JP6330603B2 - Water-based ink resin composition and water-based ink composition - Google Patents
Water-based ink resin composition and water-based ink composition Download PDFInfo
- Publication number
- JP6330603B2 JP6330603B2 JP2014191967A JP2014191967A JP6330603B2 JP 6330603 B2 JP6330603 B2 JP 6330603B2 JP 2014191967 A JP2014191967 A JP 2014191967A JP 2014191967 A JP2014191967 A JP 2014191967A JP 6330603 B2 JP6330603 B2 JP 6330603B2
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- Prior art keywords
- water
- resin
- based ink
- dispersion
- fine particle
- 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.)
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 142
- 239000000203 mixture Substances 0.000 title claims description 68
- 239000011342 resin composition Substances 0.000 title claims description 31
- 239000011347 resin Substances 0.000 claims description 144
- 229920005989 resin Polymers 0.000 claims description 144
- 239000000976 ink Substances 0.000 claims description 122
- 239000006185 dispersion Substances 0.000 claims description 120
- 239000010419 fine particle Substances 0.000 claims description 56
- 239000000049 pigment Substances 0.000 claims description 54
- 150000001875 compounds Chemical class 0.000 claims description 45
- 239000000178 monomer Substances 0.000 claims description 43
- 239000011258 core-shell material Substances 0.000 claims description 34
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims description 24
- 125000003700 epoxy group Chemical group 0.000 claims description 24
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 18
- 230000009477 glass transition Effects 0.000 claims description 10
- 239000012736 aqueous medium Substances 0.000 claims description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 9
- 125000002723 alicyclic group Chemical group 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- 238000007639 printing Methods 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000007646 gravure printing Methods 0.000 claims description 3
- -1 polyethylene terephthalate Polymers 0.000 description 69
- 239000011248 coating agent Substances 0.000 description 57
- 238000000576 coating method Methods 0.000 description 57
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 44
- 238000004519 manufacturing process Methods 0.000 description 35
- 239000000758 substrate Substances 0.000 description 34
- 238000001035 drying Methods 0.000 description 31
- 239000004593 Epoxy Substances 0.000 description 25
- 230000000903 blocking effect Effects 0.000 description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 22
- 229920005862 polyol Polymers 0.000 description 21
- 150000003077 polyols Chemical class 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- 239000002245 particle Substances 0.000 description 19
- 239000002253 acid Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 239000000306 component Substances 0.000 description 15
- 230000000704 physical effect Effects 0.000 description 15
- 239000012860 organic pigment Substances 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 229920000178 Acrylic resin Polymers 0.000 description 10
- 239000004925 Acrylic resin Substances 0.000 description 10
- 125000000468 ketone group Chemical group 0.000 description 10
- 239000003505 polymerization initiator Substances 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- 230000002411 adverse Effects 0.000 description 8
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- 229940097275 indigo Drugs 0.000 description 8
- 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 8
- 239000000126 substance Substances 0.000 description 8
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- 238000000034 method Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 150000007514 bases Chemical class 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229920005906 polyester polyol Polymers 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
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- 238000003786 synthesis reaction Methods 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- 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 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 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 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000012463 white pigment Substances 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
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- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- 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 3
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- NIYNIOYNNFXGFN-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol;7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound OCC1CCC(CO)CC1.C1C(C(=O)O)CCC2OC21.C1C(C(=O)O)CCC2OC21 NIYNIOYNNFXGFN-UHFFFAOYSA-N 0.000 description 3
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- 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
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-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
- 239000012299 nitrogen atmosphere Substances 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
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 229920002114 octoxynol-9 Polymers 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-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
- 125000000864 peroxy group Chemical group O(O*)* 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
- 239000012071 phase Substances 0.000 description 1
- FURYAADUZGZUGQ-UHFFFAOYSA-N phenoxybenzene;sulfuric acid Chemical class OS(O)(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 FURYAADUZGZUGQ-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
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol 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
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 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
- 238000010926 purge Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 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
- 230000009467 reduction Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 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
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 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
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 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
- OGRPJZFGZFQRHZ-UHFFFAOYSA-M sodium;4-octoxy-4-oxo-3-sulfobutanoate Chemical compound [Na+].CCCCCCCCOC(=O)C(S(O)(=O)=O)CC([O-])=O OGRPJZFGZFQRHZ-UHFFFAOYSA-M 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N tertiary amyl alcohol Natural products CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 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
- 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
- 230000007704 transition Effects 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
- 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
- 229960004418 trolamine Drugs 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
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Printing Methods (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明は、水性インキ用樹脂組成物及びそれを含む水性インキ組成物に関する。さらに詳しくは、低温乾燥条件下においてもフィルム基材に対して優れた基材密着性、耐水摩擦性、耐水ブロッキング性を発現し、一方でインキの分散安定性、ポットライフにも優れる水性インキ用樹脂組成物及び水性インキ組成物に関する。 The present invention relates to a resin composition for water-based ink and a water-based ink composition containing the same. More specifically, for water-based inks that exhibit excellent substrate adhesion, water rub resistance, and water blocking resistance to film substrates even under low temperature drying conditions, while having excellent ink dispersion stability and pot life The present invention relates to a resin composition and a water-based ink composition.
一般的に水性インキ組成物は、顔料、顔料分散樹脂、水、親水性溶剤、およびバインダー樹脂により構成されている。このうちバインダー樹脂は、印字物の塗膜耐性を向上させる目的で添加されている。優れた印刷適性と分散安定性、塗膜物性を両立できる点から、水溶性樹脂を高分子乳化剤として、エチレン性不飽和単量体を乳化重合したコアシェル型樹脂微粒子分散体がバインダー樹脂として多く使用されている。このような水性インキ組成物は、これまで主に紙基材を中心に検討されてきたが、近年、省エネ、低コスト、環境負荷低減の観点から、ポリオレフィン、ポリエチレンテレフタラートなど、フィルム基材に対しても、良好な塗膜耐性を発現することが求められている。 In general, a water-based ink composition is composed of a pigment, a pigment dispersion resin, water, a hydrophilic solvent, and a binder resin. Among these, the binder resin is added for the purpose of improving the coating film resistance of the printed matter. Core shell type resin fine particle dispersions obtained by emulsion polymerization of ethylenically unsaturated monomers and water-soluble resins as polymer emulsifiers are often used as binder resins because they can achieve both excellent printability, dispersion stability, and coating film properties. Has been. Such water-based ink compositions have been mainly studied mainly for paper bases, but in recent years, film base materials such as polyolefin and polyethylene terephthalate are used from the viewpoint of energy saving, low cost, and environmental load reduction. Even on the other hand, it is required to exhibit good coating film resistance.
特許文献1ならびに特許文献2では、水溶性樹脂(シェル成分)、コア成分の組成、分子量、コア成分とシェル成分の比率、粒子径、ガラス転移温度などを規定したコアシェル型樹脂微粒子分散体のバインダー樹脂組成物が開示されている。しかしながら、この樹脂微粒子分散体では、紙基材よりも乾燥性に劣るフィルム基材において、低温乾燥下で十分な塗膜耐性を発現させるには困難である。特許文献3ならびに特許文献4では、水溶性樹脂(シェル成分)やコア成分にケト基を導入したコアシェル型樹脂微粒子分散体が開示されている。たしかにケト−ヒドラジドの架橋系は、一液の状態でも安定であり、塗膜耐性向上についても期待することができる。しかしながら、この架橋系の効果を発現させるには水分を十分に揮発させる必要があるため、高速印刷を想定した低温乾燥下では水分が残留し、塗膜耐性を飛躍的に向上させることは難しい。また、残留したヒドラジド架橋剤が溶出して、耐水性が悪化する場合もある。十分な塗膜耐性を発現するために、高反応性の水性架橋剤を併用した二液タイプの水性インキも各種検討されている。しかしながら、分散安定性が大幅に悪化する、ポットライフが極端に短い等の問題が生じてしまうため、実用レベルで物性を両立するのは困難な場合が多い。 In Patent Document 1 and Patent Document 2, a binder of a core-shell type resin fine particle dispersion in which water-soluble resin (shell component), composition of core component, molecular weight, ratio of core component to shell component, particle diameter, glass transition temperature and the like are defined. A resin composition is disclosed. However, with this resin fine particle dispersion, it is difficult to develop sufficient coating film resistance under low temperature drying in a film substrate that is inferior in drying property to a paper substrate. Patent Literature 3 and Patent Literature 4 disclose a core-shell type resin particle dispersion in which a keto group is introduced into a water-soluble resin (shell component) or a core component. Certainly, the keto-hydrazide crosslinking system is stable even in a one-pack state, and it can be expected to improve the coating film resistance. However, since it is necessary to sufficiently volatilize the water in order to exhibit the effect of this crosslinking system, the water remains under low temperature drying assuming high-speed printing, and it is difficult to dramatically improve the coating film resistance. Further, the remaining hydrazide cross-linking agent may elute and the water resistance may deteriorate. In order to develop sufficient coating film resistance, various types of two-component water-based inks using a highly reactive aqueous cross-linking agent have been studied. However, problems such as significant deterioration in dispersion stability and extremely short pot life occur, and it is often difficult to achieve both physical properties at a practical level.
低温乾燥条件下で、フィルム基材に対して優れた基材密着性、耐水摩擦性、耐水ブロッキング性を発現し、一方でインキの分散安定性、ポットライフにも優れる水性インキ用樹脂組成物及び水性インキ組成物の提供に関する。 Under low-temperature drying conditions, it exhibits excellent substrate adhesion, water rub resistance, and water blocking resistance with respect to the film substrate, while at the same time exhibiting excellent ink dispersion stability and pot life. The present invention relates to provision of a water-based ink composition.
すなわち、本発明は、カルボキシル基を有する水溶性樹脂(A)を高分子乳化剤として、水性媒体中でエチレン性不飽和単量体(B)を乳化重合してなるコアシェル型樹脂微粒子分散体(C)と、
カルボジイミド基含有樹脂微粒子分散体(D)と、
非水溶性エポキシ基含有化合物(E)とを含有してなる水性インキ用樹脂組成物に関する。
That is, the present invention provides a core-shell resin fine particle dispersion (C) obtained by emulsion polymerization of an ethylenically unsaturated monomer (B) in an aqueous medium using a water-soluble resin (A) having a carboxyl group as a polymer emulsifier. )When,
A carbodiimide group-containing resin fine particle dispersion (D);
The present invention relates to a water-based ink resin composition comprising a water-insoluble epoxy group-containing compound (E).
さらに、本発明は、非水溶性エポキシ基含有化合物(E)が脂環式エポキシ基を有している上記水性インキ用樹脂組成物に関する。 Furthermore, this invention relates to the said resin composition for water-based inks in which the water-insoluble epoxy group containing compound (E) has an alicyclic epoxy group.
さらに、本発明は、コアシェル型樹脂微粒子分散体(C)のコア部のガラス転移温度が−30〜30℃である上記水性インキ用樹脂組成物に関する。 Furthermore, this invention relates to the said resin composition for water-based inks whose glass transition temperature of the core part of a core-shell type resin fine particle dispersion (C) is -30-30 degreeC.
さらに、本発明は、コアシェル型樹脂微粒子分散体(C)の重量平均分子量が200000〜500000である上記水性インキ用樹脂組成物に関する。 Furthermore, this invention relates to the said resin composition for water-based inks whose weight average molecular weights of a core-shell type resin fine particle dispersion (C) are 200000-500000.
さらに、本発明は、エチレン性不飽和単量体(B)の合計100重量部に対し、水溶性樹脂(A)の量が40〜150重量部である上記水性インキ用樹脂組成物に関する。 Furthermore, this invention relates to the said resin composition for water-based inks whose quantity of water-soluble resin (A) is 40-150 weight part with respect to a total of 100 weight part of ethylenically unsaturated monomer (B).
さらに、本発明は、顔料、顔料分散樹脂(F)、水、親水性溶剤ならびに、上記水性インキ用樹脂組成物を含有してなる水性インキ組成物に関する。 Furthermore, the present invention relates to a water-based ink composition comprising the pigment, the pigment dispersion resin (F), water, a hydrophilic solvent, and the above water-based ink resin composition.
さらに、本発明は、分分散体(C)および樹脂(F)由来のカルボキシル基1モルに対して、分散体(D)由来のカルボジイミド基が0.1〜0.5モルの範囲であり、
分散樹脂(D)由来のカルボジイミド基1モルに対して、化合物(E)由来のエポキシ基が0.3〜2モルの範囲である上記水性インキ組成物に関する。
Furthermore, in the present invention, the carbodiimide group derived from the dispersion (D) is in the range of 0.1 to 0.5 mol with respect to 1 mol of the carboxyl group derived from the dispersion (C) and the resin (F).
It is related with the said water-based ink composition whose epoxy group derived from a compound (E) is the range of 0.3-2 mol with respect to 1 mol of carbodiimide groups derived from a dispersion resin (D).
さらに、本発明は、フレキソ印刷またはグラビア印刷に用いられる、上記水性インキ組成物に関する。 Furthermore, this invention relates to the said water-based ink composition used for flexographic printing or gravure printing.
本発明により、低温乾燥条件下、フィルム基材に対して優れた基材密着性、耐水摩擦性、耐水ブロッキング性を発現し、一方でインキの分散安定性、ポットライフにも優れる水性インキ用樹脂組成物及び水性インキ組成物を提供できた。 According to the present invention, water-based ink resins exhibit excellent substrate adhesion, water rub resistance, and water blocking resistance to film substrates under low-temperature drying conditions, while also being excellent in ink dispersion stability and pot life. Compositions and aqueous ink compositions could be provided.
まず、本発明に使用するコアシェル型樹脂微粒子分散体(C)について説明する。 First, the core-shell type resin fine particle dispersion (C) used in the present invention will be described.
本発明の水性インキ用コアシェル型樹脂微粒子分散体(C)は、カルボキシル基を有する水溶性樹脂(A)の存在下、水性媒体中でエチレン性不飽和単量体(B)を、ラジカル重合開始剤で乳化重合することにより得ることができる。具体的にコアシェル型樹脂微粒子分散体の製造方法について説明する。まず、反応槽に水性媒体と塩基性化合物、水溶性樹脂(A)を仕込み、昇温して溶解させる。その後、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。反応開始後、反応槽の溶液の色が青白くなるので、粒子核の形成が確認できる。エチレン性不飽和単量体の滴下完了後、更に数時間反応させることでコアシェル樹脂微粒子分散体を得ることができる。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。水溶性樹脂(A)は水性媒体中で保護コロイド(シェル成分)として働き、析出する粒子核(コア成分)を安定化させる。この方法により得られる樹脂微粒子分散体は、ニュート二アンに近い粘性を有するため印刷適性に大変優れている。樹脂微粒子分散体を合成する際に使用する水溶性樹脂(A)はラジカル開始剤により、溶液重合もしくは塊状重合し、樹脂中のカルボキシル基を塩基性化合物で中和することで得ることができる。 The core-shell type resin fine particle dispersion (C) for aqueous ink of the present invention starts radical polymerization of an ethylenically unsaturated monomer (B) in an aqueous medium in the presence of a water-soluble resin (A) having a carboxyl group. It can be obtained by emulsion polymerization with an agent. The manufacturing method of a core-shell type resin fine particle dispersion is demonstrated concretely. First, an aqueous medium, a basic compound, and a water-soluble resin (A) are charged into a reaction vessel, and dissolved by heating. Thereafter, the radical polymerization initiator is added while dropping the ethylenically unsaturated monomer (B) under a nitrogen atmosphere. Since the color of the solution in the reaction vessel turns pale after the reaction starts, the formation of particle nuclei can be confirmed. After completion of dropping of the ethylenically unsaturated monomer, the core-shell resin fine particle dispersion can be obtained by further reacting for several hours. 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 water-soluble resin (A) acts as a protective colloid (shell component) in the aqueous medium and stabilizes the precipitated particle core (core component). Since the resin fine particle dispersion obtained by this method has a viscosity close to Newtonian, it is very excellent in printability. The water-soluble resin (A) used in synthesizing the resin fine particle dispersion can be obtained by solution polymerization or bulk polymerization with a radical initiator and neutralizing a carboxyl group in the resin with a basic compound.
水溶性樹脂(A)は、カルボキシル基を有しており、塩基性化合物で中和されたものが、水媒体中に、溶解もしくは分散し、コア成分の保護コロイドとして機能するものであれば任意のものを使用することができる。樹脂骨格としては、アクリル樹脂、スチレン・アクリル樹脂、スチレン・マレイン酸樹脂、ウレタン樹脂などが挙げられるが、粒子核や顔料分散樹脂との相溶を考慮すると、水溶性樹脂(A)はアクリル樹脂、スチレン・アクリル樹脂、スチレン・マレイン酸樹脂であることが好ましい。さらに、粒子核の安定性な形成を考慮すると、水溶性樹脂(A)は芳香族骨格を有していることが更に好ましい。 The water-soluble resin (A) is arbitrary as long as it has a carboxyl group and is neutralized with a basic compound and dissolved or dispersed in an aqueous medium and functions as a protective colloid of the core component. Can be used. Examples of the resin skeleton include acrylic resin, styrene / acrylic resin, styrene / maleic acid resin, and urethane resin. In consideration of compatibility with the particle core and the pigment dispersion resin, the water-soluble resin (A) is an acrylic resin. Styrene / acrylic resin and styrene / maleic acid resin are preferable. Furthermore, in consideration of the stable formation of particle nuclei, the water-soluble resin (A) further preferably has an aromatic skeleton.
水溶性樹脂(A)がアクリル樹脂、スチレン・アクリル樹脂、スチレン・マレイン酸樹脂である場合、水溶性樹脂(A)は、カルボキシル基含有エチレン性不飽和単量体を含むエチレン性不飽和単量体(a)を、ラジカル開始剤で、溶液もしくは塊状重合することで得られる。また、芳香族骨格は、芳香族エチレン性不飽和単量体を共重合することにより導入することができる。 When the water-soluble resin (A) is an acrylic resin, a styrene / acrylic resin, or a styrene / maleic acid resin, the water-soluble resin (A) is an ethylenically unsaturated monomer containing a carboxyl group-containing ethylenically unsaturated monomer. The body (a) is obtained by solution or bulk polymerization with a radical initiator. The aromatic skeleton can be introduced by copolymerizing an aromatic ethylenically unsaturated monomer.
エチレン性不飽和単量体(a)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の芳香族エチレン性不飽和単量体;
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、n−ブチルメタクリレート、tーブチルメタクリレート、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;
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、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;
(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、4−ヒドロキシビニルベンゼン、1−エチニル−1−シクロヘキサノール、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。
As the ethylenically unsaturated monomer (a), 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 ethylenically unsaturated monomers of glycol acrylate, phenoxytetraethylene glycol methacrylate, phenoxyhexaethylene glycol acrylate, phenoxyhexaethylene glycol methacrylate, phenyl acrylate, phenyl methacrylate;
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate Straight chain or branched alkyl group-containing ethylenically unsaturated monomers such as nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, etc. Mer;
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;
Carboxylic acid such as maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid Group-containing ethylenically unsaturated monomers;
(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, diacetoneacrylamide;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, allyl Hydroxyl group-containing ethylenically unsaturated monomers such as alcohol;
Etc.
水溶性樹脂(A)の合成時に使用するラジカル開始剤に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 synthesis of the water-soluble resin (A), a known oil-soluble polymerization initiator can be used. For example, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, tert-butyl Organic peroxides such as 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.
水溶性樹脂(A)がウレタン樹脂である場合、特に限定はされないが、従来既知の方法に従い、ポリオールとポリイソシアネートとを反応させて得ることができる。 When the water-soluble resin (A) is a urethane resin, it is not particularly limited, but it can be obtained by reacting a polyol and a polyisocyanate according to a conventionally known method.
ポリオールとしては、代表的なものとして例えば、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオールなどが挙げられる。 Typical examples of the polyol include polyester polyol, polyether polyol, and polycarbonate polyol.
ポリエステルポリオールとしては、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、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 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. Examples thereof include aliphatic or aromatic dibasic acids such as terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid and 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.
ポリエーテルポリオールとしては、例えば、テトラヒドロフラン、あるい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のアルキレンオキサイドの重合体、共重合体あるいはグラフト共重合体、またはヘキサンジオール、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、プロポキシル化またはエトキシル化されたポリエーテルポリオール類等の水酸基が2個以上のものを用いることができる。 Examples of the polyether polyol include tetrahydrofuran, or a polymer, copolymer or graft copolymer of alkylene oxide such as tetrahydrofuran, ethylene oxide, propylene oxide, butylene oxide, hexanediol, methylhexanediol, heptanediol, octanediol, or Those having two or more hydroxyl groups, such as polyether polyols obtained by condensation of these mixtures and polyether polyols which are propoxylated or ethoxylated, can be used.
ポリカーボネートポリオールとしては、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 include those obtained by a reaction between a polyol and a carbonate compound such as dialkyl carbonate, alkylene carbonate, and 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.
この他、ポリブタジエンポリオール、アクリルポリオール、ポリシロキサンポリオール、ひまし油なども挙げられる。 In addition, polybutadiene polyol, acrylic polyol, polysiloxane polyol, castor oil, and the like are also included.
これらのポリオールは、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。 These polyols may use only 1 type, or may use multiple types together.
また、カルボキシル基を有するポリオールを使用することで樹脂中にカルボキシル基が導入され、塩基性化合物で中和した際に、水性媒体中に溶解もしくは分散させることができる。 Further, by using a polyol having a carboxyl group, the carboxyl group is introduced into the resin, and when neutralized with a basic compound, it can be dissolved or dispersed in an aqueous medium.
カルボキシル基を有するポリオール成分としては、例えば、
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、ジメチロールアルカン酸等が挙がられる。
As a polyol component having a carboxyl group, for example,
Examples include dimethylol alkanoic acid such as dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, dihydroxysuccinic acid, dihydroxypropionic acid, dihydroxybenzoic acid, etc. And dimethylolalkanoic acid.
水溶性樹脂(A)の酸価は100〜250mgKOH/gであることが好ましい。水溶性樹脂(A)の酸価が100mgKOH/g未満であると、分散安定性が悪化して、コアシェル型樹脂微粒子分散体が安定に合成できない場合や、合成できてもインキの分散安定性も悪化させてしまう場合がある。一方、250mgKOH/gを超えると、乾燥不良が発生して塗膜の耐水摩擦性や耐水ブロッキング性に悪影響を及ぼす場合がある。ここで言う酸価とは、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mg数のことをいう。 It is preferable that the acid value of water-soluble resin (A) is 100-250 mgKOH / g. If the acid value of the water-soluble resin (A) is less than 100 mgKOH / g, the dispersion stability deteriorates, and the core-shell resin fine particle dispersion cannot be stably synthesized. It may make it worse. On the other hand, when it exceeds 250 mgKOH / g, poor drying may occur, which may adversely affect the water friction resistance and water blocking resistance of the coating film. The acid value mentioned here means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of resin.
さらに水溶性樹脂(A)の重量平均分子量は5000〜20000であることが好ましく、さらに好ましくは5000〜15000である。重量平均分子量が5000未満であると、樹脂微粒子分散体の分散安定性が低下するため、インキの分散安定性を悪化させる恐れがある。一方、重量平均分子量が20000を超えた場合には、インキ組成物の増粘が著しくなり、この場合も分散安定性が悪化する恐れがある。 Furthermore, it is preferable that the weight average molecular weights of water-soluble resin (A) are 5000-20000, More preferably, it is 5000-15000. If the weight average molecular weight is less than 5,000, the dispersion stability of the resin fine particle dispersion is lowered, which may deteriorate the dispersion stability of the ink. On the other hand, when the weight average molecular weight exceeds 20000, the viscosity of the ink composition is remarkably increased, and also in this case, the dispersion stability may be deteriorated.
(記載が不十分。測定機器のメーカー、溶剤、カラムの種類等記載すること)
ここで、重量平均分子量(Mw)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をいう。
⇒方法の詳細は実施例部分に記載しております。
(Inadequate description. Enter manufacturer, solvent, column type, etc.)
Here, the weight average molecular weight (Mw) refers to a value in terms of polystyrene by GPC (gel permeation chromatography) measurement.
⇒ Details of the method are described in the examples section.
中和剤として使用する塩基性化合物には、アンモニア、トリメチルアミン、トリエチルアミン、ブチルアミン、2−ジメチルアミノエタノール、2−ジエチルアミノエタノール、ジエタノールアミン、トリエタノールアミン、アミノメチルプロパノール、モルホリンなどのアミン類;
水酸化カリウム、水酸化ナトリウムなどの水酸化物塩;
等が挙げられる。
Examples of basic compounds used as neutralizing agents include amines such as ammonia, trimethylamine, triethylamine, butylamine, 2-dimethylaminoethanol, 2-diethylaminoethanol, diethanolamine, triethanolamine, aminomethylpropanol, and morpholine;
Hydroxide salts such as potassium hydroxide and sodium hydroxide;
Etc.
カルボキシル基を有する水溶性樹脂(A)は、上記の組成の条件を満たすものであれば市販品を使用しても構わない。市販品としては、例えば、
星光PMC社製X−300,VS−1029,VS−1057,TS−1316,VS−1028,TS−1315,RS−1190,VS−1030,VS−1202等のアクリル樹脂;
星光PMC社製 US−1071,X−1,RS−1193,VS−1259,TS−1318,YS−1274,VS−1047,RS−1191;
BASF社製JONCRYL67、JONCRYL678、JONCRYL611、JONCRYL680、JONCRYL682、JONCRYL693、JONCRYL690、JONCRYL52J 、JONCRYL57J、JONCRYL60J、JONCRYL61J、JONCRYL62J、JONCRYL63J、JONCRYL HPD−96J
等のスチレン・アクリル樹脂;
星光PMC社製 X−228,X−220,X−200,US−1243,X−205,X−210
Cray Valley社製 SMA1000,SMA2000, SMA1440,SMA2625等のスチレン・マレイン酸樹脂;
等が挙げられる。
As the water-soluble resin (A) having a carboxyl group, a commercially available product may be used as long as it satisfies the above-described composition conditions. As a commercial item, for example,
Acrylic resins such as X-300, VS-1029, VS-1057, TS-1316, VS-1028, TS-1315, RS-1190, VS-1030, VS-1220, etc. manufactured by Seiko PMC;
US-1071, X-1, RS-1193, VS-1259, TS-1318, YS-1274, VS-1047, RS-1191 manufactured by Seiko PMC;
BASF JONCRYL67, JONCRYL678, JONCRYL611, JONCRYL680, JONCRYL682, JONCRYL693, JONCRYL690, JONCRYL52J, JONCRYL57J, JONCRYL60J, JONCRYL96J, JONCRYL61J
Styrene acrylic resin such as
X-228, X-220, X-200, US-1243, X-205, X-210 manufactured by Seiko PMC
Styrene / maleic resin such as SMA1000, SMA2000, SMA1440, SMA2625 manufactured by Cray Valley, etc .;
Etc.
次に本発明で使用するエチレン性不飽和単量体(B)について説明する。水溶性樹脂(A)の保護コロイドのもと、エチレン性不飽和単量体(B)を重合することにより、コアシェル型樹脂微粒子分散体(C)の粒子核(コア成分)が形成される。 Next, the ethylenically unsaturated monomer (B) used in the present invention will be described. By polymerizing the ethylenically unsaturated monomer (B) under the protective colloid of the water-soluble resin (A), the particle core (core component) of the core-shell type resin particle dispersion (C) is formed.
エチレン性不飽和単量体(B)には、上述したエチレン性不飽和単量体(a)を使用することができる。コア内部を架橋させて高分子量化させたい場合には、架橋性エチレン性不飽和単量体を使用することができる。 The ethylenically unsaturated monomer (a) described above can be used for the ethylenically unsaturated monomer (B). When it is desired to increase the molecular weight by crosslinking the inside of the core, a crosslinkable ethylenically unsaturated monomer can be used.
架橋性エチレン性不飽和単量体としては、例えば、
アリル(メタ)アクリレート、1−メチルアリル(メタ)アクリレート、2−メチルアリル(メタ)アクリレート、1−ブテニル(メタ)アクリレート、2−ブテニル(メタ)アクリレート、3−ブテニル(メタ)アクリレート、1,3−メチル−3−ブテニル(メタ)アクリレート、2−クロルアリル(メタ)アクリレート、3−クロルアリル(メタ)アクリレート、o−アリルフェニル(メタ)アクリレート、2−(アリルオキシ)エチル(メタ)アクリレート、アリルラクチル(メタ)アクリレート、シトロネリル(メタ)アクリレート、ゲラニル(メタ)アクリレート、ロジニル(メタ)アクリレート、シンナミル(メタ)アクリレート、ジアリルマレエート、ジアリルイタコン酸、ビニル(メタ)アクリレート、クロトン酸ビニル、オレイン酸ビニル,リノレン酸ビニル、2−(2’−ビニロキシエトキシ)エチル(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、トリエチレングリコール(メタ)アクリレート、テトラエチレングリコール(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、1,1,1−トリスヒドロキシメチルエタンジアクリレート、1,1,1−トリスヒドロキシメチルエタントリアクリレート、1,1,1−トリスヒドロキシメチルプロパントリアクリレート、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;
N−メチロール(メタ)アクリルアミド、N,N−ジメチロール(メタ)アクリルアミド、アルキルエーテル化N−メチロール(メタ)アクリルアミド等のメチロール基含有エチレン性不飽和単量体が挙げられるが、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。
Examples of the crosslinkable ethylenically unsaturated monomer include:
Allyl (meth) acrylate, 1-methylallyl (meth) acrylate, 2-methylallyl (meth) acrylate, 1-butenyl (meth) acrylate, 2-butenyl (meth) acrylate, 3-butenyl (meth) acrylate, 1,3- Methyl-3-butenyl (meth) acrylate, 2-chloroallyl (meth) acrylate, 3-chloroallyl (meth) acrylate, o-allylphenyl (meth) acrylate, 2- (allyloxy) ethyl (meth) acrylate, allyl lactyl (meth) Acrylate, citronellyl (meth) acrylate, geranyl (meth) acrylate, rosinyl (meth) acrylate, cinnamyl (meth) acrylate, diallyl maleate, diallyl itaconic acid, vinyl (meth) acrylate, vinyl crotonic acid Vinyl oleate, vinyl linolenate, 2- (2′-vinyloxyethoxy) ethyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, trimethylol Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,1,1-trishydroxymethylethane diacrylate, 1,1,1-trishydroxymethylethane triacrylate, 1,1,1-trishydroxymethyl Ethylenically unsaturated monomers having two or more ethylenically unsaturated groups such as propane triacrylate, divinylbenzene, divinyl adipate, diallyl isophthalate, diallyl phthalate, diallyl maleate;
Epoxy group-containing ethylenically unsaturated monomers such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate;
γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltributoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxy Propyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-acryloxymethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane Alkoxysilyl group-containing ethylenically unsaturated monomers such as vinyltributoxysilane and vinylmethyldimethoxysilane;
Examples include, but are not limited to, methylol group-containing ethylenically unsaturated monomers such as N-methylol (meth) acrylamide, N, N-dimethylol (meth) acrylamide, and alkyl etherified N-methylol (meth) acrylamide. It is not something. These can be used alone or in combination of two or more.
粒子核形成時の安定性、粒子核内部への非水溶性エポキシ化合物の含浸のし易さ、低温乾燥下における優れた乾燥性の観点から、エチレン性不飽和単量体(B)は芳香族エチレン性不飽和単量体を含有していることが好ましい。芳香族骨格を有する粒子核は、インキ中での安定性に優れ、その疎水的な環境から非水溶性エポキシ化合物が内部に含浸し易い。したがってインキの状態では水相のカルボキシル基との反応が抑制され、インキの分散安定性、ポットライフが向上する。また、水分を抱きこみ難くなることから塗膜の乾燥性も向上する。 The ethylenically unsaturated monomer (B) is aromatic from the viewpoints of stability during particle nucleation, ease of impregnation of the water-insoluble epoxy compound into the particle nuclei, and excellent drying properties under low temperature drying. It preferably contains an ethylenically unsaturated monomer. Particle nuclei having an aromatic skeleton are excellent in stability in ink and are easily impregnated with a water-insoluble epoxy compound from the hydrophobic environment. Therefore, in the ink state, the reaction with the carboxyl group of the aqueous phase is suppressed, and the dispersion stability and pot life of the ink are improved. Moreover, since it becomes difficult to entrap moisture, the drying property of the coating film is also improved.
エチレン性不飽和単量体(B)100重量%中、芳香族エチレン性不飽和単量体を20〜70重量%含有することが好ましい。芳香族エチレン性不飽和単量体の含有量が20重量%未満の場合、芳香族骨格導入における効果が少なく、非水溶性エポキシ化合物が反応しやすくなり、インキの分散安定性、ポットライフが低下する場合がある。一方で、70%を超えると乾燥時のコア部分とシェル部分の相溶性が低下して、造膜が不十分となり、塗膜の耐水摩擦性が悪化する恐れがある。 It is preferable to contain 20 to 70% by weight of the aromatic ethylenically unsaturated monomer in 100% by weight of the ethylenically unsaturated monomer (B). When the content of the aromatic ethylenically unsaturated monomer is less than 20% by weight, the effect of introducing the aromatic skeleton is small, the water-insoluble epoxy compound becomes easy to react, and the ink dispersion stability and pot life are reduced. There is a case. On the other hand, if it exceeds 70%, the compatibility between the core part and the shell part at the time of drying is lowered, film formation becomes insufficient, and the water friction resistance of the coating film may be deteriorated.
さらにエチレン性不飽和単量体(B)はケト基含有不飽和単量体を含有していることが好ましい。
コアシェル型樹脂微粒子分散体(C)にケト基を導入し、インキ中に二官能以上のヒドラジド化合物を添加しておくと、乾燥時にケト基とヒドラジド基で反応する。また、非水溶性エポキシ化合物(E)由来の一部のエポキシ基もヒドラジド基と反応する。したがって、これらの官能基の組み合わせにより、強靭な塗膜形成され、耐水摩擦性が向上する。さらにフィルム基材の処理面にもケト基が存在しているため、基材に対する密着性も向上する。
Furthermore, the ethylenically unsaturated monomer (B) preferably contains a keto group-containing unsaturated monomer.
When a keto group is introduced into the core-shell type resin fine particle dispersion (C) and a bifunctional or higher hydrazide compound is added to the ink, the keto group reacts with the hydrazide group during drying. In addition, some epoxy groups derived from the water-insoluble epoxy compound (E) also react with the hydrazide group. Therefore, a combination of these functional groups forms a tough coating film and improves water friction resistance. Furthermore, since keto groups are present on the treated surface of the film substrate, the adhesion to the substrate is also improved.
コアシェル型樹脂微粒子分散体(C)において、ケト基はコア成分のみに導入することが好ましい。シェル部に導入した場合、十分に融着が進行しない間に架橋してしまい造膜が阻害され、塗膜の耐水摩擦性が低下する恐れがある。 In the core-shell resin fine particle dispersion (C), it is preferable to introduce the keto group only into the core component. When it is introduced into the shell portion, it is crosslinked while the fusion does not proceed sufficiently, and film formation is hindered, and the water friction resistance of the coating film may be lowered.
エチレン性不飽和単量体(B)100重量%中、ケト基含有エチレン性不飽和単量体は1〜5重量%含有することが好ましい。1重量%未満であると、塗膜物性において、架橋の効果が十分に発現しない場合がある。一方で5重量%を超えた場合には、十分に融着が進行しない間に架橋してしまい、造膜性が低下して耐水摩擦性が低下する恐れがある。 The keto group-containing ethylenically unsaturated monomer is preferably contained in 1 to 5% by weight in 100% by weight of the ethylenically unsaturated monomer (B). If it is less than 1% by weight, the effect of crosslinking may not be sufficiently exhibited in the physical properties of the coating film. On the other hand, if it exceeds 5% by weight, crosslinking may occur while fusion does not proceed sufficiently, so that the film forming property may be deteriorated and the water friction resistance may be deteriorated.
ケト基含有エチレン性不飽和単量体としては、例えば、ジアセトン(メタ)アクリルアミド、アセトアセトキシ(メタ)アクリレート等が挙げられる。 Examples of the keto group-containing ethylenically unsaturated monomer include diacetone (meth) acrylamide, acetoacetoxy (meth) acrylate, and the like.
コアシェル型樹脂微粒子分散体(C)のコアのガラス転移温度(Tg)は−30〜30℃の範囲であることが好ましい。コアのガラス転移温度が−30℃未満であると、塗膜強度が不足して塗膜の基材密着性、耐水摩擦性が低下する場合がある。一方でガラス転移温度が30℃を超えた場合にも、基材への濡れ性、造膜性が低下して、塗膜の基材密着性、耐水摩擦性が低下する場合がある。 The glass transition temperature (Tg) of the core of the core-shell type resin fine particle dispersion (C) is preferably in the range of -30 to 30 ° C. When the glass transition temperature of the core is less than −30 ° C., the coating film strength is insufficient, and the base material adhesion and water friction resistance of the coating film may decrease. On the other hand, even when the glass transition temperature exceeds 30 ° C., the wettability to the base material and the film-forming property may be reduced, and the base material adhesion and water friction resistance of the coating film may be reduced.
上記のガラス転移温度(Tg)は、DSC(示差走査熱量計)を用いて求めた値である。コアシェル型樹脂微粒子分散体を測定した場合、コア部とシェル部のTgをそれぞれ検出することができる。 Said glass transition temperature (Tg) is the value calculated | required using DSC (differential scanning calorimeter). When the core-shell type resin fine particle dispersion is measured, the Tg of the core part and the shell part can be detected.
コアシェル型樹脂微粒子分散体(C)の重量平均分子量は200000〜500000の範囲であることが好ましい。重量平均分子量が200000未満であると、塗膜強度が不足して塗膜の基材密着性、耐水摩擦性が低下する場合がある。一方で500000を超える場合、低温乾燥ではコア成分とシェル成分の融着が十分に進行せず、造膜性が低下して塗膜の基材密着性、耐水摩擦性が十分に発現しない場合がある。 The weight average molecular weight of the core-shell resin fine particle dispersion (C) is preferably in the range of 200,000 to 500,000. If the weight average molecular weight is less than 200,000, the coating film strength may be insufficient, and the substrate adhesion and water friction resistance of the coating film may decrease. On the other hand, when it exceeds 500,000, the fusion of the core component and the shell component does not proceed sufficiently at low temperature drying, and the film-forming property is lowered, and the substrate adhesion of the coating film and the water friction resistance may not be sufficiently exhibited. is there.
乳化重合時に用いられる水性媒体としては、水が挙げられる。また、親水性の有機溶剤も樹脂微粒子分散体の合成時の安定性を阻害しない範囲であれば併用することができる。 Water is mentioned as an aqueous medium used at the time of emulsion polymerization. A hydrophilic organic solvent can also be used in combination as long as it does not impair the stability during the synthesis of the resin fine particle dispersion.
コアシェル型樹脂微粒子分散体(C)の合成時に用いられる水溶性樹脂(A)の量は、エチレン性不飽和単量体(B)の合計100重量部に対し、40〜150重量部であることが好ましい。40重量部未満であると、樹脂微粒子分散体の合成時において、粒子核形成が不安定になる。また、造膜性が低下するので、塗膜の基材密着性、耐水摩擦性が悪化する恐れがある。一方で、150重量部を越えると、乾燥不良により塗膜の耐水摩擦性、耐水ブロッキング性が悪化する場合がある。 The amount of the water-soluble resin (A) used in the synthesis of the core-shell type resin fine particle dispersion (C) is 40 to 150 parts by weight with respect to 100 parts by weight of the total of the ethylenically unsaturated monomer (B). Is preferred. If it is less than 40 parts by weight, the formation of particle nuclei becomes unstable during the synthesis of the resin fine particle dispersion. Moreover, since film forming property falls, there exists a possibility that the base-material adhesiveness of a coating film and water friction resistance may deteriorate. On the other hand, if it exceeds 150 parts by weight, the water friction resistance and water blocking resistance of the coating film may deteriorate due to poor drying.
乳化重合の際の重合開始剤としては、ラジカル重合を開始する能力を有するものであれば特に制限はなく、公知の油溶性重合開始剤や水溶性重合開始剤を使用することができる。 The polymerization initiator used in the emulsion polymerization is not particularly limited as long as it has the ability to initiate radical polymerization, and known oil-soluble polymerization initiators and water-soluble polymerization initiators can be used.
油溶性重合開始剤としては特に限定されず、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。これらは1種類または2種類以上を混合して使用することができる。
The oil-soluble polymerization initiator is not particularly limited, and examples thereof include benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, tert-butyl peroxy (2-ethylhexanoate), and tert-butyl peroxide. Organic peroxides such as oxy-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. These can be used alone or in combination of two or more.
本発明において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 present invention, a water-soluble polymerization initiator is preferably used. For example, ammonium persulfate (APS), potassium persulfate (KPS), hydrogen peroxide, 2,2′-azobis (2-methylpropionamidine) dihydro Conventionally known materials such as chloride can be preferably used.
また、乳化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 emulsion polymerization, a reducing agent can be used together with a polymerization initiator if desired. 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.
本発明で使用する樹脂微粒子分散体をラジカル重合により得る際、前記した水溶性樹脂(A)とともに、安定性を補助する目的で低分子界面活性剤を併用することができる。これらはインキ物性に悪影響を及ぼさない範囲で併用できる。 When the resin fine particle dispersion used in the present invention is obtained by radical polymerization, a low molecular surfactant can be used in combination with the water-soluble resin (A) for the purpose of assisting stability. These can be used in combination as long as the ink physical properties are not adversely affected.
低分子界面活性剤としては例えば、
アルキルエーテル系(市販品としては、例えば、第一工業製薬株式会社製アクアロンKH−05、KH−10、KH−20、株式会社ADEKA製アデカリアソープSR−10N、SR−20N、花王株式会社製ラテムルPD−104など)、スルフォコハク酸エステル系(市販品としては、例えば、花王株式会社製ラテムルS−120、S−120A、S−180P、S−180A、三洋化成株式会社製エレミノールJS−2など)、アルキルフェニルエーテル系もしくはアルキルフェニルエステル系(市販品としては、例えば、第一工業製薬株式会社製アクアロンH−2855A、H−3855B、H−3855C、H−3856、HS−05、HS−10、HS−20、HS−30、株式会社ADEKA製アデカリアソープSDX−222、SDX−223、SDX−232、SDX−233、SDX−259、SE−10N、SE−20N、など)、(メタ)アクリレート硫酸エステル系(市販品としては、例えば、日本乳化剤株式会社製アントックスMS−60、MS−2N、三洋化成工業株式会社製エレミノールRS−30など)、リン酸エステル系(市販品としては、例えば、第一工業製薬株式会社製H−3330PL、株式会社ADEKA製アデカリアソープPP−70など)等のアニオン系反応性乳化剤;
Examples of low molecular surfactants include:
Alkyl ethers (for example, Adalon KH-05, KH-10, KH-20, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adeka Soap SR-10N, SR-20N manufactured by ADEKA Corporation, manufactured by Kao Corporation Latemul PD-104, etc.), sulfosuccinic acid ester type (commercially available products include, for example, Latemul S-120, S-120A, S-180P, S-180A, Kayo Co., Ltd., Elemiol JS-2, Sanyo Chemical Co., Ltd.) ), Alkylphenyl ethers or alkylphenyl esters (commercially available products include, for example, Aqualon H-2855A, H-3855B, H-3855C, H-3856, HS-05, HS-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) , HS-20, HS-30, Adeka Soap SDX-2 manufactured by ADEKA Corporation 2, SDX-223, SDX-232, SDX-233, SDX-259, SE-10N, SE-20N, etc.), (meth) acrylate sulfate ester system (commercially available products include, for example, Anne manufactured by Nippon Emulsifier Co., Ltd. Tox MS-60, MS-2N, Sanyo Kasei Kogyo Co., Ltd., Eleminol RS-30, etc.), phosphoric acid ester type (for example, H-3330PL manufactured by Daiichi Kogyo Seiyaku Co., Ltd., ADEKA Co., Ltd. Anionic reactive emulsifiers such as rear soap PP-70);
アルキルエーテル系(市販品としては、例えば、株式会社ADEKA製アデカリアソープER−10、ER−20、ER−30、ER−40、花王株式会社製ラテムルPD−420、PD−430、PD−450など)、アルキルフェニルエーテル系もしくはアルキルフェニルエステル系(市販品としては、例えば、第一工業製薬株式会社製アクアロンRN−10、RN−20、RN−30、RN−50、株式会社ADEKA製アデカリアソープNE−10、NE−20、NE−30、NE−40など)、(メタ)アクリレート硫酸エステル系(市販品としては、例えば、日本乳化剤株式会社製RMA−564、RMA−568、RMA−1114など)等のノニオン系反応性乳化剤; Alkyl ether type (As commercial products, for example, Adeka Soap ER-10, ER-20, ER-30, ER-40 manufactured by ADEKA Corporation, Latemul PD-420, PD-430, PD-450 manufactured by Kao Corporation Etc.), alkylphenyl ethers or alkylphenyl esters (commercially available products include, for example, Aqualon RN-10, RN-20, RN-30, RN-50, ADEKA, Inc., Adekaria, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Soap NE-10, NE-20, NE-30, NE-40, etc.), (meth) acrylate sulfate ester (commercially available products include, for example, RMA-564, RMA-568, RMA-1114 manufactured by Nippon Emulsifier Co., Ltd. Nonionic reactive emulsifiers such as
オレイン酸ナトリウムなどの高級脂肪酸塩類、ドデシルベンゼンスルホン酸ナトリウムなどのアルキルアリールスルホン酸塩類、ラウリル硫酸ナトリウムなどのアルキル硫酸エステル塩類、ポリエキシエチレンラウリルエーテル硫酸ナトリウムなどのポリオキシエチレンアルキルエーテル硫酸エステル塩類、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウムなどのポリオキシエチレンアルキルアリールエーテル硫酸エステル塩類、モノオクチルスルホコハク酸ナトリウム、ジオクチルスルホコハク酸ナトリウム、ポリオキシエチレンラウリルスルホコハク酸ナトリウムなどのアルキルスルホコハク酸エステル塩およびその誘導体類、ポリオキシエチレンジスチレン化フェニルエーテル硫酸エステル塩類
等のアニオン性非反応性乳化剤;
Higher fatty acid salts such as sodium oleate, alkylaryl sulfonates such as sodium dodecylbenzene sulfonate, alkyl sulfate salts such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate salts such as sodium polyoxyethylene lauryl ether sulfate, Polyoxyethylene alkylaryl ether sulfates such as sodium polyoxyethylene nonylphenyl ether sulfate, alkyl sulfosuccinates such as sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate and derivatives thereof, Anionic non-reactive emulsification of polyoxyethylene distyrenated phenyl ether sulfates ;
ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテルなどのポリオキシエチレンアルキルエーテル類、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテルなどのポリオキシエチレンアルキルフェニルエーテル類、ソルビタンモノラウレート、ソルビタンモノステアレート、ソルビタントリオレエートなどのソルビタン高級脂肪酸エステル類、ポリオキシエチレンソルビタンモノラウレートなどのポリオキシエチレンソルビタン高級脂肪酸エステル類、ポリオキシエチレンモノラウレート、ポリオキシエチレンモノステアレートなどのポリオキシエチレン高級脂肪酸エステル類、オレイン酸モノグリセライド、ステアリン酸モノグリセライドなどのグリセリン高級脂肪酸エステル類、ポリオキシエチレン・ポリオキシプロピレン・ブロックコポリマー、ポリオキシエチレンジスチレン化フェニルエーテル等のノニオン性非反応性乳化剤;
等が挙げられる。
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether, sorbitan monolaurate, sorbitan mono Sorbitan higher fatty acid esters such as stearate and sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene such as polyoxyethylene monolaurate and polyoxyethylene monostearate Glycerin higher fatty acid ester such as higher fatty acid esters, oleic acid monoglyceride, stearic acid monoglyceride Le ethers, polyoxyethylene polyoxypropylene block copolymer, nonionic non-reactive emulsifier polyoxyethylene distyrenated phenyl ether;
Etc.
次に本発明で使用するカルボジイミド基含有樹脂微粒子分散体(D)について説明する。本発明のカルボジイミド基含有微粒子分散体は、エマルジョンタイプの架橋剤であり、ジイソシアネート骨格由来の疎水性ポリカルボジイミド樹脂にエチレンオキサイド鎖などの親水性基を変性して得ることができる。カルボジイミド基はカルボキシル基と反応して、低温乾燥下における塗膜の乾燥性を向上させる。さらにその官能基由来の適度な弾性率の高さから低温乾燥下における耐水ブロッキング向上に有効である。 Next, the carbodiimide group-containing resin fine particle dispersion (D) used in the present invention will be described. The carbodiimide group-containing fine particle dispersion of the present invention is an emulsion type cross-linking agent, and can be obtained by modifying a hydrophilic group such as an ethylene oxide chain on a hydrophobic polycarbodiimide resin derived from a diisocyanate skeleton. The carbodiimide group reacts with the carboxyl group to improve the drying property of the coating film under low temperature drying. Furthermore, it is effective in improving water blocking resistance under low temperature drying due to its moderate elastic modulus derived from its functional group.
カルボジイミド基含有樹脂微粒子分散体(D)におけるポリカルボジイミド骨格は、ジイソシアネート化合物の脱炭酸縮合反応により得られる。ジイソシアネート化合物については任意のものを使用できるが、化学的安定性、優れた反応性、塗膜の最適な弾性率の観点から、ジシクロヘキシルメタン4,4'-ジイソシアナートであることが好ましい。 The polycarbodiimide skeleton in the carbodiimide group-containing resin fine particle dispersion (D) is obtained by a decarboxylation condensation reaction of a diisocyanate compound. Any diisocyanate compound can be used, but dicyclohexylmethane 4,4′-diisocyanate is preferable from the viewpoint of chemical stability, excellent reactivity, and optimum elastic modulus of the coating film.
カルボジイミド基含有樹脂微粒子分散体(D)は、疎水性のポリカルボジイミドに親水基を変性して合成することもできるが、市販品を使用しても構わない。 The carbodiimide group-containing resin fine particle dispersion (D) can be synthesized by modifying a hydrophilic group to hydrophobic polycarbodiimide, but a commercially available product may be used.
カルボジイミド基含有樹脂微粒子分散体(D)の市販品としては、例えば、
日清紡ケミカル社製 カルボジライトE−01、E−02、E−03A、E−04等が挙げられる。
As a commercial product of the carbodiimide group-containing resin fine particle dispersion (D), for example,
Carbodilite E-01, E-02, E-03A, E-04, etc. manufactured by Nisshinbo Chemical Co., Ltd. may be mentioned.
次に本発明で使用する非水溶性エポキシ基含有化合物(E)について説明する。本発明の水性インキ用樹脂組成物は、非水溶性のエポキシ化合物を含有する。ここで言う非水溶性エポキシ化合物とは、常圧・20℃において、水への溶解性が1%未満のエポキシ化合物のことを言う。非水溶性エポキシ化合物はインキ組成物調製時に添加する。非水溶性エポキシ基含有化合物(E)は、インキ溶剤中において、コアシェル型樹脂微粒子分散体(C)の粒子核内部に含浸される。したがって、水相の水溶性樹脂(A)もしくは顔料分散樹脂由来のカルボキシル基とエポキシ基との反応が抑制され、経時でのインキの安定性とポットライフが向上する。乾燥後は、粒子核中のエポキシ化合物が塗膜中に拡散するため、カルボキシル基との反応が促進されて耐水摩擦性が向上する。また、非極性フィルム基材の表面に存在するカルボキシル基とも反応するため、基材密着性も向上する。非水溶性エポキシ化合物(E)は、単官能タイプのものでも効果はあるが、塗膜強度向上の観点から二官能以上であることが好ましい。水溶性のエポキシ化合物を用いた場合には、インキの分散安定性、ポットライフが極端に悪化する。 Next, the water-insoluble epoxy group-containing compound (E) used in the present invention will be described. The resin composition for water-based inks of the present invention contains a water-insoluble epoxy compound. The water-insoluble epoxy compound as used herein refers to an epoxy compound having a solubility in water of less than 1% at normal pressure and 20 ° C. The water-insoluble epoxy compound is added when preparing the ink composition. The water-insoluble epoxy group-containing compound (E) is impregnated inside the core of the core-shell resin fine particle dispersion (C) in the ink solvent. Therefore, the reaction between the water phase water-soluble resin (A) or the pigment-dispersed resin-derived carboxyl group and the epoxy group is suppressed, and the stability and pot life of the ink over time are improved. After drying, since the epoxy compound in the particle core diffuses into the coating film, the reaction with the carboxyl group is promoted and the water friction resistance is improved. Moreover, since it reacts also with the carboxyl group which exists in the surface of a nonpolar film base material, base-material adhesiveness also improves. Although the water-insoluble epoxy compound (E) is effective even if it is of a monofunctional type, it is preferably bifunctional or more from the viewpoint of improving the coating film strength. When a water-soluble epoxy compound is used, the dispersion stability of the ink and the pot life are extremely deteriorated.
非水溶性エポキシ基含有化合物(E)としては、例えば、
アルキルグリシジルエーテル(アルキル炭素数C8〜20)、フェニルグリシジルエーテル、エポキシ化αオレフィン(オレフィン炭素数C8〜20)、リモネンモノオキサイド
3,4−エポキシシクロヘキサンカルボン酸アルキルエステル等の単官能のエポキシ化合物;
ネオペンチルグリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、水添ビスフェノールAジグリシジルエーテル、エポキシ基含有アクリル樹脂、エポキシ基含有スチレン・アクリル樹脂、ビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂、エポキシ化植物油、シクロヘキサンカルボン酸ジグリシジル、4−シクロヘキセン-1,2-ジカルボン酸ジグリシジル、4,5−エポキシテトラヒドロフタル酸ジグリシジルエステル、ペンタエリスリトールポリグリシジルエーテル、2,2−ビス(ヒドロキシメチル)−1−ブタノールの1,2−エポキシ−4−(2−オキシラニル)シクロヘキサン付加物
リモネンジオキサイド、ジシクロペンタジエンジエポキシド、ヘキサン二酸ビス(7-オキサビシクロ[4.1.0]ヘプタン−3−イルメチル)、4−シクロヘキサンジメタノール ビス(3,4−エポキシシクロヘキサンカルボキシレート)、4―フェニレンジメタノール ビス(3,4−エポキシシクロヘキサンカルボキシレート)、3’−4’−エポキシシクロヘキシルメチル 3−4-エポキシシクロヘキサンカルボキシレート等の二官能以上のエポキシ基含有化合物が挙げられる。
As the water-insoluble epoxy group-containing compound (E), for example,
Monofunctional epoxy compounds such as alkyl glycidyl ether (alkyl carbon number C8-20), phenyl glycidyl ether, epoxidized α-olefin (olefin carbon number C8-20), limonene monooxide 3,4-epoxycyclohexanecarboxylic acid alkyl ester;
Neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, epoxy group-containing acrylic resin, epoxy group-containing styrene-acrylic resin, bisphenol-type epoxy resin, novolac-type epoxy resin, epoxidized vegetable oil, cyclohexane 1,1 of diglycidyl carboxylate, diglycidyl 4-cyclohexene-1,2-dicarboxylate, 4,5-epoxytetrahydrophthalic acid diglycidyl ester, pentaerythritol polyglycidyl ether, 2,2-bis (hydroxymethyl) -1-butanol 2-epoxy-4- (2-oxiranyl) cyclohexane adduct limonene dioxide, dicyclopentadiene diepoxide, hexanedioic acid bis (7-oxabicyclo [4.1 0] heptane-3-ylmethyl), 4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate), 4-phenylenedimethanol bis (3,4-epoxycyclohexanecarboxylate), 3'-4'-epoxy Bifunctional or higher functional epoxy group-containing compounds such as cyclohexylmethyl 3-4-epoxycyclohexanecarboxylate are exemplified.
さらに非水溶性エポキシ基含有化合物(E)は、脂環式エポキシ基を有していることが好ましい。より疎水的な脂環式構造により、官能基が粒子核内部に存在し易い。さらに反応性もマイルドであるため、インキの分散安定性、ポットライフの面で優れた性能を発現する。また、他のエポキシ化合物と比較して、安全性も高い。 Furthermore, the water-insoluble epoxy group-containing compound (E) preferably has an alicyclic epoxy group. Due to the more hydrophobic alicyclic structure, functional groups tend to exist inside the particle core. Furthermore, since the reactivity is also mild, it exhibits excellent performance in terms of ink dispersion stability and pot life. Moreover, it is safer than other epoxy compounds.
脂環式エポキシ基を有している非水溶性エポキシ化合物(E)としては、例えば、
リモネンジオキサイド、ジシクロペンタジエンジエポキシド、ヘキサン二酸ビス(7-オキサビシクロ[4.1.0]ヘプタン−3−イルメチル)、4−シクロヘキサンジメタノール ビス(3,4−エポキシシクロヘキサンカルボキシレート)、4―フェニレンジメタノール ビス(3,4−エポキシシクロヘキサンカルボキシレート)、3’−4’−エポキシシクロヘキシルメチル 3−4-エポキシシクロヘキサンカルボキシレート等が挙げられる。
As the water-insoluble epoxy compound (E) having an alicyclic epoxy group, for example,
Limonene dioxide, dicyclopentadiene diepoxide, hexanedioic acid bis (7-oxabicyclo [4.1.0] heptan-3-ylmethyl), 4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate), Examples include 4-phenylenedimethanol bis (3,4-epoxycyclohexanecarboxylate), 3′-4′-epoxycyclohexylmethyl 3-4-epoxycyclohexanecarboxylate, and the like.
非水溶性エポキシ化合物(E)は市販品を使用しても構わない。
非水溶性エポキシ化合物(E)の市販品としては、例えば、
アルケマ社製 バイロコックス10、12、14、16、28等のエポキシ化αオレフィン類;
ダイセル社製 セロキサイド2021P、2081、2000、エポリードGT401、EHPE3150CE(エポキシ樹脂との混合品)等の脂環式エポキシ基含有化合物;
アルケマ社製 LMO/LDO等のテルペンオキサイド類;
日油社製 マープルーフG−017581、東亞合成社製、ALFON UG−4010等のグリシジル基含有アクリル樹脂;
ADEKA社製 アデカレジンEP−4000、EP−4005、7001などの脂環式エポキシ樹脂;
等が挙げられる。
A commercially available product may be used as the water-insoluble epoxy compound (E).
Examples of commercially available water-insoluble epoxy compounds (E) include:
Epoxidized α-olefins such as Birocox 10, 12, 14, 16, 28 manufactured by Arkema, Inc .;
Alicyclic epoxy group-containing compounds such as Celoxide 2021P, 2081, 2000, Epolide GT401, EHPE3150CE (mixed product with epoxy resin) manufactured by Daicel Corporation;
Terpene oxides such as LMO / LDO manufactured by Arkema Co .;
Glycidyl group-containing acrylic resins such as NOF Corporation Marproof G-017581, Toagosei Co., Ltd., ALFON UG-4010;
Adeka resin EP-4000, EP-4005, 7001 and other alicyclic epoxy resins manufactured by ADEKA;
Etc.
非水溶性エポキシ化合物と、コアシェル型樹脂微粒子分散体もしくは顔料分散樹脂との反応は、塗膜の基材密着性、耐水摩擦性を向上させる一方で、反応後に生成する水酸基等の影響により、耐水ブロッキング性を低下させる傾向にある。カルボジイミド基含有樹脂微粒子とコアシェル型樹脂微粒子分散体もしくは顔料分散樹脂との反応では、耐水ブロッキング性は向上するものの、基材によっては濡れ難く、ポットライフも短いため、塗膜耐性が発現しにくい。したがってそれぞれの架橋系を単独で使用しても要求物性を満たすことは困難である。非水溶性エポキシ化合物とカルボジイミド基含有樹脂微粒子分散体を併用した場合、基材密着性、耐水摩擦性が飛躍的に向上する上、耐水ブロッキング性も大幅に改善する。また、ポットライフも長くなり、分散安定性も良好である。これらは、非水溶性エポキシ化合物とカルボジイミド基含有樹脂微粒子分散体の相乗効果によるものと考えられる。 The reaction between the water-insoluble epoxy compound and the core-shell type resin fine particle dispersion or the pigment dispersion resin improves the adhesion of the coating film to the substrate and the water friction resistance. It tends to reduce the blocking property. In the reaction between the carbodiimide group-containing resin fine particles and the core-shell type resin fine particle dispersion or pigment-dispersed resin, the water blocking resistance is improved. However, depending on the substrate, it is difficult to wet and the pot life is short, so that the coating film resistance is hardly exhibited. Therefore, it is difficult to satisfy the required physical properties even if each crosslinking system is used alone. When the water-insoluble epoxy compound and the carbodiimide group-containing resin fine particle dispersion are used in combination, the substrate adhesion and water friction resistance are dramatically improved, and the water blocking resistance is also greatly improved. In addition, the pot life is prolonged and the dispersion stability is good. These are considered to be due to a synergistic effect of the water-insoluble epoxy compound and the carbodiimide group-containing resin fine particle dispersion.
本発明の水性インキ用樹脂組成物は、後述の水性インキ組成物での使用はもちろんのこと、顔料を含まないメジウムインキやオーバーコート剤として使用することも可能である。 The water-based ink resin composition of the present invention can be used as a water-based ink composition, which will be described later, as well as a medium ink or an overcoat agent containing no pigment.
次に本発明の水性インキ組成物について説明する。本発明の水性インキ組成物は、顔料、顔料分散樹脂(F)、水、親水性溶剤ならびに、上述の水性インキ用樹脂組成物を含有してなる水性インキ組成物である。 Next, the water-based ink composition of the present invention will be described. The water-based ink composition of the present invention is a water-based ink composition comprising the pigment, the pigment dispersion resin (F), water, a hydrophilic solvent, and the above-described resin composition for water-based ink.
水性インキ用樹脂組成物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。水性インキ用樹脂組成物が固形分換算で重量5%未満であると、基材と顔料間、顔料同士間の結着が不十分となるため、塗膜物性(基材密着性、耐水摩擦性)が低下する場合がある。また、水性インキ用樹脂組成物が固形分換算で40重量%を超えると、インキ組成物の粘度が著しく上昇し、インキの保存安定性に悪影響を及ぼしたり、乾燥不良の発生し、塗膜物性(基材密着性、耐水摩擦性)が低下する場合がある。 The water-based ink resin composition is preferably used in an amount of 5 to 40% by weight, more preferably 10 to 30% by weight, in terms of solid content in 100% by weight of the water-based ink composition. If the resin composition for water-based ink is less than 5% by weight in terms of solid content, since the binding between the base material and the pigment and between the pigments becomes insufficient, the coating film properties (base material adhesion, water friction resistance) ) May decrease. In addition, if the resin composition for water-based ink exceeds 40% by weight in terms of solid content, the viscosity of the ink composition is remarkably increased, which may adversely affect the storage stability of the ink, cause poor drying, and the physical properties of the coating film. (Substrate adhesion, water friction resistance) may decrease.
顔料分散に使用する顔料分散樹脂(F)としては、インキの安定性を維持し、顔料分散能を有するものであれば任意の水溶性樹脂を用いることができる。 As the pigment dispersion resin (F) used for pigment dispersion, any water-soluble resin can be used as long as it maintains ink stability and has pigment dispersion ability.
優れた顔料吸着能と分散安定性の観点から、顔料分散樹脂(F)は、(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共重合体であることが好ましい。さらにこれらの樹脂は、ラジカル開始剤により溶液重合もしくは塊状重合で合成しても構わないし、市販品を使用しても構わない。また、必要に応じて先述で述べた塩基性化合物を使用することができる。 From the viewpoint of excellent pigment adsorbability and dispersion stability, the pigment dispersion resin (F) is a (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer, 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 An alkyl ester copolymer and a styrene-maleic acid half ester copolymer are preferable. Further, these resins may be synthesized by solution polymerization or bulk polymerization using a radical initiator, or commercially available products may be used. Moreover, the basic compound described above can be used as needed.
顔料分散樹脂(F)の市販品としては、水溶性樹脂(A)で例示したものを使用することができる。 As a commercial item of pigment dispersion resin (F), what was illustrated by water-soluble resin (A) can be used.
顔料への効率的な吸着、コアシェル型樹脂微粒子分散体(C)との相溶性の観点から、顔料分散樹脂(F)は、芳香族骨格を有していることが好ましい。芳香族骨格は、水溶性樹脂(A)と同様に、芳香族含有エチレン性不飽和単量体を共重合するなどして導入することができる。 From the viewpoint of efficient adsorption to the pigment and compatibility with the core-shell resin fine particle dispersion (C), the pigment dispersion resin (F) preferably has an aromatic skeleton. The aromatic skeleton can be introduced by copolymerizing an aromatic-containing ethylenically unsaturated monomer, as in the case of the water-soluble resin (A).
顔料分散樹脂(F)の酸価は70〜230mgKOH/g範囲であることが好ましい。酸価が70mgKOH/g未満であると、造膜時にインキ用樹脂組成物との相溶が低下して、融着が阻害され、塗膜の耐水摩擦性が低下する場合がある。一方で230mgKOH/gを超えると、乾燥不良が発生し、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 acid value of the pigment dispersion resin (F) is preferably in the range of 70 to 230 mgKOH / g. When the acid value is less than 70 mgKOH / g, the compatibility with the resin composition for ink is lowered during the film formation, the fusion is inhibited, and the water friction resistance of the coating film may be lowered. On the other hand, when it exceeds 230 mgKOH / g, poor drying may occur, and water friction resistance and water blocking resistance may be deteriorated.
顔料分散樹脂(F)は、顔料100重量部に対し、固形分換算で10〜60重量部の範囲で使用することが好ましい。顔料分散樹脂が顔料100重量部に対して10重量部未満であると分散安定性が低下して、インキ組成物の分散安定性、保存安定性が悪化する場合がある。一方、顔料分散樹脂が顔料100重量部に対して60重量部を超えるとインキ組成物の粘度が著しく上昇し、インキの保存安定性に悪影響を及ぼす場合がある。また、塗膜の乾燥不良の発生や水への溶出成分が増加するため、塗膜物性(基材密着性、耐水摩擦性、耐ブロッキング性)についても低下する場合がある。 The pigment dispersion resin (F) is preferably used in the range of 10 to 60 parts by weight in terms of solid content with respect to 100 parts by weight of the pigment. If the pigment dispersion resin is less than 10 parts by weight with respect to 100 parts by weight of the pigment, the dispersion stability may decrease, and the dispersion stability and storage stability of the ink composition may deteriorate. On the other hand, when the pigment dispersion resin exceeds 60 parts by weight with respect to 100 parts by weight of the pigment, the viscosity of the ink composition is remarkably increased, which may adversely affect the storage stability of the ink. Moreover, since generation | occurrence | production of the poor drying of a coating film and the elution component to water increase, about a coating-film physical property (base-material adhesiveness, water-friction resistance, blocking resistance), it may fall.
本発明の水性インキ組成物は、コアシェル型樹脂微粒子分散体(C)および顔料分散樹脂(F)由来のカルボキシル基1モルに対して、カルボジイミド基含有樹脂微粒子分散体(D)由来のカルボジイミド基が0.1〜0.5モルの範囲であることが好ましい。カルボジイミド基が0.1モル未満であると、カルボジイミド基の効果が十分に発現せず、塗膜の耐水ブロッキング性が悪化する場合がある。一方で0.5モルを超えた場合、インキ組成物の分散安定性が悪化する恐れがある。また、基材への濡れ性が悪くなり、基材密着性が悪化する場合がある。さらに、カルボジイミド基1モルに対して、非水溶性エポキシ化合物(E)の由来のエポキシ基が0.3〜2モルの範囲であることが好ましい。エポキシ基が0.3モル未満であると、エポキシ基の効果が十分に発現せず、塗膜の耐水摩擦性、基材密着性が低下する場合がある。一方で2モルを超えた場合、過剰な非水溶性エポキシ化合物が塗膜の耐水ブロッキング性に悪影響を及ぼす恐れがある。 The water-based ink composition of the present invention has a carbodiimide group derived from the carbodiimide group-containing resin fine particle dispersion (D) with respect to 1 mol of the carboxyl group derived from the core-shell resin fine particle dispersion (C) and the pigment dispersion resin (F). The range is preferably 0.1 to 0.5 mol. When the carbodiimide group is less than 0.1 mol, the effect of the carbodiimide group is not sufficiently exhibited, and the water blocking resistance of the coating film may be deteriorated. On the other hand, when it exceeds 0.5 mol, the dispersion stability of the ink composition may be deteriorated. Moreover, the wettability with respect to a base material worsens, and base material adhesiveness may deteriorate. Furthermore, it is preferable that the epoxy group derived from the water-insoluble epoxy compound (E) is in the range of 0.3 to 2 mol with respect to 1 mol of the carbodiimide group. When the epoxy group is less than 0.3 mol, the effect of the epoxy group is not sufficiently exhibited, and the water friction resistance and the substrate adhesion of the coating film may be lowered. On the other hand, when it exceeds 2 mol, an excessive water-insoluble epoxy compound may adversely affect the water blocking resistance of the coating film.
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%の割合で配合することが好ましい。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 ". 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%.
さらに本発明の水性インキ組成物は、基材への濡れ性、インキの乾燥性を制御する目的で、親水性溶剤を含有している。 Furthermore, the water-based ink composition of the present invention contains a hydrophilic solvent for the purpose of controlling the wettability to the substrate and the drying property of the ink.
水性インキ組成物100重量%中、親水性溶剤は1〜10重量%含有していることが好ましく、より好ましくは2〜5重量%の範囲内である。親水性溶剤が1重量%未満であると、印刷適性が悪化して塗膜物性(基材密着性、耐水摩擦性)が低下する場合がある。一方、親水性溶剤の含有量が10重量%を超えると、塗膜の乾燥不良が発生し、塗膜物性(基材密着性、耐水摩擦性、耐ブロッキング性)が低下してしまう場合がある。 In 100% by weight of the aqueous ink composition, the hydrophilic solvent is preferably contained in an amount of 1 to 10% by weight, more preferably in the range of 2 to 5% by weight. If the hydrophilic solvent is less than 1% by weight, the printability may be deteriorated and the physical properties of the coating film (substrate adhesion, water friction resistance) may be lowered. On the other hand, when the content of the hydrophilic solvent exceeds 10% by weight, the coating film may be poorly dried, and the physical properties of the coating film (base material adhesion, water friction resistance, blocking resistance) may be deteriorated. .
親水性溶剤としては、例えば、エタノール、1−プロパノール、2−プロパノール、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
等が挙げられる。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 monovalent alcohol solvents such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, and 2-methyl-2-propanol;
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, ε-caprolactam;
Examples include amide solvents such as formamide, N-methylformamide, N, N-dimethylformamide, Idemitsu ecamide M-100, and equamide B-100. These can be used alone or in combination of two or more.
本発明の水性インキ組成物には、基材への密着性向上やケト−ヒドラジド架橋の形成を目的として水溶性のヒドラジド化合物を適宜使用することができる。ヒドラジド化合物は、樹脂組成物段階で添加しても構わないし、インキ組成物調製時に添加しても構わない。 In the water-based ink composition of the present invention, a water-soluble hydrazide compound can be appropriately used for the purpose of improving adhesion to a substrate and forming a keto-hydrazide bridge. The hydrazide compound may be added at the resin composition stage, or may be added at the time of preparing the ink composition.
水溶性のヒドラジド化合物としては、例えば、アジピン酸ジヒドラジドや、多官能のヒドラジド基が変性された水溶性樹脂などが挙げられる。 Examples of the water-soluble hydrazide compound include adipic acid dihydrazide and water-soluble resins in which a polyfunctional hydrazide group is modified.
コアシェル型樹脂微粒子分散体(C)がケト基を含有している場合、ケト−ヒドラジド架橋の形成を目的として、水溶性のヒドラジド化合物を添加することが好ましい。ヒドラジド化合物の添加量は、ケト基1.0モルに対してヒドラジド基が0.5〜1.0モルになるよう添加するのが好ましい。 When the core-shell type resin fine particle dispersion (C) contains a keto group, it is preferable to add a water-soluble hydrazide compound for the purpose of forming a keto-hydrazide bridge. The amount of the hydrazide compound added is preferably 0.5 to 1.0 mol of hydrazide group with respect to 1.0 mol of keto group.
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ことができる。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。 For the water-based 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.
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ことができる。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.
本発明の水性インキ組成物は、低温乾燥下においても、ポリプロピレンやポリエチレン、ポリエステル等のフィルム基材に対して、優れた基材密着性、耐水摩擦性を発現する。また、紙などの浸透性基材と違い、水分が逃げづらく、乾燥性の悪いフィルム基材においても、優れた耐水ブロッキング性を発現する。さらにインキの分散安定性も良好であり、ポットライフも長い。従って、フィルム基材への基材拡張、高速印刷(低温乾燥)が必要とされている水性フレキソ印刷・グラビア印刷への展開が大いに期待できる。フィルム基材の中でも、特に塗膜耐性発現が難しいポリエチレンテレフタラートフィルムに対して優れた物性を発現する。フィルム基材に限らず、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ことも可能である。 The water-based ink composition of the present invention exhibits excellent substrate adhesion and water friction resistance to film substrates such as polypropylene, polyethylene, and polyester even under low temperature drying. In addition, unlike water-permeable substrates such as paper, moisture is difficult to escape and even a film substrate with poor drying properties exhibits excellent water blocking resistance. Furthermore, the dispersion stability of the ink is good and the pot life is long. Therefore, the expansion to the base material of a film base material and the development to water-based flexographic printing and gravure printing, which require high-speed printing (low-temperature drying), can be greatly expected. Among the film bases, it exhibits excellent physical properties, especially for polyethylene terephthalate film, which is difficult to express coating film resistance. Not only the film substrate but also a conventional substrate such as a permeable substrate such as fine paper, art paper, and coated paper can be used for the purpose of improving the physical properties of the coating film.
乾燥工程は、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ことが可能である。水性フレキソ印刷においては、40〜100℃の低温で1〜180秒の範囲で処理するのが一般的である。乾燥後の印刷物については、巻き取られた状態で保管される。 In the drying step, any temperature can be applied as long as it does not adversely affect the substrate. In aqueous flexographic printing, the treatment is generally performed at a low temperature of 40 to 100 ° C. for 1 to 180 seconds. The dried printed matter is stored in a wound state.
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”.
<水溶性樹脂(A)の製造>
[製造例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、酢酸ブチル94.0部を仕込み、攪拌しながら、窒素還流下で温度100℃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、スチレン40.0部、アクリル酸28.0部、メチルメタクリレート15.0部、n−ブチルアクリレート17.0部を3時間かけて滴下した。もう一方からは、ジメチル2,2‘−アゾビスイソブチレート6.8部を酢酸ブチル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。反応完了後、乾燥させて溶剤を除去し、固形の水溶性樹脂(A)を得た。水溶性樹脂(A)の酸価は204mgKOH/g、重量平均分子量は10700であった。
<Production of water-soluble resin (A)>
[Production Example 1]
In a separate reaction vessel equipped with a stirrer, thermometer, two dropping funnels, and a refluxing device, 94.0 parts of butyl acetate was charged and the temperature was raised to 100 ° C. under nitrogen reflux while stirring. Next, in two dropping funnels, 40.0 parts of styrene, 28.0 parts of acrylic acid, 15.0 parts of methyl methacrylate, and 17.0 parts of n-butyl acrylate were dropped from one side over 3 hours. From the other side, 6.8 parts of dimethyl 2,2′-azobisisobutyrate was dissolved in 12.0 parts of butyl acetate and added dropwise over 4 hours. After completion of dropping, the reaction was further continued for 10 hours. After completion of the reaction, the solvent was removed by drying to obtain a solid water-soluble resin (A). The acid value of the water-soluble resin (A) was 204 mgKOH / g, and the weight average molecular weight was 10700.
[製造例2〜10]
製造例1と同様に、表1に示す組成で水溶性樹脂(A)を合成し、溶剤を除去して固形の水溶性樹脂(A)を得た。
[Production Examples 2 to 10]
Similarly to Production Example 1, a water-soluble resin (A) was synthesized with the composition shown in Table 1, and the solvent was removed to obtain a solid water-soluble resin (A).
[製造例11]
攪拌器、温度計、還流器を備えた別の反応容器にP-2011(クラレ社製 ポリエステルポリオール)174.0部、ジメチロールブタン酸47.9部、メチルエチルケトン128.6部を仕込み、窒素置換しながら、60℃まで昇温した。さらにイソホロンジイソシアネート78.1部、ジブチル錫ラウリレート0.02部を加え、80℃まで昇温し、8時間反応させた。得られた水溶性樹脂(A)の重量平均分子量は8900、酸価は60mgKOH/gであった。
[Production Example 11]
In a separate reaction vessel equipped with a stirrer, thermometer, and refluxer, charge 174.0 parts of P-2011 (Kuraray Polyester Polyol), 47.9 parts of dimethylolbutanoic acid, 128.6 parts of methyl ethyl ketone, and purge with nitrogen. The temperature was raised to 60 ° C. Furthermore, 78.1 parts of isophorone diisocyanate and 0.02 part of dibutyltin laurate were added, and the temperature was raised to 80 ° C. and reacted for 8 hours. The obtained water-soluble resin (A) had a weight average molecular weight of 8,900 and an acid value of 60 mgKOH / g.
[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mg数。水溶性樹脂(A)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。
[Acid value]
The number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of resin. The water-soluble resin (A) was calculated by performing potentiometric titration with a potassium hydroxide / ethanol solution according to the method described in JIS K2501.
[重量平均分子量]
乾燥させた水溶性樹脂(A)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-Super Multipore HZ−M0021488 4.6 mmI.D.×15cm×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 dried water-soluble resin (A) 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-Super Multipore HZ-M0021488 4.6 mm ID × 15 cm × 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, amount of sample solution used: 10 μL, column temperature: 40 ° C.
<コアシェル型樹脂微粒子分散体(C)の製造>
[製造例12]
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1で調製した水溶性樹脂(A)40.0部、25%アンモニア水9.9部、イオン交換水145.7部を添加し、攪拌しながら60℃に昇温して水溶性樹脂(A)を溶解させた。(アンモニア水は水溶性樹脂(A)のカルボキシル基を100%中和する量を添加した。)さらに窒素還流下で温度を80℃まで昇温した。2つの滴下ロートにおいて、一方からは、スチレン20.0部、フェノキシエチルアクリレート18.0部、n−ブチルアクリレート10.0部、2−エチルヘキシルアクリレート52.0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4時間反応させてコアシェル型樹脂微粒子分散体を得た。イオン交換水により、最終固形分を45.0%に調整した。得られたコアシェル型樹脂微粒子分散体について、平均粒子径、重量平均分子量、コア部のTgを測定した。重量平均分子量は水溶性樹脂(A)と同様の方法で測定した。得られたコアシェル型樹脂微粒子分散体の平均粒子径は84nm、重量平均分子量は420000、コア部のガラス転移温度は−28℃であった。
<Manufacture of core-shell type resin fine particle dispersion (C)>
[Production Example 12]
In a separate reaction vessel equipped with a stirrer, thermometer, two dropping funnels, and reflux, 40.0 parts of water-soluble resin (A) prepared in Production Example 1, 9.9 parts of 25% aqueous ammonia, ion exchange 145.7 parts of water was added and the temperature was raised to 60 ° C. with stirring to dissolve the water-soluble resin (A). (Ammonia water was added in an amount that neutralizes the carboxyl group of the water-soluble resin (A) 100%.) Further, the temperature was raised to 80 ° C. under nitrogen reflux. In two dropping funnels, a mixed solution of 20.0 parts of styrene, 18.0 parts of phenoxyethyl acrylate, 10.0 parts of n-butyl acrylate, and 52.0 parts of 2-ethylhexyl acrylate was dropped from one side over 2 hours. did. From the other side, 4.0 parts of a 20% aqueous solution of ammonium persulfate was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was further reacted for 4 hours to obtain a core-shell type resin fine particle dispersion. The final solid content was adjusted to 45.0% with ion-exchanged water. About the obtained core-shell type resin fine particle dispersion, the average particle diameter, the weight average molecular weight, and the Tg of the core part were measured. The weight average molecular weight was measured by the same method as that for the water-soluble resin (A). The obtained core-shell resin fine particle dispersion had an average particle diameter of 84 nm, a weight average molecular weight of 420,000, and a glass transition temperature of the core part of −28 ° C.
[平均粒子径]
樹脂微粒子分散体を500倍に水希釈し、該希釈液約5mlを動的光散乱測定法(測定装置はナノトラックUPA(株)日機装製)により測定をおこなった。この時得られた体積粒子径分布データ(ヒストグラム)のピークを平均粒子径とした。
[Average particle size]
The resin fine particle dispersion was diluted with water 500 times, and about 5 ml of the diluted solution was measured by a dynamic light scattering measurement method (measurement device manufactured by Nikkiso Co., Ltd.). The peak of the volume particle size distribution data (histogram) obtained at this time was defined as the average particle size.
[ガラス転移温度(Tg)]
ガラス転移温度(Tg)は、DSC(示差走査熱量計 TAインスツルメント社製)により測定した。樹脂微粒子分散体を乾固したサンプル約2mgをアルミニウムパン上で秤量し、該アルミニウムパンをDSC測定ホルダーにセットし、5℃/分の昇温条件にて得られるチャートの吸熱ピークを読み取り、ガラス転移温度(Tg)を得た。
[Glass transition temperature (Tg)]
The glass transition temperature (Tg) was measured by DSC (Differential Scanning Calorimeter TA Instruments). About 2 mg of a sample obtained by drying the resin fine particle dispersion is weighed on an aluminum pan, the aluminum pan is set on a DSC measurement holder, and the endothermic peak of the chart obtained under a temperature rising condition of 5 ° C./min is read. A transition temperature (Tg) was obtained.
[製造例13〜31]
表2に示す配合組成で、製造例12と同様の方法で、製造例13〜31のコアシェル型樹脂微粒子分散体(C)を合成した。この時、水溶性樹脂(A)のカルボキシル基が100%中和されるように25%アンモニア水を添加した。製造例31については、高分子乳化剤がカルボキシル基を有しておらず、中和する必要が無いため、溶解時に25%アンモニア水を添加しなかった。合成完了後、イオン交換水により、コアシェル型樹脂微粒子分散体(C)の最終固形分を45.0%に調整した。製造例15、19、26については、仕込みのジアセトンアクリルアミドに対して1/2当量に相当するアジピン酸ジヒドラジドを固形分調整時に添加した。重量平均分子量など、物性の測定はアジピン酸ヒドラジドを添加する前におこなった。
[Production Examples 13 to 31]
Core-shell type resin fine particle dispersions (C) of Production Examples 13 to 31 were synthesized by the same method as Production Example 12 with the composition shown in Table 2. At this time, 25% aqueous ammonia was added so that the carboxyl group of the water-soluble resin (A) was neutralized 100%. For Production Example 31, since the polymer emulsifier does not have a carboxyl group and does not need to be neutralized, 25% aqueous ammonia was not added during dissolution. After completion of the synthesis, the final solid content of the core-shell resin fine particle dispersion (C) was adjusted to 45.0% with ion-exchanged water. For Production Examples 15, 19, and 26, adipic acid dihydrazide corresponding to 1/2 equivalent to the charged diacetone acrylamide was added during solid content adjustment. Physical properties such as weight average molecular weight were measured before adding adipic hydrazide.
表2に記載の化合物を下記に示す。
SMA2000(CrayValley製 スチレン・無水マレイン酸樹脂、Mw7500、酸価350)
M−205(クラレ製 反応性基含有ポリビニルアルコール)
The compounds listed in Table 2 are shown below.
SMA2000 (made by Cray Valley, styrene / maleic anhydride resin, Mw7500, acid value 350)
M-205 (Kuraray Reactive Group-Containing Polyvinyl Alcohol)
<水性インキ組成物の製造> <Production of water-based ink composition>
<顔料分散樹脂(F)の製造>
[製造例32]
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、メチルイソブチルケトン94部を仕込み、攪拌しながら、窒素還流下で温度100℃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、スチレン20.0部、α−メチルスチレン5.0部、アクリル酸15.0部、メチルメタクリレート30.0部、n-ブチルアクリレート30.0部を3時間かけて滴下した。もう一方からは、ジメチル2,2‘−アゾビスイソブチレート5部をメチルイソブチルケトン5.0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。反応完了後、乾燥させて溶剤を除去し、固形の顔料分散樹脂(F)を得た。酸価ならびに重量平均分子量は水溶性樹脂(A)と同様の方法で測定した。得られた顔料分散樹脂(F)の酸価は111mgKOH/g、重量平均分子量は10300であった。この顔料分散樹脂(F)に、カルボキシル基が100%中和されるように25%アンモニア水を加え、更にイオン交換水を加えて、加熱、攪拌しながら顔料分散樹脂(F)の28.0%水溶液を得た。
<Manufacture of pigment dispersion resin (F)>
[Production Example 32]
In a separate reaction vessel equipped with a stirrer, thermometer, two dropping funnels, and reflux, 94 parts of methyl isobutyl ketone was charged, and the temperature was raised to 100 ° C. under nitrogen reflux while stirring. Next, in two dropping funnels, from one side, 20.0 parts of styrene, 5.0 parts of α-methylstyrene, 15.0 parts of acrylic acid, 30.0 parts of methyl methacrylate, 30.0 parts of n-butyl acrylate Was added dropwise over 3 hours. From the other side, 5 parts of dimethyl 2,2′-azobisisobutyrate was dissolved in 5.0 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 was completed, the solvent was removed by drying to obtain a solid pigment dispersion resin (F). The acid value and the weight average molecular weight were measured by the same method as that for the water-soluble resin (A). The obtained pigment dispersion resin (F) had an acid value of 111 mgKOH / g and a weight average molecular weight of 10,300. To this pigment dispersion resin (F), 25% ammonia water is added so that the carboxyl groups are neutralized 100%, and ion exchange water is further added, and 28.0 of the pigment dispersion resin (F) is heated and stirred. % Aqueous solution was obtained.
[製造例33〜38]
表3に示す配合組成で、製造例32と同様の方法で、製造例33〜38の顔料分散樹脂(F)を合成し、28.0%水溶液を調製した。
[Production Examples 33 to 38]
In the same manner as in Production Example 32, the pigment dispersion resins (F) of Production Examples 33 to 38 were synthesized with the composition shown in Table 3 to prepare a 28.0% aqueous solution.
<濃縮顔料分散液の製造> <Production of concentrated pigment dispersion>
[製造例39]
<濃縮白顔料分散液の製造>
顔料[タイペークCR80 石原産業社製]67.5部、製造例32の顔料分散剤水溶液(固形分28%)25.0部、イオン交換水2.1部、表面調整剤[サーフィノール420 日信化学工業社製]0.4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。
[Production Example 39]
<Production of concentrated white pigment dispersion>
67.5 parts of pigment [Taipeke CR80 made by Ishihara Sangyo Co., Ltd.], 25.0 parts of pigment dispersant aqueous solution (solid content 28%) of Production Example 32, 2.1 parts of ion-exchanged water, surface conditioner [Surfinol 420 Nissin Chemical Co., Ltd.] 0.4 parts was dispersed with a paint conditioner for 2 hours to obtain a concentrated white pigment dispersion.
[製造例40〜45]
表4に示す配合組成で、製造例39と同様の方法で濃縮白顔料分散液を調製した。
[Production Examples 40 to 45]
A concentrated white pigment dispersion was prepared in the same manner as in Production Example 39 with the formulation shown in Table 4.
[製造例46]
<濃縮藍顔料分散液の製造>
顔料[リオノールブルーFG7330 トーヨーカラー社製]34.2部、製造例32の顔料分散樹脂水溶液(固形分28%)22.0部、イオン交換水26.4部、表面調整剤[サーフィノール420 日信化学工業製]0.4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。
[Production Example 46]
<Manufacture of concentrated indigo pigment dispersion>
34.2 parts of a pigment [Lionol Blue FG7330 manufactured by Toyocolor Co., Ltd.], 22.0 parts of an aqueous pigment-dispersed resin solution (solid content 28%) of Production Example 32, 26.4 parts of ion-exchanged water, a surface conditioner [Surfinol 420 Nissin Chemical Industry Co., Ltd.] 0.4 parts was dispersed with a paint conditioner for 2 hours to obtain a concentrated indigo pigment dispersion.
[製造例47〜52]
表5に示す配合組成で、製造例46と同様の方法で濃縮藍顔料分散液を調製した。
[Production Examples 47 to 52]
A concentrated indigo pigment dispersion was prepared in the same manner as in Production Example 46 with the formulation shown in Table 5.
<水性インキ用樹脂組成物の調製>
[実施例1]
製造例12で製造したコアシェル型樹脂微粒子分散体(C)76.2部、カルボジライトE−01(日清紡ケミカル社製 カルボジイミド基含有樹脂微粒子分散体 固形分40%)11.9部、2-エチルヘキシルグリシジルエーテル11.9部を添加し、攪拌・混合して目的の水性インキ用樹脂組成物を得た。
<Preparation of water-based ink resin composition>
[Example 1]
76.2 parts of the core-shell type resin fine particle dispersion (C) produced in Production Example 12, 11.9 parts of carbodilite E-01 (Nisshinbo Chemical Co., Ltd. carbodiimide group-containing resin fine particle dispersion solid content 40%), 2-ethylhexylglycidyl 11.9 parts of ether was added and stirred and mixed to obtain the desired resin composition for water-based ink.
[実施例2〜29および比較例1〜12]
表6および表7に示す配合組成で、実施例1と同様の方法で、実施例2〜29ならびに比較例1〜12の水性インキ用樹脂組成物を得た。
[Examples 2-29 and Comparative Examples 1-12]
Resin compositions for aqueous inks of Examples 2 to 29 and Comparative Examples 1 to 12 were obtained in the same manner as in Example 1 with the blending compositions shown in Tables 6 and 7.
表6に記載の化合物を下記に示す。
カルボジライトE−01(日清紡ケミカル社製 カルボジイミド基含有エマルジョン カルボジイミド当量425)
カルボジライトE−02(日清紡ケミカル社製 カルボジイミド基含有エマルジョン カルボジイミド当量445)
カルボジライトE−03A(日清紡ケミカル社製 カルボジイミド基含有エマルジョン カルボジイミド当量365)
マープルーフG−017581(日油社製グリシジル基含有アクリル樹脂 Mw10000 エポキシ当量240)
LMO/LDO(アルケマ社製 リモネンモノオキサイドとリモネンジオキサイドの混合物 LMO/LDO=7/3)
EHPE3150CE(ダイセル社製3',4'-エポキシシクロヘキシルメチル 3,4-エポキシシクロヘキサンカルボキシレート と2,2-ビス(ヒドロキシメチル)-1-ブタノールの1,2-エポキシ-4-(2-オキシラニル)シクロヘキサン付加物の混合品 エポキシ当量152)
The compounds listed in Table 6 are shown below.
Carbodilite E-01 (Nisshinbo Chemical Co., Ltd. Carbodiimide group-containing emulsion Carbodiimide equivalent 425)
Carbodilite E-02 (Nisshinbo Chemical Co., Ltd. Carbodiimide group-containing emulsion Carbodiimide equivalent 445)
Carbodilite E-03A (Nisshinbo Chemical Co., Ltd. Carbodiimide group-containing emulsion Carbodiimide equivalent 365)
Marproof G-017581 (manufactured by NOF Corporation glycidyl group-containing acrylic resin Mw10000 epoxy equivalent 240)
LMO / LDO (mixture of limonene monooxide and limonene dioxide produced by Arkema LMO / LDO = 7/3)
EHPE3150CE (1,2-epoxy-4- (2-oxiranyl) of 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate and 2,2-bis (hydroxymethyl) -1-butanol manufactured by Daicel Corporation Mixture of cyclohexane adduct epoxy equivalent 152)
表7に記載の化合物を下記に示す。(表6と重複しているものは除く)
デナコールEX−850(ナガセケムテックス社製 ジエチレングリコールジグリシジルエーテル エポキシ当量122)
The compounds listed in Table 7 are shown below. (Excluding those that overlap with Table 6)
Denacol EX-850 (manufactured by Nagase ChemteX Corporation diethylene glycol diglycidyl ether epoxy equivalent 122)
<水性インキ組成物の調製>
[実施例30]
実施例1で得られた水性インキ用樹脂組成物42.0部に対して、製造例39の濃縮白顔料分散液47.5部、ケミパールW500(三井化学製ポリオレフィン水分散体) 5.0部、n-プロパノール部4.0部、ブチルジグリコール1.0部、イオン交換水0.5部を加えた後、混練して白色水性インキ組成物を得た。
<Preparation of water-based ink composition>
[Example 30]
47.5 parts of the concentrated white pigment dispersion of Production Example 39 and 5.0 parts of Chemipearl W500 (polyolefin aqueous dispersion manufactured by Mitsui Chemicals) with respect to 42.0 parts of the resin composition for water-based ink obtained in Example 1 Then, 4.0 parts of n-propanol part, 1.0 part of butyl diglycol and 0.5 part of ion-exchanged water were added and then kneaded to obtain a white aqueous ink composition.
[実施例31〜58および比較例13〜24]
表8および表9に示す配合組成で、実施例30と同様の方法で調製し、実施例31〜58および比較例13〜24の白色水性インキ組成物を得た。
[Examples 31-58 and Comparative Examples 13-24]
It was prepared in the same manner as in Example 30 with the composition shown in Table 8 and Table 9, and white aqueous ink compositions of Examples 31 to 58 and Comparative Examples 13 to 24 were obtained.
表8に記載の化合物を下記に示す。
ケミパールW−500(三井化学社製 ポリオレフィン水分散体 固形分40%)
The compounds listed in Table 8 are shown below.
Chemipearl W-500 (Mitsui Chemicals polyolefin water dispersion solid content 40%)
[実施例59]
実施例1で得られた水性インキ用樹脂組成物42.0部に対して、製造例46の濃縮藍顔料分散液41.5部、ケミパールW500(三井化学社製ポリオレフィン水分散体) 4.5部、n-プロパノール部3.0部、ブチルジグリコール1.0部、イオン交換水8.0部を加えた後、混練して藍色水性インキ組成物を得た。
[Example 59]
41.5 parts of the concentrated indigo pigment dispersion of Production Example 46 and Chemipearl W500 (polyolefin water dispersion manufactured by Mitsui Chemicals) 4.5% of the resin composition for water-based ink obtained in Example 1 Part, n-propanol part 3.0 part, butyl diglycol 1.0 part and ion-exchanged water 8.0 part were added and then kneaded to obtain an indigo water-based ink composition.
[実施例60〜87および比較例25〜36]
表10および表11に示す配合組成で、実施例59と同様の方法で調製し、実施例60〜87および比較例25〜36藍色水性インキ組成物を得た。
[Examples 60 to 87 and Comparative Examples 25 to 36]
The blending compositions shown in Table 10 and Table 11 were prepared in the same manner as in Example 59 to obtain Examples 60 to 87 and Comparative Examples 25 to 36 indigo water-based ink compositions.
<水性インキ組成物の評価>
上記で調製した水性インキ組成物について、経時で分散安定性(分離、沈殿、流動性の有無)を評価した。さらに水性インキ組成物を、フレキシプルーフ100(アニロックスローラー70線/cm)を用いて、処理PETフィルム(東洋紡製ポリエステルフィルムE-5100・厚み12μ)に2回塗工し、オーブンで60℃・1分ほど加熱処理してから、塗工面が空気にさらされないように、未処理PETフィルムを上から重ね合わせた。この評価用塗膜を恒温恒湿室で40℃、1日保管した後、基材密着性、耐水摩擦性、耐水ブロッキング性を評価した。(耐水ブロッキング性は、塗工面上に水を含んだ状態でのブロッキング試験であり、通常のブロッキング試験よりも、乾燥不良や水への溶出成分の影響を受けやすい。)評価は調製直後ならびに経時後のインキ組成物についておこなった。ポットライフは、経時後のインキ組成物の塗工の可否、塗膜物性(基材密着性、耐水摩擦性、耐水ブロッキング性)から評価した。表8〜表11にその結果を示す。
<Evaluation of water-based ink composition>
The aqueous ink composition prepared above was evaluated for dispersion stability (presence of separation, precipitation, fluidity) over time. Further, the water-based ink composition was applied twice to a treated PET film (Toyobo polyester film E-5100, thickness 12 μ) using Flexiproof 100 (anilox roller 70 lines / cm), and then heated in an oven at 60 ° C. After heat treatment for about minutes, the untreated PET film was overlaid from above so that the coated surface was not exposed to air. After this coating film for evaluation was stored at 40 ° C. for 1 day in a constant temperature and humidity chamber, the substrate adhesion, water friction resistance, and water blocking resistance were evaluated. (Water blocking resistance is a blocking test in which water is contained on the coated surface, and is more susceptible to drying defects and components eluted into water than normal blocking tests.) This was done for the later ink composition. The pot life was evaluated from the applicability of the ink composition after the passage of time and the physical properties of the coating film (substrate adhesion, water rub resistance, water blocking resistance). Tables 8 to 11 show the results.
[分散安定性]
水性インキ組成物について、経時で分離、沈殿物、流動性の有無を目視で確認した。分離や沈殿物の発生が無く、流動性が有る状態を安定とした。分離または沈殿物が発生する、流動性が無い状態を不安定とした。
評価基準は以下の通りである。(実用可能レベルは○△以上)
◎:調製から24時間後まで安定である。
○;調製から16時間後まで安定である。
○△;調製から12時間後まで安定である。
△;調製から8時間後まで安定である。
×;調製から4時間後まで安定である。
[Dispersion stability]
About the water-based ink composition, the presence or absence of separation, precipitate, and fluidity was visually confirmed over time. There was no separation or precipitation, and the fluid state was stabilized. A state where separation or precipitation occurs and no fluidity is regarded as unstable.
The evaluation criteria are as follows. (Practical level is more than ○ △)
A: Stable until 24 hours after preparation.
○: Stable until 16 hours after preparation.
○ △: Stable until 12 hours after preparation.
Δ: Stable until 8 hours after preparation.
X: Stable until 4 hours after preparation.
[基材密着性]
評価用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(5%未満)
○△;インキの剥がれがややある(5%以上、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 coating film for evaluation, a peel test was performed 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 ○: Ink peeling slightly (less than 5%)
○ △: Some ink peeling (5% or more, less than 10%)
Δ: Ink peeling (10% or more, less than 50%)
×: Ink peeling is considerable (50% or more)
[耐水摩擦性]
評価用塗膜を水に浸漬後、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800gで40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(1%未満)
○△;インキの剥がれがややある(1%以上、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]
After immersing the evaluation coating film in water, the surface of the coated coating film was reciprocated 40 times with a load of 800 g using a Gakushin Tester (manufactured by Tester Sangyo Co., Ltd.) using Kanakin (JIS L 0803) as a friction element. 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 1%)
○ △: Some ink peeling (1% or more, less than 5%)
Δ: Ink peeling (5% or more, less than 30%)
×: Ink peeling is considerable (30% or more)
[耐水ブロッキング性]
評価用塗膜について、塗工面に水を一滴垂らし、未処理PETフィルムを重ね合わせ、1kg/cm2の荷重をかけて、恒温恒湿室で、40℃で24時間放置した。その後、評価用塗膜を取り出し、裏写りの有無を確認した。裏移りした面積の割合から耐水ブロッキング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)
◎;剥離時に音がせず、裏移りもしていない
○;剥離時に音がするが、裏移りはしていない
○△;インキがやや裏面に裏写りしている(1%未満)
△; インキがやや裏面に裏写りしている(1%以上5%未満)
×;インキが裏面に裏写りしている(5%以上)
[Water blocking resistance]
For the coating film for evaluation, a drop of water was dropped on the coated surface, an untreated PET film was overlaid, a load of 1 kg / cm 2 was applied, and the coating film was left at 40 ° C. for 24 hours. Then, the coating film for evaluation was taken out and the presence or absence of show-through was confirmed. The water blocking resistance was evaluated from the ratio of the offset area.
The evaluation criteria are as follows. (Practical level is more than ○ △)
◎: No sound when peeling, no set-off ○: Sound when peeled, but no set-off ○ △: The ink is slightly show-through on the back (less than 1%)
△; Ink is slightly on the back (1% or more and less than 5%)
X: Ink is showing through on the back (5% or more)
[ポットライフ]
経時の水性インキ組成物について、上述の印刷機での塗工性ならびに塗膜物性(基材密着性、耐水摩擦性、耐水ブロッキング性)からポットライフを評価した。評価基準は以下の通りである(実用可能レベルは○△以上)
◎;調製から24時間後まで塗工可能かつ調製直後のインキと同等の塗膜物性を発現する
○;調製から16時間後まで塗工可能かつ調製直後のインキと同等の塗膜物性を発現する。
○△;調製から12時間後まで塗工可能かつ調製直後のインキと同等の塗膜物性を発現する。
△;調製から8時間後まで塗工可能かつ調製直後のインキと同等の塗膜物性を発現する
×;調製から4時間後まで塗工可能かつ調製直後のインキと同等の塗膜物性を発現する
[Pot life]
About the water-based ink composition of time, pot life was evaluated from the coating property by the above-mentioned printing press, and coating-film physical property (base-material adhesiveness, water friction resistance, water blocking resistance). The evaluation criteria are as follows (practical level is more than ○ △)
A: Applicable up to 24 hours after preparation and expresses coating film properties equivalent to those of ink immediately after preparation. O; Applicable up to 16 hours after preparation and expresses coating film properties equivalent to that of ink immediately after preparation. .
◯: Applicable up to 12 hours after preparation and exhibiting coating film properties equivalent to ink immediately after preparation.
Δ: Applicable up to 8 hours after preparation and expresses coating film properties equivalent to ink immediately after preparation ×: Applicable up to 4 hours after preparation and expresses coating film properties equivalent to ink immediately after preparation
表8および表11に示すように、実施例1〜29の水性インキ用樹脂組成物を使用した白色水性インキ組成物(実施例30〜58)ならびに藍色水性インキ組成物(実施例59〜87)は分散安定性が良好であり、低温乾燥下でもフィルム基材に対して優れた基材密着性、耐水摩擦性、耐水ブロッキング性を発現することが確認された。ポットライフについても、少なくとも調製から8時間までは問題なく使用できる結果であった。これらは全ての項目において、実用上可能なレベルを満たしている。一方、比較例1〜12の水性インキ用樹脂組成物を使用した白色水性インキ組成物(比較例13〜24)ならびに藍色水性インキ組成物(比較例25〜36)は、分散安定性、塗膜物性(基材密着性、耐水摩擦性、耐水ブロッキング性)、ポットライフのいずれかに問題を有しており、実用可能なレベルを満たさない結果となった。 As shown in Table 8 and Table 11, white aqueous ink compositions (Examples 30 to 58) and indigo water-based ink compositions (Examples 59 to 87) using the resin compositions for aqueous inks of Examples 1 to 29. ) Has good dispersion stability and was confirmed to exhibit excellent substrate adhesion, water friction resistance, and water blocking resistance with respect to the film substrate even under low temperature drying. The pot life was a result that could be used without any problem for at least 8 hours after preparation. All of these items satisfy practically possible levels. On the other hand, white aqueous ink compositions (Comparative Examples 13 to 24) and indigo water-based ink compositions (Comparative Examples 25 to 36) using the resin compositions for aqueous inks of Comparative Examples 1 to 12 have dispersion stability, coating The film physical properties (base material adhesion, water rub resistance, water blocking resistance), and pot life have problems, and the result does not satisfy the practical level.
Claims (8)
カルボジイミド基含有樹脂微粒子分散体(D)と、
非水溶性エポキシ基含有化合物(E)とを含有してなる水性インキ用樹脂組成物。 A core-shell resin fine particle dispersion (C) obtained by emulsion polymerization of an ethylenically unsaturated monomer (B) in an aqueous medium using a water-soluble resin (A) having a carboxyl group as a polymer emulsifier;
A carbodiimide group-containing resin fine particle dispersion (D);
A water-based ink resin composition comprising a water-insoluble epoxy group-containing compound (E).
分散樹脂(D)由来のカルボジイミド基1モルに対して、化合物(E)由来のエポキシ基が0.3〜2モルの範囲である請求項6記載の水性インキ組成物。 The carbodiimide group derived from the dispersion (D) is in the range of 0.1 to 0.5 mol with respect to 1 mol of the carboxyl group derived from the dispersion (C) and the resin (F),
The water-based ink composition according to claim 6, wherein the epoxy group derived from the compound (E) is in the range of 0.3 to 2 mol relative to 1 mol of the carbodiimide group derived from the dispersion resin (D).
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GB0427747D0 (en) * | 2004-12-18 | 2005-01-19 | Avecia Ltd | Process |
JP5811835B2 (en) * | 2011-03-29 | 2015-11-11 | 東洋インキScホールディングス株式会社 | Printing ink composition |
US20140296393A1 (en) * | 2013-03-29 | 2014-10-02 | E I Du Pont De Nemours And Company | Inkjet inks containing pigmented dispersions with improved water redispersability |
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