JP2018131553A - 接着性樹脂積層体、積層体及びこれらの製造方法 - Google Patents
接着性樹脂積層体、積層体及びこれらの製造方法 Download PDFInfo
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- JP2018131553A JP2018131553A JP2017026762A JP2017026762A JP2018131553A JP 2018131553 A JP2018131553 A JP 2018131553A JP 2017026762 A JP2017026762 A JP 2017026762A JP 2017026762 A JP2017026762 A JP 2017026762A JP 2018131553 A JP2018131553 A JP 2018131553A
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Abstract
【解決手段】少なくとも第1の接着層11、第2の接着層12を有する接着性樹脂積層体10であって、第1の接着層11が主剤と架橋剤を含み、主剤が変性ポリオレフィン樹脂であり、架橋剤がエポキシ系化合物であり、第2の接着層12がポリオレフィン系樹脂からなり、第1の接着層11の粘弾性率の測定値E(150℃)が1.0×104Pa以上1.0×108Pa以下である。
【選択図】図1
Description
例えば特許文献1には、重量平均分子量が15000〜150000、且つ、固形分酸価が100〜300である、二塩基カルボン酸無水物変性ポリオレフィン樹脂を含有するポリオレフィン多層フィルム用接着性樹脂組成物、及びこれを他の樹脂あるいは金属との接着層として積層した多層積層フィルムが開示されている。
前記第1の接着層に含まれる前記エポキシ系化合物がビスフェノールA骨格を含んでもよい。
前記第2の接着層が複数のポリオレフィン系樹脂層の積層体であってもよい。
前記第2の接着層がブロックポリプロピレンからなる層を含んでもよい。
前記第2の接着層の膜厚が、前記第1の接着層の膜厚の5倍以上の厚さであり、前記第2の接着層が支持体性を有してもよい。
前記第1の被着体が金属であり、前記第2の被着体がポリオレフィン樹脂、ポリアミド樹脂、ポリエステル樹脂のいずれかから選ばれてもよい。
図1に、本実施形態の接着性樹脂積層体を模式的に示す。接着性樹脂積層体10は、少なくとも第1の接着層11、第2の接着層12を有する積層体である。第1の接着層11は、第1の被着体21と接することが可能な表面を有する。第2の接着層12は、第2の被着体22と接することが可能な表面を有する。
1種又は2種以上の酸変性ポリオレフィン樹脂において、同一の酸官能基含有モノマーが用いられてもよく、異なる2種以上の酸官能基含有モノマーが用いられてもよい。
不飽和ジカルボン酸としては、マレイン酸、イタコン酸、シトラコン酸、フマル酸等のα,β−不飽和ジカルボン酸、テトラヒドロフタル酸、メチルテトラヒドロフタル酸、5−ノルボルネン−2,3−ジカルボン酸(ナジック酸)、エンド−ビシクロ[2.2.1]−5−ヘプテン−2,3−ジカルボン酸(エンディック酸)等の1種又は2種以上が挙げられる。
不飽和ジカルボン酸無水物としては、無水マレイン酸、無水イタコン酸、無水シトラコン酸、無水テトラヒドロフタル酸、無水メチルテトラヒドロフタル酸、無水ナジック酸、無水エンディック酸などの1種又は2種以上が挙げられる。
RXで表されるエポキシ基を有する基としては、エポキシ基を有する脂肪族基、エポキシ基を有する脂環式基、エポキシ基を有する芳香族基等が挙げられる。なかでもグリシジル基(別名2,3−エポキシプロピル基)が好ましい。
例えば式(1)で表される樹脂において、(i)R1及びR2の両方がメチル基、(ii)同一の炭素原子に結合する少なくとも1組のR3及びR4の両方がメチル基、(iii)R5及びR6の両方がメチル基、から選択される少なくとも1つを満たすことにより、ビスフェノールA骨格を有する樹脂となる。
第1の接着層11中の接着性樹脂成分の全量を100質量部として、主剤70〜99.99質量部に対して、架橋剤0.01〜30質量部の割合が好ましい。主剤80〜99.9質量部に対して、架橋剤0.1〜20質量部の割合がより好ましい。
架橋剤の割合が多すぎる場合、適切な接着条件の設定が困難になるおそれがある。架橋剤が含まれない場合、第1の被着体21に対する接着性が悪くなる。
混合溶媒における混合割合は特に限定されないが、例えばトルエンとメチルエチルケトンとを組み合わせる場合、質量比で60〜95:5〜40が好ましく、70〜90:10〜30がより好ましい。
第2の接着層12は、支持体性を有することが好ましい。例えば、第2の接着層12単体をコーティング装置やラミネート装置等でベースのフィルム等として搬送することができる場合、第2の接着層12は支持体性を有する。
第2の接着層12は、第1の接着層11との接着性に優れることから、第1の接着層11に接する面に、ランダムポリプロピレンからなる層を含むことが好ましい。
これにより、接着性樹脂積層体10と2つの被着体21,22とが、第1の被着体21、接着性樹脂積層体10の第1の接着層11、第2の接着層12、第2の被着体22の順で積層されてなる積層体が得られる。
「架橋剤A」、「架橋剤B」及び「架橋剤C」は、それぞれ種類が異なるフェノールノボラック型エポキシ樹脂を表す。具体的には、上述の式(1)において、R1〜R6がすべてメチル基であるビスフェノールA型の化合物が「架橋剤A」である。R1、R3、R5がメチル基で、R2、R4、R6が水素原子であるビスフェノールE型の化合物が「架橋剤B」である。R1〜R6がすべて水素原子であるビスフェノールF型の化合物が「架橋剤C」である。
なお、E(150)の値は、例えば「1.0×104」を「1.0E+04」とするように表記した。また、図2のグラフに接着層1−1、接着層1−2、接着層1−7、接着層1−8の貯蔵弾性率E’(Pa)の測定結果を例示する。150℃におけるE’の値が、E(150)に相当する。
逐次安定製造性は、第1の接着層11と第1の被着体21、第2の接着層12と第2の被着体22をこの順でそれぞれ貼り付ける作業を5回繰り返してn=5での評価を行った。評価基準は、5回とも問題なく作業できた場合を「○」、1〜2回の作業においてフィッシュアイが生じた場合を「△」、3回以上フィッシュアイが生じた場合を「×」とした。
1項目以上に「◎」を含み、他の項目も「○」である場合の総合評価を「◎」とした。
3項目とも「○」である場合の総合評価を「○」とした。
2項目が「○」で、1項目が「△」である場合の総合評価を「△」とした。
1項目でも「×」がある場合の総合評価を「×」とした。
なお、比較例1では、第1の接着層11に架橋剤を用いていない。
第1の接着層11のみからなる比較例3の総合評価は「×」であった。
第2の接着層12のみからなる比較例4の総合評価は「×」であった。
Claims (10)
- 少なくとも第1の接着層、第2の接着層を有する接着性樹脂積層体であって、
前記第1の接着層が主剤と架橋剤を含み、前記主剤が変性ポリオレフィン樹脂であり、前記架橋剤がエポキシ系化合物であり、
前記第2の接着層がポリオレフィン系樹脂からなり、
前記第1の接着層の粘弾性率の測定値E(150℃)が1.0×104Pa以上1.0×108Pa以下であることを特徴とする接着性樹脂積層体。 - 前記第1の接着層に含まれる前記エポキシ系化合物がフェノールノボラック型エポキシ樹脂であることを特徴とする請求項1に記載の接着性樹脂積層体。
- 前記第1の接着層に含まれる前記エポキシ系化合物がビスフェノールA骨格を含むことを特徴とする請求項1又は2に記載の接着性樹脂積層体。
- 前記第2の接着層が複数のポリオレフィン系樹脂層の積層体であることを特徴とする請求項1〜3のいずれか1項に記載の接着性樹脂積層体。
- 前記第2の接着層がブロックポリプロピレンからなる層を含むことを特徴とする請求項1〜4のいずれか1項に記載の接着性樹脂積層体。
- 前記第2の接着層の膜厚が、前記第1の接着層の膜厚の5倍以上の厚さであり、前記第2の接着層が支持体性を有することを特徴とする請求項1〜5のいずれか1項に記載の接着性樹脂積層体。
- 請求項1〜6のいずれか1項に記載の接着性樹脂積層体と2つの被着体とが、第1の被着体、前記接着性樹脂積層体の前記第1の接着層、前記接着性樹脂積層体の前記第2の接着層、第2の被着体の順で積層されてなることを特徴とする積層体。
- 請求項7に記載の積層体であって、前記第1の被着体が金属であり、前記第2の被着体がポリオレフィン樹脂、ポリアミド樹脂、ポリエステル樹脂のいずれかから選ばれることを特徴とする積層体。
- 請求項1〜6のいずれか1項に記載の接着性樹脂積層体の製造方法であって、
(1)前記変性ポリオレフィン樹脂、前記エポキシ系化合物を溶媒に溶解し塗工液を製造する工程、
(2)基材フィルム上に前記塗工液を塗布、乾燥して、前記第1の接着層を製造する工程、
(3)押出成形によりフィルム状の前記第2の接着層を得る工程、
(4)前記基材フィルム上の前記第1の接着層と、前記第2の接着層とをラミネートする工程、
(5)前記基材フィルムを剥がし前記接着性樹脂積層体を得る工程、
をこの順で含むことを特徴とする接着性樹脂積層体の製造方法。 - 請求項7又は8に記載の積層体の製造方法であって、
(1)前記第1の被着体と前記第1の接着層とを積層し、加熱圧着し、前記第1の被着体と前記接着性樹脂積層体とを積層する第1の工程、
(2)前記第2の被着体と前記第2の接着層とを積層し、前記第1の工程よりも30℃以上高い温度で加熱圧着し、前記第2の被着体と前記接着性樹脂積層体とを積層する工程、
をこの順で含むことを特徴とする積層体の製造方法。
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US10590317B2 (en) | 2020-03-17 |
CN108441127A (zh) | 2018-08-24 |
US20180230345A1 (en) | 2018-08-16 |
JP7058073B2 (ja) | 2022-04-21 |
US10723923B2 (en) | 2020-07-28 |
CN108441127B (zh) | 2021-12-31 |
US20200172776A1 (en) | 2020-06-04 |
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