JPH04335070A - Water-base printing ink - Google Patents
Water-base printing inkInfo
- Publication number
- JPH04335070A JPH04335070A JP3136002A JP13600291A JPH04335070A JP H04335070 A JPH04335070 A JP H04335070A JP 3136002 A JP3136002 A JP 3136002A JP 13600291 A JP13600291 A JP 13600291A JP H04335070 A JPH04335070 A JP H04335070A
- Authority
- JP
- Japan
- Prior art keywords
- water
- copolymer
- printing ink
- chelate compound
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 21
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000013522 chelant Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 125000002524 organometallic group Chemical group 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- -1 acrylic ester Chemical class 0.000 abstract description 14
- 239000002904 solvent Substances 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 5
- 229920006243 acrylic copolymer Polymers 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 31
- 239000011347 resin Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 14
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Chemical class 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 229940093858 ethyl acetoacetate Drugs 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- MQPPCKJJFDNPHJ-UHFFFAOYSA-K aluminum;3-oxohexanoate Chemical compound [Al+3].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O MQPPCKJJFDNPHJ-UHFFFAOYSA-K 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000002794 monomerizing effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- FLYOONQBYFVITK-UHFFFAOYSA-N propan-2-yl 3-oxohexaneperoxoate Chemical compound CCCC(=O)CC(=O)OOC(C)C.CCCC(=O)CC(=O)OOC(C)C FLYOONQBYFVITK-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、水性印刷インキに関す
るもので、耐溶剤性、耐薬品性、耐水性の優れた水性印
刷インキに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous printing ink having excellent solvent resistance, chemical resistance and water resistance.
【０００２】0002
【従来の技術】各種プラスチックフィルム、金属箔など
への印刷インキとして、有機溶剤可溶型の樹脂（ウレタ
ン、ポリアミド、ニトロセルロース、ポリエステルなど
）が単独もしくは併用の形で使用されているが、有機溶
剤による火災、大気汚染の防止もしくは省資源の観点か
らこれらに代わる、耐溶剤性、耐薬品性、耐水性などの
物性を有している水性印刷インキ開発が切望されている
。[Prior Art] Organic solvent-soluble resins (urethane, polyamide, nitrocellulose, polyester, etc.) are used alone or in combination as printing inks for various plastic films, metal foils, etc. In order to prevent fires and air pollution caused by solvents and to save resources, there is a strong desire to develop a water-based printing ink that has physical properties such as solvent resistance, chemical resistance, and water resistance as an alternative to these.
【０００３】有機溶剤型印刷インキは、バインダー自身
に耐水性を有しており、イソシアネート化合物やエポキ
シ化合物を使用し、架橋したインキ膜を得ることで、耐
溶剤性、耐薬品性など、より高い品位の物性を得ている
。[0003] Organic solvent printing ink has water resistance in the binder itself, and by using isocyanate compounds and epoxy compounds to obtain a crosslinked ink film, it has higher solvent resistance, chemical resistance, etc. Obtains quality physical properties.
【０００４】水性印刷インキのバインダーとしては、一
般的なものにスチレン−マレイン酸共重合樹脂、スチレ
ン−アクリル共重合樹脂、マレイン化ロジン、アクリル
樹脂などがあり、プラスチックフィルムや金属箔への接
着性、印刷適性の改善を目的としたバインダーとしては
、特開昭５３−８５６０６号公報、特開昭５６−４１２
７６公報、特開昭５９−１５４６１号公報等に種々の提
案がなされている。Common binders for water-based printing inks include styrene-maleic acid copolymer resins, styrene-acrylic copolymer resins, maleated rosins, and acrylic resins, which have excellent adhesion to plastic films and metal foils. , as binders for the purpose of improving printability, Japanese Patent Application Laid-Open No. 53-85606 and Japanese Patent Application Laid-Open No. 56-412
Various proposals have been made in Publication No. 76, Japanese Unexamined Patent Publication No. 59-15461, etc.
【０００５】しかしながら、これらから得られるバイン
ダーは水溶性や安定な分散液にするため、合成上、低分
子量化やカルボキシル基等の極性の大きいビニルモノマ
ーの共重合量を増さなければならないという制約があっ
た。このため、得られた印刷物の耐水性、耐溶剤性、耐
薬品性等の物性は、実用上きわめて低いレベルであった
。However, in order to make the binder obtained from these into a water-soluble and stable dispersion, there are constraints on synthesis such as lowering the molecular weight and increasing the copolymerization amount of highly polar vinyl monomers such as carboxyl groups. was there. Therefore, the physical properties of the obtained printed matter, such as water resistance, solvent resistance, and chemical resistance, were at an extremely low level for practical use.
【０００６】耐溶剤性、耐薬品性、耐水性など十分な物
性を得るために、水性印刷インキ中にアジリジン化合物
、エポキシ化合物、カルボジイミド化合物、金属キレー
ト化合物を添加し、乾燥後インキ膜を架橋させ、目的と
する物性を得ることが知られている。In order to obtain sufficient physical properties such as solvent resistance, chemical resistance, and water resistance, aziridine compounds, epoxy compounds, carbodiimide compounds, and metal chelate compounds are added to water-based printing inks, and the ink film is crosslinked after drying. It is known that the desired physical properties can be obtained.
【０００７】架橋剤としてアルミニウムキレート剤を使
い、水性樹脂に耐熱性を付与する方法（特開昭５７−８
５８６５号公報）が提案されているが、この方法では耐
熱性は得られるものの、印刷インキとして平滑性や美粧
性の優れた印刷物は得られない。[0007] A method of imparting heat resistance to a water-based resin by using an aluminum chelating agent as a crosslinking agent (Japanese Patent Laid-Open No. 57-8
No. 5865) has been proposed, but although heat resistance can be obtained with this method, printed matter with excellent smoothness and cosmetic properties cannot be obtained as a printing ink.
【０００８】低温硬化性の組成物として、カルボキシル
基を含有する樹脂を塩基物質で中和し、アジリジンとの
反応を抑え貯蔵安定性を高める方法（特開昭５４−１５
９４４７号公報）が提案されているが、この方法では貯
蔵安定性に多少の効果はあるものの、アジリジンの加水
分解との競争反応であり、長時間の効果は期待できない
。[0008] As a low-temperature curable composition, a method is proposed in which a resin containing a carboxyl group is neutralized with a basic substance to suppress the reaction with aziridine and improve storage stability (Japanese Patent Laid-Open No. 54-15
No. 9447) has been proposed, but although this method has some effect on storage stability, it is a competitive reaction with the hydrolysis of aziridine, so long-term effects cannot be expected.
【０００９】一方、有機金属キレート剤では、水中で比
較的安定であるものの、乾燥後の架橋効果に乏しく、可
使時間の長さと架橋の速さとは両立し難くい。On the other hand, although organometallic chelating agents are relatively stable in water, they have a poor crosslinking effect after drying, and it is difficult to achieve both a long pot life and a high crosslinking speed.
【００１０】さらに、印刷時には架橋に必要な熱量は得
られ難いため、反応性の高い上記のような架橋剤を必然
的に多く使うことになる。この方法では、インキの時間
と共に安定性が悪くなり、安定して印刷することが難し
い。すなわち、架橋剤の使用量を少なくして、印刷後速
い架橋を行わせることが望ましい。Furthermore, since it is difficult to obtain the amount of heat necessary for crosslinking during printing, a large amount of the highly reactive crosslinking agent mentioned above is necessarily used. With this method, the stability of the ink deteriorates over time, making it difficult to print stably. In other words, it is desirable to reduce the amount of crosslinking agent used to achieve rapid crosslinking after printing.
【００１１】[0011]
【発明が解決しようとする課題】本発明者は、検討の結
果、水性印刷インキと架橋剤とを組み合せて使用する場
合において、樹脂骨格中のカルボキシ基がアクリル酸も
しくはメタクリル酸からなるものに比べ、特定の位置に
カルボキシル基を有するモノマーと他のビニルモノマー
を溶液重合し、塩基物質で完全中和もしくは部分中和し
た樹脂からなる水性印刷インキと、有機金属キレート化
合物を組み合せて使用した場合、きわめて長時間の可使
時間と耐溶剤性、耐薬品性、耐水性に優れた印刷物を得
られることを見出し本発明に至ったものであり、本発明
は前記の従来の種々の欠点を改良し、硬化性に優れた水
性印刷インキを提供するものである。[Problems to be Solved by the Invention] As a result of studies, the present inventor found that when using a water-based printing ink and a crosslinking agent in combination, the carboxyl group in the resin skeleton is , when a water-based printing ink consisting of a resin made by solution polymerizing a monomer having a carboxyl group at a specific position and another vinyl monomer and completely or partially neutralized with a basic substance is used in combination with an organometallic chelate compound, The inventors discovered that it was possible to obtain printed matter with an extremely long pot life and excellent solvent, chemical, and water resistance, and the present invention improves the various drawbacks of the conventional methods described above. , to provide a water-based printing ink with excellent curability.
【００１２】0012
【課題を解決するための手段】本発明は、一般式；[Means for Solving the Problems] The present invention provides a general formula;
【０
０１３】0
013]
【化２】[Case 2]
【００１４】（式中、Ｒ１ は水素もしくはメチル基、
Ｒ２ はＣ、Ｈ、Ｏ原子からなり、炭素数が１〜２０で
あり−ＣＯＯＨを有する）で表わされるアクリル酸エス
テルを３〜６０重量％含むことよりなる共重合体と有機
金属キレート化合物を含むことを特徴とする水性印刷イ
ンキである。(wherein R1 is hydrogen or a methyl group,
R2 is composed of C, H, and O atoms, has 1 to 20 carbon atoms, and contains -COOH), and contains a copolymer containing 3 to 60% by weight of an acrylic ester and an organometallic chelate compound. This is a water-based printing ink that is characterized by:
【００１５】本発明を実施するに際して用いる、必須成
分である前述の一般式で特定する化合物の具体例として
Specific examples of the compounds specified by the above general formula that are essential components used in carrying out the present invention are as follows:
【００１６】[0016]
【化３】[Chemical 3]
【００１７】等、Ｒ２ の炭素数が１から２０までのビ
ニルモノマーがあげられ、ビニルモノマー混合物中の共
重合比率としては３〜６０％の範囲で使用する。使用量
が少ないと、目的とする反応性向上に対してほとんど効
果がなく、また多過ぎるとコスト高になるばかりか、耐
アルカリ性や耐水性を低下させてしまう。Examples include vinyl monomers in which R2 has 1 to 20 carbon atoms, and the copolymerization ratio in the vinyl monomer mixture is from 3 to 60%. If the amount used is small, it will have little effect on the desired improvement in reactivity, and if it is too large, it will not only increase the cost but also reduce the alkali resistance and water resistance.
【００１８】本発明に於ける共重合体のビニルモノマー
組成において、アクリル酸もしくはメタクリル酸を０〜
４０重量％の範囲で使用する。アクリル酸もしくはメタ
クリル酸が少な過ぎると水溶化性に乏しく、また多過ぎ
ると、耐アルカリ性、耐水性を低下させてしまう。In the vinyl monomer composition of the copolymer in the present invention, acrylic acid or methacrylic acid is contained in a range of 0 to 0.
It is used in a range of 40% by weight. If the amount of acrylic acid or methacrylic acid is too small, the water solubility will be poor, and if it is too large, the alkali resistance and water resistance will be reduced.
【００１９】他の共重合可能なビニルモノマーとしては
（メタ）アクリル酸メチル、（メタ）アクリル酸エチル
、（メタ）アクリル酸ブチル、（メタ）アクリル酸２エ
チルヘキシル（メタ）アクリル酸２ヒドロキシエチルな
どの（メタ）アクリル酸エステル類およびスチレン、（
メタ）アクリロニトリル、（メタ）アクリルアミド、酢
酸ビニルなどのモノマーが挙げられ、４０〜８０重量％
の範囲で使用する。Other copolymerizable vinyl monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, etc. (meth)acrylic esters and styrene, (
Examples include monomers such as meth)acrylonitrile, (meth)acrylamide, and vinyl acetate, with a content of 40 to 80% by weight.
Use within the range.
【００２０】本発明において、上記ビニルモノマー混合
物を溶液重合せしめるのは公知の方法でよく、例えばア
ゾビスイソブチロニトリルのようなラジカル基を発生す
る開始剤の存在下に、イソプロピルアルコールなどの有
機溶剤中で重合する。In the present invention, the vinyl monomer mixture may be solution-polymerized by any known method, for example, an organic polymer such as isopropyl alcohol is polymerized in the presence of an initiator that generates a radical group such as azobisisobutyronitrile. Polymerizes in a solvent.
【００２１】本発明で使用するアクリル共重合体の重量
平均分子量は２０，０００以上、７０，０００以下が望
ましい。得られたアクリル共重合体の中和に必要な塩基
としては、ジメチルエタノールアミン、ジエチルエタノ
ールアミン、トリエチルアミン、トリエタノールアミン
、モルホリンなどの有機アミンまたはアンモニア、好ま
しくはアンモニアで中和して、ｐＨが７〜９の範囲が好
適である。The weight average molecular weight of the acrylic copolymer used in the present invention is preferably 20,000 or more and 70,000 or less. The base necessary for neutralizing the obtained acrylic copolymer includes organic amines such as dimethylethanolamine, diethylethanolamine, triethylamine, triethanolamine, and morpholine, or ammonia, preferably ammonia to adjust the pH. A range of 7 to 9 is preferred.
【００２２】本発明に係る水性印刷インキは顔料などの
着色材、充填材その他必要な添加剤を加え、公知の練肉
の方法より得られる。また、本発明の水性印刷インキに
は、その性能を阻害しない範囲で必要に応じてシェラッ
ク樹脂、ロジン変性マレイン酸樹脂、カルボキシル化石
油樹脂、セルロース系樹脂、スチレン、マレイン酸樹脂
あるいはハイドロゾル樹脂と混合して使用できる。The aqueous printing ink according to the present invention can be obtained by adding colorants such as pigments, fillers and other necessary additives, and by a known kneading method. In addition, the water-based printing ink of the present invention may be mixed with shellac resin, rosin-modified maleic acid resin, carboxylated petroleum resin, cellulose resin, styrene, maleic acid resin, or hydrosol resin as necessary to the extent that does not impair its performance. It can be used as
【００２３】本発明において、有機金属キレート化合物
としては、ジ−イソ−プロポキシビス（アセチルアセト
ン）チタネート、ジ−ｎ−ブトキシビス（トリエタノー
ルアミン）チタネート（ＴＡＴ）、ジ−ヒドロキシビス
（ラクティクアシッド）チタネート（ＴＬＡ）、テトラ
−オクチレングリコールチタネート、ジ−イソ−プロポ
キシビス（アセト酢酸エチル）チタネート、ポリ−（ヒ
ドロキシチタンステアレート）、ジ−イソ−プロポキシ
アルミニウムモノエチルアセトアセテート、ジ−イソ−
プロポキシアルミニウムモノメチルアセトアセテート、
ジ−ｎ−ブトキシアルミニウム−モノ−エチルアセトア
セテート、アルミニウムトリス（エチルアセトアセテー
ト）、アルミニウムモノアセチルアセトネートビス（エ
チルアセトアセテート）（ＡＬＤ）、アルミニウムトリ
ス（アセチルアセトアセトネート）（ＡＬＡ）、アルミ
ニウム−ジ−ｎ−ブトキサイド−モノ−メチルアセトア
セテート、アルミニウム−ジイソブトキサイド−モノ−
メチルアセトアセテート、アルミニウム−ジ−ｓｅｔ−
ブトキサイド−モノ−エチルアセトアセテートトリラク
テートジルコン酸アンモニウム、トリグリコラートジル
コン酸アンモニウム、等を挙げることができる。In the present invention, examples of the organometallic chelate compound include di-iso-propoxybis(acetylacetone) titanate, di-n-butoxybis(triethanolamine)titanate (TAT), and di-hydroxybis(lactic acid)titanate. (TLA), tetra-octylene glycol titanate, di-iso-propoxy bis(ethyl acetoacetate) titanate, poly-(hydroxytitanium stearate), di-iso-propoxyaluminum monoethyl acetoacetate, di-iso-
propoxyaluminum monomethyl acetoacetate,
Di-n-butoxyaluminum-mono-ethylacetoacetate, aluminum tris(ethylacetoacetate), aluminum monoacetylacetonate bis(ethylacetoacetate) (ALD), aluminum tris(acetylacetoacetonate) (ALA), aluminum- Di-n-butoxide mono-methyl acetoacetate, aluminum diisobutoxide mono-
Methyl acetoacetate, aluminum-di-set-
Butoxide-mono-ethylacetoacetate trilactate ammonium zirconate, triglycolate ammonium zirconate, and the like can be mentioned.
【００２４】有機金属キレート化合物の使用量は、０．
１〜１０重量％である。０．１以下の場合においては、
架橋効果に乏しく、１０重量％を越えると、インキの経
時粘度上昇や、再溶解性低下による版詰りを招き結果的
に印刷効果を損う。The amount of the organometallic chelate compound used is 0.
It is 1 to 10% by weight. In the case of 0.1 or less,
The crosslinking effect is poor, and if it exceeds 10% by weight, the viscosity of the ink increases over time and plate clogging occurs due to decreased resolubility, resulting in a loss of printing effectiveness.
【００２５】[0025]
【作用】本発明を実施するに際して用いる、必須成分で
ある前述の一般式で特定する化合物は、アクリル酸ある
いはメタクリル酸に比べ、カルボキシル基が、ビニル重
合によって形成される主鎖からより離れた位置にあり、
分子運動的自由度が大きくそのことによって有機金属キ
レート化合物である架橋剤との反応にきわめて有利に働
いていると考えられる。[Operation] The compound specified by the above general formula, which is an essential component used in carrying out the present invention, has a carboxyl group located further away from the main chain formed by vinyl polymerization than acrylic acid or methacrylic acid. Located in
It has a large degree of molecular motion freedom, which is thought to work extremely favorably in the reaction with the crosslinking agent, which is an organometallic chelate compound.
【００２６】[0026]
実施例１〜４
撹拌装置、温度計、窒素ガス導入管を備えた２リットル
の４ツ口フラスコにエタノール４５０ｇを仕込み、７９
〜８１℃まで加熱し、この温度を保持する。次いで次式
で表わされるビニルモノマーExamples 1 to 4 450 g of ethanol was charged into a 2 liter four-necked flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, and 79 g of ethanol was charged.
Heat to ~81°C and maintain this temperature. Then a vinyl monomer represented by the following formula
【００２７】
ＣＨ２ ＝ＣＨＣＯＯＣ２ Ｈ４ ＯＣＯＣ２ Ｈ４
ＣＯＯＨ４５ｇ、アクリル酸６０ｇ、ｎ−ブチルメタク
リレート１５０ｇ、メチルメタクリレート４５ｇ及びア
ゾビスイソブチロニトリル１２ｇを９０分かけて滴下し
た後、更に４時間反応を続け、酸価１８０の樹脂を得た
。その後減圧蒸留により溶媒を溜去し、ｐＨ８．５、樹
脂固形分３３％になるよう、２５％アンモニア水及び水
／エタノール６０／４０（重量比）を加えた。得られた
樹脂１２０ｇ、リオノールブルーＦＧ７３３０（東洋イ
ンキ製造（株）製、商品名）１８ｇ、シリコン系消泡剤
１ｇ、ポリエチレンワックス２ｇ及び水５９ｇの混合物
をアトライターにて混練し、水性印刷インキ（Ａ）を調
製した。CH2=CHCOOC2 H4 OCOC2 H4
After 45 g of COOH, 60 g of acrylic acid, 150 g of n-butyl methacrylate, 45 g of methyl methacrylate, and 12 g of azobisisobutyronitrile were added dropwise over 90 minutes, the reaction was continued for an additional 4 hours to obtain a resin with an acid value of 180. Thereafter, the solvent was distilled off under reduced pressure, and 25% ammonia water and water/ethanol 60/40 (weight ratio) were added so that the pH was 8.5 and the resin solid content was 33%. A mixture of 120 g of the obtained resin, 18 g of Lionol Blue FG7330 (manufactured by Toyo Ink Mfg. Co., Ltd., trade name), 1 g of silicone antifoaming agent, 2 g of polyethylene wax, and 59 g of water was kneaded in an attritor to form a water-based printing ink. (A) was prepared.
【００２８】得られたインキを表１に示す有機金属キレ
ート化合物と配合し、水とエタノールの混合物（重量比
で５０：５０）で離合社製ザーンカップＮｏ．３にて１
６秒／２５℃に希釈し、グラビア方式（ヘリオ版１７５
線／インチ、乾燥温度７０℃印刷速度５０ｍ／分）で、
厚さ２０μｍのコロナ放電処理延伸ポリプロピレンフィ
ルムのコロナ放電処理面（濡れ指数４２ｄｙｎｅ／ｃｍ
）に印刷した。その後、印刷物を４０℃の恒温槽で２４
時間放置し、耐溶剤性、耐アルカリ性及び耐水性を評価
した。評価結果を表１に示す。The obtained ink was blended with the organometallic chelate compound shown in Table 1, and mixed with a mixture of water and ethanol (50:50 by weight) using Zahn Cup No. 1 manufactured by Rigosha. 1 in 3
Diluted to 6 seconds/25℃, gravure method (Helio version 175
line/inch, drying temperature 70℃, printing speed 50m/min),
Corona discharge treated surface of a 20 μm thick corona discharge treated stretched polypropylene film (wetting index 42 dyne/cm)
) was printed. After that, the printed matter was placed in a constant temperature bath at 40℃ for 24 hours.
The samples were left to stand for a period of time and their solvent resistance, alkali resistance and water resistance were evaluated. The evaluation results are shown in Table 1.
【００２９】尚、評価方法および結果の表示は次の通り
である。耐溶剤性：エタノールを含ませた脱脂綿で、印
刷物表面をラビングし、インキ膜が消失するまでの往復
ラビング回数で評価
◎：４０回以上 ○：４０〜２０回 △：２０〜１
０ ×：１０回以下耐アルカリ性：印刷物に１％水酸
化ナトリウム水溶液をスポットし、１時間後、脱脂綿で
こすり取り、印刷物の表面状態を目視評価。
◎：変化なし △：微少な脱離は認められるが、実用
上の問題はなし ×：印刷物に大きな脱離が生じる。
耐水性：８５℃の温水に印刷物を３０分間浸漬した後、
取出し、濡れたまま、脱脂綿でこすり、塗膜の表面状態
を目視判定。
経時粘度変化：有機金属キレート化合物配合後、４０℃
の恒温槽に１週間保存し、その時の粘度の変化を判定し
た。
○：粘度上昇が、初期の粘度に比較し、１〜１．５倍の
もの
△：粘度上昇が、初期の粘度に比較し、１．５〜２．０
倍のもの
×：粘度上昇が、初期の粘度に比較し、２倍以上のもの
The evaluation method and display of results are as follows. Solvent resistance: Rub the surface of the printed matter with absorbent cotton soaked in ethanol, and evaluate by the number of times of back-and-forth rubbing until the ink film disappears ◎: 40 times or more ○: 40 to 20 times △: 20 to 1
0 ×: 10 times or less Alkali resistance: A 1% aqueous sodium hydroxide solution was spotted on the printed matter, and after 1 hour, it was rubbed off with absorbent cotton, and the surface condition of the printed matter was visually evaluated. ◎: No change △: Slight detachment is observed, but there is no practical problem. ×: Large detachment occurs in printed matter. Water resistance: After soaking the printed matter in warm water at 85°C for 30 minutes,
Take it out, rub it with absorbent cotton while still wet, and visually judge the surface condition of the paint film. Change in viscosity over time: 40°C after blending the organometallic chelate compound
The sample was stored in a constant temperature bath for one week, and the change in viscosity at that time was determined. ○: The viscosity increase is 1 to 1.5 times the initial viscosity. △: The viscosity increase is 1.5 to 2.0 times the initial viscosity.
Double ×: The viscosity increase is more than double compared to the initial viscosity.
【００３０】実施例５〜８
実施例１におけるビニルモノマー混合液に代えて、次式
で表わされるビニルモノマーExamples 5 to 8 In place of the vinyl monomer mixture in Example 1, a vinyl monomer represented by the following formula was used.
【００３１】[0031]
【化４】[C4]
【００３２】６３ｇ、アクリル酸６０ｇ、ｎ−ブチルメ
タクリレート１３２ｇ、メチルメタクリレート４５ｇ及
びアゾビスイソブチロニトリル１２ｇを使用し、実施例
１と同様な操作で反応を行い、酸価１７８の樹脂を得た
。以後、実施例１と同様な操作で、水溶化した後、イン
キ化をし、水性印刷インキ（Ｂ）を調製し、表１に示す
有機金属キレート化合物を配合し、実施例１と同様に印
刷し、評価結果を表１に示す。A reaction was carried out in the same manner as in Example 1 using 63 g of acrylic acid, 60 g of acrylic acid, 132 g of n-butyl methacrylate, 45 g of methyl methacrylate, and 12 g of azobisisobutyronitrile to obtain a resin with an acid value of 178. . Thereafter, in the same manner as in Example 1, the water-based printing ink (B) was prepared by making it water-soluble and then forming it into an ink. The evaluation results are shown in Table 1.
【００３３】実施例９〜１２
実施例１におけるビニルモノマー混合液に代えて、次式
で表わされるビニルモノマーExamples 9 to 12 In place of the vinyl monomer mixture in Example 1, a vinyl monomer represented by the following formula was used.
【００３４】[0034]
【化５】[C5]
【００３５】１３２ｇ、アクリル酸４５ｇ、ｎ−ブチル
メタクリレート９０ｇ、スチレン３３ｇ及びアゾビスイ
ソブチロニトリル１２ｇを使用し、実施例１と同様な操
作で反応を行い、酸価２００の樹脂を得た。以後、実施
例１と同様な操作で、水溶化した後、インキ化をし、水
性印刷インキ（Ｃ）を調製し、表１に示す硬化剤を配合
し、実施例１と同様に印刷し、評価結果を表１に示す。A reaction was carried out in the same manner as in Example 1 using 132 g of acrylic acid, 45 g of acrylic acid, 90 g of n-butyl methacrylate, 33 g of styrene and 12 g of azobisisobutyronitrile to obtain a resin with an acid value of 200. Thereafter, in the same manner as in Example 1, after making it water-soluble, it was made into an ink to prepare a water-based printing ink (C), the curing agent shown in Table 1 was blended, and it was printed in the same manner as in Example 1. The evaluation results are shown in Table 1.
【００３６】実施例１３〜１６
実施例１におけるビニルモノマー混合液に代えて、次式
で表わされるビニルモノマーExamples 13 to 16 In place of the vinyl monomer mixture in Example 1, a vinyl monomer represented by the following formula was used.
【００３７】[0037]
【化６】[C6]
【００３８】６ｇ、アクリル酸７５ｇ、ｎ−ブチルアク
リレート１７４ｇ、エチルメタクリレート４５ｇ及びア
ゾビスイソブチロニトリル１２ｇを使用し、実施例１と
同様な操作で反応を行い、酸価１９４の樹脂を得た。以
後、実施例１と同様な操作で、水溶化した後、インキ化
をし、水性印刷インキ（Ｄ）を調製し、表１に示す有機
金属キレート化合物を配合し、実施例１と同様に印刷し
、評価結果を表１に示す。A reaction was carried out in the same manner as in Example 1 using 6 g of acrylic acid, 75 g of acrylic acid, 174 g of n-butyl acrylate, 45 g of ethyl methacrylate, and 12 g of azobisisobutyronitrile to obtain a resin with an acid value of 194. . Thereafter, in the same manner as in Example 1, the water-based printing ink (D) was prepared by making it water-soluble and then forming it into an ink. The evaluation results are shown in Table 1.
【００３９】比較例１〜４
実施例１におけるビニルモノマー混合液に代えて、アク
リル酸７５ｇ、ｎ−ブチルメタクリレート１６５ｇ、エ
チルメタクリレート６０ｇ及びアゾビスイソブチロニト
リル１２ｇを使用し、実施例１と同様な操作で反応を行
い、酸価１８５の樹脂を得た。以後、実施例１と同様な
操作で、水溶化した後、インキ化をし、水性印刷インキ
（Ｅ）を調製し、表１に示す有機金属キレート化合物を
配合し、実施例１と同様に印刷し、評価結果を表１に示
す。Comparative Examples 1 to 4 Same as Example 1 except that 75 g of acrylic acid, 165 g of n-butyl methacrylate, 60 g of ethyl methacrylate and 12 g of azobisisobutyronitrile were used in place of the vinyl monomer mixture in Example 1. The reaction was carried out in accordance with the following procedures, and a resin having an acid value of 185 was obtained. Thereafter, in the same manner as in Example 1, the water-based printing ink (E) was prepared by making it water-soluble and then forming it into an ink. The evaluation results are shown in Table 1.
【００４０】比較例５〜８
実施例１におけるビニルモノマー混合液に代えて、メタ
クリル酸９０ｇ、アクリル酸４５ｇ、ｎ−ブチルメタク
リレート７５ｇ、ｎ−ブチルアクリレート９０ｇ及びア
ゾビスイソブチロニトリル１２ｇを使用し、実施例１と
同様な操作で反応を行い、酸価２０２の樹脂を得た。以
後実施例１と同様な操作で水溶化した後、インキ化をし
、水性印刷インキ（Ｆ）を調製し、表１に示す有機金属
キレート化合物を配合し、実施例１と同様に印刷し、評
価結果を表１に示す。Comparative Examples 5 to 8 In place of the vinyl monomer mixture in Example 1, 90 g of methacrylic acid, 45 g of acrylic acid, 75 g of n-butyl methacrylate, 90 g of n-butyl acrylate, and 12 g of azobisisobutyronitrile were used. A reaction was carried out in the same manner as in Example 1 to obtain a resin having an acid value of 202. Thereafter, it was made water-solubilized in the same manner as in Example 1, and then made into an ink to prepare a water-based printing ink (F), and the organometallic chelate compound shown in Table 1 was blended, and printed in the same manner as in Example 1. The evaluation results are shown in Table 1.
【００４１】[0041]
【表１】[Table 1]
【００４２】[0042]
【発明の効果】本発明により次のような効果が確認され
た。即ち、特定の位置にカルボキシル基を有するモノマ
ーと他のビニルモノマーを溶液重合し、塩基物質で中和
した樹脂からなる水性インキが、有機金属キレート剤組
合せて使用した場合、耐溶剤性、耐薬品性、耐水性に優
れた印刷物が得られることが確認された。[Effects of the Invention] The following effects were confirmed by the present invention. That is, when a water-based ink made of a resin made by solution polymerizing a monomer having a carboxyl group at a specific position and another vinyl monomer and neutralizing it with a basic substance is used in combination with an organometallic chelating agent, it has good solvent resistance and chemical resistance. It was confirmed that printed matter with excellent durability and water resistance could be obtained.
Claims (4)
Ｈ、Ｏ原子からなり、炭素数が１〜２０であり−ＣＯＯ
Ｈを有する）で表わされるアクリル酸エステルを３〜６
０重量％含むことよりなる共重合体と有機金属キレート
化合物を含むことを特徴とする水性印刷インキ。Claim 1 General formula; [Formula 1] (wherein, R1 is hydrogen or a methyl group, R2 is C,
It consists of H and O atoms, has 1 to 20 carbon atoms, and -COO
3 to 6 acrylic esters (having H)
1. A water-based printing ink comprising a copolymer containing 0% by weight and an organometallic chelate compound.
て、アクリル酸もしくはメタクルリ酸モノマーが０〜４
０重量％、他の共重合可能なビニルモノマーが４０〜８
０重量％であることを特徴とする請求項１記載の水性印
刷インキ。2. In the vinyl monomer composition of the copolymer, 0 to 4 acrylic acid or methacrylic acid monomers are present.
0% by weight, 40-8% of other copolymerizable vinyl monomers
The water-based printing ink according to claim 1, characterized in that the content is 0% by weight.
もしくはアンモニアで少なくとも一部中和し、水に溶解
もしくは分散されていることを特徴とする請求項１記載
の水性印刷インキ。3. The aqueous printing ink according to claim 1, wherein the carboxyl group of the copolymer is at least partially neutralized with amine or ammonia and dissolved or dispersed in water.
０．１重量％〜１０重量％であることを特徴とする請求
項１記載の水性印刷インキ。[Claim 4] The amount of the organometallic chelate compound added is
The water-based printing ink according to claim 1, characterized in that the content is 0.1% to 10% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3136002A JPH04335070A (en) | 1991-05-10 | 1991-05-10 | Water-base printing ink |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3136002A JPH04335070A (en) | 1991-05-10 | 1991-05-10 | Water-base printing ink |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04335070A true JPH04335070A (en) | 1992-11-24 |
Family
ID=15164898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3136002A Pending JPH04335070A (en) | 1991-05-10 | 1991-05-10 | Water-base printing ink |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04335070A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7063895B2 (en) | 2001-08-01 | 2006-06-20 | National Starch And Chemical Investment Holding Corporation | Hydrophobically modified solution polymers and their use in surface protecting formulations |
| WO2018181058A1 (en) | 2017-03-31 | 2018-10-04 | 富士フイルム株式会社 | Aqueous ink composition, ink set, image forming method, and resin fine particles for inks |
| US10457823B2 (en) | 2015-03-31 | 2019-10-29 | Fujifilm Corporation | Aqueous ink composition, ink set, image forming method, and resin microparticles |
-
1991
- 1991-05-10 JP JP3136002A patent/JPH04335070A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7063895B2 (en) | 2001-08-01 | 2006-06-20 | National Starch And Chemical Investment Holding Corporation | Hydrophobically modified solution polymers and their use in surface protecting formulations |
| US10457823B2 (en) | 2015-03-31 | 2019-10-29 | Fujifilm Corporation | Aqueous ink composition, ink set, image forming method, and resin microparticles |
| WO2018181058A1 (en) | 2017-03-31 | 2018-10-04 | 富士フイルム株式会社 | Aqueous ink composition, ink set, image forming method, and resin fine particles for inks |
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