WO2014129461A1 - 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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- WO2014129461A1 WO2014129461A1 PCT/JP2014/053779 JP2014053779W WO2014129461A1 WO 2014129461 A1 WO2014129461 A1 WO 2014129461A1 JP 2014053779 W JP2014053779 W JP 2014053779W WO 2014129461 A1 WO2014129461 A1 WO 2014129461A1
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- ink composition
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- energy ray
- offset ink
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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
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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
Definitions
- the present invention relates to a toy that cures well under active energy ray conditions and an invention of active energy ray-curable offset ink considering safety such as low toxicity and low migration for food packaging applications, and printed matter thereof.
- 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.
- 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.
- IRGACURE907 manufactured by BASF which is 2-methyl-1- [4- (methylthio) phenyl] -2-monoforinopropan-1-one is extremely excellent. It is curable (ink-drying property) and is widely used especially for UV-curable offset inks, but it is a highly reproductive toxic substance (GHS classification: reproductive toxicity category 1B (reproductive ability) and 1B (Fetus)), and it is possible to achieve higher printability required for offset ink, such as low migration, low odor, excellent drying and fluidity, without depending on this. It is.
- 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
- An object of the present invention is to provide an active energy ray curable type which has good drying property and low toxicity for toy and food packaging use, low migration property, and has improved productivity and fluidity by excellent drying property in offset printing.
- the object is to provide an offset ink composition.
- 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 relates to an active energy ray curing comprising a color pigment, a photopolymerization initiator composition (A), a photopolymerization initiator composition (B), a tetrafunctional or higher polymerizable acrylate monomer, and a resin oligomer having a polymerization group.
- Type offset ink composition wherein (A) is an ⁇ -aminoalkylphenone photopolymerization initiator having a number average molecular weight of 350 or more and 1000 or less, and (B) is a number average molecular weight of 320 or more and 1000 or less.
- An active energy ray-curable offset ink composition is provided, which is an ⁇ -hydroxyketone photopolymerization initiator.
- the active energy ray-curable offset ink composition of the present invention With the active energy ray-curable offset ink composition of the present invention, the conventional dryness is high, but the toxicity is high and migration is high. An active energy ray-curable offset ink for toys and food packaging having low migration properties can be obtained.
- the present invention relates to a color pigment, an ⁇ -aminoalkylphenone photopolymerization initiator having a number average molecular weight of 350 or more and 1000 or less, an ⁇ -hydroxyketone photopolymerization initiator having a number average molecular weight of 320 or more and 1000 or less.
- the photopolymerization initiator composition (A) described here is an ⁇ -aminoalkylphenone photopolymerization initiator having a number average molecular weight of 350 or more and 1000 or less, and the photopolymerization initiator composition (B) is a number average molecular weight. It is an ⁇ -hydroxyketone photopolymerization initiator that is 320 or more and 1000 or less.
- the migration amount tends to increase due to the migration of the photopolymerization initiator component to the inclusion, and when the number average molecular weight exceeds 1000, This leads to a decrease in fluidity of the ink itself, a decrease in storage stability due to reprecipitation accompanying crystallization of the photopolymerization initiator, and a decrease in the drying property of the film after printing.
- the ⁇ -hydroxyketone-based photopolymerization initiator tends to increase the migration amount when the number average molecular weight is less than 320, and when the number average molecular weight exceeds 1000, the fluidity of the ink itself decreases, the photopolymerization initiator. This leads to a decrease in storage stability due to reprecipitation accompanying crystallization of the film and a decrease in film drying after printing.
- the initiator component can be made soluble even if the number average molecular weight exceeds 1000 by chemically bonding components having no conjugated double bonds such as polyhydric alcohols and fatty acids by a technique such as esterification. Although it is technically possible to provide an excellent compound, these derivatives having a number average molecular weight of 1000 lower the effective component concentration of the initiator in the compound (ratio of the conjugated double bond having ultraviolet absorbing ability). Therefore, it is difficult to obtain sufficient drying properties.
- ⁇ -aminoalkylphenone photopolymerization initiator having a number average molecular weight of 350 or more and 1000 or less, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (number average molecular weight: 366.5), 2- (dimethylamino) -2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (number average molecular weight: 380.5) ), Etc., and any one or more of these may be included, and a plurality of these may be used in combination.
- the same ⁇ -aminoalkylphenone photopolymerization initiator 2-methyl-1- [4- (methylthio) phenyl] -2-monoforinopropan-1-one has a number average molecular weight (279.4). Not included in this.
- Examples of the ⁇ -hydroxyketone photopolymerization initiator having a number average molecular weight of 320 or more and 1000 or less include 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.
- the content of the ⁇ -aminoalkylphenone photopolymerization initiator in the ink composition is preferably in the range of 1 to 3% by weight with respect to 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 3% by weight, the initiator amount becomes excessive and not only the degree of improvement in drying property is reduced but also the start. This is not preferable because the solubility of the agent in the liquid component in the ink is lowered, the ink fluidity is lowered, the amount of unreacted initiator is increased, and the low migration performance is impaired.
- 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.
- oxime ester photopolymerization initiators can also be used for the purpose of imparting ink drying properties and low migration properties.
- oxime ester photopolymerization initiators examples include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (product name IRGACURE OXE01, manufactured by BASF), ethanone, Examples include 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (product name IRGACURE OXE02, manufactured by BASF).
- These oxime ester initiators have a high molecular weight and are excellent in low migration properties, and may be used as long as they do not impair the effects of the present invention.
- 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-described tetrafunctional or higher polymerizable acrylate monomer in the ink composition is preferably 20% by weight or more based on the total amount of the ink, and less than 20% by weight. This leads to the use of a polymerizable acrylate monomer, resulting in a decrease in curability and poor drying and low migration properties.
- 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
- a bisacylphosphine oxide photopolymerization initiator may be added.
- bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is added in an amount of 0.1 to It is preferable to use in the range of 2.5% by weight.
- the addition amount is less than 0.1% by weight, there is almost no effect on improving the drying property. If the addition amount exceeds 2.5% by weight, the initiator amount becomes excessive, and further improvement in drying property cannot be expected, and offset. It is not preferable because it is difficult to dissolve in ink and causes deterioration in storage stability due to a decrease in ink fluidity and precipitation.
- an alkylaminobenzophenone compound that is an aromatic tertiary amine may be added as a sensitizer.
- 4,4'-bis (diethylamino) benzophenone (number average molecular weight 324.47) is preferable in terms of excellent drying properties and relatively high molecular weight and difficulty in migration.
- Aromatic tertiary amines other than alkylamine benzophenone include alkylaminobenzoates such as ethyl-4- (dimethylamino) benzoate (number average molecular weight 193.2), 2- (dimethylamino) ethyl benzoate (number average molecular weight 193).
- the content of the alkylaminobenzophenone compound in the ink composition is preferably in the range of 0.5 to 4% by weight based on the total amount of the ink.
- An addition amount of less than 0.5% by weight is undesirable in that a further improvement in the drying rate cannot be obtained, and addition exceeding 4% by weight is not preferred because the effect of use is not observed.
- coloring pigment examples include publicly known organic pigments for coloring, such as organic pigments for printing inks published in "Organic Pigment Handbook (Author: Isao Hashimoto, Publisher: Color Office, 2006 First Edition)" Soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinones A pigment, a quinophthalone pigment, a metal complex pigment, a diketopyrrolopyrrole pigment, a carbon black pigment, and other polycyclic pigments can be used.
- organic pigments for coloring published in "Organic Pigment Handbook (Author: Isao Hashimoto, Publisher: Color Office, 2006 First Edition)” Soluble azo pigments, insoluble azo
- the loss of ultraviolet energy that activates the photopolymerization initiator particularly in the case of black ink using carbon black having an extremely high ultraviolet absorbing ability in the range of 10 to 25% by weight.
- it is difficult to obtain a sufficient drying property and low migration performance because the photopolymerization reaction is difficult to proceed especially at the bottom of the ink film as compared with other color pigments.
- the offset ink composition described in the present invention is difficult to obtain. Can impart a suitable drying property to black ink using 10 to 25% by weight of carbon black.
- an ultraviolet curable ink in which the amount of carbon black added exceeds 25% by weight is not preferable because loss of ultraviolet energy due to carbon black becomes enormous and suitable drying properties cannot be obtained.
- the average primary particle size of the carbon black is preferably in the range of 15 to 70 nm, and particularly preferably in the range of 20 to 40 nm. When the average primary particle size is less than 15 nm, the loss of ultraviolet energy due to carbon black becomes enormous, and it is not preferable because suitable drying properties cannot be obtained. When it exceeds 70 nm, the blackness of black ink is impaired. Is not preferable.
- Examples of the carbon black include those produced by a known method such as a furnace method, a thermal method, and a contact method.
- Raven 1180, Raven 1255 above, Colombian Chemical
- Regal 400R, Regal 330R, Regal 660R, Mogul L aboveve, Cabot
- MA7, MA8, MA11 above, Mitsubishi Chemical
- 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.
- the production of the offset printing ink described in the present invention is the same as the conventional ultraviolet curable ink, the color pigment, the polymerizable acrylate monomer, the resin oligomer having a polymerization group, the photopolymerization initiator, the sensitizer, and other additives. 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.
- the colorant is 16% by weight of carbon black (as carbon black, Raven 1060 Ultra was used in Examples 1 to 12 and Raven 1180 was used in Example 13), and 3% by weight of phthalocyanine blue as a complementary color component and 2% by weight of dioxazine violet (total 21% by weight of coloring materials), 2% by weight of talc and 2% by weight of magnesium carbonate (total 4% by weight) as viscosity and fluidity regulators, 2% by weight of wax and stabilizer as auxiliary agents 1% by weight of a solution (a mixture of 10% by weight of p-methoxyphenol and 90% by weight of ethylene oxide-modified pentaerythritol tetraacrylate) (a total of 3% by weight of auxiliaries) was added in common to all examples.
- a solution a mixture of 10% by weight of p-methoxyphenol and 90% by weight of ethylene oxide-modified pentaerythritol tetraacrylate
- phthalocyanine blue and dioxazine violet which are complementary color components, are blended in a small amount for the purpose of counteracting the yellowness of carbon black itself and further enhancing the jetness of the ink.
- Such hue adjustment of the ink is called “complementary color”, and is a widely known technique.
- 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.
- RI tester manufactured by Toyoe Seiko Co., Ltd.
- the color was developed 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.
- 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.
- Magnesium carbonate basic magnesium carbonate, magnesium carbonate TT, manufactured by Naikai Shigyo Co., Ltd.
- Wax polyolefin wax, S-381-N1, Shamro ⁇ Stabilizer solution: 10% by weight of p-methoxyphenol (methoquinone, manufactured by Seiko Chemical Co., Ltd.) and 90% by weight of ethylene oxide-modified pentaerythritol tetraacrylate (SR494NS, manufactured by Sartomer) ⁇
- Irgacure 369 2-benzyl -2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1, number average molecular weight 366.5, manufactured by BASF
- Irgacure 379 2- (dimethylamino) -2- (4-methyl-benzyl)- 1- (4-morpholin-4-yl-phenyl) -butan-1-one, number average molecular weight 380.5
- ISFacure 907 2-methyl-1
- the initiator precipitation is not observed, but the photopolymerization initiator composition (A), the photopolymerization initiator composition (B), a tetrafunctional or higher functional acrylate monomer, and a resin having a polymerization group It was confirmed that even if any of the oligomers was absent, sufficient drying property and reduction in migration to the inclusion could not be obtained.
- 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.
Abstract
Description
表1~表3の組成に従って、実施例1~13および比較例1~8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、色材としてはカーボンブラック16重量%(カーボンブラックとして、実施例1~12においてはラーベン1060Ultraを使用し、実施例13においてはラーベン1180を使用した)及び補色成分としてフタロシアニンブルー3重量%及びジオキサジンバイオレット2重量%(色材合計21重量%)、粘度及び流動性調整剤としてタルク2重量%及び炭酸マグネシウム2重量%(合計4重量%)、その他助剤としてワックス2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3重量%)を、全ての実施例に共通に添加した。 尚、補色成分であるフタロシアニンブルー及びジオキサジンバイオレットはカーボンブラック自体が呈する黄味を打ち消し、インキの漆黒性を更に高める目的で少量配合している。このようなインキの色相調整は「補色」と呼ばれ、一般に広く知られる手法である。
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)の表面に墨濃度1.6~1.8(X-Rite社製SpectroEye濃度計で計測)の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、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27mm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
△:DM27以上~30nm未満
×:DM27mm未満
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120mJ/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1~3に示す諸原料及び略を以下に示す。
・ラーベン1060Ultra:カーボンブラック、平均一次粒子径30nm、比表面積(NSA)66m2/g、コロンビアンケミカル社製
・ラーベン1180:カーボンブラック、平均一次粒子径21nm、比表面積(NSA)110m2/g、コロンビアンケミカル社製
・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
・ジオキサジンバイオレット:ジオキサジンバイオレット、ホスターパームバイオレット RL 02、クラリアント社製
・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
・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
・安定剤溶液:p-メトキシフェノール(メトキノン、精工化学社製)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(SR494NS、サートマー社製)90重量%の混合溶液
・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
・Irgacure379:2-(ジメチルアミノ)-2-(4-メチル-ベンジル)-1-(4-モルフォリン-4-イル-フェニル)-ブタン-1-オン、数平均分子量380.5、 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、数平均分子量279.4、 BASF社製
・Irgacure127:2-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、数平均分子量340.4、 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
・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
・DAROCUR1173:2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、数平均分子量164.2、 BASF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、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
・MIRAMER M-300:トリメチロールプロパントリアクリレート、MIWON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、大同化成工業社製
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 (9)
- 着色顔料、光重合開始剤組成物(A)、光重合開始剤組成物(B)、4官能以上の重合性アクリレートモノマー、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(A)が数平均分子量350以上1000以下であるα-アミノアルキルフェノン系光重合開始剤であり、且つ、
前記(B)が数平均分子量320以上1000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(A)が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、2-(ジメチルアミノ)-2-(4-メチル-ベンジル)-1-(4-モルフォリン-4-イル-フェニル)-ブタン-1-オン、からなる群から選ばれる1つ以上であり、
前記(B)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(A)の含有量が全量の1~3重量%、前記(B)の含有量が全量の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20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%である請求項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を、全量の0.1~2.5重量%の範囲で含有する請求項1~5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、アルキルアミノベンゾフェノン化合物を全量の0.5~4重量%含有する請求項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。
- 前記顔料として、カーボンブラックを全量の10~25重量%含有する請求項1~7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。
- 請求項1~8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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JP2018002958A (ja) * | 2016-07-07 | 2018-01-11 | Dic株式会社 | 活性エネルギー線硬化性印刷インキ、及びその印刷物 |
JP2018002957A (ja) * | 2016-07-07 | 2018-01-11 | Dic株式会社 | 活性エネルギー線硬化性印刷インキ、及びその印刷物 |
US10011730B2 (en) * | 2014-03-20 | 2018-07-03 | Fujifilm Speciality Ink Systems Limited | Printing ink |
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