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JP6948131B2 - Lumber for skin sticking and its manufacturing method - Google Patents

Lumber for skin sticking and its manufacturing method Download PDF

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JP6948131B2
JP6948131B2 JP2017034922A JP2017034922A JP6948131B2 JP 6948131 B2 JP6948131 B2 JP 6948131B2 JP 2017034922 A JP2017034922 A JP 2017034922A JP 2017034922 A JP2017034922 A JP 2017034922A JP 6948131 B2 JP6948131 B2 JP 6948131B2
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sensitive adhesive
pressure
adhesive layer
holes
patch
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JP2018139733A (en
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明美佳 千田
明美佳 千田
新史 渡邊
新史 渡邊
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Nichiban Co Ltd
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Description

本発明は、皮膚貼付用貼付材及びその製造方法に関する。 The present invention relates to a sticking material for skin sticking and a method for producing the same.

絆創膏やドレッシングフィルム、テーピングテープ等のヒトの皮膚に貼付する貼付材は、透気度が高いことが望まれる。 Adhesive plasters, dressing films, taping tapes, and other adhesives to be attached to human skin are desired to have high air permeability.

このような特性を貼付材に持たせるためには、支持体と共に粘着剤層の透気度を高める必要がある。ここで、粘着剤層を構成する粘着剤としては、環境保護の上で、水を媒体とするエマルション型粘着剤が好適に使用される。そして、粘着剤層の透気度を高めるべくこのエマルション型粘着剤を発泡させる手段としては、機械発泡(空気混入攪拌)が一般的に行われている(例えば特許文献1)。 In order to give the patch material such characteristics, it is necessary to increase the air permeability of the pressure-sensitive adhesive layer together with the support. Here, as the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, an emulsion-type pressure-sensitive adhesive using water as a medium is preferably used for environmental protection. As a means for foaming this emulsion-type pressure-sensitive adhesive in order to increase the air permeability of the pressure-sensitive adhesive layer, mechanical foaming (air mixing and stirring) is generally performed (for example, Patent Document 1).

先行特許文献Prior patent documents

特開2004−84138号公報Japanese Unexamined Patent Publication No. 2004-84138

しかし、特許文献1に記載の貼付材では、皮膚からの剥離時にのり残りを起こす傾向があるという問題点がある。そこで、本発明は、皮膚貼付用貼付材としての基本特性である、高い透気度を担保しつつ、皮膚からの剥離時にのり残りを防止する手段を提供することを目的とする。 However, the patch material described in Patent Document 1 has a problem that it tends to leave a residue when peeled from the skin. Therefore, an object of the present invention is to provide a means for preventing adhesive residue at the time of peeling from the skin while ensuring high air permeability, which is a basic characteristic of a sticking material for skin sticking.

本発明(1)は、支持体上に粘着剤層が積層された皮膚貼付用貼付材において、
前記粘着剤層を構成する粘着剤が、エマルション型粘着剤であり、且つ
前記粘着剤層を厚み方向に貫通する微細上下貫通孔が、前記粘着剤層の全面に亘り多数形成されている
ことを特徴とする貼付材である。
本発明(2)は、前記微細上下貫通孔の平均孔径が、20〜400μmである、前記発明(1)の貼付材である。
本発明(3)は、前記微細上下貫通孔の形状が、円柱状である、前記発明(1)又は(2)の貼付材である。
本発明(4)は、前記粘着剤層における粘着剤層表面における前記微細上下貫通孔の面密度が、2〜100個/mmである、前記発明(1)〜(3)の貼付材である。
本発明(5)は、前記粘着剤層表面積に対する前記微細上下貫通孔の開孔面積率が、3〜40%である、前記発明(1)〜(4)の貼付材である。
本発明(6)は、前記貼付材の透気度が、0.1〜30sec/100mlである、前記発明(1)〜(5)の貼付材である。
本発明(7)は、支持体上に粘着剤層が積層された皮膚貼付用貼付材において、
前記粘着剤層が、発泡剤を含有するエマルション型粘着剤液が微細凹凸形状を有する剥離性シート上に適用された状態にて、前記発泡剤を分解させることにより形成された孔を有する
ことを特徴とする貼付材である。
本発明(8)は、前記剥離性シートが、算術平均粗さ0.5〜3.0μm、粗さ曲面要素の平均長さ0.05〜0.20mmの凹凸を表面に有する、前記発明(7)の貼付材である。
本発明(9)は、支持体上に粘着剤層が積層された皮膚貼付用貼付材の製造方法において、
発泡剤を含有するエマルション型粘着剤液を、微細凹凸形状を有する剥離性シート上に適用し、前記発泡剤を分解させることにより孔を形成する工程
を含むことを特徴とする製造方法である。
本発明(10)は、前記剥離性シートが、算術平均粗さ0.5〜3.0μm、粗さ曲面要素の平均長さ0.05〜0.20mmの凹凸を表面に有する、前記発明(9)の製造方法である。
本発明(11)は、前記エマルション型粘着剤液の表面張力が、35mN/m以下である、前記発明(9)又は(10)の製造方法である。
本発明(12)は、前記皮膚貼付用貼付材が、前記発明(1)〜(6)の皮膚貼付用貼付材である、前記発明(9)〜(11)の製造方法である。
The present invention (1) is a skin sticking material in which an adhesive layer is laminated on a support.
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is an emulsion-type pressure-sensitive adhesive, and a large number of fine vertical through holes penetrating the pressure-sensitive adhesive layer in the thickness direction are formed over the entire surface of the pressure-sensitive adhesive layer. It is a characteristic pasting material.
The present invention (2) is the sticking material of the present invention (1), wherein the average pore diameter of the fine upper and lower through holes is 20 to 400 μm.
The present invention (3) is the sticking material of the invention (1) or (2), wherein the shape of the fine upper and lower through holes is columnar.
The present invention (4) is the patch material of the inventions (1) to (3), wherein the surface density of the fine upper and lower through holes on the surface of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive layer is 2 to 100 pieces / mm 2. be.
The present invention (5) is the patch material of the inventions (1) to (4), wherein the opening area ratio of the fine upper and lower through holes to the surface area of the pressure-sensitive adhesive layer is 3 to 40%.
The present invention (6) is the sticking material of the inventions (1) to (5), wherein the air permeability of the sticking material is 0.1 to 30 sec / 100 ml.
The present invention (7) is a skin-sticking material in which an adhesive layer is laminated on a support.
The pressure-sensitive adhesive layer has holes formed by decomposing the foaming agent in a state where an emulsion-type pressure-sensitive adhesive liquid containing a foaming agent is applied on a peelable sheet having a fine uneven shape. It is a characteristic pasting material.
According to the present invention (8), the peelable sheet has irregularities on the surface having an arithmetic mean roughness of 0.5 to 3.0 μm and an average length of a roughness curved surface element of 0.05 to 0.20 mm. It is a pasting material of 7).
The present invention (9) is a method for manufacturing a skin sticking material in which an adhesive layer is laminated on a support.
The production method is characterized by comprising a step of applying an emulsion-type pressure-sensitive adhesive liquid containing a foaming agent onto a peelable sheet having a fine concavo-convex shape and decomposing the foaming agent to form pores.
According to the present invention (10), the peelable sheet has irregularities on the surface having an arithmetic mean roughness of 0.5 to 3.0 μm and an average length of a roughness curved surface element of 0.05 to 0.20 mm. 9) The manufacturing method.
The present invention (11) is the production method of the invention (9) or (10), wherein the surface tension of the emulsion-type pressure-sensitive adhesive liquid is 35 mN / m or less.
The present invention (12) is the manufacturing method of the inventions (9) to (11), wherein the skin sticking material is the skin sticking material of the inventions (1) to (6).

本発明によれば、皮膚貼付用貼付材としての基本特性である、高い透気度を担保しつつ、皮膚からの剥離時にのり残りを防止する手段を提供することが可能となる。更に、より好適な本発明によれば、透気性、汗の排出性、耐水性、そして貼付材表面への薬剤液塗布による皮膚表面患部の薬剤投与も担保可能である。尚、一般に、糊残り防止のために凝集力を上げると粘着力が低下して皮膚へ付着性が著しく落ちるところ、本発明によればそれも防止することができる。 According to the present invention, it is possible to provide a means for preventing adhesive residue at the time of peeling from the skin while ensuring high air permeability, which is a basic characteristic of a sticking material for skin sticking. Further, according to the more preferable invention, it is possible to ensure air permeability, sweat discharge property, water resistance, and drug administration to the affected part of the skin surface by applying a drug solution to the surface of the patch. In general, when the cohesive force is increased to prevent adhesive residue, the adhesive force is lowered and the adhesiveness to the skin is remarkably lowered. According to the present invention, this can also be prevented.

図1は、本発明に係る皮膚貼付用貼付材の斜視図である(一例)。FIG. 1 is a perspective view of a sticking material for skin sticking according to the present invention (one example). 図2は、本発明に係る皮膚貼付用貼付材の上面図である(一例)。FIG. 2 is a top view of a sticking material for skin sticking according to the present invention (one example). 図3は、本発明に係る皮膚貼付用貼付材の断面図である(一例)。FIG. 3 is a cross-sectional view of a sticking material for skin sticking according to the present invention (one example). 図4は、本発明に係る皮膚貼付用貼付材を製造する際の、凹凸を表面に有する剥離性シートの表面粗さ測定器による表面状態図である(一例)。FIG. 4 is a surface state diagram of a peelable sheet having irregularities on its surface by a surface roughness measuring instrument when the adhesive material for skin attachment according to the present invention is manufactured (one example).

以下、本発明に係る皮膚貼付用貼付材に関し、以下の順で説明する。
1.皮膚貼付用貼付材の全体構造及び物性
2.各部
2−1.粘着剤層
2−1−1.粘着剤層の構造
2−1−2.粘着剤層の材質
2−1−3.粘着剤層の物性
2−2.透気性支持体
3.皮膚貼付用貼付材の製造方法
3−1.原材料・使用部材
3−2.プロセス
4.皮膚貼付用貼付材の使用方法(用途)
Hereinafter, the patch material for skin sticking according to the present invention will be described in the following order.
1. 1. Overall structure and physical properties of the patch material for skin patch 2. Each part 2-1. Adhesive layer 2-1-1. Structure of adhesive layer 2-1-2. Material of adhesive layer 2-1-3. Physical characteristics of the adhesive layer 2-2. Air permeable support 3. Manufacturing method of patch material for skin sticking 3-1. Raw materials / materials used 3-2. Process 4. How to use the sticking material for skin sticking (use)

≪1.皮膚貼付用貼付材の全体構造及び物性≫
図1〜図3に示すように、本発明に係る皮膚貼付用貼付材1は、支持体1B上に粘着剤層1Aが積層された皮膚貼付用貼付材において、前記粘着剤層1Aを構成する粘着剤が、エマルション型粘着剤であり、且つ、前記粘着剤層1Aを厚み方向に貫通する微細上下貫通孔1Aaが、前記粘着剤層1Aの全面に亘り多数形成されていることを特徴とする貼付材である。尚、図示しないが、本発明に係る皮膚貼付用貼付材1は、粘着剤層1Aの、透気性支持体1Bとの接触面とは反対側の面上に、剥離層が存在していてもよい(加えて、当該剥離層は、下記で説明する、皮膚貼付用貼付材の製造方法において使用する剥離性シートであってもよい)。
≪1. Overall structure and physical properties of the adhesive material for skin application ≫
As shown in FIGS. 1 to 3, the skin sticking material 1 according to the present invention constitutes the pressure-sensitive adhesive layer 1A in a skin sticking material in which the pressure-sensitive adhesive layer 1A is laminated on the support 1B. The pressure-sensitive adhesive is an emulsion-type pressure-sensitive adhesive, and a large number of fine vertical through holes 1Aa penetrating the pressure-sensitive adhesive layer 1A in the thickness direction are formed over the entire surface of the pressure-sensitive adhesive layer 1A. It is a sticking material. Although not shown, the skin-adhesive patch 1 according to the present invention has a peeling layer on the surface of the pressure-sensitive adhesive layer 1A opposite to the contact surface with the air-permeable support 1B. (In addition, the peeling layer may be a peelable sheet used in the method for producing a patch material for skin sticking, which will be described below).

本発明に係る皮膚貼付用貼付材の透気度は、好適には0.1〜30sec/100mlの範囲内であり、より好適には0.1〜20sec/100mlの範囲内であり、特に好適には0.1〜10sec/100mlの範囲内である。 The air permeability of the adhesive material for skin application according to the present invention is preferably in the range of 0.1 to 30 sec / 100 ml, more preferably in the range of 0.1 to 20 sec / 100 ml, and is particularly preferable. Is in the range of 0.1 to 10 sec / 100 ml.

<2.各部>
{2−1.各部/粘着剤層}
(2−1−1.各部/粘着剤層/粘着剤層の構造)
以下、図1〜図3を参照しながら、粘着剤層の構造を説明する。
<2. Each part>
{2-1. Each part / adhesive layer}
(2-1-1. Structure of each part / adhesive layer / adhesive layer)
Hereinafter, the structure of the pressure-sensitive adhesive layer will be described with reference to FIGS. 1 to 3.

・厚み
まず、粘着剤層1Aの厚みは、好適には5〜100μm、更に好ましくは10〜80μm、特に20〜60μmが望ましい 。
-Thickness First, the thickness of the pressure-sensitive adhesive layer 1A is preferably 5 to 100 μm, more preferably 10 to 80 μm, and particularly preferably 20 to 60 μm.

・微細上下貫通孔
また、粘着剤層1Aを厚み方向に貫通する微細上下貫通孔1Aaが、粘着剤層1Aの全面に亘り多数形成されている。ここで、微細上下貫通孔とは、粘着剤層の厚み方向を基準として、上下方向に形成された筒状孔を指す。ここで、微細上下貫通孔1Aaの平均孔径は、好適には20〜400μm、更に好ましくは30〜300μm、特に40〜200μmが望ましい。また、貫通孔の形状は、好適には円柱状である。尚、微細上下貫通孔は、前記の通り、粘着剤層の厚み方向を基準として上下方向に形成された筒状孔(貫通孔)である限り特に限定されず、例えば、粘着剤層に存在する微細上下貫通孔のすべての孔が粘着剤層表面から透気性支持体まで通じている必要はない。更に、粘着剤層表面における微細上下貫通孔1Aaの面密度(発泡密度)は、好適には2〜100個/mm、更に好ましくは3〜80個/mm、特に4〜60個/mmが望ましい。更には、粘着剤層表面積に対する微細上下微細孔の開孔面積率(開孔率)は、好適には3〜40%であり、より好適には5〜30%である。これら範囲内であると、より良好な粘着剤透気度及び粘着特性を実現できる傾向にある。このように、皮膚貼付用貼付材の基本特性(透気性等)を担保すべく、従来技術では機械発泡(空気混入攪拌)により海綿状に気泡を発生させていた代わりに、本発明では粘着剤層全面に亘り微細上下貫通孔を形成させている。本発明者らは、このような構成(これに加え、エマルション型粘着剤の採用、透気性支持体の採用)を採ることにより、従来通りの基本特性を実現できるだけでなく、皮膚からの剥離時にのり残りが顕著に抑制されるという予想外の効果を実現できることを見出したのである。
Fine upper and lower through holes In addition, a large number of fine upper and lower through holes 1Aa penetrating the pressure-sensitive adhesive layer 1A in the thickness direction are formed over the entire surface of the pressure-sensitive adhesive layer 1A. Here, the fine vertical through hole refers to a cylindrical hole formed in the vertical direction with reference to the thickness direction of the pressure-sensitive adhesive layer. Here, the average hole diameter of the fine upper and lower through holes 1Aa is preferably 20 to 400 μm, more preferably 30 to 300 μm, and particularly preferably 40 to 200 μm. Further, the shape of the through hole is preferably cylindrical. As described above, the fine vertical through holes are not particularly limited as long as they are tubular holes (through holes) formed in the vertical direction with reference to the thickness direction of the pressure-sensitive adhesive layer, and are present in, for example, the pressure-sensitive adhesive layer. It is not necessary that all the fine upper and lower through holes pass from the surface of the pressure-sensitive adhesive layer to the air-permeable support. Further, the surface density (foaming density) of the fine upper and lower through holes 1Aa on the surface of the pressure-sensitive adhesive layer is preferably 2 to 100 pieces / mm 2 , more preferably 3 to 80 pieces / mm 2 , and particularly 4 to 60 pieces / mm. 2 is desirable. Further, the opening area ratio (opening ratio) of the fine upper and lower fine pores with respect to the surface area of the pressure-sensitive adhesive layer is preferably 3 to 40%, and more preferably 5 to 30%. Within these ranges, better adhesive air permeability and adhesive properties tend to be achieved. As described above, in order to ensure the basic characteristics (air permeability, etc.) of the adhesive for skin attachment, instead of generating spongy air bubbles by mechanical foaming (air mixing and stirring) in the prior art, the adhesive is used in the present invention. Fine upper and lower through holes are formed over the entire surface of the layer. By adopting such a configuration (in addition to this, the adoption of an emulsion type adhesive and the adoption of an air permeable support), the present inventors can not only realize the basic characteristics as before, but also when peeling from the skin. They found that the unexpected effect of significantly suppressing the adhesive residue could be achieved.

(2−1−2.各部/粘着剤層/粘着剤層の材質)
本発明に係るエマルション型粘着剤は、アクリル系粘着剤が好適に用いられる。以下、好適な態様である、エマルション型アクリル系粘着剤について詳述する。尚、以下の説明においては、粘着剤層を構成するエマルション型アクリル系粘着剤に関する説明の他、当該粘着剤層を形成させるための使用原料であるエマルション型粘着剤液に関する説明も含まれる。
(2-1-2. Materials of each part / adhesive layer / adhesive layer)
As the emulsion type pressure-sensitive adhesive according to the present invention, an acrylic pressure-sensitive adhesive is preferably used. Hereinafter, an emulsion-type acrylic pressure-sensitive adhesive, which is a preferred embodiment, will be described in detail. In the following description, in addition to the description of the emulsion type acrylic pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, the description of the emulsion-type pressure-sensitive adhesive liquid which is a raw material used for forming the pressure-sensitive adhesive layer is also included.

好適なエマルション型アクリル系粘着剤は、アルキル基の炭素数が4〜12である(メタ)アクリル酸アルキルエステル50〜99.5重量%、カルボキシル基含有モノマー0.5〜10重量%及びその他の共重合可能なモノマー0〜40重量%を成分とする混合モノマー100重量部に対し、界面活性剤を0.3〜12重量部添加し、水媒体中で乳化重合して得られるエマルション型アクリル系粘着剤である。以下、各原料・重合方法を詳述する。 Suitable emulsion-type acrylic pressure-sensitive adhesives include (meth) acrylic acid alkyl esters having 4 to 12 carbon atoms in alkyl groups, 0.5 to 10% by weight of carboxyl group-containing monomers, and others. Emulsion type acrylic obtained by adding 0.3 to 12 parts by weight of a surfactant to 100 parts by weight of a mixed monomer containing 0 to 40% by weight of a copolymerizable monomer and emulsion polymerization in an aqueous medium. It is an adhesive. Hereinafter, each raw material and polymerization method will be described in detail.

まず、アルキル基の炭素数が4〜12である(メタ)アクリル酸アルキルエステルは、(メタ)アクリル酸と炭素数4〜12のアルコールとのエステルである。ここで、前記アルコールは、直鎖状でも分岐状であってもよい。このエステルとしては、例えば、アクリル酸ブチル、アクリル酸−2−エチルヘキシル、アクリル酸イソオクチル、アクリル酸イソノニル、アクリル酸デシル等が挙げられる。また、1種でも、2種以上を組み合わせて用いてもよい。 First, the (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms is an ester of (meth) acrylic acid and an alcohol having 4 to 12 carbon atoms. Here, the alcohol may be linear or branched. Examples of this ester include butyl acrylate, -2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, and decyl acrylate. Further, one type or a combination of two or more types may be used.

次に、カルボキシル基含有モノマーは、カルボキシル基を一以上有し且つC=C二重結合を有する成分であれば特に限定されず、例えば、(メタ)アクリル酸、マレイン酸、イタコン酸、アクリル酸2−カルボキシエチル、2−アクロイロキシエチルコハク酸、アクリル酸ω−カルボキシポリカプロラクトン等のカルボキシル基含有モノマーが挙げられる。また、1種でも、2種以上を組み合わせて用いてもよい。 Next, the carboxyl group-containing monomer is not particularly limited as long as it is a component having one or more carboxyl groups and a C = C double bond, and is, for example, (meth) acrylic acid, maleic acid, itaconic acid, acrylic acid. Examples thereof include carboxyl group-containing monomers such as 2-carboxyethyl, 2-acyloxyethyl succinic acid, and ω-carboxypolycaprolactone acrylic acid. Further, one type or a combination of two or more types may be used.

その他の共重合可能なモノマーは、例えば、アクリル酸2−ヒドロキシエチル、アクリル酸2−ヒドロキシプロピル等の水酸基含有モノマー、(メタ)アクリルアミド、N−メチロールアクリルアミド等のアミド系モノマー、スチレン、酢酸ビニル等のビニル系モノマー、(メタ)アクリル酸グリシジル等のエポキシ基含有モノマー、(メタ)アクリルニトリル等のニトリル系モノマー、アクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸ステアリル等の上記以外の(メタ)アクリル酸アルキルエステル、トリエチレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、トリメチロールプロパントリアクリレート等の多官能モノマー等を挙げることができる。このモノマーは、1種でも2種以上を組み合わせて用いてもよい。 Other copolymerizable monomers include, for example, hydroxyl group-containing monomers such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate, amide-based monomers such as (meth) acrylamide and N-methylol acrylamide, styrene, vinyl acetate and the like. Vinyl-based monomers, epoxy group-containing monomers such as glycidyl (meth) acrylate, nitrile-based monomers such as (meth) acrylic nitrile, methyl acrylate, ethyl acrylate, isopropyl acrylate, stearyl acrylate, etc. Examples thereof include polyfunctional monomers such as meth) acrylic acid alkyl ester, triethylene glycol diacrylate, neopentyl glycol diacrylate, and trimethylolpropane triacrylate. This monomer may be used alone or in combination of two or more.

エマルション重合するための乳化剤としての界面活性剤は、特に限定されるものではなく、一般的なものを採用することができ、具体的にはポリオキシエチレンアルキルアリールエーテル、ポリオキシエチレンソルビタン脂肪酸エステルなどのノニオン性界面活性剤や、脂肪酸石鹸、アルキルスルホン酸塩、アルキルコハクスルホン酸塩、ポリオキシエチレンアルキル硫酸塩などのアニオン性界面活性剤、アルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウム塩、塩化ベンザルコニウムなどのカチオン性界面活性剤、アルキルジメチルアミノ酢酸ベタイン、アルキルジメチルアミンオキサイド、アルキルカルボキシメチルヒドロキシエチルイミダゾリウムベタインなどの両性界面活性剤などが挙げられる。 The surfactant as an emulsifier for emulsion polymerization is not particularly limited, and general surfactants can be adopted, specifically, polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan fatty acid ester and the like. Nonionic surfactants, anionic surfactants such as fatty acid soaps, alkyl sulfonates, alkyl succinates, polyoxyethylene alkyl sulfates, alkyltrimethylammonium salts, dialkyldimethylammonium salts, benzalconium chloride Cationic surfactants such as, alkyldimethylaminoacetate betaine, alkyldimethylamine oxide, and amphoteric surfactants such as alkylcarboxymethylhydroxyethyl imidazolium betaine can be mentioned.

乳化重合に関しては、特に制限はなく、公知方法、条件等が適用可能である。例えば、混合モノマー及び重合開始剤等を、界面活性剤を溶解したイオン交換水に加え、高速攪拌機で分散乳化した後、50〜95℃の一定温度に保ち、不活性雰囲気下で共重合させる。尚、上記乳化液の一部を重合し、残部を連続的或いは間欠的に滴下して重合する方法でもよい。界面活性剤のエマルション型粘着剤液全体に対する濃度は、好適には0.3〜12重量%、全モノマーのエマルション型粘着剤液全体に対する濃度は、好適には30〜70重量%の範囲内とする。また、重合開始剤としては、例えば、過硫酸アンモニウムや過硫酸カリウムといった過硫酸塩、アゾビスシアノバレリックアシッド等の水溶性アゾ化合物等が挙げられる。重合開始剤は全モノマー100重量部に対して0.01〜5重量部が好適に用いられる。 The emulsion polymerization is not particularly limited, and known methods, conditions and the like can be applied. For example, a mixed monomer, a polymerization initiator and the like are added to ion-exchanged water in which a surfactant is dissolved, dispersed and emulsified with a high-speed stirrer, and then kept at a constant temperature of 50 to 95 ° C. and copolymerized in an inert atmosphere. A method in which a part of the emulsion is polymerized and the rest is continuously or intermittently dropped to polymerize may be used. The concentration of the surfactant with respect to the entire emulsion-type pressure-sensitive adhesive liquid is preferably in the range of 0.3 to 12% by weight, and the concentration of all the monomers with respect to the entire emulsion-type pressure-sensitive adhesive liquid is preferably in the range of 30 to 70% by weight. do. Examples of the polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate, and water-soluble azo compounds such as azobiscyanovaleric acid. As the polymerization initiator, 0.01 to 5 parts by weight is preferably used with respect to 100 parts by weight of all the monomers.

前記のように調製したエマルション型粘着剤液に対し、必要に応じて、消泡剤、増粘剤、防腐剤等の添加剤、ブチルメルカプタン、ドデシルメルカプタン等の連鎖移動剤、粘着付与剤樹脂等を添加してもよい。また、多官能性化合物を架橋剤としてエマルション型粘着剤液に後添加することもできる。更に、エマルション型粘着剤液に添加される発泡剤は、水溶性の発泡剤が用いられる。具体的には、炭酸水素ナトリウム、炭酸水素アンモニウム、炭酸アンモニウム等が好適に用いられる。固形分の最終濃度は、好適には30〜70重量%とする。エマルション型粘着剤液の表面張力は、50mN/m以下が好ましく、35mN/m以下がより好ましい。表面張力の調整手段としては、濡れ剤を使用することが好適である。濡れ剤は、ポリオキシエチレンラウリルエーテル酢酸ナトリウム、ポリオキシアルキレンアルキルエーテル、ポリオキシエチレンソルビタン脂肪酸エステル、ラウリル硫酸ナトリウム、ジオクチルスルホコハク酸ナトリウム等を挙げることができる。中でもジオクチルスルホコハク酸ナトリウムが好ましい。架橋剤は、オキサゾリン基含有水溶性ポリマー、オキサゾリン基含有ポリマーエマルションやエポキシ基含有樹脂エマルション、カルボジイミド基含有水溶性ポリマーなどが挙げられる。増粘剤は、ウレタン会合型やアクリル酸ポリマー系等が好ましく用いられる。 Additives such as defoamers, thickeners and preservatives, chain transfer agents such as butyl mercaptans and dodecyl mercaptans, tackifier resins and the like, as necessary, to the emulsion-type pressure-sensitive adhesive liquid prepared as described above. May be added. Further, the polyfunctional compound can be post-added to the emulsion type pressure-sensitive adhesive liquid as a cross-linking agent. Further, as the foaming agent added to the emulsion type pressure-sensitive adhesive liquid, a water-soluble foaming agent is used. Specifically, sodium hydrogen carbonate, ammonium hydrogen carbonate, ammonium carbonate and the like are preferably used. The final concentration of the solid content is preferably 30 to 70% by weight. The surface tension of the emulsion-type pressure-sensitive adhesive liquid is preferably 50 mN / m or less, more preferably 35 mN / m or less. As a means for adjusting the surface tension, it is preferable to use a wetting agent. Examples of the wetting agent include sodium polyoxyethylene lauryl ether acetate, polyoxyalkylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sodium lauryl sulfate, sodium dioctyl sulfosuccinate and the like. Of these, sodium dioctyl sulfosuccinate is preferable. Examples of the cross-linking agent include an oxazoline group-containing water-soluble polymer, an oxazoline group-containing polymer emulsion, an epoxy group-containing resin emulsion, and a carbodiimide group-containing water-soluble polymer. As the thickener, a urethane association type, an acrylic acid polymer type, or the like is preferably used.

{2−2.各部/支持体}
以下、図1〜図3を参照しながら、支持体Bの構造を説明する。本発明の貼付材の支持体は、特に限定されないが、透気性又は/及び透湿性が良好であることが好ましい。ここで、支持体の透気度は、好適には0.1〜29sec/100mlの範囲内である。支持体の透湿度(JIS L 1099 A−1 法(塩化カルシウム法)に基づいて測定)は、3,000g/m・day以上であり、4,000g/m・day以上であることが好ましい。また、支持体の透湿度の上限は、特に制限されないが、通常、約10,000g/m・day以下、好ましくは約8,000g/m・day以下である。例えば、不織布又はフェルト状の繊維集成体などの透気性基材や穴あけ加工を施したプラスチックフィルム、微多孔を有する多孔性プラスチックフィルムなどが用いられる。不織布又はフェルト状繊維集成体の材質としては、例えば綿や麻、絹、毛、レーヨンなどの天然繊維、ポリアミド、ポリエステル、ポリエチレン、ポリプロプロピレン、ポリアクリル、ポリ塩化ビニル等の合繊繊維が挙げられる。また、穴あけ加工したプラスチックフィルムとしては、例えば、ポリエチレン、ポリプロピレン、ナイロン、ポリエステル、ポリ塩化ビニル等のプラスチックフィルム(シート)に、針やレーザー、放電加工等で小孔を形成させ透気性を持たせたものが挙げられる。このとき、開孔径として、0.1μm〜10μmの小孔が設けられるが、この範囲に限定されるものではなく、所定の透気度が得られるように設定される。多孔質フィルムとしては、例えば、ポリエチレンやポリプロピレン等のポリオレフィン系樹脂やポリテトラフルオロエチレン等のフッ素系樹脂に炭酸カルシウム等の無機充填材、特に平均粒径が30μm以下のものを配合して押出し方式等の適宜な方法にてフィルム状としたものを、1軸若しくは2軸等にて延伸処理して多孔質フィルムとしたものが挙げられる。また、高透湿フィルムとしては、例えばポリウレタンフィルムをそのまま用いることもできる。ポリウレタンフィルムの場合は、主鎖の構造がポリエーテル型のものでもポリエステル型のものでもよい。この場合は、表面への薬剤液塗布による皮膚表面患部への薬剤投与は困難であるが、透湿性の優れた貼付材を得ることができる。また支持体として不織布を使用した場合には、その目付量(坪量)が10〜200g/m程度のものが好ましく使用される。また、プラスチックフィルムを用いる場合には、その厚さが10〜200μm程度のものが好ましく使用される。更に本発明にあっては、これらの支持体は単層として用いることはもちろんのこと、異なる透気性支持体を積層した積層体のものをも使用することができる。
{2-2. Each part / support}
Hereinafter, the structure of the support B will be described with reference to FIGS. 1 to 3. The support of the patch material of the present invention is not particularly limited, but it is preferable that the support has good air permeability and / and moisture permeability. Here, the air permeability of the support is preferably in the range of 0.1 to 29 sec / 100 ml. The moisture permeability of the support (measured based on the JIS L 1099 A-1 method (calcium chloride method)) is 3,000 g / m 2 · day or more, and 4,000 g / m 2 · day or more. preferable. The upper limit of the moisture permeability of the support is not particularly limited, usually, about 10,000g / m 2 · day or less, preferably less than about 8,000g / m 2 · day. For example, a breathable base material such as a non-woven fabric or a felt-like fiber assembly, a perforated plastic film, a porous plastic film having microporous properties, and the like are used. Examples of the material of the non-woven fabric or the felt-like fiber assembly include natural fibers such as cotton, linen, silk, hair and rayon, and synthetic fibers such as polyamide, polyester, polyethylene, polypropropylene, polyacrylic and polyvinyl chloride. Further, as the perforated plastic film, for example, a plastic film (sheet) such as polyethylene, polypropylene, nylon, polyester, or polyvinyl chloride is provided with air permeability by forming small holes by needle, laser, electric discharge machining, or the like. Can be mentioned. At this time, a small hole of 0.1 μm to 10 μm is provided as the opening diameter, but the hole is not limited to this range and is set so as to obtain a predetermined air permeability. As the porous film, for example, an extrusion method is performed by blending a polyolefin resin such as polyethylene or polypropylene or a fluorine resin such as polytetrafluoroethylene with an inorganic filler such as calcium carbonate, particularly one having an average particle size of 30 μm or less. Examples thereof include a film formed by an appropriate method such as, etc., which is stretched by a uniaxial or biaxial method to form a porous film. Further, as the highly moisture permeable film, for example, a polyurethane film can be used as it is. In the case of a polyurethane film, the structure of the main chain may be a polyether type or a polyester type. In this case, it is difficult to administer the drug to the affected part of the skin surface by applying the drug solution to the surface, but a patch material having excellent moisture permeability can be obtained. When a non-woven fabric is used as the support, a weight having a basis weight (basis weight) of about 10 to 200 g / m 2 is preferably used. When a plastic film is used, one having a thickness of about 10 to 200 μm is preferably used. Further, in the present invention, these supports can be used not only as a single layer but also a laminated body in which different air permeable supports are laminated.

<3.皮膚貼付用貼付材の製造方法>
(3−1.原材料・使用部材)
本発明に係る皮膚貼付用貼付材の製造に際して使用する原材料・使用部材の内、エマルション型粘着剤液及び透気性支持体については前述したので、以下では、使用部材である剥離性シートを説明する。当該剥離性シートは、以下のプロセスにて説明するような態様で使用される。当該剥離性シートは、基材に剥離剤(例えばシリコーン樹脂)を表面処理したものである。ここで、当該剥離性シートは、表面が凹凸であることが必要である。当該凹凸は、好適には、算術平均粗さ(Ra)が0.5〜3.0μmであり、より好適には0.8〜2.0μmである。また、粗さ曲面要素の平均長さ(RSm)が0.05〜0.20mmであり、より好適には0.07〜0.18mmである。また、基材は、紙製が好適に用いられる。なかでも上質紙及びグラシン紙が好ましい。ここで、上質紙とは、化学パルプ配合率が100%の洋紙をいう。本発明では、上質紙はダイレクトシリコーン処理が可能な、クレー、樹脂エマルション、又はポリビニルアルコール(PVA)を表面処理したタイプが好ましい。また、グラシン紙は、高度な叩解処理をした化学パルプを原料として抄造し、更にスーパーカレンダー等の仕上げ設備で緻密化して得たものである。ここで、当該剥離性シートを用いると厚み方向に伸びる微細上下貫通孔ができると考えられる理由を説明する。まず、当該剥離性シート上で粘着剤液が温められると発泡剤が分解し、小さな気泡が発生する。ここで、大きな貫通孔になるためには、その小さな気泡が合一することが必要であるところ、程よい凹凸(Ra)のある剥離性シートを用いた場合には凹部分を足場として気泡が合一する(上下方向に合一)と理解される。加えて、横方向の合一(孔径に関係)はRSmに関係していると理解される。尚、中程度のRaである場合、凹部分をうまく足場にできないこともあるが、この場合には、表面張力を下げると凹部分へ粘着液が浸潤しやすくなり、凹凸の影響を受けやすくなるため気泡の合一が進むものと理解される。他方、起伏のないRaの低い剥離性シートの場合はそもそもの足場がないので、表面張力を下げても気泡の合一が進まず、貫通孔が出来ないと推定される。
<3. Manufacturing method of adhesive material for skin application>
(3-1. Raw materials / materials used)
Among the raw materials and members used in the production of the skin-attaching patch according to the present invention, the emulsion-type pressure-sensitive adhesive liquid and the air-permeable support have been described above, and therefore, the peelable sheet used will be described below. .. The peelable sheet is used in a manner as described in the following process. The peelable sheet is a base material surface-treated with a release agent (for example, silicone resin). Here, the peelable sheet needs to have an uneven surface. The unevenness preferably has an arithmetic mean roughness (Ra) of 0.5 to 3.0 μm, and more preferably 0.8 to 2.0 μm. The average length (RSm) of the roughness curved surface element is 0.05 to 0.20 mm, more preferably 0.07 to 0.18 mm. The base material is preferably made of paper. Of these, high-quality paper and glassine paper are preferable. Here, the wood-free paper refers to Western paper having a chemical pulp content of 100%. In the present invention, the woodfree paper is preferably of a type that can be directly treated with silicone and is surface-treated with clay, a resin emulsion, or polyvinyl alcohol (PVA). Further, the glassine paper is obtained by making a paper using a highly beaten chemical pulp as a raw material and further densifying it with a finishing facility such as a super calendar. Here, the reason why it is considered that fine vertical through holes extending in the thickness direction are formed by using the peelable sheet will be described. First, when the pressure-sensitive adhesive liquid is warmed on the peelable sheet, the foaming agent decomposes and small bubbles are generated. Here, in order to form a large through hole, it is necessary for the small bubbles to coalesce, but when a peelable sheet having moderate unevenness (Ra) is used, the bubbles are coalesced using the concave portion as a scaffold. It is understood to be one (union in the vertical direction). In addition, lateral coalescence (related to hole diameter) is understood to be related to RSm. In the case of medium Ra, it may not be possible to use the concave portion as a scaffolding well, but in this case, if the surface tension is lowered, the adhesive liquid easily infiltrates the concave portion and is easily affected by the unevenness. Therefore, it is understood that the coalescence of bubbles progresses. On the other hand, in the case of a peelable sheet having low Ra without undulations, since there is no scaffolding in the first place, it is presumed that even if the surface tension is lowered, the coalescence of bubbles does not proceed and a through hole cannot be formed.

(3−2.プロセス)
以下、本発明に係る皮膚貼付用貼付材の製造プロセスの一例を説明する。コータ(シート繰出し部、コータヘッド、加熱乾燥部、巻取り部がこの順に直線状に配置されており、更に第2シート繰出し部を巻取り部の近辺上方に有し、加熱乾燥部と巻取り部の間でラミネートロールを有する)にて、繰出した剥離性シート上に重合したエマルション型粘着剤液を、コータヘッドにより所定の厚さで塗布し、次に加熱乾燥部にて80〜130℃程度の熱風を塗布面に吹きつけ(及び/又は、剥離性シート裏面をヤンキードライヤーに接触させることにより)乾燥させ、同時に発泡剤を熱分解、気体を発生させ、貫通孔を有する粘着剤層とし、次に第2シート繰出し部から繰出した支持体シートを粘着剤面にラミネートロールを介して貼合せ、巻取り部で巻取る。この場合、予め支持体に、粘着剤と貼合せる面と異なる面上にシリコーン樹脂や長鎖アルキル基含有ポリマー等の剥離剤を処理しておき、ラミネート後に剥離性シートを再度剥離除去し、粘着剤が転写・積層された支持体をそのまま巻き取ってもよい。巻き取った原反は、裁断機に掛けて適当な細幅のロールとするか、解きほぐしたシートを適当な形状に裁断して貼付材とする。
(3-2. Process)
Hereinafter, an example of the manufacturing process of the patch material for skin sticking according to the present invention will be described. The coater (sheet feeding part, coater head, heat-drying part, and winding part are arranged linearly in this order, and further, the second sheet feeding part is held above the vicinity of the winding part, and the heating-drying part and the winding part are wound. The emulsion-type pressure-sensitive adhesive liquid polymerized on the releasable sheet (with a laminate roll between the parts) is applied to a predetermined thickness by a coater head, and then 80 to 130 ° C. is applied in a heat-drying part. A degree of hot air is blown onto the coated surface (and / or the back surface of the peelable sheet is brought into contact with a Yankee dryer) to dry it, and at the same time, the foaming agent is thermally decomposed to generate gas to form an adhesive layer having through holes. Next, the support sheet unwound from the second sheet feeding portion is attached to the adhesive surface via a laminate roll, and wound up at the winding portion. In this case, the support is previously treated with a release agent such as a silicone resin or a long-chain alkyl group-containing polymer on a surface different from the surface to be bonded with the adhesive, and the releaseable sheet is peeled off again after laminating to adhere. The support on which the agent is transferred and laminated may be wound as it is. The wound raw fabric is hung on a cutting machine to form a roll having an appropriate narrow width, or the unraveled sheet is cut into an appropriate shape to be used as a sticking material.

<4.皮膚貼付用貼付材の使用方法(用途)>
本発明に係る皮膚貼付用貼付材の使用方法(用途)を説明する。本発明に係る皮膚貼付用貼付材は、ヒトの皮膚に貼付する用途にて使用される。例えば、絆創膏、ドレッシングフィルム、テーピングテープ、経皮吸収製剤、サージカルテープを挙げることができる。
<4. How to use the sticking material for skin sticking (use)>
The method of using (use) of the sticking material for skin sticking according to the present invention will be described. The skin sticking material according to the present invention is used for sticking to human skin. Examples thereof include adhesive plasters, dressing films, taping tapes, transdermal preparations, and surgical tapes.

以下、本発明を、実施例を参照しながら具体的に説明する。尚、本発明は以下の実施例に何ら限定されるものではない。また、特記しない限り、部や%は質量部(重量部)や質量%(重量%)を意味する。 Hereinafter, the present invention will be specifically described with reference to Examples. The present invention is not limited to the following examples. Unless otherwise specified, parts and% mean parts by mass (parts by weight) and% by mass (% by weight).

≪製造例≫
<実施例1>
(エマルション型粘着剤液の作製)
温度計、コンデンサー、窒素導入管、撹拌機を備えた温度調節可能な反応容器にイオン交換水、連鎖移動剤であるn-オクチル-3-メルカプトプロピオネートを仕込み、攪拌機で攪拌、窒素気流下で66℃まで昇温した後、重合開始剤の過硫酸アンモニウム0.25部をイオン交換水に溶解させた液を滴下し、10分後から、2−エチルヘキシルアクリレート98部、アクリル酸2部からなるモノマー混合物を、ポリオキシエチレンアルキル硫酸塩3部、イオン交換水に乳化分散させたモノマー乳化物を、3.5時間で連続的に添加し、更に66℃で2時間反応を継続し、重合を完結させた後冷却した。金網等で濾過し、固形分50%のアクリル共重合体エマルション粘着剤液(A)を得た。尚、本実施例及び比較例で用いた他の乳化重合体は、当該製造例に従い製造して用いた。
(塗工工程)
粘着剤液(A)中にモノマー全量に対して、5重量%の炭酸水素アンモニウム、0.75重量%の架橋剤、1重量%の増粘剤、2重量%の中和剤を添加、攪拌し、塗工液とした。その後、コータにて、第1繰出し部から基材がPVA処理上質紙である剥離性シート(K8シロE(R0):リンテック株式会社)を繰出し、コンマコータにて、乾燥後の塗布量が38g/mとなるように一定の厚みで塗工液を塗工し、次工程の加熱乾燥箱内にて乾燥させ、同時に発泡剤を分解、気体を発生させ粘着剤層に貫通孔を設け、乾燥箱から出たところで第2繰出し部から繰出したポリエステル不織布(透気度0.2秒/100ml)を粘着剤面にラミネートロールを介して貼合せ、巻取り部で巻取って、支持体/粘着剤/剥離性シートの三層からなる元巻試料とした。
(貼付材の作製)
元巻試料を40℃雰囲気下で3日間熟成後、一定のサイズ、形状に裁断し、各試験に供した。
<実施例2>
実施例2に係る貼付材は、実施例1において、Ra及びRSmが異なる剥離性シート(78EVS(M):王子エフテックス株式会社)に変更した以外は、同様に作製した。
<実施例3>
実施例3に係る貼付材は、実施例1において、剥離性シートの基材をグラシン紙(64GSM−L:王子エフテックス株式会社)に変更した以外は、同様に作製した。
<実施例4>
実施例4に係る貼付材は、エマルション型粘着剤液(A)中に、全体量に対して1重量%のジオクチルスルホコハク酸ナトリウムを添加して攪拌した以外は、実施例3と同様に作製した。
<比較例1及び2>
比較例1及び2は、剥離性シートの基材をポリラミ上質紙(80EPS:王子エフテックス株式会社)、ポリエステルフィルム(フィルムバイナ:藤森工業株式会社)、にそれぞれ変更した以外は、実施例4と同様に作製した。
<比較例3>
比較例3は、エマルション型粘着剤液(A)中に発泡剤は加えることなく、液をホモミキサーにて激しく攪拌し発泡させた後に塗工した以外は、比較例2と同様に作製した。
≪Manufacturing example≫
<Example 1>
(Preparation of emulsion type adhesive liquid)
Ion-exchanged water and n-octyl-3-mercaptopropionate, which is a chain transfer agent, are charged in a temperature-adjustable reaction vessel equipped with a thermometer, condenser, nitrogen introduction tube, and stirrer, and stirred with a stirrer under a nitrogen stream. After raising the temperature to 66 ° C., a solution prepared by dissolving 0.25 part of ammonium persulfate as a polymerization initiator in ion-exchanged water was added dropwise, and after 10 minutes, it consisted of 98 parts of 2-ethylhexyl acrylate and 2 parts of acrylic acid. The monomer mixture was continuously added with 3 parts of polyoxyethylene alkyl sulfate and a monomer emulsion obtained by emulsifying and dispersing in ion-exchanged water for 3.5 hours, and the reaction was continued at 66 ° C. for 2 hours to carry out polymerization. After completion, it was cooled. The mixture was filtered through a wire mesh or the like to obtain an acrylic copolymer emulsion pressure-sensitive adhesive liquid (A) having a solid content of 50%. The other emulsified polymers used in this example and the comparative example were produced and used according to the production example.
(Coating process)
Add 5% by weight ammonium hydrogencarbonate, 0.75% by weight cross-linking agent, 1% by weight thickener, and 2% by weight neutralizer to the total amount of the monomer in the pressure-sensitive adhesive liquid (A), and stir. Then, it was used as a coating liquid. After that, a peelable sheet (K8 Shiro E (R0): Lintec Co., Ltd.) whose base material is PVA-treated high-quality paper is fed out from the first feeding portion by a coater, and the coating amount after drying is 38 g / by a comma coater. Apply the coating liquid to a certain thickness so that it becomes m 2, and dry it in the heat-drying box of the next step. At the same time, decompose the foaming agent, generate gas, provide through holes in the adhesive layer, and dry. When the box is taken out, the polyester non-woven fabric (air permeability 0.2 seconds / 100 ml) unwound from the second feeding part is attached to the adhesive surface via a laminate roll, wound by the winding part, and supported / adhesive. An original winding sample consisting of three layers of agent / removable sheet was used.
(Preparation of pasting material)
The original winding sample was aged in an atmosphere of 40 ° C. for 3 days, cut into a constant size and shape, and subjected to each test.
<Example 2>
The patch material according to Example 2 was produced in the same manner as in Example 1 except that it was changed to a peelable sheet (78EVS (M): Oji F-Tex Co., Ltd.) having different Ra and RSm.
<Example 3>
The patch material according to Example 3 was produced in the same manner except that the base material of the peelable sheet was changed to glassine paper (64 GSM-L: Oji F-Tex Co., Ltd.) in Example 1.
<Example 4>
The patch material according to Example 4 was prepared in the same manner as in Example 3 except that 1% by weight of sodium dioctyl sulfosuccinate was added to the emulsion type pressure-sensitive adhesive liquid (A) and stirred. ..
<Comparative Examples 1 and 2>
Comparative Examples 1 and 2 are the same as in Example 4 except that the base material of the peelable sheet was changed to polylami woodfree paper (80EPS: Oji F-Tex Co., Ltd.) and polyester film (film binar: Fujimori Kogyo Co., Ltd.), respectively. It was produced in the same manner.
<Comparative example 3>
Comparative Example 3 was produced in the same manner as in Comparative Example 2 except that the foaming agent was not added to the emulsion type pressure-sensitive adhesive liquid (A) and the liquid was vigorously stirred with a homomixer to foam and then coated.

≪評価≫
<試験方法>
(A.粘着剤液の表面張力)
ウィルヘルミー式自動表面張力計(KRUSS社製)を用いて表面張力を常温常圧にて測定した。
(B.剥離性シート)
1.算術平均粗さ(Ra:JIS B 0601)
サーフコーダ(株式会社小坂研究所製)を用いてZ倍率10000の条件で表面粗さを計測した。レベリングは最小二乗法、ピッチは10μmとした。
2.粗さ曲面要素の平均長さ(RSm:JIS B 0601)
上記で計測したデータから、任意のXZ平面を取り出しRSmを計測、Y方向に10面測定し、平均値を求めた(X、Y、Z軸は図4を参照)。
(C.粘着剤層の貫通孔)
1.平均孔径
電子顕微鏡にて粘着剤表面の拡大写真を撮影し、この画像における貫通孔の直径を画像解析ソフトを用いて読み取り、画像上の貫通孔全ての直径の平均値を求めた。尚、孔形が完全な円形でない場合には最も長い部分を径とした。
2.発泡密度
上記拡大写真にてランダムに選択した1mm×1mmの四方形中の貫通孔数を読み取った。
3.開孔面積率
上記拡大写真にて、画像ソフトを用いて読み取り、貫通孔面積/貼付材面積を求めた。
(D.支持体)
1.透気度
下記のEに記載の方法と同様
(E.貼付材)
1.透気度
JIS P 8117に基づき、ガーレー式デンソメーター(テスター産業株式会社製)を用いて測定した。50mm×50mmの大きさに裁断し、剥離性シートを除去した試料を用意し、締付板(土台)に貼付した。この締付板を透過する面積は642mmの面積を有する。内側シリンダーを引出し、ストッパーにセットした後で、締付板の間に試験片を締付ける。内側シリンダーを静かに下降させ、100mlのエアーが通過する秒数(sec)を測定した。 ◎:0.1秒以上10秒未満 〇:10秒以上30秒未満 ×:30秒以上
2.薬剤透過性
薬剤(軟膏及びクリーム)を少量を指先に取り、試料片を宙に浮かせた状態で支持体背面側から塗り込み、透過して出てくる薬剤の様子・量を目視で確認した。次の基準で判定した。 ○:十分に透過した △:ある程度透過した ×:ほとんど透過しなかった
3.粘着力(耐水性)
15mm×75mmにカットしたサンプルを、同一人の前腕内側部にて右腕へ4本と左腕へ3本で近接して貼付し、通常に生活(シャワーを含む)し、72時間後に貼付状態を確認、100mm/minの速度、90°の角度で剥離した。○:サンプルの剥がれ、浮きがなく、粘着力が0.5N/15mm以上である ×:サンプルの剥がれや浮きがあり、粘着力が0.5N/15mm未満である
4.のり残り
粘着力測定時に、被着体である皮膚への剥離後の粘着剤残留の有無について、目視及びフィンガータックにて判定した。
<評価結果>
表1に評価結果を示す。

Figure 0006948131
≪Evaluation≫
<Test method>
(A. Surface tension of adhesive liquid)
The surface tension was measured at normal temperature and pressure using a Wilhelmy automatic surface tension meter (manufactured by KRUSS).
(B. Detachable sheet)
1. 1. Arithmetic Mean Roughness (Ra: JIS B 0601)
The surface roughness was measured using a surf coder (manufactured by Kosaka Laboratory Co., Ltd.) under the condition of a Z magnification of 10000. The leveling was the least squares method, and the pitch was 10 μm.
2. Roughness Average length of curved surface elements (RSm: JIS B 0601)
From the data measured above, an arbitrary XZ plane was taken out, RSm was measured, 10 planes were measured in the Y direction, and the average value was obtained (see FIG. 4 for the X, Y, and Z axes).
(C. Through hole of adhesive layer)
1. 1. Average pore size An enlarged photograph of the surface of the adhesive was taken with an electron microscope, the diameters of the through holes in this image were read using image analysis software, and the average value of the diameters of all the through holes on the image was obtained. When the hole shape is not a perfect circle, the longest part is used as the diameter.
2. Foaming Density The number of through holes in a 1 mm × 1 mm square randomly selected in the above enlarged photograph was read.
3. 3. Perforation area ratio The above-mentioned enlarged photograph was read using image software, and the through-hole area / patching material area was determined.
(D. Support)
1. 1. Air permeability Same as the method described in E below (E. pasting material)
1. 1. The air permeability was measured using a Garley type densometer (manufactured by Tester Sangyo Co., Ltd.) based on JIS P 8117. A sample was prepared by cutting into a size of 50 mm × 50 mm and removing the peelable sheet, and attached to a tightening plate (base). The area that penetrates the tightening plate has an area of 642 mm 2 . After pulling out the inner cylinder and setting it on the stopper, tighten the test piece between the tightening plates. The inner cylinder was gently lowered and the number of seconds (sec) through which 100 ml of air passed was measured. ⊚: 0.1 seconds or more and less than 10 seconds 〇: 10 seconds or more and less than 30 seconds ×: 30 seconds or more 2. A small amount of a drug-permeable drug (ointment and cream) was taken on the fingertips, and the sample piece was applied from the back side of the support while floating in the air, and the state and amount of the drug that permeated and came out were visually confirmed. Judgment was made according to the following criteria. ◯: Sufficiently transparent Δ: Somewhat transparent ×: Almost no transparency 3. Adhesive strength (water resistance)
A sample cut to 15 mm x 75 mm was pasted on the inner part of the forearm of the same person with 4 on the right arm and 3 on the left arm, and lived normally (including shower), and the pasted state was confirmed after 72 hours. Peeled at a speed of 100 mm / min and an angle of 90 °. ◯: There is no peeling or floating of the sample, and the adhesive strength is 0.5 N / 15 mm or more. ×: There is peeling or floating of the sample, and the adhesive strength is less than 0.5 N / 15 mm. At the time of measuring the adhesive strength of the adhesive residue, the presence or absence of adhesive residue after peeling to the skin as an adherend was determined visually and by finger tack.
<Evaluation result>
Table 1 shows the evaluation results.

Figure 0006948131

Claims (9)

支持体上に粘着剤層が積層された皮膚貼付用貼付材において、 In a patch material for skin patch in which an adhesive layer is laminated on a support,
前記粘着剤層が、発泡剤を含有するエマルション型粘着剤液が微細凹凸形状を有する剥離性シート上に適用された状態にて、前記発泡剤を分解させることにより形成された孔を有し、 The pressure-sensitive adhesive layer has holes formed by decomposing the foaming agent in a state where an emulsion-type pressure-sensitive adhesive liquid containing a foaming agent is applied on a peelable sheet having a fine uneven shape.
前記剥離性シートが、算術平均粗さ0.5〜3.0μm、粗さ曲面要素の平均長さ0.05〜0.20mmの凹凸を表面に有する The peelable sheet has irregularities on the surface having an arithmetic average roughness of 0.5 to 3.0 μm and an average length of a roughness curved surface element of 0.05 to 0.20 mm.
ことを特徴とする貼付材。A sticking material characterized by that.
前記孔が、前記粘着剤層を厚み方向に貫通する微細上下貫通孔であり、前記粘着剤層の全面に亘り多数形成されている、請求項1記載の貼付材。 The patch material according to claim 1, wherein the holes are fine vertical through holes that penetrate the pressure-sensitive adhesive layer in the thickness direction, and a large number of the holes are formed over the entire surface of the pressure-sensitive adhesive layer. 前記微細上下貫通孔の平均孔径が、20〜400μmである、請求項2記載の貼付材。 The sticking material according to claim 2, wherein the average hole diameter of the fine upper and lower through holes is 20 to 400 μm. 前記微細上下貫通孔の形状が、円柱状である、請求項2又は3記載の貼付材。 The patch material according to claim 2 or 3, wherein the shape of the fine upper and lower through holes is cylindrical. 前記粘着剤層における粘着剤層表面における前記微細上下貫通孔の面密度が、2〜100個/mm The surface density of the fine upper and lower through holes on the surface of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive layer is 2 to 100 pieces / mm. 2 である、請求項2〜4のいずれか一項記載の貼付材。The sticking material according to any one of claims 2 to 4. 前記粘着剤層表面積に対する前記微細上下貫通孔の開孔面積率が、3〜40%である、請求項2〜5のいずれか一項記載の貼付材。 The patch according to any one of claims 2 to 5, wherein the opening area ratio of the fine upper and lower through holes to the surface area of the pressure-sensitive adhesive layer is 3 to 40%. 前記貼付材の透気度が、0.1〜30sec/100mlである、請求項1〜6のいずれか一項記載の貼付材。 The patch according to any one of claims 1 to 6, wherein the patch has an air permeability of 0.1 to 30 sec / 100 ml. 支持体上に粘着剤層が積層された皮膚貼付用貼付材の製造方法において、
発泡剤を含有するエマルション型粘着剤液を、微細凹凸形状を有する剥離性シート上に適用し、前記発泡剤を分解させることにより孔を形成する工程
を含み、
前記剥離性シートが、算術平均粗さ0.5〜3.0μm、粗さ曲面要素の平均長さ0.05〜0.20mmの凹凸を表面に有することを特徴とする製造方法。
In a method for manufacturing a patch material for skin application in which an adhesive layer is laminated on a support,
The emulsion type adhesive solution containing a foaming agent was applied on a release sheet having a fine uneven shape, it viewed including the steps of forming a hole by decomposing the foaming agent,
A manufacturing method , wherein the peelable sheet has irregularities on the surface having an arithmetic average roughness of 0.5 to 3.0 μm and an average length of a roughness curved surface element of 0.05 to 0.20 mm.
前記エマルション型粘着剤液の表面張力が、35mN/m以下である、請求項記載の製造方法。
The production method according to claim 8 , wherein the surface tension of the emulsion-type pressure-sensitive adhesive liquid is 35 mN / m or less.
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