JP6284033B2 - Method for producing rosin-modified phenolic resin for offset printing ink, gel varnish for offset printing ink, and offset printing ink - Google Patents
Method for producing rosin-modified phenolic resin for offset printing ink, gel varnish for offset printing ink, and offset printing ink Download PDFInfo
- Publication number
- JP6284033B2 JP6284033B2 JP2014184722A JP2014184722A JP6284033B2 JP 6284033 B2 JP6284033 B2 JP 6284033B2 JP 2014184722 A JP2014184722 A JP 2014184722A JP 2014184722 A JP2014184722 A JP 2014184722A JP 6284033 B2 JP6284033 B2 JP 6284033B2
- Authority
- JP
- Japan
- Prior art keywords
- rosin
- component
- offset printing
- printing ink
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 238000007645 offset printing Methods 0.000 title claims description 31
- 239000002966 varnish Substances 0.000 title claims description 18
- 239000000976 ink Substances 0.000 claims description 53
- 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 50
- 239000002904 solvent Substances 0.000 claims description 39
- 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 36
- 239000002253 acid Substances 0.000 claims description 36
- 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 36
- 239000005011 phenolic resin Substances 0.000 claims description 32
- 150000002989 phenols Chemical class 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 27
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- 238000007639 printing Methods 0.000 claims description 14
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 claims description 11
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 claims description 11
- KGMSWPSAVZAMKR-UHFFFAOYSA-N Me ester-3, 22-Dihydroxy-29-hopanoic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(=C(C)C)C=C1CC2 KGMSWPSAVZAMKR-UHFFFAOYSA-N 0.000 claims description 11
- KGMSWPSAVZAMKR-ONCXSQPRSA-N Neoabietic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CCC(=C(C)C)C=C2CC1 KGMSWPSAVZAMKR-ONCXSQPRSA-N 0.000 claims description 11
- 238000004817 gas chromatography Methods 0.000 claims description 8
- 238000005227 gel permeation chromatography Methods 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 239000007787 solid Substances 0.000 description 30
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 150000007513 acids Chemical class 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000944 linseed oil Substances 0.000 description 11
- 235000021388 linseed oil Nutrition 0.000 description 11
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000004945 emulsification Methods 0.000 description 8
- 235000015112 vegetable and seed oil Nutrition 0.000 description 8
- 239000008158 vegetable oil Substances 0.000 description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 150000001993 dienes Chemical class 0.000 description 7
- 235000011187 glycerol Nutrition 0.000 description 7
- 239000003549 soybean oil Substances 0.000 description 7
- 235000012424 soybean oil Nutrition 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- -1 aluminum compound Chemical class 0.000 description 5
- 239000003849 aromatic solvent Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229920003987 resole Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003349 gelling agent Substances 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000011787 zinc oxide Substances 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000011230 binding agent Substances 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
- 238000009835 boiling Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 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
- 238000012423 maintenance Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 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
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- 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
- JDQDSEVNMTYMOC-UHFFFAOYSA-N 3-methylbenzenesulfonic acid Chemical compound CC1=CC=CC(S(O)(=O)=O)=C1 JDQDSEVNMTYMOC-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 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
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 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
- 150000001991 dicarboxylic acids Chemical class 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
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
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- 239000001530 fumaric acid 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
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 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
- 150000002763 monocarboxylic acids Chemical class 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
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 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
- 239000001993 wax Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明は、オフセット印刷、特に湿し水を用いるオフセット印刷のバインダー樹脂として用いるロジン変性フェノール樹脂の製造方法、ならびに該製造方法で得られるロジン変性フェノール樹脂を含有するオフセット印刷インキ用ゲルワニス、当該ゲルワニスを用いて得られるオフセット印刷インキに関する。 The present invention relates to a method for producing a rosin-modified phenolic resin used as a binder resin for offset printing, particularly offset printing using fountain solution, and a gel varnish for offset printing ink containing the rosin-modified phenolic resin obtained by the production method. The present invention relates to an offset printing ink obtained using
従来、オフセット印刷、特に湿し水を用いるオフセット印刷に用いるインキのバインダー樹脂としては、インキ皮膜の乾燥性や光沢等において優れることから、ロジン類、フェノール−ホルムアルデヒド縮合物およびポリオール類を反応させて得られる所謂ロジン変性フェノール樹脂が賞用されている。 Conventionally, as an ink binder resin used for offset printing, particularly offset printing using fountain solution, it is excellent in the drying property and gloss of the ink film, so that rosins, phenol-formaldehyde condensates and polyols are reacted. The so-called rosin-modified phenolic resin obtained is used award.
ロジン変性フェノール樹脂は、植物油や石油溶剤等の溶媒に溶解させたワニスとして用いられる場合もあるが、更にアルミ系化合物等のゲル化剤を反応させたゲルワニスとして利用されることも多く、ワニスまたはゲルワニス（以下、（ゲル）ワニスと総称することがある。）に顔料およびインキ用溶剤等を加え、機械的に混練りすることにより、目的とするオフセット印刷インキも得られる。 The rosin-modified phenolic resin may be used as a varnish dissolved in a solvent such as vegetable oil or petroleum solvent, but is also often used as a gel varnish reacted with a gelling agent such as an aluminum compound. A target offset printing ink can also be obtained by adding a pigment, a solvent for ink, and the like to gel varnish (hereinafter sometimes referred to as (gel) varnish) and mechanically kneading.
オフセット印刷は湿し水とインキの反発を利用し、画線部と非画線部を形成して印刷される方式であり、湿し水とインキの乳化状態が印刷物の品質に大きな影響を与える。そのため、インキに適度な乳化特性が求められ、例えば乳化率が高すぎる（湿し水を多く含む）場合には版の非画線部にもインキが付着し、印刷物に汚れが生じるという問題がある。 Offset printing is a method that uses the repulsion of dampening water and ink to print the image area and non-image area, and the emulsified state of dampening water and ink has a significant effect on the quality of the printed matter. . For this reason, there is a problem in that an appropriate emulsification characteristic is required for the ink. For example, when the emulsification rate is too high (including a large amount of fountain solution), the ink adheres to the non-image area of the plate and the printed matter is stained. is there.
ところで、特許文献１にも記載されているように、オフセット印刷インキに用いるインキ溶剤としては、大気汚染や環境問題、作業環境の保全等の観点より、近年ではナフテンやパラフィン等の脂肪族炭化水素を主成分とする非芳香族系溶剤が主流となっている。 By the way, as described in Patent Document 1, as an ink solvent used for offset printing ink, in recent years, aliphatic hydrocarbons such as naphthene and paraffin are used from the viewpoint of air pollution, environmental problems, maintenance of work environment, and the like. The mainstream is non-aromatic solvents mainly composed of.
しかしながら、特許文献１でも指摘されているように、そうした非芳香族系溶剤は一般的にロジン変性フェノール樹脂の溶解力に乏しく、得られるオフセット印刷インキの皮膜の光沢が低下するといった問題がある。また、オフセット印刷は、従前に増して高速印刷化が進んでおり、耐ミスチング性、低タック性等の高速印刷適性を満足させるためにはロジン変性フェノール樹脂の高分子量化が不可欠とされる。 However, as pointed out in Patent Document 1, such non-aromatic solvents generally have a problem that the rosin-modified phenol resin has poor solubility and the gloss of the resulting offset printing ink film is lowered. In addition, offset printing is being performed at higher speed than ever before, and in order to satisfy high-speed printing suitability such as misting resistance and low tackiness, it is indispensable to increase the molecular weight of rosin-modified phenolic resin.
それゆえ斯界では、高分子量でありながらも脂肪族炭化水素溶剤への溶解性に優れるロジン変性フェノール樹脂の要請が強い。この点、特許文献１によれば、ロジン類、フェノール−ホルムアルデヒド縮合物およびポリオール類をパラトルエンスルホン酸等の酸性触媒の存在下で反応させることにより、かかる要請に応じたロジン変性フェノール樹脂が得られるとされる。 Therefore, in this field, there is a strong demand for a rosin-modified phenolic resin having a high molecular weight but excellent solubility in an aliphatic hydrocarbon solvent. In this respect, according to Patent Document 1, a rosin-modified phenolic resin meeting such a request is obtained by reacting rosins, phenol-formaldehyde condensates and polyols in the presence of an acidic catalyst such as paratoluenesulfonic acid. It is said that
また、特許文献２ではロジン類、アルキルフェノール−ホルムアルデヒド縮合物、およびポリオール類をスルホン酸系触媒の存在下で反応させることに加えて、金属酸化物を併用することで、更に高分子量でありながらも脂肪族炭化水素溶剤への溶解性に優れるロジン変性フェノール樹脂を製造することができるとされるが、品質の向上には更に高溶解性のロジン変性フェノール樹脂が望まれる。 In addition, in Patent Document 2, in addition to reacting rosins, alkylphenol-formaldehyde condensates, and polyols in the presence of a sulfonic acid catalyst, a metal oxide is used in combination, so that the molecular weight is further increased. It is said that a rosin-modified phenolic resin having excellent solubility in an aliphatic hydrocarbon solvent can be produced. However, a higher-solubility rosin-modified phenolic resin is desired for improving quality.
本発明は、高分子量でかつ脂肪族炭化水素溶剤への溶解性に優れ、しかもオフセット印刷インキの耐ミスチング性、低タック性を維持しながらその光沢、乳化性を向上できる、オフセット印刷インキ用ロジン変性フェノール樹脂の製造方法を提供することを課題とする。 The present invention is a rosin for offset printing inks that has a high molecular weight and excellent solubility in an aliphatic hydrocarbon solvent, and that can improve the gloss and emulsifiability while maintaining the misting resistance and low tackiness of offset printing inks. It is an object to provide a method for producing a modified phenolic resin.
本発明者は鋭意検討の結果、スルホン酸系触媒の存在下、原料ロジン類を加熱させて得られる特定条件を満たすロジン類をアルキルフェノール−ホルムアルデヒド縮合物、ポリオール類と反応させることで高分子量、且つ脂肪族炭化水素溶剤への溶解性に優れるロジン変性フェノール樹脂が得られることを意外にも見出した。 As a result of intensive studies, the inventor has reacted with rosins satisfying specific conditions obtained by heating raw material rosins in the presence of a sulfonic acid-based catalyst with an alkylphenol-formaldehyde condensate, polyols, and a high molecular weight, It was surprisingly found that a rosin-modified phenolic resin having excellent solubility in an aliphatic hydrocarbon solvent can be obtained.
すなわち本発明は、スルホン酸触媒（Ｂ）の存在下、原料ロジン類を加熱処理して得られる下記（１）及び（２）を満たすロジン類（Ａ）をアルキルフェノール−ホルムアルデヒド縮合物（Ｃ）と反応させた後、次いでポリオール類（Ｄ）とエステル化反応させて重量平均分子量５０，０００〜１３０，０００のオフセット印刷インキ用ロジン変性フェノール樹脂を得るオフセット印刷インキ用ロジン変性フェノール樹脂の製造方法に関する。
（１）前記（Ａ）成分中に、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の重量平均分子量１以上１９９以下である低分子量成分（ａ１）５〜１２％、かつ重量平均分子量４０１以上２０００以下である高分子量成分（ａ２）４〜６％が含まれる。
（２）ガスクロマトグラフィー法により得られた前記（Ａ）成分中に含まれるパラストリン酸、アビエチン酸およびネオアビエチン酸の合計含有量（ｔ１）の原料ロジン類中に含まれる前記合計含有量（ｔ２）に対する比率［（ｔ１／ｔ２）×１００］が、８８％以上である。
That is, in the present invention, rosins (A) satisfying the following (1) and (2) obtained by heat-treating raw material rosins in the presence of the sulfonic acid catalyst (B) are converted to alkylphenol-formaldehyde condensates (C). after reacting, then the method of producing polyols (D) and esterification reaction is allowed to Ru obtain an offset printing ink rosin-modified phenolic resin having a weight average molecular weight 50,000～130,000 offset printing ink rosin-modified phenolic resin About.
(1) In the component (A), a low molecular weight component (a1) having a weight average molecular weight of 1 to 199 in terms of polystyrene by gel permeation chromatography is 5 to 12% and a weight average molecular weight of 401 to 2000. The high molecular weight component (a2) is 4 to 6%.
(2) The total content (t2) contained in the raw material rosins of the total content (t1) of parastrinic acid, abietic acid and neoabietic acid contained in the component (A) obtained by the gas chromatography method ) Ratio [(t1 / t2) × 100] is 88% or more.
本発明に係るロジン変性フェノール樹脂は、高分子量でありながら、芳香族炭化水素溶剤のみならず、印刷インキ溶剤の主流となっている脂肪族炭化水素溶剤にも良く溶解し、濁りのないクリアな（ゲル）ワニスを与える。また、当該（ゲル）ワニスは芳香族溶剤を用いていないため大気汚染や環境問題、作業環境の保全等の観点より好ましい。また、当該（ゲル）ワニスを用いて得られるオフセット印刷インキは特に流動性に優れる他、耐ミスチング性、低タック性やインキ皮膜の乾燥性、光沢にも優れており、湿し水に対する耐乳化性も良好である。 The rosin-modified phenolic resin according to the present invention has a high molecular weight, but also dissolves well in not only aromatic hydrocarbon solvents but also aliphatic hydrocarbon solvents that are the mainstream of printing ink solvents, and is clear and clear. Give (gel) varnish. The (gel) varnish does not use an aromatic solvent, and therefore is preferable from the viewpoint of air pollution, environmental problems, work environment maintenance, and the like. In addition, the offset printing ink obtained using the (gel) varnish is particularly excellent in fluidity, and is also excellent in misting resistance, low tackiness, dryness of ink film, and gloss, and is resistant to emulsification in dampening water. The property is also good.
本発明のロジン変性フェノール樹脂の製造方法においては、予め、スルホン酸触媒（Ｂ）（以下、（Ｂ）成分という。）存在下で加熱処理して得られたロジン類（Ａ）（以下、（Ａ）成分という。）を用いる。
（Ａ）成分の製造に用いる原料ロジン類としては、例えば、ガムロジン、トール油ロジンおよびウッドロジン等からなる群より選ばれる天然ロジンまたは前記ロジン類を蒸留等で精製したロジンを単独で用いてもよく、２種以上を混合して用いてもよい。また、必要に応じて、前記原料ロジン類と（Ｂ）成分との反応前もしくは反応後に、不飽和カルボン酸類を付加して不飽和酸変性ロジンとすることも可能である。なお、不飽和カルボン酸類としては、例えばマレイン酸、無水マレイン酸、フマル酸、イタコン酸、クロトン酸、ケイ皮酸、アクリル酸、メタクリル酸等の不飽和モノカルボン酸や不飽和ジカルボン酸が挙げられる。また、当該不飽和酸変性ロジンは、ロジン類１００重量部に対して不飽和カルボン酸類を通常１〜３０重量部程度用いて変性（ディールス・アルダー反応）する。
In the method for producing a rosin-modified phenolic resin of the present invention, rosins (A) (hereinafter, (( A) component)) is used.
As the raw material rosins used for the production of the component (A), for example, natural rosin selected from the group consisting of gum rosin, tall oil rosin, wood rosin and the like, or rosin purified by distillation or the like may be used alone. Two or more kinds may be mixed and used. If necessary, an unsaturated carboxylic acid can be added to the unsaturated acid-modified rosin before or after the reaction between the raw material rosins and the component (B). Examples of unsaturated carboxylic acids include unsaturated monocarboxylic acids and unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid and methacrylic acid. . Further, the unsaturated acid-modified rosin is modified (Diels-Alder reaction) by using about 1 to 30 parts by weight of an unsaturated carboxylic acid with respect to 100 parts by weight of the rosin.
（Ｂ）成分の具体例としては、メタンスルホン酸、エタンスルホン酸、ベンゼンスルホン酸、オルトトルエンスルホン酸、メタトルエンスルホン酸、およびパラトルエンスルホン酸等が挙げられるが、これらの中でも、原料ロジン類と適度に反応するメタンスルホン酸、パラトルエンスルホン酸が好ましく用いられる。 Specific examples of the component (B) include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, orthotoluenesulfonic acid, metatoluenesulfonic acid, and paratoluenesulfonic acid. Among these, raw material rosins Methanesulfonic acid and p-toluenesulfonic acid that react moderately with benzene are preferably used.
通常、（Ｂ）成分は後述するポリオール類（Ｄ）（以下、（Ｄ）成分という。）との反応におけるエステル化触媒として使用されるものであるが、本発明の加熱処理においては、原料ロジン類自体の低分子量化と高分子量化反応も促進する役割がある。そして、この低分子量成分と高分子量成分を生成させたロジン類を使用してロジン変性フェノール樹脂を製造した場合、低分子量成分はロジン変性フェノール樹脂の高溶解性を促進し、高分子量成分は該樹脂の高分子量化を促進する。 Usually, the component (B) is used as an esterification catalyst in the reaction with the polyols (D) (hereinafter referred to as the component (D)) described later. In the heat treatment of the present invention, the raw material rosin is used. It has a role of promoting the molecular weight reduction and high molecular weight reaction of the class itself. When a rosin modified phenolic resin is produced using the rosins produced with the low molecular weight component and the high molecular weight component, the low molecular weight component promotes the high solubility of the rosin modified phenolic resin, and the high molecular weight component Promotes high molecular weight resin.
また一方で、（Ｂ）成分は原料ロジン類に含まれる樹脂酸類の不均化反応も促進し、得られた不均化ロジン類はアルキルフェノール−ホルムアルデヒド縮合物（Ｃ）（以下、（Ｃ）成分という。）と反応しないため、高分子量化が困難となる。そのため、ロジン変性フェノール樹脂の高分子量化の観点からは、（Ｃ）成分との反応性に富む原料ロジン類中に元々含まれるパラストリン酸、アビエチン酸およびネオアビエチン酸を所定割合で残しておく必要がある。 On the other hand, the component (B) also promotes the disproportionation reaction of the resin acids contained in the raw material rosins, and the disproportionated rosins obtained are alkylphenol-formaldehyde condensate (C) (hereinafter referred to as component (C)). It is difficult to increase the molecular weight. Therefore, from the viewpoint of increasing the molecular weight of the rosin-modified phenolic resin, it is necessary to leave the parastolic acid, abietic acid and neoabietic acid originally contained in the raw material rosins rich in reactivity with the component (C) in a predetermined ratio. There is.
加熱処理の条件としては、原料ロジン類を加熱溶融後、所定量の（Ｂ）成分を加えて、１５０℃〜２８０℃程度で１５〜６０分反応させ、前記条件（１）および（２）を満たす（Ａ）成分を調製する。（Ｂ）成分の使用量は、原料ロジン類１００部に対して、０．０１〜０．１２重量部、好ましくは０．０２〜０．１０重量部である。０．０１重量部未満の場合には、得られた（Ａ）成分中の低分子量成分および高分子量成分の含有量が少ないため、ロジン変性フェノール樹脂の高分子量化および脂肪族炭化水素溶剤への溶解性に乏しくなり、０．１２重量部を超える場合には、（Ｃ）成分との反応に寄与する（Ａ）成分中に含まれるパラストリン酸、アビエチン酸およびネオアビエチン酸の量が少なくなるため、ロジン変性フェノール樹脂の高分子量化が困難となる。 As the conditions for the heat treatment, after the raw rosins are heated and melted, a predetermined amount of the component (B) is added and reacted at about 150 ° C. to 280 ° C. for 15 to 60 minutes. The conditions (1) and (2) are The component (A) to be filled is prepared. (B) The usage-amount of a component is 0.01-0.12 weight part with respect to 100 parts of raw material rosins, Preferably it is 0.02-0.10 weight part. When the amount is less than 0.01 parts by weight, the content of the low molecular weight component and the high molecular weight component in the obtained component (A) is small. Therefore, the rosin-modified phenol resin is increased in molecular weight and added to the aliphatic hydrocarbon solvent. When the solubility is poor and the amount exceeds 0.12 parts by weight, the amount of parastrinic acid, abietic acid and neoabietic acid contained in the component (A) contributing to the reaction with the component (C) decreases. Therefore, it becomes difficult to increase the molecular weight of the rosin-modified phenol resin.
原料ロジン類に前記加熱処理を行うことにより下記（１）（以下、要件（１）と略記することがある）および要件（２）（以下、要件（２）と略記することがある）を満たすロジン（Ａ）が得られる。
（１）前記（Ａ）成分中に、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の重量平均分子量１以上１９９以下である低分子量成分（ａ１）５〜１２％、かつ重量平均分子量４０１以上２０００以下である高分子量成分（ａ２）４〜６％が含まれる。
（２）前記（Ａ）成分中に含まれるパラストリン酸、アビエチン酸およびネオアビエチン酸の合計含有量（ｔ１）（ガスクロマトグラフィー法により測定された合計含有量をいう）の原料ロジン類中に含まれる前記合計含有量（ｔ２）に対する比率［（ｔ１／ｔ２）×１００］が、８８％以上である。
By subjecting the raw material rosins to the heat treatment, the following (1) (hereinafter sometimes abbreviated as requirement (1)) and requirement (2) (hereinafter sometimes abbreviated as requirement (2)) are satisfied. Rosin (A) is obtained.
(1) In the component (A), a low molecular weight component (a1) having a weight average molecular weight of 1 to 199 in terms of polystyrene by gel permeation chromatography is 5 to 12% and a weight average molecular weight of 401 to 2000. The high molecular weight component (a2) is 4 to 6%.
(2) Included in raw material rosins of the total content (t1) (referring to the total content measured by gas chromatography method) of parastrinic acid, abietic acid and neoabietic acid contained in the component (A) The ratio [(t1 / t2) × 100] to the total content (t2) is 88% or more.
要件（１）は、（ａ１）成分（以下、（ａ１）成分という。）と（ａ２）成分（以下、（ａ２）成分という。）の含有割合を規定したものである。前記加熱処理により、原料ロジン類中には、新たに低分子量成分（ａ１）および高分子量成分（ａ２）が生成する。 Requirement (1) defines the content ratio of component (a1) (hereinafter referred to as component (a1)) and component (a2) (hereinafter referred to as component (a2)). By the heat treatment, a low molecular weight component (a1) and a high molecular weight component (a2) are newly generated in the raw material rosins.
前記処理によって得られる（Ａ）成分中に含まれる（ａ１）成分が５％未満となるとロジン変性フェノール樹脂の脂肪族炭化水素溶剤への溶解性が乏しくなり、１２％を超えると、（Ａ）成分の反応点が少なくなり、ロジン変性フェノール樹脂の高分子量化が困難となる。同様の観点から、（ａ１）成分の含有割合は、６〜１１％が好ましい。また、（ａ２）成分が４〜６％の範囲外となる場合も、高分子量化が困難となる。同様の観点から、（ａ２）成分の含有割合は、４．５〜６％が好ましい。ここで、（Ａ）成分中に含まれる前記（ａ１）成分および（ａ２）成分の含有割合は、（Ａ）成分を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とした場合において、（Ａ）成分全体を１００％とした場合の面積比として求めることができる。なお、前記（ａ１）成分には、未反応の（Ｂ）成分を含んでいても良い。 When the component (a1) contained in the component (A) obtained by the treatment is less than 5%, the solubility of the rosin-modified phenol resin in the aliphatic hydrocarbon solvent becomes poor, and when it exceeds 12%, the component (A) The reaction points of the components are reduced, and it becomes difficult to increase the molecular weight of the rosin-modified phenol resin. From the same viewpoint, the content ratio of the component (a1) is preferably 6 to 11%. Moreover, when the component (a2) is outside the range of 4 to 6%, it is difficult to increase the molecular weight. From the same viewpoint, the content ratio of the component (a2) is preferably 4.5 to 6%. Here, the content ratio of the component (a1) and the component (a2) contained in the component (A) is the component (A) when the component (A) is converted to polystyrene by gel permeation chromatography. It can be determined as an area ratio when the whole is 100%. The component (a1) may contain an unreacted component (B).
要件（２）は、（Ａ）成分中に含まれるパラストリン酸、アビエチン酸およびネオアビエチン酸の含有量が、（Ａ）成分の製造に用いた原料ロジン中の含有量に対して一定以上保持されていることを規定したものである。パラストリン酸、アビエチン酸およびネオアビエチン酸は、後述する（Ｃ）成分との反応および（Ｄ）成分とのエステル化反応に必須の共役ジエン系樹脂酸類のうち、特に、これらの成分との反応性に富む樹脂酸である。要件（２）は、得られた（Ａ）成分が、加熱処理により前記３種の樹脂酸類の合計含有割合が過度に低下したものでないことを規定する意義を有する。 In requirement (2), the content of parastrinic acid, abietic acid and neoabietic acid contained in component (A) is maintained above a certain level relative to the content in raw material rosin used for the production of component (A). It stipulates that Parastrinic acid, abietic acid, and neoabietic acid are particularly reactive among these conjugated diene resin acids that are essential for the reaction with the component (C) and the esterification reaction with the component (D) described later. It is a resin acid rich in. Requirement (2) has the meaning which prescribes | regulates that the (A) component obtained is not what the total content rate of the said 3 types of resin acids fell too much by heat processing.
（Ａ）成分中に含まれるパラストリン酸、アビエチン酸およびネオアビエチン酸の合計含有量（ｔ１）の原料ロジン類中に含まれる前記合計含有量（ｔ２）に対する比率［（ｔ１／ｔ２）×１００］が、８８％未満となる場合、後述する（Ａ）成分と（Ｃ）成分との反応が十分に進行せず、高分子量化が困難となる。同様の観点から、前記比率は、９０％以上であることが好ましく、９０〜９８％の範囲がより好ましい。 (A) Ratio of the total content (t1) of parastrinic acid, abietic acid and neoabietic acid contained in the component to the total content (t2) contained in the raw material rosins [(t1 / t2) × 100] However, if it is less than 88%, the reaction between the component (A) and the component (C) described later does not proceed sufficiently, and it becomes difficult to increase the molecular weight. From the same viewpoint, the ratio is preferably 90% or more, and more preferably in the range of 90 to 98%.
なお、前記（Ａ）成分および原料ロジン類中に含まれるパラストリン酸、アビエチン酸およびネオアビエチン酸の合計含有量（ｔ１およびｔ２）は、ガスクロマトグラフィー（ＧＣ）により得られたそれぞれの全樹脂酸ピーク面積を１００％とした際の各樹脂酸のピーク面積割合を合算して求めることができる。参考までに、本発明に用いる原料ロジン類には、通常、パラストリン酸、アビエチン酸およびネオアビエチン酸が合計含有量で５０〜９５％程度含まれているが、（Ｃ）成分との反応性の点から、原料ロジン類中の前記合計含有量が７０〜９５％程度であることが好ましく、８０〜９５％程度であることがより好ましい。 The total content (t1 and t2) of parastrinic acid, abietic acid and neoabietic acid contained in the component (A) and the raw material rosins is the total resin acid obtained by gas chromatography (GC). The peak area ratio of each resin acid when the peak area is taken as 100% can be obtained by adding up. For reference, the raw material rosins used in the present invention usually contain about 50 to 95% of total content of parastrinic acid, abietic acid and neoabietic acid, but it is reactive with the component (C). From the viewpoint, the total content in the raw material rosins is preferably about 70 to 95%, more preferably about 80 to 95%.
さらに、前記（Ａ）成分の酸価（ＪＩＳ−Ｋ５６０１に準拠）は、ロジン変性フェノール樹脂の溶解性の観点から、（Ａ）成分の製造に用いた原料ロジン類の酸価に対して、１〜６％低下していることが好ましく、２〜６％低下していることがより好ましい。 Furthermore, the acid value (based on JIS-K5601) of the component (A) is 1 with respect to the acid value of the raw material rosins used for the production of the component (A) from the viewpoint of solubility of the rosin-modified phenol resin. It is preferably reduced by -6%, more preferably 2-6%.
本発明のオフセット印刷インキ用ロジン変性フェノール樹脂の製造方法は、前記（Ａ）成分を（Ｃ）成分と反応させた後、次いで（Ｄ）成分とエステル化反応させて得られる。（Ａ）成分と（Ｃ）成分および（Ｄ）成分の反応方法および反応条件は、（Ａ）成分に対して、（Ｃ）成分を１〜１２時間かけて滴下して反応させた後、次いで続いて（Ｄ）成分を加えて、温度１００〜３００℃程度でエステル化反応させることで目的のロジン変性フェノール樹脂を得ることができる。 The method for producing a rosin-modified phenol resin for offset printing ink of the present invention is obtained by reacting the component (A) with the component (C) and then esterifying with the component (D). The reaction method and reaction conditions of the component (A), the component (C), and the component (D) are as follows. The component (C) is reacted with the component (C) dropwise over 1 to 12 hours, and then reacted. Subsequently, the desired rosin-modified phenolic resin can be obtained by adding the component (D) and performing an esterification reaction at a temperature of about 100 to 300 ° C.
本発明の製造方法で用いる（Ｃ）成分としては、各種公知のものを特に制限なく使用できる。具体的には、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が挙げられ、レゾール型フェノール樹脂としては、水酸化ナトリウムや有機アミン等の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、ノボラック型フェノール樹脂としては、塩酸や硫酸等の酸性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・水洗したものが好ましい。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。また、前記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、また、前記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。また、（Ｃ）成分としては、特にロジン変性フェノール樹脂の高分子量化および脂肪族炭化水素溶剤への溶解性等の観点より、アルキル基の炭素数が１０未満、具体的にはアルキル基の炭素数４〜９程度のアルキルフェノールとホルムアルデヒドの縮合物が好ましい。 As (C) component used with the manufacturing method of this invention, various well-known things can be especially used without a restriction | limiting. Specifically, for example, a resol type phenol resin or a novolac type phenol resin can be mentioned. As the resol type phenol resin, phenols (P) and formaldehyde in the presence of a basic catalyst such as sodium hydroxide or organic amine. Examples thereof include a condensate obtained by subjecting (F) to an addition / condensation reaction within a range in which F / P (molar ratio) is usually about 1 to 3. In addition, examples of the novolak type phenol resin include condensates obtained by addition / condensation reaction in the presence of an acidic catalyst such as hydrochloric acid or sulfuric acid within a range in which F / P is usually about 0.5 to 2. Each condensate is preferably neutralized and washed with water. Each condensate can be produced in the presence of water or an organic solvent (such as xylene). Examples of the phenols include carboxylic acid, cresol, amylphenol, bisphenol A, butylphenol, octylphenol, nonylphenol, and dodecylphenol. Examples of the formaldehyde include formalin and paraformaldehyde. In addition, as the component (C), particularly from the viewpoint of increasing the molecular weight of the rosin-modified phenol resin and the solubility in an aliphatic hydrocarbon solvent, the alkyl group has less than 10 carbon atoms, specifically, the alkyl group carbon. A condensate of alkylphenol and formaldehyde of about 4 to 9 is preferable.
本発明の製造方法においては、前記（Ｃ）成分を（Ａ）成分に滴下で加えることが望ましく、そうすることで、（Ｃ）成分同士の自己縮合を抑制し、かつ最終的に得られるロジン変性フェノール樹脂の分子量を高めることができる。（Ｃ）成分の使用量も特に限定されないが、特にロジン変性フェノール樹脂の高分子量化および脂肪族炭化水素溶剤への溶解性等の観点より、通常、原料ロジン類１００重量部に対して１０〜１３０重量部程度、好ましくは３０〜１１０重量部程度であり、より好ましくは５０〜９０重量部程度である。 In the production method of the present invention, it is desirable to add the component (C) dropwise to the component (A). By doing so, self-condensation between the components (C) is suppressed, and finally obtained rosin The molecular weight of the modified phenolic resin can be increased. The amount of the component (C) used is not particularly limited, but is usually 10 to 100 parts by weight of the raw material rosins from the viewpoint of increasing the molecular weight of the rosin-modified phenol resin and the solubility in an aliphatic hydrocarbon solvent. About 130 parts by weight, preferably about 30 to 110 parts by weight, more preferably about 50 to 90 parts by weight.
本発明の製造方法で用いる（Ｄ）成分としては、各種公知のものを特に制限なく使用できる。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５価以上のポリオール類等を例示でき、２種以上を組み合わせてもよい。（Ｄ）成分の中でも、特にロジン変性フェノール樹脂の高分子量化および脂肪族炭化水素溶剤への溶解性、ならびに印刷インキの耐ミスチング性等の観点より、トリオール類および／またはテトラオール類が好ましい。 As the component (D) used in the production method of the present invention, various known compounds can be used without particular limitation. 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 thereof include polyols having five or more valences such as all and dipentaerythritol, and two or more kinds may be combined. Among the components (D), triols and / or tetraols are preferable from the viewpoints of increasing the molecular weight of the rosin-modified phenolic resin, the solubility in an aliphatic hydrocarbon solvent, the misting resistance of the printing ink, and the like.
本発明では、ロジン変性フェノール樹脂の高分子量化の点から、（Ｃ）成分を（Ａ）成分中に滴下しながら、十分に反応させた後に（Ｄ）成分を添加することが好ましい。原料ロジン類に対する（Ｄ）成分の使用量は特に限定されないが、特にロジン変性フェノール樹脂の高分子量化および脂肪族炭化水素溶剤への溶解性、ならびに印刷インキの耐ミスチング性等の観点より、原料ロジン類の酸価（ＡＶ）（ＪＩＳ−Ｋ５６０１に準拠）と（Ｄ）成分の水酸基価（ＯＨ（Ｄ））（ＪＩＳ−Ｋ００７０に準拠）との比（ＯＨ（Ｄ）／ＡＶ）が０．５〜１．３程度、好ましくは０．５〜１．１程度となる範囲であることが好ましい。 In the present invention, from the viewpoint of increasing the molecular weight of the rosin-modified phenol resin, it is preferable to add the component (D) after sufficiently reacting the component (C) while dropping the component (C) into the component (A). The amount of component (D) used relative to the raw material rosins is not particularly limited. In particular, from the viewpoints of increasing the molecular weight of the rosin-modified phenolic resin and its solubility in aliphatic hydrocarbon solvents, and the misting resistance of printing inks, etc. The ratio (OH (D) / AV) of the acid value (AV) of rosins (based on JIS-K5601) to the hydroxyl value (OH (D)) (based on JIS-K0070) of the component (D) is 0. The range is preferably about 5 to 1.3, and more preferably about 0.5 to 1.1.
本発明においては、更にロジン変性フェノール樹脂の分子量を高めることを目的に、必要に応じて、エステル化反応時に二価金属酸化物および／または二価金属水酸化物である金属化合物（Ｅ）（以下、（Ｅ）成分という。）を添加できる。（Ｅ）成分としては、各種金属の酸化物や水酸化物などを使用できるが、ロジン変性フェノール樹脂を高分子量化させるため、二価金属酸化物および／または二価金属水酸化物を用いることが好ましい。具体的には、前記酸化物として、酸化マグネシウムや酸化カルシウム、酸化亜鉛等、前記水酸化物として、水酸化マグネシウムや水酸化カルシウム、水酸化亜鉛等が挙げられる。なお、これらは単独でも２種以上を組み合わせてもよい。また、（Ｅ）成分の使用量は、ロジン類１００重量部に対して、０．１〜０．８重量部、好ましくは０．２〜０．７重量部、より好ましくは０．４〜０．７重量部である。０．１重量部未満であると、（Ｅ）成分による高分子量化の効果が乏しくなり、０．８重量部を超えると（Ｂ）成分と不溶性の塩を形成しうる問題がある。なお、（Ｅ）成分は、単独で添加しても、（Ｃ）成分や（Ｄ）成分と同時に添加しても良い。 In the present invention, for the purpose of further increasing the molecular weight of the rosin-modified phenolic resin, a metal compound (E) (divalent metal oxide and / or divalent metal hydroxide) at the time of esterification reaction, if necessary. (Hereinafter referred to as component (E)) can be added. As the component (E), oxides or hydroxides of various metals can be used. In order to increase the molecular weight of the rosin-modified phenol resin, a divalent metal oxide and / or a divalent metal hydroxide should be used. Is preferred. Specifically, examples of the oxide include magnesium oxide, calcium oxide, and zinc oxide, and examples of the hydroxide include magnesium hydroxide, calcium hydroxide, and zinc hydroxide. In addition, these may be individual or may combine 2 or more types. Moreover, the usage-amount of (E) component is 0.1-0.8 weight part with respect to 100 weight part of rosins, Preferably it is 0.2-0.7 weight part, More preferably, it is 0.4-0. 0.7 parts by weight. When the amount is less than 0.1 parts by weight, the effect of increasing the molecular weight by the component (E) is poor, and when it exceeds 0.8 parts by weight, there is a problem that an insoluble salt can be formed with the component (B). In addition, (E) component may be added independently or may be added simultaneously with (C) component and (D) component.
本発明の前記製造方法で得られるロジン変性フェノール樹脂は高分子量であることを特徴としており、重量平均分子量（ゲルパーミエ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）としては、脂肪族炭化水素溶剤に対する溶解性および印刷インキの耐ミスチング性および流動性等の観点より、通常５０，０００〜１３０，０００程度が好ましく、７０，０００〜１００，０００程度がより好ましい。 The rosin-modified phenolic resin obtained by the production method of the present invention is characterized by having a high molecular weight, and the weight average molecular weight (polystyrene conversion value by gel permeation chromatography method) is soluble in an aliphatic hydrocarbon solvent. and from the viewpoint of resistance to misting and flowability or the like of the printing ink, it is usually preferably 5 0,000～1 3 about 0,000, 7 0,000～1 0 about 0,000 is not more preferable.
また、本発明に係るロジン変性フェノール樹脂は、前述のように、脂肪族炭化水素溶剤への溶解性に優れる。具体的には、当該ロジン変性フェノール樹脂を、脂肪族炭化水素溶剤の１０重量％溶液とした場合における曇点（濁りが生じるときの温度）が５０〜１５０℃程度、好ましくは６０〜１２０℃、より好ましくは７０〜９０℃であることを意味する。本発明ではこの曇点を溶解性の指標とする。なお、前記溶剤としては、芳香族含有量が１％未満であり且つアニリン点が７０〜１００℃のものが好ましく、市販品としては、例えばＪＸ日鉱日石エネルギー（株）製の０号ソルベントやＡＦソルベント（４号、５号、６号、７号等）などを入手できる。これらの中でも汎用性のあるＡＦソルベント６号を用いることが好ましい。また、当該脂肪族炭化水素溶剤の「１０重量％溶液」とは、具体的には、本発明に係るロジン変性フェノール樹脂（固体）／ＡＦソルベント（ＪＸ日鉱日石エネルギー（株）製 ナフテン系脂肪族炭化水素溶剤）が重量比で１／９となる溶液を意味する。 Moreover, the rosin modified phenolic resin according to the present invention is excellent in solubility in an aliphatic hydrocarbon solvent as described above. Specifically, when the rosin-modified phenol resin is a 10% by weight solution of an aliphatic hydrocarbon solvent, the cloud point (temperature when turbidity occurs) is about 50 to 150 ° C, preferably 60 to 120 ° C. More preferably, it means 70 to 90 ° C. In the present invention, this cloud point is used as an index of solubility. The solvent preferably has an aromatic content of less than 1% and an aniline point of 70 to 100 ° C., and examples of commercially available products include No. 0 Solvent manufactured by JX Nippon Mining & Energy Co., Ltd. AF solvent (4, 5, 6, 7, etc.) can be obtained. Among these, it is preferable to use versatile AF solvent No. 6. The “10 wt% solution” of the aliphatic hydrocarbon solvent specifically refers to the rosin-modified phenol resin (solid) / AF solvent according to the present invention (a naphthenic fat manufactured by JX Nippon Mining & Energy Corporation). Group hydrocarbon solvent) means a solution having a weight ratio of 1/9.
また、当該ロジン変性フェノール樹脂の他の物性は特に限定されないが、例えば３３％アマニ油粘度は、特に印刷インキの耐ミスチング性等の観点より通常５〜２５Ｐａ・ｓ程度、好ましくは７〜２０Ｐａ・ｓ程度である。 The other physical properties of the rosin-modified phenol resin are not particularly limited. For example, the 33% linseed oil viscosity is usually about 5 to 25 Pa · s, preferably 7 to 20 Pa · s, particularly from the viewpoint of misting resistance of the printing ink. It is about s.
また、軟化点（ＪＩＳ−Ｋ５９０３に準拠）は、特に印刷インキの耐ミスチング性および乾燥性等の観点より通常１２０〜２００℃程度、好ましくは１４０〜２００℃程度である。 The softening point (based on JIS-K5903) is usually about 120 to 200 ° C., preferably about 140 to 200 ° C., particularly from the viewpoint of misting resistance and drying properties of printing ink.
また、酸価（ＪＩＳ−Ｋ５６０１に準拠）は、特にロジン変性フェノール樹脂の脂肪族炭化水素溶剤中での溶解性と印刷インキの耐乳化性等の観点より、通常１０〜２５ｍｇＫＯＨ／ｇ程度、好ましくは１５〜２０ｍｇＫＯＨ／ｇである。 The acid value (based on JIS-K5601) is usually about 10 to 25 mgKOH / g, preferably from the viewpoint of the solubility of the rosin-modified phenolic resin in an aliphatic hydrocarbon solvent and the emulsification resistance of the printing ink. Is 15-20 mg KOH / g.
本発明のオフセット印刷インキ用ゲルワニスは、本発明のロジン変性フェノール樹脂とゲル化剤を非芳香族系溶剤中で反応（通常１００〜２４０℃程度）させてなるものである。該非芳香族系溶剤としては、各種公知の脂肪族炭化水素溶剤および／または植物油類といった非香族系の印刷インキ溶剤が挙げられる。 The gel varnish for offset printing ink of the present invention is obtained by reacting the rosin-modified phenol resin of the present invention and a gelling agent in a non-aromatic solvent (usually about 100 to 240 ° C.). Examples of the non-aromatic solvent include non-aromatic printing ink solvents such as various known aliphatic hydrocarbon solvents and / or vegetable oils.
前記ゲル化剤としては、各種公知のものを特に制限なく使用できる。具体的には、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系キレート剤や、テトライソプロポキシチタン、テトラブトキシチタン、ジプロポキシビス（アセチルアセトナト）チタン等のチタン系キレート剤、テトラブトキシジルコニウム等のジルコニウム系キレート剤、トリレンジイソシアネート、ジフェニルジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート等のポリイソシアネート等を例示でき、２種以上を組み合わせてもよい。これらの中でも、特に印刷インキの耐乳化性等の観点よりアルミ系キレート剤が好ましい。なお、ゲル化剤の使用量は特に限定されないが、本発明に係るロジン変性フェノール樹脂１００重量部（固形分換算）に対して通常０．５〜５重量部程度である。 As the gelling agent, various known ones can be used without particular limitation. Specifically, for example, aluminum chelates such as aluminum octylate, aluminum stearate, aluminum triisopropoxide, aluminum tributoxide, aluminum dipropoxide monoacetyl acetate, aluminum dibutoxide monoacetyl acetate, aluminum triacetyl acetate, etc. And titanium-based chelating agents such as tetraisopropoxytitanium, tetrabutoxytitanium, dipropoxybis (acetylacetonato) titanium, zirconium-based chelating agents such as tetrabutoxyzirconium, tolylene diisocyanate, diphenyl diisocyanate, hexamethylene diisocyanate, xylylene diene Examples include isocyanates, polyisocyanates such as isophorone diisocyanate, etc. . Among these, an aluminum chelating agent is particularly preferable from the viewpoint of emulsification resistance of the printing ink. In addition, although the usage-amount of a gelatinizer is not specifically limited, It is about 0.5-5 weight part normally with respect to 100 weight part (solid content conversion) of the rosin modified phenol resin which concerns on this invention.
前記脂肪族炭化水素溶剤としては、前記したＪＸ日鉱日石エネルギー（株）の０号ソルベントやＡＦソルベント（４号、５号、６号、７号等）を例示でき、芳香族含有量が１％未満であり且つアニリン点が７０〜１００℃のものが特に好ましい。また、沸点２００℃以上のものは環境面より好ましい。なお、該脂肪族炭化水素溶剤の使用量は特に限定されないが、本発明に係るロジン変性フェノール樹脂１００重量部（固形分換算）に対して通常１０〜２００重量部程度、好ましくは１０〜１５０重量部程度である。 Examples of the aliphatic hydrocarbon solvent include No. 0 solvent and AF solvent (No. 4, No. 5, No. 6, No. 7, etc.) of the above-mentioned JX Nippon Oil & Energy Corporation, and the aromatic content is 1 % Of the aniline point is preferably 70 to 100 ° C. Moreover, the thing whose boiling point is 200 degreeC or more is preferable from an environmental viewpoint. The amount of the aliphatic hydrocarbon solvent used is not particularly limited, but is usually about 10 to 200 parts by weight, preferably 10 to 150 parts by weight, based on 100 parts by weight (in terms of solid content) of the rosin-modified phenolic resin according to the present invention. It is about a part.
前記植物油類としては、各種公知のものを特に制限なく使用できる。具体的には、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などといった前記植物油のモノエステル等を例示でき、２種以上を組み合わせてもよい。植物油類としては、印刷物の特に乾燥性の点より、分子中に不飽和結合を有する脂肪酸を多く含む植物油、特に大豆油および／またはアマニ油が好ましい。なお、該植物油類の使用量は特に限定されないが、本発明に係るロジン変性フェノール樹脂１００重量部（固形分換算）に対して通常１０〜２００重量部程度、好ましくは１０〜１５０重量部程度である。 Various known oils can be used without particular limitation as the vegetable oils. Specifically, for example, flaxseed oil, tung oil, safflower oil, dehydrated castor oil, soybean oil and other vegetable oils, flaxseed oil fatty acid methyl, soybean oil fatty acid methyl, flaxseed oil fatty acid ethyl, soybean oil fatty acid ethyl, flaxseed oil Examples include monoesters of the 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 two or more of them may be combined. As the vegetable oils, vegetable oils containing a large amount of fatty acids having an unsaturated bond in the molecule, particularly soybean oil and / or linseed oil are preferable from the viewpoint of the dryness of the printed matter. In addition, although the usage-amount of this vegetable oil is not specifically limited, About 10-200 weight part normally with respect to 100 weight part (solid content conversion) of the rosin modified phenol resin which concerns on this invention, Preferably it is about 10-150 weight part. is there.
本発明のオフセット印刷インキは、本発明のゲルワニスと顔料（黄、紅、藍、墨）を含むものであり、必要に応じて各種公知の添加剤配合した後、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・調製したうえで利用に供される。前記添加剤としては、インキの流動性やインキ皮膜の表面を改質するための界面活性剤、ワックス、酸化防止剤等が挙げられる。 The offset printing ink of the present invention contains the gel varnish of the present invention and a pigment (yellow, red, indigo, black), and after blending various known additives as necessary, roll mill, ball mill, attritor, sand mill These are used after being kneaded and prepared so as to obtain an appropriate ink constant using a known ink manufacturing apparatus. Examples of the additive include surfactants, waxes, antioxidants and the like for modifying the fluidity of the ink and the surface of the ink film.
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、いずれも本発明の範囲を限定するものではない。なお、以下「部」、「％」は特に断りがない限り、重量基準で示す。 Hereinafter, the present invention will be described more specifically with reference to production examples and examples, but these do not limit the scope of the present invention. Hereinafter, “parts” and “%” are based on weight unless otherwise specified.
また、重量平均分子量は、ゲルパーメーションクロマトグラフィー（ＧＰＣ）によりテトラヒドロフラン溶媒下で測定したポリスチレン換算値である。ＧＰＣ装置としては、ＨＬＣ−８３２０（東ソー（株）製）を、カラムとしては、ＴＳＫ−ＧＥＬカラム（東ソー（株）製）を用いた。また、低分子量成分および高分子量成分の含有量は、全成分ピークの合計面積を１００にしたときの該当成分の面積比率（％）で示す。 Moreover, a weight average molecular weight is a polystyrene conversion value measured in a tetrahydrofuran solvent by gel permeation chromatography (GPC). As the GPC apparatus, HLC-8320 (manufactured by Tosoh Corporation) was used, and as the column, a TSK-GEL column (manufactured by Tosoh Corporation) was used. Moreover, content of a low molecular weight component and a high molecular weight component is shown by the area ratio (%) of an applicable component when the total area of all the component peaks is set to 100.
また、樹脂酸類中のパラストリン酸、アビエチン酸およびネオアビエチン酸（以下、共役ジエン系樹脂酸類という。）の合計含有量の比率（以下、含有比率という。）は、ガスクロマトグラフィー（ＧＣ）により測定した値を用いて、以下の式１により算出した。ＧＣ装置としては、ＧＣ−１４Ａ（（株）島津製作所製）を、カラムとしては、ＤＢ−５（アジレント・テクノロジー（株）製）を用いた。
（式１）含有比率 ＝｛成分（Ａ）中に含まれる前記樹脂酸類の合計含有量（ｔ１）｝／｛原料ロジン類中に含まれる前記樹脂酸類の合計含有量（ｔ２）｝×１００（％）
The ratio of the total content of parastrinic acid, abietic acid and neoabietic acid (hereinafter referred to as conjugated diene resin acids) in the resin acids (hereinafter referred to as content ratio) was measured by gas chromatography (GC). The calculated value was calculated by the following formula 1. As the GC device, GC-14A (manufactured by Shimadzu Corporation) was used, and as the column, DB-5 (manufactured by Agilent Technologies) was used.
(Formula 1) Content ratio = {Total content (t1) of the resin acids contained in the component (A)} / {Total content (t2) of the resin acids contained in the raw material rosins} × 100 ( %)
また、曇点は、ロジン変性フェノール樹脂（固体）／ＡＦソルベント６号が重量比で１／９となる溶液を用い、ＮＯＶＯＭＡＴＩＣＳ社製の自動曇点測定装置（製品名「ＣＨＥＭＯＴＯＲＩＣ ＩＩ」）により得られた測定値である。 The cloud point is obtained with an automatic cloud point measuring device (product name “CHEMOTORIC II”) manufactured by NOVOMATICS, using a solution in which the weight ratio of rosin-modified phenol resin (solid) / AF solvent 6 is 1/9. Measured value.
また、３３％アマニ油粘度（Ｐａ・ｓ）は、樹脂とアマニ油を１：２の重量比で加熱混合したものについて、日本レオロジー機器（株）製コーン・アンド・プレート型粘度計を用いて２５℃で測定した値である。 The 33% linseed oil viscosity (Pa · s) was obtained by mixing a resin and linseed oil at a weight ratio of 1: 2, using a cone and plate viscometer manufactured by Nippon Rheology Equipment Co., Ltd. It is the value measured at 25 ° C.
＜（Ｃ）成分の製造＞
製造例１
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１０００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６付近に調整した。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樹脂の７０％キシレン溶液（以下、（Ｃ−１）成分という。）を得た。
<Production of component (C)>
Production Example 1
A reaction vessel equipped with a stirrer, a reflux condenser with a water separator and a thermometer was charged with 1000 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. . Next, 89 parts of 45% sodium hydroxide solution was charged into the same reaction vessel, the reaction system was gradually warmed up to 90 ° C. while cooling, then kept for 2 hours, and sulfuric acid was added dropwise to bring the pH to around 6. It was adjusted. Thereafter, the aqueous layer containing formaldehyde and the like was removed, and after washing again with water, the contents were cooled to obtain a 70% xylene solution of resole type octylphenol resin (hereinafter referred to as (C-1) component).
製造例２
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、ノニルフェノール１０００部、９２％パラホルムアルデヒド４４４部、キシレン６０４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６付近に調整した。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樹脂の７０％キシレン溶液（以下、（Ｃ−２）成分という。）を得た。
Production Example 2
A reaction vessel equipped with a stirrer, a reflux condenser with a water separator and a thermometer was charged with 1000 parts of nonylphenol, 444 parts of 92% paraformaldehyde, 604 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 up to 90 ° C. while cooling, then kept for 2 hours, and sulfuric acid was added dropwise to bring the pH to around 6. It was adjusted. 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% xylene solution of resole type nonylphenol resin (hereinafter referred to as component (C-2)).
製造例３
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、ブチルフェノール１０００部、９２％パラホルムアルデヒド５４３部、キシレン６４３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６付近に調整した。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樹脂の７０％キシレン溶液（以下、（Ｃ−３）成分という。）を得た。
Production Example 3
A reaction vessel equipped with a stirrer, a reflux condenser with a water separator and a thermometer was charged with 1000 parts of butylphenol, 543 parts of 92% paraformaldehyde, 643 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 up to 90 ° C. while cooling, then kept for 2 hours, and sulfuric acid was added dropwise to bring the pH to around 6. It was adjusted. 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% xylene solution of resole-type butylphenol resin (hereinafter referred to as (C-3) component).
＜ロジン変性フェノール樹脂の製造＞
実施例１
撹拌器、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、原料ロジン類としてガムロジン１０００部（荒川化学工業（株）製、商品名「ＣＧ−ＷＷ」、重量平均分子量が１以上１９９以下である低分子量成分２．７％、４０１以上２０００以下である高分子量成分３．２％、共役ジエン系樹脂酸類の合計含有量（ｔ２）は８５．０％、酸価１７０ｍｇＫＯＨ／ｇ）を仕込み、撹拌下に２２０℃まで昇温して溶融させた。溶融後のガムロジンの物性に変化はなく、その後、（Ｂ）成分としてパラトルエンスルホン酸（以下、ＰＴＳという。）０．５部を仕込み３０分間保温して加熱処理を行い、（Ａ）成分を得た。（Ａ）成分中の低分子量成分（ａ１）の含有量は６．５％、高分子量成分（ａ２）の含有量は４．７％、共役ジエン系樹脂酸類の合計含有量（ｔ１）は８１．５％となり、含有比率［（ｔ１／ｔ２）×１００］は９５．９％であった。また、（Ａ）成分の酸価は、原料ロジンに対して２．３％低下し１６６ｍｇＫＯＨ／ｇであった。ついで製造例１で得られた（Ｃ−１）成分１０００部（固形分７００部）を、６時間かけて系内に滴下した。滴下終了後、グリセリン８４部を仕込み、２２０〜２６０℃の温度範囲内で反応系の酸価が２５以下となるまでエステル化反応を実施した。なお、反応系の樹脂溶液の外観はクリアであり、濁りは発生していなかった。その後、反応系を０．０２ＭＰａで１０分間減圧し、冷却することにより、固形状のロジン変性フェノール樹脂を得た。得られたロジン変性フェノール樹脂の重量平均分子量、曇点、３３％アマニ油粘度、酸価および軟化点を表１に示す（以下同様）。
<Production of rosin-modified phenolic resin>
Example 1
In a reaction vessel equipped with a stirrer, a reflux condenser with a water divider and a thermometer, 1000 parts of gum rosin (trade name “CG-WW” manufactured by Arakawa Chemical Industries, Ltd.) as a raw material rosin, a weight average molecular weight of 1 or more 199% or less of low molecular weight component 2.7%, 401 or more and 2000 or less high molecular weight component 3.2%, total content of conjugated diene resin acids (t2) is 85.0%, acid value 170 mgKOH / g) Was heated to 220 ° C. with stirring and melted. There was no change in the physical properties of the gum rosin after melting, and then 0.5 parts of paratoluenesulfonic acid (hereinafter referred to as PTS) was added as the component (B) and heat-treated for 30 minutes, and the component (A) was heated. Obtained. In the component (A), the content of the low molecular weight component (a1) is 6.5%, the content of the high molecular weight component (a2) is 4.7%, and the total content (t1) of the conjugated diene resin acids is 81. The content ratio [(t1 / t2) × 100] was 95.9%. The acid value of component (A) was 166 mgKOH / g, a 2.3% decrease relative to the raw material rosin. Next, 1000 parts (700 parts of solid content) of the component (C-1) obtained in Production Example 1 was dropped into the system over 6 hours. After completion of the dropwise addition, 84 parts of glycerin was charged, and the esterification reaction was carried out within the temperature range of 220 to 260 ° C. until the acid value of the reaction system became 25 or less. The appearance of the resin solution in the reaction system was clear and no turbidity was generated. Thereafter, the reaction system was depressurized at 0.02 MPa for 10 minutes and cooled to obtain a solid rosin-modified phenol resin. The weight average molecular weight, cloud point, 33% linseed oil viscosity, acid value and softening point of the obtained rosin-modified phenol resin are shown in Table 1 (the same applies hereinafter).
実施例２
加熱処理におけるＰＴＳの使用量を０．２部に変更した以外は、実施例１と同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。なお、製造途中で得られた（Ａ）成分中の低分子量成分および高分子量成分の含有量、共役ジエン系樹脂酸類の含有比率［（ｔ１／ｔ２）×１００］ならびに酸価低下率を表１に示す（以下同様）。
Example 2
A solid rosin-modified phenol resin was obtained in the same manner as in Example 1 except that the amount of PTS used in the heat treatment was changed to 0.2 parts. Table 1 shows the contents of the low molecular weight component and the high molecular weight component in the component (A) obtained during the production, the content ratio of the conjugated diene resin acids [(t1 / t2) × 100], and the acid value reduction rate. (The same applies hereinafter).
実施例３
ＰＴＳの使用量を１．０部に変更した以外は、実施例１と同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。
Example 3
A solid rosin-modified phenolic resin was obtained in the same manner as in Example 1 except that the amount of PTS used was changed to 1.0 part.
実施例４
加熱処理におけるガムロジンの温度を２４０℃で溶融させて、ＰＴＳ０．５部を仕込み２０分間保温した以外は、実施例１と同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。
Example 4
A solid rosin-modified phenolic resin was obtained in the same manner as in Example 1 except that the temperature of the gum rosin in the heat treatment was melted at 240 ° C. and 0.5 part of PTS was charged and kept warm for 20 minutes.
実施例５
（Ｂ）成分をＰＴＳからメタンスルホン酸（以下、ＭＳＡという。）０．３部に変更した以外は、実施例１と同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。
Example 5
(B) A solid rosin modified phenolic resin was obtained in the same manner as in Example 1 except that the component was changed from PTS to 0.3 part of methanesulfonic acid (hereinafter referred to as MSA).
実施例６
（Ｃ−１）成分の滴下終了後、グリセリン８４部及び（Ｅ）成分として酸化亜鉛７部を仕込んだ以外は、実施例１と同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。
Example 6
(C-1) After completion | finish of dripping of a component, it carried out by the same method as Example 1 except having prepared 7 parts of zinc oxide as 84 parts of glycerol and (E) component, and obtained solid rosin modified phenolic resin. .
実施例７
実施例６で、（Ｅ）成分を酸化亜鉛から水酸化マグネシウムに変更した以外は、実施例６と同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。
Example 7
A solid rosin-modified phenolic resin was obtained in the same manner as in Example 6 except that the component (E) was changed from zinc oxide to magnesium hydroxide in Example 6.
実施例８
加熱処理における保温時間を１５分間に変更した以外は、実施例１と同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。
Example 8
Except having changed the heat retention time in heat processing into 15 minutes, it carried out by the method similar to Example 1, and obtained the solid rosin modified phenol resin.
実施例９
加熱処理における保温時間を６０分間に変更した以外は実施例１と同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。
Example 9
Except having changed the heat retention time in heat processing into 60 minutes, it carried out by the method similar to Example 1, and obtained solid rosin modified phenolic resin.
実施例１０
（Ｃ−１）成分から（Ｃ−２）成分１１００部（固形分７７０部）に変更した以外は、実施例１と同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。
Example 10
A solid rosin-modified phenolic resin was obtained in the same manner as in Example 1 except that the component (C-1) was changed to the component (C-2) 1100 parts (solid content 770 parts).
実施例１１
（Ｃ−１）成分の滴下終了後、グリセリン４２部及びペンタエリスリトール４６部を仕込んだ以外は、実施例１と同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。
Example 11
(C-1) After completion | finish of dripping of a component, it carried out by the same method as Example 1 except having prepared 42 parts of glycerol and 46 parts of pentaerythritol, and obtained solid rosin modified phenolic resin.
比較例１
（Ｃ−１）成分の滴下終了後、グリセリン８４部及びＰＴＳ１．０部を仕込んだ以外は、実施例１と同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。得られたロジン変性フェノール樹脂の重量平均分子量、曇点、３３％アマニ油粘度、酸価および軟化点を表２に示す（以下同様）。
Comparative Example 1
(C-1) After completion | finish of dripping of a component, it carried out by the method similar to Example 1 except having prepared 84 parts of glycerol and 1.0 part of PTS, and obtained solid rosin modified phenolic resin. The weight average molecular weight, cloud point, 33% linseed oil viscosity, acid value and softening point of the obtained rosin-modified phenol resin are shown in Table 2 (the same applies hereinafter).
比較例２
加熱処理においてＰＴＳを添加せずに、実施例１と同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。
Comparative Example 2
The heat treatment was carried out in the same manner as in Example 1 without adding PTS to obtain a solid rosin-modified phenolic resin.
比較例３
低分子量成分が２．８％、高分子量成分が３．０％、共役ジエン系樹脂酸類の合計含有量が８５.２％および酸価が１６５ｍｇＫＯＨ／ｇのガムロジン（荒川化学工業（株）製、商品名「ＣＧ−ＷＷ」）を用いて、比較例２と同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。
Comparative Example 3
Gum rosin (produced by Arakawa Chemical Industries, Ltd.) having a low molecular weight component of 2.8%, a high molecular weight component of 3.0%, a total content of conjugated diene resin acids of 85.2% and an acid value of 165 mgKOH / g, Using a product name “CG-WW”), the same method as in Comparative Example 2 was performed to obtain a solid rosin-modified phenolic resin.
比較例４
ＰＴＳの使用量を１．５部に変更した以外は、実施例１と同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。なお、製造途中で得られた（Ａ）成分中の低分子量成分および高分子量成分の含有量、共役ジエン系樹脂酸類の含有比率［（ｔ１／ｔ２）×１００］ならびに酸価低下率を表２に示す（以下同様）。
Comparative Example 4
Except having changed the usage-amount of PTS into 1.5 parts, it carried out by the method similar to Example 1, and obtained the solid rosin modified phenolic resin. Table 2 shows the contents of the low molecular weight component and the high molecular weight component in the component (A) obtained during the production, the content ratio [(t1 / t2) × 100] of the conjugated diene resin acids, and the acid value reduction rate. (The same applies hereinafter).
比較例５
ＰＴＳの添加直後に（Ｃ−１）成分１０００部（固形分７００部）を滴下した以外は、実施例１と同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。
Comparative Example 5
A solid rosin-modified phenolic resin was obtained in the same manner as in Example 1 except that 1000 parts (C-1) component (700 parts solids) was added dropwise immediately after the addition of PTS.
比較例６
加熱処理における保温時間を９０分間に変更した以外は、実施例１と同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。
Comparative Example 6
Except having changed the heat retention time in heat processing into 90 minutes, it carried out by the method similar to Example 1, and obtained solid rosin modified phenolic resin.
比較例７
加熱処理においてＰＴＳを添加せずに、実施例７と同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。
Comparative Example 7
The heat treatment was carried out in the same manner as in Example 7 without adding PTS to obtain a solid rosin-modified phenolic resin.
比較例８
溶融後のガムロジンに水酸化マグネシウム７部を仕込み、（Ｃ−１）成分の滴下終了後、グリセリン８４部及びＰＴＳ０．５部を仕込んだ以外は、比較例１と同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。
Comparative Example 8
In the same manner as in Comparative Example 1 except that 7 parts of magnesium hydroxide was added to the melted gum rosin and 84 parts of glycerin and 0.5 part of PTS were added after completion of the dropwise addition of the component (C-1). A rosin-modified phenolic resin was obtained.
比較例９
比較例１で、（Ｃ−１）成分の量を５７１部（固形分４００部）にした以外は同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。
Comparative Example 9
A solid rosin-modified phenol resin was obtained in the same manner as in Comparative Example 1 except that the amount of the component (C-1) was changed to 571 parts (solid content 400 parts).
比較例１０
比較例２で、（Ｃ）成分について、（Ｃ−２）成分５００部（固形分３５０部）を３時間かけて系内に滴下し、続いて製造例３で得られた（Ｃ−３）成分５００部（固形分３５０部）を、３時間かけて系内に滴下する方法に変更し、滴下終了後、グリセリン９３部及び水酸化マグネシウム７部を仕込んだ以外は同様の方法で行い、固形状のロジン変性フェノール樹脂を得た。
Comparative Example 10
In Comparative Example 2, about component (C), 500 parts of component (C-2) (solid content 350 parts) was dropped into the system over 3 hours, and then obtained in Production Example 3 (C-3). 500 parts (solid content 350 parts) was changed to a method of dropping into the system over 3 hours, and after completion of dropping, 93 parts of glycerin and 7 parts of magnesium hydroxide were charged in the same manner. A rosin-modified phenolic resin having a shape was obtained.
＜ゲルワニスの調製＞
実施例１のロジン変性フェノール樹脂４５．０部、大豆油１０．０部およびＡＦソルベント７号（ＪＸ日鉱日石エネルギー（株）製、沸点範囲２５９〜２８２℃、芳香族炭化水素含有率０％）４４．０部を１８０℃で３０分間混合溶解した。次にこれを６０℃まで冷却した後、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）１．０部を加え、１９０℃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。また、実施例２〜１１および比較例１〜１０のロジン変性フェノール樹脂についても同様にしてゲルワニスを調製した。
<Preparation of gel varnish>
45.0 parts of rosin-modified phenolic resin of Example 1, 10.0 parts of soybean oil and AF Solvent No. 7 (manufactured by JX Nippon Oil & Energy Corporation, boiling range 259-282 ° C., aromatic hydrocarbon content 0% 44.0 parts were mixed and dissolved at 180 ° C. for 30 minutes. Next, after cooling to 60 ° C., 1.0 part of aluminum dipropoxide monoacetylacetate (trade name Kerope EP-2, manufactured by Hope Pharmaceutical Co., Ltd.) is added and heated to 190 ° C. for 1 hour to gel. The gel varnish was obtained by making it react. Moreover, the gel varnish was similarly prepared about the rosin modified phenol resin of Examples 2-11 and Comparative Examples 1-10.
＜印刷インキの調製およびインキ性能試験＞
前記実施例および比較例のゲルワニスを用い、以下の配合割合で３本ロールミルにより練肉し、２５℃におけるＣ＆Ｐ粘度が２５±５Ｐａ・ｓ、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となるような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 ６６〜７１重量部
ＡＦソルベント７号 １１〜１６重量部
<Preparation of printing ink and ink performance test>
Using the gel varnishes of the examples and comparative examples, the mixture was kneaded with a three roll mill at the following blending ratio, the C & P viscosity at 25 ° C. was 25 ± 5 Pa · s, and the flow value (diameter value) of the spread meter at 25 ° C. was 38. A printing ink was prepared to give 0.0 ± 1.0.
Phthalocyanine blue (indigo pigment) 18 parts by weight Gel varnish 66-71 parts by weight AF Solvent No. 7 11-16 parts by weight
（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。数値が大きいほど光沢に優れる。
(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 reflectance of 60 ° -60 ° was measured with a gloss meter. The larger the value, the better the gloss.
（乳化率）
インキ３．９ｍｌを動的乳化試験機（日本レオロジー機器（株）製）上に展開し、ロール温度３０℃、２００ｒｐｍにて純水を５ｍｌ／分の速度で供給した後、このインキ中の水分量を赤外水分計により測定した。数値が小さいほど耐乳化性が良好である。
(Emulsification rate)
After 3.9 ml of ink was developed on a dynamic emulsification tester (manufactured by Nippon Rheology Equipment Co., Ltd.), pure water was supplied at a roll temperature of 30 ° C. and 200 rpm at a rate of 5 ml / min. The amount was measured with an infrared moisture meter. The smaller the value, the better the emulsification resistance.
（ミスチング）
インキ２．６ｍｌをインコメーター（（株）東洋精機製作所製）上に展開し、ロール温度３０℃、４００ｒｐｍで１分間、更に１８００ｒｐｍで２分間回転させ、ロール直下に置いた白色紙上へのインキの飛散度を観察して１〜５段階で評価を行った。数値が大きいほど耐ミスチング性が良好である。
(Missing)
2.6 ml of ink is spread on an incometer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), rotated at a roll temperature of 30 ° C. for 1 minute at 400 rpm, and further rotated at 1800 rpm for 2 minutes. The scattering degree was observed and evaluated in 1 to 5 stages. The larger the value, the better the misting resistance.
（タック値）
インキ１．３ｍｌをインコメーター（（株）東洋精機製作所製）上に展開し、ロール温度３０℃、４００ｒｐｍの条件下で１分後のタック値を測定した。タック値が低いほど、紙剥けは少なくなり、高速印刷適性が高い。
(Tack value)
1.3 ml of ink was spread on an incometer (manufactured by Toyo Seiki Seisakusho), and the tack value after 1 minute was measured under the conditions of a roll temperature of 30 ° C. and 400 rpm. The lower the tack value, the less paper peeling and the higher the high-speed printing suitability.
Claims (8)
（１）前記（Ａ）成分中に、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の重量平均分子量１以上１９９以下である低分子量成分（ａ１）５〜１２％、かつ重量平均分子量４０１以上２０００以下である高分子量成分（ａ２）４〜６％が含まれる。
（２）前記（Ａ）成分中に含まれるパラストリン酸、アビエチン酸およびネオアビエチン酸の合計含有量（ｔ１）（ガスクロマトグラフィー法により測定された合計含有量をいう）の原料ロジン類中に含まれる前記合計含有量（ｔ２）に対する比率［（ｔ１／ｔ２）×１００］が、８８％以上である。 After reacting the rosins (A) satisfying the following (1) and (2) obtained by heat-treating the raw rosins in the presence of the sulfonic acid catalyst (B) with the alkylphenol-formaldehyde condensate (C), then polyols (D) and esterification reaction is allowed to a manufacturing method of an offset printing ink rosin-modified phenolic resin obtained Ru offset printing ink rosin-modified phenolic resin having a weight average molecular weight 50,000～130,000.
(1) In the component (A), a low molecular weight component (a1) having a weight average molecular weight of 1 to 199 in terms of polystyrene by gel permeation chromatography is 5 to 12% and a weight average molecular weight of 401 to 2000. The high molecular weight component (a2) is 4 to 6%.
(2) Included in raw material rosins of the total content (t1) (referring to the total content measured by gas chromatography method) of parastrinic acid, abietic acid and neoabietic acid contained in the component (A) The ratio [(t1 / t2) × 100] to the total content (t2) is 88% or more.
The offset printing ink composition containing the resin varnish composition for printing inks of Claim 7.
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