WO2023100501A1 - Adhésif pour fixation sur la peau et ruban adhésif pour fixation sur la peau - Google Patents

Adhésif pour fixation sur la peau et ruban adhésif pour fixation sur la peau Download PDF

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Publication number
WO2023100501A1
WO2023100501A1 PCT/JP2022/038428 JP2022038428W WO2023100501A1 WO 2023100501 A1 WO2023100501 A1 WO 2023100501A1 JP 2022038428 W JP2022038428 W JP 2022038428W WO 2023100501 A1 WO2023100501 A1 WO 2023100501A1
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mass
group
meth
urethane
adhesive
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PCT/JP2022/038428
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English (en)
Japanese (ja)
Inventor
岳 柏村
龍 佐藤
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Toyochem Co Ltd
Artience Co Ltd
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Toyo Ink SC Holdings Co Ltd
Toyochem Co Ltd
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Publication of WO2023100501A1 publication Critical patent/WO2023100501A1/fr
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    • 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
    • A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
    • 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
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • 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
    • 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
    • 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
    • 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
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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]

Definitions

  • Embodiments of the present invention relate to an adhesive for sticking to the skin, a cured product of the adhesive for sticking to the skin, and an adhesive tape for sticking to the skin.
  • Adhesive tapes for sticking to the skin are used as medical tapes such as adhesive plasters and surgical tapes; patch medicines such as poultices and plasters; tapes for eye make-up in the cosmetics field, for preventing slippage of wigs, and for creating wrinkles in special make-up. It is widely used (for example, Patent Document 1). Electrodes may be attached to the skin in low-frequency therapy, electroencephalogram or electrocardiogram measurements, and adhesive tapes for skin application are also used in this case.
  • the adhesive tape for skin application may be applied for a long period of time of one week or longer.
  • the adhesiveness between the base material and the adhesive deteriorated due to the influence of sebum, sweat, etc. absorbed by the adhesive over time, and there were cases in which adhesive residue occurred when the substrate was peeled off.
  • adhesives with reduced adhesive strength have been actively developed in order to suppress exfoliation of keratin when the tape is peeled off.
  • there was a problem of adhesive residue at the time of peeling In order to improve the adhesion between the base material and the pressure-sensitive adhesive, complicated processes using dedicated equipment such as primer treatment, corona treatment, and thermal lamination of the base material have been required.
  • One embodiment contains a polymer (A) having a reactive functional group, a urethane compound (B) having a mass average molecular weight of 1,500 to 40,000, and a curing agent (C), and the urethane compound
  • the content of (B) is 0.05 to 20 parts by mass with respect to 100 parts by mass of the polymer (A).
  • Another embodiment relates to a cured product obtained by curing the pressure-sensitive adhesive for skin application.
  • Another embodiment relates to an adhesive tape for sticking to the skin, which has a substrate and an adhesive layer containing the cured product.
  • a pressure-sensitive adhesive for skin application and a cured product that can provide a pressure-sensitive adhesive tape for application on skin having excellent adhesion and transparency. Further, according to another embodiment of the present invention, it is possible to provide a pressure-sensitive adhesive tape for skin application that has excellent adhesiveness and transparency.
  • the pressure-sensitive adhesive for skin application which is an embodiment of the present invention, comprises a polymer (A) having a reactive functional group (in this specification, may be simply referred to as “polymer (A)”) and a polymer having a weight average molecular weight of 1. , 500 to 40,000 (in this specification, it may be simply referred to as "urethane compound (B)”) and a curing agent (C).
  • the content of the urethane compound (B) is 0.05 to 20 parts by mass with respect to 100 parts by mass of the polymer (A).
  • Polymer (A) having a reactive functional group has at least one reactive functional group in the molecule.
  • reactive functional groups include carboxyl groups, hydroxyl groups, amide groups (groups containing an amide bond), epoxy groups, amino groups, and the like.
  • the reactive functional group preferably includes at least one selected from the group consisting of hydroxyl groups and carboxyl groups.
  • polymer (A) examples include acrylic polymers, urethane polymers, polyethers, etc. that have reactive functional groups.
  • the polymer (A) preferably contains at least one selected from the group consisting of an acrylic polymer having a reactive functional group, a urethane polymer having a reactive functional group, and a polyether having a reactive functional group. , a carboxyl group-containing acrylic polymer, a hydroxyl group-containing acrylic polymer, a hydroxyl group-containing urethane polymer, and a polyether polyol.
  • Polymer (A) can be used alone or in combination of two or more.
  • An acrylic polymer having a reactive functional group (in this specification, may be referred to as a "reactive functional group-containing acrylic polymer") is a (meth)acrylic acid ester and a reactive functional group-containing monomer (b) and preferably one or more selected from the group consisting of (meth)acrylic acid esters having an alkyl group and (meth)acrylic acid esters having an alicyclic structure. (meth)acrylic acid ester (a) and a monomer component containing a reactive functional group-containing monomer (b).
  • the reactive functional group-containing acrylic polymer preferably contains at least one selected from the group consisting of a carboxyl group-containing acrylic polymer and a hydroxyl group-containing acrylic polymer, and more preferably contains a carboxyl group-containing acrylic polymer. preferable.
  • the reactive functional group-containing acrylic polymer can be used alone or in combination of two or more.
  • the (meth)acrylic acid ester (a) can improve the adhesive strength and cohesive strength of the reactive functional group-containing acrylic polymer.
  • the adhesive strength is further improved.
  • the (meth)acrylic acid ester (a) contains a (meth)acrylic acid ester having an alicyclic structure, the cohesive force is further improved.
  • the (meth)acrylic acid ester (a) can be used alone or in combination of two or more.
  • the content of acrylic acid ester (a) is preferably 70 to 99.7% by mass in 100% by mass of the monomer component, more preferably 80 to 99.5% by mass, 88 to More preferably 99% by mass, particularly preferably 92 to 98% by mass. When it is 70 to 99.7% by mass, it becomes easier to achieve both adhesive strength and transparency.
  • the combined use of a (meth)acrylic acid ester having an alkyl group with 8 to 12 carbon atoms and a (meth)acrylic acid ester having an alicyclic structure may further improve the adhesive strength.
  • the mass ratio of the (meth)acrylic acid ester having an alkyl group having 8 to 12 carbon atoms and the (meth)acrylic acid ester having an alicyclic structure is from 100/0 to the balance between adhesive strength and cohesive strength. 50/50 is preferred, and 100/0 to 65/35 are more preferred.
  • Examples of (meth)acrylic acid esters having an alkyl group having 8 to 12 carbon atoms include 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, and nonyl (meth)acrylate. , isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate and the like.
  • 2-ethylhexyl (meth)acrylate can achieve both adhesive strength and transparency at a high level.
  • Examples of (meth)acrylic acid esters having an alicyclic structure include cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and isobornyl (meth)acrylate. mentioned. Among these, cyclohexyl (meth)acrylate can achieve both adhesive strength and transparency at a higher level.
  • the reactive functional group-containing monomer (b) can function as a cross-linking point for the cross-linking reaction with the curing agent.
  • the content of the reactive functional group-containing monomer (b) is preferably 0.3 to 30% by mass in 100% by mass of the monomer component, more preferably 0.5 to 20% by mass, and 1 to More preferably 12% by mass, particularly preferably 2 to 8% by mass. When it is 0.3 to 30% by mass, the desired crosslink density is easily obtained, and the adhesive strength and cohesive strength are easily adjusted.
  • Examples of reactive functional group-containing monomers (b) include carboxyl group-containing monomers, hydroxyl group-containing monomers, amide group-containing monomers, epoxy group-containing monomers, and amino group-containing monomers. Among these, carboxyl group-containing monomers, hydroxyl group-containing monomers, and amide group-containing monomers are preferable, carboxyl group-containing monomers and hydroxyl group-containing monomers are more preferable, and carboxyl group-containing monomers are still more preferable.
  • the reactive functional group-containing monomer (b) can be used alone or in combination of two or more.
  • Carboxyl group-containing monomers include, for example, (meth)acrylic acid, phthalic acid monohydroxyethyl acrylate, p-carboxybenzyl acrylate, ethylene oxide-modified (ethylene oxide added mole number is 2 to 18) phthalic acid acrylic acid ester, monohydroxyethyl succinate acrylate, ⁇ -carboxyethyl acrylate, itaconic acid and the like.
  • (meth)acrylic acid is preferred.
  • the content of the carboxyl group-containing monomer is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass, based on 100% by mass of the monomer component.
  • hydroxyl group-containing monomers examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, ( hydroxyalkyl (meth)acrylates such as 3-hydroxybutyl methacrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; polyethylene Glycol mono(meth)acrylates such as glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate; caprolactone-modified (meth)acrylic Acid ester; N-hydroxyalkyl(meth)acrylamide such as N-hydroxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, and the like.
  • the content of the hydroxyl group-containing monomer is preferably 0.01 to 7% by mass, more preferably 0.05 to 5% by mass, based on 100% by mass of the monomer component.
  • amide group-containing monomers examples include (meth)acrylamide, N-methyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-(butoxymethyl)acrylamide, and other (meth)acrylamide compounds containing heterocycles. compound.
  • the content of the amide group-containing monomer is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass, based on 100% by mass of the monomer component.
  • epoxy group-containing monomers examples include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate.
  • the content of the epoxy group-containing monomer is preferably 0.1 to 1 part by mass based on 100% by mass of the monomer component.
  • amino group-containing monomers examples include (meth)acrylates such as monomethylaminoethyl (meth)acrylate, monoethylaminoethyl (meth)acrylate, monomethylaminopropyl (meth)acrylate, and monoethylaminopropyl (meth)acrylate. ) acrylic acid monoalkylamino esters, and the like.
  • the content of the amino group-containing monomer is preferably 0.1 to 1 part by mass in 100% by mass of the monomer component.
  • the monomer component may contain other monomers in addition to the (meth)acrylic acid ester (a) and the reactive functional group-containing monomer (b).
  • Other monomers may be monomers that do not impair the adhesive strength and cohesive strength of the pressure-sensitive adhesive.
  • examples of other monomers include (meth)acrylic acid alkyl ester monomers having alkyl groups of 1 to 7 or 13 or more carbon atoms, aromatic ring-containing monomers, alkoxy(poly)alkylene oxide-containing monomers, and other vinyl monomers. be done.
  • Acrylic polymers containing reactive functional groups can be synthesized by radical polymerization such as solution polymerization, bulk polymerization, and emulsion polymerization.
  • solution polymerization is preferable from the viewpoint that the weight average molecular weight of the reactive functional group-containing acrylic polymer can be easily adjusted.
  • Radical polymerization preferably uses a polymerization initiator.
  • Polymerization initiators are generally azo compounds and organic peroxides.
  • the weight average molecular weight (hereinafter also referred to as Mw) of the reactive functional group-containing acrylic polymer is preferably 400,000 to 1,500,000, more preferably 500,000 to 1,400,000, and even more preferably 600,000 to 1,300,000.
  • Mw is a polystyrene-equivalent value measured by gel permeation chromatography (GPC). Specifically, Mw can be measured by the method described in Examples.
  • a urethane-based polymer having a reactive functional group (in this specification, may be referred to as a "reactive functional group-containing urethane-based polymer”) can be obtained, for example, by reacting a component containing a polyol component and a polyisocyanate component.
  • Polyurethane urea or the like obtained by urea reaction of a polyurethane obtained or a urethane prepolymer obtained by reacting a component containing a polyol component and a polyisocyanate component in excess of isocyanate groups with an amine component. .
  • the former polyurethane has at least one selected from the group consisting of an isocyanate group and a hydroxyl group as a reactive functional group, depending on the type and amount of each component.
  • the latter polyurethaneurea has at least one selected from the group consisting of an isocyanate group, an amino group and a hydroxyl group as a reactive functional group, depending on the type and amount of each component.
  • the reactive functional group-containing urethane-based polymer can be used alone or in combination of two or more.
  • the weight average molecular weight of the reactive functional group-containing urethane polymer may be, for example, 10,000 to 500,000, 25,000 to 500,000, or 30,000 to 300,000. It is preferably 45,000 to 500,000, more preferably 55,000 to 300,000, from the viewpoint of obtaining particularly excellent initial curability and adhesiveness.
  • the content of the polymer (A) in the pressure-sensitive adhesive for skin application is preferably 40-99.9% by mass, more preferably 60-99.9% by weight, based on the weight of the pressure-sensitive adhesive for skin application.
  • the pressure-sensitive adhesive can exhibit superior adhesive strength and cohesive strength.
  • Polyurethane can be obtained, for example, by reacting components containing a polyol component and a polyisocyanate component.
  • the resulting polyurethane has at least one selected from the group consisting of isocyanate groups and hydroxyl groups as a reactive functional group.
  • the polyurethane preferably has hydroxyl groups as reactive functional groups.
  • the polyurethane may be, for example, a polyurethane polyol obtained by reacting a polyol component (a) containing a polyether polyol (a1) with a component containing a polyisocyanate component (b).
  • the polyisocyanate component (b) preferably contains at least diisocyanate.
  • the hydroxyl value of the polyurethane polyol is preferably 2.0-45 mgKOH/g, more preferably 3.0-40 mgKOH/g.
  • the hydroxyl value is 2.0 mgKOH/g or more, it tends to be possible to suppress adhesive residue due to an increase in the cohesive force of the pressure-sensitive adhesive, and the increase in reaction points facilitates the development of good initial curability.
  • the hydroxyl value is 45 mgKOH/g or less, the pressure-sensitive adhesive becomes softer, the keratin exfoliation improves, and the adherence to the skin tends to improve due to the improved followability to the skin.
  • the hydroxyl value can be measured by the method described in Examples.
  • the weight average molecular weight of the polyurethane polyol is preferably 25,000 to 300,000, more preferably 30,000 to 300,000, still more preferably 45,000 to 300,000, and 55,000 to 20,000. Wan is particularly preferred. Within this range, excellent coatability and initial curability can be imparted.
  • the polyol component (a) contains at least polyether polyol (a1).
  • the polyol component (a) is preferably a polyether polyol (a1 -1) and may further contain another polyol (a2).
  • the average number of hydroxyl groups in the polyether polyol (a1-1) is preferably 3 or more.
  • Polyol component (a) can be used alone or in combination of two or more.
  • the presence of the primary hydroxyl group provides excellent initial curability, and the reaction tends to occur more uniformly than ordinary polyols, resulting in the formation of oligomers normally produced due to insufficient curing. As a result, there is a tendency that the occurrence of adhesive residue can be suppressed.
  • the content of the polyether polyol (a1-1) contained in 100% by mass of the polyol component (a) is preferably 25-100% by mass, particularly preferably 35-100% by mass. When it is within this range, it exhibits high reactivity, so that it is easy to form an adhesive layer that has excellent initial curability and is less likely to leave adhesive residue.
  • Polyether polyol (a1-1) is not particularly limited, but can be obtained by the following known methods.
  • a compound having an active oxygen atom with a functional group number of 2 or more such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and ethylenediamine, is used as an initiator to open a ring of ethylene oxide, butylene oxide, tetrahydrofuran, and the like. It is obtained by polymerizing an oxirane compound that gives a terminal primary hydroxyl group. In this case, all terminal hydroxyl groups are primary hydroxyl groups.
  • a compound having an active oxygen atom having a functional group number of 2 or more such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and ethylenediamine, is used as an initiator to open a ring of ethylene oxide, butylene oxide, tetrahydrofuran, and the like. It is obtained by randomly polymerizing an oxirane compound that gives a terminal primary hydroxyl group and an oxirane compound that gives a terminal secondary hydroxyl group by ring opening, such as propylene oxide.
  • the primary hydroxyl group content can be controlled by the compounding ratio of the oxirane compound that provides the terminal primary hydroxyl group and the oxirane compound that provides the terminal secondary hydroxyl group.
  • Commercially available products include ADEKA POLYETHER PR-3007, ADEKA POLYETHER PR-5007, ADEKA POLYETHER GR-2505, ADEKA POLYETHER GR-3308 (manufactured by ADEKA).
  • a compound having an active oxygen atom with a functional group number of 2 or more such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, ethylenediamine, etc.
  • This is a method of polymerizing oxirane compounds such as ethylene oxide, butylene oxide and tetrahydrofuran.
  • 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 of the oxirane compound added lastly, such as ethylene oxide, butylene oxide, tetrahydrofuran, etc., which provides terminal primary hydroxyl groups by ring opening.
  • the oxirane compound added lastly such as ethylene oxide, butylene oxide, tetrahydrofuran, etc., which provides terminal primary hydroxyl groups by ring opening.
  • Pronon #201 Pronon #202B (manufactured by NOF Corporation), 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.), Sannix GL-600, Sannix GL-3000 (manufactured by Sanyo Chemical Industries), and the like.
  • a compound having an active oxygen atom with a functional group number of 2 or more such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, ethylenediamine, etc.
  • propylene oxide is produced using a specific catalyst. It can be obtained by a method of ⁇ -cleavage addition (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, type, etc. of the catalyst used.
  • Commercially available products include Primepol PX1000, Primepol FX2202, and Primepol 3550 (manufactured by Sanyo Chemical Industries, Ltd.).
  • the polyether polyol (a1-1) is preferably a polyether polyol containing polypropylene glycol as a main component obtained by [Method 3] and [Method 4].
  • a polypropylene glycol By using such a polypropylene glycol, it is possible to obtain a polyurethane polyol having excellent flexibility and water resistance, and exhibit more excellent skin adhesion, low keratin exfoliation and water resistance.
  • the polyether polyol (a1-1) has a primary hydroxyl group content of 40 mol % or more, preferably 70 mol % or more and 100 mol % or less.
  • the primary hydroxyl group content can be determined by pretreating (esterifying) a sample and then measuring it by 1 H-NMR.
  • Mn number average molecular weight of the polyether polyol (a1-1) is not particularly limited, it is preferably 400 to 20,000, particularly preferably 600 to 15,000. When the number average molecular weight is within the above range, it is possible to exhibit appropriate cohesion and good initial curability.
  • Mn is a polystyrene-equivalent value measured by gel permeation chromatography (GPC). Specifically, Mn can be measured by the method described in Examples.
  • the average number of hydroxyl groups of the polyether polyol (a1-1) 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 within the above range, it is possible to have an appropriate crosslink density and exhibit suitable adhesive physical properties.
  • the average number of hydroxyl groups refers to the number of active hydrogen atoms per molecule of the initiator used as a raw material when producing the polyol component (a). Trimethylolpropane is 3.
  • Other polyols (a2) include, for example, polyester polyols, polyether polyols other than polyether polyol (a1-1), low molecular weight polyols, polybutadiene-modified polyols, polycaprolactone polyols, polycarbonate polyols, polyacrylic polyols, or castor oil-based polyols. etc.
  • polyester polyols, polyether polyols other than polyether polyol (a1-1), polycaprolactone polyols, or polycarbonate polyols are preferable, and are excellent in wettability and followability to the skin, so polyester polyols, or Polyether polyols other than polyether polyol (a1-1) are more preferred.
  • polyester polyol A known polyester polyol is used as the polyester polyol.
  • an acid component and a glycol component are essential, and it can be synthesized by an esterification reaction using a polyol component as necessary.
  • acid components include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, phthalic anhydride, isophthalic acid and trimellitic acid.
  • glycol components ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3′- Examples include dimethylolheptane, butylethylpentanediol, polyoxyethylene glycol, and polyoxypropylene glycol, and examples of polyol components include glycerin, trimethylolpropane, pentaerythritol, and the like.
  • the number average molecular weight of the polyester polyol is not particularly limited, it is preferably from 500 to 5,000. When a polyester polyol having a number average molecular weight of 500 to 5,000 is used, moderate reactivity can be obtained, and a polyurethane polyol having better cohesive strength can be easily obtained.
  • the polyester polyol content is preferably 0 to 75% by mass, more preferably 0 to 65% by mass, based on 100% by mass of the polyol component (a).
  • a known polyether polyol is used as the polyether polyol other than the polyether polyol (a1-1).
  • Polyether polyols are, for example, water; ethylene glycol, propylene glycol, glycerin, using low molecular weight polyols such as trimethylolpropane as initiators, and polymerizing oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran.
  • Polyether polyols other than polyether polyol (a1-1) are preferably polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. having one or more hydroxyl groups, more preferably polypropylene glycol.
  • the number average molecular weight of polyether polyols other than polyether polyol (a1-1) is not particularly limited, but is preferably 500 to 10,000. When the number average molecular weight is from 500 to 10,000, it is easy to obtain a polyurethane polyol having moderate flexibility and good skin adhesiveness.
  • the content of polyether polyols other than polyether polyol (a1-1) is preferably 0 to 75% by mass, more preferably 0 to 65% by mass, based on 100% by mass of 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 - Compounds having a molecular weight of less than 500 and having two or more terminal hydroxyl groups, such as glycols such as nonanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, xylitol and mannitol.
  • a low-molecular-weight polyol the number of urethane bonds in the pressure-sensitive adhesive increases, and appropriate cohesive strength and good adhesion to substrates 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, based on 100% by mass of the polyol component (a). By setting the content within the above range, it is possible to improve the adhesive residue and the adhesion to the substrate.
  • the polybutadiene-modified polyol has, for example, two or more hydroxyl groups at the terminals, and has a 1,2-vinyl site, a 1,4-cis site, a 1,4-trans site, or a hydrogenated structure thereof. , linear or branched polybutadiene.
  • the number average molecular weight (Mn) of the polybutadiene-modified polyol is preferably 500-6,000, more preferably 800-6,000. By setting the number average molecular weight within the above range, appropriate reactivity can be obtained, and a polyurethane polyol having good cohesive strength can be easily obtained.
  • the content of the polybutadiene-modified 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).
  • Polycaprolactone polyols are preferably caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ⁇ -caprolactone and ⁇ -valerolactone.
  • the number average molecular weight of the polycaprolactone polyol is not particularly limited, it is preferably from 500 to 5,000. When the number average molecular weight is within the above range, appropriate reactivity can be obtained, and skin adhesiveness and cohesive strength can be further improved.
  • the content of polycaprolactone polyol is preferably 0 to 75% by mass, more preferably 0 to 65% by mass, based on 100% by mass of polyol component (a).
  • Polycarbonate polyols include, for example, a polycarbonate polyol obtained by subjecting the above polyol component and phosgene to a polycondensation reaction; Polycarbonate polyols obtained by subjecting propylene carbonate, diphenyl carbonate, dibenzyl carbonate, and other carbonic acid diesters to transesterification condensation; Copolymerized polycarbonate polyols obtained by using two or more of the above polyol components in combination; Various polycarbonate polyols above and carboxyl group-containing polyols Polycarbonate polyol obtained by esterifying a compound; Polycarbonate polyol obtained by etherifying the above various polycarbonate polyols and a hydroxyl group-containing compound; Obtained by transesterifying the above various polycarbonate polyols and an ester compound.
  • a polycarbonate polyol obtained by subjecting the above polyol component and phosgene to a polycondensation reaction Polycarbonate polyols obtained
  • Polycarbonate polyols Polycarbonate polyols; Polycarbonate polyols obtained by transesterification of various polycarbonate polyols and hydroxyl group-containing compounds; Polyester-based polycarbonate polyols obtained by polycondensation reaction of various polycarbonate polyols and dicarboxylic acid compounds; Various polycarbonate polyols and a copolymerized polyether-based polycarbonate polyol obtained by copolymerizing alkylene oxide; and the like.
  • the number average molecular weight of the polycarbonate polyol is not particularly limited, but a number average molecular weight of 500 to 5,000 is preferred. By setting the number average molecular weight within the above range, appropriate reactivity can be obtained, and a polyurethane polyol having good cohesive strength can be easily obtained.
  • Polycarbonate polyol is preferably 0 to 75% by mass, more preferably 0 to 65% by mass, based on 100% by mass of polyol component (a).
  • the other polyol (a2) is preferably a polyol having a hydroxyl group with a functional number of 1-6, particularly preferably 1-4.
  • the polyol (a2) within the above range, the crosslink density and hydroxyl value of the polyurethane polyol can be appropriately controlled, and excellent skin adhesiveness and initial curability can be exhibited.
  • polyol component (a) when polyol component (a) contains two or more polyols, polyol component (a) preferably contains polyether polyol (a1-1) and other polyol (a2), more preferably polyether polyol It contains (a1-1) and a polyester polyol.
  • the polyether polyol (a1-1) is preferably 70 to 95% by mass, more preferably 60 to 97% by mass, based on 100% by mass of the polyol component (a).
  • the other polyol (a2) is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, based on 100% by mass of the polyol component (a).
  • polyisocyanate component (b) known ones can be used, including aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
  • Polyisocyanate component (b) can be used alone or in combination of two or more.
  • Aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tri diisocyanate, 4,4′-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, and 4,4′,4 "-triphenylmethane triisocyanate, ⁇ , ⁇ '-diisocyanate-1,3-dimethylbenzene, ⁇ , ⁇ '-diisocyanate-1,4-dimethylbenzene, ⁇ , ⁇ '-diisocyanate-1,4-diethylbenzene, 1 ,4-tetra
  • Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2 ,4,4-trimethylhexamethylene diisocyanate and the like, and hexamethylene diisocyanate and pentamethylene diisocyanate are preferred because the raw materials are readily available.
  • Alicyclic polyisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4 -cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, and 1,4-bis(isocyanatomethyl)cyclohexane.
  • 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, and 1,4-cyclohexane diisocyanate are preferred because raw materials are readily available.
  • polyisocyanates exemplified above are diisocyanates
  • triisocyanates obtained by modifying the above diisocyanates can also be used.
  • triisocyanates include trimethylolpropane adducts, biuret forms, and trimers of the above diisocyanates (the trimers contain an isocyanurate ring).
  • polyisocyanate component (b) 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and 3-isocyanatomethyl-3,5 ,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate (IPDI)) and the like are particularly preferred.
  • MDI 4,4'-diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • the polyisocyanate component (b) preferably contains diisocyanate.
  • Diisocyanate is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 90 to 100% by mass, based on 100% by mass of the polyisocyanate component (b).
  • the amount of the polyisocyanate component (b) used is preferably 0.1 to 25 parts by mass based on 100 parts by mass of the polyol component (a). When the content is within the above range, it becomes easier to appropriately control the molecular weight and urethane bond concentration of the polyurethane polyol.
  • the polymerization method of the polyurethane polyol is not particularly limited, and known polymerization methods such as bulk polymerization method and solution polymerization method can be applied.
  • a known catalyst and/or solvent can be used for the polymerization, if desired.
  • various methods are possible, they are roughly classified into the following two methods.
  • [Method 1] A method in which the polyol component (a), the polyisocyanate component (b), and, if necessary, a catalyst and/or a solvent, etc. are all charged into a flask and copolymerized.
  • Methodhod 2 A method in which the polyol component (a), optionally a catalyst, and/or a solvent, etc. are placed in a flask, and the polyisocyanate component (b) is added dropwise thereto for polymerization.
  • [Method 2] is preferable because the reaction can be easily controlled.
  • Polyurethane urea can be obtained, for example, by reacting a urethane prepolymer obtained by reacting a component containing a polyol component and a polyisocyanate component with an excess of isocyanate groups, and an amine component, through a urea reaction.
  • the resulting polyurethaneurea has at least one selected from the group consisting of an isocyanate group, an amino group and a hydroxyl group as a reactive functional group.
  • the polyurethaneurea preferably has hydroxyl groups as reactive functional groups.
  • Polyurethane urea is, for example, a urethane prepolymer obtained by reacting a polyol component (a) containing a polyether polyol (a1) and a component containing a polyisocyanate component (b) with an excess of isocyanate groups, and an amine component. and may be a polyurethane urea polyol to which the urea is reacted.
  • the polyisocyanate component (b) preferably contains at least diisocyanate.
  • the hydroxyl value of the polyurethane urea is preferably 5.0 mgKOH/g or more from the viewpoint of ensuring the cohesive strength of the adhesive, and preferably 20.0 mgKOH/g or less from the viewpoint of ensuring the adhesive strength of the adhesive. and more preferably 7.0 mgKOH/g or more and 15.0 mgKOH/g or less.
  • the weight average molecular weight of the polyurethane urea is preferably 10,000 or more from the viewpoint of ensuring the cohesive strength of the adhesive, and is preferably 500,000 or less, more preferably 500,000 or less from the viewpoint of ensuring the adhesive strength of the adhesive. is 30,000 to 300,000, more preferably 45,000 to 300,000, and particularly preferably 55,000 to 200,000.
  • Polyether polyol (a1-1) and/or other polyol (a2) can be used as the polyol component.
  • a polyol component can be used individually or in 2 or more types. When two or more types are used, it is preferable to use polypropylene glycol and/or polyethylene glycol, and polypropylene glycol alone or polypropylene glycol and polyethylene glycol in combination is more effective in terms of flexibility and cohesive strength. preferable.
  • the description of polyol component (a) in polyurethanes is also applicable to polyurethaneureas.
  • polyisocyanate component (b) described above can be used as the polyisocyanate component.
  • polyisocyanate components include the above-mentioned aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, and triisocyanates.
  • Polyisocyanate components can be used alone or in combination of two or more.
  • the description of polyisocyanate component (b) in polyurethanes is also applicable to polyurethaneureas.
  • the amine component is preferably a monoamine, a diamine, or a tri- or more functional amine, more preferably a diamine or a tri- or more functional amine, still more preferably a diamine or a tri- or more functional amine having a hydroxyl group, two or more amino groups or one Compounds with one or more amino groups and one or more hydroxyl groups are particularly preferred.
  • an amine component cohesive strength can be improved by urea bonding regardless of the molecular weight of polyurethaneurea.
  • the reaction rate is high, so the time until curing is completed is short, and the productivity is further improved.
  • the amine component can be used alone or in combination of two or more.
  • amine components include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine, and 2-hydroxyethyl.
  • amine components compounds having two or more secondary amino groups and one primary hydroxyl group are preferable from the viewpoint of controlling the urea reaction.
  • known compounds can be used without limitation.
  • An example of a method for synthesizing a compound having two or more secondary amino groups and one primary hydroxyl group is to add at least one hydroxyl group and (meth)acryloyl group to a compound having two or more primary amino groups.
  • a compound obtained by a Michael addition reaction of a compound having a specificity is preferable.
  • the hydroxyl group possessed by the compound is preferably a primary hydroxyl group.
  • Examples of compounds having two or more primary amino groups include the compounds exemplified as amine components. Among these, isophoronediamine, 2,2,4-trimethylhexamethylenediamine, and hexamethylenediamine are preferable because the Michael addition reaction can be easily controlled.
  • Compounds having at least one hydroxyl group and (meth)acryloyl group include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl Hydroxyalkyl (meth)acrylates such as (meth)acrylate, 3-hydroxybutyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate can be mentioned.
  • a Michael addition reaction can also be performed with other compounds having a (meth)acryloyl group.
  • compounds having other (meth)acryloyl groups include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ) acrylate, heptyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate , tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexa
  • the Michael addition reaction between a diamine compound and a compound having a (meth)acryloyl group 1 mol of the active hydrogen of the amino group in the diamine compound and 1 mol of the ethylenically unsaturated group in the compound having the (meth)acryloyl group reacts. Since the amino group in the diamine compound readily undergoes Michael addition to the ethylenically unsaturated group of the compound having an electron-withdrawing group, the ethylenically unsaturated compound is preferably a (meth)acrylic compound, particularly an acrylate-based compound. compounds are most preferred in terms of efficiency of the Michael addition reaction.
  • the ratio of the compound having a (meth)acryloyl group to be added to the compound having two or more primary amino groups at least two primary or secondary amino groups remain in the compound having a (meth)acryloyl group. so that it is preferably 0.1 to 1.0 mol, more preferably 0.2 to 1.0 mol, per 1 mol of the primary amino group of the compound having two or more primary amino groups. It is preferable to react the (meth)acryloyl group in the compound having the (meth)acryloyl group with.
  • the amount of the polyol component (a) used is preferably 40% by mass or more based on 100% by mass of polyurethane urea from the viewpoint of maintaining the cohesive force of the pressure-sensitive adhesive and imparting durability. It is preferably 90% by mass or less, more preferably 50 to 80% by mass, from the viewpoint of preventing and securing sufficient adhesive strength.
  • "in 100% by mass of polyurethane urea” means "in 100% by mass of synthetic raw materials for polyurethane urea”. In the total 100% by mass of the amine component to be used and the reaction terminator used as necessary (the same meaning is used in the following description).
  • the amount of the polyisocyanate component (b) used is preferably 5% by mass or more in 100% by mass of polyurethane urea from the viewpoint of maintaining the cohesive force of the pressure-sensitive adhesive and imparting durability. From the viewpoint of preventing deterioration and ensuring sufficient adhesive strength, the content is preferably 50% by mass or less, more preferably 10 to 30% by mass.
  • the amount of the amine component used is preferably 0.5% by mass or more based on 100% by mass of polyurethane urea, from the viewpoint of maintaining the cohesive force of the pressure-sensitive adhesive and imparting durability. It is preferably 20% by mass or less, more preferably 1 to 10% by mass, from the viewpoint of preventing and securing sufficient adhesive strength.
  • the polymerization method of polyurethane urea is not particularly limited, and known polymerization methods such as bulk polymerization method and solution polymerization method can be applied.
  • a known catalyst and/or solvent can be used for the polymerization, if desired.
  • various methods are possible, they are roughly classified into the following two methods.
  • Method 1 A method in which all of the polyol component, polyisocyanate component and amine component are charged and copolymerized.
  • Method 2 (Method of conducting urethanization reaction and urea formation reaction at once)
  • a polyol component and a polyisocyanate component, which are part of the raw materials, are charged and copolymerized to obtain a urethane prepolymer having at least one isocyanate group.
  • a method of further copolymerizing with a reaction terminator according to. (Method of urea-forming the obtained urethane prepolymer after urethanization reaction) [Method 2] is more preferable if the reaction is to be precisely controlled.
  • a urethane-based polymer having a reactive functional group can be obtained, for example, by copolymerizing a polyol component and a polyisocyanate component, or by copolymerizing a polyol component, a polyisocyanate component and an amine component.
  • the obtained copolymer can be further copolymerized with a monoamine compound as a reaction terminator, if necessary. That is, when synthesizing a urethane-based polymer having a reactive functional group, for the purpose of controlling the molecular weight or stabilizing the reaction activity of the polymer by reacting with the isocyanate group remaining unreacted at the end of the copolymer, A reaction quenching agent can be used.
  • reaction terminator examples include dialkylamines such as diethylamine, di-n-butylamine, di-n-octylamine, dicyclohexylamine and diisononylamine, as well as monoethanolamine, diethanolamine, 2-amino-2-methyl- Monoamines having a hydroxyl group such as 1-propanol, tri(hydroxymethyl)aminomethane, 2-amino-2-ethyl-1,3-propanediol can be used.
  • dialkylamines such as diethylamine, di-n-butylamine, di-n-octylamine, dicyclohexylamine and diisononylamine
  • monoethanolamine diethanolamine
  • 2-amino-2-methyl- Monoamines having a hydroxyl group such as 1-propanol, tri(hydroxymethyl)aminomethane, 2-amino-2-ethyl-1,3-propanediol can be used.
  • reaction terminating agents monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tri(hydroxymethyl)aminomethane, 2-amino-2-ethyl-1,3-propanediol, etc.
  • a monoamine compound having a hydroxyl group When a monoamine compound having a hydroxyl group is used, a urethane-based polymer having a terminal hydroxyl group and excellent storage stability can be obtained. Further, a urethane-based polymer having a terminal hydroxyl group is preferable because it can be used as a reaction point with the isocyanate curing agent described later.
  • both the amino group and the hydroxyl group can react with the terminal isocyanate group of the urethane-based prepolymer, but the reactivity of the amino group is higher and the isocyanate group is preferentially react with
  • the amount used is 0.05% by mass or more based on 100% by mass of the urethane polymer having a reactive functional group from the viewpoint of ensuring the reaction stability of the urethane polymer. It is preferably 5% by mass or less from the viewpoint of appropriately controlling the mass average molecular weight (Mw) of the urethane-based polymer to ensure the durability of the adhesive.
  • Mw mass average molecular weight
  • Polyethers having reactive functional groups may be, for example, polyether polyols, ether ester polyols obtained by partially ester-modified polyether polyols, and polyalkylenes having amino groups (e.g., ethylene and propylene) oxide diamines. , polyether polyols are preferred.
  • the reactive functional group-containing polyether can be used alone or in combination of two or more.
  • the weight average molecular weight of the polyether having a reactive functional group is preferably It is 12,000 or more, more preferably 13,000 or more, and still more preferably 14,000 or more.
  • the weight average molecular weight of the polyether having a reactive functional group is preferably It is 30,000 or less, more preferably 20,000 or less, and still more preferably 18,000 or less.
  • the polyether polyol has an average number of hydroxyl groups of 2 or more, preferably 3 or more.
  • polyether polyols other than the polyether polyol (a1-1) exemplified as the polyether polyol (a1-1) and other polyols (a2) can be used.
  • polyether polyols having an average number of hydroxyl groups of 3 include polyether polyols obtained by ring-opening polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, etc., using a substance having three active hydrogen groups such as glycerin and trimethylolpropane as an initiator. .
  • Preminol 7012 manufactured by AGC: polyether polyol, ethylene oxide (EO) units and propylene oxide using glycerin as an initiator (PO) unit copolymer, mass average molecular weight of 15,000, average functional group number (F) 3, manufactured by AGC
  • Preminol 3012 polyether poly
  • the pressure-sensitive adhesive for skin application contains a urethane compound (B) having a mass average molecular weight of 1,500 to 40,000.
  • the urethane compound (B) may be a compound capable of functioning as an adhesion imparting agent.
  • Favorable adhesiveness is obtained as the mass average molecular weight of the urethane compound (B) is 1,500 or more. Furthermore, it tends to be able to suppress skin irritation.
  • Favorable adhesiveness and transparency are obtained as the mass average molecular weight of the urethane compound (B) is 40,000 or less. Furthermore, it tends to have excellent compatibility with other components.
  • the weight average molecular weight may be 5,000 or greater, or 10,000 or greater.
  • the weight average molecular weight may be 30,000 or less, or 20,000 or less.
  • the urethane compound (B) can be used alone or in combination of two or more.
  • the content of the urethane compound (B) in the pressure-sensitive adhesive for skin application is 0.05 to 20 parts by mass with respect to 100 parts by mass of the polymer (A).
  • Favorable adhesiveness and transparency are obtained as content of a urethane compound (B) is in the said range.
  • the content of the urethane compound (B) may be 0.06 parts by mass or more, 0.1 parts by mass or more, or 0.3 parts by mass or more.
  • the content of the urethane compound (B) may be 17 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, or 10 parts by mass or less.
  • the urethane compound (B) is a compound containing at least one urethane bond in its molecule. However, the polymer (A) is excluded from the urethane compound (B). That is, the urethane compound (B) is a compound other than the polymer (A). Examples of the urethane compound (B) include urethane-based oligomers and urethane branched compounds.
  • the urethane compound (B) preferably contains an aromatic isocyanate-derived structure in its molecule.
  • the aromatic isocyanate preferably contains at least one selected from the group consisting of toluene diisocyanate (TDI), xylylene diisocyanate (XDI), and diphenylmethane diisocyanate (MDI), more preferably toluene diisocyanate (TDI). preferable.
  • the urethane compound (B) preferably contains a tri- or more functional isocyanate-derived structure in the molecule.
  • the number of functional groups is, for example, 3-6, preferably 3-5.
  • trifunctional or higher isocyanates include nurate forms, adduct forms, biuret forms of diisocyanates exemplified in the description of the polyisocyanate component (b), polyisocyanates exemplified by the structural formulas below, and the curing agent (C) described later. and "compounds having 3 or more isocyanate groups in the molecule".
  • the urethane compound (B) may have an amino group.
  • the urethane compound (B) has an amino group, it preferably has an amine value of 0.1 to 60 mgKOH/g.
  • the amine value is 0.1 mgKOH/g or more, good adhesion tends to be obtained.
  • the amine value is 60 mgKOH/g or less, there is a tendency to prevent deterioration of compatibility with other components.
  • the amine value may be 1 mg KOH/g or greater, 5 mg KOH/g or greater, or 10 mg KOH/g or greater.
  • the amine number may be 30 mg KOH/g or less, 25 mg KOH/g or less, or 20 mg KOH/g or less.
  • the amine value of the urethane compound (B) can be measured by the method described in Examples.
  • the urethane-based oligomer is, for example, a urethane oligomer obtained by reacting a component containing a polyol component and a polyisocyanate component, or obtained by reacting a component containing a polyol component and a polyisocyanate component with an excess of isocyanate groups.
  • a urethane urea oligomer or the like obtained by reacting a urethane pre-oligomer and an amine component with urea may be used.
  • Urethane-based oligomers are preferably urethane oligomers. Urethane-based oligomers can be used alone or in combination of two or more.
  • the urethane-based oligomer can be obtained in a similar manner using the components exemplified in the explanation of the urethane-based polymer above.
  • the weight average molecular weight of the urethane-based oligomer is preferably 1,500 to 15,000, more preferably 1,500 to 10,000, even more preferably 1,500 to 5,000. . Within this range, there is a tendency that excellent adhesiveness can be imparted to the pressure-sensitive adhesive.
  • the above description of urethane-based polymers is also applicable to urethane-based oligomers, except that the weight average molecular weight is different.
  • the polyol component preferably contains a polyol component having two functional groups (that is, a diol component), and examples thereof include polyether polyols and polyester polyols having two functional groups.
  • the polyisocyanate component preferably contains a polyisocyanate component having a functionality of 2 (that is, a diisocyanate component), such as toluene diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate ( HDI), isophorone diisocyanate (IPDI), and the like.
  • TDI toluene diisocyanate
  • XDI xylylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • the urethane branched compound includes, for example, a structure obtained by reacting a polyisocyanate component containing tri- or more functional isocyanate with an alcohol component containing monoalcohol.
  • the urethane branched compound may further include any structure.
  • a urethane branched compound can be obtained, for example, by reacting a component containing a polyisocyanate component containing a trifunctional or higher isocyanate and an alcohol component containing a monoalcohol.
  • Urethane branched compounds can be used alone or in combination of two or more.
  • Tri- or more functional isocyanates include, for example, diisocyanate nurate, adduct, and biuret forms, polyisocyanates exemplified by the structural formulas below, and "three or more in the molecule" mentioned in the explanation of the curing agent (C) described later. compound having an isocyanate group” and the like.
  • a diisocyanate nurate can be obtained by a trimerization reaction of a diisocyanate.
  • the adduct can be obtained by reacting a diisocyanate with a tri- or higher functional polyol.
  • Biuret bodies can be obtained by formation of biuret bonds with diisocyanates.
  • diisocyanate the diisocyanates exemplified above for the polyisocyanate component (b) can be used. Examples include toluene diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and pentamethylene diisocyanate (PDI). Diisocyanates preferably include aromatic isocyanates.
  • the tri- or more functional polyol used for the reaction with the diisocyanate the tri- or more functional polyols exemplified above as examples of the low-molecular-weight polyols can be used.
  • each R independently represents a substituted or unsubstituted aromatic hydrocarbon group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a group containing two or more selected from these.
  • Each R may independently be a residue of the isocyanate component (b) described above, and is specifically selected from compounds exemplified as aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. It may be a residue of a diisocyanate.
  • R 1 represents a substituted or unsubstituted aromatic hydrocarbon group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a group containing two or more selected from these. Specific examples of R 1 include the following trivalent groups.
  • each R independently represents a substituted or unsubstituted aromatic hydrocarbon group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a group containing two or more selected from these.
  • Each R may independently be a residue of the isocyanate component (b) described above, and is specifically selected from compounds exemplified as aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. It may be a residue of a diisocyanate.
  • R 1 to R 5 are each independently a substituted or unsubstituted aromatic hydrocarbon group, aliphatic hydrocarbon group, alicyclic hydrocarbon group, or two or more selected from these. represents a group.
  • n is an integer from 0 to 5;
  • Each R may independently be a residue of the isocyanate component (b) described above, and is specifically selected from compounds exemplified as aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. It may be a residue of a diisocyanate.
  • R and R 1 to R 5 in formulas (1) to (3) are as follows.
  • n an integer of 5 or 6.
  • the compounds represented by formulas (1) to (3) may be, for example, the following compounds.
  • R 1 is a group represented by formula (1-1) above, R is a group represented by formula (d), and n in formula (d) is 6 Polyisocyanate
  • R is a group represented by formula (d)
  • n in formula (d) is 6.
  • n is 1 and R 1 , R 2 and R 4 are groups represented by formula (c), and R 3 and R 5 are groups represented by formula (d).
  • n is 1 and R 1 to R 5 are groups represented by formula (c).
  • n is 2 and R 1 to R 5 are groups represented by formula (c).
  • Formula (3) wherein n is 0 and R 1 , R 4 and R 5 are groups represented by the formula (b)
  • Examples of commercially available tri- or higher functional isocyanates include the following. Desmodur ultra IL, TDI Nurate, non-volatile content 51%, NCO content 8.0%, Desmodur N3300 HDI Nurate manufactured by Sumika Covestro Urethane Co., Ltd., non-volatile content 100%, NCO content 21.8%, Sumika Co.
  • the amount of tri- or higher functional isocyanate used is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 90 to 100% by mass, based on 100% by mass of the polyisocyanate component. Within the above range, there is a tendency that good adhesiveness can be imparted to the pressure-sensitive adhesive.
  • monoalcohols examples include monoalcohols such as polyester monoalcohols, polyether monoalcohols, polyacrylic monoalcohols, polybutadiene-modified monoalcohols, polycarbonate monoalcohols, castor oil-based monoalcohols, and aliphatic alcohols having 1 to 20 carbon atoms. is mentioned.
  • the monoalcohol preferably contains at least one selected from the group consisting of polyester monoalcohols, polyether monoalcohols, and polyacrylic monoalcohols.
  • the number average molecular weight of the monoalcohol is preferably 100-6,000, more preferably 150-5,000. Within the above range, there is a tendency that excellent compatibility and substrate adhesion can be exhibited.
  • a polyester monoalcohol is, for example, a compound (ring-opening polymer) obtained by ring-opening polymerization of a lactone using a monohydric alcohol as a starting component, and an esterification reaction of a diol and an acid component in the presence of a monohydric alcohol. It may be a compound (esterified product) or the like.
  • a ring-opening polymer can be preferably used as the polyester monoalcohol.
  • an alcohol having 1 to 20 carbon atoms is preferable, and an alcohol having 3 to 10 carbon atoms is more preferable.
  • Lactones include, for example, ⁇ -butyrolactone, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -heptanolactone, ⁇ -methyl- ⁇ - and propiolactone.
  • acid components include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, phthalic anhydride, isophthalic acid, and trimellitic acid.
  • a polyether monoalcohol may be, for example, a monoalkyl ether of a polyalkylene glycol compound.
  • a polyacrylic monoalcohol may be a compound obtained by reacting a poly(meth)acrylic acid alkyl ester with a thiol compound having a hydroxyl group through a thiolene reaction.
  • Examples of (meth)acrylic acid alkyl esters that can be used in the synthesis of poly(meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylic acid. Having an alkyl group of 1 to 7 carbon atoms such as isopropyl, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, etc. Examples thereof include (meth)acrylic acid alkyl esters, and (meth)acrylic acid alkyl esters having the above-described alkyl group having 8 to 12 carbon atoms.
  • thiol compounds having a hydroxyl group examples include 2-mercaptoethanol, 2-mercaptohexanol, 6-mercapto-1-hexanol, 3-mercapto-1-propanol, 7-mercapto-1-heptanol and the like.
  • the amount of monoalcohol used is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 85 to 100% by mass, based on 100% by mass of the alcohol component. Within the above range, there is a tendency that good adhesiveness can be imparted to the pressure-sensitive adhesive.
  • a monoalcohol and a polyol can be used together as the alcohol component.
  • the monoalcohol is preferably 50 to 99% by mass, more preferably 70 to 98% by mass, and even more preferably 85 to 97% by mass, based on 100% by mass of the alcohol component.
  • the polyol is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, and even more preferably 3 to 15% by mass based on 100% by mass of the alcohol component.
  • a catalyst and/or a solvent can be used as necessary for the reaction between the polyisocyanate component containing tri- or more functional isocyanate and the alcohol component containing monoalcohol.
  • the catalyst may be a catalyst commonly used in the synthesis of polyurethanes, such as tertiary amine-based compounds, organometallic compounds, and the like. Solvents commonly used in polyurethane synthesis such as methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, benzene, dioxane, acetonitrile, tetrahydrofuran, diglyme, dimethylsulfoxide, N-methylpyrrolidone, dimethylformamide, etc. can be The reaction temperature is, for example, 100 to 180°C, preferably 120 to 180°C.
  • a urethane branched compound can be obtained by reacting a polyisocyanate component containing a trifunctional or higher isocyanate with an alcohol component containing a monoalcohol. If necessary, the obtained reactant can be reacted with an amine component to introduce an amino group into the reactant. Thereby, a urethane branched compound having an amino group is obtained.
  • the amine component may be, for example, a hydroxyl group-containing dialkylamine compound, a viridyl group-containing amine compound, or the like.
  • hydroxyl group-containing dialkylamine compounds include dimethylaminomethanol, dimethylaminoethanol, dimethylaminopropanol, dimethylaminobutanol, diethylaminomethanol, diethylaminoethanol, diethylaminopropanol, diethylaminobutanol, dipropylaminomethanol, dipropylaminoethanol, dipropyl Aminopropanol, dipropylaminobutanol, dibutylaminoethanol, dibutylaminopropanol, dibutylaminobutanol and the like. Among them, diethylaminoethanol, dimethylaminoethanol, dipropylaminoethanol and dibutylaminobutanol are preferred.
  • viridyl group-containing amine compounds examples include 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-methylpyridine, 2-aminomethylpyridine, 3-aminomethylpyridine, 4-aminomethylpyridine , 2-amino-4-methylpyridine, 2-amino-6-methylpyridine, 2-amino-4-ethylpyridine, 2-amino-4-propylpyridine and the like. 2-aminomethylpyridine, 3-aminomethylpyridine and 4-aminomethylpyridine are preferred.
  • the amount of the alcohol component used in 100% by mass of the urethane branched compound is preferably 20% by mass or more from the viewpoint of obtaining high transparency, and preferably 90% by mass or less from the viewpoint of obtaining high substrate adhesion. , more preferably 30 to 80% by mass.
  • “in 100% by mass of the urethane branched compound” means “in 100% by mass of the raw material for synthesis of the urethane branched compound", for example, the alcohol component, the polyisocyanate component, and, if necessary, It means 100% by mass of the total amount of amine components used accordingly (the same meaning applies to the following description).
  • the amount of the polyisocyanate component used is preferably 10% by mass or more from the viewpoint of obtaining high substrate adhesion, and preferably 70% by weight or less from the viewpoint of obtaining high transparency, based on 100% by weight of the branched urethane compound. It is preferably 20 to 55% by mass, more preferably 20 to 55% by mass.
  • the amount of the amine component used in 100% by mass of the urethane branched compound is preferably 0.1% by mass or more from the viewpoint of obtaining high substrate adhesion, and is 20% by mass or less from the viewpoint of obtaining high transparency. is preferred, and more preferably 0.5 to 10% by mass.
  • a commercially available product can be used as the urethane branched compound.
  • Commercially available products include, for example, DISPERBYK-110, DISPERBYK-111, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-167, DISPERBYK-170, DISPERBY K-171, DISPERBYK-174, DISPERBYK-182, DISPERBYK-183, DISPERBYK-184, DISPERBYK-185, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164 (manufactured by BYK-Chemie (BYK)); Solsperse 76500 (Lubrizol Co., Ltd.) Ajisper PB711 (manufactured by Ajinomoto Co
  • the pressure-sensitive adhesive for sticking to the skin uses a curing agent to cause a cross-linking reaction of the reactive functional groups of the polymer (A).
  • Preferred curing agents are, for example, isocyanate compounds, epoxy compounds, metal chelate compounds, amine compounds, aziridine compounds, and the like. Among these, isocyanate compounds or metal chelates are used to easily obtain a suitable cross-linking density. Curing agents can be used alone or in combination of two or more.
  • isocyanate compounds include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate.
  • a diisocyanate such as polymethylene polyphenyl isocyanate and a polyol compound such as trimethylolpropane; a biurette thereof; an isocyanurate thereof; and the diisocyanate, polyether polyol, polyester polyol, acrylic polyol, polybutadiene polyol , and compounds having 3 or more isocyanate groups in the molecule such as adducts with polyols such as polyisoprene polyol; Diisocyanates such as diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and polymethylene polyphenyl isocyanate, and allophanate forms of hexamethylene diisocyanate, etc., which have two molecules in the
  • the content of the isocyanate compound is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the polymer (A).
  • 0.05 to 10 parts by mass is included, both cohesive strength and adhesive strength can be achieved at a high level.
  • epoxy compounds include bisphenol A-epichlorohydrin type epoxy resins, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl.
  • the content of the epoxy compound is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polymer (A). When 0.01 to 1 part by mass is included, both cohesive strength and adhesive strength can be achieved at a high level.
  • metal chelates include coordination compounds of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium with acetylacetone or ethyl acetoacetate. be done.
  • the content of the metal chelate is preferably 0.1-5 parts by mass with respect to 100 parts by mass of the polymer (A). When 0.1 to 5 parts by mass is included, both cohesive strength and adhesive strength can be achieved at a high level.
  • amine compounds include hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethyltetramine, isophoronediamine, amino resins, and methylene resins.
  • the content of the amine compound is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polymer (A). When 0.01 to 1 part by mass is included, both cohesive strength and adhesive strength can be achieved at a high level.
  • aziridine compounds include N,N'-diphenylmethane-4,4'-bis(1-aziridine carboxysite), N,N'-toluene-2,4-bis(1-aziridine carboxysite), bisiso phthaloyl-1-(2-methylaziridine), tri-1-aziridinylphosphine oxide, N,N'-hexamethylene-1,6-bis(1-aziridinecarboxysite), 2,2'-bishydroxy methylbutanol-tris[3-(1-aziridinyl)propionate], trimethylolpropane tri- ⁇ -aziridinylpropionate, tetramethylolmethane tri- ⁇ -aziridinylpropionate, and tris-2,4, 6-(1-aziridinyl)-1,3,5-triazine and the like. Among them, 2,2'-bishydroxymethylbutanol-tris[3-(1-azirididine
  • the blending amount of the aziridine curing agent is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polymer (A). When 0.01 to 1 part by mass is included, both cohesive strength and adhesive strength can be achieved at a high level.
  • the pressure-sensitive adhesive for skin application can contain any component as long as the problem can be solved.
  • Optional components include, for example, plasticizers, reduction of polymerization cure shrinkage, improvement of dimensional stability, improvement of elastic modulus, suppression of redox, adjustment of viscosity, improvement of thermal conductivity, improvement of strength, improvement of toughness, and improvement of coloring, etc. , organic or inorganic additives and fillers.
  • the filler is appropriately composed of polymers, ceramics, metals, metal oxides, metal salts, dyes and pigments, and the like.
  • the shape of the filler is preferably particulate, fibrous, or the like.
  • additives include antioxidants, flame retardants, storage stabilizers, ultraviolet absorbers, thixotropy-imparting agents, dispersion stabilizers, fluidity-imparting agents, thickeners, moisturizing agents, percutaneous absorbers, and pH adjusters. agents, leveling agents, hydrolysis inhibitors, antifoaming agents, and the like.
  • plasticizers can be used for the purpose of making the polymer (A) more flexible, reducing pain when peeling off the adhesive tape, and improving exfoliation of keratin.
  • the plasticizer to be used is not particularly limited, but examples thereof include fatty acid ester plasticizers, polyether ester plasticizers, hydroxycarboxylic acid ester plasticizers, and phosphate ester plasticizers. From the viewpoint of skin irritation and compatibility with the polymer (A), the plasticizer is preferably a fatty acid ester plasticizer.
  • esters of monohydric alcohols include dibutyl phthalate, di-2-ethylhexyl phthalate, dibutyl adipate, di-2-ethylhexyl sebacate, dibutyl maleate, ethyl myriphosphate, isopropyl myristate, isopropyl palmitate, and stearin.
  • Divalent or higher alcohol esters include propylene glycol dicaprylate, propylene glycol dicaprate, propylene glycol diisostearate, glyceryl monocaprylate, glyceryl tricaprylate, glyceryl tri-2-ethylhexanoate, glyceryl tricaprate, and trilaurin.
  • Polyether ester plasticizers include polyethylene glycol dihexylate, polyethylene glycol di-2-ethylhexylate, polyethylene glycol dilaurate, polyethylene glycol dioleate, and dipolyethylene glycol methyl ether adipate.
  • Hydroxycarboxylic acid ester plasticizers include butyl citrate, triethyl citrate, tripropyl citrate, and o-acetyltriethyl citrate.
  • phosphate plasticizers examples include tributyl phosphate, tris(2-ethylhexyl) phosphate, triphenyl phosphate, and tricresyl phosphate.
  • the plasticizer may also be a compound containing a fatty acid ester structure and a polyether structure, such as polyoxyethylene ether of sorbitan fatty acid ester obtained by condensing ethylene oxide to sorbitan fatty acid ester.
  • polyether structure such as polyoxyethylene ether of sorbitan fatty acid ester obtained by condensing ethylene oxide to sorbitan fatty acid ester. Examples include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan monooleate.
  • the content of the plasticizer is not particularly limited, it is preferably 10 to 80 parts by mass, more preferably 15 to 50 parts by mass, based on 100 parts by mass of the polymer (A).
  • the content of the plasticizer is within this range, it is possible to further improve the keratin exfoliation property while ensuring the cohesive force to the extent that adhesive residue does not occur, which is preferable.
  • the adhesive force can be greatly reduced, the adhesive tape using the adhesive can be suitably used for medical applications in which the tape is directly applied to a wound.
  • Method for producing pressure-sensitive adhesive for skin application For the pressure-sensitive adhesive for skin attachment, prepare polymer (A), urethane compound (B), and curing agent (C); mix polymer (A), urethane compound (B), and curing agent (C); It can be manufactured by a manufacturing method including By using the polymer (A) and the urethane compound (B) that can function as a tackifier in the production of a pressure-sensitive adhesive for skin application, a pressure-sensitive adhesive with excellent adhesion and transparency can be obtained. .
  • a cured product which is an embodiment of the present invention, is obtained by curing the pressure-sensitive adhesive for skin application of the above-described embodiment.
  • crosslinks are formed between the polymer (A) molecules by the crosslinking reaction of the curing agent (C).
  • Curing of the pressure-sensitive adhesive for sticking to the skin can be advanced, for example, by heating the pressure-sensitive adhesive for sticking to the skin.
  • the gel fraction of the cured product is preferably 20-63%.
  • the cohesive force is high and cohesive failure at the time of peeling is suppressed, resulting in good removability. Therefore, it is easy to obtain a pressure-sensitive adhesive that is excellent in initial peeling.
  • the gel fraction is 63% or less, sufficient cohesion can be obtained, but sufficient adhesion tends to be obtained.
  • the cohesive force does not become too high, the conformability to the skin is improved, and there is a tendency that the exfoliation of keratin can be suppressed.
  • the gel fraction may be 30% or higher, or 35% or higher.
  • the gel fraction may be 55% or less, or 45% or less.
  • the gel fraction of the cured product can be measured by the method described in Examples. The gel fraction can be adjusted by changing the contents of polymer (A), urethane compound (B), and curing agent (C).
  • the cured product preferably has a permanent adhesive strength to SUS of 0.3 N/25 mm or more in an atmosphere with a temperature of 23°C and a relative humidity of 50%.
  • the permanent adhesive strength to SUS may be 0.5 N/25 mm or more, 1.0 N/25 mm or more, or 2.0 N/25 mm or more.
  • the upper limit is not particularly limited, the permanent adhesion to SUS is, for example, 30 N/25 mm or less.
  • the permanent adhesive strength to SUS can be measured by the method described in Examples.
  • a pressure-sensitive adhesive tape for skin application which is an embodiment of the present invention, has a substrate and an adhesive layer containing the cured product of the embodiment.
  • the adhesive tape for sticking to the skin can be produced, for example, by (1) applying a pressure-sensitive adhesive for sticking to the skin onto a release liner, drying it to form an adhesive layer, and then laminating a base material, or (2) a method of bonding a base material.
  • a preferred method is a method of forming an adhesive layer by applying an adhesive for sticking to the skin thereon and drying it, and then attaching a peelable sheet to the adhesive layer.
  • the thickness of the adhesive layer is usually about 10-200 ⁇ m, preferably 25-100 ⁇ m.
  • drying is usually performed at the time of coating.
  • drying method there are no particular restrictions on the drying method, and for example, hot air drying, infrared rays, reduced pressure, and the like can be used.
  • the drying temperature is preferably about 60 to 180°C, more preferably about 80 to 150°C.
  • substrates include non-woven fabrics; wood materials, processed paper products; woven fabrics, non-woven fabrics, or knitted fabrics using rayon, polyurethane yarn, cotton, wool, polyolefin yarn, polyester yarn, etc.; plastic foam films having open cells. , plastic films having holes formed by punching or the like, and films of cellulose, cellulose acetate, and the like.
  • the moisture-permeable substrate may be a single layer or a laminate obtained by laminating two or more layers of substrates. From the viewpoint of obtaining high transparency, the substrate is preferably a polyurethane film, a polyurethane nonwoven fabric, or a polyester nonwoven fabric.
  • the thickness of the base material is usually about 5 ⁇ m to 1,000 ⁇ m, preferably 15 ⁇ m to 500 ⁇ m.
  • a release liner is, for example, formed with a release treatment layer such as silicone treatment on the surface of a base material such as paper or plastic film.
  • the substrate may be a single layer or a laminate obtained by laminating two or more layers of substrates.
  • the adhesive tape for sticking to the skin can be used, for example, as a wound covering tape or bandage, a tape for fixing a medical device to the skin, an adhesive plaster, a dressing tape, a supporter, or the like. Furthermore, when the adhesive layer contains a drug, it can be used as a sustained-release sheet by blending a stably dispersible drug in the medical adhesive.
  • a polymer (A) having a reactive functional group, a urethane compound (B) having a mass average molecular weight of 1,500 to 40,000, and a curing agent (C); ) is 0.05 to 20 parts by mass per 100 parts by mass of the polymer (A).
  • (2) The above ( 1) The pressure-sensitive adhesive for skin application.
  • (6) The pressure-sensitive adhesive for application to skin according to any one of (1) to (5) above, wherein the urethane compound (B) has an amine value of 0.1 to 60 mgKOH/g.
  • part means parts by mass
  • % means mass %
  • RH means relative humidity.
  • unit of the compounding amount in the table is “mass part”.
  • amount of components other than the solvent described in the table is the amount of non-volatile matter.
  • a mixture having the same composition and an equal amount as the mixture in the reaction vessel (95.0 parts of 2-ethylhexyl acrylate, 5.0 parts of acrylic acid, 70 parts of ethyl acetate, and 0.05 parts of AIBN) was added to the dropping funnel. was dropped into the reaction vessel over 1 hour, and the polymerization reaction was carried out at reflux temperature over 7 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was cooled, and ethyl acetate was added to dilute the polymerization reaction product to obtain an acrylic copolymer solution having a non-volatile content of 40%. Moreover, when the mass average molecular weight (Mw) of the acrylic copolymer was measured using GPC, it was 630,000.
  • AIBN azobisisobutyronitrile
  • a mixture having the same composition and an equivalent amount as the mixture in the reaction vessel (97.0 parts of 2-ethylhexyl acrylate, 3.0 parts of 2-hydroxyethyl acrylate, 70 parts of ethyl acetate, 0.05 parts of AIBN) was added to the dropping funnel. Part) was added and added dropwise into the reaction vessel over 1 hour, and the polymerization reaction was carried out over 7 hours at reflux temperature under nitrogen atmosphere. After completion of the reaction, the mixture was cooled, and ethyl acetate was added to dilute the polymerization reaction product to obtain an acrylic copolymer solution having a non-volatile content of 40%. Moreover, when the mass average molecular weight (Mw) of the acrylic copolymer was measured using GPC, it was 580,000.
  • Mw mass average molecular weight
  • ⁇ Polymer (A-3) Polyurethane urea> (Synthesis of diamine compound (a)) 19.25 parts of isophoronediamine (IPDA) is placed in a four-necked flask (hereinafter sometimes simply referred to as a "four-necked flask") equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel. , and 19.25 parts of toluene were added. A mixture of 16.25 parts of 4-hydroxybutyl acrylate and 14.5 parts of butyl acrylate was dropped from the dropping funnel into the four-necked flask at room temperature.
  • IPDA isophoronediamine
  • the temperature of the mixture in the four-necked flask was gradually raised to 80°C, and the mixture was reacted for 2 hours while maintaining the temperature at 80°C. , and a diamine compound (a) solution having one primary hydroxyl group was obtained.
  • the obtained polyurethaneurea (A-3) had a mass average molecular weight (Mw) of 11,7000 and a hydroxyl value of 11.1 mgKOH/g.
  • ADEKA POLYETHER AM-302 terminal EO-modified polyether polyol, Mn 3,000, hydroxyl group number 3, manufactured by ADEKA
  • Kuraray Polyol P-1010 polyyester polyol, Mn 1,000, hydroxyl group 2, manufactured by Kuraray
  • 1 part of ethylene glycol, 70 parts of ethyl acetate, and 0.020 part of dioctyltin dilaurate as a catalyst were added and mixed. The mixture was then gradually heated to 80°C.
  • Polymer (A-5) polyether polyol> As the polymer (A-5), Preminol S3015 (polymer of propylene oxide (PO) units using glycerin as an initiator, Mw 15,000, average functional group number 3, manufactured by AGC) was used.
  • PO propylene oxide
  • Kuraray Polyol P-510 polyester polyol, Mn 500, number of hydroxyl groups: 2, manufactured by Kuraray Co., Ltd.
  • 70 parts of ethyl acetate, and 0.020 part of dioctyltin dilaurate as a catalyst were added to a four-necked flask and mixed. The mixture was then gradually heated to 78°C.
  • Urethane Oligomers (B-2), (B-3), and (B2-1) were prepared in the same manner as in Production Example (B-1), except that the types and amounts of isocyanate and polyol shown in Table 1 were used. Obtained.
  • Table 1 shows the weight average molecular weights (Mw) of the urethane oligomers (B-2), (B-3), and (B2-1).
  • TDI toluene diisocyanate
  • P-510 "Kuraray polyol P-510", Mn500, hydroxyl group number 2, polyester polyol, Kuraray Co., Ltd.
  • PP200 "Sannics PP-200", polyoxypropylene glycol, Mn200, hydroxyl group number 2, Sanyo PP1000 manufactured by Kasei Kogyo Co., Ltd.: "Sannics PP-1000", polyoxypropylene glycol, Mn1000, hydroxyl group number 2, manufactured by Sanyo Chemical Industries Co., Ltd.
  • a mixture of 11.4 parts of dimethylaminoethanol and 110 parts of xylene was dropped as the third component (amine component) into the four-necked flask.
  • the mixture in the four-necked flask was heated to 50° C. and stirred for 1 hour to obtain a slightly yellow urethane oligomer (B-4).
  • the resulting urethane oligomer (B-4) had a mass average molecular weight (Mw) of 23,000 and an amine value of 20.1 mgKOH/g.
  • Desmodur IL Desmodur ultra IL, TDI nurate, nonvolatile content 51%, NCO content 8.0%, manufactured by Sumika Covestro Urethane Co., Ltd.
  • Desmodur N3300 HDI nurate, nonvolatile content 100%, NCO content 21.8 %, Sumika Covestro Urethane Co., Ltd.
  • Desmodur Z4470 IPDI Nurate, nonvolatile content 70%, NCO content 11.9%, Sumika Covestro Urethane Co., Ltd.
  • Desmodur 44V70L Polymeric MDI, nonvolatile content 100%, NCO content
  • Evermore Japan P-1010 Kuraray polyol P-1010, Mn1000, number of hydroxyl groups 2
  • polyester polyol manufactured by Kuraray
  • Mass average molecular weight (Mw) and number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) method.
  • the measurement apparatus and measurement conditions were based on measurement conditions 1 below. However, depending on the type of polymer, an appropriate carrier (eluent) and a column suitable for it may be selected and used. For other matters, refer to JISK7252-1 to 4:2008.
  • the measuring apparatus and measuring conditions for measuring a compound having an amino group were basically based on the following measuring conditions 2. Both Mw and Mn are polystyrene equivalent values.
  • Amine value (mgKOH/g) (5.611 x a x F)/S S: Sample collection amount (g) a: consumption of 0.1N alcoholic hydrochloric acid solution (mL) F: Titer of 0.1N alcoholic hydrochloric acid solution
  • Example 1 100 parts of the polymer (A-1), 0.5 parts of the urethane branched compound (B-4), 0.6 parts of the aluminum chelate A as the curing agent (C), and 20 parts of ethyl acetate as the solvent were blended and dispersed. The mixture was stirred with a stirrer to obtain a uniform pressure-sensitive adhesive for skin application. On a 38 ⁇ m thick polyester separator (Superstick SP-PET38, manufactured by Lintec), the adhesive layer is coated so that the thickness of the adhesive layer after drying is 30 ⁇ m, and dried at 100 ° C. for 2 minutes to remove the adhesive layer. formed.
  • Superstick SP-PET38 manufactured by Lintec
  • Examples 2 to 29, Comparative Examples 1 to 10 In each of Examples 2 to 29 and Comparative Examples 1 to 10, the composition of the adhesive, the amount (parts by mass), and the substrate for adhesion evaluation were changed as shown in Table 3. In the same manner as in Example 1, an adhesive for application to the skin and an adhesive tape for application to the skin using the same were produced.
  • Curing agents (C) listed in Table 3 are as follows.
  • C-1 Aluminum chelate A (manufactured by Kawaken Fine Chemicals)
  • Base materials A to C are as follows.
  • Base material A Polyester-based urethane film (Silkron NES85, thickness 25 ⁇ m, manufactured by Okura Kogyo Co., Ltd.)
  • Base material B Urethane-based nonwoven fabric (Espancione, UHO-100, thickness 0.37 mm, manufactured by KB Seiren)
  • Base material C polyester nonwoven fabric (Sontara #8010, manufactured by DuPont, basis weight: 45 g/m 2 )
  • Adhesion to skin The adhesion state of the adhesive tape after 36 hours of application was evaluated according to the following criteria. [Evaluation criteria] ⁇ : 8 to 10 people adhered well over the entire surface of the test piece, good. ⁇ : 3 to 7 people adhered well over the entire surface of the test piece, practically acceptable. x: 0 to 2 people adhered well over the entire surface of the test piece, impractical.
  • Substrate Adhesion Peeling of the adhesive layer from the substrate when the test piece was peeled off was evaluated according to the following criteria. [Evaluation criteria] ⁇ : Good, no peeling observed by 9 to 10 persons. ⁇ : Peeling was not observed by 4 to 8 people, practically acceptable. x: Peeling was not observed by 0 to 3 persons, not practical.

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  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Inorganic Chemistry (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
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Abstract

Un mode de réalisation concerne un adhésif pour fixation sur la peau contenant (A) un polymère ayant un groupe fonctionnel réactif, (B) un composé uréthane dans lequel le poids moléculaire moyen en masse est de 1 500 à 40 000, et (C) un agent de durcissement, la teneur en composé uréthane (B) étant de 0,05 à 20 parties en masse par rapport à 100 parties en masse du polymère (A).
PCT/JP2022/038428 2021-11-30 2022-10-14 Adhésif pour fixation sur la peau et ruban adhésif pour fixation sur la peau Ceased WO2023100501A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015509117A (ja) * 2011-12-20 2015-03-26 メディカル・アドヒーシブ・レボリューション・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＭｅｄｉｃａｌ Ａｄｈｅｓｉｖｅ Ｒｅｖｏｌｕｔｉｏｎ ＧｍｂＨ ヒドロキシアミノポリマーおよびポリ尿素／ポリウレタン組織接着剤におけるその使用
JP2018002805A (ja) * 2016-06-29 2018-01-11 東洋インキＳｃホールディングス株式会社 感圧式接着剤および接着シート
JP2020081438A (ja) * 2018-11-27 2020-06-04 東洋インキＳｃホールディングス株式会社 医療用粘着剤組成物および医療用粘着シート

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015509117A (ja) * 2011-12-20 2015-03-26 メディカル・アドヒーシブ・レボリューション・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＭｅｄｉｃａｌ Ａｄｈｅｓｉｖｅ Ｒｅｖｏｌｕｔｉｏｎ ＧｍｂＨ ヒドロキシアミノポリマーおよびポリ尿素／ポリウレタン組織接着剤におけるその使用
JP2018002805A (ja) * 2016-06-29 2018-01-11 東洋インキＳｃホールディングス株式会社 感圧式接着剤および接着シート
JP2020081438A (ja) * 2018-11-27 2020-06-04 東洋インキＳｃホールディングス株式会社 医療用粘着剤組成物および医療用粘着シート

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