WO2014156812A1 - 活性エネルギー線硬化型オフセットインキ組成物 - Google Patents
活性エネルギー線硬化型オフセットインキ組成物 Download PDFInfo
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- WO2014156812A1 WO2014156812A1 PCT/JP2014/057274 JP2014057274W WO2014156812A1 WO 2014156812 A1 WO2014156812 A1 WO 2014156812A1 JP 2014057274 W JP2014057274 W JP 2014057274W WO 2014156812 A1 WO2014156812 A1 WO 2014156812A1
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- ink composition
- active energy
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- the present invention is an active energy ray-curable offset that has good curability, low yellowing, and light stability under active energy ray conditions, and is low in toxicity and low migration for toy and food packaging applications.
- the present invention relates to the invention of ink and its printed matter.
- 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.
- an ink (hereinafter referred to as a colorless and transparent ink) characterized by having a colorless and transparent, milky white and translucent appearance and containing no coloring component is (1) overprinted on the colored ink.
- Overprint varnish (OP varnish) for application of gloss and film strength, (2) Medium ink used for concentration adjustment of colored ink, (3) For the purpose of imparting colored ink to printing substrates with poor ink acceptance It is widely used in the applications shown above, such as anchor / primer agents used as
- UV curable offset inks are widely used in food packaging applications such as confectionery boxes and beverage packs, but in recent years there is a growing trend in which the migration of ink components to encapsulated foods is seen as a problem, mainly in European and American countries. There is also a strong demand for improving the safety of printing ink, which is one of various materials for producing printed matter.
- an ink composition using a polymer material has been proposed as an ink jet ink composition for toys and food packaging (see, for example, Patent Documents 1 and 2).
- this technique has insufficient drying properties in offset printing, which requires much higher productivity than ink jet printing, and cannot exhibit sufficiently low migration performance.
- the object of the present invention is to improve productivity and flow by excellent drying properties in offset printing while combining good drying properties, low yellowing, light stability and low toxicity and low migration properties for toys and food packaging applications. It is to provide an active energy ray-curable offset ink composition having properties.
- the present inventors have found that the above-mentioned problems can be achieved by appropriately combining a photopolymerization initiator and a sensitizer with a higher molecular weight than conventional and a polyfunctional monomer and a polymerizable oligomer having excellent reactivity, The present invention has been reached.
- the present invention is an active energy ray-curable offset ink composition
- an extender pigment comprising an extender pigment, a photopolymerization initiator composition, a tetrafunctional or higher polymerizable acrylate monomer, and a resin oligomer having a polymerization group, wherein the photopolymerization start
- An active energy ray-curable offset ink composition is provided, wherein the agent composition is an ⁇ -hydroxyketone photopolymerization initiator having a number average molecular weight of 320 to 1300.
- the active energy ray-curable offset ink composition of the present invention has a high drying property, but has a high toxicity and a high migration.
- An active energy ray-curable offset ink for toys and food packaging that is excellent, has little yellowing, has low toxicity, and has low migration properties can be obtained.
- the object of the present invention is to contain an appropriate amount of extender pigment, ⁇ -hydroxyketone photopolymerization initiator having a number average molecular weight of 320 or more and 1300 or less, a tetrafunctional or more polymerizable acrylate monomer, and a resin oligomer having a polymerization group.
- extender pigment ⁇ -hydroxyketone photopolymerization initiator having a number average molecular weight of 320 or more and 1300 or less
- a tetrafunctional or more polymerizable acrylate monomer e.g., a resin oligomer having a polymerization group having a polymerization group.
- the photopolymerization initiator composition described here is an ⁇ -hydroxyketone photopolymerization initiator having a number average molecular weight of 320 to 1300.
- the ⁇ -hydroxyketone photopolymerization initiator When the ⁇ -hydroxyketone photopolymerization initiator is less than the number average molecular weight 320, the migration amount tends to increase due to the transfer of the photopolymerization initiator component to the inclusion, and when the number average molecular weight exceeds 1300, the ink This leads to a decrease in fluidity of itself, a decrease in storage stability due to reprecipitation accompanying crystallization of the photopolymerization initiator, and a decrease in film drying property after printing.
- the initiator component can be made soluble even if the number average molecular weight exceeds 1300 by chemically bonding a component having no conjugated double bond such as polyhydric alcohols and fatty acids by a method such as esterification.
- ⁇ -hydroxyketone photopolymerization initiator having a number average molecular weight of 320 or more and 1300 or less, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl]- Phenyl ⁇ -2-methyl-propan-1-one (number average molecular weight: 340.4), oligo (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone) (number average Molecular weight: 424.57), 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methylpropionyl) phenoxy] phenyl ⁇ -2-methylpropanone (number average molecular weight: 342.39), etc.
- any one or more of these may be included, and a plurality of these may be used in combination.
- the same ⁇ -hydroxyketone photopolymerization initiators 1-hydroxy-cyclohexyl-phenyl-ketone (number average molecular weight: 204.3), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (number The average molecular weight: 164.2) is not included in these.
- 2,2-dimethoxy-1,2-diphenylethane-1-one (number average molecular weight 256.3) is used in a wide range of colorless and transparent inks, but its use is not preferred because of its low migration property.
- the content of the ⁇ -hydroxyketone photopolymerization initiator in the ink composition is preferably in the range of 1 to 8% by weight based on the total amount of the ink. If the addition amount is less than 1% by weight, it is difficult to obtain a good drying property. If the addition amount exceeds 8% by weight, the initiator amount becomes excessive, and the ink fluidity and low migration performance are similarly impaired. It is not preferable.
- the phenylketone composition group described in Japanese Patent No. 2514804 in which a polymerizable group is introduced into the initiator molecule also imparts ink drying properties and low migration properties.
- a polymerizable group is introduced into the initiator molecule
- 4- (2-acryloyloxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone in this composition group has been named “Darocur ZLI3331” in the past by Merck (currently BASF). And are available in the present invention.
- composition (number average molecular weight of about 1100) in which ⁇ -hydroxyketone photopolymerization initiator is polymerized and a polymerizable group is introduced is sold by BASF under the name of “Irgacure LEX201”, and has excellent low migration performance. Similarly, it can be suitably used in the present invention.
- photopolymerization initiators that take into consideration the safety and toxicity of the raw materials used in food packaging inks are as follows: 2-methyl-1- [4- (methylthio) phenyl] -2-monoforino IRGACURE907 (manufactured by BASF), which is propan-1-one, has extremely excellent curability (ink drying property) and is widely used especially for UV-curable offset inks. Because there is (GHS classification: reproductive toxicity classification 1B (reproductive ability) and 1B (fetus)), it is not dependent on this, and it has low migration, low odor, excellent drying and fluidity, etc. It is the present invention that has enabled the higher printability required.
- DAROCURE TPO manufactured by BASF
- BASF 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
- BASF 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
- the Daisodap series (DaisoDup A, Daisodap S, Daisodap K, all manufactured by Daiso Corp.), which is diallyl phthalate resin (DAP resin), has excellent film strength, so existing UV offset Unreacted diallyl phthalate monomer (diallyl phthalate, CAS No. 131-17-9) that remains in the resin is very widely used in inks, but is a former type 2 monitoring chemical and mutagenic (GHS Category 1B (germ cell mutagenicity)), it has become possible to provide food packaging inks with excellent drying characteristics and safety, without depending on this. Is the present invention.
- DAP resin diallyl phthalate resin
- a tetrafunctional or higher functional acrylate monomer may be mentioned.
- Specific examples of the tetrafunctional polymerizable acrylate monomer include ditrimethylolpropane tetraacrylate (DTMPTA), ethylene oxide modified pentaerythritol tetraacrylate (EO-PETA), propylene oxide modified pentaerythritol tetraacrylate (PO-PETA), Etc.
- pentafunctional polymerizable acrylate monomer examples include dipentaerythritol pentaacrylate, and specific examples of the hexafunctional polymerizable acrylate monomer include dipentaerythritol hexaacrylate. These may be used alone or in combination.
- the content of the above-mentioned tetrafunctional or higher polymerizable acrylate monomer in the ink composition is preferably in the range of 15% by weight to 60% by weight, and less than 15% by weight, that is, inking. In this case, it leads to the use of a polymerizable acrylate monomer having a functionality of 3 or less, the curability is lowered, the drying property and the low migration property are deteriorated, and when the addition amount exceeds 60% by weight, a viscosity suitable as an offset ink is obtained. It becomes difficult.
- the pentafunctional acrylate monomer dipentaerythritol pentaacrylate and the hexafunctional polymerizable acrylate monomer dipentaerythritol hexaacrylate may be used in an amount of 10% by weight or more based on the total amount of the ink. preferable.
- 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
- a resin oligomer having a polymerization group can be mentioned. Compared with non-reactive resins (inert resins) that do not have a polymerizable group in the molecule, the reactivity is high, and it is possible to impart more excellent low migration properties.
- the resin oligomer having a polymerization group include epoxy acrylate, aliphatic acrylate, polyester acrylate, urethane acrylate and the like. Among them, epoxy acrylate and derivatives thereof are more preferable, and examples thereof include bisphenol A diglycidyl ether diacrylate and derivatives thereof, and bisphenol A diglycidyl ether diacrylate is particularly preferable.
- the content of the resin oligomer having a polymer group in the ink composition is preferably in the range of 20 to 65% by weight with respect to the total amount of the ink.
- these polymerizable oligomers generally have high viscosity, so that they are described in the examples of the present invention. It becomes difficult to obtain a viscosity suitable as an offset ink in the composition.
- the polymerizable oligomer is added in a proportion exceeding 65% by weight in combination with a large amount of low molecular weight monomers (generally monofunctional and bifunctional acrylate monomers) for viscosity adjustment, a suitable viscosity is obtained. Even if it can be obtained, the low migration property is impaired.
- low molecular weight monomers generally monofunctional and bifunctional acrylate monomers
- an alkylaminobenzoate compound which is an aromatic tertiary amine having a number average molecular weight of 400 or more and 1500 or less and having a maximum absorption at a wavelength of 250 to 450 nm in the range of 280 to 340 nm may be added as a sensitizer.
- poly (ethylene glycol) bisdimethylaminobenzoate (number average molecular weight 488 to 532) as a bifunctional amine derivative
- poly (ethylene glycol) bisdimethylaminobenzoate (number average molecular weight 860) as a tetrafunctional amine derivative has a relatively high molecular weight. This is preferable in that migration is difficult.
- Aromatic tertiary amines other than alkylaminobenzoates include alkylaminobenzophenone compounds. Among them, 4,4'-bis (diethylamino) benzophenone (number average molecular weight 324.47) has excellent drying properties and low migration properties, but has a wavelength. Since the maximum absorption wavelength at 250 to 450 nm is as high as 365 nm and the discoloration (yellowing) of the cured film due to the curing reaction is severe, use in a colorless and transparent system is not preferred.
- the content of the alkylaminobenzoate compound in the ink composition is preferably in the range of 1 to 8% by weight based on the total amount of the ink.
- An addition amount of less than 1% by weight is undesirable in that a further improvement in the drying rate cannot be obtained, and even if it is added in excess of 8% by weight, the effect of just using it is not recognized.
- benzophenone (number average molecular weight 182.22), 4-methylbenzophenone (number average molecular weight 196.24), O-methylbenzoylbenzoate (number average molecular weight 240) which are hydrogen abstraction type photopolymerization initiators. .25) is widely used, but is not preferred because of poor migration.
- extender pigments are widely used for the purpose of improving physical properties and imparting functionality such as ink fluidity adjustment, prevention of misting during printing, and prevention of penetration into paper substrates.
- extender pigments include publicly known organic pigments for coloring, such as extender pigments for printing inks published in “Handbook of Pigments (edited by the Japan Pigment Technical Association)”, calcium carbonate, magnesium carbonate Kaolin clay, talc, bentonite, mica, barium sulfate, silica, aluminum hydroxide and the like can be used.
- the printing substrate used in the printed matter of the present invention is not particularly limited.
- paper such as fine paper, coated paper, art paper, imitation paper, thin paper, cardboard, various synthetic papers, polyester resin, acrylic resin, chloride Films or sheets of vinyl resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, nylon, polylactic acid, polycarbonate,
- Examples include cellophane, aluminum foil, and other various base materials conventionally used as printing base materials.
- offset printing ink described in the present invention is the same as the conventional ultraviolet curable ink, the extender pigment, polymerizable acrylate monomer, resin oligomer having a polymerization group, photopolymerization initiator, sensitizer, other additives, etc. Is mixed with stirring with a mixer or the like, and kneaded using a dispersing machine such as a three-roll mill or a bead mill.
- talc 3% by weight of talc, 2% by weight of hydrophobic silica and 5% by weight of magnesium carbonate (total 10% by weight) as extender pigments, 1.5% by weight of wax as auxiliary agent and 10% by weight of stabilizer solution (p-methoxyphenol) %
- stabilizer solution p-methoxyphenol
- a mixture of 90% by weight of ethylene oxide-modified pentaerythritol tetraacrylate) and 1% by weight (a total of 2.5% by weight of auxiliaries) were added in common to all examples.
- the ultraviolet curable ink composition thus obtained was uniformly stretched on a rubber roll and a 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. carton paper (polyethylene-laminated paper, tetra Rex, tetra Pak Inc.) and color exhibition as uniformly applied to an area ranging from about 220 cm 2 on the surface of the to produce a printed material.
- 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.
- [Evaluation method 2 of ink composition: light stability] Prepare 20g of the prepared ink, leave it in a place 5cm away from a fluorescent lamp (Panasonic, 3-wavelength daylight white, Hf fluorescent lamp, FHF32EX-NH), and visually check whether the ink is dry after 60 minutes. The evaluation was made in the following three stages. In the composition in which drying can be confirmed in this evaluation item, the ink is stretched on the printing press and the viscosity of the ink is increased. ⁇ : Not dried at all ⁇ : Some drying can be confirmed ⁇ : Drying can be confirmed
- the cured ink layer on the upper surface of the printed material is superposed so that the back surface of the milk carton blank paper (hereinafter, the non-printed milk carton paper on which the ink is not developed is referred to as the milk carton blank paper) is contacted with a hydraulic press.
- Unreacted components in the cured ink layer were migrated to the back side of the milk carton white paper by pressing for 48 hours under a press pressure of 40 kg / cm 2 and an atmosphere of room temperature of 25 ° C. (see FIGS. 1 and 2).
- the milk carton blank paper was removed and molded to prepare a 1000 ml liquid container. In this liquid container, the back surface to which the ink component has transferred faces inward.
- aqueous ethanol solution (mixed solution of 95% by weight of ethanol and 5% by weight of pure water) prepared as a simulated liquid food was poured into a liquid container and sealed.
- the total area of the inner surface of the liquid container in contact with 1000 ml of the ethanol aqueous solution was about 600 cm 2 .
- the sealed liquid container was allowed to stand at room temperature and 25 ° C. for 24 hours, and the ink components transferred to the back of the milk carton white paper were extracted into an aqueous ethanol solution.
- Tables 1 to 4 are% by weight.
- the raw materials and abbreviations shown in Tables 1 to 4 are shown below.
- -Talc hydrous magnesium silicate, high filler # 5000PJ, manufactured by Matsumura Sangyo Co., Ltd.-Hydrophobic silica: silicon dioxide, AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.-Magnesium carbonate: basic magnesium carbonate, magnesium carbonate TT, Naikai salt industry -Wax: polyolefin wax, S-381-N1, manufactured by Shamrock, Inc.-Stabilizer: p-methoxyphenol, methoquinone, Seiko Chemical Co., Ltd., ethylene oxide-modified pentaerythritol tetraacrylate (SR494NS), manufactured by Sartomer, Inc.
- SR494NS ethylene oxide-modified pentaerythritol tetraacrylate
- Irgacure 369 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, number average molecular weight 366.5, manufactured by BASF, Ltd.
- Esacure One oligo (2-hydroxy-2-methyl- -[4- (1-methylvinyl) phenyl] propanone), number average molecular weight 424.57, manufactured by Lamberti,
- Irgacure 819 bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, number average molecular weight 418. 5.
- ISFacure TPO manufactured by BASF 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, number average molecular weight 348.0, manufactured by BASF KIP160: 2-hydroxy-1- ⁇ 4- [4- (2- Hydroxy-2-methylpropionyl) phenoxy] phenyl ⁇ -2-methylpropanone, number average molecular weight 342.39, Irgacure 184: 1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by Lamberti Number average molecular weight 204.3, manufactured by BASF, Irgacure 651: 2,2-dimethoxy-1,2-diphenylethane-1-one, number average molecular weight 256.3, manufactured by BASF, Aronix M-400: dipentaerythritol penta Mixture of acrylate and dipentaerythritol hexaacrylate (ratio of pentaacrylate in the product: 40 to 50% by weight), manufactured by Toagosei Co
- SR355NS ditrimethylolpropane tetraacrylate, manufactured by Sartomer, Inc.
- SR494NS ethylene oxide modified pentaerythritol tetra Acrylate, manufactured by Sartomer
- MIRAMER M-3130 Ethylene oxide modified trimethylolpropane triacrylate, manufactured by MIWON, PHOTOMER 4127: Polyethylene oxide Modified neopentyl glycol diacrylate, manufactured by Cognis Japan, Inc.
- DICLITE UE-8200T Bisphenol A diglycidyl ether diacrylate
- UNIDIC V3212 Non-reactive polyester resin 40% by weight, DPHA (dipentaerythritol pentaacrylate and dipentaerythritol hexa) Mixture of acrylate) 30% by weight and 30% by weight of ditrimethylolpropane tetraacrylate, manufactured by DIC, EAB-SS: 4,4'-bis (diethylamino) benzophenone, number average molecular weight 324.47, Daido Kasei Kogyo Co., Ltd.
- -GENOPOL AB1 Poly (ethylene glycol) bisdimethylaminobenzoate, number average molecular weight 860, manufactured by RAHN AG-Omnipol ASA: Poly (ethylene group) Cole) Bisdimethylaminobenzoate, number average molecular weight 488-532, manufactured by IGM, LUNACUR EDB: ethyl-4- (dimethylamino) benzoate, number average molecular weight 193.24, manufactured by EUTEC CHEMICAL, DAROCUR EHA: 2-ethylhexyl- 4- (Dimethylamino) benzoate, number average molecular weight 277.4, manufactured by BASF
- the active energy ray-curable offset ink composition of the present invention and printed materials using the same are widely used for sanitary, cosmetics and pharmaceutical packaging and filling applications, in addition to toys and food packaging materials that emphasize safety and hygiene. Can be done.
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Abstract
Description
またα-ヒドロキシケトン系光重合開始剤を高分子量化し重合性基を導入した組成物(数平均分子量約1100)が「イルガキュアLEX201」の名称でBASF社より販売されており、低マイグレーション性能に優れており同様に本発明において好適に利用することができる。
アルキルアミノベンゾエート以外の芳香族3級アミンとしてはアルキルアミノベンゾフェノン化合物があり、中でも4,4′-ビス(ジエチルアミノ)ベンゾフェノン(数平均分子量324.47)は乾燥性に優れ低マイグレーション性を示すが波長250~450nmにおける極大吸収波長が365nmと高く硬化反応による硬化皮膜の変色(黄変)が激しいため無色透明系での使用は好ましくない。
表1~表4の組成に従って、実施例1~9および比較例1~12のインキを三本ロールミルにて練肉せしめることによって、各種の紫外線硬化型インキ組成物を得た。
尚、体質顔料としてタルク3重量%及び疎水性シリカ2重量%及び炭酸マグネシウム5重量%(合計10重量%)、その他助剤としてワックス1.5重量%及び安定剤溶液(p-メトキシフェノール10重量%とエチレンオキサイド変性ペンタエリスリトールテトラアクリレート90重量%の混合物)1重量%(助剤合計2.5重量%)を、全ての実施例に共通に添加した。
かくして得た紫外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、ミルクカートン紙(ポリエチレンラミネート紙、テトラ・レックス、テトラパック社製)の表面に約220cm2の面積範囲に均一に塗布されるように展色し、印刷物を作製した。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。
インキ塗布後の印刷物にUV照射を行い、インキ皮膜を硬化乾燥させた。水冷メタルハライドランプ(出力80W/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、印刷物をコンベア上に載せ、ランプ直下(照射距離11cm)を以下に述べる所定条件で通過させた。各条件における紫外線照射量は紫外線積算光量系(ウシオ電機社製UNIMETER UIT-150-A/受光機UVD-C365)を用いて測定した。
硬化性は、照射直後に爪スクラッチ法にて印刷物表面の傷付きの有無を確認した。前記UV照射装置のコンベア速度(m/分)を変化させながら印刷物に紫外線を照射し、傷付きが無い最速のコンベア速度を記載した。従ってコンベア速度が速いほどインキの乾燥性が良好である。
作成したインキを20g準備し、蛍光灯(パナソニック製、3波長型昼白色、Hf蛍光灯、FHF32EX-N-H)から5cmの場所に静置し60分後にインキが乾いているかどうか目視で確認し、次の3段階で評価した。本評価項目において乾燥が確認できる組成では印刷機上でのインキの皮張り、インキの粘度上昇が発生し印刷適性面での不良が発現し易くなる。
○:全く乾燥しない
△:若干の乾燥が確認できる
×:乾燥が確認できる
作成したインキを冷蔵庫内(4℃)にて1週間保管し、その後インキ約1グラムを金属グラインドゲージ(溝深さ0~25ミクロン)上に載せ、金属スクレーパーでゲージ上のインキをかき取り、インキ中の光重合開始剤の溶解性低下に伴う析出の状態を目視で確認し、次の3段階で評価した。光重合開始剤が析出し結晶化した場合、グラインドゲージ上に開始剤結晶由来のスジが新たに発生する。本評価項目において析出の発生する組成では、冬場等、低温環境下においては十分な製品性能を発揮することが出来ない。
○:析出は見られない。
△:ごく僅かに析出が確認できる。
×:析出が確認できる。
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3段階で評価した。本評価項目においてDMが34mm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。
○:DM37mm以上
△:DM34以上~37nm未満
×:DM34mm未満
紫外線照射後における硬化皮膜の変色(黄変)に起因する色変化を確認し次の3段階で評価した。
○:色変化が全く無い、もしくは殆ど無い
△:若干の黄変が確認できる
×:明確に黄変による色変化が確認できる
低マイグレーション性の評価に関しては、基本的な評価手順は欧州印刷インキ評議会であるEuPIA(European Printing Ink Association)のガイドライン(EuPIA Guideline on Printing Inks、applied to the non-food contact surface of food packaging materials and articles、November 2011(Replaces the September 2009 version))に準拠した。
先ず上述の印刷物はコンベア速度40m/min.で2回UV照射することによりインキ層を乾燥させた。本条件における紫外線積算光量は約100mJ/cm2であった。続いて印刷物上面の硬化インキ層にミルクカートン白紙(以後、インキが展色されていない非印刷状態のミルクカートン紙をミルクカートン白紙と呼ぶ)の裏面が接するよう重ね合わせ、油圧プレス機を用いてプレス圧力40kg/cm2、室温25℃雰囲気下で48時間加圧することで、硬化インキ層中の未反応成分をミルクカートン白紙の裏面に移行(マイグレーション)させた(図1及び2参照)。プレス後にミルクカートン白紙を取り外して成形し、1000ml容積の液体容器を作製した。この液体容器においてインキ成分の移行した裏面は内側に面している。次に擬似液体食品として用意したエタノール水溶液(エタノール95重量%と純水5重量%の混合溶液)1000mlを液体容器に注ぎ密閉した。なお、本条件においてエタノール水溶液1000mlと接触する液体容器内面の総面積はおよそ600cm2であった。密閉した液体容器を室温25℃雰囲気下で24時間静置し、ミルクカートン白紙裏面に移行したインキ成分をエタノール水溶液中に抽出した。この後液体容器からエタノール水溶液を取り出し、液体クロマトグラフ質量分析にて使用した開始剤の同定及び各々の溶出濃度(マイグレーション濃度)を定量し、各開始剤成分のマイグレーション濃度の合計値から、3段階でマイグレーション性能を評価した。例として、開始剤A、B、C3種を使用した紫外線硬化型インキを用いた印刷物においては、開始剤Aのマイグレーション濃度が10ppb、開始剤Bのマイグレーション濃度が5ppb、開始剤Cのマイグレーション濃度が15ppbであった場合、開始剤成分のマイグレーション濃度の合計値は、A+B+C=10+5+15=30ppbと評価される。なお液体クロマトグラフ質量分析の定量に際しては、使用する全開始剤について各々上記エタノール水溶液を用いた検量線を予め作成し、これを用いることで算出した。
○:30ppb未満
△:30ppb以上~60ppb未満
×:60ppb以上
表1~4に示す諸原料及び略を以下に示す。
・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
・疎水性シリカ:二酸化ケイ素、AEROSIL R972、日本アエロジル株式会社製
・炭酸マグネシウム:塩基性炭酸マグネシウム、炭酸マグネシウムTT、ナイカイ塩業社製
・ワックス:ポリオレフィンワックス、S-381-N1、シャムロック社製
・安定剤:p-メトキシフェノール、メトキノン、精工化学社製
エチレンオキサイド変性ペンタエリスリトールテトラアクリレート(SR494NS)、サートマー社製
・Irgacure369:2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1、数平均分子量366.5、 BASF社製
・Esacure One:オリゴ(2-ヒドロキシ-2-メチル-1-[4-(1-メチルビニル)フェニル]プロパノン)、数平均分子量424.57、 Lamberti社製
・Irgacure819: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、数平均分子量418.5、BASF社製
・IrgacureTPO: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、数平均分子量348.0、BASF社製
・KIP160:2-ヒドロキシ-1-{4-〔4-(2-ヒドロキシ-2-メチルプロピオニル)フェノキシ〕フェニル}-2-メチルプロパノン、数平均分子量342.39、 Lamberti社製
・Irgacure184:1-ヒドロキシ-シクロヘキシル-フェニル-ケトン、
数平均分子量204.3、 BASF社製
・Irgacure651:2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、数平均分子量256.3、 BASF社製
・アロニックスM-400: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(製品中のペンタアクリレートの割合:40~50重量%)、東亞合成社製
・SR355NS:ジトリメチロールプロパンテトラアクリレート、サートマー社製
・SR494NS:エチレンオキサイド変性ペンタエリスリトールテトラアクリレート、サートマー社製
・MIRAMER M-3130: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、MIWON社製
・PHOTOMER 4127:ポリエチレンオキサイド変性ネオペンチルグリコールジアクリレート、コグニスジャパン社製
・DICLITE UE-8200T:ビスフェノールAジグリシジルエーテルジアクリレート
・UNIDIC V3212:非反応性ポリエステル樹脂40重量%と、DPHA(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)30重量%と、ジトリメチロールプロパンテトラアクリレート30重量%の混合物、DIC社製
・EAB―SS:4,4′-ビス(ジエチルアミノ)ベンゾフェノン、数平均分子量324.47、大同化成工業社製
・GENOPOL AB1:ポリ(エチレングリコール)ビスジメチルアミノベンゾエート、数平均分子量860、RAHN AG社製
・Omnipol ASA:ポリ(エチレングリコール)ビスジメチルアミノベンゾエート、数平均分子量488~532、IGM社製
・LUNACUR EDB:エチル-4-(ジメチルアミノ)ベンゾエート、数平均分子量193.24、EUTEC CHEMICAL社製
・DAROCUR EHA:2-エチルヘキシル-4-(ジメチルアミノ)ベンゾエート、数平均分子量277.4、BASF社製
尚、本発明におけるGPCによる数平均分子量(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。
2 ミルクカートン紙
3 ミルクカートン白紙
Claims (7)
- 体質顔料、光重合開始剤組成物、4官能以上の重合性アクリレートモノマー、及び重合基を有する樹脂オリゴマーを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であって、前記光重合開始剤組成物が、数平均分子量320以上1300以下であるα―ヒドロキシケトン系光重合開始剤であ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。
- 前記光重合開始剤組成物が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、オリゴ(2-ヒドロキシ-2-メチル-1-[4-(1-メチルビニル)フェニル]プロパノン)、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)フェノキシ〕フェニル}-2-メチルプロパノンからなる群から選ばれる1つ以上である請求項1に記載の活性エネルギー線硬化型オフセットインキ組成物。
- 前記光重合開始剤組成物が全量の1~8重量%、4官能以上の重合性アクリレートモノマーが全量の15重量%以上、重合基を有する樹脂オリゴマーが全量の20~65重量%を含有する請求項1又は2に記載の活性エネルギー線硬化型オフセットインキ組成物。
- 前記4官能以上の重合性アクリレートモノマーが、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であって、全量の10重量%以上含有する請求項1~3の何れか1つに記載の活性エネルギー線硬化型オフセットインキ組成物。
- 前記重合基を有する樹脂オリゴマーが、エポキシアクリレートおよびその誘導体である請求項1~4の何れか1つに記載の活性エネルギー線硬化型オフセットインキ組成物。
- 更に、数平均分子量400以上1500以下であり、波長250~450nmにおける極大吸収を280~340nmの範囲に有する芳香族3級アミン化合物を、全量の1~8重量%含有することを特徴とする請求項1~5に記載の活性エネルギー線硬化型オフセットインキ組成物。
- 請求項1~6の何れか1つに記載の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。
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Cited By (9)
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JP2014065787A (ja) * | 2012-09-25 | 2014-04-17 | Dic Corp | 活性エネルギー線硬化性組成物及び硬化物 |
JP2015011209A (ja) * | 2013-06-28 | 2015-01-19 | 太陽インキ製造株式会社 | 光硬化性組成物およびその硬化物 |
CN104650646A (zh) * | 2015-03-12 | 2015-05-27 | 山东德创喷墨科技有限公司 | 一种低迁移uv柔版油墨及其制备方法 |
WO2017090663A1 (ja) * | 2015-11-25 | 2017-06-01 | 東レ株式会社 | 平版印刷用インキ |
JP2018089931A (ja) * | 2016-12-07 | 2018-06-14 | Dicグラフィックス株式会社 | 印刷物 |
JP2018090309A (ja) * | 2016-12-07 | 2018-06-14 | Dicグラフィックス株式会社 | 印刷物 |
JP7005834B1 (ja) * | 2020-06-03 | 2022-01-24 | 東洋インキScホールディングス株式会社 | 活性エネルギー線硬化型平版印刷インキ及び印刷物 |
JP2022524226A (ja) * | 2019-04-18 | 2022-04-28 | サン ケミカル コーポレイション | 低移行性電子ビーム硬化型プライマー |
JP7381357B2 (ja) | 2020-02-03 | 2023-11-15 | Dicグラフィックス株式会社 | 平版オフセット印刷用活性エネルギー線硬化型インキ、及び印刷物 |
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TW201720881A (zh) * | 2015-09-17 | 2017-06-16 | Toray Industries | 平版印刷用印墨、平版印墨用清漆及使用其之印刷物的製造方法 |
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JP2014065787A (ja) * | 2012-09-25 | 2014-04-17 | Dic Corp | 活性エネルギー線硬化性組成物及び硬化物 |
JP2015011209A (ja) * | 2013-06-28 | 2015-01-19 | 太陽インキ製造株式会社 | 光硬化性組成物およびその硬化物 |
CN104650646A (zh) * | 2015-03-12 | 2015-05-27 | 山东德创喷墨科技有限公司 | 一种低迁移uv柔版油墨及其制备方法 |
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JPWO2017090663A1 (ja) * | 2015-11-25 | 2018-02-15 | 東レ株式会社 | 平版印刷用インキ |
CN108350296A (zh) * | 2015-11-25 | 2018-07-31 | 东丽株式会社 | 平版印刷用墨水 |
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TWI694116B (zh) * | 2015-11-25 | 2020-05-21 | 日商東麗股份有限公司 | 平版印刷用印墨、及印刷物之製造方法 |
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JP2022524226A (ja) * | 2019-04-18 | 2022-04-28 | サン ケミカル コーポレイション | 低移行性電子ビーム硬化型プライマー |
JP7237199B2 (ja) | 2019-04-18 | 2023-03-10 | サン ケミカル コーポレイション | 低移行性電子ビーム硬化型プライマー |
JP7381357B2 (ja) | 2020-02-03 | 2023-11-15 | Dicグラフィックス株式会社 | 平版オフセット印刷用活性エネルギー線硬化型インキ、及び印刷物 |
JP7005834B1 (ja) * | 2020-06-03 | 2022-01-24 | 東洋インキScホールディングス株式会社 | 活性エネルギー線硬化型平版印刷インキ及び印刷物 |
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CN104854200B (zh) | 2016-10-12 |
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