WO2022091457A1 - 皮膚貼付用粘着剤、硬化物および皮膚貼付用粘着テープ - Google Patents

皮膚貼付用粘着剤、硬化物および皮膚貼付用粘着テープ Download PDF

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WO2022091457A1
WO2022091457A1 PCT/JP2021/016494 JP2021016494W WO2022091457A1 WO 2022091457 A1 WO2022091457 A1 WO 2022091457A1 JP 2021016494 W JP2021016494 W JP 2021016494W WO 2022091457 A1 WO2022091457 A1 WO 2022091457A1
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adhesive
polyol
skin
mass
skin application
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PCT/JP2021/016494
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English (en)
French (fr)
Japanese (ja)
Inventor
岳 柏村
龍 佐藤
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東洋インキＳｃホールディングス株式会社
トーヨーケム株式会社
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Priority to CN202180003981.3A priority Critical patent/CN114698371B/zh
Publication of WO2022091457A1 publication Critical patent/WO2022091457A1/ja

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    • 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
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/08—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/16—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing nitrogen, e.g. nitro-, nitroso-, azo-compounds, nitriles, cyanates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/70—Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
    • 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
    • A61L15/20—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing organic materials
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • 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
    • 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes

Definitions

  • the present invention relates to an adhesive for skin application. Further, the present invention relates to a cured product obtained by curing the skin-adhesive adhesive, and a skin-applying adhesive tape having an adhesive layer containing the cured product.
  • Adhesives and adhesive tapes for skin application which are generally used in the medical field, sports field, beauty field, etc., have strong skin adhesive strength for the purpose of surely adhering to the skin surface, and as a result, they adhere.
  • the tape When the tape is peeled off from the skin surface, it may cause damage such as damage to the stratum corneum on the skin surface.
  • the adhesive tapes to be applied to the skin surface have an appropriate skin adhesive strength, but as mentioned above, it is also an important required characteristic that the skin surface is not irritated, especially for infants.
  • the skin surface For people with weak skin such as the elderly and the elderly, it is required to reduce the damage to the skin surface such as skin irritation due to exfoliation of the keratin.
  • long-term application may cause itching and sometimes inflammation of the skin, and residual adhesive (adhesive residue) on the skin after peeling is also a problem. Therefore, it is necessary to adjust the balance between skin irritation and adhesiveness in the adhesive tapes for skin attachment as in the present invention.
  • Patent Document 1 a skin-adhesive adhesive having excellent skin irritation and adhesiveness
  • Patent Document 2 a skin-adhesive using an acrylic adhesive to which a paste-like liquid is added at room temperature.
  • Patent Document 1 a skin-adhesive using an acrylic adhesive to which a paste-like liquid is added at room temperature.
  • such a patch has insufficient keratin low exfoliation property, and also has a problem in developing skin irritation derived from an acrylic monomer contained in a trace amount.
  • Patent Documents 2 and 3 propose a tape for attaching to the skin using a polyurethane-based adhesive. These tapes have suppressed monomer-derived irritation.
  • the tapes proposed in Patent Documents 2 and 3 suppress the irritation derived from the monomer, the cohesive force of the adhesive is insufficient, and when the tape is applied to the skin for a long time, adhesive residue remains. It could occur. In addition, both had low reactivity with the curing agent and low initial curing property. When the initial curability is low, the coating layer or the adhesive layer is affected by the hot air during heating and drying of the coating layer, or the mechanical stress during winding and curing of the adhesive tape obtained after heating and drying.
  • the adhesive layer may have surface appearance defects such as winding core step marks, citron skin, and curling habits.
  • the present invention has been made in view of the above circumstances, and has excellent skin adhesiveness and keratin low exfoliation property even when applied for a long period of time, and has excellent productivity, as well as a skin-adhesive adhesive and a cured product. It is an object of the present invention to provide an adhesive tape using these.
  • the present invention contains a polyurethane polyol (P) and an organic isocyanate (C), and the polyurethane polyol (P) includes a polyol component (A) containing a polyether polyol (a1) and a polyisocyanate component (B).
  • the reaction product of the above, and the hydroxyl value is 2.0 to 45 KOHmg / g, and the weight average molecular weight is 25,000 to 300,000.
  • the polyether polyol (a1) has a hydroxyl group at the molecular end and a hydroxyl group thereof. Among them, it is a skin-adhesive pressure-sensitive adhesive having a primary hydroxyl group content of 40 mol% or more and an average number of hydroxyl groups of 2 or more.
  • the present invention relates to a cured product obtained by curing the skin-adhesive pressure-sensitive adhesive. Furthermore, the present invention relates to an adhesive tape for skin application, which comprises an adhesive layer containing the cured product on a support.
  • the present invention it is possible to provide a skin adhesive, a cured product, and an adhesive tape for skin application, which have excellent productivity, excellent skin adhesiveness even when applied for a long period of time, and exhibit excellent keratin low peelability. It will be possible.
  • the "excellent productivity" in the present invention may be excellent in pot life, coatability, and initial curability. For example, it is excellent in pot life, and coating and drying at the time of producing an adhesive tape. In the process, the adhesive can be sufficiently cured in a short drying time (good initial curability), and the adhesive is less likely to repel or lean (good coatability).
  • the pressure-sensitive adhesive sheet includes a base material and a pressure-sensitive adhesive layer containing a cured product of the pressure-sensitive adhesive composition of the present invention.
  • tape As used herein, "tape,”"film,” and “sheet” are synonymous.
  • Mw is a polystyrene-equivalent weight average molecular weight determined by gel permeation chromatography (GPC) measurement.
  • Mn is a polystyrene-equivalent number average molecular weight obtained by GPC measurement.
  • the adhesive for skin application of the present invention is a reaction product of a polyol component (A) containing a polyether polyol (a1) and a polyisocyanate component (B), and has a hydroxyl value of 2.0 to 45 KOHmg / g. It also contains a polyurethane polyol (P) having a weight average molecular weight of 25,000 to 300,000 and an organic isocyanate (C). According to the present invention, productivity is achieved by using a polyether polyol having a highly reactive primary hydroxyl group and a polyurethane polyol (P) having a specific hydroxyl value and weight average molecular weight which is a reaction product with the polyisocyanate. It is possible to provide a skin pressure-sensitive adhesive and a skin-sticking adhesive tape that are excellent in quality, have no adhesive residue even when applied for a long period of time, and exhibit excellent keratin low peelability.
  • the polyurethane polyol (P) is a reaction product of a polyol component (A) containing a polyether polyol (a1) and a polyisocyanate component (B).
  • the hydroxyl value of the polyurethane polyol (P) is 2.0 to 45 KOH mg / g, preferably 3.0 to 40 KOH mg / g.
  • the hydroxyl value is 2.0 KOH mg / g or more, it is possible to suppress the adhesive residue by increasing the cohesive force of the pressure-sensitive adhesive, and it is possible to exhibit good initial curability by increasing the reaction points.
  • the hydroxyl value is 45 KOHmg / g or less, the adhesive becomes flexible, the keratin low exfoliation property is improved, and the skin followability is improved, so that the adhesiveness to the skin is improved.
  • the weight average molecular weight of the polyurethane polyol (P) is 25,000 to 300,000, preferably 30,000 to 300,000. Within this range, excellent coatability and initial curability can be imparted. If the initial curability is good, there is a tendency that surface appearance defects and the like can be prevented.
  • the polyol component (A) contains a polyether polyol (a1) having a hydroxyl group at the molecular end, a primary hydroxyl group content of 40 mol% or more, and an average number of hydroxyl groups of 2 or more. May contain the polyol (a2) of.
  • the polyether polyol (a1) has a hydroxyl group at the molecular end, and the content of the primary hydroxyl group among the hydroxyl groups is 40 mol% or more. Further, it is a polyether polyol having an average number of hydroxyl groups of 2 or more.
  • the average number of hydroxyl groups of the polyether polyol (a1) is 2 or more, preferably 3 or more.
  • the content of the polyether polyol (a1) contained in 100% by mass of the polyol component (A) is preferably 25 to 100% by mass, and particularly preferably 35 to 100% by mass. Within this range, since it exhibits high reactivity, it is possible to form an adhesive layer having excellent initial curability and less likely to cause adhesive residue.
  • the polyether polyol (a1) is not particularly limited except in the above range, but can be obtained by the following known method.
  • a compound having two or more active hydrogen atoms such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and ethylenediamine is used as an initiator, and the terminal 1 is opened by opening the ring of ethylene oxide, butylene oxide, tetrahydrofuran, or the like. It is obtained by polymerizing a cyclic ether compound that gives a secondary hydroxyl group. In this case, all the hydroxyl groups at the ends are primary hydroxyl groups.
  • the "initiator" used in the methods for producing a polyether polyol such as Methods 1 to 4 is a compound incorporated into a polyether polyol molecule by reacting with a cyclic ether compound as a starting material. ..
  • the compound having two or more active hydrogen atoms used as an initiator may be a compound having two or more functional groups such as a hydroxyl group and an amino group.
  • the initiator is preferably a compound having two or more active oxygen atoms having two or more functional groups, and may be a compound having two or more active oxygen atoms having two or more functional groups.
  • Examples of the cyclic ether compound include an oxylan compound (three-membered ring ether compound), a four-membered ring ether compound, a five-membered ring ether compound and the like, and an oxylan compound is preferable.
  • a compound having two or more active hydrogen atoms such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and ethylenediamine is used as an initiator, and the terminal 1 is opened by opening the ring of ethylene oxide, butylene oxide, tetrahydrofuran, or the like. It is obtained by randomly polymerizing a cyclic ether compound that gives a secondary hydroxyl group and a cyclic ether compound such as propylene oxide that gives a terminal secondary hydroxyl group by opening the ring.
  • the content of the primary hydroxyl group can be controlled by the compounding ratio of the cyclic ether compound giving the terminal primary hydroxyl group and the cyclic ether compound giving the terminal secondary hydroxyl group.
  • Commercially available products include Adeka Polyether PR-3007, Adeka Polyether PR-5007, Adeka Polyether GR-2505, and Adeka Polyether GR-3308 (manufactured by ADEKA).
  • a compound having two or more active hydrogen atoms such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and ethylenediamine is used as an initiator to polymerize propylene oxide, and finally ethylene oxide and butylene oxide are used.
  • This is a method for polymerizing a cyclic ether compound such as tetrahydrofuran. By this method, polypropylene glycol having a primary hydroxyl group content of 40 mol% or more can be obtained.
  • the content of the primary hydroxyl group can be controlled by the amount of the cyclic ether compound that gives the terminal primary hydroxyl group by ring-opening such as ethylene oxide, butylene oxide, and tetrahydrofuran to be added last.
  • Pronon # 201 Pronon # 202B (manufactured by Nichiyu Co., Ltd.), Adeka Polyether BM-34, Adeka Polyether BM-54, Adeka Polyether AM-302, Adeka Polyether AM-502, Adeka Polyether AM- 702 (manufactured by ADEKA), PREMINOL7001K, PREMINOL7012 (manufactured by Asahi Glass Co., Ltd.), Sanniks GL-600, Sanniks GL-3000 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) and the like are applicable.
  • a compound having two or more active hydrogen atoms such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and ethylenediamine is used as an initiator, and propylene oxide is ⁇ -cleavage-added using a specific catalyst.
  • a specific catalyst for example, the method described in JP-A-2000-344881
  • polypropylene glycol having a primary hydroxyl group content of 40 mol% or more can be obtained.
  • the primary hydroxyl group content can be controlled by the amount and type of the catalyst used.
  • Commercially available products include Prime Pole PX1000, Prime Pole FX2202, and Prime Pole 3550 (manufactured by Sanyo Chemical Industries, Ltd.).
  • the polyether polyol (a1) is preferably a polyether polyol containing polypropylene glycol obtained by methods 3 and 4 as a main component.
  • a polyurethane polyol (P) having excellent flexibility and water resistance can be obtained, and more excellent skin adhesiveness, keratin low exfoliation property and water resistance can be exhibited.
  • the primary hydroxyl group content can be determined by pretreating (esterifying) the sample in advance and then measuring by 1 H-NMR method.
  • primary hydroxyl group means a hydroxyl group bonded to a carbon atom bonded to one other carbon atom.
  • secondary hydroxyl group means a hydroxyl group bonded to a carbon atom bonded to two other carbon atoms.
  • sample preparation method About 30 mg of the measurement sample is weighed in a sample tube for NMR having a diameter of 5 mm, and about 0.5 ml of deuterated solvent is added and dissolved. Then, about 0.1 ml of trifluoroacetic anhydride is added to the obtained solution to prepare a sample for analysis.
  • the dehydrogenation solvent for example, a solvent capable of dissolving the sample is appropriately selected from, for example, dehydrogenated chloroform, dehydrogenated toluene, dehydrogenated dimethylsulfoxide, dehydrogenated dimethylformamide, and the like.
  • NMR measurement Perform 1 H-NMR measurement under general conditions.
  • the content of the primary hydroxyl group of the polyether polyol (a1) is 40 mol% or more, preferably 70 mol% or more and 100 mol% or less.
  • the primary hydroxyl group content is 40 mol% or more, the initial curability is excellent and the generation of adhesive residue can be suppressed.
  • the number average molecular weight of the polyether polyol (a1) is not particularly limited, but is preferably 400 to 20000, and particularly preferably 600 to 15000. When the number average molecular weight is in the above range, it is possible to exhibit an appropriate cohesive force and good initial curability.
  • the average number of hydroxyl groups of the polyether polyol (a1) is not particularly limited as long as it is 2 or more, but 2 to 6 is preferable, and 3 to 4 is particularly preferable. When the average number of hydroxyl groups is in the above range, it has an appropriate crosslink density and can exhibit suitable adhesive properties.
  • the average number of hydroxyl groups of the present invention refers to the number of active hydrogen atoms per molecule of the initiator (starting material) used as a raw material in producing the polyol component (A), for example, ethylene glycol and propylene glycol. Is 2, glycerin and trimethylolpropane are 3, and ethylenediamine is 4.
  • polyester polyols examples include polyester polyols, polyether polyols other than polyether polyols (a1), low molecular weight polyols, polybutadiene-modified polyols, polycaprolactone polyols, polycarbonate polyols, polyacrylic polyols, and castor oil-based polyols. Be done.
  • a polyester polyol, a polyether polyol other than the polyether polyol (a1), a polycaprolactone polyol, or a polycarbonate polyol is preferable, and since it has excellent wettability and excellent followability to the skin, it is a polyester polyol or a polyether polyol. Polyester polyols other than (a1) are more preferable.
  • polyester polyol a known polyester polyol is used.
  • the polyester polyol requires, for example, an acid component and a glycol component, and can be synthesized by an esterification reaction using the polyol component, if necessary.
  • the acid component include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, phthalic anhydride, isophthalic acid, trimellitic acid and the like.
  • glycol component polyol component having two hydroxyl groups
  • the number average molecular weight of the polyester polyol can be used without particular limitation, but the number average molecular weight is preferably 500 to 5,000. When a number average molecular weight of 500 to 5,000 is used, appropriate reactivity can be obtained, and a polyurethane polyol (P) having better cohesive force can be easily obtained.
  • the content of the polyester polyol is preferably 0 to 75% by mass, more preferably 0 to 65% by mass, based on 100% by mass of the polyol component (A).
  • the polyether polyol other than the polyether polyol (a1) a known polyether polyol is used.
  • the polyether polyol is a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran using, for example, a low molecular weight polyol such as water, ethylene glycol, propylene glycol, glycerin, and trimethylolpropane as an initiator (starting material). Is obtained by polymerizing.
  • polyether polyol other than the polyether polyol (a1) for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like having one or more hydroxyl groups are preferable, and polypropylene glycol is more preferable.
  • the polyether polyol other than the polyether polyol (a1) preferably has two or more hydroxyl groups.
  • the number average molecular weight of the polyether polyol other than the polyether polyol (a1) can be used without particular limitation, but the number average molecular weight is preferably 500 to 10,000. When a number average molecular weight of 500 to 10,000 is used, appropriate flexibility can be obtained, and a polyurethane polyol (P) having good skin adhesion can be easily obtained.
  • the content of the polyether polyol other than the polyether polyol (a1) is preferably 0 to 75% by mass, more preferably 0 to 65% by mass, based on 100% by mass of the polyol component (A).
  • Low molecular weight polyols include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methylpentanediol, 1,6-hexanediol, butylethylpentanediol, 1,9. -A compound having a molecular weight of less than 500 and having two or more hydroxyl groups at the terminal, such as glycols such as nonanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, xylitol, and mannitol.
  • the urethane bond in the pressure-sensitive adhesive is increased, and an appropriate cohesive force and good substrate adhesion can be imparted.
  • the content of the low molecular weight polyol is preferably 0 to 10% by mass, more preferably 0 to 6% by mass, out of 100% by mass of the polyol component (A). By setting the content in the above range, it is possible to improve the adhesive residue and the adhesion to the base material.
  • the polybutadiene-modified polyol has, for example, two or more hydroxyl groups at the terminal, and is a 1,2-vinyl moiety, a 1,4-cis moiety, a 1,4-trans moiety, or hydrogenation thereof (also referred to as hydrogenation). It is a linear or branched polybutadiene having a structure.
  • the number average molecular weight (Mn) of the polybutadiene-modified polyol is preferably 500 to 6,000, more preferably 800 to 6,000. By setting the number average molecular weight in the above range, an appropriate reactivity can be obtained, and a polyurethane polyol (P) having a good cohesive force can be easily obtained.
  • polybutadiene-modified polyol is hydrogenated, it is preferable that all of the double bond sites existing before hydrogenation are hydrogenated, but in the present invention, some double bond sites remain. Is also good.
  • the polycaprolactone polyol is preferably, for example, a caprolactone-based polyester diol obtained by ring-opening polymerization of a cyclic ester monomer such as ⁇ -caprolactone or ⁇ -valerolactone.
  • the number average molecular weight of the polycaprolactone polyol can be used without particular limitation, but the number average molecular weight is preferably 500 to 5,000. By setting the number average molecular weight in the above range, appropriate reactivity can be obtained, and skin adhesiveness and cohesive force can be further improved.
  • the content of the polycaprolactone polyol is preferably 0 to 75% by mass, more preferably 0 to 65% by mass, based on 100% by mass of the polyol component (A).
  • the polycarbonate polyol is, for example, a polycarbonate polyol obtained by subjecting the polyol component to a polycondensation reaction with phosgen; the above polyol component and dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene.
  • Polycarbonate polyol obtained by esterifying a polyol and a carboxyl group-containing compound Polycarbonate polyol obtained by etherifying a various polycarbonate polyols and a hydroxyl group-containing compound; Ester exchange between the various polycarbonate polyols and an ester compound.
  • Polycarbonate polyol obtained by reaction Polycarbonate polyol obtained by ester exchange reaction between the above-mentioned various polycarbonate polyols and a hydroxyl group-containing compound; Polycarbonate-based polycarbonate polyol obtained by a polycondensation reaction between the above-mentioned various polycarbonate polyols and a dicarboxylic acid compound. ; Copolymerized polyether polycarbonate polyol obtained by copolymerizing the above-mentioned various polycarbonate polyols with alkylene oxide; and the like.
  • the number average molecular weight of the polycarbonate polyol can be used without particular limitation, but the number average molecular weight is preferably 500 to 5,000. By setting the number average molecular weight in the above range, an appropriate reactivity can be obtained, and a polyurethane polyol (P) having a good cohesive force can be easily obtained.
  • the polycarbonate polyol is preferably 0 to 75% by mass, more preferably 0 to 65% by mass, based on 100% by mass of the polyol component (A).
  • the other polyol (a2) is preferably a polyol having a hydroxyl group having 1 to 6 functional groups, and particularly preferably 1 to 4.
  • the other polyol (a2) is preferably a polyol having a hydroxyl group having 2 to 6 functional groups, and particularly preferably 2 to 4.
  • Polyisocyanate component (B) As the polyisocyanate component (B), known ones can be used, and examples thereof include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
  • aromatic polyisocyanate examples include 1,3-phenylenediisocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylenediocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-triisocyanate.
  • Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, and methyl-2,4. -Cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,4-bis (isocyanismethyl) cyclohexane, 1,4-bis (isocyanismethyl) cyclohexane and the like. 3-Ixanomethyl-3,5,5-trimethylcyclohexyl isocyanate and 1,4-cyclohexanediisocyanate are preferable because the raw materials are easily available.
  • examples of the polyisocyanate component (B) include the trimethylolpropane adduct form, the biuret form, and the trimer (the trimer contains an isocyanurate ring) of the polyisocyanate.
  • the polyisocyanate component (B) includes 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and 3-isocyanatemethyl-3,5,5-trimethylcyclohexylisocyanate because of its reactivity with the polyol and the availability of raw materials. (Isophorone diisocyanate) and the like are particularly preferable.
  • the content of the polyisocyanate component (B) is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the polyol component (A).
  • the molecular weight and urethane bond concentration of the polyurethane polyol (P) can be appropriately controlled.
  • the reaction product of the polyol component (A) and the polyisocyanate component (B) is the reaction product of the component consisting of only the polyol component (A) and the polyisocyanate component (B), but also the reaction product of the polyol component (A). It may be a reaction product of a component containing the polyisocyanate component (B).
  • the component containing the polyol component (A) and the polyisocyanate component (B) may contain any component. Examples of the optional component include a monohydric alcohol component, a monovalent isocyanate component, and the like.
  • Catalyst As a catalyst for synthesizing the polyurethane polyol (P), a known catalyst can be used, and examples thereof include a tertiary amine compound and an organometallic compound.
  • tertiary amine compound examples include triethylamine, triethylenediamine, and 1,8-diazabicyclo (5,4,0) -undecene-7 (DBU).
  • organometallic compound examples include tin-based compounds and non-tin-based compounds.
  • tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimalate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, and tributyltin acetate.
  • Non-tin compounds include dibutyltitanium dichloride, tetrabutyl titanate, titanium tetraacetylacetonate, titaniumdiisopropoxybis (ethylacetacetate) and butoxytitanium trichloride and other titanium-based compounds; lead oleate, 2-ethylhexanoic acid.
  • Lead-based compounds such as lead, lead benzoate, and lead naphthenate; iron-based such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt-based such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc naphthenate, Zinc-based compounds such as zinc carboxylate and zinc 2-ethylhexanoate; zirconium-based compounds such as zirconium naphthenate, zirconium tetraacetylacetonate and zirconium tributoxymonoacetylacetonate.
  • the difference in reactivity may cause poor polymerization stability or cloudiness of the reaction solution in a single catalyst system. ..
  • it is easy to control the reaction for example, reaction rate
  • the combination of two or more kinds of catalysts is not particularly limited, and examples thereof include a combination of a tertiary amine and an organic metal type, a combination of tin type and non-tin type, and a combination of tin type and tin type.
  • the mass ratio of tin 2-ethylhexanoate to dibutyltin dilaurate is not particularly limited, and is preferably more than 0 and less than 1, more preferably 0.2 to 0.6. be. When the mass ratio is less than 1, the balance of catalytic activity is good, gelation and cloudiness of the reaction solution are effectively suppressed, and the polymerization stability is further improved.
  • the amount of the catalyst used is not particularly limited, and is preferably 0.005 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the polyol component (A) and the polyisocyanate component (B). Within the above range, excellent reactivity can be exhibited and skin irritation derived from the catalyst can be suppressed.
  • solvent If necessary, one or more kinds of solvents can be used for the polymerization of the polyurethane polyol (P).
  • solvents can be used, and examples thereof include methyl ethyl ketone, methyl acetate, ethyl acetate, toluene, xylene, and acetone.
  • Ethyl acetate is particularly preferable from the viewpoint of the solubility of the polyurethane polyol (P), the boiling point of the solvent, and the like.
  • the polymerization method of the polyurethane polyol (P) is not particularly limited, and known polymerization methods such as a bulk polymerization method and a solution polymerization method can be applied.
  • the polymerization procedure is not particularly limited.
  • Procedure 1) A procedure in which the polyol component (A), the polyisocyanate component (B), the catalyst, and / or the solvent, etc., if necessary, are collectively charged into the flask; Step 2) Examples thereof include a procedure in which the polyol component (A), a catalyst, and / or a solvent or the like, if necessary, are charged in a flask, and the polyisocyanate component (B) is added dropwise thereto.
  • Procedure 2) is preferable because the reaction is easy to control.
  • the reaction temperature is preferably less than 100 ° C, more preferably 85 to 95 ° C.
  • the reaction temperature is 100 ° C. or higher, it becomes difficult to control the reaction rate, polymerization stability and the like, and it may be difficult to produce a polyurethane polyol (P) having a desired molecular weight.
  • the reaction temperature when no catalyst is used is preferably 100 ° C. or higher, more preferably 110 ° C. or higher.
  • the reaction time when no catalyst is used is preferably 3 hours or more.
  • Organic isocyanate (C) As the organic isocyanate (C), a known one can be used, and the compound exemplified as the polyisocyanate component (B) which is a raw material of the polyurethane polyol (P) can be used.
  • the organic isocyanate (C) is preferably an aromatic polyisocyanate, an aliphatic polyisocyanate, and / or a trimethylolpropane adduct, a burette, and a trimer (nulate) of an alicyclic polyisocyanate.
  • the organic isocyanate (C) is the above compound, it is possible to impart excellent initial curability and improve adhesive residue.
  • the ratio of the number of moles of the isocyanate group (NCO) of the organic isocyanate (C) to the number of moles of the hydroxyl group (OH) of the polyurethane polyol (P) is not particularly limited and is preferably 0.02. It is ⁇ 6.0, more preferably 0.03 to 5.0.
  • NCO / OH functional group ratio is 0.02 or more, the cohesive force of the adhesive layer is good, and when the NCO / OH functional group ratio is 6.0 or less, the adhesiveness of the adhesive layer is good, which is preferable.
  • the content of the organic isocyanate (C) with respect to 100 parts by mass of the polyurethane polyol (P) is preferably 0.2 to 15 parts by mass, and more preferably 0.4 to 10 parts by mass.
  • the content of the organic isocyanate (C) is preferably 0.2 parts by mass or more because the cohesive force of the adhesive layer is good, and when it is 15 parts by mass or less, the adhesiveness to the skin is good.
  • plasticizer (D) Any one or more plasticizers (D) can be used for the purpose of making the polyurethane polyol (P) more flexible, reducing pain at the time of tape peeling, and improving the keratin low peeling property.
  • the plasticizer (D) to be used is not particularly limited, and examples thereof include a fatty acid ester-based plasticizer, a polyether ester-based plasticizer, a hydroxycarboxylic acid ester-based plasticizer, and a phosphoric acid ester-based plasticizer.
  • the plasticizer (D) is preferably a fatty acid ester-based plasticizer from the viewpoint of skin irritation and compatibility with the polyurethane polyol (P).
  • esters of phthalic acid, maleic acid, adipic acid, stearic acid, various fatty acids and alkyl alcohols, and esters of polyhydric alcohols such as ethylene glycol and glycerin can be used. More specifically, as the ester of the monovalent alcohol, dibutylphthalate, di2-ethylhexylphthalate, dibutyladipate, di2-ethylhexyl sevacate, dibutyl maleate, ethyl myrithrate, isopropyl myristate, isopropyl palmitate, etc.
  • ester of the divalent or higher alcohol examples include propylene glycol dicaprylate, propylene glycol dicaprate, propylene glycol diisostearate, glyceryl monocaprylate, glyceryl tricaprylate, glyceryl tri-2-ethylhexanoate, glyceryl tricaprate, and trilaurin.
  • ester of the divalent or higher alcohol examples include propylene glycol dicaprylate, propylene glycol dicaprate, propylene glycol diisostearate, glyceryl monocaprylate, glyceryl tricaprylate, glyceryl tri-2-ethylhexanoate, glyceryl tricaprate, and trilaurin.
  • examples thereof include glyceryl acid, glyceryl triisostearate, glyceryl trioleate, and trimethylolpropane tri-2-ethylhexanoate.
  • polyether ester-based plasticizer examples include polyethylene glycol dihexylate, polyethylene glycol di-2-ethylhexylate, polyethylene glycol dilaurylate, polyethylene glycol dioleate, and dipolyethylene glycol adipolyamethyl ether.
  • hydroxycarboxylic acid ester-based plasticizer examples include butyl citrate, triethyl citrate, tripropyl citrate, and triethyl o-acetylcitrate.
  • Examples of the phosphoric acid ester-based plasticizer include tributyl phosphate, tris (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate and the like.
  • the plasticizer (D) may be a compound containing a fatty acid ester structure and a polyether structure, such as polyoxyethylene ether of a sorbitan fatty acid ester obtained by condensing ethylene oxide with a sorbitan fatty acid ester.
  • polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monooleate and the like can be mentioned.
  • the blending amount of the plasticizer (D) is not particularly limited, but is preferably 10 to 80 parts by mass, more preferably 15 to 50 parts by mass with respect to 100 parts by mass of the polyurethane polyol (P).
  • the content of the plasticizer (D) is in this range, it is possible to further improve the low exfoliation property of the keratin while ensuring the cohesive force to the extent that no adhesive residue is left, which is preferable.
  • the adhesive strength can be significantly reduced, the adhesive tape using the adhesive can be suitably used for medical applications in which the tape is directly attached to the wound.
  • a known curing catalyst can be used for the purpose of accelerating the reaction between the polyurethane polyol (P) and the organic isocyanate (C).
  • a curing catalyst By using a curing catalyst, excellent coatability and initial curing property can be imparted.
  • the curing catalyst the same catalyst as described in the description of the catalyst used for the polymerization of the polyurethane polyol (P) can be used, and specific examples thereof include tertiary amine compounds and organometallic compounds. Be done.
  • tertiary amine compound examples include triethylamine, triethylenediamine, and 1,8-diazabicyclo (5,4,0) -undecene-7 (DBU).
  • organometallic compound examples include tin-based compounds and non-tin-based compounds.
  • tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimalate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, and tributyltin acetate.
  • Non-tin compounds include dibutyltitanium dichloride, tetrabutyl titanate, titanium tetraacetylacetonate, titaniumdiisopropoxybis (ethylacetacetate) and butoxytitanium trichloride and other titanium-based compounds; lead oleate, 2-ethylhexanoic acid.
  • Lead-based compounds such as lead, lead benzoate, and lead naphthenate; iron-based such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt-based such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc naphthenate, Zinc-based compounds such as zinc carboxylate and zinc 2-ethylhexanoate; zirconium-based compounds such as zirconium naphthenate, zirconium tetraacetylacetonate and zirconium tributoxymonoacetylacetonate. Titanium-based compounds and zirconium-based compounds are preferable because they are less irritating to the skin and highly safe.
  • the blending amount of the curing catalyst is not particularly limited, but is preferably 0.005 to 0.5 parts by mass, and more preferably 0.01 to 0.4 parts by mass with respect to 100 parts by mass of the polyurethane polyol (P). be. Within this range, it is preferable because it exhibits excellent initial curability and can suppress the skin irritation derived from the catalyst.
  • ⁇ -diketone compound When a catalyst or a curing catalyst is used, it is preferable to use the ⁇ -diketone compound in combination with other components for the purpose of improving the pot life.
  • the ⁇ -diketone compound is not particularly limited, and is, for example, 2,4-pentanedione, 3-methyl-2,4-pentanedione, 2,4-hexanedione, 1,3-cyclohexanedione, 2,2-dimethyl-.
  • the blending amount of the ⁇ -diketone compound is preferably 2 to 1000 parts by mass, more preferably 3 to 500 parts by mass with respect to 1 part by mass of the total of the catalyst and the curing catalyst.
  • the blending amount of the ⁇ -diketone compound is within the above range, both pot life and curability can be achieved.
  • the pressure-sensitive adhesive of the present invention may contain other optional components, if necessary, as long as the effects of the present invention are not impaired.
  • Optional components include resins, fillers, metal powders, pigments, foils, softeners, conductive agents, antioxidants, UV absorbers, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat-resistant stability. Examples include agents, antifoaming agents, lubricants and the like.
  • Examples of the filler include talc, calcium carbonate, titanium oxide and the like.
  • antioxidants examples include radical chain inhibitors such as phenolic antioxidants; peroxide decomposition agents such as sulfur-based antioxidants and phosphorus-based antioxidants.
  • sulfur-based antioxidant examples include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and disstearyl 3,3'-thiodipropionate.
  • Examples of the phosphorus-based antioxidant include triphenylphosphine, diphenylisodecylphosphite, and phenyldiisodecylphosphite.
  • ultraviolet absorber examples include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, oxalic acid anilide-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. ..
  • benzophenone-based ultraviolet absorbers examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, and 2,2'-dihydroxy.
  • benzotriazole-based ultraviolet absorber examples include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, and 2- (2'). -Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-( 2'-Hydroxy-3', 5'-di-tert-butylphenyl) 5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole, 2- (2'-Hydroxy-4'-Octoxiphenyl) Benzotriazole, 2- [2'-Hydroxy-3'-(3'', 4'', 5'', 6'',
  • salicylic acid-based ultraviolet absorber examples include phenylsalicylate, p-tert-butylphenylsalicylate, and p-octylphenylsalicylate.
  • cyanoacrylate-based ultraviolet absorber examples include 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3,3'-diphenylacrylate and the like.
  • Examples of the light stabilizer include hindered amine-based light stabilizers and ultraviolet stabilizers.
  • Hindered amine light stabilizers include [bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate], bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and Examples thereof include methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate.
  • ultraviolet stabilizer examples include nickel bis (octylphenyl) sulfate, [2,2'-thiobis (4-tert-octylphenolate)]-n-butylamine nickel, nickel complex-3,5-di-tert-butyl-.
  • examples thereof include 4-hydroxybenzyl-phosphate monoethylate, nickel-dibutyldithiocarbamate, benzoate type quencher, nickel-dibutyldithiocarbamate and the like.
  • the adhesive tape for skin application of the present invention is a cured product obtained by curing the adhesive for skin application on a support (also referred to as "base material” in the present specification) by a conventional method. It can be obtained by providing a certain adhesive layer.
  • the cured product as used in the present invention refers to a material in which the polyurethane polyol (P) and the organic isocyanate (C) are reacted and the isocyanate group is eliminated (the IR peak of the isocyanate group is not observed).
  • the adhesive layer contains a cured product, and in one example, the adhesive layer is made of a cured product.
  • the adhesive tape for skin application of the present invention can be used in the medical field, sports field, beauty field, etc., and is particularly applied to the skin for medical purposes such as emergency adhesive plasters, adhesive plasters, large padded adhesive plasters, and dressings. be able to. Among them, it is less irritating to the skin and can withstand long-term application, so it can be suitably used for medical purposes, and it can also be used as a dressing material that may be repeatedly applied to the same site. It can be suitably used.
  • the gel fraction of the cured product obtained by curing the adhesive for skin application is preferably 28 to 55% by mass, more preferably 30 to 50% by mass.
  • the gel fraction is 28% by mass or more, it is possible to reduce adhesive residue and pain at the time of peeling, and when the gel fraction is 55% by mass or less, it is possible to suppress the peeling of the adhesive tape from the skin. preferable.
  • the gel content of the cured product is determined by using an adhesive tape provided with an adhesive layer and a support made of a cured product in which the isocyanate group has disappeared (the IR peak of the isocyanate group is not observed) by curing the adhesive for skin application. It is cut to a predetermined size, attached to a SUS200 mesh (opening: 0.077 mm, wire diameter: 0.05 mm), immersed in ethyl acetate, extracted at 50 ° C. for 24 hours, and then at 100 ° C. After drying for 30 minutes, it is a numerical value calculated by the following formula (1).
  • the urethane bond concentration of the cured product is preferably 0.19 to 1.45 mmol / g, and particularly preferably 0.30 to 1.30 mmol / g.
  • the urethane bond concentration is 0.19 mmol / g or more, the adhesion to the base material is improved, and an appropriate cohesive force is imparted to the pressure-sensitive adhesive, so that adhesive residue is less likely to occur.
  • the urethane bond concentration is 1.45 mmol / g or less, the pressure-sensitive adhesive is given flexibility, and it is possible to improve the low exfoliation property of the keratin and suppress the peeling of the adhesive tape, which is preferable.
  • the urethane bond concentration referred to in the present invention is a numerical value calculated by the following mathematical formula.
  • the "hydroxyl group amount (mmol) in the skin-adhesive adhesive" in the formula (2) indicates the amount of unreacted hydroxyl groups in the skin-adhesive adhesive and the isocyanate group already in the skin-adhesive adhesive. The amount of hydroxyl groups after this is included. Equation (2) When the amount of hydroxyl group mol in the adhesive for skin application is the same as or larger than the amount of isocyanate mol of the organic isocyanate (C), it is calculated by the following formula (3). Equation (3)
  • the probe tack of the cured product is preferably 0.6 to 4.0 N / cm 2 , and particularly preferably 0.7 to 3.5 N / cm 2 .
  • the probe tack is 0.6 N / cm 2 or more, the peeling of the adhesive tape for skin application from the skin can be suppressed, and when the probe tack is 4.0 N / cm 2 or less, the pain when the adhesive tape is peeled off. It is preferable because it can reduce the amount of exfoliation of keratin and keratin.
  • the adhesive tape for skin application of the present invention can be produced according to a usual method for producing an adhesive tape. Specifically, there is a method (transfer coating) in which an adhesive is applied to a peeled body and dried to form a cured product, an adhesive layer is formed, and the adhesive layer is transferred to a support. Be done. Alternatively, a method (direct coating) in which an adhesive is directly applied to the support and dried to form a cured product to form an adhesive layer can be mentioned.
  • the adhesive tape for skin application of the present invention may include a carrier and / or a peeler.
  • the carrier is provided in a peelable state on the surface of the support opposite to the surface on which the adhesive layer is provided.
  • the peeling body is provided in a state where it can be peeled off on the surface opposite to the surface on which the support of the adhesive layer is provided.
  • the adhesive tape for skin application of the present invention may include a carrier, a support, an adhesive layer, and a peeling body in this order (FIG. 1).
  • another layer may be interposed between the carrier and the support, between the support and the adhesive layer, and / or between the adhesive layer and the peeled body.
  • a primer layer, an adhesive layer, or a release agent layer may be provided, or a film, a non-woven fabric, a woven fabric, or a laminate thereof may be interposed.
  • the adhesive tape for attaching to the skin of the present invention may be provided with a pad between the adhesive layer and the peeled body for the purpose of absorbing blood or infiltrating liquid.
  • the adhesive layer is a cured product obtained by curing the adhesive for skin application of the present invention.
  • the adhesive layer may be provided by coating the support with a pattern coating, for example, in the form of a grid or diamond, but in order to improve the fixing property to the skin, the adhesive layer is applied to the entire surface of the support. It is preferable that the state is essentially covered.
  • the transparent adhesive tape for skin application of the present invention is transparent from the viewpoint of reducing the amount of exfoliation of the keratin when the adhesive tape is peeled from the skin and suppressing the deterioration of the fixing property due to the moisture accumulated between the skin and the adhesive layer.
  • the humidity is preferably 1,000 g / m 2.24 hr or more, preferably 2,000 g / m 2.24 hr or more.
  • the upper limit of the moisture permeability of the adhesive tape for skin application may be 8,000 g / m 2.24 hr or less, but the higher the moisture permeability, the more preferable, and the upper limit is not particularly limited.
  • the thickness of the adhesive layer of the adhesive tape for skin application of the present invention is not particularly limited, but 5 ⁇ m or more, particularly 10 ⁇ m or more is preferable from the viewpoint of ensuring the fixing property to the skin and the balance with the thickness of the support, and the adhesive layer is preferable. If it becomes too thick, the moisture permeability and the followability to the skin will decrease, so that it is preferably 200 ⁇ m or less, particularly 150 ⁇ m or less.
  • the thickness of the adhesive layer of the adhesive tape is around 3 to 7 ⁇ m, it is possible to give effects such as followability to the skin and inconspicuousness as the adhesive tape for skin attachment.
  • the support of the present invention is not particularly limited as long as it has appropriate elasticity, flexibility, strength and the like for being attached to the skin, but a support having high moisture permeability is suitable.
  • the moisture permeability of the support is preferably 3,000 g / m 2.24 hr or more, particularly preferably 4,000 g / m 2.24 hr or more.
  • the upper limit of the moisture permeability of the support is not particularly limited, but is usually about 10,000 g / m 2.24 hr or less, preferably about 8,000 g / m 2.24 hr or less.
  • 3,000 g / m 2.24 hr to about 10,000 g / m 2.24 hr, particularly 4,000 g / m 2.24 hr to about 8,000 g / m 2.24 hr are preferable.
  • a support having such moisture permeability can be easily achieved with a non-woven fabric or a knitted fabric, but a urethane resin support particularly useful as a dressing material is known by itself (for example, JP-A-7-231910). ), Commercially available.
  • the support When the adhesive tape for skin application of the present invention is used as a medical tape, the support preferably has a moisture permeability of 3,000 g / m 2.24 hr or more, particularly preferably 4,000 g / m 2.24 hr or more, and expands and contracts. Sexual or non-stretchable ones can also be used.
  • the support is, for example, a woven fabric, a non-woven fabric, a knitted fabric, a film, or the like.
  • the support can be selected from polyurethane, polyester, polyvinyl acetate, polyvinylidene chloride, polyethylene, polyethylene terephthalate, aluminum sheets and the like, or composite materials thereof.
  • the support can also be a laminated body.
  • the film having low moisture permeability as it is it can be used as a porous film containing calcium carbonate or the like, or processed by perforating or the like.
  • Nonwoven fabrics, woven fabrics, knitted fabrics and the like are preferable as the support in that an adhesive tape having high moisture permeability can be obtained.
  • a support manufactured from urethane resin for example, a film or the like is suitable, has flexibility and appropriate strength, and particularly has a fixing property of an adhesive tape to the skin. From the viewpoint of enhancing or reducing discomfort during application, those having low water swelling property are preferably used.
  • the support when the support is manufactured from a urethane resin, it is not particularly limited as long as it has the above-mentioned moisture permeability, and examples thereof include ether-based urethane resin and ester-based urethane resin, but the water swellability is high.
  • Ethereal urethane resin is preferably selected from the low point.
  • the support may be an ether-based urethane resin film or an ester-based urethane resin film. These ether-based urethane resins having a predetermined moisture permeability are available from BASF and the like.
  • it can be polymerized by using a conventionally used one-shot method or prepolymer method.
  • the polymerization may be carried out in a solution in order to reduce the viscosity.
  • Films produced by these polymerization methods include DINTEX FT1080-PE, DINTEX FT1881-PE (manufactured by Nippon Unipolymer), Samplen HMP-17A (manufactured by Sanyo Chemical Industries, Ltd.), and the like, which are available.
  • Additives usually used such as ultraviolet absorbers, antiaging agents, fillers, pigments, colorants, flame retardants, antistatic agents, etc., can be added to the support of the present invention, if necessary. These additives are used in normal amounts depending on the type.
  • the thickness of the support of the present invention is preferably 10 ⁇ m or more, particularly 15 ⁇ m or more from the viewpoint of improving the handleability as an adhesive tape, and 50 ⁇ m or less, particularly 40 ⁇ m from the viewpoint of facilitating the production of a highly moisture-permeable support.
  • the following is preferable. If the size is 10 ⁇ m or less, especially 5 to 10 ⁇ m, the support is very thin and difficult to handle. Therefore, devise a support, for example, increase the rigidity of the support more than the support or provide a mouthpiece. Is required.
  • the carrier serves to reinforce the support and improve the manufacturability and operability of the adhesive tape for skin application of the present invention. Further, it is desirable that the carrier is transparent or translucent in consideration of visibility so that the attachment site can be confirmed at the time of attachment. Further, it is preferable that the carrier has a relatively high elastic modulus with respect to the support and has an elastic modulus of about 3 to 20 times with respect to the support. Further, since it is necessary to laminate the carrier on the surface to be laminated on the support while maintaining an appropriate adhesiveness with the support, it is appropriate to perform various treatments. Examples of such treatment include corona treatment, plasma treatment, ultraviolet treatment, matte treatment and the like.
  • a cut may be provided near the center of the support, or two supports may be provided with a gap between the cuts between the supports.
  • a tape or a film may be laminated on the upper part of the cut of the carrier to provide a mouthpiece as a gripping piece.
  • the mouthpiece may be a film, a non-woven fabric, a woven fabric, or a laminate thereof, or may be an adhesive tape for attaching to the skin, and may be colored.
  • the end portion of the carrier may have a corrugated shape or a state in which a plurality of cuts are made, and a carrier formed larger than the support may be used.
  • Examples of the above-mentioned carrier include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polyamides such as nylon, polyvinyl chloride, and polyvinylidene chloride. Further, not only these single carriers but also a carrier of a composite laminated with paper, a non-woven fabric, a woven fabric, a knitted cloth, and a metal foil may be used, but such a carrier has visibility. It is preferable to use a polyolefin and a polyester film from the viewpoint of cost and cost.
  • the adhesive tape for skin application of the present invention can be provided with a peeling body for ease of handling, but the peeling body is also useful in the production of the adhesive tape for skin application. That is, in both transfer coating and direct coating, there is a possibility that the adhesive may come into contact with the mold release treatment agent before the reaction of the organic isocyanate (C) of the pressure-sensitive adhesive is completed.
  • a release body using a treatment agent that does not react with is convenient.
  • peeling body those commonly used in the field of adhesive tape can be used.
  • a paper base material such as high-quality paper or glassine paper that has undergone silicone mold release treatment, a polyester film, or the like can be used.
  • the basis weight of the peeled body is not limited, but is usually preferably about 50 to 150 g / m 2 , and more preferably about 60 to 100 g / m 2 .
  • the adhesive tape for skin application is in the form of a roll, it is particularly effective in making it easier to peel off the peeled body and improving the handleability. Further, even if the peeling bodies are arranged so as to cover one side or fold back so that the two or more peeling bodies can be easily peeled off from the adhesive, it is effective to improve the handleability.
  • a pad can also be used for the adhesive tape for skin application of the present invention.
  • the pad can be made of gauze, rayon, polyethylene, polyester, polypropylene or the like and has a basis weight of about 2 to 100 g / m 2 , and can be preferably placed in the center of the pressure-sensitive adhesive-coated surface.
  • the adhesive has good skin adhesiveness even when applied to the skin for a longer period of time than before, and can suppress adhesive residue and exfoliation of keratin when exfoliated.
  • Agents and adhesive tapes for skin application using the same can be provided.
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • the non-volatile content concentration is the non-volatile content concentration (%) of the sample.
  • Hydroxy group value [ ⁇ (ba) ⁇ F ⁇ 28.05 ⁇ / S] / (nonvolatile content concentration / 100) + D S: Sample collection amount (g) a: Consumption of 0.5N-alcoholic potassium hydroxide solution (ml) b: Consumption (ml) of 0.5N-alcoholic potassium hydroxide solution in the blank experiment F: Factor of 0.5N-alcoholic potassium hydroxide solution D: Acid value (KOHmg / g)
  • C Organic isocyanate
  • ⁇ Plasticizer (D)> (D-1) Glyceryl tricaprylate (fatty acid ester-based plasticizer) (D-2) Isopropyl myristate (fatty acid ester-based plasticizer)
  • D-1) Glyceryl tricaprylate fatty acid ester-based plasticizer
  • D-2) Isopropyl myristate fatty acid ester-based plasticizer
  • TC-401 Titanium Tetra Acetylacetone, manufactured by Matsumoto Fine Chemical Co., Ltd., "Organix TC-401" ⁇ -diketone compound> Acetylacetone
  • TPB Tris (pentafluorophenyl) borane catalyst
  • the pressure inside the equipment was reduced to 0.005 MPa.
  • 200 parts of propylene oxide (hereinafter referred to as PO) as a second component was continuously added to the liquid phase over 12 hours while controlling the reaction temperature to be maintained at 70 to 80 ° C.
  • a refrigerant at -30 ° C was circulated to condense and recover PO in the condensing facility.
  • 200 parts of water was added and the mixture was heated at 130 to 140 ° C. for 1 hour.
  • Polyether polyol (a1-2, 3), other polyol (a2-5) The same operation as for the polyether polyol (a1-1) is performed except that the first component and the second component are of the types shown in Table 1 and the charged amount (part by mass), and the polyether polyol (a1-2, 3) and other polyol (a2-5) were obtained.
  • ⁇ Polyether polyol (a1-4)> After charging 200 parts of glycerin and 4.0 parts of potassium hydroxide as the first component into an autoclave having a stirrer and a temperature control device, PO947 part as the second component is continuously added at a reaction temperature of 100 ° C. under stirring. I put it in. After confirming that the pressure change in the reactor had disappeared and PO had disappeared, 156 parts of ethylene oxide (hereinafter referred to as EO) as a third component was further supplied into the vessel for reaction.
  • EO ethylene oxide
  • the obtained product was added with 40.0 parts of an alkaline adsorbent "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) to 40.0 parts of water, and then mixed and stirred under 90 ° C. conditions for 1 hour. Then, the added alkaline adsorbent is removed with a filter covered with filter paper, and the product after filtration is dehydrated under the conditions of 130 ° C. and a pressure of 2.7 kPa, so that the terminal primary hydroxyl group content is 95 mol%. , A polyether polyol (a1-4) having an average number of hydroxyl groups of 3 and a number average molecular weight of 600 was obtained.
  • ⁇ Other polyol (a2-6)> After charging 10 parts of glycerin and 4.0 parts of potassium hydroxide as the first component into an autoclave having a stirrer and a temperature control device, a mixture of 946 parts of PO and 130 parts of EO as the second component under stirring is mixed at a reaction temperature of 100 ° C. It was continuously added at. The obtained product was added with 40.0 parts of an alkaline adsorbent "Kyoward 600" (manufactured by Kyowa Chemical Industry Co., Ltd.) to 40.0 parts of water, and then mixed and stirred under 90 ° C. conditions for 1 hour.
  • Kyoward 600 manufactured by Kyowa Chemical Industry Co., Ltd.
  • a2-1 Kuraray polyol P-1010, polyester polyol (manufactured by Kuraray) a2-2: Adeka Polyether G-3000B, Polyether Polyol (manufactured by ADEKA) a2-3: Praxel L212AL, polycaprolactone polyol (manufactured by Daicel) a2-4: Propylene glycol a2-7: Preminol S4013F, polyether polyol (manufactured by Asahi Glass Co., Ltd.)
  • the polyurethane polyol (P-1) is the same as the polyurethane polyol (P-1) except that the polyol (A), the type of the polyisocyanate component (B), and the blending amount (parts by mass) thereof are changed as shown in Tables 3 and 4. Solutions of P-2 to 17) and (P'-1 to 6) were obtained.
  • the main compounding composition and the hydroxyl value and weight average molecular weight of the obtained urethane prepolymer are shown in Tables 3 and 4.
  • a polyether polyurethane (Resamine P-210 manufactured by Dainichi Seika Kogyo Co., Ltd.) is heated and melted with a twin-screw screw type kneader, and then the thickness is increased with a T-die type extruder. It was extruded to 30 ⁇ m to form an elastomer film (support).
  • the stretched polypropylene film (manufactured by Gunze Co., Ltd., Sylfan MT thickness 40 ⁇ m) which had been subjected to corona treatment and adjusted so that the surface tension was 420 N / mm as measured by a wet index solution.
  • the elastomer film was brought into close contact with the corona-treated surface using a rubber roll to obtain a laminated film of the elastomer film and a carrier.
  • Example 1 Add 100 parts by mass of urethane prepolymer (P-1), 1.15 parts by mass of polyisocyanate component (B-1), and 20 parts by mass of ethyl acetate as a solvent, stir with a disper, and make a uniform adhesive for skin application. I got the agent.
  • the adhesive layer was coated on the release paper so that the thickness of the adhesive layer after drying was 30 ⁇ m, and dried at 100 ° C. for 2 minutes to form an adhesive layer.
  • the adhesive layer and the elastomer film surface of the laminated film were bonded together using a rubber roll, and then cured at 23 ° C.-50% RH for 1 week to obtain an adhesive tape for skin attachment with a release paper.
  • Examples 2-27, Comparative Examples 1-7 In each of Examples 2 to 27 and Comparative Examples 1 to 7, the same as in Example 1 except that the blending composition and the blending amount (parts by mass) of the pressure-sensitive adhesive were changed as shown in Tables 5 to 7. , A skin-sticking adhesive and a skin-sticking adhesive tape using the same were manufactured. In each of the examples 5 to 7, the conditions not shown in the table were set as common conditions.
  • ⁇ Probe tack> A test piece having a width of 30 mm and a length of 30 mm was cut out from the adhesive tape for skin application. Then, the release paper was peeled off from the test piece under a 23 ° C.-50% RH atmosphere, and the probe tack on the surface of the exposed adhesive layer was measured according to JIS Z0237. A probe tack measuring device (manufactured by Tester Sangyo Co., Ltd.) was used as the device.
  • a stainless steel probe (20 g) having a diameter of 5 mm ⁇ was brought into contact with the surface of the adhesive layer for 1 second with a contact load of 1.0 N / cm 2 , and then the probe was separated from the surface of the adhesive layer at a speed of 10 mm / sec. The peeling force of the probe at this time was measured. The measurement was carried out three times, and the average value was calculated.
  • Adhesion to the substrate The peeling of the adhesive layer from the support when the test piece was peeled was evaluated according to the following criteria. [Evaluation criteria] ⁇ : 9 to 10 people did not peel off, Yu. ⁇ : 7 to 8 people did not peel off, good. ⁇ : 4 to 6 people did not peel off, practically possible. ⁇ : 0 to 3 people did not peel off, not practical.
  • Adhesive residue The degree of adhesive residue on the skin after peeling the test piece was evaluated according to the following criteria. [Evaluation criteria] ⁇ : No adhesive residue was seen in 9 to 10 people, which was good. ⁇ : No adhesive residue was seen in 6 to 8 people, practically possible. ⁇ : No adhesive residue was seen in 0 to 5 people, not practical.
  • Staining solution composition Gentian Violet 1.0%, Brillian Green 0.5%, distilled water 98.5%
  • ⁇ : keratin peeling amount is 0% or more and less than 10%
  • excellent ⁇ : keratin peeling amount is 10% or more and less than 30%
  • good ⁇ : keratin peeling amount is 30% or more and less than 50%
  • practically possible ⁇ : keratin peeling Amount is 50% or more, 100% or less, impractical
  • Examples 1 to 20 which are adhesive tapes for skin application using an adhesive for skin application containing polyurethane polyol (P) and organic isocyanate (C), had good evaluation results for all the evaluation items.
  • Examples 22 to 27 which are adhesive tapes for skin application containing 10 to 80 parts of a plasticizer, pain at the time of peeling and low keratin peeling property are particularly good, and evaluation results are also obtained for other evaluation items. It was good.
  • Comparative Examples 1 to 7 which are adhesive tapes that did not use polyurethane polyol (P), none of them cleared all the evaluation items.

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