JP2007290341A - ハードコートフィルム、ハードコートフィルムの製造方法、光学素子および画像表示装置 - Google Patents
ハードコートフィルム、ハードコートフィルムの製造方法、光学素子および画像表示装置 Download PDFInfo
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- JP2007290341A JP2007290341A JP2006239137A JP2006239137A JP2007290341A JP 2007290341 A JP2007290341 A JP 2007290341A JP 2006239137 A JP2006239137 A JP 2006239137A JP 2006239137 A JP2006239137 A JP 2006239137A JP 2007290341 A JP2007290341 A JP 2007290341A
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Abstract
【解決手段】 透明プラスチックフィルム基材1の少なくとも一方の面に、(A)成分:ウレタンアクリレートおよびウレタンメタクリレートの少なくとも一方、(B)成分:ポリオールアクリレートおよびポリオールメタクリレートの少なくとも一方および(C)成分:特定の繰り返し単位を含むポリマーを含むハードコート層形成材料を用いてハードコート層2を形成する。
【選択図】 図1
Description
(A)成分:ウレタンアクリレートおよびウレタンメタクリレートの少なくとも一方
(B)成分:ポリオールアクリレートおよびポリオールメタクリレートの少なくとも一方
(C)成分:下記(C1)および下記(C2)の少なくとも一方から形成されたポリマー若しくはコポリマー又は前記ポリマーとコポリマーの混合ポリマー
(C1):水酸基およびアクリロイル基の少なくとも一方の基を有するアルキル基を有するアルキルアクリレート
(C2):水酸基およびアクリロイル基の少なくとも一方の基を有するアルキル基を有するアルキルメタクリレート
(A)成分:ウレタンアクリレートおよびウレタンメタクリレートの少なくとも一方
(B)成分:ポリオールアクリレートおよびポリオールメタクリレートの少なくとも一方
(C)成分:下記(C1)および下記(C2)の少なくとも一方から形成されたポリマー若しくはコポリマー又は前記ポリマーとコポリマーの混合ポリマー
(C1):水酸基およびアクリロイル基の少なくとも一方の基を有するアルキル基を有するアルキルアクリレート
(C2):水酸基およびアクリロイル基の少なくとも一方の基を有するアルキル基を有するアルキルメタクリレート
(B)成分:ポリオールアクリレートおよびポリオールメタクリレートの少なくとも一方
(C)成分:下記(C1)および下記(C2)の少なくとも一方から形成されたポリマー若しくはコポリマー又は前記ポリマーとコポリマーの混合ポリマー
(C1):水酸基およびアクリロイル基の少なくとも一方の基を有するアルキル基を有するアルキルアクリレート
(C2):水酸基およびアクリロイル基の少なくとも一方の基を有するアルキル基を有するアルキルメタクリレート
ミツトヨ社製のマイクロゲージ式厚み計を用い、ハードコートフィルムの全体厚みを測定し、前記全体厚みから、透明プラスチックフィルム基材の厚みを差し引くことにより、ハードコート層の厚みを算出した。
反射防止層の厚みは、大塚電子(株)製の瞬間マルチ側光システムであるMCPD2000(商品名)を用い、干渉スペクトルの波形より算出した。
ハードコートフィルムを10cm角に切断し、ガラス板上にハードコート層(又は反射防止層)が上になるように置き、4角に於けるガラス板からの持ち上がり長さ(mm)を測定し、その平均値をカールの評価の指標とした。尚、丸くなったものは「測定不能」とした。
JIS K7136(1981年版)のヘイズ(曇度)に準じ、商品名ヘイズメーターHR300(村上色彩技術研究所社製)を用いてヘイズ値を測定した。
ハードコートフィルムを、透明プラスチックフィルム基材を内側にして直径の異なる金属ロールに直接接する様に巻付け、ハードコート層(又は反射防止層)に於けるクラックの発生の有無を目視により判定した。クラックの入らなかった直径を屈曲性の値として計測した。
ハードコート層が形成されていない面を下にして、ハードコートフィルムをガラス板上に載せた後、前記ハードコート層表面について、JIS K−5400記載の鉛筆硬度試験に従い(ただし、荷重500g)、鉛筆硬度を測定した。
ハードコートフィルムのハードコート層が形成されていない面に黒色アクリル板(厚さ2.0mm、三菱レイヨン社製)を、厚み約20μmの粘着剤層を形成して貼り合せることにより、前記ハードコートフィルムの裏面の反射をなくした。このハードコートフィルムについて、ハードコート層表面の反射率を求めた。前記反射率は、島津製作所社製の商品名UV2400PC(8°傾斜積分球付き)分光光度計を用いて、分光反射率(鏡面反射率+拡散反射率)を測定し、C光源/2°視野の全反射率(Y値)を計算により求めた。
ハードコート層の屈折率は、多波長アッベ屈折計(株式会社アタゴ社製、商品名:DR−M2/1550)を用いて測定した。
ハードコートフィルムの耐擦傷性の強弱に対する値は、以下の試験内容にて求めた。
(1)試料を少なくとも幅25mm、長さ100mm以上の大きさに切断し、これをガラス板に載せる。その後、初期のヘイズ値を求める。
(2)直径25mmの円柱の平滑な断面に、スチールウール#0000を均一に取り付け、荷重1.5kgにて試料表面を毎秒約100mmの速度で100往復した後に、試験後のヘイズ値を求める。
(3)試験後のヘイズ値から初期のヘイズ値を差し引いた値を耐擦傷性の指標とした。
スチールウール試験に於いてハードコート層又は反射防止層の表面にキズが生じる程、試験後のヘイズ値は上昇し、初期ヘイズ値との差も上昇する。したがって、この評価では、試験後のヘイズ値と初期ヘイズ値との差、すなわち、耐擦傷性の指標となる値が大きい程、耐擦傷性が低く、前記指標となる値が小さい程、耐擦傷性が高いと判断できる。
ハードコート層の透明プラスチックフィルム基材に対する密着性は、JIS K 5400記載の碁盤目剥離試験を行うことにより評価した。即ち、100回の剥離試験を行い、ハードコート層がフィルム基材から剥離した数をカウントし、剥離数/100で表した。
下記に示す(A)成分、(B)成分、(C)成分および光重合開始剤を含む樹脂成分を、酢酸エチルおよび酢酸ブチルの混合溶媒に固形分濃度66重量%で含む樹脂原料(大日本インキ社製、商品名GRANDIC PC1071)を準備した。この樹脂原料に、レベリング剤0.5重量%を加え、さらに、酢酸ブチル:酢酸エチル(重量比)=46:54(全溶媒に対する酢酸エチル比率54重量%)であり、固形分濃度が50重量%となるように、酢酸エチルを用いて希釈することにより、ハードコート層形成材料を調製した。なお、前記レベリング剤は、ジメチルシロキサン:ヒドロキシプロピルシロキサン:6−イソシアネートヘキシルイソシアヌル酸:脂肪族ポリエステル=6.3:1.0:2.2:1.0のモル比で共重合させた共重合物である。
(B成分):ジペンタエリスリトールヘキサアクリレート(以下、B1成分(モノマー))49重量部、ペンタエリスリトールテトラアクリレート(以下、B4成分(モノマー))41部およびペンタエリスリトールトリアクリレート(以下、B5成分(モノマー))24重量部
(C)成分:前記一般式(1)で表される繰り返し単位を有するポリマー、コポリマー又は前記ポリマーおよびコポリマーの混合物(59重量部)
光重合開始剤:商品名イルガキュア184(チバ・スペシャリティケミカルズ社製)3重量部
混合溶剤:酢酸ブチル:酢酸エチル(重量比)=89:11
本実施例に於いては、ハードコート層の厚みを15μmに変更した以外は、実施例1と同様な方法にて、ハードコートフィルムを作製した。
本実施例に於いては、ハードコート層の厚みを25μmに変更した以外は、実施例1と同様な方法にて、ハードコートフィルムを作製した。
本実施例に於いては、前記(C)成分の配合量を96重量部に変更した以外は、実施例1と同様な方法にて、ハードコートフィルムを作製した。
本実施例に於いては、前記(C)成分の配合量を36重量部に変更した以外は、実施例1と同様な方法にて、ハードコートフィルムを作製した。
本実施例に於いては、ハードコート層形成材料に平均粒径10μmの架橋アクリル粒子(商品名;MX1000、綜研化学(株)製)を30重量部添加した以外は、実施例1と同様な方法にて、ハードコートフィルムを作製した。
本実施例に於いては、実施例1で得られたハードコートフィルムのハードコート層上に反射防止層を設けた以外は、実施例1と同様な方法にて、ハードコートフィルムを作製した。
本実施例に於いては、次に述べる反射防止層形成材料により形成された反射防止層(厚さ95nm)を設けた以外は、実施例7と同様な方法にて、ハードコートフィルムを作製した。
本実施例に於いては、ハードコート層の厚みを30μmに変更した以外は、実施例1と同様な方法にて、ハードコートフィルムを作製した。
本実施例に於いては、ハードコート層の厚みを10μmに変更した以外は、実施例1と同様な方法にて、ハードコートフィルムを作製した。
本実施例に於いては、混合溶媒として酢酸ブチルと酢酸エチルの混合割合が79:21(全溶媒に対する酢酸エチル比率21%)のものを使用し、更に固形分濃度を63重量%となる様に希釈して調製したハードコート層形成材料を用いてハードコート層を形成したこと以外は、実施例1と同様な方法にてハードコートフィルムを作製した。
先ず、実施例1と同様にして本実施例に係るハードコートフィルムを作製した。次に、トリアセチルセルロースフィルムの非ハードコート面(ハードコート層の形成面とは反対側の面)に、後述する塗工液をワイヤーバーにてウェットの厚みが20μmとなるように塗工し、80℃で1分間の乾燥処理を行った。なお、前記塗工液としては、アセトン:酢酸エチル:IPA(イソプロピルアルコール)=37:58:5の混合溶媒に対しジアセチルセルロースを固形分濃度が0.5%となるように配合したものを用いた。
本実施例に於いては、トリアセチルセルロースフィルムの非ハードコート面に塗工する塗工液において、アセトン:酢酸エチル:IPA=37:58:5の混合溶媒を用いたこと以外は、実施例12と同様な方法にてハードコートフィルムを作製した。
本実施例に於いては、レベリング剤としての反応性シリコーンを添加しなかったこと以外は、実施例1と同様な方法にてハードコートフィルムを作製した。
本実施例に於いては、(A)成分としてペンタエリスリトール系アクリレートとイソホロンジイソシアネートとから成るウレタンアクリレート(以下、A1成分)100重量部と、(B)成分としてB1成分59重量部、B4成分37重量部及びB5成分15重量部と、前記(C)成分26重量部と、全樹脂原料に対し前記重合開始剤重量2部を用いた樹脂原料(大日本インキ化学工業社製、商品名:PC4−Y243)を用いた以外は、実施例1と同様な方法にて、ハードコートフィルムを作製した。
本実施例に於いては、(A)成分としてA1成分100重量部と、(B)成分としてB1成分38重量部、B4成分40重量部及びB5成分16重量部と、前記(C)成分30部と、全樹脂原料に対し重合開始剤(商品名イルガキュア184を1重量部と、2,4,6−トリメチルベンゾインフェニルホスフィンオキシドを2.5重量部配合したもの)3.5重量部を用いた樹脂原料(大日本インキ化学工業社製、商品名:PC4−6097)を用いたこと以外は、実施例1と同様な方法にて、ハードコートフィルムを作製した。
本実施例に於いては、ハードコート層の厚みを29μmに変更したこと以外は、実施例6と同様な方法にて、ハードコートフィルムを作製した。
本比較例に於いては、前記(A)成分及び前記(C)成分を配合せず、かつ(B)成分としてジペンタエリスリトールヘキサアクリレートを100重量部と更にブタンジオールアクリレート(以下、B3成分)を9重量部配合したこと以外は、実施例1と同様な方法にて、ハードコートフィルムを作製した。
本比較例に於いては、(B)成分として、B4成分22重量部と、B5成分5重量部とを用いた。また、前記(C)成分に代えてポリメタクリル酸メチルアクリレートポリマー133重量部を用いたこと以外は、実施例1と同様な方法にてハードコートフィルムを作製した。
本比較例に於いては、(B)成分として、B4成分22重量部と、B5成分重量5部との混合物を用いた。また、前記(C)成分に代えてポリメタクリル酸メチルアクリレートポリマーを55重量部用いたこと以外は、実施例1と同様な方法にてハードコートフィルムを作製した。
2 ハードコート層
3、5 ハードコートフィルム
4 反射防止層
Claims (15)
- 透明プラスチックフィルム基材の少なくとも一方の面に、ハードコート層を有するハードコートフィルムであって、前記ハードコート層が、下記の(A)成分、(B)成分および(C)成分を含むハードコート層形成材料を用いて形成されたものであることを特徴とするハードコートフィルム。
(A)成分:ウレタンアクリレートおよびウレタンメタクリレートの少なくとも一方
(B)成分:ポリオールアクリレートおよびポリオールメタクリレートの少なくとも一方
(C)成分:下記(C1)および下記(C2)の少なくとも一方から形成されたポリマー若しくはコポリマー又は前記ポリマーとコポリマーの混合ポリマー
(C1):水酸基およびアクリロイル基の少なくとも一方の基を有するアルキル基を有するアルキルアクリレート
(C2):水酸基およびアクリロイル基の少なくとも一方の基を有するアルキル基を有するアルキルメタクリレート - 前記(B)成分が、ペンタエリスリトールトリアクリレートおよびペンタエリスリトールテトラアクリレートの少なくとも一方を含む請求項1記載のハードコートフィルム。
- 前記ハードコート層の外側表面構造が、凹凸構造である請求項1ないし3のいずれか一項に記載のハードコートフィルム。
- 前記ハードコート層の外側表面に、反射防止層が形成されている請求項1ないし4のいずれか一項に記載のハードコートフィルム。
- 前記反射防止層が、シロキサンオリゴマーおよびフッ素化合物を含み、前記シロキサンオリゴマーのエチレングリコール換算の数平均分子量が500〜10000であり、前記フッ素化合物のポリスチレン換算の数平均分子量が5000以上であり、前記フッ素化合物が、フルオロアルキル構造およびポリシロキサン構造を含む請求項5記載のハードコートフィルム。
- 前記反射防止層が、中空で球状の酸化ケイ素超微粒子を含有する請求項5または6記載のハードコートフィルム。
- 前記ハードコート層形成材料が、レベリング剤を含む請求項1ないし7のいずれか一項に記載のハードコートフィルム。
- 透明プラスチックフィルム基材の少なくとも一方の面に、ハードコート層を有するハードコートフィルムの製造方法であって、下記の(A)成分、(B)成分および(C)成分を溶媒に溶解若しくは分散したハードコート層形成材料を準備する工程と、前記透明プラスチックフィルム基材の少なくとも一方の面に、前記ハードコート層形成材料を塗工して塗膜を形成する工程と、前記塗膜を硬化させてハードコート層を形成する工程とを有することを特徴とするハードコートフィルムの製造方法。
(A)成分:ウレタンアクリレートおよびウレタンメタクリレートの少なくとも一方
(B)成分:ポリオールアクリレートおよびポリオールメタクリレートの少なくとも一方
(C)成分:下記(C1)および下記(C2)の少なくとも一方から形成されたポリマー若しくはコポリマー又は前記ポリマーとコポリマーの混合ポリマー
(C1):水酸基およびアクリロイル基の少なくとも一方の基を有するアルキル基を有するアルキルアクリレート
(C2):水酸基およびアクリロイル基の少なくとも一方の基を有するアルキル基を有するアルキルメタクリレート - 前記(B)成分が、ペンタエリスリトールトリアクリレートおよびペンタエリスリトールテトラアクリレートの少なくとも一方を含む請求項9記載のハードコートフィルムの製造方法。
- 前記溶媒が、酢酸エチルを含む請求項9ないし11のいずれか一項に記載のハードコートフィルムの製造方法。
- 前記溶媒全体に対する前記酢酸エチルの含有割合が、20重量%以上である請求項12記載のハードコートフィルムの製造方法。
- 光学部材の少なくとも一方の面にハードコートフィルムが配置された光学素子であって、前記ハードコートフィルムが、請求項1ないし8のいずれか一項に記載のハードコートフィルムであることを特徴とする光学素子。
- ハードコートフィルムまたは光学素子を備える画像表示装置であって、前記ハードコートフィルムが請求項1ないし8のいずれか一項に記載のハードコートフィルムであり、前記光学素子が請求項14記載の光学素子であることを特徴とする画像表示装置。
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2006
- 2006-09-04 JP JP2006239137A patent/JP4145332B2/ja active Active
-
2007
- 2007-03-26 US US11/727,394 patent/US7968183B2/en not_active Expired - Fee Related
- 2007-03-27 KR KR1020070029959A patent/KR100852561B1/ko active IP Right Grant
- 2007-03-28 TW TW96110819A patent/TWI356083B/zh not_active IP Right Cessation
Cited By (4)
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JP2009185282A (ja) * | 2008-01-11 | 2009-08-20 | Nitto Denko Corp | ハードコートフィルム、ハードコートフィルムの製造方法、光学素子および画像表示装置 |
JP2012102159A (ja) * | 2010-11-05 | 2012-05-31 | Mitsubishi Chemicals Corp | 活性エネルギー線硬化性組成物 |
CN114325916A (zh) * | 2017-03-31 | 2022-04-12 | 东洋纺株式会社 | 液晶显示装置、偏光板和偏振片保护膜 |
CN114325916B (zh) * | 2017-03-31 | 2023-10-13 | 东洋纺株式会社 | 液晶显示装置、偏光板和偏振片保护膜 |
Also Published As
Publication number | Publication date |
---|---|
US7968183B2 (en) | 2011-06-28 |
TW200745279A (en) | 2007-12-16 |
TWI356083B (en) | 2012-01-11 |
JP4145332B2 (ja) | 2008-09-03 |
US20070237966A1 (en) | 2007-10-11 |
KR20070097360A (ko) | 2007-10-04 |
KR100852561B1 (ko) | 2008-08-18 |
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