JP2020006166A - Medical patch - Google Patents
Medical patch Download PDFInfo
- Publication number
- JP2020006166A JP2020006166A JP2019122202A JP2019122202A JP2020006166A JP 2020006166 A JP2020006166 A JP 2020006166A JP 2019122202 A JP2019122202 A JP 2019122202A JP 2019122202 A JP2019122202 A JP 2019122202A JP 2020006166 A JP2020006166 A JP 2020006166A
- Authority
- JP
- Japan
- Prior art keywords
- mass
- fatty acid
- pressure
- sensitive adhesive
- acid ester
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
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- -1 alkyl acrylate ester Chemical class 0.000 claims abstract description 99
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 67
- 239000000194 fatty acid Substances 0.000 claims abstract description 67
- 229930195729 fatty acid Natural products 0.000 claims abstract description 67
- 239000000203 mixture Substances 0.000 claims abstract description 58
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 229920001577 copolymer Polymers 0.000 claims abstract description 29
- 239000012790 adhesive layer Substances 0.000 claims abstract description 18
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 103
- 239000010410 layer Substances 0.000 claims description 76
- 239000000178 monomer Substances 0.000 claims description 33
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 229920002554 vinyl polymer Polymers 0.000 claims description 32
- 230000035699 permeability Effects 0.000 claims description 22
- 239000003431 cross linking reagent Substances 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 8
- 125000005313 fatty acid group Chemical group 0.000 claims description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 64
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- 238000012360 testing method Methods 0.000 description 32
- 206010040844 Skin exfoliation Diseases 0.000 description 25
- 239000004014 plasticizer Substances 0.000 description 23
- 239000000463 material Substances 0.000 description 18
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 14
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 14
- 239000005642 Oleic acid Substances 0.000 description 14
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 14
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 14
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- BARWIPMJPCRCTP-UHFFFAOYSA-N oleic acid oleyl ester Natural products CCCCCCCCC=CCCCCCCCCOC(=O)CCCCCCCC=CCCCCCCCC BARWIPMJPCRCTP-UHFFFAOYSA-N 0.000 description 5
- BARWIPMJPCRCTP-CLFAGFIQSA-N oleyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC BARWIPMJPCRCTP-CLFAGFIQSA-N 0.000 description 5
- 239000002759 woven fabric Substances 0.000 description 5
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- 206010040914 Skin reaction Diseases 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
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- 235000019438 castor oil Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
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- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 4
- 150000002888 oleic acid derivatives Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
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- 231100000430 skin reaction Toxicity 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 3
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 description 3
- RZRNAYUHWVFMIP-GDCKJWNLSA-N 3-oleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-GDCKJWNLSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 102000011782 Keratins Human genes 0.000 description 3
- 108010076876 Keratins Proteins 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004018 acid anhydride group Chemical group 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 210000002510 keratinocyte Anatomy 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000001593 sorbitan monooleate Substances 0.000 description 3
- 235000011069 sorbitan monooleate Nutrition 0.000 description 3
- 229940035049 sorbitan monooleate Drugs 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 2
- ABEXEQSGABRUHS-UHFFFAOYSA-N 16-methylheptadecyl 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC(C)C ABEXEQSGABRUHS-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
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- 125000000623 heterocyclic group Chemical group 0.000 description 2
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 229940035676 analgesics Drugs 0.000 description 1
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- JYTMDBGMUIAIQH-ZPHPHTNESA-N palmityl oleate Chemical compound CCCCCCCCCCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC JYTMDBGMUIAIQH-ZPHPHTNESA-N 0.000 description 1
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Classifications
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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
- A61F13/0253—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
-
- 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
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/58—Adhesives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M25/00—Catheters; Hollow probes
- A61M25/01—Introducing, guiding, advancing, emplacing or holding catheters
- A61M25/02—Holding devices, e.g. on the body
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- 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
- A61F2013/00361—Plasters
- A61F2013/00365—Plasters use
- A61F2013/00412—Plasters use for use with needles, tubes or catheters
-
- 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
- A61F2013/00361—Plasters
- A61F2013/00655—Plasters adhesive
- A61F2013/00659—Plasters adhesive polymeric base
- A61F2013/00663—Plasters adhesive polymeric base acrylic
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M25/00—Catheters; Hollow probes
- A61M25/01—Introducing, guiding, advancing, emplacing or holding catheters
- A61M25/02—Holding devices, e.g. on the body
- A61M2025/0266—Holding devices, e.g. on the body using pads, patches, tapes or the like
Abstract
Description
本発明は、粘着包帯や絆創膏等の皮膚表面に貼付される医療用貼付材、及びその粘着剤層の形成に好適な粘着剤組成物に関する。 TECHNICAL FIELD The present invention relates to a medical patch applied to a skin surface such as an adhesive bandage or a bandage, and an adhesive composition suitable for forming an adhesive layer thereof.
粘着包帯や絆創膏等の医療用貼付材は、カテーテル等のチューブ等を皮膚表面に固定する際にも用いられる。カテーテル等の固定においては、誤って剥がれることのないように安定して固定することが必要であり、このため、用いられる医療用貼付材には、高い粘着力が優先される傾向にある。一方で、カテーテル等は、長時間の固定が必要とされる場合や、皮膚の同じ部位に繰り返し固定される場合がある。このため、カテーテル等の固定に使用される医療用貼付材には、連続貼付や繰り返し貼付された場合に、皮膚への影響が少ないことが求められている。また、肩や腰といった特定の部位に貼付される鎮痛消炎剤や、磁気治療器絆創膏等も、皮膚の同じ部位に繰り返し固定される場合があり、これ等に使用される医療用貼付材も、連続貼付や繰り返し貼付された場合の皮膚への影響が少ないことが望ましい。 Medical adhesive materials such as adhesive bandages and adhesive plasters are also used when fixing tubes such as catheters to the skin surface. In fixing a catheter or the like, it is necessary to stably fix the catheter and the like so as not to be accidentally peeled off. Therefore, a high adhesive strength tends to be given priority to a medical patch to be used. On the other hand, a catheter or the like may need to be fixed for a long time, or may be repeatedly fixed to the same part of the skin. For this reason, it is required that the medical patch used for fixing a catheter or the like has little effect on the skin when continuously or repeatedly applied. In addition, analgesics and anti-inflammatory drugs that are applied to specific sites such as the shoulders and hips, magnetic treatment device plasters, and the like may also be repeatedly fixed to the same site on the skin, and medical adhesive materials used for these, It is desirable that there is little effect on the skin when it is continuously or repeatedly applied.
皮膚への刺激が抑えられた医療用貼付材としては、例えば特許文献1には、粘着剤として、重量平均分子量250万以上のアクリル酸エステル系ポリマーに、これに相溶する脂肪酸エステルを液状可塑剤として含有させた粘着剤組成物を用いた医療用貼付材が記載されている。接着性が良好なアクリル酸エステル系ポリマーを粘着剤層とし、これに相溶する脂肪酸エステルを液状可塑剤として含有させることにより、粘着剤層が可塑化されて柔らかくなり、皮膚刺激性が低減される。 As a medical patch with reduced skin irritation, for example, Patent Literature 1 discloses an acrylic acid-based polymer having a weight average molecular weight of 2.5 million or more as a pressure-sensitive adhesive, and a fatty acid ester compatible with the acrylic acid-based polymer. A medical patch using a pressure-sensitive adhesive composition contained as an agent is described. The adhesive layer is made of an acrylic ester polymer having good adhesiveness, and a fatty acid ester compatible with this is contained as a liquid plasticizer, whereby the adhesive layer is plasticized and softened, and skin irritation is reduced. You.
また、粘着剤層に液状可塑剤を配合した粘着剤層を備える医療用貼付材としては、例えば特許文献2には、(メタ)アクリル酸アルキルエステルを乳化重合して得られた共重合体からなるアクリル系粘着剤に、脂肪酸エステルなどの液状可塑剤を添加した粘着剤層を支持体に形成した貼付材が開示されている。 Further, as a medical patch having an adhesive layer in which a liquid plasticizer is blended into the adhesive layer, for example, Patent Document 2 discloses a polymer obtained by emulsion polymerization of alkyl (meth) acrylate. There is disclosed a patch in which a pressure-sensitive adhesive layer obtained by adding a liquid plasticizer such as a fatty acid ester to an acrylic pressure-sensitive adhesive is formed on a support.
本発明は、充分な粘着力を有しつつ、皮膚の同じ部位に繰り返し貼付された場合に皮膚への影響が小さい医療用貼付材を提供することを目的とする。 An object of the present invention is to provide a medical adhesive material having sufficient adhesive strength and having little effect on the skin when repeatedly applied to the same part of the skin.
本発明者らは、医療用貼付材の粘着剤層を構成するアクリル系粘着剤を、アクリル系共重合体100質量部に対して、分子量が350〜550であり、室温で液状の脂肪酸エステルを5〜25質量部含有させ、さらに、透湿度が500g/m2・24h以上である支持体とすることにより、ヒト皮膚への高い粘着力を維持しつつ、角質剥離面積率が低減された医療用貼付材が得られることを見出し、本発明を完成させた。 The present inventors prepared an acrylic pressure-sensitive adhesive constituting a pressure-sensitive adhesive layer of a medical patch, by using a fatty acid ester having a molecular weight of 350 to 550 and a liquid at room temperature with respect to 100 parts by mass of an acrylic copolymer. By providing a support having 5 to 25 parts by mass and having a moisture permeability of 500 g / m 2 · 24 h or more, a medical treatment in which the exfoliation area ratio is reduced while maintaining high adhesive strength to human skin The present inventors have found that an adhesive material for use can be obtained and completed the present invention.
すなわち、本発明は、以下の医療用貼付材を提供するものである。
[1] 支持体と粘着剤層の積層体を備える医療用貼付材であって、
前記粘着剤層が、(メタ)アクリル酸アルキルエステルを主成分とした共重合体と、室温で液状の前記共重合体と相溶する脂肪酸エステルとを含有する粘着剤組成物からなり、
前記粘着剤組成物に含有されている前記脂肪酸エステルの質量平均分子量が350〜550であり、
前記粘着剤組成物は、前記共重合体100質量部に対して、前記脂肪酸エステルを5〜25質量部含有しており、
前記支持体の透湿度が500g/m2・24h以上である、
医療用貼付材。
[2] 前記脂肪酸エステルが、分子量350〜550である単一種の脂肪酸エステルを含有する、前記[1]の医療用貼付材。
[3] 前記共重合体が、炭素数が8〜12のアルキル基を有するアクリル酸アルキルエステルが65〜90質量%と、アクリル酸が2〜15質量%と、酢酸ビニルが5〜25質量%と、その他のビニル単量体が0〜10質量%とが溶液重合法により重合した共重合体を、架橋剤にて架橋させたものである、前記[1]又は[2]の医療用貼付材。
[4] 前記脂肪酸エステルが、少なくとも1個のオレイン酸残基を有する、前記[1]〜[3]のいずれかの医療用貼付材。
[5] 前記脂肪酸エステル中の脂肪酸残基が、全てオレイン酸残基である、前記[4]の医療用貼付材。
[6] さらに、前記粘着剤層の前記支持体と接している面とは逆の面にセパレーター層を備える、前記[1]〜[5]のいずれかの医療用貼付材。
[7] 皮膚の同じ部位に繰り返し貼付される、前記[1]〜[6]のいずれかの医療用貼付材。
[8] チューブ固定用である、前記[1]〜[7]のいずれかの医療用貼付材。
That is, the present invention provides the following medical patch.
[1] A medical patch comprising a laminate of a support and an adhesive layer,
The pressure-sensitive adhesive layer comprises a pressure-sensitive adhesive composition containing a copolymer containing (meth) alkyl acrylate as a main component and a fatty acid ester compatible with the copolymer which is liquid at room temperature,
The fatty acid ester contained in the pressure-sensitive adhesive composition has a mass average molecular weight of 350 to 550,
The pressure-sensitive adhesive composition contains 5 to 25 parts by mass of the fatty acid ester based on 100 parts by mass of the copolymer.
The moisture permeability of the support is 500g / m 2 · 24h or more,
Medical patch.
[2] The medical patch according to [1], wherein the fatty acid ester contains a single type of fatty acid ester having a molecular weight of 350 to 550.
[3] The copolymer has 65 to 90% by mass of an alkyl acrylate having an alkyl group having 8 to 12 carbon atoms, 2 to 15% by mass of acrylic acid, and 5 to 25% by mass of vinyl acetate. And the medical adhesive according to [1] or [2], wherein a copolymer obtained by polymerizing 0 to 10% by mass of another vinyl monomer by a solution polymerization method is cross-linked with a cross-linking agent. Wood.
[4] The medical patch according to any one of [1] to [3], wherein the fatty acid ester has at least one oleic acid residue.
[5] The medical patch according to [4], wherein the fatty acid residues in the fatty acid ester are all oleic acid residues.
[6] The medical patch according to any one of [1] to [5], further including a separator layer on a surface of the pressure-sensitive adhesive layer opposite to a surface in contact with the support.
[7] The medical patch according to any one of [1] to [6], which is repeatedly adhered to the same site on the skin.
[8] The medical patch according to any one of [1] to [7], which is for fixing a tube.
本発明によれば、高い粘着力を維持しつつ、皮膚の同じ部位に連続貼付又は繰り返し貼付した際にも皮膚刺激が低い粘着剤組成物により粘着剤層が形成された医療用貼付材を提供することができる。 According to the present invention, there is provided a medical patch in which a pressure-sensitive adhesive layer is formed by a pressure-sensitive adhesive composition having low skin irritation even when continuously or repeatedly applied to the same part of the skin while maintaining high adhesive strength. can do.
<粘着剤組成物>
本発明に係る医療用貼付材の粘着剤層を構成する粘着剤組成物は、(メタ)アクリル酸アルキルエステルを主成分とした共重合体と、室温(1〜30℃)で液状の脂肪酸エステルとを含有する。当該脂肪酸エステルは、粘着剤である(メタ)アクリル酸アルキルエステルを主成分とした共重合体に対して相溶であり、可塑性を付与する液状可塑剤である。
<Adhesive composition>
The pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer of the medical patch according to the present invention comprises a copolymer containing (meth) alkyl acrylate as a main component and a fatty acid ester liquid at room temperature (1 to 30 ° C.). And The fatty acid ester is a liquid plasticizer that is compatible with a copolymer containing an alkyl (meth) acrylate as an adhesive as a main component and imparts plasticity.
((メタ)アクリル酸アルキルエステルを主成分とした共重合体)
(メタ)アクリル酸アルキルエステルを主成分とした共重合体(以下、「アクリル系共重合体」ということがある。)とは、共重合体を構成する全構成単位に対する50%以上が(メタ)アクリル酸アルキルエステルに由来する構成単位である共重合体を意味する。なお、本発明及び本願明細書において、(メタ)アクリル酸アルキルエステルとは、「アクリル酸アルキルエステル及び/又はメタクリル酸アルキルエステル」を表す。
(Copolymer based on alkyl (meth) acrylate)
A copolymer containing (meth) acrylic acid alkyl ester as a main component (hereinafter sometimes referred to as an “acrylic copolymer”) means that 50% or more of all the constituent units constituting the copolymer are (meth) ) Means a copolymer which is a structural unit derived from an alkyl acrylate. In the present invention and the present specification, the term “alkyl (meth) acrylate” means “alkyl acrylate and / or alkyl methacrylate”.
当該共重合体の構成単位が由来する(メタ)アクリル酸アルキルエステルとしては、アルキル基部分の炭素数が1〜18である(メタ)アクリル酸アルキルエステルが好ましい。具体的には、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n−ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸t−ブチル、(メタ)アクリル酸n−ヘキシル、(メタ)アクリル酸n−オクチル、(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸n−デシル、(メタ)アクリル酸イソデシル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸ステアリル等が挙げられる。これらの(メタ)アクリル酸アルキルエステルは、それぞれ単独で、又は2種以上を組み合わせて用いることができる。 As the alkyl (meth) acrylate from which the structural unit of the copolymer is derived, an alkyl (meth) acrylate having 1 to 18 carbon atoms in the alkyl group is preferable. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n- (meth) acrylate -Hexyl, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate , Lauryl (meth) acrylate, stearyl (meth) acrylate and the like. These alkyl (meth) acrylates can be used alone or in combination of two or more.
本発明において用いられるアクリル系共重合体の構成単位が由来する(メタ)アクリル酸アルキルエステルとしては、炭素数が4〜18のアルキル基を有する(メタ)アクリル酸アルキルエステルが好ましく、炭素数が4〜12のアルキル基を有する(メタ)アクリル酸アルキルエステルがより好ましく、炭素数が6〜12のアルキル基を有する(メタ)アクリル酸アルキルエステルがさらに好ましく、炭素数が8〜12のアルキル基を有する(メタ)アクリル酸アルキルエステルがよりさらに好ましく、(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸n−オクチル、(メタ)アクリル酸イソオクチル、又は(メタ)アクリル酸イソノニルが特に好ましい。 As the alkyl (meth) acrylate derived from the structural unit of the acrylic copolymer used in the present invention, an alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms is preferable, and the carbon number is preferably Alkyl (meth) acrylates having an alkyl group of 4 to 12 are more preferable, and alkyl (meth) acrylates having an alkyl group of 6 to 12 carbon atoms are more preferable, and an alkyl group of 8 to 12 carbon atoms. Is more preferable, and 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, or isononyl (meth) acrylate is more preferable.
本発明において用いられるアクリル系共重合体としては、(メタ)アクリル酸アルキルエステルに由来する構成単位として、アルキル基部分の炭素数が4〜18である(メタ)アクリル酸アルキルエステルに由来する構成単位を少なくとも1種類含むものが好ましい。例えば、(メタ)アクリル酸アルキルエステルに由来する構成単位として、アルキル基部分の炭素数が4〜18である(メタ)アクリル酸アルキルエステルに由来する構成単位のみを有している共重合体であってもよく、アルキル基部分の炭素数が4〜18である(メタ)アクリル酸アルキルエステルに由来する構成単位と、これ以外の(メタ)アクリル酸アルキルエステルに由来する構成単位との両方を含む共重合体であってもよい。 As the acrylic copolymer used in the present invention, as a structural unit derived from an alkyl (meth) acrylate, a structural unit derived from an alkyl (meth) acrylate having an alkyl group portion of 4 to 18 carbon atoms is used. Those containing at least one unit are preferred. For example, as a structural unit derived from an alkyl (meth) acrylate, a copolymer having only a structural unit derived from an alkyl (meth) acrylate having 4 to 18 carbon atoms in the alkyl group portion is used. Both the structural unit derived from the alkyl (meth) acrylate having 4 to 18 carbon atoms in the alkyl group portion and the structural unit derived from the other alkyl (meth) acrylate may be used. May be included.
本発明において用いられるアクリル系共重合体としては、(メタ)アクリル酸アルキルエステルに由来する構成単位のみからなる共重合体であってもよく、その他の重合性化合物に由来する構成単位を含む共重合体であってもよい。その他の重合性化合物としては、ビニル基を有する化合物(ビニル単量体)が挙げられる。 The acrylic copolymer used in the present invention may be a copolymer composed only of a structural unit derived from an alkyl (meth) acrylate, or a copolymer containing a structural unit derived from another polymerizable compound. It may be a polymer. Other polymerizable compounds include compounds having a vinyl group (vinyl monomers).
当該ビニル単量体としては、例えば、水酸基、カルボキシル基、酸無水物基、アミド基、アミノ基、エポキシ基、アルコキシ基、アシル基、シアノ基、アリール基、複素環基等の官能基を有するビニル単量体が挙げられる。水酸基を有するビニル単量体としては、(メタ)アクリル酸2−ヒドロキシエチル、(メタ)アクリル酸3−ヒドロキシプロピル、(メタ)アクリル酸4−ヒドロキシブチル等の水酸基を有する(メタ)アクリル酸エステル等が挙げられる。カルボキシル基又は酸無水物基を有するビニル単量体としては、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸、マレイン酸モノブチル等が挙げられる。アミド基を有するビニル単量体としては、アクリルアミド、ジメチルアクリルアミド、ジエチルアクリルアミド、メタクリルアミド、N−メチロールアクリルアミド等が挙げられる。アミノ基を有するビニル単量体としては、ジメチルアミノエチルアクリレート等が挙げられる。エポキシ基を有するビニル単量体としては、アクリル酸グリシジル、メタクリル酸グリシジル等が挙げられる。アルコキシ基を有するビニル単量体としては、アクリル酸2−メトキシエチル、アクリル酸エトキシエチル等のアクリル酸アルコキシアルキルエステル等が挙げられる。アシル基を有するビニル単量体としては、酢酸ビニル等のビニルエステル等が挙げられる。シアノ基を有するビニル単量体としては、アクリロニトリル、メタクリロニトリル等の不飽和ニトリル等が挙げられる。アリール基を有するビニル単量体としては、スチレン等のビニル芳香族化合物等が挙げられる。複素環基を有するビニル単量体としては、N−ビニルピロリドン等のピロリドン環を有するビニル単量体等が挙げられる。これらのビニル単量体は、それぞれ単独で、又は2種以上を組み合わせて使用することができる。 The vinyl monomer has a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride group, an amide group, an amino group, an epoxy group, an alkoxy group, an acyl group, a cyano group, an aryl group, and a heterocyclic group. And vinyl monomers. Examples of the vinyl monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. And the like. Examples of the vinyl monomer having a carboxyl group or an acid anhydride group include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and monobutyl maleate. Examples of the vinyl monomer having an amide group include acrylamide, dimethylacrylamide, diethylacrylamide, methacrylamide, N-methylolacrylamide, and the like. Examples of the vinyl monomer having an amino group include dimethylaminoethyl acrylate. Examples of the vinyl monomer having an epoxy group include glycidyl acrylate and glycidyl methacrylate. Examples of the vinyl monomer having an alkoxy group include alkoxyalkyl acrylates such as 2-methoxyethyl acrylate and ethoxyethyl acrylate. Examples of the vinyl monomer having an acyl group include vinyl esters such as vinyl acetate. Examples of the vinyl monomer having a cyano group include unsaturated nitriles such as acrylonitrile and methacrylonitrile. Examples of the vinyl monomer having an aryl group include vinyl aromatic compounds such as styrene. Examples of the vinyl monomer having a heterocyclic group include a vinyl monomer having a pyrrolidone ring such as N-vinylpyrrolidone. These vinyl monomers can be used alone or in combination of two or more.
本発明において用いられるアクリル系共重合体としては、(メタ)アクリル酸アルキルエステルと、その他のビニル単量体との共重合体であることが好ましく、当該その他のビニル単量体に、水酸基、カルボキシル基、酸無水物基、アミド基、アミノ基、エポキシ基、及びアルコキシ基からなる群より選ばれる少なくとも1種の官能基を有するビニル単量体(以下、「ビニル単量体(A)」ということがある。)が少なくとも1種含まれている共重合体であることがより好ましく、さらに、官能基を有さないビニル単量体(以下、「ビニル単量体(B)」ということがある。)が少なくとも1種含まれている共重合体であることが好ましい。 The acrylic copolymer used in the present invention is preferably a copolymer of an alkyl (meth) acrylate and another vinyl monomer, and the other vinyl monomer may have a hydroxyl group, A vinyl monomer having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amide group, an amino group, an epoxy group, and an alkoxy group (hereinafter referred to as "vinyl monomer (A)" Is more preferably a copolymer containing at least one vinyl monomer having no functional group (hereinafter, referred to as “vinyl monomer (B)”). Is preferred.) Is at least one copolymer.
本発明において用いられるアクリル系共重合体としては、炭素数が4〜18、好ましくは8〜12のアルキル基を有するアクリル酸アルキルエステルが55〜95質量%、好ましくは60〜95質量%、より好ましくは65〜90質量%;ビニル単量体(A)が1〜25質量%、好ましくは1〜20質量%、より好ましくは2〜15質量%;ビニル単量体(A)以外のビニル単量体が0〜40質量%、好ましくは0〜30質量%、より好ましくは0〜25質量%;及び、その他のビニル単量体が0〜10質量%;の共重合体であることが好ましく、炭素数が4〜18、好ましくは8〜12のアルキル基を有するアクリル酸アルキルエステルが55〜95質量%、好ましくは60〜95質量%、より好ましくは65〜90質量%;ビニル単量体(A)が1〜25質量%、好ましくは1〜20質量%、より好ましくは2〜15質量%;ビニル単量体(B)が0〜40質量%、好ましくは3〜30質量%、より好ましくは5〜25質量%;及び、その他のビニル単量体が0〜10質量%;の共重合体であることがより好ましい。なかでも、ビニル単量体(A)がアクリル酸であり、ビニル単量体(B)が酢酸ビニルであることが特に好ましく、炭素数が4〜18、好ましくは8〜12のアルキル基を有するアクリル酸アルキルエステルが55〜95質量%、好ましくは60〜95質量%、より好ましくは65〜90質量%;アクリル酸が1〜25質量%、好ましくは1〜20質量%、より好ましくは2〜15質量%;酢酸ビニルが0〜40質量%、好ましくは3〜30質量%、より好ましくは5〜25質量%;及び、その他のビニル単量体が0〜10質量%;の共重合体であることがより好ましい。このような共重合組成を有するアクリル系共重合体を粘着剤として用いることにより、粘着剤層が薄くても適度の粘着性を示し、その他の特性にも優れた粘着剤層を形成することが容易となる。 As the acrylic copolymer used in the present invention, an acrylic acid alkyl ester having an alkyl group having 4 to 18, preferably 8 to 12 carbon atoms is 55 to 95% by mass, preferably 60 to 95% by mass, 65 to 90% by mass; 1 to 25% by mass, preferably 1 to 20% by mass, more preferably 2 to 15% by mass of vinyl monomer (A); Is preferably a copolymer of 0 to 40% by mass, preferably 0 to 30% by mass, more preferably 0 to 25% by mass; and 0 to 10% by mass of another vinyl monomer. An alkyl acrylate having an alkyl group having 4 to 18, preferably 8 to 12 carbon atoms, 55 to 95% by mass, preferably 60 to 95% by mass, more preferably 65 to 90% by mass; vinyl monomer A) is 1 to 25% by mass, preferably 1 to 20% by mass, more preferably 2 to 15% by mass; and the vinyl monomer (B) is 0 to 40% by mass, preferably 3 to 30% by mass, more preferably. Is preferably a copolymer of 5 to 25% by mass; and another vinyl monomer of 0 to 10% by mass. Among them, it is particularly preferable that the vinyl monomer (A) is acrylic acid and the vinyl monomer (B) is vinyl acetate, and has an alkyl group having 4 to 18, preferably 8 to 12 carbon atoms. Acrylic acid alkyl ester is 55 to 95% by mass, preferably 60 to 95% by mass, more preferably 65 to 90% by mass; acrylic acid is 1 to 25% by mass, preferably 1 to 20% by mass, more preferably 2 to 25% by mass. 15% by mass; 0 to 40% by mass, preferably 3 to 30% by mass, more preferably 5 to 25% by mass of vinyl acetate; and 0 to 10% by mass of other vinyl monomers. More preferably, there is. By using an acrylic copolymer having such a copolymer composition as a pressure-sensitive adhesive, the pressure-sensitive adhesive layer exhibits appropriate tackiness even if the pressure-sensitive adhesive layer is thin, and it is possible to form a pressure-sensitive adhesive layer excellent in other properties. It will be easier.
本発明において用いられるアクリル系共重合体の重量平均分子量は、好ましくは300,000〜1,000,000、より好ましくは450,000〜650,000である。アクリル系共重合体の重量平均分子量を上記範囲内とすることによって、凝集性、粘着力、他成分との混合作業性、他成分との親和性などをバランスさせることができる。分子量が300,000を下回ると凝集性が低下するため、剥離時に皮膚への糊残りを生ずる恐れがある。分子量が1,000,000を上回ると、製造時の取り扱い性に劣る。アクリル系共重合体の重量平均分子量は、ゲルパーミエーションクロマトグラフィ(GPC)法により、標準ポリスチレン換算値として求めた値である。 The weight average molecular weight of the acrylic copolymer used in the present invention is preferably from 300,000 to 1,000,000, more preferably from 450,000 to 650,000. By setting the weight average molecular weight of the acrylic copolymer within the above range, cohesiveness, adhesive strength, workability of mixing with other components, affinity with other components, and the like can be balanced. When the molecular weight is less than 300,000, the cohesiveness is reduced, so that there is a possibility that glue remains on the skin at the time of peeling. If the molecular weight exceeds 1,000,000, the handleability during production is poor. The weight average molecular weight of the acrylic copolymer is a value determined as a standard polystyrene equivalent value by a gel permeation chromatography (GPC) method.
本発明において用いられるアクリル系共重合体は、一般に、ラジカル重合させることにより合成することができる。当該アクリル系共重合体は、溶液重合法、懸濁重合法、又は乳化重合法により製造することができるが、良好な粘着特性が得られ易い点で、溶液重合法が好ましい。重合開始剤としては、ベンゾイルパーオキサイド、ラウロイルパーオキサイドなどの有機過酸化物;アゾビスイソブチロニトリルなどのアゾ系開始剤;などが挙げられる。全単量体に対して、0.1〜3質量%程度の割合でラジカル重合開始剤を加え、窒素気流下、40〜90℃程度の温度で、数時間から数十時間撹拌して共重合させる。溶液重合法では、溶媒として、酢酸エチル、アセトン、トルエン、これらの混合物などが汎用されている。 The acrylic copolymer used in the present invention can be generally synthesized by radical polymerization. The acrylic copolymer can be produced by a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method, but the solution polymerization method is preferable because good adhesive properties are easily obtained. Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide and lauroyl peroxide; azo-based initiators such as azobisisobutyronitrile; and the like. A radical polymerization initiator is added at a ratio of about 0.1 to 3% by mass based on all monomers, and the mixture is stirred under a nitrogen stream at a temperature of about 40 to 90 ° C. for several hours to several tens of hours to copolymerize. Let it. In the solution polymerization method, ethyl acetate, acetone, toluene, a mixture thereof and the like are widely used as a solvent.
(架橋及び架橋剤)
本発明において用いられる粘着剤組成物は、架橋剤を含有していてもよい。当該粘着剤組成物が架橋剤を含有する場合には、当該粘着剤組成物中のアクリル系共重合体を架橋処理して粘着剤層を形成することによって、粘着剤層の凝集力を向上させることができる。
(Crosslinking and crosslinking agent)
The pressure-sensitive adhesive composition used in the present invention may contain a crosslinking agent. When the pressure-sensitive adhesive composition contains a crosslinking agent, by improving the cohesive force of the pressure-sensitive adhesive layer by forming a pressure-sensitive adhesive layer by crosslinking the acrylic copolymer in the pressure-sensitive adhesive composition. be able to.
架橋剤としては、多官能イソシアネート化合物〔トリレンジイソシアネート(TDI)、4,4´−ジフェニルメタンジイソシアネート(MDI)、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、メタキシリレンジイソシアネート、1,5−ナフタレンジイソシアネート、水素化ジフェニルメタンジイソシアネート、水素化トリレンジイソシアネート、水素化キシリレンジイソシアネート、イソホロンジイソシアネート等〕や多官能エポキシ化合物、アセチルアセトン金属塩などが挙げられる。また、例えば、日本ポリウレタン工業株式会社製のコロネート(登録商標)HL、コロネートL、コロネートEH、三菱ガス化学株式会社製のTETRAD−X、(登録商標)、TETRAD−C(登録商標)、ナーセム(登録商標)アルミニウムなどの市販品を架橋剤とすることができる。架橋剤は、単独で、又は2種類以上を用いてもよい。 Examples of the crosslinking agent include polyfunctional isocyanate compounds [tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate, xylylene diisocyanate, meta-xylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenation Diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, etc.), polyfunctional epoxy compounds, acetylacetone metal salts and the like. Also, for example, Coronate (registered trademark) HL, Coronate L, Coronate EH, manufactured by Nippon Polyurethane Industry Co., Ltd., TETRAD-X, (registered trademark), TETRAD-C (registered trademark), Nursem (manufactured by Mitsubishi Gas Chemical Co., Ltd.) Commercial products such as (registered trademark) aluminum can be used as the crosslinking agent. The crosslinking agents may be used alone or in combination of two or more.
本発明において用いられる粘着剤組成物が架橋剤を含有する場合、架橋剤の含有量は、アクリル共重合体100質量部に対して、好ましくは0.01〜1質量部、より好ましくは0.03〜0.5質量部、特に好ましくは0.04〜0.1質量部である。 When the pressure-sensitive adhesive composition used in the present invention contains a crosslinking agent, the content of the crosslinking agent is preferably 0.01 to 1 part by mass, more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the acrylic copolymer. The amount is from 0.3 to 0.5 part by mass, particularly preferably from 0.04 to 0.1 part by mass.
本発明において用いられる粘着剤組成物に架橋剤を含有させる場合、架橋剤は、当該粘着組成物に予め含有させていてもよく、当該粘着剤組成物を支持体に塗工する直前又は塗工中の粘着組成物に添加してもよい。 When the pressure-sensitive adhesive composition used in the present invention contains a cross-linking agent, the cross-linking agent may be contained in the pressure-sensitive adhesive composition in advance, and immediately before or after coating the pressure-sensitive adhesive composition on a support. You may add to the adhesive composition in it.
(液状可塑剤)
本発明に係る医療用貼付材の粘着剤層に含有される液状可塑剤は、粘着剤層を可塑化してソフト感を付与するものであり、これにより皮膚刺激性が低減される。本発明において用いられる粘着剤組成物が含有する液状可塑剤は、室温で液状であり、当該粘着剤組成物が含有するアクリル系共重合体と相溶である、分子量が350〜550の脂肪酸エステルである。当該粘着剤組成物に含有されている室温で液状の脂肪酸エステルが、当該粘着剤組成物が含有するアクリル系共重合体と相溶であり、かつ分子量350〜550である単一種の脂肪酸エステルのみであってもよく、2種類以上の脂肪酸エステルを含有していてもよい。室温で液状であり、当該粘着剤組成物が含有するアクリル系共重合体と相溶である脂肪酸エステルが2種類以上含有されている場合、これらの脂肪酸エステルの質量平均分子量が350〜550の範囲内にあればよい。室温で液状であり、大きさが特定の範囲であって、アクリル系共重合体と相溶である脂肪酸エステルを用いることにより、アクリル系共重合体と脂肪酸エステルが均一に混じりあっており、ヒト皮膚への高い粘着力を維持しつつ、皮膚から剥離した際に皮膚への残留が充分に抑えられた粘着剤層が形成される。
(Liquid plasticizer)
The liquid plasticizer contained in the pressure-sensitive adhesive layer of the medical patch according to the present invention plasticizes the pressure-sensitive adhesive layer to give a soft feeling, thereby reducing skin irritation. The liquid plasticizer contained in the pressure-sensitive adhesive composition used in the present invention is a liquid at room temperature and is compatible with the acrylic copolymer contained in the pressure-sensitive adhesive composition, and has a molecular weight of 350 to 550. It is. The fatty acid ester liquid at room temperature contained in the pressure-sensitive adhesive composition is compatible with the acrylic copolymer contained in the pressure-sensitive adhesive composition, and is a single type of fatty acid ester having a molecular weight of 350 to 550. And may contain two or more fatty acid esters. When two or more fatty acid esters that are liquid at room temperature and are compatible with the acrylic copolymer contained in the pressure-sensitive adhesive composition are contained, the weight average molecular weight of these fatty acid esters is in the range of 350 to 550. It should be inside. It is liquid at room temperature, the size is in a specific range, and by using a fatty acid ester that is compatible with the acrylic copolymer, the acrylic copolymer and the fatty acid ester are uniformly mixed with each other. A pressure-sensitive adhesive layer is formed in which the adhesion to the skin is sufficiently suppressed when peeled from the skin while maintaining a high adhesive strength to the skin.
分子量が350〜550の範囲内である脂肪酸エステルであって、アクリル系共重合体との相溶性が高いものは、充分な可塑性を付与でき、さらに、粘着剤組成物塗工後の乾燥工程等の加熱工程での揮散が無い。このため、分子量が350〜550の範囲内の脂肪酸エステルを液状可塑剤として用いることにより、粘着剤層を形成した場合に適度な皮膚接着性を付与可能であり、かつ剥離時に剥離される角質の面積を抑えることが可能な粘着剤組成物が得られる。 Fatty acid esters having a molecular weight in the range of 350 to 550 and having high compatibility with the acrylic copolymer can impart sufficient plasticity, and furthermore, a drying step after application of the pressure-sensitive adhesive composition and the like. No volatilization in the heating process. For this reason, by using a fatty acid ester having a molecular weight in the range of 350 to 550 as a liquid plasticizer, it is possible to impart appropriate skin adhesion when a pressure-sensitive adhesive layer is formed, and to remove exfoliated keratin at the time of exfoliation. A pressure-sensitive adhesive composition capable of suppressing the area is obtained.
本発明において用いられる粘着剤組成物は、分子量が350〜550の範囲内の脂肪酸エステルの中でも、少なくとも1個の脂肪酸残基(脂肪酸に由来する残基。具体的には、脂肪酸から水酸基を除いた基)がオレイン酸残基(オレイン酸から水酸基を除いた基)であるオレイン酸エステルを含有することが好ましい。液状可塑剤としてオレイン酸エステル(少なくとも1個のオレイン酸残基を有する脂肪酸エステル)を用いると、本発明において用いられる粘着剤組成物から形成された粘着剤層は、連続貼付時(長期間貼付時)や繰り返し貼付時に皮膚への影響がより低減される。 In the pressure-sensitive adhesive composition used in the present invention, at least one fatty acid residue (residue derived from a fatty acid; specifically, a hydroxyl group is removed from a fatty acid) among fatty acid esters having a molecular weight in the range of 350 to 550. Oleic acid ester, which is an oleic acid residue (a group obtained by removing a hydroxyl group from oleic acid). When oleic acid ester (fatty acid ester having at least one oleic acid residue) is used as the liquid plasticizer, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition used in the present invention can be used at the time of continuous application (long-term application). ) Or repeated application, the effect on the skin is further reduced.
オレイン酸エステルとしては、1価アルコールとオレイン酸のエステルであってもよく、多価アルコールとオレイン酸のエステルであってもよい。1価アルコールとしては、カプリルアルコール、ラウリルアルコール、ミリスチルアルコール、セチルアルコール、ステアリルアルコール、イソステアリルアルコール、オレイルアルコール等のアルキルアルコールが挙げられる。多価アルコールとしては、グルセリン、ソルビトール、グリコール等が挙げられる。 The oleic acid ester may be a monohydric alcohol and oleic acid ester, or a polyhydric alcohol and oleic acid ester. Examples of the monohydric alcohol include alkyl alcohols such as caprylic alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, and oleyl alcohol. Examples of the polyhydric alcohol include glycerin, sorbitol, glycol and the like.
多価アルコールとオレイン酸のエステルの場合、多価アルコール中の1個の水酸基のみが脂肪酸とエステル結合していてもよく、2個以上の水酸基が脂肪酸とエステル結合していてもよい。2個以上の水酸基が脂肪酸とエステル結合したオレイン酸エステルの場合、エステル中の脂肪酸残基の一部のみがオレイン酸残基であってもよく、エステル中の全ての脂肪酸残基がオレイン酸残基であってもよい。 In the case of the ester of polyhydric alcohol and oleic acid, only one hydroxyl group in the polyhydric alcohol may be ester-bonded to the fatty acid, or two or more hydroxyl groups may be ester-bonded to the fatty acid. In the case of an oleic acid ester in which two or more hydroxyl groups are ester-bonded to a fatty acid, only some of the fatty acid residues in the ester may be oleic acid residues, and all the fatty acid residues in the ester may be oleic acid residues. It may be a group.
本発明において用いられる粘着剤組成物が含有する分子量が350〜550の範囲内のオレイン酸エステルとしては、具体的には、オレイン酸オクチル、オレイン酸ラウリル、オレイン酸ミリスチル、オレイン酸セチル、オレイン酸ステアリル、オレイン酸イソステアリル、オレイン酸オレイル、モノオレイン酸グリセリル、モノオレイン酸ソルビタン、ヒマシ油脂肪酸エステル等が挙げられる。これらのオレイン酸エステルは、単独で又は2種以上組み合わせて使用してもよい。本発明において用いられる粘着剤組成物が含有するオレイン酸エステルとしては、モノオレイン酸グリセリル(分子量:356.5)、モノオレイン酸ソルビタン(分子量:428.6)、オレイン酸オレイル(分子量:531)が好ましく、特に、オレイン酸オレイルが特に好ましい。 As the oleic acid ester having a molecular weight in the range of 350 to 550 contained in the pressure-sensitive adhesive composition used in the present invention, specifically, octyl oleate, lauryl oleate, myristyl oleate, cetyl oleate, oleic acid Examples include stearyl, isostearyl oleate, oleyl oleate, glyceryl monooleate, sorbitan monooleate, and castor oil fatty acid ester. These oleic acid esters may be used alone or in combination of two or more. The oleic acid ester contained in the pressure-sensitive adhesive composition used in the present invention includes glyceryl monooleate (molecular weight: 356.5), sorbitan monooleate (molecular weight: 428.6), and oleyl oleate (molecular weight: 531) Oleyl oleate is particularly preferred.
本発明において用いられる粘着剤組成物における分子量が350〜550の範囲内のオレイン酸エステルの含有量は、アクリル系共重合体100質量部に対して、好ましくは1〜35質量部、より好ましくは5〜25質量部である。この含有量が1質量部未満の場合、粘着剤層の可塑化が不充分となって皮膚刺激性を低減することができない場合があり、逆に35質量部を超える場合、粘着剤が有する凝集力が低下し、剥離時に皮膚への糊残りを生ずる恐れがある。 The content of the oleic acid ester having a molecular weight in the range of 350 to 550 in the pressure-sensitive adhesive composition used in the present invention is preferably 1 to 35 parts by mass, more preferably 100 parts by mass of the acrylic copolymer. It is 5 to 25 parts by mass. If the content is less than 1 part by mass, the plasticization of the pressure-sensitive adhesive layer may be insufficient, and the skin irritation may not be reduced. The strength may be reduced and adhesive residue may be left on the skin upon peeling.
本発明において用いられる粘着剤組成物におけるオレイン酸エステル以外の脂肪酸エステルであって、分子量が350〜550の範囲内のものとしては、イソステアリン酸イソステアリル(分子量:約537)等が挙げられる。 Examples of the fatty acid ester other than oleic acid ester in the pressure-sensitive adhesive composition used in the present invention and having a molecular weight in the range of 350 to 550 include isostearyl isostearate (molecular weight: about 537).
本発明において用いられる粘着剤組成物は、本発明の効果を損なわない限度において、分子量が350〜550の範囲内の脂肪酸エステル以外のその他の液状可塑剤を含有していてもよい。その他の液状可塑剤としては、室温で液状であり、かつアクリル系共重合体と相溶性のある可塑剤であれば特に限定されるものではない。例えば、分子量が350未満のオレイン酸エステル、分子量が550超のオレイン酸エステル、オレイン酸エステル以外の脂肪酸エステル、脂肪酸エステル以外の液状可塑剤等が挙げられる。脂肪酸エステル以外の液状可塑剤としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ポリプロピレングリコール等のグリコール;オリーブ油、ヒマシ油、スクアレン、ラノリン等の油脂;流動パラフィン等の炭化水素類;等が挙げられる。その他、室温で液状の有機溶剤や界面活性剤を用いることもできる。また、粘着剤組成物に含有されている脂肪酸エステル全体として当該粘着剤組成物を構成するアクリル系共重合体と相溶であればよく、当該アクリル系共重合体と不相溶の脂肪酸エステルを含有していてもよい。 The pressure-sensitive adhesive composition used in the present invention may contain other liquid plasticizers other than the fatty acid ester having a molecular weight in the range of 350 to 550 as long as the effects of the present invention are not impaired. Other liquid plasticizers are not particularly limited as long as they are liquid at room temperature and compatible with the acrylic copolymer. For example, oleic acid esters having a molecular weight of less than 350, oleic acid esters having a molecular weight of more than 550, fatty acid esters other than oleic acid esters, and liquid plasticizers other than fatty acid esters can be used. Examples of liquid plasticizers other than fatty acid esters include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, and polypropylene glycol; oils and fats such as olive oil, castor oil, squalene, and lanolin; and carbonization of liquid paraffin and the like. Hydrogens; and the like. In addition, an organic solvent or a surfactant that is liquid at room temperature can be used. Further, the fatty acid ester contained in the pressure-sensitive adhesive composition as a whole may be compatible with the acrylic copolymer constituting the pressure-sensitive adhesive composition, and the fatty acid ester incompatible with the acrylic copolymer may be used. It may be contained.
本発明において用いられる粘着剤組成物が含有する液状可塑剤が、分子量が350〜550の範囲内であり、かつアクリル系共重合体と相溶である脂肪酸エステルのみである場合、本発明において用いられる粘着剤組成物における分子量が350〜550の範囲内の脂肪酸エステルの含有量は、アクリル系共重合体100質量部に対して、好ましくは1〜35質量部、より好ましくは5〜25質量部である。この含有量が1質量部未満の場合、粘着剤層の可塑化が不充分となって皮膚刺激性を低減することができない場合があり、逆に35質量部を超える場合、粘着剤が有する凝集力が低下し、剥離時に皮膚への糊残りを生ずる恐れがある。なお、アクリル系共重合体が含有する分子量が350〜550の範囲内であり、かつアクリル系共重合体と相溶である脂肪酸エステルが2種類以上である場合、「粘着剤組成物における分子量が350〜550の範囲内の脂肪酸エステルの含有量」は、分子量が350〜550の範囲内であり、かつアクリル系共重合体と相溶である脂肪酸エステルに該当する脂肪酸エステルの総量を意味する。 When the liquid plasticizer contained in the pressure-sensitive adhesive composition used in the present invention has a molecular weight in the range of 350 to 550, and is only a fatty acid ester compatible with the acrylic copolymer, it is used in the present invention. The content of the fatty acid ester having a molecular weight in the range of 350 to 550 in the obtained pressure-sensitive adhesive composition is preferably 1 to 35 parts by mass, more preferably 5 to 25 parts by mass, based on 100 parts by mass of the acrylic copolymer. It is. If the content is less than 1 part by mass, the plasticization of the pressure-sensitive adhesive layer may be insufficient, and the skin irritation may not be reduced. The strength may be reduced and adhesive residue may be left on the skin upon peeling. When the molecular weight of the acrylic copolymer is in the range of 350 to 550, and the fatty acid ester compatible with the acrylic copolymer is two or more kinds, "the molecular weight in the pressure-sensitive adhesive composition is The “content of the fatty acid ester in the range of 350 to 550” means the total amount of the fatty acid ester corresponding to the fatty acid ester having a molecular weight in the range of 350 to 550 and being compatible with the acrylic copolymer.
本発明において用いられる粘着剤組成物に、分子量が350〜550の範囲内であり、かつアクリル系共重合体と相溶である脂肪酸エステルと、その他の液状可塑剤とを含有する場合、本発明において用いられる粘着剤組成物に含まれている液状可塑剤全量に対する、分子量が350〜550の範囲内の脂肪酸エステルの含有量は、50質量%以上であることが好ましく、60質量%以上であることがより好ましく、80質量%以上であることがさらに好ましく、90質量%以上であることが特に好ましい。また、粘着剤組成物に含まれている液状可塑剤全体の質量平均分子量、特に、室温で液状の脂肪酸エステル全体の質量平均分子量が、350〜550の範囲であることが好ましい。 When the pressure-sensitive adhesive composition used in the present invention contains a fatty acid ester having a molecular weight in the range of 350 to 550 and being compatible with the acrylic copolymer, and another liquid plasticizer, the present invention The content of the fatty acid ester having a molecular weight in the range of 350 to 550 with respect to the total amount of the liquid plasticizer contained in the pressure-sensitive adhesive composition used in the above is preferably 50% by mass or more, and more preferably 60% by mass or more. Is more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The mass average molecular weight of the whole liquid plasticizer contained in the pressure-sensitive adhesive composition, particularly, the mass average molecular weight of the whole fatty acid ester liquid at room temperature is preferably in the range of 350 to 550.
(添加剤)
本発明において用いられる粘着剤組成物は、前記架橋剤の他に、必要に応じて、各種添加剤を含有することができる。当該添加剤としては、薬物、充填剤、酸化防止剤(抗酸化剤、防腐剤)、着色剤、香料、粘着付与剤など、貼付材が備える粘着剤層を形成する粘着剤において慣用されている添加剤を含有することができる。例えば、粘着剤の粘着特性を調整するために、粘着付与剤を配合することができる。粘着付与剤としては、例えば、テルペン系、テルペンフェノール系、クマロンインデン系、スチレン系、ロジン系、キシレン系、フェノール系、石油系などの粘着付与樹脂を挙げることができる。
(Additive)
The pressure-sensitive adhesive composition used in the present invention may contain various additives as necessary in addition to the crosslinking agent. Such additives are commonly used in pressure-sensitive adhesives that form a pressure-sensitive adhesive layer included in a patch, such as drugs, fillers, antioxidants (antioxidants, preservatives), colorants, fragrances, and tackifiers. Additives can be included. For example, a tackifier can be blended in order to adjust the adhesive properties of the adhesive. Examples of the tackifier include terpene-based, terpene-phenol-based, coumarone-indene-based, styrene-based, rosin-based, xylene-based, phenol-based, and petroleum-based tackifier resins.
<医療用貼付材>
本発明に係る医療用貼付材は、支持体と粘着剤層の積層体を備える。本発明に係る医療用貼付材は、支持体の少なくとも片面に、本発明において用いられる粘着剤組成物からなる粘着剤層を備えることが好ましい。粘着剤層が前記粘着剤組成物により形成されるため、ヒト皮膚への充分な粘着力を維持しつつ、剥離時の角質の剥離面積を抑えることができ、皮膚表面の同じ部位に連続貼付又は繰り返し貼付した際にも皮膚刺激への影響が少ない医療用貼付材が得られる。このため、本発明に係る医療用貼付材は、カテーテル等のチューブ固定用のように皮膚の同じ部位に繰り返し貼付される貼付材や、磁気治療器絆創膏等のような皮膚の特定の部位に連続貼付や繰り返し貼付される貼付材に好適である。
<Medical patch>
The medical patch according to the present invention includes a laminate of a support and an adhesive layer. The medical patch according to the present invention preferably includes a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition used in the present invention on at least one surface of the support. Since the pressure-sensitive adhesive layer is formed of the pressure-sensitive adhesive composition, it is possible to suppress the exfoliation area of the stratum corneum at the time of exfoliation while maintaining a sufficient adhesive force to human skin, and to continuously adhere to the same site on the skin surface or A medical patch with less effect on skin irritation even when repeatedly applied is obtained. For this reason, the medical patch according to the present invention is a patch that is repeatedly applied to the same part of the skin as for fixing a tube such as a catheter, or a specific part of the skin such as a magnetic treatment device adhesive plaster. It is suitable for a sticking material that is stuck or repeatedly stuck.
(支持体)
本発明に係る医療用貼付材を構成する支持体は、透湿度が500g/m2・24h以上のものである。充分な透湿度である支持体を用いることにより、透湿度が充分に高く、皮膚に貼付した際の蒸れが少なく、皮膚刺激や貼付中のかゆみが生じにくい医療用貼付材となる。支持体の透湿度としては、500g/m2・24h以上が好ましく、700g/m2・24h以上であることがより好ましく、1,000g/m2・24h以上であることがさらに好ましく、1,500g/m2・24h以上であることがよりさらに好ましく、5,000g/m2・24h以上であることが特に好ましい。
(Support)
The support constituting the medical patch according to the present invention has a moisture permeability of 500 g / m 2 · 24 h or more. By using a support having sufficient moisture permeability, a medical adhesive material having a sufficiently high moisture permeability, less stuffiness when applied to the skin, and less likely to cause skin irritation and itching during application is obtained. The moisture permeability of the support, preferably at least 500g / m 2 · 24h, more preferably 700g / m 2 · 24h or more, still more preferably 1,000g / m 2 · 24h or more, 1, more preferably more is at 500g / m 2 · 24h or more, particularly preferably 5,000g / m 2 · 24h or more.
支持体としては、例えば、含浸紙、コート紙、上質紙、クラフト紙、和紙、グラシン紙等の紙類;ポリエチレンテレフタレートやポリブチレンテレフタレート等のポリエステルフィルム、ポリエチレンやポリプロピレン等のポリオレフィンフィルム、ポリ塩化ビニルフィルム、ポリカーボネートフィルム、ポリウレタンフィルム、セロハンフィルムなどのプラスチックフィルム;発泡体;不織布、織布、編布等の布帛類;これら2種以上の積層体;などが挙げられる。前記布帛類の材質としては、天然素材、合成樹脂素材、再生樹脂材料及びこれら適宜を組み合わせた各種の材料を用いることができ、中でもポリエステル、ポリウレタン、ポリエチレン、ポリプロピレン、ポリアミド、アクリル樹脂等を原料とする不織布、織布、編布等を用いることができる。 Examples of the support include papers such as impregnated paper, coated paper, woodfree paper, kraft paper, Japanese paper, and glassine paper; polyester films such as polyethylene terephthalate and polybutylene terephthalate; polyolefin films such as polyethylene and polypropylene; and polyvinyl chloride. Plastic films such as films, polycarbonate films, polyurethane films and cellophane films; foams; fabrics such as nonwoven fabrics, woven fabrics and knitted fabrics; and laminates of two or more of these. As the material of the cloths, natural materials, synthetic resin materials, recycled resin materials, and various materials obtained by appropriately combining these materials can be used. Among them, polyester, polyurethane, polyethylene, polypropylene, polyamide, acrylic resin, and the like are used as raw materials. Nonwoven fabric, woven fabric, knitted fabric, etc. can be used.
本発明に係る医療用貼付材の支持体の透湿度は、500g/m2・24h以上である。そのため、当該支持体としては、不織布、織布、編布等の布帛類が好ましい。中でも、皮膚に密着することができ、かつ、皮膚の動きに追随することができる程度の柔軟な材質、そして長時間貼付後において皮膚のかぶれ等の発生を抑制できる材質が好ましく、貼付下の皮膚面の動きに対する追随性に優れる点において、さらには、強度を維持しやすく、自背面接着力がより強くなる点において、織布が好ましい。 The support of the medical patch according to the present invention has a moisture permeability of 500 g / m 2 · 24 h or more. Therefore, the support is preferably a fabric such as a nonwoven fabric, a woven fabric, or a knitted fabric. Among them, a material that can be in close contact with the skin, and that is flexible enough to follow the movement of the skin, and a material that can suppress the occurrence of skin irritation and the like after long-time application are preferable. Woven fabrics are preferred in that they are excellent in following the movement of the surface, and further in that the strength is easily maintained and the self-back surface adhesive strength is further increased.
支持体の厚みは、伸び、引張り強さ、作業性などの物理的性質や、貼付時の感触や患部の密閉性等を考慮して適宜選択可能であるが、通常5μmから1mm程度である。なお、支持体の厚みが5μm〜30μm程度とごく薄い場合は、粘着剤層が設けられた支持体の一方側の面とは反対の面(以下、他方側の面という)上に、キャリア層を設けてもよい。 The thickness of the support can be appropriately selected in consideration of physical properties such as elongation, tensile strength and workability, the feel at the time of application, and the tightness of the affected part, and is usually about 5 μm to 1 mm. In the case where the thickness of the support is as thin as about 5 μm to 30 μm, the carrier layer is provided on a surface opposite to one surface of the support on which the pressure-sensitive adhesive layer is provided (hereinafter referred to as the other surface). May be provided.
支持体が布帛類である場合、その厚みは、好ましくは50μm〜1mm、より好ましくは100μm〜800μm、更に好ましくは200μm〜700μmである。また、目付けは、皮膚への追従性の点から、好ましくは400g/m2以下、より好ましくは300g/m2以下、さらに好ましくは250g/m2以下である。 When the support is a cloth, the thickness is preferably 50 μm to 1 mm, more preferably 100 μm to 800 μm, and still more preferably 200 μm to 700 μm. In addition, the basis weight is preferably 400 g / m 2 or less, more preferably 300 g / m 2 or less, and still more preferably 250 g / m 2 or less from the viewpoint of followability to the skin.
また、支持体がプラスチックフィルムである場合、その厚みは、好ましくは10μm〜300μm、より好ましくは12μm〜200μm、さらに好ましくは15μm〜150μmである。なお、支持体がフィルムである場合は、粘着剤層と支持体の投錨性を向上することを目的に、支持体の一方側の面又は他方側の面、あるいはそれら両面にサンドブラスト処理、コロナ処理等の処理を行なってもよい。 When the support is a plastic film, its thickness is preferably 10 μm to 300 μm, more preferably 12 μm to 200 μm, and still more preferably 15 μm to 150 μm. When the support is a film, for the purpose of improving the anchoring property between the pressure-sensitive adhesive layer and the support, one surface or the other surface of the support, or both surfaces thereof are sandblasted or corona-treated. May be performed.
前記支持体の厚みが5μmよりも小さいと、粘着テープの強度や取り扱い性が低下して、皮膚への貼付が困難になり、他の部材等との接触によって破れたり、入浴等の水との接触によって短時間で皮膚から剥離したりすることがある。また、支持体の厚みが大きすぎる(1mmより超える)と、粘着テープが皮膚の動きに追随しにくくなり、粘着テープの辺縁部に剥がれるきっかけを形成しやすくなるため、短時間で皮膚から剥離したり、貼付中の違和感が増えたりするおそれがある。 When the thickness of the support is less than 5 μm, the strength and handleability of the pressure-sensitive adhesive tape are reduced, and it is difficult to attach the pressure-sensitive adhesive tape to the skin. It may peel off from the skin in a short time due to contact. On the other hand, if the thickness of the support is too large (more than 1 mm), it becomes difficult for the adhesive tape to follow the movement of the skin, and it is easy to form a trigger for peeling off at the periphery of the adhesive tape. Or the discomfort during sticking may increase.
(粘着剤層)
粘着剤層は、本発明において用いられる粘着剤組成物を、支持体の表面に所望の厚みとなるように塗工し、乾燥させることにより形成される。粘着剤組成物が架橋剤を含む場合、塗工後に紫外線照射処理等の架橋剤の種類に応じた架橋処理を行う。
(Adhesive layer)
The pressure-sensitive adhesive layer is formed by applying the pressure-sensitive adhesive composition used in the present invention to the surface of the support so as to have a desired thickness, and drying the applied pressure-sensitive adhesive composition. When the pressure-sensitive adhesive composition contains a cross-linking agent, a cross-linking treatment according to the type of the cross-linking agent such as an ultraviolet irradiation treatment is performed after coating.
本発明に係る医療用貼付材における粘着剤層の厚みは、特に限定されるものではなく、好ましくは1〜200μm、より好ましくは10〜100μm、さらに好ましくは20〜80μmである。粘着力は、粘着剤層の厚みに依存し、粘着剤層の厚みが厚すぎると、粘着力が高くなりすぎ、粘着剤層の厚みが薄すぎると、粘着力が弱くなる。粘着剤層の厚みを前記範囲内とすることで、皮膚に十分な粘着力で粘着できることに加えて、貼付材を皮膚などの微細な凹凸のある被着体表面に沿って密着させることができ、さらに、使用後に剥離した際に皮膚刺激を低く抑えることができる。 The thickness of the pressure-sensitive adhesive layer in the medical patch according to the present invention is not particularly limited, and is preferably 1 to 200 μm, more preferably 10 to 100 μm, and further preferably 20 to 80 μm. The adhesive strength depends on the thickness of the adhesive layer. If the thickness of the adhesive layer is too thick, the adhesive strength becomes too high, and if the thickness of the adhesive layer is too thin, the adhesive strength becomes weak. By setting the thickness of the pressure-sensitive adhesive layer within the above range, in addition to being able to adhere to the skin with a sufficient adhesive force, the adhesive can be adhered along the surface of the adherend having fine irregularities such as the skin. Furthermore, skin irritation can be suppressed when peeled after use.
(キャリア層)
本発明に係る医療用貼付材は、支持体に仮着させてキャリア層を形成させてもよい。例えば、「キャリア層/支持体/粘着剤層/セパレーター層」の積層構成を有する貼付材とすることができる。キャリア層により、支持体の厚さが薄い場合に、支持体の製膜性、貼付材の取扱性、被着体への貼付性を向上させることができる。キャリア層は、貼付材の取扱性を向上させるために設けられるものであるから、貼付材の全面を覆っていても、貼付材の縁部のみを覆っていても、あるいは、格子状などのパターン状に覆っていてもよい。
(Carrier layer)
The medical patch according to the present invention may be temporarily attached to a support to form a carrier layer. For example, a patch having a laminated structure of “carrier layer / support / adhesive layer / separator layer” can be used. When the thickness of the support is thin, the carrier layer can improve the film forming property of the support, the handleability of the patch, and the sticking property to the adherend. Since the carrier layer is provided to improve the handleability of the patch, the carrier layer may cover the entire surface of the patch, may cover only the edge of the patch, or may have a pattern such as a lattice. It may be covered in a shape.
キャリア層は、例えば、ポリウレタン、ポリエチレン、ポリプロピレン、アイオノマー、ポリアミド、ポリ塩化ビニル、ポリ塩化ビニリデン、エチレン酢酸ビニル共重合体、熱可塑性ポリエステル、ポリテトラフルオロエチレンなどの各種熱可塑性樹脂からなるフィルムを用いて形成することが好ましい。 The carrier layer is, for example, a film made of various thermoplastic resins such as polyurethane, polyethylene, polypropylene, ionomer, polyamide, polyvinyl chloride, polyvinylidene chloride, ethylene vinyl acetate copolymer, thermoplastic polyester, and polytetrafluoroethylene. It is preferable to form it.
各種フィルムは、紙にラミネートされた状態のものでもよい。これらのキャリア層は、支持体(例えばポリウレタンエラストマーフィルム)に比べて、厚みが厚いか、腰の強いものとすることが好ましい。キャリア層の厚みは、適宜設定できるが、通常、10μm以上、好ましくは20μm以上であり、その上限値は500μm程度である。 Various films may be in a state of being laminated on paper. These carrier layers are preferably thicker or stiffer than the support (for example, a polyurethane elastomer film). The thickness of the carrier layer can be appropriately set, but is usually 10 μm or more, preferably 20 μm or more, and the upper limit is about 500 μm.
(セパレーター層)
本発明に係る医療用貼付材は、支持体層、粘着剤層の他に、通常、粘着剤層を皮膚に貼り付けるときまで、粘着剤層を保護するために、粘着剤層に隣接してセパレーター層が備えられる。
(Separator layer)
The medical patch according to the present invention, the support layer, in addition to the pressure-sensitive adhesive layer, usually, until the time of sticking the pressure-sensitive adhesive layer to the skin, to protect the pressure-sensitive adhesive layer, adjacent to the pressure-sensitive adhesive layer A separator layer is provided.
本発明におけるセパレーター層としては、特に限定されず、貼付材の技術分野において、一般に、離型紙、離型フィルム、剥離紙、剥離フィルム、剥離ライナーなどと称して使用されるものを用いることができる。具体的には、例えば、表面をシリコーン処理したポリエチレンテレフタレートフィルム、表面をシリコーン処理したポリエチレンと紙との積層体などが挙げられる。また、セパレーター層は、取扱い性(すなわち、粘着剤層からの剥離性)を向上するために、切れ目を設けてもよく、貼付材より大きな面積に形成し、周縁部に掴み部を設けてもよい。また、セパレーター層は、取扱い性の向上や印刷適性の向上等の目的で、セパレーター層の粘着剤層に対向する面又は粘着剤層の反対側の面に、サンドブラスト処理等による凹凸を設けてもよい。 The separator layer in the present invention is not particularly limited, and in the technical field of a patch, those generally used as release paper, release film, release paper, release film, release liner, and the like can be used. . Specifically, for example, a polyethylene terephthalate film having a silicone-treated surface, a laminate of polyethylene having a silicone-treated surface and paper, etc. may be mentioned. In addition, the separator layer may be provided with a cut in order to improve the handleability (that is, the releasability from the pressure-sensitive adhesive layer), may be formed in an area larger than the adhesive material, and may be provided with a grip portion on the periphery. Good. Further, the separator layer, for the purpose of improving handleability and printability, for example, may be provided with irregularities by sandblasting or the like on the surface of the separator layer facing the pressure-sensitive adhesive layer or on the surface opposite to the pressure-sensitive adhesive layer. Good.
セパレーター層の厚みは、適宜設定することができ、特に限定されないが、通常20μm以上、好ましくは40μm以上であり、その上限値は500μm程度である。 The thickness of the separator layer can be appropriately set and is not particularly limited, but is usually 20 μm or more, preferably 40 μm or more, and its upper limit is about 500 μm.
(透湿度)
本発明に係る医療用貼付材は、透湿度が500g/m2・24h以上であることが好ましい。当該貼付材は、透湿度が500g/m2・24h以上であることで、皮膚に貼付した際の蒸れが少ないため、皮膚刺激や貼付中のかゆみが生じにくい。当該貼付材の透湿度は、700g/m2・24h以上であることがより好ましく、1,000g/m2・24h以上であることがさらに好ましく、1,500g/m2・24h以上であることがよりさらに好ましく、5,000g/m2・24h以上であることが特に好ましい。透湿度は高いほど好ましく、好ましい透湿度の上限は特にないが、通常30,000g/m2・24h以下である。なお、本発明において透湿度の測定は、JIS Z0208のB条件に従って、温度40℃、相対湿度90%で測定する。すなわち、貼付材の片面側を温度40℃、相対湿度90%に調節し、他面側には塩化カルシウム等の吸湿剤を置いて貼付材を通過した水分を吸収させ、吸湿剤の重量変化量を24時間、1m2当たりに換算して算出する。
(Moisture permeability)
The medical patch according to the present invention preferably has a moisture permeability of 500 g / m 2 · 24 h or more. Since the adhesive material has a moisture permeability of 500 g / m 2 · 24 h or more and is less stuffy when applied to the skin, skin irritation and itching during application are less likely to occur. Moisture permeability of the patch, it is more preferably 700g / m 2 · 24h or more, more preferably 1,000g / m 2 · 24h or more, 1,500g / m 2 · 24h or more There further preferably more, particularly preferably 5,000g / m 2 · 24h or more. Moisture permeability higher preferably, the upper limit is not particularly preferred moisture permeability is usually at most 30,000g / m 2 · 24h. In the present invention, the moisture permeability is measured at a temperature of 40 ° C. and a relative humidity of 90% in accordance with the JIS Z0208 B condition. That is, one side of the patch is adjusted to a temperature of 40 ° C. and a relative humidity of 90%, and a hygroscopic agent such as calcium chloride is placed on the other side to absorb the moisture passing through the patch, and the weight change of the hygroscopic agent the calculated in terms of 24 hours, 1 m 2 per.
(粘着力)
本発明に係る医療用貼付材の粘着力は、対ベークライト粘着力(剥離力)として、好ましくは0.5〜12.0N/25mm、より好ましくは2.0〜8.0N/25mmの範囲内であることが好ましい。医療用貼付材の粘着力がこの範囲内であることにより、本発明に係る医療用貼付材を皮膚表面に貼付した場合、十分な貼付性能を備え、貼付中に位置ずれが生じないとともに、当該貼付材を剥離するときには、皮膚表面を剥離したり、かぶれを発生したりする恐れがない。
(Adhesive force)
The adhesive strength of the medical patch according to the present invention is preferably in the range of 0.5 to 12.0 N / 25 mm, more preferably 2.0 to 8.0 N / 25 mm as bakelite adhesive force (peeling force). It is preferred that When the adhesive strength of the medical adhesive is within this range, when the medical adhesive according to the present invention is affixed to the skin surface, the adhesive has sufficient affixing performance, does not cause displacement during affixing, and When peeling the patch, there is no risk of peeling the skin surface or causing rash.
医療用貼付材の粘着力の測定方法は以下の通りである。すなわち、貼付材を、幅25mm×長さ15mm以上、好ましくは100mmの所定の長さに裁断して試験片とする。試験片をベークライト製試験パネルに押しつけて貼着させた後、2kgのローラーで圧着速さ300mm/分、圧着回数1往復で貼着させて試験片を調製する。貼着してから20分間経過した後、JIS Z0237の引きはがし粘着力試験方法に準拠し、剥離角度180°、剥離速度300mm/分の条件で、粘着力を測定する。 The method for measuring the adhesive strength of the medical patch is as follows. That is, the patch is cut into a predetermined length of 25 mm width × 15 mm length or more, preferably 100 mm, to obtain a test piece. The test piece is pressed against a Bakelite test panel to be adhered, and then adhered with a 2 kg roller at a crimping speed of 300 mm / min with one reciprocation of the number of times of crimping to prepare a test piece. After a lapse of 20 minutes from the sticking, the adhesive force is measured under the conditions of a peel angle of 180 ° and a peel speed of 300 mm / min in accordance with the JIS Z0237 peel test method.
(医療用貼付材の製造方法)
本発明に係る医療用貼付材の製造方法は特に限定されない。例えば、いわゆる剥離ライナーとして一般に使用されるセパレーター層の上に、粘着剤溶液を塗布し、乾燥させて粘着剤層を形成する方法を採用することが好ましい。粘着剤層の連続的な形成方法としては、セパレーター層を一方向に走行させながら、その上に粘着剤溶液を塗布し、乾燥させる方法が好ましい。粘着剤を溶融してセパレーター層上に塗工する方法を採用してもよい。また、特定の形状の繰り返しパターンコーティングとすることもできる。
(Method of manufacturing medical patch)
The method for producing the medical patch according to the present invention is not particularly limited. For example, it is preferable to adopt a method in which an adhesive solution is applied onto a separator layer generally used as a so-called release liner and dried to form an adhesive layer. As a method for continuously forming the pressure-sensitive adhesive layer, a method in which the pressure-sensitive adhesive solution is applied thereon and dried while running the separator layer in one direction is preferable. A method in which the pressure-sensitive adhesive is melted and applied on the separator layer may be adopted. Moreover, it can also be set as the repetitive pattern coating of a specific shape.
セパレーター層の片面に粘着剤層を形成した積層体と支持体とを、粘着剤層と支持体の表面が密着するように貼り合わせることにより、「支持体/粘着剤層/セパレーター層」の積層構成を有する貼付材を作製することができる。また、支持体の片面に任意層であるキャリア層を形成した積層体の場合、粘着剤層と当該積層体の支持体の表面が密着するように貼り合わせることにより、「キャリア層(任意層)/支持体/粘着剤層/セパレーター層」の積層構成を有する貼付材を作製することができる。 By laminating a laminate having a pressure-sensitive adhesive layer formed on one side of a separator layer and a support so that the pressure-sensitive adhesive layer and the surface of the support are in close contact with each other, a laminate of “support / pressure-sensitive adhesive layer / separator layer” is laminated. An adhesive material having the structure can be manufactured. In the case of a laminate in which a carrier layer as an optional layer is formed on one surface of the support, the adhesive layer and the support of the laminate are bonded together so that the carrier layer (optional layer) An adhesive having a laminated structure of “/ support / adhesive layer / separator layer” can be produced.
次に実施例を示して本発明をさらに詳細に説明するが、本発明は以下の実施例に限定されるものではない。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
[実施例1〜4、比較例1〜7]
各種液状可塑剤を含有する粘着剤組成物を調製し、これで粘着剤層を形成した貼付材について、粘着力とヒト皮膚への影響を調べた。液状可塑剤としては、オレイン酸メチル(分子量:296.5)、ミリスチン酸イソプロピル(分子量:268.0)、モノオレイン酸グリセリル(分子量:356.0)、モノオレイン酸ソルビタン(分子量:428.6)、オレイン酸オレイル(分子量:531.0)、イソステアリン酸イソステアリル(分子量:537.0)、大豆油(分子量:約880、SRソイビーン−LQ−(JP)、クローダジャパン社製)、トリオレイン酸ソルビタン(分子量:935.0)、ヒマシ油脂肪酸エステル(分子量:約500、リックサイザーC−101、伊藤製油社製)、オレイン酸デシル(分子量:422.4)、特殊ヒマシ油系縮合脂肪酸(分子量:800、ミネラゾール、伊藤製油社製)、を用いた。また、支持体としては、織布(縦糸:コアスパン、横糸:綿、透湿度:21,060g/m2・24h、目付155g/m2)、ウレタン不織布(繊維径:15μm、透湿度:21,590g/m2・24h、目付65g/m2)、ポリエチレンフィルム(厚さ:50μm、透湿度:60g/m2・24h)を用いた。
[Examples 1 to 4, Comparative Examples 1 to 7]
Pressure-sensitive adhesive compositions containing various liquid plasticizers were prepared, and the adhesive material having the pressure-sensitive adhesive layer formed thereon was examined for its adhesive strength and its effect on human skin. Examples of the liquid plasticizer include methyl oleate (molecular weight: 296.5), isopropyl myristate (molecular weight: 268.0), glyceryl monooleate (molecular weight: 356.0), and sorbitan monooleate (molecular weight: 428.6). ), Oleyl oleate (molecular weight: 531.0), isostearyl isostearate (molecular weight: 537.0), soybean oil (molecular weight: about 880, SR Soybean-LQ- (JP), manufactured by Croda Japan), triolein Sorbitan acid (molecular weight: 935.0), castor oil fatty acid ester (molecular weight: about 500, Ricksizer C-101, manufactured by Ito Oil Co., Ltd.), decyl oleate (molecular weight: 422.4), special castor oil-based condensed fatty acid ( Molecular weight: 800, Minerazole, manufactured by Ito Oil Co., Ltd.). As the support, woven (warp: corespun, weft: cotton, moisture permeability: 21,060g / m 2 · 24h, basis weight 155 g / m 2), urethane nonwoven (fiber diameter: 15 [mu] m, moisture permeability: 21, 590g / m 2 · 24h, basis weight 65g / m 2), polyethylene film (thickness: 50 [mu] m, moisture permeability: 60g / m 2 · 24h) was used.
<サンプル作製>
まず、粘着剤組成物として、アクリル酸2−エチルヘキシルエステル/酢酸ビニル/アクリル酸=85/11/4(質量比)からなる単量体混合物を共重合反応して得られたアクリル系共重合体の溶液に、アクリル系共重合体100質量部に対して、表1〜3に記載の液状可塑剤を表1に示す質量部となるように混合し、さらに架橋剤としてTetrad−X(三菱ガス化学社製)0.06質量部を混合し、均一な粘着剤組成物の溶液を調製した。
この粘着剤組成物の溶液を、セパレーター(シリコーン処理ポリラミ剥離紙)の剥離処理面に、乾燥後の厚みが38μmになるよう塗布、乾燥して粘着剤層を形成した。この粘着剤層を、表1〜3に記載の支持体に貼り合わせて貼付材を作製した。
<Sample preparation>
First, as an adhesive composition, an acrylic copolymer obtained by copolymerizing a monomer mixture composed of 2-ethylhexyl acrylate / vinyl acetate / acrylic acid = 85/11/4 (mass ratio) Is mixed with 100 parts by mass of the acrylic copolymer so that the liquid plasticizers described in Tables 1 to 3 become the parts by mass shown in Table 1, and further, as a crosslinking agent, Tetrad-X (Mitsubishi Gas 0.06 parts by mass (manufactured by Kagaku Co., Ltd.) were mixed to prepare a uniform pressure-sensitive adhesive composition solution.
The solution of the pressure-sensitive adhesive composition was applied on a release-treated surface of a separator (silicone-treated polylaminate release paper) so that the thickness after drying was 38 μm, and dried to form a pressure-sensitive adhesive layer. This pressure-sensitive adhesive layer was bonded to a support described in Tables 1 to 3 to prepare a patch.
<ヒト皮膚への粘着力の測定>
サイズ15mm×70mmの被験サンプルを、ヒト被験者の前腕部に貼付した。貼付から24時間後に、インストロン型引張試験機を用いて、剥離速度100mm/分、剥離角度90°の条件で粘着力(N/15mm)を測定した(n=8)。剥離は、小指側から親指側に行った。測定結果を表1〜3に示す。
<Measurement of adhesion to human skin>
A test sample having a size of 15 mm × 70 mm was attached to the forearm of a human subject. Twenty-four hours after the application, the adhesive strength (N / 15 mm) was measured using an Instron type tensile tester at a peeling speed of 100 mm / min and a peeling angle of 90 ° (n = 8). Peeling was performed from the little finger side to the thumb side. Tables 1 to 3 show the measurement results.
<角質剥離面積率の測定>
前記の粘着力測定において剥離された後の各被験サンプルを、カチオン染色(ゲンチアナバイオレット:1.0%、ブリリアントグリーン:0.5%、蒸留水:98.5%)で染色した後、流水下で洗浄した。染色後の被験サンプルを顕微鏡(VHX−1000:VH−Z100UR、キーエンス社製)下で撮像し、得られた画像を画像処理装置(Win ROOF、三谷商事社製)で画像解析することによって、各被験サンプルに付着している角質細胞の面積を測定した。各被験サンプルについて、3視野の角質細胞付着面積率([角質細胞付着面積]/[被験サンプルの表面積]×100(%))を算出し、この平均値を各被験サンプルの角質剥離面積率とした(n=8)。測定結果を表1〜3に示す。
<Measurement of exfoliation area ratio>
Each test sample after peeling in the above-mentioned adhesive strength measurement was stained with a cationic dye (gentian violet: 1.0%, brilliant green: 0.5%, distilled water: 98.5%), and then, under running water. And washed. Each of the stained test samples is imaged under a microscope (VHX-1000: VH-Z100UR, manufactured by KEYENCE CORPORATION), and the obtained image is image-analyzed by an image processing apparatus (Win ROOF, manufactured by Mitani Corporation). The area of the keratinocytes attached to the test sample was measured. For each test sample, the keratinocyte attachment area ratio ([keratinocyte attachment area] / [test sample surface area] × 100 (%)) in three visual fields was calculated, and the average value was calculated as the keratin detachment area ratio of each test sample. (N = 8). The measurement results are shown in Tables 1 to 3.
<粘着剤の残留>
前記の粘着力測定において、各被験サンプルを剥離した後の皮膚表面に、粘着剤が残ったかどうかを目視で確認した(n=8)。結果を表1〜3に示す。表中、「×」は剥離時に粘着剤が皮膚に残ったことを、「〇」は剥離時に粘着剤が皮膚に残らなかったことを示す。
<Remaining adhesive>
In the measurement of the adhesive strength, whether or not the adhesive remained on the skin surface after peeling off each test sample was visually checked (n = 8). The results are shown in Tables 1 to 3. In the table, “x” indicates that the adhesive remained on the skin at the time of peeling, and “Δ” indicates that the adhesive did not remain on the skin at the time of peeling.
<繰り返し前腕部貼付試験>
被験サンプルを、ヒト皮膚表面に貼付し、24時間ごとに剥離し、1時間後の皮膚反応を確認した後に、新たな同種の被験サンプルを同部位に貼付する繰り返し前腕部貼付試験(最大7日間、1試験区当たり7枚の被験サンプルを使用)を行った(n=9)。皮膚反応は、剥離1時間後及び24時間後(試験終了日)に、5:反応なし、4:軽い紅斑あり、3:紅斑あり、2:紅斑+浮腫あり、1:紅斑+浮腫+丘疹あり、又は小水疱あり、0:大水疱あり、として評価した。結果を表1〜3に示す。
<Repeated forearm sticking test>
A test sample was applied to the surface of human skin, peeled off every 24 hours, and after confirming the skin reaction after 1 hour, a new test sample of the same kind was applied to the same site repeatedly. (7 test samples per test section) were used (n = 9). The skin reaction was 1 hour and 24 hours after the exfoliation (test end date), 5: no reaction, 4: slight erythema, 3: erythema, 2: erythema + edema, 1: erythema + edema + papule , Or small vesicles, and 0: large vesicles. The results are shown in Tables 1 to 3.
支持体が同一である実施例1〜6及び比較例1〜8で比較すると、各被験サンプルのヒト皮膚への粘着力は、脂肪酸エステルをアクリル系共重合体100質量部に対して、10質量部又は20質量部配合した被験サンプル(比較例2〜3、実施例1〜6、比較例5〜8)では、脂肪酸エステルを配合していない被験サンプル(比較例1)と比べて高い数値であり、脂肪酸エステルを配合することにより、粘着力を高めることができた。脂肪酸エステルをアクリル系共重合体100質量部に対して30質量部配合した被験サンプル(比較例4)では、剥離時に粘着剤残留が発生した。これは、液状可塑剤の含有量が多く、粘着剤層が柔らかくなりすぎたためと推察された。一方で、アクリル系共重合体との相溶性が劣るオレイン酸デシルを選択した被験サンプル(比較例7)は、粘着剤の残留試験において、粘着剤残留が発生し、医療用貼付材として問題があるものであった。 Comparing Examples 1 to 6 and Comparative Examples 1 to 8 in which the support is the same, the adhesive strength of each test sample to human skin is such that the fatty acid ester is 10 parts by mass with respect to 100 parts by mass of the acrylic copolymer. Parts or 20 parts by mass of the test sample (Comparative Examples 2 to 3, Examples 1 to 6, and Comparative Examples 5 to 8) have higher numerical values than the test sample without the fatty acid ester (Comparative Example 1). Yes, the adhesive force could be increased by blending the fatty acid ester. In the test sample (Comparative Example 4) in which the fatty acid ester was blended in an amount of 30 parts by mass with respect to 100 parts by mass of the acrylic copolymer, the adhesive remained when peeled. This was presumed to be because the content of the liquid plasticizer was large and the pressure-sensitive adhesive layer was too soft. On the other hand, in the test sample (Comparative Example 7) in which decyl oleate having poor compatibility with the acrylic copolymer was selected, in the residue test of the pressure-sensitive adhesive, a pressure-sensitive adhesive residue was generated, which caused a problem as a medical patch. There was something.
各被験サンプルの角質剥離面積率は、分子量が350〜550の範囲でアクリル酸系共重合体との相溶性が良好な脂肪酸エステルを配合した被験サンプル(実施例1〜6)では、比較例1と比べて角質剥離面積率が40%前後と十分に低くなった。これに対して、分子量が当該範囲から外れている脂肪酸エステルを配合した被験サンプル(比較例3、比較例5、6、8)では、角質剥離面積率が50%以上であり、低減効果が小さいことが確認できた。また、液状可塑剤として分子量が当該範囲から外れているミリスチン酸イソプロピル(分子量:268.0)を15質量部と、分子量が当該範囲内であるオレイン酸オレイル(分子量:531.0)5質量部とを含有しており、液状可塑剤の質量平均分子量が333.8[(268.0×15+531.0×5)/(15+5)]である比較例3の被験サンプルは、分子量が当該範囲から外れている脂肪酸エステルのみを配合した被験サンプルと同様に、角質剥離面積率が50%以上であり、低減効果が小さかった。 The exfoliation area ratio of each test sample is comparative example 1 in a test sample (Examples 1 to 6) in which a fatty acid ester having a molecular weight in the range of 350 to 550 and having good compatibility with the acrylic acid copolymer is blended. The exfoliation area ratio was about 40%, which was sufficiently lower than that of. On the other hand, in the test samples (Comparative Example 3, Comparative Examples 5, 6, and 8) in which the fatty acid ester whose molecular weight is out of the range is used, the exfoliation area ratio is 50% or more, and the reduction effect is small. That was confirmed. Further, 15 parts by mass of isopropyl myristate (molecular weight: 268.0) having a molecular weight out of the range as a liquid plasticizer and 5 parts by mass of oleyl oleate (molecular weight: 531.0) having a molecular weight within the range are used. And the test sample of Comparative Example 3 in which the mass average molecular weight of the liquid plasticizer is 333.8 [(268.0 × 15 + 531.0 × 5) / (15 + 5)], the molecular weight is out of the range. Similar to the test sample containing only the deviated fatty acid ester, the exfoliation area ratio was 50% or more, and the reduction effect was small.
皮膚反応は、分子量が350〜550の範囲内であってアクリル系共重合体との相溶性が良好な脂肪酸エステルを配合した被験サンプル(実施例1〜6)は、経時推移でほとんど皮膚状態が低下することなく維持できていることが確認できた。また、試験終了日の剥離24時間後においても、赤みが残った被験者が少ないことが確認できた。一方、支持体のみ異なる被験サンプル(実施例3、7、比較例9)を比較すると、透湿度が500g/m2・24h以上であるウレタン不織布を支持体とした実施例7は、透湿度が500g/m2・24h以上である織布を支持体とした実施例3と遜色の無い評価結果であったが、透湿度が60g/m2・24hであるポリエチレンフィルムを支持体とした比較例9では、角質薄利面積率は低いものの、ヒト皮膚粘着力が大きく低下し、皮膚反応も強いものであった。これらの結果より、透湿度が500g/m2・24h以上である織布又は不織布を支持体とし、アクリル系共重合体からなる粘着剤層に対して、アクリル系共重合体との相溶性が良好な分子量350〜550の脂肪酸エステルを適切な量配合することにより、高い粘着力を維持しつつ、皮膚の同じ部位に連続貼付又は繰り返し貼付した際にも皮膚刺激が低い粘着剤層を形成できることが明らかである。 As for the skin reaction, the test sample (Examples 1 to 6) containing a fatty acid ester having a molecular weight in the range of 350 to 550 and having good compatibility with the acrylic copolymer showed almost no skin condition over time. It was confirmed that it could be maintained without lowering. In addition, it was confirmed that there were few subjects who remained reddish even 24 hours after peeling on the test end day. On the other hand, when comparing the test samples (Examples 3, 7, and Comparative Example 9) which differ only in the support, Example 7 using a urethane nonwoven fabric having a moisture permeability of 500 g / m 2 · 24 h or more showed a moisture permeability of Comparative example 500 g / m 2 · but 24h the at is woven more was example 3 and comparable without evaluation result of the support, the moisture permeability was polyethylene film is 60 g / m 2 · 24h and the support In No. 9, although the keratin thinning area ratio was low, the human skin adhesion was greatly reduced and the skin reaction was strong. These results, moisture permeability of the woven or nonwoven fabric is 500g / m 2 · 24h or more as a support for the pressure-sensitive adhesive layer including the acrylic copolymer, the compatibility with the acrylic copolymer By mixing an appropriate amount of a fatty acid ester having a good molecular weight of 350 to 550, it is possible to form a pressure-sensitive adhesive layer with low skin irritation even when continuously or repeatedly applied to the same part of the skin while maintaining high adhesive strength. Is evident.
Claims (8)
前記粘着剤層が、(メタ)アクリル酸アルキルエステルを主成分とした共重合体と、室温で液状の前記共重合体と相溶する脂肪酸エステルとを含有する粘着剤組成物からなり、
前記粘着剤組成物に含有されている前記脂肪酸エステルの質量平均分子量が350〜550であり、
前記粘着剤組成物は、前記共重合体100質量部に対して、前記脂肪酸エステルを5〜25質量部含有しており、
前記支持体の透湿度が500g/m2・24h以上である、
医療用貼付材。 A medical patch comprising a support and a laminate of an adhesive layer,
The pressure-sensitive adhesive layer comprises a pressure-sensitive adhesive composition containing a copolymer containing (meth) alkyl acrylate as a main component and a fatty acid ester compatible with the copolymer which is liquid at room temperature,
The fatty acid ester contained in the pressure-sensitive adhesive composition has a mass average molecular weight of 350 to 550,
The pressure-sensitive adhesive composition contains 5 to 25 parts by mass of the fatty acid ester based on 100 parts by mass of the copolymer.
The moisture permeability of the support is 500g / m 2 · 24h or more,
Medical patch.
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JP2002065841A (en) * | 2000-09-01 | 2002-03-05 | Nitto Denko Corp | Skin-stickable adhesive composition, skin-stickable adhesive tape or sheet |
JP2005089438A (en) * | 2003-09-19 | 2005-04-07 | Kosumedei:Kk | Adhesive composition for skin and self-adhesive tape or sheet for skin |
WO2007126067A1 (en) * | 2006-04-28 | 2007-11-08 | Lion Corporation | Nonaqueous pressure-sensitive adhesive composition, patches and process for production of patches |
JP2007296120A (en) * | 2006-04-28 | 2007-11-15 | Lion Corp | Sticking agent |
JP2009155306A (en) * | 2007-12-28 | 2009-07-16 | Lion Corp | Transdermal patch |
JP2018023784A (en) * | 2016-08-09 | 2018-02-15 | 日東電工株式会社 | Adhesive skin patch and wound body of adhesive skin patch |
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JP2002065841A (en) * | 2000-09-01 | 2002-03-05 | Nitto Denko Corp | Skin-stickable adhesive composition, skin-stickable adhesive tape or sheet |
JP2005089438A (en) * | 2003-09-19 | 2005-04-07 | Kosumedei:Kk | Adhesive composition for skin and self-adhesive tape or sheet for skin |
WO2007126067A1 (en) * | 2006-04-28 | 2007-11-08 | Lion Corporation | Nonaqueous pressure-sensitive adhesive composition, patches and process for production of patches |
JP2007296120A (en) * | 2006-04-28 | 2007-11-15 | Lion Corp | Sticking agent |
JP2009155306A (en) * | 2007-12-28 | 2009-07-16 | Lion Corp | Transdermal patch |
JP2018023784A (en) * | 2016-08-09 | 2018-02-15 | 日東電工株式会社 | Adhesive skin patch and wound body of adhesive skin patch |
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WO2022092090A1 (en) | 2020-10-29 | 2022-05-05 | 日東電工株式会社 | Resin for adhesive sheet, and adhesive sheet |
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