JP7392195B1 - Liquid printing ink and laminates - Google Patents
Liquid printing ink and laminates Download PDFInfo
- Publication number
- JP7392195B1 JP7392195B1 JP2023171947A JP2023171947A JP7392195B1 JP 7392195 B1 JP7392195 B1 JP 7392195B1 JP 2023171947 A JP2023171947 A JP 2023171947A JP 2023171947 A JP2023171947 A JP 2023171947A JP 7392195 B1 JP7392195 B1 JP 7392195B1
- Authority
- JP
- Japan
- Prior art keywords
- resin
- ink
- printing ink
- liquid printing
- present
- 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.)
- Active
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- 238000007639 printing Methods 0.000 title claims abstract description 89
- 239000007788 liquid Substances 0.000 title claims abstract description 55
- 229920005989 resin Polymers 0.000 claims abstract description 80
- 239000011347 resin Substances 0.000 claims abstract description 80
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011354 acetal resin Substances 0.000 claims abstract description 7
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 7
- 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 25
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 25
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 25
- 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 24
- 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 24
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000007646 gravure printing Methods 0.000 claims description 9
- 230000009477 glass transition Effects 0.000 claims description 5
- 150000001241 acetals Chemical class 0.000 claims 1
- 238000011160 research Methods 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 107
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 45
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 42
- 239000000123 paper Substances 0.000 description 29
- 239000002904 solvent Substances 0.000 description 29
- 239000000049 pigment Substances 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 21
- 229910052709 silver Inorganic materials 0.000 description 21
- 239000004332 silver Substances 0.000 description 21
- 229910052782 aluminium Inorganic materials 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 17
- 239000002585 base Substances 0.000 description 17
- 238000007865 diluting Methods 0.000 description 17
- 239000010410 layer Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- -1 paraformaldehyde) Chemical compound 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
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- 239000007787 solid Substances 0.000 description 9
- 229920000742 Cotton Polymers 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000002987 primer (paints) Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000020 Nitrocellulose Substances 0.000 description 6
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- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 6
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- 238000013461 design Methods 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
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- 239000004698 Polyethylene Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
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- 229920000573 polyethylene Polymers 0.000 description 4
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- 238000007740 vapor deposition Methods 0.000 description 4
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- 239000001431 2-methylbenzaldehyde Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 238000006359 acetalization reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000012860 organic pigment Substances 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
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 3
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Landscapes
- Printing Methods (AREA)
- Laminated Bodies (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Paints Or Removers (AREA)
Abstract
【課題】本発明が解決しようとする課題は、本発明のリキッド印刷インキと高輝性インキを重ね刷りした積層体を形成する事で、基材との密着性、輝度感、及び印刷部分の隠蔽性を兼備するリキッド印刷インキを提供することを目的とする。【解決手段】本発明者等は、上記の課題を解決すべく鋭意研究した結果、本発明解決手段はバインダー樹脂、及び有機溶剤を含有するリキッド印刷インキであって、前記バインダー樹脂がポリビニルアセタール樹脂であることを特徴とするリキッド印刷インキに関するものである。【選択図】なし[Problem] The problem to be solved by the present invention is to form a laminate in which the liquid printing ink of the present invention and a high brightness ink are overprinted to improve adhesion to the base material, brightness, and concealment of the printed part. The purpose of the present invention is to provide a liquid printing ink that has both properties. [Solution] As a result of intensive research in order to solve the above problems, the present inventors have found that the solution of the present invention is a liquid printing ink containing a binder resin and an organic solvent, wherein the binder resin is polyvinyl acetal resin. This invention relates to a liquid printing ink characterized by: [Selection diagram] None
Description
本発明は、フレキソ印刷又はグラビア印刷に使用可能な、金インキ、銀インキ等の特殊顔料を含む反射性金属インキ印刷向けアンカーニス(プライマー)して有用なリキッド印刷インキに関する。 The present invention relates to a liquid printing ink useful as an anchor varnish (primer) for reflective metal ink printing containing special pigments such as gold ink and silver ink, which can be used in flexographic printing or gravure printing.
従来より、主に紙基材からなる各種パッケージ等包装材料向け積層体を対象に、より高意匠性を付与すべく、印刷デザイン、印刷絵柄に金インキ、銀インキ、パールインキ等の特殊顔料を含む光輝性インキを用いた高意匠性化の工夫がなされている。金属光沢を模した印刷物は、基材にアルミ貼合紙や金属蒸着紙を使用したり、仕上がった印刷物に対して後加工により金属箔を箔押しする事で、意匠感を付与しているのが一般的な手法である。
しかし、これらの手法はコスト高であり、生産性も低く、経済的ではない。
一方で、通常のフレキソ印刷やグラビア印刷により金色や銀色を表現するために、アルミペーストやブロンズパウダーを配合したインキを使用する事も可能であるが、前記したアルミ貼合紙や金属蒸着紙を基材に印刷した印刷物や、後加工で金属箔を箔押ししたものと比較すると、輝度感や印刷部分の隠蔽性が劣るがために十分な金属外観が得られず、高意匠性が得られる手法しては決して十分なものではなかった。
Traditionally, special pigments such as gold ink, silver ink, pearl ink, etc. have been applied to printing designs and patterns in order to give higher design quality to laminates for packaging materials such as various packages mainly made of paper base material. Efforts have been made to improve the design quality by using glittering ink containing. Prints that imitate metallic luster are given a sense of design by using aluminum laminated paper or metallized paper as the base material, or by stamping metal foil on the finished prints in post-processing. This is a common method.
However, these methods are expensive, have low productivity, and are not economical.
On the other hand, it is also possible to use ink containing aluminum paste or bronze powder to express gold or silver colors with regular flexographic printing or gravure printing, but it is also possible to use ink containing aluminum paste or bronze powder, but it is also possible to use ink containing aluminum paste or bronze powder. Compared to printed matter printed on a base material or stamped with metal foil in post-processing, this method does not provide a sufficient metallic appearance due to inferior brightness and concealment of the printed area, but is a method that provides a high level of design. It was never enough.
紙および板紙用のプライマーコーティングの一例として、特定の官能基を持つアクリルモノマーとアクリルオリゴマーを特定比率で用いたプライマー組成物が開示されているが、UV照射装置が必須であり、熱風乾燥が主流のグラビア印刷では汎用性が低い(例えば、特許文献1:特開2019-94506)。 As an example of primer coating for paper and paperboard, a primer composition using acrylic monomers and acrylic oligomers with specific functional groups in a specific ratio has been disclosed, but a UV irradiation device is essential and hot air drying is mainstream. Gravure printing has low versatility (for example, Patent Document 1: JP 2019-94506).
本発明が解決しようとする課題は、本発明のリキッド印刷インキと高輝性インキを重ね刷りした積層体を形成する事で、基材との密着性、輝度感、及び印刷部分の隠蔽性を兼備するリキッド印刷インキを提供することを目的とする。 The problem to be solved by the present invention is to form a laminate by overprinting the liquid printing ink of the present invention and a high brightness ink, thereby achieving both adhesion to the base material, brightness, and concealment of the printed area. The purpose is to provide a liquid printing ink that
本発明者等は、上記の課題を解決すべく鋭意研究した結果、バインダー樹脂、及び有機溶剤を含有するリキッド印刷インキであって、前記バインダー樹脂がポリビニルアセタール樹脂であることを特徴とするリキッド印刷インキを用いることで、前記課題を解決できることを見出し、本発明を完成させた。 As a result of intensive research to solve the above problems, the present inventors have discovered a liquid printing ink containing a binder resin and an organic solvent, wherein the binder resin is a polyvinyl acetal resin. The inventors have discovered that the above problems can be solved by using ink, and have completed the present invention.
即ち、本発明は、バインダー樹脂、及び有機溶剤を含有するリキッド印刷インキであって、前記バインダー樹脂がポリビニルアセタール樹脂であることを特徴とするリキッド印刷インキに関する。 That is, the present invention relates to a liquid printing ink containing a binder resin and an organic solvent, wherein the binder resin is a polyvinyl acetal resin.
また、本発明は、前記ポリビニルアセタール樹脂がポリビニルブチラール樹脂であって、ガラス転移温度が60℃~75℃であり、前記樹脂中のポリビニルアルコール成分が全樹脂中の10質量%~30質量%であるリキッド印刷インキに関する。 Further, in the present invention, the polyvinyl acetal resin is a polyvinyl butyral resin, the glass transition temperature is 60°C to 75°C, and the polyvinyl alcohol component in the resin is 10% to 30% by mass based on the total resin. Regarding a certain liquid printing ink.
また、本発明は、更にロジン系樹脂を含有するリキッド印刷インキに関する。 The present invention also relates to a liquid printing ink further containing a rosin resin.
また、本発明は、フレキソ印刷またはグラビア印刷に適用するリキッド印刷インキに関する。 The present invention also relates to a liquid printing ink applied to flexographic printing or gravure printing.
また、本発明は、紙基材に少なくとも第一の印刷層と第二の印刷層とをこの順に有する積層体であって、前記第一の印刷層が、リキッド印刷インキの印刷層であり、前記第二の印刷層が、反射性金属インキの印刷層であることを特徴とする積層体に関する。 Further, the present invention provides a laminate having at least a first printed layer and a second printed layer in this order on a paper base material, the first printed layer being a printed layer of liquid printing ink, The present invention relates to a laminate, wherein the second printed layer is a printed layer of reflective metallic ink.
本発明のリキッド印刷インキは、反射性金属インキを重ね刷りした積層体を形成する事で、基材との密着性、輝度感、及び印刷部分の隠蔽性を兼備することが出来る。 The liquid printing ink of the present invention can have adhesion to the base material, brightness, and concealment of the printed part by forming a laminate in which reflective metal ink is overprinted.
本発明のリキッド印刷インキは、バインダー樹脂、及び有機溶剤を含有するリキッド印刷インキであって、前記バインダー樹脂がポリビニルアセタール樹脂であることを必須とするものである。 The liquid printing ink of the present invention is a liquid printing ink containing a binder resin and an organic solvent, and the binder resin is essentially a polyvinyl acetal resin.
前記ポリビニルアセタール樹脂としては、ポリビニルブチラール樹脂、ポリビニルアセトアセタール樹脂等が挙げられる。
前記ポリビニルブチラール樹脂は、ポリビニルアルコールを塩酸等の酸存在下、アルデヒドでアセタール化して得られる公知のものでよい。
中でも、ポリビニルブチラール樹脂が好ましく、ポリビニルアルコールを塩酸等の酸存在下、ブチルアルコールにてブチラール化する事で得られる。
前記ポリビニルアルコール樹脂としては特に限定されず、ポリ酢酸ビニルをアルカリ、酸、アンモニア水等でけん化することにより製造されたもの等の従来公知のポリビニルアルコール樹脂を用いることができる。
上記ポリビニルアルコール樹脂としては、完全けん化されたものであってもよいが、少な
くとも主鎖の一カ所にメソ、ラセミ位に対して二連の水酸基を有するユニットが最低1 ユニットあれば完全けん化されている必要はなく、部分けん化ポリビニルアルコール樹脂であってもよい。
また、上記ポリビニルアルコール樹脂としては、エチレン- ビニルアルコール共重合体樹脂、部分けん化エチレン- ビニルアルコール共重合体樹脂等の、ビニルアルコールと、ビニルアルコールと共重合可能なモノマーとの共重合体も用いることができる。更に、一部にカルボン酸等が導入された、変性ポリビニルアルコール樹脂も用いることができる。
上記アセタール化の方法としては特に限定されず、例えば、上記ポリビニルアルコール樹脂の水溶液にアルデヒド及び酸触媒を添加し、公知の方法でアセタール化を行う方法等が挙げられる。上記アルデヒドとしては特に限定されず、例えば、ホルムアルデヒド( パラホルムアルデヒドを含む) 、アセトアルデヒド( パラアセトアルデヒドを含む) 、プロピオンアルデヒド、ブチルアルデヒド、アミルアルデヒド、ヘキシルアルデヒド、ヘプチルアルデヒド、2 - エチルヘキシルアルデヒド、シクロヘキシルアルデヒド、フルフラール、グリオキザール、グルタルアルデヒド、ベンズアルデヒド、2 - メチルベンズアルデヒド、3 - メチルベンズアルデヒド、4 - メチルベンズアルデヒド、p - ヒドロキシベンズアルデヒド、m - ヒドロキシベンズアルデヒド、フェニルアセトアルデヒド、β - フェニルプロピオンアルデヒド等が挙げられる。これらのアルデヒドは、単独で用いられてもよく、2 種類以上を併用してもよい。これらのなかでは、ブチルアルデヒド及び/ 又はアセトアルデヒドを用いることが好ましい。
上記酸触媒としては特に限定されず、例えば、酢酸、p - トルエンスルホン酸等の有機酸類、硝酸、硫酸、塩酸等の無機酸類等が挙げられる。また、上記アセタール化反応の停止剤としては特に限定されず、例えば、水酸化ナトリウム、水酸化カリウム、アンモニア、酢酸ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム等のアルカリ中和剤; エチレンオキサイド等のアルキレンオキサイド類; エチレングリコールジグリシジルエーテル等のグリシジルエーテル類が挙げられる。
Examples of the polyvinyl acetal resin include polyvinyl butyral resin, polyvinyl acetoacetal resin, and the like.
The polyvinyl butyral resin may be a known resin obtained by acetalizing polyvinyl alcohol with an aldehyde in the presence of an acid such as hydrochloric acid.
Among these, polyvinyl butyral resin is preferred, and can be obtained by butyralizing polyvinyl alcohol with butyl alcohol in the presence of an acid such as hydrochloric acid.
The polyvinyl alcohol resin is not particularly limited, and conventionally known polyvinyl alcohol resins such as those produced by saponifying polyvinyl acetate with alkali, acid, aqueous ammonia, etc. can be used.
The above-mentioned polyvinyl alcohol resin may be completely saponified, but it is completely saponified if it has at least one unit having a double hydroxyl group in the meso or racemic position at least at one location in the main chain. It is not necessary to use a partially saponified polyvinyl alcohol resin.
Furthermore, as the polyvinyl alcohol resin, a copolymer of vinyl alcohol and a monomer copolymerizable with vinyl alcohol, such as an ethylene-vinyl alcohol copolymer resin or a partially saponified ethylene-vinyl alcohol copolymer resin, may also be used. be able to. Furthermore, a modified polyvinyl alcohol resin into which a carboxylic acid or the like is introduced can also be used.
The method of acetalization is not particularly limited, and includes, for example, a method of adding an aldehyde and an acid catalyst to an aqueous solution of the polyvinyl alcohol resin and performing acetalization using a known method. The above aldehydes are not particularly limited, and include, for example, formaldehyde (including paraformaldehyde), acetaldehyde (including paraacetaldehyde), propionaldehyde, butyraldehyde, amylaldehyde, hexylaldehyde, heptylaldehyde, 2-ethylhexylaldehyde, cyclohexylaldehyde, Examples include furfural, glyoxal, glutaraldehyde, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, β-phenylpropionaldehyde, and the like. These aldehydes may be used alone or in combination of two or more. Among these, it is preferable to use butyraldehyde and/or acetaldehyde.
The acid catalyst is not particularly limited, and includes, for example, organic acids such as acetic acid and p-toluenesulfonic acid, and inorganic acids such as nitric acid, sulfuric acid, and hydrochloric acid. In addition, the terminator for the acetalization reaction is not particularly limited, and includes, for example, alkali neutralizing agents such as sodium hydroxide, potassium hydroxide, ammonia, sodium acetate, sodium carbonate, sodium bicarbonate, and potassium carbonate; ethylene oxide, etc. Alkylene oxides include glycidyl ethers such as ethylene glycol diglycidyl ether.
本発明のリキッド印刷インキで使用するポリビニルブチラール樹脂としては、ガラス転移温度(以下Tgと略す場合がある)が60℃~75℃の範囲であるものが好ましく、ガラス転移温度がこの範囲内であれば、反射性金属インキを重ね刷りした積層体を形成した際に、輝度感と印刷部分の隠蔽性を保持することが出来る。
また、前記ポリビニルブチラール樹脂中のポリビニルアルコール成分が全樹脂中の10質量%~30質量%であることが好ましい。
ポリビニルアルコール成分が全樹脂中の10質量%以上であれば、輝度感が保持できる傾向にあり、30質量%以下であれば、密着性が保持できる傾向となる。
尚、バインダー樹脂は固形分換算にてリキッド印刷インキ全量の5~35質量%の範囲である事が好ましい。5質量%以上であれば輝度感が保持できる傾向にあり、35質量%以下であれば、密着性が保持できる傾向となる。
The polyvinyl butyral resin used in the liquid printing ink of the present invention preferably has a glass transition temperature (hereinafter sometimes abbreviated as Tg) in the range of 60°C to 75°C, and even if the glass transition temperature is within this range. For example, when a laminate is formed by overprinting reflective metal ink, it is possible to maintain the brightness and concealability of the printed portion.
Further, it is preferable that the polyvinyl alcohol component in the polyvinyl butyral resin is 10% by mass to 30% by mass based on the total resin.
If the polyvinyl alcohol component is 10% by mass or more based on the total resin, brightness tends to be maintained, and if it is 30% by mass or less, adhesiveness tends to be maintained.
Incidentally, the binder resin preferably ranges from 5 to 35% by mass of the total amount of the liquid printing ink in terms of solid content. If it is 5% by mass or more, brightness tends to be maintained, and if it is 35% by mass or less, adhesion tends to be maintained.
本発明のリキッド印刷インキで使用するバインダー樹脂としては、ケトン樹脂、アルキド樹脂、硝化綿等を併用しても良い。
前記ケトン樹脂としては、公知慣用のものを挙げることができるが、ホルムアルデヒド樹脂、シクロヘキサノン・ホルムアルデヒド樹脂また、ケトンアルデヒド縮合樹脂等を好適に用いることができる。ケトン樹脂としては例えばエボニックジャパン社製のTEGOVariPlus AP、TEGOVariPlus SK、TEGOVariPlus 1201、TEGOVariPlus CA棟が例示できる。
ケトン樹脂の添加量としては、バインダー樹脂固形分全量に対し0.5~30質量%であることが好ましく、よりに好ましくは5~20質量%である。
As the binder resin used in the liquid printing ink of the present invention, ketone resin, alkyd resin, nitrified cotton, etc. may be used in combination.
Examples of the ketone resin include known and commonly used ones, and formaldehyde resins, cyclohexanone formaldehyde resins, ketone aldehyde condensation resins, and the like can be suitably used. Examples of the ketone resin include TEGOVariPlus AP, TEGOVariPlus SK, TEGOVariPlus 1201, and TEGOVariPlus CA manufactured by Evonik Japan.
The amount of ketone resin added is preferably 0.5 to 30% by mass, more preferably 5 to 20% by mass based on the total solid content of the binder resin.
本発明に用いられるアルキッド樹脂は、植物油およびそれらの脂肪酸、多価カルボン酸および多価アルコールを縮合することによって得られる。アルキッド樹脂の性質は変性に使用する油の種類とその含有量によって影響され、樹脂の軟化点及び乾燥性を考慮すれば、樹脂分に対する使用する油脂の比率を示す油長について、油長50~90%が好ましい。油長が50%より長ければ、乾燥が速くなり過ぎる事なく印刷機上での安定性が保たれる。また油長が90%より短ければ植物油としての性質が強くなりにくく、顔料分散効果が保持される傾向となる。
アルキッド樹脂の添加量としては、バインダー樹脂固形分全量に対し0.5~30質量%であることが好ましく、よりに好ましくは5~20質量%である。
The alkyd resin used in the present invention is obtained by condensing vegetable oils, their fatty acids, polyhydric carboxylic acids, and polyhydric alcohols. The properties of alkyd resin are affected by the type and content of oil used for modification, and if the softening point and drying properties of the resin are taken into consideration, the oil length, which indicates the ratio of oil to resin content, can be calculated from 50 to 50. 90% is preferred. If the oil length is longer than 50%, stability on the printing press can be maintained without drying too quickly. Moreover, if the oil length is shorter than 90%, the properties as a vegetable oil will not become strong, and the pigment dispersion effect will tend to be maintained.
The amount of alkyd resin added is preferably 0.5 to 30% by mass, more preferably 5 to 20% by mass based on the total solid content of the binder resin.
本発明に用いられる硝化綿としては、天然セルロースと硝酸とを反応させて、天然セルロース中の無水グルコピラノース基の6員環中の3個の水酸基を、硝酸基に置換した硝酸エステルとして得られるものが好ましい。
硝化綿を使用する事で、顔料への高い分散性が得られる事から、印刷インキ塗膜の強度を向上させることができ好適である。前記硝化綿としては、窒素含有量が10~13質量%、平均重合度30~500が好ましく、より好ましくは窒素含有量が10~13質量%、平均重合度45~290である。
硝化綿の添加量としては、バインダー樹脂固形分全量に対し0.5~30質量%であることが好ましく、よりに好ましくは5~20質量%である。
The nitrified cotton used in the present invention is obtained as a nitric acid ester in which three hydroxyl groups in the six-membered ring of the anhydrous glucopyranose group in natural cellulose are replaced with nitric acid groups by reacting natural cellulose with nitric acid. Preferably.
By using nitrified cotton, high dispersibility in the pigment can be obtained, and therefore the strength of the printing ink coating can be improved, which is preferable. The nitrified cotton preferably has a nitrogen content of 10 to 13% by mass and an average degree of polymerization of 30 to 500, more preferably a nitrogen content of 10 to 13% by mass and an average degree of polymerization of 45 to 290.
The amount of nitrified cotton added is preferably 0.5 to 30% by mass, more preferably 5 to 20% by mass based on the total solid content of the binder resin.
本発明のリキッド印刷インキには、基材への密着性の向上目的にバインダー樹脂としてロジン系樹脂を含有する事がより好ましい。前記ロジン系樹脂としては、ロジン、水添ロジン、酸変性ロジン、エステルロジンが挙げられる。
前記ロジンとしては、アビエチン酸、レボピマール酸、パルストリン酸、ネオアビエチン酸、デヒドロアビエチン酸、或いはジヒドロアビエチン酸など樹脂酸を主成分とするトール油ロジン、ガムロジン、ウッドロジンなどの未変性ロジンが挙げられる。
前記未変性ロジンを各々水素化したものが水添ロジンとして使用できる。
前記、酸変性ロジンとしては、ディールズ・アルダー付加反応によりロジンにフマル酸を付加したフマロピマール酸、マレイン酸を付加したマレオピマール酸等が挙げられる。
前記、酸性変性ロジンの中でも、マレイン酸ロジンが特に好ましい。
前記エステル化ロジンとしては、ロジンとグリセリンをエステル化反応させて得られるグリセリンエステルや、ペンタエリスリトールとエステル化して得られるペンタエリスリトールエステルを挙げる事ができる。
It is more preferable that the liquid printing ink of the present invention contains a rosin resin as a binder resin for the purpose of improving adhesion to the substrate. Examples of the rosin resin include rosin, hydrogenated rosin, acid-modified rosin, and ester rosin.
Examples of the rosin include unmodified rosin, such as tall oil rosin, gum rosin, and wood rosin, which are mainly composed of resin acids such as abietic acid, levopimaric acid, palustric acid, neoabietic acid, dehydroabietic acid, or dihydroabietic acid.
Each of the unmodified rosins described above can be hydrogenated and used as the hydrogenated rosin.
Examples of the acid-modified rosin include fumaropimaric acid obtained by adding fumaric acid to rosin by Diels-Alder addition reaction, maleopimaric acid obtained by adding maleic acid, and the like.
Among the aforementioned acidic modified rosins, maleic acid rosin is particularly preferred.
Examples of the esterified rosin include glycerin ester obtained by esterifying rosin and glycerin, and pentaerythritol ester obtained by esterifying pentaerythritol.
前記ロジン系樹脂としては、酸価150~250mgKOH/gが好ましい。ロジン系樹脂の酸価が150mgKOH/g以上であれば重ね刷り適性が低下する傾向が抑制でき、250mgKOH/g以下であれば溶剤に対する溶解性が低下する事なく、インキの貯蔵安定性も保持しやすい傾向となる。また、ロジン系樹脂の軟化点は、100~170℃が好ましい。ロジン系樹脂の軟化点が100℃以上であれば、インキ塗膜が柔らかくなりブロッキング性が低下する傾向が抑制でき、軟化点が170℃以下であれば、有機溶剤に対する溶解性が低下する傾向を回避でき、インキの貯蔵安定性も保持される傾向となる。
ロジン系樹脂の添加量としては、バインダー樹脂固形分全量に対し0.5~30質量%であることが好ましく、よりに好ましくは3~25質量%であり、5~20質量%の範囲であれば更に好ましい。
The rosin resin preferably has an acid value of 150 to 250 mgKOH/g. If the acid value of the rosin resin is 150 mgKOH/g or more, the tendency for overprinting suitability to decrease can be suppressed, and if it is 250 mgKOH/g or less, the solubility in solvents will not decrease and the storage stability of the ink will be maintained. It tends to be easy. Further, the softening point of the rosin resin is preferably 100 to 170°C. If the softening point of the rosin resin is 100°C or higher, the tendency for the ink coating to become soft and the blocking property to decrease can be suppressed, and if the softening point is 170°C or lower, the tendency for the solubility in organic solvents to decrease can be suppressed. This can be avoided and the storage stability of the ink tends to be maintained.
The amount of rosin resin added is preferably 0.5 to 30% by mass, more preferably 3 to 25% by mass, and even within the range of 5 to 20% by mass based on the total solid content of the binder resin. It is even more preferable.
本発明のリキッド印刷インキに使用する有機溶剤としては、特に制限はないが、たとえばトルエン、キシレン、ソルベッソ#100、ソルベッソ#150等の芳香族炭化水素系、ヘキサン、メチルシクロヘキサン、ヘプタン、オクタン、デカン等の脂肪族炭化水素系、酢酸メチル、酢酸エチル、酢酸イソプロピル、酢酸ノルマルプロピル、酢酸ブチル、酢酸アミル、ギ酸エチル、プロピオン酸ブチル等のエステル系の各種有機溶剤が挙げられる。また水混和性有機溶剤としてメタノール、エタノール、プロパノール、ブタノール、イソプロピルアルコール等のアルコール系、アセトン、メチルエチルケトン、シクロハキサノン等のケトン系、エチレングリコール(モノ,ジ)メチルエーテル、エチレングリコール(モノ,ジ)エチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノイソプロピルエーテル、モノブチルエーテル、ジエチレングリコール(モノ,ジ)メチルエーテル、ジエチレングリコール(モノ,ジ)エチルエーテル、ジエチレングリコールモノイソプロピルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコール(モノ,ジ)メチルエーテル、プロピレングリコール(モノ,ジ)メチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコール(モノ,ジ)メチルエーテル等のグリコールエーテル系の各種有機溶剤が挙げられる。これらを単独または2種以上を混合して用いることができる。
尚、印刷時の作業衛生性と包装材料の有害性の両面から、トルエン、キシレン等の芳香族炭化水素系溶剤を使用しない事がより好ましい。
The organic solvent used in the liquid printing ink of the present invention is not particularly limited, but includes aromatic hydrocarbons such as toluene, xylene, Solvesso #100 and Solvesso #150, hexane, methylcyclohexane, heptane, octane, and decane. and ester-based organic solvents such as methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, amyl acetate, ethyl formate, and butyl propionate. In addition, water-miscible organic solvents include alcohols such as methanol, ethanol, propanol, butanol, and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, and cyclohaxanone, ethylene glycol (mono, di) methyl ether, and ethylene glycol (mono, di) ethyl. Ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycol (mono, di) methyl ether, diethylene glycol (mono, di) ethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol (mono, di) Examples include various glycol ether-based organic solvents such as di)methyl ether, propylene glycol (mono,di)methyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol (mono,di)methyl ether. These can be used alone or in combination of two or more.
In addition, from the viewpoint of both operational hygiene during printing and toxicity of packaging materials, it is more preferable not to use aromatic hydrocarbon solvents such as toluene and xylene.
本発明の本発明のリキッド印刷インキは、主に金インキ、銀インキ等の特殊顔料を含む反射性金属インキ印刷向けアンカーニス(プライマー)として有用である事から、原則着色剤を併用する事は少ないが、必要に応じて輝度感や印刷部の隠蔽性が著しく低下しない範囲で一般のインキ、塗料、及び記録剤などに使用されている有機顔料及び/または無機顔料を添加してもよい。 The liquid printing ink of the present invention is mainly useful as an anchor varnish (primer) for printing with reflective metal inks containing special pigments such as gold ink and silver ink, so in principle, colorants should not be used together. Although the amount is small, organic pigments and/or inorganic pigments used in general inks, paints, recording agents, etc. may be added as necessary to the extent that the brightness and hiding properties of printed areas are not significantly reduced.
本発明のリキッド印刷インキに使用される着色顔料としては、まずは有機顔料や染料を挙げることができる。有機顔料としては、アゾ系、フタロシアニン系、アントラキノン系、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、アゾメチンアゾ系、ジクトピロロピロール系、イソインドリン系などの顔料が挙げられる。 The colored pigments used in the liquid printing ink of the present invention include organic pigments and dyes. Examples of organic pigments include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, dictopyrrolopyrrole, and isoindoline. Examples include pigments.
代表的なカラーインデックス名としては、
C.I.Pigment Yellow 1、3、12、13、14、17、42、74、83;
C.I.Pigment Orange 16;
C.I.Pigment Red 5、22、38、48:1、48:2、48:4、49:1、53:1、57:1、63:1、81、101;
C.I.Pigment Violet 19、23;
C.I.Pigment Blue 23、15:1、15:3、15:4、17:1、18、27、29
C.I.Pigment Green 7、36、58、59;
C.I.Pigment Black 7;
C.I.Pigment White 4、6、18などが挙げられる。
Typical color index names include:
C. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 42, 74, 83;
C. I. Pigment Orange 16;
C. I. Pigment Red 5, 22, 38, 48:1, 48:2, 48:4, 49:1, 53:1, 57:1, 63:1, 81, 101;
C. I. Pigment Violet 19, 23;
C. I. Pigment Blue 23, 15:1, 15:3, 15:4, 17:1, 18, 27, 29
C. I. Pigment Green 7, 36, 58, 59;
C. I. Pigment Black 7;
C. I. Pigment White 4, 6, 18 and the like.
藍インキにはC.I.Pigment Blue 15:3(銅フタロシアニン)、黄インキにはコスト・耐光性の点からC.I.Pigment Yellow83、紅インキにはC.I.Pigment Red 57:1、墨インキにはカーボンブラックを用いることが好ましい。 C. for indigo ink. I. Pigment Blue 15:3 (copper phthalocyanine), yellow ink is C. I. Pigment Yellow 83, C. I. Pigment Red 57:1 and carbon black are preferably used for the black ink.
無機顔料としては、酸化チタン、酸化亜鉛、硫化亜鉛、硫酸バリウム、炭酸カルシウム、酸化クロム、シリカ、リトボン、アンチモンホワイト、石膏などの白色無機顔料が挙げられる。無機顔料の中では酸化チタンの使用が特に好ましい。酸化チタンは白色を呈し、着色力、隠ぺい力、耐薬品性、耐候性の点から好ましく、印刷性能の観点から該酸化チタンはシリカおよび/またはアルミナ処理を施されているものが好ましい。 Examples of the inorganic pigment include white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, lithobon, antimony white, and gypsum. Among the inorganic pigments, use of titanium oxide is particularly preferred. Titanium oxide is white and is preferred from the viewpoint of coloring power, hiding power, chemical resistance, and weather resistance. From the viewpoint of printing performance, the titanium oxide is preferably treated with silica and/or alumina.
前記反射性金属インキの金、銀インキには蒸着アルミニウム顔料と必要に応じて前記着色顔料を混合することが好ましい。蒸着アルミニウム顔料(蒸着法により製造されたアルミニウム顔料)は、蒸着法により製造されたアルミニウムフレークである。上記蒸着法とは、適宜な支持基材(フィルムなど)上に金属(本発明ではアルミニウム)を蒸着して蒸着金属(アルミニウム)膜を作製した後、これを剥離、粉砕、必要に応じて、分級してフレーク状とする蒸着金属膜細片(蒸着アルミニウムフレーク)の製造方法である。上記の蒸着法によれば、従来のボールミルによる粉砕(「ボールミル法」又は「湿式ボールミル法」と称する場合がある)などにより製造する場合と比べ、板状で厚みのより薄いアルミニウムフレークを得ることができる。このため、印刷層中において、顔料であるアルミニウムフレークが紙基材と平行方向に配向しやすく配向性が向上し、入射光を正反射しやすくなる。このため、印刷層の鏡面光沢度及び透過濃度が向上し、優れた金属光沢を示す。 It is preferable that the gold or silver ink of the reflective metal ink contains a vapor-deposited aluminum pigment and, if necessary, the coloring pigment. Vapor-deposited aluminum pigments (aluminum pigments produced by vapor deposition) are aluminum flakes produced by vapor deposition. The above-mentioned vapor deposition method is to create a vapor-deposited metal (aluminum) film by vapor-depositing a metal (aluminum in the present invention) on a suitable supporting substrate (film, etc.), then peeling it off, pulverizing it, and, if necessary, This is a method for producing vapor-deposited metal film strips (vapor-deposited aluminum flakes) that are classified into flakes. According to the above vapor deposition method, it is possible to obtain aluminum flakes that are plate-shaped and thinner than those produced by conventional pulverization using a ball mill (sometimes referred to as the "ball mill method" or "wet ball mill method"). I can do it. Therefore, in the printing layer, the aluminum flakes that are pigments are easily oriented in a direction parallel to the paper base material, and the orientation is improved, making it easier to regularly reflect incident light. Therefore, the specular gloss and transmission density of the printed layer are improved, and excellent metallic luster is exhibited.
前記蒸着アルミニウム顔料の平均粒子径は5~40μmの範囲にあるものが好ましく、より好ましくは8~20μmである。前記顔料は、油性リキッド印刷インキの濃度・着色力を確保するのに充分な量、すなわちインキの総質量に対して1~60質量%、インキ中の固形分質量比では5~90質量%の割合で含まれることが好ましい。また、これらの顔料は単独で、または2種以上を併用して用いることができる。 The average particle size of the vapor-deposited aluminum pigment is preferably in the range of 5 to 40 μm, more preferably 8 to 20 μm. The pigment is used in an amount sufficient to ensure the concentration and coloring power of the oil-based liquid printing ink, that is, 1 to 60% by mass based on the total mass of the ink, and 5 to 90% by mass in terms of solid content in the ink. It is preferable that it is contained in a proportion. Further, these pigments can be used alone or in combination of two or more.
本発明においては、その他、体質顔料、顔料分散剤、レベリング剤、消泡剤、可塑剤、赤外線吸収剤、紫外線吸収剤、芳香剤、難燃剤なども含むこともできる。中でも耐摩擦性、滑り性等を付与するための高密度重合型ポリエチレン、低密度重合型ポリエチレン、酸化型ポリエチレン等のポリオレフィン類及び印刷時の発泡を抑制するためのシリコン系、非シリコン系消泡剤及び顔料の濡れを向上させる各種分散剤等が有用である。 In the present invention, extender pigments, pigment dispersants, leveling agents, antifoaming agents, plasticizers, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants, and the like may also be included. Among them, polyolefins such as high-density polymerized polyethylene, low-density polymerized polyethylene, and oxidized polyethylene to provide friction resistance and slipperiness, and silicone-based and non-silicon-based antifoaming to suppress foaming during printing. Various dispersants and the like that improve wetting of agents and pigments are useful.
(リキッド印刷インキの製造方法)
本発明のリキッド印刷インキは、バインダー樹脂、有機溶剤、その他の添加剤の混合物を分散機で分散し、撹拌混合することで得られる。分散機としてはグラビア、フレキソ印刷インキの製造に一般的に使用されているビーズミル、アイガーミル、サンドミル、ガンマミル、アトライター等を用いて製造される。
(Method for manufacturing liquid printing ink)
The liquid printing ink of the present invention can be obtained by dispersing a mixture of a binder resin, an organic solvent, and other additives using a dispersing machine, and stirring and mixing the mixture. As a dispersing machine, a bead mill, an Eiger mill, a sand mill, a gamma mill, an attritor, etc., which are commonly used in the production of gravure and flexo printing inks, are used.
(印刷物の作成)
本発明のリキッド印刷インキは、各種の基材と密着性に優れ、紙、合成紙、熱可塑性樹脂フィルム、プラスチック製品、鋼板等への印刷に使用することができるものであり、電子彫刻凹版等によるグラビア印刷版を用いたグラビア印刷用、又は樹脂版等によるフレキソ印刷版を用いたフレキソ印刷用のインキとして有用である一方で、版を使用せずインクジェットノズルからインキを吐出するインクジェット方式向けのインキを除くものである。即ち、インクジェットインキの場合、ノズルから吐出したインク滴が、直接基材に密着し印刷物を形成するのに対し、本発明の水性リキッドインキは、印刷インキを一旦印刷版又は印刷パターンに密着・転写した後、インキのみを再度基材に密着させ、必要に応じて乾燥させ印刷物とするものである。
本発明のリキッド印刷インキを用いてグラビア印刷方式やフレキソ印刷方式から形成される印刷インキの膜厚は、例えば10μm以下、好ましくは5μm以下である。
(Creation of printed matter)
The liquid printing ink of the present invention has excellent adhesion to various base materials and can be used for printing on paper, synthetic paper, thermoplastic resin film, plastic products, steel plates, etc., and can be used for printing on electronic engraving intaglio etc. While it is useful as an ink for gravure printing using a gravure printing plate made by a company, or for flexo printing using a flexo printing plate made of a resin plate, etc., it is also useful as an ink for an inkjet method in which ink is ejected from an inkjet nozzle without using a plate. This excludes ink. That is, in the case of inkjet ink, ink droplets ejected from a nozzle directly adhere to the base material and form printed matter, whereas with the water-based liquid ink of the present invention, the printing ink is once adhered to and transferred to the printing plate or printing pattern. After that, only the ink is brought into close contact with the base material again and, if necessary, dried to form a printed matter.
The film thickness of the printing ink formed by the gravure printing method or the flexographic printing method using the liquid printing ink of the present invention is, for example, 10 μm or less, preferably 5 μm or less.
本発明のリキッド印刷インキを用いれば、例えば紙基材に少なくとも第一の印刷層と第二の印刷層とをこの順に有する積層体であって、前記第一の印刷層が、該リキッド印刷インキの印刷層であり、前記第二の印刷層が、例えば銀インキ等の反射性金属インキの印刷層からなる積層体を作成する事ができる。また、必要に応じて前記第二の印刷層上にオーバープリントニスを有してもよい。
具体的には、例えば印刷用紙としてコート紙に、版深175L/inchグラビア版を備えたグラビア印刷機を用いて、本発明のリキッド印刷インキ、高輝度性インキとして銀インキの順で印刷し、積層体を得る事ができる。また、前記積層体に油性、水性のオーバープリントニスを印刷してもよい。
If the liquid printing ink of the present invention is used, for example, a laminate having at least a first printing layer and a second printing layer in this order on a paper base material, the first printing layer is a layer in which the liquid printing ink is used. It is possible to create a laminate in which the second printing layer is a printing layer of reflective metal ink such as silver ink. Further, an overprint varnish may be provided on the second printing layer as necessary.
Specifically, for example, on coated paper as printing paper, using a gravure printing machine equipped with a gravure plate with a plate depth of 175 L/inch, print the liquid printing ink of the present invention and silver ink as high brightness ink in that order, A laminate can be obtained. Furthermore, an oil-based or water-based overprint varnish may be printed on the laminate.
紙基材のような多孔質および非平滑基材に塗布された反射性金属インキは、多孔質基材に浸透して染み込み、基材の非平滑表面輪郭に続く非平滑層において乾燥し、結果として、反射性の低い低輝度の印刷外観をもたらす。本発明のリキッドインキをプライマーとして使用すれば、高輝度性インキの浸透を防止するとともに、蒸着アルミニウム顔料の配向性を制御し、輝度向上を助けるために推奨される。 Reflective metallic inks applied to porous and non-smooth substrates, such as paper substrates, penetrate and soak into the porous substrate and dry in a non-smooth layer that follows the non-smooth surface contours of the substrate, resulting in , resulting in a low-intensity print appearance with low reflectivity. Use of the liquid ink of the present invention as a primer is recommended to prevent penetration of high-brightness inks, control the orientation of vapor-deposited aluminum pigments, and help improve brightness.
本発明のリキッド印刷インキを印刷する印刷基材としては主に、例えばタバコ包装、菓子類、化粧品や飲料、医薬品、おもちゃ、電子部品等のパッケージ印刷に用いられる上質紙、コート紙、アート紙、模造紙、薄紙、厚紙等の紙、各種合成紙等、紙基材が好ましいが、ポリエステル樹脂、アクリル樹脂、塩化ビニル樹脂、塩化ビニリデン樹脂、ポリビニルアルコール、ポリエチレン、ポリプロピレン、ポリアクリロニトリル、エチレン酢酸ビニル共重合体、エチレンビニルアルコール共重合体、エチレンメタクリル酸共重合体、ナイロン、ポリ乳酸、ポリカーボネート等のフィルム又はシート、セロファン、アルミニウムフォイル、その他従来から印刷基材として使用される基材を用いて積層体を作製することが出来る。 Printing substrates on which the liquid printing ink of the present invention is printed include, for example, high-quality paper, coated paper, art paper, used for printing packages for cigarette packaging, confectionery, cosmetics, beverages, pharmaceuticals, toys, electronic parts, etc. Paper base materials such as imitation paper, thin paper, cardboard, various synthetic papers, etc. are preferred, but polyester resins, acrylic resins, vinyl chloride resins, vinylidene chloride resins, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, and ethylene vinyl acetate are also preferred. Laminated using films or sheets of polymers, ethylene vinyl alcohol copolymers, ethylene methacrylic acid copolymers, nylon, polylactic acid, polycarbonate, etc., cellophane, aluminum foil, and other base materials conventionally used as printing base materials. It is possible to create a body.
以下実施例により、本発明をより詳しく説明する。尚、実施例中の「部」は「質量部」を、「%」は「質量%」をそれぞれ表す。
尚、本発明におけるGPC(ゲルパーミエーションクロマトグラフィー)による重量平均分子量(ポリスチレン換算)の測定は東ソー(株)社製HLC8220システムを用い以下の条件で行った。
分離カラム:東ソー(株)製TSKgelGMHHR-Nを4本使用。カラム温度:40℃。移動層:和光純薬工業(株)製テトラヒドロフラン。流速:1.0ml/分。試料濃度:1.0質量%。試料注入量:100マイクロリットル。検出器:示差屈折計。
また、ガラス転移温度(Tg)の測定は、示差走査熱量計(株式会社TAインスツルメント製「DSC Q100」)を用い、窒素雰囲気下、冷却装置を用い温度範囲-80~450℃、昇温温度10℃/分の条件で走査を行う事で行った。
The present invention will be explained in more detail with reference to Examples below. In the examples, "parts" and "%" represent "parts by mass" and "% by mass," respectively.
In the present invention, the weight average molecular weight (in terms of polystyrene) was measured by GPC (gel permeation chromatography) using HLC8220 system manufactured by Tosoh Corporation under the following conditions.
Separation columns: Four TSKgelGMHHR-N manufactured by Tosoh Corporation were used. Column temperature: 40°C. Mobile layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0ml/min. Sample concentration: 1.0% by mass. Sample injection volume: 100 microliters. Detector: Differential refractometer.
In addition, the glass transition temperature (Tg) was measured using a differential scanning calorimeter (“DSC Q100” manufactured by TA Instruments Co., Ltd.) under a nitrogen atmosphere using a cooling device in the temperature range of -80 to 450°C and increasing the temperature. The scanning was performed at a temperature of 10° C./min.
〔調整例1〕
ポリビニルブチラール樹脂A(Tg63℃、ポリビニルアルコール成分19.5%)20部、イソプロピルアルコール40部、メチルエチルケトン40部を混合攪拌してリキッド印刷インキを作製した。得られたリキッド印刷インキを、粘度調整溶剤として希釈溶剤を用い、離合社製のザーンカップNo.3で18秒(25℃)になるように粘度を調整した。なお希釈溶剤としてイソプロピルアルコール:メチルエチルケトン= 50:50(質量比)を用いた。
[Adjustment example 1]
A liquid printing ink was prepared by mixing and stirring 20 parts of polyvinyl butyral resin A (Tg 63°C, polyvinyl alcohol component 19.5%), 40 parts of isopropyl alcohol, and 40 parts of methyl ethyl ketone. Using a diluting solvent as a viscosity adjusting solvent, the obtained liquid printing ink was transferred to Zahn Cup No. 1 manufactured by Rigosha. The viscosity was adjusted to 18 seconds (25° C.) at No. 3. Note that isopropyl alcohol: methyl ethyl ketone = 50:50 (mass ratio) was used as a diluting solvent.
〔調整例2〕
調整例1のポリビニルブチラール樹脂A(Tg63℃、ポリビニルアルコール成分19.5%)20部の代わりに、ポリビニルブチラール樹脂B(Tg70℃、ポリビニルアルコール成分25.5%)20部を使用した他は、調整例1と同様の配合、手順にてリキッド印刷インキを作製した。
[Adjustment example 2]
Except that 20 parts of polyvinyl butyral resin B (Tg 70°C, polyvinyl alcohol component 25.5%) was used instead of 20 parts of polyvinyl butyral resin A (Tg 63°C, polyvinyl alcohol component 19.5%) in Preparation Example 1. A liquid printing ink was prepared using the same formulation and procedure as in Preparation Example 1.
〔調整例3〕
調整例1のポリビニルブチラール樹脂A(Tg63℃、ポリビニルアルコール成分19.5%)20部の代わりに、ポリビニルブチラール樹脂C(Tg70℃、ポリビニルアルコール成分25.5%)20部を使用した他は、調整例1と同様の配合、手順にてリキッド印刷インキを作製した。
[Adjustment example 3]
Except that 20 parts of polyvinyl butyral resin C (Tg 70°C, polyvinyl alcohol content 25.5%) was used instead of 20 parts of polyvinyl butyral resin A (Tg 63°C, polyvinyl alcohol content 19.5%) in Preparation Example 1. A liquid printing ink was prepared using the same formulation and procedure as in Preparation Example 1.
〔調整例4〕
調整例1のポリビニルブチラール樹脂A(Tg63℃、ポリビニルアルコール成分19.5%)20部の代わりに、ポリビニルブチラール樹脂D(Tg72℃、ポリビニルアルコール成分25.5%)20部を使用した他は、調整例1と同様の配合、手順にてリキッド印刷インキを作製した。
[Adjustment example 4]
Except that 20 parts of polyvinyl butyral resin D (Tg 72°C, polyvinyl alcohol content 25.5%) was used instead of 20 parts of polyvinyl butyral resin A (Tg 63°C, polyvinyl alcohol content 19.5%) in Preparation Example 1. A liquid printing ink was prepared using the same formulation and procedure as in Preparation Example 1.
〔調整例5〕
ポリビニルブチラール樹脂A(Tg63℃、ポリビニルアルコール成分19.5%)20部、マレイン酸ロジンであるマルキードNO.31(荒川化学工業株式会社製)4部、イソプロピルアルコール36部、メチルエチルケトン40部を混合攪拌してリキッド印刷インキを作製した。得られたリキッド印刷インキを、粘度調整溶剤として希釈溶剤を用い、離合社製のザーンカップNo.3で18秒(25℃)になるように粘度を調整した。なお希釈溶剤としてイソプロピルアルコール:メチルエチルケトン= 50:50(質量比)を用いた。
[Adjustment example 5]
20 parts of polyvinyl butyral resin A (Tg 63°C, polyvinyl alcohol component 19.5%), Marquid NO. 31 (manufactured by Arakawa Chemical Industries, Ltd.), 36 parts of isopropyl alcohol, and 40 parts of methyl ethyl ketone were mixed and stirred to prepare a liquid printing ink. Using a diluting solvent as a viscosity adjusting solvent, the obtained liquid printing ink was transferred to Zahn Cup No. 1 manufactured by Rigosha. The viscosity was adjusted to 18 seconds (25° C.) at No. 3. Note that isopropyl alcohol: methyl ethyl ketone = 50:50 (mass ratio) was used as a diluting solvent.
〔調整例6〕
ポリビニルブチラール樹脂A(Tg63℃、ポリビニルアルコール成分19.5%)20部、ケトン樹脂としてTEGOVARIPLUS CA(エボニックジャパン株式会社製)4部、イソプロピルアルコール36部、メチルエチルケトン40部を混合攪拌してプライマーを作製した。得られたリキッド印刷インキを、粘度調整溶剤として希釈溶剤を用い、離合社製のザーンカップNo.3で18秒(25℃)になるように粘度を調整した。なお希釈溶剤としてイソプロピルアルコール:メチルエチルケトン= 50:50(質量比)を用いた。
[Adjustment example 6]
A primer was prepared by mixing and stirring 20 parts of polyvinyl butyral resin A (Tg 63°C, polyvinyl alcohol component 19.5%), 4 parts of TEGOVARI PLUS CA (manufactured by Evonik Japan Co., Ltd.) as a ketone resin, 36 parts of isopropyl alcohol, and 40 parts of methyl ethyl ketone. did. Using a diluting solvent as a viscosity adjusting solvent, the obtained liquid printing ink was transferred to Zahn Cup No. 1 manufactured by Rigosha. The viscosity was adjusted to 18 seconds (25° C.) at No. 3. Note that isopropyl alcohol: methyl ethyl ketone = 50:50 (mass ratio) was used as a diluting solvent.
〔調整例7〕
ポリビニルブチラール樹脂A(Tg63℃、ポリビニルアルコール成分19.5%)20部、アルキッド樹脂としてアルキディア1308E(DIC株式会社製)4部、イソプロピルアルコール36部、メチルエチルケトン40部を混合攪拌してプライマーを作製した。得られたリキッド印刷インキを、粘度調整溶剤として希釈溶剤を用い、離合社製のザーンカップNo.3で18秒(25℃)になるように粘度を調整した。なお希釈溶剤としてイソプロピルアルコール:メチルエチルケトン= 50:50(質量比)を用いた。
[Adjustment example 7]
A primer was prepared by mixing and stirring 20 parts of polyvinyl butyral resin A (Tg 63°C, polyvinyl alcohol component 19.5%), 4 parts of Alkydia 1308E (manufactured by DIC Corporation) as an alkyd resin, 36 parts of isopropyl alcohol, and 40 parts of methyl ethyl ketone. . Using a diluting solvent as a viscosity adjusting solvent, the obtained liquid printing ink was transferred to Zahn Cup No. 1 manufactured by Rigosha. The viscosity was adjusted to 18 seconds (25° C.) at No. 3. Note that isopropyl alcohol: methyl ethyl ketone = 50:50 (mass ratio) was used as a diluting solvent.
〔調整例8〕
ポリビニルブチラール樹脂A(Tg63℃、ポリビニルアルコール成分19.5%)20部、工業用硝化綿L1/8(ニトロセルロース、固形分70%、JIS K-6703により溶液濃度25.0%における粘度1.6~2.9%品 太平化学製品株式会社製)4部、イソプロピルアルコール36部、メチルエチルケトン40部を混合攪拌してプライマーを作製した。得られたリキッド印刷インキを、粘度調整溶剤として希釈溶剤を用い、離合社製のザーンカップNo.3で18秒(25℃)になるように粘度を調整した。なお希釈溶剤としてイソプロピルアルコール:メチルエチルケトン= 50:50(質量比)を用いた。
[Adjustment example 8]
20 parts of polyvinyl butyral resin A (Tg 63°C, polyvinyl alcohol component 19.5%), industrial nitrified cotton L1/8 (nitrocellulose, solid content 70%, viscosity 1.0 at a solution concentration of 25.0% according to JIS K-6703). A primer was prepared by mixing and stirring 4 parts of 6% to 2.9% product (manufactured by Taihei Chemical Products Co., Ltd.), 36 parts of isopropyl alcohol, and 40 parts of methyl ethyl ketone. Using a diluting solvent as a viscosity adjusting solvent, the obtained liquid printing ink was transferred to Zahn Cup No. 1 manufactured by Rigosha. The viscosity was adjusted to 18 seconds (25° C.) at No. 3. Note that isopropyl alcohol: methyl ethyl ketone = 50:50 (mass ratio) was used as a diluting solvent.
〔調整例9〕
工業用硝化綿L1/8(ニトロセルロース、固形分70%、JIS K-6703により溶液濃度25.0%における粘度1.6~2.9%品 太平化学製品株式会社製)30部、イソプロピルアルコール20部、酢酸エチル50部を混合攪拌してニトロセルロース溶液を作製した。得られたニトロセルロース溶液を、粘度調整溶剤として希釈溶剤を用い、離合社製のザーンカップNo.3で18秒(25℃)になるように粘度を調整した。なお希釈溶剤としてイソプロピルアルコール:酢酸エチル= 30:70(質量比)を用いた。
[Adjustment example 9]
30 parts of industrial nitrified cotton L1/8 (nitrocellulose, solid content 70%, viscosity 1.6 to 2.9% at a solution concentration of 25.0% according to JIS K-6703, manufactured by Taihei Chemical Products Co., Ltd.), isopropyl alcohol A nitrocellulose solution was prepared by mixing and stirring 20 parts of ethyl acetate and 50 parts of ethyl acetate. Using a diluting solvent as a viscosity adjusting solvent, the obtained nitrocellulose solution was transferred to Zahn Cup No. 1 manufactured by Rigosha. The viscosity was adjusted to 18 seconds (25° C.) at No. 3. Note that isopropyl alcohol:ethyl acetate=30:70 (mass ratio) was used as a diluting solvent.
〔調整例10〕
パラロイドA11(アクリル樹脂、Tg:100℃、Roam And Haas Company社製)20部、メチルエチルケトン40部、トルエン40部を混合攪拌してアクリル樹脂溶液を作製した。得られたアクリル樹脂溶液を、粘度調整溶剤として希釈溶剤を用い、離合社製のザーンカップNo.3で18秒(25℃)になるように粘度を調整した。なお希釈溶剤としてメチルエチルケトン:トルエン= 50:50(質量比)を用いた。
[Adjustment example 10]
An acrylic resin solution was prepared by mixing and stirring 20 parts of Paraloid A11 (acrylic resin, Tg: 100°C, manufactured by Roam and Haas Company), 40 parts of methyl ethyl ketone, and 40 parts of toluene. Using a diluting solvent as a viscosity adjusting solvent, the obtained acrylic resin solution was transferred to Zahn Cup No. 1 manufactured by Rigosha. The viscosity was adjusted to 18 seconds (25° C.) at No. 3. Note that methyl ethyl ketone:toluene=50:50 (mass ratio) was used as a diluent solvent.
〔調整例11〕
ソルバインA(塩化ビニル酢酸ビニル系樹脂、Tg:76℃、日信化学工業株式会社社製)20部、メチルエチルケトン50部、酢酸ノルマルプロピル30部を混合攪拌して塩酢ビ樹脂溶液を作製した。得られた塩化ビニル酢酸ビニル系樹脂溶液を、粘度調整溶剤として希釈溶剤を用い、離合社製のザーンカップNo.3で18秒(25℃)になるように粘度を調整した。なお希釈溶剤としてメチルエチルケトン:酢酸ノルマルプロピル=75:25(質量比)を用いた。
[Adjustment example 11]
A salt vinyl acetate resin solution was prepared by mixing and stirring 20 parts of Solvine A (vinyl chloride vinyl acetate resin, Tg: 76°C, manufactured by Nissin Chemical Industry Co., Ltd.), 50 parts of methyl ethyl ketone, and 30 parts of n-propyl acetate. The obtained vinyl chloride vinyl acetate resin solution was heated using a diluting solvent as a viscosity-adjusting solvent, using a Zahn cup No. manufactured by Rigosha. The viscosity was adjusted to 18 seconds (25° C.) at No. 3. Note that methyl ethyl ketone: normal propyl acetate = 75:25 (mass ratio) was used as a diluting solvent.
[銀インキの作製]
工業用硝化綿L1/8(ニトロセルロース、固形分70%、JIS K-6703により溶液濃度25.0%における粘度1.6~2.9%品 太平化学製品株式会社製)6部、イソプロピルアルコール6部、酢酸エチル48部を混合攪拌してニトロセルロース溶液を作製後、蒸着アルミニウム顔料BASF社製、「Metasheen 11-0010」、平均粒子径:10μm、不揮発分:10質量%)40部を混合攪拌して重ね刷り用銀インキを作製した。得られた銀インキを、粘度調整溶剤として希釈溶剤を用い、離合社製のザーンカップNo.3で18秒(25℃)になるように粘度を調整した。なお希釈溶剤として酢酸エチル:酢酸ノルマルプロピル= 50:50(重量比)を用いた。
[Preparation of silver ink]
Industrial nitrified cotton L1/8 (nitrocellulose, solid content 70%, viscosity 1.6-2.9% at a solution concentration of 25.0% according to JIS K-6703, manufactured by Taihei Chemical Products Co., Ltd.) 6 parts, isopropyl alcohol After mixing and stirring 6 parts of ethyl acetate and 48 parts of ethyl acetate to prepare a nitrocellulose solution, 40 parts of a vapor-deposited aluminum pigment (manufactured by BASF, "Metasheen 11-0010", average particle size: 10 μm, non-volatile content: 10% by mass) was mixed. A silver ink for overprinting was prepared by stirring. Using a diluting solvent as a viscosity adjusting solvent, the obtained silver ink was coated with Zahn Cup No. 1 manufactured by Rigosha. The viscosity was adjusted to 18 seconds (25° C.) at No. 3. Note that ethyl acetate: normal propyl acetate = 50:50 (weight ratio) was used as a diluting solvent.
〔実施例1〕
印刷用紙としてコート紙(CRC230g、レンゴー株式会社製)に、版深175L/inchグラビア版を備えたグラビア校正機を用いて、調整例1で得られたリキッド印刷インキ、銀インキの順で印刷してなる印刷物(積層体)を得た。
[Example 1]
The liquid printing ink obtained in Adjustment Example 1 and the silver ink were printed on coated paper (CRC 230 g, manufactured by Rengo Co., Ltd.) as printing paper using a gravure proofing machine equipped with a gravure plate with a plate depth of 175 L/inch, in that order. A printed matter (laminate) was obtained.
〔実施例2~8〕
実施例1の調整例1で得られたリキッド印刷インキの代わりに調整例2~8で得られたリキッド印刷インキ、銀インキの順で印刷し得た印刷物を其々実施例2~8とした。
[Examples 2 to 8]
In place of the liquid printing ink obtained in Preparation Example 1 of Example 1, the liquid printing inks obtained in Preparation Examples 2 to 8 and the silver ink were printed in that order, and the printed matter was designated as Examples 2 to 8, respectively. .
〔比較例1〕
印刷用紙としてコート紙(CRC230g、レンゴー株式会社製)に、版深175L/inchグラビア版を備えたグラビア校正機を用いて、印刷用紙に直に銀インキを印刷したものを比較例1とした。
[Comparative example 1]
Comparative Example 1 was prepared by printing silver ink directly on coated paper (CRC 230 g, manufactured by Rengo Co., Ltd.) as printing paper using a gravure proofing machine equipped with a gravure plate with a plate depth of 175 L/inch.
〔比較例2~4〕
実施例1の調整例1で得られたリキッド印刷インキの代わりに調整例9~11で得られたリキッド印刷インキ、銀インキの順で印刷し得た印刷物を其々比較例2~4とした。
[Comparative Examples 2 to 4]
In place of the liquid printing ink obtained in Preparation Example 1 of Example 1, the liquid printing inks obtained in Preparation Examples 9 to 11 and the silver ink were printed in that order, and the printed matter was designated as Comparative Examples 2 to 4, respectively. .
作製した各々印刷物に対し、光沢度、隠蔽性、及び基材密着性を以下の評価手順に従って評価した。 The glossiness, concealing property, and adhesion to the base material of each of the produced printed matter were evaluated according to the following evaluation procedure.
〔評価項目1:光沢度〕
印刷物の金属外観について、20°、及び60°の光沢度をJIS Z 8741に準拠して、鏡面光沢計(BYK-Gardner社製、「micro-TRI-gloss」)を用いて測定した。光沢度は数値が大きいほど光沢が高く、光輝性に優れることを示す。
[Evaluation item 1: Glossiness]
Regarding the metallic appearance of the printed matter, the glossiness at 20° and 60° was measured in accordance with JIS Z 8741 using a specular gloss meter (manufactured by BYK-Gardner, "micro-TRI-gloss"). The higher the gloss value, the higher the gloss and the better the glitter.
〔評価項目2:隠蔽性〕
印刷物の金属外観を目視評価した。評価基準は以下の通りである。
(評価基準)
○:銀インキの転移性が良好で、原紙の無地部がほとんど見られない
△:銀インキの転移性が僅かに劣り、20%未満の無地部が見られるが、
実用範囲内である
×:銀インキの転移性が劣り、20%以上の無地部が見られる
[Evaluation item 2: Concealability]
The metallic appearance of the printed matter was visually evaluated. The evaluation criteria are as follows.
(Evaluation criteria)
○: The transferability of the silver ink is good, and the plain area of the base paper is hardly seen. △: The transferability of the silver ink is slightly poor, and less than 20% of the plain area is seen.
Within the practical range ×: The transferability of silver ink is poor, and 20% or more of the plain area is observed.
〔評価項目3:基材密着性〕
作製した各々印刷物を1日放置後、印刷面にセロハンテープ(ニチバン製12mm幅)を貼り付け、これを急速に剥がしたときの印刷皮膜の外観の状態を目視評価した。
(評価基準)
○:銀インキ被膜の50%以上が紙のコート層から剥がれ、紙の繊維が見える。
△:銀インキ被膜の50%未満が紙のコート層から剥がれ、紙の繊維が見えるが
実用範囲内である。
×:銀インキ被膜は剥がれるがコート層からの剥離ではなく、紙の繊維は見えない。
[Evaluation item 3: Adhesion to base material]
After each of the produced printed matter was left for one day, cellophane tape (12 mm width, manufactured by Nichiban) was attached to the printed surface, and when this was rapidly peeled off, the appearance of the printed film was visually evaluated.
(Evaluation criteria)
○: 50% or more of the silver ink film is peeled off from the paper coating layer, and paper fibers are visible.
Δ: Less than 50% of the silver ink film was peeled off from the paper coating layer, and paper fibers were visible, but within the practical range.
×: The silver ink film peels off, but it does not peel off from the coating layer, and the paper fibers are not visible.
表1にリキッド印刷インキの各調整例の配合を、表2に作製した印刷物の各々の評価結果を示す。 Table 1 shows the formulation of each adjustment example of liquid printing ink, and Table 2 shows the evaluation results of each printed matter produced.
本発明のリキッド印刷インキは、銀インキを重ね刷りした印刷物において、基材との密着性、高い光沢度による輝度感、及び印刷部分の十分な隠蔽性を兼備することが出来る。 The liquid printing ink of the present invention can have adhesion to the substrate, brightness due to high gloss, and sufficient concealment of the printed part in printed matter overprinted with silver ink.
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JPH07299975A (en) * | 1994-05-09 | 1995-11-14 | Konica Corp | Certification and discrimination card |
JP4258673B2 (en) * | 2005-04-12 | 2009-04-30 | 東洋アルミニウム株式会社 | Laminate and ink film |
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JP2000154345A (en) | 1998-09-16 | 2000-06-06 | Toshiba Corp | Erasable printing ink |
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