JPH10330481A - Production of hydrophilic polyamide-based resin - Google Patents
Production of hydrophilic polyamide-based resinInfo
- Publication number
- JPH10330481A JPH10330481A JP10080058A JP8005898A JPH10330481A JP H10330481 A JPH10330481 A JP H10330481A JP 10080058 A JP10080058 A JP 10080058A JP 8005898 A JP8005898 A JP 8005898A JP H10330481 A JPH10330481 A JP H10330481A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- weight
- hydrophilic
- resin
- acid
- 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.)
- Pending
Links
- 229920002647 polyamide Polymers 0.000 title claims abstract description 86
- 229920005989 resin Polymers 0.000 title claims abstract description 60
- 239000011347 resin Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000003822 epoxy resin Substances 0.000 claims abstract description 44
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 44
- 239000004952 Polyamide Substances 0.000 claims abstract description 35
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 14
- 150000004985 diamines Chemical class 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 abstract description 37
- 239000003513 alkali Substances 0.000 abstract description 17
- 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 abstract description 12
- 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 abstract description 8
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 8
- 239000007864 aqueous solution Substances 0.000 abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 61
- 229920006122 polyamide resin Polymers 0.000 description 56
- -1 for example Polymers 0.000 description 28
- 239000000203 mixture Substances 0.000 description 23
- 239000003960 organic solvent Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910001873 dinitrogen Inorganic materials 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 239000010408 film Substances 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 230000007423 decrease Effects 0.000 description 13
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 12
- 238000009423 ventilation Methods 0.000 description 12
- 230000001588 bifunctional effect Effects 0.000 description 11
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- 125000001931 aliphatic group Chemical group 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 150000001408 amides Chemical class 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 9
- 239000011342 resin composition Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 125000003700 epoxy group Chemical group 0.000 description 7
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 7
- 125000005702 oxyalkylene group Chemical group 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 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 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 238000007112 amidation reaction Methods 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 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 5
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 5
- 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 4
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 125000004018 acid anhydride group Chemical group 0.000 description 4
- 229920005601 base polymer Polymers 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000006114 decarboxylation reaction Methods 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 150000002596 lactones Chemical class 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003628 tricarboxylic acids Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005273 aeration Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 3
- 229910000071 diazene Inorganic materials 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- LYANEXCVXFZQFF-UHFFFAOYSA-N 2-(2,5-dioxooxolan-3-yl)acetic acid Chemical compound OC(=O)CC1CC(=O)OC1=O LYANEXCVXFZQFF-UHFFFAOYSA-N 0.000 description 2
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2-methyl-4-methylimidazole Natural products CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 2
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000003779 heat-resistant material Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-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
- 229920003986 novolac Polymers 0.000 description 2
- 125000006353 oxyethylene group Chemical group 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
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 2
- 229960003656 ricinoleic acid Drugs 0.000 description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000004334 sorbic acid Substances 0.000 description 2
- 235000010199 sorbic acid Nutrition 0.000 description 2
- 229940075582 sorbic acid Drugs 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- 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
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- WBODDOZXDKQEFS-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-phenylbenzene Chemical group CC1=C(C)C(C)=CC(C=2C=CC=CC=2)=C1C WBODDOZXDKQEFS-UHFFFAOYSA-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
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- WBJWXIQDBDZMAW-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carbonyl chloride Chemical compound C1=CC=CC2=C(C(Cl)=O)C(O)=CC=C21 WBJWXIQDBDZMAW-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JEHFRMABGJJCPF-UHFFFAOYSA-N 2-methylprop-2-enoyl isocyanate Chemical compound CC(=C)C(=O)N=C=O JEHFRMABGJJCPF-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 description 1
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- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
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- PPQRADLPLZYEKN-UHFFFAOYSA-N tritylphosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1C(C=1C=CC=CC=1)([PH3+])C1=CC=CC=C1 PPQRADLPLZYEKN-UHFFFAOYSA-N 0.000 description 1
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- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Polyamides (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、親水性ポリアミド
系樹脂の製造法に関する。[0001] The present invention relates to a method for producing a hydrophilic polyamide resin.
【０００２】[0002]
【従来の技術】近年、プリント配線板等の保護膜やカバ
ーコートには、信頼性向上のため、耐熱性、屈曲性及び
難燃性に優れた感光性耐熱材料が強く望まれている。従
来、これらのベースポリマとしては、例えば、米国特許
第４６３８０３８号等に記載されているフェノキシ樹
脂、高分子量エポキシ樹脂、ポリアミド系樹脂、ポリイ
ミド系樹脂などが用いられているが、いずれの樹脂も使
用できる現像液は、溶剤系か、溶剤とアルカリ水溶液の
混合液である水系がほとんどであった。現像液として
は、価格及び環境衛生上の点から、溶剤を使用しない特
に無機のアルカリ水溶液が最も好ましく用いられる。ア
ルカリ現像液で現像するためには、ベースポリマのカル
ボキシル基濃度及びベースポリマ自身の親水性が、ある
一定以上必要である。しかしながら、上記の付加型又は
縮合型の樹脂の場合には、ベースポリマ自身の親水性が
不十分であり、アルカリ現像性を付与することは極めて
困難であった。2. Description of the Related Art In recent years, for a protective film or a cover coat of a printed wiring board or the like, a photosensitive heat-resistant material having excellent heat resistance, flexibility and flame retardancy has been strongly desired in order to improve reliability. Conventionally, as these base polymers, for example, phenoxy resins, high molecular weight epoxy resins, polyamide resins, polyimide resins, and the like described in U.S. Pat. No. 4,638,038 and the like have been used. In most cases, the developing solution was a solvent system or an aqueous system which was a mixture of a solvent and an aqueous alkali solution. As the developer, an inorganic alkali aqueous solution which does not use a solvent is most preferably used from the viewpoint of cost and environmental hygiene. In order to carry out development with an alkali developer, the concentration of the carboxyl group of the base polymer and the hydrophilicity of the base polymer itself must be at least a certain level. However, in the case of the addition-type or condensation-type resin, the hydrophilicity of the base polymer itself is insufficient, and it is extremely difficult to impart alkali developability.
【０００３】[0003]
【発明が解決しようとする課題】請求項１記載の発明
は、親水性が優れた、プリント配線板等の製造用のアル
カリ現像型感光性樹脂組成物のポリマ成分として好適
な、アルカリ水溶液可溶性の親水性ポリアミド系樹脂の
製造法を提供するものである。SUMMARY OF THE INVENTION The invention according to claim 1 is an aqueous solution of an alkali aqueous solution which is excellent in hydrophilicity and is suitable as a polymer component of an alkali-developable photosensitive resin composition for producing a printed wiring board and the like. It is intended to provide a method for producing a hydrophilic polyamide-based resin.
【０００４】[0004]
【課題を解決するための手段】本発明は、（Ａ）ポリオ
キシアルキレン基を有する親水性ジカルボン酸と（Ｂ）
ジイソシアネート又はジアミンを反応させてポリアミド
中間体を得、次いで、このポリアミド中間体に（Ｃ）エ
ポキシ樹脂を反応させてポリアミド系樹脂中間体を得、
このポリアミド系樹脂中間体に（Ｄ）多価カルボン酸モ
ノ無水物を反応させることを特徴とする親水性ポリアミ
ド系樹脂の製造法に関する。The present invention relates to (A) a hydrophilic dicarboxylic acid having a polyoxyalkylene group and (B)
Reacting a diisocyanate or a diamine to obtain a polyamide intermediate, and then reacting the polyamide intermediate with (C) an epoxy resin to obtain a polyamide resin intermediate;
The present invention relates to a method for producing a hydrophilic polyamide-based resin, which comprises reacting (D) a polycarboxylic acid monoanhydride with the polyamide-based resin intermediate.
【０００５】[0005]
【発明の実施の形態】本発明の親水性ポリアミド系樹脂
の製造法は、必須反応成分として（Ａ）ポリオキシアル
キレン基を有する親水性ジカルボン酸、（Ｂ）ジイソシ
アネート又はジアミン、（Ｃ）エポキシ樹脂及び（Ｄ）
多価カルボン酸モノ無水物を用いる。BEST MODE FOR CARRYING OUT THE INVENTION The process for producing a hydrophilic polyamide resin of the present invention comprises, as essential reaction components, (A) a hydrophilic dicarboxylic acid having a polyoxyalkylene group, (B) a diisocyanate or a diamine, and (C) an epoxy resin. And (D)
A polycarboxylic monoanhydride is used.
【０００６】本発明における（Ａ）ポリオキシアルキレ
ン基を有する親水性ジカルボン酸としては、特に制限は
なく、例えば、オキシアルキレン基・アミド又はイミド
結合含有ジカルボン酸、オキシアルキレン基・エステル
結合含有ジカルボン酸、オキシアルキレンジカルボン酸
等が挙げられる。The (A) hydrophilic dicarboxylic acid having a polyoxyalkylene group in the present invention is not particularly limited, and examples thereof include an oxyalkylene group / amide or imide bond-containing dicarboxylic acid and an oxyalkylene group / ester bond-containing dicarboxylic acid. And oxyalkylenedicarboxylic acids.
【０００７】オキシアルキレン基・アミド又はイミド結
合含有ジカルボン酸としては、ポリオキシアルキレンジ
アミン（例えば、ハンツマンコーポレーション製商品名
ジェファーミンＤ−２３０、Ｄ−４００、Ｄ−２００
０、Ｄ−４０００、ＥＤ−６００、ＥＤ−９００、ＥＤ
２００１、ＥＤＲ−１４８、広栄化学工業(株)製 ビス
−（３−アミノプロピル）エーテル、１，２−ビス−
（３−アミノプロピル）エタン、１，３−ビス−（３−
アミノプロピル）−２，２−ジメチルプロパン、α，ω
−（３−アミノプロピル）−ポリエチレングリコール
等）と公知のジカルボン酸とを反応当量比（ジカルボン
酸のカルボキシル基／ポリオキシアルキレンジアミンの
アミノ基）が１を超える条件で反応させて得られるポリ
オキシアルキレンアミドジカルボン酸、ポリオキシアル
キレンジアミンとトリカルボン酸モノ無水物（例えば、
トリメリット酸無水物、トリカルバリル酸無水物、マレ
イン酸無水物のリシノレイン酸脱水化物付加物、マレイ
ン酸無水物のソルビン酸付加物等）とを反応当量比（ト
リカルボン酸モノ無水物の酸無水物基／ポリオキシアル
キレンジアミンのアミノ基）が１の条件で反応させて得
られるポリオキシアルキレンジイミドジカルボン酸、ポ
リオキシアルキレンジアミンとテトラカルボン酸ニ無水
物（例えば、ピロメリット酸無水物、ベンゾフェノンテ
トラカルボン酸二無水物、ｓ−ビフェニルテトラカルボ
ン酸二無水物、ジフェニルスルホンテトラカルボン酸二
無水物、メチルシクロヘキセンテトラカルボン酸二無水
物、エチレングリコールビスアンヒドロトリメリテート
等）とを反応当量比（ポリオキシアルキレンジアミンの
アミノ基／テトラカルボン酸二無水物の酸無水物基）が
１を超える条件で反応させて得られるポリオキシアルキ
レンイミドジアミンに、上記トリカルボン酸モノ無水物
を反応当量比（トリカルボン酸モノ無水物の酸無水物基
／ポリオキシアルキレンイミドジアミンのアミノ基）が
１の条件で反応させて得られるポリオキシアルキレンポ
リイミドジカルボン酸などが挙げられる。As the dicarboxylic acid containing an oxyalkylene group / amide or imide bond, polyoxyalkylenediamine (for example, trade name: Jeffamine D-230, D-400, D-200 manufactured by Huntsman Corporation)
0, D-4000, ED-600, ED-900, ED
2001, EDR-148, bis- (3-aminopropyl) ether, 1,2-bis-, manufactured by Koei Chemical Industry Co., Ltd.
(3-aminopropyl) ethane, 1,3-bis- (3-
Aminopropyl) -2,2-dimethylpropane, α, ω
-(3-aminopropyl) -polyethylene glycol) and a known dicarboxylic acid under the condition that the reaction equivalent ratio (carboxyl group of dicarboxylic acid / amino group of polyoxyalkylenediamine) exceeds 1. Alkylene amide dicarboxylic acid, polyoxyalkylenediamine and tricarboxylic acid monoanhydride (for example,
Trimellitic anhydride, tricarballylic anhydride, ricinoleic acid dehydration adduct of maleic anhydride, sorbic acid adduct of maleic anhydride, etc.) and the reaction equivalent ratio (tricarboxylic acid monoanhydride to acid anhydride) Group / amino group of polyoxyalkylenediamine) under the condition (1), polyoxyalkylenediimide dicarboxylic acid, polyoxyalkylenediamine and tetracarboxylic dianhydride (for example, pyromellitic anhydride, benzophenone tetracarboxylic acid) Acid dianhydride, s-biphenyltetracarboxylic dianhydride, diphenylsulfonetetracarboxylic dianhydride, methylcyclohexenetetracarboxylic dianhydride, ethylene glycol bisanhydrotrimellitate, etc.) in a reaction equivalent ratio (poly Amino group of oxyalkylenediamine / tetra The reaction equivalent ratio of the above tricarboxylic acid monoanhydride to the polyoxyalkylenedimidodiamine obtained by reacting the acid anhydride group of the sulfonic acid dianhydride) under more than 1 (the acid anhydride group of the tricarboxylic acid monoanhydride) / Amino group of polyoxyalkylene imide diamine) under the condition (1).
【０００８】また、オキシアルキレン基・エステル結合
含有ジカルボン酸としては、公知のポリオキシアルキレ
ンジオールと公知のジカルボン酸とを反応当量比（ジカ
ルボン酸のカルボキシル基／ポリオキシアルキレンジオ
ールの水酸基）が１を超える条件で反応させて得られる
ポリオキシアルキレンエステルジカルボン酸などが挙げ
られる。また、オキシアルキレンジカルボン酸として
は、ポリオキシエチレンジグリコール酸（例えば、川研
ファインケミカル(株)製商品名 ＰＥＯ酸＃４００、＃
１０００、＃４０００等）などが挙げられる。これらの
うちでは、得られる親水性ポリアミド系樹脂の親水性と
耐熱性とのバランスの点で、オキシアルキレン基・アミ
ド又はイミド結合含有ジカルボン酸が好ましく、中で
も、得られる親水性ポリアミド系樹脂の３６５nmにおけ
る光透過率を大きくできる点からポリオキシアルキレン
アミドジカルボン酸が好ましい。また、同じ点からオキ
シアルキレン基・エステル結合含有ジカルボン酸も好ま
しい。これらの（Ａ）ポリオキシアルキレン基を有する
親水性ジカルボン酸は、単独で又は二種類以上組み合わ
せて用いられる。Further, as the dicarboxylic acid containing an oxyalkylene group / ester bond, a known polyoxyalkylene diol and a known dicarboxylic acid have a reaction equivalent ratio (carboxyl group of dicarboxylic acid / hydroxyl group of polyoxyalkylene diol) of 1 And polyoxyalkylene ester dicarboxylic acid obtained by reaction under the above conditions. Examples of the oxyalkylenedicarboxylic acid include polyoxyethylene diglycolic acid (for example, PEO acids # 400, #, manufactured by Kawaken Fine Chemical Co., Ltd.)
1000, # 4000, etc.). Among them, oxyalkylene group / amide or imide bond-containing dicarboxylic acid is preferable in terms of balance between hydrophilicity and heat resistance of the obtained hydrophilic polyamide-based resin, and among them, 365 nm of the obtained hydrophilic polyamide-based resin is preferable. Polyoxyalkylene amide dicarboxylic acid is preferred from the viewpoint that the light transmittance in the above can be increased. From the same point, an oxyalkylene group / ester bond-containing dicarboxylic acid is also preferable. These (A) hydrophilic dicarboxylic acids having a polyoxyalkylene group are used alone or in combination of two or more.
【０００９】（Ａ）ポリオキシアルキレン基を有する親
水性ジカルボン酸のポリオキシアルキレン基部分の分子
量としては、２００〜１００００が好ましく、５００〜
５０００がより好ましく、１０００〜３０００が特に好
ましい。この分子量が２００未満では、得られる親水性
ポリアミド系樹脂の親水性、屈曲性が低下する傾向があ
り、分子量が１００００を超えると、得られる親水性ポ
リアミド系樹脂の耐熱性が低下する傾向がある。(A) The molecular weight of the polyoxyalkylene group of the hydrophilic dicarboxylic acid having a polyoxyalkylene group is preferably from 200 to 10,000, more preferably from 500 to 10,000.
5000 is more preferable, and 1000 to 3000 is particularly preferable. When the molecular weight is less than 200, the hydrophilicity and flexibility of the obtained hydrophilic polyamide-based resin tend to decrease, and when the molecular weight exceeds 10,000, the heat resistance of the obtained hydrophilic polyamide-based resin tends to decrease. .
【００１０】本発明における（Ｂ）ジイソシアネート又
はジアミンとしては、特に制限はないが、親水性ポリア
ミド系樹脂の製造の容易さの点でジイソシアネートの方
が好ましい。The diisocyanate or diamine (B) in the present invention is not particularly limited, but diisocyanate is preferred in view of easiness of producing a hydrophilic polyamide resin.
【００１１】ジイソシアネートとしては、例えば、４，
４′−ジフェニルメタンジイソシアネート、２，６−ト
リレンジイソシアネート、２，４−トリレンジイソシア
ネート、１，５−ナフタレンジイソシアネート、トリジ
ンジイソシアネート、ｐ−フェニレンジイソシアネー
ト、４，４′−ジフェニルエーテルジイソシアネート、
ｍ−キシリレンジイソシアネート、ｍ−テトラメチルキ
シリレンジイソシアネート等の芳香族ジイソシアネー
ト、ヘキサメチレンジイソシアネート、２，２，４−ト
リメチルヘキサメチレンジイソシアネート、２，４，４
−トリメチルヘキサメチレンジイソシアネート、リジン
ジイソシアネート等の脂肪族ジイソシアネート、イソホ
ロンジイソシアネート、４，４′−ジシクロヘキシルメ
タンジイソシアネート（水添化４，４′−ジフェニルメ
タンジイソシアネート）、トランスシクロヘキサン−
１，４−ジイソシアネート、水添化ｍ−キシリレンジイ
ソシアネート等の脂環式ジイソシアネート、３，９−ビ
ス（３−イソシアネートプロピル）−２，４，８，１０
−テトラスピロ［５，５］ウンデカン等の複素環式ジイ
ソシアネートなどが挙げられ、また、ジアミンとして
は、例えば、ｐ−フェニレンジアミン、ｍ−フェニレン
ジアミン、ｐ−キシリレンジアミン、ｍ−キシリレンジ
アミン、４，４′−（又は３，４′−、３，３′−、
２，４′−、２，２′−）ジアミノジフェニルメタン、
４，４′−（又は３，４′−、３，３′−、２，４′
−、２，２′−）ジアミノジフェニルエーテル、４，
４′−（又は３，４′−、３，３′−、２，４′−、
２，２′−）ジアミノジフェニルスルホン、４，４′−
（又は３，４′−、３，３′−、２，４′−、２，２′
−）ジアミノジフェニルスルフィド、４，４′−ベンゾ
フェノンジアミン、３，３′−ベンゾフェノンジアミ
ン、２，２−ビス〔４−（４−アミノフェノキシ）フェ
ニル〕プロパン、４，４′−ジアミノベンズアニリド等
が挙げられるが、親水性ポリアミド系樹脂の製造の容易
さの点でジイソシアネートの方が好ましく、なかでも、
得られる親水性ポリアミド系樹脂の耐熱性の点で、芳香
族ジイソシアネートがより好ましい。これらの（Ｂ）ジ
イソシアネート又はジアミンは、単独で又は二種類以上
組み合わせて用いられる。As the diisocyanate, for example, 4,
4'-diphenylmethane diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl ether diisocyanate,
aromatic diisocyanates such as m-xylylene diisocyanate, m-tetramethyl xylylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4
Aliphatic diisocyanates such as trimethylhexamethylene diisocyanate and lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate (hydrogenated 4,4'-diphenylmethane diisocyanate), transcyclohexane
Alicyclic diisocyanates such as 1,4-diisocyanate and hydrogenated m-xylylene diisocyanate, 3,9-bis (3-isocyanatopropyl) -2,4,8,10
A heterocyclic diisocyanate such as -tetraspiro [5,5] undecane; and diamines such as p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4 , 4'- (or 3,4'-, 3,3'-,
2,4 '-, 2,2'-) diaminodiphenylmethane,
4,4'- (or 3,4'-, 3,3'-, 2,4 '
-, 2,2 '-) diaminodiphenyl ether, 4,
4'- (or 3,4'-, 3,3'-, 2,4'-,
2,2 '-) diaminodiphenyl sulfone, 4,4'-
(Or 3,4'-, 3,3'-, 2,4'-, 2,2 '
-) Diaminodiphenyl sulfide, 4,4'-benzophenonediamine, 3,3'-benzophenonediamine, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4'-diaminobenzanilide and the like However, diisocyanates are preferred in view of ease of production of the hydrophilic polyamide-based resin, and among them,
Aromatic diisocyanates are more preferred in view of the heat resistance of the obtained hydrophilic polyamide-based resin. These (B) diisocyanates or diamines are used alone or in combination of two or more.
【００１２】本発明における（Ｃ）エポキシ樹脂として
は、特に制限はなく、例えば、ビスフェノールＡ型エポ
キシ樹脂、テトラブロモビスフェノールＡ型エポキシ樹
脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノール
ＡＤ型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフ
ェニル型エポキシ樹脂、テトラメチルビフェニル型エポ
キシ樹脂等の２官能芳香族グリシジルエーテル、フェノ
ールノボラック型エポキシ樹脂、クレゾールノボラック
型エポキシ樹脂、ジシクロペンタジエン−フェノール型
エポキシ樹脂、テトラフェニロールエタン型エポキシ樹
脂等の多官能芳香族グリシジルエーテル、ポリエチレン
グリコール型エポキシ樹脂、ポリプロピレングリコール
型エポキシ樹脂、ネオペンチルグリコール型エポキシ樹
脂、ジブロモネオペンチルグリコール型エポキシ樹脂、
ヘキサンジオール型エポキシ樹脂等の二官能脂肪族グリ
シジルエーテル、水添化ビスフェノールＡ型エポキシ樹
脂等の二官能脂環式グリシジルエーテル、トリメチロー
ルプロパン型エポキシ樹脂、ソルビトール型エポキシ樹
脂、グリセリン型エポキシ樹脂等の多官能脂肪族グリシ
ジルエーテル、フタル酸ジグリシジルエステル等の二官
能芳香族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
ルエステル等の二官能脂環式グリシジルエステル、Ｎ，
Ｎ−ジグリシジルアニリン、Ｎ，Ｎ−ジグリシジルトリ
フルオロメチルアニリン等の二官能芳香族グリシジルア
ミン、Ｎ，Ｎ，Ｎ′，Ｎ′−テトラグリシジル−４，４
−ジアミノジフェニルメタン、１，３−ビス（Ｎ，Ｎ−
グリシジルアミノメチル）シクロヘキサン、Ｎ，Ｎ，Ｏ
−トリグリシジル−ｐ−アミノフェノール等の多官能芳
香族グリシジルアミン、アリサイクリックジエポキシア
セタール、アリサイクリックジエポキシアジペート、ア
リサイクリックジエポキシカルボキシレート、ビニルシ
クロヘキセンジオキシド等の二官能脂環式エポキシ樹
脂、ジグリシジルヒダントイン等の二官能複素環式エポ
キシ樹脂、トリグリシジルイソシアヌレート等の多官能
複素環式エポキシ樹脂、オルガノポリシロキサン型エポ
キシ樹脂等の二官能又は多官能ケイ素含有エポキシ樹脂
などが挙げられる。これらのうちでは、親水性ポリアミ
ド系樹脂の製造反応の制御し易さの点で、二官能エポキ
シ樹脂が好ましく、二官能エポキシ樹脂のなかでも、得
られる親水性ポリアミド系樹脂の耐熱性の点で、二官能
芳香族グリシジルエーテルがより好ましく、そのなかで
も、廉価等の点で、ビスフェノールＡ型エポキシ樹脂が
特に好ましく、また、得られる親水性ポリアミド系樹脂
のアルカリ水溶液に対する溶解性を向上させる点から、
ビスフェノールＦ型エポキシ樹脂が特に好ましい。これ
らの（Ｃ）エポキシ樹脂は、単独で又は二種類以上組み
合わせて用いられる。The epoxy resin (C) in the present invention is not particularly limited. Examples thereof include bisphenol A epoxy resin, tetrabromobisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, and naphthalene epoxy resin. Bifunctional aromatic glycidyl ether such as resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene-phenol type epoxy resin, tetraphenylolethane type epoxy resin Polyfunctional aromatic glycidyl ether, polyethylene glycol epoxy resin, polypropylene glycol epoxy resin, neopentyl glycol epoxy resin, dibromoneo Emissions chill glycol type epoxy resin,
Bifunctional aliphatic glycidyl ether such as hexanediol type epoxy resin, bifunctional alicyclic glycidyl ether such as hydrogenated bisphenol A type epoxy resin, trimethylolpropane type epoxy resin, sorbitol type epoxy resin, glycerin type epoxy resin etc. Difunctional alicyclic glycidyl esters such as polyfunctional aliphatic glycidyl ethers, diglycidyl phthalate, etc., bifunctional aromatic glycidyl esters such as tetrahydrophthalic acid diglycidyl ester and hexahydrophthalic acid diglycidyl ester;
Bifunctional aromatic glycidylamines such as N-diglycidylaniline and N, N-diglycidyltrifluoromethylaniline; N, N, N ', N'-tetraglycidyl-4,4
-Diaminodiphenylmethane, 1,3-bis (N, N-
Glycidylaminomethyl) cyclohexane, N, N, O
Polyfunctional aromatic glycidylamine such as triglycidyl-p-aminophenol, alicyclic diepoxy acetal, alicyclic diepoxy adipate, alicyclic diepoxycarboxylate, and bifunctional alicyclic such as vinylcyclohexene dioxide Epoxy resins, bifunctional heterocyclic epoxy resins such as diglycidyl hydantoin, polyfunctional heterocyclic epoxy resins such as triglycidyl isocyanurate, and bifunctional or polyfunctional silicon-containing epoxy resins such as organopolysiloxane type epoxy resins. Can be Among these, a bifunctional epoxy resin is preferable in terms of easy control of the production reaction of the hydrophilic polyamide resin, and among the bifunctional epoxy resins, in view of the heat resistance of the obtained hydrophilic polyamide resin. Bifunctional aromatic glycidyl ethers are more preferable, and among them, bisphenol A type epoxy resin is particularly preferable in terms of cost and the like, and from the viewpoint of improving the solubility of the obtained hydrophilic polyamide-based resin in an aqueous alkali solution. ,
Bisphenol F type epoxy resins are particularly preferred. These (C) epoxy resins are used alone or in combination of two or more.
【００１３】本発明における（Ｄ）多価カルボン酸モノ
無水物としては、特に制限はなく、例えば、テトラヒド
ロフタル酸無水物、メチルテトラヒドロフタル酸無水
物、トリアルキルテトラヒドロフタル酸無水物、ヘキサ
ヒドロフタル酸無水物、メチルヘキサヒドロフタル酸無
水物、ナジック酸無水物、メチルナジック酸無水物、メ
チル２置換ブテニルテトラヒドロフタル酸無水物、イタ
コン酸無水物、コハク酸無水物、シトラコン酸無水物、
ドデセニルコハク酸無水物、マレイン酸無水物、メチル
シクロペンタジエンのマレイン酸無水物付加物、アルキ
ル化エンドアルキレンテトラヒドロフタル酸無水物、フ
タル酸無水物、クロレンド酸無水物、テトラクロロフタ
ル酸無水物、テトラブロモフタル酸無水物、トリカルバ
リル酸無水物、マレイン酸無水物のリシノレイン酸脱水
化物付加物、マレイン酸無水物のソルビン酸付加物、ト
リメリット酸無水物などが挙げられ、なかでも、反応
性、反応収率、廉価等の点で、テトラヒドロフタル酸無
水物が好ましい。これらの（Ｄ）多価カルボン酸モノ無
水物は、単独で又は二種類以上組み合わせて用いられ
る。The polyhydric carboxylic acid monoanhydride (D) in the present invention is not particularly limited. Examples thereof include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Acid anhydride, methyl hexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, methyl 2-substituted butenyltetrahydrophthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride,
Dodecenyl succinic anhydride, maleic anhydride, maleic anhydride adduct of methylcyclopentadiene, alkylated endoalkylenetetrahydrophthalic anhydride, phthalic anhydride, chlorendic anhydride, tetrachlorophthalic anhydride, tetrabromo Phthalic anhydride, tricarballylic anhydride, ricinoleic acid dehydrated adduct of maleic anhydride, sorbic acid adduct of maleic anhydride, trimellitic anhydride and the like. Tetrahydrophthalic anhydride is preferred in terms of yield, cost and the like. These polyhydric carboxylic acid monoanhydrides (D) are used alone or in combination of two or more.
【００１４】本発明の親水性ポリアミド系樹脂の製造工
程は、まず、（Ａ）ポリオキシアルキレン骨格を有する
親水性ジカルボン酸と（Ｂ）ジイソシアネート又はジア
ミンを反応させてポリアミド中間体を得る工程、次い
で、このポリアミド中間体に（Ｃ）エポキシ樹脂を反応
させてポリアミド系樹脂中間体を得る工程、次いで、こ
のポリアミド系樹脂中間体に（Ｄ）多価カルボン酸モノ
無水物を反応させて親水性ポリアミド系樹脂を得る工程
の三工程からなる。The process for producing the hydrophilic polyamide resin of the present invention comprises (A) a step of reacting a hydrophilic dicarboxylic acid having a polyoxyalkylene skeleton with (B) a diisocyanate or diamine to obtain a polyamide intermediate. Reacting the polyamide intermediate with (C) an epoxy resin to obtain a polyamide resin intermediate, and then reacting the polyamide resin intermediate with (D) a polycarboxylic monoanhydride to form a hydrophilic polyamide. It comprises three steps of obtaining a base resin.
【００１５】ポリアミド中間体を得る工程における
（Ａ）ポリオキシアルキレン骨格を有する親水性ジカル
ボン酸と（Ｂ）ジイソシアネート又はジアミンの反応当
量比（（Ａ）のカルボキシル基／（Ｂ）のイソシアネー
ト基又はアミノ基）は、１．０３〜２とすることが好ま
しく、１．０５〜１．７がより好ましく、１．１〜１．
５が特に好ましい。この反応当量比（（Ａ）のカルボキ
シル基／（Ｂ）のイソシアネート基又はアミノ基）が
１．０３未満では、得られるポリアミド中間体の両末端
がカルボキシル基でないものが生成し易く、次の（Ｃ）
エポキシ樹脂との反応が困難になる傾向があり、反応当
量比が２を超えると、（Ａ）ポリオキシアルキレン骨格
を有する親水性ジカルボン酸が未反応物として残留し易
く、得られる親水性ポリアミド系樹脂の耐熱性が低下す
る傾向がある。In the step of obtaining a polyamide intermediate, the reaction equivalent ratio of (A) a hydrophilic dicarboxylic acid having a polyoxyalkylene skeleton and (B) a diisocyanate or a diamine ((A) carboxyl group / (B) isocyanate group or amino) Group) is preferably 1.03 to 2, more preferably 1.05 to 1.7, and 1.1 to 1.
5 is particularly preferred. When the reaction equivalent ratio (the carboxyl group of (A) / isocyanate group or amino group of (B)) is less than 1.03, a polyamide intermediate having both terminals which are not carboxyl groups is likely to be formed. C)
When the reaction with the epoxy resin tends to be difficult, and when the reaction equivalent ratio exceeds 2, (A) the hydrophilic dicarboxylic acid having a polyoxyalkylene skeleton tends to remain as an unreacted substance, and the resulting hydrophilic polyamide-based The heat resistance of the resin tends to decrease.
【００１６】ポリアミド中間体を得る工程における
（Ａ）成分と（Ｂ）成分の反応は、有機溶媒中で実施さ
れる。有機溶媒としては、特に制限はなく、例えば、γ
−ブチロラクトン、γ−カプロラクトン等のラクトン
類、エチレンカーボネート、プロピレンカーボネート等
のカーボネート類、メチルエチルケトン、メチルイソブ
チルケトン、シクロヘキサノン等のケトン類、酢酸エチ
ル、酢酸ｎ−ブチル等のエステル類、ジグライム、トリ
グライム、テトラグライム等のグライム類、トルエン、
キシレン、シクロヘキサン等の炭化水素類、Ｎ−メチル
−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、
Ｎ，Ｎ−ジメチルホルムアミド等のアミド類、Ｎ，Ｎ−
ジメチルエチレンウレア、Ｎ，Ｎ−ジメチルプロピレン
ウレア、テトラメチルウレア等のウレア類、スルホラン
等のスルホン類などが挙げられ、なかでも、ラクトン類
を主成分とするのが、親水性ポリアミド系樹脂ワニスか
ら加熱処理によって膜化する際の低温乾燥性に優れる点
で好ましい。The reaction between the components (A) and (B) in the step of obtaining the polyamide intermediate is carried out in an organic solvent. The organic solvent is not particularly limited, for example, γ
-Butyrolactone, lactones such as γ-caprolactone, carbonates such as ethylene carbonate and propylene carbonate, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate and n-butyl acetate, diglyme, triglyme, tetra Grimes such as grime, toluene,
Hydrocarbons such as xylene and cyclohexane, N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
Amides such as N, N-dimethylformamide, N, N-
Examples thereof include ureas such as dimethylethylene urea, N, N-dimethylpropylene urea, and tetramethyl urea, and sulfones such as sulfolane. Among them, lactones are mainly used as hydrophilic polyamide resin varnishes. This is preferable in that it has excellent low-temperature drying properties when formed into a film by heat treatment.
【００１７】有機溶媒の使用量は、（Ａ）成分と（Ｂ）
成分との総量１００重量部に対して、３０〜２０００重
量部が好ましく、５０〜１０００重量部がより好まし
く、７０〜４００が特に好ましい。この有機溶媒の使用
量が３０重量部未満では溶解性が乏しく、反応系の不均
一化や高粘度化を起こしやすい傾向があり、有機溶媒の
使用量が２０００重量部を超えると反応が進みにくく、
反応が完結しにくい傾向がある。これらの有機溶媒は、
単独で又は二種類以上組み合わせて用いられる。The amount of the organic solvent used is as follows: component (A) and component (B)
The amount is preferably from 30 to 2,000 parts by weight, more preferably from 50 to 1,000 parts by weight, particularly preferably from 70 to 400 parts by weight, based on 100 parts by weight of the total amount of the components. If the amount of the organic solvent used is less than 30 parts by weight, the solubility is poor, the reaction system tends to be non-uniform and the viscosity tends to be high, and if the amount of the organic solvent exceeds 2,000 parts by weight, the reaction hardly proceeds. ,
The reaction tends to be difficult to complete. These organic solvents are
They are used alone or in combination of two or more.
【００１８】ポリアミド中間体を得る工程における
（Ａ）成分と（Ｂ）成分の反応温度は、１００〜３００
℃が好ましく、１５０〜２７０℃がより好ましく、１７
０〜２５０℃が特に好ましい。この反応温度が１００℃
未満では反応が進みにくく、反応が完結しにくい傾向が
あり、反応温度が３００℃を超えると副反応によるゲル
化等が起こりやすく、反応が制御しにくい傾向がある。The reaction temperature of the component (A) and the component (B) in the step of obtaining the polyamide intermediate is from 100 to 300.
° C is preferable, 150 to 270 ° C is more preferable,
0-250 ° C is particularly preferred. The reaction temperature is 100 ° C
When the reaction temperature is lower than 300 ° C., the reaction tends to be difficult to proceed and the reaction tends to be difficult to be completed.
【００１９】ポリアミド中間体を得る工程において、
（Ａ）ポリオキシアルキレン骨格を有する親水性ジカル
ボン酸の一部を、ポリオキシアルキレン骨格を含まない
ジカルボン酸に変更して使用することができる。ポリオ
キシアルキレン骨格を含まないジカルボン酸としては、
特に制限はなく、公知のジカルボン酸、例えば、コハク
酸、グルタル酸、アジピン酸、ピメリン酸、アゼライン
酸、セバシン酸、ドデカン二酸、エイコサン二酸、カー
ボネート基含有ジカルボン酸等の脂肪族ジカルボン酸、
ダイマー酸、１，４−シクロヘキサンジカルボン酸等の
脂環式ジカルボン酸、イソフタル酸、テレフタル酸、フ
タル酸、１，５−ナフタレンジカルボン酸、４，４′−
ジフェニルエーテルジカルボン酸、４，４′−ジフェニ
ルスルホンジカルボン酸、４，４′−ベンゾフェノンジ
カルボン等の芳香族ジカルボン酸などが挙げられる。In the step of obtaining a polyamide intermediate,
(A) A part of the hydrophilic dicarboxylic acid having a polyoxyalkylene skeleton can be used after being changed to a dicarboxylic acid containing no polyoxyalkylene skeleton. As a dicarboxylic acid containing no polyoxyalkylene skeleton,
There is no particular limitation, and known dicarboxylic acids, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, dodecane diacid, eicosane diacid, aliphatic dicarboxylic acids such as carbonate group-containing dicarboxylic acids,
Alicyclic dicarboxylic acids such as dimer acid and 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, phthalic acid, 1,5-naphthalenedicarboxylic acid, and 4,4′-
Examples thereof include aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, and 4,4'-benzophenone dicarboxylic acid.
【００２０】ポリオキシアルキレン骨格を含まないジカ
ルボン酸を併用する場合、その配合量は、（Ａ）ポリオ
キシアルキレン骨格を有する親水性ジカルボン酸の一部
置換量として０〜９０重量％とされ、１０〜７０重量％
が好ましく、２０〜５０重量％がより好ましい。配合量
が９０重量％を超えると、得られる親水性ポリアミド系
樹脂の親水性が低下し、感光性樹脂組成物のポリマ成分
として用いたときに、その感光性樹脂組成物のアルカリ
現像性が低下する傾向があり、また、屈曲性が低下する
傾向がある。これらのポリオキシアルキレン骨格を含ま
ないジカルボン酸は、単独で又は二種類以上組み合わせ
て用いることができる。When a dicarboxylic acid containing no polyoxyalkylene skeleton is used in combination, the compounding amount thereof is 0 to 90% by weight as a partial substitution amount of (A) a hydrophilic dicarboxylic acid having a polyoxyalkylene skeleton. ~ 70% by weight
, Preferably 20 to 50% by weight. When the amount is more than 90% by weight, the hydrophilicity of the resulting hydrophilic polyamide-based resin decreases, and when used as a polymer component of the photosensitive resin composition, the alkali developability of the photosensitive resin composition decreases. And the flexibility tends to decrease. These dicarboxylic acids containing no polyoxyalkylene skeleton can be used alone or in combination of two or more.
【００２１】上記ポリアミド中間体に（Ｃ）エポキシ樹
脂を反応させてポリアミド系樹脂中間体を得る工程にお
いて、ポリアミド中間体と（Ｃ）エポキシ樹脂の反応当
量比（（Ｃ）のエポキシ基／ポリアミド中間体のカルボ
キシル基）は、０．５〜３が好ましく、１．１〜２．５
がより好ましく、１．２〜２．０が特に好ましい。この
反応当量比（（Ｃ）のエポキシ基／ポリアミド中間体の
カルボキシル基）が０．５未満では、高分子量化しにく
く、得られる親水性ポリアミド系樹脂の耐熱性、屈曲性
が低下する傾向があり、反応当量比が３を超えると、副
反応によるゲル化等が起こりやすく、反応が制御しにく
い傾向があり、また、橋架け密度が高くなり、得られる
親水性ポリアミド系樹脂の屈曲性が低下する傾向があ
る。In the step of reacting the polyamide intermediate with the (C) epoxy resin to obtain a polyamide resin intermediate, the reaction equivalent ratio of the polyamide intermediate to the (C) epoxy resin ((C) epoxy group / polyamide intermediate) 0.5-3, preferably 1.1-2.5
Is more preferable, and 1.2 to 2.0 is particularly preferable. When the reaction equivalent ratio (epoxy group of (C) / carboxyl group of polyamide intermediate) is less than 0.5, it is difficult to increase the molecular weight, and the heat resistance and flexibility of the resulting hydrophilic polyamide resin tend to decrease. If the reaction equivalent ratio exceeds 3, gelation or the like due to side reactions tends to occur, the reaction tends to be difficult to control, and the bridging density increases, and the flexibility of the resulting hydrophilic polyamide-based resin decreases. Tend to.
【００２２】ポリアミド系樹脂中間体を得る工程におけ
るポリアミド中間体と（Ｃ）成分の反応は、先のポリア
ミド中間体を得る工程に引き続いて、有機溶媒中で実施
される。有機溶媒としては、特に制限はなく、例えば、
先に述べたポリアミド中間体を得る工程に使用される有
機溶媒がそのまま挙げられる。なお、先のポリアミド中
間体を得る工程において、ラクトン類を主成分とする場
合は、得られる親水性ポリアミド系樹脂の溶解性、低温
乾燥性の点で、アミド類、なかでも低沸点のＮ，Ｎ−ジ
メチルホルムアミドとの併用が好ましい。The reaction between the polyamide intermediate and the component (C) in the step of obtaining the polyamide resin intermediate is carried out in an organic solvent following the step of obtaining the polyamide intermediate. The organic solvent is not particularly limited, for example,
The organic solvent used in the step of obtaining the above-mentioned polyamide intermediate can be used as it is. In the case of using a lactone as a main component in the step of obtaining the polyamide intermediate, amides, especially low-boiling N, are preferred in terms of solubility and low-temperature drying property of the obtained hydrophilic polyamide-based resin. Use in combination with N-dimethylformamide is preferred.
【００２３】有機溶媒の使用量は、ポリアミド中間体と
（Ｃ）成分との総量１００重量部に対して、３０〜２０
００重量部が好ましく、５０〜１０００重量部がより好
ましく、７０〜４００が特に好ましい。この有機溶媒の
使用量が３０重量部未満では溶解性が乏しく、反応系の
不均一化や高粘度化を起こしやすい傾向があり、有機溶
媒の使用量が２０００重量部を超えると反応が進みにく
く、反応が完結しにくい傾向がある。これらの有機溶媒
は、単独で又は二種類以上組み合わせて用いられる。The amount of the organic solvent used is 30 to 20 parts by weight based on 100 parts by weight of the total amount of the polyamide intermediate and the component (C).
00 parts by weight is preferable, 50 to 1000 parts by weight is more preferable, and 70 to 400 parts is particularly preferable. If the amount of the organic solvent used is less than 30 parts by weight, the solubility is poor, the reaction system tends to be non-uniform and the viscosity tends to be high, and if the amount of the organic solvent exceeds 2,000 parts by weight, the reaction hardly proceeds. The reaction tends to be difficult to complete. These organic solvents are used alone or in combination of two or more.
【００２４】ポリアミド系樹脂中間体を得る工程におけ
るポリアミド中間体と（Ｃ）成分の反応温度は、５０〜
２５０℃が好ましく、１００〜２００℃がより好まし
く、１２０〜１８０℃が特に好ましい。この反応温度が
５０℃未満では反応が進みにくく、反応が完結しにくい
傾向があり、反応温度が２５０℃を超えると副反応によ
るゲル化等が起こりやすく、反応が制御しにくい傾向が
ある。The reaction temperature between the polyamide intermediate and the component (C) in the step of obtaining the polyamide resin intermediate is from 50 to 50.
250 ° C is preferred, 100 to 200 ° C is more preferred, and 120 to 180 ° C is particularly preferred. When the reaction temperature is lower than 50 ° C., the reaction does not easily proceed, and the reaction tends to be difficult to complete. When the reaction temperature exceeds 250 ° C., gelation or the like due to side reactions tends to occur, and the reaction tends to be difficult to control.
【００２５】ポリアミド系樹脂中間体を得た後に、得ら
れたポリアミド系樹脂中間体のエポキシ基を封止する目
的で、ポリアミド系樹脂中間体にモノカルボン酸を反応
させることができる。モノカルボン酸としては、特に制
限はなく、例えば、メタクリル酸、アクリル酸等の光重
合性不飽和基含有脂肪族モノカルボン酸、ギ酸、酢酸、
プロピオン酸、酪酸、ヘキサン酸等の脂肪族モノカルボ
ン酸、安息香酸、ジフェニル酢酸等の芳香族モノカルボ
ン酸などが挙げられる。これらのうちでは、親水性ポリ
アミド系樹脂に光硬化性を付与できる点で、光重合性不
飽和基含有脂肪族モノカルボン酸が好ましい。After obtaining the polyamide resin intermediate, a monocarboxylic acid can be reacted with the polyamide resin intermediate for the purpose of sealing the epoxy group of the obtained polyamide resin intermediate. The monocarboxylic acid is not particularly limited, for example, methacrylic acid, a photopolymerizable unsaturated group-containing aliphatic monocarboxylic acid such as acrylic acid, formic acid, acetic acid,
Examples thereof include aliphatic monocarboxylic acids such as propionic acid, butyric acid, and hexanoic acid, and aromatic monocarboxylic acids such as benzoic acid and diphenylacetic acid. Among these, a photopolymerizable unsaturated group-containing aliphatic monocarboxylic acid is preferred because it can impart photocurability to the hydrophilic polyamide-based resin.
【００２６】モノカルボン酸を用いる場合、ポリアミド
系樹脂中間体とモノカルボン酸の反応当量比（モノカル
ボン酸のカルボキシル基／ポリアミド系樹脂中間体のエ
ポキシ基）は、０．５〜５が好ましく、０．８〜２がよ
り好ましく、１〜１．２が特に好ましい。この反応当量
比（モノカルボン酸のカルボキシル基／ポリアミド系樹
脂中間体のエポキシ基）が０．５未満では未反応のエポ
キシ基が残存し、親水性ポリアミド系樹脂の保存安定性
が低下する傾向があり、反応当量比が５を越えると未反
応のモノカルボン酸が多量に残留し、親水性ポリアミド
系樹脂ワニスの皮膚刺激性が増大する傾向がある。これ
らのモノカルボン酸は、単独で又は二種類以上組み合わ
せて用いることができる。When a monocarboxylic acid is used, the reaction equivalent ratio of the polyamide resin intermediate to the monocarboxylic acid (carboxyl group of monocarboxylic acid / epoxy group of polyamide resin intermediate) is preferably 0.5 to 5, 0.8 to 2 is more preferable, and 1 to 1.2 is particularly preferable. When the reaction equivalent ratio (carboxyl group of monocarboxylic acid / epoxy group of polyamide resin intermediate) is less than 0.5, unreacted epoxy groups remain, and the storage stability of hydrophilic polyamide resin tends to decrease. If the reaction equivalent ratio exceeds 5, a large amount of unreacted monocarboxylic acid remains, and the skin irritation of the hydrophilic polyamide resin varnish tends to increase. These monocarboxylic acids can be used alone or in combination of two or more.
【００２７】上記ポリアミド系樹脂中間体に（Ｄ）多価
カルボン酸モノ無水物を反応させて本発明の親水性ポリ
アミド系樹脂を得る工程において、ポリアミド系樹脂中
間体と（Ｄ）多価カルボン酸モノ無水物の反応当量比
（（Ｄ）の酸無水物基／ポリアミド系樹脂中間体の水酸
基）は、０．１〜１．５が好ましく、０．３〜１とする
ことがより好ましく、０．６〜０．９とすることが特に
好ましい。この反応当量比（（Ｄ）の酸無水物基／ポリ
アミド系樹脂中間体の水酸基）が０．１未満では得られ
る親水性ポリアミド系樹脂のアルカリ水溶液に対する溶
解性が乏しく、感光性樹脂組成物のポリマ成分として用
いたときに、その感光性樹脂組成物のアルカリ現像性が
低下する傾向があり、反応当量比が１．５を超えると
（Ｄ）多価カルボン酸モノ無水物が未反応物として多量
に残留し易く、親水性ポリアミド系樹脂の保存安定性が
低下する傾向がある。In the step of obtaining the hydrophilic polyamide resin of the present invention by reacting the polyamide resin intermediate with the polycarboxylic acid monoanhydride (D), the polyamide resin intermediate and the (D) polycarboxylic acid are used. The reaction equivalent ratio of the monoanhydride (acid anhydride group of (D) / hydroxyl group of the polyamide resin intermediate) is preferably 0.1 to 1.5, more preferably 0.3 to 1, and more preferably 0 to 1. It is particularly preferable to set it to 0.6 to 0.9. When the reaction equivalent ratio (acid anhydride group of (D) / hydroxyl group of polyamide resin intermediate) is less than 0.1, the resulting hydrophilic polyamide resin has poor solubility in an aqueous alkali solution, and the photosensitive resin composition has a low solubility. When used as a polymer component, the alkali developability of the photosensitive resin composition tends to decrease. When the reaction equivalent ratio exceeds 1.5, (D) polyhydric carboxylic acid monoanhydride becomes unreacted. A large amount tends to remain, and the storage stability of the hydrophilic polyamide-based resin tends to decrease.
【００２８】本発明の親水性ポリアミド系樹脂を得る工
程におけるポリアミド系樹脂中間体と（Ｄ）成分の反応
は、先のポリアミド系樹脂中間体を得る工程に引き続い
て、有機溶媒中で実施される。有機溶媒としては、特に
制限はなく、例えば、先に述べたポリアミド中間体を得
る工程に使用される有機溶媒がそのまま挙げられる。な
お、先のポリアミド系樹脂中間体を得る工程において、
ラクトン類とアミド類とからなる混合溶媒を主成分とし
た場合は、特に有機溶媒を追加して使用する必要はな
い。有機溶媒の使用量は、ポリアミド系樹脂中間体と
（Ｄ）成分との総量１００重量部に対して、３０〜２０
００重量部が好ましく、５０〜１０００重量部がより好
ましく、７０〜４００が特に好ましい。この有機溶媒の
使用量が３０重量部未満では溶解性が乏しく、反応系の
不均一化や高粘度化を起こしやすい傾向があり、有機溶
媒の使用量が２０００重量部を超えると反応が進みにく
く、反応が完結しにくい傾向がある。これらの有機溶媒
は、単独で又は二種類以上組み合わせて用いられる。The reaction between the polyamide resin intermediate and the component (D) in the step of obtaining the hydrophilic polyamide resin of the present invention is carried out in an organic solvent, following the step of obtaining the polyamide resin intermediate. . The organic solvent is not particularly limited, and for example, the organic solvent used in the step of obtaining the polyamide intermediate described above can be used as it is. In the step of obtaining the polyamide-based resin intermediate,
When a mixed solvent composed of a lactone and an amide is mainly used, it is not necessary to use an additional organic solvent. The amount of the organic solvent used is 30 to 20 parts by weight based on 100 parts by weight of the total amount of the polyamide resin intermediate and the component (D).
00 parts by weight is preferable, 50 to 1000 parts by weight is more preferable, and 70 to 400 parts is particularly preferable. If the amount of the organic solvent used is less than 30 parts by weight, the solubility is poor, the reaction system tends to be non-uniform and the viscosity tends to be high, and if the amount of the organic solvent exceeds 2,000 parts by weight, the reaction hardly proceeds. The reaction tends to be difficult to complete. These organic solvents are used alone or in combination of two or more.
【００２９】本発明の親水性ポリアミド系樹脂を得る工
程におけるポリアミド系樹脂中間体と（Ｄ）成分の反応
温度は、４０〜２５０℃が好ましく、６０〜２００℃が
より好ましく、８０〜１８０℃が特に好ましい。この反
応温度が４０℃未満では反応が進みにくく、反応が完結
しにくい傾向があり、反応温度が２５０℃を超えると副
反応によるゲル化等が起こりやすく、反応が制御しにく
い傾向がある。The reaction temperature of the polyamide resin intermediate and the component (D) in the step of obtaining the hydrophilic polyamide resin of the present invention is preferably from 40 to 250 ° C., more preferably from 60 to 200 ° C., and preferably from 80 to 180 ° C. Particularly preferred. If the reaction temperature is lower than 40 ° C., the reaction does not easily proceed and the reaction tends to be difficult to be completed.
【００３０】ポリアミド系樹脂中間体を得た後及び／又
は本発明の親水性ポリアミド系樹脂を得た後に、親水性
ポリアミド系樹脂に光硬化性を付与する目的で、ポリア
ミド系樹脂中間体及び／又は親水性ポリアミド系樹脂に
光重合性不飽和基含有脂肪族モノイソシアネートを反応
させることができる。光重合性不飽和基含有脂肪族モノ
イソシアネートとしては、特に制限はなく、例えば、２
−イソシアネートエチルメタクリレート、メタクリロイ
ルイソシアネート等が挙げられる。After obtaining the polyamide-based resin intermediate and / or the hydrophilic polyamide-based resin of the present invention, the polyamide-based resin intermediate and / or Alternatively, a hydrophilic polyamide-based resin can be reacted with a photopolymerizable unsaturated group-containing aliphatic monoisocyanate. The photopolymerizable unsaturated group-containing aliphatic monoisocyanate is not particularly limited.
-Isocyanate ethyl methacrylate, methacryloyl isocyanate and the like.
【００３１】光重合性不飽和基含有脂肪族モノイソシア
ネートを用いる場合、ポリアミド系樹脂中間体及び／又
は親水性ポリアミド系樹脂と光重合性不飽和基含有脂肪
族モノイソシアネートの反応当量比（光重合性不飽和基
含有脂肪族モノイソシアネートのイソシアネート基／ポ
リアミド系樹脂中間体及び／又は親水性ポリアミド系樹
脂の水酸基）は、０．０５〜１．５が好ましく、０．１
〜１がより好ましく、０．１〜０．４が特に好ましい。
この反応当量比（光重合性不飽和基含有脂肪族モノイソ
シアネートのイソシアネート基／ポリアミド系樹脂中間
体及び／又は親水性ポリアミド系樹脂の水酸基）が０．
０５未満では親水性ポリアミド系樹脂の光硬化性が低
く、感光性樹脂組成物のポリマ成分として用いたとき
に、その感光性樹脂組成物の感度が低下する傾向にあ
り、反応当量比が１．５を超えると光重合性不飽和基含
有脂肪族モノイソシアネートが未反応物として残留し易
く、親水性ポリアミド系樹脂の保存安定性が低下する傾
向がある。これらの光重合性不飽和基含有脂肪族モノイ
ソシアネートは、単独で又は二種類以上組み合わせて用
いることができる。When an aliphatic monoisocyanate containing a photopolymerizable unsaturated group is used, the reaction equivalent ratio of a polyamide resin intermediate and / or a hydrophilic polyamide resin to an aliphatic monoisocyanate containing a photopolymerizable unsaturated group (photopolymerization) (Isocyanate group of aliphatic unsaturated isocyanate group-containing aliphatic monoisocyanate / hydroxyl group of polyamide-based resin intermediate and / or hydrophilic polyamide-based resin) is preferably 0.05 to 1.5, more preferably 0.1 to 1.5.
To 1 is more preferable, and 0.1 to 0.4 is particularly preferable.
This reaction equivalent ratio (isocyanate group of the photopolymerizable unsaturated group-containing aliphatic monoisocyanate / hydroxyl group of the polyamide resin intermediate and / or the hydrophilic polyamide resin) is 0.
If it is less than 05, the photocurability of the hydrophilic polyamide resin is low, and when used as a polymer component of the photosensitive resin composition, the sensitivity of the photosensitive resin composition tends to decrease. If it exceeds 5, the photopolymerizable unsaturated group-containing aliphatic monoisocyanate tends to remain as an unreacted product, and the storage stability of the hydrophilic polyamide-based resin tends to decrease. These aliphatic monoisocyanates containing a photopolymerizable unsaturated group can be used alone or in combination of two or more.
【００３２】本発明においては、必要に応じて、反応触
媒が用いられる。反応触媒としては、特に制限はなく、
例えば、トリエチルアミン、トリエチレンジアミン、
Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジエチルアニリ
ン、Ｎ，Ｎ−ジメチルベンジルアミン、Ｎ−メチルモル
フォリン、Ｎ−エチルモルフォリン、Ｎ，Ｎ′−ジメチ
ルピペラジン、ピリジン、ピコリン、１，８−ジアザビ
シクロ［５，４，０］ウンデセン−７等の三級アミン、
２−メチルイミダゾール、２−エチルイミダゾール、２
−エチル−４−メチルイミダゾール、２−メチル−４−
メチルイミダゾール、１−シアノエチル−２−メチルイ
ミダゾール、１−シアノエチル−２−フェニルイミダゾ
ール、２−フェニル−４−メチル−５−ヒドロキシメチ
ルイミダゾール、２−フェニル−４，５−ジヒドロキシ
メチルイミダゾール、１−アジン−２−メチルイミダゾ
ール等のイミダゾール類、ジブチルチンジラウレート、
１，３−ジアセトキシテトラブチルジスタノキサン等の
有機スズ化合物、臭化テトラエチルアンモニウム、臭化
テトラブチルアンモニウム、塩化ベンジルトリエチルア
ンモニウム、塩化トリオクチルメチルアンモニウム、臭
化セチルトリメチルアンモニウム、ヨウ化テトラブチル
アンモニウム、ヨウ化ドデシルトリメチルアンモニウ
ム、ベンジルジメチルテトラデシルアンモニウムアセテ
ート等の４級アンモニウム塩、塩化テトラフェニルフォ
スフォニウム、塩化トリフェニルメチルフォスフォニウ
ム、臭化テトラメチルフォスフォニウム等の４級フォス
フォニウム塩、３−メチル−１−フェニル−２−フォス
フォレン−１−オキシド等の有機リン化合物、安息香酸
ナトリウム、安息香酸カリウム等の有機酸アルカリ金属
塩、塩化亜鉛、塩化鉄、塩化リチウム、臭化リチウム等
の無機塩、オクタカルボニル二コバルト（コバルトカル
ボニル）等の金属カルボニルなどが挙げられる。これら
の反応触媒は、単独でまたは二種以上組合わせて用いる
ことができる。In the present invention, a reaction catalyst is used if necessary. The reaction catalyst is not particularly limited,
For example, triethylamine, triethylenediamine,
N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N, N'-dimethylpiperazine, pyridine, picoline, 1,8- Tertiary amines such as diazabicyclo [5,4,0] undecene-7;
2-methylimidazole, 2-ethylimidazole, 2
-Ethyl-4-methylimidazole, 2-methyl-4-
Methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-azine Imidazoles such as -2-methylimidazole, dibutyltin dilaurate,
Organotin compounds such as 1,3-diacetoxytetrabutyldistannoxane, tetraethylammonium bromide, tetrabutylammonium bromide, benzyltriethylammonium chloride, trioctylmethylammonium chloride, cetyltrimethylammonium bromide, tetrabutylammonium iodide Quaternary ammonium salts such as dodecyltrimethylammonium iodide and benzyldimethyltetradecylammonium acetate; quaternary ammonium salts such as tetraphenylphosphonium chloride, triphenylmethylphosphonium chloride, tetramethylphosphonium bromide Phosphorus compounds such as, 3-methyl-1-phenyl-2-phospholene-1-oxide, alkali metal salts of organic acids such as sodium benzoate and potassium benzoate, zinc chloride, chloride , Lithium chloride, inorganic salts lithium bromide, etc., and metal carbonyls such as octacarbonyl dicobalt (cobalt carbonyl) and the like. These reaction catalysts can be used alone or in combination of two or more.
【００３３】このようにして得られる親水性ポリアミド
系樹脂の重量平均分子量（ゲルパーミエーションクロマ
トグラフィーで測定し、標準ポリスチレンを用いて作成
した検量線により換算した値）は、耐熱性、屈曲性、ア
ルカリ現像液溶解性、有機溶剤溶解性等の点から１０，
０００〜５０，００００であることが好ましく、２０，
０００〜２００，０００であることが好ましく、３０，
０００〜１００，０００であることが好ましい。また、
光硬化性、美観等の点からは、その光透過率（５０μｍ
厚のフィルムについて、３６５nmにおいて）が１％以上
であることが好ましく、２０〜８０％であることがより
好ましい。The weight-average molecular weight (measured by gel permeation chromatography and converted by a calibration curve prepared using standard polystyrene) of the hydrophilic polyamide-based resin thus obtained is determined by heat resistance, flexibility, From the viewpoint of solubility in an alkali developing solution, solubility in an organic solvent, etc., 10,
000 to 50,000, preferably 20,
000 to 200,000, preferably 30,000
It is preferably from 000 to 100,000. Also,
The light transmittance (50 μm
(At 365 nm for thick films) is preferably 1% or more, more preferably 20-80%.
【００３４】本発明の親水性ポリアミド系樹脂の製造法
により得られる親水性ポリアミド系樹脂は、プリント配
線板用ソルダーレジスト及び感光性カバーレイフィルム
をはじめ、液晶用カラーフィルタ材料、電子部品用耐熱
材料など各種用途のアルカリ現像型感光性樹脂組成物の
ポリマ成分として広く利用でき、工業的に極めて有用で
ある。The hydrophilic polyamide-based resin obtained by the method for producing a hydrophilic polyamide-based resin of the present invention includes a solder resist for a printed wiring board, a photosensitive coverlay film, a color filter material for a liquid crystal, and a heat-resistant material for an electronic component. It can be widely used as a polymer component of an alkali-developable photosensitive resin composition for various uses, and is extremely useful industrially.
【００３５】[0035]
【実施例】次に、実施例により本発明をさらに詳しく説
明するが、本発明はこれらによって制限されるものでは
ない。Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention.
【００３６】合成例１ 〔ポリオキシアルキレン基を有する親水性ジカルボン酸
の合成〕撹拌機、温度計、冷却管、留出管及び窒素ガス
導入管を装備したフラスコに、ポリオキシプロピレンジ
アミン（ハンツマンコーポレーション製商品名 ジェフ
ァーミンＤ−２０００、一分子中のオキシプロピレン単
位が平均３４個、平均分子量２０００）１０００重量
部、トリメリット酸無水物１９２重量部仕込み、窒素ガ
ス通気下、途中、副生してくる縮合水をトルエンで共沸
させて留去しながら、１時間かけて２００℃に昇温し
た。同温度で２時間保温して脱水イミド化反応を完結さ
せた後、冷却し、ポリオキシアルキレン基を有する親水
性ジカルボン酸（ポリオキシアルキレンジイミドジカル
ボン酸）を得た。Synthesis Example 1 [Synthesis of hydrophilic dicarboxylic acid having polyoxyalkylene group] In a flask equipped with a stirrer, a thermometer, a cooling tube, a distilling tube, and a nitrogen gas introducing tube, polyoxypropylene diamine (Huntsman Corporation) was added. Product name: Jeffamine D-2000, average 34 oxypropylene units in one molecule, average molecular weight of 2000) 1000 parts by weight, 192 parts by weight of trimellitic anhydride, and by-produced under nitrogen gas ventilation. The temperature was raised to 200 ° C. over 1 hour while distilling off condensed water by azeotropic distillation with toluene. After keeping the temperature at the same temperature for 2 hours to complete the dehydration imidization reaction, the mixture was cooled to obtain a hydrophilic dicarboxylic acid having a polyoxyalkylene group (polyoxyalkylene diimide dicarboxylic acid).
【００３７】合成例２ 〔ポリオキシアルキレン基を有する親水性ジカルボン酸
の合成〕撹拌機、温度計、冷却管、留出管及び窒素ガス
導入管を装備したフラスコに、ポリ（オキシエチレン・
オキシプロピレン）ジアミン（ハンツマンコーポレーシ
ョン製、商品名 ジェファーミンＥＤ−２００１、一分
子中のオキシエチレン単位が平均４０．５個、オキシプ
ロピレン単位が平均３．５個、平均分子量２０００）１
０００重量部、トリメリット酸無水物１９２重量部を仕
込み、窒素ガス通気下、途中、副生してくる縮合水をト
ルエンで共沸させて留去しながら、１時間かけて２００
℃に昇温した。同温度で２時間保温して脱水イミド化反
応を完結させた後、冷却し、ポリオキシアルキレン基を
有する親水性ジカルボン酸（ポリオキシアルキレンジイ
ミドジカルボン酸）を得た。Synthesis Example 2 [Synthesis of hydrophilic dicarboxylic acid having a polyoxyalkylene group] A flask equipped with a stirrer, a thermometer, a cooling tube, a distilling tube, and a nitrogen gas introducing tube was charged with poly (oxyethylene.
(Oxypropylene) diamine (manufactured by Huntsman Corporation, trade name: Jeffamine ED-2001, average 40.5 oxyethylene units, average 3.5 oxypropylene units, average molecular weight 2000) in one molecule 1
2,000 parts by weight, and 192 parts by weight of trimellitic anhydride were charged, and while condensed water produced as a by-product was azeotropically distilled off with toluene in the middle of the mixture under nitrogen gas aeration, 200 parts by weight was added over 1 hour.
The temperature was raised to ° C. After keeping the temperature at the same temperature for 2 hours to complete the dehydration imidization reaction, the mixture was cooled to obtain a hydrophilic dicarboxylic acid having a polyoxyalkylene group (polyoxyalkylene diimide dicarboxylic acid).
【００３８】合成例３ 〔ポリオキシアルキレン基を有する親水性ジカルボン酸
の合成〕撹拌機、温度計、冷却管、留出管及び窒素ガス
導入管を装備したフラスコに、α，ω−（３−アミノプ
ロピル）−ポリエチレングリコール（広栄化学工業(株)
製、商品名ＰＥＧＰＡ−１０００、平均分子量１１０
０）９６１重量部（１モル、１級アミン価からの算出
値）、トリメリット酸無水物を３８４重量部（２モル）
を仕込み、窒素ガス通気下、途中、副生してくる縮合水
をトルエンで共沸させて留去しながら、１時間かけて２
００℃に昇温した。同温度で３時間保温して脱水イミド
化反応を完結させた後、冷却し、ポリオキシアルキレン
基を有する親水性ジカルボン酸（ポリオキシアルキレン
ジイミドジカルボン酸）を得た。Synthesis Example 3 [Synthesis of hydrophilic dicarboxylic acid having a polyoxyalkylene group] In a flask equipped with a stirrer, a thermometer, a cooling tube, a distilling tube, and a nitrogen gas introducing tube, α, ω- (3- Aminopropyl) -polyethylene glycol (Koei Chemical Industry Co., Ltd.)
PEGPA-1000, trade name, average molecular weight 110
0) 961 parts by weight (1 mol, calculated from primary amine value), 384 parts by weight of trimellitic anhydride (2 mol)
And while the condensed water produced as a by-product is azeotropically distilled off with toluene in the middle of the reaction under nitrogen gas aeration, 2 hours over 2 hours.
The temperature was raised to 00 ° C. After keeping the temperature at the same temperature for 3 hours to complete the dehydration imidization reaction, the mixture was cooled to obtain a hydrophilic dicarboxylic acid having a polyoxyalkylene group (polyoxyalkylene diimide dicarboxylic acid).
【００３９】合成例４ ［ポリオキシアルキレン基を有する親水性ジカルボン酸
の合成］撹拌機、温度計、冷却管、留出管及び窒素ガス
導入管を装備したフラスコに、ポリオキシプロピレンジ
アミン（ハンツマンコーポレーション製商品名、ジェフ
ァーミンＤ−２０００、平均分子量２０００）１０００
重量部、セバシン酸２０２．３重量部仕込み、窒素ガス
通気下、途中、副生してくる縮合水をトルエンで共沸さ
せて留去しながら、１時間かけて２２５℃に昇温した。
同温度で３時間保温して脱水アミド化反応を完結させた
後、冷却し、ポリオキシアルキレン基を有する（ポリオ
キシアルキレンアミドジカルボン酸）を得た。Synthesis Example 4 [Synthesis of hydrophilic dicarboxylic acid having polyoxyalkylene group] In a flask equipped with a stirrer, a thermometer, a cooling tube, a distilling tube, and a nitrogen gas introducing tube, polyoxypropylene diamine (Huntsman Corporation) was added. Product name, Jeffamine D-2000, average molecular weight 2000) 1000
The mixture was charged with 202.3 parts by weight of sebacic acid and heated to 225 ° C. over 1 hour while azeotropically distilling off condensed water produced as a by-product with toluene under nitrogen gas aeration.
After maintaining the temperature at the same temperature for 3 hours to complete the dehydration amidation reaction, the mixture was cooled to obtain a polyoxyalkylene group-containing (polyoxyalkylene amide dicarboxylic acid).
【００４０】合成例５ ［ポリオキシアルキレン基を有する親水性ジカルボン酸
の合成］合成例１において、ポリオキシプロピレンジア
ミンをポリプロピレングリコール（三洋化成工業(株)製
商品名、ニューポールＰＰ−２０００、平均分子量２０
００）に変更した以外は、合成例１と同様にしてポリオ
キシアルキレン基を有する親水性ジカルボン酸（オキシ
アルキレン基・エステル結合含有ジカルボン酸）を得
た。Synthesis Example 5 [Synthesis of hydrophilic dicarboxylic acid having polyoxyalkylene group] In Synthesis Example 1, polyoxypropylenediamine was replaced with polypropylene glycol (trade name, manufactured by Sanyo Chemical Industries, Ltd., Newpol PP-2000, average Molecular weight 20
A hydrophilic dicarboxylic acid having a polyoxyalkylene group (an oxyalkylene group-ester bond-containing dicarboxylic acid) was obtained in the same manner as in Synthesis Example 1 except for changing the composition to (00).
【００４１】実施例１ 撹拌機、温度計、冷却管及び窒素ガス導入管を装備した
フラスコに、合成例１で得たポリオキシアルキレン基を
有する親水性ジカルボン酸６４.３２重量部、アジピン
酸４.８８重量部、セバシン酸６.７５重量部、イソフタ
ル酸５.５４重量部、テレフタル酸５.５４重量部、ダイ
マー酸０.１５重量部、４，４′−ジフェニルメタンジ
イソシアネート６．３３重量部、トリレンジイソシアネ
ート（２，４−異性体／２，６−異性体＝８０／２０モ
ル％）１７．６２重量部及びγ−ブチロラクトン１２０
重量部を仕込み、窒素ガス通気下、途中、副生してくる
炭酸ガスを系外に排気しながら、１．５時間かけて２０
０℃に昇温した。同温度で３時間保温して脱炭酸アミド
化反応を完結させた後、１３０℃まで冷却し、ポリアミ
ド中間体の溶液を得た。Example 1 In a flask equipped with a stirrer, a thermometer, a cooling tube and a nitrogen gas introducing tube, 64.32 parts by weight of the polyoxyalkylene group-containing hydrophilic dicarboxylic acid obtained in Synthesis Example 1 and adipic acid 4 .88 weight parts, sebacic acid 6.75 weight parts, isophthalic acid 5.54 weight parts, terephthalic acid 5.54 weight parts, dimer acid 0.15 weight parts, 4,4'-diphenylmethane diisocyanate 6.33 weight parts, 17.62 parts by weight of tolylene diisocyanate (2,4-isomer / 2,6-isomer = 80/20 mol%) and γ-butyrolactone 120
Parts by weight, and while venting carbon dioxide gas as a by-product to the outside of the system under nitrogen gas ventilation,
The temperature was raised to 0 ° C. After keeping the temperature at the same temperature for 3 hours to complete the decarboxylation amidation reaction, the mixture was cooled to 130 ° C. to obtain a polyamide intermediate solution.
【００４２】次いで、１３０℃で保温状態にあるポリア
ミド中間体の溶液に、エポミックＲ１４０Ｐ（三井石油
化学工業(株)社製商品名、ビスフェノールＡ型エポキシ
樹脂）２９．８２重量部及びＮ，Ｎ−ジメチルホルムア
ミド４０重量部を添加し、同温度で１．５時間保温して
ヒドロキシエチルエステル化反応を完結させた後、１１
５℃まで冷却し、ポリアミド系樹脂中間体の溶液を得
た。次いで、窒素ガス通気を乾燥空気通気に切替え、１
１５℃で保温状態にあるポリアミド系樹脂中間体の溶液
に、メタクリル酸５．８３重量部、メトキノン０．５８
重量部及びＮ，Ｎ−ジメチルベンジルアミン１．９７重
量部を添加し、同温度で１．５時間保温してエポキシ基
封止反応を完結させた。続いて、１１５℃保温下、テト
ラヒドロフタル酸無水物２１．７２重量部を添加し、同
温度で２時間保温してハーフエステル化反応を完結させ
た後、７０℃まで冷却し、７０℃保温下、さらに、２−
イソシアネートエチルメタクリレート２．４６重量部を
添加し、同温度で１．５時間保温して光重合性不飽和基
導入反応を完結させた後、冷却し、親水性ポリアミド系
樹脂の溶液を得た。Then, 29.82 parts by weight of Epomic R140P (trade name of bisphenol A type epoxy resin, manufactured by Mitsui Petrochemical Industry Co., Ltd.) and N, N- After adding 40 parts by weight of dimethylformamide and keeping the mixture at the same temperature for 1.5 hours to complete the hydroxyethyl esterification reaction,
After cooling to 5 ° C., a solution of a polyamide resin intermediate was obtained. Then, nitrogen gas ventilation was switched to dry air ventilation, and 1
5.83 parts by weight of methacrylic acid and 0.58 of methquinone were added to a solution of the polyamide-based resin intermediate kept at 15 ° C.
Parts by weight and 1.97 parts by weight of N, N-dimethylbenzylamine were added, and the mixture was kept at the same temperature for 1.5 hours to complete the epoxy group-capping reaction. Subsequently, while maintaining the temperature at 115 ° C, 21.72 parts by weight of tetrahydrophthalic anhydride was added, and the temperature was maintained at the same temperature for 2 hours to complete the half-esterification reaction, followed by cooling to 70 ° C and maintaining the temperature at 70 ° C. , And 2-
After adding 2.46 parts by weight of isocyanateethyl methacrylate and keeping the temperature at the same temperature for 1.5 hours to complete the photopolymerizable unsaturated group introduction reaction, the mixture was cooled to obtain a solution of a hydrophilic polyamide-based resin.
【００４３】得られた親水性ポリアミド系樹脂の固形分
酸価は５０KOHmg/gであり、重量平均分子量は６１，０
００であり、この親水性ポリアミド系樹脂は、アルカリ
水溶液（１重量％の炭酸ナトリウム水溶液）に可溶性で
あった。また、この親水性ポリアミド系樹脂の厚さ５０
μｍのフィルムの３６５nmにおける光透過率は、０．５
％であった。なお、この光透過率は、親水性ポリアミド
系樹脂の溶液を、２０μｍの厚さのポリエチレンテレフ
タレートフィルム上に乾燥膜厚が５０μｍとなるように
均一に塗布し、これを１００℃のホットプレート上で１
５分間乾燥して片面ポリエチレンテレフタレートフィル
ム付き樹脂膜被検試料を得、この被検試料について、ポ
リエチレンテレフタレートフィルムをリファレンスと
し、(株)日立製作所製２８８Ａ型スペクトロフォトメー
ターを用いて、温度２５℃、波長３６５nmで測定し算出
した（以下においても同様）。The solid polyamide acid value of the obtained hydrophilic polyamide resin is 50 KOHmg / g, and the weight average molecular weight is 61.0.
The hydrophilic polyamide-based resin was soluble in an aqueous alkali solution (1% by weight aqueous sodium carbonate solution). The thickness of the hydrophilic polyamide-based resin is 50
The light transmission at 365 nm of a μm film is 0.5
%Met. The light transmittance was determined by applying a solution of a hydrophilic polyamide-based resin uniformly on a polyethylene terephthalate film having a thickness of 20 μm so as to have a dry film thickness of 50 μm, and applying the solution on a hot plate at 100 ° C. 1
After drying for 5 minutes, a resin film test sample with a single-sided polyethylene terephthalate film was obtained. The test sample was subjected to a temperature of 25 ° C. using a 288A spectrophotometer manufactured by Hitachi, Ltd. with reference to the polyethylene terephthalate film. It was measured and calculated at a wavelength of 365 nm (the same applies hereinafter).
【００４４】実施例２ 実施例１において、合成例１で得たポリオキシアルキレ
ン基を有する親水性ジカルボン酸を合成例２で得たポリ
オキシアルキレン基を有する親水性ジカルボン酸に、エ
ポミックＲ１４０Ｐの２９．８２重量部を１７．８９重
量部に、テトラヒドロフタル酸無水物の２１．７２重量
部を１３．０３重量部に、及び、２−イソシアネートエ
チルメタクリレートの２．４６重量部を１．４８重量部
に代えた以外は、実施例１と同様にして親水性ポリアミ
ド系樹脂を得た。得られた親水性ポリアミド系樹脂の固
形分酸価は３６KOHmg/gであり、重量平均分子量は６
０，０００であり、この親水性ポリアミド系樹脂は、ア
ルカリ水溶液（１重量％の炭酸ナトリウム水溶液）に可
溶性であった。また、この親水性ポリアミド系樹脂の厚
さ５０μｍのフィルムの３６５nmにおける光透過率は、
０．５％であった。Example 2 In Example 1, the hydrophilic dicarboxylic acid having a polyoxyalkylene group obtained in Synthesis Example 1 was replaced with the hydrophilic dicarboxylic acid having a polyoxyalkylene group obtained in Synthesis Example 2 by adding 29 .82 parts by weight to 17.89 parts by weight, 21.72 parts by weight of tetrahydrophthalic anhydride to 13.03 parts by weight, and 2.46 parts by weight of 2-isocyanatoethyl methacrylate to 1.48 parts by weight A hydrophilic polyamide-based resin was obtained in the same manner as in Example 1 except that the above-mentioned was used. The solid polyamide acid value of the obtained hydrophilic polyamide resin is 36 KOHmg / g, and the weight average molecular weight is 6
The hydrophilic polyamide-based resin was soluble in an aqueous alkali solution (a 1% by weight aqueous sodium carbonate solution). The light transmittance at 365 nm of the 50 μm thick film of the hydrophilic polyamide-based resin is as follows:
0.5%.
【００４５】実施例３ 撹拌機、温度計、冷却管及び窒素ガス導入管を装備した
フラスコに、合成例３で得たポリオキシアルキレン基を
有する親水性ジカルボン酸７３．９３重量部、アジピン
酸３．３９重量部、セバシン酸４．６９重量部、イソフ
タル酸３．８５重量部、テレフタル酸３．８５重量部、
ダイマー酸０．２８重量部、４，４′−ジフェニルメタ
ンジイソシアネート４．９４重量部、トリレンジイソシ
アネート（２，４−異性体／２，６−異性体＝８０／２
０モル％）１３．７５重量部及びγ−ブチロラクトン１
２２．２重量部を仕込み、窒素ガス通気下、途中、副生
してくる炭酸ガスを系外に排気しながら、１時間かけて
２００℃に昇温した。同温度で３時間保温して脱炭酸ア
ミド化反応を完結させた後、１３０℃まで冷却し、ポリ
アミド中間体の溶液を得た。Example 3 73.93 parts by weight of the polyoxyalkylene group-containing hydrophilic dicarboxylic acid obtained in Synthesis Example 3 and adipic acid 3 in a flask equipped with a stirrer, thermometer, cooling tube and nitrogen gas introducing tube. .39 parts by weight, 4.69 parts by weight of sebacic acid, 3.85 parts by weight of isophthalic acid, 3.85 parts by weight of terephthalic acid,
0.28 parts by weight of dimer acid, 4.94 parts by weight of 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate (2,4-isomer / 2,6-isomer = 80/2
0 mol%) 13.75 parts by weight and γ-butyrolactone 1
22.2 parts by weight were charged, and the temperature was raised to 200 ° C. over 1 hour while venting the by-produced carbon dioxide gas to the outside under nitrogen gas ventilation. After keeping the temperature at the same temperature for 3 hours to complete the decarboxylation amidation reaction, the mixture was cooled to 130 ° C. to obtain a polyamide intermediate solution.
【００４６】次いで、１３０℃で保温状態にあるポリア
ミド中間体の溶液にエポミックＲ３０１（三井石油化学
工業(株)製商品名、ビスフェノールＡ型エポキシ樹脂）
０．５１重量部、エポトートＹＤＦ２００１（東都化成
(株)製商品名、ビスフェノールＦ型エポキシ樹脂）６
９．３９重量部及びＮ，Ｎ−ジメチルホルムアミド１９
３．３重量部を添加し、同温度で２．５時間保温してヒ
ドロキシエチルエステル化反応を完結させた後、１１５
℃まで冷却し、ポリアミド系樹脂中間体の溶液を得た。
次いで、窒素ガス通気を乾燥空気通気に切替え、１１５
℃で保温状態にあるポリアミド系樹脂中間体の溶液に、
メタクリル酸３．３３重量部、メトキノン０．０２２重
量部及びＮ，Ｎ−ジメチルベンジルアミン２．１９重量
部を添加し、同温度で３時間保温してエポキシ基封止反
応を完結させた。続いて、１１５℃保温下、テトラヒド
ロフタル酸無水物４５．７３重量部を添加し、同温度で
１時間保温した後、冷却し、親水性ポリアミド系樹脂の
溶液を得た。Then, Epomic R301 (trade name, bisphenol A type epoxy resin manufactured by Mitsui Petrochemical Industries, Ltd.) was added to the solution of the polyamide intermediate kept at 130 ° C.
0.51 parts by weight, Epototo YDF2001 (Toto Kasei
(Trade name, bisphenol F type epoxy resin) 6
9.39 parts by weight and N, N-dimethylformamide 19
3.3 parts by weight were added, and the mixture was kept at the same temperature for 2.5 hours to complete the hydroxyethyl esterification reaction.
It cooled to ° C, and obtained the solution of the polyamide system resin intermediate.
Next, the nitrogen gas ventilation was switched to dry air ventilation, and 115
In the solution of polyamide-based resin intermediate that is kept warm at ℃,
3.33 parts by weight of methacrylic acid, 0.022 parts by weight of methquinone and 2.19 parts by weight of N, N-dimethylbenzylamine were added, and the mixture was kept at the same temperature for 3 hours to complete the epoxy group-capping reaction. Subsequently, 45.73 parts by weight of tetrahydrophthalic anhydride was added while keeping the temperature at 115 ° C., and the mixture was kept at the same temperature for 1 hour and then cooled to obtain a solution of a hydrophilic polyamide resin.
【００４７】得られた親水性ポリアミド系樹脂の固形分
酸価は７７KOHmg/gであり、重量平均分子量は６０，０
００であり、この親水性ポリアミド系樹脂は、アルカリ
水溶液（１重量％の炭酸ナトリウム水溶液）に可溶性で
あった。また、親水性ポリアミド系樹脂の厚さ５０μｍ
のフィルムの３６５nmにおける光透過率は、１％であっ
た。The solid polyamide acid value of the obtained hydrophilic polyamide resin is 77 KOH mg / g, and the weight average molecular weight is 60,0.
The hydrophilic polyamide-based resin was soluble in an aqueous alkali solution (1% by weight aqueous sodium carbonate solution). The thickness of the hydrophilic polyamide resin is 50 μm.
The light transmittance at 365 nm of the film was 1%.
【００４８】実施例４ 撹拌機、温度計、冷却管及び窒素ガス導入管を装備した
フラスコに、合成例４で得たポリオキシアルキレン基を
有する親水性ジカルボン酸７２．７２重量部、アジピン
酸８．７７重量部、セバシン酸９．１７重量部、４，
４′−ジフェニルメタンジイソシアネート４．５３重量
部、トリレンジイソシアネート（２，４−異性体／２，
６−異性体＝８０／２０モル％）１２．６０重量部及び
γ−ブチロラクトン１２２．２重量部を仕込み、窒素ガ
ス通気下、途中、副生してくる炭酸ガスを系外に排気し
ながら、１時間かけて２００℃に昇温した。同温度で３
時間保温して脱炭酸アミド化反応を完結させた後、１３
０℃まで冷却し、ポリアミド中間体の溶液を得た。Example 4 72.72 parts by weight of the polyoxyalkylene group-containing hydrophilic dicarboxylic acid obtained in Synthesis Example 4 and adipic acid 8 were placed in a flask equipped with a stirrer, thermometer, cooling tube and nitrogen gas inlet tube. .77 parts by weight, 9.17 parts by weight of sebacic acid, 4,
4.53 parts by weight of 4'-diphenylmethane diisocyanate, tolylene diisocyanate (2,4-isomer / 2,
6-isomer = 80/20 mol%) 12.60 parts by weight and 122.2 parts by weight of γ-butyrolactone were charged, and while gaseous carbon dioxide was being produced as a by-product while ventilating with nitrogen gas, the gas was exhausted out of the system. The temperature was raised to 200 ° C. over 1 hour. 3 at the same temperature
After completion of the decarboxylation amidation reaction by keeping the temperature for 13 hours, 13
After cooling to 0 ° C., a solution of the polyamide intermediate was obtained.
【００４９】次いで、１３０℃で保温状態にあるポリア
ミド中間体の溶液にエポトートＹＤＦ２００１（東都化
成(株)製商品名、ビスフェノールＦ型エポキシ樹脂、エ
ポキシ当量４６５）６４．１２重量部及びＮ，Ｎ−ジメ
チルホルムアミド１４５．５重量部を添加し、同温度で
３時間保温してヒドロキシエチルエステル化反応を完結
させた後、１１５℃まで冷却し、ポリアミド系樹脂中間
体の溶液を得た。次いで、窒素ガス通気を乾燥空気通気
に切替え、１１５℃で保温状態にあるポリアミド系樹脂
中間体の溶液に、メタクリル酸３．０６重量部、メトキ
ノン０．０２１重量部及びＮ，Ｎ−ジメチルベンジルア
ミン２．０９重量部を添加し、同温度で３時間保温して
エポキシ基をなくす反応を完結させた。続いて、１１５
℃保温下、テトラヒドロフタル酸無水物４１．９６重量
部を添加し、同温度で１時間保温した後、冷却し、親水
性ポリアミド系樹脂の溶液を得た。Next, 64.12 parts by weight of Epotote YDF2001 (trade name, manufactured by Toto Kasei Co., Ltd., bisphenol F type epoxy resin, epoxy equivalent: 465) and 64,12 parts by weight of N, N- 145.5 parts by weight of dimethylformamide was added, and the mixture was kept at the same temperature for 3 hours to complete the hydroxyethyl esterification reaction, and then cooled to 115 ° C to obtain a solution of a polyamide resin intermediate. Next, nitrogen gas ventilation was switched to dry air ventilation, and 3.06 parts by weight of methacrylic acid, 0.021 part by weight of methquinone and N, N-dimethylbenzylamine were added to the solution of the polyamide-based resin intermediate kept at 115 ° C. 2.09 parts by weight were added, and the mixture was kept at the same temperature for 3 hours to complete the reaction for eliminating epoxy groups. Subsequently, 115
While keeping the temperature at 40 ° C., 41.96 parts by weight of tetrahydrophthalic anhydride was added, and the mixture was kept at the same temperature for 1 hour and then cooled to obtain a hydrophilic polyamide resin solution.
【００５０】得られた親水性ポリアミド系樹脂の固形分
酸価は７４KOHmg/gであり、重量平均分子量は６２，０
００であり、この親水性ポリアミド系樹脂は、アルカリ
水溶液（１重量％の炭酸ナトリウム水溶液）に可溶性で
あった。また、親水性ポリアミド系樹脂の厚さ５０μｍ
のフィルムの３６５nmにおける光透過率は、６０％であ
った。The solid polyamide acid value of the obtained hydrophilic polyamide resin is 74 KOH mg / g, and the weight average molecular weight is 62.0.
The hydrophilic polyamide-based resin was soluble in an aqueous alkali solution (1% by weight aqueous sodium carbonate solution). The thickness of the hydrophilic polyamide resin is 50 μm.
The light transmittance at 365 nm of the film was 60%.
【００５１】実施例５ 実施例４において、合成例４で得たポリオキシアルキレ
ン基を有する親水性ジカルボン酸を合成例５で得たポリ
オキシアルキレン基を有する親水性ジカルボン酸に変更
した以外は、実施例１と同様にして親水性ポリアミド系
樹脂の溶液を得た。得られた親水性ポリアミド系樹脂の
固形分酸価は７４KOHmg/gであり、重量平均分子量は５
８，０００であり、この親水性ポリアミド系樹脂は、ア
ルカリ水溶液（１重量％の炭酸ナトリウム水溶液）に可
溶性であった。また、親水性ポリアミド系樹脂の厚さ５
０μｍのフィルムの３６５nmにおける光透過率は、６０
％であった。Example 5 In Example 4, except that the hydrophilic dicarboxylic acid having a polyoxyalkylene group obtained in Synthesis Example 4 was changed to the hydrophilic dicarboxylic acid having a polyoxyalkylene group obtained in Synthesis Example 5, A hydrophilic polyamide-based resin solution was obtained in the same manner as in Example 1. The solid polyamide acid value of the obtained hydrophilic polyamide resin is 74 KOHmg / g, and the weight average molecular weight is 5
The hydrophilic polyamide-based resin was soluble in an aqueous alkali solution (1% by weight aqueous sodium carbonate solution). In addition, the thickness of the hydrophilic polyamide resin is 5
The light transmission at 365 nm of a 0 μm film is 60
%Met.
【００５２】比較例１ 撹拌機、温度計、冷却管及び窒素ガス導入管を装備した
フラスコに、アジピン酸６．９７重量部、セバシン酸
９．５３重量部、イソフタル酸７．９２重量部、テレフ
タル酸７．９２重量部、ダイマー酸０．１７重量部、
４，４′−ジフェニルメタンジイソシアネート７．５１
重量部、トリレンジイソシアネート（２，４−異性体／
２，６−異性体＝８０／２０モル％）２０．９０重量部
及びγ−ブチロラクトン７２重量部を仕込み、窒素ガス
通気下、途中、副生してくる炭酸ガスを系外に排気しな
がら、１.５時間かけて２００℃に昇温した。同温度で
３時間保温して脱炭酸アミド化反応を完結させた後、１
３０℃まで冷却し、ポリアミド中間体の溶液を得た。Comparative Example 1 6.97 parts by weight of adipic acid, 9.53 parts by weight of sebacic acid, 7.92 parts by weight of isophthalic acid, and terephthalic acid were placed in a flask equipped with a stirrer, thermometer, cooling pipe and nitrogen gas introducing pipe. 7.92 parts by weight of acid, 0.17 part by weight of dimer acid,
4,4'-diphenylmethane diisocyanate 7.51
Parts by weight, tolylene diisocyanate (2,4-isomer /
2,6-isomer = 80/20 mol%) 20.90 parts by weight and γ-butyrolactone 72 parts by weight were charged, and while the gaseous carbon dioxide produced as a by-product was exhausted to the outside of the system under nitrogen gas ventilation, The temperature was raised to 200 ° C. over 1.5 hours. After maintaining at the same temperature for 3 hours to complete the decarboxylation amidation reaction, 1
After cooling to 30 ° C., a solution of the polyamide intermediate was obtained.
【００５３】次いで、１３０℃で保温状態にあるポリア
ミド中間体の溶液に、エポミックＲ１４０Ｐ（三井石油
化学工業(株)社製商品名、ビスフェノールＡ型エポキシ
樹脂）２５．４９重量部及びＮ，Ｎ−ジメチルホルムア
ミド７２重量部を添加し、同温度で１．５時間保温して
ヒドロキシエチルエステル化反応を完結させた後、１１
５℃まで冷却し、ポリアミド系樹脂中間体の溶液を得
た。次いで、窒素ガス通気を乾燥空気通気に切替え、１
１５℃で保温状態にあるポリアミド系樹脂中間体の溶液
に、メタクリル酸４．９６重量部、メトキノン０．５０
重量部及びＮ，Ｎ−ジメチルベンジルアミン１．４８重
量部を添加し、同温度で１．５時間保温してエポキシ基
封止反応を完結させた。続いて、１１５℃保温下、テト
ラヒドロフタル酸無水物１８．５８重量部を添加し、同
温度で２時間保温してハーフエステル化反応を完結させ
た後、７０℃まで冷却し、７０℃保温下、さらに、２−
イソシアネートエチルメタクリレート２．０９重量部を
添加し、同温度で１．５時間保温して光重合性不飽和基
導入反応を完結させた後、冷却した。Next, 25.49 parts by weight of Epomic R140P (trade name of bisphenol A type epoxy resin manufactured by Mitsui Petrochemical Industry Co., Ltd.) and N, N- After adding 72 parts by weight of dimethylformamide and keeping the mixture at the same temperature for 1.5 hours to complete the hydroxyethyl esterification reaction,
After cooling to 5 ° C., a solution of a polyamide resin intermediate was obtained. Then, nitrogen gas ventilation was switched to dry air ventilation, and 1
4.96 parts by weight of methacrylic acid and 0.50 of methquinone were added to a solution of the polyamide-based resin intermediate kept at 15 ° C.
Parts by weight and 1.48 parts by weight of N, N-dimethylbenzylamine were added, and the mixture was kept at the same temperature for 1.5 hours to complete the epoxy group-capping reaction. Subsequently, 18.58 parts by weight of tetrahydrophthalic anhydride was added while maintaining the temperature at 115 ° C., and the temperature was maintained at the same temperature for 2 hours to complete the half-esterification reaction. , And 2-
2.09 parts by weight of isocyanate ethyl methacrylate was added, the mixture was kept at the same temperature for 1.5 hours to complete the photopolymerizable unsaturated group introduction reaction, and then cooled.
【００５４】得られたポリアミド系樹脂の固形分酸価は
６９KOHmg/gであり、重量平均分子量は７５，０００で
あり、このポリアミド系樹脂は、アルカリ水溶液（１重
量％の炭酸ナトリウム水溶液）に不溶性であった。ま
た、このポリアミド系樹脂の厚さ５０μｍのフィルムの
３６５nmにおける光透過率は、１０％であった。The solid content acid value of the obtained polyamide resin was 69 KOH mg / g, the weight average molecular weight was 75,000, and the polyamide resin was insoluble in an alkaline aqueous solution (1% by weight aqueous sodium carbonate solution). Met. The light transmittance at 365 nm of the film of this polyamide resin having a thickness of 50 μm was 10%.
【００５５】以上のように、本発明において得られる親
水性ポリアミド系樹脂は、通常、アルカリ現像液として
用いられている１重量％の炭酸ナトリウム水溶液に可溶
性であることから、アルカリ現像型感光性樹脂組成物の
ポリマ成分として好適であることが分かる。As described above, the hydrophilic polyamide-based resin obtained in the present invention is generally soluble in a 1% by weight aqueous solution of sodium carbonate used as an alkali developing solution. It turns out that it is suitable as a polymer component of the composition.
【００５６】[0056]
【発明の効果】本発明の親水性ポリアミド系樹脂の製造
法により、親水性が優れたプリント配線板等の製造用の
アルカリ現像型感光性樹脂組成物のポリマ成分として好
適な、アルカリ水溶液可溶性の親水性ポリアミド系樹脂
を容易に製造することができる。According to the process for producing a hydrophilic polyamide-based resin of the present invention, an aqueous alkali-soluble resin suitable as a polymer component of an alkali-developable photosensitive resin composition for producing a printed wiring board having excellent hydrophilicity is provided. A hydrophilic polyamide-based resin can be easily produced.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 平倉 裕昭 茨城県鹿島郡波崎町大字砂山五番壱 日立 化成工業株式会社鹿島工場内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroaki Hirakura In the Kashima Plant, Hitachi Chemical Co., Ltd.
Claims (1)
親水性ジカルボン酸と（Ｂ）ジイソシアネート又はジア
ミンを反応させてポリアミド中間体を得、次いで、この
ポリアミド中間体に（Ｃ）エポキシ樹脂を反応させてポ
リアミド系樹脂中間体を得、このポリアミド系樹脂中間
体に（Ｄ）多価カルボン酸モノ無水物を反応させること
を特徴とする親水性ポリアミド系樹脂の製造法。1. A polyamide intermediate is obtained by reacting (A) a hydrophilic dicarboxylic acid having a polyoxyalkylene group with (B) a diisocyanate or a diamine, and then reacting the polyamide intermediate with (C) an epoxy resin. A method for producing a hydrophilic polyamide-based resin, characterized in that a polyamide-based resin intermediate is obtained by reacting the polyamide-based resin intermediate with (D) a polycarboxylic acid monoanhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10080058A JPH10330481A (en) | 1997-03-31 | 1998-03-27 | Production of hydrophilic polyamide-based resin |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9-80417 | 1997-03-31 | ||
| JP8041797 | 1997-03-31 | ||
| JP10080058A JPH10330481A (en) | 1997-03-31 | 1998-03-27 | Production of hydrophilic polyamide-based resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10330481A true JPH10330481A (en) | 1998-12-15 |
Family
ID=26421090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10080058A Pending JPH10330481A (en) | 1997-03-31 | 1998-03-27 | Production of hydrophilic polyamide-based resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10330481A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001051991A1 (en) * | 2000-01-12 | 2001-07-19 | Nippon Kayaku Kabushiki Kaisha | Resin composition, cured object obtained therefrom, and article thereof |
| JP2001233930A (en) * | 2000-02-21 | 2001-08-28 | Bayer Ag | Acylurea group-containing polyisocyanate mixture |
| JP2002053664A (en) * | 2000-08-08 | 2002-02-19 | Asahi Kasei Corp | Hydroxypolyamides and compositions |
| JP2003026796A (en) * | 2001-07-13 | 2003-01-29 | Clariant (Japan) Kk | Photosensitive polyamide and composition |
| JP5120378B2 (en) * | 2007-06-06 | 2013-01-16 | 日立化成工業株式会社 | Photosensitive adhesive composition, film adhesive, adhesive sheet, method for forming adhesive pattern, semiconductor wafer with adhesive layer, semiconductor device, and method for manufacturing semiconductor device |
-
1998
- 1998-03-27 JP JP10080058A patent/JPH10330481A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001051991A1 (en) * | 2000-01-12 | 2001-07-19 | Nippon Kayaku Kabushiki Kaisha | Resin composition, cured object obtained therefrom, and article thereof |
| JP2001233930A (en) * | 2000-02-21 | 2001-08-28 | Bayer Ag | Acylurea group-containing polyisocyanate mixture |
| JP2002053664A (en) * | 2000-08-08 | 2002-02-19 | Asahi Kasei Corp | Hydroxypolyamides and compositions |
| JP2003026796A (en) * | 2001-07-13 | 2003-01-29 | Clariant (Japan) Kk | Photosensitive polyamide and composition |
| JP5120378B2 (en) * | 2007-06-06 | 2013-01-16 | 日立化成工業株式会社 | Photosensitive adhesive composition, film adhesive, adhesive sheet, method for forming adhesive pattern, semiconductor wafer with adhesive layer, semiconductor device, and method for manufacturing semiconductor device |
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