JP7288324B2 - Hydrocolloid adhesive composition for patching on skin and patch containing the same - Google Patents
Hydrocolloid adhesive composition for patching on skin and patch containing the same Download PDFInfo
- Publication number
- JP7288324B2 JP7288324B2 JP2019059478A JP2019059478A JP7288324B2 JP 7288324 B2 JP7288324 B2 JP 7288324B2 JP 2019059478 A JP2019059478 A JP 2019059478A JP 2019059478 A JP2019059478 A JP 2019059478A JP 7288324 B2 JP7288324 B2 JP 7288324B2
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- JP
- Japan
- Prior art keywords
- adhesive composition
- mass
- hydrocolloid
- skin
- sensitive adhesive
- 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.)
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Description
本発明は、皮膚貼付用ハイドロコロイド型粘着剤組成物に関し、特に創傷用処置剤として好適な皮膚貼付用ハイドロコロイド型粘着剤組成物、及びこれを含む貼付材に関する。 TECHNICAL FIELD The present invention relates to a hydrocolloid-type adhesive composition for application to the skin, and more particularly to a hydrocolloid-type adhesive composition for application to the skin suitable as a treatment agent for wounds, and a patch containing the same.
ハイドロコロイド型粘着剤は、それ自体が粘着性を有し、治癒過程で滲出する創傷分泌物を吸収し、且つ湿潤状態を保持することにより、良好な創傷治癒効果を示すとして近年その重要性が増している。 Hydrocolloid-type adhesives have increased their importance in recent years as they exhibit good wound-healing effects by having adhesiveness per se, absorbing wound secretions exuded during the healing process, and maintaining a moist state. ing.
一般に、ハイドロコロイド型粘着剤は、可塑性ゴムからなる連続相（母材）に吸水性のコロイド粒子（吸水剤）が分散して存在している構造を有し、その多くは、一定時間で自重の３～５倍程度の水又は創傷部位からの滲出液を吸収し得るように調製されている。水等を吸水してもその母材が一体性を失うことがないよう、且つ、所望の粘着性を発揮できるよう、ゴム成分を種々検討した提案がなされている（例えば特許文献１）。また、貼付材に用いられる粘着剤組成物として、単位体積当たりの蒸留水の吸水量が生理食塩水の吸水量と同等か、蒸留水よりも生理食塩水の吸水量が多いものを採用することにより、浸出液を吸収する性能を保持しつつ、所望の粘着性を有し、水に濡れた後であっても粘着性能の低下を抑制することができる貼付材の提案がなされている（例えば特許文献２）。また、近年、環境ホルモン作用や発がん性の疑いが持たれるＤＯＰやＤＯＡ等の可塑剤を替えた場合においても、十分な吸水量・吸水速度の調整ができる、新たな可塑剤の使用を検討した提案もなされている（例えば特許文献３）。さらに、ハイドロコロイド型粘着剤を貼付材、とりわけ救急絆創膏のパッドへの適用を検討した提案もなされている（例えば特許文献４）。これまで、創傷部位を覆い創傷治癒効果が得やすい環境とするために、ハイドロコロイド型粘着剤を添付剤に適用したときに、比較的厚いハイドロコロイド型粘着剤の層が用いられてきた。 In general, hydrocolloid-type adhesives have a structure in which water-absorbing colloidal particles (water-absorbing agents) are dispersed in a continuous phase (base material) made of plastic rubber. It is prepared so that it can absorb about 3 to 5 times as much water or exudate from the wound site. Various proposals have been made to examine rubber components so that the base material does not lose its integrity even if it absorbs water or the like and that it can exhibit the desired adhesiveness (for example, Patent Document 1). In addition, as the adhesive composition used for the adhesive material, the water absorption amount of distilled water per unit volume is equivalent to that of physiological saline, or the water absorption amount of physiological saline is greater than that of distilled water. has proposed a patch that has the desired adhesiveness while retaining the ability to absorb exudates, and that can suppress the deterioration of the adhesive performance even after getting wet with water (for example, patent Reference 2). In addition, in recent years, even when replacing plasticizers such as DOP and DOA, which are suspected of being endocrine disruptors and carcinogenic, we investigated the use of new plasticizers that can sufficiently adjust the amount and speed of water absorption. Proposals have also been made (for example, Patent Document 3). Furthermore, a proposal has been made to examine the application of a hydrocolloid-type adhesive to a patch, especially a bandage pad (for example, Patent Document 4). Hitherto, when a hydrocolloid adhesive is applied to an adhesive patch, a relatively thick layer of the hydrocolloid adhesive has been used in order to cover the wound site and create an environment in which the wound healing effect can be easily obtained.
これらハイドロコロイド型粘着剤は、絆創膏のパッド部や、フィルムを支持体とする粘着テープの粘着剤層として用いられてきた。
ハイドロコロイド型粘着剤は、創傷面における湿潤環境を維持するために、一定時間皮膚への貼付が良好である必要がある。よって、粘着剤層はある程度の柔軟性を持たせなければならない。一方で、貼付材を常温以上の環境下においても、経時で該粘着剤が過度な流動により支持体の端部(以下、「エッジ」ともいう)から染み出してしまうことも防がなければならない。支持体の端部から粘着剤が染み出してしまう傾向は、特に２００μｍ以上の厚い粘着剤層をもつ場合や架橋されていない粘着剤層をもつ粘着テープの共通した課題であり、ハイドロコロイド粘着剤においては、その組成上、顕著に起きる課題であった。貼付材がロール状の場合は、粘着剤層の幅方向の端部が支持体端部を超えて染み出しが起きると、染み出した部分が周回した自身の基材や粘着剤層に相互に付着して、解きほぐす際に解きほぐし力が重くなったり、粘着剤の糸引きを起こしたりするなど、取り扱い性が悪くなる問題がある。また染み出した部分に塵などの異物が付着すると、外観が悪くなるだけでなく衛生上も問題である。
These hydrocolloid-type adhesives have been used as pad portions of bandages and adhesive layers of adhesive tapes having a film as a support.
A hydrocolloid adhesive needs to adhere well to the skin for a certain period of time in order to maintain a moist environment on the wound surface. Therefore, the pressure-sensitive adhesive layer must have some degree of flexibility. On the other hand, it is also necessary to prevent the adhesive from exuding from the edge of the support (hereinafter also referred to as "edge") due to excessive flow over time even when the patch is placed in an environment of room temperature or higher. . The tendency of the adhesive to seep out from the edge of the support is a common problem with adhesive tapes having a thick adhesive layer of 200 μm or more and an adhesive layer that is not crosslinked. was a significant problem due to its composition. In the case of a roll-shaped patch, if the edge of the adhesive layer in the width direction oozes beyond the edge of the backing, the oozing part will be attached to the surrounding base material and the adhesive layer. There is a problem that the handleability is deteriorated, such as sticking and the unraveling force becomes heavy when unraveling, and the stickiness of the adhesive is caused. In addition, if foreign matter such as dust adheres to the exuded portion, it not only deteriorates the appearance but also poses a hygiene problem.
絆創膏や粘着テープ等の貼付材は、皮膚に貼付されて使用されるが、日常生活において、快適な貼付を可能とするために、貼付材のエッジからの染み出しを抑制することも求められている。
従来のハイドロコロイド組成物では、上記の染み出し抑制について、重点的に検討がなされてこなかった。
Adhesive materials such as adhesive plasters and adhesive tapes are used by being attached to the skin, and in order to enable comfortable application in daily life, it is also required to suppress seepage from the edges of the adhesive materials. there is
In the conventional hydrocolloid compositions, the suppression of the seepage has not been intensively studied.
本発明の目的は、上記の課題を解決した皮膚貼付用ハイドロコロイド型粘着剤組成物、すなわち、貼付材に適用したときに側面からの染み出しを抑制し、適度な貼付性とのバランスを有した、快適な貼付を可能にする皮膚貼付用ハイドロコロイド型粘着剤組成物を提供することにある。さらに、着色剤を使用せずとも皮膚の色になじむような色相とすることが可能な、皮膚貼付用ハイドロコロイド型粘着剤組成物を提供することにある。 An object of the present invention is to provide a hydrocolloid-type pressure-sensitive adhesive composition for skin application that solves the above problems, i.e., suppresses exudation from the side when applied to a patch, and has a balance with appropriate stickability. Another object of the present invention is to provide a hydrocolloid-type pressure-sensitive adhesive composition for skin application that enables comfortable application. Another object of the present invention is to provide a hydrocolloid-type pressure-sensitive adhesive composition for application to the skin, which can have a hue that matches the color of the skin without using a coloring agent.
本発明者らは上記課題に対して鋭意研究を行なった結果、貼付材に用いられる粘着剤組成物において、Ｃ５系樹脂及びＣ５／Ｃ９系樹脂からなる群より選択される少なくとも一種を有する粘着付与樹脂を採用することにより、側面からの染み出しを抑制し、適度な貼付性とのバランスを有した、快適な貼付を可能にする皮膚貼付用ハイドロコロイド型粘着剤組成物を提供し得ることを見出した。また、前記皮膚貼付用ハイドロコロイド型粘着剤組成物の△ｂ＊（Ｄ６５）を８以上１７以下とすることで、着色剤を使用せずとも皮膚の色になじむような色相とすることが可能な貼付材を提供し得ることを見出し、本発明を完成させた。 As a result of intensive research conducted by the present inventors on the above-mentioned problems, the adhesive composition used for the patch has at least one selected from the group consisting of C5-based resins and C5/C9-based resins. The inventors have found that by employing a resin, it is possible to provide a hydrocolloid-type pressure-sensitive adhesive composition for application to the skin that suppresses seepage from the sides, has a balance with appropriate application properties, and enables comfortable application. rice field. Further, by setting the Δb* (D65) of the hydrocolloid-type pressure-sensitive adhesive composition for skin application to 8 or more and 17 or less, it is possible to obtain a hue that matches the color of the skin without using a coloring agent. The present invention was completed by discovering that a patch can be provided.
本発明は、下記の構成であり、これにより本発明の上記課題が解決される。 The present invention has the following configurations, and thereby solves the above problems of the present invention.
＜１＞
（Ａ）エラストマー、（Ｂ）粘着付与樹脂、（Ｃ）可塑剤、及び（Ｄ）コロイド粒子を含有する皮膚貼付用ハイドロコロイド型粘着剤組成物であって、
前記（Ａ）エラストマーは、スチレン系ブロック共重合体及びポリイソブチレンを含み、前記ポリイソブチレンの含有量は、前記（Ａ）エラストマーの全質量に対して４０質量％～６０質量％であり、前記（Ａ）エラストマーの含有量は、前記皮膚貼付用ハイドロコロイド型粘着剤組成物の全質量に対して３０質量％～４５質量％であり、前記ポリイソブチレンの含有量は、前記皮膚貼付用ハイドロコロイド型粘着剤組成物の全質量に対して１７質量％～３０質量％であり、
前記（Ｂ）粘着付与樹脂が、Ｃ５／Ｃ９系樹脂、又はＣ５系樹脂のみを含有し、前記（Ｂ）粘着付与樹脂の含有量は、前記皮膚貼付用ハイドロコロイド型粘着剤組成物の全質量に対して１５質量％～３０質量％であり、
前記（Ｃ）可塑剤の含有量は、前記皮膚貼付用ハイドロコロイド型粘着剤組成物の全質量に対して５質量％～１５質量％であり、
前記（Ｄ）コロイド粒子の含有量は、前記皮膚貼付用ハイドロコロイド型粘着剤組成物の全質量に対して２１質量％～４０質量％であり、
前記皮膚貼付用ハイドロコロイド型粘着剤組成物の△ｂ＊（Ｄ６５）が８以上１７以下である、皮膚貼付用ハイドロコロイド型粘着剤組成物（但し、エチレン、プロピレン及び非共役化ジエンから製造される三元共重合体を含むヒドロコロイド組成物、（ａ）１０～３５重量部のポリ（スチレン／オレフィン／スチレン）ブロック共重合体、（ｂ）２０～５０重量部の粘着付与樹脂、（ｃ）２～１５重量部の－２０℃以下のガラス転移温度を有するアクリレートポリマー、（ｄ）２～２５重量部の可塑剤、（ｅ）２０～２５重量部の親水性コロイド、及び（ｆ）０．１～２重量部の少なくとも１つの酸化防止剤を含む親水性の医療用接着性組成物、並びに、疎水相と親水相からなる皮膚接着性組成物であって、（ａ）疎水相は、疎水性ポリマー、少なくとも１つのエラストマー、及び粘着付与樹脂を含み、（ｂ）親水相は、ｉ）低分子量のセルロース誘導性ポリマー、及び天然多糖類からなる群から選択される少なくとも１つの材料、ｉｉ）少なくとも１つの高分子量のセルロース誘導性ポリマー、及び、ｉｉｉ）強化粘土粒子を含む皮膚接着性組成物を除く）。
＜２＞
前記皮膚貼付用ハイドロコロイド型粘着剤組成物の△Ｅ＊ａｂ（Ｄ６５）が１０以上２０以下である、＜１＞に記載の皮膚貼付用ハイドロコロイド型粘着剤組成物。
＜３＞
＜１＞又は＜２＞に記載の皮膚貼付用ハイドロコロイド型粘着剤組成物を含む、貼付材。
本発明は、上記＜１＞～＜３＞に係る発明であるが、以下、それ以外の事項（例えば、下記［１］～［８］についても記載している。
［１］
（Ａ）エラストマー、（Ｂ）粘着付与樹脂、（Ｃ）可塑剤、及び（Ｄ）コロイド粒子を含有する皮膚貼付用ハイドロコロイド型粘着剤組成物であって、前記（Ｂ）粘着付与樹脂が、Ｃ５／Ｃ９系樹脂及びＣ５系樹脂からなる群より選択される少なくとも一種を含有し、前記皮膚貼付用ハイドロコロイド型粘着剤組成物の△ｂ＊（Ｄ６５）が８以上１７以下である、皮膚貼付用ハイドロコロイド型粘着剤組成物。
［２］
前記皮膚貼付用ハイドロコロイド型粘着剤組成物の△Ｅ＊ａｂ（Ｄ６５）が１０以上２０以下である、［１］に記載の皮膚貼付用ハイドロコロイド型粘着剤組成物。
［３］
前記（Ａ）エラストマーは、スチレン系ブロック共重合体及びポリイソブチレンを含む、［１］又は［２］に記載の皮膚貼付用ハイドロコロイド型粘着剤組成物。
［４］
前記ポリイソブチレンの含有量は、前記（Ａ）エラストマーの全質量に対して４０質量％～６０質量％である、［３］に記載の皮膚貼付用ハイドロコロイド型粘着剤組成物。
［５］
前記ポリイソブチレンの含有量は、前記皮膚貼付用ハイドロコロイド型粘着剤組成物の全質量に対して１質量％～３０質量％である、［３］又は［４］に記載の皮膚貼付用ハイドロコロイド型粘着剤組成物。
［６］
前記（Ｃ）可塑剤の含有量は、前記皮膚貼付用ハイドロコロイド型粘着剤組成物の全質量に対して５質量％～１５質量％である、［１］～［５］のいずれか１項に記載の皮膚貼付用ハイドロコロイド型粘着剤組成物。
［７］
前記（Ｂ）粘着付与樹脂の含有量は、前記皮膚貼付用ハイドロコロイド型粘着剤組成物の全質量に対して１５質量％～３０質量％である、［１］～［６］のいずれか１項に記載の皮膚貼付用ハイドロコロイド型粘着剤組成物。
［８］
［１］～［７］のいずれか１項に記載の皮膚貼付用ハイドロコロイド型粘着剤組成物を含む、貼付材。
<1>
(A) an elastomer, (B) a tackifying resin, (C) a plasticizer, and (D) a hydrocolloid adhesive composition for skin application, comprising:
The (A) elastomer contains a styrenic block copolymer and polyisobutylene, the content of the polyisobutylene is 40% by mass to 60% by mass with respect to the total mass of the (A) elastomer, and the ( A) The content of the elastomer is 30% by mass to 45% by mass with respect to the total mass of the hydrocolloid-type pressure-sensitive adhesive composition for patching on the skin, and the content of the polyisobutylene is the hydrocolloid-type pressure-sensitive adhesive for patching on the skin. 17% by mass to 30% by mass relative to the total mass of the composition,
The (B) tackifying resin contains only a C5/C9-based resin or a C5-based resin , and the content of the (B) tackifying resin is the total mass of the hydrocolloid-type adhesive composition for skin application. 15% by mass to 30% by mass with respect to
The content of the (C) plasticizer is 5% by mass to 15% by mass with respect to the total mass of the hydrocolloid adhesive composition for skin application,
The content of the colloidal particles (D) is 21% by mass to 40% by mass with respect to the total mass of the hydrocolloid-type pressure-sensitive adhesive composition for skin application,
A hydrocolloid-type pressure-sensitive adhesive composition for skin application, wherein the hydrocolloid-type pressure-sensitive adhesive composition for skin application has a Δb* (D65) of 8 or more and 17 or less (provided that three A hydrocolloid composition comprising an original copolymer, (a) 10 to 35 parts by weight of a poly(styrene/olefin/styrene) block copolymer, (b) 20 to 50 parts by weight of a tackifying resin, (c) 2 ˜15 parts by weight of an acrylate polymer having a glass transition temperature of −20° C. or less, (d) 2 to 25 parts by weight of a plasticizer, (e) 20 to 25 parts by weight of a hydrophilic colloid, and (f) 0.1. A hydrophilic medical adhesive composition comprising ~2 parts by weight of at least one antioxidant and a skin adhesive composition comprising a hydrophobic phase and a hydrophilic phase, wherein (a) the hydrophobic phase is hydrophobic (b) the hydrophilic phase comprises: i) at least one material selected from the group consisting of low molecular weight cellulose-derived polymers and natural polysaccharides; ii) at least with the exception of one high molecular weight cellulose-derived polymer and iii) a skin-adhesive composition comprising reinforced clay particles ).
<2>
The hydrocolloid-type pressure-sensitive adhesive composition for skin application according to <1>, wherein the hydrocolloid-type pressure-sensitive adhesive composition for skin application has a ΔE*ab (D65) of 10 or more and 20 or less.
<3>
An adhesive patch comprising the hydrocolloid adhesive composition for skin application according to <1> or <2> .
The present invention relates to the above <1> to <3> , but other matters (for example, the following [1] to [8] are also described below.
[1]
(A) an elastomer, (B) a tackifier resin, (C) a plasticizer, and (D) a hydrocolloid adhesive composition for skin application, wherein the (B) tackifier resin is C5 / A hydrocolloid for skin application, which contains at least one selected from the group consisting of C9-based resin and C5-based resin, and wherein the hydrocolloid-type pressure-sensitive adhesive composition for skin application has a Δb* (D65) of 8 or more and 17 or less. mold adhesive composition.
[2]
The hydrocolloid-type pressure-sensitive adhesive composition for application to skin according to [1], wherein ΔE*ab (D65) of the hydrocolloid-type pressure-sensitive adhesive composition for application to skin is 10 or more and 20 or less.
[3]
The hydrocolloid-type pressure-sensitive adhesive composition for skin application according to [1] or [2], wherein the elastomer (A) contains a styrenic block copolymer and polyisobutylene.
[4]
The hydrocolloid pressure-sensitive adhesive composition for skin application according to [3], wherein the content of the polyisobutylene is 40% by mass to 60% by mass with respect to the total mass of the (A) elastomer.
[5]
The hydrocolloid adhesive for skin application according to [3] or [4], wherein the content of the polyisobutylene is 1% by mass to 30% by mass with respect to the total mass of the hydrocolloid adhesive composition for skin application. agent composition.
[6]
Any one of [1] to [5], wherein the content of the (C) plasticizer is 5% by mass to 15% by mass with respect to the total mass of the hydrocolloid-type pressure-sensitive adhesive composition for skin application. The hydrocolloid-type pressure-sensitive adhesive composition for application to the skin as described above.
[7]
Any one of [1] to [6], wherein the content of the (B) tackifying resin is 15% by mass to 30% by mass with respect to the total mass of the hydrocolloid adhesive composition for skin application. 4. The hydrocolloid-type pressure-sensitive adhesive composition for skin application according to .
[8]
A patch comprising the hydrocolloid adhesive composition for skin patching according to any one of [1] to [7].
本発明は、貼付材に適用したときに側面からの染み出しを抑制し、適度な貼付性とのバランスを有した、快適な貼付を可能にする皮膚貼付用ハイドロコロイド型粘着剤組成物を提供することができる。さらに、着色剤を使用せずとも皮膚の色になじむような色相とすることが可能な、皮膚貼付用ハイドロコロイド型粘着剤組成物を提供することができる。
従って、本発明の皮膚貼付用ハイドロコロイド型粘着剤組成物（以下、単に「粘着剤組成物」と称する場合がある）を用いた貼付材は、適度な貼付性を有しながらも、側面からの染み出しが抑制されることから、粘着シートをロール状とした場合に、一部スリットがある箱にロール状の貼付材を封入した場合でも、箱からの引き出し性が良好となり、貼付材として皮膚に貼付した場合には、衣服などの汚れが貼付材のエッジに着きにくいことが期待できる。
そしてこの粘着剤組成物を用いた貼付材は救急絆創膏やドレッシング材等の医療・衛生分野への展開が期待できる。
The present invention provides a hydrocolloid-type pressure-sensitive adhesive composition for skin application that suppresses bleeding from the sides when applied to an adhesive material, has a balance with appropriate adhesiveness, and enables comfortable application. be able to. Furthermore, it is possible to provide a hydrocolloid-type pressure-sensitive adhesive composition for application to the skin, which can have a hue that matches the color of the skin without using a coloring agent.
Therefore, a patch using the hydrocolloid-type adhesive composition for patching to the skin of the present invention (hereinafter, sometimes simply referred to as "adhesive composition") has appropriate adhesiveness, but is not easily affected from the side. Since the seepage is suppressed, when the adhesive sheet is rolled, even if the roll-shaped patch is enclosed in a box with some slits, it can be pulled out easily from the box, and the patch can be used as a patch on the skin. When the tape is attached to the edge of the adhesive material, it can be expected that stains such as clothes are less likely to adhere to the edge of the adhesive material.
Adhesives using this pressure-sensitive adhesive composition are expected to be used in medical and hygiene fields such as first-aid plasters and dressings.
＜皮膚貼付用ハイドロコロイド型粘着剤組成物＞
本発明の皮膚貼付用ハイドロコロイド型粘着剤組成物は、（Ａ）エラストマー、（Ｂ）粘着付与樹脂、（Ｃ）可塑剤、及び（Ｄ）コロイド粒子を含有し、前記（Ｂ）粘着付与樹脂が、Ｃ５系樹脂及びＣ５／Ｃ９系樹脂からなる群より選択される少なくとも一種を含有する。本発明の皮膚貼付用ハイドロコロイド粘着剤組成物は、所望によりその他の成分を含み得る。
以下、上記各成分について詳述する。
<Hydrocolloid adhesive composition for skin application>
The hydrocolloid-type adhesive composition for skin application of the present invention contains (A) an elastomer, (B) a tackifying resin, (C) a plasticizer, and (D) colloidal particles, and the (B) tackifying resin comprises , C5-based resins and C5/C9-based resins. The hydrocolloid pressure-sensitive adhesive composition for skin application of the present invention may optionally contain other ingredients.
Each of the above components will be described in detail below.
［（Ａ）エラストマー］
本発明において使用するエラストマーは、従来使用されているエラストマーであれば特に限定されないが、好適には、スチレン系ブロック共重合体及びポリイソブチレン（以下、ＰＩＢとも称する）を含む。
前記スチレン系ブロック共重合体としては、スチレン・ブタジエンブロック共重合体（ＳＢＳ）及びその水添ゴム（ＳＥＢＳ）、スチレン・イソプレンブロック共重合体（ＳＩＳ）及びその水添ゴム（ＳＥＰＳ）、スチレン・イソブチレンブロック共重合体（ＳＩＢＳ）などが挙げられ、これらの１種あるいは複数を組合せて使用することができる。これらの中でも、ＳＩＳ及びＳＥＢＳが更に好ましく、特に好ましくはＳＩＳが用いられる。
[(A) Elastomer]
Elastomers used in the present invention are not particularly limited as long as they are conventionally used elastomers, but preferably include styrenic block copolymers and polyisobutylene (hereinafter also referred to as PIB).
Examples of the styrene block copolymer include styrene/butadiene block copolymer (SBS) and its hydrogenated rubber (SEBS), styrene/isoprene block copolymer (SIS) and its hydrogenated rubber (SEPS), styrene/ Examples include isobutylene block copolymers (SIBS) and the like, and one or more of these can be used in combination. Among these, SIS and SEBS are more preferred, and SIS is particularly preferred.
前記ポリイソブチレンは、粘着剤組成物の皮膚への接着性を良好なものとすることができ、１種単独でまたは２種類以上の組み合わせにて使用することが好ましい。
ただし、ポリイソブチレンを含む粘着剤組成物は、コールドフロー現象を起こしやすく、粘着剤の染み出しが起きる傾向が認められるため、ポリイソブチレンの含有量は、前記粘着剤組成物の全質量に対して１質量％～３０質量％であることが好ましく、１０質量％～３０質量％であることが更に好ましい。
The polyisobutylene can improve the adhesiveness of the pressure-sensitive adhesive composition to the skin, and is preferably used alone or in combination of two or more.
However, since a pressure-sensitive adhesive composition containing polyisobutylene is likely to cause a cold flow phenomenon and tends to cause the pressure-sensitive adhesive to ooze out, the content of polyisobutylene is It is preferably from 1% by mass to 30% by mass, more preferably from 10% by mass to 30% by mass.
本発明においては市販のポリイソブチレンを使用し得、たとえば、オパノールＢ３０、同Ｂ５０、同Ｂ８０、同Ｎ８０、同Ｎ１００、同Ｂ１５、同Ｂ１５ＳＦＮ、同Ｂ１２（以上、ＢＡＳＦジャパン（株））、ビスタネックスＬＭ－ＭＳ、同ＬＭ－ＭＨ、同ＬＭ－Ｈ（以上、エクソン社）、ハイモール４Ｈ、同５Ｈ、同５．５Ｈ、同６Ｈ、テトラックス３Ｔ、同４Ｔ、同５Ｔ、同６Ｔ（以上、ＪＸ日鉱日石エネルギー（株））等を挙げることができる。ポリイソブチレンの粘度平均分子量：Ｍｖの好適な範囲は１０，０００～１,１１０，０００である。なお、ここで用いる粘度平均分子量は、フローリー法によるものである。
前記ポリイソブチレンの含有量は、前記（Ａ）エラストマーの全質量に対して２０質量％～６５質量％であることが好ましく、４０質量％～６０質量％であることがより好ましい。
In the present invention, commercially available polyisobutylene can be used, for example, Oppanol B30, Oppanol B50, Oppanol B80, Oppanol N80, Oppanol N100, Oppanol B15, Oppanol B15SFN, Oppanol B12 (BASF Japan Ltd.), Vistanex LM-MS, LM-MH, LM-H (exxon), Hymol 4H, 5H, 5.5H, 6H, Tetrax 3T, 4T, 5T, 6T (above, JX Nikko Nisseki Energy Co., Ltd.) and the like can be mentioned. The preferred range of viscosity average molecular weight Mv of polyisobutylene is 10,000 to 1,110,000. The viscosity-average molecular weight used here is determined by the Flory method.
The content of the polyisobutylene is preferably 20% by mass to 65% by mass, more preferably 40% by mass to 60% by mass, based on the total mass of the elastomer (A).
その他、本発明において使用するエラストマーは、液状ゴムを含むこともできる。前記液状ゴムとしては、液状ポリイソプレン（ＬＩＲ）や液状ポリブタジエン（ＬＰＢ）、ポリブテン（ＰＢ）などの液状エラストマー成分を挙げることができる。
なお、前記液状ゴムは、上記のスチレン系ブロック共重合体、ポリイソブチレンとは異なる成分である。
例えば、液状ゴムの含有量は、粘着剤組成物の全質量に対して、０質量％～２０質量％であることが好ましい。
In addition, the elastomer used in the present invention can also contain liquid rubber. Examples of the liquid rubber include liquid elastomer components such as liquid polyisoprene (LIR), liquid polybutadiene (LPB), and polybutene (PB).
The liquid rubber is a component different from the styrene-based block copolymer and polyisobutylene described above.
For example, the content of the liquid rubber is preferably 0% by mass to 20% by mass with respect to the total mass of the adhesive composition.
本発明において、（Ａ）エラストマーの含有量は、粘着剤組成物の全質量に対して、２０質量％～６０質量％であることが好ましく、３０質量％～４５質量％であることがより好ましい。 In the present invention, the content of (A) the elastomer is preferably 20% by mass to 60% by mass, more preferably 30% by mass to 45% by mass, relative to the total mass of the pressure-sensitive adhesive composition. .
［（Ｂ）粘着付与樹脂］
本発明において使用する粘着付与樹脂としては、一般に疎水性ゴムベース成分と相溶して粘着性を発現させる疎水性の樹脂であり、具体的にはロジン樹脂、ロジンエステル樹脂、テルペン樹脂、テルペンフェノール樹脂、Ｃ５系樹脂、Ｃ５／Ｃ９系樹脂、ＤＣＰＤ系石油系樹脂、クマロン・インデン樹脂、またこれらの水添物などが挙げられる。
[(B) Tackifying resin]
The tackifying resin used in the present invention is generally a hydrophobic resin that is compatible with the hydrophobic rubber base component to develop adhesiveness. Specifically, rosin resin, rosin ester resin, terpene resin, terpene phenol resins, C5-based resins, C5/C9-based resins, DCPD-based petroleum-based resins, coumarone-indene resins, and hydrogenated products thereof.
本発明において、前記（Ｂ）粘着付与樹脂は、Ｃ５系樹脂及びＣ５／Ｃ９系樹脂からなる群より選択される少なくとも一種を含有する。 In the present invention, the (B) tackifying resin contains at least one selected from the group consisting of C5-based resins and C5/C9-based resins.
Ｃ５系樹脂としては、Ｃ５系石油樹脂が挙げられ、例えば、Ｃ５系の脂肪族系炭化水素樹脂が挙げられる。具体的には、炭素数４～５個相当の石油留分（Ｃ５留分）であるイソプレンやシクロペンタジエンなどの不飽和モノマーを重合（例えばカチオン重合）することにより得られる樹脂や、１，３－ペンタジエンを濃縮したものを原料とする樹脂である。
Ｃ５系樹脂の軟化点は、好ましくは８０℃～１００℃、更に好ましくは９０℃～１００℃である。
本願明細書において、軟化点は、ＪＩＳ－２２０７に基づいて測定した値である。
Examples of C5 resins include C5 petroleum resins, such as C5 aliphatic hydrocarbon resins. Specifically, resins obtained by polymerizing (for example, cationic polymerization) unsaturated monomers such as isoprene and cyclopentadiene, which are petroleum fractions (C5 fractions) corresponding to 4 to 5 carbon atoms, and 1,3 - A resin made from concentrated pentadiene.
The softening point of the C5 resin is preferably 80°C to 100°C, more preferably 90°C to 100°C.
As used herein, the softening point is a value measured according to JIS-2207.
Ｃ５系樹脂としては、例えば、クイントンＡ１００（日本ゼオン株式会社製）、クイントンＭ１００（日本ゼオン株式会社製）等を用いることができる。 As the C5-based resin, for example, Quinton A100 (manufactured by Nippon Zeon Co., Ltd.), Quinton M100 (manufactured by Nippon Zeon Co., Ltd.), or the like can be used.
Ｃ５／Ｃ９系樹脂としては、Ｃ５／Ｃ９系石油樹脂が挙げられ、例えば、Ｃ５／Ｃ９系の脂肪族／芳香族炭化水素樹脂が挙げられる。具体的には、上記Ｃ５留分と、炭素数８～１０個相当の石油留分（Ｃ９留分）とを重合（例えばカチオン重合）により共重合して得られる樹脂である。
Ｃ５／Ｃ９系樹脂の軟化点は、好ましくは８０℃～１１５℃、より好ましくは８５℃～１１５℃、更に好ましくは９０℃～１１５℃である。
Examples of C5/C9 resins include C5/C9 petroleum resins, such as C5/C9 aliphatic/aromatic hydrocarbon resins. Specifically, it is a resin obtained by copolymerizing the above C5 fraction and a petroleum fraction corresponding to 8 to 10 carbon atoms (C9 fraction) by polymerization (for example, cationic polymerization).
The softening point of the C5/C9 resin is preferably 80°C to 115°C, more preferably 85°C to 115°C, still more preferably 90°C to 115°C.
また、粘着剤組成物を作成したときの色相に影響を与えるために、Ｃ５／Ｃ９系樹脂のＪＩＳ－Ｋ５６００ガードナー法（トルエン５０％）の溶液色相が４以上であることが好ましく、特に７以上であることがより好ましい。例えば、溶液色相が４以上の例としてはクイントンＮ１８０（日本ゼオン株式会社製）が挙げられ、溶液色相が７以上の例としては、クイントンＧ１００Ｂ（日本ゼオン株式会社製）、クイントンＧ１１５（日本ゼオン株式会社製）等を用いることができる。 In addition, in order to affect the hue when the pressure-sensitive adhesive composition is prepared, the solution hue of the JIS-K5600 Gardner method (50% toluene) of the C5/C9 resin is preferably 4 or more, particularly 7 or more. is more preferable. For example, examples with a solution hue of 4 or more include Quinton N180 (manufactured by Nippon Zeon Co., Ltd.). manufactured by a company), etc. can be used.
本発明において、前記（Ｂ）粘着付与樹脂は、Ｃ５系樹脂及びＣ５／Ｃ９系樹脂からなる群より選択される少なくとも一種を含有するが、これ以外の粘着付与樹脂を粘着剤組成物の色相に影響を与えない範囲で含有することもできる。
成分（Ｂ）の粘着付与樹脂のＣ５系樹脂及びＣ５／Ｃ９系樹脂からなる群より選択される少なくとも一種以外の粘着付与樹脂の具体例としては、前記粘着付与樹脂の具体例における、Ｃ５系樹脂及びＣ５／Ｃ９系樹脂以外の樹脂が挙げられ、例えば、脂環族飽和炭化水素樹脂のアルコン（登録商標）Ｐ－１２５（荒川化学工業）などが挙げられる。
In the present invention, the (B) tackifying resin contains at least one selected from the group consisting of C5-based resins and C5/C9-based resins. It can also be contained within a range that does not affect it.
Specific examples of the tackifying resin other than at least one selected from the group consisting of C5-based resins and C5/C9-based resins for the tackifying resin of component (B) include the C5-based resins in the specific examples of the tackifying resin. and resins other than C5/C9 resins, for example, alicyclic saturated hydrocarbon resin Alcon (registered trademark) P-125 (Arakawa Chemical Industries).
上記（Ｂ）粘着付与樹脂は、全エラストマー成分の１００質量部に対して２０質量部～２００質量部、好ましくは５０質量部～１８０質量部の量で存在していることが好ましい。
上記（Ｂ）粘着付与樹脂の含有量は、粘着剤組成物の全質量に対し、１０質量％～４０質量％が好ましく、１５質量％～３０質量％であることが更に好ましい。
The tackifying resin (B) is preferably present in an amount of 20 to 200 parts by weight, preferably 50 to 180 parts by weight, per 100 parts by weight of the total elastomer component.
The content of the tackifying resin (B) is preferably 10% by mass to 40% by mass, more preferably 15% by mass to 30% by mass, relative to the total mass of the adhesive composition.
［（Ｃ）可塑剤］
本発明において使用する可塑剤（軟化剤）としては、パラフィン系、ナフテン系、等の石油系プロセスオイルやひまし油、大豆油などの植物油、及び植物油由来の脂肪酸エステルなどの軟化剤を使用してもよい。また、フタル酸、イソフタル酸、テレフタル酸等の芳香族ジカルボン酸や、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等の脂肪族ジカルボン酸と、例えば炭素原子数８乃至１０程度のアルキル基を有するモノアルコールとの二塩基酸エステル系可塑剤；前記芳香族ジカルボン酸や脂肪族ジカルボン酸とエチレングリコール、プロピレングリコール、ブチレングリコール、ネオペンチルグリコール、ジエチレングリコール等のグリコールとの重縮合により得られるポリエステル系可塑剤；ポリエチレングリコール、クエン酸エステル等のその他の可塑剤なども使用することができる。これら２つ以上を併用することもできる。
本発明において、成分（Ｃ）の可塑剤は、粘着剤組成物の全質量に対して、１質量％～１５質量％であることが好ましく、５質量％～１５質量％であることが更に好ましい。
[(C) plasticizer]
As the plasticizer (softener) used in the present invention, petroleum-based process oils such as paraffinic and naphthenic oils, vegetable oils such as castor oil and soybean oil, and softeners such as fatty acid esters derived from vegetable oils may be used. good. In addition, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; and aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; Dibasic acid ester plasticizer with monoalcohol having about 8 to 10 alkyl groups; With the above aromatic dicarboxylic acid or aliphatic dicarboxylic acid and glycol such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, diethylene glycol polyester plasticizers obtained by polycondensation of polycondensation; other plasticizers such as polyethylene glycol and citrate esters can also be used. Two or more of these can be used in combination.
In the present invention, the component (C) plasticizer is preferably 1% by mass to 15% by mass, more preferably 5% by mass to 15% by mass, relative to the total mass of the pressure-sensitive adhesive composition. .
［（Ｄ）コロイド粒子］
本発明において使用するコロイド粒子としては、特に制限はないが、例えば、コーンスターチ、グアーガム、ローカストビーンガム、デンプン、ペクチン、アルギン酸及びその塩、カラギーナン、コラーゲン、寒天、ゼラチン、キチン、キトサン、カラヤガム、アラビアゴム、キサンタンガム、デキストリン、デキストラン、カルボキシメチルセルロース、カルボキシメチルセルロース・ナトリウム（ＣＭＣ）、カルボキシメチルセルロース・カルシウム、ヒドロキシアルキルメチルセルロース、ヒドロキシプロピルセルロース、メチルセルロース、デンプンアセテート、デンプンホスフェート、ヒドロキシエチル化デンプン、ヒドロキシプロピルデンプン、酸化デンプン、デキストリン化デンプン、デンプン・アクリル酸グラフト重合体、ポリアクリル酸及びその塩、ポリエチレンオキシド、ポリビニルアルコール、ポリ－Ｎ－ビニルピロリドン等のハイドロコロイド粒子（親水性ポリマー）を挙げることができる。
これらのコロイド粒子のなかで、特に耐熱性のよいカルボキシメチルセルロース・ナトリウム等を使用することが好ましい。カルボキシメチルセルロース・ナトリウムの粒径は、５μｍ～５００μｍ、好ましくは１５μｍ～２５０μｍである。
上記カルボキシメチルセルロース・ナトリウムの市販品としては、セロゲン（登録商標）Ｆ－３Ｈ（第一工業製薬（株））、ＭＡＣ２００ＨＣ、サンローズ（登録商標）Ｆ３５０ＨＣ、サンローズ（登録商標）Ｆ１０ＬＣ（以上日本製紙ケミカル（株））等が挙げられる。
[(D) Colloidal particles]
The colloidal particles used in the present invention are not particularly limited, but examples include cornstarch, guar gum, locust bean gum, starch, pectin, alginic acid and its salts, carrageenan, collagen, agar, gelatin, chitin, chitosan, karaya gum, arabic. Gum, Xanthan Gum, Dextrin, Dextran, Carboxymethylcellulose, Sodium Carboxymethylcellulose (CMC), Calcium Carboxymethylcellulose, Hydroxyalkylmethylcellulose, Hydroxypropylcellulose, Methylcellulose, Starch Acetate, Starch Phosphate, Hydroxyethylated Starch, Hydroxypropyl Starch, Oxidized Examples include hydrocolloid particles (hydrophilic polymers) such as starch, dextrinized starch, starch/acrylic acid graft polymer, polyacrylic acid and its salts, polyethylene oxide, polyvinyl alcohol, and poly-N-vinylpyrrolidone.
Among these colloidal particles, it is particularly preferable to use sodium carboxymethyl cellulose or the like, which has excellent heat resistance. The particle size of sodium carboxymethylcellulose is 5 μm to 500 μm, preferably 15 μm to 250 μm.
Commercially available products of sodium carboxymethylcellulose include Cellogen (registered trademark) F-3H (Daiichi Kogyo Seiyaku Co., Ltd.), MAC200HC, Sunrose (registered trademark) F350HC, Sunrose (registered trademark) F10LC (Nippon Paper Industries Chemical Co., Ltd.) and the like.
本発明に用いるコロイド粒子は、一種を単独で使用してもよく、２種以上を併用してもよい。 Colloidal particles used in the present invention may be used singly or in combination of two or more.
これらコロイド粒子の配合量は、適度な吸水速度と吸水量を得るために、例えばカルボキシメチルセルロース・ナトリウムやカルボキシメチルセルロースであれば、粘着剤組成物の全質量に対して、好ましくは１０質量％～５０質量％、更に好ましくは２０質量％～４０質量％の割合で使用することが、吸液性、特に吸水性、創傷部位との接着性、及び適度な保形性（側面からの膏体のはみだし防止性）の観点から望ましい。 The amount of these colloidal particles is preferably 10% by mass to 50% by mass based on the total mass of the pressure-sensitive adhesive composition in the case of carboxymethylcellulose sodium or carboxymethylcellulose, in order to obtain an appropriate water absorption rate and water absorption amount. % by mass, more preferably 20% by mass to 40% by mass, is used in terms of liquid absorption, especially water absorption, adhesion to the wound site, and moderate shape retention (plaster protruding from the side) from the viewpoint of prevention).
［その他成分］
さらに本発明の粘着剤組成物には、一般的なゴム系粘着剤で使用する、酢酸トコフェロール及び／又はその誘導体、アスコルビン酸及び／又はその誘導体、亜硫酸ナトリウム、ジブチルヒドロキシトルエン等の酸化防止剤、ビスフェノール系、ヒンダードアミン系、ベンゾイミダゾール系などの老化防止剤や紫外線吸収剤、光安定剤などを１種又は複数の組合せで適宜添加してもよい。
また本発明の粘着剤組成物には、その他皮膚貼付用の粘着テープやシートに一般に用いられるようなその他の各種添加剤、例えば充填剤、脱臭剤、芳香剤などを配合してもよく、或いは内部凝集力を高めるために架橋剤を適宜配合させてもよい。
これらの任意成分の配合量は、通常、粘着剤組成物の全質量に対して５質量％以下である。
[Other ingredients]
Furthermore, the pressure-sensitive adhesive composition of the present invention includes antioxidants such as tocopherol acetate and/or derivatives thereof, ascorbic acid and/or derivatives thereof, sodium sulfite, and dibutylhydroxytoluene, which are used in general rubber-based pressure-sensitive adhesives. Bisphenol-based, hindered amine-based, and benzimidazole-based anti-aging agents, ultraviolet absorbers, light stabilizers, and the like may be appropriately added singly or in combination.
The pressure-sensitive adhesive composition of the present invention may also contain various other additives generally used in pressure-sensitive adhesive tapes and sheets for skin application, such as fillers, deodorants, and fragrances. A cross-linking agent may be appropriately blended in order to increase the internal cohesion.
The blending amount of these optional components is usually 5% by mass or less with respect to the total mass of the pressure-sensitive adhesive composition.
また、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してもよい。例えば、薬理学上有効な薬効成分としては、抗生物質、殺菌剤や抗菌剤（アクリノール、塩化ベンザルコニウム、銀系化合物等）、消毒剤、抗炎症剤及び皮膚保護剤などが挙げられる。また、セラミド等の保湿効果のある物質を添加することで、角質剥離でダメージを受けた皮膚の健常な皮膚への再生を助長することができ、或いは血流促進効果の高いγ－オリザノール等を添加することにより、褥瘡発生が懸念される部位において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。
これらの薬効成分は、粘着剤組成物の全質量に対して通常３質量％以下、好ましくは２質量％以下の含有量とすることができる。
In addition, for skin that has already been damaged or is expected to be damaged, a medicinal ingredient may be added for the purpose of treatment of the skin, prevention of damage, beauty, or the like. For example, pharmacologically effective medicinal ingredients include antibiotics, bactericides and antibacterial agents (acrinol, benzalkonium chloride, silver-based compounds, etc.), antiseptics, anti-inflammatory agents, skin protectants, and the like. In addition, by adding a substance with a moisturizing effect such as ceramide, it is possible to promote regeneration of skin damaged by exfoliation into healthy skin, or γ-oryzanol, etc., which has a high blood flow promoting effect, can be added. By adding it, blockage of blood vessels caused by body pressure at a site where pressure ulcers are likely to occur can be alleviated, and prevention of pressure ulcers can be expected.
The content of these medicinal ingredients is usually 3% by mass or less, preferably 2% by mass or less, relative to the total mass of the pressure-sensitive adhesive composition.
本発明の粘着剤組成物は、貼付材に適用された場合に、傷口を目立たなくするために、着色剤を含むことができるが、皮膚への刺激が問題となることもある。
本発明の粘着剤組成物は、着色剤を含まないことが好ましい。
本発明の粘着剤組成物の色相に関して、本発明の粘着剤組成物の△ｂ＊（Ｄ６５）は８以上１７以下である。本発明の粘着剤組成物の△ｂ＊（Ｄ６５）は８以上１７以下とすることで、着色剤を使用せずとも、創傷部位に適用された場合、傷口を目立たなくすることができ、皮膚の色になじむような色相とすることが可能となる。なお、△ｂ＊（Ｄ６５）は、粘着剤組成物の黄色の程度を示している。
また、△ｂ＊（Ｄ６５）は、８以上１７以下が好ましく、１０以上１７以下がより好ましく、１１以上１７以下がより好ましい。
The pressure-sensitive adhesive composition of the present invention may contain a coloring agent in order to make the wound inconspicuous when applied to a patch, but irritation to the skin may become a problem.
The pressure-sensitive adhesive composition of the present invention preferably does not contain a coloring agent.
Regarding the hue of the pressure-sensitive adhesive composition of the present invention, Δb* (D65) of the pressure-sensitive adhesive composition of the present invention is 8 or more and 17 or less. By setting the Δb* (D65) of the pressure-sensitive adhesive composition of the present invention to 8 or more and 17 or less, the wound can be made inconspicuous when applied to the wound site without using a coloring agent, and the skin can be It is possible to obtain a hue that blends well with the color of . Δb* (D65) indicates the degree of yellowness of the pressure-sensitive adhesive composition.
Δb*(D65) is preferably 8 or more and 17 or less, more preferably 10 or more and 17 or less, and more preferably 11 or more and 17 or less.
更に、本発明の粘着剤組成物の色相に関して、△Ｅ＊ａｂ（Ｄ６５）は、１０～２０が好ましく、１０～１９がより好ましく、１３～１９が更に好ましい。
△Ｅ＊ａｂ（Ｄ６５）は、白色を基準として、粘着剤組成物の色相の差を示している。
△Ｅ＊ａｂ（Ｄ６５）の値を上記範囲とすることで、より皮膚の色になじむような色相とすることが可能となるため、好ましい。
Furthermore, regarding the hue of the adhesive composition of the present invention, ΔE*ab (D65) is preferably 10-20, more preferably 10-19, and even more preferably 13-19.
ΔE*ab (D65) indicates the difference in hue of the pressure-sensitive adhesive composition based on white.
By setting the value of ΔE*ab (D65) within the above range, it is possible to obtain a hue that is more compatible with the skin color, which is preferable.
△ｂ＊（Ｄ６５）、及び△Ｅ＊ａｂ（Ｄ６５）は、それぞれ、分光測色計（コニカミノルタ、ＣＭ－２６００Ｄ）を用いて、ＳＣＥ方式により測定される。 Δb* (D65) and ΔE*ab (D65) are each measured by the SCE method using a spectrophotometer (Konica Minolta, CM-2600D).
上記色相は、本発明の粘着剤組成物の組成、含有量を適宜、変更することで調節することが可能である。例えば、本発明の粘着剤組成物における粘着付与樹脂の種類、含有量を調整することで、上記色相を調節することができる。 The above hue can be adjusted by appropriately changing the composition and content of the pressure-sensitive adhesive composition of the present invention. For example, the hue can be adjusted by adjusting the type and content of the tackifying resin in the pressure-sensitive adhesive composition of the present invention.
＜貼付材＞
本発明は、本発明の皮膚貼付用ハイドロコロイド型粘着剤組成物を含む、貼付材にも関する。
本発明の第一の態様における貼付材は、基材と、該基材の少なくとも一方の面に粘着剤層を有し、該粘着剤層が、本発明の皮膚貼付用ハイドロコロイド型粘着剤組成物を用いて形成された貼付材である。
<Applying material>
The present invention also relates to a patch containing the hydrocolloid pressure-sensitive adhesive composition for skin application of the present invention.
The patch in the first aspect of the present invention has a substrate and an adhesive layer on at least one surface of the substrate, and the adhesive layer comprises the hydrocolloid adhesive composition for skin application of the present invention. It is an adhesive patch formed using
本発明の貼付材は、有機溶剤が不要の塗工方法であるカレンダー法やホットメルト法などによって、好適に作製することができる。
ホットメルト法は、有機溶剤などの希釈媒体を全く使用せず、高温で急激に軟化溶融するブロック共重合体の特性を利用した方法であり、乾燥工程が不要、塗工速度が速い、爆発火災の危険がないなどの利点がある。
一例として、ホットメルト法による貼付材の製造例を以下に記載する。加熱制御可能な高速回転ミキサーで、エラストマー成分、粘着付与樹脂、可塑剤及びコロイド粒子、そして適宜その他成分を、窒素雰囲気下、通常１５０～２００℃の温度で３０～１２０分間加熱高速撹拌して溶解物として各成分が均一となった粘着剤組成物を得ることができる。
前記方法にて得られた粘着剤組成物を、ホットメルト塗工機にて、１５０～２００℃に温度制御したダイヘッド部分から押し出して剥離シート上に例えば１００～１，０００μｍの厚さに展延した後、これに、基材を積層(好ましくはラミネート)することで貼付材を作製することができる。
カレンダー法としては、加圧ニーダーを用い、エラストマー成分、粘着付与樹脂、可塑剤及びコロイド粒子、そして適宜その他成分を加えて、混練り温度８０～１４０℃、混練り時間２０～６０分の範囲で均一に練り上げて粘着剤を調製する。カレンダー法においては、数本の鋳鋼製熱ロールの間で粘着剤を加熱圧延し、ロールの周速度による摩擦により粘着剤を剥離シート上に、例えば１００～１，０００μｍの厚さに展延した後、これに、基材を積層(好ましくはラミネート)することで貼付材を作製することができる。
The patch of the present invention can be suitably produced by a coating method that does not require an organic solvent, such as a calendering method or a hot-melt method.
The hot-melt method does not use diluents such as organic solvents at all, and utilizes the properties of block copolymers that rapidly soften and melt at high temperatures. There are advantages such as no danger of
As an example, an example of producing an adhesive patch by the hot-melt method is described below. Elastomer component, tackifying resin, plasticizer and colloidal particles, and optionally other components are melted by heating at high speed for 30 to 120 minutes at a temperature of 150 to 200°C in a nitrogen atmosphere in a high-speed rotating mixer capable of controlling heating. A pressure-sensitive adhesive composition in which each component is uniform as a product can be obtained.
The pressure-sensitive adhesive composition obtained by the above method is extruded from a die head portion controlled at a temperature of 150 to 200° C. using a hot-melt coater and spread on a release sheet to a thickness of, for example, 100 to 1,000 μm. After that, the adhesive material can be produced by laminating (preferably laminating) a base material thereon.
As the calendering method, a pressure kneader is used, and the elastomer component, tackifying resin, plasticizer, colloidal particles, and other ingredients are added as appropriate, and the kneading temperature is 80 to 140° C. and the kneading time is 20 to 60 minutes. The adhesive is prepared by kneading uniformly. In the calendering method, the adhesive is heated and rolled between several cast steel hot rolls, and the adhesive is spread on the release sheet by friction due to the peripheral speed of the rolls to a thickness of, for example, 100 to 1,000 μm. After that, a base material is laminated (preferably laminated) on this, whereby an adhesive material can be produced.
ここで用いられる基材としては、適度な伸縮性、柔軟性、強度を備えるものであれば特に限定されず、適度の通気性、透湿性及び菌バリヤー性の性質を備えるものが特に好ましい。例えばポリオレフィン、ポリウレタン、ポリエステル及びポリアクリル酸等のフィルム、フォーム、不織布、織布及び編み布等が挙げられる。中でも上述の観点からポリウレタン性のフィルムが好ましい。 The substrate used here is not particularly limited as long as it has appropriate stretchability, flexibility and strength, and those having appropriate air permeability, moisture permeability and bacteria barrier properties are particularly preferred. Examples include films, foams, non-woven fabrics, woven fabrics and knitted fabrics of polyolefins, polyurethanes, polyesters and polyacrylic acids. Among them, a polyurethane film is preferable from the above-mentioned viewpoint.
また、使用する剥離シートは貼付材の分野で慣用のものを用いることができる。例えばシリコーン離型処理した上質紙、グラシン紙等の紙基材やポリエステルフィルム等を用いることができる。
本発明において、剥離シートの長さは、粘着剤の流出防止、生産性、取扱性、経済性及び製法の容易性等の観点より、粘着剤の塗工領域よりも、０．２ｍｍ以上、特に１～５ｍｍ大きくすることが好ましい。
In addition, the release sheet to be used can be one commonly used in the field of patches. For example, paper substrates such as high-quality paper and glassine paper subjected to silicone release treatment, polyester films, and the like can be used.
In the present invention, the length of the release sheet is 0.2 mm or longer than the coating area of the adhesive from the viewpoints of preventing the outflow of the adhesive, productivity, handling, economic efficiency, ease of production, etc., especially It is preferable to make it larger by 1 to 5 mm.
本発明の貼付材の形状は、使用目的に応じて、適宜、選定すればよい。具体的な形状としては、円形、楕円形や、三角形、四角形、菱形等の多角形等を示すことができる。また、これらの形状を適宜組み合わせた形状であってもよく、ロール状に形成してもよい。 The shape of the patch of the present invention may be appropriately selected according to the purpose of use. Specific shapes include circles, ellipses, and polygons such as triangles, quadrilaterals, and rhombuses. Moreover, the shape which combined these shapes suitably may be sufficient, and you may form in a roll shape.
貼付材は、基材に皮膚貼付用ハイドロコロイド型粘着剤組成物を全面或いはパターンコーティングにより積層し、粘着剤層とすることで得ることもできる。 The patch can also be obtained by laminating a hydrocolloid-type adhesive composition for skin application onto a substrate by coating the entire surface or by pattern coating to form an adhesive layer.
本発明の第二の態様における貼付材は、基材と、粘着層と、パッド層とをこの順に有し、該パッド層が、本発明の皮膚貼付用ハイドロコロイド型粘着剤組成物を含むものである。このとき、基材は、透湿性が高いことが好ましく、粘着層はパッド層よりも粘着力を高く設定することが好ましい。
なお、上記第一の態様における貼付材にパッド層を付与することにより、第二の態様における貼付材に転用することが可能である。
The patch in the second aspect of the present invention has a substrate, an adhesive layer and a pad layer in this order, and the pad layer contains the hydrocolloid adhesive composition for skin application of the present invention. At this time, the substrate preferably has high moisture permeability, and the adhesive layer preferably has a higher adhesive force than the pad layer.
By adding a pad layer to the patch of the first aspect, it can be used as the patch of the second aspect.
本発明の貼付材の粘着剤層（ハイドロコロイド組成物層）の厚さは、特に制限されないが、皮膚への固定性を担保し、基材厚みとのバランスの点から、一定厚とする場合は、１００～１，２００μｍ以下が好ましい。特に好ましくは１５０～４００μｍである。また、例えば、貼付材の縁取り部の粘着剤の使用量を、貼付材の中央部分の粘着剤の使用量より少なく、厚みを薄くすることにより、縁取り部と衣類等とのこすれを防止し、皮膚へ適用した時に剥がれにくくなる効果が得られる。この場合、粘着剤の使用量は、中央部で、好ましくは３００～１，２００μｍ、更に好ましくは６００～８００μｍであり、縁取り部の粘着剤の使用量は、好ましくは５０～３００μｍ、更に好ましくは１００～３００μｍである。 The thickness of the pressure-sensitive adhesive layer (hydrocolloid composition layer) of the patch of the present invention is not particularly limited. , 100 to 1,200 μm or less. Especially preferred is 150 to 400 μm. In addition, for example, the amount of adhesive used in the edge of the patch is less than the amount of adhesive used in the central portion of the patch, and the thickness of the adhesive is reduced, thereby preventing the edge from rubbing against clothing and the like. It has the effect of making it difficult to peel off when applied to the skin. In this case, the amount of adhesive used in the central portion is preferably 300 to 1,200 μm, more preferably 600 to 800 μm, and the amount of adhesive used in the edge portion is preferably 50 to 300 μm, more preferably 100 to 300 μm.
〔粘着剤層の粘着力〕
皮膚貼付用ハイドロコロイド型粘着剤組成物を用いて形成された粘着剤層は、創傷部位を含む貼付皮膚面に貼付されるものであり、創傷部位及び健常皮膚に損傷を与えることなく剥離できるものでなければならないこと、及び背面に配置される支持体に対する投錨性を良好に保つ必要があることから、所定の粘着力を有することが望ましい。例えば、粘着剤層の皮膚面に対する粘着力は、好ましくは０．１～２．０Ｎ／１５ｍｍ、より好ましくは０．２～１．５Ｎ／１５ｍｍの範囲である。
[Adhesive strength of adhesive layer]
The pressure-sensitive adhesive layer formed using the hydrocolloid-type pressure-sensitive adhesive composition for skin application is to be applied to the skin surface including the wound site, and can be peeled off without damaging the wound site and healthy skin. It is desirable to have a predetermined adhesive strength because it is necessary to maintain good anchoring properties with respect to the support placed on the back surface. For example, the adhesive strength of the adhesive layer to the skin surface is preferably 0.1 to 2.0 N/15 mm, more preferably 0.2 to 1.5 N/15 mm.
本発明の貼付材の物理的・化学的性質については、国際公開第２０１３／０７７１３４号パンフレットに定義されたものを好適に適用できる。 As for the physical and chemical properties of the patch of the present invention, those defined in WO 2013/077134 pamphlet can be suitably applied.
以下に実施例を挙げて、本発明をさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。なお、実施例４は、参考例４に読み替えるものとする。 EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In addition, Example 4 shall be read as Reference Example 4.
＜皮膚貼付用ハイドロコロイド型粘着剤組成物の調製＞
前記カレンダー法で、加圧ニーダーを用いて表１に示す組成にて混練り温度８０～１４０℃で３０～５０分間の混練を行い、均一な粘着剤組成物を調製した。
<Preparation of hydrocolloid adhesive composition for skin application>
According to the calendering method, the composition shown in Table 1 was kneaded at a kneading temperature of 80 to 140° C. for 30 to 50 minutes using a pressure kneader to prepare a uniform adhesive composition.
＜貼付材の作製＞
調製した粘着剤組成物を熱延伸ロールを用いてシリコーン処理したグラシン紙（厚さ１２０μｍ）上に、３００μｍの厚さに展延して粘着剤層を形成した。この粘着剤層の上に基材として１０μｍのポリエーテル系ポリウレタンフィルムをラミネートし１５×１００ｃｍのシートを作製し実施例１の貼付材を得た。
実施例２～９、比較例１～４は、実施例１と同様にして貼付材を作製した。
<Preparation of patch>
The prepared pressure-sensitive adhesive composition was spread to a thickness of 300 μm on glassine paper (thickness: 120 μm) treated with silicone using a hot stretching roll to form a pressure-sensitive adhesive layer. A 10 μm-thick polyether-based polyurethane film was laminated as a base material on this pressure-sensitive adhesive layer to prepare a sheet of 15×100 cm, and the patch of Example 1 was obtained.
In Examples 2 to 9 and Comparative Examples 1 to 4, patches were prepared in the same manner as in Example 1.
＜染み出し評価＞
各貼付材を３０ｍｍ×４０ｍｍのシート状に裁断したものを用いて、縁を揃えて１０枚重ねて試料とした。これを縦５０ｍｍ、横７０ｍｍ、厚さ２ｍｍの２枚のガラス板に挟んだ。
ガラス板の上から１０００ｇの分銅を乗せて荷重をかけて、６０℃の恒温槽に静置した。１週間静置した後に、恒温槽から取り出して、粘着剤層の側面の染み出し度合を評価した。下記の基準で目視により評価した。
○： べたつきがなく良好
△： べたつきがあるが粘着剤層の明らかな染み出しはない。
×： 粘着剤層が染み出している。
評価○、△が、実用的に問題がないレベルである。
<Exudation evaluation>
Each patch was cut into a sheet of 30 mm×40 mm, and 10 sheets were stacked with the edges aligned to obtain a sample. This was sandwiched between two glass plates having a length of 50 mm, a width of 70 mm and a thickness of 2 mm.
A weight of 1000 g was placed on the glass plate to apply a load, and the glass plate was placed in a constant temperature bath at 60°C. After standing still for 1 week, it was taken out from the constant temperature bath and the degree of seepage on the side surface of the pressure-sensitive adhesive layer was evaluated. It was visually evaluated according to the following criteria.
◯: Good with no stickiness △: Sticky, but no obvious exudation of the adhesive layer.
x: The adhesive layer bleeds out.
Evaluations of ◯ and Δ are levels at which there is no practical problem.
＜保持力の評価＞
各貼付材を、ＪＩＳ Ｚ ０２３７（保持力）に規定される手順に準じて測定する。２３℃、５０％ＲＨの条件下、幅２５ｍｍの試験片Ａをガラス板に幅２５ｍｍ×長さ２０ｍｍの面積となるように貼付し、２ｋｇのゴムロールで３００ｍｍ／分の速度で一往復圧着し、６０℃の環境下に３０分放置後、試験片Ａが垂直に垂れ下がるように吊るし、おもり１００ｇの荷重を加えて、そして取り付けてから３０分と６０分経過後までに貼付材が移動する距離（ｍｍ）をそれぞれ測定し、その平均値（試験数ｎ＝３）を保持力とする。
<Evaluation of holding force>
Each patch is measured according to the procedure specified in JIS Z 0237 (holding power). Under the conditions of 23° C. and 50% RH, a test piece A with a width of 25 mm was attached to a glass plate so as to have an area of 25 mm in width and 20 mm in length. After being left in an environment of 60°C for 30 minutes, the test piece A was hung so as to hang vertically, a load of 100 g was applied, and the distance that the patch moved after 30 minutes and 60 minutes after attachment ( mm) are measured, and the average value (number of tests n=3) is taken as the holding power.
＜色相＞
色相は、貼付材から剥離シートを剥離後、白色の上質紙に貼付して、支持体越しに（支持体層の着色を差分して）粘着剤層について評価した。色相の測定は、分光測色計（コニカミノルタ、ＣＭ－２６００Ｄ）を用いて行い、ＳＣＥ方式で、それぞれ△ｂ＊（Ｄ６５）、及び△Ｅ＊ａｂ（Ｄ６５）を測定した。本件においては、△ｂ＊（Ｄ６５）を３回測定し、その平均値を測定結果（△ｂ＊（Ｄ６５））とした。また、△Ｅ＊ａｂ（Ｄ６５）を３回測定し、その平均値を測定結果（△Ｅ＊ａｂ（Ｄ６５））とした。
<Hue>
After peeling off the release sheet from the adhesive material, the adhesive layer was evaluated through the support (by subtracting the coloration of the support layer) from the adhesive layer, which was attached to white fine paper. The hue was measured using a spectrophotometer (Konica Minolta, CM-2600D), and Δb* (D65) and ΔE*ab (D65) were measured by the SCE method. In this case, Δb*(D65) was measured three times, and the average value was used as the measurement result (Δb*(D65)). Also, ΔE*ab(D65) was measured three times, and the average value was taken as the measurement result (ΔE*ab(D65)).
＜皮膚への付着性＞
各貼付材を３０ｍｍ×５０ｍｍ（エッジは丸く切り落とし）に裁断したものを前腕内側の皮膚に貼付し、２４時間後の貼付材の皮膚への付着性について評価した。
○： １０％未満のはがれ
△： １０％以上３０％未満のはがれ
×： ３０％以上のはがれ
評価○、△が、実用的に問題がないレベルである。
<Adhesion to skin>
Each patch was cut into a size of 30 mm×50 mm (the edges were rounded off) and applied to the skin on the inner side of the forearm, and the adhesiveness of the patch to the skin was evaluated after 24 hours.
◯: less than 10% peeling Δ: 10% or more and less than 30% peeling ×: 30% or more peeling evaluation ◯ and Δ are practically acceptable levels.
＜目立ちにくさ＞
各貼付材を３０ｍｍ×５０ｍｍ（エッジは丸く切り落とし）に裁断したものを前腕内側の皮膚に貼付し、５分後の貼付材の目立ちにくさについて、下記の基準で目視により評価した。
Ａ：目立たない
Ｂ：やや目立つが問題ない
Ｃ：目立って問題がある
得られた結果を表１に示す。
<Hardness to stand out>
Each patch was cut into a size of 30 mm×50 mm (rounded edges were cut off) and applied to the skin on the inside of the forearm.
A: Inconspicuous B: Slightly conspicuous but no problem C: Noticeable problem Table 1 shows the results obtained.
実施例、比較例で使用した成分は下記の通りである。
オパノールＢ１５ＳＦＮ ： ＢＡＳＦジャパン株式会社製
クイントンＧ１００Ｂ ： 日本ゼオン株式会社製
クイントンＮ１８０ ： 日本ゼオン株式会社製
パインクリスタルＫＥ３１１： 荒川化学工業株式会社製
クイントンＡ１００ ： 日本ゼオン株式会社製
ＦＴＲ－６１００ ： 三井化学株式会社製
スーパーエステルＡ１００ ： 荒川化学工業株式会社製
ＹＳポリスターＴ１００ ： ヤスハラケミカル株式会社製
老化防止剤：ＢＨＴ ： 精工化学株式会社製
The components used in Examples and Comparative Examples are as follows.
Oppanol B15SFN: BASF Japan Co., Ltd. Quinton G100B: Nippon Zeon Co., Ltd. Quinton N180: Nippon Zeon Co., Ltd. Pine Crystal KE311: Arakawa Chemical Co., Ltd. Quinton A100: Nippon Zeon Co., Ltd. FTR-6100: Mitsui Chemicals, Inc. Super Ester A100: manufactured by Arakawa Chemical Industries, Ltd. YS Polyster T100: manufactured by Yasuhara Chemical Co., Ltd. Anti-aging agent: BHT: manufactured by Seiko Chemical Co., Ltd.
Claims (3)
前記（Ａ）エラストマーは、スチレン系ブロック共重合体及びポリイソブチレンを含み、前記ポリイソブチレンの含有量は、前記（Ａ）エラストマーの全質量に対して４０質量％～６０質量％であり、前記（Ａ）エラストマーの含有量は、前記皮膚貼付用ハイドロコロイド型粘着剤組成物の全質量に対して３０質量％～４５質量％であり、前記ポリイソブチレンの含有量は、前記皮膚貼付用ハイドロコロイド型粘着剤組成物の全質量に対して１７質量％～３０質量％であり、
前記（Ｂ）粘着付与樹脂が、Ｃ５／Ｃ９系樹脂、又はＣ５系樹脂のみを含有し、前記（Ｂ）粘着付与樹脂の含有量は、前記皮膚貼付用ハイドロコロイド型粘着剤組成物の全質量に対して１５質量％～３０質量％であり、
前記（Ｃ）可塑剤の含有量は、前記皮膚貼付用ハイドロコロイド型粘着剤組成物の全質量に対して５質量％～１５質量％であり、
前記（Ｄ）コロイド粒子の含有量は、前記皮膚貼付用ハイドロコロイド型粘着剤組成物の全質量に対して２１質量％～４０質量％であり、
前記皮膚貼付用ハイドロコロイド型粘着剤組成物の△ｂ＊（Ｄ６５）が８以上１７以下である、皮膚貼付用ハイドロコロイド型粘着剤組成物（但し、エチレン、プロピレン及び非共役化ジエンから製造される三元共重合体を含むヒドロコロイド組成物、（ａ）１０～３５重量部のポリ（スチレン／オレフィン／スチレン）ブロック共重合体、（ｂ）２０～５０重量部の粘着付与樹脂、（ｃ）２～１５重量部の－２０℃以下のガラス転移温度を有するアクリレートポリマー、（ｄ）２～２５重量部の可塑剤、（ｅ）２０～２５重量部の親水性コロイド、及び（ｆ）０．１～２重量部の少なくとも１つの酸化防止剤を含む親水性の医療用接着性組成物、並びに、疎水相と親水相からなる皮膚接着性組成物であって、（ａ）疎水相は、疎水性ポリマー、少なくとも１つのエラストマー、及び粘着付与樹脂を含み、（ｂ）親水相は、ｉ）低分子量のセルロース誘導性ポリマー、及び天然多糖類からなる群から選択される少なくとも１つの材料、ｉｉ）少なくとも１つの高分子量のセルロース誘導性ポリマー、及び、ｉｉｉ）強化粘土粒子を含む皮膚接着性組成物を除く）。 (A) an elastomer, (B) a tackifying resin, (C) a plasticizer, and (D) a hydrocolloid adhesive composition for skin application, comprising:
The (A) elastomer contains a styrenic block copolymer and polyisobutylene, the content of the polyisobutylene is 40% by mass to 60% by mass with respect to the total mass of the (A) elastomer, and the ( A) The content of the elastomer is 30% by mass to 45% by mass with respect to the total mass of the hydrocolloid-type pressure-sensitive adhesive composition for patching on the skin, and the content of the polyisobutylene is the hydrocolloid-type pressure-sensitive adhesive for patching on the skin. 17% by mass to 30% by mass relative to the total mass of the composition,
The (B) tackifying resin contains only a C5/C9-based resin or a C5-based resin , and the content of the (B) tackifying resin is the total mass of the hydrocolloid-type adhesive composition for skin application. 15% by mass to 30% by mass with respect to
The content of the (C) plasticizer is 5% by mass to 15% by mass with respect to the total mass of the hydrocolloid adhesive composition for skin application,
The content of the colloidal particles (D) is 21% by mass to 40% by mass with respect to the total mass of the hydrocolloid-type pressure-sensitive adhesive composition for skin application,
A hydrocolloid-type pressure-sensitive adhesive composition for skin application, wherein the hydrocolloid-type pressure-sensitive adhesive composition for skin application has a Δb* (D65) of 8 or more and 17 or less (provided that three A hydrocolloid composition comprising an original copolymer, (a) 10 to 35 parts by weight of a poly(styrene/olefin/styrene) block copolymer, (b) 20 to 50 parts by weight of a tackifying resin, (c) 2 ˜15 parts by weight of an acrylate polymer having a glass transition temperature of −20° C. or less, (d) 2 to 25 parts by weight of a plasticizer, (e) 20 to 25 parts by weight of a hydrophilic colloid, and (f) 0.1. A hydrophilic medical adhesive composition comprising ~2 parts by weight of at least one antioxidant and a skin adhesive composition comprising a hydrophobic phase and a hydrophilic phase, wherein (a) the hydrophobic phase is hydrophobic (b) the hydrophilic phase comprises: i) at least one material selected from the group consisting of low molecular weight cellulose-derived polymers and natural polysaccharides; ii) at least with the exception of one high molecular weight cellulose-derived polymer and iii) a skin-adhesive composition comprising reinforced clay particles ).
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| US20030225356A1 (en) | 2002-05-24 | 2003-12-04 | Kulichikhin Valery G. | Composition for cushions, wound dressings and other skin-contacting products |
| JP2004538257A (en) | 2001-01-19 | 2004-12-24 | スキャパ・ノース・アメリカ | Hydrocolloid composition |
| CN102488919A (en) | 2011-12-29 | 2012-06-13 | 湖北大学 | Hydrocolloid dressing and its preparation method |
| JP2013507487A (en) | 2009-10-08 | 2013-03-04 | ユーロームド，インコーポレイテッド | Adhesive composition |
| 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 |
| JP6247916B2 (en) | 2013-12-03 | 2017-12-13 | 古河電気工業株式会社 | Resin composition, organic electronic device element sealing resin sheet, organic electroluminescence element, and image display apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2004538257A (en) | 2001-01-19 | 2004-12-24 | スキャパ・ノース・アメリカ | Hydrocolloid composition |
| US20030225356A1 (en) | 2002-05-24 | 2003-12-04 | Kulichikhin Valery G. | Composition for cushions, wound dressings and other skin-contacting products |
| JP2013507487A (en) | 2009-10-08 | 2013-03-04 | ユーロームド，インコーポレイテッド | Adhesive composition |
| 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 |
| CN102488919A (en) | 2011-12-29 | 2012-06-13 | 湖北大学 | Hydrocolloid dressing and its preparation method |
| JP6247916B2 (en) | 2013-12-03 | 2017-12-13 | 古河電気工業株式会社 | Resin composition, organic electronic device element sealing resin sheet, organic electroluminescence element, and image display apparatus |
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