CN104854199A - Active energy ray curable offset ink composition - Google Patents
Active energy ray curable offset ink composition Download PDFInfo
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- CN104854199A CN104854199A CN201480003452.3A CN201480003452A CN104854199A CN 104854199 A CN104854199 A CN 104854199A CN 201480003452 A CN201480003452 A CN 201480003452A CN 104854199 A CN104854199 A CN 104854199A
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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
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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 which is more suitable for offset printing while also exhibiting favorable curability, and low toxicity and low migration properties for use as toy or food packaging. An active energy ray curable offset ink composition containing a coloring pigment, a photoinitiator composition (A), a photoinitiator composition (B), a tetrafunctional or higher polymerizable acrylate monomer, and a resin oligomer having a polymer group, the active energy ray curable offset ink composition being characterized in that (A) is an alpha-aminoalkylphenone photoinitiator having a number average molecular weight of 350-1000, inclusive, and (B) is an alpha-hydroxyketone photoinitiator having a number average molecular weight of 320-1000, inclusive.
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 considered the security such as toy and the hypotoxicity needed for food product pack purposes, low migration be cured well under active energy beam condition.
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.
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.
Particularly, if enumerate the example of Photoepolymerizationinitiater initiater, then 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), particularly 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, i.e. 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, be 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.
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 concurrently and for toy, the hypotoxicity of food product pack purposes, low migration, and the drying property had based on the excellence in offset printing and the productivity brought improves 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 for containing tinting pigment, photopolymerization initiator composition (A), photopolymerization initiator composition (B), 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, above-mentioned (A) is for number-average molecular weight more than 350 and the alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater of less than 1000, and, above-mentioned (B) is for number-average molecular weight more than 320 and the alpha-alcohol ketone system Photoepolymerizationinitiater initiater of less than 1000.
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 also higher and be unsuitable for toy, food product pack black liquid composition for, drying property and in no way inferior, 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 tinting pigment, number-average molecular weight more than 350 and the alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater of less than 1000, number-average molecular weight more than 320 and the alpha-alcohol ketone system Photoepolymerizationinitiater initiater of less than 1000,4 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 (A) is for number-average molecular weight more than 350 and the alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater of less than 1000, and photopolymerization initiator composition (B) is for number-average molecular weight more than 320 and the alpha-alcohol ketone system Photoepolymerizationinitiater initiater of less than 1000.
About alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater, if number-average molecular weight is lower than 350, 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 1000, 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.Similarly, about alpha-alcohol ketone system Photoepolymerizationinitiater initiater, if number-average molecular weight is lower than 320, then also there is the tendency that migration amount increases, if number-average molecular weight is more than 1000, then cause following situation: the mobility of black liquid self reduces, cause keeping quality to reduce because of the precipitation again of accompanying with the crystallization of Photoepolymerizationinitiater initiater, the tunicle drying property reduction after printing.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 1000, the compound of solvability excellence also can be provided technically, but for the derivative of these number-average molecular weights more than 1000, 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.
As above-mentioned number-average molecular weight more than 350 and the alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater of less than 1000,366.5), 2-(dimethylamino)-2-(4-Methyl-benzvl)-1-(4-morpholine-4-base-phenyl)-butane-1-ketone (number-average molecular weight: 380.5) etc. 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butanone-1 (number-average molecular weight: can be enumerated, as long as more than one comprising in them, also can combinationally use multiple.Be similarly (number-average molecular weight are 279.4) such as 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone of alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater then and be not included.
As above-mentioned number-average molecular weight more than 320 and the alpha-alcohol ketone system Photoepolymerizationinitiater initiater of less than 1000, 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.
Containing ratio in the ink composition of above-mentioned alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater is preferably the scope of 1 ~ 3 % by weight relative to black liquid total amount.If addition is less than 1 % by weight, then be difficult to obtain good drying property, if addition is more than 3 % by weight in addition, then amount of initiator becomes superfluous, not only the raising degree of drying property reduces, and the solvability in the liquid component of initiator in black liquid reduces, and black liquid mobility reduces, in addition unreacted amount of initiator increases and damages low migration energy, therefore not preferred.
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-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater, outside alpha-alcohol ketone system Photoepolymerizationinitiater initiater, oxime ester system Photoepolymerizationinitiater initiater also can be used for the object of giving black liquid drying property and low migration.As the example of oxime ester system Photoepolymerizationinitiater initiater; 1-[4-(thiophenyl)-1 can be enumerated; 2-octanedione 2-(O-benzoyl oximes)] (ProductName IRGACUREOXE01; BASF AG's system), 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base] ethyl ketone 1-(O-acetyl oxime) (ProductName IRGACURE OXE02; BASF AG's system) etc.; the molecular weight of these oxime ester series initiators is high and low migration aspect excellent, can use in the scope not damaging effect of the present invention as required.
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 above polymerizability acrylate monomer containing ratio in ink composition be preferably more than 20 % by weight relative to black liquid total amount, if lower than 20 % by weight, Jimo liquefaction time use 3 officials can following polymerizability acrylate monomer, solidified nature then can be caused to reduce, and drying property and low migration are deteriorated.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, preferred usage quantity is 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 (biochemical company limited system 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: about 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 polymerizable group, its reactivity is high, can give more excellent low migration.As the resin oligomers with polymer-based group, such as, can enumerate epoxy acrylate, aliphatic acrylate, polyester acrylate, urethane acrylate etc.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, be difficult to obtain the viscosity being suitable for offset printing ink liquid in therefore described in an embodiment of the present invention composition.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, bis-acylphosphine oxides system Photoepolymerizationinitiater initiater can also be added, particularly preferably in the scope of 0.1 ~ 2.5 % by weight, use two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide relative to black liquid total amount.
If addition is lower than 0.1 % by weight, drying property is not then almost had to improve effect, in addition, if addition is more than 2.5 % by weight, then amount of initiator becomes superfluous, not only cannot expect the further raising of drying property, and be difficult to be dissolved in offset printing ink liquid, cause the deterioration of the reduction of black liquid mobility and the storage stability caused by precipitation, therefore not preferred.
In addition, in the present invention, alkylamino benzophenone cpd as aromatic nitrile base can also be added as sensitizing agent.Wherein, for 4,4 '-bis-(diethylamino) benzophenone (number-average molecular weight 324.47), from drying property is excellent and molecular weight is higher and not easily move this respect and consider it is preferred.As the aromatic nitrile base beyond alkylamino benzophenone, there is alkylamino benzoates, ethyl-4-(dimethylamino) benzoic ether (number-average molecular weight 193.2), 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. can be enumerated, but in the drying property of offset printing ink liquid, alkylamino benzophenone is poor, and it is not molecular weight is lower and easily move, therefore preferred.
The containing ratio of above-mentioned alkylamino benzophenone cpd in ink composition is preferably the scope of 0.5 ~ 4 % by weight relative to black liquid total amount.If it is not addition is lower than 0.5 % by weight, then preferred in the further raising that cannot realize rate of drying, in addition, even if add and more than 4 % by weight, can only confirm the effect used yet, therefore not preferred.
As tinting pigment, public painted pigment dyestuff can be enumerated, such as can enumerate " pigment dyestuff handbook (author: this merit of bridge, sale room: Color Office, first edition in 2006) (author: this Isao of Bridge, the capable institute of development: カ ラ mono-オ Off イ ス, first edition in 2006) " the middle printing ink liquid pigment dyestuff etc. recorded, solubility azo pigment can be used, insoluble azo pigment, condensed azo-pigment, metal phthalocyanine pigment, metal-free phthalocyanine, quinacridone pigment, perylene dye, purple cyclic ketones pigment, isoindolenone pigments, isoindoline pigment, triazine dioxin pigment, thioindigo color, anthraquione pigmentss, quinophthalone pigments, metal complex pigment, diketopyrrolo-pyrrole pigment, charcoal blacks, other polycycle pigment etc.
In the ultraviolet hardening ink liquid comprising above-mentioned tinting pigment, particularly employ in the ink ink liquid of the high carbon black of ultraviolet absorption ability in the scope with addition being 10 ~ 25 % by weight, make the loss of the ultraviolet energy of Photoepolymerizationinitiater initiater sensitization more, compared with other tinting pigment, especially the photopolymerization reaction bottom black liquid tunicle not easily carries out, therefore be difficult to obtain sufficient drying property and low migration energy, but for the said offset printing ink fluid composition of the present invention, even if employ the ink ink liquid of the carbon black of 10 ~ 25 % by weight, also suitable drying property can be given.
But in the black liquid of the ultraviolet hardening of addition more than 25 % by weight of carbon black, the loss of the ultraviolet energy caused by carbon black is excessive, cannot obtain suitable drying property, therefore not preferred.The average primary particle diameter of above-mentioned carbon black is preferably the scope of 15 ~ 70nm, is particularly preferably the scope of 20 ~ 40nm.When average primary particle diameter is less than 15nm, the loss of the ultraviolet energy caused by carbon black is excessive, cannot obtain suitable drying property, therefore not preferred, in addition, when more than 70nm, can damage the black sense of ink ink liquid, therefore not preferred.
Above-mentioned carbon black can be enumerated and pass through oven process, thermal process (サ mono-マ Le method), the known methods such as contact process (コ Application タ Network ト method) and the carbon black manufactured, such as can enumerate RAVEN 14, RAVEN450, RAVEN 860Ultra, RAVEN 1035, RAVEN 1040, RAVEN 1060Ultra, RAVEN 1080Ultra, RAVEN 1180, RAVEN 1255 (more than, Columbian Chemical Inc.), Regal 400R, Regal 330R, Regal 660R, Mogul L (more than, Cabot Inc.), MA7, MA8, MA11 (more than, Mitsubishi Chemical Ind's system) etc., they can be used alone, in addition also can appropriately combined use two or more.
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 tinting pigment, 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 3, utilize the black liquid of three-roll mill to embodiment 1 ~ 13 and comparative example 1 ~ 8 to grind, obtain various ultraviolet hardening ink composition thus.
It should be noted that, carbon black 16 % by weight as look material is all added with (as carbon black in whole embodiments, RAVEN 1060Ultra is employed in embodiment 1 ~ 12, RAVEN1180 is employed in embodiment 13) and as the phthalocyanine blue 3 % by weight Ji dioxazine violet 2 % by weight (look material adds up to 21 % by weight) of complementary color component, as talcum 2 % by weight and the magnesiumcarbonate 2 % by weight (adding up to 4 % by weight) of viscosity and mobility adjusting agent, as wax 2 % by weight and the 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 3 % by weight) of other auxiliary agents.It should be noted that, be for eliminating jaundice that carbon black self shows and improving the object of the pitch-dark property of black liquid further and coordinate on a small quantity as the phthalocyanine blue of complementary color component and dioxazine violet.The hue adjustment of this black liquid is called as " complementary color ", is the method be usually widely known by the people.
(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 carry out color development in even spread to the mode of scope of black concentration 1.6 ~ 1.8 (X-Rite Inc. SpectroEye densitometer measures), 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 100W/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, utilize pawl to scrape embrocation (pawl ス Network ラ 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: 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 on metal grindometer (ダ ラ イ Application De ゲ mono-ジ) (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 3 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 27mm, 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 30mm
More than △: DM 27 ~ be less than 30nm
×: DM is less than 27mm
(evaluation method 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 120mJ/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]
Numerical value in table 1 ~ 3 is % by weight.
All raw materials shown in table 1 ~ 3 and abbreviation are below shown.
RAVEN 1060Ultra: carbon black, average primary particle diameter 30nm, specific surface area (NSA) 66m
2/ g, Columbian Chemical Inc.
RAVEN1180: carbon black, average primary particle diameter 21nm, specific surface area (NSA) 110m
2/ g, Columbian Chemical Inc.
Phthalocyanine blue: copper phthalocyanine, FASTOGEN BLUE TGR-1, DIC Inc.
Dioxazine violet: dioxazine violet, Hostaperm Violet RL 02, Clariant Inc.
Talcum: hydrous magnesium silicate, Hi-Filler#5000PJ, Song Cun industry companies system
Magnesiumcarbonate: magnesium basic carbonate, magnesiumcarbonate TT, Naikai Salt Company system
Wax: polyolefin-wax, S-381-N1, Shamrock Inc.
Stabiliser solution: the mixing solutions of p methoxy phenol (メ ト キ ノ Application, Seiko chemical company system) 10 % by weight and ethylene-oxide-modified tetramethylol methane tetraacrylate (SR494NS, Sartomer Inc.) 90 % by weight
Irgacure369:2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butanone-1, number-average molecular weight 366.5, BASF AG's system
Irgacure379:2-(dimethylamino)-2-(4-Methyl-benzvl)-1-(4-morpholine-4-base-phenyl)-butane-1-ketone, number-average molecular weight 380.5, BASF AG's system
Irgacure907:2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone, number-average molecular weight 279.4, BASF AG's system
Irgacure127:2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl }-2-methyl-propan-1-ketone, number-average molecular weight 340.4, 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.
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
DAROCUR1173:2-hydroxy-2-methyl-1-phenyl-propan-1-ketone, number-average molecular weight 164.2, BASF AG's system
Irgacure819: two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, 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.
MIRAMER M-300: Viscoat 295, MIWON Inc.
DICLITE UE-8200T: dihydroxyphenyl propane diglycidyl ether diacrylate
UNIDIC V3212: non-reacted vibrin 40 % by weight, DPHA (mixture of Dipentaerythritol Pentaacrylate and dipentaerythritol acrylate) 30 % by weight, with the mixture of ditrimethylolpropane tetraacrylate 30 % by weight, DIC Inc.
EAB-SS:4,4 '-bis-(diethylamino) benzophenone, Datong District changes into industrial'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 (A), photopolymerization initiator composition (B), 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, inwardly bag thing migration.
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 (9)
1. an active energy ray curable offset printing ink fluid composition, it is characterized in that, be containing tinting pigment, photopolymerization initiator composition (A), photopolymerization initiator composition (B), 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 (A) for number-average molecular weight more than 350 and the alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater of less than 1000, and,
Described (B) is for number-average molecular weight more than 320 and the alpha-alcohol ketone system Photoepolymerizationinitiater initiater of less than 1000.
2. active energy ray curable offset printing ink fluid composition according to claim 1, wherein,
Described (A) more than one for being selected from 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butanone-1,2-(dimethylamino)-2-(4-Methyl-benzvl)-1-(4-morpholine-4-base-phenyl)-butane-1-ketone
Described (B) 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,
The content of described (A) is 1 ~ 3 % by weight of total amount, the content of described (B) is 1 ~ 8 % by weight of total amount, 4 officials can polymerizability acrylate monomer above be more than 20 % 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 two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide with the scope of 0.1 of total amount ~ 2.5 % by weight.
7. the active energy ray curable offset printing ink fluid composition according to any one of claim 1 ~ 6, it also contains alkylamino benzophenone cpd with the scope of 0.5 of total amount ~ 4 % by weight.
8. the active energy ray curable offset printing ink fluid composition according to any one of claim 1 ~ 7, wherein,
As described pigment, contain carbon black with the scope of 10 of total amount ~ 25 % by weight.
9. a print, it is the print using the active energy ray curable offset printing ink fluid composition according to any one of claim 1 ~ 8 to carry out offset printing and obtain.
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| JP2013034573 | 2013-02-25 | ||
| JP2013-034573 | 2013-02-25 | ||
| JP2013176748 | 2013-08-28 | ||
| JP2013-176748 | 2013-08-28 | ||
| PCT/JP2014/053779 WO2014129461A1 (en) | 2013-02-25 | 2014-02-18 | Active energy ray curable offset ink composition |
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| CN104854199A true CN104854199A (en) | 2015-08-19 |
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| JP (1) | JP5683757B2 (en) |
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| CN106062098A (en) * | 2014-02-20 | 2016-10-26 | 东洋油墨Sc控股株式会社 | Actinic-ray-curable offset ink composition and print obtained therewith |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10011730B2 (en) * | 2014-03-20 | 2018-07-03 | Fujifilm Speciality Ink Systems Limited | Printing ink |
| JP2018002958A (en) * | 2016-07-07 | 2018-01-11 | Dic株式会社 | Active energy ray-curable printing ink and printed matter of the same |
| JP2018002957A (en) * | 2016-07-07 | 2018-01-11 | Dic株式会社 | Active energy ray-curable printing ink and printed matter of the same |
| UA124115C2 (en) * | 2016-12-09 | 2021-07-21 | Сікпа Холдінг Са | Low energy curing offset and letterpress printing inks and printing process |
| UA123605C2 (en) * | 2016-12-09 | 2021-04-28 | Сікпа Холдінг Са | Low energy curing offset and letterpress printing inks and printing process |
| US20190390073A1 (en) * | 2018-06-22 | 2019-12-26 | Xerox Corporation | LED Curable Compositions |
| US20190390072A1 (en) * | 2018-06-22 | 2019-12-26 | Xerox Corporation | LED Curable Offset Printing Ink Composition |
| BR112021016891A2 (en) * | 2019-03-01 | 2021-11-03 | Sun Chemical Corp | Microwaveable Solvent-Based Packaging Ink Composition |
| CN115044282B (en) * | 2022-08-17 | 2022-11-22 | 佛山市儒林化工有限公司 | Safe laminated non-migration UV gloss oil for external use of food cans and preparation method thereof |
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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 |
| CN101048472A (en) * | 2004-10-29 | 2007-10-03 | 大日本油墨化学工业株式会社 | Active energy ray-curable inkjet recording ink |
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| JP2010159343A (en) * | 2009-01-07 | 2010-07-22 | Toyo Ink Mfg Co Ltd | Active energy ray-curable type ink and printed matter |
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- 2014-02-18 JP JP2014535831A patent/JP5683757B2/en active Active
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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 |
| CN101048472A (en) * | 2004-10-29 | 2007-10-03 | 大日本油墨化学工业株式会社 | Active energy ray-curable inkjet recording ink |
| JP2007131737A (en) * | 2005-11-10 | 2007-05-31 | Toyo Ink Mfg Co Ltd | Coloring composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106062098A (en) * | 2014-02-20 | 2016-10-26 | 东洋油墨Sc控股株式会社 | Actinic-ray-curable offset ink composition and print obtained therewith |
| CN106062098B (en) * | 2014-02-20 | 2019-10-01 | 东洋油墨Sc控股株式会社 | Active energy ray-curable flexographic ink composition and its printed article |
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| Publication number | Publication date |
|---|---|
| WO2014129461A1 (en) | 2014-08-28 |
| JP5683757B2 (en) | 2015-03-11 |
| JPWO2014129461A1 (en) | 2017-02-02 |
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Application publication date: 20150819 |