WO2015163184A1 - Method for curing active-energy-ray-curable offset ink - Google Patents

Method for curing active-energy-ray-curable offset ink 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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WIPO (PCT)
Prior art keywords
curing
active energy
energy ray
compound
ink
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PCT/JP2015/061419
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French (fr)
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/en
Publication of WO2015163184A1 publication Critical patent/WO2015163184A1/en

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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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Abstract

　The present invention addresses the problem of providing a method for curing an active-energy-ray-curable offset ink, the method enhancing productivity by excellent curing properties in offset printing, and being suitable for printing. A method for curing an active-energy-ray-curable ink containing (I) an active-energy-ray-polymerizable compound having an ethylenic double bond and (II) a photopolymerization initiator, the method for curing an active-energy-ray-curable ink characterized in that a light source used for curing is a combination of at least two types of light-emitting diodes having different light emission wavelengths.

Description

活性エネルギー線硬化型オフセットインキの硬化方法Curing method of active energy ray-curable offset ink
　本発明は、活性エネルギー線照射により硬化するオフセット用インキの硬化方法に関する。さらには、該インキの硬化方法に用いるインキ、及びそのインキを用いた印刷物に関する。 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.
　活性エネルギー線硬化型オフセットインキは瞬間硬化の特性の利便性から、紙器等のパッケージ印刷の分野で広く使用されている。 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.
　現在広く使用されており活性エネルギー線としては、２００～４２０ｎｍの波長を発光する高圧水銀灯や、メタルハライドランプ、若しくは、単一波長発光型（３６５ｎｍ、３８５ｎｍ、３９５ｎｍ、４０５ｎｍ）の発光ダイオードである（例えば、特許文献１～３参照）。 Currently used as active energy rays are high-pressure mercury lamps emitting a wavelength of 200 to 420 nm, metal halide lamps, or light emitting diodes of single wavelength emission type (365 nm, 385 nm, 395 nm, 405 nm) (for example, Patent Documents 1 to 3).
　中でも、単一波長発光型ダイオードは、発熱性に優れ、各種産業で採用されているが、限定された波長域を用いる単一波長発光型ダイオードは、広域波長の紫外線を発する紫外線ランプ光源等と比較して紫外線エネルギーの発光波長幅が狭く、使用できる光重合開始剤が限定され、塗膜の最表面を硬化させることが困難であるため、速硬化性に対する対応が望まれている。 Among them, the single wavelength light emitting diode is excellent in heat generation and is used in various industries. However, 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. Compared to the narrow wavelength range of ultraviolet energy emission, the photopolymerization initiators that can be used are limited, and it is difficult to cure the outermost surface of the coating film.
　近年になり、発光ダイオードメーカー各社から、３５０ｎｍ未満のダイオードが発表されており、今後、２００～３４９ｎｍの発光ダイオードと３５０～４２０ｎｍの発光ダイオードを合わせた製品の登場が予想され、これらに対応したオフセットインキに必要とされるより高い硬化性を可能とさせたのが本発明である。 In recent years, light emitting diode manufacturers have announced diodes of less than 350 nm, and in the future, products that combine 200 to 349 nm light emitting diodes with 350 to 420 nm light emitting diodes are expected, and offsets corresponding to these It is the present invention that allows for the higher curability required for the ink.
特許４２８９４４１号Japanese Patent No. 4289441 特許４９３０６３０号Patent 4930630 特許５１５８２７４号Japanese Patent No. 5158274
　本発明の課題は、オフセット印刷における優れた硬化性による生産性向上及び印刷適性を有する活性エネルギー線硬化型オフセットインキの硬化方法を提供することにある。 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.
　本発明者らは、特定の活性エネルギー線重合性化合物と光重合開始剤を含有する活性エネルギー線硬化型インキの硬化手段として、発光波長の異なる２種以上の発光ダイオードを組み合わせることで上記課題を達成できることを見出し、本発明に至った。 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.
　すなわち本発明は、エチレン性二重結合を有する活性エネルギー線重合性化合物（Ｉ）と光重合開始剤（ＩＩ）を含有する活性エネルギー線硬化型インキの硬化方法であって、硬化に使用する光源が発光波長の異なる発光ダイオードを２種以上組み合わせたものであることを特徴とする活性エネルギー線硬化型インキの硬化方法に関する。 That is, 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.
　本発明は、更に、前記発光ダイオードの発光波長が２００～３５０ｎｍ未満と、３５０～４２０ｎｍである活性エネルギー線硬化型インキの硬化方法に関する。 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.
　本発明は、更に、前記光重合開始剤（ＩＩ）が２００～３５０ｎｍ未満の吸収波長を持つ光重合開始剤（Ａ）及び３５０～４２０ｎｍの吸収波長を持つ光重合開始剤（Ｂ）である活性エネルギー線硬化型インキの硬化方法に関する。 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.
　本発明は、更に、前記光重合開始剤（Ａ）が下記の（Ａ）群から選ばれる少なくとも１種以上を含有する活性エネルギー線硬化型インキの硬化方法に関する。
（Ａ）群　α（ジメチル）アミノアルキルフェノン化合物、
　　　　　αモルフォリノアルキルフェノン化合物、
　　　　　アシルフォスフィンオキサイド化合物 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 α (dimethyl) aminoalkylphenone compound,
α-morpholinoalkylphenone compound,
Acylphosphine oxide compounds
　本発明は、更に、前記光重合開始剤（Ｂ）が下記の（Ｂ）群から選ばれる少なくとも１種以上を含有する活性エネルギー線硬化型インキの硬化方法に関する。
（Ｂ）群　ヒドロキシアセトフェノン化合物、
　　　　　ジアルキルアミノベンゾフェノン化合物を除くベンゾフェノン化合物、
　　　　　αヒドロキシアルキルフェノン化合物 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,
α-Hydroxyalkylphenone compounds
　本発明は、更に、光重合開始剤（ＩＩＩ）として、ジアルキルアミノベンゾフェノン化合物及び／又はチオキサントン化合物を含有する活性エネルギー線硬化型インキの硬化方法に関する。 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).
　本発明は、更に、前記活性エネルギー線硬化型インキ硬化方法に用いるインキ、及びそのインキを用いて印刷した印刷物をも提供する。 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.
　本発明によれば、高い硬化性を発現した活性エネルギー線硬化型オフセットインキの硬化方法、その硬化方法に用いるインキ、及びそれを用いた印刷物を提供できる。 According to 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.
　本発明は、エチレン性二重結合を有する活性エネルギー線重合性化合物（Ｉ）と光重合開始剤（ＩＩ）を含有する活性エネルギー線硬化型インキの硬化方法であって、硬化に使用する光源が発光波長の異なる発光ダイオードを２種以上組み合わせることで目的とする本発明の効果を奏するものである。 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.
　本発明の活性エネルギー線硬化型インキの硬化方法に用いるインキは、エチレン性二重結合を有する活性エネルギー線重合性化合物（Ｉ）を必須成分とする。具体例としては、下記のような活性エネルギー線重合性化合物を挙げることができる。
〔エチレン性二重結合を有する活性エネルギー線重合性化合物（Ｉ）〕
　本発明の活性エネルギー線硬化型インキの硬化方法に用いるインキで使用するエチレン性二重結合を有する活性エネルギー線重合性化合物（Ｉ）としては、通常活性エネルギー線硬化性組成物に使用される公知の（メタ）アクリルモノマーおよび／または（メタ）アクリルオリゴマーから任意に選んで用いることができる。なお本発明において「（メタ）アクリル」とはアクリルとメタクリルとを総称したものである。
　（メタ）アクリルモノマーとしては、例えばアクリル酸やメタクリル酸などの不飽和カルボン酸又はそのエステル、例えばアルキル－、シクロアルキル－、ハロゲン化アルキル－、アルコキシアルキル－、ヒドロキシアルキル－、アミノアルキル－、アリル－、グリシジル－、ベンジル－、フェノキシ－（メタ）アクリレート、アルキレングリコール、ポリオキシアルキレングリコールのモノ又はジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレートなど、（メタ）アクリルアミド又はその誘導体、例えばアルキル基やヒドロキシアルキル基でモノ置換又はジ置換された（メタ）アクリルアミド、ジアセトン（メタ）アクリルアミド、Ｎ，Ｎ’－アルキレンビス（メタ）アクリルアミドなど、アリル化合物、例えばアリルアルコール、アリルイソシアネート、ジアリルフタレート、トリアリルイソシアヌレートなどを挙げることができる。 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. In the present invention, “(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. -, Glycidyl-, benzyl-, phenoxy- (meth) acrylate, alkylene glycol, mono or di (meth) acrylate of polyoxyalkylene glycol, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, (Meth) acrylamide or a derivative thereof, for example, (meth) acrylamide, diacetone (meth) acrylamide, N, N′-alkylenebis (meth) monosubstituted or disubstituted with an alkyl group or a hydroxyalkyl group T) Acrylamide and allyl compounds such as allyl alcohol, allyl isocyanate, diallyl phthalate, triallyl isocyanurate and the like.
　（メタ）アクリルモノマーの他の例としては、エチレングリコール単位を分子内にもつポリエチレングリコール（ｎは３以上であり、およそ１４以下）ジ（メタ）アクリレート、トリメチロールプロパンＥＯ変性（ｎは３以上であり、およそ１４以下）トリ（メタ）アクリレート、フェノールＥＯ変性（ｎは３以上であり、およそ１４以下）（メタ）アクリレートや、水酸基を分子内にもつ２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、フタル酸モノヒドロキシエチル（メタ）アクリレートなどを挙げることができる。
　これらの（メタ）アクリルモノマーは単独で用いてもよいし２種以上組み合わせて用いてもよい。 As another example of 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.
　また、硬化収縮が支障となる用途の場合には、例えばイソボルニル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、ジシクロペンテノキシエチル（メタ）アクリレート、ジシクロペンテノキシプロピル（メタ）アクリレートなど、ジエチレングリコールジシクロペンテニルモノエーテルのアクリル酸エステル又はメタクリル酸エステル、ポリオキシエチレン若しくはポリプロピレングリコールジシクロペンテニルモノエーテルのアクリル酸エステル又はメタクリル酸エステルなど、ジシクロペンテニルシンナメート、ジシクロペンテノキシエチルシンナメート、ジシクロペンテノキシエチルモノフマレート又はジフマレートなど、３，９－ビス（１，１－ビスメチル－２－オキシエチル）－スピロ［５，５］ウンデカン、３，９－ビス（１，１－ビスメチル－２－オキシエチル）－２，４，８，１０－テトラオキサスピロ［５，５］ウンデカン、３，９－ビス（２－オキシエチル）－スピロ［５，５］ウンデカン、３，９－ビス（２－オキシエチル）－２，４，８，１０－テトラオキサスピロ［５，５］ウンデカンなどのモノマ－、ジアクリレート又はモノ－、ジメタアクリレート、あるいはこれらのスピログリコールのエチレンオキシド又はプロピレンオキシド付加重合体のモノ－、ジアクリレート、又はモノ－、ジメタアクリレート、あるいは前記モノ（メタ）アクリレートのメチルエーテル、１－アザビシクロ［２，２，２］－３－オクテニル（メタ）アクリレート、ビシクロ［２，２，１］－５－ヘプテン－２，３－ジカルボキシルモノアリルエステルなど、ジシクロペンタジエニル（メタ）アクリレート、ジシクロペンタジエニルオキシエチル（メタ）アクリレート、ジヒドロジシクロペンタジエニル（メタ）アクリレートなどの（メタ）アクリルモノマーを用いることができる。
　これらの活性エネルギー線重合性化合物は単独で用いてもよいし２種以上組み合わせて用いてもよい。 In addition, in the case of applications where curing shrinkage is an obstacle, for example, isobornyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentenoxyethyl (meth) acrylate, dicyclopentenoxypropyl (meth) acrylate, etc. Acrylic ester or methacrylic ester of diethylene glycol dicyclopentenyl monoether, acrylic ester or methacrylic ester of polyoxyethylene or polypropylene glycol dicyclopentenyl monoether, dicyclopentenyl cinnamate, dicyclopentenoxyethyl cinnamate 3,9-bis (1,1-bismethyl-2-oxyethyl) -spiro [5,5] undecane, such as dicyclopentenoxyethyl monofumarate or difumarate, Bis (1,1-bismethyl-2-oxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (2-oxyethyl) -spiro [5,5] undecane, Monomers such as 3,9-bis (2-oxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, diacrylate or mono-, dimethacrylate, or ethylene oxide of these spiroglycols Or propylene oxide addition polymer mono-, diacrylate, or mono-, dimethacrylate, or methyl ether of the mono (meth) acrylate, 1-azabicyclo [2,2,2] -3-octenyl (meth) acrylate Bicyclo [2,2,1] -5-heptene-2,3-dicarboxyl monoallyl ester, etc. It can be used cyclopentadienyl (meth) acrylate, dicyclopentadienyl oxyethyl (meth) acrylate, dihydrodicyclopentadienyl (meth) acrylate such as a (meth) acrylic monomer.
These active energy ray polymerizable compounds may be used alone or in combination of two or more.
　本発明に特に好適な活性エネルギー線重合性化合物としては、例えば、メチル、エチル、プロピル、ブチル、アミル、２－エチルヘキシル、イソオクチル、ノニル、ドデシル、ヘキサデシル、オクタデシル、シクロヘキシル、ベンジル、メトキシエチル、ブトキシエチル、フェノキシエチル、ノニルフェノキシエチル、グリシジル、ジメチルアミノエチル、ジエチルアミノエチル、イソボルニル、ジシクロペンタニル、ジシクロペンテニル、ジシクロペンテニロキシエチル等の置換基を有する（メタ）アクリレート、ω-カルボキシ-ポリカプロラクトンモノアクリレート、フタル酸モノヒドロキシエチルアクリレート、２－ヒドロキシ－３－フェノキシプロピルアクリレート、ビニルピロリドン、Ｎ－アクリロイルモルホリン、Ｎ－ビニルホルムアミド等の１官能モノマー、 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. (Meth) acrylate having a substituent such as phenoxyethyl, nonylphenoxyethyl, glycidyl, dimethylaminoethyl, diethylaminoethyl, isobornyl, dicyclopentanyl, dicyclopentenyl, dicyclopentenyloxyethyl, ω-carboxy-poly Caprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, vinylpyrrolidone, N-acryloylmorpholine, N-vinylphenol Monofunctional monomers such as lumamide,
　１，３－ブチレングリコール、１，４－ブタンジオール、１，５－ペンタンジオール、３－メチル－１，５－ペンタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコール、１，８－オクタンジオール、１，９－ノナンジオール、トリシクロデカンジメタノール、エチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、ポリプロピレングリコール等のジ（メタ）アクリレート、トリス（２－ヒドロキシエチル）イソシアヌレートのジ（メタ）アクリレート、（メタ）アクリル酸２－（２－ビニロキシエトキシ）エチル、オペンチルグリコール１モルに４モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たジオールのジ（メタ）アクリレート、ビスフェノールＡ１モルに２モルのエチレンオキサイドもしくはプロピレンオキサイドを付加して得たジオールのジ（メタ）アクリレート、トリメチロールプロパン１モルに３モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たトリオールのジまたはトリ（メタ）アクリレート、ビスフェノールＡ１モルに４モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たジオールのジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート，ペンタエリスリトールトリ（メタ）アクリレート，ジペンタエリスリトールのポリ（メタ）アクリレート、エチレンオキサイド変性リン酸（メタ）アクリレート、エチレンオキサイド変性アルキルリン酸（メタ）アクリレート等の多官能モノマーを挙げることができる。これらは２種類以上併用して用いることができる。 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, tricyclodecane dimethanol, ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol and other di (meth) acrylates, tris (2-hydroxyethyl) isocyanurate Di (meth) acrylate of a diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of di (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, and 1 mol of pentyl glycol Lilate, di (meth) acrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane Di (tri) methacrylate, di (meth) acrylate obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, dipentaerythritol poly (meth) acrylate, ethylene oxide modified phosphoric acid (meth) acrylate, ethylene oxide modified alkyl phosphoric acid (meth) acrylate Mention may be made of a multi-functional monomer. Two or more of these can be used in combination.
（（メタ）アクリルオリゴマー）
　実施形態に係る活性エネルギー線硬化性インキに含有されるオリゴマーは、光の照射により架橋又は重合する化合物である。また、モノマーの重合体を主鎖とする化合物であるが、主鎖を構成するモノマーの数は限定されない。前記オリゴマーの分子量は、５００～２０，０００の範囲であることが好ましい。 ((Meth) acrylic oligomer)
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.
　オリゴマーの官能基数は２～２０であることが好ましく、４～２０であることがより好ましく、６～２０であるとさらに好ましい。オリゴマーが有する官能基とは光重合性官能基である。光重合性官能基とは、アクリロイル基などの炭素－炭素の二重結合などである。官能基数が多いと、硬化性オリゴマーの硬化感度が高まり、かつ硬化塗膜の硬度も高まる。一方で、官能基数が多すぎると、硬化塗膜の収縮が生じやすくなり、塗膜表面が歪みやすくなる。 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. When the number of functional groups is large, the curing sensitivity of the curable oligomer increases and the hardness of the cured coating film also increases. On the other hand, when the number of functional groups is too large, shrinkage of the cured coating film tends to occur, and the coating film surface is easily distorted.
　オリゴマーのガラス転移温度（Ｔｇ）は４０℃以上であることが好ましく、５０℃以上であるとより好ましく、７０℃以上であると更に好ましい。ガラス転移温度（Ｔｇ）の測定は示差走査熱量測定（ＤＳＣ）、熱機械分析（ＴＭＡ）等で測定することができる。 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.
　オリゴマーの粘度は特に制限はないが、活性エネルギー線硬化性組成物取扱性および粘度への影響を考慮して、２５℃での粘度が、１００～１０，０００ｍＰａ・ｓであることが好ましく、５，０００ｍＰａ・ｓ以下が好ましく、１，０００ｍＰａ・ｓ以下がより好ましい。 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.
　オリゴマーの主鎖は、ポリエポキシ、脂肪族ポリウレタン、芳香族ポリウレタン、脂肪族ポリエステル、芳香族ポリエステル、ポリアミン、ポリアクリレートなどでありうる。オリゴマーの主鎖に、前述の光重合性官能基が付加していることが好ましい。 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.
　オリゴマーの官能基は、オリゴマーの主鎖に以下の（光重合性）官能基含有化合物を反応させて導入することができる。（光重合性）官能基含有化合物の例には、（メタ）アクリル酸、イタコン酸、クロトン酸、イソクロトン酸及びマレイン酸等の不飽和カルボン酸やそれらの塩又はエステル、ウレタン、アミド及びその無水物、アクリロニトリル、スチレン、種々の不飽和ポリエステル、不飽和ポリエーテル、不飽和ポリアミド、並びに不飽和ウレタンが挙げられる。その他にＮ－ビニル化合物を含んでいてもよい。Ｎ－ビニル化合物には、Ｎ－ビニルフォルムアミド、Ｎ－ビニルカルバゾール、Ｎ－ビニルアセトアミド、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム、アクリロイルモルホリン、及びそれらの誘導体などが含まれる。 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. Examples of (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. Products, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes. In addition, 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.
　オリゴマーのガラス転移温度（Ｔｇ）を高くするには、オリゴマーの主鎖に芳香環やアミド構造等を導入して、主鎖構造を剛直にしたり、オリゴマーの側鎖に大きな置換基を導入したりすればよい。 In order to increase the glass transition temperature (Tg) of the oligomer, an aromatic ring or an amide structure is introduced into the main chain of the oligomer to make the main chain rigid, or a large substituent is introduced into the side chain of the oligomer. do it.
　オリゴマーは、直鎖状オリゴマーであっても、分岐鎖状オリゴマーであっても、樹枝状オリゴマーであってもよいが、分岐鎖状オリゴマーまたは樹枝状オリゴマーであることが好ましい場合がある。分岐鎖状オリゴマーおよび樹枝状オリゴマーは、比較的低粘度であるため、活性エネルギー線硬化型オフセットインキの粘度を上昇させにくいにも係わらず、硬化膜の硬度を高めることができる。樹枝状オリゴマーとは、１分子中に複数の分岐鎖を有するオリゴマーを意味する。 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.
　樹枝状オリゴマーの例には、デンドリマー、ハイパーブランチオリゴマー、スターオリゴマー及びグラフトオリゴマーなどが含まれる。デンドリマー、ハイパーブランチオリゴマー、スターオリゴマー及びグラフトオリゴマーは、公知の化合物でありうる。これらのなかでも、デンドリマー及びハイパーブランチオリゴマーであることが好ましく、ハイパーブランチオリゴマーがより好ましい。デンドリマーやハイパーブランチオリゴマーは、活性エネルギー線硬化型オフセットインキの粘度をより上昇させにくい。 Examples of dendritic oligomers 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.
　ハイパーブランチオリゴマーは、２個以上のモノマーが繰り返し単位として結合したオリゴマーに複数の光重合性官能基が結合したオリゴマーをいう。ハイパーブランチオリゴマーには、一般に多数の光重合性官能基が含まれる。そのため、ハイパーブランチオリゴマーは、活性エネルギー線硬化型オフセットインキの硬化速度を一層高めることができ、硬化膜の硬度も一層高めることができる。一分子のハイパーブランチオリゴマーが有する光重合性官能基の数は、６以上であることが好ましい。 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.
　ハイパーブランチオリゴマーの例には、ポリエステル６官能アクリレート、ポリエステル９官能アクリレート、ポリエステル１６官能アクリレートなどが含まれる。 Examples of hyperbranched oligomers include polyester 6-functional acrylate, polyester 9-functional acrylate, polyester 16-functional acrylate, and the like.
　オリゴマーの市販品の例には以下のものがある。
　ＣＮ１３１Ｂ、ＣＮ２９２、ＣＮ２２７２、ＣＮ２３０３、ＣＮ２３０４、ＣＮ９６８、ＣＮ９７２、ＣＮ９７５、ＣＮ９７８、ＣＮ９８０、ＣＮ９８１、ＣＮ９８３、ＣＮ９８９、ＣＮ９９１、ＣＮ９９２、ＣＮ９９４、ＣＮ９９６、ＣＮ９９７、ＣＮ９９９、ＣＮ１９６３、ＣＮ２９０１、ＣＮ２９０２、ＣＮ２９２０、ＣＮ２９２１、ＣＮ３２１０、ＣＮ３２１１、ＣＮ９００１、ＣＮ９００２、ＣＮ９００４、ＣＮ９００５、ＣＮ９００６、ＣＮ９００７、ＣＮ９００８、ＣＮ９００９、ＣＮ９０１０、ＣＮ９０１１、ＣＮ９０１４、ＣＮ９０２６、ＣＮ９１６５、ＣＮ９１７８、ＣＮ９７８２、ＣＮ９７８３、ＣＮ９７８８、ＣＮ９８９３（以上サートマー社製）、ＭＩＲＡＭＥＲ　ＰＵ２０６、ＰＵ２１００、ＰＵ２２００、ＰＵ３４０、ＰＵ３４２０、ＰＵ６１０、ＰＵ６２０、ＰＵ６６４、ＭＵ９５００、ＭＵ９８００、ＳＣ２１００、ＳＣ２１５２、ＳＣ２１５３、ＳＣ２５６５、ＰＵ４６０、ＰＵ６４０、ＭＵ３６０３、ＰＥ２１０、ＰＥ１１０、ＰＥ２３０、ＰＥ２４０、ＰＥ３２０、ＥＡ２２３５、ＥＡ２２５５、ＥＡ２２５９、ＥＡ２２８０、ＰＳ４２０、ＰＳ４６０、ＰＳ４６１０、ＰＳ６１０(以上ＭＩＷＯＮ社製)、ＥＢＥＣＲＹＬ　２１０、２２０、２３０、２７０、５１２９、８２１０、８３０１、８８０４、８８０７、９２６０、４８５８、８４０２、９２７０、９２７０、８３１１、８７０１(以上ダイセルオルネクス社製)  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, PE320, EA2235, EA2255, EA2259, EA2280, PS420 PS4610, PS610 (above made by MIWON), EBECRYL 210, 220, 230, 270, 5129, 8210, 8301, 8804, 8807, 9260, 4858, 8402, 9270, 9270, 8311, 8701 (above made by Daicel Ornex)
　なかでも、ウレタンオリゴマーの市販品の例には以下のものがある。
ＣＮ９６８、ＣＮ９７２、ＣＮ９７５、ＣＮ９７８、ＣＮ９８０、ＣＮ９８１、ＣＮ９８３、ＣＮ９８９、ＣＮ９９１、ＣＮ９９２、ＣＮ９９４、ＣＮ９９６、ＣＮ９９７、ＣＮ９９９、ＣＮ１９６３、ＣＮ２９０１、ＣＮ２９０２、ＣＮ２９２０、ＣＮ２９２１、ＣＮ３２１０、ＣＮ３２１１、ＣＮ９００１、ＣＮ９００２、ＣＮ９００４、ＣＮ９００５、ＣＮ９００６、ＣＮ９００７、ＣＮ９００８、ＣＮ９００９、ＣＮ９０１０、ＣＮ９０１１、ＣＮ９０１４、ＣＮ９０２６、ＣＮ９１６５、ＣＮ９１７８、ＣＮ９７８２、ＣＮ９７８３、ＣＮ９７８８、ＣＮ９８９３（以上サートマー社製）、ＭＩＲＡＭＥＲ　ＰＵ２０６、ＰＵ２１００、ＰＵ２２００、ＰＵ３４０、ＰＵ３４２０、ＰＵ６１０、ＰＵ６２０、ＰＵ６６４、ＭＵ９５００、ＭＵ９８００、ＳＣ２１００、ＳＣ２１５２、ＳＣ２１５３、ＳＣ２５６５、ＰＵ４６０、ＰＵ６４０、ＭＵ３６０３(以上ＭＩＷＯＮ社製)、ＥＢＥＣＲＹＬ　２１０、２２０、２３０、２７０、５１２９、８２１０、８３０１、８８０４、８８０７、９２６０、４８５８、８４０２、９２７０、９２７０、８３１１、８７０１(以上ダイセルオルネクス社製)  Among these, 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, 220, 230, 270, 5129, 8210, 8301, 8804, 8807, 9260, 4858, 8402, 9270 9270, 8311, 8701 (manufactured by Daicel Ornex)
　本発明の活性エネルギー線硬化型インキの硬化方法に使用する光源は、発光波長の異なる発光ダイオードを２種以上組み合わせたものである。 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.
　そして、前記発光波長の異なる発光ダイオードを２種とは、発光波長が２００～３５０ｎｍ未満と、３５０～４２０ｎｍである発光ダイオードの組合せを挙げることができる。 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）
　本発明で用いる活性エネルギー線源として用いるＵＶ－ＬＥＤとしては、特に制限はなく、従来公知の装置を使用することができる。ＵＶ－ＬＥＤを使用した発生エネルギー線は、水銀灯を使用した場合と比べ、エネルギー線の発生効率がはるかに優れている。従って、一定の有効エネルギー線量（塗膜の硬化に寄与するエネルギー線量）を照射するために、ＵＶ－ＬＥＤを使用したエネルギー線照射装置は、水銀灯を使用した装置と比較して、大幅に小型化が可能である。また、均一にインキ塗膜を硬化するためには、エネルギー線照射時に照射可能な照射面において、照射線量が均一であることが重要である。このため、水銀灯では、各種の高価なミラー（反射板）を使用することが行われるが、ＵＶ－ＬＥＤでは、小さなＵＶ－ＬＥＤを多数設置するだけでよいので、エネルギー線照射線量の均一なエネルギー線照射部を設計することが可能である。このようなＵＶ－ＬＥＤを使用すれば、安価で、大幅に軽量化された活性エネルギー線照射装置を作製することができる。さらに、上述のように水銀灯はエネルギー線の発生効率がよくないので、エネルギー線照射効率を上げるために塗膜面に近づけたランプが破損することが起こるが、ＵＶ－ＬＥＤでは、その構造上、破損しやすいガラス部のまわりは容易に他の保護部材で保護可能である。 (UV-LED)
The 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. For this reason, 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.
　加えて、３６０ｎｍ以下の発光ピーク波長を有するＵＶ－ＬＥＤは寿命が短く、高価であることからその普及率は緩やかではあるが、今後増加が予測されるＵＶ－ＬＥＤの短波長化に対応しつつ、発光波長の異なる発光ダイオードを２種以上組み合わせたて効率よく硬化させることが本願発明の目的である。 In addition, 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.
　更に、本発明の活性エネルギー線硬化型オフセットインキの硬化方法は、前記発光ダイオードの発光波長が２００～３５０ｎｍ未満と、３５０～４２０ｎｍである発光波長の異なる発光ダイオードを２種以上組み合わせて効率よく硬化する活性エネルギー線硬化型オフセットインキの硬化方法を提供することができる。 Furthermore, 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.
　本発明の活性エネルギー線硬化型オフセットインキの硬化方法に使用するＵＶ－ＬＥＤの具体例としては、パナソニックデバイスＳＵＮＸ社製ＬＥＤ方式ライン型ＵＶ照射器ＵＤ９０（３８５ｎｍ、８Ｗ／ｃｍ２）、日機装社製深紫外線ＬＥＤ ＳＭＤタイプ（２６５ｎｍ、４ｍＷ／ｃｍ２ または ２８０ｎｍ、１０ｍＷ／ｃｍ２ または ２９５ｎｍ、１０ｍＷ／ｃｍ２）、浜松ホトニクス社製リニア照射型ＵＶ－ＬＥＤユニット「ＬＣ－Ｌ５　 ＬＩＧＨＴＮＩＮＧ ＣＵＲＥＬ１１４０３－１１１２」（３６５ｎｍ、１．３Ｗ／ｃｍ２）、浜松ホトニクス社製リニア照射型ＵＶ－ＬＥＤユニット「ＬＣ－Ｌ５　 ＬＩＧＨＴＮＩＮＧ ＣＵＲＥＬ１１４０３－２１１２」（３８５ｎｍ、１．５Ｗ／ｃｍ２）、Ｐｈｏｓｅｏｎ　ＴＥＣＨＮＯＬＯＧＹ社製水冷式ＵＶ－ＬＥＤユニット「Ｆｉｒｅ　Ｐｏｗｅｒ」（３６５ｎｍ、８Ｗ／ｃｍ２または３９５ｎｍ、８Ｗ／ｃｍ２）等が挙げられる。 As a specific example of the 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.
　本発明の活性エネルギー線硬化型オフセットインキの硬化方法に用いるインキでは、光重合開始剤（ＩＩ）を必須成分とする。 In the ink used for the curing method of the active energy ray-curable offset ink of the present invention, the photopolymerization initiator (II) is an essential component.
　前記光重合開始剤（ＩＩ）の添加量の総計は、インキ全量の０．１～３０重量％の範囲にあることが好ましく、より好ましくは１～１５重量％である。 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.
　更に、本発明の活性エネルギー線硬化型オフセットインキの硬化方法に用いるインキで使用する前記前記光重合開始剤（ＩＩ）としては、２００～３５０ｎｍ未満の吸収波長を持つ光重合開始剤（Ａ）及び３５０～４２０ｎｍの吸収波長を持つ光重合開始剤（Ｂ）を含有する活性エネルギー線硬化型インキを提供する。 Further, 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.
　前記光重合開始剤（Ａ）としては、α（ジメチル）アミノアルキルフェノン化合物、αモルフォリノアルキルフェノン化合物、アシルフォスフィンオキサイド化合物を挙げることができる。これらは単独で用いてもよいし２種類以上添加しても良い。 Examples of the photopolymerization initiator (A) include α (dimethyl) aminoalkylphenone compounds, α morpholino alkylphenone compounds, and acyl phosphine oxide compounds. These may be used alone or in combination of two or more.
　尚、前記光重合開始剤（Ａ）の添加量の総計は、インキ全量の０．１～３０重量％の範囲にあることが好ましく、より好ましくは１～１５重量％である。 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.
　前記α（ジメチル）アミノアルキルフェノン化合物としては、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノンー１（数平均分子量：３６６．５）、２－（ジメチルアミノ）－２－（４－メチル－ベンジル）－１－（４－モルフォリン－４－イル－フェニル）－ブタン－１－オン（数平均分子量：３８０．５）等が挙げられ、これらはどちらか１つ含まれればよく、両方組み合わせて用いてもよい。 Examples of the α (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.
　前記したα（ジメチル）アミノアルキルフェノン化合物のインキ組成物中の含有率は、インキ全量に対し１～１５重量％の範囲にあることが好ましい。１重量％未満の添加量では良好な乾燥性を得ることが困難であり、また１５重量％を超える添加量では、開始剤量が過剰となり、乾燥性の向上度合いが低下するだけでなく、開始剤のインキ中液体成分への溶解性が低下しインキ流動性が低下する。 The content of the above α (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. When the addition amount is less than 1% by weight, it is difficult to obtain good drying properties. When 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.
　前記αモルフォリノアルキルフェノン化合物としては、２－メチル－１－［４－（メチルチオ）フェニル］－２－モノフォリノプロパン－１－オン（数平均分子量：２７９．４）等が挙げられる。 Examples of the α-morpholinoalkylphenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-monoforinopropan-1-one (number average molecular weight: 279.4).
　前記したαモルフォリノアルキルフェノン化合物のインキ組成物中の含有率は、インキ全量に対し１～１５重量％の範囲にあることが好ましい。１重量％未満の添加量では良好な硬化性を得ることが困難であり、また１５重量％を超える添加量では、開始剤量が過剰となり、同様にインキ流動性を損なうことから好ましくない。 The content of the α-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.
　前記アシルフォスフィンオキサイド化合物としては、ビス－（２，６－ジクロロベンゾイル）フェニルフォスフィンオキサイド、ビス－（２，６－ジクロロベンゾイル）－２，５－ジメチルフェニルフォスフィンオキサイド、ビス－（２，６－ジクロロベンゾイル）－４－プロピルフェニルフォスフィンオキサイド、ビス－（２，６－ジクロロベンゾイル）－１－ナフチルフォスフィンオキサイド、ビス－（２，６－ジメトキシベンゾイル）フェニルフォスフィンオキサイド、ビス－（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルフォスフィンオキサイド、ビス－（２，６－ジメトキシベンゾイル）－２，５－ジメチルフェニルフォスフィンオキサイド、ビス－（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド等のビスアシルフォスフィンオキサイド類、２，４，６－トリメチルベンゾイル－ジフェニルフォスフィンオキサイド、２，６－ジメトキシベンゾイル－ジフェニルフォスフィンオキサイド、２，６－ジクロロベンゾイル－ジフェニルフォスフィンオキサイド、２，４，６－トリメチルベンゾイル－フェニルフォスフィン酸メチルエステル、２－メチルベンゾイル－ジフェニルフォスフィンオキサイド、ピバロイルフェニルフォスフィン酸イソプロピルエステル等のモノアシルフォスフィンオキサイド類等が挙げられ、特に、これらの中でも、２，４，６－トリメチルベンゾイル－ジフェニルフォスフィンオキサイド、及びビス－（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイドは、３８５ｎｍや３９５ｎｍに発光波長を有するＵＶ－ＬＥＤの発光波長領域に合致するＵＶ吸収波長を有することで、好適な硬化性が得られ、且つ、硬化皮膜の黄変が少ない点でより好ましい。 Examples of the acylphosphine oxide compound 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, 2,6-dimethoxybenzoyl-diphenylphosphine oxide, 2,6-dichlorobenzoyl-diphenylphosphine oxide, 2 , 4,6-trimethylbenzoyl-phenylphosphinic acid methyl ester, 2-methylbenzoyl-diphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, and the like. Among them, 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.
　ビス（２、４、６－トリメチルベンゾイル）－フェニルフォスフィンオキサイドを例に挙げれば、インキ全量に対して１～１５重量％の範囲で使用することが好ましい。 For example, 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.
　１重量％未満の添加量では硬化性向上効果が殆ど無く、また１５重量％を超える添加量では、開始剤量が過剰となり、硬化性の更なる向上が期待出来ない上、オフセットインキ中に溶解させることが困難であり、インキ流動性の低下及び析出に起因する保存安定性の悪化を招くことから好ましくない。 If 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.
　前記したアシルフォスフィンオキサイド化合物のインキ組成物中の含有率は、インキ全量に対し１～１５重量％の範囲にあることが好ましい。１重量％未満の添加量では良好な硬化性を得ることが困難であり、また１５重量％を超える添加量では、開始剤量が過剰となり、同様にインキ流動性を損なうことから好ましくない。 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.
　前記光重合開始剤（Ｂ）としては、ヒドロキシアセトフェノン化合物、ジアルキルアミノベンゾフェノン化合物を除くベンゾフェノン化合物、αヒドロキシアルキルフェノン化合物を挙げることができる。これらは単独で用いてもよいし２種類以上添加しても良い。 Examples of the photopolymerization initiator (B) include hydroxyacetophenone compounds, benzophenone compounds excluding dialkylaminobenzophenone compounds, and α-hydroxyalkylphenone compounds. These may be used alone or in combination of two or more.
　尚、前記光重合開始剤（Ｂ）の添加量の総計は、インキ全量の０．１～３０重量％の範囲にあることが好ましく、より好ましくは１～１５重量％である。 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.
　前記ヒドロキシアセトフェノン化合物としては、ＩＲＧＡＣＵＲＥ １８４（ＢＡＳＦ社製）１－ヒドロキシ－シクロヘキシル－フェニル－ケトン　等を挙げることができる。 Examples of the hydroxyacetophenone compound include IRGACURE® 184 (manufactured by BASF) 1-hydroxy-cyclohexyl-phenyl-ketone and the like.
　前記したヒドロキシアセトフェノン化合物のインキ組成物中の含有率は、インキ全量に対し１～１５重量％の範囲にあることが好ましい。１重量％未満の添加量では良好な硬化性を得ることが困難であり、また１５重量％を超える添加量では、開始剤量が過剰となり、同様にインキ流動性を損なうことから好ましくない。 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.
　前記ジアルキルアミノベンゾフェノン化合物を除くベンゾフェノン化合物としては、ベンゾフェノン、２－メチルベンゾフェノン、３－メチルベンゾフェノン、４－メチルベンゾフェノン、メチル－２－ベンゾイルベンゾエイト、４－ベンゾイル－４‘－メチルジフェニルサルファイド、４－フェニルベンゾフェノン、Ｅｓａｃｕｒｅ　１００１（ｌａｍｂｅｒｔｉ社製）１－[４－（４－ベンゾイルフェニルサルファニル）フェニル]－２－メチル－２－（４－メチルフェニルサルファニル）プロパン－１－オン等が挙げられる。 Examples of the benzophenone compound excluding the dialkylaminobenzophenone compound 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.
　前記したベンゾフェノン化合物のインキ組成物中の含有率は、インキ全量に対し１～１５重量％の範囲にあることが好ましい。１重量％未満の添加量では硬化速度の更なる向上が得られない点で望ましくなく、また１５重量％を超えて添加しても、使用しただけの効果が認められず好ましくない。 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.
　前記αヒドロキシアルキルフェノン化合物としては、ＤＡＲＯＣＵＲ　１１７３（ＢＡＳＦ社製）２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、ＩＲＧＡＣＵＲＥ　２９５９（ＢＡＳＦ社製）１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、ＩＲＧＡＣＵＲＥ　１２７（ＢＡＳＦ社製）２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン、ＥＳＡＣＵＲＥ　ＫＩＰ １５０（ｌａｍｂｅｒｔｉ社製）ポリ｛２－ヒドロキシ－２－メチル－１－［４－（１－メチルビニル）フェニル］プロパン－１－オン｝、ＥＳＡＣＵＲＥ　ＫＩＰ １６０（ｌａｍｂｅｒｔｉ社製）２－ヒドロキシ－１－{４－〔４－(２－ヒドロキシ－２－メチルプロピオニル)フェノキシ〕フェニル}－２－メチルプロパノン、ＥＳＡＣＵＲＥ　ＯＮＥ（ｌａｍｂｅｒｔｉ社製）ポリ｛２－ヒドロキシ－２－メチル－１－［４－（１－メチルビニル）フェニル］プロパン－１－オン｝　等を挙げることができる。 Examples of the α-hydroxyalkylphenone compound 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-methylpropanone, ESACURE ONE (manufactured by Lamberti) poly {2-hydroxy-2-methyl -1- [4- (1-methylvinyl) phenyl] propan-1-one} and the like.
　前記したα－ヒドロキシケトン化合物のインキ組成物中の含有率は、インキ全量に対し１～１５重量％の範囲にあることが好ましい。１重量％未満の添加量では硬化速度の更なる向上が得られない点で望ましくなく、また１５重量％を超えて添加しても、使用しただけの効果が認められず好ましくない。 The content of the α-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.
　更に、本発明の硬化方法に用いるインキでは光重合開始剤（ＩＩＩ）として、ジアルキルアミノベンゾフェノン化合物及び／又はチオキサントン化合物を使用することが出来る。 Furthermore, in the ink used for the curing method of the present invention, a dialkylaminobenzophenone compound and / or a thioxanthone compound can be used as the photopolymerization initiator (III).
　前記したジアルキルアミノベンゾフェノン化合物としては、４，４’－ビス－（ジメチルアミノ）ベンゾフェノン、４，４’－ビス－（ジエチルアミノ）ベンゾフェノン等の４，４’－ジアルキルベンゾフェノン類、４－ベンゾイル－４’－メチルジフェニルスルフィド等が挙げられる。中でも４，４′－ビス（ジエチルアミノ）ベンゾフェノン（数平均分子量３２４．４７）は硬化性に優れる。 Examples of the dialkylaminobenzophenone compound include 4,4′-bis- (dimethylamino) benzophenone, 4,4′-dialkylbenzophenones such as 4,4′-bis- (diethylamino) benzophenone, 4-benzoyl-4 ′. -Methyldiphenyl sulfide and the like. Among these, 4,4′-bis (diethylamino) benzophenone (number average molecular weight 324.47) is excellent in curability.
　また前記したチオキサントン化合物としては、チオキサントン、２，４－ジエチルチオキサントン、２－メチルチオキサントン、２，４－ジメチルチオキサントン、イソプロピルチオキサントン、２，４－ジイソプロピルチオキサントン、２－クロロチオキサントン、２，４－ジクロロチオキサントン、１－クロロ－４－プロポキシチオキサントン等が挙げられ、黄変の発現性を考慮すると使用量は少量に限定されるが、併用することで皮膜硬化性を好適に向上させることが可能である。 Examples of the thioxanthone compound 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.
　またＵＶ－ＬＥＤ発光波長領域に合致するＵＶ吸収特性を有していないものであっても、３級アミン化合物（α－アミノアルキルフェノン化合物、および、ジアルキルアミノベンゾフェノン化合物を除く）を水素供与体として併用することで、好適な活性エネルギー線硬化を得ることが出来る。例えば、脂肪族アミン誘導体としてトリエタノールアミン、メチルジエタノールアミン、トリエチルアミン、ジブチルエタノールアミン等が、安息香酸誘導体のアミンとして２－ジメチルアミノエチル安息香酸、２－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸エチル等が、アニリン誘導体のアミンとしてＮ，Ｎ－ジヒドロキシエチルアニリン、Ｎ，Ｎ－ジメチルアニリン、Ｎ，Ｎ－ジエチルアニリン、Ｎ，Ｎ－ジメチル－p－トルイジン等が挙げられる。 In addition, a tertiary amine compound (excluding α-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. By using together, suitable active energy ray hardening can be obtained. For example, 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. Examples of amines of aniline derivatives include N, N-dihydroxyethylaniline, N, N-dimethylaniline, N, N-diethylaniline, and N, N-dimethyl-p-toluidine.
　前記した３級アミン化合物を例に挙げれば、そのインキ組成物中の含有率は、インキ全量に対し０．１～１０重量％の範囲にあることが好ましい。０．１重量％未満の添加量では硬化速度の更なる向上が得られない点で望ましくなく、また１０重量％を超えて添加しても、使用しただけの効果が認められず好ましくない。 Taking the above-mentioned tertiary amine compound as an example, 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.
　本発明の活性エネルギー線硬化型オフセットインキの硬化方法に用いるインキで使用する着色顔料としては、公知公用の着色用有機顔料を挙げることができ、例えば「有機顔料ハンドブック（著者：橋本勲、発行所：カラーオフィス、２００６年初版）」に掲載される印刷インキ用有機顔料等が挙げられ、溶性アゾ顔料、不溶性アゾ顔料、縮合アゾ顔料、金属フタロシアニン顔料、無金属フタロシアニン顔料、キナクリドン顔料、ペリレン顔料、ペリノン顔料、イソインドリノン顔料、イソインドリン顔料、ジオキサジン顔料、チオインジゴ顔料、アンスラキノン系顔料、キノフタロン顔料、金属錯体顔料、ジケトピロロピロール顔料、カーボンブラック顔料、その他多環式顔料等が使用可能である。 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. For example, “Organic Pigment Handbook (Author: Isao Hashimoto, Issuance Office) : Color Office, 2006, first edition) ”, and so on. Soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, Perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, carbon black pigments, and other polycyclic pigments can be used. is there.
　前記着色顔料を含む紫外線硬化型インキにおいては、特に紫外線吸収能の極めて高いカーボンブラックを添加量１０～２５重量％の範囲で用いた墨インキにおいては光重合開始剤を活性化せしめる紫外線エネルギーの損失が多く、他の着色顔料と比較して特にインキ皮膜底部における光重合反応が進行し難い為、十分な硬化性を得ることが困難であるが、本発明で述べるオフセットインキはカーボンブラックを１０～２５重量％用いた墨インキについても好適な硬化性を付与することが可能である。 In the ultraviolet curable ink containing the coloring pigment, 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. In many cases, 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. However, 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.
　しかし、カーボンブラックの添加量が２５重量％を超える紫外線硬化型インキにおいては、カーボンブラックによる紫外線エネルギーの損失が莫大となり、好適な乾燥性が得られないことから好ましくない。前記カーボンブラックの平均一次粒子径は、１５～７０ｎｍの範囲にあることが好ましく、２０～４０ｎｍの範囲にあることが特に好ましい。平均一次粒子径が１５ｎｍ未満である場合、カーボンブラックによる紫外線エネルギーの損失が莫大となり、好適な乾燥性が得られないことから好ましくなく、また７０ｎｍを超える場合、墨インキの黒色感が損なわれることから好ましくない。 However, 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.
　前記カーボンブラックはファーネス法、サーマル法、コンタクト法などの公知の手法により製造されたものを挙げることができ、例えば、ラーベン１４、ラーベン４５０、ラーベン８６０Ｕｌｔｒａ、ラーベン１０３５、ラーベン１０４０、ラーベン１０６０Ｕｌｔｒａ、ラーベン１０８０Ｕｌｔｒａ、ラーベン１１８０、ラーベン１２５５（以上、コロンビアンケミカル社製）、リーガル４００Ｒ、リーガル３３０Ｒ、リーガル６６０Ｒ、モーグルＬ（以上、キャボット社製）、ＭＡ７、ＭＡ８、ＭＡ１１（以上、三菱化学社製）等を挙げることができ、これらは単独で使用してもよく、また２種以上を適宜組み合わせて使用してもよい。 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.
　本発明の活性エネルギー線硬化型オフセットインキの硬化方法で使用可能な印刷基材としては、特に限定は無く、例えば、上質紙、コート紙、アート紙、模造紙、薄紙、厚紙等の紙、各種合成紙、ポリエステル樹脂、アクリル樹脂、塩化ビニル樹脂、塩化ビニリデン樹脂、ポリビニルアルコール、ポリエチレン、ポリプロピレン、ポリアクリロニトリル、エチレン酢酸ビニル共重合体、エチレンビニルアルコール共重合体、エチレンメタクリル酸共重合体、ナイロン、ポリ乳酸、ポリカーボネート等のフィルム又はシート、セロファン、アルミニウムフォイル、その他従来から印刷基材として使用されている各種基材を挙げることが出来る。 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. For example, 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, Examples thereof include films or sheets such as polylactic acid and polycarbonate, cellophane, aluminum foil, and other various base materials conventionally used as printing base materials.
　本発明で述べる活性エネルギー線硬化型オフセット印刷インキの硬化方法に用いるインキの製造は、従来の紫外線硬化型インキと同様に、前記着色顔料、重合性アクリレートモノマー、重合基を有する樹脂オリゴマー、光重合開始剤、増感剤、その他添加剤等を配合してミキサー等で撹拌混合し、三本ロールミル、ビーズミル等の分散機を用いて練肉することで製造される。 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.
　以下、実施例によって本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to examples.
　〔ベースインキの製造方法〕
　表１の組成に従って混合し三本ロールミルにて練肉することによって、まず光重合化開始剤を含まないベースインキ（Ｙ）を作成した。
尚、色材顔料としてベースインキ全量の２０重量％のフタロシアニンブルー（ＤＩＣ製ＦＡＳＴＯＧＥＮ　Ｂｌｕｅ　ＦＡ５３８０　Ｐｉｇｍｅｎｔ　Ｂｌｕｅ１５：３）を添加した。エチレン性二重結合を有する活性エネルギー線重合性化合物（Ｉ）については総計でベースインキ全量の６３．５重量％、ジアクリルフタレート樹脂（ダイソーＤＡＰ　Ａ）をベースインキ全量の１０重量％、粘度及び流動性調整剤としてタルク１重量％、クレー１重量％、炭酸マグネシウム１重量％、炭酸カルシウム１重量％及び有機ベントナイト０．５重量％（合計４．５重量％）、その他助剤としてワックス計２重量％を添加した。
エチレン性二重結合を有する活性エネルギー線重合性化合物（Ｉ）とジアリルフタレート樹脂は、１２０℃の熱を加え、予め溶解させた。 [Production method of base ink]
First, 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.
In addition, 20 weight% of phthalocyanine blue (DIC FASTOGEN Blue FA5380 Pigment Blue 15: 3) was added as a colorant pigment. For 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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　次に表２～３の実施例１～１８及び、表４～５の比較例１～１４の組成に従って前記ベースインキ（Ｙ）に各々光重合開始剤を添加し、更に三本ロールミルにて練肉することによって各種の活性エネルギー線硬化型インキを作成した。 Next, according to the compositions of Examples 1 to 18 in Tables 2 to 3 and Comparative Examples 1 to 14 in Tables 4 to 5, a photopolymerization initiator was added to each of the base inks (Y), and further kneaded in a three-roll mill. Various active energy ray-curable inks were prepared by meat.
　〔印刷物の製造方法〕
　この様にして得られた活性エネルギー線硬化型インキを、簡易展色機（ＲＩテスター、豊栄精工社製）を用い、インキ０．１０ｍｌを使用して、ＲＩテスターのゴムロール及び金属ロール上に均一に引き伸ばし、コート紙（王子製紙製「ＯＫトップコートプラス５７．５Ｋｇ、Ａ判」）の表面に、２００ｃｍ２の面崎にわったて藍濃度１．６（Ｘ－Ｒｉｔｅ社製ＳｐｅｃｔｒｏＥｙｅ濃度計で計測）で均一に塗布されるように展色し、印刷物を作製した。なおＲＩテスターとは、紙やフィルムにインキを展色する試験機であり、インキの転移量や印圧を調整することが可能である。 [Method for producing printed matter]
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ランプ光源による硬化方法〕
短波として発光ダイオードの発光波長が２００～３５０ｎｍ未満の波長域を持つＵＶ－ＬＥＤランプ光源を、長波として発光ダイオードの発光波長が３５０～４２０ｎｍの波長域を持つＵＶ－ＬＥＤランプ光源を用いて、下記のＸ１～Ｘ３の３方式によって照射を行った。
　　照射方式Ｘ１：短波＋長波による２灯照射
　　照射方式Ｘ２：長波のみによる照射
　　照射方式Ｘ３：短波のみによる照射 [Curing method using UV-LED lamp light source]
Using a 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, the following is used. 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
〔インキ組成物の評価方法：硬化性〕
　硬化性は、紫外線照射直後に爪スクラッチ法にて展色物表面の傷付きの有無を確認し次の４段階で評価した。爪で擦ってインキ硬化皮膜に傷が発生する組成では、印刷物の断裁や製函、輸送といった各工程において、印刷物が損傷し易くなる。
　　◎：硬化した塗膜に、全く傷が付かない。
　　○：硬化した塗膜に、うっすらと傷が付く。傷は基材まで到達しない。
　　△：硬化した塗膜に、傷が付く。傷は基材まで到達する。表面にべた付きない。
　　×：硬化した塗膜に、傷が付く。基材まで到達する。表面にべた付きあり。 [Evaluation method of ink composition: curability]
The curability was evaluated in the following four stages by checking the presence or absence of scratches on the surface of the developed product by the nail scratch method immediately after the ultraviolet irradiation. In the composition in which the ink cured film is scratched by rubbing with a nail, the printed material is easily damaged in each process such as cutting, box making and transportation of the printed material.
A: The cured coating film is not scratched at all.
○: The cured coating film is slightly scratched. The scratch does not reach the substrate.
Δ: The cured coating film is scratched. The wound reaches the substrate. Does not stick to the surface.
X: The cured coating film is scratched. Reach the substrate. There is stickiness on the surface.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
表２～５中の数値は重量％である。
表２～５に示す諸原料及び略を以下に示す。
・Ｉｒｇａｃｕｒｅ９０７：２－メチル－１－[４－（メチルチオ）フェニル]－２－モノフォリノプロパン－１－オン、　ＢＡＳＦ社製
・Ｉｒｇａｃｕｒｅ３６９：２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、　ＢＡＳＦ社製
・ＤＡＲＯＣＵＲ　ＴＰＯ：２，４，６－トリメチルベンゾイル－ジフェニルフォスフィンオキサイド、　ＢＡＳＦ社製
・Ｉｒｇａｃｕｒｅ１８４：1-ヒドロキシ－シクロヘキシル－フェニル－ケトン、　ＢＡＳＦ社製
・ＥＡＢ－ＳＳ：４,４’－ビス（ジエチルアミノ）ベンゾフェノール
・ＫＹ５０：芳香族３級アミン増感剤、エチル－４－（ジメチルアミノ）ベンゾエート、日本化薬株式会社製 The numerical values in Tables 2 to 5 are% by weight.
The raw materials and abbreviations shown in Tables 2 to 5 are shown below.
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.
　実施例に述べる活性エネルギー線硬化型オフセットインキの硬化方法では、エチレン性二重結合を有する活性エネルギー線重合性化合物（Ｉ）と光重合開始剤（ＩＩ）と発光波長の異なる発光ダイオードを２種以上組み合わることで充分な硬化性を保持することが出来る。 In the curing method of the active energy ray-curable offset ink described in the Examples, two types of active energy ray-polymerizable compound (I) having an ethylenic double bond, photopolymerization initiator (II), and light emitting diodes having different emission wavelengths are used. By combining the above, sufficient curability can be maintained.

Claims (8)

  1. エチレン性二重結合を有する活性エネルギー線重合性化合物（Ｉ）と光重合開始剤（ＩＩ）を含有する活性エネルギー線硬化型インキの硬化方法であって、
    硬化に使用する光源が発光波長の異なる発光ダイオードを２種以上組み合わせたものであることを特徴とする活性エネルギー線硬化型インキの硬化方法。
    A method for curing an active energy ray-curable ink comprising an active energy ray-polymerizable compound (I) having an ethylenic double bond and a photopolymerization initiator (II),
    A method for curing an active energy ray-curable ink, wherein a light source used for curing is a combination of two or more light emitting diodes having different emission wavelengths.
  2. 発光波長が２００～３５０ｎｍ未満の発光ダイオードと、３５０～４２０ｎｍの発光ダイオードを必須とする請求項１記載の活性エネルギー線硬化型インキの硬化方法。
    The method of curing an active energy ray-curable ink according to claim 1, wherein a light emitting diode having an emission wavelength of 200 to less than 350 nm and a light emitting diode having a wavelength of 350 to 420 nm are essential.
  3. 前記光重合開始剤（ＩＩ）が２００～３５０ｎｍ未満の吸収波長を持つ光重合開始剤（Ａ）及び３５０～４２０ｎｍの吸収波長を持つ光重合開始剤（Ｂ）である請求項１記載の活性エネルギー線硬化型インキの硬化方法。
    The active energy according to claim 1, 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. Curing method for line curable ink.
  4. 前記光重合開始剤（Ａ）が下記の（Ａ）群から選ばれる少なくとも１種以上である請求項３記載の活性エネルギー線硬化型インキの硬化方法。

    （Ａ）α（ジメチル）アミノアルキルフェノン化合物、
    　　　αモルフォリノアルキルフェノン化合物、
    　　　アシルフォスフィンオキサイド化合物。
    The method for curing an active energy ray-curable ink according to claim 3, wherein the photopolymerization initiator (A) is at least one selected from the following group (A).

    (A) an α (dimethyl) aminoalkylphenone compound,
    α-morpholinoalkylphenone compound,
    Acylphosphine oxide compound.
  5. 前記光重合開始剤（Ｂ）が下記の（Ｂ）群から選ばれる少なくとも１種以上である請求項３記載の活性エネルギー線硬化型インキの硬化方法。

    （Ｂ）ヒドロキシアセトフェノン化合物、
    　　　ジアルキルアミノベンゾフェノン化合物を除くベンゾフェノン化合物、
    　　　αヒドロキシアルキルフェノン化合物
    The method for curing an active energy ray-curable ink according to claim 3, wherein the photopolymerization initiator (B) is at least one selected from the following group (B).

    (B) a hydroxyacetophenone compound,
    Benzophenone compounds excluding dialkylaminobenzophenone compounds,
    α-Hydroxyalkylphenone compounds
  6. 更に光重合開始剤（ＩＩＩ）として、ジアルキルアミノベンゾフェノン化合物及び／又はチオキサントン化合物を含有する請求項１～５の何れかに記載の活性エネルギー線硬化型インキの硬化方法。
    The method for curing an active energy ray-curable ink according to any one of claims 1 to 5, further comprising a dialkylaminobenzophenone compound and / or a thioxanthone compound as the photopolymerization initiator (III).
  7. 請求項１～６の何れかに記載の活性エネルギー線硬化型インキの硬化方法に使用される活性エネルギー線硬化型インキであって、少なくとも下記光重合開始剤（Ａ）及び（Ｂ）の群から各々選ばれる少なくとも１種以上を含有する活性エネルギー線硬化型インキ。
    （Ａ）α（ジメチル）アミノアルキルフェノン化合物、
    　　　αモルフォリノアルキルフェノン化合物、
    　　　アシルフォスフィンオキサイド化合物。
    （Ｂ）ヒドロキシアセトフェノン化合物、
    　　　ジアルキルアミノベンゾフェノン化合物を除くベンゾフェノン化合物、
    　　　αヒドロキシアルキルフェノン化合物
    An active energy ray-curable ink used in the method of curing an active energy ray-curable ink according to any one of claims 1 to 6, wherein the ink is at least from the group of the following photopolymerization initiators (A) and (B): An active energy ray-curable ink containing at least one selected from each.
    (A) an α (dimethyl) aminoalkylphenone compound,
    α-morpholinoalkylphenone compound,
    Acylphosphine oxide compound.
    (B) a hydroxyacetophenone compound,
    Benzophenone compounds excluding dialkylaminobenzophenone compounds,
    α-Hydroxyalkylphenone compounds
  8. 請求項７に記載の活性エネルギー線硬化型インキを用いて印刷した印刷物。 A printed matter printed using the active energy ray-curable ink according to claim 7.
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