JP2005089620A - Thermosetting ink composition for offset printing - Google Patents
Thermosetting ink composition for offset printing Download PDFInfo
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- JP2005089620A JP2005089620A JP2003325660A JP2003325660A JP2005089620A JP 2005089620 A JP2005089620 A JP 2005089620A JP 2003325660 A JP2003325660 A JP 2003325660A JP 2003325660 A JP2003325660 A JP 2003325660A JP 2005089620 A JP2005089620 A JP 2005089620A
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- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 238000007645 offset printing Methods 0.000 title abstract description 5
- 239000011347 resin Substances 0.000 claims abstract description 52
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 20
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 239000000976 ink Substances 0.000 claims description 56
- 239000003208 petroleum Substances 0.000 claims description 18
- 239000005011 phenolic resin Substances 0.000 claims description 16
- 150000002989 phenols Chemical class 0.000 claims description 16
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 8
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229920000180 alkyd Polymers 0.000 claims description 3
- 125000004069 aziridinyl group Chemical group 0.000 claims description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 125000003566 oxetanyl group Chemical group 0.000 claims description 2
- 238000009998 heat setting Methods 0.000 abstract description 4
- 239000002966 varnish Substances 0.000 description 46
- 235000012424 soybean oil Nutrition 0.000 description 19
- 239000003549 soybean oil Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 15
- 235000014113 dietary fatty acids Nutrition 0.000 description 14
- 229930195729 fatty acid Natural products 0.000 description 14
- 239000000194 fatty acid Substances 0.000 description 14
- -1 fatty acid isobutyl ester Chemical class 0.000 description 13
- 239000002253 acid Substances 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 239000000049 pigment Substances 0.000 description 10
- 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 8
- 239000013522 chelant Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 235000010187 litholrubine BK Nutrition 0.000 description 8
- 238000007639 printing Methods 0.000 description 8
- 235000015112 vegetable and seed oil Nutrition 0.000 description 8
- 239000008158 vegetable oil Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- HIYIGPVBMDKPCR-UHFFFAOYSA-N 1,1-bis(ethenoxymethyl)cyclohexane Chemical compound C=COCC1(COC=C)CCCCC1 HIYIGPVBMDKPCR-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 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
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-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
- KAPCRJOPWXUMSQ-UHFFFAOYSA-N [2,2-bis[3-(aziridin-1-yl)propanoyloxymethyl]-3-hydroxypropyl] 3-(aziridin-1-yl)propanoate Chemical compound C1CN1CCC(=O)OCC(COC(=O)CCN1CC1)(CO)COC(=O)CCN1CC1 KAPCRJOPWXUMSQ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 235000013372 meat Nutrition 0.000 description 2
- 229960000834 vinyl ether Drugs 0.000 description 2
- GPHWXFINOWXMDN-UHFFFAOYSA-N 1,1-bis(ethenoxy)hexane Chemical compound CCCCCC(OC=C)OC=C GPHWXFINOWXMDN-UHFFFAOYSA-N 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- MWZJGRDWJVHRDV-UHFFFAOYSA-N 1,4-bis(ethenoxy)butane Chemical compound C=COCCCCOC=C MWZJGRDWJVHRDV-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- UEIPWOFSKAZYJO-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-[2-(2-ethenoxyethoxy)ethoxy]ethane Chemical compound C=COCCOCCOCCOCCOC=C UEIPWOFSKAZYJO-UHFFFAOYSA-N 0.000 description 1
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 1
- LJWZDTGRJUXOCE-UHFFFAOYSA-N 2-(2-ethylhexyl)oxetane Chemical compound CCCCC(CC)CC1CCO1 LJWZDTGRJUXOCE-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- CCHJOAVOTFFIMP-UHFFFAOYSA-N 2-phenyloxetane Chemical compound O1CCC1C1=CC=CC=C1 CCHJOAVOTFFIMP-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 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
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- FFBZKUHRIXKOSY-UHFFFAOYSA-N aziridine-1-carboxamide Chemical compound NC(=O)N1CC1 FFBZKUHRIXKOSY-UHFFFAOYSA-N 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 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
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 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
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 150000002921 oxetanes Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Abstract
Description
本発明は、安定性（常温で粘度変化や皮張り等が発生しない）、熱硬化性（ヒートセット性）、光沢、耐摩擦性等に優れたオフセットインキを与えることができる熱硬化性オフセットインキ用組成物に関する。 The present invention is a thermosetting offset ink that can provide an offset ink excellent in stability (no change in viscosity or skinning at room temperature), thermosetting (heat setting properties), gloss, and friction resistance. The present invention relates to a composition for use.
オフセットインキの乾燥は通常、蒸発乾燥、乾性油・半乾性油による酸化重合乾燥、印刷紙面への浸透乾燥等により行われ、これらの手段は単独或いは組み合わせて用いられている（例えば、非特許文献１を参照）。しかし、これらの方法では乾燥に長時間を要したり、乾燥後の印刷面のセット性が不十分であると耐摩擦性や光沢等が損なわれる傾向がある。そこで硬化性に優れる紫外線硬化型インキを採用する方法も考えられるが（例えば、非特許文献１を参照）、設備投資やランニングコストの負担が大きくなるだけでなく、使用できる樹脂の選択範囲が狭いといった問題点もある。他にもインキ内で化学的に異なる２つの成分を反応させて硬化乾燥させる方法も考えられるが（例えば、非特許文献１を参照）、このようなインキは常温で皮張りや粘度変化が生じる等、安定性に欠けるという問題がある。
本発明は、安定性（常温で粘度変化や皮張り等が発生しない）、熱硬化性（ヒートセット性）、光沢、耐摩擦性等に優れたオフセットインキを与えることができる熱硬化性オフセットインキ用組成物を提供することを目的とする。 The present invention is a thermosetting offset ink that can provide an offset ink excellent in stability (no change in viscosity or skinning at room temperature), thermosetting (heat setting properties), gloss, and friction resistance. It is an object to provide a composition for use.
本発明者らは前記課題に鑑みて、オフセットインキを硬化させる反応物質、とりわけ架橋剤などに着目して鋭意検討を重ねた。その結果、分子内にカルボキシル基を有する樹脂をバインダー樹脂とし、且つ当該樹脂のカルボキシル基と特定温度以上で反応しうる官能基を分子内に有する熱架橋性架橋剤を配合してなるオフセットインキ組成物によれば、前記課題が悉く解決されることを見出した。本発明はかかる新しい知見に基づいて完成されたものである。 In view of the above problems, the present inventors have made extensive studies focusing on reactive substances that harden offset ink, in particular, crosslinking agents. As a result, an offset ink composition comprising a resin having a carboxyl group in the molecule as a binder resin and a thermally crosslinkable crosslinking agent having a functional group capable of reacting with the carboxyl group of the resin at a specific temperature or higher in the molecule. According to the invention, the present inventors have found that the above problems can be solved ugly. The present invention has been completed based on such new findings.
すなわち、本発明は、分子内にカルボキシル基を有するバインダー樹脂（Ａ）（以下、樹脂（Ａ）という）、当該樹脂（Ａ）のカルボキシル基と５０℃以上で反応する官能基を分子内に有する熱架橋性架橋剤（Ｂ）（以下、架橋剤（Ｂ）という）、ならびに必要に応じて溶剤（Ｃ）を含有してなる熱硬化性オフセットインキ用組成物に関する。また本発明は、当該インキ用組成物を含有してなる熱硬化性オフセットインキに関する。 That is, the present invention has a binder resin (A) having a carboxyl group in the molecule (hereinafter referred to as resin (A)) and a functional group that reacts with the carboxyl group of the resin (A) at 50 ° C. or more in the molecule. The present invention relates to a thermosetting offset ink composition comprising a heat-crosslinkable crosslinking agent (B) (hereinafter referred to as a crosslinking agent (B)) and, if necessary, a solvent (C). The present invention also relates to a thermosetting offset ink comprising the ink composition.
本発明に係る熱硬化性オフセットインキ用組成物は樹脂選択の自由度が高く、また該組成物によれば、常温で粘度変化や皮張り等が発生しないため安定性に優れ、且つ、印刷面の熱硬化性（ヒートセット性）、光沢、耐摩擦性等に優れる熱硬化性オフセットインキを提供することができる。 The composition for thermosetting offset ink according to the present invention has a high degree of freedom in resin selection, and according to the composition, since there is no change in viscosity or skinning at room temperature, it has excellent stability, and the printing surface It is possible to provide a thermosetting offset ink having excellent thermosetting properties (heat setting properties), gloss, friction resistance and the like.
樹脂（Ａ）としては、分子内にカルボキシル基を有する各種公知の印刷インキ用バインダー樹脂を、格別限定することなく使用することができ、たとえば、ロジン変性フェノール樹脂、ロジンエステル樹脂、ロジンアルキド樹脂、ロジン変性石油樹脂、石油樹脂エステル等を好ましく用いることができる。 As the resin (A), various known printing ink binder resins having a carboxyl group in the molecule can be used without any particular limitation. For example, rosin-modified phenol resin, rosin ester resin, rosin alkyd resin, A rosin-modified petroleum resin, petroleum resin ester or the like can be preferably used.
なお、当該ロジンアルキド樹脂とは、例えばロジン類とグリセリンやトリメチロールアルカン等のポリオールとを常法で反応させてなる水酸基含有樹脂に、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、（無水）コハク酸、（無水）マレイン酸等の多塩基酸を常法で反応させてなる樹脂が挙げられる。このものは具体的には、特開２０００−１４３７８５号公報に記載されている。 The rosin alkyd resin is a hydroxyl group-containing resin obtained by reacting, for example, rosins and polyols such as glycerin and trimethylolalkane, and phthalic anhydride, isophthalic acid, terephthalic acid, (anhydrous) trimellit. Examples thereof include resins obtained by reacting polybasic acids such as acid, (anhydrous) succinic acid, and (anhydrous) maleic acid in a conventional manner. This is specifically described in JP-A No. 2000-143785.
また、該ロジン変性石油樹脂としては、例えばロジン類の存在下に水酸基等の極性基を含有する石油樹脂、および脂肪族モノアルコール類、脂肪族ジアルコール類、脂肪族モノアミン類、脂肪族モノエポキシ類から選択される少なくとも１種、ならびにポリオール類を反応させてなる樹脂が挙げられる。このものは具体的には、特開平４−１７５３２４号公報に記載されている。 Examples of the rosin-modified petroleum resin include petroleum resins containing a polar group such as a hydroxyl group in the presence of rosins, and aliphatic monoalcohols, aliphatic dialcohols, aliphatic monoamines, aliphatic monoepoxies. And a resin obtained by reacting at least one selected from the group and polyols. This is specifically described in JP-A-4-175324.
また、当該変性石油樹脂エステルとしては、例えばインデン等のＣ５系石油樹脂（またはその共重合物）をマレイン酸等のα，β−エチレン性不飽和カルボン酸やその無水物で変性した酸変性石油樹脂に、エチレングリコールやトリメチロールアルカン等のポリオール反応させてなる樹脂が挙げられる。このものは具体的には、特開２００２−１８８０２８号公報に記載された樹脂を利用し得る。 Further, the modified petroleum as the resin esters, such as C 5 petroleum resins indene (or a copolymer thereof) and maleic acid alpha, acid modified with β- ethylenically unsaturated carboxylic acid or its anhydride-modified A resin obtained by reacting a petroleum resin with a polyol such as ethylene glycol or trimethylolalkane is exemplified. Specifically, the resin described in JP 2002-188028 A can be used.
これら樹脂（Ａ）の分子量や粘度は格別限定されず、また、樹脂（Ａ）は２種以上を併用してもよい。 The molecular weight and viscosity of these resins (A) are not particularly limited, and two or more kinds of resins (A) may be used in combination.
前記架橋剤（Ｂ）としては、樹脂（Ａ）中のカルボキシル基と５０℃以上、好ましくは５０〜２００℃において反応する官能基を分子内に有する熱架橋性架橋剤が該当する。５０℃以下で反応するものは常温において皮張りが発生するなど安定性に欠ける。反応に２００℃以上の条件を要するものは硬化性に劣り、好ましくない。当該官能基としては水酸基、エポキシ基、アジリジニル基、グリシジル基、オキセタニル基およびビニルエーテル基等が挙げられる。架橋剤（Ｂ）の具体例としては、例えば石炭酸、ブチルフェノール、オクチルフェノール等のレゾール類；ビスフェノールＡジグリシジルエーテル、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、グリセロールポリグリシジルエーテル等のエポキシ化合物類；Ｎ，Ｎ’−ヘキサアミノエチレン−１，６−ビス（１−アジリジンカルボキシアミド）、トリメチロールプロパン−トリ−（β−アジリジニルプロピオネ−ト）、ペンタエリスリトール−トリ−（３−アジリジン−１−イルプロピオネート）等のアジリジン類；２−エチルヘキシルオキセタン、フェニルオキセタン等のオキセタン類；ジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、１，４−ブタンジオールジビニルエーテル、ヘキサンジオールジビニルエーテル、テトラエチレングリコールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル等のジビニルエーテル類などが挙げられる。これらは２種以上を併用してもよい。 As said crosslinking agent (B), the thermal crosslinkable crosslinking agent which has in the molecule | numerator the functional group which reacts with the carboxyl group in resin (A) at 50 degreeC or more, Preferably it is 50-200 degreeC corresponds. Those that react at 50 ° C. or less lack stability, such as skinning at room temperature. Those requiring conditions of 200 ° C. or higher for the reaction are inferior in curability and are not preferred. Examples of the functional group include a hydroxyl group, an epoxy group, an aziridinyl group, a glycidyl group, an oxetanyl group, and a vinyl ether group. Specific examples of the crosslinking agent (B) include resols such as carboxylic acid, butylphenol and octylphenol; bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl glycol Epoxy compounds such as diglycidyl ether and glycerol polyglycidyl ether; N, N′-hexaaminoethylene-1,6-bis (1-aziridinecarboxamide), trimethylolpropane-tri- (β-aziridinylpropione) Aziridines such as pentaerythritol-tri- (3-aziridin-1-ylpropionate); oxetanes such as 2-ethylhexyloxetane and phenyloxetane; Ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,4-butanediol divinyl ether, hexanediol divinyl ether, tetraethylene glycol divinyl ether, such as divinyl ethers such as cyclohexane dimethanol divinyl ether. Two or more of these may be used in combination.
なお、架橋剤（Ｂ）は分子中に前記した官能基を有していればよいので、例えば前記架橋剤（Ｂ）と他の化合物とを反応させてなる高分子量物であって、分子中に前記官能基を有するものを架橋剤（Ｂ）として用いてもよい。そうすることで、印刷物の塗膜の物性（光沢、耐摩擦性等）を向上させることができる。具体的には、公知のシクロペンタジエン系石油樹脂（例えば、日本ゼオン（株）製「クイントン１３２５」など）をマレイン酸等のα，β−エチレン性不飽和カルボン酸やその無水物で変性して得られる酸変性石油樹脂に、当該カルボキシル基の当量以上となるジビニルエーテルを反応させてなる、遊離のビニルエーテル基を有する高分子量物を架橋剤（Ｂ）として用いることができる。 Since the crosslinking agent (B) only needs to have the above-described functional group in the molecule, for example, it is a high molecular weight product obtained by reacting the crosslinking agent (B) with another compound, Those having the above functional group may be used as the crosslinking agent (B). By doing so, the physical properties (gloss, friction resistance, etc.) of the coating film of printed matter can be improved. Specifically, a known cyclopentadiene-based petroleum resin (for example, “Quinton 1325” manufactured by Nippon Zeon Co., Ltd.) is modified with an α, β-ethylenically unsaturated carboxylic acid such as maleic acid or its anhydride. A high molecular weight product having a free vinyl ether group obtained by reacting the resulting acid-modified petroleum resin with divinyl ether having an equivalent weight or more of the carboxyl group can be used as the crosslinking agent (B).
以上述べた樹脂（Ａ）のカルボキシル基と後述する架橋剤（Ｂ）とを反応させることにより、本発明に係るオフセットインキは熱硬化する。なお、樹脂（Ａ）に対する架橋剤（Ｂ）の使用量は特に限定されないが、通常は樹脂（Ａ）中のカルボキシル基１当量に対して、０．１〜１当量となる前記官能基を有する架橋剤（Ｂ）を使用するのが好ましい。０．１当量未満であれば得られる印刷インキの硬化性が劣り、１当量より大きいと常温でインキに皮張り等が発生するなどインキの安定性が低下する傾向にある。また、必要に応じ、樹脂（Ａ）と架橋剤（Ｂ）との反応を促進するために触媒を添加する事もできる。 The offset ink according to the present invention is thermally cured by reacting the carboxyl group of the resin (A) described above with the crosslinking agent (B) described later. In addition, although the usage-amount of the crosslinking agent (B) with respect to resin (A) is not specifically limited, Usually it has the said functional group used as 0.1-1 equivalent with respect to 1 equivalent of carboxyl groups in resin (A). It is preferable to use a crosslinking agent (B). If it is less than 0.1 equivalent, the curability of the resulting printing ink is inferior, and if it is more than 1 equivalent, the ink stability tends to decrease, for example, the ink is skinned at room temperature. Further, if necessary, a catalyst can be added to promote the reaction between the resin (A) and the crosslinking agent (B).
前記溶剤（Ｃ）としては、石油系溶剤、植物油、植物油のエステル等が挙げられる。具体的には、石油系溶剤としては新日本石油（株）製のＡＦソルベント６号やＡＦソルベント７号が挙げられ、植物油としては大豆白絞油やアマニ油が挙げられ、植物油のエステルとしては大豆油脂肪酸メチルエステルや大豆油脂肪酸ブチルエステル、大豆油脂肪酸イソブチルエステル等が挙げられる。石油系溶剤を使用せずに植物油あるいは植物油のエステルのみを溶剤とすれば、揮発分を極力低下させることができる。具体的には１１０℃において１時間加熱したときの水分を除く加熱減量が１％以下となるような環境対応型のインキが得られる。 Examples of the solvent (C) include petroleum solvents, vegetable oils, esters of vegetable oils, and the like. Specifically, examples of petroleum-based solvents include AF Solvent No. 6 and AF Solvent No. 7 manufactured by Nippon Oil Corporation. Examples of vegetable oils include soybean white extract oil and linseed oil. Examples of vegetable oil esters include Examples include soybean oil fatty acid methyl ester, soybean oil fatty acid butyl ester, and soybean oil fatty acid isobutyl ester. If only vegetable oil or an ester of vegetable oil is used as a solvent without using a petroleum solvent, the volatile matter can be reduced as much as possible. Specifically, an environmentally friendly ink is obtained in which the loss on heating excluding moisture when heated at 110 ° C. for 1 hour is 1% or less.
本発明に係る熱硬化性オフセットインキ用組成物は、前記樹脂（Ａ）〜溶剤（Ｃ）に必要に応じて公知のゲル化剤等を配合したものを適宜溶融させて得られるワニス（またはゲルワニス）である。樹脂（Ａ）〜溶剤（Ｃ）の仕込み順序は特に制限されず、例えばこれらを一度に混合してもよいし、樹脂（Ａ）に溶剤（Ｃ）を加えて一旦ワニスとした後に架橋剤（Ｂ）を添加・混合してもよい。なお、樹脂（Ａ）と架橋剤（Ｂ）が反応して当該組成物が熱硬化しないように、混合物の系の温度は少なくとも５０℃未満に保つ必要がある。 The thermosetting offset ink composition according to the present invention is a varnish (or gel varnish) obtained by appropriately melting the resin (A) to the solvent (C) with a known gelling agent blended as necessary. ). The order of charging the resin (A) to the solvent (C) is not particularly limited. For example, they may be mixed at once, or the solvent (C) may be added to the resin (A) to form a varnish once, and then a crosslinking agent ( B) may be added and mixed. In addition, it is necessary to keep the temperature of the system of the mixture at least below 50 ° C. so that the resin (A) and the cross-linking agent (B) react and the composition does not thermoset.
前記ゲル化剤としては、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、アルミにウムジプロポキシドモノアセチルアセテート等の各種公知のアルミキレート剤が好ましい。 Examples of the gelling agent include aluminum octylate and aluminum stearate. Various known aluminum chelating agents such as aluminum triisopropoxide, aluminum and umdipropoxide monoacetyl acetate are preferred.
本発明に係る熱硬化性オフセットインキは、前記熱硬化性オフセットインキ組成物に顔料（黄色、紅色、藍色、黒色など）、溶剤（Ｃ）と同様の植物油および／または石油系溶剤を加え、更に必要に応じてインキ流動性を改善するための界面活性剤、ワックスなどの添加剤を配合して得られる混合物を、ロールミル、ボールミル、アトライター、サンドミルといった公知のインキ製造装置を用いて適当なインキ恒数となるよう、練肉・調製して得られるものである。なお、本発明に係る熱硬化性オフセットインキには樹脂（Ａ）、架橋剤（Ｂ）、必要に応じて溶剤（Ｃ）が結果的に存在していればよいので、例えば樹脂（Ａ）、溶剤（Ｃ）及び顔料等を用いて練肉してから一旦インキを調製した後に架橋剤（Ｂ）を添加してもよい。かかる方法はインキの熱履歴の点で好ましい。なお、本発明に係る熱硬化性オフセットインキ中の前記熱硬化性オフセットインキ用組成物の総量は、固形分濃度で通常１０〜５０重量％程度である。 The thermosetting offset ink according to the present invention is a pigment (yellow, red, indigo, black, etc.) added to the thermosetting offset ink composition, vegetable oil and / or petroleum solvent similar to the solvent (C), Furthermore, if necessary, a mixture obtained by blending an additive such as a surfactant and a wax for improving the ink fluidity can be mixed with a known ink production apparatus such as a roll mill, a ball mill, an attritor or a sand mill. It is obtained by kneading and preparing so as to be an ink constant. In addition, since the resin (A), the cross-linking agent (B), and the solvent (C) as necessary may be present in the thermosetting offset ink according to the present invention, for example, the resin (A), The cross-linking agent (B) may be added after the ink is once prepared after kneading with a solvent (C) and a pigment. Such a method is preferable in terms of the thermal history of the ink. The total amount of the thermosetting offset ink composition in the thermosetting offset ink according to the present invention is generally about 10 to 50% by weight in terms of solid content.
本発明に係る熱硬化性オフセットインキの種類は特に制限されず、各色インキ、ＯＰニス等のアロマフリータイプ、植物油インキそれぞれに賞用しうる。オフセット印刷機の種類としては、枚葉印刷機、輪転印刷機にどちらにも好適に対応できる。 The kind of the thermosetting offset ink according to the present invention is not particularly limited, and can be used for each color ink, aroma-free type such as OP varnish, and vegetable oil ink. As the type of offset printing machine, it can be suitably applied to both sheet-fed printing presses and rotary printing presses.
前記樹脂（Ａ）と架橋剤（Ｂ）の反応は常温で実質的に進行しないため、本発明に係る熱硬化性オフセットインキは皮張りや粘度変化の発生がなく、長期に亘り安定である。また、樹脂（Ａ）と架橋剤（Ｂ）は５０℃以上の条件下で熱架橋反応を開始するので、本発明に係る熱硬化性オフセットインキはこれ以上の温度、具体的には５０℃〜２００℃で乾燥される。インキの乾燥手段は特に限定されず各種公知の方法を利用できる。 Since the reaction between the resin (A) and the cross-linking agent (B) does not substantially proceed at room temperature, the thermosetting offset ink according to the present invention is stable for a long time without causing any skinning or viscosity change. Further, since the resin (A) and the crosslinking agent (B) start a thermal crosslinking reaction under a condition of 50 ° C. or higher, the thermosetting offset ink according to the present invention has a temperature higher than this, specifically 50 ° C. to Dry at 200 ° C. The means for drying the ink is not particularly limited, and various known methods can be used.
以下、実施例および比較例をあげて本発明を更に具体的に説明するが、本発明がこれら実施例に限定されないことはもとよりである。尚、以下「部」、「％」はいずれも重量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples. In the following, “part” and “%” are based on weight.
実施例１
攪拌機、還流冷却管および温度計を備えたフラスコに、重量平均分子量５０，０００、酸価２５ｍｇＫＯＨ／ｇのロジン変性フェノール樹脂１００部、大豆油脂肪酸イソブチルエステル６７部を仕込み、攪拌下に２２０℃まで昇温し、同温度で１時間保温してワニス１６７部を得た。このワニスのうち１００部を前述したものと同じフラスコに取り、撹拌下に８０℃迄昇温した後、ＡＬＣＨ（川研ファインケミカル（株）製、アルミキレート）の５０％ＡＦ７号ソルベント（新日本石油（株）製）溶液０．４部を添加し、２００℃迄昇温した後に５０分間保温し、次いで冷却してゲルワニス１００部を得た。こうして得られたゲルワニスのＥ型粘度は２５０Ｐａ・ｓであった。このゲルワニス７０部にカーミン６Ｂ（顔料）を１５部添加し、三本ロールミルで練肉し、ＡＦ７号ソルベントを１５部添加した。練肉終了後にシクロヘキサンジメタノールジビニルエーテル２．０部（ロジン変性フェノール樹脂のカルボキシル基１当量に対し、当該ビニルエーテル基が０．４５当量に相当）を添加し、タック７．５（３０℃、４００ｒｐｍにおけるインコメーター測定値。以下、同様）のオフセットインキ１００部を得た。
Example 1
A flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 100 parts of a rosin-modified phenol resin having a weight average molecular weight of 50,000 and an acid value of 25 mgKOH / g, and 67 parts of soybean oil fatty acid isobutyl ester, and the mixture was stirred to 220 ° C. The temperature was raised and kept at that temperature for 1 hour to obtain 167 parts of varnish. 100 parts of this varnish were placed in the same flask as described above, heated to 80 ° C. with stirring, and then 50% AF7 Solvent (Shin Nippon Oil Co., Ltd.) of ALCH (manufactured by Kawaken Fine Chemical Co., Ltd., aluminum chelate). 0.4 parts of a solution was added, the temperature was raised to 200 ° C., the temperature was kept for 50 minutes, and then cooled to obtain 100 parts of a gel varnish. The gel varnish thus obtained had an E-type viscosity of 250 Pa · s. 15 parts of Carmine 6B (pigment) was added to 70 parts of this gel varnish, kneaded with a three roll mill, and 15 parts of AF7 solvent was added. After completion of the meat grinding, 2.0 parts of cyclohexanedimethanol divinyl ether (corresponding to 0.45 equivalent of the vinyl ether group with respect to 1 equivalent of the carboxyl group of the rosin-modified phenol resin) was added, and tack 7.5 (30 ° C., 400 rpm) 100 parts of offset ink was obtained.
実施例２
実施例１と同様のフラスコに、重量平均分子量５０，０００、酸価２５ｍｇＫＯＨ／ｇのロジン変性フェノール樹脂１００部、大豆油脂肪酸イソブチルエステル６７部を仕込み、攪拌下に２２０℃まで昇温し、同温度で１時間保温してワニス１６７部を得た。このワニスのうち１００部を前述したものと同じフラスコに取り、撹拌下に８０℃迄昇温した後、ＡＬＣＨ（川研ファインケミカル（株）製、アルミキレート）の５０％大豆油脂肪酸イソブチルエステル溶液０．４部を添加し、２００℃迄昇温した後に５０分間保温し、次いで冷却してゲルワニス１００部を得た。こうして得られたゲルワニスのＥ型粘度は２８０Ｐａ・ｓであった。このゲルワニス７０部にカーミン６Ｂ（顔料）を１５部添加し、三本ロールミルで練肉し、大豆油を１５部添加した。練肉終了後にシクロヘキサンジメタノールジビニルエーテル２．０部（ロジン変性フェノール樹脂のカルボキシル基に対し、当該ビニルエーテル基が？０．４５当量に相当）及び触媒として２，２’−アゾビス−２−メチルブチロニトリル０．４部を添加し、タック７．８のオフセットインキ１００部を得た。
Example 2
In a flask similar to that in Example 1, 100 parts of a rosin-modified phenol resin having a weight average molecular weight of 50,000 and an acid value of 25 mg KOH / g and 67 parts of soybean oil fatty acid isobutyl ester were charged and heated to 220 ° C. with stirring. The temperature was kept for 1 hour to obtain 167 parts of varnish. 100 parts of this varnish was placed in the same flask as described above, heated to 80 ° C. with stirring, and then a 50% soybean oil fatty acid isobutyl ester solution of ALCH (manufactured by Kawaken Fine Chemical Co., Ltd., aluminum chelate) 0 .4 parts was added, the temperature was raised to 200 ° C., kept warm for 50 minutes, and then cooled to obtain 100 parts of gel varnish. The gel varnish thus obtained had an E-type viscosity of 280 Pa · s. 15 parts of Carmine 6B (pigment) was added to 70 parts of this gel varnish, kneaded with a three roll mill, and 15 parts of soybean oil was added. After the milling is finished, 2.0 parts of cyclohexanedimethanol divinyl ether (corresponding to 0.45 equivalent of the vinyl ether group relative to the carboxyl group of the rosin-modified phenol resin) and 2,2′-azobis-2-methylbutyrate as a catalyst 0.4 part of ronitrile was added to obtain 100 parts of offset ink having a tack of 7.8.
実施例３
実施例１と同様のフラスコに、重量平均分子量５０，０００、酸価２５ｍｇＫＯＨ／ｇのロジン変性フェノール樹脂１００部、大豆油脂肪酸イソブチルエステル６７部を仕込み、攪拌下に２２０℃まで昇温し、同温度で１時間保温してワニス１６７部を得た。このワニスのうち１００部を前述したものと同じフラスコに取り、撹拌下に８０℃迄昇温した後、ＡＬＣＨ（川研ファインケミカル（株）製、アルミキレート）の５０％大豆油脂肪酸イソブチルエステル溶液０．４部を添加し、２００℃迄昇した後に５０分間保温し、次いで冷却してゲルワニス１００部を得た。こうして得られたゲルワニスのＥ型粘度は２８０Ｐａ・ｓであった。このゲルワニス７０部にカーミン６Ｂ（顔料）を１５部添加し、三本ロールミルで練肉し、大豆油を１５部添加した。練肉終了後にトリメチロールプロパントリグリシジルエーテル３．６部（ロジン変性フェノール樹脂のカルボキシル基に対し、当該グリシジル基が０．８当量に相当）添加し、タック７．７のオフセットインキ１００部を得た。
Example 3
In a flask similar to that in Example 1, 100 parts of a rosin-modified phenol resin having a weight average molecular weight of 50,000 and an acid value of 25 mg KOH / g and 67 parts of soybean oil fatty acid isobutyl ester were charged and heated to 220 ° C. with stirring. The temperature was kept for 1 hour to obtain 167 parts of varnish. 100 parts of this varnish was placed in the same flask as described above, heated to 80 ° C. with stirring, and then a 50% soybean oil fatty acid isobutyl ester solution of ALCH (manufactured by Kawaken Fine Chemical Co., Ltd., aluminum chelate) 0 4 parts were added, and after raising the temperature to 200 ° C., the mixture was kept warm for 50 minutes and then cooled to obtain 100 parts of gel varnish. The gel varnish thus obtained had an E-type viscosity of 280 Pa · s. 15 parts of Carmine 6B (pigment) was added to 70 parts of this gel varnish, kneaded with a three roll mill, and 15 parts of soybean oil was added. After completion of the meat grinding, 3.6 parts of trimethylolpropane triglycidyl ether (corresponding to 0.8 equivalent of the glycidyl group relative to the carboxyl group of the rosin-modified phenol resin) is added to obtain 100 parts of offset ink with tack 7.7. It was.
実施例４
実施例１と同様のフラスコに、重量平均分子量５０，０００、酸価２５ｍｇＫＯＨ／ｇのロジン変性フェノール樹脂１００部、大豆油脂肪酸イソブチルエステル６７部を仕込み、攪拌下に２２０℃まで昇温し、同温度で１時間保温してワニス１６７部を得た。このワニスのうち１００部を前述したものと同じフラスコに取り、撹拌下において８０℃迄昇温した後、ＡＬＣＨ（川研ファインケミカル（株）製、アルミキレート）の５０％大豆油脂肪酸イソブチルエステル溶液０．４部を添加し、２００℃迄昇温した後に５０分間保温し、次いで冷却してゲルワニス１００部を得た。こうして得られたゲルワニスのＥ型粘度は２８０Ｐａ・ｓであった。このゲルワニス７０部にカーミン６Ｂ（顔料）を１５部添加し、三本ロールミルで練肉し、大豆油を１５部添加した。練肉終了後にペンタエリスリトール−トリ−（３−アジリジン−１−イルプロピオネート）３．０部（ロジン変性フェノール樹脂のカルボキシル基に対し、アジリジン基０．４７当量に相当）添加し、タック７．７のオフセットインキ１００部を得た。
Example 4
In a flask similar to that in Example 1, 100 parts of a rosin-modified phenol resin having a weight average molecular weight of 50,000 and an acid value of 25 mg KOH / g and 67 parts of soybean oil fatty acid isobutyl ester were charged and heated to 220 ° C. with stirring. The temperature was kept for 1 hour to obtain 167 parts of varnish. 100 parts of this varnish was placed in the same flask as described above, heated to 80 ° C. with stirring, and then a 50% soybean oil fatty acid isobutyl ester solution of ALCH (produced by Kawaken Fine Chemical Co., Ltd., aluminum chelate) 0 .4 parts was added, the temperature was raised to 200 ° C., kept warm for 50 minutes, and then cooled to obtain 100 parts of gel varnish. The gel varnish thus obtained had an E-type viscosity of 280 Pa · s. 15 parts of Carmine 6B (pigment) was added to 70 parts of this gel varnish, kneaded with a three roll mill, and 15 parts of soybean oil was added. After completion of the milling, 3.0 parts of pentaerythritol-tri- (3-aziridin-1-ylpropionate) (corresponding to 0.47 equivalents of the aziridine group with respect to the carboxyl group of the rosin-modified phenol resin) was added, and tack 7 Of 100 offset ink was obtained.
実施例５
実施例１と同様のフラスコに、クイントン１３２５（日本ゼオン（株）製、シクロペンタジエン系石油樹脂）１００部を仕込み、撹拌下に２４０℃迄昇温した後、無水マレイン酸７部を仕込み２時間保温した後、ＡＦ７号ソルベント１００部を投入して７０℃迄冷却した後、保温した。ここへ２−ヒドロキシエチルビニルエーテル１２．５部を仕込みそのまま７０℃において１時間反応させた後室温迄冷却し、ビニルエーテル基を持つ石油樹脂ワニス１１９部を得た。別途実施例１と同様のフラスコに、重量平均分子量５０，０００、酸価２５ｍｇＫＯＨ／ｇのロジン変性フェノール樹脂１００部、大豆油脂肪酸イソブチルエステル６７部を仕込み、攪拌下に２２０℃まで昇温し、同温度で１時間保温してワニス１６７部を得た。このワニスのうち１００部を撹拌下８０℃迄昇温した後、ＡＬＣＨ（川研ファインケミカル（株）製、アルミキレート）の５０％ＡＦ７号ソルベント（新日本石油（株）製）溶液０．４部を添加し、２００℃迄昇温した後に５０分間保温し、冷却の後、ゲルワニス１００部を得た。こうして得られたゲルワニスのＥ型粘度は２５０Ｐａ・ｓであった。このゲルワニス７５部にカーミン６Ｂ（顔料）を１５部添加し、三本ロールミルで練肉し、熱架橋性の架橋剤として前述の石油樹脂ワニス１０部（ロジン変性フェノール樹脂のカルボキシル基に対し、ビニルエーテル基０．７６当量に相当）を添加した。こうしてタック７．４のオフセットインキ１００部を得た。
Example 5
In a flask similar to that in Example 1, 100 parts of Quinton 1325 (manufactured by Nippon Zeon Co., Ltd., cyclopentadiene petroleum resin) was charged, heated to 240 ° C. with stirring, and then charged with 7 parts of maleic anhydride for 2 hours. After keeping the temperature, 100 parts of AF7 Solvent was added, cooled to 70 ° C., and then kept warm. The mixture was charged with 12.5 parts of 2-hydroxyethyl vinyl ether, allowed to react at 70 ° C. for 1 hour and then cooled to room temperature to obtain 119 parts of a petroleum resin varnish having a vinyl ether group. Separately, in the same flask as in Example 1, 100 parts of a rosin-modified phenol resin having a weight average molecular weight of 50,000 and an acid value of 25 mg KOH / g and 67 parts of soybean oil fatty acid isobutyl ester were added, and the temperature was raised to 220 ° C. with stirring. The mixture was kept at the same temperature for 1 hour to obtain 167 parts of varnish. After 100 parts of this varnish was heated to 80 ° C. with stirring, 0.4 part of a 50% AF7 solvent (manufactured by Nippon Oil Co., Ltd.) solution of ALCH (manufactured by Kawaken Fine Chemical Co., Ltd., aluminum chelate) Was added, the temperature was raised to 200 ° C., and the temperature was kept for 50 minutes. After cooling, 100 parts of gel varnish was obtained. The gel varnish thus obtained had an E-type viscosity of 250 Pa · s. 15 parts of Carmine 6B (pigment) is added to 75 parts of this gel varnish, kneaded with a three-roll mill, and 10 parts of the aforementioned petroleum resin varnish as a thermally crosslinkable crosslinking agent (vinyl ether with respect to the carboxyl group of the rosin-modified phenol resin). Equivalent to 0.76 equivalents of group). In this way, 100 parts of offset ink with tack 7.4 was obtained.
実施例６
実施例１と同様のフラスコに、重量平均分子量５０，０００、酸価２５ｍｇＫＯＨ／ｇのロジン変性フェノール樹脂１００部、大豆油脂肪酸イソブチルエステル６７部を仕込み、攪拌下に２２０℃まで昇温し、同温度で１時間保温してワニス１６７部を得た。このワニスのうち１００部を前述のフラスコに取り、撹拌下８０℃迄昇温した後、ＡＬＣＨ（川研ファインケミカル（株）製、アルミキレート）の５０％ＡＦ７号ソルベント（新日本石油（株）製）溶液０．４部を添加し、２００℃迄昇温後５０分間保温し、冷却の後に、ゲルワニス１００部を得た。こうして得られたゲルワニスのＥ型粘度は２５０Ｐａ・ｓであった。このゲルワニス７０部にカーミン６Ｂ（顔料）を１５部添加し、三本ロールミルで練肉し、ＡＦ７号ソルベントを１５部添加した。練肉終了後にシクロヘキサンジメタノールジビニルエーテル１０．０部（ロジン変性フェノール樹脂のカルボキシル基に対し、当該ビニルエーテル基が２．３当量に相当）を添加し、タック７．４のオフセットインキ１００部を得た。
Example 6
In a flask similar to that in Example 1, 100 parts of a rosin-modified phenol resin having a weight average molecular weight of 50,000 and an acid value of 25 mg KOH / g and 67 parts of soybean oil fatty acid isobutyl ester were charged and heated to 220 ° C. with stirring. The temperature was kept for 1 hour to obtain 167 parts of varnish. 100 parts of this varnish was placed in the flask described above, heated to 80 ° C. with stirring, and then 50% AF7 Solvent (manufactured by Nippon Oil Corporation) of ALCH (manufactured by Kawaken Fine Chemical Co., Ltd., aluminum chelate). ) 0.4 part of the solution was added, the temperature was raised to 200 ° C. and kept for 50 minutes, and after cooling, 100 parts of gel varnish was obtained. The gel varnish thus obtained had an E-type viscosity of 250 Pa · s. 15 parts of Carmine 6B (pigment) was added to 70 parts of this gel varnish, kneaded with a three roll mill, and 15 parts of AF7 solvent was added. After the milling is completed, 10.0 parts of cyclohexanedimethanol divinyl ether (the vinyl ether group corresponds to 2.3 equivalents relative to the carboxyl group of the rosin-modified phenol resin) is added to obtain 100 parts of offset ink with tack 7.4. It was.
比較例１
実施例１と同様のフラスコに、重量平均分子量５０，０００、酸価２５ｍｇＫＯＨのロジン変性フェノール樹脂１００部、大豆油脂肪酸イソブチルエステル６７部を仕込み、攪拌下に２２０℃まで昇温し、この温度で１時間保温してワニス１６７部を得た。このワニスのうち１００部を前述したものと同じフラスコに取り、撹拌下において８０℃迄昇温した後、ＡＬＣＨ（川研ファインケミカル（株）製、アルミキレート）の５０％ＡＦ７号ソルベント（新日本石油（株）製）溶液０．４部を添加し、２００℃迄昇温した後に５０分間保温し、次いで冷却してゲルワニス１００部を得た。こうして得られたゲルワニスのＥ型粘度は２５０Ｐａ・ｓであった。このゲルワニス７０部にカーミン６Ｂ（顔料）を１５部添加し、三本ロールミルで練肉し、ＡＦ７号ソルベントを１５部添加した。こうしてタック７．６のオフセットインキ１００部を得た。
Comparative Example 1
In a flask similar to that in Example 1, 100 parts of a rosin-modified phenol resin having a weight average molecular weight of 50,000 and an acid value of 25 mg KOH and 67 parts of soybean oil fatty acid isobutyl ester were charged and heated to 220 ° C. with stirring. The mixture was kept warm for 1 hour to obtain 167 parts of varnish. 100 parts of this varnish was placed in the same flask as described above, heated to 80 ° C. with stirring, and then 50% AF7 Solvent (Shin Nippon Oil Co., Ltd.) of ALCH (made by Kawaken Fine Chemical Co., Ltd., aluminum chelate). 0.4 parts of a solution was added, the temperature was raised to 200 ° C., the temperature was kept for 50 minutes, and then cooled to obtain 100 parts of a gel varnish. The gel varnish thus obtained had an E-type viscosity of 250 Pa · s. 15 parts of Carmine 6B (pigment) was added to 70 parts of this gel varnish, kneaded with a three roll mill, and 15 parts of AF7 solvent was added. In this way, 100 parts of offset ink with tack 7.6 was obtained.
比較例２
実施例１と同様のフラスコに、重量平均分子量５０，０００、酸価２５ｍｇＫＯＨ／ｇのロジン変性フェノール樹脂１００部、大豆油脂肪酸イソブチルエステル６７部を仕込み、攪拌下に２２０℃まで昇温し、この温度で１時間保温してワニス１６７部を得た。このワニスのうち１００部を前述したものと同じフラスコに取り、撹拌下８０℃迄昇温した後、ＡＬＣＨ（川研ファインケミカル（株）製、アルミキレート）の５０％大豆油脂肪酸イソブチルエステル溶液０．４部を添加し、２００℃迄昇温後５０分間保温、冷却の後、ゲルワニス１００部を得た。こうして得られたゲルワニスのＥ型粘度は２８０Ｐａ・ｓであった。このゲルワニス７０部にカーミン６Ｂ（顔料）を１５部添加し、三本ロールミルで練肉し、大豆油を１５部添加した。こうしてタック７．０のオフセットインキ１００部を得た。
Comparative Example 2
A flask similar to that of Example 1 was charged with 100 parts of a rosin-modified phenol resin having a weight average molecular weight of 50,000 and an acid value of 25 mg KOH / g, and 67 parts of soybean oil fatty acid isobutyl ester. The temperature was kept for 1 hour to obtain 167 parts of varnish. 100 parts of this varnish was placed in the same flask as described above, heated to 80 ° C. with stirring, and then a 50% soybean oil fatty acid isobutyl ester solution of ALCH (manufactured by Kawaken Fine Chemical Co., Ltd., aluminum chelate). 4 parts were added, and after raising the temperature to 200 ° C., keeping the temperature for 50 minutes and cooling, 100 parts of gel varnish was obtained. The gel varnish thus obtained had an E-type viscosity of 280 Pa · s. 15 parts of Carmine 6B (pigment) was added to 70 parts of this gel varnish, kneaded with a three roll mill, and 15 parts of soybean oil was added. In this way, 100 parts of offset ink having a tack of 7.0 was obtained.
（性能試験）
セット性 ：インキ０．２７ｍｌをＪＩＳＫ５７０１に準じてＲＩテスター（石川島産業機械（株）製）を使用し、コート紙上に展色する。その展色物を１６０℃の乾燥器中に４秒間曝露し、取り出し後直ちに指触により、残留したタック感を評価した。◎残留タックなし。○：残留タック少しあり。×：残留タック有り。
光沢 ：インキ０．２７ｍｌをＪＩＳＫ５７０１に準じてＲＩテスター（石川島産業機械（株）製）を使用し、コート紙上に展色する。この展色試料を１６０℃の雰囲気下で８秒間乾燥後、ＪＩＳＺ８７４１に準じて６０度鏡面光沢度を測定した。
耐摩擦性 ：前述のセット性試験に用いた展色物をＪＩＳＫ５７０１−１に準じてS型摩擦試験機を用いて４３回往復後の表面状態を目視によって判定した。◎全く剥離なし。○：殆ど剥離なし。×：剥離あり。
安定性 ：インキを４０℃の雰囲気下に２４時間放置し、表面の皮張り状態を目視によって判定した。◎全く皮張りなし。○：殆ど皮張りなし。×：皮張りあり。
(performance test)
Setting property: ink 0.27ml to use the RI tester (Ishikawajimasangyokikai Co., Ltd.) in accordance with the JISK5701, color Exhibition on coated paper. The color-extended product was exposed to a 160 ° C. drier for 4 seconds, and immediately after removal, the remaining tackiness was evaluated by finger touch. ◎ No residual tack. ○: There is a little residual tack. X: Residual tack is present.
Gloss : 0.27 ml of ink is developed on coated paper using a RI tester (Ishikawajima Industrial Machinery Co., Ltd.) according to JISK5701. The developed color sample was dried for 8 seconds in an atmosphere of 160 ° C., and then the 60 ° specular gloss was measured according to JISZ8741.
Friction resistance : The surface condition after 43 reciprocations was visually determined using the S-type friction tester according to JISK5701-1 for the color-extracted material used in the set property test described above. ◎ No peeling at all. ○: Almost no peeling. X: There is peeling.
Stability : The ink was allowed to stand in an atmosphere of 40 ° C. for 24 hours, and the skin state of the surface was judged visually. ◎ No skin. ○: Almost no skin. X: There is skinning.
上記の各性能評価結果を表１に示す。 The performance evaluation results are shown in Table 1.
Claims (5)
A thermosetting offset ink comprising the thermosetting offset ink composition according to claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008150469A (en) * | 2006-12-15 | 2008-07-03 | Sakata Corp | Heat set type offset-printing ink composition |
| WO2013046699A1 (en) * | 2011-09-29 | 2013-04-04 | コニカミノルタホールディングス株式会社 | Active energy ray-curable inkjet ink, and inkjet recording method using same |
| JP2019048971A (en) * | 2017-09-07 | 2019-03-28 | 荒川化学工業株式会社 | Varnish composition for off-set printing ink, and off-set printing ink |
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| CN105153407B (en) * | 2015-10-20 | 2017-01-04 | 山东科技大学 | A kind of thermosetting rosin resin compositions and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04168168A (en) * | 1990-10-31 | 1992-06-16 | Sakata Corp | Varnish for lithographic ink and lithographic ink composition using the same |
| JP2000212489A (en) * | 1999-01-28 | 2000-08-02 | Pilot Ink Co Ltd | Thermally fugitive dry offset ink and printed matter by use thereof |
| JP2002363466A (en) * | 2001-06-08 | 2002-12-18 | Matsui Shikiso Chem Co Ltd | Temperature-sensitively color-changing dry offset ink and printed matter therewith |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04168168A (en) * | 1990-10-31 | 1992-06-16 | Sakata Corp | Varnish for lithographic ink and lithographic ink composition using the same |
| JP2000212489A (en) * | 1999-01-28 | 2000-08-02 | Pilot Ink Co Ltd | Thermally fugitive dry offset ink and printed matter by use thereof |
| JP2002363466A (en) * | 2001-06-08 | 2002-12-18 | Matsui Shikiso Chem Co Ltd | Temperature-sensitively color-changing dry offset ink and printed matter therewith |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008150469A (en) * | 2006-12-15 | 2008-07-03 | Sakata Corp | Heat set type offset-printing ink composition |
| WO2013046699A1 (en) * | 2011-09-29 | 2013-04-04 | コニカミノルタホールディングス株式会社 | Active energy ray-curable inkjet ink, and inkjet recording method using same |
| JP2019048971A (en) * | 2017-09-07 | 2019-03-28 | 荒川化学工業株式会社 | Varnish composition for off-set printing ink, and off-set printing ink |
| JP7040366B2 (en) | 2017-09-07 | 2022-03-23 | 荒川化学工業株式会社 | Varnish composition for offset printing ink, offset printing ink |
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