JPWO2018101242A1 - Reactive adhesive, laminated film and packaging - Google Patents
Reactive adhesive, laminated film and packaging Download PDFInfo
- Publication number
- JPWO2018101242A1 JPWO2018101242A1 JP2018518550A JP2018518550A JPWO2018101242A1 JP WO2018101242 A1 JPWO2018101242 A1 JP WO2018101242A1 JP 2018518550 A JP2018518550 A JP 2018518550A JP 2018518550 A JP2018518550 A JP 2018518550A JP WO2018101242 A1 JPWO2018101242 A1 JP WO2018101242A1
- Authority
- JP
- Japan
- Prior art keywords
- isocyanate
- polyol
- adhesive
- component
- layer
- 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
- 239000004823 Reactive adhesive Substances 0.000 title claims abstract description 36
- 238000004806 packaging method and process Methods 0.000 title claims description 7
- 229920005862 polyol Polymers 0.000 claims abstract description 81
- 150000003077 polyols Chemical class 0.000 claims abstract description 67
- 239000012948 isocyanate Substances 0.000 claims abstract description 66
- -1 polyol compound Chemical class 0.000 claims abstract description 61
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 57
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 24
- 239000003085 diluting agent Substances 0.000 claims abstract description 20
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000000539 dimer Substances 0.000 claims abstract description 6
- 239000013638 trimer Substances 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 52
- 239000002985 plastic film Substances 0.000 claims description 24
- 229920006255 plastic film Polymers 0.000 claims description 24
- 239000012790 adhesive layer Substances 0.000 claims description 18
- 238000010030 laminating Methods 0.000 claims description 11
- 125000005442 diisocyanate group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 41
- 239000000049 pigment Substances 0.000 description 34
- 239000000853 adhesive Substances 0.000 description 33
- 230000001070 adhesive effect Effects 0.000 description 33
- 239000005056 polyisocyanate Substances 0.000 description 32
- 229920001228 polyisocyanate Polymers 0.000 description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 229920005906 polyester polyol Polymers 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 229920001451 polypropylene glycol Polymers 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 229920003023 plastic Polymers 0.000 description 14
- 239000004033 plastic Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 12
- 239000004721 Polyphenylene oxide Substances 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 229920000570 polyether Polymers 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- 125000001931 aliphatic group Chemical group 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 10
- 238000010828 elution Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229920001515 polyalkylene glycol Polymers 0.000 description 9
- 239000000565 sealant Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000003599 detergent Substances 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 150000003142 primary aromatic amines Chemical class 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 238000003475 lamination Methods 0.000 description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229920002292 Nylon 6 Polymers 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 5
- 230000032798 delamination Effects 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 229920000092 linear low density polyethylene Polymers 0.000 description 5
- 239000004707 linear low-density polyethylene Substances 0.000 description 5
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000002318 adhesion promoter Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 3
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 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 3
- 239000005001 laminate film Substances 0.000 description 3
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- 239000005022 packaging material Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 2
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- 230000003449 preventive effect Effects 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Polyurethanes Or Polyureas (AREA)
- Wrappers (AREA)
Abstract
ポリオール化合物を含有するポリオール成分Aと、イソシアネート化合物を含有するイソシアネート成分Bとを有し、前記イソシアネート成分Bは、ポリオールとイソシアネートとの反応生成物(B−1)及び数平均分子量が400〜1000の範囲であるイソシアネート基を有する反応性希釈剤(B−2)を含有し、前記ポリオール成分Aとイソシアネート成分Bとを重量比の割合で配合し40℃雰囲気下で30分放置後の粘度が5000mPa・s以下である反応型接着剤、積層フィルム、及び包装体。前記イソシアネート基を有する反応性希釈剤(B−2)が、芳香族ジイソシアネート、脂肪族ジイソシアネート、またはそれらの二量体または三量体であることが好ましい。It has a polyol component A containing a polyol compound and an isocyanate component B containing an isocyanate compound, and the isocyanate component B has a reaction product (B-1) of polyol and isocyanate and a number average molecular weight of 400 to 1000. And a reactive diluent (B-2) having an isocyanate group in the range of the above, the polyol component A and the isocyanate component B are blended in a ratio by weight, and the viscosity after standing for 30 minutes in an atmosphere of 40 ° C. A reactive adhesive, a laminated film, and a package that are 5000 mPa · s or less. It is preferable that the reactive diluent (B-2) having an isocyanate group is an aromatic diisocyanate, an aliphatic diisocyanate, or a dimer or trimer thereof.
Description
本発明は反応型接着剤、それを使用してなる積層フィルム及び包装体に関する。 The present invention relates to a reactive adhesive, a laminated film using the same, and a package.
各種包装材、ラベル等に用いられる積層フィルム(ラミネートフィルムとも称する場合がある)は、各種多種多様なプラスチックフィルム、金属箔、紙等のラミネートにより、意匠性、機能性、保存性、利便性、輸送性が付与され、特に該積層フィルムを袋状に成形してなる包装体は、食品、医薬品、洗剤等の包装体として使用されている。 Laminate films (sometimes referred to as laminate films) used for various packaging materials, labels, etc. are designed, functional, storable, and convenient by laminating various types of plastic films, metal foil, paper, etc. A package that is provided with transportability and is formed by forming the laminated film into a bag shape is used as a package for foods, pharmaceuticals, detergents, and the like.
従来ラミネートフィルムには、揮発性の有機溶剤に溶解した接着剤(溶剤型ラミネート接着剤と称される場合がある)をフィルムに塗工し、オーブンを通過する過程で有機溶剤を揮発させ、別のフィルムを貼り合わせるドライラミネーション方式により得るものが主流であったが、近年、環境負荷の低減および作業環境の改善の観点から、揮発性の有機溶剤を含有しない、反応型2液タイプのラミネート接着剤(反応型接着剤、あるいは無溶剤型ラミネート接着剤と称される場合がある)の需要が高まりつつある。(例えば特許文献1参照) For conventional laminate films, an adhesive (sometimes called a solvent-type laminate adhesive) dissolved in a volatile organic solvent is applied to the film, and the organic solvent is volatilized while passing through an oven. However, in recent years, from the viewpoint of reducing the environmental burden and improving the working environment, reactive two-component laminate bonding that does not contain volatile organic solvents has been the mainstream. There is a growing demand for agents (sometimes referred to as reactive adhesives or solventless laminate adhesives). (For example, see Patent Document 1)
前記特許文献1記載の反応型接着剤は、無溶剤型接着剤における接着強度とエージング時間短縮に効果があるものの、芳香族イソシアネートとポリエステルジオールとを組み合わせることから、無溶剤型接着剤用の樹脂としては比較的ポットライフが短いものであった。ポットライフが短い場合、塗布量のバラツキを生じやすくなり、その結果ラミネート外観が著しく損なわれるおそれがある。また原反交換の際などラミネート装置が一時的に停止した場合、ポットライフが短い接着剤の場合は、接着剤の取替えやロールの掃除などの作業が必要となり、作業性が著しく損なわれるおそれもある。 Although the reactive adhesive described in Patent Document 1 is effective in shortening the adhesive strength and aging time in a solventless adhesive, it is a resin for a solventless adhesive because it combines aromatic isocyanate and polyester diol. As a relatively short pot life. If the pot life is short, variations in the coating amount are likely to occur, and as a result, the laminate appearance may be significantly impaired. Also, when the laminating equipment is temporarily stopped, such as when replacing the raw material, and when the adhesive has a short pot life, work such as adhesive replacement or roll cleaning is required, and workability may be significantly impaired. is there.
更に反応型接着剤は、原料として溶剤型ラミネート接着剤よりも若干低分子の反応性モノマーを使用することから、ラミネート後のフィルムを通して内容物に溶出する可能性があった。特に近年では、欧州を始め、プラスチック容器から化学物質の溶出(移行)する成分の規制が細かく定義されるようになり、容器からの化学物質の溶出成分が少ない製品が求められている。一般に接着剤に使用される化学物質の溶出では、SML(Specific migration limit)が規定されており、溶出物は容易に制御可能であるが、合成等で生成する非意図的添加物質(NIAS)の溶出は簡単にはクリアできない問題となっている。 Furthermore, since the reactive adhesive uses a reactive monomer having a slightly lower molecular weight than that of the solvent-type laminating adhesive as a raw material, there is a possibility that the reactive adhesive may elute into the contents through the laminated film. In recent years, in particular, regulations for components that elute (transfer) chemical substances from plastic containers have been finely defined in Europe and the like, and products with less chemical substance elution components from containers have been demanded. In general, SML (Specific migration limit) is specified for elution of chemical substances used for adhesives, and the eluate is easily controllable, but unintentionally added substances (NIAS) generated by synthesis etc. Elution is a problem that cannot be easily cleared.
これに対し、カルボジイミド修飾ジフェニルメタンジイソシアネート、アロファネート修飾ジフェニルメタンジイソシアネート、ビウレット修飾ジフェニルメタンジイソシアネート、ポリマージフェニルメタンジイソシアネート及びこれらの組み合わせからなる群から選択される修飾されたジフェニルメタンジイソシアネート(MDI)との反応生成物であるイソシアネート末端ポリウレタンプレポリマーとポリオールとを含む接着剤が、低濃度の抽出性一級芳香族アミン(PAA)を生じる接着剤であることが知られている(例えば特許文献2参照)。しかしながら該接着剤は、該修飾されたジフェニルメタンジイソシアネートをポリオールと反応させて用いるため、高粘度になりやすく、依然としてポットライフは短い傾向にあった。
従って、非意図的物質の溶出が少なく且つポットライフの長い反応性接着剤は、いまだ実用上満足のいくものが得られていないのが現状である。In contrast, an isocyanate end which is a reaction product with a modified diphenylmethane diisocyanate (MDI) selected from the group consisting of carbodiimide modified diphenylmethane diisocyanate, allophanate modified diphenylmethane diisocyanate, biuret modified diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate and combinations thereof It is known that an adhesive containing a polyurethane prepolymer and a polyol is an adhesive that produces a low concentration of extractable primary aromatic amine (PAA) (see, for example, Patent Document 2). However, the adhesive is used by reacting the modified diphenylmethane diisocyanate with a polyol, so that the viscosity tends to be high and the pot life still tends to be short.
Therefore, the present situation is that a reactive adhesive with little unintentional substance elution and a long pot life has not yet been obtained in practical use.
本発明が解決しようとする課題は、ラミネート後のフィルムを通して内容物に溶出する非意図的物質が非常に少なく、且つポットライフの長い反応性接着剤を提供することにある。 The problem to be solved by the present invention is to provide a reactive adhesive that has a very small amount of unintentional substances that elute into the contents through the film after lamination and has a long pot life.
本発明者らは、特定の数平均分子量の範囲のイソシアネート化合物を反応性希釈剤として使用し、且つ、ポリオール成分とイソシアネート成分を重量比の割合で配合し40℃雰囲気下で30分放置後の粘度が5000mPa・s以下である反応型接着剤が、上記課題を解決できることを見いだした。 The inventors of the present invention use an isocyanate compound having a specific number average molecular weight in the range of a reactive diluent, blend a polyol component and an isocyanate component in a ratio by weight, and leave the mixture in a 40 ° C. atmosphere for 30 minutes. It has been found that a reactive adhesive having a viscosity of 5000 mPa · s or less can solve the above problems.
即ち本発明は、ポリオール化合物を含有するポリオール成分Aと、イソシアネート化合物を含有するイソシアネート成分Bとを有し、
前記イソシアネート成分Bは、ポリオールとイソシアネートとの反応生成物(B−1)及び数平均分子量が400〜1000の範囲であるイソシアネート基を有する反応性希釈剤(B−2)を含有し、
前記ポリオール成分Aとイソシアネート成分Bとを重量比の割合で配合し40℃雰囲気下で30分放置後の粘度が5000mPa・s以下である反応型接着剤を提供する。That is, the present invention has a polyol component A containing a polyol compound and an isocyanate component B containing an isocyanate compound,
The isocyanate component B contains a reaction product (B-1) of a polyol and an isocyanate and a reactive diluent (B-2) having an isocyanate group having a number average molecular weight in the range of 400 to 1,000.
Provided is a reactive adhesive in which the polyol component A and the isocyanate component B are blended in a ratio by weight and the viscosity after being allowed to stand in a 40 ° C. atmosphere for 30 minutes is 5000 mPa · s or less.
また本発明は、第一のプラスチックフィルムと第二のプラスチックフィルムの間に接着剤層を積層してなる積層フィルムであって、前記接着剤層が前記記載の反応型接着剤の層である積層フィルムを提供する。 The present invention also provides a laminated film obtained by laminating an adhesive layer between a first plastic film and a second plastic film, wherein the adhesive layer is a layer of the reactive adhesive described above. Provide film.
また本発明は、第一のプラスチックフィルムと第二のプラスチックフィルムの間に接着剤層を積層してなる積層フィルムを袋状に成形してなる包装体であって、前記接着剤層が前記記載の反応型接着剤の層である包装体を提供する。 Moreover, this invention is a package formed by shape | molding the laminated film formed by laminating | stacking an adhesive bond layer between a 1st plastic film and a 2nd plastic film in a bag shape, Comprising: The said adhesive bond layer is the said description. A package that is a layer of the reactive adhesive is provided.
本発明によれば、ラミネート後のフィルムを通して内容物に溶出する非意図的物質が非常に少ないため、洗剤や薬剤などの内容物の充填時、充填後の時間経過後も、デラミネーション等のラミネート構成体の剥離を発生させず、優れた接着性、内容物耐性を有する。また低粘度でありポットライフが長いため、接着剤配合後の作業性に優れる。 According to the present invention, since there are very few unintentional substances that elute into the contents through the film after laminating, laminating such as delamination even when the contents such as detergents and drugs are filled and after the time has elapsed after filling. It does not cause peeling of the structure and has excellent adhesion and content resistance. Moreover, since it has a low viscosity and a long pot life, it is excellent in workability after blending an adhesive.
(溶剤)
本発明で使用する接着剤は、前述の通り反応型2液タイプのラミネート接着剤であり、従来の揮発性の有機溶剤を使用しないことから無溶剤型ラミネート接着剤とも称される。
本発明では、イソシアネート基と水酸基との化学反応によって硬化する接着剤を使用する。なお本発明でいう無溶剤型の接着剤の「溶剤」とは、本発明で使用するポリイソシアネートやポリオールを溶解することの可能な、溶解性が高く揮発性の有機溶剤を指し、「無溶剤」とは、これらの溶解性の高い有機溶剤を含まないことを指す。溶解性の高い有機溶剤とは、具体的には、トルエン、キシレン、塩化メチレン、テトラヒドロフラン、酢酸メチル、酢酸エチル、酢酸nープロピル、酢酸n−ブチル、アセトン、メチルエチルケトン(MEK)、シクロヘキサノン、トルオール、キシロール、n−ヘキサン、シクロヘキサン等が挙げられる。中でもトルエン、キシレン、塩化メチレン、テトラヒドロフラン、酢酸メチル、酢酸エチルは特に溶解性の高い有機溶剤として知られている。(solvent)
The adhesive used in the present invention is a reactive two-component laminate adhesive as described above, and is also referred to as a solventless laminate adhesive because a conventional volatile organic solvent is not used.
In the present invention, an adhesive that cures by a chemical reaction between an isocyanate group and a hydroxyl group is used. The “solvent” of the solventless adhesive referred to in the present invention refers to a highly soluble and volatile organic solvent capable of dissolving the polyisocyanate and polyol used in the present invention. "" Refers to the absence of these highly soluble organic solvents. Specific examples of highly soluble organic solvents include toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluol, and xylol. , N-hexane, cyclohexane and the like. Of these, toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, and ethyl acetate are known as organic solvents having particularly high solubility.
一方本発明の接着剤は、低粘度等の要求がある場合には、所望の粘度に応じて適宜前記溶解性の高い有機溶剤で希釈して使用してもよい。その場合は、ポリイソシアネート組成物(X)またはポリオール組成物(Y)のいずれか1つを希釈してもよいし両方を希釈してもよい。このような場合に使用する有機溶剤としては、例えば酢酸メチル、酢酸エチル、酢酸nープロピル、酢酸n−ブチル、アセトン、メチルエチルケトン(MEK)、シクロヘキサノン、トルオール、キシロール、n−ヘキサン、シクロヘキサン等が挙げられる。これらの中でも溶解性の点から酢酸エチルやメチルエチルケトン(MEK)が好ましく、特に酢酸エチルが好ましい。有機溶剤の使用量は所要される粘度によるが概ね0.1〜10質量%の範囲で使用することが多い。
また、本発明の接着剤の低粘度化を達成するために、トリアセチン、プロピレンカーボネート等の水酸基を有さないカルボニル基を有する沸点200℃以上の溶剤も使用してよい。これら高沸点の有機溶剤の使用量は所要される粘度と塗膜物性によるが概ね0.1〜10質量%の範囲で使用することが多い。On the other hand, when there is a demand for low viscosity or the like, the adhesive of the present invention may be appropriately diluted with the organic solvent having high solubility according to the desired viscosity. In that case, either one of the polyisocyanate composition (X) or the polyol composition (Y) may be diluted, or both may be diluted. Examples of the organic solvent used in such a case include methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluol, xylol, n-hexane, and cyclohexane. . Among these, ethyl acetate and methyl ethyl ketone (MEK) are preferable from the viewpoint of solubility, and ethyl acetate is particularly preferable. The amount of the organic solvent used depends on the required viscosity, but is generally in the range of 0.1 to 10% by mass.
Moreover, in order to achieve the low viscosity of the adhesive of the present invention, a solvent having a boiling point of 200 ° C. or higher having a carbonyl group having no hydroxyl group such as triacetin and propylene carbonate may be used. The amount of these high-boiling organic solvents to be used depends on the required viscosity and physical properties of the coating film, but is generally in the range of 0.1 to 10% by mass.
(ポリオール化合物を含有するポリオール成分A)
本発明において、ポリオール成分Aが含有するポリオール化合物は、特に限定なく公知のポリオールを使用することができる。例えばポリエステルポリオール、ポリエーテルポリオール、ポリウレタンポリオール、ポリエーテルエステルポリオール、ポリエステル(ポリウレタン)ポリオール、ポリエーテル(ポリウレタン)ポリオール、ポリエステルアミドポリオール、アクリルポリオール、ポリカーボネートポリオール、ポリヒドロキシルアルカン、ひまし油又はそれらの混合物から選ばれるポリマーポリオールを挙げることができる。(Polyol component A containing polyol compound)
In the present invention, as the polyol compound contained in the polyol component A, a known polyol can be used without any particular limitation. For example, selected from polyester polyol, polyether polyol, polyurethane polyol, polyether ester polyol, polyester (polyurethane) polyol, polyether (polyurethane) polyol, polyester amide polyol, acrylic polyol, polycarbonate polyol, polyhydroxyl alkane, castor oil or mixtures thereof And polymer polyols.
ポリ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、セバチン酸等二塩基酸若しくはそれらのジアルキルエステル又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若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ポリ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ポリオールが挙げられる。 Examples of the polyester polyol include 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, neodymium. Glycols such as pentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3′-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, or the like Ring opening polymerization of lactones such as polyester polyol or polycaprolactone, polyvalerolactone, poly (β-methyl-γ-valerolactone) obtained by reacting them with the mixture The polyester polyol obtained by combining is mentioned.
ポリエーテルポリオールとしては、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が挙げられる。 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若しくはそれらのジアルキルエステル又はそれらの混合物と、上記ポリエーテルポリオールを反応させて得られるポリエーテルエステルポリオールが挙げられる。 As the polyether polyol, for example, an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran is polymerized using, for example, water, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, and the like as a low-part polyol. The polyether polyol obtained is mentioned. Examples of the polyether ester polyol include a polybasic acid obtained by reacting the above polyether polyol with a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid or the like or a mixture thereof. Examples include ether ester polyols.
ポリウレタンポリオールとしては、1分子中にウレタン結合を有するポリオールであり、例えば、数平均分子量200〜20,000のポリエーテルポリオールと有機ポリイソシアネートとの反応物で、NCO/OHが1未満が好ましく、より好ましくは0.9以下のものを挙げることができる。有機ポリイソシアネートは後述のポリイソシアネート化合物、特にジイソシアネート化合物を使用することができる。 The polyurethane polyol is a polyol having a urethane bond in one molecule, for example, a reaction product of a polyether polyol having a number average molecular weight of 200 to 20,000 and an organic polyisocyanate, preferably having an NCO / OH of less than 1. More preferably, 0.9 or less can be mentioned. As the organic polyisocyanate, a polyisocyanate compound described later, particularly a diisocyanate compound can be used.
ポリエーテル(ポリウレタン)ポリオール、ポリエステル(ポリウレタン)ポリオールは、ポリエステルポリオールやポリエーテルエステルポリオール等と有機ポリイソシアネートとの反応物で、NCO/OHが1未満が好ましく、より好ましくは0.9以下のものを挙げることができる。 Polyether (polyurethane) polyols and polyester (polyurethane) polyols are reaction products of polyester polyols, polyether ester polyols, and the like with organic polyisocyanates, preferably having an NCO / OH of less than 1, more preferably 0.9 or less. Can be mentioned.
ポリエステルアミドポリオールとしては、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あわせて使用することによって得られる。
アクリルポリ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、メタクリル酸又はそのエステルとを共重合することによって得られる。The polyesteramide polyol can be obtained, for example, by using an aliphatic diamine having an amino group such as ethylenediamine, propylenediamine, hexamethylenediamine as a raw material in the esterification reaction.
Examples of acrylic polyols include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyhydroxybutyl, etc., or their corresponding methacrylic acid derivatives containing one or more hydroxyl groups in one molecule, such as acrylic acid, methacrylic acid, etc. It is obtained by copolymerizing an acid or its ester.
ポリカーボネートポリオールとしては、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、ビスフェノールA、水添ビスフェノールAの中から選ばれた1種又は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 polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 1,9-nonane. One selected from diol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A or The thing obtained by reaction of 2 or more types of glycol with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, etc. is mentioned.
ポリヒドロキシアルカンとしては、ブタジエン、又はブタジエンとアクリルアミド等と共重合して得られる液状ゴムが挙げられる。
中でも、ポリエーテル(ポリウレタン)ポリオールが特に好ましい。Examples of the polyhydroxyalkane include butadiene or liquid rubber obtained by copolymerization with butadiene and acrylamide.
Among these, a polyether (polyurethane) polyol is particularly preferable.
また、本発明に用いられるポリオール化合物として、ポリイソシアネートとビス(ヒドロキシアルキル)アミンの反応物であって末端にウレア結合基を有するものも好ましく用いることができる。 As the polyol compound used in the present invention, a reaction product of polyisocyanate and bis (hydroxyalkyl) amine having a urea bond group at the terminal can also be preferably used.
(イソシアネート化合物を含有するイソシアネート成分B)
本発明においてイソシアネート成分Bは、ポリオールとイソシアネートとの反応生成物(B−1)であるイソシアネート化合物、及び数平均分子量が400〜1000の範囲であるイソシアネート基を有する反応性希釈剤(B−2)であるイソシアネート化合物を含有する。(Isocyanate component B containing isocyanate compound)
In the present invention, the isocyanate component B is an isocyanate compound which is a reaction product (B-1) of a polyol and an isocyanate, and a reactive diluent (B-2) having an isocyanate group having a number average molecular weight in the range of 400 to 1,000. Isocyanate compound.
(ポリオールとイソシアネートとの反応生成物(B−1))
前記反応生成物(B−1)の原料であるイソシアネートは、例えば、トリレンジイソシアネート、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、1,5−ナフタレンジイソシアネート、トリフェニルメタントリイソシアネートなどの芳香族ポリイソシアネート;1,6−ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、4,4’−メチレンビス(シクロヘキシルイソシアネート)、リジンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、1,3−(イソシアナートメチル)シクロヘキサン等の脂肪族ポリイソシアネート;これらの芳香族又は脂肪族ポリイソシアネートのビウレット体、または、これらの芳香族又は脂肪族ポリイソシアネートのイソシアヌレート体などのポリイソシアネートの誘導体(変性物)、これらの芳香族又は脂肪族ポリイソシアネートをトリメチロールプロパン変性したアダクト体などが挙げられる。(Reaction product of polyol and isocyanate (B-1))
The isocyanate that is a raw material of the reaction product (B-1) is, for example, an aromatic polyisocyanate such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate; Aliphatic polyisocyanates such as 6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; Polyisocyanates such as biurets of aliphatic polyisocyanates or isocyanurates of these aromatic or aliphatic polyisocyanates Derivatives (modified products) of adsorbates and adducts obtained by modifying these aromatic or aliphatic polyisocyanates with trimethylolpropane.
前記反応生成物(B−1)の原料であるポリオールは、例えば、エチレングリコール、プロピレングリコール、1,3−プロパンジオール、1,4−ブタンジオール、1,5−ペンタンジオール、3−メチル−1,5−ペンタンジオール、1,6−ヘキサンジオール、ネオペンチルグリコール、メチルペンタンジオール、ジメチルブタンジオール、ブチルエチルプロパンジオール、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等のアルキレングリコール;ビスフェノールA、ビスフェノールF、水素添加ビスフェノールA、水素添加ビスフェノールF等のビスフェノール;ダイマージオール;ビスヒドロキシエトキシベンゼン;ジエチレングリコール、トリエチレングリコール、その他のポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコール等のポリアルキレングリコール;該ポリアルキレングリコールを更に前記芳香族又は脂肪族ポリイソシアネートで高分子量化したウレタン結合含有ポリエーテルポリオール;前記アルキレングリコール又はポリアルキレングリコールと、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、フマル酸、マレイン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカン二酸、ドデカン二酸、トリデカン二酸等の炭素原子数が2〜13の範囲である脂肪族ジカルボン酸とを反応させて得られるポリエステルポリオール;プロピオラクトン、ブチロラクトン、ε−カプロラクトン、σ−バレロラクトン、β−メチル−σ−バレロラクトン等の環状エステル化合物の開環重合反応によって得られるポリエステルと、前記グリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール等の多価アルコールとの反応物であるポリエステルポリオール等が挙げられる。 Examples of the polyol that is a raw material of the reaction product (B-1) include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl-1. , 5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and other alkylene glycols; bisphenol Bisphenols such as A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F; dimer diol; bishydroxyethoxybenzene; diethylene glycol, triethylene glycol, other polyethylene glycols Polyalkylene glycols such as polypropylene glycol and polybutylene glycol; a urethane bond-containing polyether polyol obtained by further polymerizing the polyalkylene glycol with the aromatic or aliphatic polyisocyanate; the alkylene glycol or polyalkylene glycol, oxalic acid, In the range of 2 to 13 carbon atoms such as malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid Polyester polyols obtained by reacting with certain aliphatic dicarboxylic acids; obtained by ring-opening polymerization reaction of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone And polyester polyol which is a reaction product of the obtained polyester and the polyhydric alcohol such as glycol, glycerin, trimethylolpropane and pentaerythritol.
芳香族又は脂肪族ポリイソシアネートとの反応に用いるポリオールとしては、これらのうち、接着剤自体の低粘度化を図りつつ、接着強度を高めることができる点から、ポリアルキレングリコール、又はポリエステルポリオールが好ましく、ポリアルキレングリコールとしては、数平均分子量(Mn)200〜6,000の範囲にあるものが好ましい。他方、ポリエステルポリオールは、前記アルキレングリコール又は分子量300以下のポリアルキレングリコールと炭素原子数2〜30の脂肪族多価カルボン酸とを反応させて得られるものが好ましい。また、後者のポリエステルポリオールはその原料アルコール成分として、グリセリン、トリメチロールプロパン、ペンタエリスリトール等の3官能以上のアルコールを該ポリオール成分中10質量%以下となる割合で用いてもよい。 Of these, the polyol used for the reaction with the aromatic or aliphatic polyisocyanate is preferably a polyalkylene glycol or a polyester polyol from the viewpoint that the adhesive strength can be increased while reducing the viscosity of the adhesive itself. As the polyalkylene glycol, those having a number average molecular weight (Mn) in the range of 200 to 6,000 are preferable. On the other hand, the polyester polyol is preferably obtained by reacting the alkylene glycol or polyalkylene glycol having a molecular weight of 300 or less with an aliphatic polyvalent carboxylic acid having 2 to 30 carbon atoms. In the latter polyester polyol, a tri- or higher functional alcohol such as glycerin, trimethylolpropane, or pentaerythritol may be used as a raw material alcohol component in a proportion of 10% by mass or less in the polyol component.
前記反応生成物(B−1)の中でも、軟包装基材用としては芳香族ポリイソシアネートと数平均分子量200〜6,000の範囲にあるポリアルキレングリコールとを反応させて得られるポリイソシアネート、芳香族ポリイソシアネートと数平均分子量200〜3,000の範囲にあるポリエステルポリオールとを反応させて得られるポリイソシアネートが硬化物に適度な柔軟性を付与できる点から好ましく、具体的には、滴定法(ジ−n−ブチルアミン使用)によるイソシアネート含有率が5〜20質量%のものが適正な樹脂粘度となって塗工性に優れる点から好ましい。 Among the reaction products (B-1), for a flexible packaging substrate, a polyisocyanate obtained by reacting an aromatic polyisocyanate with a polyalkylene glycol having a number average molecular weight in the range of 200 to 6,000, an aromatic A polyisocyanate obtained by reacting a group polyisocyanate with a polyester polyol having a number average molecular weight in the range of 200 to 3,000 is preferable from the viewpoint of imparting appropriate flexibility to the cured product. Those having an isocyanate content of from 5 to 20% by mass based on the use of di-n-butylamine are preferable from the viewpoint of having an appropriate resin viscosity and excellent coating properties.
一方、反応型接着剤の硬質基材用では芳香族ポリイソシアネートと数平均分子量200〜3,000の範囲にあるポリエステルポリオールとを反応させて得られるポリイソシアネート;芳香族ポリイソシアネートと、数平均分子量200〜3,000の範囲にあるポリエステルポリオール及び数平均分子量200〜6,000の範囲にあるポリアルキレングリコールの混合物とを反応させて得られるポリイソシアネートが接着強度に優れる点から好ましく、具体的には、滴定法(ジ−n−ブチルアミン使用)によるイソシアネート含有率が5〜20質量%のものが、やはり適正な樹脂粘度となって塗工性に優れる点から好ましい。 On the other hand, for a hard substrate of a reactive adhesive, a polyisocyanate obtained by reacting an aromatic polyisocyanate with a polyester polyol having a number average molecular weight in the range of 200 to 3,000; an aromatic polyisocyanate and a number average molecular weight A polyisocyanate obtained by reacting a mixture of a polyester polyol in the range of 200 to 3,000 and a polyalkylene glycol in the range of the number average molecular weight of 200 to 6,000 is preferable from the viewpoint of excellent adhesive strength, specifically Is preferably 5 to 20% by mass of an isocyanate content by titration method (using di-n-butylamine) from the viewpoint of an appropriate resin viscosity and excellent coating properties.
ここで、芳香族ポリイソシアネートと、ポリアルキレングリコール又はポリエステルポリオールとの混合物との反応割合は、芳香族ポリイソシアネート中のイソシアネートとポリオール中の水酸基との当量比[イソシアネート/水酸基]が1.5〜5.0の範囲であることが、接着剤の粘度が適正範囲となって塗工性が良好となる点から好ましい。 Here, the reaction ratio between the aromatic polyisocyanate and the mixture of the polyalkylene glycol or the polyester polyol is such that the equivalent ratio [isocyanate / hydroxyl group] of the isocyanate in the aromatic polyisocyanate and the hydroxyl group in the polyol is 1.5 to 1.5. The range of 5.0 is preferable from the viewpoint that the viscosity of the adhesive is in an appropriate range and the coating property is good.
(数平均分子量が400〜1000の範囲であるイソシアネート基を有する反応性希釈剤(B−2)
本発明においては、数平均分子量が400〜1000の範囲であるイソシアネート基を有する反応性希釈剤(B−2)を含むことが特徴である。反応性希釈剤(B−2)を含むことで、低粘度であり取り扱いに優れ、且つ良好なポットライフを得ることができる。
これらの反応性希釈剤(B−2)として具体的には、芳香族ジイソシアネート、脂肪族ジイソシアネート、芳香族ジイソシアネートの二量体、脂肪族ジイソシアネートの二量体、芳香族ジイソシアネートの三量体、又は脂肪族ジイソシアネートの三量体が好ましく、より具体的には、カルボジイミド修飾ジフェニルメタンジイソシアネート、アロファネート修飾ジフェニルメタンジイソシアネート、ビウレット修飾ジフェニルメタンジイソシアネート、キシリレンジイソシアネートなどの芳香族ポリイソシアネート;1,6−ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、4,4’−メチレンビス(シクロヘキシルイソシアネート)、リジンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、1,3−(イソシアナートメチル)シクロヘキサン等の脂肪族ポリイソシアネート;これらの芳香族又は脂肪族ポリイソシアネートのアロファネート体、ビウレット体、または、これらの芳香族又は脂肪族ポリイソシアネートのイソシアヌレート体などのポリイソシアネートの誘導体(変性物)、これらの芳香族又は脂肪族ポリイソシアネートをトリメチロールプロパン変性したアダクト体などが挙げられる。(Reactive diluent (B-2) having an isocyanate group having a number average molecular weight in the range of 400 to 1000)
The present invention is characterized by including a reactive diluent (B-2) having an isocyanate group having a number average molecular weight in the range of 400 to 1,000. By including the reactive diluent (B-2), the viscosity is low, the handling is excellent, and a good pot life can be obtained.
Specifically as these reactive diluents (B-2), aromatic diisocyanate, aliphatic diisocyanate, dimer of aromatic diisocyanate, dimer of aliphatic diisocyanate, trimer of aromatic diisocyanate, or Trimers of aliphatic diisocyanates are preferred, more specifically, aromatic polyisocyanates such as carbodiimide modified diphenylmethane diisocyanate, allophanate modified diphenylmethane diisocyanate, biuret modified diphenylmethane diisocyanate, xylylene diisocyanate; 1,6-hexamethylene diisocyanate, isophorone Diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, 1,3- (iso Aliphatic polyisocyanates such as cyanate methyl) cyclohexane; derivatives of polyisocyanates such as allophanates, biurets of these aromatic or aliphatic polyisocyanates, or isocyanurates of these aromatic or aliphatic polyisocyanates ( Modified products), adducts obtained by modifying these aromatic or aliphatic polyisocyanates with trimethylolpropane, and the like.
前記イソシアネート成分B中、前記反応生成物(B−1)と前記反応性希釈剤(B−2)との配合割合は、前記反応生成物(B−1)/前記反応性希釈剤(B−2)が30/70〜99/1の範囲であることが好ましく、50/50〜95/5の範囲であることがなお好ましい。 In the isocyanate component B, the mixing ratio of the reaction product (B-1) and the reactive diluent (B-2) is the reaction product (B-1) / the reactive diluent (B- 2) is preferably in the range of 30/70 to 99/1, and more preferably in the range of 50/50 to 95/5.
前記ポリオール化合物を含有するポリオール成分Aと、前記イソシアネート化合物を含有するイソシアネート成分Bとの配合割合は、ポリオール化合物の固形分水酸基当量(a)とポリイソシアネート化合物の固形分イソシアネート当量(b)の当量比〔(a)/(b)〕が1.0〜5.0、より好ましくは2.0〜3.0である。製造の詳細は、実施例に記載した。
また、前記イソシアネート成分Bのイソシアネート基濃度は5〜20%の範囲が好ましい。The blending ratio of the polyol component A containing the polyol compound and the isocyanate component B containing the isocyanate compound is equivalent to the solid content hydroxyl equivalent (a) of the polyol compound and the solid isocyanate equivalent (b) of the polyisocyanate compound. The ratio [(a) / (b)] is 1.0 to 5.0, more preferably 2.0 to 3.0. Details of the manufacture are described in the examples.
The isocyanate group concentration of the isocyanate component B is preferably in the range of 5 to 20%.
尚、本願発明において数平均分子量(Mn)は、下記条件のゲルパーミアーションクロマトグラフィー(GPC)により測定される値である。 In the present invention, the number average molecular weight (Mn) is a value measured by gel permeation chromatography (GPC) under the following conditions.
測定装置 ;東ソー株式会社製 HLC−8220GPC
カラム ;東ソー株式会社製 TSK−GUARDCOLUMN SuperHZ−L
+東ソー株式会社製 TSK−GEL SuperHZM−M×4
検出器 ;RI(示差屈折計)
データ処理;東ソー株式会社製 マルチステーションGPC−8020modelII
測定条件 ;カラム温度 40℃
溶媒 テトラヒドロフラン
流速 0.35ml/分
標準 ;単分散ポリスチレン
試料 ;樹脂固形分換算で0.2質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(100μl)Measuring device: HLC-8220GPC manufactured by Tosoh Corporation
Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation
+ Tosoh Corporation TSK-GEL SuperHZM-M x 4
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene Sample: Filtered 0.2% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)
前記反応性希釈剤(B−2)の数平均分子量は中でも400〜1000の範囲が好ましく、より好ましくは450〜900の範囲である。 The number average molecular weight of the reactive diluent (B-2) is preferably in the range of 400 to 1000, more preferably in the range of 450 to 900.
(粘度)
本発明の反応型接着剤は、前記ポリオール成分Aとイソシアネート成分Bとを重量比の割合で配合し40℃雰囲気下で30分放置後の粘度が5000mPa・s以下である。本発明においては、粘度は、下記条件の回転粘度計により測定される値である。
測定装置 ;アントンパール社製 MCR−302
測定条件 ;温度 40℃、コーンプレートΦ50mm(viscosity)
The reactive adhesive of the present invention has a viscosity of 5000 mPa · s or less after the polyol component A and the isocyanate component B are blended in a ratio by weight and left in a 40 ° C. atmosphere for 30 minutes. In the present invention, the viscosity is a value measured by a rotational viscometer under the following conditions.
Measuring device: MCR-302 manufactured by Anton Paar
Measurement conditions: Temperature 40 ° C, cone plate Φ50mm
粘度は、中でも500〜5000mPa・sの範囲が好ましく、より好ましくは1500〜4500mPa・sの範囲である。 The viscosity is preferably in the range of 500 to 5000 mPa · s, more preferably in the range of 1500 to 4500 mPa · s.
本発明で使用する反応型接着剤は、詳述した通り、ポリオール成分Aとイソシアネート成分Bとを必須成分とするものであるが、更に、肪族環状アミド化合物を、ポリオール成分Aとイソシアネート成分Bとのどちらか一方の成分に混合させるか、或いは、第3成分として塗工時に配合することにより、ラミネート包装体において芳香族アミンに代表される有害な低分子化学物質の内容物への溶出が効果的に抑制できる。 As described in detail, the reactive adhesive used in the present invention comprises a polyol component A and an isocyanate component B as essential components, and further comprises an aliphatic cyclic amide compound as a polyol component A and an isocyanate component B. Or mixed with one of these components, or by mixing at the time of coating as the third component, the laminate packaging body can be dissolved into the contents of harmful low molecular chemicals typified by aromatic amines. It can be effectively suppressed.
ここで用いる脂肪族環状アミド化合物は、例えば、δ−バレロラクタム、ε−カプロラクタム、ω−エナントールラクタム、η−カプリルラクタム、β−プロピオラクタム等が挙げられる。これらの中でも低分子化学物質の溶出量低減の効果に優れる点からε−カプロラクタムが好ましい。また、その配合量は、ポリオール成分A100質量部あたり、脂肪族環状アミド化合物を0.1〜5質量部の範囲で混合させることが好ましい。 Examples of the aliphatic cyclic amide compound used here include δ-valerolactam, ε-caprolactam, ω-enanthollactam, η-capryllactam, β-propiolactam, and the like. Among these, ε-caprolactam is preferable because it is excellent in the effect of reducing the elution amount of low molecular chemical substances. Moreover, it is preferable that the compounding quantity mixes an aliphatic cyclic amide compound in 0.1-5 mass parts per 100 mass parts of polyol components A.
本発明で使用する反応型接着剤は、必要に応じて、顔料を併用してもよい。この場合使用可能な顔料としては、特に限定されるものではなく、例えば、塗料原料便覧1970年度版(日本塗料工業会編)に記載されている体質顔料、白顔料、黒顔料、灰色顔料、赤色顔料、茶色顔料、緑色顔料、青顔料、金属粉顔料、発光顔料、真珠色顔料等の有機顔料や無機顔料、さらにはプラスチック顔料などが挙げられる。これら着色剤の具体例としては種々のものが掲げられ、有機顔料としては、例えば、ベンチジンエロー、ハンザエロー、レーキッド4R等の、各種の不溶性アゾ顔料;レーキッドC、カーミン6B、ボルドー10等の溶性アゾ顔料;フタロシアニンブルー、フタロシアニングリーン等の各種(銅)フタロシアニン系顔料;ローダミンレーキ、メチルバイオレットレーキ等の各種の塩素性染め付けレーキ;キノリンレーキ、ファストスカイブルー等の各種の媒染染料系顔料;アンスラキノン系顔料、チオインジゴ系顔料、ペリノン系顔料等の各種の建染染料系顔料;シンカシアレッドB等の各種のキナクリドン系顔料;ヂオキサジンバイオレット等の各種のヂオキサジン系顔料;クロモフタール等の各種の縮合アゾ顔料;アニリンブラックなどが挙げられる。 The reactive adhesive used in the present invention may be used in combination with a pigment, if necessary. In this case, usable pigments are not particularly limited. For example, extender pigments, white pigments, black pigments, gray pigments, red pigments described in the Paint Material Handbook 1970 edition (edited by the Japan Paint Industry Association) Examples thereof include organic pigments and inorganic pigments such as pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, and pearl pigments, and plastic pigments. Specific examples of these colorants include various types, and examples of organic pigments include various insoluble azo pigments such as Bench Gin Yellow, Hansa Yellow, Raked 4R, etc .; Soluble properties such as Raked C, Carmine 6B, Bordeaux 10 and the like. Azo pigments; various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; various chlorine dyeing lakes such as rhodamine lake and methyl violet lake; various mordant dye pigments such as quinoline lake and fast sky blue; anthraquinone Various vat dyes such as pigments, thioindigo pigments and perinone pigments; various quinacridone pigments such as Cincacia Red B; various dioxazine pigments such as dioxazine violet; various condensed azos such as chromoftal Pigment; aniline black, etc. And the like.
無機顔料としては、例えば、黄鉛、ジンククロメート、モリブデートオレンジ等の如き、各種のクロム酸塩;紺青等の各種のフェロシアン化合物;酸化チタン、亜鉛華、マピコエロー、酸化鉄、ベンガラ、酸化クロームグリーン、酸化ジルコニウム等の各種の金属酸化物;カドミウムエロー、カドミウムレッド、硫化水銀等の各種の硫化物ないしはセレン化物;硫酸バリウム、硫酸鉛等の各種の硫酸塩;ケイ酸カルシウム、群青等の各種のケイ酸塩;炭酸カルシウム、炭酸マグネシウム等の各種の炭酸塩;コバルトバイオレット、マンガン紫等の各種の燐酸塩;アルミニウム粉、金粉、銀粉、銅粉、ブロンズ粉、真鍮粉等の各種の金属粉末顔料;これら金属のフレーク顔料、マイカ・フレーク顔料;金属酸化物を被覆した形のマイカ・フレーク顔料、雲母状酸化鉄顔料等のメタリック顔料やパール顔料;黒鉛、カーボンブラック等が挙げられる。 Examples of inorganic pigments include various chromates such as chrome lead, zinc chromate, and molybdate orange; various ferrocyan compounds such as bitumen; titanium oxide, zinc white, mapico yellow, iron oxide, bengara, chrome oxide Various metal oxides such as green and zirconium oxides; various sulfides or selenides such as cadmium yellow, cadmium red and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various types such as calcium silicate and ultramarine blue Silicates; various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powders such as aluminum powder, gold powder, silver powder, copper powder, bronze powder and brass powder Pigments; these metal flake pigments, mica flake pigments; mica flakes coated with metal oxides Pigments, metallic pigments and pearl pigments such as micaceous iron oxide pigments; graphite, carbon black and the like.
体質顔料としては、例えば、沈降性硫酸バリウム、ご粉、沈降炭酸カルシウム、重炭酸カルシウム、寒水石、アルミナ白、シリカ、含水微粉シリカ(ホワイトカーボン)、超微粉無水シリカ(アエロジル)、珪砂(シリカサンド)、タルク、沈降性炭酸マグネシウム、ベントナイト、クレー、カオリン、黄土などが挙げられる。 Examples of extender pigments include precipitated barium sulfate, powder, precipitated calcium carbonate, calcium bicarbonate, cryolite, alumina white, silica, hydrous finely divided silica (white carbon), ultrafine anhydrous silica (Aerosil), and silica sand (silica). Sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, ocher and the like.
さらに、プラスチック顔料としては、例えば、DIC(株)製「グランドールPP−1000」、「PP−2000S」等が挙げられる。 Furthermore, examples of the plastic pigment include “Grandall PP-1000” and “PP-2000S” manufactured by DIC Corporation.
本発明で用いる顔料としては、耐久性、耐侯性、意匠性に優れることから、白色顔料としての酸化チタン、亜鉛華等の無機酸化物、黒色顔料としてのカーボンブラックがより好ましい。 As the pigment used in the present invention, since it is excellent in durability, weather resistance and design, inorganic oxides such as titanium oxide and zinc white as a white pigment, and carbon black as a black pigment are more preferable.
本発明で用いる顔料の質量割合は、イソシアネート成分Bとポリオール成分Aの合計100質量部に対して、1〜400質量部、中でも10〜300質量部とすることが、接着性、耐ブロッキング性などに優れることからより好ましい。 The mass ratio of the pigment used in the present invention is 1 to 400 parts by mass, particularly 10 to 300 parts by mass with respect to a total of 100 parts by mass of the isocyanate component B and the polyol component A. More preferable.
また本発明で使用する反応型接着剤には接着促進剤を用いることもできる。接着促進剤にはシランカップリング剤、チタネート系カップチング剤、アルミニウム系等のカップリング剤、エポキシ樹脂が挙げられる。 Moreover, an adhesion promoter can also be used for the reactive adhesive used in the present invention. Examples of the adhesion promoter include silane coupling agents, titanate coupling agents, aluminum coupling agents, and epoxy resins.
シランカップリング剤としては、例えば、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリメトキシシラン、N−β(アミノエチル)−γ−アミノプロピルトリメトキシシラン、N−β(アミノエチル)−γ−アミノプロピルトリメチルジメトキシシラン、N−フェニル−γ−アミノプロピルトリメトキシシラン等のアミノシラン;β−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン等のエポキシシラン;ビニルトリス(β−メトキシエトキシ)シラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン等のビニルシラン;ヘキサメチルジシラザン、γ−メルカプトプロピルトリメトキシシラン等を挙げることが出来る。 Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ. Amino silanes such as aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycine Epoxy silanes such as Sidoxypropyltriethoxysilane; Vinylsilanes such as Vinyltris (β-methoxyethoxy) silane, Vinyltriethoxysilane, Vinyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane; Hexamethyldisilazane, γ-Mel Hept trimethoxysilane and the like.
チタネート系カップリング剤としては、例えば、テトライソプロポキシチタン、テトラ−n−ブトキシチタン、ブチルチタネートダイマー、テトラステアリルチタネート、チタンアセチルアセトネート、チタンラクテート、テトラオクチレングリコールチタネート、チタンラクテート、テトラステアロキシチタン等を挙げることが出来る。 Examples of titanate coupling agents include tetraisopropoxy titanium, tetra-n-butoxy titanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, tetrastearoxy Titanium etc. can be mentioned.
また、アルミニウム系カップリング剤としては、例えば、アセトアルコキシアルミニウムジイソプロピレート等が挙げることが出来る。 Moreover, as an aluminum coupling agent, acetoalkoxy aluminum diisopropylate etc. can be mentioned, for example.
エポキシ樹脂としては、一般的に市販されているビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂、ビスフェノールのβ−メチルグリシジルエーテル、ノボラック樹脂のβ−メチルグリシジルエーテル、環状オキシラン型エポキシ樹脂、レゾルシン型エポキシ樹脂等の各種エポキシ樹脂が挙げられる。 As epoxy resins, commercially available bisphenol type epoxy resins, novolac type epoxy resins, β-methyl glycidyl ether of bisphenol, β-methyl glycidyl ether of novolac resin, cyclic oxirane type epoxy resin, resorcin type epoxy resin, etc. And various epoxy resins.
本発明で使用する反応型接着剤には、必要であれば、前記以外のその他の添加剤を含有させてもよい。添加剤としては、例えば、レベリング剤;コロイド状シリカ、アルミナゾルなどの無機微粒子;ポリメチルメタクリレート系の有機微粒子;消泡剤;タレ性防止剤;湿潤分散剤;粘性調整剤;紫外線吸収剤;金属不活性化剤;過酸化物分解剤;難燃剤;補強剤;可塑剤;潤滑剤;防錆剤;蛍光性増白剤;無機系熱線吸収剤;防炎剤;帯電防止剤;脱水剤などが挙げられる。 The reactive adhesive used in the present invention may contain other additives other than those described above, if necessary. Examples of additives include leveling agents; inorganic fine particles such as colloidal silica and alumina sol; organic fine particles of polymethyl methacrylate; antifoaming agents; anti-sagging agents; wetting and dispersing agents; viscosity modifiers; ultraviolet absorbers; Deactivator; Peroxide decomposing agent; Flame retardant; Reinforcing agent; Plasticizer; Lubricant; Rust preventive agent; Fluorescent whitening agent; Inorganic heat absorber; Flameproof agent; Antistatic agent; Is mentioned.
これらの顔料、接着促進剤、添加剤は、イソシアネート成分B又はポリオール成分Aのどちらか一方の成分に混合させるか、或いは、第3成分として塗工時に配合して使用することができる。これらのなかでも、顔料、接着促進剤、及び添加剤をポリオール成分Aに予め配合したプレミックスを本発明のラミネート接着剤用ポリオール組成物として調整し、2液型接着剤として使用することが、作業性の点から好ましい。 These pigments, adhesion promoters, and additives can be mixed with either one of the isocyanate component B or the polyol component A, or can be blended and used as a third component at the time of coating. Among these, a premix in which a pigment, an adhesion promoter, and an additive are blended in advance with the polyol component A is prepared as a polyol composition for a laminate adhesive of the present invention and used as a two-component adhesive. It is preferable from the viewpoint of workability.
(積層フィルム)
本発明の積層フィルムは、第一のプラスチックフィルムと第二のプラスチックフィルムの間に前記反応型接着剤からなる接着剤層を積層してなる。具体的には、前記反応型接着剤を第一のプラスチックフィルムに塗布、次いで塗布面に第二のプラスチックフィルムを積層し、該接着剤層を硬化させて得られるものである。例えば前記反応型接着剤を、ロールコーター塗工方式で第一のプラスチックフィルムに塗布し、次いで、乾燥工程を経ることなく、他の基材を貼り合わせる方法が挙げられる。塗工条件は、通常のロールコーターでは、30℃〜90℃まで加熱した状態で、接着剤の配合液粘度が40℃で300〜3000mPa・s程度が好ましいが、本発明の接着剤は配合し40℃雰囲気下で30分放置後の粘度が5000mPa・s以下であるので問題なく塗工できる。また塗布量は、0.5〜5g/m2が好ましく、より好ましくは、0.5〜3g/m2程度で使用するのがよい。(Laminated film)
The laminated film of the present invention is formed by laminating an adhesive layer made of the reactive adhesive between a first plastic film and a second plastic film. Specifically, the reactive adhesive is applied to a first plastic film, then a second plastic film is laminated on the application surface, and the adhesive layer is cured. For example, there is a method in which the reactive adhesive is applied to the first plastic film by a roll coater coating method, and then another substrate is bonded without passing through a drying step. The coating conditions are preferably about 300 to 3000 mPa · s at 40 ° C. with the adhesive solution being heated to 30 ° C. to 90 ° C. in a normal roll coater. Since the viscosity after leaving for 30 minutes in a 40 ° C. atmosphere is 5000 mPa · s or less, coating can be performed without any problem. The coating amount is preferably 0.5 to 5 g / m 2 , more preferably about 0.5 to 3 g / m 2 .
また、前記第一のプラスチックフィルム上に、印刷インキをグラビア又はフレキソ印刷したものを用いてもよく、この場合であっても良好なラミネート外観を呈することができる。前述の印刷インキは溶剤型、水性型又は活性エネルギー線硬化型インキを使用することがきる。 Further, a gravure or flexographic print of printing ink may be used on the first plastic film, and even in this case, a good laminate appearance can be exhibited. As the above-mentioned printing ink, a solvent type, aqueous type or active energy ray curable ink can be used.
本発明で使用する反応型接着剤を用いた場合、ラミネートした後、常温または加温下で、12〜72時間で接着剤が硬化し、実用物性を発現する。 When the reactive adhesive used in the present invention is used, the adhesive is cured in 12 to 72 hours at room temperature or under heating after lamination, and expresses practical physical properties.
ここで用いる、第一のプラスチックフィルムとしては、PET(ポリエチレンテレフタレート)フィルム、ナイロンフィルム、OPP(2軸延伸ポリプロピレン)フィルム、ポリ塩化ビニリデン等のKコートフィルム、各種蒸着フィルム等のベースフィルムやアルミ箔等が挙げられ、第二のプラスチックフィルムとしては、前記他の基材としては、CPP(無延伸ポリプロピレン)フィルム、VMCPP(アルミ蒸着無延伸ポリプロピレンフィルム)、LLDPE(直鎖状低密度ポリエチレン)、LDPE(低密度ポリエチレン)、HDPE(高密度ポリエチレン)、VMLDPE(アルミ蒸着無低密度ポリエチレンフィルム)フィルム等のシーラントフィルムが挙げられる。 The first plastic film used here is a PET (polyethylene terephthalate) film, a nylon film, an OPP (biaxially oriented polypropylene) film, a K-coated film such as polyvinylidene chloride, a base film such as various deposited films, and an aluminum foil. Examples of the second plastic film include CPP (unstretched polypropylene) film, VMCP (aluminum vapor-deposited unstretched polypropylene film), LLDPE (linear low density polyethylene), and LDPE. Examples thereof include sealant films such as (low density polyethylene), HDPE (high density polyethylene), and VMLDPE (aluminum vapor-deposited low density polyethylene film) films.
本発明においては、無溶剤型ラミネート機で高速ラミネート加工しても優れた積層フィルム外観が得られるが、例えば、PET(ポリエチレンテレフタレート)フィルム/VMCPP(アルミ蒸着無延伸ポリプロピレンフィルム)のフィルム構成の場合200m/分以上、OPP/CPPのフィルム構成の場合350m/分以上の高速加工であっても良好な外観を呈することできる。 In the present invention, an excellent laminated film appearance can be obtained even if high-speed lamination is performed with a solventless laminating machine. For example, in the case of a film configuration of PET (polyethylene terephthalate) film / VMPP (aluminum-deposited unstretched polypropylene film) In the case of a film structure of 200 m / min or more and OPP / CPP, a good appearance can be exhibited even at high speed processing of 350 m / min or more.
(包装体)
本発明の包装体は、前記積層フィルムを袋状に成形してなり、具体的には前記積層フィルムをヒートシールすることにより包装体の形態となる。また、包装体としての用途、必要な性能(易引裂性やハンドカット性)、包装体として要求される剛性や耐久性(例えば、耐衝撃性や耐ピンホール性など)などを考慮した場合、必要に応じて他の層を積層することもできる。通常は基材層、紙層、第2のシーラント層、不職布層などを伴って使用される。他の層を積層する方法としては、公知の方法を用いることができる。たとえば、他の層との層間に接着剤層を設けてドライラミネート法、熱ラミネート法、ヒートシール法、押出しラミネート法などにより積層すればよい。接着剤としては、前記反応型接着剤を使用してもよいし、他の1液タイプのウレタン系接着剤、エポキシ系接着剤、酸変性ポリオレフィンの水性分散体などを用いてもよい。(Packaging body)
The package of the present invention is formed by forming the laminated film into a bag shape. Specifically, the package is formed by heat-sealing the laminated film. In addition, when considering the use as a package, required performance (easy tearability and hand cutability), rigidity and durability required for the package (for example, impact resistance, pinhole resistance, etc.) Other layers can be laminated as required. Usually, it is used with a base material layer, a paper layer, a second sealant layer, a non-work cloth layer and the like. As a method of laminating other layers, a known method can be used. For example, an adhesive layer may be provided between other layers and laminated by a dry laminate method, a heat laminate method, a heat seal method, an extrusion laminate method, or the like. As the adhesive, the reactive adhesive may be used, or other one-component urethane adhesive, epoxy adhesive, aqueous dispersion of acid-modified polyolefin, or the like may be used.
具体的な積層体構成としては、一般の包装体や蓋材、詰め替え容器などに好適に用いることが可能な、第一のプラスチックフィルム層/接着層/第二のプラスチック層、第一のプラスチック層をバリア層にした、基材層/接着層/第一のプラスチックフィルム層/接着層/第二のプラスチック層や紙容器、紙カップなどに好適に用いることが可能な、第二のプラスチック層/紙層/接着層/第一のプラスチックフィルム層/接着層/第二のプラスチック、第二のプラスチック層/紙層/ポリオレフィン樹脂層/基材層/第一のプラスチック層/接着層/第二のプラスチック層、紙層/第一のプラスチックフィルム層/接着層/シーラント層やチューブ容器などに好適に用いることが可能な、第二のプラスチック層/接着層/第一のプラスチック層/接着層/第二のプラスチック層などが挙げられる。これら積層体は、必要に応じて、印刷層やトップコート層などを有していても構わない。 As a specific laminate structure, the first plastic film layer / adhesive layer / second plastic layer, first plastic layer, which can be suitably used for general packaging bodies, lid materials, refill containers, etc. A second plastic layer / paper that can be suitably used for a base layer / adhesive layer / first plastic film layer / adhesive layer / second plastic layer, paper container, paper cup, etc. Layer / adhesive layer / first plastic film layer / adhesive layer / second plastic, second plastic layer / paper layer / polyolefin resin layer / substrate layer / first plastic layer / adhesive layer / second plastic Layer, paper layer / first plastic film layer / adhesive layer / sealant layer, second plastic layer / adhesive layer / first plastic, which can be suitably used for tube containers, etc. Such as a layer / adhesive layer / second plastic layer. These laminates may have a print layer, a top coat layer, or the like as necessary.
第一のプラスチックフィルム層は、例えば、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)、ポリ乳酸(PLA)などのポリエステル樹脂フィルム;ポリプロピレンなどのポリオレフィン樹脂フィルム;ポリスチレン樹脂フィルム;ナイロン6、ポリ−p−キシリレンアジパミド(MXD6ナイロン)などのポリアミド樹脂フィルム;ポリカーボネート樹脂フィルム;ポリアクリルニトリル樹脂フィルム;ポリイミド樹脂フィルム;これらの複層体(例えば、ナイロン6/MXD6/ナイロン6、ナイロン6/エチレン−ビニルアルコール共重合体/ナイロン6)や混合体などが用いられる。なかでも、機械的強度や寸法安定性を有するものが好ましい。特に、これらの中で二軸方向に任意に延伸されたフィルムが好ましく用いられる。 The first plastic film layer is made of, for example, a polyester resin film such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or polylactic acid (PLA); a polyolefin resin film such as polypropylene; a polystyrene resin film; a nylon 6, a poly- Polyamide resin film such as p-xylylene adipamide (MXD6 nylon); Polycarbonate resin film; Polyacrylonitrile resin film; Polyimide resin film; Multilayers thereof (for example, nylon 6 / MXD6 / nylon 6, nylon 6 / An ethylene-vinyl alcohol copolymer / nylon 6) or a mixture is used. Among them, those having mechanical strength and dimensional stability are preferable. Of these, a film arbitrarily stretched in the biaxial direction is preferably used.
また、第一のプラスチックフィルム層は、バリア機能を付与するためにアルミニウム箔などの軟質金属箔の他、アルミ蒸着、シリカ蒸着、アルミナ蒸着、シリカアルミナ2元蒸着などの蒸着層;塩化ビニリデン系樹脂、変性ポリビニルアルコール、エチレンビニルアルコール共重合体、MXDナイロンなどからなる有機バリア層などを採用できる。 Further, the first plastic film layer is made of a soft metal foil such as an aluminum foil to provide a barrier function, as well as a vapor deposition layer such as aluminum vapor deposition, silica vapor deposition, alumina vapor deposition, and silica alumina binary vapor deposition; vinylidene chloride resin An organic barrier layer made of modified polyvinyl alcohol, ethylene vinyl alcohol copolymer, MXD nylon or the like can be used.
第二のプラスチックフィルム層としては、従来から知られたシーラント樹脂を使用できる。例えば、低密度ポリエチレン(LDPE)や直鎖状低密度ポリエチレン(LLDPE)や高密度ポリエチレン(HDPE)などのポリエチレン、酸変性ポリエチレン、ポリプロピレン(PP)、酸変性ポリプロピレン、共重合ポリプロピレン、エチレン−ビニルアセテート共重合体、エチレン−(メタ)アクリル酸エステル共重合体、エチレン−(メタ)アクリル酸共重合体、アイオノマーなどのポリオレフィン樹脂などがあげられる。なかでも低温シール性の観点からポリエチレン系樹脂が好ましく、安価であることからポリエチレンが特に好ましい。シーラント層の厚みは、特に限定されないが、包装材料への加工性やヒートシール性などを考慮して10〜60μmの範囲が好ましく、15〜40μmの範囲がより好ましい。また、シーラント層に高低差5〜20μmの凸凹を設けることで、シーラント層に滑り性や包装材料の引き裂き性を付与することが可能である。 A conventionally known sealant resin can be used as the second plastic film layer. For example, polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE), acid-modified polyethylene, polypropylene (PP), acid-modified polypropylene, copolymerized polypropylene, ethylene-vinyl acetate Examples thereof include polyolefin resins such as copolymers, ethylene- (meth) acrylic acid ester copolymers, ethylene- (meth) acrylic acid copolymers, and ionomers. Of these, polyethylene resins are preferred from the viewpoint of low temperature sealing properties, and polyethylene is particularly preferred because of its low cost. Although the thickness of a sealant layer is not specifically limited, The range of 10-60 micrometers is preferable and the range of 15-40 micrometers is more preferable in consideration of the workability to a packaging material, heat seal property, etc. Further, by providing the sealant layer with irregularities having a height difference of 5 to 20 μm, it is possible to impart slipperiness and tearability of the packaging material to the sealant layer.
紙層としては、天然紙や合成紙などが挙げられる。第1および第2のシーラント層は、上述のシーラント層と同様の材料で形成することができる。基材層および紙層の外表面または内面側には、必要に応じて印刷層を設けてもよい。 Examples of the paper layer include natural paper and synthetic paper. The first and second sealant layers can be formed of the same material as the above-described sealant layer. You may provide a printing layer in the outer surface or inner surface side of a base material layer and a paper layer as needed.
「他の層」は、公知の添加剤や安定剤、例えば帯電防止剤、易接着コート剤、可塑剤、滑剤、酸化防止剤などを含んでいてもよい。また「他の層」は、その他の材料と積層する場合の密着性を向上させるために、前処理としてフィルムの表面をコロナ処理、プラズマ処理、オゾン処理、薬品処理、溶剤処理などしたものであってもよい。 The “other layer” may contain a known additive or stabilizer, for example, an antistatic agent, an easy adhesion coating agent, a plasticizer, a lubricant, an antioxidant or the like. In addition, “other layers” are those in which the surface of the film has been subjected to corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc. as a pretreatment in order to improve adhesion when laminated with other materials. May be.
本発明の包装体の態様としては、三方シール袋、四方シール袋、ガセット包装袋、ピロー包装袋、ゲーベルトップ型の有底容器、テトラクラッシク、ブリュックタイプ、チューブ容器、紙カップ、蓋材、など種々ある。また、本発明の包装体に易開封処理や再封性手段を適宜設けてあってもよい。 As an aspect of the package of the present invention, a three-sided seal bag, a four-sided seal bag, a gusset packaging bag, a pillow packaging bag, a gobeltop-type bottomed container, a tetra classic, a backpack type, a tube container, a paper cup, a lid material, etc. There are various types. In addition, an easy-opening treatment or resealability means may be provided as appropriate in the package of the present invention.
本発明の包装体は、主に食品、洗剤、薬剤を充填する包装体として工業的に使用することができる。具体的な用途としては、洗剤、薬剤として、洗濯用液体洗剤、台所用液体洗剤、浴用液体洗剤、浴用液体石鹸、液体シャンプー、液体コンディショナー、医薬用タブレット等が挙げられる。また、上記の容器を包装する2次包装体にも使用できる。特に前記反応型接着剤を用いているため、溶出が問題となるような食品、医薬品用途の包装体として好適に使用することができる。 The package of the present invention can be industrially used as a package mainly filled with foods, detergents and drugs. Specific examples of the detergent and detergent include laundry liquid detergent, kitchen liquid detergent, bath liquid detergent, bath liquid soap, liquid shampoo, liquid conditioner, and pharmaceutical tablet. Moreover, it can be used also for the secondary package which packages said container. In particular, since the reactive adhesive is used, it can be suitably used as a package for foods and pharmaceuticals where elution is a problem.
次に、本発明を、実施例及び比較例により具体的に説明する。例中断りのない限り、「部」「%」は質量基準である。 Next, the present invention will be specifically described with reference to examples and comparative examples. Unless otherwise indicated, “part” and “%” are based on mass.
合成例1[ポリオール成分A1の合成]
ジエチレングリコール560質量部を反応容器に仕込み、窒素ガス気流下で撹拌しながら80℃に加熱した。更に撹拌しながらアジピン酸600質量部を反応容器に仕込み150℃〜240℃に加熱してエステル化反応を行った。酸価が5mgKOH/g以下になったところで反応容器を徐々に減圧し、1mmHg以下、200〜240℃で1時間反応させ、酸価0.8mgKOH/g、分子量約840の両末端に水酸基を有するポリエステルポリオール樹脂(以下、これを「ポリオール成分A1」と略記する)を得た。Synthesis Example 1 [Synthesis of polyol component A1]
560 parts by mass of diethylene glycol was charged into a reaction vessel and heated to 80 ° C. with stirring under a nitrogen gas stream. Further, 600 parts by mass of adipic acid was charged into a reaction vessel while stirring and heated to 150 ° C. to 240 ° C. to carry out an esterification reaction. When the acid value becomes 5 mgKOH / g or less, the reaction vessel is gradually depressurized and reacted at 1 mmHg or less and 200 to 240 ° C. for 1 hour to have hydroxyl groups at both ends with an acid value of 0.8 mgKOH / g and a molecular weight of about 840. A polyester polyol resin (hereinafter abbreviated as “polyol component A1”) was obtained.
合成例2[ポリオール成分A2の合成]
ジエチレングリコール 690質量部、トリメチロールプロパン8質量部を反応容器に仕込み、窒素ガス気流下で撹拌しながら80℃に加熱して溶解した。更に撹拌しながらアジピン酸810質量部を反応容器に仕込み150℃〜240℃に加熱してエステル化反応を行った。酸価が5mgKOH/g以下になったところで反応容器を徐々に減圧し、1mmHg以下、200〜220℃で1時間反応させ、酸価0.8mgKOH/g、分子量約1270の両末端に水酸基を有するポリエステルポリオール樹脂(以下、これを「ポリオール成分A2」と略記する)を得た。Synthesis Example 2 [Synthesis of polyol component A2]
690 parts by mass of diethylene glycol and 8 parts by mass of trimethylolpropane were charged into a reaction vessel, and dissolved by heating to 80 ° C. with stirring under a nitrogen gas stream. Further, 810 parts by mass of adipic acid was charged into a reaction vessel while stirring and heated to 150 ° C. to 240 ° C. to carry out esterification reaction. When the acid value becomes 5 mgKOH / g or less, the reaction vessel is gradually depressurized and reacted at 1 mmHg or less and 200 to 220 ° C. for 1 hour, and has hydroxyl groups at both ends with an acid value of 0.8 mgKOH / g and a molecular weight of about 1270. A polyester polyol resin (hereinafter abbreviated as “polyol component A2”) was obtained.
合成例3[ポリオール成分A3の合成]
2−メチル−プロパンジオール333質量部、エチレングリコール179質量部、トリメチロールプロパン39質量部、を反応容器に仕込み、窒素ガス気流下で撹拌しながら80℃に加熱して溶解した。更に撹拌しながらイソフタル酸106質量部、アジピン酸610質量部を反応容器に仕込み150℃〜240℃に加熱してエステル化反応を行った。酸価が5mgKOH/g以下になったところで反応容器を徐々に減圧し、1mmHg以下、200〜240℃で1時間反応させ、酸価0.5mgKOH/g、分子量約2100の両末端に水酸基を有するポリエステルポリオール樹脂(以下、これを「ポリオール成分A3」と略記する)を得た。Synthesis Example 3 [Synthesis of polyol component A3]
A reaction vessel was charged with 333 parts by mass of 2-methyl-propanediol, 179 parts by mass of ethylene glycol, and 39 parts by mass of trimethylolpropane, and dissolved by heating to 80 ° C. with stirring under a nitrogen gas stream. While stirring, 106 parts by mass of isophthalic acid and 610 parts by mass of adipic acid were charged into a reaction vessel and heated to 150 ° C. to 240 ° C. to carry out an esterification reaction. When the acid value becomes 5 mgKOH / g or less, the reaction vessel is gradually depressurized and reacted at 1 mmHg or less and 200 to 240 ° C. for 1 hour to have hydroxyl groups at both ends with an acid value of 0.5 mgKOH / g and a molecular weight of about 2100. A polyester polyol resin (hereinafter abbreviated as “polyol component A3”) was obtained.
合成例4 [イソシアネート成分B1の調整]
ジフェニルメタンジイソシアネート(製品名ミリオネートMT−F 東ソー社製)271部、ポリプロピレングリコール(分子量約1000)425部、ポリプロピレングリコール(分子量約400)18部を反応容器に仕込み、窒素ガス気流下で撹拌しながら80℃に加熱して反応を行い、反応が完結したところで反応容器を冷却し、両末端にイソシアネート基を有するポリオールとイソシアネートとの反応生成物(B−1−1)を得た。
続いて、該容器にイソシアネート基を有する反応性希釈剤(B−2)としてカルボジイミド修飾ジフェニルメタンジイソシアネート(製品名ルプラネートMM103 BIP社製) 285部を加えて均一になるまで攪拌し、イソシアネート基濃度が約13.5%のイソシアネート成分B1を得た。Synthesis Example 4 [Adjustment of isocyanate component B1]
271 parts of diphenylmethane diisocyanate (product name Millionate MT-F manufactured by Tosoh Corporation), 425 parts of polypropylene glycol (molecular weight of about 1000) and 18 parts of polypropylene glycol (molecular weight of about 400) are charged into a reaction vessel and stirred under a nitrogen gas stream with 80 parts. The reaction was conducted by heating to ° C., and when the reaction was completed, the reaction vessel was cooled to obtain a reaction product (B-1-1) of a polyol having an isocyanate group at both ends and an isocyanate.
Subsequently, 285 parts of carbodiimide-modified diphenylmethane diisocyanate (product name: Luplanate MM103, manufactured by BIP) was added to the vessel as a reactive diluent (B-2) having an isocyanate group, and the mixture was stirred until it became uniform. 13.5% of isocyanate component B1 was obtained.
合成例5 [イソシアネート成分B2の合成]
ジフェニルメタンジイソシアネート(製品名ミリオネートMT−F 東ソー社製)489部、ポリプロピレングリコール(分子量約1000)422部、ポリプロピレングリコール(分子量約400)19部を反応容器に仕込み、窒素ガス気流下で撹拌しながら80℃加熱して反応を行い、反応が完結したところで反応容器を冷却し、両末端にイソシアネート基を有するポリオールとイソシアネートとの反応生成物(B−1−2)を得た。
続いて、該容器にイソシアネート基を有する反応性希釈剤(B−2)として1,6−ヘキサメチレンジイソシアネートのイソシアヌレート体(製品名デスモジュールN3300 コベストロ社製) 50部を加えて均一になるまで攪拌し、イソシアネート基濃度が約13.5%のイソシアネート成分B2を得た。Synthesis Example 5 [Synthesis of Isocyanate Component B2]
Diphenylmethane diisocyanate (product name Millionate MT-F, manufactured by Tosoh Corporation) 489 parts, 422 parts of polypropylene glycol (molecular weight about 1000) and 19 parts of polypropylene glycol (molecular weight about 400) were charged in a reaction vessel and stirred under a nitrogen gas stream with 80 parts. The reaction was performed by heating at 0 ° C., and when the reaction was completed, the reaction vessel was cooled to obtain a reaction product (B-1-2) of a polyol having an isocyanate group at both ends and an isocyanate.
Subsequently, until 50 parts of isocyanurate of 1,6-hexamethylene diisocyanate (product name: Desmodur N3300 manufactured by Covestro Co., Ltd.) is added to the container as a reactive diluent (B-2) having an isocyanate group, until uniform. With stirring, an isocyanate component B2 having an isocyanate group concentration of about 13.5% was obtained.
合成例6 [イソシアネート成分B3の合成]
ジフェニルメタンジイソシアネート(製品名ミリオネートMT−F 東ソー社製)479部、ポリプロピレングリコール(分子量約1000)452部、ポリプロピレングリコール(分子量約400)19部を反応容器に仕込み、窒素ガス気流下で撹拌しながら80℃に加熱して反応を行い、反応が完結したところで反応容器を冷却し、両末端にイソシアネート基を有するポリオールとイソシアネートとの反応生成物(B−1−3)を得た。
続いて、該容器にイソシアネート基を有する反応性希釈剤(B−2)としてポリマージフェニルメタンジイソシアネート(製品名ルプラネートM20S BIP社製) 50部を加えて均一になるまで攪拌し、イソシアネート基濃度が約13.5%のイソシアネート成分B3を得た。Synthesis Example 6 [Synthesis of Isocyanate Component B3]
479 parts of diphenylmethane diisocyanate (product name Millionate MT-F, manufactured by Tosoh Corporation), 452 parts of polypropylene glycol (molecular weight of about 1000) and 19 parts of polypropylene glycol (molecular weight of about 400) were charged into a reaction vessel and stirred under a nitrogen gas stream while stirring. The reaction was conducted by heating to ° C., and when the reaction was completed, the reaction vessel was cooled to obtain a reaction product (B-1-3) of a polyol having an isocyanate group at both ends and an isocyanate.
Subsequently, 50 parts of polymer diphenylmethane diisocyanate (product name: Luplanate M20S manufactured by BIP) was added to the container as a reactive diluent (B-2) having an isocyanate group, and the mixture was stirred until it became uniform. The isocyanate group concentration was about 13 Obtained 5% of isocyanate component B3.
合成例7 [イソシアネート成分B4の合成]
ジフェニルメタンジイソシアネート(製品名ミリオネートMT−F 東ソー社製)456部、ポリプロピレングリコール(分子量約1000)473部、ポリプロピレングリコール(分子量約400)20部を反応容器に仕込み、窒素ガス気流下で撹拌しながら80℃に加熱して反応を行い、反応が完結したところで反応容器を冷却し、両末端にイソシアネート基を有するポリオールとイソシアネートとの反応生成物(B−1−4)を得た。
続いて、該容器にイソシアネート基を有する反応性希釈剤(B−2)として1,6−ヘキサメチレンジイソシアネート(製品名デスモジュールH コベストロ社製) 50部を加えて均一になるまで攪拌し、イソシアネート基濃度が約13.5%のイソシアネート成分B4を得た。Synthesis Example 7 [Synthesis of Isocyanate Component B4]
456 parts of diphenylmethane diisocyanate (product name Millionate MT-F manufactured by Tosoh Corporation), 473 parts of polypropylene glycol (molecular weight of about 1000) and 20 parts of polypropylene glycol (molecular weight of about 400) are charged into a reaction vessel and stirred under a nitrogen gas stream with 80 parts. The reaction was carried out by heating to 0 ° C., and when the reaction was completed, the reaction vessel was cooled to obtain a reaction product (B-1-4) of a polyol having an isocyanate group at both ends and an isocyanate.
Subsequently, 50 parts of 1,6-hexamethylene diisocyanate (product name: Desmodur H manufactured by Covestro Co., Ltd.) was added to the vessel as a reactive diluent (B-2) having an isocyanate group, and the mixture was stirred until uniform. An isocyanate component B4 having a group concentration of about 13.5% was obtained.
合成例8 [イソシアネート成分B5の合成]
ジフェニルメタンジイソシアネート(製品名ミリオネートMT−F 東ソー社製)474部、ポリプロピレングリコール(分子量約1000)457部、ポリプロピレングリコール(分子量約400)19部を反応容器に仕込み、窒素ガス気流下で撹拌しながら80℃に加熱して反応を行い、反応が完結したところで反応容器を冷却し、両末端にイソシアネート基を有するポリオールとイソシアネートとの反応生成物(B−1−5)を得た。
続いて、該容器にイソシアネート基を有する反応性希釈剤(B−2)として3−イソシアナートメチル−3,5,5−トリメチルシクロヘキシルイソシアネート(製品名デスモジュールI コベストロ社製) 50部を加えて均一になるまで攪拌し、イソシアネート基濃度が約13.5%のイソシアネート成分B5を得た。Synthesis Example 8 [Synthesis of isocyanate component B5]
474 parts of diphenylmethane diisocyanate (product name Millionate MT-F manufactured by Tosoh Corporation), 457 parts of polypropylene glycol (molecular weight of about 1000) and 19 parts of polypropylene glycol (molecular weight of about 400) are charged into a reaction vessel and stirred under a nitrogen gas stream with 80 parts. The reaction was conducted by heating to ° C., and when the reaction was completed, the reaction vessel was cooled to obtain a reaction product (B-1-5) of a polyol having an isocyanate group at both ends and an isocyanate.
Subsequently, 50 parts of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (product name: Desmodur I Covestro Co., Ltd.) was added as a reactive diluent (B-2) having an isocyanate group to the container. Stirring until uniform, isocyanate component B5 having an isocyanate group concentration of about 13.5% was obtained.
比較合成例1 [イソシアネート樹脂C1の合成]
カルボジイミド修飾ジフェニルメタンジイソシアネート(製品名ルプラネートMM103 BIP社製) 589部、ポリプロピレングリコール(分子量約1000)394部、ポリプロピレングリコール(分子量約400)17部を反応容器に仕込み、窒素ガス気流下で撹拌しながら80℃に加熱して反応を行い、反応が完結したところで反応容器を冷却し、両末端にイソシアネート基を有するポリオールとイソシアネートとの反応生成物であるイソシアネート樹脂(C1)を得た。このイソシアネート基濃度は約13.5%である。Comparative Synthesis Example 1 [Synthesis of Isocyanate Resin C1]
Carbodiimide-modified diphenylmethane diisocyanate (product name: Luplanate MM103, manufactured by BIP) 589 parts, polypropylene glycol (molecular weight about 1000) 394 parts, polypropylene glycol (molecular weight about 400) 17 parts were charged in a reaction vessel and stirred under a nitrogen gas stream with 80 parts. The reaction was conducted by heating to 0 ° C., and when the reaction was completed, the reaction vessel was cooled to obtain an isocyanate resin (C1) which is a reaction product of a polyol having an isocyanate group at both ends and an isocyanate. The isocyanate group concentration is about 13.5%.
比較合成例2 [イソシアネート樹脂C2の合成]
液状ジフェニルメタンジイソシアネート(製品名ルプラネートMI BIP社製) 208部、ジフェニルメタンジイソシアネート(製品名ミリオネートMT−F 東ソー社製) 320部ポリプロピレングリコール(分子量約1000)453部、ポリプロピレングリコール(分子量約400)19部を反応容器に仕込み、窒素ガス気流下で撹拌しながら80℃に加熱して反応を行い、反応が完結したところで反応容器を冷却し、両末端にイソシアネート基を有するポリオールとイソシアネートとの反応生成物であるイソシアネート樹脂(C2)を得た。このイソシアネート基濃度は約13.5%である。Comparative Synthesis Example 2 [Synthesis of Isocyanate Resin C2]
208 parts of liquid diphenylmethane diisocyanate (product name: Luplanate MIBIP) 208 parts, diphenylmethane diisocyanate (product name: Millionate MT-F, manufactured by Tosoh Corporation) 320 parts polypropylene glycol (molecular weight about 1000) 453 parts, polypropylene glycol (molecular weight about 400) 19 parts The reaction vessel is charged and heated to 80 ° C. while stirring under a nitrogen gas stream. When the reaction is completed, the reaction vessel is cooled and a reaction product of a polyol having isocyanate groups at both ends and an isocyanate. An isocyanate resin (C2) was obtained. The isocyanate group concentration is about 13.5%.
(実施例、比較例)
表1,2の組み合わせに従い反応性接着剤を得た。(Examples and comparative examples)
Reactive adhesives were obtained according to the combinations in Tables 1 and 2.
(評価方法)
[有害成分(PAA)溶出量の評価]
実施例または比較例の組み合わせで配合した反応性接着剤を、PETフィルムに、塗布量が固形分3.0g/m2程度となるように塗布し、ラミネーターでこのフィルムの塗布面とCPPフィルムと貼合し、積層フィルムを作製した。この積層フィルムを40℃の恒温槽に3日間保存した。
この積層フィルムを120mm×220mmで切り取り、CPPが内側になるように折り曲げ、3方方向を10mm幅で1atm、180℃、1秒間でヒートシールして、内容物が2dm2接触するパウチを作製した。内容物は3%酢酸酢溶液を加えた。充填したパウチを121℃−0.5hrのレトルト殺菌後、PAAをLC/MS/MSにて測定した。(Evaluation method)
[Evaluation of elution amount of harmful components (PAA)]
A reactive adhesive compounded in a combination of Examples or Comparative Examples was applied to a PET film so that the coating amount was about 3.0 g / m 2 in solid content, and a laminator was used to apply the coated surface of the film and the CPP film. Bonding was performed to produce a laminated film. This laminated film was stored in a constant temperature bath at 40 ° C. for 3 days.
This laminated film was cut out at 120 mm × 220 mm, bent so that the CPP was inside, and heat sealed at 1 atm, 180 ° C. for 1 second in 10 mm width in 3 directions, and a pouch in which the contents were in contact with 2 dm 2 was produced. . The contents were 3% vinegar acetate solution. After the filled pouch was sterilized by retort at 121 ° C.-0.5 hr, PAA was measured by LC / MS / MS.
[配合後40℃−30分後の粘度測定]
粘度は、下記条件の回転粘度計により測定し、mPa・sの値とした。
測定装置 ;アントンパール社製 MCR−302
測定条件 ;温度 40℃、コーンプレートΦ50mm
粘度評価は次の通りとした。
粘度評価A:1000〜2000mPa・s
粘度評価B:2000〜3000mPa・s
粘度評価C:3000〜4000mPa・s
粘度評価D:4000〜5000mPa・s
粘度評価E:5000mPa・s以上[Measurement of viscosity after blending at 40 ° C. for 30 minutes]
The viscosity was measured with a rotational viscometer under the following conditions, and the value was set to mPa · s.
Measuring device: MCR-302 manufactured by Anton Paar
Measurement conditions: Temperature 40 ° C, cone plate Φ50mm
The viscosity evaluation was as follows.
Viscosity evaluation A: 1000 to 2000 mPa · s
Viscosity evaluation B: 2000 to 3000 mPa · s
Viscosity evaluation C: 3000 to 4000 mPa · s
Viscosity evaluation D: 4000 to 5000 mPa · s
Viscosity evaluation E: 5000 mPa · s or more
[ラミネート強度]
印刷インキユニビアNT(DIC製)で図柄をグラビア印刷したPETフィルムに、実施例または比較例の組み合わせで配合した反応性接着剤を、塗布量が固形分3.0g/m2程度となるように塗布した。その後ラミネーターで、該フィルムの塗布面とLLDPEフィルムと貼合し、積層フィルムを作製した。この積層フィルムを40℃の恒温槽に3日間保存し、ラミネート強度試験用の積層フィルムを作成した。
該積層フィルムから試験片を15mm幅で切り取り、引張り試験機を使用して、T型剥離により剥離速度300mm/minで、接着強度(N/15mm)を測定した。[Lamination strength]
Reactive adhesive blended with a combination of Examples or Comparative Examples is applied to a PET film on which a graphic is printed by gravure printing with Printing Ink Univia NT (manufactured by DIC) so that the coating amount is about 3.0 g / m 2 in solid content. did. Thereafter, a laminator was used to bond the coated surface of the film and the LLDPE film to produce a laminated film. This laminated film was stored in a constant temperature bath at 40 ° C. for 3 days to prepare a laminated film for a laminate strength test.
A test piece was cut out from the laminated film with a width of 15 mm, and using a tensile tester, the adhesive strength (N / 15 mm) was measured by T-type peeling at a peeling speed of 300 mm / min.
(イソシアネート成分Bを経時保存後のラミネート強度)
イソシアネート成分B1〜B5、C1〜C2を製造した後、60℃にて10日間静置した後に、表の組み合わせに従い反応性接着剤を配合し、同様にしてラミネート強度を測定した。(Lamination strength after storage of isocyanate component B over time)
After producing isocyanate components B1 to B5 and C1 to C2, the mixture was allowed to stand at 60 ° C. for 10 days, and then a reactive adhesive was blended according to the combinations in the table, and the laminate strength was measured in the same manner.
[レトルト後のラミネート強度及び外観]
印刷インキ(DIC(株)製「ユニビアNT」)で図柄をグラビア印刷したPETフィルムに、実施例または比較例の組み合わせで配合した反応性接着剤を、塗布量が固形分3.0g/m2程度となるように塗布した。その後ラミネーターで、該フィルムの塗布面とLLDPEフィルムと貼合し、積層フィルムを作製した。この積層フィルムを40℃の恒温槽に3日間保存した。
この積層フィルムを150mm×300mmで切り取り、LLDPEが内側になるように折り曲げ、1atm、180℃、1秒間でヒートシールしてパウチを作製した。内容物として1/1/1ソース(ミートソース : 植物油 : 食酢=1 : 1 : 1)を加えた。
充填したパウチはスチーム殺菌処理を121℃−30分にて実施し、内容物を除去しヒートシール部のT型剥離による強度を測定した。
また、取り出し後のそれぞれのパウチの外観を観察し、デラミの発生の有無により、以下の評価を行った。
評価○:デラミなし
評価△:デラミ箇所が5点以下
評価×:デラミ箇所が6点以上[Lamination strength and appearance after retort]
A reactive adhesive compounded with a combination of an example or a comparative example on a PET film on which a design is gravure-printed with printing ink (“Univia NT” manufactured by DIC Corporation) has a coating amount of a solid content of 3.0 g / m 2. It apply | coated so that it might become a grade. Thereafter, a laminator was used to bond the coated surface of the film and the LLDPE film to produce a laminated film. This laminated film was stored in a constant temperature bath at 40 ° C. for 3 days.
This laminated film was cut out at 150 mm × 300 mm, bent so that the LLDPE was inside, and heat-sealed at 1 atm, 180 ° C. for 1 second to prepare a pouch. As a content, 1/1/1 sauce (meat sauce: vegetable oil: vinegar = 1: 1: 1) was added.
The filled pouch was subjected to steam sterilization at 121 ° C. for 30 minutes, the contents were removed, and the strength of the heat-sealed part by T-type peeling was measured.
Moreover, the external appearance of each pouch after taking out was observed, and the following evaluation was performed by the presence or absence of generation | occurrence | production of delamination.
Evaluation ○: No delamination evaluation △: 5 points or less for delamination points Evaluation: 6 points or more for delamination points
(イソシアネート成分Bを経時保存後のレトルト後のラミネート強度及び外観)
イソシアネート成分B1〜B5、C1〜C2を製造した後、60℃にて10日間静置した後に、表の組み合わせに従い反応性接着剤を配合し、同様にしてレトルト後のラミネート強度及び外観を評価した。(Laminate strength and appearance after retorting after storage of isocyanate component B over time)
After producing the isocyanate components B1 to B5 and C1 to C2, the mixture was allowed to stand at 60 ° C. for 10 days, then a reactive adhesive was blended according to the combinations in the table, and the laminate strength and appearance after retorting were evaluated in the same manner. .
結果を表1、表2に示す。 The results are shown in Tables 1 and 2.
この結果、実施例で得た反応型接着剤は、配合後40℃−30分後の粘度は5000mPa・s以下であり長いポットライフを示し、且つPAA溶出量は10ppb以下であった。またラミネート強度、外観にも優れていた。
比較例は数平均分子量が400〜1000の範囲であるイソシアネート基を有する反応性希釈剤(B−2)を含まない例である。比較例1はポリオールとカルボジイミド修飾ジフェニルメタンジイソシアネートとの反応生成物を使用した例であり、PAA溶出量は10ppb以下であったが、配合後40℃−30分後の粘度が、配合後早い段階(20分後)から6000mPa・sを超えてしまった。また、比較例2はポリオールとジフェニルメタンジイソシアネートとの反応生成物を使用した例であり、配合後40℃−30分後の粘度は5000mPa・s以下でありポットライフは問題なかったが、PAA溶出量は100ppb以上と非常に高い値を示した。As a result, the reactive adhesives obtained in the examples had a viscosity of 5000 mPa · s or less after 40 ° C. for 30 minutes after blending, showed a long pot life, and the PAA elution amount was 10 ppb or less. The laminate strength and appearance were also excellent.
A comparative example is an example which does not contain the reactive diluent (B-2) which has an isocyanate group whose number average molecular weight is the range of 400-1000. Comparative Example 1 is an example using a reaction product of a polyol and a carbodiimide-modified diphenylmethane diisocyanate, and the PAA elution amount was 10 ppb or less, but the viscosity after 40 ° C. to 30 minutes after blending was an early stage after blending ( After 20 minutes), it exceeded 6000 mPa · s. Comparative Example 2 is an example in which a reaction product of polyol and diphenylmethane diisocyanate was used. The viscosity after blending at 40 ° C. for 30 minutes was 5000 mPa · s or less and the pot life was not problematic, but the PAA elution amount Showed a very high value of 100 ppb or more.
Claims (4)
前記イソシアネート成分Bは、ポリオールとイソシアネートとの反応生成物(B−1)及び数平均分子量が400〜1000の範囲であるイソシアネート基を有する反応性希釈剤(B−2)を含有し、
前記ポリオール成分Aとイソシアネート成分Bとを重量比の割合で配合し40℃雰囲気下で30分放置後の粘度が5000mPa・s以下であることを特徴とする反応型接着剤。Having a polyol component A containing a polyol compound and an isocyanate component B containing an isocyanate compound,
The isocyanate component B contains a reaction product (B-1) of a polyol and an isocyanate and a reactive diluent (B-2) having an isocyanate group having a number average molecular weight in the range of 400 to 1,000.
A reactive adhesive, wherein the polyol component A and the isocyanate component B are blended in a ratio by weight, and the viscosity after leaving for 30 minutes in a 40 ° C. atmosphere is 5000 mPa · s or less.
前記接着剤層が請求項1または2に記載の反応型接着剤の層であることを特徴とする包装体。A package formed by forming a laminated film formed by laminating an adhesive layer between a first plastic film and a second plastic film into a bag shape,
The packaging body, wherein the adhesive layer is a layer of the reactive adhesive according to claim 1.
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AU2017368512B2 (en) | 2019-12-19 |
TWI753975B (en) | 2022-02-01 |
JP6451021B2 (en) | 2019-01-16 |
CN109983097A (en) | 2019-07-05 |
AU2017368512A1 (en) | 2019-06-06 |
CN109983097B (en) | 2021-11-16 |
WO2018101242A1 (en) | 2018-06-07 |
TW201833287A (en) | 2018-09-16 |
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