JP5708946B2 - Printing ink binder, printing ink varnish and printing ink - Google Patents
Printing ink binder, printing ink varnish and printing ink Download PDFInfo
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- JP5708946B2 JP5708946B2 JP2013034795A JP2013034795A JP5708946B2 JP 5708946 B2 JP5708946 B2 JP 5708946B2 JP 2013034795 A JP2013034795 A JP 2013034795A JP 2013034795 A JP2013034795 A JP 2013034795A JP 5708946 B2 JP5708946 B2 JP 5708946B2
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- parts
- rosin
- printing ink
- component
- varnish
- Prior art date
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- 238000007639 printing Methods 0.000 title claims description 45
- 239000002966 varnish Substances 0.000 title claims description 20
- 239000011230 binding agent Substances 0.000 title claims description 16
- 239000000976 ink Substances 0.000 claims description 65
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 41
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 32
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 32
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 32
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 18
- 239000005011 phenolic resin Substances 0.000 claims description 16
- 150000002989 phenols Chemical class 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 8
- 239000008158 vegetable oil Substances 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 7
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 26
- 238000003756 stirring Methods 0.000 description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 22
- 239000000944 linseed oil Substances 0.000 description 16
- 235000021388 linseed oil Nutrition 0.000 description 16
- 238000001816 cooling Methods 0.000 description 12
- 239000000049 pigment Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 235000011187 glycerol Nutrition 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- -1 phosphorus compound Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000003549 soybean oil Substances 0.000 description 5
- 235000012424 soybean oil Nutrition 0.000 description 5
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000007645 offset printing Methods 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 229920003987 resole Polymers 0.000 description 4
- 239000003784 tall oil Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229940097275 indigo Drugs 0.000 description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 150000004072 triols Chemical class 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical compound CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FBXFSONDSA-N Allitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-FBXFSONDSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 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
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- VAROLYSFQDGFMV-UHFFFAOYSA-K di(octanoyloxy)alumanyl octanoate Chemical compound [Al+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O VAROLYSFQDGFMV-UHFFFAOYSA-K 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007644 letterpress printing Methods 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
本発明は、ロジン変性フェノール樹脂を用いた印刷インキ用バインダー、当該印刷インキ用バインダーを含有する印刷インキ用樹脂ワニス、および該ワニスを用いて得られる印刷インキに関する。 The present invention relates to a printing ink binder using a rosin-modified phenolic resin, a printing ink resin varnish containing the printing ink binder, and a printing ink obtained using the varnish.
ロジン変性フェノール樹脂とは一般的に、ロジン類、フェノール樹脂、ポリオール類を反応させることにより得られる樹脂であり、古くより印刷インキ用樹脂、例えばオフセット印刷インキ用樹脂として賞用されている（特許文献１、２等参照）。 A rosin-modified phenolic resin is generally a resin obtained by reacting rosins, phenolic resins, and polyols, and has long been used as a printing ink resin, for example, an offset printing ink resin (patents). References 1, 2 etc.).
オフセット印刷インキは通常、かかるロジン変性フェノール樹脂をインキ用溶剤に溶解させて得られるワニスに顔料を配合し、混合することにより得られるが、顔料が十分に分散しないと印刷インキの流動性が不良となったり、印刷物の光沢が低下したりする。そこで、顔料を十分に分散させるために機械的な分散工程を長時間行うことが考えられるが、生産性の低下を招く。 Offset printing ink is usually obtained by blending and mixing a pigment in a varnish obtained by dissolving such rosin-modified phenolic resin in an ink solvent. However, if the pigment is not sufficiently dispersed, the flowability of the printing ink is poor. Or the gloss of the printed material decreases. Therefore, it is conceivable to perform a mechanical dispersion process for a long time in order to sufficiently disperse the pigment, but this leads to a decrease in productivity.
また、インキメーカーにおいては、分散工程においてロジン変性フェノール樹脂の分散作用を補う目的で種々の添加剤が検討されており、例えば特許文献３には、所定の不溶性アゾ顔料組成物等を一定量用いることによりインキの顔料分散性が改善されることが示されている。 In addition, in the ink manufacturer, various additives have been studied for the purpose of supplementing the dispersing action of the rosin-modified phenol resin in the dispersing step. For example, Patent Document 3 uses a predetermined amount of a predetermined insoluble azo pigment composition or the like. This has been shown to improve the pigment dispersibility of the ink.
一方、ロジン変性フェノール樹脂の物性面より顔料分散性を向上させる試みもなされており、例えば本出願人は、特許文献４で示すように、ロジン変性フェノール樹脂に含まれる重量平均分子量が４００以下の低分子成分の量を限定することにより、印刷インキの流動性を改善できることを見出した。しかし、更なる改善が求められている。 On the other hand, attempts have been made to improve pigment dispersibility in terms of physical properties of rosin-modified phenolic resins. For example, as shown in Patent Document 4, the present applicant has a weight average molecular weight of 400 or less contained in rosin-modified phenolic resins. It has been found that the fluidity of the printing ink can be improved by limiting the amount of the low molecular component. However, further improvements are required.
本発明は、顔料分散性が良好であり、印刷インキの流動性を向上させることができ、かつ印刷物に優れた光沢を付与できる、新規なロジン変性フェノール樹脂系の印刷インキ用バインダーを提供することを主たる目的とする。 The present invention provides a novel rosin-modified phenolic resin-based binder for printing ink that has good pigment dispersibility, can improve the fluidity of printing ink, and can impart excellent gloss to printed matter. Is the main purpose.
本発明者は、従来のロジン変性フェノール樹脂は分子量分布に大きな幅があり、このことが原因でバインダー性能が不足するケースがあると考え、その分子量分布幅を規定するべく、所定のリン系化合物を一定量用いることにより、目的とするロジン変性フェノール樹脂が得られることを見出した。 The present inventor believes that the conventional rosin-modified phenolic resin has a large range in molecular weight distribution, which may cause insufficient binder performance, and in order to define the molecular weight distribution range, a predetermined phosphorus compound It was found that the desired rosin-modified phenolic resin can be obtained by using a certain amount of.
すなわち、本発明は、トリフェニルホスファイト（Ａ）の存在下でロジン類（ｂ−１）とポリオール（ｂ−２）を、（ｂ−１）成分に対する（Ａ）成分の使用量が０．０５〜０．５重量％となる条件でエステル化させることにより得られるロジンエステル類（Ｂ）と、フェノール類とホルムアルデヒドの縮合物（Ｃ）とを反応させることにより得られる、重量平均分子量（Ｍｗ）が３０，０００〜３９，０００であり、数平均分子量（Ｍｎ）が３，０００〜４，９４０であり、かつ多分散度（Ｍｗ／Ｍｎ）が８〜９のロジン変性フェノール樹脂を用いてなる印刷インキ用バインダー；該印刷インキ用バインダーと植物油を含有する印刷インキ用ワニス；当該印刷インキ用ワニスを用いて得られる印刷インキに関する。 That is, in the present invention, rosins (b-1) and polyol (b-2) are used in the presence of triphenyl phosphite (A), and the amount of component (A) used relative to component (b-1) is 0. Weight average molecular weight (Mw) obtained by reacting rosin esters (B) obtained by esterification under the conditions of 0.5 to 0.5% by weight and a condensate (C) of phenols and formaldehyde. ) is 3 0,000～ 39,000, with number average molecular weight (Mn) is 3,000～4,940, and a polydispersity (Mw / Mn) is 8-9 rosin-modified phenolic resin The present invention relates to a printing ink binder comprising: a printing ink varnish containing the printing ink binder and vegetable oil; and a printing ink obtained using the printing ink varnish.
本発明の印刷インキ用バインダーは、これをなすロジン変性フェノール樹脂が顔料分散性に優れているため、印刷インキの流動性が良好になる他、印刷物の光沢も良好になる。それゆえ当該バインダーは、特にオフセット印刷インキ用樹脂、例えばオフセット枚葉インキ（枚葉インキ）やオフセット輪転インキ（オフ輪インキ）、新聞インキ用等のオフセット印刷インキ用樹脂等として有用である。また、凸版印刷インキ用、グラビア印刷インキ用樹脂としても使用できる。また、顔料の表面処理剤としても利用可能である。 In the printing ink binder of the present invention, the rosin-modified phenolic resin forming the binder is excellent in pigment dispersibility, so that the flowability of the printing ink is improved and the gloss of the printed matter is also improved. Therefore, the binder is particularly useful as a resin for offset printing ink, for example, a resin for offset printing ink such as offset sheet-fed ink (sheet-fed ink), offset rotary ink (off-wheel ink), and newspaper ink. It can also be used as a resin for letterpress printing inks and gravure printing inks. It can also be used as a pigment surface treatment agent.
本発明の印刷インキ用バインダーは、トリフェニルホスファイト（Ａ）（以下、（Ａ）成分という）の存在下でロジン類（ｂ−１）（以下、（ｂ−１）成分という）とポリオール（ｂ−２）（以下、（ｂ−２）成分という）をエステル化して得られるロジンエステル類（Ｂ）（以下、（Ｂ）成分という）と、フェノール類とホルムアルデヒドの縮合物（Ｃ）（以下、（Ｃ）成分という）とを反応させることにより得られるロジン変性フェノール樹脂を用いたものである。 The printing ink binder of the present invention comprises a rosin (b-1) (hereinafter referred to as component (b-1)) and a polyol (hereinafter referred to as component (b-1)) in the presence of triphenyl phosphite (A) (hereinafter referred to as component (A)). b-2) rosin esters (B) (hereinafter referred to as (B) component) obtained by esterification of (hereinafter referred to as (b-2) component), phenols and formaldehyde condensate (C) (hereinafter referred to as component (B-2)) , (C) component) and a rosin-modified phenolic resin obtained by reacting.
（Ａ）成分は、入手が容易であり、かつ本発明の所期の効果（顔料分散性、印刷インキ流動性、印刷インキ皮膜の光沢等をいう。以下、本発明の効果というときは、同様である。）を達成しやすいため好ましい。 Component (A), available at ease, and desired effect (pigment dispersion of the present invention, printing ink fluidity refers to the gloss or the like of the printing ink film. Hereinafter, the term effects of the present invention likewise It is preferable because it is easy to achieve.
（ｂ−１）成分としては、例えば、ガムロジン、トール油ロジン、ウッドロジンなどの天然ロジンやその精製物（以下、原料ロジン類という）；原料ロジン類から誘導される重合ロジン；原料ロジン類や重合ロジンを不均化および／または水素添加して得られる安定化ロジン；原料ロジン類や重合ロジンに、（メタ）アクリル酸、フマル酸、（無水）イタコン酸、クロトン酸、ケイ皮酸等のα，β不飽和カルボン酸類をディールス・アルダー付加反応させて得られるα，β不飽和酸変性ロジン；当該α，β不飽和酸変性ロジンを更に不均化または水素添加して得られる安定化ロジン等が挙げられ、これらは１種を単独で、または２種以上を組み合わせて使用できる。なお、α，β不飽和酸変性ロジンにおけるロジン種とα，β不飽和カルボン酸の使用量は特に限定されないが、本発明の効果の点より、通常は前者１００重量部に対して後者が１〜３０重量部程度となる範囲である。 Examples of the component (b-1) include natural rosins such as gum rosin, tall oil rosin, and wood rosin and purified products thereof (hereinafter referred to as raw rosins); polymerization rosins derived from raw rosins; raw rosins and polymerization Stabilized rosin obtained by disproportionating and / or hydrogenating rosin; raw material rosins and polymerized rosin, α of (meth) acrylic acid, fumaric acid, (anhydrous) itaconic acid, crotonic acid, cinnamic acid, etc. , Β-unsaturated acid-modified rosin obtained by Diels-Alder addition reaction of β-unsaturated carboxylic acids; stabilized rosin obtained by further disproportionation or hydrogenation of the α, β-unsaturated acid-modified rosin, etc. These can be used singly or in combination of two or more. The amount of the rosin species and the α, β unsaturated carboxylic acid used in the α, β unsaturated acid-modified rosin is not particularly limited. However, from the viewpoint of the effect of the present invention, the latter is usually 1 for 100 parts by weight of the former. It is the range which becomes about 30 weight part.
（ｂ−２）成分としては、１分子中に少なくとも２つのヒドロキシル基を有する化合物であれば特に限定されず、各種公知のものを使用することができる。具体的には、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ネオペンチルグリコール等のジオール類、グリセリン、トリメチロールエタン、トリメチロールプロパン等のトリオール類、ペンタエリスリトール、ジグリセリン、ジトリメチロールプロパン等のテトラオール類、ジペンタエリスリトール等の６価以上のポリオール類等が挙げられ、これらは１種を単独で、または２種以上を組み合わせて使用できる。これらのうちトリオール類および／またはテトラオール類は、本発明であるロジン変性フェノール樹脂の物性（軟化点、重量平均分子量等）の制御の容易さの観点、および本発明の効果の点より野好ましい。 The component (b-2) is not particularly limited as long as it is a compound having at least two hydroxyl groups in one molecule, and various known compounds can be used. Specifically, for example, diols such as ethylene glycol, diethylene glycol, triethylene glycol, and neopentyl glycol, triols such as glycerin, trimethylolethane, and trimethylolpropane, and tetraols such as pentaerythritol, diglycerin, and ditrimethylolpropane. Examples include polyols having a valence of 6 or more such as all and dipentaerythritol, and these can be used alone or in combination of two or more. Of these, triols and / or tetraols are preferable from the viewpoint of easy control of physical properties (softening point, weight average molecular weight, etc.) of the rosin-modified phenolic resin of the present invention, and the effects of the present invention. .
本発明においては、（Ａ）成分を、（ｂ−１）成分に対して０．０５〜０．５重量％となる条件で使用する必要がある。０．０５重量％以上とすることにより、特に印刷インキの流動性とインキ皮膜の光沢を良好にできる。また、０．５重量％以下とすることにより、本発明のロジン変性フェノール樹脂の製造の際の不溶物を低減でき、かつ、本発明の効果のうち、特に印刷インキの流動性とインキ皮膜の光沢を良好にできる。かかる観点より、（Ａ）成分の使用量は、（ｂ−１）成分に対して好ましくは０．１〜０．４重量％程度、更に好ましくは０．１５〜０．３５重量％程度であるのがよい。 In this invention, it is necessary to use (A) component on the conditions used as 0.05 to 0.5 weight% with respect to (b-1) component. By setting it as 0.05 weight% or more, especially the fluidity | liquidity of printing ink and the glossiness of an ink film can be made favorable. In addition, by adjusting the content to 0.5% by weight or less, insoluble matters in the production of the rosin-modified phenolic resin of the present invention can be reduced, and among the effects of the present invention, particularly the fluidity of the printing ink and the ink film The gloss can be improved. From this viewpoint, the amount of component (A) used is preferably about 0.1 to 0.4% by weight, more preferably about 0.15 to 0.35% by weight, based on component (b-1). It is good.
（ｂ−１）成分と（ｂ−２）成分の使用量も特に限定されないが、本発明の効果の観点より、（ｂ−２）成分の全ヒドロキシル基当量数（ＯＨ）と（ｂ−１）成分の全カルボキシル基当量数（ＣＯＯＨ）との比（ＯＨ／ＣＯＯＨ）が通常０．５〜１．５程度となる範囲であるのがよい。 Although the usage-amount of (b-1) component and (b-2) component is not specifically limited, From the viewpoint of the effect of this invention, the total hydroxyl group equivalent number (OH) of (b-2) component and (b-1) The ratio (OH / COOH) to the total number of carboxyl group equivalents (COOH) of the component is usually in the range of about 0.5 to 1.5.
（Ｂ）成分は、前記したように、所定量の（Ａ）成分の存在下、（ｂ−１）成分と（ｂ−２）成分をエステル化反応させることによって得られる。反応条件は特に限定されないが、例えば、（Ａ）成分、（ｂ−１）成分および（ｂ−２）成分を所定量ずつ反応容器に仕込み、必要に応じて各種公知の触媒の存在下、１００〜３００℃程度で１〜２４時間程度エステル化反応を進行させればよい。 As described above, the component (B) is obtained by subjecting the component (b-1) and the component (b-2) to an esterification reaction in the presence of a predetermined amount of the component (A). Although reaction conditions are not specifically limited, For example, (A) component, (b-1) component, and (b-2) component are charged to reaction container for every predetermined amount, and in the presence of various well-known catalysts as needed, 100 What is necessary is just to advance esterification reaction at about -300 degreeC for about 1 to 24 hours.
触媒としては、例えば、塩酸、硫酸等の鉱酸類；メタンスルホン酸、パラトルエンスルホン酸、ドデシルベンゼンスルホン酸等のスルホン酸類；酸化亜鉛、酸化マグネシウム、酸化カルシウム等の金属酸化物；水酸化マグネシウム、水酸化カルシウム等の金属の水酸化物；酢酸カルシウム、酢酸マグネシウム、酢酸亜鉛等の酢酸塩が挙げられ、これらは１種を単独で、または２種以上を組み合わせて使用できる。また、その使用量は特に限定されないが、後述の多分散度を達成する目的において、通常は（ｂ−１）成分および（ｂ−２）成分の合計量に対して通常０〜５重量％程度であるのが望ましい。 Examples of the catalyst include mineral acids such as hydrochloric acid and sulfuric acid; sulfonic acids such as methanesulfonic acid, paratoluenesulfonic acid and dodecylbenzenesulfonic acid; metal oxides such as zinc oxide, magnesium oxide and calcium oxide; magnesium hydroxide, Examples thereof include metal hydroxides such as calcium hydroxide; and acetates such as calcium acetate, magnesium acetate, and zinc acetate. These can be used alone or in combination of two or more. The amount used is not particularly limited, but for the purpose of achieving the polydispersity described later, it is usually about 0 to 5% by weight with respect to the total amount of the components (b-1) and (b-2). It is desirable that
（Ｃ）成分としては、フェノール類とホルムアルデヒドの縮合物であれば各種公知のもの、例えばレゾール型フェノール樹脂やノボラック型フェノール樹脂等を使用できる。 As the component (C), various known products such as a resol type phenol resin and a novolak type phenol resin can be used as long as they are condensates of phenols and formaldehyde.
フェノール類としては、石炭酸、クレゾール、アミルフェノール、ビスフェノールＡ、ブチルフェノール、オクチルフェノール、ノニルフェノール、ドデシルフェノール等が挙げられる。またホルムアルデヒドとしては、ホルマリン、パラホルムアルデヒド等が挙げられる。 Examples of phenols include carboxylic acid, cresol, amylphenol, bisphenol A, butylphenol, octylphenol, nonylphenol, and dodecylphenol. Examples of formaldehyde include formalin and paraformaldehyde.
また、前記レゾール型フェノール樹脂としては、各種塩基性触媒の存在下において、フェノール類（Ｐ）とホルムアルデヒド（Ｆ）とをＦ／Ｐ（モル比）が通常１〜３程度となる範囲内で付加・縮合反応させた縮合物が挙げられる。また、前記ノボラック型フェノール樹脂としては、各種酸触媒の存在下において、Ｆ／Ｐが通常０．５〜２程度となる範囲内で、付加・縮合反応させた縮合物が挙げられる。また、各縮合物は中和・水洗したものであってよい。また、各縮合物の製造は、水や有機溶剤（キシレン等）の存在下で実施できる。（Ｃ）成分としては、ロジン変性フェノール樹脂の高分子量化の観点、および本発明の効果（の観点より、前記レゾール型フェノール樹脂が好ましい。また、酸触媒と塩基性触媒としては、（Ｂ）成分を製造する際に用いたものと同様のものを使用できる。 In addition, as the resol type phenolic resin, phenols (P) and formaldehyde (F) are added in the range where F / P (molar ratio) is usually about 1 to 3 in the presence of various basic catalysts. -Condensates obtained by condensation reaction are mentioned. Examples of the novolak type phenol resin include condensates obtained by addition / condensation reaction in the presence of various acid catalysts within a range where F / P is usually about 0.5 to 2. Each condensate may be neutralized and washed with water. Each condensate can be produced in the presence of water or an organic solvent (such as xylene). As the component (C), from the viewpoint of increasing the molecular weight of the rosin-modified phenol resin and the effect of the present invention (from the viewpoint of the above), the resol-type phenol resin is preferable. The thing similar to what was used when manufacturing a component can be used.
（Ｂ）成分と（Ｃ）成分の使用量は特に限定されず、用途に応じてそれぞれ適宜決定すればよいが、本発明の効果の観点より、通常は、両者の合計を１００重量％とした場合において、順に４１〜８８重量％程度および５９〜１２重量％程度であり、好ましくは４６〜８０重量％程度および５４〜２０重量％程度であり、さらに好ましくは６７〜７７重量％および３３〜２３重量％である。 (B) The usage-amount of a component and (C) component is not specifically limited, What is necessary is just to determine suitably according to a use, respectively, However, from the viewpoint of the effect of this invention, the sum total of both was normally 100 weight%. In some cases, the order is about 41 to 88% by weight and about 59 to 12% by weight, preferably about 46 to 80% by weight and about 54 to 20% by weight, and more preferably 67 to 77% by weight and 33 to 23%. % By weight.
また、（Ｂ）成分と（Ｃ）成分の反応条件は特に限定されないが、例えば、両成分を所定量ずつ反応容器に仕込み、必要に応じて各種公知の触媒の存在下、２００〜３００℃程度で１〜２０時間程度反応させればよい。触媒としては前記したものを使用できる。 Further, the reaction conditions for the component (B) and the component (C) are not particularly limited. For example, both components are charged into a reaction vessel in predetermined amounts, and if necessary, in the presence of various known catalysts, about 200 to 300 ° C. For about 1 to 20 hours. As the catalyst, those described above can be used.
このようにして得られる本発明のロジン変性フェノール樹脂は、本発明の効果の観点より、重量平均分子量（Ｍｗ）が３０，０００〜３９，０００であり、数平均分子量（Ｍｎ）が３，０００〜４，９４０であり、かつ多分散度（Ｍｗ／Ｍｎ）が８〜９に設定されている点に大きな特徴がある。多分散度は分子量分布幅を示す指標であり、本発明のロジン変性フェノール樹脂はその数値が比較的小さいため、分子量分布幅が狭いといえる。そして、多分散度を８以上としたことにより特に印刷インキ皮膜の光沢が、また９以下としたことにより特に印刷インキの流動性および印刷インキ皮膜の光沢が良好になる。 Rosin-modified phenolic resin of the present invention thus obtained is, from the viewpoint of the effect of the present invention, the weight average molecular weight (Mw) was 3 0,000～ 39,000, number average molecular weight (Mn) of 3, 000 to 4,940, and the polydispersity (Mw / Mn) is set to 8 to 9, which is a great feature. The polydispersity is an index indicating the molecular weight distribution width, and the rosin-modified phenolic resin of the present invention has a relatively small numerical value, so that it can be said that the molecular weight distribution width is narrow. When the polydispersity is 8 or more, the gloss of the printing ink film is particularly good, and when it is 9 or less, the fluidity of the printing ink and the gloss of the printing ink film are particularly good.
なお、ＭｗとＭｎはいずれもゲルパーメーションクロマトグラフィー法によるポリスチレン換算値であり、市販の装置により測定可能である。ＭｗとＭｎは、例えば前記（Ａ）成分や（Ｃ）成分の使用量を変更したり、エステル化触媒の種類や使用量を変更したり、（ｂ−１）成分として多官能のもの（例えば、（無水）マレイン酸変性ロジン等）を用いたりする等して調整可能である。 In addition, both Mw and Mn are polystyrene conversion values by a gel permeation chromatography method, and can be measured by a commercially available apparatus . Mw and Mn are, for example, change the amount of the component (A) or component (C), change the type or amount of the esterification catalyst, or (b-1) a polyfunctional one (for example, , (Anhydrous) maleic acid modified rosin, etc.).
また、当該ロジン変性フェノール樹脂の他の物性も特に限定されないが、本発明の効果の観点より、通常、酸価（ＪＩＳ Ｋ５６０１−２−１）が１０〜５０ｍｇＫＯＨ／ｇ程度、好ましくは１０〜３０ｍｇＫＯＨ／ｇである。 Further, other physical properties of the rosin-modified phenol resin are not particularly limited, but from the viewpoint of the effect of the present invention, the acid value (JIS K5601-2-1) is usually about 10 to 50 mgKOH / g, preferably 10 to 30 mgKOH. / G.
また、軟化点（ＪＩＳ Ｋ５６０１−２−２）も特に限定されないが、やはり本発明の効果の観点より、通常、１４０〜１９０℃程度、好ましくは１５０〜１８０℃である。 Also, the softening point (JIS K5601-2-2) is not particularly limited, but it is usually about 140 to 190 ° C, preferably 150 to 180 ° C from the viewpoint of the effect of the present invention.
本発明の印刷インキ用ワニスは、本発明の印刷インキ用バインダー（ロジン変性フェノール樹脂）と植物油類を含むものであり、必要に応じて石油系溶剤やゲル化剤を含めることができる。 The varnish for printing ink of the present invention contains the binder for printing ink of the present invention (rosin-modified phenol resin) and vegetable oils, and can contain a petroleum solvent or a gelling agent as necessary.
植物油類としては、例えば、アマニ油、桐油、サフラワー油、脱水ヒマシ油、大豆油等の植物油の他、アマニ油脂肪酸メチル、大豆油脂肪酸メチル、アマニ油脂肪酸エチル、大豆油脂肪酸エチル、アマニ油脂肪酸プロピル、大豆油脂肪酸プロピル、アマニ油脂肪酸ブチル、大豆油脂肪酸ブチル等といった前記植物油のモノエステル等が挙げられ、これらは１種を単独で、または２種以上を組み合わせて使用できる。これらのうち、印刷物の乾燥性を考慮すると、前記植物油、特に分子中に不飽和結合を有する植物油が好ましい。 Examples of vegetable oils include vegetable oils such as linseed oil, tung oil, safflower oil, dehydrated castor oil, soybean oil, linseed oil fatty acid methyl, soybean oil fatty acid methyl, linseed oil fatty acid ethyl, soybean oil fatty acid ethyl, linseed oil Examples include monoesters of the above vegetable oils such as fatty acid propyl, soybean oil fatty acid propyl, linseed oil fatty acid butyl, soybean oil fatty acid butyl, and the like, and these can be used alone or in combination of two or more. Among these, considering the drying property of the printed matter, the vegetable oil, particularly the vegetable oil having an unsaturated bond in the molecule is preferable.
インキ用石油系溶剤としては、例えば、ＪＸ日鉱日石エネルギー（株）製の石油系溶剤である０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、７号ソルベント、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号等が挙げられ、これらは１種を単独で、または２種以上を組み合わせて使用できる。これらのうち、特に本発明のロジン変性フェノール樹脂の溶解性や、環境面への影響を考慮すると、沸点が２００℃以上で芳香族炭化水素の含有率が１重量％以下であるものが好ましい。 As the petroleum solvent for ink, for example, No. 0 Solvent, No. 4 Solvent, No. 5 Solvent, No. 6 Solvent, No. 7 Solvent, AF Solvent No. 4, which are petroleum solvents manufactured by JX Nippon Oil & Energy Corporation, Examples include AF solvent No. 5, AF solvent No. 6, AF solvent No. 7, and the like. These can be used alone or in combination of two or more. Among these, in consideration of the solubility of the rosin-modified phenolic resin of the present invention and the influence on the environment, those having a boiling point of 200 ° C. or higher and an aromatic hydrocarbon content of 1% by weight or less are preferable.
ゲル化剤としては、例えば、オクチル酸アルミニウム、ステアリン酸アルミニウム、アルミニウムトリイソプロポキシド、アルミニウムトリブトキシド、アルミニウムジプロポキシドモノアセチルアセテート、アルミニウムジブトキシドモノアセチルアセテート、アルミニウムトリアセチルアセテート等のアルミニウム系キレート剤が挙げられ、これらは１種を単独で、または２種以上を組み合わせて使用できる。 Examples of the gelling agent include aluminum chelates such as aluminum octylate, aluminum stearate, aluminum triisopropoxide, aluminum tributoxide, aluminum dipropoxide monoacetyl acetate, aluminum dibutoxide monoacetyl acetate, and aluminum triacetyl acetate. An agent is mentioned, These can be used individually by 1 type or in combination of 2 or more types.
本発明の印刷インキ用ワニスは、上記した成分を混合し、撹拌することにより製造できる。また、混合撹拌時の温度は特に制限されないが、１００〜２４０℃程度であるのが好ましい。なお、本ワニスには他に添加剤として酸化防止剤等を配合できる。 The printing ink varnish of the present invention can be produced by mixing and stirring the above-described components. The temperature during mixing and stirring is not particularly limited, but is preferably about 100 to 240 ° C. In addition, an antioxidant etc. can be mix | blended with this varnish as an additive.
本発明の印刷インキは、本発明の印刷インキ用ワニスを用いたものであり、これに顔料（黄、紅、藍、墨）及び各種公知の添加剤配合し、ロールミル、ボールミル、アトライター、サンドミルといった公知のインキ製造装置を用いて適切なインキ恒数となるよう、練肉・調製することにより得られる。添加剤としては、インキ流動性やインキ表面被膜を改善するための界面活性剤、ワックス等があげられる。 The printing ink of the present invention uses the varnish for printing ink of the present invention, and is blended with pigments (yellow, red, indigo, black) and various known additives, roll mill, ball mill, attritor, sand mill. It is obtained by kneading and preparing so as to obtain an appropriate ink constant using a known ink manufacturing apparatus. Examples of the additive include a surfactant for improving ink fluidity and an ink surface film, and wax.
以下、製造例、実施例をあげて本発明を更に具体的に説明するが、これらにより本発明の範囲が限定されることはない。なお、以下「部」とは重量部を示す。 Hereinafter, the present invention will be described more specifically with reference to production examples and examples, but the scope of the present invention is not limited by these examples. Hereinafter, “parts” means parts by weight.
また、各例中、３３重量％アマニ油粘度とは、樹脂とアマニ油を１対２重量比で加熱混合したものを、日本レオロジー（株）製コーン・アンド・プレート型粘度計を用いて２５℃で測定した粘度である（以下、同様）。 In each example, the 33% by weight linseed oil viscosity is 25 by using a cone and plate viscometer manufactured by Nippon Rheology Co., Ltd. It is the viscosity measured at ° C. (hereinafter the same).
また、数平均分子量と重量平均分子量はいずれも、ゲルパーメーションクロマトグラフィー（東ソー（株）製、ＨＬＣ−８１２０ＧＰＣ）および市販のカラム（東ソー（株）製、ＴＳＫ−ＧＥＬ）を用い、テトラヒドロフラン（ＴＨＦ）を展開溶媒として測定されたポリスチレン換算値であり、求めた数平均分子量と重量平均分子量より多分散度（Ｍｗ／Ｍｎ）を算出した。 The number average molecular weight and the weight average molecular weight are both gel permeation chromatography (manufactured by Tosoh Corporation, HLC-8120GPC) and a commercially available column (manufactured by Tosoh Corporation, TSK-GEL) and tetrahydrofuran (THF). ) As a developing solvent, and the polydispersity (Mw / Mn) was calculated from the obtained number average molecular weight and weight average molecular weight.
製造例１
（（Ｃ）成分の製造）
撹拌機、分水器付き還流冷却管および温度計を備えた反応容器に、オクチルフェノール１，０００部、９２％パラホルムアルデヒド３９６部、キシレン５８４部および水５００部を仕込み、撹拌下に５０℃まで昇温した。次いで、同反応容器に４５％水酸化ナトリウム溶液８９部を仕込み、冷却しながら反応系を９０℃まで徐々に昇温した後、２時間保温し、更に硫酸を滴下してｐＨを約６に調整した。その後、ホルムアルデヒドなどを含んだ水層部を除去し、再度水洗した後に内容物を冷却して、レゾール型オクチルフェノール（Ｃ−１）の７０重量％キシレン溶液を得た。
Production Example 1
(Production of component (C))
A reaction vessel equipped with a stirrer, a reflux condenser with a water separator and a thermometer was charged with 1,000 parts of octylphenol, 396 parts of 92% paraformaldehyde, 584 parts of xylene and 500 parts of water, and the temperature was raised to 50 ° C. with stirring. Warm up. Next, 89 parts of 45% sodium hydroxide solution was charged into the same reaction vessel, the reaction system was gradually warmed to 90 ° C. while cooling, and then kept warm for 2 hours, and sulfuric acid was added dropwise to adjust the pH to about 6. did. Thereafter, the aqueous layer containing formaldehyde and the like was removed, washed again with water, and then the contents were cooled to obtain a 70% by weight xylene solution of resol type octylphenol (C-1).
製造例２
（（Ｃ）成分の製造）
製造例１と同様の反応容器に、ブチルフェノール１，０００部、９２％パラホルムアルデヒド５４３部、キシレン６４６部および水５００部を仕込み、撹拌下に５０℃まで昇温した。次いで、同反応容器に４５％水酸化ナトリウム溶液８９部を仕込み、冷却しながら反応系を９０℃まで徐々に昇温した後、２時間保温し、更に硫酸を滴下してｐＨを約６に調整した。その後、ホルムアルデヒドなどを含んだ水層部を除去し、再度水洗した後に内容物を冷却して、レゾール型ブチルフェノール（Ｃ−２）の７０重量％キシレン溶液を得た。
Production Example 2
(Production of component (C))
A reaction vessel similar to Production Example 1 was charged with 1,000 parts of butylphenol, 543 parts of 92% paraformaldehyde, 646 parts of xylene and 500 parts of water, and the temperature was raised to 50 ° C. with stirring. Next, 89 parts of 45% sodium hydroxide solution was charged into the same reaction vessel, the reaction system was gradually warmed to 90 ° C. while cooling, and then kept warm for 2 hours, and sulfuric acid was added dropwise to adjust the pH to about 6. did. Thereafter, the aqueous layer portion containing formaldehyde and the like was removed, and after washing with water again, the contents were cooled to obtain a 70% by weight xylene solution of resol type butylphenol (C-2).
製造例３
（（Ｃ）成分の製造）
製造例１と同様の反応容器に、ノニルフェノール１，０００部、９２％パラホルムアルデヒド３７０部、キシレン５７３部および水５００部を仕込み、撹拌下に５０℃まで昇温した。次いで、同反応容器に４５％水酸化ナトリウム溶液８９部を仕込み、冷却しながら反応系を９０℃まで徐々に昇温した後、２時間保温し、更に硫酸を滴下してｐＨを約６に調整した。その後、ホルムアルデヒドなどを含んだ水層部を除去し、再度水洗した後に内容物を冷却して、レゾール型ノニルフェノール（Ｃ−３）の７０重量％キシレン溶液を得た。
Production Example 3
(Production of component (C))
A reaction vessel similar to Production Example 1 was charged with 1,000 parts of nonylphenol, 370 parts of 92% paraformaldehyde, 573 parts of xylene and 500 parts of water, and the temperature was raised to 50 ° C. with stirring. Next, 89 parts of 45% sodium hydroxide solution was charged into the same reaction vessel, the reaction system was gradually warmed to 90 ° C. while cooling, and then kept warm for 2 hours, and sulfuric acid was added dropwise to adjust the pH to about 6. did. Thereafter, the aqueous layer containing formaldehyde and the like was removed, washed again with water, and then the contents were cooled to obtain a 70% by weight xylene solution of resol type nonylphenol (C-3).
参照例１
製造例１と同様の反応容器に、ガムロジン１，０００部を仕込み、これを窒素雰囲気下に撹拌しながら１８０℃まで昇温して溶融させた。次いで、グリセリン９３部を添加し、撹拌下に２８０℃まで昇温した。昇温後、トリフェニルホスファイト０．７部を仕込み、酸価が２５ｍｇＫＯＨ／ｇ以下となるまで反応させた。更に２３０℃まで冷却した後、（Ｃ−１）成分の溶液５００部（固形分３５０部）を２３０〜２６０℃の温度範囲内で４時間かけて系内へ滴下した。滴下終了後、３３重量％アマニ油粘度が２．５Ｐａ・ｓとなるよう調整し、０．０２ＭＰａで１０分間減圧することにより、ロジン変性フェノール樹脂（１）を得た。原料と物性を表１に示す（以下、同様。）。
Reference example 1
In a reaction vessel similar to Production Example 1, 1,000 parts of gum rosin were charged, and the mixture was heated to 180 ° C. and stirred while stirring in a nitrogen atmosphere. Next, 93 parts of glycerin was added, and the temperature was raised to 280 ° C. with stirring. After raising the temperature, 0.7 part of triphenyl phosphite was added and the reaction was continued until the acid value was 25 mgKOH / g or less. Furthermore, after cooling to 230 degreeC, 500 parts (350 parts of solid content) of the solution of (C-1) component was dripped in the system over 4 hours within the temperature range of 230-260 degreeC. After completion of the dropwise addition, the rosin-modified phenolic resin (1) was obtained by adjusting the 33 wt% linseed oil viscosity to 2.5 Pa · s and reducing the pressure at 0.02 MPa for 10 minutes. The raw materials and physical properties are shown in Table 1 (the same applies hereinafter).
参照例２
製造例１と同様の反応容器に、ガムロジン１，０００部を仕込み、これを窒素雰囲気下に撹拌しながら１８０℃まで昇温して溶融させた。次いで、グリセリン９３部を添加し、撹拌下に２８０℃まで昇温した。昇温後、トリフェニルホスファイト２．５部を仕込み、酸価が２５ｍｇＫＯＨ／ｇ以下となるまで反応させた。更に２３０℃まで冷却した後、（Ｃ−１）成分の溶液５００部（固形分３５０部）を２３０〜２６０℃の温度範囲内で４時間かけて系内へ滴下した。滴下終了後、３３重量％アマニ油粘度が２．５Ｐａ・ｓとなるよう調整し、０．０２ＭＰａで１０分間減圧することにより、ロジン変性フェノール樹脂（２）を得た。
Reference example 2
In a reaction vessel similar to Production Example 1, 1,000 parts of gum rosin were charged, and the mixture was heated to 180 ° C. and stirred while stirring in a nitrogen atmosphere. Next, 93 parts of glycerin was added, and the temperature was raised to 280 ° C. with stirring. After raising the temperature, 2.5 parts of triphenyl phosphite was added and allowed to react until the acid value became 25 mgKOH / g or less. Furthermore, after cooling to 230 degreeC, 500 parts (350 parts of solid content) of the solution of (C-1) component was dripped in the system over 4 hours within the temperature range of 230-260 degreeC. After completion of dropping, the rosin-modified phenol resin (2) was obtained by adjusting the viscosity of linseed oil at 33 wt% to 2.5 Pa · s and reducing the pressure at 0.02 MPa for 10 minutes.
参照例３
製造例１と同様の反応容器に、ガムロジン１，０００部を仕込み、これを窒素雰囲気下に撹拌しながら１８０℃まで昇温して溶融させた。次いで、グリセリン９３部を添加し、撹拌下に２８０℃まで昇温した。昇温後、トリフェニルホスファイト４．８部を仕込み、酸価が２５ｍｇＫＯＨ／ｇ以下となるまで反応させた。更に２３０℃まで冷却した後、（Ｃ−１）成分の溶液５００部（固形分３５０部）を２３０〜２６０℃の温度範囲内で４時間かけて系内へ滴下した。滴下終了後、３３重量％アマニ油粘度が２．５Ｐａ・ｓとなるよう調整し、０．０２ＭＰａで１０分間減圧することにより、ロジン変性フェノール樹脂（３）を得た。
Reference example 3
In a reaction vessel similar to Production Example 1, 1,000 parts of gum rosin were charged, and the mixture was heated to 180 ° C. and stirred while stirring in a nitrogen atmosphere. Next, 93 parts of glycerin was added, and the temperature was raised to 280 ° C. with stirring. After the temperature elevation, 4.8 parts of triphenyl phosphite was charged and reacted until the acid value became 25 mgKOH / g or less. Furthermore, after cooling to 230 degreeC, 500 parts (350 parts of solid content) of the solution of (C-1) component was dripped in the system over 4 hours within the temperature range of 230-260 degreeC. After completion of the dropwise addition, the rosin-modified phenolic resin (3) was obtained by adjusting the 33% by weight linseed oil viscosity to 2.5 Pa · s and reducing the pressure at 0.02 MPa for 10 minutes.
参照例４
製造例１と同様の反応容器に、ガムロジン１，０００部を仕込み、これを窒素雰囲気下に撹拌しながら１８０℃まで昇温して溶融させた。次いで、グリセリン９３部を添加し、撹拌下に２８０℃まで昇温した。昇温後、トリフェニルホスファイト２．５部を仕込み、酸価が２５ｍｇＫＯＨ／ｇ以下となるまで反応させた。更に２３０℃まで冷却した後、（Ｃ−１）成分の溶液３８６部（固形分２７０部）、次いで（Ｃ−２）成分の溶液１１４部（固形分８０部）を２３０〜２６０℃の温度範囲内で４時間かけて系内へ滴下した。滴下終了後、３３重量％アマニ油粘度が２．５Ｐａ・ｓとなるよう調整し、０．０２ＭＰａで１０分間減圧することにより、ロジン変性フェノール樹脂（４）を得た。
Reference example 4
In a reaction vessel similar to Production Example 1, 1,000 parts of gum rosin were charged, and the mixture was heated to 180 ° C. and stirred while stirring in a nitrogen atmosphere. Next, 93 parts of glycerin was added, and the temperature was raised to 280 ° C. with stirring. After raising the temperature, 2.5 parts of triphenyl phosphite was added and allowed to react until the acid value became 25 mgKOH / g or less. After further cooling to 230 ° C., 386 parts of the component (C-1) solution (solid content 270 parts), and then 114 parts of the component (C-2) solution (solid content 80 parts) were in the temperature range of 230 to 260 ° C. The solution was dropped into the system over 4 hours. After completion of the dropwise addition, the rosin-modified phenolic resin (4) was obtained by adjusting the 33 wt% linseed oil viscosity to 2.5 Pa · s and reducing the pressure at 0.02 MPa for 10 minutes.
参照例５
製造例１と同様の反応容器に、ガムロジン１，０００部を仕込み、これを窒素雰囲気下に撹拌しながら１８０℃まで昇温して溶融させた。次いで、グリセリン９３部を添加し、撹拌下２８０℃まで昇温した。昇温後、トリフェニルホスファイト２．５部を仕込み、酸価が２５ｍｇＫＯＨ／ｇ以下となるまで反応させた。更に２３０℃まで冷却した後、（Ｃ−１）成分の溶液３５７部（固形分２５０部）、次いで（Ｃ−３）成分の溶液１４３部（固形分１００部）を２３０〜２６０℃の温度範囲内で４時間かけて系内へ滴下した。滴下終了後、３３重量％アマニ油粘度が２．５Ｐａ・ｓとなるよう調整し、０．０２ＭＰａで１０分間減圧することにより、ロジン変性フェノール樹脂（５）を得た。
Reference example 5
In a reaction vessel similar to Production Example 1, 1,000 parts of gum rosin were charged, and the mixture was heated to 180 ° C. and stirred while stirring in a nitrogen atmosphere. Next, 93 parts of glycerin was added and the temperature was raised to 280 ° C. with stirring. After raising the temperature, 2.5 parts of triphenyl phosphite was added and allowed to react until the acid value became 25 mgKOH / g or less. After further cooling to 230 ° C., 357 parts (solid content 250 parts) of the component (C-1), and then 143 parts (solid content 100 parts) of the component (C-3) are in the temperature range of 230 to 260 ° C. The solution was dropped into the system over 4 hours. After completion of the dropwise addition, the rosin-modified phenolic resin (5) was obtained by adjusting the 33% by weight linseed oil viscosity to 2.5 Pa · s and reducing the pressure at 0.02 MPa for 10 minutes.
参照例６
製造例１と同様の反応容器に、ガムロジン１，０００部を仕込み、これを窒素雰囲気下に撹拌しながら１８０℃まで昇温して溶融させた。次いで、ペンタリスリトール１０３部を添加し、撹拌下に２８０℃まで昇温した。昇温後、トリフェニルホスファイト２．５部を仕込み、酸価が２５ｍｇＫＯＨ／ｇ以下となるまで反応させた。更に２３０℃まで冷却した後、（Ｃ−１）成分の溶液５００部（固形分３５０部）を２３０〜２６０℃の温度範囲内で４時間かけて系内へ滴下した。滴下終了後、３３重量％アマニ油粘度が２．５Ｐａ・ｓとなるよう調整し、０．０２ＭＰａで１０分間減圧することにより、ロジン変性フェノール樹脂（８）を得た。
Reference example 6
In a reaction vessel similar to Production Example 1, 1,000 parts of gum rosin were charged, and the mixture was heated to 180 ° C. and stirred while stirring in a nitrogen atmosphere. Next, 103 parts of pentalysitol was added, and the temperature was raised to 280 ° C. with stirring. After raising the temperature, 2.5 parts of triphenyl phosphite was added and allowed to react until the acid value became 25 mgKOH / g or less. Furthermore, after cooling to 230 degreeC, 500 parts (350 parts of solid content) of the solution of (C-1) component was dripped in the system over 4 hours within the temperature range of 230-260 degreeC. After completion of the dropwise addition, the rosin-modified phenol resin (8) was obtained by adjusting the 33 wt% linseed oil viscosity to 2.5 Pa · s and reducing the pressure at 0.02 MPa for 10 minutes.
実施例１
製造例１と同様の反応容器に、トール油ロジン１，０００部を仕込み、これを窒素雰囲気下に撹拌しながら１８０℃まで昇温して溶融させた。次いで、グリセリン９３部を添加し、撹拌下に２８０℃まで昇温した。昇温後、トリフェニルホスファイト２．５部を仕込み、酸価が２５ｍｇＫＯＨ／ｇ以下となるまで反応させた。更に２３０℃まで冷却した後、（Ｃ−１）成分の溶液５００部（固形分３５０部）を２３０〜２６０℃の温度範囲内で４時間かけて系内へ滴下した。滴下終了後、３３重量％アマニ油粘度が２．５Ｐａ・ｓとなるよう調整し、０．０２ＭＰａで１０分間減圧することにより、ロジン変性フェノール樹脂（９）を得た。原料と物性を表１に示す（以下、同様。）。
Example 1
In a reaction vessel similar to Production Example 1, 1,000 parts of tall oil rosin was charged and heated to 180 ° C. with stirring in a nitrogen atmosphere and melted. Next, 93 parts of glycerin was added, and the temperature was raised to 280 ° C. with stirring. After raising the temperature, 2.5 parts of triphenyl phosphite was added and allowed to react until the acid value became 25 mgKOH / g or less. Furthermore, after cooling to 230 degreeC, 500 parts (350 parts of solid content) of the solution of (C-1) component was dripped in the system over 4 hours within the temperature range of 230-260 degreeC. After completion of the dropwise addition, the rosin-modified phenol resin (9) was obtained by adjusting the 33 wt% linseed oil viscosity to 2.5 Pa · s and reducing the pressure at 0.02 MPa for 10 minutes. The raw materials and physical properties are shown in Table 1 (the same applies hereinafter).
実施例２
製造例１と同様の反応容器に、ガムロジン１，０００部を仕込み、これを窒素雰囲気下に撹拌しながら１８０℃まで昇温して溶融させた。次いで、グリセリン９３部を添加し、撹拌下に２８０℃まで昇温した。昇温後、トリフェニルホスファイト２．５部を仕込み、酸価が２５ｍｇＫＯＨ／ｇ以下となるまで反応させた。更に２３０℃まで冷却した後、（Ｃ−１）成分の溶液３５７部（固形分２５０部）を２３０〜２６０℃の温度範囲内で４時間かけて系内へ滴下した。滴下終了後、３３重量％アマニ油粘度が２．５Ｐａ・ｓとなるよう調整し、０．０２ＭＰａで１０分間減圧することにより、ロジン変性フェノール樹脂（１０）を得た。原料と物性を表１に示す（以下、同様。）。
Example 2
In a reaction vessel similar to Production Example 1, 1,000 parts of gum rosin were charged, and the mixture was heated to 180 ° C. and stirred while stirring in a nitrogen atmosphere. Next, 93 parts of glycerin was added, and the temperature was raised to 280 ° C. with stirring. After raising the temperature, 2.5 parts of triphenyl phosphite was added and allowed to react until the acid value became 25 mgKOH / g or less. After further cooling to 230 ° C., 357 parts (solid content 250 parts) of the component (C-1) was dropped into the system over 4 hours within a temperature range of 230 to 260 ° C. After completion of the dropwise addition, the rosin-modified phenolic resin (10) was obtained by adjusting the 33 wt% linseed oil viscosity to 2.5 Pa · s and reducing the pressure at 0.02 MPa for 10 minutes. The raw materials and physical properties are shown in Table 1 (the same applies hereinafter).
参照例７
製造例１と同様の反応容器に、ガムロジン１，０００部を仕込み、これを窒素雰囲気下に撹拌しながら１８０℃まで昇温して溶融させた。次いで、グリセリン９３部を添加し、撹拌下に２８０℃まで昇温した。昇温後、トリフェニルホスファイト２．５部を仕込み、酸価が２５ｍｇＫＯＨ／ｇ以下となるまで反応させた。更に２３０℃まで冷却した後、（Ｃ−１）成分の溶液６００部（固形分４２０部）を２３０〜２６０℃の温度範囲内で４時間かけて系内へ滴下した。滴下終了後、３３重量％アマニ油粘度が２．５Ｐａ・ｓとなるよう調整し、０．０２ＭＰａで１０分間減圧することにより、ロジン変性フェノール樹脂（１１）を得た。原料と物性を表１に示す（以下、同様。）。
Reference example 7
In a reaction vessel similar to Production Example 1, 1,000 parts of gum rosin were charged, and the mixture was heated to 180 ° C. and stirred while stirring in a nitrogen atmosphere. Next, 93 parts of glycerin was added, and the temperature was raised to 280 ° C. with stirring. After raising the temperature, 2.5 parts of triphenyl phosphite was added and allowed to react until the acid value became 25 mgKOH / g or less. After further cooling to 230 ° C., 600 parts (component 420 parts) of component (C-1) was dropped into the system over a period of 4 hours within a temperature range of 230 to 260 ° C. After completion of the dropwise addition, the rosin-modified phenolic resin (11) was obtained by adjusting the 33% by weight linseed oil viscosity to 2.5 Pa · s and reducing the pressure at 0.02 MPa for 10 minutes. The raw materials and physical properties are shown in Table 1 (the same applies hereinafter).
比較例１
製造例１と同様の反応容器に、ガムロジン１，０００部を仕込み、撹拌下に２２０℃まで昇温して溶融させた。ついで、（Ｃ−１）成分の溶液５７１部（固形分４００部）を、４時間かけて系内に滴下した。滴下終了後、グリセリン８４部及びパラトルエンスルホン酸２．０部を仕込み、２２０〜２６０℃の温度範囲内で酸価が２５以下となるまで反応させた。その後、０．０２ＭＰａで１０分間減圧することにより、ロジン変性フェノール樹脂（１’）を得た。
Comparative Example 1
In a reaction vessel similar to Production Example 1, 1,000 parts of gum rosin were charged and heated to 220 ° C. with melting to be melted. Subsequently, 571 parts (400 parts of solid content) of the component (C-1) was dropped into the system over 4 hours. After completion of the dropwise addition, 84 parts of glycerin and 2.0 parts of paratoluenesulfonic acid were added and reacted until the acid value became 25 or less within a temperature range of 220 to 260 ° C. Then, rosin modified phenolic resin (1 ′) was obtained by reducing the pressure at 0.02 MPa for 10 minutes.
比較例２
実施例２において、トリフェニルホスファイトを０．３部に変更した他は同様にして、ロジン変性フェノール樹脂（２’）を得た。
Comparative Example 2
A rosin-modified phenolic resin (2 ′) was obtained in the same manner as in Example 2, except that triphenyl phosphite was changed to 0.3 part.
比較例３
実施例２において、トリフェニルホスファイトを５．３部に変更した他は同様にして、ロジン変性フェノール樹脂（３’）を得たが、多量の不溶物が発生していたため、物性は測定しなかった。
Comparative Example 3
In Example 2, except that triphenyl phosphite was changed to 5.3 parts, a rosin-modified phenol resin (3 ′) was obtained in the same manner. However, since a large amount of insoluble matter was generated, the physical properties were measured. There wasn't.
（ワニスの調製）
実施例１のロジン変性フェノール樹脂（１）を４５．０部、アマニ油を１０．０部、ＡＦソルベント７号（ＪＸ日鉱日石エネルギー（株）製、非芳香族石油系溶剤）を４３．５部、容器に仕込み、２００℃で３０分間混合した後、８０℃まで冷却した。次いで、アルミニウムジプロポキシドモノアセチルアセテート（商品名ケロープＥＰ−２、ホープ製薬（株）製）１．５部を加え、２００℃まで加熱して１時間ゲル化反応させることにより、ゲルワニスを得た。他の実施例および比較例の樹脂についても同様にしてゲルワニスを得た。
(Preparation of varnish)
45.0 parts of rosin-modified phenolic resin (1) of Example 1, 10.0 parts of linseed oil, AF Solvent No. 7 (manufactured by JX Nippon Oil & Energy Corporation, non-aromatic petroleum solvent) 43. 5 parts were charged into a container, mixed at 200 ° C. for 30 minutes, and then cooled to 80 ° C. Subsequently, 1.5 parts of aluminum dipropoxide monoacetylacetate (trade name Kerop EP-2, manufactured by Hope Pharmaceutical Co., Ltd.) was added, and the gel varnish was obtained by heating to 200 ° C. and allowing the gelation reaction for 1 hour. . Gel varnishes were obtained in the same manner for the resins of other examples and comparative examples.
（印刷インキの調製）
前記実施例および比較例のゲルワニスを用い、次の配合割合で３本ロールミルにより練肉して印刷インキを調製した。
フタロシアニンブルー（藍顔料） １８重量部
ゲルワニス ６２〜７０重量部
日石ＡＦソルベント７号 １２〜２０重量部
上記配合に基づいて３０℃、４００ｒｐｍにおけるインコメーターのタック値が６．５±０．５、２５℃におけるスプレッドメーターのフロー値（直径値）が３８．０±１．０となるよう適宜調製した。
(Preparation of printing ink)
Using the gel varnishes of the examples and comparative examples, printing ink was prepared by kneading with a three roll mill at the following blending ratio.
18 parts by weight of phthalocyanine blue (indigo pigment)
Gel Varnish 62-70 parts by weight Nisseki AF Solvent No. 7 12-20 parts by weight Based on the above formulation, the incometer tack value at 30 ° C. and 400 rpm is 6.5 ± 0.5, and the flow value of the spread meter at 25 ° C. ( (Diameter value) was appropriately adjusted to be 38.0 ± 1.0.
（印刷インキの性能試験）
実施例及び比較例の各ゲルワニスを用いて調製した印刷インキの諸性能を評価した。結果を表１に示す。
(Performance test of printing ink)
Various performances of printing inks prepared using the gel varnishes of Examples and Comparative Examples were evaluated. The results are shown in Table 1.
（光沢）
インキ０．４ｍｌをＲＩテスター（石川島産業機械（株）製）にてアート紙に展色した後、２３℃、５０％Ｒ．Ｈ．にて２４時間調湿し、６０゜−６０゜の反射率を光沢計により測定した。
(Glossy)
After 0.4 ml of ink was developed on art paper using an RI tester (manufactured by Ishikawajima Industrial Machinery Co., Ltd.), 23 ° C., 50% R.D. H. For 24 hours, and the reflectivity of 60 ° -60 ° was measured with a gloss meter.
（流動性）
２５℃に空調された室内において、インキ１．３ｍｌを地平面と６０゜の角度をなすガラス板の上端に置き、３０分間に流動した距離を測定した。数値が大きいほど流動性が良好であることを示す。
(Liquidity)
In a room air-conditioned at 25 ° C., 1.3 ml of ink was placed on the upper end of a glass plate forming an angle of 60 ° with the ground plane, and the distance of flowing for 30 minutes was measured. It shows that fluidity | liquidity is so favorable that a numerical value is large.
表１中、ＴＰＰはトリフェニルホスファイトを、ガムＲｏはガムロジンを、トール油Ｒｏはトール油ロジンを、ＭＡｎ−Ｒｏは無水マレイン酸変性ロジンを、Ｇｌｙはグリセリンを、Ｐｅｎはペンタエリスリトールをそれぞれ表す。 In Table 1, TPP represents triphenyl phosphite, gum Ro represents gum rosin, tall oil Ro represents tall oil rosin, MAn-Ro represents maleic anhydride-modified rosin, Gly represents glycerin, and Pen represents pentaerythritol. .
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