JP2004305725A - Hydrocolloidal material and adhesive material using the same - Google Patents
Hydrocolloidal material and adhesive material using the same Download PDFInfo
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- JP2004305725A JP2004305725A JP2004085883A JP2004085883A JP2004305725A JP 2004305725 A JP2004305725 A JP 2004305725A JP 2004085883 A JP2004085883 A JP 2004085883A JP 2004085883 A JP2004085883 A JP 2004085883A JP 2004305725 A JP2004305725 A JP 2004305725A
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- Materials For Medical Uses (AREA)
Abstract
Description
本発明は、創傷、人工的に又は自然にできた小孔、カテーテル導入部等の局所的な保護及びそこからの液体吸収、或いは褥瘡予防のための皮膚の保護や圧力の緩和、医薬物質を皮膚に送達するための基材として使用される医療用のハイドロコロイド材、及びこれを用いた貼付材に関する。 The present invention relates to local protection of wounds, artificially or naturally made pores, catheter introductions and the like, and absorption of liquids therefrom, or skin protection and pressure relief for pressure ulcer prevention, pharmaceutical substances The present invention relates to a medical hydrocolloid material used as a base material for delivery to the skin, and a patch using the same.
従来のハイドロコロイド材には次のような問題点がある。
(イ)皮膚の凹凸への追従性が悪いため、皮膚からの剥がれや浮きが発生する。
(ロ)粘着力が過剰であるため、皮膚からの剥離時に角質を多く剥がす。
(ハ)引っ張り応力が高いため、皮膚伸展に応答出来ず、皮膚からの剥がれや、皮膚への部分的圧迫による皮膚刺激が発生する。
特に(イ)の問題点は(ロ)の問題点とも密接に関係している。即ち、従来のハイドロコロイドは、柔軟性が低いため凹凸のある皮膚に貼付した場合、ハイドロコロイドと皮膚との接触面積が低くなり、少ない接触面積で必要な固定性を得るために粘着力を高くする必要があった。そのため、剥離時の角質剥離量が多くなる傾向があった。又、(ハ)の問題についても、皮膚の伸展時の剥がれを防止するために粘着力を高めようとすれば(ロ)の問題を助長させることになる。尚、ここで言う皮膚の凹凸とは、大きく見ると体の形やシワであり、微小な視点では皮膚の皮溝・皮丘である。
Conventional hydrocolloid materials have the following problems.
(B) Since the followability to the unevenness of the skin is poor, peeling or lifting from the skin occurs.
(B) Due to excessive adhesiveness, a lot of keratin is removed when peeling from the skin.
(C) Since the tensile stress is high, it cannot respond to skin extension, causing peeling from the skin or skin irritation due to partial pressure on the skin.
In particular, the problem (a) is closely related to the problem (b). In other words, conventional hydrocolloids have low flexibility, so when applied to uneven skin, the contact area between the hydrocolloid and the skin is low, and it is necessary to increase the adhesive strength in order to obtain the required fixability with a small contact area. was there. Therefore, there has been a tendency that the amount of exfoliation during exfoliation increases. As for the problem (c), if the adhesive force is increased in order to prevent peeling at the time of skin extension, the problem (b) is promoted. Note that the skin irregularities referred to here are body shapes and wrinkles when viewed broadly, and are skin grooves and dunes from a minute viewpoint.
これらの問題を解決する技術として、可塑化作用のある液状成分を配合し柔軟性を高める提案がなされている。例えば、瘻孔用の袋に用いられる粘着性のシーリング物質として、連続相を形成するスチレン-イソプレン-スチレンブロック共重合体等の弾性体、これらの中に分散されたハイドロコロイド、炭化水素樹脂粘着組成物、油延展剤を含むゲル用組成物で、変形に対して抵抗性が低く、変形後は速やかに元の形に復元するものがある(例えば、特許文献1参照。)。これは、流動パラフィン等の油延展剤を使用して組成物の弾性率を低下させ、変形に対して低い抵抗性を示すようにしたものである。しかしながら、油延展剤は弾性体と比して極端に低分子のものであるため、組成物中に多く配合するとブリーディングし易く、それにより粘着性を低下させ、さらに吸水後の凝集性を大幅に減じる傾向がある。そのため、吸水後の一体性を維持したまま柔軟性を高めるには、この種の方法では限界があった。 As a technique for solving these problems, proposals have been made to increase the flexibility by blending a liquid component having a plasticizing action. For example, as an adhesive sealing substance used for fistula bags, elastic bodies such as styrene-isoprene-styrene block copolymers that form a continuous phase, hydrocolloids dispersed in these, and hydrocarbon resin adhesive compositions Some gel compositions containing an oil spreader have low resistance to deformation, and quickly return to their original shape after deformation (see, for example, Patent Document 1). This uses an oil extender such as liquid paraffin to reduce the elastic modulus of the composition and exhibit low resistance to deformation. However, oil extenders are extremely low in molecular weight compared to elastic bodies, so if blended in a large amount in the composition, they tend to bleed, thereby lowering the tackiness and greatly increasing the cohesion after water absorption. There is a tendency to decrease. For this reason, there is a limit to this type of method in order to increase flexibility while maintaining the integrity after water absorption.
又、同じく瘻孔用の袋に用いられる粘着性物質として、高分子量ポリイソブチレン及びスチレンブロックコポリマーから構成されるエラストマー配合物、炭化水素可塑剤、吸水性ハイドロコロイド、粘着付与剤、抗酸化剤を含む感圧接着性組成物が示されている(例えば、特許文献2参照。)。これは低分子量ポリイソブチレンを使用せず、高分子ポリイソブチレン及び1種類以上のスチレンブロックコポリマーを用いることで、従来の可塑剤を添加することによる凝集性の低下を改質したものと考えられる。 Similarly, the adhesive material used in the fistula bag includes an elastomer compound composed of a high molecular weight polyisobutylene and a styrene block copolymer, a hydrocarbon plasticizer, a water-absorbing hydrocolloid, a tackifier, and an antioxidant. A pressure-bonding composition is shown (for example, see Patent Document 2). This is thought to be due to the use of high molecular weight polyisobutylene and one or more styrene block copolymers, without using low molecular weight polyisobutylene, to improve the decrease in cohesiveness caused by the addition of a conventional plasticizer.
しかし、ある程度の量の可塑剤を添加できたとしても、その一方で可塑剤により粘着性が減少するという問題があり、そのため粘着付与樹脂を添加する必要が生じる。こうすることで、粘着付与樹脂やその抗酸化剤等の多数の異なる原料が組成物中に存在することになるので、皮膚を刺激したり感作したりする物質が入り込む可能性が高くなる。さらに、粘着付与樹脂の特性として、低周波数での弾性率を小さくするが、高周波数での弾性率は高くするという特性がある。そのため、貼付時の粘着性(濡れ)は向上するが、その一方で、剥離時に皮膚に与える刺激は大きくなるという欠点があり、剥離時の皮膚への刺激性を考えると、タッキファイアの使用は控えることが望ましい。 However, even if a certain amount of plasticizer can be added, on the other hand, there is a problem that the tackiness is reduced by the plasticizer, so that it is necessary to add a tackifying resin. By doing so, a number of different raw materials such as tackifying resins and their antioxidants are present in the composition, increasing the likelihood of substances that irritate or sensitize the skin. Further, as a characteristic of the tackifying resin, there is a characteristic that the elastic modulus at a low frequency is reduced, but the elastic modulus at a high frequency is increased. Therefore, the adhesiveness (wetting) at the time of application is improved, but on the other hand, there is a disadvantage that the stimulus given to the skin at the time of peeling increases, and considering the irritation to the skin at the time of peeling, the use of tackifier is not It is desirable to refrain.
さらに、創傷ドレッシングとして、物理的に架橋した固体ゴム、相溶性の液体ゴム、樹脂材料から形成された連続相、及び親水性物質を含む不連続相の混合物を含む感圧接着剤材料が示されている(例えば、特許文献3参照。)。ここには、固体ゴムと液体ゴムの組み合わせにより形成される一体化ネットワークが高い吸収性と吸収後の形状安定性を維持することが記載されている。しかし、このような知見だけでは、皮膚における従来の問題点、即ち、皮膚の凹凸への追従性、皮膚伸展に対する応答性、皮膚剥離時の角質剥離、についての具体的な対応策は開示されていない。 In addition, a pressure sensitive adhesive material comprising a mixture of a physically crosslinked solid rubber, a compatible liquid rubber, a continuous phase formed from a resin material, and a discontinuous phase containing a hydrophilic substance is shown as a wound dressing. (For example, see Patent Document 3). Here, it is described that an integrated network formed by a combination of solid rubber and liquid rubber maintains high absorbency and shape stability after absorption. However, with such knowledge alone, specific countermeasures have been disclosed for conventional problems in skin, i.e., conformability to skin irregularities, responsiveness to skin extension, and exfoliation during skin exfoliation. Absent.
本発明の課題は、適用する患部に対して良好な接着性や皮膚伸展に対する応答性を有し、さらに患部から発生する汗や滲出液に対して十分な吸収性と吸収後の形状保持性を維持し、しかも剥離時には組成物の患部への残留がなく皮膚や創面にダメージを与えず剥離できるハイドロコロイド材及びこれを用いた貼付材を提供することを課題とする。 The object of the present invention is to have good adhesiveness and responsiveness to skin extension to the affected area to be applied, and sufficient absorbability and shape retention after absorption to sweat and exudate generated from the affected area. It is an object of the present invention to provide a hydrocolloid material that can be maintained and can be peeled off without damaging the skin or wound surface without leaving the composition on the affected area during peeling, and a patch using the hydrocolloid material.
そこで、上述の課題を解決するために、本発明者はハイドロコロイドの粘弾性について検討を重ねたところ、ある条件で特定の複素弾性率及び位相差を示すハイドロコロイド材により、上記課題を解決することを見出し、本発明を完成するに至った。 Therefore, in order to solve the above-mentioned problems, the present inventor has repeatedly studied the viscoelasticity of hydrocolloids. As a result, the hydrocolloid material exhibiting a specific complex elastic modulus and phase difference under a certain condition has solved the above problems. The headline and the present invention were completed.
即ち、本発明においては、皮膚表面上に適用するハイドロコロイド材であって、37℃で測定した複素弾性率と位相差の値が、周波数0.1Hzの時に複素弾性率10000〜80000Paで位相差10°〜40°、周波数1.0Hzの時に複素弾性率30000〜130000Paで位相差20°〜55°、周波数10.0Hzの時に複素弾性率60000〜500000Paで位相差25°〜50°を有するようにしたものである。 That is, in the present invention, it is a hydrocolloid material applied on the skin surface, and the value of the complex elastic modulus and phase difference measured at 37 ° C. is a complex elastic modulus of 10,000 to 80000 Pa and a phase difference of 10 ° when the frequency is 0.1 Hz. It has a phase difference of 20 ° to 55 ° at a complex elastic modulus of 30000 to 130,000Pa at a frequency of ~ 40 ° and a frequency of 1.0Hz, and a phase difference of 25 ° to 50 ° at a complex elastic modulus of 60000 to 500000Pa at a frequency of 10.0Hz. is there.
本発明においては、ハイドロコロイド材が、熱可塑性エラストマーと、熱可塑性エラストマーと相溶性の液状ゴムと、水溶性及び/又は水不溶性の親水性物質とを含むようにすると有利である。尚、ここでいう相溶性とは、熱可塑性エラストマーと液状ゴムを混合したときに、均質の混合物を形成する性質を示す。 In the present invention, it is advantageous that the hydrocolloid material contains a thermoplastic elastomer, a liquid rubber compatible with the thermoplastic elastomer, and a water-soluble and / or water-insoluble hydrophilic substance. The term “compatible” as used herein refers to the property of forming a homogeneous mixture when thermoplastic elastomer and liquid rubber are mixed.
ハイドロコロイドが有する粘着性能は、粘弾性の挙動と大いに関連がある。粘弾性とは粘性と弾性を併せ持つ性質のことである。即ち、外力を加えると、変形(ひずみ)を起こし、外力を取り除いたときに変形が回復し元の形に戻ろうとする弾性の挙動と、変形したままで元に戻らない粘性の挙動との両方を持つ物質に関する特性である。この粘弾性を定量的に表すのが、動的粘弾性係数とも呼ばれる複素弾性率で、これは粘性成分と弾性成分のベクトル合成成分であり、物質の硬さや柔らかさを表す一つの指標である。又、粘性成分と弾性成分の割合は、位相差によって表すことができる。純粋な粘性体の場合、位相差は90度となる。一方、純粋な弾性体の場合、位相差は0度となる。このように、粘着という機能においては、粘着物の硬さや柔らかさ(複素弾性率)と、粘着物の持つ粘性と弾性のバランス(位相差)を調整することが重要である。 The adhesive performance of hydrocolloids is highly related to viscoelastic behavior. Viscoelasticity is a property that has both viscosity and elasticity. That is, when an external force is applied, both deformation behavior that causes deformation (strain) and recovers to return to its original shape when the external force is removed, and viscous behavior that remains deformed and does not return to its original shape. It is a property related to a substance with This viscoelasticity is expressed quantitatively by the complex elastic modulus, also called the dynamic viscoelastic coefficient, which is a vector composition component of the viscous component and the elastic component, and is an indicator of the hardness and softness of the substance. . The ratio between the viscous component and the elastic component can be expressed by a phase difference. In the case of a pure viscous material, the phase difference is 90 degrees. On the other hand, in the case of a pure elastic body, the phase difference is 0 degree. Thus, in the function of adhesion, it is important to adjust the hardness and softness (complex elastic modulus) of the adhesive and the viscosity / elasticity balance (phase difference) of the adhesive.
粘性及び弾性の測定方法としては、クリープ試験(いわゆる保持力試験)のような静的な測定方法や、オシレーションと呼ばれる測定物質に変形を加えるときに変形の速度を変化させる(周波数依存)動的な測定方法がある。実際に皮膚に貼付することを考えた場合、変形の速度が変化する動的な試験方法の方が実使用に近い現象を観察できるから、本発明ではこの測定方法を採用している。 Viscosity and elasticity can be measured by static measurement methods such as a creep test (so-called holding force test), or by changing the speed of deformation (frequency-dependent) when applying deformation to a measurement substance called oscillation. There is a typical measurement method. Considering the fact that it is actually applied to the skin, the dynamic test method in which the speed of deformation changes can observe a phenomenon closer to actual use. Therefore, this measurement method is employed in the present invention.
本発明では、複素弾性率及び位相差を、人体の貼付に適すると思われる周波数帯(変形の速度)、即ち低周波数域、高周波数域及びその中間周波数域にて測定することで、動的な粘弾性のデータを得ており、低周波数域として0.1Hz、中間周波数域として1Hz、高周波数域として10Hzを使用している。周波数と粘着挙動との関係は次ぎのように考えられる。低周波数域での測定における、複素弾性率および位相差は、粘着物の被着材への付着(濡れ)やクリープ挙動(塑性変形)等の低速で微小変形の過程に関係する。低周波数域において硬い(複素弾性率が高すぎる)ものや弾性成分が多い(位相差が低すぎる)場合は、低速での良好な変形が出来ず、濡れ性が良くない。しかし、逆に柔らかすぎたり(複素弾性率が低すぎる)、粘性成分が多すぎたりする(位相差が高すぎる)と凝集性が低下し、コールドフロー(保管時の変形、ダレ)や吸水後の形状保持性の低下といった問題を生じる。高周波数域での測定における複素弾性率および位相差は、タックと剥離挙動等の高速の変形過程に関係する。高周波数域において硬い(複素弾性率が高すぎる)ものや弾性成分が多い(位相差が低すぎる)場合は、高速での良好な変形が出来ず、十分なタックが得られなかったり、剥離時に被着体に過度なストレスをかけたりすることがある。逆に柔らかすぎたり(複素弾性率が低すぎる)、粘性成分が多すぎたりする(位相差が高すぎる)と剥離時の皮膚への糊残りといった問題を生じる。さらに、低周波数と高周波数の中間領域として測定した複素弾性率および位相差は、貼付中の皮膚への追従性に影響を与えるものと考えられる。つまり、適切な複素弾性率と位相差をもつように設計されていないと、皮膚そのものの伸縮性、即ち、皮膚の伸展等による皮膚の動きに応答できず、貼付中に違和感が生じる。 In the present invention, the complex elastic modulus and the phase difference are measured in a frequency band (deformation speed) that seems to be suitable for sticking of a human body, that is, in a low frequency range, a high frequency range, and an intermediate frequency range thereof. Viscoelasticity data has been obtained, using 0.1Hz as the low frequency range, 1Hz as the intermediate frequency range, and 10Hz as the high frequency range. The relationship between frequency and adhesion behavior is considered as follows. The complex elastic modulus and phase difference in the measurement in the low frequency range are related to the process of minute deformation at a low speed such as adhesion (wetting) of the adherent to the adherend and creep behavior (plastic deformation). When it is hard in the low frequency range (complex elastic modulus is too high) or there are many elastic components (the phase difference is too low), good deformation at low speed cannot be achieved and wettability is not good. However, if it is too soft (complex elastic modulus is too low) or there are too many viscous components (phase difference is too high), the cohesiveness will be reduced, and after cold flow (deformation or sag during storage) or water absorption This causes problems such as a decrease in shape retention. The complex elastic modulus and phase difference in the measurement in the high frequency range are related to high-speed deformation processes such as tack and peeling behavior. If it is hard in the high frequency range (complex elastic modulus is too high) or has a lot of elastic components (the phase difference is too low), good deformation at high speed cannot be achieved and sufficient tack cannot be obtained, or during peeling Excessive stress may be applied to the adherend. Conversely, if it is too soft (complex elastic modulus is too low) or there are too many viscous components (phase difference is too high), problems such as adhesive residue on the skin at the time of peeling occur. Furthermore, the complex elastic modulus and phase difference measured as an intermediate region between the low frequency and the high frequency are considered to affect the followability to the skin being applied. In other words, unless it is designed so as to have an appropriate complex elastic modulus and phase difference, it cannot respond to the elasticity of the skin itself, that is, the movement of the skin due to the extension of the skin or the like, and uncomfortable feeling occurs during the application.
本発明の37℃で測定した複素弾性率と位相差の値は、周波数0.1Hzの時に複素弾性率10000〜80000Paで位相差10°〜40°が好ましく、複素弾性率15000〜40000Paで位相差20°〜35°がさらに好ましい。複素弾性率が10000Paより小さく位相差が40°より大きいと、凝集性が低下しコールドフロー(保管時の変形、ダレ)や吸水後の形状保持性が低下し易く、一方、複素弾性率が80000Paより大きく位相差が10°より小さいと、濡れ性が低下する。また、周波数1.0Hzの時に複素弾性率20000〜130000Paで位相差20°〜55°が好ましく、複素弾性率25000〜100000Paで位相差25°〜50°がさらに好ましい。複素弾性率が20000Paより小さく位相差が55°より大きいと、浸出液を吸収した時の貼付位置からのずれや変形が起こり易く、一方、複素弾性率が130000Paより大きく位相差が20°より小さいと、伸展等による皮膚の動きに応答できず、貼付中に違和感が生じる。さらに、周波数10.0Hzの時に複素弾性率60000〜500000Paで位相差25°〜50°が好ましく、複素弾性率100000〜400000Paで位相差30°〜45°がさらに好ましい。複素弾性率が60000Paより小さく位相差が50°より大きいと、吸水後のハイドロコロイドの一体保持性が低下し、剥離時に糊残りやハイドロコロイドの崩壊が起こり易く、一方、複素弾性率が500000Paより大きく位相差が25°より小さいと、貼付時には良好なタックが得られ難く、剥離時には貼付部位に過度なストレスがかかり易くなる。 The value of the complex elastic modulus and phase difference measured at 37 ° C. of the present invention is preferably a complex elastic modulus of 10,000 to 80,000 Pa and a phase difference of 10 ° to 40 ° at a frequency of 0.1 Hz, and a complex elastic modulus of 15000 to 40,000 Pa and a phase difference of 20 More preferably, the angle is 35 °. If the complex elastic modulus is less than 10000 Pa and the phase difference is greater than 40 °, the cohesiveness is reduced, and cold flow (deformation and sag during storage) and shape retention after water absorption are likely to decrease, while the complex elastic modulus is 80000 Pa. If it is larger and the phase difference is smaller than 10 °, the wettability decreases. Further, when the frequency is 1.0 Hz, a phase difference of 20 ° to 55 ° is preferable when the complex elastic modulus is 20000 to 130,000 Pa, and a phase difference of 25 ° to 50 ° is more preferable when the complex elastic modulus is 2500 to 100000 Pa. If the complex elastic modulus is less than 20000 Pa and the phase difference is greater than 55 °, displacement and deformation from the application position when the exudate is absorbed are likely to occur, while the complex elastic modulus is greater than 130,000 Pa and the phase difference is less than 20 °. Inability to respond to skin movement due to extension, etc., and uncomfortable feeling occurs during application. Furthermore, when the frequency is 10.0 Hz, a phase difference of 25 ° to 50 ° is preferable at a complex elastic modulus of 60000 to 500000 Pa, and a phase difference of 30 ° to 45 ° is more preferable at a complex elastic modulus of 100000 to 400000 Pa. If the complex elastic modulus is smaller than 60000 Pa and the phase difference is larger than 50 °, the monolithic retention of hydrocolloid after water absorption decreases, and adhesive residue and hydrocolloid collapse easily occur at the time of peeling, while the complex elastic modulus is larger than 500000 Pa. When the phase difference is less than 25 °, it is difficult to obtain a good tack at the time of application, and excessive stress is easily applied to the application site at the time of peeling.
本発明において、上記物性を発揮するハイドロコロイドの好ましい配合は、熱可塑性エラストマーと、熱可塑性エラストマーと相溶性の液状ゴムと、水溶性及び/又は水不溶性の親水性物質とからなる配合である。又、特定の使用について性質を変化させるため、酸化防止剤、凝集力補強材、可塑剤、粘着付与剤、創傷治癒剤、抗菌剤、殺菌剤、消臭剤等の他の材料を添加することができる。ただし、本発明においては、これら他の材料を加えたとしても、本発明が定める上記複素弾性率及び位相差の範囲を逸脱しないように配合することが好ましい。 In the present invention, a preferred blend of hydrocolloids exhibiting the above physical properties is a blend composed of a thermoplastic elastomer, a liquid rubber compatible with the thermoplastic elastomer, and a water-soluble and / or water-insoluble hydrophilic substance. Also add other materials such as antioxidants, cohesive strength reinforcements, plasticizers, tackifiers, wound healing agents, antibacterial agents, bactericides, deodorants to change properties for specific uses Can do. However, in the present invention, even if these other materials are added, it is preferable that they are blended so as not to depart from the ranges of the complex elastic modulus and phase difference defined by the present invention.
熱可塑性エラストマーとしては、スチレン系共重合体が利用でき、スチレン-イソプレン-スチレンブロック共重合体(SIS)、スチレン-ブタジエン-スチレンブロック共重合体(SBS)、スチレン-エチレン/プロピレン-スチレンブロック共重合体(SEPS)、スチレン-エチレン/ブチレン-スチレンブロック共重合体(SEBS)、スチレン-エチレン/エチレン/プロピレン-スチレンブロック共重合体(SEEPS)、水添スチレン-ブタジエンラバー(HSBR)、スチレン-エチレン/ブチレン-オレフィン結晶ブロック共重合体(SEBC)、オレフィン結晶-エチレン/ブチレン-オレフィン結晶ブロック共重合体(CEBC)、ウレタン系共重合体、アクリル系共重合体が好ましい。又、その粘度平均分子量としては100000〜500000の範囲のものを選択するのが好適であり、ハイドロコロイドに弾性の性質を付与している。 As the thermoplastic elastomer, a styrene copolymer can be used, such as a styrene-isoprene-styrene block copolymer (SIS), a styrene-butadiene-styrene block copolymer (SBS), and a styrene-ethylene / propylene-styrene block copolymer. Polymer (SEPS), styrene-ethylene / butylene-styrene block copolymer (SEBS), styrene-ethylene / ethylene / propylene-styrene block copolymer (SEEPS), hydrogenated styrene-butadiene rubber (HSBR), styrene- An ethylene / butylene-olefin crystal block copolymer (SEBC), an olefin crystal-ethylene / butylene-olefin crystal block copolymer (CEBC), a urethane copolymer, and an acrylic copolymer are preferable. Further, it is preferable to select a viscosity average molecular weight in the range of 100,000 to 500,000, which imparts elastic properties to the hydrocolloid.
熱可塑性エラストマーと相溶性の液状ゴムとしては、粘度平均分子量29000〜50000の液状イソプレンゴム(LIR)、粘度平均分子量30000〜50000の液状スチレン-イソプレンゴム(LSIR)、粘度平均分子量20000〜40000の液状エチレン/プロピレンゴム(LEPR)、粘度平均分子量10000〜30000の液状スチレン-エチレン/プロピレンゴム(LSEPR)、粘度平均分子量30000〜100000の液状ポリイソブチレン、粘度平均分子量200〜5000の液状ポリブテンが好ましい。この液状ゴムは、熱可塑性エラストマーの弾性を低下させ柔軟性を付与すると共に、粘着性を高める働きもする。相溶性の点から、熱可塑性エラストマーと液状ゴムの組み合わせとして好ましいのは、SISであればLIR及び/又はLSIR、SBSであれば液状ブタジエンゴム、SEPSであればLEPR及び/又はLSEPR、HSBRであればLEPR、LSEPR、液状ポリイソブチレン、液状ポリブテンのいずれか1種、もしくはこれらの混合物からなる液状ゴム、の組み合わせである。 Liquid rubbers compatible with thermoplastic elastomers include liquid isoprene rubber (LIR) with a viscosity average molecular weight of 29,000 to 50,000, liquid styrene-isoprene rubber (LSIR) with a viscosity average molecular weight of 30,000 to 50,000, and a liquid with a viscosity average molecular weight of 20,000 to 40,000. Preferred are ethylene / propylene rubber (LEPR), liquid styrene-ethylene / propylene rubber (LSEPR) having a viscosity average molecular weight of 10,000 to 30,000, liquid polyisobutylene having a viscosity average molecular weight of 30,000 to 100,000, and liquid polybutene having a viscosity average molecular weight of 200 to 5,000. This liquid rubber lowers the elasticity of the thermoplastic elastomer to give flexibility and also increases the tackiness. From the viewpoint of compatibility, the combination of thermoplastic elastomer and liquid rubber is preferably LIR and / or LSIR for SIS, liquid butadiene rubber for SBS, LEPR and / or LSEPR and HSBR for SEPS. For example, a combination of LEPR, LSEPR, liquid polyisobutylene, liquid polybutene, or a liquid rubber made of a mixture thereof.
このような相溶性の良い組み合わせにすることで、液状ゴムの配合比を増やした場合、即ち柔軟性を高めようとする場合でも、液状ゴムのブリーディングや剥離時の糊残りを防ぐことができる。さらに、この組み合わせの中でもSEPSとLEPR及び/又はLSEPRの組み合わせが特に好ましい。というのは、SEPSとLEPR及びLSEPRは2重結合を含まないのでSISよりも熱や光に対する安定性が高く、適度な粘性を有するため吸水後でも良好な接着性を示すことができるからである。さらに、液状ゴムは架橋したものを用いることができ、凝集性を向上させる目的で適宜配合すると効果的である。又、熱可塑性エラストマーと、熱可塑性エラストマーと相溶性の良い液状ゴムの重量比が1:2〜1:6の範囲であり、さらに熱可塑性エラストマーと熱可塑性エラストマーと相溶性の良い液状ゴムの混合物の粘度平均分子量が30000〜200000の範囲になるように配合するのが好ましく、30000〜100000の範囲になるように配合するのがさらに好ましい。 By making such a compatible combination, even when the blending ratio of the liquid rubber is increased, that is, when flexibility is to be increased, bleeding of the liquid rubber and adhesive residue at the time of peeling can be prevented. Further, among these combinations, a combination of SEPS and LEPR and / or LSEPR is particularly preferable. This is because SEPS, LEPR, and LSEPR do not contain a double bond, and thus have higher stability to heat and light than SIS, and have an appropriate viscosity, and thus can exhibit good adhesion even after water absorption. . Further, the liquid rubber may be a cross-linked one, and it is effective to mix it appropriately for the purpose of improving the cohesiveness. The weight ratio of the thermoplastic elastomer and the liquid rubber having good compatibility with the thermoplastic elastomer is in the range of 1: 2 to 1: 6, and the mixture of the thermoplastic elastomer and the liquid elastomer having good compatibility with the thermoplastic elastomer. The viscosity average molecular weight is preferably in the range of 30000-200000, and more preferably in the range of 30000-100,000.
水溶性及び/又は水不溶性の親水性物質としては、従来から使用されているものを単独又はいくつか組み合わせて使用することができる。親水性物質が存在することで、ハイドロコロイドは、汗や浸出液を吸収することができる。親水性物質として好ましいものは、ペクチン、カルボキシメチルセルロース・ナトリウム(CMC-Na)、グアガム、ゼラチン、カラヤガム、アルギン酸、キチン、キトサン、ポリビニルアルコール、ポリアクリル酸塩、デンプン・アクリル酸グラフト重合体である。又、親水性物質はハイドロコロイドの全重量に対して、10〜60重量%含まれていることが好ましい。 As the water-soluble and / or water-insoluble hydrophilic substance, those conventionally used can be used singly or in combination. Due to the presence of the hydrophilic substance, the hydrocolloid can absorb sweat and leachate. Preferable hydrophilic substances are pectin, carboxymethylcellulose sodium (CMC-Na), guar gum, gelatin, karaya gum, alginic acid, chitin, chitosan, polyvinyl alcohol, polyacrylate, starch / acrylic acid graft polymer. The hydrophilic substance is preferably contained in an amount of 10 to 60% by weight based on the total weight of the hydrocolloid.
さらに、特定の使用について性質を変化さる目的で、種々の物質を添加させることも有効である。例えば、熱可塑性エラストマーを軟化させる目的で、流動パラフィン、ペトロラタム等の鉱油を加えたり、粘着性を高めるために、分子量300000〜500000の範囲のブチルゴムを加えたりすることができる。又、既に損傷を受けた皮膚又は、損傷が予想される皮膚に対しては、皮膚の治療又は損傷の予防、美容等を目的とする薬効成分を添加することができる。例えば、度重なる角質剥離で、ダメージを受けた皮膚に対しては、セラミド等の保湿効果のある物質を添加させることで、本発明の剥離刺激の少ないハイドロコイド材の特性と協同し、効果的に健常皮膚に近づけることができる。他にも、褥瘡発生が懸念される部位に本発明のハイドロコロイド材を適用する場合には、血流促進効果の高いγオリザノール等を添加させることにより、体圧によって生じる血管の閉塞を緩和し、褥瘡予防が期待できる。 Furthermore, it is also effective to add various substances for the purpose of changing properties for a specific use. For example, mineral oil such as liquid paraffin and petrolatum can be added for the purpose of softening the thermoplastic elastomer, or butyl rubber having a molecular weight in the range of 300,000 to 500,000 can be added in order to increase the tackiness. In addition, a medicinal component for the purpose of skin treatment or prevention of damage, beauty and the like can be added to skin that has already been damaged or is expected to be damaged. For example, for skin that has been damaged due to repeated exfoliation, by adding a substance with a moisturizing effect such as ceramide, it is effective in cooperation with the characteristics of the hydrocoid material with less peeling irritation of the present invention. Can be close to healthy skin. In addition, when applying the hydrocolloid material of the present invention to the site where the occurrence of pressure ulcers is concerned, by adding γ oryzanol or the like with a high blood flow promoting effect, alleviation of the occlusion of blood vessels caused by body pressure, Anti-decubitus can be expected.
本発明のハイドロコロイド材を使用した貼付材は、その皮膚の適用部位に適した形状に形成することができるが、取扱い性を向上させるために、ハイドロコロイド材をシート状に形成し、その片面に支持層を設けることが好ましい。支持層としては高分子化合物を加工したものを利用できる。高分子化合物としては、例えば、ポリオレフィン(ポリエチレン、ポリプロピレン及びこれらの変性物等)、オレフィン共重合体(エチレン−ビニルアセテート共重合体、エチレン−エチル(メタ)アクリレート共重合体、エチレン−メチル(メタ)アクリレート共重合体及びエチレン−(メタ)アクリル酸共重合体等)、ポリウレタン、ポリエステル、ポリアクリル酸、ポリアミド、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリスチレン、フッ素樹脂、シリコーン樹脂、セルロース、天然繊維(綿、毛、麻及び絹等)及び化学繊維(ビスコースレイヨン、キュプラレーヨン、ポリノジック、アセテート、トリアセテート、ポリエチレン、ポリプロピレン、ポリアミド、ポリエステル、ポリアクリルニトリル、ビニロン、ポリ塩化ビニル、ビニリデン及びポリウレタン等)等が用いられる。これらのうち、好ましくは、ポリオレフィン、ポリウレタン、ポリエステル及びポリアクリル酸であり、特に好ましくはポリウレタンである。支持体の形体としては、フィルム、フォーム(スポンジ)、不織布、織布及び編み布等が挙げられる。これらのうち、フィルム及びフォームが好ましく、さらに好ましくはフィルムである。特に、柔軟性、伸縮性、適度の水蒸気透過性、菌バリヤー性の観点からポリウレタン性のフィルムが好ましい。 The patch using the hydrocolloid material of the present invention can be formed into a shape suitable for the application site of the skin. However, in order to improve the handleability, the hydrocolloid material is formed into a sheet and supported on one side. It is preferable to provide a layer. As the support layer, a processed polymer compound can be used. Examples of the polymer compound include polyolefin (polyethylene, polypropylene, and modified products thereof), olefin copolymer (ethylene-vinyl acetate copolymer, ethylene-ethyl (meth) acrylate copolymer, ethylene-methyl (meta ) Acrylate copolymer and ethylene- (meth) acrylic acid copolymer), polyurethane, polyester, polyacrylic acid, polyamide, polyvinyl chloride, polyvinylidene chloride, polystyrene, fluororesin, silicone resin, cellulose, natural fiber ( Cotton, wool, hemp and silk) and chemical fibers (viscose rayon, cupra rayon, polynosic, acetate, triacetate, polyethylene, polypropylene, polyamide, polyester, polyacrylonitrile, vinylon, polyvinyl chloride, vinyl Isopropylidene and polyurethane, etc.) and the like. Of these, preferred are polyolefin, polyurethane, polyester and polyacrylic acid, and particularly preferred is polyurethane. Examples of the shape of the support include a film, foam (sponge), nonwoven fabric, woven fabric, and knitted fabric. Of these, films and foams are preferable, and films are more preferable. In particular, a polyurethane film is preferred from the viewpoints of flexibility, stretchability, moderate water vapor permeability, and fungus barrier properties.
本発明によれば、ハイドロコロイド材に特定の複素弾性率及び位相差を持たせることにより、適用する患部に対して良好な接着性や皮膚伸展に対する応答性を有し、さらに患部から発生する汗や滲出液に対して十分な吸収性と吸収後の形状保持性を維持し、しかも剥離時には組成物の患部への残留がなく皮膚や創面にダメージを与えず剥離することができる。又、本発明のハイドロコロイド材は、ブリーディングし易い材料や皮膚を刺激し易い材料の存在を特段必要とせず、少数の材料で構成することができるため製造が簡単で経済的にも有利である。 According to the present invention, by giving the hydrocolloid material a specific complex elastic modulus and phase difference, it has good adhesiveness to the affected area to be applied and responsiveness to skin extension, and sweat and Sufficient absorbability with respect to the exudate and shape retention after absorption are maintained, and at the time of peeling, the composition does not remain on the affected area and can be peeled without damaging the skin or wound surface. Further, the hydrocolloid material of the present invention does not particularly require the presence of a material that easily bleeds or a material that easily irritates the skin, and can be composed of a small number of materials, so that it is easy to manufacture and is economically advantageous.
以下に、本発明の実施例とその評価結果について述べる。 Examples of the present invention and evaluation results thereof will be described below.
実施例1:熱可塑性エラストマーとしてS1S(エニケム社製 分子量約170000)18.2重量部と、熱可塑性エラストマーに対し相溶性の良い液状ゴムとしてLIR(クラレ社製 分子量約29000)42.3重量部と、ポリイソブチレン(日本石油化学社製)27.8重量部と、ブチルゴム(エクソン社製)11.9重量部とを加圧ニーダーに仕込み、十分均一になるまで混合する。次に、親水性物質としてCMC-Na(ダイセル社製)33.3重量部を加え均等になるまで加圧混合し、粘着配合物を作成した。 Example 1: 18.2 parts by weight of S1S as a thermoplastic elastomer (molecular weight of about 170,000 manufactured by Enychem), 42.3 parts by weight of LIR (molecular weight of about 29000, manufactured by Kuraray Co., Ltd.) as a liquid rubber having good compatibility with the thermoplastic elastomer, and polyisobutylene Charge 27.8 parts by weight (manufactured by Nippon Petrochemical Co., Ltd.) and 11.9 parts by weight of butyl rubber (manufactured by Exxon) into a pressure kneader and mix until uniform. Next, 33.3 parts by weight of CMC-Na (manufactured by Daicel) was added as a hydrophilic substance and mixed under pressure until uniform, thereby preparing an adhesive composition.
実施例2〜7は、実施例1と同様の方法を用い、異なる成分で配合した本発明の実施例で、実施例8、9は実施例7のハイドロコロイド材に、セラミドとγオリザノールを各々添加した実施例で、その配合を一覧にして、図1に示す。 Examples 2 to 7 are examples of the present invention blended with different components using the same method as in Example 1. Examples 8 and 9 are the addition of ceramide and γ oryzanol to the hydrocolloid material of Example 7, respectively. FIG. 1 shows a list of the formulations.
上記配合により得られたハイドロコロイド組成物を厚さ600μmに圧延し、15μmのポリウレタンフィルムを支持層としたハイドロコロイド貼付材の検体を作成した。この検体を対象にし、粘弾性、吸水性、粘着特性(初期粘着力、シール性)、皮膚貼付試験、角質剥離性について検証した。以下に各試験方法を説明する。 The hydrocolloid composition obtained by the above blending was rolled to a thickness of 600 μm to prepare a specimen of a hydrocolloid patch using a 15 μm polyurethane film as a support layer. Using this specimen as a target, viscoelasticity, water absorption, adhesive properties (initial adhesive strength, sealability), skin adhesion test, and exfoliation property were verified. Each test method will be described below.
粘弾性: 検体(ただし、本測定に使用する検体だけ、支持層のポリウレタンフィルムを貼り合わる前のものを使用する)から直径20mmの試験片を3枚作成する。相対湿度20%、温度20℃の環境下で回転式レオメーター(HAAKE社製 商品名「レオストレスRS150」)を用いて、測定温度37度、せん断応力100Pa、周波数域0.03〜46Hzの測定条件にてオシレーションの測定を実施し、周波数が0.1Hz、1.0Hz、10.0Hzにおける複素弾性率及び位相差を測定した。 Viscoelasticity: Three test pieces with a diameter of 20 mm are prepared from the specimen (however, only the specimen used for this measurement is the one before the polyurethane film of the support layer is attached). Using a rotary rheometer (trade name “Rheostress RS150” manufactured by HAAKE) in an environment with a relative humidity of 20% and a temperature of 20 ° C., the measurement temperature is 37 degrees, the shear stress is 100 Pa, and the frequency range is 0.03 to 46 Hz. Oscillation was measured, and the complex elastic modulus and phase difference were measured at frequencies of 0.1 Hz, 1.0 Hz, and 10.0 Hz.
吸水性: 検体から直径30mmの試験片を3枚作成する。37℃にて生理食塩液(0.9%NaCl溶液)に浸漬する。浸漬後3時間、6時間、24時間、48時間に試験片の重量を測定して、吸水量及び吸水率を求める。 Water absorption: Make 3 specimens with a diameter of 30mm from the specimen. Immerse in physiological saline (0.9% NaCl solution) at 37 ° C. The weight of the test piece is measured at 3 hours, 6 hours, 24 hours and 48 hours after immersion to determine the water absorption and water absorption.
粘着特性:
a)初期粘着力(JIS T9233 三橋法に準拠):検体から幅15〜25mm、長さ100mmの試験片を3枚作成する。接着円盤(直径50mm、厚さ14mm、アルミニウム製)の表面を有機溶剤で清浄し、乾燥させる。固定された試験片粘着面に前記接着円盤を4.90N(500gf)で2秒間接触させ、30mm/minの速度で引き上げる。接着円盤と試験片が離れるときの粘着力を測定する。
b)シール性(吸水時の初期粘着力): 検体から直径30mmの試験片を3枚作成する。37℃の生理食塩液(0.9%NaCl溶液)に浸漬する。100〜200%吸水後、初期粘着力の試験方法にてシール性を測定する。
Adhesive properties:
a) Initial adhesive strength (conforms to JIS T9233 Mitsuhashi method): Create three test specimens with a width of 15 to 25 mm and a length of 100 mm from the specimen. Clean the surface of the bonded disc (diameter 50 mm, thickness 14 mm, aluminum) with an organic solvent and dry. The adhesive disk is brought into contact with the fixed test piece adhesive surface at 4.90 N (500 gf) for 2 seconds and pulled up at a speed of 30 mm / min. Measure the adhesive strength when the bonded disk and test piece are separated.
b) Sealing property (initial adhesive strength at the time of water absorption): Prepare three test pieces with a diameter of 30 mm from the specimen. Immerse in physiological saline solution (0.9% NaCl solution) at 37 ° C. After water absorption of 100 to 200%, the sealing property is measured by the initial adhesive strength test method.
皮膚貼付試験(繰り返し貼付試験): 検体から幅25mm、長さ50mmの試験片を作成する。被験者2名の上腕内側部に試験片を貼付する。24時間ごとに試験片を交換し、それを3回繰り返す。試験片の交換時に、試験片の剥がれ(めくれ)部分の面積を測定し、試験片全体の面積より剥がれ率を算出する。また、試験片の剥離時にプッシュプルゲージを使用し剥離力を測定する。
Skin sticking test (repeated sticking test): Prepare a
角質剥離性: 皮膚貼付試験で使用した剥離後の試験片を使用する。試験片の中央部から幅15mm、長さ20mmを切り出し、それをホルマリン固定後、エオジン液にて角質を染色する。その後、それをエタノール液で洗浄し、マイクロスコープにて100倍で観察し、角質の剥離量を定性評価する。また、画像解析ソフトにより角質剥離面積を算出する。 Exfoliation: Use the specimen after peeling used in the skin patch test. Cut out 15mm width and 20mm length from the center of the test piece, fix it in formalin, and then stain the keratin with eosin solution. Then, it is washed with an ethanol solution and observed with a microscope at a magnification of 100 to evaluate the amount of exfoliated keratin. Also, the stratum corneum peeling area is calculated by image analysis software.
上記の測定方法による各試験結果は、図2〜図6に示す通りである。尚、本発明の特性の比較として、従来から存在するハイドロコロイド貼付材を比較例1(Convatec社製「デュオアクティブET」)、比較例2(スリーエム社製「テガソーブライト」)とし、併せて検証した。 Each test result by said measuring method is as showing in FIGS. In addition, as a comparison of the characteristics of the present invention, the conventional hydrocolloid patch was compared with Comparative Example 1 (“Duoactive ET” manufactured by Convatec) and Comparative Example 2 (“Tegassorbite” manufactured by 3M) and verified together. did.
図2は、粘弾性(複素弾性率・位相差)の測定結果を示す。図2において、実施例8は、セラミドの影響で、周波数0.1[Hz]における複素弾性率が、他の実施例に比較して高くなったと考えられるが、いずれの実施例も、位相差を含めて、請求項1に記載の好ましい範囲であり、後述するように、ハイドロコロイド材としては、好適な物性を備えることができる。 FIG. 2 shows the measurement results of viscoelasticity (complex elastic modulus / phase difference). In FIG. 2, in Example 8, it is considered that the complex elastic modulus at a frequency of 0.1 [Hz] is higher than that of the other examples due to the influence of ceramide. Thus, the hydrocolloid material can be provided with suitable physical properties as described later.
次に、吸水性の試験結果を示す図3について述べる。図3から分かるように、親水性物質の選択とその配合量により、吸水性の性能を操作できる。実施例2は低吸水性のものとして、発汗に対応できるものであり、健常皮膚に貼付する用途に使用できる。又、それ以外の実施例は高吸水性のものとして、創傷部や人工肛門周囲等の浸出液が比較的多い部位に適応できる。 Next, FIG. 3 showing the water absorption test results will be described. As can be seen from FIG. 3, the water-absorbing performance can be controlled by selecting a hydrophilic substance and its blending amount. Example 2 is a low water-absorbing material that can cope with sweating and can be used for application to healthy skin. In addition, other embodiments are highly water-absorbing and can be applied to sites with a relatively large amount of exudate such as wounds and around the colostomy.
次に、粘着特性の試験結果の図4について述べる。図4から分かるように、特に実施例5〜9においては、SISより粘性の高いSEPS、HSBRを使用しているため、良好なシール性(吸水時粘着性)を示すことが分かる。 Next, FIG. 4 showing the test result of the adhesive property will be described. As can be seen from FIG. 4, in Examples 5 to 9, since SEPS and HSBR having higher viscosity than SIS are used, it can be seen that good sealing properties (adhesiveness during water absorption) are exhibited.
次に、皮膚貼付試験(繰り返し貼付試験)の試験結果の図5によれば、実施例はいずれも皮膚への糊残りがなかった。又、2回目以降の剥離で、比較例は剥離力が増加する傾向にあるが、実施例はほぼ一定の値を示していた。角質は皮膚の内部に向かうほどその結合力は強いので、このような剥離力の増加は、試験片を剥離する都度、角質を剥がしていることを意味すると考えられる。 Next, according to FIG. 5 of the test results of the skin patch test (repeated patch test), none of the examples had any adhesive residue on the skin. Further, in the second and subsequent peeling, the comparative example has a tendency to increase the peeling force, but the example showed a substantially constant value. Since the stratum corneum has a stronger binding force toward the inside of the skin, such an increase in peeling force is considered to mean that the stratum corneum is peeled off every time the test piece is peeled off.
図6は、角質剥離性の試験において、画像解析ソフトにより角質剥離面積を測定した結果である。試験結果によれば、試験片により剥がされた角質は濃い赤色に染色される。1回目の剥離においては、全ての実施例及び比較例の試験片が赤く染色されたが、実施例の方が染色の程度は低かった。ただし、ここで剥離された角質は、皮膚のバリヤー機能には余り関与していない角質(いわゆる垢)であり、皮膚へのダメージはほとんどないと考えられる。2回目以降の剥離では、比較例の試験片はいずれも赤く染色され、多くの角質を剥離しているのに対し、実施例の試験片はほとんど染色されず、剥離される角質がわずかであることが確認された。 FIG. 6 shows the results of measuring the keratin exfoliation area with image analysis software in the keratin exfoliation test. According to the test results, the stratum corneum peeled off by the test piece is dyed dark red. In the first peeling, all the test pieces of Examples and Comparative Examples were stained red, but the degree of staining was lower in the Examples. However, the exfoliated exfoliation is exfoliant (so-called plaque) that is not so much involved in the barrier function of the skin, and it is considered that there is almost no damage to the skin. In exfoliation after the second time, all of the test pieces of the comparative examples are stained red and a lot of keratin is peeled off, whereas the test pieces of the examples are hardly dyed and only a few keratins are peeled off. It was confirmed.
図7は本発明の貼付材の実施例の側面図である。1はフィルム状に形成されたハイドロコロイド層、2はその一方の表面に設けられた支持層、3はもう一方の表面に配置された剥離材である。支持層2はハイドロコロイド層1の形状を保持し、取り扱いし易くする機能を有すると共に、ハイドロコロイド層1の表面を保護する。使用にあたっては、剥離材3を除去した後、ハイドロコロイド層1の露出面を適用しようとする皮膚ないし潰瘍等の上に貼り付けると、ハイドロコロイド層1はその有する粘着性でもって適用部位上に接着される。
FIG. 7 is a side view of an embodiment of the patch of the present invention. Reference numeral 1 denotes a hydrocolloid layer formed in a film shape, 2 a support layer provided on one surface thereof, and 3 a release material disposed on the other surface. The
1 ハイドロコロイド層
2 支持層
3 剥離材
1 Hydrocolloid
Claims (13)
The patch according to claim 12, wherein a support layer is provided on one surface of the sheet-like hydrocolloid material, and a release material is provided on the other surface.
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Cited By (8)
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| JP2006263042A (en) * | 2005-03-23 | 2006-10-05 | Alcare Co Ltd | Adhesive composition for skin application |
| JP2009519916A (en) * | 2005-12-17 | 2009-05-21 | パウル ハルトマン アクチェンゲゼルシャフト | Pharmaceutical composition and wound contact layer comprising the composition |
| WO2009087877A1 (en) | 2008-01-10 | 2009-07-16 | Alcare Co., Ltd. | Pressure-sensitive adhesive agent for skin, pressure-sensitive adhesive sheet for skin and face plate of ostomy appliance |
| JP2011042275A (en) * | 2009-08-21 | 2011-03-03 | Yokohama Rubber Co Ltd:The | Pneumatic tire |
| JP2012135582A (en) * | 2010-12-28 | 2012-07-19 | Alcare Co Ltd | Patch |
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| JP2006263042A (en) * | 2005-03-23 | 2006-10-05 | Alcare Co Ltd | Adhesive composition for skin application |
| JP2009519916A (en) * | 2005-12-17 | 2009-05-21 | パウル ハルトマン アクチェンゲゼルシャフト | Pharmaceutical composition and wound contact layer comprising the composition |
| JP2009519917A (en) * | 2005-12-17 | 2009-05-21 | パウル ハルトマン アクチェンゲゼルシャフト | Pharmaceutical composition comprising active ingredient, and wound contact layer comprising composition |
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| WO2009087877A1 (en) | 2008-01-10 | 2009-07-16 | Alcare Co., Ltd. | Pressure-sensitive adhesive agent for skin, pressure-sensitive adhesive sheet for skin and face plate of ostomy appliance |
| CN101909667A (en) * | 2008-01-10 | 2010-12-08 | 爱乐康株式会社 | Adhesive for skin, adhesive sheet for skin and bottom plate of ostomy appliance |
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| JP2012135582A (en) * | 2010-12-28 | 2012-07-19 | Alcare Co Ltd | Patch |
| JP2016172085A (en) * | 2011-03-31 | 2016-09-29 | ラボラトワール ユルゴ | Healing absorbent dressing and use of the same for chronic wound |
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| WO2016021271A1 (en) * | 2014-08-08 | 2016-02-11 | アルケア株式会社 | Moldable composition for skin applications |
| JPWO2016021271A1 (en) * | 2014-08-08 | 2017-05-18 | アルケア株式会社 | Moldable skin composition |
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| CN117180135A (en) * | 2023-08-25 | 2023-12-08 | 华熙生物科技股份有限公司 | Hydrocolloid dressing, preparation method and application |
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