JPS629636B2 - - Google Patents
Info
- Publication number
- JPS629636B2 JPS629636B2 JP57201624A JP20162482A JPS629636B2 JP S629636 B2 JPS629636 B2 JP S629636B2 JP 57201624 A JP57201624 A JP 57201624A JP 20162482 A JP20162482 A JP 20162482A JP S629636 B2 JPS629636 B2 JP S629636B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- sheet
- ethylene
- weight
- copolymer
- 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.)
- Expired
Links
- 230000001070 adhesive effect Effects 0.000 claims description 25
- 239000006260 foam Substances 0.000 claims description 25
- 239000000853 adhesive Substances 0.000 claims description 23
- 239000002390 adhesive tape Substances 0.000 claims description 15
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 10
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 9
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 9
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 claims description 8
- 239000003522 acrylic cement Substances 0.000 claims description 6
- -1 acrylic ester Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000004604 Blowing Agent Substances 0.000 description 7
- 229920001684 low density polyethylene Polymers 0.000 description 6
- 239000004702 low-density polyethylene Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 229920001821 foam rubber Polymers 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- 239000004156 Azodicarbonamide Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 2
- 235000019399 azodicarbonamide Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000002666 chemical blowing agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 239000003822 epoxy resin Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000647 polyepoxide Chemical class 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は発泡体を基材とする粘着テープもしく
はシートに関する。
従来自動車のサイドモールの固定はポリクロロ
プレンフオーム、ブチルゴムフオーム等のゴム系
フオームを基材とする粘着テープが使用されてい
るが、ゴム系フオームは柔軟性が不充分であり、
固定部分に段差があつたり、曲率が大であると被
着体になじみにくく、剥離しやすいという欠点が
ある。又低密度ポリエチレン発泡体を基材とする
粘着テープは、機械的強度が小さく剪断力によつ
て破壊されてしまうという欠点があつた。
本発明の目的は上記欠点に鑑み、機械的強度が
大であり、柔軟性がすぐれており、自動車のサイ
ドモールの固定の様に凹凸もしくは曲率の大なる
被着体に剪断力が加えられても破壊することなく
長期間貼着することができる粘着テープもしくは
シートを提供することにある。
即ち本発明の要旨は線状低密度ポリエチレンと
エチレン−酢酸ビニル共重合体又はエチレン−ア
クリル酸エチル共重合体とよりなる軟質発泡体の
少なくとも一面にアクリル系粘着剤が積層されて
なる粘着テープもしくはシートに存する。
本発明において用いられる線状低密度ポリエチ
レンとは、例えば中低圧下のイオン重合反応によ
り、エチレンにプロピレン、ブテン−１、ペンテ
ン−１、ヘキセン−１、オクテン−１、４−メチ
ルペンテン−１等のα−オレフインを少量（約１
〜10モル％）共重合させることにより、直鎖状の
幹ポリマーに適当数の短鎖分岐を導入し、それに
より密度を通常の高圧法低密度ポリエチレンの範
囲まで低下させたポリマーであり、密度0.915〜
0.94ｇ／cm3、メルトインデツクス0.5〜50ｇ／10
分のものが好ましく、より好ましくはメルトイン
デツクスが1.0〜10.0ｇ／10分のものであり、例
えばUItzex−3021F、2020L（三井石油化学
（株）製）、DNGA7342、GRSN7345（ユニオンカ
ーバイト社製）等が挙げられる。
本発明において用いられるエチレン−酢酸ビニ
ル共重合体としては、エチレンと酢酸ビニルの共
重合体であり、酢酸ビニル含有量が５〜28％のも
のが成形性、発泡体の柔軟性、接着性等の面から
好ましい。酢酸ビニル含有量が少なすぎると発泡
体の接着性、柔軟性が乏しくなり、多すぎると発
泡体の成形性が悪くなる。
本発明において用いられるエチレン−アクリル
酸エチル共重合体としては、エチレンとアクリル
酸エチルの共重合体であり、アクリル酸エチルの
含有量が７〜25％のものが成形性、発泡体の柔軟
性、接着性等の面から好ましい。アクリル酸エチ
ルの含有量が少なすぎると発泡体の接着性、柔軟
性が乏しくなり、多すぎると発泡体の成形性が悪
くなる。
本発明において用いられる発泡体は上記線状低
密度ポリエチレンと、エチレン−酢酸ビニル共重
合体又はエチレン−アクリル酸エチル共重合体か
らなる軟質の発泡体であり、発泡倍率は特に限定
されるものではないが、３〜20倍であるのが好ま
しく、より好ましくは５〜10倍である。又その製
造方法は従来公知の製造方法が採用されてよく、
例えば、上記樹脂混合物に発泡剤を配合し、リボ
ンブレンダー等を使用して均一に混合した混合物
を、押出機又はカレンダーロールによつて発泡剤
が実質的に分解しない温度、圧力で混練溶融して
シート状に成形し、該シート状成形体に電離性放
射線を照射することによつて架橋し、その後発泡
剤の分解温度以上に加熱することにより架橋発泡
体を得る方法、或は上記樹脂混合物に発泡剤、架
橋剤を配合し、これを均一に混合した混合物を、
押出機又はカレンダーロールによつて発泡剤及び
架橋剤が実質的に分解しない温度、圧力で混練溶
融してシート状に成形し、これを架橋剤が分解す
る温度に加熱することによつて架橋し、更に発泡
剤の分解温度以上に加熱することにより架橋発泡
体を得る方法等が挙げられる。
発泡剤としては、加熱によつて分解ガスを発生
するアゾジカルボンアミド、Ｎ−N′−ジニトロ
ソペンタメチレンテトラミン等の化学発泡剤が使
用上特別な装置を要しないので好ましい。
樹脂を架橋せしめる手段として電離性放射線を
使用する場合は、β線、γ線、ニユートロン、電
子線等が使用され、その照射量としては0.5〜
20Mradの範囲が好ましい。又、樹脂を架橋せし
める手段として架橋剤を使用する場合は、ジクミ
ルパーオキサイド、２・５−ジメチル−２・５−
ジターシヤリーパーオキシヘキサン、ジターシヤ
リーブチルパーテレフタレート等の有機過酸化物
が使用される。
線状低密度ポリエチレンと、エチレン−酢酸ビ
ニル共重合体又はエチレン−アクリル酸エチル共
重合体との混合比としては、１：４〜４：１の範
囲が発泡体の機械的強度、柔軟性、接着性、成形
性等の面から好ましい。
線状低密度ポリエチレンが少なすぎると抗張力
等の機械的強度が不足し、多すぎると柔軟性、接
着性が不足するのである。上記混合においてエチ
レン−酢酸ビニル共重合体とエチレン−アクリル
酸エチル共重合体を一緒に用いてよいのはもちろ
んである。本発明においては前記混合物に更に通
常の低密度ポリエチレン、高密度ポリエチレン、
エチレン−プロピレン共重合体、ポリプロピレン
等の樹脂を加えることも可能である。例えば通常
の低密度ポリエチレンを加える場合は、その密度
が0.91〜0.93ｇ／cm3、メルトインデツクス１〜10
ｇ／10分のものが好ましく、全体の樹脂混合物の
50重量％まで好適に加えることができる。
又、上記発泡体を製造するに当つて、安定剤、
紫外線吸収剤、滑剤、顔料、帯電防止剤、充填
剤、補強剤等、通常用いられている添加剤、助剤
を混合してもよい。
本発明の粘着テープもしくはシートは上記発泡
体の少なくとも一面にアクリル系粘着剤が積層さ
れて形成されるのであり、アクリル系粘着剤とし
ては、一般式CH2＝CHCOOR（式中Ｒは炭素数
４〜８のアルキル基）で表されるアクリル酸エス
テルよりなり、重量平均分子量が６×105〜106で
ある共重合体を主成分とする粘着剤が好ましい。
上記アクリル酸エステルとしては、たとえばア
クリル酸ｎ−ブチル、アクリル酸２エチルヘキシ
ル、アクリル酸イソアミル、アクリル酸ｎ−オク
チル等があげられ、上記共重合体はアクリル酸エ
ステルだけの（共）重合体でもよいが、上記アク
リル酸エステルと共重合可能な、アクリル酸、メ
タクリル酸、２−ビドロキシエチルメタクリレー
ト、２−ヒドロキシエチルアクリレート、Ｎ−メ
チロールアクリルアミド、酢酸ビニル、アクリロ
ニトリル、アクリル酸エチル、メタクリル酸メチ
ル等のモノマーと共重合されてもよい。
又共重合体の重量平均分子量は小さくなると耐
熱クリープ性が低下し、逆に分子量が大きくなる
と低温貼着性が低下するので６×105〜106である
のが好ましい。
又上記共重合体はイソシアネート、エポキシ樹
脂、金属塩等により架橋されてもよいし、粘着剤
には粘着特性を調整する目的で粘着付与剤、充填
剤、顔料、防錆剤等が添加されてもよい。上記粘
着剤の製造方法は、従来公知の製造方法が採用さ
れてよく、たとえば溶液重合法、エマルジヨン重
合法等があげられる。
又粘着剤を発泡体に積層する方法も従来公知の
任意の方法が採用されてよく、たとえば離型紙に
粘着剤を塗布乾燥した後発泡体に転写する方法が
採用される。
本発明の粘着テープの構成は上述の通りである
から、機械的強度が大であり、柔軟性がすぐれて
いるので凹凸面や曲率の大なる面によくなじみ、
剪断力が加えられても破壊することなく長期間貼
着することができ自動車のサイドモールの固定に
好適に使用できる。
又アクリル系粘着剤の重量平均分子量が６×
105〜106であると耐熱クリープ及び低温貼着性が
すぐれており、低温で貼着することができ、貼着
後長時間高温にさらしても剥離することがない。
次に本発明を実施例を参照して説明する。尚物
性の測定方法は次の通りである。
(1) 引張強さ……JISK6767（5.2引張強さ及び伸
びＡ法）に準拠した。
(2) 圧縮硬さ……JISK6767（5.3圧縮硬さ）に準
拠した。
(3) 剪断強さ……標準状態（23℃、65％RH）で
半硬質塩化ビニル樹脂板（巾42mm、長さ
100mm）に試料の両面粘着テープ（巾25
mm、長さ25mm）を貼着し、５Kgゴムロー
ルを一往復して圧着し、24時間放置す
る。次に上記両面粘着テープの他面にメ
ラミン塗装鋼板を貼着し、５Kgゴムロー
ルを一往復して圧着し、24時間放置後、
50mm／minの速度で引張つて破断する強
度を測定した。
(4) 有効接着面積……標準状態で半硬質塩化ビニ
ル樹脂板（巾42mm、長さ100mm）の巾方
向の略中央部に試料の両面粘着テープ
（巾25mm、長さ42mm）を貼着し、５Kgゴ
ムロールを一往復して圧着し24時間放置
する。次に両側部に厚さ25μｍ、巾８mm
長さ100mmのアルミニウム板を接着し、
巾25mmの溝が形成された透明アクリル板
に上記両面粘着テープの貼着された塩化
ビニル樹脂板を貼着し、10Kgロールを一
往復して圧着した後、アクリル板に粘着
剤が貼着している面積を測定し、貼着面
積の比率を有効接着面積とした。
(5) 低温接着力……標準状態で半硬質塩化ビニル
樹脂板（巾42mm、長さ100mm）の長さ方
向に試料の両面粘着テープ（巾25mm、長
さ100mm）を貼着し、５Kgゴムロールを
一往復して圧着し、24時間放置する。次
に５℃の恒温室に３時間放置されたメラ
ミン塗装鋼板に貼着し、５Kgゴムロール
を１往復して圧着し、20分後に50mm／
minの速度で割裂強度を測定した。
(6) 耐熱クリープ……剪断強さの測定において作
成したと同様にして三層の測定試料を作
成し、80℃の恒温室の供給して吊設し、
１時間後にメラミン塗装鋼板に１Kgの錘
を吊設し、２時間後に粘着テープのずれ
た距離を測定した。
実施例 １
密度0.918ｇ／cm3、メルトインデツクス2.0ｇ／
10分の線状低密度ポリエチレン30重量部と、酢酸
ビニル含有量18％、メルトインデツクス2.5ｇ／
10分のエチレン−酢酸ビニル共重合体70重量部
と、発泡剤（アゾジカルボンアミド）５重量部
と、助剤5.5重量部とを混合し、押出機でシート
状に押出成形し、その後、電子線照射機にて
2.5Mradの電子線を照射して架橋し、次に250℃
のオーブンを連続的に通して加熱発泡させて、厚
み約１mmの発泡シートを得た。得られた発泡シー
トは柔軟性を有し、均一に分散された独立気泡を
有していた。発泡倍率は７倍であつた。
アクリル酸２エチルヘキシル90重量部、アクリ
ル酸９重量部、メタクリル酸２ヒドロキシエチル
１重量部、酢酸エチル100重量部及びアゾビスイ
ソブチルニトリル0.02重量部よりなる配合物を70
℃で８時間重合して固形分48％の粘着剤組成物を
得た。粘着剤の重量平均分子量は65万（ゲルパー
ミエーシヨンクロマトグラフイー法）であつた。
上記粘着剤組成物100重量部にイソシアネート
（日本ポリウレタン社、コロネートＬ、固形分55
％）4.4重量部添加し、シリコン処理した厚さ25
μｍのポリエステルフイルムに塗布乾燥して厚さ
75μｍの粘着剤層の形成された粘着シートを得
た。
上記発泡シートの両面をコロナ放電処理した後
上記粘着シートから粘着剤層を転写して両面粘着
シートを得た。
得られた両面粘着シートを使用し、物性（引張
強さ、圧縮硬さ、剪断強さ、有効接着面積、低温
接着力及び耐熱クリープ）を測定し結果を第１表
に示した。
実施例 ２
実施例１と同じ線状低密度ポリエチレン30重量
部と、アクリル酸エチル含有量18％、メルトイン
デツクス６ｇ／10分のエチレン−アクリル酸エチ
ル共重合体70重量部と、発泡剤５重量部と、助剤
5.5重量部とを混合し、シート状に押圧成形し、
その後、2.5Mradの電子線を照射して架橋し、次
に250℃で加熱発泡させて、厚み約１mmの発泡シ
ートを得た。得られた架橋発泡シートは柔軟性を
有し、均一に分散された独立気泡を有していた。
発泡倍率は6.3倍であつた。
上記発泡シートに実施例１で使用した粘着剤を
実施例１で行つたと同様にして転写して両面粘着
シートを得、同様にして物性を測定し結果を第１
表に示した。
実施例 ３
実施例１と同じ線状低密度ポリエチレン30重量
部と、実施例１と同じエチレン−酢酸ビニル共重
合体50重量部と、密度0.923ｇ／cm3、メルトイン
デツクス4.0ｇ／10分の低密度ポリエチレン20重
量部と、発泡剤５重量部と、助剤5.5重量部とを
混合し、シート状に押出成形し、その後、
2.5Mradの電子線を照射して架橋し、次に250℃
で加熱発泡させて、厚み約１mmの発泡シートを得
た。
得られた架橋発泡シートは柔軟性を有し、均一
に分散された独立気泡を有していた。発泡倍率は
7.8倍であつた。
上記発泡シートに実施例１で使用した粘着剤を
実施例１で行つたと同様にして転写して両面粘着
シートを得、同様にして物性を測定し結果を第１
表に示した。
比較例 １
樹脂を実施例３と同じ低密度ポリエチレン100
重量部のみに変更した他は実施例３と同様にして
厚み約１mmの発泡シートを得た。
発泡倍率は7.5倍であつた。
上記発泡シートに実施例１で使用した粘着剤を
実施例１で行つたと同様にして転写して両面粘着
シートを得、同様にして物性を測定して結果を第
１表に示した。
比較例 ２
厚さ１mmのクロロプレン発泡シート（発泡倍率
2.0倍）の両面に実施例１で使用した粘着剤を実
施例１で行つたと同様にして転写して両面粘着シ
ートを得、同様にして物性を測定し結果を第１表
に示した。
The present invention relates to adhesive tapes or sheets based on foam. Conventionally, adhesive tapes based on rubber foams such as polychloroprene foam and butyl rubber foam have been used to fix the side moldings of automobiles, but rubber foams have insufficient flexibility.
If the fixed part has a step or a large curvature, it has a drawback that it is difficult to conform to the adherend and is easily peeled off. Adhesive tapes based on low-density polyethylene foam also have the disadvantage of having low mechanical strength and being easily destroyed by shearing force. In view of the above drawbacks, the object of the present invention is to provide a material that has high mechanical strength, excellent flexibility, and is suitable for applying shearing force to adherends with large irregularities or curvatures, such as fixing side moldings of automobiles. An object of the present invention is to provide an adhesive tape or sheet that can be stuck for a long period of time without being destroyed. That is, the gist of the present invention is an adhesive tape or an acrylic adhesive laminated on at least one surface of a flexible foam made of linear low-density polyethylene and an ethylene-vinyl acetate copolymer or an ethylene-ethyl acrylate copolymer. Exists on the sheet. The linear low-density polyethylene used in the present invention is produced by, for example, ionic polymerization reaction under medium and low pressure to produce ethylene, propylene, butene-1, pentene-1, hexene-1, octene-1, 4-methylpentene-1, etc. of α-olefin (approximately 1
~10 mol%) copolymerization to introduce an appropriate number of short chain branches into the linear backbone polymer, thereby reducing the density to the range of ordinary high-pressure low-density polyethylene. 0.915~
0.94g/ cm3 , melt index 0.5~50g/10
It is preferable to have a melt index of 1.0 to 10.0 g/10 min. ) etc. The ethylene-vinyl acetate copolymer used in the present invention is a copolymer of ethylene and vinyl acetate, and one with a vinyl acetate content of 5 to 28% has good moldability, foam flexibility, adhesive properties, etc. It is preferable from the point of view. If the vinyl acetate content is too low, the adhesiveness and flexibility of the foam will be poor, and if it is too high, the moldability of the foam will be poor. The ethylene-ethyl acrylate copolymer used in the present invention is a copolymer of ethylene and ethyl acrylate, and those with an ethyl acrylate content of 7 to 25% have good moldability and flexibility of the foam. , is preferable from the viewpoint of adhesiveness and the like. If the content of ethyl acrylate is too small, the adhesiveness and flexibility of the foam will be poor, and if it is too large, the moldability of the foam will be poor. The foam used in the present invention is a soft foam made of the above-mentioned linear low-density polyethylene and an ethylene-vinyl acetate copolymer or an ethylene-ethyl acrylate copolymer, and the expansion ratio is not particularly limited. However, it is preferably 3 to 20 times, more preferably 5 to 10 times. Moreover, the manufacturing method may be a conventionally known manufacturing method,
For example, a blowing agent is added to the above resin mixture, the mixture is uniformly mixed using a ribbon blender, etc., and the mixture is kneaded and melted using an extruder or calendar roll at a temperature and pressure that does not substantially decompose the blowing agent. A method of obtaining a crosslinked foam by forming the sheet into a sheet, crosslinking the sheet by irradiating the sheet with ionizing radiation, and then heating the foam to a temperature higher than the decomposition temperature of the blowing agent, or A mixture of a foaming agent and a crosslinking agent is mixed uniformly,
The foaming agent and crosslinking agent are kneaded and melted using an extruder or calender roll at a temperature and pressure that does not substantially decompose, formed into a sheet, and then crosslinked by heating this to a temperature at which the crosslinking agent decomposes. , and a method of obtaining a crosslinked foam by heating to a temperature higher than the decomposition temperature of the blowing agent. As the blowing agent, chemical blowing agents such as azodicarbonamide and N-N'-dinitrosopentamethylenetetramine, which generate decomposed gas when heated, are preferred because they do not require special equipment for use. When using ionizing radiation as a means of crosslinking resin, β rays, γ rays, neutrons, electron beams, etc. are used, and the irradiation dose is 0.5~
A range of 20 Mrad is preferred. In addition, when using a crosslinking agent as a means for crosslinking the resin, dicumyl peroxide, 2,5-dimethyl-2,5-
Organic peroxides such as ditertiary peroxyhexane and ditertiary butyl perterephthalate are used. The mixing ratio of linear low density polyethylene and ethylene-vinyl acetate copolymer or ethylene-ethyl acrylate copolymer is in the range of 1:4 to 4:1 to improve the mechanical strength, flexibility, and It is preferable from the viewpoint of adhesiveness, moldability, etc. If the amount of linear low density polyethylene is too small, mechanical strength such as tensile strength will be insufficient, and if it is too large, flexibility and adhesiveness will be insufficient. Of course, in the above mixing, the ethylene-vinyl acetate copolymer and the ethylene-ethyl acrylate copolymer may be used together. In the present invention, the mixture further includes ordinary low density polyethylene, high density polyethylene,
It is also possible to add resins such as ethylene-propylene copolymer and polypropylene. For example, when adding ordinary low-density polyethylene, its density is 0.91 to 0.93 g/cm 3 and the melt index is 1 to 10.
g/10 min is preferred, and the total resin mixture
Up to 50% by weight can suitably be added. In addition, in producing the above foam, stabilizers,
Commonly used additives and auxiliaries such as ultraviolet absorbers, lubricants, pigments, antistatic agents, fillers, and reinforcing agents may be mixed. The adhesive tape or sheet of the present invention is formed by laminating an acrylic adhesive on at least one surface of the foam, and the acrylic adhesive has the general formula CH 2 =CHCOOR (where R is 4 carbon atoms). A pressure-sensitive adhesive whose main component is a copolymer made of an acrylic ester represented by an alkyl group of . Examples of the acrylic ester include n-butyl acrylate, 2-ethylhexyl acrylate, isoamyl acrylate, n-octyl acrylate, etc., and the copolymer may be a (co)polymer of only acrylic ester. However, acrylic acid, methacrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, N-methylolacrylamide, vinyl acetate, acrylonitrile, ethyl acrylate, methyl methacrylate, etc., which can be copolymerized with the above acrylic esters. It may also be copolymerized with monomers. Further, the weight average molecular weight of the copolymer is preferably 6×10 5 to 10 6 because as the molecular weight becomes smaller, the heat resistance creep property decreases, and on the other hand, as the molecular weight increases, the low temperature adhesiveness decreases. The above copolymer may be crosslinked with isocyanate, epoxy resin, metal salt, etc., and tackifiers, fillers, pigments, rust preventives, etc. may be added to the adhesive for the purpose of adjusting adhesive properties. Good too. Conventionally known production methods may be employed as the method for producing the above-mentioned pressure-sensitive adhesive, such as solution polymerization method, emulsion polymerization method, and the like. Furthermore, any conventionally known method may be used for laminating the adhesive on the foam, such as applying the adhesive to release paper, drying it, and then transferring it to the foam. Since the adhesive tape of the present invention has the above-mentioned structure, it has high mechanical strength and excellent flexibility, so it adapts well to uneven surfaces and surfaces with large curvature.
It can be stuck for a long time without breaking even when shearing force is applied, and can be suitably used for fixing the side moldings of automobiles. Also, the weight average molecular weight of the acrylic adhesive is 6×
If it is 10 5 to 10 6 , it has excellent heat-resistant creep and low-temperature adhesion, can be applied at low temperatures, and will not peel off even if exposed to high temperatures for a long time after adhesion. Next, the present invention will be explained with reference to examples. The physical properties were measured as follows. (1) Tensile strength: Compliant with JISK6767 (5.2 Tensile strength and elongation A method). (2) Compression hardness: Compliant with JISK6767 (5.3 Compression hardness). (3) Shear strength...Semi-rigid vinyl chloride resin plate (width 42 mm, length
100 mm) and double-sided adhesive tape (width 25 mm) for the sample.
25mm in length), crimped with a 5Kg rubber roll back and forth once, and left for 24 hours. Next, attach a melamine-coated steel plate to the other side of the double-sided adhesive tape, press it with a 5 kg rubber roll once, and leave it for 24 hours.
The tensile strength at break was measured at a speed of 50 mm/min. (4) Effective adhesion area...In standard conditions, a double-sided adhesive tape (width 25 mm, length 42 mm) of the sample was attached to approximately the center in the width direction of a semi-rigid vinyl chloride resin plate (width 42 mm, length 100 mm). Press a 5Kg rubber roll back and forth once and leave it for 24 hours. Next, on both sides, the thickness is 25 μm and the width is 8 mm.
Glue an aluminum plate with a length of 100mm,
A vinyl chloride resin board with the double-sided adhesive tape attached above was pasted on a transparent acrylic board with grooves 25 mm wide, and after being crimped with a 10 kg roll back and forth, the adhesive was stuck to the acrylic board. The area of the adhesive was measured, and the ratio of the adhesive area was taken as the effective adhesive area. (5) Low-temperature adhesion strength...In standard conditions, a semi-rigid vinyl chloride resin plate (width 42 mm, length 100 mm) is affixed with double-sided adhesive tape (width 25 mm, length 100 mm) to the length of the sample, and a 5 kg rubber roll is attached. Crimp it by going back and forth once and leave it for 24 hours. Next, it was pasted on a melamine-coated steel plate that was left in a constant temperature room at 5℃ for 3 hours, and was crimped with a 5Kg rubber roll once.
The splitting strength was measured at a speed of min. (6) Heat-resistant creep: A three-layer measurement sample was prepared in the same manner as the one used to measure shear strength, and a constant temperature room at 80°C was provided and the sample was suspended.
After 1 hour, a weight of 1 kg was suspended from the melamine-coated steel plate, and after 2 hours, the distance by which the adhesive tape had shifted was measured. Example 1 Density 0.918g/cm 3 , Melt index 2.0g/
30 parts by weight of 10-minute linear low-density polyethylene, vinyl acetate content 18%, melt index 2.5 g/
70 parts by weight of a 10-minute ethylene-vinyl acetate copolymer, 5 parts by weight of a blowing agent (azodicarbonamide), and 5.5 parts by weight of an auxiliary agent were mixed and extruded into a sheet using an extruder. With ray irradiation machine
Cross-linked by irradiating with 2.5 Mrad electron beam, then 250℃
The foamed sheet was heated and foamed by continuously passing it through an oven to obtain a foamed sheet with a thickness of about 1 mm. The resulting foamed sheet was flexible and had uniformly dispersed closed cells. The expansion ratio was 7 times. 70 parts by weight of a blend consisting of 90 parts by weight of 2-ethylhexyl acrylate, 9 parts by weight of acrylic acid, 1 part by weight of 2-hydroxyethyl methacrylate, 100 parts by weight of ethyl acetate and 0.02 parts by weight of azobisisobutylnitrile.
Polymerization was carried out at .degree. C. for 8 hours to obtain a pressure-sensitive adhesive composition with a solid content of 48%. The weight average molecular weight of the adhesive was 650,000 (gel permeation chromatography method). Add isocyanate (Japan Polyurethane Co., Ltd., Coronate L, solid content 55 parts by weight to 100 parts by weight of the above adhesive composition).
%) 4.4 parts by weight added and siliconized thickness 25
Coated on μm polyester film and dried to achieve thickness
A pressure-sensitive adhesive sheet having a 75 μm adhesive layer formed thereon was obtained. After corona discharge treatment was applied to both sides of the foamed sheet, the adhesive layer was transferred from the adhesive sheet to obtain a double-sided adhesive sheet. Using the obtained double-sided pressure-sensitive adhesive sheet, the physical properties (tensile strength, compressive hardness, shear strength, effective adhesive area, low-temperature adhesive strength, and heat-resistant creep) were measured, and the results are shown in Table 1. Example 2 30 parts by weight of the same linear low density polyethylene as in Example 1, 70 parts by weight of an ethylene-ethyl acrylate copolymer with an ethyl acrylate content of 18% and a melt index of 6 g/10 min, and a blowing agent 5 Parts by weight and auxiliaries
5.5 parts by weight, press-molded into a sheet,
Thereafter, it was crosslinked by irradiation with an electron beam of 2.5 Mrad, and then heated and foamed at 250°C to obtain a foamed sheet with a thickness of about 1 mm. The resulting crosslinked foam sheet had flexibility and uniformly dispersed closed cells. The foaming ratio was 6.3 times. The adhesive used in Example 1 was transferred onto the foamed sheet in the same manner as in Example 1 to obtain a double-sided adhesive sheet, and the physical properties were measured in the same manner and the results were reported as
Shown in the table. Example 3 30 parts by weight of the same linear low density polyethylene as in Example 1, 50 parts by weight of the same ethylene-vinyl acetate copolymer as in Example 1, density 0.923 g/cm 3 , melt index 4.0 g/10 min. 20 parts by weight of low-density polyethylene, 5 parts by weight of a foaming agent, and 5.5 parts by weight of an auxiliary agent were mixed, extruded into a sheet, and then
Cross-linked by irradiating with 2.5 Mrad electron beam, then 250℃
The mixture was heated and foamed to obtain a foamed sheet with a thickness of approximately 1 mm. The resulting crosslinked foam sheet had flexibility and uniformly dispersed closed cells. The foaming ratio is
It was 7.8 times higher. The adhesive used in Example 1 was transferred onto the foamed sheet in the same manner as in Example 1 to obtain a double-sided adhesive sheet, and the physical properties were measured in the same manner and the results were reported as
Shown in the table. Comparative Example 1 The resin was the same low density polyethylene 100 as in Example 3.
A foamed sheet with a thickness of about 1 mm was obtained in the same manner as in Example 3, except that only the parts by weight were changed. The foaming ratio was 7.5 times. The adhesive used in Example 1 was transferred to the foamed sheet in the same manner as in Example 1 to obtain a double-sided adhesive sheet, and the physical properties were measured in the same manner and the results are shown in Table 1. Comparative example 2 Chloroprene foam sheet with a thickness of 1 mm (foaming ratio
The adhesive used in Example 1 was transferred onto both sides of the sheet (2.0 times) in the same manner as in Example 1 to obtain a double-sided adhesive sheet, and the physical properties were measured in the same manner and the results are shown in Table 1.
【表】
※ 発泡シートが破壊、他はすべて界面
破壊
[Table] * Foam sheet destroyed, all others destroyed at interface
Claims (1)
ニル共重合体又はエチレン−アクリル酸エチル共
重合体とよりなる軟質発泡体の少なくとも一面に
アクリル系粘着剤が積層されてなる粘着テープも
しくはシート。 ２ 線状低密度ポリエチレンと、エチレン−酢酸
ビニル共重合体又はエチレン−アクリル酸エチル
共重合体との混合比が１：４〜４：１の範囲であ
る特許請求の範囲第１項記載の粘着テープもしく
はシート。 ３ アクリル系粘着剤が、一般式CH2＝
CHCOOR（式中Ｒは炭素数４〜８のアルキル
基）で表されるアクリル酸エステルよりなり、重
量平均分子量が６×105〜106である共重合体を主
体とする粘着剤である特許請求の範囲第１項又は
第２項記載の粘着テープもしくはシート。[Claims] 1. An adhesive tape comprising an acrylic adhesive laminated on at least one surface of a flexible foam made of linear low-density polyethylene and an ethylene-vinyl acetate copolymer or an ethylene-ethyl acrylate copolymer. Or a sheet. 2. The adhesive according to claim 1, wherein the mixing ratio of linear low density polyethylene and ethylene-vinyl acetate copolymer or ethylene-ethyl acrylate copolymer is in the range of 1:4 to 4:1. tape or sheet. 3 The acrylic adhesive has the general formula CH 2 =
Patent for an adhesive mainly consisting of a copolymer consisting of an acrylic ester represented by CHCOOR (wherein R is an alkyl group having 4 to 8 carbon atoms) and having a weight average molecular weight of 6 x 10 5 to 10 6 An adhesive tape or sheet according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57201624A JPS5991179A (en) | 1982-11-16 | 1982-11-16 | Self-adhesive tape or sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57201624A JPS5991179A (en) | 1982-11-16 | 1982-11-16 | Self-adhesive tape or sheet |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2044110A Division JPH0341179A (en) | 1990-02-23 | 1990-02-23 | Self-adhesive tape or sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5991179A JPS5991179A (en) | 1984-05-25 |
| JPS629636B2 true JPS629636B2 (en) | 1987-03-02 |
Family
ID=16444144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57201624A Granted JPS5991179A (en) | 1982-11-16 | 1982-11-16 | Self-adhesive tape or sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5991179A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3006610U (en) * | 1994-07-13 | 1995-01-31 | 安二 長島 | Tatami repair stickers |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2633714B2 (en) * | 1990-06-11 | 1997-07-23 | 東洋ケミテック 株式会社 | Adhesive foam sheet and method for producing the same |
| JP3350266B2 (en) * | 1994-12-09 | 2002-11-25 | ダイハツ工業株式会社 | Thermosetting double-sided adhesive tape and vehicle attachment mounting structure using the same |
| JP2811052B2 (en) * | 1995-05-29 | 1998-10-15 | 大松化学工業株式会社 | Adhesive for prevention of re-sticking |
| KR100802814B1 (en) | 2006-05-11 | 2008-02-12 | 현대자동차주식회사 | A Polyethylene Resin Composition for Hot?melt adhesive |
| CN106414638B (en) * | 2015-08-25 | 2018-09-11 | 株式会社寺冈制作所 | Adhesive tape |
| EP3680305A4 (en) | 2017-08-30 | 2021-04-07 | Teraoka Seisakusho Co., Ltd. | Adhesive tape |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56155232A (en) * | 1980-05-02 | 1981-12-01 | Nippon Oil Co Ltd | Blowing composition |
| JPS56166281A (en) * | 1980-05-23 | 1981-12-21 | Soken Kagaku Kk | Pressure-sensitive adhesive composition |
-
1982
- 1982-11-16 JP JP57201624A patent/JPS5991179A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56155232A (en) * | 1980-05-02 | 1981-12-01 | Nippon Oil Co Ltd | Blowing composition |
| JPS56166281A (en) * | 1980-05-23 | 1981-12-21 | Soken Kagaku Kk | Pressure-sensitive adhesive composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3006610U (en) * | 1994-07-13 | 1995-01-31 | 安二 長島 | Tatami repair stickers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5991179A (en) | 1984-05-25 |
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