JP2004091499A - Pressure-sensitive adhesive composition for optical member and pressure-sensitive adhesive sheet for optical member using the same pressure-sensitive adhesive composition - Google Patents
Pressure-sensitive adhesive composition for optical member and pressure-sensitive adhesive sheet for optical member using the same pressure-sensitive adhesive composition Download PDFInfo
- Publication number
- JP2004091499A JP2004091499A JP2002250458A JP2002250458A JP2004091499A JP 2004091499 A JP2004091499 A JP 2004091499A JP 2002250458 A JP2002250458 A JP 2002250458A JP 2002250458 A JP2002250458 A JP 2002250458A JP 2004091499 A JP2004091499 A JP 2004091499A
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- weight
- parts
- adhesive composition
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/24—Homopolymers or copolymers of amides or imides
- C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Polyurethanes Or Polyureas (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【0001】
【発明の属する技術分野】
本発明は、透明性を要求される光学部材用粘着剤組成物、及び、この粘着剤組成物を用いた光学部材用粘着シートに関し、さらに詳しくは、特定のアクリル系共重合体と特定のイソシアネート硬化剤を含有する光学部材用粘着剤、及び、この粘着剤組成物を使用した粘着剤層を支持体の片面又は両面に設けた光学部材用粘着シートに関するものである。
【0002】
【従来の技術】
液晶ディスプレイ(LCD)やプラズマディスプレイパネル(PDP)などのフラットパネルディスプレイ(FPD)が、様々な分野で表示装置として使用されている。これらの表示装置には、外部光源からの反射を防ぐための反射防止フィルムや表示装置の擦過による傷の防止のためのプロテクトフィルムなどが使用されている。
また、カソードレイチューブ(CRT)やFPDを表示装置として利用するだけでなく、それらの表面にタッチパネルを設けて、入力装置としても利用されている。このタッチパネルにも、保護フィルム、反射防止フィルムやITO蒸着樹脂フィルムなどが使用されている。
【0003】
これらのフィルムは、粘着剤(感圧性接着剤)により貼着され使用されているが、高透明性及び高耐久性などが要求されるために、その粘着剤としては主としてアクリル系粘着剤が使用されている。さらに、LCDでは偏光板や位相差板を積層する際にもアクリル系粘着剤が使用されている。
アクリル系粘着剤としては、アルキル基の炭素数が1〜20のアクリル酸アルキルエステルを主成分としアクリル酸などの官能基含有単量体及び共重合可能なその他のモノマーを共重合させたアクリル系ポリマー、そのアクリル系ポリマーが有する官能基と反応性を有する有機基を分子内に2個以上有する架橋剤、及び、場合によっては粘着付与樹脂などを添加したものが多く、アクリル系ポリマーの単量体配合、アクリル系ポリマーの分子量や分子量分布、架橋剤及び粘着付与樹脂の配合量などを適宜選択することにより、その粘着特性を調製している。
【0004】
このアクリル系粘着剤の架橋剤としては、イソシアネート化合物、エポキシ化合物、アミン化合物、アジリジン化合物、メラミン化合物及び金属キレートなどが知られているが、中でもイソシアネート化合物は架橋反応後の粘着剤のタック感及び被着体への接着性に優れていることから広く使用されている。
しかしながら、架橋剤としてイソシアネート化合物を使用したアクリル系粘着剤は、他の架橋剤を使用したアクリル系粘着剤と比較すると、架橋後のウレタン構造に基因して耐光性、透明性が低下する傾向にあり、粘着剤組成物の養生(エージング)時間が長く、芳香族イソシアネート化合物を使用すると得られる粘着剤が黄変しやすく、脂肪族又は脂環族イソシアネート化合物を使用すると白化しやすい。
【0005】
こうした中で、特開平7−324183号公報には、ポリイソシアネート化合物とポリオールとの反応生成物であって、3級炭素に結合したイソシアネート基を少なくとも2個以上有するポリイソシアネート変性物と、遊離のカルボキシル基を含有するアクリル系共重合体とからなる粘着剤組成物が、十分満足できるポットライフを有し、塗膜の耐候性及び透明性に優れることが開示されている。しかしながら、この粘着剤組成物は支持体に塗布した後の架橋反応が遅く、粘着性能が安定するまでにかなりの時間がかかるため、生産性の向上の市場要求を満足していない。
【0006】
【発明が解決しようとする課題】
本発明は、透明性、耐光性及び耐候性を満足するだけでなく、経時的な黄変が無く、塗布(粘着加工)後の養生時間の短い、アクリル系光学部材用粘着剤組成物及びそれを用いた光学用粘着シートを提供することを課題としている。
【0007】
【課題を解決するための手段】
本発明の光学部材用粘着剤組成物は、単量体成分(a)(メタ)アクリル酸アルキルエステル100重量部に対して、単量体成分(b)分子内に水酸基を有する単量体0.1〜10重量部と、単量体成分(c)分子内に、カルボキシル基、アミド基、アミノ基の何れかの官能基を有する単量体0.05〜3重量部とを含有する単量体混合物の共重合体であり、ゲルパーミュエーションクロマトグラフィーによる重量平均分子量が50万以上200万以下のアクリル系ポリマー100重量部と、ポリオール変性キシリレンジイソシアネート架橋剤0.01〜5重量部とからなる。また、前記アクリル系ポリマーは、溶液重合又は塊状重合により得られたものが好ましい。
本発明の光学用粘着シートは、支持体の片面又は両面に、前記光学部材用粘着剤組成物からなる粘着剤層を形成したものである。
【0008】
【発明の実施の形態】
本発明の光学部材用粘着剤に使用するアクリル系ポリマーは、単量体成分(a)(メタ)アクリル酸アルキルエステル100重量部に対して、単量体成分(b)分子内に水酸基を有する単量体0.1〜10重量部と、単量体成分(c)分子内に、カルボキシル基、アミド基、アミノ基の何れかの官能基を有する単量体0.05〜3重量部とを含有する単量体混合物の共重合体である。
【0009】
単量体混合物の単量体成分(a)(メタ)アクリル酸アルキルエステルの例としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、n−ブチル(メタ)アクリレート、iso−ブチル(メタ)アクリレート、t−ブチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、n−オクチル(メタ)アクリレート、iso−オクチル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート等を挙げることができる。(メタ)アクリル酸はアクリル酸とメタクリル酸の両方を意味し、(メタ)アクリレートはアクリレートとメタクリレートの両方を意味する。
【0010】
単量体混合物の単量体成分(b)分子内に水酸基を有する単量体の例としては、2−ヒドロキシエチル(メタ)アクリレート、4−ヒドロキシブチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、2−ヒドロキシブチル(メタ)アクリレート、6−ヒドロキシヘキシル(メタ)アクリレート、1,4−シクロヘキサンジメタノールモノ(メタ)アクリレート、クロロ−2−ヒドロキシプロピルアクリレート、ジエチレングリコールモノ(メタ)アクリレート、アリルアルコール等を挙げることができる。
【0011】
単量体混合物の単量体成分(c)分子内にカルボキシル基、アミド基、アミノ基の何れかの官能基を有する単量体の例としては、(メタ)アクリル酸、2−カルボキシエチル(メタ)アクリレート、3−カルボキシプロピル(メタ)アクリレート、4−カルボキシブチル(メタ)アクリレート、イタコン酸、クロトン酸、マレイン酸、フマル酸及び無水マレイン酸等のカルボキシル基含有単量体;(メタ)アクリルアミド、N,N−ジメチル(メタ)アクリルアミド、N−イソプロピル(メタ)アクリルアミド、N,N−ジエチル(メタ)アクリルアミド、アクリロイルモルホリン、N−ビニルアセトアミド、ダイアセトン(メタ)アクリルアミド、N,N−ジメチルアミノプロピル(メタ)アクリルアミド、ビニルピロリドン、メチロール(メタ)アクリルアミド、メトキシエチル(メタ)アクリルアミド等のアミド基含有単量体;N,N−ジメチルアミノエチル(メタ)アクリレート、N,N−ジエチルアミノエチル(メタ)アクリルアミド、N,N−ジメチルアミノプロピル(メタ)アクリルアミド、モノホリノエチル(メタ)アクリレート等のアミノ基含有単量体などを挙げることができる。
【0012】
単量体成分(c)分子内にカルボキシル基、アミド基、アミノ基の何れかの官能基を有する単量体の官能基は、拡散フィルム、反射防止フィルム、ガラス飛散防止フィルムなどの紫外線を受ける場合は、アミノ基及びアミド基がより好ましく、LCDに使用される偏光板や位相差板の貼着には、カルボキシル基がより好ましい。
【0013】
前記単量体混合物の配合量は、単量体成分(a)100重量部に対して、単量体成分(b)0.1重量部以上10重量部以下、単量体成分(c)0.05重量部以上3重量部以下であるが、好ましくは、成分(a)100重量部に対して、成分(b)0.5重量部以上5重量部以下、成分(c)0.05重量部以上2重量部以下である。単量体成分(a)〜(c)をこの数値範囲にすることにより、後述するポリオール変性キシリレンジイソシアネートとの架橋反応が速やかに進行する。
【0014】
前記単量体混合物には、必要に応じて、その他の単量体(d)を混合させても良い。その他の単量体の例としては、メトキシエチル(メタ)アクリレート及びエトキシエチル(メタ)アクリレート等のアルコキシアルキル(メタ)アクリレート;グリシジル(メタ)アクリレート等のエポキシ基含有(メタ)アクリレート;アセトアセトキシエチル(メタ)アクリレート等のアセトアセチル基含有(メタ)アクリレート;スチレン、メチルスチレン及びビニルトルエン等の芳香族単量体;メタクリロキシプロピルメトキシシラン、酢酸ビニル、塩化ビニル並びに(メタ)アクリロニトリル等を挙げることができる。その他の単量体(d)の混合比は、単量体成分(a)アクリル酸アルキルエステル100重量部に対して、50重量部以下、好ましくは30重量部以下、特に好ましくは10重量部以下である。
【0015】
本発明の光学部材用粘着剤組成物に使用する前記アクリル系ポリマーは、前記単量体混合物を、溶液重合法、塊状重合法、乳化重合法及び懸濁重合法等の従来公知の重合法により製造することができるが、乳化剤や懸濁剤等の重合安定剤を含まない溶液重合法及び塊状重合法により製造したものが好ましい。また、前記アクリル系ポリマーのゲルパーミュエーションクロマトグラフィー(GPC)による重量平均分子量(Mw)は、50万以上200万以下であり、好ましくは60万以上180万以下である。Mwが、50万未満であると、接着耐久性が不十分であり、Mwが200万を超えると、支持体(基材)の伸縮に対する追従性が悪くなり、被着体からのハガレ等が生じやすくなる。
【0016】
本発明の光学部材用粘着剤組成物に使用するポリオール変性キシリレンジイソシアネートは、キシリレンジイソシアネートとポリオールの反応生成物であり、ポリオールとしては、エチレングリコール、ジ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、プロパンジオール、プロパントリオール、ブタンジオール、ブタントリオール、ヘキサンジオール、ヘキサントリオール、ペンタエリスリトール、トリメチロールプロパン、ジペンタエリスリトールなどのほか、ポリエーテルポリオールやポリエステルポリオール、アクリルポリオール、ポリブタジエンポリオール、ポリイソプレンポリオールなどを挙げることができる。中でも、トリメチロールプロパン1モルに対してキシリレンジイソシアネートを3モル付加させたトリメチロールプロパン変性キシリレンジイソシアネートが好ましい。
【0017】
前記アクリル系ポリマーと前記ポリオール変性キシリレンジイソシアネートの混合は、前記アクリル系ポリマーを溶液重合により調製した場合は、重合完了後のアクリル系ポリマー溶液にイソシアネート化合物を添加すれば良く、前記アクリル系ポリマーを塊状重合により調製する場合は、重合完了後では均一混合が困難になるため、重合の途中で混合することが好ましい。
前記アクリル系ポリマーと前記ポリオール変性キシリレンジイソシアネートとの混合比は、アクリル系ポリマー100重量部に対してポリオール変性キシリレンジイソシアネート0.01〜5重量部が好ましく、0.05〜1重量部が特に好ましい。
本発明の光学部材用粘着剤組成物には、本発明の効果を損なわない範囲で有れば、シランカップリング剤、酸化防止剤、紫外線吸収剤、粘着付与剤、可塑剤等を配合しても良い。
【0018】
本発明の光学部材用粘着シートは、支持体の片面あるいは両面に、前記光学部材用粘着剤組成物からなる粘着剤層を設けたものである。粘着剤層は、従来公知の方法で設ければよい。支持体としては、偏光フィルム、位相差フィルム、楕円偏光フィルム、反射防止フィルム、輝度向上フィルム、光拡散フィルム、ガラス飛散防止及び表面保護フィルム等が挙げられる。
【実施例】
本発明を実施例を示してさらに具体的に説明するが、本発明はこれらによって限定されるものではない。
【0019】
<製造例1>アクリル系ポリマー溶液A
n−ブチルアクリレート100重量部、2−ヒドロキシエチルアクリレート4重量部、アクリル酸0.5重量部、酢酸エチル90重量部および過酸化ベンゾイル0.1重量部を反応容器に入れ、この反応容器内の空気を窒素ガスで置換した。ついで、撹拌下に70℃に昇温して8時間反応させ、アクリル系ポリマー溶液Aを得た。得られたアクリル系ポリマーAのGPCによるMwは120万であった。
【0020】
<製造例2>アクリル系ポリマー溶液B
n−ブチルアクリレート100重量部、2−ヒドロキシエチルアクリレート2重量部、アクリルアミド1重量部、酢酸エチル100重量部およびアゾビスイソブチロニトリル0.2重量部を反応容器に入れ、この反応容器内の空気を窒素ガスで置換した。ついで、撹拌下に60℃に昇温して4時間反応させた。4時間後、トルエン100重量部、α−メチルスチレンダイマー5重量部、アゾビスイソブチロニトリル2重量部を加え、90℃に昇温し、さらに4時間反応させ、アクリル系ポリマー溶液Bを得た。得られたアクリル系ポリマーBのGPCによるMwは70万であった。
【0021】
<製造例3>アクリル系ポリマー溶液C
2−エチルヘキシルアクリレート100重量部、4−ヒドロキシブチルアクリレート0.5重量部、アクリルアミド2.5重量部、酢酸エチル90重量部および過酸化ベンゾイル0.07重量部を反応容器に入れ、この反応容器内の空気を窒素ガスで置換した。ついで、撹拌下に73℃に昇温して8時間反応させ、アクリル系ポリマー溶液Cを得た。得られたアクリル系ポリマーCのGPCによるMwは140万であった。
【0022】
<製造例4>アクリル系ポリマー溶液D
製造例1において、アクリル酸を4重量部に変更した以外は、製造例1と同様にしてアクリル系ポリマー溶液Dを得た。得られたアクリル系ポリマーEのGPCによるMwは130万であった。
【0023】
<製造例5>アクリル系ポリマー溶液E
製造例1において、アクリル酸をなくした以外は、製造例1と同様にしてアクリル系ポリマー溶液Eを得た。得られたアクリル系ポリマーFのGPCによるMwは120万であった。
【0024】
<製造例6>アクリル系ポリマー溶液F
製造例1において、2−ヒドロキシエチルアクリレートを0.05重量部に変更した以外は、製造例1と同様に反応させ、アクリル系ポリマー溶液Fを得た。得られたアクリル系ポリマーEのGPCによるMwは110万であった。
【0025】
<製造例7>アクリル系ポリマー溶液G
製造例1において、2−ヒドロキシエチルアクリレートを12重量部に変更した以外は、製造例1と同様に反応させ、アクリル系ポリマー溶液Gを得た。得られたアクリル系ポリマーHのGPCによるMwは140万であった。
【0026】
<製造例8>アクリル系ポリマー溶液H
製造例1において、酢酸エチル90重量部を酢酸エチル10重量部、トルエン80重量部に変更した以外は、製造例1と同様に反応させ、アクリル系ポリマー溶液Iを得た。得られたアクリル系ポリマーHのGPCによるMwは30万であった。
【0027】
<製造例9>塊状重合によるアクリル系ポリマーの製造
第1工程として、2−エチルヘキシルアクリレート100重量部、2−ヒドロキシエチルメタクリレート2重量部、ジメチルアミノエチルアクリレート1重量部を反応容器に入れ、この反応容器内の空気を窒素ガスで置換した後、撹拌下に50℃に昇温させた。ついで、2,2’−アゾビス(4−メトキシ−2,4−ジメチルバレロニトリル)0.025重量部を加えたところ、反応系の温度が上昇し、冷却を行わずに重合反応を進めたところ、反応系の温度が119℃まで達し、その後徐々に下がり始めた。2−エチルヘキシルアクリレート20重量部、2−ヒドロキシエチルメクリレート0.4重量部、ジメチルアミノエチルアクリレート0.2重量部を投入して、反応系の温度を110℃まで冷却した。さらに、水浴により室温まで冷却し、アクリル系部分重合物を得た。
次いで、第2工程として、このアクリル系部分重合物100重量部に、光重合開始剤(商品名:ダロキュア1173、チバガイギー(株)製)0.3重量部を添加し、よく撹拌して重合性組成物を得た。それを剥離処理したポリエステルフィルムに塗布し、窒素ガス雰囲気下において、10W/m2で360秒間、その後3000W/m2で45秒間、高圧水銀ランプより光を照射して光重合を行い、25μmのアクリル系ポリマー層を設けた。このアクリル系ポリマー層のGPCによるMwは115万であった。
【0028】
GPCの測定条件を表1に示す。
【表1】
【0029】
<実施例1>
アクリル系ポリマー溶液Aの固形分100重量部に、トリメチロールプロパンのトリレンジイソシアネート付加物0.05重量部を添加し、よく撹拌して粘着剤組成物を得た。それを剥離処理したポリエステルフィルムに塗布し乾燥させ、25μmの粘着剤層を設けた後、それを偏光フィルムの片面に転写し、温度23℃、湿度65%の条件で熟成させた。
【0030】
<実施例2>
アクリル系ポリマー溶液Bの固形分100重量部に、トリメチロールプロパンのキシリレンジイソシアネート0.7重量部を添加し、よく撹拌して粘着剤組成物を得た。それを剥離処理したポリエステルフィルムに塗布し乾燥させ、25μmの粘着剤層を設けた後、それを偏光フィルムの片面に転写し、温度23℃、湿度65%の条件で熟成させた。
【0031】
<実施例3>
アクリル系ポリマー溶液Cの固形分100重量部に、トリメチロールプロパンのキシリレンジイソシアネート付加物0.1重量部を添加し、よく撹拌して粘着剤組成物を得た。それを剥離処理したポリエステルフィルムに塗布し乾燥させ、25μmの粘着剤層を設けた後、それを偏光フィルムの片面に転写し、温度23℃、湿度65%の条件で熟成させた。
【0032】
<実施例4>
製造例9において、第2工程の重合性組成物を、アクリル系部分重合物100重量部に対して、トリメチロールプロパンのキシリレンジイソシアネート付加物0.5重量部をさらに添加した以外は同様にして、剥離処理したポリエステルフィルム上に25μmの粘着剤層を得た。それを偏光フィルムの片面に転写し、温度23℃、湿度65%の条件で熟成させた。
【0033】
<比較例1>
実施例1において、アクリル系ポリマー溶液Aをアクリルポリマー溶液Dに変更した以外は、実施例1と同様にした。
【0034】
<比較例2>
実施例1において、アクリル系ポリマー溶液Aをアクリルポリマー溶液Eに変更した以外は、実施例1と同様にした。
【0035】
<比較例3>
実施例1において、アクリル系ポリマー溶液Aをアクリルポリマー溶液Fに変更した以外は、実施例1と同様にした。
【0036】
<比較例4>
実施例1において、アクリル系ポリマー溶液Aをアクリルポリマー溶液Gに変更した以外は、実施例1と同様にした。
【0037】
<比較例5>
実施例1において、アクリル系ポリマー溶液Aをアクリルポリマー溶液Hに変更した以外は、実施例1と同様にした。
【0038】
<比較例6>
実施例1において、トリメチロールプロパンのキシリレンジイソシアネート付加物を0.001重量部に変更した以外は、実施例1と同様にした。
【0039】
<比較例7>
実施例1において、トリメチロールプロパンのキシリレンジイソシアネート付加物を6重量部に変更した以外は、実施例1と同様にした。
【0040】
<比較例8>
【0041】
実施例1において、トリメチロールプロパンのキシリレンジイソシアネート付加物をトリメチロールプロパンのヘキサメチレンジイソシアネートに変更した以外は、実施例1と同様にした。
【0042】
<比較例9>
【0043】
実施例1において、トリメチロールプロパンのキシリレンジイソシアネート付加物をトリメチロールプロパンのトリレンジイソシアネートに変更した以外は、実施例1と同様にした。
【0044】
〈評価試験〉
ゲル分率
粘着剤組成物を塗工後、1、3、5、7、10、15日におけるゲル分率を測定した。
ゲル分率は、支持体上で温度23℃、湿度65%RHの条件で熟成させている粘着剤の約0.1gをサンプル瓶に採取し、酢酸エチルを30cc加えて24時間振とうした後、該サンプル瓶の内容物を200メッシュのステンレス製金網にてろ別し、金網上の残留物を100℃で2時間乾燥させて乾燥重量を測定し、次式[I]より求めた。結果を表2に示す。
【式1】
【表2】
【0045】
黄変性
上記実施例1〜4、比較例1〜9において、偏光フィルムの代わりに25μmポリエステルフィルムを用いて光学部材用粘着シートを作成した。温度23℃、湿度65%RHで7日間熟成して得られた粘着シートを、100℃の乾燥機中に15日間静置した後、色の変化を目視で観察した。結果を表2に示す。「○」は黄変していないことを示し、「△」は僅かに黄変がみられることを示し、「×」は黄変が顕著であることを示す。
ポットライフ
上記実施例1〜4、比較例1〜9において、得られた粘着剤組成物を温度23℃、湿度65%の条件で静置し、粘着剤組成物調製後から粘度の上昇が発生するまでの時間を観察した。結果を表2に示す。「◎」は12時間以上、「○」は6時間以上〜12時間未満、「×」は6時間未満であることを示す。
【0046】
耐久性
上記実施例1〜4、比較例1〜9において、得られた光学部材用粘着シートを厚さ0.5mmの無アルカリガラス板の片面にラミネータロールを用いて貼り付けた。次いで、50℃、5気圧のオートクレーブに20分保持して接着させた。
こうして得られた試料を100℃、60℃90%RHの条件下に500時間放置し、光学部材の剥離、接着界面での発泡を目視にて観察した。結果を表3に示す。表中の「○」は実用上問題ないことを意味し、「△」は実用に問題が発生する可能性があることを意味し、「×」は実用に問題があることを示す。
【表3】
【0047】
【発明の効果】
本発明の光学部材用粘着剤は、前記実施例で示した如く、黄変性に優れ、工業的に十分なポットライフを有するだけでなく、従来の粘着剤組成物と比較して、塗工後、速やかに架橋構造が完結しゲル分率が安定するために、短時間で粘着特性が安定する。そして、本発明の光学部材用粘着剤を使用した本発明の光学部材用粘着シートは、粘着加工(塗工)後、速やかに使用することができ、生産性を大幅に向上させるものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a pressure-sensitive adhesive composition for an optical member requiring transparency, and a pressure-sensitive adhesive sheet for an optical member using the pressure-sensitive adhesive composition. More specifically, a specific acrylic copolymer and a specific isocyanate The present invention relates to a pressure-sensitive adhesive for optical members containing a curing agent, and a pressure-sensitive adhesive sheet for optical members provided with a pressure-sensitive adhesive layer using the pressure-sensitive adhesive composition on one or both sides of a support.
[0002]
[Prior art]
2. Description of the Related Art Flat panel displays (FPDs) such as liquid crystal displays (LCDs) and plasma display panels (PDPs) are used as display devices in various fields. In these display devices, an antireflection film for preventing reflection from an external light source, a protection film for preventing scratches due to abrasion of the display device, and the like are used.
In addition to using a cathode ray tube (CRT) or an FPD as a display device, a touch panel is provided on the surface thereof, and the touch panel is also used as an input device. Also in this touch panel, a protective film, an antireflection film, an ITO vapor-deposited resin film, and the like are used.
[0003]
These films are used by being adhered with an adhesive (pressure-sensitive adhesive). However, since high transparency and high durability are required, acrylic adhesives are mainly used as the adhesive. Have been. Further, in the LCD, an acrylic pressure-sensitive adhesive is also used when laminating a polarizing plate or a retardation plate.
As the acrylic pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive obtained by copolymerizing a functional group-containing monomer such as acrylic acid and other copolymerizable monomers with an alkyl acrylate having an alkyl group having 1 to 20 carbon atoms as a main component. Polymers, cross-linking agents having two or more organic groups reactive with the functional groups of the acrylic polymer in the molecule, and, in some cases, a tackifier resin, etc., are often added. The adhesive properties are adjusted by appropriately selecting the body composition, the molecular weight and molecular weight distribution of the acrylic polymer, and the blending amounts of the crosslinking agent and the tackifying resin.
[0004]
Known crosslinking agents for the acrylic pressure-sensitive adhesive include isocyanate compounds, epoxy compounds, amine compounds, aziridine compounds, melamine compounds, and metal chelates. It is widely used because of its excellent adhesion to adherends.
However, acrylic pressure-sensitive adhesives using isocyanate compounds as cross-linking agents tend to have lower light resistance and transparency due to the urethane structure after cross-linking than acrylic pressure-sensitive adhesives using other cross-linking agents. Yes, the curing (aging) time of the pressure-sensitive adhesive composition is long, the pressure-sensitive adhesive obtained when an aromatic isocyanate compound is used is apt to yellow, and when an aliphatic or alicyclic isocyanate compound is used, it is easy to whiten.
[0005]
Under these circumstances, JP-A-7-324183 discloses a modified product of a polyisocyanate, which is a reaction product of a polyisocyanate compound and a polyol and has at least two isocyanate groups bonded to a tertiary carbon, It is disclosed that a pressure-sensitive adhesive composition comprising a carboxyl group-containing acrylic copolymer has a sufficiently satisfactory pot life and is excellent in weather resistance and transparency of a coating film. However, since the pressure-sensitive adhesive composition has a slow cross-linking reaction after being applied to a support and takes a considerable amount of time to stabilize the pressure-sensitive adhesive performance, it does not satisfy the market demand for improving productivity.
[0006]
[Problems to be solved by the invention]
The present invention provides a pressure-sensitive adhesive composition for an acrylic optical member, which not only satisfies transparency, light resistance, and weather resistance, does not yellow over time, and has a short curing time after application (adhesion processing). It is an object of the present invention to provide an optical pressure-sensitive adhesive sheet using the same.
[0007]
[Means for Solving the Problems]
The pressure-sensitive adhesive composition for an optical member of the present invention comprises a monomer component (b) having a hydroxyl group in the molecule per 100 parts by weight of the monomer component (a) alkyl (meth) acrylate. 0.1 to 10 parts by weight, and 0.05 to 3 parts by weight of a monomer having any one of a carboxyl group, an amide group and an amino group in the molecule of the monomer component (c). 100 parts by weight of an acrylic polymer having a weight average molecular weight of 500,000 to 2,000,000 by gel permeation chromatography, and 0.01 to 5 parts by weight of a polyol-modified xylylene diisocyanate crosslinking agent. Consists of Further, the acrylic polymer is preferably obtained by solution polymerization or bulk polymerization.
The optical pressure-sensitive adhesive sheet of the present invention is obtained by forming a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition for an optical member on one or both surfaces of a support.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
The acrylic polymer used in the pressure-sensitive adhesive for an optical member of the present invention has a hydroxyl group in the molecule of the monomer component (b) with respect to 100 parts by weight of the monomer component (a) (meth) alkyl acrylate. 0.1 to 10 parts by weight of a monomer and 0.05 to 3 parts by weight of a monomer having any one of a carboxyl group, an amide group and an amino group in the molecule of the monomer component (c). Is a copolymer of a monomer mixture containing
[0009]
Examples of the monomer component (a) alkyl (meth) acrylate of the monomer mixture include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) Acrylate and the like can be mentioned. (Meth) acrylic acid means both acrylic acid and methacrylic acid, and (meth) acrylate means both acrylate and methacrylate.
[0010]
Examples of the monomer having a hydroxyl group in the molecule of the monomer component (b) of the monomer mixture include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl (meth). A) acrylate, 2-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, chloro-2-hydroxypropyl acrylate, diethylene glycol mono (meth) acrylate, allyl Alcohol and the like can be mentioned.
[0011]
Examples of the monomer having any one of a carboxyl group, an amide group and an amino group in the molecule of the monomer component (c) of the monomer mixture include (meth) acrylic acid, 2-carboxyethyl ( Carboxyl group-containing monomers such as (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, itaconic acid, crotonic acid, maleic acid, fumaric acid and maleic anhydride; (meth) acrylamide , N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, acryloylmorpholine, N-vinylacetamide, diacetone (meth) acrylamide, N, N-dimethylamino Propyl (meth) acrylamide, vinylpyrrolidone, methylol Amide group-containing monomers such as meth) acrylamide and methoxyethyl (meth) acrylamide; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl ( Examples include amino group-containing monomers such as (meth) acrylamide and monophorinoethyl (meth) acrylate.
[0012]
Monomer component (c) The functional group of a monomer having any one of a carboxyl group, an amide group and an amino group in the molecule receives ultraviolet rays such as a diffusion film, an antireflection film, and a glass shatterproof film. In this case, an amino group and an amide group are more preferable, and a carboxyl group is more preferable for sticking a polarizing plate or a retardation plate used for LCD.
[0013]
The compounding amount of the monomer mixture is 0.1 to 10 parts by weight of monomer component (b) and 0 to 10 parts by weight of monomer component (c) per 100 parts by weight of monomer component (a). 0.05 to 3 parts by weight, preferably 0.5 to 5 parts by weight of component (b) and 0.05 parts by weight of component (c) per 100 parts by weight of component (a). To 2 parts by weight. By setting the monomer components (a) to (c) within this numerical range, a crosslinking reaction with a polyol-modified xylylene diisocyanate described below proceeds promptly.
[0014]
The monomer mixture may be mixed with another monomer (d) as necessary. Examples of other monomers include alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate; acetoacetoxyethyl (Meth) acrylates containing an acetoacetyl group such as (meth) acrylate; aromatic monomers such as styrene, methylstyrene and vinyltoluene; methacryloxypropylmethoxysilane, vinyl acetate, vinyl chloride, and (meth) acrylonitrile. Can be. The mixing ratio of the other monomer (d) is at most 50 parts by weight, preferably at most 30 parts by weight, particularly preferably at most 10 parts by weight, based on 100 parts by weight of the monomer component (a) alkyl acrylate. It is.
[0015]
The acrylic polymer used in the pressure-sensitive adhesive composition for an optical member of the present invention, the monomer mixture, solution polymerization method, bulk polymerization method, emulsion polymerization method and suspension polymerization method by a conventionally known polymerization method such as Although it can be produced, those produced by a solution polymerization method and a bulk polymerization method which do not contain a polymerization stabilizer such as an emulsifier or a suspending agent are preferable. The weight average molecular weight (Mw) of the acrylic polymer measured by gel permeation chromatography (GPC) is from 500,000 to 2,000,000, preferably from 600,000 to 1,800,000. If the Mw is less than 500,000, the adhesion durability is insufficient, and if the Mw exceeds 2,000,000, the ability to follow the expansion and contraction of the support (substrate) is deteriorated, and peeling from the adherend is reduced. It is easy to occur.
[0016]
The polyol-modified xylylene diisocyanate used in the pressure-sensitive adhesive composition for an optical member of the present invention is a reaction product of xylylene diisocyanate and a polyol.As the polyol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, In addition to propanediol, propanetriol, butanediol, butanetriol, hexanediol, hexanetriol, pentaerythritol, trimethylolpropane, dipentaerythritol, etc., polyether polyol, polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol, etc. Can be mentioned. Among them, trimethylolpropane-modified xylylenediisocyanate obtained by adding 3 mol of xylylenediisocyanate to 1 mol of trimethylolpropane is preferable.
[0017]
Mixing of the acrylic polymer and the polyol-modified xylylene diisocyanate, when the acrylic polymer is prepared by solution polymerization, an isocyanate compound may be added to the acrylic polymer solution after completion of the polymerization, and the acrylic polymer In the case of preparing by bulk polymerization, it is difficult to uniformly mix after completion of the polymerization, and therefore it is preferable to mix during the polymerization.
The mixing ratio of the acrylic polymer and the polyol-modified xylylene diisocyanate is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 1 part by weight, based on 100 parts by weight of the acrylic polymer. preferable.
The pressure-sensitive adhesive composition for an optical member of the present invention contains a silane coupling agent, an antioxidant, an ultraviolet absorber, a tackifier, a plasticizer, and the like, as long as the effects of the present invention are not impaired. Is also good.
[0018]
The pressure-sensitive adhesive sheet for an optical member of the present invention is provided with a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition for an optical member on one or both surfaces of a support. The pressure-sensitive adhesive layer may be provided by a conventionally known method. Examples of the support include a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, a brightness enhancement film, a light diffusion film, a glass scattering prevention and a surface protection film, and the like.
【Example】
The present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
[0019]
<Production Example 1> Acrylic polymer solution A
100 parts by weight of n-butyl acrylate, 4 parts by weight of 2-hydroxyethyl acrylate, 0.5 parts by weight of acrylic acid, 90 parts by weight of ethyl acetate and 0.1 parts by weight of benzoyl peroxide are put in a reaction vessel, and The air was replaced with nitrogen gas. Then, the temperature was raised to 70 ° C. with stirring, and the reaction was carried out for 8 hours to obtain an acrylic polymer solution A. Mw of the obtained acrylic polymer A by GPC was 1.2 million.
[0020]
<Production Example 2> Acrylic polymer solution B
100 parts by weight of n-butyl acrylate, 2 parts by weight of 2-hydroxyethyl acrylate, 1 part by weight of acrylamide, 100 parts by weight of ethyl acetate and 0.2 part by weight of azobisisobutyronitrile are put into a reaction vessel, and The air was replaced with nitrogen gas. Then, the temperature was raised to 60 ° C. with stirring, and the reaction was carried out for 4 hours. Four hours later, 100 parts by weight of toluene, 5 parts by weight of α-methylstyrene dimer, and 2 parts by weight of azobisisobutyronitrile were added, the temperature was raised to 90 ° C., and the mixture was further reacted for 4 hours to obtain an acrylic polymer solution B. Was. The Mw of the obtained acrylic polymer B by GPC was 700,000.
[0021]
<Production Example 3> Acrylic polymer solution C
100 parts by weight of 2-ethylhexyl acrylate, 0.5 parts by weight of 4-hydroxybutyl acrylate, 2.5 parts by weight of acrylamide, 90 parts by weight of ethyl acetate and 0.07 parts by weight of benzoyl peroxide are placed in a reaction vessel. Was replaced with nitrogen gas. Then, the temperature was raised to 73 ° C. with stirring, and the reaction was carried out for 8 hours to obtain an acrylic polymer solution C. Mw of the obtained acrylic polymer C by GPC was 1.4 million.
[0022]
<Production Example 4> Acrylic polymer solution D
An acrylic polymer solution D was obtained in the same manner as in Production Example 1, except that the amount of acrylic acid was changed to 4 parts by weight. The Mw of the obtained acrylic polymer E by GPC was 1.3 million.
[0023]
<Production Example 5> Acrylic polymer solution E
An acrylic polymer solution E was obtained in the same manner as in Production Example 1 except that acrylic acid was eliminated in Production Example 1. The Mw of the obtained acrylic polymer F by GPC was 1.2 million.
[0024]
<Production Example 6> Acrylic polymer solution F
Acrylic polymer solution F was obtained in the same manner as in Production Example 1, except that the amount of 2-hydroxyethyl acrylate was changed to 0.05 part by weight in Production Example 1. Mw of the obtained acrylic polymer E by GPC was 1.1 million.
[0025]
<Production Example 7> Acrylic polymer solution G
The reaction was carried out in the same manner as in Production Example 1, except that the amount of 2-hydroxyethyl acrylate was changed to 12 parts by weight, to obtain an acrylic polymer solution G. The Mw of the obtained acrylic polymer H by GPC was 1.4 million.
[0026]
<Production Example 8> Acrylic polymer solution H
Acrylic polymer solution I was obtained in the same manner as in Production Example 1, except that 90 parts by weight of ethyl acetate was changed to 10 parts by weight of ethyl acetate and 80 parts by weight of toluene. Mw of the obtained acrylic polymer H by GPC was 300,000.
[0027]
<Production Example 9> As a first step of producing an acrylic polymer by bulk polymerization, 100 parts by weight of 2-ethylhexyl acrylate, 2 parts by weight of 2-hydroxyethyl methacrylate, and 1 part by weight of dimethylaminoethyl acrylate were placed in a reaction vessel, and this reaction was performed. After replacing the air in the container with nitrogen gas, the temperature was raised to 50 ° C. with stirring. Then, when 0.025 parts by weight of 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) was added, the temperature of the reaction system increased, and the polymerization reaction was advanced without cooling. Then, the temperature of the reaction system reached 119 ° C., and then gradually started to decrease. 20 parts by weight of 2-ethylhexyl acrylate, 0.4 parts by weight of 2-hydroxyethyl methacrylate, and 0.2 parts by weight of dimethylaminoethyl acrylate were added, and the temperature of the reaction system was cooled to 110 ° C. Further, the mixture was cooled to room temperature with a water bath to obtain an acrylic partial polymer.
Next, as a second step, 0.3 parts by weight of a photopolymerization initiator (trade name: Darocur 1173, manufactured by Ciba Geigy) is added to 100 parts by weight of the acrylic partial polymer, and the mixture is stirred well to polymerize. A composition was obtained. It was applied to a release-treated polyester film, and irradiated with light from a high-pressure mercury lamp under a nitrogen gas atmosphere for 360 seconds at 10 W / m 2 , and then for 45 seconds at 3000 W / m 2 to perform photopolymerization to obtain a 25 μm An acrylic polymer layer was provided. The Mw of this acrylic polymer layer determined by GPC was 1.15 million.
[0028]
Table 1 shows the measurement conditions of GPC.
[Table 1]
[0029]
<Example 1>
To 100 parts by weight of the solid content of the acrylic polymer solution A, 0.05 parts by weight of a tolylene diisocyanate adduct of trimethylolpropane was added, and the mixture was stirred well to obtain a pressure-sensitive adhesive composition. It was applied to a release-treated polyester film and dried. After providing a 25 μm pressure-sensitive adhesive layer, it was transferred to one side of a polarizing film and aged at a temperature of 23 ° C. and a humidity of 65%.
[0030]
<Example 2>
To 100 parts by weight of the solid content of the acrylic polymer solution B, 0.7 parts by weight of xylylene diisocyanate of trimethylolpropane was added and stirred well to obtain a pressure-sensitive adhesive composition. It was applied to a release-treated polyester film and dried. After providing a 25 μm pressure-sensitive adhesive layer, it was transferred to one side of a polarizing film and aged at a temperature of 23 ° C. and a humidity of 65%.
[0031]
<Example 3>
To 100 parts by weight of the solid content of the acrylic polymer solution C, 0.1 part by weight of an xylylene diisocyanate adduct of trimethylolpropane was added, and the mixture was stirred well to obtain a pressure-sensitive adhesive composition. It was applied to a release-treated polyester film and dried. After providing a 25 μm pressure-sensitive adhesive layer, it was transferred to one side of a polarizing film and aged at a temperature of 23 ° C. and a humidity of 65%.
[0032]
<Example 4>
Production Example 9 was repeated except that the polymerizable composition in the second step was further added with 0.5 part by weight of an xylylene diisocyanate adduct of trimethylolpropane, based on 100 parts by weight of the acrylic partial polymer. An adhesive layer having a thickness of 25 μm was obtained on the release-treated polyester film. It was transferred to one side of a polarizing film and aged at a temperature of 23 ° C. and a humidity of 65%.
[0033]
<Comparative Example 1>
Example 1 was the same as Example 1 except that the acrylic polymer solution A was changed to the acrylic polymer solution D.
[0034]
<Comparative Example 2>
Example 1 was the same as Example 1 except that the acrylic polymer solution A was changed to the acrylic polymer solution E.
[0035]
<Comparative Example 3>
Example 1 was the same as Example 1 except that the acrylic polymer solution A was changed to the acrylic polymer solution F.
[0036]
<Comparative Example 4>
Example 1 was the same as Example 1 except that the acrylic polymer solution A was changed to the acrylic polymer solution G.
[0037]
<Comparative Example 5>
Example 1 was the same as Example 1 except that the acrylic polymer solution A was changed to the acrylic polymer solution H.
[0038]
<Comparative Example 6>
Example 1 was carried out in the same manner as in Example 1 except that the xylylene diisocyanate adduct of trimethylolpropane was changed to 0.001 part by weight.
[0039]
<Comparative Example 7>
Example 1 is the same as Example 1 except that the xylylene diisocyanate adduct of trimethylolpropane was changed to 6 parts by weight.
[0040]
<Comparative Example 8>
[0041]
Example 1 was repeated except that the xylylene diisocyanate adduct of trimethylolpropane was changed to hexamethylene diisocyanate of trimethylolpropane.
[0042]
<Comparative Example 9>
[0043]
In the same manner as in Example 1, except that the xylylene diisocyanate adduct of trimethylolpropane was changed to tolylene diisocyanate of trimethylolpropane.
[0044]
<Evaluation test>
Gel fraction The gel fraction on days 1, 3, 5, 7, 10, and 15 after application of the pressure-sensitive adhesive composition was measured.
The gel fraction was determined by taking about 0.1 g of the adhesive aged on a support at a temperature of 23 ° C. and a humidity of 65% RH in a sample bottle, adding 30 cc of ethyl acetate and shaking for 24 hours. The contents of the sample bottle were filtered off with a 200-mesh stainless steel wire gauze, and the residue on the wire gauze was dried at 100 ° C. for 2 hours, and the dry weight was measured. Table 2 shows the results.
(Equation 1)
[Table 2]
[0045]
Yellowing In the above Examples 1 to 4 and Comparative Examples 1 to 9, pressure-sensitive adhesive sheets for optical members were prepared using a 25 μm polyester film instead of the polarizing film. The pressure-sensitive adhesive sheet obtained by aging at a temperature of 23 ° C. and a humidity of 65% RH for 7 days was allowed to stand in a dryer at 100 ° C. for 15 days, and then the color change was visually observed. Table 2 shows the results. “○” indicates that the yellowing has not occurred, “△” indicates that the yellowing is slightly observed, and “×” indicates that the yellowing is remarkable.
Pot life In the above Examples 1 to 4 and Comparative Examples 1 to 9, the obtained pressure-sensitive adhesive composition was allowed to stand at a temperature of 23 ° C and a humidity of 65%, and the viscosity was measured after the pressure-sensitive adhesive composition was prepared. The time until the rise of the temperature increased was observed. Table 2 shows the results. “◎” indicates 12 hours or more, “○” indicates 6 hours or more to less than 12 hours, and “×” indicates less than 6 hours.
[0046]
Durability In the above Examples 1 to 4 and Comparative Examples 1 to 9, the obtained pressure-sensitive adhesive sheet for an optical member was attached to one surface of a non-alkali glass plate having a thickness of 0.5 mm using a laminator roll. . Then, it was held in an autoclave at 50 ° C. and 5 atm for 20 minutes for bonding.
The sample thus obtained was left under the conditions of 100 ° C., 60 ° C. and 90% RH for 500 hours, and the peeling of the optical member and the foaming at the bonding interface were visually observed. Table 3 shows the results. In the table, “表” means that there is no problem in practical use, “△” means that a problem may occur in practical use, and “×” indicates that there is a problem in practical use.
[Table 3]
[0047]
【The invention's effect】
The pressure-sensitive adhesive for optical members of the present invention is excellent in yellowing and has not only an industrially sufficient pot life as described in the above Examples, but also has Since the crosslinked structure is completed quickly and the gel fraction is stabilized, the adhesive properties are stabilized in a short time. Then, the pressure-sensitive adhesive sheet for an optical member of the present invention using the pressure-sensitive adhesive for an optical member of the present invention can be used promptly after pressure-sensitive adhesive processing (coating), thereby greatly improving productivity.
Claims (3)
ポリオール変性キシリレンジイソシアネート架橋剤0.01重量部以上5重量部以下と
を含有することを特徴とする光学部材用粘着剤組成物。(B) 0.1 to 10 parts by weight of a monomer having a hydroxyl group in the molecule, and (c) carboxyl group and amide group in the molecule with respect to 100 parts by weight of the alkyl (meth) acrylate. Is a copolymer of a monomer mixture containing 0.05 to 3 parts by weight of a monomer having any functional group of an amino group, and has a weight average molecular weight of 500,000 or more as determined by gel permeation chromatography. 100 parts by weight of acrylic polymer of 2,000,000 or less,
A pressure-sensitive adhesive composition for an optical member, comprising 0.01 to 5 parts by weight of a polyol-modified xylylene diisocyanate crosslinking agent.
粘着剤層が、(a)(メタ)アクリル酸アルキルエステル100重量部に対して、(b)分子内に水酸基を有する単量体0.1〜10重量部と、(c)分子内に、カルボキシル基、アミド基、アミノ基の何れかの官能基を有する単量体0.05〜3重量部とを含有する単量体混合物の共重合体であり、ゲルパーミュエーションクロマトグラフィーによる重量平均分子量が50万以上200万以下のアクリル系ポリマー100重量部と、ポリオール変性キシリレンジイソシアネート架橋剤0.01重量部以上5重量部以下とを含有する粘着剤組成物からなる粘着剤層であることを特徴とする光学部材用粘着シート。A support, a pressure-sensitive adhesive sheet provided with a pressure-sensitive adhesive layer on one or both sides of the support,
The adhesive layer comprises (a) 0.1 to 10 parts by weight of a monomer having a hydroxyl group in the molecule, and (c) in the molecule, 100 parts by weight of the alkyl (meth) acrylate. It is a copolymer of a monomer mixture containing 0.05 to 3 parts by weight of a monomer having a functional group of any of a carboxyl group, an amide group and an amino group, and has a weight average determined by gel permeation chromatography. A pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive composition containing 100 parts by weight of an acrylic polymer having a molecular weight of 500,000 to 2,000,000 and 0.01 to 5 parts by weight of a polyol-modified xylylene diisocyanate crosslinking agent A pressure-sensitive adhesive sheet for an optical member, comprising:
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002250458A JP4753196B2 (en) | 2002-08-29 | 2002-08-29 | Optical member pressure-sensitive adhesive composition and optical member-use pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition |
TW092122217A TWI327589B (en) | 2002-08-29 | 2003-08-13 | Adhesive composition for optical element and adhesive sheet for optical element using the same |
KR1020030059776A KR20040030279A (en) | 2002-08-29 | 2003-08-28 | Pressure sensitive adhesive composition for optical member and adhesive seat for optical member using the same |
CNB031577903A CN1286935C (en) | 2002-08-29 | 2003-08-29 | Adhesive composition for optical component and binding film for optical component therewith |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002250458A JP4753196B2 (en) | 2002-08-29 | 2002-08-29 | Optical member pressure-sensitive adhesive composition and optical member-use pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2004091499A true JP2004091499A (en) | 2004-03-25 |
JP4753196B2 JP4753196B2 (en) | 2011-08-24 |
Family
ID=32057286
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2002250458A Expired - Lifetime JP4753196B2 (en) | 2002-08-29 | 2002-08-29 | Optical member pressure-sensitive adhesive composition and optical member-use pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP4753196B2 (en) |
KR (1) | KR20040030279A (en) |
CN (1) | CN1286935C (en) |
TW (1) | TWI327589B (en) |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20070075158A (en) * | 2006-01-12 | 2007-07-18 | 삼성코닝 주식회사 | Composite for optical film, optical filter having the same and display apparatus having the optical filter |
JP2008266514A (en) * | 2007-04-24 | 2008-11-06 | Soken Chem & Eng Co Ltd | Tacky adhesive composition comprising terminal reactive acrylic polymer and its use |
JP2009510193A (en) * | 2005-09-23 | 2009-03-12 | ナショナル スターチ アンド ケミカル インベストメント ホールディング コーポレイション | Acrylic polymer adhesive |
JP2009084399A (en) * | 2007-09-28 | 2009-04-23 | Gunze Ltd | Near-infrared absorbing pressure-sensitive adhesive composition and multilayer optical film |
JP2009084400A (en) * | 2007-09-28 | 2009-04-23 | Gunze Ltd | Near-infrared absorbing pressure-sensitive adhesive composition and multilayer optical film |
EP2053109A1 (en) | 2007-10-22 | 2009-04-29 | Nitto Denko Corporation | Pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive layer for optical film, production method thereof, pressure-sensitive adhesive optical film and image display |
EP2072552A2 (en) | 2007-12-20 | 2009-06-24 | Nitto Denko Corporation | Pressure-sensitive adhesive composition for optical films, pressure-sensitive adhesive optical film and image display |
JP2009242767A (en) * | 2008-03-14 | 2009-10-22 | Nitto Denko Corp | Pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive optical film, and image display device |
JP2010037355A (en) * | 2008-07-31 | 2010-02-18 | Big Technos Kk | Electrically peelable adhesive composition, electrically peelable adhesive product and method for peeling the same |
US7846542B2 (en) | 2008-02-15 | 2010-12-07 | Nitto Denko Corporation | Pressure-sensitive adhesive composition for optical films, pressure-sensitive adhesive optical film and image display |
JP2011074308A (en) * | 2009-10-01 | 2011-04-14 | Three M Innovative Properties Co | Transparent adhesive sheet and image display device including the same |
WO2011118183A1 (en) * | 2010-03-25 | 2011-09-29 | 日東電工株式会社 | Acrylic adhesive composition for optical use and acrylic adhesive tape for optical use |
WO2011037440A3 (en) * | 2009-09-28 | 2011-11-03 | (주)Lg화학 | Touch panel |
JP2012504512A (en) * | 2008-10-03 | 2012-02-23 | スリーエム イノベイティブ プロパティズ カンパニー | Cloud point resistant adhesive and laminate |
US8361632B2 (en) | 2008-10-03 | 2013-01-29 | 3M Innovative Properties Company | Cloud point-resistant adhesives and laminates |
JP2013047888A (en) * | 2011-08-29 | 2013-03-07 | Soken Chem & Eng Co Ltd | Laminate and touch panel having laminate |
JP2013067782A (en) * | 2011-09-09 | 2013-04-18 | Toyo Ink Sc Holdings Co Ltd | Optical adhesive, optical adhesive sheet, and laminate |
JP2013523940A (en) * | 2010-04-05 | 2013-06-17 | エルジー・ハウシス・リミテッド | Adhesive composition for touch panel, adhesive film and touch panel |
JP2013527861A (en) * | 2010-04-05 | 2013-07-04 | エルジー・ハウシス・リミテッド | Adhesive composition, adhesive sheet and touch panel |
JP2016190992A (en) * | 2015-03-31 | 2016-11-10 | アイカ工業株式会社 | Adhesive composition |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI391243B (en) * | 2005-03-30 | 2013-04-01 | Dainippon Ink & Chemicals | Light diffusion film |
KR101201079B1 (en) * | 2005-06-23 | 2012-11-14 | 키모토 컴파니 리미티드 | Adhesive and adhesive sheet |
JP4869015B2 (en) * | 2005-10-18 | 2012-02-01 | 日東電工株式会社 | Adhesive composition, adhesive layer and method for producing the same, and optical member with adhesive |
JP5000940B2 (en) * | 2006-01-13 | 2012-08-15 | リンテック株式会社 | Adhesive for polarizing plate, adhesive sheet, polarizing plate with adhesive and method for producing the same, and optical film and method for producing the same |
JP4780766B2 (en) * | 2006-03-27 | 2011-09-28 | 日東電工株式会社 | Optical adhesive, optical film with adhesive, and image display device |
KR20110127136A (en) * | 2009-02-16 | 2011-11-24 | 소켄 케미칼 앤드 엔지니어링 캄파니, 리미티드 | Radiation curable adhesive composition for optical components and adhesive optical component |
WO2012128594A2 (en) | 2011-03-23 | 2012-09-27 | 주식회사 엘지화학 | Adhesive composition for an optical film |
JP5831559B2 (en) * | 2012-01-26 | 2015-12-09 | コニカミノルタ株式会社 | LCD with touch panel |
KR101355020B1 (en) * | 2012-02-10 | 2014-01-27 | 에스케이씨하스디스플레이필름(유) | Glass scattering preventing film for thin-film display protection |
CN103045129B (en) * | 2012-12-28 | 2015-07-22 | 宁波大榭开发区综研化学有限公司 | Acrylate adhesive, protective film tape employing same and preparation method of acrylate adhesive |
CN105102574A (en) * | 2013-04-08 | 2015-11-25 | 综研化学株式会社 | Solvent-free adhesive agent composition for optical applications and method for producing same, adhesive sheet for optical applications, image display device, output-input device, and method for producing adhesive agent layer |
KR20160022367A (en) * | 2013-07-23 | 2016-02-29 | 코니카 미놀타 가부시키가이샤 | Polarizing plate and va-type liquid crystal display device |
CN114316807B (en) * | 2021-12-15 | 2023-06-02 | 武汉市科达云石护理材料有限公司 | Low-viscosity yellowing-resistant quick-setting stone surface adhesive and preparation method and application thereof |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07324183A (en) * | 1994-05-31 | 1995-12-12 | Mitsubishi Chem Corp | Self-adhesive composition |
JPH08209095A (en) * | 1995-02-06 | 1996-08-13 | Soken Chem & Eng Co Ltd | Pressure-sensitive adhesive for liquid crystal element and liquid crystal element |
JPH08302325A (en) * | 1995-05-12 | 1996-11-19 | Nippon Synthetic Chem Ind Co Ltd:The | Pressure-sensitive adhesive composition |
JPH09113724A (en) * | 1995-10-16 | 1997-05-02 | Sekisui Chem Co Ltd | Tacky adhesive type polarizing plate |
JP2001240830A (en) * | 2000-02-28 | 2001-09-04 | Saiden Chemical Industry Co Ltd | Adhesive composition and surface protective film |
JP2001335767A (en) * | 2000-05-30 | 2001-12-04 | Lintec Corp | Self-adhesive composition, self-adhesive sheet obtained by using the same and self-adhesive optical member |
JP2002121521A (en) * | 2000-10-13 | 2002-04-26 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition for polarizing film and polarizing film |
-
2002
- 2002-08-29 JP JP2002250458A patent/JP4753196B2/en not_active Expired - Lifetime
-
2003
- 2003-08-13 TW TW092122217A patent/TWI327589B/en not_active IP Right Cessation
- 2003-08-28 KR KR1020030059776A patent/KR20040030279A/en active Search and Examination
- 2003-08-29 CN CNB031577903A patent/CN1286935C/en not_active Expired - Lifetime
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07324183A (en) * | 1994-05-31 | 1995-12-12 | Mitsubishi Chem Corp | Self-adhesive composition |
JPH08209095A (en) * | 1995-02-06 | 1996-08-13 | Soken Chem & Eng Co Ltd | Pressure-sensitive adhesive for liquid crystal element and liquid crystal element |
JPH08302325A (en) * | 1995-05-12 | 1996-11-19 | Nippon Synthetic Chem Ind Co Ltd:The | Pressure-sensitive adhesive composition |
JPH09113724A (en) * | 1995-10-16 | 1997-05-02 | Sekisui Chem Co Ltd | Tacky adhesive type polarizing plate |
JP2001240830A (en) * | 2000-02-28 | 2001-09-04 | Saiden Chemical Industry Co Ltd | Adhesive composition and surface protective film |
JP2001335767A (en) * | 2000-05-30 | 2001-12-04 | Lintec Corp | Self-adhesive composition, self-adhesive sheet obtained by using the same and self-adhesive optical member |
JP2002121521A (en) * | 2000-10-13 | 2002-04-26 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition for polarizing film and polarizing film |
Cited By (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009510193A (en) * | 2005-09-23 | 2009-03-12 | ナショナル スターチ アンド ケミカル インベストメント ホールディング コーポレイション | Acrylic polymer adhesive |
KR20070075158A (en) * | 2006-01-12 | 2007-07-18 | 삼성코닝 주식회사 | Composite for optical film, optical filter having the same and display apparatus having the optical filter |
JP2008266514A (en) * | 2007-04-24 | 2008-11-06 | Soken Chem & Eng Co Ltd | Tacky adhesive composition comprising terminal reactive acrylic polymer and its use |
JP2009084399A (en) * | 2007-09-28 | 2009-04-23 | Gunze Ltd | Near-infrared absorbing pressure-sensitive adhesive composition and multilayer optical film |
JP2009084400A (en) * | 2007-09-28 | 2009-04-23 | Gunze Ltd | Near-infrared absorbing pressure-sensitive adhesive composition and multilayer optical film |
US8962135B2 (en) | 2007-10-22 | 2015-02-24 | Nitto Denko Corporation | Pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive layer for optical film, production method thereof, pressure-sensitive adhesive optical film and image display |
EP2053109A1 (en) | 2007-10-22 | 2009-04-29 | Nitto Denko Corporation | Pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive layer for optical film, production method thereof, pressure-sensitive adhesive optical film and image display |
EP2072552A2 (en) | 2007-12-20 | 2009-06-24 | Nitto Denko Corporation | Pressure-sensitive adhesive composition for optical films, pressure-sensitive adhesive optical film and image display |
US7846542B2 (en) | 2008-02-15 | 2010-12-07 | Nitto Denko Corporation | Pressure-sensitive adhesive composition for optical films, pressure-sensitive adhesive optical film and image display |
US8709597B2 (en) | 2008-02-15 | 2014-04-29 | Nitto Denko Corporation | Pressure-sensitive adhesive composition for optical films, pressure-sensitive adhesive optical film and image display |
US7862888B2 (en) | 2008-03-14 | 2011-01-04 | Nitto Denko Corporation | Pressure-sensitive adhesive composition for optical films, pressure-sensitive adhesive optical film and image display |
JP2009242767A (en) * | 2008-03-14 | 2009-10-22 | Nitto Denko Corp | Pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive optical film, and image display device |
US8784987B2 (en) | 2008-03-14 | 2014-07-22 | Nitto Denko Corporation | Pressure-sensitive adhesive composition for optical films, pressure-sensitive adhesive optical film and image display |
JP2010037355A (en) * | 2008-07-31 | 2010-02-18 | Big Technos Kk | Electrically peelable adhesive composition, electrically peelable adhesive product and method for peeling the same |
JP2012504512A (en) * | 2008-10-03 | 2012-02-23 | スリーエム イノベイティブ プロパティズ カンパニー | Cloud point resistant adhesive and laminate |
US8663811B2 (en) | 2008-10-03 | 2014-03-04 | 3M Innovative Properties Company | Cloud point-resistant adhesives and laminates |
US8361633B2 (en) | 2008-10-03 | 2013-01-29 | 3M Innovative Properties Company | Cloud point-resistant adhesives and laminates |
US8361632B2 (en) | 2008-10-03 | 2013-01-29 | 3M Innovative Properties Company | Cloud point-resistant adhesives and laminates |
KR101191117B1 (en) | 2009-09-28 | 2012-10-15 | 주식회사 엘지화학 | Touch panel |
CN102648260A (en) * | 2009-09-28 | 2012-08-22 | Lg化学株式会社 | Touch panel |
WO2011037440A3 (en) * | 2009-09-28 | 2011-11-03 | (주)Lg화학 | Touch panel |
JP2011074308A (en) * | 2009-10-01 | 2011-04-14 | Three M Innovative Properties Co | Transparent adhesive sheet and image display device including the same |
CN102812100A (en) * | 2010-03-25 | 2012-12-05 | 日东电工株式会社 | Acrylic adhesive composition for optical use and acrylic adhesive tape for optical use |
WO2011118183A1 (en) * | 2010-03-25 | 2011-09-29 | 日東電工株式会社 | Acrylic adhesive composition for optical use and acrylic adhesive tape for optical use |
US8883926B2 (en) | 2010-03-25 | 2014-11-11 | Nitto Denko Corporation | Acrylic pressure-sensitive adhesive composition for optical use and acrylic pressure-sensitive adhesive tape for optical use |
JP2013523940A (en) * | 2010-04-05 | 2013-06-17 | エルジー・ハウシス・リミテッド | Adhesive composition for touch panel, adhesive film and touch panel |
JP2013527861A (en) * | 2010-04-05 | 2013-07-04 | エルジー・ハウシス・リミテッド | Adhesive composition, adhesive sheet and touch panel |
JP2013047888A (en) * | 2011-08-29 | 2013-03-07 | Soken Chem & Eng Co Ltd | Laminate and touch panel having laminate |
JP2013067782A (en) * | 2011-09-09 | 2013-04-18 | Toyo Ink Sc Holdings Co Ltd | Optical adhesive, optical adhesive sheet, and laminate |
JP2016190992A (en) * | 2015-03-31 | 2016-11-10 | アイカ工業株式会社 | Adhesive composition |
Also Published As
Publication number | Publication date |
---|---|
JP4753196B2 (en) | 2011-08-24 |
TW200406476A (en) | 2004-05-01 |
KR20040030279A (en) | 2004-04-09 |
TWI327589B (en) | 2010-07-21 |
CN1286935C (en) | 2006-11-29 |
CN1490371A (en) | 2004-04-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4753196B2 (en) | Optical member pressure-sensitive adhesive composition and optical member-use pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition | |
JP4134350B2 (en) | Optical member pressure-sensitive adhesive and optical member using the pressure-sensitive adhesive | |
JP3997270B2 (en) | Optical film pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet, and optical member using the same | |
KR101281643B1 (en) | Adhesive composition for optical film, adhesive sheet, and optical member using such adhesive composition | |
JP4534431B2 (en) | Adhesive and optical member using the same | |
KR102253707B1 (en) | Adhesive composition for optical film, adhesive layer, optical member and image display device | |
JP2007138057A (en) | Adhesive composition for optical film and adhesive sheet, and optical member using the same | |
JP2004224873A (en) | Pressure-sensitive adhesive composition for polarizing film | |
JP2010508386A (en) | Acrylic pressure-sensitive adhesive composition for polarizing plate containing a photoinitiator group | |
KR102403283B1 (en) | Adhesive composition for optical film, adhesive layer, optical member and optical display | |
JP2003034781A (en) | Pressure sensitive adhesive for optical member and optical member provided with the adhesive | |
JP7149067B2 (en) | PSA COMPOSITION FOR OPTICAL FILM, ADHESIVE LAYER, OPTICAL MEMBER, AND IMAGE DISPLAY DEVICE | |
JP2011057794A (en) | Solvent-borne adhesive composition for optical member, adhesive layer, and optical member with adhesive | |
TW201229173A (en) | Adhesive composition and optical member using the same | |
EP2905318A1 (en) | Double-sided pressure-sensitive adhesive sheet with repeeling properties and method for repeeling same | |
WO2020230875A1 (en) | Adhesive sheet and laminate | |
JP4992337B2 (en) | Adhesive composition and adhesive film using the adhesive composition | |
JP6881500B2 (en) | Adhesive sheet and laminate | |
JP7149066B2 (en) | PSA COMPOSITION FOR OPTICAL FILM, ADHESIVE LAYER, OPTICAL MEMBER, AND IMAGE DISPLAY DEVICE | |
JP2018024756A (en) | Adhesive composition for optical films, and adhesive layer, optical member, and image display device prepared therewith | |
KR20090112103A (en) | Method for Preparing Starch-Acryl Copolymer Using Emulsifier-Free Emulsion Polymerization | |
JP7307749B2 (en) | Adhesive composition for optical film, adhesive layer for optical film, and optical film with adhesive layer | |
JP6125636B2 (en) | Optical member pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and laminate | |
JP5991833B2 (en) | Acrylic pressure-sensitive adhesive, pressure-sensitive adhesive for optical members, optical member with a pressure-sensitive adhesive layer using the same, image display device, method for producing acrylic pressure-sensitive adhesive, and acrylic pressure-sensitive adhesive composition | |
JP2018024830A (en) | Adhesive composition for optical films, adhesive layer and method for producing the same, optical member, and image display device |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050530 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080116 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080129 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080324 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20080422 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080513 |
|
A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20080627 |
|
A912 | Re-examination (zenchi) completed and case transferred to appeal board |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20080718 |
|
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: 20110517 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140603 Year of fee payment: 3 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 4753196 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
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 |