JP2016108534A - 粘着シート - Google Patents
粘着シート Download PDFInfo
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- JP2016108534A JP2016108534A JP2015164270A JP2015164270A JP2016108534A JP 2016108534 A JP2016108534 A JP 2016108534A JP 2015164270 A JP2015164270 A JP 2015164270A JP 2015164270 A JP2015164270 A JP 2015164270A JP 2016108534 A JP2016108534 A JP 2016108534A
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- pressure
- sensitive adhesive
- adhesive sheet
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
Description
ここに開示される粘着シートは、その粘着剤層表面におけるコート層非配置部の面積割合(粘着シートの接着面(粘着性表面)におけるコート層の面積割合でもあり得る。)が70%以上であることによって特徴づけられる。これにより、高い経時接着力を確保することができる。上記面積割合は、好ましくは75%以上、より好ましくは80%以上である。良好な空気抜け性を得る観点からは、上記面積割合は、好ましくは90%以下、より好ましくは85%以下である。
ここに開示されるフィルム状基材としては、例えば、樹脂フィルム、紙、布、ゴムフィルム、発泡体フィルム、金属箔、これらの複合体や積層体等を用いることができる。なかでも、貼り付け性や外観性の観点から、樹脂フィルム層を含むことが好ましい。樹脂フィルム層を含むことは、寸法安定性、厚さ精度、加工性、引張強度等の観点からも有利である。樹脂フィルムの例としては、ポリエチレン(PE)、ポリプロピレン(PP)、エチレン・プロピレン共重合体等のポリオレフィン系樹脂フィルム;ポリエチレンテレフタレート(PET)、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系樹脂フィルム;塩化ビニル系樹脂フィルム;酢酸ビニル系樹脂フィルム;ポリイミド系樹脂フィルム;ポリアミド系樹脂フィルム;フッ素系樹脂フィルム;セロハン;等が挙げられる。好適例としては、PE、PP、PETから形成された樹脂フィルムが挙げられる。樹脂フィルムのなかでは、ポリエステルフィルムがより好ましく、そのなかでもPETフィルムがさらに好ましい。フィルム状基材は、単層構造であってもよく、2層または3層以上の多層構造を有してもよい。
ここに開示される粘着剤層は、典型的には、室温付近の温度域において柔らかい固体(粘弾性体)の状態を呈し、圧力により簡単に被着体に接着する性質を有する材料(粘着剤)から構成された層をいう。ここでいう粘着剤は、「C. A. Dahlquist, “Adhesion : Fundamental and Practice”, McLaren & Sons, (1966) P. 143」に定義されているとおり、一般的に、複素引張弾性率E*(1Hz)<107dyne/cm2を満たす性質を有する材料(典型的には、25℃において上記性質を有する材料)である。
CH2=C(R1)COOR2 (1)
ここで、上記式(1)中のR1は水素原子またはメチル基である。また、R2は炭素原子数1〜20の鎖状アルキル基(以下、このような炭素原子数の範囲を「C1−20」と表すことがある。)である。粘着剤の貯蔵弾性率等の観点から、R2がC1−12(例えばC2−10、典型的にはC4−8)の鎖状アルキル基であるアルキル(メタ)アクリレートが好ましい。上記R2がC1−20の鎖状アルキル基であるアルキル(メタ)アクリレートは、1種を単独でまたは2種以上を組み合わせて用いることができる。好ましいアルキル(メタ)アクリレートとして、n−ブチルアクリレートおよび2−エチルヘキシルアクリレートが挙げられる。
架橋反応の促進、製造効率向上等の観点から、粘着剤組成物の乾燥は加熱下で行うことが好ましい。乾燥温度は、例えば40〜150℃程度とすることができ、通常は60〜130℃程度とすることが好ましい。粘着剤組成物を乾燥させた後、さらに、粘着剤層内における成分移行の調整、架橋反応の進行、基材や粘着剤層内に存在し得る歪の緩和等を目的としてエージングを行ってもよい。
粘着剤層表面を部分的に覆うコート層は、空気抜け性を付与し得るものであればよく、その限りにおいて特に制限はない。コート層材料の好適例としては樹脂材料が挙げられる。外観性の観点から、透明または半透明の樹脂材料から形成されたコート層が好ましい。
(1) フィルム状基材と、該フィルム状基材の少なくとも一方の表面に設けられた粘着剤層と、を備える粘着シートであって、
前記粘着剤層表面を部分的に覆うコート層を備え、これによって、該粘着剤層表面はコート層配置部とコート層非配置部とを有しており、
前記粘着剤層表面における前記コート層非配置部の面積割合は70%以上であり、
前記コート層配置部は、前記粘着剤層表面を上方から見たときに、該粘着剤層の一端から他端に向かって線状に延びる部分を有しており、
前記線状に延びる部分の幅は0.1〜2mmの範囲内である、粘着シート。
(2) 前記粘着剤層表面には、前記線状に延びる部分が複数配置されており、
前記複数の線状に延びる部分のうち一群を構成する複数の線状に延びる部分は、その幅方向にて間隔をおいて配置されており、これによって、前記コート層配置部はストライプ状パターンを有する、上記(1)に記載の粘着シート。
(3) 前記コート層配置部は、第1ストライプ状パターン部と、該第1ストライプ状パターン部と交差するように配置された第2ストライプ状パターン部とを含み、これによって、前記コート層配置部は格子状パターンを有する、上記(2)に記載の粘着シート。
(4) 前記コート層配置部において、一のストライプ状パターンを構成する複数の線状に延びる部分の間隔は1.0〜10mmの範囲内である、上記(2)または(3)に記載の粘着シート。
(5) 前記コート層が部分的に配置された粘着性表面は、13N/25mm以上の24時間経過後180度剥離強度を示す、上記(1)〜(4)のいずれかに記載の粘着シート。
前記アクリル系ポリマーは、モノマー成分として、式(1):
CH2=C(R1)COOR2 (1)
(上記式(1)中のR1は水素原子またはメチル基である。また、R2は炭素原子数1〜20の鎖状アルキル基である。);で表されるアルキル(メタ)アクリレートを50重量%を超える割合で含む、上記(1)〜(5)のいずれかに記載の粘着シート。
(7) 前記アルキル(メタ)アクリレートは、n−ブチルアクリレートおよび/または2−エチルヘキシルアクリレートである、上記(6)に記載の粘着シート。
(8) 前記アクリル系ポリマーは、副モノマーとしてカルボキシ基含有モノマーおよび/または水酸基含有モノマーが共重合されたアクリル系ポリマーである、上記(6)または(7)のいずれかに記載の粘着シート。
(9) 前記アクリル系ポリマーは、アクリル酸、メタクリル酸、2−ヒドロキシエチルアクリレートおよび4−ヒドロキシブチルアクリレートからなる群から選択される少なくとも1種の副モノマーが共重合されたアクリル系ポリマーである、上記(6)〜(8)のいずれかに記載の粘着シート。
(10) 前記アクリル系ポリマーには、カルボキシ基含有モノマーが共重合されており、前記カルボキシ基含有モノマーの共重合割合は、前記アクリル系ポリマーの合成に使用する全モノマー成分中、0.1〜10重量%である、上記(6)〜(9)のいずれかに記載の粘着シート。
(11) 前記アクリル系ポリマーには水酸基含有モノマーが共重合されており、
前記水酸基含有モノマーの共重合割合は、前記アクリル系ポリマーの合成に使用する全モノマー成分中、0.001〜10重量%である、上記(6)〜(10)のいずれかに記載の粘着シート。
(12) 前記粘着剤層は、イソシアネート系架橋剤および/またはエポキシ系架橋剤を含む、上記(6)〜(11)のいずれかに記載の粘着シート。
(13) 前記粘着剤層は、軟化点が100℃〜140℃である粘着付与樹脂を、前記アクリル系ポリマー100重量部に対して30〜60重量部の割合で含み、
前記粘着付与樹脂は、ロジン系粘着付与樹脂、テルペン系粘着付与樹脂および炭化水素系粘着付与樹脂からなる群から選択される少なくとも1種である、上記(6)〜(12)のいずれかに記載の粘着シート。
(15) 前記コート層は、ポリウレタン系樹脂、フェノール系樹脂、エポキシ系樹脂、ポリアミド系樹脂、尿素メラミン系樹脂、シリコーン系樹脂、ポリシラザン系樹脂、フッ素系樹脂、フェノキシ樹脂、メタクリル系樹脂、アクリル系樹脂、アクリル−ウレタン系樹脂、アクリル−スチレン系樹脂、ポリアリレート樹脂、ポリエステル系樹脂、ポリオレフィン系樹脂、ポリスチレン系樹脂、ポリ塩化ビニル、塩化ビニル−酢酸ビニル共重合体、ポリ酢酸ビニル、ポリ塩化ビニリデン、ポリカーボネート、セルロース類およびポリアセタールからなる群から選択される少なくとも1種の樹脂を含む、上記(1)〜(14)のいずれかに記載の粘着シート。
(16) 前記コート層はポリウレタン系樹脂である、上記(1)〜(15)のいずれかに記載の粘着シート。
(17) 前記コート層は、二液混合硬化型のポリウレタン系樹脂である、上記(1)〜(16)のいずれかに記載の粘着シート。
(18) 前記フィルム状基材は、ポリオレフィン系樹脂フィルム、ポリエステル系樹脂フィルム、塩化ビニル系樹脂フィルム、酢酸ビニル系樹脂フィルム、ポリイミド系樹脂フィルム、ポリアミド系樹脂フィルム、フッ素系樹脂フィルムまたはセロハンフィルムである、上記(1)〜(17)のいずれかに記載の粘着シート。
(19) 前記フィルム状基材はポリエステルフィルムである、上記(1)〜(18)のいずれかに記載の粘着シート。
(20) 前記フィルム状基材はポリエチレンテレフタレートフィルムである、上記(1)〜(19)のいずれかに記載の粘着シート。
(21) 前記フィルム状基材は80%以上の全光線透過率を示す、上記(1)〜(20)のいずれかに記載の粘着シート。
(22) 前記フィルム状基材は発泡体フィルムである、上記(1)〜(17)のいずれかに記載の粘着シート。
(23) 前記発泡体フィルムの平均気泡径は10〜200μmであり、密度は0.01〜0.7g/cm3である、上記(22)に記載の粘着シート。
(24) 前記発泡体フィルムは、アクリル系樹脂発泡体またはポリオレフィン系樹脂発泡体である、上記(22)または(23)に記載の粘着シート。
前記剥離ライナーの表面のうち前記粘着面側の表面は、平滑に形成されている、剥離ライナー付き粘着シート。
(26) 少なくとも一方の表面が剥離性表面である剥離性支持体を備える粘着シート用剥離ライナーであって、
前記剥離性支持体の剥離性表面上には、粘着シートに転写可能なコート層が設けられており、これによって、該剥離性表面はコート層配置部とコート層非配置部とを有しており、
前記剥離性表面における前記コート層非配置部の面積割合は70%以上であり、
前記コート層は、前記剥離性表面の一端から他端に向かって線状に延びる部分を有しており、
前記線状に延びる部分の幅は0.1〜2mmの範囲内である、剥離ライナー。
<例1A>
(粘着剤組成物の調製)
攪拌機、温度計、窒素ガス導入管、還流冷却器、滴下ロートを備えた反応容器に、n−ブチルアクリレート70部と、2−エチルヘキシルアクリレート30部と、アクリル酸3部と、4−ヒドロキシブチルアクリレート0.05部と、重合開始剤としてアゾビスイソブチロニトリル0.08部と、重合溶媒としてのトルエンとを仕込み、60℃で6時間溶液重合してアクリル系ポリマーのトルエン溶液(粘度28Pa・s、固形分40%)を得た。得られたアクリル系ポリマーのMwは約44万であった。
上記トルエン溶液に含まれるアクリル系ポリマー100部に対し、粘着付与樹脂としての重合ロジンペンタエリスリトールエステル(荒川化学工業社製、商品名「ペンセルD−125」、軟化点125℃)30部を加えた後、イソシアネート系架橋剤(日本ポリウレタン工業社製、商品名「コロネートL」)3部を添加、混合して、アクリル系粘着剤組成物を調製した。
厚さ75μmの剥離フィルム(フジコー社製、商品名「FMN−75WD(C1−CA1)」)の剥離性表面にコート層形成材料(ウレタン系:2液混合硬化型インク)をグラビア印刷により付与し、格子状パターンを有するコート層(塗付厚1.5μm、透明)を形成した。
厚さ75μmのPETフィルム基材(商品名「ルミラー」、東レ社製)を用意し、このPET基材のコロナ放電処理面に、上記粘着剤組成物を乾燥後の厚さが15μmとなるように塗付し、100℃で3分間乾燥させて、PETフィルム基材の片面に粘着剤層を形成した。
上記粘着剤層の表面に、上記で得たコート層形成剥離フィルムのコート層形成面を当接させて、粘着剤層表面にコート層を転写した。剥離フィルムは、そのまま粘着剤層表面の保護に用いた。このようにして本例に係る粘着シートを作製した。この粘着シートの粘着剤層表面には、図1に示すコート層からなる格子状パターンが形成されており、コート層配置部の長尺部の幅(線幅)は2mm、間隔は8mmであった。
コート層配置部の長尺部の間隔を13mmに変更した他は例1Aと同様にして本例に係る粘着シートを作製した。
コート層を形成しなかった他は例1Aと同様にして本例に係る粘着シートを作製した。
各例に係る粘着シートにつき、対SUS180度剥離強度(接着力)を評価した。具体的には、粘着シートを幅25mm、長さ100mmのサイズにカットした測定サンプルにつき、23℃、50%RHの環境下にて、上記測定サンプルの粘着性表面をステンレス鋼板(SUS304BA板)の表面に、2kgのローラを1往復させて圧着した。これを同環境下に30分間、24時間または72時間放置した後、万能引張圧縮試験機を使用して、JIS Z 0237:2000に準じて、引張速度300mm/分、剥離角度180度の条件で、剥離強度(N/25mm)を測定した。測定は、各例および各条件(圧着後経過時間)につき3回ずつ行い、その平均値を採用した。また、コート層非配置部の面積割合が100%の例1Cにおける180度剥離強度値を100%として、例1A,1Bにおける180度剥離強度値を相対値(%)で示し、コート層非配置部の面積の減少にともなう接着力の低下の度合を評価した。結果を、コート層非配置部の面積割合(%)とともに表1に示す。
<例2A〜例2J>
コート層配置部の長尺部の幅(mm)および間隔(mm)を表2に示す値に設定し、例1Aと同様の方法で各例に係る粘着シートを作製した。各例について測定した24時間経過後180度剥離強度(N/25mm)を表2に示す。その測定方法は上述のとおりである。なお、例2A、例2I、例2Jはそれぞれ、例1B、例1A、例1Cと同じ構成を有する。
各例に係る粘着シートにつき、透明被着体の平滑表面に貼り付けた際の空気抜け性を目視で観察し、下記の4段階で評価した。結果を表2に示す。
A:優れた空気抜け性を示し、粘着シートと被着体との間に気泡は残存しなかった。
B:粘着シートと被着体との間の気泡は比較的速い速度で抜け、気泡は残存しなかった。
C:粘着シートと被着体との間の気泡は比較的ゆっくりと抜け、気泡は残存しなかった。
D:粘着シートと被着体との間に気泡が残存した。
1A 粘着性表面
10 フィルム状基材
20,21,22 粘着剤層
20A 粘着剤層表面
30 コート層
40,41,42 剥離ライナー
50 コート層配置部
51 コート層非配置部
60 コート層パターン(格子状パターン)
70 第1ストライプ状パターン部
75A,75B,75C 長尺部(線状に延びる部分)
80 第2ストライプ状パターン部
85A,85B,85C 長尺部(線状に延びる部分)
110 コート層付き剥離ライナー
120 剥離性支持体
120A 剥離性表面
Claims (7)
- フィルム状基材と、該フィルム状基材の少なくとも一方の表面に設けられた粘着剤層と、を備える粘着シートであって、
前記粘着剤層表面を部分的に覆うコート層を備え、これによって、該粘着剤層表面はコート層配置部とコート層非配置部とを有しており、
前記粘着剤層表面における前記コート層非配置部の面積割合は70%以上であり、
前記コート層配置部は、前記粘着剤層表面を上方から見たときに、該粘着剤層の一端から他端に向かって線状に延びる部分を有しており、
前記線状に延びる部分の幅は0.1〜2mmの範囲内である、粘着シート。 - 前記粘着剤層表面には、前記線状に延びる部分が複数配置されており、
前記複数の線状に延びる部分のうち一群を構成する複数の線状に延びる部分は、その幅方向にて間隔をおいて配置されており、これによって、前記コート層配置部はストライプ状パターンを有する、請求項1に記載の粘着シート。 - 前記コート層配置部は、第1ストライプ状パターン部と、該第1ストライプ状パターン部と交差するように配置された第2ストライプ状パターン部とを含み、これによって、前記コート層配置部は格子状パターンを有する、請求項2に記載の粘着シート。
- 前記コート層配置部において、一のストライプ状パターンを構成する複数の線状に延びる部分の間隔は1.0〜10mmの範囲内である、請求項2または3に記載の粘着シート。
- 前記コート層が部分的に配置された粘着性表面は、13N/25mm以上の24時間経過後180度剥離強度を示す、請求項1〜4のいずれか一項に記載の粘着シート。
- 請求項1〜5のいずれか一項に記載の粘着シートと、該粘着シートの粘着面を保護する剥離ライナーと、を備えており、
前記剥離ライナーの表面のうち前記粘着面側の表面は、平滑に形成されている、剥離ライナー付き粘着シート。 - 少なくとも一方の表面が剥離性表面である剥離性支持体を備える粘着シート用剥離ライナーであって、
前記剥離性支持体の剥離性表面上には、粘着シートに転写可能なコート層が設けられており、これによって、該剥離性表面はコート層配置部とコート層非配置部とを有しており、
前記剥離性表面における前記コート層非配置部の面積割合は70%以上であり、
前記コート層は、前記剥離性表面の一端から他端に向かって線状に延びる部分を有しており、
前記線状に延びる部分の幅は0.1〜2mmの範囲内である、剥離ライナー。
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TW104139748A TWI714541B (zh) | 2014-11-28 | 2015-11-27 | 黏著片材 |
KR1020177013531A KR102463777B1 (ko) | 2014-11-28 | 2015-11-27 | 점착 시트 |
CN201580064326.3A CN107001871B (zh) | 2014-11-28 | 2015-11-27 | 粘合片 |
US15/529,634 US20170267897A1 (en) | 2014-11-28 | 2015-11-27 | Pressure-sensitive adhesive sheet |
PCT/JP2015/083445 WO2016084948A1 (ja) | 2014-11-28 | 2015-11-27 | 粘着シート |
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CN107001870A (zh) | 2017-08-01 |
TW201625757A (zh) | 2016-07-16 |
CN107001869A (zh) | 2017-08-01 |
CN107001870B (zh) | 2021-07-06 |
TWI714541B (zh) | 2021-01-01 |
JP6664167B2 (ja) | 2020-03-13 |
CN107001871A (zh) | 2017-08-01 |
CN113637419A (zh) | 2021-11-12 |
KR102506412B1 (ko) | 2023-03-07 |
CN107001869B (zh) | 2021-07-23 |
KR102463777B1 (ko) | 2022-11-07 |
US10596792B2 (en) | 2020-03-24 |
US20170260425A1 (en) | 2017-09-14 |
JP2016108532A (ja) | 2016-06-20 |
JP6679239B2 (ja) | 2020-04-15 |
KR20170092541A (ko) | 2017-08-11 |
US20170335142A1 (en) | 2017-11-23 |
JP6664166B2 (ja) | 2020-03-13 |
TWI682984B (zh) | 2020-01-21 |
KR20170090411A (ko) | 2017-08-07 |
KR102506413B1 (ko) | 2023-03-07 |
CN107001871B (zh) | 2020-11-10 |
TW201632597A (zh) | 2016-09-16 |
US20170267897A1 (en) | 2017-09-21 |
JP2016108533A (ja) | 2016-06-20 |
KR20170088833A (ko) | 2017-08-02 |
TWI682983B (zh) | 2020-01-21 |
TW201625758A (zh) | 2016-07-16 |
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