WO2015163184A1 - Procédé pour le durcissement d'une encre offset durcissable par un rayonnement d'énergie active - Google Patents

Procédé pour le durcissement d'une encre offset durcissable par un rayonnement d'énergie active Download PDF

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Publication number
WO2015163184A1
WO2015163184A1 PCT/JP2015/061419 JP2015061419W WO2015163184A1 WO 2015163184 A1 WO2015163184 A1 WO 2015163184A1 JP 2015061419 W JP2015061419 W JP 2015061419W WO 2015163184 A1 WO2015163184 A1 WO 2015163184A1
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Prior art keywords
curing
active energy
energy ray
compound
ink
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PCT/JP2015/061419
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English (en)
Japanese (ja)
Inventor
清水　英樹
謙 山崎
真 中村
和芳 星
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Ｄｉｃグラフィックス株式会社
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Priority to JP2016514872A priority Critical patent/JPWO2015163184A1/ja
Publication of WO2015163184A1 publication Critical patent/WO2015163184A1/fr

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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams

Definitions

  • the present invention relates to a method for curing an offset ink that is cured by irradiation with active energy rays. Furthermore, it is related with the ink used for the hardening method of this ink, and the printed matter using the ink.
  • Activating energy ray-curable offset ink is widely used in the field of package printing such as paper containers because of the convenience of instantaneous curing characteristics.
  • the single wavelength light emitting diode is excellent in heat generation and is used in various industries.
  • the single wavelength light emitting diode using a limited wavelength region is an ultraviolet lamp light source that emits ultraviolet light of a wide wavelength range.
  • the photopolymerization initiators that can be used are limited, and it is difficult to cure the outermost surface of the coating film.
  • An object of the present invention is to provide a method for curing an active energy ray-curable offset ink having improved productivity and printability due to excellent curability in offset printing.
  • the present inventors have solved the above problem by combining two or more light emitting diodes having different emission wavelengths as curing means for an active energy ray-curable ink containing a specific active energy ray polymerizable compound and a photopolymerization initiator. The inventors have found that this can be achieved and have reached the present invention.
  • the present invention relates to a method for curing an active energy ray-curable ink containing an active energy ray-polymerizable compound (I) having an ethylenic double bond and a photopolymerization initiator (II), and a light source used for curing Is a combination of two or more light emitting diodes having different emission wavelengths, and relates to a method for curing an active energy ray curable ink.
  • the present invention further relates to a method for curing an active energy ray-curable ink in which the light emitting wavelength of the light emitting diode is 200 to less than 350 nm and 350 to 420 nm.
  • the present invention further provides an activity wherein the photopolymerization initiator (II) is a photopolymerization initiator (A) having an absorption wavelength of 200 to less than 350 nm and a photopolymerization initiator (B) having an absorption wavelength of 350 to 420 nm.
  • the present invention relates to a method for curing an energy beam curable ink.
  • the present invention further relates to a method for curing an active energy ray-curable ink in which the photopolymerization initiator (A) contains at least one selected from the following group (A).
  • A group ⁇ (dimethyl) aminoalkylphenone compound, ⁇ -morpholinoalkylphenone compound, Acylphosphine oxide compounds
  • the present invention further relates to a method for curing an active energy ray-curable ink in which the photopolymerization initiator (B) contains at least one selected from the following group (B).
  • B group hydroxyacetophenone compound, Benzophenone compounds excluding dialkylaminobenzophenone compounds, ⁇ -Hydroxyalkylphenone compounds
  • the present invention further relates to a method for curing an active energy ray-curable ink containing a dialkylaminobenzophenone compound and / or a thioxanthone compound as a photopolymerization initiator (III).
  • the present invention further provides an ink used in the active energy ray-curable ink curing method and a printed matter printed using the ink.
  • the present invention it is possible to provide a curing method for an active energy ray-curable offset ink that exhibits high curability, an ink used for the curing method, and a printed matter using the same.
  • the present invention relates to a method for curing an active energy ray-curable ink containing an active energy ray-polymerizable compound (I) having an ethylenic double bond and a photopolymerization initiator (II), wherein a light source used for curing is used.
  • the effect of the present invention can be achieved by combining two or more light emitting diodes having different emission wavelengths.
  • the ink used for the curing method of the active energy ray-curable ink of the present invention contains the active energy ray-polymerizable compound (I) having an ethylenic double bond as an essential component.
  • Specific examples thereof include the following active energy ray polymerizable compounds.
  • Active energy ray-polymerizable compound (I) having an ethylenic double bond As the active energy ray-polymerizable compound (I) having an ethylenic double bond used in the ink used in the method of curing the active energy ray-curable ink of the present invention, it is known as a normal active energy ray-curable composition.
  • the (meth) acrylic monomer and / or (meth) acrylic oligomer can be arbitrarily selected and used.
  • “(meth) acryl” is a general term for acrylic and methacrylic.
  • Examples of (meth) acrylic monomers include unsaturated carboxylic acids such as acrylic acid and methacrylic acid or esters thereof, such as alkyl-, cycloalkyl-, halogenated alkyl-, alkoxyalkyl-, hydroxyalkyl-, aminoalkyl-, allyl.
  • the (meth) acrylic monomer polyethylene glycol having an ethylene glycol unit in the molecule (n is 3 or more, approximately 14 or less) di (meth) acrylate, trimethylolpropane EO modification (n is 3 or more) And approximately 14 or less) tri (meth) acrylate, phenol EO-modified (n is 3 or more and approximately 14 or less) (meth) acrylate, 2-hydroxyethyl (meth) acrylate having a hydroxyl group in the molecule, 2 -Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate and the like.
  • These (meth) acrylic monomers may be used alone or in combination of two or more.
  • cyclopentadienyl (meth) acrylate dicyclopentadienyl oxyethyl (meth) acrylate, dihydrodicyclopentadienyl (meth) acrylate such as a (meth) acrylic monomer.
  • active energy ray polymerizable compounds may be used alone or in combination of two or more.
  • Examples of the active energy ray polymerizable compound particularly suitable for the present invention include methyl, ethyl, propyl, butyl, amyl, 2-ethylhexyl, isooctyl, nonyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, benzyl, methoxyethyl, and butoxyethyl.
  • the oligomer contained in the active energy ray-curable ink according to the embodiment is a compound that is crosslinked or polymerized by irradiation with light. Moreover, although it is a compound which has a polymer of a monomer as a principal chain, the number of monomers which comprise a principal chain is not limited. The molecular weight of the oligomer is preferably in the range of 500 to 20,000.
  • the number of functional groups of the oligomer is preferably 2-20, more preferably 4-20, and even more preferably 6-20.
  • the functional group possessed by the oligomer is a photopolymerizable functional group.
  • the photopolymerizable functional group is a carbon-carbon double bond such as an acryloyl group.
  • the glass transition temperature (Tg) of the oligomer is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and even more preferably 70 ° C. or higher.
  • the glass transition temperature (Tg) can be measured by differential scanning calorimetry (DSC), thermomechanical analysis (TMA), or the like.
  • the viscosity of the oligomer is not particularly limited, but the viscosity at 25 ° C. is preferably 100 to 10,000 mPa ⁇ s in consideration of the handleability of the active energy ray-curable composition and the influence on the viscosity. 1,000 mPa ⁇ s or less is preferable, and 1,000 mPa ⁇ s or less is more preferable.
  • the main chain of the oligomer can be polyepoxy, aliphatic polyurethane, aromatic polyurethane, aliphatic polyester, aromatic polyester, polyamine, polyacrylate and the like.
  • the aforementioned photopolymerizable functional group is preferably added to the main chain of the oligomer.
  • the functional group of the oligomer can be introduced by reacting the following (photopolymerizable) functional group-containing compound with the main chain of the oligomer.
  • (photopolymerizable) functional group-containing compounds include (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and other unsaturated carboxylic acids and their salts or esters, urethanes, amides and anhydrides thereof.
  • an N-vinyl compound may be included.
  • N-vinyl compounds include N-vinylformamide, N-vinylcarbazole, N-vinylacetamide, N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine, and derivatives thereof.
  • Tg glass transition temperature
  • the oligomer may be a linear oligomer, a branched oligomer, or a dendritic oligomer, but may be preferably a branched oligomer or a dendritic oligomer. Since the branched-chain oligomer and the dendritic oligomer have a relatively low viscosity, the hardness of the cured film can be increased although it is difficult to increase the viscosity of the active energy ray-curable offset ink.
  • a dendritic oligomer means an oligomer having a plurality of branched chains in one molecule.
  • dendritic oligomers examples include dendrimers, hyperbranched oligomers, star oligomers and graft oligomers.
  • Dendrimers, hyperbranched oligomers, star oligomers and graft oligomers may be known compounds. Among these, a dendrimer and a hyperbranched oligomer are preferable, and a hyperbranched oligomer is more preferable. Dendrimers and hyperbranched oligomers are less likely to increase the viscosity of active energy ray-curable offset inks.
  • Hyperbranched oligomer refers to an oligomer in which a plurality of photopolymerizable functional groups are bonded to an oligomer in which two or more monomers are bonded as repeating units. Hyperbranched oligomers generally contain a large number of photopolymerizable functional groups. Therefore, the hyperbranched oligomer can further increase the curing rate of the active energy ray-curable offset ink and can further increase the hardness of the cured film.
  • the number of photopolymerizable functional groups in one molecule of hyperbranched oligomer is preferably 6 or more.
  • hyperbranched oligomers examples include polyester 6-functional acrylate, polyester 9-functional acrylate, polyester 16-functional acrylate, and the like.
  • Examples of commercially available oligomer products include the following. CN131B, CN292, CN2272, CN2303, CN2304, CN968, CN972, CN975, CN978, CN980, CN981, CN983, CN989, CN991, CN992, CN994, CN996, CN299, C63, C299, C29 CN3211, CN9001, CN9002, CN9004, CN9005, CN9006, CN9007, CN9008, CN9009, CN9010, CN9011, CN9014, CN9026, CN9165, CN9178, CN9782, CN9788, PU2200 , PU 340, PU3420, PU610, PU620, PU664, MU9500, MU9800, SC2100, SC2152, SC2153, SC2565, PU460, PU640, MU3603, PE210, PE110, PE230, PE240,
  • examples of commercially available urethane oligomers include the following. CN968, CN972, CN975, CN978, CN980, CN981, CN983, CN989, CN991, CN992, CN994, CN996, CN997, CN999, CN1963, CN2901, CN2902, C3210, CN2921, C3210 CN9006, CN9007, CN9008, CN9009, CN9010, CN9011, CN9014, CN9026, CN9165, CN9178, CN9782, CN9783, CN9888 (manufactured by Sartomer), MIRAMER PU206, PU2100, PU2200, PU34020PU MU950 0, MU 9800, SC 2100, SC 2152, SC 2153, SC 2565, PU 460, PU 640, MU 3603 (manufactured by MIWON), EBECRYL 210,
  • the light source used in the curing method of the active energy ray-curable ink of the present invention is a combination of two or more light emitting diodes having different emission wavelengths.
  • the two types of light emitting diodes having different light emission wavelengths include a combination of light emitting diodes having light emission wavelengths of 200 to less than 350 nm and 350 to 420 nm.
  • UV-LED used as the active energy ray source used in the present invention is not particularly limited, and a conventionally known device can be used.
  • the generated energy rays using UV-LEDs are much more efficient in generating energy rays than using mercury lamps. Therefore, in order to irradiate a certain effective energy dose (energy dose that contributes to the curing of the coating film), the energy beam irradiation device using UV-LED is significantly smaller than the device using mercury lamp. Is possible. Further, in order to cure the ink coating film uniformly, it is important that the irradiation dose is uniform on the irradiation surface that can be irradiated during the energy ray irradiation.
  • UV-LEDs various expensive mirrors (reflectors) are used in mercury lamps, but in UV-LEDs, it is only necessary to install many small UV-LEDs. It is possible to design a line irradiation unit. By using such a UV-LED, it is possible to produce an active energy ray irradiation apparatus that is inexpensive and greatly reduced in weight. Furthermore, as described above, the mercury lamp has poor energy ray generation efficiency, so that the lamp close to the coating surface may be damaged in order to increase the energy ray irradiation efficiency. The surroundings of the glass part that is easily broken can be easily protected by other protective members.
  • UV-LEDs having an emission peak wavelength of 360 nm or less have a short lifetime and are expensive, so their penetration rate is moderate, but in response to the shortening of UV-LEDs that are expected to increase in the future. It is an object of the present invention to efficiently cure two or more types of light emitting diodes having different emission wavelengths.
  • the curing method of the active energy ray-curable offset ink of the present invention is an effective curing method by combining two or more light emitting diodes having a light emission wavelength of 200 to less than 350 nm and a light emission wavelength of 350 to 420 nm. It is possible to provide a method for curing an active energy ray-curable offset ink.
  • UV-LED used in the method of curing the active energy ray-curable offset ink of the present invention
  • an LED-type line UV irradiator UD90 (385 nm, 8 W / cm 2 ) manufactured by Panasonic Device Sunx, manufactured by Nikkiso Co., Ltd.
  • Deep UV LED SMD type (265 nm, 4 mW / cm 2 or 280 nm, 10 mW / cm 2 or 295 nm, 10 mW / cm 2 ), linear irradiation type UV-LED unit “LC-L5 LIGHTNING CUREL 11403-1112” (365 nm, manufactured by Hamamatsu Photonics) , 1.3W / cm 2), manufactured by Hamamatsu Photonics KK linear illuminated UV-LED unit "LC-L5 LIGHTNING CUREL11403-2112" (385nm, 1.5W / cm 2) , Phoseon TECHNOLO Y Co. water-cooled UV-LED unit "Fire Power” (365nm, 8W / cm 2 or 395nm, 8W / cm 2), and the like.
  • the photopolymerization initiator (II) is an essential component.
  • the total amount of the photopolymerization initiator (II) added is preferably in the range of 0.1 to 30% by weight, more preferably 1 to 15% by weight of the total amount of ink.
  • the photopolymerization initiator (II) used in the ink used in the method for curing the active energy ray-curable offset ink of the present invention includes the photopolymerization initiator (A) having an absorption wavelength of 200 to less than 350 nm and An active energy ray-curable ink containing a photopolymerization initiator (B) having an absorption wavelength of 350 to 420 nm is provided.
  • Examples of the photopolymerization initiator (A) include ⁇ (dimethyl) aminoalkylphenone compounds, ⁇ morpholino alkylphenone compounds, and acyl phosphine oxide compounds. These may be used alone or in combination of two or more.
  • the total amount of the photopolymerization initiator (A) added is preferably in the range of 0.1 to 30% by weight, more preferably 1 to 15% by weight of the total amount of ink.
  • Examples of the ⁇ (dimethyl) aminoalkylphenone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (number average molecular weight: 366.5), 2- (dimethylamino)- 2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (number average molecular weight: 380.5), and the like. It may be included, and may be used in combination.
  • the content of the above ⁇ (dimethyl) aminoalkylphenone compound in the ink composition is preferably in the range of 1 to 15% by weight based on the total amount of the ink.
  • the addition amount is less than 1% by weight, it is difficult to obtain good drying properties.
  • the addition amount exceeds 15% by weight, the initiator amount becomes excessive, and the degree of improvement in drying property is reduced.
  • the solubility of the agent in the liquid component in the ink is lowered and the ink fluidity is lowered.
  • Examples of the ⁇ -morpholinoalkylphenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-monoforinopropan-1-one (number average molecular weight: 279.4).
  • the content of the ⁇ -morpholinoalkylphenone compound in the ink composition is preferably in the range of 1 to 15% by weight based on the total amount of the ink. If the addition amount is less than 1% by weight, it is difficult to obtain good curability. If the addition amount exceeds 15% by weight, the amount of the initiator becomes excessive, and the ink fluidity is similarly impaired.
  • acylphosphine oxide compound examples include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) -phenyl Bisacylphosphine oxides such as sphinoxide,
  • 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis- (2,4,6-trimethylbenzoyl) -phenylphosphine oxide are 385 n And 395nm in that it has a UV absorption wavelength which matches the emission wavelength region of UV-LED having an emission wavelength, suitable curing property is obtained, and, more preferred from the viewpoint yellow cured film variable is small.
  • bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is preferably used in the range of 1 to 15% by weight based on the total amount of ink.
  • the addition amount is less than 1% by weight, there is almost no effect of improving curability. If the addition amount exceeds 15% by weight, the initiator amount becomes excessive, and further improvement in curability cannot be expected, and it is dissolved in the offset ink. This is not preferable because it is difficult to cause the ink to flow and deteriorates the storage stability due to a decrease in ink fluidity and precipitation.
  • the content of the acylphosphine oxide compound in the ink composition is preferably in the range of 1 to 15% by weight based on the total amount of the ink. If the addition amount is less than 1% by weight, it is difficult to obtain good curability. If the addition amount exceeds 15% by weight, the amount of the initiator becomes excessive, and the ink fluidity is similarly impaired.
  • Examples of the photopolymerization initiator (B) include hydroxyacetophenone compounds, benzophenone compounds excluding dialkylaminobenzophenone compounds, and ⁇ -hydroxyalkylphenone compounds. These may be used alone or in combination of two or more.
  • the total amount of the photopolymerization initiator (B) added is preferably in the range of 0.1 to 30% by weight, more preferably 1 to 15% by weight of the total amount of ink.
  • hydroxyacetophenone compound examples include IRGACURE® 184 (manufactured by BASF) 1-hydroxy-cyclohexyl-phenyl-ketone and the like.
  • the content of the hydroxyacetophenone compound in the ink composition is preferably in the range of 1 to 15% by weight based on the total amount of the ink. If the addition amount is less than 1% by weight, it is difficult to obtain good curability. If the addition amount exceeds 15% by weight, the amount of the initiator becomes excessive, and the ink fluidity is similarly impaired.
  • benzophenone compound excluding the dialkylaminobenzophenone compound examples include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, methyl-2-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl sulfide, 4- And phenylbenzophenone, Esacure 1001 (manufactured by Lamberti) 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfanyl) propan-1-one, and the like.
  • the content of the benzophenone compound in the ink composition is preferably in the range of 1 to 15% by weight with respect to the total amount of the ink.
  • An addition amount of less than 1% by weight is undesirable in that a further improvement in the curing rate cannot be obtained, and even if added in an amount exceeding 15% by weight, the effect of use is not recognized, which is not preferred.
  • ⁇ -hydroxyalkylphenone compound examples include DAROCUR 1173 (manufactured by BASF) 2-hydroxy-2-methyl-1-phenyl-propan-1-one, IRGACURE 2959 (manufactured by BASF) 1- [4- (2-hydroxy Ethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, IRGACURE 127 (manufactured by BASF) 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-) Propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one, ESACURE KIP 150 (manufactured by Lamberti) poly ⁇ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane -1-ON ⁇ , ESACURE KIP 160 (lamberti) ) 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methylpropionyl) phenoxy] phenyl ⁇ -2-
  • the content of the ⁇ -hydroxyketone compound in the ink composition is preferably in the range of 1 to 15% by weight based on the total amount of the ink.
  • An addition amount of less than 1% by weight is undesirable in that a further improvement in the curing rate cannot be obtained, and even if added in an amount exceeding 15% by weight, the effect of use is not recognized, which is not preferred.
  • a dialkylaminobenzophenone compound and / or a thioxanthone compound can be used as the photopolymerization initiator (III).
  • dialkylaminobenzophenone compound examples include 4,4′-bis- (dimethylamino) benzophenone, 4,4′-dialkylbenzophenones such as 4,4′-bis- (diethylamino) benzophenone, 4-benzoyl-4 ′. -Methyldiphenyl sulfide and the like.
  • 4,4′-bis (diethylamino) benzophenone (number average molecular weight 324.47) is excellent in curability.
  • thioxanthone compound examples include thioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and 2,4-dichlorothioxanthone.
  • 1-chloro-4-propoxythioxanthone and the like can be mentioned, and the amount of use is limited to a small amount in consideration of the yellowing property, but it is possible to suitably improve the film curability by using in combination.
  • a tertiary amine compound (excluding ⁇ -aminoalkylphenone compounds and dialkylaminobenzophenone compounds) is used as a hydrogen donor even if it does not have UV absorption characteristics that match the UV-LED emission wavelength region.
  • suitable active energy ray hardening can be obtained.
  • triethanolamine, methyldiethanolamine, triethylamine, dibutylethanolamine and the like as aliphatic amine derivatives and 2-dimethylaminoethylbenzoic acid, ethyl 2-dimethylaminobenzoate, 4-dimethylaminobenzoic acid as amines of benzoic acid derivatives.
  • amines of aniline derivatives include N, N-dihydroxyethylaniline, N, N-dimethylaniline, N, N-diethylaniline, and N, N-dimethyl-p-toluidine.
  • the content in the ink composition is preferably in the range of 0.1 to 10% by weight with respect to the total amount of the ink.
  • An addition amount of less than 0.1% by weight is undesirable in that a further improvement in the curing rate cannot be obtained, and even if added in an amount exceeding 10% by weight, the effect of use is not recognized, which is not preferred.
  • Examples of the color pigment used in the ink used in the method for curing the active energy ray-curable offset ink of the present invention include publicly known organic pigments for coloring.
  • Organic Pigment Handbook Author: Isao Hashimoto, Issuance Office: Color Office, 2006, first edition
  • the loss of ultraviolet energy that activates the photopolymerization initiator particularly in the case of black ink using carbon black having an extremely high ultraviolet absorbing ability in the range of 10 to 25% by weight.
  • the photopolymerization reaction at the bottom of the ink film is difficult to proceed as compared with other color pigments, and it is difficult to obtain sufficient curability.
  • the offset ink described in the present invention has 10 to 10 carbon blacks. It is possible to impart suitable curability to the black ink used at 25% by weight.
  • an ultraviolet curable ink in which the amount of carbon black added exceeds 25% by weight is not preferable because loss of ultraviolet energy due to carbon black becomes enormous and suitable drying properties cannot be obtained.
  • the average primary particle size of the carbon black is preferably in the range of 15 to 70 nm, and particularly preferably in the range of 20 to 40 nm. When the average primary particle size is less than 15 nm, the loss of ultraviolet energy due to carbon black becomes enormous, and it is not preferable because suitable drying properties cannot be obtained. When it exceeds 70 nm, the blackness of black ink is impaired. Is not preferable.
  • Examples of the carbon black include those produced by a known method such as a furnace method, a thermal method, a contact method, and the like. , Raven 1180, Raven 1255 (above, Colombian Chemical), Regal 400R, Regal 330R, Regal 660R, Mogul L (above, Cabot), MA7, MA8, MA11 (above, Mitsubishi Chemical) These may be used singly or in combination of two or more.
  • the printing substrate that can be used in the method of curing the active energy ray-curable offset ink of the present invention is not particularly limited.
  • paper such as fine paper, coated paper, art paper, imitation paper, thin paper, cardboard, and the like, Synthetic paper, polyester resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, nylon,
  • films or sheets such as polylactic acid and polycarbonate, cellophane, aluminum foil, and other various base materials conventionally used as printing base materials.
  • the production of the ink used for the curing method of the active energy ray-curable offset printing ink described in the present invention is the same as the conventional ultraviolet curable ink, the color pigment, the polymerizable acrylate monomer, the resin oligomer having a polymerization group, and the photopolymerization. It is manufactured by blending an initiator, a sensitizer, other additives, etc., stirring and mixing with a mixer, and then kneading using a dispersing machine such as a three-roll mill or a bead mill.
  • a base ink (Y) containing no photopolymerization initiator was prepared by mixing in accordance with the composition of Table 1 and kneading with a three-roll mill.
  • 20 weight% of phthalocyanine blue was added as a colorant pigment.
  • the active energy ray-polymerizable compound (I) having an ethylenic double bond 63.5% by weight of the total amount of the base ink, 10% by weight of the total amount of the base ink, diacryl phthalate resin (Daiso DAP A), viscosity and 1% by weight of talc, 1% by weight of clay, 1% by weight of magnesium carbonate, 1% by weight of calcium carbonate and 0.5% by weight of organic bentonite (total 4.5% by weight) as fluidity adjusting agents, 2 wax meters as auxiliary agents Weight percent was added.
  • the active energy ray polymerizable compound (I) having an ethylenic double bond and diallyl phthalate resin were dissolved in advance by applying heat at 120 ° C.
  • the active energy ray-curable ink thus obtained was uniformly applied to the RI tester rubber roll and metal roll using a simple color developing machine (RI tester, manufactured by Toyoe Seiko Co., Ltd.) and 0.10 ml of ink.
  • the surface of the coated paper (Oji Paper's “OK Top Coat Plus 57.5Kg, A size”) is placed on the surface of 200 cm 2 of Uezaki with an indigo density of 1.6 (SpectroEye densitometer manufactured by X-Rite). (Measurement) was developed so as to be uniformly applied, and a printed matter was produced.
  • the RI tester is a test machine that develops ink on paper or film, and can adjust the amount of ink transferred and the printing pressure.
  • UV-LED lamp light source having a wavelength range of 200 to 350 nm as a short wave and a UV-LED lamp light source having a wavelength range of 350 to 420 nm as a long wavelength
  • Irradiation was performed by three methods of X1 to X3.
  • Irradiation method X1 Two-lamp irradiation with short wave + long wave
  • Irradiation method X2 Irradiation with only long wave
  • Irradiation method X3 Irradiation with only short wave
  • Irgacure 907 2-methyl-1- [4- (methylthio) phenyl] -2-monoforinopropan-1-one, manufactured by BASF
  • Irgacure 369 2-benzyl-2-dimethylamino-1- (4-morphol Linophenyl) -butanone-1, manufactured by BASF
  • DAROCUR TPO 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, manufactured by BASF
  • Irgacure 184 1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF
  • EAB -SS 4,4'-bis (diethylamino) benzophenol
  • KY50 aromatic tertiary amine sensitizer, ethyl-4- (dimethylamino) benzoate, manufactured by Nippon Kayaku Co., Ltd.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Printing Methods (AREA)
  • Supply, Installation And Extraction Of Printed Sheets Or Plates (AREA)

Abstract

　Le problème de la présente invention concerne un procédé pour durcir une encre offset durcissable par un rayonnement d'énergie active, le procédé améliorant la productivité par d'excellentes propriétés de durcissement dans l'impression offset et étant approprié pour une impression. L'invention concerne un procédé pour le durcissement d'une encre durcissable par un rayonnement d'énergie active contenant (I) un composé polymérisable par un rayonnement d'énergie active présentant une double liaison éthylénique et (II) un initiateur de photopolymérisation, le procédé de durcissement d'une encre durcissable par un rayonnement d'énergie active étant caractérisé en ce qu'une source lumineuse utilisée pour le durcissement est une combinaison d'au moins deux types de diodes électroluminescentes présentant différentes longueurs d'onde d'émission de lumière.
PCT/JP2015/061419 2014-04-22 2015-04-14 Procédé pour le durcissement d'une encre offset durcissable par un rayonnement d'énergie active WO2015163184A1 (fr)

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JP2016210975A (ja) * 2015-05-01 2016-12-15 東京インキ株式会社 活性エネルギー線硬化型インキ、印刷物および食品包装用容器
JP2017095527A (ja) * 2015-11-18 2017-06-01 サカタインクス株式会社 活性エネルギー線硬化型オフセット印刷用インキ組成物
JP2018021138A (ja) * 2016-08-04 2018-02-08 Ｄｉｃグラフィックス株式会社 紫外線硬化型オフセットインキの硬化方法、及び該硬化方法を用いて印刷した印刷物
JP2018119062A (ja) * 2017-01-25 2018-08-02 株式会社カネカ 紫外線硬化性組成物およびその硬化物
US10510495B2 (en) * 2015-03-31 2019-12-17 Osaka Soda Co., Ltd. Electrochemical capacitor
JP7236578B1 (ja) 2022-03-29 2023-03-09 Ｄｉｃグラフィックス株式会社 活性エネルギー線硬化型オフセット印刷インキ、これを用いた印刷物、及び印刷物の製造方法

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JP2006274025A (ja) * 2005-03-29 2006-10-12 Seiko Epson Corp インク組成物及びそれを用いた記録装置
JP2006282756A (ja) * 2005-03-31 2006-10-19 Dainippon Ink & Chem Inc 紫外線硬化型インクジェット記録用インク組成物
JP2007112117A (ja) * 2005-08-17 2007-05-10 Fujifilm Corp 画像形成装置及び画像形成方法
JP2008188983A (ja) * 2006-12-25 2008-08-21 Seiko Epson Corp 紫外線照射装置および該紫外線照射装置を用いた記録装置、ならびに記録方法
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Publication number Priority date Publication date Assignee Title
US10510495B2 (en) * 2015-03-31 2019-12-17 Osaka Soda Co., Ltd. Electrochemical capacitor
JP2016210975A (ja) * 2015-05-01 2016-12-15 東京インキ株式会社 活性エネルギー線硬化型インキ、印刷物および食品包装用容器
JP2017095527A (ja) * 2015-11-18 2017-06-01 サカタインクス株式会社 活性エネルギー線硬化型オフセット印刷用インキ組成物
JP2018021138A (ja) * 2016-08-04 2018-02-08 Ｄｉｃグラフィックス株式会社 紫外線硬化型オフセットインキの硬化方法、及び該硬化方法を用いて印刷した印刷物
JP2018119062A (ja) * 2017-01-25 2018-08-02 株式会社カネカ 紫外線硬化性組成物およびその硬化物
JP7236578B1 (ja) 2022-03-29 2023-03-09 Ｄｉｃグラフィックス株式会社 活性エネルギー線硬化型オフセット印刷インキ、これを用いた印刷物、及び印刷物の製造方法
JP2023146160A (ja) * 2022-03-29 2023-10-12 Ｄｉｃグラフィックス株式会社 活性エネルギー線硬化型オフセット印刷インキ、これを用いた印刷物、及び印刷物の製造方法

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