JP4571417B2 - Laminated film with an easy adhesion layer - Google Patents
Laminated film with an easy adhesion layer Download PDFInfo
- Publication number
- JP4571417B2 JP4571417B2 JP2004041392A JP2004041392A JP4571417B2 JP 4571417 B2 JP4571417 B2 JP 4571417B2 JP 2004041392 A JP2004041392 A JP 2004041392A JP 2004041392 A JP2004041392 A JP 2004041392A JP 4571417 B2 JP4571417 B2 JP 4571417B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesion layer
- easy
- epoxy
- group
- laminated film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- -1 vinyl aromatic compound Chemical class 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 31
- 229920006267 polyester film Polymers 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 19
- 229920001400 block copolymer Polymers 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 229920000178 Acrylic resin Polymers 0.000 claims description 8
- 239000004925 Acrylic resin Substances 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 5
- 229920001225 polyester resin Polymers 0.000 claims description 5
- 239000004645 polyester resin Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 42
- 239000010408 film Substances 0.000 description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 229920005862 polyol Polymers 0.000 description 11
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 10
- 238000001723 curing Methods 0.000 description 10
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000006735 epoxidation reaction Methods 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 150000002432 hydroperoxides Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 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
- 238000011282 treatment Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QTYUSOHYEPOHLV-FNORWQNLSA-N 1,3-Octadiene Chemical compound CCCC\C=C\C=C QTYUSOHYEPOHLV-FNORWQNLSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- XYPISWUKQGWYGX-UHFFFAOYSA-N 2,2,2-trifluoroethaneperoxoic acid Chemical compound OOC(=O)C(F)(F)F XYPISWUKQGWYGX-UHFFFAOYSA-N 0.000 description 1
- OJMJOSRCBAXSAQ-UHFFFAOYSA-N 2,2-dibutylpropane-1,3-diol Chemical compound CCCCC(CO)(CO)CCCC OJMJOSRCBAXSAQ-UHFFFAOYSA-N 0.000 description 1
- AQJBTVUWDXWSGQ-UHFFFAOYSA-N 2,2-dihexylpropane-1,3-diol Chemical compound CCCCCCC(CO)(CO)CCCCCC AQJBTVUWDXWSGQ-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
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- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
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- 125000003006 2-dimethylaminoethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- KEUDFEHZLMMIHD-UHFFFAOYSA-N 2-ethyl-2-hexylpropane-1,3-diol Chemical compound CCCCCCC(CC)(CO)CO KEUDFEHZLMMIHD-UHFFFAOYSA-N 0.000 description 1
- VNAWKNVDKFZFSU-UHFFFAOYSA-N 2-ethyl-2-methylpropane-1,3-diol Chemical compound CCC(C)(CO)CO VNAWKNVDKFZFSU-UHFFFAOYSA-N 0.000 description 1
- WIVDTFSOBMXIMK-UHFFFAOYSA-N 2-hexyl-2-methylpropane-1,3-diol Chemical compound CCCCCCC(C)(CO)CO WIVDTFSOBMXIMK-UHFFFAOYSA-N 0.000 description 1
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- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- JOZHCQBYRBGYAJ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 JOZHCQBYRBGYAJ-UHFFFAOYSA-M 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical class NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 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
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 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
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005903 polyol mixture Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- 229950006800 prenderol Drugs 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 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 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 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 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、インキ、接着剤等の密着性、特にＵＶ硬化型樹脂に対してＵＶ照射後のみならずＵＶ照射前も密着性を有する透明性に優れた易接着ポリエステルフィルムに関する。 The present invention relates to an easily-adhesive polyester film excellent in transparency such as adhesion of inks, adhesives and the like, in particular, adhesion to a UV curable resin not only after UV irradiation but also before UV irradiation.
ポリエステルフィルム、特にポリエチレンテレフテレートやポリエチレンナフタレートの二軸延伸フィルムは、優れた機械的性質、耐熱性、耐薬品性、透明性を有するため、磁気テープ、写真フィルム、包装フィルム、電子部品用フィルム、光学用フィルム、表面保護フィルム等の素材として幅広く用いられている。これらのフィルムは、磁性層、感光層、保護層、中間層、着色層等を積層して、別の被着体へ接着または粘着により貼付し使用されることが多い。最近、特に光学用途として、ディスプレイ（ＬＣＤやＣＲＴ）の画面保護の目的で、ハードコート層を積層し、さらに反射防止層、汚れ防止層を積層したポリエステルフィルムが、ディスプレイ表面に貼付され使用されている。一般にハードコート層を構成する成分は、ポリエステルフィルムに対する密着性が低いので、ハードコート層を積層する際、ポリエステルフィルム面上には表面処理がなされてきた。この表面処理としては、コロナ処理等の物理的処理が知られているが、これらの処理を行なっても、ハードコート剤等の密着性は不十分であった。また、ハードコート層を積層したポリエステルフィルムを過酷な環境条件、例えば急激な温度変化（熱衝撃）の環境で使用すると、ハードコート層とフィルム層の密着力が低下し剥がれる場合があった。また積層するハードコート層の樹脂成分によっても密着性低下が起こり、十分満足できるものではなかった。 Polyester films, especially biaxially stretched films of polyethylene terephthalate and polyethylene naphthalate, have excellent mechanical properties, heat resistance, chemical resistance, and transparency. For magnetic tapes, photographic films, packaging films, and electronic parts. It is widely used as a material for films, optical films, surface protective films and the like. These films are often used by laminating a magnetic layer, a photosensitive layer, a protective layer, an intermediate layer, a colored layer, and the like, and affixing or sticking to another adherend. Recently, a polyester film with a hard coat layer laminated and an antireflection layer and antifouling layer laminated on the display surface has been used for the purpose of protecting the screen of displays (LCD and CRT), especially for optical applications. Yes. In general, the components constituting the hard coat layer have low adhesion to the polyester film, and therefore, when the hard coat layer is laminated, surface treatment has been performed on the polyester film surface. As this surface treatment, physical treatment such as corona treatment is known, but even when these treatments are performed, the adhesion of a hard coat agent or the like is insufficient. Further, when a polyester film having a hard coat layer laminated thereon is used under severe environmental conditions, for example, in an environment of rapid temperature change (thermal shock), the adhesion between the hard coat layer and the film layer may be reduced and peeled off. In addition, the adhesiveness was lowered by the resin component of the hard coat layer to be laminated, and it was not fully satisfactory.
層間の密着性を向上させる方法として、基材フィルム上に、ビニル芳香族化合物を主体とする重合体ブロック（Ａ）と、共役ジエン化合物を主体とする重合体ブロック（Ｂ）とからなるブロック共重合体もしくはその部分水素添加物であって、共役ジエンの炭素−炭素二重結合がエポキシ化されたエポキシ変性ブロック重合体を、易接着層として形成しておき、この易接着層上に目的とする層を積層する方法がある（例えば特許文献１参照）。しかしながら、この易接着層上に、例えば、ハードコート層を構成するＵＶ硬化型樹脂層や、ダイシングテープ等に使われるＵＶ硬化型粘着剤層を形成した場合、ＵＶ照射前では、ＵＶ硬化層と基材フィルムとの密着性が良好でないことがあり、その改良が求められていた。
本発明の目的は、かかる従来技術の問題を解消し、インキや接着剤、特にハードコート剤に代表されるＵＶ硬化型樹脂に対し、硬化前の密着性に優れかつ、硬化後もその密着性が低下しない易接着層を有するポリエステルフィルムを提供することである。 The object of the present invention is to solve such problems of the prior art, and is excellent in adhesion before curing and also after curing to inks and adhesives, particularly UV curable resins represented by hard coating agents. It is providing the polyester film which has an easily bonding layer which does not fall.
本発明者は、これらの問題を解決すべく鋭意検討した結果、基材であるポリエステルフィルム上に、特定の成分からなる易接着層を設けることで、解決できることを見出し、本発明を完成した。 As a result of intensive studies to solve these problems, the present inventor has found that the problem can be solved by providing an easy-adhesion layer comprising a specific component on a polyester film as a substrate, and has completed the present invention.
すなわち、本発明の要旨は、ポリエステルフィルム上に、少なくとも一層の易接着層を介してＵＶ硬化型樹脂層を設けてなる積層フィルムであって、前記易接着層はビニル芳香族化合物を主体とする重合体ブロック（Ａ）と、共役ジエン化合物を主体とする重合体ブロック（Ｂ）とからなるブロック共重合体またはその部分水素添加物であり、前記共役ジエンの炭素−炭素二重結合がエポキシ化されたエポキシ変性ブロック重合体で構成され、かつ前記易接着層が、アクリル樹脂、ポリエステル樹脂、ウレタン樹脂から選ばれる少なくとも一種のバインダーを１０〜７０質量％含有することを特徴とする積層フィルムである。 That is, the gist of the present invention is a laminated film in which a UV curable resin layer is provided on a polyester film via at least one easy-adhesion layer, and the easy-adhesion layer is mainly composed of a vinyl aromatic compound. a polymer block (a), a block copolymer or partially hydrogenated product thereof consisting of a polymer block composed mainly of a conjugated diene compound (B), carbon of the conjugated diene - carbon double bond is epoxidized A laminated film characterized in that it is composed of an epoxy-modified block polymer, and the easy-adhesion layer contains 10 to 70% by mass of at least one binder selected from an acrylic resin, a polyester resin, and a urethane resin. .
本発明の積層フィルムは、易接着層に特定のバインダーが添加されているため、ＵＶ硬化型樹脂層との密着性に優れ、ＵＶ照射後の密着性を損なうことなく、ＵＶ硬化型樹脂層形成後のＵＶ照射前の初期密着性を改善することが出来る。 In the laminated film of the present invention, since a specific binder is added to the easy-adhesion layer, it has excellent adhesion to the UV curable resin layer, and without damaging the adhesion after UV irradiation, the UV curable resin layer can be formed. The initial adhesiveness before the subsequent UV irradiation can be improved.
以下、本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明におけるポリエステルフィルムを構成するポリエステルとは、芳香族二塩基酸またはそのエステル形成性誘導体とジオールまたはそのエステル形成性誘導体とから重縮合して得られる線状飽和ポリエステルである。ポリエステルの具体例としては、ポリエチレンテレフタレート、ポリエチレンイソフタレート、ポリブチレンテレフテレート、ポリエチレン−２，６ナフタレンジカルボキシレート等が挙げられ、これらの共重合体またはこれと小割合の他樹脂とのブレンド物等も含まれる。 The polyester constituting the polyester film in the present invention is a linear saturated polyester obtained by polycondensation from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. Specific examples of the polyester include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, polyethylene-2,6 naphthalene dicarboxylate, and the like. These copolymers or blends thereof with a small proportion of other resins. Things are also included.
ポリエステルフィルムは、従来から知られている方法で製造することができる。例えば、二軸延伸ポリエステルフィルムは、ポリエステルを乾燥後、Ｔｍ〜（Ｔｍ＋７０）℃の温度（Ｔｍ：ポリエステルの融点）で押出機にて溶融し、ダイ（例えばＴ−ダイ、Ｉ−ダイ等）から回転冷却ドラム上に押出し、４０〜９０℃で急冷して未延伸フィルムを製造し、ついで該未延伸フィルムを（Ｔｇ−１０）〜（Ｔｇ＋７０）℃の温度（Ｔｇ：ポリエステルのガラス転移温度）で縦方向に２．５〜８．０倍の倍率で延伸し、横方向に２．５〜８．０倍の倍率で延伸し、必要に応じて１８０〜２５０℃の温度で１〜６０秒間熱固定することにより製造できる。 The polyester film can be produced by a conventionally known method. For example, the biaxially stretched polyester film is obtained by drying the polyester, melting it with an extruder at a temperature of Tm to (Tm + 70) ° C. (Tm: melting point of the polyester), and from a die (for example, T-die, I-die). Extruded onto a rotating cooling drum, rapidly cooled at 40 to 90 ° C. to produce an unstretched film, and then the unstretched film was heated at a temperature of (Tg-10) to (Tg + 70) ° C. (Tg: glass transition temperature of polyester). Stretch in the longitudinal direction at a magnification of 2.5 to 8.0 times, stretch in the transverse direction at a magnification of 2.5 to 8.0 times, and heat for 1 to 60 seconds at a temperature of 180 to 250 ° C. as necessary. It can be manufactured by fixing.
フィルムの厚みは５〜２５０μｍの範囲が好ましい。フィルムの厚みが５μｍ未満であると高温域での耐変形性（寸法安定性）に劣り、また２５０μｍを超えると剛性が高すぎるという問題がある。 The thickness of the film is preferably in the range of 5 to 250 μm. When the thickness of the film is less than 5 μm, there is a problem that the deformation resistance (dimensional stability) in a high temperature range is inferior, and when it exceeds 250 μm, the rigidity is too high.
また必要により、ポリエステルフィルムに適当なフィラーを含有させることができる。このフィラーとしては、従来ポリエステルフィルムの滑り性付与剤として知られているものが挙げられ、その具体例としては、炭酸カルシウム、酸化カルシウム、酸化アルミニウム、シリカ、カオリン、酸化珪素、酸化亜鉛、カーボンブラック、炭化珪素、酸化錫、架橋アクリル樹脂粒子、架橋ポリスチレン樹脂粒子、メラミン樹脂粒子、架橋シリコーン樹脂粒子等が挙げられる。さらにポリエステル中には、着色剤、帯電防止剤、酸化防止剤、有機滑剤、触媒なども適宜添加することができる。 If necessary, an appropriate filler can be contained in the polyester film. Examples of the filler include those conventionally known as slipperiness imparting agents for polyester films, and specific examples thereof include calcium carbonate, calcium oxide, aluminum oxide, silica, kaolin, silicon oxide, zinc oxide, and carbon black. , Silicon carbide, tin oxide, crosslinked acrylic resin particles, crosslinked polystyrene resin particles, melamine resin particles, crosslinked silicone resin particles, and the like. Further, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and the like can be appropriately added to the polyester.
本発明の積層フィルムは、上記ポリエステルフィルム上に少なくとも一層易接着層を有する。この易接着層は、エポキシ変性ブロック重合体で構成され、さらに易接着層は、アクリル樹脂、ポリエステル樹脂、ウレタン樹脂から選ばれるバインダーを少なくとも一種含有するものである。そして前記エポキシ変性ブロック重合体は、ビニル芳香族化合物を主体とする重合体ブロック（Ａ）と、共役ジエン化合物を主体とする重合体ブロック（Ｂ）とからなるブロック共重合体またはその部分水素添加物であり、前記共役ジエンの炭素−炭素二重結合がエポキシ化された重合体である。 The laminated film of the present invention has at least one easy-adhesion layer on the polyester film. This easy-adhesion layer is composed of an epoxy-modified block polymer, and the easy-adhesion layer contains at least one binder selected from acrylic resins, polyester resins, and urethane resins. The epoxy-modified block polymer is a block copolymer comprising a polymer block (A) mainly composed of a vinyl aromatic compound and a polymer block (B) mainly composed of a conjugated diene compound, or a partial hydrogenation thereof. And a polymer in which the carbon-carbon double bond of the conjugated diene is epoxidized.
本発明においてブロック共重合体は、ビニル芳香族化合物を主体とする重合体ブロック（Ａ）と、共役ジエン化合物を主体とする重合体ブロック（Ｂ）とからなるブロック共重合体であり、ビニル芳香族化合物と共役ジエン化合物の共重合比は５／９５〜７０／３０、特に１０／９０〜６０／４０が好ましい。共重合比がこの範囲を超えると塗膜が固くもろくなり、耐久性が低下することがある。 In the present invention, the block copolymer is a block copolymer comprising a polymer block (A) mainly composed of a vinyl aromatic compound and a polymer block (B) mainly composed of a conjugated diene compound. The copolymerization ratio of the group compound and the conjugated diene compound is preferably 5/95 to 70/30, particularly preferably 10/90 to 60/40. When the copolymerization ratio exceeds this range, the coating film becomes brittle and durability may be lowered.
重合体ブロック（Ａ）を構成するビニル芳香族化合物としては、例えばスチレン、α−メチルスチレン、ビニルトルエン、ｐ−第３級ブチルスチレン、ジビニルベンゼン、ｐ−メチルスチレン、１，１−ジフェニルスチレン等のうちから１種または２種以上が選択でき、中でもスチレンが好ましい。 Examples of the vinyl aromatic compound constituting the polymer block (A) include styrene, α-methylstyrene, vinyltoluene, p-tertiary butylstyrene, divinylbenzene, p-methylstyrene, 1,1-diphenylstyrene, and the like. One or more can be selected from among them, and styrene is preferable among them.
また、重合体ブロック（Ｂ）を構成する共役ジエン化合物としては、例えば、ブタジエン、イソプレン、１，３−ペンタジエン、２，３−ジメチル−１，３−ブタジエン、ピペリレン、３−ブチル−１，３−オクタジエン、フェニル−１，３−ブタジエン等のうちから１種または２種以上が選ばれ、中でもブタジエン、イソプレン及びこれらの組み合わせが好ましい。 Examples of the conjugated diene compound constituting the polymer block (B) include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3. -One or more types are selected from octadiene, phenyl-1,3-butadiene, etc. Among them, butadiene, isoprene and combinations thereof are preferable.
また、ブロック共重合体の数平均分子量は５０００〜６０００００、好ましくは１００００〜５０００００の範囲であり、分子量分布［重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）］は、１０以下であることが好ましい。数平均分子量が５０００より小さいと塗膜がもろく、タックが生じる可能性があり、６０００００を超える塗剤の粘度が高くなりレベリングが悪化しやすい。また、分子量分布が１０を超えるとタックやブロッキングの問題が生じる。 The number average molecular weight of the block copolymer is in the range of 5,000 to 600,000, preferably 10,000 to 500,000, and the molecular weight distribution [ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn)]. Is preferably 10 or less. When the number average molecular weight is less than 5,000, the coating film becomes brittle and tackiness may occur, and the viscosity of the coating agent exceeding 600,000 tends to be high and the leveling tends to deteriorate. On the other hand, if the molecular weight distribution exceeds 10, problems of tack and blocking occur.
ブロック共重合体の分子構造は、直鎖状、分岐状、放射状、あるいはこれら任意の組み合わせのいずれであってもよい。例えば、Ａ−Ｂ−Ａ、Ｂ−Ａ−Ｂ−Ａ、（Ａ−Ｂ−）4Ｓｉ、Ａ−Ｂ−Ａ−Ｂ−Ａ等の構造が挙げられる。 The molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof. For example, structures such as ABA, BABA, (AB) 4 Si, ABBABA, and the like can be given.
上記ブロック共重合体は、共役ジエンの炭素−炭素二重結合が部分的に水素添加されてもよい。水素添加することによって、耐光性が向上するという効果が得られる。 In the block copolymer, a carbon-carbon double bond of a conjugated diene may be partially hydrogenated. By adding hydrogen, the effect of improving light resistance can be obtained.
本発明において、エポキシ変性ブロック重合体は、ブロック共重合体またはその部分水素添加物の共役ジエンの炭素−炭素二重結合がエポキシ化されたものである。エポキシ化の程度は、次式によって算出されるエポキシ当量（ｇ／equiv）が、１４０〜２７００であることが好ましく、５００〜１５００であることがさらに好ましい。エポキシ当量が１４０未満であるとブロッキングし、ＵＶ硬化型樹脂との密着性が低下する可能性があり、２７００を超えると基材フィルムとの密着性が不十分になることがある。
エポキシ当量＝（１６０００×［エポキシ変性ブロック重合体質量］）／（［臭化水素酸の滴定量（ｍｌ）］×［臭化水素酸のファクター］）
In the present invention, the epoxy-modified block polymer is obtained by epoxidizing a carbon-carbon double bond of a conjugated diene of a block copolymer or a partially hydrogenated product thereof. As for the degree of epoxidation, the epoxy equivalent (g / equiv) calculated by the following formula is preferably 140 to 2700, and more preferably 500 to 1500. When the epoxy equivalent is less than 140, blocking may occur and adhesion with the UV curable resin may be lowered. When the epoxy equivalent exceeds 2,700, adhesion with the substrate film may be insufficient.
Epoxy equivalent = (16000 × [epoxy-modified block polymer mass]) / ([titration amount of hydrobromic acid (ml)] × [factor of hydrobromic acid])
ブロック共重合体の製造方法としては、上記した構造を有するものが製造できればどのような製造方法もとることもできる。例えば、特公昭４０−２３７９８号、特公昭４７−３２５２号、特公昭４８−２４２３号、特願昭４９−１０５９７０号、特願昭５０−２７０９４号、特公昭４６−３２４１５号、特開昭５９−１６６５１８号、特公昭４９−３６９５７号、特公昭４３−１７９７９号、特公昭４６−３２４１５号、特公昭５６−２８９２５号公報に記載された方法により、リチウム触媒等を用いて不活性溶媒中でビニル芳香族化合物−共役ジエン化合物ブロック共重合体を合成することができる。 As a method for producing the block copolymer, any production method can be used as long as a product having the structure described above can be produced. For example, JP-B-40-23798, JP-B-47-3252, JP-B-48-2423, JP-B-49-105970, JP-B-50-27094, JP-B-46-32415, JP-A-59 166518, JP-B-49-36957, JP-B-43-17979, JP-B-46-32415, JP-B-56-28925, in an inert solvent using a lithium catalyst or the like. A vinyl aromatic compound-conjugated diene compound block copolymer can be synthesized.
さらにブロック共重合体を部分水素添加する方法としては、特公昭４２−８７０４号公報、特公昭４３−６６３６号公報、あるいは特開昭５９−１３３２０３号公報に記載された方法により、不活性溶媒中で水素添加触媒の存在下に水素添加する方法が挙げられる。 Furthermore, as a method of partially hydrogenating the block copolymer, a method described in JP-B-42-8704, JP-B-43-6636, or JP-A-59-133203 can be used in an inert solvent. And hydrogenation in the presence of a hydrogenation catalyst.
本発明におけるエポキシ変性ブロック共重合体は、上記のブロック共重合体またはその部分水素添加物を、不活性溶媒中で過酸類、ハイドロパ−オキサイド類などのエポキシ化剤と反応させることにより得ることができる。過酸類としては、過ギ酸、過酢酸、過安息香酸、トリフルオロ過酢酸などが挙げられる。このうち、過酢酸は工業的に大量に製造されており、安価に入手でき、安定度も高いので好ましい。ハイドロパーオキサイド類としては、過酸化水素、ターシャリブチルハイドロパーオキサイド、クメンパーオキサイド等が挙げられる。 The epoxy-modified block copolymer in the present invention can be obtained by reacting the above-mentioned block copolymer or a partially hydrogenated product thereof with an epoxidizing agent such as peracids and hydroperoxides in an inert solvent. it can. Examples of peracids include performic acid, peracetic acid, perbenzoic acid, and trifluoroperacetic acid. Of these, peracetic acid is preferred because it is industrially produced in large quantities, is available at low cost, and has high stability. Examples of hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide, cumene peroxide, and the like.
エポキシ化の際には必要に応じて触媒を用いることができる。例えば、過酸の場合、炭酸ソーダ等のアルカリや硫酸などの酸を触媒として用い得る。また、ハイドロパーオキサイド類の場合、タングステン酸と苛性ソーダの混合物を過酸化水素と、あるいは有機酸を過酸化水素と、あるいはモリブデンヘキサカルボニルをターシャリブチルハイドロパーオキサイドと併用して触媒効果を得ることができる。 In the epoxidation, a catalyst can be used as necessary. For example, in the case of a peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst. In the case of hydroperoxides, a catalytic effect can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl hydroperoxide. Can do.
エポキシ化剤の量に厳密な規制がなく、それぞれの場合における最適量は、使用する個々のエポキシ化剤、所望されるエポキシ化度、使用する個々のブロック共重合体等のごとき可変要因によって決めることができる。 There is no strict regulation of the amount of epoxidizing agent, and the optimum amount in each case depends on variable factors such as the particular epoxidizing agent used, the desired degree of epoxidation, the particular block copolymer used, etc. be able to.
不活性溶媒は、原料粘度の低下や、エポキシ化剤の希釈による安定化などの目的で使用され、過酢酸の場合であれば芳香族化合物、エーテル類、エステル類などが用いられる。特に好ましい溶媒は、ヘキサン、シクロヘキサン、トルエン、ベンゼン、酢酸エチル、四塩化炭素、クロロホルムである。 The inert solvent is used for the purpose of reducing the viscosity of the raw material or stabilizing by diluting the epoxidizing agent. In the case of peracetic acid, aromatic compounds, ethers, esters and the like are used. Particularly preferred solvents are hexane, cyclohexane, toluene, benzene, ethyl acetate, carbon tetrachloride, and chloroform.
エポキシ化反応条件には厳密な規制はない。用いるエポキシ化剤の反応性によって使用できる反応温度域は定まる。例えば、過酢酸についていえば０〜７０℃が好ましく、０℃未満では反応が遅く、７０℃を超えると過酢酸の分解が起こる。又、ハイドロパーオキサイドの１例であるターシャルブチルハイドロパーオキサイド／モリブデン二酸化物ジアセチルアセトナート系では同じ理由で２０〜１５０℃が好ましい。反応混合物の特別な操作は必要なく、例えば混合物を２〜１０時間攪拌すればよい。得られたエポキシ変性共重合体の単離は適当な方法、例えば貧溶媒で沈殿させる方法、重合体を熱水中に攪拌の下で投入し溶媒を蒸留除去する方法、直接脱溶媒法などで行うことができる。 There are no strict regulations on the epoxidation reaction conditions. The reaction temperature range that can be used is determined by the reactivity of the epoxidizing agent used. For example, in the case of peracetic acid, 0 to 70 ° C. is preferable. If it is less than 0 ° C., the reaction is slow, and if it exceeds 70 ° C., decomposition of peracetic acid occurs. Moreover, in the tertiary butyl hydroperoxide / molybdenum dioxide diacetylacetonate system which is an example of hydroperoxide, 20-150 degreeC is preferable for the same reason. No special operation of the reaction mixture is necessary. For example, the mixture may be stirred for 2 to 10 hours. Isolation of the resulting epoxy-modified copolymer is carried out by an appropriate method, for example, a method of precipitating with a poor solvent, a method of adding the polymer to hot water under stirring and distilling off the solvent, or a direct desolvation method. It can be carried out.
本発明において易接着層は、エポキシ変性ブロック重合体とバインダーとから構成されることが必要である。バインダーとしては、アクリル樹脂、ポリエステル樹脂、ウレタン樹脂から選ばれる一種以上が１０〜７０質量％含有されていることが必要である。易接着層におけるバインダーの含有量が１０％未満であると、濡れ性が良好でなく、コートスジが入ったり、粘着剤等の塗膜を形成しときに初期密着性が得られず、乾燥後、指でこすったり、セロテープ（登録商標）を塗膜に貼り付けてはがすと、易接着層上に設けた塗膜が比較的簡単にとれてしまうことがある。バインダーの含有量が７０質量％を超えるとＵＶ照射後の密着性が低下することがある。 In the present invention, the easy-adhesion layer needs to be composed of an epoxy-modified block polymer and a binder. As a binder, 10-70 mass% of 1 or more types chosen from an acrylic resin, a polyester resin, and a urethane resin needs to be contained. If the content of the binder in the easy-adhesion layer is less than 10%, the wettability is not good, coat streaks or initial adhesion cannot be obtained when forming a coating film such as an adhesive, after drying, If you rub with your finger or peel off the adhesive tape (registered trademark) on the coating film, the coating film provided on the easy-adhesion layer may be removed relatively easily. When the content of the binder exceeds 70% by mass, the adhesion after UV irradiation may decrease.
バインダーは、エポキシ基と反応しうる官能基例えば、アミノ基、水酸基、カルボキシル基（カルボン酸無水物も含む）を一種以上有することが好ましい。これらの官能基はエポキシ基と反応するため、分散性、凝集性が高まり透明性を損なうことがないので好ましい。 The binder preferably has at least one functional group capable of reacting with an epoxy group such as an amino group, a hydroxyl group, and a carboxyl group (including a carboxylic acid anhydride). Since these functional groups react with the epoxy group, dispersibility and agglomeration are increased and transparency is not impaired, which is preferable.
バインダーとして使用するアクリル樹脂は、例えば下記のモノマー・オリゴマーを重合して得られるものである。モノマーとしては、アルキルアクリレ−ト、アルキルメタクリレ−ト（アルキル基としてはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、２−エチルヘキシル基、ラウリル基、ステアリル基、シクロヘキシル基、フェニル基、ベンジル基など）が挙げられる。そして上記モノマーを基本骨格とし、更に上記官能基を付与するため、以下の官能基を有するモノマーと共重合される。すなわちカルボキシル基、メチロ−ル基、酸無水物基、スルホン酸基、アミド基あるいはアルキロ−ル化されたアミド基、アミノ基（置換アミノ基を含む）あるいはアルキロ−ル化されたアミノ基、水酸基、エポキシ基などの官能基を有するモノマーを例示することができ、これらの塩、エステル化物を共重合してもよい。具体的には、カルボキシル基を有する化合物としては、アクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマル酸、クロトン酸、これらのアルカリ金属塩、アンモニウム塩、あるいは無水物などが挙げられる。 The acrylic resin used as the binder is obtained by polymerizing the following monomers / oligomers, for example. Monomers include alkyl acrylate, alkyl methacrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl. Group, lauryl group, stearyl group, cyclohexyl group, phenyl group, benzyl group, etc.). And in order to give the said functional group further using the said monomer as a basic skeleton, it is copolymerized with the monomer which has the following functional groups. That is, a carboxyl group, a methylol group, an acid anhydride group, a sulfonic acid group, an amide group, an alkylated amide group, an amino group (including a substituted amino group), an alkylated amino group, or a hydroxyl group And monomers having a functional group such as an epoxy group, and salts and esterified products thereof may be copolymerized. Specifically, examples of the compound having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, their alkali metal salts, ammonium salts, and anhydrides.
バインダーとして使用するポリエステル樹脂は、ジカルボン酸成分と、分岐したグリコール成分を含有するグリコール成分とを構成成分とする樹脂である。分岐したグリコール成分としては、２，２−ジメチル−１，３−プロパンジオール、２−メチル−２−エチル−１，３−プロパンジオール、２−メチル−２−ブチル−１，３−プロパンジオール、２−メチル−２−ｎ−ヘキシル−１，３−プロパンジオール、２，２−ジエチル−１，３−プロパンジオール、２−エチル−２−ｎ−ブチル−１，３−プロパンジオール、２−エチル−２−ｎ−ヘキシル−１，３−プロパンジオール、２，２−ジ−ｎ−ブチル−１，３−プロパンジオール、および２，２−ジ−ｎ−ヘキシル−１，３−プロパンジオールなどが挙げられる。分岐したグリコール成分は、全グリコール成分の中に１０モル％以上の割合で含有されることが好ましく、更に２０モル％以上の割合で含有されることが好ましい。上記の分岐したグリコール成分以外のグリコール成分としては、エチレングリコールが最も好ましい。また、少量であればジエチレングリコール、プロピレングリコール、ブタンジオール、ヘキサンジオールまたは１，４−シクロヘキサンジメタノールなどを用いてもよい。 The polyester resin used as the binder is a resin having a dicarboxylic acid component and a glycol component containing a branched glycol component as constituent components. The branched glycol component includes 2,2-dimethyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, 2-methyl-2-butyl-1,3-propanediol, 2-methyl-2-n-hexyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-n-butyl-1,3-propanediol, 2-ethyl 2-n-hexyl-1,3-propanediol, 2,2-di-n-butyl-1,3-propanediol, 2,2-di-n-hexyl-1,3-propanediol, and the like Can be mentioned. The branched glycol component is preferably contained in the total glycol component in a proportion of 10 mol% or more, and more preferably in a proportion of 20 mol% or more. As the glycol component other than the branched glycol component, ethylene glycol is most preferable. Further, diethylene glycol, propylene glycol, butanediol, hexanediol, 1,4-cyclohexanedimethanol, or the like may be used as long as the amount is small.
ジカルボン酸成分としては、テレフタル酸、イソフタル酸が最も好ましい。また、少量であれば、他のジカルボン酸成分、例えば、アジピン酸、セバシン酸、およびアゼライン酸などの脂肪族ジカルボン酸、ジフェニルジカルボン酸、および２，６−ナフタレンジカルボン酸等の芳香族ジカルボン酸を加えて共重合させてもよい。 As the dicarboxylic acid component, terephthalic acid and isophthalic acid are most preferable. Also, in small amounts, other dicarboxylic acid components, for example, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, and azelaic acid, diphenyldicarboxylic acid, and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid are used. In addition, it may be copolymerized.
バインダーとして使用するウレタン樹脂としては、イソシアネート化合物と水酸基含有化合物との反応によって得られるものが挙げられる。イソシアネート化合物としては、同一分子内に２個以上イソシアネートを持つポリイソシアネートが挙げられる。ポリイソシアネートの具体例としては、ジフェニルメタンジイソシアネート、ポリメチレンポリフェニルイソシアネート、トルエンジイソシアネート、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が挙げられ、これらのウレタン変性物、カルボジイミド変性物、さらにこれらの混合物なども挙げられる。ジフェニルメタンジイソシアネート、ポリメチレンポリフェニルイソシアネート、これらの変性ポリイソシアネートあるいはこれらの混合物が好ましい。 Examples of the urethane resin used as the binder include those obtained by a reaction between an isocyanate compound and a hydroxyl group-containing compound. Examples of the isocyanate compound include polyisocyanates having two or more isocyanates in the same molecule. Specific examples of the polyisocyanate include diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, toluene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. These urethane-modified products, carbodiimide-modified products, and mixtures thereof are also included. Diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, modified polyisocyanates thereof, or mixtures thereof are preferred.
水酸基含有化合物は特に限定されないが、通常同一分子内に２個以上水酸基を持つポリオール化合物が用いられる。ポリオール化合物の具体例としては、プロピレングリコール、ジエチレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、蔗糖などの水酸基含有化合物、トリエタノールアミン、ジエタノールアミンなどのアミノ基と水酸基とを含有する化合物、あるいはエチレンジアミン、ジアミノトルエンなどのアミノ基含有化合物に、エチレンオキシド、プロピレンオキシドなどのアルキレンオキシドを付加した、分子中に２〜６個の水酸基を含有し、平均水酸基当量が２００以上、例えば５００〜３０００のポリエーテルポリオール、あるいはこれらのポリエーテルポリオールにビニル化合物を付加重合したポリマーポリオールなどが挙げられる。また、ポリカルボン酸と低分子量の水酸基含有化合物を反応して得られるポリエステルポリオール、カプロラクトンを開環重合して得たポリカーボネートポリオール、ポリエーテルポリオールの水酸基をアミノ化し、あるいはポリエーテルポリオールのイソシアネートプレポリマーを加水分解して得られるポリエーテルポリアミンであって、平均活性水素当量が２００以上、例えば５００〜３０００のものであってもよい。ポリオールの分子量は１０００以上であることが好ましく、１０００〜１８０００であることがさらに好ましく、２０００〜８０００であることがより好ましい。ポリオールの量は、ポリオール化合物１００質量部当たり５〜８０質量部、例えば１５〜５０質量部であってよい。 The hydroxyl group-containing compound is not particularly limited, but a polyol compound having two or more hydroxyl groups in the same molecule is usually used. Specific examples of the polyol compound include propylene glycol, diethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose and other hydroxyl group-containing compounds, triethanolamine, diethanolamine and other amino group- and hydroxyl group-containing compounds, or ethylenediamine. A polyether having 2 to 6 hydroxyl groups in the molecule obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to an amino group-containing compound such as diaminotoluene and having an average hydroxyl equivalent weight of 200 or more, for example, 500 to 3000 Examples thereof include polyols and polymer polyols obtained by addition polymerization of these polyether polyols with vinyl compounds. Polyester polyols obtained by reacting polycarboxylic acids with low molecular weight hydroxyl group-containing compounds, polycarbonate polyols obtained by ring-opening polymerization of caprolactone, amination of the hydroxyl groups of polyether polyols, or isocyanate prepolymers of polyether polyols The polyether polyamine obtained by hydrolyzing the water may have an average active hydrogen equivalent of 200 or more, for example, 500 to 3000. The molecular weight of the polyol is preferably 1000 or more, more preferably 1000 to 18000, and even more preferably 2000 to 8000. The amount of the polyol may be 5 to 80 parts by mass, for example 15 to 50 parts by mass, per 100 parts by mass of the polyol compound.
ウレタン樹脂製造時の触媒としては、トリエチレンジアミン、ペンタメチルジエチレントリアミン、１，８−ジアザビシクロ−５，４−ウンデセン−７、ジメチルアミノエタノール、テトラメチルエチレンジアミン、ジメチルベンジルアミン、テトラメチルヘキサメチレンジアミン、ビス（２−ジメチルアミノエチル）エーテルなどの第３級アミンやジブチル錫ジラウレート、オクタン酸錫、ジブチル錫ジアセテートなどの有機金属化合物が用いられる。触媒の量は、ポリオール混合物１００質量部当たり０．１〜５質量部の範囲が好ましい。 Catalysts used in the production of urethane resins include triethylenediamine, pentamethyldiethylenetriamine, 1,8-diazabicyclo-5,4-undecene-7, dimethylaminoethanol, tetramethylethylenediamine, dimethylbenzylamine, tetramethylhexamethylenediamine, bis ( Tertiary amines such as 2-dimethylaminoethyl) ether and organometallic compounds such as dibutyltin dilaurate, tin octoate, and dibutyltin diacetate are used. The amount of the catalyst is preferably in the range of 0.1 to 5 parts by mass per 100 parts by mass of the polyol mixture.
本発明において易接着層は、エポキシ基と反応する硬化剤を含有することが好ましい。そのような硬化剤としては、アミノ基、カルボキシル基、カルボン酸無水物基、ヒドロキシル基、−（Ｃ＝Ｘ）−ＮＨ−（Ｃ＝Ｙ）−単位（式中、Ｘ、Ｙは共に酸素原子もしくは硫黄原子、または一方が酸素原子他方が硫黄原子であることを表す。）から選ばれる同一または異なる官能基を１分子中に２個以上含む化合物が挙げられる。また、アミノ基を持つカップリング剤のように添加時は単官能であっても、配合後複合化し、多官能化合物として機能しうる化合物も含まれる。なお硬化剤の分子量は特に制限はなく、高分子化合物でもよい。このような硬化剤の具体例としては、例えば、脂肪族アミン類、酸無水物、フェノール、イミダゾール類、ジシアンジアミド、三弗化硼素のアミン錯体、アジピンジヒドラジド化合物が挙げられ、異なる種類の硬化剤を併せて使用してもよい。硬化剤を易接着層に含有することによって、耐溶剤性が向上する。硬化剤の含有量は、エポキシ変性ブロック重合体に対して２〜５質量％であることが好ましい。 In the present invention, the easy adhesion layer preferably contains a curing agent that reacts with an epoxy group. Examples of such a curing agent include amino group, carboxyl group, carboxylic anhydride group, hydroxyl group,-(C = X) -NH- (C = Y) -unit (wherein X and Y are oxygen atoms). Or a compound containing two or more of the same or different functional groups selected from a sulfur atom, or one of which represents an oxygen atom and the other is a sulfur atom) in one molecule. Moreover, even if it is monofunctional at the time of addition like the coupling agent which has an amino group, the compound which compounded after mixing | blending and can function as a polyfunctional compound is also contained. The molecular weight of the curing agent is not particularly limited and may be a polymer compound. Specific examples of such curing agents include aliphatic amines, acid anhydrides, phenols, imidazoles, dicyandiamide, boron trifluoride amine complexes, and adipine dihydrazide compounds. You may use together. By containing the curing agent in the easy-adhesion layer, the solvent resistance is improved. It is preferable that content of a hardening | curing agent is 2-5 mass% with respect to an epoxy-modified block polymer.
さらに硬化剤とエポキシ変性ブロック共重合体との反応を促進するため、反応促進剤を使用することが好ましい場合がある。その反応促進剤としては第４級アンモニウム塩、第４級ホスホニウム塩、ホスフィン化合物などが挙げられる。特に硬化剤としてカルボキシル基または−（Ｃ＝Ｘ）−ＮＨ−（Ｃ＝Ｙ）−単位を有する化合物を使用するときに反応促進剤を使用することが好ましい。第４級アンモニウム塩としては、テトラブチルアンモニウムブロマイド、ｎ−ドデシルトリメチルアンモニウムブロマイド、オクタデシルトリメチルアンモニウムブロマイド等が挙げられる。第４級ホスホニウム塩としては、トリフェニルベンジルホスホニウムクロライド、トリフェニルベンジルホスホニウムアイオダイド、テトラブチルホスホニウムブロマイド等があげられる。ホスフィンとしてはトリフェニルホスフィン、トリ−２，６−ジメトキシフェニルホスフィン等が挙げられる。反応促進剤の含有量はエポキシ変性ブロック共重合体に対して、５質量％以下であることが好ましい。５質量％より多く使用してもその増量効果が期待できない。 Furthermore, in order to accelerate the reaction between the curing agent and the epoxy-modified block copolymer, it may be preferable to use a reaction accelerator. Examples of the reaction accelerator include quaternary ammonium salts, quaternary phosphonium salts, and phosphine compounds. In particular, it is preferable to use a reaction accelerator when using a compound having a carboxyl group or a — (C═X) —NH— (C═Y) — unit as a curing agent. Examples of the quaternary ammonium salt include tetrabutylammonium bromide, n-dodecyltrimethylammonium bromide, and octadecyltrimethylammonium bromide. Examples of the quaternary phosphonium salt include triphenylbenzylphosphonium chloride, triphenylbenzylphosphonium iodide, tetrabutylphosphonium bromide and the like. Examples of phosphine include triphenylphosphine and tri-2,6-dimethoxyphenylphosphine. The content of the reaction accelerator is preferably 5% by mass or less with respect to the epoxy-modified block copolymer. Even if more than 5% by mass is used, the effect of increasing the amount cannot be expected.
以下実施例により、本発明をさらに説明するが、これに限定されるものではない。なお、易接着層を形成するにあたり、下記のエポキシ変性ブロック重合体とバインダーを使用した。 Hereinafter, the present invention will be further described by way of examples, but is not limited thereto. In forming the easy-adhesion layer, the following epoxy-modified block polymer and binder were used.
エポキシ変性ブロック重合体溶液（ア）：
エポキシ基含有スチレン−ブタジエン−スチレンブロック共重合体（重量平均分子量＝３００００、エポキシ当量（ｇ／ｅｑｕｉｖ）＝１９００）を固形分３０質量％となるようにトルエン／ＭＥＫの混合溶媒に溶解した液。
Epoxy-modified block polymer solution (A):
A solution obtained by dissolving an epoxy group-containing styrene-butadiene-styrene block copolymer (weight average molecular weight = 30000, epoxy equivalent (g / equiv) = 1900) in a toluene / MEK mixed solvent so as to have a solid content of 30% by mass.
エポキシ変性ブロック重合体溶液（イ）：
エポキシ基含有スチレン−ブタジエン−スチレンブロック共重合体（重量平均分子量＝３００００、エポキシ当量（ｇ／ｅｑｕｉｖ）＝１０００）を固形分３０質量％となるようにトルエン／ＭＥＫの混合溶媒に溶解した液。
Epoxy-modified block polymer solution (I):
A solution in which an epoxy group-containing styrene-butadiene-styrene block copolymer (weight average molecular weight = 30000, epoxy equivalent (g / equiv) = 1000) is dissolved in a toluene / MEK mixed solvent so as to have a solid content of 30% by mass.
バインダー液（ウ）：
エリーテルＵＥ３３００（ユニチカ製共重合ポリエステル）
Binder liquid (U):
Elitel UE3300 (Unitika Copolyester)
バインダー液（エ）：
ポリメントＮＫ３８０（日本触媒製アクリル樹脂 ３０質量％溶液）
Binder liquid (D):
Poliment NK380 (Japan Catalyst Acrylic Resin 30% by mass solution)
バインダー液（オ）：
サーモラックＥＦ−４２（綜研化学製アクリル樹脂 ３０質量％溶液）
Binder liquid (e):
Thermolac EF-42 (Acrylic resin 30% by mass solution from Soken Chemical)
また、易接着層上に形成するＵＶ硬化型樹脂として、下記の方法で調製したＵＶ硬化型粘着剤を使用した。 Further, as a UV curable resin formed on the easy-adhesion layer, a UV curable adhesive prepared by the following method was used.
ＵＶ硬化型粘着剤：
ブチルアクリレート７９質量部、エチルアクリレート１５質量部、アクリル酸１質量部、２−ヒドロキシエチルアクリレート５質量部、光重合開始剤０．２質量部（イルガキュア６５１、５０％酢酸エチル溶液）、ラウリルメルカプタン０．０２質量部からなる混合液に、紫外線を照射し、重量平均分子量７００００のアクリル共重合体を得た。得られたアクリル共重合体の酢酸エチル溶液の樹脂固形分１００質量部に対して、メタクリル酸２−イソシアネートエチル３．５質量部を加えて反応させ、更に、反応後の酢酸エチル溶液の樹脂固形分１００質量部に対して、ペンタエリスリトールトリアクリレート２０質量部、光重合開始剤（イルガキュア６５１、５０％酢酸エチル溶液）０．５質量部、ポリイソシアネート１．５質量部を混合して、ＵＶ硬化型粘着剤の酢酸エチル溶液を調製した。
UV curable adhesive:
79 parts by mass of butyl acrylate, 15 parts by mass of ethyl acrylate, 1 part by mass of acrylic acid, 5 parts by mass of 2-hydroxyethyl acrylate, 0.2 parts by mass of photopolymerization initiator (Irgacure 651, 50% ethyl acetate solution), lauryl mercaptan 0 A mixed solution composed of 0.02 parts by mass was irradiated with ultraviolet rays to obtain an acrylic copolymer having a weight average molecular weight of 70,000. With respect to 100 parts by mass of the resin solid content of the obtained acrylic copolymer ethyl acetate solution, 3.5 parts by mass of 2-isocyanatoethyl methacrylate is added and reacted, and further the resin solid of the ethyl acetate solution after the reaction UV curing by mixing 20 parts by mass of pentaerythritol triacrylate, 0.5 parts by mass of a photopolymerization initiator (Irgacure 651, 50% ethyl acetate solution) and 1.5 parts by mass of polyisocyanate with respect to 100 parts by mass. An ethyl acetate solution of a mold adhesive was prepared.
易接着層を設けたポリエステルフィルムの物性の測定法を以下に示す。なお、原理が同じであれば機械、装置等が異なってもよい。 The measuring method of the physical property of the polyester film which provided the easily bonding layer is shown below. In addition, as long as the principle is the same, a machine, an apparatus, etc. may differ.
ＵＶ硬化型樹脂との密着性：
まず上記ＵＶ硬化型粘着剤を、乾燥厚みが１５μｍとなるようにポリエステルフィルムの易接着層上に塗布して粘着剤層を形成させ、粘着テープを作成した。この粘着テープの粘着剤面を指の腹で擦り、粘着剤が取れず密着性が良好な場合を○、粘着剤層が欠落する場合を×とした。更に、このフィルムをガラス板に貼り付けた後、超高圧水銀灯を用いて、３６５ｎｍの紫外線をガラス板表面への照射強度が４０ｍＷ／ｃｍ2となるよう照度を調節して２分間照射した。照射後に粘着テープをガラス板から剥がした際に、ガラス板面に粘着剤が残らない場合を○、ガラス板面に粘着剤が取られて残る場合を×とした。
Adhesion with UV curable resin:
First, the UV curable pressure-sensitive adhesive was applied onto an easy-adhesive layer of a polyester film so as to have a dry thickness of 15 μm to form a pressure-sensitive adhesive layer, thereby preparing a pressure-sensitive adhesive tape. The pressure-sensitive adhesive surface of this pressure-sensitive adhesive tape was rubbed with the belly of the finger. Furthermore, after this film was attached to a glass plate, using an ultra-high pressure mercury lamp, irradiation with ultraviolet rays of 365 nm was performed for 2 minutes while adjusting the illuminance so that the irradiation intensity on the surface of the glass plate was 40 mW / cm 2 . When the pressure-sensitive adhesive tape was peeled off from the glass plate after irradiation, the case where no pressure-sensitive adhesive remained on the glass plate surface was marked with ◯, and the case where the pressure-sensitive adhesive remained on the glass plate surface was marked with x.
実施例１
エポキシ変性ブロック共重合体溶液（ア）１０質量部と、バインダー液（ウ）１０質量部とを混合してなる塗剤を、ポリエステルフィルム（ユニチカ社製エンブレットＳＡ−１２５）のコロナ処理面に塗布後、１３０℃で乾燥して、易接着層の形成されたポリエステルフィルムを得た。
Example 1
A coating formed by mixing 10 parts by mass of the epoxy-modified block copolymer solution (A) and 10 parts by mass of the binder liquid (U) is applied to the corona-treated surface of the polyester film (Embret SA-125 manufactured by Unitika). after coating, and dried at 130 ° C., to obtain a polyester film formed of the adhesive layer.
実施例２〜６、比較例１〜５
表１に示したエポキシ変性ブロック重合体とバインダーとに変更した以外は、実施例１と同様にして、易接着層の形成されたポリエステルフィルムを得た。
Examples 2-6, Comparative Examples 1-5
It was changed to a epoxy-modified block polymer and the binder shown in Table 1, in the same manner as in Example 1 to obtain a polyester film formed of the adhesive layer.
実施例１〜６で得られたポリエステルフィルムの易接着層は、ＵＶ照射前後とも密着性を有していたが、比較例１〜５で得られたフィルムは、照射前並びに照射後の密着性を同時に満たすことが出来なかった。 The easy adhesion layers of the polyester films obtained in Examples 1 to 6 had adhesion before and after UV irradiation, but the films obtained in Comparative Examples 1 to 5 had adhesion before irradiation and after irradiation. Could not be satisfied at the same time.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5337342B2 (en) * | 2006-12-20 | 2013-11-06 | 富士フイルム株式会社 | Translucent electromagnetic shielding film |
| JP5697461B2 (en) * | 2011-01-17 | 2015-04-08 | ユニチカ株式会社 | Polyester film and photosensitive resin structure |
| JP7490399B2 (en) | 2020-03-13 | 2024-05-27 | 日東電工株式会社 | Removable adhesive tape |
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| JPH05214298A (en) * | 1992-02-07 | 1993-08-24 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition curable by actinic radiation |
| JPH06143522A (en) * | 1992-11-09 | 1994-05-24 | Kimoto & Co Ltd | Material for display |
| JPH0939185A (en) * | 1995-07-28 | 1997-02-10 | Daicel Chem Ind Ltd | Polyester laminated film |
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| JPH11296089A (en) * | 1998-04-15 | 1999-10-29 | Toray Ind Inc | Pressure-sensitive adhesive label |
| JP2000191989A (en) * | 1998-12-28 | 2000-07-11 | Nitto Denko Corp | Tacky tape and formation of tacky agent layer |
| JP2001316594A (en) * | 2000-05-10 | 2001-11-16 | Daicel Chem Ind Ltd | Thermoplastic elastomer composition excellent in durability |
| JP2002203816A (en) * | 2000-12-28 | 2002-07-19 | Nitto Denko Corp | Adhesive sheet for dicing |
| JP2003507758A (en) * | 1999-08-17 | 2003-02-25 | エルジー・ケミカル・リミテッド | Photosensitive resin composition |
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- 2004-02-18 JP JP2004041392A patent/JP4571417B2/en not_active Expired - Fee Related
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| JPH05214298A (en) * | 1992-02-07 | 1993-08-24 | Nippon Carbide Ind Co Inc | Pressure-sensitive adhesive composition curable by actinic radiation |
| JPH06143522A (en) * | 1992-11-09 | 1994-05-24 | Kimoto & Co Ltd | Material for display |
| JPH0939185A (en) * | 1995-07-28 | 1997-02-10 | Daicel Chem Ind Ltd | Polyester laminated film |
| JPH09100361A (en) * | 1995-08-02 | 1997-04-15 | Toray Ind Inc | Easily adherable film |
| JPH11296089A (en) * | 1998-04-15 | 1999-10-29 | Toray Ind Inc | Pressure-sensitive adhesive label |
| JP2000191989A (en) * | 1998-12-28 | 2000-07-11 | Nitto Denko Corp | Tacky tape and formation of tacky agent layer |
| JP2003507758A (en) * | 1999-08-17 | 2003-02-25 | エルジー・ケミカル・リミテッド | Photosensitive resin composition |
| JP2001316594A (en) * | 2000-05-10 | 2001-11-16 | Daicel Chem Ind Ltd | Thermoplastic elastomer composition excellent in durability |
| JP2002203816A (en) * | 2000-12-28 | 2002-07-19 | Nitto Denko Corp | Adhesive sheet for dicing |
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