CN113853414B

CN113853414B - Medical adhesive material

Info

Publication number: CN113853414B
Application number: CN201980096526.5A
Authority: CN
Inventors: 辻泰辉; 宫下翼; 藤泽博充
Original assignee: Nichiban Co Ltd
Current assignee: Nichiban Co Ltd
Priority date: 2018-06-29
Filing date: 2019-12-19
Publication date: 2023-12-08
Anticipated expiration: 2039-12-19
Also published as: WO2020261609A1; JP7369552B2; JP2020006166A; KR20220027057A; CN113853414A

Abstract

A medical adhesive material comprising a laminate of a support and an adhesive layer, wherein the adhesive layer is composed of an adhesive composition comprising a copolymer containing an alkyl (meth) acrylate as a main component and a fatty acid ester which is liquid at room temperature and is compatible with the copolymer, the weight average molecular weight of the fatty acid ester contained in the adhesive composition is 350 to 550, the adhesive composition comprises 5 to 25 parts by mass of the fatty acid ester relative to 100 parts by mass of the copolymer, and the moisture permeability coefficient of the support is 500 g/(m) ² 24 h) or more.

Description

Medical adhesive material

Technical Field

The present application relates to a medical adhesive material for attaching to a skin surface such as an adhesive bandage or a plaster, and an adhesive composition suitable for forming an adhesive layer of the medical adhesive material. The present application claims priority based on Japanese patent application No. 2019-122202, 6-28, of the application, the contents of which are incorporated herein by reference.

Background

Medical adhesive materials such as adhesive bandages and plasters are also used for fixing a tube such as a catheter to the skin surface. In the fixation of a catheter or the like, since the fixation needs to be performed stably so as not to peel off erroneously, the medical adhesive material used tends to have high adhesive force priority. On the other hand, catheters and the like may be fixed to the same portion of the skin repeatedly for a long period of time. Therefore, medical adhesive materials for fixing catheters and the like are required to have little effect on the skin when continuously and repeatedly applied. In addition, analgesic and anti-inflammatory agents, magnetotherapeutic plasters, tapes (taping tapes) and the like, which are applied to specific parts such as the shoulder, the waist and the like, are sometimes repeatedly fixed to the same part of the skin, and it is desirable that medical adhesive materials used for these applications and the like have little influence on the skin even in the case of continuous and repeated application.

As a medical patch for suppressing skin irritation, for example, patent document 1 describes a medical patch using an adhesive composition containing a fatty acid ester compatible with an acrylic polymer having a weight average molecular weight of 250 ten thousand or more as a liquid plasticizer as an adhesive. By using an acrylic polymer having good adhesion as the adhesive layer and containing a fatty acid ester compatible with the acrylic polymer as the liquid plasticizer, the adhesive layer is plasticized and softened, and skin irritation is reduced.

As a medical adhesive material having an adhesive layer containing a liquid plasticizer in an adhesive layer, for example, patent document 2 discloses an adhesive material in which an adhesive layer is formed on a support, and a liquid plasticizer such as a fatty acid ester is added to an acrylic adhesive composed of a copolymer obtained by emulsion polymerization of an alkyl (meth) acrylate in the adhesive layer.

Patent document 1: japanese patent laid-open No. 11-76392

Patent document 2: japanese patent laid-open No. 2009-155306.

Disclosure of Invention

The purpose of the present invention is to provide a medical adhesive material which has sufficient adhesive force and has little influence on the skin when repeatedly applied to the same part of the skin.

The present inventors have found that an acrylic pressure-sensitive adhesive agent constituting a pressure-sensitive adhesive layer of a medical adhesive material contains 5 to 25 parts by mass of a fatty acid ester having a weight average molecular weight of 350 to 550 and a liquid state at room temperature, and has a moisture permeability coefficient of 500 g/(m), per 100 parts by mass of an acrylic copolymer ² 24 h) or more, to obtain a medical adhesive material having a reduced exfoliating area while maintaining high adhesion to human skin, and to complete the present invention.

Namely, the present invention provides the following medical adhesive material.

[1] A medical adhesive material comprising a laminate of a support and an adhesive layer,

the adhesive layer is composed of an adhesive composition containing a copolymer containing an alkyl (meth) acrylate as a main component, and a fatty acid ester which is liquid at room temperature and is compatible with the copolymer,

the weight average molecular weight of the fatty acid ester contained in the adhesive composition is 350 to 550,

the adhesive composition contains 5 to 25 parts by mass of the fatty acid ester per 100 parts by mass of the copolymer,

The moisture permeability coefficient of the support is 500 g/(m) ² 24 h) or more.

[2] The medical patch according to the item [1], wherein the fatty acid ester contains a single fatty acid ester having a weight average molecular weight of 350 to 550.

[3] The medical patch according to [1] or [2], wherein the copolymer is a polymer obtained by crosslinking a copolymer obtained by polymerizing the following substances by a solution polymerization method with a crosslinking agent: 65 to 90 mass% of an alkyl acrylate having an alkyl group having 8 to 12 carbon atoms; 2 mass% or more and 15 mass% or less of acrylic acid; 5 mass% or more and 25 mass% or less of vinyl acetate; and 0 mass% or more and 10 mass% or less of other vinyl monomers.

[4] The medical patch according to any one of [1] to [3], wherein the fatty acid ester has at least one oleic acid residue.

[5] The medical patch according to the item [4], wherein all of the fatty acid residues in the fatty acid ester are oleic acid residues.

[6] The medical adhesive material according to any one of [1] to [5], wherein a separator is further provided on a surface of the adhesive layer facing a surface of the adhesive layer contacting the support.

[7] The medical patch according to any one of [1] to [6], wherein the medical patch is repeatedly attached to the same portion of the skin.

[8] The medical patch according to any one of [1] to [7], wherein the medical patch is used for fixing a tube.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, it is possible to provide a medical adhesive material in which an adhesive layer is formed of an adhesive composition that maintains high adhesive force and has little skin irritation when continuously or repeatedly applied to the same part of the skin.

Detailed Description

< adhesive composition >

The pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer of the medical adhesive material according to the present invention contains a copolymer containing an alkyl (meth) acrylate as a main component and a fatty acid ester that is liquid at room temperature (1 ℃ to 30 ℃). The fatty acid ester is a liquid plasticizer imparting plasticity, which is compatible with a copolymer containing an alkyl (meth) acrylate as a main component as a binder.

(copolymer comprising alkyl (meth) acrylate as the main component)

A copolymer containing an alkyl (meth) acrylate as a main component (hereinafter, sometimes referred to as an "acrylic copolymer") is a copolymer in which 50 mol% or more of the entire constituent units constituting the copolymer are constituent units derived from an alkyl (meth) acrylate. In the present invention and in the present specification, the term "alkyl (meth) acrylate" means "alkyl acrylate and/or alkyl methacrylate".

The alkyl (meth) acrylate from which the constituent units of the copolymer are derived is preferably an alkyl (meth) acrylate having an alkyl moiety having 1 to 18 carbon atoms. Specifically, there may be mentioned: methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like. These alkyl (meth) acrylates may be used each alone or in combination of two or more.

The alkyl (meth) acrylate used in the present invention, which is a source of the constituent unit of the acrylic copolymer, is preferably an alkyl (meth) acrylate having an alkyl group having 4 to 18 carbon atoms, more preferably an alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms, still more preferably an alkyl (meth) acrylate having an alkyl group having 6 to 12 carbon atoms, still more preferably an alkyl (meth) acrylate having an alkyl group having 8 to 12 carbon atoms, particularly preferably 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate or isononyl (meth) acrylate.

The acrylic copolymer used in the present invention preferably contains at least one constituent unit derived from an alkyl (meth) acrylate having 4 to 18 carbon atoms in the alkyl moiety. For example, the constituent unit derived from the alkyl (meth) acrylate may be a copolymer having only the constituent unit derived from the alkyl (meth) acrylate having 4 to 18 carbon atoms in the alkyl moiety, or may be a copolymer containing both the constituent unit derived from the alkyl (meth) acrylate having 4 to 18 carbon atoms in the alkyl moiety and the constituent unit derived from the other alkyl (meth) acrylate.

The acrylic copolymer used in the present invention may be a copolymer composed of only constituent units derived from an alkyl (meth) acrylate, or may be a copolymer containing constituent units derived from another polymerizable compound. Examples of the other polymerizable compound include a compound having a vinyl group (vinyl monomer).

Examples of the vinyl monomer include vinyl monomers having a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride group, an amide group, an amino group, an epoxy group, an alkoxy group, an acyl group, a cyano group, an aryl group, or a heterocyclic group. Examples of the vinyl monomer having a hydroxyl group include (meth) acrylate having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Examples of the vinyl monomer having a carboxyl group or an acid anhydride group include acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, and monobutyl maleate. Examples of the vinyl monomer having an amide group include acrylamide, dimethylacrylamide, diethylacrylamide, methacrylamide, and N-methylolacrylamide. Examples of the vinyl monomer having an amino group include dimethylaminoethyl acrylate and the like. Examples of the vinyl monomer having an epoxy group include glycidyl acrylate and glycidyl methacrylate. Examples of the vinyl monomer having an alkoxy group include alkoxyalkyl acrylate such as 2-methoxyethyl acrylate and ethoxyethyl acrylate. Examples of the vinyl monomer having an acyl group include vinyl esters such as vinyl acetate. Examples of the vinyl monomer having a cyano group include unsaturated nitriles such as acrylonitrile and methacrylonitrile. Examples of the vinyl monomer having an aryl group include vinyl aromatic compounds such as styrene. Examples of the vinyl monomer having a heterocyclic group include vinyl monomers having a pyrrolidone ring such as N-vinylpyrrolidone. These vinyl monomers may be used each alone or in combination of two or more.

The acrylic copolymer used in the present invention is preferably a copolymer of an alkyl (meth) acrylate and another vinyl monomer, preferably a copolymer of a vinyl monomer (hereinafter, sometimes referred to as "vinyl monomer (a)") containing at least one kind of the other vinyl monomer having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, an amide group, an amino group, an epoxy group, and an alkoxy group, and further preferably a copolymer of at least one vinyl monomer (hereinafter, sometimes referred to as "vinyl monomer (B)") having no functional group.

The acrylic copolymer used in the present invention is preferably the following copolymer: an alkyl acrylate having an alkyl group with a carbon number of 4 to 18, preferably 8 to 12, and less than the total mass of the monomers used in the copolymerization reaction is 55 to 95 mass%, preferably 60 to 95 mass%, more preferably 65 to 90 mass%, still more preferably 80 to 90 mass%, particularly preferably 83 to 87 mass%, and most preferably 85 mass%; the vinyl monomer (a) is 1 to 25 mass%, preferably 1 to 20 mass%, more preferably 2 to 15 mass%, still more preferably 2 to 10 mass%, particularly preferably 2 to 6 mass%, particularly preferably 4 mass%; the vinyl monomer other than the vinyl monomer (a) is 0 mass% or more and 40 mass% or less, preferably 0 mass% or more and 30 mass% or less, more preferably 0 mass% or more and 25 mass% or less, still more preferably 5 mass% or more and 15 mass% or less, particularly preferably 9 mass% or more and 13 mass% or less, and most preferably 11 mass% or less; the other vinyl monomer is 0 mass% or more and 10 mass% or less, more preferably the following copolymer: an alkyl acrylate having an alkyl group having 4 to 18, preferably 8 to 12 carbon atoms is 55 to 95 mass%, preferably 60 to 95 mass%, more preferably 65 to 90 mass%, still more preferably 80 to 90 mass%, particularly preferably 83 to 87 mass%, most preferably 85 mass%; the vinyl monomer (a) is 1 to 25 mass%, preferably 1 to 20 mass%, more preferably 2 to 15 mass%, still more preferably 2 to 10 mass%, particularly preferably 2 to 6 mass%, particularly preferably 4 mass%; the vinyl monomer (B) is 0 to 40 mass%, preferably 3 to 30 mass%, more preferably 5 to 25 mass%, still more preferably 5 to 15 mass%, particularly preferably 9 to 13 mass%, most preferably 11 mass%; the other vinyl monomer is 0 mass% or more and 10 mass% or less. Among them, the vinyl monomer (a) is acrylic acid, the vinyl monomer (B) is vinyl acetate, and the following copolymers are more preferable: an alkyl acrylate having an alkyl group with a carbon number of 4 to 18, preferably 8 to 12, and less than the total mass of the monomers used in the copolymerization reaction is 55 to 95 mass%, preferably 60 to 95 mass%, more preferably 65 to 90 mass%, still more preferably 80 to 90 mass%, particularly preferably 83 to 87 mass%, and most preferably 85 mass%; acrylic acid is 1 to 25 mass%, preferably 1 to 20 mass%, more preferably 2 to 15 mass%, still more preferably 2 to 10 mass%, particularly preferably 2 to 6 mass%, particularly preferably 4 mass%; vinyl acetate is 0 to 40 mass%, preferably 3 to 30 mass%, more preferably 5 to 25 mass%, still more preferably 5 to 15 mass%, particularly preferably 9 to 13 mass%, most preferably 11 mass%; the other vinyl monomer is 0 mass% or more and 10 mass% or less. By using the acrylic copolymer having the above copolymer component as an adhesive, an adhesive layer which shows suitable adhesion even if the adhesive layer is thin and is excellent in other characteristics can be easily formed.

The weight average molecular weight of the acrylic copolymer used in the present invention is preferably 300,000 or more and 1,000,000 or less, more preferably 450,000 or more and 650,000 or less. By setting the weight average molecular weight of the acrylic copolymer in the above range, cohesiveness, adhesive force, mixing workability with other components, and affinity with other components can be balanced. If the molecular weight is less than 300,000, cohesiveness is lowered, and thus adhesive residue on the skin may be generated at the time of peeling. If the weight average molecular weight exceeds 1,000,000, the operability at the time of production is poor. The weight average molecular weight of the acrylic copolymer is a value obtained by Gel Permeation Chromatography (GPC) method based on polystyrene conversion values.

The acrylic copolymer used in the present invention can be generally synthesized by radical polymerization. The acrylic copolymer can be produced by a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method, and the solution polymerization method is preferable in view of easy obtaining of good adhesive properties. Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide and lauroyl peroxide; azo initiators such as azobisisobutyronitrile and the like. The radical polymerization initiator is added in a proportion of 0.1 to 3 mass% relative to the total amount of the monomers, and the mixture is stirred under a nitrogen stream at a temperature of 40 to 90 ℃ for several hours to several tens of hours to copolymerize the monomers. In the solution polymerization method, ethyl acetate, acetone, toluene, a mixture thereof, and the like are widely used as solvents.

(crosslinking and crosslinking agent)

The adhesive composition used in the present invention may contain a crosslinking agent. When the adhesive composition contains a crosslinking agent, the cohesive force of the adhesive layer can be improved by forming the adhesive layer by crosslinking the acrylic copolymer in the adhesive composition.

Examples of the crosslinking agent include: polyfunctional isocyanate compounds [ Toluene Diisocyanate (TDI), 4' -diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate, xylylene diisocyanate, m-xylylene diisocyanate, 1, 5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate and the like ], polyfunctional epoxy compounds, acetylacetonate metal salts and the like. Further, for example, commercially available products such as "コ" from Kagaku polyurethane Industrial Co., ltd., "Seisaku" (registered trademark) HL, "コ" L, "コ" 2 "and" TETRAD-X (registered trademark) from Mitsubishi gas chemical Co., ltd., "TETRAD-C (registered trademark)," Seisaku (registered trademark) aluminum and the like can be used as the crosslinking agent. The crosslinking agent may be used singly or in combination of 2 or more.

When the pressure-sensitive adhesive composition used in the present invention contains a crosslinking agent, the content of the crosslinking agent is preferably 0.01 to 1 part by mass, more preferably 0.03 to 0.5 part by mass, still more preferably 0.04 to 0.1 part by mass, particularly preferably 0.04 to 0.08 part by mass, and most preferably 0.06 part by mass, per 100 parts by mass of the acrylic copolymer.

In the case where the adhesive composition used in the present invention is made to contain a crosslinking agent, the crosslinking agent may be contained in the adhesive composition in advance, or the crosslinking agent may be added immediately before the adhesive composition is applied to the support or in the adhesive composition under application.

(liquid plasticizer)

The liquid plasticizer contained in the adhesive layer of the medical adhesive material according to the present invention plasticizes the adhesive layer to impart a soft feel, thereby reducing skin irritation. The liquid plasticizer contained in the adhesive composition used in the present invention is liquid at room temperature, and is a fatty acid ester having a weight average molecular weight of 350 to 550 inclusive, which is compatible with the acrylic copolymer contained in the adhesive composition. In the following, the term "molecular weight" refers to a weight average molecular weight. The (weight average) molecular weight of the fatty acid ester includes the weight average molecular weight of a fatty acid ester of a single kind (in this case, there is little molecular weight distribution, which is essentially the molecular weight inherent to a single kind), and the weight average molecular weights of fatty acid esters of a plurality of kinds. The fatty acid ester contained in the pressure-sensitive adhesive composition, which is liquid at room temperature, may be a single type of fatty acid ester having a molecular weight of 350 to 550 inclusive, which is compatible with the acrylic copolymer contained in the pressure-sensitive adhesive composition, or may contain two or more types of fatty acid esters. When two or more fatty acid esters which are liquid at room temperature and which are compatible with the acrylic copolymer contained in the adhesive composition are contained, the weight average molecular weight of these fatty acid esters may be in the range of 350 to 550. By using a fatty acid ester which is liquid at room temperature and has a size within a specific range and which is compatible with the acrylic copolymer, the acrylic copolymer and the fatty acid ester are uniformly mixed, whereby an adhesive layer is formed which maintains high adhesion to human skin and sufficiently suppresses residues on skin upon peeling from the skin.

Among fatty acid esters having a molecular weight in the range of 350 to 550, fatty acid esters having high compatibility with the acrylic copolymer can impart sufficient plasticity, and are not volatilized in a heating step such as a drying step after the application of the adhesive composition. Therefore, by using a fatty acid ester having a molecular weight in the range of 350 to 550 as a liquid plasticizer, an adhesive composition which can impart proper skin adhesiveness when forming an adhesive layer and can suppress the area of horny substance peeled off at the time of peeling can be obtained.

The binder composition used in the present invention is preferably an oleic acid ester in which at least one fatty acid residue (a residue derived from a fatty acid, specifically a group obtained by removing a hydroxyl group from a fatty acid) is an oleic acid residue (a group obtained by removing a hydroxyl group from oleic acid) in a fatty acid ester having a molecular weight in the range of 350 to 550. If oleate (fatty acid ester having at least one oleic acid residue) is used as the liquid plasticizer, the adhesive layer formed of the adhesive composition used in the present invention has a further reduced effect on the skin when applied continuously (when applied for a long time) or repeatedly.

The oleic acid ester may be an ester of a monohydric alcohol and oleic acid, or an ester of a polyhydric alcohol and oleic acid. Examples of the monohydric alcohol include alkyl alcohols such as octanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, and oleyl alcohol. Examples of the polyhydric alcohol include glycerin, sorbitol, and glycol.

In the case of an ester of a polyol and oleic acid, only one hydroxyl group in the polyol may be bonded to a fatty acid, or two or more hydroxyl groups may be bonded to a fatty acid. In the case of an oleic acid ester obtained by ester-bonding two or more hydroxyl groups to a fatty acid, only part of the fatty acid residues in the ester may be oleic acid residues, or all of the fatty acid residues in the ester may be oleic acid residues.

Examples of the oleic acid ester having a molecular weight of 350 to 550 inclusive contained in the adhesive composition used in the present invention include octyl oleate, lauryl oleate, myristyl oleate, cetyl oleate, stearyl oleate, isostearyl oleate, oleyl oleate, glyceryl monooleate, sorbitol monooleate, castor oil fatty acid ester and the like. These oleic acid esters may be used singly or in combination of two or more. The oleic acid ester contained in the adhesive composition used in the present invention is preferably glycerol monooleate (molecular weight: 356.5), sorbitol monooleate (molecular weight: 428.6), or oleic acid ester (molecular weight: 531), and particularly preferably oleic acid ester.

The content of oleic acid ester in the adhesive composition used in the present invention, which has a molecular weight in the range of 350 to 550, is preferably 1 to 35 parts by mass, more preferably 5 to 25 parts by mass, and still more preferably 10 to 20 parts by mass, based on 100 parts by mass of the acrylic copolymer. If the content is less than 1 part by mass, plasticization of the adhesive layer may be insufficient to reduce skin irritation, whereas if it exceeds 35 parts by mass, cohesive force of the adhesive may be reduced to cause adhesive residue on the skin at peeling.

Among fatty acid esters other than fatty acid esters in the adhesive composition used in the present invention, as fatty acid esters having a molecular weight in the range of 350 to 550 inclusive, isostearic acid isostearate (molecular weight: about 537) and the like are exemplified.

The adhesive composition used in the present invention may contain a liquid plasticizer other than the fatty acid ester having a molecular weight in the range of 350 to 550 inclusive, as far as the effect of the present invention is not impaired. The other liquid plasticizer is not particularly limited as long as it is a plasticizer which is liquid at room temperature and has compatibility with the acrylic copolymer. Examples thereof include oleic acid esters having a molecular weight of less than 350, oleic acid esters having a molecular weight of more than 550, fatty acid esters other than oleic acid esters, and liquid plasticizers other than fatty acid esters. Examples of the liquid plasticizer other than the fatty acid ester include: glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, and polypropylene glycol; oils and fats such as olive oil, castor oil, squalane, lanolin, etc.; hydrocarbons such as liquid paraffin. In addition, an organic solvent or a surfactant which is liquid at room temperature may be used. The fatty acid ester contained in the adhesive composition may be entirely compatible with the acrylic copolymer constituting the adhesive composition, and may contain a fatty acid ester that is not compatible with the acrylic copolymer.

In the case where the liquid plasticizer contained in the adhesive composition used in the present invention is only a fatty acid ester having a molecular weight in the range of 350 to 550 inclusive and being compatible with the acrylic copolymer, the content of the fatty acid ester having a molecular weight in the range of 350 to 550 inclusive in the adhesive composition used in the present invention is preferably 1 to 35 parts by mass, more preferably 5 to 25 parts by mass, and still more preferably 10 to 20 parts by mass, with respect to 100 parts by mass of the acrylic copolymer. If the content is less than 1 part by mass, plasticization of the adhesive layer may be insufficient to reduce skin irritation, whereas if it exceeds 35 parts by mass, cohesive force of the adhesive may be reduced to cause adhesive residue on the skin at peeling. In the case where the acrylic copolymer contains two or more fatty acid esters having a molecular weight of 350 to 550 inclusive and being compatible with the acrylic copolymer, the "content of the fatty acid esters having a molecular weight of 350 to 550 inclusive" in the adhesive composition means the total amount of the fatty acid esters conforming to the fatty acid esters having a molecular weight of 350 to 550 inclusive and being compatible with the acrylic copolymer.

In the case where the adhesive composition used in the present invention contains a fatty acid ester having a molecular weight of 350 to 550 inclusive and being compatible with the acrylic copolymer, and other liquid plasticizers, the content of the fatty acid ester having a molecular weight of 350 to 550 inclusive is preferably 50 mass% or more, more preferably 60 mass% or more, still more preferably 80 mass% or more, and particularly preferably 90 mass% or more, relative to the total amount of the liquid plasticizers contained in the adhesive composition used in the present invention. The weight average molecular weight of the whole liquid plasticizer contained in the adhesive composition, in particular, the weight average molecular weight of the whole fatty acid ester which is liquid at room temperature is preferably in the range of 350 to 550.

(additive)

The adhesive composition used in the present invention may contain various additives as required in addition to the crosslinking agent. The additive may contain additives conventionally used for adhesives for forming an adhesive layer provided in an adhesive material, such as drugs, fillers, oxidation inhibitors (antioxidants and preservatives), colorants, fragrances, and tackifiers. For example, in order to adjust the adhesive properties of the adhesive, a tackifier may be formulated. Examples of the tackifier include tackifying resins such as terpenes, terpene phenols, coumarone-indenes, styrenes, rosins, xylenes, phenols, and petroleum.

Medical adhesive material

The medical adhesive material according to the present invention comprises a laminate composed of a support and an adhesive layer. The medical adhesive material according to the present invention preferably includes an adhesive layer formed of the adhesive composition used in the present invention on at least one surface of the support. Since the adhesive layer is formed of the adhesive composition, the following medical patch is obtained: the peeling area of the cutin can be suppressed at the time of peeling while maintaining a sufficient adhesive force to human skin, and the influence on skin irritation is small when the skin is continuously or repeatedly applied to the same part of the skin surface. Therefore, the medical adhesive material according to the present invention is suitable for an adhesive material for repeatedly attaching to the same portion of the skin such as a tube for fixing a catheter, an adhesive material for continuously attaching to a specific portion of the skin such as a magnet therapy device plaster or a tape.

(support)

The moisture permeability coefficient of the support constituting the medical patch according to the present invention was 500 g/(m) ² 24 h) or more. By using a support having a sufficient moisture permeability coefficient, the moisture permeability coefficient is sufficiently high, and the skin irritation is less likely to occur when the support is applied to the skin with a small stuffiness And a medical patch for itching during the application. The moisture permeability coefficient of the support is preferably 500 g/(m) ² 24 h) or more, more preferably 700 g/(m) ² 24 h) or more, more preferably 1,000 g/(m) ² 24 h) or more, more preferably 1,500 g/(m2.24h) or more, particularly preferably 5,000 g/(m) ² 24 h) or more, most preferably 20,000 g/(m) ² 24 h) or more.

Examples of the support include: papers such as impregnated paper, coated paper, paper for ballast, kraft paper, japanese paper, and glassine paper; polyester films such as polyethylene terephthalate and polybutylene terephthalate, polyolefin films such as polyethylene and polypropylene, and plastic films such as polyvinyl chloride films, polycarbonate films, polyurethane films and cellophane films; a foam; cloth such as nonwoven fabric, woven fabric, knitted fabric, etc.; a laminate of two or more of the above materials, and the like. As a material of the cloth, natural materials such as cotton, synthetic resin materials, regenerated resin materials, and various materials appropriately combined with them can be used, and among them, nonwoven fabrics, woven fabrics, knitted fabrics, and the like using polyester, polyurethane, polyethylene, polypropylene, polyamide, acrylic resin, kapok, and the like as raw materials can be used.

The moisture permeability coefficient of the support of the medical adhesive material according to the present invention is 500 g/(m) ² 24 h) or more. Accordingly, the support is preferably a cloth such as a nonwoven fabric, a woven fabric, or a knitted fabric. Among them, a soft material that can be tightly bonded to the skin and can follow the skin action is preferable, and a material that can suppress the occurrence of rash or the like of the skin after long-term application is preferable, and a woven fabric is preferable from the viewpoint of excellent followability to the skin surface action at the time of application, easy maintenance of strength, and stronger self-back adhesion.

The thickness of the support may be appropriately selected in consideration of physical properties such as elongation, tensile strength, workability, feel at the time of attachment, sealability of an affected part, and the like, and is usually about 5 μm to 1 mm. In addition, in the case where the thickness of the support is extremely thin, in the range of 5 μm or more and 30 μm or less, the support layer may be provided on a surface (hereinafter referred to as the other side surface) opposite to the side surface of the support on which the adhesive layer is provided.

When the support is a cloth, the thickness thereof is preferably 50 μm or more and 1mm or less, more preferably 100 μm or more and 800 μm or less, and still more preferably 200 μm or more and 700 μm or less. Further, from the viewpoint of follow-up property to the skin, the grammage is preferably 400g/m ² Hereinafter, it is more preferably 300g/m ² Hereinafter, it is more preferably 250g/m ² The following is given.

In the case where the support is a plastic film, the thickness thereof is preferably 10 μm or more and 300 μm or less, more preferably 12 μm or more and 200 μm or less, and still more preferably 15 μm or more and 150 μm or less. In the case where the support is a film, one side surface or the other side surface of the support, or both surfaces of the support may be subjected to a treatment such as a blast treatment or a corona treatment for the purpose of improving the anchoring property between the adhesive layer and the support.

If the thickness of the support is less than 5 μm, the strength and handleability of the adhesive tape may be reduced, and the adhesive tape may be difficult to attach to the skin, and may be broken by contact with other members or the like, and may be peeled from the skin in a short time by contact with water such as bathing. Further, if the thickness of the support is too large (more than 1 mm), the pressure-sensitive adhesive tape is difficult to follow the action of the skin, and a trigger point for peeling is easily formed at the edge portion of the pressure-sensitive adhesive tape, and therefore, peeling from the skin may occur in a short time, and the uncomfortable feeling upon application may be increased.

(adhesive layer)

The adhesive layer is formed by applying the adhesive composition used in the present invention to the surface of the support in such a manner as to be a desired thickness and drying it. When the adhesive composition contains a crosslinking agent, a crosslinking treatment corresponding to the type of the crosslinking agent, such as an ultraviolet irradiation treatment, is performed after the application.

The thickness of the pressure-sensitive adhesive layer in the medical adhesive material according to the present invention is not particularly limited, but is preferably 1 μm or more and 200 μm or less, more preferably 10 μm or more and 100 μm or less, and still more preferably 20 μm or more and 80 μm or less. The adhesive force depends on the thickness of the adhesive layer, and if the thickness of the adhesive layer is too thick, the adhesive force becomes too high, and if the thickness of the adhesive layer is too thin, the adhesive force becomes weak. By setting the thickness of the adhesive layer within the above range, the adhesive material can be tightly bonded to the skin with sufficient adhesive force, and the adhesive material can be tightly bonded to the surface of the adherend having fine irregularities such as the skin, and skin irritation at the time of peeling after use can be suppressed to be low.

(Carrier layer)

The medical adhesive material according to the present invention may be temporarily adhered to a support to form a carrier layer. For example, an adhesive material having a laminated structure of "carrier layer/support/adhesive layer/separator layer" may be used. The carrier layer can improve film forming property of the support, handling property of the adhesive material, and adhesion property to the adherend when the support is thin. Since the carrier layer is provided to improve the operability of the adhesive material, the carrier layer may cover the entire surface of the adhesive material, may cover only the edge portion of the adhesive material, or may cover the adhesive material in a mesh pattern or the like.

The support layer is preferably formed using a film made of various thermoplastic resins such as polyurethane, polyethylene, polypropylene, ionomer, polyamide, polyvinyl chloride, polyvinylidene chloride, ethylene vinyl acetate copolymer, thermoplastic polyester, polytetrafluoroethylene, and the like.

The various films may be films in a state of being laminated on paper. As these carrier layers, it is preferable that the thickness is thicker or more rigid than the support (e.g., polyurethane elastomer film). The thickness of the support layer can be appropriately set, and is usually 10 μm or more, preferably 20 μm or more, and the upper limit thereof is about 500 μm.

(separation layer)

The medical adhesive material according to the present invention generally includes a separator layer adjacent to the adhesive layer in order to protect the adhesive layer before the adhesive layer is applied to the skin, in addition to the support layer and the adhesive layer.

The separator in the present invention is not particularly limited, and a separator used in the technical field of an adhesive material, which is generally called release paper, release film, release liner, or the like, can be used. Specifically, examples thereof include a polyethylene terephthalate film having a surface treated with silicone, a laminate of polyethylene and paper having a surface treated with silicone, and the like. In order to improve the handling property (i.e., the peelability from the adhesive layer), the separator may be provided with a slit, or may be formed with a larger area than the adhesive material and may be provided with a grip portion at the peripheral edge portion. Further, for the purpose of improving the handleability and printability of the separator, irregularities obtained by sandblasting or the like may be provided on the surface of the separator opposite to the pressure-sensitive adhesive layer or the surface opposite to the pressure-sensitive adhesive layer.

The thickness of the separator is not particularly limited, and is usually 20 μm or more, preferably 40 μm or more, and the upper limit thereof is about 500 μm.

(moisture permeability coefficient)

The medical patch according to the present invention preferably has a moisture permeability coefficient of 500 g/(m) ² 24 h) or more. The moisture permeability coefficient by the adhesive material was 500 g/(m) ² 24 h) or more, whereby the feeling of stuffiness when applied to the skin is reduced, and thus skin irritation and itching when applied are less likely to occur. The moisture permeability coefficient of the adhesive material is more preferably 700 g/(m) ² 24 h) or more, more preferably 1,000 g/(m) ² 24 h) or more, more preferably 1,500 g/(m) ² 24 h) or more, particularly preferably 5,000 g/(m) ² 24 h) or more, most preferably 20,000 g/(m) ² 24 h) or more. The higher the moisture permeability coefficient, the more preferable, the upper limit of the preferred moisture permeability coefficient is not particularly limited, and is usually 30,000 g/(m) ² 24 h) or below. In the present invention, the moisture permeability coefficient was measured at a temperature of 40℃and a relative humidity of 90% according to the B condition of JIS Z0208. That is, one side of the adhesive material was adjusted to a temperature of 40℃and a relative humidity of 90%, and a hygroscopic agent such as calcium chloride was placed on the other side to absorb moisture passing through the adhesive material, and the amount of change in the weight of the hygroscopic agent was 1m every 24 hours ² And converted and calculated.

(adhesive force)

The adhesive force of the medical adhesive material according to the present invention is preferably in the range of 0.5N/25mm to 12.0N/25mm, more preferably 2.0N/25mm to 8.0N/25mm, as the adhesive force (peeling force) to bakelite. When the adhesive force of the medical adhesive material is within this range, the medical adhesive material according to the present invention has sufficient adhesive performance when being adhered to the skin surface, and does not cause positional displacement during adhesion and does not cause the risk of peeling off the skin surface or causing rash when peeling off the adhesive material.

The method for measuring the adhesive force of the medical adhesive material is as follows. That is, the test piece is obtained by cutting the adhesive material into a predetermined length of 25mm wide by 15mm long, preferably 100 mm. After the test piece was pressed against the bakelite test plate and bonded, the test piece was prepared by bonding the test piece with a 2kg roller at a bonding speed of 300 mm/min and a bonding number of times of 1 reciprocation. After 20 minutes from the lamination, the adhesive force was measured under conditions of 180℃in terms of peel angle and 300 mm/min in terms of peel adhesion test method according to method 1 of ISO 29862 (JIS Z0237).

(method for producing medical adhesive Material)

The method for producing the medical patch according to the present invention is not particularly limited. For example, the following method is preferably employed: an adhesive solution is applied to a separator layer that is usually used as a so-called release liner, and the separator layer is dried to form an adhesive layer. As a continuous forming method of the adhesive layer, the following method is preferable: the separator is moved in one direction while the adhesive solution is applied thereto and dried. A method of applying the adhesive to the separator by melting the adhesive may also be employed. In addition, a repetitive pattern coating of a specific shape may be used.

An adhesive material having a laminated structure of "support/adhesive layer/separator" can be produced by bonding a laminate having an adhesive layer formed on one surface of a separator layer to a support so that the adhesive layer and the surface of the support are tightly bonded. In the case of a laminate in which a carrier layer having an arbitrary layer is formed on one surface of a support, an adhesive layer is bonded to the surface of the support of the laminate so as to be tightly bonded to the surface, whereby an adhesive material having a laminate structure of "carrier layer (arbitrary layer)/support/adhesive layer/separator" can be produced.

Examples

Next, examples are shown to further explain the present invention in detail, but the present invention is not limited to the following examples.

Examples 1 to 4 and comparative examples 1 to 7

Adhesive compositions containing various liquid plasticizers were prepared, and the adhesive force and the effect on human skin were examined for the attachment materials forming an adhesive layer from these adhesive compositions. As the liquid plasticizer, methyl oleate (molecular weight: 296.5), isopropyl myristate (molecular weight: 268.0), glycerol monooleate (molecular weight: 356.0), sorbitol monooleate (molecular weight: 428.6), oleic oil (molecular weight: 531.0), isostearic acid isostearate (molecular weight: 537.0), soyBean oil (molecular weight: about 880, SR SoyBean-LQ- (JP), manufactured by Croda Japan Co., ltd.), sorbitol trioleate (molecular weight: 935.0), castor oil fatty acid ester (molecular weight: about 500, manufactured by Itany Japan Co., ltd.), decyl oleate (molecular weight: 422.4), special castor oil condensed fatty acids (molecular weight: 800, manufactured by Itany Japan Co., ltd.), castor oil fatty acid esters (molecular weight: about 500, manufactured by Itany Japan Co., ltd.) were used. Further, as the support, woven cloth (warp: core spun yarn (core spun), weft: cotton, moisture permeability coefficient: 21,060 g/(m) ² 24 h), gram weight 155g/m ² ) Polyurethane nonwoven fabric (fiber diameter: 15 μm, moisture permeability coefficient: 21,590 g/(m) ² 24 h), grammage 65g/m ² ) Polyethylene film (thickness: 50 μm, moisture permeability coefficient: 60 g/(m) ² ·24h))。

Sample preparation

First, as an adhesive composition, a solution of a homogeneous adhesive composition was prepared by mixing 100 parts by mass of the liquid plasticizer shown in table 1 and described in tables 1 to 3 with a solution of an acrylic copolymer obtained by copolymerizing a monomer mixture composed of 2-ethylhexyl acrylate/vinyl acetate/acrylic acid=85/11/4 (mass ratio), and further mixing 0.06 parts by mass of tetra-X (manufactured by mitsubishi gas chemical company, ltd.) as a crosslinking agent with 100 parts by mass of the acrylic copolymer.

The solution of the adhesive composition was applied to the release treated surface of a separator (silicone treated) so that the thickness of the adhesive composition after drying was 38 μm, and the adhesive layer was formed after drying. The adhesive layer was bonded to the support described in tables 1 to 3, to thereby prepare a bonding material.

< determination of adhesion to human skin >

Test samples of dimensions 15mm x 70mm were attached to the forearm of the subject. After 24 hours from the attachment, the adhesive force (N/15 mm) was measured using an Instron type tensile tester at a peeling speed of 100 mm/min and a peeling angle of 90 ° (n=8). Peeling was performed from the little finger side to the thumb side. The measurement results are shown in tables 1 to 3.

< measurement of area of keratosis >

Each test specimen peeled off in the adhesion measurement was dyed with a cationic dye (gentian violet: 1.0%, brilliant green: 0.5%, distilled water: 98.5%) and then washed with running water. The stained test specimens were imaged under a microscope (VHX-1000: VH-Z100UR, manufactured by Kien's Co., ltd.), and the obtained images were subjected to image analysis by an image processing device (Win ROOF, manufactured by Sangu Co., ltd.), to thereby determine the areas of keratinocytes adhered to each of the test specimens. For each test sample, the keratinocyte adhesion area ratio ([ keratinocyte adhesion area ]/[ surface area of test sample ] ×100 (%)) in 3 fields was calculated, and the average value thereof was taken as the keratolytic area ratio (n=8) of each test sample. The measurement results are shown in tables 1 to 3.

< residue of adhesive >

In the adhesion measurement, whether or not an adhesive remains on the skin surface after peeling each test sample was visually confirmed (n=8). The results are shown in tables 1 to 3. In the table, "x" indicates that the adhesive remains on the skin at the time of peeling, and "good" indicates that the adhesive does not remain on the skin at the time of peeling.

< repeated forearm attachment test >

The following repeated forearm attachment test (up to 7 days, 7 test samples for 1 test area) was performed: the test samples were applied to the human skin surface, peeled off every 24 hours, and after confirming the skin reaction after 1 hour, a new test sample of the same kind was applied to the same site (n=9). Skin reactions after 1 hour and 24 hours (day of end of test) of peeling at 5: no reaction, 4: mild erythema, 3: erythema, 2: there are erythema + edema, 1: there were erythema + edema + papules, or small blisters, 0: the evaluation was carried out in such a manner that there was a large blister. The results are shown in tables 1 to 3.

TABLE 1

TABLE 2

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TABLE 3

By comparing examples 1 to 6 and comparative examples 1 to 8, in which the supports were the same, the adhesion to human skin was improved by containing 10 parts by mass or 20 parts by mass of fatty acid ester per 100 parts by mass of the acrylic copolymer, and the adhesion was improved by containing fatty acid ester in the test samples (comparative examples 2 to 3, examples 1 to 6, and comparative examples 5 to 8) compared with the test sample (comparative example 1) containing no fatty acid ester. In a test sample (comparative example 4) containing 30 parts by mass of the fatty acid ester with respect to 100 parts by mass of the acrylic copolymer, an adhesive residue occurred at the time of peeling. This is presumably because the content of the liquid plasticizer is large, and the adhesive layer is too soft. On the other hand, a test sample (comparative example 7) in which decyl oleate having poor compatibility with the acrylic copolymer was selected, and an adhesive residue was generated in the adhesive residue test, which was problematic as a medical patch.

The exfoliating area ratio of each of the test samples was sufficiently lower than that of comparative example 1, and was about 40% in the test samples (examples 1 to 6) containing the fatty acid esters having a molecular weight in the range of 350 to 550 inclusive and good compatibility with the acrylic copolymer. On the other hand, in the test samples (comparative example 2, comparative examples 5, 6, 8) containing fatty acid esters having molecular weights outside this range, the exfoliating area ratio was 50% or more, and it was confirmed that the reducing effect was poor. Further, the test sample of comparative example 3, which contained 15 parts by mass of isopropyl myristate (molecular weight: 268.0) having a molecular weight outside this range and 5 parts by mass of oleic acid oil ester (molecular weight: 531.0) having a molecular weight within this range and had a weight average molecular weight of 333.8[ (268.0 ×15+531.0×5)/(15+5) ] as the liquid plasticizer, had a keratolytic area ratio of 50% or more and had a poor reduction effect, as the test sample containing only the fatty acid ester having a molecular weight outside this range.

For skin reactions, the test samples (examples 1 to 6) containing fatty acid esters having a molecular weight in the range of 350 to 550 inclusive and good compatibility with the acrylic copolymer were confirmed to have little deterioration in skin state with time and to maintain skin state. Further, after 24 hours of peeling at the end of the test, it was confirmed that there were few testers who remained reddish. On the other hand, the test samples (examples 3, 7, comparative example 9) differing only in the support were compared, and the moisture permeability coefficient was 500 g/(m) ² Example 7 in which 24 h) or more polyurethane nonwoven fabric was used as a support was not inferior to the polyurethane nonwoven fabric having a moisture permeability coefficient of 500 g/(m) ² 24 h) or more weavingEvaluation of example 3 in which the cloth was used as a support, the moisture permeability coefficient was set to 60 g/(m) ² In comparative example 9 in which the polyethylene film of 24 h) was used as a support, the skin adhesion was greatly lowered and the skin reaction was also strong, although the keratolytic area ratio was low. From these results, it is clear that the moisture permeability coefficient is set to 500 g/(m) ² 24 h) or more, and an appropriate amount of a fatty acid ester having a molecular weight of 350 to 550, which is excellent in compatibility with the acrylic copolymer, is contained in the pressure-sensitive adhesive layer formed of the acrylic copolymer, whereby a pressure-sensitive adhesive layer which maintains high adhesive strength and is less in skin irritation when continuously or repeatedly applied to the same portion of the skin can be formed.

Claims

1. A medical adhesive material comprising a laminate of a support and an adhesive layer,

the moisture permeability coefficient of the support is 500 g/(m) ² 24 h) of a total of two or more,

the support body is cloth, and the cloth is non-woven fabrics, woven fabrics or knitted fabrics.

2. The medical patch according to claim 1, wherein,

the fatty acid ester contains a single type of fatty acid ester having a weight average molecular weight of 350 to 550.

3. The medical patch according to claim 1 or 2, wherein,

the copolymer is a copolymer obtained by polymerizing the following substances through a solution polymerization method and crosslinked by a crosslinking agent: 65 to 90 mass% of an alkyl acrylate having an alkyl group having 8 to 12 carbon atoms; 2 mass% or more and 15 mass% or less of acrylic acid; 5 mass% or more and 25 mass% or less of vinyl acetate; and 0 mass% or more and 10 mass% or less of other vinyl monomers.

4. The medical patch according to claim 1 or 2, wherein,

the fatty acid esters have at least one oleic acid residue.

5. The medical patch according to claim 4, wherein,

the fatty acid residues in the fatty acid ester are all oleic acid residues.

6. The medical patch according to claim 1 or 2, wherein,

the pressure-sensitive adhesive layer further includes a separator layer on a surface of the pressure-sensitive adhesive layer facing the surface in contact with the support.

7. The medical patch according to claim 1 or 2, wherein,

the medical adhesive material is repeatedly adhered to the same part of the skin.

8. The medical patch according to claim 1 or 2, wherein,

the medical attachment material is used for fixing a tube.