Patent Application
20250122391
The present invention relates to an ink composition for ultraviolet-curable inkjet printing. More specifically, the present invention relates to an ink composition for ultraviolet-curable inkjet printing capable of achieving both excellent flexibility and image quality when printed on, for example, a label base material (coated paper, PE, etc.).
Conventionally, an ultraviolet-curable ink has been used in fields such as inkjet printing because it dries quickly, does not contain volatile solvents, and can be printed on various base materials (for example, Patent Document 1). Inkjet printing has been applied to a variety of fields from normal printing to special printing because it can create an image easily and inexpensively. Moreover, an ink composition for inkjet printing has been required which can be printed on various base materials that are stretched or bent after printing.
The ink composition described in Patent Document 1 has room for improvement in flexibility and image quality when printed on, for example, a label base material (coated paper, PE, etc.).
The present invention has been made in view of such conventional problems, and it is an object of the present invention to provide an ink composition for ultraviolet-curable inkjet printing capable of achieving both excellent flexibility and image quality when printed on, for example, a label base material (coated paper, PE, etc.).
As a result of intensive studies for solving the above-described problems, the present inventors have found that the above-described problems can be solved simultaneously by adopting certain polyfunctional amine-modified oligomer, nitrogen-containing monomer, aromatic ring-containing monomer, and polyfunctional monomer, as polymerization components, and completed the present invention.
The ink composition for ultraviolet-curable inkjet printing according to one embodiment of the present invention that solves the above-described problems comprises polymerization components and a photopolymerization Initiator, wherein the polymerization components include (A) a polyfunctional amine-modified oligomer, (B) a nitrogen-containing monomer, (C) an aromatic ring-containing monomer, and (D) a polyfunctional monomer, wherein (A) the polyfunctional amine-modified oligomer comprises an acrylated amine compound having two photopolymerizable functional groups and two amino groups in a molecule, wherein (B) the nitrogen-containing monomer comprises at least one of acryloylmorpholine or vinyl caprolactam, wherein (C) the aromatic ring-containing monomer comprises benzyl acrylate and phenoxyethyl acrylate, wherein (D) the polyfunctional monomer comprises at least one of dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, or ethoxylated trimethylolpropane triacrylate, wherein a content of (A) the polyfunctional amine-modified oligomer is 0.8 to 11.0% by mass, wherein a content of (C) the aromatic ring-containing monomer is 32.0 to 75.0% by mass, and wherein a content of (D) the polyfunctional monomer is 1.5 to 14.0% by mass.
The ink composition for ultraviolet-curable inkjet printing according to one embodiment of the present invention (hereinafter also referred to as the ink composition) comprises polymerization components and a photopolymerization initiator. The polymerization components include (A) a polyfunctional amine-modified oligomer, (B) a nitrogen-containing monomer, (C) an aromatic ring-containing monomer, and (D) a polyfunctional monomer. (A) The polyfunctional amine-modified oligomer comprises an acrylated amine compound having two photopolymerizable functional groups and two amino groups in a molecule. (B) The nitrogen-containing monomer comprises at least one of acryloylmorpholine or vinyl caprolactam. (C) The aromatic ring-containing monomer comprises benzyl acrylate and phenoxyethyl acrylate. (D) The polyfunctional monomer comprises at least one of dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, or ethoxylated trimethylolpropane triacrylate. A content of (A) the polyfunctional amine-modified oligomer is 0.8 to 11.0% by mass. A content of (C) the aromatic ring-containing monomer is 32.0 to 75.0% by mass. A content of (D) the polyfunctional monomer is 1.5 to 14.0% by mass. Each component will be described below.
(A) The polyfunctional amine-modified oligomer is contained as a polymerization component and comprises an acrylated amine compound having two photopolymerizable functional groups and two amino groups in a molecule.
The acrylated amine compound having two photopolymerizable functional groups and two amino groups in the molecule is not particularly limited. By way of an example, examples of the photopolymerizable functional group in the acrylated amine compound include a functional group which may undergo polymerization reaction with visible light or invisible light including ionizing radiation such as ultraviolet rays and electron beams to form a cross-linking bond between molecules. Moreover, examples of the photopolymerizable functional group include both a photopolymerizable functional group in a narrow sense which is directly activated by light irradiation to undergo a photopolymerization reaction, and a photopolymerizable functional group in a broad sense which initiates and promotes a photopolymerization reaction due to action of an active species generated from a photopolymerization initiator when irradiated with light with the photopolymerizable functional group and the photopolymerization initiator coexisting.
The photopolymerizable functional group is one having a photoradical polymerization reactivity such as an ethylenic double bond, one having a photocationic polymerization reactivity and a photoanionic polymerization reactivity such as a cyclic ether group such as an epoxy group, or the like. Among them, the photopolymerizable functional group is preferably an ethylenic double bond such as a (meth)acryloyl group, a vinyl group, and an allyl group, and more preferably a (meth)acryloyl group. In the acrylated amine compound having two photopolymerizable functional groups and two amino groups in the molecule, it is preferable that two photopolymerizable functional groups are both (meth)acryloyl groups and that an amine value is 130 to 142 mgKOH/g. Besides, in the present embodiment, the amine value means an amine value per 1 g of solid content, which is converted to an equivalent of potassium hydroxide after measurement by a potentiometric titration method (for example, COMTITE (AUTO TITRATOR COM-900, BURET B-900, TITSTATIONK-900) manufactured by HIRANUMA Co., Ltd.) using a 0.1N aqueous hydrochloric acid.
The acrylated amine compound having two photopolymerizable functional groups and two amino groups in the molecule is preferably an acrylated amine compound obtained by reacting a bifunctional (meth)acrylate with an amine compound. The bifunctional (meth)acrylate is alkylene glycol di(meth)acrylate such as 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate, di(meth)acrylate of alkylene oxide adduct of bisphenol such as di(meth)acrylate of ethylene oxide adduct of bisphenol A, di(meth)acrylate of ethylene oxide adduct of bisphenol F, di(meth)acrylate of ethylene oxide adduct of bisphenol S, di(meth)acrylate of ethylene oxide adduct of thiobisphenol, and di(meth)acrylate of ethylene oxide adduct of brominated bisphenol A, polyalkylene glycol di(meth)acrylate such as polyethylene glycol di(meth)acrylate and polypropylene glycol di(meth)acrylate, di(meth)acrylate of hydroxypivalic acid neopentyl glycol ester, or the like. Among them, the bifunctional (meth)acrylate is preferably 1,6-hexanediol di(meth)acrylate.
The amine compound is a monofunctional amine compound such as benzylamine, phenethylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, n-pentylamine, isopentylamine, n-hexylamine, cyclohexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, n-nonylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, and n-octadecylamine, a polyfunctional amine compound such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,12-dodecamethylenediamine, o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, o-xylylenediamine, p-xylylenediamine, m-xylylenediamine, mentanediamine, bis(4-amino-3-methylcyclohexylnomethane), isophoronediamine, 1,3-diaminocyclohexane, and spiroacetal-based diamine, or the like. Moreover, the amine compound may be a high molecular weight type of polyfunctional amine compound such as polyethyleneimine, polyvinylamine, and polyallylamine.
The above-described acrylated amine compound is preferably a compound obtained by reacting 1,6-hexanediol di(meth)acrylate with an amine compound. Specifically, the acrylated amine compound is CN371 (manufactured by Sartomer), EB7100 (EBECRYL 7100, manufactured by Cytec), Agi008 (manufactured by DSM), or the like.
A content of (A) the component is preferably 0.8% by mass or more, and more preferably 1.0% by mass or more, in the ink composition. Moreover, the content of (A) the component is preferably 11.0% by mass or less, and more preferably 10.0% by mass or less, in the ink composition. When the content of (A) the component is within the above-described ranges, the ink composition has an excellent curability, and also has excellent storage stability and ejection stability.
(B) The nitrogen-containing monomer is contained as a polymerization component and comprises at least one of acryloylmorpholine or vinyl caprolactam. Preferably, both acryloylmorpholine and vinyl caprolactam are used because of their excellent curability and image quality.
A content of (B) the component is preferably 10.0% by mass or more, and more preferably 12.0% by mass or more, in the ink composition. Moreover, the content of (B) the component is preferably 33.0% by mass or less, and more preferably 31.0% by mass or less, in the ink composition. When the content of (B) the component is within the above-described ranges, the ink composition exhibits excellent curability and abrasion resistance.
Besides, (B) the component may comprise nitrogen-containing monomers other than acryloylmorpholine and vinyl caprolactam. Such other nitrogen-containing monomers include acrylamide such as acrylonitrile, (meth)acrylamide, N-methoxymethylacrylamide, diacetone acrylamide, N,N-dimethylacrylamide, and diethylacrylamide, N-alkylol (C1-5) (meth)acrylamide such as N-vinylcarbazole, N-vinylacetamide, N-vinylpyrrolidone, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, hydroxymethyl(meth)acryldiamide, di(2-hydroxyethyl)(meth)acrylamide, di(3-hydroxypropyl)(meth)acrylamide, and di(4-hydroxybutyl)(meth)acrylamide, 1 to 3 molar adducts of ethylene oxide or propylene oxide, N-vinyl caprolactam, vinylmethyloxazolidinone, (meth)acryloylpyrrolidine, and (meth)acryloylpiperidine of these N-alkylol (C1-5) (meth)acrylamide, and the like.
(C) The aromatic ring-containing monomer is contained as a polymerization component and comprises benzyl acrylate and phenoxyethyl acrylate.
A content of (C) the component is preferably 32.0% by mass or more, and more preferably 34.0% by mass or more, in the ink composition. Moreover, the content of (C) the component is preferably 75.0% by mass or less, and preferably 70.0% by mass or less, in the ink composition. When the content of (C) the component is within the above-described ranges, the ink composition has an advantage that image quality becomes improved in a high-density area typed on a label base material (coated paper, PE, etc.).
Besides, (C) the component may comprise aromatic ring-containing monomers other than benzyl acrylate and phenoxyethyl acrylate. Such other aromatic ring-containing monomers include phenoxydialkylene glycol (meth)acrylate such as phenyl (meth)acrylate, benzyl methacrylate, phenoxyethyl methacrylate, phenoxypropyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, and phenoxydipropylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, phenoxypolyethylene glycol-polypropylene glycol-(meth)acrylate, and the like.
(D) The polyfunctional monomer is contained as a polymerization component and comprises at least one of dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, or ethoxylated trimethylolpropane triacrylate.
A content of (D) the component is preferably 1.5% by mass or more, and more preferably 2.0% by mass or more, in the ink composition. Moreover, the content of (D) the component is preferably 14.0% by mass or less, and preferably 13.0% by mass or less, in the ink composition. When the content of (D) the component is within the above-described range, the ink composition has improved coating curability.
Besides, (D) the component may comprise polyfunctional monomers other than dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, and ethoxylated trimethylolpropane triacrylate. Such other polyfunctional monomers include trimethylolpropane tri(meth)acrylate, vinyloxyethoxyethyl (meth)acrylate, EO (10 or 20 molar) modified bisphenol A diacrylate, polyethylene glycol (400) di(meth)acrylate, polyethylene glycol (600) diacrylate, ethoxylated (30) bisphenol A diacrylate, alkoxylated neopentyl glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol (600) dimethacrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, polytetramethylene glycol diacrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate and an ethylene oxide modified product thereof, dipentaerythritol penta(meth)acrylate and an ethylene oxide modified product thereof, dipentaerythritol hexa(meth)acrylate and an ethylene oxide modified product thereof, urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, pentaerythritol ethoxytetraacrylate, caprolactam modified dipentaerythritol hexaacrylate, ethoxylated bisphenol A diacrylate, alkoxylated tetrahydrofurfuryl acrylate, and the like.
The ink composition of the present embodiment comprises a photopolymerization initiator.
The photopolymerization initiator is not particularly limited. By way of an example, the photopolymerization initiator is benzophenone, diethylthioxanthone, 2-methyl-1-(4-methylthio)phenyl-2-morpholinopropan-1-one, 4-benzoyl-4′-methyldiphenylsulfide, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, bis-2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphine oxide, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2,2-dimethyl-2-hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,4,6-trimethylbenzyl-diphenylphosphine oxide, 2-benzyl-2-dimethylamino-1-(morpholinophenyl)-butane-1-one, or the like. Such photopolymerization initiators are commercially available, and can be obtained, for example, under trade names of Irgacure 907, Irgacure 369, Irgacure 184, Irgacure 379, Irgacure 819, TPO, etc. from BASF, and under trade names of DETX, etc. from Lamberti. The photopolymerization initiator may be used in combination.
A content of the photopolymerization initiator is not particularly limited. By way of an example, when ultraviolet rays (UV) or ultraviolet rays (light emitting diodes (LEDs)) are used as light sources, the content of the photopolymerization initiator is preferably 3% by mass or more, and more preferably 4% by mass or more, in the ink composition. Moreover, the content of the photopolymerization initiator is preferably 15% by mass or less, and more preferably 10% by mass or less, in the ink composition. When the content of the photopolymerization initiator is within the above-described ranges, the ink composition may have sufficient curability, internal curability, and low cost.
The ink composition of the present embodiment preferably comprises a sensitizer. When the ink composition comprises a sensitizer, for example, it can promote curability against ultraviolet rays using a light emitting diode (LED) as a light source and has light absorption characteristics mainly in a wavelength range of ultraviolet rays of 400 nm or more, which makes it easy for expressing a sensitizing function of a curing reaction by light having a wavelength in that range. Besides, “expressing a sensitizing function of a curing reaction by light having a wavelength of 400 nm or more” as described above means having light absorption characteristics in a wavelength range of 400 nm or more. By using such a sensitizer, the ink composition of the present embodiment can be promoted in LED curability.
The sensitizer is preferably an anthracene-based sensitizer, a thioxanthone-based sensitizer, or the like, and more preferably a thioxanthone-based sensitizer. A photosensitizer may be used in combination. Specifically, the photosensitizer is an anthracene-based sensitizer such as 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-bis(2-ethylhexyloxy)anthracene, a thioxanthone-based sensitizer such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone, or the like. Representative examples of commercially available products include DBA and DEA (manufactured by KAWASAKI KASEI CHEMICALS LTD.) as anthracene-based sensitizers, DETX and ITX (manufactured by Lambson Ltd.) as thioxanthone-based sensitizers, and the like.
When the ink composition comprises a sensitizer, a content of the sensitizer is preferably greater than 0% and 3.5% by mass or less in the ink composition. When the content of the sensitizer is within the above-described range, an effect obtained by compounding the sensitizer in the ink composition is easily improved.
The ink composition of the present embodiment preferably comprises a colorant. When the ink composition comprises a colorant, it can produce an ink composition of each color.
The colorant is not particularly limited. By way of an example, as colorants, conventionally used pigments and dyes can be used without particular limitation, and pigments such as organic pigments and inorganic pigments are preferable. The colorant may be used in combination.
The organic pigments are dye lake pigments, azo-based, benzoimidazolone-based, phthalocyanine-based, quinacridone-based, anthraquinone-based, dioxazine-based, indigo-based, thioindigo-based, perylene-based, perinone-based, diketo-pyrrolo-pyrrole-based, isoindolinone-based, nitro-based, nitroso-based, anthraquinone-based, flavanthrone-based, quinophthalone-based, pyranthrone-based, indanthrone-based pigments, or the like.
The inorganic pigments are colored pigments such as titanium oxide, red oxide, antimony red, cadmium yellow, cobalt blue, ultramarine blue, navy blue, iron black, chrome oxide green, carbon black, and graphite (including achromatic color pigments such as white and black), extender pigments such as calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, and talc, or the like.
Specific examples of representative pigments for each hue of the ink composition of the present embodiment are as follows. A yellow pigment is C. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 42, 73, 74, 75, 81, 83, 87, 93, 95, 97, 98, 108, 109, 114, 120, 128, 129, 138, 139, 150, 151, 155, 166, 180, 184, 185, 213, or the like, preferably C. I. Pigment Yellow 150, 155, 180, 213, or the like. A content of the yellow pigment is not particularly limited. By way of an example, the content of the yellow pigment is preferably 1.0% by mass or more, and more preferably 1.5% by mass or more, in the ink composition. Moreover, the content of the yellow pigment is preferably 4.0% by mass or less, and more preferably 3.5% by mass or less, in the ink composition.
A magenta pigment is C. I. Pigment Red 5, 7, 12, 22, 38, 48:1, 48:2, 48:4, 49:1, 53:1, 57, 57:1, 63:1, 101, 102, 112, 122, 123, 144, 146, 149, 168, 177, 178, 179, 180, 184, 185, 190, 202, 209, 224, 242, 254, 255, 270, C. I. Pigment Violet 19, or the like, preferably C. I. Pigment Red 122, 202, Pigment Violet 19, or the like. A content of the magenta pigment is not particularly limited. By way of an example, the content of the magenta pigment is preferably 1.8% by mass or more, and more preferably 2.3% by mass or more, in the ink composition. Moreover, the content of the magenta pigment is preferably 4.8% by mass or less, and more preferably 4.3% by mass or less, in the ink composition.
A cyan pigment is C. I. Pigment Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 18, 22, 27, 29, 60, or the like, preferably C. I. Pigment Blue 15:4 or the like. A content of the cyan pigment is not particularly limited. By way of an example, the content of the cyan pigment is preferably 1.0% by mass or more, and more preferably 1.5% by mass or more, in the ink composition. Moreover, the content of the cyan pigment is preferably 4.0% by mass or less, and more preferably 3.5% by mass or less, in the ink composition.
A black pigment is carbon black (C. I. Pigment Black 7) or the like. A content of the black pigment is not particularly limited. By way of an example, the content of the black pigment is preferably 1.0% by mass or more, and more preferably 1.5% by mass or more, in the ink composition. Moreover, the content of the black pigment is preferably 4.0% by mass or less, and more preferably 3.5% by mass or less, in the ink composition.
A white pigment is titanium oxide, aluminum oxide, or the like, preferably titanium oxide surface-treated with various materials such as alumina and silica, or the like. A content of the white pigment is not particularly limited. By way of an example, the content of the white pigment is preferably 10% by mass or more, and more preferably 13% by mass or more, in the ink composition. Moreover, the content of the white pigment is preferably 23% by mass or less, and more preferably 19% by mass or less, in the ink composition.
A content of the colorant is preferably 1% by mass or more in the ink composition. Moreover, the content of the colorant is preferably 20% by mass or less in the ink composition. When the content of the colorant is within the above-described ranges, the ink composition has an appropriate image quality of a printed matter obtained and is excellent in viscosity property.
A pigment dispersant is appropriately compounded in order to improve dispersibility of the pigment and storage stability of the ink composition.
The pigment dispersant is not particularly limited. By way of an example, the pigment dispersant is a carbodiimide-based dispersant, a polyester amine-based dispersant, a fatty acid amine-based dispersant, a modified polyacrylate-based dispersant, a modified polyurethane-based dispersant, a multichain polymer nonionic dispersant, a polymer ion activator, or the like. The pigment dispersant may be used in combination.
When the pigment dispersant is compounded, a content of the pigment dispersant is not particularly limited. The content of the pigment dispersant is preferably 1 to 200% by mass based on 100% by mass of the pigment. When the content of the pigment dispersant is within the above-described range, an ink composition obtained has an excellent storage stability.
The ink composition of the present embodiment may contain, as other components, various additives such as a surfactant, an organic solvent, a polymerization inhibitor, a preservability improving agent, an ultraviolet absorber, an antioxidant, an anti-foaming agent, an antifungal agent, an antirust agent, a thickener, a moisturizing agent, and a pH adjusting agent.
The surfactant (leveling agent) is not particularly limited. By way of an example, the surfactant is a nonionic surfactant, a cationic surfactant, an anionic surfactant, a betaine surfactant, or the like. More specifically, the surfactant is a silicone-based surfactant such as a polyether-modified silicone oil, a polyester-modified polydimethylsiloxane, and a polyester-modified methylalkyl polysiloxane, a fluorine-based surfactant, an acetylene-based surfactant, or the like.
The silicone-based surfactant is BYK-307, BYK-315N, BYK-331, BYK-333, BYK-347, BYK-348, BYK-349, BYK-345, BYK-377, BYK-378, BYK-3455 (manufactured by BYK-Chemie), or the like.
The fluorine-based surfactant is F-410, F-444, F-553 (manufactured by DIC CORPORATION), FS-65, FS-34, FS-35, FS-31, FS-30 (manufactured by DuPont), or the like.
The acetylene-based surfactant is DYNOL 607, DYNOL 609, OLFINE E1004, OLFINE E1010, OLFINE E1020, OLFINE PD-001, OLFINE PD-002W, OLFINE PD-004, OLFINE PD-005, OLFINE EXP.4001, OLFINE EXP.4200, OLFINE EXP.4123, OLFINE EXP.4300 (manufactured by Nissin Chemical Industry Co., Ltd.), SURFYNOL 104E, SURFYNOL 104H, SURFYNOL 104A, SURFYNOL 104BC, SURFYNOL 104DPM, SURFYNOL 104PA, SURFYNOL 104PG-50, SURFYNOL 420, SURFYNOL 440, SURFYNOL 465 (manufactured by Evonik Industries AG), or the like.
When a surfactant is compounded, a content of the surfactant is not particularly limited. By way of an example, the content of the surfactant is preferably 0.005% by mass or more, and more preferably 0.01% by mass or more, from the viewpoint of improving ejection stability of the ink composition from an inkjet head. Moreover, the content of the surfactant is preferably 1.5% by mass or less, and more preferably 1% by mass or less.
A solvent may be compounded in the ink composition. The solvent is an ester-based organic solvent, an ether-based organic solvent, an ether ester-based organic solvent, a ketone-based organic solvent, an aromatic hydrocarbon solvent, a nitrogen-containing organic solvent, or the like.
When the solvent is compounded, a content of the solvent is not particularly limited. By way of an example, the content of the solvent is preferably 5% by mass or less, and more preferably 2% by mass or less, in the ink composition.
The polymerization inhibitor is not particularly limited. By way of an example, the polymerization inhibitor is a N—CH3 type, N—H type, N—OR type hindered amine, etc., or a phenol-based, amine-based, sulfur-based, phosphorus-based polymerization inhibitor, etc.
The preservability improving agent is of N—CH3 type, NH type, N—OR type, or the like.
The ultraviolet absorber is a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a salicylate-based ultraviolet absorber, a hydroxyphenyltriazine-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, a nickel complex salt-based ultraviolet absorber, or the like.
The antioxidant is a phenol-based antioxidant, an amine-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, or the like.
The anti-foaming agent is a silicone-based anti-foaming agent, a Pluronic (Registered Trademark)-based anti-foaming agent, or the like.
Returning back to the general description of the ink composition, the ink composition of the present embodiment preferably has a viscosity of 30 mPa·s or less, and more preferably 20 mPa·s or less, at 25° C. A viscosity modifier or the like is compounded in the ink composition as necessary. Besides, in the present embodiment, the viscosity can be measured at 25° C. using an E-type viscometer (RE100L-type viscometer, manufactured by Toki Sangyo Co., Ltd.).
The obtained ink composition can be printed on an appropriate base material using an inkjet printer to form an inkjet image. The base material is not particularly limited. By way of an example, the base material includes plastic base materials such as soft polyvinyl chloride, hard polyvinyl chloride, polystyrene, styrofoam, PMMA, polypropylene, polyethylene, PET, and polycarbonate, mixtures or modified products thereof, paper base materials such as high-quality paper, art paper, coated paper, and cast coated paper, metal base materials such as glass and stainless steel, and the like. The ink composition of the present embodiment is particularly appropriate when imparted to label base materials (coated paper, PE, etc.), among them, because it has crosslink densities that are not too high and it is imparted with coating film bendability.
As described above, the ink composition of the present embodiment can achieve both excellent flexibility and image quality when printed on, for example, a label base material (coated paper, PE, etc.).
One embodiment of the present invention has been described above. The present invention is not particularly limited to the above-described embodiment. Besides, the above-described embodiment mainly describes an invention having the following configurations.
(1) An ink composition for ultraviolet-curable inkjet printing comprising polymerization components and a photopolymerization initiator, wherein the polymerization components include (A) a polyfunctional amine-modified oligomer, (B) a nitrogen-containing monomer, (C) an aromatic ring-containing monomer, and (D) a polyfunctional monomer, wherein (A) the polyfunctional amine-modified oligomer comprises an acrylated amine compound having two photopolymerizable functional groups and two amino groups in a molecule, wherein (B) the nitrogen-containing monomer comprises at least one of acryloylmorpholine or vinyl caprolactam, wherein (C) the aromatic ring-containing monomer comprises benzyl acrylate and phenoxyethyl acrylate, wherein (D) the polyfunctional monomer comprises at least one of dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, or ethoxylated trimethylolpropane triacrylate, wherein a content of (A) the polyfunctional amine-modified oligomer is 0.8 to 11.0% by mass, wherein a content of (C) the aromatic ring-containing monomer is 32.0 to 75.0% by mass, and wherein a content of (D) the polyfunctional monomer is 1.5 to 14.0% by mass.
According to such a configuration, the ink composition for ultraviolet-curable inkjet printing can achieve both excellent flexibility and image quality when printed on, for example, a label base material (coated paper, PE, etc.).
(2) The ink composition for ultraviolet-curable inkjet printing of (1), wherein (B) the nitrogen-containing monomer is 10.0% by mass to 33.0% by mass.
According to such a configuration, the ink composition for ultraviolet-curable inkjet printing has a good curability.
Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to these Examples. Besides, unless otherwise specified, “%” means “% by mass”, and “part” means “part by mass”.
Raw materials used are shown below.
Amine-modified oligomer: Acrylated amine compound having two photopolymerizable functional groups and two amino groups in a molecule, CN371NS: manufactured by Sartomer
A mixture obtained by compounding each of raw materials other than a photopolymerization initiator, a sensitizer, a polymerization inhibitor, and a leveling agent so as to have compounding formulations (% by mass) shown in Table 1 was dispersed using an Eiger mill (using zirconia beads having a diameter of 0.5 mm as a medium) to obtain a conc base. Using the obtained conc base, the photopolymerization initiator, the sensitizer, the polymerization inhibitor, and the leveling agent were compounded so as to have compounding formulations (% by mass) shown in Table 1 to obtain ink compositions for ultraviolet-curable inkjet printing in Examples 1 to 14 and Comparative examples in 1 to 7.
Using the ink compositions for ultraviolet-curable inkjet printing in Examples 1 to 14 and Comparative examples 1 to 7, specific gravity, viscosity, surface tension, adhesiveness, flexibility, LED curability, image quality, and head ejection performance of the ink compositions were evaluated according to the following evaluation methods and evaluation criteria. The results are shown in Table 1.
Viscosity of the ink composition for ultraviolet-curable inkjet printing was measured under a condition of a temperature at 25° C. and a rotor rotation speed of 20 rpm using the E-type viscometer (RE100L-type viscometer, manufactured by Toki Sangyo Co., Ltd.).
Specific gravity of the ink composition for ultraviolet-curable inkjet printing was measured using a Gay-Lussac type specific gravity bottle (pycnometer).
Surface tension of the ink composition for ultraviolet-curable inkjet printing was measured at a temperature of 25° C. using a dynamic wettability tester (WET-6000, manufactured by RHESCA Co., LTD.).
Adhesiveness of the ink composition for ultraviolet-curable inkjet printing was evaluated by a cross-cut test. A test piece was created by solid-coating each base material of PVC, coated paper, and PET with an ink composition for active energy ray-curable inkjet, and then curing it by irradiating it with an ultraviolet ray. Evaluation was performed by cross-cutting a cured coating film formed on the base material with a cutter knife into 100 square pieces of cured coating film, putting cellophane tape (Cellulose tape (Registered Trademark), manufactured by NICHIBAN Co., Ltd.) on the cut part and tearing it off, and counting the number of square pieces remained on the base material, which adhered to the cellophane tape without peeling off. 100/100 in Table 1 means that all the pieces remained on the base material without peeling off, indicating that adhesiveness was good.
Evaluation was performed by printing an ink composition for ultraviolet-curable inkjet printing on coated paper and bending the printed material by 180°, according to the following evaluation criteria.
An inkjet recording device and an ink composition for ultraviolet-curable inkjet printing were placed under an atmospheric temperature at 25° C. for 24 hours, and each temperature of the inkjet recording device and the ink composition for ultraviolet-curable inkjet printing was set to 25° C. Then, the ink composition for ultraviolet-curable inkjet printing was continuously printed (typed) on a PCV sheet at 25° C. and then cured with a UV integrated light amount of 180 mJ/cm2 by use of a UV-LED light lamp manufactured by Phoseon Technology at a distance of 2 cm between a lamp and an ink-coated surface. The obtained curable coating film was rubbed with a cotton swab, and curability was evaluated depending on a degree of rubbing-off according to the following evaluation criteria.
Adhesiveness of the ink composition for ultraviolet-curable inkjet printing was determined by creating a coated paper print, visually checking a part of the coated paper print with a coverage rate of 70% density, and rating it as ⊚ if there was no unevenness.
An inkjet recording device with an inkjet nozzle and an ink composition for ultraviolet-curable inkjet printing were placed under an atmospheric temperature at 25° C. for 24 hours, and each temperature of the inkjet recording device and the ink composition for ultraviolet-curable inkjet printing was set to 25° C. Then, at 25° C., printing (typing) was continuously performed on a PCV sheet using the ink composition for ultraviolet-curable inkjet printing, and ejection stability was evaluated according to the following evaluation criteria.
As shown in Table 1, the ink compositions for ultraviolet-curable inkjet printing in Examples 1 to 14 of the present invention were easy to be ejected, easy to cure, had an excellent adhesiveness, and had an excellent flexibility on coated paper. Moreover, the obtained inkjet images had an excellent image quality. On the other hand, the ink compositions for ultraviolet-curable inkjet printing in Comparative examples 1 to 3, which did not contain both benzyl acrylate and phenoxyethyl acrylate as (C) the aromatic ring-containing monomers, had poor image quality and head ejection performance. Moreover, the ink compositions for ultraviolet-curable inkjet printing in Comparative examples 4 and 5, in which the content of (D) the polyfunctional monomer was outside the range of the present invention, had poor flexibility and LED curability. Furthermore, the ink compositions for ultraviolet-curable inkjet printing in Comparative examples 6 and 7, in which the content of (A) the amine-modified oligomer was outside the range of the present invention, had poor flexibility and LED curability.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-159458 | Sep 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2022/027156 | 7/8/2022 | WO |
