JP6067964B2 - 放射線硬化性粘着シート - Google Patents
放射線硬化性粘着シート Download PDFInfo
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- JP6067964B2 JP6067964B2 JP2011176853A JP2011176853A JP6067964B2 JP 6067964 B2 JP6067964 B2 JP 6067964B2 JP 2011176853 A JP2011176853 A JP 2011176853A JP 2011176853 A JP2011176853 A JP 2011176853A JP 6067964 B2 JP6067964 B2 JP 6067964B2
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- adhesive sheet
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- sensitive adhesive
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- pressure
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
本発明は、放射線照射前においては良好な流動性および被着体に対する良好な初期接着を伴うホットメルト特性を実現し、かつ放射線照射後においては良好な硬さを実現する、放射線硬化性粘着シートを提供する。
本開示の一実施態様は、放射線反応性部位を有する(メタ)アクリル共重合体、および、放射線照射によって該(メタ)アクリル共重合体との結合を形成することが可能な可塑剤、を含んでなる、放射線硬化性粘着シート(以下、単に「粘着シート」ともいう)を提供する。
本開示の一実施態様に係る放射線硬化性粘着シートは、放射線反応性部位を有する(メタ)アクリル共重合体(以下、単に(メタ)アクリル共重合体ともいう)を含む。(メタ)アクリル共重合体において、ある放射線反応性部位と、これと反応することになる「他の部位」とは同一分子内または異なる分子内に存在できる。
本開示の一実施態様に係る放射線硬化性粘着シートは、放射線照射によって、放射線反応性部位を有する(メタ)アクリル共重合体との結合を形成することが可能な可塑剤を含む。このような可塑剤を含む放射線硬化性粘着シートは、放射線照射前においては高い初期接着および良好な流動性を伴うホットメルト特性を有し、かつ放射線照射後においては高い硬さ(特に貯蔵弾性率)を有する。より典型的には、本開示の一実施態様に係る放射線硬化性粘着シートは、放射線照射前においては、放射線反応性部位を有する(メタ)アクリル共重合体を単独で用いて形成された粘着シートと比べて改善されたホットメルト特性を有し、かつ放射線照射後においては放射線反応性部位を有する(メタ)アクリル共重合体を単独で用いて形成された粘着シートと比べて高い硬さを有する。
本開示の一実施態様に係る放射線硬化性粘着シートは、上述した、放射線反応性部位を有する(メタ)アクリル共重合体および可塑剤に加え、任意成分を含んでもよい。任意成分としては、フィラー、酸化防止剤などが挙げられる。
該第1の基材および該第2の基材の少なくとも一方が、その主面の1つの少なくとも一部に亘る3次元表面トポグラフィーを有し、
該放射線硬化性粘着シートを該第1の基材の少なくとも一方の表面側に隣接させて配置する工程と、
該第2の基材を該放射線硬化性粘着シートに隣接させて配置する工程と、
該放射線硬化性粘着シートを加熱および/または加圧して該3次元表面トポグラフィーに追従させる工程と、
該放射線硬化性粘着シートに放射線を照射する工程と、
を含む、方法である。
上記方法において、工程順は上述の記載順に限定されない。
該第1の基材および該第2の基材の少なくとも一方が歪みに対して敏感であり、
該放射線硬化性粘着シートを該第1の基材の少なくとも一方の表面側に隣接させて配置する工程と、
該第2の基材を該放射線硬化性粘着シートに隣接させて配置する工程と、
該放射線硬化性粘着シートを加熱および/または加圧する工程と、
該放射線硬化性粘着シートに放射線を照射する工程と、
を含む、方法である。歪みに対して敏感な基材の例は前述した通りである。
本実施態様におけるそれぞれの工程の詳細は、3次元表面トポグラフィーを有する基材を用いる実施態様について上述したのと同様の手順で実施できる。
[モノマーおよび開始剤の略称]
2−EHA:2−エチルヘキシルアクリレート
ISTA:イソステアリルアクリレート(大阪有機化学工業(株)より入手可能)
AA:アクリル酸
AEBP:4−アクリロイルオキシエトキシベンゾフェノン
DCP−A:トリシクロデカンジメタノールジアクリレート
DCP−M:トリシクロデカンジメタノールジメタクリレート
SR−399:ジペンタエリスリトールペンタアクリレート(Sartomer Companyより入手可能)
V−65:熱開始剤(2,2’−アゾビス(2,4−ジメチルバレロニトリル)(和光純薬(株)より入手可能)
MOI:2−イソシアネートエチルメタクリレート(昭和電工(株)から入手可能)
TPO:2,4,6−トリメチルベンゾイルジフェニルホスフィンオキサイド
EtOAc:酢酸エチル
MEK:メチルエチルケトン
作製例1
粘着シート(PSAシート−1)は以下のように作製した。
まず、放射線反応性部位として紫外線架橋性部位を有するアクリル酸エステルを含有するモノマーのアクリル共重合体を合成した。紫外線架橋性部位を有するアクリル酸エステルとして、4−アクリロイルオキシエトキシベンゾフェノンを用いた。
転写型粘着テープ(PSAシート−2)は、ポリマー固形分/DCP−Aの混合比を90/10(質量比)に調整した以外はPSAシート−1と同様にして作製した。
転写型粘着テープ(PSAシート−3)は、ポリマー固形分/DCP−Aの混合比を85/15(質量比)に調整した以外はPSAシート−1と同様にして作製した。
接着剤転写テープ(PSAシート−4)は、ポリマー固形分/DCP−Mを混合比90/10(質量比)で用いた以外はPSAシート−1と同様にして作製した。
PSAシート−5は以下のように作製した。
次に、メタクリロイル基をポリマー構造中に導入するために、得られたポリマー溶液中にMOIを添加した。MOIのイソシアネートの反応を、23℃で24時間のエージングにおいて進行させた。ポリマー固形分/MOIの混合比は、100/0.5(質量%/質量%)に調整した。次いで、メタクリロイル基を有するアクリル共重合体(ポリマー3)の溶液を得た。
接着剤転写テープ(PSAシート−6)は、ポリマー1溶液を他のものと混合することなく直接コートした以外はPSAシート−1と同様にして作製した。
接着剤転写テープ(PSAシート−7)は、ポリマー3溶液に、ポリマー固形分/TPO混合比が100/0.5(質量比)となるようにTPOを添加し、これをPSAシート−1と同様の手順にてコートして作製した。
接着剤転写テープ(PSAシート−8)は、ポリマー2溶液に、ポリマー固形分/DCP-A/TPO混合比が95/5/0.5(質量比)となるようにDCP−AとTPOとを添加し、これをPSAシート−1と同様の手順にてコートして作製した。
[剥離強度(接着試験)(例1〜5、比較例1、2)]
接着試験サンプルを以下のように作製した。
粘着シートに対して、剥離フィルムを介して、フュージョンUVシステムズ・ジャパン(株)製の紫外線照射装置F−300(H−バルブ,120W/cm,15mpm×15pass)により紫外線を照射した。UV POWER PUCK(登録商標)II(EIT社)によって測定される総UVエネルギーは、UV−A(320〜390nm)について1940mJ/cm2、およびUV−B(280〜320nm)について74mJ/cm2であった。
紫外線照射前および紫外線照射後の粘着シートの相対的な流動性/追従性、および、貯蔵弾性率を評価するために、粘着シートの動的機械分析(DMA)を、動的粘弾性測定装置、ARES(TAインスツルメンツ社製)を用いて実施した。測定には、紫外線照射前および紫外線照射後のそれぞれの粘着シートを、約3mm厚となるように積層し、8mmφの抜き刃で打ち抜いて作製した試験片を用いた。測定は剪断モード(1Hz)で、昇温速度5℃/分にて、温度範囲−40℃〜200℃で実施した、貯蔵弾性率(G’)の結果を表2に纏める。
まず、積層体を以下のように作製した。
PSAシート−3の剥離フィルムを取り外し、PSAシート−3を188μm厚のPET(ESTER FILM E5101として、東洋紡績(株)より入手可能)に適用した。次に、他の剥離フィルムを取り外し、PSAシート−3をガラス板に適用し、積層体(PET/粘着シート/ガラス)を作製した。
積層体の作製および積層体の評価を、PSAシート−3に代えてPSAシート−4を用いた以外は例11に従って行った。結果を表3に示す。
積層体の作製および積層体の評価を、PSAシート−3に代えてPSAシート−5を用いた以外は例11に従って行った。結果を表3に示す。
積層体の作製および積層体の評価を、PSAシート−3に代えてPSAシート−6を用いた以外は例11に従って行った。結果を表3に示す。
積層体の作製および積層体の評価を、PSAシート−3に代えてPSAシート−7を用いた以外は例11に従って行った。結果を表3に示す。
まず、積層体を以下のように作製した。
例14
PSAシート−5を25mm×25mmにカットし、一方の剥離フィルムを外してから、30mm×60mm×2mm厚のガラス板に適用した。次に、もう一方の剥離フィルムを取り外し、30mm×60mm×2mm厚のガラス板に適用し、積層体(ガラス/粘着シート/ガラス)を作製した。
積層体の作製および積層体の評価を、PSAシート−5に代えてPSAシート−8を用いた以外は例14に従って行った。結果を表4に示す。
20 タッチパネルユニット
1 画像表示モジュール
2 積層体
3 粘着シート
4 表面保護層
5 連続層
6 光遮蔽層
7 タッチパネル
本開示は以下も包含する。
[1] 放射線反応性部位を有する(メタ)アクリル共重合体、および、放射線照射によって前記(メタ)アクリル共重合体との結合を形成することが可能な可塑剤、を含んでなる、放射線硬化性粘着シート。
[2] 前記放射線反応性部位が、エチレン性不飽和構造を有する、上記態様1に記載の放射線硬化性粘着シート。
[3] 前記放射線反応性部位が、ベンゾフェノン構造を有する、上記態様1または2に記載の放射線硬化性粘着シート。
[4] 前記可塑剤が、多官能(メタ)アクリレートを含む、上記態様1〜3のいずれかに記載の放射線硬化性粘着シート。
[5] 前記可塑剤が、脂環式部分を含む、上記態様1〜4のいずれかに記載の放射線硬化性粘着シート。
[6] 放射線照射前の粘着シートの貯蔵弾性率が、30℃、1Hzにおいて、1.0×10 4 Pa以上、1.0×10 6 Pa以下、かつ80℃、1Hzにおいて、5.0×10 4 Pa以下であり、
さらに、放射線照射後の粘着シートの貯蔵弾性率が、130℃、1Hzにおいて、1.0×10 3 Pa以上である、上記態様1〜5のいずれかに記載の放射線硬化性粘着シート。
[7] 放射線照射後の粘着シートの貯蔵弾性率が、130℃、1Hzにおいて、1.0×10 4 Pa以上である、上記態様6に記載の放射線硬化性粘着シート。
[8] 基材と、上記態様1〜7のいずれかに記載の放射線硬化性粘着シートとを含む、積層体。
[9] 第1の基材と、第2の基材と、前記第1の基材と前記第2の基材の間に配置された、上記態様1〜7のいずれかに記載の放射線硬化性粘着シートと、を含む積層体であって、前記第1の基材の少なくとも一方の表面が前記放射線硬化性粘着シートと接触している、積層体。
[10] 前記第1の基材が表面保護層であり、前記第2の基材が画像表示モジュールまたはタッチパネルである、上記態様9に記載の積層体。
[11] 第1の基材と、第2の基材と、前記第1の基材と前記第2の基材の間に配置された、上記態様1〜7のいずれかに記載の放射線硬化性粘着シートと、を含む積層体の製造方法であって、
前記第1の基材および前記第2の基材の少なくとも一方が、その主面の一方の少なくとも一部に亘る3次元表面トポグラフィーを有し、
前記放射線硬化性粘着シートを前記第1の基材の少なくとも一方の表面側に隣接させて配置する工程と、
前記第2の基材を前記放射線硬化性粘着シートに隣接させて配置する工程と、
前記放射線硬化性粘着シートを加熱および/または加圧して前記3次元表面トポグラフィーに追従させる工程と、
前記放射線硬化性粘着シートに放射線を照射する工程と、
を含む、方法。
[12] 第1の基材と、第2の基材と、上記態様1〜7のいずれかに記載の放射線硬化性粘着シートと、を含む積層体の製造方法であって、
前記第1の基材および前記第2の基材の少なくとも一方が歪みに対して敏感であり、
前記放射線硬化性粘着シートを前記第1の基材の少なくとも一方の表面側に隣接させて配置する工程と、
前記第2の基材を前記放射線硬化性粘着シートに隣接させて配置する工程と、
前記放射線硬化性粘着シートを加熱および/または加圧する工程と、
前記放射線硬化性粘着シートに放射線を照射する工程と、
を含む、方法。
Claims (12)
- 放射線反応性部位を有する(メタ)アクリル共重合体、および、放射線照射によって前記(メタ)アクリル共重合体との結合を形成することが可能な可塑剤、を含んでなる、放射線硬化性粘着シートであって、
前記可塑剤の量が、前記(メタ)アクリル共重合体100質量部に対して1質量部以上20質量部以下であり、
前記放射線硬化性粘着シートの放射線照射後の貯蔵弾性率が、30℃、1Hzにおいて、2.0×106Pa以上であり、
放射線照射後に粘着シートの接着性が増大する、放射線硬化性粘着シート。 - 前記可塑剤の量が、前記(メタ)アクリル共重合体100質量部に対して1質量部以上10質量部以下である、請求項1に記載の放射線硬化性粘着シート。
- 前記可塑剤が、脂環式部分を含む、請求項1又は2に記載の放射線硬化性粘着シート。
- 前記放射線反応性部位が、エチレン性不飽和構造を有する、請求項1〜3のいずれか1項に記載の放射線硬化性粘着シート。
- 前記放射線反応性部位が、ベンゾフェノン構造を有する、請求項1〜4のいずれか1項に記載の放射線硬化性粘着シート。
- 前記可塑剤が、多官能(メタ)アクリレートを含む、請求項1〜5のいずれか1項に記載の放射線硬化性粘着シート。
- 放射線照射前の粘着シートの貯蔵弾性率が、30℃、1Hzにおいて、1.0×104Pa以上、1.0×106Pa以下、かつ80℃、1Hzにおいて、5.0×104Pa以下であり、
さらに、放射線照射後の粘着シートの貯蔵弾性率が、130℃、1Hzにおいて、1.0×103Pa以上である、請求項1〜6のいずれか1項に記載の放射線硬化性粘着シート。 - 放射線照射後の粘着シートの貯蔵弾性率が、130℃、1Hzにおいて、1.0×104Pa以上である、請求項7に記載の放射線硬化性粘着シート。
- 第1の基材と、第2の基材と、前記第1の基材と前記第2の基材の間に配置された、請求項1〜8のいずれか1項に記載の放射線硬化性粘着シートと、を含む積層体であって、前記第1の基材の少なくとも一方の表面が前記放射線硬化性粘着シートと接触している、積層体。
- 前記第1の基材が表面保護層であり、前記第2の基材が画像表示モジュールまたはタッチパネルである、請求項9に記載の積層体。
- 第1の基材と、第2の基材と、前記第1の基材と前記第2の基材の間に配置された、請求項1〜8のいずれか1項に記載の放射線硬化性粘着シートと、を含む積層体の製造方法であって、
前記第1の基材および前記第2の基材の少なくとも一方が、その主面の一方の少なくとも一部に亘る3次元表面トポグラフィーを有し、
前記放射線硬化性粘着シートを前記第1の基材の少なくとも一方の表面側に隣接させて配置する工程と、
前記第2の基材を前記放射線硬化性粘着シートに隣接させて配置する工程と、
前記放射線硬化性粘着シートを加熱および/または加圧して前記3次元表面トポグラフィーに追従させる工程と、
前記放射線硬化性粘着シートに放射線を照射する工程と、
を含む、方法。 - 第1の基材と、第2の基材と、請求項1〜8のいずれか1項に記載の放射線硬化性粘着シートと、を含む積層体の製造方法であって、
前記第1の基材および前記第2の基材の少なくとも一方が歪みに対して敏感であり、
前記放射線硬化性粘着シートを前記第1の基材の少なくとも一方の表面側に隣接させて配置する工程と、
前記第2の基材を前記放射線硬化性粘着シートに隣接させて配置する工程と、
前記放射線硬化性粘着シートを加熱および/または加圧する工程と、
前記放射線硬化性粘着シートに放射線を照射する工程と、
を含む、方法。
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JP2011176853A JP6067964B2 (ja) | 2011-08-12 | 2011-08-12 | 放射線硬化性粘着シート |
US14/238,208 US20140302313A1 (en) | 2011-08-12 | 2012-08-09 | Radiation curable pressure sensitive adhesive sheet |
PCT/US2012/050154 WO2013025443A2 (en) | 2011-08-12 | 2012-08-09 | Radiation curable pressure sensitive adhesive sheet |
KR1020147006088A KR101966479B1 (ko) | 2011-08-12 | 2012-08-09 | 방사선 경화성 감압 접착제 시트 |
CN201610409779.1A CN105907328B (zh) | 2011-08-12 | 2012-08-09 | 可辐射固化的压敏粘结剂片材 |
CN201280039223.8A CN103717692B (zh) | 2011-08-12 | 2012-08-09 | 可辐射固化的压敏粘结剂片材 |
TW101129080A TWI580753B (zh) | 2011-08-12 | 2012-08-10 | 照射可固化壓敏性黏著片 |
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US (1) | US20140302313A1 (ja) |
JP (1) | JP6067964B2 (ja) |
KR (1) | KR101966479B1 (ja) |
CN (2) | CN103717692B (ja) |
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- 2012-08-09 US US14/238,208 patent/US20140302313A1/en not_active Abandoned
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WO2013025443A3 (en) | 2013-04-25 |
CN105907328A (zh) | 2016-08-31 |
US20140302313A1 (en) | 2014-10-09 |
WO2013025443A2 (en) | 2013-02-21 |
KR20140051398A (ko) | 2014-04-30 |
TWI580753B (zh) | 2017-05-01 |
CN103717692B (zh) | 2016-08-17 |
JP2013040256A (ja) | 2013-02-28 |
TW201311855A (zh) | 2013-03-16 |
KR101966479B1 (ko) | 2019-04-05 |
CN103717692A (zh) | 2014-04-09 |
CN105907328B (zh) | 2020-10-13 |
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