JP2018139733A - Skin-patching adhesive patch and its manufacturing method - Google Patents

Skin-patching adhesive patch and its manufacturing method Download PDF

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JP2018139733A
JP2018139733A JP2017034922A JP2017034922A JP2018139733A JP 2018139733 A JP2018139733 A JP 2018139733A JP 2017034922 A JP2017034922 A JP 2017034922A JP 2017034922 A JP2017034922 A JP 2017034922A JP 2018139733 A JP2018139733 A JP 2018139733A
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patch
adhesive layer
pressure
sensitive adhesive
skin
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JP6948131B2 (en
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明美佳 千田
Amika Chida
明美佳 千田
新史 渡邊
Arashi Watanabe
新史 渡邊
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Nichiban Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide means for prevention adhesive deposit in the peeling from skin while securing gas permeability being basic properties as a skin-patching adhesive patch.SOLUTION: A skin-patching adhesive patch is provided by laminating an adhesive layer on a gas permeability support. The skin-patching adhesive patch is characterized in that the pressure-sensitive adhesives constituting the adhesive layer are emulsion type pressure-sensitive adhesives, and many fine upper and lower through-holes penetrating through the adhesive layer in the thickness direction are formed over the entire surface of the adhesive layer.SELECTED DRAWING: Figure 1

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 skin patch 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。   It is desirable that the adhesive material to be applied to human skin such as a bandage, a dressing film, and a taping tape has 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 for the patch to have 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 suitably used for environmental protection. As a means for foaming the emulsion-type pressure-sensitive adhesive to increase the air permeability of the pressure-sensitive adhesive layer, mechanical foaming (aeration mixing) is generally performed (for example, Patent Document 1).

先行特許文献Prior patent documents

特開2004−84138号公報JP 2004-84138 A

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 described in Patent Document 1 has a problem in that it tends to cause residue when peeled from the skin. Then, an object of this invention is to provide the means which prevents the residue at the time of peeling from skin, ensuring the high air permeability which is a basic characteristic as a patch 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 patch, 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 upper and lower 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 patch.
The present invention (2) is the adhesive material according to the invention (1), wherein an average hole diameter of the fine upper and lower through holes is 20 to 400 μm.
The present invention (3) is the patch of the invention (1) or (2), wherein the shape of the fine upper and lower through holes is a columnar shape.
The present invention (4), the surface density of the fine vertical through hole in the adhesive layer surface of the adhesive layer is a 2 to 100 / mm 2, in patch of the invention (1) to (3) is there.
The present invention (5) is the adhesive material according to any one of the inventions (1) to (4), wherein an opening area ratio of the fine upper and lower through holes with respect to the pressure-sensitive adhesive layer surface area is 3 to 40%.
The present invention (6) is the patch according to any one of the inventions (1) to (5), wherein the air permeability of the patch is 0.1 to 30 sec / 100 ml.
The present invention (7) is a skin patch, in which an adhesive layer is laminated on a support,
The pressure-sensitive adhesive layer has pores 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 patch.
In the invention (8), the peelable sheet has irregularities having an arithmetic average roughness of 0.5 to 3.0 μm and an average length of the roughness curved surface element of 0.05 to 0.20 mm on the surface. 7) A patch.
The present invention (9) is a method for producing a skin patch, wherein a pressure-sensitive adhesive layer is laminated on a support.
It is a manufacturing method characterized by including the process of forming a hole by applying the emulsion type adhesive liquid containing a foaming agent on the peelable sheet which has fine uneven | corrugated shape, and decomposing | disassembling the said foaming agent.
In the invention (10), the peelable sheet has irregularities having an arithmetic average roughness of 0.5 to 3.0 μm and an average length of the roughness curved surface element of 0.05 to 0.20 mm on the surface. 9) The production method.
This invention (11) is a manufacturing method of the said invention (9) or (10) whose surface tension of the said emulsion type adhesive liquid is 35 mN / m or less.
This invention (12) is a manufacturing method of said invention (9)-(11) whose said patch for skin patches is the patch for skin patches of said invention (1)-(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。   ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the means which prevents the residue at the time of peeling from skin, ensuring the high air permeability which is the basic characteristic as a patch for skin sticking. Furthermore, according to the more preferable present invention, air permeability, sweat discharge, water resistance, and administration of a drug on the affected skin surface by applying a drug solution to the surface of the patch can be secured. In general, when the cohesive force is increased in order to prevent adhesive residue, the adhesive strength is reduced and the adhesion to the skin is significantly reduced. However, according to the present invention, it 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 an adhesive patch for skin application according to the present invention (an 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 the skin patch according to the present invention (an 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 an adhesive patch for skin application according to the present invention (an 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 (one example) by a surface roughness measuring instrument of a peelable sheet having irregularities on the surface when producing a skin patch according to the present invention.

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 for skin patch according to the present invention will be described in the following order.
1. 1. Overall structure and physical properties of the skin patch. Each part 2-1. Adhesive layer 2-1-1. Structure of adhesive layer 2-1-2. Material of adhesive layer 2-1-3. Physical properties of pressure-sensitive adhesive layer 2-2. 2. Air-permeable support 3. Method for producing skin patch material 3-1. Raw materials / used members 3-2. Process 4. Usage (application) of skin patch

≪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 properties of skin patch materials >>
As shown in FIG. 1 to FIG. 3, a patch 1 for skin patch according to the present invention constitutes the pressure-sensitive adhesive layer 1 </ b> A in a patch for skin patch in which a pressure-sensitive adhesive layer 1 </ b> A is laminated on a support 1 </ b> B. The pressure-sensitive adhesive is an emulsion-type pressure-sensitive adhesive, and 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. It is a patch. In addition, although not shown in figure, even if the peeling layer exists on the surface on the opposite side to the contact surface with the air-permeable support body 1B of the adhesive layer 1A, the patch 1 for skin sticking which concerns on this invention exists. (In addition, the release layer may be a peelable sheet used in the method for producing a patch for skin patch 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 skin patch 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 particularly preferably. 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.

・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 vertical through-holes 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. Here, the fine vertical through hole refers to a cylindrical hole formed in the vertical direction with respect 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. The shape of the through hole is preferably a columnar shape. In addition, as above-mentioned, a fine vertical through-hole is not specifically limited as long as it is a cylindrical hole (through-hole) formed in the up-down direction on the basis of the thickness direction of an adhesive layer, For example, it exists in an adhesive layer. It is not necessary for all of the fine upper and lower through holes to communicate from the surface of the pressure-sensitive adhesive layer to the gas-permeable support. Furthermore, 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 / mm 2 , more preferably 3 to 80 / mm 2 , and particularly 4 to 60 / mm 2 . 2 is desirable. Furthermore, the opening area ratio (opening ratio) of the fine upper and lower fine holes with respect to the adhesive layer surface area is preferably 3 to 40%, more preferably 5 to 30%. Within these ranges, better pressure-sensitive adhesive air permeability and pressure-sensitive adhesive properties tend to be realized. Thus, in order to ensure the basic characteristics (permeability, etc.) of the skin patch, in the prior art, bubbles were generated in a spongy form by mechanical foaming (aeration agitation). 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 use of an emulsion-type pressure-sensitive adhesive and the use of a gas-permeable support), the present inventors can not only realize the conventional basic characteristics but also at the time of peeling from the skin. It was found that an unexpected effect that the residue is significantly suppressed can be realized.

(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. Parts / Adhesive layer / Adhesive layer material)
As the emulsion-type pressure-sensitive adhesive according to the present invention, an acrylic pressure-sensitive adhesive is suitably used. Hereinafter, the emulsion type acrylic pressure-sensitive adhesive which is a preferred embodiment will be described in detail. In addition, in the following description, the description regarding the emulsion type adhesive liquid which is a raw material used for forming the said adhesive layer other than the description regarding the emulsion type acrylic adhesive which comprises an adhesive layer is also contained.

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 ester having 4 to 12 carbon atoms of alkyl group, 50 to 99.5% by weight, carboxyl group-containing monomer 0.5 to 10% by weight, and other An emulsion type acrylic system 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 as a component 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 4 to 12 carbon atoms in the alkyl group 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 the ester include butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, decyl acrylate, and the like. Moreover, you may use 1 type or in combination of 2 or more types.

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 has at least one carboxyl group and has a C═C double bond. For example, (meth) acrylic acid, maleic acid, itaconic acid, acrylic acid Examples thereof include carboxyl group-containing monomers such as 2-carboxyethyl, 2-acryloylethylsuccinic acid, and acrylic acid ω-carboxypolycaprolactone. Moreover, you may use 1 type or in combination of 2 or more types.

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 monomers such as (meth) acrylamide and N-methylolacrylamide, styrene, vinyl acetate, and the like. Vinyl monomers, epoxy group-containing monomers such as glycidyl (meth) acrylate, nitrile monomers such as (meth) acrylonitrile, 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. These monomers 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。   Surfactant as an emulsifier for emulsion polymerization is not particularly limited, and general ones can be adopted, specifically, polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan fatty acid ester, etc. Nonionic surfactants, anionic surfactants such as fatty acid soaps, alkyl sulfonates, alkyl succinates, polyoxyethylene alkyl sulfates, alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, benzalkonium chloride And amphoteric surfactants such as alkyldimethylaminoacetic acid betaine, alkyldimethylamine oxide, and alkylcarboxymethylhydroxyethylimidazolium betaine.

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。   There is no restriction | limiting in particular regarding emulsion polymerization, A well-known method, conditions, etc. are applicable. 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. Alternatively, a method may be used in which a part of the emulsion is polymerized and the remaining part is dropped continuously or intermittently for polymerization. The concentration of the surfactant with respect to the whole emulsion-type pressure-sensitive adhesive liquid is preferably 0.3 to 12% by weight, and the concentration of all monomers with respect to the whole emulsion-type pressure-sensitive adhesive liquid is preferably within the range of 30 to 70% by weight. To do. Examples of the polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate, and water-soluble azo compounds such as azobiscyanovaleric acid. The polymerization initiator is preferably used in an amount of 0.01 to 5 parts by weight with respect to 100 parts by weight of all 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。   For the emulsion type adhesive liquid prepared as described above, if necessary, additives such as antifoaming agent, thickener, preservative, chain transfer agent such as butyl mercaptan, dodecyl mercaptan, tackifier resin, etc. May be added. Moreover, a polyfunctional compound can also be added later to the emulsion-type pressure-sensitive adhesive liquid as a crosslinking agent. Further, a water-soluble foaming agent is used as the foaming agent added to the emulsion-type pressure-sensitive adhesive liquid. 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, and 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 preferred. Examples of the crosslinking agent include oxazoline group-containing water-soluble polymers, oxazoline group-containing polymer emulsions, epoxy group-containing resin emulsions, and carbodiimide group-containing water-soluble polymers. As the thickener, urethane association type, 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. The support for the patch of the present invention is not particularly limited, but preferably has good air permeability and / or 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 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, but is usually about 10,000 g / m 2 · day or less, preferably about 8,000 g / m 2 · day or less. For example, an air-permeable base material such as a nonwoven fabric or a felt-like fiber assembly, a plastic film subjected to perforation processing, a porous plastic film having micropores, or the like is used. Examples of the material of the nonwoven fabric or felt-like fiber assembly include natural fibers such as cotton, hemp, silk, hair, and rayon, and synthetic fibers such as polyamide, polyester, polyethylene, polypropylene, polyacryl, and polyvinyl chloride. In addition, as a plastic film that has been perforated, for example, a small hole is formed in a plastic film (sheet) such as polyethylene, polypropylene, nylon, polyester, polyvinyl chloride, etc. with a needle, laser, electric discharge machining, etc. to give air permeability. Can be mentioned. At this time, a small hole of 0.1 μm to 10 μm is provided as an opening diameter, but is not limited to this range, and is set so as to obtain a predetermined air permeability. As the porous film, for example, a polyolefin resin such as polyethylene or polypropylene, or a fluorine resin such as polytetrafluoroethylene, and an inorganic filler such as calcium carbonate, particularly those having an average particle size of 30 μm or less are extruded. What was made into a film by an appropriate method such as uniaxially or biaxially is used to make a porous film. Moreover, as a highly moisture permeable film, a polyurethane film can also be used as it is, for example. 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 skin surface by applying the drug solution to the surface, but a patch with excellent moisture permeability can be obtained. Moreover, when a nonwoven fabric is used as the support, those having a basis weight (basis weight) of about 10 to 200 g / m 2 are preferably used. Moreover, when using a plastic film, that whose thickness is about 10-200 micrometers is used preferably. Furthermore, in the present invention, these supports can be used as a single layer, or a laminate in which different 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 skin patch material>
(3-1. Raw materials and materials used)
Since the emulsion-type adhesive liquid and the air-permeable support among the raw materials and the used members used in the production of the skin patch according to the present invention have been described above, the peelable sheet as the used member will be described below. . The peelable sheet is used in a manner described in the following process. The peelable sheet is obtained by surface-treating a release agent (for example, silicone resin) on a base material. Here, the surface of the peelable sheet needs to be uneven. The irregularities preferably have an arithmetic average roughness (Ra) of 0.5 to 3.0 μm, and more preferably 0.8 to 2.0 μm. Moreover, the average length (RSm) of a roughness curved surface element is 0.05-0.20 mm, More preferably, it is 0.07-0.18 mm. The substrate is preferably made of paper. Of these, fine paper and glassine paper are preferred. Here, the fine paper refers to a western paper having a chemical pulp content of 100%. In the present invention, the high-quality paper is preferably of a type in which clay, resin emulsion, or polyvinyl alcohol (PVA) is surface-treated, capable of direct silicone treatment. Glassine paper is obtained by making paper using chemical pulp that has been subjected to a high level of beating treatment, and further densifying it with finishing equipment such as a super calender. Here, the reason why it is considered that when the peelable sheet is used, fine vertical through holes extending in the thickness direction can be formed. First, when the pressure-sensitive adhesive liquid is warmed on the peelable sheet, the foaming agent is decomposed and small bubbles are generated. Here, in order to form a large through-hole, it is necessary for the small bubbles to coalesce. When a peelable sheet with moderate unevenness (Ra) is used, the bubbles are merged using the concave portion as a scaffold. It is understood that they are united (unified in the vertical direction) In addition, it is understood that lateral coalescence (related to hole diameter) is related to RSm. In the case of a moderate Ra, the concave portion may not be used as a scaffold, but in this case, when the surface tension is lowered, the adhesive liquid tends to infiltrate into the concave portion and is easily affected by the unevenness. Therefore, it is understood that the coalescence of bubbles proceeds. On the other hand, in the case of a releasable sheet with low Ra and no undulation, there is no scaffolding in the first place, so it is presumed that even if the surface tension is lowered, the coalescence of bubbles does not progress 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 for skin patch according to the present invention will be described. The coater (sheet feeding unit, coater head, heating drying unit, winding unit is arranged in this order in a straight line, and the second sheet feeding unit is located above the winding unit, and the heating drying unit and winding unit. The emulsion-type pressure-sensitive adhesive solution polymerized on the peelable sheet that has been fed out is applied at a predetermined thickness with a coater head, and then heated to 80 to 130 ° C. in a heating and drying unit. A hot air of a certain degree is blown onto the coated surface (and / or by bringing the back side of the peelable sheet into contact with a Yankee dryer), and at the same time, the foaming agent is thermally decomposed to generate gas to form a pressure-sensitive adhesive layer having through holes. Next, the support sheet fed from the second sheet feeding unit is bonded to the pressure-sensitive adhesive surface via a laminating roll, and wound up by the winding unit. In this case, a release agent such as a silicone resin or a long-chain alkyl group-containing polymer is treated on a surface different from the surface to be bonded to the adhesive in advance, and the release sheet is peeled and removed again after lamination. The support on which the agent is transferred and laminated may be wound up as it is. The wound raw material is rolled into a suitable thin roll by a cutting machine, or the unraveled sheet is cut into an appropriate shape to obtain a patch.

<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. Usage of skin patch (application)>
The usage method (use) of the skin patch will be described. The patch for skin application according to the present invention is used for application to human skin. For example, a bandage, a dressing film, a taping tape, a transdermal absorption preparation, and a surgical tape can be mentioned.

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 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。
≪Production example≫
<Example 1>
(Preparation of emulsion type adhesive liquid)
Charged ion exchange water and chain transfer agent n-octyl-3-mercaptopropionate into a temperature-controllable reaction vessel equipped with a thermometer, condenser, nitrogen inlet tube, and stirrer. The temperature was raised to 66 ° C., and a solution prepared by dissolving 0.25 parts of ammonium persulfate as a polymerization initiator in ion-exchanged water was added dropwise. After 10 minutes, 98 parts of 2-ethylhexyl acrylate and 2 parts of acrylic acid were used. A monomer emulsion obtained by emulsifying and dispersing the monomer mixture in 3 parts of polyoxyethylene alkylsulfate and ion-exchanged water was continuously added in 3.5 hours, and the reaction was further continued at 66 ° C. for 2 hours. After completion, it was cooled. Filtration through a wire mesh or the like gave an acrylic copolymer emulsion pressure-sensitive adhesive liquid (A) having a solid content of 50%. In addition, the other emulsion polymer used by the present Example and the comparative example was manufactured according to the said manufacture example, and was used.
(Coating process)
In the adhesive liquid (A), 5% by weight of ammonium hydrogen carbonate, 0.75% by weight of a crosslinking agent, 1% by weight of a thickener, 2% by weight of a neutralizing agent are added and stirred with respect to the total amount of monomers. And it was set as the coating liquid. Thereafter, a peelable sheet (K8 Siro E (R0): Lintec Co., Ltd.) whose base material is PVA-treated fine paper is fed out from the first feeding portion with a coater, and the application amount after drying is 38 g / min with a comma coater. Apply the coating liquid with a certain thickness to m 2 and dry it in the heating and drying box of the next process. At the same time, decompose the foaming agent, generate gas, provide through-holes in the adhesive layer, and dry A polyester nonwoven fabric (air permeability: 0.2 sec / 100 ml) fed from the second feeding section when it comes out of the box is bonded to the adhesive surface via a laminating roll, wound up at the winding section, and supported / adhesive. An original sample consisting of three layers of agent / peelable sheet was used.
(Preparation of patch)
The original sample was aged for 3 days in an atmosphere of 40 ° C., then cut into a certain size and shape, and subjected to each test.
<Example 2>
The patch according to Example 2 was produced in the same manner as in Example 1 except that the peelable sheet (78EVS (M): Oji F-Tex Co., Ltd.) with different Ra and RSm was used.
<Example 3>
The patch according to Example 3 was produced in the same manner as in Example 1 except that the base material of the peelable sheet was changed to glassine paper (64GSM-L: Oji F-Tex Co., Ltd.).
<Example 4>
The patch according to Example 4 was prepared in the same manner as in Example 3 except that 1% by weight of sodium dioctylsulfosuccinate was added to the emulsion-type pressure-sensitive adhesive liquid (A) and stirred. .
<Comparative Examples 1 and 2>
Comparative Examples 1 and 2 were the same as in Example 4 except that the base material of the peelable sheet was changed to polyrami fine paper (80EPS: Oji F-Tex Co., Ltd.) and polyester film (film binder: Fujimori Kogyo Co., Ltd.). It produced similarly.
<Comparative Example 3>
Comparative Example 3 was prepared in the same manner as 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 and then foamed.

≪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 2018139733
≪Evaluation≫
<Test method>
(A. Surface tension of adhesive liquid)
The surface tension was measured at normal temperature and normal pressure using a Wilhelmy automatic surface tension meter (manufactured by KRUSS).
(B. Release sheet)
1. Arithmetic average roughness (Ra: JIS B 0601)
The surface roughness was measured using a surf coder (manufactured by Kosaka Laboratory Ltd.) at a Z magnification of 10,000. Leveling was the least square method, and the pitch was 10 μm.
2. Average length of roughness curved surface element (RSm: JIS B 0601)
An arbitrary XZ plane was taken out from the data measured above, RSm was measured, 10 planes were measured in the Y direction, and average values were obtained (refer to FIG. 4 for X, Y, and Z axes).
(C. Through-hole of adhesive layer)
1. An enlarged photograph of the pressure-sensitive adhesive surface was taken with an average hole diameter electron microscope, and the diameter of the through hole in this image was read using image analysis software, and the average value of the diameters of all the through holes on the image was determined. In addition, when the hole shape was not a perfect circle, the longest part was made into the diameter.
2. Foam density The number of through-holes in a 1 mm × 1 mm square selected at random in the above enlarged photograph was read.
3. Hole area ratio The above enlarged photograph was read using image software, and the area of the through hole / the area of the patch was determined.
(D. Support)
1. Air permeability The same as the method described in E below (E. patch)
1. The air permeability was measured using a Gurley type densometer (manufactured by Tester Sangyo Co., Ltd.) based on JIS P 8117. The sample which cut | judged to the magnitude | size of 50 mm x 50 mm and removed the peelable sheet was prepared, and it affixed on the clamping board (base). The area that passes through the clamping plate has an area of 642 mm 2 . Pull out the inner cylinder, set it on the stopper, and tighten the specimen between the clamping plates. The inner cylinder was gently lowered and the number of seconds (sec) through which 100 ml of air passed was measured. A: 0.1 seconds or more and less than 10 seconds O: 10 seconds or more and less than 30 seconds X: 30 seconds or more A small amount of the drug-permeable drug (ointment and cream) was taken on the fingertip, and the sample piece was applied from the back side of the sample with the sample piece suspended in the air, and the state and amount of the drug that permeated out were visually confirmed. Judgment was made according to the following criteria. ◯: Sufficiently transmitted Δ: Transmitted to some extent ×: Almost not transmitted Adhesive strength (water resistance)
A sample cut to 15mm x 75mm is attached in the forearm inner part of the same person in close proximity with 4 to the right arm and 3 to the left arm. And peeling at a speed of 100 mm / min and an angle of 90 °. ◯: The sample does not peel off and does not float, and the adhesive strength is 0.5 N / 15 mm or more. X: The sample peels off or floats, 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 the adhesive remaining after peeling to the skin as the adherend was determined by visual observation and finger tack.
<Evaluation results>
Table 1 shows the evaluation results.

Figure 2018139733

Claims (12)

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。
In the patch for skin patching in which the adhesive layer is laminated on the support,
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is an emulsion-type pressure-sensitive adhesive, and a large number of fine upper and lower through holes penetrating the pressure-sensitive adhesive layer in the thickness direction are formed over the entire surface of the pressure-sensitive adhesive layer. Characteristic patch material.
前記微細上下貫通孔の平均孔径が、20〜400μmである、請求項1記載の貼付材。   The patch according to claim 1, wherein an 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1又は2記載の貼付材。   The patch according to claim 1 or 2, wherein a shape of the fine upper and lower through holes is a columnar shape. 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、請求項1〜3のいずれか一項記載の貼付材。 The surface density of the fine vertical through hole in the adhesive layer surface of the adhesive layer is 2 to 100 / mm 2, the adhesive material of any one of claims 1 to 3. 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1〜4のいずれか一項記載の貼付材。   The patch according to any one of claims 1 to 4, wherein an opening area ratio of the fine upper and lower through holes with respect to a 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1〜5のいずれか一項記載の貼付材。   The patch according to any one of claims 1 to 5, wherein the air permeability of the patch is 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。
In the patch for skin patching in which the adhesive layer is laminated on the support,
The pressure-sensitive adhesive layer has pores 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. Characteristic patch material.
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、請求項7記載の貼付材。   The patch according to claim 7, wherein the peelable sheet has irregularities having an arithmetic average roughness of 0.5 to 3.0 μm and an average length of the roughness curved surface element of 0.05 to 0.20 mm on the surface. 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。
In the method for producing a patch for skin patching in which an adhesive layer is laminated on a support,
The manufacturing method characterized by including the process of forming a hole by applying the emulsion-type adhesive liquid containing a foaming agent on the peelable sheet which has a fine uneven | corrugated shape, and decomposing | disassembling the said foaming agent.
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、請求項9記載の製造方法。   The manufacturing method according to claim 9, wherein the peelable sheet has irregularities having an arithmetic average roughness of 0.5 to 3.0 μm and an average length of the roughness curved surface element of 0.05 to 0.20 mm on the surface. 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9又は10記載の製造方法。   The manufacturing method of Claim 9 or 10 whose surface tension of the said emulsion type adhesive liquid is 35 mN / m or less. 前記皮膚貼付用貼付材が、請求項1〜6のいずれか一項記載の皮膚貼付用貼付材である、請求項9〜11のいずれか一項記載の製造方法。   The manufacturing method according to any one of claims 9 to 11, wherein the patch for skin patch is the patch for skin patch according to any one of claims 1 to 6.
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JP2000128780A (en) * 1998-10-20 2000-05-09 Sanyo Chem Ind Ltd Cataplasm
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JP2008214474A (en) * 2007-03-02 2008-09-18 Nitto Denko Corp Adhesive sheet with release liner and release liner
JP2009273674A (en) * 2008-05-15 2009-11-26 Alcare Co Ltd Silicone adhesive agent for skin, silicone patch material for skin, and method for production thereof
JP2011512425A (en) * 2008-01-30 2011-04-21 エルテーエス ローマン テラピー−ジステーメ アーゲー Microstructured and / or nanostructured protective film or process film
JP2013248182A (en) * 2012-05-31 2013-12-12 Nichiban Co Ltd Water-repellent patch

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4655210A (en) * 1986-01-17 1987-04-07 Seton Company Foam bandage
JPH0711206A (en) * 1993-06-23 1995-01-13 Sekisui Chem Co Ltd Production of air-permeable self-adhesive tape
JP2000128780A (en) * 1998-10-20 2000-05-09 Sanyo Chem Ind Ltd Cataplasm
JP2007075132A (en) * 2005-09-09 2007-03-29 Nitto Denko Corp Medical adhesive tape or sheet
JP2008214474A (en) * 2007-03-02 2008-09-18 Nitto Denko Corp Adhesive sheet with release liner and release liner
JP2011512425A (en) * 2008-01-30 2011-04-21 エルテーエス ローマン テラピー−ジステーメ アーゲー Microstructured and / or nanostructured protective film or process film
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JP2013248182A (en) * 2012-05-31 2013-12-12 Nichiban Co Ltd Water-repellent patch

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