or more, and most preferably 20,000g / m 2 · 24h or more.
 支持体としては、例えば、含浸紙、コート紙、上質紙、クラフト紙、和紙、グラシン紙等の紙類;ポリエチレンテレフタレートやポリブチレンテレフタレート等のポリエステルフィルム、ポリエチレンやポリプロピレン等のポリオレフィンフィルム、ポリ塩化ビニルフィルム、ポリカーボネートフィルム、ポリウレタンフィルム、セロハンフィルム等のプラスチックフィルム;発泡体;不織布、織布、編布等の布帛類;これら2種以上の積層体;等が挙げられる。前記布帛類の材質としては、木綿等の天然素材、合成樹脂素材、再生樹脂材料及びこれら適宜を組み合わせた各種の材料を用いることができ、中でもポリエステル、ポリウレタン、ポリエチレン、ポリプロピレン、ポリアミド、アクリル樹脂、木綿等を原料とする不織布、織布、編布等を用いることができる。 Examples of the support include impregnated paper, coated paper, high-quality paper, kraft paper, Japanese paper, glassin paper, and other papers; polyester films such as polyethylene terephthalate and polybutylene terephthalate, polyolefin films such as polyethylene and polypropylene, and polyvinyl chloride. Plastic films such as films, polypropylene films, polyurethane films, cellophane films; foams; fabrics such as non-woven fabrics, woven fabrics, knitted fabrics; laminates of two or more of these; and the like. As the material of the fabrics, natural materials such as cotton, synthetic resin materials, recycled resin materials and various materials in which these are appropriately combined can be used. Among them, polyester, polyurethane, polyethylene, polypropylene, polyamide, acrylic resin, etc. Non-woven fabrics, woven fabrics, knitted fabrics, etc. made of cotton or the like can be used.
 本発明に係る医療用貼付材の支持体の透湿度は、500g/m・24h以上である。そのため、当該支持体としては、不織布、織布、編布等の布帛類が好ましい。中でも、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く、貼付下の皮膚面の動きに対する追随性に優れる点において、さらには、強度を維持しやすく、自背面接着力がより強くなる点において、織布が好ましい。 Moisture permeability of the support of the medical adhesive material according to the present invention is 500g / m 2 · 24h or more. Therefore, as the support, fabrics such as non-woven fabric, woven fabric, and knitted fabric are preferable. Among them, a material that is flexible enough to 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 are preferable, and the skin under application is preferable. The woven fabric is preferable in that it has excellent followability to the movement of the surface, and further, it is easy to maintain the strength and the self-back surface adhesive force becomes stronger.
 支持体の厚みは、伸び、引張り強さ、作業性等の物理的性質や、貼付時の感触や患部の密閉性等を考慮して適宜選択可能であるが、通常5μmから1mm程度である。なお、支持体の厚みが5μm以上30μm以下程度とごく薄い場合は、粘着剤層が設けられた支持体の一方側の面とは反対の面(以下、他方側の面という)上に、キャリア層を設けてもよい。 The thickness of the support can be appropriately selected in consideration of physical properties such as elongation, tensile strength, workability, feel at the time of application, and airtightness of the affected area, but is usually about 5 μm to 1 mm. When the thickness of the support is as thin as 5 μm or more and 30 μm or less, the carrier is placed on a surface opposite to one surface of the support provided with the adhesive layer (hereinafter referred to as the other surface). Layers may be provided.
 支持体が布帛類である場合、その厚みは、好ましくは50μm以上1mm以下、より好ましくは100μm以上800μm以下、更に好ましくは200μm以上700μm以下である。また、目付けは、皮膚への追従性の点から、好ましくは400g/m以下、より好ましくは300g/m以下、さらに好ましくは250g/m以下である。 When the support is a woven fabric, its thickness is preferably 50 μm or more and 1 mm or less, more preferably 100 μm or more and 800 μm or less, and further preferably 200 μm or more and 700 μm or less. The basis weight is preferably 400 g / m 2 or less, more preferably 300 g / m 2 or less, and further preferably 250 g / m 2 or less from the viewpoint of followability to the skin.
 また、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10μm以上300μm以下、より好ましくは12μm以上200μm以下、さらに好ましくは15μm以上150μm以下である。なお、支持体がフィルムである場合は、粘着剤層と支持体の投錨性を向上することを目的に、支持体の一方側の面又は他方側の面、あるいはそれら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。 When the support is a plastic film, its thickness is preferably 10 μm or more and 300 μm or less, more preferably 12 μm or more and 200 μm or less, and further preferably 15 μm or more and 150 μm or less. When the support is a film, sandblasting or corona treatment is performed on one side or the other side of the support, or both sides thereof, for the purpose of improving the anchoring property of the adhesive layer and the support. Etc. may be performed.
 前記支持体の厚みが5μmよりも小さいと、粘着テープ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、粘着テープが皮膚の動きに追随しにくくなり、粘着テープ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おそれがある。 If the thickness of the support is less than 5 μm, the strength and handleability of the adhesive tape will decrease, making it difficult to attach it to the skin, tearing it due to contact with other members, or using it 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 adhesive tape to follow the movement of the skin, and it becomes easy to form a trigger for peeling at the edge of the adhesive tape, so that the adhesive tape peels off from the skin in a short time. There is a risk that the feeling of discomfort during pasting will increase.
(粘着剤層)
 粘着剤層は、本発明において用いられる粘着剤組成物を、支持体の表面に所望の厚みとなるように塗工し、乾燥させることにより形成される。粘着剤組成物が架橋剤を含む場合、塗工後に紫外線照射処理等の架橋剤の種類に応じた架橋処理を行う。
(Adhesive layer)
The pressure-sensitive adhesive layer is formed by applying the pressure-sensitive adhesive composition used in the present invention to the surface of the support to a desired thickness and drying it. When the pressure-sensitive adhesive composition contains a cross-linking agent, a cross-linking treatment according to the type of the cross-linking agent such as an ultraviolet irradiation treatment is performed after coating.
 本発明に係る医療用貼付材における粘着剤層の厚みは、特に限定されるものではなく、好ましくは1μm以上200μm以下、より好ましくは10μm以上100μm以下、さらに好ましくは20μm以上80μm以下である。粘着力は、粘着剤層の厚みに依存し、粘着剤層の厚みが厚すぎると、粘着力が高くなりすぎ、粘着剤層の厚みが薄すぎると、粘着力が弱くなる。粘着剤層の厚みを前記範囲内とすることで、皮膚に十分な粘着力で粘着できることに加えて、貼付材を皮膚等の微細な凹凸のある被着体表面に沿って密着させることができ、さらに、使用後に剥離した際に皮膚刺激を低く抑えることができる。 The thickness of the pressure-sensitive adhesive layer in the medical patch according to the present invention is not particularly limited, and is preferably 1 μm or more and 200 μm or less, more preferably 10 μm or more and 100 μm or less, and further preferably 20 μm or more and 80 μm or less. The adhesive strength depends on the thickness of the adhesive layer. If the thickness of the adhesive layer is too thick, the adhesive strength becomes too high, and if the thickness of the adhesive layer is too thin, the adhesive strength becomes weak. By setting the thickness of the pressure-sensitive adhesive layer within the above range, in addition to being able to adhere to the skin with sufficient adhesive strength, the adhesive material can be adhered along the surface of the adherend having fine irregularities such as the skin. Furthermore, skin irritation can be suppressed low when peeled off after use.
(キャリア層)
 本発明に係る医療用貼付材は、支持体に仮着させてキャリア層を形成させてもよい。例えば、「キャリア層/支持体/粘着剤層/セパレーター層」の積層構成を有する貼付材とすることができる。キャリア層により、支持体の厚さが薄い場合に、支持体の製膜性、貼付材の取扱性、被着体への貼付性を向上させることができる。キャリア層は、貼付材の取扱性を向上させるために設けられるものであるから、貼付材の全面を覆っていても、貼付材の縁部のみを覆っていても、あるいは、格子状等のパターン状に覆っていてもよい。
(Career layer)
The medical patch according to the present invention may be temporarily attached to a support to form a carrier layer. For example, it can be a patch having a laminated structure of "carrier layer / support / adhesive layer / separator layer". The carrier layer can improve the film-forming property of the support, the handleability of the sticking material, and the stickability to the adherend when the thickness of the support is thin. Since the carrier layer is provided to improve the handleability of the sticking material, it may cover the entire surface of the sticking material, only the edge of the sticking material, or a pattern such as a grid pattern. It may be covered in a shape.
 キャリア層は、例えば、ポリウレタン、ポリエチレン、ポリプロピレン、アイオノマー、ポリアミド、ポリ塩化ビニル、ポリ塩化ビニリデン、エチレン酢酸ビニル共重合体、熱可塑性ポリエステル、ポリテトラフルオロエチレン等の各種熱可塑性樹脂からなるフィルムを用いて形成することが好ましい。 For the carrier layer, for example, a film made of various thermoplastic resins such as polyurethane, polyethylene, polypropylene, ionomer, polyamide, polyvinyl chloride, polyvinylidene chloride, ethylene vinyl acetate copolymer, thermoplastic polyester, and polytetrafluoroethylene is used. It is preferable to form it.
 各種フィルムは、紙にラミネートされた状態のものでもよい。これらのキャリア層は、支持体(例えばポリウレタンエラストマーフィルム)に比べて、厚みが厚いか、腰の強いものとすることが好ましい。キャリア層の厚みは、適宜設定できるが、通常、10μm以上、好ましくは20μm以上であり、その上限値は500μm程度である。 The various films may be laminated on paper. It is preferable that these carrier layers are thicker or stiffer than the support (for example, polyurethane elastomer film). The thickness of the carrier layer can be appropriately set, but is usually 10 μm or more, preferably 20 μm or more, and the upper limit thereof is about 500 μm.
(セパレーター層)
 本発明に係る医療用貼付材は、支持体層、粘着剤層の他に、通常、粘着剤層を皮膚に貼り付けるときまで、粘着剤層を保護するために、粘着剤層に隣接してセパレーター層が備えられる。
(Separator layer)
In addition to the support layer and the pressure-sensitive adhesive layer, the medical patch according to the present invention is usually adjacent to the pressure-sensitive adhesive layer in order to protect the pressure-sensitive adhesive layer until the time when the pressure-sensitive adhesive layer is attached to the skin. A separator layer is provided.
 本発明におけるセパレーター層としては、特に限定されず、貼付材の技術分野において、一般に、離型紙、離型フィルム、剥離紙、剥離フィルム、剥離ライナー等と称して使用されるものを用いることができる。具体的には、例えば、表面をシリコーン処理したポリエチレンテレフタレートフィルム、表面をシリコーン処理したポリエチレンと紙との積層体等が挙げられる。また、セパレーター層は、取扱い性(すなわち、粘着剤層からの剥離性)を向上するために、切れ目を設けてもよく、貼付材より大きな面積に形成し、周縁部に掴み部を設けてもよい。また、セパレーター層は、取扱い性の向上や印刷適性の向上等の目的で、セパレーター層の粘着剤層に対向する面又は粘着剤層の反対側の面に、サンドブラスト処理等による凹凸を設けてもよい。 The separator layer in the present invention is not particularly limited, and in the technical field of affixing materials, those generally used as release paper, release film, release paper, release film, release liner and the like can be used. .. Specific examples thereof include a polyethylene terephthalate film whose surface is treated with silicone, a laminate of polyethylene whose surface is treated with silicone, and paper. Further, the separator layer may be provided with a cut in order to improve handleability (that is, releasability from the pressure-sensitive adhesive layer), may be formed in a larger area than the sticking material, and a grip portion may be provided on the peripheral edge portion. Good. Further, the separator layer may be provided with irregularities by sandblasting or the like on the surface of the separator layer facing the adhesive layer or the surface opposite to the adhesive layer for the purpose of improving handleability and printability. Good.
 セパレーター層の厚みは、適宜設定することができ、特に限定されないが、通常20μm以上、好ましくは40μm以上であり、その上限値は500μm程度である。 The thickness of the separator layer can be appropriately set and is not particularly limited, but is usually 20 μm or more, preferably 40 μm or more, and the upper limit thereof is about 500 μm.
(透湿度)
 本発明に係る医療用貼付材は、透湿度が500g/m・24h以上であることが好ましい。当該貼付材は、透湿度が500g/m・24h以上であることで、皮膚に貼付した際の蒸れが少ないため、皮膚刺激や貼付中のかゆみが生じにくい。当該貼付材の透湿度は、700g/m・24h以上であることがより好ましく、1,000g/m・24h以上であることがさらに好ましく、1,500g/m・24h以上であることがよりさらに好ましく、5,000g/m・24h以上であることが特に好ましく、20,000g/m・24h以上であることが最も好ましい。透湿度は高いほど好ましく、好ましい透湿度の上限は特にないが、通常30,000g/m・24h以下である。なお、本発明において透湿度の測定は、JIS Z0208のB条件に従って、温度40℃、相対湿度90%で測定する。すなわち、貼付材の片面側を温度40℃、相対湿度90%に調節し、他面側には塩化カルシウム等の吸湿剤を置いて貼付材を通過した水分を吸収させ、吸湿剤の重量変化量を24時間、1m当たりに換算して算出する。
(Humidity permeability)
Medical patch according to the present invention, it is preferred moisture permeability is at 500g / m 2 · 24h or more. The patch is, moisture permeability that is 500g / m 2 · 24h or more, less stuffiness when applied to the skin, hardly occurs itchy skin irritation or sticking in. Moisture permeability of the patch, it is more preferably 700g / m 2 · 24h or more, more preferably 1,000g / m 2 · 24h or more, 1,500g / m 2 · 24h or more There still more preferably, particularly preferably at 5,000g / m 2 · 24h or more, and most preferably 20,000g / m 2 · 24h or more. Moisture permeability higher preferably, the upper limit is not particularly preferred moisture permeability is usually at most 30,000g / m 2 · 24h. In the present invention, the moisture permeability is measured at a temperature of 40 ° C. and a relative humidity of 90% according to the B condition of JIS Z0208. That is, the temperature on one side of the patch is adjusted to 40 ° C. and the relative humidity is 90%, and a moisture absorbent such as calcium chloride is placed on the other side to absorb the moisture that has passed through the patch, and the amount of change in the weight of the moisture absorbent. Is calculated by converting to 24 hours per 1 m 2 .
(粘着力)
 本発明に係る医療用貼付材の粘着力は、対ベークライト粘着力(剥離力)として、好ましくは0.5N/25mm以上12.0N/25mm以下、より好ましくは2.0N/25mm以上8.0N/25mm以下の範囲内であることが好ましい。医療用貼付材の粘着力がこの範囲内であることにより、本発明に係る医療用貼付材を皮膚表面に貼付した場合、十分な貼付性能を備え、貼付中に位置ずれが生じないとともに、当該貼付材を剥離するときには、皮膚表面を剥離したり、かぶれを発生したりする恐れがない。
(Adhesive force)
The adhesive strength of the medical patch according to the present invention is preferably 0.5 N / 25 mm or more and 12.0 N / 25 mm or less, more preferably 2.0 N / 25 mm or more and 8.0 N as the adhesive force (peeling force) against bakelite. It is preferably within the range of / 25 mm or less. Since the adhesive strength of the medical patch is within this range, when the medical patch according to the present invention is stuck on the skin surface, it has sufficient sticking performance, does not cause misalignment during sticking, and is said to be relevant. When peeling off the patch, there is no risk of peeling off the skin surface or causing a rash.
 医療用貼付材の粘着力の測定方法は以下の通りである。すなわち、貼付材を、幅25mm×長さ15mm以上、好ましくは100mmの所定の長さに裁断して試験片とする。試験片をベークライト製試験パネルに押しつけて貼着させた後、2kgのローラーで圧着速さ300mm/分、圧着回数1往復で貼着させて試験片を調製する。貼着してから20分間経過した後、ISO29862のメソッド1(対応JIS:JIS  Z0237)の引きはがし粘着力試験方法に準拠し、剥離角度180°、剥離速度300mm/分の条件で、粘着力を測定する。 The method for measuring the adhesive strength of the medical patch is as follows. That is, the sticking material is cut into a predetermined length of 25 mm in width × 15 mm in length or more, preferably 100 mm to obtain a test piece. The test piece is pressed against a Bakelite test panel to be attached, and then attached with a 2 kg roller at a crimping speed of 300 mm / min and one reciprocating crimping frequency to prepare a test piece. After 20 minutes have passed since the application, the adhesive strength is applied under the conditions of a peeling angle of 180 ° and a peeling speed of 300 mm / minute in accordance with the peeling adhesive strength test method of ISO29862 method 1 (corresponding JIS: JIS Z0237). Measure.
(医療用貼付材の製造方法)
 本発明に係る医療用貼付材の製造方法は特に限定されない。例えば、いわゆる剥離ライナーとして一般に使用されるセパレーター層の上に、粘着剤溶液を塗布し、乾燥させて粘着剤層を形成する方法を採用することが好ましい。粘着剤層の連続的な形成方法としては、セパレーター層を一方向に走行させながら、その上に粘着剤溶液を塗布し、乾燥させる方法が好ましい。粘着剤を溶融してセパレーター層上に塗工する方法を採用してもよい。また、特定の形状の繰り返しパターンコーティングとすることもできる。
(Manufacturing method of medical patch material)
The method for producing the medical patch according to the present invention is not particularly limited. For example, it is preferable to adopt a method of applying a pressure-sensitive adhesive solution on a separator layer generally used as a so-called release liner and drying it to form a pressure-sensitive adhesive layer. As a method for continuously forming the pressure-sensitive adhesive layer, a method in which the pressure-sensitive adhesive solution is applied onto the separator layer while running in one direction and dried is preferable. A method of melting the adhesive and applying it on the separator layer may be adopted. It can also be a repeating pattern coating of a specific shape.
 セパレーター層の片面に粘着剤層を形成した積層体と支持体とを、粘着剤層と支持体の表面が密着するように貼り合わせることにより、「支持体/粘着剤層/セパレーター層」の積層構成を有する貼付材を作製することができる。また、支持体の片面に任意層であるキャリア層を形成した積層体の場合、粘着剤層と当該積層体の支持体の表面が密着するように貼り合わせることにより、「キャリア層(任意層)/支持体/粘着剤層/セパレーター層」の積層構成を有する貼付材を作製することができる。 Lamination of "support / adhesive layer / separator layer" by adhering a laminate having an adhesive layer formed on one side of the separator layer and a support so that the adhesive layer and the surface of the support are in close contact with each other. A patch having a structure can be produced. Further, in the case of a laminated body in which a carrier layer which is an arbitrary layer is formed on one side of the support, the adhesive layer and the surface of the support of the laminated body are bonded so as to be in close contact with each other to form a “carrier layer (arbitrary layer)”. A patch material having a laminated structure of "/ support / adhesive layer / separator layer" can be produced.
 次に実施例を示して本発明をさらに詳細に説明するが、本発明は以下の実施例に限定されるものではない。 Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
[実施例1~4、比較例1~7]
 各種液状可塑剤を含有する粘着剤組成物を調製し、これで粘着剤層を形成した貼付材について、粘着力とヒト皮膚への影響を調べた。液状可塑剤としては、オレイン酸メチル(分子量:296.5)、ミリスチン酸イソプロピル(分子量:268.0)、モノオレイン酸グリセリル(分子量:356.0)、モノオレイン酸ソルビタン(分子量:428.6)、オレイン酸オレイル(分子量:531.0)、イソステアリン酸イソステアリル(分子量:537.0)、大豆油(分子量:約880、SRソイビーン-LQ-(JP)、クローダジャパン社製)、トリオレイン酸ソルビタン(分子量:935.0)、ヒマシ油脂肪酸エステル(分子量:約500、リックサイザーC-101、伊藤製油社製)、オレイン酸デシル(分子量:422.4)、特殊ヒマシ油系縮合脂肪酸(分子量:800、ミネラゾール、伊藤製油社製)、を用いた。また、支持体としては、織布(縦糸:コアスパン、横糸:綿、透湿度:21,060g/m・24h、目付155g/m)、ウレタン不織布(繊維径:15μm、透湿度:21,590g/m・24h、目付65g/m)、ポリエチレンフィルム(厚さ:50μm、透湿度:60g/m・24h)を用いた。
[Examples 1 to 4, Comparative Examples 1 to 7]
A pressure-sensitive adhesive composition containing various liquid plasticizers was prepared, and the adhesive strength and the effect on human skin of the adhesive material on which the pressure-sensitive adhesive layer was formed were investigated. As the liquid plasticizer, methyl oleate (molecular weight: 296.5), isopropyl myristate (molecular weight: 268.0), glyceryl monooleate (molecular weight: 356.0), sorbitan monooleate (molecular weight: 428.6). ), Oleyl oleate (molecular weight: 531.0), isostearyl isostearate (molecular weight: 537.0), soybean oil (molecular weight: about 880, SR soybean-LQ- (JP), manufactured by Claude Japan), triolein Polysorbate acid (molecular weight: 935.0), castor oil fatty acid ester (molecular weight: about 500, Ricksizer C-101, manufactured by Ito Oil Co., Ltd.), decyl oleate (molecular weight: 422.4), special castor oil-based condensed fatty acid (molecular weight: 422.4) Molecular weight: 800, Minerazole, manufactured by Ito Oil Co., Ltd.) was used. As the support, woven (warp: corespun, weft: cotton, moisture permeability: 21,060g / m 2 · 24h, basis weight 155 g / m 2), urethane nonwoven (fiber diameter: 15 [mu] m, moisture permeability: 21, 590g / m 2 · 24h, basis weight 65g / m 2), polyethylene film (thickness: 50 [mu] m, moisture permeability: 60g / m 2 · 24h) was used.
<サンプル作製>
 まず、粘着剤組成物として、アクリル酸2-エチルヘキシルエステル/酢酸ビニル/アクリル酸=85/11/4(質量比)からなる単量体混合物を共重合反応して得られたアクリル系共重合体の溶液に、アクリル系共重合体100質量部に対して、表1~3に記載の液状可塑剤を表1に示す質量部となるように混合し、さらに架橋剤としてTetrad-X(三菱ガス化学社製)0.06質量部を混合し、均一な粘着剤組成物の溶液を調製した。
 この粘着剤組成物の溶液を、セパレーター(シリコーン処理ポリラミ剥離紙)の剥離処理面に、乾燥後の厚みが38μmになるよう塗布、乾燥して粘着剤層を形成した。この粘着剤層を、表1~3に記載の支持体に貼り合わせて貼付材を作製した。
<Sample preparation>
First, as a pressure-sensitive adhesive composition, an acrylic copolymer obtained by copolymerizing a monomer mixture composed of 2-ethylhexyl ester of acrylic acid / vinyl acetate / acrylic acid = 85/11/4 (mass ratio). The liquid plastic agents shown in Tables 1 to 3 were mixed with 100 parts by mass of the acrylic copolymer in the solution of the above so as to have the parts by mass shown in Table 1, and Tetrad-X (Mitsubishi Gas) was further used as a cross-linking agent. A uniform solution of the pressure-sensitive adhesive composition was prepared by mixing 0.06 parts by mass (manufactured by Kagaku Co., Ltd.).
The solution of this pressure-sensitive adhesive composition was applied to the peel-treated surface of the separator (silicone-treated polylami release paper) so that the thickness after drying was 38 μm, and dried to form a pressure-sensitive adhesive layer. This pressure-sensitive adhesive layer was bonded to the supports shown in Tables 1 to 3 to prepare a patch.
<ヒト皮膚への粘着力の測定>
 サイズ15mm×70mmの被験サンプルを、ヒト被験者の前腕部に貼付した。貼付から24時間後に、インストロン型引張試験機を用いて、剥離速度100mm/分、剥離角度90°の条件で粘着力(N/15mm)を測定した(n=8)。剥離は、小指側から親指側に行った。測定結果を表1~3に示す。
<Measurement of adhesive strength to human skin>
A test sample having a size of 15 mm × 70 mm was attached to the forearm of a human subject. Twenty-four hours after application, the adhesive strength (N / 15 mm) was measured using an Instron type tensile tester under the conditions of a peeling speed of 100 mm / min and a peeling angle of 90 ° (n = 8). The peeling was performed from the little finger side to the thumb side. The measurement results are shown in Tables 1 to 3.
<角質剥離面積率の測定>
 前記の粘着力測定において剥離された後の各被験サンプルを、カチオン染色(ゲンチアナバイオレット:1.0%、ブリリアントグリーン:0.5%、蒸留水:98.5%)で染色した後、流水下で洗浄した。染色後の被験サンプルを顕微鏡(VHX-1000:VH-Z100UR、キーエンス社製)下で撮像し、得られた画像を画像処理装置(Win ROOF、三谷商事社製)で画像解析することによって、各被験サンプルに付着している角質細胞の面積を測定した。各被験サンプルについて、3視野の角質細胞付着面積率([角質細胞付着面積]/[被験サンプルの表面積]×100(%))を算出し、この平均値を各被験サンプルの角質剥離面積率とした(n=8)。測定結果を表1~3に示す。
<Measurement of exfoliated area ratio>
Each test sample after being peeled off in the above-mentioned adhesive strength measurement was stained with cation staining (Gentian violet: 1.0%, Brilliant green: 0.5%, Distilled water: 98.5%) and then under running water. Washed with. The stained test sample was imaged under a microscope (VHX-1000: VH-Z100UR, manufactured by KEYENCE), and the obtained image was analyzed by an image processing device (Win ROOF, manufactured by Mitani Shoji Co., Ltd.). The area of keratinocytes attached to the test sample was measured. For each test sample, the keratinocyte attachment area ratio ([keratinocyte attachment area] / [surface area of the test sample] × 100 (%)) of three visual fields was calculated, and this average value was taken as the keratin exfoliation area ratio of each test sample. (N = 8). The measurement results are shown in Tables 1 to 3.
<粘着剤の残留>
 前記の粘着力測定において、各被験サンプルを剥離した後の皮膚表面に、粘着剤が残ったかどうかを目視で確認した(n=8)。結果を表1~3に示す。表中、「×」は剥離時に粘着剤が皮膚に残ったことを、「〇」は剥離時に粘着剤が皮膚に残らなかったことを示す。
<Residual adhesive>
In the above-mentioned adhesive strength measurement, it was visually confirmed whether or not the adhesive remained on the skin surface after each test sample was peeled off (n = 8). The results are shown in Tables 1 to 3. In the table, "x" indicates that the adhesive remained on the skin at the time of peeling, and "○" indicates that the adhesive did not remain on the skin at the time of peeling.
<繰り返し前腕部貼付試験>
 被験サンプルを、ヒト皮膚表面に貼付し、24時間ごとに剥離し、1時間後の皮膚反応を確認した後に、新たな同種の被験サンプルを同部位に貼付する繰り返し前腕部貼付試験(最大7日間、1試験区当たり7枚の被験サンプルを使用)を行った(n=9)。皮膚反応は、剥離1時間後及び24時間後(試験終了日)に、5:反応なし、4:軽い紅斑あり、3:紅斑あり、2:紅斑+浮腫あり、1:紅斑+浮腫+丘疹あり、又は小水疱あり、0:大水疱あり、として評価した。結果を表1~3に示す。
<Repeated forearm sticking test>
A repeated forearm attachment test (up to 7 days) in which the test sample is attached to the surface of human skin, peeled off every 24 hours, the skin reaction after 1 hour is confirmed, and then a new test sample of the same type is attached to the same site. , 7 test samples were used per test group) (n = 9). Skin reactions were 1 hour and 24 hours after exfoliation (test end date): 5: no reaction, 4: mild erythema, 3: erythema, 2: erythema + edema, 1: erythema + edema + papules. , Or with vesicles, 0: with large erythema. The results are shown in Tables 1 to 3.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 支持体が同一である実施例1~6及び比較例1~8で比較すると、各被験サンプルのヒト皮膚への粘着力は、脂肪酸エステルをアクリル系共重合体100質量部に対して、10質量部又は20質量部配合した被験サンプル(比較例2~3、実施例1~6、比較例5~8)では、脂肪酸エステルを配合していない被験サンプル(比較例1)と比べて高い数値であり、脂肪酸エステルを配合することにより、粘着力を高めることができた。脂肪酸エステルをアクリル系共重合体100質量部に対して30質量部配合した被験サンプル(比較例4)では、剥離時に粘着剤残留が発生した。これは、液状可塑剤の含有量が多く、粘着剤層が柔らかくなりすぎたためと推察された。一方で、アクリル系共重合体との相溶性が劣るオレイン酸デシルを選択した被験サンプル(比較例7)は、粘着剤の残留試験において、粘着剤残留が発生し、医療用貼付材として問題があるものであった。 Comparing Examples 1 to 6 and Comparative Examples 1 to 8 in which the supports are the same, the adhesive strength of each test sample to human skin is 10 parts by mass of the fatty acid ester with respect to 100 parts by mass of the acrylic copolymer. In the test sample containing 20 parts by mass or 20 parts (Comparative Examples 2 to 3, Examples 1 to 6, Comparative Examples 5 to 8), the numerical value was higher than that of the test sample not containing the fatty acid ester (Comparative Example 1). Yes, the adhesive strength could be enhanced by blending the fatty acid ester. In the test sample (Comparative Example 4) in which 30 parts by mass of the fatty acid ester was mixed with 100 parts by mass of the acrylic copolymer, adhesive residue was generated at the time of peeling. It was presumed that this was because the content of the liquid plasticizer was high and the adhesive layer became too soft. On the other hand, the test sample (Comparative Example 7) in which decyl oleate, which is inferior in compatibility with the acrylic copolymer, was selected, had adhesive residue in the adhesive residue test, which caused a problem as a medical patch. It was something.
 各被験サンプルの角質剥離面積率は、分子量が350以上550以下の範囲でアクリル系共重合体との相溶性が良好な脂肪酸エステルを配合した被験サンプル(実施例1~6)では、比較例1と比べて角質剥離面積率が40%前後と十分に低くなった。これに対して、分子量が当該範囲から外れている脂肪酸エステルを配合した被験サンプル(比較例2、比較例5、6、8)では、角質剥離面積率が50%以上であり、低減効果が小さいことが確認できた。また、液状可塑剤として分子量が当該範囲から外れているミリスチン酸イソプロピル(分子量:268.0)を15質量部と、分子量が当該範囲内であるオレイン酸オレイル(分子量:531.0)5質量部とを含有しており、液状可塑剤の重量平均分子量が333.8[(268.0×15+531.0×5)/(15+5)]である比較例3の被験サンプルは、分子量が当該範囲から外れている脂肪酸エステルのみを配合した被験サンプルと同様に、角質剥離面積率が50%以上であり、低減効果が小さかった。 The exfoliation area ratio of each test sample was compared with Comparative Example 1 in the test samples (Examples 1 to 6) containing a fatty acid ester having a molecular weight in the range of 350 or more and 550 or less and having good compatibility with the acrylic copolymer. The keratin exfoliation area ratio was about 40%, which was sufficiently low. On the other hand, in the test samples (Comparative Example 2, Comparative Examples 5, 6 and 8) containing fatty acid esters having a molecular weight outside the range, the keratin exfoliation area ratio is 50% or more, and the reduction effect is small. I was able to confirm that. In addition, 15 parts by mass of isopropyl myristate (molecular weight: 268.0) whose molecular weight is out of the range as a liquid plasticizer and 5 parts by mass of oleyl oleate (molecular weight: 531.0) whose molecular weight is within the range. In the test sample of Comparative Example 3 in which the weight average molecular weight of the liquid plastic agent is 333.8 [(268.0 × 15 + 531.0 × 5) / (15 + 5)], the molecular weight is within the range. Similar to the test sample containing only the detached fatty acid ester, the keratin exfoliation area ratio was 50% or more, and the reduction effect was small.
 皮膚反応は、分子量が350以上550以下の範囲内であってアクリル系共重合体との相溶性が良好な脂肪酸エステルを配合した被験サンプル(実施例1~6)は、経時推移でほとんど皮膚状態が低下することなく維持できていることが確認できた。また、試験終了日の剥離24時間後においても、赤みが残った被験者が少ないことが確認できた。一方、支持体のみ異なる被験サンプル(実施例3、7、比較例9)を比較すると、透湿度が500g/m・24h以上であるウレタン不織布を支持体とした実施例7は、透湿度が500g/m・24h以上である織布を支持体とした実施例3と遜色の無い評価結果であったが、透湿度が60g/m・24hであるポリエチレンフィルムを支持体とした比較例9では、角質薄利面積率は低いものの、ヒト皮膚粘着力が大きく低下し、皮膚反応も強いものであった。これらの結果より、透湿度が500g/m・24h以上である織布又は不織布を支持体とし、アクリル系共重合体からなる粘着剤層に対して、アクリル系共重合体との相溶性が良好な分子量350以上550以下の脂肪酸エステルを適切な量配合することにより、高い粘着力を維持しつつ、皮膚の同じ部位に連続貼付又は繰り返し貼付した際にも皮膚刺激が低い粘着剤層を形成できることが明らかである。 As for the skin reaction, the test samples (Examples 1 to 6) containing a fatty acid ester having a molecular weight in the range of 350 or more and 550 or less and having good compatibility with the acrylic copolymer were almost in a skin state over time. It was confirmed that the amount was maintained without decreasing. In addition, it was confirmed that few subjects remained reddish even 24 hours after the peeling on the end date of the test. On the other hand, different test samples (Example 3, 7, Comparative Example 9) only supports a comparison of Example moisture permeability has a urethane nonwoven fabric is 500g / m 2 · 24h or more and the support 7, the moisture permeability Comparative example 500 g / m 2 · but 24h the at is woven more was example 3 and comparable without evaluation result of the support, the moisture permeability was polyethylene film is 60 g / m 2 · 24h and the support In No. 9, although the keratin thin area ratio was low, the human skin adhesive strength was significantly reduced and the skin reaction was also strong. These results, moisture permeability of the woven or nonwoven fabric is 500g / m 2 · 24h or more as a support for the pressure-sensitive adhesive layer including the acrylic copolymer, the compatibility with the acrylic copolymer By blending an appropriate amount of a fatty acid ester having a good molecular weight of 350 or more and 550 or less, a pressure-sensitive adhesive layer with low skin irritation is formed even when continuously or repeatedly applied to the same part of the skin while maintaining high adhesive strength. It is clear that it can be done.

Claims (8)

  1.  支持体と粘着剤層の積層体を備える医療用貼付材であって、
     前記粘着剤層が、(メタ)アクリル酸アルキルエステルを主成分とした共重合体と、室温で液状の前記共重合体と相溶する脂肪酸エステルとを含有する粘着剤組成物からなり、
     前記粘着剤組成物に含有されている前記脂肪酸エステルの重量平均分子量が350以上550以下であり、
     前記粘着剤組成物は、前記共重合体100質量部に対して、前記脂肪酸エステルを5質量部以上25質量部以下含有しており、
     前記支持体の透湿度が500g/m・24h以上である、
     医療用貼付材。
    A medical patch having a laminate of a support and an adhesive layer.
    The pressure-sensitive adhesive layer comprises a pressure-sensitive adhesive composition containing a copolymer containing a (meth) acrylic acid alkyl ester as a main component and a fatty acid ester compatible with the copolymer which is liquid at room temperature.
    The weight average molecular weight of the fatty acid ester contained in the pressure-sensitive adhesive composition is 350 or more and 550 or less.
    The pressure-sensitive adhesive composition contains 5 parts by mass or more and 25 parts by mass or less of the fatty acid ester with respect to 100 parts by mass of the copolymer.
    The moisture permeability of the support is 500g / m 2 · 24h or more,
    Medical patch material.
  2.  前記脂肪酸エステルが、重量平均分子量350以上550以下である単一種の脂肪酸エステルを含有する、請求項1に記載の医療用貼付材。 The medical patch according to claim 1, wherein the fatty acid ester contains a single type of fatty acid ester having a weight average molecular weight of 350 or more and 550 or less.
  3.  前記共重合体が、炭素数が8以上12以下のアルキル基を有するアクリル酸アルキルエステルが65質量%以上90質量%以下と、アクリル酸が2質量%以上15質量%以下と、酢酸ビニルが5質量%以上25質量%以下と、その他のビニル単量体が0質量%以上10質量%以下とが溶液重合法により重合した共重合体を、架橋剤にて架橋させたものである、請求項1又は2記載の医療用貼付材。 In the copolymer, acrylic acid alkyl ester having an alkyl group having 8 or more and 12 carbon atoms is 65% by mass or more and 90% by mass or less, acrylic acid is 2% by mass or more and 15% by mass or less, and vinyl acetate is 5. A claim in which a copolymer obtained by polymerizing a copolymer of 0% by mass or more and 25% by mass or less and 0% by mass or more and 10% by mass or less of other vinyl monomers by a solution polymerization method is crosslinked with a cross-linking agent. The medical patch according to 1 or 2.
  4.  前記脂肪酸エステルが、少なくとも1個のオレイン酸残基を有する、請求項1~3のいずれか一項に記載の医療用貼付材。 The medical patch according to any one of claims 1 to 3, wherein the fatty acid ester has at least one oleic acid residue.
  5.  前記脂肪酸エステル中の脂肪酸残基が、全てオレイン酸残基である、請求項4に記載の医療用貼付材。 The medical patch according to claim 4, wherein all the fatty acid residues in the fatty acid ester are oleic acid residues.
  6.  さらに、前記粘着剤層の前記支持体と接している面とは逆の面にセパレーター層を備える、請求項1~5のいずれか一項に記載の医療用貼付材。 The medical patch according to any one of claims 1 to 5, further comprising a separator layer on a surface of the adhesive layer opposite to the surface in contact with the support.
  7.  皮膚の同じ部位に繰り返し貼付される、請求項1~6のいずれか一項に記載の医療用貼付材。 The medical patch according to any one of claims 1 to 6, which is repeatedly applied to the same part of the skin.
  8.  チューブ固定用である、請求項1~7のいずれか一項に記載の医療用貼付材。 The medical patch according to any one of claims 1 to 7, which is for fixing a tube.
PCT/JP2019/049904 2018-06-29 2019-12-19 Medical patch material WO2020261609A1 (en)

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JP2002065841A (en) * 2000-09-01 2002-03-05 Nitto Denko Corp Skin-stickable adhesive composition, skin-stickable adhesive tape or sheet
JP2005089438A (en) * 2003-09-19 2005-04-07 Kosumedei:Kk Adhesive composition for skin and self-adhesive tape or sheet for skin
WO2007126067A1 (en) * 2006-04-28 2007-11-08 Lion Corporation Nonaqueous pressure-sensitive adhesive composition, patches and process for production of patches
JP2007296120A (en) * 2006-04-28 2007-11-15 Lion Corp Sticking agent
JP2009155306A (en) * 2007-12-28 2009-07-16 Lion Corp Transdermal patch
JP2018023784A (en) * 2016-08-09 2018-02-15 日東電工株式会社 Adhesive skin patch and wound body of adhesive skin patch

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002065841A (en) * 2000-09-01 2002-03-05 Nitto Denko Corp Skin-stickable adhesive composition, skin-stickable adhesive tape or sheet
JP2005089438A (en) * 2003-09-19 2005-04-07 Kosumedei:Kk Adhesive composition for skin and self-adhesive tape or sheet for skin
WO2007126067A1 (en) * 2006-04-28 2007-11-08 Lion Corporation Nonaqueous pressure-sensitive adhesive composition, patches and process for production of patches
JP2007296120A (en) * 2006-04-28 2007-11-15 Lion Corp Sticking agent
JP2009155306A (en) * 2007-12-28 2009-07-16 Lion Corp Transdermal patch
JP2018023784A (en) * 2016-08-09 2018-02-15 日東電工株式会社 Adhesive skin patch and wound body of adhesive skin patch

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