JP4372882B2 - Base material for patch, medical patch made using the same, and emergency bandage - Google Patents

Description

【００４２】
また、上記各実施例および比較例にて得られた貼付材用基材および医療用貼付材について下記の特性を評価し、その結果を表２に示した。
【００４３】
＜濡れ性＞
ＪＩＳ Ｚ １５２９に規定する方法に準じて、作製した貼付材用基材フィルムの表面の濡れ性（単位：μＮ／ｃｍ）を測定した。
【００４４】
＜実用評価：投錨性＞
ボランティアの腹部に、各医療用貼付材を約２４時間貼付したのち、剥離除去した際の貼付皮膚面の状態を以下の判定基準に従って判定し、投錨性を評価した。
〇：皮膚面に粘着剤層が残存せず、投錨破壊を起こさない。
△：部分的に端部部分に粘着剤層が残存する。
×：皮膚面に粘着剤層が全部転写し、完全に投錨破壊を起こす。
【００４５】
＜実用評価：柔軟性＞
ボランティアの腹部に、各医療用貼付材を約２４時間時間貼付し、貼付中の状態を以下の判定基準に従って判定し、柔軟性を評価した。
〇：皮膚追従性に優れ、極めて柔軟性が高い。（目安：５０％モジュラス０．２〜０．５ｋｇｆ／１９ｍｍ幅）
△：柔軟すぎて自己支持性に劣る。（目安：５０％モジュラス＜０．２ｋｇｆ／１９ｍｍ幅未満）
×：柔軟性に欠ける。（目安：５０％モジュラス＞０．５ｋｇｆ／１９ｍｍ幅以上）
【００４６】
＜実用評価：引き剥がし強度＞
各医療用貼付材を１９ｍｍ幅、長さ７２ｍｍに裁断し、手の第２指の第２関節に重ね合わせるように巻付け（ラップ巻き）、約２４時間貼付後、貼付材を剥離する際の状態を観察した。
〇：きれいに剥離することができる。
△：剥離時に千切れないが、基材が伸びきってしまう。
×：剥離時に基材が千切れてしまう。
【００４７】
＜実用評価：自背面接着性＞
上記引き剥がし強度測定と同様に試験を行い、剥離除去前の状態を観察し、以下の基準で判定した。
〇：２４時間貼付においても、ラップ巻きした自背面から剥がれることはなく、強固に接着していた。
×：２４時間貼付中に、ラップ巻きした自背面から貼付材端部が剥離した。
【００４８】
＜５０％モジュラス、引張強度、自背面接着力＞
各医療用貼付材を１９ｍｍ幅、長さ１５０ｍｍに裁断し、２３℃の雰囲気下、テンシロン式引張試験機を用いてチャック間距離１００ｍｍ、引張速度２００ｍｍ／分の条件下で長さ方向に引っ張り、５０％モジュラスおよび引張強度（破断強度）を測定した。自背面接着力は、上記貼付材よりも大きな貼付材をベークライト板に貼着し、その背面に上記大きさに裁断した貼付材を２ｋｇのゴムロールを１往復させることによって加圧貼着し、室温下で３０分放置後に１８０度方向に引張速度２００ｍｍ／分で引き剥がした際の剥離力を測定した。
【００４９】
【表２】

【図面の簡単な説明】
【図１】実施例１にて得られた貼付材用基材中の各共重合体の状態を示す透過型電子顕微鏡写真（２万倍）である。
【図２】実施例１にて得られた貼付材用基材中の各共重合体の状態を示す透過型電子顕微鏡写真（１０万倍）である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a base material for an adhesive material used for skin application in the medical hygiene field and the like, a medical adhesive material using the same, and an emergency adhesive bandage, and more specifically, an emergency adhesive bandage, a large adhesive bandage, a dressing material, Used for draping materials, etc., for adhesive base materials with excellent properties as substitutes for conventional polyvinyl chloride film, polyurethane film, and polyolefin film, and used for medical adhesive materials and emergency adhesive plaster It can be done.
[0002]
[Prior art]
The medical patch is usually formed by providing a pressure-sensitive adhesive layer on one side of a base film, and is used by sticking to the skin surface to be applied via the pressure-sensitive adhesive layer.
[0003]
Conventionally, as a base material used for such a patch for medical use, the main component is soft polyvinyl chloride from the viewpoint of skin followability (flexibility), stretchability, texture and the like during application. It is used for.
[0004]
However, in general, soft polyvinyl chloride contains a lot of plasticizers such as dioctyl phthalate in order to give flexibility when it is formed into a film, and these plasticizers migrate into the pressure-sensitive adhesive layer. It has been pointed out that the cohesive force of the pressure-sensitive adhesive layer is reduced to cause problems such as an adhesive residue on the skin surface and a decrease in adhesive force. On the other hand, in recent years, from the viewpoint of environmental problems such as the generation of harmful substances during film incineration, movements to reduce the amount of polyvinyl chloride resin containing halogen chlorine atoms are progressing in various fields.
[0005]
In addition, when an emergency bandage using a film base made of polyvinyl chloride resin is wrapped around a part with high movement such as a joint of a finger, it is stretched and wound moderately at the time of application. Slowly, so-called stress relaxation is easy, and after application, a gap is gradually formed between the application surface and the first-aid adhesive bandage, falling off from a finger or the like, or being displaced. Furthermore, since the polyvinyl chloride resin has a high temperature sensitivity, the film substrate becomes hard in winter, and the face may be injured when washing the face.
[0006]
Therefore, as a polyvinyl chloride substitute resin, a base film for a patch using a polyolefin resin has been studied, and products using various polyolefin resins have been put on the market.
[0007]
Polyethylene and polypropylene are used as specific polyolefin resins, but they are slightly inferior to the above polyvinyl chloride in terms of the balance of flexibility, elongation, and mechanical strength. When it is satisfied, the mechanical strength becomes inferior, and when it is made into a multilayer sheet to satisfy the mechanical strength, the release paper laminated to cover and protect the adhesive layer surface is used at the time of use. When peeled and removed, there may be a problem that the film curls due to the difference in elongation characteristics of the olefinic resins in the respective layers.
[0008]
On the other hand, polyurethane-based films are used in applications that require transparency, such as transparent dressing, and that require excellent followability to the movement of the skin surface to be applied. However, the polyurethane film has excellent stretchability and flexibility, but is inferior to the above films in terms of mechanical strength, and when a pressure-sensitive adhesive layer is formed on one side of the film as a medical patch Therefore, it is necessary to perform anchor treatment such as application of a primer and corona discharge treatment.
[0009]
[Problems to be solved by the invention]
As described above, in the polyvinyl chloride resin substitute film such as polyolefin resin and polyurethane resin, it is the actual condition that a film having characteristics equal to or higher than that of the polyvinyl chloride resin film is not obtained.
[0010]
Therefore, the present inventors diligently tried to solve the problems of conventional base film made of polyvinyl chloride and problems of base film made of polyolefin resin as an alternative. As a result of investigation, by using an ethylene-vinyl acetate copolymer as a main component and containing a specific triblock copolymer in a finely dispersed state, flexibility, stretchability, mechanical strength, The present inventors have found that a medical patch and an emergency bandage satisfying characteristics such as anti-curl properties can be obtained, and have completed the present invention.
[0011]
[Means for Solving the Problems]
That is, the present invention comprises a polystyrene unit and a vinyl-polyisoprene unit in which a vinyl group is introduced into the side chain of polyisoprene in 60 to 95 parts by weight of an ethylene-vinyl acetate copolymer to form a three-dimensional structure. The present invention provides a base material for a patch, wherein 5 to 40 parts by weight of a triblock copolymer is uniformly finely dispersed.
[0012]
Furthermore, the present invention provides a medical patch comprising a pressure-sensitive adhesive layer formed on one side of the above-mentioned patch material base material, and a part of the surface of the pressure-sensitive adhesive layer in the medical patch to protect a wound part. A first-aid bandage with a pad is provided.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The base material for a patch of the present invention contains an ethylene-vinyl acetate copolymer resin as a main component, and is blended in an amount of 60 to 95 parts by weight, preferably 70 to 85 parts by weight in the base material composition. . When the blending amount is less than 60 parts by weight, the mechanical strength of the obtained base material is insufficient, and it tends to be low modulus and tends to be inferior in handleability and the slipperiness of the back surface of the base material film. On the other hand, if the blending amount exceeds 95 parts by weight, the modulus at 50% elongation becomes too high and the wettability of the surface of the obtained base film is lowered, so that it is sufficient when an adhesive layer is formed on one side. Throwing power cannot be obtained, and skin irritation tends to increase. In addition, when the surface wettability of the base material for patch of this invention is measured according to the method prescribed | regulated to JISZ1529, it is preferable to set it as 350 microN / cm or more.
[0014]
In addition, the molecular weight of the ethylene-vinyl acetate copolymer to be used is preferably one having a weight average molecular weight of about 10,000 to 100,000 from the viewpoint of practical mechanical strength of the obtained substrate. Furthermore, it is desirable that the vinyl acetate unit content in the copolymer is 3 to 28% by weight, preferably 10 to 25% by weight. When the content of the vinyl acetate unit is less than 3% by weight, the wettability of the surface of the obtained base film is lowered, so that it is difficult to obtain a sufficient anchoring force when an adhesive layer is formed on one side. When the content exceeds 28% by weight, the mechanical strength of the obtained base film tends to be insufficient.
[0015]
In the present invention, the triblock copolymer finely dispersed in the ethylene-vinyl acetate copolymer is composed of a polystyrene unit and a vinyl-polyisoprene unit. The vinyl-polyisoprene unit has a vinyl group introduced into the side chain of polyisoprene, and the triblock copolymer has a three-dimensional structure by the action of the vinyl group. By making it exist in a finely dispersed state in a copolymer, moderate internal cohesion force is provided to the obtained base film.
[0016]
The polystyrene unit in such a triblock copolymer preferably has a styrene content of 10 to 30% by weight, and most preferably 20% by weight. The vinyl bond in the vinyl-polyisoprene unit is preferably 50 to 70% by weight. When the vinyl bond amount is less than 50% by weight, the obtained base film becomes too soft, and the mechanical strength tends to be insufficient. On the other hand, when the vinyl bond amount exceeds 70% by weight, the three-dimensional crosslink density of the triblock copolymer increases, so that the obtained base film becomes hard and tends to be inferior in flexibility.
[0017]
In the base material for a patch of the present invention, the phase composed of the triblock copolymer is present in a finely dispersed state having a size of 1 μm to several μm in the matrix phase composed of the ethylene-vinyl acetate copolymer. It has a so-called sea-island structure. That is, since it has a microphase separation structure, each characteristic of each copolymer is exhibited, and a film property with a good balance different from the uniform dissolution state is exhibited.
[0018]
That is, the base material for patch of the present invention is relatively excellent in blendability because the MFR (melt flow rate) of the ethylene-vinyl acetate copolymer used as the main component and the triblock copolymer dispersed and blended is similar. It will be. Moreover, it is presumed that the glass transition temperature of the triblock copolymer is around 0 ° C., preferably 0 ° C. or less, which contributes to the low modulus in the room temperature region (use conditions).
[0019]
Further, as apparent from the electron micrographs shown in FIGS. 1 and 2, since it has a sea-island structure, the polystyrene portion in the triblock copolymer serves as an island phase domain to reduce the surface tension of the base film, thereby improving the wettability. Presumed to have contributed.
[0020]
In addition, the base material for a patch of the present invention may contain various fillers, pigments, and additives such as a lubricant for facilitating film moldability as long as the physical properties of the film are not affected. It ’s good.
[0021]
Furthermore, it is preferable that the base material for a patch of the present invention has a 50% modulus having a value of 0.2 to 1.2 kgf / 19 mm width from the viewpoint of flexibility and followability to the movement of the applied skin surface. In addition, those with a tensile strength of 1.3 kg / 19 mm width or more measured under the same conditions as the above modulus are suitable fits when wound around fingers (emergency adhesive bandages, wound ties, etc.) Not preferable).
[0022]
The base material for a patch of the present invention can be formed into a sheet by a calendar method, a T-die method, an inflation method, etc., but preferably the point of crystallization of the film, ease of forming, and the formed sheet The calendar method is preferably used from the viewpoint of ease of processing when embossing or the like is performed.
[0023]
The base material for patch in the present invention is formed into a sheet shape as described above, and its thickness is about 30 to 150 μm, which is less uncomfortable when applied to the skin surface and tensile strength. It is desirable from the viewpoint of mechanical strength. In particular, it is preferably set to a thickness of about 30 to 80 μm from the viewpoint of transparency in a dressing application to be applied in a relatively large area for 60 to 150 μm for emergency bandages.
[0024]
The base material for patch of the present invention has a specific composition as described above, and is a medical device for sticking to the skin surface by forming an adhesive layer on one side of the base material formed into a sheet shape. It can be used as a patch. The pressure-sensitive adhesive layer to be formed is formed with a thickness of 20 to 80 μm, preferably 30 to 60 μm, from the viewpoint of skin adhesiveness. Adhesives used can be used as medical adhesives with little skin irritation, such as acrylic adhesives, natural rubber adhesives, synthetic rubber adhesives, silicone adhesives, vinyl ether adhesives, etc. For example, the organic solvent system, the emulsion system, and the hot melt system can be used. Moreover, these adhesives may be used independently or may be used in mixture of multiple types of adhesives.
[0025]
In preparing the medical patch, the patch base material of the present invention has very good wettability, so that the adhesive layer can be formed by a direct copying method or a transfer method without performing an anchor treatment. Needless to say, in order to further improve the wettability, a corona discharge treatment or a known primer can be applied. In addition, as a method of forming the pressure-sensitive adhesive layer on one side of the base material for patch material, a direct copy method in which a pressure-sensitive adhesive solution is directly applied to one side of the base material and dried, or the pressure-sensitive adhesive layer is directly formed by hot melt extrusion. However, in order to prevent unnecessary elongation and curling of the substrate due to solvent or heat, the coating on one side of the release paper for covering and protecting the adhesive layer surface of the obtained medical patch It is preferable to use a transfer method in which a pressure-sensitive adhesive layer is formed in advance by extrusion or the like, and a base material for a patch is bonded to the surface of the formed pressure-sensitive adhesive layer.
[0026]
The medical patch of the present invention can be used as a dressing or wound bond, and a pad for protecting a wound portion of the skin surface such as a gauze cloth or a sponge pad is provided on a part of the surface of the adhesive layer. It can also be an emergency bandage.
[0027]
【The invention's effect】
As described above, the base material for adhesive patch, the medical adhesive patch, and the emergency adhesive bandage of the present invention have an ethylene-vinyl acetate copolymer as a main component and finely disperse a triblock copolymer having a specific structure therein. Because it exists in the state, it has practically satisfactory flexibility and stretchability, skin followability, mechanical strength equivalent to or better than conventional polyvinyl chloride film, polyurethane film and polyolefin film, and is in use There is little sense of discomfort (such as a feeling of pressure or tension).
[0028]
Moreover, since it is a base material for a patch having such a composition, when a pressure-sensitive adhesive layer is formed on one side as a medical patch, it does not necessarily require an anchor treatment and exhibits excellent anchoring properties. Is. In particular, when the release paper laminated on the surface of the pressure-sensitive adhesive layer is peeled and removed, curling does not occur and the operability is excellent.
[0029]
Furthermore, in emergency bandage applications, it has excellent adhesion to fingers to be applied, and also has excellent adhesion to the back surface when wrapped around a finger, so-called wrapping, so that printing ink can be applied even when printed on the substrate surface. It is good. Further, even in a dressing application applied to a relatively large area, there is almost no sense of incongruity during application and the cost is low. Therefore, it is useful as a substitute for an ultra-thin polyurethane film generally used in this application.
[0030]
【Example】
Examples of the present invention will be described below and will be described in more detail. However, the present invention is not limited to these examples, and various applications are possible without departing from the technical idea of the present invention. Hereinafter, “parts” means parts by weight.
[0031]
Example 1
77 parts by weight of an ethylene-vinyl acetate copolymer (trade name: Ultrasen 5A53A, manufactured by Tosoh Corporation) having a vinyl acetate unit content of 20% by weight, a styrene content of 20% by weight and a vinyl bond content of 55 23 parts by weight of a polystyrene / vinyl-polyisoprene triblock copolymer (made by Kuraray Co., Ltd., trade name: Hibler 7125) by weight is mixed with a mixing roll in the presence of 1 part of a fatty acid-based lubricant, and then reverse L The film was formed with a calender roll to prepare a base material for a patch material having a thickness of 90 μm.
[0032]
The sticking substrate thus obtained was cut into strips with a razor blade, and then embedded in an epoxy resin, which was then stained with RuO ₄ as a thin section with a microtome and observed with a transmission electron microscope. did. The electron micrographs are shown in FIG. 1 (20,000 times) and FIG. 2 (100,000 times). In each figure, it is clear that the black dyed portion is the triblock copolymer phase and is finely dispersed in the ethylene-vinyl acetate copolymer phase as the matrix phase.
[0033]
An alkyl acrylate adhesive is applied onto a release paper so that the paste thickness after drying is 25 μm, and dried to produce an adhesive layer. This is applied to one side of the base material for patch obtained above. It was transferred to produce a medical patch.
[0034]
Example 2
For the patch of the present invention, as in Example 1, except that the blending amount of the ethylene-vinyl acetate copolymer used in Example 1 was 95 parts and the blending amount of the triblock copolymer was 5 parts. A base material and a medical patch were prepared.
[0035]
Example 3
For the patch of the present invention, as in Example 1, except that the blending amount of the ethylene-vinyl acetate copolymer used in Example 1 was 60 parts and the blending amount of the triblock copolymer was 40 parts. A base material and a medical patch were prepared.
[0036]
Example 4
The triblock copolymer used in Example 1 was a polystyrene / vinyl-polyisoprene triblock copolymer having a styrene content of 20% by weight and a vinyl bond content of 70% by weight (trade name: Hibler, manufactured by Kuraray Co., Ltd.). Except that it was set to 5127), it carried out similarly to Example 1, and produced the base material for patch materials and the medical patch material of this invention.
[0037]
Comparative Example 1
A base material for a patch and a medical patch were prepared using only the ethylene-vinyl acetate copolymer used in Example 1.
[0038]
Comparative Example 2
Using the same polyurethane-based film as the film commercially available as a dressing (thickness 25 μm, film formation by the inflation method) as the base material for the patch, the adhesive layer used in Example 1 was formed on this, A medical patch was prepared.
[0039]
A soft polyvinyl chloride film (thickness 80μm) similar to the film marketed as an emergency bandage is used as a base material for a patch, and a synthetic rubber-based adhesive layer is formed on this through a primer, for medical use. A patch was prepared.
[0040]
Table 1 summarizes the physical properties of the copolymers for preparing the base materials for patch materials used in the above Examples and Comparative Examples.
[0041]
[Table 1]

[0042]
Moreover, the following characteristics were evaluated about the base material for patch materials and the medical patch material obtained by said each Example and the comparative example, and the result was shown in Table 2.
[0043]
<Wettability>
According to the method prescribed in JIS Z 1529, the wettability (unit: μN / cm) of the surface of the prepared base film for a patch was measured.
[0044]
<Practical evaluation: Throwability>
After each medical patch was applied to the volunteer's abdomen for about 24 hours, the state of the applied skin surface when peeled and removed was determined according to the following criteria, and the anchoring property was evaluated.
◯: No pressure-sensitive adhesive layer remains on the skin surface and does not cause throwing damage.
Δ: The pressure-sensitive adhesive layer partially remains at the end portion.
X: The pressure-sensitive adhesive layer is completely transferred to the skin surface, causing complete throwing destruction.
[0045]
<Practical evaluation: Flexibility>
Each medical patch was applied to the volunteer's abdomen for about 24 hours, and the state during application was determined according to the following criteria to evaluate flexibility.
◯: Excellent skin followability and extremely high flexibility. (Guideline: 50% modulus 0.2-0.5kgf / 19mm width)
(Triangle | delta): It is too flexible and is inferior to a self-supporting property. (Guideline: 50% modulus <0.2kgf / less than 19mm width)
X: Lack of flexibility. (Guideline: 50% modulus> 0.5kgf / 19mm width or more)
[0046]
<Practical evaluation: Peel strength>
Each medical patch is cut to 19 mm width and 72 mm in length, wrapped so as to overlap the second joint of the second finger of the hand (wrap winding), and after pasting for about 24 hours, The condition was observed.
◯: It can be peeled cleanly.
(Triangle | delta): Although it is not torn at the time of peeling, a base material will extend completely.
X: The substrate is broken at the time of peeling.
[0047]
<Practical evaluation: Self-back adhesiveness>
The test was performed in the same manner as the above-described peeling strength measurement, the state before the peeling removal was observed, and the determination was made according to the following criteria.
◯: Even when pasted for 24 hours, it was not peeled off from the back surface of the wrap-wrapped self, and was firmly adhered.
X: During pasting for 24 hours, the end of the patch was peeled off from the self-wrapped back surface.
[0048]
<50% modulus, tensile strength, self-back adhesion>
Each medical patch was cut to a width of 19 mm and a length of 150 mm, and pulled in the length direction under the conditions of a distance between chucks of 100 mm and a tensile speed of 200 mm / min using a Tensilon tensile tester in an atmosphere of 23 ° C. The 50% modulus and tensile strength (breaking strength) were measured. The adhesive strength of the back surface is affixed to a bakelite plate with a larger adhesive material than the above adhesive material, and the adhesive material cut to the above size is applied to the back surface by reciprocating a 2 kg rubber roll one time. The peel force when peeled in the 180 degree direction at a pulling speed of 200 mm / min after standing for 30 minutes under was measured.
[0049]
[Table 2]

[Brief description of the drawings]
FIG. 1 is a transmission electron micrograph (20,000 times) showing the state of each copolymer in a base material for a patch obtained in Example 1. FIG.
2 is a transmission electron micrograph (magnification 100,000 times) showing the state of each copolymer in the base material for a patch obtained in Example 1. FIG.

Claims (10)

Ethylene - vinyl copolymer 60 to 95 parts by weight of acetic acid, and polystyrene units, vinyl vinyl group in the side chain of the polyisoprene has been introduced - Ri Do polyisoprene units, tri-block that has become a three-dimensional structure A base material for a patch, wherein 5 to 40 parts by weight of a copolymer are uniformly finely dispersed.  The base material for a patch according to claim 1, wherein the ethylene-vinyl acetate copolymer has a vinyl acetate unit content of 3 to 28% by weight.  The base material for patch materials of Claim 1 in which a triblock copolymer contains the polystyrene unit of 10-30 weight% of styrene content.  The base material for patch materials of Claim 1 in which a triblock copolymer contains the vinyl-polyisoprene unit of 50 to 70 weight% of vinyl bonds.  The base material for a patch according to any one of claims 1 to 4, wherein the triblock copolymer phase is finely dispersed in the ethylene-vinyl acetate copolymer phase to form a sea-island structure.  The base material for a patch according to any one of claims 1 to 5, wherein the 50% modulus is 0.2 to 1.2 kgf / 19 mm width and the tensile strength is 1.3 kg / 19 mm width or more.  The base material for patch materials in any one of Claims 1-6 whose wettability prescribed | regulated to JISZ1529 is 350 microN / cm or more.  The base material for a patch according to any one of claims 1 to 7, wherein the base material is formed into a sheet shape by a calendar method.  A medical patch comprising a pressure-sensitive adhesive layer formed on one side of the base material for a patch according to claim 1.  An emergency bandage comprising a pad for protecting a wound part on a part of the surface of the adhesive layer of the medical patch according to claim 9.

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