JP6284313B2 - Release film production method and release film - Google Patents
Release film production method and release film Download PDFInfo
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- JP6284313B2 JP6284313B2 JP2013161429A JP2013161429A JP6284313B2 JP 6284313 B2 JP6284313 B2 JP 6284313B2 JP 2013161429 A JP2013161429 A JP 2013161429A JP 2013161429 A JP2013161429 A JP 2013161429A JP 6284313 B2 JP6284313 B2 JP 6284313B2
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- release agent
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- 238000004519 manufacturing process Methods 0.000 title claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 93
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 76
- 239000000126 substance Substances 0.000 claims description 68
- 125000000217 alkyl group Chemical group 0.000 claims description 64
- 229920000642 polymer Polymers 0.000 claims description 61
- 239000010410 layer Substances 0.000 claims description 49
- 238000010438 heat treatment Methods 0.000 claims description 39
- -1 isocyanate compound Chemical class 0.000 claims description 37
- 238000000576 coating method Methods 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 30
- 239000003431 cross linking reagent Substances 0.000 claims description 29
- 239000012948 isocyanate Substances 0.000 claims description 25
- 239000011254 layer-forming composition Substances 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 22
- 125000000524 functional group Chemical group 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- 239000000010 aprotic solvent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 206010040844 Skin exfoliation Diseases 0.000 description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 229920001296 polysiloxane Polymers 0.000 description 12
- 230000032683 aging Effects 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- KCZQSKKNAGZQSZ-UHFFFAOYSA-N 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazin-2,4,6-trione Chemical compound O=C=NCCCCCCN1C(=O)N(CCCCCCN=C=O)C(=O)N(CCCCCCN=C=O)C1=O KCZQSKKNAGZQSZ-UHFFFAOYSA-N 0.000 description 6
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000007810 chemical reaction solvent Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 5
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 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 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000004820 halides Chemical group 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 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 2
- 239000005026 oriented polypropylene Substances 0.000 description 2
- 235000010292 orthophenyl phenol Nutrition 0.000 description 2
- 239000004306 orthophenyl phenol Substances 0.000 description 2
- 125000000913 palmityl 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])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 1
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- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004997 halocarbonyl group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 125000001117 oleyl 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])=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])[H] 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
Description
本発明は、剥離フィルムの製造方法および剥離フィルムに関する。 The present invention relates to a method for producing a release film and a release film.
感圧性粘着テープ、粘着シート等の基材に用いられる剥離処理剤は、前記基材に塗工して剥離剤層を形成すること（剥離処理）により、前記感圧性粘着テープ、粘着シート等の剥離性を向上させることができる。以下において、剥離剤層を形成したフィルムを「剥離フィルム」ということがある。 A release treatment agent used for a base material such as a pressure-sensitive adhesive tape or an adhesive sheet is applied to the base material to form a release agent layer (peeling treatment), whereby the pressure-sensitive adhesive tape, the adhesive sheet, etc. Peelability can be improved. Hereinafter, the film on which the release agent layer is formed may be referred to as a “release film”.
従来の剥離処理剤としては、シリコーン系剥離処理剤、非シリコーン系剥離処理剤などがある。シリコーン系剥離処理剤としては、付加型シリコーン、縮合型シリコーンなどが用いられている。シリコーン系剥離処理剤は、剥離性、残留接着性、耐熱性などの特性が優れているが、高価である。また、シリコーン系剥離処理剤は、特に剥離処理時に高温での熱処理が必要であるために、ＯＰＰ（オルトフェニルフェノール）、ポリエチレン等の耐熱性の悪い基材には使用できない。さらに、シリコーン系剥離処理剤は、剥離処理剤中に不純物として存在する低分子シリコーン化合物の問題があり、かつ、筆記性等に欠点がある。 Conventional release treatment agents include silicone release treatment agents and non-silicone release treatment agents. Addition-type silicone, condensation-type silicone, and the like are used as the silicone-based release treatment agent. Silicone release treatment agents have excellent properties such as peelability, residual adhesiveness, and heat resistance, but are expensive. In addition, since the silicone-based release treatment agent requires heat treatment at a high temperature particularly during the release treatment, it cannot be used for substrates having poor heat resistance such as OPP (orthophenylphenol) and polyethylene. Furthermore, the silicone-based release treatment agent has a problem of a low-molecular silicone compound that exists as an impurity in the release treatment agent, and has a drawback in writability and the like.
一方、非シリコーン系剥離処理剤としては、ポリビニルアルコールまたはエチレン−ビニルアルコール共重合体にアルキルイソシアネートを反応させた長鎖アルキルペンダント型ポリマーなどが知られている。非シリコーン系剥離処理剤における剥離性などの特性は、一般に、シリコーン系剥離処理剤より低い。しかし、例えば、エチレン−ビニルアルコール共重合物とアルキルイソシアネートとの反応生成物である長鎖アルキルペンダント型ポリマーによる剥離処理剤は、実用的に十分な剥離性を有している。このような剥離処理剤では、特別な触媒の併用、および熱処理などの操作が必要でなく、剥離処理剤の溶剤溶液を支持体に塗布後、乾燥するだけで剥離性能が得られる。このため、耐熱性が低い支持体（例えば、熱可塑性プラスチックなど）に対しても剥離処理が簡単に行える。 On the other hand, as a non-silicone release treatment agent, a long-chain alkyl pendant polymer in which an alkyl isocyanate is reacted with polyvinyl alcohol or an ethylene-vinyl alcohol copolymer is known. Properties such as releasability in non-silicone release treatment agents are generally lower than silicone release treatment agents. However, for example, a release treatment agent using a long-chain alkyl pendant polymer, which is a reaction product of an ethylene-vinyl alcohol copolymer and an alkyl isocyanate, has practically sufficient release properties. Such a release treatment agent does not require any special catalyst operation and heat treatment, and the release performance can be obtained simply by applying a solvent solution of the release treatment agent to the support and drying it. For this reason, the peeling treatment can be easily performed even on a support having low heat resistance (for example, a thermoplastic plastic).
ポリビニルアルコール重合体、エチレン／ビニルアルコール重合体にアルキルイソシアネートを付加させる場合、アルキルイソシアネートの付加量を調整し、ポリマー中に水酸基を残存させることで、反応性基を持たせることができる。例えば、水酸基を有するビニルアルコール／ビニルアルキルカルバメート化合物が提案されている（特許文献１）。また、粘着テープの背面処理剤として水酸基を有するビニルアルコール／ビニルアルキルカルバメート化合物を多官能イソシアネートと反応させることで、粘着剤の移行防止効果、加熱プレス板への汚染防止効果を付与することが提案されている（特許文献２）。さらに、離型フィルム用途として、水酸基量を有するビニルアルコール／ビニルアルキルカルバメート化合物を多官能イソシアネートで架橋させることで、耐溶剤性および１００℃での耐熱性が向上するとの報告がある（特許文献３）。 When adding an alkyl isocyanate to a polyvinyl alcohol polymer or an ethylene / vinyl alcohol polymer, a reactive group can be provided by adjusting the addition amount of the alkyl isocyanate and leaving a hydroxyl group in the polymer. For example, a vinyl alcohol / vinyl alkyl carbamate compound having a hydroxyl group has been proposed (Patent Document 1). Proposal is also given to prevent adhesive migration and to prevent contamination of heated press plates by reacting a vinyl alcohol / vinyl alkyl carbamate compound having a hydroxyl group with a polyfunctional isocyanate as a back treatment for adhesive tapes. (Patent Document 2). Furthermore, as a release film application, there is a report that solvent resistance and heat resistance at 100 ° C. are improved by crosslinking a vinyl alcohol / vinyl alkyl carbamate compound having a hydroxyl amount with a polyfunctional isocyanate (Patent Document 3). ).
しかし、従来技術では、どのような剥離処理剤を用いても、１００℃を超える高温条件下でも剥離力上昇（剥離性の低下）が小さく、かつ、剥離剤層の耐溶剤性に優れた剥離フィルムを製造することは困難であった。 However, in any conventional technique, any peeling treatment agent is used, and the peeling strength increase (decrease in peelability) is small even under high temperature conditions exceeding 100 ° C., and the peeling agent layer has excellent solvent resistance. It was difficult to produce a film.
そこで、本発明は、１００℃を超える高温条件下でも剥離力上昇（剥離性の低下）が小さく、かつ、剥離剤層の耐溶剤性に優れた剥離フィルムを製造可能な製造方法の提供を目的とする。さらに、本発明は、前記製造方法により製造される剥離フィルムを提供する。 Therefore, the present invention aims to provide a production method capable of producing a release film that has a small increase in peel strength (decrease in peelability) even under high temperature conditions exceeding 100 ° C. and that is excellent in the solvent resistance of the release agent layer. And Furthermore, this invention provides the peeling film manufactured by the said manufacturing method.
前記目的を達成するために、本発明の剥離フィルムの製造方法は、
基材フィルムの少なくとも片面に剥離剤層が形成された剥離フィルムの製造方法であって、
前記基材フィルムの、前記剥離剤層が形成される剥離剤層形成面に、水酸基含有長鎖アルキルポリマー（Ａ）と、水酸基と反応可能な官能基を複数有する架橋剤（Ｂ）とを含む剥離剤層形成用組成物を塗工する塗工工程と、
前記塗工工程後、前記剥離剤層形成面上で前記剥離剤層形成用組成物を６０℃以下の温度で加熱する加熱工程を含むことを特徴とする。
In order to achieve the above object, the method for producing a release film of the present invention comprises:
A method for producing a release film in which a release agent layer is formed on at least one side of a base film,
The release agent layer forming surface on which the release agent layer is formed of the base film contains a hydroxyl group-containing long-chain alkyl polymer (A) and a crosslinking agent (B) having a plurality of functional groups capable of reacting with hydroxyl groups. A coating process for coating the release agent layer-forming composition;
It comprises a heating step of heating the release agent layer forming composition at a temperature of 60 ° C. or less on the release agent layer forming surface after the coating step.
本発明の剥離フィルムは、前記本発明の製造方法により製造される剥離フィルムである。 The release film of the present invention is a release film produced by the production method of the present invention.
または、本発明の剥離フィルムは、
基材フィルムの少なくとも片面に剥離剤層が形成された剥離フィルムであって、
前記剥離剤層が、水酸基含有長鎖アルキルポリマー（Ａ）と、水酸基と反応可能な官能基を複数有する架橋剤（Ｂ）とを反応させて得られるポリマーを含み、
前記剥離剤層のゲル分率が７０重量％以上であることを特徴とする。
Alternatively, the release film of the present invention is
A release film having a release agent layer formed on at least one side of a base film,
The release agent layer includes a polymer obtained by reacting a hydroxyl group-containing long-chain alkyl polymer (A) with a crosslinking agent (B) having a plurality of functional groups capable of reacting with a hydroxyl group,
The release agent layer has a gel fraction of 70% by weight or more.
本発明の製造方法によれば、１００℃を超える高温条件下でも剥離力上昇（剥離性の低下）が小さく、かつ、剥離剤層の耐溶剤性に優れた剥離フィルムを製造可能である。また、本発明の剥離フィルムは、前記本発明の製造方法により製造されることで、１００℃を超える高温条件下でも剥離力上昇（剥離性の低下）が小さく、かつ、剥離剤層の耐溶剤性に優れている。 According to the production method of the present invention, it is possible to produce a release film having a small increase in peel strength (decrease in peelability) even under high temperature conditions exceeding 100 ° C. and excellent in solvent resistance of the release agent layer. In addition, the release film of the present invention is produced by the production method of the present invention, so that the increase in peel force (decrease in peelability) is small even under high temperature conditions exceeding 100 ° C., and the solvent resistance of the release agent layer Excellent in properties.
以下、本発明について、例を挙げて説明する。ただし、本発明は、以下の説明により限定されない。 Hereinafter, the present invention will be described with examples. However, the present invention is not limited by the following description.
本発明の剥離フィルムの製造方法は、前述のとおり、
基材フィルムの少なくとも片面に剥離剤層が形成された剥離フィルムの製造方法であって、
前記基材フィルムの、前記剥離剤層が形成される剥離剤層形成面に、水酸基含有長鎖アルキルポリマー（Ａ）と、水酸基と反応可能な官能基を複数有する架橋剤（Ｂ）とを含む剥離剤層形成用組成物を塗工する塗工工程と、
前記塗工工程後、前記剥離剤層形成面上で前記剥離剤層形成用組成物を６０℃以下の温度で加熱する加熱工程を含むことを特徴とする。
The production method of the release film of the present invention is as described above.
A method for producing a release film in which a release agent layer is formed on at least one side of a base film,
The release agent layer forming surface on which the release agent layer is formed of the base film contains a hydroxyl group-containing long-chain alkyl polymer (A) and a crosslinking agent (B) having a plurality of functional groups capable of reacting with hydroxyl groups. A coating process for coating the release agent layer-forming composition;
It comprises a heating step of heating the release agent layer forming composition at a temperature of 60 ° C. or less on the release agent layer forming surface after the coating step.
［１．水酸基含有長鎖アルキルポリマー（Ａ）］
前記水酸基含有長鎖アルキルポリマー（Ａ）は、特に限定されないが、下記化学式（１）の構造を含むビニルアルコールポリマーであることが好ましい。
The hydroxyl group-containing long-chain alkyl polymer (A) is not particularly limited, but is preferably a vinyl alcohol polymer having a structure represented by the following chemical formula (1).
前記化学式（１）に由来する主鎖炭素原子数の数は、特に限定されないが、前記水酸基含有長鎖アルキルポリマー（Ａ）の主鎖炭素原子数に対し、例えば５〜５０％である。 The number of main chain carbon atoms derived from the chemical formula (1) is not particularly limited, but is, for example, 5 to 50% with respect to the main chain carbon atom number of the hydroxyl group-containing long chain alkyl polymer (A).
前記水酸基含有長鎖アルキルポリマー（Ａ）は、主鎖中に、前記化学式（１）等の水酸基含有構造以外の構造を含んでいても良いし、含んでいなくても良い。 The hydroxyl group-containing long-chain alkyl polymer (A) may or may not contain a structure other than the hydroxyl group-containing structure such as the chemical formula (1) in the main chain.
例えば、前記水酸基含有長鎖アルキルポリマー（Ａ）が、さらに、下記化学式（２）の構造を含み、
Ｒ１は、直鎖または分枝アルキル基であり、
前記水酸基含有長鎖アルキルポリマー（Ａ）の主鎖炭素原子数に対し、前記化学式（２）で表される構造に由来する主鎖炭素原子の数が、例えば、２５％以下または２０％以下であっても良い。また、前記水酸基含有長鎖アルキルポリマー（Ａ）の溶解性（溶剤に対する溶解しやすさ）の観点から、前記化学式（２）に由来する主鎖炭素原子数を、主鎖炭素原子数に対し、例えば１５％以上、２０％以上または３０％以上と多くしても良い。また、Ｒ１において、直鎖もしくは分枝アルキル基の炭素数は、好ましくは１〜２４である。前記直鎖もしくは分枝アルキル基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、sec-ブチル基、ter-ブチル基等が挙げられる。
For example, the hydroxyl group-containing long-chain alkyl polymer (A) further includes a structure represented by the following chemical formula (2):
R 1 is a linear or branched alkyl group,
The number of main chain carbon atoms derived from the structure represented by the chemical formula (2) is, for example, 25% or less or 20% or less with respect to the number of main chain carbon atoms of the hydroxyl group-containing long-chain alkyl polymer (A). There may be. In addition, from the viewpoint of the solubility of the hydroxyl group-containing long-chain alkyl polymer (A) (easiness to dissolve in a solvent), the number of main chain carbon atoms derived from the chemical formula (2) is determined with respect to the number of main chain carbon atoms. For example, it may be increased to 15% or more, 20% or more, or 30% or more. In R 1 , the linear or branched alkyl group preferably has 1 to 24 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a ter-butyl group.
なお、前記化学式（２）中のＲ１は、前記水酸基含有長鎖アルキルポリマー（Ａ）中に複数存在する場合は、同一でも異なっていても良い。 In addition, when multiple R < 1 > in the said Chemical formula (2) exists in the said hydroxyl-containing long-chain alkyl polymer (A), it may be same or different.
また、前記水酸基含有長鎖アルキルポリマー（Ａ）が、さらに、下記化学式（３）で表されるエチレン基を含み、
前記水酸基含有長鎖アルキルポリマー（Ａ）の主鎖炭素原子数に対し、前記化学式（３）で表される構造に由来する主鎖炭素原子の数が９０％以下であっても良い。前記化学式（３）に由来する主鎖炭素原子数の数は、前記水酸基含有長鎖アルキルポリマー（Ａ）の主鎖炭素原子数に対し、より好ましくは６０％以下、さらに好ましくは５０％以下、理想的には０％である。
The hydroxyl group-containing long-chain alkyl polymer (A) further contains an ethylene group represented by the following chemical formula (3):
The number of main chain carbon atoms derived from the structure represented by the chemical formula (3) may be 90% or less with respect to the number of main chain carbon atoms of the hydroxyl group-containing long chain alkyl polymer (A). The number of main chain carbon atoms derived from the chemical formula (3) is more preferably 60% or less, still more preferably 50% or less, based on the number of main chain carbon atoms of the hydroxyl group-containing long-chain alkyl polymer (A). Ideally 0%.
また、前記水酸基含有長鎖アルキルポリマー（Ａ）が、さらに、下記化学式（４）で表される構造を含み、
Ｒ２は、直鎖または分枝脂肪族炭化水素基であり、
Ｌは、単結合または任意の原子団であっても良い。
The hydroxyl group-containing long-chain alkyl polymer (A) further includes a structure represented by the following chemical formula (4):
R 2 is a straight chain or branched aliphatic hydrocarbon group,
L may be a single bond or an arbitrary atomic group.
Ｌとしては、特に限定されないが、例えば、−ＣＯ−、−ＣＨ２−ＣＨ（ＯＨ）−、−ＣＯ−ＮＨ−、−ＳＯ２−、−ＰＯ（ＯＨ）−Ｏ−、等が挙げられる。 L is not particularly limited, and examples thereof include —CO—, —CH 2 —CH (OH) —, —CO—NH—, —SO 2 —, —PO (OH) —O—, and the like.
なお、前記化学式（４）中のＲ２およびＬは、それぞれ、前記水酸基含有長鎖アルキルポリマー（Ａ）中に複数存在する場合は、同一でも異なっていても良い。 In addition, R 2 and L in the chemical formula (4) may be the same or different when a plurality of R 2 and L are present in the hydroxyl group-containing long-chain alkyl polymer (A).
前記化学式（４）で表される構造は、下記化学式（４−２）で表される構造であることが好ましい。
前記化学式（４）に由来する主鎖炭素原子数の数は、特に限定されないが、前記水酸基含有長鎖アルキルポリマー（Ａ）の主鎖炭素原子数に対し、例えば３０〜７５％である。Ｒ２において、前記直鎖もしくは分枝脂肪族炭化水素基は、飽和でも不飽和でも良く、例えば、アルキル基でも、アルケニル基でも、アルキニル基でも良いが、アルキル基が好ましい。また、前記直鎖もしくは分枝脂肪族炭化水素基は、直鎖状であることが好ましく、直鎖アルキル基がより好ましい。前記直鎖もしくは分枝脂肪族炭化水素基の炭素数は、好ましくは１２〜３０である。前記直鎖もしくは分枝脂肪族炭化水素基としては、例えば、ドデシル基、ラウリル基（ｎ−ドデシル基）、テトラデシル基、ミリスチル基（ｎ−テトラデシル基）、ヘキサデシル基、パルミチル基（ｎ−ヘキサデシル基）、オクタデシル基、ステアリル基（ｎ−オクタデシル基）、オレイル基等が挙げられ、より好ましくはオクタデシル基、特に好ましくはステアリル基（ｎ−オクタデシル基）である。 The number of main chain carbon atoms derived from the chemical formula (4) is not particularly limited, but is, for example, 30 to 75% with respect to the main chain carbon atoms of the hydroxyl group-containing long chain alkyl polymer (A). In R 2 , the linear or branched aliphatic hydrocarbon group may be saturated or unsaturated, and may be, for example, an alkyl group, an alkenyl group, or an alkynyl group, but an alkyl group is preferable. The linear or branched aliphatic hydrocarbon group is preferably linear, and more preferably a linear alkyl group. The straight chain or branched aliphatic hydrocarbon group preferably has 12 to 30 carbon atoms. Examples of the linear or branched aliphatic hydrocarbon group include a dodecyl group, a lauryl group (n-dodecyl group), a tetradecyl group, a myristyl group (n-tetradecyl group), a hexadecyl group, and a palmityl group (n-hexadecyl group). ), Octadecyl group, stearyl group (n-octadecyl group), oleyl group and the like, more preferably octadecyl group, particularly preferably stearyl group (n-octadecyl group).
なお、前記化学式（４−２）で表される構造を含む水酸基含有長鎖アルキルポリマー（Ａ）は、例えば、ビニルアルコールポリマーの水酸基を、下記化学式（５）で表される脂肪族イソシアネート化合物と反応させて得ることができる。
また、前記水酸基含有長鎖アルキルポリマー（Ａ）の重合度は、特に限定されないが、溶剤への溶解性およびハンドリングの観点からは、前記水酸基含有長鎖アルキルポリマー（Ａ）の重合度が高すぎないことが好ましい。前記水酸基含有長鎖アルキルポリマー（Ａ）がエチレン−ビニルアルコール共重合体（前記化学式（１）および（３）を含む）である場合、その平均重合度は、例えば５００〜３，０００、好ましくは８００〜２，５００である。また、前記水酸基含有長鎖アルキルポリマー（Ａ）が、ポリビニルアセテートの一部または全部をケン化して得られたポリビニルアルコール（前記化学式（１）を含み、さらに、前記化学式（２）を含むかまたは含まない）である場合、その平均重合度は、例えば１００〜３，０００、好ましくは１５０〜５００の範囲である。なお、前記水酸基含有長鎖アルキルポリマー（Ａ）の重合度は、主鎖炭素原子数２（すなわち、エチレンまたはビニルアルコール１つ分）を１単位（重合度１）として計算する。 The degree of polymerization of the hydroxyl group-containing long chain alkyl polymer (A) is not particularly limited, but the degree of polymerization of the hydroxyl group-containing long chain alkyl polymer (A) is too high from the viewpoints of solubility in a solvent and handling. Preferably not. When the hydroxyl group-containing long-chain alkyl polymer (A) is an ethylene-vinyl alcohol copolymer (including the chemical formulas (1) and (3)), the average degree of polymerization is, for example, 500 to 3,000, preferably 800 to 2,500. Further, the hydroxyl group-containing long-chain alkyl polymer (A) is a polyvinyl alcohol obtained by saponifying a part or all of polyvinyl acetate (including the chemical formula (1), and further including the chemical formula (2)) The average degree of polymerization is, for example, in the range of 100 to 3,000, preferably 150 to 500. The degree of polymerization of the hydroxyl group-containing long-chain alkyl polymer (A) is calculated with 2 main chain carbon atoms (that is, one ethylene or vinyl alcohol) as one unit (degree of polymerization 1).
なお、前記水酸基含有長鎖アルキルポリマー（Ａ）は、市販品を用いても良いし、適宜製造しても良い。 The hydroxyl group-containing long chain alkyl polymer (A) may be a commercially available product or may be appropriately manufactured.
［２．架橋剤（Ｂ）］
前記架橋剤（Ｂ）は、前述のとおり、水酸基と反応可能な官能基を（１分子内に）複数有する。前記架橋剤（Ｂ）は、水酸基と反応可能な官能基を（１分子内に）３個以上有することが好ましい。前記水酸基と反応可能な官能基としては、例えば、カルボキシ基、カルボン酸無水物基、ハロカルボニル基（酸ハロゲン化物基）、エポキシ基、イソシアネート基、アミノ基等が挙げられ、中で、イソシアネート基が好ましい。前記架橋剤（Ｂ）は、特に限定されないが、例えば、イソシアネート化合物、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸等、それらの酸無水物および酸ハロゲン化物等が挙げられ、さらに、エポキシ基含有化合物としては、エチレングリコールジグリシジルエーテル、グリセロールポリグリシジルエーテル、ポリブタジエンジグリシジルエーテル等が挙げられ、アミノ基含有化合物としては、エチレンジアミン、１，３−ジアミノプロパン、１，４−ジアミノブタン、１，５−ジアミノペンタン、１，６−ジアミノヘキサン等の低分子化合物、ポリエチレングリコールジアミン、ポリプロピレングリコールジアミン等の高分子化合物、および、トリメチロールプロパンまたはグリセリンへのこれらの多官能アミノ基含有化合物付加体等が挙げられ、イソシアネート化合物が特に好ましい。前記イソシアネート化合物は、前記架橋剤（Ｂ）の前記水酸基と反応可能な官能基がイソシアネート基（−Ｎ＝Ｃ＝Ｏ）である場合である。前記イソシアネート化合物も特に限定されず、例えば、脂肪族イソシアネートでも、芳香族イソシアネートでも良い。前記脂肪族イソシアネートとしては、例えば、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等が挙げられる。前記芳香族イソシアネートとしては、例えば、トリレンジイソシアネート、メチレンジフェニルジイソシアネート等が挙げられる。また、前記イソシアネート化合物は、前記各脂肪族イソシアネートおよび前記各芳香族イソシアネートのうち任意の１種または複数種類の重合体、ポリオール付加体等であっても良く、脂肪族イソシアネートの重合体が特に好ましい。
[2. Crosslinking agent (B)]
As described above, the crosslinking agent (B) has a plurality of functional groups (in one molecule) capable of reacting with a hydroxyl group. The crosslinking agent (B) preferably has 3 or more functional groups (in one molecule) capable of reacting with a hydroxyl group. Examples of the functional group capable of reacting with the hydroxyl group include a carboxy group, a carboxylic acid anhydride group, a halocarbonyl group (acid halide group), an epoxy group, an isocyanate group, an amino group, and the like. Is preferred. The crosslinking agent (B) is not particularly limited, and examples thereof include isocyanate compounds, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, and suberic acid, and their acid anhydrides and acid halides. Furthermore, examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, glycerol polyglycidyl ether, and polybutadiene diglycidyl ether. Examples of the amino group-containing compound include ethylenediamine, 1,3-diaminopropane, 1 , 4-diaminobutane, 1,5-diaminopentane, low molecular compounds such as 1,6-diaminohexane, high molecular compounds such as polyethylene glycol diamine, polypropylene glycol diamine, and these to trimethylolpropane or glycerin Functional amino group-containing compound adduct and the like, isocyanate compounds are particularly preferred. The said isocyanate compound is a case where the functional group which can react with the said hydroxyl group of the said crosslinking agent (B) is an isocyanate group (-N = C = O). The isocyanate compound is not particularly limited, and may be aliphatic isocyanate or aromatic isocyanate, for example. Examples of the aliphatic isocyanate include hexamethylene diisocyanate and isophorone diisocyanate. Examples of the aromatic isocyanate include tolylene diisocyanate and methylene diphenyl diisocyanate. Further, the isocyanate compound may be any one or plural kinds of polymers, polyol adducts, etc. among the respective aliphatic isocyanates and the respective aromatic isocyanates, and polymers of aliphatic isocyanates are particularly preferable. .
また、前記イソシアネート化合物としては、例えば、下記化学式（６）で表されるビウレット、下記化学式（７）で表されるイソシアヌレート、下記化学式（８）で表されるアダクト、下記化学式（９）または（１０）で表される２官能型、下記化学式（１１）または（１２）で表されるＴＤＩ（トルエンジイソシアネート）等が挙げられる。 Examples of the isocyanate compound include biuret represented by the following chemical formula (6), isocyanurate represented by the following chemical formula (7), adduct represented by the following chemical formula (8), chemical formula (9) or Examples thereof include a bifunctional type represented by (10), TDI (toluene diisocyanate) represented by the following chemical formula (11) or (12), and the like.
前記化学式（６）〜（１０）中、各Ｒは、それぞれ、直鎖または分枝アルキレン基であり、同一でも異なっていても良く、前記直鎖または分枝アルキレン基の炭素数は、好ましくは１〜２４である。前記化学式（８）中、Ｒ３は、メチン基である。前記化学式（１０）中、Ｒ４は、直鎖または分枝アルキル基であり、同一でも異なっていても良く、前記直鎖または分枝アルキル基の炭素数は、好ましくは１〜２４である。前記架橋剤（Ｂ）としては、前記化学式（６）において各Ｒがヘキサメチレン基である、ヘキサメチレンジイソシアネートのイソシアヌレート体（ＨＤＩイソシアヌレート）が特に好ましい。 In the chemical formulas (6) to (10), each R is a linear or branched alkylene group, which may be the same or different, and the carbon number of the linear or branched alkylene group is preferably 1-24. In the chemical formula (8), R 3 is a methine group. In the chemical formula (10), R 4 is a linear or branched alkyl group, which may be the same or different, and the linear or branched alkyl group preferably has 1 to 24 carbon atoms. The crosslinking agent (B) is particularly preferably an isocyanurate of hexamethylene diisocyanate (HDI isocyanurate) in which each R is a hexamethylene group in the chemical formula (6).
なお、前記架橋剤（Ｂ）は、市販品を用いても良いし、適宜製造しても良い。 In addition, a commercial item may be used for the said crosslinking agent (B), and you may manufacture it suitably.
［３．剥離フィルムの製造方法］
本発明の剥離フィルムの製造方法は、前述のとおり、前記塗工工程および前記加熱工程を含むが、その他の工程を適宜含んでいても良いし、含んでいなくても良い。本発明の剥離フィルムの製造方法は、例えば、以下のようにして行うことができる。
[3. Method for producing release film]
Although the manufacturing method of the peeling film of this invention includes the said coating process and the said heating process as above-mentioned, the other process may be included suitably and does not need to be included. The manufacturing method of the peeling film of this invention can be performed as follows, for example.
まず、前記水酸基含有長鎖アルキルポリマー（Ａ）を準備する。前記水酸基含有長鎖アルキルポリマー（Ａ）は、前述のとおり、市販品を用いても、製造しても良い。製造する場合の製造方法は、特に限定されず、公知技術等を参考にして適宜行うことができる。例えば、前記水酸基含有長鎖アルキルポリマー（Ａ）が前記化学式（１）および前記化学式（４−２）で表される構造を含む場合は、例えば、原料ビニルアルコールポリマーに、前記化学式（５）で表される脂肪族イソシアネート化合物を反応させて製造できる。前記原料ビニルアルコールポリマーとしては、例えば、ポリビニルアセテートの一部または全部をケン化して得られたポリビニルアルコール（前記化学式（１）を含み、さらに、前記化学式（２）を含むかまたは含まない）、およびエチレン−ビニルアルコール共重合体（前記化学式（１）および（３）を含む）等が挙げられる。前記脂肪族イソシアネート化合物の物質量（モル数）は、特に限定されないが、例えば、イソシアネート基の数が、前記原料ビニルアルコールポリマーの水酸基数に対し、５０〜９５％とする。また、反応系が、前記原料ビニルアルコールポリマー、および前記化学式（５）で表される脂肪族イソシアネート化合物以外の他の物質を適宜含んでいても良いし、含んでいなくても良い。前記他の物質としては、例えば、反応溶媒（溶剤）、触媒等が挙げられる。前記反応溶媒（溶剤）は、特に限定されないが、例えば、水、芳香族炭化水素、水溶性非プロトン性溶剤等が挙げられ、１種類でも複数種類併用しても良い。前記芳香族炭化水素としては、例えば、トルエン、オルトキシレン、メタキシレン、パラキシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等が挙げられる。前記水溶性非プロトン性溶剤としては、例えば、ＤＭＳＯ（ジメチルスルホキシド）、ＤＭＡ（ジメチルアセトアミド）、ＤＭＦ（ジメチルホルムアミド）、ＮＭＰ（Ｎ−メチル−２−ピロリドン）、ＮＥＰ（Ｎ−エチル−２−ピロリドン）、アセトニトリル等が挙げられる。前記反応溶媒（溶剤）は、芳香族炭化水素および水溶性非プロトン性溶剤からなる群から選択される少なくとも１種類であることが特に好ましい。前記触媒としては、例えば、アルキルスズ触媒（例えば、ジブチルスズジラウレート、ジブチルスズジオクテート）、３級アミン（例えば、トリエチルアミン）、アルミニウムアセチルアセトナート、ジルコニウムアセチルアセトナート、亜鉛アセチルアセトナート等が挙げられる。反応温度および反応時間は、特に限定されず、適宜設定可能である。 First, the hydroxyl group-containing long chain alkyl polymer (A) is prepared. The hydroxyl group-containing long-chain alkyl polymer (A) may be a commercially available product or may be produced as described above. The manufacturing method in the case of manufacturing is not specifically limited, It can carry out suitably with reference to a well-known technique etc. For example, when the hydroxyl group-containing long-chain alkyl polymer (A) includes a structure represented by the chemical formula (1) and the chemical formula (4-2), for example, the raw material vinyl alcohol polymer is represented by the chemical formula (5). It can be produced by reacting the aliphatic isocyanate compound represented. Examples of the raw vinyl alcohol polymer include polyvinyl alcohol obtained by saponifying a part or all of polyvinyl acetate (including the chemical formula (1) and further including or not including the chemical formula (2)), And ethylene-vinyl alcohol copolymer (including the chemical formulas (1) and (3)). The amount (number of moles) of the aliphatic isocyanate compound is not particularly limited. For example, the number of isocyanate groups is 50 to 95% with respect to the number of hydroxyl groups of the raw vinyl alcohol polymer. In addition, the reaction system may or may not contain other materials other than the raw material vinyl alcohol polymer and the aliphatic isocyanate compound represented by the chemical formula (5) as appropriate. Examples of the other substance include a reaction solvent (solvent) and a catalyst. Although the said reaction solvent (solvent) is not specifically limited, For example, water, an aromatic hydrocarbon, a water-soluble aprotic solvent, etc. are mentioned, You may use together 1 type or multiple types. Examples of the aromatic hydrocarbon include toluene, orthoxylene, metaxylene, paraxylene, mesitylene, chlorobenzene, dichlorobenzene, and the like. Examples of the water-soluble aprotic solvent include DMSO (dimethyl sulfoxide), DMA (dimethylacetamide), DMF (dimethylformamide), NMP (N-methyl-2-pyrrolidone), NEP (N-ethyl-2-pyrrolidone). ), Acetonitrile and the like. The reaction solvent (solvent) is particularly preferably at least one selected from the group consisting of aromatic hydrocarbons and water-soluble aprotic solvents. Examples of the catalyst include alkyl tin catalysts (for example, dibutyltin dilaurate, dibutyltin dioctate), tertiary amines (for example, triethylamine), aluminum acetylacetonate, zirconium acetylacetonate, and zinc acetylacetonate. The reaction temperature and reaction time are not particularly limited and can be set as appropriate.
つぎに、基材フィルムの、剥離剤層が形成される剥離剤層形成面に、前記水酸基含有長鎖アルキルポリマー（Ａ）および前記架橋剤（Ｂ）を含む剥離剤層形成用組成物を塗工する（塗工工程）。前記架橋剤（Ｂ）の物質量（モル数）は、特に限定されないが、例えば、水酸基と反応可能な官能基（例えば、イソシアネート基）の数が、前記水酸基含有長鎖アルキルポリマー（Ａ）の水酸基数に対し、３０〜１００％とする。前記剥離剤層形成用組成物は、前記水酸基含有長鎖アルキルポリマー（Ａ）および前記架橋剤（Ｂ）以外の他の物質を適宜含んでいても良い。前記他の物質としては、例えば、反応溶媒（溶剤）、触媒等が挙げられる。前記反応溶媒（溶剤）は、特に限定されないが、例えば、水、芳香族炭化水素、水溶性非プロトン性溶剤等が挙げられ、１種類でも複数種類併用しても良い。前記芳香族炭化水素としては、例えば、トルエン、オルトキシレン、メタキシレン、パラキシレン、メシチレン、クロロベンゼン、ジクロロベンゼン等が挙げられる。前記水溶性非プロトン性溶剤としては、例えば、ＤＭＳＯ（ジメチルスルホキシド）、ＤＭＡ（ジメチルアセトアミド）、ＤＭＦ（ジメチルホルムアミド）、ＮＭＰ（Ｎ−メチル−２−ピロリドン）、ＮＥＰ（Ｎ−エチル−２−ピロリドン）、アセトニトリル等が挙げられる。前記反応溶媒（溶剤）は、芳香族炭化水素を含むことが好ましく、芳香族炭化水素および水溶性非プロトン性溶剤からなる群から選択される少なくとも１種類であることがより好ましく、芳香族炭化水素および水溶性非プロトン性溶剤を併用することが特に好ましい。芳香族炭化水素溶剤を用いれば、前記水酸基含有長鎖アルキルポリマー（Ａ）および前記架橋剤（Ｂ）を溶解させやすく、さらに、水溶性非プロトン性溶剤を併用することで、より低温でも塗工（塗布）しやすくなる。より具体的には、例えば、トルエンとＮメチルピロリドンまたはＮエチルピロリドンを、重量比で９８／２〜５０／５０、より好ましくは９５／５〜７０／３０で混合して用いる。前記触媒としては、例えば、アルキルスズ触媒（例えば、ジブチルスズジラウレート、ジブチルスズジオクテート）、３級アミン（例えば、トリエチルアミン）、アルミニウムアセチルアセトナート、ジルコニウムアセチルアセトナート、亜鉛アセチルアセトナート等が挙げられる。 Next, the release agent layer forming composition containing the hydroxyl group-containing long-chain alkyl polymer (A) and the crosslinking agent (B) is applied to the release agent layer forming surface of the base film on which the release agent layer is formed. Work (coating process). The amount (number of moles) of the crosslinking agent (B) is not particularly limited. For example, the number of functional groups (for example, isocyanate groups) that can react with a hydroxyl group is the number of the hydroxyl group-containing long-chain alkyl polymer (A). 30 to 100% with respect to the number of hydroxyl groups. The composition for forming a release agent layer may appropriately contain a substance other than the hydroxyl group-containing long-chain alkyl polymer (A) and the crosslinking agent (B). Examples of the other substance include a reaction solvent (solvent) and a catalyst. Although the said reaction solvent (solvent) is not specifically limited, For example, water, an aromatic hydrocarbon, a water-soluble aprotic solvent, etc. are mentioned, You may use together 1 type or multiple types. Examples of the aromatic hydrocarbon include toluene, orthoxylene, metaxylene, paraxylene, mesitylene, chlorobenzene, dichlorobenzene, and the like. Examples of the water-soluble aprotic solvent include DMSO (dimethyl sulfoxide), DMA (dimethylacetamide), DMF (dimethylformamide), NMP (N-methyl-2-pyrrolidone), NEP (N-ethyl-2-pyrrolidone). ), Acetonitrile and the like. The reaction solvent (solvent) preferably contains an aromatic hydrocarbon, more preferably at least one selected from the group consisting of an aromatic hydrocarbon and a water-soluble aprotic solvent. It is particularly preferable to use a water-soluble aprotic solvent in combination. If an aromatic hydrocarbon solvent is used, the hydroxyl group-containing long-chain alkyl polymer (A) and the cross-linking agent (B) can be easily dissolved. Further, by using a water-soluble aprotic solvent in combination, coating can be performed at a lower temperature. (Coating) is easier. More specifically, for example, toluene and N methyl pyrrolidone or N ethyl pyrrolidone are mixed at a weight ratio of 98/2 to 50/50, more preferably 95/5 to 70/30. Examples of the catalyst include alkyl tin catalysts (for example, dibutyltin dilaurate, dibutyltin dioctate), tertiary amines (for example, triethylamine), aluminum acetylacetonate, zirconium acetylacetonate, and zinc acetylacetonate.
前記基材フィルムは、特に限定されず、例えば、熱可塑性樹脂でも熱硬化性樹脂でも良いが、熱可塑性樹脂が好ましい。前記熱可塑性樹脂としては、例えば、ＰＥＴ（ポリエチレンテレフタレート）、ＰＥ（ポリエチレン）、ＰＰ（ポリプロピレン、例えば配向ポリプロピレン）、熱可塑性樹脂をラミネートした紙等が挙げられる。 The base film is not particularly limited. For example, a thermoplastic resin or a thermosetting resin may be used, but a thermoplastic resin is preferable. Examples of the thermoplastic resin include PET (polyethylene terephthalate), PE (polyethylene), PP (polypropylene, for example, oriented polypropylene), paper laminated with a thermoplastic resin, and the like.
前記塗工工程時の前記基材フィルムおよび前記剥離剤層形成用組成物の温度は、特に限定されず、適宜設定可能である。例えば、前記溶剤が芳香族炭化水素（例えば、トルエン、キシレンなど）である場合は、溶液（前記剥離剤層形成用組成物）のゲル化を防止するために、４０℃以上の温度で塗工することが好ましい。前述のとおり、水溶性非プロトン性溶媒（例えば、ジメチルスルホキシド、ジメチルホルムアミド、アセトニトリル、Ｎメチルピロリドン、Ｎエチルピロリドンなど）を併用することで、より低温でも塗工しやすくなる。具体的には、例えば、２０℃程度の温度でも、ゲル化せずに溶液状態を維持できる。前記塗工工程における塗工方法は、特に限定されず、例えば、前記剥離剤層形成用組成物を前記基材フィルムに塗布しても良いし、前記基材フィルムを前記剥離剤層形成用組成物に浸漬させても良い。塗布法も特に限定されないが、例えば、バーコータ、ロールコータ、キスコータ、スロットダイコータ、スクイズコータ、グラビアコータ等を用いる方法が挙げられる。前記剥離剤層形成用組成物の塗工量も特に限定されないが、乾燥後の膜厚が、例えば０．１〜５μｍとなるようにする。 The temperature of the base film and the release agent layer forming composition during the coating step is not particularly limited and can be set as appropriate. For example, when the solvent is an aromatic hydrocarbon (for example, toluene, xylene, etc.), the coating is performed at a temperature of 40 ° C. or higher in order to prevent gelation of the solution (the release agent layer forming composition). It is preferable to do. As described above, when a water-soluble aprotic solvent (for example, dimethyl sulfoxide, dimethylformamide, acetonitrile, N-methylpyrrolidone, N-ethylpyrrolidone, etc.) is used in combination, it becomes easier to apply even at lower temperatures. Specifically, for example, even at a temperature of about 20 ° C., the solution state can be maintained without gelation. The coating method in the coating step is not particularly limited. For example, the release agent layer forming composition may be applied to the base film, or the base film may be applied to the release agent layer forming composition. It may be immersed in an object. The coating method is not particularly limited, and examples thereof include a method using a bar coater, roll coater, kiss coater, slot die coater, squeeze coater, gravure coater and the like. The coating amount of the release agent layer-forming composition is not particularly limited, but the film thickness after drying is, for example, 0.1 to 5 μm.
前記塗工工程後、前記６０℃以下で加熱する加熱工程に先立ち、前記剥離剤層形成面上で前記剥離剤層形成用組成物を加熱し、前記水酸基含有長鎖アルキルポリマー（Ａ）と架橋剤（Ｂ）とを反応させて架橋体を形成させる工程（架橋体形成工程）を行っても良い。前記架橋体形成工程における加熱温度は、例えば、後に行う前記加熱工程より高温でも良い。また、前記剥離剤層形成用組成物が溶剤を含む場合は、前記塗工工程後に前記溶剤を揮発させて前記剥離剤層形成用組成物を乾燥させる（乾燥工程）。前記乾燥工程は、例えば、前記架橋体形成工程に先立ち、または前記架橋体形成工程と同時に行うことができる。前記乾燥工程においては、前記剥離剤層形成用組成物を加熱することが好ましい。加熱温度は、特に限定されないが、例えば６０〜１５０℃、好ましくは６０〜１００℃である。加熱時間も特に限定されないが、例えば０．１〜１分間である。また、前記架橋体形成工程における加熱温度および加熱時間は、特に限定されず、適宜設定可能である。 After the coating step, prior to the heating step of heating at 60 ° C. or lower, the release agent layer forming composition is heated on the release agent layer forming surface to crosslink with the hydroxyl group-containing long chain alkyl polymer (A). You may perform the process (crosslinked body formation process) which makes an agent (B) react and forms a crosslinked body. The heating temperature in the crosslinked body forming step may be higher than the heating step performed later, for example. When the release agent layer forming composition contains a solvent, the solvent is evaporated after the coating step to dry the release agent layer forming composition (drying step). The drying step can be performed, for example, prior to the crosslinked body forming step or simultaneously with the crosslinked body forming step. In the drying step, it is preferable to heat the release agent layer forming composition. Although heating temperature is not specifically limited, For example, it is 60-150 degreeC, Preferably it is 60-100 degreeC. The heating time is not particularly limited, but is, for example, 0.1 to 1 minute. Moreover, the heating temperature and heating time in the said crosslinked body formation process are not specifically limited, It can set suitably.
さらに、前記剥離剤層形成面上において、前記剥離剤層形成用組成物を６０℃以下の温度で加熱する（加熱工程）。加熱温度は、６０℃以下であれば特に限定されないが、例えば３５〜６０℃、好ましくは４０〜６０℃である。加熱時間も特に限定されないが、例えば１２〜１７０時間、好ましくは２４〜７２時間である。前記６０℃以下で加熱する加熱工程を行うことにより、１００℃を超える高温条件下（例えば、１５０℃またはそれ以上）でも剥離力上昇（剥離性の低下）が小さく、かつ、剥離剤層の耐溶剤性に優れた剥離フィルムを得ることができる。前記６０℃以下の温度で加熱する加熱工程において起こる現象は不明であるが、例えば、前記乾燥工程または前記架橋体形成工程において未反応であった水酸基含有長鎖アルキルポリマー（Ａ）の水酸基と架橋剤（Ｂ）の官能基との反応がさらに進行し、前記架橋体の架橋構造の数が増加してより強固になると考えられる。また、前記加熱工程に先立ち架橋体が形成されない場合（例えば、前記架橋体形成工程を行わない場合、および、前記乾燥工程を行わない場合）は、前記加熱工程において、水酸基含有長鎖アルキルポリマー（Ａ）の水酸基と架橋剤（Ｂ）の官能基との反応により架橋構造（架橋体）が形成されると推測される。なお、前記加熱工程において起こると思われる現象を、以下「熟成」ということがある。このように低温で熟成させることで、前記基材フィルムが耐熱性の低い基材（ポリエチレン、配向ポリプロピレンなど）である場合でも、耐熱性の高い剥離剤層を形成できる。 Furthermore, the release agent layer forming composition is heated on the release agent layer forming surface at a temperature of 60 ° C. or less (heating step). Although heating temperature will not be specifically limited if it is 60 degrees C or less, For example, it is 35-60 degreeC, Preferably it is 40-60 degreeC. The heating time is not particularly limited, but is, for example, 12 to 170 hours, preferably 24 to 72 hours. By performing the heating step of heating at 60 ° C. or less, the increase in peel strength (decrease in peelability) is small even under high temperature conditions exceeding 100 ° C. (for example, 150 ° C. or higher), and the resistance of the release agent layer is reduced. A release film having excellent solvent properties can be obtained. Although the phenomenon that occurs in the heating step of heating at a temperature of 60 ° C. or lower is unknown, for example, the hydroxyl group-containing long-chain alkyl polymer (A) that has not reacted in the drying step or the crosslinked body forming step is crosslinked with the hydroxyl group. It is considered that the reaction with the functional group of the agent (B) further proceeds, and the number of cross-linked structures of the cross-linked product increases and becomes stronger. Moreover, when a crosslinked body is not formed prior to the heating step (for example, when the crosslinked body forming step is not performed and when the drying step is not performed), in the heating step, a hydroxyl group-containing long chain alkyl polymer ( It is presumed that a crosslinked structure (crosslinked body) is formed by the reaction between the hydroxyl group of A) and the functional group of the crosslinking agent (B). In addition, the phenomenon considered to occur in the heating process may be hereinafter referred to as “aging”. By aging at such a low temperature as described above, a release layer with high heat resistance can be formed even when the base film is a base material with low heat resistance (polyethylene, oriented polypropylene, etc.).
以上のようにして、基材フィルムの少なくとも片面に剥離剤層を形成し、剥離フィルムを製造することができる。 As described above, a release agent layer can be formed on at least one surface of the base film to produce a release film.
［４．剥離フィルム］
本発明の剥離フィルムは、前述のとおり、前記本発明の製造方法により製造される剥離フィルムである。または、本発明の剥離フィルムは、前述のとおり、基材フィルムの少なくとも片面に剥離剤層が形成された剥離フィルムであって、前記剥離剤層が、水酸基含有長鎖アルキルポリマー（Ａ）と、水酸基と反応可能な官能基を複数有する架橋剤（Ｂ）とを反応させて得られるポリマーを含み、前記剥離剤層のゲル分率が７０重量％以上であることを特徴とする剥離フィルムであっても良い。本発明の剥離フィルムにおいて、前記剥離剤層のゲル分率は、好ましくは７０重量％以上、より好ましくは８０重量％以上、さらに好ましくは９０重量％以上、さらに好ましくは９５重量％以上、理想的には１００重量％である。前記加熱工程において熟成させることで、例えば、このようにゲル分率が高く、耐熱性の高い剥離剤層となる。なお、前記ゲル分率は、例えば、前記剥離剤層を前記基材フィルムから分離後、重量を測定し、テトラヒドロフランに浸漬し、３０℃で７２時間放置し、ステンレスメッシュでろ過し、乾燥後の残渣の重量を再度測定し、前記残渣の重量変化率から算出することができる。すなわち、前記乾燥後の残渣の重量を、前記基材フィルムから分離後の前記剥離剤層の重量で割った値が、ゲル分率となる。ただし、この測定法は一例であり、本発明がこの測定方法により限定されるものではない。
[4. Release film]
As described above, the release film of the present invention is a release film produced by the production method of the present invention. Or, as described above, the release film of the present invention is a release film in which a release agent layer is formed on at least one side of the base film, and the release agent layer is a hydroxyl group-containing long-chain alkyl polymer (A), A release film comprising a polymer obtained by reacting a crosslinking agent (B) having a plurality of functional groups capable of reacting with a hydroxyl group, wherein the gel fraction of the release agent layer is 70% by weight or more. May be. In the release film of the present invention, the gel fraction of the release agent layer is preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, and further preferably 95% by weight or more. Is 100% by weight. By aging in the heating step, for example, a release agent layer having such a high gel fraction and high heat resistance is obtained. The gel fraction can be measured by, for example, measuring the weight after separating the release agent layer from the base film, immersing it in tetrahydrofuran, leaving it at 30 ° C. for 72 hours, filtering with a stainless mesh, and drying. The weight of the residue can be measured again and calculated from the weight change rate of the residue. That is, the value obtained by dividing the weight of the residue after drying by the weight of the release agent layer after separation from the substrate film is the gel fraction. However, this measurement method is an example, and the present invention is not limited to this measurement method.
本発明の剥離フィルムの用途は特に限定されないが、例えば、粘着テープ、転写フィルム、離型フィルムなどの、耐熱性および耐溶剤性が要求される用途に特に適している。 The application of the release film of the present invention is not particularly limited, but is particularly suitable for applications requiring heat resistance and solvent resistance, such as pressure-sensitive adhesive tapes, transfer films, and release films.
以下、本発明の実施例について説明する。なお、本発明はこれらの実施例に限定されるものではない。 Examples of the present invention will be described below. The present invention is not limited to these examples.
［製造例１：水酸基を含むビニル重合体］
撹拌機、冷却器、滴下ロートを備えた反応容器中に、ビニルアルコール／酢酸ビニル共重合物(ケン化度８８モル％、平均重合度３００）３５．３重量部、トルエン４０重量部、ジメチルスルホキシド８５部、ジブチルスズジラウレート０．１部を添加し、攪拌しながら、９０℃に加温した。さらに、オクタデシルイソシアネートを１３０．８重量部（前記活性水素含有高分子の水酸基に対し７０モル％）加えた。反応進行に伴い、前記ビニルアルコール／酢酸ビニル共重合物の粒子が溶解した。このビニルアルコール／酢酸ビニル共重合物の粒子が完全に溶解してから、さらに２時間反応を続けた後、８０℃まで冷却し、反応混合物を５倍量のメタノール中へ注いで白色沈殿物を得た。この沈殿物をメタノールで洗浄し、乾燥粉砕して目的の水酸基含有長鎖アルキルポリマー（Ａ）を得た。
[Production Example 1: Vinyl polymer containing hydroxyl group]
In a reaction vessel equipped with a stirrer, a cooler and a dropping funnel, 35.3 parts by weight of vinyl alcohol / vinyl acetate copolymer (saponification degree 88 mol%, average polymerization degree 300), toluene 40 parts by weight, dimethyl sulfoxide 85 parts and dibutyltin dilaurate 0.1 part were added, and it heated at 90 degreeC, stirring. Further, 130.8 parts by weight of octadecyl isocyanate (70 mol% with respect to the hydroxyl group of the active hydrogen-containing polymer) was added. As the reaction progressed, the vinyl alcohol / vinyl acetate copolymer particles were dissolved. After the particles of the vinyl alcohol / vinyl acetate copolymer are completely dissolved, the reaction is continued for another 2 hours, and then cooled to 80 ° C., and the reaction mixture is poured into 5 times amount of methanol to form a white precipitate. Obtained. This precipitate was washed with methanol, dried and pulverized to obtain the desired hydroxyl group-containing long-chain alkyl polymer (A).
［実施例１］
製造例１で得られた水酸基含有長鎖アルキルポリマー（Ａ）（１００重量部）、トルエン（５０００重量部）、ジブチルスズジラウレート（０．１重量部）を、６０℃で、固形物が全て溶解するまで攪拌した。固形物溶解後の液を４０℃に冷却し、架橋剤（Ｂ）としてデュラネートＴＰＡ−１００（ＨＤＩイソシアヌレート、旭化成ケミカルズ製）を７重量部添加し、溶解させた。その液（剥離剤層形成用組成物）を、膜厚が２５μｍの未処理ＰＥＴフィルム（基材フィルム）にワイヤーバーを用いて塗布（塗工）し、１００℃で１分乾燥させた。塗布厚は約０．１μｍであった。塗布および乾燥後の前記フィルムを、前記５０℃の加熱炉に入れ、２４時間熟成させた。
[Example 1]
The solid group-containing long-chain alkyl polymer (A) (100 parts by weight), toluene (5000 parts by weight), and dibutyltin dilaurate (0.1 parts by weight) obtained in Production Example 1 are all dissolved at 60 ° C. Until stirred. The liquid after dissolution of the solid was cooled to 40 ° C., and 7 parts by weight of Duranate TPA-100 (HDI isocyanurate, manufactured by Asahi Kasei Chemicals) was added and dissolved as a crosslinking agent (B). The liquid (the composition for forming the release agent layer) was applied (coated) to an untreated PET film (base film) having a film thickness of 25 μm using a wire bar, and dried at 100 ° C. for 1 minute. The coating thickness was about 0.1 μm. The film after coating and drying was placed in the heating furnace at 50 ° C. and aged for 24 hours.
［実施例２］
デュラネートＴＰＡ−１００（ＨＤＩイソシアヌレート、旭化成ケミカルズ製）の添加量を１４部に変更した以外は実施例１と同様の剥離フィルムを得た。
[Example 2]
A release film similar to that of Example 1 was obtained except that the addition amount of Duranate TPA-100 (HDI isocyanurate, manufactured by Asahi Kasei Chemicals) was changed to 14 parts.
［実施例３］
トルエン（５０００重量部）に代えてトルエン（４５００重量部）およびＮ-メチル-2-ピロリドン（５００重量部）を用いた以外は実施例１と同様にして剥離フィルムを得た。
[Example 3]
A release film was obtained in the same manner as in Example 1 except that toluene (4500 parts by weight) and N-methyl-2-pyrrolidone (500 parts by weight) were used instead of toluene (5000 parts by weight).
［実施例４］
デュラネートＴＰＡ−１００（ＨＤＩイソシアヌレート、旭化成ケミカルズ製）の添加量を１．４部に変更した以外は実施例１と同様にして剥離フィルムを得た。
[Example 4]
A release film was obtained in the same manner as in Example 1 except that the amount of Duranate TPA-100 (HDI isocyanurate, manufactured by Asahi Kasei Chemicals) was changed to 1.4 parts.
［実施例５］
架橋剤（Ｂ）として、デュラネートＴＰＡ−１００（ＨＤＩイソシアヌレート、旭化成ケミカルズ製）に代えてコロネートＬ（ＴＤＩ系変性物、日本ポリウレタン製）を用いた以外は実施例１と同様にして剥離フィルムを得た。
[Example 5]
A release film was prepared in the same manner as in Example 1 except that Coronate L (TDI-based modified product, manufactured by Nippon Polyurethane) was used in place of Duranate TPA-100 (HDI isocyanurate, manufactured by Asahi Kasei Chemicals) as the crosslinking agent (B). Obtained.
［比較例１］
前記フィルムに対し、５０℃で２４時間の熟成を行わない（塗布および乾燥のみを行う）こと以外は実施例１と同様にして剥離フィルムを得た。
[Comparative Example 1]
A release film was obtained in the same manner as in Example 1 except that the film was not aged for 24 hours at 50 ° C. (only coating and drying were performed).
［比較例２］
製造例１で得られた水酸基含有長鎖アルキルポリマー（Ａ）および架橋剤（Ｂ）に代えて、酢酸ビニル／ビニルアルコール重合体をオクタデシルイソシアネートと反応させた水酸基を含まない剥離処理剤を用いることと、５０℃で２４時間の熟成を行わない（塗布および乾燥のみを行う）こと以外は、実施例１と同様にして塗工フィルムを得た。
[Comparative Example 2]
Instead of the hydroxyl group-containing long-chain alkyl polymer (A) and the crosslinking agent (B) obtained in Production Example 1, a release treatment agent containing no hydroxyl group obtained by reacting a vinyl acetate / vinyl alcohol polymer with octadecyl isocyanate is used. A coated film was obtained in the same manner as in Example 1 except that aging was not performed at 50 ° C. for 24 hours (only coating and drying were performed).
［比較例３］
製造例１で得られた水酸基含有長鎖アルキルポリマー（Ａ）および架橋剤（Ｂ）に代えて、エチレン／ビニルアルコール重合体をオクタデシルイソシアネートと反応させた水酸基を含まない剥離処理剤を用いることと、５０℃で２４時間の熟成を行わない（塗布および乾燥のみを行う）こと以外は、実施例１と同様にして塗工フィルムを得た。
[Comparative Example 3]
In place of the hydroxyl group-containing long-chain alkyl polymer (A) and the crosslinking agent (B) obtained in Production Example 1, a release treatment agent containing no hydroxyl group obtained by reacting an ethylene / vinyl alcohol polymer with octadecyl isocyanate is used. A coated film was obtained in the same manner as in Example 1 except that aging was not performed at 50 ° C. for 24 hours (only coating and drying were performed).
［フィルムの評価方法］
以下の方法により、実施例および比較例で製造した各剥離フィルムの特性を評価した。
[Film evaluation method]
The characteristics of each release film produced in Examples and Comparative Examples were evaluated by the following methods.
剥離力
評価対象の剥離フィルムに、幅２５ｍｍのアクリル系粘着テープ（製品名ポリエステルテープ３１Ｂ、日東電工製）を２ｋｇのゴムローラーで圧着して貼り付け、２３℃、５０％ＲＨの雰囲気下で１００ｇ／ｃｍ２の荷重をかけ、２時間放置し、３００ｃｍ／ｍｉｎの速度で剥離力を測定した。剥離力が小さい程、剥離性能が優れていることを示す。
A 25 mm wide acrylic adhesive tape (product name: Polyester tape 31B, manufactured by Nitto Denko) is attached to a release film subject to peel force evaluation with a 2 kg rubber roller, and 100 g in an atmosphere of 23 ° C. and 50% RH. / applying a load of cm 2, for 2 hours, it was measured the peel force at a rate of 300 cm / min. The smaller the peeling force, the better the peeling performance.
耐熱性
上記で圧着した試料を１５０℃の熱風乾燥器に９０分間放置し、２３℃で放冷後、上記と同じ条件で剥離力を測定した。
Heat resistance The sample pressure-bonded as described above was left in a hot air dryer at 150 ° C. for 90 minutes, allowed to cool at 23 ° C., and then the peel force was measured under the same conditions as above.
残留接着率
上記剥離力測定時と同じ条件で作製し、剥離した試験片を、ステンレス板に２ｋｇのゴムローラーで圧着し、貼り付けた。その剥離フィルムを、２３℃、５０％ＲＨの雰囲気下で２時間放置し、３００ｃｍ／ｍｉｎの速度で接着力Ａを側置した。一方、ステンレス板に、アクリル系粘着テープ（製品名ポリエステルテープ３１Ｂ、日東電工製）を、上記剥離力測定時と同じ条件で圧着して貼り付け、３００ｃｍ／ｍｉｎの速度で接着力Ｂを測定した。その後、接着力Ａ／接着力Ｂ×１００の式により残留接着率を算出した。残留接着率が高いほど、剥離剤の粘着剤への移行が小さいことを示す。
Residual Adhesion Rate The test piece prepared and peeled off under the same conditions as in the above-described peeling force measurement was bonded to a stainless steel plate with a 2 kg rubber roller. The release film was allowed to stand for 2 hours in an atmosphere of 23 ° C. and 50% RH, and the adhesive force A was placed on the side at a speed of 300 cm / min. On the other hand, an acrylic pressure-sensitive adhesive tape (product name: Polyester tape 31B, manufactured by Nitto Denko) was bonded to a stainless steel plate under the same conditions as those for measuring the peeling force, and the adhesive force B was measured at a speed of 300 cm / min. . Thereafter, the residual adhesion rate was calculated by the formula of adhesive force A / adhesive force B × 100. The higher the residual adhesion rate, the smaller the transfer of the release agent to the pressure-sensitive adhesive.
ゲル分率
評価対象の剥離フィルムにおける剥離剤層を基材フィルムから剥がし、前記剥離剤層をテトラヒドロフランに浸漬し、３０℃×７２時間放置し、ステンレスメッシュでろ過し、残査の重量変化率からゲル分率を算出した。また、ゲル分率が高いほど、前記剥離剤層が溶剤に溶解しにくいこと、すなわち、前記剥離剤層が耐溶剤性に優れていることを示す。
The release agent layer in the release film subject to gel fraction evaluation is peeled off from the base film, the release agent layer is immersed in tetrahydrofuran, left at 30 ° C. for 72 hours, filtered through a stainless mesh, and the weight change rate of the residue The gel fraction was calculated. Moreover, it shows that the said releasing agent layer is hard to melt | dissolve in a solvent, ie, the said releasing agent layer is excellent in solvent resistance, so that a gel fraction is high.
また、参考として、剥離剤層形成用組成物（塗工液）の液安定性も評価した。すなわち、各実施例および比較例で用いた剥離剤層形成用組成物（塗工液）を、２０℃または４０℃でそれぞれ２４時間放置し、その後の状態を目視で評価した。なお、前記各剥離剤層形成用組成物（塗工液）は、ポリマー濃度が約２重量％である。 For reference, the liquid stability of the release agent layer forming composition (coating liquid) was also evaluated. That is, the release agent layer forming composition (coating solution) used in each Example and Comparative Example was allowed to stand at 20 ° C. or 40 ° C. for 24 hours, and the subsequent state was evaluated visually. The release agent layer forming composition (coating liquid) has a polymer concentration of about 2% by weight.
上記評価方法による評価結果を、下記表１にまとめて示す。
上記表１に示したとおり、５０℃で２４時間の加熱工程（熟成）を行った実施例１〜５は、１５０℃熱処理後の剥離力(N/25mm)がいずれも低く、１５０℃熱処理後であっても剥離性能が優れていることが確認された。特に、実施例１〜３は、実施例４および５に対し、さらに、１５０℃熱処理後の剥離力（耐熱性）が優れていた。なお、架橋剤（Ｂ）として、実施例１〜４では、１分子内にイソシアネート基を３つ有するＨＤＩイソシアヌレートを用いたが、前述のとおり、実施例４は、実施例１〜３と比較して架橋剤（Ｂ）の添加量が少ない。また、実施例５では、１分子内にイソシアネート基を２つ有するＴＤＩ系変性物を用いた。 As shown in Table 1 above, Examples 1 to 5, which were subjected to a heating process (aging) at 50 ° C. for 24 hours, all had low peel strength (N / 25 mm) after 150 ° C. heat treatment, and after 150 ° C. heat treatment Even so, it was confirmed that the peeling performance was excellent. In particular, Examples 1 to 3 were superior to Examples 4 and 5 in terms of peel strength (heat resistance) after heat treatment at 150 ° C. In Examples 1-4, HDI isocyanurate having three isocyanate groups in one molecule was used as the crosslinking agent (B). However, as described above, Example 4 was compared with Examples 1-3. Thus, the amount of the crosslinking agent (B) added is small. In Example 5, a TDI modified product having two isocyanate groups in one molecule was used.
一方、５０℃で２４時間の加熱工程（熟成）を行わなかった比較例１〜３は、実施例１〜５と比較すると、１５０℃熱処理後の剥離力(N/25mm)がいずれもきわめて高く、剥離性能が低下していた。 On the other hand, Comparative Examples 1 to 3 in which the heating process (aging) at 50 ° C. for 24 hours was not performed, the peel strength (N / 25 mm) after heat treatment at 150 ° C. was extremely high as compared with Examples 1 to 5. The peeling performance was deteriorated.
また、上記表１に示したとおり、５０℃で２４時間の加熱工程（熟成）を行った実施例１〜５は、残留接着率が９０〜９８％と、いずれもきわめて高かった。これに対し、５０℃で２４時間の加熱工程（熟成）を行わない比較例１〜３は、残留接着力が３４〜３５％と低かった。 Moreover, as shown in the said Table 1, Examples 1-5 which performed the heating process (ripening) for 24 hours at 50 degreeC had 90-98% of the residual adhesive rate, and all were very high. On the other hand, Comparative Examples 1 to 3 in which the heating step (aging) for 24 hours at 50 ° C. was as low as 34 to 35% in the residual adhesive force.
さらに、上記表１に示したとおり、５０℃で２４時間の加熱工程（熟成）を行った実施例１〜５は、剥離剤層のゲル分率がいずれもきわめて高く、優れた耐溶剤性を有することが示された。これに対し、５０℃で２４時間の加熱工程（熟成）を行わない比較例１〜３は、剥離剤層のゲル分率がほぼ０％であり、耐溶剤性が低かった。 Furthermore, as shown in Table 1 above, Examples 1 to 5 which were subjected to a heating step (aging) at 50 ° C. for 24 hours had extremely high gel fractions in the release agent layer, and had excellent solvent resistance. It was shown to have. On the other hand, Comparative Examples 1 to 3 in which the heating step (aging) for 24 hours at 50 ° C. was performed, the gel fraction of the release agent layer was almost 0%, and the solvent resistance was low.
以上、説明したとおり、本発明の製造方法によれば、１００℃を超える高温条件下でも剥離力上昇（剥離性の低下）が小さく、かつ、剥離剤層の耐溶剤性に優れた剥離フィルムを製造可能である。また、本発明の剥離フィルムは、前記本発明の製造方法により製造されることで、１００℃を超える高温条件下でも剥離力上昇（剥離性の低下）が小さく、かつ、剥離剤層の耐溶剤性に優れている。本発明の剥離フィルムの用途は特に限定されないが、例えば、粘着テープ、転写フィルム、離型フィルムなどの、耐熱性および耐溶剤性が要求される用途に特に適している。 As described above, according to the production method of the present invention, a release film having a small increase in peel strength (decrease in peelability) even under high temperature conditions exceeding 100 ° C. and excellent in solvent resistance of the release agent layer is obtained. It can be manufactured. In addition, the release film of the present invention is produced by the production method of the present invention, so that the increase in peel force (decrease in peelability) is small even under high temperature conditions exceeding 100 ° C., and the solvent resistance of the release agent layer Excellent in properties. The application of the release film of the present invention is not particularly limited, but is particularly suitable for applications requiring heat resistance and solvent resistance, such as pressure-sensitive adhesive tapes, transfer films, and release films.
Claims (15)
前記基材フィルムの、前記剥離剤層が形成される剥離剤層形成面に、水酸基含有長鎖アルキルポリマー（Ａ）と、水酸基と反応可能な官能基を複数有する架橋剤（Ｂ）とを含む剥離剤層形成用組成物を塗工する塗工工程と、
前記塗工工程後、前記剥離剤層形成面上で前記剥離剤層形成用組成物を６０〜１５０℃で加熱して前記水酸基含有長鎖アルキルポリマー（Ａ）と前記架橋剤（Ｂ）とを反応させて架橋体を形成させる架橋体形成工程と、
前記架橋体形成工程後、前記剥離剤層形成面上で前記剥離剤層形成用組成物を３５〜６０℃の温度で１２〜１７０時間加熱する加熱工程と、
を含むことを特徴とする製造方法。 A method for producing a release film in which a release agent layer is formed on at least one side of a base film,
The release agent layer forming surface on which the release agent layer is formed of the base film contains a hydroxyl group-containing long-chain alkyl polymer (A) and a crosslinking agent (B) having a plurality of functional groups capable of reacting with hydroxyl groups. A coating process for coating the release agent layer-forming composition;
After the coating step, the release agent layer-forming composition is heated on the release agent layer forming surface at 60 to 150 ° C. to obtain the hydroxyl group-containing long-chain alkyl polymer (A) and the crosslinking agent (B). A crosslinked body forming step of reacting to form a crosslinked body;
After the crosslinked body forming step, a heating step of heating the release agent layer forming composition on the release agent layer forming surface at a temperature of 35 to 60 ° C. for 12 to 170 hours ;
The manufacturing method characterized by including.
Ｒ１は、直鎖または分枝アルキル基であり、
前記水酸基含有長鎖アルキルポリマー（Ａ）の主鎖炭素原子数に対し、前記化学式（２）で表される構造に由来する主鎖炭素原子の数が２５％以下である、
ことを特徴とする請求項１から６のいずれか一項に記載の製造方法。 The hydroxyl group-containing long-chain alkyl polymer (A) further includes a structure represented by the following chemical formula (2):
R 1 is a linear or branched alkyl group,
The number of main chain carbon atoms derived from the structure represented by the chemical formula (2) is 25% or less with respect to the number of main chain carbon atoms of the hydroxyl group-containing long-chain alkyl polymer (A).
The manufacturing method according to any one of claims 1 to 6, wherein:
前記水酸基含有長鎖アルキルポリマー（Ａ）の主鎖炭素原子数に対し、前記化学式（３）で表される構造に由来する主鎖炭素原子の数が９０％以下である請求項１から７のいずれか一項に記載の製造方法。 The hydroxyl group-containing long-chain alkyl polymer (A) further contains an ethylene group represented by the following chemical formula (3),
The number of main chain carbon atoms derived from the structure represented by the chemical formula (3) is 90% or less with respect to the number of main chain carbon atoms of the hydroxyl group-containing long chain alkyl polymer (A). The manufacturing method as described in any one.
Ｒ２は、直鎖または分枝脂肪族炭化水素基であり、
Ｌは、単結合または任意の原子団である請求項１から８のいずれか一項に記載の製造方法。 The hydroxyl group-containing long-chain alkyl polymer (A) further includes a structure represented by the following chemical formula (4),
R 2 is a straight chain or branched aliphatic hydrocarbon group,
L is a single bond or arbitrary atomic groups, The manufacturing method as described in any one of Claim 1 to 8.
さらに、前記塗工工程後に前記溶剤を揮発させて前記剥離剤層形成用組成物を乾燥させる乾燥工程を含む請求項１から１２のいずれか一項に記載の製造方法。 The release agent layer forming composition further contains a solvent,
Furthermore, the manufacturing method as described in any one of Claim 1 to 12 including the drying process which volatilizes the said solvent after the said application | coating process and dries the said release agent layer forming composition.
前記剥離剤層が、水酸基含有長鎖アルキルポリマー（Ａ）と、水酸基と反応可能な官能基を複数有する架橋剤（Ｂ）とを反応させて得られるポリマーを含み、
前記剥離剤層のゲル分率が７０重量％以上であることを特徴とする剥離フィルム。 A release film having a release agent layer formed on at least one side of a base film,
The release agent layer includes a polymer obtained by reacting a hydroxyl group-containing long-chain alkyl polymer (A) with a crosslinking agent (B) having a plurality of functional groups capable of reacting with a hydroxyl group,
A release film, wherein the release agent layer has a gel fraction of 70% by weight or more.
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