JP6052318B2 - Lithographic printing ink composition - Google Patents
Lithographic printing ink composition Download PDFInfo
- Publication number
- JP6052318B2 JP6052318B2 JP2015055718A JP2015055718A JP6052318B2 JP 6052318 B2 JP6052318 B2 JP 6052318B2 JP 2015055718 A JP2015055718 A JP 2015055718A JP 2015055718 A JP2015055718 A JP 2015055718A JP 6052318 B2 JP6052318 B2 JP 6052318B2
- Authority
- JP
- Japan
- Prior art keywords
- oil
- ink
- vegetable oil
- weight
- printing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000007639 printing Methods 0.000 title claims description 64
- 239000000203 mixture Substances 0.000 title claims description 41
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 94
- 239000008158 vegetable oil Substances 0.000 claims description 92
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 22
- 229910052740 iodine Inorganic materials 0.000 claims description 22
- 239000011630 iodine Substances 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 2
- 239000003921 oil Substances 0.000 description 36
- 235000019198 oils Nutrition 0.000 description 36
- 239000002904 solvent Substances 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000000049 pigment Substances 0.000 description 19
- 239000002966 varnish Substances 0.000 description 17
- 238000004945 emulsification Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 239000001993 wax Substances 0.000 description 14
- 239000003208 petroleum Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 238000007645 offset printing Methods 0.000 description 11
- 235000012424 soybean oil Nutrition 0.000 description 11
- 239000003549 soybean oil Substances 0.000 description 11
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000000194 fatty acid Substances 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- 150000004665 fatty acids Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- -1 polyoxyethylene Polymers 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
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- 239000007787 solid Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
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- 238000012546 transfer Methods 0.000 description 6
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004006 olive oil Substances 0.000 description 3
- 235000008390 olive oil Nutrition 0.000 description 3
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- 239000007858 starting material Substances 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- 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 description 3
- 239000002383 tung oil Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 235000019483 Peanut oil Nutrition 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 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 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 230000000903 blocking effect Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002170 ethers Chemical class 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
- 235000020993 ground meat Nutrition 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-M hydroperoxide group Chemical group [O-]O MHAJPDPJQMAIIY-UHFFFAOYSA-M 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
- 230000026045 iodination Effects 0.000 description 2
- 238000006192 iodination reaction Methods 0.000 description 2
- 235000013372 meat Nutrition 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- 239000005011 phenolic resin Substances 0.000 description 2
- 150000002989 phenols Chemical class 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
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- 238000003860 storage Methods 0.000 description 2
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- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
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- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical compound CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 1
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- 238000006317 isomerization reaction Methods 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000012184 mineral wax Substances 0.000 description 1
- 239000008164 mustard oil Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000015227 regulation of liquid surface tension Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 230000000630 rising effect Effects 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
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- OJQMPIICCPYCQQ-UHFFFAOYSA-N tetracos-15-en-1-ol Chemical compound CCCCCCCCC=CCCCCCCCCCCCCCCO OJQMPIICCPYCQQ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000008170 walnut oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide 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
Description
本発明は、書籍、チラシ、カタログ、ポスター等を印刷する平版印刷に使用される平版印刷インキ組成物（以下、「インキ」と略す。）に関するものであり、特に、印刷品質の向上と印刷作業性の向上に関するものであり、更には、乳化適性、光沢、着肉性に優れ、乳化トラブルを低減できるインキに関するものである。 The present invention relates to a lithographic printing ink composition (hereinafter abbreviated as “ink”) used for lithographic printing for printing books, flyers, catalogs, posters, etc., and in particular, improving printing quality and printing work. Further, the present invention relates to an ink that is excellent in emulsification suitability, gloss, and inking properties, and can reduce emulsification troubles.
近年印刷業界では、印刷時の省人、省力化、自動化、高速化の要求が高まってきている事に合わせて、様々な印刷条件下に於いてトラブルレスで長時間安定して高品位な印刷物が得られる印刷用インキが望まれており、インキメーカーでは種々の改良を実施してきている。 In recent years, in the printing industry, demands for labor saving, labor saving, automation, and high-speed printing have been increasing. Ink for printing is desired, and ink manufacturers have made various improvements.
特にドットの小さいFMスクリーン、また印刷物の精細さの向上、および印刷会社自体のインキ使用量削減の観点からAMスクリーンの高精細化が急速に普及している。そのため、先刷りインキが後刷り用のブランケットに付着して徐々に堆積していく後胴残りなどのインキのセット性に依存する印刷トラブルへのインキ面からの対応が求められている。 In particular, high-definition AM screens are rapidly spreading from the viewpoint of FM screens with small dots, improved print quality, and reduced ink usage by the printing companies themselves. Therefore, there is a demand from the ink surface for printing troubles that depend on ink setting properties such as the back cylinder residue where the preprinted ink adheres to the blanket for postprinting and gradually accumulates.
こうした後胴残りなどの問題に対してはインキのセット性を遅くすることが、対応策の一つとなっている。セット性を遅くするためには、植物油などに代表される溶解性の高い素材を用いて、樹脂との相溶性を上げることが有用な方法の一つとして挙げられる。しかし、特にヒートセットオフセット印刷では、ドライヤー部での短時間の通過での蒸発乾燥性が要求されるが、揮発性の低い植物油が多く添加されると乾燥性が不利になる。そのため、お互いトレードオフの関係にあるセット性と乾燥性のバランスを考慮し、植物油量も大幅に上げられないのが現状である。 One of the countermeasures is to slow down the ink setting for such problems as the back cylinder remaining. In order to slow the setting property, one of useful methods is to increase the compatibility with the resin by using a highly soluble material typified by vegetable oil. However, particularly in heat set offset printing, evaporative drying is required in a short time passage in the dryer section. However, if a large amount of low-volatile vegetable oil is added, the drying becomes disadvantageous. Therefore, the amount of vegetable oil cannot be increased significantly considering the balance between setability and dryness, which are in a trade-off relationship with each other.
特許文献１では、植物油脂由来の脂肪族アルコールから誘導される220〜310℃を沸点にもつジアルキルエーテルをワニス中の溶剤として使用している。しかし、このような高溶解溶剤をワニス中に用いた場合、樹脂の溶解性が大幅に向上し、プリンティングタックが大幅に上昇し、高速印刷時での紙剥けやミスチングといった印刷トラブルにつながる恐れがある。 In Patent Document 1, a dialkyl ether having a boiling point of 220 to 310 ° C. derived from a vegetable alcohol-derived aliphatic alcohol is used as a solvent in the varnish. However, if such a high-solubility solvent is used in the varnish, the solubility of the resin will be greatly improved, the printing tack will be greatly increased, and this may lead to printing problems such as paper peeling and misting during high-speed printing. is there.
また、オフセット印刷は、画線と呼ばれる親油性部に油分であるインキ、非画線部と呼ばれる親水性部に湿し水を付着させ、油と水の反発により画像を形成し、ブランケット、紙へと転写する印刷方式である。この印刷方式では必然的に湿し水と油性インキが接触し乳化状態となる。このとき、インキが水となじみやすかったり、多量に湿し水を取り込んでしまうとインキが水に散ったり、水が不足したりして、非画線部となるべき部分にインキが付着したりにじんだりして、いわゆる汚れの問題が発生する。一方、インキの乳化の許容範囲が極端に低い場合は、絵柄のバランスの関係により水の供給量が多い際にインキが過乳化し、元々の粘弾性が失われ、ローラー間の転移不良を発生し、ローラー上にインキが余ってしまうなどの問題も発生する。 In addition, offset printing is performed by attaching ink, which is oil, to the oleophilic area called the image line, and dampening water on the hydrophilic area, called the non-image area, to form an image by repulsion between oil and water. It is a printing method that transfers to the head. In this printing method, fountain solution and oil-based ink inevitably come into an emulsified state. At this time, if the ink is easy to mix with water, or if a large amount of dampening water is taken in, the ink may be scattered in the water, or the water may be insufficient, and the ink may adhere to the portion that should be the non-image area. And so-called dirt problem occurs. On the other hand, if the allowable range of ink emulsification is extremely low, the ink is over-emulsified when the amount of water supplied is large due to the balance of the pattern, and the original viscoelasticity is lost, resulting in poor transfer between rollers. In addition, problems such as ink remaining on the roller also occur.
このようにオフセット印刷方式では、幅広い水幅の間で乳化状態を安定させ、優れた印刷適性を有するインキが求められている。
こうした乳化コントロールの方法としては界面活性剤などを用いることが有用な方法の一つとしてあげられている。
Thus, in the offset printing method, there is a demand for an ink that stabilizes the emulsified state over a wide water width and has excellent printability.
As such an emulsification control method, use of a surfactant or the like is mentioned as one of useful methods.
特許文献２、３では、ポリオキシエチレンアルキルフェニルエーテル等の界面活性剤が使用されている（特許文献２および３）。しかしながら、これらの界面活性剤乳化剤の原料として広く用いられているノニルフェノールに環境ホルモンとして懸念されるようになってきており、環境面で好ましくない。 In Patent Documents 2 and 3, a surfactant such as polyoxyethylene alkylphenyl ether is used (Patent Documents 2 and 3). However, nonylphenol, which is widely used as a raw material for these surfactant emulsifiers, has come to be concerned as an environmental hormone, which is not preferable in terms of the environment.
特許文献４ではこれらの環境面での対応としてポリエーテルポリオールを用いている。界面活性剤は少量で乳化率を大幅に向上することができる一方で、界面活性自体が親水性のために添加率の制御が難しく、過剰に入れた場合が著しい汚れの発生を引き起こす。 In Patent Document 4, polyether polyol is used as a countermeasure for these environmental aspects. While the surfactant can greatly improve the emulsification rate with a small amount, the surfactant activity itself is hydrophilic, so it is difficult to control the addition rate, and when it is excessively added, the occurrence of significant stains is caused.
本発明はこのような従来の技術における印刷適性上及び印刷品質上、さらにはインキ製造中や印刷現場での作業効率を大幅に向上することを目的としている。すなわち、ドットが小さい事に由来する印刷トラブルを低減してロングランでの連続印刷を可能とし、乾燥性が良好なインキを提供する。更には、乳化コントロールを適正に行うことで、幅広い水幅の間において印刷トラブルを低減してロングランでの連続印刷を可能とするインキを提供する。更には、環境への負荷も低減することができるインキに関するものである。 The object of the present invention is to greatly improve the work efficiency on the printability and the print quality in the prior art as well as during ink production and at the printing site. That is, it is possible to reduce the printing trouble caused by small dots, enable continuous printing with a long run, and provide an ink with good drying properties. Furthermore, by appropriately performing emulsification control, an ink is provided that enables continuous printing in a long run by reducing printing troubles over a wide water width. Furthermore, the present invention relates to an ink that can reduce the burden on the environment.
バインダー樹脂、酸化重合植物油および植物油類を含有する平版印刷インキ組成物において、一定範囲の分子量、ヨウ素価を有する重合植物油を一定量含有させることにより、セット性、乾燥性、乳化適性に優れ、印刷時の後胴残り、乾燥トラブル、乳化トラブルを抑制するインキの製造に至った。
すなわち、本発明は、バインダー樹脂、重合植物油および植物油類を含有することを特徴とする平版印刷インキ組成物であって、
重合植物油が、ヨウ素価１００〜１４０（ｍｇ／１００ｍｇ）の、植物油および／または再生植物油由来の重合植物油であり、かつ、重量平均分子量３００００〜１５００００であることを特徴とする平版印刷インキ組成物に関する。
In a lithographic printing ink composition containing a binder resin, oxidatively polymerized vegetable oil and vegetable oils, by containing a certain amount of polymerized vegetable oil having a certain range of molecular weight and iodine value, it is excellent in setability, drying properties and emulsification suitability. It has led to the production of ink that suppresses back trunk, drying troubles, and emulsification troubles.
That is, the present invention is a lithographic printing ink composition comprising a binder resin, a polymerized vegetable oil, and vegetable oils ,
The present invention relates to a lithographic printing ink composition, wherein the polymerized vegetable oil is a polymerized vegetable oil derived from vegetable oil and / or regenerated vegetable oil having an iodine value of 100 to 140 (mg / 100 mg) and having a weight average molecular weight of 30,000 to 150,000. .
さらに、本発明は、平版印刷インキ組成物全量中、重合植物油を０．５〜１０重量％含有することを特徴とする上記平版印刷インキ組成物に関する。 Furthermore, this invention relates to the said lithographic printing ink composition characterized by containing 0.5 to 10weight% of polymerization vegetable oils in the lithographic printing ink composition whole quantity.
さらに、本発明は、上記平版印刷インキ組成物を、基材に印刷してなる印刷物に関する。 Furthermore, this invention relates to the printed matter formed by printing the said lithographic printing ink composition on a base material.
従来では、インキのセット性を遅延するためには樹脂自体の高溶解化、ワニス用溶剤の高溶解化が行われてきたが、樹脂設計の困難さやコストメリット性にかけていた。また、乾性油を出発原料とした重合植物油では酸化し易く空気中の不安定性による増粘や皮張りの発生などの取扱上の問題をはらんでいた。本願発明によって、インキ製造中、印刷現場で容易に添加することが可能となり、更にはその添加量を調整することで容易にインキのセット性を操作することが可能となった。
また、従来では、オフセットインキの乳化適性のコントロール方法としては界面活性剤を用いる方法が用いられてきたが、環境面、および少量で乳化率を大幅に向上させるがために水幅下限が弱くなり、汚れなどのトラブル発生の弊害があった。本発明によって、環境負荷の大幅な低減、および容易にインキの乳化コントロールを容易に操作することが可能となった。
Conventionally, in order to delay the setting property of the ink, the resin itself has been highly dissolved and the solvent for the varnish has been highly dissolved, but it has been difficult to design the resin and cost merit. In addition, polymerized vegetable oils starting from dry oils are easily oxidized and have problems in handling such as thickening and skinning due to instability in the air. According to the present invention, it is possible to easily add ink at the printing site during ink production, and furthermore, it is possible to easily operate the ink setting property by adjusting the addition amount.
Conventionally, a method using a surfactant has been used as a method for controlling the emulsification suitability of the offset ink. However, the lower limit of the water width becomes weak because the emulsification rate is greatly improved in an environmental aspect and in a small amount. There was an adverse effect of troubles such as dirt. According to the present invention, it has become possible to greatly reduce the environmental burden and to easily operate the emulsification control of the ink.
本願発明で使用されるバインダー樹脂とはロジン変性フェノール樹脂、ロジン変性マレイン酸樹脂、アルキド樹脂、ポリエステル樹脂および石油樹脂等を示し、それらは任意に単独または２種類以上を組み合わせて使用でき、好ましくは、ロジン変性フェノール樹脂を使用することが望ましい。 The binder resin used in the present invention refers to rosin-modified phenolic resin, rosin-modified maleic acid resin, alkyd resin, polyester resin, petroleum resin, etc., which can be used alone or in combination of two or more, preferably It is desirable to use a rosin modified phenolic resin.
バインダー樹脂であるロジン変性フェノール樹脂の重量平均分子量は、２００００〜２０００００の範囲が望ましく、より好ましくは２５０００〜１６００００、さらに好ましくは３００００〜１２００００の範囲であることが望ましい。２００００未満では弾性が低くなりミスチングを増大させる懸念があり、２０００００を超える重量平均分子量では流動性や着肉性を劣化させる懸念がある。 The weight average molecular weight of the rosin-modified phenol resin that is a binder resin is preferably in the range of 20000 to 200000, more preferably 25000 to 16000, and still more preferably in the range of 30000 to 120,000. If it is less than 20000, there is a concern that elasticity will be low and misting will increase, and if it exceeds 200,000, there is a concern that fluidity and inking properties will be deteriorated.
本願発明に関するロジン変性フェノール樹脂は、ノルマルパラフィン白濁温度が４０〜１６０℃の範囲が望ましく、さらに好ましくは５０〜１３０℃の範囲である。本願発明において、ノルマルパラフィン白濁温度とは、樹脂１０重量％と１４〜１６の炭素数を有するノルマルパラフィン９０重量％を加熱混合した際に、白濁する下限の温度をいう（それ以上の温度では白濁が観察されない。）。４０℃未満では樹脂の溶解性が高すぎるのでインキのタックが高くなり、１６０℃を超える白濁温度では樹脂の溶解性が低すぎるので溶剤が離脱し易く機上でインキが締まり易くなる。 The rosin-modified phenolic resin relating to the present invention preferably has a normal paraffin turbidity temperature in the range of 40 to 160 ° C, more preferably in the range of 50 to 130 ° C. In the present invention, the normal paraffin white turbidity temperature means a lower limit temperature at which white turbidity occurs when 10% by weight of the resin and 90% by weight of normal paraffin having 14 to 16 carbon atoms are heated and mixed (at higher temperatures, the white turbidity). Is not observed.) If the temperature is lower than 40 ° C., the resin has too high solubility, and the tackiness of the ink becomes high. If the clouding temperature exceeds 160 ° C., the solubility of the resin is too low, so that the solvent is easily removed and the ink is easily tightened on the machine.
本願発明における酸化重合植物油は、特にヨウ素価が１００〜１４０（ｍｇ／１００ｍｇ）の植物油および／または再生植物油を酸素を含む空気を吹き込みながら加熱・攪拌することで得られる。特にヨウ素価が１００〜１４０（ｍｇ／１００ｍｇ）の植物油および／または再生植物油を原料とする場合、二重結合が少なく反応点が少ないがため、これまで使われていた重合植物油である熱重合タイプのものでは、重合反応が進まず、所望の分子量が得られない。植物油原料は１００〜１４０（ｍｇ／１００ｍｇ）である菜種油、ごま油、大豆油などの半乾性油、またはその範囲内にある再生植物油とすることで、重合反応も円滑に進行し、生成した重合植物油のヨウ素価は１００（ｍｇ／１００ｍｇ）以下となり、空気中での酸化進行による増粘や皮張りの発生が抑制され、取扱い性も良好である。なお、この際、反応を円滑に進める上でヨウ素価が１４０（ｍｇ／１００ｍｇ）以上ある亜麻仁油や桐油を全植物油原料中の１〜３０重量％加えるのも有効である。 The oxidation-polymerized vegetable oil in the present invention is obtained by heating and stirring a vegetable oil and / or a regenerated vegetable oil having an iodine value of 100 to 140 (mg / 100 mg) while blowing air containing oxygen. In particular, when vegetable oil and / or regenerated vegetable oil having an iodine value of 100 to 140 (mg / 100 mg) is used as a raw material, since there are few double bonds and few reaction points, the thermal polymerization type that is a polymerized vegetable oil used so far However, the polymerization reaction does not proceed and the desired molecular weight cannot be obtained. The vegetable oil raw material is 100-140 (mg / 100 mg) rapeseed oil, sesame oil, soybean oil and other semi-dry oils, or regenerated vegetable oils within the range, so that the polymerization reaction proceeds smoothly, and the produced polymer vegetable oil Has an iodine value of 100 (mg / 100 mg) or less, suppresses the occurrence of thickening and skinning due to the progress of oxidation in the air, and is easy to handle. In this case, it is also effective to add 1-30% by weight of linseed oil or tung oil having an iodine value of 140 (mg / 100 mg) or more in order to facilitate the reaction.
酸化重合による重合植物油は空気を吹き込むことで得られるが、このとき金属ドライヤーなどの触媒を添加すると反応速度が速くなる。前者を一般に吹き込み油、後者をボイル油という。この酸化重合の過程では植物油中の植物油の脂肪酸同士が酸素原子の連結されるともに、水酸基、カルボキシル基、ヒドロペルオキシド基、カルボニル基などが生成し、分子全体として酸素の割合が増加する。また、同時に空気中に含まれる、もしくは反応中に発生する水により植物油のエステル結合が加水分解されることで、カルボキシル基、水酸基が生成することで、熱重合品と比較し、乳化しやすくなる。よって、適切量の酸化重合による重合植物油を添加することで、インキの乳化率もより増加させ、適度な乳化適性を付与させることが可能となる。 Polymerized vegetable oil by oxidative polymerization can be obtained by blowing air. At this time, the addition of a catalyst such as a metal dryer increases the reaction rate. The former is generally called blown oil and the latter is called boiled oil. In the process of this oxidative polymerization, the fatty acids of the vegetable oil in the vegetable oil are linked with oxygen atoms, and a hydroxyl group, a carboxyl group, a hydroperoxide group, a carbonyl group, and the like are generated, and the proportion of oxygen increases as a whole molecule. At the same time, the ester bond of the vegetable oil is hydrolyzed by water contained in the air or generated during the reaction, so that a carboxyl group and a hydroxyl group are generated, which makes it easier to emulsify compared to a thermal polymerized product. . Therefore, by adding an appropriate amount of polymerized vegetable oil by oxidative polymerization, the emulsification rate of the ink can be further increased, and appropriate emulsification suitability can be imparted.
一方で、熱重合は空気の吹き込みなどは行わず、加熱操作のみで得られる。熱重合は,二重結合の移動を伴う共役異性化とディールス-アルダ-型の付加重合反応で進行し、植物油の脂肪酸部の分子内および分子間の反応でシクロヘキセン環を生成する。また、酸化重合と同様に二重結合の開裂や原料となる植物油中に元から含まれる若干の水分により加水分解され、カルボキシル基や水酸基もわずかに発生するが、分子全体の酸素原子割合は酸化重合時よりも低いため、乳化率アップへの寄与が乏しいと考えられる。特に、ヨウ素価が１４０（ｍｇ／１００ｍｇ）以上ある高い亜麻仁油や桐油、紅花油などの乾性油は熱重合でも容易に重合させることが容易であるが、重合後も多くの二重結合が残存し、酸化し易く、皮張りが発生し保存安定性や取扱い性が非常に悪い。しかし、ヨウ素価が１４０（ｍｇ／１００ｍｇ）以下となる菜種油、ごま油、大豆油などの反応点が少ないため、半乾性油を熱重合により重合させるには乾性油より容易ではない。さらに、ヨウ素価が１００（ｍｇ／１００ｍｇ）以下であるオリーブ油、落花生油などの不乾性油を出発原料とした場合、不乾性油以上に反応点が少なく、より熱重合は困難となる。 On the other hand, thermal polymerization is not performed by blowing air or the like and can be obtained only by a heating operation. Thermal polymerization proceeds by conjugate isomerization with double bond transfer and Diels-Alda-type addition polymerization reaction, and forms cyclohexene ring by intramolecular and intermolecular reactions in the fatty acid part of vegetable oil. In addition, as with oxidative polymerization, double bonds are cleaved and hydrolyzed by some moisture originally contained in the raw vegetable oil, producing a small amount of carboxyl groups and hydroxyl groups, but the oxygen atom ratio of the whole molecule is oxidized. It is considered that the contribution to increasing the emulsification rate is poor because it is lower than at the time of polymerization. In particular, dry oils such as linseed oil, tung oil, safflower oil and the like having an iodine value of 140 (mg / 100 mg) or more can be easily polymerized by thermal polymerization, but many double bonds remain after polymerization. However, it is easy to oxidize, a skin is generated, and storage stability and handling are very poor. However, since there are few reaction points of rapeseed oil, sesame oil, soybean oil, etc. with an iodine value of 140 (mg / 100 mg) or less, it is not easy to polymerize semi-drying oil by thermal polymerization. Furthermore, when non-drying oils such as olive oil and peanut oil having an iodine value of 100 (mg / 100 mg) or less are used as starting materials, there are fewer reactive sites than non-drying oils, making thermal polymerization more difficult.
また、重合植物油と顔料の濡れ性に関して、水酸基、カルボキシル基、ヒドロペルオキシド基、カルボニル基などの熱重合品よりも極性基が多く存在する酸化重合品が良好である。さらに、重合反応した植物油の多数のアルキル基が複雑に配置し、これらの立体障害により顔料の再凝集を防ぐ働きもある。また、本願発明における酸化重合植物油は平版印刷インキ組成物で用いられる植物油や石油系溶剤との相溶性もよく、セット遅延効果も非常に高い。 Further, regarding the wettability of the polymerized vegetable oil and the pigment, an oxidation polymer product having more polar groups is better than a thermal polymer product such as a hydroxyl group, a carboxyl group, a hydroperoxide group, and a carbonyl group. Furthermore, a large number of alkyl groups of the vegetable oil subjected to the polymerization reaction are arranged in a complicated manner, and these steric hindrances also serve to prevent reaggregation of the pigment. In addition, the oxidation-polymerized vegetable oil in the present invention has good compatibility with the vegetable oil and petroleum solvent used in the lithographic printing ink composition, and has a very high set delay effect.
本願発明における重合植物油は、重量平均分子量が３００００〜１５００００であることが好ましい。重量平均分子量が３００００以下では重合植物油の粘度が低く、インキに添加した際にインキの粘度も大幅に低下し、印刷中の汚れや網点形状の崩れなどのトラブルが発生する。一方で、重量平均分子量が１５００００を超える範囲では、重合大豆油の粘度が高くなり、弾性が大幅に増し、製造時や印刷現場の取扱性の低下、インキ中に大量に添加した際のインキの流動性低下が誘発される。また、重量平均分子量が１５００００を超えると酸化重合時間が大幅に超過するために過剰な加水分解が誘発され、酸価が上がり、乳化コントロールが困難となる。 The polymerized vegetable oil in the present invention preferably has a weight average molecular weight of 30,000 to 150,000. When the weight average molecular weight is 30000 or less, the viscosity of the polymerized vegetable oil is low, and when added to the ink, the viscosity of the ink is greatly reduced, causing troubles such as smudges during printing and breakage of the halftone dot shape. On the other hand, in the range where the weight average molecular weight exceeds 150,000, the viscosity of the polymerized soybean oil is increased, the elasticity is greatly increased, the handling property at the time of production and printing is lowered, and the ink when added in a large amount in the ink A decrease in fluidity is induced. On the other hand, if the weight average molecular weight exceeds 150,000, the oxidative polymerization time is greatly exceeded, so excessive hydrolysis is induced, the acid value is increased, and emulsification control becomes difficult.
すなわち、以上の条件を満たす本願発明の重合植物油は、従来のヨウ素価の高い植物油を出発原料とした重合植物油と比較し、増粘や皮張り適性などの保存安定性、取扱い性にも長けている点で優れている。更には、その添加量を調整することで容易にインキのセット性、および乳化率をコントロールできるという点で本願発明には必須の成分である。 That is, the polymerized vegetable oil of the present invention that satisfies the above conditions is superior in storage stability and handling properties such as thickening and skinning suitability compared to conventional vegetable oils starting from vegetable oils having a high iodine value. It is excellent in that it is. Furthermore, it is an essential component for the present invention in that the setting property of the ink and the emulsification rate can be easily controlled by adjusting the addition amount.
上記に示す重合植物油は分散工程前のプレミックス段階、または分散後の調整段階で添加してもどちらでも構わない。 The polymerized vegetable oil shown above may be added either in the premix stage before the dispersion process or in the adjustment stage after dispersion.
なお、一般的な植物油としては、大豆油、再生大豆油、菜種油、ヤシ油、オリーブ油、アサ実油、アマニ油、エノ油、オイチシカ油、オリーブ油、カカオ油、カポック油、カヤ油、カラシ油、キョウニン油、キリ油、ククイ油、クルミ油、ケシ油、ゴマ油、サフラワー油、ダイコン種油、大豆油、大風子油、ツバキ油、トウモロコシ油、ナタネ油、ニガー油、ヌカ油、パーム油、ヒマシ油、ヒマワリ油、ブドウ種子油、ヘントウ油、松種子油、綿実油、ヤシ油、落花生油、脱水ヒマシ油、ヤトロファ油等の植物油由来のものや、それらの熱重合油および酸素吹き込み重合油等を例示することができる。 In addition, as general vegetable oil, soybean oil, regenerated soybean oil, rapeseed oil, palm oil, olive oil, flaxseed oil, flaxseed oil, eno oil, jute oil, olive oil, cacao oil, kapok oil, kaya oil, mustard oil, Kyounin oil, Kiri oil, Kukui oil, Walnut oil, Poppy oil, Sesame oil, Safflower oil, Daikon seed oil, Soybean oil, Daifu oil, Camellia oil, Corn oil, Rapeseed oil, Niger oil, Nuka oil, Palm oil, Castor oil, sunflower oil, grape seed oil, gentian oil, pine seed oil, cottonseed oil, coconut oil, peanut oil, dehydrated castor oil, Jatropha oil, etc., their thermal polymerized oil and oxygen-blown polymerized oil, etc. Can be illustrated.
本願発明における植物油類とは植物油および植物油由来の化合物であり、グリセリンと脂肪酸とのトリグリセリドにおいて、少なくとも１つの脂肪酸が炭素−炭素不飽和結合を少なくとも１つ有する脂肪酸であるトリグリセリドと、それらのトリグリセリドから飽和または不飽和アルコールとをエステル反応させてなる脂肪酸モノエステル、あるいは植物油の脂肪酸とモノアルコールを直接エステル反応させた脂肪酸モノエステル、エーテル類が挙げられる。また、本願発明では必要に応じて油としてそれ以外の動植物油、合成油を併用しても良い。 The vegetable oils in the present invention are vegetable oils and compounds derived from vegetable oils. Among triglycerides of glycerin and fatty acids, at least one fatty acid is a fatty acid having at least one carbon-carbon unsaturated bond, and those triglycerides. Examples include fatty acid monoesters obtained by ester reaction with saturated or unsaturated alcohols, or fatty acid monoesters obtained by direct ester reaction between fatty acids of vegetable oil and monoalcohols, and ethers. Moreover, in this invention, you may use together other animal and vegetable oils and synthetic oil as oil as needed.
脂肪酸モノエステルは上記植物油とモノアルコールとをエステル交換したものや植物油の脂肪酸とモノアルコールを直接エステル反応させた脂肪酸モノエステルである。モノアルコールの代表的なものは、メタノール、エタノール、ｎ−またはｉｓｏ−プロパノール、ｎ，ｓｅｃまたはｔｅｒｔ−ブタノール、ヘプチノール、２−エチルヘキサノール、ヘキサノール、オクタノール、デカノール、ドデカノール等の飽和アルコール、オレイルアルコール、ドデセノール、フイセテリアルコール、ゾンマリルアルコール、ガドレイルアルコール、１１−イコセノール、１１−ドコセノール、１５−テトラコセノール等の不飽和脂肪族系アルコールが挙げられる。 The fatty acid monoester is a fatty acid monoester obtained by transesterification of the above vegetable oil and monoalcohol or a direct ester reaction between the fatty acid of the vegetable oil and monoalcohol. Representative examples of monoalcohol include methanol, ethanol, n- or iso-propanol, n, sec or tert-butanol, heptynol, 2-ethylhexanol, hexanol, octanol, decanol, dodecanol and other saturated alcohols, oleyl alcohol, Examples thereof include unsaturated aliphatic alcohols such as dodecenol, ficesteryl alcohol, somaryl alcohol, gadrelyl alcohol, 11-icosenol, 11-docosenol, and 15-tetracosenol.
エーテル類として代表的なものは、ジ−ｎ−オクチルエーテル、ジノニルエーテル、ジへプチルエーテル、ジヘキシルエーテル、ジデシルエーテル、ノニルへキシルエーテル、ノニルヘプチルエーテル、ノニルオクチルエーテル等が挙げられる。 Representative examples of ethers include di-n-octyl ether, dinonyl ether, diheptyl ether, dihexyl ether, didecyl ether, nonyl hexyl ether, nonyl heptyl ether, nonyl octyl ether and the like.
本発明の平版インキ組成物は、顔料を含むことができる。顔料を使用しなければ、クリアインキとして使用できる。
本願発明において顔料としては、一般的な無機顔料および有機顔料を示すことができる。
本願発明において無機顔料としては黄鉛、亜鉛黄、紺青、硫酸バリウム、カドミムレッド、酸化チタン、亜鉛華、弁柄、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、などを示すことができる。無機顔料の添加量は、印刷インキ組成物の全量に対して0.01〜10重量％である。
The lithographic ink composition of the present invention can contain a pigment. If no pigment is used, it can be used as a clear ink.
In the present invention, examples of the pigment include general inorganic pigments and organic pigments.
In the present invention, examples of the inorganic pigment include chrome yellow, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, dial, alumina white, calcium carbonate, ultramarine, carbon black, graphite, aluminum powder, and the like. it can. The addition amount of the inorganic pigment is 0.01 to 10% by weight with respect to the total amount of the printing ink composition.
本願発明において有機顔料としては、アゾ系として、Ｃ系（βナフトール系）、２Ｂ系および６Ｂ系（βオキシナフトエ系）などの溶性アゾ顔料、βナフトール系、βオキシナフトエ酸アニリド系、モノアゾイエロー系、ジスアゾイエロー系、ピラゾロン系などの不溶性アゾ顔料、アセト酢酸アリリド系などの縮合アゾ顔料、フタロシアニン系として、銅フタロシアニン（αブルー、βブルー、εブルー）、塩素、臭素などのハロゲン化銅フタロシアン、金属フリーのフタロシアニン顔料、多環顔料としてペリレン系、ペリノン系、キナクリドン系、チオインジゴ系、ジオキサジン系、イソインドリノン系、キノフタロン系顔料を挙げることができる。有機顔料の添加量は、印刷インキ組成物の全量に対して0.01〜３０重量％である。 In the present invention, the organic pigment is an azo-based, soluble azo pigment such as C-based (β-naphthol-based), 2B-based or 6B-based (β-oxynaphthoic-based), β-naphthol-based, β-oxynaphthoic acid anilide-based, monoazo yellow. , Disazo yellow, pyrazolone, and other insoluble azo pigments, acetoacetate allylide, condensed azo pigments, phthalocyanine, copper phthalocyanine (α blue, β blue, ε blue), halogenated copper lids such as chlorine and bromine Examples of Russian, metal-free phthalocyanine pigments and polycyclic pigments include perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, and quinophthalone pigments. The addition amount of the organic pigment is 0.01 to 30% by weight with respect to the total amount of the printing ink composition.
本発明の平版インキ組成物は、植物油、重合植物油以外の溶剤を含むことができる。このような溶剤として、石油系溶剤がある。
本願発明における石油系溶剤としては、芳香族炭化水素の含有率が１重量％以下で、アニリン点が６０〜１３０℃、沸点が２３０〜４００℃の石油系溶剤であり、好ましくはアニリン点が８０〜１００℃、沸点が２４０〜３１０℃である。平版印刷インキ全量中、石油系溶剤を０〜３０％含有するのが好ましく、５〜１５重量％含有するのがさらに好ましい。石油系溶剤のアニリン点が６０〜１３０℃の場合には、樹脂を溶解させる能力が好適であり、インキのセット性、光沢、着肉等の点で好ましい。このような非芳香族系石油溶剤としては、ＪＸ日鉱日石エネルギー株式会社製ＡＦソルベント４号、ＡＦソルベント５号、ＡＦソルベント６号、ＡＦソルベント７号等がある。
The lithographic ink composition of the present invention can contain a solvent other than vegetable oil and polymerized vegetable oil. Such solvents include petroleum solvents.
The petroleum solvent in the present invention is a petroleum solvent having an aromatic hydrocarbon content of 1% by weight or less, an aniline point of 60 to 130 ° C, and a boiling point of 230 to 400 ° C, preferably an aniline point of 80. It is -100 degreeC and a boiling point is 240-310 degreeC. The total amount of the lithographic printing ink preferably contains 0-30% petroleum solvent, more preferably 5-15% by weight. When the aniline point of the petroleum solvent is 60 to 130 ° C., the ability to dissolve the resin is suitable, and it is preferable in terms of ink setting properties, glossiness, and inking. Examples of such non-aromatic petroleum solvents include AF Solvent No. 4, AF Solvent No. 5, AF Solvent No. 6, and AF Solvent No. 7 manufactured by JX Nippon Oil & Energy Corporation.
本願発明においては必要に応じてワックスを使用することが出来る。
ワックスは、天然ワックスおよび合成ワックスに分類され、天然ワックスとしては、植物系ワックス、動物系ワックス、鉱物系ワックス、石油ワックスに分類される。本願発明の石油ワックスは、石油ワックスに分類されるパラフィンワックスおよびマイクロクリスタリンワックスが挙げられる。本願発明の溶融型の石油ワックスの製造工程の一例は、原油を原料として、常圧蒸留、減圧蒸留、溶剤精製、水素化精製、脱ろう、脱油を行った後、水素化精製または白土処理工程を経て得られるが、この限りではない。一方、粉砕型の石油ワックスは、いったんワックスを適度な大きさで製造し、それを所望通りに、粉砕を行うものである。
In the present invention, a wax can be used as necessary.
Waxes are classified into natural waxes and synthetic waxes, and natural waxes are classified into vegetable waxes, animal waxes, mineral waxes, and petroleum waxes. The petroleum wax of the present invention includes paraffin wax and microcrystalline wax classified as petroleum wax. An example of the production process of the melt type petroleum wax of the present invention is as follows: crude oil as a raw material, atmospheric distillation, vacuum distillation, solvent refining, hydrorefining, dewaxing, deoiling, hydrotreating or clay treatment Although it is obtained through the process, it is not limited to this. On the other hand, a pulverized petroleum wax is one in which a wax is once manufactured in an appropriate size and pulverized as desired.
また、合成ワックスは、合成炭化水素、変性ワックス、水素化ワックスに分けられ、本願発明で好ましく使用されるものとしてポリエチレンワックスが挙げられ、ポエチレンワックスは、フィッシャートロップスワックスと共に合成炭化水素に分類される。 Synthetic waxes are classified into synthetic hydrocarbons, modified waxes, and hydrogenated waxes. Examples of the waxes that are preferably used in the present invention include polyethylene waxes. Polyethylene waxes are classified as synthetic hydrocarbons together with Fischer-Trops waxes. Is done.
また、インキ組成物中への、その他添加剤として、耐摩擦、ブロッキング防止、スベリ、スリキズ防止を目的とする各種添加剤を使用することができるが、パイリングを誘発する懸念があるため、全インキ組成中の６％未満であることが望ましい。 Also, as other additives in the ink composition, various additives for the purpose of anti-friction, anti-blocking, slip and scratch prevention can be used. Desirably, it is less than 6% of the composition.
本願発明の印刷インキ組成物を製造するには、従来公知の方法で実施する事が出来る。一例としてバインダー樹脂、石油系溶剤、植物油類、必要に応じてゲル化剤を加えて、１９０℃１時間のクッキング条件でワニスを製造する。次いで、例えば、前記のワニスに顔料、石油系溶剤、植物油類、顔料分散剤または顔料分散樹脂を加え、ビーズミルや３本ロール等で分散する事により印刷インキ用ベースを得る事が出来る。次いで、石油系溶剤、植物油類、その他の添加剤を加え、所定粘度に調整し印刷インキ組成物を得る事が出来る。インキの種類としては、オフセット輪転印刷機用インキ、新聞印刷機用インキ、枚葉印刷機用インキが主なものであるが、これに限定されるものではない。 The printing ink composition of the present invention can be produced by a conventionally known method. As an example, a binder resin, petroleum-based solvent, vegetable oil, and a gelling agent as necessary are added, and varnish is produced under cooking conditions of 190 ° C. for 1 hour. Next, for example, a base for printing ink can be obtained by adding a pigment, petroleum solvent, vegetable oil, pigment dispersant or pigment dispersion resin to the varnish and dispersing with a bead mill or three rolls. Subsequently, petroleum-based solvents, vegetable oils, and other additives are added to adjust to a predetermined viscosity to obtain a printing ink composition. The main types of ink include, but are not limited to, ink for offset rotary printing presses, ink for newspaper printing presses, and ink for sheet-fed printing presses.
本願発明のインキ組成物の組成の一例としては、
・顔料0〜３０重量％
・バインダー樹脂１８〜４０重量％
・石油系溶剤０〜45重量％
・植物油類７〜３０重量％
・ワックス０．５〜６重量％
・酸化重合植物油0.5〜１０％
・その他添加剤１〜５重量％
などが好ましい組成として挙げられる。
As an example of the composition of the ink composition of the present invention,
・ Pigment 0-30% by weight
-Binder resin 18-40% by weight
・ Petroleum solvent 0-45% by weight
・ 7-30% by weight of vegetable oil
・ Wax 0.5-6% by weight
・ Oxidative polymerization vegetable oil 0.5-10%
・ 1-5% by weight of other additives
Etc. are mentioned as preferred compositions.
本願発明に使用される基材としては塗工紙、微塗工紙、非塗工紙、更紙が印刷用紙として挙げられる。
Examples of the substrate used in the present invention include coated paper, finely coated paper, non-coated paper, and reprinted paper as printing paper.
以下に、実施例により本願発明をさらに詳細に説明するが、以下の実施例は本願発明の権利範囲を何ら制限するものではない。なお、本願発明において、特に断らない限り、「部」は、「重量部」を表し、「％」は「重量％」を表す。 Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples do not limit the scope of rights of the present invention in any way. In the present invention, “parts” represents “parts by weight” and “%” represents “% by weight” unless otherwise specified.
本願発明において、重量平均分子量は、東ソー(株)製ゲルパーミネイションクロマトグラフィ（ＨＬＣ−８０２０）で測定した。検量線は標準ポリスチレンサンプルにより作成した。溶離液はテトラヒドロフランを、カラムにはＴＳＫｇｅｌＳｕｐｅｒＨＭ−Ｍ（東ソー(株)製）３本を用いた。測定は流速０．６ｍｌ／分、注入量１０μｌ、カラム温度４０℃で行った。さらに、本願発明において、特に断らない限り、「分子量」とは、重量平均分子量を示す。 In the present invention, the weight average molecular weight was measured by gel permeation chromatography (HLC-8020) manufactured by Tosoh Corporation. A calibration curve was prepared with a standard polystyrene sample. Tetrahydrofuran was used as the eluent, and three TSKgelSuperHM-M (manufactured by Tosoh Corporation) were used as the column. The measurement was performed at a flow rate of 0.6 ml / min, an injection volume of 10 μl, and a column temperature of 40 ° C. Furthermore, in the present invention, unless otherwise specified, “molecular weight” indicates a weight average molecular weight.
本願発明において、ヨウ素価はウイイス―ヘキサン法によって測定した。測定方法としては、対象となる重合植物油０．１５ｇをシクロヘキサン１０ｍｌに溶解させ、ウイイス液２５ｍｌを加え、フラスコを常温、暗所にて約１時間放置した。その後、０．１ｍｏｌ／ｌチオ硫酸ナトリウム標準液で滴定した。単位はｍｇ／１００ｍｇである。 In the present invention, iodine value U i chair - as measured by hexane method. As measuring method, the polymerization vegetable oil 0.15g of interest is dissolved in cyclohexane 10 ml, added c i chair solution 25 ml, and the flask ambient temperature and allowed to stand for about 1 hour in the dark. Then, it titrated with 0.1 mol / l sodium thiosulfate standard solution. The unit is mg / 100 mg.
本願発明においてそれぞれの粘度は２５℃でＬＡ型粘度計（日本レオロジー機器株式会社製）を用いて測定した。 In the present invention, each viscosity was measured at 25 ° C. using an LA type viscometer (manufactured by Nippon Rheology Equipment Co., Ltd.).
（ロジン変性フェノール樹脂製造例）
反応容器中でガムロジン１５００重量部に、予めキシレン溶媒中でターシャリーブチルフェノール６００重量部と９２重量％のパラホルムアルデヒド２１０重量部を水酸化ナトリウム触媒下、１００℃で４時間反応させ、水分除去したフェノール樹脂を１５０℃で滴下し２時間反応させた。さらに、ペンタエリスリトール１６０重量部を添加し、触媒として酸化カルシウム１．５重量部を使用して２５０℃で１２時間反応させた。反応の過程で順次取り出す事により、ロジン変性フェノール樹脂a（重量平均分子量７００００）を得た。
(Rosin modified phenolic resin production example)
Moisture-removed phenol obtained by reacting 1500 parts by weight of gum rosin in a reaction container with 600 parts by weight of tertiary butylphenol and 210 parts by weight of 92% by weight of paraformaldehyde in a xylene solvent at 100 ° C. for 4 hours under a sodium hydroxide catalyst. The resin was dropped at 150 ° C. and reacted for 2 hours. Further, 160 parts by weight of pentaerythritol was added, and the mixture was reacted at 250 ° C. for 12 hours using 1.5 parts by weight of calcium oxide as a catalyst. By sequentially taking out in the course of the reaction, rosin-modified phenol resin a (weight average molecular weight 70000) was obtained.
（ヒートセット型オフセット印刷インキ用ゲルワニスの製造）
撹拌機、リービッヒ冷却管、温度計付４つ口フラスコに樹脂a（重量平均分子量７００００）４４重量部、大豆油３５重量部、ＡＦソルベント７号（ＪＸ日鉱日石エネルギー株式会社製）２０重量部を仕込み、１９０℃に昇温、同温で３０分間攪拌した後、放冷し、ゲル化剤としてエチルアセトアセテートアルミニウムジイソプロポキシド１重量部（川研ファインケミカル株式会社製ＡＬＣＨ、以下ＡＬＣＨと称す）を仕込み、１９０℃で３０分間攪拌してインキ用ゲルワニス（以下ゲルワニスと称す）を得た。
(Manufacture of gel varnish for heat-set offset printing ink)
A stirrer, Liebig condenser, 4 parts flask with thermometer, 44 parts by weight of resin a (weight average molecular weight 70000), 35 parts by weight of soybean oil, 20 parts by weight of AF Solvent No. 7 (manufactured by JX Nippon Oil & Energy Corporation) The mixture was heated to 190 ° C., stirred at the same temperature for 30 minutes, allowed to cool, and 1 part by weight of ethyl acetoacetate aluminum diisopropoxide as gelling agent (ALCH from Kawaken Fine Chemical Co., Ltd., hereinafter referred to as ALCH) ) And stirred at 190 ° C. for 30 minutes to obtain an ink gel varnish (hereinafter referred to as gel varnish).
（重合植物油Ａ合成例）
撹拌機、リービッヒ冷却管、温度計付４つ口フラスコに大豆油（ヨウ素価１２８）を１００重量部仕込み、エアーポンプの先に中空のガラス管を接続し、液面上部に空気を送り込みながら１２０℃において３０時間、加熱・撹拌し、重合植物油Ａを得た。
(Polymerized vegetable oil A synthesis example)
A stirrer, a Liebig condenser, and a four-necked flask with a thermometer are charged with 100 parts by weight of soybean oil (iodine value 128), a hollow glass tube is connected to the tip of an air pump, and air is sent to the top of the liquid while 120 Polymerized vegetable oil A was obtained by heating and stirring at 30 ° C. for 30 hours.
（重合植物油Ｂ合成例）
撹拌機、リービッヒ冷却管、温度計付４つ口フラスコに再生大豆油（ヨウ素価１１５）を１００重量部仕込み、エアーポンプの先に中空のガラス管を接続し、液面上部に空気を送り込みながら１２０℃において３２時間、加熱・撹拌し、重合植物油Ｂを得た。
(Polymerized vegetable oil B synthesis example)
A stirrer, a Liebig condenser, and a four-neck flask with a thermometer are charged with 100 parts by weight of regenerated soybean oil (iodine value 115), a hollow glass tube is connected to the tip of an air pump, and air is sent to the top of the liquid level. Polymerized vegetable oil B was obtained by heating and stirring at 120 ° C. for 32 hours.
（重合植物油Ｃ〜Ｆ合成例）
さらに、表１の反応時間に基づいて、重合植物油Ｃ〜Ｆを得た。
(Polymerized vegetable oil C to F synthesis example)
Furthermore, polymerized vegetable oils C to F were obtained based on the reaction times in Table 1.
（重合植物油Ｇ合成例）
撹拌機、リービッヒ冷却管、温度計付４つ口フラスコに再生大豆油（ヨウ素価１１５）を７０重量部、亜麻仁油（ヨウ素価１７８）を３０重量部仕込み、エアーポンプの先に中空のガラス管を接続し、液面上部に空気を送り込みながら１２０℃において３０時間、加熱撹拌し、重合植物油Ｇ（原料となる植物油の平均ヨウ素化１３４）を得た。
(Synthesis example of polymerized vegetable oil G)
A stirrer, a Liebig condenser, and a four-neck flask with a thermometer were charged with 70 parts by weight of regenerated soybean oil (iodine value 115) and 30 parts by weight of linseed oil (iodine number 178), and a hollow glass tube at the tip of the air pump And heated and stirred at 120 ° C. for 30 hours while feeding air to the upper part of the liquid surface to obtain polymerized vegetable oil G (average iodination 134 of vegetable oil as a raw material).
（重合植物油Ｈ合成例）
撹拌機、リービッヒ冷却管、温度計付４つ口フラスコに菜種油（ヨウ素価１０５）を１００重量部仕込み、エアーポンプの先に中空のガラス管を接続し、液面上部に空気を送り込みながら１２０℃において４８時間、加熱・撹拌し、重合植物油Ｈを得た。
(Polymerized vegetable oil H synthesis example)
Charge 100 parts by weight of rapeseed oil (iodine value 105) into a four-neck flask with a stirrer, Liebig condenser and thermometer, connect a hollow glass tube to the tip of the air pump, and feed air to the top of the liquid level at 120 ° C And heated and stirred for 48 hours to obtain a polymerized vegetable oil H.
（重合植物油Ｉ合成例）
撹拌機、リービッヒ冷却管、温度計付４つ口フラスコに亜麻仁油（ヨウ素価１７８）を１００重量部仕込み、エアーポンプの先に中空のガラス管を接続し、液面上部に空気を送り込みながら１２０℃において２時間、加熱撹拌し、重合植物油Ｉを得た。
(Polymerized vegetable oil I synthesis example)
100 parts by weight of linseed oil (iodine value 178) was charged into a four-necked flask equipped with a stirrer, Liebig condenser, and thermometer, a hollow glass tube was connected to the tip of the air pump, and air was fed into the upper part of the liquid level. Polymerized vegetable oil I was obtained by heating and stirring at 2 ° C. for 2 hours.
（重合植物油Ｊ合成例）
撹拌機、リービッヒ冷却管、温度計付４つ口フラスコに桐油（ヨウ素価１６８）を７０重量部、亜麻仁油（ヨウ素価１７８）を３０重量部仕込み、窒素雰囲気下、１２０℃において５時間、加熱撹拌し、上記重合植物油Ｊ（原料となる植物油の平均ヨウ素化１７１）を得た。
(Polymerized vegetable oil J synthesis example)
A four-neck flask with a stirrer, Liebig condenser, and thermometer was charged with 70 parts by weight of Tung oil (iodine number 168) and 30 parts by weight of linseed oil (iodine number 178), and heated at 120 ° C. for 5 hours under a nitrogen atmosphere. The mixture was stirred to obtain the above-described polymerized vegetable oil J (average iodination 171 of vegetable oil as a raw material).
（重合植物油の皮張り適性）
表１の重合植物油の皮張り適性は、重合植物油を膜厚3μmとなるようにガラス板に塗布し、６０℃、２４時間に静置した際に、指の接触試験にて、以下の評価基準に基づいて、３段階で評価した。「1」の場合、皮張りの発生によりインキ製造中の作業性が著しく低下する。
(Applicability of polymerized vegetable oil for skinning)
The suitability of the polymerized vegetable oils in Table 1 is evaluated by the following contact criteria when the polymerized vegetable oil is applied to a glass plate so as to have a film thickness of 3 μm and left at 60 ° C. for 24 hours. Based on the above, it was evaluated in three stages. In the case of “1”, workability during ink production is significantly reduced due to the occurrence of skinning.
１：べたつきが完全にない（完全に皮張りしている）
２：膜表面に指紋が残る程度である（表面が皮張りしている）
３：指にかなりのべたつきがある（皮張りしていない）
「２」以上が実用レベルである。
1: No stickiness (completely skinned)
2: The fingerprint remains on the film surface (the surface is skinned)
3: Fingers are very sticky (not skinned)
“2” or higher is a practical level.
ヨウ素価の低い半乾性油・再生大豆油を出発原料とした重合植物油Ａ〜Ｇは皮張りの発生がなかったが、ヨウ素価の高い乾性油を出発原料とした重合植物油I、Jは皮張りの発生が見られた。 Polymerized vegetable oils A to G using semi-drying oil / regenerated soybean oil with low iodine value as the starting material did not have skinning, but polymerized vegetable oils I and J using drying oil with high iodine value as the starting material were skinned The occurrence of was seen.
（ヒートセット型オフセット印刷インキ組成物実施例１）
カーボンブラック（三菱化学株式会社製、ＤＢＰ吸油量７２ｍｌ／１００ｇ、ＢＥＴ比表面積９９ｍ2／ｇ）を２０重量部、ゲルワニスを70重量部、石油系溶剤を（ＡＦソルベント７号（ＪＸ日鉱日石エネルギー株式会社製））５重量部、重合植物油Aを５重量部を仕込み、常法に従い三本ロールを用いてヒートセット型オフセット印刷インキ組成物の実施例１を得た。
(Heat set type offset printing ink composition Example 1)
Carbon black (Mitsubishi Chemical Co., Ltd., DBP oil absorption 72 ml / 100 g, BET specific surface area 99 m 2 / g) 20 parts by weight, gel varnish 70 parts by weight, petroleum solvent (AF Solvent No. 7 (JX Nippon Oil & Energy) Co., Ltd.)) 5 parts by weight, 5 parts by weight of polymerized vegetable oil A were charged, and Example 1 of a heat-set offset printing ink composition was obtained using a three roll according to a conventional method.
さらに、表２の組成に基づいて、常法に従い三本ロールを用いてヒートセットオフセット印刷インキ組成物の実施例２〜１１および比較例１〜３を得た。 Furthermore, based on the composition of Table 2, Examples 2 to 11 and Comparative Examples 1 to 3 of heat set offset printing ink compositions were obtained using three rolls according to a conventional method.
（ヒートセット型オフセット印刷インキ組成物実施例２１）
２．５Ｌのフラッシャーに黄顔料としてリオノールイエローＮｏ．１２１３−Ｐ（トーヨーカラー（株）製）のプレスケーキを８１８重量部（固形分２２％）を仕込み撹拌しながら上記のインキ用ゲルワニスを５００重量部用いてフラッシングを行い顔料をワニス中に置換した。その後水を捨て、インキ用ゲルワニスを５２０重量部追加混合して、ベースインキ中の水分率が０．５％以下になるまで１２０℃で減圧脱水を行い、３本ロールで練肉して練肉ベースαを得た。得られた練肉ベースαを４０重量部とインキ用ゲルワニスを５０重量部、ＡＦソルベント７号（ＪＸ日鉱日石エネルギー株式会社製）を５重量部、重合植物油Aを ５重量部を混合し、実施例２１とした。
(Heat set type offset printing ink composition Example 21)
Lionol Yellow No. 2 as a yellow pigment on a 2.5 L flasher. A press cake of 1213-P (manufactured by Toyocolor Co., Ltd.) was charged with 818 parts by weight (solid content 22%), and flushed with 500 parts by weight of the gel varnish for ink to replace the pigment in the varnish. . Thereafter, water is discarded, 520 parts by weight of ink gel varnish is additionally mixed, dehydrated under reduced pressure at 120 ° C. until the water content in the base ink is 0.5% or less, and the mixture is kneaded with three rolls to give the meat Base α was obtained. 40 parts by weight of the obtained ground meat base α, 50 parts by weight of gel varnish for ink, 5 parts by weight of AF Solvent No. 7 (manufactured by JX Nippon Oil & Energy Corporation), 5 parts by weight of polymerized vegetable oil A are mixed, Example 21 was taken.
さらに、表３の組成に基づいて、常法に従い三本ロールを用いてインキ組成物の実施例２２〜３２および比較例２１〜２３を得た。 Furthermore, based on the composition of Table 3, Examples 22 to 32 and Comparative Examples 21 to 23 of ink compositions were obtained using three rolls according to a conventional method.
（ヒートセット型オフセット印刷インキ組成物実施例３３）
２．５Ｌのフラッシャーに藍顔料としてリオノールブルーＮｏ．７３３４Ｐ（トーヨーカラー（株）製）のプレスケーキ571重量部（固形分49％）を仕込み撹拌しながら上記のインキ用ゲルワニスを５００重量部用いてフラッシングを行い顔料をワニス中に置換した。その後水を捨て、インキ用ゲルワニスを５２０重量部追加混合して、ベースインキ中の水分率が０．５％以下になるまで１２０℃で減圧脱水を行い、３本ロールで練肉して練肉ベースβを得た。得られた練肉ベースβを８３．７重量部とインキ用ゲルワニスを１０．８重量部、ＡＦソルベント７号（ＪＸ日鉱日石エネルギー株式会社製）を ５重量部、重合植物油Aを ０．5重量部を混合し、実施例３３とした。
(Heat set type offset printing ink composition Example 33)
Rionol Blue No. 2 as an indigo pigment on a 2.5 L flasher. While charging 571 parts by weight (solid content 49%) of 7334P (made by Toyocolor Co., Ltd.) and stirring, 500 parts by weight of the gel varnish for ink was used for flushing to replace the pigment in the varnish. Thereafter, water is discarded, 520 parts by weight of ink gel varnish is additionally mixed, dehydrated under reduced pressure at 120 ° C. until the water content in the base ink is 0.5% or less, and the mixture is kneaded with three rolls to give the meat Base β was obtained. 83.7 parts by weight of the resulting ground meat base β, 10.8 parts by weight of gel varnish for ink, 5 parts by weight of AF Solvent No. 7 (manufactured by JX Nippon Oil & Energy Corporation), 0.5 of polymerized vegetable oil A The parts by weight were mixed to give Example 33.
さらに、表３の組成に基づいて、常法に従い三本ロールを用いてインキ組成物の実施例３４〜３６および比較例２４〜２６を得た。 Furthermore, based on the composition of Table 3, Examples 34 to 36 and Comparative Examples 24 to 26 of the ink compositions were obtained using three rolls according to a conventional method.
（性能評価試験（０１）後胴残り適性試験）
後胴残り適性試験は、ヒートセット型オフセット印刷機としてＬＩＴＨＯＰＩＡＢＴ２−８００ＮＥＯ（三菱重工株式会社）にて、AM２３０線の網点チャート、ベタチャートを含む絵柄、一般的な濃度にて以下の印刷条件にて実施し、先刷りインキの黄のブランケットへの付着の程度を、以下の評価基準に基いて５段階の相対評価を実施した。
用紙：パールコートN（６５．５ｇ／ｍ2）（三菱製紙株式会社）
（測色値：Ｌ*：97.43、ａ*：0.07、ｂ*：-2.14）
印刷速度：６００ｒｐｍ
ドライヤー通過後紙面温度：１０５℃
版：ＣＴＰ版（富士フィルム株式会社）
湿し水：アクワユニティWKK20KGGN（東洋インキ株式会社）
印刷部数：１０万部
(Performance evaluation test (01) Rear trunk remaining suitability test)
The rear cylinder remaining suitability test was performed under the following printing conditions with a pattern including a halftone dot chart of AM230 line, a solid chart, and general density at LITHOPIABT2-800NEO (Mitsubishi Heavy Industries, Ltd.) as a heat set type offset printing press. The degree of adhesion of the preprinted ink to the yellow blanket was subjected to a five-step relative evaluation based on the following evaluation criteria.
Paper: Pearl coat N (65.5 g / m 2 ) (Mitsubishi Paper Corporation)
(Colorimetric value: L * : 97.43, a * : 0.07, b * : -2.14)
Printing speed: 600rpm
Paper surface temperature after passing through the dryer: 105 ° C
Edition: CTP version (Fuji Film Co., Ltd.)
Dampening water: Akwa Unity WKK20KGGN (Toyo Ink Co., Ltd.)
Number of copies: 100,000 copies
１：黄胴への墨インキの固着が極めて多い
２：黄胴への墨インキの固着が多い
３：黄胴への墨インキの固着が通常程度である
４：黄胴への墨インキの固着があまりない
５：黄胴への墨インキの固着が極めて少ない
「３」以上が実用レベルである。
1: Black ink sticks to the yellow drum very much 2: Black ink sticks to the yellow drum much 3: Black ink sticks to the yellow drum is normal 4: Black ink sticks to the yellow drum There is not much 5: “3” or more with very little black ink sticking to the yellow drum is a practical level.
（性能評価試験（０２）１次ブロッキング適性試験＞
上記印刷試験で得られた印刷物のベタ部について、ベタ部×白紙で重ね合わせ、印刷後３分後から１分間２ｋｇ／ｃｍ2の圧力をかけた時の白紙へのインキの取られ度合いを観測し、目視により以下の評価基準に基いて５段階の相対評価を実施した。
(Performance Evaluation Test (02) Primary Blocking Suitability Test>
The solid part of the printed matter obtained in the above printing test was overlaid with a solid part x white paper, and the degree of ink taken on the white paper was observed when a pressure of 2 kg / cm 2 was applied for 1 minute from 3 minutes after printing. Then, a five-stage relative evaluation was performed visually based on the following evaluation criteria.
１：印刷面上に当てた白紙へインキが極めて多く移る
２：印刷面上に当てた白紙へインキが多く移る
３：印刷面上に当てた白紙へインキへの移りは通常程度である
４：印刷面上に当てた白紙へインキが余り移らない
５：印刷面上に当てた白紙へインキがほとんど移らない
「３」以上が実用レベルである。
1: Very large amount of ink transferred to the white paper applied on the printing surface 2: Large amount of ink transferred to the white paper applied on the printing surface 3: Normal transfer of ink to the white paper applied on the printing surface 4: Ink does not transfer much to the white paper applied on the printing surface 5: “3” or more that the ink hardly transfers to the white paper applied on the printing surface is a practical level.
（性能評価試験（０３）光沢）
上記印刷時の５万部印刷時の得られた印刷物のベタ部分について、村上色彩研究所製光沢計ＧＭ２６Ｄにて測定した。
実用レベルは「７０」以上である。
(Performance evaluation test (03) gloss)
The solid portion of the printed matter obtained at the time of printing 50,000 copies was measured with a gloss meter GM26D manufactured by Murakami Color Research Laboratory.
The practical level is “70” or more.
実施例１〜１１は、後胴残り適性、１次ブロッキング適性、光沢の評価結果が良好である。実施例１２は、若干物性が劣る項目があるものの実用上は問題ない。一方、比較例１は物性が実用レベルに満たない項目がある。比較例２、３は実用上問題ないが、使用している重合植物油I、Jは皮張り適性が非常に劣っており、製造現場・印刷現場での作業効率を著しく下げる欠点がある。
In Examples 1 to 11, the evaluation results of the back waist suitability, the primary blocking suitability, and the gloss are good. Although there are items in Example 12 that are slightly inferior in physical properties, there is no problem in practical use. On the other hand, Comparative Example 1 has items whose physical properties are less than the practical level. Comparative Examples 2 and 3 have no problem in practical use, but the polymerized vegetable oils I and J used have a very poor suitability for skinning and have a drawback of significantly reducing the work efficiency at the production site and the printing site.
（性能評価試験（１１）汚れの回復ポイントの評価試験）
後胴残り適性試験は、ヒートセット型オフセット印刷機としてＬＩＴＨＯＰＩＡＢＴ２−８００ＮＥＯ（三菱重工株式会社）にて、AM２３０線の網点チャート、ベタチャートを含む絵柄、印刷方向に対して絵柄が全くない箇所を設け、一般的な濃度にて以下の印刷条件にて実施し、印刷物上の汚れの取れる水ダイヤル値を計測した。比較例1に対して＋10ポイント以内が実用範囲内である。＋12ポイントを超える場合、水上がり量が多く、乾燥性などへも支障をきたすレベルとなる。
用紙：パールコートN（６５．５ｇ／ｍ2）（三菱製紙株式会社）
（測色値：Ｌ*：97.43、ａ*：0.07、ｂ*：-2.14）
印刷速度：６００ｒｐｍ
ドライヤー通過後紙面温度：１０５℃
版：ＣＴＰ版（富士フィルム株式会社）
湿し水：アクワユニティWKK20KGGN（東洋インキ株式会社）
(Performance evaluation test (11) Evaluation test of soil recovery point)
In the rear cylinder suitability test, a heat-set type offset printing machine with a LITHOPI ABT2-800NEO (Mitsubishi Heavy Industries, Ltd.), a pattern including a dot chart of AM230 line, a solid chart, and a place where there is no pattern at all in the printing direction. The water dial value at which stains can be removed on the printed matter was measured at a general density under the following printing conditions. Within Comparative Example 1, +10 points or less is within the practical range. If the point exceeds +12 points, the amount of water rising will be large, and it will be a level that will impair the dryness.
Paper: Pearl coat N (65.5 g / m 2 ) (Mitsubishi Paper Corporation)
(Colorimetric value: L * : 97.43, a * : 0.07, b * : -2.14)
Printing speed: 600rpm
Paper surface temperature after passing through the dryer: 105 ° C
Edition: CTP version (Fuji Film Co., Ltd.)
Dampening water: Akwa Unity WKK20KGGN (Toyo Ink Co., Ltd.)
（性能評価試験（１２）インキ余り＞
汚れが回復した水ダイヤルポイントに対し、＋20ポイント水ダイヤルを上げ、1万部印刷後の水つけローラーへのインキの余りを観測し、目視により以下の評価基準に基いて５段階の相対評価を実施した。
(Performance evaluation test (12) Ink residue>
Raise the +20 point water dial to the water dial point where the smudge has been recovered, observe the remainder of the ink on the watering roller after printing 10,000 copies, and visually evaluate the relative value in five stages based on the following evaluation criteria. Carried out.
１：通常よりも水つけローラーへの余りが非常に多い。
２：通常よりも水つけローラーへの余りが多い。
３：通常の水つけローラーへの余り具合である。
４：通常よりも水つけローラーへの余りが軽度である
５：水つけローラーへの余りが全くない。
「３」以上が実用レベルである。
1: There is much surplus to a watering roller rather than usual.
2: There is more remainder to the watering roller than usual.
3: It is a surplus to a normal watering roller.
4: The remainder to the watering roller is lighter than usual. 5: There is no remainder to the watering roller.
“3” or higher is a practical level.
黄顔料、藍顔料ともに結果の傾向に差はなく、同様の結果であった。実施例２１〜２５、２７〜３１、３３〜３５は汚れの回復、インキ余りも良好である。実施例２６、３２、３６は重合植物油の酸価重合反応が過剰に進行し、カルボキシル基や水酸基などの極性基量が多くなり、汚れが発生しやすくなっている。一方、比較例２１〜２６は物性が実用レベルに満たない項目がある。比較例２２、２５は重合植物油Iの粘度も低いため、インキの粘度も相対的に低くなり、汚れやすい。比較例２３、２６重合植物油Jが熱重合のため、他の酸化重合植物油と比較し、相対的にインキ余りは劣っている。 There was no difference in the tendency of the results for both the yellow pigment and the indigo pigment, and the results were similar. In Examples 21 to 25, 27 to 31, and 33 to 35, the recovery of stains and the ink surplus are good. In Examples 26, 32, and 36, the acid value polymerization reaction of the polymerized vegetable oil proceeds excessively, the amount of polar groups such as carboxyl groups and hydroxyl groups increases, and stains are likely to occur. On the other hand, Comparative Examples 21 to 26 have items whose physical properties are less than the practical level. In Comparative Examples 22 and 25, the viscosity of the polymerized vegetable oil I is low, so that the viscosity of the ink is relatively low, and the ink is easily soiled. Comparative Examples 23 and 26 Since the polymerized vegetable oil J is thermally polymerized, the ink surplus is relatively inferior compared to other oxidized polymerized vegetable oils.
Claims (3)
重合植物油が、ヨウ素価１００〜１４０（ｍｇ／１００ｍｇ）の、植物油および／または再生植物油由来の重合植物油であり、かつ、重量平均分子量３００００〜１５００００であることを特徴とする平版印刷インキ組成物。 A lithographic printing ink composition comprising a binder resin, an oxidative polymerization vegetable oil and a vegetable oil ,
A lithographic printing ink composition, wherein the polymerized vegetable oil is a polymerized vegetable oil derived from vegetable oil and / or regenerated vegetable oil having an iodine value of 100 to 140 (mg / 100 mg) and having a weight average molecular weight of 30,000 to 150,000.
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