JPH0122314B2 - - Google Patents
Info
- Publication number
- JPH0122314B2 JPH0122314B2 JP59056281A JP5628184A JPH0122314B2 JP H0122314 B2 JPH0122314 B2 JP H0122314B2 JP 59056281 A JP59056281 A JP 59056281A JP 5628184 A JP5628184 A JP 5628184A JP H0122314 B2 JPH0122314 B2 JP H0122314B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- polymer
- parts
- gram
- sulfonic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- 229920000642 polymer Polymers 0.000 claims description 43
- 229920003169 water-soluble polymer Polymers 0.000 claims description 29
- 239000000981 basic dye Substances 0.000 claims description 24
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000000976 ink Substances 0.000 description 42
- 239000000178 monomer Substances 0.000 description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 239000000975 dye Substances 0.000 description 12
- 238000004043 dyeing Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- 239000003086 colorant Substances 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000980 acid dye Substances 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 description 2
- 239000000982 direct dye Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- ZOMLUNRKXJYKPD-UHFFFAOYSA-N 1,3,3-trimethyl-2-[2-(2-methylindol-3-ylidene)ethylidene]indole;hydrochloride Chemical compound [Cl-].C1=CC=C2C(C)(C)C(/C=C/C=3C4=CC=CC=C4NC=3C)=[N+](C)C2=C1 ZOMLUNRKXJYKPD-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- CBQFBEBEBCHTBK-UHFFFAOYSA-N 1-phenylprop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)C(C=C)C1=CC=CC=C1 CBQFBEBEBCHTBK-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- QAMCXJOYXRSXDU-UHFFFAOYSA-N 2,4-dimethoxy-n-[2-(1,3,3-trimethylindol-1-ium-2-yl)ethenyl]aniline;chloride Chemical compound [Cl-].COC1=CC(OC)=CC=C1NC=CC1=[N+](C)C2=CC=CC=C2C1(C)C QAMCXJOYXRSXDU-UHFFFAOYSA-N 0.000 description 1
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 description 1
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 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
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- GQTFHSAAODFMHB-UHFFFAOYSA-N 2-prop-2-enoyloxyethanesulfonic acid Chemical compound OS(=O)(=O)CCOC(=O)C=C GQTFHSAAODFMHB-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-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
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- RFQSMLBZXQOMKK-UHFFFAOYSA-N [3-[(4,8-diamino-6-bromo-1,5-dioxonaphthalen-2-yl)amino]phenyl]-trimethylazanium;chloride Chemical compound [Cl-].C[N+](C)(C)C1=CC=CC(NC=2C(C3=C(N)C=C(Br)C(=O)C3=C(N)C=2)=O)=C1 RFQSMLBZXQOMKK-UHFFFAOYSA-N 0.000 description 1
- GRPFBMKYXAYEJM-UHFFFAOYSA-M [4-[(2-chlorophenyl)-[4-(dimethylamino)phenyl]methylidene]cyclohexa-2,5-dien-1-ylidene]-dimethylazanium;chloride Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C(=CC=CC=1)Cl)=C1C=CC(=[N+](C)C)C=C1 GRPFBMKYXAYEJM-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- VJDDAARZIFHSQY-UHFFFAOYSA-N basic black 2 Chemical compound [Cl-].C=1C2=[N+](C=3C=CC=CC=3)C3=CC(N(CC)CC)=CC=C3N=C2C=CC=1NN=C1C=CC(=O)C=C1 VJDDAARZIFHSQY-UHFFFAOYSA-N 0.000 description 1
- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- BOOMOFPAGCSKKE-UHFFFAOYSA-N butane-2-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCC(C)S(O)(=O)=O BOOMOFPAGCSKKE-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- ABMDIECEEGFXNC-UHFFFAOYSA-N n-ethylpropanamide Chemical compound CCNC(=O)CC ABMDIECEEGFXNC-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 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
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000003755 preservative agent Substances 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
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- -1 richer colors Chemical compound 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- NWKBFCIAPOSTKG-UHFFFAOYSA-M trimethyl-[3-[(3-methyl-5-oxo-1-phenyl-4h-pyrazol-4-yl)diazenyl]phenyl]azanium;chloride Chemical compound [Cl-].CC1=NN(C=2C=CC=CC=2)C(=O)C1N=NC1=CC=CC([N+](C)(C)C)=C1 NWKBFCIAPOSTKG-UHFFFAOYSA-M 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明は、着色されたポリマーを基材とする水
性インク組成物に関する。さらに詳しくは、ポリ
マー中にヒドロキシル基とスルホン酸基を含有し
た水溶性ポリマーを塩基性染料で染色した着色ポ
リマーと水溶性有機溶剤とからなる水性インク組
成物に関するものである。
従来、水性染料、例えば直接染料、酸性染料お
よび塩基性染料等を水に溶解し、湿潤剤、防腐剤
等を添加した水性インクが知られているが、この
様な従来の水性インクは水性染料であるため記録
されたインクが、水や湿つたものに接触すると簡
単に溶け出し、印刷部位が滲んで汚れたり、不鮮
明となり、耐水性が悪いという欠点を有してい
た。
また、塩基性染料を使用した水性インクは、直
接染料および酸性染料を使用した水性インクに比
べ、色の豊富さ、色の鮮明さ、あるいは重量単位
当り濃い色を呈する等の優れた利点を有する反
面、耐光性が悪い、溶解性に限度があるという欠
点があり使用範囲が著しく限定されていた。
本発明者は、上記の水性染料を使用した水性イ
ンクの耐水性および塩基性染料の耐光性、溶解性
の欠点を解消し、優れたインク組成物を提供する
目的で研究した結果、ポリマー中にヒドロキシル
基とスルホン酸基を含有した水溶性ポリマーを塩
基性染料で染色した着色ポリマーと水溶性有機溶
剤とからなる水性インク組成物が耐水性、耐光性
および溶解性に優れていることを見い出し、本発
明を完成した。
すなわち、本発明は、1×10-3グラム当量/グ
ラムポリマー以上のヒドロキシル基および1×
10-4グラム当量/グラムポリマー以上のスルホン
酸基を含有する水溶性ポリマーが塩基性染料によ
つて染色されて水不溶性となつている着色ポリマ
ーの、水と水溶性有機溶剤との混合溶剤溶液から
なる水性インク組成物、を要旨とするものであ
る。
本発明は、ポリマー中にヒドロキシル基とスル
ホン酸基を含有した水溶性ポリマーを一般に行わ
れている染色方法により、塩基性染料で染色して
いくと、水不溶性の着色ポリマーが得られる。こ
の着色ポリマーを水に溶解する目的で水溶性有機
溶剤を、染色前あるいは染色後に加えることで基
本的に達成できる。
本発明の着色ポリマーが何故、水に不溶なの
か、理論的に定かでないが、水溶性ポリマー中の
スルホン酸基と塩基性染料とがイオン結合して疎
水化され、スルホン酸基の大部分を塩基性染料と
イオン結合させた時、水不溶性の着色ポリマーに
なるものと推考される。一方、得られた着色ポリ
マーは、ポリマー中にヒドロキシル基とイオン結
合基を有しているため、水との親和性に優れてお
り、水不溶性であつても、比較的少量の水溶性有
機溶剤で水に溶解することができるものと推考さ
れる。もつとも、水不溶性のポリマーを塩基性染
料によつて染色したものを、少量の水溶性有機溶
剤で水に溶解させることはできない。
これらのことから、本発明の水性インク組成物
は、水不溶性の着色ポリマーが基材であるため耐
水性に優れ、しかも塩基性染料がポリマー中のス
ルホン酸基とイオン結合しているので、耐光性お
よび溶解性に優れているものと考えられる。さら
にポリマー中のスルホン酸基の含有量を増すこと
により、従来では得られなかつた量の塩基性染料
が染着でき、濃い色の水性インクが得られる。
本発明で使用されるヒドロキシル基とスルホン
酸基を含有した水溶性ポリマーは、あらかじめ製
造したポリマーに後からヒドロキシル基、スルホ
ン酸基を導入する方法も採用されるが、一般には
操作的に簡単な、ヒドロキシル基を含有するラジ
カル重合可能なビニルモノマーとスルホン酸基を
含有するラジカル重合可能なビニルモノマーおよ
び/または、これらモノマーと他のラジカル重合
可能なビニルモノマーを重合して得る方法が採用
される。
ヒドロキシル基を含有するラジカル重合可能な
ビニルモノマーとしては、例えばヒドロキシエチ
ルアクリレート、ヒドロキシプロピルアクリレー
ト、ヒドロキシエチルメタクリレート、ヒドロキ
シプロピルメタクリレート、ポリエチレングリコ
ールモノメタクリレート、メチロールアクリアミ
ド、メチロールメタクリルアミドなどを挙げるこ
とができる。
また、スルホン酸基を含有するラジカル重合可
能なビニルモノマーとしては、例えばビニルスル
ホン酸、アリルスルホン酸、メタリルスルホン
酸、アクリルアミドメチルプロパンスルホン酸、
スチレンスルホン酸、ビニルベンジルスルホン
酸、アクロイルオキシエチルスルホン酸、メタク
ロイルオキシエチルスルホン酸等の不飽和スルホ
ン酸およびこれらの塩、例えばリチウム塩、ナト
リウム塩、カリウム塩、アンモニウム塩等が挙げ
ることができる。
さらに上記のヒドロキシル基、スルホン酸基を
含有するモノマーとラジカル重合可能な他のビニ
ルモノマーとしては、アクリルアミド、メタクリ
ルアミド、アミノエチルアクリレート、アミノエ
チルメタクリレート等の親水性ビニルモノマーと
メチルアクリレート、エチルアクリレート、プロ
ピルアクリレート、ブチルアクリレート、メチル
メタクリレート、エチルメタクリレート、プロピ
ルメタクリレート、ブチルメタクリレート、酢酸
ビニル、アクリロニトリル、メタクリロニトリ
ル、スチレン等の疎水性ビニルモノマーを挙げる
ことができるが、疎水性モノマーを用いた場合で
も得られたポリマーが水溶性であるような組成に
しなければならない。
次に、これらモノマーを重合して水溶性ポリマ
ーを得る重合方法であるが、例えば、水等の溶媒
中において、100℃以下の重合温度で通常のラジ
カル重合開始剤と共に、各モノマーを一括あるい
は部分的または連続的に重合容器に導入する事で
容易に実施できる。
使用されるラジカル重合開始剤は、例えば過硫
酸カリウム、過硫酸アンモニウム等の過硫酸塩、
あるいはキユメンハイドロペルオキシド、t―ブ
チルハイドロペルオキシドのような有機過酸化物
等が使用できる。また、酸性亜硫酸塩、硫酸第一
鉄等の還元剤と組み合せて使用するレドツクス系
開始剤も使用できる。
得られる水溶性ポリマーの分子量は、重合系に
存在する各モノマーの濃度、ラジカル重合開始剤
の使用量、重合温度等によつて左右される。
モノマーの濃度は、任意に選択できるが一般的
に5〜50%で実施できる。高濃度での重合は、重
合系の粘度が高くなり重合熱の除去も困難となり
好ましくない。また、低濃度の重合は、経済的な
理由から好ましくない。ラジカル重合開始剤の使
用量は、多くすると水溶性ポリマーの分子量が小
さくなる傾向を示し、少なくすると水溶性ポリマ
ーの分子量は大きくなる傾向を示す。
かくして得られたヒドロキシル基とスルホン酸
基を含有する水溶性ポリマーの分子量は、水性イ
ンクの粘度に影響を与えるため重要な因子となる
が、平均分子量は5×105以下、好ましくは1×
105以下であればよい。
本発明において、上記の重合方法等によつて得
られた水溶性ポリマー中に含有するヒドロキシル
基、およびスルホン酸基の量は、インクの耐水
性、耐光性、溶解性および粘度安定性等から、ヒ
ドロキシル基は少なくとも1×10-3グラム当量/
グラムポリマー以上、好ましくは3×10-3グラム
当量/グラムポリマー以上、またスルホン酸基の
含有量は1×10-4グラム当量/グラムポリマー以
上、実質的には2×10-4グラム当量/グラムポリ
マー以上、3×10-3グラム当量/グラムポリマー
以下含有されておれば、本発明の水性インク組成
物の基材として満足する物性を得ることができ
る。ヒドロキシル基の含有量が少ないと、水溶性
有機溶剤の使用量が多くなりインクの滲み、裏移
り等の問題が起り好ましくない。一方、スルホン
酸基の含有量は、少ないとインク濃度が低くなる
ばかりか、インクの粘度安定性も悪くなる。ま
た、多過ぎるとインクの耐光性が悪くなり好まし
くない。
本発明の目的からして、かかる水溶性ポリマー
を得る方法は、本発明の趣旨から限定されるもの
ではない。
次に、得られたヒドロキシル基とスルホン酸基
を含有する水溶性ポリマーを染色する塩基性染料
としては、通常のトリフエニルメタン系、アゾ
系、メチン系、オキサジン系およびアンスラキノ
ン系等で知られている染料で、染料便覧(有機合
成化学協会編、株式会社丸善発行)に分類されて
いる塩基性染料およびカチオン染料が使用され
る。すなわち、本明細書における「塩基性染料」
とは、カチオン染料をも意味する広義のものであ
る。
例えば、黄色系では
C.I.(Color Indexの略)ベーシツクイエロー 11
C.I.ベーシツクイエ
ロー 13
C.I.ベーシツクイエ
ロー 14
〃 19 〃 21
〃 25 〃 28
〃 32 〃 36
〃 67 〃 73
等が挙げられる。
例えば、オレンジ色系では
C.I.ベーシツクオレ
ンジ 15
C.I.ベーシツクオレ
ンジ 21
〃 22 〃 32
〃 33 〃 34
等が挙げられる。
例えば、赤色系では
C.I.ベーシツクレツ
ド 9
C.I.ベーシツクレツ
ド 13
〃 14 〃 15
〃 18 〃 23
〃 24 〃 27
〃 29 〃 36
〃 38 〃 46
C.I.ベーシツクバイ
オレツト 1
C.I.ベーシツクバイ
オレツト 3
〃 10 〃 14
〃 15 〃 21
〃 25 〃 27
〃 28
等があげられる。
例えば、青色系では
C.I.ベーシツクブル
ー 1
C.I.ベーシツクブル
ー 3
〃 5 〃 7
〃 9 〃 21
〃 22 〃 25
〃 26 〃 41
〃 44 〃 45
〃 47 〃 64
〃 65 〃 129
等が挙げられる。
例えば、縁色系では
C.I.ベーシツクグリ
ーン 1
C.I.ベーシツクグリ
ーン 4
〃 6
等が挙げられる。
例えば、黒色では
C.I.ベーシツクブラ
ツク 2
C.I.ベーシツクブラ
ツク 8
等が挙げられる。
かかる塩基性染料は、水溶性ポリマーのスルホ
ン酸基とイオン結合により染着され、着色ポリマ
ーを与える。染料を染着させるための染色方法
は、ヒドロキシル基とスルホン酸基を含有した水
溶性ポリマーを蟻酸、酢酸、酪酸、酒石酸、リン
ゴ酸のような有機酸、あるいは塩酸、硫酸のよう
な無機酸、または水酸化ナトリウム、炭酸ナトリ
ウム等の水溶液を用いてPH2〜7の範囲に調節し
た後、染料溶液を添加することで実施できる。ま
た、この際に例えば、下記一般式〔〕や〔〕
で示される水溶性有機溶剤を染色前あるいは染色
後に添加することにより本発明の水性インク組成
物を得ることができる。
一般式〔〕
The present invention relates to colored polymer-based aqueous ink compositions. More specifically, the present invention relates to an aqueous ink composition comprising a colored polymer obtained by dyeing a water-soluble polymer containing a hydroxyl group and a sulfonic acid group with a basic dye and a water-soluble organic solvent. Conventionally, water-based inks have been known in which water-based dyes, such as direct dyes, acid dyes, and basic dyes, are dissolved in water, and wetting agents, preservatives, etc. are added. Therefore, the recorded ink easily dissolves when it comes into contact with water or a damp object, causing the printed area to smear and become smudged or unclear, and has the drawback of poor water resistance. In addition, water-based inks using basic dyes have superior advantages over water-based inks using direct dyes and acid dyes, such as richer colors, more vivid colors, and a darker color per unit of weight. On the other hand, it has drawbacks such as poor light resistance and limited solubility, and its range of use is extremely limited. As a result of research aimed at providing an excellent ink composition by eliminating the drawbacks of the water resistance of water-based inks using the above-mentioned water-based dyes and the light resistance and solubility of basic dyes, the present inventors found that We have discovered that an aqueous ink composition consisting of a colored polymer obtained by dyeing a water-soluble polymer containing hydroxyl groups and sulfonic acid groups with a basic dye and a water-soluble organic solvent has excellent water resistance, light resistance, and solubility. The invention has been completed. That is, the present invention provides hydroxyl groups greater than or equal to 1 x 10 -3 gram equivalents/gram polymer and 1 x
A mixed solvent solution of water and a water-soluble organic solvent of a colored polymer containing sulfonic acid groups of 10 -4 gram equivalent/gram polymer or more and dyed with a basic dye to become water-insoluble. The gist is an aqueous ink composition comprising: In the present invention, a water-insoluble colored polymer is obtained by dyeing a water-soluble polymer containing a hydroxyl group and a sulfonic acid group with a basic dye using a commonly used dyeing method. This can basically be achieved by adding a water-soluble organic solvent before or after dyeing to dissolve the colored polymer in water. It is not theoretically clear why the colored polymer of the present invention is insoluble in water, but the sulfonic acid groups in the water-soluble polymer and the basic dye are ionicly bonded to become hydrophobic, and most of the sulfonic acid groups are It is thought that when ionically bonded with a basic dye, it becomes a water-insoluble colored polymer. On the other hand, the obtained colored polymer has a hydroxyl group and an ionic bonding group in the polymer, so it has excellent affinity with water, and even if it is water-insoluble, it can be used in a relatively small amount of water-soluble organic solvent. It is assumed that it can be dissolved in water. However, a water-insoluble polymer dyed with a basic dye cannot be dissolved in water using a small amount of a water-soluble organic solvent. Based on these facts, the aqueous ink composition of the present invention has excellent water resistance because it uses a water-insoluble colored polymer as a base material, and also has excellent light resistance because the basic dye is ionically bonded to the sulfonic acid group in the polymer. It is considered to have excellent properties and solubility. Furthermore, by increasing the content of sulfonic acid groups in the polymer, it is possible to dye with a basic dye in an amount that could not be obtained conventionally, and a deep-colored aqueous ink can be obtained. For the water-soluble polymer containing hydroxyl groups and sulfonic acid groups used in the present invention, a method of introducing hydroxyl groups and sulfonic acid groups into a pre-produced polymer is also adopted, but in general, a method that is easy to operate is adopted. , a method is employed in which a radically polymerizable vinyl monomer containing a hydroxyl group and a radically polymerizable vinyl monomer containing a sulfonic acid group are polymerized, and/or these monomers and other radically polymerizable vinyl monomers are polymerized. . Examples of the radically polymerizable vinyl monomer containing a hydroxyl group include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, methylol acrylamide, and methylol methacrylamide. Examples of radically polymerizable vinyl monomers containing sulfonic acid groups include vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, acrylamide methylpropanesulfonic acid,
Examples include unsaturated sulfonic acids such as styrene sulfonic acid, vinylbenzyl sulfonic acid, acroyloxyethyl sulfonic acid, methacroyloxyethyl sulfonic acid, and salts thereof, such as lithium salts, sodium salts, potassium salts, ammonium salts, etc. can. Furthermore, other vinyl monomers that can be radically polymerized with the above-mentioned hydroxyl group- and sulfonic acid group-containing monomers include hydrophilic vinyl monomers such as acrylamide, methacrylamide, aminoethyl acrylate, aminoethyl methacrylate, methyl acrylate, ethyl acrylate, Examples include hydrophobic vinyl monomers such as propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, vinyl acetate, acrylonitrile, methacrylonitrile, and styrene; The composition must be such that the polymer obtained is water soluble. Next, these monomers are polymerized to obtain a water-soluble polymer. For example, in a solvent such as water, at a polymerization temperature of 100°C or less, each monomer is combined in bulk or in portions with a normal radical polymerization initiator. This can be easily carried out by introducing the polymer into the polymerization vessel either selectively or continuously. Examples of the radical polymerization initiator used include persulfates such as potassium persulfate and ammonium persulfate;
Alternatively, organic peroxides such as kyumene hydroperoxide and t-butyl hydroperoxide can be used. Further, redox initiators used in combination with reducing agents such as acidic sulfites and ferrous sulfates can also be used. The molecular weight of the resulting water-soluble polymer depends on the concentration of each monomer present in the polymerization system, the amount of radical polymerization initiator used, the polymerization temperature, and the like. The monomer concentration can be selected arbitrarily, but it can generally be carried out at 5 to 50%. Polymerization at a high concentration is not preferred because the viscosity of the polymerization system increases and it becomes difficult to remove the heat of polymerization. Furthermore, polymerization at low concentrations is not preferred for economic reasons. When the amount of the radical polymerization initiator used is increased, the molecular weight of the water-soluble polymer tends to decrease, and when it is decreased, the molecular weight of the water-soluble polymer tends to increase. The molecular weight of the thus obtained water-soluble polymer containing hydroxyl groups and sulfonic acid groups is an important factor as it affects the viscosity of the aqueous ink, and the average molecular weight is 5×10 5 or less, preferably 1×
It should be 10 5 or less. In the present invention, the amount of hydroxyl groups and sulfonic acid groups contained in the water-soluble polymer obtained by the above polymerization method etc. is determined based on the water resistance, light resistance, solubility, viscosity stability, etc. of the ink. The hydroxyl group is at least 1×10 -3 gram equivalent/
gram polymer or more, preferably 3×10 −3 gram equivalent/gram polymer or more, and the content of sulfonic acid groups is 1×10 −4 gram equivalent/gram polymer or more, substantially 2×10 −4 gram equivalent/gram polymer. If it is contained in an amount of gram polymer or more and 3×10 -3 gram equivalent/gram polymer or less, satisfactory physical properties can be obtained as a base material for the aqueous ink composition of the present invention. If the content of hydroxyl groups is low, the amount of water-soluble organic solvent used will be large, causing problems such as ink bleeding and set-off, which is not preferable. On the other hand, if the content of sulfonic acid groups is low, not only the ink concentration will be low but also the viscosity stability of the ink will be poor. On the other hand, if the amount is too large, the light resistance of the ink deteriorates, which is not preferable. For the purpose of the present invention, the method of obtaining such a water-soluble polymer is not limited. Next, as basic dyes for dyeing the obtained water-soluble polymer containing hydroxyl groups and sulfonic acid groups, conventional triphenylmethane-based, azo-based, methine-based, oxazine-based, and anthraquinone-based dyes are known. The basic dyes and cationic dyes classified in the Dye Handbook (edited by the Organic Synthetic Chemistry Association, published by Maruzen Co., Ltd.) are used. That is, the "basic dye" in this specification
In a broad sense, it also means cationic dyes. For example, for yellow colors, CI (abbreviation for Color Index) Basic Yellow 11 CI Basic Yellow 13 CI Basic Yellow 14 〃 19 〃 21 〃 25 〃 28 〃 32 〃 36 〃 67 〃 73 etc. For example, examples of orange colors include CI Basic Orange 15 CI Basic Orange 21 〃 22 〃 32 〃 33 〃 34. For example, for red colors, CI Basic Cred 9 CI Basic Cred 13 〃 14 〃 15 〃 18 〃 23 〃 24 〃 27 〃 29 〃 36 〃 38 〃 46 CI Basic Violet 1 CI Basic Violet 3 〃 10 〃 14 〃 15 〃 21 〃 25 〃 27 〃 28 etc. For example, in blue colors, CI Basic Blue 1 CI Basic Blue 3 5 7 9 21 22 25 26 41 44 45 47 64 65 129, etc. For example, in the border color system, CI Basic Green 1 CI Basic Green 4 〃 6 etc. For example, for black, CI Basic Black 2 CI Basic Black 8 etc. are available. Such basic dyes are dyed through ionic bonds with sulfonic acid groups of water-soluble polymers to give colored polymers. The dyeing method is to dye a water-soluble polymer containing hydroxyl groups and sulfonic acid groups with an organic acid such as formic acid, acetic acid, butyric acid, tartaric acid, or malic acid, or with an inorganic acid such as hydrochloric acid or sulfuric acid. Alternatively, it can be carried out by adjusting the pH to a range of 2 to 7 using an aqueous solution of sodium hydroxide, sodium carbonate, etc., and then adding a dye solution. In addition, at this time, for example, the following general formula [] or []
The aqueous ink composition of the present invention can be obtained by adding the water-soluble organic solvent represented by the formula before or after dyeing. General formula []
【式】
(R1はHまたはCH3を;R2およびR3はいずれ
もH,CH3またはC2H5を表す。)
一般式〔〕[Formula] (R 1 represents H or CH 3 ; R 2 and R 3 both represent H, CH 3 or C 2 H 5. ) General formula []
【式】
(R4はHまたはCH3を;XはNH,NCH3また
はOを;YはCH2またはOを表す。)
一般式〔〕で表わされる水溶性有機溶剤とし
ては、例えばホルムアミド、N―メチルホルムア
ミド、N,N′―ジメチルホルムアミド、N,
N′―ジエチルホルムアミド、アセトアミド、N
―メチルアセトアミド等が挙げられる。
一般式〔〕で表わされる水溶性有機溶剤とし
ては、例えばエチレンカーボネート、プロピレン
カーボネート、γ―ブチロラクトン、γ―メチル
ブチロラクトン、2―ピロリドン、N―メチル―
2―ピロリドン、1,3―ジメチルイミダゾリジ
ノン等が挙げられる。水溶性有機溶剤の使用量は
通常5〜50wt%、好ましくは10〜40wt%でよい。
水溶性有機溶剤の使用量が多いと、インクの滲
み、裏移り等の問題が起り、好ましくない。
本発明の目的からして、かかる染色方法は本発
明の趣旨から限定されるものではない。
本発明の水性インク組成物は、それ自体でも水
性インクとして使用できるが、必要に応じて通
常、水性インクに使用されている補助剤、例えば
エチレングリコール、プロピレングリコール、ジ
エチレングリコール、ポリエチレングリコール、
グリセリン、トリエタノールアミンのような湿潤
剤、フエノール、パラオキシ安息香酸アルキルエ
ステル、ナトリウムオマジン、ジオキシンのよう
な防カビ、防菌剤あるいは防錆剤、界面活性剤等
を添加することもできる。
このようにして得られた本発明の水性インク組
成物は、次のような特徴を有する。
第一に水不溶性の着色ポリマーを基材としてい
るため耐水性に優れている点である。したがつて
インクが水や汗等によつて滲みを生じたり、印刷
部位が消失したりするような従来の水性インクの
欠点が解消されるのである。
第二に耐光性および溶解性が低いとされていた
塩性染料の欠点が、水溶性ポリマーに塩基性染料
を染着することにより、解消されるようになつ
た。すなわち、塩基性染料の色の豊富さ、色の鮮
明さあるいは重量単位当り濃い色を呈する等の塩
基性染料の特徴を持ち、かつ耐光性、溶解性に優
れた水性インクが提供されることにある。
以下実施例を示し本発明をさらに具体的に説明
するが、本発明は、これらの実施例によつて何ら
限定されるものではない。なお、実施例中の部お
よび組成に係わる%は重量基準を示す。
水溶性ポリマー合成例 1
窒素置換した重合フラスコに水40部を仕込み90
℃に昇温した。スピノマーNaSS(P―スチレン
スルホン酸ナトリウム 純度81.0%東洋曹達工業
製)56部,2―ヒドロキシエチルメタクリレート
116部を水488部に溶解してモノマー水溶液を調製
した。
過硫酸アンモニウム3部を水97部に溶解して重
合開始剤水溶液を調整した。
モノマー水溶液と重合開始剤水溶液とを3時間
で添加して90℃で重合した。さらに90℃で2時間
重合して冷却した。25℃での溶液粘度は32cpsで
あつた。
未反応モノマーを臭素付加法により定量したと
ころ、モノマーの重合率は、99.1%であつた。ま
た、ゲルパーミツシンクロマトグラフイー法によ
りポリマーの平均分子量を求めたところ、w3
×104であつた。
ポリマーを精製して、イオウの分析値からポリ
マー中には1.70×10-3グラム当量/グラムポリマ
ーのスルホン酸基が含有されており、モノマー仕
込み量よりの計算値と同じであつた。同様にヒド
ロキシル基の含有量は5.6×10-3グラム当量/グ
ラムポリマーである。
水溶性ポリマー合成例 2
窒素置換した重合フラスコに水50部を仕込み90
℃に昇温した。スピノマーNaSS(P―スチレン
スルホン酸ナトリウム 純度81.9%東洋曹達工業
製)73部、2―ヒドロキシエチルメタクリレート
122部、2―ヒドロキシエチルアクリレート122部
を水603部に溶解してモノマー水溶液を調整した。
過硫酸アンモニウム24部を水56部に溶解して重
合開始剤水溶液を調整した。
モノマー水溶液と重合開始剤水溶液とを3時間
で添加して90℃で重合した。さらに90℃2時間重
合して冷却した。25℃での溶液粘度は、255cpsで
あつた。
合成例―1と同様にしてモノマーの重合率は
99.5%であり平均分子量w1×104であつた。ま
た、ポリマー中のスルホン酸基は9×10-4グラム
当量/グラムポリマー、ヒドロキシル基は6.6×
10-3グラム当量/グラムポリマーであつた。
水溶性ポリマー合成例 3
窒素置換した重合フラスコに水50部を仕込み90
℃に昇温した。スピノマーNaSS(P―スチレン
スルホン酸ナトリウム 純度81.9%東洋曹達工業
製)117部、2―ヒドロキシエチルメタクリレー
ト106部、アクリルアミド40部を水657部に溶解し
てモノマー水溶液を調整した。
過硫酸アンモニウム19部を水61部に溶解して重
合開始剤水溶液を調整した。
モノマー水溶液と重合開始剤水溶液とを3時間
で添加して90℃で重合した。さらに90℃で2時間
重合して冷却した。25℃での溶液粘度は65cpsで
あつた。
合成例―1と同様にしてモノマーの重合率は
99.3%であり、平均分子量はw=1×104であ
つた。また、ポリマー中のスルホン酸基は1.9×
10-3グラム当量/グラムポリマー、ヒドロキシル
基は3.4×10-3グラム当量/グラムポリマーであ
つた。
実施例 1〜3
水溶性ポリマー合成例―1で得られた水溶性ポ
リマー25部に塩基性染料(保土谷化学製)3部,
酢酸1部を水51部に溶解させて添加し、60℃で1
時間撹拌し着色ポリマーをつくり、これにγ―ブ
チロラクトン20部を加えて水性インクを調整し
た。[Formula] (R 4 represents H or CH 3 ; X represents NH, NCH 3 or O; Y represents CH 2 or O.) Examples of the water-soluble organic solvent represented by the general formula [] include formamide, N-methylformamide, N,N'-dimethylformamide, N,
N'-diethylformamide, acetamide, N
- Examples include methylacetamide. Examples of the water-soluble organic solvent represented by the general formula [] include ethylene carbonate, propylene carbonate, γ-butyrolactone, γ-methylbutyrolactone, 2-pyrrolidone, N-methyl-
Examples include 2-pyrrolidone and 1,3-dimethylimidazolidinone. The amount of water-soluble organic solvent used is usually 5 to 50 wt%, preferably 10 to 40 wt%.
If the amount of water-soluble organic solvent used is large, problems such as ink bleeding and set-off may occur, which is not preferable. For the purposes of the present invention, such dyeing methods are not limited. The aqueous ink composition of the present invention can be used as an aqueous ink by itself, but if necessary, adjuvants commonly used in aqueous inks may be added, such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, etc.
Wetting agents such as glycerin and triethanolamine, phenols, paraoxybenzoic acid alkyl esters, sodium omazine, antifungal agents or rust inhibitors such as dioxin, surfactants, and the like can also be added. The aqueous ink composition of the present invention thus obtained has the following characteristics. First, it has excellent water resistance because it is based on a water-insoluble colored polymer. Therefore, the drawbacks of conventional water-based inks, such as ink smearing due to water, sweat, etc., and printed areas disappearing, are eliminated. Second, the disadvantages of salt dyes, which were thought to have low light resistance and solubility, have been overcome by dyeing water-soluble polymers with basic dyes. In other words, it is possible to provide a water-based ink that has the characteristics of a basic dye, such as the richness of colors, the vividness of the color, or the appearance of a deep color per weight unit, and has excellent light resistance and solubility. be. EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited by these Examples. Note that parts and percentages in the examples are based on weight. Water-soluble polymer synthesis example 1 Add 40 parts of water to a nitrogen-substituted polymerization flask and add 90 parts of water.
The temperature was raised to ℃. Spinomer NaSS (sodium P-styrene sulfonate purity 81.0% manufactured by Toyo Soda Kogyo) 56 parts, 2-hydroxyethyl methacrylate
A monomer aqueous solution was prepared by dissolving 116 parts in 488 parts of water. A polymerization initiator aqueous solution was prepared by dissolving 3 parts of ammonium persulfate in 97 parts of water. A monomer aqueous solution and a polymerization initiator aqueous solution were added over 3 hours and polymerized at 90°C. The mixture was further polymerized at 90° C. for 2 hours and cooled. The solution viscosity at 25°C was 32 cps. When the amount of unreacted monomer was determined by the bromine addition method, the polymerization rate of the monomer was 99.1%. In addition, when the average molecular weight of the polymer was determined using the gel permits chromatography method, w3
It was ×10 4 . The polymer was purified, and the sulfur analysis revealed that the polymer contained 1.70×10 -3 gram equivalent/gram polymer of sulfonic acid groups, which was the same as the calculated value from the amount of monomer charged. Similarly, the content of hydroxyl groups is 5.6 x 10 -3 gram equivalents/gram polymer. Water-soluble polymer synthesis example 2 Pour 50 parts of water into a nitrogen-substituted polymerization flask and add 90 parts of water.
The temperature was raised to ℃. Spinomer NaSS (sodium P-styrene sulfonate purity 81.9% manufactured by Toyo Soda Kogyo) 73 parts, 2-hydroxyethyl methacrylate
A monomer aqueous solution was prepared by dissolving 122 parts of 2-hydroxyethyl acrylate in 603 parts of water. A polymerization initiator aqueous solution was prepared by dissolving 24 parts of ammonium persulfate in 56 parts of water. A monomer aqueous solution and a polymerization initiator aqueous solution were added over 3 hours and polymerized at 90°C. The mixture was further polymerized at 90°C for 2 hours and cooled. The solution viscosity at 25°C was 255 cps. In the same manner as Synthesis Example-1, the polymerization rate of the monomer is
99.5%, and the average molecular weight was w1×10 4 . In addition, the sulfonic acid group in the polymer is 9×10 -4 gram equivalent/gram polymer, and the hydroxyl group is 6.6×
It was 10 -3 gram equivalent/gram polymer. Water-soluble polymer synthesis example 3 Pour 50 parts of water into a nitrogen-substituted polymerization flask and add 90 parts of water.
The temperature was raised to ℃. A monomer aqueous solution was prepared by dissolving 117 parts of spinomer NaSS (sodium P-styrene sulfonate, purity 81.9%, manufactured by Toyo Soda Kogyo Co., Ltd.), 106 parts of 2-hydroxyethyl methacrylate, and 40 parts of acrylamide in 657 parts of water. A polymerization initiator aqueous solution was prepared by dissolving 19 parts of ammonium persulfate in 61 parts of water. A monomer aqueous solution and a polymerization initiator aqueous solution were added over 3 hours and polymerized at 90°C. The mixture was further polymerized at 90° C. for 2 hours and cooled. The solution viscosity at 25°C was 65 cps. In the same manner as Synthesis Example-1, the polymerization rate of the monomer is
99.3%, and the average molecular weight was w=1×10 4 . In addition, the sulfonic acid group in the polymer is 1.9×
10 −3 gram equivalents/gram polymer, the hydroxyl groups were 3.4×10 −3 gram equivalents/gram polymer. Examples 1 to 3 25 parts of the water-soluble polymer obtained in Water-soluble polymer synthesis example-1, 3 parts of basic dye (manufactured by Hodogaya Chemical),
1 part of acetic acid was dissolved in 51 parts of water and added, and 1 part of acetic acid was dissolved at 60°C.
A colored polymer was prepared by stirring for a period of time, and 20 parts of γ-butyrolactone was added to prepare a water-based ink.
【表】
実施例1〜3で得られた各水性インクを充てん
したサインペンを用いてJIS P3201の筆記用紙A
に筆記し、1分後に筆記用紙を1時間水に浸漬し
筆跡の状態を観察したが、筆跡は滲み、汚れがほ
とんどなく、濃さも変らなかつた。さらに、各水
性インクを1ミルのドクターブレードを用いて上
記の筆記用紙に塗布し、キセノンフエードメータ
(ブラツクパネル温度65℃±3℃相対湿度35±5
%)により、日光堅ろう度を試験し、JIS L―
0841ブルースケールの変色程度と比較したとこ
ろ、各染料自体の日光堅ろう度はいずれもブルー
スケール1級程度であつたが、上記の水性インク
はいずれもブルースケール3〜4級であつた。
実施例 4〜6
水溶性ポリマー合成例―2で得られた水溶性ポ
リマー10部に塩基性染料(日本化薬製)2部、酢
酸1部、N―メチル―2―ピロリドン20部、水67
部を添加して60℃で1時間撹拌して着色ポリマー
をつくり、これにエチレングリコール10部、P―
ヒドロキシ安息香酸メチル0.5部を加えて水性イ
ンクを調整した。[Table] JIS P3201 writing paper A using felt-tip pens filled with each water-based ink obtained in Examples 1 to 3.
After 1 minute, the writing paper was immersed in water for 1 hour and the state of the handwriting was observed.The handwriting was hardly smudged or smeared, and the density did not change. Furthermore, each water-based ink was applied to the above writing paper using a 1 mil doctor blade and measured using a xenon fade meter (black panel temperature 65°C ± 3°C relative humidity 35 ± 5°C).
%), the sunlight fastness was tested and JIS L-
When compared with the degree of discoloration on the 0841 blue scale, the sunlight fastness of each dye itself was about 1st grade on the blue scale, but all of the above water-based inks were 3rd to 4th grade on the blue scale. Examples 4 to 6 10 parts of the water-soluble polymer obtained in Water-soluble Polymer Synthesis Example-2, 2 parts of basic dye (manufactured by Nippon Kayaku), 1 part of acetic acid, 20 parts of N-methyl-2-pyrrolidone, and 67 parts of water.
10 parts of ethylene glycol and P-
A water-based ink was prepared by adding 0.5 part of methyl hydroxybenzoate.
【表】
実施例―4〜6で得られた各水性インクを実施
例1〜3と同様に耐水性試験を行つたが、筆跡は
滲み、汚れがほとんどなく、濃さも変らなかつ
た。また、各水性インクの日光堅ろう度は4級程
度であつた。
実施例 7〜9
水溶性ポリマー合成例―3で得られた水溶性ポ
リマー20部に塩基性染料(保土谷化学製)6部、
酢酸1部、N,N′―ジメチルホルムアミド20部、
水53部を添加し、60℃で1時間撹拌し、着色ポリ
マーをつくり、これにジエチレングリコール15部
を加えて水性インクを調整した。[Table] Each of the water-based inks obtained in Examples 4 to 6 was subjected to a water resistance test in the same manner as in Examples 1 to 3, but the handwriting did not smear or stain, and the density did not change. Further, the sunlight fastness of each aqueous ink was about grade 4. Examples 7 to 9 20 parts of the water-soluble polymer obtained in Water-soluble polymer synthesis example-3, 6 parts of basic dye (manufactured by Hodogaya Chemical),
1 part acetic acid, 20 parts N,N'-dimethylformamide,
53 parts of water was added and stirred at 60°C for 1 hour to produce a colored polymer, and 15 parts of diethylene glycol was added to prepare a water-based ink.
【表】
実施例―7〜9で得られた水性インクを実施例
1〜3と同様にして耐水性試験を行つたところ、
筆跡は滲み、汚れがほとんどなく、濃さも変らな
かつた。また、各水性インクの日光堅ろう度は4
級程度であつた。
実施例 10〜12
水溶性ポリマー合成例―2で得られた水溶性ポ
リマー50部に塩基性染料(保土谷化学製)10部、
水40部を添加し、60℃で1時間撹拌し着色ポリマ
ーをつくり、これにγ―ブチロラクトン30部を加
え水性インクを調整した。[Table] The water-based inks obtained in Examples 7 to 9 were subjected to water resistance tests in the same manner as in Examples 1 to 3.
The handwriting did not smear, there was hardly any dirt, and the density remained the same. In addition, the sunlight fastness of each water-based ink is 4.
It was about average. Examples 10-12 10 parts of a basic dye (manufactured by Hodogaya Chemical Co., Ltd.) was added to 50 parts of the water-soluble polymer obtained in Water-soluble Polymer Synthesis Example-2.
40 parts of water was added and stirred at 60°C for 1 hour to produce a colored polymer, and 30 parts of γ-butyrolactone was added to prepare a water-based ink.
【表】
実施例10〜12で得られた各水性インクの耐水
性、日光堅ろう度は、実施例1〜3と同程度であ
つた。また、上記の各水性インクは均一な水溶液
であるのに対して、水溶性ポリマーを用いず、そ
の他の条件を同一にしたものにおいては、各染料
自体の水性インクは塩基性染料の不溶物が多量あ
り、均一な水溶液にならなかつた。[Table] The water resistance and sunlight fastness of each of the aqueous inks obtained in Examples 10 to 12 were comparable to those of Examples 1 to 3. In addition, while each of the water-based inks mentioned above is a uniform aqueous solution, in the case where no water-soluble polymer is used and other conditions are the same, the water-based ink of each dye itself contains insoluble matter of the basic dye. There was a large amount of it, and it was not possible to form a uniform aqueous solution.
Claims (1)
ヒドロキシル基および1×10-4グラム当量/グラ
ムポリマー以上のスルホン酸基を含有する水溶性
ポリマーが塩基性染料で染色されて水不溶性とな
つている着色ポリマーの、水と水溶性有機溶剤と
の混合溶剤溶液からなる水性インク組成物。 2 水溶性有機溶剤が下記一般式〔〕または
〔〕で表わされるものである特許請求の範囲第
1項記載の水性インク組成物。 一般式〔〕 【式】 (R1はHまたはCH3を;R2およびR3はいずれ
もH,CH3またはC2H5を表す。) 一般式〔〕 【式】 (R4はHまたはCH3を;XはNH,NCH3また
はOを;YはCH2またはOを表す。)[Scope of Claims] 1. A water-soluble polymer containing hydroxyl groups of 1×10 -3 gram equivalent/gram polymer or more and sulfonic acid groups of 1×10 -4 gram equivalent/gram polymer or more is dyed with a basic dye. An aqueous ink composition comprising a solution of a colored polymer that is water-insoluble in a mixed solvent of water and a water-soluble organic solvent. 2. The water-based ink composition according to claim 1, wherein the water-soluble organic solvent is represented by the following general formula [] or []. General formula [] [Formula] (R 1 represents H or CH 3 ; R 2 and R 3 both represent H, CH 3 or C 2 H 5. ) General formula [] [Formula] (R 4 represents H or CH 3 ; X represents NH, NCH 3 or O; Y represents CH 2 or O.)
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59056281A JPS60202167A (en) | 1984-03-26 | 1984-03-26 | Water based ink composition |
AU29967/84A AU565936B2 (en) | 1983-06-29 | 1984-06-26 | Aqueous colored polymer |
DE8484304373T DE3466398D1 (en) | 1983-06-29 | 1984-06-27 | Aqueous colored polymer, process for preparing same and ink comprising same |
EP84304373A EP0130789B1 (en) | 1983-06-29 | 1984-06-27 | Aqueous colored polymer, process for preparing same and ink comprising same |
US06/625,254 US4623689A (en) | 1983-06-29 | 1984-06-27 | Aqueous colored polymer, process for preparing same and ink comprising same |
CA000457731A CA1250072A (en) | 1983-06-29 | 1984-06-28 | Aqueous colored polymer, process for preparing same and ink comprising same |
KR1019840003722A KR920008346B1 (en) | 1983-06-29 | 1984-06-29 | Process for the preparation of aqueous colored polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59056281A JPS60202167A (en) | 1984-03-26 | 1984-03-26 | Water based ink composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60202167A JPS60202167A (en) | 1985-10-12 |
JPH0122314B2 true JPH0122314B2 (en) | 1989-04-26 |
Family
ID=13022704
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP59056281A Granted JPS60202167A (en) | 1983-06-29 | 1984-03-26 | Water based ink composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60202167A (en) |
-
1984
- 1984-03-26 JP JP59056281A patent/JPS60202167A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS60202167A (en) | 1985-10-12 |
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