JPH0583075B2 - - Google Patents
Info
- Publication number
- JPH0583075B2 JPH0583075B2 JP62327950A JP32795087A JPH0583075B2 JP H0583075 B2 JPH0583075 B2 JP H0583075B2 JP 62327950 A JP62327950 A JP 62327950A JP 32795087 A JP32795087 A JP 32795087A JP H0583075 B2 JPH0583075 B2 JP H0583075B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- layer
- release agent
- base material
- manufactured
- 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 - Fee Related
Links
- 239000010410 layer Substances 0.000 claims description 85
- 239000000853 adhesive Substances 0.000 claims description 71
- 230000001070 adhesive effect Effects 0.000 claims description 71
- 239000000463 material Substances 0.000 claims description 50
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 239000012790 adhesive layer Substances 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 229920001296 polysiloxane Polymers 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002075 main ingredient Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 description 19
- 239000005060 rubber Substances 0.000 description 19
- 239000006082 mold release agent Substances 0.000 description 18
- 229920002379 silicone rubber Polymers 0.000 description 11
- 239000004945 silicone rubber Substances 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- -1 In particular Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004873 anchoring Methods 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- 239000013464 silicone adhesive Substances 0.000 description 6
- 239000002390 adhesive tape Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- UDPGUMQDCGORJQ-UHFFFAOYSA-N (2-chloroethyl)phosphonic acid Chemical class OP(O)(=O)CCCl UDPGUMQDCGORJQ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 229920001973 fluoroelastomer Polymers 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 238000010292 electrical insulation Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 108700042658 GAP-43 Proteins 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- PMDCZENCAXMSOU-UHFFFAOYSA-N N-ethylacetamide Chemical group CCNC(C)=O PMDCZENCAXMSOU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ULFUTCYGWMQVIO-PCVRPHSVSA-N [(6s,8r,9s,10r,13s,14s,17r)-17-acetyl-6,10,13-trimethyl-3-oxo-2,6,7,8,9,11,12,14,15,16-decahydro-1h-cyclopenta[a]phenanthren-17-yl] acetate;[(8r,9s,13s,14s,17s)-3-hydroxy-13-methyl-6,7,8,9,11,12,14,15,16,17-decahydrocyclopenta[a]phenanthren-17-yl] pentano Chemical compound C1CC2=CC(O)=CC=C2[C@@H]2[C@@H]1[C@@H]1CC[C@H](OC(=O)CCCC)[C@@]1(C)CC2.C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 ULFUTCYGWMQVIO-PCVRPHSVSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical group CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000006309 butyl amino group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical group CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-AZXPZELESA-N n-methylacetamide Chemical group C[15NH]C(C)=O OHLUUHNLEMFGTQ-AZXPZELESA-N 0.000 description 1
- NCCHARWOCKOHIH-UHFFFAOYSA-N n-methylbenzamide Chemical group CNC(=O)C1=CC=CC=C1 NCCHARWOCKOHIH-UHFFFAOYSA-N 0.000 description 1
- NAQQTJZRCYNBRX-UHFFFAOYSA-N n-pentan-3-ylidenehydroxylamine Chemical group CCC(CC)=NO NAQQTJZRCYNBRX-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229920000260 silastic Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229920003249 vinylidene fluoride hexafluoropropylene elastomer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
Description
〔産業上の利用分野〕
本発明は、粘着性構造体に関する。
〔従来の技術〕
基材の両面又は片面に粘着剤層、離型剤層、場
合によつてはさらに貼合基材を積層してなる粘着
性構造体、例えば粘着テープ、ラベル等が種々の
用途に使用されている。近年、この粘着性構造体
に用いられる粘着剤としてシリコーン系粘着剤、
特にジメチルポリシロキサンを主成分とするシリ
コーン系粘着剤が、耐熱性、耐寒性、耐薬品性、
電気絶縁性及び無毒性等に優れているため、広範
囲の用途に使用されている。
〔発明が解決しようとする問題点〕
しかし、上記粘着剤は、非常に粘着力が強いた
め、従来の粘着性構造体では、粘着剤層を離型剤
層から剥離する際に要する剥離力が大き過ぎ、特
に粘着性構造体を長期間保存すると、粘着剤層の
離型剤層からの剥離力が著しく増大し、剥離時
に、粘着剤層や離型剤層の破壊を招き易く、さら
に離型剤の成分が粘着剤層に移行し、粘着剤の粘
着力が低下する欠点があり、粘着性構造体として
の用をなさなくなることが多い。
そこで本発明の目的は、ジメチルポリシロキサ
ンを主成分とするシリコーン系粘着剤を用いた場
合でも剥離力が小さく離型性が良好であり、しか
も長期間保存後においてもその良好な離型性が高
い安定性で保持される粘着性構造体を提供するこ
とにある。
〔問題点を解決するための手段〕
本発明は、上記問題点を解決するものとして、
基材層、粘着剤層及び離型剤層を有する粘着性構
造体において、前記離型剤層が、
１ ポリフルオロアルキル基を有するビニル単量
体 50〜98重量％、
２ 分子中に少なくとも１個のけい素原子に結合
した加水分解可能な基を含有するシリコーン系
ビニル単量体 ２〜50重量％、
及び
３ 前記第１成分のポリフルオロアルキル基を有
するビニル単量体と共重合可能なビニル系単量
体 ０〜49重量％
からなる単量体混合物の共重合体を主剤とする離
型性組成物の硬化物からなることを特徴とする粘
着性構造体を提供するものである。
本発明の粘着性構造体は、前記の通りの３層を
有するものであるが、通常、基材層に対して少な
くとも１層の粘着剤層と少なくとも１層の離型剤
層とが積層されてなり、複数の粘着剤層及び／又
は複数の離型剤層が存在するときは、それらの層
は基材層の同じ片面側に位置してもよく、それぞ
れ異なる片面側又は両面側に位置してもよい。
また、本発明の粘着性構造体は、前記基材層、
粘着剤層及び離型剤層のみに限定されず、必要に
応じて他の層、例えば貼合基材を前記３層の間又
は外側に有することができる。この貼合基材は、
粘着性構造体に要求される機能、用途等により適
宜選択使用されるものであり、特に限定されない
が、通常、粘着性構造体の使用時には、剥離され
て廃棄されるものであるから、材料としては紙等
の安価なものが使用される。また、厚さ等も用
途、機能等に従つて適宜選択される。
本発明の粘着性構造体の構造例としては、図示
のものが挙げられる。
図１に示す例は、基材層の一面に粘着剤層が積
層され、他方の面に離型剤層が積層されているも
のである。これは、紙芯等に巻き取る等の操作
で、このままの構造を繰り返して作れば、片面粘
着テープとして用いることができるものである。
次に、図２に示す例は、基材層の片面に離型剤
層が積層され、その上に粘着剤層が積層されてい
るものである。これも紙芯等に巻き取る等の操作
により、片面粘着テープとして使用できる粘着性
構造体である。
さらに、図３に示す例は、両面に離型剤層が積
層された貼合基材と、両面に粘着剤層が積層され
た基材層とを貼り合わせたものである。この構造
体は、紙芯等に巻き取る等の操作で、両面粘着シ
ートとしてだけでなく、両面粘着テープとして用
いることができる。
最後に、図４に示す例は、片面に粘着剤層を積
層させた基材層と、片面に離型剤層を積層させた
貼合基材を貼り合わせた構造のものである。この
構造体は、ラベル等へ応用できるものである。
本発明の粘着性構造体の基材層は、粘着性構造
体の用途、機能等によつて選択され、特に限定さ
れないが、例えば、紙、ゴム、PETシート、カ
プトンシート、金属箔、テフロンシート及びアス
ベストクロス等を挙げることができる。このゴム
としては、例えばフツ素系ゴム、シリコーン系ゴ
ム等を用いることができる。ゴムを基材として用
いた場合には、弾力性、耐熱性及び電気絶縁性に
優れる粘着性構造体を得ることができる。
フツ素系ゴムとしては、市販され良く用いられ
ている。例えば、。デユポン社製バイトンシリー
ズ、3M社製フローレルシリーズ、ダイキン工業
社製ダイエルシリーズ、旭硝子社製アフラスシリ
ーズ等のフツ素ゴムが挙げられる。又、シリコー
ン系ゴムとしては、信越化学工業(株)製KE・FE・
SEPシリーズ、トーレシリコーン(株)製SH・SE・
SRXシリーズ、東芝シリコーン(株)製TSE・YEシ
リーズ、ダウコーニング社製SS・WC・HS・
Silasticシリーズ等のシリコーンゴムが挙げられ
る。
これらのゴムは、シート状にして用いるが、余
り厚くしすぎると、伸縮に大きな力を必要とした
り、重ね巻きで段差が出すぎたり、凹凸追随性が
減つたり、構造体の重さが増し且つ、厚さが厚く
なりすぎるので、0.01〜10mm程度にするのが好ま
しい。
また基材層は、粘着剤又は離型剤を積層させる
面を粗面化することによつて粘着剤や離型剤の投
錨効果を高めることができる。
この粗面は、通常のマツト加工とか、シート又
はフイルム製造時のエンボス加工プロセス、或い
は、マツト加工されたPET等のシートに未加硫
ゴムを貼り合わせて加硫する等の方法で得られ
る。
さらに基材層には、充填剤、例えば補強用繊維
材（カーボン繊維、ガラスクロス、ホイスカー、
アラミツド繊維等）、機能性混和材（磁性、発光、
導電、収縮、吸水、粘着性等の機能を付与する材
料）、金属粉、金属の酸化物、水酸化物等を添加
したり、さらに種々の表面処理（ラミネート、粘
着性付与処理、プラズマ処理等）を施すことがで
きる。特に、これらの充填剤の添加によつて、粘
着剤又は離型剤との接触面が粗くなり、粘着剤や
離型剤の投錨効果を高めることができる。
さらに、十分な投錨効果が得られない場合に
は、プライマー又は接着剤等を用いることができ
るが、このプライマー、接着剤等も粗面上に積層
させることが好ましい。
本発明の構造体は、粘着剤層を有するものであ
る。この粘着剤層は、基材層の積層する面上に、
粘着剤を通常、厚さ10〜300μm程度、好ましくは
20〜80μm程度に公知の方法で塗布し、50〜300℃
で加熱することにより得られる。この場合、厚さ
が薄すぎると、凹凸を埋めきれずにいたり、塗り
むらが生じたりして得られる粘着性が弱く、また
厚すぎると粘着性構造体のコストが上がる不利が
ある反面、粘着性が強まらない。
前記粘着剤層に用いられる粘着剤としては、シ
リコーン系粘着剤、アクリル系粘着剤、ゴム系粘
着剤、フエノール系粘着剤、SIS（スチレン・イ
ソプレン共重合体）、EVA（エチレン・酢ビ共重
合体）、SBS（スチレン・ブタジエン共重合体）等
の単独及び／又は混合物が挙げられ、これらは、
エマルジヨン型、溶剤型、無溶剤型に分けられる
が、粘着力が高い点で、ジメチルポリシロキサン
を主成分とするシリコーン系粘着剤、アクリル系
粘着剤、天然ゴム、イソブチレン、SISが好まし
く、この場合にも良好で、経時安定性の高い離型
性が得られる。これらは、一種単独でも二種以上
でも用いることができる。
前記粘着剤の具体的な市販品としては、信越化
学工業(株)性KR−130・KR−120・KR−101−10、
トーレシリコーン(株)製SH4280、東芝シリコーン
(株)製YR3340、ダウコーニング社製DC282、東洋
インキ製造社製BPS2411・8170・5127、総研化
学社製SK−801B、大日本インキ化学工業社製
FL・FA・PK・Ｒ・E5・DK・HM・SR・Ｃ・
FYN・A2・Ｎ等を挙げることができる。
本発明の構造体は、離型剤層を有するものであ
る。この離型剤層は、基材層の積層する面上に、
前記の離型性組成物を通常、厚さ0.1〜50μm、好
ましくは１〜10μm程度に公知の方法で塗布し、
50〜300℃で加熱することにより得られる。離型
剤層が薄すぎると、凹凸を埋めきれず、離型性が
悪化し、また厚すぎると粘着剤の粘着力を弱め、
その上コストが上がる原因となる。
前記離型剤層に用いられる離型性組成物は、特
開昭61−228078号に記載のものであり、該組成物
の主剤である共重合体を構成する第１成分はポリ
フルオロアルキル共重合体を含有するビニル系単
量体である。このポリフルオロアルキル基はメチ
ル基、エチル基、プロピル基、ブチル基、オクチ
ル基などのアルキル基の炭素原子に結合した水素
原子の一部又は全部をフツ素原子で置換した基で
あればよく、このような基を含有するビニル系単
量体としては、例えば下記式：
CH2＝CHCO2CH2CF3、
CH2＝Ｃ（CH3）CO2CH2CF3、
CH2＝CHCO2CH2CF2CF2Ｈ、
CH2＝Ｃ（CH3）CO2CH（CH3）2、
CH2＝CHCO2CH（CH3）C3F7、
CH2＝CHCO2CH2C4F9、
CH2＝Ｃ（CH3）CO2CH2C4H9、
CH2＝CHCO2CH2（CF2）4Ｈ、
CH2＝Ｃ（CH3）CO2CH2C6H13、
CH2＝Ｃ（CH3）CO2（CH2）2C8H17、
CH2＝CHCO2（CH2）2C8H17、
等で示される化合物、また次式：
CH2＝CHCOH2CH2C8F17、
CH2＝CHCO2CH2CH2OCH2CF3、
[Industrial Field of Application] The present invention relates to an adhesive structure. [Prior art] Adhesive structures, such as adhesive tapes and labels, are made by laminating an adhesive layer, a release agent layer, and in some cases a laminated base material on both or one side of a base material. used for a purpose. In recent years, silicone adhesives,
In particular, silicone adhesives whose main component is dimethylpolysiloxane have excellent heat resistance, cold resistance, chemical resistance,
It is used in a wide range of applications because of its excellent electrical insulation and non-toxic properties. [Problems to be Solved by the Invention] However, since the above-mentioned adhesive has a very strong adhesive force, the peeling force required to peel the adhesive layer from the release agent layer is insufficient in the conventional adhesive structure. If the adhesive structure is too large, especially if the adhesive structure is stored for a long period of time, the peeling force of the adhesive layer from the release agent layer will increase significantly, which will easily lead to destruction of the adhesive layer and the release agent layer during peeling. There is a drawback that the components of the molding agent migrate to the adhesive layer and the adhesive force of the adhesive decreases, so that it is often useless as an adhesive structure. Therefore, the object of the present invention is to provide a low peeling force and good mold releasability even when using a silicone adhesive mainly composed of dimethylpolysiloxane, and to maintain good mold releasability even after long-term storage. An object of the present invention is to provide an adhesive structure that is maintained with high stability. [Means for solving the problems] The present invention solves the above problems by:
In the adhesive structure having a base layer, an adhesive layer, and a release agent layer, the release agent layer contains: 1. 50 to 98% by weight of a vinyl monomer having a polyfluoroalkyl group, 2. At least 1 vinyl monomer in the molecule. 2 to 50% by weight of a silicone vinyl monomer containing a hydrolyzable group bonded to silicon atoms, and 3 copolymerizable with the vinyl monomer having a polyfluoroalkyl group of the first component. The present invention provides an adhesive structure comprising a cured product of a releasable composition whose main ingredient is a copolymer of a monomer mixture containing 0 to 49% by weight of a vinyl monomer. The adhesive structure of the present invention has three layers as described above, but usually at least one adhesive layer and at least one release agent layer are laminated to the base material layer. When there are multiple pressure-sensitive adhesive layers and/or multiple release agent layers, these layers may be located on the same side of the base material layer, or may be located on different sides or both sides of the base material layer. You may. Further, the adhesive structure of the present invention includes the base layer,
The present invention is not limited to only the pressure-sensitive adhesive layer and the release agent layer, and may have other layers, such as a bonding base material, between or outside the three layers, if necessary. This laminated base material is
It is selected and used as appropriate depending on the function, purpose, etc. required of the adhesive structure, and is not particularly limited, but since the adhesive structure is usually peeled off and discarded when used, it can be used as a material. An inexpensive material such as paper is used. Further, the thickness and the like are appropriately selected according to the purpose, function, etc. Examples of the structure of the adhesive structure of the present invention include those shown in the drawings. In the example shown in FIG. 1, an adhesive layer is laminated on one side of the base material layer, and a mold release agent layer is laminated on the other side. This can be used as a single-sided adhesive tape if the same structure is repeated by winding it around a paper core or the like. Next, in the example shown in FIG. 2, a release agent layer is laminated on one side of the base material layer, and an adhesive layer is laminated thereon. This is also an adhesive structure that can be used as a single-sided adhesive tape by winding it around a paper core or the like. Furthermore, the example shown in FIG. 3 is one in which a bonded base material on which release agent layers are laminated on both sides and a base material layer on which adhesive layers are laminated on both sides are bonded together. This structure can be used not only as a double-sided adhesive sheet but also as a double-sided adhesive tape by winding it around a paper core or the like. Finally, the example shown in FIG. 4 has a structure in which a base material layer with an adhesive layer laminated on one side and a laminated base material with a release agent layer laminated on one side are bonded together. This structure can be applied to labels, etc. The base material layer of the adhesive structure of the present invention is selected depending on the use, function, etc. of the adhesive structure, and is not particularly limited, but includes, for example, paper, rubber, PET sheet, Kapton sheet, metal foil, Teflon sheet. and asbestos cloth. As this rubber, for example, fluorine rubber, silicone rubber, etc. can be used. When rubber is used as the base material, an adhesive structure with excellent elasticity, heat resistance, and electrical insulation can be obtained. Fluorine rubbers are commercially available and often used. for example,. Examples include fluorocarbon rubbers such as the Viton series manufactured by DuPont, the Florel series manufactured by 3M, the Daiel series manufactured by Daikin Industries, and the Afras series manufactured by Asahi Glass. In addition, as silicone rubber, KE, FE, manufactured by Shin-Etsu Chemical Co., Ltd.
SEP series, SH/SE manufactured by Toray Silicone Co., Ltd.
SRX series, TSE/YE series manufactured by Toshiba Silicone Corporation, SS/WC/HS/manufactured by Dow Corning
Examples include silicone rubber such as the Silastic series. These rubbers are used in the form of sheets, but if they are made too thick, a large amount of force is required for expansion and contraction, excessive steps are created by overlapping, the ability to follow irregularities is reduced, and the weight of the structure increases. It is preferable to set the thickness to about 0.01 to 10 mm, since this would increase the thickness and make it too thick. Moreover, the anchoring effect of the adhesive or mold release agent can be enhanced by roughening the surface of the base material layer on which the adhesive or mold release agent is laminated. This rough surface can be obtained by ordinary matte processing, an embossing process during sheet or film production, or by bonding unvulcanized rubber to a matted PET sheet and vulcanizing it. Furthermore, the base material layer contains fillers such as reinforcing fiber materials (carbon fiber, glass cloth, whiskers,
aramid fiber, etc.), functional admixtures (magnetic, luminescent,
Materials that provide functions such as conductivity, shrinkage, water absorption, and adhesiveness), metal powders, metal oxides, hydroxides, etc., and various surface treatments (laminate, tackifier treatment, plasma treatment, etc.) ) can be applied. In particular, by adding these fillers, the contact surface with the adhesive or mold release agent becomes rough, and the anchoring effect of the adhesive or mold release agent can be enhanced. Furthermore, if a sufficient anchoring effect cannot be obtained, a primer or an adhesive can be used, but it is preferable that this primer, adhesive, etc. also be laminated on the rough surface. The structure of the present invention has an adhesive layer. This adhesive layer is placed on the surface of the base material layer to be laminated.
The adhesive is usually about 10 to 300 μm thick, preferably
Apply to approximately 20 to 80 μm using a known method and heat at 50 to 300℃.
It can be obtained by heating at In this case, if the thickness is too thin, it may not be possible to fill in the unevenness or cause uneven coating, resulting in weak adhesion.If it is too thick, the cost of the adhesive structure will increase, but the adhesive Sexuality is not strengthened. Adhesives used in the adhesive layer include silicone adhesives, acrylic adhesives, rubber adhesives, phenol adhesives, SIS (styrene/isoprene copolymer), and EVA (ethylene/vinyl acetate copolymer). Examples include single and/or mixtures of SBS (styrene-butadiene copolymer), etc.
They are divided into emulsion type, solvent type, and solvent-free type, but silicone adhesives mainly composed of dimethylpolysiloxane, acrylic adhesives, natural rubber, isobutylene, and SIS are preferred because of their high adhesive strength. It also provides good mold releasability with high stability over time. These can be used singly or in combination of two or more. Specific commercially available adhesives include Shin-Etsu Chemical Co., Ltd. KR-130, KR-120, KR-101-10,
Toray Silicone Co., Ltd. SH4280, Toshiba Silicone
YR3340 manufactured by Dow Corning Co., Ltd., DC282 manufactured by Dow Corning Co., Ltd., BPS2411/8170/5127 manufactured by Toyo Ink Manufacturing Co., Ltd., SK-801B manufactured by Soken Chemical Co., Ltd., manufactured by Dainippon Ink Chemical Co., Ltd.
FL・FA・PK・R・E5・DK・HM・SR・C・
Examples include FYN, A2, N, etc. The structure of the present invention has a release agent layer. This mold release agent layer is placed on the surface of the base material layer to be laminated.
The above mold release composition is usually applied to a thickness of about 0.1 to 50 μm, preferably about 1 to 10 μm, by a known method,
Obtained by heating at 50-300°C. If the mold release agent layer is too thin, it will not be able to fill in the unevenness and the mold release properties will deteriorate; if it is too thick, the adhesive force of the adhesive will be weakened.
Furthermore, this causes an increase in costs. The mold release composition used in the mold release agent layer is described in JP-A No. 61-228078, and the first component constituting the copolymer which is the main ingredient of the composition is a polyfluoroalkyl copolymer. It is a vinyl monomer containing a polymer. This polyfluoroalkyl group may be a group in which part or all of the hydrogen atoms bonded to the carbon atoms of an alkyl group such as a methyl group, ethyl group, propyl group, butyl group, or octyl group are replaced with fluorine atoms, Examples of vinyl monomers containing such groups include the following formulas: CH 2 = CHCO 2 CH 2 CF 3 , CH 2 = C(CH 3 )CO 2 CH 2 CF 3 , CH 2 = CHCO 2 CH 2 CF 2 CF 2 H, CH 2 = C (CH 3 ) CO 2 CH (CH 3 ) 2 , CH 2 = CHCO 2 CH (CH 3 ) C 3 F 7 , CH 2 = CHCO 2 CH 2 C 4 F 9 , CH2 =C ( CH3 ) CO2CH2C4H9 , CH2 = CHCO2CH2 ( CF2 )4H , CH2 = C ( CH3 ) CO2CH2C6H13 , CH 2 = C (CH 3 ) CO 2 (CH 2 ) 2 C 8 H 17 , CH 2 = CHCO 2 (CH 2 ) 2 C 8 H 17 , etc., and the following formula: CH 2 = CHCOH 2 CH 2 C 8 F 17 , CH 2 = CHCO 2 CH 2 CH 2 OCH 2 CF 3 ,
【化】
CH2＝CHCO2CF（CF3）〔−OCF2CF（CF3）〕oOC3
F7、
CH2＝Ｃ（CH3）CO2CH2CH2OCF2CF2Ｈ、
CH2＝CHCO2CH2CH2OCH2C4F9、
等で示されるような誘導体が挙げられるが、式：[Chemical] CH 2 = CHCO 2 CF (CF 3 ) [-OCF 2 CF (CF 3 )] o OC 3
Examples include derivatives such as F 7 , CH 2 =C(CH 3 )CO 2 CH 2 CH 2 OCF 2 CF 2 H, CH 2 =CHCO 2 CH 2 CH 2 OCH 2 C 4 F 9 , etc. ,formula:
【式】
のように極性基を有するものは除外される。
上記例示の化合物は１種単独でも２種以上でも
用いることができる。この単量体としては、フツ
素含有量が高い程、離型性が向上するため、上記
ポリフルオロアルキル基がブチル基以上のものが
好ましい。また、第１成分の共重合体中における
含有量は、50〜98重量％、好ましくは70〜95重量
％である。第１成分の含有量が50重量％未満であ
ると粘着剤に対する離型性が不十分となり、98重
量％を超えると、離型性はあるが基材との接着性
が悪化し、離型剤層が粘着剤層に移行し、粘着剤
の粘着性が保持されなくなる。
前記共重合体の第２成分であるシリコーン系ビ
ニル単量体は、分子中に少なくとも１個のけい素
原子に結合した加水分解可能な基を有するもので
ある。
上記加水分解可能な基としては、例えばアセト
キシ基、オクタノイルオキシ基、ベンゾイルオキ
シ基等のアシロキシ基、ジメチルケトオキシム
基、メチルエチルケトオキシム基、ジエチルケト
オキシム基等のケトオキシム基、メトキシ基、エ
トキシ基、プロポキシ基等のアルコキシ基、イソ
プロペニルオキシ基、１−エチル−２−メチルビ
ニルオキシ基等のアルケニルオキシ基、ジメチル
アミノ基、ジエチルアミノ基、ブチルアミノ基、
シクロヘキシルアミノ基等のアミノ基、ジメチル
アミノキシ基、ジエチルアミノキシ基等のアミノ
オキシ基、Ｎ−メチルアセトアミド基、Ｎ−エチ
ルアセトアミド基、Ｎ−メチルベンズアミド基等
のアミド基等を挙げることができる。これらのう
ち、反応時に加水分解性基自身がけい素原子から
脱離して系外に飛散するものでなければならない
ため、電子的に安定なもの、立体障害性の大きい
もの、加水分解分解後に高沸点物質を生成するも
のは好ましくない。
したがつて、このシリコーン系ビニル単量体と
しては、次式：
CH2＝CHCO2（CH2）3Si（OCH3）3、
CH2＝CHCO2（CH2）3Si（OC2H5）3、
CH2＝Ｃ（CH3）CO2（CH2）3Si（OCH3）3、
CH2＝Ｃ（CH3）CO2（CH2）3Si（OC2H5）3、
CH2＝CHCO2（CH2）3SiCH3（OC2H5）2、
CH2＝Ｃ（CH3）CO2（CH2）3SiC2H5（OCH3）2、
CH2＝Ｃ（CH3）CO2（CH2）3Si（CH3）2（OC2H5）、
CH2＝Ｃ（CH3）CO2（CH2）3Si（CH3）2OH、Those having a polar group such as [Formula] are excluded. The compounds exemplified above can be used alone or in combination of two or more. This monomer is preferably one in which the polyfluoroalkyl group is a butyl group or more, since the higher the fluorine content, the better the mold releasability. Further, the content of the first component in the copolymer is 50 to 98% by weight, preferably 70 to 95% by weight. If the content of the first component is less than 50% by weight, the releasability from the adhesive will be insufficient, and if it exceeds 98% by weight, there will be releasability but the adhesion to the base material will deteriorate, resulting in mold release. The agent layer transfers to the adhesive layer, and the tackiness of the adhesive is no longer maintained. The silicone vinyl monomer, which is the second component of the copolymer, has at least one hydrolyzable group bonded to a silicon atom in its molecule. Examples of the hydrolyzable groups include acyloxy groups such as acetoxy, octanoyloxy, and benzoyloxy groups, ketoxime groups such as dimethylketoxime, methylethylketoxime, and diethylketoxime, methoxy, and ethoxy groups; Alkoxy groups such as propoxy groups, isopropenyloxy groups, alkenyloxy groups such as 1-ethyl-2-methylvinyloxy groups, dimethylamino groups, diethylamino groups, butylamino groups,
Examples include amino groups such as a cyclohexylamino group, aminooxy groups such as a dimethylaminoxy group and diethylaminoxy group, and amide groups such as an N-methylacetamide group, an N-ethylacetamide group, and an N-methylbenzamide group. Among these, the hydrolyzable group itself must be detached from the silicon atom and scattered out of the system during the reaction, so those that are electronically stable, those that have large steric hindrance, and those that have high Those that produce boiling point substances are not preferred. Therefore, this silicone vinyl monomer has the following formula: CH 2 = CHCO 2 (CH 2 ) 3 Si (OCH 3 ) 3 , CH 2 = CHCO 2 (CH 2 ) 3 Si (OC 2 H 5 ) 3 , CH2 =C( CH3 )CO2 ( CH2 ) 3Si(OCH3) 3 , CH2 =C( CH3 ) CO2 ( CH2 ) 3Si ( OC2H5 ) 3 , CH 2 = CHCO 2 (CH 2 ) 3 SiCH 3 (OC 2 H 5 ) 2 , CH 2 = C(CH 3 ) CO 2 (CH 2 ) 3 SiC 2 H 5 (OCH 3 ) 2 , CH 2 = C(CH 3 ) CO2 ( CH2 ) 3Si ( CH3 ) 2 ( OC2H5 ) , CH2 =C( CH3 ) CO2 ( CH2 ) 3Si ( CH3 ) 2OH ,
【式】【formula】
【化】[ka]
【式】
CH2＝CHCO2（CH2）3SiCH3〔ON（CH3）C2H5〕2、
CH2＝Ｃ（CH3）CO2（CH2）3SiC6H5〔ON（CH3）
C2H5〕2、[Formula] CH 2 = CHCO 2 (CH 2 ) 3 SiCH 3 [ON (CH 3 ) C 2 H 5 ] 2 , CH 2 = C (CH 3 ) CO 2 (CH 2 ) 3 SiC 6 H 5 [ON ( CH3 )
C2H5 〕 2 ,
【式】 CH2＝CHSi（OCH3）3、 CH2＝CHSi（OC2H5）3、 CH2＝CHSiCH3（OCH3）2、[Formula] CH 2 = CHSi(OCH 3 ) 3 , CH 2 = CHSi(OC 2 H 5 ) 3 , CH 2 = CHSiCH 3 (OCH 3 ) 2 ,
【式】 CH2＝CHSi（CH3）2（OC2H5）、 CH2＝CHSi（CH3）2SiCH3（OCH3）2、[Formula] CH 2 = CHSi(CH 3 ) 2 (OC 2 H 5 ), CH 2 = CHSi(CH 3 ) 2 SiCH 3 (OCH 3 ) 2 ,
以下、実施例及び比較例を挙げて本発明を詳細
に説明する。
調製例
実施例及び比較例で使用する離型性組成物を下
記の方法で調製した。
攪拌装置、不活性ガス導入口、還流冷却器及び
温度計をとりつけた四つ口フラスコに、ダイフロ
ンS2−Ｔ（前出）235重量部、式
CH2＝Ｃ（CH3）CO2CH2CH2C8F17
で示されるポリフルオロアルキルビニル単量体90
重量部、ビニルトリエトキシシラン10重量部及び
アゾビスイソブチロニトリル0.5重量部を仕込み、
窒素ガスをバブリングさせながら60〜70℃で５時
間反応させ、ついでそのままの温度で15時間熟成
させてから冷却し、不揮発分が30％となるように
フロン113で調整して組成物を得た。
実施例 １
以下に示す方法で基材層、離型剤層及び粘着剤
層を形成することにより、図１に示す構造を有
し、材質の異なる基材層を有する二種の粘着性構
造体を製造した。
基材層：シリコーンゴムシート（信越化学工業(株)
製TC−45A、厚さ0.45mm）、及びフツ素ゴム
シート（デユポン社製バイトンＢ−50、厚さ
１mm）の２種類を使用した。
離型剤層：上記調整例で得られた組成物を、
MXHF（メタキシレンヘキサフロリド）で希
釈して得られた５％溶液を、基材層の表面に
バーコーターを用いて塗布し、200℃で10分
間加熱して厚さ1μmの層を形成した。
粘着剤層：信越化学工業(株)製KR−130をバーコ
ーターにより、離型剤層の反対側の基材層面
に塗布し、200℃で10分間加熱して、厚さ
60μmの層を形成させた。
実施例 ２
フツ素ゴムシートとして、デユポン社製バイト
ンＢ−50の代わりにダイキン工業(株)製ダイエルＧ
−621の厚さ２mmのシートを使用し、離型剤層上
に粘着剤層を形成した以外は、実施例１と同様に
して、図２に示す構造の粘着性構造体を製造し
た。
実施例 ３
まず、両面に粘着剤層を有する基材層と、両面
に離型剤層を有する貼合基材を作成した。次に、
これらを貼合わせて、図３に示す構造を有し、材
質の異なる基材層を有する二種の粘着性構造体を
製造した。
基材層：シリコーンゴムシート（信越化学工業(株)
製TC−30Aシート、厚さ0.3mm）及びフツ素
ゴムシート（3M社製フローレルFC−2176よ
りなる厚さ１mmのシート）の２種類を使用し
た。
貼合基材：四国製紙(株)製、青グラシン紙（厚さ60
ｇ／m2）。
離型剤層：貼合基材の両面に、前記調製例の組成
物のMXHF5％溶液を塗布し、150℃で30秒
間加熱して厚さ1.4ｇ／m2の層を形成した。
粘着剤層：基材層の両面に実施例１と同様にして
形成した。
上記のようにして、両面に離型剤層を設けた貼
合基材を、両面に粘着剤層を設けた基材層の片面
に積層することにより、粘着性構造体を得た。
実施例 ４
以下に示す基材層、離型剤層及び粘着剤層の形
成並びに貼合基材の貼合わせにより、図４に示す
構造を有し、基材層の材質が異なる二種の粘着性
構造体を製造した。
基材層：シリコーンゴムシート（信越化学工業(株)
製TC−20Aシート、厚さ0.2mm）及びフツ素
ゴムシート（ダイキン工業(株)製ダイエルＧ−
801よりなる厚さ１mmのシート）の２種類を
使用した。
離型剤層、粘着剤層及び貼合基材：実施例３と同
様にして形成した。
実施例 ５
基材層として、片面を粗面化したシリコーンゴ
ムシート（信越化学工業(株)製TC−45Aシート、
厚さ0.45mm）、同様に粗面化したフツ素ゴムシー
ト（ダイキン工業(株)製ダイエルＧ−621シート、
厚さ１mm）を用いた以外は、実施例１と同様にし
て図１に示す構造の粘着性構造体を製造した。
なお、シリコーンゴムシート及びフツ素ゴムシ
ートの片面の粗面化は、マツト加工により片面を
粗面化（表面粗度：10〜50μm）したPETシート
を用い、この上で未加硫ゴムシートを熱加硫する
ことにより行つた。
実施例 ６
基材層として、信越化学工業(株)製KE−
174U100重量部にアルミナを200重量部配合して
得られた組成物を厚さ２mmに成形したシリコーン
ゴムシート、及びデユポン社製バイトンＥ−
60C100重量部にアルミナを200重量部配合して得
られた組成物を厚さ１mmに成形したフツ素ゴムシ
ートを使用した以外は、実施例１と同様にして、
図１に示す構造の粘着性構造体二種を製造した。
実施例 ７
ガラスクロス入りのシリコーンゴムシート（信
越化学工業(株)製TC−45AGシート、厚さ0.45mm）、
及びフツ素ゴムシート（ダイキン工業(株)製ダイエ
ルＧ−501にガラスクロスを添加して成形した厚
さ１mmのシート）を基材層として用いた以外は、
実施例１と同様にして、図１に示す構造の粘着性
構造体を製造した。
実施例 ８
シリコーンゴムシート（信越化学工業(株)製KE
−951シート、厚さ0.5mm）及びフツ素ゴムシート
（3M社製、フローレルFC−2120を厚さ２mmに成
形したシート）を基材層とし、この基材層の上に
実施例１と同様にして離型剤層を形成した。さら
に、その上にテフロンを基材とする粘着テープ
（日東電工(株)製ニトフロンNo.−903UL）を貼合基
材として貼り合わせ、図４に示す構造の粘着性構
造体を製造した。
比較例 １
フツ素ゴムシートとして3M社製フローレルFC
−2174を厚さ１mmに成形したシートを用い、離型
剤層をジメチルポリシロキサンを主成分とするシ
リコーン系離型剤（信越化学工業(株)製、KS−
778）の５％トルエン溶液を使用して形成した以
外は実施例１と同様にして、図１に示す構造の粘
着性構造体を製造した。
比較例 ２
離型剤層を、ジメチルポリシロキサンを主成分
とするシリコーン系離型剤（信越化学工業(株)製、
KS−778）の５％トルエン溶液を使用して形成し
た以外は実施例８と同様にして、図４に示す構造
の粘着性構造体を製造した。
以上の実施例１〜８及び比較例１〜２によつて
得られた粘着性構造体について、以下の特性を評
価した。
〔評価特性〕
１ 製造後、室温で48時間放置した後の剥離力及
び接着力
２ 製造後、100℃で40ｇ／cm2の一定加重下で24
時間保存した後の剥離力、接着力及び投錨性
〔評価方法〕
１ 剥離力及び接着力
図１、図２及び図３に示す粘着性構造体は、粘
着性構造体の粘着剤層の上に離型剤層で使用した
ものと同じ離型剤を塗布してなる離型紙を積層し
たのち試験した。次に、JIS C2107記載の２Kg加
重のゴムローラーを粘着性構造体の端から端まで
１往復させて圧着し、粘着剤層と離型剤層又は粘
着剤層と貼合基材を十分に粘着させた。このよう
に処理した構造体を幅19mmの試験細片に切断した
後、25℃の恒温室で、引張試験機を用いて、剥離
角180°、剥離速度0.3ｍ／分で、離型剤層から粘
着剤層を剥離させることにより剥離力を測定し
た。その後、剥離された粘着剤層を基材層上に積
層させたまま、PETシートに粘着させ、前記の
２Kg加重ゴムローラーを１往復させて圧着後、剥
離力と同様の方法で粘着させたPETシートを剥
離させることにより接着力を測定した。
２ 投錨性
上記剥離力及び接着力の測定時に、粘着剤層及
び離型剤層を観察して評価した。
なお、表面粗度は、表面粗さ計を用いて測定
し、JIS B0601の中心線平均粗さの方法を用いて
測定した。
結果を表１及び表２に示す。
表１、表２より以下のことがわかる。
まず、本発明の構造体の離型剤層は、従来良く
用いられてきたジメシルポリシロキサンを主成分
とするシリコーン系離型剤層より投錨性が良い。
次に本発明の構造体は、ジメチルポリシロキサ
ンを主成分とするシリコーン系離型剤層に比べて
剥離時に大きな力を必要とせず、高い接着力を有
する。しかも、高温で保存した後も、他の粘着性
構造体より、小さな剥離力で剥離し、高い接着力
を有する。
Hereinafter, the present invention will be explained in detail by giving Examples and Comparative Examples. Preparation Example The mold release composition used in the Examples and Comparative Examples was prepared by the following method. In a four-necked flask equipped with a stirring device, an inert gas inlet, a reflux condenser, and a thermometer, 235 parts by weight of Daiflon S2-T (described above) and the formula CH 2 =C(CH 3 )CO 2 CH 2 CH were added. 2 C 8 F 17 polyfluoroalkyl vinyl monomer 90
parts by weight, 10 parts by weight of vinyltriethoxysilane and 0.5 parts by weight of azobisisobutyronitrile,
The mixture was reacted at 60 to 70°C for 5 hours while bubbling nitrogen gas, then aged at that temperature for 15 hours, cooled, and adjusted with Freon 113 so that the nonvolatile content was 30% to obtain a composition. . Example 1 By forming a base material layer, a mold release agent layer, and an adhesive layer by the method shown below, two types of adhesive structures having the structure shown in FIG. 1 and having base material layers made of different materials were obtained. was manufactured. Base layer: Silicone rubber sheet (Shin-Etsu Chemical Co., Ltd.)
Two types of sheets were used: TC-45A manufactured by Dupont Co., Ltd., thickness 0.45 mm) and a fluorocarbon rubber sheet (Viton B-50 manufactured by DuPont, thickness 1 mm). Release agent layer: The composition obtained in the above preparation example,
A 5% solution obtained by diluting with MXHF (meta-xylene hexafluoride) was applied to the surface of the base layer using a bar coater, and heated at 200°C for 10 minutes to form a 1 μm thick layer. . Adhesive layer: Apply KR-130 manufactured by Shin-Etsu Chemical Co., Ltd. to the surface of the base material layer opposite to the release agent layer using a bar coater, and heat at 200°C for 10 minutes to determine the thickness.
A layer of 60 μm was formed. Example 2 As a fluorocarbon rubber sheet, Daiel G manufactured by Daikin Industries, Ltd. was used instead of Viton B-50 manufactured by DuPont.
An adhesive structure having the structure shown in FIG. 2 was produced in the same manner as in Example 1, except that a 2 mm thick sheet of -621 was used and an adhesive layer was formed on the release agent layer. Example 3 First, a bonded base material having a base layer having an adhesive layer on both sides and a release agent layer on both sides was created. next,
These were pasted together to produce two types of adhesive structures having the structure shown in FIG. 3 and having base layers made of different materials. Base layer: Silicone rubber sheet (Shin-Etsu Chemical Co., Ltd.)
Two types of sheets were used: a TC-30A sheet (made by 3M Co., Ltd., 0.3 mm thick) and a fluorocarbon rubber sheet (1 mm thick sheet made of Florel FC-2176, made by 3M Co.). Lamination base material: Shikoku Paper Co., Ltd., blue glassine paper (thickness 60
g/ m2 ). Release agent layer: A 5% MXHF solution of the composition of the above preparation example was applied to both sides of the laminated base material, and heated at 150° C. for 30 seconds to form a layer with a thickness of 1.4 g/m 2 . Adhesive layer: Formed on both sides of the base layer in the same manner as in Example 1. An adhesive structure was obtained by laminating the bonded base material provided with release agent layers on both sides on one side of the base material layer provided with adhesive layers on both sides as described above. Example 4 By forming the base material layer, release agent layer, and adhesive layer shown below and laminating the laminated base materials, two types of adhesives having the structure shown in FIG. 4 and having different materials for the base material layers were obtained. A sexual structure was manufactured. Base layer: Silicone rubber sheet (Shin-Etsu Chemical Co., Ltd.)
TC-20A sheet, 0.2 mm thick) and fluorocarbon rubber sheet (Dai-el G- manufactured by Daikin Industries, Ltd.)
Two types of sheets (1 mm thick sheet made of 801) were used. Release agent layer, adhesive layer, and bonding base material: Formed in the same manner as in Example 3. Example 5 A silicone rubber sheet with one side roughened (TC-45A sheet manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the base material layer.
0.45 mm thick), similarly roughened fluororubber sheet (Daiel G-621 sheet manufactured by Daikin Industries, Ltd.),
An adhesive structure having the structure shown in FIG. 1 was produced in the same manner as in Example 1, except that a film having a thickness of 1 mm was used. To roughen one side of the silicone rubber sheet and fluorocarbon rubber sheet, use a PET sheet that has been roughened on one side by matte processing (surface roughness: 10 to 50 μm), and then apply an unvulcanized rubber sheet on top of the PET sheet. This was done by heat vulcanization. Example 6 As the base material layer, KE- manufactured by Shin-Etsu Chemical Co., Ltd.
A silicone rubber sheet made of a composition obtained by blending 200 parts by weight of alumina with 100 parts by weight of 174U and molded to a thickness of 2 mm, and Viton E-
The same procedure as in Example 1 was carried out, except that a fluororubber sheet formed by molding a composition obtained by blending 200 parts by weight of alumina into 100 parts by weight of 60C to a thickness of 1 mm was used.
Two types of adhesive structures having the structure shown in FIG. 1 were manufactured. Example 7 Silicone rubber sheet containing glass cloth (TC-45AG sheet manufactured by Shin-Etsu Chemical Co., Ltd., thickness 0.45 mm),
and a fluorocarbon rubber sheet (a sheet with a thickness of 1 mm formed by adding glass cloth to Daiel G-501 manufactured by Daikin Industries, Ltd.) was used as the base material layer.
In the same manner as in Example 1, an adhesive structure having the structure shown in FIG. 1 was manufactured. Example 8 Silicone rubber sheet (KE made by Shin-Etsu Chemical Co., Ltd.)
-951 sheet, thickness 0.5 mm) and a fluoro rubber sheet (manufactured by 3M, a sheet made of Florel FC-2120 molded to a thickness of 2 mm) as the base material layer, and on this base material layer, the same as in Example 1 was applied. A release agent layer was formed. Furthermore, a Teflon-based adhesive tape (Nitoflon No.-903UL, manufactured by Nitto Denko Corporation) was laminated thereon as a bonding base material to produce an adhesive structure having the structure shown in FIG. 4. Comparative example 1 Florel FC manufactured by 3M as a fluoro rubber sheet
-2174 molded to a thickness of 1 mm, the mold release agent layer was a silicone mold release agent containing dimethylpolysiloxane as the main component (manufactured by Shin-Etsu Chemical Co., Ltd., KS-2174).
An adhesive structure having the structure shown in FIG. 1 was manufactured in the same manner as in Example 1 except that a 5% toluene solution of 778) was used. Comparative Example 2 The mold release agent layer was formed using a silicone mold release agent mainly composed of dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.).
An adhesive structure having the structure shown in FIG. 4 was manufactured in the same manner as in Example 8 except that it was formed using a 5% toluene solution of KS-778). The adhesive structures obtained in Examples 1 to 8 and Comparative Examples 1 to 2 above were evaluated for the following characteristics. [Evaluation characteristics] 1 Peeling force and adhesive strength after being left at room temperature for 48 hours after production 2 After production, 24 hours under a constant load of 40 g/cm 2 at 100°C
Peeling force, adhesive strength, and anchoring property after time storage [Evaluation method] 1 Peeling force and adhesive strength The adhesive structure shown in Figures 1, 2, and 3 is A release paper coated with the same release agent as that used in the release agent layer was laminated and then tested. Next, a rubber roller with a load of 2 kg as described in JIS C2107 is moved back and forth once from one end of the adhesive structure to the other, and the adhesive layer and the release agent layer or the adhesive layer and the laminating base material are bonded together to ensure sufficient adhesion. I let it happen. After cutting the thus treated structure into test strips with a width of 19 mm, the release agent layer was applied in a constant temperature room at 25°C using a tensile tester at a peeling angle of 180° and a peeling speed of 0.3 m/min. The peeling force was measured by peeling the adhesive layer from the sample. After that, the peeled adhesive layer was laminated on the base material layer and was adhered to a PET sheet, and the 2 kg weighted rubber roller described above was made to reciprocate once to press it, and then the PET sheet was adhered using the same method as the peeling force. Adhesive strength was measured by peeling off the sheet. 2. Anchoring property When measuring the above-mentioned peeling force and adhesive force, the adhesive layer and the mold release agent layer were observed and evaluated. Note that the surface roughness was measured using a surface roughness meter, and was measured using the center line average roughness method of JIS B0601. The results are shown in Tables 1 and 2. The following can be seen from Tables 1 and 2. First, the mold release agent layer of the structure of the present invention has better anchoring properties than the silicone mold release agent layer mainly composed of dimesylpolysiloxane, which has been commonly used in the past. Next, the structure of the present invention does not require a large force during peeling and has high adhesive strength compared to a silicone mold release agent layer containing dimethylpolysiloxane as a main component. Moreover, even after being stored at high temperatures, it peels off with a smaller peeling force than other adhesive structures, and has high adhesive strength.
【表】【table】
【表】【table】
【表】【table】
本発明の粘着性構造体は、離型剤層に用いられ
る離型性組成物が、シリコーン系粘着剤に対して
も、従来のものよりも離型性が良いため、剥離時
に粘着剤層及び離型剤層が破壊されることがな
い。しかも、この良好な離型性は長期にわたつて
高い安定性を有する。又、このような離型剤層を
有する粘着性構造体は、耐候性にも優れるもので
ある。さらに本発明の構造体は、特にゴムを基材
とした場合には、基材が持つ弾力性、耐熱性、電
気絶縁性に優れるという特性を活かした粘着性構
造体として、多種、多目的の用途に活用できる。
In the adhesive structure of the present invention, the release composition used in the release agent layer has better releasability than conventional ones, even with respect to silicone adhesives. The mold release agent layer is not destroyed. Moreover, this good mold releasability has high stability over a long period of time. Moreover, the adhesive structure having such a release agent layer has excellent weather resistance. Furthermore, the structure of the present invention can be used as an adhesive structure for a wide variety of purposes, particularly when rubber is used as the base material, by taking advantage of the excellent elasticity, heat resistance, and electrical insulation properties of the base material. It can be used for
図１〜図４は、本発明の粘着性構造体の実施態
様の断面構成を示す断面図である。
1 to 4 are cross-sectional views showing cross-sectional configurations of embodiments of the adhesive structure of the present invention.
Claims (1)
性構造体において、前記離型剤層が、 １ ポリフルオロアルキル基を有するビニル単量
体 50〜98重量％、 ２ 分子中に少なくとも１個のけい素原子に結合
した加水分解可能な基を含有するシリコーン系
ビニル単量体 ２〜50重量％、 及び ３ 前記第１成分のポリフルオロアルキル基を有
するビニル単量体と共重合可能なビニル系単量
体 ０〜49重量％ からなる単量体混合物の共重合体を主剤とする離
型性組成物の硬化物からなることを特徴とする粘
着性構造体。[Scope of Claims] 1. An adhesive structure having a base material layer, an adhesive layer, and a release agent layer, wherein the release agent layer comprises: 1. 50 to 98% by weight of a vinyl monomer having a polyfluoroalkyl group. , 2 2 to 50% by weight of a silicone vinyl monomer containing a hydrolyzable group bonded to at least one silicon atom in the molecule, and 3 a vinyl monomer having a polyfluoroalkyl group as the first component. An adhesive structure comprising a cured product of a releasable composition whose main ingredient is a copolymer of a monomer mixture consisting of 0 to 49% by weight of a vinyl monomer copolymerizable with a vinyl monomer. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62327950A JPH01166949A (en) | 1987-12-24 | 1987-12-24 | Adhesive structural body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62327950A JPH01166949A (en) | 1987-12-24 | 1987-12-24 | Adhesive structural body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01166949A JPH01166949A (en) | 1989-06-30 |
| JPH0583075B2 true JPH0583075B2 (en) | 1993-11-24 |
Family
ID=18204824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62327950A Granted JPH01166949A (en) | 1987-12-24 | 1987-12-24 | Adhesive structural body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01166949A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4689075B2 (en) * | 2001-05-21 | 2011-05-25 | 日東電工株式会社 | Protective sheet for semiconductor wafer processing |
| KR100880388B1 (en) | 2005-04-20 | 2009-01-23 | 주식회사 엘지화학 | Housing Member For Battery Module |
| JP5589661B2 (en) * | 2010-08-13 | 2014-09-17 | 信越化学工業株式会社 | Releasable composition for pressure-sensitive adhesive |
| JP2013248874A (en) * | 2012-05-30 | 2013-12-12 | Saint-Gobain Performance Plastics Corp | Modified perfluoropolymer material |
| JP5880390B2 (en) * | 2012-10-24 | 2016-03-09 | 信越化学工業株式会社 | Releasable composition for pressure-sensitive adhesive |
| JP7248480B2 (en) * | 2019-03-29 | 2023-03-29 | 株式会社巴川製紙所 | Encapsulant and its manufacturing method |
-
1987
- 1987-12-24 JP JP62327950A patent/JPH01166949A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01166949A (en) | 1989-06-30 |
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