JP5731796B2 - Aqueous coating composition for paper containers and method for producing printed matter - Google Patents
Aqueous coating composition for paper containers and method for producing printed matter Download PDFInfo
- Publication number
- JP5731796B2 JP5731796B2 JP2010247866A JP2010247866A JP5731796B2 JP 5731796 B2 JP5731796 B2 JP 5731796B2 JP 2010247866 A JP2010247866 A JP 2010247866A JP 2010247866 A JP2010247866 A JP 2010247866A JP 5731796 B2 JP5731796 B2 JP 5731796B2
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- JP
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- Prior art keywords
- aqueous
- paper containers
- coating composition
- resin
- paper
- 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.)
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- 239000008199 coating composition Substances 0.000 title claims description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 229920005989 resin Polymers 0.000 claims description 86
- 239000011347 resin Substances 0.000 claims description 86
- 239000000203 mixture Substances 0.000 claims description 61
- 238000007646 gravure printing Methods 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000000178 monomer Substances 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 24
- 230000009477 glass transition Effects 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 239000003995 emulsifying agent Substances 0.000 claims description 22
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims description 21
- 239000012736 aqueous medium Substances 0.000 claims description 21
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 14
- 239000004606 Fillers/Extenders Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000003086 colorant Substances 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 239000000976 ink Substances 0.000 description 75
- 238000007639 printing Methods 0.000 description 51
- 239000002966 varnish Substances 0.000 description 44
- 238000001035 drying Methods 0.000 description 38
- 239000000049 pigment Substances 0.000 description 26
- 239000000463 material Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 239000002585 base Substances 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000012855 volatile organic compound Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000001993 wax Substances 0.000 description 7
- 239000002518 antifoaming agent Substances 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- -1 2-ethylhexyl Chemical group 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 235000013405 beer Nutrition 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 239000002023 wood Substances 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
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 101000614399 Homo sapiens Serine/threonine-protein phosphatase 2A regulatory subunit B'' subunit beta Proteins 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 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
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000005995 Aluminium silicate Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 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 1
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- 235000013334 alcoholic beverage Nutrition 0.000 description 1
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- 229910021529 ammonia Inorganic materials 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
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- 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
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- 239000001052 yellow pigment Substances 0.000 description 1
Description
本発明は、紙器用水性被覆剤組成物に関し、より詳しくは、コート紙などの浸透性の低い紙基材を対象としたときに、組成物中に含まれている低級アルコールの量を極力少なくした中で、良好な乾燥性とレベリング性を有する紙器用水性オーバープリントニス組成物、及び、良好な乾燥性と印刷適性を有する紙器用水性グラビア印刷インキ組成物として適用が可能な紙器用水性被覆剤組成物及び印刷物の製造方法に関する。 The present invention relates to a water-based coating composition for paper containers, and more specifically, the amount of lower alcohol contained in the composition is reduced as much as possible when targeting a paper substrate with low permeability such as coated paper. Among these, an aqueous overprint varnish composition for paper containers having good drying and leveling properties, and an aqueous coating for paper containers that can be applied as an aqueous gravure printing ink composition for paper containers having good drying properties and printability. The present invention relates to an agent composition and a method for producing a printed material.
菓子、ティッシュ、洗剤等の食品から家庭用品までの外装箱、酒類や飲料のマルチパック用パッケージ等には、美粧化のために水性インキがグラビア方式で印刷され、さらに、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ッ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。
Water-based inks are printed in a gravure system for cosmetics on exterior boxes from confectionery, tissues, detergents and other foods to household items, and multipack packages for alcoholic beverages and beverages. For this reason, an aqueous overprint varnish is applied.
For example, recently, canned beer has been very often displayed and sold as a six-can pack. What is particularly noticeable is the print quality of these 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.
このような６缶パックの印刷用紙基材には、表面に炭酸カルシウムなどの無機粒子と樹脂等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、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高光沢の付与を可能にする。しかし、被覆剤組成物の印刷・塗工の際に、コート紙は非塗工紙と比較して乾燥性を低下させるという欠点がある。本来、紙基材中への浸透による乾燥が期待できるときは、水性被覆剤組成物の水性媒体が水だけでも良好な乾燥性が得られることも多い。ところが、コート紙を利用すると、浸透の抑制により乾燥が阻害される分、乾燥性が低下する。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る。 For such a 6-can pack printing paper substrate, a coated paper having a dense coating layer made 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 has the characteristics of suppressing the penetration of the coating composition and improving the yield, thereby enabling precise and high-density printing and imparting high gloss. . However, when printing / coating the coating composition, the coated paper has a drawback that the drying property is lowered as compared with the non-coated paper. Originally, when drying by penetration into a paper substrate can be expected, good drying properties are often obtained even if the aqueous medium of the aqueous coating composition is water alone. However, when the coated paper is used, the drying property is lowered by the amount that the drying is inhibited by the suppression of the permeation. Dryability 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. Therefore, how to eliminate the decrease in drying property using coated paper is a major issue to be investigated.
また、コート紙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、印刷物の場合に、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るといった結果になる。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 coated paper also suppresses the spread of the coating composition on the paper surface, so in the case of printed matter, printing may be lost in the shadow area (the area with a high dot area ratio). As a result, the highlight portion (the portion with a low dot area ratio) 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、その中に一度インキを充填し、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、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出る。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。オーバープリントニスは着色されていないので、塗工抜けやざらつき感はあまり見られないが、塗膜表面に微細な凹凸が生じで光沢が損なわれる等の問題があり、レベリング性は同様に要求される。 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 once filled with ink, the doctor This is a printing method in which after a plate-like member called a blade scrapes off ink adhering to a portion other than the concave portion, the printing substrate is pressed against the plate surface, and only the ink remaining in the cells is transferred to the printing substrate. Here, if the ink does not spread after transferring from the cell to the printing substrate, the ink will be scattered on the printing substrate, resulting in a feeling of omission or roughness. 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. Since the overprint varnish is not colored, there is not much coating omission or rough feeling, but there are problems such as fine irregularities on the surface of the coating resulting in loss of gloss, and leveling properties are also required. The
以上のような水性のインキやオーバープリントニスの乾燥性やレベリング性を向上させるためには、低級アルコール成分を含有させるのが効果的であることが知られている。そこで、通常、これら水性のグラビアインキやオーバープリントニスがコート紙に印刷・塗工される際には、低級アルコールが４０％程度と多量に含まれている（特許文献１参照）。 In order to improve the drying property and leveling property of the above water-based ink and overprint varnish, it is known that it is effective to contain a lower alcohol component. Therefore, usually, when these water-based gravure inks and overprint varnishes are printed / coated on coated paper, a lower alcohol is contained in a large amount of about 40% (see 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、改正大気汚染防止法の施行により、２０１０年末までに業界全体で揮発性有機化合物（ＶＯＣ）の排出量を３割削減することが義務つけられている。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。
この対応手段としては、インキやオーバープリントニスのような水性被覆剤組成物中に含まれる低級アルコール量を低減する方法が最も基本的と言える。
However, in recent years, there has been a strong demand for protection of the natural environment and improvement of the working environment, and in the printing industry, due to the enforcement of the revised Air Pollution Control Law, volatile organic compounds (VOC) have been developed throughout the industry by the end of 2010. It is obliged to reduce emissions by 30%. 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.
As this countermeasure, the most basic method is to reduce the amount of lower alcohol contained in the aqueous coating composition such as ink or overprint varnish.
しかしながら、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を低減しただけの場合、グラビアインキでは、印刷適性や乾燥性が低下し、オーバープリントニスでは、乾燥性やレベリング性が低下するという問題が発生していた。 However, when the lower alcohol is simply reduced from the aqueous coating compositions that have been used so far, the gravure ink has reduced printability and drying properties, and the overprint varnish has reduced drying properties and leveling properties. There was a problem to do.
そこで、本発明では、水性被覆剤組成物中に含まれる低級アルコールの量を極力少なくして、コート紙などの浸透性の低い紙基材を対象としたときに、印刷適性、乾燥性が良好な紙器用水性グラビア印刷インキ、乾燥性、レベリング性が良好な紙器用水性オーバープリントニスとして適用できる紙器用水性被覆剤を提供することを目的とする。 Therefore, in the present invention, when the amount of the lower alcohol contained in the aqueous coating composition is reduced as much as possible to target a paper substrate having low permeability such as a coated paper, the printability and drying property are good. It is an object of the present invention to provide an aqueous coating agent for paper containers that can be applied as an aqueous overprint varnish for paper containers having good water-based gravure printing ink for paper containers, drying properties and leveling properties.
上記のように、乾燥性は印刷物の生産効率に直結する極めて重要な性能である。そこで、特に浸透乾燥性があまり期待できないコート紙での印刷物の製造においては、従来、インキやオーバープリントニスの水性媒体として、蒸発乾燥性を向上させる低級アルコールが利用されている。さらに、低級アルコールには系の表面張力を低下させる機能があり、レベリング性が良好で浸透乾燥についても有利になるなど、多面にわたって利点がある。
しかしながら、その一方で、自然環境と作業環境の両面から、揮発性有機化合物の排出が厳しく規制されるようになり、印刷業界でも、有機溶剤の利用量を抑えた組成物の要望が強くなっている。ところが、このような場合、単純にアルコール含有量を減量すると、乾燥性の他にもレベリング性や印刷適性が低下することが知られている。
As described above, the drying property is a very important performance that is directly related to the production efficiency of the printed matter. Therefore, in the production of printed matter on coated paper, which is not particularly expected to have osmotic drying properties, conventionally, lower alcohols that improve evaporation drying properties have been used as aqueous media for inks and overprint varnishes. Furthermore, the lower alcohol has a function of lowering the surface tension of the system, and has many advantages such as good leveling and advantageous for osmotic drying.
However, on the other hand, emissions of volatile organic compounds have become severely regulated from both the natural and work environments, and the printing industry is increasingly demanding compositions that reduce the use of organic solvents. Yes. However, in such a case, it is known that if the alcohol content is simply reduced, the leveling property and the printability are lowered in addition to the drying property.
そこで、本発明者らは、まず、高固形分−低粘度化が可能で、系からの水性媒体の離脱を速めるエマルジョン型の水性樹脂を利用することとした。そして、固形分総量の多いインキやオーバープリントニスで印刷・塗工を行った結果、低級アルコールの含有量を抑えた中で、乾燥性を速くすることに成功した。 Therefore, the present inventors first decided to use an emulsion-type aqueous resin that can achieve a high solid content-low viscosity and accelerate the release of the aqueous medium from the system. As a result of printing and coating with ink and overprint varnish with a large total amount of solids, we succeeded in speeding up drying while suppressing the content of lower alcohol.
ところが、粒子状のエマルジョン型の水性樹脂の高固形分化は流動性の低下をもたらし、それに伴って、レベリング性や印刷適性の不良をまねくことになる。そこで、本発明者らは、さらにレベリング性や印刷適性の改善として、２−エチル−１，３−ヘキサンジオールを含有させると、特異的に効果が得られることを見出し、本発明を完成するに至った。 However, the high solid differentiation of the particulate emulsion-type aqueous resin results in a decrease in fluidity, which leads to poor leveling and printability. Therefore, the present inventors have found that when 2-ethyl-1,3-hexanediol is further contained as an improvement in leveling property and printability, a specific effect can be obtained, and the present invention is completed. It came.
すなわち、本発明は、（１）水性媒体及びエマルジョン型の水性樹脂を含有する紙器用水性被覆剤組成物であって、上記水性媒体は、水及び２−エチル−１，３−ヘキサンジオールからなり、上記２−エチル−１，３−ヘキサンジオールの含有量が０．１〜２．５質量％であり、上記エマルジョン型の水性樹脂は、高分子乳化剤の存在下で、芳香環を有するエチレン性不飽和単量体Ａを主成分とするエチレン性不飽和単量体を乳化重合させてコア部を形成し、次いで、単独で重合したときに得られる重合体のガラス転移温度が−５０℃以下であるエチレン性不飽和単量体Ｂを乳化重合させてシェル部を形成して得られる樹脂であり、更に、上記エマルジョン型の水性樹脂は、酸価が５０〜７０ｍｇＫＯＨ／ｇであり、ガラス転移温度が４０〜７０℃であることを特徴とする紙器用水性被覆剤組成物に関する。
また、本発明は、（２）水性媒体及びエマルジョン型の水性樹脂を含有する紙器用水性被覆剤組成物であって、更に、着色剤、及び、アルカリ可溶型水溶性樹脂を含有し、上記水性媒体は、水、２−エチル−１，３−ヘキサンジオール及び炭素数１〜４の低級アルコールからなるものであり、上記炭素数１〜４の低級アルコールの含有量が１５〜３０質量％であり、上記２−エチル−１，３−ヘキサンジオールの含有量が０．１〜２．５質量％であり、上記エマルジョン型の水性樹脂は、酸価が２５〜４０ｍｇＫＯＨ／ｇであり、ガラス転移温度が１５〜６０℃であることを特徴とする紙器用水性被覆剤組成物に関する。
また、本発明は、（３）上記エマルジョン型の水性樹脂は、高分子乳化剤の存在下、芳香環を有するエチレン性不飽和単量体Ａ及び単独で重合したときに得られる重合体のガラス転移温度が−５０℃以下であるエチレン性不飽和単量体Ｂを主成分とする不飽和単量体混合物を乳化重合して得られる樹脂である上記（２）項に記載の紙器用水性被覆剤組成物に関する。
また、本発明は、（４）更に、体質顔料を含有する上記（２）項又は（３）項に記載の紙器用水性被覆剤組成物に関する。
また、本発明は、（５）紙基材に、上記（２）項〜（４）項のいずれか一項に記載の紙器用水性被覆剤組成物をグラビア印刷方式により被覆処理した後、上記（１）項に記載の紙器用水性被覆剤組成物を塗工することを特徴とする紙器用印刷物の製造方法に関する。
以下、本発明の紙器用水性被覆剤組成物（水性被覆剤組成物と略記することがある）について具体的に説明する。
That is, the present invention is (1) an aqueous coating composition for paper containers containing an aqueous medium and an emulsion-type aqueous resin, wherein the aqueous medium comprises water and 2-ethyl-1,3-hexanediol. The content of 2-ethyl-1,3-hexanediol is 0.1 to 2.5% by mass, and the emulsion-type aqueous resin is ethylenic having an aromatic ring in the presence of a polymer emulsifier. The glass transition temperature of the polymer obtained when the core part is formed by emulsion polymerization of an ethylenically unsaturated monomer having the unsaturated monomer A as a main component and then polymerized alone is -50 ° C or lower. Is a resin obtained by emulsion polymerization of the ethylenically unsaturated monomer B, and the emulsion type aqueous resin has an acid value of 50 to 70 mgKOH / g, and has a glass transition. Temperature is 40 ~ About Shiki aqueous coating composition which is a 0 ° C..
The present invention also provides (2) an aqueous coating composition for paper containers containing an aqueous medium and an emulsion-type aqueous resin, further comprising a colorant and an alkali-soluble water-soluble resin, The aqueous medium is composed of water, 2-ethyl-1,3-hexanediol, and a lower alcohol having 1 to 4 carbon atoms, and the content of the lower alcohol having 1 to 4 carbon atoms is 15 to 30% by mass. The content of 2-ethyl-1,3-hexanediol is 0.1 to 2.5% by mass; the emulsion-type aqueous resin has an acid value of 25 to 40 mgKOH / g; The present invention relates to an aqueous coating composition for paper containers characterized by a temperature of 15 to 60 ° C.
Also, the present invention provides (3) the emulsion type of aqueous resin, the presence of a polymeric emulsifier, glass ethylenically unsaturated monomers A and alone obtained when polymerized polymer having an aromatic ring The aqueous coating for paper containers described in the above item ( 2 ), which is a resin obtained by emulsion polymerization of an unsaturated monomer mixture mainly composed of an ethylenically unsaturated monomer B having a transition temperature of −50 ° C. or lower. The agent composition.
Moreover, this invention relates to the aqueous | water-based coating composition for paper containers as described in said ( 2 ) term | claim or ( 3 ) term | claim which contains extender pigment ( 4 ) further.
In addition, the present invention provides ( 5 ) a paper base material, after coating the aqueous coating composition for paper containers according to any one of ( 2 ) to ( 4 ) by a gravure printing method, (1) a method of manufacturing a paper container for printed materials, which comprises coating the paper containers aqueous coating composition according to item.
Hereinafter, the aqueous coating composition for paper containers of the present invention (sometimes abbreviated as an aqueous coating composition) will be specifically described.
本発明の紙器用水性被覆剤組成物は、水性媒体及びエマルジョン型の水性樹脂を必須成分として含有する。
上記水性媒体は、水及び２−エチル−１，３−ヘキサンジオールからなるか、又は、水、２−エチル−１，３−ヘキサンジオール及び炭素数１〜４の低級アルコールからなるものである。
The aqueous coating composition for paper containers of the present invention contains an aqueous medium and an emulsion-type aqueous resin as essential components.
The aqueous medium is composed of water and 2-ethyl-1,3-hexanediol, or composed of water, 2-ethyl-1,3-hexanediol, and a lower alcohol having 1 to 4 carbon atoms.
すなわち本発明の紙器用水性被覆剤組成物では、水性媒体は、２−エチル−１，３−ヘキサンジオールを含有するものである。これにより、上記水性被覆剤組成物の乾燥性やレベリング性を向上させたり、また、上記水性被覆剤組成物をグラビア印刷方式で塗工するときの印刷適性を向上させることができる。 That is, in the aqueous coating composition for paper containers of the present invention, the aqueous medium contains 2-ethyl-1,3-hexanediol. Thereby, the drying property and leveling property of the aqueous coating composition can be improved, and the printability when the aqueous coating composition is applied by a gravure printing method can be improved.
また、上記２−エチル−１，３−ヘキサンジオールの含有量は、上記紙器用水性被覆剤組成物中０．１〜２．５質量％である。
上記含有量が０．１質量％未満であると、低級アルコールの含有量を抑えたときに、乾燥性やレベリング性が低下する。一方、２．５質量％を超えると、紙器用水性被覆剤組成物の経時安定性が低下する傾向がある。
Moreover, content of the said 2-ethyl- 1, 3- hexanediol is 0.1-2.5 mass% in the said aqueous | water-based coating composition for paper containers.
When the content is less than 0.1% by mass, when the content of the lower alcohol is suppressed, drying properties and leveling properties are deteriorated. On the other hand, when it exceeds 2.5 mass%, the temporal stability of the aqueous coating composition for paper containers tends to decrease.
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被覆剤組成物に使用されているものであれば特に限定されず、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、イソブタノールのいずれも利用することができる。 The lower alcohol having 1 to 4 carbon atoms is not particularly limited as long as it is conventionally used in an aqueous coating composition for paper containers, and includes methanol, ethanol, n-propanol, isopropanol, n-butanol, sec. -Any of butanol, tert-butanol, and isobutanol can be used.
上記炭素数１〜４の低級アルコールの含有量は、上記紙器用水性被覆剤組成物中３０質量％以下である。
本発明の水性被覆剤組成物は、上述したように、２−エチル−１，３−ヘキサンジオールを含有するため、揮発性有機化合物である上記低級アルコールの含有量をできるだけ少なくすることができ、かつ、印刷適性、乾燥性に優れたものとすることができる。
なお、本発明の水性被覆剤組成物を後述する紙器用グラビア印刷インキ組成物として使用する場合は、上記炭素数１〜４の低級アルコールの含有量は、上記水性被覆剤組成物中１５〜３０質量％であることが好ましく、１５〜２５質量％であることがより好ましい。１５質量％より少ないと印刷適性が低下するおそれがある。３０質量％を超えると、ＶＯＣ排出濃度が高くなるおそれがある。
Content of the said C1-C4 lower alcohol is 30 mass% or less in the said aqueous | water-based coating composition for paper containers.
As described above, since the aqueous coating composition of the present invention contains 2-ethyl-1,3-hexanediol, the content of the lower alcohol, which is a volatile organic compound, can be reduced as much as possible. And it can be excellent in printability and drying property.
In addition, when using the aqueous | water-based coating composition of this invention as a gravure printing ink composition for paper containers mentioned later, content of the said C1-C4 lower alcohol is 15-30 in the said aqueous | water-based coating composition. It is preferable that it is mass%, and it is more preferable that it is 15-25 mass%. If it is less than 15% by mass, the printability may be lowered. If it exceeds 30% by mass, the VOC emission concentration may increase.
上記水と２−エチル−１，３−ヘキサンジオールとからなる水性媒体は、本発明の紙器用水性被覆剤組成物を紙器用オーバープリントニス組成物に利用する場合、好適に用いられる。なお、この場合、上記水性媒体は、更に炭素数１〜４の低級アルコールを紙器用オーバープリントニス組成物中３０質量％以下で含有していてもよいが、該炭素数１〜４の低級アルコールの含有量は、極力少ないことが好ましい。
また、上記水と２−エチル−１，３−ヘキサンジオールと炭素数１〜４の低級アルコールとからなる水性媒体は、本発明の紙器用水性被覆剤組成物を紙器用グラビア印刷インキ組成物に利用する場合、好適に用いられる。
なお、通常、印刷インキの水性媒体で利用される、多価アルコールやその誘導体等のその他の有機溶媒については、本発明の効果を低下させない範囲で任意に含んでも良いが、もちろん、有機溶媒の大気中への放出を防止するという目的からは、極力、その他の有機溶媒を含まないことが望ましい。
The aqueous medium composed of water and 2-ethyl-1,3-hexanediol is preferably used when the aqueous coating composition for paper containers of the present invention is used for an overprint varnish composition for paper containers. In this case, the aqueous medium may further contain a lower alcohol having 1 to 4 carbon atoms in an overprint varnish composition for paper containers in an amount of 30% by mass or less, but the lower alcohol having 1 to 4 carbon atoms. The content of is preferably as small as possible.
The aqueous medium comprising water, 2-ethyl-1,3-hexanediol, and a lower alcohol having 1 to 4 carbon atoms is used as a gravure printing ink composition for paper containers. When used, it is preferably used.
Normally, other organic solvents such as polyhydric alcohols and derivatives thereof, which are usually used in an aqueous medium for printing inks, may optionally be included within a range not deteriorating the effect of the present invention. For the purpose of preventing release to the atmosphere, it is desirable to contain no other organic solvent as much as possible.
次に、本発明の紙器用水性被覆剤組成物を構成する水性樹脂について説明する。
上記水性樹脂は、エマルジョン型の水性樹脂である。
上記エマルジョン型の水性樹脂としては、具体的には、高分子乳化剤を用いて乳化重合して得られるスチレン−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を挙げることができる。
Next, the aqueous resin constituting the aqueous coating composition for paper containers of the present invention will be described.
The aqueous resin is an emulsion-type aqueous resin.
Specific examples of the emulsion-type aqueous resin include styrene-acrylic aqueous resin, styrene-maleic acid-based aqueous resin, and styrene-acrylic-maleic acid-based aqueous resin obtained by emulsion polymerization using a polymer emulsifier. Etc.
上記高分子乳化剤としては、カルボキシル基含有α，β−モノエチレン性不飽和単量体、疎水性の高い芳香環を有するエチレン性不飽和単量体Ａ、及び、必要に応じて、その他の共重合可能なエチレン性不飽和単量体を共重合して得られる酸価１００〜２００ｍｇＫＯＨ／ｇの共重合樹脂を挙げることができる。 Examples of the polymer emulsifier include a carboxyl group-containing α, β-monoethylenically unsaturated monomer, an ethylenically unsaturated monomer A having a highly hydrophobic aromatic ring, and other co-polymerizers as necessary. Examples thereof include a copolymer resin having an acid value of 100 to 200 mg KOH / g obtained by copolymerizing a polymerizable ethylenically unsaturated monomer.
上記カルボキシル基含有α，β−モノエチレン性不飽和単量体としては、（メタ）アクリル酸、イタコン酸、クロトン酸、フマール酸、無水マレイン酸、マレイン酸、マレイン酸モノエステル等を挙げることができる。 Examples of the carboxyl group-containing α, β-monoethylenically unsaturated monomer include (meth) acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, maleic acid, and maleic acid monoester. it can.
上記芳香環を有するエチレン性不飽和単量体Ａとしては、例えば、スチレン、α−メチルスチレン、ビニルトルエン、それらの誘導体等のスチレン系単量体、（メタ）アクリル酸ベンジル、（メタ）アクリル酸ナフチル等を挙げることができる。 Examples of the ethylenically unsaturated monomer A having an aromatic ring include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, and derivatives thereof, benzyl (meth) acrylate, and (meth) acrylic. Examples include acid naphthyl.
上記その他の共重合可能なエチレン性不飽和単量体としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、２−ヒドロキシステアリル（メタ）アクリレート等を挙げることができる。 Examples of the other copolymerizable ethylenically unsaturated monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) ) Acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxystearyl (meth) acrylate, and the like.
上記高分子乳化剤は、酸価が１００〜２００ｍｇＫＯＨ／ｇであることが好ましい。１００ｍｇＫＯＨ／ｇ未満であると、高分子乳化剤の水中での溶解性が低下するおそれがある。２００ｍｇＫＯＨ／ｇを超えると、得られる印刷物の耐水性が低下するおそれがある。
上記酸価は、１５０〜２００ｍｇＫＯＨ／ｇであることがより好ましい。
The polymer emulsifier preferably has an acid value of 100 to 200 mgKOH / g. If it is less than 100 mgKOH / g, the solubility of the polymer emulsifier in water may be reduced. If it exceeds 200 mgKOH / g, the water resistance of the resulting printed matter may be reduced.
The acid value is more preferably 150 to 200 mgKOH / g.
上記高分子乳化剤を水中に溶解又は分散するために使用する塩基性化合物としては、アンモニア、有機アミン、アルカリ金属水酸化物等を挙げる事ができる。具体的には、上記有機アミンとしては、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を挙げることができる。上記アルカリ金属水酸化物としては、水酸化ナトリウム、水酸化カリウム等が挙げられる。その中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。 Examples of the basic compound used for dissolving or dispersing the polymer emulsifier in water include ammonia, organic amines, alkali metal hydroxides, and the like. Specifically, 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. Among them, those that readily volatilize at normal temperature or slight heating are desirable in order to improve drying properties.
なかでも上記エマルジョン型の水性樹脂は、本発明の紙器用水性被覆剤組成物を、紙器として印刷が施された後、印刷表面に塗工させる紙器用水性オーバープリントニス組成物として使用する場合、乾燥性付与や強靭な塗膜が得られる点より、上記高分子乳化剤の存在下で、芳香環を有するエチレン性不飽和単量体Ａを主成分とするエチレン性不飽和単量体を乳化重合させてコア部を形成し、次いで、単独で重合したときに得られる重合体のガラス転移温度が−５０℃以下であるエチレン性不飽和単量体Ｂを重合させてシェル部を形成して得られる樹脂であり、酸価が５０〜７０ｍｇＫＯＨ／ｇであり、ガラス転移温度が４０〜７０℃であることが好ましい。 Among them, the emulsion-type aqueous resin is used as an aqueous overprint varnish composition for paper containers that is applied to the printing surface after printing the paper container aqueous coating composition of the present invention as a paper container. Emulsion polymerization of an ethylenically unsaturated monomer composed mainly of an ethylenically unsaturated monomer A having an aromatic ring in the presence of the above-mentioned polymer emulsifier, in terms of imparting drying properties and obtaining a tough coating film. Obtained by polymerizing an ethylenically unsaturated monomer B having a glass transition temperature of −50 ° C. or lower to form a shell part. It is preferable that the acid value is 50 to 70 mgKOH / g and the glass transition temperature is 40 to 70 ° C.
上記芳香環を有するエチレン性不飽和単量体Ａとしては、上述した高分子乳化剤の構成成分である芳香環を有するエチレン性不飽和単量体Ａと同様のものを挙げることができる。
上記単独で重合したときに得られる重合体のガラス転移温度が−５０℃以下であるエチレン性不飽和単量体Ｂとしては、例えば、（メタ）アクリル酸２−エチルヘキシル、ブチルアクリレート等を挙げることができる。
Examples of the ethylenically unsaturated monomer A having an aromatic ring include those similar to the ethylenically unsaturated monomer A having an aromatic ring which is a constituent component of the above-described polymer emulsifier.
Examples of the ethylenically unsaturated monomer B having a glass transition temperature of −50 ° C. or lower when obtained by polymerizing the above alone include 2-ethylhexyl (meth) acrylate, butyl acrylate and the like. Can do.
この様なコア−シェル構造を有する水性樹脂は、例えば、下記の重合条件によりパワーフィード重合法を利用して得ることができる。
重合条件
（第一段階）
核（コア部）の形成
例えば、共重合成分として上記単量体Ａ及び上記単量体Ｂを用いて、上記高分子乳化剤の存在下で、上記単量体Ａの方が上記単量体Ｂの添加時間より長くなる様な添加速度で添加し、乳化重合させることにより上記単量体Ａを主成分としたコア部を形成する。
（第二段階）
第一段階の反応終了後、形成させたコア部をシードとし、上記単量体Ｂを添加して、乳化重合を行うことにより、柔軟な膜を形成するソフトポリマーをコア部の表面に付着させ、上記単量体Ｂの重合物からなるシェル部を形成し、２層構造のエマルジョンを得る。尚、柔軟な膜を形成するソフトポリマーは、コア部表面に局在化するように重合させることが好ましい。
An aqueous resin having such a core-shell structure can be obtained, for example, using a power feed polymerization method under the following polymerization conditions.
Polymerization conditions (first stage)
Formation of core (core part) For example, the monomer A and the monomer B are used as a copolymerization component, and in the presence of the polymer emulsifier, the monomer A is more preferable than the monomer B. The core part which has the monomer A as a main component is formed by adding at an addition rate which becomes longer than the addition time of the above and emulsion polymerization.
(Second stage)
After the completion of the first stage reaction, the formed core part is used as a seed, the monomer B is added, and emulsion polymerization is performed to attach a soft polymer that forms a flexible film to the surface of the core part. Then, a shell portion made of the polymer of the monomer B is formed to obtain a two-layer emulsion. The soft polymer that forms a flexible film is preferably polymerized so as to be localized on the surface of the core.
その他、上記コア−シェル構造を有する水性樹脂を製造する方法としては、シード重合法、コア−シェル重合法等の多段重合法が利用できる。
このような、剛性や皮膜強度に寄与するコア部と、成膜性や耐久性に寄与するシェル部との両方を有するエマルジョン型の水性樹脂を含有することにより、本発明の紙器用水性被覆剤組成物は、水性オーバープリントニス組成物として優れた性能を発揮する。
In addition, as a method for producing the aqueous resin having the core-shell structure, a multistage polymerization method such as a seed polymerization method or a core-shell polymerization method can be used.
By containing an emulsion-type aqueous resin having both a core part contributing to rigidity and film strength and a shell part contributing to film formability and durability, the aqueous coating agent for paper containers of the present invention The composition exhibits excellent performance as an aqueous overprint varnish composition.
また、上記エマルジョン型の水性樹脂は、本発明の紙器用水性被覆剤組成物を紙器用水性グラビア印刷インキ組成物として使用する場合、上記単量体Ａと上記単量体Ｂとを主成分とするエチレン性不飽和単量体混合物を、上記高分子乳化剤の存在下で、乳化重合して得られた樹脂であることが好ましい。 In addition, the emulsion-type aqueous resin contains the monomer A and the monomer B as main components when the paper container aqueous coating composition of the present invention is used as a paper container aqueous gravure printing ink composition. It is preferable that the ethylenically unsaturated monomer mixture to be obtained is a resin obtained by emulsion polymerization in the presence of the polymer emulsifier.
本発明の紙器用水性被覆剤組成物を紙器用水性グラビア印刷インキ組成物として使用する場合の上記エマルジョン型の水性樹脂は、酸価が２５〜４０ｍｇＫＯＨ／ｇであることが好ましい。
上記エマルジョン型の水性樹脂の酸価が２５ｍｇＫＯＨ／ｇより小さいと、再溶解性が低下する傾向にあり、酸価が４０ｍｇＫＯＨ／ｇより大きいと、乾燥性が低下する傾向があり、好ましくない。
When the aqueous coating composition for paper containers of the present invention is used as an aqueous gravure printing ink composition for paper containers, the emulsion type aqueous resin preferably has an acid value of 25 to 40 mgKOH / g.
When the acid value of the emulsion-type aqueous resin is less than 25 mgKOH / g, the re-solubility tends to be lowered, and when the acid value is larger than 40 mgKOH / g, the drying property tends to be lowered.
本発明の紙器用水性被覆剤組成物を紙器用水性グラビア印刷インキ組成物として使用する場合の上記エマルジョン型の水性樹脂は、ガラス転移温度が１５〜６０℃であることが好ましい。
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、得られる印刷物のブロッキング性が低下するおそれがある、６０℃を超えると、得られる印刷物の耐摩性が低下するおそれがある。
When the aqueous coating composition for paper containers of the present invention is used as an aqueous gravure printing ink composition for paper containers, the emulsion-type aqueous resin preferably has a glass transition temperature of 15 to 60 ° C.
When the glass transition temperature of the emulsion-type aqueous resin is less than 15 ° C, the blocking property of the obtained printed matter may be lowered. When the glass transition temperature exceeds 60 ° C, the wear resistance of the obtained printed matter may be lowered.
なお、本発明において、ガラス転移温度、及び、酸価は、以下の方法により求めることができる。
＜ガラス転移温度＞
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。
Ｗｏｏｄの式：１／Ｔｇ＝Ｗ１／Ｔｇ１＋Ｗ２／Ｔｇ２＋Ｗ３／Ｔｇ３＋・・・・・・・・・＋Ｗｘ／Ｔｇｘ
（式中、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）
In the present invention, the glass transition temperature and the acid value can be determined by the following methods.
<Glass transition temperature>
The glass transition temperature is a theoretical glass transition temperature obtained by the following wood equation.
Wood formula: 1 / Tg = W1 / Tg1 + W2 / Tg2 + W3 / Tg3 +... + Wx / Tgx
(Wherein Tg1 to Tgx are the glass transition temperatures of the respective homopolymers of monomers 1, 2, 3,..., X constituting the copolymer, and W1 to Wx are the monomers 1, 2, 3,..., X each mass fraction, Tg represents the theoretical glass transition temperature (however, the glass transition temperature in the wood equation is an absolute temperature)
＜酸価＞
共重合体１ｇを得るために理論上必要な各エチレン性不飽和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。
そして、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エチレン性不飽和単量体を、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。
また、上記酸価は、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。
<Acid value>
For the amount of each ethylenically unsaturated monomer that is theoretically required to obtain 1 g of copolymer, the theoretical neutralization amount of KOH is obtained, and the total number of mg of the neutralization amount is determined as the copolymer. The acid value (theoretical acid value) is considered.
The glass transition temperature of the emulsion-type aqueous resin is obtained when all ethylenically unsaturated 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 of the copolymer.
The acid value is derived from the polymer emulsifier. For example, the acid value when 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 is the acid value. The value is 10 mgKOH / g.
上記エマルジョン型の水性樹脂の含有量は、上記紙器用水性被覆剤組成物中固形分で１０〜４５質量％であることが好ましい。
また、本発明の紙器用水性被覆剤組成物を紙器用水性オーバープリントニス組成物として使用する場合は、上記エマルジョン型の水性樹脂の含有量は、上記紙器用水性被覆剤組成物中固形分で２０〜４５質量％であることが好ましく、乾燥性の点から、固形分が高いほうがより好ましい。
The content of the emulsion-type aqueous resin is preferably 10 to 45% by mass in the solid content in the paper container aqueous coating composition.
Moreover, when using the aqueous coating composition for paper containers of the present invention as an aqueous overprint varnish composition for paper containers, the content of the emulsion-type aqueous resin is a solid content in the aqueous coating composition for paper containers. It is preferable that it is 20-45 mass%, and the one where solid content is higher is more preferable from the point of drying property.
本発明の紙器用水性被覆剤組成物は、使用用途に応じて、任意成分を適宜含有していてもよい。上記任意成分としては、顔料、水溶性樹脂、界面活性剤、顔料分散剤、体質顔料、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、種々の添加剤を挙げることができる。 The aqueous coating composition for paper containers of the present invention may optionally contain optional components depending on the intended use. Examples of the optional components include pigments, water-soluble resins, surfactants, pigment dispersants, extender pigments, waxes, wetting agents, antifoaming agents, pH adjusting agents, viscosity adjusting agents, drying adjusting agents, brightening agents, and crosslinking agents. Various additives can be mentioned.
さらに、本発明の紙器用水性被覆剤組成物は、紙器用水性グラビア印刷インキ組成物として使用する場合、着色剤とアルカリ可溶型水溶性樹脂とを含有することが好ましい。 Furthermore, when the aqueous coating composition for paper containers of the present invention is used as an aqueous gravure printing ink composition for paper containers, it preferably contains a colorant and an alkali-soluble water-soluble resin.
ここで、利用可能な着色剤としては、特に限定されず、通常、水性印刷インキで使用される顔料が挙げられる。具体的に、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、黒鉛等の有色顔料；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、タルク等の体質顔料等を挙げることができる。また、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、縮合多環顔料等を挙げることができる。 Here, the colorant that can be used is not particularly limited, and examples thereof include pigments usually used in water-based printing inks. Specifically, as inorganic pigments, colored pigments such as titanium oxide, bengara, antimony red, cadmium yellow, cobalt blue, bitumen, ultramarine, carbon black, graphite, etc .; calcium carbonate, kaolin, barium sulfate, aluminum hydroxide, clay, Examples include extender pigments such as talc. Examples of organic pigments include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments.
また、顔料分散性向上の目的で顔料分散剤を含有しても良く、乾燥性や流動性の改善等の目的で体質顔料を含有していても良い。
上記体質顔料の具体例としては、炭酸カルシウム、炭酸マグネシウム、沈降性硫酸バリウム、水酸化アルミニウム等を挙げることができる。
上記体質顔料の含有量は、上記紙器用水性被覆剤組成物中１５質量％以下であることが好ましい。１５質量％を超えると、上記紙器用水性被覆剤組成物を水性グラビア印刷インキ組成物として使用した場合に、該インキ組成物の安定性が低下するおそれがある。
In addition, a pigment dispersant may be contained for the purpose of improving pigment dispersibility, and an extender pigment may be contained for the purpose of improving drying properties and fluidity.
Specific examples of the extender include calcium carbonate, magnesium carbonate, precipitated barium sulfate, aluminum hydroxide and the like.
The content of the extender pigment is preferably 15% by mass or less in the aqueous coating composition for paper containers. When the content exceeds 15% by mass, the stability of the ink composition may be lowered when the paper container aqueous coating composition is used as an aqueous gravure printing ink composition.
上記アルカリ可溶型水溶性樹脂としては、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エチレン性不飽和単量体を重合させて得られる、塩基性化合物の存在下で、水中に可溶となるような樹脂であって、水性印刷インキで使用できる公知のものを挙げることができる。
具体的には、アクリル系、スチレン−アクリル系、スチレン−マレイン酸系、および、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例示できる。
これらの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、水中に溶解させて水溶性樹脂ワニスとして使用する。
上記アルカリ可溶型水溶性樹脂の含有量は、通常、上記紙器用水性被覆剤組成物中に１〜１５質量％であることが好ましい。
The alkali-soluble water-soluble resin is obtained by polymerizing an ethylenically unsaturated monomer having as essential components a monomer having an acid group such as a carboxyl group and an ethylenically unsaturated double bond in the molecule. Examples of the obtained resin that is soluble in water in the presence of a basic compound and that can be used in water-based printing inks can be given.
Specific examples include alkali-soluble water-soluble resins such as acrylic, styrene-acrylic, styrene-maleic acid, and styrene-acrylic-maleic acid.
These alkali-soluble water-soluble resins are usually dissolved in water in the presence of a basic compound and used as a water-soluble resin varnish.
In general, the content of the alkali-soluble water-soluble resin is preferably 1 to 15% by mass in the aqueous coating composition for paper containers.
本発明の紙器用水性被覆剤組成物は、紙器用水性グラビア印刷インキ組成物として使用する場合、本発明の効果を低下させない範囲で、更に、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いてもよい。 When used as an aqueous gravure printing ink composition for paper containers, the aqueous coating composition for paper containers of the present invention is a range that does not reduce the effect of the present invention, and further, other aqueous binder resin varnishes, such as aqueous shellac varnishes, An aqueous casein varnish, an aqueous rosin maleic resin varnish, an aqueous polyester resin varnish, a water-soluble cellulose varnish, and the like may be contained.
以上の構成材料を用いて、本発明の紙器用水性被覆剤組成物を製造する方法を説明する。
本発明の紙器用水性被覆剤組成物を紙器用水性オーバープリントニス組成物として使用する場合、上記水性被覆剤組成物を製造する方法としては、各構構成材料をディスパー等の攪拌装置で均一に攪拌することにより得る方法が挙げられる。
また、本発明の紙器用水性被覆剤組成物を紙器用水性グラビア印刷インキ組成物として使用する場合、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顔料分散剤等を混合し、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、混練り後、水性樹脂、２−エチル−１，３−ヘキサンジオール、必要に応じて、体質顔料分散物、ワックス、消泡剤等を添加混合して製造する方法が挙げられる。
上記体質顔料を添加する場合は、上記エマルジョン型の水性樹脂又は上記アルカリ可溶性水溶性樹脂等で、上記体質顔料を水性媒体中に分散させたものを使用することが好ましい。
A method for producing the aqueous coating composition for paper containers of the present invention using the above constituent materials will be described.
When using the aqueous coating composition for paper containers of the present invention as an aqueous overprint varnish composition for paper containers, as a method for producing the aqueous coating composition, each constituent material is uniformly mixed with a stirring device such as a disper. The method obtained by stirring is mentioned.
Moreover, when using the aqueous coating composition for paper containers of the present invention as an aqueous gravure printing ink composition for paper containers, first, a colorant, an alkali-soluble water-soluble resin, and a pigment dispersant to be added as necessary Etc., and after stirring and kneading using a normal ink production apparatus (for example, ball mill, attritor, sand mill, etc.), aqueous resin, 2-ethyl-1,3-hexanediol, and if necessary, constitution Examples thereof include a method in which a pigment dispersion, wax, antifoaming agent and the like are added and mixed.
When the extender is added, it is preferable to use the emulsion-type aqueous resin or the alkali-soluble water-soluble resin in which the extender is dispersed in an aqueous medium.
本発明の紙器用水性被覆剤組成物の塗布、印刷方法及び印刷物の製造方法の好ましい例について説明する。
本発明の紙器用水性被覆剤組成物を高品位印刷用途として使用する方法として、コート紙等の紙基材に、上述した着色剤等を含有し、紙器用水性グラビア印刷インキ組成物とした紙器用水性被覆剤組成物をグラビア印刷方式で被覆処理した後、上述した紙器用水性オーバープリントニス組成物とした紙器用水性被覆剤組成物を塗工する方法であることが好ましい。上記塗工は、グラビアやフレキソのロールコーター、バーコーター等の各種塗工手段を用いて行うとよい。
The preferable example of application | coating of the aqueous | water-based coating composition for paper containers of this invention, the printing method, and the manufacturing method of printed matter is demonstrated.
As a method of using the aqueous coating composition for paper containers of the present invention for high-quality printing applications, a paper container containing the above-described colorant or the like in a paper base material such as coated paper and made into an aqueous gravure printing ink composition for paper containers. It is preferable that the aqueous coating composition for paper containers is coated by the gravure printing method, and then the aqueous coating composition for paper containers is applied as the above-described aqueous overprint varnish composition for paper containers. The coating may be performed using various coating means such as a gravure or flexo roll coater or a bar coater.
印刷物の製造効率を考慮すると、印刷及び塗工スピードは１５０ｍ／分以上が好ましい。また、上述の印刷及び塗工スピードとするために、印刷後及び塗工後に、各種加熱乾燥装置を利用した乾燥工程を有していてもよい。 Considering the production efficiency of printed matter, the printing and coating speed is preferably 150 m / min or more. Moreover, in order to set it as the above-mentioned printing and coating speed, you may have the drying process using various heat drying apparatuses after printing and after coating.
なお、印刷時、上記紙器用水性グラビア印刷インキ組成物の粘度は、ザーンカップＮｏ．３の流出秒数が１５〜１８秒程度であることが好ましい。
また、通常、上記紙器用水性グラビア印刷インキ組成物は、濃縮の状態で保存され、印刷時に希釈剤により希釈される。上記希釈は、希釈後の上記紙器用水性グラビア印刷インキ組成物中の炭素数１〜４の低級アルコールが所定の含有量となるように、水と炭素数１〜４の低級アルコールとの混合溶媒で行うことが好ましい。
更に、乾燥性やＶＯＣ排出量の観点から、印刷時の上記紙器用水性グラビア印刷インキ組成物中の固形分総量は、１５〜２５質量％であることが好ましい。
また、同様に、上記水性オーバープリントニス組成物についても、塗工方法に適した粘度と、炭素数１〜４の低級アルコールとが所定の含有量となるように希釈する。
When printing, the viscosity of the waterborne gravure printing ink composition for paper containers is Zahn Cup No. 3 is preferably about 15 to 18 seconds.
In addition, the above-mentioned aqueous gravure printing ink composition for paper containers is usually stored in a concentrated state and diluted with a diluent during printing. The dilution is a mixed solvent of water and a lower alcohol having 1 to 4 carbon atoms so that the lower alcohol having 1 to 4 carbon atoms in the aqueous gravure printing ink composition for paper containers after dilution has a predetermined content. It is preferable to carry out with.
Furthermore, from the viewpoint of drying property and VOC discharge, the total solid content in the aqueous gravure printing ink composition for paper containers at the time of printing is preferably 15 to 25% by mass.
Similarly, the aqueous overprint varnish composition is also diluted so that the viscosity suitable for the coating method and the lower alcohol having 1 to 4 carbon atoms have a predetermined content.
上述の紙器用水性グラビア印刷インキ組成物の印刷と紙器用水性オーバープリントニス組成物の塗工とは、一連の工程で行われても良く、別々の機会に工程を分けて行われても良い。また、例えば、６缶パックのパッケージなどは、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、印刷、塗工と一連の工程で行われても良く、別々の機会に工程を分けて行われても良い。
このようなグラビア印刷、塗工、後加工まで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が挙げられる。 具体的には、紙基材を給紙部に供給し、給紙部から上記紙器用水性グラビア印刷インキ組成物のグラビア印刷方式による被覆、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、印刷・塗工スピードとして１５０〜２００ｍ／ｍｉｎで印刷及び塗工を行い、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。
さらに、上記紙器用水性グラビア印刷インキ組成物を印刷後、及び、紙器用水性オーバープリントニス組成物を塗工後、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が高くなる。
The printing of the above-described aqueous gravure printing ink composition for paper containers and the application of the aqueous overprint varnish composition for paper containers may be performed in a series of steps, or may be performed separately on different occasions. . In addition, for example, a package of 6 can packs is subjected to post-processing such as punching after manufacturing a printed material. However, this post-processing may be performed in a series of processes such as printing and coating. The process may be divided into occasions.
As an apparatus that can perform such gravure printing, coating, and post-processing at once, for example, a Bobst Champlein Remanic gravure rotary punching machine can be cited. Specifically, a paper base material is supplied to a paper feeding unit, and the water-based gravure printing ink composition for paper containers is coated by a gravure printing method from the paper feeding unit, and the water-based overprint varnish composition for paper containers is coated by coating. Can be printed and coated at a printing / coating speed of 150 to 200 m / min, and then subjected to a punching process to obtain a desired printed matter.
Furthermore, after printing the water based gravure printing ink composition for paper containers and after coating the water based overprint varnish composition for paper containers, by using a hot air drying device for drying, printing efficiency, coating efficiency, overall The production efficiency of the printed matter is increased.
このように、本発明の紙器用水性被覆剤組成物を、紙器用水性グラビア印刷インキ組成物及び水性オーバープリントニス組成物として適用し、紙基材に、上記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り被覆処理した後、上記水性オーバープリントニス組成物を塗工することを特徴とする紙器用印刷物の製造方法もまた本発明の一つである。
上記紙器用印刷物の製造方法により、印刷適性も従来のものに比べて低下させることなく、ＶＯＣ排出濃度を規定濃度以下に削減することができる。
Thus, the aqueous coating composition for paper containers of the present invention is applied as an aqueous gravure printing ink composition for paper containers and an aqueous overprint varnish composition, and the aqueous gravure printing ink composition for paper containers is applied to a paper substrate. A method for producing a printed matter for paper containers, wherein the aqueous overprint varnish composition is applied after coating by a gravure printing method, is also one aspect of the present invention.
By the method for producing a printed matter for paper containers, the VOC emission concentration can be reduced to a specified concentration or less without lowering the printability as compared with the conventional one.
本発明の紙器用水性被覆剤組成物は、上記構成からなるものであるため、含まれる低級アルコールの量を極力少なくして、印刷適性、乾燥性に優れた紙器用水性グラビア印刷インキ組成物、又は、乾燥性、レベリング性が良好な紙器用水性オーバープリントニス組成物として好適に適用することができる。 Since the aqueous coating composition for paper containers of the present invention has the above-described configuration, the amount of the lower alcohol contained is reduced as much as possible, and the aqueous gravure printing ink composition for paper containers excellent in printability and drying properties, Or it can apply suitably as a water-based overprint varnish composition for paper containers with favorable drying property and leveling property.
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１〜５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 1-5.
＜紙器用水性オーバープリントニス用途の紙器用水性被覆剤組成物（以下、水性オーバープリントニス又はＯＰニスと略記）＞
構成材料
水性媒体：水、２−エチル−１，３−ヘキサンジオール
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）
水性樹脂：下記の水性樹脂製造例により得られた水性樹脂１、２及び市販の水性樹脂３
<Aqueous overprint varnish for paper containers Aqueous coating composition for paper containers (hereinafter abbreviated as aqueous overprint varnish or OP varnish)>
Constituent material aqueous medium: water, 2-ethyl-1,3-hexanediol antifoaming agent: BYK-028 # C (trade name, manufactured by Big Chemie)
Wax: Chemipearl-400W (trade name, manufactured by Mitsui Chemicals)
Aqueous resin: aqueous resins 1 and 2 obtained by the following aqueous resin production examples and commercially available aqueous resin 3
（水性樹脂製造例）
水性樹脂１の製造
アクリル酸２８質量％、スチレン５０質量％、α−メチルスチレン２２質量％からなるエチレン性不飽和単量体混合物を共重合して得たアルカリ可溶性樹脂のアンモニア水溶液を高分子乳化剤として調製した。この高分子乳化剤３０質量部に対し、スチレン５６．５質量部を添加しながら、常法により乳化重合し、エマルジョンを得た。その後、このエマルジョンをシードとして、２−エチルヘキシルアクリレート１３．５質量部を加えて、常法により重合し、酸価６５ｍｇＫＯＨ／ｇ、ガラス転移温度６０℃、固形分４６％のエマルジョン型水性樹脂１を得た。
(Water-based resin production example)
Production of aqueous resin 1 An aqueous ammonia solution of an alkali-soluble resin obtained by copolymerizing an ethylenically unsaturated monomer mixture comprising 28% by mass of acrylic acid, 50% by mass of styrene, and 22% by mass of α-methylstyrene is a polymer emulsifier. As prepared. While adding 56.5 parts by mass of styrene to 30 parts by mass of this polymer emulsifier, emulsion polymerization was carried out by an ordinary method to obtain an emulsion. Thereafter, 13.5 parts by mass of 2-ethylhexyl acrylate was added using this emulsion as a seed, and polymerization was carried out by a conventional method. Obtained.
水性樹脂２の製造
アクリル酸２５質量％、スチレン５０質量％、α−メチルスチレン２５質量％からなるからなるエチレン性不飽和単量体混合物を共重合して得たアルカリ可溶性樹脂のアンモニア水溶液を高分子乳化剤として調製した。この高分子乳化剤に、該高分子乳化剤の樹脂固形分３０質量部に対し、２−エチルヘキシルアクリレートの１２質量部を３０分間、スチレンの５２．７質量部を１時間、同時に滴下開始し、所定の時間をかけて滴下し、常法のパワーフィード乳化重合法でエマルジョンを得た。その後、このエマルジョンをコア部として、２−エチルヘキシルアクリレートの５．３質量部を加え重合し、酸価５８ｍｇＫＯＨ／ｇ、ガラス転移温度４９℃、固形分４６％のエマルジョン型水性樹脂２を得た。
Production of aqueous resin 2 An aqueous ammonia solution of an alkali-soluble resin obtained by copolymerizing an ethylenically unsaturated monomer mixture comprising 25% by mass of acrylic acid, 50% by mass of styrene, and 25% by mass of α-methylstyrene Prepared as molecular emulsifier. To this polymer emulsifier, dropwise addition of 12 parts by mass of 2-ethylhexyl acrylate for 30 minutes and 52.7 parts by mass of styrene for 1 hour with respect to 30 parts by mass of the resin solid content of the polymer emulsifier, The solution was added dropwise over time, and an emulsion was obtained by a conventional power feed emulsion polymerization method. Thereafter, 5.3 parts by mass of 2-ethylhexyl acrylate was added and polymerized using this emulsion as a core part to obtain an emulsion-type aqueous resin 2 having an acid value of 58 mgKOH / g, a glass transition temperature of 49 ° C., and a solid content of 46%.
市販エマルジョン型水性樹脂
水性樹脂３
ジョンクリル３５２（商品名、ジョンソンポリマー社製、酸価５３ｍｇＫＯＨ／ｇ、ガラス転移温度６０℃、固形分４５％）
Commercially available emulsion type aqueous resin 3
Jonkrill 352 (trade name, manufactured by Johnson Polymer Co., Ltd., acid value 53 mgKOH / g, glass transition temperature 60 ° C., solid content 45%)
実施例ＯＰニス１〜５、比較例ＯＰニス１〜３の調製
表１の配合組成となるように上記構成材料をディスパーで均一に攪拌して、実施例ＯＰニス１〜５、比較例ＯＰニス１〜３を得た。
Preparation of Example OP Varnishes 1 to 5 and Comparative Example OP Varnishes 1 to 3 The above constituent materials were uniformly stirred with a disper so as to have the composition shown in Table 1, and Example OP Varnishes 1 to 5 and Comparative Example OP Varnishes 1-3 were obtained.
＜紙器用水性グラビア印刷インキ組成物用途の紙器用水性被覆剤組成物（以下、水性グラビア印刷インキと略記）＞
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）
体質顔料：白艶華Ｔ−ＤＤ（商品名、白石工業社製、炭酸カルシウム）
水性媒体：水、イソプロパノール、２−エチル−１，３−ヘキサンジオール
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）
水性樹脂：下記の水性樹脂製造例により得られた水性樹脂４及び市販のアルカリ可溶型水溶性樹脂
<Aqueous Gravure Printing Ink Composition for Paper Containers Aqueous Coating Composition for Paper Containers (hereinafter abbreviated as Aqueous Gravure Printing Ink)>
Constituent material Colored pigment: Red pigment (PR48: 3), yellow pigment (PY14), blue pigment (PB15: 3), black pigment (PB7)
Extender pigment: white glaze T-DD (trade name, manufactured by Shiroishi Kogyo Co., Ltd., calcium carbonate)
Aqueous medium: water, isopropanol, 2-ethyl-1,3-hexanediol antifoaming agent: BYK-028 # C (trade name, manufactured by Big Chemie)
Wax: Chemipearl-400W (trade name, manufactured by Mitsui Chemicals, polyethylene wax)
Aqueous resin: aqueous resin 4 obtained by the following aqueous resin production example and commercially available alkali-soluble water-soluble resin
（水性樹脂製造例）
水性樹脂４の製造
アクリル酸８質量％、メタクリル酸メチル７０質量％、アクリル酸ブチル２２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。この高分子乳化剤の樹脂固形分５３質量部に対し、２−エチルヘキシルアクリレートの１９質量部、スチレンの２８質量部を添加し、常法により乳化重合し、酸価３３、ガラス転移温度２２℃、固形分４０％のエマルジョンである水性樹脂４を得た。
(Water-based resin production example)
Production of aqueous resin 4 An aqueous dimethylethanolamine solution of an alkali-soluble resin consisting of 8% by mass of acrylic acid, 70% by mass of methyl methacrylate and 22 parts by mass of butyl acrylate was prepared as a polymer emulsifier. 19 parts by mass of 2-ethylhexyl acrylate and 28 parts by mass of styrene are added to 53 parts by mass of the resin solid content of this polymer emulsifier, and emulsion polymerization is carried out by a conventional method. Acid value 33, glass transition temperature 22 ° C., solid An aqueous resin 4 was obtained which was an emulsion having a content of 40%.
市販アルカリ可溶型水溶性樹脂
ジョンクリルＨＰＤ−６７１（商品名、ジョンソンポリマー社製、スチレン−アクリル系水溶性樹脂、固形分２５％）
Commercially available alkali-soluble water-soluble resin Joncrill HPD-671 (trade name, manufactured by Johnson Polymer Co., Ltd., styrene-acrylic water-soluble resin, solid content 25%)
水性グラビア印刷インキベースの調製
表２の配合に従って、顔料（赤色：ＰＲ４８：３、黄色：ＰＹ１４、青色：ＰＢ１５：３、黒色：カーボンブラック）、アルカリ可溶型水溶性樹脂、水の混合物をビーズミルで混合した後、残りの材料を添加混合して、各色の水性グラビア印刷インキベースを得た。
Preparation of aqueous gravure printing ink base According to the composition of Table 2, a mixture of pigment (red: PR48: 3, yellow: PY14, blue: PB15: 3, black: carbon black), alkali-soluble water-soluble resin, and water is bead mill After mixing, the remaining materials were added and mixed to obtain an aqueous gravure printing ink base of each color.
水性グラビア印刷用体質顔料ベースの調製
表３の配合に従って、体質顔料（商品名：白艶華Ｔ−ＤＤ、白石工業社製、炭酸カルシウム）、水性樹脂４、イソプロパノール、ジエチレングリコール、水の混合物をビーズミルで混合して水性グラビア印刷用体質顔料ベースを得た。
Preparation of base pigment base for aqueous gravure printing Mixture of extender pigment (trade name: Hakujyo Hana T-DD, manufactured by Shiroishi Kogyo Co., Ltd., calcium carbonate), aqueous resin 4, isopropanol, diethylene glycol and water in a bead mill Thus, an extender base for aqueous gravure printing was obtained.
実施例各色インキ１〜５、比較例各色インキ２、３の調製
表４の配合組成となるように、上述の赤色、黄色、青色の水性グラビア印刷インキベース、表３の水性グラビア印刷用体質顔料ベース、水性樹脂４、市販のアルカリ可溶型水溶性樹脂、イソプロパノール、消泡剤、ワックス、２−エチル−１，３−ヘキサンジオール、水を攪拌混合した。その後、イソプロパノール／水が７０／３０の希釈剤Ａを用いて、ザーンカップＮｏ.３で１５〜１８秒となる範囲で、インキ組成物中のイソプロパノールの含有量が２２質量％又は２６質量％となるように希釈し、赤色、黄色、青色の実施例各色インキ１〜５、比較例各色インキ２、３を得た。
Examples Preparation of each color ink 1 to 5 and comparative example color inks 2 and 3 The above-mentioned red, yellow and blue aqueous gravure printing ink bases and the aqueous pigment for aqueous gravure printing shown in Table 3 so as to have the composition shown in Table 4 Base, aqueous resin 4, commercially available alkali-soluble water-soluble resin, isopropanol, antifoaming agent, wax, 2-ethyl-1,3-hexanediol, and water were mixed with stirring. Thereafter, the content of isopropanol in the ink composition was 22% by mass or 26% by mass in the range of 15 to 18 seconds in Zahn Cup No. 3 using Diluent A with 70/30 isopropanol / water. It diluted so that red, yellow, and blue Example each color ink 1-5 and comparative example each color ink 2, 3 were obtained.
実施例黒色インキ１〜５、比較例黒色インキ２、３の調製
表４の配合組成となるように、黒色の水性グラビア印刷インキベース、水性樹脂４、市販のアルカリ可溶型水溶性樹脂、イソプロパノール、消泡剤、ワックス、２−エチル−１，３−ヘキサンジオールを攪拌混合し、その後、希釈剤Ａを用いて、ザーンカップＮｏ.３で１５〜１８秒となる範囲で、インキ組成物中のイソプロパノールの含有量が２２質量％又は２６質量％となるように希釈し、実施例黒色インキ１〜５、比較例黒色インキ２、３を得た。
Preparation of Examples Black Inks 1 to 5 and Comparative Examples Black Inks 2 and 3 Black aqueous gravure printing ink base, aqueous resin 4, commercially available alkali-soluble water-soluble resin, isopropanol so as to have the composition shown in Table 4 , Defoaming agent, wax, 2-ethyl-1,3-hexanediol with stirring, and then using Diluent A in the range of 15-18 seconds in Zahn Cup No. 3, in the ink composition Were diluted so that the content of isopropanol was 22% by mass or 26% by mass, and Example Black Inks 1 to 5 and Comparative Example Black Inks 2 and 3 were obtained.
比較例各色インキ１
各色の水性グラビア印刷インキとして、市販品を用いた。
表５に、用いた市販品の黄色、赤色、青色、黒色のそれぞれの水性グラビア印刷インキの配合組成を示す。
Comparative Example Each color ink 1
Commercial products were used as water-based gravure printing inks for each color.
Table 5 shows the composition of each of the commercially available yellow, red, blue and black aqueous gravure printing inks used.
＜印刷物の製造＞
実施例（赤色、黄色、青色、黒色）インキ１〜５、比較例（赤色、黄色、青色、黒色）インキ１〜３、実施例ＯＰニス１〜５、比較例ＯＰニス１〜３を表６の組合せとなるように下記の方法によりインライン方式で印刷及び塗工して、実施例１〜６、比較例１〜３の印刷物を得た。
（印刷条件）
用紙：コート紙（商品名：ＣＲＣ２３０、レンゴー（株）社製）
印刷機械：東芝グラビア印刷機
インキを印刷する刷版：ヘリオ１７５ｌｉｎｅ／ｉｎｃｈ
（図柄：網点濃度５〜１００％の諧調を有する諧調版）
ニスを塗布する刷版：ヘリオ１７５ｌｉｎｅ／ｉｎｃｈ
印刷速度：１５０〜２００ｍ／ｍｉｎ
乾燥条件：８０℃・８０ｃｍ３／ｍｉｎ
印圧：２．２ｔ
<Manufacture of printed matter>
Example (red, yellow, blue, black) inks 1-5, comparative example (red, yellow, blue, black) inks 1-3, example OP varnishes 1-5, comparative example OP varnishes 1-3 are shown in Table 6. The printed materials of Examples 1 to 6 and Comparative Examples 1 to 3 were obtained by printing and coating in an inline manner by the following method so as to obtain a combination of
(Printing conditions)
Paper: Coated paper (trade name: CRC230, manufactured by Rengo Co., Ltd.)
Printing machine: Toshiba gravure printing press Printing plate for printing ink: Helio 175 line / inch
(Pattern: gradation version with gradation of halftone dot concentration 5-100%)
Printing plate to apply varnish: Helio 175line / inch
Printing speed: 150 to 200 m / min
Drying conditions: 80 ° C./80 cm 3 / min
Printing pressure: 2.2t
＜印刷評価＞
（乾燥性）
水性グラビア印刷（黄色、赤色、青色、黒色）インキ及び水性オーバープリントニスの乾燥性は、東芝グラビア印刷機にて印刷速度をかえて印刷・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、ニス）が付着して汚れる度合いを目視にて評価した。その結果を表６に示した。
評価
○：ガイドロールに付着しない。
△：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。
<Printing evaluation>
(Drying)
The dryness of water-based gravure printing (yellow, red, blue, black) ink and water-based overprint varnish is printed and coated at different printing speeds on the Toshiba gravure printing machine and printed on the guide roll (printed surface, coated surface) ), The degree of (ink, varnish) adhering to the guide roll and soiling was visually evaluated. The results are shown in Table 6.
Evaluation (circle): It does not adhere to a guide roll.
Δ: Amount of adhesion to the guide roll is small.
X: The amount of adhesion to the guide roll is large.
（レベリング性）
実施例１〜６、比較例１〜３の印刷物のレベリング性を目視にて評価した。その結果を表６に示した。
○：なみうちがないもの
△：少しなみうちがあるもの
×：なみうちが多いもの
(Leveling)
The leveling properties of the printed materials of Examples 1 to 6 and Comparative Examples 1 to 3 were visually evaluated. The results are shown in Table 6.
○: Things with no Nanamiuchi △: Things with a little Nauchiuchi ×: Things with a lot of Nauchiuchi
（耐摩擦性）
実施例１〜６、比較例１〜３の印刷物を２．５ｃｍ×２５ｃｍに切断してテストピースとし、学振型耐摩擦試験機（（株）大宋科学精器製作所製）を使用して、当て紙（非印刷状態のコート紙）を印刷物の印刷面に当てて、５００ｇの荷重で５００回ずつ摩擦して耐摩擦性を評価した。その結果を表６に示した。
評価
○：当て紙が全く損傷しないもの
△：当て紙に少し損傷が認められないもの
×：当て紙に損傷が認められるもの。
(Abrasion resistance)
The printed materials of Examples 1 to 6 and Comparative Examples 1 to 3 were cut into 2.5 cm × 25 cm to make test pieces, and using a Gakushin type anti-friction tester (manufactured by Otsuki Scientific Instruments). Then, a paper sheet (non-printed coated paper) was applied to the printed surface of the printed material and rubbed 500 times with a load of 500 g to evaluate the friction resistance. The results are shown in Table 6.
Evaluation ○: No damage to the patch paper Δ: No damage to the patch paper X: Damage to the patch paper
（耐水耐摩擦性）
実施例１〜６、比較例１〜３の印刷物を２．５ｃｍ×２５ｃｍに切断してテストピースとし、学振型耐摩擦試験機を使用して（（株）大宋科学精器製作所製）、当て紙として非印刷状態のコート紙にガーゼを被せ、さらに注射針で水を５滴浸透させたものを用い、２００ｇの荷重で５０回ずつ摩擦して耐水耐摩擦性を評価した。その結果を表６に示した。
評価基準
○：ガーゼが全く汚れないもの
△：ガーゼがうっすらと汚れるもの
×：ガーゼが汚れるもの
(Water and friction resistance)
The printed materials of Examples 1 to 6 and Comparative Examples 1 to 3 were cut into 2.5 cm × 25 cm to make test pieces, and using a Gakushin type anti-friction tester (manufactured by Otsuka Scientific Seiki Seisakusho) The coated paper in a non-printed state was covered with gauze as a backing paper, and further 5 drops of water were infiltrated with an injection needle, and the water friction resistance was evaluated by rubbing 50 times with a load of 200 g. The results are shown in Table 6.
Evaluation criteria ○: Gauze is not soiled △: Gauze is slightly soiled x: Gauze is soiled
（耐ブロッキング性）
実施例１〜６、比較例１〜３の印刷物を５ｃｍ×５ｃｍに切断した各サンプルピースの印刷面同士を合わせ、１０００ｇ／ｃｍ２の荷重をかけて、３５℃／９０％ＲＨの環境条件下で２４時間放置した後、サンプルピース同士の接触面を剥離したときのブロッキングの程度からブロッキング性を評価した。その結果を表６に示した。
評価基準
○：接触面が抵抗なく剥離するもの
△：少し取られるもの
×：多く取られるもの
(Blocking resistance)
The printed surfaces of Examples 1 to 6 and Comparative Examples 1 to 3 were cut to 5 cm × 5 cm, the print surfaces of each sample piece were put together, a load of 1000 g / cm 2 was applied, and an environmental condition of 35 ° C./90% RH Then, the blocking property was evaluated from the degree of blocking when the contact surfaces of the sample pieces were peeled off. The results are shown in Table 6.
Evaluation criteria ○: The contact surface peels without resistance Δ: A little removed ×: Many removed
（溶剤排出量（炭化水素濃度ｐｐｍＣ））
上記印刷方法の際に排出される溶剤排出量（ＶＯＣ排出濃度）を簡易型炭化水素濃度測定装置により測定した。その結果を表６に示した。
(Solvent emissions (hydrocarbon concentration ppmC))
The amount of solvent discharged (VOC discharge concentration) discharged during the printing method was measured with a simple hydrocarbon concentration measuring device. The results are shown in Table 6.
紙器用水性グラビア印刷（黄色、赤色、青色、黒色）インキ組成物のレベリング性、網点再現性については、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印刷し、その印刷物について評価した。
＜印刷条件＞
用紙：コート紙（商品名：ＣＲＣ２３０、レンゴー（株）社製）
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：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℃
Water-based gravure printing for paper containers (yellow, red, blue, black) For leveling and halftone dot reproducibility of ink compositions, water-based gravure printing ink compositions for paper containers are printed on coated paper under the following conditions. Was evaluated.
<Printing conditions>
Paper: Coated paper (trade name: CRC230, manufactured by Rengo Co., Ltd.)
Printing machine: Gravure proofing machine Printing plate for printing ink: Helio 175ine / inch
(Pattern: gradation version with gradation of halftone dot concentration 5-100%)
Printing speed: 80m / min
Drying conditions: 80 ° C
＜印刷物評価＞
（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、抜けを目視にて評価した。その結果を表６に示した。
評価基準
○：濃淡むら、抜けがないもの
△：濃淡むら又は抜けが少しあるもの
×：濃淡むら又は抜けが多いもの
<Evaluation of printed matter>
(Leveling)
The obtained printed matter was visually evaluated for density unevenness and omission in a solid portion having a dot density of 100%. The results are shown in Table 6.
Evaluation criteria ○: Shading unevenness, no missing △: Shading unevenness or a little missing ×: Shading unevenness or missing much
（網点再現性）
得られた各印刷物の網点の状態を目視にて評価した。その結果を表６に示した。
評価基準
○：比較インキ１（市販インキ）より優れるもの
△：比較インキ１（市販インキ）と同等なもの
×：比較インキ１（市販インキ）より劣るもの
(Halftone dot reproducibility)
The state of the halftone dot of each obtained printed matter was visually evaluated. The results are shown in Table 6.
Evaluation criteria ○: superior to comparative ink 1 (commercial ink) Δ: equivalent to comparative ink 1 (commercial ink) ×: inferior to comparative ink 1 (commercial ink)
本発明の紙器用水性被覆剤組成物は、紙器用水性グラビア印刷インキ組成物、又は、紙器用水性オーバープリントニス組成物として適用することができる。 The aqueous coating composition for paper containers of the present invention can be applied as an aqueous gravure printing ink composition for paper containers or an aqueous overprint varnish composition for paper containers.
Claims (5)
前記水性媒体は、水及び２−エチル−１，３−ヘキサンジオールからなり、The aqueous medium consists of water and 2-ethyl-1,3-hexanediol,
前記２−エチル−１，３−ヘキサンジオールの含有量が０．１〜２．５質量％であり、The content of the 2-ethyl-1,3-hexanediol is 0.1 to 2.5% by mass,
前記エマルジョン型の水性樹脂は、高分子乳化剤の存在下で、芳香環を有するエチレン性不飽和単量体Ａを主成分とするエチレン性不飽和単量体を乳化重合させてコア部を形成し、次いで、単独で重合したときに得られる重合体のガラス転移温度が−５０℃以下であるエチレン性不飽和単量体Ｂを乳化重合させてシェル部を形成して得られる樹脂であり、The emulsion-type aqueous resin forms a core part by emulsion polymerization of an ethylenically unsaturated monomer having an aromatic ring as a main component in the presence of a polymer emulsifier. Then, a resin obtained by emulsion polymerization of an ethylenically unsaturated monomer B having a glass transition temperature of −50 ° C. or lower of a polymer obtained when polymerized alone to form a shell part,
更に、前記エマルジョン型の水性樹脂は、酸価が５０〜７０ｍｇＫＯＨ／ｇであり、ガラス転移温度が４０〜７０℃であるFurthermore, the emulsion-type aqueous resin has an acid value of 50 to 70 mgKOH / g and a glass transition temperature of 40 to 70 ° C.
ことを特徴とする紙器用水性被覆剤組成物。An aqueous coating composition for paper containers.
更に、着色剤、及び、アルカリ可溶型水溶性樹脂を含有し、Furthermore, it contains a colorant and an alkali-soluble water-soluble resin,
前記水性媒体は、水、２−エチル−１，３−ヘキサンジオール及び炭素数１〜４の低級アルコールからなるものであり、The aqueous medium is composed of water, 2-ethyl-1,3-hexanediol, and a lower alcohol having 1 to 4 carbon atoms,
前記炭素数１〜４の低級アルコールの含有量が１５〜３０質量％であり、前記２−エチル−１，３−ヘキサンジオールの含有量が０．１〜２．５質量％であり、The content of the lower alcohol having 1 to 4 carbon atoms is 15 to 30% by mass, the content of the 2-ethyl-1,3-hexanediol is 0.1 to 2.5% by mass,
前記エマルジョン型の水性樹脂は、酸価が２５〜４０ｍｇＫＯＨ／ｇであり、ガラス転移温度が１５〜６０℃であるThe emulsion type aqueous resin has an acid value of 25 to 40 mgKOH / g and a glass transition temperature of 15 to 60 ° C.
ことを特徴とする紙器用水性被覆剤組成物。An aqueous coating composition for paper containers.
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| CN102952431A (en) * | 2012-11-20 | 2013-03-06 | 义乌市伟航水性油墨有限公司 | Cigarette tipping paper water-based ink and preparation method |
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