JP6640007B2 - Varnish for printing ink, printing ink, and printed matter - Google Patents
Varnish for printing ink, printing ink, and printed matter Download PDFInfo
- Publication number
- JP6640007B2 JP6640007B2 JP2016080298A JP2016080298A JP6640007B2 JP 6640007 B2 JP6640007 B2 JP 6640007B2 JP 2016080298 A JP2016080298 A JP 2016080298A JP 2016080298 A JP2016080298 A JP 2016080298A JP 6640007 B2 JP6640007 B2 JP 6640007B2
- Authority
- JP
- Japan
- Prior art keywords
- varnish
- oil
- printing ink
- meth
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000007639 printing Methods 0.000 title claims description 78
- 239000002966 varnish Substances 0.000 title claims description 78
- 229920005989 resin Polymers 0.000 claims description 59
- 239000011347 resin Substances 0.000 claims description 59
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 53
- 239000000178 monomer Substances 0.000 claims description 37
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 37
- 239000004925 Acrylic resin Substances 0.000 claims description 36
- 229920000178 Acrylic resin Polymers 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 33
- 239000008158 vegetable oil Substances 0.000 claims description 31
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 25
- 239000000049 pigment Substances 0.000 claims description 23
- 229920002554 vinyl polymer Polymers 0.000 claims description 23
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims 1
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- 239000002904 solvent Substances 0.000 description 68
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 4
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- 239000003505 polymerization initiator Substances 0.000 description 4
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000019483 Peanut oil Nutrition 0.000 description 3
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 3
- 235000011613 Pinus brutia Nutrition 0.000 description 3
- 241000018646 Pinus brutia Species 0.000 description 3
- 235000019484 Rapeseed oil Nutrition 0.000 description 3
- 244000088415 Raphanus sativus Species 0.000 description 3
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 3
- 235000019485 Safflower oil Nutrition 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 235000019486 Sunflower oil Nutrition 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
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- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
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- 239000005995 Aluminium silicate Substances 0.000 description 1
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000270722 Crocodylidae Species 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
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- 239000005909 Kieselgur Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
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- 239000004698 Polyethylene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
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- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
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- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 150000002170 ethers Chemical class 0.000 description 1
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- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
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- 239000010649 ginger oil Substances 0.000 description 1
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
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- 239000010440 gypsum Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 239000010460 hemp oil Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 238000000691 measurement method Methods 0.000 description 1
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical group NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical group CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 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
- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-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
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SMYREFDDLSTNKQ-UHFFFAOYSA-N oxocan-2-ol Chemical compound OC1CCCCCCO1 SMYREFDDLSTNKQ-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000005459 perfluorocyclohexyl group Chemical group 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
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- YOSXAXYCARLZTR-UHFFFAOYSA-N prop-2-enoyl isocyanate Chemical compound C=CC(=O)N=C=O YOSXAXYCARLZTR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-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
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- MQVCTPXBBSKLFS-UHFFFAOYSA-N tri(propan-2-yloxy)-propylsilane Chemical compound CCC[Si](OC(C)C)(OC(C)C)OC(C)C MQVCTPXBBSKLFS-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、ロジンまたはトール油由来のインキ用樹脂、すなわちコロホニウム樹脂に代替可能な、アクリル系樹脂を主成分とする印刷インキ用樹脂ワニス、それを含有する印刷インキ、およびその印刷物に関する。 TECHNICAL FIELD The present invention relates to a resin varnish for a printing ink mainly composed of an acrylic resin, which can be substituted for a resin for an ink derived from rosin or tall oil, that is, a colophonium resin, a printing ink containing the same, and a printed material thereof.
オフセット用平版インキ用ワニスには、ロジン変性フェノール樹脂がその性能の安定性に優れる点から広く使用されている。然しながら、現在、このロジン変性フェノール樹脂の原料として用いられるロジンは、松資源の保護の観点から生産量は減少している一方で、タイヤ、接着剤等の製造に使われるために需要は増加する傾向にあり、需給バランスが崩れている状況にある。 Rosin-modified phenolic resins are widely used in offset lithographic ink varnishes because of their excellent performance stability. However, at present, the amount of rosin used as a raw material of this rosin-modified phenolic resin is decreasing from the viewpoint of protection of pine resources, but the demand is increasing because it is used for manufacturing tires, adhesives, and the like. There is a tendency for the supply and demand balance to collapse.
オフセット用平版インキにおけるロジン変性フェノール樹脂の他の樹脂材料としては、例えば、アルキッド樹脂が印刷物の光沢向上させる目的でロジン変性フェノール樹脂に一部配合して用いられている。 As another resin material of the rosin-modified phenol resin in the lithographic ink for offset, for example, an alkyd resin is used by partially blending it with the rosin-modified phenol resin for the purpose of improving the gloss of printed matter.
然しながら、アルキッド樹脂を印刷インキ用ワニスとして使用する場合、インキ樹脂として一般に広く使用されているロジン変性フェノール樹脂に対して相溶性は必ずしも良好ではなく、また、アルキッド樹脂を処方した平版インキは粘度が低下して、印刷作業性に支障を来たすため、ロジン変性フェノール樹脂に対する配合割合はごく少量とならざるを得ないのが現状であった。更に、アルキッド樹脂は酸価、水酸基価が高いために印刷インキに用いた場合、乳化特性を低下させしまう問題があり、そのため、例えば酸価及び水酸基価を著しく低減し、この乳化特性を改善する技術などが知られている（例えば、特許文献１参照）。 However, when alkyd resins are used as varnishes for printing inks, their compatibility with rosin-modified phenolic resins, which are generally widely used as ink resins, is not always good, and lithographic inks formulated with alkyd resins have low viscosity. At the same time, the mixing ratio with respect to the rosin-modified phenolic resin has to be very small because it lowers and hinders the printing workability. Further, the alkyd resin has a problem that when used in a printing ink due to a high acid value and a high hydroxyl value, the emulsifying property is reduced. Therefore, for example, the acid value and the hydroxyl value are significantly reduced, and this emulsifying property is improved. Techniques and the like are known (for example, see Patent Document 1).
然しながら、特許文献１記載のワニス配合処方ではアルキッド樹脂の酸価や水酸基が低い為にこれをロジン変性フェノール樹脂に対して一部配合してワニスを調整する場合には印刷インキ自体の乳化特性を改善することが出来るものの、アルキッド樹脂自体の粘度が低く、それ自体単独で使用しようとする場合にミスチングが生じやすい、といった印刷作業性に劣り、到底、ロジン変性フェノール樹脂に代替できるものではなかった。 However, in the varnish compounding formulation described in Patent Document 1, since the alkyd resin has a low acid value and a low hydroxyl group, when the varnish is adjusted by partially adding the alkyd resin to the rosin-modified phenol resin, the emulsifying properties of the printing ink itself are reduced. Although it can be improved, the viscosity of the alkyd resin itself is low, misting is likely to occur when it is used by itself, and the printing workability is inferior, and at all, it could not be replaced with a rosin-modified phenol resin .
石油原料から得られる樹脂はメタンハイドレート資源の発掘が進み安定化され、また、植物油も安定的な栽培による供給が継続する見通しである。この中、石油化学原料と植物油等を主原料として、市場に豊富に供給された樹脂技術で、平版インキ用のロジンフェノール樹脂に代替する主たる樹脂として設計することは重要である。 Resins obtained from petroleum feedstocks are expected to be stabilized by the progress of excavation of methane hydrate resources, and the supply of vegetable oil through stable cultivation is expected to continue. Among them, it is important to design as a main resin that replaces rosin phenol resin for lithographic inks with abundantly supplied resin technology using petrochemical raw materials and vegetable oils as main raw materials.
従って本発明が解決しようとする課題は、ロジン変性フェノール樹脂と同等な乳化特性や印刷作業性を有する、該ロジン変性フェノール樹脂に代替可能な印刷インキ用ワニス、印刷インキ、これを印刷してなる印刷物を提供することにある。 Therefore, an object of the present invention is to provide a varnish for a printing ink, a printing ink, and a printing ink, which have the same emulsifying properties and printing workability as a rosin-modified phenol resin, and which can be substituted for the rosin-modified phenol resin. To provide printed matter.
本発明者らは上記課題を解決すべく鋭意検討を重ねた結果、特定構造を有するビニル系モノマーを必須成分として用いてなるアクリル系樹脂が、従来使用されてきたロジン系フェノール樹脂と同等の印刷特性を発現することを見出し、本発明を完成するに至った。 The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, an acrylic resin using a vinyl monomer having a specific structure as an essential component has a printing property equivalent to that of a conventionally used rosin phenol resin. The inventors have found that the characteristics are exhibited, and have completed the present invention.
即ち、本発明は、ジシクロペンタジエン（メタ）アクリレートを必須とするビニル系単量体混合物を重合してなるアクリル系樹脂を樹脂成分とすることを特徴とする印刷インキ用ワニス、前記印刷インキ用ワニスに、顔料を配合してなる印刷インキ及び紙基材上に前記印刷インキを用いて印刷してなる印刷物を提供するものである。 That is, the present invention provides a varnish for a printing ink and a varnish for a printing ink, wherein the resin component is an acrylic resin obtained by polymerizing a vinyl monomer mixture containing dicyclopentadiene (meth) acrylate as an essential component. An object of the present invention is to provide a printing ink obtained by mixing a varnish with a pigment and a printed matter obtained by printing on a paper substrate using the printing ink.
本発明によれば、ロジン変性フェノール樹脂と同等な乳化特性や印刷作業性などの印刷特性を有する、該ロジン変性フェノール樹脂に代替可能な印刷インキ用ワニス、印刷インキ、これを印刷してなる印刷物を提供できる。 According to the present invention, a varnish for a printing ink, a printing ink, and a printed matter obtained by printing the same, having printing properties such as emulsification properties and printing workability equivalent to those of a rosin-modified phenol resin, which can be substituted for the rosin-modified phenol resin Can be provided.
本発明の印刷インキ用ワニスに用いるジシクロペンタジエンメタアクリレート（ａ）は、下記構造式のビニル系単量体であり、例えば、ＢＩＭＡＸ社等から市販されているものをそのまま用いることができる。 The dicyclopentadiene methacrylate (a) used in the varnish for printing ink of the present invention is a vinyl monomer having the following structural formula, and for example, those commercially available from BIMAX or the like can be used as they are.
前記市販品には、当該構造を有するビニル系単量体以外の、例えば、シクロ環が３個以上連結した構造を有する化合物も含まれた混合物である場合もあるが、本発明においては、前記構造を有するビニル系単量体が含まれていればよく、他の構造の化合物との混合物をそのまま使用してもよい。 The commercially available product may be a mixture other than the vinyl monomer having the structure, for example, a mixture containing a compound having a structure in which three or more cyclo rings are linked. It is sufficient that a vinyl monomer having a structure is included, and a mixture with a compound having another structure may be used as it is.
なお、本発明においてメタアクリレートとは、アクリレート、メタクリレート及びそれらの混合物をいうものである。 In the present invention, methacrylate refers to acrylate, methacrylate, and a mixture thereof.
ジシクロペンタジエン構造を有する化合物を、フェノール樹脂あるいはロジンエステルの変性剤として使用し、得られたジシクロペンタジエン変性樹脂を印刷インキ用ワニスの樹脂成分として用いることは、例えば、特開平８−６００６４号公報、特開２０１１−１６８６９号公報等により周知ではあるが、これらの文献には、ジシクロペンタジエン構造を有するビニル系単量体については言及されておらず、さらに、当該単量体を含むビニル系単量体を重合してなるアクリル系樹脂が、印刷インキ用ワニスの樹脂成分として有用であることは一切記載されていない。 The use of a compound having a dicyclopentadiene structure as a modifier of a phenol resin or a rosin ester, and the use of the obtained dicyclopentadiene-modified resin as a resin component of a varnish for printing ink is disclosed, for example, in JP-A-8-60064. Japanese Patent Application Laid-Open No. 2011-16869 and the like, but these documents do not mention a vinyl-based monomer having a dicyclopentadiene structure, and furthermore, a vinyl-containing monomer containing the monomer. There is no description that an acrylic resin obtained by polymerizing a system monomer is useful as a resin component of a varnish for printing ink.
本発明の印刷インキ用ワニスの樹脂成分として用いるアクリル系樹脂は、前述のジシクロペンタジエンメタアクリレート（ａ）（以下ＤＣＰＭＡと示す。）を必須の原料として重合して得られるものであるが、その他のビニル系単量体との共重合体であってもよい。 The acrylic resin used as a resin component of the varnish for printing ink of the present invention is obtained by polymerizing the above-mentioned dicyclopentadiene methacrylate (a) (hereinafter referred to as DCPMA) as an essential raw material. May be a copolymer with a vinyl monomer.
ＤＣＰＭＡを用いたアクリル系樹脂を平版印刷用ワニスの樹脂成分として使用すると、他のエステル類を使用した場合よりも粘度が高くなり、また、ＤＣＰＭＡホモポリマーは１６０℃以上のガラス転移温度を持つと推定されるために、他のビニル系単量体との共重合体も高いガラス転移点を有し、高速で印刷を行う印刷機および乾燥工程中でより速い乾燥性、セット性を実現することができる。 When an acrylic resin using DCPMA is used as a resin component of a lithographic printing varnish, the viscosity becomes higher than when other esters are used, and the DCPMA homopolymer has a glass transition temperature of 160 ° C. or more. It is presumed that copolymers with other vinyl monomers also have a high glass transition point, and realize faster drying and setting properties in printing machines that perform high-speed printing and in the drying process. Can be.
前記その他のビニル系単量体としては、例えば、（メタ）アクリル酸エステル系単量体が挙げられる。具体的には、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ヘキシル（メタ）アクリレート、シクロヘキシル（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、ドデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、２，２，２−トリフルオロエチル（メタ）アクリレート、２，２，３，３−ペンタフルオロプロピル（メタ）アクリレート、パーフルオロシクロヘキシル（メタ）アクリレート、２，２，３，３，−テトラフルオロプロピル（メタ）アクリレート、β−（パーフルオロオクチル）エチル（メタ）アクリレート、グリシジル（メタ）アクリレート、アリルグリシジルエーテル、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、ポリエチレングリコールモノ（メタ）アクリレート、グリセロールモノ（メタ）アクリレート、アミノエチル（メタ）アクリレート、Ｎ−モノアルキルアミノアルキル（メタ）アクリレート、Ｎ，Ｎ−ジアルキルアミノアルキル（メタ）アクリレート、２−アジリジニルエチル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、アリル（メタ）アクリレート、アセトアセトキシエチル（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、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、アリル（メタ）アクリレート等が挙げられる。これらは、１種または２種以上の混合物として用いることができる。 Examples of the other vinyl monomers include (meth) acrylate monomers. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (Meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) ) Acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3- Tet Fluoropropyl (meth) acrylate, β- (perfluorooctyl) ethyl (meth) acrylate, glycidyl (meth) acrylate, allyl glycidyl ether, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol Mono (meth) acrylate, glycerol mono (meth) acrylate, aminoethyl (meth) acrylate, N-monoalkylaminoalkyl (meth) acrylate, N, N-dialkylaminoalkyl (meth) acrylate, 2-aziridinylethyl ( (Meth) acrylate, dicyclopentenyl (meth) acrylate, allyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, allyl (meth) acrylate, etc. Is mentioned. These can be used alone or as a mixture of two or more.
更に一般にラジカル重合反応に用いることができるものであってもよく、例えば、酢酸ビニル、プロピオン酸ビニル、ビニルブチラート、バーサチック酸ビニル等のビニルエステル類；メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、アミルビニルエーテル、ヘキシルビニルエーテル等のビニルエーテル類；（メタ）アクリロニトリル等のニトリル基含有エチレン性不飽和単量体；スチレン、α−メチルスチレン、ビニルトルエン、ビニルアニソール、α−ハロスチレン、ビニルナフタリン、ジビニルベンゼン、ジアリルフタレート等の芳香族環を有するビニル化合物等が挙げられる。これらは、１種または２種以上の混合物として用いることができる。 Further, those which can be generally used for a radical polymerization reaction may be used. For example, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl versatate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, and butyl vinyl ether , Vinyl ethers such as amyl vinyl ether and hexyl vinyl ether; ethylenically unsaturated monomers containing a nitrile group such as (meth) acrylonitrile; styrene, α-methylstyrene, vinyltoluene, vinylanisole, α-halostyrene, vinylnaphthalene, divinylbenzene And vinyl compounds having an aromatic ring such as diallyl phthalate. These can be used alone or as a mixture of two or more.
更に、官能基を有するエチレン性不飽和単量体も用いることが可能で、例としては、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−イソプロポキシメチル（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−イソブトキシメチル（メタ）アクリルアミド等のメチロールアミド基またはそのアルコキシ化物含有重合性単量体；ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルメチルジメトキシシラン、γ−（メタ）アクリロキシプロピルメチルジエトキシシラン、γ−（メタ）アクリロキシプロピルトリイソプロポキシシラン、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシラン及びその塩酸塩等のシリル基含有重合性単量体；（メタ）アクリロイルイソシアナート、（メタ）アクリロイルイソシアナートエチルのフェノール或いはメチルエチルケトオキシム付加物等のイソシアナート基及び／またはブロック化イソシアナート基含有重合性単量体；２−イソプロペニル−２−オキサゾリン、２−ビニル−２−オキサゾリン等のオキサゾリン基含有重合性単量体；（メタ）アクリルアミド、Ｎ−モノアルキル（メタ）アクリルアミド、Ｎ，Ｎ−ジアルキル（メタ）アクリルアミド等のアミド基含有重合性単量体；アクロレイン、ジアセトン（メタ）アクリルアミド等のカルボニル基含有重合性単量体等が挙げられる。 Further, an ethylenically unsaturated monomer having a functional group can also be used. Examples thereof include N-methylol (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide. , N-isobutoxymethyl (meth) acrylamide and other methylolamide groups or their alkoxylated polymerizable monomers; vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ -(Meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (Meta) acryloki Silyl group-containing polymerizable monomers such as propyltriisopropoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and its hydrochloride; (meth) acryloyl isocyanate; ) Polymerizable monomers containing isocyanate groups and / or blocked isocyanate groups such as phenol or methyl ethyl ketoxime adduct of acryloyl isocyanatoethyl; 2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline and the like. Oxazoline group-containing polymerizable monomer; amide group-containing polymerizable monomer such as (meth) acrylamide, N-monoalkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide; acrolein, diacetone (meth) acrylamide Such as carbonyl group-containing polymerizable Mer, and the like.
その他のビニル単量体としては、イソプレン、クロロプレン、ブタジエン、エチレン、テトラフルオロエチレン、フッ化ビニリデン、Ｎ−ビニルピロリドン等を使用することができる。 As other vinyl monomers, isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N-vinylpyrrolidone and the like can be used.
これらのその他のビニル系単量体を併用する場合、本発明で提供するワニス及びインキが、従来使用されてきたロジン変性フェノール樹脂と同等以上の印刷特性を有する点より、（メタ）アクリル酸エステル及び／又はスチレン系単量体を用いることが好ましく、特に、長鎖アルキル基を有する（メタ）アクリル酸エステル及び／又はスチレンモノマーを用いることが好ましい。 When these other vinyl monomers are used in combination, the varnish and the ink provided by the present invention have a printing property equal to or higher than that of a rosin-modified phenol resin conventionally used, and therefore, a (meth) acrylate ester It is preferable to use a styrene monomer and / or a styrene monomer having a long-chain alkyl group, and / or a styrene monomer.
本発明で用いるビニル系単量体混合物（Ａ）中には、前記ジシクロペンタジエン（メタ）アクリレート（ａ）を含むことが必須であるが、その質量割合としては、得られる印刷インキの印刷特性、特に、乾燥性に優れる点から、５〜６０質量％の範囲で含まれることが好ましく、５〜４０質量％の範囲であることが特に好ましい。 It is essential that the vinyl-based monomer mixture (A) used in the present invention contains the above-mentioned dicyclopentadiene (meth) acrylate (a). Particularly, from the viewpoint of excellent drying properties, the content is preferably in the range of 5 to 60% by mass, and particularly preferably in the range of 5 to 40% by mass.
ＤＣＰＭＡを単量体として用いると、得られるアクリル樹脂のガラス転移点を非常に高くすることが可能であり、このためＤＣＰＭＡと共重合してなる樹脂は高速印刷機上で短時間にセットでき、乾燥性に優れる。一般的な（メタ）アクリル酸エステルからなるアクリル樹脂は、ＤＣＰＭＡを用いてなるアクリル樹脂よりもガラス転移点が下がることになるため、前記ビニル系単量体混合物（Ａ）中に（メタ）アクリル酸エステルが含まれる場合には、得られる印刷インキの印刷特性の観点より、その質量割合としては、５〜６０質量％の範囲にすることが好ましい。 When DCPMA is used as a monomer, the glass transition point of the obtained acrylic resin can be made extremely high, so that the resin copolymerized with DCPMA can be set in a short time on a high-speed printer, Excellent drying property. An acrylic resin comprising a general (meth) acrylic acid ester has a lower glass transition point than an acrylic resin using DCPMA. Therefore, the (meth) acrylic resin is contained in the vinyl monomer mixture (A). When an acid ester is contained, the mass ratio is preferably in the range of 5 to 60% by mass from the viewpoint of the printing characteristics of the resulting printing ink.
更に安価に製造するためにスチレンモノマーに代表される汎用の原料を多く使用することを念頭に置くと、得られるアクリル樹脂のガラス転移点と価格とのバランス、並びに乾燥性とのバランスの観点より、スチレンモノマーを使用する場合のその質量割合としては、５〜４０質量％の範囲にすることが好ましい。 In view of using many general-purpose raw materials typified by styrene monomer in order to produce more inexpensively, from the viewpoint of the balance between the glass transition point of the obtained acrylic resin and the price, and the balance between the drying property and When a styrene monomer is used, its mass ratio is preferably in the range of 5 to 40% by mass.
更に、近年の環境対応の観点からは、印刷インキは溶解性の低い溶剤や植物油への溶解性が重視されるために、特にインキ溶剤や植物油への溶解性を向上させることができる点より、ビニル系単量体として、炭素数が４〜２０程度の長鎖アルキル基を有する（メタ）アクリル酸エステルを用いることが好ましく、例えば、汎用性と溶解性との観点より、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、エチルヘキシル（メタ）アクリレート、イソボロニル（メタ）アクリレートを併用することが好ましい。 Furthermore, from the viewpoint of environmental friendliness in recent years, since the printing ink is emphasized on solubility in a low-solubility solvent or vegetable oil, the solubility in an ink solvent or vegetable oil can be particularly improved. As the vinyl monomer, it is preferable to use a (meth) acrylate having a long-chain alkyl group having about 4 to 20 carbon atoms. For example, from the viewpoint of versatility and solubility, butyl (meth) acrylate , Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, and isobornyl (meth) acrylate are preferably used in combination.
本発明で用いるアクリル系樹脂は、前述のビニル系単量体混合物（Ａ）を従来知られている溶液重合法によりラジカル重合することによって製造することができる。 The acrylic resin used in the present invention can be produced by subjecting the above-mentioned vinyl monomer mixture (A) to radical polymerization by a conventionally known solution polymerization method.
具体的には、溶剤の存在下、前記ビニル系単量体混合物（ａ）と重合開始剤とを、好ましくは４０℃〜１６０℃の温度下で混合、攪拌し、ラジカル重合を進行させる方法が挙げられる。 Specifically, a method in which the vinyl monomer mixture (a) and the polymerization initiator are mixed and stirred at a temperature of preferably 40 ° C to 160 ° C in the presence of a solvent to advance radical polymerization. No.
前記重合開始剤としては、例えば、メチルエチルケトンパーオキサイド、ベンゾイルパーオキサイド、ジクミルパーオキサイド、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ラウロイルパーオキサイド、ｔ−ブチルパーオキシオクトエート、ｔ−ブチルパーオキシベンゾエート、ラウロイルパーオキサイド、商品名「ナイパーＢＭＴ−Ｋ４０」（日油（株）製；ｍ−トルオイルパーオキサイドとベンゾイルパーオキサイドの混合物）等の有機過酸化物や、アゾビスイソブチロニトリル、商品名「ＡＢＮ−Ｅ」［（株）日本ファインケム製；２，２’−アゾビス（２−メチルブチロニトリル）］等のアゾ系化合物等を使用することができる。 Examples of the polymerization initiator include, for example, methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, lauroyl peroxide, t-butyl peroxyoctoate, and t-butyl peroxide. Organic peroxides such as oxybenzoate, lauroyl peroxide, trade name "Niper BMT-K40" (manufactured by NOF Corp .; a mixture of m-toluoyl peroxide and benzoyl peroxide), and azobisisobutyronitrile And an azo compound such as "ABN-E" (trade name, manufactured by Nippon Finechem Co., Ltd .; 2,2'-azobis (2-methylbutyronitrile)).
また、前記アクリル系樹脂を製造する際に使用可能な溶剤としては、例えばメタノール、エタノール、プロパノール、ブタノール、エチレングリコールメチルエーテル、ジエチレングリコールメチルエーテルなどのアルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン類、テトラヒドロフラン、ジオキサン、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などのエーテル類、ヘキサン、ヘプタン、オクタンなどの炭化水素類、ベンゼン、トルエン、キシレン、クメンなどの芳香族類、酢酸エチル、酢酸ブチル等を使用することができる。 Examples of solvents that can be used when producing the acrylic resin include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol methyl ether, diethylene glycol methyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketones, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, hydrocarbons such as hexane, heptane, octane, aromatics such as benzene, toluene, xylene, cumene, ethyl acetate, butyl acetate and the like. Can be used.
インキ配合を前提とした樹脂の作製をするために、インキ用の溶剤を溶剤とすることも可能で、例えば、ＪＸ社製「１号スピンドル油」、「３号ソルベント」、「４号ソルベント」、「５号ソルベント」、「６号ソルベント」、「ナフテゾールＨ」、「アルケン５６ＮＴ」、三菱化学（株）製「ダイヤドール１３」、「ダイヤレン１６８」；日産化学（株）製「Ｆオキソコール」、「Ｆオキソコール１８０」；ＪＸ社製「ＡＦソルベント４号」、「ＡＦソルベント５号」「ＡＦソルベント６号」「ＡＦソルベント７号」、ＩＳＵ社製ＤＳＯＬ溶剤、「ソルベントＨ」；ＩＳＵ（株）製「Ｎ−パラフィンＣ１４−Ｃ１８」；出光興産（株）「スーパーゾルＬＡ３５」、「スーパーゾルＬＡ３８」；エクソン化学（株）の「エクソールＤ８０」、「エクソールＤ１１０」、「エクソールＤ１２０」、「エクソールＤ１３０」、「エクソールＤ１６０」、「エクソールＤ１００Ｋ」、「エクソールＤ１２０Ｋ」、「エクソールＤ１３０Ｋ」、「エクソールＤ２８０」、「エクソールＤ３００」、「エクソールＤ３２０」；マギーブラザーズ社製の「マギーソル−４０」、「マギーソル−４４」、「マギーソル−４７」、「マギーソル−５２」、「マギーソル−６０」等を重合用の溶剤とすることができる。 In order to prepare a resin on the premise of ink formulation, it is also possible to use a solvent for ink as a solvent. For example, "No. 1 spindle oil", "No. 3 solvent", and "No. 4 solvent" manufactured by JX Corporation , "No. 5 Solvent", "No. 6 Solvent", "Naphthesol H", "Alken 56NT", "Diadoll 13", "Dialen 168" manufactured by Mitsubishi Chemical Corporation; "F Oxocall" manufactured by Nissan Chemical Industries, Ltd. "F Oxocol 180"; "AF Solvent 4", "AF Solvent 5", "AF Solvent 6", "AF Solvent 7" manufactured by JX, DSOL solvent manufactured by ISU, "Solvent H"; "N-paraffin C14-C18"; Idemitsu Kosan Co., Ltd. "Super Sol LA35", "Super Sol LA38"; Exxon Chemical Co., Ltd. "Exsol D80"; Exor D110, Exor D120, Exor D130, Exor D160, Exor D100K, Exor D120K, Exor D130K, Exor D280, Exor D300, Exor D320; Maggie; "Magisol 40", "Magisol 44", "Magisol 47", "Magisol 52", "Magisol 60", etc. manufactured by Brothers can be used as the solvent for polymerization.
同様に、インキ配合を前提とした樹脂の作製をするために、植物油を溶剤とすることも可能で、例えば、アサ実油、アマニ油、エノ油、オイチシカ油、オリーブ油、カカオ油、カポック油、カヤ油、カラシ油、キョウニン油、キリ油、ククイ油、クルミ油、ケシ油、ゴマ油、サフラワー油、ダイコン種油、大豆油、大風子油、ツバキ油、トウモロコシ油、ナタネ油、ニガー油、ヌカ油、パーム油、ヒマシ油、ヒマワリ油、ブドウ種子油、ヘントウ油、松種子油、綿実油、ヤシ油、落花生油、南洋油桐油（ジャトロファ）、脱水ヒマシ油などが挙げられる。中でも、ラジカル重合を行うため、サフラワー油、ダイコン種油、大豆油、トウモロコシ油、ナタネ油、ヌカ油、ヒマシ油、ヒマワリ油、ブドウ種子油、綿実油、落花生油、脱水ヒマシ油が好ましい。その他、回収／再生された再生植物油も用いることができる。再生植物油としては、含水率を０．３質量％以下、ヨウ素価を１００以上、酸価を３以下として再生処理した油が好ましい。 Similarly, it is also possible to use a vegetable oil as a solvent in order to prepare a resin on the premise of ink formulation, for example, asa seed oil, linseed oil, eno oil, euca deer oil, olive oil, cacao oil, kapok oil, Kaya oil, mustard oil, ginger oil, kiri oil, kukui oil, walnut oil, poppy oil, sesame oil, safflower oil, radish seed oil, soybean oil, soybean oil, camellia oil, corn oil, rapeseed oil, niger oil, Nuka oil, palm oil, castor oil, sunflower oil, grape seed oil, gentian oil, pine seed oil, cottonseed oil, coconut oil, peanut oil, southern oil tung oil (jatropha), dehydrated castor oil and the like. Among them, safflower oil, radish seed oil, soybean oil, corn oil, rapeseed oil, bran oil, castor oil, sunflower oil, grape seed oil, cottonseed oil, peanut oil, and dehydrated castor oil are preferable for performing radical polymerization. In addition, recovered / regenerated regenerated vegetable oil can also be used. As the regenerated vegetable oil, an oil regenerated with a water content of 0.3% by mass or less, an iodine value of 100 or more, and an acid value of 3 or less is preferable.
更に、印刷インキに含まれる各種植物油を単独で、あるいは、前述の溶剤と併用して用いてもよい。 Further, various vegetable oils contained in the printing ink may be used alone or in combination with the above-mentioned solvent.
反応後、残留モノマー除去の為、反応系に窒素を吹き込むみ、減圧下にモノマーを除く工程をとることが出来る。 After the reaction, in order to remove the residual monomer, a step of removing the monomer under reduced pressure can be performed by blowing nitrogen into the reaction system.
本発明で用いるアクリル系樹脂としては、その重量平均分子量（Ｍｗ）が５，０００〜２００，０００の範囲であり、また数平均分子量（Ｍｎ）が１,０００〜１００，０００の範囲のものであることが、得られる印刷インキの乾燥性と塗膜強度の観点から好ましい。 The acrylic resin used in the present invention has a weight average molecular weight (Mw) of 5,000 to 200,000 and a number average molecular weight (Mn) of 1,000 to 100,000. This is preferable from the viewpoints of drying properties and coating film strength of the obtained printing ink.
なお、本発明で用いるアクリル系樹脂の分子量は、以下の方法により、測定した。
測定装置 ；東ソー株式会社製 ＨＬＣ−８２２０ＧＰＣ
カラム ；東ソー株式会社製 ＴＳＫ−ＧＵＡＲＤＣＯＬＵＭＮ ＳｕｐｅｒＨＺ−Ｌ
＋東ソー株式会社製 ＴＳＫ−ＧＥＬ ＳｕｐｅｒＨＺＭ−Ｍ×４
検出器 ；ＲＩ（示差屈折計）
データ処理；東ソー株式会社製 マルチステーションＧＰＣ−８０２０ｍｏｄｅｌＩＩ
測定条件 ；カラム温度 ４０℃
溶媒 テトラヒドロフラン
流速 ０．３５ｍｌ／分
標準 ；単分散ポリスチレン
試料 ；樹脂固形分換算で０．２質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（１００μｌ）
The molecular weight of the acrylic resin used in the present invention was measured by the following method.
Measurement device: Tosoh Corporation HLC-8220GPC
Column: Tosoh Corporation TSK-GUARDCOLUMN SuperHZ-L
+ TSK-GEL SuperHZM-M x 4 manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent Tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodisperse polystyrene sample: 0.2% by mass of resin in solid tetrahydrofuran solution filtered through a microfilter (100 μl)
この様にして得られるアクリル系樹脂は、これにインキ用の溶剤、植物油、又は脂肪酸エステルを加えて粘度とタックの調整がなされ、ワニスとなる。ここで、アクリル系樹脂を製造する際に使用した植物油が多量に系内に残存する場合には、そのままワニスとすることもできるが、通常は溶剤又は植物油を加えて粘度を調整し、更に必要により、更にキレート剤を配合して粘度調整することができる。 The acrylic resin thus obtained is added with a solvent for ink, vegetable oil, or fatty acid ester to adjust the viscosity and tack, and becomes a varnish. Here, when a large amount of the vegetable oil used in producing the acrylic resin remains in the system, it can be used as a varnish as it is, but usually, the viscosity is adjusted by adding a solvent or vegetable oil, and further necessary. Thus, the viscosity can be adjusted by further mixing a chelating agent.
ここで、溶剤を加える工程は、後述するインキ用の溶剤を、アクリル系樹脂の製造後に加える方法、及び、アクリル系樹脂を製造する当初から加える方法が挙げられる。後者の場合、反応生成物の粘度上昇に対して、攪拌をより容易にすることができる。また、この場合に反応後に粘度の微調整を行うために、２回目以降の添加を行ってもよい。然しながら、前者のアクリル系樹脂を製造する反応が終了した後に溶剤を加える方法が、粘度調整が容易であり、かつ、調整を一度にできる方法であり好ましい。 Here, the step of adding the solvent includes a method of adding a solvent for an ink described later after the production of the acrylic resin and a method of adding the solvent for the acrylic resin from the beginning of the production of the acrylic resin. In the latter case, stirring can be made easier with respect to the increase in the viscosity of the reaction product. In this case, the second and subsequent additions may be performed in order to finely adjust the viscosity after the reaction. However, the former method of adding a solvent after the completion of the reaction for producing an acrylic resin is a method in which the viscosity can be easily adjusted and the adjustment can be performed at one time, and is preferred.
また、ワニス調整に使用できるインキ用の溶剤は、沸点１６０℃以上の溶剤であり、例えば、ＪＸ社製「１号スピンドル油」、「３号ソルベント」、「４号ソルベント」、「５号ソルベント」、「６号ソルベント」、「ナフテゾールＨ」、「アルケン５６ＮＴ」、三菱化学（株）製「ダイヤドール１３」、「ダイヤレン１６８」；日産化学（株）製「Ｆオキソコール」、「Ｆオキソコール１８０」；ＪＸ社製「ＡＦソルベント４号」、「ＡＦソルベント５号」「ＡＦソルベント６号」「ＡＦソルベント７号」、ＩＳＵ社製ＤＳＯＬ溶剤、「ソルベントＨ」；ＩＳＵ（株）製「Ｎ−パラフィンＣ１４−Ｃ１８」；出光興産（株）「スーパーゾルＬＡ３５」、「スーパーゾルＬＡ３８」；エクソン化学（株）の「エクソールＤ８０」、「エクソールＤ１１０」、「エクソールＤ１２０」、「エクソールＤ１３０」、「エクソールＤ１６０」、「エクソールＤ１００Ｋ」、「エクソールＤ１２０Ｋ」、「エクソールＤ１３０Ｋ」、「エクソールＤ２８０」、「エクソールＤ３００」、「エクソールＤ３２０」；マギーブラザーズ社製の「マギーソル−４０」、「マギーソル−４４」、「マギーソル−４７」、「マギーソル−５２」、「マギーソル−６０」等が挙げられる。 The solvent for the ink that can be used for varnish adjustment is a solvent having a boiling point of 160 ° C. or higher. For example, “No. 1 spindle oil”, “No. 3 solvent”, “No. 4 solvent”, and “No. 5 solvent” manufactured by JX Corporation "No. 6 Solvent", "Naphthesol H", "Alken 56NT", "Diadoll 13", "Dialen 168" manufactured by Mitsubishi Chemical Corporation; "F Oxocall", "F Oxocall 180" manufactured by Nissan Chemical Industries, Ltd. "AF Solvent 4", "AF Solvent 5", "AF Solvent 6", "AF Solvent 7" manufactured by JX, DSOL solvent manufactured by ISU, "Solvent H"; "N- manufactured by ISU Corporation" Paraffin C14-C18 "; Idemitsu Kosan Co., Ltd." Super Sol LA35 "," Super Sol LA38 "; Exxon Chemical Co., Ltd." Exor D80 "," Exor " Maggie Brothers D110, Exol D120, Exor D130, Exor D160, Exor D100K, Exor D120K, Exor D130K, Exor D280, Exor D300, Exor D320; "Magisol-44", "Magisol-47", "Magisol-52", and "Magisol-60" manufactured by the company.
これらのなかでもＡＦソルベントが溶解性と芳香族成分が少ない点から好ましく、特に、芳香族成分が１．０％以下である所謂アロマフリー溶剤であることが好ましい。更に具体的には、例えば、熱乾燥型オフセット輪転インキ用ワニスの調製には、ＪＸ社製「ＡＦソルベント４号」、ＪＸ社製「ＡＦソルベント５号」、ＪＸ社製「ＡＦソルベント７号」が好ましく、浸透乾燥型新聞インキ用ワニスの調整にはＪＸ社製「ＡＦソルベント６号」、ＩＳＵ社製「ＤＳＯＬ３００」が好ましく、酸化重合型枚葉インキ用ワニスの調整にはＪＸ社製「ＡＦソルベント６号」が好ましい。 Among these, AF solvent is preferable from the viewpoint of solubility and a small amount of aromatic components. In particular, a so-called aroma-free solvent having an aromatic component of 1.0% or less is preferable. More specifically, for example, for preparing a varnish for a hot-drying offset rotary ink, "AF Solvent 4" manufactured by JX, "AF Solvent 5" manufactured by JX, and "AF Solvent 7" manufactured by JX are used. Preferably, "X Solvent No. 6" manufactured by JX and "DSOL300" manufactured by ISU are used for preparation of a varnish for a permeation-drying news ink, and "AF" manufactured by JX is used for preparation of a varnish for an oxidation polymerization type sheet-fed ink. Solvent No. 6 "is preferred.
一方、植物油を溶剤として使用する場合には、前記したとおり、通常、アクリル系樹脂製造時に未反応のまま残存する植物油をそのまま溶剤として利用でき、更に、反応終了後に別途加えてワニスの粘度を調整することができる。 On the other hand, when vegetable oil is used as the solvent, as described above, usually, the vegetable oil remaining unreacted during the production of the acrylic resin can be used as a solvent as it is, and further, after the reaction is completed, the viscosity of the varnish is separately adjusted. can do.
ここで用いることのできる植物油は、例えば、アサ実油、アマニ油、エノ油、オイチシカ油、オリーブ油、カカオ油、カポック油、カヤ油、カラシ油、キョウニン油、キリ油、ククイ油、クルミ油、ケシ油、ゴマ油、サフラワー油、ダイコン種油、大豆油、大風子油、ツバキ油、トウモロコシ油、ナタネ油、ニガー油、ヌカ油、パーム油、ヒマシ油、ヒマワリ油、ブドウ種子油、ヘントウ油、松種子油、綿実油、ヤシ油、落花生油、南洋油桐油（ジャトロファ）、脱水ヒマシ油などが挙げられる。その他、回収／再生された再生植物油も用いることができる。再生植物油としては、含水率を０．３質量％以下、ヨウ素価を１００以上、酸価を３以下として再生処理した油が好ましい。 Vegetable oils that can be used here include, for example, hemp seed oil, linseed oil, eno oil, euca deer oil, olive oil, cacao oil, kapok oil, kaya oil, mustard oil, kyonin oil, kiri oil, kukui oil, walnut oil, Poppy oil, sesame oil, safflower oil, radish seed oil, soybean oil, soybean oil, camellia oil, corn oil, rapeseed oil, niger oil, nuka oil, palm oil, castor oil, sunflower oil, grape seed oil, gentian oil Pine seed oil, cottonseed oil, coconut oil, peanut oil, southern oil tung oil (jatropha), dehydrated castor oil and the like. In addition, recovered / regenerated regenerated vegetable oil can also be used. As the regenerated vegetable oil, an oil regenerated with a water content of 0.3% by mass or less, an iodine value of 100 or more, and an acid value of 3 or less is preferable.
また、脂肪酸エステルを溶剤として使用する場合には、各種植物油由来の脂肪酸のエステル化合物を反応終了後に添加することによりワニスを調整できる。 When a fatty acid ester is used as a solvent, a varnish can be prepared by adding an ester compound of a fatty acid derived from various vegetable oils after completion of the reaction.
また、キレート剤によって粘度の調整を行う場合は、溶剤を先にアクリル系樹脂と混合溶解させて、次いで、キレート剤を均質にワニス中に分散できるため好ましい。この際、キレート化の温度は１００℃以上、２００℃以下であることが好ましい。また、キレート剤の量は通常、溶剤を除く樹脂分に対して０．1〜５質量％の範囲であることが好ましいが、更に０．５〜２質量％の範囲であることが特に好ましい。 When the viscosity is adjusted by a chelating agent, the solvent is preferably mixed and dissolved with the acrylic resin first, and then the chelating agent can be uniformly dispersed in the varnish. In this case, the temperature for chelation is preferably 100 ° C. or more and 200 ° C. or less. The amount of the chelating agent is usually preferably in the range of 0.1 to 5% by mass, more preferably 0.5 to 2% by mass, based on the resin content excluding the solvent.
ここで用いることのできるキレート剤は、例えば、有機アルミニウム化合物、有機チタネート化合物、有機亜鉛化合物、有機力ルシウム化合物等が挙げられる。これらのなかでも有機アルミニウム化合物が好ましい。 The chelating agent that can be used here includes, for example, an organic aluminum compound, an organic titanate compound, an organic zinc compound, an organic lithium compound, and the like. Of these, organoaluminum compounds are preferred.
有機アルミニウム化合物としては、アルミニウムアルコラート、アルミニウムキレート化合物が挙げられ、なかでもアルミニウムイソプロピレート、モノｓｅｃ−ブトキシアルミニウムジイソプロピレート、アルミニウムｓｅｃ−ブチレート、エチルアセトアセテートアルミニウムジイソプレピレート、エチルアセチルアセテートアルミニウムジ−ｎ−ブチレート、エチルアセチルアセテートアルミニウム−ｎ−ブチレート、アルミニウムトリスエチルアセチルアセテートが好ましい。 Examples of the organic aluminum compound include aluminum alcoholate and aluminum chelate compound. Among them, aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, ethyl acetoacetate aluminum diisopropylate, ethyl acetylacetate aluminum Preferred are -n-butyrate, aluminum ethyl acetylacetate-n-butyrate and aluminum trisethyl acetyl acetate.
本発明の印刷インキ用ワニスは、上記した各成分に加え、更に必要により、インキオイルを配合してもよい。インキオイルは、例えば長鎖脂肪酸とアルコールから得られるもの、及び揮発性の無いアルカン、アルケンなどが挙げられる。 The varnish for printing ink of the present invention may further contain an ink oil, if necessary, in addition to the components described above. Examples of the ink oil include those obtained from long-chain fatty acids and alcohols, and non-volatile alkanes and alkenes.
このワニスには、更に、インキの粘度や光沢等の特性を与えるための石油樹脂、レベリング剤等の添加剤を添加することができる。 Additives such as a petroleum resin and a leveling agent for giving properties such as viscosity and gloss of the ink can be further added to the varnish.
本発明の印刷インキ用ワニスは、オフセットインキ、樹脂凸版インキに使用されるが、その中でも特に熱乾燥型オフセット輪転インキ、浸透乾燥型新聞インキ、又は、酸化重合型枚葉インキのワニスとしてとりわけ有用である。特に本発明では、熱乾燥型オフセット輪転インキに用いた場合、印刷特性が良好となるのみならず、その印刷物の光沢に優れたものとなる。 The varnish for printing inks of the present invention is used for offset inks and resin letterpress inks, and is particularly useful as a varnish for heat-drying offset rotary printing inks, permeation-drying newspaper inks, or oxidative polymerization type sheet-fed inks. It is. In particular, in the present invention, when used in a hot-drying type offset rotary ink, not only the printing characteristics are improved, but also the gloss of the printed matter is excellent.
上記印刷インキ用ワニスの各成分の配合割合は、アクリル系樹脂２５〜６０質量％、植物油、脂肪酸エステル、又は溶剤を４０〜７５質量％、その他キレート化剤またはゲル化剤、乾燥抑制剤など５質量％以下の範囲で加えることができる。また、必要に応じて上記のワニスに石油樹脂、ロジンエステル樹脂、又はロジン変性フェノール樹脂を一部添加してもよい。この場合、該ワニス中の全樹脂成分に占める前記アクリル系樹脂の存在割合が４５質量％以上であることが好ましい。本発明では、このようなアクリル系樹脂を多量に使用しても印刷作業性に優れ、実用的な印刷インキが得られることを特長としている。よって、斯かる観点から該ワニス中の全樹脂成分に占める前記アクリル系樹脂の存在割合は、更に、７０質量％以上であることが好ましく、樹脂成分としてアクリル系樹脂を単独で使用することが望ましい。また、植物油を用いる場合には、ワニス中の該植物油の量は３〜６０質量％であることが望ましい。 The mixing ratio of each component of the printing ink varnish is 25 to 60% by mass of an acrylic resin, 40 to 75% by mass of a vegetable oil, a fatty acid ester, or a solvent, and other chelating agents or gelling agents, drying inhibitors, and the like. It can be added in a range of not more than mass%. If necessary, a petroleum resin, a rosin ester resin, or a rosin-modified phenol resin may be partially added to the above varnish. In this case, the proportion of the acrylic resin in all the resin components in the varnish is preferably 45% by mass or more. The present invention is characterized in that even if such an acrylic resin is used in a large amount, printing workability is excellent and a practical printing ink can be obtained. Therefore, from such a viewpoint, the proportion of the acrylic resin in the total resin component in the varnish is preferably 70% by mass or more, and it is preferable to use the acrylic resin alone as the resin component. . When vegetable oil is used, the amount of the vegetable oil in the varnish is desirably 3 to 60% by mass.
この様にして調整される印刷インキ用ワニスは、ワニスのタック値が５〜２０の範囲であること、ワニス粘度が３０〜１０００Ｐａ・ｓの範囲であることが印刷インキにした際の印刷作業性が良好となる点から好ましい。また、ｎ−ヘプタントレランスが５ｍｌ／ｇ以上であるワニスがインキ調整時に加えられる植物油、溶剤への溶解性の点から好ましい。 The varnish for a printing ink adjusted in this way has a varnish tack value in a range of 5 to 20 and a varnish viscosity in a range of 30 to 1000 Pa · s. Is preferable in that it becomes favorable. Further, a varnish having an n-heptane tolerance of 5 ml / g or more is preferred from the viewpoint of solubility in a vegetable oil and a solvent added during ink preparation.
ここでワニスのタック値の測定は、２５℃に空調された室内において、ＪＩＳＫ５７０１−１（平版インキ試験方法）の４．２粘着性の項に記載のロータリータックメータにより、温度が３２℃、ローラーの回転数が４００ｒｐｍの条件で測定した場合の１分値である。測定サンプル量は１．３１ｍｌである。また、ワニス粘度は、Ｅ型粘度計を用い、被験試料０．２ｍｌ、スピンドルＲ９．７、回転数１〜１０ｒｐｍ、２５℃の条件で測定した値である。ワニスのｎ−ヘプタントレランスは、ワニス１ｇを２５℃に保ちながら、その溶液にｎ−ヘプタンを滴下し、完全に白濁した時のｎ−ヘプタンの添加量（ｍｌ）がｎ−ヘプタントレランスの値である（単位はｍｌ／ｇ）。 Here, the tack value of the varnish was measured using a rotary tack meter described in 4.2 Adhesion section of JIS K5701-1 (lithographic ink test method) at a temperature of 32 ° C. Is a 1-minute value when measured under the condition that the rotation speed is 400 rpm. The measurement sample volume is 1.31 ml. The varnish viscosity is a value measured using an E-type viscometer under the conditions of a test sample of 0.2 ml, a spindle R of 9.7, a rotation speed of 1 to 10 rpm, and 25 ° C. The n-heptane tolerance of the varnish was determined by adding n-heptane to the solution while keeping 1 g of the varnish at 25 ° C., and the amount (ml) of n-heptane added when completely turbid was determined by the value of n-heptane tolerance. Yes (unit is ml / g).
本発明の印刷インキは、上記した印刷インキ用ワニスに顔料を配合し、必要により更に添加剤等を配合して調整することができる。添加剤としては、アルキッド樹脂、前述の本願で必須とするアクリル系樹脂以外のアクリル系樹脂、ギルソナイト、パラフィン、セレシン、ポリエチレン、ポリテトラフルオロエチレン等の樹脂類、アルコール類、脂肪酸エステル類、シリコーン類、界面活性剤が挙げられる。配合比としてインキ全量に対して０．１〜２５質量％が好ましく、経済性、インキとしての品質の全体バランスを考慮すると０．１〜５％質量％とする。但し、樹脂類に関してはバインダーとしての性状を兼ね備えるために１〜１５質量％の範囲とすることもできる。特に顔料分散用にはアルキッド樹脂、長鎖アルキル基を持った（メタ）アクリル樹脂、ギルソナイトが効果的である。 The printing ink of the present invention can be adjusted by blending a pigment with the above-described varnish for printing ink and, if necessary, further blending additives and the like. As additives, alkyd resins, acrylic resins other than the acrylic resins essential in the present application, resins such as Gilsonite, paraffin, ceresin, polyethylene, polytetrafluoroethylene, alcohols, fatty acid esters, silicones And surfactants. The mixing ratio is preferably 0.1 to 25% by mass based on the total amount of the ink, and is 0.1 to 5% by mass in consideration of the economy and the overall balance of the quality as the ink. However, the resin may be in the range of 1 to 15% by mass in order to also have properties as a binder. In particular, alkyd resins, (meth) acrylic resins having long-chain alkyl groups, and Gilsonite are effective for dispersing pigments.
上記の印刷インキ用ワニスを使って作られる印刷インキ組成物中の必須成分の好ましい比率は以下のようになる。ヒートセット輪転インキ、すなわち熱乾燥型オフセット輪転インキの場合、有機又は無機顔料１０〜３０質量％、樹脂２５〜３５質量％、沸点１６０℃以上の炭化水素系溶剤が０〜４５質量％、植物油又は植物油エステル、植物油エーテル７〜４０質量％、乾燥抑制剤、汚れ防止剤、ワックス等の添加剤０〜８質量％となる割合であることが好ましい。 The preferred ratio of the essential components in the printing ink composition prepared using the above-described printing ink varnish is as follows. In the case of a heat-set rotary ink, that is, a hot-drying offset rotary ink, 10 to 30% by mass of an organic or inorganic pigment, 25 to 35% by mass of a resin, 0 to 45% by mass of a hydrocarbon solvent having a boiling point of 160 ° C. or more, vegetable oil or It is preferable that the ratio is 7 to 40% by mass of a vegetable oil ester, a vegetable oil ether, and 0 to 8% by mass of additives such as a drying inhibitor, an antifouling agent, and a wax.
コールドセットインキ、すなわち浸透乾燥型新聞インキの場合、有機又は無機顔料１０〜３０質量％、樹脂１５〜２５質量％、溶剤が１０〜３０質量％、植物油又は植物油エステル２０〜４０質量％、乾燥抑制剤、汚れ防止剤、ワックス等の添加剤１〜５質量％、となる割合であることが好ましい。ここで過乳化を防ぎ、画線と非画線部を分画よく印刷するためには、植物油は４０％を上限とすることが好ましい。 In the case of a cold set ink, that is, a permeation-drying news ink, 10 to 30% by mass of an organic or inorganic pigment, 15 to 25% by mass of a resin, 10 to 30% by mass of a solvent, 20 to 40% by mass of vegetable oil or vegetable oil ester, and drying suppression It is preferable that the amount is 1 to 5% by mass of an additive such as an agent, a stain inhibitor, and a wax. Here, in order to prevent over-emulsification and print the image area and the non-image area with good separation, the upper limit of the vegetable oil is preferably set to 40%.
また、酸化重合型枚葉インキの場合、有機又は無機顔料１０〜３０質量％、樹脂２５〜４０質量％、溶剤が１０〜３０質量％、植物油又は植物油エステル１０〜４０質量％、金属ドライヤー０〜３．０質量％、汚れ防止剤、ワックス等の添加剤０〜１０．０質量％となる割合であることが好ましい。なお、ここで金属ドライヤーは、汎用のマンガン系ドライヤー、コバルト系ドライヤーがいずれも使用できる。 In the case of an oxidation polymerization type sheet-fed ink, 10 to 30% by mass of an organic or inorganic pigment, 25 to 40% by mass of a resin, 10 to 30% by mass of a solvent, 10 to 40% by mass of vegetable oil or vegetable oil ester, and 0 to 0% of a metal dryer. The ratio is preferably 3.0% by mass, and 0 to 10.0% by mass of additives such as an antifouling agent and wax. Here, as the metal dryer, any of a general-purpose manganese-based dryer and a cobalt-based dryer can be used.
本発明で用いることのできる有機顔料としては、種々の着色用有機顔料を挙げることができ、例えば「有機顔料ハンドブック（著者：橋本勲、発行所：カラーオフィス、２００６年初版）」に掲載される印刷インキ用有機顔料等が挙げられ、溶性アゾ顔料、不溶性アゾ顔料、縮合アゾ顔料、金属フタロシアニン顔料、無金属フタロシアニン顔料、キナクリドン顔料、ペリレン顔料、ペリノン顔料、イソインドリノン顔料、イソインドリン顔料、ジオキサジン顔料、チオインジゴ顔料、アンスラキノン系顔料、キノフタロン顔料、金属錯体顔料、ジケトピロロピロール顔料、カーボンブラック顔料、その他多環式顔料等が使用可能である。 Examples of the organic pigment that can be used in the present invention include various organic pigments for coloring, and are described, for example, in “Organic Pigment Handbook (Author: Isao Hashimoto, Publisher: Color Office, First Edition of 2006)”. Organic pigments for printing inks, and the like; soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazines Pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, carbon black pigments, and other polycyclic pigments can be used.
一方、本発明で用いることのできる無機顔料は、無機顔料は、酸化チタン、クラファイト、亜鉛華等の無機着色顔料の他、炭酸石灰粉、沈降性炭酸カルシウム、石膏、クレー（ＣｈｉｎａＣｌａｙ）、シリカ粉、珪藻土、タルク、カオリン、アルミナホワイト、硫酸バリウム、ステアリン酸アルミニウム、炭酸マグネシウム、バライト粉、砥の粉等の無機体質顔料や、シリコーン、ガラスビーズなどがあげられる。 On the other hand, inorganic pigments that can be used in the present invention include inorganic coloring pigments such as titanium oxide, graphite and zinc white, as well as lime powder, precipitated calcium carbonate, gypsum, clay (ChinaClay), and silica. Inorganic pigments such as powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, aluminum stearate, magnesium carbonate, barite powder, abrasive powder, etc., and silicone and glass beads.
このようにして調整された本発明の印刷インキは、オフセットインキ、樹脂凸版インキ、その中でも特に熱乾燥型オフセット輪転インキ、浸透乾燥型新聞インキ、酸化重合型枚葉インキとして好適に用いることができる。また、本発明の印刷インキは、前記したとおり、優れた乳化特性を発現することから、特に、ＰＳ版など水を用いた印刷方式である、オフセット輪転印刷又はオフセット枚葉印刷によって印刷物を得ることが好ましい。 The printing ink of the present invention adjusted in this manner can be suitably used as an offset ink, a resin letterpress ink, and especially a heat-drying offset rotary ink, a permeation-drying newspaper ink, and an oxidation polymerization type sheet ink. . In addition, since the printing ink of the present invention exhibits excellent emulsifying properties as described above, in particular, it is possible to obtain a printed material by offset rotary printing or offset sheet-fed printing, which is a printing method using water such as a PS plate. Is preferred.
以下に参考例、実施例、比較例を挙げて本発明をより具体的に説明するが、本発明はこれ制限されるものではない。なお、例中の部および％は、特に断りのない限り質量基準である。また、各実施例及び比較例にて得られた樹脂及びワニスの各種性状値は以下の方法によって測定した。 Hereinafter, the present invention will be described more specifically with reference to Reference Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. The parts and percentages in the examples are on a mass basis unless otherwise specified. Various property values of the resin and varnish obtained in each of Examples and Comparative Examples were measured by the following methods.
樹脂の粘度：Ｅ型粘度計を用い、被験試料０．２ｍｌ、スピンドルＲ９．７、回転数１〜１０ｒｐｍ、２５℃の条件で測定を行った。 Resin viscosity: Measurement was performed using an E-type viscometer under the conditions of a test sample of 0.2 ml, a spindle R of 9.7, a rotation speed of 1 to 10 rpm, and 25 ° C.
重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）：下記条件のゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定した。 Weight average molecular weight (Mw) and number average molecular weight (Mn): Measured by gel permeation chromatography (GPC) under the following conditions.
測定装置 ；東ソー株式会社製 ＨＬＣ−８２２０ＧＰＣ
カラム ；東ソー株式会社製 ＴＳＫ−ＧＵＡＲＤＣＯＬＵＭＮ ＳｕｐｅｒＨＺ−Ｌ
＋東ソー株式会社製 ＴＳＫ−ＧＥＬ ＳｕｐｅｒＨＺＭ−Ｍ×４
検出器 ；ＲＩ（示差屈折計）
データ処理；東ソー株式会社製 マルチステーションＧＰＣ−８０２０ｍｏｄｅｌＩＩ
測定条件 ；カラム温度 ４０℃
溶媒 テトラヒドロフラン
流速 ０．３５ｍｌ／分
標準 ；単分散ポリスチレン
試料 ；樹脂固形分換算で０．２質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（１００μｌ）
Measurement device: Tosoh Corporation HLC-8220GPC
Column: Tosoh Corporation TSK-GUARDCOLUMN SuperHZ-L
+ TSK-GEL SuperHZM-M x 4 manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent Tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodisperse polystyrene sample: 0.2% by mass of resin in solid tetrahydrofuran solution filtered through a microfilter (100 μl)
タック値：２５℃に空調された室内において、ＪＩＳＫ５７０１−１（平版インキ試験方法）の４．２粘着性の項に記載のロータリータックメータを、温度が３２℃、ローラーの回転数が４００ｒｐｍの条件での１分値である。測定サンプル量は１．３１ｍｌ。 Tack value: In a room air-conditioned to 25 ° C., a rotary tack meter described in 4.2 Adhesion section of JIS K5701-1 (lithographic ink test method) was used at a temperature of 32 ° C. and a roller rotation speed of 400 rpm. Is one minute value. The measurement sample volume was 1.31 ml.
ワニスのｎ−ヘプタントレランスは、ワニス１ｇを２５℃に保ちながら、その溶液にｎ−ヘプタンを滴下し、完全に白濁した時のｎ−ヘプタンの添加量（ｍｌ）がｎ−ヘプタントレランスの値である（単位はｍｌ／ｇ）。 The n-heptane tolerance of the varnish was determined by adding n-heptane to the solution while keeping 1 g of the varnish at 25 ° C., and the amount (ml) of n-heptane added when completely turbid was determined by the value of n-heptane tolerance. Yes (unit is ml / g).
［浸透乾燥型インキの評価］
ラレー粘度：ＪＩＳＫ５７０１−１に記載のＬ型粘度計による方法にて測定した。
流度：２５±０．５℃の恒温環境にて測定。インキ０．５ＣＣをガラス板流度測定器（傾斜９０°）の上端に置き、１０分後、ガラス板上端からインキが流動した距離を測定した。
セット試験：インキ０．０６２５ｍｌをＲＩテスター（株式会社明製作所製)を使用し、４分割ロールで新聞用更紙に展色後、展色紙と上質紙を重ねて自動セット試験機（東洋精機製作所製）により、セット時間（分）即ち、インキが上質紙に付着しなくなる時間を測定した。
リソトロニック乳化性
インキの乳化適性は、Ｎｏｖｏｍａｔｉｃｓ社製のリソトロニック高速乳化試験機を用いて、以下の条件で測定を行った。
コンディショニングタイム（水を加えない予備撹拌時間）・・・３００ｓｅｃ．
撹拌速度・・・１２００ｒｐｍ
インキサンプルの量・・・２５ｇ
温度・・・４０±２℃
水の滴下量・・・２ｍＬ／分、
プロペラ・・・プロペラ角度１０°、厚み１．５ｍｍ
プロペラとカップ底面の距離・・・１ｍｍ
液体温度・・・２２±２℃
水として蒸留水を用いる。水を滴下する際は、水を注入するニードルをカップ壁面に接触させて静かに水がインキに入るようにし、水滴によるトルクカーブのノイズを最小限に抑える。
ＥＣ（ＥｍｕｌｓｉｆｉｃａｔｉｏｎＣａｐａｃｉｔｙ：単位％）を次式で定義する。
ＥＣ（％）＝（水の滴下量）／（サンプル量） ×１００
[Evaluation of penetration drying type ink]
Raleigh viscosity: Measured by a method using an L-type viscometer described in JIS K5701-1.
Flow rate: measured in a constant temperature environment of 25 ± 0.5 ° C. 0.5 CC of the ink was placed on the upper end of a glass plate flowmeter (tilt 90 °), and after 10 minutes, the distance that the ink flowed from the upper end of the glass plate was measured.
Set test: 0.0625 ml of ink was spread on a newspaper newspaper with 4-split rolls using an RI tester (manufactured by Akira Seisakusho Co., Ltd.). ), The time during which the ink did not adhere to the high quality paper was measured.
The emulsification suitability of the lithotronic emulsifying ink was measured under the following conditions using a lysotronic high-speed emulsification tester manufactured by Novomatics.
Conditioning time (preliminary stirring time without adding water) ... 300 sec.
Stirring speed: 1200 rpm
Amount of ink sample: 25 g
Temperature: 40 ± 2 ° C
Water dripping rate: 2 mL / min,
Propeller: Propeller angle 10 °, thickness 1.5mm
Distance between propeller and cup bottom: 1 mm
Liquid temperature: 22 ± 2 ° C
Distilled water is used as water. When the water is dropped, a needle for injecting the water is brought into contact with the cup wall surface so that the water enters the ink gently, and the noise of the torque curve due to the water droplet is minimized.
EC (Emulsification Capacity: unit%) is defined by the following equation.
EC (%) = (dropping amount of water) / (sample amount) × 100
本試験機ではトルク（単位ｍＮ・ｍ）は２回／秒計測される。カップに入れたサンプルのワニスやインキに、撹拌しながら水を滴下していくと、最初トルクが減少し最小トルク値（Ｔｍｉｎ）を示す。その後、水の滴下量の増加とともに、トルク値は増加し、最大トルク値（Ｔｍａｘ）を示す。更に滴下を続けると、サンプルから水が一部分離し、トルクの急激な低下やトルクカーブが不安定になる。トルクが不安定に変動し始めて、トルク値の直近１０回の計測値の標準偏差が１００を超えた時のＥＣの値をＥＣｍａｘと定義する。ＥＣｍａｘが８０％以上である印刷インキは、印刷試験において絡み汚れ、水棒絡みが発生し易い。 In this tester, the torque (unit: mN · m) is measured twice / second. When water is dripped into the varnish or ink of the sample placed in the cup with stirring, the torque decreases at first and shows the minimum torque value (Tmin). Thereafter, the torque value increases with an increase in the amount of water dripping, and indicates a maximum torque value (Tmax). If the dropping is further continued, water is partially separated from the sample, so that the torque sharply decreases and the torque curve becomes unstable. The EC value when the torque starts to fluctuate unstablely and the standard deviation of the ten most recent measured values of the torque value exceeds 100 is defined as ECmax. A printing ink having an ECmax of 80% or more easily causes entanglement dirt and water rod entanglement in a printing test.
［ヒートセット型印刷インキの評価］
光沢：インキ０．１２５ｍｌを、ＲＩテスター（株式会社明製作所製）を用いて２分割ロールでアート紙に展色したのち、雰囲気温度１００℃の乾燥機に１０秒放置し、ヒートセットさせた展色物（インキを紙等の被印刷物に印刷・塗布したもの）を濃度、光沢測定に用いた。そしてヒートセットしてから２４時間後の展色物の光沢値を６０°光沢計にて測定した。
ヒートセット試験：インキ０．１５ｍｌをＲＩテスター（株式会社明製作所製）で２分割ロールを使用してアート紙に展色したのち，雰囲気温度１００℃の乾燥機に５秒間放置した。その後乾燥機から展色紙を取り出してインキ展色面のベタツキの程度を比較した。
評価は、べた付く→ヒートセット性「劣る＝×」、べた付かない→ヒートセット性「優れる＝○」とした。
リソトロニック乳化性：浸透乾燥型インキの評価法と同じ。
[Evaluation of heat-set type printing ink]
Gloss: 0.125 ml of the ink was spread on art paper with a two-part roll using an RI tester (manufactured by Akira Seisakusho Co., Ltd.). A color product (a product obtained by printing and applying ink on a printing material such as paper) was used for measuring the density and gloss. The gloss value of the developed product 24 hours after the heat setting was measured with a 60 ° gloss meter.
Heat set test: 0.15 ml of the ink was spread on art paper using an RI tester (manufactured by Akira Seisakusho Co., Ltd.) using a two-part roll, and then left in a dryer at an ambient temperature of 100 ° C. for 5 seconds. Thereafter, the developed paper was taken out of the dryer, and the degree of stickiness of the ink developed color surface was compared.
The evaluation was as follows: stickiness → heat setting property “poor = ×”, non-stickiness → heat setting property “excellent = ○”.
Lithotronic emulsifiability: Same as the evaluation method for the penetrating dry ink.
[酸価重合型枚葉インキの評価]
タック値：ワニスタック値測定法と同じ
乾燥性：２５℃に空調された室内において、ＪＩＳＫ５７０１−１（平版インキ試験方法）４．４乾燥性に記載の装置を用い、展色用紙：アート紙：当て紙用紙：上質紙にて測定。比較例１３を標準として、乾燥性を比較した。
光沢：インキ０．１２５ｍｌを、ＲＩテスター（株式会社明製作所製）を用いて２分割ロールでアート紙に展色したのち、室温で２４時間静置させた展色物（インキを紙等の被印刷物に印刷・塗布したもの）を光沢測定に用いた。展色物の光沢値を６０°光沢計にて測定した。
リソトロニック乳化性：浸透乾燥型インキの評価法と同じ。
[Evaluation of acid value polymerization type sheet-fed ink]
Tack value: Same as the crocodile stack value measurement method Drying property: In a room air-conditioned at 25 ° C., using an apparatus described in JIS K5701-1 (lithographic ink test method) 4.4 Drying property, color paper: art paper: Backing paper: Measured with high quality paper. The drying property was compared using Comparative Example 13 as a standard.
Gloss: 0.125 ml of ink was spread on art paper with a two-part roll using an RI tester (manufactured by Mei Seisakusho Co., Ltd.), and then allowed to stand at room temperature for 24 hours. (Printed and applied to printed matter) was used for gloss measurement. The gloss value of the developed product was measured with a 60 ° gloss meter.
Lithotronic emulsifiability: Same as the evaluation method for the penetrating dry ink.
実施例１（ジシクロペンタジエン（メタ）アクリレートを用いるアクリル系樹脂を樹脂成分とするワニスの調製）
撹拌装置、温度計、還流管及び滴下ロートを装備した反応容器に、大豆油２００部を仕込み、加熱して１２０℃に保持した。そこへ、ＤＣＰＭＡ１３５部、スチレンモノマー１２０部、メタクリル酸２−ヒドロキシエチル４５部、エチレングリコールジメタクリレート１部、パーブチル−Ｏ ７．５部を混合したものを滴下ロートから同温度を保ちながら３時間かけて滴下した。滴下終了後、同温度を保ち１時間撹拌を続け、追加開始剤としてパーブチル−Ｏ ４部を加え、さらに１時間撹拌を続け、更に同温度を保ち１時間撹拌を続け、パーブチル−Ｏ ４部を加え、さらに１時間撹拌を続けた。重合終了後、得られた溶液の粘度は２００Ｐａ・ｓｅｃ、樹脂の重量平均分子量２４，０００、数平均分子量１２，０００、水酸基価８０ｍｇＫＯＨ／ｇ、酸価７ｍｇＫＯＨ／ｇであった。
Example 1 (Preparation of varnish containing acrylic resin using dicyclopentadiene (meth) acrylate as resin component)
200 parts of soybean oil was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux tube, and a dropping funnel, and heated to 120 ° C. A mixture of 135 parts of DCPMA, 120 parts of styrene monomer, 45 parts of 2-hydroxyethyl methacrylate, 1 part of ethylene glycol dimethacrylate, and 7.5 parts of perbutyl-O was added thereto over 3 hours while maintaining the same temperature from the dropping funnel. And dropped. After completion of the dropwise addition, stirring was continued for 1 hour while maintaining the same temperature, 4 parts of perbutyl-O was added as an additional initiator, stirring was further continued for 1 hour, stirring was continued for 1 hour while maintaining the same temperature, and 4 parts of perbutyl-O was added. In addition, stirring was continued for another hour. After the polymerization was completed, the viscosity of the obtained solution was 200 Pa · sec, the weight average molecular weight of the resin was 24,000, the number average molecular weight was 12,000, the hydroxyl value was 80 mgKOH / g, and the acid value was 7 mgKOH / g.
実施例２〜５
表１に示す種類と量の溶媒、モノマー及び重合開始剤を用い、実施例１と同様にして樹脂溶液を製造した。
Examples 2 to 5
A resin solution was produced in the same manner as in Example 1 using the types and amounts of solvent, monomer and polymerization initiator shown in Table 1.
比較例１〜２（ジシクロペンタジエン（メタ）アクリレートを用いないアクリル系樹脂を樹脂成分とするワニスの調製）
表２に示す種類と量の溶媒、モノマー及び重合開始剤を用い、実施例１と同様にして樹脂溶液を製造した。なお、ＩＢＸＭＡはメタクリル酸イソボルニルを示す。
Comparative Examples 1 and 2 (Preparation of a varnish containing an acrylic resin without using dicyclopentadiene (meth) acrylate as a resin component)
A resin solution was produced in the same manner as in Example 1 using the types and amounts of solvent, monomer and polymerization initiator shown in Table 2. In addition, IBXMA shows isobornyl methacrylate.
比較例３
撹拌器および温度計を備えた加圧反応釜に、ｐ−ｔｅｒｔ−ブチルフェノール１５０部を仕込み、１２０℃で加熱溶解し、９２％パラホルムアルデヒド粉末（水分含有率８％）６５部と水酸化カルシウム０．９部を加えて１３０℃まで加熱し、２時間反応させてレゾール型フェノール樹脂を調製した。得られたレゾール樹脂は、ＧＰＣ法で測定したポリスチレン換算の重量平均分子量（Ｍｗ）が９２０であった。このレゾール樹脂４０部にＪＸ日鉱日石エネルギー製ＡＦソルベント７号１０部を加えて１１０℃で１時間攪拌し、樹脂分濃度８０％のレゾール型フェノール樹脂溶液を調製した。以下、得られたレゾール型フェノール樹脂溶液を「レゾール樹脂溶液（１）」と略記する。
Comparative Example 3
In a pressurized reaction vessel equipped with a stirrer and a thermometer, 150 parts of p-tert-butylphenol were charged and dissolved by heating at 120 ° C., and 65 parts of 92% paraformaldehyde powder (water content 8%) and 0 parts of calcium hydroxide were added. After adding 9 parts, the mixture was heated to 130 ° C. and reacted for 2 hours to prepare a resol type phenol resin. The obtained resol resin had a weight average molecular weight (Mw) in terms of polystyrene of 920 as measured by the GPC method. To 40 parts of this resole resin was added 10 parts of AF Solvent No. 7 manufactured by JX Nippon Oil & Energy, and the mixture was stirred at 110 ° C. for 1 hour to prepare a resol type phenol resin solution having a resin concentration of 80%. Hereinafter, the obtained resol-type phenol resin solution is abbreviated as “resole resin solution (1)”.
撹拌器、温度計、縮合水分離器および窒素導入管を備えた反応釜に、酸価１６５ｍｇＫＯＨ／ｇのガムロジン１００部、無水マレイン酸４部を仕込み、昇温して温度が２００℃に到達した時点でペンタエリスリトール８部、グリセリン５部と蟻酸カルシウムの０．９部を加え、さらに２７０℃に昇温した。その後２７０℃で酸価が１７ｍｇＫＯＨ／ｇ以下になった時点で温度を下げてロジンエステル樹脂を得た。以下、得られたロジンエステル樹脂を「ＲＥ樹脂（１）」と略記する。 A reaction vessel equipped with a stirrer, a thermometer, a condensation water separator, and a nitrogen inlet tube was charged with 100 parts of gum rosin having an acid value of 165 mgKOH / g and 4 parts of maleic anhydride, and the temperature was raised to 200 ° C. At this time, 8 parts of pentaerythritol, 5 parts of glycerin and 0.9 part of calcium formate were added, and the temperature was further raised to 270 ° C. Thereafter, when the acid value at 270 ° C. became 17 mgKOH / g or less, the temperature was lowered to obtain a rosin ester resin. Hereinafter, the obtained rosin ester resin is abbreviated as “RE resin (1)”.
このＲＥ樹脂（１）１００部にＡＦソルベント７号２５部を加えて混合し１７０℃に保持した混合物を仕込み、さらに１１０℃に加温したレゾール樹脂溶液（１）３０部を加えながら、２２０℃へ昇温し１時間反応させた時点で反応を終了させて、樹脂分濃度８０質量％の印刷インキワニス用樹脂溶液（１）〔以下、「樹脂溶液（１）」と略記する。〕を得た。得られた樹脂溶液は、この樹脂溶液に同量のトルエンを加えた場合の２５℃におけるガードナー粘度がＫ〔樹脂分の重量平均分子量（Ｍｗ）は１１万であった。〕であった。 25 parts of AF Solvent No. 7 was added to 100 parts of this RE resin (1) and mixed, and a mixture kept at 170 ° C. was charged. Further, while adding 30 parts of a resole resin solution (1) heated to 110 ° C., 220 ° C. The reaction was terminated when the temperature was raised to 1 hour, and the reaction was terminated. A resin solution (1) for a printing ink varnish having a resin concentration of 80% by mass [hereinafter abbreviated as “resin solution (1)”. ] Was obtained. The resulting resin solution had a Gardner viscosity at 25 ° C. K (the weight average molecular weight (Mw) of the resin component was 110,000) when the same amount of toluene was added to the resin solution. 〕Met.
比較例４（浸透乾燥型新聞インキ用のワニスの調整）
２００℃の樹脂溶液（１）１００部に大豆油３０部を加え、温度を１８０℃に調整して６０分間加熱混合し、次いでＡＦソルベント６号５０部およびＢＨＴ０．２部を加えた。１５０℃でエチルアセトアセテートアルミニウムジノルマルブチレート０．１部を加えて１時間加熱攪拌して、印刷インキ用ワニスを得た。以下、得られたワニスを「ロジン変性フェノール樹脂ワニス（１）」と略記する。このワニス（１）は、タック値１４、Ｅ型粘度は３７０Ｐａ・ｓ、ｎＨ−トレランスは１５ｍｌ／ｇであった。
Comparative Example 4 (Preparation of varnish for permeation drying type news ink)
30 parts of soybean oil was added to 100 parts of the resin solution (1) at 200 ° C., the temperature was adjusted to 180 ° C., and the mixture was heated and mixed for 60 minutes. Then, 50 parts of AF Solvent No. 6 and 0.2 parts of BHT were added. At 150 ° C., 0.1 part of ethyl acetoacetate aluminum dinormal butyrate was added, and the mixture was heated and stirred for 1 hour to obtain a varnish for printing ink. Hereinafter, the obtained varnish is abbreviated as “rosin-modified phenol resin varnish (1)”. This varnish (1) had a tack value of 14, an E-type viscosity of 370 Pa · s, and an nH-tolerance of 15 ml / g.
比較例５（ヒートセット型オフセットインキ用ワニスの調製）
２００℃の樹脂溶液（１）１００部に大豆油３３部を加え、温度を２００℃に調整して６０分間加熱混合し、次いでＡＦソルベント７号５５部およびＢＨＴ０．２部を加えた。１５０℃でエチルアセトアセテートアルミニウムジノルマルブチレート０．２部を加えて１時間加熱攪拌して、印刷インキ用ワニスを得た。以下、得られたワニスを「ロジン変性フェノール樹脂ワニス（２）」と略記する。 このワニス（２）は、タック値１０、Ｅ型粘度は２７０Ｐａ・ｓ、ｎＨ−トレランスは１４ｍｌ／ｇであった。
Comparative Example 5 (Preparation of varnish for heat-set type offset ink)
33 parts of soybean oil was added to 100 parts of the resin solution (1) at 200 ° C., the temperature was adjusted to 200 ° C., and the mixture was heated and mixed for 60 minutes. Then, 55 parts of AF Solvent 7 and 0.2 parts of BHT were added. At 150 ° C., 0.2 parts of ethyl acetoacetate aluminum dinormal butyrate was added, and the mixture was heated and stirred for 1 hour to obtain a varnish for printing ink. Hereinafter, the obtained varnish is abbreviated as “rosin-modified phenolic resin varnish (2)”. This varnish (2) had a tack value of 10, an E-type viscosity of 270 Pa · s, and an nH-tolerance of 14 ml / g.
比較例６（ヒートセット型オフセットインキ用ワニスの調製）
ロジン変性フェノール樹脂（「ＢＥＣＫＡＣＩＴＥ１１２６ＨＶ」ＤＩＣ株式会社製）４８部に対して、大豆油２０部、ＡＦソルベント７号（新日本石油（株）社製）１５部を添加して、２２０℃で１時間保持した。その後、ＡＦソルベント７号１５．７部、エチルアセトアセテートアルミニウムジノルマルブチレート１部を添加して、１６０℃で１時間保持し、さらに、酸価２．３、固形分水酸基価１１．０、イソフタル酸を酸成分として含有する油長７８のアルキッド樹脂を１２部加え、最後にＢＨＴ（２，６−ジ−tert−ブチル−４−メチルフェノール）０．３部を加え、アルキッド樹脂添加ロジン変性フェノール樹脂ワニスを調製した（樹脂成分中に占めるアルキッド樹脂の割合：２０質量％）。以下、得られたワニスを「ロジン変性フェノール樹脂ワニス（３）」と略記する。
Comparative Example 6 (Preparation of varnish for heat-set type offset ink)
20 parts of soybean oil and 15 parts of AF Solvent 7 (manufactured by Nippon Oil Co., Ltd.) were added to 48 parts of a rosin-modified phenol resin (“BECKACITE 1126HV” manufactured by DIC Corporation), and the mixture was heated at 220 ° C. for 1 hour. Held. Thereafter, 15.7 parts of AF Solvent No. 7 and 1 part of ethyl acetoacetate aluminum dinormal butyrate were added, and the mixture was kept at 160 ° C. for 1 hour. Further, the acid value was 2.3, the hydroxyl value of the solid content was 11.0, 12 parts of an alkyd resin having an oil length of 78 containing isophthalic acid as an acid component were added, and finally 0.3 parts of BHT (2,6-di-tert-butyl-4-methylphenol) was added. A phenolic resin varnish was prepared (ratio of alkyd resin in resin component: 20% by mass). Hereinafter, the obtained varnish is abbreviated as “rosin-modified phenolic resin varnish (3)”.
実施例６、７、８及び比較例７、８［浸透乾燥型新聞インキの調製例及び評価］を表３にまとめて示す Table 3 shows Examples 6, 7, and 8 and Comparative Examples 7 and 8 [Examples of preparation and evaluation of permeation-drying news ink].
具体的には、表３の配合割合で、３本ロールミルを用いて練肉し、グラインドメーター値で７．５μｍ以下になるように調整した。２５℃におけるインキのラレー粘度値が７．５〜８．５（Ｐａ．ｓ）になるようにＪＸ日鉱日石エネルギー製ＡＦソルベント６号を用いて調整した。尚、カーボンブラックは三菱化学株式会社製カラー用カーボンブラック＃９５である。炭酸カルシウムは白石工業（株）製の白艶華Ｏを使用した。 Specifically, the mixture was kneaded with a three-roll mill at the mixing ratio shown in Table 3 and adjusted to a grindometer value of 7.5 μm or less. It was adjusted using AF Solvent No. 6 manufactured by JX Nippon Oil & Energy Co., Ltd. so that the Raleigh viscosity value of the ink at 25 ° C. became 7.5 to 8.5 (Pa.s). The carbon black is color carbon black # 95 manufactured by Mitsubishi Chemical Corporation. As the calcium carbonate, Shiraishi O, manufactured by Shiraishi Industry Co., Ltd., was used.
実施例９、１０、１１及び比較例９、１０，１１［ヒートセット型印刷インキの調整及び評価］を表４にまとめて示す。 Table 4 collectively shows Examples 9, 10, and 11 and Comparative Examples 9, 10, and 11 [Adjustment and Evaluation of Heat Set Printing Inks].
具体的には、表４の配合割合で、ＡＦソルベント７号５部を三本ロールミルで混合練肉し、ＪＩＳＫ５７０１−１に記載の練和度試験にて練和度が２．５μｍ以下になっている事を確認した。そして、２５℃におけるインキのラレー粘度値が１８〜２０（Ｐａ．ｓ）になるようにＡＦソルベント７号、ワニスを追加し合計１００部になるように調整した。炭酸カルシウムは白石工業（株）製の白艶華Ｏを使用した。アルキド樹脂ワニスは、ＤＩＣ（株）製のベッコゾールＥＬ−８００１を使用した。 Specifically, 5 parts of AF Solvent No. 7 were mixed and kneaded with a three-roll mill at the compounding ratio shown in Table 4, and the kneading degree became 2.5 μm or less in a kneading degree test described in JIS K5701-1. I confirmed that. Then, AF Solvent No. 7 and a varnish were added so that the Ralay viscosity value of the ink at 25 ° C. became 18 to 20 (Pa.s), and the total was adjusted to 100 parts. As the calcium carbonate, Shiraishi O, manufactured by Shiraishi Industry Co., Ltd., was used. The alkyd resin varnish used was Veccosol EL-8001 manufactured by DIC Corporation.
実施例１２、１３及び比較例１２，１３［酸価重合型枚葉インキの調製例及び評価］を表５にまとめて示す Tables 5 and 6 summarize Examples 12 and 13 and Comparative Examples 12 and 13 [Preparation Examples and Evaluations of Acid Value Polymerization Type Sheet-fed Ink].
具体的には、表５の配合割合で、３本ロールミルを用いて練肉し、グラインドメーター値で７．５μｍ以下になるように調整した。２５℃におけるインキのタックが１０〜１１になるようにＪＸ日鉱日石エネルギー製ＡＦソルベント６号を用いて調整した。アルキド樹脂ワニスは、ＤＩＣ（株）製のベッコゾールＥＬ−８００１を使用した。 Specifically, the mixture was kneaded with a three-roll mill at the mixing ratio shown in Table 5 and adjusted to a grindometer value of 7.5 μm or less. It was adjusted using AF Solvent No. 6 manufactured by JX Nippon Oil & Energy Co., Ltd. so that the tackiness of the ink at 25 ° C. was 10 to 11. The alkyd resin varnish used was Veccosol EL-8001 manufactured by DIC Corporation.
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