JPWO2016103449A1 - Adhesive material - Google Patents

Abstract

The pressure-sensitive adhesive layer is (a) pressure-sensitive adhesive A: 65 to 99.5% by mass of a (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms, and 0.5 to 0.5% of a vinyl monomer having a functional group. 8% by mass, an acrylic pressure-sensitive adhesive containing a copolymer consisting of 0 to 34.5% by mass of a non-hydrophilic vinyl monomer, and (b) pressure-sensitive adhesive B: an alkyl group having 8 to 12 carbon atoms (Meth) acrylic acid alkyl ester having 50 to 90% by mass, functional group-containing vinyl monomer 0.5 to 8% by mass, hydrophilic vinyl monomer 9.5 to 49.5% by mass And (i) a mixing ratio of the pressure-sensitive adhesive A and the pressure-sensitive adhesive B is 15/85 to 85. / Ii and (ii) the mixed adhesive is cross-linked Adhesive material to be.

Description

  The present invention is applied to the medical field, particularly for the purpose of promoting healing of wounds and minor burns such as cuts, scratches, scratches, scratches, shoe slippage, relief of pain, maintenance of a moist environment, or protection. In particular, the present invention relates to a patch suitable for an emergency bandage. The present invention also relates to a patch useful as a medical adhesive tape or a transdermally absorbable preparation capable of transdermal administration of a drug.

  The patch material generally has a layer structure including a support layer made of a plastic film, a woven fabric, a nonwoven fabric, a knitted fabric, paper, and the like, and an adhesive layer provided on at least one side of the support layer. Furthermore, a separator layer is disposed to protect the surface of the pressure-sensitive adhesive layer, or, for example, when the support layer is extremely thin, the support layer is provided with a carrier layer.

  When using a woven fabric, non-woven fabric, knitted fabric, paper, etc. as the support for the patch, it is excellent in moisture permeability, but its waterproofness is low. There was a problem such as lowering and peeling off.

  On the other hand, when a film is used for the support in order to maintain waterproofness, the film has a problem that moisture permeability is lowered due to the film, and the skin becomes soft and rash. Therefore, there is a demand for a pressure-sensitive adhesive that is waterproof and has excellent moisture permeability and adhesiveness.

  In general, as the adhesive constituting the adhesive layer in the patch, rubber-based, acrylic-based, silicone-based and urethane-based adhesives are known, and among them, they are excellent in heat resistance and weather resistance and also in adhesive strength. In addition, acrylic pressure-sensitive adhesives are often used because they are easily modified.

  In the case of an acrylic pressure-sensitive adhesive, a pressure-sensitive adhesive made of a copolymer having a high ratio of hydrophilic monomers has a high moisture permeability but a low adhesive strength. On the other hand, when the ratio of alkyl acrylate ester (hydrophobic monomer) is high, It has been reported that the adhesive strength is high but the moisture permeability is low. In order to increase the adhesive strength and moisture permeability of acrylic adhesives, the types of (meth) acrylic acid ester monomers, which are the main components of acrylic adhesives, are changed, and hydrophilic monomers and copolymers are used to increase moisture permeability. Copolymers with various monomers and the like have been produced, and acrylic adhesives having many characteristics have been produced. However, even when a copolymer having both high adhesive strength and moisture permeability is predicted, both adhesive strength and moisture permeability are halfway, and both adhesive strength and moisture permeability are provided. In many cases, a sufficiently satisfactory pressure-sensitive adhesive could not be obtained. Therefore, it has been considered to use a mixture of acrylic adhesives having different characteristics.

  In Patent Document 1, as a pressure-sensitive adhesive layer, (A) a monomer containing a carboxy group or a hydroxy group, a copolymer obtained by copolymerizing (meth) acrylic acid ester as an essential component, and (B) A copolymer obtained by copolymerizing, as essential components, a monomer having a nitrogen atom having no salt structure in the side chain and (meth) acrylic acid ester, and (C) the above component (A) and (B And) a cross-linked adhesive containing an organic liquid component compatible with the component. Patent Document 2 discloses a component (A) composed of a copolymer having a carboxy group-containing monomer and a (meth) acrylic acid ester as monomer units, and a pyrrolidone group-containing monomer and a (meth) acrylic acid ester as monomer units. (B) component which consists of a copolymer which has, and the copolymer which is the said (A) component is at least 1 sort (s) of crosslinking chosen from the group which consists of a metal chelate compound, a metal oxide, and a metal hydroxide A pressure-sensitive adhesive crosslinked by reaction with an agent is disclosed. However, both literatures are effective on drug solubility as well as adhesiveness, and do not consider moisture permeability when a waterproof film is used as a support.

  In Patent Document 3, (A) adhesive polymer A containing a copolymer having 2-acetoacetoxyethyl ester of methacrylic acid and other vinyl monomers as constituent components, and (B) 4 carbon atoms in the alkyl group Use a mixture of two types of adhesives, adhesive polymer B, which contains 10 (meth) acrylic acid alkyl esters and other vinyl monomers as constituents and contains a copolymer different from adhesive polymer A. Is disclosed. Patent Document 4 discloses a non-crosslinked adhesive for medical use comprising an adhesive polymer A having a weight average molecular weight of 500,000 to 1,000,000, an adhesive polymer B having a weight average molecular weight of 1,000,000 to 1,500,000, and a liquid plasticizer. The adhesive polymer A is a polymer obtained by copolymerizing (meth) acrylic acid alkyl ester with N-vinyl-2-pyrrolidone, and the adhesive polymer B is a single (meth) acrylic acid alkyl ester. Disclosed is a non-crosslinked adhesive for medical use, which is a polymer obtained by polymerization or a polymer obtained by copolymerizing a comonomer other than N-vinyl-2-pyrrolidone with a (meth) acrylic acid alkyl ester. ing. However, both documents consider adhesiveness and skin irritation, but liquid plasticizers are used to improve compatibility in mixing of adhesives, and waterproof, moisture permeable and adhesive It does not consider sex.

  As described above, when two types of acrylic pressure-sensitive adhesives having different compositions are mixed, compatibility is deteriorated, and it is often necessary to add a plasticizer. In addition, when a film with improved waterproofness is used as a support, there is a demand for a patch material that increases moisture permeability and adhesiveness and is excellent in compatibility between two types of acrylic adhesives.

JP 2000-44904 A JP 2006-241179 A International Publication No. 2006/64747 JP-A-2005-314251

  An object of the present invention is to provide a mixed pressure-sensitive adhesive in which two types of acrylic pressure-sensitive adhesives are mixed, so that even when a film material is used as a support for imparting waterproofness, the skin may be swollen or rashed. The object is to provide a patch having waterproofness, moisture permeability and adhesiveness.

  As a result of diligent research on solving the above-mentioned problems, the inventors of the present invention include blending two specific types of acrylic pressure-sensitive adhesives having good compatibility at a specific ratio as the pressure-sensitive adhesive layer, and further crosslinking. Therefore, even when a film material is used as the support, it has been thought that a patch material having all of waterproofness, flexibility, and adhesiveness may be possible.

  In general, acrylic pressure-sensitive adhesives are mainly composed of (meth) acrylic acid alkyl esters as monomer units. When the content of the (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms is a certain level or more, the adhesive easily absorbs the sebum component secreted from the skin, and the patch (Meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms as a main component has been conceived based on the knowledge that is difficult to peel off.

  That is, two types of acrylic pressure-sensitive adhesives, the main component of which is a (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms, are mixed pressure-sensitive adhesives, and are further cross-linked to provide the required waterproofness and transparency. The idea was that a pressure-sensitive adhesive having both wetness and adhesiveness would be possible.

  Since it can be said that the acrylic pressure-sensitive adhesive, which is a (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms as a main component, has a hydrophobic property, it is hydrophilic to this. It was conceived that an acrylic pressure-sensitive adhesive having the characteristics described above was mixed and further crosslinked to provide a pressure-sensitive adhesive having both waterproofness and moisture permeability.

  Therefore, the present inventors have added a vinyl monomer having a functional group that can be copolymerized with (meth) acrylic acid alkyl ester to (meth) acrylic acid alkyl ester for crosslinking, to the extent necessary for crosslinking. Based on the adhesive compounded in a small amount, a third component that produces hydrophilic properties was sought. In this case, it must be taken into account that the compatibility of the two acrylic pressure-sensitive adhesives is appropriate in mixing. However, the use of a plasticizer is not preferable because it reduces the properties of the pressure-sensitive adhesive.

  In order to obtain an acrylic pressure-sensitive adhesive having hydrophilic characteristics in consideration of compatibility, the present inventors may use a hydrophilic vinyl monomer as the third component. I found it appropriate. That is, the present inventors have found a mixed pressure-sensitive adhesive of an acrylic pressure-sensitive adhesive having different characteristics of pressure-sensitive adhesive A (without the third component) and pressure-sensitive adhesive B (with the third component) depending on the presence or absence of the third component, It was found that by cross-linking this mixed pressure-sensitive adhesive, a pressure-sensitive adhesive having both waterproofness and moisture permeability and adhesiveness was obtained.

That is, according to the present invention, (1) a patch comprising a support layer and an adhesive layer, wherein the adhesive layer is
(A) Adhesive A: (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms as an essential component, 65 to 99.5% by mass, a function copolymerizable with the (meth) acrylic acid alkyl ester In the range of 0.5 to 8% by mass of the vinyl monomer having a group and the remaining monomer as a total of 100% by mass, the (meth) acrylic acid alkyl ester and the vinyl monomer are Acrylic polymer containing a copolymer comprising 0 to 34.5% by mass of a vinyl monomer which is a different vinyl monomer and is copolymerizable with the alkyl (meth) acrylate and has no hydrophilicity Pressure-sensitive adhesive, and (b) pressure-sensitive adhesive B: 50 to 90% by mass of a (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms as an essential component within the range of 100% by mass of the monomers. The 0.5 to 8% by mass of a vinyl monomer having a functional group copolymerizable with a (meth) acrylic acid alkyl ester, a vinyl monomer different from the (meth) acrylic acid alkyl ester or the vinyl monomer An acrylic pressure-sensitive adhesive containing a copolymer composed of 9.5 to 49.5% by mass of a hydrophilic vinyl monomer copolymerizable with the alkyl (meth) acrylate. It is a mixed adhesive obtained by mixing, and (i) the mixing ratio of the adhesive A and the adhesive B (adhesive A / adhesive B) is the total mass of the adhesive A and the adhesive B When the weight is 100 parts by mass, the patch is 15/85 to 85/15 (mass ratio), and (ii) the mixed pressure-sensitive adhesive is crosslinked.

Moreover, according to this invention, (2) The adhesive material of said (1) whose bridge | crosslinking of the said adhesive layer is based on a crosslinking agent is provided.
According to the present invention, there is also provided (3) the patch according to (1), wherein the functional group is a carboxy group or a hydroxy group.
Moreover, according to this invention, (4) The adhesive material in any one of said (1)-(3) in which the said adhesive layer does not contain the plasticizer which is liquid at room temperature is provided.
Moreover, according to this invention, (5) The adhesive material in any one of said (1)-(4) in which the said support body contains a film is provided.
According to the present invention, there is also provided (6) a patch of the patch according to any one of (1) to (4), wherein the support is a laminate of a film and a fabric.
Moreover, according to this invention, the adhesive material in any one of said (1)-(6) whose moisture permeability is 300 g / m < ² > * 24h or more is provided.
Moreover, according to this invention, (8) Mixing ratio (adhesive A / adhesive B) of this adhesive A and this adhesive B is 100 mass parts with the total mass of the adhesive A and the adhesive B. When it does, the patch in any one of said (1)-(7) which is 35 / 65-65 / 35 (mass ratio) is provided.
Moreover, according to this invention, the difference of SP value of the solubility parameter of the (meth) acrylic-acid alkylester which has a C8-C12 alkyl group which is a main structural component of the adhesive A and the adhesive B is (9). The patch according to any one of (1) to (8), which is within 0.50.
Moreover, according to this invention, the patch in any one of said (1)-(9) which is (10) emergency bandage is provided.

  According to the present invention, the adhesive of the patch is a mixed adhesive composed of a compatible hydrophobic acrylic adhesive and a hydrophilic acrylic adhesive without the need for a plasticizer, By cross-linking the mixed pressure-sensitive adhesive, even if the support is a waterproof film, the skin does not swell or rash, and the adhesive material has both waterproofness, moisture permeability and adhesiveness. There is an effect that can be.

  These patch materials are useful as an emergency bandage, as a medical adhesive tape, or as a transdermal absorption preparation.

The patch of the present invention is basically a patch having a support layer and an adhesive layer.
1. Support layer The support layer of the patch of the present invention includes films, fabrics such as woven fabrics, knitted fabrics, and non-woven fabrics. Among others, it has waterproofness and can adhere to the skin, and the skin. It is preferable to include a film that is a flexible material that can follow the movement of the skin and that can suppress the occurrence of skin irritation and the like after being applied for a long time.

Examples of the film used as the support layer of the present invention include polyethylene, polypropylene, polyethylene terephthalate (hereinafter sometimes referred to as “PET”), polybutylene terephthalate, polyethylene naphthalate, polystyrene, nylon, cotton, acetate rayon, Rayon, rayon / polyethylene terephthalate composite, polyacrylonitrile, polyvinyl alcohol, acrylic polyurethane, polyester polyurethane, polyether polyurethane, styrene-isoprene-styrene copolymer, styrene-butadiene-styrene copolymer, styrene-ethylene- Single layer or laminate of films containing propylene-styrene copolymer, styrene-butadiene rubber, ethylene-vinyl acetate copolymer, cellophane, etc. It is. In order to suppress the occurrence of skin irritation and the like, the support layer has a moisture permeability of the support layer (measured under the B condition (temperature 40 ° C., relative humidity 90%) defined in JIS Z0208). Those having a viscosity of 2,000 g / m ² · 24 hours or more, particularly 2,000 g / m ² · 24 hours or more are preferably used.

  In the present invention, an elastomer film is also preferably used as a support layer that is waterproof and has flexibility and moisture permeability. Examples of the elastomer forming the elastomer film include polyurethane elastomers, 1,2-polybutadiene thermoplastic elastomers, polystyrene thermoplastic elastomers, polyolefin thermoplastic elastomers, and mixtures of two or more thereof. it can. Among these elastomers, polyurethane elastomer films are preferable.

  As the support layer of the present invention, a laminate obtained by laminating a fabric in order to further provide flexibility and hygroscopicity to the waterproof film is preferably used. The fabric is a non-woven fabric, a woven fabric or a knitted fabric made of polyester fiber, polyacrylic fiber or polyurethane fiber in addition to natural fiber. Among them, a non-woven fabric made of polyurethane fiber is preferable because of its elasticity. In the lamination of the film and the fabric, the side to which the adhesive is applied may be either a film or a fabric.

(Thickness of support layer)
The support layer provided in the patch of the present invention has a thickness in the range of 10 to 50 μm in the case of a film alone, but may be 20 to 250 μm in the case of a laminate comprising a film and a fabric, preferably 70. ~ 200 μm. In the case of a laminate composed of a film and a fabric, the thickness of the film is 2 to 20 μm, preferably 3 to 10 μm. When the thickness of the support layer is too thin, the strength of the support layer becomes insufficient, and the support layer is supported when the patch is applied to the skin or peeled off from the skin. The body layer may break. In addition, if the thickness of the support layer is too large, the thickness of the patch becomes large. As a result, the patch is less likely to adhere along the skin surface with fine irregularities such as skin grooves, making the sticking state more noticeable and uncomfortable. Also tends to be large.

(Additive)
The film that forms the support layer is preferably a plastic film with excellent transparency in that the adhesive is not noticeable during application, that is, it is easy to show through the color tone of the skin under application. In many cases, the film forming the support layer may contain various additives such as colorants such as pigments and dyes, stabilizers, ultraviolet absorbers, and lubricants, if desired. The content of these additives may be selected in an optimum range depending on the type of additive, but is usually 0.001 to 30 parts by mass, preferably 0.01 to 100 parts by mass of the resin material constituting the film. It is often in the range of ˜25 parts by mass, more preferably in the range of 0.1 to 20 parts by mass.

[Embossing]
When the patch is applied to the human skin surface, in order to improve the touch, slipperiness, appearance, etc. of the patch, the back surface of the support layer constituting the patch (the adhesive layer side of the support layer) Means a surface located on the opposite side.), It may be preferable to form minute irregularities. That is, it can be set as the sticking material by which the surface on the opposite side to the adhesive layer side of a support body layer is embossed. By embossing, the dynamic friction coefficient of the support layer surface can be reduced to less than 1.0. In addition, if minute irregularities are formed on the surface of the carrier layer by embossing and a support layer is formed on the minute irregular surface, the surface (back surface) of the support layer formed from an elastomer film Minute irregularities can be transferred.

  The support layer may be subjected to surface treatment such as sandblasting or corona treatment on one side or both sides for the purpose of improving anchoring properties with the adhesive. Moreover, in order to make it easy to take out the patch from the packaging material, irregularities can be provided on one side or both sides of the support layer by a method other than sandblasting.

2. Adhesive layer The patch of the present invention is a mixed adhesive in which the adhesive forming the adhesive layer is a mixture of the following two acrylic adhesives.

(A) Adhesive A:
As essential components, 65 to 99.5% by mass of (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms, and a vinyl monomer having a functional group copolymerizable with the (meth) acrylic acid alkyl ester 0.5 to 8% by mass of the remaining component, and a vinyl monomer different from the (meth) acrylic acid alkyl ester and the vinyl monomer in the range of the total monomer of 100% by mass. An acrylic pressure-sensitive adhesive containing a copolymer composed of 0 to 34.5% by mass of a vinyl monomer having no hydrophilicity and copolymerizable with the alkyl (meth) acrylate.

(B) Adhesive B:
Copolymerized with 50 to 90% by mass of (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms as an essential component within the range of 100% by mass of the total monomer. 0.5 to 8% by mass of a vinyl monomer having a possible functional group, the (meth) acrylic acid alkyl ester and a vinyl monomer different from the vinyl monomer, the (meth) acrylic acid An acrylic pressure-sensitive adhesive containing a copolymer comprising 9.5 to 49.5% by mass of a hydrophilic vinyl monomer copolymerizable with an alkyl ester.

  Further, the mixed pressure-sensitive adhesive has a mixing ratio of pressure-sensitive adhesive A and pressure-sensitive adhesive B (pressure-sensitive adhesive A / pressure-sensitive adhesive B), when the total mass of pressure-sensitive adhesive A and pressure-sensitive adhesive B is 100 parts by mass. 85 to 85/15 (mass ratio), preferably 25/75 to 75/25 (mass ratio), more preferably 35/65 to 65/35, and adhesive A and adhesive B are cross-linked. Is.

  The pressure-sensitive adhesive A is a two-component system or a three-component system, but the method of determining the component ratio is to determine the amount of the pressure-sensitive adhesive A, and then make the essential components within a predetermined range, and 100% by mass as a whole. So that the remaining components are within a predetermined range. The pressure-sensitive adhesive B is a three-component system, and the component ratio is determined so as to be 100% by mass as a whole.

(1) Adhesive A
The pressure-sensitive adhesive A is hydrophobic.
The acrylic pressure-sensitive adhesive A used in the patch of the present invention contains 65 to 99.5 mass%, preferably 75 to (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms as an essential component. 99.3% by mass, more preferably 80 to 98% by mass, and 0.5 to 8% by mass of vinyl monomer having a functional group copolymerizable with the alkyl (meth) acrylate, preferably 0 0.7 to 6% by mass, more preferably 0.9 to 5% by mass, and as the remaining components, the (meth) acrylic acid alkyl ester and the vinyl monomer are within the range of a total monomer of 100% by mass. 0 to 34.5% by mass, preferably 0 to 24.3% by weight of a vinyl monomer that is different from the polymer and is copolymerizable with the alkyl (meth) acrylate and has no hydrophilicity. Mass%, more preferred Ku is from 0 to 19.1% by mass.

(1-1) (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms As the (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms, which is an essential component in the pressure-sensitive adhesive A, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, (meta ) Lauryl acrylate and the like. Among these (meth) acrylic acid alkyl esters, acrylic acid alkyl esters having an alkyl group having 8 to 9 carbon atoms such as 2-ethylhexyl acrylate and isononyl acrylate are particularly preferable. These alkyl (meth) acrylates can be used alone or in combination of two or more.

(1-2) Vinyl monomer having a functional group copolymerizable with (meth) acrylic acid alkyl ester The functional group functions as a functional group for crosslinking the adhesive A and the adhesive B, and the functional group Have a carboxy group, a hydroxy group, an amino group, an amide group and an epoxy group, and among them, a carboxy group and a hydroxy group are preferable. Examples of the carboxy group-containing monomer include (meth) acrylic acid, itaconic acid, and maleic acid. Examples of the hydroxy group-containing monomer include hydroxyl methyl (meth) acrylate, hydroxyethyl (meth) acrylate, ( Examples thereof include hydroxypropyl methacrylate, and (meth) acrylic acid monoesters of polyalkylene glycols such as (meth) acrylic acid diethylene glycol monoester. Examples of the monomer having an amino group include aminoethyl (meth) acrylate, examples of the amide group-containing monomer include (meth) acrylamide, and examples of the epoxy group-containing monomer include glycidyl acrylate. These may be used in combination of two or more. Acrylic acid and polyethylene glycol monomethacrylate are preferred.

(1-3) Vinyl monomer that is copolymerizable with (meth) acrylic acid alkyl ester and has no hydrophilicity This vinyl monomer is a vinyl monomer of (1-1) or (1-2). It is a monomer different from the body and does not have hydrophilicity.

  That is, here, the vinyl monomer having no hydrophilicity is the (meth) acrylic acid alkyl ester of (1-1) or the functional group used as the vinyl monomer of (1-2). Vinyl monomers having groups are excluded.

  That is, in the pressure-sensitive adhesive A, a vinyl monomer having a (meth) acrylic acid alkyl ester or a functional group and a vinyl monomer having no hydrophilicity do not overlap.

  Examples of the vinyl monomer different from the vinyl monomers (1-1) and (1-2) include (meth) acrylic acid alkyl esters and vinyl esters having an alkyl group having 1 to 6 carbon atoms. It is done.

  That is, (meth) acrylic acid alkyl ester having an alkyl group having 1 to 6 carbon atoms is methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate. , T-butyl (meth) acrylate, n-hexyl (meth) acrylate, and the like.

  In addition, (meth) acrylic acid esters having saturated carbon rings such as cyclohexyl groups, vinyl esters such as vinyl acetate and vinyl propionate, cyano group-containing vinyl monomers such as acrylonitrile and methacrylonitrile (unsaturated nitriles) , Vinyl aromatic compounds such as styrene, and acrylamide. These may be used in combination of two or more. Preferably, vinyl acetate is used.

(1-4) Specifically, as such an adhesive A, for example, an adhesive containing a copolymer composed of 96% by mass of isonolyl acrylate and 4% by mass of acrylic acid, or 98% by mass of isonolyl acrylate. %, An adhesive containing a copolymer consisting of 2% by mass of acrylic acid, and an adhesive containing a copolymer consisting of 85% 2-ethylhexyl acrylate, 4% acrylic acid, and 11% by mass of vinyl acetate. Can be mentioned.

(2) Adhesive B
The pressure-sensitive adhesive B is hydrophilic.
The acrylic pressure-sensitive adhesive B used in the patch of the present invention is a (meth) acrylic acid alkyl ester 50 having an alkyl group having 8 to 12 carbon atoms as an essential component in a range where the total amount of monomers is 100% by mass. ~ 90 mass%, preferably 51 to 88 mass%, more preferably 52 to 86 mass%, 0.5 to 8 mass% of a vinyl monomer having a functional group copolymerizable with the alkyl (meth) acrylate. %, Preferably 0.7 to 6% by weight, more preferably 0.9 to 5% by weight, a vinyl monomer different from the (meth) acrylic acid alkyl ester and the vinyl monomer, 9.5 to 49.5% by mass, preferably 11.3 to 48.3% by mass, more preferably a vinyl monomer having hydrophilicity that can be copolymerized with (meth) acrylic acid alkyl ester. Is 13.1 7.1 is an acrylic adhesive having a hydrophilicity which contains a copolymer composed of mass%.

(2-1) The (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms of the adhesive B is selected from the above (1-1).

(2-2) The vinyl monomer having a functional group copolymerizable with the (meth) acrylic acid alkyl ester of the adhesive B is selected from the above (1-2).

(2-3) Hydrophilic vinyl monomer copolymerizable with (meth) acrylic acid alkyl ester In order to produce hydrophilic characteristics, a hydrophilic vinyl monomer is used as the third component. Use.

  This vinyl monomer is a vinyl monomer different from the (meth) acrylic acid alkyl ester of (2-1) and the vinyl monomer of (2-2), and has hydrophilicity.

  That is, here, the vinyl monomer having hydrophilicity is the (meth) acrylic acid alkyl ester of (2-1) or the vinyl monomer having the functional group described in (2-2). Vinyl monomers having a functional group used as a body are excluded.

  That is, in the adhesive B, the (meth) acrylic acid alkyl ester or the vinyl monomer having a functional group does not overlap with the hydrophilic vinyl monomer.

  As the vinyl monomer having hydrophilicity, a vinyl monomer having an alkoxy group is usually used.

  Examples of vinyl monomers having an alkoxy group include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, and 2-butoxyethyl (meth) acrylate. , (Meth) acrylic acid 2-ethoxymethyl. Further, (meth) acrylic acid esters of methoxyethylene glycol and (meth) acrylic acid esters of alkoxy (poly) alkylene glycols such as methoxydiethylene glycol can be mentioned. Preferably, there are 2-methoxyethyl acrylate and methoxypolyethylene glycol acrylate.

(2-4) As such an adhesive B, for example, an adhesive containing a copolymer composed of 68% by mass of isononyl acrylate, 2% by mass of acrylic acid, and 30% by mass of 2-methoxyethyl acrylate, It contains a copolymer comprising 83% by mass of isononyl acrylate, CH ₂ ═CHCOO— (CH ₂ CH ₂ O) ₉ H 1% by mass, CH ₂ ═CHCOO— (CH ₂ CH ₂ O) ₉ CH ₃ 16% by mass. An adhesive is mentioned.

(Manufacture of acrylic copolymer)
The acrylic copolymer constituting the pressure-sensitive adhesive A and the pressure-sensitive adhesive B forming the pressure-sensitive adhesive layer of the patch of the present invention can be produced by radical polymerization. As a polymerization method of the acrylic copolymer, a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and the like are known, but the adhesive layer provided in the adhesive material of the present invention is easy to obtain good adhesive properties. The solution polymerization method is preferred. Examples of the polymerization initiator for obtaining the acrylic copolymer include organic peroxides such as benzoyl peroxide and lauroyl peroxide; azo initiators such as azobisisobutyronitrile; and the like. Specifically, 0.1 to 3 parts by mass of radicals per 100 parts by mass of all the monomers consisting of the above b-1), b-2) and b-3) forming the acrylic copolymer. A polymerization initiator is added, and the mixture is stirred for 30 minutes to 30 hours at a temperature of about 40 to 90 ° C. in a nitrogen stream for copolymerization. In the solution polymerization method, ethyl acetate, acetone, toluene, or a mixture thereof is generally used as a solvent.

  The weight average molecular weight of the acrylic copolymer constituting the adhesive A and the adhesive B is usually 100,000 to 1,500,000, preferably 300,000 to 1,000,000, more preferably 450,000 to It is in the range of 650,000. By setting the weight average molecular weight of the acrylic copolymer within the above range, the cohesiveness, adhesive strength, mixing workability with other components, affinity with other components, and the like can be balanced. The weight average molecular weight of an acrylic copolymer is the value calculated | required as a standard polystyrene conversion value by the gel permeation chromatography (GPC) method.

(Compatibility)
In the pressure-sensitive adhesive layer of the present invention, the pressure-sensitive adhesive A and the pressure-sensitive adhesive B are in a ratio of 15/85 to 85/15 (mass ratio) when the total mass of the pressure-sensitive adhesive A and the pressure-sensitive adhesive B is 100 parts by mass. It has a mixed and further crosslinked structure. Adhesive A has hydrophobicity and Adhesive B has hydrophilicity, but since the mixed adhesive is integrated as an adhesive layer, it is important to have compatibility with each other. In the present invention, even if the (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms, which is the main component of both, is the same or not the same, the solubility parameter Those having a difference of SP values within 0.50 are preferably used. The preferable mixing ratio of the adhesive A and the adhesive B is 25/75 to 75/25% (mass ratio), and 35/65 to 65/35 (mass ratio) is more preferable.

(Crosslinking and crosslinking agent)
In the present invention, the pressure-sensitive adhesive A and the pressure-sensitive adhesive B may be cross-linked without a cross-linking agent by a mixing treatment, but are preferably cross-linked by a cross-linking agent. The cross-linking agent may be a polyfunctional isocyanate compound [tolylene diisocyanate. (TDI), 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diene Isocyanate, isophorone diisocyanate, etc.], polyfunctional epoxy compounds, acetylacetone metal salts, and the like. Examples of commercially available products include, for example, Coronate (registered trademark) manufactured by Nippon Polyurethane Industry Co., Ltd. L, Coronate L, Coronate EH, TETRAD-X manufactured by Mitsubishi Gas Chemical Co., Inc., (R), TETRAD-C (TM), available as such Nasemu (registered trademark) aluminum. 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 with respect to 100 parts by mass of the total amount of the acrylic copolymer in the adhesive A and the adhesive B. Parts, particularly preferably 0.04 to 0.1 parts by mass. The cross-linking agent may be used alone or in combination of two or more types, and at the same time, it is not necessary to add two or more types, and is added before or during the application of the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer. The method of doing is mentioned.

(Additive)
The pressure-sensitive adhesive layer of the present invention may contain various additives in addition to the above-mentioned pressure-sensitive adhesive A, pressure-sensitive adhesive B, and crosslinking agent. As additives, drugs, fillers, antioxidants (antioxidants, preservatives), colorants, fragrances, tackifiers, plasticizers, and the like are commonly used in pressure-sensitive adhesives that form a pressure-sensitive adhesive layer included in a patch. Additive may be contained. For example, a tackifier can be blended in order to adjust the adhesive properties of the adhesive. Examples of the tackifier include tackifier resins such as terpene, terpene phenol, coumarone indene, styrene, rosin, xylene, phenol, and petroleum.

(Plasticizer)
The pressure-sensitive adhesive A and pressure-sensitive adhesive B that form the pressure-sensitive adhesive layer in the present invention are those having compatibility and further subjected to a crosslinking treatment. Therefore, the plasticizer contained in the pressure-sensitive adhesive in the patch is usually used. It is not necessary to contain. Examples of the plasticizer include polyhydric alcohols (glycerin, sorbitol, propylene glycol, 1,3-butylene glycol, 1,3-tetramethylene glycol, polyethylene glycol, etc.); phenols (thymol, safrole, isosafrole, Eugenol, isoeugenol, etc.); higher alcohols (benzyl alcohol, oleyl alcohol, cetyl alcohol, stearyl alcohol, cetostearyl alcohol, octyldodecanol, etc.); ester surfactants (sorbitan sesquioleate, polyoxyethylene hydrogenated castor oil) Fatty acid esters (isopropyl myristate, octyldodecyl myristate, oleyl oleate, diethyl phthalate, dibutyl phthalate, etc.) ; Organic acids (lactic acid, citric acid, tartaric acid, maleic acid, malic acid); plasticizers are known in liquid form at room temperature such.

  In the present invention, it is preferable not to include a plasticizer that is liquid at room temperature. In the present invention, “does not include a plasticizer that is liquid at room temperature” means that the content does not affect the adhesive properties by including a plasticizer that is liquid at room temperature, In some cases, the content is usually 2 parts by mass or less, preferably 0.5 parts by mass or less with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive.

(Drugs, etc.)
The adhesive layer in the present invention can contain various drugs usually contained in the adhesive in the patch. Examples of such drugs include pyridoxine dicaprylate, dipotassium glycyrrhizinate, pyridoxine dipalmitate, glycyrrhizic acid, diphenhydramine hydrochloride, buckwheat extract, glycyrrhizyl stearate, lysozyme chloride, aminocaproic acid, litchi extract, yocuinine, merirot extract, button extract, toki extract Anti-inflammatory agents such as citrus root extract, root extract, genus cucumber extract, alloin extract, and arnica extract; antibacterial agents such as shikonin, hinokitiol, cedrol, benzalkonium chloride, benzethonium chloride, photosensitizer 201, and adipic acid Sebum secretion inhibitors such as estradiol, vitamin B2, vitamin B6, royal jelly extract, riboflavin; porous nylon powder and porous cellulose powder Oil-absorbing porous powder such as kaolin, talc, clay, zinc oxide, etc .; exfoliating agent such as salicylic acid, sulfur, bentonite, cyclodextrin; dibutylhydroxytoluene, tocopherol acetate, ascorbic acid, benzoic acids, Antioxidants (preservatives) such as parabens, benzalkonium chloride, and benzethonium chloride; Arnica montana extract, licorice extract, retinol, dipotassium glycyrrhizinate, peony extract, sage leaf extract, loquat leaf extract, rosemary extract, etc. Skin roughening agents; antioxidants such as vitamins and butylhydroxytoluene; various analgesics and anti-inflammatory agents; antihistamines; corticosteroids; moisturizers; vitamins;

  When the patch of the present invention is used as a transdermally absorbable preparation, it is a drug that is absorbed through the skin, and a drug required for treating a disease is added depending on the purpose. Examples of analgesics include steroidal analgesics, non-steroidal anti-inflammatory analgesics, narcotic analgesics, and local anesthetics. Other drugs include tranquilizers, antidepressants, insomnia remedies, antihypertensives, and the like.

  Furthermore, the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer in the present invention may contain a filler such as calcium carbonate, magnesium carbonate, silicate, zinc oxide, titanium oxide, magnesium sulfate, and calcium sulfate as necessary. it can.

  The content of the drug or filler described above varies in effective content depending on the type of drug or filler. Preferably, 0.001 to 10% by mass when the total mass of the adhesive layer is 100% by mass, It is preferable to contain 0.01-2 mass% especially.

(Adhesive layer thickness)
The thickness of the pressure-sensitive adhesive layer in the patch of the present invention is in the range of 10 to 200 μm, preferably 15 to 150 μm, more preferably 20 to 100 μm.

3. Separator layer In addition to the support layer and the pressure-sensitive adhesive layer, the patch of the present invention is usually used with an emergency bandage to protect the pressure-sensitive adhesive layer until the pressure-sensitive adhesive layer is applied to the skin. A separator layer is provided adjacent to the pressure-sensitive adhesive layer.

  The separator layer in the present invention is not particularly limited, and those generally used as release paper, release film, release paper, release film, release liner and the like can be used in the technical field of patch materials. . Specifically, for example, a polyethylene terephthalate film whose surface is treated with silicone, a laminate of polyethylene whose surface is treated with silicone and paper, and the like can be given. The separator layer may protect the pressure-sensitive adhesive layer as two or more sheets having the same or different thickness. Further, the separator layer may be provided with a cut line in order to improve handleability (that is, peelability from the pressure-sensitive adhesive layer), be formed in a larger area than the adhesive material, and be provided with a grip portion at the peripheral portion. Also good. In addition, the separator layer may be provided with unevenness by sandblasting or the like on the surface facing the pressure-sensitive adhesive layer of the separator layer or on the surface opposite to the pressure-sensitive adhesive layer for the purpose of improving the handleability and the printability. Good. Furthermore, the separator layer may be provided as a single large sheet, and a plurality of combinations of the pressure-sensitive adhesive layer, the support layer, and the carrier layer may be arranged on the separator layer. Will be shared.

  The thickness of the separator layer can be appropriately set and is not particularly limited, but is usually 20 μm or more, preferably 40 μm or more, and the upper limit is about 500 μm.

4). Carrier layer Normally, when the support layer is thin, the patch is preferably a patch comprising a carrier layer, a support layer, an adhesive layer and a separator layer laminated in this order. By providing a carrier layer in contact with the support layer, the patch can improve the handleability of the patch and the adhesiveness to the skin. Also, in the method of manufacturing the patch, the support layer is formed. Can be made easier. In other words, when the patch is applied to the skin, the support layer may wrinkle or the patch may be bent and the adhesive layers may adhere to each other, but the patch is adjacent to the support layer. By providing the carrier layer, the shape retaining property of the patch is improved, so that such a problem can be prevented. The thickness of the carrier layer can be appropriately set and is not particularly limited, but is usually 20 μm or more, preferably 40 μm, and the upper limit is about 500 μm.

  The carrier layer can be formed using a film made of various thermoplastic resins, for example, polyurethane, polyethylene, polypropylene, ionomer, polyamide, polyvinyl chloride, polyvinylidene chloride, ethylene vinyl acetate copolymer, thermoplastic. A film made of polyester, polytetrafluoroethylene, or the like can be used. Moreover, the laminated body of these films and paper can be used.

  The carrier layer can be easily peeled off from the support layer during use, that is, when the patch is applied to the skin. Therefore, the carrier layer and the support layer are formed so as to be peelable by thermocompression bonding or adhesion. In order to adjust the peeling force between the carrier layer and the support layer, an adhesive, a liquid plasticizer, a release agent, or the like may be applied to the surface of the carrier layer facing the support layer.

5. Patch The patch of the present invention comprises a support for imparting waterproofness and an adhesive layer, and has high moisture permeability and high adhesive strength as a patch. The moisture permeability is preferably 300 g / m ² · 24 h or more, and the probe tack is preferably 1.0 to 4.0 N / 5 mmφ.

(Pattern shape)
The patch of the present invention is a patch comprising a support layer and a pressure-sensitive adhesive layer, and the shape is not particularly limited as long as it has the above-mentioned various properties. First-aid adhesive plaster, adhesive tape or transdermal It can be shaped to suit the characteristics of the absorption preparation, for example, when it is used as an adhesive tape, it can be in the form of a roll. It is possible to adopt a shape corresponding to the above.

(Moisture permeability)
The adhesive material of the present invention has a moisture permeability of 300 g / m ² · 24 h or more, preferably 600 g / m ² · 24 h or more, more preferably 650 g / m ² · 24 h or more, further preferably 700 g / m ² · 24 h or more, Particularly preferably, it is 750 g / m ² · 24 h or more. The upper limit is, 1500g ^/ m 2 · 24h, preferably 1,070g ^/ m 2 · 24h. Since the moisture permeability is large, it is possible to prevent moisture and sweat from accumulating when the patch is applied to the skin. The moisture permeability is measured under the B condition (temperature 40 ° C., relative humidity 90%) defined in JIS Z0208.

(Probe tack)
The patch of the present invention preferably has a probe tack of 1.0 to 4.0 N / 5 mmφ, more preferably 1.95 to 3.70 N / 5 mmφ, and 1.96 to 3.60 N / 5 mmφ is more preferable, and 1.97 to 3.57 N / 5 mφ is particularly preferable. If the probe tack is too small, the adhesive material may fall off during application. In addition, if the probe tack is too large, a resistance or pain may be felt when the patch is peeled off from the skin surface after being applied.

(Manufacturing method of patch material)
The patch of the present invention is a patch comprising a support layer and an adhesive layer, and the adhesive layer is
(A) Adhesive A: (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms as an essential component is 65 to 99.5% by mass, and can be copolymerized with the (meth) acrylic acid alkyl ester. (Meth) acrylic acid alkyl ester and vinyl monomer in the range of 0.5 to 8% by mass of the monomer having various functional groups and the remaining components as a total of 100% by mass of the monomers. And a copolymer composed of 0 to 34.5% by mass of a vinyl monomer having no alkoxy group, which is copolymerizable with the (meth) acrylic acid alkyl ester. Acrylic pressure-sensitive adhesive, and (b) pressure-sensitive adhesive B: 50 to 90 (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms as an essential component in the range where the total amount of monomers is 100% by mass. A vinyl having a functional group copolymerizable with the (meth) acrylic acid alkyl ester in an amount of 0.5 to 8% by mass and a vinyl different from the (meth) acrylic acid alkyl ester or the vinyl monomer An acrylic pressure-sensitive adhesive comprising a monomer and a copolymer comprising 9.5 to 49.5% by mass of a vinyl monomer having an alkoxy group, which is copolymerizable with the alkyl (meth) acrylate And (i) the mixing ratio of the pressure-sensitive adhesive A and the pressure-sensitive adhesive B is 100 parts by mass of the total mass of the pressure-sensitive adhesive A and the pressure-sensitive adhesive B. The production method is not limited as long as it is possible to obtain a patch having a ratio of 15/85 to 85/15 (mass ratio) and (ii) the mixed adhesive is crosslinked. The patch of the present invention can be produced as a sheet-like laminate or can be produced as a roll-like laminate. A normal method for producing a patch can be employed, and a hot melt method, a calendar method, a welding method, or the like, which is a general method for producing a patch, can be employed. Of these, the melting method is preferable. The melting method is a method in which necessary components are dissolved in a solvent and spread on a support, and then the solvent is evaporated to be bonded to the support and then cut into an appropriate shape to obtain a patch.

  As one method for producing the patch of the present invention, a mixed adhesive of two types of acrylic adhesive and a crosslinking agent are added, mixed with stirring uniformly, and mixed on the process paper coated with a silicone release agent or the like. After the pressure-sensitive adhesive solution or emulsion is applied to form the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer can be produced by a method of integrating with a support including a film. The coating method is not particularly limited, and for example, the adhesive solution containing each component can be applied using a general-purpose coating machine such as a knife coater, a comma coater, or a reverse coater. The obtained patch may be wound into a roll to obtain a roll-shaped patch, or cut into a predetermined shape and size such as an oval, a circle, a square, and a rectangle according to the intended use.

(Application of adhesive material)
The patch of the present invention can be used as a general emergency adhesive bandage by adding a carrier layer and a separator layer, if necessary, in a shape according to the use site. Moreover, it can be used as a medical adhesive tape as it is, or it can be made into a transdermal absorption preparation to which a specific drug is added.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these examples. The measuring method of the characteristic and physical property of each layer with which the adhesive material and the adhesive material of this invention are provided is as follows.

(Thickness)
The thicknesses of the support layer, the pressure-sensitive adhesive layer, and the patch were measured using a dial thickness gauge (unit: μm, n = 3 average value).

(Moisture permeability)
The moisture permeability of the patch was measured under the condition B (temperature: 40 ° C., relative humidity: 90%) defined in JIS Z0208 (unit: g / m ² · 24 h, average value of n = 3).

(Probe tack)
The probe tack of the pressure-sensitive adhesive layer was determined by using a probe tack tester manufactured by Nichiban Co., Ltd., in accordance with the probe tack test method described in JIS Z0237 (1996 edition) as a reference. It was determined by measuring the force required to peel off (unit: N / 5 mmφ, average value of n = 3).

(Practical evaluation)
As a practical evaluation of the patch, wipe off the water after bathing in five adult male and female subjects, and then apply the patch to the second joint of the finger, apply it for 12 hours, and then bathe. “Adhesiveness after bathing” evaluated. Then, 24 hours after application, after evaluating “adhesiveness after application for 24 hours”, the adhesive material was peeled off, and “skin dandruff” was evaluated. The evaluation was performed by 1 to 5 according to the following criteria for each of 5 subjects, rounded off the average value, and evaluated according to the following criteria. Moreover, the present inventors evaluated comprehensive evaluation based on the results of characteristic evaluation and practical evaluation.

<Adhesion after bathing>
5: The whole surface is well attached 4: The periphery is slightly peeled off or turned up 3: About 1/3 peeled off or turned up 2: Half or more peeled off or turned up 1: Dropped

A: The average value is 4.0 or more. B: The average value is 3.5 to 3.9.
C: Average value is 3.4 or less

<Adhesiveness after 24 hours>
5: The whole surface is well attached 4: The periphery is slightly peeled off or turned up 3: About 1/3 peeled off or turned up 2: Half or more peeled off or turned up 1: Dropped

A: Average value is 3.6 or more B: Average value is 3.1 to 3.5
C: Average value is 3.0 or less

<Dry skin>
5: No dullness 4: Slightly fuzzy, but no problem 3: Buzzy problem 2: Buzzy, very problematic 1: Overblown blistering

A: The average value is 4.0 or more. B: The average value is 3.5 to 3.9.
C: Average value is 3.4 or less

<Comprehensive evaluation>
AA: Overall, particularly excellent A: Overall excellent, C: Overall problem occurred

[Compatibility analysis of adhesive A and adhesive B]
Adhesive A1: Acrylic adhesive of 2-ethylhexyl acrylate / vinyl acetate / acrylic acid (mass ratio 85/11/4) copolymer and epoxy crosslinking agent (TETRAD-X, manufactured by Mitsubishi Gas Chemical Company) It was obtained by adding 05 parts and crosslinking.

  Adhesive B1: Isononyl acrylate / 2-methoxyethyl acrylate / acrylic acid (mass ratio 68/30/2) copolymer acrylic adhesive and epoxy cross-linking agent (TETRAD-X), manufactured by Mitsubishi Gas Chemical Co., Ltd. ) 0.05 parts was added and crosslinked.

  Mixed adhesive C1: Adhesive A (: acrylic adhesive of 2-ethylhexyl acrylate / vinyl acetate / acrylic acid (mass ratio 85/11/4) copolymer) and adhesive B (: isononyl acrylate / A total of 100 parts by mass of 2-methoxyethyl acrylate / acrylic acid (mass ratio 68/30/2) copolymer acrylic adhesive), epoxy-based crosslinking agent (TETRAD-X), manufactured by Mitsubishi Gas Chemical Company, Inc. ) It was obtained by adding 0.05 part by mass and crosslinking.

  The dynamic viscoelasticity measurement is performed on the adhesive A1, the adhesive B1, and the mixed adhesive C1, and the temperature dependency of each tan δ (loss tangent), the temperature dependency of the storage elastic modulus (G ′), and the loss elastic modulus (G ″). The solubility parameter SP values of 2-ethylhexyl acrylate and isononyl acrylate are 8.36 and 8.38, respectively, and the difference is within the range of 0.50.

(result)
From the temperature dependence of tan δ (loss tangent) of dynamic viscoelasticity measurement, the glass transition temperature (Tg) is obtained by the peak, the glass transition temperature of the adhesive A1 is −33.2 ° C., and the glass transition temperature of the adhesive B1. With respect to −19.4 ° C., only one peak was confirmed in the glass transition temperature of the mixed pressure-sensitive adhesive C1 in the range of −29.3 to −27.6 ° C. Therefore, the glass transition temperature of the mixed pressure-sensitive adhesive C1 was close to −26.3 ° C. at the midpoint between the glass transition temperatures of the pressure-sensitive adhesive A1 and the pressure-sensitive adhesive B1, and compatibility was recognized.

  The temperature-dependent change of the storage elastic modulus (G ′) and loss elastic modulus (G ″) of the mixed adhesive C1 is located between the adhesive A1 and the adhesive B1, and shows the same change. Compatibility was confirmed.

[Examples 1-7 and Comparative Examples 1-4]
An adhesive material (support layer thickness 170 μm, pressure-sensitive adhesive layer thickness 40 μm) provided with a pressure-sensitive adhesive layer made of mixed pressure-sensitive adhesive C1 on a support obtained by laminating a polyurethane non-woven fabric on a polyurethane film by a normal production method. Obtained. By changing the mixing ratio of the pressure-sensitive adhesive A1 and the pressure-sensitive adhesive B1, the effect of the mixing ratio of the pressure-sensitive adhesive A1 and the pressure-sensitive adhesive B1 was examined as a patch by the same method. Practical evaluation and characteristic evaluation of each patch were performed. The results are shown in Table 1.

[Example 8]
A patch having a pressure-sensitive adhesive layer (thickness 40 μm) made of the mixed pressure-sensitive adhesive C1 was obtained on a polyurethane elastomer film (thickness 30 μm). Practical evaluation and characteristic evaluation were performed at a mixing ratio of 50 parts by mass of adhesive A1 and 50 parts by mass of adhesive B1. The results are shown in Table 1.

[Discussion]
From Table 1, in the case of Examples 1 to 7 in which the support is a film / nonwoven fabric, the pressure-sensitive adhesive A alone has a low water vapor transmission rate of 594 g / m ² · 24 h, but the pressure-sensitive adhesive B with good moisture permeability is mixed with the pressure-sensitive adhesive 100. It was found that when blending 15 parts by mass or more in parts by mass, the moisture permeability exceeds 650 g / m ² · 24 h. The best practical evaluation was obtained when the mixing ratio of the adhesive A and the adhesive B was 35/65 to 65/35 (mass ratio).

  However, although the mixing ratio of the adhesive A and the adhesive B (adhesive A / adhesive B) is excellent in practical evaluation up to 15/85 to 85/15 (mass ratio), the adhesive B is increased and mixed adhesive. It turned out that practical evaluation will be inferior when it exceeds 85 mass parts in 100 mass parts of agents.

  In the case of Example 8 in which the support was a film, since the support was a film, the moisture permeability decreased, but the film adhered to the skin, and in the evaluation of practicality, the adhesion after bathing was good. This is considered because water does not enter from the side.

  In contrast to the examples, Comparative Examples 1 to 4 had a C evaluation in the practical evaluation, and the overall evaluation was C, which was problematic.

  The patch of the present invention is applied to skin and the like, and is suitably used, for example, for medical purposes, for example, in the fields of medical hygiene and external use. Specifically, it can be used for adhesive bandages, medical adhesive tapes, adhesive bandages, dressing materials, surgical surgical tapes, transdermal absorption preparations, and the like.

  In the present invention, the adhesive layer of the patch is a mixed adhesive composed of a hydrophobic acrylic adhesive and a hydrophilic acrylic adhesive, so that even if the support is a waterproof film, the skin Since it can provide adhesives that are both waterproof, breathable and adhesive, it can be used industrially as an adhesive suitable for medical adhesive tapes and emergency adhesive plasters. Is expensive. Especially suitable for emergency bandages.

Claims (10)

A patch comprising a support layer and an adhesive layer, wherein the adhesive layer is
(A) Adhesive A: (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms as an essential component, 65 to 99.5% by mass, a function copolymerizable with the (meth) acrylic acid alkyl ester In the range of 0.5 to 8% by mass of the vinyl monomer having a group and the remaining monomer as a total of 100% by mass, the (meth) acrylic acid alkyl ester and the vinyl monomer are Acrylic polymer containing a copolymer comprising 0 to 34.5% by mass of a vinyl monomer which is a different vinyl monomer and is copolymerizable with the alkyl (meth) acrylate and has no hydrophilicity Pressure-sensitive adhesive, and (b) pressure-sensitive adhesive B: 50 to 90% by mass of a (meth) acrylic acid alkyl ester having an alkyl group having 8 to 12 carbon atoms as an essential component within the range of 100% by mass of the monomers. The 0.5 to 8% by mass of a vinyl monomer having a functional group copolymerizable with a (meth) acrylic acid alkyl ester, a vinyl monomer different from the (meth) acrylic acid alkyl ester or the vinyl monomer An acrylic pressure-sensitive adhesive containing a copolymer composed of 9.5 to 49.5% by mass of a hydrophilic vinyl monomer copolymerizable with the alkyl (meth) acrylate. It is a mixed adhesive obtained by mixing, and (i) the mixing ratio of the adhesive A and the adhesive B (adhesive A / adhesive B) is the total mass of the adhesive A and the adhesive B The adhesive is characterized by being 15/85 to 85/15 (mass ratio), and (ii) the mixed pressure-sensitive adhesive is cross-linked.   The patch according to claim 1, wherein the pressure-sensitive adhesive layer is crosslinked by a crosslinking agent.   The patch according to claim 1, wherein the functional group is a carboxy group or a hydroxy group.   The patch according to any one of claims 1 to 3, wherein the pressure-sensitive adhesive layer does not contain a plasticizer in which the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is liquid at room temperature.   The patch according to any one of claims 1 to 4, wherein the support layer includes a film.   The patch according to any one of claims 1 to 5, wherein the support layer is a laminate of a film and a fabric. The patch according to any one of claims 1 to 6, wherein the moisture permeability is 300 g / m ² · 24 h or more.   When the mixing ratio of the adhesive A and the adhesive B (adhesive A / adhesive B) is 100 parts by mass of the total mass of the adhesive A and the adhesive B, 35/65 to 65/35 The patch according to any one of claims 1 to 7, wherein the patch is (mass ratio).   The solubility parameter (SP) of the alkyl (meth) acrylate having an alkyl group having 8 to 12 carbon atoms of the pressure-sensitive adhesive A and the alkyl (meth) acrylate having an alkyl group having 8 to 12 carbon atoms of the pressure-sensitive adhesive B The patch according to any one of claims 1 to 8, wherein the difference is within a range of 0.50.   The patch according to any one of claims 1 to 9, which is an emergency bandage.