JP2008167787A - Adhesive agent composition for adhering to skin and skin adhesive material - Google Patents
Adhesive agent composition for adhering to skin and skin adhesive material Download PDFInfo
- Publication number
- JP2008167787A JP2008167787A JP2007001013A JP2007001013A JP2008167787A JP 2008167787 A JP2008167787 A JP 2008167787A JP 2007001013 A JP2007001013 A JP 2007001013A JP 2007001013 A JP2007001013 A JP 2007001013A JP 2008167787 A JP2008167787 A JP 2008167787A
- Authority
- JP
- Japan
- Prior art keywords
- skin
- pressure
- sensitive adhesive
- skin patch
- adhesive layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 66
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 42
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 117
- 239000007933 dermal patch Substances 0.000 claims description 95
- 239000010410 layer Substances 0.000 claims description 64
- 229920000058 polyacrylate Polymers 0.000 claims description 29
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 18
- -1 isocyanate compound Chemical class 0.000 claims description 13
- 238000004132 cross linking Methods 0.000 claims description 10
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Landscapes
- Materials For Medical Uses (AREA)
Abstract
Description
本発明は、皮膚貼付用粘着剤組成物と皮膚貼付材に関し、特に、長期貼付が可能で、かつ、良好な糊残り性を有する皮膚貼付用粘着剤組成物と皮膚貼付材に関する。 The present invention relates to a pressure-sensitive adhesive composition for skin application and a skin patch, and more particularly to a pressure-sensitive adhesive composition for skin application and a skin patch that can be applied for a long period of time and have good adhesive residue.
皮膚面に貼付して使用する皮膚貼付材は、通常、プラスチックや不織布の片面に皮膚貼付用粘着剤層を設けてなる。この皮膚貼付材は、救急絆創膏、ドレッシング材、皮膚面固定シート、経皮吸収薬を含有する皮膚貼付材等、様々な用途に適用されている。これらの皮膚貼付材は、いずれも粘着剤層を皮膚面に直接貼付して使用するものであり、粘着剤層には、皮膚面に対する接着性と、皮膚に対する低刺激性が要求される。また、皮膚貼付用基材を貼付後に皮膚から剥離した際に、粘着剤層が皮膚面へ残存する、いわゆる糊残りが生じないことが好ましい。粘着剤に対して要求されるこれらの特性は、皮膚貼付材を長期にわたって皮膚に貼付する場合には、特に重要になってくる。 The skin patch used by sticking on the skin surface is usually provided with a pressure-sensitive adhesive layer for skin patch on one surface of plastic or nonwoven fabric. This skin patch is applied to various uses such as an emergency bandage, a dressing material, a skin surface fixing sheet, and a skin patch containing a transdermal drug. These skin patches are used by directly sticking the pressure-sensitive adhesive layer to the skin surface, and the pressure-sensitive adhesive layer is required to have adhesion to the skin surface and low irritation to the skin. Moreover, when the skin sticking substrate is peeled off from the skin after sticking, it is preferable that the adhesive layer remains on the skin surface, so-called adhesive residue does not occur. These characteristics required for the adhesive are particularly important when the skin patch is applied to the skin over a long period of time.
しかしながら、人体の皮膚には皮脂、汗の分泌があり、これらが多く分泌される部位では皮脂等の影響によって皮膚貼付材の粘着剤層が液状化することがあり、粘着剤層の層状態を維持することが困難になって皮膚貼付材の貼付性能の低下を引き起こすことがある。したがって、皮膚貼付材を皮膚に長期間貼付し続けることは極めて難しく、従来の皮膚貼付材では要求される糊残り性などの特性を満足することはできなかった。 However, there is sebum and sweat secretion in the human skin, and the adhesive layer of the skin patch may be liquefied due to the effect of sebum etc. at the site where many of these are secreted. It may be difficult to maintain and may cause deterioration in the performance of the skin patch. Therefore, it is extremely difficult to keep the skin patch on the skin for a long period of time, and conventional skin patches cannot satisfy the properties such as adhesive residue required.
本発明は上記問題点を解決すべくなされたものであり、本発明は、長期貼付が可能であり、かつ、糊残り性が良好な皮膚貼付用粘着剤組成物および、この皮膚貼付用粘着剤組成物を用いて成る皮膚貼付材を提供することを目的とする。 The present invention has been made to solve the above problems, and the present invention provides an adhesive composition for skin application, which can be applied for a long period of time and has good adhesive residue, and the adhesive for skin application. An object is to provide a skin patch comprising the composition.
本発明の皮膚貼付用粘着剤組成物は、（メタ）アクリル酸エステルを主成分とするアクリル系ポリマーと球状のシリカとを含有する皮膚貼付用粘着剤組成物であって、該アクリル系ポリマーと球状のシリカとの合計重量が１００重量％に対し、球状のシリカを５重量％以上、３５重量％以下の比率で含有し、かつ、ポリマー成分に対するゲル分率が５％以上、６５％以下であることを特徴とする。 The pressure-sensitive adhesive composition for skin patch of the present invention is a pressure-sensitive adhesive composition for skin patch containing an acrylic polymer mainly composed of (meth) acrylic acid ester and spherical silica, When the total weight with the spherical silica is 100% by weight, the spherical silica is contained in a ratio of 5% by weight or more and 35% by weight or less, and the gel fraction with respect to the polymer component is 5% or more and 65% or less. It is characterized by being.
本発明の皮膚貼付材は、上記皮膚貼付用粘着剤組成物を用いてなる粘着剤層を有することを特徴とする。 The skin patch of the present invention has a pressure-sensitive adhesive layer formed using the above-mentioned pressure-sensitive adhesive composition for skin patch.
ここで、前記粘着剤層は架橋剤によって架橋処理されていることができる。
この架橋剤はイソシアネート系化合物であることができる。
Here, the pressure-sensitive adhesive layer may be crosslinked with a crosslinking agent.
The crosslinking agent can be an isocyanate compound.
本発明の皮膚貼付材は、さらに基材を有することができる。
前記基材は、不織布、織布、またはフィルムであることができる。
また、前記基材の材質は、ウレタン系樹脂、オレフィン系樹脂、エステル系樹脂、アクリル系樹脂、および、アミド系樹脂からなる群から選ばれる少なくとも１種であることができる。
The skin patch of the present invention can further have a substrate.
The substrate can be a nonwoven fabric, a woven fabric, or a film.
The base material may be at least one selected from the group consisting of urethane resins, olefin resins, ester resins, acrylic resins, and amide resins.
本発明においては、前記基材の厚みが、１０μｍ以上、２５０μｍ以下であることができる。 In this invention, the thickness of the said base material can be 10 micrometers or more and 250 micrometers or less.
本発明においては、さらに剥離処理された剥離シートを粘着剤層の上に有することができる。 In the present invention, a release sheet that has been further subjected to a release treatment can be provided on the pressure-sensitive adhesive layer.
本発明によれば、長期貼付が可能であり、かつ、糊残り性が良好な皮膚貼付用粘着剤組成物および、この皮膚貼付用粘着剤組成物を用いて成る皮膚貼付材を提供することができる。
According to the present invention, it is possible to provide an adhesive composition for skin application that can be applied for a long period of time and has a good adhesive residue, and a skin adhesive material using the adhesive composition for skin application. it can.
本発明の皮膚貼付用粘着剤組成物は、（メタ）アクリル酸エステルを主成分とするアクリル系ポリマーを含有し、さらに球状のシリカを含有する。球状のシリカの含有量は、（メタ）アクリル系ポリマー：球状のシリカ＝９５〜６５重量％：５〜３５重量％であり、９５〜９０重量％：５〜１０重量％であることが好ましく、約９０重量％：約１０重量％であることが特に好ましい。球状のシリカの含有量が５重量％より少ないと、長期貼付に対する接着効果がうすれ、球状のシリカの含有量が３５重量％より多いと、粘着性を阻害し、更には得られる粘着剤組成物の中で分散不良、粘着性低下等を生じる恐れがある。 The pressure-sensitive adhesive composition for skin application of the present invention contains an acrylic polymer mainly composed of (meth) acrylic acid ester, and further contains spherical silica. The content of spherical silica is (meth) acrylic polymer: spherical silica = 95 to 65% by weight: 5 to 35% by weight, preferably 95 to 90% by weight: 5 to 10% by weight, Particularly preferred is about 90% by weight: about 10% by weight. When the content of spherical silica is less than 5% by weight, the adhesive effect on long-term sticking is lost, and when the content of spherical silica is more than 35% by weight, the tackiness is inhibited, and furthermore, a pressure-sensitive adhesive composition is obtained. In such a case, there is a risk of causing poor dispersion and reduced adhesiveness.
本発明に用いられる球状のシリカは、無孔質でも多孔質でもよく、これらが混合されていてもよい。すなわち、球状の無孔質シリカ粉体および／または球状の多孔質シリカ粉体が使用される。使用される球状のシリカ粉体は、平均粒径が５〜６０μｍであることが好ましい。球状のシリカの平均粒径が５μ未満であると、継粉となりやすくて粘着剤中に均一に配合することが難しくなる。また、平均粒径が５μｍ未満であると、粘着剤の強度の保持が困難になる傾向にあると推測される。一方、球状シリカの平均粒径が６０μｍを超えると、粘着表面に凹凸が発生することがある。また、平均粒径が大きくなるほど球状シリカを粘着剤中に均一に分散させることが難しくなり品質にバラツキが生じやすくなる。 The spherical silica used in the present invention may be nonporous or porous, and these may be mixed. That is, spherical non-porous silica powder and / or spherical porous silica powder are used. The spherical silica powder used preferably has an average particle size of 5 to 60 μm. If the average particle size of the spherical silica is less than 5 μm, it is easy to become a spatter and it is difficult to mix it uniformly in the pressure-sensitive adhesive. Further, when the average particle size is less than 5 μm, it is presumed that it is difficult to maintain the strength of the pressure-sensitive adhesive. On the other hand, if the average particle size of the spherical silica exceeds 60 μm, irregularities may occur on the adhesive surface. Further, as the average particle size increases, it becomes more difficult to uniformly disperse the spherical silica in the pressure-sensitive adhesive, and the quality tends to vary.
本発明の皮膚貼付用粘着剤組成物に含まれるアクリル系ポリマーは、（メタ）アクリル酸エステルを主成分モノマーとする。例えば、（メタ）アクリル酸エステルを主成分モノマーとし、他の共重合性モノマーと共重合して得られるアクリル系ポリマーを用いることが好ましい。なお、本発明において、「（メタ）アクリル」と表記する場合には、アクリル、もしくはメタアクリルを意味するものとする。 The acrylic polymer contained in the adhesive composition for skin patch of the present invention contains (meth) acrylic acid ester as a main component monomer. For example, it is preferable to use an acrylic polymer obtained by copolymerizing (meth) acrylic acid ester as a main component monomer with another copolymerizable monomer. In the present invention, the expression “(meth) acryl” means acryl or methacryl.
上記（メタ）アクリル酸エステルとしては、（メタ）アクリル酸アルキルエステルが好ましいものとして挙げられる。（メタ）アクリル酸アルキルエステルとしては、具体的にはブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシルなどの炭素数が４〜１３の直鎖アルキル基または分岐アルキル基などのアルキル基を有する（メタ）アクリル酸アルキルエステルを用いることができる。本発明においては（メタ）アクリル酸アルキルエステルとして、これらの一種を単独で、あるいは、これらの二種以上を併用して用いることができる。 As said (meth) acrylic acid ester, (meth) acrylic-acid alkylester is mentioned as a preferable thing. Specific examples of the (meth) acrylic acid alkyl ester include straight-chain alkyl groups or branched alkyl groups having 4 to 13 carbon atoms such as butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl and the like. (Meth) acrylic acid alkyl ester having an alkyl group such as can be used. In the present invention, these (meth) acrylic acid alkyl esters can be used alone or in combination of two or more thereof.
なお、本発明に用いられる（メタ）アクリル酸アルキルエステルは上記例示のものに限定されるものではなく、粘着特性を著しく低下させない範囲であれば、炭素数１〜３の低級アルキル基を有する（メタ）アクリル酸アルキルエステル、炭素数１４以上の高級アルキル基を有する（メタ）アクリル酸アルキルエステルなどを併用しても良い。 The (meth) acrylic acid alkyl ester used in the present invention is not limited to those exemplified above, and has a lower alkyl group having 1 to 3 carbon atoms as long as the adhesive properties are not significantly reduced ( A (meth) acrylic acid alkyl ester and a (meth) acrylic acid alkyl ester having a higher alkyl group having 14 or more carbon atoms may be used in combination.
上記（メタ）アクリル酸エステルと共重合することができる他の共重合性モノマーとしては、共重合反応に関与する不飽和二重結合を分子内に少なくとも一個有すると共に、カルボキシル基（例えば（メタ）アクリル酸、イタコン酸、マレイン酸、無水マレイン酸など）、ヒドロキシル基（例えば（メタ）アクリル酸ヒドロキシエチルエステル、（メタ）アクリル酸ヒドロキシプロピルエステルなど）、スルホキシル基（例えばスチレンスルホン酸、アリルスルホン酸、（メタ）アクリル酸スルホプロピルエステル、（メタ）アクリル酸オキシナフタレンスルホン酸、アクリルアミドメチルプロパンスルホン酸など）、アミノ基(例えば（メタ）アクリル酸アミノエチルエステル、（メタ）アクリル酸ｔｅｒｔ−ブチルアミノエチルエステルなど)、アミド基（たとえば（メタ）アクリルアミド、ジメチル（メタ）アクリルアミド、Ｎ−ブチルアクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−メチロールプロパン（メタ）アクリルアミドなど）、アルコキシル基（例えば（メタ）アクリル酸メトキシエチルエステル、（メタ）アクリル酸エトキシエチルエステル、（メタ）アクリル酸メトキシエチレングリコールエステル、（メタ）アクリル酸メトキシジエチレングリコールエステル、（メタ）アクリル酸メトキシポリエチレングリコールエステル、（メタ）アクリル酸テトラヒドロフルフリルエステルなど）などの官能基を側鎖に有するモノマーを用いることができる。これら以外にも、共重合可能なモノマーとして、例えば、（メタ）アクリロニトリル、酢酸ビニル、プロピオン酸ビニル、Ｎ−ビニル−２−ピロリドン、メチルビニルピロリドン、ビニルピリジン、ビニルピペリドン、ビニルピリミジン、ビニルピペラジン、ビニルピラジン、ビニルピロール、ビニルイミダゾール、ビニルカプロラクタム、ビニルオキサゾール、ビニルモルホリンなどを用いることができる。 Other copolymerizable monomers that can be copolymerized with the (meth) acrylic acid ester include at least one unsaturated double bond involved in the copolymerization reaction in the molecule, and a carboxyl group (for example, (meth) Acrylic acid, itaconic acid, maleic acid, maleic anhydride, etc.), hydroxyl group (eg (meth) acrylic acid hydroxyethyl ester, (meth) acrylic acid hydroxypropyl ester etc.), sulfoxyl group (eg styrene sulfonic acid, allyl sulfonic acid) , (Meth) acrylic acid sulfopropyl ester, (meth) acrylic acid oxynaphthalene sulfonic acid, acrylamidomethylpropane sulfonic acid, etc.), amino group (for example, (meth) acrylic acid aminoethyl ester, (meth) acrylic acid tert-butylamino) Ethyl ester ), Amide groups (for example (meth) acrylamide, dimethyl (meth) acrylamide, N-butylacrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, etc.), alkoxyl groups (for example (meth) acrylic) Acid methoxyethyl ester, (meth) acrylic acid ethoxyethyl ester, (meth) acrylic acid methoxyethylene glycol ester, (meth) acrylic acid methoxydiethylene glycol ester, (meth) acrylic acid methoxypolyethylene glycol ester, (meth) acrylic acid tetrahydrofur A monomer having a functional group such as a furyl ester in the side chain can be used. Besides these, examples of copolymerizable monomers include (meth) acrylonitrile, vinyl acetate, vinyl propionate, N-vinyl-2-pyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinyl. Pyrazine, vinyl pyrrole, vinyl imidazole, vinyl caprolactam, vinyl oxazole, vinyl morpholine, and the like can be used.
これらの他の共重合性モノマー（官能性モノマー）などは一種もしくは二種以上を共重合することができる。粘着特性としての接着性や凝集性、また、必要に応じて行う粘着剤層の架橋処理する際の反応性などの点から、カルボキシル基含有モノマーおよびヒドロキシル基含有モノマーからなる群から選ばれる少なくとも一種を必須成分とし、必要に応じて、上記例示の他の共重合性モノマー、共重合可能なモノマーなどを共重合することが特に好ましい。上記他の共重合性モノマーなどの共重合量は、アクリル系ポリマーを構成する全モノマー（上記（メタ）アクリル酸アルキルエステルなどを含む）中、５０重量％以下、好ましくは２〜４０重量％の範囲となるように任意に設定することができる。 These other copolymerizable monomers (functional monomers) can be copolymerized singly or in combination. At least one selected from the group consisting of a carboxyl group-containing monomer and a hydroxyl group-containing monomer from the viewpoints of adhesiveness and cohesiveness as adhesive properties, and reactivity when crosslinking treatment of the pressure-sensitive adhesive layer is performed as necessary Is an essential component, and it is particularly preferable to copolymerize other copolymerizable monomers, copolymerizable monomers, etc., as necessary, as necessary. The copolymerization amount of the other copolymerizable monomer is 50% by weight or less, preferably 2 to 40% by weight in all monomers constituting the acrylic polymer (including the (meth) acrylic acid alkyl ester and the like). It can be arbitrarily set to be in the range.
本発明の皮膚貼付用粘着剤組成物は、上記（メタ）アクリル系ポリマーと球状シリカとを含むものであるが、形成される粘着剤層の凝集性を必要に応じてコントロールするために、架橋処理を施して粘着剤層を形成することができる。 The pressure-sensitive adhesive composition for skin patch of the present invention comprises the above (meth) acrylic polymer and spherical silica, but in order to control the cohesiveness of the pressure-sensitive adhesive layer to be formed, a crosslinking treatment is performed. It can be applied to form an adhesive layer.
架橋方法としては、紫外線照射、電子線照射などの放射線照射による物理的架橋、イソシアネート系化合物、有機過酸化物、有機金属塩、金属アルコラート、金属キレート、金属キレート化合物、多官能性化合物（多官能性外部架橋剤、ジアクリレートやジメタクリレートなどの多官能性内部架橋用モノマー）などの架橋剤を用いた化学的架橋などの架橋処理などが挙げられる。これらの架橋処理のうち、架橋反応性や加工度合いの調整のしやすさ、取扱い性の容易さの点から、三官能性イソシアネートなどのイソシアネート系化合物を用いた外部架橋処理を行うことが好ましい。例えば、イソシアネート系化合物としては、日本ポリウレタン工業株式会社製の「コロネートＬ」、「コロネートＨＬ」などを用いることができる。これらの架橋剤の配合量は、粘着剤組成物のアクリル系ポリマー１００重量部に対して０．０１〜１．０重量部程度であることが好ましい。 As the crosslinking method, physical crosslinking by radiation irradiation such as ultraviolet irradiation and electron beam irradiation, isocyanate compound, organic peroxide, organic metal salt, metal alcoholate, metal chelate, metal chelate compound, polyfunctional compound (polyfunctional compound) Cross-linking treatment such as chemical cross-linking using a cross-linking agent such as a functional external cross-linking agent or a polyfunctional internal cross-linking monomer such as diacrylate or dimethacrylate). Among these crosslinking treatments, it is preferable to perform an external crosslinking treatment using an isocyanate compound such as a trifunctional isocyanate from the viewpoint of easy adjustment of crosslinking reactivity, processing degree, and ease of handling. For example, as the isocyanate compound, “Coronate L”, “Coronate HL” manufactured by Nippon Polyurethane Industry Co., Ltd. can be used. It is preferable that the compounding quantity of these crosslinking agents is about 0.01-1.0 weight part with respect to 100 weight part of acrylic polymers of an adhesive composition.
皮膚貼付用粘着剤組成物には、必要に応じて、グリセリン、ポリエチレングリコール、ポリプロピレングリコールなどの多価アルコールに代表される可塑剤、ポリアクリル酸、ポリアクリル酸架橋体、ポリビニルピロリドンなどの水溶性又は吸水性の樹脂、ロジン系、テルペン系、石油系等の粘着付与剤、各種軟化剤、充填剤、顔料などの各種添加剤を配合することができる。 If necessary, the adhesive composition for skin application may be water-soluble such as plasticizers typified by polyhydric alcohols such as glycerin, polyethylene glycol, and polypropylene glycol, polyacrylic acid, crosslinked polyacrylic acid, and polyvinylpyrrolidone. Alternatively, water-absorbing resins, rosin-based, terpene-based, petroleum-based tackifiers, various softeners, fillers, pigments, and other various additives can be blended.
本発明の皮膚貼付用粘着剤組成物は、所定のゲル分率を有することが必要である。本発明においては、形成した粘着剤層のゲル分率がアクリル系ポリマー１００％に対して５％以上、６５％以下であることが必要であり、４０％以上、６５％以下であることが好ましい。ゲル分率が５％未満では、皮脂の分泌による影響で粘着剤層が液状化しやすく、皮膚に対して糊残りが生じることがある。一方、ゲル分率が６５％を越えると、長時間の接着性を維持することが困難になる。このように、特定範囲のゲル分率を有する粘着剤組成物を用いれば、形成された粘着剤層は、皮膚に長時間貼付することによって皮脂が分泌されたとしても接着力が低下することがなく、しかも、分泌された皮脂によって粘着剤層が液状化して、例えば極めてゆるいゼリー状態になることがないので、長時間貼付後の剥離時に糊残りが生じることはない。 The adhesive composition for skin patch of the present invention needs to have a predetermined gel fraction. In the present invention, the gel fraction of the formed pressure-sensitive adhesive layer is required to be 5% or more and 65% or less with respect to 100% of the acrylic polymer, and preferably 40% or more and 65% or less. . When the gel fraction is less than 5%, the pressure-sensitive adhesive layer tends to be liquefied due to the influence of sebum secretion, and adhesive residue may be generated on the skin. On the other hand, if the gel fraction exceeds 65%, it is difficult to maintain long-time adhesion. As described above, if a pressure-sensitive adhesive composition having a gel fraction in a specific range is used, the adhesive layer formed may be less adhesive even if sebum is secreted by applying it to the skin for a long time. Moreover, since the adhesive layer does not liquefy due to the secreted sebum and becomes, for example, a very loose jelly state, no adhesive residue is produced when peeling after sticking for a long time.
本発明の皮膚貼付材は、上記皮膚貼付用粘着剤組成物を用いて形成される。例えば、剥離処理された剥離シート上に粘着剤組成物を用いて粘着剤層を形成した後、剥離シートを剥がして、粘着剤層のみからなる皮膚貼付材を形成することができる。この場合には両面に粘着剤層が露出した皮膚貼付材、すなわち、両面粘着テープのように両面が接着可能な皮膚貼付材が形成される。あるいはまた、基材上に皮膚貼付用粘着剤組成物を用いて粘着剤層を形成することにより、基材の少なくとも一方の面に粘着剤層を有する皮膚貼付材を形成してもよい。なお、本発明の皮膚貼付材は、基材及び粘着剤層の他に他の層を有してもよいし、基材が２層以上の層からなってもよい。 The skin patch of the present invention is formed using the above adhesive composition for skin patch. For example, after a pressure-sensitive adhesive composition is used to form a pressure-sensitive adhesive composition on a release sheet that has been subjected to a release treatment, the release sheet is peeled off to form a skin patch consisting only of the pressure-sensitive adhesive layer. In this case, a skin patch having an adhesive layer exposed on both sides, that is, a skin patch capable of adhering both sides, such as a double-sided adhesive tape, is formed. Or you may form the skin patch which has an adhesive layer in at least one surface of a base material by forming an adhesive layer on the base material using the adhesive composition for skin sticking. In addition, the skin patch of this invention may have another layer other than a base material and an adhesive layer, and a base material may consist of two or more layers.
粘着剤層の厚みは、１０〜１５０μｍ程度の範囲内に設定することが好ましい。粘着剤層の厚みが１０μｍ未満では、皮膚に貼着中、十分な接着性が発揮されないことがある。また、厚みが１５０μｍを超えると、皮膚貼付材に要求されるレベルの水蒸気透過性が得られないことがあるので、耐汗性を付与しにくく、また、長期間の貼付によって皮膚刺激性を発現する場合がある。 The thickness of the pressure-sensitive adhesive layer is preferably set within a range of about 10 to 150 μm. When the thickness of the pressure-sensitive adhesive layer is less than 10 μm, sufficient adhesiveness may not be exhibited during sticking to the skin. If the thickness exceeds 150 μm, the level of water vapor permeability required for skin patches may not be obtained, making it difficult to impart sweat resistance and exhibiting skin irritation when applied for a long period of time. There is a case.
粘着剤層の形成方法としては、特に限定はないが、その一例を挙げれば、皮膚貼付用粘着剤組成物を必要に応じて溶剤等に溶解して塗布液を形成し、この塗布液を基材あるいは剥離処理したシートの一方の面に刷毛塗り、スプレーコーティング、ナイフコーティングなどにより付着せしめた後、必要に応じて溶媒等を除去し、次いで、加熱して硬化させることができる。ここで用いられる溶媒としては、ベンゼン、トルエン、キシレン、ナフサなどの芳香族系有機溶媒などが挙げられる。これらの溶媒の使用量は、例えば粘着剤層を形成するための作業性、粘度等を考慮して、適宜決定されることが好ましい。 The method for forming the pressure-sensitive adhesive layer is not particularly limited. For example, the adhesive composition for skin application is dissolved in a solvent or the like as necessary to form a coating solution. After adhering to one surface of the material or the release-treated sheet by brushing, spray coating, knife coating or the like, the solvent or the like can be removed if necessary, and then heated and cured. Examples of the solvent used here include aromatic organic solvents such as benzene, toluene, xylene, and naphtha. The amount of these solvents used is preferably determined as appropriate in consideration of, for example, workability and viscosity for forming the pressure-sensitive adhesive layer.
本発明の皮膚貼付材を構成する基材としては、粘着剤層を投錨性よく積層保持することができるものであることが好ましく、例えば、基材の材質がウレタン系樹脂、オレフィン系樹脂、エステル系樹脂、アクリル系樹脂およびアミド系樹脂からなる群から選ばれる少なくとも１種であることが好ましい。具体的には、ポリスチレン系の熱可塑性エラストマーフィルム、ポリエチレン、ポリプロピレン、エチレン／メタクリル酸共重合体、エチレン／メタクリル酸メチル共重合などのポリオレフィン系フィルム、エーテル系、エステル系などのポリウレタン系フィルム、ポリエステル系フィルム、各種プラスチック材料からなる織布や不織布、編布、紙などが挙げられ、その他にも、これらの積層体が挙げられ、例えば、フィルム同士の積層体、布帛や紙同士の積層体、フィルムと布帛との積層体などを用いることができる。 As the base material constituting the skin patch of the present invention, it is preferable that the pressure-sensitive adhesive layer can be laminated and held with good castability. For example, the base material is urethane resin, olefin resin, ester It is preferably at least one selected from the group consisting of a series resin, an acrylic resin, and an amide resin. Specifically, polystyrene-based thermoplastic elastomer film, polyethylene, polypropylene, ethylene / methacrylic acid copolymer, polyolefin-based film such as ethylene / methyl methacrylate copolymer, ether-based, ester-based polyurethane-based film, polyester, etc. Film, woven fabric and non-woven fabric made of various plastic materials, knitted fabric, paper, and the like. Besides, these laminates are mentioned, for example, laminates of films, laminates of fabrics and papers, A laminate of a film and a fabric can be used.
使用する基材の厚みは、材質、用途などによって適宜、決定することが好ましいが、通常、フィルムを基材とする場合には１０〜２５０μｍ程度であることが好ましく、更に好ましくは１０〜１００μｍ程度であり、織布や不織布などの布帛や紙などを基材とする場合には５０〜５００μｍ程度であることが好ましく、更に好ましくは１００〜３００μｍ程度である。なお、後者のように布帛、紙などを基材に用いる場合には、絶対厚みを測定することが困難であるので、坪量が８〜２００ｇ／ｍ２程度のものを用いることが好適である。 The thickness of the base material to be used is preferably determined as appropriate depending on the material, use, etc., but usually it is preferably about 10 to 250 μm, more preferably about 10 to 100 μm when a film is used as the base material. When the base material is a fabric such as a woven fabric or a non-woven fabric, or paper, the thickness is preferably about 50 to 500 μm, more preferably about 100 to 300 μm. In addition, when using cloth, paper, etc. as a base material like the latter, since it is difficult to measure absolute thickness, it is suitable to use a thing with a basis weight of about 8-200 g / m < 2 >. .
基材としては、これらのうち、感温性（温度変化に対して特性変化が少ない）や柔軟性（皮膚追従性）が良好で、適度な透湿性および引張強度を有することなどの点からポリウレタン系フィルムを用いることが好ましく、特にポリエステル系ポリウレタンフィルムまたはポリエーテル系ポリウレタンフィルムを用いることが好ましい。また、厚さが１５〜５０μｍのポリウレタン系フィルムを使用することによって、皮膚への追従性および密着性に優れ、かつ、フィルムの端縁部、すなわち皮膚との境界が目立たない皮膚貼付材とすることができる。 Among these, polyurethane is preferable from the viewpoints of temperature sensitivity (less characteristic change with respect to temperature change) and flexibility (skin followability), and appropriate moisture permeability and tensile strength. It is preferable to use a polyester film, and it is particularly preferable to use a polyester polyurethane film or a polyether polyurethane film. In addition, by using a polyurethane film having a thickness of 15 to 50 μm, a skin patch having excellent followability and adhesion to the skin, and the edge of the film, that is, the boundary with the skin is inconspicuous. be able to.
本発明の皮膚貼付材は、基材の露出表面の全部または一部に印刷を施してもよい。このように基材面に印刷を施した皮膚貼付材を皮膚に貼着すれば皮膚を装飾することができる。例えば、皮膚貼付材に刺青の模様を印刷しておけば、このような皮膚貼付材を貼着することによって、簡単に皮膚に刺青を施したように模すことができる。また、ピアスの模様を印刷した皮膚貼付材を耳朶に貼付すれば、ピアスを付けたように模すことができるし、ホクロの印刷を施した皮膚貼付材を顔面等に貼付すれば、ホクロをつけた顔ができあがる。 The skin patch of the present invention may be printed on all or part of the exposed surface of the substrate. Thus, the skin can be decorated by sticking the skin patch with the substrate surface printed on the skin. For example, if a tattoo pattern is printed on the skin patch, it can be imitated as if the skin was tattooed by sticking such a skin patch. In addition, if a skin patch with a pierced pattern printed on it is applied to the earlobe, it can be imitated with a piercing, and if a skin patch with a mole printed on it is applied to the face, the mole The attached face is completed.
基材に印刷を施すことによって形成された印刷層は、基材表面の耐磨耗性を向上させると共に、滑り性を向上させることができる。例えば滑り性が悪いと皮膚面へ貼付使用している最中に、衣服などと擦れることによって、シート端部に捲くれ（剥がれ）などが生じやすい。ところが、印刷層を熱融着や塗工処理によって支持体の露出表面に形成すれば、これらの欠点を解消することができる。 The printed layer formed by printing on the substrate can improve the wear resistance of the surface of the substrate and improve the slipperiness. For example, if the slipperiness is poor, the sheet end tends to be crushed (peeled) by rubbing against clothes during application to the skin surface. However, these defects can be eliminated if the printed layer is formed on the exposed surface of the support by heat-sealing or coating.
印刷層は、アクリル系樹脂やブチラール樹脂、ポリ塩化ビニル樹脂、塩化ビニル／酢酸ビニル共重合樹脂、エチルセルロース、ポリウレタンなどを主成分とするものを用いて形成することができる。防水性などを向上させるためには印刷層を形成したのち、その上にシリコーン系またはフッ素系の撥水処理剤などを塗布することが好ましい。 The printing layer can be formed using an acrylic resin, butyral resin, polyvinyl chloride resin, vinyl chloride / vinyl acetate copolymer resin, ethyl cellulose, polyurethane, or the like as a main component. In order to improve waterproofness, it is preferable to form a printing layer and then apply a silicone-based or fluorine-based water repellent agent or the like thereon.
基材として透湿性がないフィルムなどを用いた皮膚貼付材を皮膚面に長時間貼付すると、貼付部位にムレが生じ、その結果、皮膚カブレなどを起こすことがある。従って、透湿性がない基材を用いる場合、あるいは、透湿性を有する基材を用いる場合であっても更に透湿性を付与したい場合には、基材及び粘着剤層に穿孔処理を施すことが好ましい。穿孔処理は、穿孔ロールによる方法や、パンチング、レーザ照射などの方法を用いて施すことができる。施される穿孔の大きさは、孔径が０．２〜２ｍｍ程度であることが好ましい。 When a skin patch using a non-moisture permeable film or the like as a base material is applied to the skin surface for a long time, the applied site may become stuffy, resulting in skin fogging. Therefore, when using a base material that does not have moisture permeability, or when using a base material that has moisture permeability, if it is desired to impart moisture permeability, the base material and the pressure-sensitive adhesive layer may be subjected to perforation treatment. preferable. The perforating process can be performed by a method using a perforating roll, a method such as punching or laser irradiation. As for the size of the perforations to be applied, the hole diameter is preferably about 0.2 to 2 mm.
本発明の皮膚貼付材は、粘着剤層表面の中央域に吸液性パッドを設けて救急絆創膏としてもよい。吸液性パッドとしては、例えばガーゼ、綿布、不織布、脱脂綿と不織布との複合品、脱脂綿と編ネットとの複合品などを用いることができる。吸液パッドは、創傷部からの滲出液を吸収し、しかも創傷部を保護することができる。また、これ以外の医療用テープやシートとしても利用することができる。 The skin patch of the present invention may be provided as a first-aid adhesive bandage by providing a liquid-absorbing pad in the central area of the adhesive layer surface. As the liquid absorbent pad, for example, gauze, cotton cloth, nonwoven fabric, a composite product of absorbent cotton and nonwoven fabric, a composite product of absorbent cotton and knitted net, or the like can be used. The liquid absorption pad can absorb exudate from the wound part and protect the wound part. It can also be used as other medical tapes and sheets.
本発明の皮膚貼付材は、皮膚に物品を固定するための貼着手段として使用することもできる。例えば、両面に粘着剤層が露出している皮膚貼付材は、かつらを頭皮に固定するための貼着手段として、あるいは、装飾品などを皮膚に固定するための貼着手段として利用することができる。また、本発明の皮膚貼付材は、使い捨て用かつらの部材として利用することもできるし、金属製品が直に肌に触れないように金属製品と皮膚との間に介入させる部材として利用することもできる。
The skin patch of the present invention can also be used as a sticking means for fixing an article to the skin. For example, a skin patch with an adhesive layer exposed on both sides can be used as a sticking means for fixing a wig to the scalp or as a sticking means for fixing a decorative article to the skin. it can. Further, the skin patch of the present invention can be used as a member for a disposable wig, or can be used as a member for intervening between the metal product and the skin so that the metal product does not directly touch the skin. it can.
以下に実施例を示し、本発明をさらに具体的に説明するが、本発明はこれらに限定されるものではなく、本発明の技術的思想を逸脱しない範囲内で種々の応用が可能である。なお、以下の実施例において、「部」とあるのは「重量部」を意味する。また、以下の実施例において使用された測定方法及び評価方法を下記に示す。 The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples, and various applications are possible without departing from the technical idea of the present invention. In the following examples, “part” means “part by weight”. The measurement methods and evaluation methods used in the following examples are shown below.
<測定方法及び評価方法>
（１）粘着剤層のゲル分率（アクリル系ポリマー成分に換算）の測定
粘着剤組成物の乾燥後の所定量（約１ｇ）を初期重量として測定する。ただし、粘着剤組成物中のシリカの配合比率からシリカの重量を算出しておく。この粘着剤組成物を、ポリテトラフルオロエチレン膜（日東電工株式会社製のＮＴＦ膜、平均孔径０．２μｍ）に入れて試料とする。この試料の重量を測定した後、トルエン中にて、常温で７日間抽出した後試料を取り出し、乾燥後の試料の重量を測定する。重量法にてポリマー残渣（不溶分）を求め、ポリマーの初期重量のアクリル系ポリマー成分１００に換算し、それに対する残渣（不溶分）の割合をゲル分率として算出する。
<Measurement method and evaluation method>
(1) Measurement of gel fraction (converted to acrylic polymer component) of pressure-sensitive adhesive layer A predetermined amount (about 1 g) after drying of the pressure-sensitive adhesive composition is measured as an initial weight. However, the weight of silica is calculated from the mixing ratio of silica in the pressure-sensitive adhesive composition. This pressure-sensitive adhesive composition is put into a polytetrafluoroethylene membrane (NTF membrane manufactured by Nitto Denko Corporation, average pore size 0.2 μm) to make a sample. After measuring the weight of this sample, it is extracted in toluene at room temperature for 7 days, then the sample is taken out, and the weight of the dried sample is measured. A polymer residue (insoluble matter) is obtained by a weight method, converted to the acrylic polymer component 100 of the initial weight of the polymer, and the ratio of the residue (insoluble matter) to the polymer weight is calculated as a gel fraction.
（２）皮膚接着力の評価
皮膚貼付材を１．７ｃｍ×１．３ｃｍの大きさに切断して試験用サンプルとした。この試験用サンプルをボランティア６人の額に５日間貼着して接着性の評価を行った。ただし、評価は下記基準に基づいて点数を付け、その点数の平均値を求めた。
評価基準：
５点 剥がれが生じなかった
４点 試験用サンプルの周囲に剥がれが認められたがしっかり接着していた
３点 試験用サンプルの面積の１／３程度に剥がれが認められた
２点 試験用サンプルの面積の２／３程度に剥がれが認められた
１点 剥がれた
(2) Evaluation of skin adhesive strength The skin patch was cut into a size of 1.7 cm × 1.3 cm to obtain a test sample. This test sample was attached to the forehead of 6 volunteers for 5 days to evaluate adhesion. However, the evaluation was scored based on the following criteria, and the average value of the scores was obtained.
Evaluation criteria:
5 points 4 points where peeling did not occur 3 points where peeling was observed around the test sample but firmly adhered 2 points where peeling was observed about 1/3 of the area of the test sample One point where peeling was observed in about 2/3 of the area.
（３）糊残り性の評価
上記「（２）皮膚接着力の評価」において、評価後に使用した試験用サンプルを剥離して糊残り性の評価を行った。すなわち、剥離後の皮膚面を肉眼で観察し、糊残りが生じたか否か評価を行った。ただし、評価は下記基準に基づいて行った。
評価基準：
５点 糊残りの発生が認められない
４点 貼付材の周囲または端部に多少糊残りが発生したが問題ない程度である
３点 糊残りが発生し、その面積は貼付材の面積の１／３程度である
２点 糊残りが発生し、その面積は貼付材の面積の２／３程度である
１点 貼付材の面積の全面積に糊残りが発生した
(3) Evaluation of adhesive residue In the above "(2) Evaluation of skin adhesive strength", the test sample used after the evaluation was peeled off to evaluate the adhesive residue. That is, the skin surface after peeling was observed with the naked eye, and it was evaluated whether or not adhesive residue was generated. However, the evaluation was performed based on the following criteria.
Evaluation criteria:
5 points No adhesive residue is observed 4 points Adhesive residue is slightly generated around or at the edge of the patch, but there is no problem 3 points Adhesive residue is generated, the area of which is 1 / of the adhesive material area 2 points, which is about 3 glue residue is generated, and the area is about 2/3 of the area of the adhesive material. 1 point The adhesive residue is generated in the entire area of the adhesive material.
（実施例１）
アクリル酸イソノニルエステル９５部とアクリル酸５部を、重合溶媒としての酢酸エチルと共に反応容器内に仕込み、重合開始剤としての過酸化ベンゾイル０．２部の存在下、常法によって重合反応を行い、アクリル系ポリマーを得た。得られたアクリル系ポリマーの固形分濃度は５５重量％であった。
(Example 1)
95 parts of isononyl acrylate and 5 parts of acrylic acid are charged into a reaction vessel together with ethyl acetate as a polymerization solvent, and a polymerization reaction is carried out in the usual manner in the presence of 0.2 part of benzoyl peroxide as a polymerization initiator. An acrylic polymer was obtained. The resulting acrylic polymer had a solid content concentration of 55% by weight.
次に、上記アクリル系ポリマーと球状のシリカ粉体として平均粒径６．２μｍの球状の無孔質シリカ（固形分１００％）とを用い、固形分の重量比で、アクリル系ポリマー：球状の無孔質シリカ＝９０：１０となるように混合して粘着剤組成物を作製した。この粘着剤組成物と、溶媒として酢酸エチルを用い、固形分濃度が３５％の粘着剤溶液を作製した。このようにして得られた粘着剤溶液を、片面をシリコーン系離型剤にて処理したセパレータの離型処理面に、乾燥後の厚みが６０μｍとなるように塗布し、乾燥して粘着剤層を形成した。 Next, using the acrylic polymer and spherical nonporous silica (solid content: 100%) having an average particle diameter of 6.2 μm as the spherical silica powder, the acrylic polymer: spherical It mixed so that it might become nonporous silica = 90: 10, and the adhesive composition was produced. Using this pressure-sensitive adhesive composition and ethyl acetate as a solvent, a pressure-sensitive adhesive solution having a solid concentration of 35% was prepared. The pressure-sensitive adhesive solution thus obtained was applied to a release-treated surface of a separator whose one surface was treated with a silicone-based release agent so that the thickness after drying was 60 μm, and dried to obtain a pressure-sensitive adhesive layer. Formed.
次いで、形成された粘着剤層を、３０μｍ厚のポリエステル系ポリウレタンフィルムの片面に転着して本発明の皮膚貼付材を作製した。
得られた皮膚貼付材について、ゲル分率を求めたところ５０％であった。
Subsequently, the formed pressure-sensitive adhesive layer was transferred onto one side of a 30 μm thick polyester polyurethane film to prepare the skin patch of the present invention.
With respect to the obtained skin patch, the gel fraction was determined to be 50%.
（実施例２）
球状のシリカ粉体として平均粒径６．２μｍの球状の多孔質シリカを用いた以外は実施例１と同様にして、すなわち、球状の多孔質シリカと、実施例１において用いたアクリル系ポリマーとを、固形分の重量比率が９０：１０の割合となるように混合した以外は、実施例１と同様にして、皮膚貼付用粘着剤組成物を作製した。また、実施例１と同様にして皮膚貼付材を作製した。ただし、粘着剤層のゲル分率は５０％であった。
(Example 2)
Except for using spherical porous silica having an average particle size of 6.2 μm as the spherical silica powder, the same procedure as in Example 1, that is, the spherical porous silica and the acrylic polymer used in Example 1 were used. Was mixed in the same manner as in Example 1 except that the weight ratio of the solid content was 90:10. A skin patch was prepared in the same manner as in Example 1. However, the gel fraction of the pressure-sensitive adhesive layer was 50%.
（実施例３）
実施例１において作製した粘着剤組成物を用いて、実施例１と同様にして粘着剤溶液を調整した。このようにして得られた粘着剤溶液を、片面がシリコーン系離型剤にて処理されたセパレータの離型処理面に、乾燥後の厚みが６０μｍとなるように塗布し、乾燥して粘着剤層を形成した。ただし、乾燥条件を適宜調節してゲル分率が１０％の粘着剤層を得た。
(Example 3)
Using the pressure-sensitive adhesive composition prepared in Example 1, a pressure-sensitive adhesive solution was prepared in the same manner as in Example 1. The pressure-sensitive adhesive solution thus obtained was applied to a release-treated surface of a separator whose one side was treated with a silicone-based mold release agent so that the thickness after drying was 60 μm, and dried to obtain a pressure-sensitive adhesive. A layer was formed. However, the pressure-sensitive adhesive layer having a gel fraction of 10% was obtained by appropriately adjusting the drying conditions.
次いで、形成された粘着剤層を、３０μｍ厚のポリエステル系ポリウレタンフィルムの片面に転着して本発明の皮膚貼付材を作製した。 Subsequently, the formed pressure-sensitive adhesive layer was transferred onto one side of a 30 μm thick polyester polyurethane film to prepare the skin patch of the present invention.
（実施例４）
実施例２において作製した粘着剤組成物を用いて、実施例１と同様にして粘着剤溶液を調整した。このようにして得られた粘着剤溶液を、片面がシリコーン系離型剤にて処理されたセパレータの離型処理面に、乾燥後の厚みが６０μｍとなるように塗布し、乾燥して粘着剤層を形成した。ただし、乾燥条件を適宜調節してゲル分率が１０％の粘着剤層を得た。
Example 4
Using the pressure-sensitive adhesive composition prepared in Example 2, a pressure-sensitive adhesive solution was prepared in the same manner as in Example 1. The pressure-sensitive adhesive solution thus obtained was applied to a release-treated surface of a separator whose one side was treated with a silicone-based mold release agent so that the thickness after drying was 60 μm, and dried to obtain a pressure-sensitive adhesive. A layer was formed. However, the pressure-sensitive adhesive layer having a gel fraction of 10% was obtained by appropriately adjusting the drying conditions.
次いで、形成された粘着剤層を、３０μｍ厚のポリエステル系ポリウレタンフィルムの片面に転着して本発明の皮膚貼付材を作製した。 Subsequently, the formed pressure-sensitive adhesive layer was transferred onto one side of a 30 μm thick polyester polyurethane film to prepare the skin patch of the present invention.
（実施例５）
実施例１において作製した粘着剤組成物を用いて、実施例１と同様にして粘着剤溶液を調整した。このようにして得られた粘着剤溶液を、片面がシリコーン系離型剤にて処理されたセパレータの離型処理面に、乾燥後の厚みが６０μｍとなるように塗布し、乾燥して粘着剤層を形成した。ただし、乾燥条件を適宜調節してゲル分率が２０％の粘着剤層を得た。
(Example 5)
Using the pressure-sensitive adhesive composition prepared in Example 1, a pressure-sensitive adhesive solution was prepared in the same manner as in Example 1. The pressure-sensitive adhesive solution thus obtained was applied to a release-treated surface of a separator whose one side was treated with a silicone-based mold release agent so that the thickness after drying was 60 μm, and dried to obtain a pressure-sensitive adhesive. A layer was formed. However, the pressure-sensitive adhesive layer having a gel fraction of 20% was obtained by appropriately adjusting the drying conditions.
次いで、形成された粘着剤層を、３０μｍ厚のポリエステル系ポリウレタンフィルムの片面に転着して本発明の皮膚貼付材を作製した。 Subsequently, the formed pressure-sensitive adhesive layer was transferred onto one side of a 30 μm thick polyester polyurethane film to prepare the skin patch of the present invention.
（実施例６）
実施例２において作製した粘着剤組成物を用いて、実施例１と同様にして粘着剤溶液を調整した。このようにして得られた粘着剤溶液を、片面がシリコーン系離型剤にて処理されたセパレータの離型処理面に、乾燥後の厚みが６０μｍとなるように塗布し、乾燥して粘着剤層を形成した。ただし、乾燥条件を適宜調節してゲル分率が２０％の粘着剤層を得た。
(Example 6)
Using the pressure-sensitive adhesive composition prepared in Example 2, a pressure-sensitive adhesive solution was prepared in the same manner as in Example 1. The pressure-sensitive adhesive solution thus obtained was applied to a release-treated surface of a separator whose one side was treated with a silicone-based mold release agent so that the thickness after drying was 60 μm, and dried to obtain a pressure-sensitive adhesive. A layer was formed. However, the pressure-sensitive adhesive layer having a gel fraction of 20% was obtained by appropriately adjusting the drying conditions.
次いで、形成された粘着剤層を、３０μｍ厚のポリエステル系ポリウレタンフィルムの片面に転着して本発明の皮膚貼付材を作製した。 Subsequently, the formed pressure-sensitive adhesive layer was transferred onto one side of a 30 μm thick polyester polyurethane film to prepare the skin patch of the present invention.
（比較例１）
実施例１において作製した粘着剤組成物を用いて、実施例１と同様にして粘着剤溶液を調整した。このようにして得られた粘着剤溶液を、片面がシリコーン系離型剤にて処理されたセパレータの離型処理面に、乾燥後の厚みが６０μｍとなるように塗布し、乾燥して粘着剤層を形成した。ただし、乾燥条件を適宜調節してゲル分率が０％の粘着剤層を得た。
(Comparative Example 1)
Using the pressure-sensitive adhesive composition prepared in Example 1, a pressure-sensitive adhesive solution was prepared in the same manner as in Example 1. The pressure-sensitive adhesive solution thus obtained was applied to a release-treated surface of a separator whose one side was treated with a silicone-based mold release agent so that the thickness after drying was 60 μm, and dried to obtain a pressure-sensitive adhesive. A layer was formed. However, the pressure-sensitive adhesive layer having a gel fraction of 0% was obtained by appropriately adjusting the drying conditions.
次いで、形成された粘着剤層を、３０μｍ厚のポリエステル系ポリウレタンフィルムの片面に転着して本発明の皮膚貼付材を作製した。 Subsequently, the formed pressure-sensitive adhesive layer was transferred onto one side of a 30 μm thick polyester polyurethane film to prepare the skin patch of the present invention.
（比較例２）
実施例２において作製した粘着剤組成物を用いて、実施例１と同様にして粘着剤溶液を調整した。このようにして得られた粘着剤溶液を、片面がシリコーン系離型剤にて処理されたセパレータの離型処理面に、乾燥後の厚みが６０μｍとなるように塗布し、乾燥して粘着剤層を形成した。ただし、乾燥条件を適宜調節してゲル分率が０％の粘着剤層を得た。
(Comparative Example 2)
Using the pressure-sensitive adhesive composition prepared in Example 2, a pressure-sensitive adhesive solution was prepared in the same manner as in Example 1. The pressure-sensitive adhesive solution thus obtained was applied to a release-treated surface of a separator whose one side was treated with a silicone-based mold release agent so that the thickness after drying was 60 μm, and dried to obtain a pressure-sensitive adhesive. A layer was formed. However, the pressure-sensitive adhesive layer having a gel fraction of 0% was obtained by appropriately adjusting the drying conditions.
次いで、形成された粘着剤層を、３０μｍ厚のポリエステル系ポリウレタンフィルムの片面に転着して本発明の皮膚貼付材を作製した。 Subsequently, the formed pressure-sensitive adhesive layer was transferred onto one side of a 30 μm thick polyester polyurethane film to prepare the skin patch of the present invention.
（比較例３）
実施例１において作製した粘着剤組成物を用いて、実施例１と同様にして粘着剤溶液を調整した。このようにして得られた粘着剤溶液を、片面がシリコーン系離型剤にて処理されたセパレータの離型処理面に、乾燥後の厚みが６０μｍとなるように塗布し、乾燥して粘着剤層を形成した。ただし、乾燥条件を適宜調節して、ゲル分率が７０％の粘着剤層を得た。
(Comparative Example 3)
Using the pressure-sensitive adhesive composition prepared in Example 1, a pressure-sensitive adhesive solution was prepared in the same manner as in Example 1. The pressure-sensitive adhesive solution thus obtained was applied to a release-treated surface of a separator whose one side was treated with a silicone-based mold release agent so that the thickness after drying was 60 μm, and dried to obtain a pressure-sensitive adhesive. A layer was formed. However, the pressure-sensitive adhesive layer having a gel fraction of 70% was obtained by appropriately adjusting the drying conditions.
次いで、形成された粘着剤層を、３０μｍ厚のポリエステル系ポリウレタンフィルムの片面に転着して本発明の皮膚貼付材を作製した。 Subsequently, the formed pressure-sensitive adhesive layer was transferred onto one side of a 30 μm thick polyester polyurethane film to prepare the skin patch of the present invention.
（比較例４）
実施例２において作製した粘着剤組成物を用いて、実施例１と同様にして粘着剤溶液を調整した。このようにして得られた粘着剤溶液を、片面がシリコーン系離型剤にて処理されたセパレータの離型処理面に、乾燥後の厚みが６０μｍとなるように塗布し、乾燥して粘着剤層を形成した。ただし、乾燥条件を適宜調節してゲル分率が７０％の粘着剤層を得た。
(Comparative Example 4)
Using the pressure-sensitive adhesive composition prepared in Example 2, a pressure-sensitive adhesive solution was prepared in the same manner as in Example 1. The pressure-sensitive adhesive solution thus obtained was applied to a release-treated surface of a separator whose one side was treated with a silicone-based mold release agent so that the thickness after drying was 60 μm, and dried to obtain a pressure-sensitive adhesive. A layer was formed. However, the pressure-sensitive adhesive layer having a gel fraction of 70% was obtained by appropriately adjusting the drying conditions.
次いで、形成された粘着剤層を、３０μｍ厚のポリエステル系ポリウレタンフィルムの片面に転着して本発明の皮膚貼付材を作製した。 Subsequently, the formed pressure-sensitive adhesive layer was transferred onto one side of a 30 μm thick polyester polyurethane film to prepare the skin patch of the present invention.
実施例１〜６、比較例１〜４で得られた皮膚貼付材について、皮膚接着性の評価と糊残り性の評価を行った。その結果をそれぞれ表１および表２に示す。 The skin adhesives obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were evaluated for skin adhesiveness and adhesive residue. The results are shown in Table 1 and Table 2, respectively.
（実施例７）
アクリル酸２−エチルヘキシルエステル６５部、アクリル酸２−メトキシエチルエステル３０部、及び、アクリル酸５部を、重合溶媒としての酢酸エチルと共に反応容器内に仕込み、重合開始剤としてのアゾビスイソブチロニトリル０．２部の存在下、常法によって重合反応を行い、アクリル系ポリマーを得た。
(Example 7)
65 parts of acrylic acid 2-ethylhexyl ester, 30 parts of acrylic acid 2-methoxyethyl ester and 5 parts of acrylic acid are charged into a reaction vessel together with ethyl acetate as a polymerization solvent, and azobisisobutyroyl as a polymerization initiator. In the presence of 0.2 part of nitrile, a polymerization reaction was performed by a conventional method to obtain an acrylic polymer.
次に、得られたアクリル系ポリマーと球状のシリカ粉末として平均粒径６．２μｍの球状の無孔質シリカ（固形分１００％）とを用い、これらを固形分の重量比が９０：１０の割合となるように混合して粘着剤組成物を作製した。この粘着剤組成物、および、溶媒として酢酸エチルを用い、固形分濃度が３５％の粘着剤溶液を作製した。このようにして得られた粘着剤溶液を、片面をシリコーン系離型剤にて処理したセパレータの離型処理面に、乾燥後の厚みが６０μｍとなるように塗布し、乾燥して粘着剤層を形成した。 Next, using the obtained acrylic polymer and spherical nonporous silica (solid content: 100%) having an average particle size of 6.2 μm as the spherical silica powder, the weight ratio of the solid content is 90:10 A pressure-sensitive adhesive composition was prepared by mixing in proportions. Using this pressure-sensitive adhesive composition and ethyl acetate as a solvent, a pressure-sensitive adhesive solution having a solid concentration of 35% was prepared. The pressure-sensitive adhesive solution thus obtained was applied to a release-treated surface of a separator whose one surface was treated with a silicone-based release agent so that the thickness after drying was 60 μm, and dried to obtain a pressure-sensitive adhesive layer. Formed.
次いで、形成された粘着剤層を、３０μｍ厚のポリエステル系ポリウレタンフィルムの片面に転着して本発明の皮膚貼付材を作製した。
得られた皮膚貼付材について、ゲル分率を求めたところ５０％であった。
Subsequently, the formed pressure-sensitive adhesive layer was transferred onto one side of a 30 μm thick polyester polyurethane film to prepare the skin patch of the present invention.
With respect to the obtained skin patch, the gel fraction was determined to be 50%.
（実施例８）
球状のシリカ粉体として平均粒径６．２μｍの球状の多孔質シリカを用いた以外は実施例１と同様にして、すなわち、実施例７において用いたアクリル系ポリマーと、球状の多孔質シリカとを、固形分の重量比が９０：１０の割合となるように混合した以外は、実施例７と同様にして、皮膚貼付用粘着剤組成物を作製した。また、得られた皮膚貼付用粘着剤を用いた以外は実施例７と同様にして、皮膚貼付材を作製した。ただし、粘着剤層のゲル分率は５０％であった。
(Example 8)
Except for using spherical porous silica having an average particle size of 6.2 μm as the spherical silica powder, the same procedure as in Example 1, that is, the acrylic polymer used in Example 7, the spherical porous silica, and Was mixed in the same manner as in Example 7 except that the weight ratio of the solid content was 90:10. Thus, a pressure-sensitive adhesive composition for skin application was prepared. Further, a skin patch was prepared in the same manner as in Example 7 except that the obtained adhesive for skin patch was used. However, the gel fraction of the pressure-sensitive adhesive layer was 50%.
（実施例９）
実施例７において用いたアクリル系ポリマーと球状の無孔質シリカとを、固形分の重量比が８０：２０の割合となるように混合した以外は、実施例７と同様にして、皮膚貼付用粘着剤組成物を作製した。また、得られた皮膚貼付用粘着剤組成物を用いた以外は実施例７と同様にして、皮膚貼付材を作製した。ただし、粘着剤層のゲル分率は５０％であった。
Example 9
For skin patch application in the same manner as in Example 7, except that the acrylic polymer used in Example 7 and spherical nonporous silica were mixed so that the weight ratio of the solid content was 80:20. A pressure-sensitive adhesive composition was prepared. In addition, a skin patch was prepared in the same manner as in Example 7 except that the obtained adhesive composition for skin patch was used. However, the gel fraction of the pressure-sensitive adhesive layer was 50%.
（実施例１０）
実施例８において用いたアクリル系ポリマーと球状の多孔質シリカとを、固形分の重量比が８０：２０の割合となるように混合した以外は実施例８と同様にして、皮膚貼付用粘着剤組成物を作製した。また、得られた皮膚貼付用粘着剤組成物を用いた以外は実施例７と同様にして、皮膚貼付材を作製した。ただし、粘着剤層のゲル分率は５０％であった。
(Example 10)
Adhesive for skin application in the same manner as in Example 8 except that the acrylic polymer used in Example 8 and spherical porous silica were mixed so that the weight ratio of the solid content was 80:20. A composition was prepared. In addition, a skin patch was prepared in the same manner as in Example 7 except that the obtained adhesive composition for skin patch was used. However, the gel fraction of the pressure-sensitive adhesive layer was 50%.
（実施例１１）
実施例７において用いたアクリル系ポリマーと球状の無孔質シリカとを、固形分の重量比が７０：３０の割合となるように混合した以外は、実施例７と同様にして、皮膚貼付用粘着剤組成物を作製した。また、得られた皮膚貼付用粘着剤組成物を用いた以外は実施例７と同様にして、皮膚貼付材を作製した。ただし、粘着剤層のゲル分率は５０％であった。
(Example 11)
For skin patch application in the same manner as in Example 7, except that the acrylic polymer used in Example 7 and spherical nonporous silica were mixed so that the weight ratio of the solid content was 70:30. A pressure-sensitive adhesive composition was prepared. In addition, a skin patch was prepared in the same manner as in Example 7 except that the obtained adhesive composition for skin patch was used. However, the gel fraction of the pressure-sensitive adhesive layer was 50%.
（実施例１２）
実施例８において用いたアクリル系ポリマーと球状の多孔質シリカとを、固形分の重量比が７０：３０の割合となるように混合した以外は、実施例８と同様にして、皮膚貼付用粘着剤組成物を作製した。また、得られた皮膚貼付用粘着剤組成物を用いた以外は実施例７と同様にして、皮膚貼付材を作製した。ただし、粘着剤層のゲル分率は５０％であった。
(Example 12)
Adhesive for skin application in the same manner as in Example 8, except that the acrylic polymer used in Example 8 and spherical porous silica were mixed so that the weight ratio of the solid content was 70:30. An agent composition was prepared. In addition, a skin patch was prepared in the same manner as in Example 7 except that the obtained adhesive composition for skin patch was used. However, the gel fraction of the pressure-sensitive adhesive layer was 50%.
（比較例５）
球状のシリカ粉体は使用せずに、実施例７において用いたアクリル系ポリマーのみを用いて粘着剤組成物とした。このアクリル系ポリマーのみからなる粘着剤組成物を、酢酸エチルに入れ、実施例７と同様にして、皮膚貼付用粘着剤組成物を作製した。また、得られた皮膚貼付用粘着剤組成物を用いた以外は実施例７と同様にして、皮膚貼付材を作製した。ただし、粘着剤層のゲル分率は５０％であった。
(Comparative Example 5)
A spherical silica powder was not used, and only the acrylic polymer used in Example 7 was used to form an adhesive composition. The pressure-sensitive adhesive composition consisting only of this acrylic polymer was put in ethyl acetate, and a pressure-sensitive adhesive composition for skin application was prepared in the same manner as in Example 7. In addition, a skin patch was prepared in the same manner as in Example 7 except that the obtained adhesive composition for skin patch was used. However, the gel fraction of the pressure-sensitive adhesive layer was 50%.
（比較例６）
実施例７において用いたアクリル系ポリマーと球状の無孔質シリカとを、固形分の重量比が６０：４０の割合となるように混合した以外は、実施例７と同様にして、皮膚貼付用粘着剤組成物を作製した。また、得られた皮膚貼付用粘着剤組成物を用いた以外は実施例７と同様にして、皮膚貼付材を作製した。ただし、粘着剤層のゲル分率は５０％であった。
(Comparative Example 6)
For skin patch application in the same manner as in Example 7, except that the acrylic polymer used in Example 7 and spherical nonporous silica were mixed so that the weight ratio of the solid content was 60:40. A pressure-sensitive adhesive composition was prepared. In addition, a skin patch was prepared in the same manner as in Example 7 except that the obtained adhesive composition for skin patch was used. However, the gel fraction of the pressure-sensitive adhesive layer was 50%.
（比較例７）
実施例８において用いたアクリル系ポリマーと球状の多孔質シリカ粉体とを、固形分の重量比が６０：４０の割合となるように混合した以外は、実施例８と同様にして、皮膚貼付用粘着剤組成物を作製した。また、得られた皮膚貼付用粘着剤組成物を用いた以外は実施例７と同様にして、皮膚貼付材を作製した。ただし、粘着剤層のゲル分率は５０％であった。
(Comparative Example 7)
The skin patch was applied in the same manner as in Example 8 except that the acrylic polymer used in Example 8 and the spherical porous silica powder were mixed so that the weight ratio of the solid content was 60:40. A pressure-sensitive adhesive composition was prepared. In addition, a skin patch was prepared in the same manner as in Example 7 except that the obtained adhesive composition for skin patch was used. However, the gel fraction of the pressure-sensitive adhesive layer was 50%.
実施例７〜１２、比較例５〜７で得られた皮膚貼付材について、皮膚接着性の評価と糊残り性の評価を行った。その結果をそれぞれ表２および表３に示す。 The skin adhesives obtained in Examples 7 to 12 and Comparative Examples 5 to 7 were evaluated for skin adhesiveness and adhesive residue. The results are shown in Table 2 and Table 3, respectively.
表１から明らかなように、実施例１〜６の皮膚貼付材は平均値が４．０以上の優れた皮膚接着性を示し、かつ、糊残り性の評価においても平均値が４．０以上であり優れた結果が得られた。
一方、表２から明らかなように、比較例１〜２の皮膚貼付材は、皮膚接着性および糊残り性の両方に劣っていた。また、比較例３〜４の皮膚貼付材は、糊残り性は良好であったが、皮膚接着性に劣っていた。
As is apparent from Table 1, the skin patches of Examples 1 to 6 showed excellent skin adhesion with an average value of 4.0 or more, and the average value was 4.0 or more in the evaluation of adhesive residue. Excellent results were obtained.
On the other hand, as is clear from Table 2, the skin patch materials of Comparative Examples 1 and 2 were inferior in both skin adhesiveness and adhesive residue. Moreover, although the adhesive adhesive property of the skin patch of Comparative Examples 3-4 was favorable, it was inferior to skin adhesiveness.
また、表３から明らかなように、実施例７〜１２の皮膚貼付材は平均値が４．０以上の優れた皮膚接着性を示し、かつ、糊残り性の評価においても平均値が４．０以上であり優れた結果が得られた。
一方、表４から明らかなように、比較例５〜７の皮膚貼付材は、皮膚接着性および糊残り性の両方に劣っていた。また、とりわけ比較例６〜７の皮膚貼付材は、皮膚接着性に劣っていた。
Further, as apparent from Table 3, the skin patch materials of Examples 7 to 12 showed excellent skin adhesion with an average value of 4.0 or more, and the average value was 4. Excellent results were obtained with a value of 0 or more.
On the other hand, as is clear from Table 4, the skin patches of Comparative Examples 5 to 7 were inferior in both skin adhesiveness and adhesive residue. Moreover, especially the skin patch of Comparative Examples 6-7 was inferior to skin adhesiveness.
すなわち、本発明によれば、長期貼付が可能で、かつ、剥離後において問題のある糊残りが生じることがない皮膚貼付用粘着剤組成物および皮膚貼付材を得ることができた。 That is, according to the present invention, it was possible to obtain a pressure-sensitive adhesive composition for skin patch and a skin patch that can be applied for a long period of time and that does not cause a problematic adhesive residue after peeling.
本発明の皮膚貼付用粘着剤組成物は皮膚への長期貼付が可能であり、かかる用途に適応することができる。また、本発明の皮膚貼付材は、種々の大きさのシート状、テープ状等の形態で使用することができ、また、ロール状形態で保存することもできる。これらの皮膚貼付材は、皮膚貼付用途、例えば医療衛生分野、外用用途等の分野で使用することができ、具体的には、絆創膏、粘着包帯、ドレッシング材等に好適に使用される。 The pressure-sensitive adhesive composition for skin application of the present invention can be applied to the skin for a long period of time, and can be applied to such applications. In addition, the skin patch of the present invention can be used in the form of sheets and tapes of various sizes, and can also be stored in a roll form. These skin patch materials can be used in the fields of skin patch application, for example, medical hygiene field, external use, and the like. Specifically, they are suitably used for bandages, adhesive bandages, dressing materials and the like.
Claims (9)
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| WO2013180008A1 (en) * | 2012-05-28 | 2013-12-05 | ニチバン株式会社 | Sebum-absorbent pasting material, and method for manufacturing same |
| JP2015193162A (en) * | 2014-03-31 | 2015-11-05 | リンテック株式会社 | carrier sheet and laminate |
| JP2016067358A (en) * | 2014-09-26 | 2016-05-09 | 東洋紡株式会社 | Adhesive film for emergency adhesive tape, and emergency adhesive tape using the adhesive film |
| JP6149148B1 (en) * | 2016-12-07 | 2017-06-14 | 株式会社アートネイチャー | Wig pressure-sensitive adhesive and method of using the wig pressure-sensitive adhesive |
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| WO2013180008A1 (en) * | 2012-05-28 | 2013-12-05 | ニチバン株式会社 | Sebum-absorbent pasting material, and method for manufacturing same |
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| JP2015193162A (en) * | 2014-03-31 | 2015-11-05 | リンテック株式会社 | carrier sheet and laminate |
| JP2016067358A (en) * | 2014-09-26 | 2016-05-09 | 東洋紡株式会社 | Adhesive film for emergency adhesive tape, and emergency adhesive tape using the adhesive film |
| JP6149148B1 (en) * | 2016-12-07 | 2017-06-14 | 株式会社アートネイチャー | Wig pressure-sensitive adhesive and method of using the wig pressure-sensitive adhesive |
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| JP4912159B2 (en) | 2012-04-11 |
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