JP6856475B2 - 粘着フィルムおよびその製造方法 - Google Patents
粘着フィルムおよびその製造方法 Download PDFInfo
- Publication number
- JP6856475B2 JP6856475B2 JP2017161477A JP2017161477A JP6856475B2 JP 6856475 B2 JP6856475 B2 JP 6856475B2 JP 2017161477 A JP2017161477 A JP 2017161477A JP 2017161477 A JP2017161477 A JP 2017161477A JP 6856475 B2 JP6856475 B2 JP 6856475B2
- Authority
- JP
- Japan
- Prior art keywords
- polyurethane layer
- adhesive film
- layer
- meth
- polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002313 adhesive film Substances 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000010410 layer Substances 0.000 claims description 138
- 229920002635 polyurethane Polymers 0.000 claims description 121
- 239000004814 polyurethane Substances 0.000 claims description 121
- -1 isocyanate compound Chemical class 0.000 claims description 93
- 239000012948 isocyanate Substances 0.000 claims description 42
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 39
- 229920000515 polycarbonate Polymers 0.000 claims description 34
- 239000004417 polycarbonate Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 28
- 239000002981 blocking agent Substances 0.000 claims description 26
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- 230000009477 glass transition Effects 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 11
- 239000012790 adhesive layer Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 description 60
- 239000005056 polyisocyanate Substances 0.000 description 53
- 229920001228 polyisocyanate Polymers 0.000 description 53
- 150000003077 polyols Chemical class 0.000 description 51
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 39
- 239000000178 monomer Substances 0.000 description 29
- 238000004383 yellowing Methods 0.000 description 19
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- 238000000576 coating method Methods 0.000 description 16
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- 125000001931 aliphatic group Chemical group 0.000 description 10
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 10
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 7
- 125000002723 alicyclic group Chemical group 0.000 description 7
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- 125000003277 amino group Chemical group 0.000 description 5
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
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- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
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- 238000011156 evaluation Methods 0.000 description 4
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- 238000005227 gel permeation chromatography Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
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- 239000003999 initiator Substances 0.000 description 4
- 150000003951 lactams Chemical class 0.000 description 4
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- 239000002356 single layer Substances 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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Images
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- Adhesives Or Adhesive Processes (AREA)
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Description
ポリウレタン層(A)は、ウレタン系樹脂を含む層である。
ポリウレタン層(B)は、ポリカーボネート系ウレタン樹脂およびブロック型イソシアネート化合物を含む組成物を硬化してなる。
ポリウレタン層(B)は基材としての役割を果たすため、耐久性(耐熱性、耐光性)が高いことが求められる。このため、本実施形態では、ポリウレタン層(B)を構成するウレタン系樹脂としてポリカーボネート系ウレタン樹脂を用いる。
式中、Rは脂肪族炭化水素基又は脂環族炭化水素基であり、nは2以上の整数であり、複数あるRは同一であってもよく、異なるものであってもよい。
ブロック型イソシアネート化合物は、常温(25℃)では不活性であるが、加熱するとポリイソシアネートに結合しているブロック剤が可逆的に解離してイソシアネート基を再生する化合物である。ブロック剤の解離温度は80〜120℃のものが好ましい。
さらに、ポリウレタン層(A)上の最表面に防汚層を設けてもよい。防汚層を形成する材料としては、フッ素系樹脂、ポリウレタン、ポリアクリル樹脂、シリコーン樹脂などが挙げられる。防汚層の厚さは0.5〜20μm程度である。
粘着剤層に用いられる粘着剤としては、特に限定されず、アクリル系粘着剤、ゴム系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤、ポリエステル系粘着剤、スチレン−ジエンブロック共重合体粘着剤、ビニルアルキルエーテル系粘着剤、ポリアミド系粘着剤、フッ素系粘着剤などを用いることができる。上記粘着剤は1種単独で用いても2種以上併用してもよい。
剥離ライナーは、粘着剤層を保護し、粘着性の低下を防止する機能を有する部材である。そして、剥離ライナーは、塗膜に貼付する際に塗膜保護シートから剥離される。このため、本発明における塗膜保護シートは、剥離ライナーを有していないものも包含される。
本実施形態の粘着フィルムは、塗装面を有する被着体に粘着剤層面が貼付されて用いられ、すなわち、本実施形態の粘着フィルムは塗膜保護フィルムである。また、本実施形態の塗膜保護フィルムは、耐チッピング性に優れるため、耐チッピング性塗膜保護フィルムであることがより好ましい。このような用途で用いられるフィルムは、塗装面の意匠性を損なわないよう、透明であることが好ましい。具体的には、本実施形態の(剥離ライナーを剥離した)粘着フィルムのJIS K7136:2000に準じて測定したヘーズは、透明性の観点から、1.5%以下であることが好ましく、1.0%以下であることがより好ましい。
本実施形態の粘着フィルムの製造方法は特に限定されず、例えば、ポリカーボネート系ウレタン樹脂およびブロック型イソシアネート化合物を含む組成物を用いてポリウレタン層(A)上にポリウレタン層(B)を形成し、ポリウレタン層(B)のポリウレタン層(A)形成面の反対側に粘着剤層を形成する、粘着フィルムの製造方法であって、ポリウレタン層(A)のガラス転移温度が130℃以下である、粘着フィルムの製造方法が挙げられる。
1.動的粘弾性測定
動的粘弾性自動測定器(ORIENTEC社製、RHEOVIBRON DDV−01FP)を用い、JIS K7244−4:1999 プラスチック−動的機械特性の試験方法−第4部:引張振動−非共振法に基づいて、周波数11Hz、振幅±16μmおよび昇温速度3℃/minの条件下で、20℃から150℃までの温度範囲で、損失係数tanδの温度分布曲線(横軸に温度、縦軸にtanδ)を測定した。
引張弾性率は、JIS K7161:1994に準拠し、温度23℃、湿度50%の環境下において、チャック間距離40mm、引張速度200mm/分で測定した(サンプルサイズ:長さ100mm×幅15mm)。
1.ポリウレタン層(A)およびポリウレタン層(B)の積層体の形成
ポリカーボネート系ウレタン樹脂100質量部および溶媒であるN,N,−ジメチルホルムアミド 200質量部を混合し、得られた組成物を、キャスティングライナー上にナイフコーターを用いて塗布した。塗布後、200℃、10分加熱し、厚さ10μmのポリウレタン層(A)を得た。ポリウレタン層(A)のMD方向の引張弾性率は800MPa、ガラス転移温度112℃、損失係数の最大値が0.8であった。
還流器および攪拌機を備えたフラスコに、アクリル酸ブチル95質量部、アクリル酸5質量部、過酸化物系開始剤およびトルエン(溶剤)を混合し、窒素置換を行いながら加温し、重合を行って、アクリル系ポリマーを得た(重量平均分子量Mw=500,000)。
厚さ10μm、MD方向の引張弾性率830MPa、ガラス転移温度116℃、損失係数の最大値が0.5であるポリウレタン層(A)を用いたこと以外は、実施例1と同様にして粘着フィルムを得た。
厚さ10μm、MD方向の引張弾性率1080MPa、ガラス転移温度132℃、損失係数の最大値が0.9であるポリウレタン層(A)を用いたこと以外は、実施例1と同様にして粘着フィルムを得た。
得られた粘着シートにおける黄変度ΔYIを評価した。
11 ポリウレタン層(A)、
12 ポリウレタン層(B)、
13 粘着剤層、
14 剥離ライナー。
Claims (12)
- ポリウレタン層(A)と、
該ポリウレタン層(A)に隣接して配置され、ポリカーボネート系ウレタン樹脂およびブロック型イソシアネート化合物を含む組成物を硬化してなるポリウレタン層(B)と、
粘着剤層と、をこの順に有し、
前記ポリウレタン層(A)のガラス転移温度が130℃以下である、粘着フィルム。 - 前記ブロック型イソシアネート化合物のブロック剤がアミン系である、請求項1に記載の粘着フィルム。
- 前記ポリウレタン層(A)の20〜150℃における損失係数(tanδ)の最大値が0.7以上である、請求項1または2に記載の粘着フィルム。
- 前記ポリウレタン層(A)の引張弾性率が500MPa以上であり、前記ポリウレタン層(B)の引張弾性率が、100MPa以下である、請求項1〜3のいずれか1項に記載の粘着フィルム。
- 前記ポリウレタン層(A)の厚さが、1〜30μmである、請求項1〜4のいずれか1項に記載の粘着フィルム。
- 前記ポリウレタン層(B)の厚さが、50μm以上である、請求項1〜5のいずれか1項に記載の粘着フィルム。
- ポリカーボネート系ウレタン樹脂およびブロック型イソシアネート化合物を含む組成物を用いてポリウレタン層(A)上にポリウレタン層(B)を形成し、
前記ポリウレタン層(B)の前記ポリウレタン層(A)形成面の反対側に粘着剤層を形成する、粘着フィルムの製造方法であって、
前記ポリウレタン層(A)のガラス転移温度が130℃以下である、粘着フィルムの製造方法。 - 前記ブロック型イソシアネート化合物のブロック剤がアミン系である、請求項7に記載の粘着フィルムの製造方法。
- 前記ポリウレタン層(A)の20〜150℃における損失係数(tanδ)の最大値が0.7以上である、請求項7または8に記載の粘着フィルムの製造方法。
- 前記ポリウレタン層(A)の引張弾性率が500MPa以上であり、前記ポリウレタン層(B)の引張弾性率が、100MPa以下である、請求項7〜9のいずれか1項に記載の粘着フィルムの製造方法。
- 前記ポリウレタン層(A)の厚さが、1〜30μmである、請求項7〜10のいずれか1項に記載の粘着フィルムの製造方法。
- 前記ポリウレタン層(B)の厚さが、50μm以上である、請求項7〜11のいずれか1項に記載の粘着フィルムの製造方法。
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EP3088179A1 (en) * | 2015-04-30 | 2016-11-02 | Impact Protection Technology AG | Multilayer polyurethane protective films |
JP6700542B2 (ja) * | 2016-09-30 | 2020-05-27 | Jnc株式会社 | 積層フィルム |
JP6853738B2 (ja) * | 2017-06-13 | 2021-03-31 | 三菱瓦斯化学株式会社 | ポリウレタン多層フィルム |
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