JP4623485B2 - Adhesive composition and surface protective film - Google Patents
Adhesive composition and surface protective film Download PDFInfo
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- JP4623485B2 JP4623485B2 JP2004056947A JP2004056947A JP4623485B2 JP 4623485 B2 JP4623485 B2 JP 4623485B2 JP 2004056947 A JP2004056947 A JP 2004056947A JP 2004056947 A JP2004056947 A JP 2004056947A JP 4623485 B2 JP4623485 B2 JP 4623485B2
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- 239000000853 adhesive Substances 0.000 title claims description 83
- 230000001070 adhesive effect Effects 0.000 title claims description 83
- 239000000203 mixture Substances 0.000 title claims description 30
- 230000001681 protective effect Effects 0.000 title claims description 30
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 22
- 229920006243 acrylic copolymer Polymers 0.000 claims description 21
- 239000003431 cross linking reagent Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- -1 isocyanurate compound Chemical class 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000012948 isocyanate Substances 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 239000004033 plastic Substances 0.000 claims description 7
- 229920003023 plastic Polymers 0.000 claims description 7
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 claims description 6
- 239000002985 plastic film Substances 0.000 claims description 6
- 229920006255 plastic film Polymers 0.000 claims description 6
- 238000003419 tautomerization reaction Methods 0.000 claims description 6
- 239000013522 chelant Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229930194542 Keto Natural products 0.000 claims 1
- 150000002085 enols Chemical class 0.000 claims 1
- 125000000468 ketone group Chemical group 0.000 claims 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 20
- 239000000758 substrate Substances 0.000 description 15
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical class O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 229920006267 polyester film Polymers 0.000 description 6
- 238000011109 contamination Methods 0.000 description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 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 4
- 239000005058 Isophorone diisocyanate Chemical class 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical class CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 230000005641 tunneling Effects 0.000 description 3
- 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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000463 material Substances 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
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000012360 testing 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
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- QNRSQFWYPSFVPW-UHFFFAOYSA-N 5-(4-cyanobutyldiazenyl)pentanenitrile Chemical compound N#CCCCCN=NCCCCC#N QNRSQFWYPSFVPW-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本発明は、プラスチック製品や金属製品の保護に適した適度な粘着力と剥離性に優れた表面保護フィルム用粘着剤組成物及び該粘着剤組成物を塗布した表面保護フィルムに関するものである。本発明の表面保護フィルムは、特に偏光フィルム、プラスチック板、家電製品、自動車さらに電子機器などの表面保護フィルムとして使用することができる。 The present invention relates to a pressure-sensitive adhesive composition for a surface protective film excellent in moderate adhesive strength and peelability suitable for protecting plastic products and metal products, and a surface protective film coated with the pressure-sensitive adhesive composition. The surface protective film of the present invention can be used particularly as a surface protective film for polarizing films, plastic plates, home appliances, automobiles and electronic devices.
一般に、プラスチック板や金属製品などを保護するための表面保護フィルム用粘着剤としては、耐候性や透明性の点からアクリル系粘着剤が多く使用されている。アクリル系粘着剤としては、（メタ）アクリル酸アルキルエステル単量体とカルボキシル基、水酸基、エポキシ基などの官能基を含有する単量体とを共重合させた粘着剤組成物をポリイソシアネート化合物、メラミン樹脂、エポキシ樹脂、金属キレート化合物などで架橋させたものが使用される。これらアクリル系粘着剤では、貼付初期と経時の粘着力の差を少なくし再剥離性を向上させ、被着体への濡れを抑制し、さらに剥離後の被着体表面への汚染をなくするために架橋剤を多く使用して凝集力を高く設定するのが一般的である。 In general, acrylic pressure-sensitive adhesives are often used as surface protective film pressure-sensitive adhesives for protecting plastic plates and metal products from the viewpoint of weather resistance and transparency. As the acrylic pressure-sensitive adhesive, a pressure-sensitive adhesive composition obtained by copolymerizing a (meth) acrylic acid alkyl ester monomer and a monomer containing a functional group such as a carboxyl group, a hydroxyl group, or an epoxy group is a polyisocyanate compound, Those crosslinked with melamine resin, epoxy resin, metal chelate compound or the like are used. These acrylic pressure-sensitive adhesives reduce the difference in adhesive strength between the initial application and time, improve re-peelability, suppress wetting on the adherend, and eliminate contamination on the adherend surface after peeling. Therefore, it is common to set a high cohesive force by using a large amount of a crosslinking agent.
しかしながら、アクリル系粘着剤では、単に架橋度合を高くして粘着力を下げた場合、貼付後の加熱処理による被着体の表面の水分、被着体内部から発生するガスや基材フィルムの収縮などにより、フクレやトンネリングの現象が起こる。これらの現象を防ぐためには、架橋剤の使用量を少なくして架橋度合を下げて濡れ性を向上させればよいが、そのために架橋速度が遅くなるために、粘着剤塗工品を加熱熟成したり、室温で長期間養生する必要があった。このことは在庫量が増大するとか、納期が遅れるなどの問題がある。 However, with acrylic adhesives, when the degree of crosslinking is simply increased to lower the adhesive strength, the moisture on the surface of the adherend, the gas generated from the inside of the adherend, and the shrinkage of the substrate film are reduced by the heat treatment after application. For example, the phenomenon of swelling and tunneling occurs. In order to prevent these phenomena, the amount of the crosslinking agent used may be reduced to lower the degree of crosslinking and improve the wettability. Or curing at room temperature for a long time. This causes problems such as an increase in inventory and a delay in delivery.
上記のことを解決するために多くの手段が検討されてきた。例えば特許文献１の特開２００１−２４０８３０号公報ではアミド基及び水酸基を含有する官能基モノマーと（メタ）アクリル酸アルキルエステル系モノマーとを共重合して得られるアクリル系共重合体に金属キレート化合物とイソシアネート化合物を添加してなる粘着剤組成物が開示されている。しかし金属キレート化合物を添加しているために経時で皮膜に金属粉末が析出してくる恐れがある。また、特許文献２の特開昭５７−１６２７７０号公報ではイソシアネート基と反応しうる官能基を持ったアクリル系共重合体にケト−エノール互変異性をおこす化合物を添加することで経時的な粘度上昇やゲル化が抑えられると開示されているが、表面保護フィルム用に使用できる粘着性能を有していない。
本発明の目的は、ポットライフが長く作業性が良好で、適度な粘着力と経時粘着力変化の少ない、剥離後の被着体表面への汚染のない、さらに加熱処理時のフクレやトンネリングの現象のない表面保護フィルム用粘着剤組成物及び該組成物を塗布した表面保護フィルムを提供することである。 The object of the present invention is that the pot life is long, the workability is good, the moderate adhesive force and the change in adhesive force with time are small, there is no contamination on the surface of the adherend after peeling, and there is no swelling or tunneling during the heat treatment. It is an object to provide a pressure-sensitive adhesive composition for a surface protective film having no phenomenon and a surface protective film coated with the composition.
以上の課題を解決するために、本発明者らは鋭意研究を重ねた結果、水酸基を含むアクリル系共重合体と特定の架橋剤と特定の添加剤からなる粘着剤組成物において、ポットライフが長いにもかかわらず架橋速度が速く、養生期間を短縮できること、また、貼付初期と経時の粘着力の差が少なくなること、さらに、剥離後の被着体表面への汚染がないことを見出し本発明に至った。 In order to solve the above problems, the present inventors have conducted intensive research, and as a result, in the pressure-sensitive adhesive composition comprising an acrylic copolymer containing a hydroxyl group, a specific crosslinking agent, and a specific additive, the pot life is increased. Despite being long, the cross-linking speed is fast, the curing period can be shortened, the difference in adhesive strength between the initial application and time is reduced, and there is no contamination on the adherend surface after peeling. Invented.
すなわち、本発明は、架橋剤として金属キレート化合物を添加していない、（メタ）アクリル酸アルキルエステル単量体を主成分とし、水酸基を含有する共重合可能な単量体０．１〜８重量％とカルボキシル基を含有する共重合可能な単量体０〜０．３重量％からなるアクリル系共重合体（Ａ）の固形分１００重量部に対して、脂肪族系及び／又は脂環族系の多官能イソシアネート系化合物及び／又は多官能イソシアヌレート系化合物（Ｂ）を固形分で０．５〜７重量部、ケト−エノール互変異性をおこす化合物（Ｃ）０．１〜１５重量部からなる表面保護フィルム用粘着剤組成物である。該粘着剤組成物を塗布してなる粘着シートを、２３℃、６５％ＲＨ中に７日間養生した後ステンレス板に貼り合わせたときの粘着力が０．０５〜０．５Ｎ／２５ｍｍ以内であり、２３℃、６５％ＲＨ中に７日間養生後の粘着力に対する同条件下３日間養生後の粘着力の割合が１．３以下であり、２３℃、６５％ＲＨ中に７日養生後の粘着力に対する同条件下５時間養生後の粘着力の割合が１．５〜４である表面保護フィルム用粘着剤組成物である。また、上記の粘着剤組成物をプラスチックフィルムに塗布してなるプラスチック製品や金属製品の保護に用いる表面保護フィルムである。 That is, in the present invention, a metal chelate compound is not added as a crosslinking agent. A copolymerizable monomer having a (meth) acrylic acid alkyl ester monomer as a main component and containing a hydroxyl group is 0.1 to 8 weights. % And an aliphatic and / or alicyclic group with respect to 100 parts by weight of the solid content of the acrylic copolymer (A) comprising 0 to 0.3% by weight of a copolymerizable monomer containing a carboxyl group 0.5 to 7 parts by weight of a polyfunctional isocyanate-based compound and / or polyfunctional isocyanurate-based compound (B) in a solid content and 0.1 to 15 parts by weight of a compound (C) that causes keto-enol tautomerism It is the adhesive composition for surface protection films which consists of. The pressure-sensitive adhesive sheet obtained by applying the pressure-sensitive adhesive composition is cured within 23 ° C. and 65% RH for 7 days, and then adhered to a stainless steel plate, the adhesive strength is within 0.05 to 0.5 N / 25 mm. The ratio of the adhesive strength after curing for 3 days under the same conditions to the adhesive strength after curing for 7 days in 23 ° C. and 65% RH is 1.3 or less, and after curing for 7 days in 23 ° C. and 65% RH. the proportion of the adhesive force of the conditions for 5 hours after curing for adhesion is a surface protective film pressure-sensitive adhesive composition Ru der 1.5-4. Moreover , it is a surface protection film used for protection of a plastic product and a metal product which apply | coat said adhesive composition to a plastic film.
本発明の粘着剤組成物は適度な粘着力を有し、基材に対する密着性が良く、再剥離性を有しており、ポットライフも良好であることから、表面保護フィルム、特に偏光フィルム、プラスチック板、家電製品、自動車、電子機器などの表面保護フィルム用として有利に使用することができる。また架橋速度が早いことから、粘着剤塗工品を加熱熟成したり、室温で長期間養生する必要がなく、生産性を向上させることができる。 The pressure-sensitive adhesive composition of the present invention has a suitable pressure-sensitive adhesive force, has good adhesion to a substrate, has good removability, and has a good pot life. It can be advantageously used as a surface protective film for plastic plates, home appliances, automobiles, electronic devices and the like. Further, since the crosslinking rate is high, it is not necessary to heat and age the pressure-sensitive adhesive coated product or to cure it for a long time at room temperature, thereby improving productivity.
以下、本発明の構成を詳細に説明する。本発明に使用するアクリル系共重合体（Ａ）は、（メタ）アクリル酸アルキルエステル単量体と水酸基を含有する共重合可能な単量体とカルボキシル基を含有する共重合可能な単量体とを共重合してなる共重合体である。該（メタ）アクリル酸アルキルエステル単量体は、アルキル基の炭素数が４以上が好ましく、より好ましくは４〜１４のものであり、具体的には、ブチル基、ペンチル基、ヘキシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基を有する炭素数４〜１４のアルキルアルコールと（メタ）アクリル酸のエステル化合物からなる単量体であり、これらより選ばれる少なくとも１種以上使用することができる。なお、アルキル基は直鎖でも分岐鎖でも使用することができる。該アクリル酸アクリルアルキルエステル単量体の使用量は、９１．７〜９９．９重量％である。９１．７重量％より少ない場合は、粘着力が低くなり被着体からの浮きや剥れを生じやすい。 Hereinafter, the configuration of the present invention will be described in detail. The acrylic copolymer (A) used in the present invention comprises a (meth) acrylic acid alkyl ester monomer, a copolymerizable monomer containing a hydroxyl group, and a copolymerizable monomer containing a carboxyl group. Is a copolymer obtained by copolymerizing The (meth) acrylic acid alkyl ester monomer preferably has an alkyl group having 4 or more carbon atoms, more preferably 4 to 14 carbon atoms, specifically, butyl group, pentyl group, hexyl group, undecyl. It is a monomer comprising a C4-C14 alkyl alcohol having a group, dodecyl group, tridecyl group or tetradecyl group and an ester compound of (meth) acrylic acid, and at least one selected from these can be used. . The alkyl group can be used as a straight chain or a branched chain. The amount of the acrylic acid acrylic alkyl ester monomer used is 91.7 to 99.9% by weight. When the amount is less than 91.7% by weight, the adhesive strength is low, and the float or peel from the adherend tends to occur.
本発明に使用する水酸基を含有する共重合可能な単量体は、具体的には、２−ヒドロキシエチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、２ーヒドロキシプロピル（メタ）アクリレート、カプロラクトン変性（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレートなどが挙げられ、これらの群より選ばれる少なくとも１種以上使用することができる。水酸基を含有する共重合可能な単量体の使用量は、０．１〜８重量％必要である。好ましくは１〜６重量％、より好ましくは２〜５重量％である。その使用量が０．１重量％より少ない場合、架橋剤を添加した場合に架橋効果が少なく十分な凝集力が得られず、凝集破壊により被着体へ糊の転着が起こる。その使用量が８重量％より多い場合は、粘着剤の製造時にゲル化を起こしやすい。架橋剤を添加したときには、ポットライフが短く作業性に問題があり、凝集力が高くなり過ぎ粘着力が低下して基材に対する密着性が悪くなる。 Specific examples of the copolymerizable monomer containing a hydroxyl group used in the present invention include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Caprolactone-modified (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate and the like can be mentioned, and at least one selected from these groups can be used. The amount of the copolymerizable monomer containing a hydroxyl group needs to be 0.1 to 8% by weight. Preferably it is 1-6 weight%, More preferably, it is 2-5 weight%. When the amount used is less than 0.1% by weight, when a crosslinking agent is added, the crosslinking effect is small and sufficient cohesive force cannot be obtained, and transfer of glue to the adherend occurs due to cohesive failure. When the amount used is more than 8% by weight, gelation tends to occur during the production of the pressure-sensitive adhesive. When the cross-linking agent is added, the pot life is short and there is a problem in workability, the cohesive force becomes too high, the adhesive force is lowered, and the adhesion to the substrate is deteriorated.
本発明に使用するカルボキシル基を含有する共重合可能な単量体は、具体的には、（メタ）アクリル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸、及びマレイン酸、イタコン酸の炭素数１〜１２の直鎖又は分岐鎖を有するアルコールとのハーフエステルなどが挙げられ、これらの群より選ばれる少なくとも１種以上使用することができる。カルボキシル基を含有する共重合可能な単量体の使用量は、０〜０．３重量％である。その使用量が０．３重量％を超える場合、ポットライフが短く作業性に問題がある。 Specific examples of the copolymerizable monomer containing a carboxyl group used in the present invention include (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, and maleic acid, itaconic acid. And a half ester with an alcohol having a linear or branched chain having 1 to 12 carbon atoms, and at least one selected from these groups can be used. The amount of the copolymerizable monomer containing a carboxyl group is 0 to 0.3% by weight. If the amount used exceeds 0.3% by weight, the pot life is short and there is a problem in workability.
本発明に使用するイソシアネート化合物（Ｂ）は脂肪族系及び／又は脂環族系の多官能イソシアネート系化合物及び／又は多官能イソシアヌレート系化合物である。具体的には、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、それらのアダクト体などのポリイソシアネート系化合物、水添キシレンジイソシアネート、水添ジフェニルメタンジイソシアネートなどが挙げられ、これらの群から選ばれる少なくとも１種以上使用することができる。好ましくはヘキサメチレンジイソシアネート系、イソホロンジイソシアネート系化合物及びこれらから変性されたプレポリマーである。より好ましくはヘキサメチレンジイソシアネート化合物／イソホロンジイソシアネート系化合物の割合が１００／０〜５０／５０の混合物及びこれらから変性されたプレポリマーである。イソシアネート系化合物の添加量は、上記アクリル系共重合体（Ａ）の固形分１００重量部に対して固形分で０．５〜７重量部である。好ましくは１〜５重量部である。添加量が０．５重量部より少ないと加熱後の粘着シートの粘着力や高温多湿時の凝集力が低下し、７重量部を超えるとポットライフが短く作業性に問題があり、また、架橋が進みすぎ粘着力が低下してフクレやトンネリング現象が発生する。 The isocyanate compound (B) used in the present invention is an aliphatic and / or alicyclic polyfunctional isocyanate compound and / or a polyfunctional isocyanurate compound. Specific examples include hexamethylene diisocyanate, isophorone diisocyanate, polyisocyanate compounds such as adducts thereof, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like. Use at least one selected from these groups. Can do. Preferred are hexamethylene diisocyanate type, isophorone diisocyanate type compounds and prepolymers modified from these. More preferred are mixtures of hexamethylene diisocyanate compound / isophorone diisocyanate compound of 100/0 to 50/50 and prepolymers modified from these. The addition amount of the isocyanate compound is 0.5 to 7 parts by weight in solid content with respect to 100 parts by weight of solid content in the acrylic copolymer (A). Preferably it is 1-5 weight part. If the amount added is less than 0.5 parts by weight, the adhesive strength of the pressure-sensitive adhesive sheet after heating and the cohesive strength at high temperature and high humidity will decrease, and if it exceeds 7 parts by weight, the pot life will be short and there will be a problem in workability. Proceeds too much and the adhesive strength decreases, causing bulge and tunneling.
本発明に使用するケト−エノール互変異性をおこす化合物（Ｃ）は、イソシアネート化合物（Ｂ）単独で使用された場合、ポットライフが短く作業性に問題があったが、添加することにより粘度上昇及びゲル化を抑え、ポットライフを長くするため必要である。具体的にはアセチルアセトン、アセト酢酸エステル及びマロン酸エステルから選ばれる少なくとも１種以上を使用することができる。該ケト−エノール互変異性をおこす化合物の添加量はアクリル系共重合体（Ａ）の固形分１００重量部に対して固形分で０．１〜１５重量部である。好ましくは０．５〜１０重量部であり、より好ましくは２〜７重量部である。添加量が０．１〜１５重量部の範囲内であれば、粘度上昇及びゲル化を抑える効果が得られ、経済的にも良好な範囲である。 The compound (C) causing keto-enol tautomerism used in the present invention has a short pot life and a problem in workability when used alone, but the viscosity is increased by addition. And it is necessary to suppress gelation and lengthen the pot life. Specifically, at least one selected from acetylacetone, acetoacetic acid ester and malonic acid ester can be used. The addition amount of the compound causing the keto-enol tautomerism is 0.1 to 15 parts by weight in solid content with respect to 100 parts by weight of solid content of the acrylic copolymer (A). Preferably it is 0.5-10 weight part, More preferably, it is 2-7 weight part. If the addition amount is in the range of 0.1 to 15 parts by weight, the effect of suppressing the increase in viscosity and gelation can be obtained, which is also in an economically favorable range.
本発明の粘着剤組成物は、該粘着剤をポリエステルフィルム（２５μｍ厚）に乾燥塗膜厚が２５μｍになるように直接塗工して、９０℃で６０秒間乾燥させた後、粘着面をシリコーン処理されたポリエステルフィルムセパレター（３８μｍ厚）で被覆して、２３℃、６５％ＲＨ中に７日間養生した後の試料シートをステンレス板に貼り合わせた時の０．３ｍ／分の剥離速度における粘着力が０．０５〜０．５Ｎ/２５ｍｍ（ＪＩＳ Ｚ０２３７粘着テープ・粘着シート試験方法に準じて測定）であることが必要である。粘着力が０．０５Ｎ/２５ｍｍより低い場合は、被着体からの浮きや剥れを生じやすい。０．５Ｎ/２５ｍｍを超える場合は、保護フィルムを剥がす際に、被着体を汚染するなど再剥離性が悪くなる。 In the pressure-sensitive adhesive composition of the present invention, the pressure-sensitive adhesive is directly applied to a polyester film (25 μm thickness) so that the dry coating thickness is 25 μm, dried at 90 ° C. for 60 seconds, and then the pressure-sensitive adhesive surface is coated with silicone. At a peeling speed of 0.3 m / min when a sample sheet coated with a treated polyester film separator (38 μm thickness) and cured for 7 days in 23 ° C. and 65% RH is bonded to a stainless steel plate It is necessary that the adhesive strength is 0.05 to 0.5 N / 25 mm (measured according to the JIS Z0237 adhesive tape / adhesive sheet test method). When the adhesive force is lower than 0.05 N / 25 mm, it tends to float or peel from the adherend. When it exceeds 0.5 N / 25 mm, the removability is deteriorated, for example, the adherend is contaminated when the protective film is peeled off.
従来、架橋剤を添加して架橋させた再剥離用粘着剤は実用粘着性能に達するまでの養生期間は、７〜１０日間程度必要であり、該期間を短縮することが必要であった。本発明の粘着剤組成物を使用することにより、養生期間が３日間という短期間で実用粘着性能に達する。そのためには、２３℃、６５％ＲＨ中に７日間養生後の粘着力に対する同条件下３日間養生後の粘着力の割合が１．３以下となることが必要であり、２３℃、６５％ＲＨ中に７日養生後の粘着力に対する同条件下５時間養生後の粘着力の割合が１．５〜４の範囲に入ることが必要である。１．３を超え、また４を超える場合は３〜７日間の養生が必要となり、１．５より小さい場合は基材に対する密着性が低下する。 Conventionally, a re-peeling adhesive that has been cross-linked by adding a cross-linking agent requires a curing period of about 7 to 10 days to reach practical adhesive performance, and it has been necessary to shorten the period. By using the pressure-sensitive adhesive composition of the present invention, the practical pressure-sensitive adhesive performance is reached in a short period of 3 days. For this purpose, the ratio of the adhesive strength after curing for 3 days under the same conditions to the adhesive strength after curing for 7 days in 23 ° C. and 65% RH must be 1.3 or less. It is necessary that the ratio of the adhesive strength after curing for 5 hours under the same condition to the adhesive strength after 7 days curing during RH is in the range of 1.5-4. When it exceeds 1.3 and exceeds 4, curing for 3 to 7 days is required, and when it is less than 1.5, adhesion to the substrate is lowered.
本発明のアクリル系共重合体（Ａ）は、通常の塊状重合、溶液重合、懸濁重合、乳化重合などで製造することができるが、好ましくは溶液重合である。重合に使用する溶剤としては、酢酸エチル、トルエン、ヘキサン、アセトンなどの一般的な有機溶剤である。また重合に使用する重合開始剤は、ベンゾイルパーオキサイド、ラウロイルパーオキサイドなどの過酸化物、アゾビスイソブチロニトリル、アゾビスバレロニトリルなどのアゾビス化合物など油溶性の開始剤を使用することができる。 The acrylic copolymer (A) of the present invention can be produced by ordinary bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and the like, preferably solution polymerization. The solvent used for the polymerization is a general organic solvent such as ethyl acetate, toluene, hexane, or acetone. As the polymerization initiator used for polymerization, an oil-soluble initiator such as a peroxide such as benzoyl peroxide or lauroyl peroxide, or an azobis compound such as azobisisobutyronitrile or azobisvaleronitrile can be used. .
本発明のアクリル系共重合体（Ａ）の粘着性を調整する目的で必要に応じ種々のものを本発明の効果を損なわない範囲で配合してもよい。配合に使用される具体例としては、テルペン系、テルペンーフェノール系、クマロンインデン系、スチレン系、ロジン系、キシレン系、フェノール系、石油系などの粘着付与剤、メラミン樹脂、アミンーエポキシ樹脂、酸化防止剤、紫外線吸収剤、充填剤、顔料、可塑剤、界面活性剤などが挙げられる。 You may mix | blend various things in the range which does not impair the effect of this invention as needed in order to adjust the adhesiveness of the acrylic copolymer (A) of this invention. Specific examples used for blending include terpene, terpene-phenol, coumarone indene, styrene, rosin, xylene, phenol, petroleum, and other tackifiers, melamine resins, and amine-epoxy resins. , Antioxidants, ultraviolet absorbers, fillers, pigments, plasticizers, surfactants and the like.
本発明の粘着剤組成物を、各種プラスチックフィルム基材に塗布して表面保護フィルムを得ることができる。基材としてはポリエチレン、ポリプロピレン、エチレン-酢酸ビニル共重合体、ポリエステル、ポリ塩化ビニル、ポリカーボネート、ポリアミド、ポリスチレンなどのフィルムあるいはこれらの複合フィルムなどが使用できる。粘着剤を塗布するに先立ち、密着性を向上させるためプラスチックフィルムの表面にコロナ処理などを行って使用することができる。また、シリコン剥離剤、ウレタン、シリコンアクリル樹脂などで背面処理されたプラスチックフィルムを使用することができる。さらに、塗布されたプラスチックフィルムは汎用のシリコン剥離紙、シリコン剥離フィルムなどで粘着層を保護することもできる。 The pressure-sensitive adhesive composition of the present invention can be applied to various plastic film substrates to obtain a surface protective film. As the substrate, films of polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyester, polyvinyl chloride, polycarbonate, polyamide, polystyrene, or a composite film of these can be used. Prior to application of the adhesive, the surface of the plastic film can be used after corona treatment or the like in order to improve adhesion. Also, a plastic film that has been back-treated with a silicon release agent, urethane, silicon acrylic resin, or the like can be used. Furthermore, the applied plastic film can protect the adhesive layer with a general-purpose silicon release paper, silicon release film or the like.
本発明の粘着組成物は、通常使用されている塗布装置、例えばロール塗布装置などで塗工することができる。塗布量は、使用される用途により異なるが塗布厚として通常５〜３００μｍである。乾燥は通常７０〜１５０℃、３０〜１２０秒間で行われる。 The pressure-sensitive adhesive composition of the present invention can be applied with a commonly used coating apparatus such as a roll coating apparatus. The coating amount varies depending on the intended use, but is usually 5 to 300 μm as the coating thickness. Drying is usually performed at 70 to 150 ° C. for 30 to 120 seconds.
以下、本発明を実施例において詳しく説明するが、本発明はこれによって制限されるものではない。なお、実施例および比較例における部とあるのは特にことわりのない限り、重量部を示す。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not restrict | limited by this. In the examples and comparative examples, “parts” means “parts by weight” unless otherwise specified.
製造例１（アクリル系共重合体Ａ−１）
攪拌機、温度計、還流冷却器、窒素導入管を備えた反応装置に、窒素ガスを封入後、酢酸エチル９０部、ブチルアクリレート６５部、２−エチルヘキシルアクリレート３０部、２−ヒドロキシエチルアクリレート５部、重合開始剤アゾビスイソブチロニトリル０．２部を仕込む。攪拌しながら酢酸エチルの還流温度で７時間反応する。反応終了後、トルエン９５部を添加して室温まで冷却する。粘度３,５００ｍＰａ・ｓ、固形分３５％であるアクリル系共重合体Ａ−１を得た。
Production Example 1 (acrylic copolymer A-1)
Nitrogen gas is sealed in a reactor equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube, and then 90 parts of ethyl acetate, 65 parts of butyl acrylate, 30 parts of 2-ethylhexyl acrylate, 5 parts of 2-hydroxyethyl acrylate, Charge 0.2 parts of polymerization initiator azobisisobutyronitrile. The reaction is carried out for 7 hours at the reflux temperature of ethyl acetate with stirring. After completion of the reaction, 95 parts of toluene is added and cooled to room temperature. An acrylic copolymer A-1 having a viscosity of 3,500 mPa · s and a solid content of 35% was obtained.
製造例２〜５（アクリル系共重合体Ａ−２〜Ａ−５）
製造例１と同様の方法にて、表１に示すように単量体の種類および量を変える以外は全く同様にアクリル系共重合体Ａ−２〜Ａ−５を得た。
Production Examples 2 to 5 (acrylic copolymers A-2 to A-5)
Acrylic copolymers A-2 to A-5 were obtained in the same manner as in Production Example 1 except that the types and amounts of monomers were changed as shown in Table 1.
表１中、単量体組成物の種類を下記の略号で示した。
ＢＡ ：ブチルアクリレート
２ＥＨＡ ：２−エチルヘキシルアクリレート
２ＨＥＡ ：２−ヒドロキシエチルアクリルート
ＡＡｃ ：アクリル酸
In Table 1, the types of monomer compositions are indicated by the following abbreviations.
BA: butyl acrylate 2EHA: 2-ethylhexyl acrylate 2HEA: 2-hydroxyethyl acrylate AAc: acrylic acid
実施例１は、製造例１で得られたアクリル系共重合体Ａ−１の固形分１００部に対して、架橋剤としてＢ−１であるヘキサメチレンジイソシアネート・イソシアヌレート型、旭化成ケミカルズ（株）製、商品名デュラネートＴＰＡ−１００を２部、アセチルアセトンを２部添加して充分に混合して粘着剤組成物を得た。該粘着剤組成物を塗膜厚が２５μｍになるように２５μｍ厚のポリエステルフィルムに直接塗工して、９０℃で６０秒乾燥させた後、粘着面にシリコーンコートされた３８μｍ厚のポリエステルフィルムセパレーターを被覆して表面保護フィルムシートを作製した。ポットライフが良好で、２３℃、６５％ＲＨ中で７日間養生後の粘着力（０．３ｍ／分の剥離速度で、ＪＩＳ Ｚ０２３７粘着テープ・粘着シート試験方法に準じて測定）は、０．１２Ｎ／２５ｍｍで適度な強度であった。７日間養生後の粘着力に対する３日間養生後の粘着力の割合は、１．１と小さく、また７日養生後の粘着力に対する５時間養生後の粘着力の割合が３．３と１．５〜４の範囲内にあることから架橋速度が速く、長い養生期間を必要としない粘着剤組成物である。さらに基材に対する密着性、再剥離性ともに良好であった。結果を表２に示す。 Example 1 is a hexamethylene diisocyanate isocyanurate type B-1 as a cross-linking agent for Asahi Kasei Chemicals Co., Ltd. with respect to 100 parts of the solid content of the acrylic copolymer A-1 obtained in Production Example 1. 2 parts of Duranate TPA-100 and 2 parts of acetylacetone were added and mixed well to obtain an adhesive composition. The pressure-sensitive adhesive composition was directly applied to a 25 μm-thick polyester film so that the coating thickness was 25 μm, dried at 90 ° C. for 60 seconds, and then the pressure-sensitive adhesive surface was coated with a silicone-coated 38 μm-thick polyester film separator. Was coated to prepare a surface protective film sheet. The pot life is good, and the adhesive strength after 7 days of curing at 23 ° C. and 65% RH (measured according to the JIS Z0237 adhesive tape / adhesive sheet test method at a peeling speed of 0.3 m / min) is 0. The strength was moderate at 12 N / 25 mm. The ratio of the adhesive strength after the 3-day curing to the adhesive strength after the 7-day curing is as small as 1.1, and the ratio of the adhesive strength after the 5-hour curing to the adhesive strength after the 7-day curing is 3.3 and 1. Since it is in the range of 5 to 4, it is a pressure-sensitive adhesive composition that has a high crosslinking rate and does not require a long curing period. Furthermore, both the adhesion to the substrate and the removability were good. The results are shown in Table 2.
実施例２は、実施例１の架橋剤をＢ−２であるヘキサメチレンジイソシアネート・ビュレット型 旭化成ケミカルズ（株）製、商品名デュラネート２１Ｓ−７５Ｅに変更する以外は実施例１とまったく同様にして表面保護フィルムを得、実施例１と同様に試験をした。結果は、ポットライフ、７日間養生後の粘着力、７日間養生後の粘着力に対する３日間養生後の粘着力の割合、７日養生後の粘着力に対する５時間養生後の粘着力の割合、基材に対する密着性、再剥離性すべて良好であった。結果は表２に示す。 Example 2 is the same as Example 1 except that the cross-linking agent of Example 1 is changed to B-2 hexamethylene diisocyanate bullet type Asahi Kasei Chemicals Co., Ltd., trade name Duranate 21S-75E. A protective film was obtained and tested as in Example 1. The results are: pot life, adhesive strength after 7 days curing, ratio of adhesive strength after 3 days curing to adhesive strength after 7 days curing, ratio of adhesive strength after 5 hours curing to adhesive strength after 7 days curing, The adhesion to the substrate and the removability were all good. The results are shown in Table 2.
実施例３は、実施例１の架橋剤をＢ−３であるヘキサメチレンジイソシアネート・ビュレット型 旭化成ケミカルズ（株）製、商品名デュラネートＷ３３３０−７５Ｅ及びアセチルアセトンを４部に変更する以外は、実施例１とまったく同様にして表面保護フィルムを得、実施例１と同様に試験をした。結果は、ポットライフ、７日間養生後の粘着力、７日間養生後の粘着力に対する３日間養生後の粘着力の割合、７日養生後の粘着力に対する５時間養生後の粘着力の割合、基材に対する密着性、再剥離性すべて良好であった。結果は表２に示す。 Example 3 is the same as Example 1 except that the cross-linking agent of Example 1 is B-3, which is a hexamethylene diisocyanate bullet type, manufactured by Asahi Kasei Chemicals Corporation, trade name Duranate W3330-75E and acetylacetone are changed to 4 parts. A surface protective film was obtained in exactly the same manner as in Example 1 and tested in the same manner as in Example 1. The results are: pot life, adhesive strength after 7 days curing, ratio of adhesive strength after 3 days curing to adhesive strength after 7 days curing, ratio of adhesive strength after 5 hours curing to adhesive strength after 7 days curing, The adhesion to the substrate and the removability were all good. The results are shown in Table 2.
実施例４は、実施例１の架橋剤をＢ−４であるイソシアヌレート型（ヘキサメチレンジイソシアネート／イソホロンジイソシアネート＝７０／３０）旭化成ケミカルズ（株）製、 商品名デュラネートＴ４３３０−７５Ｂを４部、アセチルアセトンを６部に変更する以外は、実施例１とまったく同様にして表面保護フィルムを得、実施例１と同様に試験をした。結果は、ポットライフ、７日間養生後の粘着力、７日間養生後の粘着力に対する３日間養生後の粘着力の割合、７日養生後の粘着力に対する５時間養生後の粘着力の割合、基材に対する密着性、再剥離性すべて良好であった。結果は表２に示す。 Example 4 is an isocyanurate type B-4 (hexamethylene diisocyanate / isophorone diisocyanate = 70/30) manufactured by Asahi Kasei Chemicals Co., Ltd., trade name Duranate T4330-75B, acetylacetone. A surface protective film was obtained in the same manner as in Example 1 except that the value was changed to 6 parts, and the test was performed in the same manner as in Example 1. The results are: pot life, adhesive strength after 7 days curing, ratio of adhesive strength after 3 days curing to adhesive strength after 7 days curing, ratio of adhesive strength after 5 hours curing to adhesive strength after 7 days curing, The adhesion to the substrate and the removability were all good. The results are shown in Table 2.
実施例５は、製造例２で得られたアクリル系共重合体Ａ−２を使用して、架橋剤は実施例１で使用したＢ−１を３部、アセチルアセトン４部使用する以外は、実施例１とまったく同様にして表面保護フィルムを得、実施例１と同様に試験をした。結果は、ポットライフ、７日間養生後の粘着力、７日間養生後の粘着力に対する３日間養生後の粘着力の割合、７日養生後の粘着力に対する５時間養生後の粘着力の割合、基材に対する密着性、再剥離性すべて良好であった。結果は表２に示す。 Example 5 was carried out except that the acrylic copolymer A-2 obtained in Production Example 2 was used, and the crosslinking agent was 3 parts of B-1 used in Example 1 and 4 parts of acetylacetone. A surface protective film was obtained in exactly the same manner as in Example 1 and tested in the same manner as in Example 1. The results are: pot life, adhesive strength after 7 days curing, ratio of adhesive strength after 3 days curing to adhesive strength after 7 days curing, ratio of adhesive strength after 5 hours curing to adhesive strength after 7 days curing, The adhesion to the substrate and the removability were all good. The results are shown in Table 2.
実施例６は、製造例３で得られたアクリル系共重合体Ａ−３を使用して、架橋剤は実施例１で使用したＢ−１を５部、アセチルアセトン２部使用する以外は、実施例１とまったく同様にして表面保護フィルムを得、実施例１と同様に試験をした。結果は、ポットライフ、７日間養生後の粘着力、７日間養生後の粘着力に対する３日間養生後の粘着力の割合、７日養生後の粘着力に対する５時間養生後の粘着力の割合、基材に対する密着性、再剥離性すべて良好であった。結果は表２に示す。 Example 6 was carried out except that the acrylic copolymer A-3 obtained in Production Example 3 was used, and the crosslinking agent was 5 parts of B-1 used in Example 1 and 2 parts of acetylacetone. A surface protective film was obtained in exactly the same manner as in Example 1 and tested in the same manner as in Example 1. The results are: pot life, adhesive strength after 7 days curing, ratio of adhesive strength after 3 days curing to adhesive strength after 7 days curing, ratio of adhesive strength after 5 hours curing to adhesive strength after 7 days curing, The adhesion to the substrate and the removability were all good. The results are shown in Table 2.
比較例１
比較例１は、実施例１からアセチルアセトンを除いた例である。アセチルアセトンを添加しないためにポットライフが短く、作業性が悪く使用するには困難であった。結果は表３に示す。
Comparative Example 1
Comparative Example 1 is an example in which acetylacetone was removed from Example 1. Since acetylacetone was not added, the pot life was short, the workability was poor and it was difficult to use. The results are shown in Table 3.
比較例２
比較例２は、製造例４で得られた水酸基の含有量が範囲外のアクリル系共重合体Ａ−４を使用し、架橋剤は実施例１で使用しているＢ−１を４部、アセチルアセトンを４部使用する以外は、実施例１とまったく同様にして表面保護フィルムを得、実施例１と同様に試験をした。結果は、特に基材への密着性が悪い。結果は表３に示す。
Comparative Example 2
Comparative Example 2 uses an acrylic copolymer A-4 having a hydroxyl group content outside the range obtained in Production Example 4, and the crosslinking agent is 4 parts of B-1 used in Example 1. A surface protective film was obtained in the same manner as in Example 1 except that 4 parts of acetylacetone was used, and the test was conducted in the same manner as in Example 1. The result is particularly poor adhesion to the substrate. The results are shown in Table 3.
比較例３
比較例３は、製造例４で得られたカルボキシル基の含有量が範囲外のアクリル系共重合体Ａ−５を使用し、架橋剤を添加すると、架橋が早く進みポットライフが短く、作業性が悪く使用するには困難であった。結果は表３に示す。
Comparative Example 3
In Comparative Example 3, when the acrylic copolymer A-5 having a carboxyl group content outside the range obtained in Production Example 4 was used and a crosslinking agent was added, the crosslinking progressed quickly, the pot life was short, and workability was improved. However, it was difficult to use. The results are shown in Table 3.
表２及び３中、架橋剤の種類を下記の略号で示した。
Ｂ−１：ヘキサメチレンジイソシアネート・イソシアヌレート型、旭化成ケミカルズ
（株）製、商品名デュラネートＴＰＡ−１００
Ｂ−２：ヘキサメチレンジイソシアネート・ビュレット型、旭化成ケミカルズ（株）
製、商品名デュラネート２１Ｓ−７５Ｅ
Ｂ−３：ヘキサメチレンジイソシアネート・ビュレット型、旭化成ケミカルズ（株）
製、商品名デュラネートＷ３３３０−７５Ｅ
Ｂ−４：イソシアヌレート型（ヘキサメチレンジイソシアネート／イソホロンジイソ
シアネート＝７０／３０）旭化成ケミカルズ（株）製、商品名デュラネート
Ｔ４３３０−７５Ｂ
In Tables 2 and 3, the types of crosslinking agents are indicated by the following abbreviations.
B-1: Hexamethylene diisocyanate isocyanurate type, manufactured by Asahi Kasei Chemicals Corporation, trade name Duranate TPA-100
B-2: Hexamethylene diisocyanate burette type, Asahi Kasei Chemicals Corporation
Product name Duranate 21S-75E
B-3: Hexamethylene diisocyanate burette type, Asahi Kasei Chemicals Corporation
Product name Duranate W3330-75E
B-4: Isocyanurate type (hexamethylene diisocyanate / isophorone diisocyanate = 70/30) manufactured by Asahi Kasei Chemicals Corporation, trade name Duranate T4330-75B
表２及び３中の性能試験に示す項目を下記の略号で示した。
５時間：表面保護フィルムシートを２３℃、６５％ＲＨ中に５時間放置。
３日間：表面保護フィルムシートを２３℃、６５％ＲＨ中に３日間放置。
７日間：表面保護フィルムシートを２３℃、６５％ＲＨ中に７日間放置。
３日間／７日間：２３℃、６５％ＲＨ中に７日間養生後の粘着力に対する同条件下３
日間養生後の粘着力の割合。
５時間／７日間：２３℃、６５％ＲＨ中に７日養生後の粘着力に対する同条件下５時
間養生後の粘着力の割合。
Items shown in performance tests in Tables 2 and 3 are indicated by the following abbreviations.
5 hours: The surface protective film sheet was left in 23 ° C. and 65% RH for 5 hours.
3 days: The surface protective film sheet was left in 23 ° C. and 65% RH for 3 days.
7 days: The surface protective film sheet was left in 23 ° C. and 65% RH for 7 days.
3 days / 7 days: the same condition for adhesive strength after curing for 7 days in 23 ° C., 65% RH 3
Percentage of adhesive strength after daily curing.
5 hours / 7 days: Ratio of adhesive strength after 5 hours of curing under the same conditions to adhesive strength after 7 days of curing at 23 ° C. and 65% RH.
試験方法
１．ポットライフ
アクリル系共重合体、イソシアネート系架橋剤、ケトーエノール互変異性をおこす化合物などを配合後の粘度、液状態を測定し観察する。
○：配合８時間後の粘度が、３０℃で５０００ｍＰａ・ｓ未満のもの。
×：ゲル化するもの、配合８時間後の粘度が、３０℃で５０００ｍＰａ・ｓ以上のもの。
Test method 1. Measure and observe the viscosity and liquid state after blending a pot life acrylic copolymer, an isocyanate crosslinking agent, a compound that causes ketoeenol tautomerism, and the like.
A: The viscosity after 8 hours of blending is less than 5000 mPa · s at 30 ° C.
X: Gelling, viscosity of 8 hours after blending is 5000 mPa · s or more at 30 ° C.
２．粘着力
アクリル系共重合体、イソシアネート系架橋剤、アセチルアセトンを添加して撹拌機にて約１０分間混合して粘着剤組成物を得、該粘着剤組成物を塗膜厚が２５μｍになるように２５μｍ厚のポリエステルフィルムに直接塗工して、９０℃で６０秒乾燥させた後、粘着面にシリコーンコートされた３８μｍ厚のポリエステルフィルムセパレーターを被覆して表面保護フィルムシートを作製した。該シートを２３℃、６５％ＲＨ中に５時間、３、７日間放置したものを、０．３ｍ／分の剥離速度で、ＪＩＳ Ｚ０２３７粘着テープ・粘着シート試験方法に準じて粘着力を測定した。
2. Adhesive acrylic copolymer, isocyanate cross-linking agent, and acetylacetone are added and mixed with a stirrer for about 10 minutes to obtain a pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition is adjusted to have a coating thickness of 25 μm. The film was directly applied to a 25 μm thick polyester film and dried at 90 ° C. for 60 seconds, and then a 38 μm thick polyester film separator coated with silicone on the adhesive surface was coated to prepare a surface protective film sheet. The sheet was allowed to stand at 23 ° C. and 65% RH for 5 hours, 3 and 7 days, and the adhesive strength was measured at a peeling speed of 0.3 m / min according to the JIS Z0237 adhesive tape / adhesive sheet test method. .
３．粘着力の変化割合
上記粘着力から得られた強度の変化を７日間放置後の粘着強度を基準に、２３℃、６５％ＲＨ中に７日間養生後の粘着力に対する同条件下３日間養生後の粘着力の割合、２３℃、６５％ＲＨ中に７日養生後の粘着力に対する同条件下５時間養生後の粘着力の割合を求め、養生期間の長短の目安とする。
3. Adhesive strength change rate Based on the adhesive strength after standing for 7 days based on the strength change obtained from the above adhesive strength, after curing for 3 days under the same conditions as for adhesive strength after curing for 7 days in 23 ° C, 65% RH The ratio of the adhesive strength after 5 hours of curing under the same conditions with respect to the adhesive strength after 7 days curing at 23 ° C. and 65% RH is determined as a measure of the length of the curing period.
４．基材に対する密着性
２３℃、６５％ＲＨ中に７日間放置した表面保護フィルムシートの塗膜面を指で擦ったときの基材に対する密着性を評価した。
○：粘着剤が基材よりまったく剥がれない
×：粘着剤が基材より剥がれる
4). Adhesiveness to base material Adhesiveness to the base material when the coating surface of the surface protective film sheet left in 23 ° C. and 65% RH for 7 days was rubbed with a finger was evaluated.
○: Adhesive is not peeled off from the substrate at all ×: Adhesive is peeled off from the substrate
５．再剥離性
２３℃、６５％ＲＨ中に７日間放置した表面保護フィルムを偏光板に貼付した後、９０℃の恒温槽で２４時間放置した後、２３℃、６５％ＲＨ中に取り出し、同雰囲気中で剥がしたときの再剥離の状態を目視で観察した。
○：糊残りや汚染性などなく良好
×：糊残りや汚染性が見られる
5. Re-peelability A surface protective film that was allowed to stand in 23 ° C. and 65% RH for 7 days was attached to the polarizing plate, then left in a 90 ° C. constant temperature bath for 24 hours, and then taken out in 23 ° C. and 65% RH. The state of re-peeling when peeled inside was visually observed.
○: Good with no adhesive residue or contamination ×: Adhesive residue or contamination is observed
偏光フィルム、プラスチック板、家電製品、自動車さらに電子機器などの表面保護フィルムとして使用することができ、必要に応じて剥離することもできる。 It can be used as a surface protective film for polarizing films, plastic plates, home appliances, automobiles and electronic devices, and can be peeled off as necessary.
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| JP5168917B2 (en) * | 2007-01-26 | 2013-03-27 | Ｊｓｒ株式会社 | Near-infrared cut filter and manufacturing method thereof |
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| JPS57162770A (en) * | 1981-03-30 | 1982-10-06 | Nitto Electric Ind Co Ltd | Preparation of pressure-sensitive adhesive tape |
| JPH08259922A (en) * | 1995-03-17 | 1996-10-08 | Nippon Synthetic Chem Ind Co Ltd:The | Pressure-sensitive adhesive composition |
| JP2001240830A (en) * | 2000-02-28 | 2001-09-04 | Saiden Chemical Industry Co Ltd | Adhesive composition and surface protective film |
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| JPS57162770A (en) * | 1981-03-30 | 1982-10-06 | Nitto Electric Ind Co Ltd | Preparation of pressure-sensitive adhesive tape |
| JPH08259922A (en) * | 1995-03-17 | 1996-10-08 | Nippon Synthetic Chem Ind Co Ltd:The | Pressure-sensitive adhesive composition |
| JP2001240830A (en) * | 2000-02-28 | 2001-09-04 | Saiden Chemical Industry Co Ltd | Adhesive composition and surface protective film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130111359A (en) | 2012-03-30 | 2013-10-10 | 린텍 가부시키가이샤 | Adhesive composition, adhesive and adhesive sheet |
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| JP2005247909A (en) | 2005-09-15 |
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