JP6591040B2 - Hot melt adhesive - Google Patents
Hot melt adhesive Download PDFInfo
- Publication number
- JP6591040B2 JP6591040B2 JP2018503000A JP2018503000A JP6591040B2 JP 6591040 B2 JP6591040 B2 JP 6591040B2 JP 2018503000 A JP2018503000 A JP 2018503000A JP 2018503000 A JP2018503000 A JP 2018503000A JP 6591040 B2 JP6591040 B2 JP 6591040B2
- Authority
- JP
- Japan
- Prior art keywords
- glycol
- bisphenol
- hot melt
- melt adhesive
- polyol
- 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.)
- Active
Links
- 239000004831 Hot glue Substances 0.000 title claims description 32
- 150000003077 polyols Chemical class 0.000 claims description 63
- 229920005862 polyol Polymers 0.000 claims description 60
- 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 claims description 58
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- -1 bisphenol compound Chemical class 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 24
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 20
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 16
- 229920006324 polyoxymethylene Polymers 0.000 claims description 15
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000005442 diisocyanate group Chemical group 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 claims description 8
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 229930185605 Bisphenol Natural products 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 40
- 238000004519 manufacturing process Methods 0.000 description 37
- 239000003054 catalyst Substances 0.000 description 22
- 239000000126 substance Substances 0.000 description 21
- 238000004817 gas chromatography Methods 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- 239000000853 adhesive Substances 0.000 description 16
- 230000001070 adhesive effect Effects 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000004359 castor oil Substances 0.000 description 11
- 235000019438 castor oil Nutrition 0.000 description 11
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920005906 polyester polyol Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229920005992 thermoplastic resin Polymers 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- 239000005062 Polybutadiene Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- IIRDTKBZINWQAW-UHFFFAOYSA-N hexaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCO IIRDTKBZINWQAW-UHFFFAOYSA-N 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 2
- QUPKOUOXSNGVLB-UHFFFAOYSA-N 1,8-diisocyanatooctane Chemical compound O=C=NCCCCCCCCN=C=O QUPKOUOXSNGVLB-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- 125000006697 (C1-C3) aminoalkyl group Chemical group 0.000 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- VNMOIBZLSJDQEO-UHFFFAOYSA-N 1,10-diisocyanatodecane Chemical compound O=C=NCCCCCCCCCCN=C=O VNMOIBZLSJDQEO-UHFFFAOYSA-N 0.000 description 1
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 1
- SKBCSCHPOLWLCN-UHFFFAOYSA-N 2-sulfohexanedioic acid Chemical compound OC(=O)CCCC(C(O)=O)S(O)(=O)=O SKBCSCHPOLWLCN-UHFFFAOYSA-N 0.000 description 1
- ZCXNPIWNNTXPSE-UHFFFAOYSA-N 2-sulfopentanedioic acid Chemical compound OC(=O)CCC(C(O)=O)S(O)(=O)=O ZCXNPIWNNTXPSE-UHFFFAOYSA-N 0.000 description 1
- MFWSRADQRNGSHU-UHFFFAOYSA-N 2-sulfopropanedioic acid Chemical compound OC(=O)C(C(O)=O)S(O)(=O)=O MFWSRADQRNGSHU-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- QGWJHTDEMCBYFL-UHFFFAOYSA-N 4-(4-hydroxyphenyl)phenol;oxirane Chemical compound C1CO1.C1=CC(O)=CC=C1C1=CC=C(O)C=C1 QGWJHTDEMCBYFL-UHFFFAOYSA-N 0.000 description 1
- ZRWNRAJCPNLYAK-UHFFFAOYSA-N 4-bromobenzamide Chemical compound NC(=O)C1=CC=C(Br)C=C1 ZRWNRAJCPNLYAK-UHFFFAOYSA-N 0.000 description 1
- IXHCMWNYFGLCBS-UHFFFAOYSA-N 4-piperidin-1-ylhexan-2-amine Chemical compound CC(N)CC(CC)N1CCCCC1 IXHCMWNYFGLCBS-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N Alizarin Natural products C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical group OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- TUEIURIZJQRMQE-UHFFFAOYSA-N [2-(tert-butylsulfamoyl)phenyl]boronic acid Chemical compound CC(C)(C)NS(=O)(=O)C1=CC=CC=C1B(O)O TUEIURIZJQRMQE-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- SFHGONLFTNHXDX-UHFFFAOYSA-N [4-[4-(hydroxymethyl)phenyl]phenyl]methanol Chemical group C1=CC(CO)=CC=C1C1=CC=C(CO)C=C1 SFHGONLFTNHXDX-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QFNNDGVVMCZKEY-UHFFFAOYSA-N azacyclododecan-2-one Chemical compound O=C1CCCCCCCCCCN1 QFNNDGVVMCZKEY-UHFFFAOYSA-N 0.000 description 1
- JTQGMAIGACKGFO-UHFFFAOYSA-N benzene-1,2-diol;oxirane Chemical compound C1CO1.OC1=CC=CC=C1O JTQGMAIGACKGFO-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 229930004069 diterpene Natural products 0.000 description 1
- 125000000567 diterpene group Chemical group 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- SEIUOYFQDIJJEO-UHFFFAOYSA-N hexane-1,1,1-tricarboxylic acid Chemical compound CCCCCC(C(O)=O)(C(O)=O)C(O)=O SEIUOYFQDIJJEO-UHFFFAOYSA-N 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-N methyl hydrogen carbonate Chemical compound COC(O)=O CXHHBNMLPJOKQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- GZUCMODGDIGMBI-UHFFFAOYSA-N n',n'-dipropylpropane-1,3-diamine Chemical compound CCCN(CCC)CCCN GZUCMODGDIGMBI-UHFFFAOYSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- KOOMFXGDLMRWSN-UHFFFAOYSA-N n-phenylnitrous amide Chemical compound O=NNC1=CC=CC=C1 KOOMFXGDLMRWSN-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical class 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- LGOPTUPXVVNJFH-UHFFFAOYSA-N pentadecanethioic s-acid Chemical compound CCCCCCCCCCCCCCC(O)=S LGOPTUPXVVNJFH-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OOCYPIXCHKROMD-UHFFFAOYSA-M phenyl(propanoyloxy)mercury Chemical compound CCC(=O)O[Hg]C1=CC=CC=C1 OOCYPIXCHKROMD-UHFFFAOYSA-M 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- UKHQRARQNZOXRL-UHFFFAOYSA-N trimethyltin Chemical compound C[SnH](C)C UKHQRARQNZOXRL-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-VBJOUPRGSA-N triricinolein Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/C[C@H](O)CCCCCC)COC(=O)CCCCCCC\C=C/C[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-VBJOUPRGSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000003221 volumetric titration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は熱可塑性ウレタン樹脂を含有するホットメルト接着剤に関する。 The present invention relates to a hot melt adhesive containing a thermoplastic urethane resin.
熱可塑性樹脂は、通常温度の上昇に伴い樹脂強度が低下するため、使用する際には耐熱性が問題となることがある。熱可塑性樹脂を使用した製品の品質安定性の観点から、広い温度領域で、温度依存性の少ない熱可塑性樹脂が望まれている。また、使用する際の扱いやすさから、シャープメルト性（融点を超えると、すぐに流動性が発現）を有するような熱可塑性樹脂が望まれている。このような温度依存性の少ない熱可塑性樹脂として、対称構造を有するジイソシアネートと対称構造を有する低分子ジオールおよび／または対称構造を有する低分子ジアミン類とから構成されるハードセグメントを有するホットメルト接着剤が知られている（特許文献１）。しかし、上記ホットメルト接着剤は凝集力が低く、引張破断強度が低いという課題がある。 Thermoplastic resins usually have lower resin strength as the temperature rises, so heat resistance may be a problem when used. From the viewpoint of product quality stability using a thermoplastic resin, a thermoplastic resin having a small temperature dependency in a wide temperature range is desired. In addition, a thermoplastic resin having sharp melt properties (fluidity immediately appears when the melting point is exceeded) is desired for ease of handling when used. A hot melt adhesive having a hard segment composed of a diisocyanate having a symmetric structure and a low molecular diol having a symmetric structure and / or a low molecular diamine having a symmetric structure as a thermoplastic resin having a low temperature dependency. Is known (Patent Document 1). However, the hot melt adhesive has a problem that the cohesive force is low and the tensile strength at break is low.
本発明の目的は、温度依存性が少なく、融点を超えるとすぐに流動性が発現し、かつ引張破断強度に優れるホットメルト接着剤を提供することにある。 An object of the present invention is to provide a hot melt adhesive that is less temperature dependent, exhibits fluidity as soon as the melting point is exceeded, and is excellent in tensile strength at break.
本発明者らは、上述の状況に鑑み鋭意検討した結果、本発明に到達した。即ち、本発明は、芳香環を有するポリオール（Ａ）、対称性を有するジイソシアネート（Ｂ）、一般式（１）で示されるポリメチレングリコール（Ｃ１）及び／又は一般式（２）で示されるポリエチレングリコール（Ｃ２）であるグリコール（Ｃ）、並びに高分子ポリオール（Ｄ）を必須構成単量体とする熱可塑性ウレタン樹脂（Ｆ）を含有するホットメルト接着剤である。
ＨＯ−（ＣＨ２）ｎ−ＯＨ （１）
［ｎは２〜８の整数である。］
ＨＯ−（ＣＨ２ＣＨ２Ｏ）ｍ−Ｈ （２）
［ｍは２〜８の整数である。］The inventors of the present invention have reached the present invention as a result of intensive studies in view of the above situation. That is, the present invention relates to a polyol (A) having an aromatic ring, a diisocyanate (B) having symmetry, a polymethylene glycol (C1) represented by the general formula (1) and / or a polyethylene represented by the general formula (2). It is a hot melt adhesive containing a thermoplastic urethane resin (F) whose essential constituent monomer is glycol (C), which is glycol (C2), and polymer polyol (D).
HO— (CH 2 ) n —OH (1)
[N is an integer of 2 to 8. ]
HO- (CH 2 CH 2 O) m-H (2)
[M is an integer of 2 to 8. ]
本発明のホットメルト接着剤に含まれる熱可塑性ウレタン樹脂は、温度依存性が少ないため、これを使用した製品の品質安定性に優れ、ホットメルト接着剤として使用した際には、接着力が安定する。また、シャープメルト性（融点を超えると比較的すぐに流動性が発現）を有するため、取り扱いが容易である。さらに、引張破断強度にも優れる。 The thermoplastic urethane resin contained in the hot melt adhesive of the present invention has little temperature dependence, so it has excellent product quality stability and stable adhesive strength when used as a hot melt adhesive. To do. Further, since it has sharp melt properties (fluidity appears relatively soon when the melting point is exceeded), it is easy to handle. Furthermore, the tensile strength at break is also excellent.
本発明における芳香環を有するポリオール（Ａ）としては、例えば、ビスフェノールＡ、ビスフェノールＢ、ビスフェノールＥ及びビスフェノールＦからなる群より選ばれる少なくとも１種のビスフェノール化合物（Ｊ）のエチレンオキサイド付加物、ジヒドロキシベンゼンのエチレンオキサイド付加物、ジヒドロキシビフェニールのエチレンオキサイド付加物、ビス（ヒドロキシメチル）ベンゼン、該化合物のエチレンオキサイド付加物、ビス（ヒドロキシメチル）ビフェニール、該化合物のエチレンオキサイド付加物、フタル酸のエチレンオキサイド付加物及びそれらの２種以上の混合物等が挙げられる。 As the polyol (A) having an aromatic ring in the present invention, for example, an ethylene oxide adduct of at least one bisphenol compound (J) selected from the group consisting of bisphenol A, bisphenol B, bisphenol E and bisphenol F, dihydroxybenzene Ethylene oxide adduct, dihydroxybiphenyl ethylene oxide adduct, bis (hydroxymethyl) benzene, ethylene oxide adduct of the compound, bis (hydroxymethyl) biphenyl, ethylene oxide adduct of the compound, ethylene oxide addition of phthalic acid And a mixture of two or more thereof.
上記エチレンオキサイド（以下、ＥＯ）付加物のＥＯ平均付加モル数は、好ましくは水酸基あたり０．９０〜１．１０であり、より好ましくは０．９１〜１．０９であり、さらに好ましくは０．９２〜１．０８である。
上記ＥＯ付加物のＥＯ平均付加モル数が水酸基あたり０．９０以上であれば接着力が向上し、１．１０以下であれば引張破断強度が向上する。
芳香環を有するポリオール（Ａ）のうち、ビスフェノールＡ、ビスフェノールＢ、ビスフェノールＥ及びビスフェノールＦからなる群より選ばれる少なくとも１種のビスフェノール化合物のエチレンオキサイド付加物（Ａ１）が好ましく、エチレンオキサイド付加物（Ａ１）のうち、エチレンオキサイド平均付加モル数が水酸基あたり０．９０〜１．１０であり、下記式（１）で示される単分散度が８０％以上であるエチレンオキサイド付加物（Ａ１１）がさらに好ましい。
単分散度（％）＝｛［水酸基あたりエチレンオキサイド付加モル数が１モルであるエチレンオキサイド付加物（Ａ１）の重量］／［エチレンオキサイド付加物（Ａ）の重量］｝×１００ （１）The EO average addition mole number of the ethylene oxide (hereinafter referred to as EO) adduct is preferably 0.90 to 1.10 per hydroxyl group, more preferably 0.91 to 1.09, and still more preferably 0.8. 92 to 1.08.
If the EO average addition mole number of the EO adduct is 0.90 or more per hydroxyl group, the adhesive strength is improved, and if it is 1.10 or less, the tensile strength at break is improved.
Among the polyols (A) having an aromatic ring, an ethylene oxide adduct (A1) of at least one bisphenol compound selected from the group consisting of bisphenol A, bisphenol B, bisphenol E and bisphenol F is preferred, and an ethylene oxide adduct ( Among A1), the ethylene oxide adduct (A11) having an average ethylene oxide addition mole number of 0.90 to 1.10 per hydroxyl group and a monodispersity of 80% or more represented by the following formula (1) is further provided preferable.
Monodispersity (%) = {[weight of ethylene oxide adduct (A1) having 1 mol of ethylene oxide added per hydroxyl group] / [weight of ethylene oxide adduct (A)]} × 100 (1)
エチレンオキサイド付加物（Ａ１）のうち、エチレンオキサイド平均付加モル数が水酸基あたり０．９０〜１．１０であり、上記式（１）で示される単分散度が８０％以上であるエチレンオキサイド付加物（Ａ１１）を使用すると、接着力を特に高くすることができ、かつ、引張破断強度も高くすることができる。 Among the ethylene oxide adducts (A1), the ethylene oxide average addition mole number is 0.90 to 1.10 per hydroxyl group, and the monodispersity represented by the above formula (1) is 80% or more. When (A11) is used, the adhesive force can be particularly increased, and the tensile strength at break can also be increased.
ビスフェノール化合物（Ｊ）の内、特に好ましいのは、ビスフェノールＡである。
なお、ビスフェノールＢは、２，２−ビス（ｐ−ヒドロキシフェニル）ブタンであり、フェノールＥは１，１−ビス（ｐ−ヒドロキシフェニル）エタンであり、ビスフェノールＦはビス（ｐ−ヒドロキシフェニル）メタンである。
上記式（１）で示される（Ａ１１）の単分散度は８０％以上であり、好ましくは８５％以上、さらに好ましくは９０％以上である。
（Ａ１１）の単分散度が８０％未満であれば、引張破断強度が低下し、温度依存性が高くなり高温での接着力が低下する。Of the bisphenol compounds (J), bisphenol A is particularly preferable.
Note that bisphenol B is 2,2-bis (p-hydroxyphenyl) butane, phenol E is 1,1-bis (p-hydroxyphenyl) ethane, and bisphenol F is bis (p-hydroxyphenyl) methane. It is.
The monodispersity of (A11) represented by the above formula (1) is 80% or more, preferably 85% or more, and more preferably 90% or more.
If the monodispersity of (A11) is less than 80%, the tensile strength at break is lowered, the temperature dependency is increased, and the adhesive force at high temperature is lowered.
単分散度、ＥＯ平均付加モル数は、シリル化剤で前処理した上でガスクロマトグラフ（ＧＣ）によって確認できる。測定条件は次の通りである。
＜試料の予備調製方法＞
試料１ｇを採取し、次いでアセトン１９ｇを加えて溶解させる。この試料にＴＭＳ−Ｈ１（Ｔｒｉｍｅｔｈｙｌｃｈｌｏｒｏｓｉｌａｎｅのシリル化剤、東京化成工業株式会社製）を０．１ｍｌ加え、２〜３分間、５０〜７０℃に温めシリル化を完結させる。この上澄みを１μｌ採取し、ガスクロマトグラフで測定を行う。
＜ＧＣの測定条件＞
ＧＣ機種 ：ＧＣ−１４Ｂ（株式会社島津製作所製）
充填剤：シリコンＧＥ−ＳＥ−５２（４％）、担体ＣｒｏｍｏｓｏｒｂＧ（ＡＷ−ＤＭＣＳ）;１５０〜１８０μｍ（和光純薬工業株式会社製パックドカラム）
カラム温度 ：２５０〜３５０℃（昇温速度１０℃／分）
検出器 ：ＦＩＤ
溶媒 ：アセトンまたはメチルエチルケトン
キャリアガス ：窒素 流量５０ｍｌ／分
＜単分散度の計算方法＞
ガスクロマトグラムにおける各モル数のＥＯ付加物のピーク面積から、下記式（２）によって計算する。
単分散度（％）＝１００×水酸基あたり１モル付加物ピーク面積／（水酸基あたり０〜４モル付加物ピーク面積） （２）
上記ピーク面積は各ＥＯ付加物の重量に比例する。The monodispersity and EO average addition mole number can be confirmed by gas chromatography (GC) after pretreatment with a silylating agent. The measurement conditions are as follows.
<Preparation method of sample>
A 1 g sample is taken and then 19 g acetone is added and dissolved. To this sample, 0.1 ml of TMS-H1 (Trimethylchlorosilane silylating agent, manufactured by Tokyo Chemical Industry Co., Ltd.) is added and heated to 50-70 ° C. for 2-3 minutes to complete the silylation. 1 μl of this supernatant is sampled and measured with a gas chromatograph.
<Measurement conditions for GC>
GC model: GC-14B (manufactured by Shimadzu Corporation)
Filler: Silicon GE-SE-52 (4%), carrier Cromosorb G (AW-DMCS); 150 to 180 μm (packed column manufactured by Wako Pure Chemical Industries, Ltd.)
Column temperature: 250-350 ° C. (temperature increase rate: 10 ° C./min)
Detector: FID
Solvent: Acetone or methyl ethyl ketone Carrier gas: Nitrogen Flow rate 50 ml / min <Calculation method of monodispersity>
From the peak area of each mole number of EO adducts in the gas chromatogram, calculation is performed according to the following formula (2).
Monodispersity (%) = 100 × 1 mol adduct peak area per hydroxyl group / (0-4 mol adduct peak area per hydroxyl group) (2)
The peak area is proportional to the weight of each EO adduct.
本発明における対称性を有するジイソシアネート（Ｂ）としては、ポリメチレンジイソシアネート（Ｂ１）［例えば、エチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート（ＨＤＩ）、オクタメチレンジイソシアネート、デカメチレンジイソシアネート、ドデカメチレンジイソシアネート等］、対称性を有し環構造を有するジイソシアネート［例えば、メチレンビス（４，１−フェニレン）＝ジイソシアネート、ジシクロヘキシルメタン−４，４’−ジイソシアネート等］等が挙げられる。
上記（Ｂ）のうち、イソシアネート基中の炭素を除く炭素数が、２〜１８の偶数であるものが好ましい。
これらの内、結晶性の観点から好ましいのは、ポリメチレンジイソシアネート（Ｂ１）であり、さらに好ましいのは炭素数（イソシアネート基中の炭素を除く）が６〜１０の偶数を有するポリメチレンジイソシアネートである。As the diisocyanate (B) having symmetry in the present invention, polymethylene diisocyanate (B1) [for example, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, etc.] And diisocyanates having symmetry and a ring structure [for example, methylenebis (4,1-phenylene) = diisocyanate, dicyclohexylmethane-4,4′-diisocyanate and the like] and the like.
Among the above (B), those having an even number of 2 to 18 carbon atoms excluding carbon in the isocyanate group are preferable.
Of these, polymethylene diisocyanate (B1) is preferable from the viewpoint of crystallinity, and more preferable is polymethylene diisocyanate having an even number of 6 to 10 carbon atoms (excluding carbon in the isocyanate group). .
グリコール（Ｃ）は、一般式（１）で示されるポリメチレングリコール（Ｃ１）及び／又は一般式（２）で示されるポリエチレングリコール（Ｃ２）であるグリコール（Ｃ）であり、結晶性の観点からグリコール（Ｃ）に含まれるポリメチレングリコール（Ｃ１）及びポリエチレングリコール（Ｃ２）の炭素数がそれぞれ偶数であることが好ましい。
これは、グリコール（Ｃ）がポリメチレングリコール（Ｃ１）だけを含むときはポリメチレングリコール（Ｃ１）の炭素数が偶数であり、グリコール（Ｃ）がポリエチレングリコール（Ｃ２）だけを含むときはポリエチレングリコール（Ｃ２）の炭素数が偶数であり、グリコール（Ｃ）がポリメチレングリコール（Ｃ１）及びポリエチレングリコール（Ｃ２）を含むときはポリメチレングリコール（Ｃ１）の炭素数が偶数であり、かつ、ポリエチレングリコール（Ｃ２）の炭素数が偶数であることを意味する。
本発明におけるポリメチレングリコール（Ｃ１）としては、エチレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、１，８―オクタンジオール等が挙げられる。
繰り返し数が２〜８のポリエチレングリコール（Ｃ２）としては、ジエチレングリコール、トリエチレングリコール、ヘキサエチレングリコール等が挙げられる。
これら（Ｃ）の内、結晶性の観点から好ましいのは（Ｃ１）であり、更に好ましいのは炭素数が４〜８の偶数を有するポリメチレングリコールであり、特に好ましいのは炭素数が６〜８の偶数を有するポリメチレングリコールである。Glycol (C) is glycol (C) which is polymethylene glycol (C1) represented by general formula (1) and / or polyethylene glycol (C2) represented by general formula (2), from the viewpoint of crystallinity. The polymethylene glycol (C1) and polyethylene glycol (C2) contained in the glycol (C) preferably have an even number of carbon atoms.
This is because when the glycol (C) contains only polymethylene glycol (C1), the polymethylene glycol (C1) has an even number of carbon atoms, and when the glycol (C) contains only polyethylene glycol (C2), the polyethylene glycol When (C2) has an even number of carbon atoms and the glycol (C) contains polymethylene glycol (C1) and polyethylene glycol (C2), the polymethylene glycol (C1) has an even number of carbon atoms and polyethylene glycol It means that the number of carbon atoms in (C2) is an even number.
Examples of the polymethylene glycol (C1) in the present invention include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, and the like.
Examples of the polyethylene glycol (C2) having 2 to 8 repeats include diethylene glycol, triethylene glycol, hexaethylene glycol and the like.
Among these (C), from the viewpoint of crystallinity, (C1) is preferable, more preferable is polymethylene glycol having an even number of 4 to 8 carbon atoms, and particularly preferable is 6 to 6 carbon atoms. Polymethylene glycol having an even number of 8.
本発明における熱可塑性ウレタン樹脂（Ｆ）の必須構成単量体としては、ポリメチレンジイソシアネート（Ｂ１）とポリメチレングリコール（Ｃ１）の組合せが好ましく、（Ｂ１）のイソシアネート基中の炭素を除く炭素数と（Ｃ１）の炭素数は、結晶性の観点から同数であることが好ましい。例えば、テトラメチレンジイソシアネートと１，４−ブタンジオール、ヘキサメチレンジイソシアネートと１，６−ヘキサンジオール、オクタメチレンジイソシアネートと１，８―オクタンジオールの組合せ等である。 As an essential constituent monomer of the thermoplastic urethane resin (F) in the present invention, a combination of polymethylene diisocyanate (B1) and polymethylene glycol (C1) is preferable, and the number of carbon atoms excluding carbon in the isocyanate group of (B1). And (C1) preferably have the same number of carbon atoms from the viewpoint of crystallinity. For example, combinations of tetramethylene diisocyanate and 1,4-butanediol, hexamethylene diisocyanate and 1,6-hexanediol, octamethylene diisocyanate and 1,8-octanediol, and the like.
高分子ポリオール（Ｄ）としては、ポリエーテルポリオール（Ｄ１）、ポリエステルポリオール（Ｄ２）及びその他のポリオール（Ｄ３）等が挙げられる。高分子ポリオール（Ｄ）の数平均分子量（以下Ｍｎ）は４００〜１００００であることが好ましく、１０００〜５０００であることがさらに好ましい。 Examples of the polymer polyol (D) include polyether polyol (D1), polyester polyol (D2), and other polyol (D3). The number average molecular weight (hereinafter referred to as Mn) of the polymer polyol (D) is preferably 400 to 10,000, and more preferably 1000 to 5000.
ポリエーテルポリオール（Ｄ１）としては、例えばポリアルキレングリコール［ポリエチレングリコール、ポリプロピレングリコール及びポリテトラメチレンエーテルグリコール、ポリ−３−メチルテトラメチレンエーテルグリコール等］、共重合ポリオキシアルキレンジオール［ＥＯ／ＰＯ共重合ジオール、ＴＨＦ／ＥＯ共重合ジオール及びＴＨＦ／３−メチルテトラヒドロフラン共重合ジオール等（重量比は例えば１／９〜９／１）］及びビスフェノール系化合物のＡＯ付加物；３官能以上のポリエーテルポリオール、例えば３価以上の多価アルコールのＡＯ付加物［グリセリンのＡＯ付加物及びトリメチロールプロパンのＡＯ付加物等］；並びにこれらの１種以上をメチレンジクロライドでカップリングしたもの等が挙げられる。 Examples of the polyether polyol (D1) include polyalkylene glycol [polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol, poly-3-methyltetramethylene ether glycol, etc.], copolymer polyoxyalkylene diol [EO / PO copolymerization]. Diol, THF / EO copolymerized diol, THF / 3-methyltetrahydrofuran copolymer diol and the like (weight ratio is, for example, 1/9 to 9/1)] and an AO adduct of a bisphenol-based compound; Examples thereof include AO adducts of trihydric or higher polyhydric alcohols [AO adducts of glycerin and AO adducts of trimethylolpropane]; and those obtained by coupling one or more of these with methylene dichloride.
ポリエステルポリオール（Ｄ２）としては、例えば縮合ポリエステルポリオール、ポリラクトンポリオール、ヒマシ油系ポリオール及びポリカーボネートポリオールが挙げられる。 Examples of the polyester polyol (D2) include condensed polyester polyols, polylactone polyols, castor oil-based polyols, and polycarbonate polyols.
縮合ポリエステルポリオールとしては、Ｍｎが３００未満の低分子量ポリオール又はポリエーテルポリオール（Ｄ１）と、ポリカルボン酸又はそのエステル形成性誘導体（酸無水物及び炭素数１〜４のアルキルエステル等）との重縮合物等が挙げられる。 As the condensed polyester polyol, a low molecular weight polyol or polyether polyol (D1) having an Mn of less than 300 and a polycarboxylic acid or an ester-forming derivative thereof (an acid anhydride, an alkyl ester having 1 to 4 carbon atoms, etc.) Examples include condensates.
ポリカルボン酸としては、ジカルボン酸及び３価〜４価又はそれ以上のポリカルボン酸が挙げられ、具体的には、炭素数２〜３０又はそれ以上（好ましくは炭素数２〜１２）の飽和又は不飽和の脂肪族ポリカルボン酸［炭素数２〜１５のジカルボン酸（シュウ酸、コハク酸、マロン酸、アジピン酸、スベリン酸、アゼライン酸、セバチン酸、ドデカンジカルボン酸、マレイン酸、フマル酸及びイタコン酸等）及び炭素数６〜２０のトリカルボン酸（トリカルバリル酸及びヘキサントリカルボン酸）］；炭素数８〜１５の芳香族ポリカルボン酸［テレフタル酸、イソフタル酸及びフタル酸等のジカルボン酸並びにトリメリット酸及びピロメリット酸等のトリ又はテトラカルボン酸等）；炭素数６〜４０の脂環式ポリカルボン酸（ダイマー酸等）；及びスルホ基含有ポリカルボン酸［上記ポリカルボン酸にスルホ基を導入してなるもの、例えばスルホコハク酸、スルホマロン酸、スルホグルタル酸、スルホアジピン酸及びスルホイソフタル酸及びそれらの塩（例えば金属塩、アンモニウム塩、アミン塩及び４級アンモニウム塩）；並びにカルボキシ末端のポリマーが挙げられる。 Examples of the polycarboxylic acid include dicarboxylic acids and trivalent to tetravalent or higher polycarboxylic acids, and specifically, saturated or saturated with 2 to 30 or more carbon atoms (preferably 2 to 12 carbon atoms). Unsaturated aliphatic polycarboxylic acids [dicarboxylic acids having 2 to 15 carbon atoms (oxalic acid, succinic acid, malonic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid and itacone Acid) and tricarboxylic acids having 6 to 20 carbon atoms (tricarballylic acid and hexanetricarboxylic acid)]; aromatic polycarboxylic acids having 8 to 15 carbon atoms [dicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic acid, and trimellit Tri- or tetracarboxylic acid such as acid and pyromellitic acid); alicyclic polycarboxylic acid having 6 to 40 carbon atoms (such as dimer acid) And a sulfo group-containing polycarboxylic acid [the one obtained by introducing a sulfo group into the polycarboxylic acid, such as sulfosuccinic acid, sulfomalonic acid, sulfoglutaric acid, sulfoadipic acid, sulfoisophthalic acid and salts thereof (for example, metal salts, ammonium Salts, amine salts and quaternary ammonium salts); and carboxy-terminated polymers.
カルボキシ末端のポリマーとしては、ポリエーテルポリカルボン酸［例えばＭｎが３００未満の低分子量ポリオール又はポリエーテルポリオール（Ｄ１）等のポリオールのカルボキシメチルエーテル（アルカリの存在下にモノクロル酢酸を反応させて得られるもの等）］；ポリアミド及び／又はポリエステルポリカルボン酸［例えば上記ポリカルボン酸を開始剤として炭素数４〜１５のラクタム（カプロラクタム、エナントラクタム、ラウロラクタム及びウンデカノラクタム等）又は炭素数４〜１５のラクトン（γ−ブチロラクトン、γ−バレロラクトン及びε−カプロラクトン等）を開環重合させてなるポリラクタムポリカルボン酸及びポリラクトンポリカルボン酸］が挙げられる。 As the carboxy-terminated polymer, a polyether polycarboxylic acid [for example, a low molecular weight polyol having an Mn of less than 300 or a carboxymethyl ether of a polyol such as a polyether polyol (D1) (obtained by reacting monochloroacetic acid in the presence of alkali) Polyamides and / or polyester polycarboxylic acids (for example, lactams having 4 to 15 carbon atoms (such as caprolactam, enantolactam, laurolactam, undecanolactam, etc.) or carbon atoms having 4 to 15 carbon atoms using the polycarboxylic acid as an initiator. Polylactam polycarboxylic acids and polylactone polycarboxylic acids obtained by ring-opening polymerization of lactones (γ-butyrolactone, γ-valerolactone, ε-caprolactone, etc.).
ポリラクトンポリオールとしては、水又はＭｎが３００未満の低分子量ポリオールを開始剤とする炭素数４〜１５のラクトン（γ−ブチロラクトン、γ−バレロラクトン及びε−カプロラクトン等）の開環付加物等が挙げられる。 Examples of polylactone polyols include ring-opened adducts of lactones having 4 to 15 carbon atoms (γ-butyrolactone, γ-valerolactone, ε-caprolactone, etc.), which are initiated by water or a low molecular weight polyol having an Mn of less than 300. Can be mentioned.
ヒマシ油系ポリオールとしては、ヒマシ油（リシノール酸トリグリセリド）、部分脱水ヒマシ油、部分アシル化ヒマシ油、水添ヒマシ油及びこれらの変性物［ポリエーテルポリオール（Ｄ１）若しくはＭｎが３００未満の低分子ポリオールとヒマシ油、部分脱水ヒマシ油若しくは水添ヒマシ油とのエステル交換反応により得られるエステルポリオール、及びポリエーテルポリオール（Ｄ１）若しくはＭｎが３００未満の低分子ポリオールとヒマシ油脂肪酸若しくは水添ヒマシ油脂肪酸とのエステル化反応により得られるエステル等］等が挙げられる。 Castor oil-based polyols include castor oil (ricinoleic acid triglyceride), partially dehydrated castor oil, partially acylated castor oil, hydrogenated castor oil, and modified products thereof [polyether polyol (D1) or low molecular weight Mn of less than 300 Ester polyol obtained by transesterification reaction between polyol and castor oil, partially dehydrated castor oil or hydrogenated castor oil, and polyether polyol (D1) or low molecular polyol having Mn of less than 300 and castor oil fatty acid or hydrogenated castor oil Ester obtained by esterification reaction with fatty acid, etc.].
ポリカーボネートポリオールとしては、Ｍｎが３００未満の低分子量ポリオールを開始剤とするアルキレンカーボネートの開環付加／重縮合物及び、Ｍｎが３００未満の低分子量ポリオールとジフェニル又はジアルキルカーボネートの重縮合（エステル交換）物等が挙げられる。 Polycarbonate polyols include ring-opening addition / polycondensation products of alkylene carbonates whose initiator is a low molecular weight polyol having an Mn of less than 300, and polycondensation (transesterification) of a low molecular weight polyol having an Mn of less than 300 and diphenyl or dialkyl carbonate. Thing etc. are mentioned.
その他のポリオール（Ｄ３）としては、ポリマーポリオール、ポリオレフィンポリオール、ポリアルカジエンポリオール及びアクリルポリオール等が挙げられる。 Examples of the other polyol (D3) include polymer polyol, polyolefin polyol, polyalkadiene polyol, and acrylic polyol.
ポリマーポリオールとしては、１種以上のポリオール中で炭素数３〜２４のビニル単量体（例えばスチレン、アクリロニトリル）をラジカル重合開始剤の存在下で重合させた重合体粒子を分散安定化させてなるポリオール（重合体含量は例えば５〜３０重量％）が挙げられる。 The polymer polyol is obtained by dispersing and stabilizing polymer particles obtained by polymerizing a vinyl monomer having 3 to 24 carbon atoms (for example, styrene or acrylonitrile) in the presence of a radical polymerization initiator in one or more kinds of polyols. Examples include polyol (polymer content is, for example, 5 to 30% by weight).
ポリオレフィンポリオールとしては、ポリイソブテンポリオール等が挙げられる。 Examples of the polyolefin polyol include polyisobutene polyol.
ポリアルカジエンポリオールとしては、ポリイソプレンポリオール、ポリブタジエンポリオール、水添化ポリイソプレンポリオール及び水添化ポリブタジエンポリオール等が挙げられる。 Examples of the polyalkadiene polyol include polyisoprene polyol, polybutadiene polyol, hydrogenated polyisoprene polyol, and hydrogenated polybutadiene polyol.
アクリルポリオールとしては、（メタ）アクリル酸アルキル（アルキルの炭素数１〜３０）エステル［ブチル（メタ）アクリレート等］と水酸基含有アクリルモノマー［ヒドロキシエチル（メタ）アクリレート等］との共重合体等が挙げられる。 Examples of the acrylic polyol include a copolymer of an alkyl (meth) acrylate (alkyl 1 to 30 carbon atoms) ester [butyl (meth) acrylate and the like] and a hydroxyl group-containing acrylic monomer [hydroxyethyl (meth) acrylate and the like]. Can be mentioned.
上記及び以下においてＭｎはゲルパーミエーションクロマトグラフィーにより測定される数平均分子量を意味する。
なお、数平均分子量は、Ｎ，Ｎ−ジメチルホルムアミドを溶剤として用い、ポリスチレンを標準物質としてゲルパーミエーションクロマトグラフィーにより測定される。サンプル濃度は０．１２５重量％、カラム固定相はＴＳＫｇｅｌ Ｇｕａｒｄｃｏｌｕｍｎ α、ＴＳＫｇｅｌ α−Ｍ（いずれも東ソー株式会社製）を各１本連結したもの、カラム温度は４０℃とすればよい。In the above and the following, Mn means the number average molecular weight measured by gel permeation chromatography.
The number average molecular weight is measured by gel permeation chromatography using N, N-dimethylformamide as a solvent and polystyrene as a standard substance. The sample concentration may be 0.125% by weight, the column stationary phase may be TSKgel Guardcolumn α, TSKgel α-M (both manufactured by Tosoh Corporation), and the column temperature may be 40 ° C.
上記高分子ポリオール（Ｄ）のうち、ポリテトラメチレンエーテルグリコールが好ましい。また、末端に位置するヒドロキシプロピル基の内の４０モル％以上、好ましくは７０モル％以上が下記化学式（３）で表される基（１級ＯＨ基）である、ポリプロピレングリコールが好ましい。
−ＣＨ（ＣＨ３）−ＣＨ２−ＯＨ （３）Of the polymer polyol (D), polytetramethylene ether glycol is preferred. Polypropylene glycol in which 40 mol% or more, preferably 70 mol% or more of the hydroxypropyl groups located at the terminals is a group (primary OH group) represented by the following chemical formula (3) is preferable.
-CH (CH 3) -CH 2 -OH (3)
熱可塑性ウレタン樹脂（Ｆ）の必須構成単量体である芳香環を有するポリオール（Ａ）、対称性を有するジイソシアネート（Ｂ）、グリコール（Ｃ）、高分子ポリオール（Ｄ）の重量割合は、（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）の合計重量に対して、（Ａ）は好ましくは５〜２０重量％、さらに好ましくは１０〜２０重量％であり、（Ｂ）は好ましくは１５〜３０重量％、さらに好ましくは２０〜３０重量％であり、（Ｃ）は好ましくは１〜１５重量％、さらに好ましくは３〜１５重量％であり、（Ｄ）は好ましくは４０〜６０重量％、さらに好ましくは４５〜６０重量％である。 The weight ratio of the polyol (A) having an aromatic ring, which is an essential constituent monomer of the thermoplastic urethane resin (F), the diisocyanate (B) having symmetry, the glycol (C), and the polymer polyol (D) is ( (A) is preferably 5 to 20% by weight, more preferably 10 to 20% by weight, and (B) is preferably based on the total weight of A), (B), (C) and (D). 15 to 30% by weight, more preferably 20 to 30% by weight, (C) is preferably 1 to 15% by weight, more preferably 3 to 15% by weight, and (D) is preferably 40 to 60% by weight. %, More preferably 45 to 60% by weight.
熱可塑性ウレタン樹脂（Ｆ）のウレア基含有量としては、シャープメルト性の観点から好ましくは０．０６ｍｍｏｌ／ｇ以下、より好ましくは０．０３ｍｍｏｌ／ｇ以下、さらに好ましくは０．０２ｍｍｏｌ／ｇ以下である。 The urea group content of the thermoplastic urethane resin (F) is preferably 0.06 mmol / g or less, more preferably 0.03 mmol / g or less, still more preferably 0.02 mmol / g or less from the viewpoint of sharp melt properties. is there.
熱可塑性ウレタン樹脂（Ｆ）の製造方法
熱可塑性ウレタン樹脂（Ｆ）の製造方法としては、例えば、芳香環を有するポリオール（Ａ）、グリコール（Ｃ）、高分子ポリオール（Ｄ）とを均一に混合した後、対称性を有するジイソシアネート（Ｂ）を反応させる方法などが挙げられる。
熱可塑性ウレタン樹脂（Ｆ）の必須構成単量体である芳香環を有するポリオール（Ａ）、グリコール（Ｃ）、高分子ポリオール（Ｄ）の混合物中に含まれる水分割合は、（Ａ）、（Ｃ）、（Ｄ）の合計重量に対して、好ましくは０．００〜０．１０重量％、さらに好ましくは０．００〜０．０３重量％である。Production method of thermoplastic urethane resin (F) As a production method of thermoplastic urethane resin (F), for example, polyol (A) having an aromatic ring, glycol (C), and polymer polyol (D) are uniformly mixed. Then, a method of reacting diisocyanate (B) having symmetry is exemplified.
The water content contained in the mixture of polyol (A), glycol (C) and polymer polyol (D) having an aromatic ring which is an essential constituent monomer of the thermoplastic urethane resin (F) is (A), ( Preferably it is 0.00-0.10 weight% with respect to the total weight of C) and (D), More preferably, it is 0.00-0.03% weight.
ウレタン化反応に際しては、ウレタン化触媒を使用してもよい。ウレタン化触媒としては種々のものが使用でき、例えば金属触媒〔錫触媒［トリメチルチンラウレート、トリメチルチンヒドロキサイド、ジメチルチンジラウレート、ジブチルチンジアセテート、ジブチルチンジラウレート、スタナスオクトエート、ジブチルチンマレエート等］、鉛触媒［オレイン酸鉛、２−エチルヘキサン酸鉛、ナフテン酸鉛、オクテン酸鉛等］、その他の金属触媒［ナフテン酸金属塩（ナフテン酸コバルト等）、フェニル水銀プロピオン酸塩等］等〕；アミン触媒｛トリエチレンジアミン、テトラメチルエチレンジアミン、ジアザビシクロアルケン〔１，８−ジアザビシクロ［５，４，０］ウンデセン−７［ＤＢＵ（サンアプロ(株)製、登録商標）］等〕、ジアルキル（炭素数１〜３）アミノアルキル（炭素数２〜４）アミン［ジメチルアミノエチルアミン、ジメチルアミノプロピルアミン、ジエチルアミノプロピルアミン、ジプロピルアミノプロピルアミン等］、複素環式アミノアルキル（炭素数２〜６）アミン［２−（１−アジリジニル）エチルアミン、４−（１−ピペリジニル）−２−ヘキシルアミン等］、およびこれらの炭酸塩および有機酸（炭素数１〜３、例えばギ酸）塩等；Ｎ−メチルおよび−エチルモルホリン、トリエチルアミン、ジメチル−およびジエチルエタノールアミン等｝；およびこれらの２種以上の併用系が挙げられる。 In the urethanization reaction, a urethanization catalyst may be used. Various catalysts can be used as urethanization catalysts such as metal catalysts [tin catalysts [trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, dibutyltin maleate]. Etc.], lead catalysts [lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.], other metal catalysts [metal salts of naphthenate (cobalt naphthenate, etc.), phenylmercuric propionate, etc.] Etc.]; amine catalyst {triethylenediamine, tetramethylethylenediamine, diazabicycloalkene [1,8-diazabicyclo [5,4,0] undecene-7 [DBU (manufactured by San Apro Co., Ltd., registered trademark)]], dialkyl (C1-C3) aminoalkyl (C2-C4) Min [dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, etc.], heterocyclic aminoalkyl (2 to 6 carbon atoms) amine [2- (1-aziridinyl) ethylamine, 4- (1 -Piperidinyl) -2-hexylamine and the like], and carbonates and organic acids thereof (C1-C3, for example formate) and the like; N-methyl and -ethylmorpholine, triethylamine, dimethyl- and diethylethanolamine, etc.} And combinations of two or more of these.
本発明のホットメルト接着剤は、熱可塑性ウレタン樹脂（Ｆ）を含有するが、種々の目的および用途に応じ、本発明の効果を阻害しない範囲で他の樹脂用添加剤（Ｅ）を任意に含有させることができる。 The hot melt adhesive of the present invention contains a thermoplastic urethane resin (F), but according to various purposes and applications, other resin additives (E) can be arbitrarily added within a range not inhibiting the effects of the present invention. It can be included.
樹脂用添加剤（Ｅ）としては、粘着性付与剤、酸化防止剤、紫外線吸収剤、光安定剤、可塑剤、吸着剤、着色剤、充填剤、核剤、滑剤、離型剤、水、難燃剤および香料からなる群から選ばれる少なくとも１種の添加剤が挙げられる。 Additives for resins (E) include tackifiers, antioxidants, UV absorbers, light stabilizers, plasticizers, adsorbents, colorants, fillers, nucleating agents, lubricants, mold release agents, water, Examples include at least one additive selected from the group consisting of a flame retardant and a fragrance.
粘着性付与剤としては、例えばテルペン樹脂、テルペンフェノール樹脂、フェノール樹脂、芳香族炭化水素変性テルペン樹脂、ロジン樹脂、変性ロジン樹脂、合成石油樹脂（脂肪族、芳香族又は脂環式合成石油樹脂等）、クマロン−インデン樹脂、キシレン樹脂、スチレン系樹脂、ジシクロペンタジエン樹脂、及びこれらの内の水素添加可能な不飽和二重結合を有するものの水素添加物等が挙げられる。 Examples of the tackifier include terpene resin, terpene phenol resin, phenol resin, aromatic hydrocarbon modified terpene resin, rosin resin, modified rosin resin, synthetic petroleum resin (aliphatic, aromatic or alicyclic synthetic petroleum resin, etc. ), Coumarone-indene resin, xylene resin, styrene resin, dicyclopentadiene resin, and hydrogenated products of these having hydrogenated unsaturated double bonds.
酸化防止剤としては、ヒンダードフェノール化合物〔ペンタエリスチル−テトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート等〕、リン化合物［トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト等］、イオウ化合物［ペンタエリスチル−テトラキス（３−ラウリルチオプロピオネート）、ジラウリル−３，３’−チオジプロピオネート等］等が挙げられる。 Antioxidants include hindered phenol compounds [pentaerystyl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t. -Butyl-4-hydroxyphenyl) propionate, etc.], phosphorus compound [tris (2,4-di-t-butylphenyl) phosphite, etc.], sulfur compound [pentaerystyl-tetrakis (3-laurylthiopropionate) , Dilauryl-3,3′-thiodipropionate, etc.].
紫外線吸収剤としては、ベンゾトリアゾール化合物［２−（３，５−ジ−ｔ−アミル−２−ヒドロキシフェニル）ベンゾトリアゾール、２−（５−メチル−２−ヒドロキシフェニル）ベンゾトリアゾール等］等が挙げられる。 Examples of the ultraviolet absorber include benzotriazole compounds [2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, etc.]. It is done.
光安定剤としては、ヒンダードアミン化合物［（ビス−２，２，６，６−テトラメチル−４−ピペリジル）セバケート等］等が挙げられる。 Examples of the light stabilizer include hindered amine compounds [(bis-2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like] and the like.
可塑剤としては、種々の可塑剤［例えば接着の技術Ｖｏｌ．２０，（２），２１（２０００）等に記載のもの］が使用でき、プロセスオイル（パラフィン、ナフテンもしくは芳香族化合物型）；液状樹脂（Ｍｎ３００〜６，０００、例えば液状ポリブテン、液状ポリブタジエン、液状ポリイソプレン）；該液状樹脂の水素化体；低分子量（Ｍｎ３００〜１０，０００）ポリイソブチレン；およびこれらの２種以上の混合物等が挙げられる。 As the plasticizer, various plasticizers [for example, adhesive technology Vol. 20, (2), 21 (2000), etc.], process oil (paraffin, naphthene or aromatic compound type); liquid resin (Mn 300 to 6,000, for example, liquid polybutene, liquid polybutadiene, liquid Polyisoprene); hydrogenated product of the liquid resin; low molecular weight (Mn 300 to 10,000) polyisobutylene; and mixtures of two or more thereof.
吸着剤としては、アルミナ、シリカゲル、モレキュラーシーブ等が挙げられる。 Examples of the adsorbent include alumina, silica gel, molecular sieve and the like.
着色剤としては、顔料（酸化チタン、カーボンブラック等）、染料（アゾ、アンスラキノン、インジゴイド、アリザリン、アクリジン、ニトロソおよびアニリン染料等）等が挙げられる。 Examples of the colorant include pigments (titanium oxide, carbon black, etc.), dyes (azo, anthraquinone, indigoid, alizarin, acridine, nitroso, aniline dyes, etc.) and the like.
充填剤としては、タルク、マイカ、炭酸カルシウム等が挙げられる。 Examples of the filler include talc, mica, calcium carbonate and the like.
核剤としては、ソルビトール、ホスフェート金属塩、安息香酸金属塩、リン酸金属塩等が挙げられる。 Examples of the nucleating agent include sorbitol, phosphate metal salt, benzoic acid metal salt, and phosphate metal salt.
滑剤としては、ステアリン酸カルシウム、ステアリン酸ブチル、オレイン酸アミド等が挙げられる。 Examples of the lubricant include calcium stearate, butyl stearate, oleic amide and the like.
離型剤としては、カルボキシル変性シリコーンオイル、ヒドロキシル変性シリコーンオイル等が挙げられる。 Examples of the release agent include carboxyl-modified silicone oil and hydroxyl-modified silicone oil.
難燃剤としては、ハロゲン含有難燃剤、リン含有難燃剤、アンチモン含有難燃剤、金属水酸化物含有難燃剤等が挙げられる。 Examples of the flame retardant include a halogen-containing flame retardant, a phosphorus-containing flame retardant, an antimony-containing flame retardant, and a metal hydroxide-containing flame retardant.
香料としては、ジテルペン、リモネン等が挙げられる。 Examples of the fragrances include diterpenes and limonene.
樹脂用添加剤（Ｅ）の合計含有量は熱可塑性ウレタン樹脂（Ｆ）の全重量に基づいて、４０重量％以下であることが好ましく、添加効果および接着性の観点からより好ましくは０．００２〜３０重量％、さらに好ましくは０．１〜１０重量％である。 The total content of the resin additive (E) is preferably 40% by weight or less based on the total weight of the thermoplastic urethane resin (F), and more preferably 0.002 from the viewpoint of the addition effect and adhesiveness. -30% by weight, more preferably 0.1-10% by weight.
本発明のホットメルト接着剤は、温度依存性の観点と塗工性の観点から、融点は８０℃〜１５０℃が好ましく、９０℃〜１２０℃がさらに好ましい。 The hot melt adhesive of the present invention has a melting point of preferably 80 ° C. to 150 ° C., more preferably 90 ° C. to 120 ° C., from the viewpoints of temperature dependency and coatability.
また、本発明のホットメルト接着剤は、接着力等の品質安定性の観点から、貯蔵弾性率（以下、Ｇ’と略記）の温度依存性が低いことが好ましい。
本発明のホットメルト接着剤は、接着力の安定性に優れている。これは貯蔵弾性率（Ｇ’）の温度依存性で評価することが出来る。
具体的には、下記式（３）で示されるＧ’の温度変化率が１００以下であれば温度依存性が低いため好ましく、下記式（４）で示されるＧ’の温度変化率が１０以下であればさらに好ましい。
Ｇ’の温度変化率（−２０／７０）＝Ｇ’（−２０℃）／Ｇ’（７０℃） （３）
Ｇ’の温度変化率（０／７０）＝Ｇ’（０℃）／Ｇ’（７０℃） （４）
［式（３）、式（４）中のＧ’（Ｔ℃）は、Ｔ℃におけるＧ’の数値を表す。］In addition, the hot melt adhesive of the present invention preferably has a low temperature dependency of storage elastic modulus (hereinafter abbreviated as G ′) from the viewpoint of quality stability such as adhesive strength.
The hot melt adhesive of the present invention is excellent in adhesive strength stability. This can be evaluated by the temperature dependence of the storage elastic modulus (G ′).
Specifically, it is preferable that the temperature change rate of G ′ represented by the following formula (3) is 100 or less because the temperature dependency is low, and the temperature change rate of G ′ represented by the following formula (4) is 10 or less. More preferably.
Temperature change rate of G ′ (−20/70) = G ′ (−20 ° C.) / G ′ (70 ° C.) (3)
Temperature change rate of G ′ (0/70) = G ′ (0 ° C.) / G ′ (70 ° C.) (4)
[G ′ (T ° C.) in Formulas (3) and (4) represents a numerical value of G ′ at T ° C. ]
本発明のホットメルト接着剤の製造方法については特に限定されないが、本発明のホットメルト接着剤の各成分を加熱溶融して混合する方法；及び本発明のホットメルト接着剤の各成分を有機溶剤（トルエン又はキシレン等）と共に加熱溶融して均一混合した後に溶剤を留去する方法等が適用できる。これらのうち、工業的に好ましいのは前者の方法である。 The method for producing the hot melt adhesive of the present invention is not particularly limited, but the components of the hot melt adhesive of the present invention are heated and melted and mixed; and the components of the hot melt adhesive of the present invention are mixed with an organic solvent. A method of distilling off the solvent after heating and melting together with (toluene, xylene, etc.) and uniformly mixing can be applied. Of these, the former method is industrially preferred.
以下、実施例により本発明を更に説明するが、本発明はこれに限定されるものではない。実施例中、部及び％は特に断りのない限り、それぞれ重量部及び重量％を示す。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In the examples, “parts” and “%” represent “parts by weight” and “% by weight” unless otherwise specified.
製造例１
〔ビスフェノールＡのＥＯ付加物（Ａ−１）の合成〕
ガラス製オートクレーブに、トルエン１３７．０ｇ（ビスフェノール類に対して４０％）、ビスフェノールＡ（三菱化学株式会社製「ビスフェノールＡ」）３４２．４ｇ（１．５０ｍｏｌ）を仕込み、窒素置換を行った後、７５℃まで昇温し、ビスフェノールＡをトルエンに分散させた。ここにテトラメチルアンモニウムヒドロキシド２５％水溶液を２．７３ｇ添加した。
再度窒素置換を行い、ＥＯを７５〜９５℃、反応圧０．２ＭＰａ以下の範囲で滴下反応させた。反応中、適宜サンプリングし、ＧＣで反応物のビスフェノールへの付加モル分布を追跡し、１モル付加物が０．１％以下になった時点で反応を終了した。要したＥＯは１３９．９ｇ（３．１８ｍｏｌ）であり、反応時間は７時間であった。
反応後、１３０〜１６０℃、減圧下で未反応ＥＯ、触媒、溶剤等を留去し、ビスフェノールＡのＥＯ付加物（Ａ−１）を得た。
この（Ａ−１）をＧＣにて分析したところ、得られた（Ａ−１）の水酸基あたりのＥＯ平均付加モル数は１．０２であり、単分散度は９７．４％であった。Production Example 1
[Synthesis of bisphenol A EO adduct (A-1)]
A glass autoclave was charged with 137.0 g of toluene (40% based on bisphenols) and 342.4 g (1.50 mol) of bisphenol A (Mitsubishi Chemical Corporation “bisphenol A”), and after nitrogen substitution, The temperature was raised to 75 ° C., and bisphenol A was dispersed in toluene. To this, 2.73 g of a 25% aqueous solution of tetramethylammonium hydroxide was added.
Nitrogen substitution was performed again, and EO was dropped and reacted in a range of 75 to 95 ° C. and a reaction pressure of 0.2 MPa or less. During the reaction, sampling was performed as appropriate, and the addition mole distribution of the reaction product to bisphenol was traced by GC, and the reaction was terminated when the 1 mol addition product was 0.1% or less. The required EO was 139.9 g (3.18 mol), and the reaction time was 7 hours.
After the reaction, unreacted EO, catalyst, solvent and the like were distilled off at 130 to 160 ° C. under reduced pressure to obtain an EO product of bisphenol A (A-1).
When this (A-1) was analyzed by GC, the EO average added mole number per hydroxyl group of the obtained (A-1) was 1.02, and the monodispersity was 97.4%.
製造例２
〔ビスフェノールＡのＥＯ付加物（Ａ−２）の合成〕
ガラス製オートクレーブに、実施例１で得られた（Ａ−１）８５．６ｇ（後に加えるビスフェノールＡに対して２５重量％）を溶融させて反応系の溶媒として入れた。１１０℃まで加熱してこれを溶融した後、ビスフェノールＡ３４２．４ｇ（１．５０ｍｏｌ）を仕込み、窒素置換を行った後、９５℃まで冷却し、ビスフェノールＡを分散させた。ここに水酸化ナトリウム０．３０ｇを添加した。
再度窒素置換を行い、ＥＯを７５〜９５℃、反応圧０．２ＭＰａ以下の範囲で滴下反応させた。反応中、適宜サンプリングし、ＧＣで反応物のビスフェノールへの付加モル分布を追跡した。１モル付加物が０．１％以下になった時点で反応を終了した。要したＥＯは１５０．５ｇ（３．４２ｍｏｌ）であり、反応時間は７時間であった。
反応後、燐酸で触媒を中和し、１３０〜１６０℃、減圧下で未反応ＥＯを留去し、ビスフェノールＡのＥＯ付加物（Ａ−２）を得た。
この（Ａ−２）をＧＣにて分析したところ、得られた（Ａ−２）の水酸基あたりのＥＯ平均付加モル数は１．０９であり、単分散度は８２．５％であった。Production Example 2
[Synthesis of bisphenol A EO adduct (A-2)]
In a glass autoclave, 85.6 g of (A-1) obtained in Example 1 (25% by weight based on bisphenol A added later) was melted and added as a solvent for the reaction system. After heating up to 110 ° C. and melting it, 342.4 g (1.50 mol) of bisphenol A was charged and purged with nitrogen, and then cooled to 95 ° C. to disperse bisphenol A. To this was added 0.30 g of sodium hydroxide.
Nitrogen substitution was performed again, and EO was dropped and reacted in a range of 75 to 95 ° C. and a reaction pressure of 0.2 MPa or less. During the reaction, sampling was performed as appropriate, and the distribution of addition moles of the reaction product to bisphenol was monitored by GC. The reaction was terminated when the 1 mol adduct was 0.1% or less. The required EO was 150.5 g (3.42 mol), and the reaction time was 7 hours.
After the reaction, the catalyst was neutralized with phosphoric acid, and unreacted EO was distilled off under reduced pressure at 130 to 160 ° C. to obtain an EO adduct (A-2) of bisphenol A.
When this (A-2) was analyzed by GC, the EO average added mole number per hydroxyl group of the obtained (A-2) was 1.09, and the monodispersity was 82.5%.
製造例３
〔ビスフェノールＡのＥＯ付加物（Ａ−３）の合成〕
製造例２で滴下反応させたＥＯの量を１５４．０ｇ（３．５０ｍｏｌ）として、１モル付加物が０．１％以下になった時点で反応を終了した以外は製造例２と同様にして反応させた。
反応後、燐酸で触媒を中和し、１３０〜１６０℃、減圧下で未反応ＥＯを留去し、ビスフェノールＡのＥＯ付加物（Ａ−３）を得た。
この（Ａ−３）をＧＣにて分析したところ、得られた（Ａ−３）の水酸基あたりのＥＯ平均付加モル数は１．１０であり、単分散度は８１．３％であった。Production Example 3
[Synthesis of bisphenol A EO adduct (A-3)]
The amount of EO dropped in Production Example 2 was set to 154.0 g (3.50 mol), and the reaction was terminated when 1 mol of adduct became 0.1% or less. Reacted.
After the reaction, the catalyst was neutralized with phosphoric acid, and unreacted EO was distilled off under reduced pressure at 130 to 160 ° C. to obtain an EO adduct (A-3) of bisphenol A.
When this (A-3) was analyzed by GC, the EO average added mole number per hydroxyl group of the obtained (A-3) was 1.10, and the monodispersity was 81.3%.
製造例４
〔ビスフェノールＡのＥＯ付加物（Ａ−４）の合成〕
製造例１で滴下反応させたＥＯの量を１２４．８ｇ（２．８４ｍｏｌ）として、１モル付加物が０．１％以下になった時点で反応を終了した以外は製造例１と同様にして反応させた。
反応後、燐酸で触媒を中和し、１３０〜１６０℃、減圧下で未反応ＥＯを留去し、ビスフェノールＡのＥＯ付加物（Ａ−４）を得た。
この（Ａ−４）をＧＣにて分析したところ、得られた（Ａ−４）の水酸基あたりのＥＯ平均付加モル数は０．９１であり、単分散度は８８．３％であった。Production Example 4
[Synthesis of bisphenol A EO adduct (A-4)]
In the same manner as in Production Example 1, except that the amount of EO reacted dropwise in Production Example 1 was 124.8 g (2.84 mol) and the reaction was terminated when 1 mol adduct was 0.1% or less. Reacted.
After the reaction, the catalyst was neutralized with phosphoric acid, and unreacted EO was distilled off at 130 to 160 ° C. under reduced pressure to obtain an EO adduct (A-4) of bisphenol A.
When this (A-4) was analyzed by GC, the EO average added mole number per hydroxyl group of the obtained (A-4) was 0.91, and the monodispersity was 88.3%.
製造例５
〔ビスフェノールＡのＥＯ付加物（Ａ−５）の合成〕
製造例２で用いた水酸化ナトリウムの量を０．２７ｇに代えた以外は製造例２と同様にして反応させた。
１モル付加物が０．１％以下になった時点で反応を終了し、要したＥＯは、１２１．８ｇ（２．７７ｍｏｌ）であり、反応時間は７時間であった。
反応後、燐酸で触媒を中和し、１３０〜１６０℃、減圧下で未反応ＥＯを留去し、ビスフェノールＡのＥＯ付加物（Ａ−５）を得た。
この（Ａ−５）をＧＣにて分析したところ、得られた（Ａ−５）の水酸基あたりのＥＯ平均付加モル数は１．０３であり、単分散度は８０．５％であった。Production Example 5
[Synthesis of bisphenol A EO adduct (A-5)]
The reaction was conducted in the same manner as in Production Example 2 except that the amount of sodium hydroxide used in Production Example 2 was changed to 0.27 g.
The reaction was terminated when 1 mol adduct was 0.1% or less, and EO required was 121.8 g (2.77 mol), and the reaction time was 7 hours.
After the reaction, the catalyst was neutralized with phosphoric acid, and unreacted EO was distilled off at 130 to 160 ° C. under reduced pressure to obtain an EO adduct (A-5) of bisphenol A.
When this (A-5) was analyzed by GC, the EO average added mole number per hydroxyl group of the obtained (A-5) was 1.03, and the monodispersity was 80.5%.
製造例６
〔ビスフェノールＢのＥＯ付加物（Ａ−６）の合成〕
製造例１で用いたビスフェノールＡをビスフェノールＢ（東京化成工業株式会社製）３６３．４ｇ（１．５０ｍｏｌ）に代えた以外は製造例１と同様にして反応させた。
１モル付加物が０．１％以下になった時点で反応を終了した。要したＥＯは１５０．８ｇ（３．４３ｍｏｌ）であり、反応時間は７時間であった。
反応後、１３０〜１６０℃、減圧下で未反応ＥＯ、触媒、溶剤等を留去し、ビスフェノールＢのＥＯ付加物（Ａ−６）を得た。
この（Ａ−６）をＧＣにて分析したところ、得られた（Ａ−６）の水酸基あたりのＥＯ平均付加モル数は１．０３であり、単分散度は９６．７％であった。Production Example 6
[Synthesis of bisphenol B EO adduct (A-6)]
The reaction was conducted in the same manner as in Production Example 1 except that bisphenol A used in Production Example 1 was replaced with 363.4 g (1.50 mol) of bisphenol B (manufactured by Tokyo Chemical Industry Co., Ltd.).
The reaction was terminated when the 1 mol adduct was 0.1% or less. The required EO was 150.8 g (3.43 mol), and the reaction time was 7 hours.
After the reaction, unreacted EO, catalyst, solvent and the like were distilled off under reduced pressure at 130 to 160 ° C. to obtain an EO product of bisphenol B (A-6).
When this (A-6) was analyzed by GC, the EO average addition mole number per hydroxyl group of the obtained (A-6) was 1.03, and the monodispersity was 96.7%.
製造例７
〔ビスフェノールＥのＥＯ付加物（Ａ−７）の合成〕
製造例１で用いたビスフェノールＡをビスフェノールＥ（本州化学工業株式会社製「ビスフェノールＥ」）３２１．４ｇ（１．５０ｍｏｌ）に代えた以外は製造例１と同様にして反応させた。
１モル付加物が０．１％以下になった時点で反応を終了した。要したＥＯは１５０．６ｇ（３．４２ｍｏｌ）であり、反応時間は７時間であった。
反応後、１３０〜１６０℃、減圧下で未反応ＥＯ、触媒、溶剤等を留去し、ビスフェノールＥのＥＯ付加物（Ａ−７）を得た。
この（Ａ−７）をＧＣにて分析したところ、得られた（Ａ−７）の水酸基あたりのＥＯ平均付加モル数は１．０３であり、単分散度は９６．４％であった。Production Example 7
[Synthesis of bisphenol E EO adduct (A-7)]
The reaction was conducted in the same manner as in Production Example 1 except that bisphenol A used in Production Example 1 was replaced with 321.4 g (1.50 mol) of bisphenol E (“Bisphenol E” manufactured by Honshu Chemical Industry Co., Ltd.).
The reaction was terminated when the 1 mol adduct was 0.1% or less. The required EO was 150.6 g (3.42 mol), and the reaction time was 7 hours.
After the reaction, unreacted EO, catalyst, solvent and the like were distilled off under reduced pressure at 130 to 160 ° C. to obtain an EO product of bisphenol E (A-7).
When this (A-7) was analyzed by GC, the average added mole number of EO per hydroxyl group of the obtained (A-7) was 1.03, and the monodispersity was 96.4%.
製造例８
〔ビスフェノールＦのＥＯ付加物（Ａ−８）の合成〕
製造例１で用いたビスフェノールＡをビスフェノールＦ（本州化学工業株式会社製「ビスフェノールＦ」）３００．４ｇ（１．５０ｍｏｌ）に代えた以外は製造例１と同様にして反応させた。
１モル付加物が０．１％以下になった時点で反応を終了した。要したＥＯは１５０．３ｇ（３．４２ｍｏｌ）であり、反応時間は７時間であった。
反応後、１３０〜１６０℃、減圧下で未反応ＥＯ、触媒、溶剤等を留去し、ビスフェノールＦのＥＯ付加物（Ａ−８）を得た。
この（Ａ−８）をＧＣにて分析したところ、得られた（Ａ−８）の水酸基あたりのＥＯ平均付加モル数は１．０２であり、単分散度は９７．５％であった。Production Example 8
[Synthesis of bisphenol F EO adduct (A-8)]
The reaction was conducted in the same manner as in Production Example 1 except that bisphenol A used in Production Example 1 was replaced with 300.4 g (1.50 mol) of bisphenol F (“Bisphenol F” manufactured by Honshu Chemical Industry Co., Ltd.).
The reaction was terminated when the 1 mol adduct was 0.1% or less. The required EO was 150.3 g (3.42 mol), and the reaction time was 7 hours.
After the reaction, unreacted EO, catalyst, solvent and the like were distilled off at 130 to 160 ° C. under reduced pressure to obtain an EO product of bisphenol F (A-8).
When this (A-8) was analyzed by GC, the EO average addition mole number per hydroxyl group of the obtained (A-8) was 1.02, and the monodispersity was 97.5%.
製造例９
〔ビスフェノールＡのＥＯ付加物（Ａ−９）の合成〕
製造例２で用いた水酸化ナトリウムをトリメチルアミン４０％水溶液０．２２ｇに代えた以外は製造例２と同様にして反応させた。
反応後、１５時間後でも１モル付加物が１３％であり、０．１％以下になるまでは相当の時間を要することが予想され、実用的ではないと判断し、反応を打ち切った。この段階までに滴下したＥＯは、１３２ｇ（３．００ｍｏｌ）であった。
反応後、燐酸で触媒を中和し、１３０〜１６０℃、減圧下で未反応ＥＯを留去し、ビスフェノールＡのＥＯ付加物（Ａ−９）を得た。
この（Ａ−９）をＧＣにて分析したところ、得られた（Ａ−９）の水酸基あたりのＥＯ平均付加モル数は０．９８であり、単分散度は７８．９％であった。Production Example 9
[Synthesis of bisphenol A EO adduct (A-9)]
The reaction was conducted in the same manner as in Production Example 2 except that sodium hydroxide used in Production Example 2 was replaced with 0.22 g of a 40% aqueous solution of trimethylamine.
Even after 15 hours from the reaction, the 1 mol adduct was 13%, and it was expected that a considerable amount of time was required until it was 0.1% or less. EO dripped by this stage was 132 g (3.00 mol).
After the reaction, the catalyst was neutralized with phosphoric acid, and unreacted EO was distilled off at 130 to 160 ° C. under reduced pressure to obtain an EO adduct (A-9) of bisphenol A.
When this (A-9) was analyzed by GC, the average added mole number of EO per hydroxyl group of the obtained (A-9) was 0.98, and the monodispersity was 78.9%.
製造例１０
〔ビスフェノールＡのＥＯ付加物（Ａ−１０）の合成〕
製造例２で用いた水酸化ナトリウムの量を０．２４ｇに代えた以外は製造例２と同様にして反応させた。
１モル付加物が０．１％以下になった時点で反応を終了し、要したＥＯは、１２１．８ｇ（２．７７ｍｏｌ）であり、反応時間は７時間であった。
反応後、燐酸で触媒を中和し、１３０〜１６０℃、減圧下で未反応ＥＯを留去し、ビスフェノールＡのＥＯ付加物（Ａ−１０）を得た。
この（Ａ−１０）をＧＣにて分析したところ、得られた（Ａ−１０）の水酸基あたりのＥＯ平均付加モル数は０．８９であり、単分散度は８０．３％であった。Production Example 10
[Synthesis of bisphenol A EO adduct (A-10)]
The reaction was conducted in the same manner as in Production Example 2 except that the amount of sodium hydroxide used in Production Example 2 was changed to 0.24 g.
The reaction was terminated when 1 mol adduct was 0.1% or less, and EO required was 121.8 g (2.77 mol), and the reaction time was 7 hours.
After the reaction, the catalyst was neutralized with phosphoric acid, and unreacted EO was distilled off at 130 to 160 ° C. under reduced pressure to obtain an EO adduct (A-10) of bisphenol A.
When this (A-10) was analyzed by GC, the average added mole number of EO per hydroxyl group of the obtained (A-10) was 0.89, and the monodispersity was 80.3%.
製造例１１
〔ビスフェノールＡのＥＯ付加物（Ａ−１１）の合成〕
製造例２で滴下反応させたＥＯの量を１５７．５ｇ（３．５８ｍｏｌ）として、１モル付加物が０．１％以下になった時点で反応を終了した以外は製造例２と同様にして反応させた。
反応後、燐酸で触媒を中和し、１３０〜１６０℃、減圧下で未反応ＥＯを留去し、ビスフェノールＡのＥＯ付加物（Ａ−１１）を得た。
この（Ａ−１１）をＧＣにて分析したところ、得られた（Ａ−１１）の水酸基あたりのＥＯ平均付加モル数は１．１２であり、単分散度は８０．１％であった。Production Example 11
[Synthesis of bisphenol A EO adduct (A-11)]
The amount of EO dropped in Production Example 2 was 157.5 g (3.58 mol), and the reaction was terminated when 1 mol adduct became 0.1% or less. Reacted.
After the reaction, the catalyst was neutralized with phosphoric acid, and unreacted EO was distilled off under reduced pressure at 130 to 160 ° C. to obtain an EO adduct (A-11) of bisphenol A.
When this (A-11) was analyzed by GC, the EO average addition mole number per hydroxyl group of the obtained (A-11) was 1.12, and the monodispersity was 80.1%.
製造例１２
〔ｐ−フタル酸のＥＯ付加物（Ａ−１２）の合成〕
製造例１で用いたビスフェノールＡをｐ−フタル酸（東京化成工業株式会社製）２４９．２ｇ（１．５０ｍｏｌ）に代えた以外は製造例１と同様にして反応させた。
１モル付加物が０．１％以下になった時点で反応を終了した。要したＥＯは１４９．２ｇ（３．３９ｍｏｌ）であり、反応時間は６時間であった。
反応後、１３０〜１６０℃、減圧下で未反応ＥＯ、触媒、溶剤等を留去し、ｐ−フタル酸のＥＯ付加物（Ａ−１２）を得た。Production Example 12
[Synthesis of p-phthalic acid EO adduct (A-12)]
The reaction was carried out in the same manner as in Production Example 1 except that bisphenol A used in Production Example 1 was replaced with 249.2 g (1.50 mol) of p-phthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.).
The reaction was terminated when the 1 mol adduct was 0.1% or less. The required EO was 149.2 g (3.39 mol), and the reaction time was 6 hours.
After the reaction, unreacted EO, catalyst, solvent and the like were distilled off under reduced pressure at 130 to 160 ° C. to obtain an EO adduct (A-12) of p-phthalic acid.
製造例１３
〔１，４−ジヒドロキシベンゼンのＥＯ付加物（Ａ−１３）の合成〕
製造例１で用いたビスフェノールＡを１，４−ジヒドロキシベンゼン（東京化成工業株式会社製）１６５．２ｇ（１．５０ｍｏｌ）に代えた以外は製造例１と同様にして反応させた。
１モル付加物が０．１％以下になった時点で反応を終了した。要したＥＯは１５１．２ｇ（３．４４ｍｏｌ）であり、反応時間は７時間であった。
反応後、１３０〜１６０℃、減圧下で未反応ＥＯ、触媒、溶剤等を留去し、１，４−ジヒドロキシベンゼンのＥＯ付加物（Ａ−１３）を得た。Production Example 13
[Synthesis of EO adduct of 1,4-dihydroxybenzene (A-13)]
The reaction was conducted in the same manner as in Production Example 1 except that bisphenol A used in Production Example 1 was replaced with 165.2 g (1.50 mol) of 1,4-dihydroxybenzene (Tokyo Chemical Industry Co., Ltd.).
The reaction was terminated when the 1 mol adduct was 0.1% or less. The required EO was 151.2 g (3.44 mol), and the reaction time was 7 hours.
After the reaction, unreacted EO, catalyst, solvent and the like were distilled off at 130 to 160 ° C. under reduced pressure to obtain 1,4-dihydroxybenzene EO adduct (A-13).
実施例１〜２６、比較例１〜３
［ホットメルト接着剤（Ｈ）の調製］
攪拌機、コンデンサー、温度計を備えたフラスコに、表１に記載の配合部数の芳香環を有するポリオール（Ａ）、グリコール（Ｃ）及び高分子ポリオール（Ｄ）を一括で投入し、１０５℃で均一攪拌後、８０℃まで冷却して、水分を測定した。表１に記載の配合部数のジイソシアネート（Ｂ）とウレタン化触媒（日東化成株式会社製「ネオスタンＵ−６００」）０．０１部を仕込み、窒素気流下、攪拌、混合して温度を１００〜１６０℃に保ちながら、８時間反応させることで目的とする熱可塑性ウレタン樹脂（Ｆ−１）〜（Ｆ−２６）及び比較用の熱可塑性樹脂（Ｆ'−１）〜（Ｆ'−３）を得た。これらを本発明のホットメルト接着剤（Ｈ−１）〜（Ｈ−２６）及び比較用のメルト接着剤（Ｈ'−１）〜（Ｈ'−３）とした。Examples 1-26, Comparative Examples 1-3
[Preparation of hot melt adhesive (H)]
Into a flask equipped with a stirrer, a condenser, and a thermometer, the polyol (A), glycol (C) and polymer polyol (D) having an aromatic ring having the number of blending parts shown in Table 1 are charged all at once, and uniform at 105 ° C. After stirring, the mixture was cooled to 80 ° C., and moisture was measured. The amount of the diisocyanate (B) and the urethanization catalyst (“Neostan U-600” manufactured by Nitto Kasei Co., Ltd.) 0.01 parts shown in Table 1 are charged, and the mixture is stirred and mixed in a nitrogen stream to adjust the temperature to 100 to 160. The target thermoplastic urethane resins (F-1) to (F-26) and comparative thermoplastic resins (F′-1) to (F′-3) are allowed to react for 8 hours while being kept at ° C. Obtained. These were designated as hot melt adhesives (H-1) to (H-26) of the present invention and comparative melt adhesives (H′-1) to (H′-3).
表１〜３に記載の（Ｂ）、（Ｃ）、（Ｄ）、（Ｅ）、（Ｂ’）及び（Ｃ’）は以下を使用した。
１，６−ヘキサメチレンジイソシアネート（Ｂ−１）：住化コベストロウレタン株式会社製「デスモジュールＨ」
４，４’−ジフェニルメタンジイソシアネート（Ｂ−２）：東ソー株式会社製「ミリオネートＭＴ」
ジシクロヘキシルメタン−４，４’−ジイソシアネート（Ｂ−３）：住化コベストロウレタン株式会社製「デスモジュールＷ」
イソホロンジイソシアネート（Ｂ’−１）：住化コベストロウレタン株式会社製「デスモジュールＩ」
１，４−ブタンジオール（Ｃ−１）：：三菱化学株式会社製「１４ＢＧ」
１，６−ヘキサンジオール（Ｃ−２）：宇部興産株式会社製「１，６−ヘキサンジオール」
１，８−オクタンジオール（Ｃ−３）：東京化成工業株式会社製
ヘキサエチレングリコール（Ｃ−４）：東京化成工業株式会社製
１，５−ネオペンチルグリコール（Ｃ’−１）：東京化成工業株式会社製
ポリテトラメチレンエーテルグリコール（Ｄ−１）：三菱化学株式会社製「ＰＴＭＧ １０００」
ポリプロピレングリコール（Ｄ−２）：三洋化成工業株式会社製「プライムポールＰＸ−１０００」（１級ＯＨ基率：７０モル％）
ポリエステルポリオール（Ｄ−３）：東ソー株式会社製「ニッポラン １６４」
ポリプロピレングリコール（Ｄ−４）：三洋化成工業株式会社製「サンニックスＰＰ−１０００」（１級ＯＨ基率：２モル％）
ポリテトラメチレンエーテルグリコール（Ｄ−５）：三菱化学株式会社製「ＰＴＭＧ ６５０」
ポリエステルポリオール（Ｄ−６）：東ソー株式会社製「ニッポラン １３６」
ウレタン化触媒（Ｅ）：日東化成株式会社製「ネオスタン Ｕ−６００」The following were used for (B), (C), (D), (E), (B ′) and (C ′) described in Tables 1 to 3.
1,6-hexamethylene diisocyanate (B-1): “Desmodur H” manufactured by Sumika Covestrourethane Co., Ltd.
4,4′-diphenylmethane diisocyanate (B-2): “Millionate MT” manufactured by Tosoh Corporation
Dicyclohexylmethane-4,4′-diisocyanate (B-3): “Death Module W” manufactured by Sumika Covestrourethane Co., Ltd.
Isophorone diisocyanate (B'-1): "Death Module I" manufactured by Sumika Covestrourethane Co., Ltd.
1,4-butanediol (C-1): “14BG” manufactured by Mitsubishi Chemical Corporation
1,6-hexanediol (C-2): “1,6-hexanediol” manufactured by Ube Industries, Ltd.
1,8-octanediol (C-3): Tokyo Chemical Industry Co., Ltd. Hexaethylene glycol (C-4): Tokyo Chemical Industry Co., Ltd. 1,5-neopentyl glycol (C'-1): Tokyo Chemical Industry Polytetramethylene ether glycol (D-1) manufactured by Mitsubishi Electric Corporation “PTMG 1000”
Polypropylene glycol (D-2): “Prime Paul PX-1000” manufactured by Sanyo Chemical Industries, Ltd. (primary OH group ratio: 70 mol%)
Polyester polyol (D-3): “Nipporan 164” manufactured by Tosoh Corporation
Polypropylene glycol (D-4): “SANNICS PP-1000” manufactured by Sanyo Chemical Industries, Ltd. (primary OH group ratio: 2 mol%)
Polytetramethylene ether glycol (D-5): “PTMG 650” manufactured by Mitsubishi Chemical Corporation
Polyester polyol (D-6): “Nipporan 136” manufactured by Tosoh Corporation
Urethane catalyst (E): “Neostan U-600” manufactured by Nitto Kasei Co., Ltd.
表１〜３に記載のポリオール［（Ａ）＋（Ｃ）＋（Ｄ）］の水分量（％）は、カールフィッシャー水分計(容量滴定方式)を使用して測定した。カールフィッシャー水分計は、京都電子工業株式会社製：カールフィッシャー水分計（ＭＫＳ−５００）を用いた。希釈溶剤としてメタノールを用いて、測定試料約１ｇを有効数字４桁まで精秤し、メタノール中に投入し、１分間攪拌した。攪拌後、適定によって求められた水分量を読み取った。
なお、この計算における（Ｃ）には（Ｃ’）を含む。The moisture content (%) of the polyols [(A) + (C) + (D)] listed in Tables 1 to 3 was measured using a Karl Fischer moisture meter (volumetric titration method). As the Karl Fischer moisture meter, a Karl Fischer moisture meter (MKS-500) manufactured by Kyoto Electronics Industry Co., Ltd. was used. Using methanol as a diluting solvent, about 1 g of a measurement sample was precisely weighed to 4 significant digits, put into methanol, and stirred for 1 minute. After stirring, the water content determined by titration was read.
Note that (C) in this calculation includes (C ′).
ホットメルト接着剤（Ｈ−１）〜（Ｈ−２６）及び比較用のメルト接着剤（Ｈ'−１）〜（Ｈ'−３）について、以下の方法で性能評価を行った結果を表１〜３に示す。 Table 1 shows the results of performance evaluation of hot melt adhesives (H-1) to (H-26) and comparative melt adhesives (H'-1) to (H'-3) by the following methods. Shown in ~ 3.
評価方法は、次の通りである。
ホットメルト接着剤（Ｈ−１）〜（Ｈ−２６）及び比較用のメルト接着剤（Ｈ'−１）〜（Ｈ'−３）について、以下では単に接着剤という。
（１）１５０℃溶融粘度
ＪＩＳ−Ｋ７１１７（１９９９年）に準拠し、Ｂ型粘度計（東機産業株式会社製「ＲＢ−８０Ｈ」）を用いて１５０℃での粘度を測定した。The evaluation method is as follows.
The hot melt adhesives (H-1) to (H-26) and the comparative melt adhesives (H′-1) to (H′-3) are hereinafter simply referred to as adhesives.
(1) 150 degreeC melt viscosity Based on JIS-K7117 (1999), the viscosity at 150 degreeC was measured using the B-type viscosity meter ("RB-80H" by Toki Sangyo Co., Ltd.).
（２）融点
示差走査熱量測定（ＤＳＣ）（ティー・エイ・インスツルメント・ジャパン株式会社製「Ｑ２０」）における吸熱ピークより求めた。(2) It calculated | required from the endothermic peak in melting | fusing point differential scanning calorimetry (DSC) ("Q20" by TA Instruments Japan Co., Ltd.).
（３）引張破断強度
接着剤を厚さ１ｍｍになるようにプレス機（テスター産業株式会社製「ＳＡ−３０２ 卓上型テストプレス」）を使用して２３０℃でプレスすることで樹脂フィルムを作成し、塗膜の引張破断強度をＪＩＳ Ｋ ７３１１（１９９５年）に準拠して測定した。(3) Tensile strength at break The adhesive film was pressed at 230 ° C. using a press machine (“SA-302 desktop test press” manufactured by Tester Sangyo Co., Ltd.) to a thickness of 1 mm. The tensile breaking strength of the coating film was measured according to JIS K 7311 (1995).
（４）温度依存性
下記の測定条件で、−２０℃及び７０℃での、接着剤の貯蔵弾性率（Ｇ’）を測定し、Ｇ'（−２０℃）／Ｇ'（７０℃）を求めて温度依存性を評価した。この数値が１００以下であると温度依存性が少ないと評価した。
貯蔵弾性率（Ｇ’）は、樹脂フィルムを「（３）引張破断強度」と同じ方法でプレスし下記サンプルサイズに切り抜いて作製し、粘弾性を以下の測定条件で測定することによって求めた。
＜粘弾性測定条件＞
測定装置：Ｒｈｅｏｇｅｌ−Ｅ４０００［株式会社ＵＢＭ製］
測定治具：固体せん断
測定温度：−２０〜１３０℃
昇温速度：５℃／ｍｉｎ
測定周波数：１０Ｈｚ
サンプルサイズ：約７ｍｍ（縦）×約６ｍｍ（横）(4) Temperature dependence Under the following measurement conditions, the storage elastic modulus (G ′) of the adhesive at −20 ° C. and 70 ° C. is measured, and G ′ (−20 ° C.) / G ′ (70 ° C.) is calculated. The temperature dependence was evaluated. When this value was 100 or less, it was evaluated that the temperature dependency was small.
The storage elastic modulus (G ′) was determined by pressing a resin film in the same manner as “(3) Tensile strength at break” and cutting out to the following sample size, and measuring viscoelasticity under the following measurement conditions.
<Viscoelasticity measurement conditions>
Measuring device: Rheogel-E4000 [manufactured by UBM Co., Ltd.]
Measurement jig: Solid shear measurement temperature: -20 to 130 ° C
Temperature increase rate: 5 ° C / min
Measurement frequency: 10Hz
Sample size: about 7mm (length) x about 6mm (width)
（５）シャープメルト性
上記の測定条件で、７０℃及び「（２）融点」で測定した融点＋２０℃での、接着剤の貯蔵弾性率（Ｇ’）を測定し、Ｇ'（７０℃）／Ｇ'（融点＋２０℃）を求めてシャープメルト性を評価した。この数値が８０以上であるとシャープメルト性が良好と評価した。(5) Sharp melt property Under the above measurement conditions, the storage elastic modulus (G ′) of the adhesive was measured at 70 ° C. and the melting point + 20 ° C. measured by “(2) melting point”, and G ′ (70 ° C.). / G ′ (melting point + 20 ° C.) was determined to evaluate the sharp melt property. It was evaluated that the sharp melt property was good when this value was 80 or more.
（６）接着力（８０℃）
接着剤を、２枚のＰＥＴフィルム（厚さ１００μｍ）の間に挟みこみ、厚みが１ｍｍとなるように貼り合わせてサンプルを作製した。上記サンプルを２００ｍｍ×２５ｍｍの大きさに裁断し、引張試験機を用い、測定温度（８０℃）で引っ張り速度１００ｍｍ／分の条件でＴ型剥離強度（単位：Ｎ／２５ｍｍ）を測定した。(6) Adhesive strength (80 ° C)
An adhesive was sandwiched between two PET films (thickness: 100 μm) and bonded to a thickness of 1 mm to prepare a sample. The sample was cut into a size of 200 mm × 25 mm, and a T-type peel strength (unit: N / 25 mm) was measured at a measurement temperature (80 ° C.) under a pulling rate of 100 mm / min using a tensile tester.
＜ウレア基含有量＞
ウレア基含有量は、窒素分析計［ＡＮＴＥＫ７０００（アンテック社製）］によって定量されるＮ原子含量と１Ｈ−ＮＭＲによって定量されるウレタン基とウレア基の比率から算出する。１Ｈ−ＮＭＲ測定については、「ＮＭＲによるポリウレタン樹脂の構造研究：武田研究所報３４（２）、２２４−３２３（１９７５）」に記載の方法で行う。すなわち１Ｈ−ＮＭＲを測定して、脂肪族イソシアネートを使用した場合、化学シフト６ｐｐｍ付近のウレア基由来の水素の積分量と化学シフト７ｐｐｍ付近のウレタン基由来の水素の積分量の比率からウレア基とウレタン基の重量比を測定し、該重量比と上記のＮ原子含量及びアロハネート基及びビューレット基含量からウレタン基及びウレア基含量を算出する。芳香族イソシアネートを使用した場合、化学シフト８ｐｐｍ付近のウレア基由来の水素の積分量と化学シフト９ｐｐｍ付近のウレタン基由来の水素の積分量の比率からウレア基とウレタン基の重量比を算出し、該重量比と上記のＮ原子含量からウレア基含有量を算出する。<Urea group content>
The urea group content is calculated from the N atom content determined by a nitrogen analyzer [ANTEK7000 (manufactured by Antec)] and the ratio of urethane group and urea group determined by 1 H-NMR. The 1 H-NMR measurement is carried out by the method described in “Structural study of polyurethane resin by NMR: Takeda Laboratory Report 34 (2), 224-323 (1975)”. That is, when 1 H-NMR is measured and an aliphatic isocyanate is used, the urea group is calculated from the ratio of the integral amount of hydrogen derived from a urea group near a chemical shift of 6 ppm and the integral amount of hydrogen derived from a urethane group near a chemical shift of 7 ppm. The urethane group and the urea group content are calculated from the weight ratio, the N atom content, the allophanate group and the burette group content. When aromatic isocyanate is used, the weight ratio of urea group and urethane group is calculated from the ratio of the integral amount of hydrogen derived from urea groups near the chemical shift of 8 ppm and the integral amount of hydrogen derived from urethane groups near the chemical shift of 9 ppm, The urea group content is calculated from the weight ratio and the N atom content.
ホットメルト接着剤（Ｈ−１）〜（Ｈ−２６）は、温度依存性が少ないため、これを使用した製品の品質安定性に優れる。そして、ホットメルト接着剤として使用した際には、接着力が安定する。さらに、引張破断強度にも優れる。 Since the hot melt adhesives (H-1) to (H-26) have little temperature dependency, the quality stability of products using the hot melt adhesives (H-1) to (H-26) is excellent. And when it uses as a hot-melt-adhesive, adhesive force is stabilized. Furthermore, the tensile strength at break is also excellent.
本発明のホットメルト接着剤は衣料用途や各種産業資材の芯地の製造にとくに有用である。 The hot melt adhesive of the present invention is particularly useful for apparel use and production of various industrial materials.
Claims (8)
上記芳香環を有するポリオール（Ａ）がビスフェノールＡ、ビスフェノールＢ、ビスフェノールＥ及びビスフェノールＦからなる群より選ばれる少なくとも１種のビスフェノール化合物のエチレンオキサイド付加物（Ａ１）であり、
上記高分子ポリオール（Ｄ）がポリエーテルポリオール（Ｄ１）であるホットメルト接着剤。
ＨＯ−（ＣＨ２）ｎ−ＯＨ （１）
［ｎは２〜８の整数である。］
ＨＯ−（ＣＨ２ＣＨ２Ｏ）ｍ−Ｈ （２）
［ｍは２〜８の整数である。］ Polyol (A) having an aromatic ring, diisocyanate (B) having symmetry, polymethylene glycol (C1) represented by general formula (1) and / or polyethylene glycol (C2) represented by general formula (2) A hot melt adhesive containing a thermoplastic urethane resin (F) having a glycol (C) and a polymer polyol (D) as essential constituent monomers ,
The polyol (A) having an aromatic ring is an ethylene oxide adduct (A1) of at least one bisphenol compound selected from the group consisting of bisphenol A, bisphenol B, bisphenol E and bisphenol F,
A hot melt adhesive, wherein the polymer polyol (D) is a polyether polyol (D1).
HO— (CH 2 ) n —OH (1)
[N is an integer of 2 to 8. ]
HO- (CH 2 CH 2 O) m-H (2)
[M is an integer of 2 to 8. ]
単分散度（％）＝｛［水酸基あたりエチレンオキサイド付加モル数が１モルであるエチレンオキサイド付加物（Ａ１）の重量］／［エチレンオキサイド付加物（Ａ）の重量］｝×１００ （１） The ethylene oxide adduct (A1) has an ethylene oxide average addition mole number of 0.90 to 1.10 per hydroxyl group, and a monodispersity represented by the following formula (1) is 80% or more. The hot melt adhesive according to claim 1 , which is (A11).
Monodispersity (%) = {[weight of ethylene oxide adduct (A1) having 1 mol of ethylene oxide added per hydroxyl group] / [weight of ethylene oxide adduct (A)]} × 100 (1)
上記ポリメチレンジイソシアネート（Ｂ１）中のイソシアネート基中の炭素を除く炭素数が、上記ポリメチレングリコール（Ｃ１）の炭素数と同数である請求項５に記載のホットメルト接着剤。 The glycol (C) includes the polymethylene glycol (C1),
The hot melt adhesive according to claim 5 , wherein the number of carbon atoms in the isocyanate group in the polymethylene diisocyanate (B1) is the same as the number of carbon atoms in the polymethylene glycol (C1).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016042530 | 2016-03-04 | ||
| JP2016042530 | 2016-03-04 | ||
| PCT/JP2017/004895 WO2017150142A1 (en) | 2016-03-04 | 2017-02-10 | Hot-melt adhesive |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019168418A Division JP6836636B2 (en) | 2016-03-04 | 2019-09-17 | Hot melt adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2017150142A1 JPWO2017150142A1 (en) | 2018-10-18 |
| JP6591040B2 true JP6591040B2 (en) | 2019-10-16 |
Family
ID=59744024
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018503000A Active JP6591040B2 (en) | 2016-03-04 | 2017-02-10 | Hot melt adhesive |
| JP2019168418A Active JP6836636B2 (en) | 2016-03-04 | 2019-09-17 | Hot melt adhesive |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019168418A Active JP6836636B2 (en) | 2016-03-04 | 2019-09-17 | Hot melt adhesive |
Country Status (3)
| Country | Link |
|---|---|
| JP (2) | JP6591040B2 (en) |
| CN (1) | CN108603088B (en) |
| WO (1) | WO2017150142A1 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0730297B2 (en) * | 1986-03-25 | 1995-04-05 | 旭硝子株式会社 | Hot melt adhesive |
| JPH06271830A (en) * | 1993-03-18 | 1994-09-27 | Sekisui Chem Co Ltd | Hot-melt adhesive |
| JP2984921B2 (en) * | 1997-01-20 | 1999-11-29 | 三洋化成工業株式会社 | Hot melt adhesive |
| EP2025730B1 (en) * | 2006-12-01 | 2014-04-16 | DIC Corporation | Moisture-curable polyurethane hot melt adhesive and multilayer sheet using the same |
| JP2009286941A (en) * | 2008-05-30 | 2009-12-10 | Henkel Japan Ltd | Moisture-curable hot melt adhesive |
-
2017
- 2017-02-10 WO PCT/JP2017/004895 patent/WO2017150142A1/en active Application Filing
- 2017-02-10 CN CN201780009827.0A patent/CN108603088B/en active Active
- 2017-02-10 JP JP2018503000A patent/JP6591040B2/en active Active
-
2019
- 2019-09-17 JP JP2019168418A patent/JP6836636B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108603088A (en) | 2018-09-28 |
| CN108603088B (en) | 2020-12-01 |
| JP2020015918A (en) | 2020-01-30 |
| JPWO2017150142A1 (en) | 2018-10-18 |
| WO2017150142A1 (en) | 2017-09-08 |
| JP6836636B2 (en) | 2021-03-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101691870B1 (en) | Moisture-curable polyurethane hot melt resin composition, adhesive and article | |
| US8686076B2 (en) | Silane moisture curable hot melts | |
| KR100583926B1 (en) | Polyurethane and preparation containing polyurethane | |
| CN102482549B (en) | Hot melt adhesive composition | |
| US8383728B2 (en) | Adhesives based on polyester-graft-poly(meth)acrylate copolymers | |
| US8865842B2 (en) | Polyurethane hot-melt adhesive with reduced viscosity | |
| US20130210989A1 (en) | Polyurethane hot-melt adhesive produced from polyacrylates and polyesters | |
| CN101679593A (en) | Resin composition containing thermoplastic polyurethane and hot-melt adhesive | |
| CN102549095A (en) | Radiation-cure removal type pressure-sensitive adhesive sheet | |
| CN111433244B (en) | Toughened cyanoacrylate compositions | |
| Lopez et al. | A perfluoropolyether-based elastomers library with on-demand thermorheological features | |
| EP0001166B1 (en) | Liquid polymer compositions, process for the preparation of adhesives and laminate structures | |
| EP0001165B1 (en) | Polyurethane based compositions, a process for their preparation and their use as adhesives in laminate structures | |
| JP6591040B2 (en) | Hot melt adhesive | |
| JP7176425B2 (en) | Polyamide compound | |
| JP2023103299A (en) | Polycarbonate diol composition | |
| JP2017105992A (en) | Hot-melt adhesive composition and bonded body thereof | |
| JP2023005131A (en) | Adhesive composition and adhesive sheet | |
| US3829526A (en) | Hydrogenated polyphenols as sulfur solubilizers in polythiol sealants | |
| JP7295341B2 (en) | Two-component polyurethane adhesive and adherend | |
| JP2018111748A (en) | Reactive hot-melt adhesive | |
| JP4232094B2 (en) | Composition for flexible resin molding excellent in high-temperature shear bonding performance and flexible resin molding obtained therefrom | |
| US4243789A (en) | Hydroxyl-containing liquid polymers and pressure-sensitive adhesives prepared therefrom | |
| WO2024181569A1 (en) | Carbonate group-containing polyol | |
| JPS63218782A (en) | Adhesive composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180605 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190312 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190419 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20190903 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190917 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6591040 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |