JP2018075057A - Skin-pasting pressure sensitive adhesive sheet, and production method thereof - Google Patents
Skin-pasting pressure sensitive adhesive sheet, and production method thereof Download PDFInfo
- Publication number
- JP2018075057A JP2018075057A JP2016216989A JP2016216989A JP2018075057A JP 2018075057 A JP2018075057 A JP 2018075057A JP 2016216989 A JP2016216989 A JP 2016216989A JP 2016216989 A JP2016216989 A JP 2016216989A JP 2018075057 A JP2018075057 A JP 2018075057A
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- adhesive layer
- pressure
- hot
- skin
- 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
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 151
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000010410 layer Substances 0.000 claims abstract description 107
- 239000006260 foam Substances 0.000 claims abstract description 32
- 239000004831 Hot glue Substances 0.000 claims abstract description 19
- 239000012943 hotmelt Substances 0.000 claims description 80
- 239000000853 adhesive Substances 0.000 claims description 54
- 230000001070 adhesive effect Effects 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 11
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- 230000005540 biological transmission Effects 0.000 claims 1
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Images
Abstract
Description
本発明は、皮膚に貼り付ける用途の粘着シートに関する。 The present invention relates to a pressure-sensitive adhesive sheet for use on a skin.
絆創膏、サージカルテープ、心電図測定用の電極固定用シート等のように、医療分野で
使用される粘着シートには、その粘着性の高さからアクリル系重合体が一般的に使用されている。しかし、アクリル系重合体は合成後に未反応のモノマーが残留し易く、アクリル系重合体を使用した粘着シートを、皮膚に貼付すると発疹等の炎症の原因となる場合がある。
そのため、炎症の原因物質を含まないホットメルト粘着剤を使用した粘着シートが使用される場合が多い。
しかし、ホットメルト粘着剤を使用した粘着シートは、粘着剤層に透湿性が無いため、皮膚に貼付して長時間が経過すると、汗が粘着剤層を透過できず滞留して、皮膚の蒸れやかゆみの原因になっていた。
Acrylic polymers are generally used for adhesive sheets used in the medical field, such as adhesive bandages, surgical tapes, and electrode fixing sheets for electrocardiogram measurement, because of their high adhesiveness. However, unreacted monomers tend to remain after the synthesis of the acrylic polymer, and if an adhesive sheet using the acrylic polymer is applied to the skin, it may cause inflammation such as a rash.
For this reason, an adhesive sheet using a hot-melt adhesive that does not contain inflammation-causing substances is often used.
However, the pressure-sensitive adhesive sheet using hot-melt pressure-sensitive adhesive does not have moisture permeability in the pressure-sensitive adhesive layer, so that after a long time has passed since it was applied to the skin, sweat cannot permeate the pressure-sensitive adhesive layer and stay in the skin. It was a cause of itching.
そこで、特許文献1および特許文献2には、ホットメルト粘着剤の透湿性確保を目的として一定パターンの開口部を有する粘着剤層を用いた粘着シートが開示されている。
In view of this,
しかし、従来の粘着シートは、粘着剤層の開口部には透湿性があったが、非開口部には透湿性が無いため、粘着剤層の非開口部と接する皮膚に蒸れやかゆみが発生する問題があった。 However, conventional pressure-sensitive adhesive sheets have moisture permeability in the opening of the pressure-sensitive adhesive layer, but the non-opening is not moisture-permeable, so stuffiness and itching occur on the skin in contact with the non-opening of the pressure-sensitive adhesive layer. There was a problem to do.
本発明は、皮膚に長時間貼付した場合に蒸れやかゆみが生じ難い、皮膚貼付用粘着シートおよびその製造方法の提供を目的とする。 An object of the present invention is to provide a pressure-sensitive adhesive sheet for skin application and a method for producing the same, which are less likely to cause stuffiness or itching when applied to the skin for a long time.
本発明の皮膚貼付用粘着シートは、通気性フォーム体、およびホットメルト粘着剤層(A)を備え、前記ホットメルト粘着剤層(A)は、表面の空隙率が5〜50%であり、1平方ミリメートル当たりに円相当径が10〜400μmの孔を2個以上有する。 The pressure-sensitive adhesive sheet for skin application of the present invention comprises a breathable foam body and a hot-melt pressure-sensitive adhesive layer (A), and the hot-melt pressure-sensitive adhesive layer (A) has a surface porosity of 5 to 50%, Two or more holes having an equivalent circle diameter of 10 to 400 μm per square millimeter are provided.
上記の本発明によれば、ホットメルト粘着剤層(A)は、一定面積当たり所定の貫通孔を有することで適度な表面空隙率を有する。そのため、汗等の水分が粘着剤層を通過し、さらに通気性フォーム体を通じて放出されやすくなることで、皮膚の蒸れやかゆみを抑制できる。 According to the present invention described above, the hot melt pressure-sensitive adhesive layer (A) has an appropriate surface porosity by having predetermined through holes per certain area. Therefore, moisture such as sweat passes through the pressure-sensitive adhesive layer, and is easily released through the breathable foam body, so that it is possible to suppress skin stuffiness and itching.
本発明により皮膚に長時間貼付した場合に蒸れやかゆみが生じ難い、皮膚貼付用粘着シートおよびその製造方法を提供できる。 According to the present invention, it is possible to provide a pressure-sensitive adhesive sheet for skin application and a method for producing the same, which are less likely to cause stuffiness or itching when applied to the skin for a long time.
本発明の皮膚貼付用粘着シート(以下、単に「粘着シート」という)は、通気性フォーム体、およびホットメルト粘着剤層(A)を備え、前記ホットメルト粘着剤層(A)は、表面の空隙率が5〜50%であり、1平方ミリメートル当たりに円相当径が10〜400μmの孔を2個以上有する。なお、本明細書で粘着シート、粘着テープおよび粘着フィルムは同義語である。 The pressure-sensitive adhesive sheet for skin application of the present invention (hereinafter simply referred to as “pressure-sensitive adhesive sheet”) includes a breathable foam body and a hot-melt pressure-sensitive adhesive layer (A), and the hot-melt pressure-sensitive adhesive layer (A) The porosity is 5 to 50%, and there are two or more holes having a circle equivalent diameter of 10 to 400 μm per square millimeter. In addition, in this specification, an adhesive sheet, an adhesive tape, and an adhesive film are synonymous.
本発明の粘着シートは、もともと皮膚を刺激し難い成分で構成されたホットメルト粘着剤を用いた粘着シートである。後述するが一定の透湿性を有するホットメルト粘着剤層(A)の塗工形状は、いわゆるベタ塗りの粘着剤層、開口部を有するパターン状の粘着剤層、あるいは、点状ないし島状のように粘着剤層が連続しないパターンの粘着剤層であっても良い。 The pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet that uses a hot-melt pressure-sensitive adhesive originally composed of components that are difficult to irritate the skin. As will be described later, the coating shape of the hot-melt pressure-sensitive adhesive layer (A) having a certain moisture permeability is a so-called solid pressure-sensitive adhesive layer, a patterned pressure-sensitive adhesive layer having an opening, or a dot-like or island-like shape. Thus, the pressure-sensitive adhesive layer may have a pattern in which the pressure-sensitive adhesive layer is not continuous.
本発明の粘着シートは、皮膚に直接使用する用途が好ましい。 The adhesive sheet of the present invention is preferably used directly on the skin.
<通気性フォーム体>
本発明で用いる通気性フォーム体は、汗等の水分(水ないし水蒸気)を透過できる連続気泡ないし貫通孔を有している。そのため通気性フォーム体は、ホットメルト粘着剤層(A)を通過(ないし透過)した水分を通過できる程度の連続気泡を有すればよいため特に限定されないところ、その水蒸気透過性を挙げるとすれば3000g/m2・24時間以上である。水蒸気透過性は、通気性フォーム体が粘着シートとして使用できる強度を有する範囲内であれば高ければ高いほど好ましいため特に上限値はないところ、強いて挙げれば10000g/m2・24時間程度である。なお、水蒸気透過性は、JIS―Z0208に準じた方法で測定された数値である。なお連続気泡とは、例えば、通気性フォーム体を製造する際に使用した発泡剤に起因して生じた気泡であるが、発泡剤を用いて作製されたものに限定されないことはいうまでもない。なお、本明細書で孔は、貫通孔を意味する。
<Breathable foam body>
The breathable foam used in the present invention has open cells or through-holes that can permeate moisture such as sweat (water or water vapor). Therefore, the breathable foam body is not particularly limited because it has only to have open cells that can pass the water that has passed (or passed through) the hot melt pressure-sensitive adhesive layer (A). It is 3000 g / m 2 · 24 hours or more. The water vapor permeability is preferably as high as possible as long as the breathable foam body has a strength that can be used as a pressure-sensitive adhesive sheet. Therefore, there is no particular upper limit, but if it is mentioned, it is about 10,000 g / m 2 · 24 hours. The water vapor permeability is a numerical value measured by a method according to JIS-Z0208. Note that the open cells are, for example, bubbles generated due to the foaming agent used in producing the breathable foam body, but it is needless to say that the open cells are not limited to those produced using the foaming agent. . In addition, in this specification, a hole means a through hole.
通気性フォーム体の素材は、粘着シートとして使用可能な柔軟性および通気性を有する公知の素材であればよく限定されない。前記素材は、プラスチックス、合成ゴムが好ましい。素材は、例えば、ポリウレタン、ポリエステル、ポリオレフィン、エチレンプロピレンゴム等が挙げられる。 The material of the breathable foam body is not limited as long as it is a known material having flexibility and breathability that can be used as an adhesive sheet. The material is preferably plastics or synthetic rubber. Examples of the material include polyurethane, polyester, polyolefin, ethylene propylene rubber, and the like.
通気性フォーム体の厚みは、通常0.05mm〜10mm程度であり、0.5mm〜5mmが好ましい。 The thickness of the breathable foam body is usually about 0.05 mm to 10 mm, preferably 0.5 mm to 5 mm.
<ホットメルト粘着剤>
ホットメルト粘着剤層(A)は、ホットメルト粘着剤を塗工することで形成する。
ホットメルト粘着剤は、例えばスチレン系共重合体、粘着付与剤、軟化剤を含むことが好ましい。
<Hot melt adhesive>
The hot melt pressure-sensitive adhesive layer (A) is formed by applying a hot melt pressure-sensitive adhesive.
The hot melt adhesive preferably contains, for example, a styrene copolymer, a tackifier, and a softener.
スチレン系共重合体は、ホットメルト粘着剤層(A)に凝集力を付与する主成分であり、公知のスチレンブロック共重合体を用いることが好ましい。
スチレン系共重合体は、例えばスチレン−エチレン−ブチレン−スチレンブロック共重合体(以下、「SEBS」とも略記する)、スチレン−イソプレン−スチレンブロック共重合物(以下、「SIS」とも略記する)、スチレン−イソプレン−スチレンブロック共重合物の水素添加物(以下、「SEPS」とも略記する)、スチレン−ブタジエン−スチレンブロック共重合物(以下、「SBS」とも略記する) 、スチレン−ブタジエン−スチレンブロック共重合物の水素添加物(以下、「SEBS」とも略記する)、スチレン−ブタジエン−イソプレン−スチレンブロック共重合物(以下、「SBIS」とも略記する)、スチレン−ブタジエン−イソプレン−スチレンブロック共重合物の水素添加物(以下、「SEEPS」とも略記する)等が挙げられる。スチレン系共重合体は、単独または2種類以上を併用できる。
The styrene-based copolymer is a main component that imparts cohesive force to the hot melt pressure-sensitive adhesive layer (A), and it is preferable to use a known styrene block copolymer.
Examples of the styrene copolymer include a styrene-ethylene-butylene-styrene block copolymer (hereinafter abbreviated as “SEBS”), a styrene-isoprene-styrene block copolymer (hereinafter abbreviated as “SIS”), Hydrogenated product of styrene-isoprene-styrene block copolymer (hereinafter also abbreviated as “SEPS”), styrene-butadiene-styrene block copolymer (hereinafter abbreviated as “SBS”), styrene-butadiene-styrene block Hydrogenated copolymer (hereinafter also abbreviated as “SEBS”), styrene-butadiene-isoprene-styrene block copolymer (hereinafter also abbreviated as “SBIS”), styrene-butadiene-isoprene-styrene block copolymer Hydrogenated product (hereinafter also abbreviated as “SEEPS”) Etc. Styrenic copolymers can be used alone or in combination of two or more.
スチレン系共重合体は、メルトフローレイト(MFR)が0.5g/10分以上100g/10分(190℃、2.16kg)以下であることが好ましい。MFRを前記範囲内にあることで塗工適性がより向上する。なおMFRとは溶液状態にある樹脂の流動性を示す指標であり、JIS K7210に準拠して測定したものである。 The styrene copolymer preferably has a melt flow rate (MFR) of 0.5 g / 10 min or more and 100 g / 10 min (190 ° C., 2.16 kg) or less. When the MFR is within the above range, the coating suitability is further improved. MFR is an index indicating the fluidity of a resin in a solution state, and is measured according to JIS K7210.
スチレン系共重合体の配合量は、ホットメルト粘着剤100重量%のうち、3〜65重量%が好ましく、25〜35重量%がより好ましい。配合量が前記範囲内にあると凝集力とホットメルト粘着剤の製造し易さを両立し易い。 The blending amount of the styrene copolymer is preferably 3 to 65% by weight, more preferably 25 to 35% by weight, out of 100% by weight of the hot melt adhesive. When the blending amount is within the above range, it is easy to achieve both cohesion and ease of manufacturing a hot melt pressure-sensitive adhesive.
粘着付与剤は、ホットメルト粘着剤層(A)に粘着力を付与できる公知の化合物である。粘着付与剤は、その軟化点が80〜160℃であることが好ましい。軟化点が前記範囲内にあることで凝集力と粘着力を両立し易い。なお、本発明で軟化点とは、JISK6863に規定される方法により求められる温度である。すなわち、ホットメルト粘着剤を充填した規定の環を12時間以上静置させた後、熱媒体中に入れて規定の球を、ホットメルト粘着剤を充填した規定の環の上に置き、一定の割合で熱媒体の温度を上昇させたとき、ホットメルト粘着剤の軟化により球が沈み環台の底板に触れたときの温度である。 A tackifier is a well-known compound which can provide adhesive force to a hot-melt-adhesive layer (A). The tackifier preferably has a softening point of 80 to 160 ° C. When the softening point is within the above range, it is easy to achieve both cohesion and adhesion. In the present invention, the softening point is a temperature determined by a method defined in JISK6863. That is, after leaving the specified ring filled with the hot-melt pressure-sensitive adhesive to stand for 12 hours or more, it is placed in a heat medium and the specified sphere is placed on the specified ring filled with the hot-melt pressure-sensitive adhesive. When the temperature of the heat medium is increased by a ratio, the temperature is when the sphere sinks due to softening of the hot melt adhesive and touches the bottom plate of the ring platform.
粘着付与剤は、例えばロジン系樹脂、水素添加されたロジン系樹脂、テルペン系樹脂、水素添加されたテルペン系樹脂、炭化水素系樹脂、水素添加された炭化水素系樹脂、エポキシ系樹脂、水素添加されたエポキシ系樹脂、ポリアミド系樹脂、水素添加されたポリアミド系樹脂、エラストマー系樹脂、水素添加されたエラストマー系樹脂、フェノール系樹脂、水素添加されたフェノール系樹脂、ケトン系樹脂、水素添加されたケトン系樹脂、石油径樹脂、水素添加された石油径樹脂、スチレン系樹脂および水素添加されたスチレン系樹脂などが挙げられる。これらの中でも色相の観点から水素添加されたテルペン系樹脂がより好ましい。粘着付与剤は、単独または2種以上併用できる。 Tackifiers include, for example, rosin resins, hydrogenated rosin resins, terpene resins, hydrogenated terpene resins, hydrocarbon resins, hydrogenated hydrocarbon resins, epoxy resins, hydrogenated Epoxy resin, polyamide resin, hydrogenated polyamide resin, elastomer resin, hydrogenated elastomer resin, phenol resin, hydrogenated phenol resin, ketone resin, hydrogenated Examples thereof include ketone resins, petroleum diameter resins, hydrogenated petroleum diameter resins, styrene resins, and hydrogenated styrene resins. Among these, hydrogenated terpene resins are more preferable from the viewpoint of hue. The tackifiers can be used alone or in combination of two or more.
粘着付与剤の配合量は、ホットメルト粘着剤100重量%のうち、3〜60重量%が好ましく、20〜35重量%がより好ましい。配合量が前記範囲内にあると粘着力と凝集力を高いレベルで両立しやすくなる。 The amount of the tackifier is preferably 3 to 60% by weight, more preferably 20 to 35% by weight, out of 100% by weight of the hot melt pressure-sensitive adhesive. When the blending amount is within the above range, it becomes easy to achieve both adhesive strength and cohesive strength at a high level.
軟化剤は、ホットメルト粘着剤を加熱塗工する際に、ホットメルト粘着剤の粘度を塗工に適する粘度に下げる機能を有する。 The softening agent has a function of reducing the viscosity of the hot melt pressure-sensitive adhesive to a viscosity suitable for coating when the hot melt pressure-sensitive adhesive is applied by heating.
軟化剤は、その分子量が100〜10000であることが好ましい。分子量が前記範囲内にあるとホットメルト粘着剤を塗工するために加熱する際の粘度が低下し易い一方、ブリードアウトがより生じ難くなる。本発明で分子量は、単一化合物の場合は化学式量、混合物の場合は重量平均分子量である。また、本発明で重量平均分子量は、ゲルパーミエーションクロマトグラフィー法(以下、「GPC」とも略記する)によるポリスチレン換算された重量平均分子量である。 The softener preferably has a molecular weight of 100 to 10,000. When the molecular weight is within the above range, the viscosity at the time of heating to coat the hot melt pressure-sensitive adhesive is likely to decrease, but bleeding out is more difficult to occur. In the present invention, the molecular weight is a chemical formula weight in the case of a single compound, and a weight average molecular weight in the case of a mixture. In the present invention, the weight average molecular weight is a polystyrene-converted weight average molecular weight obtained by gel permeation chromatography (hereinafter also abbreviated as “GPC”).
軟化剤は、ホットメルト粘着剤に使用できる公知の軟化剤が使用できるところ、例えば例えば流動パラフィン、パラフィン、スクワラン、ミスチル酸、ミスチル酸イソプロピル、ミスチル酸亜鉛、ミリスチン酸オクチルドデシル、トリイソオクタン酸グリセリン、オクチルドデカノール、ヘキシルデカノール、アジピン酸ジイソプロピル、セバシン酸ジエチル、ステアリン酸、イソステアリン酸、クロタミトン、中鎖脂肪酸トリグリセリト、サリチル酸エチレングリコール、エチルヘキサン酸セチル、オレイン酸、オリーブ油、カルナウバロウ、米胚芽油、コーン油、サザンカ油、ジステアリン酸グリコール、セテアリルアルコール、セタノール、ツバキ油、パルミチン酸セチル、パルミチン酸エチルヘキシル、パルミチン酸イソプロピル、ヒマシ油、ベヘニルアルコール、ホホバ種子油、ミンク油、ワセリン、ミツロウ、ユーカリ葉油、はちみつ、パラフィン鎖炭素数が全炭素数の50%以上を占めるパラフィン系鉱物油、ナフテン環炭素数が全炭素数の30〜40重量%を占めるナフテン系鉱物油、および芳香族炭素数が全炭素数の30重量%以上を占める芳香族系鉱物油などが挙げられる。これらの中でも粘着テープの生産性の面から流動パラフィン、パラフィン鎖炭素数が全炭素数の50%以上を占めるパラフィン系鉱物油がより好ましい。軟化剤は、単独または2種類以上を併用できる。 As the softener, known softeners that can be used for hot melt adhesives can be used.For example, liquid paraffin, paraffin, squalane, misty acid, isopropyl myristate, zinc myristate, octyldodecyl myristate, glycerin triisooctanoate, Octyldodecanol, hexyldecanol, diisopropyl adipate, diethyl sebacate, stearic acid, isostearic acid, crotamiton, medium chain fatty acid triglyceride, ethylene glycol salicylate, cetyl ethylhexanoate, oleic acid, olive oil, carnauba wax, rice germ oil, corn oil, Sasanqua oil, glycol distearate, cetearyl alcohol, cetanol, camellia oil, cetyl palmitate, ethylhexyl palmitate, isopropyl palmitate, Masi oil, behenyl alcohol, jojoba seed oil, mink oil, petrolatum, beeswax, eucalyptus leaf oil, honey, paraffinic mineral oil with paraffin chain carbon number accounting for 50% or more of the total carbon number, naphthenic ring carbon number of total carbon number Examples thereof include naphthenic mineral oil occupying 30 to 40% by weight, and aromatic mineral oil occupying 30% by weight or more of the total number of carbon atoms. Among these, liquid paraffin and paraffinic mineral oil in which the number of carbon atoms in the paraffin chain accounts for 50% or more of the total number of carbon atoms are more preferable from the viewpoint of productivity of the adhesive tape. The softeners can be used alone or in combination of two or more.
軟化剤の配合量は、ホットメルト粘着剤100重量%のうち、20〜60重量%が好ましく、30〜50重量%がより好ましい。配合量が前記範囲内にあることで加工性と凝集力をより高いレベルで両立しやすくなる。 The blending amount of the softener is preferably 20 to 60% by weight, more preferably 30 to 50% by weight, out of 100% by weight of the hot melt pressure-sensitive adhesive. When the blending amount is in the above range, it becomes easy to achieve both workability and cohesion at a higher level.
ホットメルト粘着剤は、さらに以下の添加剤を配合できる。例えば酸化防止剤、紫外線吸収剤、光安定剤、接着昂進防止剤、シランカップリング剤、抗菌剤、消臭剤、香料、保湿剤、吸水剤、電解質塩が挙げられる。 The hot melt pressure-sensitive adhesive can further contain the following additives. For example, antioxidants, ultraviolet absorbers, light stabilizers, adhesion progress inhibitors, silane coupling agents, antibacterial agents, deodorants, fragrances, humectants, water absorbing agents, and electrolyte salts can be mentioned.
酸化防止剤は、例えばフェノール系酸化防止剤およびリン系酸化防止剤が好ましい。
酸化防止剤は、例えばペンタエリスリトールテトラキス[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート]、オクタデシル−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート、ジエチル〔[3,5−ビス(1,1−ジメチルエチル)−4−ヒドロキシフェニル]メチル〕ホスフォネート、4,6−ビス(オクチルチオメチル)−o−クレゾール、エチレンビス(オキシエチレン)ビス[3−(5−t−ブチル−4−ヒドロキシ−m−トリル]プロピオネート、トリス(2,4−ジ−t−ブチルフェニル)フォスファイト、ビス(2,4−ジ−t−ブチルフェニル)ペンタエリスリトールジフォスファイト等が挙げられる。酸化防止剤は、単独または2種類以上を併用できる。
As the antioxidant, for example, a phenol-based antioxidant and a phosphorus-based antioxidant are preferable.
Examples of the antioxidant include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl). ) Propionate, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) Bis [3- (5-t-butyl-4-hydroxy-m-tolyl] propionate, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) Examples thereof include pentaerythritol diphosphite, etc. The antioxidants can be used alone or in combination of two or more.
紫外線吸収剤は、公知の化合物が使用できる。例えば、サリチル酸系化合物、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物が挙げられる。紫外線吸収剤は、単独または2種類以上を併用できる。 Known compounds can be used as the ultraviolet absorber. Examples include salicylic acid compounds, benzophenone compounds, and benzotriazole compounds. The ultraviolet absorber can be used alone or in combination of two or more.
光安定剤は、公知の化合物が使用できる。例えば、ヒンダードアミン系化合物が挙げられる。紫外線吸収剤は、単独または2種類以上を併用できる。 Known compounds can be used as the light stabilizer. Examples include hindered amine compounds. The ultraviolet absorber can be used alone or in combination of two or more.
シランカップリング剤は、例えばビニルトリメトキシシラン、ビニルトリエトキシシラン、メタクリロキシプロピルトリメトキシシラン、3−メタクリロキシプロピルメチルジメトキシシラン、3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルトリエトキシシラン、3−グリシドキシプロピルメチルジメトキシシラン、3−グリシドキシプロピルメチルジエトキシシラン、2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、3−アミノプロピルトリメトキシシラン、3−アミノプロピルトリエトキシシラン、3−アミノプロピルメチルジメトキシシラン、N−(2−アミノエチル)3−アミノプロピルトリメトキシシラン、N−(2−アミノエチル)3−アミノプロピルメチルジメトキシシラン、3−メルカプトプロピルトリメトキシシラン、3−メルカプトプロピルトリエトキシシラン、メルカプトブチルトリメトキシシラン、3−メルカプトプロピルメチルジメトキシシランが挙げられる。シランカップリング剤は、単独または2種類以上を併用できる。 Silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltri Ethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxy silane, mercaptopropyl butyl trimethoxy silane include 3-mercaptopropyl methyl dimethoxy silane. A silane coupling agent can be used alone or in combination of two or more.
抗菌剤は、例えばブテナフィン及びその塩等のベンジルアミン系抗菌剤;ビフォナゾール、ネチコナゾール、ケトコナゾール、ラノコナゾール、クロトリマゾール、ミコナゾール、オキシコナゾール、チオコナゾール、クロコナゾール、オモコナゾール、スルコナゾール及びこれらの塩等のイミダゾール系抗菌剤;テルビナフィン及びその塩などのアリルアミン系抗菌剤;アモロルフィン及びその塩等のモルホリン系抗菌剤;リラナフタート、トルナフテート及びトルシクラート等のチオカルバミン酸系抗菌剤;ナイスタチン、トリコマイシン、バリオチン、シッカニン、ピロールニトリン等の抗生物質等の抗菌剤;熊笹エキス、茶カテキンが挙げられる。抗菌剤は、単独または2種類以上を併用できる。 Antibacterial agents include benzylamine antibacterial agents such as butenafine and salts thereof; imidazoles such as bifonazole, neticonazole, ketoconazole, ranoconazole, clotrimazole, miconazole, oxyconazole, thioconazole, croconazole, omoconazole, sulconazole and salts thereof Allylamine antibacterial agents such as terbinafine and its salts; morpholine antibacterial agents such as amorolfine and its salts; thiocarbamic acid antibacterial agents such as lirannaphthate, tolnaftate and tolcyclate; nystatin, tricomycin, variotin, siccanin, pyrrolnitrile Antibacterial agents such as antibiotics such as urine; Kumagusu extract and tea catechin. Antibacterial agents can be used alone or in combination of two or more.
消臭剤は、消臭効果を有する公知の化合物が好ましい。例えば、ラウリルメタクリレート、ゲラニルクロリネート、シトロネリルセネシオネート、テルペンアルデヒド類、ピルビン酸エステル、2−エチルヘキサン酸亜鉛、リシノール酸亜鉛が挙げられる。消臭剤は、単独または2種類以上を併用できる。 The deodorant is preferably a known compound having a deodorizing effect. For example, lauryl methacrylate, geranyl chloride, citronellyl senecionate, terpene aldehydes, pyruvate, zinc 2-ethylhexanoate, zinc ricinoleate can be mentioned. The deodorizer can be used alone or in combination of two or more.
香料は、例えばピネン、リモネン等の炭化水素系香料、リナロール、ゲラニオール、シトロネロール、メントール、ボルネオール、ベンジルアルコール、アニスアルコール、β−フェネチルアルコール等のアルコール系香料、アネトール、オイゲノール等のフェノール系香料、n−ブチルアルデヒド、イソブチルアルデヒド、ヘキシルアルデヒド、シトラール、シトロネラール、ベンズアルデヒド、シンナミックアルデヒド等のアルデヒド系香料、カルボン、メントン、樟脳、アセトフェノン、イオノン等のケトン系香料、γ―ブチルラクトン、クマリン、シネオール等のラクトン系香料、オクチルアセテート、ベンジルアセテート、シンナミルアセテート、プロピオン酸ブチル、安息香酸メチル等のエステル系香料が挙げられる。香料は、単独または2種類以上を併用できる。 Fragrances include, for example, hydrocarbon-based fragrances such as pinene and limonene, linalool, geraniol, citronellol, menthol, borneol, benzyl alcohol, anis alcohol, β-phenethyl alcohol, and other phenol-based fragrances such as anethole and eugenol, n -Aldehyde fragrances such as butyraldehyde, isobutyraldehyde, hexyl aldehyde, citral, citronellal, benzaldehyde, cinnamic aldehyde, ketone fragrances such as carvone, menthone, camphor, acetophenone, ionone, γ-butyl lactone, coumarin, cineol, etc. Examples include lactone-based fragrances, ester-based fragrances such as octyl acetate, benzyl acetate, cinnamyl acetate, butyl propionate, and methyl benzoate. A fragrance | flavor can be used individually or in combination of 2 or more types.
保湿剤は、例えば1,3−ブチレングリコール、プロピレングリコール、ジプロピレングリコール、グリセリン、マルチトール、トレハロースなどの多価アルコール、ピロリドンカルボン酸、乳酸、尿素、アミノ酸などの天然保湿因子(Natural Moisturizing Factor/NMF成分)、ヘパリン、ヒアルロン酸、コンドロイチン硫酸、キチン、キトサン、アルギン酸ナトリウム、アロエ、ペクチンなどの多糖類、コラーゲン、エラスチン、ケラチン、ゼラチン、カゼイン、シルク、小麦プロテイン、ワセリン、大豆プロテイン、DNAなどのペブチド及びその加水分解物、塩化ナトリウム、海水などのミネラル、セラミド、コレステロールエステルが挙げられる。保湿剤は、単独または2種類以上を併用できる。 Examples of the humectant include natural moisturizing factors such as polyhydric alcohols such as 1,3-butylene glycol, propylene glycol, dipropylene glycol, glycerin, maltitol and trehalose, pyrrolidone carboxylic acid, lactic acid, urea and amino acids. NMF component), heparin, hyaluronic acid, chondroitin sulfate, chitin, chitosan, sodium alginate, aloe, pectin and other polysaccharides, collagen, elastin, keratin, gelatin, casein, silk, wheat protein, petrolatum, soy protein, DNA, etc. Peptides and hydrolysates thereof, sodium chloride, minerals such as seawater, ceramides, cholesterol esters. The humectant can be used alone or in combination of two or more.
吸水剤は、例えばデンプン、架橋カルボキシルメチル化セルロース、アクリル酸またはアクリル酸アルカリ金属塩の重合体ならびにその共重合体、架橋ポリアクリル酸およびその塩ならびにポリアクリル酸塩グラフト重合体が挙げられる。吸水剤は、単独または2種類以上を併用できる。 Examples of the water absorbing agent include starch, crosslinked carboxylmethylated cellulose, a polymer of acrylic acid or an alkali metal acrylate and a copolymer thereof, a crosslinked polyacrylic acid and a salt thereof, and a polyacrylate graft polymer. The water absorbing agent can be used alone or in combination of two or more.
電解質塩は、例えばハロゲン化ナトリウム、ハロゲン化カリウム、ハロゲン化マグネシウム、ハロゲン化カルシウム等のハロゲン化アルカリ金属;ハロゲン化アルカリ土類金属または他の金属ハロゲン化物;各種金属の次亜塩素酸塩、亜塩素酸塩、塩素酸塩、過塩素酸塩、硫酸塩、硝酸塩、燐酸塩、アンモニウム塩;各種錯塩等の無機塩;酢酸、安息香酸、乳酸、酒石酸等の一価カルボン酸塩;フマル酸、コハク酸、アジビン酸、クエン酸等の多価カルボン酸塩;スルホン酸、アミノ酸金属塩;有機アンモニウム塩;ポリ(メタ)アクリル酸、ポリビニルスルホン酸、ポリターシャルブチルアクリルアミドスルホン酸、ポリアリルアミン、ポリエチレンイミン等の高分子電解質の塩が挙げられる。電解質塩は、単独または2種類以上を併用できる。 The electrolyte salt includes, for example, alkali metal halides such as sodium halide, potassium halide, magnesium halide, and calcium halide; alkaline earth metal halides or other metal halides; hypochlorites of various metals, Chlorates, chlorates, perchlorates, sulfates, nitrates, phosphates, ammonium salts; inorganic salts such as various complex salts; monovalent carboxylates such as acetic acid, benzoic acid, lactic acid, tartaric acid; fumaric acid, Polycarboxylic acid salts such as succinic acid, adipic acid and citric acid; sulfonic acid, amino acid metal salt; organic ammonium salt; poly (meth) acrylic acid, polyvinyl sulfonic acid, polytertiary butylacrylamide sulfonic acid, polyallylamine, polyethylene Examples thereof include a salt of a polymer electrolyte such as imine. The electrolyte salt can be used alone or in combination of two or more.
添加剤の配合量は、ホットメルト粘着剤100重量%のうち、合計0.01〜10重量%程度である。 The compounding amount of the additive is about 0.01 to 10% by weight in total in 100% by weight of the hot melt pressure-sensitive adhesive.
<ホットメルト粘着剤層(A)>
ホットメルト粘着剤層(A)は、水分を透過させるため表面の空隙率が5%〜50%であることが好ましい。空隙率が5%以上になると皮膚の蒸れやかゆみを抑制できる。また、空隙率が50%以下になると粘着シートが意図せずに皮膚から剥がれることが減少する。なお、表面の空隙率とは粘着剤層1平方ミリメートルあたりに存在する孔の面積比率である。なお、ホットメルト粘着剤層(A)がパターン塗工されている場合、粘着剤層の非形成部は、表面の空隙率を算出する場所として使用しない。
<Hot-melt adhesive layer (A)>
The hot melt pressure-sensitive adhesive layer (A) preferably has a surface porosity of 5% to 50% in order to allow moisture to permeate. When the porosity is 5% or more, it is possible to suppress stuffiness and itching of the skin. Moreover, when the porosity is 50% or less, the adhesive sheet is less intentionally peeled off from the skin. The surface porosity is an area ratio of holes existing per square millimeter of the pressure-sensitive adhesive layer. In addition, when the hot-melt pressure-sensitive adhesive layer (A) is pattern-coated, the non-formed portion of the pressure-sensitive adhesive layer is not used as a place for calculating the surface porosity.
また、ホットメルト粘着剤層(A)は、1平方ミリメートル当たりに円相当径が10〜400μmの孔を2個以上有する。円相当径が10μm以上になると孔の形状を経時で保持しやすい。また、円相当径が400μm以下になると粘着力と透湿性のバランスを取りやすい。孔を2個以上になると皮膚の蒸れやかゆみを抑制できる。孔は水分を透過できる貫通孔であればよく、その形状は限定されない。なお、円相当径は、30μm〜300μmがより好ましく、30μm〜200μmがさらに好ましい。
孔の個数は、100mm四方のサンプルの任意の5か所について、1平方ミリメートルあたりの孔の個数を数え、任意の5か所の平均値を孔の個数とした。孔の形状は、例えば、円、楕円等の形状;勾玉、アメーバ状等の不定形が挙げられる。なお、孔は、3個以上が好ましく、5個以上がより好ましい。孔の個数の上限は、円相当径の大小により変動するため正確に定めることが難しいため規定できない。そのため孔の個数の上限は、表面の空隙率が50%を超えない個数であれば良い。
The hot melt pressure-sensitive adhesive layer (A) has two or more holes having an equivalent circle diameter of 10 to 400 μm per square millimeter. When the equivalent circle diameter is 10 μm or more, the shape of the hole is easily retained over time. Further, when the equivalent circle diameter is 400 μm or less, it is easy to balance the adhesive force and moisture permeability. When there are two or more holes, it is possible to suppress the stuffiness and itching of the skin. The hole should just be a through-hole which can permeate | transmit moisture, and the shape is not limited. The equivalent circle diameter is more preferably 30 μm to 300 μm, and even more preferably 30 μm to 200 μm.
As for the number of holes, the number of holes per square millimeter was counted at any five locations of a 100 mm square sample, and the average value at any five locations was defined as the number of holes. Examples of the shape of the hole include shapes such as a circle and an ellipse; In addition, 3 or more holes are preferable, and 5 or more holes are more preferable. The upper limit of the number of holes cannot be specified because it varies depending on the equivalent circle diameter and is difficult to determine accurately. For this reason, the upper limit of the number of holes may be any number as long as the porosity of the surface does not exceed 50%.
前記孔は、真円や楕円のように径を算出し易い形状が少なく不定形が多いため、円相当径(面積円相当径)で定義する。なお、円相当径は、空隙(孔)一つの面積をSとする場合に相当する直径(円相当径):L=√(4×S/π)で規定する。表面の空隙率の測定は、レーザーマイクロスコープ VK−X100(キーエンス社製)を用い、100mm四方のサンプルの任意5か所について、1平方ミリメートルあたりの空隙部分の面積の和を算出し、任意5か所の平均値を空隙率とした。また、円相当径:Lは、空隙1個あたりの面積を求めた後、上述式より算出した。 The hole is defined by a circle-equivalent diameter (area-equivalent circle diameter) because there are few irregular shapes such as a perfect circle and an ellipse and the shape is easy to calculate. The equivalent circle diameter is defined by a diameter (circle equivalent diameter) corresponding to a case where the area of one void (hole) is S: L = √ (4 × S / π). The surface porosity is measured by using a laser microscope VK-X100 (manufactured by Keyence Corporation), and calculating the sum of the area of the void portion per square millimeter for any five locations of a 100 mm square sample. The average value of the places was defined as the porosity. The equivalent circle diameter L was calculated from the above formula after obtaining the area per void.
ホットメルト粘着剤層(A)の形状は、全面べた塗工で粘着剤層が形成されていても、パターン状に形成されていても、ドッド状に形成されていても、全くランダムな形状に形成されていても構わない。粘着剤層の形状に関わらず、所定の空隙率および孔の数を満たせばよい。 The shape of the hot melt pressure-sensitive adhesive layer (A) is completely random regardless of whether the pressure-sensitive adhesive layer is formed by solid coating, formed in a pattern, or formed in a dod shape. It may be formed. What is necessary is just to satisfy | fill predetermined porosity and the number of holes irrespective of the shape of an adhesive layer.
パターン状とは、格子状、ブロック状、ストライプ状、など一定絵柄の繰り返し模様をいい、粘着剤層部分と非粘着剤層が繰り返される。
パターン状にホットメルト粘着剤層を塗工する方法としては、公知の方法を使用できる。粘着剤層と非粘着剤層の面積比は、粘着剤層:非粘着剤層=10:1〜10:10の範囲が好ましい。粘着剤層の比率が非粘着剤層と同等以上であると粘着力がより向上する。
The pattern shape means a repetitive pattern having a certain pattern such as a lattice shape, a block shape, or a stripe shape, and the adhesive layer portion and the non-adhesive layer are repeated.
As a method for applying the hot melt pressure-sensitive adhesive layer in a pattern, a known method can be used. The area ratio between the pressure-sensitive adhesive layer and the non-pressure-sensitive adhesive layer is preferably in the range of pressure-sensitive adhesive layer: non-pressure-sensitive adhesive layer = 10: 1 to 10:10. When the ratio of the pressure-sensitive adhesive layer is equal to or higher than that of the non-pressure-sensitive adhesive layer, the adhesive force is further improved.
ホットメルト粘着剤層(A)は、厚さ10〜200μmであることが好ましく、より好ましくは30μm〜100μmの範囲である。この範囲を満たすことで、粘着力がより向上する。 The hot melt pressure-sensitive adhesive layer (A) preferably has a thickness of 10 to 200 μm, more preferably 30 μm to 100 μm. By satisfy | filling this range, adhesive force improves more.
<粘着シートの製造方法>
本発明の粘着シートの製造方法は、ホットメルト粘着剤層(X)と、通気性フォーム体とを加熱圧着して、表面の空隙率が5〜50%、かつ1平方ミリメートル当たり円相当径が10〜400μmの孔を2個以上有するホットメルト粘着剤層(A)を形成できれば良く、その製造方法は限定されない。
<Method for producing adhesive sheet>
In the method for producing the pressure-sensitive adhesive sheet of the present invention, the hot-melt pressure-sensitive adhesive layer (X) and the breathable foam body are heat-pressed, and the surface porosity is 5 to 50% and the equivalent circle diameter per square millimeter is The manufacturing method is not limited as long as the hot melt pressure-sensitive adhesive layer (A) having two or more 10 to 400 μm holes can be formed.
粘着シートの製造方法の好ましい実施態様の一つは、下記の通りである。
ホットメルト粘着剤層(X)と、通気性フォーム体とを加熱圧着して、ホットメルト粘着剤層(A)を形成することが好ましい。前記加熱圧着によりホットメルト粘着剤層(X)と通気性フォーム体が圧縮されながらホットメルト粘着剤層(X)の一部が多数の孔を有する通気性フォーム体に沈み込みつつ(含浸しつつ)、粘着剤層に通気性フォーム体の孔に基づく孔が形成されることでホットメルト粘着剤層(A)が得られる。
加熱圧着に用いる装置は、例えば加熱ロールラミネーターが挙げられる。
One of the preferable embodiments of the method for producing the pressure-sensitive adhesive sheet is as follows.
The hot melt pressure-sensitive adhesive layer (X) and the breathable foam body are preferably heat-pressed to form the hot-melt pressure-sensitive adhesive layer (A). While the hot-melt pressure-sensitive adhesive layer (X) and the breathable foam body are compressed by the thermocompression bonding, a part of the hot-melt pressure-sensitive adhesive layer (X) is submerged (impregnated) into the breathable foam body having a large number of holes. ), A hot melt pressure-sensitive adhesive layer (A) is obtained by forming holes based on the holes of the breathable foam body in the pressure-sensitive adhesive layer.
An apparatus used for thermocompression bonding includes, for example, a heated roll laminator.
ホットメルト粘着剤層(X)は、剥離性シート上に予め加熱溶融させたホットメルト粘着剤を塗工し、形成する。ホットメルト粘着剤層(X)の厚さは、50μm〜300μmが好ましく、80〜200μmがより好ましい。厚さが所定の範囲内にあることで通気性フォーム体との密着性および粘着力がより向上し、所望の空隙率および孔が得易い。
粘着剤の加熱溶融温度は、粘着剤の組成に応じて100℃〜200℃に設定され、塗工は、例えばコンマコーター、ダイコーターなど公知のホットメルト塗工機で一定膜厚塗工する。
The hot-melt pressure-sensitive adhesive layer (X) is formed by applying a hot-melt pressure-sensitive adhesive previously heated and melted on a peelable sheet. The thickness of the hot melt pressure-sensitive adhesive layer (X) is preferably 50 μm to 300 μm, and more preferably 80 to 200 μm. When the thickness is within the predetermined range, the adhesiveness and adhesive strength with the breathable foam body are further improved, and desired porosity and pores are easily obtained.
The heating and melting temperature of the pressure-sensitive adhesive is set to 100 ° C. to 200 ° C. according to the composition of the pressure-sensitive adhesive, and the coating is performed with a constant film thickness using a known hot melt coating machine such as a comma coater or a die coater.
剥離性シートは、表面に剥離剤を塗布し、公知の素材を使用したシートを使用できるところ表面が平滑なシートが好ましい。素材は、例えば、ポリエチレンテレフタレート(PET)等のプラスチック、ならびに紙のシートにポリエチレンテレフタレートを貼り合わせた、いわゆるポリラミシートが挙げられる。 The release sheet is preferably a sheet having a smooth surface where a release agent is applied to the surface and a sheet using a known material can be used. Examples of the material include plastics such as polyethylene terephthalate (PET), and so-called polylaminated sheets in which polyethylene terephthalate is bonded to a paper sheet.
加熱圧着は、例えばロール圧着、平版圧着が挙げられる。これらの中でも生産性の面でロール圧着がより好ましい。
加熱圧着の温度は、ホットメルト粘着剤に配合する原料の選択により適宜設定すれば良く限定されないところ、60〜120℃程度が好ましく、70〜100℃程度がより好ましい。
Examples of the thermocompression bonding include roll pressure bonding and planographic pressure bonding. Among these, roll press bonding is more preferable in terms of productivity.
The temperature for thermocompression bonding is not particularly limited as long as it is appropriately set depending on the selection of raw materials to be blended in the hot melt pressure-sensitive adhesive, but is preferably about 60 to 120 ° C, more preferably about 70 to 100 ° C.
加熱圧着の圧力は、通気性フォーム体の硬さや孔等の密度の程度、ならびにホットメルト粘着剤に配合する原料の選択により適宜設定すれば良く限定されないところ、平版圧着であれば、例えば1平方cm当たり0.2〜5kg程度が好ましい。また、ロール圧着であれば、例えば1cm当たりの線圧が0.1〜5kg程度が好ましい。 The pressure of thermocompression bonding is not limited as long as it is set appropriately depending on the hardness of the breathable foam body, the density of pores, etc., and the selection of the raw material to be blended in the hot melt pressure-sensitive adhesive. About 0.2-5 kg per cm is preferable. In the case of roll pressure bonding, for example, the linear pressure per 1 cm is preferably about 0.1 to 5 kg.
ホットメルト粘着剤層(A)は、プレス前のホットメルト粘着剤層(X)の一部が通気性フォーム体に沈み込むことで、厚さ10〜200μmの粘着剤層が形成されることが好ましく、より好ましくは30μm〜100μmである。 In the hot melt pressure-sensitive adhesive layer (A), a part of the hot-melt pressure-sensitive adhesive layer (X) before pressing sinks into the breathable foam body, whereby a pressure-sensitive adhesive layer having a thickness of 10 to 200 μm is formed. Preferably, it is 30 μm to 100 μm.
また、所望の空隙率および孔を有するホットメルト粘着剤層(A)を作成する他の実施態様は、例えば、通気性フォーム体および粘着剤層を備えた粘着シートの粘着剤層側から剣山(けんざん)のように複数の針を有する装置(ないし機材等)を通気性フォーム体側に向けて押し込むことでホットメルト粘着剤層(A)を形成する方法や、ホットメルト粘着剤層(X)を、エアを混入し加熱溶融されたホットメルト粘着剤を従来公知の塗工方式で塗工したり、ホットメルト粘着剤をスプレー状に塗工して形成し、ホットメルト粘着剤層(X)と通気性フォーム体と加熱圧着し、所望の空隙率および孔を有するホットメルト粘着剤層(A)を形成する方法、通気性基材に、エアを混入し加熱溶融されたホットメルト粘着剤を従来公知の塗工方式で直接塗工したり、ホットメルト粘着剤をスプレー状に直接塗工しホットメルト粘着剤層(A)を形成する方法などが挙げられる。
なお、本発明の皮膚貼付用粘着シートは、ホットメルト粘着剤層(A)が、表面の空隙率が5〜50%であり、1平方ミリメートル当たりに円相当径が10〜400μmの孔を2個以上有するという構成を満たせば良いため、その製造方法は、これまでに説明した方法に限定されないことはいうまでもない。
Another embodiment for producing a hot melt pressure-sensitive adhesive layer (A) having a desired porosity and pores is, for example, from the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive sheet provided with a breathable foam body and a pressure-sensitive adhesive layer from Kenzan ( A method of forming a hot melt pressure-sensitive adhesive layer (A) by pushing a device (or equipment, etc.) having a plurality of needles toward the breathable foam body side, such as Kenzan, or a hot-melt pressure-sensitive adhesive layer (X) The hot-melt pressure-sensitive adhesive mixed with air and heated and melted is applied by a conventionally known coating method, or the hot-melt pressure-sensitive adhesive is applied in a spray form to form a hot-melt pressure-sensitive adhesive layer (X) A method of forming a hot-melt pressure-sensitive adhesive layer (A) having a desired porosity and pores by thermocompression bonding with a breathable foam body, and a conventional hot-melt pressure-sensitive adhesive that is heated and melted by mixing air into a breathable base material Known coating method Direct or coating, and a method of forming a hot-melt adhesive layer (A) directly applying a hot melt adhesive to the spray shape and the like.
In the pressure-sensitive adhesive sheet for skin application of the present invention, the hot melt pressure-sensitive adhesive layer (A) has a surface porosity of 5 to 50% and 2 holes with an equivalent circle diameter of 10 to 400 μm per square millimeter. Needless to say, the manufacturing method is not limited to the methods described so far, as long as the configuration of having more than one is satisfied.
ホットメルト粘着剤層(A)の厚さは、ホットメルト粘着剤層(X)が通気性フォーム体に沈み込んだ部分を除き、通気性フォーム体から独立して観察できる粘着剤層部分のみの厚さである。ホットメルト粘着剤層(A)の厚さは、粘着テープの断面を光学顕微鏡や電子顕微鏡を用いて測定できる。 The thickness of the hot-melt pressure-sensitive adhesive layer (A) is such that only the pressure-sensitive adhesive layer portion that can be observed independently from the breathable foam body, excluding the portion where the hot-melt pressure-sensitive adhesive layer (X) sinks into the breathable foam body. Is the thickness. The thickness of the hot melt pressure-sensitive adhesive layer (A) can be measured using an optical microscope or an electron microscope for the cross section of the pressure-sensitive adhesive tape.
<粘着シートの用途>
本発明の粘着シートの用途は、皮膚貼付用途に限らず、被着体から放出される液体を通過させる用途に使用できる。皮膚貼付用途でいうと、例えば、絆創膏、貼付剤、パップ剤、テーピング、医療機器固定用テープ、サージカルテープなどが挙げられる。なお、被着体とは、粘着シートを貼り付ける相手方である。
<Use of adhesive sheet>
The application of the pressure-sensitive adhesive sheet of the present invention is not limited to the application to the skin, and can be used for the purpose of allowing the liquid released from the adherend to pass through. In terms of skin application, examples thereof include adhesive bandages, patches, poultices, taping, medical device fixing tapes, and surgical tapes. In addition, a to-be-adhered body is the other party which affixes an adhesive sheet.
以下、本発明を実施例により具体的かつ詳細に説明するが、これらの実施例は本発明の
一態様に過ぎず、本発明はこれらの例によって限定されるものではない。なお、以下「部」は「重量部」を意味し、「%」は「重量%」を意味する。
EXAMPLES Hereinafter, the present invention will be described specifically and in detail with reference to examples. However, these examples are only one aspect of the present invention, and the present invention is not limited to these examples. Hereinafter, “part” means “part by weight”, and “%” means “% by weight”.
実施例で使用する原料は下記の通りである。
<スチレン系ブロック共重合体>
SEBS1:SEBS、スチレンの比率30重量%、トリブロック含有100%
SEBS2:SEBS、スチレンの比率30重量%、トリブロック含有30%、ジブロック含有70%
SEBS3:SEBS、スチレンの比率60重量%、トリブロック含有100%
SEPS1:SEPS、スチレンの比率20重量%、トリブロック含有100%
SEPS2:SEPS、スチレンの比率25重量%、トリブロック含有100%
SIS1:SIS、スチレンの比率19重量%、トリブロック含有100%
SIS2:SIS、スチレンの比率24重量%、トリブロック含有70%、ジブロック含有30%
The raw materials used in the examples are as follows.
<Styrenic block copolymer>
SEBS1: SEBS, styrene ratio 30% by weight, triblock content 100%
SEBS2: SEBS, styrene ratio 30% by weight, triblock content 30%, diblock content 70%
SEBS3: SEBS, styrene ratio 60% by weight, triblock content 100%
SEPS1: SEPS, styrene ratio 20% by weight, triblock content 100%
SEPS2: SEPS, styrene ratio 25% by weight, triblock content 100%
SIS1: SIS, styrene ratio 19% by weight, triblock content 100%
SIS2: SIS, styrene ratio 24% by weight, triblock content 70%, diblock content 30%
<軟化剤>
軟化剤1:パラフィン系鉱物油
軟化剤2:流動パラフィン
軟化剤3:ナフテン系鉱物油
<Softener>
Softener 1: Paraffinic mineral oil softener 2: Liquid paraffin softener 3: Naphthenic mineral oil
<粘着付与剤>
粘着付与剤1:テルペン系樹脂 軟化点100℃
粘着付与剤2:ロジンエステル系樹脂 軟化点110℃
粘着付与剤3:水素添加された石油系樹脂 軟化点90℃
<Tackifier>
Tackifier 1: Terpene resin Softening point 100 ° C
Tackifier 2: Rosin ester resin Softening point 110 ° C
Tackifier 3: Hydrogenated petroleum resin Softening point 90 ° C
<粘着剤の作成>
スチレン系ブロック共重合体としてSEBS1を10部、SEBS2を3部、SEPS1を20部、軟化剤1を40部、粘着付与剤1を27部を攪拌機を備えたニーダーに投入し、160℃加熱下3時間撹拌を行い、粘着剤1を得た。
<Creation of adhesive>
As a styrenic block copolymer, 10 parts of SEBS1, 3 parts of SEBS2, 20 parts of SEPS1, 40 parts of
粘着剤1の原料および配合量を表1に記載された通りに変更した以外は、粘着剤1と同様に行うことでそれぞれ粘着剤2〜8を得た。 Except having changed the raw material and compounding quantity of adhesive 1 as described in Table 1, it carried out similarly to adhesive 1, and obtained adhesives 2-8, respectively.
<実施例1>
得られた粘着剤1をホットメルト塗工機を使用してPET製剥離性シート上に厚さ150μmにべた塗り塗工して、ホットメルト粘着剤層(X)を得た。得られたホットメルト粘着剤層(X)と、厚さ1mmの軟質ポリウレタンフォーム(水蒸気透過率4000g/m2・24時間)とをロール式の加熱ラミネーターを用いて温度80℃・圧力2MPa・速度1M/分の加熱圧着条件で貼り合せ、ホットメルト粘着剤層(A)の厚さが100μmの皮膚貼付用粘着テープを得た。
得られた皮膚貼付用粘着テープのホットメルト粘着剤層(A)の表面をレーザーマイクロスコープ(VK−X100 キーエンス社製)で観察したところ、1平方ミリメートル当たり平均4個の孔を有し、その表面空隙率は20%であった。
<Example 1>
The obtained pressure-
When the surface of the hot melt pressure-sensitive adhesive layer (A) of the obtained adhesive tape for skin application was observed with a laser microscope (VK-X100, manufactured by Keyence Corporation), it had an average of 4 holes per square millimeter. The surface porosity was 20%.
<実施例2〜8ならびに比較例1〜2>
実施例1の粘着剤1を表2に記載された粘着剤、ホットメルト粘着剤層厚み、加熱圧着条件に変更した以外は、実施例1と同様に行うことでそれぞれ実施例2〜8ならびに比較例1〜2の皮膚貼付用粘着テープを得た。次いで実施例1と同様にホットメルト粘着剤層(A)の表面を観察した。孔の平均個数および空隙率は表2に記載した。
<Examples 2-8 and Comparative Examples 1-2>
Except having changed the
<実施例9>
図1に示す粘着剤層の幅11 2mm、および着剤層の塗工間隔12 2mmのストライプ状に粘着剤層を形成可能な塗工ヘッドを有するホットメルトダイコーターにて、PET製剥離性シート上に、粘着剤1を厚さ100μm塗工して、ホットメルト粘着剤層(X)を作製した。得られたホットメルト粘着剤層(X)と、軟質ポリウレタンフォームを加熱ラミネーターを用いて表2に記載された条件で加熱圧着することで、厚さ50μmのホットメルト粘着剤層(A)を有する皮膚貼付用粘着テープを得た。
得られた皮膚貼付用粘着テープのホットメルト粘着剤層(A)は、レーザーマイクロスコープで観察したところ、1平方ミリメートル当たり平均3個の孔を有し、その表面空隙率は10%であった。
<Example 9>
In a hot melt die coater having a coating head capable of forming a pressure-sensitive adhesive layer in a stripe shape having a width of 112 mm of the pressure-sensitive adhesive layer and a coating interval of 122 mm of the adhesive layer shown in FIG. On top, the adhesive 1 was applied to a thickness of 100 μm to prepare a hot-melt adhesive layer (X). The obtained hot melt pressure-sensitive adhesive layer (X) and the hot polyurethane pressure-sensitive adhesive layer (A) having a thickness of 50 μm are obtained by thermocompression bonding the flexible polyurethane foam under the conditions described in Table 2 using a heating laminator. An adhesive tape for skin application was obtained.
When the hot melt pressure-sensitive adhesive layer (A) of the obtained adhesive tape for skin application was observed with a laser microscope, it had an average of 3 holes per square millimeter and its surface porosity was 10%. .
<実施例10>
図2に示す粘着剤層の幅21(メッシュ幅)2mm、および粘着剤層の塗工間隔22(幅)2mm・粘着剤層の塗工間隔23(縦)2mmのメッシュ状に粘着剤層を形成可能な塗工ヘッドを有するホットメルトダイコーターにて、PET製剥離性シート上に粘着剤2を厚さ150μm塗工して、ホットメルト粘着剤層(X)を作製した。得られたホットメルト粘着剤層(X)と、軟質ポリウレタンフォーム(厚み1mm)を加熱ラミネーターを用いて表2に記載しした条件で加熱圧着することで、厚さ100μmのホットメルト粘着剤層(A)を有する皮膚貼付用粘着テープを得た。
得られた皮膚貼付用粘着テープのホットメルト粘着剤層(A)は、レーザーマイクロスコープで観察したところ、1平方ミリメートル当たり平均6個の孔を有し、その表面空隙率は30%であった。
<Example 10>
The pressure-sensitive adhesive layer is formed into a mesh having a width 21 (mesh width) of the pressure-sensitive adhesive layer shown in FIG. 2 and a coating interval 22 (width) of the pressure-sensitive adhesive layer of 2 mm and a coating interval 23 (length) of the pressure-sensitive adhesive layer of 2 mm. A hot melt pressure-sensitive adhesive layer (X) was prepared by coating the adhesive 2 with a thickness of 150 μm on a PET peelable sheet using a hot melt die coater having a coatable coating head. The obtained hot-melt pressure-sensitive adhesive layer (X) and a flexible polyurethane foam (
The hot melt pressure-sensitive adhesive layer (A) of the obtained adhesive tape for skin application had an average of 6 holes per square millimeter when observed with a laser microscope, and the surface porosity was 30%. .
<比較例3>
アクリル系粘着剤(BPS4849−40:トーヨーケム社製、不揮発分40%)を100部、硬化剤(BHS8515:イソシアネート硬化剤 トーヨーケム社製 不揮発分37.5%)を2.5部混合し、ハンドアプリケーターを使用してPET製剥離性シート上にべた塗り塗工し、乾燥を行うことで厚さ50μmの粘着剤層(X)を得た。得られた粘着剤層(X)と軟質ポリウレタンフォーム(厚み1mm)とをラミネーターを用いて表2に記載する条件で加熱圧着することで、厚さ20μmの粘着剤層(A)を有する皮膚貼付用粘着テープを得た。
得られた皮膚貼付用粘着テープの粘着剤層(A)は、1平方ミリメートル当たり円相当径10〜400μmの範囲内の孔を0個有し、表面空隙率は0%であった。
<Comparative Example 3>
Mix 100 parts of acrylic pressure-sensitive adhesive (BPS4849-40: manufactured by Toyochem, nonvolatile content 40%) and 2.5 parts of curing agent (BHS8515: isocyanate curing agent, nonvolatile content 37.5% manufactured by Toyochem), and then apply a hand applicator. The adhesive layer (X) having a thickness of 50 μm was obtained by applying a solid coating on a PET peelable sheet using a lye and drying. A skin patch having a pressure-sensitive adhesive layer (A) having a thickness of 20 μm by thermocompression bonding of the obtained pressure-sensitive adhesive layer (X) and flexible polyurethane foam (
The pressure-sensitive adhesive layer (A) of the obtained pressure-sensitive adhesive tape for skin application had 0 holes in a circle equivalent diameter of 10 to 400 μm per square millimeter, and the surface porosity was 0%.
<比較例4>
比較例3の粘着剤および硬化剤をウレタン系粘着剤(SP700:トーヨーケム社製、不揮発分45%)に、硬化剤(BXX5627:イソシアネート硬化剤 トーヨーケム社製 不揮発分50%)を1部に変更した以外は比較例3と同様の方法で行うことで、表2に示す皮膚貼付用粘着テープを作製した。
<Comparative Example 4>
The pressure-sensitive adhesive and curing agent in Comparative Example 3 were changed to a urethane-based pressure-sensitive adhesive (SP700: manufactured by Toyochem Corp., nonvolatile content: 45%), and the curing agent (BXX5627: isocyanate curing agent, manufactured by Toyochem Corp., nonvolatile content: 50%) was changed to 1 part. Except for the above, the same method as in Comparative Example 3 was followed to produce the adhesive tape for skin application shown in Table 2.
<比較例5>
得られた粘着剤1を、ホットメルト塗工機を使用してPET製剥離性シート上に厚さ50μmにべた塗り塗工して、ホットメルト粘着剤層(X)を得た。表2に記載した条件で得られたホットメルト粘着剤層(X)と、厚さ1mmの軟質ポリウレタンフォーム(水蒸気透過率4000g/m2・24時間)とを加熱ラミネーターを用いて温度80℃・圧力2MPa・速度1M/分の加熱圧着条件で貼り合せ、ホットメルト粘着剤層(A)の厚さが30μmの皮膚貼付用粘着テープを得た。
得られた皮膚貼付用粘着テープのホットメルト粘着剤層(A)の表面をレーザーマイクロスコープ(VK−X100 キーエンス社製)で観察したところ、1平方ミリメートル当たり平均4個の孔を有し、その表面空隙率は70%であった。
<Comparative Example 5>
The obtained pressure-
When the surface of the hot melt pressure-sensitive adhesive layer (A) of the obtained adhesive tape for skin application was observed with a laser microscope (VK-X100, manufactured by Keyence Corporation), it had an average of 4 holes per square millimeter. The surface porosity was 70%.
<比較例6>
実施例9と同様にストライプ状の厚さ100μmのホットメルト粘着剤層(X)を作製した。表2に記載した条件で得られたホットメルト粘着剤層(X)と、軟質ポリウレタンフォームを加熱ラミネーターを用いて加熱圧着することで、厚さ50μmのホットメルト粘着剤層(A)を有する皮膚貼付用粘着テープを得た。
得られた皮膚貼付用粘着テープのホットメルト粘着剤層(A)は、レーザーマイクロスコープで観察したところ、1平方ミリメートル当たり平均0個の孔を有し、その表面空隙率は0%であった。
<Comparative Example 6>
In the same manner as in Example 9, a stripe-shaped hot melt pressure-sensitive adhesive layer (X) having a thickness of 100 μm was produced. Skin having a hot-melt pressure-sensitive adhesive layer (A) having a thickness of 50 μm by hot-pressing a hot-melt pressure-sensitive adhesive layer (X) obtained under the conditions described in Table 2 and a flexible polyurethane foam using a heating laminator A sticky adhesive tape was obtained.
The hot melt pressure-sensitive adhesive layer (A) of the obtained adhesive tape for skin application had an average of 0 holes per square millimeter when observed with a laser microscope, and the surface porosity was 0%. .
得られた皮膚貼付用粘着テープについて下記項目を評価した。 The following items were evaluated for the obtained adhesive tape for skin application.
<自着面粘着力>
自着面粘着力は、皮膚に貼付する前に粘着剤層同士を誤って接触させた場合、剥離後の粘着シートを使用できるか否かの面で評価する。
得られた皮膚貼付用粘着シートを縦25mm横150mmの大きさに2枚準備して試料として。次いで2枚の試料から剥離性フィルムを剥がし、試料の粘着剤層同士を重ね、通気性フォーム体上からローラー(重さ500g)を1往復させて圧着し貼り合せた。貼り合せ後、一方の通気性フォーム体の面をステンレス(SUS)板上に両面粘着テープで固定し、他方の方の通気性フォーム体の面を剥離角度180度、剥離速度50mm/分の速度で剥がし、粘着剤層同士の粘着力の測定し自着面粘着力とした。
<Self-adhesive surface adhesive strength>
The self-adhesive surface adhesive strength is evaluated in terms of whether or not the adhesive sheet after peeling can be used when the adhesive layers are mistakenly contacted before being attached to the skin.
Two sheets of the obtained adhesive sheet for skin application were prepared in a size of 25 mm in length and 150 mm in width and used as samples. Subsequently, the peelable film was peeled off from the two samples, the adhesive layers of the samples were overlapped, and the roller (weight 500 g) was reciprocated once from above the breathable foam body, followed by bonding. After bonding, the surface of one air permeable foam body is fixed on a stainless steel (SUS) plate with a double-sided adhesive tape, and the surface of the other air permeable foam body has a peeling angle of 180 degrees and a peeling speed of 50 mm / min. The adhesive strength between the pressure-sensitive adhesive layers was measured and used as the self-adhesive surface adhesive strength.
<粘着力>
得られた皮膚貼付用粘着シートを縦25mm横100mmの大きさに2準備して試料としJIS Z0237に準拠して粘着力を測定した。試料から剥離性シートを剥がし、露出した粘着剤層をSUS板に貼付し、通気性フォーム体上にロール(重さ2kg)を1往復させて圧着し、20分経過後に粘着力を測定した。剥離条件は、剥離角度180度、剥離速度50mm/分で行った。なお、皮膚の状態は個人差があり、数値がばらつくためSUS板を使用している。
<Adhesive strength>
Two prepared adhesive sheets for skin application having a size of 25 mm in length and 100 mm in width were used as samples, and the adhesive force was measured according to JIS Z0237. The peelable sheet was peeled off from the sample, the exposed pressure-sensitive adhesive layer was affixed to a SUS board, and a roll (weight 2 kg) was reciprocated once on the breathable foam body, and the adhesive strength was measured after 20 minutes. The peeling conditions were a peeling angle of 180 degrees and a peeling speed of 50 mm / min. The skin condition varies from individual to individual, and SUS plates are used because the values vary.
<再貼付性>
再貼付性は、皮膚貼付用粘着シートの貼付位置を誤った場合の貼り直しが可能か否か面で評価する。
上記粘着力試験を行った後の試料をローラー(重さ500g)を1往復させて圧着しSUS板に貼付し20分経過後の粘着力を測定した。剥離条件は、剥離角度180度、剥離速度50mm/分の速度で行った。再貼付性の評価基準は以下の通りである。
〇:2回目の粘着力と1回目の粘着力の差が20%未満、良好
×:2回目の粘着力と1回目の粘着力の差が20%以上、実用不可
<Re-stickability>
The re-stickability is evaluated in terms of whether or not the sticking position of the adhesive sheet for skin sticking is incorrect.
The sample after performing the above-mentioned adhesive strength test was reciprocated once by a roller (weight 500 g), adhered to an SUS plate, and the adhesive strength after 20 minutes was measured. The peeling conditions were a peeling angle of 180 degrees and a peeling speed of 50 mm / min. The evaluation criteria for re-stickability are as follows.
◯: The difference between the second adhesive strength and the first adhesive strength is less than 20%, good ×: The difference between the second adhesive strength and the first adhesive strength is 20% or more, impractical
<皮膚貼付性>
得られた粘着シートを、縦10mm横50mmの大きさに準備して試料とした。次いで試料から剥離性シートを剥がし露出した粘着剤層を上腕の内側に貼付した。貼付24時間後に試料を剥がし、剥離後に皮膚状態を目視で観察し以下の基準で評価した。なお、対象とした被験者数は20名で、貼付箇所の蒸れ及びかゆみの発生有無を○△×で評価した。
1.蒸れ(水分による皮膚の白化)
○:蒸れが発生した人数が3人以下、良好
△:蒸れが発生した人数が4人〜8人、実用可
×:蒸れが発生した人数が9人以上、実用不可
××:貼付24時間経過前に粘着シートが剥がれた。実用不可
2.かゆみ
○:かゆみが発生した人数が3人以下、良好
△:かゆみが発生した人数が4人〜8人、実用可
×:かゆみが発生した人数が9人以上、実用不可
××:貼付24時間経過前に粘着シートが剥がれた。実用不可
<Skin adhesiveness>
The obtained adhesive sheet was prepared in a size of 10 mm in length and 50 mm in width and used as a sample. Next, the peelable sheet was peeled off from the sample, and the exposed pressure-sensitive adhesive layer was attached to the inner side of the upper arm. The sample was peeled off 24 hours after application, and the skin condition was visually observed after peeling and evaluated according to the following criteria. In addition, the subject number of subjects was 20 people, and the presence or absence of the occurrence of stuffiness and itching at the pasting site was evaluated by ○ △ ×.
1. Steaming (whitening of skin due to moisture)
○: Number of people with sultry is 3 or less, good △: Number of people with sultry is 4-8 people, practical use ×: Number of people with steaming is 9 or more, impractical use ××: Pasting 24 hours The adhesive sheet was peeled off before. 1. Not practical Itching ○: Number of people with itching is 3 or less, good △: Number of people with itching is 4-8, practical use ×: Number of people with itching is 9 or more, impractical use ××: 24 hours pasting The adhesive sheet peeled off before progress. Impractical
表2の結果から実施例1〜10は、皮膚貼付で皮膚に蒸れやかゆみの発生が少ない効果に加え、適度な自着面粘着力を有することで粘着シートのロスが少なく、再貼付可能という予想外の効果が得られた。 From the results shown in Table 2, Examples 1 to 10 have the effect of less stuffiness and itching on the skin when applied to the skin, and have moderate self-adhesive surface adhesion, resulting in less loss of the adhesive sheet and being able to be reapplied. An unexpected effect was obtained.
11 粘着剤層の塗工幅
12 粘着剤層の塗工間隔
21 粘着剤層の幅
22 粘着剤層の塗工間隔
23 粘着剤層の塗工間隔
11 Adhesive
Claims (7)
前記ホットメルト粘着剤層(A)は、表面の空隙率が5〜50%であり、1平方ミリメートル当たりに円相当径が10〜400μmの孔を2個以上有する、皮膚貼付用粘着シート。 A breathable foam body and a hot melt pressure-sensitive adhesive layer (A),
The hot-melt pressure-sensitive adhesive layer (A) is a pressure-sensitive adhesive sheet for skin application, having a surface porosity of 5 to 50% and two or more holes having a circle equivalent diameter of 10 to 400 μm per square millimeter.
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CN114305869A (en) * | 2022-01-07 | 2022-04-12 | 福智医疗科技(苏州)有限公司 | Medical auxiliary material with sterilization and nourishing effects |
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