JP4134350B2 - Optical member pressure-sensitive adhesive and optical member using the pressure-sensitive adhesive - Google Patents

Optical member pressure-sensitive adhesive and optical member using the pressure-sensitive adhesive Download PDF

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Publication number
JP4134350B2
JP4134350B2 JP2002250459A JP2002250459A JP4134350B2 JP 4134350 B2 JP4134350 B2 JP 4134350B2 JP 2002250459 A JP2002250459 A JP 2002250459A JP 2002250459 A JP2002250459 A JP 2002250459A JP 4134350 B2 JP4134350 B2 JP 4134350B2
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weight
parts
pressure
sensitive adhesive
optical member
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JP2004091500A (en
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明 野村
貞彦 仁科
幸二 冨田
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Soken Chemical and Engineering Co Ltd
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Soken Chemical and Engineering Co Ltd
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Priority to KR1020030059780A priority patent/KR20040030280A/en
Priority to TW092123708A priority patent/TWI294452B/en
Priority to CNB031577881A priority patent/CN1305987C/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08Homopolymers or copolymers of acrylic acid esters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062Copolymers with monomers not covered by C09J133/06
    • C09J133/066Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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
    • C09J133/24Homopolymers or copolymers of amides or imides
    • C09J133/26Homopolymers or copolymers of acrylamide or methacrylamide
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)

Description

【0001】
【発明の属する技術分野】
本発明は、光学部材用粘着剤、およびこの粘着剤を用いた光学部材、特に液晶表示装置(LCD)の液晶セルに貼着される粘着剤層付き偏光フィルム等を構成する光学部材に関するものである。
【0002】
【従来の技術】
LCDは、電卓、時計、テレビや各種測定器の表示装置等に利用され、様々な条件下で使用されてきた。このLCDの液晶セルには、一般的には、ポリビニールアルコール系の偏光子の両面にトリアセテート系保護フィルムで挟んだ3層構造を有する偏光フィルム等が、粘着剤層を介して貼着されている。この粘着剤層に関して、例えば、特開平3-12471号公報には、アクリル系ポリマーの架橋度をゲル分率に基づいて50〜95重量%と高くし、未架橋ポリマーの重量平均分子量を10万以上とすることで、耐久性に優れる感圧接着剤層を有する偏光フィルムが得られることが開示されている。
【0003】
しかしながら、粘着剤の分子量をあげたり、架橋度をあげて粘着剤層を過酷な条件における使用に耐えられるようすることは、偏光フィルムの寸法変化を粘着剤で抑制しようとするものであり、熱または湿熱条件で生じる偏光フィルムの寸法変化に起因する応力を十分に吸収、緩和することができない。このため、偏光フィルムに作用する残留応力の分布が不均一となり、特に外周部に応力集中が生じる結果、液晶表示装置において、光漏れ、色むらが起こりやすいという問題が発生する。そして、液晶表示装置が車載用や屋外計測器用等に利用分野に拡大されるとともに、偏光板等の基材に寸法変化が起こるような過酷な条件で使用されるようになってきた。
【0004】
こうした中で、例えば特開2000-109771号公報には、高分子量ポリマーと低分子量ポリマーとを含む粘着剤組成物を用いることにより、基材の寸法変化に起因する応力を吸収・緩和させ、湿熱条件下での光学的欠陥を防止するできることが開示されている。パソコンのディスプレイ、車載用テレビ、車載用ナビゲーションシステムのディスプレイ、壁掛けテレビ等の分野では、より苛酷な湿熱条件での使用やLCDの表示面積が拡大する傾向にあり、従来の粘着剤組成物では、その応力を吸収・緩和する能力が不十分であった。そのため、基材の寸法変化量が増大しても、十分に応力を吸収・緩和できる粘着剤が要望されている。
また、LCD市場の拡大とともに、偏光フィルムの使用量が増え、生産性の向上のために、粘着剤の塗工(粘着加工)後に、速やかに使用できる粘着剤が要求されている。しかしながら、アクリル系粘着剤は、通常、アクリル系ポリマーと架橋剤を混合して粘着加工しており、架橋反応が完了し粘着性能が安定するまでに常温で7日程度のエージング時間が必要となっている。
【0005】
【発明が解決しようとする課題】
本発明は、特に貼り付け面積の大きい、偏光フィルム、位相差フィルム、楕円偏光フィルム等の部材の寸法変化による応力を緩和し、高湿熱条件下で剥がれや発泡をを防止するだけでなく、光漏れによる色むらを抑制する光学部材用アクリル系粘着剤を提供すること、及び、該粘着剤を用いた光学部材を提供することを課題とする。
【0006】
【課題を解決するための手段】
本発明の光学部材用粘着剤は、(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0.5〜5重量部、及び、(c)分子内にカルボキシル、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重量部からな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、イソシアネート化合物0.01〜1重量部とからなる粘着剤組成物を、架橋反応させることによりゲル分率を10%以上45%以下としたものである。また、アクリル系ポリマーは溶液重合、塊状重合により得られたものが好ましい。
本発明の光学部材は、支持体の片面あるいは両面に、前記光学部材用粘着剤からなる粘着剤層を形成したものであり、その支持体が、偏光フィルム、位相差フィルム、楕円偏光フィルムのいずれかである場合に効果的である。
【0007】
【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、(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重量部及び(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重量部以上3重量部以下からなる単量体混合物の共重合体である。
【0008】
単量体混合物の成分(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、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。
【0009】
単量体混合物の成分(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。
【0010】
単量体混合物の成分(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、アミノエチル(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。
【0011】
前記単量体混合物の配合量は、成分(a)100重量部に対して、成分(b)0.1重量部以上10重量部以下、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。これらの配合量がこの数値範囲から逸脱すると、長いエージング時間が必要であったり、高温又は高湿熱条件下での剥がれや発泡が生じたり、光漏れによる色むらが発生する。
【0012】
前記単量体混合物には、必要に応じて、その他の単量体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。その他の単量体の混合比は、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。
【0013】
本発明の光学部材用粘着剤に使用する前記アクリル系ポリマーは、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50万以上180万以下である。Mwが、50万未満であると、後述するゲル分率を好適な範囲に調製しても、熱時の粘着剤の凝集力が十分でなく、高温条件下での発泡が生じやすく、200万を超えると、粘着剤の応力緩和性が低下して、例えばガラス基板と偏光板の貼り合わせに使用する場合には、貼付面周端部での光漏れ現象が生じやすい。
【0014】
本発明の光学部材用粘着剤に使用するイソシアネート化合物の例としては、トリレンジイソシアネート、クロルフェニレンジイソシアナート、ヘキサメチレンジイソシアナート、テトラメチレンジイソシアナート、イソホロンジイソシアネート、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、水添されたジフェニルメタンジイソシアネートなどのイソシアネートモノマー及びこれらイソシアネートモノマーをトリメチロールプロパンなどと付加したイソシアネート化合物やイソシアヌレート化物、ビュレット型化合物、さらには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付加反応させたウレタンプレポリマー型のイソシアネートなどを挙げることができる。
【0015】
本発明の光学部材用粘着剤は、前記アクリル系ポリマー100重量部に対してイソシアネート化合物0.01〜1重量部からなる粘着剤組成物を、常温又は加熱下で架橋反応させてゲル分率を1%以上50%以下としたものであるが、ゲル分率10%以上45%以下であることがより好ましい。このゲル分率が低いと、粘着剤の凝集力不足による高温雰囲気下での発泡が生じやすくなる。また、ゲル分率が高すぎると、粘着剤の応力緩和性が低下して、例えばガラス基板と偏光板の貼り合わせに使用する場合には、貼付面周端部での光漏れ現象が生じやすい。
【0016】
前記アクリル系ポリマーと前記イソシアネート化合物の混合は、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。
【0017】
ゲル分率は、粘着剤約0.1gをサンプル瓶に採取し、酢酸エチルを30ccを加えて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でろ別し、金網上の残留物を100℃で2時間乾燥して乾燥重量を測定し、次式[I]により求める。
【式1】

Figure 0004134350
【0018】
本発明の粘着剤は、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。
【0019】
本発明の光学部材は、支持体の片面あるいは両面に、前記光学部材用粘着剤からなる粘着剤層を形成したものである。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、輝度向上フィルム及び光拡散フィルム等が挙げられるが、特に、支持体が偏光フィルム、位相差フィルム、または、楕円偏光フィルムとした場合に、前記光学部材用粘着剤の応力緩和性がより発揮できる。
【0020】
本発明の偏光フィルム、位相差フィルム、楕円偏光フィルムに前記光学部材用粘着剤からなる粘着剤層を形成した光学部材は、ガラス基板などに貼着したときに、粘着剤層が熱応力を十分緩和するために、光漏れなどが生じない。
【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。
【0021】
<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。
【0022】
<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。
【0023】
<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。
【0024】
<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のGPCによるMwは130万であった。
【0025】
<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のGPCによるMwは120万であった。
【0026】
<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と同様にして、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のGPCによるMwは110万であった。
【0027】
<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と同様にして、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のGPCによるMwは140万であった。
【0028】
<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と同様にして、アクリル系ポリマー溶液を得た。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。
【0029】
<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/mで360秒間、その後3000W/m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。
【0030】
GPCの測定条件を表1に示す。
【表1】
Figure 0004134350
【0031】
<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7日間熟成させ、粘着剤層を有する光学部材を得た。
【0032】
<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トリレンジイソシアネート付加物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7日間熟成させ、粘着剤層を有する光学部材を得た。
【0033】
<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7日間熟成させ、粘着剤層を有する光学部材を得た。
【0034】
<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ト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7日間熟成させ、粘着剤層を有する光学部材を得た。
【0035】
<実施例5>
【0036】
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7日間熟成させ、粘着剤層を有する光学部材を得た。
【0037】
<実施例6>
【0038】
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7日間熟成させ、粘着剤層を有する光学部材を得た。
【0039】
<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と同様にして光学部材を得た。
【0040】
<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と同様にして光学部材を得た。
【0041】
<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と同様にして光学部材を得た。
【0042】
<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と同様にして光学部材を得た。
【0043】
<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と同様にして光学部材を得た。
【0044】
<比較例6>
実施例3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3と同様にして光学部材を得た。
【0045】
<比較例7>
実施例3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3重量部に変更した以外は、実施例3と同様にして光学部材を得た。
【0046】
ゲル分率
実施例1〜6、比較例1〜7において、偏光フィルムに代わりに剥離処理したポリエステルフィルムを使用して、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2】
Figure 0004134350
【表2】
Figure 0004134350
【0047】
耐久性
上記実施例1〜4、比較例1〜7において、温度23℃、湿度65%RHで7日間熟成して得られた15インチサイズの光学部材を厚さ0.5mmの無アルカリガラス板の両面に直交ニコルになるよう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。
こうして得られたサンプルを120℃、80℃90%RHの条件下に500時間放置し、光学部材の剥離、接着界面での発泡および寸法変化による残留応力に起因して生じる光漏れを目視にて観察した。結果を、前記ゲル分率の評価結果と合わせて表2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。尚、比較例4及び比較例7の発泡及び光漏れは剥がれが大きく、観察できる状態でなかった。
【表3】
Figure 0004134350
【0048】
【発明の効果】
本発明の光学部材用粘着剤及びそれを使用した光学部材は、前記実施例で示した如く、従来の光学部材用粘着剤を使用した光学部材と比較して明らかなように、耐熱性及び耐湿熱性を満足するだけでなく、偏光フィルム等の部材の寸法変化による応力を緩和して、光漏れや色むらを大幅に抑制できるものである。さらに、本発明の光学部材用粘着剤は、従来の粘着剤と比較して短時間で架橋構造が完結して、ゲル分率及び粘着性能が安定するため、本発明の光学部材用粘着剤を使用した光学部材は、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]
BACKGROUND OF THE INVENTION
The present invention relates to an optical member pressure-sensitive adhesive, and an optical member using the pressure-sensitive adhesive, particularly an optical member constituting a polarizing film with a pressure-sensitive adhesive layer and the like attached to a liquid crystal cell of a liquid crystal display (LCD). is there.
[0002]
[Prior art]
LCDs are used in calculators, watches, televisions, display devices for various measuring instruments, and the like, and have been used under various conditions. Generally, a polarizing film having a three-layer structure sandwiched between triacetate protective films on both sides of a polyvinyl alcohol polarizer is attached to the LCD liquid crystal cell via an adhesive layer. Yes. Regarding this pressure-sensitive adhesive layer, for example, JP-A-3-24771 discloses that the crosslinking degree of an acrylic polymer is increased to 50 to 95% by weight based on the gel fraction, and the weight average molecular weight of the uncrosslinked polymer is 100,000. By making it above, it is disclosed that a polarizing film having a pressure-sensitive adhesive layer having excellent durability can be obtained.
[0003]
However, increasing the molecular weight of the pressure-sensitive adhesive or increasing the degree of crosslinking so that the pressure-sensitive adhesive layer can withstand use under severe conditions is intended to suppress the dimensional change of the polarizing film with the pressure-sensitive adhesive. Or the stress resulting from the dimensional change of the polarizing film produced on wet heat conditions cannot fully be absorbed and relieved. For this reason, the distribution of the residual stress acting on the polarizing film becomes non-uniform, and stress concentration occurs particularly in the outer peripheral portion. As a result, in the liquid crystal display device, there is a problem that light leakage and color unevenness are likely to occur. Liquid crystal display devices have been expanded to use fields such as in-vehicle and outdoor measuring instruments, and have been used under severe conditions such that dimensional changes occur in substrates such as polarizing plates.
[0004]
Among these, for example, in JP 2000-109771 A, a pressure-sensitive adhesive composition containing a high molecular weight polymer and a low molecular weight polymer is used to absorb and relieve stress caused by a dimensional change of the base material. It is disclosed that optical defects under conditions can be prevented. In the fields of personal computer displays, in-vehicle TVs, in-vehicle navigation system displays, wall-mounted TVs, etc., there is a tendency for the use under more severe wet heat conditions and the display area of LCDs to expand. With conventional adhesive compositions, The ability to absorb and relieve the stress was insufficient. Therefore, there is a demand for an adhesive that can sufficiently absorb and relieve stress even when the dimensional change amount of the substrate increases.
In addition, with the expansion of the LCD market, the amount of polarizing film used has increased, and in order to improve productivity, there is a demand for an adhesive that can be used promptly after application of adhesive (adhesive processing). However, acrylic pressure-sensitive adhesives are usually subjected to pressure-sensitive adhesive processing by mixing an acrylic polymer and a crosslinking agent, and an aging time of about 7 days at room temperature is required until the crosslinking reaction is completed and the pressure-sensitive adhesive performance is stabilized. ing.
[0005]
[Problems to be solved by the invention]
The present invention relieves stress due to dimensional changes of members such as polarizing films, retardation films, and elliptically polarizing films that have a particularly large bonding area, and prevents not only peeling and foaming under high-humidity heat conditions, but also light. It is an object to provide an acrylic pressure-sensitive adhesive for optical members that suppresses uneven color due to leakage, and to provide an optical member using the pressure-sensitive adhesive.
[0006]
[Means for Solving the Problems]
The pressure-sensitive adhesive for optical members of the present invention comprises (b) 0.5 to 5 parts by weight of a monomer having a hydroxyl group in the molecule and (b) 100 parts by weight of (meth) acrylic acid alkyl ester, and ( c) Copolymer of a monomer mixture consisting of 0.05 to 3 parts by weight of a monomer having a functional group of carboxyl, amide group or amino group in the molecule, and by gel permeation chromatography and weight-average molecular weight of 500,000 or more to 2,000,000 acrylic polymer 100 parts by weight, the adhesive composition comprising an isocyanate compound 0.01 to 1 part by weight, the gel fraction of 10% or more by crosslinking 45 % Or less . The acrylic polymer is preferably obtained by solution polymerization or bulk polymerization.
The optical member of the present invention is obtained by forming a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive for optical members on one side or both sides of a support, and the support is any of a polarizing film, a retardation film, and an elliptically polarizing film. It is effective when it is.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The acrylic polymer used for the pressure-sensitive adhesive for optical members of the present invention is (b) monomer (0.1-10) having a hydroxyl group in the molecule with respect to 100 parts by weight of (meth) acrylic acid alkyl ester. And (c) a monomer mixture copolymer comprising 0.05 part by weight or more and 3 parts by weight or less of a monomer having any functional group of carboxyl group, amide group, and amino group in the molecule. is there.
[0008]
Examples of monomer mixture component (a) (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-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.
[0009]
Examples of the monomer mixture component (b) monomer having a hydroxyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) 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, etc. Can be mentioned.
[0010]
Component (c) of monomer mixture Examples of monomers having any functional group of carboxyl group, amide group and amino group in the molecule include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate , Carboxyl group-containing monomers such as 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-dimethylaminopropyl (meth) ) Acrylamide, vinylpyrrolidone, methylol (meth) acrylamide, methoxyethyl Amide group-containing monomers such as ru (meth) acrylamide; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, amino Examples thereof include amino group-containing monomers such as ethyl (meth) acrylate.
[0011]
The amount of the monomer mixture is 0.1 part by weight or more and 10 parts by weight or less of component (b) and 0.05 part by weight or more and 3 parts by weight or less of component (b) with respect to 100 parts by weight of component (a). However, the amount of the component (b) is 0.5 to 5 parts by weight and the component (c) is 0.05 to 2 parts by weight with respect to 100 parts by weight of the component (a). When these blending amounts deviate from this numerical range, a long aging time is required, peeling or foaming occurs under high temperature or high heat and humidity conditions, and uneven color due to light leakage occurs.
[0012]
The monomer mixture may be mixed with other monomers 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 Acetacetyl group-containing (meth) acrylates such as (meth) acrylate; aromatic monomers such as styrene, methylstyrene and vinyltoluene; methacryloxypropylmethoxysilane, vinyl acetate, vinyl chloride and (meth) acrylonitrile Can do. The mixing ratio of other monomers is 50 parts by weight or less, preferably 30 parts by weight or less, particularly preferably 10 parts by weight or less, relative to 100 parts by weight of component (a) alkyl acrylate ester.
[0013]
The acrylic polymer used for the pressure-sensitive adhesive for optical members of the present invention can be produced by a conventionally known polymerization method such as a solution polymerization method, a bulk polymerization method, an emulsion polymerization method and a suspension polymerization method. What was manufactured by the solution polymerization method and bulk polymerization method which do not contain polymerization stabilizers, such as a suspension agent, is preferable. Moreover, the weight average molecular weight (Mw) by the gel permeation chromatography (GPC) of the said acrylic polymer is 500,000 or more and 2 million or less, Preferably it is 500,000 or more and 1.8 million or less. When Mw is less than 500,000, even when the gel fraction described below is adjusted within a suitable range, the cohesive force of the adhesive during heating is not sufficient, and foaming tends to occur under high temperature conditions. If it exceeds 1, the stress relaxation property of the pressure-sensitive adhesive is lowered, and, for example, when used for bonding a glass substrate and a polarizing plate, a light leakage phenomenon tends to occur at the peripheral edge of the pasting surface.
[0014]
Examples of isocyanate compounds used in the pressure-sensitive adhesive for optical members of the present invention include tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, Isocyanate monomers such as hydrogenated diphenylmethane diisocyanate, isocyanate compounds obtained by adding these isocyanate monomers with trimethylolpropane, isocyanurates, burette compounds, polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprenes Urethane prepolymer-type isocyanate that has undergone addition reaction such as polyol And the like.
[0015]
The pressure-sensitive adhesive for optical members of the present invention has a gel fraction obtained by subjecting a pressure-sensitive adhesive composition comprising 0.01 to 1 part by weight of an isocyanate compound to a crosslinking reaction at room temperature or under heating with respect to 100 parts by weight of the acrylic polymer. Although it is 1% or more and 50% or less, it is more preferable that the gel fraction is 10% or more and 45% or less. When this gel fraction is low, foaming in a high-temperature atmosphere tends to occur due to insufficient cohesive force of the pressure-sensitive adhesive. Moreover, when the gel fraction is too high, the stress relaxation property of the pressure-sensitive adhesive is lowered. For example, when used for bonding a glass substrate and a polarizing plate, a light leakage phenomenon is likely to occur at the peripheral edge of the bonding surface. .
[0016]
When the acrylic polymer is prepared by solution polymerization, the acrylic polymer and the isocyanate compound may be mixed by adding an isocyanate compound to the acrylic polymer solution after the polymerization is completed. In the case of preparation, since uniform mixing becomes difficult after completion of the polymerization, it is preferable to mix during the polymerization.
[0017]
The gel fraction was obtained by collecting about 0.1 g of an adhesive in a sample bottle, adding 30 cc of ethyl acetate and shaking for 24 hours, and then filtering the contents of the sample bottle with a 200-mesh stainless steel wire mesh. The above residue is dried at 100 ° C. for 2 hours, and the dry weight is measured.
[Formula 1]
Figure 0004134350
[0018]
The pressure-sensitive adhesive of the present invention may contain 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.
[0019]
In the optical member of the present invention, a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive for optical members is formed on one side or both sides of a support. Examples of the support include a polarizing film, a retardation film, an elliptical polarizing film, an antireflection film, a brightness enhancement film, a light diffusion film, and the like. In particular, the support is a polarizing film, a retardation film, or an elliptical polarizing film. In this case, the stress relaxation property of the pressure-sensitive adhesive for optical members can be exhibited more.
[0020]
The optical member in which the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive for the optical member is formed on the polarizing film, the retardation film, and the elliptical polarizing film of the present invention has sufficient thermal stress when the pressure-sensitive adhesive layer is attached to a glass substrate or the like. In order to alleviate, no light leakage occurs.
【Example】
The present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
[0021]
<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 part by weight of acrylic acid, 90 parts by weight of ethyl acetate and 0.1 part by weight of benzoyl peroxide are placed in a reaction vessel. Air was replaced with nitrogen gas. Next, the mixture was heated to 70 ° C. with stirring and reacted for 8 hours to obtain an acrylic polymer solution A. Mw by GPC of the obtained acrylic polymer A was 1,200,000.
[0022]
<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 parts by weight of azobisisobutyronitrile are placed in a reaction vessel. 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. After 4 hours, 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 reaction was further continued for 4 hours to obtain an acrylic polymer solution B. It was. Mw by GPC of the obtained acrylic polymer B was 700,000.
[0023]
<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. The air was replaced with nitrogen gas. Next, the mixture was heated to 73 ° C. with stirring and reacted for 8 hours to obtain an acrylic polymer solution C. Mw of the obtained acrylic polymer C by GPC was 1.4 million.
[0024]
<Production Example 4> Acrylic polymer solution D
In Production Example 1, an acrylic polymer solution D was obtained in the same manner as Production Example 1 except that acrylic acid was changed to 4 parts by weight. Mw by GPC of the obtained acrylic polymer D was 1.3 million.
[0025]
<Production Example 5> Acrylic polymer solution E
In Production Example 1, an acrylic polymer solution E was obtained in the same manner as in Production Example 1 except that acrylic acid was eliminated. Mw of the obtained acrylic polymer E by GPC was 1,200,000.
[0026]
<Production Example 6> Acrylic polymer solution F
An acrylic polymer solution F was obtained in the same manner as in Production Example 1 except that 2-hydroxyethyl acrylate was changed to 0.05 parts by weight in Production Example 1. Mw of the obtained acrylic polymer F by GPC was 1.1 million.
[0027]
<Production Example 7> Acrylic polymer solution G
An acrylic polymer solution G was obtained in the same manner as in Production Example 1 except that 2-hydroxyethyl acrylate was changed to 12 parts by weight in Production Example 1. Mw by GPC of the obtained acrylic polymer G was 1.4 million.
[0028]
<Production Example 8> Acrylic polymer solution H
An acrylic polymer solution H 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 in Production Example 1. Mw by GPC of the obtained acrylic polymer H was 300,000.
[0029]
<Production Example 9> Production of acrylic polymer by bulk polymerization As the first step, 100 parts by weight of 2-ethylhexyl acrylate, 2 parts by weight of 2-hydroxyethyl methacrylate, and 1 part by weight of dimethylaminoethyl acrylate are placed in a reaction vessel, and this reaction is performed. After the air in the container was replaced with nitrogen gas, the temperature was raised to 50 ° C. with stirring. Next, when 0.025 part by weight of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) was added, the temperature of the reaction system increased, and the polymerization reaction proceeded without cooling. The temperature of the reaction system reached 119 ° C. and then gradually began 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. Furthermore, it cooled to room temperature with the water bath, and obtained the acrylic type partial polymer.
Next, as a second step, 0.3 parts by weight of a photopolymerization initiator (trade name: Darocur 1173, manufactured by Ciba Geigy Co., Ltd.) is added to 100 parts by weight of this acrylic partial polymer, and the mixture is thoroughly stirred to polymerize. A composition was obtained. It was applied to a peeled polyester film, and under a nitrogen gas atmosphere, photopolymerization was performed by irradiating light from a high-pressure mercury lamp for 360 seconds at 10 W / m 2 and then for 45 seconds at 3000 W / m 2 . An acrylic polymer layer was provided. Mw by GPC of this acrylic polymer layer was 1.15 million.
[0030]
Table 1 shows the GPC measurement conditions.
[Table 1]
Figure 0004134350
[0031]
<Example 1>
To 100 parts by weight of the solid content of the acrylic polymer solution A, 0.05 part by weight of tolylene diisocyanate adduct of trimethylolpropane was added and stirred well to obtain an adhesive composition. After applying it to the peeled polyester film and drying it, providing a 25 μm adhesive layer, transferring it to one side of the polarizing film and aging it for 7 days at a temperature of 23 ° C. and a humidity of 65%. An optical member having a layer was obtained.
[0032]
<Example 2>
To 100 parts by weight of the solid content of the acrylic polymer solution B, 0.7 part by weight of a tolylene diisocyanate adduct of trimethylolpropane was added and stirred well to obtain an adhesive composition. After applying it to the peeled polyester film and drying it, providing a 25 μm adhesive layer, transferring it to one side of the polarizing film and aging it for 7 days at a temperature of 23 ° C. and a humidity of 65%. An optical member having a layer was obtained.
[0033]
<Example 3>
To 100 parts by weight of the solid content of the acrylic polymer solution C, 0.1 part by weight of a trimethylolpropane xylylene diisocyanate adduct was added and stirred well to obtain a pressure-sensitive adhesive composition. After applying it to the peeled polyester film and drying it, providing a 25 μm adhesive layer, transferring it to one side of the polarizing film and aging it for 7 days at a temperature of 23 ° C. and a humidity of 65%. An optical member having a layer was obtained.
[0034]
<Example 4>
In Production Example 9, the polymerizable composition in the second step was the same except that 0.5 parts by weight of a tolylene diisocyanate adduct of trimethylolpropane was further added to 100 parts by weight of the acrylic partial polymer. A 25 μm pressure-sensitive adhesive layer was obtained on the release-treated polyester film. It was transferred to one surface of a polarizing film and aged for 7 days under the conditions of a temperature of 23 ° C. and a humidity of 65% to obtain an optical member having an adhesive layer.
[0035]
<Example 5>
[0036]
In Example 1, except that the xylylene diisocyanate adduct of trimethylolpropane was changed to hexamethylene diisocyanate of trimethylolpropane, a 25 μm pressure-sensitive adhesive layer was obtained on the peel-treated polyester film in the same manner as in Example 1. It was. It was transferred to one surface of a polarizing film and aged for 7 days under the conditions of a temperature of 23 ° C. and a humidity of 65% to obtain an optical member having an adhesive layer.
[0037]
<Example 6>
[0038]
In Example 1, except that the xylylene diisocyanate adduct of trimethylolpropane was changed to tolylene diisocyanate of trimethylolpropane, a 25 μm pressure-sensitive adhesive layer was obtained on the peel-treated polyester film in the same manner as in Example 1. It was. It was transferred to one surface of a polarizing film and aged for 7 days under the conditions of a temperature of 23 ° C. and a humidity of 65% to obtain an optical member having an adhesive layer.
[0039]
<Comparative Example 1>
An optical member was obtained in the same manner as in Example 1 except that the acrylic polymer solution A was changed to the acrylic polymer solution D in Example 1.
[0040]
<Comparative example 2>
An optical member was obtained in the same manner as in Example 1 except that the acrylic polymer solution A was changed to the acrylic polymer solution E in Example 1.
[0041]
<Comparative Example 3>
An optical member was obtained in the same manner as in Example 1 except that the acrylic polymer solution A was changed to the acrylic polymer solution F in Example 1.
[0042]
<Comparative example 4>
An optical member was obtained in the same manner as in Example 1 except that the acrylic polymer solution A was changed to the acrylic polymer solution G in Example 1.
[0043]
<Comparative Example 5>
An optical member was obtained in the same manner as in Example 1 except that the acrylic polymer solution A was changed to the acrylic polymer solution H in Example 1.
[0044]
<Comparative Example 6>
In Example 3, an optical member was obtained in the same manner as Example 3 except that the xylylene diisocyanate adduct of trimethylolpropane was changed to 0.001 part by weight.
[0045]
<Comparative Example 7>
In Example 3, an optical member was obtained in the same manner as in Example 3 except that the xylylene diisocyanate adduct of trimethylolpropane was changed to 3 parts by weight.
[0046]
Gel fraction In Examples 1-6 and Comparative Examples 1-7, using a polyester film that had been subjected to a release treatment instead of a polarizing film, after coating, 1, 3, 5, 7, 10, 15 The gel fraction in the day was measured.
The gel fraction was obtained by collecting about 0.1 g of an 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 mesh, the residue on the wire mesh was dried at 100 ° C. for 2 hours, the dry weight was measured, and the content was obtained from the following formula [I]. The results are shown in Table 2.
[Formula 2]
Figure 0004134350
[Table 2]
Figure 0004134350
[0047]
Durability <br/> above Examples 1 to 4 and Comparative Examples 1 to 7, temperature 23 ° C., having a thickness of 0.5mm 15-inch optical member obtained by aging for 7 days at a humidity 65% RH Laminator rolls were attached to both sides of the alkali-free glass plate so as to be orthogonal Nicols. Subsequently, it was bonded to an autoclave at 50 ° C. and 5 atm for 20 minutes.
The sample thus obtained was left under conditions of 120 ° C., 80 ° C. and 90% RH for 500 hours, and light leakage caused by residual stress due to peeling of the optical member, foaming at the adhesive interface and dimensional change was visually observed. Observed. The results are shown in Table 2 together with the evaluation results of the gel fraction. “◯” in the table means that there is no problem in practical use, “Δ” means that a problem may occur in practical use, and “×” indicates that there is a problem in practical use. In addition, the foaming and light leakage of Comparative Example 4 and Comparative Example 7 were largely peeled off and were not in an observable state.
[Table 3]
Figure 0004134350
[0048]
【The invention's effect】
As shown in the above embodiment, the pressure-sensitive adhesive for optical members of the present invention and the optical member using the same have heat resistance and moisture resistance, as is apparent from the comparison with optical members using conventional pressure-sensitive adhesive for optical members. In addition to satisfying thermal properties, stress due to dimensional change of a member such as a polarizing film can be relieved, and light leakage and color unevenness can be significantly suppressed. Furthermore, the pressure-sensitive adhesive for optical members of the present invention has a cross-linked structure completed in a short time compared with conventional pressure-sensitive adhesives, and the gel fraction and pressure-sensitive adhesive performance are stabilized. The used optical member can be used promptly after adhesion processing (coating), and greatly improves productivity.

Claims (4)

(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0.5〜5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、
イソシアネート化合物0.01重量部以上1.0重量部以下と
からなる粘着剤組成物を、架橋反応させることによりゲル分率を10%以上45%以下としたことを特徴とする光学部材用粘着剤。
(A) (b) 0.5 to 5 parts by weight of a monomer having a hydroxyl group in the molecule with respect to 100 parts by weight of the (meth) acrylic acid alkyl ester, and (c) a carboxyl group or an amide group in the molecule. , A copolymer of a monomer mixture containing 0.05 to 3 parts by weight of a monomer having any functional group of amino group, and having a weight average molecular weight of 500,000 or more by gel permeation chromatography 100 parts by weight of 2 million or less acrylic polymer,
A pressure-sensitive adhesive for an optical member, wherein the pressure-sensitive adhesive composition comprising 0.01 parts by weight or more and 1.0 parts by weight or less of an isocyanate compound is subjected to a crosslinking reaction so that the gel fraction is 10% to 45%. .
アクリル系ポリマーが、溶液重合又は塊状重合により得られたものであることを特徴とする請求項記載の光学部材用粘着剤。Acrylic polymer, an optical member for a pressure-sensitive adhesive of claim 1, wherein a is obtained by solution polymerization or bulk polymerization. 支持体の片面あるいは両面に、請求項1又は2記載の粘着剤からなる粘着剤層を形成したことを特徴とする光学部材。An optical member comprising an adhesive layer made of the adhesive according to claim 1 or 2 formed on one side or both sides of a support. 支持体が偏光フィルム、位相差フィルム、又は、楕円偏光フィルムであることを特徴とする請求項3記載の光学部材。The optical member according to claim 3, wherein the support is a polarizing film, a retardation film, or an elliptically polarizing film.
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