JPH0115543B2 - - Google Patents
Info
- Publication number
- JPH0115543B2 JPH0115543B2 JP12263979A JP12263979A JPH0115543B2 JP H0115543 B2 JPH0115543 B2 JP H0115543B2 JP 12263979 A JP12263979 A JP 12263979A JP 12263979 A JP12263979 A JP 12263979A JP H0115543 B2 JPH0115543 B2 JP H0115543B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- acrylic resin
- emulsion
- adherend
- 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
- 239000000203 mixture Substances 0.000 claims description 34
- 239000004925 Acrylic resin Substances 0.000 claims description 33
- 229920000178 Acrylic resin Polymers 0.000 claims description 33
- 239000000839 emulsion Substances 0.000 claims description 28
- -1 acrylic ester Chemical class 0.000 claims description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 239000010410 layer Substances 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 239000012790 adhesive layer Substances 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229920002457 flexible plastic Polymers 0.000 claims description 4
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical group NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 description 27
- 239000000853 adhesive Substances 0.000 description 23
- 230000001070 adhesive effect Effects 0.000 description 23
- 239000000178 monomer Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 13
- 239000000523 sample Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 150000003672 ureas Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- JZVIGYINCGLMQW-UHFFFAOYSA-N 1-(oxiran-2-yl)ethyl prop-2-enoate Chemical compound C=CC(=O)OC(C)C1CO1 JZVIGYINCGLMQW-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N octan-3-ol Chemical compound CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- OUTQTRJBSUBFPJ-UHFFFAOYSA-N 1-(oxiran-2-yl)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)C1CO1 OUTQTRJBSUBFPJ-UHFFFAOYSA-N 0.000 description 1
- HGOUNPXIJSDIKV-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl 2-methylprop-2-enoate Chemical compound CCC(CO)(CO)COC(=O)C(C)=C HGOUNPXIJSDIKV-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical group C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical group N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 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
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は輸送時或いは板金加工時の損傷防止の
為ステンレス、アルミニユーム、その他金属板、
樹脂塗装板、プラスチツク化粧板等の如き被着体
となる表面に仮着及び該表面から剥離可能な表面
保護シート（以下表面保護シートと略称）に関す
るものであり、詳しくは可撓性のあるプラスチツ
クフイルム、例えばポリ塩化ビニール、ポリエチ
レン、ポリプロピレン、ポリアミド、ポリエステ
ル等の表面に優れた品質のアクリル系樹脂層を設
けた表面保護シートに関する。
表面保護シートとして要求される品質として被
着体に貼付ける際は粘着力が強く使用後に剥がす
際は粘着力が弱く剥がし易いことという一見矛盾
する性質が要求される。従来の表面保護シートで
は被着体に貼合せた後粘着力が経時的に逐次アツ
プし、貼付け時に比し数倍にも達し、剥がし難い
ばかりか、著しい場合には剥離不能となることも
あるので、粘着力の変化が少ない表面保護シート
が要望される。
従来の表面保護シートでは特公昭51−14554号
公報に記載されるとおり被着体に貼付ける粘着層
の部分は、アクリルゴムを溶剤に溶した均一系に
於いて且つ、ベンゾイルパーオキサイド、ジクミ
ルパーオキサイドの如き有機過酸化物又はブチル
エーテル化メラミン、ブチルエーテル化尿素、イ
ソシアネート樹脂などの官能性化合物の架橋剤を
添加して一部架橋させ板金加工性を向上させたも
のであるが、これらのフイルムは被着体に貼合せ
た時から経時的に粘着力がアツプし、剥ぎ取る場
合には初期の数倍の粘着力となり、剥がし難いと
いう欠点が指摘されていた。
而して本発明は、表面保護シートとして実用時
の被着体への粘着層部分におけるアクリル系樹脂
層に関し、例えば既述特公昭51−14554号公報に
記載されているような公知のものとは異なり、該
公報に記載のないような架橋性成分とエマルジヨ
ン重合技術を用いて得られる架橋された微細なア
クリル樹脂系の粒子をして重積構造を有するアク
リル系樹脂層を形成せしめることにより、後述す
るが如き実用価値の極めて高い特性を有する表面
保護シートの粘着層を得、これに基づいて本発明
を達成したものである。
本発明の目的は被着体に貼付け後の粘着力の変
化が少なく経時的に粘着力が増大しない表面保護
シートを提供することにある。
本発明は、被着体への貼付け部分の粘着層とし
てアクリル系樹脂層を可撓性のプラスチツク表面
に展着した、該被着体に対し仮着及び剥離可能な
表面保護シートにおいて、上記アクリル系樹脂が
(A) アクリル酸エステルと、
(B) アクリル酸エステルと共重合しうるビニール
系化合物とを主成分として含有し、更に
(C) エポキシ基とカルボキシル基をそれぞれ有す
るビニール化合物の対を含有する架橋性成分、
Ｎ−メチロールアミド基とエポキシ基をそれぞ
れ有するビニール化合物の対を含有する架橋性
成分及びジー又はトリービニール化合物を含有
する架橋性成分から選ばれる架橋性成分を含有
する組成のエマルジヨン重合と同時に分子構造
的に架橋された微細な重合体粒子の重積構造を
有することを特徴とする。
本発明によればエマルジヨン重合系に於いて重
合の進行と同時に分子構造的に架橋生成したアク
リル系樹脂のエマルジヨン粒子を得、次いで該粒
子を含むエマルジヨンを可撓性プラスチツクシー
トに塗布乾燥させて、微細な上記エマルジヨン粒
子の重積構造を有するアクリル樹脂層を設けてい
るが、これにより、実用時の表面保護シートとし
て、被着体に貼付け後の粘着力のアツプが少ない
優れた性質を賦与させることができる。本発明に
おける上記アクリル系樹脂は、その生成における
重合時に架橋反応が殆んど進行しているため、実
質的に有機溶剤には不溶であり、エマルジヨン重
合体粒子のままの形で残存し、重積された不均一
層からなる構造を有する。
本発明におけるアクリル系樹脂層では個々の粒
子内部で重合生成分子が充分に架橋されており、
粒子個々にゴム弾性を有するが、このような構造
を有する粘着層は、実用時被着体に対し満足しう
る程度の仮着及び剥離可能な性能を有することは
勿論、被着体へ貼付けた後、室内又は直射日光の
あたる屋外に放置しても粘着力が安定しており、
粘着力の経時的増大は僅かである。
ここでいうアクリル系樹脂はアクリル酸エステ
ル及びそれと共重合可能なビニール系化合物を主
成分として、本発明で特定した既述(C)の架橋性成
分である架橋性モノマーを併用してエマルジヨン
系にて重合して得られる。
かゝる本発明における既述(C)の架橋性成分は、
相互に反応性を有する官能基を含有するビニール
化合物の対からなる構成成分かあるいはジー又は
トリービニール化合物成分である。即ち、相互に
反応性を有する官能基の対としては、エポキシ基
とカルボキシル基との組合わせ又はＮ−メチロー
ルアミド基とエポキシ基との組合せである。
上記のエポキシ基含有のビニール化合物の例と
しては、グリシジルメタアクリレート、グリシジ
ルアクリレート、メチルグリシジルメタアクリレ
ート及びメチルグリシジルアクリレート等があ
る。カルボキシル基含有のビニール化合物の例と
しては、メタアクリル酸、アクリル酸、イタコン
酸、クロトン酸、マレイン酸、フマル酸等があ
る。
次に上記のＮ−メチロールアミド基含有のビニ
ール化合物の例としてはＮ−メチロールアクリル
アミド、Ｎ−メチロールメタアクリルアミド等が
ある。
本発明における上記相互に反応性を有する官能
基を有するビニール化合物は、その対として用い
るビニール化合物の双方の合計量が全モノマーの
合計量に対し0.1〜15重量％の間が好ましく、0.1
重量％未満ではエマルジヨン粒子内での架橋が不
充分であり、15重量％をこえると架橋度が高すぎ
て粘着力が低くなりすぎる。
本発明における(C)の架橋性成分のうちジー又は
トリービニール化合物の例としては、ジビニール
ベンゼン、トリメチロールプロパントリメタクレ
ート、トリメチロールプロパントリアクリレート
等があげられる。これらの化合物は全モノマーの
合計量に対し0.1〜７重量％の範囲が好ましい。
本発明におけるアクリル酸エステルは、例えば
アクリル酸とメタノール、エタノール、プロパノ
ール、ブタノール、ｎ−アミルアルコール、ヘプ
チルアルコール、ｎ−オクチルアルコール、メチ
ルペンタノール、２−エチルブタノール、エチル
ヘキシルアルコール等とのエステル反応によつて
得られるが、このアクリル酸エステルは全モノマ
ーの合計量に対し過半量でよい。
次にアクリル酸エステルと共重合可能なビニー
ル系化合物としての例は、メタアクリル酸エステ
ル、スチレン、アクリロニトリル、アクリル酸、
イタコン酸、メタアクリル酸、無水マレイン酸、
ブタジエン、イソプレン、クロロプレンの如き反
応性ビニール結合を有する化合物が用いられる。
これら共重合性ビニール系化合物は全モノマーの
合計量に対し１〜50重量％で使用される。
本発明におけるアクリル系樹脂粒子のエマルジ
ヨンは、可撓性のあるプラスチツクフイルムの表
面に単体で塗布乾燥しても本発明の目的を達成す
るための優れた性質を有するが、更に柔軟性を与
えるためにジオクチルフタレート等の如き可塑剤
を、又、粘着力を調整するためメチロール化メラ
ミン、メチル化尿素などの添加剤を上記塗布にあ
たり、あらかじめ上記エマルジヨンに添加しても
良い。
本発明の表面保護シートは粘着力が被着体へ貼
付け後に長期間安定しているという特徴を有して
いるばかりでなく、長期間貼付け後の剥離時又は
板金深絞り加工時の高剪断力による粘着層の破壊
に起因する被着体への粘着剤の汚染がない良好な
品質も併せ有する利点がある。
上記本発明の表面保護シートの実用時における
経時安定性を評価する方法として室内放置さらに
屋外に暴露された状態の目安としてウエザオメー
ター試験法で測定した。その結果、室内放置の場
合、本発明の表面保護シートは６ケ月間経時後の
粘着力と初期粘着力の比は1.5以下であり、たと
えば特公昭51−14554号の実施例で得られたよう
な公知のものに比し極めて良好であり、一方ウエ
ザオメーター試験結果でも、例えば200hr〔屋外放
置６ケ月に相当〕に於いて1.4以下である如く、
上記したように従来公知の表面保護シートに比し
優れていることが判る。
以下実施例を記載する。
実施例 １
塩化ビニール100重量部ジオクチルフタレート
35重量部、ステアリン酸カルシウム１重量部及び
ステアリン酸0.5重量部の組成の物をカレンダー
法で0.1m/m厚のフイルムに圧延して可撓性の塩
化ビニールフイルムを得た。温度計、還流冷却
器、滴下ロート、窒素導入口及び撹拌器を付した
フラスコに脱イオン水150重量部、ラウリル硫酸
ソーダ（界面活性剤）２重量部を入れ、窒素雰囲
気下で撹拌しながら70℃まで昇温する。過硫酸カ
リ（重合開始剤）0.5重量部を添加し溶解させる。
更にメタクリル酸メチル23重量部、アクリル酸２
−エチルヘキシル73重量部、メタアクリル酸グリ
シジル２重量部、メタアクリル酸２重量部よりな
るモノマー混合物100重量部を４時間で連続滴下
し、滴下終了後も３時間撹拌を続け重合を完了さ
せる。
このようにして得たアクリル系樹脂粒子のエマ
ルジヨン100重量部とジオクチルフタレート５重
量部の配合物をリバースコーターにて前記の塩化
ビニールフイルムに5μの厚さに塗布し130℃で１
分間加熱乾燥して試料を得た。
実施例 ２
実施例−１で用いた構成割合のモノマー混合物
100重量部の代りに、メタアクリル酸メチル21重
量部、アクリル酸ブチル75重量部、Ｎ−メチロー
ルアクリルアミド２重量部及びグリシジルアクリ
レート２重量部を用いた以外は、実施例−１と同
様な重合方法によりアクリル系樹脂粒子のエマル
ジヨン100重量部を得た。実施例−１と同一の塩
化ビニールフイルムの片側表面に上記得られたア
クリル系樹脂粒子のエマルジヨン100重量部及び
メチル化尿素３重量部からなる配合物をリバース
コーターで5μの厚さに塗布し130℃で１分間加熱
乾燥して試料を得た。
実施例 ３
実施例−２の方法において、メチル化尿素を使
用しない以外は、全く実施例−２の方法によつ
て、試料を得た。
実施例 ４
実施例−１で用いた構成割合のモノマー混合物
100重量部の代りに、アクリル酸エチル68重量部、
アクリル酸ブチル29重量部、メタアクリル酸２重
量部及びトリメチロールプロパンメタクリレート
１重量部の構成割合からなるモノマー混合物100
重量部を用いた以外は、実施例−１と同様な重合
方法によりアクリル系樹脂粒子のエマルジヨン
100重量部を得た。
次いで、実施例−１と同一の塩化ビニールフイ
ルムの片側表面に、上記得られたアクリル系樹脂
粒子のエマルジヨン100重量部及びメチロール化
メラミン３重量部からなる配合物をリバースコー
ターで10μの厚さに塗布し130℃で１分間加熱乾
燥して試料を得た。
実施例 ５
実施例−１で用いた構成割合のモノマー混合物
100重量部の代りに、メタアクリル酸メチル22重
量部、アクリル酸ブチル75重量部、アクリル酸２
重量部及びジビニルベンゼン１重量部の構成割合
からなるモノマー混合物100重量部を用いた以外
は、実施例−１と同様な重合方法によりアクリル
系樹脂粒子のエマルジヨン100重量部を得た。
次いで、低密度ポリエチレン〔メルトインデツ
クス2.0〕をＴダイ押出法にて0.06m/m厚さのフ
イルムを作り、このフイルムの片面をコロナ処理
し、その処理面にリバースコーターで上記アクリ
ル系樹脂粒子のエマルジヨンを3μの厚さに塗布
し100℃で２分間加熱乾燥して試料を得た。
実施例 ６
実施例−１で用いた構成割合のモノマー混合物
100重量部の代りに、スチレン34重量部、アクリ
ル酸２−エチルヘキシル64重量部、メチルグリシ
ジルアクリレート１重量部及びメタアクリル酸１
重量部の構成割合からなるモノマー混合物100重
量部を用いた以外は、実施例−１と同様な重合方
法によりアクリル系樹脂粒子のエマルジヨン100
重量部を得た。
次いで、実施例−５と同じポリエチレンフイル
ムのコロナ処理面に、上記アクリル系樹脂粒子の
エマルジヨン100重量部及びメチロール化メラミ
ン３重量部との配合物をリバースコーターにて
10μの厚さになるように塗布し、100℃で２分間
加熱乾燥して試料を得た。
比較例 １
実施例−１におけるアクリル系樹脂粒子のエマ
ルジヨンの製造に用いたモノマー混合物の構成成
分におけるメタアクリル酸グリシジル２重量部と
メタアクリル酸２重量部の使用の代りに、メタア
クリル酸４重量部を使用した以外は、実施例−１
で用いたモノマー混合物の構成成分及びこれらそ
れぞれの該当使用量で構成される組成のモノマー
混合物100重量部を用いて実施例−１で示すと同
じ重合方法でアクリル系樹脂粒子のエマルジヨン
を得、該エマルジヨン100重量部とジオクチルフ
タレート５重量部の配合物を実施例−１に示す方
法と同様にして試料を得た。
比較例 ２
実施例−１におけるアクリル系樹脂粒子のエマ
ルジヨンの製造に用いたモノマー混合物の構成成
分におけるメタアクリル酸グリシジル２重量部、
メタアクリル酸２重量部の使用の代りにメタアク
リル酸グリシジル４重量部を使用した以外は、実
施例−１で用いたモノマー混合物の構成成分及び
それらそれぞれの該当使用量で構成される組成の
モノマー混合物100重量部を用いて実施例１で示
すと同じ重合方法でアクリル系樹脂粒子のエマル
ジヨンを得、該エマルジヨン100重量部とジオク
チルフタレート５重量部の配合物を実施例−１に
示す方法と同様にして試料を得た。
比較例 ３
実施例−２におけるアクリル系樹脂粒子のエマ
ルジヨンの製造に用いたモノマー混合物の構成成
分におけるＮ−メチロールアクリルアミド２重量
部及びグリシジルアクリレート２重量部の使用の
代りにＮ−メチロールアクリルアミド２重量部を
使用した以外は、実施例−２で用いたモノマー混
合物の構成成分及びそれらそれぞれの該当使用量
で構成される組成モノマー混合物100重量部を用
いて実施例１で示すと同じ重合方法で得られたア
クリル系樹脂粒子のエマルジヨン100重量部に、
メチル化尿素３重量部を配合する等実施例−２で
得られたアクリル系樹脂粒子のエマルジヨンの場
合と全く同様に処理して、実施例−２で得られた
試料の対照例となる試料を得た。
比較例 ４
エマルジヨン重合により得られたアクリル系樹
脂粒子のエマルジヨンを乾燥して得た比較例−１
と同じ組成即ち、メタアクリル酸メチル23重量
部、アクリル酸２−エチルヘキシル73重量部及び
メタアクリル酸４重量部からなるアクリル系樹脂
100重量部に、ベンゾイルパーオキサイド５重量
部及びトルオール600重量部を添加混合してなる
上記アクリル系樹脂の溶解した溶液をリバースコ
ーターにて実施例−１と同じ可撓性の塩化ビニー
ルフイルムに、5μの厚さに塗布し130℃で１分間
加熱乾燥して試料を得た。
以上述べた実施例及び比較例においてそれぞれ
得られた各試料を、これら各試料の間における次
記性能試験を同じ実験条件下に行つて、得られる
表面保護シートとしての要求される性能の測定結
果は次記表−１及び表−２の通りである。
なお、本願性能試験では、表−１及び表−２に
示す試料は表面保護シートをゴムローラーなどに
よりステンレス板（SUS−430BA板）に圧着さ
せて調製された。
The present invention is designed to prevent damage to stainless steel, aluminum, and other metal plates during transportation or sheet metal processing.
It relates to a surface protection sheet (hereinafter abbreviated as "surface protection sheet") that can be temporarily attached to and peeled off from an adherend surface such as a resin-coated board or a plastic decorative board. The present invention relates to a surface protection sheet in which an acrylic resin layer of excellent quality is provided on the surface of a film such as polyvinyl chloride, polyethylene, polypropylene, polyamide, polyester, etc. The qualities required for a surface protection sheet include the seemingly contradictory properties of having strong adhesive strength when pasting it on an adherend, and having weak adhesive strength and ease of peeling when peeled off after use. With conventional surface protection sheets, the adhesive strength gradually increases over time after being attached to the adherend, reaching several times the strength at the time of attachment, making it not only difficult to remove, but in extreme cases, it may become impossible to remove. Therefore, a surface protection sheet with little change in adhesive strength is desired. In conventional surface protection sheets, as described in Japanese Patent Publication No. 51-14554, the adhesive layer attached to the adherend is made of a homogeneous system of acrylic rubber dissolved in a solvent, benzoyl peroxide, dicumyl, etc. These films are partially crosslinked by adding a crosslinking agent such as an organic peroxide such as peroxide or a functional compound such as butyl etherified melamine, butyl etherified urea, or isocyanate resin to improve sheet metal processability. It has been pointed out that the adhesive strength increases over time from the time it is pasted to the adherend, and when it is peeled off, the adhesive strength is several times the initial adhesive strength, making it difficult to peel off. Accordingly, the present invention relates to an acrylic resin layer in the adhesive layer portion to an adherend when used as a surface protection sheet in practical use, and the present invention relates to a known acrylic resin layer as described in Japanese Patent Publication No. Sho 51-14554, for example. However, by forming an acrylic resin layer having a layered structure by using crosslinked fine acrylic resin particles obtained using a crosslinking component and emulsion polymerization technology that are not described in the publication, The present invention was achieved based on an adhesive layer of a surface protection sheet having properties of extremely high practical value as will be described later. An object of the present invention is to provide a surface protection sheet that exhibits little change in adhesive strength after being applied to an adherend and does not increase in adhesive strength over time. The present invention provides a surface protection sheet that can be temporarily attached to and peeled off from the adherend, in which an acrylic resin layer is spread on a flexible plastic surface as an adhesive layer for the part to be attached to the adherend. The system resin contains (A) an acrylic ester and (B) a vinyl compound copolymerizable with the acrylic ester as main components, and further contains (C) a pair of vinyl compounds each having an epoxy group and a carboxyl group. Crosslinkable component contained,
Emulsion polymerization of a composition containing a crosslinkable component selected from a crosslinkable component containing a pair of vinyl compounds each having an N-methylolamide group and an epoxy group, and a crosslinkable component containing a di- or tri-vinyl compound, and the molecular structure It is characterized by having a stacked structure of finely crosslinked polymer particles. According to the present invention, in an emulsion polymerization system, emulsion particles of an acrylic resin are molecularly crosslinked as the polymerization progresses, and then the emulsion containing the particles is coated on a flexible plastic sheet and dried. An acrylic resin layer is provided that has a layered structure of the fine emulsion particles mentioned above, which gives it an excellent property that it can be used as a surface protection sheet in practical use with less increase in adhesive strength after being applied to an adherend. be able to. In the acrylic resin of the present invention, most of the crosslinking reaction has progressed during polymerization during its production, so it is substantially insoluble in organic solvents and remains in the form of emulsion polymer particles. It has a structure consisting of stacked non-uniform layers. In the acrylic resin layer of the present invention, polymerization molecules are sufficiently crosslinked inside each particle,
Each particle has rubber elasticity, but an adhesive layer with such a structure not only has satisfactory temporary adhesion and peelability properties to the adherend in practical use, but also The adhesive strength remains stable even when left indoors or outdoors in direct sunlight.
The increase in adhesion over time is slight. The acrylic resin referred to here is an emulsion-based resin whose main components are an acrylic acid ester and a vinyl compound copolymerizable with it, in combination with a crosslinkable monomer, which is the crosslinkable component (C) specified in the present invention. It is obtained by polymerization. The crosslinkable component (C) mentioned above in the present invention is
A component consisting of a pair of vinyl compounds containing mutually reactive functional groups or a di- or tri-vinyl compound component. That is, a pair of mutually reactive functional groups is a combination of an epoxy group and a carboxyl group or a combination of an N-methylolamide group and an epoxy group. Examples of the above-mentioned epoxy group-containing vinyl compounds include glycidyl methacrylate, glycidyl acrylate, methylglycidyl methacrylate, and methylglycidyl acrylate. Examples of carboxyl group-containing vinyl compounds include methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, and fumaric acid. Next, examples of the above-mentioned N-methylolamide group-containing vinyl compounds include N-methylol acrylamide, N-methylol methacrylamide, and the like. In the vinyl compound having mutually reactive functional groups in the present invention, the total amount of both vinyl compounds used as a pair is preferably between 0.1 and 15% by weight based on the total amount of all monomers, and 0.1
If it is less than 15% by weight, crosslinking within the emulsion particles will be insufficient, and if it exceeds 15% by weight, the degree of crosslinking will be too high and the adhesive strength will be too low. Among the crosslinkable components (C) in the present invention, examples of di- or trivinyl compounds include divinylbenzene, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, and the like. The amount of these compounds preferably ranges from 0.1 to 7% by weight based on the total amount of all monomers. The acrylic ester in the present invention can be used, for example, in an ester reaction between acrylic acid and methanol, ethanol, propanol, butanol, n-amyl alcohol, heptyl alcohol, n-octyl alcohol, methylpentanol, 2-ethylbutanol, ethylhexyl alcohol, etc. However, the amount of this acrylic ester may be a majority of the total amount of all monomers. Next, examples of vinyl compounds that can be copolymerized with acrylic esters include methacrylic esters, styrene, acrylonitrile, acrylic acid,
itaconic acid, methacrylic acid, maleic anhydride,
Compounds having reactive vinyl bonds such as butadiene, isoprene, chloroprene are used.
These copolymerizable vinyl compounds are used in an amount of 1 to 50% by weight based on the total amount of all monomers. The emulsion of acrylic resin particles in the present invention has excellent properties to achieve the object of the present invention even when applied alone to the surface of a flexible plastic film and dried. A plasticizer such as dioctyl phthalate may be added to the emulsion, and additives such as methylolated melamine and methylated urea may be added to the emulsion in advance to adjust the adhesive strength. The surface protection sheet of the present invention not only has the characteristic that the adhesive strength is stable for a long period of time after being pasted on the adherend, but also has the characteristic of high shearing force when peeling off after long-time pasting or during deep drawing of sheet metal. It also has the advantage of good quality, with no contamination of the adhesive on the adherend due to destruction of the adhesive layer. As a method of evaluating the stability over time of the surface protection sheet of the present invention in practical use, measurements were made using a weather-o-meter test method as a measure of the state of being left indoors and exposed outdoors. As a result, when left indoors, the surface protection sheet of the present invention had a ratio of adhesive strength after 6 months of aging to initial adhesive strength of 1.5 or less, as was obtained, for example, in the example of Japanese Patent Publication No. 14554/1983. It is extremely good compared to known products, and on the other hand, the weatherometer test results show that it is 1.4 or less after 200 hours (equivalent to 6 months left outdoors).
As mentioned above, it can be seen that this sheet is superior to conventionally known surface protection sheets. Examples will be described below. Example 1 Vinyl chloride 100 parts by weight dioctyl phthalate
A flexible vinyl chloride film was obtained by rolling a film having a composition of 35 parts by weight, 1 part by weight of calcium stearate, and 0.5 part by weight of stearic acid into a film having a thickness of 0.1 m/m using a calendar method. Put 150 parts by weight of deionized water and 2 parts by weight of sodium lauryl sulfate (surfactant) into a flask equipped with a thermometer, reflux condenser, dropping funnel, nitrogen inlet, and stirrer, and add 70 parts by weight of sodium lauryl sulfate (surfactant) while stirring under a nitrogen atmosphere. Raise the temperature to ℃. Add and dissolve 0.5 parts by weight of potassium persulfate (polymerization initiator).
Furthermore, 23 parts by weight of methyl methacrylate, 2 parts by weight of acrylic acid
- 100 parts by weight of a monomer mixture consisting of 73 parts by weight of ethylhexyl, 2 parts by weight of glycidyl methacrylate, and 2 parts by weight of methacrylic acid was continuously added dropwise over a period of 4 hours, and stirring was continued for 3 hours even after the addition was completed to complete the polymerization. A mixture of 100 parts by weight of the emulsion of acrylic resin particles thus obtained and 5 parts by weight of dioctyl phthalate was coated on the above vinyl chloride film to a thickness of 5μ using a reverse coater, and heated at 130°C for 10 minutes.
A sample was obtained by heating and drying for a minute. Example 2 Monomer mixture with the composition ratio used in Example-1
Polymerization method similar to Example-1 except that 21 parts by weight of methyl methacrylate, 75 parts by weight of butyl acrylate, 2 parts by weight of N-methylol acrylamide, and 2 parts by weight of glycidyl acrylate were used instead of 100 parts by weight. 100 parts by weight of an emulsion of acrylic resin particles was obtained. A mixture consisting of 100 parts by weight of the acrylic resin particle emulsion obtained above and 3 parts by weight of methylated urea was coated on one surface of the same vinyl chloride film as in Example 1 to a thickness of 5μ using a reverse coater. A sample was obtained by heating and drying at ℃ for 1 minute. Example 3 A sample was obtained in the same manner as in Example 2 except that methylated urea was not used. Example 4 Monomer mixture with the composition ratio used in Example-1
68 parts by weight of ethyl acrylate instead of 100 parts by weight,
Monomer mixture 100 consisting of 29 parts by weight of butyl acrylate, 2 parts by weight of methacrylic acid, and 1 part by weight of trimethylolpropane methacrylate
An emulsion of acrylic resin particles was prepared by the same polymerization method as in Example 1 except that parts by weight were used.
100 parts by weight were obtained. Next, a mixture consisting of 100 parts by weight of the emulsion of acrylic resin particles obtained above and 3 parts by weight of methylolated melamine was coated on one surface of the same vinyl chloride film as in Example-1 to a thickness of 10μ using a reverse coater. It was coated and dried by heating at 130°C for 1 minute to obtain a sample. Example 5 Monomer mixture with the composition ratio used in Example-1
Instead of 100 parts by weight, 22 parts by weight of methyl methacrylate, 75 parts by weight of butyl acrylate, 2 parts by weight of acrylic acid.
100 parts by weight of an emulsion of acrylic resin particles was obtained by the same polymerization method as in Example 1, except that 100 parts by weight of a monomer mixture consisting of 1 part by weight and 1 part by weight of divinylbenzene was used. Next, a film with a thickness of 0.06 m/m is made from low-density polyethylene (melt index 2.0) by T-die extrusion, one side of this film is corona treated, and the above-mentioned acrylic resin particles are coated on the treated side with a reverse coater. The emulsion was applied to a thickness of 3μ and dried by heating at 100°C for 2 minutes to obtain a sample. Example 6 Monomer mixture with the composition ratio used in Example-1
Instead of 100 parts by weight, 34 parts by weight of styrene, 64 parts by weight of 2-ethylhexyl acrylate, 1 part by weight of methylglycidyl acrylate, and 1 part by weight of methacrylic acid.
An emulsion of acrylic resin particles was prepared by the same polymerization method as in Example 1, except that 100 parts by weight of the monomer mixture having the composition ratio of 100 parts by weight was used.
Parts by weight were obtained. Next, a mixture of 100 parts by weight of the emulsion of the acrylic resin particles and 3 parts by weight of methylolated melamine was applied to the corona-treated surface of the same polyethylene film as in Example 5 using a reverse coater.
It was coated to a thickness of 10 μm and dried by heating at 100° C. for 2 minutes to obtain a sample. Comparative Example 1 Instead of using 2 parts by weight of glycidyl methacrylate and 2 parts by weight of methacrylic acid in the constituent components of the monomer mixture used for producing the emulsion of acrylic resin particles in Example-1, 4 parts by weight of methacrylic acid was used. Example-1 except that part was used.
An emulsion of acrylic resin particles was obtained by the same polymerization method as shown in Example-1 using 100 parts by weight of a monomer mixture having a composition composed of the constituent components of the monomer mixture used in 1 and the corresponding amounts used of each of these. A sample of a blend of 100 parts by weight of emulsion and 5 parts by weight of dioctyl phthalate was obtained in the same manner as in Example-1. Comparative Example 2 2 parts by weight of glycidyl methacrylate in the constituent components of the monomer mixture used to produce the emulsion of acrylic resin particles in Example-1,
The monomer composition was composed of the constituent components of the monomer mixture used in Example-1 and their respective usage amounts, except that 4 parts by weight of glycidyl methacrylate was used instead of 2 parts by weight of methacrylic acid. An emulsion of acrylic resin particles was obtained by the same polymerization method as shown in Example 1 using 100 parts by weight of the mixture, and a blend of 100 parts by weight of the emulsion and 5 parts by weight of dioctyl phthalate was prepared by the same method as shown in Example-1. A sample was obtained. Comparative Example 3 2 parts by weight of N-methylol acrylamide was used instead of 2 parts by weight of N-methylol acrylamide and 2 parts by weight of glycidyl acrylate in the constituent components of the monomer mixture used for producing the emulsion of acrylic resin particles in Example-2. was obtained by the same polymerization method as shown in Example 1 using 100 parts by weight of a monomer mixture composed of the constituent components of the monomer mixture used in Example-2 and their respective usage amounts. To 100 parts by weight of an emulsion of acrylic resin particles,
A control sample for the sample obtained in Example 2 was prepared in exactly the same manner as in the case of the emulsion of acrylic resin particles obtained in Example 2, including adding 3 parts by weight of methylated urea. Obtained. Comparative Example 4 Comparative Example 1 obtained by drying an emulsion of acrylic resin particles obtained by emulsion polymerization
An acrylic resin having the same composition as 23 parts by weight of methyl methacrylate, 73 parts by weight of 2-ethylhexyl acrylate, and 4 parts by weight of methacrylic acid.
A solution of the acrylic resin dissolved in 100 parts by weight, 5 parts by weight of benzoyl peroxide and 600 parts by weight of toluene was added and mixed using a reverse coater onto the same flexible vinyl chloride film as in Example-1. It was applied to a thickness of 5 μm and dried by heating at 130° C. for 1 minute to obtain a sample. The following performance tests were conducted on each of the samples obtained in the Examples and Comparative Examples described above under the same experimental conditions, and the results were obtained of the required performance as a surface protection sheet. are as shown in Tables 1 and 2 below. In the present performance test, the samples shown in Tables 1 and 2 were prepared by pressing the surface protection sheet onto a stainless steel plate (SUS-430BA plate) using a rubber roller or the like.
【表】
対する増加率であり％で表示した。
粘着力は180゜剥離法にもとづいた300m/m／分
の引剥がし速度によつて測定された。実施例は何
れも粘着力の増加率は50％以下であり粘着力の安
定性が極めて良好なことが判る。それに対して比
較例では100％以上の増加率となり明らかに品性
質の差が認められる。[Table] The increase rate is expressed in %.
Adhesion was measured using a peel rate of 300 m/m/min based on the 180° peel method. In all Examples, the rate of increase in adhesive strength was 50% or less, indicating that the stability of adhesive strength was extremely good. On the other hand, in the comparative example, the increase rate was more than 100%, clearly showing a difference in quality.
【表】【table】
【表】
耐候促進試験法はウエザオメーターで行ない、
63℃の温度で60分間に12分の割合での水スプレー
を実施した。50hrは屋外暴露の約２ケ月間に相当
し200hrは７〜８ケ月間の屋外暴露に相当すると
一般に言われている。
本願における絞り加工試験は日刊工業新聞社発
行雑誌「プレス技術」臨時増刊号第152頁の表−
２及び表−３に関する説明の記載の方法に従つて
試験した。
なお、表面保護シート（既述試料）及びステン
レス板（既述被着体）とを用いて上記加工試験を
行う際の実体を明らかにするために、該試験に用
いたエレクセン試験機におけるポンチ底部とダイ
ス孔部分の関連位置を示す部分拡大縦断面図とし
て第１図を示した。第１図においてポンチ底部の
形状は丸み半径3Rは３mm、ポンチ直径は35mmで
あり、又、ダイス孔直径37mm、ダイス肩半径3R
は３mmである。本願における絞り加工試験では絞
り深さは16m/mで被着体はSUS430BA板で0.6
ｍ／ｍ厚の試料を用い５m/m／分で絞り加工を実
施した。評価は絞り後1hr経過後に表面保護シー
トを被着体であるステンレス板から既述の180゜剥
離法にもとづいて引き剥がし、該被着体への糊汚
染を調べた。表−２の如く実施例ではまつたく汚
染はなく比較例に比して優れている事が判る。
耐候促進試験に於いては本実施例のシートは粘
着力の変化が極めて少ないのに対して比較例のシ
ートでは著しく大きくなることが判る。又被着体
への糊汚染も実施例では観察されなかつた。[Table] The accelerated weathering test method is carried out using a weather meter.
Water spraying was carried out at a rate of 12 minutes in 60 minutes at a temperature of 63°C. It is generally said that 50 hours corresponds to about 2 months of outdoor exposure, and 200 hours corresponds to 7 to 8 months of outdoor exposure. The drawing test in this application is shown in the table on page 152 of the special issue of "Press Technology", a magazine published by Nikkan Kogyo Shimbun.
The test was conducted according to the method described in the explanation regarding Table 2 and Table 3. In addition, in order to clarify the substance when performing the above processing test using a surface protection sheet (previously described sample) and a stainless steel plate (previously described adherend), the bottom of the punch in the Elecsen testing machine used in the test was FIG. 1 is a partially enlarged longitudinal sectional view showing the relative positions of the die hole portion and the die hole portion. In Figure 1, the shape of the bottom of the punch has a roundness radius of 3R, a punch diameter of 35mm, a die hole diameter of 37mm, and a die shoulder radius of 3R.
is 3mm. In the drawing test in this application, the drawing depth was 16m/m, and the adherend was a SUS430BA plate with 0.6
Drawing was carried out at 5 m/m/min using a sample with a thickness of m/m. For evaluation, 1 hour after drawing, the surface protection sheet was peeled off from the adherend, which was a stainless steel plate, using the previously described 180° peeling method, and the adhesive contamination on the adherend was examined. As shown in Table 2, there was no contamination in the Examples and it was found that they were superior to the Comparative Examples. It can be seen that in the accelerated weathering test, the adhesive strength of the sheet of this example shows very little change, whereas the change of adhesive strength of the sheet of comparative example increases significantly. Also, no adhesive staining on the adherend was observed in the examples.
第１図は絞り加工の評価を行うエレクセン試験
装置の部分拡大断面略図である。
１……試料である表面保護シート、２……被着
体として例示のステンレス板。
FIG. 1 is a partially enlarged cross-sectional schematic diagram of an Eleksen test device for evaluating drawing processing. 1...Surface protection sheet as a sample, 2...Stainless steel plate as an adherend.
Claims (1)
ル系樹脂層を可撓性のプラスチツク表面に展着し
た、該被着体に対し仮着及び剥離可能な表面保護
シートにおいて、上記アクリル系樹脂が (A) アクリル酸エステルと、 (B) アクリル酸エステルと共重合しうるビニール
系化合物とを主成分として含有し、更に (C) エポキシ基とカルボキシル基をそれぞれ有す
るビニール化合物の対を含有する架橋性成分、
Ｎ−メチロールアミド基とエポキシ基をそれぞ
れ有するビニール化合物の対を含有する架橋性
成分及びジー又はトリービニール化合物を含有
する架橋性成分から選ばれる架橋性成分を含有
する組成の、エマルジヨン重合−架橋生成物で
あることを特徴とする表面保護シート。[Scope of Claims] 1. A surface protection sheet that can be temporarily attached to and peeled off from an adherend, in which an acrylic resin layer is spread on a flexible plastic surface as an adhesive layer for the part to be attached to the adherend. , the acrylic resin contains (A) an acrylic ester and (B) a vinyl compound copolymerizable with the acrylic ester as main components, and further (C) a vinyl compound having an epoxy group and a carboxyl group, respectively. a crosslinkable component containing a pair of
Emulsion polymerization-crosslinking of a composition containing a crosslinkable component selected from a crosslinkable component containing a pair of vinyl compounds each having an N-methylolamide group and an epoxy group, and a crosslinkable component containing a di- or tri-vinyl compound. A surface protection sheet characterized by being a material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12263979A JPS5646749A (en) | 1979-09-26 | 1979-09-26 | Protective sheet for surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12263979A JPS5646749A (en) | 1979-09-26 | 1979-09-26 | Protective sheet for surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5646749A JPS5646749A (en) | 1981-04-28 |
| JPH0115543B2 true JPH0115543B2 (en) | 1989-03-17 |
Family
ID=14840942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12263979A Granted JPS5646749A (en) | 1979-09-26 | 1979-09-26 | Protective sheet for surface |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5646749A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019011364A (en) * | 2013-05-17 | 2019-01-24 | インサイト・コーポレイションＩｎｃｙｔｅ Ｃｏｒｐｏｒａｔｉｏｎ | Bipyrazole derivative as jak inhibitor |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61501856A (en) * | 1984-04-12 | 1986-08-28 | エイベリ インタナシヨナル コ−ポレイシヨン | peelable label |
| JPS61268782A (en) * | 1985-05-22 | 1986-11-28 | Nitto Electric Ind Co Ltd | Surface-protection sheet |
| CN115636898B (en) * | 2022-10-24 | 2023-05-30 | 广东银洋环保新材料有限公司 | Strippable acrylic emulsion, preparation method thereof and strippable protective film |
-
1979
- 1979-09-26 JP JP12263979A patent/JPS5646749A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019011364A (en) * | 2013-05-17 | 2019-01-24 | インサイト・コーポレイションＩｎｃｙｔｅ Ｃｏｒｐｏｒａｔｉｏｎ | Bipyrazole derivative as jak inhibitor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5646749A (en) | 1981-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2898348B2 (en) | Preparation of copolymers that can be cross-linked by ultraviolet irradiation in air oxygen atmosphere | |
| US5294688A (en) | UV-crosslinkable copolymers | |
| GB2048274A (en) | Pressure sensitive hot melt adhesive curable by exposure to electron beam radiation | |
| US4495243A (en) | Release agent and product | |
| EP2718385B1 (en) | Hot melt adhesive containing radiation curable poly(meth)acrylate and oligo(meth)acrylate having non-acrylic c-c double bonds | |
| JPS6010553B2 (en) | pressure sensitive adhesive | |
| DE102012218335A1 (en) | Pressure sensitive adhesive in the form of a radiation-crosslinkable hot melt adhesive or non-aqueous adhesive, useful e.g. for producing adhesive labels, and adhesive tapes, comprises poly(meth)acrylate made of alkyl(meth)acrylates | |
| US3563953A (en) | Curable copolymer of an alkyl acrylate,a glycidyl acrylate or methacrylate and diketene | |
| EP0633918A1 (en) | Ultraviolet radiation curable acrylate pressure-sensitive adhesive compositions | |
| JPH0115543B2 (en) | ||
| JPS6124426B2 (en) | ||
| EP3322764A1 (en) | Hot-melt adhesive, containing poly(meth)acrylate made from alkyl(meth)acrylates and from determined heterocyclic groups containing (meth)acrylates | |
| JPS60207101A (en) | Polarizing plate | |
| EP0355683B1 (en) | Radiation cross-linkable contact adhesive mixtures | |
| JPH02196879A (en) | Pressure-sensitive adhesive composition | |
| US20220306909A1 (en) | Pressure sensitive adhesive article | |
| DE602004009127T2 (en) | Two-layer plastic film and adhesive tape | |
| JPS5952616A (en) | Production for surface protective layer | |
| JPS6147187B2 (en) | ||
| TWI797993B (en) | Photoresist film and application thereof | |
| JP2686303B2 (en) | Radiation-curable pressure-sensitive adhesive composition | |
| JPS6210181A (en) | Production of pressure-sensitive adhesive tape | |
| JP2752862B2 (en) | One-component aqueous primer composition | |
| JPS6030354B2 (en) | Manufacturing method of surface protection sheet | |
| JPH01203412A (en) | Resin composition for tacky agent |