JP4285069B2 - Gravure printing ink composition for surface printing - Google Patents
Gravure printing ink composition for surface printing Download PDFInfo
- Publication number
- JP4285069B2 JP4285069B2 JP2003130376A JP2003130376A JP4285069B2 JP 4285069 B2 JP4285069 B2 JP 4285069B2 JP 2003130376 A JP2003130376 A JP 2003130376A JP 2003130376 A JP2003130376 A JP 2003130376A JP 4285069 B2 JP4285069 B2 JP 4285069B2
- Authority
- JP
- Japan
- Prior art keywords
- ink composition
- printing ink
- resin
- parts
- printing
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 34
- 238000003854 Surface Print Methods 0.000 title claims description 20
- 238000007646 gravure printing Methods 0.000 title claims description 18
- -1 diamine compound Chemical class 0.000 claims description 38
- 239000004925 Acrylic resin Substances 0.000 claims description 25
- 229920000178 Acrylic resin Polymers 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 25
- 229920005749 polyurethane resin Polymers 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229920005862 polyol Polymers 0.000 claims description 17
- 238000007639 printing Methods 0.000 claims description 16
- 125000000524 functional group Chemical group 0.000 claims description 12
- 150000003077 polyols Chemical class 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 11
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 239000003849 aromatic solvent Substances 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 1
- 239000000976 ink Substances 0.000 description 50
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 28
- 239000002966 varnish Substances 0.000 description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 17
- 230000000903 blocking effect Effects 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 239000000049 pigment Substances 0.000 description 15
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
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- 238000002845 discoloration Methods 0.000 description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- 239000004970 Chain extender Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000020 Nitrocellulose Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000539 dimer Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 6
- 229920001220 nitrocellulos Polymers 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 150000002334 glycols Chemical class 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
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- 239000001993 wax Substances 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
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- 229910001873 dinitrogen Inorganic materials 0.000 description 4
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- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
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- 229920000642 polymer Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000003860 storage Methods 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
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
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- 240000000972 Agathis dammara Species 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
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- 229920001971 elastomer Polymers 0.000 description 1
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- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
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- 235000011187 glycerol Nutrition 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は表刷り用グラビア印刷インキ組成物に関し、より詳しくは、長期高温・多湿下での保存においてフィルム中に含まれる酸化防止剤の変色の低減とテーブルクロスなどに用いられている軟質塩化ビニルシートと印刷物が接着しないための耐塩ビブロッキング性が良好で、さらに環境衛生にも優れた表刷り用グラビア印刷インキ組成物に関するものである。
【０００２】
【従来の技術】
近年、包装容器の多様化に伴い、インキ・印刷業界に対する要望は非常に多岐に渡るようになっている。
【０００３】
例えば、従来より食品メーカーが包装容器の印刷に求めてきた機能は、消費者が購入する際に、いかにして、内容物がおいしそうで、また、高級であるという感じを抱かせるかという点であり、これら印刷物の品質の良し悪しがそのまま製品の売り上げに直結するといっても過言ではない。
【０００４】
さらに、表刷り印刷の分野では、種々のプラスチック製包装容器の表側にインキが印刷されるため、この分野のインキ性能として、印刷適性の他にもフィルムに対する接着性、印刷物同士が接着しないための耐ブロッキング性、テーブルクロスなどに用いられている軟質塩化ビニルシートと印刷物が接着しないための耐塩ビブロッキング性、こすれに対する耐摩擦性、油に対する耐油性、袋の口を溶封する際の耐熱性などといった各種耐性が要求される。
【０００５】
そこで、これらの要求性能を満足するように研究を重ねてきた結果、ポリアミド樹脂とセルロース誘導体をバインダーとし、さらに、バインダー樹脂の溶解性が高くなるように、トルエン等の芳香族化合物系有機溶剤を含むインキが用いられてきた。
【０００６】
しかしながら、最近では、地球環境にやさしい材料を用いて製品を構成することが産業界全体の大きなトレンドであり、特に食品メーカーでは、消費者にクリーンなイメージを持ってもらう事を第一とすることから、より積極的に環境問題に取り組む姿勢が見られるようになっている。
【０００７】
そこで、これらの要求性能を満足するように研究を重ねてきた結果、特開平９−２９６１４３号公報などで開示されているトルエンを含有しないポリアミド樹脂とセルロース誘導体をバインダーとするインキが用いられてきたが、ポリアミド樹脂を主なバインダーするインキは高速での印刷には適さず、印刷機の反転ロールにインキが転移し、印刷物の外観を損ねてしまう問題があった。
【０００８】
また、要求性能を満足させるために、特開昭６１−３７８５１、特願平７−１８３０３９等で開示されているようにインキ組成中にチタネート化合物等のキレート化剤を添加する方法が知られているが、インキの経時安定性が低下するという問題があった。
【０００９】
一方、トルエンを含有せずに高速での印刷に適したインキとして、ポリウレタン樹脂とニトロセルロースをバインダーとするインキが用いられてきた。例えば、特開２００２−６０６６８などで開示されている。
【００１０】
しかしながら、ポリウレタン樹脂とニトロセルロースをバインダーとするインキは、フェノール系酸化防止剤を含有するフィルムを用いた際、火薬学会誌．Vol．６３，No．3，2002で報告されているように長期間高温・多湿の状況に置かれるとニトロセルロースの分解が促進されNOｘが発生する。この発生したＮＯｘはフェノール系酸化防止剤と反応し、フェノール系酸化防止剤がキノン構造をとりフィルムの変色を引き起こすという問題はよく知られている。
【００１１】
さらに、表刷りグラビアインキとしては、テーブルクロスなどに用いられている軟質塩化ビニルシートと印刷物が接着しないための耐塩ビブロッキング性が充分でないという問題があった。
【００１２】
【先行文献１】
特開平９−２９６１４３号公報
【先行文献２】
特開昭６１−３７８５１号公報
【先行文献３】
特願平７−１８３０３９号
【先行文献４】
特開２００２−６０６６８号公報
【発明が解決しようとする課題】
【００１３】
本発明は、芳香族炭化水素系溶剤を含有しない溶剤組成であり、長期高温・多湿下での保存においてフィルム中の酸化防止剤の変色を低減し、かつ、光沢、耐油性、耐熱性、耐揉み性、耐ブロッキング性、特に軟質塩ビシートに対する耐ブロッキング性が良好な表刷り用グラビア印刷インキ組成物を提供することである。
【００１４】
【課題を解決するための手段】
すなわち、本発明は、アクリル樹脂とポリオール成分と有機ジイソシアネートとを反応して得られるウレタンプレポリマーをジアミン化合物で鎖延長し、末端をＣ 8 以上Ｃ 22 以下の長鎖アルキル基またはアルケニル基を有する脂肪族アミン化合物またはＣ 8 以上Ｃ 22 以下の長鎖アルキル基またはアルケニル基を有する脂肪族アミド化合物で反応を停止させたものであるポリウレタン樹脂とをバインダーとして含有し、その含有率が重量換算でアクリル樹脂：ポリウレタン樹脂＝２０：８０〜８０：２０であり、かつ非芳香族系溶剤を含有することを特徴とする表刷り用グラビア印刷インキ組成物に関する。
【００１５】
また、本発明は、一分子中に炭素炭素不飽和二重結合を有し、かつ架橋性の官能基を有しない単量体（a）からなるアクリル樹脂Ａを含有する上記表刷り用グラビア印刷インキ組成物に関する。
【００１６】
また、本発明は、一分子中に炭素炭素不飽和二重結合を有し、かつ架橋性の官能基を有しない単量体（a）５０〜９０重量％と、一分子中に炭素炭素不飽和二重結合を有し、かつ架橋性の官能基を有する単量体（ｂ）１０〜５０重量％とからなるアクリル樹脂Bを含有する上記表刷り用グラビア印刷インキ組成物に関する。
【００１８】
さらに、本発明は、ハードレジンを含有してなる上記表刷り用グラビア印刷インキ組成物に関する。
【００１９】
加えて、本発明は、架橋剤を含有してなる上記表刷り用グラビア印刷インキ組成物、及び上記印刷インキ組成物を基材に印刷してなる印刷物に関する。
【００２０】
以下、本発明を詳細に説明する。
【００２１】
【発明の実施の形態】
本発明では、まず、バインダー樹脂としてアクリル樹脂とポリウレタン樹脂を含有する事を特徴とする。
【００２２】
本発明で利用可能なアクリル樹脂AおよびBは、従来からの既知の方法で製造でき、製造方法は特に制限されるものではない。アクリル樹脂Aは、一分子中に炭素炭素不飽和二重結合を有し、かつ架橋性の官能基を有しない単量体（a）を重合開始剤を用いて溶媒中で重合させることで得られる。アクリル樹脂Bは、一分子中に炭素−炭素不飽和二重結合を有し、かつ架橋性の官能基を有しない単量体（a）と一分子中に炭素炭素不飽和二重結合と架橋性の官能基を有する単量体（ｂ）とを重合開始剤を用いて溶媒中で重合させることで得られる。
【００２３】
ここで、一分子中に炭素−炭素不飽和二重結合を有し、かつ架橋性の官能基を有しない単量体（a）は、(i)（メタ）アクリル酸誘導体、(ii)芳香族ビニル単量体、(iii)オレフィン系炭化水素単量体、(iv)ビニルエステル単量体、(v)ビニルハライド単量体、(vi)ビニルエーテル単量体等があげられる。
【００２４】
(i)（メタ）アクリル酸誘導体の例として、（メタ）アクリロニトリル、（メタ）アクリル酸塩、メチル（メタ）アクリレート、ブチル（メタ）アクリレート、エチルヘキシル（メタ）アクリレート、ステアリル（メタ）アクリレート等のアルキル（メタ）アクリレート、ベンジル（メタ）アクリレート等が挙げられる。
(ii)芳香族ビニル単量体の例として、スチレン、メチルスチレン、エチルスチレン、クロロスチレン、モノフルオロメチルスチレン、ジフルオロメチルスチレン、トリフルオロメチルスチレ等の一部の水素がフッ素置換されたスチレン類等が挙げられる。
(iii)オレフィン系炭化水素単量体の例として、エチレン、プロピレン、ブタジエン、イソブチレン、イソプレン、１、４−ペンタジエン等が挙げられる。
(iv)ビニルエステル単量体の例として、酢酸ビニル等が挙げられる。
(v)ビニルハライド単量体の例として、塩化ビニル、塩化ビニリデン等が挙げられる。
(vi)ビニルエーテル単量体の例として、ビニルメチルエーテル等が挙げられる。これらは、２種以上用いても良く、アクリル樹脂A中では、酸価の値は耐油性、耐熱性の両耐性の面から５０以上２００以下にすることが好ましい。アクリル樹脂B中では、５０〜９０重量％、好ましくは５５〜８０重量％、更に好ましくは６０〜７５重量％の範囲で用いる。この上限を上回った場合には、充分な各種耐性を得ることが困難になる。
【００２５】
つぎに、一分子中に炭素炭素不飽和二重結合と架橋性の官能基を有する単量体（ｂ）の官能基としては、ヒドロキシル基、イソシアノ基、エポキシ基等が挙げられる。
ヒドロキシル基を有する単量体（ｂ）の例としては、２ーヒドロキシエチル（メタ）アクリレート、１ーヒドロキシプロピル（メタ）アクリレート、２ーヒドロキシプロピル（メタ）アクリレート、４ーヒドロキシブチル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、ポリテトラメチレングリコールモノ（メタ）アクリレート、ヒドロキシスチレン等が挙げられる。
【００２６】
また、イソシアノ基を有する単量体（ｂ）の例としては、（メタ）アクリロイルオキシエチルイソシアネート、（メタ）アクリロイルオキシプロピルイソシアネート等の他、２−ヒドロキシエチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレートを、トルエンジイソシアネート、イソホロンジイソシアネート等のポリイソシアネートと反応させて得られるものが挙げられる。
【００２７】
また、エポキシ基を有する単量体（ｂ）の例としては、グリシジルメタクリレート、グリシジルシンナメート、グリシジルアリルエーテル、グリシジルビニルエーテル、ビニルシクロヘキサンモノエポキサイド、１、３−ブタジエンモノエポキサイドなどが挙げられる。
【００２８】
要求性能に応じてこれらの内から１種、または２種以上を混合して用いることができる。
【００２９】
単量体（ｂ）は、アクリル樹脂B中に、１０〜５０重量％、好ましくは２０〜４５重量％、さらに好ましくは２５〜４０重量％の共重合比率で用いられる。この下限を下回った場合には、充分な各種耐性を得ることが困難になる。
【００３０】
重合開始剤としては、通常の過酸化物またはアゾ化合物、例えば、過酸化ベンゾイル、アゾイソブチルバレノニトリル、アゾビスイソブチロニトリル、ジ−ｔ−ブチルペルオキシド、ｔ−ブチルペルベンゾエート、ｔ−ブチルペルオクトエート、クメンヒドロキシペルオキシドなどが用いられ、重合温度は、５０〜１４０℃、好ましくは７０〜１４０℃である。
得られる重合体の好ましい重量平均分子量は、５，０００〜１００，０００である。
【００３１】
上記製造方法に使用される非芳香族系溶剤としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン類、テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテルなどのエーテル類、酢酸エチル、酢酸ブチルなどのエステル類などの使用が可能である。溶剤は２種以上の混合物でもよい。
【００３２】
次に、本発明で利用可能なポリウレタン樹脂は、従来からの既知の方法で製造でき、製造方法は特に制限されるものではない。例えば、ポリオール化合物と有機ジイソシアネート化合物とをイソシアネート基が過剰となる割合で反応させ、ポリオールの末端にイソシアネート基を有するプレポリマーを調整し、次いでこれを溶媒中で鎖延長剤、反応停止剤とを反応させる二段法があげられる。二段法は均一な重合体溶液が得られやすい点で好ましい。溶媒としては、エステル系溶剤、ケトン系溶剤およびアルコール系溶剤の単独または２種以上の混合物を用いることができる。
【００３３】
ここで、利用可能なポリオール化合物としては、酸化エチレン、酸化プロピレン、テトラヒドロフランなどの重合体または共重合体などのポリエーテルポリオール類；エチレングリコール、1,2-プロパンジオール、1,3-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、ネオペンチルグリコール、ペンタジオール、メチルペンタジオール、ヘキサジオール、オクタンジオール、ノナンジオール、メチルノナンジオール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコールなどの飽和および不飽和の低分子グリコール類と、n-ブチルグリシジルエーテル、2-エチルヘキシルグリシジルエーテル等のアルキルグリシジルエーテル類、バーサティック酸グリシジルエステル等のモノカルボン酸グリシジルエステルと、アジピン酸、フタル酸、イソフタル酸、テレフタル酸、マレイン酸、フマル酸、こはく酸、しゅう酸、マロン酸、グルタル酸、ピメリン酸、アゼライン酸、セバシン酸、ダイマー酸などの二塩基酸もしくはこれらの無水物とを脱水縮合せしめて得られるポリエステルポリオール類；その他ポリカーボネートジオール類、ポリブタジエングリコール類、ビスフェノールＡ酸化エチレンまたは酸化プロピレンを付加して得られるグリコール類；ダイマージオール類などの各種公知のポリオールが挙げることができる。これらのポリオールは、単独で用いても、２種以上併用しても良い。
【００３４】
なお、これらのポリオールのうち、グリコール類と二塩基酸から得られるポリオールを用いる場合には、グリコール類のうち５モル％までを各種ポリオールに置換することができる。すなわち、例えばグリセリン、トリメチロールプロパン、トリメチロールエタン、1,2,6-ヘキサントリオール、1,2,4-ブタントリオール、ペンタエリスリトール等のポリオールに置換してもよい。
【００３５】
ポリオールの平均分子量は、得られるポリウレタン樹脂の溶解性、乾燥性、耐ブロッキング性等を考慮して適宜決定されるが、通常は５００〜６０００が好ましい。分子量が５００未満になると溶解性の低下に伴い印刷適性が劣る傾向にあり、また６０００を超えると乾燥性および耐ブロッキング性が低下する。
【００３６】
次に、利用可能な有機ジイソシアネート化合物としては，芳香族、脂肪族または脂環族の各種公知のジイソシアネート類が挙げることができる。たとえば、１，５ーナフチレンジイソシアネート、４，４’ージフェニルメタンジイソシアネート、４，４’ージフェニルジメチルメタンジイソシアネート、４，４’ージベンジルイソシアネート、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、１，３ーフェニレンジイソシアネート、１，４ーフェニレンジイソシアネート、トリレンジイソシアネート、ブタンー１，４ージイソシアネート、ヘキサメチレンジイソシアネート、イソプロピレンジイソシアネート、メチレンジイソシアネート、２，２，４ートリメチルヘキサメチレンジイソシアネート、シクロヘキサンー１，４ージイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、リジンジイソシアネート、ジシクロヘキシルメタンー４、４’ージイソシアネート、１，３ービス（イソシアネートメチル）シクロヘキサン、メチルシクロヘキサンジイソシアネート、ノルボルナンジイソシアネート、ｍーテトラメチルキシリレンジイソシアネートやダイマー酸のカルボキシル基をイソシアネート基に転化したダイマージイソシアネート等である。
【００３７】
次に、ポリオール化合物と有機ジイソシアネートとを反応させる際のポリウレタン樹脂の製造方法は特に限定されるものではない。たとえば、ポリオール化合物と有機ジイソシアネートとを反応させる際の条件はポリオールを過剰にする他に特に限定はないが、イソシアネート基／水酸基の等量比が1．２／１〜３／１の範囲内にあることが望ましい。イソシアネート基／水酸基の等量比が１．２／1以下であると得られたポリウレタン樹脂が脆弱なため、印刷インキに使用した際にブロッキングが発生し易くなる。一方、イソシアネート基／水酸基の等量比が３／１以上であると樹脂の製造に粘度が高くなってしまい、反応中にゲル化し易くなる。また反応温度は通常８０℃〜２００℃の間で行われ、好ましくは９０℃〜１５０℃の間で行うのがよい。
【００３８】
上記のポリウレタン化反応は、溶剤中で行ってもよいし、無溶剤雰囲気下で行ってもよい。溶剤を使用する場合は、後に示す溶剤を反応時の温度および粘度、副反応の制御の面から適宜選択して用いるとよい。また無溶剤雰囲気下でポリウレタン化反応をする場合は、均一なポリウレタン樹脂を得るために、攪拌が十分可能な程度に温度を上げて粘度を下げて行うことが望ましい。ウレタン化反応は10分〜5時間行うのが望ましく、反応の終点は粘度測定、ＩＲ測定によるＮＣＯピーク、滴定によるＮＣＯ％測定等により判断される。
【００３９】
更に、ポリオール化合物と有機ジイソシアネートを反応させて末端イソシアネート基を有するプレポリマーを合成した後、鎖延長剤および反応停止剤を用いてポリウレタン樹脂中に尿素結合を導入し、ポリウレタン・ウレア樹脂とすることで、塗膜物性は更に向上する。
【００４０】
次に、尿素結合を導入する際に利用可能な鎖延長剤としては、各種公知のアミン類を使用することが出来る。たとえばエチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン、トリエチレンテトラミン、ジエチレントリアミン、イソホロンジアミン、ジシクロヘキシルメタン-4，4’-ジアミンなどが挙げられる。その他、２-ヒドロキシエチルエチレンジアミン、２-ヒドロキシエチルプロピレンジアミン、ジ-２-ヒドロキシエチルエチレンジアミン、ジ-2-ヒドロキシエチルプロピレンジアミン、2-ヒドロキシプロピルエチレンジアミン、ジ-２-ヒドロキシプロピルエチレンジアミン等の分子内に水酸基を有するジアミン類およびダイマー酸のカルボキシル基をアミノ基に転化したダイマージアミン等もその代表例として挙げられる。
【００４１】
次に、利用可能な反応停止剤としては、Ｃ８以上Ｃ２２以下の長鎖アルキル基を有する脂肪族アミン化合物またはＣ８以上Ｃ２２以下の長鎖アルキル基を有する脂肪族アミド化合物が挙げられる。脂肪族アミン化合物としては、オクチルアミン、ラウリルアミン、ココナットアミン、ミリスチルアミン、ステアリルアミン、オレイルアミン、パルミチルアミン等の単独もしくは2種以上混合して用いられる。脂肪酸アミド化合物としては、オクタン酸アミド、デカン酸アミド、ラウリン酸アミド、ミリスチン酸アミド、パルミチン酸アミド、ステアリン酸アミド、ベヘン酸アミド、オレイン酸アミド、エルカ酸アミド、リノール酸アミド、リノレン酸アミド等の単独もしくは2種以上混合して用いられる。
【００４２】
Ｃ８以上Ｃ２２以下の長鎖アルキル基を有する脂肪族アミン化合物またはＣ８以上Ｃ２２以下の長鎖アルキル基を有する脂肪族アミド化合物をポリウレタン樹脂の末端に導入することにより耐ブロッキング性が向上する。長鎖アルキル基は表面活性な性質を示すため、塗膜形成過程で表面に配向し、ポリウレタン樹脂の耐ブロッキング性を改善していると考えられる。これら脂肪酸アミンまたは脂肪酸アミドをポリウレタン樹脂に導入することにより、塗膜表面の光沢低下も起こらない。
【００４３】
なお、ポリウレタン樹脂中に尿素結合を導入する製造方法も、特に限定されるものではないが、プレポリマーの両末端に有する遊離のイソシアネート基の数を１とした場合の鎖延長剤および反応停止剤中のアミノ基の合計数量が０．５〜１．３の範囲内であることが好ましい。アミノ基の合計数量が０．５未満の場合、乾燥性、耐ブロッキング性、塗膜強度が充分でなく、１．３より過剰になると、鎖延長剤および反応停止剤が未反応のまま残存し、印刷物に臭気が残りやすい。
【００４４】
上記製造法において使用される溶剤としては、通常、印刷インキ用の溶剤としてよく知られているメタノール、エタノール、イソプロパノール、ｎ−プロパノール、ｎ−ブタノール等のアルコール系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤、酢酸エチル、酢酸プロピル、酢酸ブチル等のエステル系溶剤、メチルシクロヘキサン、エチルシクロヘキサン等の非芳香族炭化水素系溶剤が挙げられ、これらを単独または２種類以上の混合物で用いる。なお反応時に、上記のケトン系溶剤を使用した場合、ケトンと鎖延長剤として使用するアミンとの間でケチミンが生じ、円滑な反応を阻害する。ケチミンの発生を抑え、反応を円滑にするために少量の水を併用することが望ましい。
【００４５】
本発明の表刷り用グラビア印刷インキは、長期高温・多湿下での保存においてフィルム中に含有される酸化防止剤の変色の面から、アクリル樹脂とポリウレタン樹脂を、アクリル樹脂：ポリウレタン樹脂を２０：８０〜８０：２０の重量比率となる量で併用するものである。さらに、得られるインキ組成物の耐ブロッキング性、特にテーブルクロスなどに用いられている軟質塩化ビニルシートと印刷物が接着しないための耐塩ビブロッキング性と耐油性の面から、アクリル樹脂とポリウレタン樹脂が３０：７０の重量比率よりアクリル樹脂を多く含有させることが好適であり、また、アクリル樹脂とポリウレタン樹脂が７０：３０の重量比率よりポリウレタン樹脂を多く含有させることが、接着性の面から好適である。さらに、インキ組成物中における両方の樹脂を合わせた含有量は、５〜３０重量％が好適である。
【００４６】
次に、本発明で利用可能な顔料は、一般に印刷インキや塗料で使用できる各種の無機顔料としては、酸化チタン、ベンガラ、紺青、群青、カーボンブラック、黒鉛などの有色顔料、および、炭酸カルシウム、カオリン、クレー、硫酸バリウム、水酸化アルミニウム、タルク等の体質顔料を挙げることができる。さらに有機顔料としては、溶性アゾ顔料、不溶性アゾ顔料、アゾキレート顔料、縮合アゾ顔料、銅フタロシアニン顔料、縮合多環顔料などが挙げることができる。これらの顔料の含有量としては、インキ組成物中に０．５〜５０重量％が適量である。
【００４７】
次に、本発明のインキ組成物で利用する溶剤としては、主に、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ブタノールなどのアルコール系有機溶剤、アセトン，メチルエチルケトン、メチルイソブチルケトンなどのケトン系有機溶剤、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチルなどのエステル系有機溶剤、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタンなどの脂肪族炭化水素系有機溶剤、および、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、シクロヘプタン、シクロオクタンなどの脂環族炭化水素系有機溶剤が挙げることができ、バインダー樹脂の溶解性や乾燥性などを考慮して、混合して利用することが好ましい。これらの有機溶剤の使用量としては、通常のインキでは３０重量％以上含有される。
【００４８】
さらに、本発明では、接着性や各種耐性の向上を目的として、各種ハードレジン、架橋剤、ワックスを添加することができる。
【００４９】
ここで、ハードレジンとしては、ダイマー酸系樹脂、マレイン酸系樹脂、石油樹脂、テルペン樹脂、ケトン樹脂、ダンマー樹脂、コーパル樹脂、塩素化ポリプロピレン等が挙げられる。これらのハードレジンを利用すると、特に表面処理の行われていないプラスチックフィルムに対して、接着性の向上効果が期待できる。
【００５０】
また、表刷り用グラビア印刷インキでは、耐熱性、耐油性や耐摩擦性の向上を目的として、架橋剤やワックス成分を含有させることができる。
【００５１】
主に利用される架橋剤は、アルキルチタネート系、イソシアネート系であり、具体的に、アルキルチタネート系としては、テトライソプロポキシチタン、テトラ−ｎ−ブトキシチタン、テトラキス（２−エチルヘキシルオキシ）チタン、テトラステアリルオキシチタン、トリイソプロポキシチタンモノステアレート、トリ−ｎ−ブトキシチタンモノステアレート、ジイソプロポキシチタンジステアレート、ジ−ｎ−ブトキシチタンジステアレートなどが挙げられる。イソシアネート系としては、脂肪族ポリイソシアネート化合物、脂環族ポリイソシアネート化合物、芳香脂肪族ポリイソシアネート化合物、芳香族ポリイソシアネート、および、各種ビュレット化合物やイソシアネレート化合物などが挙げられる。その中でも、耐熱性の面から、アルコキシチタンセテアレート系化合物がより好適であり、フィルムに対する接着性の向上にはイシシアネート系架橋剤等も有効である。
【００５２】
一方、ワックスとしては、ポリオレフィンワックス、パラフィンワックスなどの既知の各種ワックスが利用できる。
【００５３】
さらに、顔料分散剤、レベリング剤、界面活性剤、可塑剤等の各種インキ用添加剤の添加は任意である。
【００５４】
これらの材料を利用して印刷インキを製造する方法として、まず、顔料、バインダー樹脂、有機溶剤、および必要に応じて顔料分散剤、界面活性剤などを攪拌混合した後、各種練肉機、例えば、ビーズミル、ボールミル、サンドミル、アトライター、ロールミル、パールミル等を利用して練肉し、さらに、残りの材料を添加混合する方法がある。
【００５５】
以上の材料と製造方法から得られた表刷り用グラビア印刷インキ組成物は、グラビア印刷方式で、各種プラスチックフィルム等の被着体に印刷することができる。具体的に、印刷可能なプラスチックフィルムとしては、ポリエチレン、ポリプロピレンなどの延伸および無延伸ポリオレフィン、ポリエステル、ナイロン、セロファン、ビニロンなどを挙げることができる。
【００５６】
さらに、得られた印刷物は製袋されて、食品などの包装容器に利用される。
【００５７】
【実施例】
以下，実施例でもって本発明をより具体的に説明するが、本発明はこれらに実施例に限定されるものではない。なお、特に断りのない限り、本実施例において「部」および「％」は「重量部」および「重量％」を表す。
【００５８】
＜アクリル樹脂の調製＞
（アクリル樹脂Aの重合例）
撹拌機、温度計、還流冷却器および窒素ガス導入管を備えた四ツ口フラスコに、メチルアクリレート１６部、メチルメタクリレート５８部、アクリル酸８部、スチレン１８部およびメチルエチルケトン２００部を仕込み、窒素気流下で、攪拌しながら９０℃まで昇温して、アゾビスイソブチロニトリル２部を加えて２時間重合反応を行い、分離・精製したもの４２部を、酢酸エチル４０部とイソプロピルアルコール１８部を添加し、固形分４２％、酸価１６０、重量平均分子量１３０００のアクリル樹脂ワニス（PAワニスA）を得た。
（アクリル樹脂Bの重合例）
撹拌機、温度計、還流冷却器および窒素ガス導入管を備えた四ツ口フラスコに、２−ヒドロキシエチルメタクリレート２５部、メチルメタクリレート４０部、ブチルメタクリレート３１部、アクリル酸１部、スチレン１部およびメチルイソブチルケトン１００部を仕込み、窒素気流下で、攪拌しながら９０℃まで昇温して、アゾビスイソブチロニトリル１部を加えて２時間重合反応を行い、分離・精製したもの５１部を、酢酸エチル２９部とｎ−プロピルアセテート２０部を添加し、固形分５１％、酸価３．４、重量平均分子量３５０００のアクリル樹脂ワニス（PAワニスB）を得た。
【００５９】
＜ポリウレタン樹脂の調製＞
（重合例）撹拌機、温度計、還流冷却器および窒素ガス導入管を備えた四ツ口フラスコに数平均分子量２０００のポリプロピレングリコール３１３．２７部とイソホロンジイソシアネート６２．６６部および酢酸エチル６０．０部を仕込み、窒素気流下に９０℃で６時間反応させた。次いでイソホロンジアミン２０．７０部、ステアリルアミン３．３８部、酢酸エチル３６０．０部、イソプロピルアルコール１８０．０部を添加し、固形分４０％、２５℃における粘度２００ｍＰａＳ、数平均分子量９，０００のポリウレタン樹脂ワニスA（PUワニスA）を得た。（比較重合例）撹拌機、温度計、還流冷却器および窒素ガス導入管を備えた四ツ口フラスコにアジピン酸と3-メチル-1,5-ペンタンジオールから得られる数平均分子量２０００のポリエステルジオール３１５．３４部とイソホロンジイソシアネート６３．０８部および酢酸エチル６０．０部を仕込み、窒素気流下に９０℃で６時間反応させた。次いでイソホロンジアミン２０．８３部、アセトアミド０．７５部、酢酸エチル３６０．０部、イソプロピルアルコール １８０．０部を添加し、固形分４０％、２５℃における粘度６００ｍＰａＳ、数平均分子量１２，０００のポリウレタン樹脂ワニスB（PUワニスB）を得た。
【００６０】
＜ニトロセルロースワニスの調製＞ニトロセルロース（1／８H、旭化成（株）製）30部を、酢酸エチル30部とイソプロピルアルコール40部に混合溶解させて、試験用ニトロセルロースワニス（NCワニス）を得た。
【００６１】
＜エチルセルロースワニスの調製＞エチルセルロースN7（ダウ・ケミカル（株）製）15部を、酢酸エチル５５部とイソプロピルアルコール30部に混合溶解させて、試験用エチルセルロースワニス（ECワニス）を得た。
【００６２】
＜酢酸セルロースワニスの調製＞酢酸セルロース（LAC30ダイセル（株）製）１０部を、酢酸エチル５５部とイソプロピルアルコール30部に混合溶解させて、試験用酢酸セルロースワニス（ACワニス）を得た。
【００６３】
＜ブチラールワニスの調製＞ブチラール（エスレックB BL10 積水化学（株）製）25部を、酢酸エチル２５部とイソプロピルアルコール５０部に混合溶解させて、試験用ブチラールワニス（BLワニス）を得た。
【００６４】
＜塩化ビニル−酢酸ビニル共重合体ワニスの調製＞塩化ビニル−酢酸ビニル共重合体（ソルバインTA５R 日信化学（株）製 ）25部を、酢酸エチル７５部に混合溶解させて、試験用塩化ビニル−酢酸ビニル共重合体ワニス（PVC-PVAcワニス）を得た。
【００６５】
まず、表１に示すバインダーを混合し、下記の方法でウレタン樹脂との相溶性の評価を行った。それぞれの評価結果を表１に示した。
【００６６】
相溶性：２種類の樹脂を攪拌混合し、５℃中で１日静置し外観と状態を評価した。
〇：白濁、ゲル化、分離せずに相溶した。
△：白濁のみした。
×：ゲル化または分離した。
【表１】
次に、相溶性があった実施例１〜４、１０、１１の各樹脂を用いて、調製表２に示す材料をサンドミルで混練し、試験用インキ組成物を調製した。なお、顔料、ハードレジン、架橋剤、離型剤、混合溶剤としては下記のものを用いた。
顔料 タイペーク ＣＲ６７（石原産業（株）製）
ハードレジン ダンマルゴム樹脂（小島化工（株）製）
架橋剤 テトライソプロポキシチタン（日本曹達（株）製）
離型剤 パルメチン酸アミド（花王（株）製）
混合溶剤 メチルシクロヘキサン：ｎ−プロピルアセテート：酢酸エチル：イソプロピルアルコール＝４０：２０：２０：２０（重量比）
【表２】
調製した試験印刷インキ組成物を用いて、コロナ放電処理したポリプロピレンフィルム（FOH、二村化学（株）製）にグラビア校正機を利用して印刷し、１日経過させた後、下記の方法で光沢、接着性、耐塩ビブロッキング性、耐熱性、耐油性、変色の評価を行った。それぞれの試験印刷インキ組成物の評価結果を表２に示した。
【００６９】
光沢：印刷物の光沢を光沢計（６０゜−６０°）にて測定した。
A：光沢値４０以上
B：光沢値３０以上４０未満
C：光沢値３０未満
【００７０】
接着性：印刷面にセロハンテープを貼り付け、すばやく剥がした。テープを貼り付けた面積と、インキがフィルムから剥離した面積との比較から、インキのフィルムに対する接着性を評価した。
A：インキが全く剥離しなかったもの。
B：インキがフィルムから剥離した面積がテープ接着面積の２０〜５０％のもの。
C：インキがフィルムから剥離した面積がテープ接着面積の５０％を超えるもの。
【００７１】
耐塩ビブロッキング性：印刷物と同じ大きさに切った軟質塩化ビニルシートと印刷面とを重ね合わせて、０．５ｋｇ／ｃｍ２の荷重をかけ、５０℃８０％RHの雰囲気で２４時間放置後、印刷面と塩化ビニルシートを引き剥がし、インキの剥離の程度から耐塩ビブロッキング性を評価した。
A：インキが全く剥離しなかったもの。
B：インキがフィルムから剥離した面積が２０〜５０％のもの。
C：インキがフィルムから剥離した面積が５０％を超えるもの。
【００７２】
耐熱性：印刷物と同じ大きさに切ったアルミ箔と印刷面とを重ね合わせ、ヒートシール試験機を用いて２ｋｇ／ｃｍ２の圧力で１秒間アルミ箔を押圧し、インキがアルミ箔に転移する最低温度からインキ組成物の耐熱性を評価した。
Ａ：最低温度が１６０℃以上のもの
Ｂ：最低温度が１４０℃以上、１６０℃未満のもの。
Ｃ：最低温度が１４０℃未満のもの。
【００７３】
耐油性：印刷面に溶解したバターを全面に塗布し、２４時間静置した後、学振型耐摩擦試験機で擦り、印刷面が全体の２０％以上取られたときの回数で評価した。
Ａ：５０回以上
Ｂ：１０回以上５０回未満
Ｃ：１０回未満
【００７４】
変色：印刷物と印刷をしていないフィルムを６０℃８０％RHで1週間保存し、色彩色差計を用いて１０枚重ねた印刷物の未印刷部分と印刷していないフィルムのｂ値を測定しそのｂ値の差Δｂで変色を評価した。
Ａ： Δｂが０．５ 以下
Ｂ： Δｂが０．５以上３未満
Ｃ： Δｂが３以上
【００７５】
【発明の効果】
以上、実施例を挙げて具体的に説明したように、本発明の印刷インキ組成物は、長期高温・多湿下での保存においてフィルム中に含まれる酸化防止剤の変色の低減とテーブルクロスなどに用いられている軟質塩化ビニルシートと印刷物が接着しないための耐塩ビブロッキング性が良好で、さらに環境衛生にも優れた表刷り用グラビア印刷インキ組成物である。[0001]
[Industrial application fields]
The present invention relates to a gravure printing ink composition for surface printing, and more specifically, soft vinyl chloride used for reducing discoloration of an antioxidant contained in a film and storing a table cloth, etc. during long-term storage under high temperature and high humidity. The present invention relates to a gravure printing ink composition for surface printing, which has good polyvinyl chloride blocking resistance for preventing adhesion of a sheet and printed matter, and is excellent in environmental sanitation.
[0002]
[Prior art]
In recent years, with the diversification of packaging containers, demands for the ink and printing industry have become very diverse.
[0003]
For example, the function that food manufacturers have traditionally demanded for printing packaging containers is how consumers can feel that the contents are delicious and high-class when they purchase. It is no exaggeration to say that the quality of these printed materials is directly related to the sales of the products.
[0004]
Furthermore, in the field of surface printing, since ink is printed on the front side of various plastic packaging containers, as ink performance in this field, in addition to printability, adhesion to films, and printed materials do not adhere to each other Blocking resistance, vinyl chloride blocking resistance to prevent the printed material from adhering to the soft vinyl chloride sheet used for table cloth, friction resistance against rubbing, oil resistance against oil, heat resistance when sealing the bag mouth Various resistances such as are required.
[0005]
Therefore, as a result of repeated research to satisfy these required performances, polyamide resins and cellulose derivatives are used as binders, and aromatic compound-based organic solvents such as toluene are used so that the solubility of the binder resin is increased. Ink containing has been used.
[0006]
However, recently, the composition of products using materials that are friendly to the global environment has been a major trend for the entire industry, and in food manufacturers in particular, the first priority is to have consumers have a clean image. Therefore, the attitude to tackle environmental issues more actively can be seen.
[0007]
Therefore, as a result of repeated studies to satisfy these required performances, inks containing a polyamide resin not containing toluene and a cellulose derivative as disclosed in JP-A-9-296143 have been used. However, the ink mainly composed of polyamide resin is not suitable for high-speed printing, and there is a problem that the ink is transferred to the reversing roll of the printing machine and the appearance of the printed matter is impaired.
[0008]
Further, in order to satisfy the required performance, a method of adding a chelating agent such as a titanate compound to the ink composition as disclosed in JP-A-61-37851, Japanese Patent Application No. 7-183039, etc. is known. However, there is a problem in that the stability of the ink with time decreases.
[0009]
On the other hand, as an ink suitable for high-speed printing without containing toluene, an ink using a polyurethane resin and nitrocellulose as a binder has been used. For example, it is disclosed by Unexamined-Japanese-Patent No. 2002-60668.
[0010]
However, the ink using a polyurethane resin and nitrocellulose as a binder is the same as that published by the Japanese Society of Fire Pharmacy, when a film containing a phenolic antioxidant is used. Vol. 63, no. As reported in 3, 2002, the decomposition of nitrocellulose is promoted and NOx is generated when placed in a high temperature and high humidity condition for a long time. It is well known that the generated NOx reacts with a phenolic antioxidant and the phenolic antioxidant has a quinone structure and causes discoloration of the film.
[0011]
Further, the surface printing gravure ink has a problem that the vinyl chloride blocking resistance is not sufficient because the soft vinyl chloride sheet used for the table cloth and the printed material do not adhere to each other.
[0012]
[Prior Document 1]
JP-A-9-296143
[Prior Document 2]
JP 61-37851 A
[Prior Document 3]
Japanese Patent Application No.7-183039
[Prior Document 4]
JP 2002-60668 A
[Problems to be solved by the invention]
[0013]
The present invention is a solvent composition that does not contain an aromatic hydrocarbon solvent, reduces discoloration of the antioxidant in the film during long-term storage under high temperature and high humidity, and has gloss, oil resistance, heat resistance, and resistance. An object of the present invention is to provide a gravure printing ink composition for surface printing, which has good stagnation and blocking resistance, in particular, blocking resistance to a soft PVC sheet.
[0014]
[Means for Solving the Problems]
That is, the present invention is an acrylic resin andA urethane prepolymer obtained by reacting a polyol component with an organic diisocyanate is chain-extended with a diamine compound, and the terminal is C 8 C twenty two Aliphatic amine compounds having the following long-chain alkyl groups or alkenyl groups or C 8 C twenty two The reaction is stopped with an aliphatic amide compound having the following long-chain alkyl group or alkenyl group.A gravure for surface printing comprising a polyurethane resin as a binder, a content ratio of acrylic resin: polyurethane resin = 20: 80 to 80:20 in terms of weight, and a non-aromatic solvent. The present invention relates to a printing ink composition.
[0015]
The present invention also provides the above gravure printing for surface printing, which comprises the acrylic resin A comprising the monomer (a) having a carbon-carbon unsaturated double bond in one molecule and having no crosslinkable functional group. The present invention relates to an ink composition.
[0016]
In addition, the present invention relates to 50 to 90% by weight of a monomer (a) having a carbon-carbon unsaturated double bond in one molecule and having no crosslinkable functional group, and carbon-carbon unsaturated in one molecule. It is related with the said gravure printing ink composition for surface printing containing the acrylic resin B which has a saturated double bond and has 10-50 weight% of monomers (b) which have a crosslinkable functional group.
[0018]
Furthermore, this invention relates to the said gravure printing ink composition for surface printing formed by containing a hard resin.
[0019]
In addition, this invention relates to the said gravure printing ink composition for surface printing formed by containing a crosslinking agent, and the printed matter formed by printing the said printing ink composition on a base material.
[0020]
Hereinafter, the present invention will be described in detail.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, first, an acrylic resin and a polyurethane resin are contained as a binder resin.
[0022]
The acrylic resins A and B that can be used in the present invention can be produced by a conventionally known method, and the production method is not particularly limited. Acrylic resin A is obtained by polymerizing monomer (a) having a carbon-carbon unsaturated double bond in one molecule and having no crosslinkable functional group in a solvent using a polymerization initiator. It is done. Acrylic resin B has a carbon-carbon unsaturated double bond in one molecule and a monomer (a) having no crosslinkable functional group, and a carbon-carbon unsaturated double bond and a crosslink in one molecule. It is obtained by polymerizing the monomer (b) having a functional functional group in a solvent using a polymerization initiator.
[0023]
Here, the monomer (a) having a carbon-carbon unsaturated double bond in one molecule and having no crosslinkable functional group is (i) (meth) acrylic acid derivative, (ii) aromatic Group vinyl monomers, (iii) olefinic hydrocarbon monomers, (iv) vinyl ester monomers, (v) vinyl halide monomers, (vi) vinyl ether monomers, and the like.
[0024]
(i) Examples of (meth) acrylic acid derivatives include (meth) acrylonitrile, (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, stearyl (meth) acrylate, etc. Examples include alkyl (meth) acrylate and benzyl (meth) acrylate.
(ii) Examples of aromatic vinyl monomers include styrene, methyl styrene, ethyl styrene, chloro styrene, monofluoromethyl styrene, difluoromethyl styrene, trifluoromethyl styrene and the like in which some hydrogen is fluorine-substituted. Etc.
(iii) Examples of the olefinic hydrocarbon monomer include ethylene, propylene, butadiene, isobutylene, isoprene and 1,4-pentadiene.
(iv) Examples of vinyl ester monomers include vinyl acetate.
(v) Examples of the vinyl halide monomer include vinyl chloride and vinylidene chloride.
(vi) Examples of vinyl ether monomers include vinyl methyl ether. Two or more of these may be used. In the acrylic resin A, the acid value is preferably 50 or more and 200 or less in terms of both oil resistance and heat resistance. In the acrylic resin B, it is used in the range of 50 to 90% by weight, preferably 55 to 80% by weight, more preferably 60 to 75% by weight. When this upper limit is exceeded, it becomes difficult to obtain sufficient various resistances.
[0025]
Next, examples of the functional group of the monomer (b) having a carbon-carbon unsaturated double bond and a crosslinkable functional group in one molecule include a hydroxyl group, an isocyano group, and an epoxy group.
Examples of the monomer (b) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. , Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, hydroxystyrene and the like.
[0026]
Examples of the monomer (b) having an isocyano group include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxypropyl isocyanate, and the like, as well as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl ( Examples thereof include those obtained by reacting a hydroxyalkyl (meth) acrylate such as (meth) acrylate with a polyisocyanate such as toluene diisocyanate and isophorone diisocyanate.
[0027]
Examples of the monomer (b) having an epoxy group include glycidyl methacrylate, glycidyl cinnamate, glycidyl allyl ether, glycidyl vinyl ether, vinylcyclohexane monoepoxide, 1,3-butadiene monoepoxide, and the like.
[0028]
Depending on the required performance, one of these or a mixture of two or more may be used.
[0029]
The monomer (b) is used in the acrylic resin B at a copolymerization ratio of 10 to 50% by weight, preferably 20 to 45% by weight, and more preferably 25 to 40% by weight. When the lower limit is not reached, it is difficult to obtain sufficient various resistances.
[0030]
Examples of the polymerization initiator include ordinary peroxides or azo compounds such as benzoyl peroxide, azoisobutylvalenonitrile, azobisisobutyronitrile, di-t-butyl peroxide, t-butyl perbenzoate, and t-butyl. Peroctoate, cumene hydroxy peroxide and the like are used, and the polymerization temperature is 50 to 140 ° C, preferably 70 to 140 ° C.
The preferred weight average molecular weight of the resulting polymer is 5,000 to 100,000.
[0031]
Non-aromatic solvents used in the above production methods include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethyl acetate, butyl acetate, etc. These esters can be used. The solvent may be a mixture of two or more.
[0032]
Next, the polyurethane resin usable in the present invention can be produced by a conventionally known method, and the production method is not particularly limited. For example, a polyol compound and an organic diisocyanate compound are reacted in an excess ratio of an isocyanate group to prepare a prepolymer having an isocyanate group at the end of the polyol, and then a chain extender and a reaction terminator in a solvent. A two-stage method of reacting is mentioned. The two-stage method is preferable because a uniform polymer solution can be easily obtained. As the solvent, an ester solvent, a ketone solvent, and an alcohol solvent may be used alone or in combination of two or more.
[0033]
Here, usable polyol compounds include polyether polyols such as polymers or copolymers such as ethylene oxide, propylene oxide and tetrahydrofuran; ethylene glycol, 1,2-propanediol, 1,3-propanediol, Saturation of 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentadiol, methylpentadiol, hexadiol, octanediol, nonanediol, methylnonanediol, diethylene glycol, triethylene glycol, dipropylene glycol, etc. And unsaturated low molecular weight glycols, alkyl glycidyl ethers such as n-butyl glycidyl ether and 2-ethylhexyl glycidyl ether, monocarboxylic acid glycidyl esters such as versatic acid glycidyl ester, Dibasic acids such as dipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid, dimer acid or their anhydrides Polyester polyols obtained by dehydrating and condensing products; other polycarbonate diols, polybutadiene glycols, glycols obtained by adding bisphenol A ethylene oxide or propylene oxide; various known polyols such as dimer diols Can do. These polyols may be used alone or in combination of two or more.
[0034]
In addition, when using the polyol obtained from glycols and a dibasic acid among these polyols, up to 5 mol% of glycols can be substituted by various polyols. That is, for example, a polyol such as glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, pentaerythritol may be substituted.
[0035]
Although the average molecular weight of a polyol is suitably determined in consideration of the solubility, drying property, blocking resistance, etc. of the resulting polyurethane resin, it is usually preferably from 500 to 6000. When the molecular weight is less than 500, the printability tends to be inferior with a decrease in solubility, and when it exceeds 6000, the drying property and blocking resistance are lowered.
[0036]
Next, examples of the organic diisocyanate compound that can be used include various known diisocyanates of aromatic, aliphatic, and alicyclic groups. For example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3- Phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate , Xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate Dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, m-tetramethylxylylene diisocyanate, dimerisocyanate converted from dimer acid carboxyl group to isocyanate group, etc. is there.
[0037]
Next, the method for producing the polyurethane resin when the polyol compound and the organic diisocyanate are reacted is not particularly limited. For example, the conditions for reacting the polyol compound with the organic diisocyanate are not particularly limited except that the polyol is excessive, but the equivalent ratio of isocyanate group / hydroxyl group is within the range of 1.2 / 1 to 3/1. It is desirable to be. When the equivalent ratio of isocyanate group / hydroxyl group is 1.2 / 1 or less, the obtained polyurethane resin is fragile, so that blocking tends to occur when used in printing ink. On the other hand, if the equivalent ratio of isocyanate group / hydroxyl group is 3/1 or more, the viscosity becomes high in the production of the resin, and gelation tends to occur during the reaction. Moreover, reaction temperature is normally performed between 80 degreeC-200 degreeC, Preferably it is good to carry out between 90 degreeC-150 degreeC.
[0038]
The polyurethane forming reaction may be performed in a solvent or may be performed in a solvent-free atmosphere. In the case of using a solvent, a solvent shown later may be appropriately selected and used from the viewpoints of temperature and viscosity during reaction and control of side reactions. When the polyurethane-forming reaction is carried out in a solvent-free atmosphere, it is desirable to raise the temperature and lower the viscosity to such an extent that stirring is sufficient in order to obtain a uniform polyurethane resin. The urethanization reaction is desirably carried out for 10 minutes to 5 hours, and the end point of the reaction is judged by viscosity measurement, NCO peak by IR measurement, NCO% measurement by titration, and the like.
[0039]
Furthermore, after reacting a polyol compound and an organic diisocyanate to synthesize a prepolymer having a terminal isocyanate group, a urea bond is introduced into the polyurethane resin using a chain extender and a reaction terminator to obtain a polyurethane / urea resin. Thus, the physical properties of the coating film are further improved.
[0040]
Next, various known amines can be used as a chain extender that can be used when a urea bond is introduced. For example, ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine and the like can be mentioned. Other molecules such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, etc. Representative examples thereof include diamines having a hydroxyl group and dimer diamine obtained by converting a carboxyl group of dimer acid into an amino group.
[0041]
Next, available reaction terminators include C8C22Aliphatic amine compounds having the following long-chain alkyl groups or C8C22Examples include aliphatic amide compounds having the following long-chain alkyl groups. As the aliphatic amine compound, octylamine, laurylamine, coconutamine, myristylamine, stearylamine, oleylamine, palmitylamine and the like can be used alone or in combination. Fatty acid amide compounds include octanoic acid amide, decanoic acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, linoleic acid amide, linolenic acid amide, etc. These are used alone or in combination of two or more.
[0042]
C8C22Aliphatic amine compounds having the following long-chain alkyl groups or C8C22Blocking resistance is improved by introducing an aliphatic amide compound having the following long-chain alkyl group into the end of the polyurethane resin. Since the long-chain alkyl group exhibits surface-active properties, it is considered that the long-chain alkyl group is oriented on the surface in the process of forming the coating film, thereby improving the blocking resistance of the polyurethane resin. By introducing these fatty acid amines or fatty acid amides into the polyurethane resin, the gloss of the coating film surface does not decrease.
[0043]
The production method for introducing the urea bond into the polyurethane resin is not particularly limited, but the chain extender and the reaction terminator when the number of free isocyanate groups at both ends of the prepolymer is 1 are used. It is preferable that the total quantity of the amino groups in it is in the range of 0.5 to 1.3. When the total number of amino groups is less than 0.5, the drying property, blocking resistance and coating strength are not sufficient, and when it exceeds 1.3, the chain extender and the reaction terminator remain unreacted. , Odor is likely to remain on the printed matter.
[0044]
As the solvent used in the above production method, alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, n-butanol, etc., well known as solvents for printing ink, acetone, methyl ethyl ketone, methyl isobutyl ketone Ketone solvents such as ethyl acetate, propyl acetate, and butyl acetate, and non-aromatic hydrocarbon solvents such as methylcyclohexane and ethylcyclohexane. These may be used alone or in a mixture of two or more. In addition, when said ketone solvent is used at the time of reaction, a ketimine arises between a ketone and the amine used as a chain extender, and smooth reaction is inhibited. It is desirable to use a small amount of water in order to suppress the generation of ketimine and facilitate the reaction.
[0045]
The gravure printing ink for surface printing according to the present invention comprises acrylic resin and polyurethane resin, acrylic resin: polyurethane resin 20 from the aspect of discoloration of the antioxidant contained in the film during long-term storage under high temperature and high humidity. It is used in combination in an amount that gives a weight ratio of 80 to 80:20. Furthermore, from the viewpoint of blocking resistance of the resulting ink composition, in particular, vinyl chloride blocking resistance and oil resistance so that the soft vinyl chloride sheet used for the table cloth and the printed material do not adhere to each other, 30 acrylic resins and polyurethane resins are used. : It is preferable to contain more acrylic resin than the weight ratio of 70, and it is preferable from the viewpoint of adhesiveness that the acrylic resin and the polyurethane resin contain more polyurethane resin than the weight ratio of 70:30. . Furthermore, the combined content of both resins in the ink composition is preferably 5 to 30% by weight.
[0046]
Next, the pigments that can be used in the present invention are generally various pigments such as titanium oxide, bengara, bitumen, ultramarine, carbon black, and graphite, and calcium carbonate, Examples of extender pigments include kaolin, clay, barium sulfate, aluminum hydroxide, and talc. Furthermore, examples of organic pigments include soluble azo pigments, insoluble azo pigments, azo chelate pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments. The content of these pigments is 0.5 to 50% by weight in the ink composition.
[0047]
Next, as the solvent used in the ink composition of the present invention, alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol and butanol, and ketone organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone are mainly used. Ester organic solvents such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate, aliphatic hydrocarbon organic solvents such as n-hexane, n-heptane and n-octane, and cyclohexane, methylcyclohexane, ethylcyclohexane, Examples thereof include alicyclic hydrocarbon organic solvents such as cycloheptane and cyclooctane, and it is preferable to use them by mixing in consideration of solubility and drying property of the binder resin. The amount of these organic solvents used is 30% by weight or more in ordinary ink.
[0048]
Furthermore, in the present invention, various hard resins, crosslinking agents, and waxes can be added for the purpose of improving adhesiveness and various resistances.
[0049]
Here, examples of the hard resin include dimer acid resin, maleic acid resin, petroleum resin, terpene resin, ketone resin, dammar resin, copal resin, and chlorinated polypropylene. When these hard resins are used, an effect of improving adhesiveness can be expected particularly for a plastic film that has not been surface-treated.
[0050]
Moreover, in the gravure printing ink for surface printing, a crosslinking agent and a wax component can be contained for the purpose of improving heat resistance, oil resistance, and friction resistance.
[0051]
The mainly used crosslinking agents are alkyl titanate and isocyanate. Specifically, as the alkyl titanate, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetrakis (2-ethylhexyloxy) titanium, tetra Examples include stearyloxytitanium, triisopropoxytitanium monostearate, tri-n-butoxytitanium monostearate, diisopropoxytitanium distearate, di-n-butoxytitanium distearate and the like. Examples of the isocyanate type include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, araliphatic polyisocyanate compounds, aromatic polyisocyanates, various burette compounds, and isocyanate compounds. Among these, from the viewpoint of heat resistance, an alkoxytitanium cetearate compound is more suitable, and an isocyanate-based cross-linking agent is also effective for improving the adhesion to the film.
[0052]
On the other hand, various known waxes such as polyolefin wax and paraffin wax can be used as the wax.
[0053]
Furthermore, the addition of various ink additives such as pigment dispersants, leveling agents, surfactants, and plasticizers is optional.
[0054]
As a method for producing printing ink using these materials, first, after stirring and mixing a pigment, a binder resin, an organic solvent, and, if necessary, a pigment dispersant, a surfactant, and the like, There is a method of kneading using a bead mill, a ball mill, a sand mill, an attritor, a roll mill, a pearl mill or the like, and further adding and mixing the remaining materials.
[0055]
The gravure printing ink composition for surface printing obtained from the above materials and production method can be printed on an adherend such as various plastic films by a gravure printing method. Specifically, examples of the printable plastic film include stretched and unstretched polyolefins such as polyethylene and polypropylene, polyester, nylon, cellophane, and vinylon.
[0056]
Furthermore, the obtained printed matter is made into a bag and used for a packaging container such as food.
[0057]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to an Example. Unless otherwise specified, “parts” and “%” in this example represent “parts by weight” and “% by weight”.
[0058]
<Preparation of acrylic resin>
(Example of polymerization of acrylic resin A)
A four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube was charged with 16 parts of methyl acrylate, 58 parts of methyl methacrylate, 8 parts of acrylic acid, 18 parts of styrene and 200 parts of methyl ethyl ketone, and a nitrogen stream Then, the temperature was raised to 90 ° C. with stirring, 2 parts of azobisisobutyronitrile was added and the polymerization reaction was carried out for 2 hours, and 42 parts separated and purified were mixed with 40 parts ethyl acetate and 18 parts isopropyl alcohol. Was added to obtain an acrylic resin varnish (PA varnish A) having a solid content of 42%, an acid value of 160, and a weight average molecular weight of 13,000.
(Example of polymerization of acrylic resin B)
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 25 parts 2-hydroxyethyl methacrylate, 40 parts methyl methacrylate, 31 parts butyl methacrylate, 1 part acrylic acid, 1 part styrene and Charge 100 parts of methyl isobutyl ketone, raise the temperature to 90 ° C. with stirring under a nitrogen stream, add 1 part of azobisisobutyronitrile, conduct a polymerization reaction for 2 hours, and separate and purify 51 parts. 29 parts of ethyl acetate and 20 parts of n-propyl acetate were added to obtain an acrylic resin varnish (PA varnish B) having a solid content of 51%, an acid value of 3.4, and a weight average molecular weight of 35,000.
[0059]
<Preparation of polyurethane resin>
(Polymerization example) In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, 313.27 parts of polypropylene glycol having a number average molecular weight of 2000, 62.66 parts of isophorone diisocyanate and 60.0 ethyl acetate The parts were charged and reacted at 90 ° C. for 6 hours under a nitrogen stream. Next, 20.70 parts of isophoronediamine, 3.38 parts of stearylamine, 360.0 parts of ethyl acetate, and 180.0 parts of isopropyl alcohol were added, the solid content was 40%, the viscosity at 25 ° C. was 200 mPaS, and the number average molecular weight was 9,000. A polyurethane resin varnish A (PU varnish A) was obtained. (Comparative polymerization example) Polyester diol having a number average molecular weight of 2000 obtained from adipic acid and 3-methyl-1,5-pentanediol in a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introduction tube 315.34 parts, 63.08 parts of isophorone diisocyanate and 60.0 parts of ethyl acetate were charged and reacted at 90 ° C. for 6 hours under a nitrogen stream. Next, 20.83 parts of isophoronediamine, 0.75 parts of acetamide, 360.0 parts of ethyl acetate, and 180.0 parts of isopropyl alcohol were added, and a polyurethane having a solid content of 40%, a viscosity of 600 mPaS at 25 ° C., and a number average molecular weight of 12,000. Resin varnish B (PU varnish B) was obtained.
[0060]
<Preparation of nitrocellulose varnish> 30 parts of nitrocellulose (1 / 8H, manufactured by Asahi Kasei Co., Ltd.) are mixed and dissolved in 30 parts of ethyl acetate and 40 parts of isopropyl alcohol to obtain a test nitrocellulose varnish (NC varnish). It was.
[0061]
<Preparation of ethyl cellulose varnish> 15 parts of ethyl cellulose N7 (manufactured by Dow Chemical Co., Ltd.) was mixed and dissolved in 55 parts of ethyl acetate and 30 parts of isopropyl alcohol to obtain a test ethyl cellulose varnish (EC varnish).
[0062]
<Preparation of Cellulose Acetate Varnish> 10 parts of cellulose acetate (LAC30 manufactured by Daicel Corporation) were mixed and dissolved in 55 parts of ethyl acetate and 30 parts of isopropyl alcohol to obtain a cellulose acetate varnish for testing (AC varnish).
[0063]
<Preparation of Butyral Varnish> 25 parts of butyral (Eslec B BL10 manufactured by Sekisui Chemical Co., Ltd.) was mixed and dissolved in 25 parts of ethyl acetate and 50 parts of isopropyl alcohol to obtain a butyral varnish for testing (BL varnish).
[0064]
<Preparation of Vinyl Chloride-Vinyl Acetate Copolymer Varnish> 25 parts of vinyl chloride-vinyl acetate copolymer (Solvain TA5R manufactured by Nissin Chemical Co., Ltd.) was mixed and dissolved in 75 parts of ethyl acetate, and vinyl chloride for testing was used. -A vinyl acetate copolymer varnish (PVC-PVAc varnish) was obtained.
[0065]
First,Mix the binder shown in Table 1The compatibility with urethane resin was evaluated by the following method. The respective evaluation results are shown in Table 1.
[0066]
Compatibility: Two types of resins were stirred and mixed and allowed to stand at 5 ° C. for 1 day to evaluate the appearance and state.
○: White turbidity, gelation, compatibility without separation.
Δ: Cloudy only.
X: Gelled or separated.
[Table 1]
Next, there was compatibilityExamples 1-4Using each of the resins Nos. 10 and 11, the materials shown in Preparation Table 2 were kneaded with a sand mill to prepare a test ink composition. In addition, the following were used as a pigment, a hard resin, a crosslinking agent, a release agent, and a mixed solvent.
Pigment Typeke CR67 (Ishihara Sangyo Co., Ltd.)
Hard resin Dammar rubber resin (manufactured by Kojima Chemical Co., Ltd.)
Crosslinking agent Tetraisopropoxytitanium (Nippon Soda Co., Ltd.)
Mold release agent Palmetic acid amide (manufactured by Kao Corporation)
Mixed solvent Methylcyclohexane: n-propyl acetate: ethyl acetate: isopropyl alcohol = 40: 20: 20: 20 (weight ratio)
[Table 2]
Using the prepared test printing ink composition, a corona discharge-treated polypropylene film (FOH, manufactured by Futamura Chemical Co., Ltd.) is printed using a gravure proofing machine, and after 1 day, it is glossed by the following method. Evaluation of adhesiveness, PVC blocking resistance, heat resistance, oil resistance, and discoloration was performed. The evaluation results of each test printing ink composition are shown in Table 2.
[0069]
Gloss: The gloss of the printed material was measured with a gloss meter (60 ° -60 °).
A: Gloss value of 40 or more
B: Gloss value of 30 or more and less than 40
C: Gloss value less than 30
[0070]
Adhesiveness: Cellophane tape was applied to the printed surface and quickly removed. From the comparison between the area where the tape was applied and the area where the ink was peeled from the film, the adhesion of the ink to the film was evaluated.
A: The ink did not peel at all.
B: The area where the ink peeled from the film was 20 to 50% of the tape adhesion area.
C: The area where the ink peeled from the film exceeded 50% of the tape adhesion area.
[0071]
PVC blocking resistance: 0.5 kg / cm with a soft vinyl chloride sheet cut to the same size as the printed material and the printed surface.2After being left for 24 hours in an atmosphere of 50 ° C. and 80% RH, the printed surface and the vinyl chloride sheet were peeled off, and the vinyl chloride blocking resistance was evaluated from the degree of ink peeling.
A: The ink did not peel at all.
B: The area where the ink peeled from the film was 20 to 50%.
C: The area where the ink peeled from the film exceeded 50%.
[0072]
Heat resistance: Aluminum foil cut to the same size as the printed material and the printed surface are stacked and 2kg / cm using a heat seal tester2The aluminum foil was pressed at a pressure of 1 second for 1 second, and the heat resistance of the ink composition was evaluated from the lowest temperature at which the ink transferred to the aluminum foil.
A: The minimum temperature is 160 ° C or higher
B: The minimum temperature is 140 ° C or higher and lower than 160 ° C.
C: The minimum temperature is less than 140 ° C.
[0073]
Oil resistance: Butter dissolved on the printed surface was applied to the entire surface, allowed to stand for 24 hours, then rubbed with a Gakushin type friction tester, and evaluated by the number of times when 20% or more of the printed surface was taken.
A: 50 times or more
B: 10 times or more and less than 50 times
C: Less than 10 times
[0074]
Discoloration: Printed material and unprinted film are stored at 60 ° C and 80% RH for 1 week, and the b value of the unprinted portion of the printed material and the unprinted film of 10 sheets are measured using a color difference meter. Discoloration was evaluated by the difference b in the b value.
A: Δb is 0.5 or less
B: Δb is 0.5 or more and less than 3
C: Δb is 3 or more
[0075]
【The invention's effect】
As described above in detail with reference to the examples, the printing ink composition of the present invention reduces the discoloration of the antioxidant contained in the film and preserves the table cloth, etc. when stored under high temperature and high humidity for a long time. It is a gravure printing ink composition for surface printing, which has good vinyl chloride blocking resistance for preventing the soft vinyl chloride sheet used from being printed and the printed product from adhering, and is excellent in environmental sanitation.
Claims (6)
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| JP2003130376A JP4285069B2 (en) | 2003-05-08 | 2003-05-08 | Gravure printing ink composition for surface printing |
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| JP2003130376A JP4285069B2 (en) | 2003-05-08 | 2003-05-08 | Gravure printing ink composition for surface printing |
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| JP4285069B2 true JP4285069B2 (en) | 2009-06-24 |
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| JP4769582B2 (en) * | 2005-01-14 | 2011-09-07 | 大日精化工業株式会社 | Printing ink |
| JP4839666B2 (en) * | 2005-04-22 | 2011-12-21 | 東洋インキＳｃホールディングス株式会社 | Gravure printing ink composition for surface printing |
| JP2007246649A (en) | 2006-03-15 | 2007-09-27 | Dainippon Ink & Chem Inc | Printing ink composition |
| JP5510153B2 (en) * | 2010-07-27 | 2014-06-04 | 東洋インキＳｃホールディングス株式会社 | Gravure printing method and printed matter obtained by the method |
| JP6034558B2 (en) * | 2011-12-05 | 2016-11-30 | セーレン株式会社 | Advertising medium and manufacturing method thereof |
| JP7026519B2 (en) * | 2018-01-29 | 2022-02-28 | 株式会社パイロットコーポレーション | Oil-based ink composition for writing tools and writing tools using it |
| JP2022085539A (en) * | 2020-11-27 | 2022-06-08 | セイコーエプソン株式会社 | Ink set and recording method |
| CN114083849A (en) * | 2021-10-13 | 2022-02-25 | 广东天进新材料有限公司 | Film with three-dimensional sense and preparation method and application thereof |
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