Active energy ray-curable lithographic printing ink composition and printed matter

Abstract

To provide an active energy ray-curable planographic ink composition that reduces ink deposition on a blanket of a printer, and has high flowability and high gloss, and a printed material including the same.SOLUTION: An active energy ray-curable planographic ink contains a pigment, a photopolymerization initiator, a polymerizable compound, a surfactant, and silica. The surfactant includes a polyoxyethylene polyoxypropyleneglycol surfactant.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an active energy ray-curable lithographic printing ink composition and a printed matter using the same. [Background technology]

[0002] In recent years, the demand for active energy ray-curable inks has been increasing to replace oil-based inks due to their quick drying properties and ease of use, such as the ability to move on to post-processing immediately after printing, and there is a demand for ink coatings that are equivalent to those of oil-based inks. Furthermore, in the case of active energy ray-curable lithographic printing inks, attempts to improve the fluidity and gloss can lead to problems such as scumming during printing and ink accumulation on the blanket, so there is a demand for inks with printability and physical properties equivalent to those of oil-based inks.

[0003] As a method for improving the ink deposition on the blanket, for example, Patent Document 1 discloses a method of adding sodium hexametaphosphate to an active energy ray-curable lithographic printing ink, and Patent Document 2 discloses a method of adding a phosphoric acid compound and silica to an active energy ray-curable lithographic printing ink.

[0004] Furthermore, for example, Patent Document 3 discloses a method of adding a specific surfactant to an oil-based lithographic printing ink.

[0005] However, the methods described in Patent Documents 1 and 2 improve the problem of blanket staining, but are insufficient in terms of fluidity and gloss. Also, when this surfactant is used in an active energy ray-curable lithographic printing ink as described in Patent Document 3, the improvement of ink deposition on the blanket is insufficient. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2004-292553 A [Patent Document 2] JP 2016-196596 A [Patent Document 3] JP 2010-229299 A Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide an actinic ray-curable lithographic printing ink composition which improves ink deposition on a blanket of a printing press and has excellent fluidity and high gloss, and to provide a printed matter using the same. [Means for solving the problem]

[0008] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by the active energy ray-curable lithographic printing ink composition described below, and a printed matter using the same, and have thus completed the present invention.

[0009] That is, the present invention provides an active energy ray-curable lithographic printing ink comprising a pigment, a photopolymerization initiator, a polymerizable compound, a surfactant, and silica, The present invention relates to an active energy ray-curable lithographic printing ink, wherein the surfactant comprises a polyoxyethylene polyoxypropylene glycol-based surfactant.

[0010] The present invention also relates to the above-mentioned active energy ray-curable lithographic printing ink, wherein the content of the polyoxyethylene polyoxypropylene glycol surfactant is 0.1 to 1 mass % based on the total amount of the active energy ray-curable lithographic printing ink.

[0011] The present invention also relates to the above-mentioned active energy ray-curable lithographic printing ink, wherein the silica is hydrophilic silica.

[0012] The present invention also relates to the above-mentioned active energy ray-curable lithographic printing ink, wherein the content of the silica is 0.4 to 2 mass % based on the total amount of the active energy ray-curable lithographic printing ink.

[0013] The present invention also relates to a printed matter obtained by printing the above-mentioned active energy ray-curable lithographic printing ink on a substrate and curing the ink with active energy rays. Effect of the Invention

[0014] INDUSTRIAL APPLICABILITY The present invention makes it possible to provide an actinic ray-curable lithographic printing ink composition which improves ink deposition on the blanket of a printing press and has excellent fluidity and high gloss, as well as a printed matter using the same. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The present invention will be described in detail below. Note that the present invention is not limited to the following embodiments, and can be practiced with various modifications within the scope of the spirit of the invention. In addition, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass". <Active energy ray curable lithographic printing ink composition> The active energy ray-curable lithographic printing ink composition of the present invention is an active energy ray-curable lithographic printing ink composition containing a colorant, a polymerizable compound, a photopolymerization initiator, a polyoxyethylene polyoxypropylene glycol-based surfactant, and silica.

[0016] Hereinafter, the components that are or can be contained in the active energy ray-curable lithographic printing ink composition of the present invention (hereinafter also simply referred to as "ink") will be described.

[0017] [Coloring agent] The active energy ray-curable lithographic printing ink composition of the present invention contains a colorant. As the colorant, at least one of a pigment and a dye can be used. From the viewpoint of light resistance, a pigment is preferred. The pigment that can be used in the present invention is not particularly limited, and any known pigment can be used. The pigment can be either an inorganic pigment or an organic pigment.

[0018] Examples of the inorganic pigment include carbon blacks such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide.

[0019] Examples of the organic pigment include soluble azo pigments such as β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid anilide, acetoacetate anilide, and pyrazolone; Examples of the pigments include insoluble azo pigments such as β-naphthol, β-oxynaphthoic acid anilide, acetoacetate anilide monoazo, acetoacetate anilide disazo, and pyrazolone; phthalocyanine pigments such as copper phthalocyanine blue, halogenated (e.g., chlorinated or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, and metal-free phthalocyanine; and polycyclic pigments and heterocyclic pigments such as quinacridone, dioxazine, threne (pyranthrone, anthranthrone, indanthrone, anthrapyrimidine, flavanthrone, thioindigo, anthraquinone, perinone, perylene, etc.), isoindolinone, metal complex, quinophthalone, and diketopyrrolopyrrole.

[0020] More specifically, in terms of the CI color index, black pigments include CI Pigment Black 1, 6, 7, 9, 10, 11, 28, 26, 31, and the like.

[0021] Examples of white pigments include CI Pigment White 5, 6, 7, 12, and 28.

[0022] Examples of yellow pigments include CI Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 18, 24, 73, 74, 75, 83, 93, 95, 97, 98, 100, 108, 109, 110, 114, 120, 128, 129, 138, 139, 174, 150, 151, 154, 155, 167, 180, 185, and 213.

[0023] Blue or cyan pigments include CI Pigment Blue 1, 2, 14, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and the like.

[0024] Red or crimson pigments include CI Pigment RED 1, 3, 5, 19, 21, 22, 31, 38, 42, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 50, 52, 53:1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 83, 90, 104, 108, 11 2, 114, 122, 144, 146, 148, 149, 150, 166, 168, 169, 170, 172, 173, 176, 177, 178, 184, 185, 187, 193, 202, 209, 214, 242, 254, 255, 264, 266, 269, CI Pigment Violet 19, etc.

[0025] Green pigments include CI Pigment Green 1, 2, 3, 4, 7, 8, 10, 15, 17, 26, 36, 45, 50, and the like.

[0026] Purple pigments include CI Pigment Violet 1, 2, 3, 4, 5:1, 12, 13, 15, 16, 17, 19, 23, 25, 29, 31, 32, 36, 37, 39, and 42. Orange pigments include CI Pigment Orange 13, 16, 20, 34, 36, 38, 39, 43, 51, 61, 63, 64, 74, and the like.

[0027] In the present invention, the above pigments may be used alone or in combination of two or more.

[0028] In the present invention, the above pigment can be used in any content as long as the desired density can be reproduced on the printed paper surface, and the content is preferably 5 to 30 mass % relative to the total mass of the ink, and more preferably 10 to 25 mass %.

[0029] [Polymerizable compound] In this specification, unless otherwise specified, the terms "(meth)acryloyl", "(meth)acrylic acid", "(meth)acrylate", and "(meth)acryloyloxy" respectively mean "acryloyl and / or methacryloyl", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", and "acryloyloxy and / or methacryloyloxy". In addition, "PO" stands for "propylene oxide" and "EO" stands for "ethylene oxide".

[0030] The active energy ray-curable lithographic printing ink composition of the present invention contains a polymerizable compound. The polymerizable compound that can be used in the present invention is not particularly limited as long as it is a compound having one or more ethylenically unsaturated bonds in the molecule as a polymerizable group, and includes any of the forms of a monomer, oligomer, and polymer. In the present invention, the polymerizable compound may be used alone or in combination of two or more kinds.

[0031] In the present invention, the content of the polymerizable compound is preferably from 40 to 80% by mass, and more preferably from 45 to 70% by mass, based on the total mass of the ink.

[0032] (monomer) The present invention preferably contains a monomer as the polymerizable compound. In the present invention, the term "monomer" refers to a compound that is the minimum structural unit for constituting an oligomer or a polymer. The monomer is preferably a compound having a polymerizable group selected from a (meth)acryloyl group, an allyl group, a vinyl group, and a vinyl ether group in the molecule. Among them, from the viewpoint of curability, a (meth)acrylate monomer, which is a compound having a (meth)acryloyl group as the polymerizable group, is more preferable. Specifically, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, β-carboxyethyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, tetrahydrofurfuryl acrylate, alkoxylated tetrahydrofurfuryl acrylate, caprolactone (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isoamyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isodecyl (meth)acrylate, 3,3,5-trimethylcyclohexanol (meth)acrylate, monofunctional (meth)acrylate monomers having one (meth)acryloyl group in the molecule, such as acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (oxyethyl) (meth)acrylate, 1,4-cyclohexanedimethanol (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, benzyl (meth)acrylate, EO-modified (2) nonylphenol acrylate, 2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate, and acryloylmorpholine; Monofunctional vinyl monomers having one vinyl group in the molecule, such as N-vinylcarbazole, 1-vinylimidazole, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and N-vinylformamide; 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-dodecanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol (200) di(meth)acrylate, polyethylene glycol (300) di(meth)acrylate, polyethylene glycol (400) di(meth)acrylate, polyethylene glycol (600) di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate , dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, EO-modified (2) 1,6-hexanediol di(meth)acrylate, PO-modified (2) neopentyl glycol di(meth)acrylate, (neopentyl glycol-modified) trimethylolpropane di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, EO-modified (4) bisphenol A di(meth)acrylate, PO-modified (4) bisphenol A di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and other bifunctional (meth)acrylate monomers having two (meth)acryloyl groups in the molecule; Trifunctional (meth)acrylate monomers having three (meth)acryloyl groups in the molecule, such as trimethylolpropane tri(meth)acrylate, EO-modified (3) trimethylolpropane tri(meth)acrylate, EO-modified (6) trimethylolpropane tri(meth)acrylate, PO-modified (3) trimethylolpropane tri(meth)acrylate, ε-caprolactone-modified tris-(2-acryloxyethyl)isocyanurate, ethoxylated isocyanuric acid tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and pentaerythritol tri(meth)acrylate; Pentaerythritol tetra(meth)acrylate, EO-modified (4) pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and other tetrafunctional (meth)acrylate monomers having four acryloyl groups in the molecule; Pentafunctional (meth)acrylate monomers having five (meth)acryloyl groups in the molecule, such as dipentaerythritol penta(meth)acrylate; and hexafunctional (meth)acrylate monomers having six (meth)acryloyl groups in the molecule, such as dipentaerythritol hexa(meth)acrylate.

[0033] Among them, from the viewpoint of curability, it is preferable that the polymerizable compound contains a trifunctional to hexafunctional (meth)acrylate monomer.

[0034] The total content of tri- to hexafunctional (meth)acrylate monomers is preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the polymerizable compound.

[0035] When a monofunctional (meth)acrylate monomer is contained, from the viewpoint of curability, its content is preferably 10 mass % or less, and more preferably 5 mass % or less, based on the total mass of the active energy ray-curable ink.

[0036] (Oligomer) The present invention may include an oligomer as the polymerizable compound. In the present invention, the "oligomer" refers to a polymer having constitutional units based on 2 to 100 monomers.

[0037] The oligomer is preferably a compound having a (meth)acryloyl group as a polymerizable group in the molecule, and in this case, the number of (meth)acryloyl groups per molecule is preferably 1 to 6, and more preferably 2 to 4, from the viewpoint of flexibility.

[0038] The weight average molecular weight of the oligomer is preferably 400 to 10,000, more preferably 500 to 5,000. Here, the "weight average molecular weight" can be determined as a styrene-equivalent molecular weight by general gel permeation chromatography (hereinafter, GPC).

[0039] Examples of the oligomer include urethane acrylate oligomers such as aliphatic urethane acrylate oligomers and aromatic urethane acrylate oligomers, acrylic ester oligomers, polyester acrylate oligomers, epoxy acrylate oligomers, etc. The oligomers may be used alone or in combination of two or more.

[0040] [Photopolymerization initiator] The active energy ray-curable lithographic printing ink composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator that can be used in the present invention is not particularly limited, and any known photopolymerization initiator can be used. Specific examples include benzophenone-based compounds, dialkoxyacetophenone-based compounds, α-hydroxyalkylphenone-based compounds, α-aminoalkylphenone-based compounds, acylphosphine oxide-based compounds, and thioxanthone-based compounds. The photopolymerization initiator may be used alone or in combination of two or more kinds.

[0041] Examples of the benzophenone-based compounds include benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, and [4-(methylphenylthio)phenyl]-phenylmethanone.

[0042] Examples of the dialkoxyacetophenone compounds include 2,2-dimethoxy-2-phenylacetophenone, dimethoxyacetophenone, and diethoxyacetophenone.

[0043] Examples of the α-hydroxyalkylphenone compounds include 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxymethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one.

[0044] Examples of the α-aminoalkylphenone compounds include 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-1-butanone.

[0045] Examples of the acylphosphine oxide compound include diphenylacylphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0046] Examples of the thioxanthone compounds include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone.

[0047] The content of the photopolymerization initiator is preferably 1 to 20% by mass, and more preferably 5 to 15% by mass, based on the total mass of the ink.

[0048] [Polyoxyethylene polyoxypropylene glycol surfactant and silica] The active energy ray-curable lithographic printing ink composition of the present invention contains a polyoxyethylene polyoxypropylene glycol surfactant and silica.

[0049] [Polyoxyethylene polyoxypropylene glycol surfactants] From the viewpoints of fluidity and gloss, the content of the polyoxyethylene polyoxypropylene glycol surfactant is preferably 0.1 to 1 mass %, more preferably 0.2 to 0.8 mass %, and even more preferably 0.3 to 0.5 mass %, relative to the total mass of the ink.

[0050] Examples of the polyoxyethylene polyoxypropylene glycol surfactant include Pepol B-181, Pepol B-182, Pepol B-184, Pepol B-188, Pepol A-0638, Pepol A-0858, Pepol D-301A, Pepol D-304, Pepol AS-053X, Pepol AS-054C, Pepol BS-184, Pepol BS-201, Pegnol D-202, Pegnol D-206Y, Pegnol D-210Y, Pegnol D-9, Pegnol DA-5, and Musheul T-401 manufactured by Toho Chemical Industry Co., Ltd., and Pronon #124P and Pronon #188P manufactured by NOF Corporation.

[0051] [silica] From the viewpoints of fluidity and gloss, the content of the silica is preferably from 0.4 to 2 mass %, and more preferably from 0.5 to 1.5 mass %, relative to the total mass of the ink. The silica is preferably hydrophilic silica, since the use of hydrophilic silica can suppress the decrease in fluidity during ink emulsification, compared to the use of hydrophobic silica.

[0052] The silica may be AEROSIL90, AEROSIL130, AEROSIL150, AEROSIL200, AEROSIL255, AEROSI L300, AEROSIL380, AEROSIL OX50, AEROSIL TT600, AEROSIL200Pharma, AEROSIL300Pharma, AEROSIL R972, AEROSIL R974, AEROSIL R104, AERO SIL R106, AEROSIL R202, AEROSIL R805, AEROSIL R812, AEROSIL R812S, AEROSIL R816, AEROSIL R7200, AEROSIL R8200, AEROSIL R9200, AEROSIL R711, AEROSIL RY50, AEROSIL Examples include NY50, AERO SIL RY200, AEROSIL RY200S, AEROSIL RX50, AE ROSIL NAX50, AEROSIL RX200, AEROSIL RX300, AEROSIL R504, AEROSIL R972Pharma, and Nipsil LP manufactured by Tosoh Silica Corporation. Among these, examples of hydrophilic silica include AEROSIL 50, AEROSIL 90G, AEROSIL 130, AEROSIL 200, AEROSIL 200CF, AEROSIL 200V, AEROSIL 300, AEROSIL 300CF, and Nipsil LP.

[0053] The polyoxyethylene polyoxypropylene glycol surfactant and silica do not exert a sufficient effect when used alone, but exert a remarkable effect when used in combination. This is thought to be due to the synergistic effect of the two different methods of improving stains: polyoxyethylene polyoxypropylene glycol surfactants suppress emulsification, making the material less susceptible to stains, and silica suppresses the drop in viscosity, making the material less susceptible to stains.

[0054] [Other ingredients] The active energy ray-curable lithographic printing ink composition of the present invention may contain, in addition to the above-mentioned components, a resin, a sensitizer, a polymerization inhibitor, an extender pigment, and the like, as required.

[0055] (resin) The active energy ray-curable lithographic printing ink composition of the present invention may contain a resin. By containing a resin, the curing shrinkage of the coating film that occurs during curing is alleviated, curling of the substrate is suppressed, and adhesion to the substrate is improved. In the present invention, the "resin" means a compound having a weight average molecular weight of 10,000 or more.

[0056] The weight average molecular weight of the resin is preferably 10,000 to 100,000, and more preferably 10,000 to 70,000.

[0057] The resins may be used alone or in combination of two or more kinds. The content of the resin is preferably 5 to 15% by mass based on the total mass of the ink composition.

[0058] Specific examples of the resin include polyvinyl chloride, (meth)acrylic resin, styrene (meth)acrylic resin, epoxy resin, polyester resin, polyurethane resin, cellulose derivatives (e.g., ethyl cellulose, cellulose acetate, nitrocellulose), vinyl chloride-vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, diallyl phthalate resin, alkyd resin, rosin-modified alkyd resin, petroleum resin, urea resin, synthetic rubber such as butadiene-acrylonitrile copolymer, etc. Among them, diallyl phthalate resin and polyester resin are more preferable from the viewpoint of dispersibility.

[0059] (sensitizer) The active energy ray-curable lithographic printing ink composition of the present invention may contain a sensitizer. By containing a sensitizer, the curability can be further improved. Specific examples of the sensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, aliphatic amines, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and dibutylethanolamine.

[0060] (Polymerization inhibitor) The active energy ray-curable lithographic printing ink composition of the present invention may contain a polymerization inhibitor, specific examples of which include 4-methoxyphenol, hydroquinone, methylhydroquinone, t-butylhydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, and aluminum salt of N-nitrosophenylhydroxylamine.

[0061] The content of the polymerization inhibitor is preferably 0.01 to 2% by mass relative to the total mass of the ink composition, from the viewpoint of increasing the stability of the ink composition while maintaining the curability.

[0062] In the present invention, the active energy ray-curable lithographic printing ink composition preferably contains substantially no water, where "substantially no water" means that the water content is 3% by mass or less relative to the total mass of the ink composition.

[0063] (Extender pigment) The active energy ray-curable lithographic printing ink composition of the present invention may contain an extender pigment (except for silica). Examples of the extender pigment include clay, talc, barium sulfate, calcium carbonate, ground calcium carbonate, barium carbonate, magnesium carbonate, silica, and bentonite.

[0064] <Printed material> The printed matter of the present invention can be obtained by printing an active energy ray-curable lithographic printing ink composition on a substrate and curing it with active energy rays.

[0065] The substrate of the present invention is not particularly limited, and known substrates can be used.Specific examples include coated paper such as art paper, coated paper, and cast paper, uncoated paper such as fine paper, medium-quality paper, and newsprint, synthetic paper such as Yupo paper, and plastic films such as PET (polyethylene terephthalate), PP (polypropylene), and OPP (biaxially oriented polypropylene).

[0066] The active energy rays in the present invention can be any known energy rays that can generate radical active species, and examples of the active energy rays that can be used include ultraviolet rays, electron beams, X-rays, ionizing radiation such as α-rays, β-rays, and γ-rays, visible light, infrared rays, microwaves, high frequency waves, and laser beams.

[0067] In the present invention, the method for curing the active energy ray-curable lithographic printing ink composition is not particularly limited, and a known method can be used, and the composition can be cured by irradiating the active energy ray. Among them, ultraviolet rays and electron beams are preferred, and ultraviolet rays are more preferred. The peak wavelength of the ultraviolet rays is preferably 200 to 600 nm, and more preferably 350 to 420 nm.

[0068] The active energy ray source is not particularly limited and may be any known source, specifically including mercury lamps, xenon lamps, metal hydride lamps, LEDs (light-emitting diodes) such as ultraviolet light-emitting diodes (UV-LEDs) and ultraviolet laser diodes (UV-LDs), gas and solid-state lasers, and the like. EXAMPLES

[0069] The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the following examples. In the examples and comparative examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

[0070] <Preparation of resin varnish> 30 parts of a diallyl phthalate resin having a weight average molecular weight of 50,000 (Daiso DAP A, manufactured by Daiso Co., Ltd.) was dissolved in 70 parts of ditrimethylolpropane tetraacrylate, and the mixture was heated and mixed (80° C.) to prepare a resin varnish.

[0071] <Preparation of Black and Yellow Base Ink> Black-based ink 15 parts of carbon black, 9.7 parts of EO(3) modified trimethololpropane triacrylate, 1.7 parts of dimethylolpropane tetraacrylate, 30 parts of dipentaerythritol hexaacrylate, 2 parts of Omnirad379, 2 parts of Omnirad819, 2 parts of OmniradDETX, 2 parts of OmniradEMK, 0.4 parts of Pepol B-184, 1 part of talc, 0.3 parts of polymerization inhibitor, and 33.4 parts of resin varnish were mixed and stirred using a butterfly mixer, then dispersed using a three-roll mill so that the maximum particle size was 7.5 μm or less to prepare a black base ink.

[0072] Yellow base ink 15 parts of LIONOL YELLOW 1315, 9.7 parts of EO(3) modified trimethylolpropane triacrylate, 1.7 parts of dimethylolpropane tetraacrylate, 30 parts of dipentaerythritol hexaacrylate, 2 parts of Omnirad379, 2 parts of Omnirad819, 2 parts of OmniradDETX, 2 parts of OmniradEMK, 1 part of talc, 0.3 parts of polymerization inhibitor, and 33.4 parts of resin varnish were mixed and stirred using a butterfly mixer, then dispersed using a three-roll mill so that the maximum particle size was 7.5 μm or less to prepare a yellow base ink.

[0073] Details of the materials used in the base ink are shown below. [Coloring agent] Carbon black: Mitsubishi Chemical Corporation, Carbon Black MA11 · LIONOL YELLOW 1315 (yellow pigment): Toyo Color Co., Ltd., LIONOL YELLOW 1315 [(Meth)acrylic compounds] EO(3) modified trimethololpropane triacrylate: BASF, LAROMER LR8863 Dimethylolpropane tetraacrylate: Daicel-Allnex, EBECRYL 1142 Dipentaerythritol hexaacrylate: Toyo Chemicals, MIRAMER M600 [Polymerization initiator] Omnirad379: 2-Dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-1-butanone, manufactured by iGM RESINS Omnirad819: iGM RESINS, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide OmniradDETX: 2,4-Dimethylthioxanthone, manufactured by iGM RESINS OmniradEMK: Manufactured by iGM RESINS, 4,4'-bis(diethylamino)benzophenone [others] (Extender pigment) Talc: Hi-Filler 5000PJ (Matsumura Sangyo Co., Ltd.) (Polymerization inhibitor) Polymerization inhibitor: N-nitrosophenylhydroxylamine aluminum

[0074] <Preparation of active energy ray-curable lithographic printing ink composition> Example 1 0.4 parts of Pepol B-184 and 0.5 parts of Erosile R972V were mixed into the black base ink, and dispersed using a three-roll mill so that the maximum particle size was 7.5 μm or less to create the ink.

[0075] Example 13 0.4 parts of Pepol B-184 and 1.5 parts of Erosile 200V were mixed into the yellow base ink, and the mixture was dispersed using a three-roll mill so that the maximum particle size was 7.5 μm or less to prepare an ink.

[0076] Examples 2 to 12, 14 to 21 Comparative Examples 1 to 10 Black inks of Examples 2 to 12 and Comparative Examples 1, 3 to 6 were obtained in the same manner as Example 1, except that the raw materials and amounts shown in Table 1 were changed. Yellow inks of Examples 14 to 21 and Comparative Examples 2, 7 to 10 were obtained in the same manner as Example 13. Note that blanks indicate that no ingredients were blended.

[0077] [Table 1]

[0078] In Table 1, the notations are explained as follows: [Surfactants] Pepol B-184: Toho Chemical Industry Co., Ltd., polyoxyethylene (25) polyoxypropylene (30) Pronon #124P: NOF Corporation, polyoxyethylene (20) polyoxypropylene (20) Pronon #188P: NOF Corporation, polyoxyethylene (160) polyoxypropylene (30) Lipar 860K: Lion Specialty Chemicals, dialkyl sulfosuccinate, N-methyl-N-acyltauride Hexyl diglycol: Sankyo Chemical Co., Ltd., diethylene glycol monohexyl ether hexyl carbitol [silica] Aerosil R972V: Aerosil R972V hydrophobic dry silica manufactured by Toshin Kasei Co., Ltd. Aerosil 200V: Aerosil 200V hydrophilic dry silica manufactured by Toshin Kasei Co., Ltd. Nipsil LP: Tosoh Silica, hydrophilic wet silica

[0079] The performance of the resulting ink composition was evaluated by the following methods, and the results are shown in Table 2. [Liquidity] 3 g of the ink composition obtained was dropped onto a brass inclined plate tilted at 60°C in an atmosphere of 25°C, and the distance the ink flowed from the landing point in 10 minutes was measured and evaluated as static fluidity. The evaluation criteria were that the longer the ink flowed, the better the performance. 5: Static flow is 40 mm or more 4: Static flow is 30 mm or more and less than 40 mm 3: Static flow is 20mm or more and less than 30mm 2: Static flow is 10 mm or more and less than 20 mm 1: Static flow is less than 10 mm

[0080] [How to create a test sample] The obtained ink composition was used to print a solid image on the substrate, Tokubishi art paper, in an amount of 0.25 ml using an RI tester (manufactured by Tester Sangyo Co., Ltd.). The ink composition was then cured at a conveyor speed of 60 m / min with an LED lamp ("XP-9" manufactured by Air Motion Systems Co., Ltd., irradiation distance 10 mm, output 70%) to prepare a test sample. The RI tester is a test machine that prints ink on paper or film, and can adjust the amount of ink transfer and printing pressure. [Gloss] Using the test piece prepared by the above method, the gloss value (based on JIS Z 8741) of the surface on which the ink composition is spread is measured at a reflection angle of 60° using a gloss meter GM62D manufactured by Murakami Color Laboratory. A value of 3 or more is evaluated as a level that is acceptable for practical use. 5: Gloss value is 70° or more 4: Gloss value is 65° or more and less than 70° 3: Gloss value is 60° or more and less than 65° 2: Gloss value is 55° or more and less than 60° 1: Gloss value is less than 55°

[0081] [Ink deposition on blanket] The ink adhesion evaluation test was carried out on a UV sheet-fed offset printing press under the following printing conditions with a general pattern and density, and the amount of ink accumulated on the printing press blanket after printing 20,000 copies was visually evaluated on a four-level scale. A score of 2 or higher is considered to be at a level that is acceptable for practical use. 5: Even after printing 20,000 copies, no ink composition was found on the non-printing areas of the blanket. 4: The number of printed copies is 15,000 or more but less than 20,000, and the printing ink composition is deposited on the non-printing areas of the blanket. 3: The number of printed copies is 10,000 or more but less than 15,000, and the printing ink composition is deposited on the non-printing areas of the blanket. 2: The number of printed copies is 5,000 or more but less than 10,000, and the printing ink composition is deposited on the non-printing areas of the blanket. 1: The number of printed copies is less than 5,000, and the printing ink composition is deposited on the non-printing area of ​​the blanket. (Printing conditions) Printing machine: LITHRONE26 (manufactured by Komori Corporation) Paper: Mirror Coat Platinum (127.9g / m2) (Oji Paper Co., Ltd.) Wetting solution: Tap water / PRESSMAX W-P1 (FFGS) mixed in a mass ratio of 98 / 2 Lamp: Metal halide lamp (I-Graphics, output 120W / cm, 3 lamps used) Printing temperature: 25±1℃ Printing speed: 10000 sheets / hour Version: XP-F (FFGS)

[0082] [Table 2]

[0083] From the above, it was found that the active energy ray-curable lithographic printing ink composition of the present invention has excellent fluidity and high gloss, and has excellent printability by suppressing ink deposition on the blanket of the printing press.

Claims

1. An active energy ray-curable lithographic printing black ink comprising a pigment, a photopolymerization initiator, a polymerizable compound, a resin, a surfactant, and silica, The surfactant includes a polyoxyethylene polyoxypropylene glycol surfactant, the content of the polyoxyethylene polyoxypropylene glycol surfactant is 0.8% by mass or less based on the total amount of the active energy ray-curable lithographic printing ink, The content of the polymerizable compound is 40 to 80% by mass based on the total amount of the active energy ray-curable lithographic printing ink, the resin comprises a diallyl phthalate resin; An active energy ray-curable lithographic printing black ink, in which the content of the silica is 0.4 to 2.5% by mass based on the total amount of the active energy ray-curable lithographic printing black ink (excluding the case where the content of the polyoxyethylene polyoxypropylene glycol surfactant is 0.398% by mass or less based on the total amount of the active energy ray-curable lithographic printing black ink).

2. 2. A printed matter obtained by printing the active energy ray-curable lithographic printing ink according to claim 1 onto a substrate and curing the ink by exposure to active energy rays.

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