JP2018016785A - 樹脂組成物、樹脂層、および積層シート - Google Patents
樹脂組成物、樹脂層、および積層シート Download PDFInfo
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- JP2018016785A JP2018016785A JP2017108906A JP2017108906A JP2018016785A JP 2018016785 A JP2018016785 A JP 2018016785A JP 2017108906 A JP2017108906 A JP 2017108906A JP 2017108906 A JP2017108906 A JP 2017108906A JP 2018016785 A JP2018016785 A JP 2018016785A
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Abstract
【解決手段】ホモポリマーのTgが−50℃以下であり、かつ炭素数8〜18の分岐したアルキル基をエステル基の末端に有するアルキル(メタ)アクリレート(a1)を50〜97重量%、及びホモポリマーのTgが−40℃以下であり、かつ分子骨格内にエーテル結合を有する(メタ)アクリレート(a2)を3〜50重量%を含むモノマー成分を重合することにより得られたTgが−40℃以下である(メタ)アクリル系ポリマーを含むことを特徴とする樹脂組成物。
【選択図】なし
Description
本発明の炭素数8〜18の分岐したアルキル基をエステル基の末端に有するアルキル(メタ)アクリレート(a1)のホモポリマーのTgは、−50℃以下である。前記アルキル(メタ)アクリレート(a1)のTgは、粗面を有する被着体に対する接着力を高める観点から、−55℃以下であることが好ましく、−60℃以下であることがより好ましい。前記アルキル(メタ)アクリレート(a1)のTgは、粗面を有する被着体に対する保持力を高める観点から、−80℃以上であることが好ましく、−75℃以上であることがより好ましい。前記アルキル(メタ)アクリレート(a1)のアルキル基の炭素数は、樹脂層に適度な柔らかさを付与する観点、及び樹脂層の凝集力を高める観点から、8〜16であることが好ましく、8〜14であることがより好ましい。
本発明のエーテル結合を有する(メタ)アクリレート(a2)のホモポリマーのTgは、−40℃以下である。前記エーテル結合を有する(メタ)アクリレート(a2)のTgは、粗面を有する被着体に対する接着力を高める観点から、−45℃以下であることが好ましく、−50℃以下であることがより好ましい。前記エーテル結合を有する(メタ)アクリレート(a2)のTgは、粗面を有する被着体に対する接着力及び保持力を高める観点から、−90℃以上であることが好ましく、−80℃以上であることがより好ましい。尚、前記エーテル結合は、鎖状エーテル結合を意味し、エポキシ基、オキセタン基等の環状エーテル結合とは異なる。
本発明の(メタ)アクリル系ポリマーを形成するモノマー成分には、さらに、ヒドロキシル基を有するモノマー、カルボキシル基を有するモノマー、及びエポキシ基を有するモノマーから選ばれるいずれか少なくとも1つの官能基を有するモノマーを含むことができる。
本発明の(メタ)アクリル系ポリマーを形成するモノマー成分には、前記官能基を有するモノマー以外の共重合モノマーを含むことができる。前記共重合モノマーとしては、例えば、一般式(2):CH2=CR3−COO−R4(前記R3は水素原子又はメチル基、R4は炭素数1〜24の無置換のアルキル基又は置換されたアルキル基を表す。但し、炭素数8〜18の分岐したアルキル基の場合を除く。)で表されるモノマーが挙げられる。共重合モノマーは単独でまたは組み合わせて使用できる。
本発明の(メタ)アクリル系ポリマーを形成するモノマー成分には、樹脂組成物の凝集力を調整するために、必要に応じて多官能性モノマーを含有することができる。多官能性モノマーは単独でまたは組み合わせて使用できる。
本発明の(メタ)アクリル系ポリマーのTgは、−40℃以下である。前記(メタ)アクリル系ポリマーのTgは、粗面を有する被着体に対する接着力を高める観点から、−45℃以下であることが好ましく、−50℃以下であることがより好ましい。前記(メタ)アクリル系ポリマーのTgは、粗面を有する被着体に対する接着力及び保持力を高める観点から、−85℃以上であることが好ましく、−80℃以上であることがより好ましい。尚、(メタ)アクリル系ポリマーのTgは、(メタ)アクリル系ポリマーを構成するモノマー単位とその割合から、以下のFOXの式より算出される理論値である。
[式中、Tgは(メタ)アクリル系ポリマーのガラス転移温度(単位:K)、Tgi(i=1、2、・・・n)は、モノマーiがホモポリマーを形成した際のガラス転移温度(単位:K)、Wi(i=1、2、・・・n)は、モノマーiの全モノマー成分中の質量分率を表す。]
・分析装置:東ソー社製、HLC−8120GPC
・カラム:東ソー社製、(メタ)アクリル系ポリマー:GM7000HXL+GMHXL+GMHXL
芳香族系ポリマー:G3000HXL+2000HXL+G1000HXL
・カラムサイズ;各7.8mmφ×30cm 計90cm・溶離液:テトラヒドロフラン(濃度0.1重量%)
・流量:0.8ml/min
・入口圧:1.6MPa
・検出器:示差屈折計(RI)
・カラム温度:40℃
・注入量:100μl
・溶離液:テトラヒドロフラン
・検出器:示差屈折計
・標準試料:ポリスチレン
本発明の樹脂組成物は、架橋剤を含有することができる。架橋剤としては、イソシアネート系架橋剤、エポキシ系架橋剤、シリコーン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、シラン系架橋剤、アルキルエーテル化メラミン系架橋剤、金属キレート系架橋剤、過酸化物等の架橋剤が含まれる。前記架橋剤としては、イソシアネート系架橋剤、エポキシ系架橋剤が好適である。
本発明の樹脂層は、前記樹脂組成物から形成される。樹脂層の厚さは、特に制限されず、例えば、1〜1000μm程度である。前記樹脂層の厚さは、好ましくは、3〜500μm、より好ましくは5〜200μmである。
<(メタ)アクリル系ポリマーの調製>
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、2−エチルヘキシルアクリレート(2EHA)90重量部、エチルカルビトールアクリレート(CBA)10重量部、4−ヒドロキシブチルアクリレート(4HBA)0.25重量部、アクリル酸(AA)1重量部、重合開始剤として2,2´−アゾビスイソブチロニトリル0.07重量部を酢酸エチル105重量部と共に仕込み、緩やかに攪拌しながら窒素ガスを導入して1時間窒素置換した後、フラスコ内の液温を60〜65℃付近に保って10時間重合反応を行い、重量平均分子量77万の(メタ)アクリル系ポリマー溶液を調製した。得られた(メタ)アクリル系ポリマーのTgは−68.7℃であった。
実施例1において、(メタ)アクリル系ポリマーの調製に用いたモノマーの種類とその組成比、架橋剤の種類とその配合量を表1に示すように変えたこと以外は、実施例1と同様の操作を行い、積層シートを作製した。得られた(メタ)アクリル系ポリマーの重量平均分子量、Tgを表1に示す。
<(メタ)アクリル系ポリマーシロップの調製>
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、2−エチルヘキシルアクリレート(2EHA)90重量部、エチルカルビトールアクリレート(CBA)10重量部、4−ヒドロキシブチルアクリレート(4HBA)0.25重量部、アクリル酸(AA)1重量部、光重合開始剤(商品名:イルガキュア184、BASF社製)0.15重量部および光重合開始剤(商品名:イルガキュア651、BASF社製)0.15重量部を4つ口フラスコに投入してモノマー混合物を調製した。次いで、前記モノマー混合物を窒素雰囲気下で紫外線に曝露して部分的に光重合させることによって、重合率約10重量%の部分重合物((メタ)アクリル系ポリマーシロップ)を得た。
実施例30において、(メタ)アクリル系ポリマーシロップの調製に用いたモノマーの組成比を表2に示すように変えたこと以外は、実施例30と同様の操作を行い、積層シートを作製した。得られた(メタ)アクリル系ポリマーのTgを表2に示す。
積層シートにおける樹脂層から所定量(最初の重量W1)を取り出し、酢酸エチル溶液に浸漬して、室温で1週間放置した後、不溶分を取り出し、乾燥させた重量(W2)を測定し、下記のように求めた。
ゲル分率(%)=(W2/W1)×100
実施例及び比較例で得られたサンプルの粘着面に厚み25μmのPETフィルム(東レ社製,ルミラーS10)を貼り付けたものを評価用サンプルとした。当該評価用サンプルを、幅20mm×長さ約100mmに裁断した後、前記セパレーター(三菱樹脂社製,ダイアホイルMRF)を剥離して、各種被着体として、石膏ボード(吉野石膏社製、商品名タイガーボード 9.5mm厚)、針葉樹合板(島忠ホームズ入手 12mm厚)、又はケイ酸カルシウム板(ケイカル板、島忠ホームズ入手 5mm厚)に、2kgのロールを1往復で貼付けた。次いで、室温(23℃)で30分静置した後、剥離角度180°、剥離速度300mm/分でピール接着力(N/20mm)を測定した。尚、前記ピール接着力は、10N/20mm以上であることが好ましく、12N/20mm以上であることがより好ましく、15N/20mm以上であることがさらに好ましい。
実施例及び比較例で得られたサンプルの粘着面に厚み25μmのPETフィルム(東レ社製,ルミラーS10)を貼り付けたものを評価用サンプルとした。当該評価用サンプルを、幅10mm×長さ100mmに裁断した後、前記セパレーター(三菱樹脂社製,ダイアホイルMRF)を剥離して、被着体として、針葉樹合板(島忠ホームズ入手 12mm厚)に、貼りつけ面積が幅10mm×長さ20mmになるように2kgのロールを1往復で貼付けた。次いで、室温(23℃)で30分静置した後、針葉樹合板を垂下し、試料片の自由端に500gの荷重を付与した。当該荷重が付与された状態で40℃の環境下に1時間放置し、最初の貼り付け位置からの試料テープのズレ距離(mm)を測定し、保持力(mm/h)を算出した。尚、前記保持力は、2.0mm/h以下であることが好ましく、1.5mm/h以下であることがより好ましく、1.0mm/h以下であることがより好ましい。
INAは、イソノニルアクリレート(大阪有機化学工業社製,ホモポリマーのTg=−58℃);
IMAは、イソミスチリルアクリレート(共栄社化学株式会社,ホモポリマーのTg=−56℃);
CBAは、エチルカルビトールアクリレート(大阪有機化学工業社製,ホモポリマーのTg=−67℃);
♯MTGは、メトキシトリエチレングリコールアクリレート(大阪有機化学工業社製,ホモポリマーのTg=−57℃);
4HBAは、4−ヒドロキシブチルアクリレート(大阪有機化学工業社製,ホモポリマーのTg=−32℃);
HEAは、ヒドロキシエチルアクリレート(大阪有機化学工業社製,ホモポリマーのTg=−15℃);
AAはアクリル酸(東亜合成社製,ホモポリマーのTg=106℃);
BAは、ブチルアクリレート(東亜合成社製,ホモポリマーのTg=−55℃);を示す。
D110Nは、キシリレンジイソシアネートのトリメチロールプロパン付加物(三井化学社製,商品名:タケネートD110N);
D120Nは、キシリレンジイソシアネートのトリメチロールプロパン付加物(三井化学社製,商品名:タケネートD120N);
D140Nは、イソホロンジイソシアネートのトリメチロールプロパン付加物(三井化学社製,商品名:タケネートD140N);
T/Cは、1,3−ビス(N,N−ジグリシジルアミノメチル)シクロヘキサン(三菱ガス化学社製,商品名テトラッドC);
TMPTAは、トリメチロールプロパントリアクリレート((大阪有機化学工業社製);を示す。
Claims (13)
- ホモポリマーのTgが−50℃以下であり、かつ炭素数8〜18の分岐したアルキル基をエステル基の末端に有するアルキル(メタ)アクリレート(a1)を50〜97重量%、及びホモポリマーのTgが−40℃以下であり、かつ分子骨格内にエーテル結合を有する(メタ)アクリレート(a2)を3〜50重量%を含むモノマー成分を重合することにより得られたTgが−40℃以下である(メタ)アクリル系ポリマーを含むことを特徴とする樹脂組成物。
- 前記アルキル(メタ)アクリレート(a1)及び前記エーテル結合を有する(メタ)アクリレート(a2)の合計の割合が、(メタ)アクリル系ポリマーを形成する全モノマー成分に対して、75重量%以上であることを特徴とする請求項1記載の樹脂組成物。
- 前記エーテル結合を有する(メタ)アクリレート(a2)が、
一般式(1):CH2=CR1−COO−(AO)n−R2
[前記一般式(1)中、R1は水素原子又はメチル基、AOは炭素数2〜3のアルキレンオキシ基、nはアルキレンオキシ基の平均付加モル数を示す1〜8であり、R2は芳香環、又は直鎖、分岐鎖、もしくは脂環式アルキル基である。]で表されるモノマーであることを特徴とする請求項1又は2記載の樹脂組成物。 - 前記モノマー成分が、さらに、ヒドロキシル基を有するモノマー、カルボキシル基を有するモノマー、及びエポキシ基を有するモノマーから選ばれるいずれか少なくとも1つの官能基を有するモノマーを含むことを特徴とする請求項1〜3のいずれか1項に記載の樹脂組成物。
- 前記モノマー成分が、さらに、多官能性モノマーを、(メタ)アクリル系ポリマーを形成する全モノマー成分に対して、5重量%以下含むことを特徴とする請求項1〜4のいずれか1項に記載の樹脂組成物。
- 前記(メタ)アクリル系ポリマーの重量平均分子量が、35万以上であることを特徴とする請求項1〜5のいずれか1項に記載の樹脂組成物。
- さらに、前記(メタ)アクリル系ポリマー100重量部に対して、架橋剤を、0.01〜5重量部含むことを特徴とする請求項1〜6のいずれか1項に記載の樹脂組成物。
- 前記架橋剤が、イソシアネート系架橋剤、及び/又はエポキシ系架橋剤であることを特徴とする請求項7記載の樹脂組成物。
- 請求項1〜8のいずれか1項に記載の樹脂組成物から得られることを特徴とする樹脂層。
- ゲル分率が20〜95重量%であることを特徴とする請求項9記載の樹脂層。
- 支持体の少なくとも片側に、請求項9又は10記載の樹脂層が設けられていることを特徴とする積層シート。
- 前記樹脂層の被着体に対する180°ピール接着力が、剥離速度300mm/分の条件下で、10N/20mm以上であることを特徴とする請求項11記載の積層シート。
- 前記支持体が、プラスチックフィルム、紙、不織布及び気泡含有シート、のいずれかであることを特徴とする請求項11又は12記載の積層シート。
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WO2019130822A1 (ja) * | 2017-12-28 | 2019-07-04 | 日東電工株式会社 | 樹脂組成物、樹脂層、および積層シート |
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KR102470448B1 (ko) * | 2017-12-15 | 2022-11-24 | 주식회사 엘지화학 | 의류용 수성 아크릴계 점착제 및 이의 제조 방법 |
JP7185479B2 (ja) * | 2017-12-28 | 2022-12-07 | 日東電工株式会社 | 樹脂組成物、樹脂層、および積層シート |
US11851589B2 (en) | 2018-02-02 | 2023-12-26 | Lg Chem, Ltd. | Adhesive composition for foldable display, adhesive film using same, and foldable display comprising |
KR102193854B1 (ko) | 2018-02-02 | 2020-12-22 | 주식회사 엘지화학 | 폴더블 디스플레이용 점착제 조성물, 이를 이용한 점착필름, 및 이를 포함한 폴더블 디스플레이 |
WO2022107689A1 (ja) * | 2020-11-19 | 2022-05-27 | 旭化成株式会社 | ポリイソシアネート組成物、硬化膜、塗膜、粘着剤組成物、粘着シート及び樹脂組成物 |
JP2022159124A (ja) * | 2021-03-31 | 2022-10-17 | 旭化成株式会社 | 光学用樹脂組成物及び光学用樹脂シート |
CN114773942B (zh) * | 2022-04-02 | 2023-06-23 | 广东希贵光固化材料有限公司 | 一种led固化涂料 |
CN116536001A (zh) * | 2023-07-07 | 2023-08-04 | 江苏康辉新材料科技有限公司 | 可折叠粘合胶膜及其制法和在柔性显示光学器件中的应用 |
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JP2010189545A (ja) * | 2009-02-18 | 2010-09-02 | Nitto Denko Corp | 両面粘着シートおよび粘着型光学部材 |
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WO2015133497A1 (ja) * | 2014-03-05 | 2015-09-11 | デクセリアルズ株式会社 | 両面黒色粘着テープ |
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EP3486284A4 (en) | 2020-02-12 |
CN109312139A (zh) | 2019-02-05 |
EP3486284A1 (en) | 2019-05-22 |
TWI824998B (zh) | 2023-12-11 |
KR20190029507A (ko) | 2019-03-20 |
JP6893124B2 (ja) | 2021-06-23 |
TW201823341A (zh) | 2018-07-01 |
KR102288096B1 (ko) | 2021-08-11 |
US20190292414A1 (en) | 2019-09-26 |
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