JP2013142150A - Water-based gravure printing ink composition for carton - Google Patents
Water-based gravure printing ink composition for carton Download PDFInfo
- Publication number
- JP2013142150A JP2013142150A JP2012004363A JP2012004363A JP2013142150A JP 2013142150 A JP2013142150 A JP 2013142150A JP 2012004363 A JP2012004363 A JP 2012004363A JP 2012004363 A JP2012004363 A JP 2012004363A JP 2013142150 A JP2013142150 A JP 2013142150A
- Authority
- JP
- Japan
- Prior art keywords
- water
- gravure printing
- ink composition
- aqueous
- printing ink
- 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.)
- Granted
Links
- 238000007646 gravure printing Methods 0.000 title claims abstract description 76
- 239000000203 mixture Substances 0.000 title claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000007639 printing Methods 0.000 claims abstract description 81
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000011347 resin Substances 0.000 claims abstract description 54
- 229920005989 resin Polymers 0.000 claims abstract description 54
- 239000002028 Biomass Substances 0.000 claims abstract description 26
- 239000012736 aqueous medium Substances 0.000 claims abstract description 19
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 239000003086 colorant Substances 0.000 claims abstract description 12
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 229940117955 isoamyl acetate Drugs 0.000 claims abstract description 6
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZMFWEWMHABZQNB-UHFFFAOYSA-N 6-acetyloxyhexyl acetate Chemical compound CC(=O)OCCCCCCOC(C)=O ZMFWEWMHABZQNB-UHFFFAOYSA-N 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- VPJOGDPLXNTKAZ-UHFFFAOYSA-N 2-methylpropanoic acid;2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)=O.CC(C)C(O)C(C)(C)CO VPJOGDPLXNTKAZ-UHFFFAOYSA-N 0.000 claims description 4
- UOWSVNMPHMJCBZ-UHFFFAOYSA-N 1-[2-(2-butoxypropoxy)propoxy]butane Chemical compound CCCCOCC(C)OCC(C)OCCCC UOWSVNMPHMJCBZ-UHFFFAOYSA-N 0.000 claims description 2
- KJOVIRMWPFJSTR-UHFFFAOYSA-N 1-butan-2-yloxypropan-2-ol Chemical compound CCC(C)OCC(C)O KJOVIRMWPFJSTR-UHFFFAOYSA-N 0.000 claims description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 2
- DBUMQODMPXCGAY-UHFFFAOYSA-N 2-(2-butan-2-yloxypropoxy)propan-1-ol Chemical compound CCC(C)OC(C)COC(C)CO DBUMQODMPXCGAY-UHFFFAOYSA-N 0.000 claims description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 2
- DRLRGHZJOQGQEC-UHFFFAOYSA-N 2-(2-methoxypropoxy)propyl acetate Chemical compound COC(C)COC(C)COC(C)=O DRLRGHZJOQGQEC-UHFFFAOYSA-N 0.000 claims description 2
- OADIZUFHUPTFAG-UHFFFAOYSA-N 2-[2-(2-ethylhexoxy)ethoxy]ethanol Chemical compound CCCCC(CC)COCCOCCO OADIZUFHUPTFAG-UHFFFAOYSA-N 0.000 claims description 2
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 claims description 2
- CIURCIMZEPBPPG-UHFFFAOYSA-N CC(CCC)OC(C)COC(C)CO Chemical compound CC(CCC)OC(C)COC(C)CO CIURCIMZEPBPPG-UHFFFAOYSA-N 0.000 claims description 2
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 58
- 239000001569 carbon dioxide Substances 0.000 abstract description 29
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 29
- 238000001035 drying Methods 0.000 abstract description 29
- 239000012855 volatile organic compound Substances 0.000 abstract description 16
- 239000000839 emulsion Substances 0.000 abstract description 3
- DLTXRGFRPZKYNS-UHFFFAOYSA-N 2-methylpropan-1-ol;2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)CO.CC(C)C(O)C(C)(C)CO DLTXRGFRPZKYNS-UHFFFAOYSA-N 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 83
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 17
- 239000000049 pigment Substances 0.000 description 17
- 239000002253 acid Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
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- 235000013405 beer Nutrition 0.000 description 5
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- 229920000642 polymer Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
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- 230000007935 neutral effect Effects 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
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- 102100040471 Serine/threonine-protein phosphatase 2A regulatory subunit B'' subunit beta Human genes 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
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- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
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- HGERSUQOJQWENV-UHFFFAOYSA-N 1-pentan-2-yloxypropan-2-ol Chemical compound CCCC(C)OCC(C)O HGERSUQOJQWENV-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
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- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- 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 1
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Abstract
Description
本発明は、紙器用水性グラビア印刷インキ組成物に関し、より詳しくは、印刷により発生する揮発性有機化合物や二酸化炭素の排出量を低減でき、良好な乾燥性と印刷適性とを有する紙器用水性グラビア印刷インキ組成物に関する。 The present invention relates to a water-based gravure printing ink composition for paper containers, and more specifically, can reduce the discharge amount of volatile organic compounds and carbon dioxide generated by printing, and has a good drying property and printability. The present invention relates to a printing ink composition.
菓子等の食品や、ティッシュ、洗剤等の家庭用品等の外装箱、酒等の飲料のマルチパック用パッケージ等には、通常、美粧化のために水性インキがグラビア方式で印刷され表面保護や光沢付与のために水性オーバープリントニスが塗工されている。
例えば、最近、缶ビールは、６缶パックとして陳列・販売される機会が非常に多くなっている。そして、特に目につくのがそれらのパーケージの印刷のきれいさである。ビール業界の市場シェア争いは熾烈を極め、最近では０．１％程度の差で売り上げランキングが入れ替わる可能性すらある。ビール業界に限ったことではないが、売り上げランキングのトップ企業には高いステイタスがあり、それが世間の信用や認知度にも結びつく。そこで、ビール業界では広告・宣伝への注力はもとより、お客様が製品を手に取ったときの印象が少しでも良くなるように、印刷業界を巻き込んで、缶やパッケージの印刷品質にまでこだわった販売戦略がとられている。このような外装箱や飲料のマルチパック用パッケージ等の印刷用基材には、表面に炭酸カルシウム等の無機粒子と樹脂等とからなる塗工層を緻密に設けたコート紙が利用されている。コート紙は、表面が平滑で光沢があり、また、水性インキ等の被覆剤組成物の浸透を抑制して歩留まり性を高めるという特徴を有するために、精緻で高濃度な印刷と光沢の付与とを可能にする。しかし、コート紙は、水性媒体を有する被覆剤組成物を印刷・塗工した際に、被覆剤組成物の乾燥を阻害するという欠点がある。内部への浸透による被覆剤組成物の乾燥が期待できる印刷用基材を用いた場合は、通常、被覆剤組成物の水性媒体が水のみでも良好な乾燥性が得られる。ところが、コート紙を用いた場合、浸透の抑制により乾燥が阻害されるため、被覆剤組成物の乾燥性が低下する。被覆剤組成物の乾燥性は印刷物の生産効率に直結するファクターであり、特に大量に消費される缶ビール等のパッケージの印刷では極めて重要な性能となる。そこで、コート紙を利用して、いかに乾燥性の低下をなくすかが大きな検討課題になっていた。
For food such as confectionery, exterior boxes for household items such as tissues and detergents, and multipack packages for beverages such as liquor, water-based inks are usually printed in a gravure system for cosmetics and are used for surface protection and gloss. A water-based overprint varnish is applied for application.
For example, recently, canned beer has been very often displayed and sold as a six-can pack. And what is particularly noticeable is the cleanness of the printing of those packages. The competition for market share in the beer industry is extremely fierce, and recently there is a possibility that the sales ranking will change by about 0.1%. Although it is not limited to the beer industry, the top companies in sales rankings have high status, which leads to public trust and recognition. Therefore, in the beer industry, sales focused on the printing quality of cans and packages, not only focusing on advertising and publicity, but also involving the printing industry so that the impression that the customer picks up the product is as good as possible. Strategy is taken. For such printing substrates such as exterior boxes and beverage multipack packages, coated paper having a coating layer densely composed of inorganic particles such as calcium carbonate and a resin is used on the surface. . The coated paper has a smooth surface and gloss, and also has the characteristics of suppressing the penetration of a coating composition such as a water-based ink and improving the yield. Enable. However, the coated paper has a drawback in that drying of the coating composition is inhibited when the coating composition having an aqueous medium is printed and applied. When a printing substrate that can be expected to dry the coating composition by penetrating into the inside is used, usually good drying properties can be obtained even if the aqueous medium of the coating composition is water alone. However, when coated paper is used, drying is inhibited by suppressing permeation, so that the drying property of the coating composition is lowered. The drying property of the coating composition is a factor directly related to the production efficiency of printed matter, and is extremely important for printing packages such as canned beer that are consumed in large quantities. Thus, how to use coated paper to eliminate the decrease in drying property has been a major study subject.
また、コート紙における、被覆剤組成物の浸透を抑制する性能は、同時に被覆剤組成物の紙面での広がりも抑制することから、コート紙を用いた場合、印刷時に、シャドウ部（網点面積率の高い部分）では印刷抜けが生じたり、ハイライト部（網点面積率の低い部分）ではざらついた感じに見えたりするといった問題があった。そして、グラビア印刷方式では、この様な印刷抜けやざらつき感が顕著になりやすい。 In addition, the ability to suppress the penetration of the coating composition in the coated paper also suppresses the spread of the coating composition on the paper surface. There is a problem that printing omission occurs in a portion where the rate is high) and that the highlight portion (a portion where the dot area ratio is low) looks rough. In the gravure printing method, such omission of printing and a feeling of roughness tend to be remarkable.
グラビア印刷とは、円筒状の版材の表面に、画像部として“セル”と呼ばれる円筒状、格子状、ピラミッド状等の独立した微細な凹部を設け、その中に水性インキを充填し、ドクターブレードと呼ばれる板状の部材で凹部以外の部分に付着した水性インキを掻き取った後、版面に印刷基材を押圧し、セル内に残った水性インキのみを印刷基材に転移させる印刷方式である。ここで、水性インキがセルから印刷基材に転移した後に広がらないと、インキは印刷基材上で点在することになり、印刷抜けやざらつき感が生じる。したがって、インキの広がり性（レベリング性）は、印刷抜けやざらつき感をなくすために必要な性能と言える。なお、インキが広がりすぎると、今度はぼやけた感じになるため、レベリング性には適度な範囲が求められる。 In gravure printing, the surface of a cylindrical plate material is provided with independent fine concave portions called “cells” as image portions such as cylindrical, lattice, and pyramid shapes, and filled with water-based ink in it. In this printing method, after scraping off the water-based ink adhering to the parts other than the recesses with a plate-like member called a blade, the printing substrate is pressed against the plate surface, and only the water-based ink remaining in the cells is transferred to the printing substrate. is there. Here, if water-based ink does not spread after transferring from a cell to a printing base material, the ink will be scattered on the printing base material, and printing omission and a rough feeling will arise. Therefore, the spreadability (leveling property) of the ink can be said to be a performance necessary for eliminating the lack of printing and the feeling of roughness. Note that if the ink spreads too much, it will become blurred this time, so an appropriate range is required for leveling properties.
グラビア印刷における水性インキの乾燥性やレベリング性を向上させるためには、水性インキに水性媒体として低級アルコールを含有させることが効果的である。そこで、通常、コート紙に印刷・塗工される際の水性インキには、低級アルコールが４０質量％程度と多量に含まれている（例えば、特許文献１参照）。 In order to improve the drying property and leveling property of the water-based ink in gravure printing, it is effective to contain a lower alcohol as an aqueous medium in the water-based ink. Therefore, the water-based ink used for printing / coating on coated paper usually contains a large amount of lower alcohol of about 40% by mass (see, for example, Patent Document 1).
しかし、近年、自然環境の保護や労働環境の改善が強く求められるようになり、印刷業界においても、揮発性有機化合物（ＶＯＣ）や二酸化炭素の排出量削減することが求められている。そして、グラビア印刷で規制対象となるのは、「グラビア印刷の用に供する乾燥施設の送風能力が２７０００ｍ３／時間以上」の場合であり、ＶＯＣ排出濃度を、これまでの１３００ｐｐｍＣ（ｐｐｍＣ＝溶剤排出量×炭素数）から７００ｐｐｍＣまで削減する必要がある。
クラビア印刷を行う場合において、ＶＯＣや二酸化炭素の排出量を削減する方法として、（１）インキに含まれる低級アルコール量を低減する方法、（２）グラビア印刷版深度（セルの深さ）を浅くして（浅版化）印刷することによって、印刷時のインキ使用量を低減する方法（例えば、特許文献２参照）が考えられる。
しかしながら、（１）のこれまで利用されてきた水性被覆剤組成物から、単に低級アルコール量を低減しただけの場合、紙器用水性グラビア印刷インキ組成物では、印刷適性や乾燥性が低下するという問題があった。
また、（２）の方法では、グラビア印刷版の浅版化に伴ってセル容積が減少して印刷時のインキ組成物の転移量が少なくなるため、有機溶剤の蒸発量は抑えられ、ＶＯＣや二酸化炭素の排出量を削減することはできるが、インキ皮膜が薄膜となるため、相対的に顔料分が少なくなり、色濃度が低下する等の問題があった。
However, in recent years, protection of the natural environment and improvement of the working environment have been strongly demanded, and the printing industry is also required to reduce emissions of volatile organic compounds (VOC) and carbon dioxide. And, the subject of regulation in gravure printing is the case where “the air blowing capacity of the drying facility used for gravure printing is 27000 m 3 / hour or more”, and the VOC emission concentration is 1300 ppmC (ppmC = solvent emission) Amount x carbon number) to 700 ppmC.
In the case of performing gravure printing, (1) a method of reducing the amount of lower alcohol contained in the ink, and (2) a gravure printing plate depth (cell depth) as a method for reducing the amount of VOC and carbon dioxide emission. Then, a method of reducing the amount of ink used during printing by printing (shallow printing) (for example, see Patent Document 2) can be considered.
However, when the amount of the lower alcohol is simply reduced from the aqueous coating composition that has been used in the past (1), the water-based gravure printing ink composition for paper containers has a problem that printability and drying properties are lowered. was there.
Further, in the method (2), the cell volume decreases with the shallowing of the gravure printing plate, and the transfer amount of the ink composition at the time of printing decreases. Therefore, the evaporation amount of the organic solvent can be suppressed, and VOC and Although the amount of carbon dioxide emission can be reduced, the ink film becomes a thin film, so that there is a problem that the pigment content is relatively reduced and the color density is lowered.
以上の様に、印刷中に蒸発する低級アルコールの絶対量を減量しながら、グラビア印刷特有の美粧印刷物を得ることについては相当な困難が伴うことになる。そこで、低級アルコールの絶対量を減少させる代わりに、利用する低級アルコールをバイオマス由来のものとする方法も提唱されている（例えば、特許文献３、４参照）。大気中にそのまま有機溶剤が排出されると大気汚染の原因となるため、最近では、印刷中に蒸発する有機溶剤を回収して燃焼処理するようになっている。アルコールが燃焼処理される際には水と二酸化炭素が発生する。このとき、バイオマス由来のアルコールであれば、発生する二酸化炭素は、植物が成長する過程で大気中から吸収した二酸化炭素と同量（カーボンニュートラル）と考えられ、差し引きするとバイオマス由来のアルコールを用いることにより新たに発生する二酸化炭素の量はゼロとみなされる。ただし、現在のところ、バイオマス由来のアルコールとして実用的なのは、ほぼエタノールのみという状況であり、インキ用溶剤としてもエタノールに限定される。 As described above, it is considerably difficult to obtain a cosmetic print peculiar to gravure printing while reducing the absolute amount of lower alcohol evaporated during printing. Then, instead of reducing the absolute amount of the lower alcohol, a method in which the lower alcohol to be used is derived from biomass has been proposed (see, for example, Patent Documents 3 and 4). If the organic solvent is discharged into the atmosphere as it is, it causes air pollution, and recently, the organic solvent that evaporates during printing has been recovered and burned. When alcohol is burned, water and carbon dioxide are generated. At this time, if it is alcohol derived from biomass, the generated carbon dioxide is considered to be the same amount (carbon neutral) as carbon dioxide absorbed from the atmosphere during the growth of the plant, and if subtracted, use alcohol derived from biomass. Therefore, the amount of newly generated carbon dioxide is regarded as zero. However, at present, only ethanol is practical as a biomass-derived alcohol, and the ink solvent is limited to ethanol.
従来、水性タイプのインキでは、乾燥性や印刷改質性の制御が容易な（イソ）プロパノールが好んで利用されてきたが、エタノールに置き換えても得られる利点は多い。たとえば、（イソ）プロパノールよりエタノールの方が、有害性が低いため大気汚染や作業環境などに悪影響を及ぼす可能性が低くなる。また、（イソ）プロパノールとエタノールが同質量のときに、燃焼処理によって発生する二酸化炭素の量はエタノールの方が１３％程度少なくなる。従って、環境負荷を軽減するには、バイオマス由来のエタノールの利用は好ましいと言える。しかし、水性タイプのインキではアルコール成分をエタノール主体とした時に、印刷改質性が充分でなく、印刷抜けやざらつき感が出やすいという問題がある。 Conventionally, (iso) propanol, which is easy to control drying properties and print modification properties, has been used favorably for water-based inks, but there are many advantages that can be obtained by replacing it with ethanol. For example, ethanol is less harmful than (iso) propanol, so it is less likely to adversely affect air pollution or the work environment. Further, when (iso) propanol and ethanol have the same mass, the amount of carbon dioxide generated by the combustion treatment is about 13% less in ethanol. Therefore, it can be said that the use of biomass-derived ethanol is preferable to reduce the environmental burden. However, in the case of water-based ink, there is a problem that when the alcohol component is mainly ethanol, the printing property is not sufficient, and printing omission and rough feeling are likely to occur.
新しいインキの開発において環境問題の解決は、確かに社会的な命題であり、（イソ）プロパノールからバイオマス由来のエタノールへの置き換えは望ましい。しかし、如何に環境対応といえども、印刷物の良し悪しが商品の売れ行きを左右する可能性がある中で、高品質印刷物を得るというグラビア印刷本来の目的からすると、ざらつき感が目立つと実用性を損なう大きな要因になる。したがって、上記で提唱されているような、単にバイオマス由来のアルコールを利用するというだけでは、環境問題を解決するという効果は期待できるものの、印刷物としての実用性能に乏しいために、市場としては受け入れ難いというのが現状である。 Solving environmental problems is certainly a social proposition in the development of new inks, and the replacement of (iso) propanol with biomass-derived ethanol is desirable. However, even though it is environmentally friendly, there is a possibility that the quality of the printed matter may affect the sales of the product. From the original purpose of gravure printing to obtain a high-quality printed matter, if the roughness is noticeable, it will be useful. It becomes a big factor to lose. Therefore, simply using biomass-derived alcohol, as proposed above, can be expected to solve environmental problems, but it is difficult to accept as a market because it lacks practical performance as a printed matter. That is the current situation.
本発明は、印刷により発生する揮発性有機化合物や二酸化炭素の排出量を低減でき、良好な乾燥性と印刷適性とを有する紙器用水性グラビア印刷インキ組成物を提供することを目的とする。 An object of the present invention is to provide an aqueous gravure printing ink composition for paper containers that can reduce emissions of volatile organic compounds and carbon dioxide generated by printing and has good drying properties and printability.
本発明は、着色剤、アルカリ可溶型水溶性樹脂、エマルジョン型の水性樹脂、印刷改質剤、及び、水性媒体を含有する紙器用水性グラビア印刷インキ組成物であって、上記水性媒体は、水と炭素数１〜４の低級アルコールとを含有し、上記低級アルコールは、バイオマス由来のアルコールを含有し、上記印刷改質剤は、下記式（１）で表わされる化合物、下記式（２）で表わされる化合物、２−ブチル−２−エチル−１，３−プロパンジオール、２，４−ジエチル−１，５−ペンタンジオール、２，２，４−トリメチル−１，３−ペンタンジオールイソブチレート、２−エチル−１，３−ヘキサンジオール、１，６−ヘキサンジオールジアセテート、及び、イソアミルアセテートからなる群より選択される少なくとも１種である紙器用水性グラビア印刷インキ組成物である。 The present invention is a water gravure printing ink composition for paper containers containing a colorant, an alkali-soluble water-soluble resin, an emulsion-type aqueous resin, a printing modifier, and an aqueous medium, wherein the aqueous medium is It contains water and a lower alcohol having 1 to 4 carbon atoms, the lower alcohol contains biomass-derived alcohol, and the printing modifier is a compound represented by the following formula (1), the following formula (2) 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol isobutyrate , 2-ethyl-1,3-hexanediol, 1,6-hexanediol diacetate, and at least one selected from the group consisting of isoamyl acetate A via printing ink composition.
式（１）中、Ｒ１、Ｒ２は、それぞれ独立して水素又はアルキル基であって、Ｒ１の炭素数とＲ２の炭素数の和が４以上であり、ｍは２又は３、ｎは１、２又は３である。 In formula (1), R 1 and R 2 are each independently hydrogen or an alkyl group, the sum of the carbon number of R 1 and the carbon number of R 2 is 4 or more, m is 2 or 3, n is 1, 2 or 3.
式（２）中、Ｒ３は炭素数が１〜４のアルキル基であり、ｍは２又は３である。
以下、本発明について詳述する。
In Formula (2), R 3 is an alkyl group having 1 to 4 carbon atoms, and m is 2 or 3.
Hereinafter, the present invention will be described in detail.
本発明者らは、鋭意検討した結果、バイオマス由来の低級アルコールを含有する水性媒体と、特定の印刷改質剤とを組み合わせて用いることにより、印刷により発生する揮発性有機化合物や二酸化炭素の排出量を低減でき、良好な乾燥性と印刷適性とを有する紙器用水性グラビア印刷インキ組成物を得ることができることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have used a combination of an aqueous medium containing a biomass-derived lower alcohol and a specific printing modifier to discharge volatile organic compounds and carbon dioxide generated by printing. It has been found that a water-based gravure printing ink composition for paper containers having a reduced amount and good drying properties and printability can be obtained, and the present invention has been completed.
本発明の紙器用水性グラビア印刷インキ組成物は、着色剤を含有する。
上記着色剤としては特に限定されず、通常、水性印刷インキに使用される従来公知の顔料が挙げられる。具体的には、無機顔料としては、例えば、酸化チタン、ベンガラ、アンチモンレッド、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、黒鉛等が挙げられる。また、有機顔料としては、例えば、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、縮合多環顔料等が挙げられる。
The aqueous gravure printing ink composition for paper containers of the present invention contains a colorant.
The colorant is not particularly limited, and examples thereof include conventionally known pigments that are usually used in aqueous printing inks. Specifically, examples of the inorganic pigment include titanium oxide, bengara, antimony red, cadmium yellow, cobalt blue, bitumen, ultramarine blue, carbon black, and graphite. Examples of organic pigments include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments.
本発明の紙器用水性グラビア印刷インキ組成物において、上記着色剤の含有量は、印刷時において、好ましい下限が４質量％、好ましい上限が１１質量％である。印刷時の着色剤の含有量が４質量％未満であると、印刷物の印刷濃度が低くなることがある。印刷時の着色剤の含有量が１１質量％を超えると、得られる紙器用水性グラビア印刷インキ組成物の粘度が高くなりすぎることがある。 In the aqueous gravure printing ink composition for paper containers of the present invention, the content of the colorant is preferably 4% by mass in the preferred lower limit and 11% by mass in the preferred upper limit during printing. When the content of the colorant at the time of printing is less than 4% by mass, the print density of the printed matter may be lowered. When content of the coloring agent at the time of printing exceeds 11 mass%, the viscosity of the aqueous gravure printing ink composition for paper containers obtained may become high too much.
本発明の紙器用水性グラビア印刷インキ組成物は、上記着色剤の分散性を向上させることを目的として分散剤を含有してもよい。
上記分散剤としては特に限定されず、従来の紙器用水性グラビア印刷インキ組成物において、顔料等の分散性向上に使用される公知の分散剤が挙げられる。
The aqueous gravure printing ink composition for paper containers of the present invention may contain a dispersant for the purpose of improving the dispersibility of the colorant.
It does not specifically limit as said dispersing agent, In the conventional water-based gravure printing ink composition for paper containers, the well-known dispersing agent used for dispersibility improvement of a pigment etc. is mentioned.
また、本発明の紙器用水性グラビア印刷インキ組成物は、乾燥性や流動性を向上させることを目的として、体質顔料を含有してもよい。
上記体質顔料としては、例えば、炭酸カルシウム、カオリン、硫酸バリウム、水酸化アルミニウム、クレー、タルク等が挙げられる。
Moreover, the water based gravure printing ink composition for paper containers of the present invention may contain extender pigments for the purpose of improving drying properties and fluidity.
Examples of the extender pigment include calcium carbonate, kaolin, barium sulfate, aluminum hydroxide, clay, and talc.
本発明の紙器用水性グラビア印刷インキ組成物は、水性媒体を含有する。
上記水性媒体は、水と炭素数１〜４の低級アルコールとを含有する。
上記炭素数１〜４の低級アルコールとしては、従来から紙器用水性グラビア印刷インキ組成物に使用されているものであれば特に限定されず、石油由来のメタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、ｓｅｃ−ブタノール、ｔｅｒｔ−ブタノール、イソブタノール等が挙げられる。なかでも、印刷時の揮発性有機化合物の排出量や、燃焼した場合の二酸化炭素の発生量を低減させることができることから、エタノールが好ましい。
The aqueous gravure printing ink composition for paper containers of the present invention contains an aqueous medium.
The aqueous medium contains water and a lower alcohol having 1 to 4 carbon atoms.
The lower alcohol having 1 to 4 carbon atoms is not particularly limited as long as it is conventionally used in water-based gravure printing ink compositions for paper containers, and petroleum-derived methanol, ethanol, n-propanol, isopropanol, n -Butanol, sec-butanol, tert-butanol, isobutanol and the like. Among these, ethanol is preferable because it can reduce the amount of volatile organic compounds discharged during printing and the amount of carbon dioxide generated when burned.
上記炭素数１〜４の低級アルコールは、バイオマス由来のアルコールを含有する。ＶＯＣや二酸化炭素の排出量を低減させることができるため、上記低級アルコールは、全部がバイオマス由来のアルコールであることが好ましい。バイオマス由来のアルコールから発生する二酸化炭素は、植物が成長する過程で大気中から吸収した二酸化炭素と同量（カーボンニュートラル）と考えられ、差し引きすると、バイオマス由来のアルコールを使用することにより新たに発生する二酸化炭素の量はゼロとみなされる。
上記バイオマス由来のアルコールとしては、例えば、さとうきび、トウモロコシ等の穀物や木材等から得られる植物由来のアルコールが挙げられる。
The C1-C4 lower alcohol contains biomass-derived alcohol. Since the amount of VOC and carbon dioxide emissions can be reduced, the lower alcohol is preferably a biomass-derived alcohol. Carbon dioxide generated from biomass-derived alcohol is considered to be the same amount (carbon neutral) as carbon dioxide absorbed from the atmosphere during plant growth, and when subtracted, it is newly generated by using biomass-derived alcohol The amount of carbon dioxide to do is considered zero.
Examples of the biomass-derived alcohol include plant-derived alcohol obtained from cereals such as sugar cane and corn, wood, and the like.
本発明の紙器用水性グラビア印刷インキ組成物において、上記炭素数１〜４の低級アルコールの含有量の好ましい下限は１５質量％、好ましい上限は４０質量％である。上記炭素数１〜４の低級アルコールの含有量が１５質量％未満であると、印刷物に印刷抜けやざらつき感が生じることがある。上記炭素数１〜４の低級アルコールの含有量が４０質量％を超えると、ＶＯＣや二酸化炭素の大気中への放出が増加するので好ましくない。なお、上記炭素数１〜４の低級アルコールとしてバイオマス由来のアルコールを使用する場合は、含有量が４０質量％を超える場合でも、上述したように新たに発生する二酸化炭素の量はゼロとみなされるが、ＶＯＣや二酸化炭素の大気中への放出量が増加するので好ましくない。上記炭素数１〜４の低級アルコールの含有量のより好ましい上限は３０質量％である。 In the aqueous gravure printing ink composition for paper containers of the present invention, the preferable lower limit of the content of the lower alcohol having 1 to 4 carbon atoms is 15% by mass, and the preferable upper limit is 40% by mass. When the content of the lower alcohol having 1 to 4 carbon atoms is less than 15% by mass, the printed matter may have a print omission or a rough feeling. When the content of the lower alcohol having 1 to 4 carbon atoms exceeds 40% by mass, the release of VOC and carbon dioxide into the atmosphere is not preferable. In addition, when using biomass-derived alcohol as the lower alcohol having 1 to 4 carbon atoms, the amount of newly generated carbon dioxide is considered to be zero as described above even when the content exceeds 40% by mass. However, this is not preferable because the amount of VOC and carbon dioxide released into the atmosphere increases. The upper limit with more preferable content of the said C1-C4 lower alcohol is 30 mass%.
なお、通常の紙器用水性グラビア印刷インキ組成物に使用される、多価アルコールやその誘導体等のその他の有機溶剤については、本発明の効果を阻害しない範囲で含有してもよいが、ＶＯＣや二酸化炭素の大気中への放出を防止するという目的から、極力、その他の有機溶剤を含まないことが好ましい。 In addition, other organic solvents such as polyhydric alcohols and derivatives thereof used in a normal water-based gravure printing ink composition for paper containers may be contained within a range that does not impair the effects of the present invention. For the purpose of preventing the release of carbon dioxide into the atmosphere, it is preferable to contain no other organic solvent as much as possible.
本発明の紙器用水性グラビア印刷インキ組成物は、アルカリ可溶型水溶性樹脂を含有する。
上記アルカリ可溶型水溶性樹脂としては、例えば、分子内にカルボキシル基等の酸基とエチレン性不飽和二重結合とを有する単量体を必須成分とする単量体混合物を重合させて得られる樹脂等が挙げられる。具体的には例えば、アクリル系、スチレン−アクリル系、スチレン−マレイン酸系、及び、スチレン−アクリル−マレイン酸系等のアルカリ可溶型水溶性樹脂が挙げられる。
The aqueous gravure printing ink composition for paper containers of the present invention contains an alkali-soluble water-soluble resin.
The alkali-soluble water-soluble resin is obtained, for example, by polymerizing a monomer mixture containing as essential components a monomer having an acid group such as a carboxyl group and an ethylenically unsaturated double bond in the molecule. And the like. Specific examples include alkali-soluble water-soluble resins such as acrylic, styrene-acrylic, styrene-maleic acid, and styrene-acrylic-maleic acid.
上記アルカリ可溶型水溶性樹脂の酸価は、好ましい下限が３０ｍｇＫＯＨ／ｇ、好ましい上限が３００ｍｇＫＯＨ／ｇである。上記アルカリ可溶型水溶性樹脂の酸価が３０ｍｇＫＯＨ／ｇ未満であると、上述した水性媒体中での溶解性に劣ることがある。上記アルカリ可溶型水溶性樹脂の酸価が３００ｍｇＫＯＨ／ｇを超えると、得られる印刷物の耐水性が低下することがある。
なお、本明細書において、上記「酸価」は、共重合体１ｇを得るために理論上必要な各単量体の量に対して、ＫＯＨの理論上の中和量を求め、その中和量の総和のｍｇ数を共重合体の酸価（理論酸価）とみなすことにより求めることができる。
A preferable lower limit of the acid value of the alkali-soluble water-soluble resin is 30 mgKOH / g, and a preferable upper limit is 300 mgKOH / g. When the acid value of the alkali-soluble water-soluble resin is less than 30 mg KOH / g, the solubility in an aqueous medium may be inferior. When the acid value of the alkali-soluble water-soluble resin exceeds 300 mgKOH / g, the water resistance of the obtained printed matter may be lowered.
In the present specification, the “acid value” refers to the theoretical neutralization amount of KOH with respect to the amount of each monomer theoretically necessary to obtain 1 g of the copolymer, It can be determined by regarding the total number of mg as the acid value (theoretical acid value) of the copolymer.
本発明の紙器用水性グラビア印刷インキ組成物において、上記アルカリ可溶型水溶性樹脂の含有量の好ましい下限は１質量％、好ましい上限は２５質量％である。上記アルカリ可溶型水溶性樹脂の含有量が１質量％未満であると、顔料の分散性が低下することがある。上記アルカリ可溶型水溶性樹脂の含有量が２５質量％を超えると、紙器用水性グラビア印刷インキ組成物の設計が困難となることがある。 In the aqueous gravure printing ink composition for paper containers of the present invention, the preferable lower limit of the content of the alkali-soluble water-soluble resin is 1% by mass, and the preferable upper limit is 25% by mass. When the content of the alkali-soluble water-soluble resin is less than 1% by mass, the dispersibility of the pigment may be lowered. If the content of the alkali-soluble water-soluble resin exceeds 25% by mass, it may be difficult to design an aqueous gravure printing ink composition for paper containers.
上記アルカリ可溶型水溶性樹脂は、通常、塩基性化合物の存在下で水中に溶解させて水溶性樹脂ワニスとして使用する。
上記塩基性化合物としては、例えば、有機アミン、アルカリ金属水酸化物等が挙げられる。上記有機アミンとしては、例えば、ジエチルアミン、トリエチルアミン、エチレンジアミン等のアルキルアミン、モノエタノールアミン、エチルエタノールアミン、ジエチルエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン等が挙げられる。
上記アルカリ金属水酸化物としては、例えば、水酸化ナトリウム、水酸化カリウム等が挙げられる。なかでも乾燥性を向上させるために、常温あるいはわずかの加温で容易に揮発するものが望ましい。
The alkali-soluble water-soluble resin is usually dissolved in water in the presence of a basic compound and used as a water-soluble resin varnish.
Examples of the basic compound include organic amines and alkali metal hydroxides. Examples of the organic amine include alkylamines such as diethylamine, triethylamine, and ethylenediamine, and alkanolamines such as monoethanolamine, ethylethanolamine, diethylethanolamine, diethanolamine, and triethanolamine.
Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. In particular, in order to improve the drying property, those that readily volatilize at normal temperature or slightly heated are desirable.
本発明の紙器用水性グラビア印刷インキ組成物は、本発明の効果を阻害しない範囲で、更に、上記アルカリ可溶型水溶性樹脂以外の他の水性バインダー樹脂ワニス、例えば、水性シェラックワニス、水性カゼインワニス、水性ロジンマレイン酸樹脂ワニス、水性ポリエステル樹脂ワニス、水溶性セルロースワニス等を含有してもよい。 The aqueous gravure printing ink composition for paper containers of the present invention is a range that does not impair the effects of the present invention, and further, an aqueous binder resin varnish other than the alkali-soluble water-soluble resin, such as an aqueous shellac varnish, aqueous casein A varnish, an aqueous rosin maleic acid resin varnish, an aqueous polyester resin varnish, a water-soluble cellulose varnish, and the like may be contained.
本発明の紙器用水性グラビア印刷インキ組成物は、エマルジョン型の水性樹脂を含有する。
上記エマルジョン型の水性樹脂としては、例えば、スチレン系単量体とエチレン性不飽和単量体とを含有する単量体混合物を、高分子乳化剤の存在下で、乳化重合して得られた樹脂、スチレン−アクリル系水性樹脂、スチレン−マレイン酸系水性樹脂、スチレン−アクリル−マレイン酸系水性樹脂等が挙げられる。
The aqueous gravure printing ink composition for paper containers of the present invention contains an emulsion-type aqueous resin.
As the emulsion-type aqueous resin, for example, a resin obtained by emulsion polymerization of a monomer mixture containing a styrene monomer and an ethylenically unsaturated monomer in the presence of a polymer emulsifier Styrene-acrylic aqueous resin, styrene-maleic acid-based aqueous resin, styrene-acrylic-maleic acid-based aqueous resin, and the like.
上記エマルジョン型の水性樹脂の酸価の好ましい下限は１０ｍｇＫＯＨ／ｇ、好ましい上限は１００ｍｇＫＯＨ／ｇである。上記エマルジョン型の水性樹脂の酸価が１０ｍｇＫＯＨ／ｇ未満であると、再溶解性が低下することがある。上記エマルジョン型の水性樹脂の酸価が１００ｍｇＫＯＨ／ｇより大きいと、得られる紙器用水性グラビア印刷インキ組成物が乾燥性に劣るものとなることがある。上記エマルジョン型の水性樹脂の酸価のより好ましい下限は３０ｍｇＫＯＨ／ｇ、より好ましい上限は５０ｍｇＫＯＨ／ｇである。
なお、上記エマルジョン型の水性樹脂の酸価は、高分子乳化剤に由来するものであり、例えば、酸価１００ｍｇＫＯＨ／ｇの高分子乳化剤が、水性樹脂の固形分比率として１０質量％含まれているときの酸価は酸価１０ｍｇＫＯＨ／ｇとなる。
The preferable lower limit of the acid value of the emulsion-type aqueous resin is 10 mgKOH / g, and the preferable upper limit is 100 mgKOH / g. If the acid value of the emulsion-type aqueous resin is less than 10 mgKOH / g, the re-solubility may be lowered. If the acid value of the emulsion-type aqueous resin is greater than 100 mgKOH / g, the resulting aqueous gravure printing ink composition for paper containers may be inferior in drying properties. The more preferable lower limit of the acid value of the emulsion-type aqueous resin is 30 mgKOH / g, and the more preferable upper limit is 50 mgKOH / g.
The acid value of the emulsion-type aqueous resin is derived from the polymer emulsifier. For example, the polymer emulsifier having an acid value of 100 mgKOH / g is contained in an amount of 10% by mass as the solid content ratio of the aqueous resin. The acid value at that time is 10 mg KOH / g.
上記エマルジョン型の水性樹脂のガラス転移温度の好ましい下限は１５℃、好ましい上限は１００℃である。また、上記エマルジョン型の水性樹脂のガラス転移温度が１５℃未満であると、印刷物のブロッキング性が低下することがある。上記エマルジョン型の水性樹脂のガラス転移温度が１００℃を超えると、印刷物の耐摩性が低下することがある。
なお、上記エマルジョン型の水性樹脂のガラス転移温度とは、乳化重合に利用される全ての単量体を、コア部、シェル部と分けずに１度に共重合した時に得られる共重合体のガラス転移温度を表す。
上記ガラス転移温度は、下記のｗｏｏｄの式により求めた理論ガラス転移温度である。
１／Ｔｇ＝Ｗ１／Ｔｇ１＋Ｗ２／Ｔｇ２＋Ｗ３／Ｔｇ３＋・・・・・＋Ｗｘ／Ｔｇｘ
上式ｗｏｏｄの中、Ｔｇ１〜Ｔｇｘは共重合体を構成する単量体１、２、３、・・・、ｘのそれぞれの単独重合体のガラス転移温度、Ｗ１〜Ｗｘは単量体１、２、３、・・・、ｘのそれぞれの質量分率、Ｔｇは理論ガラス転移温度を表す。ただし、ｗｏｏｄの式におけるガラス転移温度は絶対温度である。
The preferable lower limit of the glass transition temperature of the emulsion-type aqueous resin is 15 ° C., and the preferable upper limit is 100 ° C. Further, when the glass transition temperature of the emulsion-type aqueous resin is less than 15 ° C., the blocking property of the printed matter may be lowered. When the glass transition temperature of the emulsion type aqueous resin exceeds 100 ° C., the abrasion resistance of the printed matter may be lowered.
The glass transition temperature of the emulsion-type aqueous resin refers to the copolymer obtained when all monomers used for emulsion polymerization are copolymerized at one time without being divided into a core part and a shell part. Represents the glass transition temperature.
The glass transition temperature is a theoretical glass transition temperature obtained by the following wood equation.
1 / Tg = W 1 / Tg 1 + W 2 / Tg 2 + W 3 / Tg 3 + ····· + W x / Tg x
In the above formula wood, Tg 1 to Tg x are glass transition temperatures of homopolymers of monomers 1, 2, 3,..., X constituting the copolymer, and W 1 to W x are simply Each mass fraction of T1, 2, 3, ..., x, Tg represents a theoretical glass transition temperature. However, the glass transition temperature in the wood equation is an absolute temperature.
上記エマルジョン型の水性樹脂の含有量は、本発明の紙器用水性グラビア印刷インキ組成物に含まれる固形分中において、好ましい下限が１０質量％、好ましい上限が６０質量％である。固形分中における上記エマルジョン型の水性樹脂の含有量のより好ましい下限は３０質量％である。 The content of the emulsion-type aqueous resin has a preferable lower limit of 10% by mass and a preferable upper limit of 60% by mass in the solid content contained in the aqueous gravure printing ink composition for paper containers of the present invention. A more preferable lower limit of the content of the emulsion-type aqueous resin in the solid content is 30% by mass.
本発明の紙器用水性グラビア印刷インキ組成物は、印刷改質剤を含有する。上記バイオマス由来の炭素数１〜４の低級アルコールを含有する水性媒体と、上記印刷改質剤とを組み合わせて用いることにより、本発明の紙器用水性グラビア印刷インキ組成物は、印刷により発生する揮発性有機化合物や二酸化炭素の排出量を低減でき、かつ、良好な乾燥性と印刷適性とを有するものとなる。 The aqueous gravure printing ink composition for paper containers of the present invention contains a printing modifier. The aqueous gravure printing ink composition for paper containers of the present invention is a volatilization generated by printing by using a combination of the aqueous medium containing the lower alcohol having 1 to 4 carbon atoms derived from biomass and the printing modifier. The amount of discharge of organic organic compounds and carbon dioxide can be reduced, and it has good drying properties and printability.
上記印刷改質剤は、上記式（１）で表わされる化合物、上記式（２）で表わされる化合物、トリエチレングリコールジメチルエーテル、２−ブチル−２−エチル−１，３−プロパンジオール、２，４−ジエチル−１，５−ペンタンジオール、２，２，４−トリメチル−１，３−ペンタンジオールイソブチレート、２−エチル−１，３−ヘキサンジオール、１，６−ヘキサンジオールジアセテート、及び、イソアミルアセテートからなる群より選択される少なくとも１種である。
なかでも、印刷物の印刷抜けやざらつき感を抑制する効果に特に優れることから、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノ−２−エチルへキシルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、ジエチレングリコールモノブチルエーテルアセテート、トリエチレングリコールジメチルエーテル、プロピレングリコールメチル−ｎ−プロピルエーテル、プロピレングリコールメチル−ｎ−ブチルエーテル、ジプロピレングリコールメチル−ｎ−プロピルエーテル、ジプロピレングリコールメチル−ｎ−ブチルエーテル、ジプロピレングリコールジブチルエーテル、ジプロピレングリコールモノメチルエーテルアセテート、２−ブチル−２−エチル−１，３−プロパンジオール、２，４−ジエチル−１，５−ペンタンジオール、２，２，４−トリメチル−１，３−ペンタンジオールイソブチレート、２−エチル−１，３−ヘキサンジオール、１，６−ヘキサンジオールジアセテート、イソアミルアセテートの群より選択される少なくとも１種が好適である。
The printing modifier includes a compound represented by the above formula (1), a compound represented by the above formula (2), triethylene glycol dimethyl ether, 2-butyl-2-ethyl-1,3-propanediol, 2,4 -Diethyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol isobutyrate, 2-ethyl-1,3-hexanediol, 1,6-hexanediol diacetate, and It is at least one selected from the group consisting of isoamyl acetate.
Among these, diethylene glycol monobutyl ether, diethylene glycol mono-2-ethylhexyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol monobutyl ether acetate, triethylene glycol are particularly excellent in the effect of suppressing printing omission and rough feeling of printed matter. Dimethyl ether, propylene glycol methyl-n-propyl ether, propylene glycol methyl-n-butyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl-n-butyl ether, dipropylene glycol dibutyl ether, dipropylene glycol monomethyl ether acetate 2-butyl-2-ethyl-1,3-propane All, 2,4-diethyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol isobutyrate, 2-ethyl-1,3-hexanediol, 1,6-hexanediol At least one selected from the group of diacetate and isoamyl acetate is preferred.
本発明の紙器用水性グラビア印刷インキ組成物において、上記印刷改質剤の含有量は、印刷時において、好ましい下限が０．５質量％、好ましい上限が５質量％である。印刷時における上記印刷改質剤の含有量が０．５質量％未満であると、印刷物に印刷抜けやざらつき感が生じることがある。印刷時における上記印刷改質剤の含有量が５質量％を超えると、得られる紙器用水性グラビア印刷インキ組成物が乾燥性に劣るものとなることがある。 In the aqueous gravure printing ink composition for paper containers of the present invention, the content of the print modifier is preferably 0.5% by mass at the time of printing, and 5% by mass at the preferable upper limit. When the content of the printing modifier at the time of printing is less than 0.5% by mass, the printed matter may have a feeling of omission or roughness. If the content of the printing modifier during printing exceeds 5% by mass, the resulting aqueous gravure printing ink composition for paper containers may be inferior in drying properties.
本発明の紙器用水性グラビア印刷インキ組成物は、使用用途に応じて、任意成分を適宜含有してもよい。上記任意成分としては、ワックス、湿潤剤、消泡剤、ｐＨ調整剤、粘度調整剤、乾燥調整剤、光沢剤、架橋剤等、種々の添加剤が挙げられる。 The aqueous gravure printing ink composition for paper containers of the present invention may appropriately contain optional components depending on the intended use. Examples of the optional component include various additives such as a wax, a wetting agent, an antifoaming agent, a pH adjusting agent, a viscosity adjusting agent, a drying adjusting agent, a brightening agent, and a crosslinking agent.
本発明の紙器用水性グラビア印刷インキ組成物を製造する方法を説明する。
まず、着色剤、アルカリ可溶型水溶性樹脂、及び、必要に応じて添加する分散剤等を混合し、通常のインキ製造装置（例えば、ボールミル、アトライター、サンドミル等）を用いて攪拌、混練した後、アルカリ可溶型水溶性樹脂、エマルジョン型の水性樹脂、印刷改質剤、水とバイオマス由来の炭素数１〜４の低級アルコールを含有する水性媒体、必要に応じて、消泡剤等の添加剤を添加混合して製造する方法が挙げられる。
The method for producing the aqueous gravure printing ink composition for paper containers of the present invention will be described.
First, a colorant, an alkali-soluble water-soluble resin, and a dispersant added as necessary are mixed, and stirred and kneaded using a normal ink production apparatus (for example, a ball mill, an attritor, a sand mill, etc.). After that, an alkali-soluble water-soluble resin, an emulsion-type aqueous resin, a printing modifier, an aqueous medium containing water and a biomass-derived lower alcohol having 1 to 4 carbon atoms, if necessary, an antifoaming agent, etc. The method of adding and mixing these additives may be mentioned.
本発明の紙器用水性グラビア印刷インキ組成物の固形分の含有量の好ましい下限は１５質量％、好ましい上限は３０質量％である。上記固形分の含有量が１５質量％未満であると、乾燥性が低下することがある。上記固形分の含有量が３０質量％を超えると、粘度が高くなりすぎることがある。
なお、本明細書において、上記固形分とは、グラビア印刷されるときの固形分を意味する。
The minimum with preferable content of solid content of the aqueous | water-based gravure printing ink composition for paper containers of this invention is 15 mass%, and a preferable upper limit is 30 mass%. If the solid content is less than 15% by mass, the drying property may decrease. When content of the said solid content exceeds 30 mass%, a viscosity may become high too much.
In the present specification, the solid content means a solid content when gravure printing is performed.
本発明の紙器用水性グラビア印刷インキ組成物の印刷方法について説明する。
本発明の紙器用水性グラビア印刷インキ組成物は、コート紙等の紙基材に、グラビア印刷方式で印刷することができる。
印刷物の製造効率を考慮すると、印刷スピードは１５０ｍ／分以上が好ましい。また、印刷スピードを１５０ｍ／分以上とするために、印刷後に、各種加熱乾燥装置を利用した乾燥工程を行ってもよい。
なお、印刷時、本発明の紙器用水性グラビア印刷インキ組成物の粘度としては、ザーンカップＮｏ．３の流出秒数が１５〜１９秒程度であることが好ましい。上記流出秒数が１５秒未満であると、レベリング性が低下することがある。上記流出秒数が１９秒を超えると、印刷適性が低下することがある。
The printing method of the aqueous gravure printing ink composition for paper containers of the present invention will be described.
The aqueous gravure printing ink composition for paper containers of the present invention can be printed on a paper substrate such as coated paper by a gravure printing method.
Considering the production efficiency of printed matter, the printing speed is preferably 150 m / min or more. Moreover, in order to make a printing speed 150 m / min or more, you may perform the drying process using various heat drying apparatuses after printing.
In addition, as the viscosity of the aqueous gravure printing ink composition for paper containers of the present invention during printing, 3 is preferably about 15 to 19 seconds. If the outflow time is less than 15 seconds, the leveling property may be lowered. If the outflow time exceeds 19 seconds, the printability may deteriorate.
また、通常、本発明の紙器用水性グラビア印刷インキ組成物は、印刷時に希釈剤により希釈される。上記希釈剤による希釈は、印刷時の本発明の紙器用水性グラビア印刷インキ組成物中の固形分の含有量が、１５〜３０質量％となる範囲となるようになされることが好ましい。ただし、浅版化した刷版を使用する場合は、印刷適性及び印刷性能の観点から、印刷時の本発明の紙器用水性グラビア印刷インキ組成物中の固形分の含有量が、２０〜３０質量％となるようになされることが好ましく、２５〜３０質量％となるようになされることがより好ましい。 Moreover, the aqueous gravure printing ink composition for paper containers of the present invention is usually diluted with a diluent during printing. The dilution with the diluent is preferably performed so that the solid content in the aqueous gravure printing ink composition for paper containers of the present invention during printing is in the range of 15 to 30% by mass. However, when using a shallow printing plate, the solid content in the aqueous gravure printing ink composition for paper containers of the present invention at the time of printing is 20 to 30 masses from the viewpoint of printability and printing performance. %, And more preferably 25-30% by mass.
更に、本発明の紙器用水性グラビア印刷インキ組成物を用いて印刷した印刷物には、紙器用水性オーバープリントニス組成物を塗工してもよい。上記紙器用水性オーバープリントニス組成物としては、従来公知の紙器用ものが使用できるが、水性媒体、エマルジョン型の水性樹脂、及び、上述した印刷改質剤を含有するものが好ましい。
上記水性オーバープリントニス組成物に用いる水性媒体は、ＶＯＣや二酸化炭素の排出量を削減するために、炭素数１〜４の低級アルコール等の有機溶媒を極力少なくすることが好ましく、有機溶剤を使用しない水がより好ましい。
Furthermore, you may apply the aqueous overprint varnish composition for paper containers to the printed matter printed using the water-based gravure printing ink composition for paper containers of this invention. As the above-mentioned aqueous overprint varnish composition for paper containers, conventionally known ones for paper containers can be used, but those containing an aqueous medium, an emulsion-type aqueous resin, and the above-described printing modifier are preferable.
The aqueous medium used for the aqueous overprint varnish composition is preferably an organic solvent such as a lower alcohol having 1 to 4 carbon atoms as much as possible in order to reduce VOC and carbon dioxide emissions. Water that does not is more preferred.
本発明の紙器用水性グラビア印刷インキ組成物を印刷する工程、及び、上記紙器用水性オーバープリントニス組成物を塗工する工程は、一連の工程で行われてもよいし、別々の機会に工程を分けて行われてもよい。
また、例えば、６缶パックのパッケージ等では、印刷物を製造後、打ち抜き加工等の後加工が行われるが、この後加工は、本発明の紙器用水性グラビア印刷インキ組成物を印刷する工程や、上記水性オーバープリントニス組成物を塗工する工程と一連の工程で行われてもよいし、別々の機会に工程を分けて行われてもよい。
グラビア印刷、塗工、後加工を一度に行える装置としては、例えば、ボブストチャンプレンレマニックグラビア輪転打抜機等が挙げられる。
具体的には、コート紙等の紙基材を給紙部に供給し、本発明の紙器用水性グラビア印刷インキ組成物をグラビア印刷方式によって印刷した後、上記紙器用水性オーバープリントニス組成物の塗工による被覆を、１５０〜２００ｍ／ｍｉｎの印刷・塗工スピードで行い、その後、打ち抜き工程を経て、目的の印刷物を得ることができる。
The step of printing the aqueous gravure printing ink composition for paper containers of the present invention and the step of applying the aqueous overprint varnish composition for paper containers may be performed in a series of steps, or steps on separate occasions. May be performed separately.
In addition, for example, in a package of 6 can packs, after manufacturing the printed matter, post-processing such as punching is performed, and this post-processing is a step of printing the aqueous gravure printing ink composition for paper containers of the present invention, The aqueous overprint varnish composition may be applied in a series of steps, or may be performed on separate occasions.
Examples of the apparatus that can perform gravure printing, coating, and post-processing at once include a Bobst Champlein Remanic gravure rotary punching machine.
Specifically, a paper base material such as coated paper is supplied to the paper feeding unit, and after the aqueous gravure printing ink composition for paper containers of the present invention is printed by the gravure printing method, the aqueous overprint varnish composition for paper containers is used. Coating by coating is performed at a printing / coating speed of 150 to 200 m / min, and then a target printed matter can be obtained through a punching process.
更に、本発明の紙器用水性グラビア印刷インキ組成物を印刷後、及び、上記紙器用水性オーバープリントニス組成物を塗工した後、乾燥にあたっては熱風乾燥装置を利用することにより、印刷効率、塗工効率、全体の印刷物の製造効率を高くすることができる。 Furthermore, after printing the water-based gravure printing ink composition for paper containers of the present invention and after coating the water-based overprint varnish composition for paper containers, the drying can be performed by using a hot air drying device, so that the printing efficiency, coating It is possible to increase the work efficiency and the overall printed matter production efficiency.
本発明の紙器用水性グラビア印刷インキ組成物は、紙器カートンのグラビア印刷に特に好適に用いられる。 The aqueous gravure printing ink composition for paper containers of the present invention is particularly suitably used for gravure printing of paper container cartons.
本発明によれば、印刷により発生する揮発性有機化合物や二酸化炭素の排出量を低減でき、良好な乾燥性と印刷適性とを有する紙器用水性グラビア印刷インキ組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the discharge | emission amount of the volatile organic compound and carbon dioxide which generate | occur | produce by printing can be reduced, and the water-based gravure printing ink composition for paper containers which has favorable drying property and printability can be provided.
以下に、実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「％」は「質量％」を意味し、「部」は「質量部」を意味するものである。また、表１〜１３中の各材料の分量の数字についても「質量部」である。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited only to these examples. Unless otherwise specified, “%” means “% by mass”, and “part” means “part by mass”. Moreover, it is a "mass part" also about the number of the quantity of each material in Tables 1-13.
＜紙器用水性グラビア印刷インキ組成物＞
構成材料
（有色顔料）
赤色顔料（ＰＲ４８：３）
黄色顔料（ＰＹ１４）
青色顔料（ＰＢ１５：３）
黒色顔料（ＰＢ７）
（水性媒体）
水
バイオマス由来のエタノール
イソプロピルアルコール
（消泡剤）
ＢＹＫ−０２８＃Ｃ（商品名、ビックケミー社製）
（ワックス）
ケミパール４００Ｗ（商品名、三井化学社製、ポリエチレンワックス）
（エマルジョン型の水性樹脂）
アクリル酸１２質量部、メタクリル酸メチル７１質量部、アクリル酸ブチル１７質量部からなるアルカリ可溶性樹脂のジメチルエタノールアミン水溶液を、高分子乳化剤として調製した。得られた高分子乳化剤の樹脂固形分６０質量部に対し、２−エチルヘキシルアクリレート８質量部、スチレン２０質量部、メタクリルメチル１２質量部を添加し、乳化重合し、酸価４７、ガラス転移温度５５℃、固形分４０％のエマルジョン型の水性樹脂を得た。
（アルカリ可溶型水溶性樹脂）
スチレン２２質量部、α−メチルスチレン６質量部、メタクリル酸６質量部、メチルメタクリレート２８質量部、無水マレイン酸のイソブタノールのハーフエステル３４質量部を重合し、酸価１５０ｍｇＫＯＨ／ｇ、重量平均分子量１９０００の共重合体を得た。得られた共重合体をアンモニア水で中和し、固形分２０．２％のアルカリ可溶型水溶性樹脂を得た。
<Water-based gravure printing ink composition for paper containers>
Constituent material (colored pigment)
Red pigment (PR48: 3)
Yellow pigment (PY14)
Blue pigment (PB15: 3)
Black pigment (PB7)
(Aqueous medium)
Ethanol isopropyl alcohol (antifoaming agent) derived from water biomass
BYK-028 # C (Brand name, manufactured by Big Chemie)
(wax)
Chemipearl 400W (trade name, manufactured by Mitsui Chemicals, polyethylene wax)
(Emulsion type aqueous resin)
A dimethylethanolamine aqueous solution of an alkali-soluble resin consisting of 12 parts by mass of acrylic acid, 71 parts by mass of methyl methacrylate and 17 parts by mass of butyl acrylate was prepared as a polymer emulsifier. Eight parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of styrene, and 12 parts by mass of methyl methacrylate are added to 60 parts by mass of the resin solid content of the obtained polymer emulsifier, and emulsion polymerization is performed. An emulsion-type aqueous resin having a solid content of 40% at 0 ° C. was obtained.
(Alkali-soluble water-soluble resin)
Styrene 22 parts by mass, α-methylstyrene 6 parts by mass, methacrylic acid 6 parts by mass, methyl methacrylate 28 parts by mass, maleic anhydride isobutanol 34 parts by mass are polymerized, acid value 150 mgKOH / g, weight average molecular weight 19000 copolymers were obtained. The obtained copolymer was neutralized with aqueous ammonia to obtain an alkali-soluble water-soluble resin having a solid content of 20.2%.
（紙器用水性グラビア印刷インキベースの調製）
下記の配合に従って、各顔料（赤色顔料（ＰＲ４８：３）、黄色顔料（ＰＹ１４）、青色顔料（ＰＢ１５：３）、黒色顔料（ＰＢ７、カーボンブラック））、アルカリ可溶型水溶性樹脂、及び、水をビーズミルで混合した後、残りの材料を添加混合して、赤、黄、青、黒の各色の紙器用水性グラビア印刷インキベースを得た。
＜紙器用水性グラビア印刷インキベース＞
アルカリ可溶型水溶性樹脂（Ｎ．Ｖ．２０．２％） ２５質量部
水 １７質量部
顔料 ３０質量部
ビーズミル練肉
アルカリ可溶型水溶性樹脂（Ｎ．Ｖ．２０．２％） ２０質量部
水 ８質量部
合計 １００質量部
(Preparation of water-based gravure printing ink base for paper containers)
According to the following formulation, each pigment (red pigment (PR48: 3), yellow pigment (PY14), blue pigment (PB15: 3), black pigment (PB7, carbon black)), alkali-soluble water-soluble resin, and After mixing water with a bead mill, the remaining materials were added and mixed to obtain an aqueous gravure printing ink base for paper containers of red, yellow, blue and black colors.
<Water-based gravure printing ink base for paper containers>
Alkali-soluble water-soluble resin (N.V. 20.2%) 25 parts by mass Water 17 parts by mass Pigment 30 parts by mass Bead mill kneaded alkali-soluble water-soluble resin (N.V. 20.2%) 20 parts by mass Part water 8 parts by weight total 100 parts by weight
（実施例１〜２０、比較例１〜８）
表１〜１２の配合組成となるように、上述の赤（表１〜３）、黄（表４〜６）、青（表７〜９）、黒（表１０〜１２）の各色の紙器用水性グラビア印刷インキベース、エマルジョン型の水性樹脂、アルカリ可溶型水溶性樹脂、水性媒体、イソプロピルアルコール、消泡剤、ワックス、印刷改質剤を攪拌混合した。その後、バイオマス由来のエタノールと水とからなる希釈剤Ａ（バイオマス由来のエタノール：水＝７０：３０（質量比））又はイソプロピルアルコールと水とからなる希釈剤Ｂ（イソプロピルアルコール：水＝７０：３０（質量比））を用いて、粘度が表１〜１２に示した範囲で、組成物中の固形分、及び、バイオエタノール又はイソプロピルアルコールの含有量が表１〜１２に示した値となるように希釈し、赤、黄、青、黒の各色の実施例及び比較例の紙器用水性グラビア印刷インキ組成物を得た。
(Examples 1-20, Comparative Examples 1-8)
For paper containers of each color of the above red (Tables 1 to 3), yellow (Tables 4 to 6), blue (Tables 7 to 9), and black (Tables 10 to 12) so as to have the composition of Tables 1 to 12 An aqueous gravure printing ink base, an emulsion-type aqueous resin, an alkali-soluble water-soluble resin, an aqueous medium, isopropyl alcohol, an antifoaming agent, a wax, and a printing modifier were mixed with stirring. Thereafter, diluent A (biomass-derived ethanol: water = 70: 30 (mass ratio)) consisting of biomass-derived ethanol and water or diluent B (isopropyl alcohol: water = 70: 30) consisting of isopropyl alcohol and water. (Mass ratio)), the viscosity is in the range shown in Tables 1-12, so that the solid content in the composition and the content of bioethanol or isopropyl alcohol become the values shown in Tables 1-12. To obtain an aqueous gravure printing ink composition for paper containers of Examples and Comparative Examples of red, yellow, blue and black colors.
（参照例１）
参照例の各色の紙器用水性グラビア印刷インキ組成物として、市販品を用いた。
表１３に、用いた市販品の赤、黄、青、黒の各色の紙器用水性グラビア印刷インキ組成物の配合組成を示す。
(Reference Example 1)
A commercially available product was used as the water-based gravure printing ink composition for paper containers of each color of the reference example.
Table 13 shows the composition of the commercially available water based gravure printing ink compositions for paper containers of red, yellow, blue and black.
＜評価＞
実施例、比較例、及び、参照例に係る各色の紙器用水性グラビア印刷インキ組成物の乾燥性、印刷改質性、網点再現性について、下記の条件で各紙器用水性グラビア印刷インキ組成物をコート紙にグラビア印刷し、その印刷物について評価した。なお、印刷時に排出される二酸化炭素の排出量は、実施例では大幅に低減できる（実施例では炭素数１〜４の低級アルコールとしてバイオマス由来のアルコールを使用しており、バイオマス由来のアルコールから発生する二酸化炭素は、植物が成長する過程で大気中から吸収した二酸化炭素と同量（カーボンニュートラル）と考えられ、差し引きするとバイオマス由来のアルコールを使用することにより新たに発生する二酸化炭素の量はゼロとみなされるため）。
<Evaluation>
The waterborne gravure printing ink composition for each paper container under the following conditions with respect to the drying property, print modification property, and halftone dot reproducibility of the waterborne gravure printing ink composition for each color paper container according to Examples, Comparative Examples, and Reference Examples Was printed on a coated paper and evaluated for the printed matter. The amount of carbon dioxide emitted during printing can be greatly reduced in the examples (in the examples, biomass-derived alcohol is used as a lower alcohol having 1 to 4 carbon atoms, and is generated from biomass-derived alcohol. The amount of carbon dioxide to be generated is considered to be the same amount (carbon neutral) as the carbon dioxide absorbed from the atmosphere in the process of plant growth, and when subtracted, the amount of carbon dioxide newly generated by using biomass-derived alcohol is zero To be considered).
（印刷条件）
用紙：コート紙（商品名：ＣＲＣ２３０、レンゴー社製）
印刷機械：グラビア校正機（東芝社製）
インキを印刷する刷版：ヘリオ１７５ｉｎｅ／ｉｎｃｈ（図柄：網点濃度５〜１００％の諧調を有する諧調版）
印刷速度：８０ｍ／ｍｉｎ
乾燥条件：８０℃
(Printing conditions)
Paper: Coated paper (Product name: CRC230, manufactured by Rengo)
Printing machine: Gravure proofing machine (manufactured by Toshiba)
Printing plate for printing ink: Helio 175ine / inch (design: tone plate with tone of 5 to 100% halftone dot density)
Printing speed: 80m / min
Drying conditions: 80 ° C
（乾燥性）
各色の紙器用水性グラビア印刷インキ組成物の乾燥性は、グラビア校正機にて印刷速度を変えて印刷・塗工を行い、ガイドロールに（印刷面、塗工面）が触れた時に、ガイドロールにインキが付着して汚れる度合いを、目視にて、下記基準で評価した。結果を表１４に示した。
○：ガイドロールへの付着量が少ない
×：ガイドロールへの付着量が多い
(Drying)
The dryness of the water-based gravure printing ink composition for paper containers is determined by changing the printing speed with a gravure proofing machine when printing and coating are performed, and the guide roll (printed surface, coated surface) touches the guide roll. The degree of ink adhering and soiling was visually evaluated according to the following criteria. The results are shown in Table 14.
○: Adhesion amount on the guide roll is small ×: Adhesion amount on the guide roll is large
（レベリング性）
得られた各印刷物の網点濃度１００％であるベタ部の濃淡ムラ、抜けを、目視にて、下記基準で評価した。結果を表１４に示した。
◎：濃淡むら、抜けがない
○：濃淡むら又は抜けが少しある
△：濃淡むら及び抜けが少しある
×：濃淡むら又は抜けが多い
(Leveling)
The obtained printed materials were visually evaluated on the following standards for density unevenness and omission in a solid portion having a dot density of 100%. The results are shown in Table 14.
◎: Shading unevenness and no omission ○: Shading shading or slight omission Δ: Shading unevenness and omission a little ×: Shading unevenness or omission many
（網点再現性）
得られた各印刷物の網点の状態を、目視にて、下記基準で評価した。結果を表１４に示した。
○：参照例１（市販インキ）と同等以上
△：参照例１（市販インキ）より少し劣る
×：参照例１（市販インキ）より劣る
(Halftone dot reproducibility)
The state of the halftone dot of each obtained printed matter was visually evaluated according to the following criteria. The results are shown in Table 14.
○: At least equivalent to Reference Example 1 (commercial ink) Δ: Slightly inferior to Reference Example 1 (commercial ink) ×: Inferior to Reference Example 1 (commercial ink)
本発明によれば、印刷により発生する揮発性有機化合物や二酸化炭素の排出量を低減でき、良好な乾燥性と印刷適性とを有する紙器用水性グラビア印刷インキ組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the discharge | emission amount of the volatile organic compound and carbon dioxide which generate | occur | produce by printing can be reduced, and the water-based gravure printing ink composition for paper containers which has favorable drying property and printability can be provided.
Claims (3)
前記水性媒体は、水と炭素数１〜４の低級アルコールとを含有し、
前記炭素数１〜４の低級アルコールは、バイオマス由来のアルコールを含有し、
前記印刷改質剤は、下記式（１）で表わされる化合物、下記式（２）で表わされる化合物、２−ブチル−２−エチル−１，３−プロパンジオール、２，４−ジエチル−１，５−ペンタンジオール、２，２，４−トリメチル−１，３−ペンタンジオールイソブチレート、２−エチル−１，３−ヘキサンジオール、１，６−ヘキサンジオールジアセテート、及び、イソアミルアセテートからなる群より選択される少なくとも１種である
ことを特徴とする紙器用水性グラビア印刷インキ組成物。
The aqueous medium contains water and a lower alcohol having 1 to 4 carbon atoms,
The lower alcohol having 1 to 4 carbon atoms contains alcohol derived from biomass,
The printing modifier is a compound represented by the following formula (1), a compound represented by the following formula (2), 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1, The group consisting of 5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol isobutyrate, 2-ethyl-1,3-hexanediol, 1,6-hexanediol diacetate, and isoamyl acetate An aqueous gravure printing ink composition for paper containers, characterized in that it is at least one selected from the above.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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