JP2014159548A - Adhesive agent composition, laminate and method producing thereof - Google Patents
Adhesive agent composition, laminate and method producing thereof Download PDFInfo
- Publication number
- JP2014159548A JP2014159548A JP2013247979A JP2013247979A JP2014159548A JP 2014159548 A JP2014159548 A JP 2014159548A JP 2013247979 A JP2013247979 A JP 2013247979A JP 2013247979 A JP2013247979 A JP 2013247979A JP 2014159548 A JP2014159548 A JP 2014159548A
- Authority
- JP
- Japan
- Prior art keywords
- polyol
- adhesive composition
- component
- less
- adhesive
- 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.)
- Granted
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 113
- 239000000203 mixture Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title description 9
- 150000003077 polyols Chemical class 0.000 claims abstract description 114
- 229920005862 polyol Polymers 0.000 claims abstract description 87
- 150000002009 diols Chemical class 0.000 claims abstract description 82
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 60
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 60
- 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 claims abstract description 47
- 229920000728 polyester Polymers 0.000 claims abstract description 36
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 35
- 229920000570 polyether Polymers 0.000 claims abstract description 35
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 28
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims abstract description 22
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000001070 adhesive effect Effects 0.000 claims description 109
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 26
- 239000012790 adhesive layer Substances 0.000 claims description 15
- 239000012948 isocyanate Substances 0.000 claims description 11
- 150000002513 isocyanates Chemical class 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000010030 laminating Methods 0.000 claims description 5
- 239000005022 packaging material Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 22
- 230000007613 environmental effect Effects 0.000 abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 34
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 21
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 21
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 19
- -1 aromatic isocyanate Chemical class 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 238000007740 vapor deposition Methods 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 8
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000002985 plastic film Substances 0.000 description 7
- 229920006255 plastic film Polymers 0.000 description 7
- 229920005906 polyester polyol Polymers 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 150000004072 triols Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000001361 adipic acid Substances 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 230000001588 bifunctional effect Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 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 4
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 241000951471 Citrus junos Species 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- PXIPZIPSDBXFQR-UHFFFAOYSA-N 4,5-dimethyloxolan-2-one Chemical compound CC1CC(=O)OC1C PXIPZIPSDBXFQR-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- AFINAILKDBCXMX-PBHICJAKSA-N (2s,3r)-2-amino-3-hydroxy-n-(4-octylphenyl)butanamide Chemical compound CCCCCCCCC1=CC=C(NC(=O)[C@@H](N)[C@@H](C)O)C=C1 AFINAILKDBCXMX-PBHICJAKSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- WBSRHBNFOLDTGU-UHFFFAOYSA-N nonane-1,8-diol Chemical compound CC(O)CCCCCCCO WBSRHBNFOLDTGU-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes 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
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2405/00—Adhesive articles, e.g. adhesive tapes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/80—Medical packaging
-
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
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Abstract
Description
本発明は、接着剤組成物に関する。また、前述の接着剤組成物を用いた積層体およびその製造方法に関する。 The present invention relates to an adhesive composition. Moreover, it is related with the laminated body using the above-mentioned adhesive composition, and its manufacturing method.
各種プラスチックフィルム同士の貼り合わせや、プラスチックフィルムと金属蒸着フィルムや金属箔との貼り合わせは、従来、水酸基/イソシアネート系の溶剤型接着剤を用いるドライラミネート方式により行われていた。しかし、ドライラミネート方式は有機溶剤を含有する接着剤を用いるので、環境汚染や火災を抑止・防止する特別な設備が必要である。 The pasting of various plastic films and the pasting of a plastic film with a metal vapor-deposited film or a metal foil have been conventionally performed by a dry laminating method using a hydroxyl group / isocyanate solvent adhesive. However, since the dry laminating method uses an adhesive containing an organic solvent, special equipment for suppressing and preventing environmental pollution and fire is required.
近年、簡便な設備への要求から接着剤の脱有機溶剤化の要求が強くなり、無溶剤化の研究が盛んに行われている。
例えば、特許文献1には、ポリオール成分(1)と2種類のポリイソシアネート化合物からなるポリイソシアネート成分(2)とを含有する無溶剤型のラミネート用接着剤組成物が開示されている。
また、特許文献2には、ポリオール成分(1)と3官能ポリイソシアネート化合物を必須とするポリイソシアネート成分(2)とを含有する、分岐点濃度が特定の範囲にあり、水酸基モル数:イソシアネート基モル数=1:1〜1:3である無溶剤型ラミネート接着剤組成物が開示されている。
特許文献3には、ポリオール成分(A)と、イソホロンジイソシアネートを必須とするイソシアネート成分(B)とを含有する無溶剤型接着剤組成物が開示されている。
特許文献4には、ポリオール成分(A)とポリイソシアネート化合物(B)と特定粒子径の紛体(C)とを含有する無溶剤型接着剤組成物が開示されている。
更に特許文献5には、ポリイソシアネートコンポーネント(a)とポリオールコンポーネント(b)とを含有する接着剤組成物であって、ポリイソシアネートコンポーネント(a)が、モノマー系4,4’−メチレンジフェニルジイソシアナート(i)とイソシアナート官能性プレポリマー(ii)とを含む接着剤組成物が開示されている。イソシアナート官能性プレポリマー(ii)は、モノマー系4,4’−メチレンジフェニルジイソシアナートと、1種以上のポリオールとを含むプレポリマー反応物質混合物の反応生成物であり、1種以上のポリオールとして、所定の範囲にある平均分子量を有するトリオールを含むことを特定する。
In recent years, demands for removing organic solvents from adhesives have become stronger due to demands for simple equipment, and research into solvent-free has been actively conducted.
For example, Patent Document 1 discloses a solventless laminating adhesive composition containing a polyol component (1) and a polyisocyanate component (2) composed of two types of polyisocyanate compounds.
Further, Patent Document 2 contains a polyol component (1) and a polyisocyanate component (2) essential for a trifunctional polyisocyanate compound, the branching point concentration is in a specific range, and the hydroxyl group mole number: isocyanate group. A solventless laminate adhesive composition having a mole number of 1: 1 to 1: 3 is disclosed.
Patent Document 3 discloses a solvent-free adhesive composition containing a polyol component (A) and an isocyanate component (B) essentially containing isophorone diisocyanate.
Patent Document 4 discloses a solventless adhesive composition containing a polyol component (A), a polyisocyanate compound (B), and a powder (C) having a specific particle size.
Further, Patent Document 5 discloses an adhesive composition containing a polyisocyanate component (a) and a polyol component (b), wherein the polyisocyanate component (a) is a monomer system 4,4′-methylenediphenyl diisocyanate. An adhesive composition is disclosed comprising a narto (i) and an isocyanate functional prepolymer (ii). The isocyanate functional prepolymer (ii) is a reaction product of a prepolymer reactant mixture comprising a monomer system 4,4′-methylenediphenyl diisocyanate and one or more polyols, wherein the one or more polyols To contain a triol having an average molecular weight in a predetermined range.
接着剤組成物を用いて積層体を得る方法としては、基材(接着の対象)に接着剤組成物を塗工した後、形成された接着剤層に他の基材(接着の対象)を重ね合せた状態で両基材に挟まれた接着剤層の硬化を進行させる方法が一般的である。以下、前記の「接着剤層の硬化を進行させる」工程を「エージング工程」と称する。
特許文献1〜4記載の発明は、ポリイソシアネート成分として、具体的には脂環族系ポリイソシアネート成分や脂肪族系ポリイソシアネート成分を用いていた。脂環族系ポリイソシアネート成分や脂肪族系ポリイソシアネート成分は、反応が比較的穏やかなのでエージング工程に40〜50℃で2〜5日間を要していた。しかしながら、市場においては、従来よりも短時間エージングで同等以上の接着性能を発現できる接着剤組成物の提供が求められている。
As a method of obtaining a laminate using an adhesive composition, after applying the adhesive composition to a base material (target of adhesion), another base material (target of adhesion) is applied to the formed adhesive layer. A general method is to advance the curing of the adhesive layer sandwiched between the two substrates in a superposed state. Hereinafter, the above-mentioned “progress of curing of the adhesive layer” is referred to as an “aging step”.
The inventions described in Patent Documents 1 to 4 specifically use an alicyclic polyisocyanate component or an aliphatic polyisocyanate component as the polyisocyanate component. Since the reaction of the alicyclic polyisocyanate component and the aliphatic polyisocyanate component is relatively mild, the aging process requires 2 to 5 days at 40 to 50 ° C. However, in the market, it is required to provide an adhesive composition that can exhibit the same or better adhesive performance by aging in a shorter time than before.
脂環族系ポリイソシアネート成分や脂肪族系ポリイソシアネート成分に比して、芳香族系ポリイソシアネート成分は反応性に富むので、エージング時間の短時間化という課題に合致する。しかし、反応性に富むが故に、ポリオール成分との反応と環境湿度中の水との反応が競合してしまうこととなり、充分な接着力を発現するためには、塗工時、重ね合せ時およびエージング時の環境湿度を厳しく低湿度に管理する必要があった。このため、市場においては、環境湿度を厳しく低湿度に管理せずとも、従来よりも短時間エージングで同等以上の接着性能を発現できる接着剤組成物の提供が求められている。 Compared with the alicyclic polyisocyanate component and the aliphatic polyisocyanate component, the aromatic polyisocyanate component is rich in reactivity, and therefore meets the problem of shortening the aging time. However, because of its high reactivity, the reaction with the polyol component and the reaction with water in the ambient humidity will compete, and in order to develop sufficient adhesive force, It was necessary to strictly control the environmental humidity during aging to low humidity. For this reason, in the market, there is a demand for providing an adhesive composition capable of exhibiting the same or better adhesive performance by aging in a shorter time than before, without strictly controlling the environmental humidity to a low humidity.
特許文献5記載の発明は、比較的短時間のエージングで接着性能を発現できるが、ポリオール成分とポリイソシアネート成分との混合後、短時間で粘度を極めて大きくしてしまう、即ち接着剤組成物のポットライフを短くしてしまうという問題があった。 The invention described in Patent Document 5 can exhibit adhesive performance with relatively short aging, but after mixing the polyol component and the polyisocyanate component, the viscosity becomes extremely large in a short time. There was a problem of shortening the pot life.
本発明は、上記背景に鑑みて成されたものであり、その目的とするところは、環境湿度を厳しく低湿度に管理せずとも、従来よりも短時間エージングで同等以上の接着性能を発現でき、且つポットライフの長い接着剤組成物、および前記接着剤組成物を用いた積層体とその製造方法を提供することである。 The present invention has been made in view of the above-mentioned background, and the object of the present invention is to achieve the same or better adhesive performance by aging in a shorter time than before without strictly managing the environmental humidity to a low humidity. And an adhesive composition having a long pot life, a laminate using the adhesive composition, and a method for producing the same.
本発明は上記課題に鑑みて成されたものであって、ポリイソシアネート成分(A)として2種類の芳香族系イソシアネートとポリエーテルポリオールとから誘導されるポリイソシアネート成分を含有し、ポリオール成分(B)として特定の分子量のポリエステルジオールと相対的に低分子量のジオールもしくはトリオールとを含有するポリオール成分を含有する。
即ち、本発明は、ポリイソシアネート成分(A)とポリオール成分(B)とを含む接着剤組成物であって、前記ポリイソシアネート成分(A)が、2,4’−ジフェニルメタンジイソシアネート(a1)および4,4’−ジフェニルメタンジイソシアネート(a2)を必須とするイソシアネートと、ポリエーテルポリオール(a3)を必須とするポリオールと、をイソシアネート基過剰の条件下で反応させてなる反応性生成物であり、前記ポリオール成分(B)が、数平均分子量500以上、3,000以下のポリエステルジオール(b1)を必須とし、更に数平均分子量50以上、500未満のジオール(b2)および数平均分子量50以上、500未満のトリオール(b3)の少なくともいずれか一方を含む、ポリオール組成物である、接着剤組成物に関する。
This invention is made in view of the said subject, Comprising: The polyisocyanate component induced | guided | derived from two types of aromatic isocyanate and polyether polyol is included as a polyisocyanate component (A), and a polyol component (B And a polyol component containing a specific molecular weight polyester diol and a relatively low molecular weight diol or triol.
That is, the present invention is an adhesive composition comprising a polyisocyanate component (A) and a polyol component (B), wherein the polyisocyanate component (A) is 2,4′-diphenylmethane diisocyanate (a1) and 4 , 4′-diphenylmethane diisocyanate (a2) is a reactive product obtained by reacting an isocyanate essential to polyether polyol (a3) under an isocyanate group-excess condition. The component (B) essentially comprises a polyester diol (b1) having a number average molecular weight of 500 or more and 3,000 or less, a diol (b2) having a number average molecular weight of 50 or more and less than 500, and a number average molecular weight of 50 or more and less than 500. A polyol composition containing at least one of the triols (b3), About composition.
本発明の接着剤組成物は、2,4’−ジフェニルメタンジイソシアネート(a1)と4,4’−ジフェニルメタンジイソシアネート(a2)との合計の100モル%中、2,4’−ジフェニルメタンジイソシアネート(a1)を10モル%以上、60モル%以下、4,4’−ジフェニルメタンジイソシアネート(a2)を40モル%以上、90モル%以下とすることが好ましい。
また、本発明の接着剤組成物は、ポリオール成分(B)100質量%中に、ポリエステルジオール(b1)を60質量%以上、99質量%以下、ジオール(b2)とトリオール(b3)とを合わせて1質量%以上、40質量%以下含むことが好ましい。
また、ポリオール成分(B)中の水酸基モル数を100モルとした場合、ポリイソシアネート成分(A)中のイソシアネート基のモル数が70モル以上、300モル以下であることが好ましい。
また、本発明の接着剤組成物は、無溶剤型であることが好ましい。
また、本発明の接着剤組成物は、包装材形成用ラミネート用接着剤であることが好ましい。
The adhesive composition of the present invention comprises 2,4′-diphenylmethane diisocyanate (a1) in 100 mol% of the total of 2,4′-diphenylmethane diisocyanate (a1) and 4,4′-diphenylmethane diisocyanate (a2). It is preferable that 10 mol% or more and 60 mol% or less, and 4,4′-diphenylmethane diisocyanate (a2) be 40 mol% or more and 90 mol% or less.
Moreover, the adhesive composition of this invention combines polyester diol (b1) with 60 mass% or more and 99 mass% or less, diol (b2), and triol (b3) in 100 mass% of polyol components (B). It is preferable to contain 1 mass% or more and 40 mass% or less.
Further, when the number of hydroxyl groups in the polyol component (B) is 100 mol, the number of moles of isocyanate groups in the polyisocyanate component (A) is preferably 70 mol or more and 300 mol or less.
Moreover, it is preferable that the adhesive composition of this invention is a solventless type.
Moreover, it is preferable that the adhesive composition of this invention is an adhesive agent for laminates for packaging material formation.
更に本発明は、前記本発明の接着剤組成物を用いて少なくとも2つのシート状基材を積層してなる積層体に関する。 Furthermore, this invention relates to the laminated body formed by laminating | stacking at least 2 sheet-like base material using the adhesive composition of the said this invention.
更に本発明は、前記本発明の接着剤組成物を第1のシート状基材に塗布して接着剤層を形成し、前記接着剤層に第2のシート状基材を重ね合わせ、両シート状基材の間に位置する前記接着剤層を硬化する積層体の製造方法に関する。 In the present invention, the adhesive composition of the present invention is applied to a first sheet-like substrate to form an adhesive layer, and the second sheet-like substrate is overlaid on the adhesive layer. It is related with the manufacturing method of the laminated body which hardens the said adhesive bond layer located between the shaped base materials.
本発明によれば、環境湿度を厳しく低湿度に管理せずとも、従来よりも短時間エージングで同等以上の接着性能を発現でき、且つポットライフの長い接着剤組成物、および前記接着剤組成物を用いた積層体とその製造方法を提供することができるという優れた効果を有する。 ADVANTAGE OF THE INVENTION According to this invention, even if it does not manage environmental humidity severely and low humidity, the adhesive performance which can express the adhesive performance equivalent or better by aging for a short time than before, and has a long pot life, and the said adhesive composition It has the outstanding effect that the laminated body using this and its manufacturing method can be provided.
本発明に係る接着剤組成物は、ポリイソシアネート成分(A)とポリオール成分(B)とを含む。
ポリイソシアネート成分(A)は、2,4’−ジフェニルメタンジイソシアネート(2,4'-diphenylmethane diisocyanate)(a1)および4,4’−ジフェニルメタンジイソシアネート(4,4’-diphenylmethane diisocyanate)(a2)を必須とするイソシアネートと、ポリエーテルポリオール(a3)を必須とするポリオールと、をイソシアネート基過剰の条件下で反応させてなる反応性生成物である。以下、2,4’−ジフェニルメタンジイソシアネート(a1)を2,4’−MDI(a1)、4,4’−ジフェニルメタンジイソシアネート(a2)を4,4’−MDI(a2)と略すこともある。
ポリオール成分(B)は、数平均分子量500以上、3,000以下のポリエステルジオール(b1)を必須とし、更に数平均分子量50以上、500未満のジオール(b2)および数平均分子量50以上、500未満のトリオール(b3)の少なくともいずれか一方を含むポリオール組成物である。
The adhesive composition according to the present invention includes a polyisocyanate component (A) and a polyol component (B).
The polyisocyanate component (A) includes 2,4′-diphenylmethane diisocyanate (a1) and 4,4′-diphenylmethane diisocyanate (a2) as essential components. It is a reactive product obtained by reacting an isocyanate to be reacted with a polyol having the polyether polyol (a3) as an essential component under an excess of isocyanate groups. Hereinafter, 2,4′-diphenylmethane diisocyanate (a1) may be abbreviated as 2,4′-MDI (a1), and 4,4′-diphenylmethane diisocyanate (a2) may be abbreviated as 4,4′-MDI (a2).
The polyol component (B) essentially comprises a polyester diol (b1) having a number average molecular weight of 500 or more and 3,000 or less, a diol (b2) having a number average molecular weight of 50 or more and less than 500, and a number average molecular weight of 50 or more and less than 500. The polyol composition containing at least one of the triols (b3).
上記構成により、環境湿度を厳しく低湿度に管理せずとも、従来よりも短時間エージングで同等以上の接着性能を発現でき、且つポットライフの長い接着剤組成物を提供できる。本発明の接着剤組成物は、溶剤を含むことを排除するものではないが、無溶剤型においても適用できる点において優れている。なお、無溶剤型とは、実質的に溶剤を含まないものであり、製造工程等において不可避的に残留する溶剤や、特性に影響を与えない微量の溶剤を含んでいるものも本発明では無溶剤型に含まれるものとする。以下、本発明について詳細に説明する。 With the above configuration, it is possible to provide an adhesive composition that can exhibit the same or better adhesive performance by aging in a shorter time than before and has a long pot life without strictly controlling the environmental humidity to a low humidity. The adhesive composition of the present invention does not exclude the inclusion of a solvent, but is excellent in that it can be applied to a solventless type. The solvent-free type is substantially free of solvent, and the present invention does not include a solvent that inevitably remains in the manufacturing process or a solvent that contains a trace amount of solvent that does not affect the characteristics. It shall be included in the solvent mold. Hereinafter, the present invention will be described in detail.
ポリイソシアネート成分(A)は、2,4’−MDI(a1)とポリオールとが反応したウレタンプレポリマーおよび4,4’−MDI(a2)とポリオールとが反応したウレタンプレポリマーをブレンドしたもの、または/および2,4’−MDI(a1)と4,4’−MDI(a2)とポリオールとが反応したウレタンプレポリマーを含む。また、未反応の2,4’−MDI(a1)や未反応の4,4’−MDI(a2)を含み得る。 The polyisocyanate component (A) is a blend of a urethane prepolymer obtained by reacting 2,4′-MDI (a1) and a polyol and a urethane prepolymer obtained by reacting 4,4′-MDI (a2) and a polyol, Or / and a urethane prepolymer obtained by reacting 2,4′-MDI (a1), 4,4′-MDI (a2) and a polyol. Moreover, unreacted 2,4'-MDI (a1) and unreacted 4,4'-MDI (a2) may be included.
ポリイソシアネート成分(A)として、4,4’−MDI(a2)を2,4’−MDI(a1)と併用することにより、短時間エージングであっても、充分な接着性能を発揮できる。一方、2,4’−MDI(a1)を4,4’−MDI(a2)と併用することにより、高湿度環境下での塗工・重ね合わせ・エージングであっても、充分な接着性能を発揮できる。また、2,4’−MDI(a1)と4,4’−MDI(a2)との合計の100モル%中、2,4’−MDI(a1)は10〜60モル%(上限値と下限値を含む。以下同様)、4,4’−MDI(a2)は40〜90モル%とすることが好ましい。2種類のMDIの組成比を上記範囲とすることによって、環境湿度を厳しく低湿度に管理せずとも、従来よりも短時間エージングで同等以上の接着性能をより効果的に発現できる。 By using 4,4'-MDI (a2) in combination with 2,4'-MDI (a1) as the polyisocyanate component (A), sufficient adhesive performance can be exhibited even with short-time aging. On the other hand, by using 2,4'-MDI (a1) together with 4,4'-MDI (a2), sufficient adhesion performance can be achieved even in coating, superposition and aging under high humidity environment. Can demonstrate. Of the total of 2,4′-MDI (a1) and 4,4′-MDI (a2), 100 mol%, 2,4′-MDI (a1) is 10 to 60 mol% (upper limit and lower limit). In the same manner, 4,4′-MDI (a2) is preferably 40 to 90 mol%. By setting the composition ratio of the two types of MDI in the above range, it is possible to more effectively express adhesive performance equal to or higher than that in the past by aging in a shorter time than before without strictly controlling the environmental humidity to low humidity.
ポリイソシアネート成分(A)を形成するポリオールについて説明する。ポリオールは、ポリエーテルポリオール(a3)を必須成分として含有し、その他にポリエステルポリオールを含有することができる。ポリエーテルポリオールは、一般にポリエステルポリオールに比して溶融状態での粘度が低いので、接着剤の構成成分であるポリイソシアネート成分(A)を形成する際のポリオールとしては、ポリエーテルポリオール(a3)を必須とすることが重要である。更に、ポリエステルポリオールを併用することにより、後述するポリオール成分(B)との相溶性を高めると共に、接着剤組成物の凝集力を高めることができる。
ポリエステルポリオールを併用する場合には、ポリオール100質量%中、接着剤組成物の粘度の点から30質量%以下であることが好ましく、1〜30質量%であることがより好ましく、1〜20質量%であることが更に好ましい。
The polyol that forms the polyisocyanate component (A) will be described. The polyol contains the polyether polyol (a3) as an essential component, and can further contain a polyester polyol. Since the polyether polyol generally has a lower viscosity in the molten state than the polyester polyol, the polyether polyol (a3) is used as the polyol for forming the polyisocyanate component (A) which is a constituent component of the adhesive. It is important to make it mandatory. Furthermore, by using a polyester polyol in combination, the compatibility with the polyol component (B) described later can be enhanced, and the cohesive force of the adhesive composition can be enhanced.
When the polyester polyol is used in combination, it is preferably 30% by mass or less, more preferably 1 to 30% by mass, and more preferably 1 to 20% by mass in terms of the viscosity of the adhesive composition in 100% by mass of the polyol. % Is more preferable.
ポリエーテルポリオール(a3)としては、例えば、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、テトラヒドロフラン等のオキシラン化合物を、例えば、水、エチレングリコール、プロピレングリコール、トリメチロールプロパン、グリセリン等の低分子量ポリオールを開始剤として重合して得られるポリエーテルポリオール等が挙げられる。 As the polyether polyol (a3), for example, an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, and a low molecular weight polyol such as water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerin are used as initiators. Examples include polyether polyols obtained by polymerization.
ポリエーテルポリオール(a3)としては、2官能の他、3官能以上のものを用いることができる。また、官能基数の異なるものを複数組み合わせて用いることもできる。ポリエーテルポリオール(a3)の数平均分子量は、100以上、5,000以下のものが好ましい。なお、異なる数平均分子量のポリエーテルポリオール(a3)を複数組み合わせて用いることもできる。 As the polyether polyol (a3), a bifunctional or trifunctional or higher functional can be used. In addition, a plurality of different functional groups can be used in combination. The number average molecular weight of the polyether polyol (a3) is preferably from 100 to 5,000. A plurality of polyether polyols (a3) having different number average molecular weights can be used in combination.
併用されるポリエステルポリオールとしては、多価カルボン酸成分とグリコール成分とを反応させて得られるポリエステルポリオール等が挙げられる。
多価カルボン酸成分としては、例えば、テレフタル酸、イソフタル酸、アジピン酸、アゼライン酸、セバチン酸等の多価カルボン酸もしくはそれらのジアルキルエステルまたはそれらの混合物が挙げられる。グリコール成分としては、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、ブチレングリコール、ネオペンチルグリコール、1,6−ヘキサンジオール、3−メチル−1,5−ペンタンジオール、3,3−ジメチロールヘプタン、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリテトラメチレンエーテルグリコール等のグリコール類もしくはそれらの混合物が挙げられる。
Examples of the polyester polyol used in combination include polyester polyols obtained by reacting a polyvalent carboxylic acid component and a glycol component.
Examples of the polyvalent carboxylic acid component include polyvalent carboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid, dialkyl esters thereof, or mixtures thereof. Examples of the glycol component include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, polyoxy Examples thereof include glycols such as ethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, and mixtures thereof.
本発明に用いられるポリイソシアネート成分(A)は、例えば、2,4’−MDI(a1)と4,4’−MDI(a2)との混合物と、ポリエーテルポリオール(a3)を必須とするポリオールとを反応させて得ることができる。あるいは、ポリイソシアネート成分(A)は、2,4’−MDI(a1)と4,4’−MDI(a2)とをそれぞれ、ポリエーテルポリオール(a3)を必須とするポリオールとを反応させ、得られた反応生成物を混合することによっても得ることができる。更に、ポリイソシアネート成分(A)は、2,4’−MDI(a1)と4,4’−MDI(a2)とを順番に、ポリエーテルポリオール(a3)を必須とするポリオールに反応させることによって得ることもできる。 The polyisocyanate component (A) used in the present invention is, for example, a polyol essentially comprising a mixture of 2,4′-MDI (a1) and 4,4′-MDI (a2) and a polyether polyol (a3). Can be obtained by reaction. Alternatively, the polyisocyanate component (A) is obtained by reacting 2,4′-MDI (a1) and 4,4′-MDI (a2) with a polyol essentially comprising the polyether polyol (a3), respectively. The reaction product obtained can also be obtained by mixing. Furthermore, the polyisocyanate component (A) is obtained by reacting 2,4′-MDI (a1) and 4,4′-MDI (a2) in turn with a polyol essentially comprising the polyether polyol (a3). It can also be obtained.
本発明に用いられるポリイソシアネート成分(A)は、イソシアネート基過剰の条件下に上記成分を反応させればよく、イソシアネート基/水酸基の当量比を1越え、6以下の範囲で反応させることが好ましく、1.5以上、4以下の範囲で反応させることがより好ましい。
前記範囲の当量比にて、2,4’−MDI(a1)と4,4’−MDI(a2)とポリールとを反応させることにより、適度な数平均分子量のウレタンプレポリマーと、適度な量のイソシアネート基を有することができる。その結果、ポリイソシアネート成分(A)を後述するポリオール成分(B)と混合して接着剤組成物を得、前記接着剤組成物を用いて積層体を得た場合、充分な接着強度を得ることができる。
The polyisocyanate component (A) used in the present invention may be reacted with the above components under an excess of isocyanate groups, and the isocyanate group / hydroxyl group equivalent ratio is preferably more than 1 and preferably 6 or less. More preferably, the reaction is conducted in the range of 1.5 or more and 4 or less.
By reacting 2,4′-MDI (a1), 4,4′-MDI (a2) and polyol with an equivalence ratio in the above range, an appropriate number average molecular weight urethane prepolymer and an appropriate amount It is possible to have an isocyanate group. As a result, when the polyisocyanate component (A) is mixed with the polyol component (B) described later to obtain an adhesive composition, and a laminate is obtained using the adhesive composition, sufficient adhesive strength is obtained. Can do.
次に本発明に用いられるポリオール成分(B)について説明する。ポリオール成分(B)は、前述した様に、数平均分子量500以上、3,000以下のポリエステルジオール(b1)を必須とし、更に数平均分子量50以上、500未満のジオール(b2)または数平均分子量50以上、500未満のトリオール(b3)の少なくともいずれか一方を含む。本発明者らが鋭意検討を重ねた結果、ポリエステルジオール(b1)を単独でポリオール成分(B)として用いると、充分な接着強度が得られないことがわかった。また、ポリエステルジオール(b1)を使用しないで、ジオール(b2)または/およびトリオール(b3)をポリオール成分(B)として用いると、ポットライフが短いばかりでなく、充分な接着強度が得られないことがわかった。即ち、ポリオール成分(B)として、特定の数平均分子量を有するポリエステルジオール(b1)を用い、且つ特定の数平均分子量を有するジオール(b2)または/およびトリオールを用いることにより、従来と同等以上の接着性能を実現しながら、ポットライフを改善できることを突き止めた。 Next, the polyol component (B) used in the present invention will be described. As described above, the polyol component (B) essentially comprises a polyester diol (b1) having a number average molecular weight of 500 or more and 3,000 or less, and a diol (b2) having a number average molecular weight of 50 or more and less than 500 or a number average molecular weight. 50 or more and less than 500 triol (b3) is included. As a result of extensive studies by the present inventors, it has been found that when the polyester diol (b1) is used alone as the polyol component (B), sufficient adhesive strength cannot be obtained. Further, when the diol (b2) or / and the triol (b3) is used as the polyol component (B) without using the polyester diol (b1), not only the pot life is short, but also sufficient adhesive strength cannot be obtained. I understood. That is, as the polyol component (B), by using the polyester diol (b1) having a specific number average molecular weight and using the diol (b2) or / and triol having a specific number average molecular weight, it is equal to or higher than the conventional one. We have found that pot life can be improved while realizing adhesive performance.
ポリエステルジオール(b1)としては、例えば、テレフタル酸、イソフタル酸、アジピン酸、アゼライン酸、セバチン酸等の多価カルボン酸もしくはそれらのジアルキルエステルまたはそれらの混合物と、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、ブチレングリコール、ネオペンチルグリコール、1,6−ヘキサンジオール、3−メチル−1,5−ペンタンジオール、3,3−ジメチロールヘプタン、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリテトラメチレンエーテルグリコール等のグリコール類もしくはそれらの混合物とを反応させて得られるポリエステルジオールが挙げられる。また、前述の多価カルボン酸もしくはそれらのジアルキルエステルまたはそれらの混合物と、ポリカプロラクトン、ポリバレロラクトン、ポリ(β−メチル−γ−バレロラクトン)等のラクトン類を開環重合して得られるポリエステルジオール等が挙げられる。
数平均分子量が上記範囲内のポリエステルジオール(b1)を用いることによって、ポリエーテルポリウレタンを必須の構成成分とする前述のポリイソシアネート成分(A)との相溶性がよくなり、透明な接着剤組成物を得ることができ、充分な接着性能を発現できる。
Examples of the polyester diol (b1) include polycarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid, or dialkyl esters thereof or mixtures thereof, and, for example, ethylene glycol, propylene glycol, diethylene glycol. , Butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, etc. The polyester diol obtained by making it react with these glycols or mixtures thereof is mentioned. In addition, polyesters obtained by ring-opening polymerization of the aforementioned polycarboxylic acids or their dialkyl esters or mixtures thereof and lactones such as polycaprolactone, polyvalerolactone, poly (β-methyl-γ-valerolactone) Diol etc. are mentioned.
By using the polyester diol (b1) having a number average molecular weight within the above range, compatibility with the aforementioned polyisocyanate component (A) having polyether polyurethane as an essential constituent component is improved, and a transparent adhesive composition Can be obtained, and sufficient adhesive performance can be expressed.
数平均分子量50以上、500未満のジオール(b2)としては、例えば、ポリエステルジオール、ポリエーテルジオール、ポリエーテルエステルジオール、ポリエステルアミドジオール、アクリルジオール、ポリカーボネートジオール;エチレングリコール、プロピレングリコール、ジエチレングリコール、ブチレングリコール、ネオペンチルグリコール、1,6−ヘキサンジオール、3−メチル−1,5−ペンタンジオール、3,3−ジメチロールヘプタン、2−メチル−1,3−プロパンジオール等の低分子ジオール類;またはそれらの混合物が挙げられる。これらの中でも、反応性の観点から、低分子ジオール類が好ましい。 Examples of the diol (b2) having a number average molecular weight of 50 or more and less than 500 include, for example, polyester diol, polyether diol, polyether ester diol, polyester amide diol, acrylic diol, polycarbonate diol; ethylene glycol, propylene glycol, diethylene glycol, butylene glycol , Low molecular diols such as neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, 2-methyl-1,3-propanediol; Of the mixture. Among these, low molecular diols are preferable from the viewpoint of reactivity.
上記ポリエステルジオールとしては、例えば、テレフタル酸、イソフタル酸、アジピン酸、アゼライン酸、セバチン酸等二塩基酸もしくはそれらのジアルキルエステルまたはそれらの混合物と、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、ブチレングリコール、ネオペンチルグリコール、1,6−ヘキサンジオール、3−メチル−1,5−ペンタンジオール、3,3’−ジメチロールヘプタン、ポリオキシエチレングリコール、ポリオキシプロピレングリコール等の2官能グリコール類もしくはそれらの混合物とを反応させて得られるポリエステルジオール或いはポリカプロラクトン、ポリバレロラクトン、ポリ(β−メチル−γ−バレロラクトン)等のラクトン類を開環重合して得られるポリエステルジオールが挙げられる。 Examples of the polyester diol include, for example, dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid or dialkyl esters thereof, or mixtures thereof, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, Bifunctional glycols such as neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3′-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, or mixtures thereof Polyesterdiol obtained by ring-opening polymerization of lactones such as polyester diol or polycaprolactone, polyvalerolactone, poly (β-methyl-γ-valerolactone) obtained by reacting For example.
上記ポリエーテルジオールとしては、例えば、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、テトラヒドロフラン等のオキシラン化合物を、例えば、水、エチレングリコール、プロピレングリコール、等の2官能低分量ポリオールを開始剤として重合して得られるポリエーテルジオールが挙げられる。 Examples of the polyether diol are obtained by polymerizing an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, for example, using a bifunctional low-part polyol such as water, ethylene glycol, and propylene glycol as an initiator. Examples include polyether diol.
上記ポリエーテルエステルポリオールとしては、例えば、テレフタル酸、イソフタル酸、アジピン酸、アゼライン酸、セバチン酸等の二塩基酸もしくはそれらのジアルキルエステルまたはそれらの混合物と、上記ポリエーテルジオールを反応させて得られるポリエーテルエステルジオールが挙げられる。 Examples of the polyether ester polyol are obtained by reacting the above polyether diol with a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid or a dialkyl ester thereof or a mixture thereof. Examples include polyether ester diols.
上記ポリエステルアミドジオールとしては、上記エステル化反応に際し、例えば、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン等のアミノ基を有する脂肪族ジアミンを原料として合わせて使用することによって得られる。 In the esterification reaction, the polyesteramide diol can be obtained, for example, by using an aliphatic diamine having an amino group such as ethylenediamine, propylenediamine, and hexamethylenediamine as a raw material.
上記アクリルジオールの例としては、1分子中に1個以上の水酸基を含むアクリル酸ヒドロキシエチル、アクリル酸ヒドロキシプロプル、アクリルヒドロキシブチル等、或いはこれらの対応するメタクリル酸誘導体等と、例えばアクリル酸、メタクリル酸またはそのエステルとを共重合することによって得られる。 Examples of the acrylic diol include hydroxyethyl acrylate having one or more hydroxyl groups in one molecule, hydroxypropyl acrylate, acrylhydroxybutyl, etc., or their corresponding methacrylic acid derivatives, for example, acrylic acid, It is obtained by copolymerizing methacrylic acid or its ester.
上記ポリカーボネートジオールとしては、例えば、エチレングリコール、プロピレングリコール、1,4−ブタンジオール、1,5−ペンタンジオール、1,6−ヘキサンジオール、3−メチル−1,5−ペンタンジオール、1,9−ノナンジオール、1,8−ノナンジオール、ネオペンチルグリコール、ジエチレングリコール、ジプロピレングリコール、1,4−シクロヘキサンジオール、1,4−シクロヘキサンジメタノール、の中から選ばれた1種または2種以上のグリコールをジメチルカーボネート、ジフェニルカーボネート、エチレンカーボネート、ホスゲン等との反応によって得られたものが挙げられる。 Examples of the polycarbonate diol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9- Nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, one or more glycols selected from Examples thereof include those obtained by reaction with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene and the like.
数平均分子量50以上、500未満のトリオール(b3)としては、ポリエーテルトリオール、ひまし油;トリメチロールプロパン、グリセリン等の低分子トリオール類;またはそれらの混合物が挙げられる。これらの中でも、反応性の観点から、低分子トリオール類やポリエーテルトリオールが好ましい。 Examples of the triol (b3) having a number average molecular weight of 50 or more and less than 500 include polyether triol, castor oil; low molecular triols such as trimethylolpropane and glycerin; or a mixture thereof. Among these, low molecular triols and polyether triols are preferable from the viewpoint of reactivity.
上記ポリエーテルトリオールとしては、例えば、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、テトラヒドロフラン等のオキシラン化合物に、例えば、トリメチロールプロパン、グリセリン等の低分量トリオールを用いて重合して得られるポリエーテルトリオールが挙げられる。 Examples of the polyether triol include polyether triols obtained by polymerizing oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using low-amount triols such as trimethylolpropane and glycerin. .
ポリオール成分(B)は、ポリオール成分(B)100質量%中に、ジオール(b1)を60質量%以上、99質量%以下、ジオール(b2)とトリオール(b3)とを合わせて1質量%以上、40質量%以下含むことが好ましい。ジオール(b1)等の組成比が上記範囲にあることによって、充分なポットライフと接着性能とを発現できる。より好ましい範囲は、ポリオール成分(B)100質量%中に、ジオール(b1)を80質量%以上、95質量%以下、ジオール(b2)とトリオール(b3)とを合わせて5質量%以上、20質量%以下含むことがより好ましい。 The polyol component (B) is 60% by mass or more and 99% by mass or less of the diol (b1) in 100% by mass of the polyol component (B), and 1% by mass or more of the diol (b2) and the triol (b3). 40 mass% or less is preferable. When the composition ratio of the diol (b1) and the like is in the above range, sufficient pot life and adhesive performance can be expressed. More preferable range is 80% by mass or more and 95% by mass or less of diol (b1) in 100% by mass of the polyol component (B), and 5% by mass or more of diol (b2) and triol (b3). More preferably, the content is less than or equal to mass%.
ポリオール成分(B)は、前記ジオール(b1)、ジオール(b2)、トリオール(b3)の他に、本発明の目的を損なわない範囲で、その他のポリオール成分を含むことができる。 The polyol component (B) can contain other polyol components in addition to the diol (b1), diol (b2), and triol (b3) as long as the object of the present invention is not impaired.
本発明の接着剤組成物は、ポリオール成分(B)中の水酸基モル数を100モルとした場合、ポリイソシアネート成分(A)中のイソシアネート基モル数が、70モル以上、300モル以下であることが好ましい。70モル以上にすることにより、充分な接着強度を保有し、また、300モル以下で、蒸着面上の接着剤層の状態を良好に形成することができる。上限値のより好ましい範囲は250モル以下であり、更に好ましい範囲は230モル以下であり、下限値のより好ましい範囲は100モル以上であり、更に好ましい範囲は150モル以上である。 In the adhesive composition of the present invention, when the number of hydroxyl groups in the polyol component (B) is 100 moles, the number of moles of isocyanate groups in the polyisocyanate component (A) is 70 to 300 moles. Is preferred. By making it 70 mol or more, sufficient adhesive strength is retained, and when it is 300 mol or less, the state of the adhesive layer on the vapor deposition surface can be satisfactorily formed. A more preferable range of the upper limit is 250 mol or less, a further preferable range is 230 mol or less, a more preferable range of the lower limit is 100 mol or more, and a further preferable range is 150 mol or more.
本発明の接着剤組成物は、溶剤を含有しないことが好ましい。各成分の流動性が乏しい場合には、それぞれを流動性が確保できる程度に加熱した後、配合することが好ましい。流動性が確保できるのであれば、配合時は加熱しなくてもよい。
前記ポリイソシアネート成分(A)、ポリオール成分(B)成分、その他の後述する各種添加剤等を混合した直後の粘度は、25℃〜50℃の温度範囲の少なくともいずれかにおいて、好ましくは50mPa・s以上、5,000mPa・s以下、更に好ましくは100mPa・s以上、3,000mPa・s以下である。
なお、本発明において、混合した直後とは、均一混合後5分以内であることを意味し、粘度はB型粘度計により求めた値を示す。25℃〜50℃の温度範囲のいずれにおいても粘度が5,000mPa・sを超える場合には、塗工が困難になり良好な作業性を確保することが難しく、塗工温度を100℃に上げても良好な塗装外観は得られない可能性がある。また、100℃以上で塗工するとフィルムが伸びて印刷柄のピッチずれを起こし、ラミネートができなくなる傾向にある。一方、25℃〜50℃の温度範囲のいずれにおいても粘度が50mPa・s未満の場合には、初期凝集力が弱いために充分な接着性能が得られなかったり、基材に接着剤を塗工する際に塗膜の厚みが均一にならず外観不良を生じたり、反りが発生する傾向にある。
The adhesive composition of the present invention preferably contains no solvent. When the fluidity of each component is poor, it is preferable to blend after heating each component to such an extent that fluidity can be secured. As long as fluidity can be secured, it is not necessary to heat at the time of blending.
The viscosity immediately after mixing the polyisocyanate component (A), polyol component (B) component, and other various additives described later is preferably 50 mPa · s in at least one of a temperature range of 25 ° C. to 50 ° C. The above is 5,000 mPa · s or less, more preferably 100 mPa · s or more and 3,000 mPa · s or less.
In the present invention, “immediately after mixing” means within 5 minutes after uniform mixing, and the viscosity is a value determined by a B-type viscometer. When the viscosity exceeds 5,000 mPa · s in any temperature range of 25 ° C. to 50 ° C., coating becomes difficult and it is difficult to ensure good workability, and the coating temperature is raised to 100 ° C. However, a good paint appearance may not be obtained. Moreover, when it coats at 100 degreeC or more, there exists a tendency for a film to elongate and to produce pitch shift of a printed pattern, and to become unable to laminate. On the other hand, if the viscosity is less than 50 mPa · s in any temperature range of 25 ° C. to 50 ° C., the initial cohesive force is weak, so that sufficient adhesive performance cannot be obtained, or an adhesive is applied to the substrate. When doing so, the thickness of the coating film is not uniform, and there is a tendency for appearance defects or warping.
本発明の接着剤組成物は、更に、例えば、酸化防止剤、紫外線吸収剤、加水分解防止剤、防徽剤、増粘剤、可塑剤、消泡剤、顔料、充填剤等の添加剤を必要に応じて使用することができる。また、接着性能を更に高めるために、シランカップリング剤、リン酸、リン酸誘導体、酸無水物、粘着性樹脂等の接着助剤を使用することができる。また、硬化反応を調節するため公知の触媒、添加剤等を使用することができる。 The adhesive composition of the present invention further includes additives such as an antioxidant, an ultraviolet absorber, a hydrolysis inhibitor, an antifungal agent, a thickener, a plasticizer, an antifoaming agent, a pigment, and a filler. Can be used as needed. Moreover, in order to further improve the adhesive performance, an adhesion aid such as a silane coupling agent, phosphoric acid, phosphoric acid derivative, acid anhydride, or adhesive resin can be used. In addition, known catalysts, additives and the like can be used to control the curing reaction.
本発明の接着剤組成物の使用方法は、特に限定されるものではないが、好適な方法として以下の方法を例示できる。即ち、ポリイソシアネート成分(A)、ポリオール成分(B)を混合し、無溶剤型のラミネーターによって接着剤組成物をシート状基材の表面に塗布する。接着剤組成物の塗布量は、基材の種類や塗工条件等に応じて適宜選択されるが、通常、1.0g/m2以上、5.0g/m2以下であり、好ましくは1.5g/m2以上、4.5g/m2以下である。
その後、シート状基材の接着面と別のシート状基材を貼り合せ、常温または加温下にエージングして硬化させる。本発明の接着剤組成物の場合、エージングに要する時間は1日程度である。また、本発明の接着剤組成物の場合、塗工からエージングの際の環境湿度が高くても充分な接着性能を発現できる。
Although the usage method of the adhesive composition of this invention is not specifically limited, The following method can be illustrated as a suitable method. That is, the polyisocyanate component (A) and the polyol component (B) are mixed, and the adhesive composition is applied to the surface of the sheet-like substrate by a solventless laminator. The coating amount of the adhesive composition is appropriately selected according to the type of substrate, coating conditions, etc., but is usually 1.0 g / m 2 or more and 5.0 g / m 2 or less, preferably 1 .5g / m 2 or more and 4.5 g / m 2 or less.
Thereafter, the adhesive surface of the sheet-like substrate and another sheet-like substrate are bonded together and aged at room temperature or under heating to be cured. In the case of the adhesive composition of the present invention, the time required for aging is about 1 day. Moreover, in the case of the adhesive composition of this invention, sufficient adhesive performance can be expressed even if the environmental humidity at the time of aging from coating is high.
本発明の接着剤組成物を用いてシート状基材を積層することにより積層体を得ることができる。シート状基材としては、ポリエステル、ポリアミド、ポリエチレン、ポリプロピレン等のプラスチックフィルム、アルミニウム、酸化珪素、酸化アルミ等を蒸着した金属蒸着フィルム、ステンレス、鉄、銅、鉛等の金属箔などが用いられる。かかる基材の組合せは、プラスチックフィルム同士であっても、プラスチックフィルムと金属蒸着フィルムまたは金属箔でもよい。 A laminated body can be obtained by laminating a sheet-like substrate using the adhesive composition of the present invention. As the sheet-like substrate, a plastic film such as polyester, polyamide, polyethylene, or polypropylene, a metal vapor deposition film obtained by vapor deposition of aluminum, silicon oxide, aluminum oxide, or the like, or a metal foil such as stainless steel, iron, copper, or lead is used. Such a combination of substrates may be a plastic film or a plastic film and a metal vapor deposition film or a metal foil.
上記特許文献5においては、前述した様に、接着剤組成物のポットライフが短いという問題があった。特許文献5においては、ポリオールコンポーネント(b)がトリオールのみからなることが好適であることが開示されている(第52、54段落等)が、トリオールは、ジオール成分に比して反応性に富むが故に、ポリオール成分とポリイソシアネート成分との混合後、短時間で粘度を極めて大きくしてしまい、接着剤組成物のポットライフが短くなってしまったものと推測する。 In the said patent document 5, there existed a problem that the pot life of adhesive composition was short as mentioned above. In Patent Document 5, it is disclosed that the polyol component (b) is preferably composed only of triol (paragraphs 52 and 54, etc.), but the triol is richer in reactivity than the diol component. Therefore, it is presumed that after mixing the polyol component and the polyisocyanate component, the viscosity was extremely increased in a short time, and the pot life of the adhesive composition was shortened.
一方、本発明によれば、ポリオール成分として特定の数平均分子量のポリエステルジオール(b1)と、特定の数平均分子量のジオール(b2)または/およびトリオール(b3)を用い、且つ上述のポリイソシアネート成分(A)に、上述のポリオール成分(B)を用いているので、環境湿度を厳しく低湿度に管理せずとも、従来よりも短時間エージングで同等以上の接着性能を発現でき、且つポットライフが長い接着剤組成物を提供できる。特に、無溶剤型接着剤の場合、短時間での粘度増加は、塗工性・生産性に多大な影響を及ぼすので、工業的観点から大きな課題となっていたが、本発明の接着剤組成物によれば、前述したとおり無溶剤型の場合においても、環境湿度を厳しく低湿度に管理せずとも、従来よりも短時間エージングで同等以上の接着性能を発現でき、且つ長いポットライフを実現できる。 On the other hand, according to the present invention, a polyester diol (b1) having a specific number average molecular weight and a diol (b2) or / and a triol (b3) having a specific number average molecular weight are used as the polyol component, and the polyisocyanate component described above is used. Since the above-described polyol component (B) is used in (A), even if the environmental humidity is not strictly controlled to low humidity, the adhesive performance equivalent to or higher than that can be expressed by aging in a shorter time than before, and the pot life is increased. A long adhesive composition can be provided. In particular, in the case of a solventless adhesive, an increase in viscosity in a short time has had a great problem from an industrial viewpoint because it has a great influence on coating properties and productivity, but the adhesive composition of the present invention According to the product, even in the case of the solvent-free type as described above, it is possible to express the same or better adhesive performance with a shorter time aging than before and realize a long pot life even if the environmental humidity is not strictly controlled to low humidity. it can.
≪実施例≫
以下、実施例により本発明を更に具体的に説明する。実施例および比較例中の%および部は、断りのない限りは全て質量基準である。
<Example>
Hereinafter, the present invention will be described more specifically with reference to examples. Unless otherwise indicated,% and part in Examples and Comparative Examples are based on mass.
ポリエーテルポリオール、ポリエステルジオール等の数平均分子量はゲルパーミエーションクロマトグラフィー(GPC)より求めた。数平均分子量測定は下記の条件で測定を行った。機種:TOSOH HLC−8220GPC カラム:TSKGEL SuperHM-M、溶媒:THF、溶液流出速度:0.6ml毎分、温度:40℃、検出器:示差屈折計、分子量標準:ポリスチレン
酸価、水酸基価は、1gのポリマーポリオール当りのKOHのmgで表わす。酸価は、KOHによる中和滴定で、水酸基価はピリジンと無水酢酸を用いるアセチル化により測定した。また、NCO含有率は試料中に存在するイソシアネート基量を質量分率で表わす。NCO含有率は過剰のジブチルアミンのトルエン溶液を加えて反応させ、相当する尿素を生成させた後、塩酸標準溶液を用いて、指示薬滴定法によって逆滴定を行い、測定を行った。
The number average molecular weights of polyether polyol, polyester diol and the like were determined by gel permeation chromatography (GPC). Number average molecular weight was measured under the following conditions. Model: TOSOH HLC-8220GPC Column: TSKGEL SuperHM-M, solvent: THF, solution outflow rate: 0.6 ml per minute, temperature: 40 ° C., detector: differential refractometer, molecular weight standard: polystyrene acid value, hydroxyl value is Expressed in mg of KOH per gram of polymer polyol. The acid value was measured by neutralization titration with KOH, and the hydroxyl value was measured by acetylation using pyridine and acetic anhydride. Moreover, NCO content rate represents the amount of isocyanate groups present in the sample as a mass fraction. The NCO content was measured by adding an excessive toluene solution of dibutylamine to react to produce the corresponding urea, followed by back titration by an indicator titration method using a hydrochloric acid standard solution.
(合成例1) 水にプロピレンオキシドを付加した数平均分子量約400の2官能ポリプロピレングリコール30部、数平均分子量約2,000の2官能ポリプロピレングリコール40部、グリセリンにプロピレンオキシドを付加した数平均分子量約400の3官能ポリプロピレングリコール20部、4,4’−ジフェニルメタンジイソシアネート40部と2,4’−ジフェニルメタンジイソシアネート60部を反応容器に仕込み、窒素ガス気流下で攪拌しながら70〜80℃で3時間加熱してウレタン化反応を行った。イソシアネート基を有するポリエーテルポリウレタンポリイソシアネート樹脂を得た。イソシアネート基含有率は14.4%であった。以下、この樹脂をポリイソシアネートA-(1)と記す。 (Synthesis Example 1) 30 parts of bifunctional polypropylene glycol having a number average molecular weight of about 400 obtained by adding propylene oxide to water, 40 parts of bifunctional polypropylene glycol having a number average molecular weight of about 2,000, and number average molecular weight obtained by adding propylene oxide to glycerin About 400 trifunctional polypropylene glycol (20 parts), 4,4′-diphenylmethane diisocyanate (40 parts) and 2,4′-diphenylmethane diisocyanate (60 parts) were charged into a reaction vessel and stirred at 70 to 80 ° C. for 3 hours while stirring in a nitrogen gas stream. The urethanization reaction was performed by heating. A polyether polyurethane polyisocyanate resin having an isocyanate group was obtained. The isocyanate group content was 14.4%. Hereinafter, this resin is referred to as polyisocyanate A- (1).
(合成例2) 4,4’−ジフェニルメタンジイソシアネート:70部、2,4’−ジフェニルメタンジイソシアネート:10部とした以外は合成例1と同様にして、イソシアネート基を有するポリエーテルポリウレタンポリイソシアネート樹脂を得た。イソシアネート基含有率は11.5%であった。以下、この樹脂をポリイソシアネートA-(2)と記す。 Synthesis Example 2 A polyether polyurethane polyisocyanate resin having an isocyanate group is obtained in the same manner as in Synthesis Example 1 except that 4,4′-diphenylmethane diisocyanate: 70 parts and 2,4′-diphenylmethane diisocyanate: 10 parts. It was. The isocyanate group content was 11.5%. Hereinafter, this resin is referred to as polyisocyanate A- (2).
(合成例3) 4,4’−ジフェニルメタンジイソシアネート:76部、2,4’−ジフェニルメタンジイソシアネート:38部とした以外は合成例1と同様にして、イソシアネート基を有するポリエーテルポリウレタンポリイソシアネート樹脂を得た。イソシアネート基含有率は16.5%であった。以下、この樹脂をポリイソシアネートA-(3)と記す。 Synthesis Example 3 A polyether polyurethane polyisocyanate resin having an isocyanate group was obtained in the same manner as in Synthesis Example 1 except that 4,4′-diphenylmethane diisocyanate: 76 parts and 2,4′-diphenylmethane diisocyanate: 38 parts. It was. The isocyanate group content was 16.5%. Hereinafter, this resin is referred to as polyisocyanate A- (3).
(合成例4) 4,4’−ジフェニルメタンジイソシアネート:100部とし、2,4’−ジフェニルメタンジイソシアネートを使わなかった以外は合成例1と同様にして、イソシアネート基を有するポリエーテルポリウレタンポリイソシアネート樹脂を得た。イソシアネート基含有率は14.4%であった。以下、この樹脂をポリイソシアネートA-(4)と記す。 (Synthesis Example 4) 4,4′-diphenylmethane diisocyanate: 100 parts, and a polyether polyurethane polyisocyanate resin having an isocyanate group is obtained in the same manner as in Synthesis Example 1 except that 2,4′-diphenylmethane diisocyanate is not used. It was. The isocyanate group content was 14.4%. Hereinafter, this resin is referred to as polyisocyanate A- (4).
(合成例5) 4,4’−ジフェニルメタンジイソシアネートを使わず、2,4’−ジフェニルメタンジイソシアネート:100部とした以外は合成例1と同様にして、イソシアネート基を有するポリエーテルポリウレタンポリイソシアネート樹脂を得た。イソシアネート基の量は14.4%であった。以下、この樹脂をポリイソシアネートA-(5)と記す。 Synthesis Example 5 A polyether polyurethane polyisocyanate resin having an isocyanate group is obtained in the same manner as in Synthesis Example 1 except that 4,4′-diphenylmethane diisocyanate is not used and 2,4′-diphenylmethane diisocyanate is 100 parts. It was. The amount of isocyanate groups was 14.4%. Hereinafter, this resin is referred to as polyisocyanate A- (5).
(合成例6) 4,4’−ジフェニルメタンジイソシアネート及び2,4’−ジフェニルメタンジイソシアネートを使わず、代わりにイソホロンジイソシアネート(IPDI):90部とした以外は合成例A−1と同様にして、イソシアネート基を有するポリエーテルポリウレタンポリイソシアネート樹脂を得た。イソシアネート基の量は14.6%であった。以下、この樹脂をポリイソシアネートA-(6)と記す。 (Synthesis Example 6) Isocyanate group as in Synthesis Example A-1, except that 4,4′-diphenylmethane diisocyanate and 2,4′-diphenylmethane diisocyanate were not used and instead isophorone diisocyanate (IPDI) was 90 parts. A polyether polyurethane polyisocyanate resin having was obtained. The amount of isocyanate groups was 14.6%. Hereinafter, this resin is referred to as polyisocyanate A- (6).
(合成例7) イソフタル酸438部、エチレングリコール106部、ネオペンチルグリコール179部を反応容器に仕込み、窒素ガス気流下で攪拌しながら150℃〜240℃に加熱してエステル化反応を行った。酸価が1.3(mgKOH/g)になったところで反応温度を200℃にし、反応容器内部を徐々に減圧し、1.3kPa以下で30分反応させ、酸価0.4(mgKOH/g)、水酸基価137(mgKOH/g)、数平均分子量約800の両末端に水酸基を有するポリエステルジオール樹脂を得た。以下、このポリオールをポリオール(b1)-1と記す。 (Synthesis Example 7) 438 parts of isophthalic acid, 106 parts of ethylene glycol, and 179 parts of neopentyl glycol were charged into a reaction vessel and heated to 150 ° C. to 240 ° C. while stirring under a nitrogen gas stream to conduct an esterification reaction. When the acid value reached 1.3 (mg KOH / g), the reaction temperature was set to 200 ° C., the pressure inside the reaction vessel was gradually reduced, and the reaction was carried out at 1.3 kPa or less for 30 minutes to give an acid value of 0.4 (mg KOH / g ), A hydroxyl group value of 137 (mgKOH / g) and a number average molecular weight of about 800, a polyester diol resin having hydroxyl groups at both ends was obtained. Hereinafter, this polyol is referred to as polyol (b1) -1.
(合成例8) イソフタル酸373部、テレフタル酸42部、エチレングリコール109部、ネオペンチルグリコール182部を反応容器に仕込み、窒素ガス気流下で攪拌しながら150℃〜240℃に加熱してエステル化反応を行った。酸価が1.3(mgKOH/g)になったところで反応温度を200℃にし、反応容器内部を徐々に減圧し、1.3kPa以下で30分反応させ、酸価0.5(mgKOH/g)、水酸基価184(mgKOH/g)、数平均分子量約600の両末端に水酸基を有するポリエステルジオール樹脂を得た。以下、この樹脂をポリエステルジオール(b1)-2と記す。 (Synthesis Example 8) 373 parts of isophthalic acid, 42 parts of terephthalic acid, 109 parts of ethylene glycol, and 182 parts of neopentyl glycol are charged into a reaction vessel and heated to 150 ° C. to 240 ° C. with stirring in a nitrogen gas stream to perform esterification. Reaction was performed. When the acid value reached 1.3 (mgKOH / g), the reaction temperature was set to 200 ° C., the pressure inside the reaction vessel was gradually reduced, and the reaction was carried out at 1.3 kPa or less for 30 minutes to give an acid value of 0.5 (mgKOH / g ), A hydroxyl group value of 184 (mg KOH / g) and a number average molecular weight of about 600, a polyester diol resin having hydroxyl groups at both ends was obtained. Hereinafter, this resin is referred to as polyester diol (b1) -2.
(合成例9) イソフタル酸298部、アジピン酸262部、エチレングリコール341部、ジエチレングリコール219部を反応容器に仕込み、窒素ガス気流下で攪拌しながら150℃〜240℃に加熱してエステル化反応を行った。酸価が1.3(mgKOH/g)になったところで反応温度を200℃にし、反応容器内部を徐々に減圧し、1.3kPa以下で30分反応させ、酸価0.5(mgKOH/g)、水酸基価40.7(mgKOH/g)、数平均分子量約2,800の両末端に水酸基を有するポリエステルジオール樹脂を得た。以下、この樹脂をポリエステルジオール(b1)-3と記す。 (Synthesis Example 9) 298 parts of isophthalic acid, 262 parts of adipic acid, 341 parts of ethylene glycol, and 219 parts of diethylene glycol were charged into a reaction vessel and heated to 150 ° C. to 240 ° C. with stirring under a nitrogen gas stream to carry out the esterification reaction. went. When the acid value reached 1.3 (mgKOH / g), the reaction temperature was set to 200 ° C., the pressure inside the reaction vessel was gradually reduced, and the reaction was carried out at 1.3 kPa or less for 30 minutes to give an acid value of 0.5 (mgKOH / g ), A hydroxyl group value of 40.7 (mgKOH / g) and a number average molecular weight of about 2,800, a polyester diol resin having hydroxyl groups at both ends was obtained. Hereinafter, this resin is referred to as polyester diol (b1) -3.
(合成例10) イソフタル酸186部、アジピン酸383部、ネオペンチルグリコール429部を反応容器に仕込み、窒素ガス気流下で攪拌しながら150℃〜240℃に加熱してエステル化反応を行った。酸価が1.3(mgKOH/g)になったところで反応温度を200℃にし、反応容器内部を徐々に減圧し、1.3kPa以下で30分反応させ、酸価0.4(mgKOH/g)、水酸基価27.3(mgKOH/g)、数平均分子量約4,000の両末端に水酸基を有するポリエステルジオール樹脂を得た。以下、この樹脂をポリエステルジオール(b1)-4と記す。 (Synthesis Example 10) 186 parts of isophthalic acid, 383 parts of adipic acid, and 429 parts of neopentyl glycol were charged into a reaction vessel and heated to 150 ° C. to 240 ° C. with stirring under a nitrogen gas stream to conduct an esterification reaction. When the acid value reached 1.3 (mg KOH / g), the reaction temperature was set to 200 ° C., the pressure inside the reaction vessel was gradually reduced, and the reaction was carried out at 1.3 kPa or less for 30 minutes to give an acid value of 0.4 (mg KOH / g ), A polyester diol resin having a hydroxyl value of 27.3 (mgKOH / g) and a number average molecular weight of about 4,000 and having hydroxyl groups at both ends. Hereinafter, this resin is referred to as polyester diol (b1) -4.
(合成例11) シス−1,4−シクロヘキサンジカルボン酸310部、1,4−シクロヘキサンジメタノール415部を反応容器に仕込み、窒素ガス気流下で攪拌しながら150℃〜220℃に加熱してエステル化反応を行った。酸価が3.0(mgKOH/g)になったところで反応温度を200℃にし、反応容器内部を徐々に減圧し、1.3kPa以下で30分反応させ、酸価2.0(mgKOH/g)、水酸基価332(mgKOH/g)、数平均分子量約300の両末端に水酸基を有するポリエステルジリオール樹脂を得た。以下、この樹脂をポリエステルポリオール(b2)-1と記す。 (Synthesis Example 11) 310 parts of cis-1,4-cyclohexanedicarboxylic acid and 415 parts of 1,4-cyclohexanedimethanol were charged into a reaction vessel and heated to 150 ° C. to 220 ° C. with stirring under a nitrogen gas stream to form an ester. The reaction was carried out. When the acid value reached 3.0 (mg KOH / g), the reaction temperature was adjusted to 200 ° C., the pressure inside the reaction vessel was gradually reduced, and the reaction was carried out at 1.3 kPa or less for 30 minutes. ), A hydroxyl group value of 332 (mgKOH / g), and a number average molecular weight of about 300, a polyester diriol resin having hydroxyl groups at both ends was obtained. Hereinafter, this resin is referred to as polyester polyol (b2) -1.
(実施例1) 合成例1で得たポリイソシアネートA-(1)を200部容器に仕込み、窒素ガス気流下で攪拌しながら、合成例7で得たポリエステルジオール(b1)-1を90部、ジエチレングリコールを10部、加え、25℃の温水浴中で混合して、無溶剤型接着剤組成物を得た。
この組成物の25℃における粘度を、均一混合後5分以内に測定したところ、2,500mPa・sであった。
なお、前記無溶剤型接着剤組成物は、ポリオール成分中の水酸基:100モルに対し、ポリイソシアネートA-(1)由来のイソシアネート基を166モル含有する。水酸基100モルに対するイソシアネート基の量は、以下のようにして求める。
水酸基100モルに対するイソシアネート基の量=[イソシアネート基(eq.)/水酸基(eq.)]×100
イソシアネート基(eq.)=NCO含有率(質量%)/(42×100)
水酸基(eq.)=56110/水酸基価
NCO含有率(質量%)はJIS K7301に準じて求め、水酸基価はJIS K1557−1に準じて求める。
得られた無溶剤型接着剤組成物のポットライフを以下の方法にて評価した。また、得られた無溶剤型接着剤組成物を用いて、下記の方法に従い積層体を得、積層体の接着力、積層体の界面状態を評価した。結果を表2に示す。
(Example 1) Polyisocyanate A- (1) obtained in Synthesis Example 1 was charged into a 200-part container, and 90 parts of polyester diol (b1) -1 obtained in Synthesis Example 7 was stirred while stirring in a nitrogen gas stream. Then, 10 parts of diethylene glycol was added and mixed in a warm water bath at 25 ° C. to obtain a solventless adhesive composition.
When the viscosity at 25 ° C. of this composition was measured within 5 minutes after uniform mixing, it was 2,500 mPa · s.
In addition, the said solventless type adhesive composition contains 166 mol of isocyanate groups derived from polyisocyanate A- (1) with respect to 100 mol of hydroxyl groups in the polyol component. The amount of the isocyanate group with respect to 100 mol of the hydroxyl group is determined as follows.
Amount of isocyanate group per 100 mol of hydroxyl group = [isocyanate group (eq.) / Hydroxyl group (eq.)] × 100
Isocyanate group (eq.) = NCO content (mass%) / (42 × 100)
Hydroxyl group (eq.) = 56110 / Hydroxyl value The NCO content (mass%) is determined according to JIS K7301, and the hydroxyl value is determined according to JIS K1557-1.
The pot life of the obtained solventless adhesive composition was evaluated by the following method. Moreover, using the obtained solventless adhesive composition, a laminate was obtained according to the following method, and the adhesive strength of the laminate and the interface state of the laminate were evaluated. The results are shown in Table 2.
(実施例2〜11、比較例1〜8) 表2と表3に示すポリイソシアネート成分(A)およびポリオール成分(B)を所定の割合で用いること以外は、実施例1と同様に操作して無溶剤型接着剤組成物を得た。また、実施例1と同様にして、ポットライフ、積層体の接着力および積層体の界面状態を評価した。結果を表2と表3に示す。
なお、数平均分子量約2,800のポリエステルジオール(b1)−3を用いた実施例4、9、数平均分子量約4,000のポリエステルジオール(b1)−4を用いた比較例8は、前記ポリエステルジオール(b1)−3、ポリエステルジオール(b1)−3をそれぞれ70℃に加熱した後、25℃の温水浴中でポリイソシアネートA−(1)等と混合し、混合後5分以内の粘度をB型粘度計にて測定した。測定時の接着剤組成物の温度は約50℃であった。
(Examples 2 to 11 and Comparative Examples 1 to 8) The same operations as in Example 1 were performed except that the polyisocyanate component (A) and the polyol component (B) shown in Tables 2 and 3 were used in a predetermined ratio. Thus, a solventless adhesive composition was obtained. In the same manner as in Example 1, the pot life, the adhesive strength of the laminate, and the interface state of the laminate were evaluated. The results are shown in Tables 2 and 3.
Examples 4 and 9 using a polyester diol (b1) -3 having a number average molecular weight of about 2,800, and Comparative Example 8 using a polyester diol (b1) -4 having a number average molecular weight of about 4,000 are as described above. Polyester diol (b1) -3 and polyester diol (b1) -3 are each heated to 70 ° C. and then mixed with polyisocyanate A- (1) and the like in a warm water bath at 25 ° C., and the viscosity is within 5 minutes after mixing. Was measured with a B-type viscometer. The temperature of the adhesive composition at the time of measurement was about 50 ° C.
<ポットライフ> 各実施例または比較例で得られた無用剤型接着剤組成物を200gの250mL容量の蓋付きガラス瓶に封入し、50℃温水浴で30分経時した後の粘度をB型粘度計にて測定することによりポットライフを検討した。測定時の接着剤組成物の温度は約50℃であった。 <Pot life> The useless adhesive composition obtained in each example or comparative example was sealed in a glass bottle with a lid of 200 g and a capacity of 250 mL, and the viscosity after 30 minutes of aging in a 50 ° C. hot water bath was measured as B type viscosity. The pot life was examined by measuring with a meter. The temperature of the adhesive composition at the time of measurement was about 50 ° C.
[積層体の作製] 50℃に調整した各実施例または比較例で得られた無溶剤型接着剤組成物を、PET(ポリエチレンテレフタレート)フィルム(厚さ:12μm)の表面に、無溶剤テストコーターで70℃にて塗布し(塗布量:2.0g/m2)、この塗布面にアルミニウム蒸着無延伸ポリプロピレンフィルム(VMCPP、厚さ:25μm)の蒸着面を重ね、準備段階の積層体(プレ積層体)を得た。これらプレ積層体を25℃、湿度60%RTまたは80%RTの環境下にて、1日間または2日間エージングして時間放置し、積層体を作製した。得られた各積層体について、接着力および積層体の界面状態を下記の要領で観察・測定し、それらの結果を表2と表3に示す。 [Production of Laminate] The solventless adhesive composition obtained in each Example or Comparative Example adjusted to 50 ° C. was coated on the surface of a PET (polyethylene terephthalate) film (thickness: 12 μm) with a solventless test coater. At a temperature of 70 ° C. (application amount: 2.0 g / m 2 ), and a vapor-deposited surface of an aluminum vapor-deposited unstretched polypropylene film (VMPP, thickness: 25 μm) is layered on the coated surface. A laminate was obtained. These pre-laminated bodies were aged for 1 day or 2 days in an environment of 25 ° C. and humidity of 60% RT or 80% RT, and allowed to stand for a period of time to produce laminated bodies. About each obtained laminated body, the adhesive force and the interface state of a laminated body were observed and measured in the following way, and those results are shown in Table 2.
(接着力) 積層体を長さ300mm、幅15mmに切り取り、テストピースとした。インストロン型引張試験機を使用し、25℃の環境下にて、剥離速度300mm/分の剥離速度で引張り、PET/VMCPP間のT型剥離強度(N/15mm)を測定した。この試験を5回行い、その平均値を求めた。 (Adhesive force) The laminate was cut to a length of 300 mm and a width of 15 mm to obtain a test piece. Using an Instron type tensile tester, the sample was pulled at a peeling rate of 300 mm / min in an environment of 25 ° C., and the T-type peeling strength (N / 15 mm) between PET / VMCP was measured. This test was performed 5 times, and the average value was obtained.
(積層体の界面状態) 積層体をPETフィルム側からPETフィルムを透して下地の蒸着面を目視観察し、以下の基準にて積層体の界面状態(蒸着面上の接着剤層の状態)を評価した。
○:蒸着面上に、ゆず肌状の模様や小さな斑点状の模様がなく、接着剤層が均一である。
△:蒸着面上に、ゆず肌状の模様や小さな斑点状の模様が多少観測されるが、使用上問題ないレベルである。
×:蒸着面上に、ゆず肌状の模様や小さな斑点状の模様が多数観察された。
(Interfacial state of the laminate) Through the PET film side from the PET film side, the underlying vapor deposition surface is visually observed, and the interface state of the laminate (adhesive layer state on the vapor deposition surface) is as follows. Evaluated.
○: There is no yuzu skin-like pattern or small spot-like pattern on the deposition surface, and the adhesive layer is uniform.
(Triangle | delta): Although a yuzu skin-like pattern and a small spot-like pattern are somewhat observed on a vapor deposition surface, it is a level which does not have a problem in use.
X: Many yuzu skin-like patterns and small spot-like patterns were observed on the vapor deposition surface.
表2より、実施例1〜11は、蒸着面上の接着剤層の状態が良好で接着強度にも優れていることがわかる。特に実施例1、2は、エージング時の環境湿度が高くても短時間で充分な接着強度を発現できる。これに対し、イソシアネート成分として4,4’−MDI由来の成分のみを用いる比較例1は、エージング時の環境湿度の影響を著しく受け、25℃、80%RT環境下でエージングした場合、蒸着面上の接着剤層の状態が著しく悪く、接着強度も極めて小さい。また、イソシアネート成分として2,4’−MDI由来の成分のみを用いる比較例2、イソホロンジイソシアネートのみを用いる比較例3は、蒸着面上の接着剤層の状態は良好ではあるが、接着強度が著しく劣っていることがわかる。なお、比較例3の場合、初期粘度測定時の温度が25℃であり、混合後30分経過後の粘度測定時の温度が50℃なので、一見30分経過後の粘度が低下しているかのように見える。2,4’−MDIおよび4,4’−MDIを用いる実施例や比較例の場合、測定時の温度が相違しても、30分経過後の粘度の方が大きいのは、ポリオール成分(A)との反応が進行しているからである。言い換えると、イソホロンジイソシアネートは、2,4’−MDIおよび4,4’−MDIに比して反応性に劣り、50℃で30分程度ではポリオール成分(A)との反応があまり進行しないので、粘度上昇がほとんど観察されず、測定温度の影響による見かけの粘度低下が観察される。また、接着強度が著しく小さいのは、低温短時間(25℃×1日または2日)のエージングでは、反応があまり進行していないことが原因と考察される。 From Table 2, it can be seen that in Examples 1 to 11, the state of the adhesive layer on the vapor deposition surface is good and the adhesive strength is also excellent. In particular, Examples 1 and 2 can exhibit sufficient adhesive strength in a short time even when the environmental humidity during aging is high. On the other hand, Comparative Example 1 using only the component derived from 4,4′-MDI as the isocyanate component is significantly affected by the environmental humidity during aging, and when aging is performed at 25 ° C. and 80% RT, The state of the upper adhesive layer is extremely poor, and the adhesive strength is extremely small. In Comparative Example 2 using only a component derived from 2,4′-MDI as an isocyanate component and Comparative Example 3 using only isophorone diisocyanate, the adhesive layer on the deposition surface is in a good state, but the adhesive strength is remarkably high. It turns out that it is inferior. In the case of Comparative Example 3, the temperature at the time of initial viscosity measurement is 25 ° C., and the temperature at the time of viscosity measurement after 30 minutes after mixing is 50 ° C. looks like. In Examples and Comparative Examples using 2,4′-MDI and 4,4′-MDI, the viscosity after 30 minutes is greater even when the temperature during measurement is different. This is because the reaction with) proceeds. In other words, isophorone diisocyanate is less reactive than 2,4′-MDI and 4,4′-MDI, and the reaction with the polyol component (A) does not proceed much at 50 ° C. for about 30 minutes. Almost no increase in viscosity is observed, and an apparent decrease in viscosity due to the influence of the measurement temperature is observed. Moreover, it is considered that the reason why the adhesive strength is remarkably low is that the reaction does not proceed so much in aging at a low temperature for a short time (25 ° C. × 1 day or 2 days).
また、ポリオール成分(B)として低分子量のジオール(b2)やトリオール(b3)を含有しない比較例4は、蒸着面上の接着剤層の状態は良好ではあるが、接着強度が著しく劣っていることがわかる。更に、ポリオール成分(B)として低分子量ジオール(b2)やトリオール(b3)のみを用いたり(比較例5、6、7)、ポリエステルジオール(b1)として、Mnが4,000のポリエステルジオール(b1)-4を用いたり(比較例8)した場合には、蒸着面上の接着剤層の状態も劣り、接着強度が著しく劣っていることがわかる。
なお、比較例7は、混合直後の粘度は実施例と遜色ないが、ポリオール成分(B)が低分子量のトリオール(b3)のみから成るので、ポリイソシアネート成分(A)との反応点が多く、短時間で粘度が著しく上昇するという結果となった。
In Comparative Example 4 which does not contain the low molecular weight diol (b2) or triol (b3) as the polyol component (B), the state of the adhesive layer on the vapor deposition surface is good, but the adhesive strength is extremely inferior. I understand that. Further, only the low molecular weight diol (b2) or the triol (b3) is used as the polyol component (B) (Comparative Examples 5, 6, 7), or the polyester diol (b1) having an Mn of 4,000 as the polyester diol (b1). ) -4 is used (Comparative Example 8), it can be seen that the state of the adhesive layer on the vapor deposition surface is also inferior and the adhesive strength is remarkably inferior.
In Comparative Example 7, the viscosity immediately after mixing is comparable to that of the Example, but since the polyol component (B) consists only of the low molecular weight triol (b3), there are many reactive points with the polyisocyanate component (A). As a result, the viscosity increased remarkably in a short time.
本発明の接着剤組成物は、各種プラスチックフィルム同士、並びにプラスチックフィルムと金属蒸着フィルムまたは金属箔とを貼り合せる用途として好適であり、特に、食品、医療品、化粧品等の包装材形成用ラミネート用接着剤として好適である。また、薄膜状のフィルム同士の接合に好適なものであるが、厚みに限定されず、種々の形状や形態の接合にも本発明の接着剤組成物を好適に用いることができる。更に、本発明の接着剤組成物は、無溶剤型に好適に適用できるので、溶剤フリーの接着剤全般に広く適用できる。 The adhesive composition of the present invention is suitable for use in bonding various plastic films and between plastic films and metal-deposited films or metal foils, and in particular for laminates for forming packaging materials for foods, medical products, cosmetics and the like. Suitable as an adhesive. Moreover, although it is a thing suitable for joining of thin film films, it is not limited to thickness, The adhesive composition of this invention can be used suitably also for joining of various shapes and forms. Furthermore, since the adhesive composition of the present invention can be suitably applied to a solvent-free type, it can be widely applied to general solvent-free adhesives.
Claims (8)
前記ポリイソシアネート成分(A)が、
2,4’−ジフェニルメタンジイソシアネート(a1)および4,4’−ジフェニルメタンジイソシアネート(a2)を必須とするイソシアネートと、
ポリエーテルポリオール(a3)を必須とするポリオールと、
をイソシアネート基過剰の条件下で反応させてなる反応性生成物であり、
前記ポリオール成分(B)が、数平均分子量500以上、3,000以下のポリエステルジオール(b1)を必須とし、更に数平均分子量50以上、500未満のジオール(b2)および数平均分子量50以上、500未満のトリオール(b3)の少なくともいずれか一方を含む、ポリオール組成物である、接着剤組成物。 An adhesive composition comprising a polyisocyanate component (A) and a polyol component (B),
The polyisocyanate component (A) is
An isocyanate essentially comprising 2,4′-diphenylmethane diisocyanate (a1) and 4,4′-diphenylmethane diisocyanate (a2);
A polyol essentially comprising the polyether polyol (a3);
Is a reactive product obtained by reacting under an excess of isocyanate groups,
The polyol component (B) essentially comprises a polyester diol (b1) having a number average molecular weight of 500 or more and 3,000 or less, a diol (b2) having a number average molecular weight of 50 or more and less than 500, and a number average molecular weight of 50 or more, 500 The adhesive composition which is a polyol composition containing at least any one of less than triol (b3).
2,4’−ジフェニルメタンジイソシアネート(a1)が10モル%以上、60モル%以下、
4,4’−ジフェニルメタンジイソシアネート(a2)が40モル%以上、90モル%以下である請求項1に記載の接着剤組成物。 In a total of 100 mol% of 2,4′-diphenylmethane diisocyanate (a1) and 4,4′-diphenylmethane diisocyanate (a2),
2,4′-diphenylmethane diisocyanate (a1) is 10 mol% or more and 60 mol% or less,
The adhesive composition according to claim 1, wherein 4,4'-diphenylmethane diisocyanate (a2) is 40 mol% or more and 90 mol% or less.
ポリエステルジオール(b1)を60質量%以上、99質量%以下、
ジオール(b2)とトリオール(b3)とを合わせて1質量%以上、40質量%以下含む、請求項1または2記載の接着剤組成物。 In 100% by mass of the polyol component (B),
60% by mass or more and 99% by mass or less of polyester diol (b1),
The adhesive composition of Claim 1 or 2 which contains 1 mass% or more and 40 mass% or less of diol (b2) and triol (b3) together.
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PCT/JP2014/000225 WO2014115521A1 (en) | 2013-01-22 | 2014-01-17 | Adhesive composition, and laminate and method for manufacturing same |
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MY169045A (en) | 2019-02-08 |
TW201430086A (en) | 2014-08-01 |
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CN104955913B (en) | 2017-05-17 |
PH12015501618A1 (en) | 2015-09-28 |
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WO2014115521A1 (en) | 2014-07-31 |
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