JP4427216B2 - Adhesive, method for connecting objects to be adhered, and optical device - Google Patents

Adhesive, method for connecting objects to be adhered, and optical device Download PDF

Info

Publication number
JP4427216B2
JP4427216B2 JP2001344572A JP2001344572A JP4427216B2 JP 4427216 B2 JP4427216 B2 JP 4427216B2 JP 2001344572 A JP2001344572 A JP 2001344572A JP 2001344572 A JP2001344572 A JP 2001344572A JP 4427216 B2 JP4427216 B2 JP 4427216B2
Authority
JP
Japan
Prior art keywords
adhesive
component
optical
optical component
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP2001344572A
Other languages
Japanese (ja)
Other versions
JP2003147281A (en
Inventor
美恵子 田中
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dexerials Corp
Original Assignee
Sony Chemical and Information Device Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sony Chemical and Information Device Corp filed Critical Sony Chemical and Information Device Corp
Priority to JP2001344572A priority Critical patent/JP4427216B2/en
Publication of JP2003147281A publication Critical patent/JP2003147281A/en
Application granted granted Critical
Publication of JP4427216B2 publication Critical patent/JP4427216B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Landscapes

  • Mounting And Adjusting Of Optical Elements (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Description

【0001】
【発明の属する技術分野】
本発明は接着剤にかかり、特に、光学装置に用いられるガラス部品と樹脂部品とを貼り合わせる接着剤に関する。
【0002】
【従来の技術】
従来より、光ピックアップ用の光学装置に用いられる種々のレンズや支持部材、受光素子などの光学部品の材質には、ガラスが用いられており、光学部品同士の接続には、紫外線硬化型の接着剤が広く用いられている。
【0003】
ところで、各光学部品を構成する材質として、ポリメチルメタクリレート(以下PMMAと略記する)やポリカーボネ−ト等の樹脂が注目されている。これらの樹脂はガラスに比べて軽く、成形が容易であり、樹脂からなる光学部品を用いることで光学装置全体の小型軽量化が可能である上、製造にかかるコストも安い。
従って、光学部品の材質はガラスから樹脂へ移行しつつあり、現状では一つの光学装置内にガラスからなる光学部品と樹脂からなる光学部品とが混在することが多い。
【0004】
しかしながら、PMMA等の樹脂とガラスとでは熱膨張率が異なるため、樹脂からなる光学部品とガラスからなる光学部品とを接着剤で貼り合わせた場合、光学装置周囲の温度が上昇した場合に、膨張率の差により生じる応力により、光学部品が接着剤から剥がれる場合がある。
【0005】
【発明が解決しようとする課題】
本発明は上記従来技術の不都合を解決するために創作されたものであり、線膨張係数が高く、かつ、適度な弾性を有する接着剤を提供することである。
【0006】
【課題を解決するための手段】
上記課題を解決するために、請求項1記載の発明は、重合性成分と、ゴム成分と、光重合開始剤とを含有し、紫外線の照射で前記重合性成分と前記ゴム成分とが重合するように構成された接着剤であって、前記重合性成分は、アクリルモノマーであるフェノキシエチルアクリレートと、ウレタンアクリレートの低重合体であるアクリルオリゴマーを含有し、前記ゴム成分は、ニトリルブタジエンゴム含有し、200mW/cm2の照度で300mJ/cm2の積算光量での紫外線照射による重合後の状態では、引張切断において、切断時の標線間距離L1と引張り前の標線間距離L0から、下記式、
N = (L1−L0)/L0×100
で求めた伸び率N(%)が200%以上であり、前記アクリルオリゴマーを単独重合させた場合に得られるポリマーの前記伸び率N(%)は150%以上である接着剤である。
請求項2記載の発明は、請求項1記載の接着剤であって、前記重合性成分100重量部に対する前記ニトリルブタジエンゴムの添加量は、0.5重量部以上である接着剤である。
請求項3記載の発明は、貼着対象物の接続方法であって、ガラスからなる第一の貼着対象物と、樹脂からなる第二の貼着対象物とを、請求項1又は請求項2のいずれか1項記載の接着剤からなる塗布層を介して密着させる工程と、前記塗布層に紫外線を照射させ、前記塗布層を構成する接着剤を硬化させる工程とを有する貼着対象物の接続方法である。
請求項4記載の発明は、光学装置であって、ガラスからなる第一の光学部品と、樹脂からなる第二の光学部品とを有し、前記第一の光学部品と前記第二の光学部品との間に、請求項1又は請求項2のいずれか1項記載の接着剤が配置され、前記接着剤が前記第一の光学部品と前記第二の光学部品の両方に密着した状態で、紫外線照射により前記接着剤が硬化された光学装置である。
請求項5記載の発明は、請求項4記載の光学装置であって、前記第二の光学部品を構成する樹脂は、ポリメチルメタクリレートと、ポリエチレンテレフタレートと、ポリカーボネートと、ノルボルネン樹脂ポリマーとからなる群より選択される樹脂を含有する光学装置である。
【0007】
本発明において、「アクリルモノマー」とは、アクリレートとメタクリレートの両方を意味し、「アクリルオリゴマー」とは、アクリレートとメタクリレートの一方又は両方からなる低重合体を意味する。
【0008】
本発明は上記のように構成されており、重合性成分を構成するアクリルオリゴマーとアクリルモノマーによって、硬化した後の接着剤全体の伸び率が200%以上と柔軟性が高くなっている。また、ゴムが添加されることによって、硬化した後の接着剤は適度な弾性をも有する。
【0009】
従って、本発明の接着剤によってガラスと樹脂のように、膨張率が大きく異なる貼着対象物同士を貼り合わせた場合に、膨張率の差により生じる応力は、該接着剤によって緩和される上、応力によって変形した接着剤は弾性により復元するので、貼り合わされた貼着対象物の位置がずれない。
【0010】
また、上記のような接着剤は樹脂やガラスに対する接着性も高いので、接着剤が貼着対象物から剥れ難い。本発明の接着剤には着色剤等の種々の添加剤を添加することができる。また、本発明の接着剤は、着色剤が添加されていない状態では、硬化した後の硬化物の透明性が高い。
【0011】
尚、本発明で「伸び率」とは、JIS K6251の「引張試験」に記載されている「切断時伸び」のことであり、下記の方法により測定した。
測定対象物である接着剤やオリゴマーに、ランプ出力120W/cmのメタルハライドランプを用いて、照度200mW/cm2、積算光量300mJ/cm2の紫外線を照射し、完全に硬化させてフィルム状の硬化物(膜厚約0.5mm)を得た後、ダンベル4号の金型で打ち抜いたものを試験片とした。
【0012】
試験片はJIS K6251の「引張試験方法」に記載されている条件で、切断する時点の標線間の距離を測定し、切断時の標線間距離L1から引張り前の標線間距離L0を引き、その値から更に引張り前の標線間距離L0を除し、100を乗じたものを伸び率とした((L1−L0)/L0×100、単位:%)。
【0013】
【発明の実施の形態】
以下に本発明の接着剤の製造方法を説明する。
先ず、単独重合した場合に得られるポリマーの伸び率が150%以上となるアクリルオリゴマーを用意し、該アクリルオリゴマーとアクリルモノマーとを混合して重合性成分とする。
【0014】
次に、重合性成分に、光重合開始剤とゴム成分とを添加、混合し、本発明の接着剤を作成する。
この接着剤は、紫外線を照射しない条件では常温で液状であり、可視光や近赤外線に対して高い透過性を有している。
【0015】
次に、上記の接着剤を用いて本発明の光学装置を製造する工程について説明する。
図1(a)の符号11はガラスからなる透明な第一の貼着対象物を示している。この第一の貼着対象物11の表面に上記工程で作製された接着剤を塗布し、接着剤の塗布層14を形成する(図1(b))。
【0016】
次いで、塗布層14に樹脂フィルムからなる透明な第二の貼着対象物17を押し当てる(図1(c))。その状態で、第二の貼着対象物17に向かって紫外線を照射し、紫外線が透明な第二の貼着対象物17を透過して塗布層14に到達すると、塗布層14を構成する接着剤の重合性成分が紫外線により重合して接着剤が硬化する。
【0017】
図1(d)の符号15は硬化した接着剤からなる接着剤層を示しており、該接着剤層15によって第一、第二の貼着対象物11、17が互いに貼り合わされる。
図1(d)の符号10は第一、第二の貼着対象物11、17が貼り合わされてなる積層体を示している。
【0018】
次に、本発明の接着剤を用いた光学装置の一例について説明する。
図2の符号20は光学装置の一例を示している。光学装置20はガラスレンズである第一の光学部品25と、支持部材であり、PMMAなどの樹脂からなる第二の光学部品27とを有している。
【0019】
第一の光学部品25は、図1(a)〜(d)に示した工程で接着剤層26を介して第二の光学部品27に貼りつけられており、第一の光学部品25は第二の光学部品27に支持されることによって所定位置で保持されている。
【0020】
この光学装置20を用いて光学的記録媒体21の情報を読み取るには、先ず、レーザー照射装置28から光学的記録媒体22にレーザー光21を照射する。光学的記録媒体22で反射されたレーザー光21は光学装置20の第一の光学部品25から光学装置20内に入射し、不図示の受光素子によって検出される。
【0021】
光学的記録媒体22では、情報が凹凸のパターンとして記録されており、光学的記録媒体22で反射されるレーザー光21の強度は凹凸のパターンで変化するので、反射されるレーザー光21の強度変化を検出することで、光学的記録媒体22の情報を読み取ることができる。
【0022】
本発明の接着剤では、特定のアクリルオリゴマーとアクリルモノマーとを配合することで、硬化した接着剤層26の伸び率が200%以上と高くなっており、異なる線膨張係数を有する第一、第二の光学部品25、27が加熱し、膨張した場合であっても、膨張率の差により生じる応力は硬化した接着剤層26によって吸収、緩和されるので、第一、第二の光学部品25、27が接着剤層26から剥がれることがない。
【0023】
また、ゴム成分添加されたことによって接着剤層26が適度な弾性を示すので、外部からの物理的衝撃や温度変化などにより接着剤層26が変形した場合も、接着剤層26はその弾性により復元する。
【0024】
従って、接着剤層26を介して第二の光学部品27に取り付けられた第一の光学部品25は、常に所定位置に保持されるので、第一の光学部品25から入射するレーザー光21の焦点距離や結像のずれが防止される。
【0025】
【実施例】
<実施例1>
単独重合させた場合のポリマーの伸び率が150%以上であるアクリルオリゴマー(サートマー(株)社製の商品名「CN966J75」)30重量部に対し、アクリルモノマーであるフェノキシエチルアクリレート70重量部を添加、混合し、アクリルモノマーとアクリルオリゴマーとからなる重合性成分を作製した。
尚、ここで用いたアクリルオリゴマーはウレタンアクリレートの低重合体であり、単独重合させた場合に得られるポリマーの伸び率は238%であった。
【0026】
次いで、重合性成分100重量部に対し、ゴム成分であるニトリルブタジエンゴム2重量部と、ラジカル系の光重合開始剤である長瀬産業(株)社製の商品名「イルガキュア184」とを添加、混合し、液状で透明な実施例1の接着剤を得た。
【0027】
<実施例2〜7>
実施例1で用いたアクリルモノマーとアクリルオリゴマーの添加量と、ゴム成分の添加量とをそれぞれ下記表1に示すように変えた以外は実施例1と同じ条件で実施例2〜7の接着剤を作製した。
【0028】
【表1】

Figure 0004427216
【0029】
<比較例1>
ゴム成分を添加しない以外は、実施例2〜7と同じ条件で比較例2の接着剤を作製した。
【0030】
<比較例2、3>
アクリルオリゴマーとして、単独重合させた場合に得られるポリマーの伸び率が150%未満であるアクリルオリゴマー(サートマー(株)社製の商品名「CN980」)を用い、上記表1に記載した配合比率で比較例2、3の接着剤を作製した。尚、比較例2、3で用いたアクリルオリゴマーは、ウレタンアクリレートの低重合体であり、単独重合させた場合に得られるポリマーの伸び率は63%であった。
これら実施例1〜7、比較例1〜3の接着剤を用いて下記に示す「線膨張係数」、「弾性」、「信頼性試験」、「伸び率」各評価試験を行った。
【0031】
〔伸び率〕
実施例1〜7、比較例1〜3の接着剤を剥離紙上に塗布し、塗布層を形成し、ランプ出力120W/cmのメタルハライドランプを用いて、照度200mW/cm2、積算光量300mJ/cm2の紫外線を照射して硬化させた後、硬化した接着剤を剥離紙から剥離し、10種類のフィルム状試験片をそれぞれ作製した。これら10種類の試験片を用いて、上述したようにJIS K6251の「引張り試験」の方法に準じて試験片の伸び率を測定し、得られた伸び率(%)を上記表1にそれぞれ記載した。
【0032】
〔線膨張係数〕
上記「伸び率」試験と同じ工程で10種類の試験片を作製し、それらの試験片に所定の荷重を加えた状態で初期長さLを測定した後、測定雰囲気の温度を25℃から85℃まで上昇させて試験片の温度上昇による長さの増加量dLを測定した。長さの増加量dLと、温度の変化量dTと、試料片の初期長さLとをそれぞれ下記式(1)に当てはめ、線膨張係数bを求めた。
式(1):b=(dL/dT)/L
得られた線膨張係数(×10-5/K)を上記表1にそれぞれ記載した。
【0033】
〔戻り率〕
上記「線膨張係数」試験で作製した試験片に1gの荷重を加えた状態で−40℃まで冷却する冷却処理と、85℃まで昇温する加熱処理とを繰り返し行い、−40℃のときと85℃のときの長さを測定した。
初期状態の温度は25℃の室温であり、最初に冷却処理を行った。
【0034】
第1回目の冷却処理のとき(25℃から−40℃まで冷却したとき)の試験片の長さP1と、第2回目、第3回目の冷却処理(85℃から−40℃まで冷却したとき)の試験片の長さP2、P3と、第1回目、第2回目の加熱処理のとき(−40℃から85℃まで加熱したとき)の試験片の長さQ1、Q2を測定し、低温時戻り率R1、R2(%)と、高温時戻り率S1(%)を、下記式、
1 = (P2−P1)/P1×100
2 = (P3−P1)/P1×100
1 = (Q2−Q1)/Q1×100
によって求めた。
尚、1回の加熱処理と1回の冷却処理に要する時間の合計は30分間であった。戻り率の値が低いほど、試料片の弾性は高いことを示している。
【0035】
〔信頼性試験〕
白板ガラスからなる第一の貼着対象物11に実施例1〜7、比較例1〜3の10種類の接着剤をスピンコート法によって塗布して塗布層14を形成し、該塗布層14に第二の貼着対象物17であるPMMA樹脂フィルムを密着させた後、上記「伸び率」試験と同じ照射条件で紫外線を照射し、積層体10からなる10種類の試験片を作製した。これら10種類の試験片を、「戻り率」と同じ条件で冷却処理と加熱処理とを繰り返しながら観察した。
【0036】
加熱冷却処理が400時間未満で接着剤層15の剥がれやクラック(亀裂)等が観察された場合を「NG」、400時間未満では外観の変化が起こらなかったものを「OK」として評価した。評価結果と外観変化が確認されたときの時間とを上記表1に記載した。
【0037】
上記表1から明らかなように、本発明実施例1〜7は、硬化した後の伸び率が200%以上であり、線膨張係数も大きく、充分な柔軟性を有していることがわかる。また、実施例1〜7では、戻り率も充分に低く、硬化後の接着剤が充分な弾性を有していることがわかる。
また信頼性試験の結果から明らかなように、柔軟性と弾性を併せ持つ実施例1〜7の接着剤では、比較例1〜3に比べて温度変化による耐久性が高い。
【0038】
これらの中でも、ゴム成分の添加量が0.5重量部以上15重量部以下である実施例1〜6は、ゴム成分の添加量が0.1重量部である実施例7に比べて戻り率が低く、信頼性試験においても高い結果が得られた。
他方、実施例2〜7と同じ重合性成分を含有するが、ゴム成分を含有しない比較例1の場合、線膨張係数や伸び率の結果は実施例1〜7と同程度であったが、各温度における戻り率が高かった。
【0039】
また、ゴム成分を含有するが、アクリルオリゴマーの単独重合させた場合に得れられるポリマーの伸び率が150%未満である比較例2、3では、弾性試験の戻り率の値は実施例1〜7と同程度に低かったが、線膨張係数や伸び率の値が低くかった。線膨張係数等で示される柔軟性や、戻り率で示される弾性のいずれかが充分ではない比較例1〜3では、信頼性試験の結果も悪く、比較例1では200時間で接着剤層の剥がれが見られ、比較例2、3ではそれぞれ100時間で接着剤層にクラックが見られた。
【0040】
尚、単独重合させた場合に得られるポリマーの伸び率が81%であるアクリルオリゴマー(サートマー(株)社製の商品名「CN981」)を用いた以外は比較例2、3と同じ条件で試験片を作製したところ、比較例2、3と同様に線膨張係数や伸び率の値が低かった。
【0041】
これらのことから、本発明の接着剤は、特定の重合性成分を用いることによって硬化後の伸び率や線膨張係数が高く、ゴム成分が添加されることによって硬化後に適度な弾性を有し、結果、信頼性が高くなっていることが確認された。
【0042】
以上は、アクリルモノマーとしてフェノキシエチルアクリレートを用いる場合について説明したが、本発明はこれに限定されるものではなく、例えば、テトラヒドロフルフリルアクリレート等種々のアクリレートを用いることができ、これらのアクリレートを単独で用いても良いし、2種類以上混合させたものを用いてもよい。
【0043】
また、アクリルオリゴマーもウレタンアクリレートの低重合体に限定されるものではなく、単独重合させた場合に得られるポリマーの伸び率が150%以上であれば、エステルアクリレート、エポキシアクリレート、メラミンアクリレート等種々のアクリレートの低重合体を用いることができる。
また、光重合開始剤も特に限定されるものではない。
【0044】
以上は、ゴム成分としてニトリルブタジエンゴムを用いる場合について説明したが、ニトリルブタジエンゴム以外にも、例えば、天然ゴム、イソプロピレンゴム、ブタジエンゴム、1、2ポリブタジエンゴム、スチレンブタジエンゴム、クロロプレンゴム、ブチルゴム等種々のゴムを用いることができる。これらのゴム成分は単独で用いてもよいし、2種類以上混合したものを用いてもよい。
【0045】
また、接着剤の貼着対象物を構成する材質はガラスや樹脂に限定されるものではない。貼着対象物を構成する樹脂は、PMMAに限定されるものではなく、例えばポリエチレンテレフタレート、ポリカーボネ−ト、ノルボルネン樹脂ポリマー、トリアセチルセルロース、ポリオレフィン、ポリプロピレン等種々のものを用いることができる。
【0046】
紫外線の照射方法も特に限定されるものではなく、紫外線を透過する貼着対象物を用いるのであれば、該貼着対象物に紫外線を照射することで、接着剤に紫外線を到達させることができる。
また、紫外線の照射条件も特に限定されるものではないが、紫外線の照射量が多くなりすぎると重合性成分とゴム成分とが過度に重合し、弾性率が失われるので、照度が5mW/cm2以上1000mW/cm2以下であり、かつ積算光量が300mJ/cm2以上5000mJ/cm2以下であることが好ましい。
【0047】
以上は、光学部品25、27であるレンズと支持部材とを貼り合わせる場合について説明したが、本発明はこれに限定されるものではなく、例えば、異なる材質からなる複数のレンズの貼り合わせや、受光素子やホログラムフィルム等種々の光学部品の貼り合わせに用いることができる。
【0048】
また、貼着対象物は光学部品に限定されるものではなく、本発明の接続方法によれば、例えば、液晶表示装置に用いられる液晶パネルと偏光板とを貼り合わせたり、樹脂フィルムとガラス板とを貼り合わせることができる。例えば、可撓性を有する樹脂フィルムと、ガラス板とを貼り合わせれば、耐衝撃性に優れた複合ガラス板を得ることができる。
【0049】
【発明の効果】
本発明によれば、接着剤が硬化した後の伸び率や線膨張係数が高く、かつ適度な弾性を有しているので、熱膨張率が異なる貼着対象物を貼り合わせた場合でも接着剤が剥離せず、貼着対象物の位置ずれも起こり難い。
【図面の簡単な説明】
【図1】(a)〜(d):本発明の接着剤を用いて貼着対象物の貼り合わせる工程を説明するための断面図
【図2】本発明の光学装置の一例を説明するための図
【符号の説明】
10……光学装置
14……接着剤(接着剤の塗布層)
15、26……接着剤層(硬化した接着剤)
11……第一の貼着対象物
17……第二の貼着対象物
20……光学装置
25……第一の光学部品
27……第二の光学部品[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an adhesive, and more particularly to an adhesive that bonds a glass component and a resin component used in an optical device.
[0002]
[Prior art]
Conventionally, glass has been used as a material for optical components such as various lenses, support members, and light receiving elements used in optical devices for optical pickups, and UV curable adhesive is used for connecting optical components. Agents are widely used.
[0003]
By the way, resins such as polymethylmethacrylate (hereinafter abbreviated as PMMA) and polycarbonate are attracting attention as materials constituting each optical component. These resins are lighter than glass and easy to mold, and by using optical parts made of resin, the entire optical device can be reduced in size and weight, and the manufacturing cost is low.
Therefore, the material of optical components is shifting from glass to resin, and at present, optical components made of glass and optical components made of resin are often mixed in one optical device.
[0004]
However, since the thermal expansion coefficient differs between resin such as PMMA and glass, when the optical component made of resin and the optical component made of glass are bonded together with an adhesive, the expansion occurs when the temperature around the optical device rises. The optical component may be peeled off from the adhesive due to the stress caused by the difference in rate.
[0005]
[Problems to be solved by the invention]
The present invention was created to solve the above-described disadvantages of the prior art, and is to provide an adhesive having a high linear expansion coefficient and appropriate elasticity.
[0006]
[Means for Solving the Problems]
In order to solve the above problems, the invention described in claim 1 includes a polymerizable component, a rubber component, and a photopolymerization initiator, and the polymerizable component and the rubber component are polymerized by irradiation with ultraviolet rays. The polymerizable component contains phenoxyethyl acrylate which is an acrylic monomer and an acrylic oligomer which is a low polymer of urethane acrylate, and the rubber component contains nitrile butadiene rubber . In a state after polymerization by ultraviolet irradiation at an illuminance of 200 mW / cm 2 and an integrated light amount of 300 mJ / cm 2 , in tensile cutting, the distance L 1 between the marked lines at the time of cutting and the distance L between the marked lines before tensioning From 0 , the following formula:
N = (L 1 −L 0 ) / L 0 × 100
In the obtained elongation N (%) is not less than 200%, the elongation N (%) of the polymer obtained when the acrylic oligomer was homopolymerization is an adhesive Ru der least 150%.
Invention of Claim 2 is an adhesive agent of Claim 1, Comprising: The addition amount of the said nitrile butadiene rubber with respect to 100 weight part of said polymeric components is an adhesive agent which is 0.5 weight part or more.
The invention described in claim 3 is a method for connecting an object to be adhered, wherein the first object to be adhered made of glass and the second object to be adhered made of resin are defined in claim 1 or claim. The sticking target object which has the process of closely_contact | adhering via the application layer which consists of an adhesive agent of any one of 2, and the process of irradiating the said application layer with an ultraviolet-ray and hardening the adhesive agent which comprises the said application layer. This is the connection method.
The invention of claim 4, wherein is an optical device, a first optical component made of glass, and a second optical component made of a resin, said second optical component and said first optical component Between the first optical component and the second optical component, wherein the adhesive according to any one of claims 1 and 2 is disposed, and the adhesive is in close contact with both the first optical component and the second optical component, An optical device in which the adhesive is cured by ultraviolet irradiation.
Invention of Claim 5 is an optical apparatus of Claim 4, Comprising: Resin which comprises said 2nd optical component is a group which consists of a polymethylmethacrylate, a polyethylene terephthalate, a polycarbonate, and a norbornene resin polymer. It is an optical device containing a more selected resin.
[0007]
In the present invention, “acrylic monomer” means both acrylate and methacrylate, and “acrylic oligomer” means a low polymer composed of one or both of acrylate and methacrylate.
[0008]
The present invention is configured as described above, and the acrylic oligomer and the acrylic monomer constituting the polymerizable component have a high flexibility such that the elongation percentage of the entire adhesive after curing is 200% or more. Moreover, the adhesive after hardening also has moderate elasticity by adding rubber | gum.
[0009]
Therefore, the stress caused by the difference in expansion coefficient when the objects to be bonded with each other having a large expansion coefficient are bonded together like glass and resin by the adhesive of the present invention is alleviated by the adhesive. Since the adhesive deformed by the stress is restored by elasticity, the position of the bonded object to be bonded does not shift.
[0010]
Moreover, since the above adhesives have high adhesiveness with respect to resin and glass, an adhesive is hard to peel off from a sticking target object. Various additives such as a colorant can be added to the adhesive of the present invention. Moreover, the adhesive of this invention has high transparency of the hardened | cured material after hardening | curing in the state in which the coloring agent is not added.
[0011]
In the present invention, the “elongation rate” is “elongation at break” described in “tensile test” of JIS K6251 and was measured by the following method.
Using a metal halide lamp with a lamp output of 120 W / cm, the adhesive or oligomer that is the object to be measured is irradiated with ultraviolet rays with an illuminance of 200 mW / cm 2 and an integrated light amount of 300 mJ / cm 2 , and cured completely to form a film. After obtaining an object (film thickness of about 0.5 mm), a test piece was punched with a dumbbell No. 4 mold.
[0012]
Measure the distance between the marked lines at the time of cutting under the conditions described in “Tensile test method” of JIS K6251, and measure the distance between marked lines before tension from the distance L 1 between the marked lines at the time of cutting. 0 was subtracted, and the distance L 0 between the pre-tension lines was further subtracted from that value and multiplied by 100 to obtain the elongation ((L 1 −L 0 ) / L 0 × 100, unit:%).
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The manufacturing method of the adhesive of this invention is demonstrated below.
First, an acrylic oligomer having a polymer elongation of 150% or more obtained when homopolymerized is prepared, and the acrylic oligomer and acrylic monomer are mixed to obtain a polymerizable component.
[0014]
Next, a photopolymerization initiator and a rubber component are added to and mixed with the polymerizable component to produce the adhesive of the present invention.
This adhesive is in a liquid state at normal temperature under the condition where it is not irradiated with ultraviolet rays, and has high transparency to visible light and near infrared rays.
[0015]
Next, the process of manufacturing the optical device of the present invention using the above adhesive will be described.
The code | symbol 11 of Fig.1 (a) has shown the transparent 1st sticking target object which consists of glass. The adhesive prepared in the above step is applied to the surface of the first object 11 to form an adhesive coating layer 14 (FIG. 1B).
[0016]
Next, a transparent second sticking object 17 made of a resin film is pressed against the coating layer 14 (FIG. 1 (c)). In this state, when the ultraviolet light is irradiated toward the second sticking object 17 and the ultraviolet light passes through the transparent second sticking object 17 and reaches the coating layer 14, the adhesive constituting the coating layer 14. The polymerizable component of the agent is polymerized by ultraviolet rays to cure the adhesive.
[0017]
Reference numeral 15 in FIG. 1D denotes an adhesive layer made of a cured adhesive, and the first and second objects to be adhered 11 and 17 are bonded to each other by the adhesive layer 15.
The code | symbol 10 of FIG.1 (d) has shown the laminated body by which the 1st, 2nd sticking target objects 11 and 17 are bonded together.
[0018]
Next, an example of an optical device using the adhesive of the present invention will be described.
Reference numeral 20 in FIG. 2 indicates an example of an optical device. The optical device 20 includes a first optical component 25 that is a glass lens, and a second optical component 27 that is a support member and is made of a resin such as PMMA.
[0019]
The first optical component 25 is attached to the second optical component 27 via the adhesive layer 26 in the steps shown in FIGS. 1A to 1D, and the first optical component 25 is the first optical component 25. By being supported by the second optical component 27, it is held at a predetermined position.
[0020]
In order to read information on the optical recording medium 21 using the optical device 20, first, the laser light 21 is irradiated from the laser irradiation device 28 to the optical recording medium 22. The laser beam 21 reflected by the optical recording medium 22 enters the optical device 20 from the first optical component 25 of the optical device 20, and is detected by a light receiving element (not shown).
[0021]
In the optical recording medium 22, information is recorded as a concavo-convex pattern, and the intensity of the laser beam 21 reflected by the optical recording medium 22 changes depending on the concavo-convex pattern. By detecting this, information on the optical recording medium 22 can be read.
[0022]
In the adhesive of the present invention, by adding a specific acrylic oligomer and an acrylic monomer, the elongation rate of the cured adhesive layer 26 is as high as 200% or more, and the first and second having different linear expansion coefficients. Even when the second optical components 25 and 27 are heated and expanded, the stress caused by the difference in expansion coefficient is absorbed and alleviated by the cured adhesive layer 26, and therefore the first and second optical components 25. 27 are not peeled off from the adhesive layer 26.
[0023]
Further, since the adhesive layer 26 exhibits appropriate elasticity due to the addition of the rubber component, even when the adhesive layer 26 is deformed due to an external physical impact or a temperature change, the adhesive layer 26 is not elastic. Restore.
[0024]
Accordingly, the first optical component 25 attached to the second optical component 27 via the adhesive layer 26 is always held at a predetermined position, so that the focus of the laser light 21 incident from the first optical component 25 is increased. Deviations in distance and image formation are prevented.
[0025]
【Example】
<Example 1>
70 parts by weight of phenoxyethyl acrylate, an acrylic monomer, is added to 30 parts by weight of an acrylic oligomer (trade name “CN966J75” manufactured by Sartomer Co., Ltd.) having an elongation of 150% or more when homopolymerized. And a polymerizable component composed of an acrylic monomer and an acrylic oligomer was prepared.
The acrylic oligomer used here was a low polymer of urethane acrylate, and the elongation percentage of the polymer obtained when homopolymerized was 238%.
[0026]
Next, 2 parts by weight of a nitrile butadiene rubber as a rubber component and a trade name “Irgacure 184” manufactured by Nagase Sangyo Co., Ltd. as a radical photopolymerization initiator are added to 100 parts by weight of the polymerizable component. By mixing, a liquid and transparent adhesive of Example 1 was obtained.
[0027]
<Examples 2 to 7>
The adhesives of Examples 2 to 7 under the same conditions as in Example 1 except that the addition amount of the acrylic monomer and acrylic oligomer and the addition amount of the rubber component used in Example 1 were changed as shown in Table 1 below. Was made.
[0028]
[Table 1]
Figure 0004427216
[0029]
<Comparative Example 1>
An adhesive of Comparative Example 2 was produced under the same conditions as in Examples 2 to 7 except that no rubber component was added.
[0030]
<Comparative Examples 2 and 3>
As an acrylic oligomer, an acrylic oligomer (trade name “CN980” manufactured by Sartomer Co., Ltd.) having an elongation rate of less than 150% when obtained by homopolymerization is used, and the blending ratio described in Table 1 above is used. The adhesives of Comparative Examples 2 and 3 were prepared. The acrylic oligomer used in Comparative Examples 2 and 3 was a low polymer of urethane acrylate, and the elongation percentage of the polymer obtained when homopolymerized was 63%.
Using the adhesives of Examples 1 to 7 and Comparative Examples 1 to 3, the following “linear expansion coefficient”, “elasticity”, “reliability test”, and “elongation ratio” evaluation tests were performed.
[0031]
〔Growth rate〕
The adhesives of Examples 1 to 7 and Comparative Examples 1 to 3 were applied onto release paper to form a coating layer, and using a metal halide lamp with a lamp output of 120 W / cm, an illuminance of 200 mW / cm 2 and an integrated light amount of 300 mJ / cm After curing by irradiating with ultraviolet rays of 2 , the cured adhesive was peeled off from the release paper, and 10 types of film-like test pieces were produced. Using these 10 kinds of test pieces, the elongation percentage of the test pieces was measured according to the method of “tensile test” of JIS K6251 as described above, and the obtained elongation percentages (%) are shown in Table 1 above. did.
[0032]
[Linear expansion coefficient]
Ten types of test pieces were prepared in the same process as the “elongation rate” test, and the initial length L was measured with a predetermined load applied to the test pieces. Then, the temperature of the measurement atmosphere was changed from 25 ° C. to 85 ° C. The amount of increase dL in length due to the temperature rise of the test piece was measured by raising the temperature to ° C. The linear expansion coefficient b was obtained by applying the length increase dL, the temperature change dT, and the initial length L of the sample piece to the following equation (1).
Formula (1): b = (dL / dT) / L
The obtained linear expansion coefficients (× 10 −5 / K) are shown in Table 1 above.
[0033]
[Return rate]
When the test piece prepared in the above “linear expansion coefficient” test is subjected to a cooling process of cooling to −40 ° C. with a 1 g load applied and a heating process of raising the temperature to 85 ° C., and at −40 ° C. The length at 85 ° C. was measured.
The temperature in the initial state was room temperature of 25 ° C., and the cooling treatment was first performed.
[0034]
Test piece length P 1 during the first cooling process (when cooled from 25 ° C. to −40 ° C.) and the second and third cooling processes (cooled from 85 ° C. to −40 ° C. ) Test piece lengths P 2 and P 3, and test piece lengths Q 1 and Q 2 during the first and second heat treatments (when heated from −40 ° C. to 85 ° C.) The low temperature return rate R 1 , R 2 (%) and the high temperature return rate S 1 (%)
R 1 = (P 2 −P 1 ) / P 1 × 100
R 2 = (P 3 −P 1 ) / P 1 × 100
S 1 = (Q 2 −Q 1 ) / Q 1 × 100
Sought by.
The total time required for one heat treatment and one cooling treatment was 30 minutes. The lower the return rate value, the higher the elasticity of the sample piece.
[0035]
〔Reliability test〕
Ten kinds of adhesives of Examples 1 to 7 and Comparative Examples 1 to 3 are applied to the first sticking object 11 made of white plate glass by a spin coat method to form a coating layer 14. After the PMMA resin film as the second object to be adhered 17 was adhered, ultraviolet rays were irradiated under the same irradiation conditions as in the “elongation rate” test, and 10 types of test pieces made of the laminate 10 were produced. These ten kinds of test pieces were observed while repeating the cooling treatment and the heat treatment under the same conditions as the “return rate”.
[0036]
The case where peeling or cracking (cracking) of the adhesive layer 15 was observed when the heating and cooling treatment was performed for less than 400 hours was evaluated as “NG”, and the case where the change in appearance did not occur after 400 hours was evaluated as “OK”. Table 1 shows the evaluation results and the time when the appearance change was confirmed.
[0037]
As is clear from Table 1 above, Examples 1 to 7 of the present invention have an elongation rate after curing of 200% or more, a large linear expansion coefficient, and sufficient flexibility. Moreover, in Examples 1-7, a return rate is also low enough, and it turns out that the adhesive agent after hardening has sufficient elasticity.
Further, as is clear from the results of the reliability test, the adhesives of Examples 1 to 7 having both flexibility and elasticity have higher durability due to temperature changes than Comparative Examples 1 to 3.
[0038]
Among these, Examples 1-6 in which the addition amount of the rubber component is 0.5 parts by weight or more and 15 parts by weight or less are compared with Example 7 in which the addition amount of the rubber component is 0.1 parts by weight. And a high result was obtained in the reliability test.
On the other hand, in the case of Comparative Example 1 which contains the same polymerizable component as in Examples 2 to 7, but does not contain a rubber component, the results of the linear expansion coefficient and elongation rate were similar to those in Examples 1 to 7, The return rate at each temperature was high.
[0039]
Moreover, in Comparative Examples 2 and 3 which contain a rubber component but the elongation percentage of the polymer obtained when the acrylic oligomer is homopolymerized is less than 150%, the value of the return rate of the elastic test is as in Examples 1 to 3. Although it was as low as 7, the linear expansion coefficient and elongation rate were low. In Comparative Examples 1 to 3, in which either the flexibility indicated by the linear expansion coefficient or the elasticity or the elasticity indicated by the return rate is not sufficient, the result of the reliability test is also bad. Peeling was observed, and in Comparative Examples 2 and 3, cracks were observed in the adhesive layer in 100 hours.
[0040]
The test was performed under the same conditions as in Comparative Examples 2 and 3 except that an acrylic oligomer (trade name “CN981” manufactured by Sartomer Co., Ltd.) having an elongation of 81% when homopolymerized was used. When a piece was produced, the linear expansion coefficient and elongation were low as in Comparative Examples 2 and 3.
[0041]
From these, the adhesive of the present invention has a high elongation rate and linear expansion coefficient after curing by using a specific polymerizable component, and has an appropriate elasticity after curing by adding a rubber component, As a result, it was confirmed that the reliability was high.
[0042]
The above describes the case where phenoxyethyl acrylate is used as an acrylic monomer, but the present invention is not limited to this, and various acrylates such as tetrahydrofurfuryl acrylate can be used. May be used, or a mixture of two or more types may be used.
[0043]
In addition, the acrylic oligomer is not limited to a low polymer of urethane acrylate, and various polymers such as ester acrylate, epoxy acrylate, and melamine acrylate can be used as long as the elongation rate of the polymer obtained by homopolymerization is 150% or more. A low polymer of acrylate can be used.
Also, the photopolymerization initiator is not particularly limited.
[0044]
The above describes the case where nitrile butadiene rubber is used as the rubber component, but besides nitrile butadiene rubber, for example, natural rubber, isopropylene rubber, butadiene rubber, 1, 2 polybutadiene rubber, styrene butadiene rubber, chloroprene rubber, butyl rubber Various rubbers can be used. These rubber components may be used alone or in combination of two or more.
[0045]
Moreover, the material which comprises the adhesive sticking target object is not limited to glass or resin. The resin constituting the object to be attached is not limited to PMMA, and various materials such as polyethylene terephthalate, polycarbonate, norbornene resin polymer, triacetyl cellulose, polyolefin, polypropylene, and the like can be used.
[0046]
The method of irradiating ultraviolet rays is not particularly limited, and if a sticking target that transmits ultraviolet rays is used, the ultraviolet rays can reach the adhesive by irradiating the sticking target with ultraviolet rays. .
Further, the irradiation condition of ultraviolet rays is not particularly limited, but if the irradiation amount of ultraviolet rays is too large, the polymerizable component and the rubber component are excessively polymerized and the elastic modulus is lost, so that the illuminance is 5 mW / cm. 2 above 1000 mW / cm 2 or less, and is preferably integrated light quantity is 300 mJ / cm 2 or more 5000 mJ / cm 2 or less.
[0047]
The above has described the case where the lenses that are the optical components 25 and 27 and the support member are bonded together, but the present invention is not limited to this, for example, bonding of a plurality of lenses made of different materials, It can be used for bonding various optical components such as a light receiving element and a hologram film.
[0048]
Further, the object to be attached is not limited to an optical component. According to the connection method of the present invention, for example, a liquid crystal panel and a polarizing plate used in a liquid crystal display device are bonded together, or a resin film and a glass plate are bonded. Can be pasted together. For example, if a resin film having flexibility and a glass plate are bonded together, a composite glass plate having excellent impact resistance can be obtained.
[0049]
【The invention's effect】
According to the present invention, since the elongation and the linear expansion coefficient after the adhesive is cured are high and have an appropriate elasticity, the adhesive can be used even when the objects to be adhered having different thermal expansion coefficients are bonded together. Does not peel off, and the positional displacement of the object to be stuck is unlikely to occur.
[Brief description of the drawings]
FIGS. 1A to 1D are cross-sectional views for explaining a process of bonding an object to be bonded using the adhesive of the present invention. FIG. 2 illustrates an example of an optical apparatus of the present invention. Figure [Explanation of symbols]
10: Optical device 14: Adhesive (adhesive coating layer)
15, 26 ... Adhesive layer (cured adhesive)
DESCRIPTION OF SYMBOLS 11 ... 1st sticking object 17 ... 2nd sticking object 20 ... Optical apparatus 25 ... 1st optical component 27 ... 2nd optical component

Claims (5)

重合性成分と、ゴム成分と、光重合開始剤とを含有し、紫外線の照射で前記重合性成分と前記ゴム成分とが重合するように構成された接着剤であって、
前記重合性成分は、アクリルモノマーであるフェノキシエチルアクリレートと、ウレタンアクリレートの低重合体であるアクリルオリゴマーを含有し、前記ゴム成分は、ニトリルブタジエンゴム含有し、
200mW/cm2の照度で300mJ/cm2の積算光量での紫外線照射による重合後の状態では、引張切断において、切断時の標線間距離L1と引張り前の標線間距離L0から、下記式、
N = (L1−L0)/L0×100
で求めた伸び率N(%)が200%以上であり、
前記アクリルオリゴマーを単独重合させた場合に得られるポリマーの前記伸び率N(%)は150%以上である接着剤。
An adhesive comprising a polymerizable component, a rubber component, and a photopolymerization initiator, and configured to polymerize the polymerizable component and the rubber component by irradiation with ultraviolet rays,
The polymerizable component contains a phenoxyethyl acrylate acrylic monomer, an acrylic oligomer is a low polymer of urethane acrylate, wherein the rubber component contains a nitrile-butadiene rubber,
In the state after polymerization by ultraviolet irradiation at an illuminance of 200 mW / cm 2 and an integrated light amount of 300 mJ / cm 2 , in tensile cutting, from the distance L 1 between marked lines at the time of cutting and the distance L 0 between marked lines before tension. , The following formula,
N = (L 1 −L 0 ) / L 0 × 100
The elongation rate N (%) obtained in the step is 200% or more,
The elongation N (%) adhesive Ru der least 150% of the polymer obtained in the case where the allowed homopolymerizing acrylic oligomer.
前記重合性成分100重量部に対する前記ニトリルブタジエンゴムの添加量は、0.5重量部以上である請求項1記載の接着剤。  The adhesive according to claim 1, wherein the amount of the nitrile butadiene rubber added to 100 parts by weight of the polymerizable component is 0.5 parts by weight or more. ガラスからなる第一の貼着対象物と、樹脂からなる第二の貼着対象物とを、請求項1又は請求項2のいずれか1項記載の接着剤からなる塗布層を介して密着させる工程と、
前記塗布層に紫外線を照射させ、前記塗布層を構成する接着剤を硬化させる工程とを有する貼着対象物の接続方法。
The first sticking object made of glass and the second sticking object made of resin are brought into close contact with each other via the coating layer made of the adhesive according to any one of claims 1 and 2. Process,
A method of connecting an object to be adhered, the method comprising: irradiating the coating layer with ultraviolet rays and curing an adhesive constituting the coating layer.
ガラスからなる第一の光学部品と、樹脂からなる第二の光学部品とを有し、前記第一の光学部品と前記第二の光学部品との間に、請求項1又は請求項2のいずれか1項記載の接着剤が配置され、前記接着剤が前記第一の光学部品と前記第二の光学部品の両方に密着した状態で、紫外線照射により前記接着剤が硬化された光学装置。A first optical component made of glass, and a second optical component made of a resin, between the first optical component and the second optical component one of the claims 1 or claim 2 An optical device in which the adhesive according to claim 1 is disposed, and the adhesive is cured by ultraviolet irradiation in a state where the adhesive is in close contact with both the first optical component and the second optical component. 前記第二の光学部品を構成する樹脂は、ポリメチルメタクリレートと、ポリエチレンテレフタレートと、ポリカーボネートと、ノルボルネン樹脂ポリマーとからなる群より選択される樹脂を含有する請求項4記載の光学装置。  5. The optical device according to claim 4, wherein the resin constituting the second optical component contains a resin selected from the group consisting of polymethyl methacrylate, polyethylene terephthalate, polycarbonate, and norbornene resin polymer.
JP2001344572A 2001-11-09 2001-11-09 Adhesive, method for connecting objects to be adhered, and optical device Expired - Lifetime JP4427216B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2001344572A JP4427216B2 (en) 2001-11-09 2001-11-09 Adhesive, method for connecting objects to be adhered, and optical device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2001344572A JP4427216B2 (en) 2001-11-09 2001-11-09 Adhesive, method for connecting objects to be adhered, and optical device

Publications (2)

Publication Number Publication Date
JP2003147281A JP2003147281A (en) 2003-05-21
JP4427216B2 true JP4427216B2 (en) 2010-03-03

Family

ID=19158074

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2001344572A Expired - Lifetime JP4427216B2 (en) 2001-11-09 2001-11-09 Adhesive, method for connecting objects to be adhered, and optical device

Country Status (1)

Country Link
JP (1) JP4427216B2 (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4833558B2 (en) * 2005-02-07 2011-12-07 パナソニック株式会社 Laser torch
TWI359850B (en) * 2007-08-30 2012-03-11 Ind Tech Res Inst Photo-sensitive adhesive for liquid crystal displa
JP6085078B2 (en) * 2008-08-19 2017-02-22 日立マクセル株式会社 Energy ray curable inkjet ink composition
TWI485214B (en) * 2008-09-05 2015-05-21 Kyoritsu Chemical Co Ltd And a photohardenable resin composition for bonding an optical functional material
JP5235619B2 (en) 2008-11-12 2013-07-10 キヤノン株式会社 Optical element and optical system having the same
US20110278797A1 (en) * 2010-05-12 2011-11-17 Freudenberg-Nok General Partnership Ultraviolet curable sealant compositions
KR101987441B1 (en) 2015-06-22 2019-06-11 주식회사 엘지화학 Adhesive sheet for optical use
KR102301938B1 (en) * 2017-10-20 2021-09-14 동우 화인켐 주식회사 Flexible Display Device

Also Published As

Publication number Publication date
JP2003147281A (en) 2003-05-21

Similar Documents

Publication Publication Date Title
JP4468972B2 (en) Microstructure-containing products
KR101915337B1 (en) Multilayer adhesive and bonding film for curved substrates
JP2009104002A (en) Protective film for image display device, and image display device including the same
JP4158409B2 (en) Manufacturing method of optical disc
JP4427216B2 (en) Adhesive, method for connecting objects to be adhered, and optical device
JP5192542B2 (en) Manufacturing method of sheet having through hole / uneven pattern
JP5271486B2 (en) Release agent, method for forming concave / convex pattern using the same, method for producing optical information recording medium, and optical information recording medium
JP4479907B2 (en) Photocurable transfer sheet, method for producing optical information recording medium using the same, and optical information recording medium
JP2007017521A (en) Resin sheet for manufacturing planar optical waveguide
CN115003769B (en) Dual cure adhesive composition
JP4165635B2 (en) Manufacturing method of optical information recording medium
JPS63167301A (en) Transmission type screen
JP4764173B2 (en) Photocurable transfer sheet, method for producing optical information recording medium using the same, and optical information recording medium
JP4658858B2 (en) Photocurable transfer sheet, method for producing optical information recording medium using the same, and optical information recording medium
JP2947812B2 (en) Replica plate, method of manufacturing the same, and projection television using the same
JP4764158B2 (en) Photocurable transfer sheet, method for producing optical information recording medium using the same, and optical information recording medium
JP5016368B2 (en) Photocurable transfer sheet, method for producing optical information recording medium using the same, and optical information recording medium
JP4262669B2 (en) Optical disk resin composition, dry film, sheet
KR102516093B1 (en) Coating method
JP4833737B2 (en) Photocurable transfer sheet, method for producing optical information recording medium using the same, and optical information recording medium
JP5158923B2 (en) Photocurable transfer sheet, method for producing optical information recording medium using the same, and optical information recording medium
JP4070440B2 (en) Optical information recording medium and manufacturing method thereof
JP4656991B2 (en) Photocurable transfer sheet, method for producing optical information recording medium using the same, and optical information recording medium
JPS58119859A (en) Manufacture of synthetic resin laminate
JPH04151242A (en) Plastic component and optical component

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20040513

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20060824

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20060829

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A821

Effective date: 20061030

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20061030

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20061128

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20070129

Free format text: JAPANESE INTERMEDIATE CODE: A821

Effective date: 20070129

A911 Transfer to examiner for re-examination before appeal (zenchi)

Free format text: JAPANESE INTERMEDIATE CODE: A911

Effective date: 20070209

A912 Re-examination (zenchi) completed and case transferred to appeal board

Free format text: JAPANESE INTERMEDIATE CODE: A912

Effective date: 20070302

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A821

Effective date: 20090306

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20091008

Free format text: JAPANESE INTERMEDIATE CODE: A821

Effective date: 20091008

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20091214

R150 Certificate of patent or registration of utility model

Ref document number: 4427216

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20121218

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20121218

Year of fee payment: 3

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20131218

Year of fee payment: 4

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

EXPY Cancellation because of completion of term