JP3872702B2 - Adhesive composition and use thereof - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、コラーゲン加水分解物を主成分とする接着剤組成物およびその用途に関する。
【０００２】
【従来の技術】
コラーゲン加水分解物（ゼラチン・にかわ等）を主成分とした接着剤組成物は、その取り扱いの容易さや優れた初期接着性から、例えば製本背糊用接着剤として汎用されている。また、コラーゲン加水分解物を主成分とした接着剤組成物は、近年、用途が広がりつつある水溶性粘着剤としても、従来のアクリル系ポリマーをベースとした水溶性粘着剤にはない生分解性を有する点で望ましい材料として利用され始めている。
ところが、コラーゲン加水分解物の皮膜は、平衡水分状態では非常に堅く脆いため、例えば製本背糊用接着剤として用いた場合、本を開いたときに“割れ”やそれに伴う“バリ音”が発生するといった問題を生じる。皮膜を柔軟にして、この問題を解決するため、製本背糊用接着剤として用いる場合には通常、グリセリン等の多価アルコールや蔗糖等の糖類が配合されているが、塗付直後には比較的柔軟な皮膜を形成するものの、経時的に柔軟性を失い、長期間経過後にはやはり“割れ”や“バリ音”が生じるという問題が起こっていた。
【０００３】
他方、コラーゲン加水分解物を水溶性粘着剤として利用する場合、水分を吸収することによって粘着性を発現する、いわゆる水賦活型粘着剤として用いられるのであるが、平衡水分状態では粘着力が低く、しかも経時的に柔軟性を損なうため、その用途は限定されるものであった。
例えば、皮膚に貼り付けることにより、皮膚に適度な緊張感と潤いを与えるとともに皮膚表面の汚れを除去するといった化粧効果を発揮するシート状パック材として、コラーゲン加水分解物／保水剤／ゼリー化防止剤からなる水溶性粘着配合物を不織布等の支持体に塗付したものが開発されている。このようなシート状パック材においては、適度な粘着性を発揮させるために、保水剤やゼリー化防止剤を多量に配合する必要があるが、保水剤やゼリー化防止剤を多量に配合すると、粘着剤層の流動やダレが起こりやすく、保型性に劣る傾向があり、特に、夏場など商品を高温環境下で保存や使用した場合には、保型性の悪化が顕著であった。
【０００４】
【発明が解決しようとする課題】
そこで、本発明の課題は、良好な柔軟性を長期にわたり維持することができ、かつ、平衡水分状態においても優れた粘着性を発揮しうる接着剤組成物を提供することを目的とする。さらに、該接着剤組成物を用いて、長期間にわたり“割れ”や“バリ音”が生じることのない製本背糊用接着剤、平衡水分状態においても優れた粘着性を発揮する水溶性粘着剤、および粘着性と保型性とを兼ね備えたシート状パック材を提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明者らはこれらの問題点を解決すべく鋭意検討を行った結果、コラーゲン加水分解物に乳酸ナトリウムを配合することにより、前記課題を解決することができることを見出し、本発明を完成させたものである。
すなわち、本発明の接着剤組成物は、コラーゲン加水分解物を主成分とする接着剤組成物であって、保水剤として少なくとも乳酸ナトリウムを含有してなる。
本発明の製本背糊用接着剤は、本発明の接着剤組成物からなり、前記乳酸ナトリウムの含有量がコラーゲン加水分解物１００重量部に対して５〜４０重量部である。
【０００６】
本発明の水溶性粘着剤は、本発明の記載の接着剤組成物からなり、前記乳酸ナトリウムの含有量がコラーゲン加水分解物１００重量部に対して３０〜２００重量部である。
本発明のシート状パック材は、本発明の接着剤組成物からなり、前記乳酸ナトリウムの含有量がコラーゲン加水分解物１００重量部に対して３５〜２００重量部である水溶性粘着配合物の層を少なくとも含む。
【０００７】
【発明の実施の形態】
本発明の接着剤組成物は、コラーゲン加水分解物を主成分とする。前記コラーゲン加水分解物は、コラーゲンを加水分解することにより得られる物質であれば、特に制限されるものではなく、例えば、ニカワ、ゼラチン等が挙げられる。このようなコラーゲン加水分解物は、優れた初期接着性を発揮することができるので、高速作業性が必要とされる製本用途に適している。また、このようなコラーゲン加水分解物は、水溶性を有しているので、水溶性粘着剤のベース原料としても適しており、さらに、生体親和性や保水性にも優れるので、例えば、皮膚に潤いを与える、いわゆる化粧効果を目的としたシート状パック材等の各種用途に適用することができる。なお、コラーゲン加水分解物は、１種のみを用いてもよく、２種以上を併用してもよい。
【０００８】
本発明の接着剤組成物中、コラーゲン加水分解物の占める割合は、用途に応じて適宜設定すればよく、特に制限はない。具体的には、用途に応じた最適な粘度になるように、組成物中のコラーゲン加水分解物の割合を調整すればよい。
本発明の接着剤組成物は、保水剤として少なくとも乳酸ナトリウムを含有してなることが重要である。乳酸ナトリウムは、その優れた保水能力で水を保持することによって、コラーゲン加水分解物を可塑化すると同時に、粘着性を発揮させることができる。また、水素結合破壊剤としても作用するため、コラーゲン加水分解物を柔軟にする効果があり、しかもその効果を長期間持続させることができる。
【０００９】
本発明の接着剤組成物中、乳酸ナトリウムの占める割合は、用途に応じて適宜設定すればよく、特に制限はないが、例えば、製本背糊用接着剤とする場合には、コラーゲン加水分解物１００重量部に対して５〜４０重量部、好ましくは１０〜２５重量部とするのがよく、水溶性粘着剤とする場合には、コラーゲン加水分解物１００重量部に対して３０〜２００重量部、好ましくは６０〜１５０重量部とするのがよく、シート状パック材を構成する水溶性粘着配合物とする場合には、コラーゲン加水分解物１００重量部に対して３５〜２００重量部、好ましくは８０〜１５０重量部とするのがよい。
【００１０】
本発明の接着剤組成物は、必要に応じて、さらに、前記乳酸ナトリウム以外の保水剤を含有していてもよい。例えば、水溶性粘着剤やシート状ハップ材を構成する水溶性粘着配合物とする場合など前記乳酸ナトリウムの含有量が多いと、場合によってはコラーゲン加水分解物が沈殿してしまうことがあるが、乳酸ナトリウム以外の保水剤を共存させることにより、該乳酸ナトリウム以外の保水剤が相溶化剤的な効果を発揮し、コラーゲン加水分解物の沈殿を防止することができる。乳酸ナトリウム以外の保水剤としては、例えば、ソルビトール、グルコース、ショ糖、砂糖、マルトース等の糖類；グリセリン、ポリグリセリン、エチレングリコール、ポリエチレングリコール、プロピレングリコール、ポリプロピレングリコール等の多価アルコール類；ピロリドンカルボン酸ソーダ等の湿潤剤；等が挙げられる。なお、これら保水剤は、１種のみを用いてもよく、２種以上を併用してもよい。また、本発明の接着剤組成物中、乳酸ナトリウム以外の保水剤の占める割合は、用途に応じて適宜設定すればよい。
【００１１】
本発明の接着剤組成物は、さらに、ゼリー化防止剤を含有していてもよい。ゼリー化防止剤は、コラーゲン加水分解物の水素結合を阻害して、そのゼリー化を抑制し、コラーゲン加水分解物に柔軟性や粘着性を付与する効果を発揮する。ゼリー化防止剤としては、例えば、尿素、酢酸、クエン酸、塩化カルシウム、ロダン塩（例えば、ロダンアンモン等）等が挙げられる。特に、化粧用シート状パック剤など皮膚刺激性が問題となる用途においては、尿素が好ましい。なお、これらゼリー化防止剤は、１種のみを用いてもよく、２種以上を併用してもよい。また、本発明の接着剤組成物中、ゼリー化防止剤の占める割合は、用途に応じて適宜設定すればよい。
【００１２】
本発明の接着剤組成物は、さらに、架橋剤を含有していてもよい。架橋剤を含有させることにより、コラーゲン加水分解物を高分子量化させて三次元架橋構造を構成し、これによってコラーゲン加水分解物が高温付近で融解するのを防止し、保型性を高める効果を発揮させることができる。また、コラーゲン加水分解物を高分子量化することによって、粘着性の温度依存性を低減することができる。架橋剤としては、例えば、ホルムアルデヒドやグリオキザール（例えば、グルタルアルデヒド等）やジアルデヒド澱粉等のアルデヒド類、エポキシ類、ケトン類、キノン類等の有機化合物；アルミニウム、亜鉛、ジルコニウム、鉄、クロム等の多価金属イオンおよびこれらの金属塩（例えば、炭酸ジルコニウムアンモニウム、硫酸カリウムアルミニウム等）；等が挙げられる。なお、これら架橋剤は、１種のみを用いてもよく、２種以上を併用してもよい。また、本発明の接着剤組成物中、架橋剤の占める割合は、用途に応じて適宜設定すればよい。
【００１３】
本発明の接着剤組成物は、必要に応じてさらに、他の添加剤を含有していてもよい。他の添加剤としては、例えば、硫酸マグネシウム等の無機塩類等が挙げられる。なお、他の添加剤は、１種のみを用いてもよく、２種以上を併用してもよい。また、本発明の接着剤組成物中、他の添加剤の占める割合は、用途に応じて適宜設定すればよい。
本発明の接着剤組成物は、例えば、各種製本用接着剤、衛生材料（紙おむつ、生理用ナプキン、パンティーライナー等）、絆創膏、パップ剤、便座固定シート、メディカル用テープ材等の各種用途に有用であるが、とりわけ、製本背糊用接着剤、水溶性粘着剤、シート状パック材として好適である。
【００１４】
本発明の製本背糊用接着剤は、前記本発明の接着剤組成物からなり、前記乳酸ナトリウムの含有量がコラーゲン加水分解物１００重量部に対して５〜４０重量部である。本発明の製本背糊用接着剤を構成する接着剤組成物における乳酸ナトリウムの含有量が、コラーゲン加水分解物１００重量部に対して５重量部未満であると、十分な皮膜の柔軟性が得られないこととなり、一方、４０重量部を超えると、皮膜の凝集力が低下し、初期接着力が不足したり、皮膜の耐熱性が損なわれることなる。
本発明の製本背糊用接着剤を構成する接着剤組成物には、前記乳酸ナトリウム以外の保水剤、前記ゼリー化防止剤、無機塩類等を、必要に応じて配合することが好ましい。
【００１５】
本発明の製本背糊用接着剤を構成する接着剤組成物の好ましい形態は、例えば、コラーゲン加水分解物１００重量部と、保水剤（乳酸ナトリウム以外の保水剤をも含めて）５〜５０重量部と、ゼリー化防止剤１〜１０重量部とからなる組成物である。
本発明の製本背糊用接着剤は、長期にわたり優れた柔軟性を発揮することができるので、これを用いて製本を行うと、本背部の“割れ”や“バリ音”を生じない、見開き性に優れた本を得ることができる。また、本発明の製本背糊用接着剤は、優れた初期接着性を有するので、製本時の高速作業性に優れる。さらに、本発明の製本背糊用接着剤は、水溶性であるため古紙回収時のリサイクル適性に優れると同時に、生分解性を有するので、環境にも優しい。
【００１６】
本発明の水溶性粘着剤は、前記本発明の接着剤組成物からなり、前記乳酸ナトリウムの含有量がコラーゲン加水分解物１００重量部に対して３０〜２００重量部である。本発明の水溶性粘着剤を構成する接着剤組成物における乳酸ナトリウムの含有量が、コラーゲン加水分解物１００重量部に対して３０重量部未満であると、粘着力が不足することとなり、一方、２００重量部を超えると、粘着性が極度に高くなってベタベタしたものとなり、離型フィルム等との剥離時に凝集破壊し、いわゆる“糊移り”を起こすものとなる。
本発明の水溶性粘着剤を構成する接着剤組成物には、前記乳酸ナトリウム以外の保水剤、前記ゼリー化防止剤、前記架橋剤、無機塩類等を、必要に応じて配合することが好ましい。
【００１７】
本発明の水溶性粘着剤を構成する接着剤組成物の好ましい形態は、例えば、コラーゲン加水分解物１００重量部と、保水剤（乳酸ナトリウム以外の保水剤をも含めて）８０〜１９０重量部と、ゼリー化防止剤５〜１５重量部と、架橋剤０．１〜２重量部とからなる組成物である。
本発明の水溶性粘着剤は、優れた粘着性を発揮することができる。また、本発明の水溶性粘着剤は、水溶性があるので、リサイクル適性に優れると同時に、生分解性をも有するので、廃棄が容易で環境にも優しい。さらに、本発明の水溶性粘着剤は、生体親和性に優れ、医療用途などの人体に対する安全性が重視される用途にも好適である。
【００１８】
本発明のシート状パック材は、前記本発明の接着剤組成物からなり、前記乳酸ナトリウムの含有量がコラーゲン加水分解物１００重量部に対して３５〜２００重量部である水溶性粘着配合物の層を少なくとも含む。このように、本発明のシート状パック材は、少量で優れた保水性を発揮する乳酸ナトリウムを必須とすることから、従来の保水剤を用いた場合よりも少ない量の保水剤（乳酸ナトリウム以外の保水剤をも含めて）で優れた粘着性を発現させることができるので、保型性を損なうことがない。本発明のシート状パック材を構成する接着剤組成物（水溶性粘着配合物）における乳酸ナトリウムの含有量が、コラーゲン加水分解物１００重量部に対して３５重量部未満であると、粘着力が不足して皮膚への密着感が不足することとなり、一方、２００重量部を超えると、粘着性が極度に高くなってベタベタしたものとなり、離型フィルム等との剥離時に凝集破壊し、いわゆる“糊移り”を起こすものとなる。
【００１９】
本発明のシート状パック材を構成する接着剤組成物は、前記架橋剤を含有していることが好ましい。架橋剤によりコラーゲン加水分解物を高分子量化することによって、高温環境下であっても充分に保型性を向上させることができる。架橋の度合いは、体温付近（約４０℃）では溶融せず、６０〜７０℃程度で溶融する程度とするのが好ましい。
本発明のシート状パック材を構成する接着剤組成物は、前記コラーゲン加水分解物としてゼラチンを含有することが好ましい。また、本発明のシート状パック材を構成する接着剤組成物には、前記乳酸ナトリウム以外の保水剤、前記ゼリー化防止剤、防腐剤等を、要求される粘着特性に応じて配合することが好ましい。
【００２０】
本発明のシート状パック材を構成する接着剤組成物の好ましい形態は、例えば、コラーゲン加水分解物１００重量部と、保水剤（乳酸ナトリウム以外の保水剤をも含めて）８０〜１５０重量部と、ゼリー化防止剤５〜１５重量部と、架橋剤０．１〜２重量部とからなる組成物である。
本発明のシート状パック材は、前記の接着剤組成物からなる水溶性粘着配合物の層を少なくとも含むものであり、例えば、該水溶性粘着配合物を基材シート表面に積層形成したものでもよいし、あるいは、該水溶性粘着配合物自体をシート状に形成したものでもよい。
【００２１】
水溶性粘着配合物を基材シート表面に積層形成してなるシート状パック材は、基材シートの表面に前記水溶性粘着配合物を従来公知の方法で塗布することにより得ることができる。基材シートとしては、特に限定されないが、皮膚表面に柔軟に密着させるためには、例えば、厚み０．０１〜２ｍｍ程度の薄く柔軟な多孔性高分子フィルム、不織布、綿布、紙等が好ましい。また、粘着剤で形成された面を離型フィルム等で保護しておき、使用時に該フィルムを剥離するようにしてもよい。
一方、水溶性粘着配合物自体をシート状に形成してなるシート状パック材は、例えば、離型フィルム等の表面に、ドクターブレード、ロールコーター、ナイフコーター等の方法で前記水溶性粘着配合物を塗布することにより得ることができる。なお、離型フィルムは、使用時に剥離すればよい。
【００２２】
本発明のシート状パック材は、保存中の汚染や水分の蒸発等を防止するために、使用時までは密封して保存することが望ましい。
本発明のシート状パック材は、皮膚に対する適度な粘着性と、優れた保型性とを兼ね備えると同時に、皮膚に対する安全性にも優れるので、例えば、皮膚表面の汚れを除去するとともに皮膚に適度な水分を保持させるといった、いわゆる化粧効果を目的とする化粧用途や医療用途等に好適である。すなわち本発明にかかるシート状パック材はいわゆる「パップ材」を含む概念である。
なお、本発明にかかる接着材組成物はそれ自体が上記製本背糊用接着剤、水溶性粘着剤、水溶性粘着配合物層のごとき最終物であっても良いが、これらの最終物となる前の原料（中間体）であっても良い。
【００２３】
【実施例】
以下、実施例および比較例により本発明をさらに具体的に説明するが、本発明はこれらにより何ら限定されるものではない。なお、以下、特にことわりのない限り、「部」は「重量部」を、「％」は「重量％」を示すものとする。
＜製本背糊用接着剤＞
（実施例１−１）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水９０部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに乳酸ナトリウム５０％水溶液１０部を加えて撹拌混合し、本発明の接着剤組成物からなる本発明の製本背糊用接着剤を得た。
【００２４】
（実施例１−２）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水９０部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに乳酸ナトリウム５０％水溶液２０部を加えて撹拌混合し、本発明の接着剤組成物からなる本発明の製本背糊用接着剤を得た。
（実施例１−３）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水７５部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに乳酸ナトリウム５０％水溶液５０部を加えて撹拌混合し、本発明の接着剤組成物からなる本発明の製本背糊用接着剤を得た。
【００２５】
（実施例１−４）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水７５部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに乳酸ナトリウム５０％水溶液８０部を加えて撹拌混合し、本発明の接着剤組成物からなる本発明の製本背糊用接着剤を得た。
（実施例１−５）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水９０部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに乳酸ナトリウム５０％水溶液２０部および尿素５部を加えて撹拌混合し、本発明の接着剤組成物からなる本発明の製本背糊用接着剤を得た。
【００２６】
（比較例１−１）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水１００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに乳酸ナトリウム５０％水溶液４部を加えて撹拌混合し、本発明の接着剤組成物からなるが、乳酸ナトリウムの含有量が過少である、比較用の製本背糊用接着剤を得た。
（比較例１−２）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水７５部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに乳酸ナトリウム５０％水溶液１３２部を加えて撹拌混合し、本発明の接着剤組成物からなるが、乳酸ナトリウムの含有量が過多である、比較用の製本背糊用接着剤を得た。
【００２７】
（比較例１−３）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水１００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これにショ糖２５部を加えて撹拌混合し、乳酸ナトリウムを含まない、比較用の製本背糊用接着剤を得た。
（比較例１−４）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水１００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これにグリセリン２５部を加えて撹拌混合し、乳酸ナトリウムを含まない、比較用の製本背糊用接着剤を得た。
【００２８】
（比較例１−５）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水１００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させ、さらに撹拌混合して、乳酸ナトリウムを含まない、比較用の製本背糊用接着剤を得た。
以上で得られた製本背糊用接着剤について、次のようにして皮膜柔軟性を評価した。すなわち、得られた接着剤を１００μｍ・ｗｅｔでＰＥＴフィルム上に塗工して試験片を作製し、該試験片を２３℃６５％ＲＨの環境条件で放置した。そして、２４時間後ならびに３０日後の試験片を手で折り曲げたときの折り曲げ易さにより下記の判定基準で柔軟性を評価した。該評価でＳＳ〜Ｍであると、長期間にわたり“割れ”や“バリ音”が生じることがない。結果を表１に示す。
ＳＳ：非常に柔らかく、極めて容易に折り曲げ可能
Ｓ ：柔らかく、容易に折り曲げ可能
Ｍ ：やや柔らかく、折り曲げ可能
Ｈ ：柔らかさに欠け、折り曲げにくいが、割れない
ＨＨ：硬く、折り曲げると簡単に割れる
【００２９】
【表１】
＜水溶性粘着剤＞
（実施例２−１）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水３００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに炭酸ジルコニウムアンモニウム２０％水溶液３部を加え、６０℃で３０分間反応させて、ゼラチンを架橋した。得られた架橋ゼラチン水溶液に、乳酸ナトリウム５０％水溶液６０部、グリセリン５０部および尿素１５部を加えて撹拌混合し、本発明の接着剤組成物からなる本発明の水溶性粘着剤を得た。
【００３１】
（実施例２−２）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水３０部と乳酸ナトリウム５０％水溶液２００部とを加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させ、さらに撹拌混合して、本発明の接着剤組成物からなる本発明の水溶性粘着剤を得た。
（実施例２−３）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水１５部と乳酸ナトリウム５０％水溶液３００部とを加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これにグリセリン４０部を加えて撹拌混合し、本発明の接着剤組成物からなる本発明の水溶性粘着剤を得た。
【００３２】
（実施例２−４）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に乳酸ナトリウム５０％水溶液４００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これにグリセリン４０部を加えて撹拌混合し、本発明の接着剤組成物からなる本発明の水溶性粘着剤を得た。
（実施例２−５）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水８０部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに乳酸ナトリウム５０％水溶液１２０部および尿素１５部を加えて撹拌混合し、本発明の接着剤組成物からなる本発明の水溶性粘着剤を得た。
【００３３】
（実施例２−６）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水３００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに硫酸カリウムアルミニウム（１２水和物）１０％水溶液１８部を加え、６０℃で３０分間反応させて、ゼラチンを架橋した。得られた架橋ゼラチン水溶液に、乳酸ナトリウム５０％水溶液６０部、グリセリン５０部、およびロダンアンモン５部を加えて撹拌混合し、本発明の接着剤組成物からなる本発明の水溶性粘着剤を得た。
【００３４】
（実施例２−７）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水３００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これにグルタルアルデヒド１０％水溶液３部を加え、６０℃で３０分間反応させて、ゼラチンを架橋した。得られた架橋ゼラチン水溶液に、乳酸ナトリウム５０％水溶液６０部、グリセリン５０部、およびロダンアンモン５部を加えて撹拌混合し、本発明の接着剤組成物からなる本発明の水溶性粘着剤を得た。
【００３５】
（比較例２−１）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水８０部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに乳酸ナトリウム５０％水溶液４０部を加えて撹拌混合し、本発明の接着剤組成物からなるが、乳酸ナトリウムの含有量が過少である、比較用の水溶性粘着剤を得た。
（比較例２−２）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に乳酸ナトリウム５０％水溶液５００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これにグリセリン１００部を加えて撹拌混合し、本発明の接着剤組成物からなるが、乳酸ナトリウムの含有量が過多である、比較用の水溶性粘着剤を得た。
【００３６】
（比較例２−３）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水１００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これにショ糖１５０部を加えて撹拌混合し、乳酸ナトリウムを含まない、比較用の水溶性粘着剤を得た。
（比較例２−４）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水１００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これにグリセリン１５０部を加えて撹拌混合し、乳酸ナトリウムを含まない、比較用の水溶性粘着剤を得た。
【００３７】
以上で得られた水溶性粘着剤について、次のようにして粘着性を評価した。すなわち、得られた粘着剤を１００μｍ・ｗｅｔでＰＥＴフィルム上に塗工して試験片を作製し、該試験片を２３℃６５％ＲＨの環境条件で放置した。そして、３０日後の試験片のピクマタックをピクマタックテスターを用いて測定することにより、平衡水分状態における粘着性を評価した。結果を表２に示す。
【００３８】
【表２】
＜シート状パック材＞
（実施例３−１）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水３００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに炭酸ジルコニウムアンモニウム２０％水溶液３部を加え、６０℃で３０分間反応させて、ゼラチンを架橋した。得られた架橋ゼラチン水溶液に、乳酸ナトリウム５０％水溶液７０部、グリセリン５０部および尿素１５部を加えて撹拌混合し、水溶性粘着配合物を得た。次に、該水溶性粘着配合物を、離型フィルム上に厚み１ｍｍになるように塗工し、本発明のシート状パック材を得た。
【００４０】
（実施例３−２）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水３００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに硫酸カリウムアルミニウム（１２水和物）１０％水溶液１８部を加え、６０℃で３０分間反応させて、ゼラチンを架橋した。得られた架橋ゼラチン水溶液に、乳酸ナトリウム５０％水溶液７０部、グリセリン５０部および尿素１５部を加えて撹拌混合し、水溶性粘着配合物を得た。次に、該水溶性粘着配合物を、離型フィルム上に厚み１ｍｍになるように塗工し、本発明のシート状パック材を得た。
【００４１】
（実施例３−３）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水１００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに乳酸ナトリウム５０％水溶液１６０部および尿素１５部を加えて撹拌混合し、水溶性粘着配合物を得た。次に、該水溶性粘着配合物を、離型フィルム上に厚み１ｍｍになるように塗工し、本発明のシート状パック材を得た。
（実施例３−４）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水１００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに乳酸ナトリウム５０％水溶液１６０部およびロダンアンモン５部を加えて撹拌混合し、水溶性粘着配合物を得た。次に、該水溶性粘着配合物を、離型フィルム上に厚み１ｍｍになるように塗工し、本発明のシート状パック材を得た。
【００４２】
（実施例３−５）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水３００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに炭酸ジルコニウムアンモニウム２０％水溶液３部を加え、６０℃で３０分間反応させて、ゼラチンを架橋した。得られた架橋ゼラチン水溶液に、乳酸ナトリウム５０％水溶液３００部を加えて撹拌混合し、水溶性粘着配合物を得た。次に、該水溶性粘着配合物を、離型フィルム上に厚み１ｍｍになるように塗工し、本発明のシート状パック材を得た。
【００４３】
（実施例３−６）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水３００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに炭酸ジルコニウムアンモニウム２０％水溶液３部を加え、６０℃で３０分間反応させて、ゼラチンを架橋した。得られた架橋ゼラチン水溶液に、乳酸ナトリウム５０％水溶液４００部およびグリセリン４０部を加えて撹拌混合し、水溶性粘着配合物を得た。次に、該水溶性粘着配合物を、離型フィルム上に厚み１ｍｍになるように塗工し、本発明のシート状パック材を得た。
【００４４】
（比較例３−１）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水３００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに炭酸ジルコニウムアンモニウム２０％水溶液３部を加え、６０℃で３０分間反応させて、ゼラチンを架橋した。得られた架橋ゼラチン水溶液に、乳酸ナトリウム５０％水溶液４０部および尿素１５部を加えて撹拌混合し、乳酸ナトリウムの含有量が過少である水溶性粘着配合物を得た。次に、該水溶性粘着配合物を、離型フィルム上に厚み１ｍｍになるように塗工し、比較用のシート状パック材を得た。
【００４５】
（比較例３−２）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に乳酸ナトリウム５０％水溶液５００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これにグリセリン４０部を加えて撹拌混合し、乳酸ナトリウムの含有量が過多である水溶性粘着配合物を得た。次に、該水溶性粘着配合物を、離型フィルム上に厚み１ｍｍになるように塗工し、比較用のシート状パック材を得た。
（比較例３−３）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水１００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これにグリセリン８０部および尿素１５部を加えて撹拌混合し、乳酸ナトリウムを含まない水溶性粘着配合物を得た。次に、該水溶性粘着配合物を、離型フィルム上に厚み１ｍｍになるように塗工し、比較用のシート状パック材を得た。
【００４６】
（比較例３−４）
ゼラチン（アルカリ処理ゼラチン：粘度３ｍＰａ・ｓ、JIS6503法によるゼリー強度１００Ｂｌｏｏｍ）１００部に水３００部を加えて室温にて３０分間膨潤させた後、６０℃に加温してゼラチンを溶解させた。これに炭酸ジルコニウムアンモニウム２０％水溶液３部を加え、６０℃で３０分間反応させて、ゼラチンを架橋した。得られた架橋ゼラチン水溶液に、グリセリン１５０部を加えて撹拌混合し、乳酸ナトリウムを含まない水溶性粘着配合物を得た。次に、該水溶性粘着配合物を、離型フィルム上に厚み１ｍｍになるように塗工し、比較用のシート状パック材を得た。
【００４７】
以上で得られたシート状パック材を実際に使用した時の使用感について、下記各項目毎に下記判定基準で被験者１０名によるモニター調査を行い、各項目毎に最も多い評価を得た判定をもって、その使用感を評価した。結果を表３に示す。
密着感（粘着性） ；○：良好、△：あまり良くない、×：悪い
緊張感 ；○：良好、△：あまり良くない、×：悪い
湿潤感 ；○：良好、△：あまり良くない、×：悪い
パック材のダレ（保型性）；○：ダレがない、△：ややダレがある、×：ダレがある
【００４８】
【表３】
【発明の効果】
本発明の接着剤組成物は、良好な柔軟性を長期にわたり維持することができ、かつ、平衡水分状態においても優れた粘着性を発揮することができるので、これを用いて、例えば、長期間にわたり“割れ”や“バリ音”が生じることのない製本背糊用接着剤、平衡水分状態においても優れた粘着性を発揮する水溶性粘着剤、および粘着性と保型性とを兼ね備えたシート状パック材を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an adhesive composition mainly composed of a collagen hydrolyzate and use thereof.
[0002]
[Prior art]
Adhesive compositions mainly composed of collagen hydrolyzate (gelatin, glue, etc.) are widely used as, for example, an adhesive for bookbinding back glue because of their ease of handling and excellent initial adhesiveness. In addition, the adhesive composition based on collagen hydrolyzate is a biodegradable product not found in conventional water-soluble adhesives based on acrylic polymers, even as a water-soluble adhesive whose use is expanding in recent years. It has begun to be used as a desirable material in that it has
However, the collagen hydrolyzate film is very hard and brittle in the equilibrium moisture state. For example, when used as an adhesive for bookbinding back glue, when the book is opened, "cracking" and accompanying "burr noise" occur. Cause problems. In order to solve this problem by softening the film, polyhydric alcohols such as glycerin and sugars such as sucrose are usually blended when used as an adhesive for bookbinding back glue, but comparison is made immediately after application. However, there was a problem that the film lost its flexibility over time and “cracking” and “burr” occurred after a long period of time.
[0003]
On the other hand, when using a collagen hydrolyzate as a water-soluble adhesive, it is used as a so-called water-activated adhesive that expresses adhesiveness by absorbing moisture, but in an equilibrium moisture state, the adhesive strength is low, In addition, since its flexibility is lost over time, its use is limited.
For example, by applying it to the skin, the sheet hydrolyzate / water retention agent / prevention of jelly can be used as a sheet-like pack material that gives the skin an appropriate tension and moisturization and removes dirt on the skin surface. A product in which a water-soluble adhesive compound composed of an agent is applied to a support such as a nonwoven fabric has been developed. In such a sheet-shaped pack material, it is necessary to blend a large amount of a water retaining agent and an anti-jelly agent in order to exhibit appropriate tackiness, but when a large amount of a water retaining agent and an anti-jelly agent is blended, The pressure-sensitive adhesive layer tends to flow and sag, and tends to be inferior in shape retention. In particular, when products are stored or used in a high temperature environment such as in summer, the deterioration in shape retention is remarkable.
[0004]
[Problems to be solved by the invention]
Then, the subject of this invention aims at providing the adhesive composition which can maintain favorable softness | flexibility over a long period of time, and can exhibit the outstanding adhesiveness also in an equilibrium moisture state. Furthermore, using the adhesive composition, an adhesive for bookbinding back glue that does not cause "cracking" or "burr" over a long period of time, a water-soluble adhesive that exhibits excellent tackiness even in an equilibrium moisture state Another object of the present invention is to provide a sheet-like pack material having both adhesiveness and shape retention.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve these problems, the present inventors have found that the above-mentioned problems can be solved by adding sodium lactate to a collagen hydrolyzate, and the present invention has been completed. Is.
That is, the adhesive composition of the present invention is an adhesive composition mainly composed of a collagen hydrolyzate, and contains at least sodium lactate as a water retention agent.
The adhesive for bookbinding back paste of the present invention comprises the adhesive composition of the present invention, and the content of the sodium lactate is 5 to 40 parts by weight with respect to 100 parts by weight of the collagen hydrolyzate.
[0006]
The water-soluble pressure-sensitive adhesive of the present invention comprises the adhesive composition described in the present invention, and the content of the sodium lactate is 30 to 200 parts by weight with respect to 100 parts by weight of the collagen hydrolyzate.
The sheet-like pack material of the present invention is composed of the adhesive composition of the present invention, wherein the sodium lactate content is 35 to 200 parts by weight with respect to 100 parts by weight of the collagen hydrolyzate layer. At least.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The adhesive composition of the present invention contains a collagen hydrolyzate as a main component. The collagen hydrolyzate is not particularly limited as long as it is a substance obtained by hydrolyzing collagen, and examples thereof include glue and gelatin. Since such a collagen hydrolyzate can exhibit excellent initial adhesiveness, it is suitable for bookbinding applications that require high-speed workability. In addition, since such a collagen hydrolyzate is water-soluble, it is also suitable as a base material for a water-soluble adhesive, and also has excellent biocompatibility and water retention. It can be applied to various uses such as a sheet-like pack material for the purpose of giving a so-called cosmetic effect. In addition, a collagen hydrolyzate may use only 1 type and may use 2 or more types together.
[0008]
The proportion of the collagen hydrolyzate in the adhesive composition of the present invention may be appropriately set depending on the application, and is not particularly limited. Specifically, the ratio of the collagen hydrolyzate in the composition may be adjusted so as to obtain an optimum viscosity according to the application.
It is important that the adhesive composition of the present invention contains at least sodium lactate as a water retention agent. By maintaining water with its excellent water retention capacity, sodium lactate can plasticize the collagen hydrolyzate and exhibit adhesiveness. Moreover, since it acts also as a hydrogen bond breaking agent, there exists an effect which makes a collagen hydrolyzate soft, and also the effect can be maintained for a long period of time.
[0009]
In the adhesive composition of the present invention, the proportion of sodium lactate may be appropriately set depending on the application, and is not particularly limited. For example, when an adhesive for bookbinding back glue is used, a collagen hydrolyzate 5 to 40 parts by weight with respect to 100 parts by weight, preferably 10 to 25 parts by weight, and in the case of a water-soluble adhesive, 30 to 200 parts by weight with respect to 100 parts by weight of the collagen hydrolyzate Preferably, the amount is 60 to 150 parts by weight. When the water-soluble adhesive compound constituting the sheet-shaped pack material is used, it is 35 to 200 parts by weight, preferably 100 parts by weight of the collagen hydrolyzate. It is good to set it as 80-150 weight part.
[0010]
The adhesive composition of the present invention may further contain a water retention agent other than the sodium lactate as necessary. For example, when the content of the sodium lactate is high, such as when forming a water-soluble adhesive or a water-soluble adhesive composition constituting a sheet-shaped hap material, collagen hydrolyzate may precipitate in some cases, By allowing a water retention agent other than sodium lactate to coexist, the water retention agent other than sodium lactate exerts an effect as a compatibilizer and can prevent the precipitation of collagen hydrolyzate. Examples of water-retaining agents other than sodium lactate include saccharides such as sorbitol, glucose, sucrose, sugar, and maltose; polyhydric alcohols such as glycerin, polyglycerin, ethylene glycol, polyethylene glycol, propylene glycol, and polypropylene glycol; Wetting agents such as acid soda; In addition, these water retention agents may use only 1 type, and may use 2 or more types together. Moreover, what is necessary is just to set suitably the ratio for which water retention agents other than sodium lactate occupy in the adhesive composition of this invention according to a use.
[0011]
The adhesive composition of the present invention may further contain a jelly formation inhibitor. The jelly formation inhibitor inhibits hydrogen bonding of the collagen hydrolyzate, suppresses its jelly formation, and exhibits the effect of imparting flexibility and tackiness to the collagen hydrolyzate. Examples of the jelly formation inhibitor include urea, acetic acid, citric acid, calcium chloride, rhodan salts (for example, rhodanammon etc.) and the like. In particular, urea is preferable in applications where skin irritation is a problem, such as a cosmetic sheet pack. In addition, only 1 type may be used for these jelly formation inhibitors, and 2 or more types may be used together. Moreover, what is necessary is just to set suitably the ratio for which a jelly formation inhibitor accounts in the adhesive composition of this invention according to a use.
[0012]
The adhesive composition of the present invention may further contain a crosslinking agent. By containing a cross-linking agent, the collagen hydrolyzate is made to have a high molecular weight to form a three-dimensional cross-linked structure, thereby preventing the collagen hydrolyzate from melting near high temperatures and improving the shape retention. It can be demonstrated. Moreover, the temperature dependency of adhesiveness can be reduced by increasing the molecular weight of the collagen hydrolyzate. Examples of the crosslinking agent include aldehydes such as formaldehyde, glyoxal (eg, glutaraldehyde) and dialdehyde starch, organic compounds such as epoxies, ketones, and quinones; aluminum, zinc, zirconium, iron, chromium, and the like. Polyvalent metal ions and metal salts thereof (for example, zirconium ammonium carbonate, potassium aluminum sulfate, etc.); In addition, these crosslinking agents may use only 1 type and may use 2 or more types together. Moreover, what is necessary is just to set suitably the ratio for which a crosslinking agent accounts in the adhesive composition of this invention according to a use.
[0013]
The adhesive composition of the present invention may further contain other additives as necessary. Examples of other additives include inorganic salts such as magnesium sulfate. In addition, only 1 type may be used for another additive and it may use 2 or more types together. Moreover, what is necessary is just to set suitably the ratio for which another additive accounts in the adhesive composition of this invention according to a use.
The adhesive composition of the present invention is useful in various applications such as adhesives for bookbinding, hygiene materials (paper diapers, sanitary napkins, panty liners, etc.), adhesive bandages, poultices, toilet seat fixing sheets, medical tape materials, and the like. However, it is particularly suitable as an adhesive for bookbinding back glue, a water-soluble adhesive, and a sheet-like pack material.
[0014]
The adhesive for bookbinding back paste of the present invention comprises the adhesive composition of the present invention, and the content of the sodium lactate is 5 to 40 parts by weight with respect to 100 parts by weight of the collagen hydrolyzate. When the content of sodium lactate in the adhesive composition constituting the adhesive for binding bookbinding of the present invention is less than 5 parts by weight based on 100 parts by weight of the collagen hydrolyzate, sufficient film flexibility is obtained. On the other hand, when the amount exceeds 40 parts by weight, the cohesive strength of the film is lowered, the initial adhesive force is insufficient, and the heat resistance of the film is impaired.
In the adhesive composition constituting the adhesive for bookbinding back paste of the present invention, it is preferable to add a water retention agent other than the sodium lactate, the jelly inhibitor, inorganic salts, and the like as necessary.
[0015]
The preferable form of the adhesive composition constituting the binding adhesive for bookbinding of the present invention is, for example, 100 parts by weight of collagen hydrolyzate and 5 to 50 weights of water retention agent (including water retention agents other than sodium lactate). Part and a jelly-forming inhibitor 1 to 10 parts by weight.
The binding adhesive for bookbinding back glue of the present invention can exhibit excellent flexibility over a long period of time. When bookbinding is performed using this adhesive, there is no “cracking” or “burr” in the book back. A book with excellent properties can be obtained. Moreover, since the adhesive for bookbinding back paste of the present invention has excellent initial adhesiveness, it is excellent in high-speed workability during bookbinding. Furthermore, since the adhesive for bookbinding back paste of the present invention is water-soluble, it is excellent in recycling suitability at the time of waste paper collection and at the same time has biodegradability and is therefore environmentally friendly.
[0016]
The water-soluble pressure-sensitive adhesive of the present invention comprises the adhesive composition of the present invention, and the content of the sodium lactate is 30 to 200 parts by weight with respect to 100 parts by weight of the collagen hydrolyzate. When the content of sodium lactate in the adhesive composition constituting the water-soluble pressure-sensitive adhesive of the present invention is less than 30 parts by weight with respect to 100 parts by weight of the collagen hydrolyzate, the adhesive force will be insufficient, When the amount exceeds 200 parts by weight, the tackiness becomes extremely high and becomes sticky, and when it is peeled off from the release film or the like, the material breaks down and causes so-called “glue transfer”.
In the adhesive composition constituting the water-soluble pressure-sensitive adhesive of the present invention, a water retention agent other than the sodium lactate, the jelly formation inhibitor, the crosslinking agent, inorganic salts, and the like are preferably blended as necessary.
[0017]
The preferable form of the adhesive composition constituting the water-soluble pressure-sensitive adhesive of the present invention is, for example, 100 parts by weight of a collagen hydrolyzate, and 80 to 190 parts by weight of a water retention agent (including a water retention agent other than sodium lactate) , A composition comprising 5 to 15 parts by weight of an anti-jelly agent and 0.1 to 2 parts by weight of a crosslinking agent.
The water-soluble adhesive of the present invention can exhibit excellent adhesiveness. In addition, since the water-soluble pressure-sensitive adhesive of the present invention is water-soluble, it is excellent in recyclability and at the same time has biodegradability, so that it can be easily discarded and is environmentally friendly. Furthermore, the water-soluble pressure-sensitive adhesive of the present invention is excellent in biocompatibility, and is also suitable for uses such as medical use where safety for the human body is important.
[0018]
The sheet-like pack material of the present invention is composed of the adhesive composition of the present invention, wherein the content of the sodium lactate is 35 to 200 parts by weight with respect to 100 parts by weight of the collagen hydrolyzate. Including at least a layer. Thus, since the sheet-like pack material of the present invention requires sodium lactate that exhibits excellent water retention in a small amount, a smaller amount of water retention agent (other than sodium lactate other than sodium lactate) is used. (Including the water retaining agent) can exhibit excellent adhesiveness, and thus the shape retaining property is not impaired. When the content of sodium lactate in the adhesive composition (water-soluble adhesive compound) constituting the sheet-like pack material of the present invention is less than 35 parts by weight with respect to 100 parts by weight of the collagen hydrolyzate, the adhesive strength is When the amount exceeds 200 parts by weight, the adhesiveness becomes extremely high and becomes sticky, and cohesive failure occurs when peeling from a release film or the like. It will cause “glue transfer”.
[0019]
The adhesive composition constituting the sheet-shaped pack material of the present invention preferably contains the crosslinking agent. By increasing the molecular weight of the collagen hydrolyzate with a crosslinking agent, the shape retention can be sufficiently improved even in a high temperature environment. The degree of crosslinking is preferably such that it does not melt near body temperature (about 40 ° C.) but melts at about 60 to 70 ° C.
The adhesive composition constituting the sheet-shaped pack material of the present invention preferably contains gelatin as the collagen hydrolyzate. Further, the adhesive composition constituting the sheet-like pack material of the present invention may contain a water retention agent other than the sodium lactate, the anti-jelly agent, an antiseptic, and the like according to required adhesive properties. preferable.
[0020]
The preferable form of the adhesive composition constituting the sheet-like pack material of the present invention is, for example, 100 parts by weight of a collagen hydrolyzate, and 80 to 150 parts by weight of a water retention agent (including a water retention agent other than sodium lactate) , A composition comprising 5 to 15 parts by weight of an anti-jelly agent and 0.1 to 2 parts by weight of a crosslinking agent.
The sheet-like pack material of the present invention includes at least a layer of a water-soluble pressure-sensitive adhesive composition comprising the above-mentioned adhesive composition. For example, the water-soluble pressure-sensitive adhesive composition may be laminated on the surface of a base sheet. Alternatively, the water-soluble adhesive composition itself may be formed into a sheet shape.
[0021]
The sheet-like pack material formed by laminating and forming the water-soluble adhesive compound on the surface of the base sheet can be obtained by applying the water-soluble adhesive compound to the surface of the base sheet by a conventionally known method. Although it does not specifically limit as a base material sheet, In order to make it closely_contact | adhere to the skin surface flexibly, a thin flexible polymer film with a thickness of about 0.01-2 mm, a nonwoven fabric, cotton cloth, paper etc. are preferable, for example. Moreover, the surface formed with the adhesive may be protected with a release film or the like, and the film may be peeled off during use.
On the other hand, the sheet-like pack material formed by forming the water-soluble adhesive compound itself into a sheet is formed on the surface of a release film or the like by a method such as a doctor blade, a roll coater, or a knife coater. It can obtain by apply | coating. In addition, what is necessary is just to peel a release film at the time of use.
[0022]
The sheet-shaped pack material of the present invention is preferably sealed and stored until use in order to prevent contamination during storage and evaporation of moisture.
The sheet-shaped pack material of the present invention has both moderate adhesiveness to the skin and excellent shape retention, and at the same time, is excellent in safety against the skin. It is suitable for cosmetic use, medical use, etc. for the purpose of so-called cosmetic effects, such as retaining sufficient moisture. That is, the sheet-shaped pack material according to the present invention is a concept including a so-called “pap material”.
The adhesive composition according to the present invention may itself be a final product such as the above-mentioned binding back adhesive, water-soluble pressure-sensitive adhesive, and water-soluble pressure-sensitive adhesive compound layer, but these are final products. The previous raw material (intermediate) may be used.
[0023]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited at all by these. In the following, “part” means “part by weight” and “%” means “% by weight” unless otherwise specified.
<Adhesive for binding back paste>
(Example 1-1)
90 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this was added 10 parts of a 50% aqueous solution of sodium lactate, and the mixture was stirred and mixed to obtain an adhesive for bookbinding back paste of the present invention comprising the adhesive composition of the present invention.
[0024]
(Example 1-2)
90 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this was added 20 parts of a 50% aqueous solution of sodium lactate and mixed by stirring to obtain an adhesive for bookbinding back paste of the present invention comprising the adhesive composition of the present invention.
(Example 1-3)
75 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. 50 parts of 50% aqueous solution of sodium lactate was added to this, and mixed by stirring to obtain an adhesive for bookbinding back paste of the present invention comprising the adhesive composition of the present invention.
[0025]
(Example 1-4)
75 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this, 80 parts of 50% aqueous solution of sodium lactate was added and stirred and mixed to obtain the binding adhesive for bookbinding back glue of the present invention comprising the adhesive composition of the present invention.
(Example 1-5)
90 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this, 20 parts of a 50% aqueous solution of sodium lactate and 5 parts of urea were added and mixed with stirring to obtain an adhesive for bookbinding back glue of the present invention comprising the adhesive composition of the present invention.
[0026]
(Comparative Example 1-1)
100 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. 4 parts of 50% aqueous solution of sodium lactate was added to this and stirred and mixed to obtain a comparative binding adhesive for bookbinding back paste comprising the adhesive composition of the present invention, but containing a small amount of sodium lactate.
(Comparative Example 1-2)
75 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this, 132 parts of a 50% aqueous solution of sodium lactate was added and mixed by stirring to obtain a comparative binding adhesive for bookbinding back paste comprising the adhesive composition of the present invention, but containing an excessive amount of sodium lactate.
[0027]
(Comparative Example 1-3)
100 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this, 25 parts of sucrose was added and mixed by stirring to obtain a comparative binding adhesive for bookbinding back paste containing no sodium lactate.
(Comparative Example 1-4)
100 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this was added 25 parts of glycerin and mixed with stirring to obtain a comparative binding adhesive for bookbinding back paste containing no sodium lactate.
[0028]
(Comparative Example 1-5)
Add 100 parts of water to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swell for 30 minutes at room temperature, then warm to 60 ° C. to dissolve the gelatin, By stirring and mixing, a comparative adhesive for bookbinding back paste containing no sodium lactate was obtained.
The adhesiveness for bookbinding back paste obtained above was evaluated for film flexibility as follows. That is, the obtained adhesive was coated on a PET film at 100 μm · wet to prepare a test piece, and the test piece was left under an environmental condition of 23 ° C. and 65% RH. Then, the flexibility was evaluated according to the following criteria based on the ease of folding the test piece after 24 hours and 30 days by hand. When the evaluation is SS to M, “cracking” and “burr” do not occur over a long period of time. The results are shown in Table 1.
SS: Very soft and can be folded very easily
S: Soft and easy to bend
M: Slightly soft and bendable
H: Lack of softness, difficult to bend but not cracked
HH: Hard and easy to break when bent
[0029]
[Table 1]
<Water-soluble adhesive>
(Example 2-1)
300 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this was added 3 parts of a 20% aqueous solution of ammonium zirconium carbonate and reacted at 60 ° C. for 30 minutes to crosslink the gelatin. To the obtained crosslinked gelatin aqueous solution, 60 parts of a 50% aqueous solution of sodium lactate, 50 parts of glycerin and 15 parts of urea were stirred and mixed to obtain the water-soluble pressure-sensitive adhesive of the present invention comprising the adhesive composition of the present invention.
[0031]
(Example 2-2)
30 parts of water and 200 parts of a 50% aqueous solution of sodium lactate were added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen for 30 minutes at room temperature, and then heated to 60 ° C. The gelatin was dissolved by heating and further stirred and mixed to obtain the water-soluble pressure-sensitive adhesive of the present invention comprising the adhesive composition of the present invention.
(Example 2-3)
15 parts of water and 300 parts of 50% aqueous solution of sodium lactate are added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swelled at room temperature for 30 minutes, and then heated to 60 ° C. The gelatin was dissolved by warming. 40 parts of glycerin was added to this and mixed by stirring to obtain the water-soluble pressure-sensitive adhesive of the present invention comprising the adhesive composition of the present invention.
[0032]
(Example 2-4)
400 parts of 50% aqueous solution of sodium lactate is added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swelled at room temperature for 30 minutes, and then heated to 60 ° C. for gelatin. Dissolved. 40 parts of glycerin was added to this and mixed by stirring to obtain the water-soluble pressure-sensitive adhesive of the present invention comprising the adhesive composition of the present invention.
(Example 2-5)
80 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen for 30 minutes at room temperature, and then heated to 60 ° C. to dissolve the gelatin. To this, 120 parts of a 50% aqueous solution of sodium lactate and 15 parts of urea were added and mixed by stirring to obtain a water-soluble pressure-sensitive adhesive of the present invention comprising the adhesive composition of the present invention.
[0033]
(Example 2-6)
300 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this, 18 parts of a 10% aqueous solution of potassium aluminum sulfate (12 hydrate) was added and reacted at 60 ° C. for 30 minutes to crosslink the gelatin. To the obtained crosslinked gelatin aqueous solution, 60 parts of a 50% aqueous solution of sodium lactate, 50 parts of glycerin and 5 parts of rhodanammon are stirred and mixed to obtain the water-soluble pressure-sensitive adhesive of the present invention comprising the adhesive composition of the present invention. It was.
[0034]
(Example 2-7)
300 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this, 3 parts of a 10% aqueous solution of glutaraldehyde was added and reacted at 60 ° C. for 30 minutes to crosslink the gelatin. To the obtained crosslinked gelatin aqueous solution, 60 parts of a 50% aqueous solution of sodium lactate, 50 parts of glycerin and 5 parts of rhodanammon are stirred and mixed to obtain the water-soluble pressure-sensitive adhesive of the present invention comprising the adhesive composition of the present invention. It was.
[0035]
(Comparative Example 2-1)
80 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen for 30 minutes at room temperature, and then heated to 60 ° C. to dissolve the gelatin. 40 parts of 50% aqueous solution of sodium lactate was added thereto and mixed by stirring to obtain a comparative water-soluble pressure-sensitive adhesive consisting of the adhesive composition of the present invention, but containing too little sodium lactate.
(Comparative Example 2-2)
Add 500 parts of 50% aqueous solution of sodium lactate to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method), swell for 30 minutes at room temperature, then warm to 60 ° C to gelatin Dissolved. To this, 100 parts of glycerin was added and stirred and mixed to obtain a comparative water-soluble pressure-sensitive adhesive comprising the adhesive composition of the present invention, but containing an excessive amount of sodium lactate.
[0036]
(Comparative Example 2-3)
100 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. 150 parts of sucrose was added thereto and mixed by stirring to obtain a comparative water-soluble pressure-sensitive adhesive not containing sodium lactate.
(Comparative Example 2-4)
100 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this, 150 parts of glycerin was added and mixed with stirring to obtain a comparative water-soluble pressure-sensitive adhesive not containing sodium lactate.
[0037]
About the water-soluble adhesive obtained above, adhesiveness was evaluated as follows. That is, the obtained pressure-sensitive adhesive was coated on a PET film at 100 μm · wet to produce a test piece, and the test piece was left under an environmental condition of 23 ° C. and 65% RH. And the adhesiveness in an equilibrium moisture state was evaluated by measuring the Pikuma tack of the test piece after 30 days using a Pikuma tack tester. The results are shown in Table 2.
[0038]
[Table 2]
<Sheet pack material>
(Example 3-1)
300 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this was added 3 parts of a 20% aqueous solution of ammonium zirconium carbonate and reacted at 60 ° C. for 30 minutes to crosslink the gelatin. To the obtained crosslinked gelatin aqueous solution, 70 parts of a 50% aqueous solution of sodium lactate, 50 parts of glycerin and 15 parts of urea were mixed with stirring to obtain a water-soluble adhesive formulation. Next, this water-soluble adhesive compound was applied on the release film so as to have a thickness of 1 mm to obtain a sheet-like pack material of the present invention.
[0040]
(Example 3-2)
300 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this, 18 parts of a 10% aqueous solution of potassium aluminum sulfate (12 hydrate) was added and reacted at 60 ° C. for 30 minutes to crosslink the gelatin. To the obtained crosslinked gelatin aqueous solution, 70 parts of a 50% aqueous solution of sodium lactate, 50 parts of glycerin and 15 parts of urea were mixed with stirring to obtain a water-soluble adhesive formulation. Next, this water-soluble adhesive compound was applied on the release film so as to have a thickness of 1 mm to obtain a sheet-like pack material of the present invention.
[0041]
(Example 3-3)
100 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this, 160 parts of a 50% aqueous solution of sodium lactate and 15 parts of urea were added and stirred to obtain a water-soluble adhesive compound. Next, this water-soluble adhesive compound was applied on the release film so as to have a thickness of 1 mm to obtain a sheet-like pack material of the present invention.
(Example 3-4)
100 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this, 160 parts of a 50% aqueous solution of sodium lactate and 5 parts of rhodanammon were added and stirred to obtain a water-soluble adhesive formulation. Next, this water-soluble adhesive compound was applied on the release film so as to have a thickness of 1 mm to obtain a sheet-like pack material of the present invention.
[0042]
(Example 3-5)
300 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this was added 3 parts of a 20% aqueous solution of ammonium zirconium carbonate and reacted at 60 ° C. for 30 minutes to crosslink the gelatin. To the obtained crosslinked gelatin aqueous solution, 300 parts of a 50% aqueous solution of sodium lactate was added and stirred to obtain a water-soluble adhesive compound. Next, this water-soluble adhesive compound was applied on the release film so as to have a thickness of 1 mm to obtain a sheet-like pack material of the present invention.
[0043]
(Example 3-6)
300 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this was added 3 parts of a 20% aqueous solution of ammonium zirconium carbonate and reacted at 60 ° C. for 30 minutes to crosslink the gelatin. To the obtained crosslinked gelatin aqueous solution, 400 parts of a 50% aqueous solution of sodium lactate and 40 parts of glycerin were added and mixed by stirring to obtain a water-soluble adhesive formulation. Next, this water-soluble adhesive compound was applied on the release film so as to have a thickness of 1 mm to obtain a sheet-like pack material of the present invention.
[0044]
(Comparative Example 3-1)
300 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this was added 3 parts of a 20% aqueous solution of ammonium zirconium carbonate and reacted at 60 ° C. for 30 minutes to crosslink the gelatin. To the obtained crosslinked gelatin aqueous solution, 40 parts of a 50% aqueous solution of sodium lactate and 15 parts of urea were added and mixed by stirring to obtain a water-soluble pressure-sensitive adhesive composition having an excessive content of sodium lactate. Next, the water-soluble adhesive compound was applied on the release film so as to have a thickness of 1 mm to obtain a sheet-like pack material for comparison.
[0045]
(Comparative Example 3-2)
Add 500 parts of 50% aqueous solution of sodium lactate to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method), swell for 30 minutes at room temperature, then warm to 60 ° C to gelatin Dissolved. To this, 40 parts of glycerin was added and mixed by stirring to obtain a water-soluble pressure-sensitive adhesive composition having an excessive content of sodium lactate. Next, the water-soluble adhesive compound was applied on the release film so as to have a thickness of 1 mm to obtain a sheet-like pack material for comparison.
(Comparative Example 3-3)
100 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this, 80 parts of glycerin and 15 parts of urea were added and mixed with stirring to obtain a water-soluble adhesive compound not containing sodium lactate. Next, the water-soluble adhesive compound was applied on the release film so as to have a thickness of 1 mm to obtain a sheet-like pack material for comparison.
[0046]
(Comparative Example 3-4)
300 parts of water was added to 100 parts of gelatin (alkali-treated gelatin: viscosity 3 mPa · s, jelly strength 100 Bloom according to JIS6503 method) and swollen at room temperature for 30 minutes, and then heated to 60 ° C. to dissolve the gelatin. To this was added 3 parts of a 20% aqueous solution of ammonium zirconium carbonate and reacted at 60 ° C. for 30 minutes to crosslink the gelatin. To the obtained crosslinked gelatin aqueous solution, 150 parts of glycerin was added and mixed by stirring to obtain a water-soluble adhesive formulation not containing sodium lactate. Next, the water-soluble adhesive compound was applied on the release film so as to have a thickness of 1 mm to obtain a sheet-like pack material for comparison.
[0047]
Regarding the feeling of use when the sheet-shaped pack material obtained above is actually used, a monitor survey is conducted by 10 subjects according to the following criteria for each of the following items, with the most highly evaluated evaluation for each item. And evaluated its feeling of use. The results are shown in Table 3.
Adhesion (adhesiveness): ○: good, Δ: not good, ×: bad
Sense of tension: ○: Good, △: Not good, ×: Bad
Wet feeling; ○: good, Δ: not so good, x: bad
Sagging of pack material (shape retention): ○: No sagging, Δ: Slight sagging, ×: Sagging
[0048]
[Table 3]
【The invention's effect】
The adhesive composition of the present invention can maintain good flexibility over a long period of time, and can exhibit excellent tackiness even in an equilibrium moisture state. Adhesive for bookbinding back paste that does not cause “cracking” and “burr” over time, water-soluble adhesive that exhibits excellent tackiness even in equilibrium moisture conditions, and a sheet that combines tackiness and shape retention A pack material can be provided.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2002039353A JP3872702B2 (en) | 2002-02-15 | 2002-02-15 | Adhesive composition and use thereof |
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| JP2002039353A JP3872702B2 (en) | 2002-02-15 | 2002-02-15 | Adhesive composition and use thereof |
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| WO2006079251A1 (en) * | 2005-01-31 | 2006-08-03 | Shenzhen Bak Battery Co., Ltd | The aqueous adhesive, preparation method thereof and its uses for making anode of the lithium ion battery |
| JP2009051962A (en) * | 2007-08-28 | 2009-03-12 | Toho Sangyosha:Kk | Adhesive |
| JP5550166B2 (en) * | 2008-06-17 | 2014-07-16 | 大阪シーリング印刷株式会社 | Adhesives and labels |
| JP5427590B2 (en) * | 2008-12-26 | 2014-02-26 | 良治 馬場 | Dressing material and manufacturing method thereof |
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