WO2019171965A1 - Actinic-ray-curable ink, method for producing cured ink, and printed matter - Google Patents
Actinic-ray-curable ink, method for producing cured ink, and printed matter Download PDFInfo
- Publication number
- WO2019171965A1 WO2019171965A1 PCT/JP2019/006471 JP2019006471W WO2019171965A1 WO 2019171965 A1 WO2019171965 A1 WO 2019171965A1 JP 2019006471 W JP2019006471 W JP 2019006471W WO 2019171965 A1 WO2019171965 A1 WO 2019171965A1
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- WO
- WIPO (PCT)
- Prior art keywords
- ink
- acrylate
- meth
- energy ray
- active energy
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000007639 printing Methods 0.000 claims abstract description 36
- 239000003999 initiator Substances 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 14
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- -1 tertiary amine compound Chemical class 0.000 claims description 35
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- 238000007645 offset printing Methods 0.000 claims description 4
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- 238000000034 method Methods 0.000 abstract description 10
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- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 5
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- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
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- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 2
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- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
Definitions
- the present invention relates to an active energy ray-curable ink, a method for producing a cured product of the active energy ray-curable ink, and a printed matter.
- the active energy ray curable ink is solventless and instantaneously dries and cures the active energy ray, so that it is environmentally friendly, has excellent printing workability, and can produce high-quality printed materials. It is used as an ink in various printing methods such as ordinary lithographic plates and waterless lithographic plates that do not use dampening water), relief printing, intaglio printing, stencil printing, offset printing, etc., printed materials for forms, printed materials for various books, carton paper, etc. It is applied to various printed materials such as printed materials for packaging, printed materials for plastics, seals, printed materials for labels, printed materials for arts, printed materials for metal (printed products for arts, printed beverages, cans, etc.).
- UV lamps such as low-pressure and high-pressure mercury lamps, xenon lamps, metal halide lamps and the like have been widely used.
- UV-LEDs ultraviolet light-emitting diodes
- Irradiation modules with a light source have been developed, and their application in the UV printing field is advancing.
- UV-LEDs Ultraviolet light emitting diodes emit ultraviolet light having an emission peak wavelength in the range of 350 to 420 nm. That is, when an ink using a light source such as a conventional metal halide lamp or a high-pressure mercury lamp is to be applied to a UV-LED, it is necessary to use a photopolymerization initiator having absorption in the vicinity of a wavelength of 350 to 420 nm. Since the pigment itself used in the ink absorbs light in the wavelength range of 350 to 420 nm, in many cases, even if a photopolymerization initiator having absorption at a wavelength of 350 to 420 nm is used, there is a problem that curing is insufficient. .
- Examples of the ink composition applied to the UV-LED include an ⁇ - (dimethyl) aminoalkylphenone compound and / or an ⁇ -morpholinoalkylphenone compound and a dialkylaminobenzophenone compound (A2-1) as a photopolymerization initiator. And / or an active energy ray-curable ink combined with a thioxanthone compound (see, for example, Patent Document 1), an ⁇ -aminoalkylphenone compound and an acylphosphine oxide compound as a photopolymerization initiator, and a specific alcohol There is known an active energy ray-curable ink containing selenium (for example, see Patent Document 2).
- the ⁇ -aminoalkylphenone compound has an ultraviolet absorption region on the shorter wavelength side, and when cured with a UV-LED, the curability of the coating film surface may be inferior.
- 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907) a general-purpose ⁇ -morpholinoalkylphenone compound, generates a unique odor immediately after UV irradiation. For this reason, there is a limit to the amount of compounding in applications where high hygiene is required, and sufficient curability could not be obtained.
- the present inventors are to provide an active energy ray-curable ink that cures very quickly and is less likely to cause odor even when a UV-LED light source is used.
- the present inventors have found that an active energy ray-curable ink containing a specific photopolymerization initiator solves the above problems.
- the present invention provides an active energy ray-curable ink containing a monomer having an ethylenically unsaturated double bond and a photopolymerization initiator represented by the general formula (1).
- n 0 or 1
- R 1 to R 4 each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms.
- the present invention also provides a method for producing an ink cured product that is printed using the active energy ray-curable ink described above and that cures the printed ink using the active energy ray.
- the present invention also provides a method for producing an ink cured product, in which offset printing is performed using the active energy ray-curable ink described above, and the printed ink is cured using the active energy ray.
- the present invention also provides a printed matter obtained by the above-described method for producing an ink cured product.
- the ink of the present invention can be used as an ink of various conventionally known printing methods such as offset ink, relief printing ink, intaglio printing ink, and stencil printing ink.
- n 0 or 1
- R 1 to R 4 are each independently a straight chain or branched chain having 1 to 10 carbon atoms. Represents an alkyl group.
- Examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by R 1 to R 4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, Examples thereof include a tert-butyl group, a pentyl group, an amyl group, an isoamyl group, a hexyl group, a heptyl group, an isoheptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, and a decyl group.
- R 1 to R 4 are each independently preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and n is more preferably 0.
- Examples of the photopolymerization initiator according to the present invention include 2-benzyl-2-dimethylamino-1- (4-piperidinophenyl) -butan-1-one (also known as 2-benzyl-2-dimethyl) shown below. Amino-1- (4-piperidinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-piperidinophenyl) -1-butanone, etc.).
- the content of the photopolymerization initiator represented by the general formula (1) is preferably 0.5 to 10% by mass, and 1.0 to 5.0% by mass with respect to the total amount of ink solids. More preferred. In the case of 0.5% by mass or less, active radicals generated by ultraviolet irradiation are deactivated by oxygen in the air, and the curability of the ink is remarkably reduced.
- a general-purpose photopolymerization initiator in addition to the photopolymerization initiator represented by the general formula (1), the type of ultraviolet light source to be used, the irradiation intensity of the ultraviolet light source, and the integrated amount of irradiation with ultraviolet light In view of color, printed film thickness, hygiene, etc., a general-purpose photopolymerization initiator may be suitably used in combination.
- bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl- Examples include acylphosphine oxide compounds such as pentylphosphine oxide.
- benzophenone 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 2,3,4-trimethylbenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4 -(1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, methyl-o-benzoylbenzoate, [4- (methylphenylthio) phenyl] phenylmethanone, diethoxyacetophenone, Examples include dibutoxyacetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether.
- the general-purpose photopolymerization initiator used in combination with the photopolymerization initiator represented by the general formula (1) may be used alone or in combination.
- a photopolymerization initiator represented by the general formula (1) and an acyl phosphine oxide compound in combination
- 2,4,6-trimethylbenzoyldiphenylphosphine is particularly preferable from the viewpoint of solubility in a resin.
- an oxide in combination it is more preferable to use an oxide in combination.
- the content of 2,4,6-trimethylbenzoyldiphenylphosphine oxide may be 70 to 2000% by mass with respect to the photopolymerization initiator represented by the general formula (1).
- the amount of 2,4,6-trimethylbenzoyldiphenylphosphine oxide used is preferably 1.0 to 15% by mass, more preferably 3.0 to 10% by mass, based on the total amount of ink solids.
- the amount is less than 1.0% by mass, a sufficient effect of improving curability cannot be obtained.
- the amount exceeds 15% by mass, unreacted acylphosphine oxide remains in the cured coating film even after UV irradiation. The color of the cured coating film changes to an unacceptable yellowish color, the initiator is deposited, and the fluidity of the ink is significantly reduced.
- the photosensitizer absorbs ultraviolet rays and transitions to an electronically excited singlet state, and then transitions to a triplet state due to intersystem crossing. And, it is a compound that acts to shift the photopolymerization initiator to the excited triplet state when energy transfer occurs when colliding with the photopolymerization initiator in the ground state.
- a sensitizer when using a light source having a narrow emission wavelength range such as an LED, it is preferable to combine a sensitizer in order to efficiently generate radicals from the photoinitiator and support the function of the photopolymerization initiator.
- the photoinitiator aid is a secondary or tertiary amine compound having at least one hydrogen on the ⁇ -position carbon.
- the hydrogen on the ⁇ -position carbon of these compounds is extracted by radicals, and the tertiary amine compounds become ⁇ -aminoalkyl radicals.
- the ⁇ -aminoalkyl radical can efficiently initiate the polymerization of the (meth) acrylate monomer.
- the ⁇ -aminoalkyl radical reacts with oxygen in the air, an oxyl radical is generated and the polymerization initiating ability of the (meth) acrylate monomer is lost. This oxyl radical is converted from an unreacted photoinitiator to hydrogen. To produce a new ⁇ -aminoalkyl radical that can initiate polymerization of the (meth) acrylate monomer.
- a photoinitiator aid it is possible to suitably suppress the deactivation of the photoinitiator due to oxygen in the air, and therefore it is preferable to combine a photoinitiator aid.
- a tertiary amine compound having a lower basicity is used in order to suppress ink adhesion to hydrophilic non-image areas. It is more preferable to suppress over-emulsification of the linear curable ink.
- Preferred photosensitizers include, but are not limited to, thioxanthone series, benzophenone series such as 4,4′-bis (diethylamino) benzophenone, anthraquinone series, and coumarin series.
- thioxanthone compounds such as 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4,4′-dialkylaminobenzophenones such as Michler's ketone and 4,4′-bis- (diethylamino) benzophenone are preferable.
- the sensitizer is preferably from 0.05 to 10% by mass, more preferably from 0.1 to 7.0% by mass, based on the total amount of ink solids.
- the amount is less than 0.05% by mass, a sufficient effect of improving the curability cannot be obtained.
- the amount exceeds 10% by mass, the color of the cured coating film changes to an unacceptable yellowish color, or a sensitizer is used. Precipitation may occur or the fluidity of the ink may be significantly reduced.
- the tertiary amine is not particularly limited, but ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-diethylaniline.
- the tertiary amine is preferably used in combination as long as it does not impair the printing performance of the active energy ray-curable ink of the present invention, preferably 0.1 to 10% by weight, and preferably 0.1 to 5.0% by weight based on the total amount of ink solids. It is more preferable to use in the range of mass%.
- high molecular weight compounds in which a plurality of photosensitizers or tertiary amines are branched in one molecule with a polyhydric alcohol or the like can be used as appropriate.
- the active energy ray-curable monomer and / or oligomer used in the present invention can be used without particular limitation as long as it is a monomer and / or oligomer used in the active energy ray-curable technical field.
- Particularly preferred are those having a (meth) acryloyl group, a vinyl ether group or the like as a reactive group.
- UV-LEDs can be suitably cured by low-energy irradiation, combining more reactive trifunctional or more active energy ray-curable monomers, depending on the application, adhesion to the printing substrate, coating
- a monofunctional or bifunctional monomer alone or in combination.
- those that have a proven record in lamp systems such as monofunctional (meth) acrylates, polyfunctional (meth) acrylates, and polymerizable oligomers, can be used as they are in the ultraviolet light-emitting diode system described in the present invention. Is possible. *
- Examples of the monofunctional (meth) acrylate include ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, hexadecyl (Meth) acrylate, octadecyl (meth) acrylate, isoamyl (meth) acrylate, isodecyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxy Ethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, nonylphenoxy
- bifunctional or higher functional (meth) acrylate examples include 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.
- polymerizable oligomer examples include amine-modified polyether acrylate, amine-modified epoxy acrylate, amine-modified aliphatic acrylate, amine-modified polyester acrylate, amine-modified acrylate such as amino (meth) acrylate, thiol-modified polyester acrylate, and thiol (meth) acrylate.
- a tetra- or higher functional (meth) acrylate is used for printing on paper such as fine paper, coated paper, art paper, imitation paper, thin paper, cardboard, etc. It is preferably used because it greatly contributes to the improvement in strength, and it is preferably used in the range of 15 to 70% by mass with respect to the total amount of ink solids.
- the crosslink density of the cured coating increases, the adhesiveness between the substrate and the cured coating decreases, so the content of tetrafunctional or higher (meth) acrylates is reduced accordingly. It is necessary to let In this case, it is preferable to use tetrafunctional or higher functional (meth) acrylate in the range of 0 to 50% by mass with respect to the total amount of ink solids.
- the active energy ray curable ink of the present invention comprises the monomer having the ethylenically unsaturated double bond and the photopolymerization initiator represented by the general formula (1) as essential components. Resins, pigments, and various additives can be used.
- binder resin As the resin, various publicly known binder resins can be used.
- the binder resin described here refers to all resins having appropriate pigment affinity and dispersibility, and rheological properties required for printing inks.
- non-reactive resins include diallyl orthophthalate and / or Alternatively, diallyl phthalate resin obtained by polymerizing diallyl isophthalate and / or diallyl terephthalate, epoxy resin, polyurethane resin, polyester resin, petroleum resin, rosin ester resin, poly (meth) acrylate ester, cellulose derivative, vinyl chloride-vinyl acetate Examples thereof include copolymers, polyamide resins, polyvinyl acetal resins, butadiene-acrylonitrile copolymers, and epoxy acrylate compounds, urethane acrylate compounds, polyester acrylate compounds having at least one polymerizable group in the molecule.
- these binder resins may be used alone or may be used in combination of one or more
- the photopolymerization initiator represented by the general formula (1) and diallyl phthalate resin are used in combination, the curability of the active energy ray-curable ink is improved and the fluidity of the ink is improved. Therefore, it is possible to suppress the occurrence of defects in printability such as fraying and poor transfer between ink rollers.
- pigment examples include publicly known organic pigments for coloring, such as organic pigments for printing inks published in “Organic Pigment Handbook (Author: Isao Hashimoto, Publisher: Color Office, 2006 First Edition)”. Soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinones A pigment, a quinophthalone pigment, a metal complex pigment, a diketopyrrolopyrrole pigment, a carbon black pigment, and other polycyclic pigments can be used.
- organic pigments for coloring published in “Organic Pigment Handbook (Author: Isao Hashimoto, Publisher: Color Office, 2006 First Edition)”. Soluble azo pigments, insoluble azo pigment
- inorganic fine particles may be used as extender pigments.
- Inorganic fine particles include inorganic coloring pigments such as titanium oxide, graphite, zinc white; lime carbonate powder, precipitated calcium carbonate, gypsum, clay (ChinaClay), silica powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, stearin Inorganic pigments such as aluminum oxide, magnesium carbonate, barite powder, and abrasive powder; inorganic pigments such as silicone, glass beads, and the like.
- additives include, for example, carnauba wax, wax, lanolin, montan wax, paraffin wax, and microcrystalline wax as additives that impart friction resistance, antiblocking properties, slipperiness, and scratch resistance.
- waxes Fischer-Trops waxes
- polyethylene waxes polypropylene waxes
- polytetrafluoroethylene waxes polyamide waxes
- synthetic waxes such as silicone compounds.
- additives that impart ink storage stability include (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picryl.
- additives such as ultraviolet absorbers, infrared absorbers and antibacterial agents can be added according to the required performance. *
- the active energy ray-curable ink of the present invention can be used without a solvent, and an appropriate solvent can be used as necessary.
- the solvent is not particularly limited as long as it does not react with each of the above components, and can be used alone or in combination of two or more.
- the active energy ray curable ink of the present invention may be carried out by the same method as in the prior art.
- the pigment, the resin, the acrylic monomer or oligomer, the polymerization inhibitor, the initiator, and the amine between room temperature and 100 ° C.
- Ink composition components such as sensitizers such as compounds and other additives are produced using kneading, mixing, and adjusting machines such as a kneader, three rolls, attritor, sand mill, and gate mixer.
- the active energy ray-curable ink layer is formed on a substrate or a printing ink layer printed on the substrate, and has a peak wavelength at 350 to 420 nm.
- a printed matter obtained by irradiating ultraviolet rays with an ultraviolet light emitting diode light source.
- the printing substrate used in the printed matter of the present invention is not particularly limited.
- paper such as fine paper, coated paper, art paper, imitation paper, thin paper, cardboard, polyester resin, acrylic resin, vinyl chloride resin, chloride.
- Vinylidene resin polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, nylon or polylactic acid, polycarbonate film or sheet, cellophane, aluminum foil
- various base materials conventionally used as printing base materials can be mentioned. *
- the printing ink used in the production of the printed matter of the present invention is not particularly limited as long as it is a composition that is suitably cured with respect to ultraviolet rays emitted from ultraviolet light emitting diodes.
- a composition that is suitably cured with respect to ultraviolet rays emitted from ultraviolet light emitting diodes.
- offset for example, depending on the printing method, offset, no water, It is possible to employ gravure, flexo, silk screen, ink jet, and other UV curable inks conventionally used for printing.
- the emission wavelength of ultraviolet rays emitted from the ultraviolet light emitting diode light source used for producing the printed matter of the present invention for example, those having an emission peak wavelength of about 350 to 420 nm are preferable.
- the integrated light quantity value of the ultraviolet light irradiated to the UV curable composition from the ultraviolet light emitting diode light source varies depending on the type of the UV curable composition on the printing substrate and the thickness of the printing layer, and thus cannot be specified strictly.
- the preferable conditions are selected as appropriate.
- the sum of the integrated light amounts is about 5 to 200 mJ / cm 2 , and more preferably about 10 to 100 mJ / cm 2 .
- the irradiation intensity (mW / cm 2 ) of ultraviolet rays irradiated from the ultraviolet light emitting diode light source to the UV curable composition on the printing substrate the number of ultraviolet light emitting diode light sources arranged in the printing direction and the irradiation from the light source to the composition Since the appropriate irradiation intensity range fluctuates depending on various conditions such as distance, there is no particular limitation, but the moving speed of the printing substrate in the printing method described in the present invention is 60 to 400 m / min. Therefore, it is preferable that the irradiation intensity is such that the integrated light quantity value is as described above for the UV curable composition on the printing substrate moving at the printing speed.
- 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. And spread on a PET original fabric (DIC Corporation, Daitac UVPET Transparent 25FL) so that it can be uniformly applied at an ink density of 1.8 (measured with a X-Rite SpectroEye densitometer) over an area of approximately 220 cm2. Colored and produced an exhibition color.
- 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.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Polymerisation Methods In General (AREA)
Abstract
An actinic-ray-curable ink which includes a monomer having an ethylenically unsaturated double bond and a photopolymerization initiator represented by general formula (1); a method for producing a cured ink, the method comprising printing the actinic-ray-curable ink and curing the printed ink using actinic rays; and printed matter. The photopolymerization initiator represented by general formula (1) is preferably 2-benzyl-2-dimethylamino-1-(4-piperidinophenyl)butan-1-one. (In formula (1), n is 0 or 1 and R1 to R4 each independently represent a linear or branched C1-10 alkyl group.)
Description
本発明は、活性エネルギー線硬化型インキ、該活性エネルギー線硬化型インキの硬化物の製造方法および印刷物に関する。
The present invention relates to an active energy ray-curable ink, a method for producing a cured product of the active energy ray-curable ink, and a printed matter. *
活性エネルギー線硬化型インキは、無溶剤型であり瞬間的に活性エネルギー線硬化乾燥することから、環境対応、印刷作業性に優れ、且つ高品質の印刷物が得られるとして、平版（湿し水を使用する通常の平版および湿し水を使用しない水無し平版）、凸版、凹版、孔版印刷、オフセット印刷など種々の印刷方式におけるインクとして使用されており、フォーム用印刷物、各種書籍印刷物、カルトン紙等の各種包装用印刷物、各種プラスチック印刷物、シール、ラベル用印刷物、美術印刷物、金属印刷物（美術印刷物、飲料缶印刷物、缶詰等の食品印刷物）などの種々の印刷物に適用されている。
The active energy ray curable ink is solventless and instantaneously dries and cures the active energy ray, so that it is environmentally friendly, has excellent printing workability, and can produce high-quality printed materials. It is used as an ink in various printing methods such as ordinary lithographic plates and waterless lithographic plates that do not use dampening water), relief printing, intaglio printing, stencil printing, offset printing, etc., printed materials for forms, printed materials for various books, carton paper, etc. It is applied to various printed materials such as printed materials for packaging, printed materials for plastics, seals, printed materials for labels, printed materials for arts, printed materials for metal (printed products for arts, printed beverages, cans, etc.).
これら活性エネルギー線硬化型インキの光源としては、従来低圧や高圧の水銀灯、キセノンランプ、メタルハライドランプ等の紫外線ランプ（ＵＶランプ）が広く用いられてきたが、近年、紫外線発光ダイオード（ＵＶ－ＬＥＤ）を光源とした照射モジュールが開発され、ＵＶ印刷分野への適用が進んでいる。
As a light source for these active energy ray-curable inks, ultraviolet lamps (UV lamps) such as low-pressure and high-pressure mercury lamps, xenon lamps, metal halide lamps and the like have been widely used. However, in recent years, ultraviolet light-emitting diodes (UV-LEDs) have been used. Irradiation modules with a light source have been developed, and their application in the UV printing field is advancing.
紫外線発光ダイオード（ＵＶ－ＬＥＤ）は、発光ピーク波長が３５０～４２０ｎｍの範囲の紫外線を発生する。即ち、従来のメタルハライドランプや高圧水銀灯等の光源を用いていたインクをＵＶ－ＬＥＤに適用させようとした場合、波長３５０～４２０ｎｍ付近に吸収を有する光重合開始剤を使用する必要があるが、インキに使用する顔料自身が波長３５０～４２０ｎｍの範囲の光を吸収するため、多くの場合、波長３５０～４２０ｎｍに吸収を有する光重合開始剤を使用しても硬化が不十分となる問題が生じる。
Ultraviolet light emitting diodes (UV-LEDs) emit ultraviolet light having an emission peak wavelength in the range of 350 to 420 nm. That is, when an ink using a light source such as a conventional metal halide lamp or a high-pressure mercury lamp is to be applied to a UV-LED, it is necessary to use a photopolymerization initiator having absorption in the vicinity of a wavelength of 350 to 420 nm. Since the pigment itself used in the ink absorbs light in the wavelength range of 350 to 420 nm, in many cases, even if a photopolymerization initiator having absorption at a wavelength of 350 to 420 nm is used, there is a problem that curing is insufficient. .
ＵＶ－ＬＥＤに適用させたインキ組成物としては、例えば、光重合開始剤としてα－（ジメチル）アミノアルキルフェノン化合物および／またはα－モルフォリノアルキルフェノン化合物と、ジアルキルアミノベンゾフェノン化合物（Ａ２－１）および／またはチオキサントン化合物とを併用した活性エネルギー線硬化型インキや（例えば特許文献１参照）、光重合開始剤としてα－アミノアルキルフェノン化合物とアシルフォスフィンオキサイド化合物とを併用し、且つ特定のアルコールを含有した活性エネルギー線硬化型インキ（例えば特許文献２参照）が知られている。しかしながらα－アミノアルキルフェノン化合物は、紫外線吸収領域がより短波長側にあり、ＵＶ－ＬＥＤで硬化させた場合、塗膜表面の硬化性に劣ることがあった。またα－モルフォリノアルキルフェノン化合物として汎用の２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン（Ｉｒｇａｃｕｒｅ９０７）は、紫外線照射直後に特異な臭気を発生させるため、高い衛生性が求められる用途では配合量に限界があり、十分な硬化性を得ることができなかった。
Examples of the ink composition applied to the UV-LED include an α- (dimethyl) aminoalkylphenone compound and / or an α-morpholinoalkylphenone compound and a dialkylaminobenzophenone compound (A2-1) as a photopolymerization initiator. And / or an active energy ray-curable ink combined with a thioxanthone compound (see, for example, Patent Document 1), an α-aminoalkylphenone compound and an acylphosphine oxide compound as a photopolymerization initiator, and a specific alcohol There is known an active energy ray-curable ink containing selenium (for example, see Patent Document 2). However, the α-aminoalkylphenone compound has an ultraviolet absorption region on the shorter wavelength side, and when cured with a UV-LED, the curability of the coating film surface may be inferior. Further, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907), a general-purpose α-morpholinoalkylphenone compound, generates a unique odor immediately after UV irradiation. For this reason, there is a limit to the amount of compounding in applications where high hygiene is required, and sufficient curability could not be obtained.
本発明者らは、ＵＶ－ＬＥＤ光源を使用した場合であっても非常に硬化が早く、且つ臭気等が生じにくい活性エネルギー線硬化型インキを提供することにある。
The present inventors are to provide an active energy ray-curable ink that cures very quickly and is less likely to cause odor even when a UV-LED light source is used.
本発明者らは、特定の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が上記課題を解決することを見出した。
The present inventors have found that an active energy ray-curable ink containing a specific photopolymerization initiator solves the above problems.
即ち本発明は、エチレン性不飽和二重結合を有するモノマー、及び一般式（１）で表される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を提供する。
That is, the present invention provides an active energy ray-curable ink containing a monomer having an ethylenically unsaturated double bond and a photopolymerization initiator represented by the general formula (1).
（１）
(1)
（式中、ｎは０または１を表し、Ｒ１～Ｒ４はそれぞれ独立して、炭素原子数１～１０の直鎖または分岐のアルキル基を表す。）
(In the formula, n represents 0 or 1, and R 1 to R 4 each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms.)
また本発明は、前記記載の活性エネルギー線硬化型インキを用いて印刷し、印刷されたインキを活性エネルギー線を用いて硬化させるインキ硬化物の製造方法を提供する。
The present invention also provides a method for producing an ink cured product that is printed using the active energy ray-curable ink described above and that cures the printed ink using the active energy ray.
また本発明は、前記記載の活性エネルギー線硬化型インキを用いてオフセット印刷し、印刷されたインキを活性エネルギー線を用いて硬化させるインキ硬化物の製造方法を提供する。
The present invention also provides a method for producing an ink cured product, in which offset printing is performed using the active energy ray-curable ink described above, and the printed ink is cured using the active energy ray. *
また本発明は、前記記載のインキ硬化物の製造方法で得られた印刷物を提供する。
The present invention also provides a printed matter obtained by the above-described method for producing an ink cured product.
本発明により、紫外線光源としてＵＶ－ＬＥＤ光源を使用した場合であっても非常に硬化が早く、且つ臭気等が生じにくい活性エネルギー線硬化型インキを得ることができるため、衛生性が求められるパッケージ印刷の分野でも問題なく使用することができる。
本発明のインキはオフセットインキ、凸版印刷用インキ、凹版印刷用インキ、孔版印刷用インキなど、従来の公知の種々の印刷方式のインキとして利用することができる。 According to the present invention, even when a UV-LED light source is used as an ultraviolet light source, an active energy ray-curable ink that can be cured very quickly and does not easily generate odors can be obtained. It can also be used without problems in the field of printing.
The ink of the present invention can be used as an ink of various conventionally known printing methods such as offset ink, relief printing ink, intaglio printing ink, and stencil printing ink.
本発明のインキはオフセットインキ、凸版印刷用インキ、凹版印刷用インキ、孔版印刷用インキなど、従来の公知の種々の印刷方式のインキとして利用することができる。 According to the present invention, even when a UV-LED light source is used as an ultraviolet light source, an active energy ray-curable ink that can be cured very quickly and does not easily generate odors can be obtained. It can also be used without problems in the field of printing.
The ink of the present invention can be used as an ink of various conventionally known printing methods such as offset ink, relief printing ink, intaglio printing ink, and stencil printing ink.
（一般式（１）で表される光重合開始剤）
本発明で使用する一般式（１）で表される光重合開始剤において、ｎは０または１を表し、Ｒ１～Ｒ４はそれぞれ独立して、炭素原子数１～１０の直鎖または分岐のアルキル基を表す。 (Photopolymerization initiator represented by general formula (1))
In the photopolymerization initiator represented by the general formula (1) used in the present invention, n represents 0 or 1, and R 1 to R 4 are each independently a straight chain or branched chain having 1 to 10 carbon atoms. Represents an alkyl group.
本発明で使用する一般式（１）で表される光重合開始剤において、ｎは０または１を表し、Ｒ１～Ｒ４はそれぞれ独立して、炭素原子数１～１０の直鎖または分岐のアルキル基を表す。 (Photopolymerization initiator represented by general formula (1))
In the photopolymerization initiator represented by the general formula (1) used in the present invention, n represents 0 or 1, and R 1 to R 4 are each independently a straight chain or branched chain having 1 to 10 carbon atoms. Represents an alkyl group.
前記Ｒ１～Ｒ４が表す炭素原子数１～１０の直鎖上または分岐上のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、アミル基、イソアミル基、ヘキシル基、ヘプチル基、イソヘプチル基、オクチル基、イソオクチル基、２－エチルヘキシル基、ノニル基、イソノニル基、デシル基等が挙げられる。
Examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by R 1 to R 4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, Examples thereof include a tert-butyl group, a pentyl group, an amyl group, an isoamyl group, a hexyl group, a heptyl group, an isoheptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, and a decyl group.
前記一般式（１）中、Ｒ１～Ｒ４はそれぞれ独立に、炭素原子数１～５の直鎖または分岐のアルキル基が好ましく、ｎは０であることがより好ましい。本発明にかかる上記光重合開始剤は例えば、下記に示す２－ベンジル－２－ジメチルアミノ－１－（４－ピペリジノフェニル）－ブタン－１－オン（別名：２－ベンジル－２－ジメチルアミノ－１－（４－ピペリジノフェニル）－ブタノン－１、２－ベンジル－２－ジメチルアミノ－１－（４－ピペリジノフェニル）－１－ブタノン等）等が挙げられる。
In the general formula (1), R 1 to R 4 are each independently preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and n is more preferably 0. Examples of the photopolymerization initiator according to the present invention include 2-benzyl-2-dimethylamino-1- (4-piperidinophenyl) -butan-1-one (also known as 2-benzyl-2-dimethyl) shown below. Amino-1- (4-piperidinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-piperidinophenyl) -1-butanone, etc.).
本発明においては、前記一般式（１）で表される光重合開始剤の含有量は、インキ固形分全量に対し０．５～１０質量％が好ましく、１．０～５．０質量％がより好ましい。０．５質量％以下の場合、紫外線照射で発生した活性なラジカルが空気中の酸素により失活し、インキの硬化性が著しく減少する。そのため、インキ原料の未反応物に由来する臭気が強くなったり、印刷物表面に傷が付き外観不良を起こしたり、印刷物の表面とその印刷物の上に排出された印刷物の裏面が重ねられ積み重なった場合に印刷物の表面とその上部の印刷物の裏面が密着するブロッキングと呼ばれる不具合が生じる。一方、１０質量％以上の場合は、光重合開始剤の析出する可能性が非常に高くなり、インキ製造直後から数日のうちに開始剤がインキ中に析出してしまい、設計通りのインキの硬化性能を発現できなくなる。更に、印刷機のローラーや版に、インキ中に析出した開始剤の粒子が堆積し、正しい画像を形成できなくなる可能性がある。
In the present invention, the content of the photopolymerization initiator represented by the general formula (1) is preferably 0.5 to 10% by mass, and 1.0 to 5.0% by mass with respect to the total amount of ink solids. More preferred. In the case of 0.5% by mass or less, active radicals generated by ultraviolet irradiation are deactivated by oxygen in the air, and the curability of the ink is remarkably reduced. Therefore, when the odor derived from the unreacted material of the ink material becomes strong, the printed surface is scratched and the appearance is deteriorated, or the printed surface and the back side of the printed material are stacked on top of each other and stacked In addition, there arises a problem called blocking in which the front surface of the printed matter and the back surface of the printed matter on the top are in close contact with each other. On the other hand, in the case of 10% by mass or more, the possibility of precipitation of the photopolymerization initiator becomes very high, and the initiator is precipitated in the ink within a few days immediately after the production of the ink. Curing performance cannot be expressed. In addition, initiator particles deposited in the ink may accumulate on the rollers and plates of the printing press, making it impossible to form a correct image.
〔汎用光重合開始剤の併用〕
本発明においては、本発明の効果を損なわない範囲で、前記一般式（１）で表される光重合開始剤以外に、使用する紫外線光源の種類、紫外線光源の照射強度、紫外線の照射積算光量、色、印刷膜厚、衛生性などを鑑みて、適宜、汎用の光重合開始剤を併用してもよく好ましい。一例を挙げると、例えば、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、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、２－ヒロドキシ－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、フェニル グリオキシリック アシッド メチル エステル、オキシフェニル酢酸、２－［２－オキソ－２－フェニルアセトキシエトキシ］エチルエステルとオキシフェニル酢酸、２－（２－ヒドロキシエトキシ）エチルエステルの混合物、１．２－オクタンジオン，１－［４－（フェニルチオ）－，２－（Ｏ－ベンゾイルオキシム）］、エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（０－アセチルオキシム）、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノンなどの化合物が挙げられる。 [Combination of general-purpose photopolymerization initiators]
In the present invention, within the range that does not impair the effects of the present invention, in addition to the photopolymerization initiator represented by the general formula (1), the type of ultraviolet light source to be used, the irradiation intensity of the ultraviolet light source, and the integrated amount of irradiation with ultraviolet light In view of color, printed film thickness, hygiene, etc., a general-purpose photopolymerization initiator may be suitably used in combination. For example, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- ON, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy- 2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, phenyl glyoxylic acid methyl ester, oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester Oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester mixture, 1.2-octanedione, 1- [ 4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0- Acetyloxime), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Examples include 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone.
本発明においては、本発明の効果を損なわない範囲で、前記一般式（１）で表される光重合開始剤以外に、使用する紫外線光源の種類、紫外線光源の照射強度、紫外線の照射積算光量、色、印刷膜厚、衛生性などを鑑みて、適宜、汎用の光重合開始剤を併用してもよく好ましい。一例を挙げると、例えば、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、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、２－ヒロドキシ－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、フェニル グリオキシリック アシッド メチル エステル、オキシフェニル酢酸、２－［２－オキソ－２－フェニルアセトキシエトキシ］エチルエステルとオキシフェニル酢酸、２－（２－ヒドロキシエトキシ）エチルエステルの混合物、１．２－オクタンジオン，１－［４－（フェニルチオ）－，２－（Ｏ－ベンゾイルオキシム）］、エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（０－アセチルオキシム）、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノンなどの化合物が挙げられる。 [Combination of general-purpose photopolymerization initiators]
In the present invention, within the range that does not impair the effects of the present invention, in addition to the photopolymerization initiator represented by the general formula (1), the type of ultraviolet light source to be used, the irradiation intensity of the ultraviolet light source, and the integrated amount of irradiation with ultraviolet light In view of color, printed film thickness, hygiene, etc., a general-purpose photopolymerization initiator may be suitably used in combination. For example, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- ON, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy- 2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, phenyl glyoxylic acid methyl ester, oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester Oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester mixture, 1.2-octanedione, 1- [ 4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0- Acetyloxime), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Examples include 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone.
また、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、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、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等のアシルフォスフィンオキサイド化合物が挙げられる。
Further, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl- Examples include acylphosphine oxide compounds such as pentylphosphine oxide.
また、２，４－ジエチルチオキサントン、２，４－ジメチルチオキサントン、２，４－ジイソプロピルチオキサントン、２－イソプロピルチオキサントン、４－ジイソプロピルチオキサントン、２－イソプロピルチオキサントン、４－イソプロピルチオキサントン、２，４－ジクロロチオキサントン、２－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、２－ヒドロキシ－３－（３，４－ジメチル－９－オキソ－９Ｈチオキサントン－２－イロキシ－Ｎ，Ｎ，Ｎ－トリメチル－１－プロパンアミン塩酸塩等のチオキサントン化合物が挙げられる。
2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-isopropylthioxanthone, 4-diisopropylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H thioxanthone-2-iroxy-N, N, N-trimethyl-1-propanamine Examples thereof include thioxanthone compounds such as hydrochloride.
また、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’－ジアルキルアミノベンゾフェノン類、４－ベンゾイル－４’－メチルジフェニルスルフィド等のベンゾフェノン化合物が挙げられる。
In addition, 4,4′-bis- (dimethylamino) benzophenone, 4,4′-bis- (diethylamino) benzophenone and the like, 4,4′-dialkylaminobenzophenones, 4-benzoyl-4′-methyldiphenyl sulfide and the like A benzophenone compound is mentioned.
それ以外には、例えばベンゾフェノン、４－メチル－ベンゾフェノン、２，４，６－トリメチルベンゾフェノン、２，３，４－トリメチルベンゾフェノン、４－フェニルベンゾフェノン、３，３‘－ジメチル－４－メトキシベンゾフェノン、４－（１，３－アクリロイル－１，４，７，１０，１３－ペンタオキソトリデシル）ベンゾフェノン、メチル－ｏ－ベンゾイルベンゾエート、〔４－（メチルフェニルチオ）フェニル〕フェニルメタノン、ジエトキシアセトフェノン、ジブトキシアセトフェノン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンゾインノルマルブチルエーテルなどが挙げられる。
Other than that, for example, benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 2,3,4-trimethylbenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4 -(1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, methyl-o-benzoylbenzoate, [4- (methylphenylthio) phenyl] phenylmethanone, diethoxyacetophenone, Examples include dibutoxyacetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether.
本発明においては、前記一般式（１）で表される光重合開始剤と併用する前記汎用の光重合開始剤は、１種でも数種併用して使用してもよい。中でも、前記一般式（１）で表される光重合開始剤とアシルフォスフィンオキサイド化合物とを併用することが好ましく、特に樹脂に対する溶解性の点から、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を併用することがより好ましい。併用する場合、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の含有量は、前記一般式（１）で表される光重合開始剤に対し７０～２０００質量％となるように含有することが好ましく、７０～１０００質量％がより好ましい。また併用する場合の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の使用量は、インキ固形分全量に対し１．０～１５質量％が好ましく、３．０～１０質量％がより好ましい。１．０質量％未満の場合は、十分な硬化性の向上効果が得られず、１５質量％を超える場合は、ＵＶ照射後でも未反応のアシルフォスフィンオキサイドが硬化塗膜中に残存し、硬化塗膜の色相が許容できないくらい黄味に変色したり、開始剤が析出したり、インキの流動性が著しく低下したりする。
In the present invention, the general-purpose photopolymerization initiator used in combination with the photopolymerization initiator represented by the general formula (1) may be used alone or in combination. Among these, it is preferable to use a photopolymerization initiator represented by the general formula (1) and an acyl phosphine oxide compound in combination, and 2,4,6-trimethylbenzoyldiphenylphosphine is particularly preferable from the viewpoint of solubility in a resin. It is more preferable to use an oxide in combination. When used in combination, the content of 2,4,6-trimethylbenzoyldiphenylphosphine oxide may be 70 to 2000% by mass with respect to the photopolymerization initiator represented by the general formula (1). 70 to 1000% by mass is more preferable. When used in combination, the amount of 2,4,6-trimethylbenzoyldiphenylphosphine oxide used is preferably 1.0 to 15% by mass, more preferably 3.0 to 10% by mass, based on the total amount of ink solids. When the amount is less than 1.0% by mass, a sufficient effect of improving curability cannot be obtained. When the amount exceeds 15% by mass, unreacted acylphosphine oxide remains in the cured coating film even after UV irradiation. The color of the cured coating film changes to an unacceptable yellowish color, the initiator is deposited, and the fluidity of the ink is significantly reduced.
〔増感剤・光開始助剤〕
光増感剤は、紫外線を吸収して電子励起一重項状態に遷移した後、系間交差により三重項状態に遷移する。そして、基底状態の光重合開始剤と衝突した際にエネルギー移動が生じ、光重合開始剤を励起三重項状態に遷移させる働きをする化合物である。例えばＬＥＤ等の発光波長域が狭い光源を使用する場合は、光開始剤からラジカルを効率よく発生させ、光重合開始剤の働きをサポートする為、増感剤を組み合わせることが好ましい。
また、光開始助剤は、α位の炭素上に少なくとも１つの水素を持つ２級、３級アミン化合物である。これらの化合物のα位の炭素上の水素は、ラジカルにより引き抜かれ、３級アミン化合物はα－アミノアルキルラジカルとなる。α－アミノアルキルラジカルは（メタ）アクリレートモノマーの重合を効率よく開始させることができる。一方、α－アミノアルキルラジカルは空気中の酸素と反応すると、オキシルラジカルが生成し、（メタ）アクリレートモノマーの重合開始能が失われるが、このオキシルラジカルは、未反応の光開始助剤から水素を引き抜き、（メタ）アクリレートモノマーの重合を開始させることのできる新たなα－アミノアルキルラジカルを生じさせる。従って、空気中の酸素による光開始剤の失活を好適に抑制することができるため、光開始助剤を組み合わせることが好ましい。更に、活性エネルギー線硬化型インキをオフセット印刷用途に使用する場合、親水性の非画線部へのインキの付着を抑制させるため、塩基性度のより低い３級アミン化合物を使用し、活性エネルギー線硬化型インキの過乳化を抑制することがより好ましい。 [Sensitizer / Photoinitiator]
The photosensitizer absorbs ultraviolet rays and transitions to an electronically excited singlet state, and then transitions to a triplet state due to intersystem crossing. And, it is a compound that acts to shift the photopolymerization initiator to the excited triplet state when energy transfer occurs when colliding with the photopolymerization initiator in the ground state. For example, when using a light source having a narrow emission wavelength range such as an LED, it is preferable to combine a sensitizer in order to efficiently generate radicals from the photoinitiator and support the function of the photopolymerization initiator.
The photoinitiator aid is a secondary or tertiary amine compound having at least one hydrogen on the α-position carbon. The hydrogen on the α-position carbon of these compounds is extracted by radicals, and the tertiary amine compounds become α-aminoalkyl radicals. The α-aminoalkyl radical can efficiently initiate the polymerization of the (meth) acrylate monomer. On the other hand, when the α-aminoalkyl radical reacts with oxygen in the air, an oxyl radical is generated and the polymerization initiating ability of the (meth) acrylate monomer is lost. This oxyl radical is converted from an unreacted photoinitiator to hydrogen. To produce a new α-aminoalkyl radical that can initiate polymerization of the (meth) acrylate monomer. Accordingly, it is possible to suitably suppress the deactivation of the photoinitiator due to oxygen in the air, and therefore it is preferable to combine a photoinitiator aid. Furthermore, when an active energy ray-curable ink is used for offset printing, a tertiary amine compound having a lower basicity is used in order to suppress ink adhesion to hydrophilic non-image areas. It is more preferable to suppress over-emulsification of the linear curable ink.
光増感剤は、紫外線を吸収して電子励起一重項状態に遷移した後、系間交差により三重項状態に遷移する。そして、基底状態の光重合開始剤と衝突した際にエネルギー移動が生じ、光重合開始剤を励起三重項状態に遷移させる働きをする化合物である。例えばＬＥＤ等の発光波長域が狭い光源を使用する場合は、光開始剤からラジカルを効率よく発生させ、光重合開始剤の働きをサポートする為、増感剤を組み合わせることが好ましい。
また、光開始助剤は、α位の炭素上に少なくとも１つの水素を持つ２級、３級アミン化合物である。これらの化合物のα位の炭素上の水素は、ラジカルにより引き抜かれ、３級アミン化合物はα－アミノアルキルラジカルとなる。α－アミノアルキルラジカルは（メタ）アクリレートモノマーの重合を効率よく開始させることができる。一方、α－アミノアルキルラジカルは空気中の酸素と反応すると、オキシルラジカルが生成し、（メタ）アクリレートモノマーの重合開始能が失われるが、このオキシルラジカルは、未反応の光開始助剤から水素を引き抜き、（メタ）アクリレートモノマーの重合を開始させることのできる新たなα－アミノアルキルラジカルを生じさせる。従って、空気中の酸素による光開始剤の失活を好適に抑制することができるため、光開始助剤を組み合わせることが好ましい。更に、活性エネルギー線硬化型インキをオフセット印刷用途に使用する場合、親水性の非画線部へのインキの付着を抑制させるため、塩基性度のより低い３級アミン化合物を使用し、活性エネルギー線硬化型インキの過乳化を抑制することがより好ましい。 [Sensitizer / Photoinitiator]
The photosensitizer absorbs ultraviolet rays and transitions to an electronically excited singlet state, and then transitions to a triplet state due to intersystem crossing. And, it is a compound that acts to shift the photopolymerization initiator to the excited triplet state when energy transfer occurs when colliding with the photopolymerization initiator in the ground state. For example, when using a light source having a narrow emission wavelength range such as an LED, it is preferable to combine a sensitizer in order to efficiently generate radicals from the photoinitiator and support the function of the photopolymerization initiator.
The photoinitiator aid is a secondary or tertiary amine compound having at least one hydrogen on the α-position carbon. The hydrogen on the α-position carbon of these compounds is extracted by radicals, and the tertiary amine compounds become α-aminoalkyl radicals. The α-aminoalkyl radical can efficiently initiate the polymerization of the (meth) acrylate monomer. On the other hand, when the α-aminoalkyl radical reacts with oxygen in the air, an oxyl radical is generated and the polymerization initiating ability of the (meth) acrylate monomer is lost. This oxyl radical is converted from an unreacted photoinitiator to hydrogen. To produce a new α-aminoalkyl radical that can initiate polymerization of the (meth) acrylate monomer. Accordingly, it is possible to suitably suppress the deactivation of the photoinitiator due to oxygen in the air, and therefore it is preferable to combine a photoinitiator aid. Furthermore, when an active energy ray-curable ink is used for offset printing, a tertiary amine compound having a lower basicity is used in order to suppress ink adhesion to hydrophilic non-image areas. It is more preferable to suppress over-emulsification of the linear curable ink.
好ましい光増感剤としては、特に限定されないが、チオキサントン系、４，４’－ビス（ジエチルアミノ）ベンゾフェノン等のベンゾフェノン系、アントラキノン系、クマリン系などが挙げられる。
これらの中でも、特に２，４－ジエチルチオキサントン、２，４－ジメチルチオキサントン、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、２－クロロチオキサントン、２－イソプロピルチオキサントンなどのチオキサントン系化合物や、ミヒラーケトン、４，４´－ビス－（ジエチルアミノ）ベンゾフェノンなど４，４’－ジアルキルアミノベンゾフェノン類が好ましく、性能、安全性や入手しやすさなどの観点から、２，４－ジエチルチオキサントン，２－イソプロピルチオキサントン、４，４´－ビス－（ジエチルアミノ）ベンゾフェノンが特に好ましい。
増感剤は、インキ固形分全量に対し０．０５～１０質量％が好ましく、０．１～７．０質量％の範囲がより好ましい。０．０５質量％未満の場合は、十分な硬化性の向上効果が得られず、１０質量％を超える場合は、硬化塗膜の色相が許容できないくらい黄味に変色したり、増感剤が析出したり、インキの流動性が著しく低下したりする。 Preferred photosensitizers include, but are not limited to, thioxanthone series, benzophenone series such as 4,4′-bis (diethylamino) benzophenone, anthraquinone series, and coumarin series.
Among these, in particular, thioxanthone compounds such as 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4,4′-dialkylaminobenzophenones such as Michler's ketone and 4,4′-bis- (diethylamino) benzophenone are preferable. From the viewpoint of performance, safety, and availability, 2,4-diethylthioxanthone, 2- Isopropylthioxanthone and 4,4′-bis- (diethylamino) benzophenone are particularly preferred.
The sensitizer is preferably from 0.05 to 10% by mass, more preferably from 0.1 to 7.0% by mass, based on the total amount of ink solids. When the amount is less than 0.05% by mass, a sufficient effect of improving the curability cannot be obtained. When the amount exceeds 10% by mass, the color of the cured coating film changes to an unacceptable yellowish color, or a sensitizer is used. Precipitation may occur or the fluidity of the ink may be significantly reduced.
これらの中でも、特に２，４－ジエチルチオキサントン、２，４－ジメチルチオキサントン、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、２－クロロチオキサントン、２－イソプロピルチオキサントンなどのチオキサントン系化合物や、ミヒラーケトン、４，４´－ビス－（ジエチルアミノ）ベンゾフェノンなど４，４’－ジアルキルアミノベンゾフェノン類が好ましく、性能、安全性や入手しやすさなどの観点から、２，４－ジエチルチオキサントン，２－イソプロピルチオキサントン、４，４´－ビス－（ジエチルアミノ）ベンゾフェノンが特に好ましい。
増感剤は、インキ固形分全量に対し０．０５～１０質量％が好ましく、０．１～７．０質量％の範囲がより好ましい。０．０５質量％未満の場合は、十分な硬化性の向上効果が得られず、１０質量％を超える場合は、硬化塗膜の色相が許容できないくらい黄味に変色したり、増感剤が析出したり、インキの流動性が著しく低下したりする。 Preferred photosensitizers include, but are not limited to, thioxanthone series, benzophenone series such as 4,4′-bis (diethylamino) benzophenone, anthraquinone series, and coumarin series.
Among these, in particular, thioxanthone compounds such as 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4,4′-dialkylaminobenzophenones such as Michler's ketone and 4,4′-bis- (diethylamino) benzophenone are preferable. From the viewpoint of performance, safety, and availability, 2,4-diethylthioxanthone, 2- Isopropylthioxanthone and 4,4′-bis- (diethylamino) benzophenone are particularly preferred.
The sensitizer is preferably from 0.05 to 10% by mass, more preferably from 0.1 to 7.0% by mass, based on the total amount of ink solids. When the amount is less than 0.05% by mass, a sufficient effect of improving the curability cannot be obtained. When the amount exceeds 10% by mass, the color of the cured coating film changes to an unacceptable yellowish color, or a sensitizer is used. Precipitation may occur or the fluidity of the ink may be significantly reduced.
一方、三級アミンとしては、特に限定されないが、ｐ－ジメチルアミノ安息香酸エチル、ｐ－ジメチルアミノ安息香酸イソアミル、Ｎ，Ｎ－ジメチルベンジルアミン、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、Ｎ，Ｎ－ジヒドロキシエチルアニリン、トリエチルアミンおよびＮ，Ｎ－ジメチルヘキシルアミン等が挙げられ、酸素による重合阻害を低減させたり、紫外線により活性化されたチオキサントン類、４，４’－ジアルキルアミノベンゾフェノン類と反応し、活性ラジカル供与体となり、インキの硬化性能を向上させる。三級アミンは本発明の活性エネルギー線硬化型インキの印刷性能を損なわない範囲で併用することが好ましく、インキ固形分全量に対し０．１～１０質量％が好ましく、０．１～５．０質量％の範囲で使用することがより好ましい。
On the other hand, the tertiary amine is not particularly limited, but ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-diethylaniline. N, N-dimethyl-p-toluidine, N, N-dihydroxyethylaniline, triethylamine, N, N-dimethylhexylamine, etc., and thioxanthones reduced in polymerization by oxygen or activated by ultraviolet rays , Reacts with 4,4′-dialkylaminobenzophenones to become active radical donors, and improves the curing performance of the ink. The tertiary amine is preferably used in combination as long as it does not impair the printing performance of the active energy ray-curable ink of the present invention, preferably 0.1 to 10% by weight, and preferably 0.1 to 5.0% by weight based on the total amount of ink solids. It is more preferable to use in the range of mass%.
また高い衛生性を求められる用途においては、１分子内に複数の光増感剤や三級アミンを多価アルコール等で分岐させた高分子量化合物も適宜使用することができる。
In applications where high hygiene is required, high molecular weight compounds in which a plurality of photosensitizers or tertiary amines are branched in one molecule with a polyhydric alcohol or the like can be used as appropriate.
（エチレン性不飽和二重結合を有するモノマー）
本発明で使用する活性エネルギー線硬化性モノマー及び又はオリゴマーは、活性エネルギー線硬化性技術分野で使用されるモノマー及び又はオリゴマーであれば特に限定なく使用することができる。特に反応基として（メタ）アクリロイル基、ビニルエーテル基等を有するものが好ましい。また反応基数や分子量にも特に限定はなく、反応基数の多いものほど反応性は高いが粘度や結晶性が高くなる傾向にあり、また分子量が高いものほど粘度が高くなる傾向にあることから、所望の物性に応じて適宜組み合わせて使用することができる。例えばＵＶ－ＬＥＤのような低エネルギー照射で好適に硬化させるという点では、より反応性の高い３官能以上の活性エネルギー線硬化性モノマーを組み合わせ、用途に応じて印刷基材への接着性、皮膜の柔軟性等の必要物性を得る為に、適宜単官能、２官能のモノマーを単独もしくは併用することが好ましい。 (Monomer having an ethylenically unsaturated double bond)
The active energy ray-curable monomer and / or oligomer used in the present invention can be used without particular limitation as long as it is a monomer and / or oligomer used in the active energy ray-curable technical field. Particularly preferred are those having a (meth) acryloyl group, a vinyl ether group or the like as a reactive group. Also, there is no particular limitation on the number of reactive groups and molecular weight, and the higher the number of reactive groups, the higher the reactivity but the higher the viscosity and crystallinity, and the higher the molecular weight, the higher the viscosity. They can be used in appropriate combinations according to the desired physical properties. For example, UV-LEDs can be suitably cured by low-energy irradiation, combining more reactive trifunctional or more active energy ray-curable monomers, depending on the application, adhesion to the printing substrate, coating In order to obtain necessary physical properties such as flexibility, it is preferable to appropriately use a monofunctional or bifunctional monomer alone or in combination.
本発明で使用する活性エネルギー線硬化性モノマー及び又はオリゴマーは、活性エネルギー線硬化性技術分野で使用されるモノマー及び又はオリゴマーであれば特に限定なく使用することができる。特に反応基として（メタ）アクリロイル基、ビニルエーテル基等を有するものが好ましい。また反応基数や分子量にも特に限定はなく、反応基数の多いものほど反応性は高いが粘度や結晶性が高くなる傾向にあり、また分子量が高いものほど粘度が高くなる傾向にあることから、所望の物性に応じて適宜組み合わせて使用することができる。例えばＵＶ－ＬＥＤのような低エネルギー照射で好適に硬化させるという点では、より反応性の高い３官能以上の活性エネルギー線硬化性モノマーを組み合わせ、用途に応じて印刷基材への接着性、皮膜の柔軟性等の必要物性を得る為に、適宜単官能、２官能のモノマーを単独もしくは併用することが好ましい。 (Monomer having an ethylenically unsaturated double bond)
The active energy ray-curable monomer and / or oligomer used in the present invention can be used without particular limitation as long as it is a monomer and / or oligomer used in the active energy ray-curable technical field. Particularly preferred are those having a (meth) acryloyl group, a vinyl ether group or the like as a reactive group. Also, there is no particular limitation on the number of reactive groups and molecular weight, and the higher the number of reactive groups, the higher the reactivity but the higher the viscosity and crystallinity, and the higher the molecular weight, the higher the viscosity. They can be used in appropriate combinations according to the desired physical properties. For example, UV-LEDs can be suitably cured by low-energy irradiation, combining more reactive trifunctional or more active energy ray-curable monomers, depending on the application, adhesion to the printing substrate, coating In order to obtain necessary physical properties such as flexibility, it is preferable to appropriately use a monofunctional or bifunctional monomer alone or in combination.
具体的には例えば、単官能（メタ）アクリレート、多官能（メタ）アクリレート、重合性オリゴマー等の、ランプ方式で実績のあるものが、本発明で述べる紫外線発光ダイオード方式においてもそのまま使用することが可能である。
Specifically, for example, those that have a proven record in lamp systems, such as monofunctional (meth) acrylates, polyfunctional (meth) acrylates, and polymerizable oligomers, can be used as they are in the ultraviolet light-emitting diode system described in the present invention. Is possible. *
単官能（メタ）アクリレートとしては、例えば、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、オクタデシル（メタ）アクリレート、イソアミル（メタ）アクリレート、イソデシル（メタ）アクリレート、イソステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、ノニルフェノキシエチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、グリシジル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシー３－フェノキシプロピル（メタ）アクリレート、３－クロロ－２－ヒドロキシプロピル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ノニルフェノキシエチルテトラヒドロフルフリル（メタ）アクリレート、カプロラクトン変性テトラヒドロフルフリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニロキシエチル（メタ）アクリレート等が挙げられる。
Examples of the monofunctional (meth) acrylate include ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, hexadecyl (Meth) acrylate, octadecyl (meth) acrylate, isoamyl (meth) acrylate, isodecyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxy Ethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate Tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, Diethylaminoethyl (meth) acrylate, nonylphenoxyethyl tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl ( And (meth) acrylate. *
２官能以上の（メタ）アクリレートとしては、例えば、１，４－ブタンジオールジ（メタ）アクリレート、３－メチル－１，５－ペンタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、２－メチル－１，８－オクタンジオールジ（メタ）アクリレート、２－ブチルー２－エチルー１，３－プロパンジオールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート等の２価アルコールのジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（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、ネ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トリ（メタ）アクリレート、グリセリントリ（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、ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールのポリ（メタ）アクリレート等の３価以上の多価アルコールのポリ（メタ）アクリレート、グリセリン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トリ（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又はトリ（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）アクリレート等のポリオキシアルキレンポリオールのポリ（メタ）アクリレート等が挙げられる。
Examples of the bifunctional or higher functional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. ) Acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, tricyclodecanedi Such as methanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, etc. 2 Di (meth) acrylate of alcohol, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, 4 moles or more per mole of neopentyl glycol Di (meth) acrylate of diol obtained by adding ethylene oxide or propylene oxide, di (meth) acrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, trimethylolpropane tri ( (Meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolprop Obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of poly (meth) acrylate of trihydric or higher polyhydric alcohol such as tetra (meth) acrylate or poly (meth) acrylate of dipentaerythritol Triol tri (meth) acrylate, triol di- or tri (meth) acrylate obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane, 4 mol or more of ethylene oxide or 1 mol of bisphenol A Examples include poly (meth) acrylates of polyoxyalkylene polyols such as di (meth) acrylates of diols obtained by adding propylene oxide. *
重合性オリゴマーとしては、アミン変性ポリエーテルアクリレート、アミン変性エポキシアクリレート、アミン変性脂肪族アクリレート、アミン変性ポリエステルアクリレート、アミノ（メタ）アクリレートなどのアミン変性アクリレート、チオール変性ポリエステルアクリレート、チオール（メタ）アクリレートなどのチオール変性アクリレート、ポリエステル（メタ）アクリレート、ポリエーテル（メタ）アクリレート、ポリオレフィン（メタ）アクリレート、ポリスチレン（メタ）アクリレート、エポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート等が挙げられる。
Examples of the polymerizable oligomer include amine-modified polyether acrylate, amine-modified epoxy acrylate, amine-modified aliphatic acrylate, amine-modified polyester acrylate, amine-modified acrylate such as amino (meth) acrylate, thiol-modified polyester acrylate, and thiol (meth) acrylate. Thiol-modified acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polyolefin (meth) acrylate, polystyrene (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and the like.
また前記活性エネルギー線硬化性モノマー及び又はオリゴマーとして、４官能以上の（メタ）アクリレートは、上質紙、コート紙、アート紙、模造紙、薄紙、厚紙等の紙への印刷用途において、硬化性や強度の向上に大きく寄与するため使用することが好ましく、インキ固形分全量に対し１５～７０質量％の範囲で使用することが好ましい。一方、プラスチックへの印刷用途においては、硬化塗膜の架橋密度が上昇するに従って、基材と硬化塗膜との密着性が減少するため、４官能以上の（メタ）アクリレートの含有量を適宜減少させる必要がある。この場合、４官能以上の（メタ）アクリレートはインキ固形分全量に対し０～５０質量％の範囲で使用することが好ましい。
Further, as the active energy ray-curable monomer and / or oligomer, a tetra- or higher functional (meth) acrylate is used for printing on paper such as fine paper, coated paper, art paper, imitation paper, thin paper, cardboard, etc. It is preferably used because it greatly contributes to the improvement in strength, and it is preferably used in the range of 15 to 70% by mass with respect to the total amount of ink solids. On the other hand, in printing applications on plastics, as the crosslink density of the cured coating increases, the adhesiveness between the substrate and the cured coating decreases, so the content of tetrafunctional or higher (meth) acrylates is reduced accordingly. It is necessary to let In this case, it is preferable to use tetrafunctional or higher functional (meth) acrylate in the range of 0 to 50% by mass with respect to the total amount of ink solids.
本発明の活性エネルギー線硬化型インキは、前記エチレン性不飽和二重結合を有するモノマー、及び前記一般式（１）で表される光重合開始剤とを必須成分とするものであるが、その他、樹脂や顔料、各種添加剤を使用することができる。
The active energy ray curable ink of the present invention comprises the monomer having the ethylenically unsaturated double bond and the photopolymerization initiator represented by the general formula (1) as essential components. Resins, pigments, and various additives can be used.
（樹脂）
樹脂としては、公知公用の各種バインダー樹脂を利用することができる。ここで述べるバインダー樹脂とは、適切な顔料親和性と分散性を有し、印刷インキに要求されるレオロジー特性を有する樹脂全般を示しており、例えば非反応性樹脂としては、オルソフタル酸ジアリル及び／またはイソフタル酸ジアリル及び／またはテレフタル酸ジアリルを重合させたジアリルフタレート樹脂、エポキシ樹脂、ポリウレタン樹脂、ポリエステル樹脂、石油樹脂、ロジンエステル樹脂、ポリ（メタ）アクリル酸エステル、セルロース誘導体、塩化ビニル－酢酸ビニル共重合体、ポリアマイド樹脂、ポリビニルアセタール樹脂、ブタジエン－アクリルニトリル共重合体等を挙げることができ、また分子中に少なくとも１つ以上の重合性基を有するエポキシアクリレート化合物、ウレタンアクリレート化合物、ポリエステルアクリレート化合物等を使用することもでき、これらバインダー樹脂は、単独で使用しても、いずれか１種以上を組合せて使用してもよい。 (resin)
As the resin, various publicly known binder resins can be used. The binder resin described here refers to all resins having appropriate pigment affinity and dispersibility, and rheological properties required for printing inks. For example, non-reactive resins include diallyl orthophthalate and / or Alternatively, diallyl phthalate resin obtained by polymerizing diallyl isophthalate and / or diallyl terephthalate, epoxy resin, polyurethane resin, polyester resin, petroleum resin, rosin ester resin, poly (meth) acrylate ester, cellulose derivative, vinyl chloride-vinyl acetate Examples thereof include copolymers, polyamide resins, polyvinyl acetal resins, butadiene-acrylonitrile copolymers, and epoxy acrylate compounds, urethane acrylate compounds, polyester acrylate compounds having at least one polymerizable group in the molecule. Can also use over preparative compounds, these binder resins may be used alone or may be used in combination of one or more either.
樹脂としては、公知公用の各種バインダー樹脂を利用することができる。ここで述べるバインダー樹脂とは、適切な顔料親和性と分散性を有し、印刷インキに要求されるレオロジー特性を有する樹脂全般を示しており、例えば非反応性樹脂としては、オルソフタル酸ジアリル及び／またはイソフタル酸ジアリル及び／またはテレフタル酸ジアリルを重合させたジアリルフタレート樹脂、エポキシ樹脂、ポリウレタン樹脂、ポリエステル樹脂、石油樹脂、ロジンエステル樹脂、ポリ（メタ）アクリル酸エステル、セルロース誘導体、塩化ビニル－酢酸ビニル共重合体、ポリアマイド樹脂、ポリビニルアセタール樹脂、ブタジエン－アクリルニトリル共重合体等を挙げることができ、また分子中に少なくとも１つ以上の重合性基を有するエポキシアクリレート化合物、ウレタンアクリレート化合物、ポリエステルアクリレート化合物等を使用することもでき、これらバインダー樹脂は、単独で使用しても、いずれか１種以上を組合せて使用してもよい。 (resin)
As the resin, various publicly known binder resins can be used. The binder resin described here refers to all resins having appropriate pigment affinity and dispersibility, and rheological properties required for printing inks. For example, non-reactive resins include diallyl orthophthalate and / or Alternatively, diallyl phthalate resin obtained by polymerizing diallyl isophthalate and / or diallyl terephthalate, epoxy resin, polyurethane resin, polyester resin, petroleum resin, rosin ester resin, poly (meth) acrylate ester, cellulose derivative, vinyl chloride-vinyl acetate Examples thereof include copolymers, polyamide resins, polyvinyl acetal resins, butadiene-acrylonitrile copolymers, and epoxy acrylate compounds, urethane acrylate compounds, polyester acrylate compounds having at least one polymerizable group in the molecule. Can also use over preparative compounds, these binder resins may be used alone or may be used in combination of one or more either.
この中でも、前記一般式（１）で表される光重合開始剤とジアリルフタレート樹脂を併用すると、活性エネルギー線硬化型インキの硬化性が向上する他、インキの流動性が向上し、印刷機上で壺切れ、インキローラ間の転移不良といった印刷適性面での不良の発生を抑制することができる。
Among these, when the photopolymerization initiator represented by the general formula (1) and diallyl phthalate resin are used in combination, the curability of the active energy ray-curable ink is improved and the fluidity of the ink is improved. Therefore, it is possible to suppress the occurrence of defects in printability such as fraying and poor transfer between ink rollers.
（顔料）
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。 (Pigment)
Examples of the pigment include publicly known organic pigments for coloring, such as organic pigments for printing inks published in “Organic Pigment Handbook (Author: Isao Hashimoto, Publisher: Color Office, 2006 First Edition)”. Soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinones A pigment, a quinophthalone pigment, a metal complex pigment, a diketopyrrolopyrrole pigment, a carbon black pigment, and other polycyclic pigments can be used.
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。 (Pigment)
Examples of the pigment include publicly known organic pigments for coloring, such as organic pigments for printing inks published in “Organic Pigment Handbook (Author: Isao Hashimoto, Publisher: Color Office, 2006 First Edition)”. Soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinones A pigment, a quinophthalone pigment, a metal complex pigment, a diketopyrrolopyrrole pigment, a carbon black pigment, and other polycyclic pigments can be used.
また、本発明の活性エネルギー線硬化型インキには、体質顔料として無機微粒子を用いてもよい。無機微粒子としては、酸化チタン、グラファイト、亜鉛華等の無機着色顔料；炭酸石灰粉、沈降性炭酸カルシウム、石膏、クレー（ＣｈｉｎａＣｌａｙ）、シリカ粉、珪藻土、タルク、カオリン、アルミナホワイト、硫酸バリウム、ステアリン酸アルミニウム、炭酸マグネシウム、バライト粉、砥の粉等の無機体質顔料； 等の無機顔料や、シリコーン、ガラスビーズなどがあげられる。これら無機微粒子は、インキ中に０．１～６０重量％の範囲で使用することにより、着色やインキのレオロジー特性を調整したりすることが可能である。
In the active energy ray-curable ink of the present invention, inorganic fine particles may be used as extender pigments. Inorganic fine particles include inorganic coloring pigments such as titanium oxide, graphite, zinc white; lime carbonate powder, precipitated calcium carbonate, gypsum, clay (ChinaClay), silica powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, stearin Inorganic pigments such as aluminum oxide, magnesium carbonate, barite powder, and abrasive powder; inorganic pigments such as silicone, glass beads, and the like. By using these inorganic fine particles in the ink in the range of 0.1 to 60% by weight, it is possible to adjust coloring and rheological properties of the ink.
（その他添加剤）
その他の添加剤としては、例えば耐摩擦性、ブロッキング防止性、スベリ性、スリキズ防止性を付与する添加剤としては、カルナバワックス、木ろう、ラノリン、モンタンワックス、パラフィンワックス、マイクロクリスタリンワックスなどの天然ワックス、フィッシャートロプスワックス、ポリエチレンワックス、ポリプロピレンワックス、ポリテトラフルオロエチレンワックス、ポリアミドワックス、およびシリコーン化合物などの合成ワックス等を例示することができる。 (Other additives)
Other additives include, for example, carnauba wax, wax, lanolin, montan wax, paraffin wax, and microcrystalline wax as additives that impart friction resistance, antiblocking properties, slipperiness, and scratch resistance. Examples thereof include waxes, Fischer-Trops waxes, polyethylene waxes, polypropylene waxes, polytetrafluoroethylene waxes, polyamide waxes, and synthetic waxes such as silicone compounds.
その他の添加剤としては、例えば耐摩擦性、ブロッキング防止性、スベリ性、スリキズ防止性を付与する添加剤としては、カルナバワックス、木ろう、ラノリン、モンタンワックス、パラフィンワックス、マイクロクリスタリンワックスなどの天然ワックス、フィッシャートロプスワックス、ポリエチレンワックス、ポリプロピレンワックス、ポリテトラフルオロエチレンワックス、ポリアミドワックス、およびシリコーン化合物などの合成ワックス等を例示することができる。 (Other additives)
Other additives include, for example, carnauba wax, wax, lanolin, montan wax, paraffin wax, and microcrystalline wax as additives that impart friction resistance, antiblocking properties, slipperiness, and scratch resistance. Examples thereof include waxes, Fischer-Trops waxes, polyethylene waxes, polypropylene waxes, polytetrafluoroethylene waxes, polyamide waxes, and synthetic waxes such as silicone compounds.
また例えば、インキの保存安定性を付与する添加剤としては、（アルキル）フェノール、ハイドロキノン、カテコール、レゾルシン、ｐ －メトキシフェノール、ｔ －ブチルカテコール、ｔ －ブチルハイドロキノン、ピロガロール、１，１－ピクリルヒドラジル、フェノチアジン、ｐ －ベンゾキノン、ニトロソベンゼン、２，５－ジ－ｔｅｒｔ－ブチル－ｐ －ベンゾキノン、ジチオベンゾイルジスルフィド、ピクリン酸、クペロン、アルミニウムＮ－ニトロソフェニルヒドロキシルアミン、トリ－ｐ －ニトロフェニルメチル、Ｎ－（３－オキシアニリノ－１，３－ジメチルブチリデン）アニリンオキシド、ジブチルクレゾール、シクロヘキサノンオキシムクレゾール、グアヤコール、ｏ－イソプロピルフェノール、ブチラルドキシム、メチルエチルケトキシム、シクロヘキサノンオキシム等の重合禁止剤が例示される。
Also, for example, additives that impart ink storage stability include (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picryl. Hydrazyl, phenothiazine, p-benzoquinone, nitrosobenzene, 2,5-di-tert-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl N- (3-oxyanilino-1,3-dimethylbutylidene) aniline oxide, dibutylcresol, cyclohexanone oximecresol, guaiacol, o-isopropylphenol, butyraldoxy Arm, methyl ethyl ketoxime, a polymerization inhibitor such as cyclohexanone oxime can be exemplified. *
その他、要求性能に応じて、紫外線吸収剤、赤外線吸収剤、抗菌剤等の添加剤を添加することができる。
Other additives such as ultraviolet absorbers, infrared absorbers and antibacterial agents can be added according to the required performance. *
本発明の活性エネルギー線硬化型インキは、無溶剤で使用することもできるし、必要に応じて適当な溶媒を使用する事も可能である。溶媒としては、上記各成分と反応しないものであれば特に限定されるものではなく、単独あるいは２種以上を組み合わせて使用することができる。
The active energy ray-curable ink of the present invention can be used without a solvent, and an appropriate solvent can be used as necessary. The solvent is not particularly limited as long as it does not react with each of the above components, and can be used alone or in combination of two or more.
本発明の活性エネルギー線硬化型インキは、従来と同様の方法によって行えばよく、例えば、常温から１００℃の間で、前記顔料、樹脂、アクリル系モノマーもしくはオリゴマー、重合禁止剤、開始剤およびアミン化合物等の増感剤、その他添加剤などインキ組成物成分を、ニーダー、三本ロール、アトライター、サンドミル、ゲートミキサーなどの練肉、混合、調整機を用いて製造される。
The active energy ray curable ink of the present invention may be carried out by the same method as in the prior art. For example, the pigment, the resin, the acrylic monomer or oligomer, the polymerization inhibitor, the initiator, and the amine between room temperature and 100 ° C. Ink composition components such as sensitizers such as compounds and other additives are produced using kneading, mixing, and adjusting machines such as a kneader, three rolls, attritor, sand mill, and gate mixer. *
（インキ硬化物の製造方法、印刷物）
本発明の第二の形態は、基材上、又は、基材上に印刷された印刷インキ層の上に、前記活性エネルギー線硬化型インキの層を形成し、３５０～４２０ｎｍにピーク波長を有する紫外線発光ダイオード光源で紫外線を照射することにより得られることを特徴とする印刷物である。 (Method for producing ink cured product, printed matter)
In the second embodiment of the present invention, the active energy ray-curable ink layer is formed on a substrate or a printing ink layer printed on the substrate, and has a peak wavelength at 350 to 420 nm. A printed matter obtained by irradiating ultraviolet rays with an ultraviolet light emitting diode light source.
本発明の第二の形態は、基材上、又は、基材上に印刷された印刷インキ層の上に、前記活性エネルギー線硬化型インキの層を形成し、３５０～４２０ｎｍにピーク波長を有する紫外線発光ダイオード光源で紫外線を照射することにより得られることを特徴とする印刷物である。 (Method for producing ink cured product, printed matter)
In the second embodiment of the present invention, the active energy ray-curable ink layer is formed on a substrate or a printing ink layer printed on the substrate, and has a peak wavelength at 350 to 420 nm. A printed matter obtained by irradiating ultraviolet rays with an ultraviolet light emitting diode light source.
本発明の印刷物で使用する印刷基材としては、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、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 used in the printed matter of the present invention is not particularly limited. For example, paper such as fine paper, coated paper, art paper, imitation paper, thin paper, cardboard, polyester resin, acrylic resin, vinyl chloride resin, chloride. Vinylidene resin, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, nylon or polylactic acid, polycarbonate film or sheet, cellophane, aluminum foil In addition, various base materials conventionally used as printing base materials can be mentioned. *
本発明の印刷物の製造に用いられる印刷インキとしては、紫外線発光ダイオードより発せられる紫外線に対して好適に硬化する組成物であれば特に限定は無く、例えば印刷方式に応じて、オフセット、水無し、グラビア、フレキソ、シルクスクリーン、インクジェット、その他従来から印刷用途に使用されているＵＶ硬化性インキを採用することが可能である。
The printing ink used in the production of the printed matter of the present invention is not particularly limited as long as it is a composition that is suitably cured with respect to ultraviolet rays emitted from ultraviolet light emitting diodes. For example, depending on the printing method, offset, no water, It is possible to employ gravure, flexo, silk screen, ink jet, and other UV curable inks conventionally used for printing. *
本発明の印刷物を製造するために使用する紫外線発光ダイオード光源より発せられる紫外線の発光波長としては、例えば、発光ピーク波長が３５０～４２０ｎｍ程度であるものが好ましい。
As the emission wavelength of ultraviolet rays emitted from the ultraviolet light emitting diode light source used for producing the printed matter of the present invention, for example, those having an emission peak wavelength of about 350 to 420 nm are preferable. *
紫外線発光ダイオード光源よりＵＶ硬化性組成物へ照射される紫外線の積算光量値に関しては、印刷基材上のＵＶ硬化性組成物の種別や印刷層の厚み等により異なる為、厳密には特定出来ず、適宜好ましい条件を選択するものであるが、例えば、積算光量の総和が５～２００ｍＪ／ｃｍ２程度であり、より好ましくは、１０～１００ｍＪ／ｃｍ２程度である。
The integrated light quantity value of the ultraviolet light irradiated to the UV curable composition from the ultraviolet light emitting diode light source varies depending on the type of the UV curable composition on the printing substrate and the thickness of the printing layer, and thus cannot be specified strictly. The preferable conditions are selected as appropriate. For example, the sum of the integrated light amounts is about 5 to 200 mJ / cm 2 , and more preferably about 10 to 100 mJ / cm 2 .
積算光量値５ｍＪ／ｃｍ２を下回る条件では十分な硬化性を得ることが困難となり、一方、積算光量値２００ｍＪ／ｃｍ２を超える条件は、本発明で述べる印刷方式においては不必要であり、紫外線発光ダイオード光源の特徴である省エネルギー性を維持する目的においても過剰量のエネルギー照射は行わない。
It is difficult to obtain sufficient curability at conditions below the integrated light quantity values 5 mJ / cm 2, whereas the condition exceeding the accumulated light quantity value 200 mJ / cm 2, in the printing method described in the present invention is unnecessary, ultraviolet Excessive energy irradiation is not performed for the purpose of maintaining the energy saving characteristic of the light emitting diode light source.
紫外線発光ダイオード光源より印刷基材上のＵＶ硬化性組成物へ照射される紫外線の照射強度（ｍＷ／ｃｍ２）に関しては、印刷方向に並べる紫外線発光ダイオード光源の個数、光源から組成物までの照射距離等の諸条件によっても適切な照射強度範囲が変動することから特に規定はしないが、本発明で述べる印刷方式における印刷基材の移動速度は６０～４００ｍ／ｍｉｎ．程度であるから、該印刷速度で移動する印刷基材上のＵＶ硬化性組成物に対して、積算光量値が先に述べた程度となる照射強度であることが好ましい。
Regarding the irradiation intensity (mW / cm 2 ) of ultraviolet rays irradiated from the ultraviolet light emitting diode light source to the UV curable composition on the printing substrate, the number of ultraviolet light emitting diode light sources arranged in the printing direction and the irradiation from the light source to the composition Since the appropriate irradiation intensity range fluctuates depending on various conditions such as distance, there is no particular limitation, but the moving speed of the printing substrate in the printing method described in the present invention is 60 to 400 m / min. Therefore, it is preferable that the irradiation intensity is such that the integrated light quantity value is as described above for the UV curable composition on the printing substrate moving at the printing speed.
次に実施例により更に具体的に説明するが、本発明はこれらに限定されるものでは無い。
Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
〔活性エネルギー線硬化型オフセットインキの製造方法〕
表１～表３の組成に従って、実施例１～８及び比較例１～１０のインキを３本ロールミルにて練肉することによって、各種のインキ組成物を得た。尚、表中の空欄は、未配合を意味している。 [Method for producing active energy ray-curable offset ink]
Various ink compositions were obtained by kneading the inks of Examples 1 to 8 and Comparative Examples 1 to 10 with a three roll mill according to the compositions of Tables 1 to 3. In addition, the blank in a table | surface means the unblending.
表１～表３の組成に従って、実施例１～８及び比較例１～１０のインキを３本ロールミルにて練肉することによって、各種のインキ組成物を得た。尚、表中の空欄は、未配合を意味している。 [Method for producing active energy ray-curable offset ink]
Various ink compositions were obtained by kneading the inks of Examples 1 to 8 and Comparative Examples 1 to 10 with a three roll mill according to the compositions of Tables 1 to 3. In addition, the blank in a table | surface means the unblending.
〔展色物の製造方法〕
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、ＰＥＴ原反（ＤＩＣ社製、ダイタックＵＶＰＥＴ透明２５ＦＬ）上、約２２０ｃｍ２の面積範囲にわたって墨濃度１．８（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、展色物を作製した。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。 [Manufacturing method of exhibition colors]
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. And spread on a PET original fabric (DIC Corporation, Daitac UVPET Transparent 25FL) so that it can be uniformly applied at an ink density of 1.8 (measured with a X-Rite SpectroEye densitometer) over an area of approximately 220 cm2. Colored and produced an exhibition color. 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.
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、ＰＥＴ原反（ＤＩＣ社製、ダイタックＵＶＰＥＴ透明２５ＦＬ）上、約２２０ｃｍ２の面積範囲にわたって墨濃度１．８（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、展色物を作製した。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。 [Manufacturing method of exhibition colors]
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. And spread on a PET original fabric (DIC Corporation, Daitac UVPET Transparent 25FL) so that it can be uniformly applied at an ink density of 1.8 (measured with a X-Rite SpectroEye densitometer) over an area of approximately 220 cm2. Colored and produced an exhibition color. 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.
（紫外線発光ダイオード光源による乾燥方法）
水冷式ＵＶ－ＬＥＤ（中心発光波長３８５ｎｍ±５ｎｍＵＶ－ＬＥＤの出力１００％）およびベルトコンベアを搭載したＵＶ照射装置（アイグラフィックス社製）を使用し、展色物をコンベア上に載せ、コンベアスピード１００ｍ／ｍｉｎの速度で、ＬＥＤ直下（照射距離９ｃｍ）を通過させた。前記の方法で得られた光硬化性インキ塗布後の展色物に紫外線（ＵＶ）照射を行いインキ皮膜を硬化乾燥させた。 (Drying method using ultraviolet light-emitting diode light source)
Using a water-cooled UV-LED (central emission wavelength 385 nm ± 5 nm UV-LED output 100%) and a UV irradiation device (made by Eye Graphics Co., Ltd.) equipped with a belt conveyor, the color-exposed product is placed on the conveyor, and the conveyor speed The LED was passed directly under the LED (irradiation distance 9 cm) at a speed of 100 m / min. The color-extended product obtained by applying the photocurable ink obtained by the above method was irradiated with ultraviolet rays (UV) to cure and dry the ink film.
水冷式ＵＶ－ＬＥＤ（中心発光波長３８５ｎｍ±５ｎｍＵＶ－ＬＥＤの出力１００％）およびベルトコンベアを搭載したＵＶ照射装置（アイグラフィックス社製）を使用し、展色物をコンベア上に載せ、コンベアスピード１００ｍ／ｍｉｎの速度で、ＬＥＤ直下（照射距離９ｃｍ）を通過させた。前記の方法で得られた光硬化性インキ塗布後の展色物に紫外線（ＵＶ）照射を行いインキ皮膜を硬化乾燥させた。 (Drying method using ultraviolet light-emitting diode light source)
Using a water-cooled UV-LED (central emission wavelength 385 nm ± 5 nm UV-LED output 100%) and a UV irradiation device (made by Eye Graphics Co., Ltd.) equipped with a belt conveyor, the color-exposed product is placed on the conveyor, and the conveyor speed The LED was passed directly under the LED (irradiation distance 9 cm) at a speed of 100 m / min. The color-extended product obtained by applying the photocurable ink obtained by the above method was irradiated with ultraviolet rays (UV) to cure and dry the ink film.
〔光硬化性インキの硬化性評価方法〕
硬化直後に硬化インキ層を爪で擦ることにより硬化皮膜の硬化性を評価した。
評価基準は以下とした。
◎：強い力で擦っても傷が付かず、ＵＶ硬化性は非常に良好である。
〇：強い力で擦ると僅かに傷が付く。
△：強い力で擦ると明確に傷が付く
×：弱い力で擦っても明確に傷が付き、ＵＶ硬化性は不良である。 [Method for evaluating curability of photocurable ink]
Immediately after curing, the curability of the cured film was evaluated by rubbing the cured ink layer with a nail.
The evaluation criteria were as follows.
(Double-circle): Even if it rubs with strong force, it is not damaged and UV sclerosis | hardenability is very favorable.
◯: Slightly scratched when rubbed with strong force.
Δ: Scratches clearly when rubbed with a strong force ×: Scratches clearly even when rubbed with a weak force, and the UV curability is poor.
硬化直後に硬化インキ層を爪で擦ることにより硬化皮膜の硬化性を評価した。
評価基準は以下とした。
◎：強い力で擦っても傷が付かず、ＵＶ硬化性は非常に良好である。
〇：強い力で擦ると僅かに傷が付く。
△：強い力で擦ると明確に傷が付く
×：弱い力で擦っても明確に傷が付き、ＵＶ硬化性は不良である。 [Method for evaluating curability of photocurable ink]
Immediately after curing, the curability of the cured film was evaluated by rubbing the cured ink layer with a nail.
The evaluation criteria were as follows.
(Double-circle): Even if it rubs with strong force, it is not damaged and UV sclerosis | hardenability is very favorable.
◯: Slightly scratched when rubbed with strong force.
Δ: Scratches clearly when rubbed with a strong force ×: Scratches clearly even when rubbed with a weak force, and the UV curability is poor.
〔硬化塗膜の臭気評価方法〕
前記硬化方法で硬化させた硬化物を縦５ｃｍ横２．５ｃｍに切り取り、この切片を１０枚用意した。この切片１０枚を素早く外径４０ｍｍ、高さ７５ｍｍ、口内径２０．１ｍｍ、容量５０ｍｌのコレクションバイアルに入れ、ふたを閉めて６０℃の恒温槽に１時間保管し、コレクションバイアル中に臭気を充満させた。つぎに、このコレクションバイアルを室温になるまで放置し、臭気の強さを評価するモニター１０名により、各サンプルの臭気の強さを１０段階で評価した。
１０名の臭気評価結果を平均し、そのサンプルの臭気の強さとした。なお、数値が高い方が、低臭であることを意味している。
○： １０～７
△： ６～３
×： ２～０
[Method for evaluating odor of cured coating film]
The cured product cured by the above-described curing method was cut into a length of 5 cm and a width of 2.5 cm, and 10 sections were prepared. 10 pieces are quickly placed in a collection vial with an outer diameter of 40 mm, a height of 75 mm, a mouth inner diameter of 20.1 mm, and a volume of 50 ml. The lid is closed and stored in a constant temperature bath at 60 ° C. for 1 hour. I let you. Next, the collection vial was allowed to stand until it reached room temperature, and the odor intensity of each sample was evaluated in 10 stages by 10 monitors who evaluated the odor intensity.
The odor evaluation results of 10 people were averaged to determine the odor intensity of the sample. A higher numerical value means a lower odor.
○: 10-7
Δ: 6-3
×: 2 to 0
前記硬化方法で硬化させた硬化物を縦５ｃｍ横２．５ｃｍに切り取り、この切片を１０枚用意した。この切片１０枚を素早く外径４０ｍｍ、高さ７５ｍｍ、口内径２０．１ｍｍ、容量５０ｍｌのコレクションバイアルに入れ、ふたを閉めて６０℃の恒温槽に１時間保管し、コレクションバイアル中に臭気を充満させた。つぎに、このコレクションバイアルを室温になるまで放置し、臭気の強さを評価するモニター１０名により、各サンプルの臭気の強さを１０段階で評価した。
１０名の臭気評価結果を平均し、そのサンプルの臭気の強さとした。なお、数値が高い方が、低臭であることを意味している。
○： １０～７
△： ６～３
×： ２～０
[Method for evaluating odor of cured coating film]
The cured product cured by the above-described curing method was cut into a length of 5 cm and a width of 2.5 cm, and 10 sections were prepared. 10 pieces are quickly placed in a collection vial with an outer diameter of 40 mm, a height of 75 mm, a mouth inner diameter of 20.1 mm, and a volume of 50 ml. The lid is closed and stored in a constant temperature bath at 60 ° C. for 1 hour. I let you. Next, the collection vial was allowed to stand until it reached room temperature, and the odor intensity of each sample was evaluated in 10 stages by 10 monitors who evaluated the odor intensity.
The odor evaluation results of 10 people were averaged to determine the odor intensity of the sample. A higher numerical value means a lower odor.
○: 10-7
Δ: 6-3
×: 2 to 0
使用した原料の詳細は下記である。
「ラーベン１０６０Ｕｌｔｒａ」：ＢＩＲＬＡ ＣＡＲＢＯＮ製 カーボンブラック
「ＦＡＳＴＯＧＥＮ ＢＬＵＥ ＴＧＲ－１」：ＤＩＣ製 Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：３
「ホスタパームバイオレット ＲＬ ０２」：クラリアント製 Ｐｉｇｍｅｎｔ Ｖｉｏｌｅｔ ２３
「ハイフィラー＃５０００ＰＪ」：松村産業製 タルク
「Ｓ－３８１－Ｎ１」：シャムロック製 オレフィン系微粉末ワックス
「ジアリルフタレート樹脂ワニス」：大阪ソーダ製ダイソーダップ ３５質量％をＳＲ３５５ＮＳ ６５質量％に溶解させた混合物
「ステアラーＴＢＨ」：精工化学製 ｔｅｒｔ－ブチルハイドロキノン
「アロニックスＭ－４００」：東亞合成製 ジペンタエリスリトールペンタ及びヘキサアクリレート
「ＳＲ３５５ＮＳ」：アルケマ製 ジトリメチロールプロパンテトラアクリレート
「光重合開始剤Ａ」：（１）に記載の光重合開始剤において、下記の構造式で表される化合物 ２－ベンジル－２－ジメチルアミノ－１－（４－ピペリジノフェニル）－ブタン－１－オン Details of the raw materials used are as follows.
“Raven 1060 Ultra”: Carbon black made by BIRLA CARBON “FASTOGEN BLUE TGR-1”: Pigment Blue 15: 3 made by DIC
“Hosta Palm Violet RL 02”: Pigment Violet 23 made by Clariant
“High filler # 5000PJ”: Matsumura Sangyo Talc “S-381-N1”: Shamrock Olefin fine powder wax “Dialylphthalate Resin Varnish”: Osaka Soda Daisodap "Stearer TBH": Seiko Chemical's tert-butyl hydroquinone "Aronix M-400": Toagosei dipentaerythritol penta- and hexaacrylate "SR355NS": Arkema ditrimethylolpropane tetraacrylate
“Photoinitiator A”: a compound represented by the following structural formula in the photoinitiator described in (1): 2-benzyl-2-dimethylamino-1- (4-piperidinophenyl) -butane -1-On
「ラーベン１０６０Ｕｌｔｒａ」：ＢＩＲＬＡ ＣＡＲＢＯＮ製 カーボンブラック
「ＦＡＳＴＯＧＥＮ ＢＬＵＥ ＴＧＲ－１」：ＤＩＣ製 Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：３
「ホスタパームバイオレット ＲＬ ０２」：クラリアント製 Ｐｉｇｍｅｎｔ Ｖｉｏｌｅｔ ２３
「ハイフィラー＃５０００ＰＪ」：松村産業製 タルク
「Ｓ－３８１－Ｎ１」：シャムロック製 オレフィン系微粉末ワックス
「ジアリルフタレート樹脂ワニス」：大阪ソーダ製ダイソーダップ ３５質量％をＳＲ３５５ＮＳ ６５質量％に溶解させた混合物
「ステアラーＴＢＨ」：精工化学製 ｔｅｒｔ－ブチルハイドロキノン
「アロニックスＭ－４００」：東亞合成製 ジペンタエリスリトールペンタ及びヘキサアクリレート
「ＳＲ３５５ＮＳ」：アルケマ製 ジトリメチロールプロパンテトラアクリレート
「光重合開始剤Ａ」：（１）に記載の光重合開始剤において、下記の構造式で表される化合物 ２－ベンジル－２－ジメチルアミノ－１－（４－ピペリジノフェニル）－ブタン－１－オン Details of the raw materials used are as follows.
“Raven 1060 Ultra”: Carbon black made by BIRLA CARBON “FASTOGEN BLUE TGR-1”: Pigment Blue 15: 3 made by DIC
“Hosta Palm Violet RL 02”: Pigment Violet 23 made by Clariant
“High filler # 5000PJ”: Matsumura Sangyo Talc “S-381-N1”: Shamrock Olefin fine powder wax “Dialylphthalate Resin Varnish”: Osaka Soda Daisodap "Stearer TBH": Seiko Chemical's tert-butyl hydroquinone "Aronix M-400": Toagosei dipentaerythritol penta- and hexaacrylate "SR355NS": Arkema ditrimethylolpropane tetraacrylate
“Photoinitiator A”: a compound represented by the following structural formula in the photoinitiator described in (1): 2-benzyl-2-dimethylamino-1- (4-piperidinophenyl) -butane -1-On
以下の光重合開始剤は全てＩＧＭ ＲＥＳＩＮＳ 製である。
Ｏｍｎｉｒａｄ ３６９ ２－ベンジル－２－（ジメチルアミノ）－４’－モルフォリノブチロフェノン
Ｏｍｎｉｒａｄ ９０７ ２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン
Ｏｍｎｉｒａｄ 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シド
Ｏｍｎｉｒａｄ ８１９ 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シド
Ｏｍｎｉｒａｄ ＤＥＴＸ ２，４－ジエチルチオキサントン
Ｏｍｎｉｒａｄ ＥＭＫ ４，４’－ビス（ジエチルアミノ）ベンゾフェノン
Ｏｍｎｉｒａｄ ＥＤＢ ４－（ジメチルアミノ）安息香酸エチル The following photopolymerization initiators are all made by IGM RESINS.
Omnirad 369 2-benzyl-2- (dimethylamino) -4′-morpholinobutyrophenone Omnirad 907 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one Omnirad TPO 2,4 , 6-Trimethylbenzoyl-diphenylphosphine oxide Omnirad 819 bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide Omnirad DETX 2,4-diethylthioxanthone Omnirad EMK 4,4'-bis (diethylamino) benzophenone Omnirad EDB 4 -(Dimethylamino) ethyl benzoate
Ｏｍｎｉｒａｄ ３６９ ２－ベンジル－２－（ジメチルアミノ）－４’－モルフォリノブチロフェノン
Ｏｍｎｉｒａｄ ９０７ ２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン
Ｏｍｎｉｒａｄ 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シド
Ｏｍｎｉｒａｄ ８１９ 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シド
Ｏｍｎｉｒａｄ ＤＥＴＸ ２，４－ジエチルチオキサントン
Ｏｍｎｉｒａｄ ＥＭＫ ４，４’－ビス（ジエチルアミノ）ベンゾフェノン
Ｏｍｎｉｒａｄ ＥＤＢ ４－（ジメチルアミノ）安息香酸エチル The following photopolymerization initiators are all made by IGM RESINS.
Omnirad 369 2-benzyl-2- (dimethylamino) -4′-morpholinobutyrophenone Omnirad 907 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one Omnirad TPO 2,4 , 6-Trimethylbenzoyl-diphenylphosphine oxide Omnirad 819 bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide Omnirad DETX 2,4-diethylthioxanthone Omnirad EMK 4,4'-bis (diethylamino) benzophenone Omnirad EDB 4 -(Dimethylamino) ethyl benzoate
この結果、実施例１～８の活性エネルギー線硬化型インキは硬化性に優れることが明らかである。
As a result, it is clear that the active energy ray-curable inks of Examples 1 to 8 are excellent in curability.
Claims (7)
- エチレン性不飽和二重結合を有するモノマー、及び一般式（１）で表される光重合開始剤を含有することを特徴とする活性エネルギー線硬化型インキ。
（式中、ｎは０または１を表し、Ｒ１～Ｒ４はそれぞれ独立して、炭素原子数１～１０の直鎖または分岐のアルキル基を表す。） An active energy ray-curable ink comprising a monomer having an ethylenically unsaturated double bond and a photopolymerization initiator represented by the general formula (1).
(In the formula, n represents 0 or 1, and R 1 to R 4 each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms.) - 前記一般式（１）で表される光重合開始剤が、２－ベンジル－２－ジメチルアミノ－１－（４－ピペリジノフェニル）－ブタン－１－オンである請求項１に記載の活性エネルギー線硬化型インキ。 2. The activity according to claim 1, wherein the photopolymerization initiator represented by the general formula (1) is 2-benzyl-2-dimethylamino-1- (4-piperidinophenyl) -butan-1-one. Energy ray curable ink.
- アシルフォスフィンオキシド系光開始剤及び／または光増感剤を含有する請求項１または２に記載の活性エネルギー線硬化型インキ。 The active energy ray-curable ink according to claim 1 or 2, comprising an acylphosphine oxide photoinitiator and / or a photosensitizer.
- 第三級アミン化合物を含有する請求項１～３のいずれかに記載の活性エネルギー線硬化型インキ。 The active energy ray-curable ink according to any one of claims 1 to 3, comprising a tertiary amine compound.
- 請求項１～４のいずれか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、印刷されたインキを活性エネルギー線を用いて硬化させることを特徴とするインキ硬化物の製造方法。 A method for producing an ink cured product, comprising: printing using the active energy ray-curable ink according to any one of claims 1 to 4, and curing the printed ink using the active energy ray. *
- 請求項１～４のいずれかに記載の活性エネルギー線硬化型インキを用いてオフセット印刷し、印刷されたインキを活性エネルギー線を用いて硬化させることを特徴とするインキ硬化物の製造方法。 A method for producing an ink cured product, comprising performing offset printing using the active energy ray-curable ink according to any one of claims 1 to 4, and curing the printed ink using the active energy ray. *
- 請求項５又は６に記載のインキ硬化物の製造方法で得られた印刷物。 Printed matter obtained by the method for producing an ink cured product according to claim 5 or 6.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63264560A (en) * | 1987-03-26 | 1988-11-01 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Alpha-aminoacetophenone derivative |
| JPH02151822A (en) * | 1988-12-05 | 1990-06-11 | Sumitomo Electric Ind Ltd | Coated optical fiber |
| JP2014157356A (en) * | 2013-01-15 | 2014-08-28 | Taiyo Ink Mfg Ltd | Curable resin composition, dry film and cured product thereof, and printed wiring board using the same |
| JP2015043060A (en) * | 2013-07-26 | 2015-03-05 | 太陽インキ製造株式会社 | Photocurable composition for printed wiring board production, and cured product thereof and printed wiring board |
| JP2018002958A (en) * | 2016-07-07 | 2018-01-11 | Dic株式会社 | Active energy ray-curable printing ink and printed matter of the same |
| GB2561985A (en) * | 2017-04-24 | 2018-10-31 | Fujifilm Speciality Ink Systems Ltd | Printing ink |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61147596A (en) * | 1984-12-21 | 1986-07-05 | 大日本インキ化学工業株式会社 | Manufacture of double side through hole printed circuit board |
| JPS63264686A (en) * | 1987-04-22 | 1988-11-01 | Toyo Ink Mfg Co Ltd | Resist ink |
| JPH02283486A (en) * | 1988-10-11 | 1990-11-20 | Ookurashiyou Insatsu Kyokucho | Multicolor printed matter which shows continuous change in print color, its printing method and printing mechanism |
| JP4134017B2 (en) * | 2004-12-10 | 2008-08-13 | ケーニッヒ ウント バウエル アクチエンゲゼルシャフト | Newspaper printing machine |
| JP2006229127A (en) * | 2005-02-21 | 2006-08-31 | Showa Denko Kk | Thermosetting composition for solder resist and its curing object |
| CN103926791B (en) * | 2013-01-15 | 2016-11-16 | 太阳油墨制造株式会社 | Hardening resin composition, its dry film and solidfied material and use their printed circuit board (PCB) |
| JP6317070B2 (en) * | 2013-05-07 | 2018-04-25 | 太陽ホールディングス株式会社 | Printed wiring board material and printed wiring board using the same |
| JP6172484B1 (en) * | 2016-04-22 | 2017-08-02 | 東洋インキＳｃホールディングス株式会社 | Active energy ray-curable printing ink and printed matter |
-
2019
- 2019-02-21 JP JP2019532152A patent/JP6861282B2/en active Active
- 2019-02-21 WO PCT/JP2019/006471 patent/WO2019171965A1/en active Application Filing
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63264560A (en) * | 1987-03-26 | 1988-11-01 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Alpha-aminoacetophenone derivative |
| JPH02151822A (en) * | 1988-12-05 | 1990-06-11 | Sumitomo Electric Ind Ltd | Coated optical fiber |
| JP2014157356A (en) * | 2013-01-15 | 2014-08-28 | Taiyo Ink Mfg Ltd | Curable resin composition, dry film and cured product thereof, and printed wiring board using the same |
| JP2015043060A (en) * | 2013-07-26 | 2015-03-05 | 太陽インキ製造株式会社 | Photocurable composition for printed wiring board production, and cured product thereof and printed wiring board |
| JP2018002958A (en) * | 2016-07-07 | 2018-01-11 | Dic株式会社 | Active energy ray-curable printing ink and printed matter of the same |
| GB2561985A (en) * | 2017-04-24 | 2018-10-31 | Fujifilm Speciality Ink Systems Ltd | Printing ink |
Non-Patent Citations (1)
| Title |
|---|
| BAI,XUE ET AL.: "Theoretical Study on Novel Photoinitiators", JOURNAL OF SOUTH CHINA NORMAL UNIVERSITY, vol. 45, no. 2, March 2013 (2013-03-01), pages 69 - 73, XP055637297 * |
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| JP6861282B2 (en) | 2021-04-21 |
| CN111801393A (en) | 2020-10-20 |
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