JP6839585B2 - Dispersant composition for printing ink - Google Patents
Dispersant composition for printing ink Download PDFInfo
- Publication number
- JP6839585B2 JP6839585B2 JP2017066605A JP2017066605A JP6839585B2 JP 6839585 B2 JP6839585 B2 JP 6839585B2 JP 2017066605 A JP2017066605 A JP 2017066605A JP 2017066605 A JP2017066605 A JP 2017066605A JP 6839585 B2 JP6839585 B2 JP 6839585B2
- Authority
- JP
- Japan
- Prior art keywords
- printing ink
- less
- composition
- mass
- dispersant composition
- 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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- 238000007639 printing Methods 0.000 title claims description 125
- 239000000203 mixture Substances 0.000 title claims description 105
- 239000002270 dispersing agent Substances 0.000 title claims description 60
- 229920001577 copolymer Polymers 0.000 claims description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 150000001336 alkenes Chemical class 0.000 claims description 23
- 229940059260 amidate Drugs 0.000 claims description 23
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 claims description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 23
- 150000002168 ethanoic acid esters Chemical class 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003086 colorant Substances 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- -1 imidazoline compound Chemical class 0.000 claims description 9
- 150000002430 hydrocarbons Chemical group 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 230000002862 amidating effect Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000976 ink Substances 0.000 description 114
- 239000002904 solvent Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 14
- 239000000049 pigment Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000006229 carbon black Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 238000007112 amidation reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007646 gravure printing Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000009435 amidation Effects 0.000 description 5
- 239000002635 aromatic organic solvent Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 2
- WGTDLPBPQKAPMN-KTKRTIGZSA-N 2-[2-[(z)-heptadec-8-enyl]-4,5-dihydroimidazol-1-yl]ethanol Chemical compound CCCCCCCC\C=C/CCCCCCCC1=NCCN1CCO WGTDLPBPQKAPMN-KTKRTIGZSA-N 0.000 description 2
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 2
- QVIAMKXOQGCYCV-UHFFFAOYSA-N 4-methylpentan-1-amine Chemical compound CC(C)CCCN QVIAMKXOQGCYCV-UHFFFAOYSA-N 0.000 description 2
- LPULCTXGGDJCTO-UHFFFAOYSA-N 6-methylheptan-1-amine Chemical compound CC(C)CCCCCN LPULCTXGGDJCTO-UHFFFAOYSA-N 0.000 description 2
- LJQFHDUFUVMPSP-UHFFFAOYSA-N 8-methylnonan-1-amine Chemical compound CC(C)CCCCCCCN LJQFHDUFUVMPSP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 150000002462 imidazolines Chemical class 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- LVXCIYPLCDLCHC-UHFFFAOYSA-N 1-icosyl-4,5-dihydroimidazole Chemical compound C(CCCCCCCCCCCCCCCCC)CCN1C=NCC1 LVXCIYPLCDLCHC-UHFFFAOYSA-N 0.000 description 1
- PWBYEVGYPCMAKF-UHFFFAOYSA-N 10-methylundecan-1-amine Chemical compound CC(C)CCCCCCCCCN PWBYEVGYPCMAKF-UHFFFAOYSA-N 0.000 description 1
- QFGCJUXQVRMUDZ-UHFFFAOYSA-N 2-dodecyl-1-ethyl-4,5-dihydroimidazole Chemical compound CCCCCCCCCCCCC1=NCCN1CC QFGCJUXQVRMUDZ-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- PPKVREKQVQREQD-UHFFFAOYSA-N antimony pentasulfide Chemical compound S=[Sb](=S)S[Sb](=S)=S PPKVREKQVQREQD-UHFFFAOYSA-N 0.000 description 1
- 229960001283 antimony pentasulfide Drugs 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- NCEXYHBECQHGNR-UHFFFAOYSA-N chembl421 Chemical compound C1=C(O)C(C(=O)O)=CC(N=NC=2C=CC(=CC=2)S(=O)(=O)NC=2N=CC=CC=2)=C1 NCEXYHBECQHGNR-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007647 flexography Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 125000001117 oleyl 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])=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
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
Description
本発明は、印刷インキ用分散剤組成物、印刷インキ組成物及び印刷インキ用分散剤組成物の製造方法に関する The present invention relates to a method for producing a dispersant composition for printing inks, a printing ink composition, and a dispersant composition for printing inks.
印刷方式には、グラビア印刷、オフセット印刷、フレキソグラフィー印刷などが知られており、それぞれに適した印刷インキが用いられている。通常、インキは、有機溶剤や水などの溶剤を含有している。例えば、グラビア印刷用インキの溶剤としては、トルエン、キシレン、ベンゼン等の芳香族系溶剤や、酢酸エチル、イソプロピルアルコール等のような非芳香族系溶剤が使用されてきた。トルエンは、インキに使用される樹脂や添加剤に対する高い溶解性、印刷時の適切な乾燥性等のために、従来、好んで使用されてきた。しかしながら、労働安全衛生法の改正により、トルエンの濃度規制が強化され、そのための環境改善への対応からインキ中の溶剤組成の見直しが迫られており、トルエンを使用しないインキ、例えば、酢酸エチル、イソプロピルアルコールを用いたインキの需要が高まっている。 Known printing methods include gravure printing, offset printing, flexography printing, and the like, and printing inks suitable for each are used. Ink usually contains a solvent such as an organic solvent or water. For example, as a solvent for gravure printing ink, aromatic solvents such as toluene, xylene and benzene, and non-aromatic solvents such as ethyl acetate and isopropyl alcohol have been used. Toluene has traditionally been preferred because of its high solubility in resins and additives used in inks, its proper drying properties during printing, and the like. However, due to the revision of the Industrial Safety and Health Law, the concentration regulation of toluene has been tightened, and the solvent composition in the ink has been urged to be reviewed in order to improve the environment for that purpose. The demand for inks using isopropyl alcohol is increasing.
特許文献１には、オレフィンと不飽和二塩基酸との共重合体のアミド化物又はエステル化物で、不飽和二塩基酸に対するアミド化率又はエステル化率が１０〜６０モル％であるものから選ばれる少なくとも１種の分散剤と、溶解度パラメーターが８．５〜２２（ｃａｌ／ｃｍ３）１／２の非芳香族系有機溶剤とを含有する電子材料用油中分散剤組成物を用いて、カーボンブラックなどの電子材料用粉体の油中分散体を得ることが記載されている。
また、特許文献２には、オレフィンと不飽和二塩基酸との共重合体のアミド化物を用いて、染料や顔料などの非水溶媒中に微粒子を分散させることが開示されている。
Patent Document 1 describes an amidate or esterified product of a copolymer of an olefin and an unsaturated dibasic acid, which has an amidation rate or an esterification rate of 10 to 60 mol% with respect to the unsaturated dibasic acid. A dispersant composition in oil for electronic materials containing at least one dispersant and a non-aromatic organic solvent having a solubility parameter of 8.5 to 22 (cal / cm 3 ) 1/2 is used. It is described to obtain a dispersion in oil of a powder for an electronic material such as carbon black.
Further, Patent Document 2 discloses that fine particles are dispersed in a non-aqueous solvent such as a dye or a pigment by using an amidate of a copolymer of an olefin and an unsaturated dibasic acid.
本発明は、環境に影響の少ない非芳香族系有機溶剤を用いても着色剤に対する充分な分散性能を有し、インキが乾燥しても有機溶剤に再度混合した際に容易に分散し、且つ保存後の分散性に優れた印刷インキが得られる印刷インキ用分散剤組成物を提供する。 INDUSTRIAL APPLICABILITY The present invention has sufficient dispersion performance with respect to a colorant even when a non-aromatic organic solvent having little influence on the environment is used, and even if the ink dries, it is easily dispersed when remixed with the organic solvent, and Provided is a dispersant composition for a printing ink, which can obtain a printing ink having excellent dispersibility after storage.
本発明は、オレフィンと不飽和二塩基酸との共重合体の、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンによるアミド化物又はその塩（ａ）と、酢酸エステル（ｂ１）と低級アルコール（ｂ２）との混合有機溶剤（ｂ）とを含有する、印刷インキ用分散剤組成物に関する。 In the present invention, an amidate of a copolymer of an olefin and an unsaturated dibasic acid with an amine having a branched alkyl group having 6 or more and 10 or less carbon atoms or a salt thereof (a), an acetic acid ester (b1) and a lower grade. The present invention relates to a dispersant composition for a printing ink containing a mixed organic solvent (b) with an alcohol (b2).
また、本発明は、
印刷インキ用粉体と、
オレフィンと不飽和二塩基酸との共重合体の、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンによるアミド化物又はその塩（ａ）と、
酢酸エステル（ｂ１）と低級アルコール（ｂ２）との混合有機溶剤（ｂ）と、
を含有する、印刷インキ組成物に関する。
In addition, the present invention
Printing ink powder and
An amidate of a copolymer of an olefin and an unsaturated dibasic acid with an amine having a branched alkyl group having 6 to 10 carbon atoms or a salt (a) thereof.
A mixed organic solvent (b) of an acetic acid ester (b1) and a lower alcohol (b2),
The present invention relates to a printing ink composition containing.
また、本発明は、
オレフィンと不飽和二塩基酸とを、酢酸エステル（ｂ１）と低級アルコール（ｂ２）とを含む反応溶媒中で反応させて共重合体を得る工程、及び
前記共重合体を、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンでアミド化して前記共重合体のアミド化物を得る工程、
を有する、印刷インキ用分散剤組成物の製造方法に関する。
In addition, the present invention
A step of reacting an olefin and an unsaturated dibasic acid in a reaction solvent containing an acetic acid ester (b1) and a lower alcohol (b2) to obtain a copolymer, and the copolymer having 6 or more carbon atoms and 10 carbon atoms. The step of amidating with an amine having the following branched chain alkyl group to obtain an amidated product of the copolymer.
The present invention relates to a method for producing a dispersant composition for printing ink.
以下、オレフィンと不飽和二塩基酸との共重合体の、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンによるアミド化物又はその塩（ａ）を（ａ）成分、酢酸エステル（ｂ１）を（ｂ１）成分、低級アルコール（ｂ２）を（ｂ２）成分、前記混合有機溶剤（ｂ）を（ｂ）成分として説明する。 Hereinafter, an amidate of a copolymer of an olefin and an unsaturated dibasic acid with an amine having a branched alkyl group having 6 or more and 10 or less carbon atoms or a salt thereof (a) is used as a component (a) and an acetic acid ester (b1). Will be described as the component (b1), the lower alcohol (b2) as the component (b2), and the mixed organic solvent (b) as the component (b).
本発明によれば、環境に影響の少ない非芳香族系有機溶剤を用いても着色剤に対する充分な分散性能を有し、インキが乾燥しても有機溶剤に再度混合した際に容易に分散し、且つ保存後、例えば高温、長期間の保存後の分散性に優れた印刷インキが得られる印刷インキ用分散剤組成物が提供される。例えば、グラビア印刷をする場合、グラビア印刷機のロール上で印刷インキが乾燥固結し、ロールが回転している間に本固結物がロールから落下して、新たに供給される印刷インキ中に混入するような事態が生じても、本発明の印刷インキ用分散剤組成物を用いて調製された印刷インキ組成物であれば、印刷インキ用粉体は容易に印刷インキに再分散するため、作業効率や印刷インキの品質を維持できる。 According to the present invention, even if a non-aromatic organic solvent having little influence on the environment is used, the ink has sufficient dispersion performance with respect to the colorant, and even if the ink dries, it is easily dispersed when remixed with the organic solvent. Further, there is provided a dispersant composition for a printing ink, which can obtain a printing ink having excellent dispersibility after storage, for example, after storage at a high temperature for a long period of time. For example, in the case of gravure printing, the printing ink dries and solidifies on the roll of the gravure printing machine, and the solidified product drops from the roll while the roll is rotating, and the printing ink is newly supplied. Even if a situation occurs in which the powder is mixed with the printing ink, the printing ink powder can be easily redispersed in the printing ink if the printing ink composition is prepared by using the printing ink dispersant composition of the present invention. , Work efficiency and printing ink quality can be maintained.
〔印刷インキ用分散剤組成物〕
（ａ）成分は、オレフィンと不飽和二塩基酸との共重合体の、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンによるアミド化物又はその塩である。（ａ）成分は、印刷インキ用粉体の分散剤として機能する。
[Dispersant composition for printing ink]
The component (a) is an amidate of a copolymer of an olefin and an unsaturated dibasic acid with an amine having a branched-chain alkyl group having 6 to 10 carbon atoms or a salt thereof. The component (a) functions as a dispersant for powder for printing ink.
（ａ）成分を構成するオレフィンとしては、良好な分散性能を得る観点から、炭素数３以上１２以下のオレフィンが好ましく、ジイソブチレン及びイソブチレンからなる群から選ばれる少なくとも１種がより好ましく、ジイソブチレンが更に好ましい。 As the olefin constituting the component (a), from the viewpoint of obtaining good dispersion performance, an olefin having 3 or more carbon atoms and 12 or less carbon atoms is preferable, and at least one selected from the group consisting of diisobutylene and isobutylene is more preferable, and diisobutylene is more preferable. Is more preferable.
（ａ）成分を構成する不飽和二塩基酸としては、良好な分散性能を得る観点から、炭素数４以上６以下の脂肪族不飽和二塩基酸が好ましく、無水マレイン酸、マレイン酸及びイタコン酸からなる群から選ばれる少なくとも１種がより好ましく、無水マレイン酸及びマレイン酸からなる群から選ばれる少なくとも１種が更に好ましい。 As the unsaturated dibasic acid constituting the component (a), an aliphatic unsaturated dibasic acid having 4 or more and 6 or less carbon atoms is preferable from the viewpoint of obtaining good dispersion performance, and maleic anhydride, maleic acid and itaconic acid. At least one selected from the group consisting of maleic anhydride is more preferable, and at least one selected from the group consisting of maleic anhydride and maleic acid is further preferable.
（ａ）成分の構成モノマーとしてのオレフィンと不飽和二塩基酸の割合は、良好な分散性能を得る観点から、オレフィン／不飽和二塩基酸のモル比が、好ましくは０．２５以上、より好ましくは０．４０以上、更に好ましくは０．５０以上、そして、好ましくは４以下、より好ましくは２．５以下、更に好ましくは２．０以下である。 Regarding the ratio of the olefin and the unsaturated dibasic acid as the constituent monomer of the component (a), the molar ratio of the olefin / unsaturated dibasic acid is preferably 0.25 or more, more preferably from the viewpoint of obtaining good dispersion performance. Is 0.40 or more, more preferably 0.50 or more, and preferably 4 or less, more preferably 2.5 or less, still more preferably 2.0 or less.
（ａ）成分のオレフィンと不飽和二塩基酸との共重合体のアミド化物は、オレフィン及び不飽和二塩基酸の共重合体と、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンとを反応させることにより得ることができる。ここで用いられるアミンは、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンであり、炭素数６以上１０以下の分岐鎖アルキル基を有する１級アミンが好ましい。具体的には、イソヘキシルアミン、２−エチルヘキシルアミン、イソオクチルアミン、イソデシルアミン等が挙げられる。これらのアミンは１種又は２種以上を混合して用いることができる。当該アミンが有する前記分岐鎖アルキル基は、好ましくは炭素数８以上１０以下の分岐鎖アルキル基である。 The amidate of the copolymer of the olefin and the unsaturated dibasic acid of the component (a) is a copolymer of the olefin and the unsaturated dibasic acid and an amine having a branched alkyl group having 6 or more and 10 or less carbon atoms. Can be obtained by reacting. The amine used here is an amine having a branched chain alkyl group having 6 or more and 10 or less carbon atoms, and a primary amine having a branched chain alkyl group having 6 or more and 10 or less carbon atoms is preferable. Specific examples thereof include isohexylamine, 2-ethylhexylamine, isooctylamine, and isodecylamine. These amines can be used alone or in admixture of two or more. The branched-chain alkyl group contained in the amine is preferably a branched-chain alkyl group having 8 to 10 carbon atoms.
（ａ）成分であるアミド化物のアミド化率（対不飽和二塩基酸）は、良好な分散性能、及び（ｂ）成分への良好な溶解性を得る観点から、好ましくは６０モル％超、より好ましくは７０モル％以上、更に好ましくは８０モル％以上、そして、好ましくは１５０モル％以下、より好ましくは１２０モル％以下、更に好ましくは１１０モル％以下である。
尚、このアミド化率は、（ａ）成分製造時の原料の仕込みモル％に基づいて算出できる。アミド化率が、２００モル％を超える場合は、遊離アミド化物が存在するものと推察される。
The amidation rate (vs. unsaturated dibasic acid) of the amidate as the component (a) is preferably more than 60 mol% from the viewpoint of obtaining good dispersion performance and good solubility in the component (b). It is more preferably 70 mol% or more, further preferably 80 mol% or more, and preferably 150 mol% or less, more preferably 120 mol% or less, still more preferably 110 mol% or less.
The amidation rate can be calculated based on (a) the molar% of the raw material charged at the time of producing the component. If the amidation rate exceeds 200 mol%, it is presumed that a free amidate is present.
オレフィンと不飽和二塩基酸との共重合体のアミド化物は、塩であってもよい。塩は、アミン、ベタイン等で中和して得ることができる。塩は、イミダゾリン塩が好ましく、下記式（１）のイミダゾリン化合物の塩がより好ましい。 The amidate of the copolymer of the olefin and the unsaturated dibasic acid may be a salt. The salt can be obtained by neutralizing with amine, betaine or the like. The salt is preferably an imidazoline salt, and more preferably a salt of the imidazoline compound of the following formula (1).
〔式中、Ｒ１は炭素数７以上２１以下の炭化水素基、Ｒ２は炭素数１以上５以下の２価の炭化水素基である。〕 [In the formula, R 1 is a hydrocarbon group having 7 or more and 21 or less carbon atoms, and R 2 is a divalent hydrocarbon group having 1 or more and 5 or less carbon atoms. ]
前記式（１）中、Ｒ１の炭化水素基は、アルキル基、アルケニル基が挙げられる。また、Ｒ１の炭素数は、好ましくは８以上、より好ましくは１０以上、そして、好ましくは２２以下、より好ましくは２０以下である。Ｒ２の２価の炭化水素基は、アルキレン基が挙げられる。Ｒ２の炭素数は、好ましくは１以上、そして、好ましくは４以下である。 In the formula (1), examples of the hydrocarbon group of R 1 include an alkyl group and an alkenyl group. The carbon number of R 1 is preferably 8 or more, more preferably 10 or more, and preferably 22 or less, more preferably 20 or less. Divalent hydrocarbon group R 2 include alkylene groups. The number of carbon atoms in R 2 is preferably 1 or more, and is preferably 4 or less.
オレフィンと不飽和二塩基酸との共重合体のアミド化物が塩である場合、中和度は、好ましくは５０モル％以上、より好ましくは６０モル％、そして、好ましくは１００モル％以下、より好ましくは９０モル％以下である。 When the amidate of the copolymer of the olefin and the unsaturated dibasic acid is a salt, the degree of neutralization is preferably 50 mol% or more, more preferably 60 mol%, and preferably 100 mol% or less. It is preferably 90 mol% or less.
（ａ）成分である、前記アミド化物の重量平均分子量は、良好な分散性能、及び非芳香族系有機溶剤への良好な溶解性を得る観点から、好ましくは７００以上、より好ましくは３０００以上、更に好ましくは５０００以上、そして、好ましくは５０万以下、より好ましくは３０万以下、更に好ましくは１０万以下である。なお、本明細書における（ａ）成分のアミド化物の重量平均分子量は、下記条件のＧＰＣ（ゲルパーミエーションクロマトグラフィー、ポリスチレン換算）で測定した値である。
カラム：α−Ｍ＋α−Ｍ（東ソー株式会社製）
カラム温度：４０℃
検出器：ＲＩ
溶離液：６０ｍｍｏｌ／Ｌリン酸、５０ｍｍｏｌ／Ｌ臭化リチウム、ＤＭＦ溶剤
流速：１．０ｍＬ／ｍｉｎ
注入量：０．１ｍＬ
標準：ポリスチレン
The weight average molecular weight of the amidate, which is the component (a), is preferably 700 or more, more preferably 3000 or more, from the viewpoint of obtaining good dispersion performance and good solubility in a non-aromatic organic solvent. It is more preferably 5,000 or more, preferably 500,000 or less, more preferably 300,000 or less, still more preferably 100,000 or less. The weight average molecular weight of the amidate of the component (a) in the present specification is a value measured by GPC (gel permeation chromatography, polystyrene conversion) under the following conditions.
Column: α-M + α-M (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Detector: RI
Eluent: 60 mmol / L phosphoric acid, 50 mmol / L lithium bromide, DMF solvent Flow rate: 1.0 mL / min
Injection volume: 0.1 mL
Standard: polystyrene
本発明では共重合体の重合率の向上並びに好ましい重量平均分子量を得る観点から、共重合体を製造する際に重合開始剤を使用できる。重合開始剤は、有機過酸化物、アゾ系等が挙げられ、このうち有機過酸化物が好ましく、具体的にはパーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、ジアシルパーオキサイド、パーオキシジカーボネート、パーオキシエステルが挙げられ、更に具体的には過酸化ベンゾイル、過酸化ラウロイル、ｔ−ブチルパーオキシ−２−エチルヘキサノエート等が挙げられる。
重合開始剤の使用量（対不飽和二塩基酸）は、良好な重合率並びに分散性能を得る観点から、好ましくは０．１モル％以上、より好ましくは０．３モル％以上、更に好ましくは０．５モル％以上、そして、好ましくは２０モル％以下、より好ましくは１０モル％以下、更に好ましくは５モル％以下である。
重合開始剤は重合終了後の熟成工程において共重合体の重合率を更に向上させる目的で添加しても良い。その際の使用量は０．０１モル％以上０．１モル％以下（対不飽和二塩基酸）が好ましい。
In the present invention, a polymerization initiator can be used when producing the copolymer from the viewpoint of improving the polymerization rate of the copolymer and obtaining a preferable weight average molecular weight. Examples of the polymerization initiator include organic peroxides and azo compounds, of which organic peroxides are preferable, and specifically, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, and peroxydicarbonate. , Peroxy ester, and more specifically, benzoyl peroxide, lauroyl peroxide, t-butylperoxy-2-ethylhexanoate and the like.
The amount of the polymerization initiator used (against unsaturated dibasic acid) is preferably 0.1 mol% or more, more preferably 0.3 mol% or more, still more preferably 0.3 mol% or more, from the viewpoint of obtaining a good polymerization rate and dispersion performance. It is 0.5 mol% or more, preferably 20 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less.
The polymerization initiator may be added for the purpose of further improving the polymerization rate of the copolymer in the aging step after the completion of polymerization. The amount used at that time is preferably 0.01 mol% or more and 0.1 mol% or less (against unsaturated dibasic acid).
本発明では、（ａ）成分と共に未反応のオレフィンや不飽和二塩基酸等を本発明の効果を阻害しない範囲で含有する混合物を、（ａ）成分の供給原料として用いてもよい。 In the present invention, a mixture containing an unreacted olefin, unsaturated dibasic acid, or the like together with the component (a) within a range that does not impair the effects of the present invention may be used as a feedstock for the component (a).
（ａ）成分は、前記アミド化合物の塩が好ましく、前記アミド化物のイミダゾリン塩がより好ましい。 As the component (a), the salt of the amide compound is preferable, and the imidazoline salt of the amidate is more preferable.
本発明に用いられる（ｂ）成分の混合有機溶剤は、環境への配慮から、非芳香族系有機溶剤であり、また、（ａ）成分の溶解性を向上させる観点から、（ｂ１）成分の酢酸エステルと（ｂ２）成分の低級アルコールとの混合有機溶剤が用いられる。本発明の印刷インキ用分散剤組成物は、いわゆる油中分散型スラリーの形態の印刷インキ組成物の調製に好適に用いられる。 The mixed organic solvent of the component (b) used in the present invention is a non-aromatic organic solvent in consideration of the environment, and from the viewpoint of improving the solubility of the component (a), the component (b1) is used. A mixed organic solvent of an acetic acid ester and a lower alcohol of the component (b2) is used. The dispersant composition for printing ink of the present invention is suitably used for preparing a printing ink composition in the form of a so-called dispersion type slurry in oil.
（ｂ１）成分の酢酸エステルとしては、総炭素数２以上６以下の酢酸エステルが挙げられ、具体的には、酢酸エチル、酢酸プロピル、酢酸ブチル等が挙げられる。（ｂ１）成分は、酢酸エチル及び酢酸ブチルからなる群から選ばれる少なくとも１種が好ましい。
また、（ｂ２）成分の低級アルコールとしては、炭素数２以上６以下のアルコールが挙げられ、具体的には、イソプロピルアルコール、ｎ−プロピルアルコール、イソブチルアルコール、ｎ−ブチルアルコール等が挙げられる。（ｂ２）成分は、イソプロピルアルコール及びｎ−ブチルアルコールからなる群から選ばれる少なくとも１種が好ましい。
Examples of the acetic acid ester of the component (b1) include acetic acid esters having a total carbon number of 2 or more and 6 or less, and specific examples thereof include ethyl acetate, propyl acetate, and butyl acetate. The component (b1) is preferably at least one selected from the group consisting of ethyl acetate and butyl acetate.
Examples of the lower alcohol of the component (b2) include alcohols having 2 or more and 6 or less carbon atoms, and specific examples thereof include isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, and n-butyl alcohol. The component (b2) is preferably at least one selected from the group consisting of isopropyl alcohol and n-butyl alcohol.
（ｂ）成分は、良好な分散性能、及び（ａ）成分の（ｂ）成分への良好な溶解性を得る観点から、（ｂ１）成分の含有量と（ｂ２）成分の含有量の質量比（ｂ１）／（ｂ２）が、好ましくは０．０１以上、より好ましくは０．２５以上、更に好ましくは０．４５以上、より更に好ましくは０．８以上、そして、好ましくは１００以下、より好ましくは９９以下、更に好ましくは５０以下、より更に好ましく９は以下、より更に好ましくは３以下である。 The component (b) has a mass ratio of the content of the component (b1) to the content of the component (b2) from the viewpoint of obtaining good dispersion performance and good solubility of the component (a) in the component (b). (B1) / (b2) is preferably 0.01 or more, more preferably 0.25 or more, still more preferably 0.45 or more, still more preferably 0.8 or more, and preferably 100 or less, more preferably. Is 99 or less, more preferably 50 or less, still more preferably 9 or less, still more preferably 3 or less.
本発明の印刷インキ用分散剤組成物は、（ｂ）成分以外の有機溶剤を含有してもよいが、全有機溶剤中、（ｂ）成分の占める割合は、好ましくは１０質量％以上、より好ましくは３０質量％以上、更に好ましくは７０質量％以上、そして、好ましくは１００質量％以下であり、１００質量％であってもよい。
また、本発明の印刷インキ用分散剤組成物は、水の含有量が少ないものが好ましい。更に好ましくは、水を実質的に含有しないものが好ましい。ここで、「水を実質的に含有しない」とは、組成物中の水の含有量が好ましくは５質量％以下、より好ましくは３質量％以下、更に好ましくは１質量％以下であることをいう。
The dispersant composition for printing ink of the present invention may contain an organic solvent other than the component (b), but the proportion of the component (b) in the total organic solvent is preferably 10% by mass or more. It is preferably 30% by mass or more, more preferably 70% by mass or more, and preferably 100% by mass or less, and may be 100% by mass.
Further, the dispersant composition for printing ink of the present invention preferably has a low water content. More preferably, it contains substantially no water. Here, "substantially free of water" means that the content of water in the composition is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less. Say.
本発明の印刷インキ用分散剤組成物は、分散性向上の観点から、（ａ）成分の含有量と（ｂ）成分の含有量との質量比（ａ）／（ｂ）が、好ましくは０．１以上、より好ましくは０．２以上、更に好ましくは０．３以上、そして、好ましくは０．９以下、より好ましくは０．７以下、更に好ましくは０．５以下である。 In the dispersant composition for printing ink of the present invention, the mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) is preferably 0 from the viewpoint of improving the dispersibility. .1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and preferably 0.9 or less, more preferably 0.7 or less, still more preferably 0.5 or less.
本発明の印刷インキ用分散剤組成物は、分散性向上の観点から、（ａ）成分を、好ましくは１０質量％以上、より好ましくは１５質量％以上、更に好ましくは２０質量％以上、そして、好ましくは８０質量％以下、より好ましくは６０質量％以下、更に好ましくは４０質量％以下含有する。 From the viewpoint of improving dispersibility, the dispersant composition for printing ink of the present invention contains the component (a) in an amount of preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and It is preferably contained in an amount of 80% by mass or less, more preferably 60% by mass or less, still more preferably 40% by mass or less.
本発明の印刷インキ用分散剤組成物は、任意成分として、高級アルコール、脂肪酸、脂肪酸エステル、脂肪アミンなどを含有することができる。 The dispersant composition for printing ink of the present invention can contain higher alcohols, fatty acids, fatty acid esters, fatty amines and the like as optional components.
なお、本発明の印刷インキ用分散剤組成物は、（ｂ）成分をそのまま印刷インキ組成物の溶剤として用いることができるため、組成によっては、本発明の印刷インキ用分散剤組成物に印刷インキ用粉体を混合するだけで、本発明の印刷インキ組成物を得ることができる。例えば、本発明の印刷インキ用分散剤組成物は、印刷インキ用ビヒクルやその溶剤、更には、印刷インキ組成物用溶剤等として使用することができる。 In the printing ink dispersant composition of the present invention, the component (b) can be used as it is as a solvent of the printing ink composition. Therefore, depending on the composition, the printing ink may be used in the printing ink dispersant composition of the present invention. The printing ink composition of the present invention can be obtained only by mixing the powders for use. For example, the dispersant composition for printing ink of the present invention can be used as a vehicle for printing ink, a solvent thereof, a solvent for a printing ink composition, and the like.
本発明の印刷インキ組成物は、印刷インキ用粉体又は他の有機溶剤との混合性の向上の観点から、液体であることが好ましい。 The printing ink composition of the present invention is preferably a liquid from the viewpoint of improving the mixability with the printing ink powder or other organic solvent.
〔印刷インキ組成物〕
本発明の印刷インキ組成物は、印刷インキ用粉体と、前記（ａ）成分と、前記（ｂ）成分とを含有する。（ａ）成分、及び（ｂ）成分の具体例及び好ましい態様は、本発明の印刷インキ用分散剤組成物と同じである。
[Printing ink composition]
The printing ink composition of the present invention contains the powder for printing ink, the component (a), and the component (b). Specific examples and preferred embodiments of the component (a) and the component (b) are the same as those of the dispersant composition for printing ink of the present invention.
印刷インキ用粉体としては、着色剤、着色剤以外の無機粉体が挙げられる。
着色剤は、顔料が挙げられる。顔料としては、印刷インキで一般的に用いられている各種無機顔料、有機顔料等が使用できる。無機顔料としては、例えば、酸化チタン、ベンガラ、アンチモンレッド、カドミウムイエロー、コバルトブルー、紺青、群青、カーボンブラック、黒鉛、サチンホワイト、亜鉛華、等の有色顔料、シリカ、炭酸カルシウム、カオリン、クレー、硫酸バリウム、水酸化アルミニウム、タルク等の体質顔料、アクリル樹脂で表面処理したアルミニウム粒子を含有するアルミペースト、表面に酸化チタンと酸化スズと酸化ジルコニウムとがコーティングされたマイカ等のパール顔料を挙げることができる。有機顔料としては、例えば、溶性アゾ顔料、不溶性アゾ顔料、アゾレーキ顔料、縮合アゾ顔料、銅フタロシアニン顔料、縮合多環顔料等を挙げることができる。
また、着色剤以外の無機粉体としては、リン酸カルシウム、リン酸亜鉛、ベントナイト、フェライト、アルミナ、酸化マグネシウム、ホワイトカーボン、セメント、石膏、チタン酸塩、珪酸塩等が挙げられる。
Examples of the powder for printing ink include a colorant and an inorganic powder other than the colorant.
Examples of the colorant include pigments. As the pigment, various inorganic pigments, organic pigments and the like generally used in printing inks can be used. Examples of inorganic pigments include colored pigments such as titanium oxide, red iron oxide, antimony red, cadmium yellow, cobalt blue, dark blue, ultramarine blue, carbon black, graphite, satin white, zinc white, etc., silica, calcium carbonate, kaolin, clay, etc. Examples include extender pigments such as barium sulfate, aluminum hydroxide, and talc, aluminum pastes containing aluminum particles surface-treated with acrylic resin, and pearl pigments such as mica whose surface is coated with titanium oxide, tin oxide, and zirconium oxide. Can be done. Examples of the organic pigment include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments and the like.
Examples of the inorganic powder other than the colorant include calcium phosphate, zinc phosphate, bentonite, ferrite, alumina, magnesium oxide, white carbon, cement, gypsum, titanate, and silicate.
印刷インキ用粉体は、着色剤を含むことが好ましい。本発明の印刷インキ組成物は、良好な分散性が得られる観点から、着色剤を、好ましくは５質量％以上、より好ましくは７質量％以上、更に好ましくは９質量％以上、そして、好ましくは５０質量％以下、より好ましくは３０質量％以下含有する。 The printing ink powder preferably contains a colorant. From the viewpoint of obtaining good dispersibility, the printing ink composition of the present invention contains a colorant, preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 9% by mass or more, and preferably 9% by mass or more. It is contained in an amount of 50% by mass or less, more preferably 30% by mass or less.
また、本発明の印刷インキ組成物が、印刷インキ用粉体として着色剤以外の無機粉体を含有する場合、印刷インキ用粉体中、着色剤以外の無機粉体を、好ましくは１０質量％以上、より好ましくは２０質量％以上、更に好ましくは３０質量％以上、そして、好ましくは７０質量％以下、より好ましくは６０質量％以下含有する。 When the printing ink composition of the present invention contains an inorganic powder other than the colorant as the powder for the printing ink, the inorganic powder other than the colorant is preferably 10% by mass in the powder for the printing ink. As described above, the content is more preferably 20% by mass or more, further preferably 30% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less.
本発明の印刷インキ組成物は、良好な分散性が得られる観点から、（ａ）成分を、印刷インキ用粉体１００質量部に対し、好ましくは１質量部以上、より好ましくは２質量部以上、更に好ましくは５質量部以上、そして、好ましくは３０質量部以下、より好ましくは２０質量部以下含有する。 From the viewpoint of obtaining good dispersibility, the printing ink composition of the present invention contains the component (a) in an amount of preferably 1 part by mass or more, more preferably 2 parts by mass or more, based on 100 parts by mass of the printing ink powder. , More preferably 5 parts by mass or more, preferably 30 parts by mass or less, and more preferably 20 parts by mass or less.
本発明の印刷インキ組成物は、（ｂ）成分を、好ましくは８０質量％以上、より好ましくは８５質量％以上、そして、好ましくは９５質量％以下、より好ましくは９０質量％以下含有する。 The printing ink composition of the present invention contains the component (b) in an amount of preferably 80% by mass or more, more preferably 85% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less.
本発明の印刷インキ組成物の組成は種々設定できるが、例えば、グラビア印刷用インキ組成物であれば、各成分の含有量は、例えば、以下の通りとすることができる。
・着色剤 組成物中、好ましくは７質量％以上３０質量％以下
・（ａ）成分 着色剤１００質量部に対して、好ましくは０．５質量部以上３０質量部以下
・（ｂ）成分 組成物中、好ましくは４０質量％以上９２．５質量％以下
The composition of the printing ink composition of the present invention can be set in various ways. For example, in the case of an ink composition for gravure printing, the content of each component can be set as follows, for example.
-Preferably 7% by mass or more and 30% by mass or less in the colorant composition-Component (a) component preferably 0.5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the colorant- (b) component composition Medium, preferably 40% by mass or more and 92.5% by mass or less
本発明の印刷インキ組成物は、２５℃での分散粒子の平均粒径が、好ましくは３μｍ以下、より好ましくは２．５μｍ以下であり、一例として、２μｍ近傍が好ましい。平均粒径の下限値は、１．１μｍ以上が好ましい。尚、平均粒径は、実施例に記載した方法で測定する。 In the printing ink composition of the present invention, the average particle size of the dispersed particles at 25 ° C. is preferably 3 μm or less, more preferably 2.5 μm or less, and as an example, the vicinity of 2 μm is preferable. The lower limit of the average particle size is preferably 1.1 μm or more. The average particle size is measured by the method described in Examples.
本発明の印刷インキ組成物は、バインダー、可塑剤等を含有することができる。バインダーとしては例えば、エチルセルロース、アクリル、ポリビニルブチラール、ポリビニルアセタール、ポリビニルアルコール、ポリオレフィン、ポリウレタン、ポリスチレン、あるいはこれらの混合物等が挙げられる。可塑剤としては例えば、フタル酸ジオクチル、アジピン酸、リン酸エステル、グリコール等が挙げられる。 The printing ink composition of the present invention may contain a binder, a plasticizer, and the like. Examples of the binder include ethyl cellulose, acrylic, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyolefin, polyurethane, polystyrene, or a mixture thereof. Examples of the plasticizer include dioctyl phthalate, adipic acid, phosphoric acid ester, glycol and the like.
また、本発明の印刷インキ組成物の粘度も、印刷方式に応じて設定することができる。例えば、グラビア印刷用インキ組成物であれば、２５℃の粘度は、好ましくは０．５ｍＰａ・ｓ以上２０ｍＰａ・ｓ以下である。 Further, the viscosity of the printing ink composition of the present invention can also be set according to the printing method. For example, in the case of an ink composition for gravure printing, the viscosity at 25 ° C. is preferably 0.5 mPa · s or more and 20 mPa · s or less.
本発明の印刷インキ組成物の、分散安定化のメカニズムは明らかではないが、本発明の（ａ）成分を構成する不飽和二塩基酸から誘導される基が印刷インキ用粉体に吸着し、本発明の（ａ）成分を構成するオレフィンから誘導される基が有機溶剤中に溶解拡散することにより、印刷インキ用粉体の分散安定化が向上するものと推察される。 Although the mechanism of dispersion stabilization of the printing ink composition of the present invention is not clear, the group derived from the unsaturated dibasic acid constituting the component (a) of the present invention is adsorbed on the printing ink powder. It is presumed that the group derived from the olefin constituting the component (a) of the present invention dissolves and diffuses in the organic solvent to improve the dispersion stabilization of the printing ink powder.
本発明の印刷インキ組成物は、油中分散型スラリーであることが好ましい。本発明の印刷インキ組成物を得る方法としては、通常のスラリー化の方法を用いることができる。例えば本発明の印刷インキ用分散剤組成物に印刷インキ用粉体を添加して撹拌、混合する方法、印刷インキ用粉体に本発明の印刷インキ用分散剤組成物を加えて撹拌、混合する方法等が挙げられる。撹拌、混合する方法としては、例えば高速ディスパー、ホモミキサー、ボールミル等一般に用いられる撹拌装置を使用することができる。
また、印刷インキ用粉体の顔料又は粗粒子を粉砕と同時にスラリー化する場合には、印刷インキ用粉体の鉱石又は粗粒子に本発明の印刷インキ用分散剤組成物を添加して、粉砕と同時にスラリー化する方法等を行うこともできる。粉砕と同時にスラリー化する方法には、ビーズミル等一般に用いられる湿式粉砕機を使用することが出来る。
The printing ink composition of the present invention is preferably a dispersion-type slurry in oil. As a method for obtaining the printing ink composition of the present invention, a usual slurrying method can be used. For example, a method of adding a printing ink powder to the printing ink dispersant composition of the present invention and stirring and mixing, and a method of adding the printing ink dispersant composition of the present invention to the printing ink powder and stirring and mixing. The method and the like can be mentioned. As a method of stirring and mixing, for example, a commonly used stirring device such as a high-speed dispenser, a homomixer, or a ball mill can be used.
When the pigment or coarse particles of the printing ink powder are slurried at the same time as crushing, the dispersant composition for printing ink of the present invention is added to the ore or coarse particles of the printing ink powder and crushed. At the same time, a method of making a slurry or the like can be performed. A commonly used wet crusher such as a bead mill can be used as a method of slurrying at the same time as crushing.
〔印刷インキ用分散剤組成物又は印刷インキ組成物の製造方法〕
本発明は、オレフィンと不飽和二塩基酸とを、酢酸エステル（ｂ１）と低級アルコール（ｂ２）とを含む反応溶媒中で反応させて共重合体を得る工程、及び
前記共重合体を、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンでアミド化して前記共重合体のアミド化物を得る工程、
を有する、印刷インキ用分散剤組成物の製造方法を提供する。
[Manufacturing method of dispersant composition for printing ink or printing ink composition]
In the present invention, an olefin and an unsaturated dibasic acid are reacted in a reaction solvent containing an acetic acid ester (b1) and a lower alcohol (b2) to obtain a copolymer, and the copolymer is carbon. A step of amidating with an amine having a branched alkyl group having a number of 6 or more and 10 or less to obtain an amidated product of the copolymer.
Provided is a method for producing a dispersant composition for printing ink.
上記製造方法においては、前記共重合体のアミド化物は、（ａ）成分である。（ｂ１）成分と（ｂ２）成分とを含む反応溶媒はそのまま印刷インキ用分散剤組成物の（ｂ）成分とすることができる。
本発明の印刷インキ用分散剤組成物や本発明の印刷インキ組成物で述べた事項は、本発明の印刷インキ用分散剤組成物の製造方法に適用できる。
本発明の印刷インキ用分散剤組成物の製造方法は、前記共重合体のアミド化物を、前記式（１）のイミダゾリン化合物で中和する工程を有することができる。
In the above production method, the amidate of the copolymer is the component (a). The reaction solvent containing the component (b1) and the component (b2) can be used as it is as the component (b) of the dispersant composition for printing ink.
The matters described in the dispersant composition for printing ink of the present invention and the printing ink composition of the present invention can be applied to the method for producing the dispersant composition for printing ink of the present invention.
The method for producing a dispersant composition for printing ink of the present invention can include a step of neutralizing the amidazoline of the copolymer with the imidazoline compound of the formula (1).
また、本発明は、
印刷インキ用粉体と、
オレフィンと不飽和二塩基酸との共重合体の、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンによるアミド化物又はその塩（ａ）と、
酢酸エステル（ｂ１）と低級アルコール（ｂ２）との混合有機溶剤（ｂ）と、
を混合する、印刷インキ組成物の製造方法を提供する。
In addition, the present invention
Printing ink powder and
An amidate of a copolymer of an olefin and an unsaturated dibasic acid with an amine having a branched alkyl group having 6 to 10 carbon atoms or a salt (a) thereof.
A mixed organic solvent (b) of an acetic acid ester (b1) and a lower alcohol (b2),
To provide a method for producing a printing ink composition.
上記製造方法においては、（ａ）成分及び（ｂ）成分を含有する本発明の印刷インキ用分散剤組成物を用いることができる。その場合、必要に応じて、（ｂ１）成分及び／又は（ｂ２）成分を添加して組成を調整することができる。本発明の印刷インキ用分散剤組成物や本発明の印刷インキ組成物で述べた事項は、この印刷インキ組成物の製造方法に適用できる。 In the above-mentioned production method, the dispersant composition for printing ink of the present invention containing the component (a) and the component (b) can be used. In that case, the composition can be adjusted by adding the component (b1) and / or the component (b2), if necessary. The matters described in the dispersant composition for printing ink of the present invention and the printing ink composition of the present invention can be applied to the method for producing this printing ink composition.
製造例１
攪拌機、温度計、還流冷却管、窒素導入管、滴下ロートを備えた反応容器に無水マレイン酸（三井化学（株）製）７０．６ｇ、酢酸エチル（シノケム・ジャパン（株）製）３２．５ｇ及びイソプロピルアルコール（以下ＩＰＡと略記）（ＪＸエネルギー（株）製）３２．５ｇを仕込み、窒素気流下で９３℃に加熱後、この温度を維持しながら、８５質量％ジイソブチレン（丸善石油化学（株）製）の酢酸エチルとＩＰＡ混合溶液９５．０ｇ及び重合開始剤として２質量％パーブチルＯ（日油社製、ｔ−ブチルパーオキシ−２−エチルヘキサノエート）の酢酸エチルとＩＰＡ混合溶液７４．０ｇをそれぞれ別の滴下ロートから１．５時間かけて滴下し重合反応を行った。滴下終了１５分後に２質量％パーブチルＯの酢酸エチルとＩＰＡ混合溶液３．０ｇを一括で添加し、その後、９３℃で９時間熟成し、重合反応を完結させた。反応終了後、冷却し、６５℃に保持しながら２−エチルヘキシルアミン（広栄化学工業（株）製）９３．０ｇを滴下ロートから１時間かけて滴下しアミド化反応を行った。滴下終了後、６５℃で２時間熟成した。その後、冷却し、４０℃に保持しながら中和剤であるオレイルヒドロキシエチルイミダゾリン（（株）八代製）１８５．５ｇを滴下ロートから１．５時間かけて滴下し中和反応を行った。滴下終了後、４０℃で１時間熟成し、反応を完結させ、無水マレイン酸／ジイソブチレン共重合体アミド化物のオレイルエチルイミダゾリンによる中和物を得た。本アミド化物の中和物のアミド化率、重量平均分子量（前記方法により測定した値、以下同じ）、合成時の使用溶剤、中和剤及び中和度を表１に示す。なお、オレイルヒドロキシエチルイミダゾリンは、式（１）中のＲ１がオレイル基、Ｒ２がエチレン基の化合物である。
この方法により得られた反応生成物を、そのまま印刷インキ用分散剤組成物とした。
Manufacturing example 1
Maleic anhydride (manufactured by Mitsui Kagaku Co., Ltd.) 70.6 g, ethyl acetate (manufactured by Shinochem Japan Co., Ltd.) 32.5 g in a reaction vessel equipped with a stirrer, thermometer, reflux cooling tube, nitrogen introduction tube, and dropping funnel. And isopropyl alcohol (hereinafter abbreviated as IPA) (manufactured by JX Energy Co., Ltd.) 32.5 g, heated to 93 ° C. under a nitrogen stream, and then 85% by mass diisobutylene (Maruzen Petrochemical (Maruzen Petrochemical (Maruzen Petrochemical)) while maintaining this temperature. 95.0 g of ethyl acetate and IPA mixed solution (manufactured by Nichiyu Co., Ltd.) and 2 mass% perbutyl O (t-butylperoxy-2-ethylhexanoate, manufactured by Nichiyu Co., Ltd.) as a polymerization initiator mixed solution of ethyl acetate and IPA. 74.0 g was added dropwise from different dropping funnels over 1.5 hours to carry out a polymerization reaction. Fifteen minutes after the completion of the dropping, 3.0 g of a mixed solution of 2 mass% perbutyl O ethyl acetate and IPA was added in a batch, and then aged at 93 ° C. for 9 hours to complete the polymerization reaction. After completion of the reaction, the mixture was cooled and 93.0 g of 2-ethylhexylamine (manufactured by Koei Chemical Industry Co., Ltd.) was added dropwise from the dropping funnel over 1 hour while maintaining the temperature at 65 ° C. to carry out an amidation reaction. After completion of the dropping, the mixture was aged at 65 ° C. for 2 hours. Then, while cooling and maintaining at 40 ° C., 185.5 g of oleyl hydroxyethyl imidazoline (manufactured by Yashiro Co., Ltd.) as a neutralizing agent was added dropwise from the dropping funnel over 1.5 hours to carry out a neutralization reaction. After completion of the dropwise addition, the mixture was aged at 40 ° C. for 1 hour to complete the reaction, and a neutralized product of maleic anhydride / diisobutylene copolymer amidate with oleylethylimidazoline was obtained. Table 1 shows the amidation rate, weight average molecular weight (value measured by the above method, the same applies hereinafter), the solvent used during synthesis, the neutralizing agent, and the degree of neutralization of the neutralized product of this amidated product. In addition, oleyl hydroxyethyl imidazoline is a compound in which R 1 in the formula (1) is an oleyl group and R 2 is an ethylene group.
The reaction product obtained by this method was used as it was as a dispersant composition for printing ink.
製造例２〜４、比較製造例１〜８
製造条件を表１の通りとする以外は製造例１と同様にして、表１に示すアミド化物もしくはその中和物又はエステル化物を含む反応生成物を得た。得られた反応生成物は、そのまま印刷インキ用分散剤組成物とした。
尚表１中、イタコン酸は磐田化学工業（株）製、イソブチレンは（株）クラレ社製、オレイルアミン、ステアリルアミン、ｎ−オクチルアミンは花王（株）製、ｎ−ブチルアミン、ｎ−デシルアミン、２−エチルヘキシルアルコール、プロピレングリコールメチルエーテルアセテート（ＰＧＭＥＡ）、メチルイソブチルケトン（ＭＩＢＫ）、トルエン、メチルエチルケトン（ＭＥＫ）、キシレンは和光純薬工業（株）製、イソヘキシルアミン、イソオクチルアミン、イソデシルアミン、イソペンチルアミン、イソドデシルアミン、ステアリルエチルイミダゾリン、ラウリルエチルイミダゾリンは東京化成工業（株）製である。
Production Examples 2-4, Comparative Production Examples 1-8
A reaction product containing the amidate shown in Table 1 or its neutralized product or esterified product was obtained in the same manner as in Production Example 1 except that the production conditions were as shown in Table 1. The obtained reaction product was used as it was as a dispersant composition for printing ink.
In Table 1, itaconic acid is manufactured by Iwata Chemical Industry Co., Ltd., isobutylene is manufactured by Clare Co., Ltd., oleylamine, stearylamine, n-octylamine is manufactured by Kao Co., Ltd., n-butylamine, n-decylamine, 2 -Ethylhexyl alcohol, propylene glycol methyl ether acetate (PGMEA), methyl isobutyl ketone (MIBK), toluene, methyl ethyl ketone (MEK), xylene manufactured by Wako Pure Chemical Industries, Ltd., isohexylamine, isooctylamine, isodecylamine, Isopentylamine, isododecylamine, stearylethyl imidazoline, and lauryl ethyl imidazoline are manufactured by Tokyo Kasei Kogyo Co., Ltd.
表１中、モル％は、いずれも不飽和二塩基酸に対するモル％である。
表１中、製造例１〜４では、共重合体のアミド化物が（ａ）成分、合成時の使用溶剤が（ｂ）成分である。
In Table 1, mol% is mol% with respect to unsaturated dibasic acid.
In Table 1, in Production Examples 1 to 4, the amidate of the copolymer is the component (a), and the solvent used in the synthesis is the component (b).
実施例１〜４、比較例１〜９
表１の印刷インキ用分散剤組成物と比較の分散剤とを用いて印刷インキ組成物を調製し、以下の評価を行った。結果を表２に示した。
Examples 1 to 4, Comparative Examples 1 to 9
A printing ink composition was prepared using the dispersant composition for printing ink shown in Table 1 and the dispersant for comparison, and the following evaluation was performed. The results are shown in Table 2.
（１）分散性の評価（Ｉ）（調製直後の分散性）
１００ｍＬのスクリュー管に、平均粒径が２４ｎｍのカーボンブラック（三菱化学（株）製ＭＡ１００）４ｇ、溶剤、表１の印刷インキ用分散剤組成物又は比較の分散剤を仕込んだ。ここで、比較の分散剤は、ルブリゾール２４０００（ポリエチレンイミン系分散剤、ルブリゾール社製）であった。また、表１の印刷インキ用分散剤組成物と比較の分散剤は、それぞれ、合成時に使用した溶剤と同じ溶剤で希釈して固形分３０質量％に調製したものを使用した。表１の印刷インキ用分散剤組成物については、固形分の量は、共重合体のアミド化物もしくはエステル化物又は塩の量であるとみなすことができる。なお、比較の分散剤では、溶剤は、酢酸エチル／ＩＰＡの質量比が１／１の混合有機溶剤を用いた。
その後、ブランソン社製の超音波分散装置Ｂ１５１０で３時間処理を行い、スラリーを調製した。これを印刷インキ組成物とした。印刷インキ組成物におけるカーボンブラック濃度が１０質量％となるように溶剤の量を調製した。
印刷インキ用分散剤組成物又は比較の分散剤の添加量が、８、１０、又は１２質量％（対カーボンブラック（固形分換算））の印刷インキ組成物を用意した。
各分散剤添加量の印刷インキ組成物について、調製直後に、堀場製作所社製のレーザー散乱粒度分布計ＬＡ−９２０を用いて、２５℃における印刷インキ組成物のカーボンブラックの平均粒径を測定した。結果を表２に示す。
尚、印刷インキ組成物は、各分散剤添加量において平均粒径が２μｍ以下であるものを分散性が良好であるとした。
(1) Evaluation of dispersibility (I) (Dispersibility immediately after preparation)
A 100 mL screw tube was charged with 4 g of carbon black (MA100 manufactured by Mitsubishi Chemical Corporation) having an average particle size of 24 nm, a solvent, a dispersant composition for printing ink shown in Table 1, or a comparative dispersant. Here, the comparative dispersant was Lubrizol 24000 (polyethyleneimine-based dispersant, manufactured by Lubrizol). Further, as the dispersant for comparison with the dispersant composition for printing ink in Table 1, those prepared by diluting with the same solvent as the solvent used at the time of synthesis to a solid content of 30% by mass were used. For the dispersant compositions for printing inks in Table 1, the amount of solids can be considered to be the amount of copolymer amidate or esterified or salt. In the comparative dispersant, a mixed organic solvent having a mass ratio of ethyl acetate / IPA of 1/1 was used as the solvent.
Then, the treatment was carried out for 3 hours with the ultrasonic disperser B1510 manufactured by Branson Co., Ltd. to prepare a slurry. This was used as a printing ink composition. The amount of the solvent was adjusted so that the carbon black concentration in the printing ink composition was 10% by mass.
A printing ink composition in which the amount of the dispersant composition for printing ink or the comparative dispersant added was 8, 10, or 12% by mass (with respect to carbon black (solid content equivalent)) was prepared.
Immediately after preparation, the average particle size of carbon black in the printing ink composition at 25 ° C. was measured using a laser scattering particle size distribution meter LA-920 manufactured by HORIBA, Ltd. for each dispersant-added amount of the printing ink composition. .. The results are shown in Table 2.
The printing ink composition having an average particle size of 2 μm or less at each dispersant addition amount was considered to have good dispersibility.
（２）分散性の評価（II）（再分散性）
（１）で得られた印刷インキ組成物を、アドバンテック社製減圧乾燥機ＶＯ−３２０で８０℃、２４時間で減圧乾燥を行い、溶剤を完全に除去した。その後、再度、酢酸エチル／ＩＰＡの質量比が１／１の混合有機溶剤を加えてカーボンブラック濃度１０質量％に調整し、超音波分散装置で１時間分散処理を行い、カーボンブラックを再分散させた印刷インキ組成物を得た。次いで（１）と同様に印刷インキ組成物のカーボンブラックの平均粒径を測定した。結果を表２に示す。
尚、印刷インキ組成物は、各分散剤添加量において平均粒径が２μｍ以下であるものを再分散性が良好であるとした。
(2) Evaluation of dispersibility (II) (redispersibility)
The printing ink composition obtained in (1) was dried under reduced pressure at 80 ° C. for 24 hours with a vacuum dryer VO-320 manufactured by Advantech Co., Ltd. to completely remove the solvent. After that, the mixed organic solvent having a mass ratio of ethyl acetate / IPA of 1/1 was added again to adjust the carbon black concentration to 10% by mass, and the carbon black was redispersed by performing a dispersion treatment for 1 hour with an ultrasonic disperser. A printing ink composition was obtained. Next, the average particle size of carbon black in the printing ink composition was measured in the same manner as in (1). The results are shown in Table 2.
The printing ink composition having an average particle size of 2 μm or less at each dispersant addition amount was considered to have good redispersibility.
（３）分散性の評価（III）（保存後の分散性）
（２）で得られた印刷インキ組成物を、ヤマト社製乾燥機ＤＫ６００中に５０℃、７日間静置した。その後、（１）と同様に印刷インキ組成物のカーボンブラックの平均粒径を測定した。結果を表２に示す。
尚、印刷インキ組成物は、各分散剤添加量において平均粒径が２μｍ以下であるものを分散性が良好であるとし、２μｍを超える場合は、２μｍにより近いものの方がより分散性が良好であるとした。
(3) Evaluation of dispersibility (III) (Dispersibility after storage)
The printing ink composition obtained in (2) was allowed to stand in a dryer DK600 manufactured by Yamato Co., Ltd. at 50 ° C. for 7 days. Then, the average particle size of carbon black in the printing ink composition was measured in the same manner as in (1). The results are shown in Table 2.
As for the printing ink composition, those having an average particle size of 2 μm or less at each dispersant addition amount have good dispersibility, and those having an average particle size of more than 2 μm have better dispersibility when they are closer to 2 μm. There was.
Claims (13)
〔式中、Ｒ１は炭素数７以上２１以下の炭化水素基、Ｒ２は炭素数１以上５以下の２価の炭化水素基である。〕 The dispersant composition for printing ink according to claim 1, wherein the salt of the amidate is a salt of the imidazoline compound of the following formula (1).
[In the formula, R 1 is a hydrocarbon group having 7 or more and 21 or less carbon atoms, and R 2 is a divalent hydrocarbon group having 1 or more and 5 or less carbon atoms. ]
オレフィンと不飽和二塩基酸との共重合体の、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンによるアミド化物又はその塩（ａ）と、
酢酸エステル（ｂ１）と低級アルコール（ｂ２）との混合有機溶剤（ｂ）と、
を含有する、印刷インキ組成物。 Printing ink powder and
An amidate of a copolymer of an olefin and an unsaturated dibasic acid with an amine having a branched alkyl group having 6 to 10 carbon atoms or a salt (a) thereof.
A mixed organic solvent (b) of an acetic acid ester (b1) and a lower alcohol (b2),
A printing ink composition containing.
前記共重合体を、炭素数６以上１０以下の分岐鎖アルキル基を有するアミンでアミド化して前記共重合体のアミド化物を得る工程、
を有する、印刷インキ用分散剤組成物の製造方法。 A step of reacting an olefin and an unsaturated dibasic acid in a reaction solvent containing an acetic acid ester (b1) and a lower alcohol (b2) to obtain a copolymer, and the copolymer having 6 or more carbon atoms and 10 carbon atoms. The step of amidating with an amine having the following branched chain alkyl group to obtain an amidated product of the copolymer.
A method for producing a dispersant composition for printing ink.
〔式中、Ｒ１は炭素数７以上２１以下の炭化水素基、Ｒ２は炭素数１以上５以下の２価の炭化水素基である。〕 The method for producing a dispersant composition for printing ink according to claim 12, further comprising a step of neutralizing the amidazoline of the copolymer with an imidazoline compound of the following formula (1).
[In the formula, R 1 is a hydrocarbon group having 7 or more and 21 or less carbon atoms, and R 2 is a divalent hydrocarbon group having 1 or more and 5 or less carbon atoms. ]
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