JP2007204677A - Pigment-coating agent, coating pigment and printing ink composition - Google Patents
Pigment-coating agent, coating pigment and printing ink composition Download PDFInfo
- Publication number
- JP2007204677A JP2007204677A JP2006027404A JP2006027404A JP2007204677A JP 2007204677 A JP2007204677 A JP 2007204677A JP 2006027404 A JP2006027404 A JP 2006027404A JP 2006027404 A JP2006027404 A JP 2006027404A JP 2007204677 A JP2007204677 A JP 2007204677A
- Authority
- JP
- Japan
- Prior art keywords
- rosin
- pigment
- acid
- polyester resin
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 72
- 238000007639 printing Methods 0.000 title claims abstract description 43
- 239000011248 coating agent Substances 0.000 title claims abstract description 38
- 238000000576 coating method Methods 0.000 title claims abstract description 18
- 239000000203 mixture Substances 0.000 title claims description 26
- 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 abstract description 76
- 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 abstract description 76
- 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 abstract description 76
- 229920005989 resin Polymers 0.000 claims abstract description 64
- 239000011347 resin Substances 0.000 claims abstract description 64
- 229920001225 polyester resin Polymers 0.000 claims abstract description 50
- 239000004645 polyester resin Substances 0.000 claims abstract description 50
- 239000003208 petroleum Substances 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 150000007824 aliphatic compounds Chemical class 0.000 claims abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 7
- 229920005862 polyol Polymers 0.000 claims abstract description 5
- 150000003077 polyols Chemical class 0.000 claims abstract description 5
- 125000000524 functional group Chemical group 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 229920001568 phenolic resin Polymers 0.000 abstract description 5
- 150000002989 phenols Chemical class 0.000 abstract description 5
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000020169 heat generation Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 53
- 239000000976 ink Substances 0.000 description 51
- 239000002253 acid Substances 0.000 description 33
- 238000004519 manufacturing process Methods 0.000 description 30
- 238000003756 stirring Methods 0.000 description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 239000000944 linseed oil Substances 0.000 description 11
- 235000021388 linseed oil Nutrition 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- -1 trimethylol pullane Chemical compound 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 7
- 238000007645 offset printing Methods 0.000 description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 239000003549 soybean oil Substances 0.000 description 5
- 235000012424 soybean oil Nutrition 0.000 description 5
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 5
- XWAMHGPDZOVVND-UHFFFAOYSA-N 1,2-octadecanediol Chemical compound CCCCCCCCCCCCCCCCC(O)CO XWAMHGPDZOVVND-UHFFFAOYSA-N 0.000 description 4
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- MZZSDCJQCLYLLL-UHFFFAOYSA-N Secalonsaeure A Natural products COC(=O)C12OC3C(CC1=C(O)CC(C)C2O)C(=CC=C3c4ccc(O)c5C(=O)C6=C(O)CC(C)C(O)C6(Oc45)C(=O)OC)O MZZSDCJQCLYLLL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- DWPDSISGRAWLLV-JHZYRPMRSA-L calcium;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Ca+2].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O.C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O DWPDSISGRAWLLV-JHZYRPMRSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 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 2
- 238000007646 gravure printing Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- HPSSZFFAYWBIPY-UHFFFAOYSA-N malvalic acid Chemical compound CCCCCCCCC1=C(CCCCCCC(O)=O)C1 HPSSZFFAYWBIPY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- UZSAQAWEIQNGJT-UHFFFAOYSA-N tetracontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO UZSAQAWEIQNGJT-UHFFFAOYSA-N 0.000 description 2
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- BEOUGZFCUMNGOU-UHFFFAOYSA-N tuberculostearic acid Chemical compound CCCCCCCCC(C)CCCCCCCCC(O)=O BEOUGZFCUMNGOU-UHFFFAOYSA-N 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- DSZTYVZOIUIIGA-UHFFFAOYSA-N 1,2-Epoxyhexadecane Chemical compound CCCCCCCCCCCCCCC1CO1 DSZTYVZOIUIIGA-UHFFFAOYSA-N 0.000 description 1
- LRTOHSLOFCWHRF-UHFFFAOYSA-N 1-methyl-1h-indene Chemical compound C1=CC=C2C(C)C=CC2=C1 LRTOHSLOFCWHRF-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 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
- 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
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-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
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 1
- MPGABYXKKCLIRW-UHFFFAOYSA-N 2-decyloxirane Chemical compound CCCCCCCCCCC1CO1 MPGABYXKKCLIRW-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
- IOHJQSFEAYDZGF-UHFFFAOYSA-N 2-dodecyloxirane Chemical compound CCCCCCCCCCCCC1CO1 IOHJQSFEAYDZGF-UHFFFAOYSA-N 0.000 description 1
- QBJWYMFTMJFGOL-UHFFFAOYSA-N 2-hexadecyloxirane Chemical compound CCCCCCCCCCCCCCCCC1CO1 QBJWYMFTMJFGOL-UHFFFAOYSA-N 0.000 description 1
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- AAMHBRRZYSORSH-UHFFFAOYSA-N 2-octyloxirane Chemical compound CCCCCCCCC1CO1 AAMHBRRZYSORSH-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- OOKDYUQHMDBHMB-UHFFFAOYSA-N 3,6-dichloro-2-methoxybenzoic acid;2-(2,4-dichlorophenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CNC.COC1=C(Cl)C=CC(Cl)=C1C(O)=O.OC(=O)COC1=CC=C(Cl)C=C1Cl OOKDYUQHMDBHMB-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 238000006596 Alder-ene reaction Methods 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
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- 239000004793 Polystyrene Substances 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-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
- MQQXUGFEQSCYIA-OAWHIZORSA-M aluminum;(z)-4-ethoxy-4-oxobut-2-en-2-olate;propan-2-olate Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CCOC(=O)\C=C(\C)[O-] MQQXUGFEQSCYIA-OAWHIZORSA-M 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229940051881 anilide analgesics and antipyretics Drugs 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000001639 calcium acetate Substances 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
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- KIZFHUJKFSNWKO-UHFFFAOYSA-M calcium monohydroxide Chemical compound [Ca]O KIZFHUJKFSNWKO-UHFFFAOYSA-M 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000011109 contamination 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
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-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
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 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
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 239000010439 graphite Substances 0.000 description 1
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- BUHXFUSLEBPCEB-UHFFFAOYSA-N icosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCN BUHXFUSLEBPCEB-UHFFFAOYSA-N 0.000 description 1
- BTFJIXJJCSYFAL-UHFFFAOYSA-N icosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCO BTFJIXJJCSYFAL-UHFFFAOYSA-N 0.000 description 1
- JNNNAJIAXISWGB-UHFFFAOYSA-N icosane-1,1-diol Chemical compound CCCCCCCCCCCCCCCCCCCC(O)O JNNNAJIAXISWGB-UHFFFAOYSA-N 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- 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 1
- 239000003999 initiator Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000007644 letterpress printing Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 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
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- YDLYQMBWCWFRAI-UHFFFAOYSA-N n-Hexatriacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC YDLYQMBWCWFRAI-UHFFFAOYSA-N 0.000 description 1
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 208000008842 sick building syndrome Diseases 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- KQOMUSLQKQAVTD-UHFFFAOYSA-N sodium 4-hydroxy-3-[(4-nitrophenyl)diazenyl]naphthalene-1,5-disulfonic acid Chemical compound C1=CC2=C(C=C(C(=C2C(=C1)S(=O)(=O)O)O)N=NC3=CC=C(C=C3)[N+](=O)[O-])S(=O)(=O)O.[Na+] KQOMUSLQKQAVTD-UHFFFAOYSA-N 0.000 description 1
- TYVJJYHBZVERDC-UHFFFAOYSA-N sodium 8-hydroxy-7-[(4-nitrophenyl)diazenyl]naphthalene-1,6-disulfonic acid Chemical compound C1=CC2=CC(=C(C(=C2C(=C1)S(=O)(=O)O)O)N=NC3=CC=C(C=C3)[N+](=O)[O-])S(=O)(=O)O.[Na+] TYVJJYHBZVERDC-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WFLJHDLVVWUGGZ-UHFFFAOYSA-N triacontan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCN WFLJHDLVVWUGGZ-UHFFFAOYSA-N 0.000 description 1
- LGWZGBCKVDSYPH-UHFFFAOYSA-N triacontane Chemical compound [CH2]CCCCCCCCCCCCCCCCCCCCCCCCCCCCC LGWZGBCKVDSYPH-UHFFFAOYSA-N 0.000 description 1
- OLTHARGIAFTREU-UHFFFAOYSA-N triacontane Natural products CCCCCCCCCCCCCCCCCCCCC(C)CCCCCCCC OLTHARGIAFTREU-UHFFFAOYSA-N 0.000 description 1
- YSRGUFACXHZRMY-UHFFFAOYSA-N triacontane-1,1-diol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)O YSRGUFACXHZRMY-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
- 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
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0004—Coated particulate pigments or dyes
- C09B67/0008—Coated particulate pigments or dyes with organic coatings
- C09B67/0013—Coated particulate pigments or dyes with organic coatings with polymeric coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は、顔料コーティング剤、被覆顔料、および印刷インキ組成物に関する。 The present invention relates to a pigment coating agent, a coated pigment, and a printing ink composition.
従来、印刷インキ（オフセット印刷、新聞印刷インキ等）の各種性能（鮮明性、着色性、色調、分散性等、耐水性等）を向上させるために、顔料をロジン類で表面処理することがよく行われており、顔料コーティング剤としては前記性能の点より、ロジン変性フェノール樹脂が賞用されている。例えば特許文献１には、ロジン変成フェノール樹脂を顔料とともに乾式粉砕してなる被覆顔料が提案されている。 Conventionally, pigments are often surface treated with rosins to improve various performances of printing inks (offset printing, newspaper printing inks, etc.) (clearness, coloring, color tone, dispersibility, water resistance, etc.) As a pigment coating agent, a rosin-modified phenolic resin is awarded for its performance. For example, Patent Document 1 proposes a coated pigment obtained by dry pulverizing a rosin modified phenolic resin together with a pigment.
しかし、ロジン変性フェノール樹脂は、一般的に大気中で酸化されて劣化しやすいためか、当該被覆顔料は貯蔵時や運搬時に自己発熱するなど、潜在的な危険性を有している。また、酸化・劣化した被覆顔料を用いると、得られる印刷インキの色調が劣るなど、品質面で問題が生ずる。 However, the rosin-modified phenolic resin generally has a potential danger such that it is easily oxidized and deteriorated in the air, or the coated pigment self-heats during storage or transportation. Further, when an oxidized or deteriorated coated pigment is used, problems arise in terms of quality, such as poor color tone of the printing ink obtained.
そこで、例えば特許文献２や特許文献３のように、前記乾式粉砕を不活性ガス雰囲気下で行う方法が考えられるが、得られた被覆顔料がその後の流通過程や作業現場において大気に一切触れない保証はないため、かかる方法は長期貯蔵・運搬の観点から、前記問題の本質的解決に至っていない。 Therefore, for example, as in Patent Document 2 and Patent Document 3, a method of performing the dry pulverization in an inert gas atmosphere is conceivable, but the obtained coated pigment does not touch the atmosphere at all in the subsequent distribution process or work site. Since there is no guarantee, this method has not led to an essential solution of the above problem from the viewpoint of long-term storage and transportation.
一方、自己発熱の問題を回避するには、例えば特許文献４の技術のように、顔料を、ロジン変性フェノール樹脂とロジンソープ（ロジンカルシウム塩等）の水分散液で表面処理し、水系の被覆顔料（レーキ顔料）とする方法も考えられる。しかし、当該被覆顔料は、水系であるが故に吸水性が強く、種々の問題が生ずる。例えば、当該被覆顔料をオフセット印刷に使用した場合には、湿し水によってインキが過乳化してしまい、印刷作業時に種々のトラブルが生ずる。 On the other hand, in order to avoid the problem of self-heating, the pigment is surface-treated with an aqueous dispersion of rosin-modified phenolic resin and rosin soap (rosin calcium salt, etc.) as in the technique of Patent Document 4, for example, and a water-based coated pigment A method of using (rake pigment) is also conceivable. However, since the coated pigment is water-based, it has a strong water absorption and causes various problems. For example, when the coated pigment is used for offset printing, the ink is excessively emulsified by the fountain solution, and various troubles occur during the printing operation.
加えて、ロジン変性フェノール樹脂は、原料のフェノール−ホルムアルデヒド縮合物として、環境ホルモンの疑いがあるフェノール類や、シックハウス症候群の要因の一つであるホルムアルデヒドを用いているので、環境や人体に対する影響が大きく懸念されている。 In addition, rosin-modified phenolic resins use phenols that are suspected of environmental hormones as the raw material phenol-formaldehyde condensate and formaldehyde, which is one of the causes of sick house syndrome. There is great concern.
本発明は、フェノール類やホルムアルデヒドを原料とせず、また酸化による自己発熱が殆ど生じず、更に印刷インキの各種性能を向上させうる被覆顔料を与えることができる、新規な顔料コーティング剤を提供することを主な目的とする。 The present invention provides a novel pigment coating agent that does not use phenols or formaldehyde as a raw material, hardly generates self-heating due to oxidation, and can provide a coating pigment that can improve various performances of printing ink. Is the main purpose.
本発明者は、下記特定の顔料コーティング剤により前記課題を解決できることを見いだした。 The present inventor has found that the above-mentioned problems can be solved by the following specific pigment coating agent.
即ち本発明は、フェノール−ホルムアルデヒドフリーのロジン系ポリエステル樹脂（以下、単にロジン系ポリエステル樹脂という）を含有する顔料コーティング剤；前記ロジン系ポリエステル樹脂が、ロジン類（ａ）、ポリオール類（ｂ）、カルボキシル基または水酸基と共有結合可能な官能基を分子内に１つ以上有する脂肪族化合物（ｃ）（以下、化合物（ｃ）という）、ならびに、必要に応じて芳香族多塩基酸類（ｄ）および／または極性基含有石油樹脂（ｅ）を含む原料を反応させて得られるものである、顔料コーティング剤；前記ロジン系ポリエステル樹脂の、走査型示差熱量測定装置を用いて空気存在下で測定して得た熱量ピーク面積に対応する発熱量（ｍＪ）と、固形分重量（ｍｇ）との比〔ｍＪ／ｍｇ〕が、１５以下であることを特徴とする、顔料コーティング剤；前記顔料コーティング剤を用いた被覆顔料；前記被覆顔料を含有する印刷インキ組成物、に関する。 That is, the present invention is a pigment coating agent containing a phenol-formaldehyde-free rosin polyester resin (hereinafter simply referred to as rosin polyester resin); the rosin polyester resin comprises rosins (a), polyols (b), An aliphatic compound (c) having at least one functional group covalently bonded to a carboxyl group or a hydroxyl group in the molecule (hereinafter referred to as compound (c)), and, if necessary, aromatic polybasic acids (d) and / Or pigment coating agent obtained by reacting a raw material containing a polar group-containing petroleum resin (e); measured in the presence of air using a scanning differential calorimeter of the rosin-based polyester resin The ratio [mJ / mg] of the calorific value (mJ) corresponding to the obtained heat quantity peak area to the solid content weight (mg) is 15 or less. Wherein the pigment coating; coated pigment using the pigment coating agent; printing ink compositions containing the coated pigment, relates.
本発明に係る顔料コーティング剤は、前記ロジン系ポリエステル樹脂を含有するので、酸化による自己発熱が殆ど生じない。そのため、当該顔料コーティング剤を用いれば、長期に亘り安全に貯蔵・運搬できるなど、品質管理面で優れた被覆顔料が得られる。また、当該顔料コーティング剤は、フェノール類やホルムアルデヒドを原料としないので、環境や人体への影響が殆どない。 Since the pigment coating agent according to the present invention contains the rosin-based polyester resin, self-heating due to oxidation hardly occurs. Therefore, when the pigment coating agent is used, a coated pigment excellent in quality control, such as being able to be safely stored and transported over a long period of time, can be obtained. Further, since the pigment coating agent does not use phenols or formaldehyde as raw materials, it has little influence on the environment and the human body.
また、本発明に係る被覆顔料によれば、印刷インキの各種性能（鮮明性、着色性、分散性、耐水性等）を向上させることができる。よって、当該被覆顔料は、新聞印刷インキ組成物、凸版印刷インキ組成物、グラビア印刷インキ組成物、特にオフセット印刷インキ組成物の顔料として、好適に用いることができる。 Moreover, according to the coating pigment which concerns on this invention, the various performances (clearness, coloring property, dispersibility, water resistance, etc.) of printing ink can be improved. Therefore, the said covering pigment can be used suitably as a pigment of a newspaper printing ink composition, a relief printing ink composition, a gravure printing ink composition, especially an offset printing ink composition.
また、本発明に係る印刷インキ組成物は、前記被覆顔料を含有するので、鮮明性や着色性、分散性、被膜の耐水性等の各種性能に優れる。また、当該印刷インキ組成物は、特にオフセット印刷インキ組成物として用いた場合には、湿し水による過乳化が殆ど生じないという利点がある。 Moreover, since the printing ink composition which concerns on this invention contains the said coating pigment, it is excellent in various performances, such as sharpness, coloring property, dispersibility, and the water resistance of a film. In addition, the printing ink composition has an advantage that over-emulsification with a fountain solution hardly occurs particularly when used as an offset printing ink composition.
〔顔料コーティング剤について〕
本発明の顔料コーティング剤に含有される前記ロジン系ポリエステル樹脂は、大気中で酸化による自己発熱を殆ど生じないという特徴を有する。（なお、前記「フェノール−ホルムアルデヒドフリー」とは、フェノール類やホルムアルデヒド、あるいはフェノール−ホルムアルデヒド縮合物を原料に用いていないことを意味する。）
[About pigment coating agents]
The rosin-based polyester resin contained in the pigment coating agent of the present invention is characterized in that it hardly generates self-heating due to oxidation in the atmosphere. (The above “phenol-formaldehyde-free” means that phenols, formaldehyde, or phenol-formaldehyde condensates are not used as raw materials.)
ロジン類（ａ）としては、各種公知のものを特に制限なく用いることができる。具体的には、例えば天然ロジン〔ガムロジン、トール油ロジン、ウッドロジン等〕；天然ロジン誘導体〔α，β−不飽和カルボン酸（アクリル酸、メタクリル酸、（無水）マレイン酸、フマル酸等）でディールス・アルダー変性したロジン（例えばアクリル酸変性ロジン、マレイン酸変性ロジン、無水マレイン酸変性ロジン、フマル酸変性ロジン等）、重合ロジン、不均化ロジン、水素化ロジン等〕を例示することができ、これらは１種を単独で、または２種以上を組み合わせて用いることができる。
ロジン類（ａ）の物性は特に制限されないが、酸価が通常１３０〜３５０ｍｇＫＯＨ／ｇ程度、軟化点が通常６０〜２００℃程度である。
これらの中でも、ロジン系ポリエステル樹脂の分子量や軟化点を高めやすく、また顔料をコーティングする際にコーティング装置の汚染が生じにくくなるため、前記α，β−不飽和カルボン変性ロジンおよび／または前記重合ロジンが好ましい。
ロジン類（ａ）の使用量は、ロジン系ポリエステル樹脂の全原料において、通常１０〜９０重量％程度である。
Various known rosins (a) can be used without particular limitation. Specifically, for example, natural rosin [gum rosin, tall oil rosin, wood rosin, etc.]; natural rosin derivative [α, β-unsaturated carboxylic acid (acrylic acid, methacrylic acid, (anhydrous) maleic acid, fumaric acid, etc.) -Alder-modified rosins (for example, acrylic acid-modified rosin, maleic acid-modified rosin, maleic anhydride-modified rosin, fumaric acid-modified rosin, etc.), polymerized rosin, disproportionated rosin, hydrogenated rosin, etc.) These can be used alone or in combination of two or more.
The physical properties of the rosins (a) are not particularly limited, but the acid value is usually about 130 to 350 mgKOH / g, and the softening point is usually about 60 to 200 ° C.
Among these, the α, β-unsaturated carboxylic modified rosin and / or the polymerized rosin are easy to increase the molecular weight and softening point of the rosin polyester resin, and are less likely to cause contamination of the coating apparatus when coating the pigment. Is preferred.
The amount of rosins (a) used is usually about 10 to 90% by weight in all raw materials of the rosin polyester resin.
ポリオール類（ｂ）は、各種公知のものを特に制限なく用いることができる。具体的には、例えば、２価アルコール〔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、トリプロピレングリコール等〕；３価アルコール〔グリセリン、トリメチロールプルパン、トリメチロールエタン等〕；４価アルコール〔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、ジトリメチロールエタン等〕；６価アルコール〔ジペンタエリスリトール等〕を例示することができ、これらは１種を単独で、または２種以上を組み合わせて用いることができる。
これらの中でも、ロジン系ポリエステル樹脂の分子量や軟化点を調整しやすくなるため、前記３価アルコールおよび／または４価アルコール、特にグリセリンおよび／またはペンタエリスリトールが好ましい。
ポリオール類（ｂ）の使用量は、ロジン系ポリエステル樹脂の全原料において、通常１〜３０重量％程度である。
Various known polyols (b) can be used without particular limitation. Specifically, for example, dihydric alcohol [ethylene glycol, diethylene glycol, triethylene glycol, tripropylene glycol, etc.]; trivalent alcohol [glycerin, trimethylol pullane, trimethylol ethane, etc.]; tetrahydric alcohol [pentaerythritol, Diglycerin, ditrimethylolpropane, ditrimethylolethane and the like]; hexavalent alcohol [dipentaerythritol and the like] can be exemplified, and these can be used alone or in combination of two or more.
Among these, the trihydric alcohol and / or tetrahydric alcohol, particularly glycerin and / or pentaerythritol is preferable because the molecular weight and softening point of the rosin polyester resin can be easily adjusted.
The amount of the polyols (b) used is usually about 1 to 30% by weight in all raw materials of the rosin polyester resin.
脂肪族化合物（ｃ）は、主にロジン系ポリエステル樹脂のインキ用溶剤への溶解性を高める目的で、各種公知のものを特に制限なく用いることができる。具体的には、例えば、脂肪族塩基酸類、脂肪族アルコール類、脂肪族モノアミン類、脂肪族モノエポキシ類等の低分子脂肪族化合物；α，β−不飽和カルボン酸と疎水性重合性不飽和化合物とからなるポリマーと、当該ポリマー中のカルボン酸類に対し反応性を有する疎水性化合物とを、部分的に反応させてなる樹脂等の高分子脂肪族化合物、を例示でき、これらは１種を単独で、または２種以上を組み合わせて用いることができる。
脂肪族化合物（ｃ）の使用量は、ロジン系ポリエステル樹脂の全原料において、通常３〜４０重量％程度である。
As the aliphatic compound (c), various known compounds can be used without particular limitation for the purpose of mainly increasing the solubility of the rosin-based polyester resin in the ink solvent. Specifically, for example, low molecular weight aliphatic compounds such as aliphatic basic acids, aliphatic alcohols, aliphatic monoamines, aliphatic monoepoxies; α, β-unsaturated carboxylic acid and hydrophobic polymerizable unsaturated And a polymer aliphatic compound such as a resin obtained by partially reacting a polymer composed of a compound and a hydrophobic compound having reactivity with a carboxylic acid in the polymer. It can be used alone or in combination of two or more.
The usage-amount of an aliphatic compound (c) is about 3 to 40 weight% normally in all the raw materials of a rosin-type polyester resin.
前記低分子脂肪族化合物のうち、脂肪族塩基酸類としては、具体的には、例えば、炭素数１０〜４０程度の直鎖状脂肪酸〔カプリン酸、ステアリン酸、オレイン酸、リノレン酸等〕；炭素数１０〜４０程度の分岐状脂肪酸〔イソ酸、ツベルクロステアリン酸等〕；環状脂肪酸〔マルバリン酸、ショールムーグリン酸等〕；炭素数８〜４０程度のアルキル（無水）コハク酸〔オクチル（無水）コハク酸、ドデシル（無水）コハク酸、トリアコチル（無水）コハク酸、テトラコンチ（無水）コハク酸等〕；炭素数８〜４０程度のアルキル（無水）コハク酸〔オクテニル（無水）コハク酸、ドデセニル（無水）コハク酸、トリアコンテニル（無水）コハク酸、テトラコンテニル（無水）コハク酸等〕；炭素数１０〜４０程度のα，ω−ジカルボン酸〔セバシン酸、エイコサン二酸、トリアコンタン二酸等〕；α，β−不飽和カルボン酸と（半）乾性油（アマニ油、大豆油、脱水ヒマシ油等）からなる化合物；α，β−不飽和カルボン酸類とオレフィンオリゴマーからなる化合物；ダイマー酸を例示できる。 Among the low molecular weight aliphatic compounds, specific examples of the aliphatic basic acids include linear fatty acids having about 10 to 40 carbon atoms [capric acid, stearic acid, oleic acid, linolenic acid, etc.]; carbon Branched fatty acid having about 10 to 40 [iso acid, tuberculostearic acid, etc.]; Cyclic fatty acid [malvalic acid, shawl moulinic acid, etc.]; Alkyl (anhydrous) succinic acid [octyl (anhydrous) having about 8 to 40 carbon atoms ) Succinic acid, dodecyl (anhydrous) succinic acid, triacotyl (anhydrous) succinic acid, tetraconti (anhydrous) succinic acid, etc.]; alkyl (anhydrous) succinic acid having about 8 to 40 carbon atoms [octenyl (anhydrous) succinic acid, dodecenyl ( Anhydrous) succinic acid, triacontenyl (anhydrous) succinic acid, tetracontenyl (anhydrous) succinic acid, etc.]; α, ω-dicarboxylic acid having about 10 to 40 carbon atoms [ Sebacic acid, eicosane diacid, triacontane diacid, etc.]; α, β-unsaturated carboxylic acid and (semi) drying oil (linseed oil, soybean oil, dehydrated castor oil, etc.); α, β-unsaturated Compound consisting of carboxylic acid and olefin oligomer; dimer acid can be exemplified.
前記脂肪族アルコール類としては、具体的には、例えば、炭素数１０〜４０程度のモノアルコール〔デシルアルコール、イコサノール、トリアコンタノール、テトラコンタノール等〕；炭素数１０〜４０程度のジオール〔１，２−オクタデカンジオール、デカンジオール、イコサンジオール、トリアコンタンジオール、テトラコンタンジオール等〕；ダイマー酸を水添したジオールを例示できる。 Specific examples of the aliphatic alcohols include monoalcohols having about 10 to 40 carbon atoms (decyl alcohol, icosanol, triacontanol, tetracontanol and the like); diols having about 10 to 40 carbon atoms [1 , 2-octadecanediol, decanediol, icosanediol, triacontanediol, tetracontanediol, etc.]; diols obtained by hydrogenating dimer acid can be exemplified.
前記脂肪族モノアミン類としては、具体的には、例えば、炭素数１０〜４０程度のモノアミン〔デシルアミン、イコシルアミン、トリアコンチルアミン、テトラコンチルアミン等〕；炭素数１０〜４０程度の動植物由来アミン〔牛脂アルキルアミン、大豆アルキルアミン等〕を例示できる。 Specific examples of the aliphatic monoamines include monoamines having about 10 to 40 carbon atoms (decylamine, icosylamine, triacontylamine, tetracontylamine and the like); animals and plant-derived amines having about 10 to 40 carbon atoms [tallow Alkylamine, soybean alkylamine, etc.].
前記脂肪族モノエポキシ類としては、具体的には、例えば、炭素数１０〜４０程度の脂肪族モノエポキシ類〔例えば１,２−エポキシヘキサン、１,２−エポキシオクタン、１,２−エポキシデカン、１,２−エポキシドデカン、１,２−エポキシテトラデカン、１,２−エポキシヘキサデカン、１,２−エポキシオクタデカン、エチルヘキシルグリシジルエーテル〕などを例示できる。 Specific examples of the aliphatic monoepoxies include aliphatic monoepoxies having about 10 to 40 carbon atoms [for example, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane. 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, ethylhexyl glycidyl ether] and the like.
前記高分子脂肪族化合物としては、例えば特許３４４６７２８号公報に記載された樹脂を用いることができる。 As the polymer aliphatic compound, for example, a resin described in Japanese Patent No. 3446728 can be used.
芳香族多塩基酸類（ｄ）は、主にロジン系ポリエステル樹脂の軟化点を高める目的で、各種公知のものを任意に用いることができる。具体的には、例えば、芳香族多塩基酸類〔（無水）フタル酸、イソフタル酸、テレフタル酸、（無水）トリメリット酸、ピロメリット酸等〕；該芳香族多塩基酸類に対応するモノアルキルエステル〔モノメチルエステル、モノエチルエステル、ジメチルエステル、ジエチルエステル等〕を例示でき、これらは１種を単独で、または２種以上を組み合わせて用いることができる。芳香族多塩基酸類（ｄ）の使用量は、ロジン系ポリエステル樹脂の全原料において、通常０〜２０重量％程度である。 As the aromatic polybasic acid (d), various known ones can be arbitrarily used mainly for the purpose of increasing the softening point of the rosin-based polyester resin. Specifically, for example, aromatic polybasic acids [(anhydrous) phthalic acid, isophthalic acid, terephthalic acid, (anhydrous) trimellitic acid, pyromellitic acid, etc.]; monoalkyl esters corresponding to the aromatic polybasic acids [Monomethyl ester, monoethyl ester, dimethyl ester, diethyl ester and the like] can be exemplified, and these can be used alone or in combination of two or more. The usage-amount of aromatic polybasic acid (d) is about 0 to 20 weight% normally in all the raw materials of a rosin-type polyester resin.
極性基含有石油樹脂（ｅ）は、主にロジン系ポリエステル樹脂の分子量や軟化点を高める目的で、各種公知のものを任意に用いることができる。具体的には、各種公知の石油樹脂に、カルボキシル基や水酸基などの極性基を、各種公知の手段で導入したものを用いることができる（例えば、特許３４４６７２８号公報を参照）。
当該石油樹脂としては、例えば、ＤＣＰＤ系石油樹脂〔原料として、例えばシクロペンタジエン、ジシクロペンタジエンを用いる〕；Ｃ５系石油樹脂〔原料として、例えばペンテン、シクロペンテン、ペンタジエン、イソプレン用いる〕；Ｃ９系石油樹脂〔原料として、例えばメチルブテン、インデン、メチルインデン、ビニルトルエン、スチレン、α−メチルスチレン、β−メチルスチレン用いる〕；該ＤＣＰＤ系石油樹脂の原料と、該Ｃ５系石油樹脂の原料からなる共重合石油樹脂；該Ｃ５系石油樹脂の原料と、該Ｃ９系石油樹脂の原料からなる共重合石油樹脂；該ＤＣＰＤ系石油樹脂の原料と、該Ｃ９系石油樹脂の原料からなる共重合石油樹脂；該ＤＣＰＤ系石油樹脂の原料と、該Ｃ５系石油樹脂の原料と、該Ｃ９系石油樹脂の原料からなる共重合石油樹脂、などを例示できる。
なお、石油樹脂に極性基を導入する方法としては、例えばカルボキシル基を導入する場合には、（１）前記α，β−不飽和カルボン酸と、前記石油樹脂を、各種公知のラジカル反応開始剤の存在下でラジカル共重合反応させる方法や、（２）前記α，β−不飽和カルボン酸と、前記石油樹脂を、エン反応させる方法、を例示できる。
また、例えば水酸基を導入する場合には、（３）アリルアルコール等の分子内に二重結合と水酸基を有する化合物を、前記石油樹脂に熱重合させる方法を例示できる。
極性基含有石油樹脂（ｅ）の物性は特に制限されないが、重量平均分子量が通常４，０００〜３０，０００程度である。極性基含有石油樹脂（ｅ）がカルボキシル基を有するものである場合には、その理論酸価は通常５〜１０２ｍｇＫＯＨ／ｇ程度である。
極性基含有石油樹脂（ｅ）の使用量は、ロジン系ポリエステル樹脂の全原料において、通常０〜６６重量％程度である。
As the polar group-containing petroleum resin (e), various known resins can be arbitrarily used mainly for the purpose of increasing the molecular weight and softening point of the rosin-based polyester resin. Specifically, what introduced polar groups, such as a carboxyl group and a hydroxyl group, into various known petroleum resins by various known means can be used (for example, refer to patent 3446728).
Examples of the petroleum resin include DCPD petroleum resins (for example, cyclopentadiene and dicyclopentadiene are used as raw materials); C5 petroleum resins (for example, pentene, cyclopentene, pentadiene and isoprene are used as raw materials); C9 petroleum resins [For example, methylbutene, indene, methylindene, vinyltoluene, styrene, α-methylstyrene, β-methylstyrene are used as raw materials]; Copolymer petroleum consisting of a raw material of the DCPD petroleum resin and a raw material of the C5 petroleum resin Resin; Copolymer petroleum resin composed of C5 petroleum resin raw material and C9 petroleum resin raw material; Copolymer petroleum resin composed of DCPD petroleum resin raw material and C9 petroleum resin raw material; DCPD From the raw material of the petroleum-based petroleum resin, the raw material of the C5-based petroleum resin, and the raw material of the C9-based petroleum resin And a copolymerized petroleum resin.
In addition, as a method for introducing a polar group into a petroleum resin, for example, when introducing a carboxyl group, (1) the α, β-unsaturated carboxylic acid and the petroleum resin are mixed with various known radical reaction initiators. And (2) a method of subjecting the α, β-unsaturated carboxylic acid and the petroleum resin to an ene reaction.
For example, when a hydroxyl group is introduced, (3) a method of thermally polymerizing a compound having a double bond and a hydroxyl group in the molecule such as allyl alcohol to the petroleum resin can be exemplified.
The physical properties of the polar group-containing petroleum resin (e) are not particularly limited, but the weight average molecular weight is usually about 4,000 to 30,000. When the polar group-containing petroleum resin (e) has a carboxyl group, the theoretical acid value is usually about 5 to 102 mgKOH / g.
The amount of the polar group-containing petroleum resin (e) used is usually about 0 to 66% by weight in all raw materials of the rosin polyester resin.
ロジン系ポリエステル樹脂の製造方法は特に制限されず、各種公知のエステル方法を採用することができる。具体的には、例えば、攪拌機、分水器付き還流冷却管、温度計等を備えた反応容器に、前記原料を所定量ずつ仕込み、１００〜３００℃程度の温度で、１〜２０時間程度エステル反応を進行させればよい。また、反応系は窒素等の不活性ガス雰囲気とするのが好ましい。 The production method of the rosin polyester resin is not particularly limited, and various known ester methods can be employed. Specifically, for example, a predetermined amount of the raw material is charged into a reaction vessel equipped with a stirrer, a reflux condenser with a water separator, a thermometer, etc., and the ester is used at a temperature of about 100 to 300 ° C. What is necessary is just to advance reaction. The reaction system is preferably an inert gas atmosphere such as nitrogen.
なお、各原料の使用重量は前記の通りであるが、用いる原料に含まれる水酸基とアミノ基の全当量（Ｘ ｅｑ）と、用いる原料に含まれるカルボキシル基の全当量（Ｙ ｅｑ）の比（Ｘ／Ｙ）を、通常０．５〜１．１程度の範囲となるように調整した場合には、本発明に係る印刷インキ組成物の耐過乳化性が、いっそう向上するため好ましい。そのため、当該印刷インキ組成物は、特にオフセット印刷用途に好適に用いることができる。 In addition, although the use weight of each raw material is as above-mentioned, ratio (Xeq) of the total equivalent (Xeq) of the hydroxyl group and amino group contained in the raw material to be used, and the total equivalent (Yeq) of the carboxyl group contained in the raw material to be used ( When X / Y) is usually adjusted to be in the range of about 0.5 to 1.1, the overemulsification resistance of the printing ink composition according to the present invention is further improved, which is preferable. Therefore, the printing ink composition can be suitably used particularly for offset printing applications.
エステル反応時には、各種公知のエステル化触媒を用いることができる。具体的には、例えば、酸触媒〔塩酸、硫酸、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〕；アルカリ金属水酸化物〔水酸化リチウム、水酸化ナトリウム、水酸化カリウム等〕；アルカリ土類金属水酸化物〔水酸化カルシウム、水酸化マグネシウム等〕；金属酸化物〔酸化カルシウム、酸化マグネシウム、酸化亜鉛等〕；酢酸金属塩〔酢酸カルシウム、酢酸マグネシウム、酢酸亜鉛等〕などを例示できる。 In the ester reaction, various known esterification catalysts can be used. Specifically, for example, an acid catalyst [hydrochloric acid, sulfuric acid, methanesulfonic acid, paratoluenesulfonic acid, dodecylbenzenesulfonic acid, etc.]; alkali metal hydroxide [lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.]; Examples include alkaline earth metal hydroxides [calcium hydroxide, magnesium hydroxide, etc.]; metal oxides [calcium oxide, magnesium oxide, zinc oxide, etc.]; acetate metal salts [calcium acetate, magnesium acetate, zinc acetate, etc.] it can.
また、エステル反応時には、各種公知の有機溶剤を用いることができる。具体的には、例えば、芳香族溶剤〔トルエン、キシレン等〕、脂環族溶剤〔メチルシクロヘキサン、エチルシクロヘキサン、新日本石油製ＡＦソルベント４号、新日本石油製ＡＦソルベント５号、新日本石油製ＡＦソルベント６号、新日本石油製ＡＦソルベント７号等〕、エステル系溶剤〔例えば酢酸エチル、酢酸ブチル等〕などを例示できる。 In the ester reaction, various known organic solvents can be used. Specifically, for example, aromatic solvents [toluene, xylene, etc.], alicyclic solvents [methylcyclohexane, ethylcyclohexane, Nippon Oil AF Solvent No. 4, Nippon Oil AF Solvent No. 5, Nippon Oil AF solvent No. 6, Shin Nippon Petroleum AF solvent No. 7, etc.], ester solvents (for example, ethyl acetate, butyl acetate, etc.) and the like can be exemplified.
得られるロジン系ポリエステル樹脂の物性は特に限定されないが、ロジン系ポリエステル樹脂の印刷インキ溶剤への溶解性や、印刷インキ組成物の被膜の乾燥性や、セット性を良好に保つために、軟化点が通常１４０〜２００℃程度、重量平均分子量が通常３０，０００〜４００，０００程度（好ましくは５０，０００〜２００，０００）であるのがよい。また、ロジン系ポリエステル樹脂の３３％アマニ油粘度は、通常２〜１５程度である。（ここに、３３％アマニ油粘度とは、ポリエステル樹脂とアマニ油の１対２混合物の２５℃における粘度を、コーン＆プレート型粘度計（日本レオロジー機器（株）製）で測定した粘度をいう（以下、同様）。） The physical properties of the obtained rosin-based polyester resin are not particularly limited, but in order to maintain the solubility of the rosin-based polyester resin in the printing ink solvent, the drying property of the coating film of the printing ink composition, and the setability, the softening point Is usually about 140 to 200 ° C., and the weight average molecular weight is usually about 30,000 to 400,000 (preferably 50,000 to 200,000). Moreover, the 33% linseed oil viscosity of a rosin-type polyester resin is about 2-15 normally. (Here, 33% linseed oil viscosity refers to the viscosity of a one-to-two mixture of polyester resin and linseed oil measured at 25 ° C. with a cone and plate viscometer (manufactured by Nippon Rheology Equipment Co., Ltd.)). (The same applies hereinafter.)
本発明に係るロジン系ポリエステル樹脂は、大気中において、酸化による自己発熱が殆ど生じないという特徴を有する。
ここに「自己発熱が殆ど生じない」とは、具体的には、“該ロジン系ポリエステル樹脂の、走査型示差熱量測定装置を用いて空気存在下で測定して得た熱量ピーク面積に対応する発熱量（ｍＪ）”と、“該ロジン系ポリエステル樹脂の固形分重量（ｍｇ）”からなる比〔ｍＪ／ｍｇ〕が、通常１５以下、好ましくは１０以下、特に好ましくは５以下、一層好ましくは実質的に０であることをいう。
なお、前記熱量ピーク面積は、各種公知の走査型示差熱量測定装置を用いて、昇温速度が１０℃／分程度、測定温度範囲が室温〜２００℃程度、測定雰囲気が大気中という条件で得られる面積である。
The rosin-based polyester resin according to the present invention has a feature that almost no self-heating due to oxidation occurs in the atmosphere.
Here, “substantially no self-heating” specifically corresponds to “a calorific peak area obtained by measuring the rosin polyester resin in the presence of air using a scanning differential calorimeter”. The ratio [mJ / mg] consisting of “calorific value (mJ)” and “solid weight of the rosin polyester resin (mg)” is usually 15 or less, preferably 10 or less, particularly preferably 5 or less, more preferably It means substantially zero.
The calorific peak area is obtained by using various known scanning differential calorimeters under the conditions of a temperature rising rate of about 10 ° C./min, a measuring temperature range of room temperature to about 200 ° C., and a measuring atmosphere in the air. Area.
〔被覆顔料について〕
本発明に係る被覆顔料は、前記ロジン系ポリエステル樹脂を用いて、各種公知の印刷インキ用顔料を表面処理（コーティング）することにより、得ることができる。
なお、ロジン系ポリエステル樹脂は、顔料に対して通常１〜２００重量％程度の範囲で用いればよい。
[Coated pigment]
The coated pigment according to the present invention can be obtained by subjecting various known printing ink pigments to surface treatment (coating) using the rosin polyester resin.
The rosin-based polyester resin may be used usually in the range of about 1 to 200% by weight with respect to the pigment.
コーティング手段は特に限定されず、乾式や湿式のいずれかの方法を用いればよい。例えば乾式コーティングの場合には、各種公知の粉砕機〔アトライター、ボールミル、振動ミル等〕において、ロジン系ポリエステル樹脂の存在下で顔料を乾式粉砕すればよい。また粉砕は、酸素が存在しない雰囲気（例えば窒素雰囲気）で行うのがよい。また粉砕温度は、通常８０〜１７０℃程度である。また粉砕時間は、粉砕機の種類や、所望の顔料粒径に応じて、適宜設定すればよい。また、粉砕時には、前記した有機溶剤を適宜用いても良い。 The coating means is not particularly limited, and any one of a dry method and a wet method may be used. For example, in the case of dry coating, the pigment may be dry pulverized in the presence of a rosin polyester resin in various known pulverizers (attritor, ball mill, vibration mill, etc.). The pulverization is preferably performed in an atmosphere in which oxygen is not present (for example, a nitrogen atmosphere). The grinding temperature is usually about 80 to 170 ° C. The pulverization time may be appropriately set according to the type of pulverizer and the desired pigment particle size. Moreover, you may use the above-mentioned organic solvent suitably at the time of a grinding | pulverization.
顔料としては、各種公知の無機顔料あるいは有機顔料を用いることができる。無機顔料としては、例えば黄鉛、亜鉛黄、紺青、硫酸バリウム、カドミウムレッド、酸化チタン、亜鉛華、ベンガラ、アルミナホワイト、炭酸カルシウム、群青、カーボンブラック、グラファイト、アルミニウム粉などを例示できる。また、有機顔料としては、可溶性アゾ顔料〔Ｃ系（βナフトール系）顔料、２Ｂ系顔料、６Ｂ系（βオキシナフトエ系）顔料等〕、不溶性アゾ顔料〔βナフトール系顔料、βオキシナフトエ酸アニリド系顔料、モノアゾイエロー系顔料、ジスアゾイエロー系顔料、ピラゾロン系顔料等〕、フタロシアニン系顔料〔銅フタロシアニン（αブルー、βブルー、εブルー）顔料、ハロゲン化銅フタロシアン顔料、金属フリーフタロシアニン顔料〕などを例示できる。 As the pigment, various known inorganic pigments or organic pigments can be used. Examples of inorganic pigments include chrome lead, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, bengara, alumina white, calcium carbonate, ultramarine, carbon black, graphite, and aluminum powder. Organic pigments include soluble azo pigments [C (β-naphthol) pigments, 2B pigments, 6B (β-oxynaphthoic) pigments, etc.], insoluble azo pigments (β-naphthol pigments, β-oxynaphthoic acid anilides). Pigments, monoazo yellow pigments, disazo yellow pigments, pyrazolone pigments, etc.], phthalocyanine pigments (copper phthalocyanine (α blue, β blue, ε blue) pigments, halogenated copper phthalocyanine pigments, metal-free phthalocyanine pigments), etc. Can be illustrated.
〔印刷インキ組成物について〕
本発明に係る印刷インキ組成物は、前記被覆顔料と各種公知の印刷インキ用ワニスを、各種公知の分散・攪拌機器〔ボールミル、アトライター、サンドミル、三本ロールミル等〕で練肉することにより、得ることができる。
[About printing ink composition]
The printing ink composition according to the present invention is obtained by kneading the coated pigment and various known printing ink varnishes with various known dispersing / stirring equipment (ball mill, attritor, sand mill, three-roll mill, etc.), Obtainable.
前記印刷インキ用ワニスの製造方法は特に制限されない。例えば、各種バインダー樹脂と、各種インキ溶剤と、各種ゲル化剤を用い、各種公知の手段により調製することができる。 The method for producing the printing ink varnish is not particularly limited. For example, it can be prepared by various known means using various binder resins, various ink solvents, and various gelling agents.
該バインダー樹脂としては、アルキド樹脂、石油樹脂、ロジンエステル等の公知バインダー樹脂の他、本発明に係るロジン系ポリエステル樹脂を用いることもできる。 As the binder resin, in addition to known binder resins such as alkyd resins, petroleum resins, and rosin esters, rosin-based polyester resins according to the present invention can also be used.
また、該インキ溶剤としては、前記有機溶剤の他、各種公知の植物油や、脂肪酸エステル等を用いることができる。なお、当該植物油としては、アマニ油、桐油、これらの重合油、サフラワー油、脱水ヒマシ油、大豆油等を例示できる。これらの中でも、印刷インキ被膜の乾燥性の点からは、不飽和結合を有する植物油が好ましく、また環境への影響を考慮すると、大豆油が好ましい。 In addition to the organic solvent, various known vegetable oils, fatty acid esters, and the like can be used as the ink solvent. Examples of the vegetable oil include linseed oil, tung oil, polymerized oils thereof, safflower oil, dehydrated castor oil, soybean oil, and the like. Among these, from the viewpoint of the drying property of the printing ink film, vegetable oil having an unsaturated bond is preferable, and soybean oil is preferable in consideration of the influence on the environment.
また、該ゲル化剤としては、各種公知のものを特に限定なく使用することができる。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、アルミニウムジプロポキシドモノアセチルアセテート等のアルミ系キレート化剤を用いることができる。 Moreover, as this gelling agent, various well-known things can be used without limitation. Specifically, aluminum-based chelating agents such as aluminum octylate, aluminum stearate, aluminum triisopropoxide, aluminum dipropoxide monoacetyl acetate can be used.
なお、本発明に係る印刷インキ組成物には、必要に応じて各種公知の界面活性剤、ワックス、添加剤などを用いてもよい。 In addition, you may use various well-known surfactant, wax, an additive, etc. as needed for the printing ink composition which concerns on this invention.
かかる印刷インキ組成物は、該被覆顔料を含有するので、鮮明性や着色性、分散性、被膜の耐水性等の各種性能に優れる。また、当該印刷インキ組成物は、種々のインキ用途、例えば新聞印刷インキ組成物、凸版印刷インキ組成物、グラビア印刷インキ組成物、特にオフセット印刷インキに供することができる。また、特にオフセット印刷インキ組成物として用いた場合には、湿し水による過乳化が殆ど生じないという利点がある。 Since the printing ink composition contains the coating pigment, it is excellent in various performances such as sharpness, colorability, dispersibility, and water resistance of the coating. The printing ink composition can be used for various ink applications, such as newspaper printing ink compositions, letterpress printing ink compositions, gravure printing ink compositions, and particularly offset printing inks. In particular, when used as an offset printing ink composition, there is an advantage that over-emulsification with dampening water hardly occurs.
以下、製造例、実施例を挙げて本発明を更に具体的に説明するが、本発明を限定するものではない。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 present invention is not limited thereto. Hereinafter, “parts” means parts by weight.
（ロジン類（ａ）の製造）
攪拌機、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、ガムロジン１,０００部を仕込み、窒素雰囲気下で反応系を攪拌しながら１８０℃まで昇温して、これを溶融した。次いで、同反応容器にフマル酸２６７部を仕込み、攪拌下に反応系を２３０℃まで昇温して、１時間保温した。その後、反応容器を冷却して、固形フマル酸変性ロジン（酸価３４２．０、軟化点１４８℃）を得た。
(Production of rosins (a))
A reaction vessel equipped with a stirrer, a reflux condenser with a water separator and a thermometer was charged with 1,000 parts of gum rosin and heated to 180 ° C. while stirring the reaction system in a nitrogen atmosphere to melt it. Next, 267 parts of fumaric acid was charged in the same reaction vessel, and the reaction system was heated to 230 ° C. with stirring and kept warm for 1 hour. Thereafter, the reaction vessel was cooled to obtain solid fumaric acid-modified rosin (acid value 342.0, softening point 148 ° C.).
（極性基含有石油樹脂（ｅ）の製造）
前記同様の反応容器に、ＤＣＰＤ系石油樹脂（商品名
クイントン１３２５、日本ゼオン（株）製）１，０００部を仕込み、窒素雰囲気下で反応系を攪拌しながら１８０℃まで昇温して、これを溶融した。次いで、同反応容器に無水マレイン酸７０部を仕込み、攪拌下に反応系を２３０℃まで昇温して、３時間保温した。その後、同反応容器を冷却して、固形状のカルボキシル基含有石油樹脂樹脂（理論当量６５、重量平均分子量１，５００）を得た。該石油樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によりＴＨＦ溶媒下で測定したポリスチレン換算値をいい、ＧＰＣ装置としてはＨＬＣ−８０２０（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。（以下、同様。）
(Production of polar group-containing petroleum resin (e))
In the same reaction vessel, 1,000 parts of DCPD petroleum resin (trade name Quinton 1325, manufactured by Nippon Zeon Co., Ltd.) was charged, and the temperature was raised to 180 ° C. while stirring the reaction system in a nitrogen atmosphere. Melted. Next, 70 parts of maleic anhydride was charged into the same reaction vessel, and the reaction system was heated to 230 ° C. with stirring and kept warm for 3 hours. Thereafter, the reaction vessel was cooled to obtain a solid carboxyl group-containing petroleum resin resin (theoretical equivalent 65, weight average molecular weight 1,500). The weight average molecular weight of the petroleum resin is a polystyrene equivalent value measured in a THF solvent by gel permeation chromatography (GPC). As a GPC apparatus, HLC-8020 (manufactured by Tosoh Corporation) is used, and as a column, TSK. -A GEL column (manufactured by Tosoh Corporation) was used. (The same applies hereinafter.)
（フェノール−ホルムアルデヒド縮合物の製造）
前記同様の反応容器に、ノニルフェノール１,０００部、パラホルムアルデヒド２７０部および水１,０００部を仕込み、攪拌下に５０℃まで昇温した。次いで、同反応容器に水酸化ナトリウム１００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、２．５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、キシレン１５０部を加え、ホルムアルデヒドなどを含んだ水層部を除去し、更に内容物を冷却して、レゾール型ノニルフェノールの７０％キシレン溶液を得た。
(Production of phenol-formaldehyde condensate)
In the same reaction vessel, 1,000 parts of nonylphenol, 270 parts of paraformaldehyde and 1,000 parts of water were charged, and the temperature was raised to 50 ° C. with stirring. Next, 100 parts of sodium hydroxide was charged into the same reaction vessel, the reaction system was gradually heated to 90 ° C. while cooling, and then kept warm for 2.5 hours, and sulfuric acid was added dropwise to adjust the pH to around 6. . Thereafter, 150 parts of xylene was added, the aqueous layer part containing formaldehyde and the like was removed, and the contents were further cooled to obtain a 70% xylene solution of resol-type nonylphenol.
製造例１
（ロジン系ポリエステル樹脂１の製造）
製造例１と同様の反応容器に、重合ロジン（商品名 シルバタック１４０、シルバケム社製、酸価１４０）５８８部、製造例１の固形フマル酸変性ロジン２６６部、および炭素数１８のアルケニル無水コハク酸５２部を仕込み、反応系を窒素雰囲気下に攪拌しながら１８０℃まで昇温し、これらを溶融した。次いで、同反応容器にペンタエリスリトール４７部、グリセリン４７部を添加し、攪拌下に反応系を２６０℃で保温し、樹脂の酸価が３０以下となった時点でパラトルエンスルホン酸１部を仕込み、酸価が２０以下となるまでエステル化反応させた。反応終了後、反応系を３３重量％アマニ油粘度が８．０Ｐａ・ｓとなるように調整し、更に０．０２ＭＰａで１０分間減圧し、次いで冷却して、固形状のロジン系ポリエステル樹脂１を得た。ロジン系ポリエステル樹脂１の酸価は１５．８、軟化点は１７３℃、重量平均分子量は１３０，０００であった。
Production Example 1
(Production of rosin-based polyester resin 1)
In a reaction vessel similar to Production Example 1, 588 parts of polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value 140), 266 parts of solid fumaric acid-modified rosin of Production Example 1, and alkenyl anhydride succinate having 18 carbon atoms 52 parts of acid was charged, and the reaction system was heated to 180 ° C. while stirring in a nitrogen atmosphere to melt them. Next, 47 parts of pentaerythritol and 47 parts of glycerin were added to the reaction vessel, and the reaction system was kept warm at 260 ° C. with stirring. When the acid value of the resin became 30 or less, 1 part of paratoluenesulfonic acid was charged. The esterification reaction was continued until the acid value became 20 or less. After completion of the reaction, the reaction system was adjusted so that the 33 wt% linseed oil viscosity was 8.0 Pa · s, further reduced in pressure at 0.02 MPa for 10 minutes, and then cooled to obtain solid rosin polyester resin 1. Obtained. The acid value of the rosin-based polyester resin 1 was 15.8, the softening point was 173 ° C., and the weight average molecular weight was 130,000.
製造例２
（ロジン系ポリエステル樹脂２の製造）
製造例１と同様の反応容器に、重合ロジン（商品名 シルバタック１４０、シルバケム社製、酸価：１４０）３５３部、製造例１で得たフマル酸変性ロジン１０１部、製造例２で得た極性基含有石油樹脂樹脂４２６部を仕込み、反応系を窒素雰囲気下に攪拌しながら１８０℃まで昇温し、これらを溶融した。次いで、同反応容器にペンタエリスリトール２２部、グリセリン２２部および１，２−オクタデカンジオール７６部を添加し、攪拌下に反応系を２６０℃で保温し、樹脂の酸価が３０以下となった時点でパラトルエンスルホン酸１部を仕込み、酸価が２０以下となるまでエステル化反応させた。反応終了後、反応系を３３重量％アマニ油粘度が８．０Ｐａ・ｓとなるように調整し、更に０．０２ＭＰａで１０分間減圧し、次いで冷却して、固形状のロジン系ポリエステル樹脂２を得た。該ロジン系ポリエステル樹脂２の酸価は１４．２、軟化点は１６８℃、重量平均分子量は１０３，０００であった。
Production Example 2
(Production of rosin-based polyester resin 2)
In the same reaction vessel as in Production Example 1, 353 parts of polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value: 140), 101 parts of fumaric acid-modified rosin obtained in Production Example 1, obtained in Production Example 2 426 parts of polar group-containing petroleum resin resin were charged, and the reaction system was heated to 180 ° C. with stirring in a nitrogen atmosphere to melt them. Next, 22 parts of pentaerythritol, 22 parts of glycerin and 76 parts of 1,2-octadecanediol were added to the reaction vessel, and the reaction system was kept warm at 260 ° C. with stirring, so that the acid value of the resin became 30 or less. Then, 1 part of p-toluenesulfonic acid was charged and the esterification reaction was carried out until the acid value became 20 or less. After completion of the reaction, the reaction system was adjusted so that the 33 wt% linseed oil viscosity was 8.0 Pa · s, further reduced in pressure at 0.02 MPa for 10 minutes, and then cooled to obtain a solid rosin polyester resin 2. Obtained. The acid value of the rosin-based polyester resin 2 was 14.2, the softening point was 168 ° C., and the weight average molecular weight was 103,000.
製造例３
（ロジン系ポリエステル樹脂３の製造）
製造例１と同様の反応容器に、重合ロジン（商品名 シルバタック１４０、シルバケム社製、酸価：１４０）６７６部、炭素数１８のアルケニル無水コハク酸６８部、イソフタル酸１３５部を仕込み、反応系を窒素雰囲気下に攪拌しながら１８０℃まで昇温し、これらを溶融した。次いで、同反応容器にペンタエリスリトール１２１部を添加し、攪拌下に反応系を２６０℃で保温し、樹脂の酸価が５０以下となった時点でパラトルエンスルホン酸１部を仕込み、酸価が２０以下となるまでエステル化反応させた。反応終了後、反応系の３３重量％アマニ油粘度が８．０Ｐａ・ｓに調整し、０．０２ＭＰａで１０分間減圧、冷却してロジン系ポリエステル樹脂３を得た。該ロジン系ポリエステル樹脂３の酸価は１４．０、軟化点は１７２℃、重量平均分子量は１３１，０００であった。
Production Example 3
(Production of rosin-based polyester resin 3)
In a reaction vessel similar to Production Example 1, 676 parts of polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value: 140), 68 parts of alkenyl succinic anhydride having 18 carbon atoms, and 135 parts of isophthalic acid were charged and reacted. While stirring the system in a nitrogen atmosphere, the temperature was raised to 180 ° C. to melt them. Next, 121 parts of pentaerythritol was added to the reaction vessel, and the reaction system was kept warm at 260 ° C. with stirring. When the acid value of the resin became 50 or less, 1 part of paratoluenesulfonic acid was added. The esterification reaction was continued until it became 20 or less. After the completion of the reaction, the 33 wt% linseed oil viscosity of the reaction system was adjusted to 8.0 Pa · s, and the pressure was reduced at 0.02 MPa for 10 minutes to cool down to obtain a rosin polyester resin 3. The rosin polyester resin 3 had an acid value of 14.0, a softening point of 172 ° C., and a weight average molecular weight of 131,000.
製造例４
（ロジン系ポリエステル樹脂４の製造）
製造例１と同様の反応容器に、重合ロジン（商品名 シルバタック１４０、シルバケム社製、酸価：１４０）３１１部、製造例１のフマル酸変性ロジン５１部、および製造例２の極性基含有樹脂４７８部を仕込み、反応系を窒素雰囲気下に攪拌しながら１８０℃まで昇温し、これらを溶融した。次いで、同反応容器にペンタエリスリトール３１部、グリセリン３１部を添加し、攪拌下に反応系を１８０℃で１時間保温保温し、樹脂の酸価が５０以下となった時点でパラトルエンスルホン酸１部を仕込み、酸価が２０以下となるまでエステル化反応させた。その後、同反応容器に大豆油脂肪酸（商品名「ＴＯＥＮＯＬ＃１１２５」、当栄ケミカル（株）製、酸価１９８）８５部を添加し、反応系を２６０℃で１時間保温した。その後、樹脂の酸価が３０以下となった時点で、同反応容器にイソフタル酸１２部、パラトルエンスルホン酸１部を仕込み、同温度で酸価が２０以下となるまでエステル化反応させた。反応終了後、反応系の３３重量％アマニ油粘度が８．０Ｐａ・ｓに調整し、０．０２ＭＰａで１０分間減圧、冷却してロジン系ポリエステル樹脂４を得た。該ロジン系ポリエステル樹脂４の酸価は１３．８、軟化点は１７８℃、重量平均分子量は１５８，０００であった。
Production Example 4
(Manufacture of rosin-based polyester resin 4)
In a reaction vessel similar to Production Example 1, 311 parts of polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value: 140), 51 parts of fumaric acid-modified rosin of Production Example 1, and polar group content of Production Example 2 478 parts of resin was charged and the reaction system was heated to 180 ° C. while stirring in a nitrogen atmosphere to melt them. Next, 31 parts of pentaerythritol and 31 parts of glycerin were added to the same reaction vessel, and the reaction system was kept warm at 180 ° C. for 1 hour with stirring. When the acid value of the resin became 50 or less, paratoluenesulfonic acid 1 The esterification reaction was carried out until the acid value was 20 or less. Thereafter, 85 parts of soybean oil fatty acid (trade name “TOENOL # 1125”, manufactured by Toei Chemical Co., Ltd., acid value 198) was added to the reaction vessel, and the reaction system was kept at 260 ° C. for 1 hour. Thereafter, when the acid value of the resin became 30 or less, 12 parts of isophthalic acid and 1 part of paratoluenesulfonic acid were charged into the reaction vessel, and the esterification reaction was carried out at the same temperature until the acid value became 20 or less. After the completion of the reaction, the 33 wt% linseed oil viscosity of the reaction system was adjusted to 8.0 Pa · s, and the pressure was reduced at 0.02 MPa for 10 minutes, followed by cooling to obtain rosin-based polyester resin 4. The acid value of the rosin-based polyester resin 4 was 13.8, the softening point was 178 ° C., and the weight average molecular weight was 158,000.
比較製造例１
（ロジン変性フェノール樹脂の製造）
製造例１と同様の反応容器に、ガムロジン５５２部を仕込み、これを窒素雰囲気下に攪拌しながら２３０℃まで昇温して溶融した。次いで、ペンタエリスリトール５２部および酸化亜鉛２部を添加し、攪拌下に２６０℃まで昇温し、酸価が２０以下となるまで反応した。更に２３０℃まで冷却した後、前記レゾール型ノニルフェノール７０％キシレン溶液３９４部（固形分２７６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８．０Ｐａ・ｓとなるよう調整し、０．０２ＭＰａで１０分間減圧後、内容物を冷却してロジン変性フェノール樹脂（以下、樹脂Ａという）を得た。なお、酸価は１６．８、軟化点は１６８℃、重量平均分子量は９２，０００であった。
Comparative production example 1
(Production of rosin-modified phenolic resin)
In a reaction vessel similar to Production Example 1, 552 parts of gum rosin was charged, and the mixture was heated to 230 ° C. and stirred while stirring in a nitrogen atmosphere. Next, 52 parts of pentaerythritol and 2 parts of zinc oxide were added, the temperature was raised to 260 ° C. with stirring, and the reaction was continued until the acid value became 20 or less. After further cooling to 230 ° C., 394 parts of the resol-type nonylphenol 70% xylene solution (solid content: 276 parts) was dropped into the system over a period of 4 hours within a temperature range of 230 to 260 ° C. After completion of the dropping, the 33% by weight linseed oil viscosity was adjusted to 8.0 Pa · s, and after reducing the pressure at 0.02 MPa for 10 minutes, the contents were cooled to obtain a rosin-modified phenolic resin (hereinafter referred to as “resin A”). It was. The acid value was 16.8, the softening point was 168 ° C., and the weight average molecular weight was 92,000.
参照例１
ガムロジンカルシウム塩（商品名 ライムレジンＮｏ．１、荒川化学工業（株）製）をそのまま顔料コーティング剤として用いた。（以下、樹脂Ｂという。）
Reference example 1
Gum rosin calcium salt (trade name: Lime Resin No. 1, manufactured by Arakawa Chemical Industries, Ltd.) was used as it was as a pigment coating agent. (Hereinafter referred to as Resin B)
参照例２
（バインダー樹脂用のロジン系ポリエステル樹脂の製造）
製造例１と同様の反応容器に、炭素数１６〜１８のα−オレフィン（商品名「ダイアレン１６８」、三菱化学（株）製）２３８部を仕込み、反応系を窒素雰囲気下に攪拌しながら１５５〜１６０℃まで昇温し、これを溶融した。次いで、同反応容器に、無水マレイン酸９８部、ジ−ｔ−ブチルパーオキサイド（商品名「パーブチルＤ」、日本油脂（株）製）１３．５部を、１時間かけて連続的に添加し、攪拌下に反応系を１５５〜１６０℃で１時間保温し、更にステアリルアルコール２７１部を添加して、２２０℃で４時間反応させ、樹脂（重量平均分子量：４，３００）を製造した。次いで、製造例１と同様の反応容器に、当該樹脂を９４部、他にも重合ロジン（商品名 シルバタック１４０、シルバケム社製、酸価：１４０）を３５９部、前記フマル酸変性ロジンを５７部、前記カルボキシル基含有石油樹脂樹脂４３３部を仕込み、窒素雰囲気下に攪拌しながら１８０℃まで昇温してこれらを溶融した。次いで、同反応容器にペンタエリスリトール２９部、グリセリン２９部を添加し、攪拌下に２６０℃まで昇温し、酸価が２０以下となるまでエステル化反応させた。反応終了後、３３重量％アマニ油粘度を８．０Ｐａ・ｓに調整し、０．０２ＭＰａで１０分間減圧、冷却して固形バインダー樹脂を得た。当該バインダー樹脂の酸価は１５．５、軟化点は１６５℃、重量平均分子量は１５０，０００であった。
Reference example 2
(Manufacture of rosin polyester resin for binder resin)
A reaction vessel similar to Production Example 1 was charged with 238 parts of an α-olefin having a carbon number of 16 to 18 (trade name “Dialene 168”, manufactured by Mitsubishi Chemical Corporation), and the reaction system was stirred at 155 under a nitrogen atmosphere. The temperature was raised to ˜160 ° C. and melted. Next, 98 parts of maleic anhydride and 13.5 parts of di-t-butyl peroxide (trade name “Perbutyl D”, manufactured by NOF Corporation) were continuously added to the reaction vessel over 1 hour. While stirring, the reaction system was kept at 155 to 160 ° C. for 1 hour, and 271 parts of stearyl alcohol was further added and reacted at 220 ° C. for 4 hours to produce a resin (weight average molecular weight: 4,300). Next, 94 parts of the resin, 359 parts of polymerized rosin (trade name: Silvatac 140, manufactured by Silvachem, acid value: 140), 57 parts of the fumaric acid-modified rosin were added to the same reaction vessel as in Production Example 1. And 433 parts of the carboxyl group-containing petroleum resin resin were charged and heated to 180 ° C. with stirring in a nitrogen atmosphere to melt them. Subsequently, 29 parts of pentaerythritol and 29 parts of glycerin were added to the reaction vessel, and the temperature was raised to 260 ° C. with stirring, and the esterification reaction was performed until the acid value became 20 or less. After completion of the reaction, the 33% by weight linseed oil viscosity was adjusted to 8.0 Pa · s, and the pressure was reduced at 0.02 MPa for 10 minutes, followed by cooling to obtain a solid binder resin. The binder resin had an acid value of 15.5, a softening point of 165 ° C., and a weight average molecular weight of 150,000.
実施例・比較例
（自己発熱評価）
ロジン系ポリエステル樹脂１〜４、および樹脂Ｂの自己発熱量（ｍＪ）を、セイコーインスツルメンツ（株）製走査型示差熱量測定装置（ＥＸＳＴＡＲ６０００ ＤＳＣ６２００）を用いて測定した。具体的には、各樹脂１０ｍｇを装置に入れ、昇温速度が１０℃／分、温度範囲が室温〜２００℃、測定雰囲気が大気の条件下で測定した。結果、ロジン系ポリエステル樹脂１〜４、樹脂Ｂは、いずれについても発熱の発生を示すピークが認められなかった。（即ち、前記比〔ｍＪ／ｍｇ〕はいずれについても実質的に０であった。）
一方、樹脂Ａの前記比〔ｍＪ／ｍｇ〕は、３７であった。
Examples and comparative examples (self-heating evaluation)
The rosin polyester resins 1 to 4 and the self-heating value (mJ) of the resin B were measured using a scanning differential calorimeter (EXSTAR6000 DSC6200) manufactured by Seiko Instruments Inc. Specifically, 10 mg of each resin was placed in the apparatus, and the measurement was performed under the conditions of a temperature rising rate of 10 ° C./min, a temperature range of room temperature to 200 ° C., and a measurement atmosphere. As a result, none of the rosin-based polyester resins 1 to 4 and the resin B showed a peak indicating the generation of heat. (That is, the ratio [mJ / mg] was substantially 0 in all cases.)
On the other hand, the ratio [mJ / mg] of the resin A was 37.
（被覆顔料の製造）
アトライターに、ロジン系ポリエステル樹脂１を７重量部、粗製フタロシアニンブルー（藍顔料）を７０重量部加え、窒素気流下に１６０℃で１時間乾式粉砕を行った。得られた顔料を被覆顔料１とする。同様に、ロジン系ポリエステル樹脂２〜４について被覆顔料２〜４を、また、樹脂Ａ、樹脂Ｂについて被覆顔料Ａ、被覆顔料Ｂを得た。
(Manufacture of coated pigments)
7 parts by weight of rosin-based polyester resin 1 and 70 parts by weight of crude phthalocyanine blue (indigo pigment) were added to the attritor, and dry pulverization was performed at 160 ° C. for 1 hour in a nitrogen stream. The resulting pigment is referred to as coated pigment 1. Similarly, coated pigments 2 to 4 were obtained for rosin polyester resins 2 to 4, and coated pigment A and coated pigment B were obtained for resins A and B.
（印刷インキ組成物の調整）
前記参照例２で得たバインダー樹脂を４５．０部、大豆油を１０部、ＡＦソルベント７号を４５．０部、容器に仕込み、１８０℃において３０分混合・溶解して、ワニスを得た。次いで、該ワニスを６０℃まで冷却し、更にアルミキレート(商品名 ＡＬＣＨ、川研ファインケミカル（株）製)を１．０部加えて系を攪拌、混合した。その後、生成物を１９０℃で１時間保温し、ゲルワニスとした。
(Adjustment of printing ink composition)
45.0 parts of binder resin obtained in Reference Example 2, 10 parts of soybean oil, 45.0 parts of AF solvent 7 were charged in a container, and mixed and dissolved at 180 ° C. for 30 minutes to obtain a varnish. . Subsequently, the varnish was cooled to 60 ° C., and further 1.0 part of aluminum chelate (trade name: ALCH, manufactured by Kawaken Fine Chemical Co., Ltd.) was added, and the system was stirred and mixed. Thereafter, the product was kept at 190 ° C. for 1 hour to obtain a gel varnish.
次いで、該ゲルワニスを用いて、被覆顔料や他の原料を表１に示した配合割合となるように三本ロールミルで練肉し、タック値が６．５±０．５、フロー値が４１．０±１．０となるように調整した印刷インキ１を得た。また、被覆顔料２〜４、被覆顔料Ａ、被覆顔料Ｂについても同様にして、印刷インキ２〜４、印刷インキＡ、印刷インキＢを得た。 Next, using the gel varnish, the coated pigment and other raw materials were kneaded with a three roll mill so as to have the blending ratio shown in Table 1, and the tack value was 6.5 ± 0.5 and the flow value was 41. Printing ink 1 adjusted to be 0 ± 1.0 was obtained. Moreover, the printing inks 2-4, the printing ink A, and the printing ink B were obtained similarly about the coating pigments 2-4, the coating pigment A, and the coating pigment B.
（印刷インキの乳化試験）
印刷インキＡの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、次いで純水を５ｍｌ／分の速度で供給し（ロール温度３０℃、ロール回転速度２００ｒｐｍ）、当該印刷インキ中の水分量を、赤外水分計を用いて測定した。結果、印刷インキ１の乳化率は４０％、印刷インキ２は３８％、印刷インキ３は３７％、印刷インキ４は３６％であった。一方、印刷インキＡは３９％、また印刷インキＢは６８％（過乳化）であった。
(Printing ink emulsification test)
3.9 ml of printing ink A is developed on a dynamic emulsification tester (manufactured by Nippon Rheology Equipment Co., Ltd.), and then pure water is supplied at a rate of 5 ml / min (roll temperature 30 ° C., roll rotation speed 200 rpm). ), The moisture content in the printing ink was measured using an infrared moisture meter. As a result, the emulsification rate of printing ink 1 was 40%, printing ink 2 was 38%, printing ink 3 was 37%, and printing ink 4 was 36%. On the other hand, the printing ink A was 39% and the printing ink B was 68% (overemulsification).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014172962A (en) * | 2013-03-07 | 2014-09-22 | Arakawa Chem Ind Co Ltd | Resin composition for printing ink, varnish for printing ink, and printing ink |
| JP2020033430A (en) * | 2018-08-28 | 2020-03-05 | サカタインクス株式会社 | Ink composition for plasma curing, and additive for ink composition for plasma curing |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53134032A (en) * | 1977-04-28 | 1978-11-22 | Toyo Soda Mfg Co Ltd | Production of easy dispersion granular pigment |
| JP2001139670A (en) * | 1999-08-31 | 2001-05-22 | Arakawa Chem Ind Co Ltd | Polyester resin, its preparation process, printing ink binder and printing ink |
| JP2003020431A (en) * | 2001-07-09 | 2003-01-24 | Toyo Ink Mfg Co Ltd | Printing ink and printed article using the same |
| JP2004018619A (en) * | 2002-06-14 | 2004-01-22 | Arakawa Chem Ind Co Ltd | Polyester resin, its manufacturing method, binder for printing ink and printing ink |
| JP2004155908A (en) * | 2002-11-06 | 2004-06-03 | Arakawa Chem Ind Co Ltd | Polyester resin, production method therefor, printing ink binder, and printing ink |
| JP2004224820A (en) * | 2003-01-20 | 2004-08-12 | Harima Chem Inc | Modified carbon black |
| JP2004285255A (en) * | 2003-03-24 | 2004-10-14 | Seiko Polymer Corp | Resin for printing ink, and printing ink using the same |
| JP2006016514A (en) * | 2004-07-02 | 2006-01-19 | Toyo Ink Mfg Co Ltd | Crushed composition of carbon black and resin, carbon black resin composition, and offset printing ink using the same |
| JP2007112966A (en) * | 2005-10-24 | 2007-05-10 | Toyo Ink Mfg Co Ltd | Manufacturing method of pigment composition, pigment composition obtained thereby, printing ink using the same and its printed matter |
-
2006
- 2006-02-03 JP JP2006027404A patent/JP5546091B2/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53134032A (en) * | 1977-04-28 | 1978-11-22 | Toyo Soda Mfg Co Ltd | Production of easy dispersion granular pigment |
| JP2001139670A (en) * | 1999-08-31 | 2001-05-22 | Arakawa Chem Ind Co Ltd | Polyester resin, its preparation process, printing ink binder and printing ink |
| JP2003020431A (en) * | 2001-07-09 | 2003-01-24 | Toyo Ink Mfg Co Ltd | Printing ink and printed article using the same |
| JP2004018619A (en) * | 2002-06-14 | 2004-01-22 | Arakawa Chem Ind Co Ltd | Polyester resin, its manufacturing method, binder for printing ink and printing ink |
| JP2004155908A (en) * | 2002-11-06 | 2004-06-03 | Arakawa Chem Ind Co Ltd | Polyester resin, production method therefor, printing ink binder, and printing ink |
| JP2004224820A (en) * | 2003-01-20 | 2004-08-12 | Harima Chem Inc | Modified carbon black |
| JP2004285255A (en) * | 2003-03-24 | 2004-10-14 | Seiko Polymer Corp | Resin for printing ink, and printing ink using the same |
| JP2006016514A (en) * | 2004-07-02 | 2006-01-19 | Toyo Ink Mfg Co Ltd | Crushed composition of carbon black and resin, carbon black resin composition, and offset printing ink using the same |
| JP2007112966A (en) * | 2005-10-24 | 2007-05-10 | Toyo Ink Mfg Co Ltd | Manufacturing method of pigment composition, pigment composition obtained thereby, printing ink using the same and its printed matter |
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| JP2014172962A (en) * | 2013-03-07 | 2014-09-22 | Arakawa Chem Ind Co Ltd | Resin composition for printing ink, varnish for printing ink, and printing ink |
| JP2020033430A (en) * | 2018-08-28 | 2020-03-05 | サカタインクス株式会社 | Ink composition for plasma curing, and additive for ink composition for plasma curing |
| JP7139194B2 (en) | 2018-08-28 | 2022-09-20 | サカタインクス株式会社 | Plasma-curable ink composition and additive for plasma-curable ink composition |
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