JP5347212B2 - Polyester resin and method for producing the same - Google Patents
Polyester resin and method for producing the same Download PDFInfo
- Publication number
- JP5347212B2 JP5347212B2 JP2006074288A JP2006074288A JP5347212B2 JP 5347212 B2 JP5347212 B2 JP 5347212B2 JP 2006074288 A JP2006074288 A JP 2006074288A JP 2006074288 A JP2006074288 A JP 2006074288A JP 5347212 B2 JP5347212 B2 JP 5347212B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- molecular weight
- acid
- average molecular
- hydroxyl group
- 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
- 239000004645 polyester resin Substances 0.000 title claims abstract description 150
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 150
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 66
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 58
- 239000002253 acid Substances 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 150000002009 diols Chemical class 0.000 claims abstract description 23
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 16
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 9
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 31
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 5
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 46
- 150000008064 anhydrides Chemical class 0.000 abstract description 24
- 150000007519 polyprotic acids Polymers 0.000 abstract description 18
- 238000004132 cross linking Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 230000015271 coagulation Effects 0.000 abstract 1
- 238000005345 coagulation Methods 0.000 abstract 1
- 238000005728 strengthening Methods 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 description 49
- 230000001070 adhesive effect Effects 0.000 description 49
- 230000015572 biosynthetic process Effects 0.000 description 36
- 238000003786 synthesis reaction Methods 0.000 description 36
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 30
- -1 ester compound Chemical class 0.000 description 27
- 238000012360 testing method Methods 0.000 description 26
- 239000003431 cross linking reagent Substances 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 239000000758 substrate Substances 0.000 description 18
- 239000010408 film Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001723 curing Methods 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000012790 adhesive layer Substances 0.000 description 12
- 239000012948 isocyanate Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000003973 paint Substances 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 229920003180 amino resin Polymers 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 10
- 229920001721 polyimide Polymers 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 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 6
- 230000008961 swelling Effects 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229910001335 Galvanized steel Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 239000008397 galvanized steel Substances 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920003987 resole Polymers 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000007718 adhesive strength test Methods 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 150000002513 isocyanates Chemical group 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 239000005028 tinplate Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- RYRZSXJVEILFRR-UHFFFAOYSA-N 2,3-dimethylterephthalic acid Chemical compound CC1=C(C)C(C(O)=O)=CC=C1C(O)=O RYRZSXJVEILFRR-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229920006311 Urethane elastomer Polymers 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 239000013039 cover film Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000002483 hydrogen compounds Chemical class 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- 229940051269 1,3-dichloro-2-propanol Drugs 0.000 description 1
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-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
- 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 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- QBDAFARLDLCWAT-UHFFFAOYSA-N 2,3-dihydropyran-6-one Chemical compound O=C1OCCC=C1 QBDAFARLDLCWAT-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- PWOUDGCZDZTZAN-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethyl)but-2-enyl]oxirane;urea Chemical compound NC(N)=O.C1OC1CC(=CC)CC1CO1 PWOUDGCZDZTZAN-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- PLDLPVSQYMQDBL-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethoxy)-2,2-bis(oxiran-2-ylmethoxymethyl)propoxy]methyl]oxirane Chemical compound C1OC1COCC(COCC1OC1)(COCC1OC1)COCC1CO1 PLDLPVSQYMQDBL-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- RDNPPYMJRALIIH-UHFFFAOYSA-N 3-methylcyclohex-3-ene-1,1,2,2-tetracarboxylic acid Chemical compound CC1=CCCC(C(O)=O)(C(O)=O)C1(C(O)=O)C(O)=O RDNPPYMJRALIIH-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- HAYIPGIFANTODX-UHFFFAOYSA-N 4,6-dimethylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC(C)=C(C(O)=O)C=C1C(O)=O HAYIPGIFANTODX-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- HGINADPHJQTSKN-UHFFFAOYSA-N Monoethyl malonic acid Chemical compound CCOC(=O)CC(O)=O HGINADPHJQTSKN-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 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
- 150000001412 amines Chemical class 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- ZXOATMQSUNJNNG-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,3-dicarboxylate Chemical compound C=1C=CC(C(=O)OCC2OC2)=CC=1C(=O)OCC1CO1 ZXOATMQSUNJNNG-UHFFFAOYSA-N 0.000 description 1
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 description 1
- JQDCYGOHLMJDNA-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) butanedioate Chemical compound C1OC1COC(=O)CCC(=O)OCC1CO1 JQDCYGOHLMJDNA-UHFFFAOYSA-N 0.000 description 1
- KTPIWUHKYIJBCR-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-4-ene-1,2-dicarboxylate Chemical compound C1C=CCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KTPIWUHKYIJBCR-UHFFFAOYSA-N 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- NFVGWOSADNLNHZ-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) decanedioate Chemical compound C1OC1COC(=O)CCCCCCCCC(=O)OCC1CO1 NFVGWOSADNLNHZ-UHFFFAOYSA-N 0.000 description 1
- KBWLNCUTNDKMPN-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) hexanedioate Chemical compound C1OC1COC(=O)CCCCC(=O)OCC1CO1 KBWLNCUTNDKMPN-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 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
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- SOOARYARZPXNAL-UHFFFAOYSA-N methyl-thiophenol Natural products CSC1=CC=CC=C1O SOOARYARZPXNAL-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000005029 tin-free steel Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- UMEJBQAJSACPLX-UHFFFAOYSA-K trisodium 4,6-dimethyl-5-sulfonatobenzene-1,3-dicarboxylate Chemical compound [Na+].CC1=C(C(=C(C=C1C(=O)[O-])C(=O)[O-])C)S(=O)(=O)[O-].[Na+].[Na+] UMEJBQAJSACPLX-UHFFFAOYSA-K 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明はポリエステル樹脂に関し、特に接着剤や塗料に用いた場合に基材との接着性に優れ、また、フィルム状に成型した場合には良好な造膜性を有するポリエステル樹脂に関する。さらに詳しくは、多塩基酸もしくはその無水物と水酸基を有するポリエステル樹脂との鎖延長反応により、ポリエステル樹脂の分子量を増大させると共に、官能基が両末端にしか存在しない直鎖型ポリエステル樹脂の分子中にカルボキシル基を導入することにより基材との接着性を良好ならしめるポリエステル樹脂の製造方法とそれにより得られるポリエステル樹脂に関する。 The present invention relates to a polyester resin, and particularly relates to a polyester resin having excellent adhesion to a substrate when used in an adhesive or a paint, and having good film forming properties when molded into a film. More specifically, the molecular weight of the polyester resin is increased by a chain extension reaction between a polybasic acid or an anhydride thereof and a polyester resin having a hydroxyl group, and at the same time, the molecular weight of the linear polyester resin in which the functional groups exist only at both ends is obtained. The present invention relates to a method for producing a polyester resin, which can improve the adhesion to a substrate by introducing a carboxyl group into the polyester, and a polyester resin obtained thereby.
従来より、接着剤や塗料分野において、そのバインダーとしてポリエステル樹脂が広く用いられている。両末端にのみ官能基を有する所謂直鎖型ポリエステル樹脂は、架橋剤を用いて架橋させても架橋密度は相対的に低くなり、被膜の物性を向上させるために高分子量化している。一方、多官能成分を導入して両末端と末端以外の分子中にも官能基を有する所謂分岐型ポリエステル樹脂は、架橋剤を用いて架橋させた場合、架橋密度が相対的に高くなりすぎて被膜物性が脆くなるという欠点を有する。被膜物性を向上させようとして分子量を大きくしようとしてもゲル化のために限りがある。 Conventionally, polyester resins have been widely used as binders in the field of adhesives and paints. A so-called linear polyester resin having functional groups only at both ends has a relatively low crosslinking density even when crosslinked using a crosslinking agent, and has a high molecular weight in order to improve the physical properties of the coating. On the other hand, when a polyfunctional component is introduced and a so-called branched polyester resin having functional groups in both terminals and molecules other than the terminals is crosslinked with a crosslinking agent, the crosslinking density becomes relatively high. It has the disadvantage that the physical properties of the film become brittle. An attempt to increase the molecular weight in order to improve the physical properties of the film is limited due to gelation.
プラスチック同士、金属同士、あるいはプラスチックと金属などの構造物の接合において、従来はボルトやネジなどを用いて接合していたが、近年、工程の簡略化やコスト削減の目的から、接着剤で接合する方法が用いられるようになった。このような構造物の接合においては、基材の強度に匹敵するような強固な接着性が要求される。強固な接着性を発現させるためには、基材との密着性とともに接着剤自身の凝集力を強くする必要がある。接着剤自身の凝集力を強くするためには、高架橋密度と分子量の増大が必須である。 In the past, bolts and screws were used to join plastics, metals, or plastic and metal structures, but in recent years they have been joined with adhesives to simplify the process and reduce costs. The method to do came to be used. In joining such a structure, strong adhesiveness comparable to the strength of the base material is required. In order to develop strong adhesiveness, it is necessary to strengthen the cohesive strength of the adhesive itself as well as the adhesion to the substrate. In order to strengthen the cohesive strength of the adhesive itself, it is essential to increase the high crosslinking density and the molecular weight.
ポリエステル樹脂と酸無水物を用いる接着剤の例としては、例えば特開平5−70758号公報(特許文献1参照)ではポリエステル樹脂に無水トリメリット酸を付加させているが、ポリエステル樹脂の末端に付加させているだけで、分子量の増大は狙っていない。
また、特開2001−31940号公報(特許文献2参照)ではポリエステル樹脂とベンゾフェノンテトラカルボン酸二無水物とグリセロールトリスアンヒドロトリメリテートとエポキシ化合物をブレンドしているが、硬化の過程ではエポキシ化合物と酸無水物との反応が優先し、ポリエステル樹脂の分子量増大が起きるとは考えにくい。
塗料組成物の例としては、密着性や加工性の向上を狙いとして、特開平11−116667号公報(特許文献3参照)や特開2001−40278号公報(特許文献4参照)、特開2003−213201号公報(特許文献5参照)が公開されている。
特開平11−116667号公報では、ポリエステル樹脂中の水酸基に、分子中に2個以上のカルボン酸無水基を含有するエステル化合物を反応させているが、反応後の数平均分子量は10000以下であり、また、反応前後における数平均分子量の変化は小さいものであり、この反応における分子量の増大は意図していないと考えられる。
特開2001−40278号公報では、ポリエステル樹脂の末端にカルボキシル基の導入を意図している。
As an example of an adhesive using a polyester resin and an acid anhydride, for example, in JP-A-5-70758 (see Patent Document 1), trimellitic anhydride is added to the polyester resin, but it is added to the end of the polyester resin. It does not aim to increase molecular weight.
Japanese Patent Laid-Open No. 2001-31940 (see Patent Document 2) blends a polyester resin, benzophenonetetracarboxylic dianhydride, glycerol trisanhydro trimellitate, and an epoxy compound. It is unlikely that the molecular weight of the polyester resin will increase due to the reaction of the acid anhydride with the acid anhydride.
Examples of the coating composition are disclosed in JP-A-11-116667 (see Patent Document 3), JP-A-2001-40278 (see Patent Document 4), and JP-A-2003, with the aim of improving adhesion and workability. -213201 (see Patent Document 5).
In JP-A-11-116667, an ester compound containing two or more carboxylic anhydride groups in a molecule is reacted with a hydroxyl group in a polyester resin, but the number average molecular weight after the reaction is 10,000 or less. In addition, the change in the number average molecular weight before and after the reaction is small, and it is considered that the increase in the molecular weight in this reaction is not intended.
Japanese Patent Laid-Open No. 2001-40278 intends to introduce a carboxyl group at the terminal of the polyester resin.
特開2003−213201号公報では、分子鎖途中にカルボキシル基がペンダント状に導入された分子を含むポリエステル樹脂が開示されているが、この反応の好ましい方法としては、ポリエステル樹脂が目標の分子量に達した段階でカルボン酸無水物を添加して、無溶剤下で反応している。また、反応温度は150℃〜280℃と高温であり、このような方法ではカルボキシル基はポリエステル樹脂の末端には導入され得るものの、さらに反応を進行させ、分子鎖途中にペンダント状に導入され得るまで反応を続けるとようとすると、過度に高分子量化が進行し、ゲル化してしまう。
特許文献1、3、4、及び5はポリエステル樹脂と分子内に2個以上のカルボン酸無水物基を有する化合物とを反応させているが、いずれも酸価の付与だけで、分子量の増大は狙っていない。
Patent Documents 1, 3, 4, and 5 react a polyester resin with a compound having two or more carboxylic acid anhydride groups in the molecule, but all increase the molecular weight only by giving an acid value. Not aiming.
本発明の課題は、基材の強度に匹敵するような強固な接着性を発現するために、基材との密着性を向上させるだけでなく、硬化後の架橋密度と凝集力を強固にすることの出来るポリエステル樹脂の製造方法と、それにより得られるポリエステル樹脂を提供することにある。
さらには、フイルム同士の接着で嫌われる硬化時にアウトガスを発生させる様な架橋剤、アミノ樹脂などの所謂縮合系架橋剤を用いることなく、硬化時にアウトガスを発生させない所謂付加反応型の架橋剤を用いることの出来るポリエステル樹脂を提供することにある。
The object of the present invention is not only to improve the adhesion to the substrate, but also to strengthen the crosslink density and cohesion after curing in order to develop a strong adhesion comparable to the strength of the substrate. It is in providing the manufacturing method of the polyester resin which can be performed, and the polyester resin obtained by it.
Furthermore, without using a so-called condensation-type cross-linking agent such as an amino resin, or a so-called addition reaction type cross-linking agent that does not generate an out-gas at the time of curing without using a cross-linking agent that generates an out-gas at the time of curing that is hated by adhesion between films. It is in providing the polyester resin which can be used.
本発明者らは上記課題を解決すべく鋭意検討した結果、水酸基を有するポリエステル樹脂を、多塩基酸もしくはその無水物と反応させてカルボキシル基を有するポリエステル樹脂を得る製造方法と、それによって得られるポリエステル樹脂を見出し、本発明を完成させるに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a polyester resin having a carboxyl group by reacting a polyester resin having a hydroxyl group with a polybasic acid or an anhydride thereof, and thus obtained. The present inventors have found a polyester resin and completed the present invention.
即ち、第1の発明は、ジオール(c1)と、二塩基酸、二塩基酸無水物、及び二塩基酸のアルキルエステルからなる群より選ばれる少なくとも1種以上のカルボン酸成分(c2)とを無溶剤下に反応させて、数平均分子量(Mn1)15000〜30000かつ重量数平均分子量(Mw1)25000〜60000の水酸基を有するポリエステル樹脂(c3)を得、
次いで前記水酸基を有するポリエステル樹脂(c3)を溶剤に溶解した後、前記溶剤の沸点以下の温度で、水酸基を有するポリエステル樹脂(c3)を無水ピロメリット酸またはエチレングリコールビストリメリテート二無水物(c4)と反応させて、数平均分子量(Mn2)が21000以上及び重量平均分子量(Mw2)が42300以上のカルボキシル基を有するポリエステル樹脂を得、
前記カルボキシル基を有するポリエステル樹脂の数平均分子量(Mn2)及び重量平均分子量(Mw2)のいずれもが、前記水酸基を有するポリエステル樹脂(c3)の数平均分子量(Mn1)及び重量平均分子量(Mw1)のそれぞれ3倍以下である、カルボキシル基を有するポリエステル樹脂の製造方法である。
That is, the first invention comprises a diol (c1) and at least one carboxylic acid component (c2) selected from the group consisting of a dibasic acid, a dibasic acid anhydride, and an alkyl ester of a dibasic acid. By reacting in the absence of a solvent, a polyester resin (c3) having a hydroxyl group with a number average molecular weight (Mn1) of 15000 to 30000 and a weight number average molecular weight (Mw1) of 25000 to 60000 is obtained.
Next, after the polyester resin (c3) having a hydroxyl group is dissolved in a solvent, the polyester resin (c3) having a hydroxyl group is dissolved in pyromellitic anhydride or ethylene glycol bistrimellitate dianhydride (c4) at a temperature not higher than the boiling point of the solvent. ) To obtain a polyester resin having a carboxyl group having a number average molecular weight (Mn2) of 21,000 or more and a weight average molecular weight (Mw2) of 42300 or more,
The number average molecular weight (Mn2) and the weight average molecular weight (Mw2) of the polyester resin having a carboxyl group are both the number average molecular weight (Mn1) and the weight average molecular weight (Mw1) of the polyester resin (c3) having a hydroxyl group. It is a manufacturing method of the polyester resin which has a carboxyl group which is 3 times or less respectively.
第2の発明は、カルボキシル基を有するポリエステル樹脂の酸価が5〜40mgKOH/gであることを特徴とする、上記発明のカルボキシル基を有するポリエステル樹脂の製造方法である。 2nd invention is a manufacturing method of the polyester resin which has the carboxyl group of the said invention, The acid value of the polyester resin which has a carboxyl group is 5-40 mgKOH / g.
第3の発明は、四級アンモニウム塩の存在下に、水酸基を有するポリエステル樹脂(c3)を無水ピロメリット酸またはエチレングリコールビストリメリテート二無水物(c4)と反応させることを特徴とする上記いずれかの発明のカルボキシル基を有するポリエステル樹脂の製造方法である。 According to a third aspect of the present invention, any one of the above, wherein the polyester resin (c3) having a hydroxyl group is reacted with pyromellitic anhydride or ethylene glycol bistrimellitate dianhydride (c4) in the presence of a quaternary ammonium salt. It is a manufacturing method of the polyester resin which has a carboxyl group of the invention.
本発明のポリエステル樹脂は、水酸基を有するポリエステル樹脂(c3)を、溶剤の存在下に多塩基酸もしくはその無水物と反応させてなるカルボキシル基を有するポリエステル樹脂であって、その反応方法を工夫することにより、カルボキシル基が分子途中に導入されることに特徴がある。
このように、本来、末端にしか官能基の存在しない直鎖型ポリエステル樹脂の分子途中にカルボキシル基を導入することにより、高凝集力で且つ架橋密度の高い被膜を形成できる。さらには、高酸価を付与することにより、基材との密着性に優れ、またアミノ樹脂等の硬化時にアウトガスを発生させる架橋剤を用いることなく、付加反応型の架橋剤を用いることができる。
The polyester resin of the present invention is a polyester resin having a carboxyl group obtained by reacting a polyester resin (c3) having a hydroxyl group with a polybasic acid or its anhydride in the presence of a solvent, and devise the reaction method. This is characterized in that the carboxyl group is introduced in the middle of the molecule.
In this way, by introducing a carboxyl group into the middle of a molecule of a linear polyester resin that originally has a functional group only at the terminal, a film having a high cohesive force and a high crosslinking density can be formed. Furthermore, it is possible to use an addition-reactive type crosslinking agent without using a crosslinking agent that is excellent in adhesion to the substrate by generating a high acid value and generates outgas upon curing of an amino resin or the like. .
本発明で用いられる水酸基を有するポリエステル樹脂(c3)は、ジオール(c1)と、二塩基酸、二塩基酸無水物、及び二塩基酸のアルキルエステルからなる群より選ばれる少なくとも1種以上のカルボン酸成分(c2)とを反応させて得られる。
(c3)は、広く知られている多価アルコールと多価カルボン酸もしくはその無水物やアルキルエステルとの重縮合反応(エステル化反応ないしエステル交換反応)により合成することができる。
例えば、ジオール(c1)とカルボン酸成分(c2)とを反応釜に仕込み、加熱昇温することにより、エステル化反応またはエステル交換反応を行い、この反応で生じた水またはアルコールを留去しながら所定の酸価になるまで反応を続ける。必要に応じて、テトラブチルチタネート、ジブチルスズオキサイド、酢酸マンガン、酢酸亜鉛、酢酸スズなどの重合触媒を用いることが出来る。
この反応は常圧下、減圧下の何れで行っても良いが、高分子量にするためには減圧下での反応が好ましい。又分子量の調節はジオール(c1)と、カルボン酸成分(c2)との仕込み比等によって行うことができる。
なお、ジオール(c1)とカルボン酸成分(c2)との反応は、無溶剤下でおこなうことが好ましい。
ジオール(c1)とカルボン酸成分(c2)との反応は、脱水もしくは脱アルコール反応が始まる温度から徐々に昇温し、200〜250℃で数時間保持することが好ましく、220〜240℃で3〜5時間保持することがより好ましい。また、減圧下で高分子量にする場合には、5mmHg以下の減圧度で、230〜250℃で1〜8時間反応を続ける。
The polyester resin (c3) having a hydroxyl group used in the present invention comprises at least one carboxylic acid selected from the group consisting of a diol (c1), a dibasic acid, a dibasic acid anhydride, and an alkyl ester of a dibasic acid. Obtained by reacting with the acid component (c2).
(C3) can be synthesized by a polycondensation reaction (esterification reaction or transesterification reaction) between a widely known polyhydric alcohol and a polyhydric carboxylic acid or its anhydride or alkyl ester.
For example, the diol (c1) and the carboxylic acid component (c2) are charged into a reaction kettle and heated to raise the temperature, thereby carrying out an esterification reaction or a transesterification reaction, while distilling off water or alcohol produced in this reaction. The reaction is continued until a predetermined acid value is reached. If necessary, a polymerization catalyst such as tetrabutyl titanate, dibutyltin oxide, manganese acetate, zinc acetate, tin acetate can be used.
This reaction may be carried out under normal pressure or reduced pressure, but in order to obtain a high molecular weight, a reaction under reduced pressure is preferred. The molecular weight can be adjusted by adjusting the charging ratio between the diol (c1) and the carboxylic acid component (c2).
The reaction between the diol (c1) and the carboxylic acid component (c2) is preferably performed in the absence of a solvent.
In the reaction of the diol (c1) and the carboxylic acid component (c2), the temperature is gradually raised from the temperature at which the dehydration or dealcoholization reaction starts, and is preferably maintained at 200 to 250 ° C. for several hours, and at 220 to 240 ° C. for 3 hours. It is more preferable to hold for 5 hours. Moreover, when making it high molecular weight under pressure reduction, reaction is continued at 230-250 degreeC for 1 to 8 hours by the pressure reduction degree of 5 mmHg or less.
本発明で用いられる水酸基を有するポリエステル樹脂(c3)の原料として、ジオール(c1)と、二塩基酸、二塩基酸無水物、及び二塩基酸のアルキルエステルからなる群より選ばれる少なくとも1種以上のカルボン酸成分(c2)に特に制限はないが、得られる水酸基を有するポリエステル樹脂(c3)としては、分岐型より直鎖型のものが好ましい。
即ち、原料として用いるジオール(c1)と、カルボン酸成分(c2)は、両者とも2官能であるが、必要に応じて3官能以上の多価アルコールや多塩基酸類を併用する場合には、アルコール成分・酸成分の内、それぞれ3モル%以下に留めることが好ましい。3官能以上のアルコール成分・酸成分が3モル%以上になると、分子量を大きくすることが出来ず、接着強度が低下する。
また、多価アルコール及び多塩基酸に特に制限はないが、ジオール(c1)、カルボン酸成分(c2)、および必要に応じて用いられる3官能以上の多価アルコールや多塩基酸類の組み合わせとしては、得られる水酸基を有するポリエステル樹脂(c3)のガラス転移温度が30℃〜60℃になるように組み合わせることが好ましい。ガラス転移温度が30℃以下になると、本発明のカルボキシル基を有するポリエステル樹脂から得られる塗料や接着剤の耐熱性が低下したり、ブロッキング現象が生じやすい。一方、ガラス転移温度が60℃以上になると、加工性が低下したり、接着強度が低下する場合がある。
As a raw material of the polyester resin (c3) having a hydroxyl group used in the present invention, at least one selected from the group consisting of diol (c1), dibasic acid, dibasic acid anhydride, and alkyl ester of dibasic acid Although there is no restriction | limiting in particular in carboxylic acid component (c2) of this, As a polyester resin (c3) which has a hydroxyl group obtained, a linear type thing is preferable rather than a branched type.
That is, the diol (c1) and the carboxylic acid component (c2) used as raw materials are both bifunctional, but if necessary, a trifunctional or higher polyhydric alcohol or a polybasic acid is used together with alcohol. Of the components and acid components, it is preferable to keep them at 3 mol% or less. When the trifunctional or higher alcohol component / acid component is 3 mol% or more, the molecular weight cannot be increased and the adhesive strength is lowered.
There are no particular restrictions on the polyhydric alcohol and polybasic acid, but as a combination of the diol (c1), the carboxylic acid component (c2), and a trifunctional or higher functional polyhydric alcohol and polybasic acids used as necessary. The polyester resin (c3) having a hydroxyl group to be obtained is preferably combined so that the glass transition temperature is 30 ° C to 60 ° C. When the glass transition temperature is 30 ° C. or lower, the heat resistance of the paint or adhesive obtained from the polyester resin having a carboxyl group of the present invention is lowered or a blocking phenomenon tends to occur. On the other hand, when the glass transition temperature is 60 ° C. or higher, the workability may be reduced or the adhesive strength may be reduced.
本発明における水酸基を有するポリエステル樹脂(c3)の合成に用いる二塩基酸、二塩基酸無水物、あるいは二塩基酸のアルキルエステルであるカルボン酸成分(c2)のうち、芳香族ジカルボン酸類としては、例えばテレフタル酸、イソフタル酸、オルソフタル酸、2,6−ナフタレンジカルボン酸、5−ナトリウムスルホイソフタル酸、無水フタル酸等、
あるいはジメチルテレフタル酸、ジメチルイソフタル酸、ジメチル−5−スルホイソフタル酸ナトリウム塩等の芳香族ジカルボン酸アルキルエステルが挙げられる。
脂環族ジカルボン酸類としては、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、1,4−シクロヘキサンジカルボン酸等が挙げられる。
脂肪族ジカルボン酸類としては、(無水)コハク酸、フマル酸、(無水)マレイン酸、アジピン酸、セバシン酸、アゼライン酸、ハイミック酸等が挙げられる。
カルボン酸成分(c2)は、得られる塗膜の硬度と可撓性を勘案してこれらのうちから適宜選択して使用することができる。
また、必要に応じて用いられる3官能以上の多価カルボン酸類としては、(無水)トリメリット酸、(無水)ピロメリット酸等が挙げられる。
Of the dibasic acid, dibasic acid anhydride, or carboxylic acid component (c2) that is an alkyl ester of dibasic acid used for the synthesis of the polyester resin having a hydroxyl group in the present invention (c3), For example, terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, phthalic anhydride, etc.
Alternatively, aromatic dicarboxylic acid alkyl esters such as dimethylterephthalic acid, dimethylisophthalic acid, and dimethyl-5-sulfoisophthalic acid sodium salt can be used.
Examples of the alicyclic dicarboxylic acids include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, and the like.
Examples of the aliphatic dicarboxylic acids include (anhydrous) succinic acid, fumaric acid, (anhydrous) maleic acid, adipic acid, sebacic acid, azelaic acid, and hymic acid.
The carboxylic acid component (c2) can be used by appropriately selecting from these in consideration of the hardness and flexibility of the obtained coating film.
Examples of the tri- or higher functional carboxylic acid used as necessary include (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid and the like.
本発明における水酸基を有するポリエステル樹脂(c3)の合成に用いるジオール(c1)としては、エチレングリコール、ジエチレングリコール、プロピレングリコール、ネオペンチルグリコール、1,2−プロパンジオール、1,2−ブタンジオール、1,3−ブタンジオール、1,4−ブタンジオール、1,5−ペンタンジオール、1,6−ヘキサンジオール、2−メチル−1,3−プロパンジオール、2−n−ブチル−2−エチル−1,3−プロパンジオール、2,2,4−トリメチル−1,3−ペンタンジオール、2−エチル−1,3−ヘキサンジオール、2−ジエチル−1,3−プロパンジオール、1,9−ノナンジオール、2−メチル−1,8−オクタンジオール、1,4−シクロヘキサンジメタノール、3−メチル−1,5−ペンタンジオール、ビスフェノールAもしくはビスフェノールFにエチレンオキサイドやプロピレンオキサイドを付加したもの、水添ビスフェノールA等の脂肪族二価アルコールが挙げられ、得られる塗膜の硬度と可撓性を勘案してこれらのうちから適宜選択して使用することができる。
また、必要に応じて用いられる3官能以上の多価アルコールとしては、トリメチロールエタン、トリメチロールプロパン、グリセリン、ペンタエリスリトール等が挙げられる。
As the diol (c1) used for the synthesis of the polyester resin (c3) having a hydroxyl group in the present invention, ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, 1,2-propanediol, 1,2-butanediol, 1, 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3 -Propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-diethyl-1,3-propanediol, 1,9-nonanediol, 2- Methyl-1,8-octanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5 Examples include pentanediol, bisphenol A or bisphenol F with addition of ethylene oxide or propylene oxide, and aliphatic dihydric alcohols such as hydrogenated bisphenol A. These are considered in consideration of the hardness and flexibility of the resulting coating film. It can be used by appropriately selecting from among them.
Examples of the trifunctional or higher functional polyhydric alcohol used as necessary include trimethylolethane, trimethylolpropane, glycerin, pentaerythritol and the like.
本発明の水酸基を有するポリエステル樹脂(c3)の数平均分子量(Mn1)は10000〜50000、重量平均分子量(Mw1)は20000〜70000であることが好ましい。より好ましくは、数平均分子量(Mn1)は15000〜30000、重量平均分子量(Mw1)は25000〜60000である。
本発明のカルボキシル基を有するポリエステル樹脂は、前述のように水酸基を有するポリエステル樹脂(c3)を、溶剤の存在下に多塩基酸もしくはその無水物(c4)と反応させて得られるものであり、その反応方法を工夫することにより、水酸基を有するポリエステル樹脂(c3)の分子末端のみならず、末端以外の部位にもカルボキシル基を導入することに特徴がある。
なお、本発明でいう「多塩基酸」とは、「二塩基酸」は含まないものである。
さらに、本発明は、水酸基を有するポリエステル樹脂(c3)を多塩基酸もしくはその無水物(c4)で鎖延長して分子量を増大することに特徴があり、本発明のカルボキシル基を有するポリエステル樹脂の数平均分子量(Mn2)及び重量平均分子量(Mw2)のいずれもが、前記水酸基を有するポリエステル樹脂(c3)の数平均分子量(Mn1)及び重量平均分子量(Mw1)それぞれの少なくとも1.2倍であることが重要である。
水酸基を有するポリエステル樹脂(c3)の分子量が小さいと、被膜の硬化時に、分子中に導入されたカルボキシル基と架橋剤との架橋点間分子量が小さくなり、強固な接着性を得ることが出来ない。
また、水酸基を有するポリエステル樹脂(c3)と多塩基酸もしくはその無水物(c4)との反応は逐次的に次々と鎖延長する反応ではなく、水酸基を有するポリエステル樹脂(c3)の2分子づつが繋がって1分子を形成しているものと推察される。
カルボキシル基を有するポリエステル樹脂の数平均分子量(Mn2)及び重量平均分子量(Mw2)のいずれもが、前記水酸基を有するポリエステル樹脂(c3)の数平均分子量(Mn1)及び重量平均分子量(Mw1)それぞれの少なくとも1.2倍となるためには、水酸基を有するポリエステル樹脂(c3)の分子の35%以上が2分子づつ繋がる必要があり、100%の分子が2分子づつ繋がると、前記水酸基を有するポリエステル樹脂(c3)の数平均分子量(Mn1)及び重量平均分子量(Mw1)それぞれの2倍となる。100%の分子が2分子づつ繋がり、さらにそれらが繋がった場合には2倍以上の分子量となる。
従って、本発明の分子量の大きなカルボキシル基を有するポリエステル樹脂を得るためには、水酸基を有するポリエステル樹脂(c3)の分子量もある程度大きくなければならない。
The number average molecular weight (Mn1) of the polyester resin (c3) having a hydroxyl group of the present invention is preferably 10,000 to 50,000 and the weight average molecular weight (Mw1) is 20,000 to 70000. More preferably, the number average molecular weight (Mn1) is 15000 to 30000, and the weight average molecular weight (Mw1) is 25000 to 60000.
The polyester resin having a carboxyl group of the present invention is obtained by reacting a polyester resin having a hydroxyl group (c3) with a polybasic acid or its anhydride (c4) in the presence of a solvent as described above. By devising the reaction method, it is characterized in that a carboxyl group is introduced not only at the molecular terminal of the polyester resin (c3) having a hydroxyl group but also at a site other than the terminal.
The “polybasic acid” in the present invention does not include “dibasic acid”.
Furthermore, the present invention is characterized in that the molecular weight is increased by chain-extending the polyester resin (c3) having a hydroxyl group with a polybasic acid or its anhydride (c4). Both the number average molecular weight (Mn2) and the weight average molecular weight (Mw2) are at least 1.2 times the number average molecular weight (Mn1) and the weight average molecular weight (Mw1) of the polyester resin (c3) having a hydroxyl group. This is very important.
When the molecular weight of the polyester resin (c3) having a hydroxyl group is small, the molecular weight between the crosslinking points between the carboxyl group introduced into the molecule and the crosslinking agent becomes small at the time of curing the film, and it is not possible to obtain strong adhesiveness. .
Further, the reaction between the polyester resin (c3) having a hydroxyl group and the polybasic acid or its anhydride (c4) is not a reaction in which the chain is successively extended, but two molecules of the polyester resin (c3) having a hydroxyl group. It is assumed that they are connected to form one molecule.
Both the number average molecular weight (Mn2) and the weight average molecular weight (Mw2) of the polyester resin having a carboxyl group are the number average molecular weight (Mn1) and the weight average molecular weight (Mw1) of the polyester resin (c3) having a hydroxyl group. In order to be at least 1.2 times, it is necessary that 35% or more of the molecules of the polyester resin (c3) having a hydroxyl group are linked by 2 molecules, and when 100% of the molecules are linked by 2 molecules, the polyester having the hydroxyl group This is twice the number average molecular weight (Mn1) and the weight average molecular weight (Mw1) of the resin (c3). When 100% of the molecules are connected two by two, and when they are connected, the molecular weight is twice or more.
Therefore, in order to obtain the polyester resin having a carboxyl group having a large molecular weight according to the present invention, the molecular weight of the polyester resin (c3) having a hydroxyl group must be large to some extent.
また、本発明のカルボキシル基を有するポリエステル樹脂の数平均分子量(Mn2)及び重量平均分子量(Mw2)のいずれもが、水酸基を有するポリエステル樹脂(c3)の数平均分子量(Mn1)及び重量平均分子量(Mw1)それぞれの3倍以下であることが好ましい。3倍を超えると、得られる塗料や接着剤の粘度が高くなり、取り扱いや基材への塗布が困難になる。 Moreover, both the number average molecular weight (Mn2) and the weight average molecular weight (Mw2) of the polyester resin having a carboxyl group of the present invention are the number average molecular weight (Mn1) and the weight average molecular weight of the polyester resin (c3) having a hydroxyl group ( Mw1) It is preferably 3 times or less of each. When it exceeds 3 times, the viscosity of the obtained paint or adhesive becomes high, and handling and application to a substrate become difficult.
水酸基を有するポリエステル樹脂(c3)と反応させる多塩基酸もしくはその無水物(c4)は、四塩基酸もしくはその無水物を用いることが好ましい。このような化合物としては、例えば、(無水)ピロメリット酸やメチルシクロヘキセンテトラカルボン酸(二無水物)、ベンゾフェノンテトラカルボン酸(二無水物)、エチレングリコールビストリメリテート(二無水物)、グリセリルビス(アンヒドロトリメリテート)モノアセテート等が挙げられる。
これらの内、(無水)ピロメリット酸やエチレングリコールビストリメリテート(二無水物)が反応制御や経済性の面で好ましい。これら四塩基酸もしくはその無水物の添加量としては、本発明のカルボキシル基を有するポリエステル樹脂に与える酸価で決められる。
例えば、エチレングリコールビストリメリテート(二無水物)を反応させる場合、酸価を5mgKOH/gとしたいときには、前記水酸基含有ポリエステル樹脂(c3)100重量部に対して2.0重量部程度添加し、酸価を40mgKOH/gとしたい時には、15重量部程度添加すればよい。
四塩基酸もしくはその無水物の添加量が少ないと、水酸基を有するポリエステル樹脂末端の水酸基の当量に対して不足となり、鎖延長反応が不十分となり、十分に大きな分子量が得られなくなる。また四塩基酸もしくはその無水物の添加量が多過ぎると、水酸基を有するポリエステル樹脂末端の水酸基の当量に対して過剰となり、鎖延長反応が途中で停止してしまい、同様に十分に大きな分子量が得られなくなる。
As the polybasic acid or its anhydride (c4) to be reacted with the polyester resin (c3) having a hydroxyl group, it is preferable to use a tetrabasic acid or its anhydride. Examples of such compounds include (anhydrous) pyromellitic acid, methylcyclohexene tetracarboxylic acid (dianhydride), benzophenone tetracarboxylic acid (dianhydride), ethylene glycol bistrimellitate (dianhydride), glyceryl bis And (anhydrotrimellitate) monoacetate.
Of these, (anhydrous) pyromellitic acid and ethylene glycol bistrimellitate (dianhydride) are preferred in terms of reaction control and economy. The addition amount of these tetrabasic acids or their anhydrides is determined by the acid value given to the polyester resin having a carboxyl group of the present invention.
For example, in the case of reacting ethylene glycol bistrimellitate (dianhydride), when the acid value is 5 mgKOH / g, about 2.0 parts by weight is added to 100 parts by weight of the hydroxyl group-containing polyester resin (c3). When the acid value is desired to be 40 mgKOH / g, about 15 parts by weight may be added.
If the amount of tetrabasic acid or its anhydride is small, the amount of the hydroxyl group-terminated polyester resin will be insufficient with respect to the equivalent amount of the hydroxyl group, the chain extension reaction will be insufficient, and a sufficiently large molecular weight will not be obtained. If the amount of tetrabasic acid or its anhydride added is too large, it will be excessive with respect to the equivalent amount of the hydroxyl group at the end of the polyester resin having a hydroxyl group, and the chain extension reaction will be stopped in the middle, as well as a sufficiently large molecular weight. It can no longer be obtained.
本発明のカルボキシル基を有するポリエステル樹脂の酸価は5〜40mgKOH/gであることが望ましい。酸価が5mgKOH/g未満では、基材に対する密着性が不十分となりやすく、また架橋剤との架橋反応が不十分となりやすい。酸価が40mgKOH/gを超えると架橋剤との架橋が進み過ぎて密着性が低下したり、被膜の耐水性が低下したりする傾向にある。また、酸価が40mgKOH/g以上になるように多塩基酸もしくはその無水物を添加すると、カルボキシル基を有するポリエステル樹脂の分子量が、水酸基を有するポリエステル樹脂(c3)の分子量より小さくなる場合がある。 The acid value of the polyester resin having a carboxyl group of the present invention is preferably 5 to 40 mgKOH / g. When the acid value is less than 5 mgKOH / g, the adhesion to the substrate tends to be insufficient, and the crosslinking reaction with the crosslinking agent tends to be insufficient. When the acid value exceeds 40 mgKOH / g, the crosslinking with the crosslinking agent proceeds excessively, and the adhesiveness tends to decrease, or the water resistance of the coating tends to decrease. Moreover, when a polybasic acid or its anhydride is added so that an acid value may be 40 mgKOH / g or more, the molecular weight of the polyester resin which has a carboxyl group may become smaller than the molecular weight of the polyester resin (c3) which has a hydroxyl group. .
本発明のカルボキシル基を有するポリエステル樹脂のガラス転移温度は30℃〜60℃であることが好ましい。より好ましくは40℃〜50℃である。ガラス転移温度が30℃以下になると、得られる塗膜と基材との密着性は良好となるが、ポリエステル樹脂の凝集力が不十分となりやすく、凝集破壊を引き起こしやすくなる。ガラス転移温度が60℃以上になると、基材との界面において内部応力が増大し、密着性の低下を引き起こしやすくなる。
本発明のカルボキシル基を有するポリエステル樹脂は、塗料や接着剤に用いられるが、これらは常温の環境下だけではなく、低温や高温の環境下で使用される場合が多い。低温の環境下で使用される場合には、ポリエステル樹脂のガラス転移温度は低い方が好ましく、高温の環境下で使用される場合にはガラス転移温度は高い方が好ましい。
It is preferable that the glass transition temperature of the polyester resin which has a carboxyl group of this invention is 30 to 60 degreeC. More preferably, it is 40 degreeC-50 degreeC. When the glass transition temperature is 30 ° C. or lower, the adhesion between the obtained coating film and the substrate is good, but the cohesive force of the polyester resin tends to be insufficient, and cohesive failure is likely to occur. When the glass transition temperature is 60 ° C. or higher, the internal stress increases at the interface with the base material, which tends to cause a decrease in adhesion.
The polyester resin having a carboxyl group of the present invention is used in paints and adhesives, and these are often used not only in a normal temperature environment but also in a low or high temperature environment. When used in a low temperature environment, the glass transition temperature of the polyester resin is preferably low, and when used in a high temperature environment, the glass transition temperature is preferably high.
本発明においては、水酸基を有するポリエステル樹脂(c3)を溶剤に溶解した後、前記溶剤の沸点以下の温度、もしくは前記溶剤の沸点の温度で還流下に、水酸基を有するポリエステル樹脂(c3)を多塩基酸もしくはその無水物(c4)と反応させることに特徴がある。即ち、このような方法によりカルボキシル基を有するポリエステル樹脂の数平均分子量(Mn2)及び重量平均分子量(Mw2)のいずれもが、前記水酸基を有するポリエステル樹脂(c3)の数平均分子量(Mn1)及び重量平均分子量(Mw1)の少なくとも1.2倍となり得る。 In the present invention, after the polyester resin (c3) having a hydroxyl group is dissolved in a solvent, the polyester resin (c3) having a hydroxyl group is added under reflux at a temperature not higher than the boiling point of the solvent or at a boiling point of the solvent. It is characterized by reacting with a basic acid or its anhydride (c4). That is, the number average molecular weight (Mn2) and the weight average molecular weight (Mw2) of the polyester resin having a carboxyl group by such a method are the same as the number average molecular weight (Mn1) and the weight of the polyester resin (c3) having a hydroxyl group. It can be at least 1.2 times the average molecular weight (Mw1).
水酸基を有するポリエステル樹脂(c3)と多塩基酸もしくはその無水物(c4)との反応は、溶剤の存在下においておこなうことが重要であり、使用できる溶剤としては、アルコール類やセロソルブ類のような、水酸基を有する溶剤を除いて、水酸基を有するポリエステル樹脂(c3)及びカルボキシル基を有するポリエステル樹脂のいずれも溶解するような溶剤であれば制限なく使用できる。
例えばトルエン、キシレン、ソルベッソ#100、ソルベッソ#150等の芳香族炭化水素類、
ヘキサン、ヘプタン、オクタン、デカン等の脂肪族炭化水素類、
酢酸メチル、酢酸エチル、酢酸イソプロピル、酢酸ブチル、酢酸アミル、ギ酸エチル、プロピオン酸ブチル、セロソルブアセテート等のエステル類、
アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、イソホロン等のケトン類、
ジオキサン、ジエチルエーテル、テトラヒドロフラン等のエーテル類の各種溶剤が挙げられ、これらの中でも芳香族炭化水素類とケトン類との混合溶剤が好適に用いられる。
これら溶剤は単独で用いてもよいし、2種類以上を混合して用いても良い。
水酸基を有するポリエステル樹脂(c3)と多塩基酸もしくはその無水物(c4)との反応を無溶剤下でおこなった場合、目的の生成物が得られる以前にゲル化に至りやすい。
また、水酸基を有するポリエステル樹脂(c3)と多塩基酸もしくはその無水物(c4)との反応においては、反応温度は70〜140℃であることが好ましく、90〜120℃であることがより好ましい。
また、上記反応温度は、水酸基を有するポリエステル樹脂(c3)を得るためのジオール(c1)とカルボン酸成分(c2)との反応における反応温度よりも低い温度であることが好ましい。
水酸基を有するポリエステル樹脂(c3)を溶剤に溶解して、比較的低い温度で多塩基酸もしくはその無水物(c4)を反応させることにより、前記水酸基を有するポリエステル樹脂(c3)の数平均分子量(Mn1)及び重量平均分子量(Mw1)それぞれの少なくとも1.2倍となり得る。
It is important that the reaction between the polyester resin (c3) having a hydroxyl group and the polybasic acid or its anhydride (c4) is carried out in the presence of a solvent. Examples of usable solvents include alcohols and cellosolves. Any solvent that can dissolve both the polyester resin having a hydroxyl group (c3) and the polyester resin having a carboxyl group, excluding the solvent having a hydroxyl group, can be used without limitation.
For example, aromatic hydrocarbons such as toluene, xylene, Solvesso # 100, Solvesso # 150,
Aliphatic hydrocarbons such as hexane, heptane, octane, decane,
Esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, ethyl formate, butyl propionate, cellosolve acetate,
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone,
Examples of the solvent include ethers such as dioxane, diethyl ether, and tetrahydrofuran. Among these, a mixed solvent of an aromatic hydrocarbon and a ketone is preferably used.
These solvents may be used alone or in combination of two or more.
When the reaction between the polyester resin (c3) having a hydroxyl group and the polybasic acid or its anhydride (c4) is carried out in the absence of a solvent, gelation is likely to occur before the desired product is obtained.
Moreover, in the reaction of the polyester resin (c3) having a hydroxyl group and the polybasic acid or anhydride (c4), the reaction temperature is preferably 70 to 140 ° C, more preferably 90 to 120 ° C. .
The reaction temperature is preferably lower than the reaction temperature in the reaction of the diol (c1) and the carboxylic acid component (c2) for obtaining the polyester resin (c3) having a hydroxyl group.
The polyester resin (c3) having a hydroxyl group is dissolved in a solvent and reacted with a polybasic acid or its anhydride (c4) at a relatively low temperature, whereby the number average molecular weight of the polyester resin (c3) having a hydroxyl group ( Mn1) and weight average molecular weight (Mw1) can be at least 1.2 times each.
本発明のカルボキシル基を有するポリエステル樹脂を得るための、水酸基を有するポリエステル樹脂(c3)と多塩基酸もしくはその無水物(c4)との反応においては、四級アンモニウム塩を触媒として用いることが好ましい。
触媒として用いられる四級アンモニウム塩としては、臭化テトラメチルアンモニウム、臭化テトラエチルアンモニウム、臭化テトラ−n−ブチルアンモニウム、塩化テトラメチルアンモニウム、塩化トリメチルベンジルアンモニウム、塩化トリエチルベンジルアンモニウム、水酸化テトラメチルアンモニウム、水酸化トリメチルベンジルアンモニウム、水酸化テトラ−n−ブチルアンモニウム、ヨウ化テトラメチルアンモニウム、ヨウ化テトラ−n−ブチルアンモニウム等が挙げられる。これらの触媒の添加量としては、反応温度にもよるが通常、水酸基を有するポリエステル樹脂(c3)100重量部に対して0.1〜1重量部用いられる。
In the reaction of the polyester resin having a hydroxyl group (c3) and the polybasic acid or its anhydride (c4) for obtaining the polyester resin having a carboxyl group of the present invention, it is preferable to use a quaternary ammonium salt as a catalyst. .
The quaternary ammonium salts used as catalysts include tetramethylammonium bromide, tetraethylammonium bromide, tetra-n-butylammonium bromide, tetramethylammonium chloride, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetramethyl hydroxide. Examples include ammonium, trimethylbenzylammonium hydroxide, tetra-n-butylammonium hydroxide, tetramethylammonium iodide, and tetra-n-butylammonium iodide. The amount of these catalysts added is usually 0.1 to 1 part by weight with respect to 100 parts by weight of the polyester resin (c3) having a hydroxyl group, although it depends on the reaction temperature.
本発明のカルボキシル基を有するポリエステル樹脂は、エポキシ化合物を架橋剤として配合したポリエステル樹脂組成物として特に好ましく用いられる。架橋剤としてはエポキシ化合物以外に、アミノ樹脂、イソシアネート化合物、レゾール型フェノール樹脂等も好適に用いられる。
エポキシ化合物の例としては、ビスフェノールAのジグリシジルエーテル及びそのオリゴマー、オルトフタル酸ジグリシジルエステル、イソフタル酸ジグリシジルエステル、テレフタル酸ジグリシジルエステル、p−ヒドロキシ安息香酸ジグリシジルエステル、テトラヒドロフタル酸ジグリシジルエステル、ヘキサヒドロフタル酸ジグリシジルエステル、コハク酸ジグリシジルエステル、アジピン酸ジグリシジルエステル、セバシン酸ジグリシジルエステル、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、1,4−ブタンジオールジグリシジルエーテル、1,6−ヘキサンジオールジグリシジルエーテル、及びアルキレングリコールジグリシジルエーテル類、トリメリット酸トリグリシジルエステル、トリグリシジルイソシアヌレート、1,4−グリシジルオキシベンゼン、ジグリシジルプロピレン尿素、グリセロールトリグリシジルエーテル、トリメチロールエタングリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテル、グリセロールアルキレンオキサイド付加物のトリグリシジルエーテル、テトラフェニルグリシジルエーテルエタン、トリフェニルグリシジルエーテルエタン等が挙げられる。また、フェノールやクレゾールのノボラック型エポキシ樹脂やナフタレン型やジシクロペンタジエン型エポキシ樹脂等も挙げられる。これらは、それぞれ単独、または併用して用いることが出来る。
The polyester resin having a carboxyl group of the present invention is particularly preferably used as a polyester resin composition containing an epoxy compound as a crosslinking agent. As the crosslinking agent, in addition to the epoxy compound, an amino resin, an isocyanate compound, a resol type phenol resin, and the like are also preferably used.
Examples of epoxy compounds include diglycidyl ether of bisphenol A and oligomers thereof, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-hydroxybenzoic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester , Hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, and alkylene glycol diglycidyl ethers, trimellitic acid triglycidyl ester , Triglycidyl isocyanurate, 1,4-glycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylol ethane glycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerol alkylene oxide adduct tri Examples thereof include glycidyl ether, tetraphenyl glycidyl ether ethane, and triphenyl glycidyl ether ethane. Moreover, the novolak-type epoxy resin of phenol or cresol, the naphthalene type, the dicyclopentadiene type epoxy resin, etc. are mentioned. These can be used alone or in combination.
アミノ樹脂の例としては、尿素、メラミン、ベンゾグアナミン、アセトグアナミン、ステログアナミン、スピログアナミン、ジシアンジアミド等のアミノ成分と、ホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、ベンツアルデヒド等のアルデヒド成分との反応によって得られるメチロール化アミノ樹脂が挙げられる。このメチロール化アミノ樹脂のメチロール基を、炭素数1〜6のアルコールによってエーテル化したものも上記アミノ樹脂に含まれる。これらは、単独もしくは併用して使用できる。 Examples of amino resins include methylols obtained by reaction of amino components such as urea, melamine, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, and dicyandiamide with aldehyde components such as formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde. An amino resin is mentioned. Those obtained by etherifying the methylol group of the methylolated amino resin with an alcohol having 1 to 6 carbon atoms are also included in the amino resin. These can be used alone or in combination.
架橋剤として用いられるイソシアネート化合物の例としては、芳香族、脂環族、脂肪族のジイソシアネート化合物、3価以上のポリイソシアネート化合物があり、低分子化合物、高分子化合物のいずれでも良い。例えば、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、トルエンジイソシアネート、ジフェニルメタンジイソシアネート、水素化ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、水素化キシリレンジイソシアネート、イソホロンジイソシアネート、或いはこれらイソシアネート化合物の3量体、及びこれらイソシアネート化合物の過剰量と例えばエチレングリコール、プロピレングリコール、トリメチロールプロパン、ソルビトール、エチレンジアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等の低分子活性水素化合物または各種ポリエステルポリオール類、ポリエーテルポリオール類、ポリアミド類等の高分子活性水素化合物等と反応させて得られる末端イソシアネート基含有化合物が挙げられる。これらはそれぞれ単独または併用して使用できる。 Examples of the isocyanate compound used as a crosslinking agent include aromatic, alicyclic, and aliphatic diisocyanate compounds, and trivalent or higher polyisocyanate compounds, which may be either low molecular compounds or high molecular compounds. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, or trimers of these isocyanate compounds, and excess amounts of these isocyanate compounds And low molecular active hydrogen compounds such as ethylene glycol, propylene glycol, trimethylolpropane, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, and triethanolamine, or high molecular activities such as various polyester polyols, polyether polyols, and polyamides Terminal isocyanate obtained by reacting with hydrogen compounds, etc. Over preparative group-containing compound. These can be used alone or in combination.
また、接着剤組成物や塗料組成物としてポットライフが必要な場合、イソシアネート化合物としてはブロック化イソシアネートの使用が好ましい。イソシアネートブロック化剤としては、例えば、フェノール、チオフェノール、メチルチオフェノール、クレゾール、キシレノール、レゾルシノール、ニトロフェノール、クロロフェノール等のフェノール類、アセトオキシム、メチルエチルケトオキシム、シクロヘキサノンオキシム等のオキシム類、
メタノール、エタノール、プロパノール、ブタノール等のアルコール類、
エチレンクロルヒドリン、1,3−ジクロロ−2−プロパノール等のハロゲン置換アルコール類、
t−ブタノール、t−ペンタノール等の第3級アルコール類、
ε−カプロラクタム等のラクタム類
が挙げられ、その他、芳香族アミン類、イミド類、アセチルアセトン、アセト酢酸エステル、マロン酸エチルエステル等の活性メチレン化合物、メルカプタン類、イミン類、尿素類、ジアリール化合物類、重亜硫酸ソーダ等も挙げられる。
ブロック化イソシアネート化合物は前記イソシアネート化合物とブロック化剤とを従来公知の方法により、反応させて得られ、それぞれ単独、もしくは併用して使用できる。
Moreover, when a pot life is required as an adhesive composition or a coating composition, it is preferable to use a blocked isocyanate as the isocyanate compound. As the isocyanate blocking agent, for example, phenols such as phenol, thiophenol, methylthiophenol, cresol, xylenol, resorcinol, nitrophenol, chlorophenol, oximes such as acetooxime, methyl ethyl ketoxime, cyclohexanone oxime,
Alcohols such as methanol, ethanol, propanol, butanol,
Halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol;
tertiary alcohols such as t-butanol and t-pentanol;
Examples include lactams such as ε-caprolactam, other active amine compounds such as aromatic amines, imides, acetylacetone, acetoacetate ester, and malonic acid ethyl ester, mercaptans, imines, ureas, diaryl compounds, Examples include sodium bisulfite.
The blocked isocyanate compound is obtained by reacting the isocyanate compound and the blocking agent by a conventionally known method, and each can be used alone or in combination.
本発明のポリエステル樹脂組成物は、カルボキシル基を有するポリエステル樹脂/架橋剤が99/1〜50/50(重量比)の範囲内で含有することが好ましい。さらに好ましくは、カルボキシル基を有するポリエステル樹脂/架橋剤が97/3〜60/40(重量比)の範囲内が良好な性能を示す。架橋剤の含有量が1%未満の場合、ポリエステル樹脂の硬化が不十分となり、強固な接着強度が得られない。架橋剤の含有量が50%を超えると硬化が過度になり、所謂硬化歪が生じて接着強度が低下する。エポキシ化合物やイソシアネート化合物を架橋剤として用いる場合には、カルボキシル基を有するポリエステル樹脂のカルボキシル基と当量の架橋剤量とすることが好ましい。アミノ樹脂やレゾール型フェノール樹脂を架橋剤として用いる場合には、アミノ樹脂やレゾール型フェノール樹脂は自己縮合反応も生じるので、カルボキシル基を有するポリエステル樹脂のカルボキシル基の当量より多く用いた方が好ましい。 The polyester resin composition of the present invention preferably contains a carboxyl group-containing polyester resin / crosslinking agent within a range of 99/1 to 50/50 (weight ratio). More preferably, the polyester resin / crosslinking agent having a carboxyl group has a good performance within a range of 97/3 to 60/40 (weight ratio). When the content of the cross-linking agent is less than 1%, the polyester resin is not sufficiently cured and a strong adhesive strength cannot be obtained. When the content of the crosslinking agent exceeds 50%, curing becomes excessive, so-called curing strain is generated, and the adhesive strength is lowered. When using an epoxy compound or an isocyanate compound as a crosslinking agent, the amount of the crosslinking agent is preferably equivalent to the carboxyl group of the polyester resin having a carboxyl group. When an amino resin or a resol type phenol resin is used as a crosslinking agent, the amino resin or the resol type phenol resin also causes a self-condensation reaction. Therefore, it is preferable to use more than the equivalent of the carboxyl group of the polyester resin having a carboxyl group.
本発明のポリエステル樹脂組成物には、硬化触媒を用いることが出来る。例えば、架橋剤にエポキシ化合物を用いる場合には3級アミン化合物、トリフェニルホスフィン等の有機リン化合物等を使用することが出来る。架橋剤にアミノ樹脂やレゾール型フェノール樹脂を用いる場合には、p−トルエンスルフォン酸、ドデシルベンゼンスルフォン酸、ジノニルナフタレンジスルフォン酸等の有機スルフォン酸化合物やそれらのアミン中和物、リン酸化合物などを使用することが出来る。イソシアネート化合物を架橋剤として用いる場合には、3級アミン化合物、有機スズ化合物等を使用することが出来る。これらは単独もしくは2種類以上を任意に選択できる。 A curing catalyst can be used in the polyester resin composition of the present invention. For example, when an epoxy compound is used as the crosslinking agent, a tertiary amine compound, an organic phosphorus compound such as triphenylphosphine, or the like can be used. When an amino resin or a resol type phenol resin is used as a crosslinking agent, organic sulfonic acid compounds such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenedisulfonic acid, neutralized amines thereof, and phosphoric acid compounds Etc. can be used. When an isocyanate compound is used as a crosslinking agent, a tertiary amine compound, an organic tin compound, or the like can be used. These can be arbitrarily selected alone or in combination of two or more.
本発明のポリエステル樹脂組成物は、接着剤組成物として用いる場合には、必要に応じて難燃剤やフィラーを添加することが出来る。難燃剤としては、窒素系難燃剤、リン系難燃剤、無機物系難燃剤等が挙げられ、フィラーとしては、熱膨張収縮の抑制や疎水化を目的として、シリカ、アルミナ、珪藻土、酸化チタン、酸化亜鉛、酸化マグネシウム等が挙げられる。一方、塗料組成物として用いる場合には、必要に応じて酸化チタンや有機顔料等の着色剤や、塗膜表面に潤滑性を付与するための、シリコーン系やワックス系の潤滑剤、消泡剤、分散剤等を添加しても良い。 When the polyester resin composition of the present invention is used as an adhesive composition, a flame retardant or a filler can be added as necessary. Examples of flame retardants include nitrogen-based flame retardants, phosphorus-based flame retardants, inorganic-based flame retardants, and fillers include silica, alumina, diatomaceous earth, titanium oxide, and oxide for the purpose of suppressing thermal expansion and shrinkage and making them hydrophobic. Examples include zinc and magnesium oxide. On the other hand, when used as a coating composition, if necessary, colorants such as titanium oxide and organic pigments, silicone-based and wax-based lubricants and antifoaming agents for imparting lubricity to the coating surface. A dispersant or the like may be added.
本発明のポリエステル樹脂組成物は、前記したカルボキシル基を有するポリエステル樹脂と架橋剤とを公知の有機溶剤に溶解した状態で使用してもよいし、溶融押し出しで用いてもよい。使用する有機溶剤としては、トルエン、キシレン、ソルベッソ等の芳香族系炭化水素類、酢酸エチル、酢酸ブチル、エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のエステル類、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、イソホロン等のケトン類、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノ−n−ブチルエーテル等のエーテル類等が挙げられ、溶解性や蒸発速度等を考慮して選択される。 The polyester resin composition of the present invention may be used in a state where the above-described polyester resin having a carboxyl group and a crosslinking agent are dissolved in a known organic solvent, or may be used by melt extrusion. Organic solvents to be used include aromatic hydrocarbons such as toluene, xylene and solvesso, esters such as ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. And ketones such as isophorone, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol mono-n-butyl ether, and the like, which are selected in consideration of solubility and evaporation rate.
本発明のポリエステル樹脂組成物は、接着剤としては自動車・電気機器・電子機器・産業機器・建材等の用途に使用される各種プラスチック、プラスチックフィルム、金属、無機材料等の基材に対して強固な接着性を有するものとして、それらの分野で広く用いられるものである。一方、塗料用としては、家電・建材・自動車等に使用する金属材料やプラスチック材料、また、食品や飲料を入れる金属容器やキャップ等に広く用いられる。
プラスチックとしては、PET、PP、PE、ポリウレタン、ポリカーボネート、ポリイミド等の各種プラスチック及びそれらのフィルムが用いられ、それらの素材そのままで、あるいはコロナ処理や、電子線照射、UV照射等の表面処理を施した素材が用いられる。
また、PVAやトリアセチルセルロース、シクロオレフィンフィルム等のフラットパネル光学用途フィルムの接着剤としても用いることが出来る。
金属素材としては、熱延鋼板、冷延鋼板、溶融亜鉛メッキ鋼板、電気亜鉛メッキ鋼板、スズメッキ鋼板、ステンレス鋼板、銅メッキ鋼板、ティンフリスチール、ニッケルメッキ鋼板、クロム処理鋼板、アルミニウム板等が用いられる。また、ポリイミドフィルムに銅箔をラミネートしてエッチング処理により電気回路を形成した所謂フレキシブルプリントサーキット(FPC)基板等にも好適に用いられる。
The polyester resin composition of the present invention is strong as an adhesive against substrates such as various plastics, plastic films, metals, and inorganic materials used in applications such as automobiles, electrical equipment, electronic equipment, industrial equipment, and building materials. As such, it is widely used in those fields. On the other hand, for paints, it is widely used for metal materials and plastic materials used for home appliances, building materials, automobiles, etc., and metal containers and caps for food and beverages.
As plastics, various plastics such as PET, PP, PE, polyurethane, polycarbonate, polyimide, and films thereof are used, and those materials are used as they are or subjected to surface treatment such as corona treatment, electron beam irradiation, and UV irradiation. Material is used.
It can also be used as an adhesive for flat panel optical films such as PVA, triacetylcellulose, and cycloolefin films.
Metal materials include hot-rolled steel sheet, cold-rolled steel sheet, hot-dip galvanized steel sheet, electrogalvanized steel sheet, tin-plated steel sheet, stainless steel sheet, copper-plated steel sheet, tin-free steel, nickel-plated steel sheet, chrome-treated steel sheet, aluminum plate, etc. It is done. Further, it is also suitably used for a so-called flexible printed circuit (FPC) substrate in which an electric circuit is formed by laminating a copper foil on a polyimide film and etching treatment.
本発明のポリエステル樹脂組成物を用いた接着剤組成物や塗料組成物は、刷毛塗りや、浸漬塗布、ロールコーター塗装、スプレー塗装、カーテン塗装等の従来公知の方法により塗布される。各種基材に直接塗布して硬化させる方法が一般的であるが、剥離紙等に塗布して、乾燥により有機溶剤を揮発させたフィルム状のものを基材に貼って、積層物を作った後に硬化させる方法も好適に用いられる。 The adhesive composition or coating composition using the polyester resin composition of the present invention is applied by a conventionally known method such as brush coating, dip coating, roll coater coating, spray coating, curtain coating or the like. The method of applying and curing directly on various substrates is common, but it was applied to release paper, etc., and a film was formed by volatilizing the organic solvent by drying, and a laminate was made. A method of later curing is also preferably used.
本発明のポリエステル樹脂組成物の硬化方法は、従来公知の各種方法を用いることが出来る。例えば、40〜60℃の温度で3日〜5日程度放置して硬化させる所謂エージング方法や、100℃〜150℃の温度で1時間〜3時間程度の硬化、180℃〜200℃の温度で5分〜10分程度の硬化、200℃以上の温度で数秒〜1分間程度の硬化方法等が用いられる。具体的な方法としては、恒温室でのエージングや、熱風乾燥炉、遠赤外線乾燥炉、高周波誘導加熱炉等の加熱方法が用いられる。また、加熱プレス機による加圧下での加熱等の方法も用いられることもある。 The conventionally well-known various methods can be used for the hardening method of the polyester resin composition of this invention. For example, a so-called aging method in which it is allowed to stand for 3 to 5 days at a temperature of 40 to 60 ° C., curing at a temperature of 100 to 150 ° C. for about 1 to 3 hours, or at a temperature of 180 to 200 ° C. Curing for about 5 minutes to 10 minutes, a curing method for about several seconds to 1 minute at a temperature of 200 ° C. or higher, and the like are used. As a specific method, aging in a thermostatic chamber, a heating method such as a hot air drying furnace, a far infrared drying furnace, a high frequency induction heating furnace, or the like is used. In addition, a method such as heating under pressure by a heating press may be used.
以下、実施例を挙げて、本発明を具体的に説明する。実施例において単に部あるいは%とあるものは、重量部あるいは重量%をそれぞれ示す。 Hereinafter, the present invention will be specifically described with reference to examples. In the examples, “parts” or “%” means “parts by weight” or “% by weight”, respectively.
合成例I:水酸基を有するポリエステル樹脂の合成
[合成例1](水酸基を有するポリエステル樹脂A−1の合成)
撹拌機、温度計、窒素ガス導入管及び還流脱水装置を備えたフラスコに、ジメチルテレフタル酸262.7部、エチレングリコール91.1部、ネオペンチルグリコール91.7部、2−メチル−1,3−プロパンジオール52.9部及び酢酸亜鉛0.035部を仕込んだ。原料を加熱溶融して撹拌できるようになったら撹拌を開始して、留出するメタノールを常圧下に系外に除きながら170℃から220℃まで3時間かけて徐々に昇温し、220℃で1時間保持した。内温を一旦170℃まで冷却し、イソフタル酸135.7部、1,4−シクロヘキサンジカルボン酸65.9部を加え、留出する水を常圧下に系外に除きながら240℃まで3時間かけて昇温し、さらに240℃で保持して、酸価が14.6になるまで反応を続けた。次いで、テトラブチルチタネート0.056部を加え、1時間かけて10mmHgまで減圧初期重合を行い、その後、5mmHg以下に減圧して8時間重合を続け、目標分子量に達したことを確認して水酸基を有するポリエステル樹脂A−1を得た。その特性値を表−1に示す。
Synthesis Example I: Synthesis of polyester resin having hydroxyl group [Synthesis Example 1] (Synthesis of polyester resin A-1 having hydroxyl group)
In a flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and reflux dehydrator, dimethyl terephthalic acid 262.7 parts, ethylene glycol 91.1 parts, neopentyl glycol 91.7 parts, 2-methyl-1,3 -Charge 52.9 parts propanediol and 0.035 parts zinc acetate. When the raw material can be heated and melted and stirred, stirring is started and the temperature is gradually increased from 170 ° C. to 220 ° C. over 3 hours while removing distilled methanol out of the system at normal pressure. Hold for 1 hour. The internal temperature is once cooled to 170 ° C., 135.7 parts of isophthalic acid and 65.9 parts of 1,4-cyclohexanedicarboxylic acid are added, and the distilled water is removed from the system under atmospheric pressure, taking 240 hours to 240 ° C. over 3 hours. The reaction was continued until the acid value reached 14.6. Next, 0.056 part of tetrabutyl titanate was added, and the initial polymerization was performed under reduced pressure to 10 mmHg over 1 hour, and then the polymerization was continued under reduced pressure to 5 mmHg or less for 8 hours. Polyester resin A-1 was obtained. The characteristic values are shown in Table-1.
[合成例2〜合成例5](水酸基を有するポリエステル樹脂A−2〜A−5の合成)
合成例1と同様の方法で、表−1の仕込みモル比に従って、それらの合計量を700部として合成を行い、表−1に示した特性値の水酸基を有するポリエステル樹脂A−2〜A−5を得た。
[Synthesis Example 2 to Synthesis Example 5] (Synthesis of polyester resins A-2 to A-5 having a hydroxyl group)
Synthesis was carried out in the same manner as in Synthesis Example 1 according to the charged molar ratios in Table 1, with the total amount being 700 parts, and polyester resins A-2 to A- having hydroxyl groups having the characteristic values shown in Table 1. 5 was obtained.
合成例II:カルボキシル基を有するポリエステル樹脂の合成
[合成例6](カルボキシル基を有するポリエステル樹脂B−1の合成)
合成例1で得られた水酸基を有するポリエステル樹脂A−1、100部をトルエン100部に溶解した。次いで無水ピロメリット酸を2.5部、TBAB(触媒:テトラ−n−ブチルアンモニウムブロミド)を0.5部加え、100℃で6時間反応を続けた。目標の酸価と分子量を確認し、さらにメチルエチルケトンを53.8部加えて均一に溶解した後取り出した。得られたカルボキシル基を有するポリエステル樹脂B−1の特性値を表−2に示す。
Synthesis Example II: Synthesis of polyester resin having carboxyl group [Synthesis Example 6] (Synthesis of polyester resin B-1 having carboxyl group)
100 parts of the polyester resin A-1 having a hydroxyl group obtained in Synthesis Example 1 was dissolved in 100 parts of toluene. Next, 2.5 parts of pyromellitic anhydride and 0.5 part of TBAB (catalyst: tetra-n-butylammonium bromide) were added, and the reaction was continued at 100 ° C. for 6 hours. The target acid value and molecular weight were confirmed, and 53.8 parts of methyl ethyl ketone was further added and dissolved uniformly. The characteristic values of the obtained polyester resin B-1 having a carboxyl group are shown in Table 2.
[合成例7〜15](カルボキシル基を有するポリエステル樹脂B−2〜B−10の合成)
合成例6と同様の方法で、表−2の仕込み重量比に従って合成を行い、表−2に示した特性値のカルボキシル基を有するポリエステル樹脂B−2〜B−10を得た。
[Synthesis Examples 7 to 15] (Synthesis of polyester resins B-2 to B-10 having a carboxyl group)
Synthesis was performed in the same manner as in Synthesis Example 6 according to the charged weight ratios shown in Table 2, and polyester resins B-2 to B-10 having carboxyl groups having the characteristic values shown in Table 2 were obtained.
比較合成例
[比較合成例1](水酸基を有するポリエステル樹脂A−2の溶解)
合成例2で得られた水酸基を有するポリエステル樹脂A−2、100部をトルエン100部、メチルエチルケトン50部に溶解して、水酸基を有するポリエステル樹脂溶液C−1を得た。
Comparative synthesis example [Comparative synthesis example 1] (dissolution of polyester resin A-2 having a hydroxyl group)
100 parts of the polyester resin A-2 having a hydroxyl group obtained in Synthesis Example 2 was dissolved in 100 parts of toluene and 50 parts of methyl ethyl ketone to obtain a polyester resin solution C-1 having a hydroxyl group.
[比較合成例2](カルボキシル基を有するポリエステル樹脂C−2)
合成例2で得られた水酸基を有するポリエステル樹脂A−2、100部をトルエン100部に溶解した。次いで無水トリメリット酸を3.5部、TBABを0.5部加え、100℃で6時間反応を続けた。目標の酸価と分子量を確認し、さらにメチルエチルケトンを55.3部加えて均一に溶解した後取り出した。
得られたカルボキシル基を有するポリエステル樹脂C−2の特性値を表−2に示す。
[Comparative Synthesis Example 2] (Polyester resin C-2 having a carboxyl group)
100 parts of the polyester resin A-2 having a hydroxyl group obtained in Synthesis Example 2 was dissolved in 100 parts of toluene. Next, 3.5 parts of trimellitic anhydride and 0.5 parts of TBAB were added, and the reaction was continued at 100 ° C. for 6 hours. The target acid value and molecular weight were confirmed, and 55.3 parts of methyl ethyl ketone was further added and dissolved uniformly.
The characteristic values of the obtained polyester resin C-2 having a carboxyl group are shown in Table 2.
[比較合成例3、4](カルボキシル基を有するポリエステル樹脂C−3、C−4)
比較合成例2と同様の方法で、表−3の仕込み重量比と反応条件に従って合成を行い、表−3に示した特性値のカルボキシル基を有するポリエステル樹脂C−3、C−4を得た。
[Comparative Synthesis Examples 3 and 4] (Polyester resins C-3 and C-4 having a carboxyl group)
Synthesis was performed in the same manner as in Comparative Synthesis Example 2 in accordance with the charged weight ratios and reaction conditions shown in Table 3, and polyester resins C-3 and C-4 having carboxyl groups having the characteristic values shown in Table 3 were obtained. .
[比較合成例5、6](カルボキシル基を有するポリエステル樹脂C−5、C−6)
トルエンを用いずに無溶剤下で反応をおこなったこと以外は比較合成例2と同様に反応をおこなった。
なお、C−6は反応途中にゲル化したので、以後の評価は行わなかった。
[Comparative Synthesis Examples 5 and 6] (Polyester resins C-5 and C-6 having a carboxyl group)
The reaction was performed in the same manner as in Comparative Synthesis Example 2 except that the reaction was performed in the absence of solvent without using toluene.
In addition, since C-6 gelatinized in the middle of reaction, subsequent evaluation was not performed.
《分子量の測定》
合成例I、合成例II、比較合成例で合成した水酸基を有するポリエステル樹脂及びカルボキシル基を有するポリエステル樹脂を、夫々0.1%の濃度でテトラヒドロフラン(THF)に溶解して、0.45μmのフィルターで濾過して試料とし、ゲル浸透型クロマトグラフィー(GPC)により測定した。測定装置には昭和電工製GPC101を用い、カラムはShodex KF−806L×2 + KF−804L + KF−802 の4本連結カラムを用いた。移動相には上記と同様のテトラヒドロフラン(THF)を用い、注入量200μl、カラム温度40℃、流速1.0ml/minの条件で測定を行った。分子量の算出は標準ポリスチレン換算で行った。
<Measurement of molecular weight>
A 0.45 μm filter was prepared by dissolving the polyester resin having a hydroxyl group and the polyester resin having a carboxyl group synthesized in Synthesis Example I, Synthesis Example II, and Comparative Synthesis Example in tetrahydrofuran (THF) at a concentration of 0.1%, respectively. The sample was filtered through a gel and measured by gel permeation chromatography (GPC). Showa Denko GPC101 was used as the measuring device, and a four-column column of Shodex KF-806L × 2 + KF-804L + KF-802 was used as the column. The same tetrahydrofuran (THF) as above was used for the mobile phase, and measurement was performed under the conditions of an injection amount of 200 μl, a column temperature of 40 ° C., and a flow rate of 1.0 ml / min. The molecular weight was calculated in terms of standard polystyrene.
《酸価の測定》
ポリエステル樹脂1gをトルエン/イソプロピルアルコール=2/1(重量)の混合溶剤20mlに溶解し、0.1mol/LのKOHエタノール溶液で滴定して、樹脂1g当りのKOHのmg数を求めた。
<Measurement of acid value>
1 g of the polyester resin was dissolved in 20 ml of a mixed solvent of toluene / isopropyl alcohol = 2/1 (weight) and titrated with a 0.1 mol / L KOH ethanol solution to obtain the number of mg of KOH per 1 g of resin.
《ガラス転移温度の測定》
示差走査熱量計(DSC)を用いて、10℃/minの昇温速度で測定した。
上記、分子量、酸価、ガラス転移温度の結果を表−1、表−2、表−3に示す。
<Measurement of glass transition temperature>
It measured with the temperature increase rate of 10 degree-C / min using the differential scanning calorimeter (DSC).
The results of the molecular weight, acid value, and glass transition temperature are shown in Table-1, Table-2, and Table-3.
実施例I(FPC用接着剤)
[実施例I−1]
合成例IIで得られたカルボキシル基を有するポリエステル樹脂(B−1)を樹脂分換算(以下樹脂分換算で示す)で90部、ビスフェノールA型エポキシ樹脂エピコート828を10部、メチルエチルケトンを用いて固形分濃度が30%となるように混合溶解して、接着剤溶液を得た。
Example I (adhesive for FPC)
[Example I-1]
90 parts of the polyester resin (B-1) having a carboxyl group obtained in Synthesis Example II in terms of resin content (hereinafter referred to in terms of resin content), 10 parts of bisphenol A type epoxy resin Epicoat 828, solid using methyl ethyl ketone The mixture was dissolved so that the partial concentration was 30% to obtain an adhesive solution.
[実施例I−2〜9]
実施例1と同様の方法で、表−4の組成に従って接着剤溶液を得た。
[Examples I-2 to 9]
In the same manner as in Example 1, an adhesive solution was obtained according to the composition of Table-4.
比較例(FPC用接着剤)
[比較例I−1〜6]
実施例1と同様の方法で、表−4の組成に従って接着剤溶液を得た。
Comparative example (adhesive for FPC)
[Comparative Examples I-1 to 6]
In the same manner as in Example 1, an adhesive solution was obtained according to the composition of Table-4.
(I)FPC用接着剤としての評価
1.接着強度試験
上記接着剤溶液を厚さ50μmのポリイミドフィルムに、乾燥後の厚みが30μmと なる様に塗布し80℃で2分乾燥して接着剤積層物を得た。次に厚さ50μmのポリイ ミドフィルム上に、上記接着剤積層物を接着剤層の面がポリイミドフィルムと接する様 に重ね合わせ、80℃、1kgf/cm2、100mm/minの条件でラミネートし た。
この様にして得られた、ポリイミドフィルム/接着剤/ポリイミドフィルムの積層物 を加熱プレス機にて、150℃、10MPa、の条件下で2分間熱圧着した後、150 ℃のオーブンで3時間熱処理して硬化させた。このサンプルを10mmの幅にカットし て、引っ張り速度50mm/minで180度剥離試験を行った。
(I) Evaluation as an adhesive for FPC Adhesive strength test The above adhesive solution was applied to a polyimide film having a thickness of 50 µm so that the thickness after drying was 30 µm, and dried at 80 ° C for 2 minutes to obtain an adhesive laminate. Next, the adhesive laminate was laminated on a polyimide film having a thickness of 50 μm so that the surface of the adhesive layer was in contact with the polyimide film, and was laminated at 80 ° C., 1 kgf / cm 2 , and 100 mm / min. .
The polyimide film / adhesive / polyimide film laminate thus obtained was heat-pressed for 2 minutes under the conditions of 150 ° C. and 10 MPa using a heat press, and then heat treated in an oven at 150 ° C. for 3 hours. And cured. This sample was cut into a width of 10 mm, and a 180 degree peel test was performed at a pulling speed of 50 mm / min.
2.半田耐熱性試験(常態)
上記接着強度試験で作製したサンプルを10mmの幅にカットしたものを、260℃ で溶融した鉛フリー半田浴に1分間平らに乗せた後、取り出して接着剤層の発泡状態を 観察した。
〇 :試験前の状態と全く変化なし
〇△:試験片に5個以下の膨れが発生
△ :試験片の面積の1/2に膨れが発生
× :試験片全面に膨れが発生
2. Solder heat resistance test (normal state)
The sample prepared in the above adhesive strength test was cut to a width of 10 mm, placed on a lead-free solder bath melted at 260 ° C. for 1 minute, then taken out, and the foamed state of the adhesive layer was observed.
○: No change from the state before the test ○ △: Swelling of 5 or less occurs in the test piece △: Swelling occurs in half of the area of the test piece ×: Swelling occurs on the entire surface of the test piece
3.半田耐熱試験(加湿処理後)
上記接着強度試験で作製したサンプルを10mmの幅にカットしたものを、40℃、 80%加湿下にて2日間放置した後、260℃で溶融した鉛フリー半田浴に1分間平ら に乗せた後、取り出して接着剤層の発泡状態を観察した。
〇 :試験前の状態と全く変化なし
〇△:試験片に5個以下の膨れが発生
△ :試験片の面積の1/2に膨れが発生
× :試験片全面に膨れが発生
3. Solder heat resistance test (after humidification treatment)
After the sample prepared in the above adhesive strength test was cut to a width of 10 mm and left for 2 days at 40 ° C. and 80% humidification, it was placed flat on a lead-free solder bath melted at 260 ° C. for 1 minute. Then, it was taken out and the foaming state of the adhesive layer was observed.
○: No change from the state before the test ○ △: Swelling of 5 or less occurs in the test piece △: Swelling occurs in half of the area of the test piece ×: Swelling occurs on the entire surface of the test piece
4.耐マイグレーション性
接着剤溶液を厚さ25μmのポリイミドフィルムに、乾燥後の厚みが30μmとなる ように塗布し、80℃で2分間乾燥させた。この様にして得られた接着剤積層物を厚さ 35μmの圧延銅箔と貼り合せる際、圧延銅箔の酸処理面が接着剤層と接するようにし て、150℃、10MPaの加圧下で2分間プレスした。得られた、ポリイミドフィル ム/接着剤/圧延銅箔の積層物を150℃にて3時間熱処理して硬化させた。この様に して銅貼り積層板を得た。この銅貼り積層板を常法により銅箔面にフォトレジスト塗布 、パターン露光、現像、銅箔パターンエッチング、フォトレジスト剥離工程を経て、銅 線間が100μmとなる櫛型のパターン基板を形成した。
また、上記接着剤溶液を厚さ50μmのポリイミドフィルムに、乾燥後の厚みが30 μmとなる様に塗布し、80℃で2分間乾燥させた。この積層物を140℃で1時間熱 処理してフレキシブルプリント配線板用カバーフィルムを得た。このカバーフイルムの 接着剤層と上記パターン基板のパターン形成面とを貼り合わせ、150℃、10MPa の加圧下にて2分間プレスし、ラミネートした。この積層物を150℃にて3時間熱処 理して目的のサンプルを得た。この様にして得られた耐マイグレーション試験用FPC について、温度85℃、湿度85%の環境下で、印加電圧DC24V、1000時間の 導電試験を行った。
〇 :短絡の発生、及び基板の変色が全くなし
〇△:短絡の発生は無いが、基板が僅かに変色
△ :600時間で短絡が発生、基板の変色が著しい
× :300時間で短絡が発生、基板の変色が著しい
上記1〜4までの結果を表−4に示す。
4). Migration Resistance The adhesive solution was applied to a polyimide film having a thickness of 25 μm so that the thickness after drying was 30 μm, and dried at 80 ° C. for 2 minutes. When the adhesive laminate thus obtained is bonded to a rolled copper foil having a thickness of 35 μm, the acid-treated surface of the rolled copper foil is brought into contact with the adhesive layer, and the pressure is increased at 150 ° C. under a pressure of 10 MPa. Pressed for a minute. The obtained polyimide film / adhesive / rolled copper foil laminate was heat-treated at 150 ° C. for 3 hours to be cured. In this way, a copper-clad laminate was obtained. This copper-clad laminate was subjected to a photoresist coating, pattern exposure, development, copper foil pattern etching, and photoresist stripping steps on a copper foil surface by a conventional method to form a comb-shaped pattern substrate having a copper wire spacing of 100 μm.
The adhesive solution was applied to a polyimide film having a thickness of 50 μm so that the thickness after drying was 30 μm and dried at 80 ° C. for 2 minutes. This laminate was heat-treated at 140 ° C. for 1 hour to obtain a cover film for a flexible printed wiring board. The adhesive layer of the cover film and the pattern forming surface of the pattern substrate were bonded together, pressed and laminated at 150 ° C. under a pressure of 10 MPa for 2 minutes. This laminate was heat-treated at 150 ° C. for 3 hours to obtain a target sample. The thus obtained FPC for migration resistance test was subjected to a conductivity test at an applied voltage of DC 24 V for 1000 hours in an environment of a temperature of 85 ° C. and a humidity of 85%.
○: No short circuit and no discoloration of the substrate ○ △: No short circuit occurred, but the substrate slightly discolored Δ: Short circuit occurred in 600 hours, significant discoloration of the substrate ×: Short circuit occurred in 300 hours Table 4 shows the results of 1 to 4 described above.
実施例II(一般用接着剤)
[実施例II−1]
合成例IIで得られたカルボキシル基を有するポリエステル樹脂(B−2)を樹脂分換算(以下樹脂分換算で示す)で90部、多官能エポキシ化合物エピコート1031Sを10部、メチルエチルケトンを用いて固形分濃度が30%となるように混合溶解して、接着剤溶液を得た。この接着剤溶液を用いて、乾燥後の厚みが30μmとなる様に離形紙に塗布し、80℃で2分間乾燥させた。この様な方法で離形紙/接着剤層の積層物を作製した。
Example II (General Adhesive)
[Example II-1]
Polyester resin (B-2) having a carboxyl group obtained in Synthesis Example II is 90 parts in terms of resin content (hereinafter referred to in terms of resin content), 10 parts of polyfunctional epoxy compound Epicoat 1031S, and solid content using methyl ethyl ketone. An adhesive solution was obtained by mixing and dissolving so that the concentration was 30%. Using this adhesive solution, it was applied to release paper so that the thickness after drying was 30 μm, and dried at 80 ° C. for 2 minutes. In this way, a release paper / adhesive layer laminate was prepared.
[実施例II−2〜7]
実施例1と同様の方法で、表−5の組成に従って接着剤溶液を得、同様の方法で接着剤積層物を作製した。
[Examples II-2 to 7]
In the same manner as in Example 1, an adhesive solution was obtained according to the composition of Table-5, and an adhesive laminate was produced in the same manner.
比較例(一般接着剤)
[比較例II−1〜5]
実施例1と同様の方法で、表−5の組成に従って接着剤溶液を得、同様の方法で接着剤積層物を作製した。
Comparative example (general adhesive)
[Comparative Examples II-1 to 5]
In the same manner as in Example 1, an adhesive solution was obtained according to the composition of Table-5, and an adhesive laminate was produced in the same manner.
(II)一般接着剤としての評価
1.接着強度の測定
(1)亜鉛鋼板/亜鉛鋼板
表面を脱脂した亜鉛鋼板(0.5mm厚×15mm幅×100mm長)に、実施例I I−1〜7、比較例II−1〜5で作製した接着剤積層物を接着剤層の面を亜鉛鋼板に 接するようにして重ね合わせ、80℃、1kgf/cm2、200m/minの条件で ラミネートした。次に、離形紙を剥がして露出した接着剤層の面に、もう一方の亜鉛鋼 板を重ね合わせ、80℃、1kgf/cm2、200m/minの条件でラミネートし て、亜鉛鋼板/接着剤層/亜鉛鋼板の積層物を得た。この積層物を、150℃、3MP aの加圧下で2分間プレスして、接着強度測定用サンプルを作製した。
(2)亜鉛鋼板/ウレタンゴム
(1)と同様の方法で亜鉛鋼板/接着剤層をラミネートし、離形紙を剥がして露出した 接着剤層の面に、ウレタンゴムシート(2mm厚×15mm幅×100mm長)を重ね 合わせて、(1)と同様の方法で接着強度測定用サンプルを作製した。
(3)アルミニウム板/アルミニウム板
(1)と同様の方法で、表面を脱脂したアルミニウム板(5182Al材、0.28m m厚×15mm幅×100mm長)に、接着剤積層物を重ねあわせ、同様の方法で、ア ルミニウム板/接着剤層/アルミニウム板の積層物を作製した。
(4)コロナ処理PET/コロナ処理PET
(1)と同様の方法で、コロナ表面処理を施したPET(ポリエチレンテレフタレート )フィルム(100μm厚×15mm幅×100mm長)同士を接着剤層を介して貼り 合わせて、接着強度測定用サンプルを作製した。
(II) Evaluation as a general adhesive Measurement of Adhesive Strength (1) Zinc Steel Sheet / Zinc Steel Sheet Prepared in Examples I I-1 to 7 and Comparative Examples II-1 to 5 on a galvanized steel sheet (0.5 mm thickness × 15 mm width × 100 mm length) with the surface degreased The obtained adhesive laminate was laminated so that the surface of the adhesive layer was in contact with the galvanized steel sheet, and was laminated at 80 ° C., 1 kgf / cm 2 and 200 m / min. Next, the other galvanized steel plate is placed on the surface of the adhesive layer exposed by peeling off the release paper and laminated under the conditions of 80 ° C., 1 kgf / cm 2 , 200 m / min, and galvanized steel plate / adhesive A laminate of the agent layer / zinc steel plate was obtained. This laminate was pressed at 150 ° C. under a pressure of 3 MPa for 2 minutes to prepare a sample for measuring adhesive strength.
(2) Zinc steel plate / urethane rubber Laminate zinc steel plate / adhesive layer in the same manner as (1), peel off release paper, and expose urethane rubber sheet (2mm thickness x 15mm width) on the exposed adhesive layer surface × 100 mm length) were stacked and a sample for measuring adhesive strength was produced in the same manner as in (1).
(3) Aluminum plate / aluminum plate In the same manner as in (1), the adhesive laminate is overlapped on the aluminum plate (5182Al material, 0.28 mm thickness × 15 mm width × 100 mm length) degreased on the surface. Thus, an aluminum plate / adhesive layer / aluminum plate laminate was produced.
(4) Corona-treated PET / Corona-treated PET
Using a method similar to (1), corona surface-treated PET (polyethylene terephthalate) films (100 μm thick × 15 mm wide × 100 mm long) are bonded together via an adhesive layer to produce a sample for measuring adhesive strength. did.
上記(1)(2)(3)(4)で作製した接着強度測定用サンプルについて、引っ張り速度50mm/minで180度剥離試験を行った。その結果を表−5に示す。 About the sample for the adhesive strength measurement produced by said (1) (2) (3) (4), the 180 degree | times peeling test was done with the tension | pulling speed of 50 mm / min. The results are shown in Table-5.
実施例III(塗料)
[実施例III−1]
合成例IIで得られたカルボキシル基を有するポリエステル樹脂(B−1)を樹脂分換算(以下樹脂分換算で示す)で90部、多官能エポキシ化合物エピコート1031Sを10部、メチルエチルケトンを用いて固形分濃度が30%となるように混合溶解した。これに酸化チタン(タイペークCR−93、石原産業製)100部を加えて、アイガーミルにて顔料分散を行い、ホワイト塗料を作製した。
Example III (paint)
[Example III-1]
Polyester resin (B-1) having a carboxyl group obtained in Synthesis Example II is 90 parts in terms of resin content (hereinafter referred to in terms of resin content), 10 parts of polyfunctional epoxy compound Epicoat 1031S, and solid content using methyl ethyl ketone. The mixture was dissolved so that the concentration was 30%. To this, 100 parts of titanium oxide (Taipeku CR-93, manufactured by Ishihara Sangyo Co., Ltd.) was added, and pigment dispersion was performed with an Eiger mill to prepare a white paint.
[実施例III−2〜6、比較例III−1〜5]
実施例1と同様の方法で、表−6の組成に従って、ホワイト塗料を作製した。
[Examples III-2 to 6, Comparative Examples III-1 to 5]
A white paint was produced in the same manner as in Example 1 according to the composition shown in Table-6.
実施例III−1〜6及び比較例III−1〜5で得られたホワイト塗料を、厚さ0.25mmのブリキ板に乾燥後の膜厚が8〜10μmとなる様に塗布し、200℃のオーブン中で10分間焼付けを行って、試験板を作製した。 The white paint obtained in Examples III-1 to 6 and Comparative Examples III-1 to 5 was applied to a tin plate having a thickness of 0.25 mm so that the film thickness after drying was 8 to 10 μm, and 200 ° C. The test plate was produced by baking for 10 minutes in the oven.
(III)塗料としての評価
1.硬化性試験
試験片の表面にメチルエチルケトン(MEK)溶剤を浸した脱脂綿を当てて、これに加重1kgを掛けながら往復させる。その際、素地に達した往復回数から硬化の程度を判断した。
◎ :優良、50回以上
〇△:良好、20回以上〜50回未満
△ :やや硬化不良、5回以上〜20回未満
× :未硬化、5回未満
2.折り曲げ加工性試験
試験板を3cm×5cmの大きさに裁断し、塗膜面を外側にして、折り曲げ部の幅が3cmとなるようにして、厚さ0.25mmのブリキ板を一枚はさんで試験片を180度折り曲げ、1kgの錘を50cmの高さから落下させて試験片を完全に折り曲げる。この曲げ加工部を、1%食塩水溶液に浸漬したスポンジに接触させ、6Vの電圧をかけたときの通電量(mA、少ないほど折り曲げ加工性が良好)により、評価した。
◎ :優良、1mA以下
〇△:良好、1mA以上〜5mA未満
△ :やや折り曲げ加工性不良、5mA以上〜20mA未満
× :折り曲げ加工性不良、20mA以上
3.絞り加工性
塗膜面を外側にして、直径3cm、深さ3cmのキャップ形に絞り加工を行い、そのキャップを沸騰水中で30分間、熱水処理を行った。キャップ壁面の塗膜の剥離状態を観察した。
◎ :優良、キャップの壁面に剥離が認められない
〇△:良好、キャップの底面から5mmの高さまで剥離が発生
△ :絞り加工性不良、キャップの底面から10mmの高さまで剥離が発生
× :絞り加工性不良、キャップの底面から10mmを超える高さまで剥離が発生
4.耐ブロッキング試験
試験板を10cm×10cmの大きさに切り、試験板の塗膜面とブリキ板を重ね合わ せて、40℃、5kgf/cm2の条件で1時間プレスした後、試験板を固定して、ブ リキ板を引っ張り試験機にて100mm/minの速度で面方向に引き剥がし、その時 の引っ張り荷重で耐ブロッキング性を評価した(50g未満が実用レベル)。
◎ :優良、10g未満
〇△:良好、10g以上〜50g未満
△ :やや耐ブロッキング性不良、50g以上〜100g未満
× :耐ブロッキング性不良、100g以上
上記1〜4までの試験結果を表−6に示す。
(III) Evaluation as a paint Curability test Put absorbent cotton soaked with methyl ethyl ketone (MEK) solvent on the surface of the test piece and reciprocate while applying a weight of 1 kg. At that time, the degree of curing was judged from the number of round trips that reached the substrate.
◎: Excellent, 50 times or more ○ Δ: Good, 20 times to less than 50 times Δ: Slightly poor curing, 5 times to less than 20 times ×: Uncured, less than 5 times Bending workability test The test plate is cut into a size of 3cm x 5cm, the coating surface is outside, the width of the bent part is 3cm, and a sheet of 0.25mm thick tin plate is sandwiched. Then, the test piece is bent 180 degrees and a 1 kg weight is dropped from a height of 50 cm to completely fold the test piece. This bent portion was brought into contact with a sponge immersed in a 1% saline solution and evaluated by the amount of current applied when a voltage of 6 V was applied (mA, the smaller the bending workability, the better).
◎: Excellent, 1 mA or less ○ △: Good, 1 mA to less than 5 mA △: Slightly bending workability, 5 mA to less than 20 mA ×: Bending workability, 20 mA or more Drawing workability With the coating surface facing outside, drawing was performed into a cap shape having a diameter of 3 cm and a depth of 3 cm, and the cap was subjected to hot water treatment in boiling water for 30 minutes. The peeling state of the coating film on the cap wall surface was observed.
◎: Excellent, no peeling on the wall of the cap △△: Good, peeling occurred to a height of 5 mm from the bottom of the cap △: Poor drawing workability, peeling occurred to a height of 10 mm from the bottom of the cap ×: Drawing 3. Processability is poor and peeling occurs from the bottom of the cap to a height exceeding 10 mm. Anti-blocking test The test plate was cut to a size of 10 cm x 10 cm, the coating surface of the test plate and the tin plate were overlapped, pressed for 1 hour at 40 ° C and 5 kgf / cm 2 , and then the test plate was fixed. Then, the black plate was peeled off in the surface direction at a speed of 100 mm / min with a tensile tester, and the blocking resistance was evaluated by the tensile load at that time (less than 50 g was a practical level).
◎: Excellent, less than 10 g ○ Δ: Good, 10 g or more but less than 50 g Δ: Slightly blocking resistance poor, 50 g or more but less than 100 g x: Poor blocking resistance, 100 g or more Test results up to 1 to 4 are shown in Table-6. Shown in
Claims (3)
次いで前記水酸基を有するポリエステル樹脂(c3)を溶剤に溶解した後、前記溶剤の沸点以下の温度で、水酸基を有するポリエステル樹脂(c3)を無水ピロメリット酸またはエチレングリコールビストリメリテート二無水物(c4)と反応させて、数平均分子量(Mn2)が21000以上及び重量平均分子量(Mw2)が42300以上のカルボキシル基を有するポリエステル樹脂を得、
前記カルボキシル基を有するポリエステル樹脂の数平均分子量(Mn2)及び重量平均分子量(Mw2)のいずれもが、前記水酸基を有するポリエステル樹脂(c3)の数平均分子量(Mn1)及び重量平均分子量(Mw1)のそれぞれの少なくとも1.2倍であり、かつそれぞれ3倍以下である、カルボキシル基を有するポリエステル樹脂の製造方法。 Reacting the diol (c1) with at least one carboxylic acid component (c2) selected from the group consisting of dibasic acid, dibasic acid anhydride, and alkyl ester of dibasic acid in the absence of a solvent; A polyester resin (c3) having a hydroxyl group having a number average molecular weight (Mn1) of 15000 to 30000 and a weight number average molecular weight (Mw1) of 25000 to 60000 is obtained.
Next, after the polyester resin (c3) having a hydroxyl group is dissolved in a solvent, the polyester resin (c3) having a hydroxyl group is dissolved in pyromellitic anhydride or ethylene glycol bistrimellitate dianhydride (c4) at a temperature not higher than the boiling point of the solvent. ) To obtain a polyester resin having a carboxyl group having a number average molecular weight (Mn2) of 21,000 or more and a weight average molecular weight (Mw2) of 42300 or more,
The number average molecular weight (Mn2) and the weight average molecular weight (Mw2) of the polyester resin having a carboxyl group are both the number average molecular weight (Mn1) and the weight average molecular weight (Mw1) of the polyester resin (c3) having a hydroxyl group. A method for producing a polyester resin having a carboxyl group, which is at least 1.2 times each and 3 times or less each.
The carboxyl resin according to claim 1 or 2, wherein the polyester resin (c3) having a hydroxyl group is reacted with pyromellitic anhydride or ethylene glycol bistrimellitate dianhydride (c4) in the presence of a quaternary ammonium salt. The manufacturing method of the polyester resin which has group.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006074288A JP5347212B2 (en) | 2006-03-17 | 2006-03-17 | Polyester resin and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006074288A JP5347212B2 (en) | 2006-03-17 | 2006-03-17 | Polyester resin and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2007246802A JP2007246802A (en) | 2007-09-27 |
JP5347212B2 true JP5347212B2 (en) | 2013-11-20 |
Family
ID=38591436
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2006074288A Active JP5347212B2 (en) | 2006-03-17 | 2006-03-17 | Polyester resin and method for producing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5347212B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2731097C2 (en) * | 2016-01-15 | 2020-08-28 | БАСФ Коатингс ГмбХ | Carboxy-functional reaction products based on polyether and aqueous primer materials, including reaction products |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5678773B2 (en) * | 2011-03-31 | 2015-03-04 | 東洋インキScホールディングス株式会社 | Conductive resin composition and conductive adhesive sheet |
JP2021070497A (en) | 2019-10-31 | 2021-05-06 | 大和製罐株式会社 | cap |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02178370A (en) * | 1988-12-29 | 1990-07-11 | Toyo Ink Mfg Co Ltd | Thermosetting paint |
JPH0381334A (en) * | 1989-08-24 | 1991-04-05 | Tonen Corp | Production of polyolefin-polyester graft copolymer |
JP3422066B2 (en) * | 1994-02-07 | 2003-06-30 | チッソ株式会社 | Viscoelastic resin for vibration damping material and composition thereof |
JPH11116667A (en) * | 1997-08-13 | 1999-04-27 | Kansai Paint Co Ltd | Polyester resin and powder coating composition using the same |
JP2002088136A (en) * | 2000-09-12 | 2002-03-27 | Nagase Kasei Kogyo Kk | Photopolymerizable unsaturated resin and photosensitive resin composition containing the resin |
JP4189718B2 (en) * | 2002-01-24 | 2008-12-03 | 東洋紡績株式会社 | Resin composition for paint and coated metal plate coated with the same |
JP4299495B2 (en) * | 2002-05-02 | 2009-07-22 | 三菱レイヨン株式会社 | Thermosetting coating composition, and paint comprising the composition |
JP2005194494A (en) * | 2003-12-09 | 2005-07-21 | Kansai Paint Co Ltd | Method for producing aqueous polyester resin composition, thermosetting water-borne coating composition obtained by using aqueous polyester resin composition and coating material obtained by using thermosetting water-borne coating composition |
-
2006
- 2006-03-17 JP JP2006074288A patent/JP5347212B2/en active Active
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2731097C2 (en) * | 2016-01-15 | 2020-08-28 | БАСФ Коатингс ГмбХ | Carboxy-functional reaction products based on polyether and aqueous primer materials, including reaction products |
Also Published As
Publication number | Publication date |
---|---|
JP2007246802A (en) | 2007-09-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109553766B (en) | Modified polyester polyol and preparation method and application thereof | |
CN110268030B (en) | Polyester-based adhesive composition containing carboxylic acid group | |
JP7388485B2 (en) | Adhesive compositions and adhesives | |
JP7334827B2 (en) | Adhesive composition and adhesive | |
JP5347212B2 (en) | Polyester resin and method for producing the same | |
JP6380710B1 (en) | Carboxylic acid group-containing polymer compound and adhesive composition containing the same | |
JP5326188B2 (en) | Resin composition, phenoxy resin, coating composition, adhesive composition, adhesive film, prepreg, multilayer printed wiring board, and resin-coated copper foil | |
JPWO2017047197A1 (en) | Copolyester and metal primer coating using the same | |
JP2019119841A (en) | Laminate | |
WO2021079670A1 (en) | Adhesive composition for flexible printed wiring board, adhesive for flexible printed wiring board, and flexible printed wiring board | |
JP2007070481A (en) | Adhesive composition and flexible printed wiring board using the same | |
JP7279842B2 (en) | Polyester resin, adhesive composition and adhesive | |
JP2018044094A (en) | Resin composition, and coated film and laminate using the same | |
JP2009029933A (en) | Ester type epoxy resin, resin composition containing the same and adhesive composition | |
JP4717236B2 (en) | Adhesive polyester and laminate | |
JP7156562B1 (en) | Adhesive composition for flexible printed wiring board | |
CN111683988A (en) | Copolymerized saturated polyester resin and coating composition comprising the same | |
JP7318838B2 (en) | Adhesive composition, adhesive sheet, laminate and printed wiring board | |
JP4789761B2 (en) | Flame retardant sheet | |
JP2003252972A (en) | Polyester for adhesive use and laminate using the same | |
WO2023063386A1 (en) | Crosslinked polyester resin, adhesive composition, and adhesive sheet | |
JP2024007384A (en) | Adhesive agent composition and adhesive agent | |
JP2023176914A (en) | Adhesive composition and adhesive |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080901 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110926 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20111004 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20111201 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120925 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121122 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20130129 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130410 |
|
A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20130524 |
|
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: 20130723 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130805 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5347212 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |