JP3875072B2 - Rubber substrate / thermal adhesive material composite and method for producing the composite - Google Patents
Rubber substrate / thermal adhesive material composite and method for producing the composite Download PDFInfo
- Publication number
- JP3875072B2 JP3875072B2 JP2001343185A JP2001343185A JP3875072B2 JP 3875072 B2 JP3875072 B2 JP 3875072B2 JP 2001343185 A JP2001343185 A JP 2001343185A JP 2001343185 A JP2001343185 A JP 2001343185A JP 3875072 B2 JP3875072 B2 JP 3875072B2
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- Prior art keywords
- glove
- sheet
- acrylonitrile
- rubber
- butadiene rubber
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
Landscapes
- Gloves (AREA)
- Laminated Bodies (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、ゴム基体/熱接着性材料の複合材及び該複合材の製造方法に関し、更に詳しくは、熱可塑性エラストマーを塗布した面を接着面とするゴム基体と、熱接着性材料とを熱接着することにより、両者が強固に接着されるゴム基体/熱接着性材料の複合材及びその製造方法に関する。
【0002】
【従来の技術】
従来より、ゴム基体を用いたゴム製品は、種々の用途に使用されており、特に手袋の分野では、ゴム、特にアクリロニトリル−ブタジエンゴム(NBR)やクロロプレンゴム(CR)等の合成ゴムは、手袋用の素材として耐油性、耐候性等の特性に優れるため、従来の塩化ビニル製の手袋に代わるものとして注目されている。
【0003】
また、これらのゴム基体と他の材料との複合製品も種々提案されている。しかしながら、ゴム基体自体はヒートシール性がなく、同種もしくは異種のゴム同士はもちろんのこと、ゴム基体と他の材料とを接着させることは非常に難しく、特に手袋用途に使用されるような伸び率が大きいゴムに他の材料を接着させることは極めて困難であった。
【0004】
すなわち、合成ゴムと他の材料とを接着させるには、主としてに接着剤が用いられるが、それに先だって、接着面の処理工程、例えば、サンドペーパーやワイヤーブラシでゴム表面を粗す工程、ゴムの削りかすをエアで飛ばす工程、溶剤で拭き取る工程などが必要とされる。例えば加硫ゴムとポリオレフィンを接着する方法としては、ポリオレフィンに対してはコロナ放電処理を施し、加硫ゴム表面に対しては擬ハロゲン化合物処理を施した後、エポキシ系接着剤及びNBR系接着剤から選ばれた少なくとも1つを前記各処理した面のいずれか一方または双方に塗布後、積層することを特徴とするポリオレフィンと加硫ゴムとの接着方法が提案されている(特開昭58−98234号公報)。
【0005】
しかし、接着剤による合成ゴムと他の材料との接着は、一般に合成ゴムの接着性が乏しく、特に上記したNBRは、他の材料と接着した場合に十分な接着強度を有するものではなかった。また、接着剤で接着させる場合には、合成ゴムに塗布した接着剤が乾燥する前に被接着物を接着させる必要があり、接着後も圧着及び乾燥することが必要であるため、特に伸びが大きく、かつ複雑な形状のゴム基体を使用した場合には製造上の管理が困難であった。
【0006】
一方、これ以外にも合成ゴムと他の材料とを接着する方法が提案されている。例えば、▲1▼水素添加アクリロニトリル・ブタジエン共重合体ゴム、メタクリル酸、酸化亜鉛及び有機過酸化物を含有する未硬化ゴム組成物と、原料ゴム組成としてアクリロニトリル・ブタジエン共重合体ゴム又はイソブチレン・イソプレン共重合体ゴムを含有する未加硫ゴム組成物とを硬化加硫し、接着・一体化したゴム・ゴム接着複合体とする方法(特開平5−186609号公報)や、▲2▼特定の構造式を有するシラン化合物を標準的な市販ゴムに配合することにより通常のゴムとポリアミドとが強固に接合する複合体を製造する方法(特開平7−11013号公報)等が提案されていた。
【0007】
しかし、▲1▼の方法では、未加硫状態のもの同士を加硫、硬化して接着するものであり、成形されたもの同士を接合する方法ではないため、応用範囲が狭いものであった。また、▲2▼の方法では、接着されるものがポリアミドに限定され、また、ゴムに他の成分を配合するため、ゴム自体の性質が変化してしまうという問題点を有していた。
【0008】
【発明が解決しようとする課題】
したがって、ゴム基体と他の熱接着性材料とを簡単に、しかも十分な接着強度で熱接着できる技術の開発が望まれていた。
【0009】
【課題を解決するための手段】
本発明者らは、ゴムの熱接着性について鋭意研究を重ねていたところ、ゴム基体に塗布した熱可塑性エラストマーは、他の熱接着性材料と簡単に熱接着させることが可能であり、しかも当該部分での接着強度は十分なものであることを見出し、本発明を完成した。
【0010】
すなわち、本発明は、熱可塑性エラストマーを塗布した面を接着面とするゴム基体と、熱接着性材料とを熱接着してなるゴム基体/熱接着性材料の複合材及び該複合材の製造方法を提供するものである。
【0011】
【発明の実施の形態】
本発明のゴム基体/熱接着性材料の複合材(以下「複合材」とする)に用いられるゴム基体としては、従来公知のゴム、例えば天然ゴム、合成ゴム等で形成されたものを使用することができる。このうち合成ゴムとしては、例えば、アクリロニトリル−ブタジエンゴム(NBR)、クロロプレンゴム(CR)、スチレン−ブタジエンゴム(SBR)、イソプレンゴム(IR)、ポリウレタン(PU)等を使用することができる。これらの合成ゴムは、そのままゴム基体の原料として用いることができるが、これら合成ゴムに加硫剤、加硫促進剤、軟化剤、充填剤等を配合したものを基体の原料としてもよい。
【0012】
また、このゴム基体の形状は、任意の形状であって良いが、後述の熱接着性材料と接着することからも、面状部を有する形状、例えばシート状、フィルム状、板状であることが好ましい。さらに、ゴムを原料とする手袋、長靴、エプロン等であって、その一部に面状部を有する製品形態のものであってもよい。
【0013】
上記ゴム基体に接着面を形成するには、必要な部分に熱可塑性エラストマーを塗布し、これを乾燥させれば良い。塗布される熱可塑性エラストマーとしては、伸縮性を有する熱可塑性エラストマーが好ましい。この伸縮性を有する熱可塑性エラストマーの例としては、例えば、ウレタン系エラストマー、ポリスチレン系エラストマー、ポリオレフィン系エラストマー、ポリ塩化ビニル系エラストマー、ポリエステル系エラストマー、ポリアミド系エラストマー、ポリブタジエン系エラストマー、エチレン−ビニルアセテート(EVA)共重合体、エチレン−アクリル酸(EAA)共重合体、エチレン−メチルメタクリレート(EMA)共重合体等のオレフィン系樹脂溶液、アイオノマー等を熱接着性材料に合わせて使用することができる。
【0014】
上記熱可塑性エラストマーをゴム基体の接着面に塗布する方法としては、特に制限はなく、従来より公知の方法、例えば刷毛等で塗布する方法、ゴム基体を熱可塑性エラストマー液に浸漬して塗布する方法、スプレー噴射により塗布する方法、印刷により塗布する方法等の手段を用いて塗布することができる。この塗布における塗布厚等は特に制約はないが、1μm〜500μm程度とすることが好ましい。また、塗布後の乾燥は、自然乾燥若しくは熱風等の強制乾燥等の手段により行うことができる。
【0015】
一方、本発明の複合材に用いられる熱接着性材料は、各種プラスチックや熱可塑性エラストマー等、熱接着性を有するものであれば特には制限はないが、熱可塑性樹脂を用いるのが好ましい。熱可塑性樹脂としては、例えば、ポリエチレン、ポリプロピレン、エチレン−ビニルアセテート共重合体、エチレン−アクリル酸共重合体、エチレン−エチルアクリレート共重合体、エチレン−メチルメタクリレート共重合体等のオレフィン系樹脂を挙げることができる。また、その形状は、被着体であるゴム基体と同様、面状部を有する形状、例えばシート状、フィルム状、板状であることが好ましいが、一部に面状部を有するものであれば、その製品形態には特に制限はない。
【0016】
さらに、熱接着性材料として、基材自体または基材全体が熱接着性を有しない材料(以下「非熱接着性材料」とする)であっても、少なくてもゴム基体と接着する面が熱接着性を有しているものであれば問題はない。例えば、非熱接着性材料のゴム基体と接着する面に対して、熱接着性材料をコーティングまたはラミネート等の加工を施し、該面に熱接着性を有するようにした材料を用いることができる。これにより、ゴム基体以外の材料はもちろん、熱接着性材料としてゴム基体自体に熱可塑性エラストマーを塗布・乾燥させたものを用い、これを、熱可塑性エラストマーを塗布した面を接着面としたゴム基体と接着することもでき、ゴム基体同士等の熱接着も可能となる。
【0017】
また、これらの熱接着性材料は、接着面に対してプライマー処理を施すことにより、さらに接着強度を高めることができる。プライマー処理としては、例えば、熱接着性材料にオゾン処理またはコロナ放電を行うことにより極性基を導入する。更に好ましくはTiO2 やSiO2を混入したウレタン樹脂、エポキシ樹脂等の極性樹脂を塗布する等の処理方法等を挙げることができる。
【0018】
熱可塑性エラストマーを塗布したゴム基体と他の熱接着性材料を接着する方法としては、例えば、ゴム基体の接着面と熱接着性材料の接着面を合わせ、ヒートシール機等を用いて熱接着する方法が挙げられる。両者を熱接着するための温度、圧力及び時間等の条件は、ゴム基体の種類や厚さ、また熱接着性材料の種類や厚さ及び熱可塑性エラストマーの種類により、適宜最適な条件を選択して行うことができる。
【0019】
以上説明した方法により調製された本発明の複合材は、ゴム基体、特に合成ゴムのゴム基体と他の熱接着性材料とを確実に接着することができるものである。特に、従来から接着が困難とされていた、伸び率の大きいゴム基体、例えば、伸び率が50〜1200%程度のゴム基体と熱接着性材料を熱接着して複合体とした場合であっても、十分にその接着効果を発揮することができる。
【0020】
すなわち、伸び率の大きいゴム基体の代表例として、ゴム手袋が挙げられるが、本発明の複合材は、このようなゴム基体に対して高い接着効果を与えることができるため、従来塩化ビニル手袋でしか実現できなかった種々の付加機能を与えることができる。
【0021】
例えば、塩化ビニル製手袋においては、特開昭57−157715号公報の図に開示されるような、塩化ビニル製手袋の裾部に筒状の袖(腕カバーと同意。以下同)をつけた袖つき袋や、特開昭55−128002号公報に開示されるような、塩化ビニル製の手袋の裾部に面ファスナー(いわゆるマジックテープ(登録商標))をつけた手袋など、種々の付加機能を有するものが提案されてきたが、これは、塩化ビニルがヒートシール性を有するため可能となったものであった。
【0022】
従来、このような腕カバー付き手袋や面ファスナー付き手袋を、塩化ビニルに代え、ゴムを用いて製造することは、前述したようにゴムがヒートシール性を有しないため、縫製によりゴム手袋に腕カバーや面ファスナーを取り付けるしか手段がなく、非常に手間の掛かるものであった。加えて、縫製により取り付けた場合には、水を取り扱った際に、縫製部から手袋内部に水等が入ってしまうという問題点を有していた。
【0023】
これに対し本発明の複合材は、伸び率の大きいゴム基体と熱接着性材料とを、高い接着強度で熱接着することが可能であるので、ゴムを基体とする手袋に対しても、塩化ビニル製手袋と同様な付加機能を与えることができるのである。
【0024】
より具体的に、本発明の複合材を用いて、腕カバー付き手袋を製造する方法の一例を示せば次の通りである。すなわち、まず常法により製造したゴム手袋の裾部周縁に熱可塑性エラストマーを塗布して、これを十分乾燥させる。次に、熱接着性材料で構成されるシートの片面にプライマー処理を施した後、この処理面とゴム手袋の裾部周縁(熱可塑性エラストマー塗布部)と合わせ、圧着ずれしないように固定した後、熱接着させる。最後に、シートのプライマー処理を施していない面の端部を熱接着して、筒状の腕カバーを形成することにより、腕カバー付きゴム製手袋を製造することができる。なお、予め熱接着性材料で腕カバーを形成したあと、該腕カバーの開口部の一端の周縁部に、ゴム手袋の裾部周縁(エラストマー塗布部)とを合わせ、熱接着させてもよい。手袋と袖部とのヒートシールの方法は、加熱したバーを用いて複数回押すことにより行ってもよく、また、特開昭57−157715号公報記載の方法により行ってもよい。
【0025】
また、手袋の裾部に面ファスナーを付けたゴム手袋を製造する方法の一例としては、常法に従って製造したゴム手袋に熱可塑性エラストマーを塗布、乾燥させて接着面を調製し、これと、熱接着性材料で構成される面ファスナーの裏面(面ファスナーにおける雌雄部を有しない面。以下同)に必要により熱可塑性エラストマーを塗布、乾燥したものとを圧着した後熱接着する方法が挙げられる。この場合、面ファスナーの裏面は、凹凸がある場合が多いので、特にプライマー処理を施さなくても容易に接着することができる。また、面ファスナーの裏面に熱接着性樹脂である発泡シートや弾性シートを接着し、これをゴム手袋に熱可塑性エラストマーを塗布、乾燥させたものとを熱接着することもできる。
【0026】
なお、本発明の複合材は、伸び率が大きいゴム基体と熱接着性材料とを接着すること可能としたものであるが、熱接着性材料にも伸び率の大きいものを用いても、ゴム基体と熱接着性材料を接着して複合材を得ることもできる。これは、熱可塑性エラストマーが、ゴム基体と熱接着性材料の伸びに追従して伸びることができるため、両者を熱接着したときに剥がれにくい複合材を得ることができる。
【0027】
上記の腕カバー付手袋の場合でも、ゴム基体であるゴム製手袋と熱接着性材料である腕カバーは、通常両者とも伸び率が大きいものであるが、本発明の手段により、両者を熱接着した複合材(腕カバー付手袋)を簡便に得ることができる。
【0028】
【実施例】
次に、実施例および比較例をあげ、本発明を更に詳しく説明するが、本発明はこれらになんら制約されるものではない。
【0029】
実 施 例 1
ゴム基体/熱接着性材料複合材の剥離強度の測定:
表1に示すゴム基体及び熱接着性材料を、それぞれ10cm×1cmの大きさに切り取った。ゴム基体の接着面に、これも表1に示す熱可塑性エラストマーを塗布し、約15分間自然放置して乾燥した。これをヒートシール機(富士インパルスシーラー:(株)富士包装社製)を用いて温度170℃、圧力1MPaの条件で熱接着し、本発明品1〜7及び比較品1〜3のゴム基体/熱接着性材料複合材を得た。なお、比較品3は、ゴムの接着面に熱可塑性エラストマーを塗布し、乾燥前に熱接着性材料を圧着させただけであり、熱接着を行っていないものである。材料構成を表1に示す。
【0030】
( 材 料 構 成 )
【表1】
熱可塑性エラストマー:
ウレタン系エラストマー;ボンドG350(コニシ(株)製)
EVA系エラストマー;デンカEVAテックス(電気化学工業(株)製)
【0031】
上記で作成した本発明品1〜7及び比較品1〜3を、引張試験機(ジョッパー式抗張力試験機:上島製作所社製)を用いて、引張速度200mm/minの条件で剥離強度を測定した。結果を表2に示す。
【0032】
( 結 果 )
【表2】
【0033】
表2の結果のように、本発明品の複合材は、剥離強度が大きく、両者が強固に接着されていることが確認できた。一方、比較品の複合材は、両者が接着しなかったり、接着しても剥離強度は小さかった。
【0034】
実 施 例 2
面ファスナー付きNBR製手袋の製造:
常法で製造したNBR製手袋の裾部に、ウレタン系熱可塑性エラストマー(ボンドG350:コニシ(株)製)を塗布し、乾燥した。一方、2cm×4cmの大きさに切ったナイロン製面ファスナーの雌部及び2cm×2cmのナイロン製面ファスナーの雄部のそれぞれの裏面(接着面)にも同様に、ウレタン系熱可塑性エラストマー(ボンドG350:コニシ(株)製)を塗布して、上記と同様の条件で乾燥させた。
【0035】
このNBR製手袋の塗布面と面ファスナーの接着面を合わせ、ヒートシール機(富士インパルスシーラー:(株)富士包装社製)を用いて、温度170℃、圧力1MPaの条件で約1秒間熱接着して、袖部に面ファスナーを付けたNBR製手袋を得た。
【0036】
このNBR製手袋の、手袋と面ファスナーの接着面の剥離強度を引張試験機(ジョッパー式抗張力試験器:上島製作所社製)を用いて測定したところ15N/cmであった。また、本手袋に対して、約1000回の面ファスナーの付けはずしを実施したが、NBR製手袋と面ファスナーの接着面に剥がれは生じなかった。
【0037】
一方、対照として、常法により製造したNBR製手袋の裾部に2cm×4cmの大きさに切った面ファスナーの雌部及び2cm×2cmの面ファスナーの雄部の裏面を合わせ、温度170℃、圧力約1MPaの条件で約1秒間熱接着したものを調製したが、面ファスナーとNBR製手袋は熱接着されなかった。
【0038】
実 施 例 3
腕カバー付きNBR製手袋の製造:
常法で製造したNBR製手袋の裾部周縁表面にウレタン系熱可塑性エラストマー(ボンドG350(コニシ(株)製))を塗布し、乾燥した。
【0039】
一方、袖部材として、EVAフィルム(厚さ0.2mm)の片面にコロナ放電を行った後、二液硬化タイプのウレタン系樹脂(Bayflex:バイエル社製)を塗布し、プライマー処理を施した。このフィルムの非プライマー処理面同士を向かい合わせて熱接着し、これを裏返して筒状の腕カバーを形成した。
【0040】
この腕カバーの開口部一端の周縁の裏面(内側)を、NBR手袋のウレタン系熱可塑性エラストマー塗布面と合わせ、ヒートシール機(富士インパルスシーラー:(株)富士包装社製)で、温度170℃、圧力1MPaの条件で約1秒間熱接着して、腕カバー付きNBR製手袋を得た。
【0041】
この腕カバー付きNBR製手袋の、接着部の剥離強度を引張試験機(ジョッパー式抗張力試験機:上島製作所社製)で測定したところ、15N/cmであった。また、本手袋を自家用車の洗車に使用したところ、手袋本体と袖部の接着は剥がれるものではなかった。
【0042】
一方、常法で製造したNBR製手袋の裾部に、EVA系熱可塑性エラストマー(ボンドG350(コニシ(株)製))を塗布した。上記方法と同様にしてEVAフィルム製筒状腕カバーを製造し、その裏面をウレタン系熱可塑性エラストマー塗布直後のNBR手袋の塗布面と合わせて押圧し、接着した後、乾燥させて腕カバー付きNBR製手袋を比較品として得た。
【0043】
得られた腕カバー付きNBR製手袋の接着部の剥離強度は2N/cmであり、手袋を手に装着するときに、簡単に手袋と袖部が剥がれてしまうものであった。
【0044】
【発明の効果】
本発明によれば、従来接着が困難とされていたゴム基体と熱接着性材料の複合材を得ることができる。特に、伸び率の大きいゴム基体であっても高い接着性能を有するため、種々のゴムを基体とする製品に応用することができる。
【0045】
具体的には、本発明により、ゴム基体であるゴム製手袋に面ファスナーや腕カバー等を接着することを可能とし、ゴム製手袋に種々の新たな付加機能を与えることができる。
以 上[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a rubber substrate / thermoadhesive material composite material and a method for producing the composite material. More specifically, the present invention relates to a rubber substrate having a surface coated with a thermoplastic elastomer as an adhesive surface, and a thermal adhesive material. The present invention relates to a rubber substrate / thermoadhesive material composite material in which both are firmly bonded to each other and a method for producing the same.
[0002]
[Prior art]
Conventionally, rubber products using a rubber base have been used for various applications. Especially in the field of gloves, rubbers, especially synthetic rubbers such as acrylonitrile-butadiene rubber (NBR) and chloroprene rubber (CR), are gloves. It is attracting attention as an alternative to conventional vinyl chloride gloves because of its excellent properties such as oil resistance and weather resistance.
[0003]
Various composite products of these rubber substrates and other materials have also been proposed. However, the rubber substrate itself does not have heat-sealability, and it is very difficult to bond the rubber substrate and other materials as well as the same or different types of rubber, especially the elongation rate used for glove applications. It was extremely difficult to bond other materials to a large rubber.
[0004]
That is, an adhesive is mainly used to bond synthetic rubber and other materials, but prior to that, a process for treating the adhesive surface, for example, a process of roughening the rubber surface with sandpaper or a wire brush, A process of flying the scraps with air, a process of wiping with a solvent, and the like are required. For example, as a method of adhering vulcanized rubber and polyolefin, after applying corona discharge treatment to polyolefin and treating the vulcanized rubber surface with pseudo-halogen compound, epoxy adhesive and NBR adhesive A method of adhering polyolefin and vulcanized rubber has been proposed, characterized in that at least one selected from the above is applied to one or both of the treated surfaces and then laminated (Japanese Patent Laid-Open No. 58-86). 98234).
[0005]
However, the adhesion between the synthetic rubber and the other material by the adhesive is generally poor in the adhesion of the synthetic rubber. In particular, the NBR described above does not have a sufficient adhesive strength when adhered to the other material. In addition, when bonding with an adhesive, it is necessary to bond the object to be bonded before the adhesive applied to the synthetic rubber dries, and it is necessary to press and dry after bonding. When a rubber substrate having a large and complicated shape is used, management in manufacturing is difficult.
[0006]
On the other hand, methods for adhering synthetic rubber and other materials have been proposed. For example, (1) uncured rubber composition containing hydrogenated acrylonitrile / butadiene copolymer rubber, methacrylic acid, zinc oxide and organic peroxide, and acrylonitrile / butadiene copolymer rubber or isobutylene / isoprene as raw rubber composition A method of curing and vulcanizing an unvulcanized rubber composition containing a copolymer rubber to form a bonded / integrated rubber / rubber bonded composite (Japanese Patent Laid-Open No. 5-186609), or (2) a specific There has been proposed a method (Japanese Patent Laid-Open No. 7-11013) for producing a composite in which a normal rubber and a polyamide are firmly bonded by blending a silane compound having a structural formula with a standard commercial rubber.
[0007]
However, in the method (1), the unvulcanized ones are vulcanized, cured and bonded, and not the method of joining the molded ones, so the application range is narrow. . In addition, the method (2) has a problem that the material to be bonded is limited to polyamide, and the properties of the rubber itself change because other components are added to the rubber.
[0008]
[Problems to be solved by the invention]
Therefore, it has been desired to develop a technique capable of easily and thermally bonding a rubber substrate and another heat-adhesive material with sufficient adhesive strength.
[0009]
[Means for Solving the Problems]
The inventors of the present invention have made extensive studies on the thermal adhesiveness of rubber, and the thermoplastic elastomer applied to the rubber substrate can be easily thermally bonded to other thermal adhesive materials. It was found that the adhesive strength at the part was sufficient, and the present invention was completed.
[0010]
That is, the present invention relates to a rubber substrate / thermoadhesive material composite material obtained by thermally bonding a rubber substrate having a surface coated with a thermoplastic elastomer as an adhesive surface and a heat adhesive material, and a method for producing the composite material. Is to provide.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
As the rubber substrate used in the rubber substrate / thermoadhesive material composite material of the present invention (hereinafter referred to as “composite material”), a conventionally known rubber such as a natural rubber or a synthetic rubber is used. be able to. Among these, as the synthetic rubber, for example, acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), styrene-butadiene rubber (SBR), isoprene rubber (IR), polyurethane (PU) and the like can be used. These synthetic rubbers can be used as raw materials for rubber substrates as they are, but those obtained by blending these synthetic rubbers with vulcanizing agents, vulcanization accelerators, softeners, fillers, etc. may be used as raw materials for the substrates.
[0012]
Moreover, the shape of the rubber substrate may be any shape, but it is a shape having a planar portion, for example, a sheet shape, a film shape, or a plate shape because it adheres to a heat-adhesive material described later. Is preferred. Furthermore, it may be a glove, boots, apron or the like made of rubber as a raw material, and a product having a planar portion in a part thereof.
[0013]
In order to form an adhesive surface on the rubber substrate, a thermoplastic elastomer may be applied to a necessary portion and dried. As the thermoplastic elastomer to be applied, a thermoplastic elastomer having stretchability is preferable. Examples of the thermoplastic elastomer having elasticity include, for example, urethane elastomer, polystyrene elastomer, polyolefin elastomer, polyvinyl chloride elastomer, polyester elastomer, polyamide elastomer, polybutadiene elastomer, ethylene-vinyl acetate ( An olefin resin solution such as an EVA) copolymer, an ethylene-acrylic acid (EAA) copolymer, an ethylene-methyl methacrylate (EMA) copolymer, an ionomer, or the like can be used in accordance with the thermal adhesive material.
[0014]
The method of applying the thermoplastic elastomer to the adhesive surface of the rubber substrate is not particularly limited, and a conventionally known method, for example, a method of applying with a brush or the like, a method of applying the rubber substrate by immersing it in a thermoplastic elastomer liquid. It can be applied using means such as a method of applying by spraying or a method of applying by printing. The coating thickness and the like in this coating are not particularly limited, but are preferably about 1 μm to 500 μm. Moreover, the drying after application | coating can be performed by means, such as forced drying, such as natural drying or a hot air.
[0015]
On the other hand, the heat-adhesive material used for the composite material of the present invention is not particularly limited as long as it has heat-adhesive properties such as various plastics and thermoplastic elastomers, but it is preferable to use a thermoplastic resin. Examples of the thermoplastic resin include olefin resins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl methacrylate copolymer. be able to. In addition, the shape is preferably a shape having a planar portion, for example, a sheet shape, a film shape, or a plate shape, similar to the rubber substrate as the adherend, but any shape having a planar portion in part. For example, the product form is not particularly limited.
[0016]
Further, as the heat-adhesive material, even if the base material itself or the whole base material is a material that does not have the heat-adhesive property (hereinafter referred to as “non-heat-adhesive material”), at least the surface that adheres to the rubber substrate. There is no problem as long as it has thermal adhesiveness. For example, it is possible to use a material in which a surface of a non-thermal adhesive material to be bonded to a rubber base is subjected to a process such as coating or laminating, and the surface has thermal adhesiveness. As a result, not only materials other than the rubber substrate, but also a rubber substrate in which a thermoplastic elastomer is applied to the rubber substrate itself and dried is used as a heat-adhesive material, and this is a rubber substrate having a surface coated with the thermoplastic elastomer as an adhesive surface. It is also possible to bond the rubber substrates together.
[0017]
Moreover, these heat-adhesive materials can further raise adhesive strength by giving a primer process with respect to an adhesive surface. As the primer treatment, for example, polar groups are introduced by performing ozone treatment or corona discharge on the heat-adhesive material. More preferably, a treatment method such as applying a polar resin such as urethane resin or epoxy resin mixed with TiO 2 or SiO 2 can be used.
[0018]
As a method for adhering a rubber base coated with a thermoplastic elastomer and another heat-adhesive material, for example, the adhesive surface of the rubber base and the adhesive surface of the heat-adhesive material are combined and heat-bonded using a heat sealer or the like. A method is mentioned. The conditions for temperature, pressure, time, etc. for thermally bonding the two are appropriately selected according to the type and thickness of the rubber substrate, the type and thickness of the heat adhesive material, and the type of thermoplastic elastomer. Can be done.
[0019]
The composite material of the present invention prepared by the method described above is capable of reliably bonding a rubber substrate, particularly a synthetic rubber rubber substrate, and another heat-adhesive material. In particular, it is a case where a rubber substrate having a high elongation rate, which has been conventionally difficult to bond, for example, a rubber substrate having an elongation rate of about 50 to 1200% and a heat-adhesive material is thermally bonded to form a composite. However, the adhesive effect can be sufficiently exhibited.
[0020]
That is, as a representative example of a rubber base having a high elongation rate, rubber gloves can be mentioned. However, since the composite material of the present invention can give a high adhesive effect to such a rubber base, Various additional functions that could only be realized can be provided.
[0021]
For example, in a vinyl chloride glove, as shown in the figure of JP-A-57-157715, a cylindrical sleeve (same as an arm cover; the same applies below) is attached to the hem of the vinyl chloride glove. Various additional functions such as a bag with a sleeve and a glove with a hook-and-loop fastener (so-called Velcro (registered trademark)) attached to the hem of a vinyl chloride glove as disclosed in Japanese Patent Laid-Open No. 55-128002 However, this has become possible because vinyl chloride has heat sealability.
[0022]
Conventionally, such a glove with an arm cover or a glove with a hook-and-loop fastener is manufactured by using rubber instead of vinyl chloride. The only way was to attach a cover or hook-and-loop fastener, which was very time-consuming. In addition, when attached by sewing, when water is handled, there is a problem that water or the like enters the glove from the sewing portion.
[0023]
On the other hand, the composite material of the present invention can thermally bond a rubber substrate having a high elongation rate and a heat-adhesive material with high adhesive strength. An additional function similar to that of vinyl gloves can be provided.
[0024]
More specifically, an example of a method for producing a glove with an arm cover using the composite material of the present invention is as follows. That is, first, a thermoplastic elastomer is applied to the periphery of the bottom of a rubber glove manufactured by a conventional method, and this is sufficiently dried. Next, after applying a primer treatment to one side of a sheet made of a heat-adhesive material, this treated surface is combined with the hem edge of the rubber glove (the thermoplastic elastomer application part) and fixed so as not to be displaced by pressure bonding. And heat-bond. Finally, a rubber glove with an arm cover can be manufactured by thermally bonding the end portions of the surface of the sheet not subjected to primer treatment to form a cylindrical arm cover. In addition, after forming an arm cover with a heat-adhesive material in advance, the peripheral edge of one end of the opening of the arm cover may be aligned with the peripheral edge of the rubber glove (elastomer application part) and thermally bonded. The heat sealing method between the glove and the sleeve may be performed by pressing a heated bar a plurality of times, or by the method described in JP-A-57-157715.
[0025]
In addition, as an example of a method of manufacturing a rubber glove having a hook-and-loop fastener at the hem portion of the glove, a thermoplastic elastomer is applied to a rubber glove manufactured according to a conventional method and dried to prepare an adhesive surface. There is a method in which a thermoplastic elastomer is applied to a back surface of a surface fastener made of an adhesive material (a surface having no male and female parts in the surface fastener, the same applies hereinafter), and a thermoplastic elastomer is pressure-bonded with a dried one, and then thermally bonded. In this case, since the back surface of the hook-and-loop fastener is often uneven, it can be easily bonded without any primer treatment. It is also possible to bond a foamed sheet or elastic sheet, which is a heat-adhesive resin, to the back surface of the hook-and-loop fastener, and heat-bond it to a rubber glove coated with a thermoplastic elastomer and dried.
[0026]
The composite material of the present invention is capable of adhering a rubber base having a high elongation and a heat-adhesive material, but even if a heat-adhesive material having a high elongation is used, the rubber A composite material can also be obtained by bonding the substrate and the heat-adhesive material. This is because the thermoplastic elastomer can be stretched following the elongation of the rubber substrate and the heat-adhesive material, so that it is possible to obtain a composite material that does not easily peel off when they are thermally bonded.
[0027]
Even in the case of the above-mentioned gloves with an arm cover, both the rubber glove which is a rubber base and the arm cover which is a heat-adhesive material usually have a high elongation rate. The obtained composite material (gloves with arm cover) can be easily obtained.
[0028]
【Example】
EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated in more detail, this invention is not restrict | limited at all to these.
[0029]
Example 1
Measurement of peel strength of rubber substrate / thermoadhesive material composite:
The rubber substrate and the heat-adhesive material shown in Table 1 were each cut to a size of 10 cm × 1 cm. The thermoplastic elastomer shown in Table 1 was also applied to the adhesive surface of the rubber substrate, and it was left to stand for about 15 minutes and dried. This was heat-bonded using a heat sealing machine (Fuji Impulse Sealer: manufactured by Fuji Packaging Co., Ltd.) under the conditions of a temperature of 170 ° C. and a pressure of 1 MPa. A heat-adhesive material composite was obtained. The comparative product 3 is obtained by simply applying a thermoplastic elastomer to the adhesive surface of rubber and press-bonding a heat-adhesive material before drying, and does not perform heat-adhesion. Table 1 shows the material structure.
[0030]
(Material composition)
[Table 1]
Thermoplastic elastomer:
Urethane elastomer; Bond G350 (manufactured by Konishi Co., Ltd.)
EVA elastomer; Denka EVA Tex (manufactured by Denki Kagaku Kogyo Co., Ltd.)
[0031]
The peel strengths of the inventive products 1 to 7 and comparative products 1 to 3 prepared above were measured under a tensile speed of 200 mm / min using a tensile tester (Jopper type tensile tester: manufactured by Ueshima Seisakusho). . The results are shown in Table 2.
[0032]
(Result)
[Table 2]
[0033]
As shown in Table 2, the composite material of the present invention had high peel strength, and it was confirmed that the two were firmly bonded. On the other hand, the composite material of the comparative product did not adhere to each other, or the peel strength was small even if they were adhered.
[0034]
Example 2
Production of NBR gloves with hook-and-loop fasteners:
A urethane-based thermoplastic elastomer (Bond G350: manufactured by Konishi Co., Ltd.) was applied to the bottom of an NBR glove manufactured by a conventional method and dried. On the other hand, the urethane-based thermoplastic elastomer (bond) is similarly applied to the back surface (adhesive surface) of the female part of the nylon surface fastener cut to a size of 2 cm × 4 cm and the male part of the nylon surface fastener of 2 cm × 2 cm. G350: manufactured by Konishi Co., Ltd.) was applied and dried under the same conditions as described above.
[0035]
The coated surface of the NBR gloves and the adhesive surface of the hook-and-loop fastener are aligned, and heat-bonded for about 1 second at a temperature of 170 ° C. and a pressure of 1 MPa using a heat sealer (Fuji Impulse Sealer: manufactured by Fuji Packaging Co., Ltd.). Thus, an NBR glove with a hook-and-loop fastener on the sleeve was obtained.
[0036]
The peel strength of the adhesive surface of the NBR glove and the hook-and-loop fastener was measured using a tensile tester (Jopper type tensile tester: manufactured by Ueshima Seisakusho Co., Ltd.) and found to be 15 N / cm. In addition, the surface fastener was removed about 1000 times from the glove, but no peeling occurred on the adhesive surface between the NBR glove and the surface fastener.
[0037]
On the other hand, as a control, a female part of a hook-and-loop fastener cut to a size of 2 cm × 4 cm and a back surface of a male part of a hook-and-loop fastener of 2 cm × 2 cm are combined with the hem of an NBR glove manufactured by a conventional method, and the temperature is 170 ° C. Although what was heat-bonded for about 1 second on the conditions of a pressure of about 1 MPa was prepared, the surface fastener and the gloves made from NBR were not heat-bonded.
[0038]
Example 3
Manufacture of NBR gloves with arm covers:
A urethane-based thermoplastic elastomer (Bond G350 (manufactured by Konishi Co., Ltd.)) was applied to the peripheral surface of the hem portion of the NBR glove manufactured by a conventional method and dried.
[0039]
On the other hand, after performing corona discharge on one side of an EVA film (thickness 0.2 mm) as a sleeve member, a two-component curing type urethane-based resin (Bayflex: manufactured by Bayer) was applied and subjected to a primer treatment. The non-primer-treated surfaces of this film face each other and thermally bonded, and this was turned over to form a cylindrical arm cover.
[0040]
The back surface (inner side) of the periphery of one end of the opening of this arm cover is aligned with the urethane-based thermoplastic elastomer application surface of the NBR gloves, and the temperature is 170 ° C. with a heat seal machine (Fuji Impulse Sealer: manufactured by Fuji Packaging Co., Ltd.). Then, heat-bonding was performed for about 1 second under conditions of a pressure of 1 MPa to obtain an NBR glove with an arm cover.
[0041]
The peel strength of the bonded portion of the NBR glove with an arm cover was measured with a tensile tester (Jopper type tensile tester: manufactured by Ueshima Seisakusho Co., Ltd.) and found to be 15 N / cm. Moreover, when this glove was used for car washing of a private car, the adhesion between the glove body and the sleeve was not peeled off.
[0042]
On the other hand, an EVA thermoplastic elastomer (Bond G350 (manufactured by Konishi Co., Ltd.)) was applied to the bottom of an NBR glove manufactured by a conventional method. A cylindrical arm cover made of EVA film is manufactured in the same manner as described above, and the back side is pressed together with the application surface of the NBR glove immediately after the application of the urethane-based thermoplastic elastomer, bonded, dried, and dried. Gloves made were obtained as comparative products.
[0043]
The peel strength of the bonded portion of the obtained NBR glove with an arm cover was 2 N / cm, and when the glove was attached to the hand, the glove and the sleeve were easily peeled off.
[0044]
【The invention's effect】
According to the present invention, it is possible to obtain a composite material of a rubber base and a heat-adhesive material, which has conventionally been difficult to bond. In particular, even a rubber substrate having a high elongation rate has high adhesion performance, and therefore can be applied to products having various rubber substrates.
[0045]
Specifically, according to the present invention, it is possible to bond a hook-and-loop fastener, an arm cover or the like to a rubber glove that is a rubber base, and it is possible to give various new additional functions to the rubber glove.
more than
Claims (12)
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