WO2013076875A1 - Adhesive patch - Google Patents

Adhesive patch Download PDF

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Publication number
WO2013076875A1
WO2013076875A1 PCT/JP2011/077239 JP2011077239W WO2013076875A1 WO 2013076875 A1 WO2013076875 A1 WO 2013076875A1 JP 2011077239 W JP2011077239 W JP 2011077239W WO 2013076875 A1 WO2013076875 A1 WO 2013076875A1
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WO
WIPO (PCT)
Prior art keywords
layer
pressure
sensitive adhesive
patch
skin
Prior art date
Application number
PCT/JP2011/077239
Other languages
French (fr)
Japanese (ja)
Inventor
南波真広
原口洋
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 PCT/JP2011/077239 priority Critical patent/WO2013076875A1/en
Priority to PCT/JP2012/077449 priority patent/WO2013077134A1/en
Priority to JP2012554115A priority patent/JP5342702B1/en
Publication of WO2013076875A1 publication Critical patent/WO2013076875A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS 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
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/02—Adhesive plasters or dressings
    • A61F13/0246—Adhesive plasters or dressings characterised by the skin adhering layer
    • A61F13/0256—Adhesive plasters or dressings characterised by the skin adhering layer characterized by the parametric properties of the adhesive
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS 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
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/02—Adhesive plasters or dressings
    • A61F13/0203—Adhesive plasters or dressings having a fluid handling member
    • A61F13/0213—Adhesive plasters or dressings having a fluid handling member the fluid handling member being a layer of hydrocoloid, gel forming material
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS 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
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/02—Adhesive plasters or dressings
    • A61F13/0203—Adhesive plasters or dressings having a fluid handling member
    • A61F13/0226—Adhesive plasters or dressings having a fluid handling member characterised by the support layer
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS 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
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/02—Adhesive plasters or dressings
    • A61F13/0246—Adhesive plasters or dressings characterised by the skin adhering layer
    • A61F13/025—Adhesive plasters or dressings characterised by the skin adhering layer having a special distribution arrangement of the adhesive
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS 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
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/02—Adhesive plasters or dressings
    • A61F13/0246—Adhesive plasters or dressings characterised by the skin adhering layer
    • A61F13/0253—Adhesive plasters or dressings characterised by the skin adhering layer characterized by the adhesive material
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS 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
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/02—Adhesive plasters or dressings
    • A61F13/0259—Adhesive plasters or dressings characterised by the release liner covering the skin adhering layer

Definitions

  • the present invention is applied to the medical field, particularly for the purpose of promoting healing of wounds and minor burns such as cuts, scratches, scratches, scratches, shoe slippage, relief of pain, maintenance of a moist environment, or protection.
  • the present invention relates to a patch suitable for an emergency bandage.
  • hydrocolloid wound dressing developed relatively early has dispersed the hydrophilic colloid in the hydrophobic resin base material, and the colloid absorbs the exudate that emerges from the wound, so that a moderate wet state is achieved. Designed to maintain. For example, what are called hydrocolloid dressings can absorb exudate from the wound.
  • the hydrocolloid dressing material is provided with a hydrocolloid plaster layer having both body fluid absorbency and skin adhesion on one side of a support fabric or support film (Patent Document 1).
  • the plaster layer not only quickly absorbs body fluid that exudes from the applied site due to its liquid absorbency, but also has adhesiveness, and therefore gradually adheres to the skin surface shape of the applied site.
  • a patch hereinafter sometimes referred to as “emergency adhesive bandage” in which a pad composed of the hydrocolloid plaster layer and a backing material is placed in the central region of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet.
  • the problem of the present invention is that the wound part maintains a moist environment, normal skin does not become an excessive moist environment, and when the patch is peeled off, both the wound part and the normal skin part are less painful and normal around the wound.
  • An object of the present invention is to provide a patch material such as an emergency bandage that can prevent the invasion of water into a hydrocolloid part due to the use of water at a daily life level without deforming the skin.
  • the present inventors have determined that the material of the pressure-sensitive adhesive tape comprising the support layer and the pressure-sensitive adhesive layer and the configuration of the pad layer including the hydrocolloid layer are specific. As a result, it was found that the problems could be solved, and the present invention was completed.
  • a pressure-sensitive adhesive tape comprising a support layer (a1) made of a fabric formed from elastic fibers and a gas-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin, and An adhesive patch comprising a pad layer (b) comprising a flexible film layer (b1) adjacent to the air-permeable pressure-sensitive adhesive layer (a2) containing the synthetic resin and a hydrocolloid composition layer (b2).
  • the hydrocolloid composition layer (b2) is i) an elastomer component which is at least one selected from the group consisting of polyisobutylene, polyisoprene, styrene / isoprene / styrene block copolymer, acrylic elastomer, urethane elastomer, and silicone elastomer; ii) The above-mentioned patch containing at least one hygroscopic substance selected from the group consisting of carboxymethylcellulose, dextrin, pectin, gelatin, sodium polyacrylate, and polyvinylpyrrolidone.
  • a pressure-sensitive adhesive tape comprising a support layer (a1) made of a fabric formed from elastic fibers, a breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin, and the synthesis It is a patch comprising a pad layer (b) composed of a flexible film layer (b1) adjacent to a breathable pressure-sensitive adhesive layer (a2) containing a resin and a hydrocolloid composition layer (b2).
  • the wound part maintains a moist environment, the normal skin does not become an excessive moist environment, there is no pain when peeling the adhesive material from the skin, the normal skin around the wound is not deformed, and the daily life level
  • a patch is provided that can prevent water from entering the hydrocolloid part due to the use of water.
  • the patch of the present invention comprises a pressure-sensitive adhesive tape (a) comprising a support layer (a1) comprising a fabric formed from elastic fibers, and a breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin, and A patch comprising a pad layer (b) comprising a flexible film layer (b1) adjacent to an air-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin and a hydrocolloid composition layer (b2). .
  • Support layer (a1) comprising a fabric formed from elastic fibers
  • the adhesive tape (a) is formed from a support layer and an adhesive layer.
  • the support layer forming the adhesive tape (a) is a support layer (a1) made of a fabric formed from elastic fibers.
  • the fabric formed from elastic fibers polyurethane elastic fibers, polyacrylic elastic fibers, polyester elastic fibers, rubber elastic fibers, and other nonwoven fabrics, woven fabrics or knitted fabrics using other elastic fibers can be used.
  • the elastic fiber is preferably a polyurethane elastic fiber.
  • the fabric is preferably a nonwoven fabric.
  • the elastic fiber one having an average fiber diameter of usually 3 to 25 ⁇ m, preferably 4 to 20 ⁇ m, more preferably 5 to 15 ⁇ m can be used. Therefore, the elastic fiber in the support layer (a1) is particularly preferably a polyurethane elastic fiber having an average fiber diameter of 3 to 25 ⁇ m.
  • the fabric formed from elastic fibers has a basis weight of usually 20 to 300 g / m 2 , preferably 25 to 250 g / m 2 , more preferably 30 to 200 g / m 2 , and a thickness of usually 50 to The range is 500 ⁇ m, preferably 80 to 450 ⁇ m, more preferably 120 to 400 ⁇ m.
  • the thickness of the support layer (a1) made of the fabric exceeds 500 ⁇ m, the patch becomes difficult to follow the movement of the skin, and may peel off from the skin in a short period of time or may increase the uncomfortable feeling during application. .
  • the thickness of the support layer (a1) is less than 50 ⁇ m, the strength of the patch is insufficient, and it may be peeled off from the skin in a short period of time.
  • the support layer (a1) as the nonwoven fabric formed from polyurethane elastic fibers that are particularly preferably used, for example, polyurethane elastic fibers are laminated, and the contact points of the elastic fibers are joined by the elastic fibers themselves.
  • Tapirus registered trademark, manufactured by Tapirus Co., Ltd.
  • Espancione registered trademark, manufactured by KB Seiren Co., Ltd.
  • others can be suitably used.
  • nonwoven fabric formed from elastic fibers a melt blow method, a spun bond method, an airlaid method, a needle punch method, or the like, which is a known nonwoven fabric manufacturing method, can be employed. Moreover, a nonwoven fabric is wound as it is or after embossing, and becomes a nonwoven fabric.
  • additives such as UV absorbers, anti-aging agents, fillers, pigments, colorants, flame retardants, antistatic agents, etc. to fabrics such as non-woven fabrics formed from elastic fibers as necessary can do.
  • additives may be added to the raw material of the fiber, or may be added by performing a surface treatment on a cloth such as a non-woven fabric. Unless the moisture permeability is impaired, the additives are used in a usual amount. It is done.
  • a fabric such as a nonwoven fabric formed from elastic fibers may be impregnated with a synthetic resin having affinity and adhesion with the elastic fibers.
  • the synthetic resin can be used by mixing with an appropriate adhesive so that it can be bonded to elastic fibers.
  • urethane resins acrylic resins can be used.
  • resin the adhesiveness with the fibers (filaments) of the nonwoven fabric or the like is good.
  • the adhesive tape (a) is formed from a support layer and an adhesive layer.
  • the pressure-sensitive adhesive layer forming the pressure-sensitive adhesive tape (a) is characterized in that it is a gas-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin.
  • the synthetic resin contained in the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer (a2) is not particularly limited as long as it has low skin irritation, and is acrylic, urethane-based, silicone-based, rubber-based, polyvinyl alcohol-based, polyamide.
  • a pressure-sensitive adhesive containing a base, polyvinyl acetate, or other synthetic resin can be used.
  • acrylic pressure-sensitive adhesives made of acrylic resins; urethane-based pressure-sensitive adhesives such as polyether-based polyurethane and polyester-based polyurethane; silicone-based pressure-sensitive adhesives such as organopolysiloxane and alkylarylpolysiloxane; polyisobutylene, Butyl rubber, styrene / butadiene copolymer (SBR), styrene / isoprene / styrene block copolymer (SIS), styrene / butadiene / styrene block copolymer (SBS), styrene / ethylene / butylene / styrene block copolymer (SBS) SEBS), rubber adhesives such as styrene / ethylene / propylene / styrene block copolymer (SEPS) and hydrogenated products of SBR are preferably
  • the acrylic resin contained in the acrylic pressure-sensitive adhesive is a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 15, preferably 1 to 12, and more preferably 1 to 10 carbon atoms.
  • (meth) acrylic acid alkyl esters include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isoamyl acrylate, 2-ethylhexyl acrylate, and n-acrylate.
  • -Acrylic acid alkyl esters such as octyl, isooctyl acrylate, isononyl acrylate, decyl acrylate, dodecyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, methacryl Alkyl methacrylates such as isoamyl acid, 2-ethylhexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, isononyl methacrylate, decyl methacrylate, dodecyl methacrylate; And the like.
  • acrylic acid alkyl esters include acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid and other carboxyl group-containing monomers; 2-hydroxyethyl acrylate, acrylic acid Hydroxyl-containing monomers such as 2-hydroxypropyl; (meth) acrylic acid alkoxypolyalkylene such as methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, ethoxydiethylene glycol acrylate Glycol ester; amino group-containing monomer such as N, N-dimethylaminomethyl acrylate, N, N-dimethylaminoethyl methacrylate, Nt-butylaminoethyl acrylate Amide group-containing monomers such as acrylamide and methacrylamide; Glycidyl group-containing
  • the (meth) acrylic acid alkyl ester is usually used in a proportion of 50% by mass or more, preferably 60% by mass or more, more preferably 70 to 97% by mass, and further preferably 75 to 95% by mass.
  • the other monomer copolymerizable with the (meth) acrylic acid alkyl ester is usually 50% by mass or less, preferably 40% by mass or less, more preferably 30 to 3% by mass, and still more preferably 25 to 5% by mass. Used.
  • the production method of the acrylic resin is not particularly limited, and can be produced by a generally employed solution polymerization method, suspension polymerization method or emulsion polymerization method.
  • These pressure-sensitive adhesives can be mixed with a tackifier as desired in order to adjust the pressure-sensitive adhesive properties.
  • the tackifier include tackifier resins such as terpene, terpene phenol, coumarone indene, styrene, rosin, xylene, phenol, and petroleum.
  • cross-linking agents such as polyisocyanates, melamine resins, epoxy resins, peroxides, metal chelate compounds; softeners, fillers, antioxidants, etc. may be added to the acrylic resin as necessary. Can do.
  • these tackifiers can be used in an amount of 20 parts by mass or less, preferably 15 parts by mass or less based on 100 parts by mass of the acrylic resin.
  • the additive can be used in a proportion of 10 parts by mass or less, more preferably 0.01 to 5 parts by mass, and even more preferably 0.02 to 2 parts by mass depending on the type of additive.
  • the pressure-sensitive adhesive layer in the patch of the present invention is a gas-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin.
  • the air-permeable pressure-sensitive adhesive layer (a2) containing the synthetic resin is known per se and measured using a Gurley type densometer (Tester Sangyo Co., Ltd.) in accordance with JIS P8117.
  • the pressure-sensitive adhesive has an air permeability of 60 seconds / 300 cm 3 or less.
  • the air permeability of the pressure-sensitive adhesive layer is more preferably 0.05 to 50 seconds / 300 cm 3 , still more preferably 0.1 to 40 seconds / 300 cm 3 , and particularly preferably 0.2 to 35 seconds / 300 cm 3 . Since the air permeability of the pressure-sensitive adhesive layer (a2) itself cannot be measured, the value measured in the state of being laminated with a material having air permeability higher than that of the pressure-sensitive adhesive layer (a2), such as a nonwoven fabric or a woven fabric, The air permeability of the agent layer (a2) is set. The measurement of the air permeability of the pressure-sensitive adhesive layer (a2) is specifically as follows.
  • an adhesive tape (a) [support layer (a1) and adhesive layer (a2) cut to a size of 5 cm ⁇ 5 cm. ] Is affixed to the fastening plate (base).
  • the area that penetrates the clamping plate is 645.16 mm 2 .
  • the air permeability of the pressure-sensitive adhesive tape (a) obtained by gently lowering the inner cylinder and measuring the number of seconds through which the amount of air of 300 cm 3 passes is the air permeability (seconds / 300 cm 3 ) of the pressure-sensitive adhesive layer (a2).
  • the air permeability of the particularly preferred adhesive tape (a) is 0.2 to 35 seconds / 300 cm 3 .
  • the pressure-sensitive adhesive layer (a2) formed of a gas-permeable pressure-sensitive adhesive containing a synthetic resin As the pressure-sensitive adhesive layer, the air-permeability and cushioning properties of the pressure-sensitive adhesive layer and the patch are improved, and the skin The followability to the skin is improved, and the adhesion to the skin is improved.
  • the air-permeable pressure-sensitive adhesive layer (a2) containing the synthetic resin in the present invention can be obtained by a usual method. Specifically, the adhesive is mixed with a physical foaming agent such as air, nitrogen gas or carbon dioxide, a decomposable chemical foaming agent, an aqueous solution or an organic solvent, and then applied to the release paper or adhered.
  • a foaming method that uses foaming or vaporization. Examples include a method of forming fine holes by applying mist-like moisture, a method of discharging an adhesive on a release paper in the form of threads and fibers, and these methods allow a number of fine holes to be formed in a synthetic resin.
  • a pressure-sensitive adhesive layer is formed. From the viewpoint of forming fine and uniform pores, the foaming method is more preferable.
  • the air-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin has an expansion ratio of usually 1.1 to 10 times, preferably 1.2 to 8 times, more preferably 1.5 to 6 times, and still more preferably. Is in the range of 2 to 5 times, and the density is usually 0.1 to 0.9 g / cm 3 , preferably 0.12 to 0.8 g / cm 3 , more preferably 0.15 to 0.6 g / cm 3 . 3 and more preferably in the range of 0.2 to 0.5 g / cm 3 .
  • the air-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin is usually provided on the entire surface of one side of the support layer (a1), but if desired, not provided on the entire surface of the support layer (a1), It can also be provided in a part.
  • the thickness of the air-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin is not particularly limited, but is usually in the range of 10 to 200 ⁇ m, preferably 15 to 150 ⁇ m, more preferably 20 to 100 ⁇ m.
  • Adhesive tape (a)
  • the patch of the present invention comprises a pressure-sensitive adhesive tape (a) comprising a support layer (a1) made of a fabric formed from elastic fibers and a gas-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin. is there.
  • the adhesive material of the present invention has a moisture permeability of an adhesive tape (a) comprising a support layer (a1) made of a fabric formed from elastic fibers and a breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin. It is preferably 2000 g / m 2 ⁇ 24 hr or more, and when the patch is applied to the skin surface, peeling due to perspiration or rash is effectively suppressed.
  • Moisture permeability of the adhesive tape (a) is more preferably 2500g / m 2 ⁇ 24hr or more, more preferably 3000g / m 2 ⁇ 24hr or more, and particularly preferably 3500g / m 2 ⁇ 24hr or more.
  • the upper limit of the water vapor transmission rate of the pressure-sensitive adhesive tape (a) is usually about 50000 g / m 2 ⁇ 24 hr.
  • the moisture permeability of the pressure-sensitive adhesive tape (a) is the pressure-sensitive adhesive tape (a) composed of a support layer (a1) made of a fabric formed from elastic fibers and a gas-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin.
  • the measurement was performed under the measurement conditions of a temperature of 40 ° C. and a relative humidity of 90%. Specifically, the atmosphere on the adhesive layer side of the adhesive tape (a) is adjusted to a temperature of 40 ° C. and a relative humidity of 90%, and about 15 g of a hygroscopic agent (calcium chloride) is placed on the other side, Moisture that has passed is absorbed, and the mass change amount of the hygroscopic agent is converted to moisture permeability by converting it to 1 m 2 per 24 hours.
  • a hygroscopic agent calcium chloride
  • the adhesive strength of the pressure-sensitive adhesive tape (a) in the patch of the present invention specifically, the adhesive strength of the pressure-sensitive adhesive layer (a2) containing a synthetic resin, ) Is preferably in the range of 0.5 to 4.2 N / 15 mm, more preferably 0.7 to 3.5 N / 15 mm, and still more preferably 0.8 to 3.1 N / 15 mm.
  • the adhesive strength of the adhesive tape (a) is within this range, when the adhesive material of the present invention is applied to the skin surface, the adhesive tape has sufficient adhesive performance and does not cause misalignment during application, When the patch is peeled off, there is no risk of peeling the normal skin surface around the wound or causing rash as well as the wound site on the skin.
  • the adhesive strength with the polyurethane film forming the pad layer (b) is improved and the anchoring property is sufficiently ensured by using the above adhesive strength. There is no inconvenience such as slippage.
  • the measuring method of the adhesive strength of the adhesive tape (a) is as follows. That is, the pressure-sensitive adhesive tape (a) is cut into a predetermined length of 15 mm width ⁇ 15 mm length, preferably 100 mm, to obtain a test piece.
  • a YUPO (registered trademark) FPG-130 synthetic paper manufactured by YUPO Corporation
  • the test piece is pressed against the test panel and adhered. After 20 minutes have passed since sticking, the adhesive strength is measured under the conditions of a peeling angle of 180 ° and a peeling speed of 300 mm / min according to JIS Z0237.
  • the pressure-sensitive adhesive tape (a) in the patch of the present invention has a support layer (a1) made of a fabric formed from elastic fibers and a breathability containing a synthetic resin, preferably foamed.
  • the pressure-sensitive adhesive layer (a2) The production method of the pressure-sensitive adhesive tape (a) is not particularly limited, but a solution or emulsion of a synthetic resin to be a pressure-sensitive adhesive is directly applied on the support layer (a1) made of a fabric such as a nonwoven fabric formed from elastic fibers. Then, the pressure-sensitive adhesive layer (a2) containing the foamed synthetic resin may be formed by foaming the pressure-sensitive adhesive.
  • a pressure-sensitive adhesive layer (a2) containing a foamed synthetic resin is applied by applying a synthetic resin solution or emulsion to be a pressure-sensitive adhesive on a process paper coated with a silicone release agent, and foaming the pressure-sensitive adhesive.
  • a method of laminating with a support layer (a1) made of a fabric such as a nonwoven fabric formed from elastic fibers may be employed.
  • the application of the synthetic resin solution or emulsion to be the pressure-sensitive adhesive may be performed according to other patterns such as dots, stripes, etc. Just do it.
  • Pad layer (b) The patch of the present invention comprises a pad layer (b) composed of a flexible film layer (b1) and a hydrocolloid composition layer (b2).
  • the pad layer (b) may be formed by integrating the flexible film layer (b1) and the hydrocolloid composition layer (b2) formed in advance by bonding or other methods.
  • a pad layer (b) may be obtained by forming the hydrocolloid composition layer (b2) integrated with the flexible film layer (b1) by extruding the hydrocolloid composition onto a film having .
  • Flexible film layer (b1) The flexible film layer (b1) forming the pad layer (b) in the patch of the present invention is a flexible film adjacent to the air-permeable pressure-sensitive adhesive layer (a2) containing the synthetic resin. Layer (b1). That is, a flexible film layer (b1) is provided on the surface opposite to the support layer (a1) made of a cloth such as a nonwoven fabric formed from elastic fibers. The flexible film layer (b1) is located between the air-permeable pressure-sensitive adhesive layer (a2) containing the synthetic resin and the hydrocolloid composition layer (b2) described later, and the hydrocolloid composition layer (b2).
  • the flexible film layer (b1) preferably has a moisture permeability of 1000 g / m 2 ⁇ 24 hr or more measured by the same method as the moisture permeability measurement method of the adhesive tape (a) described above. more preferably 2000g / m 2 ⁇ 24hr or more, more preferably 3000g / m 2 ⁇ 24hr or more, and particularly preferably 3500g / m 2 ⁇ 24hr or more.
  • the upper limit of the moisture permeability of the adhesive layer is usually 10000g / m 2 ⁇ 24hr or so, often 8000g / m 2 ⁇ 24hr approximately.
  • the thickness of the flexible film layer (b1) is usually 5 to 45 ⁇ m, preferably 6 to 40 ⁇ m, more preferably 7 to 35 ⁇ m. If the thickness is too small, strength and moisture intrusion prevention functions are insufficient, and the handleability during production may be deteriorated. If the thickness is too large, high moisture permeability as the whole patch is not exhibited, and the stretchability may be insufficient.
  • the flexible film layer (b1) is a film layer formed from a flexible film that is capable of following the skin and that allows the adhesive material to adhere to the skin.
  • a material for forming the flexible film layer (b1) a conventionally known material can be used, but it is a thermoplastic resin, and safety for human skin has been confirmed.
  • a film made of polyethylene such as LLDPE, LDPE, etc. provided with fine pores of about 0.01 to 10 ⁇ m, or containing calcium carbonate and stretched as desired, and polyurethane as a material.
  • a polyurethane film is preferred.
  • the flexible film layer (b1) is a polyurethane film layer
  • the tensile stress is superior to that of other materials.
  • the polyurethane for forming the polyurethane film layer either polyether-based polyurethane or polyester-based polyurethane can be used.
  • the polyurethane film can be obtained by an ordinary method for producing a polyurethane film.
  • Silklon (registered trademark) NES85 manufactured by Okura Kogyo Co., Ltd.
  • DINTEX registered trademark
  • DINTEXFT1881-PE Nehon Unipolymer Co., Ltd.
  • Samprene (registered trademark) HMP-17A manufactured by Sanyo Kasei Kogyo Co., Ltd.
  • Corona treatment or undercoating may be performed on one or both surfaces of the polyurethane film.
  • Hydrocolloid composition layer (b2) The hydrocolloid composition layer (b2) forming the pad layer (b) in the patch of the present invention is a breathable pressure-sensitive adhesive layer (a2) containing the synthetic resin of the flexible film layer (b1). It is provided on the opposite surface.
  • hydrocolloid composition examples of the hydrocolloid composition contained in the hydrocolloid composition layer (b2) in the patch of the present invention include, for example, acrylic, silicone, urethane, polyvinyl acetate, natural rubber, and synthetic rubber adhesives.
  • acrylic, silicone, urethane, polyvinyl acetate, natural rubber, and synthetic rubber adhesives for example, carboxymethyl cellulose, karaya gum, dextrin, pectin, gelatin, polyvinyl alcohol, a hydrophilic polymer compound having water absorption, such as sodium polyacrylate, is used as a hygroscopic substance (hereinafter, referred to as a hygroscopic substance). It is sometimes called "absorbent").
  • the adhesive polymer materials include polyisobutylene, polyisoprene, polybutadiene, styrene / butadiene / styrene block copolymer, styrene / isoprene / styrene block copolymer (SIS). ) And the like, and those mainly composed of elastomers such as acrylic elastomers, urethane elastomers, and silicone elastomers are preferred, and SIS is particularly preferably used. Quintac 3421 (registered trademark, Japan) is commercially available. Zeon Corporation). These materials can be used alone or in combination of two or more.
  • a tackifier resin can be added to the polymer material having tackiness in order to impart appropriate tackiness to the hydrocolloid composition layer (b2).
  • Preferable tackifying resins include rosin ester resins, terpene resins, alicyclic resins, and hydrogenated products thereof.
  • Alcon P125 registered trademark, manufactured by Arakawa Chemical Industries, Ltd.
  • Petrochemical resin is a commercially available product.
  • the tackifying resin is added in an amount of usually 200 parts by mass or less, preferably 190 parts by mass or less, and more preferably 180 parts by mass or less with respect to 100 parts by mass of the adhesive polymer material.
  • a softener plasticizer
  • Preferred softeners include petroleum-based softeners such as liquid paraffin; liquid polyisoprene, polybutene, polyisobutylene and the like. Liquid rubber softeners; dibasic acid ester plasticizers such as phthalate esters and adipates; and other plasticizers such as polyethylene glycol and citrate esters.
  • the addition amount of the softening agent is usually 100 parts by mass or less, preferably 90 parts by mass or less, more preferably 80 parts by mass or less with respect to 100 parts by mass of the polymer material having adhesiveness.
  • CMC carboxymethylcellulose
  • dextrin As the hygroscopic substance, carboxymethylcellulose (hereinafter sometimes referred to as “CMC”), dextrin, pectin, gelatin, sodium polyacrylate, polyvinylpyrrolidone, carboxymethylcellulose calcium, hydroxypropylcellulose, guar gum, locust bean gum, xanthan gum Sodium alginate, calcium alginate, carrageenan, collagen and the like are preferably used.
  • Serogen F-3H registered trademark, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • a particularly preferable combination of the adhesive polymer material and the hygroscopic substance is: i) an elastomer component which is at least one selected from the group consisting of polyisobutylene, polyisoprene, styrene / isoprene / styrene block copolymer, acrylic elastomer, urethane elastomer, and silicone elastomer; ii) a hydrocolloid composition layer (b2) containing at least one hygroscopic substance selected from the group consisting of carboxymethylcellulose, dextrin, pectin, gelatin, sodium polyacrylate, and polyvinylpyrrolidone.
  • the hygroscopic substance can be contained in the hydrocolloid composition so as to be 75 to 10% by mass with respect to 25 to 90% by mass of the adhesive polymer material.
  • the hygroscopic substance is 70 to 15% by mass with respect to 30 to 85% by mass of the polymer material, and more preferably 65 to 20% by mass with respect to the polymer material of 35 to 80% by mass.
  • the hygroscopic substance be contained so that the hygroscopic substance is 60 to 25% by mass with respect to 40 to 75% by mass of the polymer material. From the viewpoint of adhesion to the wound site and moderate shape retention (prevention of the plaster from the side).
  • the hygroscopic substance is added to the total amount of the polymer material and the tackifying resin and / or softening agent.
  • the content ratio may be the same as the content ratio between the polymer material and the hygroscopic substance.
  • the hydrocolloid composition can usually contain other optional components of 5% by mass or less.
  • an antioxidant, a deodorant, and a fragrance can be contained.
  • a crosslinking agent may be appropriately contained.
  • the hydrocolloid composition layer (b2) since the hydrocolloid composition layer (b2) is in contact with the wound site, it may contain a required amount of a pharmacologically effective drug.
  • pharmacologically effective drugs to be included in the hydrocolloid composition include antibiotics, bactericides and antibacterial agents (acrinol, benzalkonium chloride, silver compounds, etc.), disinfectants, anti-inflammatory agents and skin protective agents. These may have a content of usually 3% by mass or less, preferably 2% by mass or less.
  • the hydrocolloid composition may contain 1% by mass or less of a physical reinforcing agent (forms a Van der Waals bond with an adhesive polymer material or the like), for example, carbon. Examples thereof include black, polyaramids, hydrated silicas and the like.
  • the thickness of the hydrocolloid composition layer (b2) is usually in the range of 100 ⁇ m to 2 mm, preferably 150 ⁇ m to 1.5 mm, more preferably 200 ⁇ m to 1 mm. If the thickness is too small, absorption of the exudate from the wound site may be insufficient. If the thickness is too large, the stretchability will be poor, and there will be problems such as applying stress to the wound site during application.
  • the hydrocolloid composition layer (b2) is prepared by mixing the hydrocolloid composition with heating, extruding the obtained mixture, and rolling or press-molding it into a molded product having a desired thickness. It can be manufactured by cutting into a shape. Also, the hydrocolloid composition layer (b2) integrated with the flexible film layer (b1) by extruding the hydrocolloid composition onto a polyurethane film forming the flexible film layer (b1). Can also be formed.
  • a layer having a water absorption rate (liquid absorption rate) of 50 to 400% by mass of its own weight is preferably employed.
  • the water absorption is more preferably 100 to 250% by mass.
  • the water absorption is calculated from the mass before and after immersing the hydrocolloid composition layer (b2) forming the pad layer (b) in physiological saline at a temperature of 37 ° C. for 24 hours.
  • the body fluid that exudes from the wound site cannot be sufficiently absorbed, the body fluid leaks to the surroundings, and the clothes may be stained, or a large amount of moisture on the healthy skin may be adversely affected. If the water absorption rate is too large, many hydrocolloid composition layers (b2) may absorb body fluid and soften, and may remain on the skin surface including the wound site.
  • the hydrocolloid composition layer (b2) forming the pad layer (b) is to be applied to the skin surface including the wound site and must be able to be peeled without damaging the wound site and healthy skin.
  • the adhesive strength of the hydrocolloid composition layer (b2) is evaluated by measuring the adhesive strength against the skin surface and the adhesive strength against YUPO.
  • the adhesive strength of the hydrocolloid composition layer (b2) to the skin surface is preferably in the range of 0.3 to 2 N / 15 mm, more preferably 0.4 to 1.5 N / 15 mm, still more preferably 0.5 to 1 N / 15 mm. It is.
  • the adhesive material of the hydrocolloid composition layer (b2) on the skin surface is made smaller than the adhesive force of the adhesive tape (a) on the skin surface, so that the wound site and healthy skin are not damaged. Can be peeled off.
  • the method for measuring the adhesion of the hydrocolloid composition layer (b2) to the skin surface is as follows.
  • the hydrocolloid composition layer (b2) cut to a predetermined length of 15 mm in width ⁇ 15 mm in length, preferably 70 mm may be a preliminarily formed hydrocolloid composition layer (b2) or a flexible film layer ( It may be a hydrocolloid composition layer (b2) integrated with b1).
  • the hydrocolloid composition layer (b2) on the opposite surface of the support tape is set to a range of 30 to 65% of the forearm inner region heel (from the elbow toward the wrist) of a predetermined number of subjects. Affix to the heel and press the palm for 10 seconds to crimp. After 20 minutes have elapsed since the application, the adhesive strength is measured in accordance with JIS Z0237 under conditions of a peeling angle of 90 ° and a peeling speed of 100 mm / min.
  • the hydrocolloid composition layer (b2) has an adhesive strength to YUPO of preferably 0.3 to 4 N / 15 mm, more preferably 0.4 to The range is 3.5 N / 15 mm, more preferably 0.5 to 3 N / 15 mm.
  • the adhesive tape (a ) From the pad layer (b) can be prevented.
  • the method for measuring the YUPO adhesive strength of the hydrocolloid composition layer (b2) is as follows.
  • the hydrocolloid composition layer (b2) [the previously formed hydrocolloid composition layer (b2) may be used, or the hydrocolloid composition layer (b2) integrated with the flexible film layer (b1) may be used.
  • a YUPO (registered trademark) FPG-130 synthetic paper manufactured by YUPO Corporation
  • the test piece is pressed against the test panel and adhered. After 20 minutes have passed since sticking, the adhesive strength is measured under the conditions of a peeling angle of 90 ° and a peeling speed of 100 mm / min according to JIS Z0237.
  • the adhesive material of the present invention comprises an adhesive tape (a) comprising a support layer (a1) made of a fabric formed from elastic fibers, and an air-permeable adhesive layer (a2) containing a synthetic resin, and A patch comprising a pad layer (b) comprising a flexible film layer (b1) adjacent to the air-permeable pressure-sensitive adhesive layer (a2) containing the synthetic resin and a hydrocolloid composition layer (b2) It is.
  • the patch of the present invention is a patch formed by sequentially laminating the layers (a1) to (b2) above, and in particular, (1) By providing the support layer (a1) made of a fabric formed from elastic fibers, it is possible to provide a patch material excellent in stretchability, moisture permeability, followability to skin, and tensile strength, (2) By providing the air-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin, an adhesive material that is excellent in moisture permeability, air permeability, cushioning and followability to the skin and has little skin irritation is provided.
  • the flexible film layer (b1) is adjacent to the air-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin, and the hydrocolloid composition layer (b2) is laminated to form the pad layer (b).
  • the hydrocolloid composition layer (b2) does not collapse due to exudate from the wound site or moisture from the external environment of the patch.
  • the pressure-sensitive adhesive tape (a) is usually composed of a support layer (a1) made of a fabric formed from elastic fibers and a gas-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin.
  • the pad layer (b) is more extensible than the pad layer, and as a result, the application to the skin surface and the peeling operation from the skin surface are facilitated, and it is easy to follow the bending of the skin during application. It is possible to provide a patch that is excellent in moisture permeability, daily waterproofing, followability to skin and tensile strength, prevents whitening of healthy skin, and has little skin irritation.
  • excess leachate from the wound site absorbed by the hydrocolloid composition layer (b2) is diffused laterally by the flexible film layer (b1) disposed on the upper surface of the pad layer,
  • the breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin, and the support layer (a1) made of a fabric formed from elastic fibers can be quickly used. Volatilized to the outside world. Therefore, normal skin hardly retains the above-mentioned excessive exudate, and can prevent whitening of healthy skin when the patch is peeled off.
  • the hydrocolloid composition layer (b2) when applying to a skin surface having a wound with relatively little exudate, such as a scratch, a scratch, a shoe slip, etc., the hydrocolloid composition layer (b2) has appropriate adhesiveness. Glue to cover the surrounding skin. As a result, since the hydrocolloid composition layer (b2) absorbs the leachate, the adhesive strength is appropriately reduced, so that the wet environment of the wound site is adjusted.
  • the healthy skin located outside the pad layer (b) has a pressure-sensitive adhesive layer composed of a support layer (a1) made of a fabric formed of elastic fibers and a breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin. Since the tape (a) is highly moisture permeable, it can prevent whitening of the skin caused by preventing moisture from evaporating even when it is applied to the skin for about 24 hours.
  • the flexible film layer (b1) is laminated on the back surface of the hydrocolloid composition layer (b2), even in a scene where water is used in daily life activities such as hand washing, dishwashing, bathing, etc. Since the water invasion to the pad layer (b) can be prevented, the hydrocolloid composition layer (b2) does not absorb water more than necessary and expands.
  • the area of the pad layer (b) is preferably 5 to 50% of the area of the adhesive tape (a), more The area ratio is preferably 8 to 47%, particularly preferably 10 to 45%.
  • the area of the support layer (a1) made of a fabric formed from elastic fibers and the breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin, and the flexible film layer (b1) and hydrocolloid composition is usually the same.
  • the hydrocolloid composition layer (b2) can keep the wound site of the skin in a moist environment, and the Since the hydrocolloid composition layer (b2) itself does not need to adhere strongly to the skin, it is possible to suppress pain and skin damage when the patch is peeled off.
  • an optimum patch can be selected according to the size of the wound. Basically, it is only necessary to select a patch having a pad layer that is slightly larger than the target wound and has a size that does not cover normal skin as much as possible.
  • the patch of the present invention can be preferably applied to skin having a wound such as a cut, scratch, stab, scratch, and shoe slip.
  • a support layer (a1) made of a fabric formed from elastic fibers, a breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin, a flexible film layer (b1), and a hydrocolloid composition layer (b2)
  • the thickness of each layer is as described above, but the edge of the hydrocolloid composition layer (b2) is prevented from being turned over when the patch is applied to the skin surface, and the application is continued or continued. It is preferable to incline the thickness of the hydrocolloid composition layer (b2) so as to gradually become thinner toward the edge in order to sufficiently adhere and fix the skin surface without wrinkles or the like.
  • the following methods can be used to evaluate skin stuffiness, adhesion strength to the skin during peeling, and comprehensive evaluation.
  • the adhesive was applied to multiple adults in their 20s to 50s as subjects, and the pad layer (b) was applied to the first joint of the finger on the back side of the hand. Etc.) or obligate bathing, and observe and evaluate the condition 24 hours after application.
  • the patch of the present invention can further include release paper (c).
  • the release paper (c) is usually a surface opposite to the flexible film layer (b1) of the hydrocolloid composition layer (b2), and thus has a breathable pressure-sensitive adhesive layer containing the synthetic resin ( It is laminated on the surface opposite to the support layer (a1) made of a fabric formed from the elastic fiber of a2).
  • the patch of the present invention has a release paper (c) disposed opposite to the air-permeable pressure-sensitive adhesive layer (a2) and hydrocolloid composition layer (b2) containing a synthetic resin. It is preferable that c) is supplied in a state of covering the surface of the pressure-sensitive adhesive.
  • the release paper (c) those commonly used in the field of patch materials can be used.
  • a high-quality paper a paper substrate such as glassine paper, a polyester film, or the like that has been subjected to a release treatment by applying a release agent is used.
  • the release paper (c) may be of a size and shape that covers the entire patch with a single sheet, or may be larger than the area of the patch. Further, the release paper (c) may be divided into two or more sheets, and at least one of the two or more divided release papers (c) may be provided with a folded portion.
  • two or more release papers (c) may be arranged on the air-permeable pressure-sensitive adhesive layer (a2) containing the synthetic resin, so that a release paper (c) divided into a total of 3 or more can be obtained.
  • the adhesive tape (a) can be selected by selecting the release agent to be applied to the release paper (c) and selecting the air-permeable adhesive layer (a2) and hydrocolloid composition layer (b2) containing a synthetic resin.
  • the release force between the adhesive layer and the release paper By making the release force between the adhesive layer and the release paper larger than the release force between the pad layer (b) and the release paper, it is easy to release the release paper from the adhesive material, and the handling property is improved. Prevents the pad layer from falling off It is preferable.
  • the method for manufacturing the patch material of the present invention is not particularly limited, and can be produced by a conventional method for manufacturing a patch material.
  • a synthetic resin solution or emulsion to be a pressure-sensitive adhesive on a process paper coated with a silicone release agent, and foaming the pressure-sensitive adhesive, it has a breathability containing a synthetic resin, preferably After forming the foamed pressure-sensitive adhesive layer (a2), the pressure-sensitive adhesive tape (a) can be prepared by a method of laminating the support layer (a1) made of a fabric formed from elastic fibers.
  • the flexible film layer (b1) and the hydrocolloid composition layer (b2) formed thereon are cut into an appropriate size, and are arranged at the approximate center on the adhesive tape (a).
  • a release paper (c) is further arranged and cut into a bandage shape (usually an oval shape) or the like to obtain a patch.
  • a patch is enclosed in a wrapping paper formed of paper, a plastic film, or a composite material thereof at room temperature in a later step to obtain a product.
  • the measuring method of the physical property or characteristic in an Example and a comparative example is as follows.
  • Air permeability of adhesive tape (a) The air permeability of the adhesive tape (a) was measured using a Gurley type densometer (Tester Sangyo Co., Ltd.) in accordance with JIS P8117. Specifically, the adhesive tape (a) cut to a size of 5 cm ⁇ 5 cm was peeled off when there was release paper, and was stuck on a clamping plate (base). The area permeating through the clamping plate was 645.16 mm 2 . Pull the inner cylinder Gurley Densometer, after setting the stopper, tighten the specimen plates tightening, gently lower the inner cylinder, by measuring the number of seconds to pass the air quantity of 300 cm 3, air permeability (Second / 300 cm 3 ).
  • the measurement was performed until 600 seconds had elapsed, and when an air amount of 300 cm 3 did not pass after the elapse of 600 seconds, the air permeability (seconds / 300 cm 3 ) was set to “> 600 (seconds / 300 cm 3 )”.
  • the pressure-sensitive adhesive force of the pressure-sensitive adhesive tape (a) was a pressure-sensitive adhesive tape (a) cut into a width of 15 mm and a length of 100 mm.
  • YUPO registered trademark
  • FPG-130 synthetic paper made by YUPO Corporation
  • the test piece was pressed against the test panel and adhered. After 20 minutes had elapsed from the sticking, the adhesive strength against YUPO was measured under the conditions of a peeling angle of 180 ° and a peeling speed of 300 mm / min in accordance with JIS Z0237.
  • the adhesive strength of the hydrocolloid composition layer (b2) was evaluated by measuring 1) adhesive strength to the skin surface and 2) YUPO adhesive strength by the following method. 1) The adhesive strength of the hydrocolloid composition layer (b2) to the skin surface was measured by the following method, that is, the preformed hydrocolloid composition layer (b2) was cut into a width of 15 mm and a length of 70 mm, and the support tape The hydrocolloid composition layer (b2) was affixed to the inner part of the forearm of 3 adult male subjects (within the range of 30 to 65% from the elbow toward the wrist), and the palm was applied for 10 seconds. Pressed and crimped.
  • the adhesive strength was measured under the conditions of a peeling angle of 90 ° and a peeling speed of 100 mm / min according to JIS Z0237.
  • the YUPO adhesive strength of the hydrocolloid composition layer (b2) was measured by the following method, that is, the hydrocolloid composition layer (b2) [the hydrocolloid composition integrated with the flexible film layer (b1). Layer (b2) was used. ] was fixed to a support tape, and cut into a width of 15 mm and a length of 70 mm to obtain a test piece.
  • YUPO registered trademark
  • FPG-130 synthetic paper made by YUPO Corporation
  • the test piece was stuck to the test panel. After 20 minutes had passed from the sticking, the adhesive strength was measured under the conditions of a peeling angle of 90 ° and a peeling speed of 100 mm / min according to JIS Z0237.
  • SIS As hydrocolloid compositions, SIS [Quintac 3421 (registered trademark, manufactured by Nippon Zeon Co., Ltd.)], CMC [Serogen F-3H (registered trademark, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)], tackifying resin [Arcon P125 (registered) Trademark, hydrogenated petroleum resin manufactured by Arakawa Chemical Co., Ltd.)) and liquid paraffin (manufactured by Wako Pure Chemical Industries, Ltd.) are blended as shown in Table 1, mixed uniformly with a kneader, and then extruded from an extruder.
  • a hydrocolloid composition layer (b2) Extruded onto the treated process paper to form a hydrocolloid composition layer (b2) having a thickness of 0.33 mm.
  • a polyether-based polyurethane elastomer solution (Lackskin (registered trademark) US2268, manufactured by Seiko Kasei Co., Ltd.) is subjected to silicone treatment on a 75 ⁇ m-thick polyester film subjected to silicone treatment on one side.
  • the polyurethane urethane film (b1) is formed as a flexible film layer by laminating a polyether urethane film obtained by applying and drying to a thickness of 10 ⁇ m. Except for the pad layer (b).
  • Example 1 Polyhexamethylene diol having a number average molecular weight of 2,000, 4,4-diphenylmethane diisocyanate and 1,4-butanediol were melt polymerized by a biaxial polymerization machine to obtain a polyether polyurethane elastic body having a Shore A hardness of 90. This polyurethane was melt blown and the resulting molten fiber group was dropped onto a net conveyor to obtain a melt blown nonwoven fabric (thickness 240 ⁇ m) having a basis weight of 65 g / m 2 . The average fiber diameter of the polyurethane elastic fiber forming the nonwoven fabric was 10.6 ⁇ m.
  • the obtained polyurethane elastic fiber nonwoven fabric was subjected to hot embossing by a point hot pressing method to obtain a support layer (a1) of a patch.
  • the thermocompression bonding spots were set to 1.4 mm pitch in both MD (machine direction) and CD (width direction).
  • acrylic pressure-sensitive adhesive [2-ethylhexyl acrylate / vinyl acetate / acrylic acid (87/10/3) 100 parts by mass and epoxy crosslinking agent (Tetrad X, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 0.03 parts by mass was applied to the process paper treated with silicone so that the thickness after drying was 40 ⁇ m, and as a breathable treatment, distilled water was sprayed onto the undried coated surface, and then 130 ° C. After heating to form fine pores and forming a pressure-sensitive adhesive layer (a2) made of a breathable acrylic resin, it was bonded to the polyurethane elastic fiber nonwoven fabric to produce a pressure-sensitive adhesive tape (a).
  • the pad layer (b) having the hydrocolloid composition layer (b2) of Formulation 1 is cut in advance to a width of 13 mm and a length of 22 mm, and the polyurethane film layer (b1) peels the process paper from the adhesive tape (a). It was placed on the pressure-sensitive adhesive layer (a2) with an interval of 12 mm in length and 50 mm in width so as to face the pressure-sensitive adhesive layer (a2) made of acrylic resin having air permeability. Subsequently, a release paper (c) made of glassine paper peel-treated with a silicone resin covers the adhesive tape (a) and the pad layer (b), and is an approximately rectangular shape with R taken at the corner of 25 mm width and 72 mm length. Then, it was punched out so that the pad layer (b) was positioned substantially at the center to obtain a patch. The ratio of the area of the pad layer (b) to the area of the adhesive tape (a) was about 16%.
  • the obtained patch has a fine-grained appearance, is flexible, has excellent breathability, and shrinkability, and has a good appearance after sticking. Was good and excellent in fit.
  • Example 2 In the same manner as in Example 1, except that a melt blown nonwoven fabric (thickness: 370 ⁇ m) having a basis weight of 100 g / m 2 was used as the support layer (a1) instead of the polyurethane elastic fiber nonwoven fabric, an adhesive tape (a ) And a patch was obtained. About the obtained patch, the results of measuring the moisture permeability and air permeability of the pressure-sensitive adhesive tape (a) constituting the patch, the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer (a2) and the hydrocolloid composition layer (b2), and the practical evaluation The results are shown in Table 2.
  • Example 3 A patch was obtained in the same manner as in Example 1 except that the hydrocolloid composition layer (b2) forming the pad layer (b) was changed to the composition of Formulation 2. About the obtained patch, the results of measuring the moisture permeability and air permeability of the pressure-sensitive adhesive tape (a) constituting the patch, the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer (a2) and the hydrocolloid composition layer (b2), and the practical evaluation The results are shown in Table 2.
  • Example 2 A pressure-sensitive adhesive tape was produced in the same manner as in Example 1 except that a polyurethane film (weight per unit area: 33.5 g / m 2 ) was used as the support layer in place of the polyurethane elastic fiber nonwoven fabric. I got the material. About the obtained adhesive material, the moisture permeability and the air permeability of the adhesive tape constituting the adhesive material, the results of measuring the adhesive strength of the adhesive layer (a2) and the hydrocolloid composition layer (b2), and the results of practical evaluation are shown. It is shown in 2.
  • Example 4 In the adhesive material of Example 1, the hydrocolloid composition forming the pad layer was changed to the composition of Formulation 3, and the polyurethane film layer (b1) was not provided, and the same as in Example 1, An adhesive tape was produced and a patch was obtained. About the obtained adhesive material, the moisture permeability and the air permeability of the adhesive tape constituting the adhesive material, the results of measuring the adhesive strength of the adhesive layer (a2) and the hydrocolloid composition layer (b2), and the results of practical evaluation are shown. It is shown in 2.
  • Table 2 shows the results of measuring the adhesive strength and the results of practical evaluation for a commercially available patch (not provided with a layer corresponding to an adhesive tape) in which the hydrocolloid composition is laminated on almost the entire surface of the film support. Shown in In addition, when the air permeability was measured, it exceeded 600 seconds / 300 cm 3 .
  • a pressure-sensitive adhesive tape (a1) comprising a support layer (a1) made of a nonwoven fabric or a knitted fabric formed from elastic fibers and a breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin.
  • a pad layer (b) comprising a polyurethane film layer (b1) adjacent to the air-permeable pressure-sensitive adhesive layer (a2) containing the synthetic resin and a hydrocolloid composition layer (b2). It was found that the adhesive materials 1 to 4 were excellent in adhesive strength and strength as an adhesive material, and had good air permeability and practical evaluation.
  • a pressure-sensitive adhesive layer a comparative example provided with a pressure-sensitive adhesive layer made of a non-breathable acrylic resin that does not include a breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin and does not perform a breathable treatment. It was found that the patch of No. 1 was poor in air permeability of the patch, apt to cause skin stuffiness, and low in practical evaluation.
  • the adhesive material of Comparative Example 2 which does not include a fabric formed of elastic fibers as a support layer and includes a polyurethane film, has low air permeability, has no air permeability, causes skin stuffiness, and has a low practical evaluation. I understood that.
  • the patch of Comparative Example 3 provided with a polyester film (polyethylene terephthalate) layer was used in practical evaluation. All three subjects pointed out that when they applied the fingers, they felt a little resistance when bending and stretching their fingers. This is presumed to be because the flexibility of the pad layer was lost, and it was suggested that the same result was obtained when a film other than the polyurethane film layer (b1) in the present invention was used, which lost flexibility.
  • Comparative Example 4 formed from the hydrocolloid composition layer having a high adhesive strength of the pad layer was strongly felt to adhere to the skin when the adhesive material was peeled off.
  • the urethane film is not disposed on the back surface of the hydrocolloid, when the water work is performed, the hydrocolloid absorbs water and swells, which is difficult for practical use.
  • Comparative Example 5 pointed out that all of the three subjects felt pain because of strong adhesion to the skin at the time of peeling.
  • Example 1 the left and right knees of four subjects (adult males) were applied to Example 1 and Comparative Example 5 at locations where they were scratched using a brass wire brush for a mini router until minor bleeding occurred evenly.
  • the adhesive material was applied and the adhesive material was peeled off after 4 days when the exudate was reduced, the adhesive material of Example 1 was easily peelable by 4 out of 4 subjects.
  • the re-bleeding did not occur in the patch of Comparative Example 5, 3 out of 4 subjects replied that they felt significant pain around the wound at the time of peeling.
  • the present invention comprises a support layer (a1) comprising a fabric formed from elastic fibers, a breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin, and a breathable pressure-sensitive adhesive layer containing the synthetic resin (
  • the wound part maintains a moist environment and is normal by being a patch comprising a pad layer (b) composed of a flexible film layer (b1) adjacent to a2) and a hydrocolloid composition layer (b2) Healthy skin does not become an excessively moist environment, there is no pain when peeling the patch from the skin, normal skin around the wound is not deformed, and the collapse of hydrocolloid due to the use of water at the daily life level is prevented Therefore, the present invention is highly applicable to the industry.
  • a1 Support layer made of a fabric formed from elastic fibers a2: Breathable pressure-sensitive adhesive layer containing a synthetic resin a: Adhesive tape b1: Flexible film layer b2: Hydrocolloid composition layer b: Pad layer c : Release paper

Abstract

An adhesive patch provided with: an adhesive tape (a) comprising a support layer (a1) that comprises a fabric formed from elastic fibers, preferably polyurethane elastic fibers, and an air-permeable adhesive layer (a2) that contains a synthetic resin and has preferably been foamed; and a pad layer (b) comprising a flexible film layer (b1), preferably a polyurethane film layer, which is adjacent to the air-permeable adhesive layer (a2) that contains a synthetic resin and has preferably been foamed, and a hydrocolloid composition layer (b2).

Description

貼付材Adhesive material
　本発明は、医療分野、特に切り傷、すり傷、さし傷、かき傷、靴ずれ等の創傷及び軽度の熱傷の治癒の促進、痛みの軽減、湿潤環境の維持、または保護の目的で用いられる貼付材に関し、特に救急絆創膏に適する貼付材に関する。 The present invention is applied to the medical field, particularly for the purpose of promoting healing of wounds and minor burns such as cuts, scratches, scratches, scratches, shoe slippage, relief of pain, maintenance of a moist environment, or protection. In particular, the present invention relates to a patch suitable for an emergency bandage.
　創傷の治療を行う際、従来は創傷面を乾燥させることに重点を置いた治療が行われてきた。ところが近年、創傷面を湿潤状態にすることにより治癒が促進されることが見いだされ、「ウェットヒーリング」または「モイストヒーリング」として広く認知されるようになり、これを利用した創傷治療材が種々開発されている。比較的早期に開発されたハイドロコロイド創傷被覆材は、疎水性の樹脂基材中に、親水性コロイドを分散させ、コロイドが、傷口に出てくる滲出液を吸収することにより、適度な湿潤状態を維持するよう設計されている。例えば、ハイドロコロイドドレッシング材と呼ばれるものは、創傷からの滲出液を吸収することができる。 When performing wound treatment, conventionally, treatment focused on drying the wound surface has been performed. However, in recent years, it has been found that healing is promoted by moistening the wound surface, and it has been widely recognized as “wet healing” or “moist healing”, and various wound treatment materials using this have been developed. Has been. The hydrocolloid wound dressing developed relatively early has dispersed the hydrophilic colloid in the hydrophobic resin base material, and the colloid absorbs the exudate that emerges from the wound, so that a moderate wet state is achieved. Designed to maintain. For example, what are called hydrocolloid dressings can absorb exudate from the wound.
　ハイドロコロイドドレッシング材は、支持体布帛または支持体フィルムの片面に体液吸液性と皮膚接着性を兼ね備えるハイドロコロイドの膏体層を設けたものである（特許文献１）。膏体層は、その吸液性によって貼付部位から滲出する体液を速やかに吸収するだけでなく、粘着性を備えているため、貼付部位の皮膚面形状に次第に密着する。該ハイドロコロイドの膏体層と裏打ち材とからなるパッドを粘着シートの粘着剤層の中央域に載置してなる貼付材（以下、「救急絆創膏」ということがある。）も知られている（特許文献２）。 The hydrocolloid dressing material is provided with a hydrocolloid plaster layer having both body fluid absorbency and skin adhesion on one side of a support fabric or support film (Patent Document 1). The plaster layer not only quickly absorbs body fluid that exudes from the applied site due to its liquid absorbency, but also has adhesiveness, and therefore gradually adheres to the skin surface shape of the applied site. There is also known a patch (hereinafter sometimes referred to as “emergency adhesive bandage”) in which a pad composed of the hydrocolloid plaster layer and a backing material is placed in the central region of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet. Patent Document 2).
　しかし、従来のハイドロコロイドドレッシング材等は、それ自体で皮膚に接着する機能を持たせなければならないため、必要以上の接着力で皮膚に接着させることになり、この結果、皮膚から剥離するときに痛みを伴うことがあるため、改良の余地があった。 However, since conventional hydrocolloid dressing materials, etc. must have the function of adhering to the skin by themselves, they will adhere to the skin with an unnecessarily strong adhesive force, resulting in pain when peeling from the skin. There is room for improvement.
　すなわち、創傷部の保護と治癒及び健常皮膚の状態維持という点で、ｉ）創傷部の湿潤環境を維持し、正常な皮膚は過度な湿潤環境にしない、ｉｉ）創傷部に密着することができるとともに、創傷部を傷つけず、貼付中の動きで剥がれず、パッド部位サイドからの水の浸入を防ぐことができるような粘着力を有する、ｉｉｉ）皮膚から剥離するときの痛みが小さい、などの特性を備える貼付材が、求められていた。 That is, in terms of protecting and healing the wound and maintaining the state of healthy skin, i) maintains the moist environment of the wound, normal skin does not become an excessive moist environment, ii) can adhere to the wound. In addition, it does not damage the wound part, does not peel off during movement during application, and has an adhesive force that can prevent water from entering from the side of the pad part, iii) has little pain when peeling from the skin, etc. There has been a demand for a patch having characteristics.
特開２０００－３７４１３号公報JP 2000-37413 A 特開２００２－６３９号公報JP 2002-639 A
　本発明の課題は、創傷部は湿潤環境を維持し、正常な皮膚は過度な湿潤環境にならず、貼付材を剥離するとき、創傷部及び正常皮膚部ともに痛みが小さく、創傷回りの正常な皮膚を変形させず、日常生活レベルの水の使用によるハイドロコロイド部への水の浸入を防止することができる救急絆創膏などの貼付材を提供することにある。 The problem of the present invention is that the wound part maintains a moist environment, normal skin does not become an excessive moist environment, and when the patch is peeled off, both the wound part and the normal skin part are less painful and normal around the wound. An object of the present invention is to provide a patch material such as an emergency bandage that can prevent the invasion of water into a hydrocolloid part due to the use of water at a daily life level without deforming the skin.
　本発明者らは、上記の課題を解決することについて鋭意研究した結果、支持体層と粘着剤層とからなる粘着テープの材料、及び、ハイドロコロイドの層を備えるパッド層の構成を特定のものとすることにより課題を解決できることを見いだし、本発明を完成した。 As a result of earnest research on solving the above problems, the present inventors have determined that the material of the pressure-sensitive adhesive tape comprising the support layer and the pressure-sensitive adhesive layer and the configuration of the pad layer including the hydrocolloid layer are specific. As a result, it was found that the problems could be solved, and the present invention was completed.
　すなわち、本発明によれば、弾性繊維から形成した布帛からなる支持体層（ａ１）と、合成樹脂を含有する通気性を有する粘着剤層（ａ２）とからなる粘着テープ（ａ）、及び、該合成樹脂を含有する通気性を有する粘着剤層（ａ２）に隣接する柔軟性のあるフィルム層（ｂ１）と、ハイドロコロイド組成物層（ｂ２）とからなるパッド層（ｂ）を備える貼付材が提供される。 That is, according to the present invention, a pressure-sensitive adhesive tape (a) comprising a support layer (a1) made of a fabric formed from elastic fibers and a gas-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin, and An adhesive patch comprising a pad layer (b) comprising a flexible film layer (b1) adjacent to the air-permeable pressure-sensitive adhesive layer (a2) containing the synthetic resin and a hydrocolloid composition layer (b2). Provided.
　また、本発明によれば、実施の態様として、以下（１）～（１２）の貼付材が提供される。 Also, according to the present invention, the following (1) to (12) patch materials are provided as embodiments.
（１）前記柔軟性のあるフィルム層（ｂ１）が、ポリウレタンフィルム層である前記の貼付材。 (1) The adhesive patch, wherein the flexible film layer (b1) is a polyurethane film layer.
（２）前記支持体層（ａ１）における弾性繊維が、平均繊維径が３～２５μｍのポリウレタン弾性繊維である前記の貼付材。 (2) The patch, wherein the elastic fiber in the support layer (a1) is a polyurethane elastic fiber having an average fiber diameter of 3 to 25 μm.
（３）前記支持体層（ａ１）における布帛が、不織布、織布または編布である前記の貼付材。 (3) The patch, wherein the fabric in the support layer (a1) is a nonwoven fabric, a woven fabric, or a knitted fabric.
（４）前記粘着剤層（ａ２）に含有される合成樹脂が、アクリル系樹脂である前記の貼付材。 (4) The patch, wherein the synthetic resin contained in the pressure-sensitive adhesive layer (a2) is an acrylic resin.
（５）前記粘着テープ（ａ）の透湿度が、２０００ｇ/ｍ２・２４ｈｒ以上である前記の貼付材。 (5) The said adhesive material whose moisture permeability of the said adhesive tape (a) is 2000 g / m < 2 > * 24hr or more.
（６）前記柔軟性のあるフィルム層（ｂ１）の厚みが、５～４５μｍの範囲である前記の貼付材。 (6) The patch, wherein the flexible film layer (b1) has a thickness in the range of 5 to 45 μm.
（７）前記ハイドロコロイド組成物層（ｂ２）が、
ｉ）ポリイソブチレン、ポリイソプレン、スチレン・イソプレン・スチレンブロック共重合体、アクリル系エラストマー、ウレタン系エラストマー、及びシリコーン系エラストマーからなる群より選ばれる少なくとも一種であるエラストマー成分；と、
ｉｉ）カルボキシメチルセルロース、デキストリン、ペクチン、ゼラチン、ポリアクリル酸ナトリウム、及びポリビニルピロリドンからなる群より選ばれる少なくとも一種である吸湿性物質；とを含有する前記の貼付材。 (7) The hydrocolloid composition layer (b2) is
i) an elastomer component which is at least one selected from the group consisting of polyisobutylene, polyisoprene, styrene / isoprene / styrene block copolymer, acrylic elastomer, urethane elastomer, and silicone elastomer;
ii) The above-mentioned patch containing at least one hygroscopic substance selected from the group consisting of carboxymethylcellulose, dextrin, pectin, gelatin, sodium polyacrylate, and polyvinylpyrrolidone.
（８）前記ハイドロコロイド組成物層（ｂ２）が、薬剤を含有するものである前記の貼付材。 (8) The patch, wherein the hydrocolloid composition layer (b2) contains a drug.
（９）前記ハイドロコロイド組成物層（ｂ２）の皮膚面に対する粘着力が、０．３～２Ｎ／１５ｍｍである前記の貼付材。 (9) The adhesive patch, wherein the hydrocolloid composition layer (b2) has an adhesive strength to the skin surface of 0.3 to 2 N / 15 mm.
（１０）前記粘着テープ（ａ）の面積に対する前記パッド層（ｂ）の面積の比が、５～５０％である前記の貼付材。 (10) The patch, wherein the ratio of the area of the pad layer (b) to the area of the adhesive tape (a) is 5 to 50%.
（１１）前記粘着テープ（ａ）の通気度が、０．２～３５秒／３００ｃｍ３である前記の貼付材。 (11) The patch, wherein the pressure-sensitive adhesive tape (a) has an air permeability of 0.2 to 35 seconds / 300 cm 3 .
（１２）さらに剥離紙（ｃ）を備える前記の貼付材。 (12) The above-mentioned patch, further comprising a release paper (c).
　本発明によれば、弾性繊維から形成した布帛からなる支持体層（ａ１）と、合成樹脂を含有する通気性を有する粘着剤層（ａ２）とからなる粘着テープ（ａ）、及び、該合成樹脂を含有する通気性を有する粘着剤層（ａ２）に隣接する柔軟性のあるフィルム層（ｂ１）と、ハイドロコロイド組成物層（ｂ２）とからなるパッド層（ｂ）を備える貼付材であることによって、創傷部は湿潤環境を維持し、正常な皮膚は過度な湿潤環境にならず、貼付材を皮膚から剥離するときの痛みがなく、創傷回りの正常な皮膚を変形させず、日常生活レベルの水の使用によるハイドロコロイド部への水の浸入を防止することができる貼付材が提供されるという効果が奏される。 According to the present invention, a pressure-sensitive adhesive tape (a) comprising a support layer (a1) made of a fabric formed from elastic fibers, a breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin, and the synthesis It is a patch comprising a pad layer (b) composed of a flexible film layer (b1) adjacent to a breathable pressure-sensitive adhesive layer (a2) containing a resin and a hydrocolloid composition layer (b2). The wound part maintains a moist environment, the normal skin does not become an excessive moist environment, there is no pain when peeling the adhesive material from the skin, the normal skin around the wound is not deformed, and the daily life level An effect is provided that a patch is provided that can prevent water from entering the hydrocolloid part due to the use of water.
本発明の貼付材の一例の略断面図である。It is a schematic sectional drawing of an example of the adhesive material of this invention.
　本発明の貼付材は、弾性繊維から形成した布帛からなる支持体層（ａ１）と、合成樹脂を含有する通気性を有する粘着剤層（ａ２）とからなる粘着テープ（ａ）、及び、該合成樹脂を含有する通気性を有する粘着剤層（ａ２）に隣接する柔軟性のあるフィルム層（ｂ１）と、ハイドロコロイド組成物層（ｂ２）とからなるパッド層（ｂ）を備える貼付材である。 The patch of the present invention comprises a pressure-sensitive adhesive tape (a) comprising a support layer (a1) comprising a fabric formed from elastic fibers, and a breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin, and A patch comprising a pad layer (b) comprising a flexible film layer (b1) adjacent to an air-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin and a hydrocolloid composition layer (b2). .
１．弾性繊維から形成した布帛からなる支持体層（ａ１）
　本発明の貼付材において、粘着テープ（ａ）は、支持体層と粘着剤層とから形成される。粘着テープ（ａ）を形成する支持体層は、弾性繊維から形成した布帛からなる支持体層（ａ１）である。 1. Support layer (a1) comprising a fabric formed from elastic fibers
In the patch of the present invention, the adhesive tape (a) is formed from a support layer and an adhesive layer. The support layer forming the adhesive tape (a) is a support layer (a1) made of a fabric formed from elastic fibers.
　弾性繊維から形成した布帛としては、ポリウレタン弾性繊維、ポリアクリル弾性繊維、ポリエステル弾性繊維、ゴム弾性繊維、その他の弾性繊維を用いた不織布、織布または編布を使用することができる。弾性繊維として、好ましくは、ポリウレタン弾性繊維である。また、布帛として、好ましくは、不織布である。弾性繊維としては、平均繊維径が、通常３～２５μｍ、好ましくは４～２０μｍ、より好ましくは５～１５μｍの範囲のものを使用することができる。したがって、支持体層（ａ１）における弾性繊維は、平均繊維径が３～２５μｍのポリウレタン弾性繊維であることが、特に好ましい。また、弾性繊維から形成した布帛は、目付が、通常２０～３００ｇ／ｍ２、好ましくは２５～２５０ｇ／ｍ２、より好ましくは３０～２００ｇ／ｍ２の範囲であり、厚みが、通常５０～５００μｍ、好ましくは８０～４５０μｍ、より好ましくは１２０～４００μｍの範囲である。布帛からなる支持体層（ａ１）の厚みが５００μｍを超えると、貼付材が、皮膚の動きに追随しにくくなり、短期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ことがある。支持体層（ａ１）の厚みが５０μｍ未満であると、貼付材の強度が不足し、また、短期間で皮膚から剥離することがある。 As the fabric formed from elastic fibers, polyurethane elastic fibers, polyacrylic elastic fibers, polyester elastic fibers, rubber elastic fibers, and other nonwoven fabrics, woven fabrics or knitted fabrics using other elastic fibers can be used. The elastic fiber is preferably a polyurethane elastic fiber. The fabric is preferably a nonwoven fabric. As the elastic fiber, one having an average fiber diameter of usually 3 to 25 μm, preferably 4 to 20 μm, more preferably 5 to 15 μm can be used. Therefore, the elastic fiber in the support layer (a1) is particularly preferably a polyurethane elastic fiber having an average fiber diameter of 3 to 25 μm. In addition, the fabric formed from elastic fibers has a basis weight of usually 20 to 300 g / m 2 , preferably 25 to 250 g / m 2 , more preferably 30 to 200 g / m 2 , and a thickness of usually 50 to The range is 500 μm, preferably 80 to 450 μm, more preferably 120 to 400 μm. When the thickness of the support layer (a1) made of the fabric exceeds 500 μm, the patch becomes difficult to follow the movement of the skin, and may peel off from the skin in a short period of time or may increase the uncomfortable feeling during application. . When the thickness of the support layer (a1) is less than 50 μm, the strength of the patch is insufficient, and it may be peeled off from the skin in a short period of time.
　支持体層（ａ１）として、特に好ましく使用されるポリウレタン弾性繊維から形成した不織布としては、例えば、ポリウレタン弾性繊維が積層され、その弾性繊維の接触点が該弾性繊維自体によって接合されているようなもので、タピルス（登録商標、タピルス株式会社製）、エスパンシオーネ（登録商標、ＫＢセーレン株式会社製）その他が好適に使用できる。 As the support layer (a1), as the nonwoven fabric formed from polyurethane elastic fibers that are particularly preferably used, for example, polyurethane elastic fibers are laminated, and the contact points of the elastic fibers are joined by the elastic fibers themselves. However, Tapirus (registered trademark, manufactured by Tapirus Co., Ltd.), Espancione (registered trademark, manufactured by KB Seiren Co., Ltd.) and others can be suitably used.
　弾性繊維から形成する不織布は、公知の不織布の製造方法であるメルトブロー法、スパンボンド法、エアレイド法、ニードルパンチ法などを採用することができる。また、不織布は、そのままで、またはエンボス加工した後、巻き取られ、不織布となる。 As the nonwoven fabric formed from elastic fibers, a melt blow method, a spun bond method, an airlaid method, a needle punch method, or the like, which is a known nonwoven fabric manufacturing method, can be employed. Moreover, a nonwoven fabric is wound as it is or after embossing, and becomes a nonwoven fabric.
　弾性繊維から形成した不織布等の布帛には、必要に応じて、通常使用される添加剤、例えば紫外線吸収剤、老化防止剤、充填剤、顔料、着色剤、難燃剤、帯電防止剤などを添加することができる。これらの添加剤は、繊維の原料に配合してもよいし、不織布等の布帛に表面処理を行って添加してもよく、透湿性を損なわない限り、その種類に応じて通常の量で用いられる。 Addition of commonly used additives such as UV absorbers, anti-aging agents, fillers, pigments, colorants, flame retardants, antistatic agents, etc. to fabrics such as non-woven fabrics formed from elastic fibers as necessary can do. These additives may be added to the raw material of the fiber, or may be added by performing a surface treatment on a cloth such as a non-woven fabric. Unless the moisture permeability is impaired, the additives are used in a usual amount. It is done.
　また、弾性繊維から形成した不織布等の布帛に、該弾性繊維と親和性及び接着性がある合成樹脂を含浸させてもよい。該合成樹脂には、弾性繊維と接着できるように適宜の接着剤を混合して使用することができ、ポリウレタン弾性繊維やポリアクリル弾性繊維から形成した不織布の場合には、ウレタン系樹脂、アクリル系樹脂を使用すると該不織布等の布帛の繊維（フィラメント）との接着性がよい。 Further, a fabric such as a nonwoven fabric formed from elastic fibers may be impregnated with a synthetic resin having affinity and adhesion with the elastic fibers. The synthetic resin can be used by mixing with an appropriate adhesive so that it can be bonded to elastic fibers. In the case of nonwoven fabrics formed from polyurethane elastic fibers or polyacrylic elastic fibers, urethane resins, acrylic resins can be used. When resin is used, the adhesiveness with the fibers (filaments) of the nonwoven fabric or the like is good.
２．合成樹脂を含有する通気性を有する粘着剤層（ａ２）
〔粘着剤〕
　本発明の貼付材において、粘着テープ（ａ）は、支持体層と粘着剤層とから形成される。粘着テープ（ａ）を形成する粘着剤層は、合成樹脂を含有する通気性を有する粘着剤層（ａ２）である点に特徴を有する。 2. Breathable pressure-sensitive adhesive layer containing a synthetic resin (a2)
[Adhesive]
In the patch of the present invention, the adhesive tape (a) is formed from a support layer and an adhesive layer. The pressure-sensitive adhesive layer forming the pressure-sensitive adhesive tape (a) is characterized in that it is a gas-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin.
　粘着剤層（ａ２）を形成する粘着剤に含有される合成樹脂は、皮膚刺激性が低いものであれば特に制限はなく、アクリル系、ウレタン系、シリコーン系、ゴム系、ポリビニルアルコール系、ポリアミド系、ポリ酢酸ビニル系、その他の合成樹脂を含有する粘着剤を使用することができる。これらの粘着剤の中でも、アクリル系樹脂からなるアクリル系粘着剤；ポリエーテル系ポリウレタン、ポリエステル系ポリウレタン等のウレタン系粘着剤；オルガノポリシロキサン、アルキルアリールポリシロキサン等のシリコーン系粘着剤；ポリイソブチレン、ブチルゴム、スチレン・ブタジエン共重合体（ＳＢＲ）、スチレン・イソプレン・スチレンブロック共重合体（ＳＩＳ）、スチレン・ブタジエン・スチレンブロック共重合体（ＳＢＳ）、スチレン・エチレン・ブチレン・スチレンブロック共重合体（ＳＥＢＳ）、スチレン・エチレン・プロピレン・スチレンブロック共重合体（ＳＥＰＳ）やＳＢＲの水素添加物等のゴム系粘着剤；が好ましく用いられる。アクリル系粘着剤が、粘着性及び皮膚刺激性の観点から、特に好ましい。 The synthetic resin contained in the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer (a2) is not particularly limited as long as it has low skin irritation, and is acrylic, urethane-based, silicone-based, rubber-based, polyvinyl alcohol-based, polyamide. A pressure-sensitive adhesive containing a base, polyvinyl acetate, or other synthetic resin can be used. Among these pressure-sensitive adhesives, acrylic pressure-sensitive adhesives made of acrylic resins; urethane-based pressure-sensitive adhesives such as polyether-based polyurethane and polyester-based polyurethane; silicone-based pressure-sensitive adhesives such as organopolysiloxane and alkylarylpolysiloxane; polyisobutylene, Butyl rubber, styrene / butadiene copolymer (SBR), styrene / isoprene / styrene block copolymer (SIS), styrene / butadiene / styrene block copolymer (SBS), styrene / ethylene / butylene / styrene block copolymer (SBS) SEBS), rubber adhesives such as styrene / ethylene / propylene / styrene block copolymer (SEPS) and hydrogenated products of SBR are preferably used. Acrylic adhesives are particularly preferred from the viewpoints of adhesiveness and skin irritation.
　アクリル系粘着剤に含有されるアクリル系樹脂としては、炭素数が１～１５、好ましくは１～１２、より好ましくは１～１０の範囲内であるアルキル基を有する（メタ）アクリル酸アルキルエステルの単独重合体、または、２種以上の（メタ）アクリル酸アルキルエステルの共重合体、あるいは、該（メタ）アクリル酸アルキルエステルの１種以上と、これと共重合可能な他のモノマーの１種以上とを共重合してなる共重合体が挙げられる。 The acrylic resin contained in the acrylic pressure-sensitive adhesive is a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 15, preferably 1 to 12, and more preferably 1 to 10 carbon atoms. A homopolymer, a copolymer of two or more (meth) acrylic acid alkyl esters, or one or more of the (meth) acrylic acid alkyl esters and another monomer copolymerizable therewith Examples thereof include copolymers obtained by copolymerizing the above.
　（メタ）アクリル酸アルキルエステルの具体例としては、アクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸ｎ－ブチル、アクリル酸ｔ－ブチル、アクリル酸イソアミル、アクリル酸２－エチルヘキシル、アクリル酸ｎ－オクチル、アクリル酸イソオクチル、アクリル酸イソノニル、アクリル酸デシル、アクリル酸ドデシル等のアクリル酸アルキルエステル；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ－ブチル、メタクリル酸イソブチル、メタクリル酸ｔ－ブチル、メタクリル酸イソアミル、メタクリル酸２－エチルヘキシル、メタクリル酸ｎ－オクチル、メタクリル酸イソオクチル、メタクリル酸イソノニル、メタクリル酸デシル、メタクリル酸ドデシル等のメタクリル酸アルキルエステル；等が挙げられる。 Specific examples of (meth) acrylic acid alkyl esters include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isoamyl acrylate, 2-ethylhexyl acrylate, and n-acrylate. -Acrylic acid alkyl esters such as octyl, isooctyl acrylate, isononyl acrylate, decyl acrylate, dodecyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, methacryl Alkyl methacrylates such as isoamyl acid, 2-ethylhexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, isononyl methacrylate, decyl methacrylate, dodecyl methacrylate; And the like.
　（メタ）アクリル酸アルキルエステルと共重合可能な他のモノマーとしては、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、クロトン酸等のカルボキシル基含有単量体；アクリル酸２－ヒドロキシエチル、アクリル酸２－ヒドロキシプロピル等の水酸基含有単量体；アクリル酸メトキシジエチレングリコール、メタクリル酸メトキシジエチレングリコール、アクリル酸メトキシジプロピレングリコール、メタクリル酸メトキシジプロピレングリコール、アクリル酸エトキシジエチレングリコール等の（メタ）アクリル酸アルコキシポリアルキレングリコールエステル；Ｎ，Ｎ－ジメチルアミノメチルアクリレート、Ｎ，Ｎ－ジメチルアミノエチルメタクリレート、Ｎ－ｔ－ブチルアミノエチルアクリレート等のアミノ基含有単量体；アクリルアミド、メタクリルアミド等のアミド基含有単量体；グリシジルメタクリレート等のグリシジル基含有単量体；酢酸ビニル等のビニルエステル；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；スチレン等のビニル芳香族化合物；塩化ビニル；ビニルピロリドン等のビニル系単量体などが挙げられる。（メタ）アクリル酸アルキルエステルと共重合可能な他のモノマーとして好ましいのは、酢酸ビニルである。なお、「（メタ）アクリル」とは、「アクリル」及び「メタクリル」を総称する表現である（以下、同様。）。アクリル系樹脂において、（メタ）アクリル酸アルキルエステルは、通常５０質量％以上、好ましくは６０質量％以上、より好ましくは７０～９７質量％、更に好ましくは７５～９５質量％の割合で用いられる。（メタ）アクリル酸アルキルエステルと共重合可能な他のモノマーは、通常５０質量％以下、好ましくは４０質量％以下、より好ましくは３０～３質量％、更に好ましくは２５～５質量％の割合で用いられる。 Other monomers copolymerizable with (meth) acrylic acid alkyl esters include acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid and other carboxyl group-containing monomers; 2-hydroxyethyl acrylate, acrylic acid Hydroxyl-containing monomers such as 2-hydroxypropyl; (meth) acrylic acid alkoxypolyalkylene such as methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, ethoxydiethylene glycol acrylate Glycol ester; amino group-containing monomer such as N, N-dimethylaminomethyl acrylate, N, N-dimethylaminoethyl methacrylate, Nt-butylaminoethyl acrylate Amide group-containing monomers such as acrylamide and methacrylamide; Glycidyl group-containing monomers such as glycidyl methacrylate; Vinyl esters such as vinyl acetate; Unsaturated nitriles such as acrylonitrile and methacrylonitrile; Vinyl aromatic compounds such as styrene; Vinyl chloride; vinyl monomers such as vinyl pyrrolidone. Preferred as another monomer copolymerizable with the (meth) acrylic acid alkyl ester is vinyl acetate. “(Meth) acryl” is a general term for “acryl” and “methacryl” (hereinafter the same). In the acrylic resin, the (meth) acrylic acid alkyl ester is usually used in a proportion of 50% by mass or more, preferably 60% by mass or more, more preferably 70 to 97% by mass, and further preferably 75 to 95% by mass. The other monomer copolymerizable with the (meth) acrylic acid alkyl ester is usually 50% by mass or less, preferably 40% by mass or less, more preferably 30 to 3% by mass, and still more preferably 25 to 5% by mass. Used.
　アクリル系樹脂は、特に製造方法が限定されず、一般に採用される溶液重合法、懸濁重合法または乳化重合法により製造することができる。 The production method of the acrylic resin is not particularly limited, and can be produced by a generally employed solution polymerization method, suspension polymerization method or emulsion polymerization method.
　これら粘着剤は、粘着特性を調整するために、所望により、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、石油系などの粘着付与樹脂を挙げることができる。また、アクリル系樹脂には、必要に応じて、さらに、ポリイソシアネート、メラミン樹脂、エポキシ樹脂、過酸化物、金属キレート化合物等の架橋剤；軟化剤、充填剤、酸化防止剤などを添加することができる。これらの粘着付与剤は、多くの場合、アクリル系樹脂１００質量部に対して、２０質量部以下、好ましくは１５質量部以下を用いることができる。また、添加剤は、同じく１０質量部以下、より好ましくは０．０１～５質量部、添加剤の種類によっては、更に好ましくは０．０２～２質量部の割合で用いることができる。 These pressure-sensitive adhesives can be mixed with a tackifier as desired in order to adjust the pressure-sensitive adhesive properties. Examples of the tackifier include tackifier resins such as terpene, terpene phenol, coumarone indene, styrene, rosin, xylene, phenol, and petroleum. In addition, cross-linking agents such as polyisocyanates, melamine resins, epoxy resins, peroxides, metal chelate compounds; softeners, fillers, antioxidants, etc. may be added to the acrylic resin as necessary. Can do. In many cases, these tackifiers can be used in an amount of 20 parts by mass or less, preferably 15 parts by mass or less based on 100 parts by mass of the acrylic resin. Similarly, the additive can be used in a proportion of 10 parts by mass or less, more preferably 0.01 to 5 parts by mass, and even more preferably 0.02 to 2 parts by mass depending on the type of additive.
〔合成樹脂を含有する通気性を有する粘着剤層〕
　本発明の貼付材における粘着剤層は、合成樹脂を含有する通気性を有する粘着剤層（ａ２）である。該合成樹脂を含有する通気性を有する粘着剤層（ａ２）は、それ自体は公知のものであり、ＪＩＳ　Ｐ８１１７に準拠して、ガーレー式デンソメーター（テスター産業株式会社）を使用して測定した通気度が６０秒／３００ｃｍ３以下の粘着剤である。粘着剤層の通気度は、より好ましくは０．０５～５０秒／３００ｃｍ３、更に好ましくは０．１～４０秒／３００ｃｍ３、特に好ましくは０．２～３５秒／３００ｃｍ３である。粘着剤層（ａ２）自体の通気性を測定することはできないため、不織布や織布など、粘着剤層（ａ２）以上の通気性がある材料と積層した状態で測定を行った値を、粘着剤層（ａ２）の通気性とする。粘着剤層（ａ２）の通気度の測定は、具体的には、以下のとおりである。すなわち、５ｃｍ×５ｃｍの大きさに裁断した粘着テープ（ａ）〔支持体層（ａ１）及び粘着剤層（ａ２）とからなる。〕を、締付板（土台）に貼付する。締付板を透過する面積は６４５．１６ｍｍ２とする。ガーレー式デンソメーターの内側シリンダーを引き出し、ストッパーにセットした後、締付板の間に試験片を締め付ける。内側シリンダーを静かに下降させ、３００ｃｍ３の空気量が通過する秒数を測定して得た粘着テープ（ａ）の通気度を、粘着剤層（ａ２）の通気度（秒／３００ｃｍ３）とする。したがって、特に好ましい粘着テープ（ａ）の通気度は、０．２～３５秒／３００ｃｍ３である。 [Breathable pressure-sensitive adhesive layer containing a synthetic resin]
The pressure-sensitive adhesive layer in the patch of the present invention is a gas-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin. The air-permeable pressure-sensitive adhesive layer (a2) containing the synthetic resin is known per se and measured using a Gurley type densometer (Tester Sangyo Co., Ltd.) in accordance with JIS P8117. The pressure-sensitive adhesive has an air permeability of 60 seconds / 300 cm 3 or less. The air permeability of the pressure-sensitive adhesive layer is more preferably 0.05 to 50 seconds / 300 cm 3 , still more preferably 0.1 to 40 seconds / 300 cm 3 , and particularly preferably 0.2 to 35 seconds / 300 cm 3 . Since the air permeability of the pressure-sensitive adhesive layer (a2) itself cannot be measured, the value measured in the state of being laminated with a material having air permeability higher than that of the pressure-sensitive adhesive layer (a2), such as a nonwoven fabric or a woven fabric, The air permeability of the agent layer (a2) is set. The measurement of the air permeability of the pressure-sensitive adhesive layer (a2) is specifically as follows. That is, it is composed of an adhesive tape (a) [support layer (a1) and adhesive layer (a2) cut to a size of 5 cm × 5 cm. ] Is affixed to the fastening plate (base). The area that penetrates the clamping plate is 645.16 mm 2 . Pull out the inner cylinder of the Gurley densometer, set it on the stopper, and tighten the test piece between the clamping plates. The air permeability of the pressure-sensitive adhesive tape (a) obtained by gently lowering the inner cylinder and measuring the number of seconds through which the amount of air of 300 cm 3 passes is the air permeability (seconds / 300 cm 3 ) of the pressure-sensitive adhesive layer (a2). To do. Therefore, the air permeability of the particularly preferred adhesive tape (a) is 0.2 to 35 seconds / 300 cm 3 .
　粘着剤層として、合成樹脂を含有する通気性を有する粘着剤で形成した粘着剤層（ａ２）を用いることにより、該粘着剤層及び貼付材の通気性やクッション性が良好となり、また、皮膚に対する追従性が向上して、皮膚への密着性が良好となる。本発明における合成樹脂を含有する通気性を有する粘着剤層（ａ２）は、通常の方法で得ることができる。具体的には、粘着剤と、空気、窒素ガス、炭酸ガス等の物理的発泡剤や分解型の化学発泡剤、水溶液や有機溶剤とを混合した後に、剥離紙に塗工し、あるいは、粘着剤を、あらかじめ水溶液や有機溶剤を塗布または散布した剥離紙に塗工し、次いで、加熱を行って、発泡または気化作用を利用する発泡方法のほか、塗工後の未乾燥の粘着剤表面に霧状の水分を塗布して、微細な孔を形成する方法、粘着剤を糸状・繊維状に剥離紙上に吐出する方法などが挙げられ、これらの方法により、合成樹脂中に多数の微細な孔を有する粘着剤層が形成される。微細かつ均一な孔を形成することができる観点から、より好ましくは発泡による方法である。合成樹脂を含有する通気性を有する粘着剤層（ａ２）は、発泡倍率が、通常１．１～１０倍、好ましくは１．２～８倍、より好ましくは１．５～６倍、更に好ましくは２～５倍の範囲であり、密度が、通常０．１～０．９ｇ／ｃｍ３、好ましくは０．１２～０．８ｇ／ｃｍ３、より好ましくは０．１５～０．６ｇ／ｃｍ３、更に好ましくは０．２～０．５ｇ／ｃｍ３の範囲である。合成樹脂を含有する通気性を有する粘着剤層（ａ２）は、通常支持体層（ａ１）の一方の面の全面に設けられるが、所望により、支持体層（ａ１）の全面に設けず、一部分に設けることもできる。合成樹脂を含有する通気性を有する粘着剤層（ａ２）の厚みは、特に限定されないが、通常１０～２００μｍ、好ましくは１５～１５０μｍ、より好ましくは２０～１００μｍの範囲である。 By using the pressure-sensitive adhesive layer (a2) formed of a gas-permeable pressure-sensitive adhesive containing a synthetic resin as the pressure-sensitive adhesive layer, the air-permeability and cushioning properties of the pressure-sensitive adhesive layer and the patch are improved, and the skin The followability to the skin is improved, and the adhesion to the skin is improved. The air-permeable pressure-sensitive adhesive layer (a2) containing the synthetic resin in the present invention can be obtained by a usual method. Specifically, the adhesive is mixed with a physical foaming agent such as air, nitrogen gas or carbon dioxide, a decomposable chemical foaming agent, an aqueous solution or an organic solvent, and then applied to the release paper or adhered. Apply the agent to release paper that has been coated or sprayed with an aqueous solution or organic solvent in advance, and then apply heat to the surface of the undried adhesive after coating, in addition to a foaming method that uses foaming or vaporization. Examples include a method of forming fine holes by applying mist-like moisture, a method of discharging an adhesive on a release paper in the form of threads and fibers, and these methods allow a number of fine holes to be formed in a synthetic resin. A pressure-sensitive adhesive layer is formed. From the viewpoint of forming fine and uniform pores, the foaming method is more preferable. The air-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin has an expansion ratio of usually 1.1 to 10 times, preferably 1.2 to 8 times, more preferably 1.5 to 6 times, and still more preferably. Is in the range of 2 to 5 times, and the density is usually 0.1 to 0.9 g / cm 3 , preferably 0.12 to 0.8 g / cm 3 , more preferably 0.15 to 0.6 g / cm 3 . 3 and more preferably in the range of 0.2 to 0.5 g / cm 3 . The air-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin is usually provided on the entire surface of one side of the support layer (a1), but if desired, not provided on the entire surface of the support layer (a1), It can also be provided in a part. The thickness of the air-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin is not particularly limited, but is usually in the range of 10 to 200 μm, preferably 15 to 150 μm, more preferably 20 to 100 μm.
３．粘着テープ（ａ）
　本発明の貼付材は、弾性繊維から形成した布帛からなる支持体層（ａ１）と、合成樹脂を含有する通気性を有する粘着剤層（ａ２）とからなる粘着テープ（ａ）を備えるものである。 3. Adhesive tape (a)
The patch of the present invention comprises a pressure-sensitive adhesive tape (a) comprising a support layer (a1) made of a fabric formed from elastic fibers and a gas-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin. is there.
〔粘着テープ（ａ）の透湿度〕
　本発明の貼付材は、弾性繊維から形成した布帛からなる支持体層（ａ１）と、合成樹脂を含有する通気性を有する粘着剤層（ａ２）とからなる粘着テープ（ａ）の透湿度が、２０００ｇ/ｍ２・２４ｈｒ以上であることが好ましく、貼付材を皮膚面に貼付したとき、発汗により剥離したり、かぶれが生じたりすることが効果的に抑制される。粘着テープ（ａ）の透湿度は、より好ましくは２５００ｇ／ｍ２・２４ｈｒ以上、更に好ましくは３０００ｇ／ｍ２・２４ｈｒ以上、特に好ましくは３５００ｇ／ｍ２・２４ｈｒ以上である。粘着テープ（ａ）の透湿度の上限は、通常５００００ｇ／ｍ２・２４ｈｒ程度である。粘着テープ（ａ）の透湿度は、弾性繊維から形成した布帛からなる支持体層（ａ１）と、合成樹脂を含有する通気性を有する粘着剤層（ａ２）とからなる粘着テープ（ａ）について、ＪＩＳ　Ｚ０２０８の（塩化カルシウム法）に従って、温度４０℃、相対湿度９０％の測定条件で測定したものである。具体的には、粘着テープ（ａ）の粘着剤層側の雰囲気を温度４０℃、相対湿度９０％に調節し、他面側には約１５ｇの吸湿剤（塩化カルシウム）を置いて、試料を通過した水分を吸収させ、吸湿剤の質量変化量を１ｍ２、２４時間当りに換算して透湿度とする。 [Water vapor transmission rate of adhesive tape (a)]
The adhesive material of the present invention has a moisture permeability of an adhesive tape (a) comprising a support layer (a1) made of a fabric formed from elastic fibers and a breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin. It is preferably 2000 g / m 2 · 24 hr or more, and when the patch is applied to the skin surface, peeling due to perspiration or rash is effectively suppressed. Moisture permeability of the adhesive tape (a) is more preferably 2500g / m 2 · 24hr or more, more preferably 3000g / m 2 · 24hr or more, and particularly preferably 3500g / m 2 · 24hr or more. The upper limit of the water vapor transmission rate of the pressure-sensitive adhesive tape (a) is usually about 50000 g / m 2 · 24 hr. The moisture permeability of the pressure-sensitive adhesive tape (a) is the pressure-sensitive adhesive tape (a) composed of a support layer (a1) made of a fabric formed from elastic fibers and a gas-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin. According to JIS Z0208 (calcium chloride method), the measurement was performed under the measurement conditions of a temperature of 40 ° C. and a relative humidity of 90%. Specifically, the atmosphere on the adhesive layer side of the adhesive tape (a) is adjusted to a temperature of 40 ° C. and a relative humidity of 90%, and about 15 g of a hygroscopic agent (calcium chloride) is placed on the other side, Moisture that has passed is absorbed, and the mass change amount of the hygroscopic agent is converted to moisture permeability by converting it to 1 m 2 per 24 hours.
〔粘着テープ（ａ）の粘着力〕
　本発明の貼付材における粘着テープ（ａ）の粘着力、具体的には、合成樹脂を含有する通気性を有する粘着剤層（ａ２）の粘着剤の粘着力は、対ユポ粘着力（剥離力）として、好ましくは０．５～４．２Ｎ／１５ｍｍ、より好ましくは０．７～３．５Ｎ／１５ｍｍ、更に好ましくは０．８～３．１Ｎ／１５ｍｍの範囲内であることが望ましい。粘着テープ（ａ）の粘着力が、この範囲内であることにより、本発明の貼付材を皮膚面に貼付した場合、十分な貼付性能を備え、貼付中に位置ずれが生じたりしないとともに、該貼付材を剥離するときには、皮膚の創傷部位はもちろん、創傷回りの正常な皮膚表面を剥離したり、かぶれを発生したりするおそれがない。また、上記の粘着力とすることで、パッド層（ｂ）を形成するポリウレタンフィルムとの接着を良好なものにし、投錨性が十分担保されるため、貼付材の使用中にパッド層（ｂ）がずれるなどの不都合がない。 [Adhesive strength of adhesive tape (a)]
The adhesive strength of the pressure-sensitive adhesive tape (a) in the patch of the present invention, specifically, the adhesive strength of the pressure-sensitive adhesive layer (a2) containing a synthetic resin, ) Is preferably in the range of 0.5 to 4.2 N / 15 mm, more preferably 0.7 to 3.5 N / 15 mm, and still more preferably 0.8 to 3.1 N / 15 mm. Since the adhesive strength of the adhesive tape (a) is within this range, when the adhesive material of the present invention is applied to the skin surface, the adhesive tape has sufficient adhesive performance and does not cause misalignment during application, When the patch is peeled off, there is no risk of peeling the normal skin surface around the wound or causing rash as well as the wound site on the skin. In addition, the adhesive strength with the polyurethane film forming the pad layer (b) is improved and the anchoring property is sufficiently ensured by using the above adhesive strength. There is no inconvenience such as slippage.
　粘着テープ（ａ）の粘着力の測定方法は以下のとおりである。すなわち、粘着テープ（ａ）を、幅１５ｍｍ×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。一方、ベークライト製試験パネルに、ユポ（登録商標）ＦＰＧ－１３０ (株式会社ユポ・コーポレーション製の合成紙) を両面テープで貼り付けて対ユポ粘着力試験パネルを作製する。試験片を試験パネルに押しつけて貼着させる。貼着してから２０分間経過した後、ＪＩＳ　Ｚ０２３７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 measuring method of the adhesive strength of the adhesive tape (a) is as follows. That is, the pressure-sensitive adhesive tape (a) is cut into a predetermined length of 15 mm width × 15 mm length, preferably 100 mm, to obtain a test piece. On the other hand, a YUPO (registered trademark) FPG-130 (synthetic paper manufactured by YUPO Corporation) is attached to a Bakelite test panel with a double-sided tape to produce a YUPO adhesion test panel. The test piece is pressed against the test panel and adhered. After 20 minutes have passed since sticking, the adhesive strength is measured under the conditions of a peeling angle of 180 ° and a peeling speed of 300 mm / min according to JIS Z0237.
４．粘着テープ（ａ）の製造方法
　本発明の貼付材における粘着テープ（ａ）は、弾性繊維から形成した布帛からなる支持体層（ａ１）と、合成樹脂を含有する通気性を有する、好ましくは発泡した粘着剤層（ａ２）とからなる。粘着テープ（ａ）の製造方法は、特に限定されないが、弾性繊維から形成した不織布等の布帛からなる支持体層（ａ１）の上に、粘着剤となる合成樹脂の溶液またはエマルションを直接塗工し、該粘着剤を発泡させることによって、発泡した合成樹脂を含有する粘着剤層（ａ２）を形成してもよい。また、シリコーン系剥離剤等を塗布した工程紙上に、粘着剤となる合成樹脂の溶液またはエマルションを塗工し、該粘着剤を発泡させることによって、発泡した合成樹脂を含有する粘着剤層（ａ２）を形成した後に、弾性繊維から形成した不織布等の布帛からなる支持体層（ａ１）と積層する方法を採用することもできる。粘着剤層（ａ２）が、支持体層（ａ１）の全面に設けられない場合、その他所望により、粘着剤となる合成樹脂の溶液またはエマルションの塗工を、点状、縞状その他のパターンによって行えばよい。 4). Manufacturing method of pressure-sensitive adhesive tape (a) The pressure-sensitive adhesive tape (a) in the patch of the present invention has a support layer (a1) made of a fabric formed from elastic fibers and a breathability containing a synthetic resin, preferably foamed. The pressure-sensitive adhesive layer (a2). The production method of the pressure-sensitive adhesive tape (a) is not particularly limited, but a solution or emulsion of a synthetic resin to be a pressure-sensitive adhesive is directly applied on the support layer (a1) made of a fabric such as a nonwoven fabric formed from elastic fibers. Then, the pressure-sensitive adhesive layer (a2) containing the foamed synthetic resin may be formed by foaming the pressure-sensitive adhesive. Further, a pressure-sensitive adhesive layer (a2) containing a foamed synthetic resin is applied by applying a synthetic resin solution or emulsion to be a pressure-sensitive adhesive on a process paper coated with a silicone release agent, and foaming the pressure-sensitive adhesive. ), And a method of laminating with a support layer (a1) made of a fabric such as a nonwoven fabric formed from elastic fibers may be employed. When the pressure-sensitive adhesive layer (a2) is not provided on the entire surface of the support layer (a1), the application of the synthetic resin solution or emulsion to be the pressure-sensitive adhesive may be performed according to other patterns such as dots, stripes, etc. Just do it.
５．パッド層（ｂ）
　本発明の貼付材は、柔軟性のあるフィルム層（ｂ１）と、ハイドロコロイド組成物層（ｂ２）とからなるパッド層（ｂ）を備えるものである。パッド層（ｂ）は、あらかじめ形成した柔軟性のあるフィルム層（ｂ１）とハイドロコロイド組成物層（ｂ２）とを、接着その他の方法により一体化させてもよいし、後述するように、柔軟性のあるフィルム上に上記ハイドロコロイド組成物を押し出すことによって、柔軟性のあるフィルム層（ｂ１）と一体となったハイドロコロイド組成物層（ｂ２）を形成して、パッド層（ｂ）を得てもよい。 5. Pad layer (b)
The patch of the present invention comprises a pad layer (b) composed of a flexible film layer (b1) and a hydrocolloid composition layer (b2). The pad layer (b) may be formed by integrating the flexible film layer (b1) and the hydrocolloid composition layer (b2) formed in advance by bonding or other methods. A pad layer (b) may be obtained by forming the hydrocolloid composition layer (b2) integrated with the flexible film layer (b1) by extruding the hydrocolloid composition onto a film having .
６．柔軟性のあるフィルム層（ｂ１）
　本発明の貼付材におけるパッド層（ｂ）を形成する柔軟性のあるフィルム層（ｂ１）は、前記の合成樹脂を含有する通気性を有する粘着剤層（ａ２）に隣接する柔軟性のあるフィルム層（ｂ１）である。すなわち、弾性繊維から形成した不織布等の布帛からなる支持体層（ａ１）と反対側の面に、柔軟性のあるフィルム層（ｂ１）を備えるものである。柔軟性のあるフィルム層（ｂ１）は、前記の合成樹脂を含有する通気性を有する粘着剤層（ａ２）と、後述のハイドロコロイド組成物層（ｂ２）との間にあって、ハイドロコロイド組成物層（ｂ２）が吸収した水分を前記の粘着テープ（ａ）側に移行させる高透湿性を備えるとともに、該ハイドロコロイド組成物層（ｂ２）を支持する強度と伸縮性とを併せ備え、かつ、貼付材外部からの水分の浸入を防止する機能を有する裏打ち材である。 6). Flexible film layer (b1)
The flexible film layer (b1) forming the pad layer (b) in the patch of the present invention is a flexible film adjacent to the air-permeable pressure-sensitive adhesive layer (a2) containing the synthetic resin. Layer (b1). That is, a flexible film layer (b1) is provided on the surface opposite to the support layer (a1) made of a cloth such as a nonwoven fabric formed from elastic fibers. The flexible film layer (b1) is located between the air-permeable pressure-sensitive adhesive layer (a2) containing the synthetic resin and the hydrocolloid composition layer (b2) described later, and the hydrocolloid composition layer (b2). ) Has a high moisture permeability for transferring moisture absorbed to the pressure-sensitive adhesive tape (a) side, has strength and elasticity to support the hydrocolloid composition layer (b2), and from the outside of the adhesive material It is a backing material having a function of preventing the intrusion of moisture.
　したがって、該柔軟性のあるフィルム層（ｂ１）は、前記した粘着テープ（ａ）の透湿度の測定方法と同様の方法により測定した透湿度が１０００ｇ／ｍ２・２４ｈｒ以上であることが好ましく、より好ましくは２０００ｇ／ｍ２・２４ｈｒ以上、更に好ましくは３０００ｇ／ｍ２・２４ｈｒ以上、特に好ましくは３５００ｇ／ｍ２・２４ｈｒ以上である。粘着剤層の透湿度の上限は、通常１００００ｇ／ｍ２・２４ｈｒ程度、多くの場合８０００ｇ／ｍ２・２４ｈｒ程度である。 Therefore, the flexible film layer (b1) preferably has a moisture permeability of 1000 g / m 2 · 24 hr or more measured by the same method as the moisture permeability measurement method of the adhesive tape (a) described above. more preferably 2000g / m 2 · 24hr or more, more preferably 3000g / m 2 · 24hr or more, and particularly preferably 3500g / m 2 · 24hr or more. The upper limit of the moisture permeability of the adhesive layer is usually 10000g / m 2 · 24hr or so, often 8000g / m 2 · 24hr approximately.
　柔軟性のあるフィルム層（ｂ１）の厚みは、通常５～４５μｍ、好ましくは６～４０μｍ、より好ましくは７～３５μｍである。厚みが小さすぎると、強度と水分の浸入防止機能が不足し、製造時の取り扱い性が悪化するおそれがある。厚みが大きすぎると、貼付材全体としての高透湿性が発揮されず、また伸縮性が不足するおそれがある。 The thickness of the flexible film layer (b1) is usually 5 to 45 μm, preferably 6 to 40 μm, more preferably 7 to 35 μm. If the thickness is too small, strength and moisture intrusion prevention functions are insufficient, and the handleability during production may be deteriorated. If the thickness is too large, high moisture permeability as the whole patch is not exhibited, and the stretchability may be insufficient.
　柔軟性のあるフィルム層（ｂ１）とは、皮膚に対する追従性があり、貼付材を皮膚に密着させることが可能な程度に柔軟なフィルムから形成されたフィルム層である。柔軟性のあるフィルム層（ｂ１）を形成する素材は、従来から公知の素材を用いることができるが、熱可塑性の樹脂で、ヒト皮膚に対する安全性が確認されており、フィルム状としたときに、柔軟性、伸縮性が認められ、日常防水性があり、高透湿性の機能を備えるものを用いることが好ましい。具体的には、ＬＬＤＰＥ、ＬＤＰＥ等のポリエチレン製のフィルムに０．０１～１０μｍ程度の微細孔を設けたものや、炭酸カルシウム等を含有させ、所望により延伸加工したもののほか、ポリウレタンを素材とするポリウレタンフィルムが好ましい。特に、柔軟性のあるフィルム層（ｂ１）をポリウレタンフィルム層とすると、引張り応力が他の素材よりも優れるため、関節などの稼動部付近の皮膚の創傷部にも柔軟に適合するので、より好ましい。ポリウレタンフィルム層を形成するためのポリウレタンは、ポリエーテル系ポリウレタンまたはポリエステル系ポリウレタンのいずれも使用することができる。ポリウレタンフィルムは、通常のポリウレタンフィルムの製造方法によって得ることができ、また、シルクロン（登録商標）ＮＥＳ８５（大倉工業株式会社社製）、ＤＩＮＴＥＸ（登録商標）ＦＴ１０８０－ＰＥ、ＤＩＮＴＥＸＦＴ１８８１－ＰＥ（日本ユニポリマー株式会社製）、サンプレン（登録商標）ＨＭＰ－１７Ａ（三洋化成工業株式会社製）等として、それぞれ入手可能であり、該ポリウレタンフィルムをポリウレタンフィルム層（ｂ１）に用いることもできる。ポリウレタンフィルムの一方の表面または両面にコロナ処理や下塗り処理などを行ってもよい。 The flexible film layer (b1) is a film layer formed from a flexible film that is capable of following the skin and that allows the adhesive material to adhere to the skin. As a material for forming the flexible film layer (b1), a conventionally known material can be used, but it is a thermoplastic resin, and safety for human skin has been confirmed. In addition, it is preferable to use a material that is recognized for flexibility and stretchability, has daily waterproofness, and has a highly moisture-permeable function. Specifically, a film made of polyethylene such as LLDPE, LDPE, etc. provided with fine pores of about 0.01 to 10 μm, or containing calcium carbonate and stretched as desired, and polyurethane as a material. A polyurethane film is preferred. In particular, when the flexible film layer (b1) is a polyurethane film layer, the tensile stress is superior to that of other materials. . As the polyurethane for forming the polyurethane film layer, either polyether-based polyurethane or polyester-based polyurethane can be used. The polyurethane film can be obtained by an ordinary method for producing a polyurethane film. Also, Silklon (registered trademark) NES85 (manufactured by Okura Kogyo Co., Ltd.), DINTEX (registered trademark) FT1080-PE, DINTEXFT1881-PE (Nihon Unipolymer) Co., Ltd.), Samprene (registered trademark) HMP-17A (manufactured by Sanyo Kasei Kogyo Co., Ltd.), etc., and the polyurethane film can be used for the polyurethane film layer (b1). Corona treatment or undercoating may be performed on one or both surfaces of the polyurethane film.
７．ハイドロコロイド組成物層（ｂ２）
　本発明の貼付材におけるパッド層（ｂ）を形成するハイドロコロイド組成物層（ｂ２）は、前記の柔軟性のあるフィルム層（ｂ１）の合成樹脂を含有する通気性を有する粘着剤層（ａ２）と反対側の面に設けられる。 7). Hydrocolloid composition layer (b2)
The hydrocolloid composition layer (b2) forming the pad layer (b) in the patch of the present invention is a breathable pressure-sensitive adhesive layer (a2) containing the synthetic resin of the flexible film layer (b1). It is provided on the opposite surface.
〔ハイドロコロイド組成物〕
　本発明の貼付材におけるハイドロコロイド組成物層（ｂ２）に含有されるハイドロコロイド組成物とは、例えば、アクリル系、シリコーン系、ウレタン系、ポリ酢酸ビニル系、天然ゴム系、合成ゴム系等の粘着性を有する高分子材料に、例えば、カルボキシメチルセルロース、カラヤガム、デキストリン、ペクチン、ゼラチン、ポリビニルアルコール、ポリアクリル酸ナトリウム等の吸液性、特に吸水性を有する親水性高分子化合物を吸湿性物質（以下、「吸収剤」ということがある。）として加えてなるものである。 [Hydrocolloid composition]
Examples of the hydrocolloid composition contained in the hydrocolloid composition layer (b2) in the patch of the present invention include, for example, acrylic, silicone, urethane, polyvinyl acetate, natural rubber, and synthetic rubber adhesives. For example, carboxymethyl cellulose, karaya gum, dextrin, pectin, gelatin, polyvinyl alcohol, a hydrophilic polymer compound having water absorption, such as sodium polyacrylate, is used as a hygroscopic substance (hereinafter, referred to as a hygroscopic substance). It is sometimes called "absorbent").
　粘着性を有する高分子材料としては、皮膚刺激性及び保形性の観点から、ポリイソブチレン、ポリイソプレン、ポリブタジエン、スチレン・ブタジエン・スチレンブロック共重合体、スチレン・イソプレン・スチレンブロック共重合体（ＳＩＳ）等の合成ゴムやアクリル系エラストマー、ウレタン系エラストマー、及びシリコーン系エラストマー等のエラストマーを主成分とするものが好ましく、特に好ましくはＳＩＳが用いられ、市販品として、クインタック３４２１(登録商標、日本ゼオン株式会社製)等がある。これらの材料は、１種または２種以上を用いることができる。 From the viewpoint of skin irritation and shape retention, the adhesive polymer materials include polyisobutylene, polyisoprene, polybutadiene, styrene / butadiene / styrene block copolymer, styrene / isoprene / styrene block copolymer (SIS). ) And the like, and those mainly composed of elastomers such as acrylic elastomers, urethane elastomers, and silicone elastomers are preferred, and SIS is particularly preferably used. Quintac 3421 (registered trademark, Japan) is commercially available. Zeon Corporation). These materials can be used alone or in combination of two or more.
　粘着性を有する高分子材料には、該ハイドロコロイド組成物層（ｂ２）に適度な粘着性を付与するために、粘着付与樹脂を添加することができる。好ましい粘着付与樹脂としては、ロジンエステル樹脂、テルペン系樹脂、脂環族系樹脂、及び、それらの水添物が挙げられ、市販品として、アルコンＰ１２５(登録商標、荒川化学工業株式会社製の水素化石油樹脂)等がある。粘着付与樹脂は、粘着性を有する高分子材料１００質量部に対して、通常２００質量部以下、好ましくは１９０質量部以下、より好ましくは１８０質量部以下の添加量とする。また、粘着性を有する高分子材料には、更に軟化剤（可塑剤）を添加することができる、好ましい軟化剤としては、流動パラフィンなどの石油系軟化剤；液状ポリイソプレン、ポリブテン、ポリイソブチレンなどの液状ゴム系軟化剤；フタル酸エステル、アジピン酸エステル等の二塩基酸エステル系可塑剤；ポリエチレングリコール、クエン酸エステル等のその他の可塑剤；などが挙げられる。軟化剤の添加量は、粘着性を有する高分子材料１００質量部に対して、通常１００質量部以下、好ましくは９０質量部以下、より好ましくは８０質量部以下の添加量とする。 A tackifier resin can be added to the polymer material having tackiness in order to impart appropriate tackiness to the hydrocolloid composition layer (b2). Preferable tackifying resins include rosin ester resins, terpene resins, alicyclic resins, and hydrogenated products thereof. Alcon P125 (registered trademark, manufactured by Arakawa Chemical Industries, Ltd.) is a commercially available product. Petrochemical resin). The tackifying resin is added in an amount of usually 200 parts by mass or less, preferably 190 parts by mass or less, and more preferably 180 parts by mass or less with respect to 100 parts by mass of the adhesive polymer material. Further, a softener (plasticizer) can be further added to the adhesive polymer material. Preferred softeners include petroleum-based softeners such as liquid paraffin; liquid polyisoprene, polybutene, polyisobutylene and the like. Liquid rubber softeners; dibasic acid ester plasticizers such as phthalate esters and adipates; and other plasticizers such as polyethylene glycol and citrate esters. The addition amount of the softening agent is usually 100 parts by mass or less, preferably 90 parts by mass or less, more preferably 80 parts by mass or less with respect to 100 parts by mass of the polymer material having adhesiveness.
　吸湿性物質としては、カルボキシメチルセルロース（以下、「ＣＭＣ」ということがある。）、デキストリン、ペクチン、ゼラチン、ポリアクリル酸ナトリウム、ポリビニルピロリドン、カルボキシメチルセルロースカルシウム、ヒドロキシプロピルセルロース、グアーガム、ローカストビーンガム、キサンタンガム、アルギン酸ナトリウム、アルギン酸カルシウム、カラギーナン、コラーゲン等が好ましく用いられる。ＣＭＣの市販品としては、セロゲンＦ－３Ｈ(登録商標、第一工業製薬株式会社製)等がある。 As the hygroscopic substance, carboxymethylcellulose (hereinafter sometimes referred to as “CMC”), dextrin, pectin, gelatin, sodium polyacrylate, polyvinylpyrrolidone, carboxymethylcellulose calcium, hydroxypropylcellulose, guar gum, locust bean gum, xanthan gum Sodium alginate, calcium alginate, carrageenan, collagen and the like are preferably used. As a commercial product of CMC, there is Serogen F-3H (registered trademark, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
　粘着性を有する高分子材料と吸湿性物質との、特に好ましい組み合わせは、
ｉ）ポリイソブチレン、ポリイソプレン、スチレン・イソプレン・スチレンブロック共重合体、アクリル系エラストマー、ウレタン系エラストマー、及びシリコーン系エラストマーからなる群より選ばれる少なくとも一種であるエラストマー成分；と、
ｉｉ）カルボキシメチルセルロース、デキストリン、ペクチン、ゼラチン、ポリアクリル酸ナトリウム、及びポリビニルピロリドンからなる群より選ばれる少なくとも一種である吸湿性物質；とを含有するハイドロコロイド組成物層（ｂ２）である。 A particularly preferable combination of the adhesive polymer material and the hygroscopic substance is:
i) an elastomer component which is at least one selected from the group consisting of polyisobutylene, polyisoprene, styrene / isoprene / styrene block copolymer, acrylic elastomer, urethane elastomer, and silicone elastomer;
ii) a hydrocolloid composition layer (b2) containing at least one hygroscopic substance selected from the group consisting of carboxymethylcellulose, dextrin, pectin, gelatin, sodium polyacrylate, and polyvinylpyrrolidone.
　吸湿性物質は、ハイドロコロイド組成物中において、粘着性を有する高分子材料２５～９０質量％に対して、７５～１０質量％となるように含有させることができる。好ましくは前記高分子材料３０～８５質量％に対して、吸湿性物質７０～１５質量％、より好ましくは前記高分子材料３５～８０質量％に対して、吸湿性物質６５～２０質量％となる含有量であり、特に好ましくは前記高分子材料４０～７５質量％に対して、吸湿性物質６０～２５質量％となるように、吸湿性物質を含有させることが、吸液性、特に吸水性、創傷部位との接着性、及び適度な保形性（側面からの膏体のはみだし防止性）の観点から望ましい。高分子材料が、必要に応じて添加する粘着付与樹脂及び／または軟化剤を含有する場合は、高分子材料と、粘着付与樹脂及び／または軟化剤との合計量に対して、吸湿性物質を、前記した高分子材料と吸湿性物質との含有比率と同様の比率で含有させるようにすればよい。 The hygroscopic substance can be contained in the hydrocolloid composition so as to be 75 to 10% by mass with respect to 25 to 90% by mass of the adhesive polymer material. Preferably, the hygroscopic substance is 70 to 15% by mass with respect to 30 to 85% by mass of the polymer material, and more preferably 65 to 20% by mass with respect to the polymer material of 35 to 80% by mass. It is preferable that the hygroscopic substance be contained so that the hygroscopic substance is 60 to 25% by mass with respect to 40 to 75% by mass of the polymer material. From the viewpoint of adhesion to the wound site and moderate shape retention (prevention of the plaster from the side). When the polymer material contains a tackifying resin and / or softening agent to be added as necessary, the hygroscopic substance is added to the total amount of the polymer material and the tackifying resin and / or softening agent. The content ratio may be the same as the content ratio between the polymer material and the hygroscopic substance.
　ハイドロコロイド組成物には、前記粘着性を有する高分子材料及び吸湿性物質のほかに、通常５質量％以下の他の任意成分を含有させることができる。例えば、酸化防止剤、脱臭剤、芳香剤を含有させることができる。内部凝集力を高めるために架橋剤を適宜含有させてもよい。 In addition to the adhesive polymer material and the hygroscopic substance, the hydrocolloid composition can usually contain other optional components of 5% by mass or less. For example, an antioxidant, a deodorant, and a fragrance can be contained. In order to increase the internal cohesive force, a crosslinking agent may be appropriately contained.
　特に、該ハイドロコロイド組成物層（ｂ２）は、創傷部位に接触するものであることから、薬理学上有効な薬剤を所要量含有させてもよい。ハイドロコロイド組成物に含有させる薬理学上有効な薬剤としては、抗生物質、殺菌剤や抗菌剤（アクリノール、塩化ベンザルコニウム、銀系化合物等）、消毒剤、抗炎症剤及び皮膚保護剤などが挙げられ、これらは通常３質量％以下、好ましくは２質量％以下の含有量でもよい。さらに、ハイドロコロイド組成物には、該組成物中１質量％以下の物理的補強剤（粘着性を有する高分子材料等とフアンデル・ワールズ結合を形成する。）を含有させることもでき、例えば、カーボンブラツク、ポリアラミド類、水和化シリカ類等が挙げられる。 In particular, since the hydrocolloid composition layer (b2) is in contact with the wound site, it may contain a required amount of a pharmacologically effective drug. Examples of pharmacologically effective drugs to be included in the hydrocolloid composition include antibiotics, bactericides and antibacterial agents (acrinol, benzalkonium chloride, silver compounds, etc.), disinfectants, anti-inflammatory agents and skin protective agents. These may have a content of usually 3% by mass or less, preferably 2% by mass or less. Further, the hydrocolloid composition may contain 1% by mass or less of a physical reinforcing agent (forms a Van der Waals bond with an adhesive polymer material or the like), for example, carbon. Examples thereof include black, polyaramids, hydrated silicas and the like.
　ハイドロコロイド組成物層（ｂ２）の厚みは、通常１００μｍ～２ｍｍ、好ましくは１５０μｍ～１．５ｍｍ、より好ましくは２００μｍ～１ｍｍの範囲である。厚みが小さすぎると、創傷部位からの浸出液の吸収が不足することがあり、厚みが大きすぎると、伸縮性が悪くなり、貼付時に創傷部位にストレスを与えるなどの不具合がある。 The thickness of the hydrocolloid composition layer (b2) is usually in the range of 100 μm to 2 mm, preferably 150 μm to 1.5 mm, more preferably 200 μm to 1 mm. If the thickness is too small, absorption of the exudate from the wound site may be insufficient. If the thickness is too large, the stretchability will be poor, and there will be problems such as applying stress to the wound site during application.
　ハイドロコロイド組成物層（ｂ２）は、前記のハイドロコロイド組成物を、加熱しながら混合し、得られた混合物を押し出し、ロールまたはプレス成形して所望厚みの成形物とし、該成形物を所定の寸法及び形状に切り出すことによって製造することができる。また、前記柔軟性のあるフィルム層（ｂ１）を形成するポリウレタンのフィルム上に上記ハイドロコロイド組成物を押し出すことによって、柔軟性のあるフィルム層（ｂ１）と一体となったハイドロコロイド組成物層（ｂ２）を形成することもできる。 The hydrocolloid composition layer (b2) is prepared by mixing the hydrocolloid composition with heating, extruding the obtained mixture, and rolling or press-molding it into a molded product having a desired thickness. It can be manufactured by cutting into a shape. Also, the hydrocolloid composition layer (b2) integrated with the flexible film layer (b1) by extruding the hydrocolloid composition onto a polyurethane film forming the flexible film layer (b1). Can also be formed.
〔ハイドロコロイド組成物層（ｂ２）の吸水率〕
　パッド層（ｂ）を形成するハイドロコロイド組成物層（ｂ２）としては、自重の５０～４００質量％の吸水率（吸液率）を有するものを採用することが好ましい。吸水率は、より好ましくは１００～２５０質量％である。吸水率は、パッド層（ｂ）を形成するハイドロコロイド組成物層（ｂ２）を温度３７℃の生理食塩水中に２４時間浸漬する前後の質量から算出したものである。吸水率が小さすぎると、創傷部位から滲出する体液を充分に吸収しきれず、周囲に体液が漏れ、衣服を汚したり、健常皮膚部への多量の水分により悪い影響を及ぼすことがある。吸水率が大きすぎると、多くのハイドロコロイド組成物層（ｂ２）が体液を吸収しすぎて軟化し、創傷部位を含む貼付皮膚面に残留するおそれが生じることもある。 [Water Absorption Rate of Hydrocolloid Composition Layer (b2)]
As the hydrocolloid composition layer (b2) forming the pad layer (b), a layer having a water absorption rate (liquid absorption rate) of 50 to 400% by mass of its own weight is preferably employed. The water absorption is more preferably 100 to 250% by mass. The water absorption is calculated from the mass before and after immersing the hydrocolloid composition layer (b2) forming the pad layer (b) in physiological saline at a temperature of 37 ° C. for 24 hours. If the water absorption rate is too small, the body fluid that exudes from the wound site cannot be sufficiently absorbed, the body fluid leaks to the surroundings, and the clothes may be stained, or a large amount of moisture on the healthy skin may be adversely affected. If the water absorption rate is too large, many hydrocolloid composition layers (b2) may absorb body fluid and soften, and may remain on the skin surface including the wound site.
〔ハイドロコロイド組成物層（ｂ２）の粘着力〕
　パッド層（ｂ）を形成するハイドロコロイド組成物層（ｂ２）は、創傷部位を含む貼付皮膚面に貼付されるものであり、創傷部位及び健常皮膚に損傷を与えることなく剥離できるものでなければならないこと、及び背面に配置される柔軟性のあるフィルム層（ｂ１）に対する投錨性を良好に保つ必要があることから、所定の粘着力を有することが望ましい。したがって、ハイドロコロイド組成物層（ｂ２）の粘着力は、皮膚面に対する粘着力と、対ユポ粘着力とを測定して、評価する。 [Adhesive strength of hydrocolloid composition layer (b2)]
The hydrocolloid composition layer (b2) forming the pad layer (b) is to be applied to the skin surface including the wound site and must be able to be peeled without damaging the wound site and healthy skin. In addition, since it is necessary to keep the anchoring property with respect to the flexible film layer (b1) disposed on the back surface, it is desirable to have a predetermined adhesive force. Therefore, the adhesive strength of the hydrocolloid composition layer (b2) is evaluated by measuring the adhesive strength against the skin surface and the adhesive strength against YUPO.
　ハイドロコロイド組成物層（ｂ２）の皮膚面に対する粘着力は、好ましくは０．３～２Ｎ／１５ｍｍ、より好ましくは０．４～１．５Ｎ／１５ｍｍ、更に好ましくは０．５～１Ｎ／１５ｍｍの範囲である。また、好ましくは、皮膚面に対するハイドロコロイド組成物層（ｂ２）の粘着力を、皮膚面に対する粘着テープ（ａ）の粘着力より小さくすることにより、創傷部位及び健常皮膚に損傷を与えることなく貼付材を剥離することができる。皮膚面に対するハイドロコロイド組成物層（ｂ２）の粘着力の測定方法は、以下のとおりである。すなわち、幅１５ｍｍ×長さ１５ｍｍ以上、好ましくは７０ｍｍの所定の長さに裁断したハイドロコロイド組成物層（ｂ２）〔あらかじめ形成したハイドロコロイド組成物層（ｂ２）でもよいし、柔軟性のあるフィルム層（ｂ１）と一体となったハイドロコロイド組成物層（ｂ２）でもよい。〕を支持テープに固定し、該支持テープの反対側の面にあるハイドロコロイド組成物層（ｂ２）を、所定人数の被験者の前腕内側部位 (肘から手首方向に向かって３０～６５％の範囲とする。) に貼付し、手のひらを１０秒間押し当てて圧着する。貼付してから２０分間経過した後、ＪＩＳ　Ｚ０２３７に準拠し、剥離角度９０°、剥離速度１００ｍｍ／分の条件で、粘着力を測定する。 The adhesive strength of the hydrocolloid composition layer (b2) to the skin surface is preferably in the range of 0.3 to 2 N / 15 mm, more preferably 0.4 to 1.5 N / 15 mm, still more preferably 0.5 to 1 N / 15 mm. It is. Preferably, the adhesive material of the hydrocolloid composition layer (b2) on the skin surface is made smaller than the adhesive force of the adhesive tape (a) on the skin surface, so that the wound site and healthy skin are not damaged. Can be peeled off. The method for measuring the adhesion of the hydrocolloid composition layer (b2) to the skin surface is as follows. That is, the hydrocolloid composition layer (b2) cut to a predetermined length of 15 mm in width × 15 mm in length, preferably 70 mm [may be a preliminarily formed hydrocolloid composition layer (b2) or a flexible film layer ( It may be a hydrocolloid composition layer (b2) integrated with b1). Is fixed to the support tape, and the hydrocolloid composition layer (b2) on the opposite surface of the support tape is set to a range of 30 to 65% of the forearm inner region heel (from the elbow toward the wrist) of a predetermined number of subjects. Affix to the heel and press the palm for 10 seconds to crimp. After 20 minutes have elapsed since the application, the adhesive strength is measured in accordance with JIS Z0237 under conditions of a peeling angle of 90 ° and a peeling speed of 100 mm / min.
　柔軟性のあるフィルム層（ｂ１）に対する投錨性を良好に保つために、ハイドロコロイド組成物層（ｂ２）の対ユポ粘着力は、好ましくは０．３～４Ｎ／１５ｍｍ、より好ましくは０．４～３．５Ｎ／１５ｍｍ、更に好ましくは０．５～３Ｎ／１５ｍｍの範囲である。また、好ましくは、ハイドロコロイド組成物層（ｂ２）の対ユポ粘着力を、粘着テープ（ａ）の対ユポ粘着力より小さくすることにより、貼付材を皮膚面から剥離するときに、粘着テープ（ａ）からのパッド層（ｂ）の脱落を防止することができる。ハイドロコロイド組成物層（ｂ２）の対ユポ粘着力の測定方法は、以下のとおりである。すなわち、ハイドロコロイド組成物層（ｂ２）〔あらかじめ形成したハイドロコロイド組成物層（ｂ２）でもよいし、柔軟性のあるフィルム層（ｂ１）と一体となったハイドロコロイド組成物層（ｂ２）でもよい。〕を支持テープに固定し、幅１５ｍｍ×長さ１５ｍｍ以上、好ましくは、７０ｍｍに裁断して試験片とする。一方、ベークライト製試験パネルに、ユポ（登録商標）ＦＰＧ－１３０ (株式会社ユポ・コーポレーション製の合成紙) を両面テープで貼り付けて対ユポ粘着力試験パネルを作製する。試験片を試験パネルに押しつけて貼着させる。貼着してから２０分間経過した後、ＪＩＳ　Ｚ０２３７に準拠し、剥離角度９０°、剥離速度１００ｍｍ／分の条件で、粘着力を測定する。 In order to keep the anchoring property to the flexible film layer (b1) in good condition, the hydrocolloid composition layer (b2) has an adhesive strength to YUPO of preferably 0.3 to 4 N / 15 mm, more preferably 0.4 to The range is 3.5 N / 15 mm, more preferably 0.5 to 3 N / 15 mm. Preferably, when the adhesive material is peeled from the skin surface by reducing the adhesive strength of the hydrocolloid composition layer (b2) to less than the adhesive strength of the adhesive tape (a), the adhesive tape (a ) From the pad layer (b) can be prevented. The method for measuring the YUPO adhesive strength of the hydrocolloid composition layer (b2) is as follows. That is, the hydrocolloid composition layer (b2) [the previously formed hydrocolloid composition layer (b2) may be used, or the hydrocolloid composition layer (b2) integrated with the flexible film layer (b1) may be used. ] Is fixed to the support tape, and is cut into a width of 15 mm × length of 15 mm or more, preferably 70 mm to obtain a test piece. On the other hand, a YUPO (registered trademark) FPG-130 (synthetic paper manufactured by YUPO Corporation) is attached to a Bakelite test panel with a double-sided tape to produce a YUPO adhesion test panel. The test piece is pressed against the test panel and adhered. After 20 minutes have passed since sticking, the adhesive strength is measured under the conditions of a peeling angle of 90 ° and a peeling speed of 100 mm / min according to JIS Z0237.
８．貼付材
　本発明の貼付材は、弾性繊維から形成した布帛からなる支持体層（ａ１）と、合成樹脂を含有する通気性を有する粘着剤層（ａ２）とからなる粘着テープ（ａ）、及び、該合成樹脂を含有する通気性を有する粘着剤層（ａ２）に隣接する柔軟性のあるフィルム層（ｂ１）と、ハイドロコロイド組成物層（ｂ２）とからなるパッド層（ｂ）を備える貼付材である。 8). The adhesive material of the present invention comprises an adhesive tape (a) comprising a support layer (a1) made of a fabric formed from elastic fibers, and an air-permeable adhesive layer (a2) containing a synthetic resin, and A patch comprising a pad layer (b) comprising a flexible film layer (b1) adjacent to the air-permeable pressure-sensitive adhesive layer (a2) containing the synthetic resin and a hydrocolloid composition layer (b2) It is.
　本発明の貼付材は、上記（ａ１）～（ｂ２）の各層を順に積層してなる貼付材であって、特に、
（１）弾性繊維から形成した布帛からなる支持体層（ａ１）を備えることにより、伸縮性、透湿性、皮膚への追随性及び引張強度に優れた貼付材を提供することができ、
（２）合成樹脂を含有する通気性を有する粘着剤層（ａ２）を備えることにより、透湿性、通気性、クッション性及び皮膚への追随性に優れ、皮膚刺激性が少ない貼付材を提供することができ、
（３）柔軟性のあるフィルム層（ｂ１）を、合成樹脂を含有する通気性を有する粘着剤層（ａ２）に隣接させ、ハイドロコロイド組成物層（ｂ２）を積層してパッド層（ｂ）を形成することにより、ハイドロコロイド組成物層（ｂ２）が、創傷部位からの浸出液や貼付材の外部環境からの水分によって崩壊することがなく、
（４）特に、粘着テープ（ａ）は、弾性繊維から形成した布帛からなる支持体層（ａ１）と、合成樹脂を含有する通気性を有する粘着剤層（ａ２）とからなることから、通常、パッド層（ｂ）より伸張性に富んでおり、その結果、皮膚面への貼付と皮膚面からの剥離操作が容易となり、また、貼付中の皮膚の屈曲に追随しやすくなるので、
透湿性、日常防水性、皮膚への追随性及び引張強度に優れ、健常な皮膚の白化を防ぎ、皮膚刺激性が少ない貼付材を提供することができる。 The patch of the present invention is a patch formed by sequentially laminating the layers (a1) to (b2) above, and in particular,
(1) By providing the support layer (a1) made of a fabric formed from elastic fibers, it is possible to provide a patch material excellent in stretchability, moisture permeability, followability to skin, and tensile strength,
(2) By providing the air-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin, an adhesive material that is excellent in moisture permeability, air permeability, cushioning and followability to the skin and has little skin irritation is provided. It is possible,
(3) The flexible film layer (b1) is adjacent to the air-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin, and the hydrocolloid composition layer (b2) is laminated to form the pad layer (b). By forming, the hydrocolloid composition layer (b2) does not collapse due to exudate from the wound site or moisture from the external environment of the patch,
(4) In particular, the pressure-sensitive adhesive tape (a) is usually composed of a support layer (a1) made of a fabric formed from elastic fibers and a gas-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin. The pad layer (b) is more extensible than the pad layer, and as a result, the application to the skin surface and the peeling operation from the skin surface are facilitated, and it is easy to follow the bending of the skin during application.
It is possible to provide a patch that is excellent in moisture permeability, daily waterproofing, followability to skin and tensile strength, prevents whitening of healthy skin, and has little skin irritation.
　更に詳述すると、ハイドロコロイド組成物層（ｂ２）で吸収された創傷部位からの過剰な浸出液は、該パッド層上面に配置した柔軟性のあるフィルム層（ｂ１）により、横方向に拡散され、該柔軟性のあるフィルム層（ｂ１）周辺に移動し、合成樹脂を含有する通気性を有する粘着剤層（ａ２）、及び、弾性繊維から形成した布帛からなる支持体層（ａ１）により、速やかに外界に揮散される。よって、正常な皮膚は、前記の過剰な浸出液をほとんど保持しないため、貼付材の剥離時に健常な皮膚が白化することを防ぐことができる。 More specifically, excess leachate from the wound site absorbed by the hydrocolloid composition layer (b2) is diffused laterally by the flexible film layer (b1) disposed on the upper surface of the pad layer, By moving to the periphery of the flexible film layer (b1), the breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin, and the support layer (a1) made of a fabric formed from elastic fibers can be quickly used. Volatilized to the outside world. Therefore, normal skin hardly retains the above-mentioned excessive exudate, and can prevent whitening of healthy skin when the patch is peeled off.
　また、すり傷、かき傷、靴ずれなど、浸出液が比較的少ない創傷がある皮膚面に貼付する場合は、ハイドロコロイド組成物層（ｂ２）は、適度な粘着性を有しているため、傷とその周辺の皮膚を覆うように接着する。その結果、該ハイドロコロイド組成物層（ｂ２）が、浸出液を吸収することによって、適度に粘着力が低下するので、創傷部位の湿潤環境が整えられる。一方、パッド層（ｂ）より外側に位置する健常な皮膚は、弾性繊維から形成した布帛からなる支持体層（ａ１）と合成樹脂を含有する通気性を有する粘着剤層（ａ２）からなる粘着テープ（ａ）が、高透湿性であるため、２４時間程度皮膚に貼付した場合でも皮膚からの水分の蒸散を妨げることに起因する皮膚の白化を防ぐことができる。 In addition, when applying to a skin surface having a wound with relatively little exudate, such as a scratch, a scratch, a shoe slip, etc., the hydrocolloid composition layer (b2) has appropriate adhesiveness. Glue to cover the surrounding skin. As a result, since the hydrocolloid composition layer (b2) absorbs the leachate, the adhesive strength is appropriately reduced, so that the wet environment of the wound site is adjusted. On the other hand, the healthy skin located outside the pad layer (b) has a pressure-sensitive adhesive layer composed of a support layer (a1) made of a fabric formed of elastic fibers and a breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin. Since the tape (a) is highly moisture permeable, it can prevent whitening of the skin caused by preventing moisture from evaporating even when it is applied to the skin for about 24 hours.
　また、ハイドロコロイド組成物層（ｂ２）の背面には、柔軟性のあるフィルム層（ｂ１）が積層されているため、手洗い、食器洗い、入浴など、日常の生活活動で水を使用する場面においても、パッド層（ｂ）への水の侵襲を防ぐことができるので、該ハイドロコロイド組成物層（ｂ２）が必要以上に吸水して膨張することがない。 Moreover, since the flexible film layer (b1) is laminated on the back surface of the hydrocolloid composition layer (b2), even in a scene where water is used in daily life activities such as hand washing, dishwashing, bathing, etc. Since the water invasion to the pad layer (b) can be prevented, the hydrocolloid composition layer (b2) does not absorb water more than necessary and expands.
〔ハイドロコロイド組成物層（ｂ２）の面積〕
　貼付材を貼付する皮膚における損傷部位及び健常な皮膚を保護する観点から、パッド層（ｂ）の面積を、粘着テープ（ａ）の面積に対して、好ましくは５～５０％の面積比、より好ましくは８～４７％、特に好ましくは１０～４５％の面積比とすることが望ましい。なお、弾性繊維から形成した布帛からなる支持体層（ａ１）と合成樹脂を含有する通気性を有する粘着剤層（ａ２）の面積、及び、柔軟性のあるフィルム層（ｂ１）とハイドロコロイド組成物層（ｂ２）の面積は、通常同一である。粘着テープ（ａ）とパッド層（ｂ）との面積比を、上記の比率とすることによって、ハイドロコロイド組成物層（ｂ２）が、皮膚の創傷部位を湿潤環境に保つことができ、かつ、該ハイドロコロイド組成物層（ｂ２）自体が皮膚に強く接着する必要がないため、貼付材を剥離するときの痛みや皮膚の損傷を抑えることができる。 [Area of hydrocolloid composition layer (b2)]
From the viewpoint of protecting damaged sites and healthy skin on the skin to which the patch is applied, the area of the pad layer (b) is preferably 5 to 50% of the area of the adhesive tape (a), more The area ratio is preferably 8 to 47%, particularly preferably 10 to 45%. The area of the support layer (a1) made of a fabric formed from elastic fibers and the breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin, and the flexible film layer (b1) and hydrocolloid composition The area of the layer (b2) is usually the same. By setting the area ratio of the adhesive tape (a) and the pad layer (b) to the above ratio, the hydrocolloid composition layer (b2) can keep the wound site of the skin in a moist environment, and the Since the hydrocolloid composition layer (b2) itself does not need to adhere strongly to the skin, it is possible to suppress pain and skin damage when the patch is peeled off.
　したがって、ハイドロコロイド組成物層（ｂ２）の面積、すなわちパッド層（ｂ）の面積が異なる貼付材を用意することによって、創傷の大きさに合わせて、最適な貼付材を選択することができる。基本的には、対象となる傷より若干大きめで、かつ正常な皮膚をなるべく覆わない程度の大きさの該パッド層を備える貼付材を選択すればよい。本発明の貼付材は、切りキズ、擦りキズ、刺しキズ、掻きキズ、靴ずれ等の創傷がある皮膚に、好ましく適用することができる。 Therefore, by preparing a patch having a different area of the hydrocolloid composition layer (b2), that is, the area of the pad layer (b), an optimum patch can be selected according to the size of the wound. Basically, it is only necessary to select a patch having a pad layer that is slightly larger than the target wound and has a size that does not cover normal skin as much as possible. The patch of the present invention can be preferably applied to skin having a wound such as a cut, scratch, stab, scratch, and shoe slip.
　また、弾性繊維から形成した布帛からなる支持体層（ａ１）、合成樹脂を含有する通気性を有する粘着剤層（ａ２）、柔軟性のあるフィルム層（ｂ１）、及びハイドロコロイド組成物層（ｂ２）の各層の厚みは、先に述べたとおりであるが、貼付材を皮膚面に貼付するときのハイドロコロイド組成物層（ｂ２）の端縁部のめくれを防ぎ、かつ、貼付するときや貼付継続中に皺などが生じずに皮膚面に充分に密着固定させるために、該ハイドロコロイド組成物層（ｂ２）の厚みを端縁に向かって徐々に薄くなるように傾斜させておくことが好ましい。 Further, a support layer (a1) made of a fabric formed from elastic fibers, a breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin, a flexible film layer (b1), and a hydrocolloid composition layer (b2) The thickness of each layer is as described above, but the edge of the hydrocolloid composition layer (b2) is prevented from being turned over when the patch is applied to the skin surface, and the application is continued or continued. It is preferable to incline the thickness of the hydrocolloid composition layer (b2) so as to gradually become thinner toward the edge in order to sufficiently adhere and fix the skin surface without wrinkles or the like.
〔実用評価〕
　貼付材の実用評価として、以下の方法により、皮膚のムレ、剥離時の皮膚への接着強さ、及び総合評価を行うことができる。具体的には、貼付材を、２０～５０歳代の成人の複数名を被験者とし、指の第１関節に、パッド層（ｂ）を手の甲側として貼付し、試験中に、水仕事（皿洗い等）や入浴を義務づけて、貼付してから２４時間経過後の状態を観察して評価する。 [Practical evaluation]
As a practical evaluation of the patch, the following methods can be used to evaluate skin stuffiness, adhesion strength to the skin during peeling, and comprehensive evaluation. Specifically, the adhesive was applied to multiple adults in their 20s to 50s as subjects, and the pad layer (b) was applied to the first joint of the finger on the back side of the hand. Etc.) or obligate bathing, and observe and evaluate the condition 24 hours after application.
（１）貼付部位の皮膚のムレ
　被験者において、２４時間貼付後の貼付材の貼付部位の皮膚のふやけを下記の基準で評価する。
○：　被験者のほぼ全員に、皮膚のふやけがない。
△：　被験者のうち若干名に、皮膚のふやけが認められる。
×：　被験者の過半数に、皮膚のふやけが認められる。 (1) Skin swelling at the application site In the subject, the skin dandruff at the application site of the patch after 24 hours application is evaluated according to the following criteria.
○: Almost all subjects have no skin dandruff.
Δ: Skin dandruff is observed in some subjects.
×: Skin dandruff is observed in the majority of the subjects.
（２）剥離時の皮膚への接着強さ
　貼付材を皮膚から剥がすときのパッド層（ｂ）の皮膚への接着強さ（剥離時のパッド剥離強さ）について、下記の基準で評価する。
適度：　被験者のほぼ全員が、皮膚への付着性がほどよいと感じる。
強い：　被験者の過半数が、皮膚への付着性が若干強いと感じる。
痛い：　被験者の過半数が、皮膚への付着性が強く剥離時に痛いと感じる。 (2) Adhesive strength to the skin at the time of peeling About the adhesive strength to the skin (pad peeling strength at the time of peeling) of the pad layer (b) when peeling a patch from skin, it evaluates with the following reference | standard.
Moderate: Almost all subjects feel that the adhesion to the skin is moderate.
Strong: The majority of the subjects feel that the adhesion to the skin is slightly strong.
Pain: A majority of the subjects feel strongly adhering to the skin and hurt during peeling.
（３）貼付感
　貼付材の貼付直後、指の第１関節に貼付材を貼付したまま指を数度曲げ伸ばしし、その感触を下記の基準で評価する。
○：　被験者のほぼ全員が、曲げ伸ばしに抵抗感がない。
△：　被験者のうち半数程度が、曲げ伸ばしに少し抵抗を感じる。
×：　被験者の過半数が、曲げ伸ばしで抵抗感がある。 (3) Sticking feeling Immediately after sticking the patch, the finger is bent and stretched several times with the patch applied to the first joint of the finger, and the touch is evaluated according to the following criteria.
○: Almost all subjects have no resistance to bending and stretching.
Δ: About half of the subjects feel a little resistance to bending and stretching.
X: A majority of the subjects have resistance due to bending and stretching.
（４）総合評価
　貼付後に、『付着性（貼付のしやすさ）』、『皮膚のふやけ』及び『剥離時の皮膚への接着強さ』から総合的に、各被験者が以下の５段階の評価点で評価し、被験者の平均値を求めて、総合評価とする。
　５：　良い
　４：　やや良い
　３：　普通
　２：　やや悪い
　１：　悪い (4) Comprehensive evaluation After application, each subject was evaluated on the basis of the following five levels based on “adhesiveness (ease of application)”, “skin dandruff” and “adhesion strength to the skin at the time of peeling”. Evaluate with an evaluation point, obtain the average value of subjects, and make it a comprehensive evaluation.
5: Good 4: Somewhat good 3: Normal 2: Somewhat bad 1: Bad
９．剥離紙（ｃ）
　本発明の貼付材は、さらに、剥離紙（ｃ）を備えるものとすることができる。剥離紙（ｃ）は、通常、前記ハイドロコロイド組成物層（ｂ２）の前記柔軟性のあるフィルム層（ｂ１）と反対側の面、したがって、前記合成樹脂を含有する通気性を有する粘着剤層（ａ２）の前記弾性繊維から形成した布帛からなる支持体層（ａ１）と反対側の面に積層される。本発明の貼付材は、合成樹脂を含有する通気性を有する粘着剤層（ａ２）及びハイドロコロイド組成物層（ｂ２）に対向して、剥離紙（ｃ）を配置することにより、該剥離紙（ｃ）が粘着剤の表面を覆った状態のものとして供給されることが好ましい。剥離紙（ｃ）は、貼付材の分野で慣用されているものを用いることができ、例えば、剥離剤を塗布して剥離処理した上質紙、グラシン紙等の紙基材やポリエステルフィルム等を用いることができる。剥離紙（ｃ）は、貼付材の全体を１枚で覆う寸法及び形状のものでもよく、貼付材の面積より大きいものでもよい。また、剥離紙（ｃ）は、２枚以上に区分されたものでもよく、該２枚以上の区分された剥離紙（ｃ）の少なくとも１つに折り返し部を設けてもよい。さらに、ハイドロコロイド組成物層（ｂ２）の一部以上を覆う１枚の剥離紙（ｃ）、及び該パッド層周辺の粘着テープ（すなわち、弾性繊維から形成した布帛からなる支持体層（ａ１）、及び合成樹脂を含有する通気性を有する粘着剤層（ａ２）上に２枚以上の剥離紙（ｃ）を配置して、合計３枚以上に区分された剥離紙（ｃ）とすることもできる。また、剥離紙（ｃ）塗布する剥離剤の選択、並びに、合成樹脂を含有する通気性を有する粘着剤層（ａ２）及びハイドロコロイド組成物層（ｂ２）の選択などにより、粘着テープ（ａ）と剥離紙との剥離力を、パッド層（ｂ）と剥離紙との剥離力より大きくすることによって、貼付材からの剥離紙の剥離を容易として、取り扱い性を向上させるとともに、貼付材からのパッド層の脱落を防止することが好ましい。 9. Release paper (c)
The patch of the present invention can further include release paper (c). The release paper (c) is usually a surface opposite to the flexible film layer (b1) of the hydrocolloid composition layer (b2), and thus has a breathable pressure-sensitive adhesive layer containing the synthetic resin ( It is laminated on the surface opposite to the support layer (a1) made of a fabric formed from the elastic fiber of a2). The patch of the present invention has a release paper (c) disposed opposite to the air-permeable pressure-sensitive adhesive layer (a2) and hydrocolloid composition layer (b2) containing a synthetic resin. It is preferable that c) is supplied in a state of covering the surface of the pressure-sensitive adhesive. As the release paper (c), those commonly used in the field of patch materials can be used. For example, a high-quality paper, a paper substrate such as glassine paper, a polyester film, or the like that has been subjected to a release treatment by applying a release agent is used. be able to. The release paper (c) may be of a size and shape that covers the entire patch with a single sheet, or may be larger than the area of the patch. Further, the release paper (c) may be divided into two or more sheets, and at least one of the two or more divided release papers (c) may be provided with a folded portion. Furthermore, one release paper (c) covering a part or more of the hydrocolloid composition layer (b2), and an adhesive tape around the pad layer (that is, a support layer (a1) made of a fabric formed from elastic fibers, In addition, two or more release papers (c) may be arranged on the air-permeable pressure-sensitive adhesive layer (a2) containing the synthetic resin, so that a release paper (c) divided into a total of 3 or more can be obtained. Further, the adhesive tape (a) can be selected by selecting the release agent to be applied to the release paper (c) and selecting the air-permeable adhesive layer (a2) and hydrocolloid composition layer (b2) containing a synthetic resin. By making the release force between the adhesive layer and the release paper larger than the release force between the pad layer (b) and the release paper, it is easy to release the release paper from the adhesive material, and the handling property is improved. Prevents the pad layer from falling off It is preferable.
１０．貼付材の製造方法
　本発明の貼付材の製造方法は、特に限定されず、従来の貼付材の製造方法で作製することができる。例えば、シリコーン系剥離剤等を塗布した工程紙上に、粘着剤となる合成樹脂の溶液またはエマルションを塗工し、該粘着剤を発泡させることによって、合成樹脂を含有する通気性を持つ、好ましくは発泡した粘着剤層（ａ２）を形成した後に、弾性繊維から形成した布帛からなる支持体層（ａ１）と積層する方法によって、粘着テープ（ａ）を用意することができる。一方、柔軟性のあるフィルム層（ｂ１）と、その上に形成したハイドロコロイド組成物層（ｂ２）とを適切な大きさに裁断し、前記の粘着テープ（ａ）上の略中央に配置し、通常は、更に剥離紙（ｃ）を配置して、絆創膏の形状（通常、小判形）等に裁断して、貼付材を得る。通常は、後の工程で室温において、紙、プラスチックフィルム、またはそれらの複合材で形成された包装紙中に貼付材を封入して製品となる。 10. Method for Manufacturing Patch Material The method for manufacturing the patch material of the present invention is not particularly limited, and can be produced by a conventional method for manufacturing a patch material. For example, by applying a synthetic resin solution or emulsion to be a pressure-sensitive adhesive on a process paper coated with a silicone release agent, and foaming the pressure-sensitive adhesive, it has a breathability containing a synthetic resin, preferably After forming the foamed pressure-sensitive adhesive layer (a2), the pressure-sensitive adhesive tape (a) can be prepared by a method of laminating the support layer (a1) made of a fabric formed from elastic fibers. On the other hand, the flexible film layer (b1) and the hydrocolloid composition layer (b2) formed thereon are cut into an appropriate size, and are arranged at the approximate center on the adhesive tape (a). Usually, a release paper (c) is further arranged and cut into a bandage shape (usually an oval shape) or the like to obtain a patch. Usually, a patch is enclosed in a wrapping paper formed of paper, a plastic film, or a composite material thereof at room temperature in a later step to obtain a product.
　以下に実施例及び比較例を示して本発明を更に説明するが、本発明は本実施例に限定されるものではない。実施例及び比較例における物性または特性の測定方法は、以下のとおりである。 Hereinafter, the present invention will be further described with reference to examples and comparative examples, but the present invention is not limited to these examples. The measuring method of the physical property or characteristic in an Example and a comparative example is as follows.
〔透湿度〕
　粘着テープ（ａ）及び柔軟性のあるフィルム層（ｂ１）の透湿度は、ＪＩＳ　Ｚ０２０８の（塩化カルシウム法）に従って、温度４０℃、相対湿度９０％の測定条件で測定した。 [Moisture permeability]
The moisture permeability of the adhesive tape (a) and the flexible film layer (b1) was measured under the measurement conditions of a temperature of 40 ° C. and a relative humidity of 90% according to JIS Z0208 (calcium chloride method).
〔粘着テープ（ａ）の通気度〕
　粘着テープ（ａ）の通気度は、ＪＩＳ　Ｐ８１１７に準拠して、ガーレー式デンソメーター（テスター産業株式会社）を使用して測定した。具体的には、５ｃｍ×５ｃｍの大きさに裁断した粘着テープ（ａ）を、剥離紙がある場合は該剥離紙を剥がして、締付板（土台）に貼付した。締付板を透過する面積は６４５．１６ｍｍ２とした。ガーレー式デンソメーターの内側シリンダーを引き出し、ストッパーにセットした後、締付板の間に試験片を締め付け、内側シリンダーを静かに下降させ、３００ｃｍ３の空気量が通過する秒数を測定して、通気度（秒／３００ｃｍ３）とした。測定は、６００秒間経過まで行い、６００秒間経過時に３００ｃｍ３の空気量が通過しない場合は、通気度（秒／３００ｃｍ３）を、「＞６００（秒／３００ｃｍ３）」とした。 [Air permeability of adhesive tape (a)]
The air permeability of the adhesive tape (a) was measured using a Gurley type densometer (Tester Sangyo Co., Ltd.) in accordance with JIS P8117. Specifically, the adhesive tape (a) cut to a size of 5 cm × 5 cm was peeled off when there was release paper, and was stuck on a clamping plate (base). The area permeating through the clamping plate was 645.16 mm 2 . Pull the inner cylinder Gurley Densometer, after setting the stopper, tighten the specimen plates tightening, gently lower the inner cylinder, by measuring the number of seconds to pass the air quantity of 300 cm 3, air permeability (Second / 300 cm 3 ). The measurement was performed until 600 seconds had elapsed, and when an air amount of 300 cm 3 did not pass after the elapse of 600 seconds, the air permeability (seconds / 300 cm 3 ) was set to “> 600 (seconds / 300 cm 3 )”.
〔粘着テープ（ａ）の粘着力〕
　粘着テープ（ａ）の粘着力は、幅１５ｍｍ×長さ１００ｍｍに裁断した粘着テープ（ａ）を試験片とした。一方、ベークライト製試験パネルに、ユポ（登録商標）ＦＰＧ－１３０ (株式会社ユポ・コーポレーション製の合成紙) を両面テープで貼り付けて対ユポ粘着力試験パネルを作製した。試験片をこの試験パネルに押しつけて貼着させた。貼着してから２０分間経過した後、ＪＩＳ　Ｚ０２３７に準拠し、剥離角度１８０°、剥離速度３００ｍｍ／分の条件で、対ユポ粘着力を測定した。 [Adhesive strength of adhesive tape (a)]
The pressure-sensitive adhesive force of the pressure-sensitive adhesive tape (a) was a pressure-sensitive adhesive tape (a) cut into a width of 15 mm and a length of 100 mm. On the other hand, YUPO (registered trademark) FPG-130 (synthetic paper made by YUPO Corporation) was attached to a Bakelite test panel with a double-sided tape to produce a YUPO adhesion test panel. The test piece was pressed against the test panel and adhered. After 20 minutes had elapsed from the sticking, the adhesive strength against YUPO was measured under the conditions of a peeling angle of 180 ° and a peeling speed of 300 mm / min in accordance with JIS Z0237.
〔ハイドロコロイド組成物層（ｂ２）の粘着力〕
　ハイドロコロイド組成物層（ｂ２）の粘着力は、以下の方法により、１）皮膚面に対する粘着力と、２）対ユポ粘着力とを測定して、評価した。
１）皮膚面に対するハイドロコロイド組成物層（ｂ２）の粘着力は、以下の方法によって測定した、すなわち、あらかじめ形成したハイドロコロイド組成物層（ｂ２）を幅１５ｍｍ×長さ７０ｍｍに裁断して、支持テープに固定し、該ハイドロコロイド組成物層（ｂ２）を、成人男子３名の被験者の前腕内側部位 (肘から手首方向に向かって３０～６５％の範囲とした。) に貼付し、手のひらを１０秒間押し当てて圧着した。貼付してから２０分間経過した後、ＪＩＳ　Ｚ０２３７に準拠し、剥離角度９０°、剥離速度１００ｍｍ／分の条件で、粘着力を測定した。
２）ハイドロコロイド組成物層（ｂ２）の対ユポ粘着力は、以下の方法によって測定した、すなわち、ハイドロコロイド組成物層（ｂ２）〔柔軟性のあるフィルム層（ｂ１）と一体となったハイドロコロイド組成物層（ｂ２）を使用した。〕を支持テープに固定し、幅１５ｍｍ×長さ７０ｍｍに裁断して試験片とした。一方、ベークライト製試験パネルに、ユポ（登録商標）ＦＰＧ－１３０ (株式会社ユポ・コーポレーション製の合成紙) を両面テープで貼り付けて対ユポ粘着力試験パネルを作製した。試験片を試験パネルに押しつけて貼着させた。貼着してから２０分間経過した後、ＪＩＳ　Ｚ０２３７に準拠し、剥離角度９０°、剥離速度１００ｍｍ／分の条件で、粘着力を測定した。 [Adhesive strength of hydrocolloid composition layer (b2)]
The adhesive strength of the hydrocolloid composition layer (b2) was evaluated by measuring 1) adhesive strength to the skin surface and 2) YUPO adhesive strength by the following method.
1) The adhesive strength of the hydrocolloid composition layer (b2) to the skin surface was measured by the following method, that is, the preformed hydrocolloid composition layer (b2) was cut into a width of 15 mm and a length of 70 mm, and the support tape The hydrocolloid composition layer (b2) was affixed to the inner part of the forearm of 3 adult male subjects (within the range of 30 to 65% from the elbow toward the wrist), and the palm was applied for 10 seconds. Pressed and crimped. After 20 minutes had passed since the application, the adhesive strength was measured under the conditions of a peeling angle of 90 ° and a peeling speed of 100 mm / min according to JIS Z0237.
2) The YUPO adhesive strength of the hydrocolloid composition layer (b2) was measured by the following method, that is, the hydrocolloid composition layer (b2) [the hydrocolloid composition integrated with the flexible film layer (b1). Layer (b2) was used. ] Was fixed to a support tape, and cut into a width of 15 mm and a length of 70 mm to obtain a test piece. On the other hand, YUPO (registered trademark) FPG-130 (synthetic paper made by YUPO Corporation) was attached to a Bakelite test panel with a double-sided tape to produce a YUPO adhesion test panel. The test piece was stuck to the test panel. After 20 minutes had passed from the sticking, the adhesive strength was measured under the conditions of a peeling angle of 90 ° and a peeling speed of 100 mm / min according to JIS Z0237.
〔実用評価〕
　貼付材の実用評価として、以下の方法により、皮膚のムレ、剥離時の皮膚への接着強さ、及び総合評価を行った。具体的には、実施例及び比較例の貼付材を、２０～５０歳代の成人男子３名の被験者の指の第１関節に、パッド層（ｂ）を手の甲側として貼付し、試験中に、水仕事（皿洗い等）や入浴を義務づけて、貼付してから２４時間経過後の状態を観察して評価した。 [Practical evaluation]
As a practical evaluation of the patch material, the following methods were used to evaluate skin stuffiness, adhesion strength to the skin at the time of peeling, and comprehensive evaluation. Specifically, the patch materials of Examples and Comparative Examples were affixed to the first joints of the fingers of three adult male subjects aged 20 to 50 with the pad layer (b) on the back side of the hand, and during the test Water work (washing dishes, etc.) and bathing were obligatory, and the state after 24 hours from pasting was observed and evaluated.
（１）貼付部位の皮膚のムレ
　２４時間貼付後の貼付材の貼付部位の皮膚のふやけを下記の基準で評価した。
○：　３名の被験者の全員に、皮膚のふやけがない。
△：　３名の被験者のうち１～２名に、皮膚のふやけが認められる。
×：　３名の被験者の全員に、皮膚のふやけが認められる。 (1) Skin irregularity at the site of application The skin dandruff at the site of application of the patch after application for 24 hours was evaluated according to the following criteria.
○: All three subjects have no skin dandruff.
Δ: Skin dandruff is observed in 1 to 2 of 3 subjects.
×: Skin dandruff is observed in all three subjects.
（２）剥離時の皮膚への接着強さ
　貼付材を皮膚から剥がすときのパッド層（ｂ）の皮膚への接着強さ（剥離時のパッド剥離強さ）について、下記の基準で評価した。
適度：　３名の被験者の全員が、皮膚への付着性がほどよいと感じる。
強い：　３名の被験者のうち１～２名が、皮膚への付着性が若干強いと感じる。
痛い：　３名の被験者の全員が、皮膚への付着性が強く剥離時に痛いと感じる。 (2) Adhesive strength to the skin at the time of peeling About the adhesive strength to the skin (pad peeling strength at the time of peeling) of the pad layer (b) when peeling a patch from skin, it evaluated on the following reference | standard.
Moderate: All three subjects feel good adhesion to the skin.
Strong: 1 to 2 out of 3 subjects feel a little stronger on the skin.
Pain: All three subjects feel strongly adherent to the skin and hurt when peeled.
（３）貼付感
　貼付材の貼付直後、指の第１関節に貼付材を貼付したまま指を数度曲げ伸ばしし、その感触を下記の基準で評価した。
○：　３名の被験者の全員が、曲げ伸ばしに抵抗感がない。
△：　３名の被験者のうち１～２名が、曲げ伸ばしに少し抵抗を感じる。
×：　３名の被験者の全員が、曲げ伸ばしで抵抗感がある。 (3) Sticking feeling Immediately after sticking the patch, the finger was bent and stretched several times while the patch was stuck to the first joint of the finger, and the touch was evaluated according to the following criteria.
○: All three subjects have no resistance to bending and stretching.
Δ: One to two of the three subjects feel a little resistance to bending and stretching.
X: All of the three test subjects are resistant to bending and stretching.
（４）総合評価
　貼付後に、『付着性（貼付のしやすさ）』、『皮膚のふやけ』及び『剥離時の皮膚への接着強さ』から総合的に、各被験者が以下の５段階の評価点で評価し、３名の被験者の平均値を求めて、総合評価とした。
　５：　良い
　４：　やや良い
　３：　普通
　２：　やや悪い
　１：　悪い (4) Comprehensive evaluation After application, each subject was evaluated on the basis of the following five levels based on “adhesiveness (ease of application)”, “skin dandruff” and “adhesion strength to the skin at the time of peeling”. Evaluation was made based on evaluation points, and an average value of three subjects was obtained to obtain a comprehensive evaluation.
5: Good 4: Somewhat good 3: Normal 2: Somewhat bad 1: Bad
［パッド層の形成］
　ハイドロコロイド組成物として、ＳＩＳ〔クインタック３４２１(登録商標、日本ゼオン株式会社製)〕、ＣＭＣ〔セロゲンＦ－３Ｈ(登録商標、第一工業製薬株式会社製)〕、粘着付与樹脂〔アルコンＰ１２５(登録商標、荒川化学工業株式会社製の水素化石油樹脂)〕及び流動パラフィン(和光純薬工業株式会社製)を、表１に示す配合とし、ニーダーにて均一に混合した後、押出し加工機からシリコーン処理した工程紙上に押し出して、厚み０．３３ｍｍのハイドロコロイド組成物層（ｂ２）を形成した。該ハイドロコロイド組成物層（ｂ２）に、ポリエーテル系ポリウレタンエラストマー溶液〔セイコー化成株式会社製、ラックスキン（登録商標）ＵＳ２２６８〕を、片面シリコーン処理した７５μｍ厚のポリエステルフィルムの、シリコーン処理した表面に、乾燥後厚みが１０μｍとなるように塗布し、乾燥して得たポリエーテル系ウレタンフィルムをラミネートして、柔軟性のあるフィルム層としてポリウレタンフィルム層（ｂ１）を形成した後、両面の剥離紙を除いてパッド層（ｂ）を得た。 [Formation of pad layer]
As hydrocolloid compositions, SIS [Quintac 3421 (registered trademark, manufactured by Nippon Zeon Co., Ltd.)], CMC [Serogen F-3H (registered trademark, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)], tackifying resin [Arcon P125 (registered) Trademark, hydrogenated petroleum resin manufactured by Arakawa Chemical Co., Ltd.)) and liquid paraffin (manufactured by Wako Pure Chemical Industries, Ltd.) are blended as shown in Table 1, mixed uniformly with a kneader, and then extruded from an extruder. Extruded onto the treated process paper to form a hydrocolloid composition layer (b2) having a thickness of 0.33 mm. To the hydrocolloid composition layer (b2), a polyether-based polyurethane elastomer solution (Lackskin (registered trademark) US2268, manufactured by Seiko Kasei Co., Ltd.) is subjected to silicone treatment on a 75 μm-thick polyester film subjected to silicone treatment on one side. After drying, the polyurethane urethane film (b1) is formed as a flexible film layer by laminating a polyether urethane film obtained by applying and drying to a thickness of 10 μm. Except for the pad layer (b).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
［実施例１］
　数平均分子量が２０００のポリヘキサメチレンジオールと４，４－ジフェニルメタンジイソシアネートと１，４－ブタンジオールを２軸重合機で溶融重合して、ショアＡ硬度９０のポリエーテルポリウレタン弾性体を得た。このポリウレタンを、溶融ブロー紡糸し、得られた溶融繊維群をネットコンベヤ上に落として、目付６５ｇ／ｍ２のメルトブロー不織布（厚み２４０μｍ）を得た。不織布を形成するポリウレタン弾性体繊維の平均繊維径は、１０．６μｍであった。得られたポリウレタン弾性繊維不織布に、内部強度を向上させるため、ポイント加熱圧着法により加熱エンボス加工を施して、貼付材の支持体層（ａ１）とした。加熱圧着スポットは、ＭＤ（マシン方向）及びＣＤ（幅方向）とも１．４ｍｍピッチとした。 [Example 1]
Polyhexamethylene diol having a number average molecular weight of 2,000, 4,4-diphenylmethane diisocyanate and 1,4-butanediol were melt polymerized by a biaxial polymerization machine to obtain a polyether polyurethane elastic body having a Shore A hardness of 90. This polyurethane was melt blown and the resulting molten fiber group was dropped onto a net conveyor to obtain a melt blown nonwoven fabric (thickness 240 μm) having a basis weight of 65 g / m 2 . The average fiber diameter of the polyurethane elastic fiber forming the nonwoven fabric was 10.6 μm. In order to improve internal strength, the obtained polyurethane elastic fiber nonwoven fabric was subjected to hot embossing by a point hot pressing method to obtain a support layer (a1) of a patch. The thermocompression bonding spots were set to 1.4 mm pitch in both MD (machine direction) and CD (width direction).
　一方、アクリル系粘着剤〔アクリル酸２－エチルヘキシル・酢酸ビニル・アクリル酸（８７／１０／３）１００質量部と、エポキシ系架橋剤（テトラッドＸ、三菱ガス化学株式会社製）０.０３質量部とを反応させたもの〕を、乾燥後の厚みが４０μｍとなるように、シリコーン処理した工程紙に塗工し、通気性処理として、未乾燥の塗布面に蒸留水を噴霧した後、１３０℃で加熱して、微細な孔を形成させ、通気性を有するアクリル系樹脂からなる粘着剤層（ａ２）を形成した後、上記ポリウレタン弾性繊維不織布に貼り合わせて粘着テープ（ａ）を製造した。 On the other hand, acrylic pressure-sensitive adhesive [2-ethylhexyl acrylate / vinyl acetate / acrylic acid (87/10/3) 100 parts by mass and epoxy crosslinking agent (Tetrad X, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 0.03 parts by mass Was applied to the process paper treated with silicone so that the thickness after drying was 40 μm, and as a breathable treatment, distilled water was sprayed onto the undried coated surface, and then 130 ° C. After heating to form fine pores and forming a pressure-sensitive adhesive layer (a2) made of a breathable acrylic resin, it was bonded to the polyurethane elastic fiber nonwoven fabric to produce a pressure-sensitive adhesive tape (a).
　配合１のハイドロコロイド組成物層（ｂ２）を備えるパッド層（ｂ）を、あらかじめ幅１３ｍｍ、長さ２２ｍｍにカッティングし、ポリウレタンフィルム層（ｂ１）が、前記粘着テープ（ａ）から工程紙を剥離して露出させた通気性を有するアクリル系樹脂からなる粘着剤層（ａ２）と対向するようにして、縦１２ｍｍ、横５０ｍｍの間隔を開けながら該粘着剤層（ａ２）の上に載置した。続いて、シリコーン系樹脂で剥離処理したグラシン紙からなる剥離紙（ｃ）で、粘着テープ（ａ）及びパッド層（ｂ）を覆い、幅２５ｍｍ、長さ７２ｍｍの角にＲをとった略矩形に、パッド層（ｂ）が略中心に位置するようにしながら打ち抜いて、貼付材を得た。粘着テープ（ａ）の面積に対するパッド層（ｂ）の面積の比は、約１６％であった。 The pad layer (b) having the hydrocolloid composition layer (b2) of Formulation 1 is cut in advance to a width of 13 mm and a length of 22 mm, and the polyurethane film layer (b1) peels the process paper from the adhesive tape (a). It was placed on the pressure-sensitive adhesive layer (a2) with an interval of 12 mm in length and 50 mm in width so as to face the pressure-sensitive adhesive layer (a2) made of acrylic resin having air permeability. Subsequently, a release paper (c) made of glassine paper peel-treated with a silicone resin covers the adhesive tape (a) and the pad layer (b), and is an approximately rectangular shape with R taken at the corner of 25 mm width and 72 mm length. Then, it was punched out so that the pad layer (b) was positioned substantially at the center to obtain a patch. The ratio of the area of the pad layer (b) to the area of the adhesive tape (a) was about 16%.
　得られた貼付材は、きめの細かい外観をもち、柔軟で、通気性、収縮性に優れており、そして、貼付後の外観が良好で、指に巻いた場合に巻締まりが良く、貼りごこちが良好で、フィット性に優れたものであった。この貼付材について、貼付材を構成する粘着テープ（ａ）の透湿度及び通気度、粘着剤層（ａ２）及びハイドロコロイド組成物層（ｂ２）の粘着力を測定した結果と、実用評価の結果を表２に示す。 The obtained patch has a fine-grained appearance, is flexible, has excellent breathability, and shrinkability, and has a good appearance after sticking. Was good and excellent in fit. About this patch, the results of measuring the moisture permeability and air permeability of the adhesive tape (a) constituting the patch, the adhesive strength of the adhesive layer (a2) and the hydrocolloid composition layer (b2), and the results of practical evaluation It shows in Table 2.
［実施例２］
　支持体層（ａ１）として、上記のポリウレタン弾性繊維不織布に代えて、目付１００ｇ／ｍ２のメルトブロー不織布（厚み３７０μｍ）を用いたことを除いて、実施例１と同様にして、粘着テープ（ａ）を製造し、更に貼付材を得た。得られた貼付材について、貼付材を構成する粘着テープ（ａ）の透湿度及び通気度、粘着剤層（ａ２）及びハイドロコロイド組成物層（ｂ２）の粘着力を測定した結果と、実用評価の結果を表２に示す。 [Example 2]
In the same manner as in Example 1, except that a melt blown nonwoven fabric (thickness: 370 μm) having a basis weight of 100 g / m 2 was used as the support layer (a1) instead of the polyurethane elastic fiber nonwoven fabric, an adhesive tape (a ) And a patch was obtained. About the obtained patch, the results of measuring the moisture permeability and air permeability of the pressure-sensitive adhesive tape (a) constituting the patch, the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer (a2) and the hydrocolloid composition layer (b2), and the practical evaluation The results are shown in Table 2.
［実施例３］
　パッド層（ｂ）を形成するハイドロコロイド組成物層（ｂ２）を、配合２の組成物に変更したことを除いて、実施例１と同様にして、貼付材を得た。得られた貼付材について、貼付材を構成する粘着テープ（ａ）の透湿度及び通気度、粘着剤層（ａ２）及びハイドロコロイド組成物層（ｂ２）の粘着力を測定した結果と、実用評価の結果を表２に示す。 [Example 3]
A patch was obtained in the same manner as in Example 1 except that the hydrocolloid composition layer (b2) forming the pad layer (b) was changed to the composition of Formulation 2. About the obtained patch, the results of measuring the moisture permeability and air permeability of the pressure-sensitive adhesive tape (a) constituting the patch, the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer (a2) and the hydrocolloid composition layer (b2), and the practical evaluation The results are shown in Table 2.
［実施例４］
　支持体層（ａ１）として、ポリウレタン弾性繊維不織布に代えて、ポリウレタン弾性繊維の編布（目付１７８ｇ／ｍ２）を用いたことを除いて、実施例１と同様にして、粘着テープ（ａ）を製造し、更に貼付材を得た。得られた貼付材について、貼付材を構成する粘着テープ（ａ）の透湿度及び通気度、粘着剤層（ａ２）及びハイドロコロイド組成物層（ｂ２）の粘着力を測定した結果と、実用評価の結果を表２に示す。 [Example 4]
Adhesive tape (a) in the same manner as in Example 1, except that a polyurethane elastic fiber knitted fabric (weight per unit area: 178 g / m 2 ) was used as the support layer (a1) instead of the polyurethane elastic fiber nonwoven fabric. And a patch was obtained. About the obtained patch, the results of measuring the moisture permeability and air permeability of the pressure-sensitive adhesive tape (a) constituting the patch, the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer (a2) and the hydrocolloid composition layer (b2), and the practical evaluation The results are shown in Table 2.
［比較例１］
　上記の通気性を有するアクリル系樹脂からなる粘着剤層（ａ２）に代えて、実施例１で行った通気性処理を行わずにアクリル系樹脂からなる粘着剤層を用いたことを除いて、実施例１と同様にして、粘着テープを製造し、更に貼付材を得た。この貼付材は、合成樹脂を含有する通気性を有する粘着剤層（ａ２）を備えていない。得られた貼付材について、貼付材を構成する粘着テープの透湿度及び通気度、粘着剤層及びハイドロコロイド組成物層（ｂ２）の粘着力を測定した結果と、実用評価の結果を表２に示す。 [Comparative Example 1]
In place of the pressure-sensitive adhesive layer (a2) made of acrylic resin having air permeability described above, except that the pressure-sensitive adhesive layer made of acrylic resin was used without performing the air-permeable treatment performed in Example 1, In the same manner as in Example 1, an adhesive tape was produced, and a patch was further obtained. This patch does not have a breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin. Table 2 shows the results of measuring the moisture permeability and air permeability of the adhesive tape constituting the adhesive material, the adhesive strength of the adhesive layer and the hydrocolloid composition layer (b2), and the results of practical evaluation for the obtained adhesive material. .
［比較例２］
　支持体層として、上記のポリウレタン弾性繊維不織布に代えて、ポリウレタンフィルム（目付３３．５ｇ／ｍ２）を用いたことを除いて、実施例１と同様にして、粘着テープを製造し、更に貼付材を得た。得られた貼付材について、貼付材を構成する粘着テープの透湿度及び通気度、粘着剤層（ａ２）及びハイドロコロイド組成物層（ｂ２）の粘着力を測定した結果と、実用評価の結果を表２に示す。 [Comparative Example 2]
A pressure-sensitive adhesive tape was produced in the same manner as in Example 1 except that a polyurethane film (weight per unit area: 33.5 g / m 2 ) was used as the support layer in place of the polyurethane elastic fiber nonwoven fabric. I got the material. About the obtained adhesive material, the moisture permeability and the air permeability of the adhesive tape constituting the adhesive material, the results of measuring the adhesive strength of the adhesive layer (a2) and the hydrocolloid composition layer (b2), and the results of practical evaluation are shown. It is shown in 2.
［比較例３］
　実施例１におけるポリウレタンフィルム層（ｂ１）であるポリエーテル系ポリウレタンフィルム（厚み１０μｍ）に代えて、ポリエステルフィルム〔ポリエチレンテレフタレートフィルム（ルミラー（登録商標）、東レ株式会社製、厚み２５μｍ）を用いたことを除いて、実施例１と同様にして、粘着テープを製造し、更に貼付材を得た。得られた貼付材について、貼付材を構成する粘着テープの透湿度及び通気度、粘着剤層（ａ２）及びハイドロコロイド組成物層（ｂ２）の粘着力を測定した結果と、実用評価の結果を表２に示す。 [Comparative Example 3]
Instead of the polyether-based polyurethane film (thickness 10 μm) which is the polyurethane film layer (b1) in Example 1, a polyester film [polyethylene terephthalate film (Lumirror (registered trademark), manufactured by Toray Industries, Inc., thickness 25 μm) was used. A pressure-sensitive adhesive tape was produced in the same manner as in Example 1 except that the patch was further obtained. About the obtained adhesive material, the moisture permeability and the air permeability of the adhesive tape constituting the adhesive material, the results of measuring the adhesive strength of the adhesive layer (a2) and the hydrocolloid composition layer (b2), and the results of practical evaluation are shown. It is shown in 2.
［比較例４］
　実施例１の貼付材において、パッド層を形成するハイドロコロイド組成物を、配合３の組成物に変更するとともに、ポリウレタンフィルム層（ｂ１）を備えないことを除いて、実施例１と同様にして、粘着テープを製造し、更に貼付材を得た。得られた貼付材について、貼付材を構成する粘着テープの透湿度及び通気度、粘着剤層（ａ２）及びハイドロコロイド組成物層（ｂ２）の粘着力を測定した結果と、実用評価の結果を表２に示す。 [Comparative Example 4]
In the adhesive material of Example 1, the hydrocolloid composition forming the pad layer was changed to the composition of Formulation 3, and the polyurethane film layer (b1) was not provided, and the same as in Example 1, An adhesive tape was produced and a patch was obtained. About the obtained adhesive material, the moisture permeability and the air permeability of the adhesive tape constituting the adhesive material, the results of measuring the adhesive strength of the adhesive layer (a2) and the hydrocolloid composition layer (b2), and the results of practical evaluation are shown. It is shown in 2.
［比較例５］
　フィルムの支持体のほぼ全面にハイドロコロイド組成物が積層されている市販の貼付材（粘着テープに相当する層を備えていない。）につき、粘着力を測定した結果と、実用評価の結果を表２に示す。なお、通気度を測定したところ、６００秒／３００ｃｍ３を超過していた。 [Comparative Example 5]
Table 2 shows the results of measuring the adhesive strength and the results of practical evaluation for a commercially available patch (not provided with a layer corresponding to an adhesive tape) in which the hydrocolloid composition is laminated on almost the entire surface of the film support. Shown in In addition, when the air permeability was measured, it exceeded 600 seconds / 300 cm 3 .
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２の結果から、弾性繊維から形成した不織布や編布である布帛からなる支持体層（ａ１）と、合成樹脂を含有する通気性を有する粘着剤層（ａ２）とからなる粘着テープ（ａ）、及び、該合成樹脂を含有する通気性を有する粘着剤層（ａ２）に隣接するポリウレタンフィルム層（ｂ１）と、ハイドロコロイド組成物層（ｂ２）とからなるパッド層（ｂ）を備える実施例１～４の貼付材は、貼付材としての粘着力及び強度に優れ、さらに、通気性や実用評価が良好であることが分かった。 From the results in Table 2, a pressure-sensitive adhesive tape (a1) comprising a support layer (a1) made of a nonwoven fabric or a knitted fabric formed from elastic fibers and a breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin. And a pad layer (b) comprising a polyurethane film layer (b1) adjacent to the air-permeable pressure-sensitive adhesive layer (a2) containing the synthetic resin and a hydrocolloid composition layer (b2). It was found that the adhesive materials 1 to 4 were excellent in adhesive strength and strength as an adhesive material, and had good air permeability and practical evaluation.
　これに対して、粘着剤層として、合成樹脂を含有する通気性を有する粘着剤層（ａ２）を備えず、通気性処理を行わない非通気性アクリル系樹脂からなる粘着剤層を備える比較例１の貼付材は、貼付材の通気性が悪く、皮膚のムレが生じやすく、実用評価が低いことが分かった。支持体層として、弾性繊維から形成した布帛を備えず、ポリウレタンフィルムを備える比較例２の貼付材は、目付が小さいにもかかわらず、通気性がなく、皮膚のムレが生じ、実用評価が低いことが分かった。また、合成樹脂を含有する通気性を有する粘着剤層（ａ２）に隣接するポリウレタンフィルム層（ｂ１）に代えて、ポリエステルフィルム（ポリエチレンテレフタレート）層を備える比較例３の貼付材は、実用評価において、３名の被験者の全員が、貼付時に、指を曲げ伸ばしすると、少し抵抗感が感じられることを指摘し、貼付感が悪かった。これは、パッド層の柔軟性がなくなったためと推察され、本発明におけるポリウレタンフィルム層（ｂ１）以外の、柔軟性が損なわれるフィルムを使用した場合は同じ結果になることが示唆された。さらに、パッド層の粘着力が高いハイドロコロイド組成物層から形成された比較例４の貼付材は、貼付材剥離時に、皮膚への付着性が強く感じられた。またウレタンフィルムをハイドロコロイド背面に配さないため、水仕事を行うとハイドロコロイドが吸水し、膨潤して実用性に難があった。さらにまた、比較例４の貼付材については、皮膚刺激を指摘する被験者があった。比較例５は、３名の被験者の全員が、剥離時に皮膚への付着性が強く痛みを感じたと指摘した。 On the other hand, as a pressure-sensitive adhesive layer, a comparative example provided with a pressure-sensitive adhesive layer made of a non-breathable acrylic resin that does not include a breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin and does not perform a breathable treatment. It was found that the patch of No. 1 was poor in air permeability of the patch, apt to cause skin stuffiness, and low in practical evaluation. The adhesive material of Comparative Example 2, which does not include a fabric formed of elastic fibers as a support layer and includes a polyurethane film, has low air permeability, has no air permeability, causes skin stuffiness, and has a low practical evaluation. I understood that. Moreover, instead of the polyurethane film layer (b1) adjacent to the air-permeable pressure-sensitive adhesive layer (a2) containing a synthetic resin, the patch of Comparative Example 3 provided with a polyester film (polyethylene terephthalate) layer was used in practical evaluation. All three subjects pointed out that when they applied the fingers, they felt a little resistance when bending and stretching their fingers. This is presumed to be because the flexibility of the pad layer was lost, and it was suggested that the same result was obtained when a film other than the polyurethane film layer (b1) in the present invention was used, which lost flexibility. Furthermore, the adhesive material of Comparative Example 4 formed from the hydrocolloid composition layer having a high adhesive strength of the pad layer was strongly felt to adhere to the skin when the adhesive material was peeled off. In addition, since the urethane film is not disposed on the back surface of the hydrocolloid, when the water work is performed, the hydrocolloid absorbs water and swells, which is difficult for practical use. Furthermore, with respect to the patch of Comparative Example 4, there were subjects who pointed out skin irritation. Comparative Example 5 pointed out that all of the three subjects felt pain because of strong adhesion to the skin at the time of peeling.
　さらに、４名の被験者（成人男性）の左右ひざに対して、ミニルーター用真鍮製ワイヤーブラシを用いて均等に微出血を生じるまで擦過傷をつけた箇所に、実施例１及び比較例５の貼付材を適用し、浸出液が少なくなってきた４日間経過後に、貼付材を剥離したところ、実施例１の貼付材は、４名の被験者中４名が、容易に剥離することが可能であったが、比較例５の貼付材は、再出血は発生しなかったものの、４名の被験者中３名が、剥離時に創部周辺の著しい痛みを感じたと回答した。 In addition, the left and right knees of four subjects (adult males) were applied to Example 1 and Comparative Example 5 at locations where they were scratched using a brass wire brush for a mini router until minor bleeding occurred evenly. When the adhesive material was applied and the adhesive material was peeled off after 4 days when the exudate was reduced, the adhesive material of Example 1 was easily peelable by 4 out of 4 subjects. However, although the re-bleeding did not occur in the patch of Comparative Example 5, 3 out of 4 subjects replied that they felt significant pain around the wound at the time of peeling.
　本発明は、弾性繊維から形成した布帛からなる支持体層（ａ１）と、合成樹脂を含有する通気性を有する粘着剤層（ａ２）、該合成樹脂を含有する通気性を有する粘着剤層（ａ２）に隣接する柔軟性のあるフィルム層（ｂ１）と、ハイドロコロイド組成物層（ｂ２）とからなるパッド層（ｂ）を備える貼付材であることによって、創傷部は湿潤環境を維持し、正常な皮膚は過度な湿潤環境にならず、貼付材を皮膚から剥離するときの痛みがなく、創傷回りの正常な皮膚を変形させず、日常生活レベルの水の使用によるハイドロコロイドの崩壊を防止することができる貼付材を提供することができるので、産業上の利用可能性が高い。 The present invention comprises a support layer (a1) comprising a fabric formed from elastic fibers, a breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin, and a breathable pressure-sensitive adhesive layer containing the synthetic resin ( The wound part maintains a moist environment and is normal by being a patch comprising a pad layer (b) composed of a flexible film layer (b1) adjacent to a2) and a hydrocolloid composition layer (b2) Healthy skin does not become an excessively moist environment, there is no pain when peeling the patch from the skin, normal skin around the wound is not deformed, and the collapse of hydrocolloid due to the use of water at the daily life level is prevented Therefore, the present invention is highly applicable to the industry.
ａ１：　弾性繊維から形成した布帛からなる支持体層
ａ２：　合成樹脂を含有する通気性を有する粘着剤層
ａ：　　粘着テープ
ｂ１：　柔軟性のあるフィルム層
ｂ２：　ハイドロコロイド組成物層
ｂ：　　パッド層
ｃ：　　剥離紙 a1: Support layer made of a fabric formed from elastic fibers a2: Breathable pressure-sensitive adhesive layer containing a synthetic resin a: Adhesive tape b1: Flexible film layer b2: Hydrocolloid composition layer b: Pad layer c : Release paper

Claims (13)

  1. 　弾性繊維から形成した布帛からなる支持体層（ａ１）と、合成樹脂を含有する通気性を有する粘着剤層（ａ２）とからなる粘着テープ（ａ）、及び、
    該合成樹脂を含有する通気性を有する粘着剤層（ａ２）に隣接する柔軟性のあるフィルム層（ｂ１）と、ハイドロコロイド組成物層（ｂ２）とからなるパッド層（ｂ）
    を備える貼付材。     A pressure-sensitive adhesive tape (a) comprising a support layer (a1) made of a fabric formed from elastic fibers, and a breathable pressure-sensitive adhesive layer (a2) containing a synthetic resin; and
    A pad layer (b) comprising a flexible film layer (b1) adjacent to the air-permeable pressure-sensitive adhesive layer (a2) containing the synthetic resin and a hydrocolloid composition layer (b2)
    A patch comprising:
  2. 　前記柔軟性のあるフィルム層（ｂ１）が、ポリウレタンフィルム層である請求項１記載の貼付材。 The patch according to claim 1, wherein the flexible film layer (b1) is a polyurethane film layer.
  3. 　前記支持体層（ａ１）における弾性繊維が、平均繊維径が３～２５μｍのポリウレタン弾性繊維である請求項１記載の貼付材。 The patch according to claim 1, wherein the elastic fibers in the support layer (a1) are polyurethane elastic fibers having an average fiber diameter of 3 to 25 µm.
  4. 　前記支持体層（ａ１）における布帛が、不織布、織布または編布である請求項１記載の貼付材。 The patch according to claim 1, wherein the fabric in the support layer (a1) is a nonwoven fabric, a woven fabric or a knitted fabric.
  5. 　前記粘着剤層（ａ２）に含有される合成樹脂が、アクリル系樹脂である請求項１記載の貼付材。 The adhesive material according to claim 1, wherein the synthetic resin contained in the pressure-sensitive adhesive layer (a2) is an acrylic resin.
  6. 　前記粘着テープ（ａ）の透湿度が、２０００ｇ/ｍ２・２４ｈｒ以上である請求項１記載の貼付材。 The patch according to claim 1, wherein the pressure-sensitive adhesive tape (a) has a moisture permeability of 2000 g / m 2 · 24 hr or more.
  7. 　前記柔軟性のあるフィルム層（ｂ１）の厚みが、５～４５μｍの範囲である請求項１記載の貼付材。 The patch according to claim 1, wherein the thickness of the flexible film layer (b1) is in the range of 5 to 45 µm.
  8. 　前記ハイドロコロイド組成物層（ｂ２）が、
    ｉ）ポリイソブチレン、ポリイソプレン、スチレン・イソプレン・スチレンブロック共重合体、アクリル系エラストマー、ウレタン系エラストマー、及びシリコーン系エラストマーからなる群より選ばれる少なくとも一種であるエラストマー成分；と、
    ｉｉ）カルボキシメチルセルロース、デキストリン、ペクチン、ゼラチン、ポリアクリル酸ナトリウム、及びポリビニルピロリドンからなる群より選ばれる少なくとも一種である吸湿性物質；とを含有する請求項１記載の貼付材。     The hydrocolloid composition layer (b2)
    i) an elastomer component which is at least one selected from the group consisting of polyisobutylene, polyisoprene, styrene / isoprene / styrene block copolymer, acrylic elastomer, urethane elastomer, and silicone elastomer;
    The adhesive material according to claim 1, comprising ii) a hygroscopic substance that is at least one selected from the group consisting of carboxymethylcellulose, dextrin, pectin, gelatin, sodium polyacrylate, and polyvinylpyrrolidone.
  9. 　前記ハイドロコロイド組成物層（ｂ２）が、薬剤を含有するものである請求項１記載の貼付材。 The patch according to claim 1, wherein the hydrocolloid composition layer (b2) contains a drug.
  10. 　前記ハイドロコロイド組成物層（ｂ２）の皮膚面に対する粘着力が、０．３～２Ｎ／１５ｍｍである請求項１記載の貼付材。 The adhesive material according to claim 1, wherein the adhesive strength of the hydrocolloid composition layer (b2) to the skin surface is 0.3 to 2 N / 15 mm.
  11. 　前記粘着テープ（ａ）の面積に対する前記パッド層（ｂ）の面積の比が、５～５０％である請求項１記載の貼付材。 The adhesive material according to claim 1, wherein the ratio of the area of the pad layer (b) to the area of the adhesive tape (a) is 5 to 50%.
  12. 　前記粘着テープ（ａ）の通気度が、０．２～３５秒／３００ｃｍ３である請求項１記載の貼付材。 The patch according to claim 1, wherein the pressure-sensitive adhesive tape (a) has an air permeability of 0.2 to 35 seconds / 300 cm 3 .
  13. 　さらに剥離紙（ｃ）を備える請求項１記載の貼付材。 The patch according to claim 1, further comprising a release paper (c).
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JP2017064083A (en) * 2015-09-30 2017-04-06 株式会社麻生 Umbilical hernia treatment material fixation patch

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KR102524880B1 (en) * 2017-12-21 2023-04-21 한양대학교 산학협력단 Hydrocolloid composition and bio patch including the same
US11355822B2 (en) * 2020-01-23 2022-06-07 Duracell U.S. Operations, Inc. Battery peel off assembly for exposing a safety feature comprising an aversive agent

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JP2017064083A (en) * 2015-09-30 2017-04-06 株式会社麻生 Umbilical hernia treatment material fixation patch

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