CN104854200A - Active energy ray-curable offset ink composition - Google Patents
Active energy ray-curable offset ink composition Download PDFInfo
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- CN104854200A CN104854200A CN201480003461.2A CN201480003461A CN104854200A CN 104854200 A CN104854200 A CN 104854200A CN 201480003461 A CN201480003461 A CN 201480003461A CN 104854200 A CN104854200 A CN 104854200A
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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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- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The present invention addresses the problem of providing an active energy ray-curable offset ink composition for reproduction at higher printability by offset printing while providing good curability, low yellowing, light stability, and low toxicity and low migration for use in toys and food packaging. An active energy ray-curable offset ink composition containing an extender pigment, a photopolymerization initiator composition, a tetrafunctional or higher polymerizable acrylate monomer, and a resin oligomer having polymerizable groups, the active energy ray-curable offset ink composition being characterized in that the photopolymerization initiator composition is an [alpha]-hydroxyketone-based photopolymerization initiator having a number-average molecular weight of 320-1300.
Description
Technical field
The present invention relates to invention and its print of active energy ray curable offset printing ink liquid, described active energy ray curable offset printing ink liquid has good solidified nature, low-yellowing, light stability under active energy beam condition, and take into account the security such as toy and the hypotoxicity needed for food product pack purposes, low migration.
Background technology
Under active energy beam condition occur solidification, particularly ultraviolet hardening offset printing ink liquid due to the convenience of the characteristic of wink-dry, be therefore widely used in the packages printing field towards food product pack such as toy, implements made of paper.
In ultraviolet hardening offset printing ink liquid, to present water white transparency, oyster white, translucent outward appearance and be not feature containing coloring components black liquid (being designated as water white transparency system ink liquid below) is widely used in purposes shown below, that is, (1) painted black liquid is implemented further printing to give gloss, by the coating varnish of the purposes of film toughness (OP varnish); (2) medium ink liquid (medium ink) used in the consistency adjusting agent purposes of painted black liquid; (3) by the anchoring priming paint agent (anchor primeragent) etc. that painted black liquid uses for the purpose of the bonding imparting of the printing element of black liquid acceptability difference.
Ultraviolet hardening offset printing ink liquid is widely used in the such food product pack purposes of pastry case, beverage packets, but, in recent years, centered by European and American countries, notice the black liquid composition inside bag food transfer problem of (migration) and this trend just constantly expands, for for the printing ink liquid for one of each material making print, also strong hope improves its security.
As the formula of ultraviolet hardening offset printing ink liquid, the migration of the Photoepolymerizationinitiater initiater of lower molecular weight or the inside bag food of the composition of sensitizing agent easily becomes problem.
Such as, as the inkjet ink composition of toy and food product pack purposes, propose the scheme (for example, referring to patent documentation 1 and 2) of the ink composition using macromolecular material.But for this technology, needing in the offset printing far above the productivity of ink jet printing, drying property is not enough, cannot show enough low migration energy.
In addition, not only to consider the number of the amount of the migration towards interior bag food, also will consider the security of starting material self that food packaging black liquid uses, the presence or absence of toxicity.
Patent documentation 1: Japanese Unexamined Patent Application Publication 2011-502188
Patent documentation 2: Japanese Unexamined Patent Application Publication 2011-500932
Summary of the invention
The problem that invention will solve
Problem of the present invention is to provide a kind of active energy ray curable offset printing ink fluid composition, it has good drying property, low-yellowing, light stability and for toy, the hypotoxicity of food product pack purposes, low migration concurrently, and the drying property had based on the excellence in offset printing and the raising of the productivity brought and mobility.
Solve the method for problem
The discoveries such as the present inventor, compared with the past, by polyfunctional monomer and the polyreactive oligomers of the high molecular Photoepolymerizationinitiater initiater of appropriately combined employing, sensitizing agent and reactivity excellence, thus above-mentioned problem can be realized, and then complete the present invention.
Namely, the invention provides a kind of active energy ray curable offset printing ink fluid composition, it is characterized in that, its be containing pigment extender, photopolymerization initiator composition, 4 officials can above polymerizability acrylate monomer, there is the active energy ray curable offset printing ink fluid composition of the resin oligomers of polymer-based group, wherein, described photopolymerization initiator composition is number-average molecular weight more than 320 and the alpha-alcohol ketone system Photoepolymerizationinitiater initiater of less than 1300.
The effect of invention
Utilize active energy ray curable offset printing ink fluid composition of the present invention, following active energy ray curable offset printing ink liquid can be obtained, namely, high relative to drying property in the past but there is toxicity and migration is also higher and be unsuitable for the black liquid composition of toy, food product pack, drying property and in no way inferior, have excellent photostability, xanthochromia also less, toxicity is low and have the active energy ray curable offset printing ink liquid towards toy, food product pack of low migration concurrently.
Accompanying drawing explanation
Fig. 1 represents using active energy ray curable offset printing ink fluid composition of the present invention to carry out the print irradiation ultraviolet radiation that color development obtain, makes the solidification of black liquid layer and the figure of print that obtains.
Fig. 2 makes the back side of milk carton blank sheet of paper overlap with the mode connected of the print after uviolizing above, and carries out the figure that extrudes.
Embodiment
The present invention in right amount containing pigment extender, number-average molecular weight more than 320 and the alpha-alcohol ketone system Photoepolymerizationinitiater initiater of less than 1300,4 officials can above polymerizability acrylate monomer, there are whole compositions of the resin oligomers of polymer-based group, realize target effect of the present invention thus.
Photopolymerization initiator composition mentioned here is number-average molecular weight more than 320 and the alpha-alcohol ketone system Photoepolymerizationinitiater initiater of less than 1300.
About alpha-alcohol ketone system Photoepolymerizationinitiater initiater, if number-average molecular weight is lower than 320, then there is the tendency that migration amount increases along with the transfer of Photoepolymerizationinitiater initiater composition inside bag thing, if number-average molecular weight is more than 1300, then cause following situation: the mobility of black liquid self reduces, cause storage stability to reduce because of the precipitation again of accompanying with the crystallization of Photoepolymerizationinitiater initiater, the tunicle drying property after printing reduces.In addition, for above-mentioned initiator composition, polyalcohols, fatty acid etc. is made not to have the Components Chemical bonding of conjugated double bond by gimmicks such as esterifications, even if thus make number-average molecular weight more than 1300, the compound of solvability excellence also can be provided technically, but for the derivative of these number-average molecular weights more than 1300, because the actual effect constituent concentration (having the ratio of the conjugated double bond of ultraviolet absorption ability) of the initiator in compound reduces, be therefore difficult to obtain sufficient drying property.
Excellent low migration is demonstrated in colour system ink liquid, and number-average molecular weight more than 350 and alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butanone-1 (number-average molecular weight: 366.5) of less than 1000, 2-(dimethylamino)-2-(4-Methyl-benzvl)-1-(4-morpholine-4-base-phenyl)-butane-1-ketone (number-average molecular weight: 380.5), or acylphosphine oxide system Photoepolymerizationinitiater initiater two (2, 4, 6-trimethylbenzoyl)-phenyl phosphine oxide (number-average molecular weight 418.5), 2, 4, 6-trimethylbenzoy-dipheny phosphine oxide (number-average molecular weight 348.0), there is the variable color (xanthochromia) of the solidification tunicle caused by curing reaction, the reduction of light stability, therefore water white transparency system is not preferred for.
As above-mentioned number-average molecular weight more than 320 and the alpha-alcohol ketone system Photoepolymerizationinitiater initiater of less than 1300, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl can be enumerated }-2-methyl-propan-1-ketone (number-average molecular weight: 340.4), oligomeric (2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone) (number-average molecular weight: 424.57), 2-hydroxyl-1-{4-(4-(2-hydroxy-2-methyl propionyl) phenoxy group) phenyl }-2-methylacetone (number-average molecular weight: 342.39) etc., as long as more than one comprising in them, also can combinationally use multiple.204.3), 2-hydroxy-2-methyl-1-phenyl-propan-1-ketone (number-average molecular weight: 164.2) etc. and be not included the 1-hydroxy-cyclohexyl-phenyl-one (number-average molecular weight: of alpha-alcohol ketone system Photoepolymerizationinitiater initiater is similarly.In addition, in water white transparency system ink liquid, 2,2-dimethoxy-1,2-diphenylethane-1-ketone (number-average molecular weight 256.3), though be widely used, because low migration is poor, does not therefore preferably use.
The containing ratio of above-mentioned alpha-alcohol ketone system Photoepolymerizationinitiater initiater in ink composition is preferably the scope of 1 ~ 8 % by weight relative to black liquid total amount.If addition is less than 1 % by weight, be then difficult to obtain good drying property, in addition, if addition is more than 8 % by weight, then amount of initiator becomes superfluous, can damage black liquid mobility, low migration energy equally, therefore not preferred.
Except above-mentioned alpha-alcohol ketone system Photoepolymerizationinitiater initiater, that record in No. 2514804th, Japanese Patent, imported polymerizable group in initiator molecule phenyl ketone system: compositions group also can be used for the object of giving black liquid drying property and low migration.Such as, particularly, in said composition group, 4-(2-acryloyloxyethoxy) phenyl-(2-hydroxyl-2-propyl group) ketone, can be used by being called that Merck company (existing BASF AG) sells in the past in the present invention with the title of " DAROCUR ZLI3331 ".
In addition, alpha-alcohol ketone system Photoepolymerizationinitiater initiater polymer is quantized and the composition (number-average molecular weight about 1100) that imported by polymerizable group and obtain is sold by BASF AG with the title of " Irgacure LEX201 ", its low migration can be excellent, therefore can be suitable for equally being used in the present invention.
The security of the starting material self that food packaging black liquid uses is take into account if enumerate, there is the concrete example of the Photoepolymerizationinitiater initiater after nontoxicity, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone, namely IRGACURE907 (BASF AG's system) has very excellent solidified nature (black liquid drying property), especially be widely used in ultraviolet hardening offset printing ink liquid, but due to the excessive risk material (GHS classifies: genotoxicity classification 1B (reproductive performance) and 1B (fetus)) being genotoxicity, therefore, the present invention does not rely on it, and can low migration be realized, low odor, the higher printing adaptability needed for offset printing ink liquid such as excellent drying property and mobility.
In addition; as the example of Photoepolymerizationinitiater initiater; 2; 4; 6-trimethylbenzoy-dipheny-phosphine oxide and DAROCURE TPO (BASF AG's system) have excellent inside solidification performance; similarly be widely used; but in security, monitor that chemical substance is by publicity as former Equations of The Second Kind; suspect that there is long term toxicity; therefore; the present invention does not rely on it, and can realize the higher printing adaptability needed for offset printing ink liquid such as low migration, low odor, excellent drying property and mobility.
In addition, as the example of material resin, diallyl phthalate resin (DAP resin) is i.e. Daiso DAP series (Daiso DAP A, Daiso DAP S, Daiso DAP K is Daiso Inc.) have excellent in film toughness, therefore used very widely in existing UV offset printing ink liquid, but unreacted Phthalic acid, diallyl ester monomer (Phthalic acid, diallyl ester remaining in resin, CAS numbering 131-17-9) be former Equations of The Second Kind supervision chemical substance, and be the excessive risk material (GHS classification 1B (sexual cell mutagenicity)) of mutagenicity, therefore, the present invention does not rely on it, and drying property can be provided excellent and consider the food packaging black liquid of security.
As the required composition of active energy ray curable offset printing ink fluid composition of the present invention, can enumerate 4 officials can above polymerizability acrylate monomer.As the concrete example of the polymerizability acrylate monomer of 4 officials' energy, ditrimethylolpropane tetraacrylate (DTMPTA), ethylene-oxide-modified tetramethylol methane tetraacrylate (EO-PETA), epoxy pronane modification tetramethylol methane tetraacrylate (PO-PETA) etc. can be enumerated.As the concrete example of the polymerizability acrylate monomer of 5 functionalities, can Dipentaerythritol Pentaacrylate etc. be enumerated, as the concrete example of the polymerizability acrylate monomer of 6 functionalities, can dipentaerythritol acrylate etc. be enumerated.They may be used alone, can also be used in combination multiple.
4 above-mentioned officials can the containing ratio of polymerizability acrylate monomer in ink composition above relative to black liquid total amount be preferably 15 % by weight to 60 % by weight scope, if lower than 15 % by weight, use 3 officials can following polymerizability acrylate monomer during Jimo liquefaction, solidified nature then can be caused to reduce, drying property and low migration are deteriorated, in addition, if addition is more than 60 % by weight, then the viscosity being difficult to obtain and being suitable for offset printing ink liquid is become.In addition, about above-mentioned as 5 officials can polymerizability acrylate monomer Dipentaerythritol Pentaacrylate and as 6 officials can the dipentaerythritol acrylate of polymerizability acrylate monomer, usage quantity is preferably more than 10 % by weight relative to black liquid total amount.Usually, Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate manufacture sale with the state of monomer or mixture, as ProductName, can enumerate: " DPHA (Sartomer Inc., the ratio of six acrylate in product: about 100 % by weight) " " ARONIX M-400 (East Asia Synesis Company system, the ratio of five acrylate in product: 40 ~ 50 % by weight) " " ARONIX M-402 (East Asia Synesis Company system, the ratio of five acrylate in product: 30 ~ 40 % by weight) " " ARONIX M-403 (East Asia Synesis Company system, the ratio of five acrylate in product: 50 ~ 60 % by weight) " " and ARONIX M-404 (East Asia Synesis Company system, the ratio of five acrylate in product: 30 ~ 40 % by weight) " " ARONIX M-405 (East Asia Synesis Company system, the ratio of five acrylate in product: 10 ~ 20 % by weight) " " ARONIX M-406 (East Asia Synesis Company system, the ratio of five acrylate in product: 25 ~ 35 % by weight) " " LUMICURE DPA-600T (Inc. of biochemical company limited liked by East Asia, Zhangjiagang oil) " " KAYARAD DPHA (Japanese chemical drug Inc.) " " SR399 (Sartomer Inc., the ratio of five acrylate in product: about 100 % by weight) " " MIRAMER M600 (MIWON Inc., the ratio of six acrylate in product: 100 % by weight) " etc., although the mixture ratio of 5 officials' energy and 6 functional acrylates is different, can both be suitable in the present invention.
In addition, as the required composition of active energy ray curable offset printing ink fluid composition of the present invention, the resin oligomers with polymer-based group can be enumerated.Compared with the non-reacted resene (torpescence resin) in molecule without polymerizability base, its reactivity is high, can give more excellent low migration.As the resin oligomers with polymer-based group, such as, epoxy acrylate, aliphatic acrylate, polyester acrylate, urethane acrylate etc. can be enumerated.Wherein, be more preferably epoxy acrylate and derivative thereof, exemplarily, dihydroxyphenyl propane diglycidyl ether diacrylate and derivative thereof can be enumerated, particularly preferably dihydroxyphenyl propane diglycidyl ether diacrylate.
The containing ratio of the above-mentioned resin oligomers with polymer-based group in ink composition is preferably the scope of 20 ~ 65 % by weight relative to black liquid total amount.If lower than 20 % by weight, then cannot obtain sufficient tunicle drying property, offset printing adaptability, in addition, if addition is more than 65 % by weight, then usual due to these polyreactive oligomerses be high viscosity, in the composition described in embodiments of the invention, be therefore difficult to obtain the viscosity being suitable for offset printing ink liquid.On the other hand, in order to adjust viscosity and a large amount of and with low viscous low molecular monomer class (being generally simple function and 2 functional acrylate monomers), when adding polyreactive oligomers with the ratio more than 65 % by weight thus, even if suitable viscosity can be obtained, also low migration can be damaged.
In addition, in the present invention, number-average molecular weight more than 400 can also be added and less than 1500 and the aromatic nitrile base of maximum absorption under there is wavelength 250 ~ 450nm in the scope of 280 ~ 340nm and alkylamino benzoic acid ester compounds as sensitizing agent.Wherein, the two dimethylaminobenzoic acid ester (number-average molecular weight 860) of the PEG of the two dimethylaminobenzoic acid ester (number-average molecular weight 488 ~ 532) of the PEG of 2 functional amine's derivatives, 4 functional amine's derivatives molecular weight higher and not easily move in be preferred.Be similarly ethyl-4-(dimethylamino) benzoic ether (number-average molecular weight 193.2) of alkylamino benzoic acid ester compounds, 2-(dimethylamino) ethylamino benzonitrile acid esters (number-average molecular weight 193.2), 2-ethylhexyl-4-(dimethylamino) benzoic ether (number-average molecular weight 277.4) etc. and be not included.
As the aromatic nitrile base beyond alkylamino benzoic ether, there is alkylamino benzophenone cpd, wherein, 4,4 '-bis-(diethylamino) benzophenone (number-average molecular weight 324.47) is although drying property is excellent and demonstrate low migration, but the maximum absorption wavelength under wavelength 250 ~ 450nm is up to 365nm, the variable color (xanthochromia) of the solidification tunicle caused by curing reaction is serious, does not therefore preferably use in water white transparency system.
The containing ratio of above-mentioned alkylamino benzoic acid ester compounds in ink composition is preferably the scope of 1 ~ 8 % by weight relative to black liquid total amount.If it is not addition is lower than 1 % by weight, then preferred at the further raising this respect that cannot obtain rate of drying, in addition, also can only confirm more than 8 % by weight the effect used even if add, therefore not preferred.
In addition; in water white transparency system ink liquid; although be widely used as the benzophenone (number-average molecular weight 182.22), 4-methyl benzophenone (number-average molecular weight 196.24), O-methyl benzoyl benzoic ether (number-average molecular weight 240.25) etc. of dehydrogenation type Photoepolymerizationinitiater initiater; but because transport property is poor, therefore preferably do not use.
In ultraviolet hardening offset printing ink liquid, for the black liquid of adjustment mobility, prevent flying ink, prevent the physical property improving such as to soak into, give functional object to paper base material when printing, and widely use pigment extender.As pigment extender, public painted pigment dyestuff can be enumerated, such as printing ink liquid pigment extender disclosed in " pigment brief guide (compiling: Japanese pigment technology association compiles) " etc., can use calcium carbonate, magnesiumcarbonate, kaolin clay, talcum, wilkinite, mica, barium sulfate, silicon-dioxide and aluminium hydroxide etc.
As the printing element that print of the present invention uses, be not particularly limited, such as, can enumerate: the paper such as bond paper, enamelled paper (coated paper), art paper (art paper), simile(printing)paper, thin paper, ground paper; Various synthetic paper; The film of vibrin, acrylic resin, vinyl chloride resin, permalon, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, nylon, poly(lactic acid), polycarbonate etc. or sheet; Cellulose film, aluminium foil, other in the past as printing element use various base materials.
The manufacture of offset printing ink liquid of the present invention is in the same manner as ultraviolet hardening ink liquid in the past, above-mentioned pigment extender, polymerizability acrylate monomer, the resin oligomers with polymer-based group, Photoepolymerizationinitiater initiater, sensitizing agent, other additives etc. coordinated and is uniformly mixed with mixing machine etc., using the dispersion machine such as three-roll mill, ball mill to carry out grinding and manufacturing.
Embodiment
Below, embodiment is utilized to illustrate the present invention.
(manufacture method of ink composition)
According to the composition of table 1 ~ table 4, utilize the black liquid of three-roll mill to embodiment 1 ~ 9 and comparative example 1 ~ 12 to grind, obtain various ultraviolet hardening ink composition thus.
It should be noted that, be all added with in whole embodiments as the talcum 3 % by weight of pigment extender and hydrophobic silica 2 % by weight and magnesiumcarbonate 5 % by weight (adding up to 10 % by weight), as the wax 1.5 % by weight of other auxiliary agents and stabiliser solution (mixture of p methoxy phenol 10 % by weight and ethylene-oxide-modified tetramethylol methane tetraacrylate 90 % by weight) 1 % by weight (auxiliary agent adds up to 2.5 % by weight).
(manufacture method of print)
Use simple and easy color development machine (RI TESTER, Feng Rong Seiko Inc.), use black liquid 0.10ml and the ultraviolet hardening ink composition as above obtained is elongated equably in the rubber rollers of RI TESTER and metallic roll, at milk carton paper (polyethylene layer platen, Tetra-Rex, Tetra Pak Inc.) surface be about 220cm with even spread
2the mode of areal extent carry out color development, produce print.It should be noted that, RI TESTER refers to that transfer amount or the printing that can adjust black liquid are pressed by the trier of black liquid color development on paper or film.
(utilizing the drying means of UV lamp source)
UV irradiation is carried out to the print after black liquid coating, black liquid tunicle is solidified dry.Use is equipped with UV irradiating unit (the iGrafx Inc. of water-cooled metal halide lamp (output rating 80W/cm 1 lamp) and belt conveyer, subsidiary cold mirror), print is placed on conveyer, passes through immediately below lamp (irradiation distance 11cm) according to the prescribed condition of the following stated.Ultraviolet irradiation amount under each condition uses ultraviolet accumulated light system (Ushio Motor Corporation UNIMETER UIT-150-A/ is by ray machine UVD-C365) to measure.
(evaluation method 1 of ink composition: solidified nature)
For solidified nature, after just irradiating, pawl is utilized to scrape embrocation (pawl ス Network
star チ method) confirm that print surface is with or without scar.Make conveyor speeds (m/ minute) change of above-mentioned UV irradiating unit while to print irradiation ultraviolet radiation, record is without the fastest conveyor speeds in scar situation.Therefore, conveyor speeds is faster, and the drying property of black liquid is good.
(evaluation method 2 of ink composition: light stability)
Prepare made black liquid 20g, be statically placed in the position of distance luminescent lamp (Panasonic system, 3 wave length type colors of sunshine, Hf luminescent lamp, FHF32EX-N-H) 5cm, after 60 minutes, whether the black liquid of visual confirmation is dry, evaluates according to following 3 grades.For confirming for dry composition in this assessment item, its viscosity that black liquid skinning, black liquid on the printer occur rises, become easily in printing adaptability performance bad.
Zero: there is no drying completely
△: a little drying can be confirmed
×: can drying be confirmed
(evaluation method 3 of ink composition: initiator solvability)
The black liquid made (4 DEG C) in refrigerator is taken care of 1 week, afterwards the black liquid of about 1 gram is placed in metal grindometer (グ
イ Application De ゲ mono-ジ) in (groove depth 0 ~ 25 micron), with metallic spatula, scraping is carried out to the black liquid on grindometer, Photoepolymerizationinitiater initiater in the black liquid of visual confirmation reduce precipitation state together with solvability, evaluate according to following 3 grades.When Photoepolymerizationinitiater initiater separate out and crystallization, newly on grindometer produce the texture (ス ジ) being derived from initiator crystallization.For the composition occurring to separate out in this assessment item, under waiting low temperature environment in the winter time, sufficient product performance cannot be given play to.
Zero: do not observe precipitation.
△: few precipitation can be confirmed.
×: can precipitation be confirmed.
(evaluation method 4 of ink composition: mobility)
The methods enforcement mensuration that ink liquid mobility specifies by Spread Meter method (parallel-plate viscometer) and according to JIS K5101,5701, through time observe the black liquid that clamps between 2 parallel plates of horizontal positioned because of the deadweight (115 grams) of load plate with the characteristic of concentric circles expansion, the expansion diameter of the black liquid after 60 seconds is set to diameter value (DM [mm]), reaches good following 3 grades according to black liquid printing adaptability and evaluate.In this assessment item, DM is less than to the composition of 34mm, is cut (Pot cuts れ) by tank on the printer, become the bad of bad and so on the printing adaptability aspect of transfer easily between performance liquid roller out of ink.
More than zero: DM 37mm
More than △: DM 34 ~ be less than 37nm
×: DM is less than 34mm
(evaluation method 1 of print: xanthochromia)
Confirm the colour-change caused by variable color (xanthochromia) of the solidification tunicle after uviolizing, and evaluate according to following 3 grades.
Zero: there is no colour-change completely, or almost there is no colour-change
△: a little xanthochromia can be confirmed
×: obviously can confirm the colour-change caused by xanthochromia
(evaluation method 2 of print: low migration)
About the evaluation of low migration, basic evaluation order is according to criterion (the EuPIA Guideline onPrinting Inks of Europe printing ink liquid appraisal meeting and EuPIA (European Printing Ink Association), applied to the non-food contact surface of food packagingmaterials and articles, November 2011 (Replaces the September 2009version)).
First, above-mentioned print irradiates 2 UV with the conveyor speeds of 40m/min, makes black liquid layer dry thus.Ultraviolet accumulated light under this condition is about 100mJ/cm
2.Next, with make milk carton blank sheet of paper (after, black liquid is not called milk carton blank sheet of paper by the milk carton paper of the non-printing state of color development) the back side overlap with the mode that connects of solidification ink liquid layer above print, use oil pressure extrusion machine at squeeze pressure 40kg/cm
2, pressurization 48 hours under room temperature 25 DEG C of atmosphere, make the unreacted component in solidification ink liquid layer shift (migration) (with reference to attached Fig. 1 and 2) to the back side of milk carton blank sheet of paper thus.Take off milk carton blank sheet of paper after extrusion and form, producing the fluid container of 1000ml volume.In this fluid container, the back side after black liquid composition transfer is towards inner side.Then, aqueous ethanolic solution (mixing solutions of alcohol 95 % by weight and the pure water 5 % by weight) 1000ml for preparing as model fluid food is injected fluid container and airtight.It should be noted that, the total area of the fluid container inner face contacted with aqueous ethanolic solution 1000ml in this condition is about 600cm
2.Airtight fluid container is left standstill 24 hours under room temperature 25 DEG C of atmosphere, will the black liquid constituents extraction at the milk carton blank sheet of paper back side be transferred to in aqueous ethanolic solution.Afterwards, aqueous ethanolic solution is taken out from fluid container, utilize liquid chromatographic mass analysis to identify used initiator and carry out quantitatively, according to the aggregate value of the migration concentration of each initiator composition, according to 3 grade evaluation migration performances to each stripping concentration (migration concentration).Exemplarily, in the print utilizing the ultraviolet hardening ink liquid employing A, B, C 3 kinds of initiators, when the migration concentration of initiator A be 10ppb, the migration concentration of initiator B is 5ppb, the migration concentration of initiator C is 15ppb, the aggregate value of the migration concentration of initiator composition is be evaluated as A+B+C=10+5+15=30ppb.It should be noted that, liquid chromatographic mass analyze quantitative time, for used whole initiators, made the calibration curve employing above-mentioned aqueous ethanolic solution separately in advance, re-used calibration curve and calculate.
Zero: be less than 30ppb
△: more than 30ppb ~ be less than 60ppb
×: more than 60ppb
[table 1]
[table 2]
[table 3]
[table 4]
Numerical value in table 1 ~ 4 is % by weight.
All raw materials shown in table 1 ~ 4 and abbreviation are below shown.
Talcum: hydrous magnesium silicate, Hi-Filler#5000PJ, Song Cun industry companies system
Hydrophobic silica: diacid SiClx, AEROSIL R972, Japanese AEROSIL Inc.
Magnesiumcarbonate: magnesium basic carbonate, magnesiumcarbonate TT, Naikai Salt Company system
Wax: polyolefin-wax, S-381-N1, Shamrock Inc.
Stablizer: p methoxy phenol, メ ト キ ノ Application, Seiko chemical company system
Ethylene-oxide-modified tetramethylol methane tetraacrylate (SR494NS), Sartomer Inc.
Irgacure369:2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butanone-1, number-average molecular weight 366.5, BASF AG's system
Esacure One: oligomeric (2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone), number-average molecular weight 424.57, Lamberti Inc.
Irgacure819: two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, number-average molecular weight 418.5, BASF AG's system
IrgacureTPO:2,4,6-trimethylbenzoy-dipheny phosphine oxide, number-average molecular weight 348.0, BASF AG's system
KIP160:2-hydroxyl-1-{4-(4-(2-hydroxy-2-methyl propionyl) phenoxy group) phenyl }-2-methylacetone, number-average molecular weight 342.39, Lamberti Inc.
Irgacure184:1-hydroxy-cyclohexyl-phenyl-one, number-average molecular weight 204.3, BASF AG's system
Irgacure651:2,2-dimethoxy-1,2-diphenylethane-1-ketone, number-average molecular weight 256.3, BASF AG's system
ARONIX M-400: mixture (ratio of five acrylate in product: 40 ~ 50 % by weight), East Asia Synesis Company system of Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate
SR355NS: ditrimethylolpropane tetraacrylate, Sartomer Inc.
SR494NS: ethylene-oxide-modified tetramethylol methane tetraacrylate, Sartomer Inc.
MIRAMER M-3130: ethylene-oxide-modified Viscoat 295, MIWON Inc.
PHOTOMER 4127: polyethylene oxide modified neopentylglycol diacrylate, CognisJapan Inc.
DICLITE UE-8200T: dihydroxyphenyl propane diglycidyl ether diacrylate
UNIDIC V3212: the mixture of non-reacted vibrin 40 % by weight, DPHA (mixture of Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate) 30 % by weight and ditrimethylolpropane tetraacrylate 30 % by weight, DIC Inc.
EAB-SS:4,4 '-bis-(diethylamino) benzophenone, number-average molecular weight 324.47, Datong District changes into industrial's system
GENOPOL AB1: the two dimethylaminobenzoic acid ester of PEG, number-average molecular weight 860, RAHN AG Inc.
Omnipol ASA: the two dimethylaminobenzoic acid ester of PEG, number-average molecular weight 488 ~ 532, IGM Inc.
LUNACUR EDB: ethyl-4-(dimethylamino) benzoic ether, number-average molecular weight 193.24, EUTEC CHEMICAL Inc.
DAROCUR EHA:2-ethylhexyl-4-(dimethylamino) benzoic ether, number-average molecular weight 277.4, BASF AG's system
(mensuration of number-average molecular weight)
It should be noted that, the mensuration of the number-average molecular weight based on GPC (polystyrene conversion) in the present invention uses eastern Cao (strain) Inc. HLC8220 system to carry out under the following conditions.
Separator column: use 4 eastern Cao (strain) TSKgelGMH processed
hR-N.Column temperature: 40 DEG C.Moving phase: with light pure pharmaceutical worker industry (strain) tetrahydrofuran (THF) processed.Flow velocity: 1.0ml/ minute.Sample solution concentration: 1.0 % by weight.Sample injection rate: 100 microlitres.Detector: differential refractometer.
For the active energy ray curable offset printing ink fluid composition described in embodiment, obtained good drying property by ultraviolet light source.In addition, by coordinating each starting material in the scope of above-mentioned % by weight, thus as necessary characteristic of the present invention, depend on storage stability that initiator separates out, bring the mobility of impact to printing adaptability, reach good result in assessment item that inwardly reduction of bag thing migration is such.
In the result of comparative example, although do not observe initiator to separate out, but confirm: if lack photopolymerization initiator composition, 4 officials can above polymerizability acrylate monomer, have in the resin oligomers of polymer-based group any one, just cannot obtain the reduction of sufficient drying property, the inwardly migration of bag thing.
Utilizability in industry
Active energy ray curable offset printing ink fluid composition of the present invention and use its print can not only be applied to safety-sensitive, the toy of wholesomeness, various packaging material for food, can also be widely used in the packaging of sanitation, makeup, pharmaceuticals etc., fill purposes.
Nomenclature
1, black liquid layer is solidified
2, milk carton paper
3, milk carton blank sheet of paper
Claims (7)
1. an active energy ray curable offset printing ink fluid composition, it is characterized in that, be containing pigment extender, photopolymerization initiator composition, 4 officials can above polymerizability acrylate monomer and have the active energy ray curable offset printing ink fluid composition of resin oligomers of polymer-based group
Wherein,
Described photopolymerization initiator composition is number-average molecular weight more than 320 and the alpha-alcohol ketone system Photoepolymerizationinitiater initiater of less than 1300.
2. active energy ray curable offset printing ink fluid composition according to claim 1, wherein,
Described photopolymerization initiator composition is for being selected from 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl }-2-methyl-propan-1-ketone, oligomeric (2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone), 2-hydroxyl-1-{4-(4-(2-hydroxy-2-methyl propionyl) phenoxy group) phenyl more than one in-2-methylacetone.
3. active energy ray curable offset printing ink fluid composition according to claim 1 and 2, wherein,
Described photopolymerization initiator composition is 1 ~ 8 % by weight, 4 official of total amount can polymerizability acrylate monomer above be more than 15 % by weight of total amount, and the resin oligomers with polymer-based group is 20 ~ 65 % by weight of total amount.
4. the active energy ray curable offset printing ink fluid composition according to any one of claims 1 to 3, wherein,
Described 4 officials can polymerizability acrylate monomer above be the mixture of Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate, and with more than 10 % by weight of total amount scope contain described 4 officials can above polymerizability acrylate monomer.
5. the active energy ray curable offset printing ink fluid composition according to any one of Claims 1 to 4, wherein,
The described resin oligomers with polymer-based group is epoxy acrylate and derivative thereof.
6. the active energy ray curable offset printing ink fluid composition according to any one of Claims 1 to 5, it also contains the aromatic uncle amine compound of 1 ~ 8 % by weight of total amount, the number-average molecular weight more than 400 of described aromatic uncle amine compound and less than 1500, and described aromatic uncle amine compound has maximum absorption under wavelength 250 ~ 450nm in the scope of wavelength 280 ~ 340nm.
7. a print, it is the print using the active energy ray curable offset printing ink fluid composition according to any one of claim 1 ~ 6 to carry out offset printing and obtain.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013066368 | 2013-03-27 | ||
| JP2013-066368 | 2013-03-27 | ||
| JP2013173410 | 2013-08-23 | ||
| JP2013-173410 | 2013-08-23 | ||
| PCT/JP2014/057274 WO2014156812A1 (en) | 2013-03-27 | 2014-03-18 | Active energy ray-curable offset ink composition |
Publications (2)
| Publication Number | Publication Date |
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| CN104854200A true CN104854200A (en) | 2015-08-19 |
| CN104854200B CN104854200B (en) | 2016-10-12 |
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| CN201480003461.2A Expired - Fee Related CN104854200B (en) | 2013-03-27 | 2014-03-18 | Active energy ray curable offset printing ink composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5634652B1 (en) |
| CN (1) | CN104854200B (en) |
| WO (1) | WO2014156812A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108026399A (en) * | 2015-09-17 | 2018-05-11 | 东丽株式会社 | Lithographic printing ink, lithographic plate ink varnish and the manufacture method using its printed article |
| CN113072836A (en) * | 2021-03-30 | 2021-07-06 | 中山市中益油墨涂料有限公司 | Low-migration ultraviolet curing ink and preparation method thereof |
| US11161991B2 (en) | 2015-11-25 | 2021-11-02 | Toray Industries, Inc. | Lithographic ink |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6205696B2 (en) * | 2012-09-25 | 2017-10-04 | Dic株式会社 | Active energy ray-curable composition and cured product |
| JP6230300B2 (en) * | 2013-06-28 | 2017-11-15 | 太陽インキ製造株式会社 | Photocurable composition and cured product thereof |
| CN104650646A (en) * | 2015-03-12 | 2015-05-27 | 山东德创喷墨科技有限公司 | Low-migration UV flexible printing ink and preparation method thereof |
| JP6925121B2 (en) * | 2016-12-07 | 2021-08-25 | Ｄｉｃグラフィックス株式会社 | Printed matter |
| JP2018089931A (en) * | 2016-12-07 | 2018-06-14 | Ｄｉｃグラフィックス株式会社 | Printed matter |
| EP3743473B1 (en) * | 2019-04-18 | 2022-01-12 | Sun Chemical Corporation | Low migration electron beam curable primer |
| JP7381357B2 (en) | 2020-02-03 | 2023-11-15 | Ｄｉｃグラフィックス株式会社 | Active energy ray-curable ink for lithographic offset printing and printed matter |
| WO2021245846A1 (en) * | 2020-06-03 | 2021-12-09 | 東洋インキＳｃホールディングス株式会社 | Active energy ray-curable lithographic printing ink, and printed matter |
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| JP2000160086A (en) * | 1998-11-25 | 2000-06-13 | Dainippon Ink & Chem Inc | Radiation curable printing ink composition |
| JP2007131737A (en) * | 2005-11-10 | 2007-05-31 | Toyo Ink Mfg Co Ltd | Coloring composition |
| JP2010076271A (en) * | 2008-09-26 | 2010-04-08 | National Printing Bureau | Genuineness-determinable printed matter using special luminescence |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4511822B2 (en) * | 2003-06-03 | 2010-07-28 | 東洋インキ製造株式会社 | Active energy ray-curable dry lithographic printing ink composition, printing method and printed matter thereof |
-
2014
- 2014-03-18 WO PCT/JP2014/057274 patent/WO2014156812A1/en active Application Filing
- 2014-03-18 JP JP2014535832A patent/JP5634652B1/en active Active
- 2014-03-18 CN CN201480003461.2A patent/CN104854200B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000160086A (en) * | 1998-11-25 | 2000-06-13 | Dainippon Ink & Chem Inc | Radiation curable printing ink composition |
| JP2007131737A (en) * | 2005-11-10 | 2007-05-31 | Toyo Ink Mfg Co Ltd | Coloring composition |
| JP2010076271A (en) * | 2008-09-26 | 2010-04-08 | National Printing Bureau | Genuineness-determinable printed matter using special luminescence |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108026399A (en) * | 2015-09-17 | 2018-05-11 | 东丽株式会社 | Lithographic printing ink, lithographic plate ink varnish and the manufacture method using its printed article |
| US11161991B2 (en) | 2015-11-25 | 2021-11-02 | Toray Industries, Inc. | Lithographic ink |
| CN113072836A (en) * | 2021-03-30 | 2021-07-06 | 中山市中益油墨涂料有限公司 | Low-migration ultraviolet curing ink and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5634652B1 (en) | 2014-12-03 |
| WO2014156812A1 (en) | 2014-10-02 |
| CN104854200B (en) | 2016-10-12 |
| JPWO2014156812A1 (en) | 2017-02-16 |
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