JP2024505993A - Cationic urethane resin composition - Google Patents
Cationic urethane resin composition Download PDFInfo
- Publication number
- JP2024505993A JP2024505993A JP2023547254A JP2023547254A JP2024505993A JP 2024505993 A JP2024505993 A JP 2024505993A JP 2023547254 A JP2023547254 A JP 2023547254A JP 2023547254 A JP2023547254 A JP 2023547254A JP 2024505993 A JP2024505993 A JP 2024505993A
- Authority
- JP
- Japan
- Prior art keywords
- urethane resin
- cationic urethane
- resin composition
- formula
- 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
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 48
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 44
- 239000011342 resin composition Substances 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 150000003077 polyols Chemical class 0.000 claims description 45
- 229920005862 polyol Polymers 0.000 claims description 35
- 125000003277 amino group Chemical group 0.000 claims description 20
- 239000005056 polyisocyanate Substances 0.000 claims description 11
- 229920001228 polyisocyanate Polymers 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 238000005956 quaternization reaction Methods 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 229920006264 polyurethane film Polymers 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- 239000004566 building material Substances 0.000 abstract description 2
- 239000003365 glass fiber Substances 0.000 abstract description 2
- 238000007641 inkjet printing Methods 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920006255 plastic film Polymers 0.000 abstract description 2
- 239000002985 plastic film Substances 0.000 abstract description 2
- 238000004513 sizing Methods 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 18
- 239000004793 Polystyrene Substances 0.000 description 16
- 229920002223 polystyrene Polymers 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- -1 anionic ion Chemical class 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000001302 tertiary amino group Chemical group 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 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
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- MBABOKRGFJTBAE-UHFFFAOYSA-N methyl methanesulfonate Chemical compound COS(C)(=O)=O MBABOKRGFJTBAE-UHFFFAOYSA-N 0.000 description 2
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-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
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BATCUENAARTUKW-UHFFFAOYSA-N 0.000 description 1
- KHFRJOPGKUBZLL-UHFFFAOYSA-N 7-methyl-n-(7-methyloctyl)octan-1-amine Chemical compound CC(C)CCCCCCNCCCCCCC(C)C KHFRJOPGKUBZLL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- NKGSHSILLGXYDW-UHFFFAOYSA-N N-undecylundecan-1-amine Chemical compound CCCCCCCCCCCNCCCCCCCCCCC NKGSHSILLGXYDW-UHFFFAOYSA-N 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-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
- 125000001931 aliphatic group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 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
- 238000011088 calibration curve Methods 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- XJTQJERLRPWUGL-UHFFFAOYSA-N iodomethylbenzene Chemical compound ICC1=CC=CC=C1 XJTQJERLRPWUGL-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 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
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- OBYVIBDTOCAXSN-UHFFFAOYSA-N n-butan-2-ylbutan-2-amine Chemical compound CCC(C)NC(C)CC OBYVIBDTOCAXSN-UHFFFAOYSA-N 0.000 description 1
- GMTCPFCMAHMEMT-UHFFFAOYSA-N n-decyldecan-1-amine Chemical compound CCCCCCCCCCNCCCCCCCCCC GMTCPFCMAHMEMT-UHFFFAOYSA-N 0.000 description 1
- MJCJUDJQDGGKOX-UHFFFAOYSA-N n-dodecyldodecan-1-amine Chemical compound CCCCCCCCCCCCNCCCCCCCCCCCC MJCJUDJQDGGKOX-UHFFFAOYSA-N 0.000 description 1
- CPTXPDMOZQHSFO-UHFFFAOYSA-N n-icosylicosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCCCC CPTXPDMOZQHSFO-UHFFFAOYSA-N 0.000 description 1
- UQLQVWLBTRWAIP-UHFFFAOYSA-N n-nonadecylnonadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCCC UQLQVWLBTRWAIP-UHFFFAOYSA-N 0.000 description 1
- MFHKEJIIHDNPQE-UHFFFAOYSA-N n-nonylnonan-1-amine Chemical compound CCCCCCCCCNCCCCCCCCC MFHKEJIIHDNPQE-UHFFFAOYSA-N 0.000 description 1
- HKUFIYBZNQSHQS-UHFFFAOYSA-N n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC HKUFIYBZNQSHQS-UHFFFAOYSA-N 0.000 description 1
- YDFFPEXFCAUTSL-UHFFFAOYSA-N n-pentadecylpentadecan-1-amine Chemical compound CCCCCCCCCCCCCCCNCCCCCCCCCCCCCCC YDFFPEXFCAUTSL-UHFFFAOYSA-N 0.000 description 1
- CATWEXRJGNBIJD-UHFFFAOYSA-N n-tert-butyl-2-methylpropan-2-amine Chemical compound CC(C)(C)NC(C)(C)C CATWEXRJGNBIJD-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 239000002562 thickening agent 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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
- C08G18/0814—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups containing ammonium groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
- C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
Abstract
カチオン性ウレタン樹脂（Ａ）、及び、水（Ｂ）を含有するカチオン性ウレタン樹脂組成物であって、前記カチオン性ウレタン樹脂（Ａ）が、特定の構造単位を有することを特徴とするカチオン性ウレタン樹脂組成物を提供する。本発明のカチオン性ウレタン樹脂組成物は、耐久性に優れるポリウレタン皮膜を付与することができる。また、本発明のカチオン性ウレタン樹脂組成物は、水中での分散性、及び、長期保存時の安定性に優れるものである。よって、本発明のカチオン性ウレタン樹脂組成物は、建材や家電用の鋼板、プラスチックフィルムやプラスチック成型品、インクジェット印刷用被記録材の受理剤、ガラス繊維用集束剤の製造に特に好適に用いることができる。A cationic urethane resin composition containing a cationic urethane resin (A) and water (B), wherein the cationic urethane resin (A) has a specific structural unit. A urethane resin composition is provided. The cationic urethane resin composition of the present invention can provide a polyurethane film with excellent durability. Further, the cationic urethane resin composition of the present invention has excellent dispersibility in water and stability during long-term storage. Therefore, the cationic urethane resin composition of the present invention is particularly suitable for use in the production of steel plates for building materials and home appliances, plastic films and plastic molded products, receiving agents for recording materials for inkjet printing, and sizing agents for glass fibers. Can be done.
Description
本発明は、カチオン性ウレタン樹脂組成物に関する。 The present invention relates to a cationic urethane resin composition.
ウレタン樹脂が水中に分散したウレタン樹脂組成物は、従来の有機溶剤系ウレタン樹脂組成物と比較して、環境への負荷を低減できることから、合成皮革、手袋、カーテンやシーツ等のコーティング剤などを製造する材料として、近年好適に使用され始めている（例えば、特許文献１を参照。）。 Urethane resin compositions in which urethane resin is dispersed in water have a lower environmental impact than conventional organic solvent-based urethane resin compositions, so they are used as coating agents for synthetic leather, gloves, curtains, sheets, etc. In recent years, it has begun to be suitably used as a manufacturing material (see, for example, Patent Document 1).
前記ウレタン樹脂組成物に対する要求特性としては、水中での分散性や長期保存時の安定性に優れることは勿論のこと、ポリウレタン皮膜の耐久性の更なる向上が求められている。 The properties required for the urethane resin composition are not only excellent dispersibility in water and stability during long-term storage, but also further improvement in the durability of the polyurethane film.
本発明が解決しようとする課題は、ポリウレタン皮膜の耐久性に優れるカチオン性ウレタン樹脂組成物を提供することである。 The problem to be solved by the present invention is to provide a cationic urethane resin composition that provides a polyurethane film with excellent durability.
本発明は、カチオン性ウレタン樹脂（Ａ）、及び、水（Ｂ）を含有するカチオン性ウレタン樹脂組成物であって、前記カチオン性ウレタン樹脂（Ａ）が、下記式（１）で示される構造単位を有することを特徴とするカチオン性ウレタン樹脂組成物を提供するものである。 The present invention provides a cationic urethane resin composition containing a cationic urethane resin (A) and water (B), wherein the cationic urethane resin (A) has a structure represented by the following formula (1). The object of the present invention is to provide a cationic urethane resin composition characterized by having a unit.
本発明のカチオン性ウレタン樹脂組成物は、耐久性に優れるポリウレタン皮膜を付与することができる。また、本発明のカチオン性ウレタン樹脂組成物は、水中での分散性、及び、長期保存時の安定性に優れるものである。 The cationic urethane resin composition of the present invention can provide a polyurethane film with excellent durability. Further, the cationic urethane resin composition of the present invention has excellent dispersibility in water and stability during long-term storage.
本発明のカチオン性ウレタン樹脂組成物は、特定の構造単位を有するカチオン性ウレタン樹脂（Ａ）、及び、水（Ｂ）を含有するものである。 The cationic urethane resin composition of the present invention contains a cationic urethane resin (A) having a specific structural unit and water (B).
前記カチオン性ウレタン（Ａ）は、優れた耐久性を得るうえで、下記式（１）で示される構造単位を有することが必須である。 In order to obtain excellent durability, the cationic urethane (A) must have a structural unit represented by the following formula (1).
前記式（１）中、Ｒ２及びＲ３は、互いに独立して脂環構造を含んでいてもよいアルキル基を示し、好ましくは、プロピル基、ブチル基、ペンチル基が好ましく、ブチル基がより好ましい。前記４級化剤の残基としては、好ましくはメチル基又はエチル基である。前記Ｘ－は、後述する酸や４級化剤として、酢酸、リン酸、ジブチル酸、ベンジルクロライド等を使用したときに形成されるアニオン性のイオンが好ましい。 In the formula (1), R 2 and R 3 independently represent an alkyl group which may contain an alicyclic structure, preferably a propyl group, a butyl group, or a pentyl group, and a butyl group is more preferable. preferable. The residue of the quaternizing agent is preferably a methyl group or an ethyl group. The above X - is preferably an anionic ion formed when acetic acid, phosphoric acid, dibutyric acid, benzyl chloride, etc. are used as the acid or quaternizing agent described later.
前記カチオン性ウレタン樹脂（Ａ）は、前記の硬い化学構造のエポキシ原料を用いることで、特にポリウレタン皮膜の伸長応力が向上でき、更に耐熱性も向上することができる。 By using the above-mentioned epoxy raw material having a hard chemical structure as the cationic urethane resin (A), the elongation stress of the polyurethane film can be particularly improved, and the heat resistance can also be improved.
前記カチオン性ウレタン樹脂（Ａ）は、例えば、前記式（２）又は式（３）で示される構造を有するジグリシジルエーテル（ｓ１）と２級アミン（ｓ２）との反応物であるアミノ基含有ポリオール（ａ１－１）を含むポリオール（ａ１）、及び、ポリイソシアネート（ａ２）の反応物を用いることができる。 The cationic urethane resin (A) is, for example, an amino group-containing resin that is a reaction product of a diglycidyl ether (s1) having a structure represented by the above formula (2) or formula (3) and a secondary amine (s2). A reaction product of polyol (a1) containing polyol (a1-1) and polyisocyanate (a2) can be used.
前記式（２）で示される構造を有するジグリシジルエーテルとしては、例えば、ビスフェノールＡ型ジグリシジルエーテル、ビスフェノールＡＰ型ジグリシジルエーテル、ビスフェノールＢ型ジグリシジルエーテル、ビスフェノールＢＰ型ジグリシジルエーテル、ビスフェノールＥ型ジグリシジルエーテル、ビスフェノールＦ型ジグリシジルエーテル、ビスフェノールＣ型ジグリシジルエーテル等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。これらの中でも、より一層優れた耐久性が得られる点から、ビスフェノールＦ型ジグリシジルエーテルが好ましい。 Examples of the diglycidyl ether having the structure represented by formula (2) include bisphenol A type diglycidyl ether, bisphenol AP type diglycidyl ether, bisphenol B type diglycidyl ether, bisphenol BP type diglycidyl ether, and bisphenol E type diglycidyl ether. Diglycidyl ether, bisphenol F type diglycidyl ether, bisphenol C type diglycidyl ether, etc. can be used. These compounds may be used alone or in combination of two or more. Among these, bisphenol F-type diglycidyl ether is preferred because it provides even better durability.
前記式（３）で示される構造を有するジグリシジルエーテルとしては、例えば、下記式（３－１）で示される化合物、式（３－２）で示される化合物等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。これらの中でも、より一層優れた耐久性が得られる点から、下記式（３－１）で示される化合物が好ましい。 As the diglycidyl ether having the structure represented by the formula (3), for example, a compound represented by the following formula (3-1), a compound represented by the formula (3-2), etc. can be used. These compounds may be used alone or in combination of two or more. Among these, the compound represented by the following formula (3-1) is preferred because it provides even better durability.
前記２級アミン（ｓ２）としては、例えば、ジメチルアミン、ジエチルアミン、ジ－ｎ－プロピルアミン、ジイソプロピルアミン、ジ－ｎ－ペンチルアミン、ジ－ｔｅｒｔ－ブチルアミン、ジ－ｓｅｃ－ブチルアミン、ジ－ｎ－ブチルアミン、ジ－ｎ－ペンチルアミン、ジ－ｎ－ペプチルアミン、ジ－ｎ－オクチルアミン、ジイソオクチルアミン、ジノニルアミン、ジイソノニルアミン、ジ－ｎ－デシルアミン、ジ－ｎ－ウンデシルアミン、ジ－ｎ－ドデシルアミン、ジ－ｎ－ペンタデシルアミン、ジ－ｎ－オクタデシルアミン、ジ－ｎ－ノナデシルアミン、ジ－ｎ－エイコシルアミン等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。これらの中でも、より一層優れた耐久性、水分散安定性が得られる点から、炭素原子数が２～１８の範囲の脂肪族アミンが好ましく、炭素原子数３～８の範囲の脂肪族アミンがより好ましい。 Examples of the secondary amine (s2) include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-pentylamine, di-tert-butylamine, di-sec-butylamine, di-n- Butylamine, di-n-pentylamine, di-n-peptylamine, di-n-octylamine, diisooctylamine, dinonylamine, diisononylamine, di-n-decylamine, di-n-undecylamine, di-n- Dodecylamine, di-n-pentadecylamine, di-n-octadecylamine, di-n-nonadecylamine, di-n-eicosylamine, etc. can be used. These compounds may be used alone or in combination of two or more. Among these, aliphatic amines having a carbon number of 2 to 18 are preferred, and aliphatic amines having a carbon number of 3 to 8 are preferred because they provide even better durability and water dispersion stability. More preferred.
前記アミノ基含有ポリオール（ａ１－１）の製造方法は、例えば、前記ジグリシジルエーテル（ｓ１）と前記２級アミン（ｓ２）とを、エポキシ基１当量に対して、ＮＨ基１当量となるように配合し、無触媒で、常温下又は加熱下で開環付加反応させることが挙げられる。前記反応は、必要に応じて有機溶剤の下で行ってもよく、また例えば、６０～１２０℃の範囲で、３０分～１４時間行うことが挙げられる。 The method for producing the amino group-containing polyol (a1-1) includes, for example, mixing the diglycidyl ether (s1) and the secondary amine (s2) in such a manner that the amount of the NH group is 1 equivalent per 1 equivalent of the epoxy group. For example, the ring-opening addition reaction may be carried out without a catalyst at room temperature or under heating. The reaction may be carried out in an organic solvent if necessary, and may be carried out, for example, at a temperature in the range of 60 to 120°C for 30 minutes to 14 hours.
前記有機溶剤としては、例えば、アセトン、ジエチルケトン、メチルエチルケトン、メチルイソブチルケトン等のケトン溶剤；ジエチルエーテル、エチレングリコールジメチルエーテル等のエーテル溶剤；酢酸エチル、酢酸ブチル等の酢酸エステル溶剤；ベンゼン、ヘキサン、トルエン、キシレン等の炭化水素溶剤；ジメチルホルムアミド等のアミド溶剤などを用いることができる。これらの有機溶剤は単独で用いても２種以上を併用してもよい。 Examples of the organic solvent include ketone solvents such as acetone, diethyl ketone, methyl ethyl ketone, and methyl isobutyl ketone; ether solvents such as diethyl ether and ethylene glycol dimethyl ether; acetate ester solvents such as ethyl acetate and butyl acetate; benzene, hexane, and toluene. , hydrocarbon solvents such as xylene; amide solvents such as dimethylformamide, etc. can be used. These organic solvents may be used alone or in combination of two or more.
前記アミノ基含有ポリオール（ａ１－１）の使用量としては、より一層優れた耐久性が得られる点から、前記カチオン性ウレタン樹脂（Ａ）の合計質量中０．１～３０質量％の範囲が好ましく、１～１５質量％の範囲が好ましい。 The amount of the amino group-containing polyol (a1-1) to be used is within the range of 0.1 to 30% by mass based on the total mass of the cationic urethane resin (A) in order to obtain even better durability. Preferably, the range is from 1 to 15% by weight.
前記ポリオール（ａ１）は、前記アミノ基含有ポリオール（ａ１－１）を必須成分として含有するが、必要に応じて、その他のポリオールを含有してもよい。前記ポリオール（ａ１）中における前記アミノ基含有ポリオール（ａ１－１）の含有量としては、より一層優れた耐久性が得られる点から、０．２～５０質量％の範囲が好ましく、０．５～３０質量％の範囲が好ましい。 The polyol (a1) contains the amino group-containing polyol (a1-1) as an essential component, but may contain other polyols as necessary. The content of the amino group-containing polyol (a1-1) in the polyol (a1) is preferably in the range of 0.2 to 50% by mass, and 0.5% by mass from the viewpoint of obtaining even better durability. A range of 30% by mass is preferred.
前記その他のポリオールとしては、例えば、ポリカーボネートポリオール、ポリエステルポリオール、ポリエーテルポリオール等を用いることができる。これらのポリオールは単独で用いても２種以上を併用してもよい。これらの中での、より一層優れた耐候性が得られる点から、ポリカーボネートポリオールが好ましい。 As the other polyols, for example, polycarbonate polyols, polyester polyols, polyether polyols, etc. can be used. These polyols may be used alone or in combination of two or more. Among these, polycarbonate polyols are preferred because they provide even better weather resistance.
前記その他のポリオールの数平均分子量としては、より一層優れた耐久性が得られる点から、５００～１０，０００の範囲が好ましく、７００～５，０００の範囲がより好ましい。なお、前記その他のポリオールの数平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により測定した値を示す。 The number average molecular weight of the other polyol is preferably in the range of 500 to 10,000, more preferably in the range of 700 to 5,000, from the standpoint of obtaining even better durability. The number average molecular weights of the other polyols are values measured by gel permeation chromatography (GPC).
前記アミノ基含有ポリオール（ａ１－１）は、より一層優れた水分散安定性を得るうえで、有する３級アミノ基の一部又は全てを酸で中和し、又は、４級化剤で４級化することが好ましい。 In the amino group-containing polyol (a1-1), in order to obtain even better water dispersion stability, some or all of the tertiary amino groups it has are neutralized with an acid, or quaternized with a quaternizing agent. It is preferable to grade.
前記酸としては、例えば、ギ酸、酢酸、プロピオン酸、コハク酸、グルタル酸、酪酸、乳酸、リンゴ酸、クエン酸、酒石酸、マロン酸、アジピン酸等の有機酸；スルホン酸、パラトルエンスルホン酸、メタンスルホン酸等の有機スルホン酸；塩酸、硫酸、硝酸、リン酸、ホウ酸、亜リン酸、フッ酸等の無機酸などを用いることができる。これらの酸は単独で用いても２種以上を併用してもよい。 Examples of the acid include organic acids such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, butyric acid, lactic acid, malic acid, citric acid, tartaric acid, malonic acid, and adipic acid; sulfonic acid, paratoluenesulfonic acid, Organic sulfonic acids such as methanesulfonic acid; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, phosphorous acid, and hydrofluoric acid can be used. These acids may be used alone or in combination of two or more.
前記４級化剤としては、例えば、ジメチル隆さん、ジエチル硫酸等のジアルキル硫酸；メチルクロライド、エチルクロライド、ベンジルクロライド、メチルブロマイド、エチルブロマイド、ベンジルブロマイド、メチルヨーダイド、エチルヨーダイド、ベンジルヨーダイド等のハロゲン化アルキル化合物；メタンスルホン酸メチル、パラトルエンスルホン酸メチル、メタンスルホン酸メチル等のスルホン酸メチル化合物；エチレンオキシド、プロピレンオキサイド、スチレンオキサイド、エピクロルヒドリン、アリルグリシジルエーテル、ブチルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、フェニルグリシジルエーテル等のエポキシ化合物などを用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 Examples of the quaternizing agent include dialkyl sulfates such as dimethyl Takashi and diethyl sulfate; methyl chloride, ethyl chloride, benzyl chloride, methyl bromide, ethyl bromide, benzyl bromide, methyl iodide, ethyl iodide, and benzyl iodide. halogenated alkyl compounds such as methyl methanesulfonate, methyl paratoluenesulfonate, methyl sulfonate compounds such as methyl methanesulfonate; ethylene oxide, propylene oxide, styrene oxide, epichlorohydrin, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl Epoxy compounds such as glycidyl ether and phenyl glycidyl ether can be used. These compounds may be used alone or in combination of two or more.
前記酸又は４級化剤の使用量としては、例えば、前記アミノ基含有ポリオール（ａ１－１）の３級アミノ基１当量に対して、０．１～３当量の範囲が挙げられる。 The amount of the acid or quaternizing agent used is, for example, in the range of 0.1 to 3 equivalents per equivalent of the tertiary amino group of the amino group-containing polyol (a1-1).
前記ポリイソシアネート（ａ２）としては、例えば、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ポリイソシアネート；シクロヘキサンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、テトラメチルキシリレンジイソシアネート、ノルボルネンジイソシアネート等の脂環式ポリイソシアネート；フェニ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、キシリレンジイソシアネート、ナフタレンジイソシアネート、ポリメチレンポリフェニルポリイソシアネート、カルボジイミド化ジフェニルメタンポリイソシアネート等の芳香族ポリイソシアネートなどを用いることができる。これらのポリイソシアネートは単独でも用いても２種以上を併用してもよい。 Examples of the polyisocyanate (a2) include aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; cycloaliphatic polyisocyanates such as cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, and norbornene diisocyanate; Aromatic polyisocyanates such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidized diphenylmethane polyisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more.
前記ポリイソシアネート（ａ２）の使用量としては、より一層優れた耐久性が得られる点から、前記カチオン性ウレタン樹脂（Ａ）の合計質量中５～６０質量％の範囲が好ましく、１０～４５質量％の範囲が好ましい。 The amount of the polyisocyanate (a2) to be used is preferably in the range of 5 to 60% by mass, based on the total mass of the cationic urethane resin (A), and 10 to 45% by mass, in order to obtain even better durability. A range of % is preferred.
前記カチオン性ウレタン樹脂（Ａ）の製造方法としては、例えば、前記アミノ基含有ポリオール（ａ１－１）、その他のポリオール、及び、前記ポリイソシアネート（ａ２）を一括に容器に仕込み、有機溶剤中又は無溶剤下で反応させてポリウレタン樹脂を得、更に、ポリウレタン樹脂中の３級アミノ基の一部又は全部を酸で中和し、及び／又は、前記４級化剤で４級化した後、水（Ｂ）を投入して水分散させる方法などが挙げられる。 As a method for producing the cationic urethane resin (A), for example, the amino group-containing polyol (a1-1), other polyols, and the polyisocyanate (a2) are charged all at once into a container, and the mixture is heated in an organic solvent or After reacting in the absence of a solvent to obtain a polyurethane resin, further neutralizing some or all of the tertiary amino groups in the polyurethane resin with an acid and/or quaternizing with the quaternizing agent, Examples include a method of adding water (B) and dispersing it in water.
前記カチオン性ウレタン樹脂（Ａ）の重量平均分子量としては、より一層優れた耐久性、及び、水分散安定性が得られる点から、４，０００～３００，０００の範囲が好ましく、７，０００～２００，０００の範囲がより好ましい。なお、前記カチオン性ウレタン樹脂（Ａ）の重量平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により測定した値を示す。 The weight average molecular weight of the cationic urethane resin (A) is preferably in the range of 4,000 to 300,000, and 7,000 to A range of 200,000 is more preferred. The weight average molecular weight of the cationic urethane resin (A) is a value measured by gel permeation chromatography (GPC).
前記水（Ｂ）としては、例えば、イオン交換水、蒸留水等を用いることができる。これらの水は単独で用いても２種以上を併用してもよい。前記水（Ｂ）の含有率としては、例えば、３５～９０質量％の範囲である。 As the water (B), for example, ion exchange water, distilled water, etc. can be used. These waters may be used alone or in combination of two or more. The content of water (B) is, for example, in the range of 35 to 90% by mass.
本発明のカチオン性ウレタン樹脂組成物は、前記カチオン性ウレタン樹脂（Ａ）と前記水（Ｂ）とを含有するものであるが、必要に応じて、その他の添加剤を含有していてもよい。 The cationic urethane resin composition of the present invention contains the cationic urethane resin (A) and the water (B), but may contain other additives as necessary. .
前記その他の添加剤としては、例えば、中和剤、乳化剤、架橋剤、増粘剤、ウレタン化触媒、充填剤、発泡剤、顔料、染料、撥油剤、中空発泡体、難燃剤、消泡剤、レベリング剤、ブロッキング防止剤等を用いることができる。これらの添加剤は単独で用いても２種以上を併用してもよい。 Examples of the other additives include neutralizers, emulsifiers, crosslinking agents, thickeners, urethanization catalysts, fillers, blowing agents, pigments, dyes, oil repellents, hollow foams, flame retardants, and antifoaming agents. , a leveling agent, an antiblocking agent, etc. can be used. These additives may be used alone or in combination of two or more.
以上、本発明のカチオン性ウレタン樹脂組成物は、耐久性に優れるポリウレタン皮膜を付与することができる。また、本発明のカチオン性ウレタン樹脂組成物は、水中での分散性、及び、長期保存時の安定性に優れるものである。よって、本発明のカチオン性ウレタン樹脂組成物は、建材や家電用の鋼板、プラスチックフィルムやプラスチック成型品、インクジェット印刷用被記録材の受理剤、ガラス繊維用集束剤の製造に特に好適に用いることができる。 As described above, the cationic urethane resin composition of the present invention can provide a polyurethane film with excellent durability. Further, the cationic urethane resin composition of the present invention has excellent dispersibility in water and stability during long-term storage. Therefore, the cationic urethane resin composition of the present invention is particularly suitable for use in the production of steel plates for building materials and home appliances, plastic films and plastic molded products, receiving agents for recording materials for inkjet printing, and sizing agents for glass fibers. I can do it.
以下、実施例を用いて、本発明をより詳細に説明する。 Hereinafter, the present invention will be explained in more detail using Examples.
［合成例１］アミノ基含有ポリオール（ａ１－１－１）の合成
攪拌機、還流冷却器、温度計、及び、滴下装置を備えた四つ口フラスコに、ビスフェノールＦ型ジグリシジルエーテル５６質量部を仕込んだ後、フラスコ内を窒素置換した。次いで、前記フラスコ内の温度が７０℃になるまで加熱した後、滴下装置を使用してジ－ｎ－ブチルアミン４４質量部を３０分間滴下し、終了後、９０℃で１０時間反応させることで、アミノ基含有ポリオール（ａ１－１－１）を得た。
[Synthesis Example 1] Synthesis of amino group-containing polyol (a1-1-1) In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and dropping device, 56 parts by mass of bisphenol F-type diglycidyl ether was added. After charging, the inside of the flask was replaced with nitrogen. Next, after heating until the temperature inside the flask reached 70 ° C., 44 parts by mass of di-n-butylamine was added dropwise for 30 minutes using a dropping device, and after completion of the reaction, the reaction was carried out at 90 ° C. for 10 hours. An amino group-containing polyol (a1-1-1) was obtained.
［合成例２］アミノ基含有ポリオール（ａ１－１－２）の合成
ビスフェノールＦ型ジグリシジルエーテル５６質量部に代え、式（３－１）で示される化合物５６質量部を用いた以外は、合成例１と同様にしてアミノ基含有ポリオール（ａ１－１－２）を得た。
[Synthesis Example 2] Synthesis of amino group-containing polyol (a1-1-2) Synthesis except that 56 parts by mass of the compound represented by formula (3-1) was used in place of 56 parts by mass of bisphenol F-type diglycidyl ether. An amino group-containing polyol (a1-1-2) was obtained in the same manner as in Example 1.
［比較合成例１］アミノ基含有ポリオール（ａＲ１）の合成
攪拌機、還流冷却器、温度計、及び、滴下装置を備えた四つ口フラスコに、ポリプロピレンングリコールジグリシジルエーテル（エポキシ当量；２０１ｇ／当量）５９０質量部を仕込んだ後、フラスコ内を窒素置換した。次いで、前記フラスコ内の温度が７０℃になるまで加熱した後、滴下装置を使用してジ－ｎ－ブチルアミン３８０質量部を３０分間滴下し、終了後、９０℃で１０時間反応させることで、アミノ基含有ポリオール（ａＲ１）を得た。
[Comparative Synthesis Example 1] Synthesis of amino group-containing polyol (aR1) Polypropylene glycol diglycidyl ether (epoxy equivalent; 201 g/equivalent) was placed in a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and dropping device. ) After charging 590 parts by mass, the inside of the flask was purged with nitrogen. Next, after heating until the temperature inside the flask reached 70 ° C., 380 parts by mass of di-n-butylamine was added dropwise for 30 minutes using a dropping device, and after completion, the reaction was carried out at 90 ° C. for 10 hours. An amino group-containing polyol (aR1) was obtained.
［実施例１］
温度計、攪拌装置、還流冷却管、及び滴下装置を備えた４つ口フラスコに、ポリカーボネートポリオール（日本ポリウレタン工業株式会社製「ニッポラン９８０Ｒ」）を３０．６質量部、ＭＥＫ１８．７質量部を加え、５０℃まで冷却しながら攪拌した。攪拌後、４，４‘－ジシクロヘキシルメタンジイソシアネート８．７質量部、オクチル酸第一錫０．０１質量部を加え、７０℃で２時間反応させた。
その後、合成例１で得られたアミノ基含有ポリオール（ａ１－１－１）３．１質量部を添加し、４時間反応させた。その後、アミノエチルエタノールアミン０．８５質量部を加え、鎖伸長反応を１時間行った。
次いで、ＭＥＫを１０．６質量部、酢酸を０．７５質量部添加し、５５℃で１時間保持した後、４０℃に冷却し、イオン交換水８５質量部添加し、水分散体を調製した。これを減圧留去し、不揮発分が３５質量％のカチオン性ウレタン樹脂組成物（１）を得た。
[Example 1]
Add 30.6 parts by mass of polycarbonate polyol ("Nipporan 980R" manufactured by Nippon Polyurethane Industries, Ltd.) and 18.7 parts by mass of MEK to a four-necked flask equipped with a thermometer, stirring device, reflux condenser, and dropping device. The mixture was stirred while cooling to 50°C. After stirring, 8.7 parts by mass of 4,4'-dicyclohexylmethane diisocyanate and 0.01 parts by mass of stannous octylate were added, and the mixture was reacted at 70°C for 2 hours.
Thereafter, 3.1 parts by mass of the amino group-containing polyol (a1-1-1) obtained in Synthesis Example 1 was added and reacted for 4 hours. Thereafter, 0.85 parts by mass of aminoethylethanolamine was added, and a chain extension reaction was carried out for 1 hour.
Next, 10.6 parts by mass of MEK and 0.75 parts by mass of acetic acid were added, held at 55°C for 1 hour, cooled to 40°C, and 85 parts by mass of ion-exchanged water were added to prepare an aqueous dispersion. . This was distilled off under reduced pressure to obtain a cationic urethane resin composition (1) with a nonvolatile content of 35% by mass.
［実施例２］
合成例１で得られたアミノ基含有ポリオール（ａ１－１－１）３．１質量部を、合成例２で得られたアミノ基含有ポリオール（ａ１－１－２）３．２質量部に変更した以外は、実施例１と同様にして、カチオン性ウレタン樹脂組成物（２）を得た。
[Example 2]
3.1 parts by mass of the amino group-containing polyol (a1-1-1) obtained in Synthesis Example 1 was changed to 3.2 parts by mass of the amino group-containing polyol (a1-1-2) obtained in Synthesis Example 2. A cationic urethane resin composition (2) was obtained in the same manner as in Example 1 except for the following steps.
［比較例１］
合成例１で得られたアミノ基含有ポリオール（ａ１－１－）３．１質量部を、比較合成例１で得られたアミノ基含有ポリオール（ａＲ１）３．５質量部に変更した以外は、実施例１と同様にして、カチオン性ウレタン樹脂組成物（Ｒ１）を得た。
[Comparative example 1]
Except that 3.1 parts by mass of the amino group-containing polyol (a1-1-) obtained in Synthesis Example 1 was changed to 3.5 parts by mass of the amino group-containing polyol (aR1) obtained in Comparative Synthesis Example 1. A cationic urethane resin composition (R1) was obtained in the same manner as in Example 1.
［数平均分子量・重量平均分子量の測定方法］
ポリオールの数平均分子量、カチオン性ウレタン樹脂の重量平均分子量は、ゲル・パーミエーション・カラムクロマトグラフィー（ＧＰＣ）法により、下記の条件で測定し得られた値を示す。
[Measurement method of number average molecular weight/weight average molecular weight]
The number average molecular weight of the polyol and the weight average molecular weight of the cationic urethane resin are the values measured by gel permeation column chromatography (GPC) under the following conditions.
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ－８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
「ＴＳＫｇｅｌ Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度０．４質量％のテトラヒドロフラン溶液）
標準試料：下記の標準ポリスチレンを用いて検量線を作成した。
Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were used by connecting them in series.
"TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000" (7.8mm I.D. x 30cm) x 1 "TSKgel G3000" (7.8mm I.D. x 30cm) x 1 Book "TSKgel G2000" (7.8mm I.D. x 30cm) x 1 Detector: RI (differential refractometer)
Column temperature: 40℃
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL/min Injection volume: 100 μL (Tetrahydrofuran solution with sample concentration 0.4% by mass)
Standard sample: A calibration curve was created using the following standard polystyrene.
（標準ポリスチレン）
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－１０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－２５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－５０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－４」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－４０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－８０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１２８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２８８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－５５０」
(Standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
“TSKgel Standard Polystyrene F-1” manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation
［耐久性の評価方法］
（１）伸長応力の評価
離型紙上に乾燥後の膜厚が１５０μｍとなるように、実施例及び比較例で得られたカチオン性ウレタン樹脂組成物を塗工し、２３℃湿度６５％で１日乾燥後に１５０℃で５分間乾燥させることで、ポリウレタン皮膜を得た。離型紙から剥離し、５ｍｍ幅に裁断したものを試験片とした。この試験片を、株式会社エー・アンド・デイ製「テンシロン万能材料試験機」を使用して、３００ｍｍ／ｍｉｎで引張り、１００％引張時、２００％引張時、３００％引張時の伸長応力（ＭＰａ）を測定した。なお、伸長応力が高い値であるほど良好な耐久性を示す。
[Durability evaluation method]
(1) Evaluation of elongation stress The cationic urethane resin compositions obtained in the Examples and Comparative Examples were coated on a release paper so that the film thickness after drying was 150 μm. After drying in the sun, a polyurethane film was obtained by drying at 150° C. for 5 minutes. The test piece was peeled off from the release paper and cut into 5 mm width pieces. This test piece was pulled at 300 mm/min using "Tensilon Universal Material Testing Machine" manufactured by A&D Co., Ltd., and the elongation stress (MPa) was measured at 100% tension, 200% tension, and 300% tension. ) was measured. Note that the higher the elongation stress value, the better the durability.
（２）耐熱変色性の評価
離型紙上に乾燥後の膜厚が１５０μｍとなるように、実施例及び比較例で得られたカチオン性ウレタン樹脂組成物を塗工し、２３℃湿度６５％で１日乾燥後に１５０℃で５分間乾燥させることで、ポリウレタン皮膜を得た。離型紙から剥離した試験片を、２００℃で１時間加熱し、加熱前後の色差ΔＥをコニカミノルタ株式会社製「ＣＭ－５」を使用して測定した。なお、ΔＥが低い値であるほど良好な耐久性を示す。
(2) Evaluation of heat resistance to discoloration The cationic urethane resin compositions obtained in the Examples and Comparative Examples were coated on release paper so that the film thickness after drying was 150 μm, and the mixture was heated at 23°C with a humidity of 65%. After drying for one day, a polyurethane film was obtained by drying at 150° C. for 5 minutes. The test piece peeled off from the release paper was heated at 200° C. for 1 hour, and the color difference ΔE before and after heating was measured using “CM-5” manufactured by Konica Minolta, Inc. Note that the lower the value of ΔE, the better the durability.
本発明のカチオン性ウレタン樹脂組成物は、実施例１及び２の通り、耐久性に優れるポリウレタン皮膜が得られることが分かった。 As shown in Examples 1 and 2, it was found that the cationic urethane resin composition of the present invention provides a polyurethane film with excellent durability.
一方、比較例１は、本発明で規定する以外のカチオン性ウレタン樹脂組成物を用いた態様であるが、耐久性が不十分であった。 On the other hand, Comparative Example 1 was an embodiment using a cationic urethane resin composition other than that specified in the present invention, but the durability was insufficient.
Claims (2)
前記カチオン性ウレタン樹脂（Ａ）が、下記式（１）で示される構造単位を有することを特徴とするカチオン性ウレタン樹脂組成物。
A cationic urethane resin composition, wherein the cationic urethane resin (A) has a structural unit represented by the following formula (1).
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