JP2018080312A - Aqueous composite resin dispersion and method for producing the same, aqueous ink composition, and printed matter - Google Patents
Aqueous composite resin dispersion and method for producing the same, aqueous ink composition, and printed matter Download PDFInfo
- Publication number
- JP2018080312A JP2018080312A JP2016225428A JP2016225428A JP2018080312A JP 2018080312 A JP2018080312 A JP 2018080312A JP 2016225428 A JP2016225428 A JP 2016225428A JP 2016225428 A JP2016225428 A JP 2016225428A JP 2018080312 A JP2018080312 A JP 2018080312A
- Authority
- JP
- Japan
- Prior art keywords
- group
- composite resin
- aqueous
- urethane
- ethylenically unsaturated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000805 composite resin Substances 0.000 title claims abstract description 80
- 239000006185 dispersion Substances 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 239000000178 monomer Substances 0.000 claims abstract description 64
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 150000003077 polyols Chemical class 0.000 claims abstract description 37
- 229920005862 polyol Polymers 0.000 claims abstract description 34
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 229920001807 Urea-formaldehyde Polymers 0.000 claims abstract description 21
- OYQYHJRSHHYEIG-UHFFFAOYSA-N ethyl carbamate;urea Chemical compound NC(N)=O.CCOC(N)=O OYQYHJRSHHYEIG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 14
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000012736 aqueous medium Substances 0.000 claims abstract description 7
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 77
- 239000002904 solvent Substances 0.000 claims description 33
- 239000000758 substrate Substances 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 21
- 239000000049 pigment Substances 0.000 claims description 19
- 125000002947 alkylene group Chemical group 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 125000000732 arylene group Chemical group 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 238000001035 drying Methods 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 54
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 47
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 37
- 229920005989 resin Polymers 0.000 description 36
- 239000011347 resin Substances 0.000 description 36
- -1 specifically Substances 0.000 description 33
- 239000011248 coating agent Substances 0.000 description 29
- 238000000576 coating method Methods 0.000 description 29
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 229920000178 Acrylic resin Polymers 0.000 description 18
- 239000004925 Acrylic resin Substances 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 16
- 239000012860 organic pigment Substances 0.000 description 15
- 125000000524 functional group Chemical group 0.000 description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 13
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 239000000306 component Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 229920005906 polyester polyol Polymers 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000003759 ester based solvent Substances 0.000 description 6
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 6
- 229940097275 indigo Drugs 0.000 description 6
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000005453 ketone based solvent Substances 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 3
- TXHZNLCKXHJYNX-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound COCCOCCOCCOCCOCCOCCOCCOCCOCCOC(=O)C(C)=C TXHZNLCKXHJYNX-UHFFFAOYSA-N 0.000 description 3
- ALEBYBVYXQTORU-UHFFFAOYSA-N 6-hydrazinyl-6-oxohexanoic acid Chemical compound NNC(=O)CCCCC(O)=O ALEBYBVYXQTORU-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-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
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 239000005456 alcohol based solvent Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000003638 chemical reducing agent 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
- 239000008358 core component Substances 0.000 description 3
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 3
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 125000000468 ketone group Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 3
- 229940090181 propyl acetate Drugs 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- LLBIOIRWAYBCKK-UHFFFAOYSA-N pyranthrene-8,16-dione Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3C=C4C5=CC=CC=C5C(=O)C5=C4C4=C3C2=C1C=C4C=C5 LLBIOIRWAYBCKK-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- NOGBEXBVDOCGDB-NRFIWDAESA-L (z)-4-ethoxy-4-oxobut-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].CCOC(=O)\C=C(\C)[O-].CCOC(=O)\C=C(\C)[O-] NOGBEXBVDOCGDB-NRFIWDAESA-L 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 2
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 2
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical class NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920005731 JONCRYL® 67 Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 2
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- NEXZVOLIDKSFBH-UHFFFAOYSA-N (1,1-diphenyl-2-phosphonooxyethyl) 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C(COP(O)(O)=O)(OC(=O)C(=C)C)C1=CC=CC=C1 NEXZVOLIDKSFBH-UHFFFAOYSA-N 0.000 description 1
- YRIOTLGRXFJRTJ-UHFFFAOYSA-N (1,1-diphenyl-2-phosphonooxyethyl) prop-2-enoate Chemical compound C=1C=CC=CC=1C(OC(=O)C=C)(COP(O)(=O)O)C1=CC=CC=C1 YRIOTLGRXFJRTJ-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-UHFFFAOYSA-N 0.000 description 1
- JWTGRKUQJXIWCV-UHFFFAOYSA-N 1,2,3-trihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(O)C(O)CO JWTGRKUQJXIWCV-UHFFFAOYSA-N 0.000 description 1
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-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
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- 229940015975 1,2-hexanediol Drugs 0.000 description 1
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-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
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-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
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- FKOMNQCOHKHUCP-UHFFFAOYSA-N 1-[n-(2-hydroxypropyl)anilino]propan-2-ol Chemical compound CC(O)CN(CC(C)O)C1=CC=CC=C1 FKOMNQCOHKHUCP-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- UHAMPPWFPNXLIU-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)pentanoic acid Chemical compound CCCC(CO)(CO)C(O)=O UHAMPPWFPNXLIU-UHFFFAOYSA-N 0.000 description 1
- HPQUMJNDQVOTAZ-UHFFFAOYSA-N 2,2-dihydroxypropanoic acid Chemical compound CC(O)(O)C(O)=O HPQUMJNDQVOTAZ-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 1
- PITLEXLWAKFCAI-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.OCCOCC(O)OC1=CC=CC=C1 PITLEXLWAKFCAI-UHFFFAOYSA-N 0.000 description 1
- IAMASUILMZETHW-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOCC(O)OC1=CC=CC=C1 IAMASUILMZETHW-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
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- HHAPGMVKBLELOE-UHFFFAOYSA-N 2-(2-methylpropoxy)ethanol Chemical compound CC(C)COCCO HHAPGMVKBLELOE-UHFFFAOYSA-N 0.000 description 1
- HRWADRITRNUCIY-UHFFFAOYSA-N 2-(2-propan-2-yloxyethoxy)ethanol Chemical compound CC(C)OCCOCCO HRWADRITRNUCIY-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- YJTIFIMHZHDNQZ-UHFFFAOYSA-N 2-[2-(2-methylpropoxy)ethoxy]ethanol Chemical compound CC(C)COCCOCCO YJTIFIMHZHDNQZ-UHFFFAOYSA-N 0.000 description 1
- FETMDPWILVCFLL-UHFFFAOYSA-N 2-[2-(2-propan-2-yloxyethoxy)ethoxy]ethanol Chemical compound CC(C)OCCOCCOCCO FETMDPWILVCFLL-UHFFFAOYSA-N 0.000 description 1
- VLTSFMBMFCXCKB-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]-1-phenoxyethanol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.OCCOCCOCCOCC(O)OC1=CC=CC=C1 VLTSFMBMFCXCKB-UHFFFAOYSA-N 0.000 description 1
- AJSNIWUHRQAZOS-UHFFFAOYSA-N 2-[2-[2-(2-methylpropoxy)ethoxy]ethoxy]ethanol Chemical compound CC(C)COCCOCCOCCO AJSNIWUHRQAZOS-UHFFFAOYSA-N 0.000 description 1
- XMIYEVCXHOOJMF-UHFFFAOYSA-N 2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]-1-phenoxyethanol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.OCCOCCOCCOCCOCCOCC(O)OC1=CC=CC=C1 XMIYEVCXHOOJMF-UHFFFAOYSA-N 0.000 description 1
- ADRHDZXSVIPHAF-UHFFFAOYSA-N 2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]-1-phenoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOCCOCCOCCOCCOCC(O)OC1=CC=CC=C1 ADRHDZXSVIPHAF-UHFFFAOYSA-N 0.000 description 1
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 1
- UYXQLQUXXCIFQM-UHFFFAOYSA-N 2-hydroxy-1,3,2$l^{5}-dioxaphospholane 2-oxide Chemical compound OP1(=O)OCCO1 UYXQLQUXXCIFQM-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- UPTHZKIDNHJFKQ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.OCC(O)CO UPTHZKIDNHJFKQ-UHFFFAOYSA-N 0.000 description 1
- SMBRHGJEDJVDOB-UHFFFAOYSA-N 2-methylpropanimidamide;dihydrochloride Chemical compound Cl.Cl.CC(C)C(N)=N SMBRHGJEDJVDOB-UHFFFAOYSA-N 0.000 description 1
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 1
- KFFUEVDMVNIOHA-UHFFFAOYSA-N 3-aminobenzenethiol Chemical compound NC1=CC=CC(S)=C1 KFFUEVDMVNIOHA-UHFFFAOYSA-N 0.000 description 1
- CARSMBZECAABMO-UHFFFAOYSA-N 3-chloro-2,6-dimethylbenzoic acid Chemical compound CC1=CC=C(Cl)C(C)=C1C(O)=O CARSMBZECAABMO-UHFFFAOYSA-N 0.000 description 1
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- ULMZOZMSDIOZAF-UHFFFAOYSA-N 3-hydroxy-2-(hydroxymethyl)propanoic acid Chemical compound OCC(CO)C(O)=O ULMZOZMSDIOZAF-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- IMDPTYFNMLYSLH-UHFFFAOYSA-N 3-silylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[SiH3] IMDPTYFNMLYSLH-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-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
- ZEHOVWPIGREOPO-UHFFFAOYSA-N 4,5,6,7-tetrachloro-2-[2-(4,5,6,7-tetrachloro-1,3-dioxoinden-2-yl)quinolin-8-yl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C(=O)N1C(C1=N2)=CC=CC1=CC=C2C1C(=O)C2=C(Cl)C(Cl)=C(Cl)C(Cl)=C2C1=O ZEHOVWPIGREOPO-UHFFFAOYSA-N 0.000 description 1
- WZSFTHVIIGGDOI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3-[2-methyl-3-[(4,5,6,7-tetrachloro-3-oxoisoindol-1-yl)amino]anilino]isoindol-1-one Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C2=C1C(NC1=CC=CC(NC=3C4=C(C(=C(Cl)C(Cl)=C4Cl)Cl)C(=O)N=3)=C1C)=NC2=O WZSFTHVIIGGDOI-UHFFFAOYSA-N 0.000 description 1
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 description 1
- RIRRYXTXJAZPMP-UHFFFAOYSA-N 4-aminobutane-1-thiol Chemical compound NCCCCS RIRRYXTXJAZPMP-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- HBOSQVFEPQCBNL-UHFFFAOYSA-N 4-propyloctane-3,3-diol Chemical compound CCCCC(CCC)C(O)(O)CC HBOSQVFEPQCBNL-UHFFFAOYSA-N 0.000 description 1
- NEJMTSWXTZREOC-UHFFFAOYSA-N 4-sulfanylbutan-1-ol Chemical compound OCCCCS NEJMTSWXTZREOC-UHFFFAOYSA-N 0.000 description 1
- ZZTIQZXRIJXCPC-UHFFFAOYSA-N 5-(phosphonooxymethyl)nonan-5-yl prop-2-enoate Chemical compound CCCCC(CCCC)(COP(O)(O)=O)OC(=O)C=C ZZTIQZXRIJXCPC-UHFFFAOYSA-N 0.000 description 1
- CGLVZFOCZLHKOH-UHFFFAOYSA-N 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo(3,2-b:3',2'-m)triphenodioxazine Chemical compound CCN1C2=CC=CC=C2C2=C1C=C1OC3=C(Cl)C4=NC(C=C5C6=CC=CC=C6N(C5=C5)CC)=C5OC4=C(Cl)C3=NC1=C2 CGLVZFOCZLHKOH-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N Alizarin Natural products C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RBUWQEHTCBTJBF-UHFFFAOYSA-N CCCC(=C)C(=O)N(NCC)NCC Chemical compound CCCC(=C)C(=O)N(NCC)NCC RBUWQEHTCBTJBF-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 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
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical group CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920005732 JONCRYL® 678 Polymers 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- GPDWNEFHGANACG-UHFFFAOYSA-L [dibutyl(2-ethylhexanoyloxy)stannyl] 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)O[Sn](CCCC)(CCCC)OC(=O)C(CC)CCCC GPDWNEFHGANACG-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000007774 anilox coating Methods 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- XDIJWRHVEDUFGP-UHFFFAOYSA-N azanium;2-phenylethenesulfonate Chemical compound [NH4+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 XDIJWRHVEDUFGP-UHFFFAOYSA-N 0.000 description 1
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical group C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- SMTOKHQOVJRXLK-UHFFFAOYSA-N butane-1,4-dithiol Chemical compound SCCCCS SMTOKHQOVJRXLK-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- ZLFVRXUOSPRRKQ-UHFFFAOYSA-N chembl2138372 Chemical compound [O-][N+](=O)C1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 ZLFVRXUOSPRRKQ-UHFFFAOYSA-N 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- PLYDMIIYRWUYBP-UHFFFAOYSA-N ethyl 4-[[2-chloro-4-[3-chloro-4-[(3-ethoxycarbonyl-5-oxo-1-phenyl-4h-pyrazol-4-yl)diazenyl]phenyl]phenyl]diazenyl]-5-oxo-1-phenyl-4h-pyrazole-3-carboxylate Chemical compound CCOC(=O)C1=NN(C=2C=CC=CC=2)C(=O)C1N=NC(C(=C1)Cl)=CC=C1C(C=C1Cl)=CC=C1N=NC(C(=N1)C(=O)OCC)C(=O)N1C1=CC=CC=C1 PLYDMIIYRWUYBP-UHFFFAOYSA-N 0.000 description 1
- NVPXEWPKAICFCQ-UHFFFAOYSA-N ethyl acetate;titanium Chemical compound [Ti].CCOC(C)=O NVPXEWPKAICFCQ-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 229940017705 formaldehyde sulfoxylate Drugs 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 1
- LSSQTAFYHNYODP-UHFFFAOYSA-N heptane-2,2-diol Chemical compound CCCCCC(C)(O)O LSSQTAFYHNYODP-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- SBGKURINHGJRFN-UHFFFAOYSA-N hydroxymethanesulfinic acid Chemical compound OCS(O)=O SBGKURINHGJRFN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- ZKIAYSOOCAKOJR-UHFFFAOYSA-M lithium;2-phenylethenesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 ZKIAYSOOCAKOJR-UHFFFAOYSA-M 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 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
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GZPVGWXZCDJAGP-UHFFFAOYSA-N n,n-bis(butoxymethyl)prop-2-enamide Chemical compound CCCCOCN(C(=O)C=C)COCCCC GZPVGWXZCDJAGP-UHFFFAOYSA-N 0.000 description 1
- YOPHLFVSHAHNMB-UHFFFAOYSA-N n,n-bis(ethoxymethyl)prop-2-enamide Chemical compound CCOCN(C(=O)C=C)COCC YOPHLFVSHAHNMB-UHFFFAOYSA-N 0.000 description 1
- FKUCXJWFJBFVHQ-UHFFFAOYSA-N n,n-bis(methoxymethyl)prop-2-enamide Chemical compound COCN(COC)C(=O)C=C FKUCXJWFJBFVHQ-UHFFFAOYSA-N 0.000 description 1
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 description 1
- BDGYUEIEAPRCRS-UHFFFAOYSA-N n,n-bis(pentoxymethyl)prop-2-enamide Chemical compound CCCCCOCN(C(=O)C=C)COCCCCC BDGYUEIEAPRCRS-UHFFFAOYSA-N 0.000 description 1
- FEAREGDDZJVSTE-UHFFFAOYSA-N n,n-bis(propoxymethyl)prop-2-enamide Chemical compound CCCOCN(C(=O)C=C)COCCC FEAREGDDZJVSTE-UHFFFAOYSA-N 0.000 description 1
- DPLUMPJQXVYXBH-UHFFFAOYSA-N n,n-diethyl-2-phenylethenamine Chemical compound CCN(CC)C=CC1=CC=CC=C1 DPLUMPJQXVYXBH-UHFFFAOYSA-N 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- SDYRIBONPHEWCT-UHFFFAOYSA-N n,n-dimethyl-2-phenylethenamine Chemical compound CN(C)C=CC1=CC=CC=C1 SDYRIBONPHEWCT-UHFFFAOYSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- CWXODBOOPJEYLA-UHFFFAOYSA-N n-(ethoxymethyl)-n-(methoxymethyl)-2-methylprop-2-enamide Chemical compound CCOCN(COC)C(=O)C(C)=C CWXODBOOPJEYLA-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NKZQKINFDLZVRY-UHFFFAOYSA-N n-butylbutan-1-amine;toluene Chemical compound CC1=CC=CC=C1.CCCCNCCCC NKZQKINFDLZVRY-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- MADOXCFISYCULS-UHFFFAOYSA-N octyl 2-sulfanylacetate Chemical compound CCCCCCCCOC(=O)CS MADOXCFISYCULS-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- KMTUBAIXCBHPIZ-UHFFFAOYSA-N pentane-1,5-dithiol Chemical compound SCCCCCS KMTUBAIXCBHPIZ-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ZZSIDSMUTXFKNS-UHFFFAOYSA-N perylene red Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N(C(=O)C=1C2=C3C4=C(OC=5C=CC=CC=5)C=1)C(=O)C2=CC(OC=1C=CC=CC=1)=C3C(C(OC=1C=CC=CC=1)=CC1=C2C(C(N(C=3C(=CC=CC=3C(C)C)C(C)C)C1=O)=O)=C1)=C2C4=C1OC1=CC=CC=C1 ZZSIDSMUTXFKNS-UHFFFAOYSA-N 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- USGIERNETOEMNR-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO.CCCO USGIERNETOEMNR-UHFFFAOYSA-N 0.000 description 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- DVQHRBFGRZHMSR-UHFFFAOYSA-N sodium methyl 2,2-dimethyl-4,6-dioxo-5-(N-prop-2-enoxy-C-propylcarbonimidoyl)cyclohexane-1-carboxylate Chemical compound [Na+].C=CCON=C(CCC)[C-]1C(=O)CC(C)(C)C(C(=O)OC)C1=O DVQHRBFGRZHMSR-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N tertiary amyl alcohol Natural products CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 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
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は、水性複合樹脂分散体とその製造方法、水性インキ組成物、印刷物に関する。 The present invention relates to an aqueous composite resin dispersion and a method for producing the same, an aqueous ink composition, and a printed matter.
近年、省エネや低コスト、環境負荷低減の観点から、グラビアやフレキソ、インクジェットなど、各種インキ市場において、非極性フィルム基材への密着性に優れ、強靭な塗膜耐性を発現する水性インキの開発が急がれている。これらの水性インキには、顔料分散性や耐擦性に優れるアクリル樹脂や、基材密着性に優れるウレタン樹脂が使用されている。また、各々の樹脂の利点を活かすため、アクリル樹脂とウレタン樹脂のブレンドや複合化についても活発に検討されている。しかしながら、一般的に、アクリル樹脂とウレタン樹脂の相溶が不良である場合が多い。したがって、単純なブレンドや複合化では、塗膜耐性の向上は図れず、むしろ脆弱な塗膜となり、塗膜耐性が大幅に悪化する傾向にあった。 In recent years, from the viewpoints of energy saving, low cost, and reduction of environmental impact, development of water-based inks that have excellent adhesion to non-polar film substrates and that exhibit strong coating resistance in various ink markets such as gravure, flexo, and inkjet. Is in a hurry. In these water-based inks, an acrylic resin excellent in pigment dispersibility and abrasion resistance and a urethane resin excellent in substrate adhesion are used. In addition, in order to make use of the advantages of each resin, active studies are also being conducted on blending and combining acrylic resins and urethane resins. However, generally, the compatibility between the acrylic resin and the urethane resin is often poor. Therefore, with simple blending or complexing, the coating film resistance cannot be improved, but rather a fragile coating film, and the coating film resistance tends to deteriorate significantly.
特許文献1では、シェル成分が水性ウレタン樹脂、コア成分がアクリル樹脂で構成される水性インキ用コアシェル型複合樹脂が開示されている。ウレタン樹脂にヒドラジド基、アクリル樹脂にケト基を導入し、異種樹脂間で常温架橋させる事で、塗膜耐性の向上を試みている。しかしながら、この設計では架橋前のウレタン樹脂とアクリル樹脂の相溶が悪く、最終的に架橋させても飛躍的な塗膜耐性向上には至らない。 Patent Document 1 discloses a core-shell composite resin for water-based ink in which the shell component is an aqueous urethane resin and the core component is an acrylic resin. By introducing a hydrazide group into a urethane resin and a keto group into an acrylic resin, and crosslinking at different temperatures between different resins, we are trying to improve coating film resistance. However, in this design, the compatibility between the urethane resin and the acrylic resin before cross-linking is poor, and even if the cross-linking is finally performed, the coating film resistance is not dramatically improved.
特許文献2では、ウレタン骨格にエチレン性不飽和基を導入し、エチレン性不飽和単量体と共重合させる事で、アクリル部分をグラフトさせた水性インキ用アクリル・ウレタン複合樹脂が開示されている。しかしながら、この方法では、ウレタン樹脂部分が3次元的に高分子量化してしまう。したがって、分子鎖の運動性が低下し、ウレタン部分とアクリル部分の相溶も著しく低下するため、低温乾燥条件では、樹脂間で十分に融着できず、優れた塗膜耐性を発現する事はできない。 Patent Document 2 discloses an acrylic / urethane composite resin for water-based ink in which an acrylic moiety is grafted by introducing an ethylenically unsaturated group into a urethane skeleton and copolymerizing with an ethylenically unsaturated monomer. . However, in this method, the urethane resin portion has a three-dimensional high molecular weight. Therefore, the mobility of the molecular chain is reduced, and the compatibility between the urethane part and the acrylic part is also significantly reduced. Under low temperature drying conditions, sufficient fusion cannot be achieved between the resins, and excellent film resistance can be expressed. Can not.
特許文献3では、ウレタン樹脂末端にメルカプト基を導入し、連鎖移動反応により、アクリル骨格がグラフトされた水性インキ用アクリル・ウレタン複合樹脂が開示されている。この方法であればウレタン部分の3次元的な高分子量化は避けられ、異種樹脂間の相溶性は良好になる。しかしながら、厳しい条件下での塗膜耐性発現は困難である。 Patent Document 3 discloses an acrylic / urethane composite resin for water-based ink in which a mercapto group is introduced at the end of a urethane resin and an acrylic skeleton is grafted by a chain transfer reaction. With this method, the three-dimensional increase in the molecular weight of the urethane portion can be avoided, and the compatibility between different resins can be improved. However, it is difficult to develop coating film resistance under severe conditions.
塗膜物性として優れたスクラッチ性、耐水摩擦性を発現する水性複合樹脂の樹脂分散体ならびにそれを用いた水性インキ組成物の提供を目的とする。 It is an object of the present invention to provide a resin dispersion of a water-based composite resin that exhibits excellent scratch properties and water friction resistance as coating film properties, and a water-based ink composition using the same.
すなわち本発明は、
アクリル・ウレタン複合樹脂(A)を高分子乳化剤として、水媒体中でエチレン性不飽和単量体(B)を重合してなる水性複合樹脂分散体であって、
アクリル・ウレタン複合樹脂(A)が、
ポリオール(C)とポリイソシアネート(D)とを反応させてなるウレタンプレポリマー(E−1)に、一般式(1)で表される化合物(F)を反応させてなる両末端メルカプト基含有ウレタンウレア樹脂(E−2)を連鎖移動剤として、エチレン性不飽和単量体(G)を重合したものである水性複合樹脂分散体に関する。
一般式(1)
Rはアルキレン基、アリーレン基、およびアルキレンオキサイド基からなる群より選ばれる少なくとも一種の2価の基である。)
That is, the present invention
An aqueous composite resin dispersion obtained by polymerizing an ethylenically unsaturated monomer (B) in an aqueous medium using an acrylic / urethane composite resin (A) as a polymer emulsifier,
Acrylic / urethane composite resin (A)
Both-end mercapto group-containing urethane obtained by reacting the compound (F) represented by the general formula (1) with the urethane prepolymer (E-1) obtained by reacting the polyol (C) and the polyisocyanate (D). The present invention relates to an aqueous composite resin dispersion obtained by polymerizing an ethylenically unsaturated monomer (G) using a urea resin (E-2) as a chain transfer agent.
General formula (1)
R is at least one divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide group. )
また、本発明は、一般式(1)で表される化合物(D)が、アミノアルカンチオールである前記水性複合樹脂分散体に関する。 The present invention also relates to the aqueous composite resin dispersion, wherein the compound (D) represented by the general formula (1) is an aminoalkanethiol.
また、本発明は、エチレン性不飽和単量体(G)の配合量が、両末端メルカプト基含有ウレタンウレア樹脂(E-2)100重量部に対して30〜180重量部の範囲である前記水性複合樹脂分散体に関する。 Further, in the present invention, the blending amount of the ethylenically unsaturated monomer (G) is in the range of 30 to 180 parts by weight with respect to 100 parts by weight of both terminal mercapto group-containing urethane urea resins (E-2). The present invention relates to an aqueous composite resin dispersion.
また、本発明は、エチレン性不飽和単量体(B)の配合量が、アクリル・ウレタン複合樹脂(A)100重量部に対して10〜120重量部の範囲である前記水性複合樹脂分散体に関する。 The present invention also provides the aqueous composite resin dispersion, wherein the blending amount of the ethylenically unsaturated monomer (B) is in the range of 10 to 120 parts by weight with respect to 100 parts by weight of the acrylic / urethane composite resin (A). About.
また、本発明は、前記水性複合樹脂の酸価が、15〜150mgKOH/gの範囲である前記水性複合樹脂分散体に関する。 The present invention also relates to the aqueous composite resin dispersion, wherein the acid value of the aqueous composite resin is in the range of 15 to 150 mgKOH / g.
また、本発明は、前記水性複合樹脂分散体と、顔料と、親水性溶剤とを含有する水性インキ組成物に関する。 The present invention also relates to an aqueous ink composition containing the aqueous composite resin dispersion, a pigment, and a hydrophilic solvent.
また、本発明は、基材上に、前記水性インキ組成物から形成された印刷層を有する印刷物に関する。 Moreover, this invention relates to the printed matter which has a printing layer formed from the said water-based ink composition on the base material.
また、本発明は、ポリオール(C)とポリイソシアネート(D)とを反応させてなるウレタンプレポリマー(E−1)に、一般式(1)で表される化合物(F)を反応させてなる両末端メルカプト基含有ウレタンウレア樹脂(E−2)を連鎖移動剤として、エチレン性不飽和単量体(G)を重合し、
得られたアクリル・ウレタン複合樹脂(A)を高分子乳化剤として、水媒体中でエチレン性不飽和単量体(B)を重合する、水性複合樹脂分散体の製造方法に関する。
一般式(1)
Rはアルキレン基、アリーレン基、およびアルキレンオキサイド基からなる群より選ばれる少なくとも一種の2価の基である。)
Moreover, this invention makes the compound (F) represented by General formula (1) react with the urethane prepolymer (E-1) formed by making a polyol (C) and polyisocyanate (D) react. The ethylenically unsaturated monomer (G) is polymerized using the both-end mercapto group-containing urethane urea resin (E-2) as a chain transfer agent,
The present invention relates to a method for producing an aqueous composite resin dispersion in which an ethylenically unsaturated monomer (B) is polymerized in an aqueous medium using the obtained acrylic / urethane composite resin (A) as a polymer emulsifier.
General formula (1)
R is at least one divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide group. )
本発明の水性複合樹脂は、非極性フィルム基材に対して、優れた基材密着性、耐水摩擦性、耐スクラッチ性を発現する。 The aqueous composite resin of the present invention exhibits excellent substrate adhesion, water friction resistance, and scratch resistance with respect to a nonpolar film substrate.
まず、本発明で高分子乳化剤として使用するアクリル・ウレタン複合樹脂(A)について説明する。アクリル・ウレタン複合樹脂(A)は、ポリオール(C)とポリイソシアネート(D)とを反応させてなるウレタンプレポリマー(E-1)に、一般式(1)で表される化合物(F)を反応させて、両末端メルカプト基含有ウレタンウレア樹脂(E-2)を合成し、さらにそれを連鎖移動剤として、エチレン性不飽和単量体(G)を重合する事で得る事ができる。
具体的に本発明のアクリル・ウレタン複合樹脂(A)の製造方法について説明する。始めに、反応槽にポリオール(C)とポリイソシアネート(D)を仕込み、触媒を加えて反応させ、両末端がイソシアネート基のウレタンプレポリマー(E-1)を合成する。続いて、そのウレタンプレポリマーに一般式(1)で示される化合物(F)を添加して反応させる。これにより、両末端にメルカプト基が導入されたウレタンウレア樹脂(E-2)が合成できる。さらにエチレン性不飽和単量体(G)と溶媒を添加し、窒素雰囲気下でラジカル開始剤を添加する事で、連鎖移動反応が生じ、ウレタンウレア樹脂(E-2)の両末端からアクリル樹脂骨格がグラフトされる。これによりアクリル・ウレタン複合樹脂(A)が合成できる。
First, the acrylic / urethane composite resin (A) used as a polymer emulsifier in the present invention will be described. Acrylic / urethane composite resin (A) is obtained by adding compound (F) represented by general formula (1) to urethane prepolymer (E-1) obtained by reacting polyol (C) and polyisocyanate (D). It can be obtained by reacting to synthesize a urethane urea resin containing both terminal mercapto groups (E-2) and further polymerizing the ethylenically unsaturated monomer (G) using it as a chain transfer agent.
The method for producing the acrylic / urethane composite resin (A) of the present invention will be specifically described. First, a polyol (C) and a polyisocyanate (D) are charged into a reaction vessel, and a catalyst is added to react to synthesize a urethane prepolymer (E-1) having isocyanate groups at both ends. Subsequently, the urethane prepolymer is reacted with the compound (F) represented by the general formula (1). As a result, a urethane urea resin (E-2) having mercapto groups introduced at both ends can be synthesized. Furthermore, by adding an ethylenically unsaturated monomer (G) and a solvent and adding a radical initiator in a nitrogen atmosphere, a chain transfer reaction occurs, and an acrylic resin is formed from both ends of the urethane urea resin (E-2). The skeleton is grafted. Thereby, the acrylic / urethane composite resin (A) can be synthesized.
<ポリオール(C)>
ウレタンプレポリマー(E-1)に使用するポリオール(C)には、代表的なものとして、ポリエーテルポリオール(c−1)、ポリエステルポリオール(c−2)、ポリカーボネートポリオール(c−3)、ポリオレフィン系ポリオール(c−4)、ひまし油ポリオール等が挙げられる。これらのポリオールは、1種だけを用いてもよいし、複数種を併用してもよい。
<Polyol (C)>
Representative examples of the polyol (C) used in the urethane prepolymer (E-1) include polyether polyol (c-1), polyester polyol (c-2), polycarbonate polyol (c-3), and polyolefin. Based polyol (c-4), castor oil polyol, and the like. These polyols may use only 1 type and may use multiple types together.
ポリエーテルポリオール(c−1)としては、例えば、酸化メチレン、酸化エチレン、酸化プロピレン、テトラヒドロフランなどの重合体または共重合体、具体的には、ポリエチレングリコール、ポリプロピレングリコール、ポリ(エチレン/プロピレン)グリコール、ポリテトラメチレングリコール等が挙げられる。また、ヘキサンジオール、メチルヘキサンジオール、ヘプタンジオール、オクタンジオールあるいはこれらの混合物の縮合によるポリエーテルポリオール類等が挙げられる。 Examples of the polyether polyol (c-1) include polymers or copolymers such as methylene oxide, ethylene oxide, propylene oxide, and tetrahydrofuran, specifically, polyethylene glycol, polypropylene glycol, poly (ethylene / propylene) glycol. And polytetramethylene glycol. Moreover, the polyether polyols by condensation of hexanediol, methylhexanediol, heptanediol, octanediol, or a mixture thereof can be used.
ポリエステルポリオール(c−2)としては、例えば、ポリオール成分と二塩基酸成分とが縮合反応したポリエステルポリオールがある。ポリオールのうちジオールとしては、エチレングリコール、プロピレングリコール、ジプロピレングリコール、ジエチレングリコール、トリエチレングリコール、ブチレングリコール、1,6−ヘキサンジオール、3−メチル−1,5−ペンタンジオール、3,3’−ジメチロールヘプタン、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、1,3−ブタンジオール、1,4−ブタンジオール、ネオペンチルグリコール、オクタンジオール、ブチルエチルペンタンジオール、2−エチル−1,3−ヘキサンジオール、シクロヘキサンジオール、ビスフェノールA等が挙げられ、3個以上の水酸基を有するポリオールとしては、グリセリン、トリメチロールプロパン、ペンタエリスリトール等が挙げられ、二塩基酸成分としてテレフタル酸、アジピン酸、アゼライン酸、セバチン酸、ダイマー酸、水添ダイマー酸、無水フタル酸、イソフタル酸、トリメリット酸等の脂肪族あるいは芳香族二塩基酸、およびそれらの無水物が挙げられる。また、ε−カプロラクトン、ポリ(β−メチル−γ−バレロラクトン)、ポリバレロラクトン等のラクトン類等の環状エステル化合物の開環重合により得られるポリエステルポリオールが挙げられる。 Examples of the polyester polyol (c-2) include a polyester polyol obtained by condensation reaction of a polyol component and a dibasic acid component. Among the polyols, diols include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 3,3′-diene. Methylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, Examples of the polyol having three or more hydroxyl groups include glycerin, trimethylolpropane, pentaerythritol, and the like as dibasic acid components. Terephthalic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, hydrogenated dimer acid, phthalic acid anhydride, isophthalic acid, aliphatic or aromatic dibasic acids such as trimellitic acid, and anhydrides thereof. Moreover, the polyester polyol obtained by ring-opening polymerization of cyclic ester compounds, such as lactones, such as (epsilon) -caprolactone, poly ((beta) -methyl-gamma-valerolactone), and polyvalerolactone, is mentioned.
ポリカーボネートポリオール(c−3)としては、例えば、ポリオールとジアルキルカーボネート、アルキレンカーボネート、ジアリールカーボネートなどのカーボネート化合物との反応により得られるものを挙げることができる。ポリカーボネートポリオールを構成するポリオールとしては、ポリエステルポリオールの構成成分として先に例示したポリオールを用いることができる。また、ジアルキルカーボネートとしてはジメチルカーボネート、ジエチルカーボネートなどを、アルキレンカーボネートとしてはエチレンカーボネートなどを、ジアリールカーボネートとしてはジフェニルカーボネートなどを挙げることができる。 Examples of the polycarbonate polyol (c-3) include those obtained by a reaction between a polyol and a carbonate compound such as dialkyl carbonate, alkylene carbonate, or diaryl carbonate. As a polyol which comprises a polycarbonate polyol, the polyol illustrated previously as a structural component of a polyester polyol can be used. Examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate, examples of the alkylene carbonate include ethylene carbonate, and examples of the diaryl carbonate include diphenyl carbonate.
ポリオレフィン系ポリオール(c−4)としては、水酸基含有ポリブタジエン、水添した水酸基含有ポリブタジエン、水酸基含有ポリイソプレン、水添した水酸基含有ポリイソプレン、水酸基含有塩素化ポリプロピレン、水酸基含有塩素化ポリエチレン等が挙げられる。 Examples of the polyolefin-based polyol (c-4) include hydroxyl group-containing polybutadiene, hydrogenated hydroxyl group-containing polybutadiene, hydroxyl group-containing polyisoprene, hydrogenated hydroxyl group-containing polyisoprene, hydroxyl group-containing chlorinated polypropylene, and hydroxyl group-containing chlorinated polyethylene. .
ひまし油ポリオールは植物由来のひまし油を原料としたバイオマスポリオールである。 Castor oil polyol is a biomass polyol made from castor oil derived from plants.
上記以外にも、ウレタン結合濃度の調節や各種官能基導入の目的で低分子ジオールを併用する事ができる。低分子ジオールとしては分子量500以下のジオールが好ましく、例えば、
エチレングリコール、1,2−プロパンジオール、1,3−プロパンジオール、1,3−ブタンジオール、1,4−ブタンジオール、ネオペンチルグリコール、ペンタンジオール、ヘキサンジオール、オクタンジオール、2−ブチル−2−エチル−1,3−プロパンジオール、1,4−ブチレンジオール、ジプロピレングリコール、グリセリン、トリメチロールプロパン、トリメチロールエタン、1,2,6−ブタントリオール、ペンタエリスリトール、ソルビトール、N,N-ビス(2−ヒドロキシプロピル)アニリン、ジメチロール酢酸、ジメチロールプロピオン酸、ジメチロールブタン酸、2,2−ジメチロール酪酸、2,2−ジメチロールペンタン酸等のジメチロールアルカン酸や、ジヒドロキシコハク酸、ジヒドロキシプロピオン酸、ジヒドロキシ安息香酸等が挙げられる。
In addition to the above, a low molecular diol can be used in combination for the purpose of adjusting the urethane bond concentration and introducing various functional groups. As the low molecular diol, a diol having a molecular weight of 500 or less is preferable.
Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, hexanediol, octanediol, 2-butyl-2- Ethyl-1,3-propanediol, 1,4-butylenediol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-butanetriol, pentaerythritol, sorbitol, N, N-bis ( 2-hydroxypropyl) aniline, dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, dimethylolalkanoic acid such as 2,2-dimethylolpentanoic acid, dihydroxysuccinic acid, dihydroxypropionic acid , Dihydroxy And benzoic acid.
<ポリイソシアネート(D)>
ポリオール(C)と反応させるポリイソシアネート(D)としては、芳香族、脂肪族、脂環式のポリイソシアネートが挙げられる。これらは、1種だけを用いてもよいし、あるいは、複数種を併用してもよい。
<Polyisocyanate (D)>
Examples of the polyisocyanate (D) to be reacted with the polyol (C) include aromatic, aliphatic and alicyclic polyisocyanates. These may use only 1 type or may use multiple types together.
芳香族ポリイソシアネートとしては、例えば、2,4−トリレンジイソシアネート、2,6−トリレンジイソシアネート、m−フェニレ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’−ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、リジンジイソシアネート、3,3’−ジメチル−4,4’−ビフェニレンジイソシアネート、3,3’−ジメトキシ−4,4’−ビフェニレンジイソシアネート、3,3’−ジクロロ−4,4’−ビフェニ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、1,5−テトラヒドロナフタレンジイソシアネート等が挙げられる。 Examples of the aromatic polyisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, lysine diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate, 3,3′-dichloro-4,4′-biphenylene diisocyanate, 1,5-naphthalene Examples include diisocyanate and 1,5-tetrahydronaphthalene diisocyanate.
脂肪族ポリイソシアネートとしては、例えば、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート等が挙げられる。 Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.
脂環式ポリイソシアネートとしては、例えば、イソホロンジイソシアネート、1,4−シクロヘキシレ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等が挙げられる。 Examples of the alicyclic polyisocyanate include isophorone diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and the like.
ウレタンプレポリマー(E−1)を得る反応に際して、触媒を用いることもできる。使用できる触媒としては、公知の金属系触媒、アミン系触媒が使用できる。金属系触媒としては、ジブチル錫ジラウレート、オクトエ酸錫、ジブチル錫ジ(2−エチルヘキソエート)、 2−エチルヘキソエート鉛、チタン酸2−エチルヘキシル、チタンエチルアセテート、2−エチルヘキソエート鉄、2−エチルヘキソエートコバルト、ナフテン酸亜鉛、ナフテン酸コバルト、テトラ−n−ブチル錫等が挙げられる。アミン系触媒としてはテトラメチルブタンジアミン等の3級アミン等が挙げられる。これらの触媒はポリマーポリオールに対して0.001〜1モル%の範囲で使用される。 In the reaction for obtaining the urethane prepolymer (E-1), a catalyst may be used. As the catalyst that can be used, a known metal catalyst or amine catalyst can be used. Examples of metal catalysts include dibutyltin dilaurate, tin octoate, dibutyltin di (2-ethylhexoate), lead 2-ethylhexoate, 2-ethylhexyl titanate, titanium ethyl acetate, 2-ethylhexoate Examples thereof include iron, 2-ethylhexoate cobalt, zinc naphthenate, cobalt naphthenate, and tetra-n-butyltin. Examples of amine-based catalysts include tertiary amines such as tetramethylbutanediamine. These catalysts are used in the range of 0.001 to 1 mol% with respect to the polymer polyol.
ウレタンプレポリマー(E−1)を得る反応は、50〜150℃で2〜10時間行うのが好ましい。反応の終点は、滴定によるNCO%測定により判断することができる。 The reaction for obtaining the urethane prepolymer (E-1) is preferably carried out at 50 to 150 ° C. for 2 to 10 hours. The end point of the reaction can be judged by measuring NCO% by titration.
ウレタンプレポリマー(E−1)を得る際に使用できる溶媒としては、イソシアネート基と反応しないものであれば任意のものを使用する事ができるが、後の脱溶剤の工程を考慮し、水と共沸して除去しやすい溶剤を使用する事が好ましい。また、無溶媒で反応をおこない、後で溶媒希釈する事も可能である。好ましい溶剤としては、アセトン、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系溶剤;
酢酸エチル、酢酸プロピル、酢酸ブチル等のエステル系溶剤;
エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のグリコールエステル系溶剤;等が挙げられる。
As a solvent that can be used when obtaining the urethane prepolymer (E-1), any solvent can be used as long as it does not react with the isocyanate group. It is preferable to use a solvent that is azeotropically and easily removed. It is also possible to carry out the reaction without solvent and dilute the solvent later. Preferred solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone;
Ester solvents such as ethyl acetate, propyl acetate, butyl acetate;
And glycol ester solvents such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate.
<一般式(1)で表される化合物(F)>
上述のウレタンプレポリマー(E-1)に一般式(1)で表されるメルカプト基含有化合物(F)を反応させる事で両末端にメルカプト基を有するウレタンウレア樹脂(E-2)を得る。
一般式(1)
(一般式(1)中、Xは−OH、−NH2、−NHR1、および−SHからなる群より選ばれる少なくとも一種であり、R1はアルキル基である。
Rはアルキレン基、アリーレン基、およびアルキレンオキサイド基からなる群より選ばれる少なくとも一種の2価の基である。)
<Compound (F) Represented by General Formula (1)>
By reacting the above-mentioned urethane prepolymer (E-1) with the mercapto group-containing compound (F) represented by the general formula (1), a urethane urea resin (E-2) having mercapto groups at both ends is obtained.
General formula (1)
(In the general formula (1), X is -OH, -NH 2, -NHR 1, and at least one selected from the group consisting of -SH, R 1 is an alkyl group.
R is at least one divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide group. )
Rのうちアルキレン基としては、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、へキシレン基、ヘプチレン基、オクチレン基、ドデシレン基等の炭素数1〜12のアルキレン基が挙げられ、炭素数1〜6のアルキレン基が好ましい。
アリーレン基としては、フェニレン基等が挙げられ、アルキレンオキサイド基としては、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド等が挙げられる。Rは、アルキレン基またはフェニレン基が好ましい。
Examples of the alkylene group in R include an alkylene group having 1 to 12 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, and a dodecylene group. The alkylene group of number 1-6 is preferable.
Examples of the arylene group include a phenylene group, and examples of the alkylene oxide group include ethylene oxide, propylene oxide, and butylene oxide. R is preferably an alkylene group or a phenylene group.
一般式(1)で表される化合物(F)としては例えば、
2−ヒドロキシエタンチオール、3−ヒドロキシプロピル−1−チオール、1−ヒドロキシプロピル−2−チオール、4−ヒドロキシ−1−ブタンチオール等のヒドロキシアルカンチオール類;
1,2−エタンジチオール、1,3−プロパンジチオール、1,4−ブタンジチオール、1,5−ペンタンジチオール、1,6−ヘキサンジチオール等のジチオール類、
2−アミノエタンチオール、3−アミノプロピル−1−チオール、1−アミノプロピル−2−チオール、4−アミノ−1−ブタンチオール等のアミノアルカンチオール類;
2−アミノチオフェノール、3−アミノチオフェノール、4−アミノチオフェノール等のアミノベンゼンチオール類;
が挙げられる。
Examples of the compound (F) represented by the general formula (1) include
Hydroxyalkanethiols such as 2-hydroxyethanethiol, 3-hydroxypropyl-1-thiol, 1-hydroxypropyl-2-thiol, 4-hydroxy-1-butanethiol;
Dithiols such as 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol,
Aminoalkanethiols such as 2-aminoethanethiol, 3-aminopropyl-1-thiol, 1-aminopropyl-2-thiol, 4-amino-1-butanethiol;
Aminobenzenethiols such as 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol;
Is mentioned.
一般式(1)の化合物(F)の中でも、反応性に優れ、毒性が低く、ウレア結合を形成する点で、Xが−NH2または−NHR1であり、Rがアルキレン基であるアミノアルカンチオール類を使用する事が好ましい。ウレア結合を導入する事で、樹脂の凝集力が上がり、樹脂の塗膜耐性、基材への接着強度が向上する。さらにアミノ基のモル数に対して、イソシアネート基のモル数が過剰になるように仕込む事で、残存したイソシアネート基がメルカプト基と反応して鎖延長され、ウレタンプレポリマー(E-1)が高分子量化される。この時、両末端の他に、ウレタン樹脂内部にもウレア結合が導入されるため、さらに凝集力が向上し、塗膜耐性、接着強度が向上する。 Among the compounds (F) of the general formula (1), aminoalkane in which X is —NH 2 or —NHR 1 and R is an alkylene group in that it has excellent reactivity, low toxicity, and forms a urea bond. It is preferable to use thiols. By introducing a urea bond, the cohesive strength of the resin is increased, and the coating film resistance of the resin and the adhesive strength to the substrate are improved. Furthermore, by charging the number of moles of isocyanate groups with respect to the number of moles of amino groups, the remaining isocyanate groups react with mercapto groups to extend the chain, and the urethane prepolymer (E-1) has a high content. Molecular weight. At this time, since the urea bond is introduced inside the urethane resin in addition to both ends, the cohesive force is further improved, and the coating film resistance and the adhesive strength are improved.
一般式(1)で表される化合物(F)としてアミノアルカンチオールを用いると、ウレタンプレポリマー(E-1)中のイソシアネート基に対してアミノ基が優先的に反応してウレア結合を形成する。さらに一般式(1)で表される化合物(F)のモル数に対して、イソシアネート基のモル数が過剰になるように仕込むことで、残存したイソシアネート基がメルカプト基と反応して鎖延長され、ウレタンプレポリマー(F-1)が高分子量化される。この時、ウレタンプレポリマー(F-1)の両末端の他に、その骨格内部にもウレア結合が導入されるため、ウレタン樹脂の凝集力が向上し、接着強度が向上する。また、未反応の化合物(F)も低減されるため、樹脂塗膜の臭気も大幅に改善される。 When aminoalkanethiol is used as the compound (F) represented by the general formula (1), the amino group preferentially reacts with the isocyanate group in the urethane prepolymer (E-1) to form a urea bond. . Furthermore, the remaining isocyanate group reacts with the mercapto group to extend the chain by charging so that the number of moles of the isocyanate group is excessive with respect to the number of moles of the compound (F) represented by the general formula (1). The urethane prepolymer (F-1) is increased in molecular weight. At this time, in addition to the both ends of the urethane prepolymer (F-1), urea bonds are introduced into the skeleton, so that the cohesive force of the urethane resin is improved and the adhesive strength is improved. Moreover, since the unreacted compound (F) is also reduced, the odor of the resin coating film is greatly improved.
上記の理由から、両末端メルカプト基含有ウレタンウレア樹脂(E-2)を製造する際、ウレタンプレポリマー(E-1)のイソシアネート基が、一般式(1)で表される化合物(F)に対して、過剰になるように仕込む事が好ましい。さらに一般式(1)で表される化合物(F)は、ウレタンプレポリマー(E-1)のイソシアネート基1モルに対して、0.60〜0.90モルになるように反応させる事が好ましい。仕込み量が0.6モル以上であると、ウレタン骨格にアクリル骨格が組み込まれやすくなり、目的の複合樹脂を得やすいため好ましく、樹脂溶液の保存安定性、基材密着性に優れる。一方で、0.90モル以下であると、樹脂に組み込まれない未反応の化合物(E)の量が少なくなるため、樹脂塗膜の臭気の点で優れる。 For the above reasons, when the urethane urea resin (E-2) containing both terminal mercapto groups is produced, the isocyanate group of the urethane prepolymer (E-1) is converted into the compound (F) represented by the general formula (1). On the other hand, it is preferable to prepare to be excessive. Furthermore, the compound (F) represented by the general formula (1) is preferably reacted so as to be 0.60 to 0.90 mol with respect to 1 mol of the isocyanate group of the urethane prepolymer (E-1). . When the charged amount is 0.6 mol or more, the acrylic skeleton is easily incorporated into the urethane skeleton, and the target composite resin is easily obtained, which is excellent in the storage stability of the resin solution and the substrate adhesion. On the other hand, when it is 0.90 mol or less, the amount of the unreacted compound (E) that is not incorporated into the resin is reduced, and this is excellent in terms of the odor of the resin coating film.
両末端メルカプト基含有ウレタンウレア樹脂(E-2)を得る際に使用できる溶媒としては、原料を溶解可能で、イソシアネート基と反応しない溶媒であれば任意のものを使用する事ができるが、後の脱溶剤工程を考慮し、水と共沸して除去しやすい溶剤を使用する事が好ましい。好ましい溶剤としては、アセトン、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系溶剤;酢酸エチル、酢酸プロピル、酢酸ブチル等のエステル系溶剤;エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のグリコールエステル系溶剤;等が挙げられ、ケトン系溶剤が好ましい。 As the solvent that can be used for obtaining the both-end mercapto group-containing urethane urea resin (E-2), any solvent that can dissolve the raw material and does not react with the isocyanate group can be used. It is preferable to use a solvent that is easy to remove by azeotropy with water. Preferred solvents include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate, propyl acetate, and butyl acetate; glycol ester solvents such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; Etc., and ketone solvents are preferred.
<エチレン性不飽和単量体(G)>
前記両末端メルカプト基含有ウレタンウレア樹脂(E-2)を連鎖移動剤として、エチレン性不飽和単量体(G)を重合する事により、アクリル・ウレタン複合樹脂(A)を得られる。
<Ethylenically unsaturated monomer (G)>
Acrylic / urethane composite resin (A) can be obtained by polymerizing the ethylenically unsaturated monomer (G) using the above-described mercapto group-containing urethane urea resin (E-2) as a chain transfer agent.
アクリル骨格部分は親水基として機能するため、エチレン性不飽和単量体(G)は親水性基含有エチレン性不飽和単量体(g−1)を含むことが好ましい。使用するエチレン性不飽和単量体の官能基により、アニオン性、カチオン性、非イオン性の親水基を適宜導入する事が可能である。アニオン性親水基としては、カルボキシル基、スルホン酸基、リン酸基等が挙げられ、カチオン性親水基としては、アミノ基等が挙げられ、非イオン性の親水基としては、ポリエチレンオキサイド基、アミド基、ヒドロキシル基等が挙げられる。 Since the acrylic skeleton part functions as a hydrophilic group, the ethylenically unsaturated monomer (G) preferably contains a hydrophilic group-containing ethylenically unsaturated monomer (g-1). Depending on the functional group of the ethylenically unsaturated monomer to be used, an anionic, cationic or nonionic hydrophilic group can be appropriately introduced. Examples of the anionic hydrophilic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Examples of the cationic hydrophilic group include an amino group. Examples of the nonionic hydrophilic group include a polyethylene oxide group and an amide group. Group, hydroxyl group and the like.
親水性基含有エチレン性不飽和単量体(g−1)としては、例えば、
アニオン性の親水基を有するものとして、
マレイン酸、無水マレイン酸、フマル酸、イタコン酸、シトラコン酸、または、これらのアルキルもしくはアルケニルモノエステル、ヘキサヒドロフタル酸β−(メタ)アクリロキシエチルモノエステル、コハク酸β−(メタ)アクリロキシエチルモノエステル、アクリル酸、メタクリル酸、クロトン酸、けい皮酸等のカルボキシル基含有エチレン性不飽和単量体;スチレンスルホン酸、スチレンスルホン酸ナトリウム、スチレンスルホン酸アンモニウム、スチレンスルホン酸リチウム、2−アクリルアミド2−メチルプロパンスルホン酸、2−アクリルアミド2−メチルプロパンスルホン酸ナトリウム、メタリルスルホン酸、メタリルスルホン酸ナトリウム、アリルスルホン酸、アリルスルホン酸ナトリウム、アリルスルホン酸アンモニウム、ビニルスルホン酸、アリルオキシベンゼンスルホン酸、アリルオキシベンゼンスルホン酸ナトリウム、アリルオキシベンゼンスルホン酸アンモニウム等のスルホン酸基含有エチレン性不飽和単量体;
2−メタクリロイルオキシエチルアシッドホスフェート、2−アクリロイルオキシエチルアシッドホスフェート、ジフェニル−2−アクリロイルオキシエチルホスフェート、ジフェニル−2−メタクリロイルオキシエチルホスフェート、ジブチル−2−アクリロイルオキシシエチルホスフェート等のリン酸基本含有エチレン性不飽和単量体;
カチオン性の親水基を有するものとして、
ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート、メチルエチルアミノエチル(メタ)アクリレート、ジメチルアミノスチレン、ジエチルアミノスチレン等のアミノ基含有エチレン性不飽和単量体;
非イオン性の親水基を有するものとして、
ポリエチレングリコールモノ(メタ)アクリレート(日本油脂社製、ブレンマーPE−90、200、350、350G、AE−90、200、400等)ポリエチレングリコール・ポリプロピレングリコールモノ(メタ)アクリレート(日本油脂社製、ブレンマー50PEP−300、70PEP−350等)、メトキシポリエチレングリコールモノ(メタ)アクリレート(日本油脂社製、ブレンマーPME−400、550、1000、4000等)等のポリエチレンオキサイド基含有エチレン性不飽和単量体;
(メタ)アクリルアミド、N−メトキシメチル−(メタ)アクリルアミド、N−エトキシメチル−(メタ)アクリルアミド、N−プロポキシメチル−(メタ)アクリルアミド、N−ブトキシメチル−(メタ)アクリルアミド、N−ペントキシメチル−(メタ)アクリルアミド、N,N−ジ(メトキシメチル)アクリルアミド、N−エトキシメチル−N−メトキシメチルメタアクリルアミド、N,N−ジ(エトキシメチル)アクリルアミド、N−エトキシメチル−N−プロポキシメチルメタアクリルアミド、N,N−ジ(プロポキシメチル)アクリルアミド、N−ブトキシメチル−N−(プロポキシメチル)メタアクリルアミド、N,N−ジ(ブトキシメチル)アクリルアミド、N−ブトキシメチル−N−(メトキシメチル)メタアクリルアミド、N,N−ジ(ペントキシメチル)アクリルアミド、N−メトキシメチル−N−(ペントキシメチル)メタアクリルアミド、N,N−ジメチルアミノプロピルアクリルアミド、N,N−ジエチルアミノプロピルアクリルアミド、N,N−ジメチルアクリルアミド、N,N−ジエチルアクリルアミド、ジアセトン(メタ)アクリルアミド等のアミド基含有エチレン性不飽和単量体;
2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、4−ヒドロキシブチル(メタ)アクリレート、グリセロールモノ(メタ)アクリレート、アリルアルコール等のヒドロキシル基含有エチレン性不飽和単量体;
等が挙げられるが、特にこれらに限定されるものではない。これらは1種類または2種以上を併用して用いることができる。
As the hydrophilic group-containing ethylenically unsaturated monomer (g-1), for example,
As having an anionic hydrophilic group,
Maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, hexahydrophthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxy Carboxyl group-containing ethylenically unsaturated monomers such as ethyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid; styrene sulfonic acid, sodium styrene sulfonate, ammonium styrene sulfonate, lithium styrene sulfonate, 2- Acrylamide 2-methylpropanesulfonic acid, sodium 2-acrylamido-2-methylpropanesulfonate, methallylsulfonic acid, sodium methallylsulfonate, allyl sulfonic acid, sodium allyl sulfonate, ammonium allyl sulfonate Sulfonic acid group-containing ethylenically unsaturated monomers such as vinyl sulfonic acid, allyloxybenzene sulfonic acid, sodium allyloxybenzene sulfonate, ammonium allyloxybenzene sulfonate;
Ethylene phosphate-containing ethylene such as 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxyethyl phosphate Unsaturated monomers;
As having a cationic hydrophilic group,
Amino group-containing ethylenically unsaturated monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylaminostyrene;
As having a nonionic hydrophilic group,
Polyethylene glycol mono (meth) acrylate (Nippon Yushi Co., Ltd., Bremer PE-90, 200, 350, 350G, AE-90, 200, 400, etc.) Polyethylene glycol / polypropylene glycol mono (meth) acrylate (Nippon Yushi Co., Ltd., Blemmer 50PEP-300, 70PEP-350, etc.), polyethylene oxide group-containing ethylenically unsaturated monomers such as methoxypolyethylene glycol mono (meth) acrylate (manufactured by NOF Corporation, BLEMMER PME-400, 550, 1000, 4000, etc.);
(Meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl -(Meth) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmeta Acrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) meta Acrylic net N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) methacrylamide, N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide, N, N-dimethyl Amide group-containing ethylenically unsaturated monomers such as acrylamide, N, N-diethylacrylamide, diacetone (meth) acrylamide;
Hydroxyl group-containing ethylenically unsaturated monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, allyl alcohol;
However, it is not particularly limited to these. These can be used alone or in combination of two or more.
親水性基含有エチレン性不飽和単量体(g−1)の中でも、乾燥後の樹脂塗膜の耐水性を考慮すると、カルボキシル基含有エチレン性不飽和単量体を使用する事が好ましい。 Among the hydrophilic group-containing ethylenically unsaturated monomers (g-1), it is preferable to use a carboxyl group-containing ethylenically unsaturated monomer in consideration of the water resistance of the resin coating film after drying.
エチレン性不飽和単量体(g)において、親水性基含有エチレン性不飽和単量体(g−1)と共重合可能なその他のエチレン性不飽和単量体(g−2)としては、例えば、
スチレン、α−メチルスチレン、o−メチルスチレン、p−メチルスチレン、m−メチルスチレン、ビニルナフタレン、ベンジルアクリレート、ベンジルメタクリレート、フェノキシエチルアクリレート、フェノキシエチルメタクリレート、フェノキシジエチレングリコールアクリレート、フェノキシジエチレングリコールメタクリレート、フェノキシテトラエチレングリコールアクリレート、フェノキシテトラエチレングリコールメタクリレート、フェノキシヘキサエチレングリコールアクリレート、フェノキシヘキサエチレングリコールメタクリレート、フェニルアクリレート、フェニルメタクリレート等の芳香族含有エチレン性不飽和単量体;
メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、n−ブチル(メタ)アクリレート、tーブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、ヘプチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、ノニル(メタ)アクリレート、デシル(メタ)アクリレート、ウンデシル(メタ)アクリレート、ドデシル(メタ)アクリレート、トリデシル(メタ)アクリレート、テトラデシル(メタ)アクリレート等の直鎖または分岐アルキル基含有エチレン性不飽和単量体;
シクロヘキシル(メタ)アクリレート、イソボニル(メタ)アクリレート等の脂環式アルキル基含有エチレン性不飽和単量体;
トリフルオロエチル(メタ)アクリレート、ヘプタデカフルオロデシル(メタ)アクリレート等のフッ素化アルキル基含有エチレン性不飽和単量体;
2−アセトアセトキシエチル(メタ)アクリレート等のケト基含有エチレン性不飽和単量体;
アリル(メタ)アクリレート、ビニル(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、ポリエチレングリコール(メタ)アクリレート、1,4−ブタンジオールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、1,9−ノナンジオールジ(メタ)アクリレート、1,10−デカンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、グリセリンジメタクリレート、ジメチロールトリシクロデカンジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリストールテトラ(メタ)アクリレート、ジビニルベンゼン、アジピン酸ジビニル、イソフタル酸ジアリル、フタル酸ジアリル、マレイン酸ジアリル等の2個以上のエチレン性不飽和基を有するエチレン性不飽和単量体;
グリシジル(メタ)アクリレート、3,4−エポキシシクロヘキシル(メタ)アクリレート等のエポキシ基含有エチレン性不飽和単量体;γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルトリブトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルメチルジエトキシシラン、γ−アクリロキシプロピルトリメトキシシラン、γ−アクリロキシプロピルトリエトキシシラン、γ−アクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシメチルトリメトキシシラン、γ−アクリロキシメチルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリブトキシシラン、ビニルメチルジメトキシシラン等のアルコキシシリル基含有エチレン性不飽和単量体;等が挙げられるが、特にこれらに限定されるものではない。これらは1種類または2種類以上を併用して用いることができる。
In the ethylenically unsaturated monomer (g), as the other ethylenically unsaturated monomer (g-2) copolymerizable with the hydrophilic group-containing ethylenically unsaturated monomer (g-1), For example,
Styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, m-methyl styrene, vinyl naphthalene, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol acrylate, phenoxydiethylene glycol methacrylate, phenoxytetraethylene Aromatic-containing ethylenically unsaturated monomers such as glycol acrylate, phenoxytetraethylene glycol methacrylate, phenoxyhexaethylene glycol acrylate, phenoxyhexaethylene glycol methacrylate, phenyl acrylate, and phenyl methacrylate;
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate Linear or branched alkyl group-containing ethylenically unsaturated monomers such as
Alicyclic alkyl group-containing ethylenically unsaturated monomers such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate;
Fluorinated alkyl group-containing ethylenically unsaturated monomers such as trifluoroethyl (meth) acrylate and heptadecafluorodecyl (meth) acrylate;
Keto group-containing ethylenically unsaturated monomers such as 2-acetoacetoxyethyl (meth) acrylate;
Allyl (meth) acrylate, vinyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Glycerin dimethacrylate, dimethylol tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( Data) acrylate, divinylbenzene, divinyl adipate, diallyl isophthalate, diallyl phthalate, ethylenically unsaturated monomer having two or more ethylenically unsaturated groups such as diallyl maleate;
Epoxy group-containing ethylenically unsaturated monomers such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate; γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacrylic Roxypropyltributoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxy Silane, γ-methacryloxymethyltrimethoxysilane, γ-acryloxymethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethyl Alkoxysilyl group-containing ethylenically unsaturated monomers such as dimethoxysilane; and others as mentioned, but the invention is not particularly limited thereto. These can be used alone or in combination of two or more.
上述のエチレン性不飽和単量体(G)を重合してなるアクリル樹脂部分のガラス転移温度(Tg)は、−10〜60℃の範囲であることが好ましい。ガラス転移温度が−10℃以上であると、アクリル樹脂部分が硬く耐ブロッキング性に優れる。一方でガラス転移温度が60℃以下であると、低温乾燥下における分子鎖の運動性が阻害されにくいため接着強度に優れる。 The glass transition temperature (Tg) of the acrylic resin portion obtained by polymerizing the above ethylenically unsaturated monomer (G) is preferably in the range of −10 to 60 ° C. When the glass transition temperature is −10 ° C. or higher, the acrylic resin portion is hard and excellent in blocking resistance. On the other hand, when the glass transition temperature is 60 ° C. or less, the mobility of the molecular chain under low temperature drying is difficult to be inhibited, so that the adhesive strength is excellent.
上記のガラス転移温度とは、以下のFOXの式より計算した理論値の事をさす。
<FOX式>
1/Tg=W1/Tg1+W2/Tg2+…+Wi/Tgi+…Wn/Tgn
〔上記FOX式は、n種の単量体からなる重合体を構成する各モノマーのホモポリマーのガラス転移温度をTgi(K)とし、各モノマーの質量分率をWiとしており、(W1+W2+…Wi+…Wn=1)である。〕
The glass transition temperature is a theoretical value calculated from the following FOX equation.
<FOX type>
1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wi / Tgi + ... Wn / Tgn
[In the FOX formula, the glass transition temperature of the homopolymer of each monomer constituting the polymer composed of n types of monomers is Tgi (K), the mass fraction of each monomer is Wi, and (W1 + W2 +... Wi + ... Wn = 1). ]
アクリル・ウレタン複合化の際、両末端メルカプト基含有ウレタンウレア樹脂(E-2)100重量部に対して、エチレン性不飽和単量体(G)の量は30〜180重量部である事が好ましい。上記範囲内であると、樹脂の分散安定性が向上する。また、塗膜硬度が向上し耐水摩擦性、耐ブロッキング性に優れ、また非極性フィルム基材への密着性に優れる。より好ましくは50〜150重量部である。 At the time of the acrylic-urethane composite, the amount of the ethylenically unsaturated monomer (G) is 30 to 180 parts by weight with respect to 100 parts by weight of the both-end mercapto group-containing urethane urea resin (E-2). preferable. Within the above range, the dispersion stability of the resin is improved. In addition, the coating film hardness is improved, water rub resistance and blocking resistance are excellent, and adhesion to a nonpolar film substrate is excellent. More preferably, it is 50-150 weight part.
アクリル・ウレタン複合化反応の際に使用するラジカル開始剤としては、公知の油溶性重合開始剤を使用でき、例えば、ベンゾイルパーオキサイド、tert−ブチルパーオキシベンゾエート、tert−ブチルハイドロパーオキサイド、tert−ブチルパーオキシ(2−エチルヘキサノエート)、tert−ブチルパーオキシ−3,5,5−トリメチルヘキサノエート、ジ−tert−ブチルパーオキサイドなどの有機過酸化物;
2,2’−アゾビスイソブチロニトリル、2,2’−アゾビス−2,4−ジメチルバレロニトリル、2,2’−アゾビス(4−メトキシ−2,4−ジメチルバレロニトリル)、1,1’−アゾビス−シクロヘキサン−1−カルボニトリルなどのアゾビス化合物を挙げることができる。
As the radical initiator used in the acrylic / urethane complexing reaction, a known oil-soluble polymerization initiator can be used. For example, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, tert- Organic peroxides such as butyl peroxy (2-ethylhexanoate), tert-butylperoxy-3,5,5-trimethylhexanoate, di-tert-butyl peroxide;
2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1 Mention may be made of azobis compounds such as' -azobis-cyclohexane-1-carbonitrile.
ラジカル開始剤は、エチレン性不飽和単量体(G)100重量%に対して、0.1〜0.5重量部の範囲で使用する事が好ましい。0.1重量%未満であると、重合反応が十分に進行せず、原料成分が残留し、経時安定性、臭気などを悪化させる恐れがある。一方で、0.5重量部を超えると、両末端メルカプト基含有ウレタンウレア樹脂(E−2)のメルカプト基に連鎖移動せず、単独で生成するアクリル樹脂成分が増加するため、密着性が悪化する場合がある。 The radical initiator is preferably used in the range of 0.1 to 0.5 parts by weight with respect to 100% by weight of the ethylenically unsaturated monomer (G). If it is less than 0.1% by weight, the polymerization reaction does not proceed sufficiently, the raw material components remain, and the stability over time, odor and the like may be deteriorated. On the other hand, when the amount exceeds 0.5 parts by weight, the chain transfer to the mercapto group of the both-end mercapto group-containing urethane urea resin (E-2) does not occur, and the acrylic resin component produced alone increases, resulting in poor adhesion. There is a case.
反応に使用する溶媒としては、原料ならびに生成物を溶解するものであれば、任意のものを使用する事ができるが、後の脱溶剤工程を考慮し、水と共沸して除去しやすい溶剤を使用する事が好ましい。好ましい溶剤としては、アセトン、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系溶剤;酢酸エチル、酢酸プロピル、酢酸ブチル等のエステル系溶剤;エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のグリコールエステル系溶剤;
エタノール、イソプロピルアルコール、n-プロパノール、イソブタノールn-ブタノール等のアルコール系溶剤;
等が挙げられる。
これらの溶媒は単独で使用しても、2種類以上併用しても構わない。
As the solvent used in the reaction, any solvent can be used as long as it dissolves the raw materials and products. However, in consideration of the subsequent solvent removal step, the solvent is azeotropically removed with water and easily removed. It is preferable to use Preferred solvents include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate, propyl acetate, and butyl acetate; glycol ester solvents such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate;
Alcohol solvents such as ethanol, isopropyl alcohol, n-propanol, isobutanol and n-butanol;
Etc.
These solvents may be used alone or in combination of two or more.
次に本発明の複合樹脂を水性化する工程について説明する。
まず、反応が完了した複合樹脂に、イオン交換水ならびに必要であれば塩基性化合物を添加して攪拌する。塩基性化合物は、複合樹脂の親水性基がアニオン性で未中和の場合に、中和剤として使用する。全体が均一になった段階で、脱溶剤処理を開始して有機溶剤を除去する。脱溶剤には必要に応じてアスピレーターや真空ポンプを使用し、減圧下でおこなう事もできる。
Next, the process of making the composite resin of the present invention aqueous will be described.
First, ion-exchanged water and, if necessary, a basic compound are added to the composite resin that has undergone the reaction and stirred. The basic compound is used as a neutralizing agent when the hydrophilic group of the composite resin is anionic and unneutralized. When the whole becomes uniform, the solvent removal treatment is started to remove the organic solvent. Solvent removal can be performed under reduced pressure using an aspirator or a vacuum pump as necessary.
中和剤として使用する塩基性化合物としては、例えば、
アンモニア、トリエチルアミン、トリイソプロピルアミン、トリブチルアミン、トリエタノールアミン、N−メチルジエタノールアミン、N−フェニルジエタノールアミン、モノエタノールアミン、ジメチルエタノールアミン、ジエチルエタノールアミン、モルホリン、N−メチルモルホリン、2−アミノ−2−エチル−1−プロパノール、ピリジン等のアミン類、水酸化ナトリウム、水酸化カリウム等の無機アルカリ類等が挙げられる。
As a basic compound used as a neutralizing agent, for example,
Ammonia, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2- Examples include amines such as ethyl-1-propanol and pyridine, and inorganic alkalis such as sodium hydroxide and potassium hydroxide.
<エチレン性不飽和単量体(B)>
続いて、アクリル・ウレタン複合樹脂(A)を高分子乳化剤として、エチレン性不飽和単量体(B)を重合する工程について説明する。上記で得られたアクリル・ウレタン複合樹脂(A)の水溶液を反応槽に仕込み、昇温する。そこに、窒素雰囲気下でエチレン性不飽和単量体(B)を滴下しながら、ラジカル重合開始剤を添加する。エチレン性不飽和単量体(B)はそのまま反応槽に滴下しても良いし、水性媒体中であらかじめ乳化液にしてから滴下しても構わない。アクリル・ウレタン樹脂(A)は、水性媒体中で保護コロイド(シェル成分)として働き、エチレン性不飽和単量体(B)の重合体からなる粒子核成分(コア成分)を安定化させる。これにより、目的のコアシェル型複合樹脂の水分散体を得る事ができる。
<Ethylenically unsaturated monomer (B)>
Next, a process for polymerizing the ethylenically unsaturated monomer (B) using the acrylic / urethane composite resin (A) as a polymer emulsifier will be described. The aqueous solution of acrylic / urethane composite resin (A) obtained above is charged into a reaction vessel and heated. A radical polymerization initiator is added there, dripping an ethylenically unsaturated monomer (B) in nitrogen atmosphere there. The ethylenically unsaturated monomer (B) may be added dropwise to the reaction vessel as it is, or may be added dropwise after an emulsion is prepared in advance in an aqueous medium. The acrylic urethane resin (A) acts as a protective colloid (shell component) in an aqueous medium, and stabilizes the particle core component (core component) made of a polymer of the ethylenically unsaturated monomer (B). Thereby, the water dispersion of the target core-shell type composite resin can be obtained.
エチレン性不飽和単量体(B)は、エチレン性不飽和単量体(G)で例示したものを使用する事ができ、エチレン性不飽和単量体(G)と同じであっても異なっていても良いが、粒子核として析出させ、保護コロイドで安定化させる点を鑑みると、親水基を含有していないエチレン性不飽和単量体(g−2)を主成分として使用する事が好ましい。 As the ethylenically unsaturated monomer (B), those exemplified for the ethylenically unsaturated monomer (G) can be used. However, in view of the point of precipitation as particle nuclei and stabilization with protective colloid, it is possible to use an ethylenically unsaturated monomer (g-2) containing no hydrophilic group as a main component. preferable.
エチレン性不飽和単量体(B)の配合量は、アクリル・ウレタン複合樹脂(A)100重量部に対して10〜120重量部の範囲である事が好ましい。上記範囲内であると、塗膜耐性、耐水摩擦性、耐スクラッチ性が良化する。 The blending amount of the ethylenically unsaturated monomer (B) is preferably in the range of 10 to 120 parts by weight with respect to 100 parts by weight of the acrylic / urethane composite resin (A). Within the above range, the coating film resistance, water friction resistance, and scratch resistance are improved.
エチレン性不飽和単量体(B)の重合の際には、水溶性重合開始剤を使用することが好ましく、例えば、過硫酸アンモニウム(APS)、過硫酸カリウム(KPS)、過酸化水素、2,2’−アゾビス(2−メチルプロピオンアミジン)ジハイドロクロライドなど、従来既知のものを好適に使用することができる。 In the polymerization of the ethylenically unsaturated monomer (B), it is preferable to use a water-soluble polymerization initiator. For example, ammonium persulfate (APS), potassium persulfate (KPS), hydrogen peroxide, 2, Conventionally known ones such as 2′-azobis (2-methylpropionamidine) dihydrochloride can be preferably used.
また、重合を行うに際して、所望により重合開始剤とともに還元剤を併用することができる。これにより、乳化重合速度を促進したり、低温において乳化重合を行ったりすることが容易になる。 Moreover, when performing superposition | polymerization, a reducing agent can be used together with a polymerization initiator depending on necessity. Thereby, it becomes easy to accelerate the emulsion polymerization rate or to perform the emulsion polymerization at a low temperature.
このような還元剤としては、例えば、アスコルビン酸、エルソルビン酸、酒石酸、クエン酸、ブドウ糖、ホルムアルデヒドスルホキシラートなどの金属塩等の還元性有機化合物、チオ硫酸ナトリウム、亜硫酸ナトリウム、重亜硫酸ナトリウム、メタ重亜硫酸ナトリウムなどの還元性無機化合物、塩化第一鉄、ロンガリット、二酸化チオ尿素などを例示できる。これら還元剤は、エチレン性不飽和単量体100重量部に対して、0.05〜5.0重量部の量を用いるのが好ましい。なお、前記した重合開始剤によらずとも、光化学反応や、放射線照射等によっても重合を行うことができる。重合温度は各重合開始剤の重合開始温度以上とする。例えば、過酸化物系重合開始剤では、通常80℃程度とすればよい。重合時間は特に制限されないが、通常2〜24時間である。 Examples of such a reducing agent include reducing organic compounds such as metal salts such as ascorbic acid, ersorbic acid, tartaric acid, citric acid, glucose, formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, Examples include reducing inorganic compounds such as sodium bisulfite, ferrous chloride, Rongalite, thiourea dioxide, and the like. These reducing agents are preferably used in an amount of 0.05 to 5.0 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer. In addition, it can superpose | polymerize also by a photochemical reaction, radiation irradiation, etc. irrespective of an above described polymerization initiator. The polymerization temperature is not less than the polymerization start temperature of each polymerization initiator. For example, in the case of a peroxide-based polymerization initiator, it may be usually about 80 ° C. The polymerization time is not particularly limited, but is usually 2 to 24 hours.
さらに必要に応じて、緩衝剤として、酢酸ナトリウム、クエン酸ナトリウム、重炭酸ナトリウムなどが、また、連鎖移動剤としてのオクチルメルカプタン、チオグリコール酸2−エチルヘキシル、チオグリコール酸オクチル、ステアリルメルカプタン、ラウリルメルカプタン、t−ドデシルメルカプタンなどのメルカプタン類が適量使用できる。 Further, if necessary, sodium acetate, sodium citrate, sodium bicarbonate, etc. as a buffering agent, and octyl mercaptan, 2-ethylhexyl thioglycolate, octyl thioglycolate, stearyl mercaptan, lauryl mercaptan as a chain transfer agent A suitable amount of mercaptans such as t-dodecyl mercaptan can be used.
親水性基がアニオン性基の場合、本発明の複合樹脂の酸価は15〜150mgKOH/gの範囲である事が好ましい。上記範囲内であると、複合樹脂の分散安定性が良化し、造膜性に優れた塗膜が得られるため、基材密着性、耐水摩擦性が良化する。さらに、複合樹脂の乾燥性が上がるため、基材密着性、耐水摩擦性、耐スクラッチ性が良化する。より好ましくは15〜75mgKOH/gである。 When the hydrophilic group is an anionic group, the acid value of the composite resin of the present invention is preferably in the range of 15 to 150 mgKOH / g. Within the above range, since the dispersion stability of the composite resin is improved and a coating film having excellent film forming property is obtained, adhesion to the substrate and water friction resistance are improved. Furthermore, since the drying property of the composite resin is improved, the substrate adhesion, water friction resistance, and scratch resistance are improved. More preferably, it is 15-75 mgKOH / g.
本発明の水性複合樹脂は、塗膜耐性と基材密着性に優れるアクリル・ウレタン複合樹脂(A)のシェル部と、塗膜強度を更に向上させる高分子量のエチレン性不飽和単量体(B)の重合体からなるコア部から構成されるコアシェル型水性複合樹脂であり、コア部とシェル部の相溶が良く、造膜性に優れるため、良好な塗膜耐性、基材密着性を発現する。 The aqueous composite resin of the present invention comprises an acrylic / urethane composite resin (A) shell portion excellent in coating film resistance and substrate adhesion, and a high molecular weight ethylenically unsaturated monomer (B) that further improves coating film strength. ) Is a core-shell type water-based composite resin composed of a core part made of a polymer, and has good compatibility between the core part and the shell part and excellent film-forming properties, so that it exhibits good film resistance and substrate adhesion. To do.
<水性インキ組成物>
本発明の水性インキ組成物は、前記水性複合樹脂と、顔料と、親水性溶剤と、水を含有してなるインキ組成物である。
<Water-based ink composition>
The water-based ink composition of the present invention is an ink composition comprising the water-based composite resin, a pigment, a hydrophilic solvent, and water.
本発明の複合樹脂は水性インキ組成物100重量%中、固形分換算で5〜40重量%使用するのが好ましく、10〜30重量%使用するのがより好ましい。複合樹脂の添加量が固形分換算で重量5%未満であると、インキの分散安定性、保存安定性、塗膜物性(基材密着性、耐水摩擦性)が低下する場合がある。一方、複合樹脂が固形分換算で40重量%を超えると、インキ組成物の粘度が著しく上昇し、塗膜における乾燥不良の発生し、塗膜物性(基材密着性、耐水摩擦性、耐水ブロッキング性)が低下する場合がある。 The composite resin of the present invention is preferably used in an amount of 5 to 40% by weight in terms of solid content in 100% by weight of the water-based ink composition, and more preferably 10 to 30% by weight. If the addition amount of the composite resin is less than 5% by weight in terms of solid content, the dispersion stability of the ink, the storage stability, and the physical properties of the coating film (substrate adhesion, water friction resistance) may be deteriorated. On the other hand, when the composite resin exceeds 40% by weight in terms of solid content, the viscosity of the ink composition is remarkably increased, resulting in poor drying in the coating film, and physical properties of the coating film (substrate adhesion, water friction resistance, water blocking resistance). Property) may decrease.
顔料としては、例えば、カーボンブラック、酸化チタン、炭酸カルシウム等の無彩色の顔料または有彩色の有機顔料が使用できる。有機顔料としては、トルイジンレッド、トルイジンマルーン、ハンザエロー、ベンジジンエロー、ピラゾロンレッドなどの不溶性アゾ顔料、リトールレッド、ヘリオボルドー、ピグメントスカーレット、パーマネントレッド2Bなどの溶性アゾ顔料、アリザリン、インダントロン、チオインジゴマルーンなどの建染染料からの誘導体、フタロシアニンブルー、フタロシアニングリーンなどのフタロシアニン系有機顔料、キナクリドンレッド、キナクリドンマゼンタなどのキナクリドン系有機顔料、ペリレンレッド、ペリレンスカーレットなどのペリレン系有機顔料、イソインドリノンエロー、イソインドリノンオレンジなどのイソインドリノン系有機顔料、ピランスロンレッド、ピランスロンオレンジなどのピランスロン系有機顔料、チオインジゴ系有機顔料、縮合アゾ系有機顔料、ベンズイミダゾロン系有機顔料、キノフタロンエローなどのキノフタロン系有機顔料、イソインドリンエローなどのイソインドリン系有機顔料、その他の顔料として、フラバンスロンエロー、アシルアミドエロー、ニッケルアゾエロー、銅アゾメチンエロー、ペリノンオレンジ、アンスロンオレンジ、ジアンスラキノニルレッド、ジオキサジンバイオレット等が挙げられる。 As the pigment, for example, an achromatic pigment such as carbon black, titanium oxide, calcium carbonate, or a chromatic organic pigment can be used. Examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa Yellow, Benzidine Yellow, and pyrazolone red, soluble azo pigments such as Ritol Red, Helio Bordeaux, Pigment Scarlet, and Permanent Red 2B, alizarin, indanthrone, and thioindigo. Derivatives from vat dyes such as maroon, phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green, quinacridone organic pigments such as quinacridone red and quinacridone magenta, perylene organic pigments such as perylene red and perylene scarlet, isoindolinone yellow , Isoindolinone organic pigments such as isoindolinone orange, pyranthrone organic pigments such as pyranthrone red and pyranthrone orange, thioy Digo-based organic pigments, condensed azo-based organic pigments, benzimidazolone-based organic pigments, quinophthalone-based organic pigments such as quinophthalone yellow, isoindoline-based organic pigments such as isoindoline yellow, and other pigments such as flavanthrone yellow and acylamide yellow Nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red, dioxazine violet and the like.
有機顔料をカラーインデックス(C.I.)ナンバーで例示すると、C.I.ピグメントエロー12、13、14、17、20、24、74、83、86 93、109、110、117、120、125、128、129、137、138、139、147、148、150、151、153、154、155、166、168、180、185、C.I.ピグメントオレンジ16、36、43、51、55、59、61、C.I.ピグメントレッド9、48、49、52、53、57、97、122、123、149、168、177、180、192、202、206、215、216、217、220、223、224、226、227、228、238、240、C.I.ピグメントバイオレット19、23、29、30、37、40、50、C.I.ピグメントブルー15、15:1、15:3、15:4、15:6、22、60、64、C.I.ピグメントグリーン7、36、C.I.ピグメントブラウン23、25、26等が挙げられる。 When organic pigments are exemplified by color index (CI) numbers, C.I. I. Pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 8893, 109, 110, 117, 120, 125, 128, 129, 137, 138, 139, 147, 148, 150, 151, 153 154, 155, 166, 168, 180, 185, C.I. I. Pigment orange 16, 36, 43, 51, 55, 59, 61, C.I. I. Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 123, 149, 168, 177, 180, 192, 202, 206, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, C.I. I. Pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 22, 60, 64, C.I. I. Pigment green 7, 36, C.I. I. Pigment brown 23, 25, 26, and the like.
カーボンブラックの具体例としては、デグサ社製「Special Black350、250、100、550、5、4、4A、6」「PrintexU、V、140U、140V、95、90、85、80、75、55、45、40、P、60、L6、L、300、30、3、35、25、A、G」、キャボット社製「REGAL400R、660R、330R、250R」「MOGUL E、L」、三菱化学社製「MA7、8、11、77、100、100R、100S、220、230」「#2700、#2650、#2600、#200、#2350、#2300、#2200、#1000、#990、#980、#970、#960、#950、#900、#850、#750、#650、#52、#50、#47、#45、#45L、#44、#40、#33、#332、#30、#25、#20、#10、#5、CF9、#95、#260」等が挙げられる。 Specific examples of carbon black include “Special Black 350, 250, 100, 550, 5, 4, 4A, 6” “Printex U, V, 140 U, 140 V, 95, 90, 85, 80, 75, 55, manufactured by Degussa. 45, 40, P, 60, L6, L, 300, 30, 3, 35, 25, A, G ", Cabot's" REGAL 400R, 660R, 330R, 250R "," MOGUL E, L ", Mitsubishi Chemical “MA7, 8, 11, 77, 100, 100R, 100S, 220, 230” “# 2700, # 2650, # 2600, # 200, # 2350, # 2300, # 2200, # 1000, # 990, # 980, # 970, # 960, # 950, # 900, # 850, # 750, # 650, # 52, # 50, # 47, # 45, # 4 5L, # 44, # 40, # 33, # 332, # 30, # 25, # 20, # 10, # 5, CF9, # 95, # 260 ”and the like.
酸化チタンの具体例としては、石原産業社製「タイペークCR−50、50−2、57、80、90、93、95、953、97、60、60−2、63、67、58、58−2、85」「タイペークR−820,830、930、550、630、680、670、580、780、780−2、850、855」「タイペークA−100、220」「タイペークW−10」「タイペークPF−740、744」「TTO−55(A)、55(B)、55(C)、55(D)、55(S)、55(N)、51(A)、51(C)」「TTO−S−1、2」「TTO−M−1、2」、テイカ社製「チタニックスJR−301、403、405、600A、605、600E、603、805、806、701、800、808」「チタニックスJA−1、C、3、4、5」、デュポン社製「タイピュアR−900、902、960、706、931」などが挙げられる。イエロー、マゼンタ、シアン、ブラックなどの有機顔料は、水性インキ組成物100重量%中、5〜30重量%の割合で配合する事が好ましい。また、白の酸化チタンの場合は通常10〜60重量%の割合で配合することが好ましい。 Specific examples of titanium oxide include “Taipeku CR-50, 50-2, 57, 80, 90, 93, 95, 953, 97, 60, 60-2, 63, 67, 58, 58- manufactured by Ishihara Sangyo Co., Ltd. 2, 85 "" Tipekes R-820, 830, 930, 550, 630, 680, 670, 580, 780, 780-2, 850, 855 "," Tipekes A-100, 220 "," Tipekes W-10 "," Tipekes " PF-740, 744 "" TTO-55 (A), 55 (B), 55 (C), 55 (D), 55 (S), 55 (N), 51 (A), 51 (C) " "TTO-S-1, 2", "TTO-M-1, 2", "Titanics JR-301, 403, 405, 600A, 605, 600E, 603, 805, 806, 701, 800, 808" manufactured by Teika "Titanic EN-1, C, 3, 4, 5 ", and the like manufactured by Du Pont" Taipyua R-900,902,960,706,931 ". The organic pigments such as yellow, magenta, cyan and black are preferably blended at a ratio of 5 to 30% by weight in 100% by weight of the water-based ink composition. Moreover, in the case of white titanium oxide, it is preferable to mix | blend normally in the ratio of 10-60 weight%.
親水性溶剤としては、例えば、エタノール、1−プロパノール(n−プロパノール)、2−プロパノール(イソプロピルアルコール)、1−ブタノール、2−メチル−1−プロパノール、2−ブタノール、2−メチル−2−プロパノールなどの一価のアルコール溶剤;
エチレングリコール、1,3−プロパンジオール、プロピレングリコール、1,2−ブタンジオール、1,4−ブタンジオール、ペンチレングリコール、1,2−ヘキサンジオール、1,6−ヘキサンジオール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール等のグリコール系溶剤;
エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテル、トリエチレングリコールモノエチルエーテル、エチレングリコールモノイソプロピルエーテル、ジエチレングリコールモノイソプロピルエーテル、トリエチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノブチルエーテル、エチレングリコールモノイソブチルエーテル、ジエチレングリコールモノイソブチルエーテル、トリエチレングリコールモノイソブチルエーテル、エチレングリコールモノヘキシルエーテル、ジエチレングリコールモノヘキシルエーテル、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノメチルエーテル等のグリコールエーテル系溶剤;
N−メチル−2−ピロリドン、N−ヒドロキシエチル−2−ピロリドン、2−ピロリドン、ε−カプロラクタム等のラクタム系溶剤;
ホルムアミド、N−メチルホルムアミド、N,N−ジメチルホルムアミド、出光製エクアミドM−100、エクアミドB−100等のアミド系溶剤
等が挙げられ、一価のアルコール溶剤、グリコールエーテル系溶剤が好ましい。
これらは1種類または2種以上を併用して用いることができる。
Examples of the hydrophilic solvent include ethanol, 1-propanol (n-propanol), 2-propanol (isopropyl alcohol), 1-butanol, 2-methyl-1-propanol, 2-butanol, and 2-methyl-2-propanol. Monohydric alcohol solvents;
Ethylene glycol, 1,3-propanediol, propylene glycol, 1,2-butanediol, 1,4-butanediol, pentylene glycol, 1,2-hexanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol Glycol solvents such as tetraethylene glycol;
Ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, triethylene glycol monoisopropyl Ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether , Diethylene glycol monohexyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, glycol ethers such as tripropylene glycol monomethyl ether solvent;
Lactam solvents such as N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, and ε-caprolactam;
Examples include amide solvents such as formamide, N-methylformamide, N, N-dimethylformamide, Idemitsu Examide M-100, and Ecamide B-100, and monovalent alcohol solvents and glycol ether solvents are preferred.
These can be used alone or in combination of two or more.
本発明の水性インキ組成物は、顔料分散樹脂として、(メタ)アクリル酸−(メタ)アクリル酸アルキルエステル共重合体、スチレン−(メタ)アクリル酸−(メタ)アクリル酸アルキルエステル共重合体、スチレン−(メタ)アクリル酸共重合体、マレイン酸−(メタ)アクリル酸アルキルエステル共重合体、スチレン−マレイン酸共重合体、スチレン−マレイン酸−(メタ)アクリル酸アルキルエステル共重合体、スチレン−マレイン酸ハーフエステル教重合体、水性ウレタン樹脂等を使用する事ができる。本発明の水性複合樹脂は、これらの顔料分散樹脂との相溶しやすく、造膜性に優れるため、良好な塗膜耐性を発現する。顔料分散樹脂には市販品を使用しても構わない。 The water-based ink composition of the present invention includes, as a pigment dispersion resin, a (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer, a styrene- (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer, Styrene- (meth) acrylic acid copolymer, maleic acid- (meth) acrylic acid alkyl ester copolymer, styrene-maleic acid copolymer, styrene-maleic acid- (meth) acrylic acid alkyl ester copolymer, styrene -A maleic acid half ester polymer, a water-based urethane resin, etc. can be used. Since the aqueous composite resin of the present invention is easily compatible with these pigment-dispersed resins and has excellent film-forming properties, it exhibits good coating film resistance. A commercially available product may be used as the pigment dispersion resin.
市販品としては、例えば、BASF社製JONCRYL67、JONCRYL678、JONCRYL586、JONCRYL611、JONCRYL683、JONCRYL690、JONCRYL57J、JONCRYL60J、JONCRYL61J、 JONCRYL62J、JONCRYL63J、JONCRYLHPD−96J、JONCRYL501J、JONCRYLPDX-6102B、ビックケミー社製DISPERBYK、DISPERBYK180、DISPERBYK187、DISPERBYK190、DISPERBYK191、DISPERBYK194、DISPERBYK2010、DISPERBYK2015、DISPERBYK2090、DISPERBYK2091、DISPERBYK2095、DISPERBYK2155、ゼネカ社製SOLSPERS41000、サートマー社製、SMA1000H、SMA1440H、SMA2000H、SMA3000H、SMA17352H等が挙げられる。 As commercially available products, for example, BASF Corp. JONCRYL67, JONCRYL678, JONCRYL586, JONCRYL611, JONCRYL683, JONCRYL690, JONCRYL57J, JONCRYL60J, JONCRYL61J, JONCRYL62J, JONCRYL63J, JONCRYLHPD-96J, JONCRYL501J, JONCRYLPDX-6102B, manufactured by BYK Chemie DISPERBYK, DISPERBYK180, DISPERBYK187 , DISPERBYK190, DISPERBYK191, DISPERBYK194, DISPERBYK2010, DISPERBYK2015, DISPERBYK2090, DISPERBYK2091, DISPERBYK2095, DISPERBYK2155, Zeneca SOLSPERS41000, Sartomer, SMA1000H, SMA1440H, SMA2000H, SMA3000H, etc.
また、本発明の水性インキ組成物は、耐水摩擦性や耐水ブロッキング性をさらに向上させる目的で、カルボジイミド基を含有した樹脂微粒子分散体を併用する事もできる。本発明の複合樹脂は疎水性のウレタン骨格を有しているため、カルボジイミド基含有樹脂微粒子分散体との造膜時の相溶が良好であり、複合樹脂のカルボキシル基とカルボジイミド基が反応したインキ塗膜は、耐水摩擦性がさらに向上する。 In addition, the water-based ink composition of the present invention can be used in combination with a resin fine particle dispersion containing a carbodiimide group for the purpose of further improving water friction resistance and water blocking resistance. Since the composite resin of the present invention has a hydrophobic urethane skeleton, the compatibility with the film formation with the carbodiimide group-containing resin fine particle dispersion is good, and the ink in which the carboxyl group and carbodiimide group of the composite resin have reacted The coating film is further improved in water friction resistance.
カルボジイミド基含有樹脂微粒子分散体としては、ジシクロヘキシルメタン−4,4'-ジイソシアナートや1,3-ビス(2-イソシアナト−2−プロピル)ベンゼンから製造したポリカルボジイミドに親水基を変性した水分散体等が挙げられる。市販品としては、例えば、日清紡社製、カルボジライトE−02、E−03A、SV−02、V−02、V−02−L2、V−04、E−04等が挙げられる。 As the carbodiimide group-containing resin fine particle dispersion, polycarbodiimide produced from dicyclohexylmethane-4,4′-diisocyanate or 1,3-bis (2-isocyanato-2-propyl) benzene is modified with water dispersion. Examples include the body. Examples of commercially available products include Nisshinbo Co., Ltd., Carbodilite E-02, E-03A, SV-02, V-02, V-02-L2, V-04, E-04, and the like.
カルボジイミド基含有樹脂微粒子分散体の添加量は、水性インキ組成物100重量%中、固形分換算で0.5〜10重量%程度使用するのが好ましい。添加量が0.5重量%未満であると、添加量が少ないために、耐水摩擦性や耐水ブロッキング性向上の効果が確認できない場合がある。一方で、10重量%を超えると、インキの分散安定性や保存安定性が悪化する恐れがある。 The addition amount of the carbodiimide group-containing resin fine particle dispersion is preferably about 0.5 to 10% by weight in terms of solid content in 100% by weight of the water-based ink composition. When the addition amount is less than 0.5% by weight, the effect of improving the water friction resistance and water blocking resistance may not be confirmed because the addition amount is small. On the other hand, if it exceeds 10% by weight, the dispersion stability and storage stability of the ink may be deteriorated.
また、本発明の水性インキ組成物には、塗膜の耐摩擦性を向上させる目的で市販のワックス微粒子分散体を使用する事ができる。ワックス樹脂微粒子分散体としては、例えば、三井化学社製、ケミパールW100、W200、W300、W310、W306、W400、W401、W4005、W410、W500、WF640、W700、W800、W900、W950、WH201、WP100などが挙げられる。 In the aqueous ink composition of the present invention, a commercially available wax fine particle dispersion can be used for the purpose of improving the friction resistance of the coating film. Examples of the wax resin fine particle dispersion include Chemipearl W100, W200, W300, W310, W306, W400, W401, W4005, W410, W500, WF640, W700, W800, W900, W950, WH201, and WP100 manufactured by Mitsui Chemicals, Inc. Is mentioned.
ワックス微粒子分散体の添加量は、塗膜物性における耐摩擦性向上と色相への悪影響のバランスを考慮して、水性インキ組成物100重量%中、固形分換算で1〜5重量%程度使用するのが好ましい。 The amount of the wax fine particle dispersion added is about 1 to 5% by weight in terms of solid content in 100% by weight of the water-based ink composition in consideration of the balance between the improvement of the friction resistance in the physical properties of the coating film and the adverse effect on the hue. Is preferred.
また、本発明の水性インキ組成物は、基材へのレベリング性を調節する目的で各種表面調整剤を使用する事ができる。表面調整剤としては例えば、日信化学社製、サーフィノール104E,104H、104A、104PA,104PG−50、104S、420、440、465、485、SE,SE−F、PSA−336、61、2502、ダイノール604、607、ビックケミー社製BYK−381、3441、302、307、325、331、333、342、345、346、347、348、349、378、3455等が挙げられるがこれらに限らない。 The water-based ink composition of the present invention can use various surface conditioners for the purpose of adjusting the leveling property to the substrate. As the surface conditioner, for example, Surfinol 104E, 104H, 104A, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, PSA-336, 61, 2502, manufactured by Nissin Chemical Co., Ltd. , DYNOL 604, 607, BYK-381, 3441, 302, 307, 325, 331, 333, 342, 345, 346, 347, 348, 349, 378, 3455, etc., manufactured by BYK Chemie.
表面調整剤の添加量は、塗膜物性への悪影響のバランスを考慮して、水性インキ組成物100重量%中、固形分換算で0〜1.0重量%程度使用するのが好ましい。 The addition amount of the surface modifier is preferably about 0 to 1.0% by weight in terms of solid content in 100% by weight of the water-based ink composition in consideration of the balance of adverse effects on the coating film properties.
また、本発明の水性インキ組成物は、基材への密着性向上や、樹脂の常温架橋(ケト基含有の場合)等の目的で、ヒドラジド系添加剤を使用する事ができる。ヒドラジド系添加剤としては、例えば、アジピン酸ヒドラジド等が挙げられる。 In addition, the water-based ink composition of the present invention can use a hydrazide-based additive for the purpose of improving adhesion to a base material, room temperature crosslinking of a resin (in the case of containing a keto group), and the like. Examples of the hydrazide additive include adipic acid hydrazide.
本発明の水性インキ組成物は、低温乾燥条件下においても、ポリエチレンテレフタラートやポリオレフィン等の非極性フィルム基材において、良好な基材密着性、耐水摩擦性や耐スクラッチ性を発現する。したがって、近年、水性化、基材拡張が強く求められている、フレキソ、グラビア、インクジェットなどの各種インキの分野において大変有用である。また、上質紙などの浸透性基材やアート紙、コート紙など、従来の基材に対しても塗膜物性向上の目的で使用する事ができる。 The water-based ink composition of the present invention exhibits good substrate adhesion, water rub resistance, and scratch resistance even in low-temperature drying conditions on nonpolar film substrates such as polyethylene terephthalate and polyolefin. Therefore, it is very useful in the field of various inks such as flexo, gravure and ink jet, which have recently been strongly demanded to be water-based and extend the base material. Moreover, it can be used for the purpose of improving the physical properties of the coating film even on conventional substrates such as permeable substrates such as fine paper, art paper, and coated paper.
水性インキ組成物の乾燥工程であるが、基材に悪影響を及ぼさない範囲であれば任意の温度をかける事が可能である。フレキソ印刷、グラビア印刷、インクジェット印刷においては、40〜100℃の低温乾燥で1〜200秒の範囲で処理する事が一般的である。 Although it is a drying process of a water-based ink composition, any temperature can be applied as long as it does not adversely affect the substrate. In flexographic printing, gravure printing, and inkjet printing, it is common to process at a low temperature of 40 to 100 ° C. for 1 to 200 seconds.
以下に、実施例により本発明をさらに具体的に説明するが、以下の実施例は本発明の権利範囲を何ら制限するものではない。なお、実施例における「部」は「重量部」、「%」は「重量%」を表す。 EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.
<両末端メルカプト基含有ウレタンウレア樹脂の製造>
[製造例1]
攪拌器、温度計、還流器を備えた反応容器に、ポリオール(C)としてポリテトラメチレングリコール(保土谷化学製PTG−2000 官能基数2、水酸基価57.0mgKOH/g)51.5部、ポリエステル系ポリオール(クラレ製P−2010 官能基数2 水酸基価56.0mgKOH/g)34.9部、ポリイソシアネート(D)としてイソホロンジイソシアネート13.6部を仕込み、窒素雰囲気下で攪拌しながら80℃まで昇温させた。そこに、触媒として、チタンジイソプロポキシビス(エチルアセトアセテート)を0.02部添加して、110℃に昇温して、5時間反応させた後、80℃まで温度を下げた。この時、生成したウレタンプレポリマー(E−1)の重量平均分子量は12700であった。続いて、メチルエチルケトン40.0部、メルカプト基含有化合物(F)として2−アミノエタンチオール2.3部を加え、75℃で2時間反応させた。反応の終点は、FT−IRによりイソシアネート基由来のピーク(2270cm-1付近)の消失により確認した。さらにメチルエチルケトンを添加して、樹脂溶液の最終固形分を70.0%に調製した。得られた両末端メルカプト基含有ウレタンウレア樹脂(E−2)の酸価は0mgKOH/g、重量平均分子量は19600であった。
<Manufacture of both terminal mercapto group-containing urethane urea resins>
[Production Example 1]
In a reaction vessel equipped with a stirrer, a thermometer, and a refluxer, 51.5 parts of polytetramethylene glycol (PTG-2000 functional group number 2, hydroxyl value 57.0 mgKOH / g, manufactured by Hodogaya Chemical) as polyol (C), polyester -Based polyol (Kuraray P-2010 Functional group number 2 Hydroxyl value 56.0 mgKOH / g) 34.9 parts, Polyisocyanate (D) 13.6 parts of isophorone diisocyanate was added, and the temperature was raised to 80 ° C. with stirring in a nitrogen atmosphere. Allowed to warm. Thereto, 0.02 part of titanium diisopropoxybis (ethyl acetoacetate) was added as a catalyst, the temperature was raised to 110 ° C. and reacted for 5 hours, and then the temperature was lowered to 80 ° C. At this time, the weight average molecular weight of the produced urethane prepolymer (E-1) was 12700. Subsequently, 40.0 parts of methyl ethyl ketone and 2.3 parts of 2-aminoethanethiol as the mercapto group-containing compound (F) were added and reacted at 75 ° C. for 2 hours. The end point of the reaction was confirmed by the disappearance of the peak derived from the isocyanate group (around 2270 cm −1 ) by FT-IR. Further, methyl ethyl ketone was added to adjust the final solid content of the resin solution to 70.0%. The acid value of the obtained both-end mercapto group-containing urethane urea resin (E-2) was 0 mgKOH / g, and the weight average molecular weight was 19,600.
[酸価]
樹脂1g中に含まれる酸性成分を中和するのに要する水酸化カリウムのミリグラム数。乾燥させた樹脂について、JIS K2501に記載の方法に従い、水酸化カリウム・エタノール溶液で電位差滴定をおこない算出した。滴定には平沼産業社製:自動滴定装置COM−1600を使用した。
[Acid value]
Number of milligrams of potassium hydroxide required to neutralize acidic components contained in 1 g of resin. The dried resin was calculated by performing potentiometric titration with a potassium hydroxide / ethanol solution according to the method described in JIS K2501. For the titration, an automatic titrator COM-1600 manufactured by Hiranuma Sangyo Co., Ltd. was used.
[重量平均分子量]
重量平均分子量は、GPC(ゲルパーミエーションクロマトグラフィー)測定によるポリスチレン換算の値である。乾燥させた樹脂をテトラヒドロフランに溶解させ、0.1%溶液を調製し、以下の装置ならびに測定条件により重量平均分子量を測定した。
装置:HLC−8320−GPCシステム(東ソー社製)
カラム;TSKgel-SuperMultiporeHZ−M0021488
4.6 mmI.D.×15 cm×3本(分子量測定範囲2千〜約200万)
溶出溶媒;テトラヒドロフラン
標準物質;ポリスチレン(東ソー社製)
流速;0.6mL/分、試料溶液使用量;10μL、カラム温度;40℃。
[Weight average molecular weight]
The weight average molecular weight is a value in terms of polystyrene as measured by GPC (gel permeation chromatography). The dried resin was dissolved in tetrahydrofuran to prepare a 0.1% solution, and the weight average molecular weight was measured using the following apparatus and measurement conditions.
Apparatus: HLC-8320-GPC system (manufactured by Tosoh Corporation)
Column; TSKgel-SuperMultiporeHZ-M0021488
4.6 mm I.D. x 15 cm x 3 (molecular weight measurement range 2,000 to about 2 million)
Elution solvent; Tetrahydrofuran standard substance; Polystyrene (Tosoh Corporation)
Flow rate: 0.6 mL / min, sample solution usage: 10 μL, column temperature: 40 ° C.
[イソシアネート基の定量]
ウレタンプレポリマー0.5gをサンプリングして、0.2モル/L(リットル)のジブチルアミン−トルエン溶液10mL、トルエン25mLを加えて10分攪拌した。その後、イソプロピルアルコール40mLを加え、0.1モル/Lの塩酸エタノール溶液で未消費のジブチルアミンを滴定した。滴定には、平沼産業社製:自動滴定装置COM−1600を使用した。この滴定値とブランク実験との差より、樹脂中に残存するイソシアネート基の量(mmol/g)を算出した。
[Quantification of isocyanate groups]
0.5 g of urethane prepolymer was sampled, 10 mL of a 0.2 mol / L (liter) dibutylamine-toluene solution and 25 mL of toluene were added, and the mixture was stirred for 10 minutes. Thereafter, 40 mL of isopropyl alcohol was added, and unconsumed dibutylamine was titrated with a 0.1 mol / L hydrochloric acid ethanol solution. For the titration, an automatic titrator COM-1600 manufactured by Hiranuma Sangyo Co., Ltd. was used. From the difference between this titration value and the blank experiment, the amount (mmol / g) of isocyanate groups remaining in the resin was calculated.
[製造例2〜12]
表1に示す配合組成で、製造例1と同様の方法により、ウレタンプレポリマー(E−1)を合成し、さらに一般式(1)で表される化合物(F)と反応させ、両末端メルカプト基含有ウレタンウレア樹脂(E-2)を得た。反応後、製造例1と同様の操作をおこない、樹脂溶液の最終固形分を70.0%に調製した。得られた両末端メルカプト基含有ウレタンウレア樹脂についても同様に酸価、重量平均分子量を測定した。
[Production Examples 2 to 12]
A urethane prepolymer (E-1) was synthesized by the same method as in Production Example 1 with the composition shown in Table 1, and further reacted with the compound (F) represented by the general formula (1), and both terminal mercapto A group-containing urethane urea resin (E-2) was obtained. After the reaction, the same operation as in Production Example 1 was performed to adjust the final solid content of the resin solution to 70.0%. The acid value and the weight average molecular weight were also measured in the same manner for the obtained both-end mercapto group-containing urethane urea resin.
表1中の略語について下記に示す。
<ポリオール>
・ユニオールD−2000;日油製ポリプロピレングリコール(官能基数2、OH基価56.0、分子量2000)
・PEG#2000;日油製ポリエチレングリコール(官能基数2、OH基価56.0、分子量2000)
・PTG−2000SN;保土谷化学製ポリテトラメチレングリコール(官能基数2、OH基価57.0、分子量2000)
・P−2010;クラレ製MPD/AA系ポリエステルポリオール(官能基数2、OH価56.0、分子量2000)
・P−2011;クラレ製MPD/AA/TPA系ポリエステルポリオール(官能基数2、 OH価55.0、分子量2000)
・HS2P−203S;豊国製油製1,3PD/SA系ポリエステルポリオール(官能基数2、OH価54.6、分子量2000)
・T5652;旭化成製ポリカーボネートポリオール(官能基数2、OH価56.0、分子量2000)
・GI−1000;日本曹達製水素化ポリブタジエン系ポリオール(官能基数2、OH価64.0、分子1000)
Abbreviations in Table 1 are shown below.
<Polyol>
・ Uniol D-2000; NOF polypropylene glycol (number of functional groups 2, OH group value 56.0, molecular weight 2000)
PEG # 2000: NOF polyethylene glycol (functional group number 2, OH group value 56.0, molecular weight 2000)
PTG-2000SN: Hodogaya Chemical polytetramethylene glycol (number of functional groups 2, OH group value 57.0, molecular weight 2000)
P-2010: Kuraray MPD / AA-based polyester polyol (number of functional groups 2, OH value 56.0, molecular weight 2000)
P-2011: Kuraray MPD / AA / TPA polyester polyol (number of functional groups 2, OH number 55.0, molecular weight 2000)
HS2P-203S: Toyokuni Oil 1,3PD / SA polyester polyol (functional group number 2, OH number 54.6, molecular weight 2000)
-T5652: Asahi Kasei polycarbonate polyol (functional group number 2, OH value 56.0, molecular weight 2000)
GI-1000: Nippon Soda's hydrogenated polybutadiene-based polyol (number of functional groups 2, OH number 64.0, molecule 1000)
<アクリル・ウレタン複合樹脂(A)の製造>
[製造例13]
攪拌器、温度計、滴下ロート、還流器を備えた反応容器に、製造例1で得られた両末端メルカプト基含有ウレタンウレア樹脂溶液142.9部(不揮発成分は100.0部)、メチルメタクリレート40.0部、n−ブチルメタクリレート40.0部、メタクリル酸13.0部、3−メタクリロキシプロピルシラン2.0部、イソプロピルアルコール37.0部を加え、窒素雰囲気下で攪拌しながら70℃まで昇温させた。滴下ロートに、メチルエチルケトン20.0部、開始剤として2,2’−アゾビス(2,4−ジメチルバレロニトリル)を0.35部仕込み、5時間かけて反応槽に滴下した。70℃で8時間反応させ、アクリル樹脂部分のグラフト反応を終了した。反応後、イオン交換水670.0部、25%アンモニア水10.3部を加え、中和した後、脱溶剤処理して水性アクリル・ウレタン複合樹脂の水分散体を得た。イオン交換水により、複合樹脂水分散体の最終固形分を25.0%に調製した。得られた水性アクリル・ウレタン複合樹脂の酸価は42.4mgKOH/g、分子量は39600であった。
[製造例14〜27]
表2に示す配合組成で、製造例13同様の方法でアクリル・ウレタン複合樹脂(A)の水分散体を調製した。
<Manufacture of acrylic / urethane composite resin (A)>
[Production Example 13]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a refluxer, 142.9 parts of a urethane urea resin solution containing both terminal mercapto groups obtained in Production Example 1 (non-volatile component is 100.0 parts), methyl methacrylate 40.0 parts, 40.0 parts of n-butyl methacrylate, 13.0 parts of methacrylic acid, 2.0 parts of 3-methacryloxypropylsilane, and 37.0 parts of isopropyl alcohol were added, and the mixture was stirred at 70 ° C. in a nitrogen atmosphere. The temperature was raised to. In a dropping funnel, 20.0 parts of methyl ethyl ketone and 0.35 part of 2,2′-azobis (2,4-dimethylvaleronitrile) as an initiator were charged and dropped into the reaction vessel over 5 hours. The reaction was performed at 70 ° C. for 8 hours to complete the graft reaction of the acrylic resin portion. After the reaction, 670.0 parts of ion exchange water and 10.3 parts of 25% ammonia water were added to neutralize, and then the solvent was removed to obtain an aqueous dispersion of an aqueous acrylic / urethane composite resin. The final solid content of the composite resin water dispersion was adjusted to 25.0% with ion-exchanged water. The resulting aqueous acrylic / urethane composite resin had an acid value of 42.4 mgKOH / g and a molecular weight of 39600.
[Production Examples 14 to 27]
An aqueous dispersion of acrylic / urethane composite resin (A) was prepared in the same manner as in Production Example 13 with the composition shown in Table 2.
表2中の略語を下記に示す。
・PME−400:日油製メトキシポリエチレングリコールメタクリレート(エチレンオキサイド付加モル数9)
Abbreviations in Table 2 are shown below.
PME-400: NOF's methoxypolyethylene glycol methacrylate (ethylene oxide addition mole number 9)
<水性ウレタン樹脂の合成>
[製造例28]
攪拌器、温度計、還流器を備えた反応容器に、ポリテトラメチレングリコール(保土谷化学製PTG−2000 官能基数2、水酸基価57.0mgKOH/g)31.6部、ポリエステル系ポリオール(クラレ製P−2010 官能基数2 水酸基価56.0mgKOH/g)48.2部、ジメチロールブタン酸5.9部、イソホロンジイソシアネート14.3部を仕込み、窒素雰囲気下で攪拌しながら80℃まで昇温させた。そこに、触媒として、チタンジイソプロポキシビス(エチルアセトアセテート)を0.02部添加して、110℃に昇温して、5時間反応させ、ウレタン樹脂を得た。反応後、イオン交換水330部、25%アンモニア水2.8部を加え、中和した後、脱溶剤処理して水性ウレタン樹脂の水分散体を得た。イオン交換水により、ウレタン樹脂水分散の最終固形分を25.0%に調製した。得られた水性ウレタン樹脂の酸価は22.5mgKOH/g、分子量は12900であった。
<Synthesis of aqueous urethane resin>
[Production Example 28]
In a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 31.6 parts of polytetramethylene glycol (PTG-2000 functional group number 2, hydroxyl value 57.0 mgKOH / g, manufactured by Hodogaya Chemical), polyester polyol (manufactured by Kuraray) P-2010 Functional group number 2 Hydroxyl value 56.0 mgKOH / g) 48.2 parts, dimethylolbutanoic acid 5.9 parts, isophorone diisocyanate 14.3 parts were charged, and the temperature was raised to 80 ° C. with stirring in a nitrogen atmosphere. It was. Thereto, 0.02 part of titanium diisopropoxybis (ethyl acetoacetate) was added as a catalyst, heated to 110 ° C. and reacted for 5 hours to obtain a urethane resin. After the reaction, 330 parts of ion exchange water and 2.8 parts of 25% aqueous ammonia were added to neutralize, and then the solvent was removed to obtain an aqueous dispersion of an aqueous urethane resin. The final solid content of urethane resin water dispersion was adjusted to 25.0% with ion-exchanged water. The obtained water-based urethane resin had an acid value of 22.5 mgKOH / g and a molecular weight of 12,900.
<水性アクリル樹脂の合成>
[製造例29]
攪拌器、温度計、2つの滴下ロート、還流器を備えた別の反応容器に、イソプロピルアルコール94.0部を仕込み、攪拌しながら、窒素雰囲気下で温度75℃まで昇温した。次に、2つの滴下ロートにおいて、一方からは、メチルメタクリレート30.0部、シクロヘキシルメタクリレート20.0部、スチレン15.0部を3時間かけて滴下した。もう一方からは、2,2’−アゾビス(2,4−ジメチルバレロニトリル)5.0部をメチルイソブチルケトン12.0部に溶解させ、4時間かけてそれを滴下した。滴下完了後、更に10時間反応させた。反応後、イオン交換水330部、25%アンモニア水27.7部を加え、中和した後、脱溶剤処理して水性アクリル樹脂の水分散体を得た。
<Synthesis of aqueous acrylic resin>
[Production Example 29]
In a separate reaction vessel equipped with a stirrer, thermometer, two dropping funnels, and a reflux condenser, 94.0 parts of isopropyl alcohol was charged, and the temperature was raised to 75 ° C. in a nitrogen atmosphere while stirring. Next, in two dropping funnels, 30.0 parts of methyl methacrylate, 20.0 parts of cyclohexyl methacrylate, and 15.0 parts of styrene were dropped from one side over 3 hours. From the other side, 5.0 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 12.0 parts of methyl isobutyl ketone and added dropwise over 4 hours. After completion of dropping, the reaction was further continued for 10 hours. After the reaction, 330 parts of ion exchange water and 27.7 parts of 25% ammonia water were added to neutralize, and then the solvent was removed to obtain an aqueous dispersion of an aqueous acrylic resin.
<水性ウレタン樹脂ならびに水性アクリル樹脂の混合液の調製>
[製造例30]
製造例28で得た水性ウレタン樹脂溶液を50.0部、製造例29で得た水性アクリル樹脂溶液を50.0部混合し、水性ウレタン樹脂ならびに水性アクリル樹脂の混合水溶液を調製した。最終固形分は25.0%であった。
<Preparation of liquid mixture of aqueous urethane resin and aqueous acrylic resin>
[Production Example 30]
50.0 parts of the aqueous urethane resin solution obtained in Production Example 28 and 50.0 parts of the aqueous acrylic resin solution obtained in Production Example 29 were mixed to prepare a mixed aqueous solution of the aqueous urethane resin and the aqueous acrylic resin. The final solid content was 25.0%.
<コアシェル型水性複合樹脂分散体の製造>
[実施例1]攪拌器、温度計、2つの滴下ロート、還流器を備えた別の反応容器に、製造例13で調製したアクリル・ウレタン複合樹脂溶液(A)333.3部(不揮発成分は100部)、を仕込み、攪拌しながら、窒素還流下で温度を80℃まで昇温した。昇温後、2つの滴下ロートにおいて、一方からは、メチルメタクリレート30.0部、スチレン10.0部、n−ブチルアクリレート60.0部の混合溶液を2時間かけて滴下した。もう一方からは、過硫酸アンモニウム20%水溶液4.0部を2時間かけて滴下した。滴下完了後、更に6時間反応させてコアシェル型水性複合樹脂分散体を得た。反応後、イオン交換水により、最終固形分を25.0%に調整した。得られた分散体について、重量平均分子量、酸価を測定した。得られた樹脂の重量平均分子量は125000、酸価は21.2mgKOH/gであった。
<Manufacture of core-shell type aqueous composite resin dispersion>
[Example 1] In another reaction vessel equipped with a stirrer, a thermometer, two dropping funnels, and a reflux condenser, 333.3 parts of the acrylic / urethane composite resin solution (A) prepared in Production Example 13 (nonvolatile components are 100 parts), and the temperature was raised to 80 ° C. under nitrogen reflux while stirring. After raising the temperature, in two dropping funnels, a mixed solution of 30.0 parts of methyl methacrylate, 10.0 parts of styrene, and 60.0 parts of n-butyl acrylate was dropped from one side over 2 hours. From the other side, 4.0 parts of a 20% aqueous solution of ammonium persulfate was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 6 hours to obtain a core-shell type aqueous composite resin dispersion. After the reaction, the final solid content was adjusted to 25.0% with ion-exchanged water. About the obtained dispersion, the weight average molecular weight and the acid value were measured. The obtained resin had a weight average molecular weight of 125,000 and an acid value of 21.2 mgKOH / g.
[実施例2〜17]
表3に示す配合組成で、実施例1と同様の方法で複合樹脂を合成した。反応後、実施例1と同様に、脱溶剤処理をおこない、目的の水性複合樹脂の水分散体を得た。得られた複合樹脂の水分散体の最終固形分は25.0%に調製した。得られた樹脂について、実施例1と同様に酸価を測定した。
[Examples 2 to 17]
A composite resin was synthesized in the same manner as in Example 1 with the composition shown in Table 3. After the reaction, the solvent removal treatment was performed in the same manner as in Example 1 to obtain an aqueous dispersion of the target aqueous composite resin. The final solid content of the obtained aqueous dispersion of composite resin was adjusted to 25.0%. The acid value of the obtained resin was measured in the same manner as in Example 1.
表3中の略語を下記に示す。
・PME−400:日油製メトキシポリエチレングリコールメタクリレート(エチレンオキサイド付加モル数9)
Abbreviations in Table 3 are shown below.
PME-400: NOF's methoxypolyethylene glycol methacrylate (ethylene oxide addition mole number 9)
[比較例1〜3]
表4に示す配合組成で、実施例1と同様の方法で水性樹脂を合成した。反応後、実施例1と同様に、脱溶剤処理をおこない、目的の樹脂の水分散体を得た。得られた樹脂水分散体の最終固形分は25.0%に調製した。得られた樹脂について、実施例1と同様に酸価を測定した。
[Comparative Examples 1-3]
A water-based resin was synthesized in the same manner as in Example 1 with the composition shown in Table 4. After the reaction, a solvent removal treatment was performed in the same manner as in Example 1 to obtain an aqueous dispersion of the target resin. The final solid content of the obtained resin water dispersion was adjusted to 25.0%. The acid value of the obtained resin was measured in the same manner as in Example 1.
<水性インキ組成物の製造> <Production of water-based ink composition>
<白色インキ組成物の製造>
[実施例18]酸化チタン系無機顔料[タイペークCR80 石原産業社製]40.5部、ジョンクリル67(スチレン・アクリル樹脂)水溶液(固形分25%)13.5部、イオン交換水11.0部、表面調整剤[サーフィノール420 日信化学工業社製]0.2部、アジピン酸ヒドラジド0.3部、n−プロパノール2.0部をペイントコンディショナーにて2時間分散し、濃縮白顔料分散液を得た。この濃縮白顔料分散液に、実施例1で得られた水性複合樹脂の水分散体29.0部、ケミパールW500(固形分40.0%)3.0部、ジエチレングリコールモノエチルエーテル0.5部を加えた後、混練して目的の白色水性インキ組成物を得た。
<Manufacture of white ink composition>
[Example 18] Titanium oxide-based inorganic pigment [Taipec CR80 manufactured by Ishihara Sangyo Co., Ltd.] 40.5 parts, Jonkrill 67 (styrene / acrylic resin) aqueous solution (solid content 25%) 13.5 parts, ion-exchanged water 11.0 Parts, surface conditioner [Surfinol 420 manufactured by Nissin Chemical Industry Co., Ltd.] 0.2 parts, adipic acid hydrazide 0.3 parts, n-propanol 2.0 parts are dispersed for 2 hours with a paint conditioner, concentrated white pigment dispersion A liquid was obtained. To this concentrated white pigment dispersion, 29.0 parts of the aqueous dispersion of the aqueous composite resin obtained in Example 1, 3.0 parts of Chemipearl W500 (solid content 40.0%), 0.5 parts of diethylene glycol monoethyl ether Was added and kneaded to obtain the desired white aqueous ink composition.
[実施例19〜34および比較例4〜7]
表5、6に示す配合組成で、実施例18と同様の方法で調製し、白色水性インキ組成物を得た。
<藍色インキ組成物の製造>
[実施例35]
フタロシアニン系有機顔料[リオノールブルーFG7330 トーヨーカラー社製]17.2部、ジョンクリル67(スチレン・アクリル樹脂)水溶液(固形分25.0%)11.6部、イオン交換水18.6部、表面調整剤[サーフィノール420 日信化学工業製]0.2部、アジピン酸ヒドラジド0.2部、n−プロパノール2.7部をペイントコンディショナーにて2時間分散し、濃縮藍顔料分散液を得た。さらに、実施例1の水性複合樹脂の水分散体39.5部、三井化学社製ケミパールW500(固形分40.0%)4.5部、親水性溶剤としてジエチレングリコールモノエチルエーテル0.5部、イオン交換水5.0部を加えた後、混練して藍色水性インキ組成物を得た。
[Examples 19 to 34 and Comparative Examples 4 to 7]
With the composition shown in Tables 5 and 6, it was prepared in the same manner as in Example 18 to obtain a white aqueous ink composition.
<Manufacture of indigo ink composition>
[Example 35]
Phthalocyanine-based organic pigment [Lionol Blue FG7330 manufactured by Toyocolor Co., Ltd.] 17.2 parts, Joncryl 67 (styrene / acrylic resin) aqueous solution (solid content 25.0%) 11.6 parts, ion-exchanged water 18.6 parts, Surface adjuster [Surfinol 420 manufactured by Nissin Chemical Industry Co., Ltd.] 0.2 parts, adipic acid hydrazide 0.2 parts, and n-propanol 2.7 parts were dispersed for 2 hours with a paint conditioner to obtain a concentrated indigo pigment dispersion. It was. Furthermore, 39.5 parts of an aqueous dispersion of the aqueous composite resin of Example 1, 4.5 parts of Chemipearl W500 (solid content 40.0%) manufactured by Mitsui Chemicals, 0.5 part of diethylene glycol monoethyl ether as a hydrophilic solvent, After adding 5.0 parts of ion-exchanged water, the mixture was kneaded to obtain an indigo water-based ink composition.
[実施例36〜51および比較例8〜11]
表7、8に示す配合組成で、実施例35と同様の方法で調製し、藍色水性インキ組成物を得た。
[Examples 36 to 51 and Comparative Examples 8 to 11]
The blending compositions shown in Tables 7 and 8 were prepared in the same manner as in Example 35 to obtain an indigo water-based ink composition.
<水性インキ組成物の評価>
上述の水性インキ組成物について、フレキシプルーフ100(アニロックスローラー80線/cm)を用いて、処理PET基材に塗工した。塗工後、基材をオーブンで80℃・2分で加熱処理して評価用の印刷物塗膜を得た。これを用いて、基材密着性、耐水摩擦性、耐スクラッチ性を評価した。表5〜8にその結果を示す。
<Evaluation of water-based ink composition>
About the above-mentioned water-based ink composition, it apply | coated to the process PET base material using the flexiproof 100 (anilox roller 80 line / cm). After coating, the substrate was heat-treated in an oven at 80 ° C. for 2 minutes to obtain a printed film for evaluation. This was used to evaluate substrate adhesion, water rub resistance, and scratch resistance. The results are shown in Tables 5-8.
[基材密着性]
印刷物塗膜にセロハンテープ(ニチバン社製18mm幅)を貼り付け、垂直方向に剥離試験をおこない、インキの剥がれた面積の割合から基材密着性について評価した。
評価基準は以下の通りである。(実用可能レベルは○以上)
◎;インキの剥がれがない
○;インキの剥がれがややある(10%未満)
△;インキの剥がれがある(10%以上、50%未満)
×;インキの剥がれがかなりある(50%以上)
[Base material adhesion]
Cellophane tape (18 mm width manufactured by Nichiban Co., Ltd.) was applied to the printed film, and a peel test was conducted in the vertical direction, and the substrate adhesion was evaluated from the ratio of the area where the ink was peeled off.
The evaluation criteria are as follows. (Practical level is more than ○)
◎: No ink peeling ○: Some ink peeling (less than 10%)
Δ: Ink peeling (10% or more, less than 50%)
×: Ink peeling is considerable (50% or more)
[耐水摩擦性]
印刷物塗膜を1分間水に浸漬させた。浸漬後、摩擦子にカナキン(JIS L 0803)を用い、水をたらした塗膜表面を学振試験機(テスター産業社製)により、荷重500gで800往復させた。インキの剥がれた面積の割合から耐水摩擦性について評価した。評価基準は以下の通りである。(実用可能レベルは○以上)
◎;インキの剥がれがない
○;インキの剥がれがややある(5%未満)
△;インキの剥がれがある(5%以上、30%未満)
×;インキの剥がれがかなりある(30%以上)
[Water friction resistance]
The printed film was immersed in water for 1 minute. After dipping, using Kanakin (JIS L 0803) as the friction element, the surface of the coated film with water was reciprocated 800 times with a load of 500 g using a Gakushin tester (manufactured by Tester Sangyo Co., Ltd.). The water friction resistance was evaluated from the ratio of the area where the ink was peeled off. The evaluation criteria are as follows. (Practical level is more than ○)
◎: No ink peeling ○: Ink peeling slightly (less than 5%)
Δ: Ink peeling (5% or more, less than 30%)
×: Ink peeling is considerable (30% or more)
[耐スクラッチ性]
各印刷物塗膜について、爪で20回擦って塗工面の傷付き易さを観察した。評価基準は以下の通りである。(実用可能レベルは○)
〇;印刷物塗膜全てに傷がつかなかった
×;印刷塗膜のいずれかに傷が付いた。
[Scratch resistance]
Each printed film was rubbed with nails 20 times to observe the ease of scratches on the coated surface. The evaluation criteria are as follows. (Practical level is ○)
◯: All the printed film was not damaged. ×: Either of the printed films was damaged.
表5、7に示すように、実施例1〜17の水性複合樹脂を使用した白色水性インキ組成物(実施例18〜34)ならびに藍色水性インキ組成物(実施例35〜51)は、印刷物塗膜の基材密着性、耐水摩擦性、耐スクラッチ性、耐水ブロッキング性に優れ、実用可能なレベルである事がわかった。
実施例の中でも、化合物(D)が、アミノアルカンチオールであり、酸価が15〜150mgKOH/gであり、エチレン性不飽和単量体(G)の配合量が、両末端メルカプト基含有ウレタンウレア樹脂(E-2)100重量部に対して30〜180重量部の範囲であり、エチレン性不飽和単量体(B)の配合量が、アクリル・ウレタン複合樹脂(A)100重量部に対して10〜120重量部の範囲である水性複合樹脂を使用した実施例18、19、21、22、26〜28、30、32は基材密着性及び耐水摩擦性が優れる結果となった。
一方、比較例1〜3、製造例13の水性樹脂を使用した白色水性インキ組成物(比較例4〜7)ならびに藍色水性インキ組成物(比較例8〜11)は、表6、8に示すように印刷物塗膜への基材密着性、耐水摩擦性、耐スクラッチ性が劣っており、実用可能なレベルを満たさない結果となった。
これにより、本発明の水性複合樹脂分散体の優位性が証明された。
As shown in Tables 5 and 7, the white aqueous ink compositions (Examples 18 to 34) and the indigo aqueous ink compositions (Examples 35 to 51) using the aqueous composite resins of Examples 1 to 17 are printed matter. It was found that the coating had excellent substrate adhesion, water rub resistance, scratch resistance and water blocking resistance, and was at a practical level.
Among the examples, the compound (D) is an aminoalkanethiol, the acid value is 15 to 150 mgKOH / g, and the blending amount of the ethylenically unsaturated monomer (G) is a urethane urea containing both end mercapto groups. The amount of the ethylenically unsaturated monomer (B) is in the range of 30 to 180 parts by weight with respect to 100 parts by weight of the resin (E-2), and the amount of the ethylenically unsaturated monomer (B) is 100 parts by weight of the acrylic / urethane composite resin (A). Examples 18, 19, 21, 22, 26 to 28, 30, and 32 using the aqueous composite resin in the range of 10 to 120 parts by weight resulted in excellent substrate adhesion and water friction resistance.
On the other hand, white aqueous ink compositions (Comparative Examples 4 to 7) and indigo water-based ink compositions (Comparative Examples 8 to 11) using the aqueous resins of Comparative Examples 1 to 3 and Production Example 13 are shown in Tables 6 and 8, respectively. As shown, the substrate adhesion to the printed film, water rub resistance, and scratch resistance were inferior, and the results did not satisfy the practical level.
This proved the superiority of the aqueous composite resin dispersion of the present invention.
Claims (8)
アクリル・ウレタン複合樹脂(A)が、
ポリオール(C)とポリイソシアネート(D)とを反応させてなるウレタンプレポリマー(E−1)に、一般式(1)で表される化合物(F)を反応させてなる両末端メルカプト基含有ウレタンウレア樹脂(E−2)を連鎖移動剤として、エチレン性不飽和単量体(G)を重合したものである水性複合樹脂分散体。
一般式(1)
Rはアルキレン基、アリーレン基、およびアルキレンオキサイド基からなる群より選ばれる少なくとも一種の2価の基である。) An aqueous composite resin dispersion obtained by polymerizing an ethylenically unsaturated monomer (B) in an aqueous medium using an acrylic / urethane composite resin (A) as a polymer emulsifier,
Acrylic / urethane composite resin (A)
Both-end mercapto group-containing urethane obtained by reacting the compound (F) represented by the general formula (1) with the urethane prepolymer (E-1) obtained by reacting the polyol (C) and the polyisocyanate (D). An aqueous composite resin dispersion obtained by polymerizing an ethylenically unsaturated monomer (G) using a urea resin (E-2) as a chain transfer agent.
General formula (1)
R is at least one divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide group. )
得られたアクリル・ウレタン複合樹脂(A)を高分子乳化剤として、水媒体中でエチレン性不飽和単量体(B)を重合する、水性複合樹脂分散体の製造方法。
一般式(1)
Rはアルキレン基、アリーレン基、およびアルキレンオキサイド基からなる群より選ばれる少なくとも一種の2価の基である。) Both-end mercapto group-containing urethane obtained by reacting the compound (F) represented by the general formula (1) with the urethane prepolymer (E-1) obtained by reacting the polyol (C) and the polyisocyanate (D). Using urea resin (E-2) as a chain transfer agent, polymerizing ethylenically unsaturated monomer (G),
A method for producing an aqueous composite resin dispersion, wherein the ethylenically unsaturated monomer (B) is polymerized in an aqueous medium using the obtained acrylic / urethane composite resin (A) as a polymer emulsifier.
General formula (1)
R is at least one divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide group. )
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016225428A JP6852361B2 (en) | 2016-11-18 | 2016-11-18 | Aqueous composite resin dispersion and its manufacturing method, water-based ink composition, printed matter |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016225428A JP6852361B2 (en) | 2016-11-18 | 2016-11-18 | Aqueous composite resin dispersion and its manufacturing method, water-based ink composition, printed matter |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2018080312A true JP2018080312A (en) | 2018-05-24 |
JP6852361B2 JP6852361B2 (en) | 2021-03-31 |
Family
ID=62198057
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2016225428A Active JP6852361B2 (en) | 2016-11-18 | 2016-11-18 | Aqueous composite resin dispersion and its manufacturing method, water-based ink composition, printed matter |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6852361B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020002257A (en) * | 2018-06-28 | 2020-01-09 | 星光Pmc株式会社 | Resin dispersion for inkjet ink, and water-based inkjet ink |
JP2021102741A (en) * | 2019-12-26 | 2021-07-15 | 東洋インキScホールディングス株式会社 | Resin composition and laminate |
WO2022196396A1 (en) * | 2021-03-16 | 2022-09-22 | 三菱ケミカル株式会社 | Aqueous resin dispersion, method for producing same, and ink containing said dispersion |
CN117304741A (en) * | 2023-09-26 | 2023-12-29 | 广东炎墨方案科技有限公司 | Solder resist ink for packaging substrate and preparation method thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0222302A (en) * | 1988-04-21 | 1990-01-25 | S C Johnson & Son Inc | Stable emulsion polymer and production thereof |
JPH03244611A (en) * | 1990-02-23 | 1991-10-31 | Toyo Ink Mfg Co Ltd | Aqueous resin composition |
JPH10204134A (en) * | 1997-01-24 | 1998-08-04 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition of water dispersion type |
JP2000345092A (en) * | 1998-09-22 | 2000-12-12 | Nippon Polyurethane Ind Co Ltd | Aqueous printing ink |
US20090020036A1 (en) * | 2007-07-17 | 2009-01-22 | Sivapackia Ganapathiappan | Compositions and methods for producing latexes containing urethanes |
JP2016155340A (en) * | 2015-02-26 | 2016-09-01 | 東洋インキScホールディングス株式会社 | Printing ink laminate |
-
2016
- 2016-11-18 JP JP2016225428A patent/JP6852361B2/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0222302A (en) * | 1988-04-21 | 1990-01-25 | S C Johnson & Son Inc | Stable emulsion polymer and production thereof |
JPH03244611A (en) * | 1990-02-23 | 1991-10-31 | Toyo Ink Mfg Co Ltd | Aqueous resin composition |
JPH10204134A (en) * | 1997-01-24 | 1998-08-04 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition of water dispersion type |
JP2000345092A (en) * | 1998-09-22 | 2000-12-12 | Nippon Polyurethane Ind Co Ltd | Aqueous printing ink |
US20090020036A1 (en) * | 2007-07-17 | 2009-01-22 | Sivapackia Ganapathiappan | Compositions and methods for producing latexes containing urethanes |
JP2016155340A (en) * | 2015-02-26 | 2016-09-01 | 東洋インキScホールディングス株式会社 | Printing ink laminate |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020002257A (en) * | 2018-06-28 | 2020-01-09 | 星光Pmc株式会社 | Resin dispersion for inkjet ink, and water-based inkjet ink |
JP7035850B2 (en) | 2018-06-28 | 2022-03-15 | 星光Pmc株式会社 | Resin dispersion for inkjet ink and water-based inkjet ink |
JP2021102741A (en) * | 2019-12-26 | 2021-07-15 | 東洋インキScホールディングス株式会社 | Resin composition and laminate |
JP7447484B2 (en) | 2019-12-26 | 2024-03-12 | artience株式会社 | Resin composition and laminate |
WO2022196396A1 (en) * | 2021-03-16 | 2022-09-22 | 三菱ケミカル株式会社 | Aqueous resin dispersion, method for producing same, and ink containing said dispersion |
CN117304741A (en) * | 2023-09-26 | 2023-12-29 | 广东炎墨方案科技有限公司 | Solder resist ink for packaging substrate and preparation method thereof |
CN117304741B (en) * | 2023-09-26 | 2024-03-29 | 广东炎墨方案科技有限公司 | Solder resist ink for packaging substrate and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
JP6852361B2 (en) | 2021-03-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6565356B2 (en) | Acrylic / urethane composite resin for water-based ink and water-based ink composition. | |
JP6680025B2 (en) | Acrylic / urethane composite resin for water-based adhesive, method for producing the same, and water-based adhesive. | |
JP6852361B2 (en) | Aqueous composite resin dispersion and its manufacturing method, water-based ink composition, printed matter | |
JP6065036B2 (en) | Printing ink laminate | |
JP6900668B2 (en) | Aqueous composite resin and its manufacturing method | |
WO2011010719A1 (en) | Aqueous polyurethane resin dispersion and method for producing the same | |
JPH093400A (en) | Two-pack water-born crosslinkable polyurethane/acrylate mixed system | |
JP6668857B2 (en) | Laminated body and method for manufacturing the same | |
JP6330603B2 (en) | Water-based ink resin composition and water-based ink composition | |
KR20070120173A (en) | Two-component curable aqueous urethane-alkyd resin composition and use thereof | |
EP2338922B1 (en) | Low voc aqueous compositions of acrylic-urethane block copolymers | |
CN110352204B (en) | Aqueous coating composition | |
US10047479B2 (en) | Printing agent, printed fabric, and method for producing printing agent | |
JP6142721B2 (en) | Binder resin composition for water-based ink and water-based ink composition | |
JP6149586B2 (en) | Core-shell type resin fine particle dispersion for water-based ink and water-based ink composition | |
JP2009143969A (en) | Water-based reactive resin and its manufacturing method | |
JP2018131548A (en) | Water-based flexo ink | |
JP6809160B2 (en) | Water-based composite resin and its manufacturing method, water-based ink composition, printed matter | |
JP6168080B2 (en) | Printing ink laminate | |
JP2020019853A (en) | Aqueous composite resin, and coating agent for exterior | |
JPH1036767A (en) | Two pack type aqueous coating composition | |
JP3598623B2 (en) | Method for producing aqueous urethane compound | |
JP4826688B2 (en) | Method for producing polyurethane resin aqueous dispersion | |
JP2017145350A (en) | Pigment dispersion, and laminate | |
JP7255135B2 (en) | An aqueous composite resin and an exterior coating agent containing the same. |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20190710 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20200610 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200630 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200804 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20201006 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20201201 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20210209 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210222 |
|
R151 | Written notification of patent or utility model registration |
Ref document number: 6852361 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |