JP2019077779A - Paper solvent type gravure printing ink composition and printing method - Google Patents
Paper solvent type gravure printing ink composition and printing methodInfo
- Publication number
- JP2019077779A JP2019077779A JP2017205465A JP2017205465A JP2019077779A JP 2019077779 A JP2019077779 A JP 2019077779A JP 2017205465 A JP2017205465 A JP 2017205465A JP 2017205465 A JP2017205465 A JP 2017205465A JP 2019077779 A JP2019077779 A JP 2019077779A
- Authority
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- Prior art keywords
- ink composition
- paper
- printing
- gravure printing
- organic solvent
- Prior art date
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- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 78
- 238000007639 printing Methods 0.000 title claims abstract description 42
- 238000007646 gravure printing Methods 0.000 title claims abstract description 31
- 239000002904 solvent Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 55
- 239000011347 resin Substances 0.000 claims abstract description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 27
- 239000000049 pigment Substances 0.000 claims abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 17
- 239000002635 aromatic organic solvent Substances 0.000 claims abstract description 6
- 239000000020 Nitrocellulose Substances 0.000 claims description 17
- 229920001220 nitrocellulos Polymers 0.000 claims description 17
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 25
- 230000003287 optical effect Effects 0.000 abstract description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000004014 plasticizer Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 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 description 6
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000001023 inorganic pigment Substances 0.000 description 4
- 239000012860 organic pigment Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- -1 bengala Chemical compound 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002168 ethanoic acid esters Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002123 temporal effect Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- PMOTYADHFATPGX-UHFFFAOYSA-N 1-phenylpropane-1-sulfonamide Chemical compound CCC(S(N)(=O)=O)C1=CC=CC=C1 PMOTYADHFATPGX-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical group OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910002039 SYLYSIA SY350 Inorganic materials 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PPKVREKQVQREQD-UHFFFAOYSA-N antimony pentasulfide Chemical compound S=[Sb](=S)S[Sb](=S)=S PPKVREKQVQREQD-UHFFFAOYSA-N 0.000 description 1
- 229960001283 antimony pentasulfide Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical group CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は、紙用溶剤型グラビア印刷インキ組成物および印刷方法に関する。より詳細には、本発明は、光学濃度が高く、マイレージ、耐アルコール性が良好な印刷物を作製し得る紙用溶剤型グラビア印刷インキ組成物および印刷方法に関する。 The present invention relates to a solvent-based gravure printing ink composition for paper and a printing method. More specifically, the present invention relates to a solvent-based gravure printing ink composition for paper and a printing method capable of producing a printed material having high optical density and good mileage and alcohol resistance.
タバコ、紙コップ、お菓子箱等の紙基材には、紙用溶剤型グラビア印刷インキ組成物を用いてグラビア方式で印刷が施される。紙用溶剤型グラビア印刷インキ組成物に含まれるバインダー樹脂としては、ウレタン樹脂、塩化ビニル−酢酸ビニル共重合体樹脂、アクリル系樹脂、ニトロセルロース樹脂、ポリアマイド樹脂、塩素化ポリオレフィン樹脂等が知られている。さらに、近年、環境に与える負荷を削減するために、溶剤は、ノントルエン型のものが使用されつつある。バインダー樹脂は、ノントルエン型の溶剤に適した、ウレタン樹脂、塩化ビニル−酢酸ビニル共重合体樹脂、アクリル系樹脂、ニトロセルロース樹脂から選ばれる１種または２種以上を混合したものが用いられる。バインダー樹脂は、紙基材への接着性の観点から、ニトロセルロース樹脂を単独、または、ニトロセルロース樹脂とアクリル樹脂とが併用されている（たとえば、特許文献１参照）。また、バインダー樹脂として、ニトロセルロース樹脂と、ロジン、酸変性ロジンおよびエステル化ロジンから選ばれる１種以上のロジン系樹脂とを併用する紙用溶剤型グラビア印刷インキ組成物（たとえば、特許文献２参照）が提案されている。 Printing is performed on a paper substrate such as a cigarette, a paper cup, a candy box or the like by a gravure method using a solvent type gravure printing ink composition for paper. As a binder resin contained in a solvent type gravure printing ink composition for paper, a urethane resin, a vinyl chloride-vinyl acetate copolymer resin, an acrylic resin, a nitrocellulose resin, a polyamide resin, a chlorinated polyolefin resin, etc. are known. There is. Further, in recent years, non-toluene type solvents are being used to reduce the burden on the environment. As the binder resin, one or a mixture of one or more selected from a urethane resin, a vinyl chloride-vinyl acetate copolymer resin, an acrylic resin, and a nitrocellulose resin suitable for non-toluene type solvents is used. The binder resin is a nitrocellulose resin alone or a combination of a nitrocellulose resin and an acrylic resin from the viewpoint of adhesion to a paper substrate (see, for example, Patent Document 1). In addition, a solvent-based gravure printing ink composition for paper using a nitrocellulose resin and at least one rosin-based resin selected from rosin, acid-modified rosin and esterified rosin as a binder resin (see, for example, Patent Document 2) ) Has been proposed.
しかしながら、特許文献１〜２に記載のインキ組成物は、未コート紙に印刷した場合に浸透しやすく、要求される印刷濃度を達成するためには多くのインキが必要であった。 However, the ink compositions described in Patent Documents 1 and 2 easily penetrate when printed on uncoated paper, and a large amount of ink is required to achieve the required printing density.
本発明は、このような従来の課題に鑑みてなされたものであり、光学濃度が高く、マイレージ、耐アルコール性が良好な印刷物を作製し得る紙用溶剤型グラビア印刷インキ組成物および印刷方法を提供することを目的とする。 The present invention has been made in view of such conventional problems, and a solvent-based gravure printing ink composition for paper and a printing method capable of producing a printed material having high optical density and good mileage and alcohol resistance. Intended to be provided.
本発明者らは、上記課題を解決するために鋭意検討を行った結果、紙用溶剤型グラビア印刷インキ組成物において、平均粒子径６μｍ以下のシリカ粒子をインキ組成物中に０．１〜２質量％となるよう含ませることにより、上記の課題を解決し得ることを見出し、本発明を完成させた。上記課題を解決する本発明は、以下の構成を主に備える。 As a result of intensive studies to solve the above problems, the present inventors have found that, in a solvent type gravure printing ink composition for paper, silica particles having an average particle diameter of 6 μm or less in the ink composition are 0.1 to 2 By containing so that it may become mass%, it discovers that said subject can be solved and completed this invention. The present invention for solving the above problems mainly comprises the following configuration.
（１）顔料と、バインダー樹脂と、有機溶剤と、平均粒子径が６μｍ以下であるシリカ粒子とを含み、前記シリカ粒子の含有量は、インキ組成物中、０．１〜２質量％であり、前記有機溶剤は、非芳香族系有機溶剤を含む、紙用溶剤型グラビア印刷インキ組成物。 (1) A pigment, a binder resin, an organic solvent, and a silica particle having an average particle diameter of 6 μm or less, and the content of the silica particle is 0.1 to 2% by mass in the ink composition The solvent-based gravure printing ink composition for paper, wherein the organic solvent comprises a non-aromatic organic solvent.
このような構成によれば、紙用溶剤型グラビア印刷インキ組成物は、光学濃度が高く、マイレージ、耐アルコール性が良好な印刷物を作製し得る。 According to such a configuration, the solvent type gravure printing ink composition for paper can produce a printed product having a high optical density and good mileage and alcohol resistance.
（２）前記バインダー樹脂は、ニトロセルロース樹脂または塩化ビニル−酢酸ビニル共重合体樹脂を含む、（１）記載の紙用溶剤型グラビア印刷インキ組成物。 (2) The solvent-based gravure printing ink composition for paper according to (1), wherein the binder resin comprises a nitrocellulose resin or a vinyl chloride-vinyl acetate copolymer resin.
このような構成によれば、紙用溶剤型グラビア印刷インキ組成物は、光学濃度がより高く、マイレージ、耐アルコール性が良好で基材との密着性が良好である。 According to such a configuration, the solvent type gravure printing ink composition for paper has a higher optical density, good mileage and alcohol resistance, and good adhesion to a substrate.
（３）（１）または（２）記載の紙用溶剤型グラビア印刷インキ組成物を、グラビア版を用いてグラビア印刷方式にて印刷する、印刷方法。 (3) A printing method, wherein the solvent-based gravure printing ink composition for paper according to (1) or (2) is printed by a gravure printing method using a gravure plate.
このような構成によれば、印刷方法は、マイレージが良好で、得られる印刷物は、光学濃度が高く、耐アルコール性が良好となる。 According to such a configuration, the printing method has good mileage, and the resulting printed matter has high optical density and good alcohol resistance.
本発明によれば、光学濃度が高く、マイレージ、耐アルコール性が良好な印刷物を作製し得る紙用溶剤型グラビア印刷インキ組成物および印刷方法を提供することができる。 According to the present invention, it is possible to provide a solvent-based gravure printing ink composition for paper and a printing method capable of producing a printed material having high optical density and good mileage and alcohol resistance.
＜紙用溶剤型グラビア印刷インキ組成物＞
本発明の一実施形態の紙用溶剤型グラビア印刷インキ組成物（以下、インキ組成物ともいう）は、顔料と、バインダー樹脂と、有機溶剤と、平均粒子径が６μｍ以下であるシリカ粒子とを主に含む。シリカ粒子の含有量は、インキ組成物中、０．１〜２質量％である。有機溶剤は、非芳香族系有機溶剤を含む。以下、それぞれについて説明する。
<Solvent-type gravure printing ink composition for paper>
A solvent-based gravure printing ink composition for paper (hereinafter also referred to as an ink composition) according to an embodiment of the present invention comprises a pigment, a binder resin, an organic solvent, and silica particles having an average particle diameter of 6 μm or less. Mainly includes. The content of the silica particles is 0.1 to 2% by mass in the ink composition. Organic solvents include non-aromatic organic solvents. Each of these will be described below.
（顔料）
顔料は、一般にインキ組成物で使用され得る各種無機顔料、有機顔料等が例示される。無機顔料としては、酸化チタン、ベンガラ、アンチモンレッド、カドミウムレッド、カドミウムイエロー、コバルトブルー、紺青、群青、カーボンブラック、黒鉛等が例示される。有機顔料としては、溶性アゾ顔料、不溶性アゾ顔料、アゾレーキ顔料、縮合アゾ顔料、銅フタロシアニン顔料、縮合多環顔料等が例示される。
(Pigment)
Examples of the pigment generally include various inorganic pigments, organic pigments and the like which can be used in the ink composition. Examples of the inorganic pigment include titanium oxide, bengala, antimony red, cadmium red, cadmium yellow, cobalt blue, bitumen, ultramarine blue, carbon black, graphite and the like. Examples of the organic pigment include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments and the like.
印刷時における顔料の含有量は、特に限定されない。一例を挙げると、有機顔料は、インキ組成物中、５質量％以上であることが好ましく、７質量％以上であることがより好ましい。また、有機顔料は、インキ組成物中、１３質量％以下であることが好ましい。無機顔料は、インキ組成物中、５質量％以上であることが好ましく、７質量％以上であることがより好ましい。また、無機顔料は、インキ組成物中、３５質量％以下であることが好ましい。なお、各顔料によって着色力が異なるため、たとえばカーボンブラックのように着色力が高い顔料が用いられる場合には、含有量は、５〜１３質量％の範囲であってもよく、たとえば酸化チタンのように着色力が低い顔料が用いられる場合には、含有量は、１５〜３５質量％の範囲であってもよい。インキ組成物中の顔料の含有量が上記範囲よりも少ない場合、得られる印刷物は、光学濃度が低下する傾向がある。一方、インキ組成物中の顔料の含有量が上記の範囲よりも多い場合、どの顔料でもインキ組成物の粘度が高くなり、印刷物が汚れやすい傾向がある。また、必要に応じて、上記顔料と共に染料が併用されてもよい。 The content of the pigment at the time of printing is not particularly limited. If an example is given, it is preferable that it is 5 mass% or more in an ink composition, and, as for an organic pigment, it is more preferable that it is 7 mass% or more. The organic pigment is preferably 13% by mass or less in the ink composition. The content of the inorganic pigment in the ink composition is preferably 5% by mass or more, and more preferably 7% by mass or more. Moreover, it is preferable that an inorganic pigment is 35 mass% or less in an ink composition. In addition, since coloring power changes with each pigment, when a pigment with high coloring power like carbon black is used, for example, content may be in the range of 5 to 13% by mass, for example, titanium oxide When a pigment having a low coloring power is used, the content may be in the range of 15 to 35% by mass. When the content of the pigment in the ink composition is less than the above range, the resulting printed matter tends to have a reduced optical density. On the other hand, when the content of the pigment in the ink composition is larger than the above range, the viscosity of the ink composition becomes high with any pigment, and the printed matter tends to be stained. In addition, a dye may be used in combination with the above-mentioned pigment, if necessary.
（バインダー樹脂）
バインダー樹脂は特に限定されない。一例を挙げると、バインダー樹脂は、ニトロセルロース樹脂、塩化ビニル−酢酸ビニル共重合体樹脂、ロジン系樹脂、アクリル系樹脂、ウレタン系樹脂等である。これらは併用されてもよい。これらの中でも、バインダー樹脂は、基材との密着性が優れる観点から、ニトロセルロース樹脂または塩化ビニル−酢酸ビニル共重合体樹脂を含むことが好ましい。
(Binder resin)
The binder resin is not particularly limited. As an example, the binder resin is nitrocellulose resin, vinyl chloride-vinyl acetate copolymer resin, rosin resin, acrylic resin, urethane resin and the like. These may be used in combination. Among these, the binder resin preferably contains a nitrocellulose resin or a vinyl chloride-vinyl acetate copolymer resin from the viewpoint of excellent adhesion with the substrate.
・ニトロセルロース樹脂
ニトロセルロース樹脂は、たとえば、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。
-Nitrocellulose resin Nitrocellulose resin is obtained, for example, by reacting natural cellulose with nitric acid to obtain three hydroxyl groups in the six-membered ring of anhydrous glucopyranose group in natural cellulose as a nitrate ester substituted with a nitrate group. Be
本実施形態において好適に使用されるニトロセルロース樹脂は、窒素量が１０〜１３％であり、平均重合度が３５〜９０である。ニトロセルロース樹脂の具体例は、ＫＯＲＥＡ ＣＮＣ社製の硝化綿ＳＳ１／２、ＳＳ１／４（０．１５５Ｐａ・ｓ）、ＳＳ１／８（０．１５０Ｐａ・ｓ）、ＴＲ１／１６（０．０６５Ｐａ・ｓ）等である。なお、上記粘度は、いずれも固形分２０％、酢酸エチル溶液：イソプロピルアルコール＝９０：１０の混合溶液における２５℃における３０ｒｐｍでの粘度である。本実施形態のインキ組成物中の顔料濃度を高くする場合には、粘度が０．０３〜０．１０Ｐａ・ｓにあるニトロセルロース樹脂であるＴＲ１／１６を使用することが好ましい。 The nitrocellulose resin suitably used in the present embodiment has a nitrogen content of 10 to 13% and an average degree of polymerization of 35 to 90. Specific examples of the nitrocellulose resin are nitrified cotton SS1 / 2, SS1 / 4 (0.155 Pa · s), SS1 / 8 (0.150 Pa · s), TR1 / 16 (0.065 Pa · s) manufactured by KOREA CNC. Etc. The above viscosity is the viscosity at 30 rpm at 25 ° C. in a mixed solution of solid content of 20% and ethyl acetate solution: isopropyl alcohol = 90: 10. In order to increase the pigment concentration in the ink composition of the present embodiment, it is preferable to use TR1 / 16, which is a nitrocellulose resin having a viscosity of 0.03 to 0.10 Pa · s.
本実施形態のニトロセルロース樹脂の数平均分子量は、１０，０００以上であることが好ましく、１５，０００以上であることがより好ましい。また、ニトロセルロース樹脂の数平均分子量は、３０，０００以下であることが好ましく、２５，０００以下であることがより好ましい。 The number average molecular weight of the nitrocellulose resin of the present embodiment is preferably 10,000 or more, and more preferably 15,000 or more. The number average molecular weight of the nitrocellulose resin is preferably 30,000 or less, more preferably 25,000 or less.
・塩化ビニル−酢酸ビニル共重合体樹脂
塩化ビニル−酢酸ビニル共重合体樹脂は、従来、インキ組成物に使用されている塩化ビニルモノマーと酢酸ビニルモノマーとの共重合体が使用され得る。中でも、塩化ビニル−酢酸ビニル共重合体樹脂は、環境に配慮したインキの有機溶剤系において、本実施形態の課題に関する諸性能をバランスよく向上させるのに有利である点から、水酸基を有する塩化ビニル−酢酸ビニル共重合体樹脂が好適である。このような水酸基を有する塩化ビニル−酢酸ビニル共重合体樹脂は、たとえば、酢酸エステル部分の一部をケン化することにより得られ得る。酢酸エステル部分の一部をケン化することにより得られた水酸基を有する塩化ビニル−酢酸ビニル共重合体樹脂の場合、分子中の塩化ビニルの反応部位に基づく構成単位（下記式１）、酢酸ビニルの反応部位に基づく構成単位（下記式２）、および酢酸ビニルの反応部位のケン化に基づく構成単位（下記式３）の比率により樹脂の皮膜物性や溶解挙動が決定される。すなわち、塩化ビニルの反応部位に基づく構成単位は、樹脂皮膜の強靭さや硬さを付与し、酢酸ビニルの反応部位に基づく構成単位は接着性や柔軟性を付与し、酢酸ビニルの反応部位のケン化に基づく構成単位は環境に配慮したインキの有機溶剤系への良好な溶解性を付与する。
式１ ‐ＣＨ2−ＣＨＣｌ−
式２ ‐ＣＨ2−ＣＨ（ＯＣＯＣＨ3）−
式３ ‐ＣＨ2−ＣＨ（ＯＨ）−（重合ロジン）
-Vinyl chloride-vinyl acetate copolymer resin The vinyl chloride-vinyl acetate copolymer resin may be a copolymer of a vinyl chloride monomer and a vinyl acetate monomer which are conventionally used in ink compositions. Above all, vinyl chloride-vinyl acetate copolymer resin is a vinyl chloride having a hydroxyl group from the viewpoint of being advantageous for improving various performances related to the problems of the present embodiment in a well-balanced manner in an organic solvent system of an environmentally friendly ink. -Vinyl acetate copolymer resins are preferred. Such a vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group can be obtained, for example, by saponifying part of an acetic acid ester portion. In the case of a vinyl chloride-vinyl acetate copolymer resin having a hydroxyl group obtained by saponifying a part of an acetic acid ester moiety, a constituent unit based on the reaction site of vinyl chloride in the molecule (the following formula 1), vinyl acetate The film physical properties and dissolution behavior of the resin are determined by the ratio of the structural unit based on the reaction site of (formula 2 below) and the structural unit based on the saponification of the reaction site of vinyl acetate (formula 3 below). That is, the structural unit based on the reactive site of vinyl chloride imparts toughness and hardness of the resin film, and the structural unit based on the reactive site of vinyl acetate imparts adhesiveness and flexibility, and Constituting structural units provide good solubility of the environmentally friendly ink in organic solvent systems.
Equation 1 -CH 2 -CHCl-
Formula 2-CH 2- CH (OCOCH 3 )-
Formula 3-CH 2- CH (OH)-(polymerized rosin)
本実施形態の塩化ビニル−酢酸ビニル共重合体樹脂の数平均分子量は、１０，０００以上であることが好ましく、１５，０００以上であることがより好ましい。また、塩化ビニル−酢酸ビニル共重合体樹脂の数平均分子量は、３５，０００以下であることが好ましく、３０，０００以下であることがより好ましい。 The number average molecular weight of the vinyl chloride-vinyl acetate copolymer resin of the present embodiment is preferably 10,000 or more, and more preferably 15,000 or more. The number average molecular weight of the vinyl chloride-vinyl acetate copolymer resin is preferably 35,000 or less, more preferably 30,000 or less.
印刷時におけるバインダー樹脂の含有量は、特に限定されない。一例を挙げると、バインダー樹脂の含有量は、インキ組成物中、７質量％以上であることが好ましく、１０質量％以上であることがより好ましい。また、バインダー樹脂の含有量は、インキ組成物中、１５質量％以下であることが好ましく、１３質量％以下であることがより好ましい。バインダー樹脂の含有量が上記範囲内であることにより、得られるインキ組成物は、印刷物における良好な塗膜物性を発現させたり、適正な粘度範囲となる。 The content of the binder resin at the time of printing is not particularly limited. As an example, the content of the binder resin in the ink composition is preferably 7% by mass or more, and more preferably 10% by mass or more. The content of the binder resin in the ink composition is preferably 15% by mass or less, and more preferably 13% by mass or less. When the content of the binder resin is in the above range, the obtained ink composition can exhibit good coating film physical properties in the printed matter, and has an appropriate viscosity range.
・有機溶剤
有機溶剤は、顔料およびバインダー樹脂を溶解させるために配合される。有機溶剤は特に限定されない。一例を挙げると、有機溶剤は、ケトン系有機溶剤（アセトン、メチルエチルケトン、メチルイソブチルケトン等）、エステル系有機溶剤（酢酸メチル、酢酸エチル、酢酸ｎ−プロピル、酢酸ｎ−ブチル、酢酸イソブチル等）、アルコール系有機溶剤（メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ブタノール等）等の非芳香族系有機溶剤である。これら非芳香族系有機溶剤が用いられることにより、インキ組成物は、環境面において有利である。
Organic Solvent The organic solvent is blended to dissolve the pigment and the binder resin. The organic solvent is not particularly limited. As an example, the organic solvent is ketone organic solvent (acetone, methyl ethyl ketone, methyl isobutyl ketone etc.), ester organic solvent (methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate etc.), Non-aromatic organic solvents such as alcohol-based organic solvents (methanol, ethanol, n-propanol, isopropanol, butanol and the like). By using these non-aromatic organic solvents, the ink composition is environmentally advantageous.
有機溶剤は、環境問題への対応と、インキの印刷適性や乾燥性等を考慮して、エステル系有機溶剤とアルコール系有機溶剤との混合有機溶剤が、エステル系有機溶剤：アルコール系有機溶剤＝４０／６０〜９５／５の範囲となるように使用されることが好ましい。 The organic solvent is a mixed organic solvent of an ester-based organic solvent and an alcohol-based organic solvent in consideration of the response to environmental problems, the printability and drying properties of the ink, etc .; Preferably, it is used in the range of 40/60 to 95/5.
有機溶剤の含有量は、得られるインキ組成物の印刷性が優れる点から、インキ組成物中１５．０質量％以上であることが好ましい。また、有機溶剤の含有量は、９０質量％以下であることが好ましい。有機溶剤の含有量が１５．０質量％未満である場合、インキ組成物は、印刷適性が低位となる傾向がある。一方、有機溶剤の含有量が９０質量％を超える場合、得られる印刷物は、充分な発色が得られない傾向がある。 The content of the organic solvent is preferably 15.0% by mass or more in the ink composition from the viewpoint that the printability of the obtained ink composition is excellent. Moreover, it is preferable that content of the organic solvent is 90 mass% or less. When the content of the organic solvent is less than 15.0% by mass, the ink composition tends to have low printability. On the other hand, when the content of the organic solvent exceeds 90% by mass, the resulting printed matter tends to fail to obtain sufficient color development.
（シリカ粒子）
シリカ粒子は、平均粒子径が６μｍ以下のものが使用される。平均粒子径は、６μｍ以下であればよく、３μｍ以下であることが好ましい。平均粒子径が６μｍを超える場合、得られるインキ組成物を用いると、耐アルコール性が低下する傾向がある。なお、シリカ粒子の平均粒子径の下限は特に限定されない。
(Silica particles)
As the silica particles, those having an average particle diameter of 6 μm or less are used. The average particle size may be 6 μm or less, preferably 3 μm or less. When the average particle size exceeds 6 μm, alcohol resistance tends to decrease when the resulting ink composition is used. The lower limit of the average particle size of the silica particles is not particularly limited.
シリカ粒子の含有量は、得られるインキ組成物の印刷性が優れる点から、インキ組成物中、０．１質量％以上であることが好ましく、０．５質量％以上であることがより好ましい。また、シリカ粒子の含有量は、２．０質量％以下であることが好ましく、１．０質量％以下であることがより好ましい。シリカ粒子の含有量が０．１質量％未満である場合、得られるインキ組成物は、印刷適性およびマイレージが低下する傾向がある。一方、シリカ粒子の含有量が２質量％を超える場合、インキ組成物は、耐アルコール性が低下する傾向がある。 The content of the silica particles is preferably 0.1% by mass or more in the ink composition, and more preferably 0.5% by mass or more from the viewpoint that the printability of the obtained ink composition is excellent. The content of the silica particles is preferably 2.0% by mass or less, and more preferably 1.0% by mass or less. When the content of the silica particles is less than 0.1% by mass, the resulting ink composition tends to have poor printability and mileage. On the other hand, when the content of silica particles exceeds 2% by mass, the ink composition tends to have reduced alcohol resistance.
（任意成分）
本実施形態のインキ組成物は、適宜、可塑剤、粘着付与剤、架橋剤、滑剤、耐ブロッキング剤、帯電防止剤、界面活性剤等の各種添加剤が配合されてもよい。
(Optional ingredient)
In the ink composition of the present embodiment, various additives such as a plasticizer, a tackifier, a crosslinking agent, a lubricant, a blocking agent, an antistatic agent, and a surfactant may be appropriately blended.
可塑剤は、インキ組成物における残留溶剤を低減するために、好適に配合される。可塑剤は特に限定されない。一例を挙げると、可塑剤は、セバチン酸ジオクチル、エポキシ化大豆油、脂肪酸トリグリセリド、エチルトルエンスルホン酸アミド、アセチルクエン酸トリブチル、ステアリン酸２エチルヘキシルエステル、パルミチン酸２−エチルヘキシルエステル等である。 The plasticizer is suitably blended to reduce the residual solvent in the ink composition. The plasticizer is not particularly limited. As an example, the plasticizer is dioctyl sebacate, epoxidized soybean oil, fatty acid triglyceride, ethyltoluenesulfonic acid amide, tributyl acetyl citrate, 2-ethylhexyl stearic acid ester, 2-ethylhexyl palmitate ester and the like.
可塑剤が含まれる場合、可塑剤の含有量は特に限定されない。一例を挙げると、可塑剤の含有量は、インキ組成物中、０．１質量％以上であることが好ましく、０．５質量％以上であることがより好ましい。また、可塑剤の含有量は、インキ組成物中、５．０質量％以下であることが好ましく、３．０質量％以下であることがより好ましい。可塑剤の含有量が上記範囲内であることにより、得られるインキ組成物は、残留溶剤が低減されやすい。 When a plasticizer is included, the content of the plasticizer is not particularly limited. As an example, the content of the plasticizer in the ink composition is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. In addition, the content of the plasticizer in the ink composition is preferably 5.0% by mass or less, and more preferably 3.0% by mass or less. When the content of the plasticizer is in the above range, the residual solvent of the obtained ink composition tends to be reduced.
本実施形態のインキ組成物の製造方法は特に限定されない。一例を挙げると、インキ組成物は、顔料、バインダー樹脂、有機溶剤、および各種任意成分を攪拌混合した後、各種の分散・混練装置を使用してマスターバッチを製造し、次いで、残りの材料を加えて調整することにより製造し得る。なお、インキ組成物の粘度が低い場合、顔料等の分散安定性が低下する可能性がある。一方、粘度が高い場合、インキ組成物は、印刷に適した粘度とするために多量の希釈が必要となり、浅版を利用した印刷版への対応が困難になる可能性がある。そこで、インキ組成物の粘度は、３〜２０ｍＰａ・ｓの範囲に適宜調整されることが好ましい。 The method for producing the ink composition of the present embodiment is not particularly limited. For example, the ink composition comprises a pigment, a binder resin, an organic solvent, and various optional components after stirring and mixing, and then a masterbatch is manufactured using various dispersing and kneading apparatuses, and then the remaining materials are In addition, it can manufacture by adjusting. When the viscosity of the ink composition is low, the dispersion stability of the pigment or the like may be reduced. On the other hand, when the viscosity is high, the ink composition needs a large amount of dilution to obtain a viscosity suitable for printing, which may make it difficult to cope with a printing plate using a shallow printing plate. Therefore, it is preferable that the viscosity of the ink composition be appropriately adjusted in the range of 3 to 20 mPa · s.
インキ組成物は、印刷時の雰囲気温度において、印刷条件に応じて適切な秒数となるように、具体的にはザーンカップ３号の流出秒数が１４〜１８秒、好ましくは１５〜１７秒程度となるまで、必要に応じて有機溶剤で希釈されることが好ましい。また、インキ組成物は、上記製造方法に代えて、マスターバッチ等を経由せず、材料を混合して印刷時のインキ組成物が作製されてもよい。 Specifically, the ink composition has an outflow second number of 14 to 18 seconds, preferably 15 to 17 seconds, so that the appropriate number of seconds can be obtained according to the printing conditions at the ambient temperature at the time of printing. Preferably, it is diluted with an organic solvent to the extent necessary. Further, the ink composition may be prepared by mixing the materials without using the master batch or the like instead of the above-mentioned production method to produce an ink composition at the time of printing.
以上、本実施形態によれば、光学濃度が高く、マイレージ、耐アルコール性が良好な印刷物を作製し得るインキ組成物が得られる。 As described above, according to this embodiment, an ink composition capable of producing a printed material having a high optical density and good mileage and alcohol resistance can be obtained.
＜印刷方法＞
本発明の一実施形態の印刷方法は、上記した紙用溶剤型グラビア印刷インキ組成物を、グラビア版を用いてグラビア印刷方式にて印刷する方法である。すなわち、上記インキ組成物は、一般的なグラビア印刷方式を採用することができる。印刷用基材は、タバコ、紙コップ、お菓子箱等に使用されている紙基材が好適に使用され得る。これらの中でも、印刷用基材は、未コート紙であることが好ましい。上記実施形態のインキ組成物は、未コート紙に対して印刷される場合であっても、より小さい膜厚の場合（マイレージが高い場合）においても光学濃度が高く、かつ、耐アルコール性を良好に発揮し得る。なお、グラビア印刷方式の条件は、従来公知の方法、条件と同様である。
<Printing method>
The printing method according to an embodiment of the present invention is a method of printing the above-described solvent-based gravure printing ink composition for paper using a gravure plate by a gravure printing method. That is, the said ink composition can employ | adopt a general gravure printing system. As the printing substrate, a paper substrate used for cigarettes, paper cups, candy boxes and the like can be suitably used. Among these, the printing substrate is preferably an uncoated paper. The ink composition of the above embodiment has high optical density and good alcohol resistance even when printed on uncoated paper or when the film thickness is smaller (when mileage is high). Can be The conditions of the gravure printing method are the same as those of conventionally known methods and conditions.
使用する印刷版は、従来の版胴（通常のグラビア製版方式によって作られる凹版で、その製版方式は、彫刻グラビア等が例示できる）であってもよく、従来の版胴より浅いセルを形成（浅版化）したものであってもよい。本実施形態の発明の印刷方法においては、上記の印刷時の上記インキ組成物を、上記の従来の印刷版、上記の浅版化した印刷版を用いて印刷することにより印刷物を得ることができる。 The printing plate to be used may be a conventional plate cylinder (an intaglio plate made by a usual gravure plate making method, and the plate making method may be exemplified by engraving gravure etc.), and forms a shallower cell than the conventional plate cylinder ( It may be a shallow plate). In the printing method of the invention of the present embodiment, a printed material can be obtained by printing the above-mentioned ink composition at the time of printing using the above-mentioned conventional printing plate and the above-described printing plate which has been made thin .
以上、本実施形態によれば、光学濃度が高く、マイレージ、耐アルコール性が良好な印刷物が得られる。 As described above, according to the present embodiment, a printed material having high optical density and good mileage and alcohol resistance can be obtained.
以下、実施例により本発明をより具体的に説明する。本発明は、これら実施例に何ら限定されない。なお、特に制限のない限り、「％」は「質量％」を意味し、「部」は「質量部」を意味する。 Hereinafter, the present invention will be more specifically described by way of examples. The present invention is not limited to these examples. In addition, unless there is a restriction in particular, "%" means "mass%" and "part" means "mass part."
使用した原料および調製方法を以下に示す。
＜顔料＞
ＰＢ１５：４
＜ニトロセルロース樹脂＞
ＫＯＲＥＡ ＣＮＣ社製の硝化綿：ＴＲ１／１６（０．０６５Ｐａ・ｓ）
（固形分７０％、イソプロピルアルコール３０％）
ＫＯＲＥＡ ＣＮＣ社製の硝化綿：ＳＳ１／４（０．１５５Ｐａ・ｓ）
（固形分７０％、イソプロピルアルコール３０％）
なお、上記粘度はいずれも、固形分２０％、酢酸エチル溶液：イソプロピルアルコール＝９０：１０の混合溶液における２５℃における３０ｒｐｍでの粘度である。
＜塩化ビニル−酢酸ビニル共重合体樹脂＞
塩化ビニル酢酸ビニル共重合体（商品名：ソルバインＡ、日信化学工業（株）製）
＜シリカ粒子＞
シリカ粒子：平均粒子径が０．０１６μｍ（アエロジルＲ９７２、日本アエロジル（株）製）
シリカ粒子：平均粒子径が２．７μｍ（サイリシア３１０、富士シリシア（株）製）
シリカ粒子：平均粒子径が３．９μｍ（サイリシア３５０、富士シリシア（株）製）
シリカ粒子：平均粒子径が５．０μｍ（サイロイド７０００、グレース社製）
シリカ粒子：平均粒子径が８．０μｍ（サイロイド４５０、グレース社製）
The raw materials used and the preparation method are shown below.
<Pigment>
PB 15: 4
<Nitrocellulose resin>
KOREA CNC's Nitrified Cotton: TR 1/16 (0.065 Pa · s)
(70% solids, 30% isopropyl alcohol)
KOREA CNC's Nitrified Cotton: SS1 / 4 (0.155 Pa · s)
(70% solids, 30% isopropyl alcohol)
The above viscosities are all the viscosities at 30 rpm at 25 ° C. in a mixed solution of solid content of 20% and ethyl acetate solution: isopropyl alcohol = 90: 10.
<Vinyl chloride-vinyl acetate copolymer resin>
Vinyl chloride-vinyl acetate copolymer (trade name: Solvaine A, manufactured by Nisshin Chemical Industry Co., Ltd.)
<Silica particles>
Silica particles: average particle diameter 0.016 μm (Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.)
Silica particles: 2.7 μm in average particle size (Sylysia 310, manufactured by Fuji Silysia Co., Ltd.)
Silica particles: average particle size 3.9 μm (Sylysia 350, manufactured by Fuji Silysia Co., Ltd.)
Silica particles: average particle size 5.0 μm (Tyroid 7000, manufactured by Grace)
Silica particles: average particle size 8.0 μm (Tyroid 450, manufactured by Grace)
＜実施例１〜８、比較例１〜３＞
（紙用溶剤型グラビア印刷インキ組成物の調製）
以下の表１に示される質量割合（質量％）にしたがって、それぞれの材料をペイントコンディショナーにて混練し、紙用溶剤型グラビア印刷インキ組成物を調製した。得られたインキ組成物について、経時安定性、印刷適性を評価した。また、得られたインキ組成物について、以下の条件にてグラビア印刷を行い、印刷物を得た。得られた印刷物について、以下の評価方法にしたがって、印刷濃度、耐アルコール性およびマイレージを評価した。結果を表１に示す。
Examples 1 to 8 and Comparative Examples 1 to 3
(Preparation of solvent-based gravure printing ink composition for paper)
Each material was kneaded with a paint conditioner in accordance with the mass ratio (mass%) shown in Table 1 below to prepare a solvent type gravure printing ink composition for paper. The temporal stability and printability of the obtained ink composition were evaluated. Moreover, about the obtained ink composition, gravure printing was performed on condition of the following, and the printed matter was obtained. The print density, alcohol resistance and mileage were evaluated according to the following evaluation method for the obtained printed matter. The results are shown in Table 1.
（グラビア印刷条件）
用紙：未コート紙
印刷機械：グラビア校正機
インキを印刷する刷版：ヘリオ１７５ｉｎｅ／ｉｎｃｈ（図柄：ベタ印刷版）
印刷速度：８０ｍ／ｍｉｎ
乾燥条件：８０℃
(Gravure printing conditions)
Paper: Uncoated paper Printing machine: Gravure proofer Printing plate for printing ink: Helio 175ine / inch (pattern: solid printing plate)
Printing speed: 80m / min
Drying conditions: 80 ° C
＜経時安定性＞
実施例１〜８、比較例１〜３のインキ組成物について、４０℃で７日間経時前後の粘度の値の変化（Ｂ型粘度計の３０ｒｐｍでのインキ粘度測定データ）から経時粘度安定性の評価を行い、以下の評価基準にしたがって評価した。
（評価基準）
Ａ：経時後／経時前の粘度比が１．５未満であった。
Ｂ：経時後／経時前の粘度比が１．５以上、３．０未満であった。
Ｃ：経時後／経時前の粘度比が３．０以上であった。
<Temporal stability>
The ink compositions of Examples 1 to 8 and Comparative Examples 1 to 3 have viscosity stability over time from change in viscosity value (ink viscosity measurement data at 30 rpm of a B-type viscometer) before and after aging for 7 days at 40 ° C. Evaluation was performed and evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: The viscosity ratio after aging / before aging was less than 1.5.
B: The viscosity ratio after aging / before aging was 1.5 or more and less than 3.0.
C: The viscosity ratio after aging / before aging was 3.0 or more.
＜印刷適性＞
印刷適性については、印刷終了時のベタ部分におけるレベリング性より、以下の評価基準にしたがって評価した。
（評価基準）
Ａ：レベリングが良好であり、ベタ部の濃淡がなかった。
Ｂ：レベリングが悪く、ベタ部の濃淡があった。
<Printability>
The printability was evaluated according to the following evaluation criteria from the leveling property of the solid portion at the end of printing.
(Evaluation criteria)
A: The leveling was good and there was no shading of the solid part.
B: The leveling was bad, and there was a shade of the solid part.
＜印刷濃度＞
印刷濃度については、藍色の印刷物の反射濃度を濃度計（ＲＤ−９１８ マクベス社製）にて測定した。
<Print density>
Regarding the printing density, the reflection density of the amber printed matter was measured with a densitometer (manufactured by RD-918 Macbeth).
＜耐アルコール性＞
各印刷面をエタノール／水＝８／２の混合液で浸した綿棒でこすり、印刷面の取れ具合から耐アルコール性を、以下の評価基準にしたがって評価した。
（評価基準）
Ａ：５０回以上こすっても印刷面が取れなかった。
Ｂ：１０回〜４９回こすって印刷面が取れた。
Ｃ：１回〜９回こすって印刷面がとれた。
<Alcohol resistance>
Each printed surface was rubbed with a cotton swab soaked with a mixed solution of ethanol / water = 8/2, and the alcohol resistance was evaluated according to the following evaluation criteria from the degree of removal of the printed surface.
(Evaluation criteria)
A: I could not get the printing surface even after rubbing 50 times or more.
B: The printed surface was removed 10 to 49 times.
C: The printing surface was taken off by rubbing once to 9 times.
＜マイレージ＞
印刷前の未コート紙を温度２３℃、湿度５０％に調湿しておき、未コート紙（３ｃｍ×２０ｃｍ）の重量を計測し、印刷後に同様の条件で調湿後、印刷物（３ｃｍ×２０ｃｍ）の重量を計測し塗布量を算出し、以下の評価基準にしたがってマイレージを評価した。
（評価基準）
Ａ：塗布量が６〜８ｇ／ｍ2であった。
Ｂ：塗布量が８〜１０ｇ／ｍ2であった。
Ｃ：塗布量が１０〜１２ｇ／ｍ2であった。
<Mileage>
The uncoated paper before printing is conditioned at a temperature of 23 ° C. and a humidity of 50%, the weight of the uncoated paper (3 cm × 20 cm) is measured, and after printing under the same conditions after printing, the printed matter (3 cm × 20 cm) The weight of the above was measured, the application amount was calculated, and the mileage was evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: The application amount was 6 to 8 g / m 2 .
B: The application amount was 8 to 10 g / m 2 .
C: The application amount was 10 to 12 g / m 2 .
表１に示されるように、実施例１〜８のインキ組成物は、いずれも、経時安定性が良好であり、かつ、レベリング性も優れていた。また、得られた印刷物は、高濃度であり、耐アルコール性、マイレージのいずれも優れていた。一方、シリカ粒子を配合しなかった比較例１のインキ組成物は、得られた印刷物のマイレージが劣った。また、平均粒子径の小さなシリカ粒子を配合した比較例２のインキ組成物は、耐アルコール性が劣った。さらに、シリカ粒子の配合量を少なくした比較例３のインキ組成物は、耐アルコール性が劣った。 As shown in Table 1, all of the ink compositions of Examples 1 to 8 had good stability over time, and also had excellent leveling properties. Moreover, the obtained printed matter was high in concentration, and both of the alcohol resistance and the mileage were excellent. On the other hand, in the ink composition of Comparative Example 1 in which no silica particles were blended, the mileage of the obtained printed matter was inferior. Moreover, the ink composition of Comparative Example 2 in which silica particles having a small average particle size were blended was inferior in alcohol resistance. Furthermore, the ink composition of Comparative Example 3 in which the amount of the silica particles was reduced was inferior in alcohol resistance.
Claims (3)
前記シリカ粒子の含有量は、インキ組成物中、０．１〜２質量％であり、
前記有機溶剤は、非芳香族系有機溶剤を含む、紙用溶剤型グラビア印刷インキ組成物。 A pigment, a binder resin, an organic solvent, and silica particles having an average particle diameter of 6 μm or less,
The content of the silica particles is 0.1 to 2% by mass in the ink composition,
The solvent-based gravure printing ink composition for paper, wherein the organic solvent comprises a non-aromatic organic solvent.
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| JP6993529B1 (en) | 2021-06-02 | 2022-01-13 | 大日精化工業株式会社 | Gravure ink composition for plastic base material and its manufacturing method |
| JP2022185246A (en) * | 2021-06-02 | 2022-12-14 | 大日精化工業株式会社 | Gravure ink composition for plastic substrates and method for producing the same |
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