JP6451978B2 - Active energy ray-curable offset ink composition - Google Patents
Active energy ray-curable offset ink composition Download PDFInfo
- Publication number
- JP6451978B2 JP6451978B2 JP2014208982A JP2014208982A JP6451978B2 JP 6451978 B2 JP6451978 B2 JP 6451978B2 JP 2014208982 A JP2014208982 A JP 2014208982A JP 2014208982 A JP2014208982 A JP 2014208982A JP 6451978 B2 JP6451978 B2 JP 6451978B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- ink
- ethylene oxide
- active energy
- energy ray
- 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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- 239000000203 mixture Substances 0.000 title claims description 70
- -1 ethylene oxide-modified trimethylolpropane triacrylate Chemical class 0.000 claims description 48
- 239000000049 pigment Substances 0.000 claims description 28
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 claims description 9
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- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 6
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Images
Description
本発明は、活性エネルギー線条件下で優れた硬化性、及び紙器等のパッケージインキ印刷用のために優れた印刷適性と印刷品質を保持することを特徴とする活性エネルギー線硬化型オフセットインキ組成物に関する。更には、該組成物を用いた印刷物に関する。 The present invention provides an active energy ray-curable offset ink composition characterized by maintaining excellent curability under active energy ray conditions and excellent printability and print quality for package ink printing of paper containers and the like About. Furthermore, the present invention relates to a printed matter using the composition.
活性エネルギー線条件下で硬化する、中でも紫外線硬化型オフセットインキは、瞬間乾燥の特性の利便性から、玩具や紙器等の食品包装向けパッケージ印刷の分野で広く使用されている。 UV curable offset inks that cure under active energy ray conditions are widely used in the field of package printing for food packaging such as toys and paper containers because of the convenience of instant drying characteristics.
一方で、紫外線硬化型オフセットインキは、一般の油性オフセットインキと比較して、印刷時水量を減量させた際の印刷物の汚れポイントと、水量を増量させた際の印刷物の濃度低下を招くポイントの領域幅を示すいわゆる印刷時の「水幅の狭さ」に関連して、網点再現性等、オフセット印刷適性が劣ることが問題点として挙げられる。 On the other hand, UV-curing offset ink is a point that causes a stain point of printed matter when the amount of water during printing is reduced and a decrease in density of printed matter when the amount of water is increased compared to general oil-based offset ink. In relation to the so-called “narrow water width” at the time of printing indicating the area width, there is a problem that the offset printability such as halftone dot reproducibility is inferior.
活性エネルギー線硬化型、或いは紫外線硬化型オフセットインキの原料である重合性モノマーの構造により極性、粘度、反応性が相異なることから、オフセットインキの性能面で重要である硬化性、流動性、オフセット印刷適性の全てについて高いレベルに保持すべく、これらの特性を制御しうる重合性モノマーの選定・組合せが効果的である。 The polarity, viscosity, and reactivity differ depending on the structure of the polymerizable monomer that is the raw material of the active energy ray-curable or UV-curable offset ink, so the curability, fluidity, and offset are important in terms of offset ink performance. In order to maintain a high level of all printability, it is effective to select and combine polymerizable monomers capable of controlling these characteristics.
例えば、インプリント用の光硬化性樹脂組成物として、エチレンオキサイド変性トリメチロールプロパントリアクリレート等のモノマーを用いた樹脂組成物が提案されている（例えば、特許文献１）。しかし、該樹脂組成物は転写対象の樹脂との剥離性やインプリント用モールドの柔軟性が目的であり、インキと水の乳化バランスの生じる微妙な影響下において、インキの硬化性、流動性、オフセット印刷適性すべてを発現することは出来ない。 For example, as a photocurable resin composition for imprinting, a resin composition using a monomer such as ethylene oxide-modified trimethylolpropane triacrylate has been proposed (for example, Patent Document 1). However, the resin composition is intended to be peelable from the resin to be transferred and the flexibility of the imprint mold, and under the delicate influence that the emulsification balance of the ink and water occurs, the curability, fluidity of the ink, Not all offset printing aptitudes can be expressed.
また、印刷時の水幅を考慮した活性エネルギー線硬化性被覆組成物として、エチレンオキサイド変性ビスフェノールＡジアクリレート等のモノマーを用いた被覆組成物（例えば、特許文献２）や、硬化性、接着性に優れる紫外線硬化型オフセットインキとして、ケトンアルデヒド樹脂にトリメチロールプロパントリアクリレート等のモノマーを用いた樹脂組成物が提案されている（例えば、特許文献３）。
しかしインキの硬化性、流動性、オフセット印刷適性をバランスよく全てを網羅するに充分であるとは言えない。
Moreover, as an active energy ray-curable coating composition considering the water width at the time of printing, a coating composition using a monomer such as ethylene oxide-modified bisphenol A diacrylate (for example, Patent Document 2), curability and adhesiveness As an ultraviolet curable offset ink excellent in the above, a resin composition using a monomer such as trimethylolpropane triacrylate in a ketone aldehyde resin has been proposed (for example, Patent Document 3).
However, it cannot be said that the ink curability, fluidity, and offset printability are all well-balanced.
本発明の課題は、インキの硬化性、流動性に優れ、版面上に水を連続供給するオフセット印刷適性を有する活性エネルギー線硬化型オフセットインキ組成物を提供することにある。 An object of the present invention is to provide an active energy ray-curable offset ink composition having excellent ink curability and fluidity, and having offset printing suitability for continuously supplying water onto a plate surface.
モノマーは各々異なる粘度、親水／疎水バランス、硬化性能を有することから、流動性、硬化性、乳化率、印刷適性（水幅）といった様々なインキ特性に影響を及ぼすが、本発明者らは、特定のエチレンオキサイド変性トリメチロールプロパントリアクリレートと、適量の特定のエチレンオキサイド変性ビスフェノールＡジアクリレート、および顔料を適宜組合せ採用することで、上記課題を達成できることを見出した。 Since each monomer has different viscosity, hydrophilic / hydrophobic balance, and curing performance, it affects various ink properties such as fluidity, curability, emulsification rate, and printability (water width). It has been found that the above-mentioned problems can be achieved by appropriately combining a specific ethylene oxide-modified trimethylolpropane triacrylate, an appropriate amount of the specific ethylene oxide-modified bisphenol A diacrylate, and a pigment.
すなわち本発明は、モノマー分子１モルあたりのエチレンオキサイドの平均付加モル数が２〜６の範囲にあるエチレンオキサイド変性トリメチロールプロパントリアクリレート（Ａ）、モノマー分子１モルあたりのエチレンオキサイドの平均付加モル数が２〜６の範囲にあるエチレンオキサイド変性ビスフェノールＡジアクリレート（Ｂ）、および顔料を含有し、前記エチレンオキサイド変性ビスフェノールＡジアクリレート（Ｂ）を１〜３３重量％の範囲で含有することを特徴とする活性エネルギー線硬化型オフセットインキ組成物を提供する。 That is, the present invention relates to an ethylene oxide-modified trimethylolpropane triacrylate (A) in which the average number of moles of ethylene oxide added per mole of monomer molecules is in the range of 2 to 6, and the average number of moles of ethylene oxide added per mole of monomer molecules. Containing ethylene oxide-modified bisphenol A diacrylate (B) having a number in the range of 2 to 6 and a pigment, and containing the ethylene oxide-modified bisphenol A diacrylate (B) in a range of 1 to 33% by weight. An active energy ray-curable offset ink composition is provided.
更に、本発明は、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物を、全量の１〜３０重量％の範囲で含有する活性エネルギー線硬化型オフセットインキ組成物に関する。 Furthermore, the present invention relates to an active energy ray-curable offset ink composition containing a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in a range of 1 to 30% by weight of the total amount.
更に、本発明は、ウレタン（メタ）アクリレートを１０〜５０重量％の範囲で含有する活性エネルギー線硬化型オフセットインキ組成物に関する。 Furthermore, the present invention relates to an active energy ray-curable offset ink composition containing urethane (meth) acrylate in the range of 10 to 50% by weight.
更に、本発明は、基材上に、該活性エネルギー線硬化型オフセットインキ組成物を用いてオフセット印刷された印刷物をも提供する。 Furthermore, the present invention also provides a printed matter that is offset-printed on a substrate using the active energy ray-curable offset ink composition.
本発明の活性エネルギー線硬化型オフセットインキ組成物により、インキの硬化性、流動性に優れ、版面上に水を連続供給するオフセット印刷適性が一般の油性オフセットインキと遜色なく再現できる活性エネルギー線硬化型オフセットインキ組成物を得ることができる。 The active energy ray-curable offset ink composition of the present invention is excellent in ink curability and fluidity, and active energy ray curing that can reproduce the offset printing suitability for continuously supplying water onto the plate surface is similar to general oil-based offset inks. A mold offset ink composition can be obtained.
本発明は、モノマー分子１モルあたりのエチレンオキサイドの平均付加モル数が２〜６の範囲にあるエチレンオキサイド変性トリメチロールプロパントリアクリレート（Ａ）、モノマー分子１モルあたりのエチレンオキサイドの平均付加モル数が２〜６の範囲にあるエチレンオキサイド変性ビスフェノールＡジアクリレート（Ｂ）、および顔料を含有し、前記エチレンオキサイド変性ビスフェノールＡジアクリレート（Ｂ）を１〜３３重量％の範囲で含有することで目的とする本発明の効果を奏するものである。 The present invention relates to an ethylene oxide-modified trimethylolpropane triacrylate (A) having an average number of moles of ethylene oxide added per mole of monomer molecules in the range of 2 to 6, and an average number of moles of ethylene oxide added per mole of monomer molecules. Contains ethylene oxide-modified bisphenol A diacrylate (B) in a range of 2 to 6 and a pigment, and contains the ethylene oxide-modified bisphenol A diacrylate (B) in a range of 1 to 33% by weight. The effects of the present invention are obtained.
エチレンオキサイド変性トリメチロールプロパントリアクリレート（ＣＡＳ登録番号２８９６１−４３−５）の一般化学構造は式（１）で示される。 The general chemical structure of ethylene oxide-modified trimethylolpropane triacrylate (CAS registration number 28961-43-5) is represented by formula (1).
式（１）において、Ｃは炭素原子、Ｈは水素原子、Ｏは酸素原子であり、−（ＣＨ２−ＣＨ２−Ｏ）−はエチレンオキサイド基を示し、ａ、ｂ、ｃはそれぞれゼロを含む正の整数（０，１，２，３・・・）である。従ってモノマー分子１モルあたりのエチレンオキサイドの平均付加モル数はａ＋ｂ＋ｃで表される。
本発明で述べる活性エネルギー線硬化型オフセットインキ組成物の必須成分であるエチレンオキサイド変性トリメチロールプロパントリアクリレート（Ａ）においては、ａ＋ｂ＋ｃ＝２〜６の範囲にあることが好ましい。
エチレンオキサイドの平均付加モル数が２未満である場合は親水性が低くなり過ぎ、浮き汚れなどのオフセット印刷適性不良が発現しやすくなり、６を超える場合は親水性が高くなり過ぎインキの過剰乳化に伴う印刷時の濃度低下が発現しやすくなり、また分子内の重合性基濃度が低下しインキ硬化性が悪化する傾向があり、また他原料との相溶性が低下しインキ流動性が低下する傾向がある。
In the formula (1), C is a carbon atom, H is a hydrogen atom, O is an oxygen atom, — (CH 2 —CH 2 —O) — represents an ethylene oxide group, and a, b, and c are positive numbers each including zero. Is an integer (0, 1, 2, 3,...). Therefore, the average number of moles of ethylene oxide added per mole of monomer molecule is represented by a + b + c.
In the ethylene oxide-modified trimethylolpropane triacrylate (A), which is an essential component of the active energy ray-curable offset ink composition described in the present invention, a + b + c = 2 to 6 is preferable.
When the average added mole number of ethylene oxide is less than 2, the hydrophilicity becomes too low, and offset printing suitability such as floating stains is likely to appear, and when it exceeds 6, the hydrophilicity becomes too high and the ink is excessively emulsified. It tends to cause a decrease in density at the time of printing due to printing, and tends to deteriorate the ink curability due to a decrease in the concentration of polymerizable groups in the molecule. In addition, the compatibility with other raw materials decreases and the ink fluidity decreases. Tend.
エチレンオキサイド変性ビスフェノールＡジアクリレート（ＣＡＳ登録番号６４４０１−０２−１）の一般化学構造は式（２）で示される。 The general chemical structure of ethylene oxide modified bisphenol A diacrylate (CAS Registry Number 64401-02-1) is shown by Formula (2).
式（２）において、Ｃは炭素原子、Ｈは水素原子、Ｏは酸素原子であり、−（ＣＨ２−ＣＨ２−Ｏ）−はエチレンオキサイド基を示し、ｄ、ｅはそれぞれゼロを含む正の整数（０，１，２，３・・・）である。従ってモノマー分子１モルあたりのエチレンオキサイドの平均付加モル数はｄ＋ｅで表される。
本発明で述べる活性エネルギー線硬化型オフセットインキ組成物の必須成分であるエチレンオキサイド変性ビスフェノールＡジアクリレート（Ｂ）においては、ｄ＋ｅ＝２〜６の範囲にあることが好ましい。
エチレンオキサイドの平均付加モル数が２未満である場合は粘度が過多となり、インキ粘度調整の際に相対的にバインダー成分である樹脂、オリゴマー量を削減する必要がありオフセット印刷適性が悪化する傾向があり、６を超える場合は親水性が高くなり過ぎインキの過剰乳化に伴う印刷時の濃度低下が発現しやすくなり、また分子内の重合性基濃度が低下しインキ硬化性が悪化する傾向があり、また他原料との相溶性が低下しインキ流動性が低下する傾向がある。
In the formula (2), C is a carbon atom, H is a hydrogen atom, O is an oxygen atom,-(CH2-CH2-O)-represents an ethylene oxide group, and d and e are positive integers each including zero. (0, 1, 2, 3...). Accordingly, the average number of moles of ethylene oxide added per mole of monomer molecule is expressed as d + e.
In the ethylene oxide-modified bisphenol A diacrylate (B), which is an essential component of the active energy ray-curable offset ink composition described in the present invention, it is preferably in the range of d + e = 2-6.
When the average added mole number of ethylene oxide is less than 2, the viscosity is excessive, and it is necessary to reduce the amount of resin and oligomer as binder components when adjusting the ink viscosity, which tends to deteriorate the offset printing suitability. Yes, if it exceeds 6, the hydrophilicity becomes too high, and the density decrease during printing due to the excessive emulsification of the ink tends to occur, and the concentration of polymerizable groups in the molecule tends to decrease and the ink curability tends to deteriorate. In addition, compatibility with other raw materials tends to decrease and ink fluidity tends to decrease.
前記エチレンオキサイド変性ビスフェノールＡジアクリレート（Ｂ）の添加量は、好ましくはインキ組成物全量の１〜３３重量％であり、より好ましくは３〜２５重量％である。１重量％を下回るとインキ乳化率が低下し過ぎ、浮き汚れなどのオフセット印刷適性不良が発現しやすくなり、３３重量％を上回ると乳化率が過剰となり濃度低下等の印刷適性不良が発現しやすくなる。
本発明の活性エネルギー線硬化型オフセットインキ組成物においては上記エチレンオキサイド変性トリメチロールプロパントリアクリレート（Ａ）およびエチレンオキサイド変性ビスフェノールＡジアクリレート（Ｂ）を同時に併用する相乗効果によって、良好なインキ流動性、硬化性、オフセット印刷適性の全てを満たすことができる。
The amount of the ethylene oxide-modified bisphenol A diacrylate (B) added is preferably 1 to 33% by weight, more preferably 3 to 25% by weight, based on the total amount of the ink composition. If the amount is less than 1% by weight, the ink emulsification rate decreases too much, and offset printing aptitude such as floating stains is likely to appear. If the amount exceeds 33% by weight, the emulsification rate becomes excessive and printing aptitude such as a decrease in density tends to occur. Become.
In the active energy ray-curable offset ink composition of the present invention, good ink fluidity is obtained by the synergistic effect of simultaneously using the ethylene oxide-modified trimethylolpropane triacrylate (A) and the ethylene oxide-modified bisphenol A diacrylate (B). , Curability and offset printing suitability can be satisfied.
更に、本発明の活性エネルギー線硬化型オフセットインキ組成物は、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物を、インキ組成物全量の１〜３０重量％の範囲で含有することができる。ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物はモノマーとして極めて硬化性に優れる一方、高粘度である。使用量が１重量％を下回ると硬化性の向上効果が期待できず、３０重量％を上回るとインキ粘度調整の際に相対的にバインダー成分である樹脂、オリゴマー量を削減する必要があり、インキ流動性やオフセット印刷適性が悪化する傾向がある。 Furthermore, the active energy ray-curable offset ink composition of the present invention can contain a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in the range of 1 to 30% by weight of the total amount of the ink composition. A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate is extremely excellent in curability as a monomer, but has a high viscosity. If the amount used is less than 1% by weight, the effect of improving curability cannot be expected. If the amount used exceeds 30% by weight, it is necessary to reduce the amount of resin and oligomer as binder components when adjusting the ink viscosity. There is a tendency for fluidity and offset printability to deteriorate.
通常、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートは単体もしくは混合物の状態で製造販売されており、製品名として「ＤＰＨＡ（サートマー社製、製品中のヘキサアクリレートの割合：ほぼ１００重量％）」「アロニックスＭ−４００（東亞合成社製、製品中のペンタアクリレートの割合：４０〜５０重量％）」「アロニックスＭ−４０２（東亞合成社製、製品中のペンタアクリレートの割合：３０〜４０重量％）」「アロニックスＭ−４０３（東亞合成社製、製品中のペンタアクリレートの割合：５０〜６０重量％）」「アロニックスＭ−４０４（東亞合成社製、製品中のペンタアクリレートの割合：３０〜４０重量％）」「アロニックスＭ−４０５（東亞合成社製、製品中のペンタアクリレートの割合：１０〜２０重量％）」「アロニックスＭ−４０６（東亞合成社製、製品中のペンタアクリレートの割合：２５〜３５重量％）」「ＬＵＭＩＣＵＲＥ ＤＰＡ−６００Ｔ（張家港東亜油愛生化学有限公司社製）」「カヤラッドＤＰＨＡ（日本化薬社製）」「ＳＲ３９９（サートマー社製、製品中のペンタアクリレートの割合：ほぼ１００重量％）」「ＭＩＲＡＭＥＲ Ｍ６００（ＭＩＷＯＮ社製、製品中のヘキサアクリレートの割合：ほぼ１００重量％）」等が挙げられ、５官能および６官能アクリレートの混合比率は各々異なるが、いずれも本発明において好適に使用することができる。 Usually, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are manufactured and sold in the form of a single substance or a mixture, and the product name is “DPHA (manufactured by Sartomer, ratio of hexaacrylate in the product: almost 100% by weight)” “Aronix M-400 (manufactured by Toagosei Co., Ltd., ratio of pentaacrylate in the product: 40-50% by weight)” “Aronix M-402 (manufactured by Toagosei Co., Ltd., ratio of pentaacrylate in the product: 30-40% by weight) ) “Aronix M-403 (manufactured by Toagosei Co., Ltd., ratio of pentaacrylate in the product: 50-60% by weight)” “Aronix M-404 (manufactured by Toagosei Co., Ltd., ratio of pentaacrylate in the product: 30-40) % By weight) "" Aronix M-405 (Toagosei Co., Ltd. "Aronix M-406 (manufactured by Toagosei Co., Ltd., ratio of pentaacrylate in the product: 25-35% by weight)" "LUMICURE DPA-600T (Zhangjiagang Dong-A Oil Biochemical Co., Ltd.) "Kayarad DPHA (Nippon Kayaku Co., Ltd.)" "SR399 (Sartomer, ratio of pentaacrylate in the product: almost 100% by weight)" "MIRAMER M600 (MIWON, hexaacrylate in the product) The ratio of pentafunctional and hexafunctional acrylates is different, but both can be suitably used in the present invention.
更に、本発明の活性エネルギー線硬化型オフセットインキ組成物は、インキのバインダー成分として、重合性オリゴマーであるウレタン（メタ）アクリレートをインキ組成物全量の１０〜５０重量％の範囲で使用することができる。ウレタン（メタ）アクリレートは非反応性樹脂類と比較して硬化性に優れ、またエポキシアクリレート等の他のアクリレートオリゴマー類と比較して乳化特性やオフセット印刷適性に優れる特性があるが、使用量が１０重要％を下回ると硬化性の向上硬化が期待できず、５０重量％を超えるとインキ組成物を適切な粘度範囲に調整し諸性能を得ることが困難となる傾向がある。 Furthermore, in the active energy ray-curable offset ink composition of the present invention, urethane (meth) acrylate that is a polymerizable oligomer may be used as a binder component of the ink in a range of 10 to 50% by weight of the total amount of the ink composition. it can. Urethane (meth) acrylate has excellent curability compared to non-reactive resins, and has excellent emulsifying properties and offset printability compared to other acrylate oligomers such as epoxy acrylate, but the amount used is If it is less than 10% by weight, improvement in curability cannot be expected, and if it exceeds 50% by weight, it tends to be difficult to adjust the ink composition to an appropriate viscosity range and obtain various performances.
前記ウレタン（メタ）アクリレートとしては、イソシアネート基を有するイソシアネート化合物と水酸基を有する（メタ）アクリレートモノマーをウレタン化反応させてなる化合物全般を示し、前記イソシアナート化合物は分子中に２つ以上のイソシアネート基を有するジイソシアネート化合物およびポリイソシアネート化合物が好ましく、例えば、２，４−トルエンジイソシアネート、２，６−トルエンジイソシアネート、３，４−トルエンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、２，４’−ジフェニルメタンジイソシアネート、１，３−キシリレンジイソシアネート、１，５−ナフタレンジイソシアネート、イソホロンジイソシアネート、１，４−シクロヘキシレンジイソシアネート、４，４‘−メチレンビスシクロヘキシルジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４−トリメチルヘキサメチレンジイソシアネート等のジイソシアネート化合物や、ポリメチレンポリフェニルポリイソシアネート（通称ポリメリックＭＤＩ）等のポリイソシアネート化合物等が挙げられる。これらイソシアネート化合物は単独で用いてもよく、２種以上を混合してもよい。 Examples of the urethane (meth) acrylate include all compounds obtained by urethanation of an isocyanate compound having an isocyanate group and a (meth) acrylate monomer having a hydroxyl group. The isocyanate compound has two or more isocyanate groups in the molecule. And diisocyanate compounds and polyisocyanate compounds having, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 3,4-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 1,3-xylylene diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4′-methylene bi Cyclohexyl diisocyanate, hexamethylene diisocyanate, or a diisocyanate compound such as 2,2,4-trimethylhexamethylene diisocyanate, polyisocyanate compounds such as polymethylene polyphenyl polyisocyanates (commonly known as polymeric MDI), and the like. These isocyanate compounds may be used independently and may mix 2 or more types.
これらの中でも芳香族イソシアネート化合物が良好な硬化性が得られる点で好ましく、とりわけ１分子中の平均イソシアネート基数が３以上のポリメチレンポリフェニルポリイソシアネートが良好な印刷適性が得られる点で好ましい。 Among these, an aromatic isocyanate compound is preferable in that good curability can be obtained, and polymethylene polyphenyl polyisocyanate having an average number of isocyanate groups in one molecule of 3 or more is particularly preferable in that good printability can be obtained.
前記水酸基を有する（メタ）アクリレートモノマーは分子中に１つの水酸基を有するアクリレートモノマーが良好な乳化適性と硬化性が得られる点で好ましく、例えば、２−ヒドロキシエチルアクリレート、２−ヒドロキシプロピルアクリレート、２−ヒドロキシブチルアクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレート、及びこれらのエチレンオキサイド、プロピレンオキサイド、テトラヒドロフランあるいはεカプロラクトンを付加重合した化合物等を挙げることが出来る。 As the (meth) acrylate monomer having a hydroxyl group, an acrylate monomer having one hydroxyl group in the molecule is preferable in that good emulsifiability and curability are obtained. For example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2 Examples thereof include hydroxybutyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and compounds obtained by addition polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, or ε-caprolactone.
本発明の活性エネルギー線硬化型オフセットインキ組成物は、基材に印刷後、活性エネルギー線を照射することで硬化皮膜とすることができる。この活性エネルギー線とは、紫外線、電子線、α線、β線、γ線等の電離放射線が挙げられる。これらのなかでも特に、硬化性および利便性の点から紫外線（ＵＶ）が好ましい。 The active energy ray-curable offset ink composition of the present invention can be formed into a cured film by irradiating active energy rays after printing on a substrate. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Of these, ultraviolet (UV) is particularly preferred from the viewpoint of curability and convenience.
本発明の活性エネルギー線硬化型オフセットインキ組成物を硬化させる活性エネルギー線としては、上記の通り、紫外線、電子線、α線、β線、γ線のような電離放射線であるが、具体的なエネルギー源又は硬化装置としては、例えば、殺菌灯、紫外線用蛍光灯、紫外線発光ダイオード（ＵＶ−ＬＥＤ）、カーボンアーク、キセノンランプ、複写用高圧水銀灯、中圧又は高圧水銀灯、超高圧水銀灯、無電極ランプ、メタルハライドランプ、自然光等を光源とする紫外線、又は走査型、カーテン型電子線加速器による電子線等が挙げられる。 As described above, the active energy rays for curing the active energy ray-curable offset ink composition of the present invention are ionizing radiations such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Examples of energy sources or curing devices include germicidal lamps, fluorescent lamps for ultraviolet rays, ultraviolet light emitting diodes (UV-LEDs), carbon arcs, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, and no electrodes Examples thereof include lamps, metal halide lamps, ultraviolet rays using natural light as a light source, or electron beams using a scanning type or curtain type electron beam accelerator.
次に、本発明の活性エネルギー線硬化型オフセットインキ組成物が紫外線硬化型組成物である場合に用いる光重合開始剤は、分子内開裂型光重合開始剤及び水素引き抜き型光重合開始剤が挙げられる。分子内開裂型光重合開始剤としては、例えば、ジエトキシアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、ベンジルジメチルケタール、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、４−（２−ヒドロキシエトキシ）フェニル−（２−ヒドロキシ−２−プロピル）ケトン、１−ヒドロキシシクロヘキシル−フェニルケトン、２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチル−プロピオニル）−ベンジル］−フェニル｝−２−メチル−プロパン−１−オン、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、２，２−ジエトキシ−１，２−ジフェニルエタン−１−オン等のアセトフェノン系化合物；１−［４−（フェニルチオ）−，２−（Ｏ−ベンゾイルオキシム）］、１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−，１−（Ｏ−アセチルオキシム）等のオキシム系化合物、３，６−ビス（２−メチル−２−モルフォリノプロパノニル）−９−ブチルカルバゾール等のカルバゾール系化合物、ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル等のベンゾイン系化合物； Next, examples of the photopolymerization initiator used when the active energy ray-curable offset ink composition of the present invention is an ultraviolet curable composition include an intramolecular cleavage type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator. It is done. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy. 2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-hydroxy-1- {4- [4 -(2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2- Acetophenone compounds such as diethoxy-1,2-diphenylethane-1-one; 1- [4- (phenylthio)-, 2- O-benzoyloxime)], 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), 3, 6 A carbazole compound such as bis (2-methyl-2-morpholinopropanonyl) -9-butylcarbazole, a benzoin compound such as benzoin, benzoin methyl ether, and benzoin isopropyl ether;
２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）ブタン−１−オン、２−（ジメチルアミノ）−２−（４−メチルベンジル）−１−（４−モルフォリノフェニル）ブタン−１−オン、２−メチル−２−モルホリノ（（４−メチルチオ）フェニル）プロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン等のアミノアルキルフェノン系化合物；ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス（２，６−ジメトキシベンゾイル）−２，４，４−トリメチル−ペンチルフォスフィンオキサイド等のアシルホスフィンオキシド系化合物；ベンジル、メチルフェニルグリオキシエステル等が挙げられる。 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (dimethylamino) -2- (4-methylbenzyl) -1- (4-morpholinophenyl) butane Aminoalkylphenones such as -1-one, 2-methyl-2-morpholino ((4-methylthio) phenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone Compounds: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl -Acylphosphine oxide compounds such as pentylphosphine oxide; benzyl, methylphenyl Li oxy esters.
一方、水素引き抜き型光重合開始剤としては、例えば、ベンゾフェノン、ｏ−ベンゾイル安息香酸メチル−４−フェニルベンゾフェノン、４，４’−ジクロロベンゾフェノン、
ヒドロキシベンゾフェノン、４−ベンゾイル−４’−メチル−ジフェニルサルファイド、
アクリル化ベンゾフェノン、３，３’，４，４’−テトラ（ｔ−ブチルペルオキシカルボニル）ベンゾフェノン、３，３’−ジメチル−４−メトキシベンゾフェノン等のベンゾフェノン系化合物；２−イソプロピルチオキサントン、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２，４−ジクロロチオキサントン等のチオキサントン系化合物；４，４’−ビスジメチルアミノベンゾフェノン、４，４’−ビスジエチルアミノベンゾフェノン等のアミノベンゾフェノン系化合物；その他１０−ブチル−２−クロロアクリドン、２−エチルアンスラキノン、９，１０−フェナンスレンキノン、カンファーキノン等が挙げられる。これらの光重合開始剤は、単独で用いることも、２種以上を併用することもできる。これらのなかでも特に硬化性に優れる点からアミノアルキルフェノン系化合物が好ましく、また、特に発光ピーク波長が３５０〜４２０ｎｍの範囲の紫外線を発生するＵＶ−ＬＥＤ光源を活性エネルギー線源として用いた場合には、アミノアルキルフェノン系化合物、アシルホスフィンオキシド系化合物、及びアミノベンゾフェノン系化合物を併用することが硬化性に優れる点から好ましい。
On the other hand, as the hydrogen abstraction type photopolymerization initiator, for example, benzophenone, methyl 4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone,
Hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide,
Benzophenone compounds such as acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4- Thioxanthone compounds such as dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone; aminobenzophenone compounds such as 4,4′-bisdimethylaminobenzophenone and 4,4′-bisdiethylaminobenzophenone; Examples include butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, and the like. These photopolymerization initiators can be used alone or in combination of two or more. Among these, aminoalkylphenone compounds are preferable from the viewpoint of excellent curability, and particularly when a UV-LED light source that generates ultraviolet rays having an emission peak wavelength in the range of 350 to 420 nm is used as an active energy ray source. Is preferably used in combination with an aminoalkylphenone compound, an acylphosphine oxide compound, and an aminobenzophenone compound from the viewpoint of excellent curability.
これらの重合開始剤の使用量は、本発明の活性エネルギー線硬化型オフセットインキ組成物中の不揮発成分１００重量％に対し、その合計使用量として１〜２０重量％となる範囲であることが好ましい。即ち、重合開始剤の合計使用量が１重量％以上の場合は良好な硬化性を得ることができ、また２０重量％以下の場合は、未反応の重合開始剤が硬化物中に残存することによるマイグレーション、耐溶剤性、耐候性等の物性低下といった問題を回避できる。これらの性能バランスがより良好なものとなる点から、特に、本発明の活性エネルギー線硬化型インキ組成物中の不揮発成分１００重量％に対し、その合計使用量が３〜１５重量％となる範囲であることがより好ましい。ただし活性エネルギー線として電子線を用いる場合には、原理的にこれら光重合開始剤の使用は必須ではない。 The amount of these polymerization initiators used is preferably in the range of 1 to 20% by weight as the total amount used with respect to 100% by weight of the non-volatile components in the active energy ray-curable offset ink composition of the present invention. . That is, when the total amount of the polymerization initiator used is 1% by weight or more, good curability can be obtained, and when it is 20% by weight or less, an unreacted polymerization initiator remains in the cured product. The problem of physical properties such as migration, solvent resistance, weather resistance and the like can be avoided. From the point that these performance balances become better, in particular, the total amount used is 3 to 15% by weight with respect to 100% by weight of the nonvolatile components in the active energy ray-curable ink composition of the present invention. It is more preferable that However, when an electron beam is used as the active energy ray, the use of these photopolymerization initiators is not essential in principle.
また、前記した重合開始剤の他に、光増感剤を利用することで硬化性を一層向上させることが可能である。斯かる光増感剤は、例えば、脂肪族アミン等のアミン化合物、ｏ−トリルチオ尿素等の尿素類、ナトリウムジエチルジチオホスフェート、ｓ−ベンジルイソチウロニウム−ｐ−トルエンスルホネート等の硫黄化合物などが挙げられる。これら光増感剤の使用量は、硬化性向上の効果が良好なものとなる点から本発明の活性エネルギー線硬化型インキ組成物中の不揮発成分１００重量％に対し、その合計使用量として１〜２０重量％となる範囲であることが好ましい。 Moreover, it is possible to improve sclerosis | hardenability further by utilizing a photosensitizer other than an above described polymerization initiator. Such photosensitizers include, for example, amine compounds such as aliphatic amines, ureas such as o-tolylthiourea, sulfur compounds such as sodium diethyldithiophosphate, s-benzylisothiouronium-p-toluenesulfonate, and the like. It is done. The use amount of these photosensitizers is 1 as the total use amount with respect to 100% by weight of the non-volatile component in the active energy ray-curable ink composition of the present invention from the viewpoint that the effect of improving curability is good. A range of ˜20% by weight is preferred.
本発明の活性エネルギー線硬化型オフセットインキ組成物では、硬化性を向上させる目的でワックスを添加することができる。前記ワックスとしては、パラフィンワックス、カルナバワックス、みつろう、マイクロクリスタリンワックス、ポリエチレンワックス、酸化ポリエチレンワックス、ポリテトラフルオロエチレンワックス、アマイドワックスなどのワックス、ヤシ油脂肪酸や大豆油脂肪酸などのＣ８〜Ｃ１８程度の範囲にある脂肪酸等を挙げることができる。 In the active energy ray-curable offset ink composition of the present invention, a wax can be added for the purpose of improving curability. Examples of the wax include paraffin wax, carnauba wax, beeswax, microcrystalline wax, polyethylene wax, polyethylene oxide wax, polytetrafluoroethylene wax, amide wax and the like, and C8-C18 grades such as coconut oil fatty acid and soybean oil fatty acid. The fatty acid etc. which are in the range can be mentioned.
中でもポリエチレンワックス、酸化ポリエチレンワックスに代表されるパウダータイプ又は粒子タイプのポリオレフィンワックスは良好なインキ流動性と硬化性が得られるため好ましく、さらに前記ポリオレフィンワックスの融点が９０〜１３０℃の範囲にありかつ平均粒子径Ｄ５０が１〜１０マイクロメートルの範囲にあるポリオレフィンワックスであればより好ましい。平均粒子径Ｄ５０が１マイクロメートル未満の場合は硬化性を向上させることが難しく、１０マイクロメートルを超える場合は印刷機上のインキ転移性が著しく低下しオフセット印刷適性を損なうことから好ましくない。また本発明の活性エネルギー線硬化型組成物中の不揮発成分１００重量％に対し、ワックスの総使用量が０．１〜５重量％となる範囲であることが好ましい。 Among these, a powder type or particle type polyolefin wax typified by polyethylene wax and oxidized polyethylene wax is preferable because good ink fluidity and curability are obtained, and the melting point of the polyolefin wax is in the range of 90 to 130 ° C. A polyolefin wax having an average particle diameter D50 in the range of 1 to 10 micrometers is more preferable. When the average particle diameter D50 is less than 1 micrometer, it is difficult to improve the curability, and when it exceeds 10 micrometers, the ink transfer property on the printing press is remarkably deteriorated and the offset printability is impaired. The total amount of wax used is preferably in the range of 0.1 to 5% by weight with respect to 100% by weight of the nonvolatile component in the active energy ray-curable composition of the present invention.
また、本発明の活性エネルギー線硬化型オフセットインキ組成物に用いる顔料としては、公知公用の着色用有機顔料を挙げることができ、例えば「有機顔料ハンドブック（著者：橋本勲、発行所：カラーオフィス、２００６年初版）」に掲載される印刷インキ用有機顔料等が挙げられ、溶性アゾ顔料、不溶性アゾ顔料、縮合アゾ顔料、金属フタロシアニン顔料、無金属フタロシアニン顔料、キナクリドン顔料、ペリレン顔料、ペリノン顔料、イソインドリノン顔料、イソインドリン顔料、ジオキサジン顔料、チオインジゴ顔料、アンスラキノン系顔料、キノフタロン顔料、金属錯体顔料、ジケトピロロピロール顔料、カーボンブラック顔料、その他多環式顔料等が使用可能である。 Examples of the pigment used in the active energy ray-curable offset ink composition of the present invention include publicly known organic pigments for coloring, such as “Organic Pigment Handbook (Author: Isao Hashimoto, Publisher: Color Office, Organic pigments for printing inks, etc., which are listed in the first edition of 2006), soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, Indolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, carbon black pigments, and other polycyclic pigments can be used.
また、本発明の活性エネルギー線硬化型オフセットインキ組成物には、体質顔料として無機微粒子を用いてもよい。無機微粒子としては、酸化チタン、グラファイト、亜鉛華等の無機着色顔料；炭酸石灰粉、沈降性炭酸カルシウム、石膏、クレー(ＣｈｉｎａＣｌａｙ)、シリカ粉、珪藻土、タルク、カオリン、アルミナホワイト、硫酸バリウム、ステアリン酸アルミニウム、炭酸マグネシウム、バライト粉、砥の粉等の無機体質顔料； 等の無機顔料や、シリコーン、ガラスビーズなどがあげられる。これら無機微粒子は、インキ中に０．１〜２０重量％の範囲で使用することにより、インキの流動性調整、ミスチング防止、紙等の印刷基材への浸透防止といった効果を得ることが可能である。 In the active energy ray-curable offset ink composition of the present invention, inorganic fine particles may be used as extender pigments. Inorganic fine particles include inorganic coloring pigments such as titanium oxide, graphite, zinc white; lime carbonate powder, precipitated calcium carbonate, gypsum, clay (ChinaClay), silica powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, stearin Inorganic pigments such as aluminum oxide, magnesium carbonate, barite powder, and abrasive powder; inorganic pigments such as silicone, glass beads, and the like. By using these inorganic fine particles in the ink in the range of 0.1 to 20% by weight, it is possible to obtain effects such as ink fluidity adjustment, prevention of misting, and prevention of penetration into printing substrates such as paper. is there.
本発明の活性エネルギー硬化型オフセットインキ組成物では、更に公知公用の各種バインダー樹脂を利用することができる。ここで述べるバインダー樹脂とは、適切な顔料親和性と分散性を有し、印刷インキに要求されるレオロジー特性を有する樹脂全般を示しており、例えば非反応性樹脂としては、ジアリルフタレート樹脂、エポキシ樹脂、ポリウレタン樹脂、ポリエステル樹脂、石油樹脂、ロジンエステル樹脂、ポリ（メタ）アクリル酸エステル、セルロース誘導体、塩化ビニル−酢酸ビニル共重合体、ポリアマイド樹脂、ポリビニルアセタール樹脂、ブタジエン−アクリルニトリル共重合体等を挙げることができ、これらバインダー樹脂化合物は、単独で使用しても、いずれか１種以上を組合せて使用してもよい。 In the active energy curable offset ink composition of the present invention, various publicly known binder resins can be used. The binder resin described here refers to all resins having appropriate pigment affinity and dispersibility, and rheological properties required for printing inks. For example, non-reactive resins include diallyl phthalate resin and epoxy resin. Resin, polyurethane resin, polyester resin, petroleum resin, rosin ester resin, poly (meth) acrylate ester, cellulose derivative, vinyl chloride-vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, butadiene-acrylonitrile copolymer, etc. These binder resin compounds may be used alone or in combination of any one or more thereof.
本発明の活性エネルギー線硬化型オフセットインキ組成物では、上記した各成分の他の配合物として、染料、有機溶剤、帯電防止剤、消泡剤、粘度調整剤、耐光安定剤、耐候安定剤、耐熱安定剤、紫外線吸収剤、酸化防止剤、レベリング剤、顔料分散剤等の添加剤を使用することができる。 In the active energy ray-curable offset ink composition of the present invention, as other blends of the above-described components, dyes, organic solvents, antistatic agents, antifoaming agents, viscosity modifiers, light-resistant stabilizers, weather-resistant stabilizers, Additives such as a heat stabilizer, an ultraviolet absorber, an antioxidant, a leveling agent, and a pigment dispersant can be used.
本発明の活性エネルギー線硬化型オフセットインキ組成物で使用する印刷基材としては特に限定は無く、例えばカタログ、ポスター、チラシ、ＣＤジャケット、ダイレクトメール、パンフレット、化粧品や飲料、医薬品、おもちゃ、機器等のパッケージ等の印刷に用いられる上質紙、コート紙、アート紙、模造紙、薄紙、厚紙等の紙、各種合成紙、ポリエステル樹脂、アクリル樹脂、塩化ビニル樹脂、塩化ビニリデン樹脂、ポリビニルアルコール、ポリエチレン、ポリプロピレン、ポリアクリロニトリル、エチレン酢酸ビニル共重合体、エチレンビニルアルコール共重合体、エチレンメタクリル酸共重合体、ナイロン、ポリ乳酸、ポリカーボネート等のフィルム又はシート、セロファン、アルミニウムフォイル、その他従来から印刷基材として使用されている各種基材を挙げることが出来る。 The printing substrate used in the active energy ray-curable offset ink composition of the present invention is not particularly limited. For example, catalogs, posters, flyers, CD jackets, direct mails, brochures, cosmetics and beverages, pharmaceuticals, toys, equipment, etc. Quality paper, coated paper, art paper, imitation paper, thin paper, cardboard, etc., various synthetic paper, polyester resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, Polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, nylon or polylactic acid, polycarbonate film or sheet, cellophane, aluminum foil, etc. It can be mentioned various substrates that are used.
本発明で述べる活性エネルギー線硬化型オフセットインキ組成物の製造は、従来の活性エネルギー線硬化型オフセットインキ組成物紫と同様に、前記着色顔料、重合性アクリレートモノマー、ウレタンオリゴマー(ワニス)、バインダー樹脂、光重合開始剤、増感剤、その他添加剤等を配合してミキサー等で撹拌混合し、三本ロールミル、ビーズミル等の分散機を用いて練肉することで製造される。 The active energy ray-curable offset ink composition described in the present invention is produced in the same manner as the conventional active energy ray-curable offset ink composition purple, the color pigment, the polymerizable acrylate monomer, the urethane oligomer (varnish), and the binder resin. , A photopolymerization initiator, a sensitizer, other additives and the like are mixed, stirred and mixed with a mixer, and then kneaded using a dispersing machine such as a three-roll mill or a bead mill.
以下、実施例によって本発明を具体的に説明する。 Hereinafter, the present invention will be described specifically by way of examples.
〔インキ組成物の製造方法〕
表１〜３の組成に従って、実施例１〜４および比較例１〜１２のインキを三本ロールミルにて練肉することによって、各種の活性エネルギー線硬化型インキ組成物を得た。
表１〜３の数値は重量％である。
尚、全てのインキ組成物に対し着色成分として藍顔料であるＤＩＣ株式会社製ＦＡＳＴＯＧＥＮ ＢＬＵＥ ＴＧＲ−１（Ｐｉｇｍｅｎｔ Ｂｌｕｅ１５：３、フタロシアニンブルー）１９重量％、粘度及び流動性調整剤としてタルク２重量％、助剤としてポリオレフィンワックス１重量％、光重合開始剤としてＢＡＳＦ社製Ｉｒｇａｃｕｒｅ９０７（２−メチル−１−［４−（メチルチオ）フェニル］−２−モノフォリノプロパン−１−オン）３重量％および大同化成工業社製ＥＡＢ−ＳＳ（４，４′−ビス（ジエチルアミノ）ベンゾフェノン）２．５重量％、重合禁止剤として重合禁止剤ベース１（和光純薬工業社製Ｑ１３０１（Ｎ‐ニトロソフェニルヒドロキシルアミンアルミニウム塩）５重量％をＭＩＷＯＮ社製ＭＩＲＡＭＥＲ Ｍ３００（トリメチロールプロパントリアクリレート）９５重量％に溶解させた液状混合物）１重量％を共通に添加した。
また、作製した各インキ組成物１．３１ｍｌを東洋精機（株）製インコメーターに塗布し、ローラー温度３２℃、回転スピード４００ｒｐｍに設定して回転させ、１分後のタックバリュー（Ｔ．Ｖ．）値を読み取り、タックバリュー（Ｔ．Ｖ．）値が全例とも標準的な１０である事を確認した。
[Method for producing ink composition]
According to the composition of Tables 1-3, various active energy ray hardening-type ink compositions were obtained by kneading the ink of Examples 1-4 and Comparative Examples 1-12 with a three roll mill.
The numerical values in Tables 1 to 3 are% by weight.
DIC Corporation FASTOGEN BLUE TGR-1 (Pigment Blue 15: 3, phthalocyanine blue) 19% by weight as a coloring component for all ink compositions, talc 2% by weight as a viscosity and fluidity modifier, 1% by weight of polyolefin wax as an auxiliary agent, 3% by weight of Irgacure 907 (2-methyl-1- [4- (methylthio) phenyl] -2-monoforinopropan-1-one) manufactured by BASF as a photopolymerization initiator, and Daido EAB-SS (4,4'-bis (diethylamino) benzophenone) manufactured by Kasei Kogyo Co., Ltd. 2.5% by weight, polymerization inhibitor base 1 as a polymerization inhibitor (Q1301 manufactured by Wako Pure Chemical Industries, Ltd. (N-nitrosophenylhydroxylamine aluminum) Salt) 5% by weight MIRAMER M300 manufactured by MIWON 1% by weight of (liquid mixture dissolved in 95% by weight of trimethylolpropane triacrylate) was added in common.
Further, 1.31 ml of each ink composition thus prepared was applied to an incometer manufactured by Toyo Seiki Co., Ltd., rotated at a roller temperature of 32 ° C. and a rotation speed of 400 rpm, and the tack value (T.V. ) Value was read and it was confirmed that the tack value (T.V.) value was standard 10 in all cases.
〔展色物の製造方法〕
この様にして得られた活性エネルギー線硬化型インキ組成物を、簡易展色機（ＲＩテスター、豊栄精工社製）を用い、インキ０．１０ｍｌを使用して、ＲＩテスターのゴムロール及び金属ロール上に均一に引き伸ばし、コートボール紙（王子マテリア社製ＵＦコート、米坪３５０ｇ／ｍ２）の表面に、２００ｃｍ２の面積にわたって藍濃度１．６（Ｘ−Ｒｉｔｅ社製ＳｐｅｃｔｒｏＥｙｅ濃度計で計測）で均一に塗布されるように展色し、展色物を作製した。なおＲＩテスターとは、紙やフィルムにインキを展色する試験機であり、インキの転移量や印圧を調整することが可能である。
[Manufacturing method of exhibition colors]
The active energy ray-curable ink composition thus obtained was used on a rubber roll and metal roll of the RI tester using a simple color developing machine (RI tester, manufactured by Toyoe Seiko Co., Ltd.) and using 0.10 ml of ink. And uniformly coated on the surface of a coated cardboard (UF coat manufactured by Oji Materia Co., Ltd., 350 g / m 2 ) with an indigo density of 1.6 (measured with a SpectroEye densitometer manufactured by X-Rite) over an area of 200 cm 2. The color was developed so as to be applied uniformly, and a color-extended product was produced. The RI tester is a test machine that develops ink on paper or film, and can adjust the amount of ink transferred and the printing pressure.
〔ＵＶランプ光源による硬化方法〕
インキ塗布後の展色物に活性エネルギー線である紫外線（ＵＶ）照射を行い、インキ皮膜を硬化させた。水冷メタルハライドランプ（出力１００Ｗ／ｃｍ１灯）およびベルトコンベアを搭載したＵＶ照射装置（アイグラフィックス社製、コールドミラー付属）を使用し、展色物をコンベア上に載せ、ランプ直下（照射距離１１ｃｍ）を分速１００メートルの速度で通過させることにより、インキ皮膜を硬化させた。各条件における紫外線照射量は紫外線積算光量計（ウシオ電機社製ＵＮＩＭＥＴＥＲ ＵＩＴ−１５０−Ａ／受光機ＵＶＤ−Ｃ３６５）を用いて測定した。
[Curing method using UV lamp light source]
Irradiation with ultraviolet rays (UV), which is an active energy ray, was performed on the color-extended product after the ink application to cure the ink film. Using a UV irradiation device equipped with a water-cooled metal halide lamp (output: 100 W / cm1 light) and a belt conveyor (made by Eye Graphics Co., Ltd., with a cold mirror), the color-exposed product is placed on the conveyor and directly under the lamp (irradiation distance: 11 cm) Was passed through at a speed of 100 meters per minute to cure the ink film. The ultraviolet irradiation amount in each condition was measured using an ultraviolet integrated light meter (UNIMETER UIT-150-A / receiver UVD-C365 manufactured by USHIO INC.).
〔活性エネルギー線硬化型インキ組成物の評価方法１：流動性〕
インキ流動性はスプレッドメーター法（平行板粘度計）によりＪＩＳ Ｋ５１０１、５７０１に則った方法で測定を実施し、水平に置いた２枚の平行板の間に挟まれたインキが、荷重板の自重（１１５グラム）によって、同心円状に広がる特性を経時的に観察し、６０秒後のインキの広がり直径をダイアメーター値（ＤＭ［ｍｍ］）とし、インキ印刷適性が良好となる次の２段階で評価した。本評価項目においてＤＭが３０ｍｍ未満となる組成では、印刷機上で壺切れ、インキローラ間の転移不良といった印刷適性面での不良が発現し易くなる。
○：ＤＭ３０ｍｍ以上であり、流動性は良好である。
×：ＤＭ３０ｍｍ未満であり、流動性は不良である。
[Evaluation method of active energy ray-curable ink composition 1: fluidity]
Ink fluidity is measured by a spread meter method (parallel plate viscometer) according to JIS K5101, 5701. The ink sandwiched between two parallel plates placed horizontally is the weight of the load plate (115 )), The characteristics spreading concentrically over time were observed over time, and the ink spreading diameter after 60 seconds was taken as a diameter value (DM [mm]) and evaluated in the following two stages where ink printing suitability was good. . In the composition where DM is less than 30 mm in this evaluation item, defects in printability such as fraying on a printing machine and transfer failure between ink rollers are likely to occur.
○: DM is 30 mm or more, and fluidity is good.
X: DM is less than 30 mm, and fluidity is poor.
〔活性エネルギー線硬化型インキ組成物の評価方法２：硬化性〕
硬化性は、紫外線照射直後に爪スクラッチ法にて展色物表面の傷付きの有無を確認し次の５段階で評価した。爪で擦ってインキ硬化皮膜に傷が発生する組成では、印刷物の断裁や製函、輸送といった各工程において、印刷物が損傷し易くなる。
５：爪スクラッチで傷が発生せず、硬化性は良好である。
４：３（良好）と５（中位）の中間の硬化性が確認できた。
３：爪スクラッチで微小な傷が僅かに発生し、硬化性は中位である。
２：３（中位）と１（不良）の中間の硬化性が確認できた。
１：爪スクラッチで傷が明確に発生し、硬化性は不良である。
[Evaluation method 2 of active energy ray-curable ink composition: curability]
The curability was evaluated in the following five stages by checking the presence or absence of scratches on the surface of the developed product by the nail scratch method immediately after the ultraviolet irradiation. In the composition in which the ink cured film is scratched by rubbing with a nail, the printed material is easily damaged in each process such as cutting, box making and transportation of the printed material.
5: No scratches are generated by the nail scratch, and the curability is good.
An intermediate curability between 4: 3 (good) and 5 (medium) was confirmed.
3: Slight scratches are slightly generated by the nail scratch and the curability is moderate.
An intermediate curability between 2: 3 (medium) and 1 (poor) was confirmed.
1: Scratches are clearly generated by claw scratches and the curability is poor.
〔活性エネルギー線硬化型インキ組成物の評価方法３：乳化率〕
インキの乳化率（乳化適性）の評価については、ダクテット試験機（川村理研製）を用いて実施した。本試験装置は特開２００３−３１２１６１、特開平１１−５３７６、特開平０６−０１１４３２において用いられた試験機と同一の測定装置である。
[Evaluation method 3: active energy ray-curable ink composition 3: emulsification rate]
The ink emulsification rate (emulsification suitability) was evaluated using a ductt tester (manufactured by Kawamura Riken). This test apparatus is the same measurement apparatus as the test machine used in Japanese Patent Application Laid-Open Nos. 2003-312161, 11-5376, and 06-011432.
ダクテット試験機の断面図を図１に示す。外筒３は内部がくりぬかれた、底面を有する円筒状の金属であり、内部に評価インキ７を投入できる構造となっている。評価インキ７（５グラム）投入後に円柱棒状の金属である内筒２を図１に示す通り、外筒３の底面から１ミリメートルの距離に近接するまで差し込む。その後内筒を２０００ｒｐｍで時計回りに、外筒も６０ｒｐｍで時計回りに回転させ、速度差をつけることで評価インキ７にシェアーがかかり撹拌される。撹拌後３分間が経過した時点で、撹拌を継続しながら蒸留水を０．５（グラム／分）の速度で評価インキ７の直上に滴下することで、評価インキ７と滴下された蒸留水は即時に撹拌混合される（乳化）。蒸留水の滴下は１０分間継続され、蒸留水の滴下量が合計５グラムに達した時点で終了される。
ダクテット試験機は、外筒３は外筒用駆動モーター５によって回転し、内筒２は内筒用駆動モーター１によって回転する構造を有し、また外筒３内部の評価インキ７の温度が一定となるよう、恒温水槽４を備え水道水６の温度は常に３０℃に保たれている。
評価インキ７（５グラム）と蒸留水（５グラム）の撹拌混合が終了した後、内筒２内部にある余剰蒸留水（インキ中に取り込まれずに余った水）の重量（グラム）を秤量する。これにより、評価インキ７中に取り込まれた蒸留水の総重量Ｙは
A cross-sectional view of the ductt tester is shown in FIG. The outer cylinder 3 is a cylindrical metal having a bottom surface hollowed out, and has a structure in which the evaluation ink 7 can be put inside. After the evaluation ink 7 (5 grams) is charged, the inner cylinder 2 that is a cylindrical bar-shaped metal is inserted from the bottom surface of the outer cylinder 3 until it approaches a distance of 1 millimeter as shown in FIG. Thereafter, the inner cylinder is rotated clockwise at 2000 rpm, the outer cylinder is also rotated clockwise at 60 rpm, and the evaluation ink 7 is sheared and stirred by giving a speed difference. When 3 minutes have passed after stirring, by dropping distilled water immediately above the evaluation ink 7 at a rate of 0.5 (g / min) while continuing stirring, the evaluation ink 7 and the distilled water dropped are Immediately stirring and mixing (emulsification). The dropping of distilled water is continued for 10 minutes and is terminated when the amount of distilled water dropped reaches a total of 5 grams.
The ductette testing machine has a structure in which the outer cylinder 3 is rotated by the outer cylinder drive motor 5, the inner cylinder 2 is rotated by the inner cylinder drive motor 1, and the temperature of the evaluation ink 7 inside the outer cylinder 3 is constant. The temperature of the tap water 6 is always kept at 30 ° C. so that the constant temperature water tank 4 is provided.
After stirring and mixing of the evaluation ink 7 (5 grams) and distilled water (5 grams) is completed, the weight (gram) of excess distilled water (remaining water not taken into the ink) in the inner cylinder 2 is weighed. . Thus, the total weight Y of distilled water taken into the evaluation ink 7 is
Ｙ（グラム）＝全投入蒸留水（５グラム）−余剰蒸留水の重量
で示され、評価インキ７の乳化率Ｚは、
Y (grams) = total input distilled water (5 grams) —represented by the weight of excess distilled water, the emulsification rate Z of the evaluation ink 7 is
Ｚ（％）＝Ｙ÷（評価インキ７（５グラム）＋Ｙ）×１００
で示される。
（ここで、例えば、投入した蒸留水５グラム全てがインキ中に取り込まれ、余剰蒸留水が０グラムであった場合には、Ｙ＝５（グラム）、Ｚ＝５０（％）と計算される。）
Z (%) = Y ÷ (Evaluation ink 7 (5 grams) + Y) × 100
Indicated by
(Here, for example, when all the 5 grams of distilled water charged is taken into the ink and the excess distilled water is 0 grams, Y = 5 (grams) and Z = 50 (%) are calculated. .)
インキ乳化率Ｚ（％）の数値が適切な範囲（約２０〜３３％程度）にあれば、適度な乳化適性、すなわち水の取り込みと吐き出しのバランスに優れたインキと評価できる。インキ乳化率Ｚ（％）の数値が２０％未満の場合、インキが水を内包する能力が不足し、浮き汚れ等の印刷不良を発現する傾向があり、３３％を上回る場合、インキが過乳化し易くなり濃度低下や濃度安定性不良等の印刷不良を発現する傾向がある。
一方でインキ乳化率Ｚ（％）の数値が２０〜３３％の範囲に収まっていれば必ずしも優れた印刷適性を示すとは限らない。オフセット印刷適性は使用する各原料の親水／疎水バランスやインキのレオロジー特性等の様々な性質が複雑に相乗的に影響し合い決定されるものであるが、本発明の実施例においては適切な乳化率とオフセット印刷適性を満たしたことを確認した。
If the numerical value of the ink emulsification rate Z (%) is in an appropriate range (about 20 to 33%), it can be evaluated as an ink having an appropriate emulsification ability, that is, an excellent balance of water uptake and discharge. If the value of the ink emulsification rate Z (%) is less than 20%, the ink has insufficient ability to enclose water and tends to exhibit printing defects such as floating stains. If it exceeds 33%, the ink is over-emulsified. This tends to cause printing defects such as density reduction and density stability failure.
On the other hand, if the numerical value of the ink emulsification rate Z (%) is within the range of 20 to 33%, it does not necessarily show excellent printability. The offset printability is determined by various synergistic effects of various properties such as the hydrophilic / hydrophobic balance of each raw material used and the rheological properties of the ink. In the embodiment of the present invention, suitable emulsification is performed. Rate and offset printability were confirmed.
〔活性エネルギー線硬化型インキ組成物のオフセット印刷方法〕
製造された実施例１〜４、比較例１〜１２の活性エネルギー線硬化型インキについて、オフセット印刷適性を評価した。紫外線照射装置としてアイグラフィックス社製水冷メタルハライドランプ（出力１６０Ｗ／ｃｍ、３灯使用）を搭載したマンローランド社製オフセット印刷機（ローランドＲ７００印刷機、幅４０インチ機）を用いて、毎時９０００枚の印刷速度にてオフセット印刷を実施した。印刷用紙には王子製紙社製ＯＫトップコートプラス（５７．５ｋｇ、Ａ判）を使用した。版面に供給される湿し水は、水道水９８重量％とエッチ液（ＦＳＴ−７００、ＤＩＣ社製）２重量％を混合した水溶液を用いた。
[Offset printing method of active energy ray-curable ink composition]
With respect to the produced active energy ray-curable inks of Examples 1 to 4 and Comparative Examples 1 to 12, the offset printability was evaluated. 9000 sheets per hour using a Man Roland offset printing machine (Roland R700 printing machine, 40-inch wide machine) equipped with a water-cooled metal halide lamp (output: 160 W / cm, 3 lamps used) as an ultraviolet irradiation device. Offset printing was performed at a printing speed of. For the printing paper, OK Top Coat Plus (57.5 kg, A size) manufactured by Oji Paper Co., Ltd. was used. The dampening water supplied to the printing plate was an aqueous solution in which 98% by weight of tap water and 2% by weight of an etchant (FST-700, manufactured by DIC) were mixed.
〔活性エネルギー線硬化型インキ組成物の評価方法４：印刷適性（耐汚れ性）〕
オフセット印刷適性（耐汚れ性）の評価方法としては、まず印刷機の水供給ダイヤルを４０（標準水量）にセットし、印刷物濃度が標準プロセス藍濃度１．６（Ｘ−Ｒｉｔｅ社製ＳｐｅｃｔｒｏＥｙｅ濃度計で計測）となるようインキ供給キーを操作し、濃度が安定した時点でインキ供給キーを固定した。その後インキ供給キーを固定したままの条件で、水供給ダイヤルを４０から３５に変更し水供給量を減らした条件で３００枚印刷し、３００枚後の印刷物の「浮き汚れ」の有無を確認した。水とインキのバランスが上手く保たれていない場合、インキ粒子が湿し水中に浮遊する、あるいは版面非画線部上に付着することで印刷物の画線が明瞭でなくなり汚れが発生するが、このような印刷不良は「浮き汚れ」と呼ばれる。もし浮き汚れが発生しなかった場合は、続けて水供給ダイヤルを３５から３０に変更し水供給量を減らした条件で更に３００枚印刷し、３００枚後の印刷物の「浮き汚れ」の有無を確認する。このようにして同様に水供給量を５ポイントずつ段階的に減らしていき、「浮き汚れ」が発生し始める水供給ダイヤル値を記録した。汚れ発生時の水供給ダイヤル値が低いほど、耐汚れ性は良好であると評価できる。下記の基準に従って活性エネルギー線硬化型インキの印刷適性（耐汚れ性）を評価した。
３：浮き汚れ発生時の水供給ダイヤル値が２０未満であり、耐汚れ性は良好である。
２：浮き汚れ発生時の水供給ダイヤル値が２０〜３０の範囲にあり、耐汚れ性は中位である。
１：浮き汚れ発生時の水供給ダイヤルが３０を上回り、耐汚れ性は不良である。
[Evaluation method 4 of active energy ray-curable ink composition: printability (stain resistance)]
As an evaluation method of offset printing suitability (stain resistance), first, set the water supply dial of the printing press to 40 (standard water amount), and the print density is standard process indigo density 1.6 (SpectroEye densitometer manufactured by X-Rite). The ink supply key was operated so that the ink supply key was measured, and the ink supply key was fixed when the density was stable. Then, with the ink supply key fixed, 300 sheets were printed under the condition that the water supply dial was changed from 40 to 35 and the amount of water supply was reduced, and the presence of “floating stains” on the printed material after 300 sheets was confirmed. . If the balance between water and ink is not maintained well, the ink particles will damp and float in the water, or may adhere to the non-image area of the printing plate, resulting in unclear lines on the printed matter. Such printing defects are called “floating stains”. If floating stains did not occur, continue to change the water supply dial from 35 to 30 and reduce the amount of water supply to print another 300 sheets. Check. Similarly, the water supply amount was gradually reduced by 5 points step by step, and the water supply dial value at which “floating contamination” began to occur was recorded. It can be evaluated that the lower the water supply dial value at the time of occurrence of dirt, the better the dirt resistance. The printability (stain resistance) of the active energy ray-curable ink was evaluated according to the following criteria.
3: The water supply dial value when floating dirt is generated is less than 20, and the dirt resistance is good.
2: The water supply dial value at the time of occurrence of floating dirt is in the range of 20 to 30, and the dirt resistance is moderate.
1: The water supply dial when floating dirt is generated exceeds 30 and the dirt resistance is poor.
〔活性エネルギー線硬化型インキ組成物の評価方法５：印刷適性（濃度安定性）〕
オフセット印刷適性（濃度安定性）の評価方法としては、まず印刷機の水供給ダイヤルを４０（標準水量）にセットし、印刷物濃度が標準プロセス藍濃度１．６（Ｘ−Ｒｉｔｅ社製ＳｐｅｃｔｒｏＥｙｅ濃度計で計測）となるようインキ供給キーを操作し、濃度が安定した時点でインキ供給キーを固定した。その後インキ供給キーを固定したままの条件で、水供給ダイヤルを４０から５５に変更し水供給量を増やした条件で３００枚印刷し、３００枚後の印刷物の藍濃度を測定した。水供給量を増やした状態においても印刷物の濃度低下が少ないほど、乳化適性に優れ、濃度安定性に優れたインキと評価できる。下記の基準に従って活性エネルギー線硬化型インキの印刷適性（濃度安定性）を評価した。
３：印刷物の藍濃度が１．５以上であり、オフセット印刷適性は良好である。
２：印刷物の藍濃度が１．４以上〜１．５未満であり、オフセット印刷適性は中位であ
る。
１：印刷物の藍濃度が１．４未満であり、オフセット印刷適性は不良である。
[Evaluation method 5 of active energy ray-curable ink composition: printability (concentration stability)]
As an evaluation method of offset printing suitability (density stability), first, set the water supply dial of the printing press to 40 (standard water amount), and the print density is standard process indigo density 1.6 (SpectroEye densitometer manufactured by X-Rite). The ink supply key was operated so that the ink supply key was measured, and the ink supply key was fixed when the density was stable. Thereafter, 300 sheets were printed under the condition that the water supply dial was changed from 40 to 55 and the water supply amount was increased with the ink supply key fixed, and the indigo density of the printed material after 300 sheets was measured. Even in a state where the amount of water supply is increased, the smaller the decrease in the density of the printed matter, the better the emulsification suitability, and the ink can be evaluated as having excellent density stability. The printability (density stability) of the active energy ray-curable ink was evaluated according to the following criteria.
3: The indigo density of the printed material is 1.5 or more, and the offset printability is good.
2: The indigo density of the printed material is 1.4 or more and less than 1.5, and the offset printability is moderate.
1: The indigo density of the printed material is less than 1.4, and the offset printability is poor.
表１及び表２中の数値は重量％である。
表１、２に示す諸原料及び略を以下に示す。尚、粘度（ｍＰａ・ｓ）は全て２５℃の数値を示す。
・フタロシアニンブルー：銅フタロシアニン、ＦＡＳＴＯＧＥＮ ＢＬＵＥ ＴＧＲ−１、ＤＩＣ社製
・タルク：含水ケイ酸マグネシウム、ハイフィラー ＃５０００ＰＪ、松村産業社製
・ポリオレフィンワックス、Ｓ−３８１−Ｎ１、シャムロック社製
・Ｉｒｇａｃｕｒｅ９０７：２−メチル−１−［４−（メチルチオ）フェニル］−２−モノフォリノプロパン−１−オン、ＢＡＳＦ社製
・ＥＡＢ―ＳＳ：４，４′−ビス（ジエチルアミノ）ベンゾフェノン、大同化成工業社製
・重合禁止剤ベース１（和光純薬工業社製Ｑ１３０１（Ｎ‐ニトロソフェニルヒドロキシルアミンアルミニウム塩）５重量％をＭＩＷＯＮ社製ＭＩＲＡＭＥＲ Ｍ３００（トリメチロールプロパントリアクリレート）９５重量％に溶解させた液状混合物）
・ウレタンアクリレートワニス１：ウレタンアクリレート１（下記）６０重量％とエチレンオキサイド（平均３モル付加）変性トリメチロールプロパントリアクリレート（ＭＩＲＡＭＥＲ Ｍ３１３０、ＭＩＷＯＮ社製）４０重量％の混合物
・ウレタンアクリレートワニス２：ウレタンアクリレート１（下記）５５重量％とトリメチロールプロパントリアクリレート（ＭＩＲＡＭＥＲ Ｍ３００、ＭＩＷＯＮ社製）４５重量％の混合物
・ウレタンアクリレートワニス３：ウレタンアクリレート１（下記）５５重量％とエチレンオキサイド（平均９モル付加）変性トリメチロールプロパントリアクリレート（ＭＩＲＡＭＥＲ Ｍ３１９０、ＭＩＷＯＮ社製）４５重量％の混合物
・ウレタンアクリレート１：撹拌機、ガス導入管、コンデンサー、及び温度計を備えた１リットルのフラスコに、ポリメチレンポリフェニルポリイソシアネート（ミリオネートＭＲ−４００、日本ポリウレタン工業株式会社製）３２８．１質量部、ターシャリブチルヒドロキシトルエン３質量部、メトキシハイドロキノン０．１２質量部、ジブチル錫ジアセテート１．２質量部を加え、７０℃に昇温し、２−ヒドロキシエチルアクリレート２７１．９質量部を２時間にわたって攪拌下で滴下した。滴下後、７０℃で反応させ、イソシアネート基を示す２２５０ｃｍ−１の赤外吸収スペクトルが消失するまで反応を行いウレタンアクリレート１を得た
・ＤＡＰワニス１：ジアリルフタレート樹脂（ダイソーダップＡ、ダイソー社製）４５重量％とエチレンオキサイド（平均３モル付加）変性トリメチロールプロパントリアクリレート（ＭＩＲＡＭＥＲ Ｍ３１３０、ＭＩＷＯＮ社製）５５重量％の混合物
・ＥＯ３ＴＭＰＴＡ：エチレンオキサイド（平均３モル付加）変性トリメチロールプロパントリアクリレート、ＭＩＲＡＭＥＲ Ｍ３１３０、粘度５０〜７０ｍＰａ・ｓ、重量平均分子量４２８、ＭＩＷＯＮ社製
・ＢｉｓＡ ＥＯ４ＤＡ：エチレンオキサイド（平均４モル付加）変性ビスフェノールＡジアクリレート、ＭＩＲＡＭＥＲ Ｍ２４０、粘度９００〜１３００ｍＰａ・ｓ、重量平均分子量５１２、ＭＩＷＯＮ社製
・ＤＰＨＡ：ジペンタエリスリトールヘキサアクリレート、ＭＩＲＡＭＥＲ Ｍ６００、粘度４０００〜７０００ｍＰａ・ｓ、重量平均分子量５７８、ＭＩＷＯＮ社製
・ＤＴＭＰＴＡ：ジトリメチロールプロパンテトラアクリレート、ＳＲ３５５ＮＳ、粘度４５０〜７５０ｍＰａ・ｓ、重量平均分子量４６７、サートマー社製
・ＴＭＰＴＡ：トリメチロールプロパントリアクリレート、ＭＩＲＡＭＥＲ Ｍ３００、粘度８０〜１２０ｍＰａ・ｓ、重量平均分子量２９６、ＭＩＷＯＮ社製
・ＥＯ９ＴＭＰＴＡ：エチレンオキサイド（平均９モル付加）変性トリメチロールプロパントリアクリレート、粘度８５〜１４０ｍＰａ・ｓ、重量平均分子量６９２、ＭＩＲＡＭＥＲ Ｍ３１９０、ＭＩＷＯＮ社製
・ＢｉｓＡＥ０１０ＤＡ：エチレンオキサイド（平均１０モル付加）変性ビスフェノールＡジアクリレート、ＭＩＲＡＭＥＲ Ｍ２１００、粘度６００〜７００ｍＰａ・ｓ、重量平均分子量７７０、ＭＩＷＯＮ社製
・ＧＰＴＡ：プロピレンオキサイド（平均３モル付加）変性グリセリントリアクリレート、ＭＩＲＡＭＥＲ Ｍ３２０、粘度８０〜１２０ｍＰａ・ｓ、重量平均分子量４２８、ＭＩＷＯＮ社製
・ＰＯ３ＴＭＰＴＡ：プロピレンオキサイド（平均３モル付加）変性トリメチロールプロパントリアクリレート、ＭＩＲＡＭＥＲ Ｍ３６０、粘度７０〜１００ｍＰａ・ｓ、重量平均分子量４７０、ＭＩＷＯＮ社製
・ＥＯ４ＰＥＴＡ：エチレンオキサイド（平均４モル付加）変性ペンタエリスリトールテトラアクリレート、粘度１２０〜２００ｍＰａ・ｓ、重量平均分子量６９２、ＭＩＲＡＭＥＲ Ｍ４００４、ＭＩＷＯＮ社製
The numerical values in Tables 1 and 2 are% by weight.
Various raw materials and abbreviations shown in Tables 1 and 2 are shown below. The viscosity (mPa · s) is a value of 25 ° C.
・ Phthalocyanine blue: Copper phthalocyanine, FASTOGEN BLUE TGR-1, manufactured by DIC ・ Talc: hydrous magnesium silicate, high filler # 5000PJ, manufactured by Matsumura Sangyo Co., Ltd. ・ Polyolefin wax, S-381-N1, manufactured by Shamrock ・ Irgacure 907: 2-methyl-1- [4- (methylthio) phenyl] -2-monoforinopropan-1-one, manufactured by BASF, EAB-SS: 4,4′-bis (diethylamino) benzophenone, manufactured by Daido Kasei Kogyo Co., Ltd. Polymerization inhibitor base 1 (liquid mixture in which 5% by weight of Q1301 (N-nitrosophenylhydroxylamine aluminum salt) manufactured by Wako Pure Chemical Industries, Ltd. is dissolved in 95% by weight of MIRAMER M300 (trimethylolpropane triacrylate) manufactured by MIWON)
・ Urethane acrylate varnish 1: 60% by weight of urethane acrylate 1 (below) and 40% by weight of ethylene oxide (average 3 mol addition) modified trimethylolpropane triacrylate (MIRAMER M3130, manufactured by MIWON) ・ Urethane acrylate varnish 2: Urethane Mixture of 55% by weight of acrylate 1 (below) and 45% by weight of trimethylolpropane triacrylate (MIRAMER M300, manufactured by MIWON) ・ Urethane acrylate varnish 3: 55% by weight of urethane acrylate 1 (below) and ethylene oxide (average 9 mol addition) ) Modified trimethylolpropane triacrylate (MIRAMER M3190, manufactured by MIWON) 45 wt% mixture and urethane acrylate 1: stirrer, gas inlet tube, condenser, and In a 1 liter flask equipped with a meter, 328.1 parts by mass of polymethylene polyphenyl polyisocyanate (Millionate MR-400, manufactured by Nippon Polyurethane Industry Co., Ltd.), 3 parts by mass of tertiary butylhydroxytoluene, 0.12 of methoxyhydroquinone Part by mass and 1.2 parts by mass of dibutyltin diacetate were added, the temperature was raised to 70 ° C., and 271.9 parts by mass of 2-hydroxyethyl acrylate was added dropwise over 2 hours with stirring. After dropping, the reaction was carried out at 70 ° C., and the reaction was carried out until the infrared absorption spectrum of 2250 cm −1 indicating the isocyanate group disappeared to obtain urethane acrylate 1. DAP varnish 1: diallyl phthalate resin (Daisodap A, manufactured by Daiso Corporation) ) A mixture of 45% by weight and 55% by weight of ethylene oxide (average 3 mole addition) modified trimethylolpropane triacrylate (MIRAMER M3130, manufactured by MIWON) EO3TMPTA: ethylene oxide (average 3 mole addition) modified trimethylolpropane triacrylate, MIRAMER M3130, viscosity 50 to 70 mPa · s, weight average molecular weight 428, manufactured by MIWON, Inc. • BisA EO4DA: ethylene oxide (average 4 mol addition) modified bisphenol A diacrylate, MIRAMER M24 0, viscosity 900-1300 mPa · s, weight average molecular weight 512, manufactured by MIWON • DPHA: dipentaerythritol hexaacrylate, MIRAMER M600, viscosity 4000-7000 mPa · s, weight average molecular weight 578, manufactured by MIWON • DTMPTA: ditrimethylolpropane Tetraacrylate, SR355NS, viscosity 450-750 mPa · s, weight average molecular weight 467, manufactured by Sartomer, TMPTA: trimethylolpropane triacrylate, MIRAMER M300, viscosity 80-120 mPa · s, weight average molecular weight 296, manufactured by MIWON, EO9TMPTA: Ethylene oxide (average 9 mol addition) modified trimethylolpropane triacrylate, viscosity 85-140 mPa · s, weight average molecular weight 692, MIRAM RM3190, manufactured by MIWON, BisAE010DA: ethylene oxide (average 10 mol addition) modified bisphenol A diacrylate, MIRAMER M2100, viscosity 600-700 mPa · s, weight average molecular weight 770, manufactured by MIWON, GPTA: propylene oxide (average 3 mol) Addition) Modified glycerin triacrylate, MIRAMER M320, viscosity 80-120 mPa · s, weight average molecular weight 428, manufactured by MIWON, PO3TMPTA: propylene oxide (average 3 mol addition) modified trimethylolpropane triacrylate, MIRAMER M360, viscosity 70-100 mPa · S, weight average molecular weight 470, manufactured by MIWON · EO4PETA: ethylene oxide (average 4 mol addition) modified pentaerythritol tetra Acrylate, viscosity 120~200mPa · s, a weight average molecular weight 692, MIRAMER M4004, MIWON Co.
（重量平均分子量の測定）
尚、本発明におけるＧＰＣによる重量平均分子量（ポリスチレン換算）の測定は東ソー(株)社製ＨＬＣ８２２０システムを用い以下の条件で行った。
分離カラム：東ソー（株）製ＴＳＫｇｅｌＧＭＨＨＲ−Ｎを４本使用。カラム温度：４０℃。移動層：和光純薬工業（株）製テトラヒドロフラン。流速：１．０ｍｌ／分。試料濃度：１.０重量％。試料注入量：１００マイクロリットル。検出器：示差屈折計。
(Measurement of weight average molecular weight)
In addition, the measurement of the weight average molecular weight (polystyrene conversion) by GPC in this invention was performed on condition of the following using the Tosoh Corp. HLC8220 system.
Separation column: 4 TSKgelGMH HR- N manufactured by Tosoh Corporation are used. Column temperature: 40 ° C. Moving layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0 ml / min. Sample concentration: 1.0% by weight. Sample injection volume: 100 microliters. Detector: differential refractometer.
実施例に述べる活性エネルギー線硬化型オフセットインキ組成物では、紫外線光源により良好な硬化性が得られた。また各原材料を前記の重量％の範囲で配合することにより、本願発明の必要特性であるインキの流動性、適度な乳化率、及びこれらに影響を受ける印刷適性の各評価項目において良好な結果となった。ウレタンアクリレートオリゴマーを用いた実施例１〜３は特に良好な硬化性を発現した。 In the active energy ray-curable offset ink composition described in the Examples, good curability was obtained with an ultraviolet light source. In addition, by blending each raw material in the range of the above-mentioned weight%, good results in each evaluation item of ink fluidity, appropriate emulsification rate, and printability affected by these, which are necessary characteristics of the present invention, became. Examples 1 to 3 using the urethane acrylate oligomer exhibited particularly good curability.
比較例の結果においては、比較例１はエチレンオキサイド変性ビスフェノールＡジアクリレートを含まないため乳化率が低く印刷適性が劣る結果となった。比較例２はエチレンオキサイド変性ビスフェノールＡジアクリレートの使用量が過剰であり乳化率が高く濃度安定性が劣る結果となった。比較例３〜１０は各モノマーの有する粘度、硬化性、親水／疎水バランス、相溶性といった性状の差異により、インキ組成物の流動性、硬化性、印刷適性、いずれか１つ以上のインキ性能が実施例と比較して劣る結果となった。比較例１１、１２は平均付加モル数が２〜６の範囲にあるエチレンオキサイド変性トリメチロールプロパントリアクリレートを含んでおらず、ＴＭＰＴＡ（比較例１１、平均０モル付加）、ＥＯ９ＴＭＰＴＡ（比較例１２、平均９モル付加）を使用したが、実施例に劣る結果となった。 In the result of the comparative example, since Comparative Example 1 did not contain ethylene oxide-modified bisphenol A diacrylate, the emulsification rate was low and the printability was poor. In Comparative Example 2, the amount of ethylene oxide-modified bisphenol A diacrylate used was excessive, resulting in a high emulsification rate and poor concentration stability. In Comparative Examples 3 to 10, due to differences in properties such as viscosity, curability, hydrophilicity / hydrophobicity balance, and compatibility of each monomer, the fluidity, curability, and printability of the ink composition have any one or more ink performances. The results were inferior to those of the examples. Comparative Examples 11 and 12 do not contain ethylene oxide-modified trimethylolpropane triacrylate having an average addition mole number in the range of 2 to 6, and include TMPTA (Comparative Example 11, average 0 mole addition), EO9TMPTA (Comparative Example 12, An average of 9 mole addition) was used, but the results were inferior to the examples.
本発明の活性エネルギー線オフセットインキおよびそれを用いて印刷された印刷物は、食品・飲料・サニタリー・コスメ・おもちゃ・機器・医薬品等の紙器パッケージ用途や、書籍・チラシ・ポスター・カタログ・カード・ダイレクトメール・パンフレット・ＣＤジャケット・シールラベル等の商業印刷用途に幅広く展開され得る。 The active energy ray offset ink of the present invention and printed matter printed using the same are used for paper packaging for food, beverages, sanitary, cosmetics, toys, equipment, pharmaceuticals, etc., books, flyers, posters, catalogs, cards, direct It can be widely deployed in commercial printing applications such as mail, brochures, CD jackets, and seal labels.
１ 内筒用駆動モーター
２ 内筒
３ 外筒
４ 恒温水槽
５ 外筒用駆動モーター
６ 水道水
７ 評価インキ
DESCRIPTION OF SYMBOLS 1 Inner cylinder drive motor 2 Inner cylinder 3 Outer cylinder 4 Constant temperature water tank 5 Outer cylinder drive motor 6 Tap water 7 Evaluation ink
Claims (4)
但し、前記（Ａ）と（Ｂ）との合計は組成物全量の２３〜３０．５重量％である。
[化１]
（但し、ａ、ｂ、ｃは各々独立に０〜６の整数であり、モノマー分子１モルあたりのエチレンオキサイドの平均付加モル数ａ＋ｂ＋ｃが２〜６である。）
[化２]
（但し、ｄ、ｅは各々独立に０〜６の整数であり、モノマー分子１モルあたりのエチレンオキサイドの平均付加モル数はｄ＋ｅが２〜６である。）
An ethylene oxide-modified trimethylolpropane triacrylate (A) having an average addition mole number of ethylene oxide per mole of monomer molecule represented by the general formula (1) in the range of 2 to 6, represented by the general formula (2) Containing ethylene oxide-modified bisphenol A diacrylate (B) having an average addition mole number of ethylene oxide per mole of monomer molecules to be made in the range of 2 to 6, and a pigment, the ethylene oxide-modified trimethylolpropane triacrylate (A ) In the range of 10.5 to 18% by weight of the total amount of the composition, and the ethylene oxide-modified bisphenol A diacrylate (B) in the range of 5 to 20 % by weight of the total amount of the composition. A linear curable offset ink composition.
However, the sum of (A) and (B) is 23 to 30.5% by weight of the total amount of the composition.
[Chemical 1]
(However, a, b, and c are each independently an integer of 0-6, and the average added mole number of ethylene oxide per mole of monomer molecule a + b + c is 2-6.)
[Chemical 2]
(However, d and e are each independently an integer of 0 to 6, and the average added mole number of ethylene oxide per mole of the monomer molecule is d + e of 2 to 6.)
The active energy ray-curable offset ink composition according to claim 1, further comprising a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in a range of 1 to 30% by weight of the total amount.
Furthermore, the active energy ray hardening-type offset ink composition of Claim 1 or 2 which contains urethane (meth) acrylate in the range of 10 to 50 weight% of the whole quantity.
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| JP7173781B2 (en) * | 2018-08-07 | 2022-11-16 | Ｄｉｃグラフィックス株式会社 | Actinic energy ray-curable offset ink and printed matter |
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