CN113853414A

CN113853414A - Adhesive materials for medical use

Info

Publication number: CN113853414A
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: 2021-12-28
Anticipated expiration: 2039-12-19
Also published as: KR20220027057A; JP2020006166A; WO2020261609A1; JP7369552B2; CN113853414B; KR102741324B1

Abstract

一种医疗用贴附材料，其具备支撑体和粘合剂层构成的层叠体，所述粘合剂层由粘合剂组合物构成，所述粘合剂组合物含有以(甲基)丙烯酸烷基酯作为主要成分的共聚物、以及在室温下为液态且与所述共聚物相溶的脂肪酸酯，所述粘合剂组合物中含有的所述脂肪酸酯的重均分子量为350以上而550以下，所述粘合剂组合物相对于100质量份的所述共聚物含有5质量份以上而25质量份以下的所述脂肪酸酯，所述支撑体的透湿系数为500g/(m²·24h)以上。A medical sticking material comprising a support body and a laminate composed of a pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer being formed of a pressure-sensitive adhesive composition containing (meth)acrylic acid A copolymer containing an alkyl ester as a main component, and a fatty acid ester that is liquid at room temperature and that is compatible with the copolymer, wherein the weight average molecular weight of the fatty acid ester contained in the adhesive composition is 350 more than 550 parts by mass, the adhesive composition contains 5 parts by mass or more and 25 parts by mass or less of the fatty acid ester based on 100 parts by mass of the copolymer, and the moisture permeability coefficient of the support is 500 g/ (m ² ·24h) or more.

Description

Medical adhesive sheet

Technical Field

The present invention relates to a medical adhesive patch to be applied 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 patch. The present application claims priority based on Japanese application No. 2019-122202, filed in 6/28/2019, the contents of which are incorporated herein by reference.

Background

Medical patches such as adhesive bandages and plasters are also used for fixing tubes of catheters and the like to the skin surface. In fixing a catheter or the like, it is necessary to stably fix the catheter or the like so as not to be erroneously peeled off, and therefore, a medical adhesive material to be used tends to have a high priority for high adhesion. On the other hand, catheters and the like sometimes require long-term fixation and sometimes repeated fixation at the same part of the skin. Therefore, medical patch materials for fixing catheters and the like are required to have little influence on the skin when continuously and repeatedly applied. In addition, analgesic and anti-inflammatory agents, magnetic therapy plasters, tapes (taping tapes), and the like, which are applied to specific parts such as shoulders, waists, and the like, may be repeatedly fixed to the same part of the skin, and medical patch materials used for these applications and the like are expected to have little influence on the skin even when applied continuously or repeatedly.

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

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

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

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

Disclosure of Invention

The purpose of the present invention is to provide a medical adhesive patch that has sufficient adhesive force and that has little effect on the skin when repeatedly attached to the same area of the skin.

The inventors have found that a fatty acid ester having a weight average molecular weight of 350 to 550 inclusive and being liquid at room temperature is contained in an acrylic adhesive constituting an adhesive layer of a medical patch in an amount of 5 to 25 parts by mass with respect to 100 parts by mass of an acrylic copolymer, and that the acrylic adhesive uses a moisture permeability coefficient of 500 g/(m)²24h) or more as a support for a medical patch, thereby obtaining a medical patch in which the area ratio of exfoliating keratin is reduced while maintaining high adhesion to human skin, and the present invention has been completed.

Namely, the present invention provides the following medical patch.

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

the pressure-sensitive adhesive layer is composed of a pressure-sensitive 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 or more and 550 or less,

the adhesive composition contains 5 parts by mass or more and 25 parts by mass or less of the fatty acid ester per 100 parts by mass of the copolymer,

the moisture permeability coefficient of the support body is 500 g/(m)²24h) above.

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

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

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

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

[6] The medical patch according to any one of [1] to [5], wherein a separator layer is further provided on a surface of the adhesive layer opposite to a surface thereof which is in contact with the support.

[7] The medical patch according to any one of [1] to [6], wherein the medical patch is repeatedly attached to the same part 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 patch in which the adhesive layer is formed of an adhesive composition that maintains high adhesive force and causes little skin irritation when continuously or repeatedly applied to the same part of the skin.

Detailed Description

< adhesive composition >

The adhesive composition constituting the adhesive layer of the medical patch 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 which is compatible with a copolymer containing an alkyl (meth) acrylate as a main component as a binder and imparts plasticity.

(copolymer containing alkyl (meth) acrylate as a main component)

A copolymer containing an alkyl (meth) acrylate as a main component (hereinafter, sometimes referred to as "acrylic copolymer") means a copolymer in which 50 mol% or more of the total constituent units constituting the copolymer are constituent units derived from an alkyl (meth) acrylate. In the present invention and the present specification, the 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 in which the number of carbon atoms in the alkyl moiety is 1 or more and 18 or less. Specifically, there may be mentioned: methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-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 that is a source of the constituent unit of the acrylic copolymer used in the present invention is preferably an alkyl (meth) acrylate having an alkyl group having 4 or more and 18 or less carbon atoms, more preferably an alkyl (meth) acrylate having an alkyl group having 4 or more and 12 or less carbon atoms, more preferably an alkyl (meth) acrylate having an alkyl group having 6 or more and 12 or less carbon atoms, more preferably an alkyl (meth) acrylate having an alkyl group having 8 or more and 12 or less carbon atoms, and 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, as a constituent unit derived from an alkyl (meth) acrylate, at least one constituent unit derived from an alkyl (meth) acrylate having 4 or more and 18 or less carbon atoms in the alkyl moiety. For example, the constituent unit derived from an alkyl (meth) acrylate may be a copolymer having only a constituent unit derived from an alkyl (meth) acrylate having 4 or more and 18 or less carbon atoms in the alkyl moiety, or may be a copolymer including both a constituent unit derived from an alkyl (meth) acrylate having 4 or more and 18 or less carbon atoms in the alkyl moiety and a constituent unit derived from the other alkyl (meth) acrylate.

The acrylic copolymer used in the present invention may be a copolymer composed of only a constituent unit derived from an alkyl (meth) acrylate, or may be a copolymer containing a constituent unit 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, and a heterocyclic group. Examples of the vinyl monomer having a hydroxyl group include (meth) acrylates 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 acrylates such as 2-methoxyethyl acrylate and ethoxyethyl acrylate. Examples of the vinyl monomer having an acyl group include vinyl esters such as vinyl acetate. Examples of the vinyl monomer having a cyano group include unsaturated nitriles such as acrylonitrile and methacrylonitrile. Examples of the vinyl monomer having an aryl group include vinyl aromatic compounds such as styrene. Examples of the vinyl monomer having a heterocyclic group include 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 containing at least one 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 (hereinafter, sometimes referred to as "vinyl monomer (a)"), and further preferably a copolymer containing at least one vinyl monomer having no functional group (hereinafter, sometimes referred to as "vinyl monomer (B)").

The acrylic copolymer used in the present invention is preferably the following copolymer: the alkyl acrylate having an alkyl group with 4 to 18 carbon atoms, preferably 8 to 12 carbon atoms, is 55 to 95 mass%, preferably 60 to 95 mass%, more preferably 65 to 90 mass%, even more preferably 80 to 90 mass%, particularly preferably 83 to 87 mass%, most preferably 85 mass%, based on the total mass of the monomers used for copolymerization; the vinyl monomer (a) is 1% by mass or more and 25% by mass or less, preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, further preferably 2% by mass or more and 10% by mass or less, particularly preferably 2% by mass or more and 6% by mass or less, and particularly preferably 4% by 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, further 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%; and other vinyl monomers in an amount of 0 to 10% by mass, more preferably the following copolymers: the alkyl acrylate having an alkyl group with 4 to 18 carbon atoms, 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% by mass or more and 25% by mass or less, preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, further preferably 2% by mass or more and 10% by mass or less, particularly preferably 2% by mass or more and 6% by mass or less, and particularly preferably 4% by mass; the vinyl monomer (B) is 0 mass% or more and 40 mass% or less, preferably 3 mass% or more and 30 mass% or less, more preferably 5 mass% or more and 25 mass% or less, further 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%; and the other vinyl monomers in an amount of 0 to 10 mass%. Among them, the vinyl monomer (a) is particularly preferably acrylic acid, the vinyl monomer (B) is vinyl acetate, and the following copolymers are more preferably used: the alkyl acrylate having an alkyl group with 4 to 18 carbon atoms, preferably 8 to 12 carbon atoms, is 55 to 95 mass%, preferably 60 to 95 mass%, more preferably 65 to 90 mass%, even more preferably 80 to 90 mass%, particularly preferably 83 to 87 mass%, most preferably 85 mass%, based on the total mass of the monomers used for copolymerization; acrylic acid is 1% by mass or more and 25% by mass or less, preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, further preferably 2% by mass or more and 10% by mass or less, particularly preferably 2% by mass or more and 6% by mass or less, and particularly preferably 4% by mass; the vinyl acetate is 0 mass% or more and 40 mass% or less, preferably 3 mass% or more and 30 mass% or less, more preferably 5 mass% or more and 25 mass% or less, further 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%; and the other vinyl monomers in an amount of 0 to 10 mass%. By using the acrylic copolymer having the above copolymer component as the adhesive, an adhesive layer showing appropriate adhesiveness even if the adhesive layer is thin and excellent in other properties is 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 within the above range, the cohesion, adhesion, workability in mixing with other components, and affinity with other components can be balanced. If the molecular weight is less than 300,000, the cohesion is reduced, and thus adhesive residue on the skin may be generated upon peeling. If the weight average molecular weight exceeds 1,000,000, the workability in the production is poor. The weight average molecular weight of the acrylic copolymer is a value obtained by Gel Permeation Chromatography (GPC) method using standard 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 terms of easily obtaining good adhesive properties. Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide and lauroyl peroxide; azo initiators such as azobisisobutyronitrile. The radical polymerization initiator is added in a proportion of about 0.1 to 3% by mass relative to all monomers, and the mixture is stirred under a nitrogen gas flow at a temperature of about 40 to 90 ℃ for several hours to several tens of hours to be copolymerized. In the solution polymerization method, ethyl acetate, acetone, toluene, a mixture thereof, and the like are widely used as a solvent.

(crosslinking agent)

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

Examples of the crosslinking agent include: polyfunctional isocyanate compounds [ Tolylene Diisocyanate (TDI),4,4' -diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate, xylylene diisocyanate, m-xylylene diisocyanate, 1, 5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, etc. ], polyfunctional epoxy compounds, acetylacetone metal salts, etc. Further, commercially available products such as "コロネート" (CORONATE, registered trademark) HL, "コロネート" L, "コロネート" EH, TETRAD-X (registered trademark), TETRAD-C (registered trademark), and "ナーセム" (Nursem, registered trademark) aluminum, which are manufactured by Mitsubishi gas chemical corporation, for example, can be used as the crosslinking agent. The crosslinking agent may be used alone or in an amount 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 part by mass or more and 1 part by mass or less, more preferably 0.03 part by mass or more and 0.5 part by mass or less, still more preferably 0.04 part by mass or more and 0.1 part by mass or less, particularly preferably 0.04 part by mass or more and 0.08 part by mass or less, and most preferably 0.06 part by mass, relative to 100 parts by mass of the acrylic copolymer.

When the binder composition used in the present invention contains a crosslinking agent, the crosslinking agent may be contained in the binder composition in advance, or the crosslinking agent may be added to the binder composition immediately before the binder composition is applied to a support or during the application.

(liquid plasticizer)

The liquid plasticizer contained in the adhesive layer of the medical adhesive patch according to the present invention plasticizes the adhesive layer to give a soft feeling, thereby reducing skin irritation. The liquid plasticizer contained in the pressure-sensitive adhesive composition used in the present invention is a fatty acid ester having a weight average molecular weight of 350 or more and 550 or less, which is liquid at room temperature and is compatible with the acrylic copolymer contained in the pressure-sensitive adhesive composition. Hereinafter, 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 single type of fatty acid ester (in this case, there is almost no molecular weight distribution, and the molecular weight is substantially inherent to a single type), and the weight average molecular weights of a plurality of types of fatty acid esters. The fatty acid ester that is liquid at room temperature and contained in the pressure-sensitive adhesive composition may be only a single type of fatty acid ester that is compatible with the acrylic copolymer contained in the pressure-sensitive adhesive composition and has a molecular weight of 350 or more and 550 or less, or may contain two or more types of fatty acid esters. When two or more kinds of fatty acid esters which are liquid at room temperature and are compatible with the acrylic copolymer contained in the pressure-sensitive adhesive composition are contained, the weight average molecular weight of these fatty acid esters may be in the range of 350 to 550. By using a fatty acid ester which is liquid at room temperature, has a size within a specific range, and is compatible with the acrylic copolymer, the acrylic copolymer and the fatty acid ester are uniformly mixed, and an adhesive layer which maintains high adhesion to human skin and sufficiently suppresses the residue on the skin when peeled from the skin is formed.

Among fatty acid esters having a molecular weight in the range of 350 to 550 inclusive, a fatty acid ester having high compatibility with an acrylic copolymer can impart sufficient plasticity, and is not volatilized in a heating step such as a drying step after coating 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 can be obtained which can impart appropriate skin adhesion when forming an adhesive layer and can suppress the area of keratin to be peeled off when peeling.

The binder composition used in the present invention is preferably an oleate containing at least one fatty acid residue (residue derived from a fatty acid; specifically, a group obtained by removing a hydroxyl group from a fatty acid) as an oleic acid residue (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 effect of the adhesive layer formed from the adhesive composition used in the present invention on the skin is further reduced when the adhesive layer is continuously applied (when the adhesive layer is applied for a long time) or repeatedly applied.

The oleate 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 octyl alcohol, 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 polyhydric alcohol and oleic acid, only one hydroxyl group in the polyhydric alcohol may be ester-bonded to a fatty acid, or two or more hydroxyl groups may be ester-bonded to a fatty acid. In the case of an oleate in which two or more hydroxyl groups are ester-bonded to a fatty acid, only a 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.

Specific examples of the oleate having a molecular weight in the range of 350 to 550 inclusive, which is 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 esters, and the like. These oleic acid esters may be used alone or in combination of two or more. The oleate contained in the adhesive composition used in the present invention is preferably glyceryl monooleate (molecular weight: 356.5), sorbitol monooleate (molecular weight: 428.6), or oleic acid oleyl ester (molecular weight: 531), and particularly preferably oleic acid oleyl ester.

The content of the oleate in the pressure-sensitive adhesive composition used in the present invention, which has a molecular weight in the range of 350 to 550 inclusive, 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. When the content is less than 1 part by mass, the plasticization of the adhesive layer may be insufficient and the skin irritation may not be reduced, whereas when it exceeds 35 parts by mass, the cohesive force of the adhesive may be reduced and the adhesive may remain on the skin when peeled off.

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

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 long as the effects of the present invention are not impaired. The other liquid plasticizer is not particularly limited as long as it is a 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; olive oil, castor oil, squalane, lanolin and other oils; hydrocarbons such as liquid paraffin, and the like. In addition, an organic solvent or a surfactant which is liquid at room temperature may be used. The whole of the fatty acid ester contained in the pressure-sensitive adhesive composition may be compatible with the acrylic copolymer constituting the pressure-sensitive adhesive composition, and may contain a fatty acid ester incompatible with the acrylic copolymer.

When 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 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, based on 100 parts by mass of the acrylic copolymer. When the content is less than 1 part by mass, the plasticization of the adhesive layer may be insufficient and the skin irritation may not be reduced, whereas when it exceeds 35 parts by mass, the cohesive force of the adhesive may be reduced and the adhesive may remain on the skin when peeled off. In the case where the acrylic copolymer contains two or more types of fatty acid esters having a molecular weight in the range of 350 to 550 inclusive and 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 pressure-sensitive adhesive composition" represents the total amount of the fatty acid ester corresponding to the fatty acid ester having a molecular weight in the range of 350 to 550 inclusive and compatible with the acrylic copolymer.

When the adhesive composition used in the present invention contains a fatty acid ester having a molecular weight in the range of 350 to 550 inclusive and compatible with the acrylic copolymer and another liquid plasticizer, the content of the fatty acid ester having a molecular weight in the range of 350 to 550 inclusive is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total amount of the liquid plasticizer contained in the adhesive composition used in the present invention. The weight average molecular weight of the entire liquid plasticizer contained in the adhesive composition, particularly the weight average molecular weight of the entire fatty acid ester that is liquid at room temperature, is preferably in the range of 350 to 550.

(additives)

The adhesive composition used in the present invention may contain various additives as needed, in addition to the crosslinking agent. The additive may contain additives commonly used in adhesives for forming adhesive layers of adhesive materials, such as drugs, fillers, antioxidants (antioxidants and preservatives), coloring agents, perfumes, and tackifiers. For example, a tackifier may be formulated in order to adjust the adhesive characteristics of the adhesive. Examples of the tackifier include tackifying resins such as terpenes, terpene phenols, coumarone-indenes, styrenes, rosins, xylenes, phenols, and petroleum.

< medical adhesive sheet >

The medical patch according to the present invention includes a laminate composed of a support and an adhesive layer. The medical patch 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 was formed from the adhesive composition, the following medical patch was obtained: the adhesive sheet can suppress the area of peeling of keratin when peeled off while maintaining sufficient adhesive force to human skin, and has little effect on skin irritation when continuously or repeatedly attached to the same part of the skin surface. Therefore, the medical patch according to the present invention is suitable for use as a patch that repeatedly adheres to the same part of the skin such as a tube for fixing a catheter or the like, or a patch that continuously adheres to a specific part of the skin such as a magnetic therapeutic plaster or a tape or the like, and repeatedly adheres thereto.

(support)

The moisture permeability coefficient of the support constituting the medical patch of the present invention is 500 g/(m)²24h) above. By using the support having a sufficient moisture permeability coefficient, the medical patch has a sufficiently high moisture permeability coefficient, is less stuffy when applied to the skin, and is less likely to cause skin irritation or itching when applied. The moisture permeability coefficient of the support is preferably 500 g/(m)²24h) or more, more preferably 700 g/(m)²24h) or more, and more preferably 1,000 g/(m)²24h) or more, more preferably 1,500g/(m 2-24 h) or more, and particularly preferably 5,000 g/(m)²24h) or more, most preferably 20,000 g/(m)²24h) above.

Examples of the support include: papers such as impregnated paper, coated paper, dow paper, kraft paper, japanese paper, glassine paper, and the like; plastic films such as polyethylene terephthalate, polybutylene terephthalate and other polyester films, polyethylene, polypropylene and other polyolefin films, polyvinyl chloride films, polycarbonate films, polyurethane films, cellophane films and other plastic films; a foam; fabrics such as nonwoven fabrics, woven fabrics, and knitted fabrics; a laminate of two or more of the above substances, and the like. As the material of the cloth, natural materials such as cotton, synthetic resin materials, regenerated resin materials, and various materials obtained by appropriately combining them can be used, and among them, non-woven fabrics, knitted fabrics, and the like, which are made of polyester, polyurethane, polyethylene, polypropylene, polyamide, acrylic resin, kapok, and the like, can be used.

The moisture permeability coefficient of the support of the medical adhesive patch of the present invention is 500 g/(m)²24h) above. Therefore, the support is preferably a cloth such as a nonwoven fabric, a woven fabric, or a knitted fabric. Among them, a soft material is preferable to be capable of closely adhering to the skin and following the skin action, and a material capable of suppressing the occurrence of rash or the like of the skin after long-time adhesion is preferable in that the following property to the skin surface action at the time of adhesion is excellent, and further, the strength is easily maintained and the self-back adhesive force is further strong, and woven cloth is preferable.

The thickness of the support can be appropriately selected in consideration of physical properties such as elongation, tensile strength and workability, feeling at the time of application, and sealing property of the affected part, and is usually about 5 μm to 1 mm. In the case where the support is very thin, such as 5 μm or more and 30 μm or less, the support layer may be provided on a surface (hereinafter, referred to as the other surface) facing the one 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, the grammage is preferably 400g/m in terms of the ability to follow the skin²Hereinafter, more preferably 300g/m²Hereinafter, it is more preferably 250g/m²The following.

When 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 of them 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 adhesive tape may be deteriorated in strength and handling property, may be difficult to adhere to the skin, may be damaged by contact with other members, and may be peeled off from the skin in a short time by contact with water in a bath or the like. Further, if the thickness of the support is too large (more than 1mm), the adhesive tape is difficult to follow the movement of the skin, and a trigger point for peeling is easily formed at the edge portion of the adhesive tape, and therefore, the adhesive tape may be peeled from the skin in a short time, which may increase the uncomfortable feeling during application.

(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 have a desired thickness and drying it. When the adhesive composition contains a crosslinking agent, crosslinking treatment corresponding to the kind of the crosslinking agent such as ultraviolet irradiation treatment is performed after coating.

The thickness of the pressure-sensitive adhesive layer in the medical patch 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 pressure-sensitive adhesive layer within the above range, the adhesive sheet can be adhered to the skin with sufficient adhesive force, and the patch can be tightly bonded along the surface of an adherend having fine irregularities such as the skin, and skin irritation at the time of peeling after use can be suppressed to a low level.

(Carrier layer)

The medical patch according to the present invention may be temporarily bonded to a support to form a carrier layer. For example, it may be an attachment material having a laminated structure of "carrier layer/support body/adhesive layer/separation layer". The presence of the carrier layer can improve the film forming property of the support, the workability of the adhesive material, and the adhesiveness to the adherend when the thickness of the support is small. Since the carrier layer is provided to improve the workability of the patch, the carrier layer may cover the entire surface of the patch, may cover only the edge portion of the patch, or may cover the patch in a pattern such as a mesh pattern.

As the carrier layer, it is preferable to use a film formed 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 they are thicker or harder than the support (e.g., polyurethane elastomer film). The thickness of the support layer can be suitably set, and is usually 10 μm or more, preferably 20 μm or more, and its upper limit value is about 500 μm.

(separation layer)

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

The separator in the present invention is not particularly limited, and those generally called release paper, release film, release liner, and the like in the technical field of the adhesive material can be used. Specifically, for example, a polyethylene terephthalate film whose surface is treated with silicone, a laminate of polyethylene and paper whose surface is treated with silicone, and the like can be given. In addition, in order to improve the handling property (i.e., the peelability from the adhesive layer), the separator may be provided with a notch or may be formed in a larger area than the patch and provided with a grip portion at the peripheral edge portion. For the purpose of improving the handling properties and the printability of the separator, the surface of the separator facing the pressure-sensitive adhesive layer or the surface opposite to the pressure-sensitive adhesive layer may be provided with irregularities obtained by sandblasting or the like.

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

(moisture permeability coefficient)

The medical patch according to the present invention preferably has a moisture permeability coefficient of 500 g/(m)²24h) above. The moisture permeability coefficient of the patch is 500 g/(m)²24h) or more, the feeling of stuffiness when attached to the skin is reduced, and thus skin irritation and itching at the time of attachment are less likely to be caused.The moisture permeability coefficient of the patch is more preferably 700 g/(m)²24h) or more, and more preferably 1,000 g/(m)²24h) or more, and more preferably 1,500 g/(m)²24h) or more, particularly preferably 5,000 g/(m)²24h) or more, most preferably 20,000 g/(m)²24h) above. The higher the moisture permeability coefficient is, the more preferable the upper limit of the moisture permeability coefficient is, the more preferable the moisture permeability coefficient is, the lower the moisture permeability coefficient is, and the lower the moisture permeability coefficient is, the lower the moisture permeability is, and the lower the moisture permeability is, the lower the moisture permeability is, and the lower the moisture permeability is, and the lower the moisture permeability is, and the lower the moisture permeability is, and the lower the moisture permeability is, and the lower the moisture permeability is, and the moisture resistance is, and the lower the moisture resistance is, and the lower the moisture resistance, and the moisture resistance is, and the lower the moisture resistance, and the lower the moisture resistance, and the moisture resistance is, and the lower the moisture resistance is, and the lower the moisture resistance, and the lower the moisture resistance is, and the lower the²24h) or less. In the present invention, the moisture permeability coefficient is measured at a temperature of 40 ℃ and a relative humidity of 90% according to B condition of JIS Z0208. That is, one surface side of the patch is adjusted to 40 ℃ and 90% relative humidity, a moisture absorbent such as calcium chloride is placed on the other surface side, moisture passing through the patch is absorbed, and the amount of change in weight of the moisture absorbent is 1m per 24 hours²And then converted to calculate.

(adhesive force)

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

The method of measuring the adhesive force of the medical patch is as follows. That is, the patch is cut into a predetermined length of 25mm in width by 15mm in length, preferably 100mm, to obtain a test piece. After pressing the test piece against the electric wooden test board to bond the test piece, the test piece was bonded by a 2kg roller at a bonding speed of 300 mm/min and 1 reciprocating press cycle to prepare a test piece. After 20 minutes from the bonding, the adhesive force was measured under the conditions of a peel angle of 180 ° and a peel speed of 300 mm/minute in accordance with the peel adhesion test method of ISO 29862, method 1 (corresponding to JIS: JIS Z0237).

(method for producing medical adhesive sheet)

The method for producing the medical patch according to the present invention is not particularly limited. For example, the following method is preferably employed: a pressure-sensitive adhesive solution is applied to a separator usually used as a so-called release liner, and dried to form a pressure-sensitive adhesive layer. As a method for continuously forming the adhesive layer, the following method is preferable: the separator is moved in one direction while the binder solution is applied thereto and allowed to dry. A method of melting the binder and coating it on the separator may also be used. Further, repetitive pattern coating of a specific shape is also possible.

By bonding a laminate having a pressure-sensitive adhesive layer formed on one surface of a separator to a support so that the pressure-sensitive adhesive layer is tightly bonded to the surface of the support, a patch having a laminate structure of "support/pressure-sensitive adhesive layer/separator" can be produced. In the case of a laminate having a support layer of an arbitrary layer formed on one surface of a support, an adhesive material having a laminate structure of "support layer (arbitrary layer)/support/adhesive layer/separator layer" can be produced by bonding an adhesive layer to the surface of the support of the laminate so as to be closely adhered.

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 with respect to patches in which adhesive layers were formed 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), oleyl oleate (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 K.K.), sorbitol trioleate (molecular weight: 935.0), castor oil fatty acid ester (molecular weight: about 500, リックサイザー C-101, manufactured by Ito oil Co., Ltd.), decyl oleate (molecular weight: about 500, manufactured by Ito oil Co., Ltd.), and the like were used: 422.4), special castor oil condensed fatty acids (molecular weight: 800, ミネラゾール, by itai corporation). Furthermore, as the support, a woven fabric (warp: core yarn (core spun), weft: cotton, moisture permeability coefficient: 21,060 g/(m)²24h), a grammage of 155g/m²) Polyurethane nonwoven fabric (fiber diameter: 15 μm, moisture permeability coefficient: 21,590 g/(m)²24h), a gram weight of 65g/m²) Polyethylene film (thickness: 50 μm, moisture permeability coefficient: 60 g/(m)²·24h))。

< sample preparation >

First, as an adhesive composition, a solution of an acrylic copolymer obtained by copolymerization of a monomer mixture consisting of 2-ethylhexyl acrylate/vinyl acetate/acrylic acid (mass ratio) 85/11/4 was mixed with the liquid plasticizers shown in table 1 and described in tables 1 to 3 in an amount of 100 parts by mass of the acrylic copolymer, and further mixed with tetra-X (manufactured by mitsubishi gas chemical corporation) in an amount of 0.06 part by mass as a crosslinking agent to prepare a uniform adhesive composition solution.

The solution of the adhesive composition was applied to the release treated surface of the divider (silicone treatment "ポリラミ decorticated") in such a manner that the dried thickness was 38 μm, and dried to form an adhesive layer. The adhesive layer was bonded to the support described in tables 1 to 3 to prepare a patch.

< determination of adhesion to human skin >

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

< measurement of area ratio of exfoliation of keratin >

Each test sample after being peeled off in the adhesion force measurement was stained 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 Kenzhi Co., Ltd.), and the obtained images were subjected to image analysis using an image processing apparatus (Win ROOF, manufactured by Sango Co., Ltd.), thereby measuring the areas of keratinocytes adhered to the respective test specimens. For each test sample, the keratinocyte adhesion area ratio ([ keratinocyte adhesion area ]/[ surface area of test sample ] × 100 (%)) of 3 visual fields was calculated, and the average value thereof was taken as the keratinocyte exfoliation area ratio of each test sample (n ═ 8). 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 off 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 when peeled off, and "good quality" indicates that the adhesive does not remain on the skin when peeled off.

< repetitive forearm attachment test >

The forearm attachment test was repeated as follows (up to 7 days, using 7 test specimens for 1 test area): the test sample was attached to the surface of human skin, peeled off every 24 hours, and after confirming the skin reaction after 1 hour, a new same test sample was attached to the same site (n-9). Skin reactions after 1 hour of exfoliation and 24 hours (day of end of test), the ratio of 5: no reaction, 4: mild erythema, 3: erythema, 2: erythema + edema, 1: erythema + edema + papule, or small blisters, 0: the evaluation was performed in the form of large blisters. The results are shown in tables 1 to 3.

[ Table 1]

[ Table 2]

[ Table 3]

Comparing examples 1 to 6 and comparative examples 1 to 8, in which the supports were the same, the adhesive force to human skin of each test sample was higher in the test samples (comparative examples 2 to 3, examples 1 to 6, and comparative examples 5 to 8) in which the fatty acid ester was contained in an amount of 10 parts by mass or 20 parts by mass per 100 parts by mass of the acrylic copolymer than in the test sample (comparative example 1) in which no fatty acid ester was contained, and the adhesive force could be improved by containing the fatty acid ester. In the 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, adhesive residue occurred at the time of peeling. This is presumably because the adhesive layer is too soft due to the large content of the liquid plasticizer. On the other hand, the test sample (comparative example 7) in which decyl oleate having poor compatibility with the acrylic copolymer was selected had a problem as a medical patch because adhesive residue occurred in the adhesive residue test.

The area ratio of the keratin removed from each test sample was sufficiently lower than that of comparative example 1, and was about 40%, in the test samples (examples 1 to 6) containing a fatty acid ester 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, and 8) containing fatty acid esters having molecular weights outside the above ranges, the exfoliating area ratio was 50% or more, and it was confirmed that the reduction 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 the above range and 5 parts by mass of oleyl oleate (molecular weight: 531.0) having a molecular weight within the above range as a liquid plasticizer, and which had a weight average molecular weight of 333.8[ (268.0 × 15+531.0 × 5)/(15+5) ] as well as the test sample containing only fatty acid ester having a molecular weight outside the above range, exhibited a cutin peeling area ratio of 50% or more and a poor effect of reduction.

With respect to the skin reaction, it was confirmed that the skin condition hardly deteriorated with time and the skin condition could be maintained in the test samples (examples 1 to 6) containing the fatty acid ester having a molecular weight in the range of 350 to 550 inclusive and good compatibility with the acrylic copolymer. Further, it was confirmed that there were few testers remaining reddish after 24 hours of peeling on the test completion day. On the other hand, test samples (examples 3 and 7 and comparative example 9) differing only in the support were compared, and the moisture permeability coefficient was 500 g/(m)²24h) or more of the polyurethane nonwoven fabrics as the support in example 7, the moisture permeability coefficient was 500 g/(m)²24h) of the above woven fabric as a support, the moisture permeability coefficient was 60 g/(m)²Comparative example 9, in which the polyethylene film of 24h) was used as a support, had a low exfoliating area ratio, but the human skin adhesive force was greatly reduced, and the skin reaction was also strong. From these results, it was found that the moisture permeability coefficient was 500 g/(m)²24h) or more, and an appropriate amount of a fatty acid ester having a molecular weight of 350 or more and 550 or less, which is well compatible with the acrylic copolymer, is contained in the pressure-sensitive adhesive layer formed of the acrylic copolymer, thereby forming a pressure-sensitive adhesive layer which maintains high adhesive force and causes little skin irritation when continuously or repeatedly attached to the same part of the skin.

Claims

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

The pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive composition containing a copolymer containing an alkyl (meth)acrylate as a main component, and a liquid at room temperature and a copolymer with the copolymer. Compatible fatty acid esters,

The adhesive composition contains 5 parts by mass or more and 25 parts by mass or less of the fatty acid ester with respect to 100 parts by mass of the copolymer,

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

2. The medical adhesive material 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 or more and 550 or less.

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

The copolymer is a polymer obtained by polymerizing the following substances by a solution polymerization method and cross-linking with a cross-linking agent: 65% by mass or more and 90% by mass or less, and having an alkyl group having a carbon number of 8 or more and 12 or less acrylic acid at 2 mass% or more and 15 mass% or less; vinyl acetate at 5 mass% or more and 25 mass% or less; and 0 mass% or more and 10 mass% or less of other vinyl monomers.

4. The medical adhesive material according to any one of claims 1 to 3, wherein

The fatty acid ester has at least one oleic acid residue.

5. The medical adhesive material according to claim 4, wherein

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

6. The medical adhesive material according to any one of claims 1 to 5, wherein

A separator layer is further provided on the surface opposite to the surface in contact with the support of the pressure-sensitive adhesive layer.

7. The medical adhesive material according to any one of claims 1 to 6, wherein

The medical sticking material is repeatedly stuck on the same part of the skin.

8. The medical adhesive material according to any one of claims 1 to 7, wherein

The medical adhesive material is used to fix the tube.