JP2015113330A - Skin care film - Google Patents

Skin care film Download PDF

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JP2015113330A
JP2015113330A JP2013258654A JP2013258654A JP2015113330A JP 2015113330 A JP2015113330 A JP 2015113330A JP 2013258654 A JP2013258654 A JP 2013258654A JP 2013258654 A JP2013258654 A JP 2013258654A JP 2015113330 A JP2015113330 A JP 2015113330A
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film
skin care
ointment
mass
vinylidene chloride
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JP6175363B2 (en
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美央 久保田
Bio Kubota
美央 久保田
偉 入矢
Isamu Iriya
偉 入矢
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Asahi Kasei Chemicals Corp
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Asahi Kasei Chemicals Corp
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Abstract

PROBLEM TO BE SOLVED: To provide a skin care film having an excellent skin-following property.SOLUTION: A skin care film comprises a film that satisfies a density of 1.3-1.9 g/cm, a thickness of 5-50 μm, a tensile elasticity of 200-600 MPa and a tensile elongation of 60-150%.

Description

本発明はスキンケアフィルムに関する。   The present invention relates to a skin care film.

従来から、軟膏剤をフィルムに担持したスキンケアフィルムが医療用途に広く用いられている。上記フィルムにあらかじめ軟膏剤を塗布して皮膚へ貼りつけることにより、素手で塗布する際の不衛生性の改善や、投与量の管理、衣服や他部位への転着の防止を図ることができる。一方、上記スキンケアフィルムは、皮膚への貼付け時の違和感や、また軟膏剤の移行による機械強度の低下といった問題をかかえている。   Conventionally, skin care films in which an ointment is carried on a film have been widely used for medical purposes. By applying an ointment to the film in advance and sticking it to the skin, it is possible to improve unsanitary conditions when applying with bare hands, manage dosage, and prevent transfer to clothes and other parts. . On the other hand, the above-mentioned skin care film has problems such as an uncomfortable feeling when applied to the skin and a decrease in mechanical strength due to the transfer of the ointment.

このような問題を解決するため、特許文献1〜2では、関節などの屈曲部で伸びることにより、屈曲部を曲げ伸ばしした際に生じうる突っ張り感が低減されたフィルムを用いたスキンケアフィルムが提案されている。   In order to solve such a problem, Patent Documents 1 and 2 propose a skin care film using a film in which a tension feeling that may occur when the bent portion is bent and stretched is reduced by extending at a bent portion such as a joint. Has been.

特許第4616542号公報Japanese Patent No. 4616542 特許第3400026号公報Japanese Patent No. 3400026

しかしながら、特許文献1〜2に記載の技術では、皮膚へ貼り付けた際に肌に沿ってなじみ、違和感なく貼付けられるフィルムを得ることはできない。   However, with the techniques described in Patent Documents 1 and 2, it is not possible to obtain a film that fits along the skin when applied to the skin and can be applied without a sense of incongruity.

本発明は、上記の従来技術が有する課題に鑑みてなされたものであり、肌沿い性に優れたスキンケアフィルムを提供することを目的とする。   This invention is made | formed in view of the subject which said prior art has, and aims at providing the skin care film excellent in the along-skin property.

本発明者らは上記課題を解決するため鋭意検討を重ね、本発明を完成させるに至った。すなわち本発明は、次のとおりである。
[1]
密度1.3〜1.9g/cm3、厚み5〜50μm、引張弾性率200〜600MPa及び引張伸び60〜150%を満たすフィルムを有する、スキンケアフィルム。
[2]
前記フィルムの表面に接する軟膏剤をさらに有する、[1]に記載のスキンケアフィルム。
[3]
前記フィルムの20℃におけるZismanプロットにより求めた臨界表面張力が35〜50mN/mである、[1]又は[2]に記載のスキンケアフィルム。
[4]
前記フィルムの主成分が塩化ビニリデン共重合体である、[1]〜[3]のいずれかに記載のスキンケアフィルム。
[5]
前記フィルムが、質量平均分子量7万〜14万及び塩化ビニリデン単量体単位75〜96質量%を満たす塩化ビニリデン共重合体100質量部と、脂肪酸エステル類とエポキシ化化合物との混合物1〜10質量部と、を含む、[1]〜[4]のいずれかに記載のスキンケアフィルム。
[6]
前記軟膏剤がパラフィンワックス及び流動パラフィンの少なくとも一方を含む、[2]〜[5]のいずれかに記載のスキンケアフィルム。
In order to solve the above-mentioned problems, the present inventors have made extensive studies and have completed the present invention. That is, the present invention is as follows.
[1]
A skin care film having a film satisfying a density of 1.3 to 1.9 g / cm 3 , a thickness of 5 to 50 μm, a tensile elastic modulus of 200 to 600 MPa, and a tensile elongation of 60 to 150%.
[2]
The skin care film according to [1], further comprising an ointment in contact with the surface of the film.
[3]
The skin care film according to [1] or [2], wherein a critical surface tension obtained by a Zisman plot at 20 ° C. of the film is 35 to 50 mN / m.
[4]
The skin care film according to any one of [1] to [3], wherein the main component of the film is a vinylidene chloride copolymer.
[5]
100 to 10 parts by mass of a vinylidene chloride copolymer satisfying a mass average molecular weight of 70,000 to 140,000 and a vinylidene chloride monomer unit of 75 to 96% by mass, and a mixture of a fatty acid ester and an epoxidized compound of 1 to 10 mass. A skin care film according to any one of [1] to [4].
[6]
The skin care film according to any one of [2] to [5], wherein the ointment contains at least one of paraffin wax and liquid paraffin.

本発明によれば、皮膚へ貼り付けた際に肌へ沿ってなじみ違和感なく貼付けられる肌沿い性に優れたスキンケアフィルムを提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, when affixed on skin, the skin care film excellent in the along-skin property which can be affixed along a skin without a strange feeling can be provided.

以下、本発明を実施するための形態(以下、「本実施形態」と略記する。)について詳細に説明する。なお、本発明は、以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。   Hereinafter, a mode for carrying out the present invention (hereinafter abbreviated as “this embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

本実施形態のスキンケアフィルムは、密度1.3〜1.9g/cm3、厚み5〜50μm、引張弾性率200〜600MPa及び引張伸び60〜150%を満たすフィルムを有する。このように構成されているため、本実施形態のスキンケアフィルムは皮膚へ貼り付けた際に肌へ沿ってなじみ、違和感なく貼付けられる。すなわち、本実施形態のスキンケアフィルムは優れた肌沿い性を発揮することができる。 The skin care film of this embodiment has a film satisfying a density of 1.3 to 1.9 g / cm 3 , a thickness of 5 to 50 μm, a tensile elastic modulus of 200 to 600 MPa, and a tensile elongation of 60 to 150%. Since it is comprised in this way, the skin care film of this embodiment is familiar along skin when it affixes on skin, and is affixed without discomfort. That is, the skin care film of the present embodiment can exhibit excellent along-skin properties.

本実施形態におけるフィルムは、密度1.3〜1.9g/cm3、厚み5〜50μm、引張弾性率200〜600MPa及び引張伸び60〜150%を満たす。この範囲とすることで、貼り付けた際に肌へ沿ってなじみ、破けるなどの心配もなく、腰があって取扱い性がよく、また多少の実用変形にも耐えることができる。上記のような効果を一層高める観点から、好ましい範囲としては、密度1.5〜1.8g/cm3、厚み10〜20μm、引張弾性率400〜600MPa、引張伸び100〜140%である。なお、上記密度、厚み、引張弾性率及び引張伸びについては、後述する実施例に記載の方法で求めることができる。また、本実施形態におけるフィルムは、当該フィルムを構成する重合体の構成成分や重合度等を適宜調整することで、本実施形態の所望の物性(密度、引張弾性率、引張伸び)に制御することができる。 The film in the present embodiment satisfies a density of 1.3 to 1.9 g / cm 3 , a thickness of 5 to 50 μm, a tensile elastic modulus of 200 to 600 MPa, and a tensile elongation of 60 to 150%. By setting it within this range, there is no fear of conforming to the skin and tearing when it is pasted, it has a waist and is easy to handle, and can withstand some practical deformation. From the viewpoint of further enhancing the above effects, preferable ranges are a density of 1.5 to 1.8 g / cm 3 , a thickness of 10 to 20 μm, a tensile elastic modulus of 400 to 600 MPa, and a tensile elongation of 100 to 140%. In addition, about the said density, thickness, a tensile elasticity modulus, and tensile elongation, it can obtain | require by the method as described in the Example mentioned later. Moreover, the film in the present embodiment is controlled to have the desired physical properties (density, tensile elastic modulus, tensile elongation) of the present embodiment by appropriately adjusting the constituent components and degree of polymerization of the polymer constituting the film. be able to.

本実施形態におけるフィルムは上述した条件を満たす限り、材質や形状等は特に限定されない。例えば、本実施形態におけるフィルムに対して、コロナ処理やプラズマ処理などの表面処理や穿孔加工、印刷加工、粘着剤の塗工などを施してもよい。また、上述した条件の範囲で複数のフィルムや不織布を含む多層で構成されていてもよい。   The material and shape of the film in the present embodiment are not particularly limited as long as the above-described conditions are satisfied. For example, the film in the present embodiment may be subjected to surface treatment such as corona treatment or plasma treatment, perforation, printing, adhesive coating, or the like. Moreover, you may be comprised by the multilayer containing a some film and nonwoven fabric in the range of the conditions mentioned above.

本実施形態のスキンケアフィルムは、上記フィルムの表面に接する軟膏剤をさらに有するものとすることができる。本明細書において、「軟膏剤」とは、室温下で流動しないものの展延性を有する半固形状の物質であって、凝固点を持たない又は凝固点が−10℃以下のものを示す。上記軟膏剤としては、以下に限定されないが、例えば、油脂性軟膏剤、水溶性軟膏剤、乳剤性軟膏剤などが挙げられる。上記油脂性軟膏剤としては、以下に限定されないが、例えば、ワセリン、プラスチベース、単軟膏、亜鉛華軟膏が挙げられる。上記水溶性軟膏剤としては、以下に限定されないが、例えば、マクロゴール軟膏が挙げられる。上記乳剤性軟膏剤としては、以下に限定されないが、例えば、ハイドロゲル軟膏が挙げられる。   The skin care film of this embodiment may further have an ointment that contacts the surface of the film. In the present specification, the term “ointment” refers to a semi-solid substance that does not flow at room temperature but has spreadability and does not have a freezing point or has a freezing point of −10 ° C. or lower. Examples of the ointment include, but are not limited to, an oleaginous ointment, a water-soluble ointment, and an emulsion ointment. Examples of the oily ointment include, but are not limited to, petrolatum, plastibase, simple ointment, and zinc white ointment. Examples of the water-soluble ointment include, but are not limited to, macrogol ointment. Examples of the emulsion ointment include, but are not limited to, hydrogel ointment.

本実施形態において、軟膏剤は、精製したり、異種の軟膏剤を組み合わせたり、さらに粘着剤や各種添加剤、また薬理活性成分などを加えたりしてもよい。添加剤としては、以下に限定されないが、例えば、安定剤、界面活性剤、抗酸化剤、防腐剤、pH調整剤、香料などである。薬理活性成分としては、以下に限定されないが、例えば、殺菌消毒剤やビタミン剤、消炎鎮痛剤、抗ウイルス剤、抗生物質製剤などが挙げられる。   In the present embodiment, the ointment may be purified, combined with different types of ointments, and further added with an adhesive, various additives, pharmacologically active ingredients, and the like. Examples of additives include, but are not limited to, stabilizers, surfactants, antioxidants, preservatives, pH adjusters, and fragrances. Examples of pharmacologically active ingredients include, but are not limited to, bactericidal disinfectants, vitamins, anti-inflammatory analgesics, antiviral agents, antibiotic preparations, and the like.

本実施形態における軟膏剤はパラフィンワックス及び流動パラフィンの少なくとも一方を含むことが好ましく、ワセリン、プラスチベースを含むことがより好ましい。上記のほか、本実施形態における軟膏剤としては、以下に限定されないが、例えば、ミネラルオイル、医療用パラフィン、ベビーオイル等も挙げられる。   The ointment in this embodiment preferably contains at least one of paraffin wax and liquid paraffin, and more preferably contains petrolatum or plastibase. In addition to the above, examples of the ointment in the present embodiment include, but are not limited to, mineral oil, medical paraffin, baby oil, and the like.

また、本実施形態において、軟膏剤が転着しないよう必要に応じて、剥離材を設けたり、軟膏剤を内側にしてスキンケアフィルムを2つ折りにして周囲を封止するなどの形状にしてもよい。上記剥離材は、以下に限定されないが、例えば、シリコーン樹脂やフッ素樹脂で離型処理されたフィルムや紙、不織布、織物、編物などを用いることができる。上記剥離材の好ましい厚みの範囲は10〜1000μmである。   In the present embodiment, if necessary, a release material may be provided so that the ointment does not transfer, or the skin care film may be folded in half with the ointment inside, and the periphery may be sealed. . The release material is not limited to the following, but for example, a film, paper, nonwoven fabric, woven fabric, knitted fabric or the like that has been subjected to a release treatment with a silicone resin or a fluororesin can be used. The preferable thickness range of the release material is 10 to 1000 μm.

本実施形態における軟膏剤は目付1〜100g/cm2で基材に塗布することが好ましい。上記目付けを1g/cm2以上とする場合、軟膏剤をより均一に塗布することができる傾向にあり、上記目付けを100g/cm2以下とする場合、スキンケアフィルム貼り付けの際の肌への過度なべたつき感を効果的に低減させることができる傾向にある。なお、上記目付けはスキンケアフィルムを10cm角に切り出して重量を測定し、フィルムのみの重量を減じてから面積で割り返すことによりにより求めることができる。 The ointment in this embodiment is preferably applied to the substrate with a basis weight of 1 to 100 g / cm 2 . When the basis weight is 1 g / cm 2 or more, the ointment tends to be applied more uniformly. When the basis weight is 100 g / cm 2 or less, the skin care film is excessively applied to the skin. There exists a tendency which can reduce a sticky feeling effectively. The basis weight can be obtained by cutting the skin care film into a 10 cm square, measuring the weight, and reducing the weight of the film alone and then dividing it by the area.

本実施形態において、上記塗布の方法としては、以下に限定されないが、例えば、ホットメルト塗工機やダイコーター、バーコーター、ロールコーターなどの塗工機を用いることができる。また軟膏剤の塗布パターンとしては、以下に限定されないが、線状、ドット状、スパイラル状、市松状などの塗布パターンを採用することができる。   In the present embodiment, the application method is not limited to the following, and for example, a coating machine such as a hot melt coating machine, a die coater, a bar coater, or a roll coater can be used. The application pattern of the ointment is not limited to the following, but an application pattern such as a linear shape, a dot shape, a spiral shape, or a checkered shape can be adopted.

密度1.3〜1.9g/cm3、厚み5〜50μm、引張弾性率200〜600MPa及び引張伸び60〜150%を満たすフィルムであれば、本実施形態のスキンケアフィルムとして好適に用いられるが、さらに20℃におけるZismanプロットにより求めた臨界表面張力が35〜50mN/mであるフィルムを本実施形態のスキンケアフィルムとして用いることがより好ましい。すなわち、本実施形態におけるフィルムの20℃におけるZismanプロットにより求めた臨界表面張力が35〜50mN/mであることが好ましい。臨界表面張力が上記範囲にある場合、軟膏剤がフィルム表面になじみやすく、経時でも軟膏剤がフィルム表面に留まりやすい傾向にある。さらに好ましくは38〜42mN/mの範囲であり、当該範囲にある場合、塗工の均一性をより良好に維持しやすくなる傾向にある。 If it is a film satisfying a density of 1.3 to 1.9 g / cm 3 , a thickness of 5 to 50 μm, a tensile elastic modulus of 200 to 600 MPa and a tensile elongation of 60 to 150%, it is suitably used as the skin care film of the present embodiment. Furthermore, it is more preferable to use a film having a critical surface tension of 35 to 50 mN / m determined by a Zisman plot at 20 ° C. as the skin care film of this embodiment. That is, it is preferable that the critical surface tension of the film in the present embodiment determined by a Zisman plot at 20 ° C. is 35 to 50 mN / m. When the critical surface tension is in the above range, the ointment tends to be familiar with the film surface, and the ointment tends to stay on the film surface over time. More preferably, it is the range of 38-42 mN / m, and when it exists in the said range, it exists in the tendency which becomes easy to maintain the uniformity of coating more favorably.

本実施形態におけるフィルムとしては、以下に限定されないが、例えば、ポリ塩化ビニリデンやポリエチレン、ポリプロピレンなどのポリオレフィン類、ポリエチレンテレフタレートなどのポリエステル類、エチレン/ビニルアルコール共重合体、エチレン/酢酸ビニル共重合体、ポリアミド、ポリウレタン等をその材料として適用することができる。これらは単独で又は適宜組み合わせて用いることができる。上記した中でも塩化ビニリデン共重合体を主成分とするフィルムを特に好適に用いることができる。すなわち、本実施形態におけるフィルムの主成分が塩化ビニリデン共重合体であることが好ましい。塩化ビニリデン共重合体を主成分とするフィルムは軟膏剤が含浸しにくいため、より良好な機械強度を維持できる傾向にある。なお、本明細書における「主成分」とは、典型的には50質量%以上を意味する。   The film in the present embodiment is not limited to the following. For example, polyolefins such as polyvinylidene chloride, polyethylene and polypropylene, polyesters such as polyethylene terephthalate, ethylene / vinyl alcohol copolymer, ethylene / vinyl acetate copolymer Polyamide, polyurethane and the like can be applied as the material. These can be used alone or in appropriate combination. Among those described above, a film containing a vinylidene chloride copolymer as a main component can be particularly preferably used. That is, the main component of the film in this embodiment is preferably a vinylidene chloride copolymer. Since a film containing a vinylidene chloride copolymer as a main component is difficult to be impregnated with an ointment, it tends to maintain better mechanical strength. In addition, the “main component” in this specification typically means 50% by mass or more.

上記塩化ビニリデン共重合体としては、質量平均分子量が7万〜14万であり、かつ塩化ビニリデン単量体単位が75〜96質量%であることが好ましい。質量平均分子量がこの範囲の場合、フィルムが延伸性を保ってクラックのないフィルムが作りやすくなる。また塩化ビニリデン単量体単位がこの範囲の場合、フィルムの結晶性がよく、成型後の融着が妨げられやすくなり、取扱い性が向上する。なお、質量平均分子量は後述する実施例に記載の方法により求めることができる。   The vinylidene chloride copolymer preferably has a mass average molecular weight of 70,000 to 140,000 and a vinylidene chloride monomer unit of 75 to 96% by mass. When the mass average molecular weight is within this range, the film can be easily stretched and a crack-free film can be easily produced. When the vinylidene chloride monomer unit is within this range, the crystallinity of the film is good, the fusion after molding tends to be hindered, and the handleability is improved. In addition, a mass average molecular weight can be calculated | required by the method as described in the Example mentioned later.

また、上記塩化ビニリデン共重合体100質量部に対して、脂肪酸エステル類とエポキシ化化合物の混合物を合計1〜10質量部添加することは、より好ましい。脂肪酸エステル類は樹脂を可塑化して押出性を改善する効果がある。ポリ塩化ビニリデン共重合体を含む組成物と相分離を起こさない相溶性のある脂肪酸エステル類としては、以下に限定されないが、例えば、ジブチルセバケート、アセチルトリブチルシトレート、グリセリンジアセトモノラウレート、などが挙げられる。   Moreover, it is more preferable to add a total of 1 to 10 parts by mass of a mixture of a fatty acid ester and an epoxidized compound with respect to 100 parts by mass of the vinylidene chloride copolymer. Fatty acid esters have the effect of plasticizing the resin to improve extrudability. Examples of compatible fatty acid esters that do not cause phase separation with a composition containing a polyvinylidene chloride copolymer include, but are not limited to, dibutyl sebacate, acetyltributyl citrate, glycerin diacetomonolaurate, and the like. Is mentioned.

すなわち、上述した観点から、本実施形態におけるフィルムが、質量平均分子量7万〜14万及び塩化ビニリデン単量体単位75〜96質量%を満たす塩化ビニリデン共重合体100質量部と、脂肪酸エステル類とエポキシ化化合物との混合物1〜10質量部と、を含むことが好ましい。   That is, from the above-mentioned viewpoint, the film in this embodiment has a mass average molecular weight of 70,000 to 140,000 and vinylidene chloride copolymer 100 parts by mass satisfying 75 to 96% by mass of vinylidene chloride monomer units, and fatty acid esters. It is preferable that 1-10 mass parts of mixtures with an epoxidized compound are included.

上記エポキシ化化合物は、塩化ビニリデン共重合体が押出中に熱劣化して発生する塩酸により黄変するのを防ぐ効果がある。上記エポキシ化化合物としては、以下に限定されないが、例えば、エポキシ化大豆油、エポキシ化亜麻仁油、ビスフェノールAジグリシジルエーテル、エポキシ化ステアリン酸オクチル、エポキシ化パーム油などを用いることができる。   The epoxidized compound has an effect of preventing the vinylidene chloride copolymer from yellowing due to hydrochloric acid generated by thermal degradation during extrusion. Examples of the epoxidized compound include, but are not limited to, epoxidized soybean oil, epoxidized linseed oil, bisphenol A diglycidyl ether, epoxidized octyl stearate, and epoxidized palm oil.

さらに本実施形態のスキンケアフィルムの形態としては、特に限定されず、ロール状に巻いて化粧箱に収納した形態や、一定のサイズに切りだし包装した枚葉の形態としてもよい。さらに、必要に応じてγ線や電子線、エチレンオキサイドガスなどの滅菌処理を行ってもよい。   Furthermore, the form of the skin care film of the present embodiment is not particularly limited, and may be a form wound in a roll and housed in a decorative box, or a sheet cut out and packaged to a certain size. Furthermore, you may perform sterilization processing, such as a gamma ray, an electron beam, and ethylene oxide gas, as needed.

本実施形態に係るスキンケアフィルムの製造方法としては、特に限定されないが、例えば、インフレーション法により得られたフィルムに、ホットメルト塗工機でワセリンを目付30g/cm2で塗布し、得られたスキンケアフィルムを100mmの幅にスリットし、さらにそれを直径30mmの小径紙管に巻き返したのちに、化粧箱へ収納する方法を挙げることができる。 Although it does not specifically limit as a manufacturing method of the skin care film which concerns on this embodiment, For example, the petrolatum is apply | coated to the film obtained by the inflation method with 30 g / cm < 2 > of fabric weight with a hot-melt coating machine, and the obtained skin care An example is a method in which the film is slit to a width of 100 mm, and further wound around a small-diameter paper tube having a diameter of 30 mm, and then stored in a decorative box.

次に、実施例及び比較例を挙げて本実施の形態をより具体的に説明するが、本実施の形態はその要旨を超えない限り、以下の実施例に限定されるものではない。   Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless it exceeds the gist.

フィルムの密度、厚み、引張弾性率、引張伸び、フィルムの構成成分として塩化ビニリデン共重合体が含まれる場合における塩化ビニリデン共重合体中の塩化ビニリデン単量体単位の割合、質量平均分子量、製造したスキンケアフィルムの肌沿い性、軟膏剤の移行性は以下の方法で測定した。軟膏剤が塗布されている場合は、軟膏剤が溶解する溶媒を用いてこれを取り除き評価した。   Density, thickness, tensile modulus, tensile elongation of film, proportion of vinylidene chloride monomer unit in vinylidene chloride copolymer when vinylidene chloride copolymer is included as a film component, mass average molecular weight, manufactured The along-skin property of the skin care film and the transferability of the ointment were measured by the following methods. When an ointment was applied, it was removed and evaluated using a solvent in which the ointment was dissolved.

(1)密度
JISK7112プラスチック、非発泡プラスチックの密度および比重の測定方法に基づき、A法水中置換法を用いて測定した。
(1) Density Based on the measurement method of the density and specific gravity of JISK7112 plastic and non-foamed plastic, it was measured using the method A underwater substitution method.

(2)厚み
JISK7130プラスチックフィルムおよびシート厚さ測定方法に基づき、試料の質量法による厚さの試験方法B1法を用いて測定した。
(2) Thickness Based on the JISK7130 plastic film and sheet thickness measuring method, the thickness was measured using the thickness test method B1 method of the sample.

(3)引張弾性率
ASTM−D882に従って測定した。すなわち、各例のスキンケアフィルムをMD、TD方向に沿うように、それぞれ幅10mm、長さ100mmに切り出してサンプルとし、5mm/分の引張速度にて測定を行った。得られた応力−歪のグラフに接線を引き、2%伸長時の応力値をサンプルの厚みに換算した値を算出し、5回の測定の平均値を測定値とし、MD方向とTD方向の平均値を引張弾性率の値とした。測定装置には、商品名「AUTOGRAPH AG−IS」(島津製作所社製)を用いた。
(3) Tensile modulus Measured according to ASTM-D882. That is, the skin care film of each example was cut into a width of 10 mm and a length of 100 mm along the MD and TD directions, respectively, and measured at a tensile speed of 5 mm / min. A tangent line is drawn on the obtained stress-strain graph to calculate a value obtained by converting the stress value at the time of 2% elongation into the thickness of the sample, and the average value of five measurements is taken as a measured value, and the MD direction and the TD direction are calculated. The average value was taken as the value of tensile modulus. The trade name “AUTOGRAPH AG-IS” (manufactured by Shimadzu Corporation) was used for the measuring apparatus.

(4)引張伸び
ASTM−D882に従って測定した。すなわち、スキンケアフィルムをMD、TD方向に沿うように、それぞれ幅10mm、長さ100mmに切り出してサンプルとし、300mm/分の引張速度にて測定を行い破断した際の伸びについて、5回の測定の平均値を測定値とし、MD方向とTD方向の平均値を引張伸びの値とした。測定には、商品名「AUTOGRAPH AG−IS」(島津製作所社製)を用いた。
(4) Tensile elongation Measured according to ASTM-D882. That is, the skin care film was cut into a width of 10 mm and a length of 100 mm along the MD and TD directions, respectively, and measured at a tensile speed of 300 mm / min. The average value was the measured value, and the average value in the MD direction and the TD direction was the tensile elongation value. The trade name “AUTOGRAPH AG-IS” (manufactured by Shimadzu Corporation) was used for the measurement.

(5)塩化ビニリデン共重合体中の塩化ビニリデン単量体単位の割合
高分解のプロトン核磁気共鳴測定装置(1H−NMR:日本電子製α−400)を用いて測定した。この際、塩化ビニリデン共重合体以外の成分が含まれていた場合はあらかじめ取り除いてから測定を行うこととした。例えば、脂肪酸エステル類やエポキシ化合物の場合は次のようにして測定サンプルを得た。
(5) Ratio of vinylidene chloride monomer unit in vinylidene chloride copolymer It was measured using a high resolution proton nuclear magnetic resonance measuring apparatus ( 1 H-NMR: α-400 manufactured by JEOL Ltd.). At this time, in the case where components other than the vinylidene chloride copolymer were contained, the measurement was carried out after removing in advance. For example, in the case of fatty acid esters and epoxy compounds, measurement samples were obtained as follows.

塩化ビニリデン共重合体を主成分とするフィルム1gをテトラヒドロフラン20mlメタノール80mlで再沈させて測定サンプルを得た。この測定サンプルを重水素化テトラヒドロフランに5%溶解した溶液を、測定温度約27℃の条件下、400MHzのH−NMRで測定した。塩化ビニリデン単量体単位はスペクトル中のテトラメチルシランを基準とした特有の化学シフトを用いて計算することとした。   A measurement sample was obtained by reprecipitating 1 g of a film mainly composed of vinylidene chloride copolymer with 20 ml of tetrahydrofuran and 80 ml of methanol. A solution obtained by dissolving 5% of this measurement sample in deuterated tetrahydrofuran was measured by 400 MHz H-NMR under a measurement temperature of about 27 ° C. The vinylidene chloride monomer unit was calculated using a specific chemical shift based on tetramethylsilane in the spectrum.

例えば、塩化ビニリデン樹脂との共重合体樹脂が塩化ビニルの場合には、3.50〜4.20ppm、2.80〜3.50ppm、2.00〜2.80ppmの間のピークから溶媒由来のピークを差し引いて求めた積分値、各々(A)、(B)、(C)として、下記計算式にて求めた。
VDC含有量(質量%)={97.0×((A)+(B)/2)×100}/{97.0×((A)+(B)/2)+62.5×((C)+(B)/2)}
For example, when the copolymer resin with vinylidene chloride resin is vinyl chloride, it is derived from the solvent from the peak between 3.50 to 4.20 ppm, 2.80 to 3.50 ppm, and 2.00 to 2.80 ppm. The integral values obtained by subtracting the peaks were obtained as the following formulas as (A), (B), and (C), respectively.
VDC content (% by mass) = {97.0 × ((A) + (B) / 2) × 100} / {97.0 × ((A) + (B) / 2) + 62.5 × (( C) + (B) / 2)}

また、共重合体樹脂が塩化ビニル以外の場合も、これに準じて特有の化学シフトの積分値から計算して求めた。   Further, when the copolymer resin is other than vinyl chloride, it was calculated from the integral value of the specific chemical shift according to this.

(6)質量平均分子量
ゲルパーミエーションクロマトグラフ(GPC)法を使用して測定した。具体的に説明すると、塩化ビニリデン共重合体を主成分とするフィルムをテトラヒドロフランに0.05質量%溶解し、分子量既知の単分散ポリスチレンを標準物質として測定することとした。測定装置としては東ソー(株)製8000シリーズ<商品名>を使用した。カラムは東ソー(株)製GMH6(3/8インチ×60cm)を直列に2本使用し、展開溶媒はテトラヒドロフランを用いた。
(6) Mass average molecular weight It measured using the gel permeation chromatograph (GPC) method. More specifically, a film containing a vinylidene chloride copolymer as a main component was dissolved in 0.05% by mass in tetrahydrofuran, and measurement was performed using monodisperse polystyrene having a known molecular weight as a standard substance. As a measuring device, Tosoh Co., Ltd. 8000 series <trade name> was used. The column used two GMH6 (3/8 inch x 60 cm) manufactured by Tosoh Corporation in series, and tetrahydrofuran was used as the developing solvent.

(7)肌沿い性
40mm角にスキンケアフィルムをサンプリングし、20代〜40代の男性10人女性10人の前腕部へ貼り付けて肌沿い性を官能評価で判定した。違和感なしと判断した人数で次のように判定した。なお、突っ張り感や異物感などを感じることを上記の「違和感」に当たるものとして評価した。
○:16人以上が違和感なし
△:10人〜15人が違和感なし
×:9人以下が違和感なし
(7) Skin alignment The skin care film was sampled in a 40 mm square and pasted on the forearms of 10 men and 10 women in their 20s to 40s, and the skin alignment was determined by sensory evaluation. The number of people judged to be uncomfortable was determined as follows. In addition, it was evaluated that feeling a sense of urgency, a foreign body feeling, etc. was equivalent to the above-mentioned “discomfort”.
○: 16 or more people have no discomfort △: 10 to 15 people have no discomfort ×: 9 people or less have no discomfort

(8)軟膏剤移行性
ワセリン塗布前のフィルムと、30g/cm2の目付でワセリンをフィルムに塗布し、室温23℃±1℃、湿度50%±2%の条件で1週間エージングした後のフィルムの引張強度の変化量によって評価した。
(8) Ointment transferability Vaseline was applied to the film before application of petrolatum and 30 g / cm 2 , and after aging for 1 week under conditions of room temperature 23 ° C. ± 1 ° C. and humidity 50% ± 2%. Evaluation was based on the amount of change in the tensile strength of the film.

引張強度の測定は、ASTM−D882に従った。サンプルフィルムは、スキンケアフィルムをMD、TD方向に沿うように、それぞれ幅10mm、長さ100mmに切り出したものを使用した。引張速度は300mm/分で、5回の測定の平均値を測定値とし、MD方向とTD方向の平均値を引張強度の値とした。測定には、商品名「AUTOGRAPH AG−IS」(島津製作所社製)を用いた。得られた結果を以下の基準により評価した。
○:引張強度の変化が5%未満
△:引張強度の変化が5%以上20%未満
×:引張強度の変化が20%以上
Measurement of tensile strength was in accordance with ASTM-D882. The sample film used was a skin care film cut into a width of 10 mm and a length of 100 mm along the MD and TD directions, respectively. The tensile speed was 300 mm / min, the average value of five measurements was taken as the measured value, and the average value in the MD and TD directions was taken as the tensile strength value. The trade name “AUTOGRAPH AG-IS” (manufactured by Shimadzu Corporation) was used for the measurement. The obtained results were evaluated according to the following criteria.
○: Change in tensile strength is less than 5% Δ: Change in tensile strength is 5% or more and less than 20% ×: Change in tensile strength is 20% or more

(9)臨界表面張力
Zismanプロットに用いられる既知の表面張力を持つ液体に対する接触角を測定し、x軸に表面張力、y軸に接触角のcosθをプロットした。上記プロットに基づいて得られた直線をcosθ=1まで外挿したときの値を臨界表面張力とした。既知の表面張力を持つ液体としては、n−アルカン類のヘプタン、デカン、アルコール類のエタノール、エチレングリコール、アルキルハライド類の1−クロロヘキサン、1−クロロオクタンを用いた。測定は、接触角計DM−501(協和界面科学株式会社)を用いた。
(9) Critical surface tension The contact angle for a liquid having a known surface tension used in the Zisman plot was measured, and the surface tension was plotted on the x-axis and cos θ of the contact angle was plotted on the y-axis. The value obtained by extrapolating the straight line obtained based on the above plot to cos θ = 1 was defined as the critical surface tension. As the liquid having a known surface tension, n-alkanes such as heptane, decane, alcohols such as ethanol, ethylene glycol, and alkyl halides such as 1-chlorohexane and 1-chlorooctane were used. For the measurement, a contact angle meter DM-501 (Kyowa Interface Science Co., Ltd.) was used.

[実施例1]
塩化ビニリデン−塩化ビニル共重合体(塩化ビニリデン単量体単位含有量/塩化ビニル単量体単位含有量=80質量%/20質量%、質量平均分子量12万、表1中では「PVDC」と表記)100質量部に対し、脂肪酸エステル類としてジブチルセバケートを3質量部、アセチルトリブチルシトレートを4質量部、エポキシ化化合物としてエポキシ化大豆油を2質量部、添加してヘンシェルミキサーで5分混合した。得られた混合物を溶融押出機で管状に押出し、約10℃の冷水槽で過冷却後、35℃の水中に通し、延伸温度30℃、長手(MD)方向に3.0倍、幅(TD)方向に4.0倍のインフレーション2軸延伸を行って得た管状フィルムをピンチロールで折りたたみ、厚み40μmの平坦長尺状のスキンケアフィルム用フィルムを作製した。フィルム物性の評価結果を表1に示す。
[Example 1]
Vinylidene chloride-vinyl chloride copolymer (vinylidene chloride monomer unit content / vinyl chloride monomer unit content = 80% by mass / 20% by mass, mass average molecular weight 120,000, expressed as “PVDC” in Table 1 ) 3 parts by weight of dibutyl sebacate as fatty acid esters, 4 parts by weight of acetyltributyl citrate, 2 parts by weight of epoxidized soybean oil as an epoxidized compound for 100 parts by weight, and mixed for 5 minutes with a Henschel mixer did. The obtained mixture was extruded into a tubular shape with a melt extruder, supercooled in a cold water bath at about 10 ° C., passed through 35 ° C. water, stretched at 30 ° C., 3.0 times in the longitudinal (MD) direction, and width (TD) ) A tubular film obtained by biaxial stretching of 4.0 times in the direction was folded with a pinch roll to produce a flat and long film for skin care film having a thickness of 40 μm. The evaluation results of film properties are shown in Table 1.

[実施例2]
塩化ビニリデン−塩化ビニル共重合体(塩化ビニリデン含有量/塩化ビニル含有量=90質量%/10質量%、質量平均分子量7万)100質量部に対し、アセチルトリブチルシトレートを2.5質量部、エポキシ化大豆油を0.5質量部、添加して同様に混合した。得られた混合物を実施例1と同様の方法で延伸して巻き取り、厚み20μmの平坦長尺状のダブルプライフィルム原反を作製した。その後スリッターを用いてシングルフィルムに剥離させ10μmのフィルムとした。得られた結果を表1に示す。
[Example 2]
2.5 parts by mass of acetyltributyl citrate with respect to 100 parts by mass of vinylidene chloride-vinyl chloride copolymer (vinylidene chloride content / vinyl chloride content = 90 mass% / 10 mass%, mass average molecular weight 70,000), 0.5 parts by mass of epoxidized soybean oil was added and mixed in the same manner. The obtained mixture was stretched and wound up in the same manner as in Example 1 to prepare a flat long double-ply film original fabric having a thickness of 20 μm. Thereafter, it was peeled off to a single film using a slitter to form a 10 μm film. The obtained results are shown in Table 1.

[実施例3]
ポリエチレン(低密度ポリエチレン、密度0.9g/cm3、表1中では「PE」と表記)に炭酸カルシウム(平均粒径0.2μm)を40質量%添加して混合し、溶融押出機で筒状に押出してバブルを形成して巻き取り、厚み20μmのフィルムを作製した。得られた結果を表1に示す。
[Example 3]
40% by mass of calcium carbonate (average particle size 0.2 μm) is added to polyethylene (low density polyethylene, density 0.9 g / cm 3 , expressed as “PE” in Table 1) and mixed, and the mixture is mixed with a melt extruder. The film was extruded to form a bubble and wound up to prepare a film having a thickness of 20 μm. The obtained results are shown in Table 1.

[実施例4]
実施例1と同様の方法で得たフィルムにワセリン(イワキ製白色ワセリンノースホワイト)を、ホットメルト塗工機を用いて目付30g/cm2に塗布した。得られた結果を表1に示す。
[Example 4]
Vaseline (Iwaki white petrolatum north white) was applied to the film obtained in the same manner as in Example 1 with a basis weight of 30 g / cm 2 using a hot melt coater. The obtained results are shown in Table 1.

[実施例5]
実施例1と同様の方法で得たフィルムにプラスチベース(大正富山医薬品製プラスチベース)を、ホットメルト塗工機を用いて目付50g/cm2に塗布した。得られた結果を表1に示す。
[Example 5]
A plastic base (Plastic base manufactured by Taisho Toyama Pharmaceutical Co., Ltd.) was applied to the film obtained in the same manner as in Example 1 with a basis weight of 50 g / cm 2 using a hot melt coating machine. The obtained results are shown in Table 1.

[実施例6]
実施例1と同様の方法で得たフィルムにラノリン(クローダ製ラノリン)を、ホットメルト塗工機を用いて目付3g/cm2に塗布した。得られた結果を表1に示す。
[Example 6]
Lanolin (Crano Lanolin) was applied to a film obtained in the same manner as in Example 1 with a basis weight of 3 g / cm 2 using a hot melt coater. The obtained results are shown in Table 1.

[実施例7]
実施例1と同様の方法で得たフィルムにマクロゴール軟膏(司生堂製薬製マクロゴール軟膏)を、ホットメルト塗工機を用いて目付80g/cm2に塗布した。得られた結果を表1に示す。
[Example 7]
Macrogol ointment (Macrogol ointment manufactured by Shiseido Pharmaceutical Co., Ltd.) was applied to the film obtained in the same manner as in Example 1 at a basis weight of 80 g / cm 2 using a hot melt coater. The obtained results are shown in Table 1.

[実施例8]
実施例2と同様の方法で得たフィルムにワセリン(イワキ製白色ワセリンノースホワイト)を、ホットメルト塗工機を用いて目付30g/cm2に塗布した。得られた結果を表1に示す。
[Example 8]
Vaseline (Iwaki white petrolatum north white) was applied to the film obtained in the same manner as in Example 2 with a basis weight of 30 g / cm 2 using a hot melt coater. The obtained results are shown in Table 1.

[実施例9]
実施例3と同様の方法で得たフィルムにワセリン(イワキ製白色ワセリンノースホワイト)を、ホットメルト塗工機を用いて目付30g/cm2に塗布した。得られた結果を表1に示す。
[Example 9]
Vaseline (Iwaki white petrolatum north white) was applied to the film obtained in the same manner as in Example 3 with a basis weight of 30 g / cm 2 using a hot melt coater. The obtained results are shown in Table 1.

[比較例1]
ポリエチレン(直鎖状低密度ポリエチレン、密度0.9g/cm3)を、溶融押出機で筒状に押出してバブルを形成して巻き取り、厚み10μmのフィルムを作製した。得られた結果を表1に示す。
[Comparative Example 1]
Polyethylene (linear low density polyethylene, density 0.9 g / cm 3 ) was extruded into a cylindrical shape with a melt extruder to form bubbles and wound up to produce a film having a thickness of 10 μm. The obtained results are shown in Table 1.

[比較例2]
ポリテトラフルオロエチレン(表1中では「PTFE」と表記、PTFEファインパウダー)をペースト押出して圧延、焼成し、厚み50μmのフィルムを得た。
[Comparative Example 2]
Polytetrafluoroethylene (indicated as “PTFE” in Table 1, PTFE fine powder) was paste extruded, rolled and fired to obtain a film having a thickness of 50 μm.

[比較例3]
実施例1と同様の方法で厚み3μmのフィルムを得た。得られた結果を表1に示す。
[Comparative Example 3]
A film having a thickness of 3 μm was obtained in the same manner as in Example 1. The obtained results are shown in Table 1.

[比較例4]
実施例1と同様の方法で厚み70μmのフィルムを得た。得られた結果を表1に示す。
[Comparative Example 4]
A film having a thickness of 70 μm was obtained in the same manner as in Example 1. The obtained results are shown in Table 1.

[比較例5]
6ナイロン(表1中では「Ny」と表記)を溶融押出機で押出し、2軸延伸して厚み25μmのフィルムを得た。得られた結果を表1に示す。
[Comparative Example 5]
6 nylon (indicated as “Ny” in Table 1) was extruded with a melt extruder and biaxially stretched to obtain a film having a thickness of 25 μm. The obtained results are shown in Table 1.

[比較例6]
インフレーションは行わない以外は実施例1と同様にしてフィルムを採取した。得られた結果を表1に示す。
[Comparative Example 6]
A film was collected in the same manner as in Example 1 except that no inflation was performed. The obtained results are shown in Table 1.

Figure 2015113330
Figure 2015113330

本発明は、皮膚へ貼り付けた際に肌へ沿ってなじむ肌沿い性に優れるスキンケアフィルムを提供できるものであり、さらには軟膏剤が移行せずに機械強度を維持するスキンケアフィルムを提供できる。特に皮膚の肌沿い性について厳しい水準の性能が要求される用途において有用である。   INDUSTRIAL APPLICABILITY The present invention can provide a skin care film excellent in along-skin properties that conforms to the skin when applied to the skin, and further can provide a skin care film that maintains mechanical strength without the ointment shifting. In particular, it is useful in applications that require a strict level of performance in terms of the along-skin property of the skin.

Claims (6)

密度1.3〜1.9g/cm3、厚み5〜50μm、引張弾性率200〜600MPa及び引張伸び60〜150%を満たすフィルムを有する、スキンケアフィルム。 A skin care film having a film satisfying a density of 1.3 to 1.9 g / cm 3 , a thickness of 5 to 50 μm, a tensile elastic modulus of 200 to 600 MPa, and a tensile elongation of 60 to 150%. 前記フィルムの表面に接する軟膏剤をさらに有する、請求項1に記載のスキンケアフィルム。   The skin care film according to claim 1, further comprising an ointment in contact with the surface of the film. 前記フィルムの20℃におけるZismanプロットにより求めた臨界表面張力が35〜50mN/mである、請求項1又は2に記載のスキンケアフィルム。   The skin care film of Claim 1 or 2 whose critical surface tension calculated | required by the Zisman plot in 20 degreeC of the said film is 35-50 mN / m. 前記フィルムの主成分が塩化ビニリデン共重合体である、請求項1〜3のいずれか一項に記載のスキンケアフィルム。   The skin care film according to any one of claims 1 to 3, wherein a main component of the film is a vinylidene chloride copolymer. 前記フィルムが、質量平均分子量7万〜14万及び塩化ビニリデン単量体単位75〜96質量%を満たす塩化ビニリデン共重合体100質量部と、脂肪酸エステル類とエポキシ化化合物との混合物1〜10質量部と、を含む、請求項1〜4のいずれか一項に記載のスキンケアフィルム。   100 to 10 parts by mass of a vinylidene chloride copolymer satisfying a mass average molecular weight of 70,000 to 140,000 and a vinylidene chloride monomer unit of 75 to 96% by mass, a mixture of a fatty acid ester and an epoxidized compound, 1 to 10 mass The skin care film as described in any one of Claims 1-4 containing a part. 前記軟膏剤がパラフィンワックス及び流動パラフィンの少なくとも一方を含む、請求項2〜5のいずれか一項に記載のスキンケアフィルム。   The skin care film according to any one of claims 2 to 5, wherein the ointment contains at least one of paraffin wax and liquid paraffin.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0198130U (en) * 1987-12-22 1989-06-30
JPH0268059A (en) * 1988-09-01 1990-03-07 Bertek Inc Skin coating applicator
JP2002539986A (en) * 1999-03-31 2002-11-26 ザ ダウ ケミカル カンパニー Method for producing thermoplastic film by inflation method and film produced by the method
WO2007018204A1 (en) * 2005-08-10 2007-02-15 Asahi Kasei Chemicals Corporation Polyvinylidene chloride resin wrapping film and process for producing the same
JP2014015590A (en) * 2012-07-11 2014-01-30 Asahi Kasei Chemicals Corp Vinylidene chloride resin wrap film
WO2014054414A1 (en) * 2012-10-01 2014-04-10 株式会社クレハ Vinylidene chloride-based copolymer resin composition and wrap film

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0198130U (en) * 1987-12-22 1989-06-30
JPH0268059A (en) * 1988-09-01 1990-03-07 Bertek Inc Skin coating applicator
JP2002539986A (en) * 1999-03-31 2002-11-26 ザ ダウ ケミカル カンパニー Method for producing thermoplastic film by inflation method and film produced by the method
WO2007018204A1 (en) * 2005-08-10 2007-02-15 Asahi Kasei Chemicals Corporation Polyvinylidene chloride resin wrapping film and process for producing the same
JP2014015590A (en) * 2012-07-11 2014-01-30 Asahi Kasei Chemicals Corp Vinylidene chloride resin wrap film
WO2014054414A1 (en) * 2012-10-01 2014-04-10 株式会社クレハ Vinylidene chloride-based copolymer resin composition and wrap film

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