How to create a digital embossing

Abstract

To provide a method that can form embossed patterns with clear concavoconvex areas, by requiring no etching or brushing process to form an embossed surface and by forming any range and convex shape by inkjet printing on demand and with a known device so as to form more delicate and sharper protrusions.SOLUTION: A creation method of a digital emboss with an active energy ray curable inkjet ink composition satisfies the following conditions 1 and 2. Condition 1: A viscosity of a first and second active energy ray curable inkjet ink composition is 14.0 cps (25°C) or higher. Condition 2: (Surface tension of the second active energy beam curable inkjet ink composition before curing)-(Surface tension of the first active energy beam curable inkjet ink composition before curing) is greater than 4.0 mN / m.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for creating a digital embossment. [Background technology]

[0002] It is known that by adding three-dimensional decorative printing to printed materials and adding foil, partial coating varnish, and texture to graphic designs, it is possible to create images that are more lustrous and shiny to the eye and to the touch, and that have a particularly three-dimensional feel when touched, making them dynamic, eye-catching, and inviting to be touched. For example, Patent Document 1 describes that although it is not based on a curable ink composition, a realistic wood grain pattern can be easily expressed using a clear ink. However, in this case, there is a limit to how thick the clear varnish can be formed. Patent Document 2 describes a method for forming raised images using a curable gel composition and performing digital embossing. The method describes that the height of the resulting raised images is 40 to 60 μm, and furthermore, Figures 1 and 2 showing examples and their results indicate that convex portions with a height of about 2 mm can be formed using a composition with a specific composition. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-173003 [Patent Document 2] Japanese Patent Application Publication No. 2019-181937 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a method for forming an embossed surface, which does not require an etching step or a brushing step, can be performed on demand using various known inkjet printing devices, can produce convex portions of any range and shape, can form more delicate and sharp convex portions, and can form an embossed pattern with clearly defined concave and convex portions. [Means for solving the problem]

[0005] The present inventors have conducted extensive research to solve the above problems and have completed the present invention as described below. That is, the present invention is as follows. 1. A method for creating a digital embossment using an actinic radiation-curable inkjet ink composition, comprising: a first actinic energy ray-curable inkjet ink composition is deposited on a substrate surface in droplets with a volume of 10.0 pL or more, and then the ink composition is irradiated with actinic energy rays to perform pinning curing to form a first layer; Next, a second actinic energy ray-curable inkjet ink composition is deposited in droplets having a volume of 10.0 pL or more on the first layer, and then the ink is irradiated with actinic energy rays to perform pinning curing to form a second layer. A method for forming a digital embossment, Furthermore, a method for creating a digital embossment that satisfies the following conditions 1 and 2. Condition 1: The viscosity of the first and second actinic energy ray-curable inkjet ink compositions is 14.0 cps (25° C.) or more. Condition 2: (surface tension of the second actinic energy ray-curable inkjet ink composition before curing) - (surface tension of the first actinic energy ray-curable inkjet ink composition before curing) is 4.0 mN / m or more 2. The method for creating a digital embossment according to 1, wherein condition 3: (surface tension of the first actinic energy ray-curable inkjet ink composition before curing) - (surface tension of the substrate surface) is -15.0 mN / m or more. 3. The method for creating a digital embossment according to 1 or 2, wherein the surface tension of the substrate surface is 22.0 to 40.0 mN / m, the surface tension of the first actinic energy ray-curable inkjet ink composition before curing is 22.0 to 29.0 mN / m, and the surface tension of the second actinic energy ray-curable inkjet ink composition before curing is 26.0 to 34.0 mN / m. 4. The method for creating a digital embossment according to any one of 1 to 3, wherein, after the first actinic energy ray-curable inkjet ink composition and the second actinic energy ray-curable inkjet ink composition have been deposited, the time required for pinning and curing of each coating film by irradiating the coating film with actinic energy rays is within 0.5 seconds. 5. The method for creating a digital embossment according to any one of 1 to 4, wherein the first actinic energy ray-curable inkjet ink composition and the second actinic energy ray-curable inkjet ink composition each independently contain a monofunctional photopolymerizable compound, a polyfunctional photopolymerizable compound, and a surfactant. 6. The method for creating a digital embossment according to any one of 1 to 5, wherein the sum of the film thickness of the cured layer of the first actinic energy ray-curable inkjet ink composition and the film thickness of the cured layer of the second actinic energy ray-curable inkjet ink composition is 80.0 μm or more. 7. The method for creating a digital embossment according to any one of 1 to 6, wherein the first and second actinic energy ray-curable inkjet ink compositions contain one or more monomers selected from the group consisting of alicyclic alkyl group-containing (meth)acrylates, acryloylmorpholine, and amine-modified acrylate monomers. [Effects of the Invention]

[0006] According to the present invention, the embossed surface is formed not by etching or brushing, but by layering ink compositions to obtain a digital embossment with delicate dots having sufficiently high heights. Digital embossing refers to a method of forming convex portions on a substrate using an inkjet coating device. DETAILED DESCRIPTION OF THE INVENTION

[0007] The present invention is a method for producing a digital embossment using an actinic ray-curable inkjet ink composition, and it is essential that the following requirements be satisfied. A method for creating a digital embossment using an actinic ray-curable inkjet ink composition, comprising: a first actinic energy ray-curable inkjet ink composition is deposited on a substrate surface in droplets with a volume of 10.0 pL or more, and then the ink composition is irradiated with actinic energy rays to perform pinning curing to form a first layer; Next, a second actinic energy ray-curable inkjet ink composition is deposited in droplets having a volume of 10.0 pL or more on the first layer, and then the ink is irradiated with actinic energy rays to perform pinning curing to form a second layer. A method for forming a digital embossment, Furthermore, a method for creating a digital embossment that satisfies the following conditions 1 and 2. Condition 1: The viscosity of the first and second actinic energy ray-curable inkjet ink compositions is 14.0 cps (25° C.) or more. Condition 2: (surface tension of the second actinic energy ray-curable inkjet ink composition before curing) - (surface tension of the first actinic energy ray-curable inkjet ink composition before curing) is 4.0 mN / m or more

[0008] <Viscosity> The viscosity in the present invention is a value measured using a Brookfield viscometer at 25° C. and 60 rpm (unit: cps).

[0009] <Surface tension> Measurements were made using an automatic surface tensiometer DY-300 manufactured by Kyowa Interface Science Co., Ltd. The surface tension in the present invention is measured at 25°C.

[0010] <Active energy rays> The active energy rays in the present invention may be any rays capable of curing the active energy ray-curable component described below, such as ultraviolet rays, electron beams, α rays, β rays, and γ rays.

[0011] <Active energy ray-curable component> The actinic ray-curable component (all polymerizable components) contained in the first and second actinic ray-curable inkjet ink compositions of the present invention is at least one of the following compounds. Among the compounds listed below, it is preferable to contain one or more selected from alicyclic alkyl group-containing (meth)acrylates, acryloylmorpholine, and amine-modified acrylate monomers. Furthermore, the inclusion of these compounds facilitates the formation of better adhesion and larger embossing irregularities. Furthermore, the composition may or may not contain an oligomer. The alicyclic alkyl group-containing (meth)acrylate preferably contains isobornyl acrylate and / or tert-butylcyclohexyl acrylate. In this case, the total content of isobornyl acrylate and tert-butylcyclohexyl acrylate in the total polymerizable components is preferably 25.0% by mass or more, more preferably 30.0% by mass or more. Also, it is preferably 90.0% by mass or less, more preferably 85.0% by mass or less. The total content of the alicyclic alkyl group-containing (meth)acrylates in all polymerizable components is preferably 15.0% by mass or more, more preferably 30.0% by mass or more, even more preferably 60.0% by mass or more, and most preferably 80.0% by mass or more, and is preferably 93.0% by mass or less, more preferably 90.0% by mass or less. When an amine-modified acrylate monomer is further contained, the content of the amine-modified acrylate monomer in all polymerizable components is preferably 8.0% by mass or more, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less. It is preferable that the actinic ray-curable components contained in the first and second actinic ray-curable inkjet ink compositions of the present invention are monomers and oligomers of the same compound, since this allows for the formation of finer convex portions when the first and second actinic ray-curable inkjet ink compositions are cured to form a digital embossment. In this case, the first and second actinic ray-curable inkjet ink compositions differ in the compounds and contents of the components other than the polymerizable component.

[0012] -Unsaturated carboxylic acid compounds- Examples of unsaturated carboxylic acid compounds include unsaturated carboxylic acids such as (meth)acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, fumaric acid, and maleic acid, as well as salts and acid anhydrides thereof.

[0013] -Alkyl (meth)acrylate compounds- Examples of alkyl(meth)acrylate compounds include methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, i-butyl(meth)acrylate, t-butyl acrylate, amyl(meth)acrylate, isoamyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate, decyl(meth)acrylate, dodecyl(meth)acrylate, isooctyl(meth)acrylate, lauryl(meth)acrylate, stearyl(meth)acrylate, isostearyl(meth)acrylate, isodecyl(meth)acrylate, and isomyristyl(meth)acrylate. Examples of alicyclic alkyl group-containing (meth)acrylates include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 1-adamantyl (meth)acrylate, 3,5,5-trimethylcyclohexyl acrylate, 4-t-butylcyclohexyl (meth)acrylate, and benzyl (meth)acrylate.

[0014] -Hydroxyl group-containing (meth)acrylate compounds- Examples of the hydroxyl group-containing (meth)acrylate compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, 2-hydroxy-3-methoxypropyl (meth)acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate. and (poly)alkylene glycol-modified (meth)acrylates such as 2-ethylhexyl EO-modified (meth)acrylate, 1,6-hexanediol mono(meth)acrylate, glycerin mono(meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-allyloxypropyl (meth)acrylate, 2-hydroxy-3-allyloxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, 2-ethylhexyl EO-modified (meth)acrylate, o-phenylphenol EO-modified (meth)acrylate, p-cumylphenol EO-modified (meth)acrylate, and nonylphenol EO-modified (meth)acrylate.

[0015] -Halogen-containing (meth)acrylate compounds- Examples of halogen-containing (meth)acrylate compounds include trifluoromethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H-hexafluoroisopropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, 1H,1H,2H,2H-heptadecafluorodecyl (meth)acrylate, 2,6-dibromo-4-butylphenyl (meth)acrylate, 2,4,6-tribromophenoxyethyl (meth)acrylate, and 2,4,6-tribromophenol 3EO (ethylene oxide) adduct (meth)acrylate.

[0016] -Ether group-containing (meth)acrylate compounds- Examples of the ether group-containing (meth)acrylate compounds include 1,3-butylene glycol methyl ether (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, ethyl carbitol (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, tetrahydrofuran (meth)acrylate, methyl methyl ether ... Furyl (meth)acrylate, cresyl polyethylene glycol (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, phenoxyethyl (meth)acrylate, p-nonylphenoxyethyl (meth)acrylate, p-nonylphenoxypolyethylene glycol (meth)acrylate, glycidyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, hexaethylene glycol monophenyl ether mono(meth)acrylate , diethylene glycol monobutyl ether acrylate, dipropylene glycol monomethyl ether (meth)acrylate, 3-methoxybutyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate (EO repeating unit number 400, 700, etc.), 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxy Butyl acrylate, ethoxyethyl acrylate, ethoxyethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, alkoxylated 2-phenoxyethyl (meth)acrylate (ethoxylated 2-phenoxyethyl (meth)acrylate, propoxylated 2-phenoxyethyl (meth)acrylate, etc.), alkoxylated nonylphenyl (meth)acrylate (ethoxylated (4) nonylphenol acrylate, etc.), 2-phenoxyethyl (meth)acrylate, paracumylphenoxyethylene glycol (meth)acrylate,Examples of such alkoxy and / or phenoxy (meth)acrylates include methylphenoxyethyl acrylate, ethoxylated succinic acid (meth)acrylate, ethoxylated tribromophenyl acrylate, and ethoxylated nonylphenyl (meth)acrylate.

[0017] -Carboxyl group-containing (meth)acrylate compounds- Examples of the carboxyl group-containing (meth)acrylate compounds include β-carboxyethyl (meth)acrylate, succinic acid monoacryloyloxyethyl ester, ω-carboxypolycaprolactone mono(meth)acrylate, 2-(meth)acryloyloxyethyl ester, β-carboxyethyl ester, ω-carboxyethyl ester, 2-(meth)acryloyloxy ...ω-carboxyethyl ester, 2-(meth)acryloyloxyethyl ester, ω-carboxyethyl ester, ω-carboxyethyl ester, 2-(meth)acryloyloxyethyl ester, Diethyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hexahydrogen phthalate acrylate, 2-(meth)acryloyloxypropyl tetrahydrohydrogen phthalate etc.

[0018] -Vinyl ether group-containing (meth)acrylate compounds- Examples of vinyl ether group-containing (meth)acrylate compounds include 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 1-methyl-3-vinyloxypropyl (meth)acrylate, 1-vinyloxymethylpropyl (meth)acrylate, and 2-methyl-3-vinyloxypropyl (meth)acrylate. Pyr, (meth)acrylate-3-methyl-3-vinyloxypropyl, (meth)acrylate-1,1-dimethyl-2-vinyloxyethyl, (meth)acrylate-3-vinyloxybutyl, (meth)acrylate-1-methyl-2-vinyloxypropyl, (meth)acrylate-2-vinyloxybutyl, (meth)acrylate-4-vinyloxycyclohexyl, (meth)acrylate-5-vinyloxypentyl, (meth)acrylate-6-vinyloxyhexyl, (meth)acrylate-4-vinyloxymethylcyclohexyl xylmethyl, (meth)acrylate-3-vinyloxymethylcyclohexylmethyl, (meth)acrylate-2-vinyloxymethylcyclohexylmethyl, (meth)acrylate-p-vinyloxymethylphenylmethyl, (meth)acrylate-m-vinyloxymethylphenylmethyl, (meth)acrylate-o-vinyloxymethylphenylmethyl, (meth)acrylate-2-(vinyloxyisopropoxy)ethyl, (meth)acrylate-2-(vinyloxyethoxy)propyl, (meth)acrylate-2-( (vinyloxyethoxy)isopropyl, (meth)acrylate-2-(vinyloxyisopropoxy)propyl, (meth)acrylate-2-(vinyloxyisopropoxy)isopropyl, (meth)acrylate-2-(vinyloxyethoxyethoxy)ethyl, (meth)acrylate-2-(vinyloxyethoxyisopropoxy)ethyl, (meth)acrylate-2-(vinyloxyisopropoxyethoxy)ethyl, (meth)acrylate-2-(vinyloxyisopropoxyisopropoxy)ethyl, (meth)acrylate-2-(vinyloxyisopropoxyisopropoxy)ethyl.

[0019] -Other (meth)acrylate compounds- Other (meth)acrylate compounds include, for example, acryloylmorpholine, amine-modified acrylate monomers such as N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, morpholinoethyl (meth)acrylate, trimethylsiloxyethyl (meth)acrylate, diphenyl-2-(meth)acryloyloxyethyl phosphate, 2-(meth)acryloyloxyethyl acid phosphate, caprolactone-modified 2-(meth) Acryloyloxyethyl acid phosphate, 2-hydroxy-1-(meth)acryloxy-3-methacryloxypropane, acryloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, tricyclodecane monomethylol (meth)acrylate, (meth)acrylic acid dimer, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl Ethylhexahydrophthalic acid, 2-ethylhexyl-diglycol (meth)acrylate, aminoethyl (meth)acrylate, ethyl carbitol acrylate, ethyl diglycol acrylate, dimethylaminoethyl acrylate benzyl chloride quaternary salt, tribromophenyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, cresol (meth)acrylate, trimethylolpropane formal (meth)acrylate, neopentyl glycol (meth)acrylate Examples of the acrylates include benzoic acid ester, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 1-(meth)acryloylpiperidin-2-one, 2-(meth)acrylic acid-1,4-dioxaspiro[4,5]dec-2-ylmethyl, N-(meth)acryloyloxyethylhexahydrophthalimide, γ-butyrolactone (meth)acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, imide acrylate, vinyl (meth)acrylate, and maleimide.

[0020] -Styrene-based compounds- Examples of styrene compounds include styrene, vinyltoluene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene, pt-butoxycarbonyloxystyrene, 2,4-diphenyl-4-methyl-1-pentene, and divinylbenzene. -N-vinyl compounds- Examples of N-vinyl compounds include N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinyl-2-caprolactam, and N-vinylcarbazole. -Arylate compounds- Examples of the arylate compounds include allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, and isocyanuric acid triallylate.

[0021] -Other compounds with one ethylenically unsaturated bond- As the compound having one ethylenically unsaturated bond, "other compounds having one ethylenically unsaturated bond" other than the above compounds can be used. Examples of such compounds include vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipate, vinyl crotonate, vinyl 2-ethylhexanoate, three-membered ring compounds (e.g., vinylcyclopropanes, 1-phenyl-2-vinylcyclopropanes, 2-phenyl-3-vinyloxiranes, 2,3-divinyloxiranes, etc.), and cyclic ketene acetals (e.g., 2-methylene-1,3-dioxepane, dioxolanes, 2-methylene-4-phenyl-1,3-dioxepane, 4,7-dimethyl-2-methylene-1,3-dioxepane, 5,6-benzo-2-methylene-1,3-dioxepane, etc.).

[0022] (Compound with two ethylenically unsaturated bonds) The actinic ray-curable inkjet ink composition of the present invention can use a known compound having two ethylenically unsaturated bonds. As such a compound having two ethylenically unsaturated bonds, known compounds can be used without any limitation, and examples thereof include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol diacrylate, polyethylene glycol di(meth)acrylate, polyethylene glycol (100) di(meth)acrylate, polyethylene glycol (400) di(meth)acrylate, polyethylene glycol Coal (700) di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, dimethylol octane di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, dimethylolpropane di(meth)acrylate Acrylate, tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-dimethyl-2,4-pentanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate acrylate, 1,5-dimethyl-2,5-hexanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, pentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxypivalyl hydroxypivalate di(meth)acrylate, hydroxypivalyl hydroxypivalate dicaprolactonate di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,2-hexanediol di(meth)acrylate, 1,5-hexanediol di(meth)acrylate, 2,5-Hexanediol di(meth)acrylate, 1,7-Heptanediol di(meth)acrylate, 1,8-Octanediol di(meth)acrylate, 1,2-Octanediol di(meth)acrylate, 1,9-Nonanediol di(meth)acrylate, 1,10-Decanediol di(meth)acrylate, 1,2-Decanediol di(meth)acrylate, 1,12-Dodecanediol di(meth)acrylate, 1,2-Dodecanediol di(meth)acrylate, 1,14-Tetradecanediol di(meth)acrylate, 1,2-Tet Ladecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 1,2-hexadecanediol di(meth)acrylate, 2-methyl-2,4-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-methyl-2-propyl-1,3-propanediol di(meth)acrylate, 2,4-dimethyl-2,4-pentanediol di(meth)acrylate, 2,2-diethyl-1,3-propanediol di(meth)acrylate, 2,2,4-trimethyl 2-methyl-1,3-pentanediol di(meth)acrylate, dimethylol octane di(meth)acrylate, 2-ethyl-1,3-hexanediol di(meth)acrylate, 2,5-dimethyl-2,5-hexanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2,4-diethyl-1,5-pentanediol di(meth)acrylate, 2-methyl-1,3-butylene glycol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, trimethylol octane di(meth)acrylate, Chlodecane dimethylol dicaprolactonate di(meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, 1,6-hexanediol bis(2-hydroxy-3-(meth)acryloyloxypropyl) ether, bis(4-(meth)acryloxypolyethoxyphenyl)propane, pentaerythritol di(meth)acrylate, pentaerythritol di(meth)acrylate monostearate, pentaerythritol di(meth)acrylate monobenzoate, glycerin di(meth)acrylate, 2-hydroxy-1,Examples of the vinyl ether include 3-di(meth)acryloxypropane, diethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, dipropylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane divinyl ether, butanediol divinyl ether, propylene glycol divinyl ether, hexanediol divinyl ether, trimethylolpropane diallyl ether, vinyloxyalkyl (meth)acrylate, vinyloxyethoxyethyl (meth)acrylate, N,N'-methylenebisacrylamide, bisphenol A di(meth)acrylate, bisphenol F di(meth)acrylate, hydroxypivalyl hydroxypivalate di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, and hydrogenated bisphenol F di(meth)acrylate. Further examples include alkoxylated products (e.g., ethoxylated, propoxylated, butoxylated products, etc.) of the compound having two ethylenically unsaturated bonds, which may be, for example, ethoxylated 1,6-hexanediol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, or propoxylated neopentyl glycol di(meth)acrylate.

[0023] Further, for example, ethylene oxide (EO)-modified bisphenol A di(meth)acrylate, propylene oxide (PO)-modified bisphenol A di(meth)acrylate, EO-modified hydrogenated bisphenol A di(meth)acrylate, PO-modified hydrogenated bisphenol A di(meth)acrylate, EO-modified bisphenol F di(meth)acrylate, PO-modified bisphenol F di(meth)acrylate, EO-modified tetrabromobisphenol A di(meth)acrylate, bisphenol A tetraethylene oxide adduct di(meth)acrylate, acrylate, bisphenol F tetraethylene oxide adduct di(meth)acrylate, bisphenol S tetraethylene oxide adduct di(meth)acrylate, hydrogenated bisphenol A tetraethylene oxide adduct di(meth)acrylate, hydrogenated bisphenol F tetraethylene oxide adduct di(meth)acrylate, EO-modified neopentyl glycol di(meth)acrylate, PO-modified neopentyl glycol di(meth)acrylate, polyethylene glycol monovinyl ether (meth)acrylate, polypropylene glycol monovinyl ether (meth)acrylate, neopentyl glycol PO (propylene oxide)-modified di(meth)acrylate, and isocyanuric acid EO-modified di(meth)acrylate. One or more alkylene oxide-modified compounds (e.g., ethylene oxide, propylene oxide, etc.) of the compound having two ethylenically unsaturated bonds may be used. Furthermore, one or more caprolactone-modified compounds of the compound having two ethylenically unsaturated bonds may be used, which may be one or more selected from the group consisting of bisphenol A tetraethylene oxide adduct dicaprolactonate di(meth)acrylate, bisphenol F tetraethylene oxide adduct dicaprolactonate di(meth)acrylate, hydroxypivalyl hydroxypivalate dicaprolactonate di(meth)acrylate, and caprolactone adduct di(meth)acrylate of hydroxypivalic acid neopentyl glycol ester.

[0024] (Compound with three ethylenically unsaturated bonds) The actinic ray-curable inkjet ink composition of the present invention may contain a known compound having three ethylenically unsaturated bonds. As such a compound having three ethylenically unsaturated bonds, known compounds can be used without limitation, and examples thereof include glycerin tri(meth)acrylate, tetramethylolmethane triacrylate, tetramethylolpropane tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethyloloctane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane trivinyl ether, trimethylolhexane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol triallyl ether, pentaerythritol trivinyl ether, 1,3,5-tri(meth)acryloylhexahydro-s-tolyl ether, and the like. Examples thereof include liazine, dipentaerythritol tri(meth)acrylate tripropionate, isocyanuric acid tri(meth)acrylate, and tris(acryloyloxy)phosphate. Further examples include alkoxylated products (e.g., ethoxylated, propoxylated, butoxylated) of the trifunctional monomers such as ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, glycerin propoxy tri(meth)acrylate, trimethylolpropane tricaprolactonate tri(meth)acrylate, glycerin PO-modified tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, isocyanuric acid EO-modified ε-caprolactone-modified tri(meth)acrylate, and caprolactone-modified trimethylolpropane tri(meth)acrylate; alkylene oxide-modified products (e.g., ethylene oxide, propylene oxide); and caprolactone-modified products.

[0025] (Compounds with four or more ethylenically unsaturated bonds) The actinic ray-curable inkjet ink composition of the present invention can use a known compound having four or more ethylenically unsaturated bonds. Such compounds having four or more ethylenically unsaturated bonds are not limited to known compounds. Examples of compounds that can be used include compounds having four ethylenically unsaturated bonds, compounds having five ethylenically unsaturated bonds, compounds having six ethylenically unsaturated bonds, and compounds having seven or more ethylenically unsaturated bonds. Examples of compounds having four or more ethylenically unsaturated bonds include diglycerin tetra(meth)acrylate, ditrimethylolethane tetra(meth)acrylate, ditrimethyloloctane tetra(meth)acrylate, ditrimethylolbutane tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ditrimethylolpropane tetracaprolactonate tetra(meth)acrylate, ditrimethylolhexane tetra(meth)acrylate, trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetraallyl ether, and pentaerythritol tetra(meth)acrylate. Examples of the acrylate include dipentaerythritol tetracaprolactonate tetra(meth)acrylate, pentaerythritol tetravinyl ether, dipentaerythritol tetra(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, oligoester tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol polyalkylene oxide hepta(meth)acrylate, and tripentaerythritol octa(meth)acrylate. Other examples include alkoxylated products such as ethoxylated, propoxylated, and butoxylated products of the tetrafunctional or higher monomers, such as ethylene oxide-modified pentaerythritol tetra(meth)acrylate and ethoxylated pentaerythritol tetra(meth)acrylate; alkylene oxide-modified products such as ethylene oxide and propylene oxide; and caprolactone-modified products.

[0026] <Epoxidized vegetable oil (meth)acrylate compound> The actinic radiation-curable inkjet ink composition of the present invention may also contain a known epoxidized vegetable oil (meth)acrylate compound. Since the epoxidized vegetable oil (meth)acrylate is derived from vegetable oil, it is possible to increase the amount of biomass components in the actinic radiation-curable inkjet ink composition. The epoxidized vegetable oil (meth)acrylate compound is obtained by (meth)acrylic-modifying an epoxidized vegetable oil, and examples thereof include compounds obtained by ring-opening addition polymerization of (meth)acrylic acid to the epoxy groups of an epoxidized vegetable oil in which the double bonds of an unsaturated vegetable oil are epoxidized with an oxidizing agent such as peracetic acid or perbenzoic acid.

[0027] (oligomer or polymer) The actinic ray-curable inkjet ink composition of the present invention may contain a known polymer or oligomer having an ethylenically unsaturated bond. The polymer or oligomer having an ethylenically unsaturated bond may be one having one or more ethylenically unsaturated bonds of one or more types selected from the group consisting of a (meth)acryloyl group, a vinyl group, and the like. Examples of polymers or oligomers having an ethylenically unsaturated bond include polydiallyl phthalate, neopentyl glycol oligo(meth)acrylate, 1,4-butanediol oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, urethane (meth)acrylates such as polyester urethane diacrylate oligomer, polyester (meth)acrylates such as polyester acrylate oligomer, epoxy (meth)acrylate, rosin-modified epoxy (meth)acrylate, unsaturated polyester, polyether (meth)acrylate, acrylic resins having unreacted unsaturated groups, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, acrylic-modified phenolic resins, and oligomers of acrylated amine compounds. The vegetable oil-modified polyfunctional polyester oligomer may or may not be contained.

[0028] (Other resins not containing ethylenically unsaturated bonds) As the other resins not having an ethylenically unsaturated bond, any known resin can be used without particular limitation within a range in which performance is not reduced, depending on the properties to be imparted to the actinic energy ray-curable inkjet ink composition, particularly appropriate viscoelastic properties and printing properties when the ink composition is constituted. Examples of other resins that do not have ethylenically unsaturated bonds include acrylic resins, polyester resins, styrene resins, polyolefin resins, epoxy resins, polyurethane resins, phenolic resins, rosin resins, block polymers, graft polymers (core-shell polymers), acrylic-modified phenolic resins, rosin-modified phenolic resins, rosin-modified alkyd resins, rosin-modified petroleum-based resins, rosin-modified maleic acid resins, rosin ester-based resins, fatty acid-modified rosin resins, petroleum-based resin-modified phenolic resins, alkyd resins, vegetable oil-modified alkyd resins, petroleum-based resins, hydrocarbon-based resins (such as polybutene and polybutadiene), fluororesins (such as tetrafluoroethylene (PTFE) resin wax), and ketone resins. Particularly preferably, one or more resins selected from the group consisting of acrylic resins (such as acrylic ester-styrene copolymer resins), styrene resins (such as styrene-acrylic ester copolymer resins), rosin-modified phenolic resins, rosin-modified alkyd resins, rosin-modified maleic acid resins, rosin ester resins, fatty acid-modified rosin resins, alkyd resins, and vegetable oil-modified alkyd resins can be used. Such a resin preferably has a weight average molecular weight of 500 to 300,000. From the viewpoint of quick drying when irradiated with active energy rays, the acid value is preferably 1 to 100 mgKOH / g. When the actinic ray-curable inkjet ink composition contains the above-mentioned resin component, the content of the resin component in the actinic ray-curable inkjet ink composition can be set to 0 to 30.0% by mass, and preferably 0 to 20.0% by mass. The acrylate prepolymer having a silicone structure may or may not be contained.

[0029] <Polymerization initiator> The actinic ray-curable inkjet ink composition may contain a known polymerization initiator. The polymerization initiator is not particularly limited as long as it generates active species such as radicals upon irradiation with active energy rays and initiates polymerization of the active energy ray-curable inkjet ink composition, and for example, one or more types selected from the group consisting of redox initiators, thermal polymerization initiators, photopolymerization initiators, etc. It is not necessarily required to contain a polymerization initiator when the active energy ray-curable inkjet ink composition of the present invention is cured by electron beams. A redox initiator exhibits a polymerization initiation function by a redox reaction under mild conditions by combining a peroxide and a reducing agent. The thermal polymerization initiator or the photopolymerization initiator exhibits a polymerization initiation function by generating radicals when irradiated with active energy rays (infrared rays, ultraviolet rays, LED, electron beams, etc.).

[0030] The polymerization initiator is appropriately selected depending on the application, purpose, etc., and it is usually preferable to use a photopolymerization initiator. However, when toxicity needs to be considered, a redox initiator, which is relatively less toxic than thermal polymerization initiators and photopolymerization initiators, which have high potential toxicity, can also be used. Among these, it is preferable to use a photoradical polymerization initiator that has light absorption characteristics over a wavelength range of 450 to 300 nm and can exhibit initiator function for the curing reaction (radical polymerization) with light of wavelengths in that range, in order to improve the curing properties with respect to ultraviolet light emitted from a light-emitting diode (LED) as a light source. Examples of the photoradical polymerization initiator include acylphosphine oxide compounds, triazine compounds, aromatic ketone compounds, aromatic onium salt compounds, organic peroxides, thioxanthone compounds, thiophenyl compounds, anthracene compounds, hexaarylbisimidazole compounds, ketoxime ester compounds, borate compounds, azides, and the like. One or more compounds selected from the group consisting of iodonium compounds, metallocene compounds, active ester compounds, halogenated hydrocarbon compounds and alkylamine compounds, iodonium salt compounds, and sulfonium salt compounds can be used. As the acylphosphine oxide compound, for example, one or more compounds selected from the group consisting of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like can be used. Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-pipenyl-4,6-bis(trichloromethyl)-s-triazine, and 2,4-bis(trichloromethyl).

[0033] One or more compounds selected from the group consisting of 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, and 2,4-trichloromethyl(4'-methoxystyryl)-6-triazine can be used. Furthermore, for example, one or more selected from the group consisting of benzophenone, diethylthioxanthone, 2-methyl-1-(4-methylthio)phenyl-2-morpholinopropan-1-one, 4-benzoyl-4'-methyldiphenyl sulfide, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2,2-dimethyl-2-hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-benzyl-2-dimethylamino-1-(morpholinophenyl)-butan-1-one, and the like can be used. Examples of such photopolymerization initiators that can be used include Irgacure 907, 369, 184, 379, and 819 manufactured by BASF, TPO and DETX manufactured by Lamberti, and TAZ-204 manufactured by Midori Chemical Industry. The content of the photopolymerization initiator in the ink composition can be determined appropriately depending on the components of the actinic energy ray-curable inkjet ink composition, and is, for example, 0.1 to 25.0% by mass, preferably 0.1 to 15.0% by mass, and more preferably 1.0 to 15.0% by mass in the actinic energy ray-curable inkjet ink composition. By setting the content of the photopolymerization initiator in the ink composition within the above range, it is possible to achieve sufficient curability of the ink composition, good internal curability, and cost-effectiveness, which is preferable.

[0031] <Sensitizer> The actinic ray-curable inkjet ink composition of the present invention may contain a sensitizer to improve curability, as long as the effect of the present invention is not impaired. The sensitizers may be used alone or in combination of two or more. Other sensitizers are not particularly limited, but examples include thioxanthone-based sensitizers, benzophenone-based sensitizers such as 4,4'-bis(diethylamino)benzophenone, anthraquinone-based sensitizers, and coumarin-based sensitizers. Among these, particularly preferred are thioxanthone compounds such as 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthen-9-one, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone; anthracene compounds such as 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-bis(2-ethylhexyloxy)anthracene; and 4,4'-dialkylaminobenzophenones such as Michler's ketone and 4,4'-bis-(diethylamino)benzophenone. Polymeric sensitizers may also be used, and examples of thioxanthone-based polymeric sensitizers and acylphosphine-based polymeric sensitizers include Omnipol-TX ((2-carboxymethoxythioxanthone)-(polytetramethylene glycol 250) diester) (number average molecular weight: 660) (manufactured by IGM Resins BV), SpeedCure 7010 (molecular weight: 1839) (manufactured by Lambson), and Genopol TX-1 (number average molecular weight: 820) (manufactured by RaHN). Further, oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propane) (manufactured by Lamberti, "ESACURE KIP 150" and "ESACURE 1"), polyethylene glycol 200-di(β-4(4-(2-dimethylamino-2-benzyl)butanonylphenyl)piperazine) (manufactured by IGM, "Omnipol 910"), (2-carboxymethoxythioxanthone)-(polytetramethylene glycol 250) diester (manufactured by IGM, "Omnipol TX"), (carboxymethoxymethoxybenzophenone)-(polyethylene glycol 250) diester (manufactured by IGM, "Omnipol BP"), etc. These may be used alone or in combination. The amount of the sensitizer contained in the actinic ray-curable inkjet ink composition is preferably 0.5 to 10.0 parts by mass relative to 100 parts by mass of the total amount of all polymerizable components, more preferably 1.0 part by mass or more, even more preferably 1.5 parts by mass or more, and most preferably 2.0 parts by mass or more, and more preferably 6.0 parts by mass or less, even more preferably 4.0 parts by mass or less, and most preferably 3.5 parts by mass or less.

[0032] <Pigments and dyes> The first actinic energy ray-curable inkjet ink composition and the second actinic energy ray-curable inkjet ink composition of the present invention may or may not independently contain a pigment or a dye. When they do not contain a pigment or a dye, they become colorless clear compositions. As the pigment, various inorganic pigments, organic pigments, etc. that are generally used in actinic ray-curable inkjet ink compositions can be used, or a clear composition that does not contain these pigments may also be used. Specific examples of inorganic pigments include colored pigments such as titanium oxide, red iron oxide, antimony red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, and graphite, and extender pigments such as calcium carbonate, kaolin, clay, barium sulfate, aluminum hydroxide, and talc. Furthermore, examples of organic pigments include soluble azo pigments, insoluble azo pigments, azo lake pigments, condensed azo pigments, copper phthalocyanine pigments, and condensed polycyclic pigments. White pigments such as titanium oxide and rutile-type titanium oxide having a treated layer made of silica and / or alumina, as well as other colored pigments, may also be used. When a pigment is contained, the content is 1 to 50% by mass based on the total mass of the actinic radiation-curable inkjet ink composition of the present invention. The present invention is useful for titanium oxide, an inorganic pigment. As the dye, various known dyes can be contained.

[0033] <Pigment dispersant> When the actinic ray-curable inkjet ink composition of the present invention contains a pigment, it is preferable to use a pigment dispersant. The pigment dispersant is used to improve the dispersibility of the pigment and the storage stability of the actinic energy ray-curable inkjet ink composition, and any conventionally used dispersant can be used without any particular limitation, but among them, it is preferable to use a polymeric pigment dispersant. The pigment dispersants can be used alone or in combination of two or more.

[0034] Examples of the polymer pigment dispersant include carbodiimide-based dispersants, polyester amine-based dispersants, fatty acid amine-based dispersants, modified polyacrylate-based dispersants, modified polyurethane-based dispersants, multi-chain polymer nonionic dispersants, and polymer ionic surfactants. Such polymeric pigment dispersants include BYKJET-9150, BYKJET-9151, BYKJET-9170, DISPERBYK-168, DISPERBYK-190, DISPERBYK-198, DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2015 (BYK), SMA1440, SMA2625, SMA17352, SMA3840, SMA1000, SMA2000, SMA3000 (CrayValley), JONCRYL67, JONCRYL678, JONCRYL586, JONCRYL611, JONCRYL680, JONCRYL682, JONCRYL690, JONCRYL81 9, JONCRYL-JDX5050, EFKA4550, EFKA4560, EFKA4585, EFKA4701, EFKA5220, EFKA6230 (BASF), SOLSPERSE20000, SOLSPERSE270 00, SOLSPERSE36000, SOLSPERSE41000, SOLSPERSE41090, SOLSPERSE43000, SOLSPERSE44000, SOLSPERSE46000, SOLSPERSE47000, SOLSPERSE54000, SOLSPERSE56000 (Lubrizol Corporation), Ajisper PB821, Ajisper PB822, Ajisper PB824, Ajisper PB881 (Ajinomoto Fine-Techno Co., Ltd.), and the like.

[0035] From the viewpoint of improving the dispersibility of the pigment and the storage stability of the actinic energy ray-curable inkjet ink composition, the content of the pigment dispersant is preferably 1.0% by mass or more, more preferably 5.0% by mass or more, and is preferably 100% by mass or less, more preferably 60.0% by mass or less, relative to the total mass of the pigment.

[0036] The actinic ray-curable inkjet ink composition of the present invention may contain, as other components, various additives such as a polymerization inhibitor, a surfactant, an organic solvent, a polymerization inhibitor, a storage stability improver, an ultraviolet absorber, an antioxidant, an antifoaming agent, an antifungal agent, an antirust agent, a thickener, a moisturizer, and a pH adjuster.

[0037] (polymerization inhibitor) The photocurable inkjet ink composition of the present invention may contain a known polymerization inhibitor for the purpose of preventing polymerization during storage. Examples of the polymerization inhibitor include phenolic compounds such as p-methoxyphenol, catechol, tert-butylcatechol, and butylhydroxytoluene, hydroquinone, alkyl-substituted hydroquinone, phenothiazine, tocopherol acetate, nitrosamine, benzotriazole, and hindered amine.

[0038] (surfactant) In the photocurable inkjet ink composition of the present invention, any known surfactant used in photocurable inkjet ink compositions can be used without particular limitation depending on the inkjet head used, including, for example, nonionic surfactants, cationic surfactants, anionic surfactants, and betaine surfactants. Specific examples of the surfactant include silicone-based surfactants such as hydroxyl group-containing polyether-modified polydimethylsiloxanes, polyether-modified silicone oils such as polyether-modified polydimethylsiloxanes, polyester-modified polydimethylsiloxanes, polyester-modified methylalkylpolysiloxanes such as polyester-modified polymethylalkylsiloxanes, fluorine-based surfactants, and acetylene-based surfactants. The surfactants can be used alone or in combination of two or more. Among these, silicone-based surfactants are preferred. When a surfactant is contained, its content is not particularly limited, but is preferably such that the surface tension of the first and second actinic energy ray-curable inkjet ink compositions before curing is 22.0 to 35.0 mN / m, and more preferably 0.10 to 1.50 mass% in the actinic energy ray-curable inkjet ink composition.

[0039] Examples of the silicone surfactant include BYK-307, BYK-315, BYK-331, BYK-333, BYK-347, BYK-348, BYK-349, BYK-345, BYK-377, BYK-378, and BYK-3455 (BYK).

[0040] Examples of the fluorine-based surfactant include F-410, F-444, and F-553 (DIC Corporation), and FS-65, FS-34, FS-35, FS-31, and FS-30 (DuPont).

[0041] Examples of the acetylene surfactant include 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 (Nissin Chemical Co., Ltd.), Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol 104BC, Surfynol 104DPM, Surfynol 104PA, Surfynol 104PG-50, Surfynol 420, Surfynol 440, and Surfynol 465 (EVONIK).

[0042] The proportion of the surfactant in the actinic ray-curable inkjet ink composition of the present invention is preferably 0.005% by mass or more, and more preferably 0.01% by mass or more, from the viewpoint of reducing the surface tension of the ink composition and improving the ejection stability from an inkjet head, and is preferably 1.5% by mass or less, and more preferably 1.0% by mass or less, from the viewpoint of suppressing bubbles that are generated in the ink composition during blending and improving the ejection stability.

[0043] (solvent) The actinic radiation-curable inkjet ink composition of the present invention may be solvent-free, but a solvent can be blended as needed. Examples of the solvent include ester-based organic solvents, ether-based organic solvents, ether ester-based organic solvents, ketone-based organic solvents, aromatic hydrocarbon solvents, and nitrogen-containing organic solvents. Examples of the solvent include those having a boiling point of 150 to 220°C at 1 atmosphere. From the perspectives of curability of the ink composition and environmental concerns, it is preferable to avoid the use of such solvents as much as possible. The proportion of the solvent in the ink composition is preferably 5% by mass or less, and more preferably 2% by mass or less.

[0044] <Additives> Various additives can be added to the actinic ray-curable inkjet ink composition of the present invention to exhibit various functionalities as needed. Specific examples include light stabilizers, ultraviolet absorbers, surface treatment agents, storage stability improvers, antioxidants, antiaging agents, crosslinking accelerators, polymerization inhibitors, plasticizers, preservatives, pH adjusters, antifoaming agents, and humectants. A resin that functions as a vehicle but is not curable may or may not be blended. A solvent may or may not be included. A wax may or may not be added.

[0045] (Storage improver) As the storage stability improver, hindered amines such as N-CH3 type, NH type, and N-OR type can be used.

[0046] (ultraviolet absorber) Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, hydroxyphenyltriazine-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and nickel complex salt-based ultraviolet absorbers.

[0047] (antioxidant) The antioxidant may be a phenol-based antioxidant, an amine-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, or the like.

[0048] (Antifoaming agent) The antifoaming agent may be a silicone-based antifoaming agent, a Pluronic (registered trademark)-based antifoaming agent, or the like.

[0049] <First actinic energy ray-curable inkjet ink composition>

[0043] The first actinic energy ray-curable inkjet ink composition of the present invention is required to be able to exhibit sufficient curability upon irradiation with actinic energy rays, and also to have sufficient adhesiveness to a substrate on which a digital embossing is to be formed, and to have sufficient adhesiveness to the second actinic energy ray-curable inkjet ink composition that is a layer thereon. Furthermore, it is necessary to satisfy condition 1 that the viscosity of the first actinic energy ray-curable inkjet ink composition be 14.0 cps (25°C) or more. It is preferably 30.0 cps (25°C) or more. It is also preferably 80.0 cps (25°C) or less, more preferably 70.0 cps (25°C) or less, and even more preferably 60.0 cps (25°C) or less. Furthermore, it is preferable that the substrate satisfies condition 3, that is, (surface tension of the first actinic energy ray-curable inkjet ink composition before curing) - (surface tension of the substrate surface) is -15.0 mN / m or more. Furthermore, the second actinic energy ray-curable inkjet ink composition must satisfy condition 2, that is, (surface tension of the second actinic energy ray-curable inkjet ink composition before curing) - (surface tension of the first actinic energy ray-curable inkjet ink composition before curing) is 4.0 mN / m or more. The first actinic ray-curable inkjet ink composition contains a compound selected from the actinic ray-curable components described above so as to satisfy these conditions. Among these, it is preferable to contain a monofunctional photopolymerizable compound, a polyfunctional photopolymerizable compound, and a surfactant. Furthermore, the surface tension of the first actinic energy ray-curable inkjet ink composition before curing is preferably 22.0 mN / m or more, more preferably 23.0 mN / m or more, and even more preferably 24.0 mN / m or more, and is preferably 29.0 mN / m or less, and more preferably 27.0 mN / m or less. Furthermore, after the first actinic energy ray-curable inkjet ink composition has landed, it is preferable that the time from irradiating the coating with actinic energy rays to pinning curing be within 0.5 seconds.

[0050] <Second actinic ray-curable inkjet ink composition>

[0047] The second actinic energy ray-curable inkjet ink composition of the present invention is required to exhibit sufficient curability upon irradiation with actinic energy rays, and also to have sufficient adhesiveness to the layer composed of the first actinic energy ray-curable inkjet ink composition. The layer made of the second actinic energy ray-curable inkjet ink composition may be a single layer, or multiple layers may be formed. In this case, it is also necessary that the laminated layers made of the second actinic energy ray-curable inkjet ink composition have sufficient adhesion to each other. Furthermore, when the layer made of the second actinic energy ray-curable inkjet ink composition is formed from multiple layers, the compositions making up these multiple layers may differ in composition or physical properties as long as the requirements of the present invention are met. Furthermore, at least a portion of the compositions making up the multiple layers may have the same composition or physical properties. In any case, it is necessary to satisfy condition 1, that is, the viscosity of the second actinic radiation-curable inkjet ink composition be 14.0 cps (25°C) or more. It is preferably 30.0 cps (25°C) or more. It is also preferably 80.0 cps (25°C) or less, more preferably 70.0 cps (25°C) or less, and even more preferably 60.0 cps (25°C) or less. Furthermore, for the first actinic energy ray-curable inkjet ink composition, it is necessary to satisfy condition 2, that is, (surface tension of the second actinic energy ray-curable inkjet ink composition before curing) - (surface tension of the first actinic energy ray-curable inkjet ink composition before curing) is 4.0 mN / m or more, preferably 6.0 mN / m or more, more preferably 8.0 mN / m or more, and even more preferably 10.0 mN / m or more. When 4.0 mN / m or more is satisfied, in combination with satisfying conditions 1 and 2, it is possible to obtain high dots having a height of 80 μm or more from the substrate surface by inkjet printing the first and second actinic energy ray-curable inkjet ink compositions once each. The second actinic ray-curable inkjet ink composition contains a compound selected from the actinic ray-curable components described above so as to satisfy these conditions. Among these, it is preferable to contain a monofunctional photopolymerizable compound, a polyfunctional photopolymerizable compound, and a surfactant. Furthermore, the surface tension of the second actinic energy ray-curable inkjet ink composition before curing is preferably 26.0 mN / m or more, more preferably 27.0 mN / m or more, and even more preferably 28.0 mN / m or more, and is preferably 34.0 mN / m or less, more preferably 33.0 mN / m or less, and even more preferably 32.0 mN / m or less. Furthermore, after the second actinic ray-curable inkjet ink composition has landed, it is preferable that the time from irradiating the coating with actinic ray to pinning curing be within 0.5 seconds.

[0051] <Method for preparing active energy ray-curable inkjet ink composition> Next, a method for producing the actinic ray-curable ink jet ink composition of the present invention using these materials will be described. The actinic energy ray-curable inkjet ink composition of the present invention can be obtained by dispersing and mixing the components using a dispersing machine such as a wet circulation mill, bead mill, ball mill, sand mill, attritor, roll mill, DCP mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, high-pressure homogenizer (Microfluidizer, Nanomizer, Ultimizer, Genus PY, DeBEE2000, etc.), or pearl mill, and adjusting the viscosity of the actinic energy ray-curable inkjet ink composition as necessary. The actinic energy ray-curable inkjet ink composition may also be prepared by first preparing a base ink composition by mixing a dye or pigment with the pigment dispersant and the photopolymerizable monomer, and then adding the remaining components to obtain the desired composition. Alternatively, a clear composition may be prepared. Alternatively, the above components may be mixed and milled in a bead mill, a three-roll mill, or the like to disperse the pigments (i.e., the coloring components and the extender pigments), and then additives (polymerization initiators, polymerization inhibitors, waxes, and other additives, etc.) may be added as needed, and the viscosity may be adjusted by further adding other components.

[0052] <Surface of base material> The substrate on which the digital embossing is performed according to the present invention may be made of one or more materials such as plastic, metal, paper, or inorganic materials other than metal, as long as it can be coated (printed) with an active energy ray-curable inkjet ink composition. The substrate may have a printed layer, a coating layer, a primer or other underlayer formed thereon by known means, or may have undergone pretreatment such as corona discharge treatment or plasma discharge treatment, or a chemical conversion treatment or other underlayer treatment. A combination of these underlayer formations and underlayer treatments may also be used. In this specification, the substrate surface refers to a layer on which a layer made of the first active energy ray-curable inkjet ink composition is directly formed, and refers to the surface of the substrate after the above-mentioned printed layer or underlayer or underlayer has been formed or underlayer treatment has been performed. In particular, when a substrate is used that has a pattern formed in advance using a printing layer or the like, the creation of the digital embossing of the present invention can improve the aesthetics, for example, by synchronizing the pattern with the digital embossing. Such a printed layer can be formed by any printing method depending on the properties and material of the substrate.

[0053] The surface of the substrate surface that comes into direct contact with the layer comprising the first actinic-energy-ray-curable inkjet ink composition may have any surface tension. Preferably, the relationship between the surface tension of the layer comprising the first actinic-energy-ray-curable inkjet ink composition before curing satisfies condition 3 ((surface tension of the first actinic-energy-ray-curable inkjet ink composition before curing) - (surface tension of the substrate surface) is -15.0 mN / m or greater). By satisfying condition 3, the layer comprising the first actinic-energy-ray-curable inkjet ink composition will be able to sufficiently conform to the substrate surface and, at the same time, will be more likely to adhere with sufficient adhesive strength. The surface tension of the substrate surface is preferably 22.0 to 40.0 mN / m. In this case, the layer made of the first actinic energy ray-curable inkjet ink composition, i.e., the layer ejected from an inkjet coating device, adhered to the substrate surface, and cured, can be formed with a sufficient height.

[0054] Examples of plastics used in the substrate include polyester polymers (e.g., polyethylene terephthalate (PET), polyethylene naphthalate, etc.), cellulose polymers (e.g., diacetyl cellulose, triacetyl cellulose (TAC), etc.), polycarbonate polymers, polyacrylic polymers (e.g., polymethyl methacrylate, etc.), vinyl chloride polymers, polyolefin polymers (e.g., polyethylene, polypropylene, polyolefin polymers having a cyclic or norbornene structure, ethylene-propylene copolymer polymers, etc.), polyamide polymers (e.g., nylon, aromatic polyamide polymers, etc.), polystyrene polymers (e.g., polystyrene, acrylonitrile-styrene copolymer polymers, etc.), polyimide polymers, polysulfone polymers, polyethersulfone polymers, polyetherketone polymers, polyphenylsulfide polymers, polyvinyl alcohol polymers, polyvinylidene chloride polymers, polyvinyl butyral polymers, polyarylate polymers, polyoxymethylene polymers, and polyepoxy polymers, as well as blends of these polymers. As the metal used in the substrate, for example, metals known as printing targets, such as aluminum, iron, zinc, nickel, copper, tin, and titanium, and alloys thereof can be used. As the paper used in the above substrates, for example, uncoated paper, coated paper, cardboard paper, and other papers known to be used as printing substrates can be used. Among the above substrates, inorganic substrates other than metals that can be used include known ceramics, earthenware, gypsum, etc. that can be used as printing substrates.

[0055] <Digital embossing method> In the method of forming a digital embossment in the present invention, a first actinic energy ray-curable inkjet ink composition is printed onto the surface of a substrate using an inkjet coating device (hereinafter also referred to as an "inkjet printing device"), and then the printed layer is irradiated with energy rays to cure. However, it is also possible to enlarge each droplet in the method of the present invention so that an office or ordinary printing device is not used. Subsequently, a second actinic energy ray-curable inkjet ink composition is printed on the surface of the printed layer of the cured first actinic energy ray-curable inkjet ink composition using an apparatus capable of inkjet printing, and then this printed layer is irradiated with energy rays to be cured. In this way, the digital embossment of the present invention may be created by printing the second actinic ray-curable inkjet ink composition only once using an inkjet printing device. However, to obtain a three-dimensional pattern with higher protrusions, the second actinic ray-curable inkjet ink composition is again printed on the surface of the printed layer of the cured second actinic ray-curable inkjet ink composition using an inkjet printing device, and then this printed layer is irradiated with energy rays to be cured. This operation can then be repeated 1 to 10 times, or if necessary, the second actinic ray-curable inkjet ink composition can be printed up to 15 times in total to overlap the cured layer formed by the second actinic ray-curable inkjet ink composition, thereby creating a digital embossment with even higher protrusions. The size of a single droplet when printing the first actinic energy ray-curable inkjet ink composition is 10.0 pL or more, and the size of a single droplet when printing the second actinic energy ray-curable inkjet ink composition to be laminated one or more times on the printed layer formed by the first actinic energy ray-curable inkjet ink composition is 10.0 pL or more. Furthermore, with regard to the first actinic energy ray-curable inkjet ink composition and the second actinic energy ray-curable inkjet ink composition, the size of a single droplet during inkjet printing is preferably 15.0 pL or more, more preferably 20.0 pL or more, even more preferably 25.0 pL or more, and most preferably 30.0 pL or more, and is preferably 120.0 pL or less.

[0056] By forming a digital embossment in this manner, the total thickness of one cured layer of the first active energy ray-curable inkjet ink composition and one cured layer of the second-layer active energy ray-curable inkjet ink composition can be made 10.0 μm or more. The shape of the embossed convex portions can be formed as desired by controlling the inkjet printing. However, in the present invention, it is preferable that the embossing be formed under specific conditions, so that the smallest convex portion has a planar size of 120 μm or less. Furthermore, the height of the digital embossment formed by inkjet printing using the first actinic energy ray-curable inkjet ink composition and the second actinic energy ray-curable inkjet ink composition can be set to an extremely high value in the range of 80 to 110%, where the numerical value of the dot height (μm) of the digital embossment formed is the total volume (pl (picoliters)) of each droplet ejected at each point on the substrate by each inkjet printing.

[0057] <Digital embossing applications> The digital embossing obtained by the present invention can be used for interior materials such as flooring and wall materials, furniture, automobile interiors, storage containers, and other articles that require anti-slip properties and aesthetic appeal. [Example]

[0058] The present invention will be described in more detail below with reference to examples. The present invention is not limited to these examples. Unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass" (the numerical values ​​shown in the tables are parts by mass). The raw materials used and their preparation methods are shown below.

[0059] <Creation of digital embossing in Examples 1 to 7 and Comparative Examples 1 to 4> A first actinic ray-curable inkjet ink composition was obtained based on the formulation shown in Table 1. Furthermore, a second actinic ray-curable inkjet ink composition was obtained based on the formulation shown in Table 2. A first layer was inkjet printed onto the surface of a polyethylene terephthalate film (surface tension: 36 mN / m) using the first actinic ray-curable inkjet ink composition of Example 1 in Table 1, and pinning was performed by irradiating this layer with ultraviolet light. The ink droplets used to form the first layer each had a volume of 35 pl. Next, a second layer was inkjet printed on the substrate using the second actinic ray-curable inkjet ink composition of Example 1 in Table 2, and this layer was cured by irradiating with ultraviolet light. This second actinic ray-curable inkjet ink composition was laminated twice. The ink droplets used to form the second layer had an average volume of 35 pL per droplet. Since the second layer was laminated by two inkjet printings, each printed area of ​​the second layer was laminated by a total of two overlapping printings, and was formed using 35 pL x 2 = 70 pL of ink composition. As a result, a total of three layers were laminated using the first actinic ray-curable inkjet ink composition and the second actinic ray-curable inkjet ink composition. In the same manner, Example 2 and subsequent Examples and Comparative Examples were carried out. In Example 8, the ink compositions used for the first and second layers were the same as those used in Example 1, but the number of overprints to form the second layer was increased from two to seven, and the droplet volume in each of the seven inkjet printings was set to 10 pL. In each of the examples and comparative examples, printing was performed in the form of dots.

[0060] IBXA: Isobornyl acrylate ACMO: acryloylmorpholine CN371: Amine-modified acrylate monomer (Sartomer) SR217: 4-t-butylcyclohexyl acrylate (Sartomer) HDDA: 1,6-hexanediol diacrylate CN991: Polyester urethane diacrylate oligomer (Sartomer) CN2271: Polyester acrylate oligomer (Sartomer) TPO: Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (Omnirad-TPO (IGM)) BYK-377: Hydroxyl-containing polyether-modified polydimethylsiloxane (BYK) BYK-331: Polyether-modified polydimethylsiloxane (BYK) BYK-315: Polyester-modified polymethylalkylsiloxane (25% solids) (BYK) BYK-381: Acrylic polymer (BYK)

[0061] <Dot height> The substrate after digital embossing was cut in a plane perpendicular to the substrate surface, and the cut surface was examined under a microscope to visually measure the height of each of 100 embosses, i.e., the height of the portion where the cured products of the first actinic energy ray-curable inkjet ink composition and the second actinic energy ray-curable inkjet ink composition were laminated, and the average value was calculated.

[0062] [Table 1]

[0063] [Table 2]

[0064] [Table 3]

[0065] In each example, sufficiently high cured dots were obtained. The same result was obtained when a larger amount of inkjet ink composition was layered to form a second layer, as in Example 8. In contrast, in Comparative Examples 1, 2, and 4, which did not satisfy Condition 2, and in Comparative Example 3, in which a first actinic energy ray-curable inkjet ink composition was deposited and then a second actinic energy ray-curable inkjet ink composition was deposited without pinning, dots of sufficient height were not obtained.

Claims

1. A method for creating a digital embossment using an actinic ray-curable inkjet ink composition, comprising: a first actinic energy ray-curable inkjet ink composition is deposited on a surface of a substrate in droplets with a volume of 10.0 pl or more per droplet, and then the ink composition is irradiated with actinic energy rays to perform pinning curing to form a first layer; Next, a second actinic energy ray-curable inkjet ink composition is deposited in droplets having a volume of 10.0 pl or more on the first layer, and then the ink is irradiated with actinic energy rays to perform pinning curing to form a second layer. A method for forming a digital embossment, Furthermore, the method for creating a digital embossment satisfies the following conditions 1 and 2. Condition 1: The viscosity of the first and second actinic ray-curable inkjet ink compositions is 14.0 cps (25° C.) or more. Condition 2: (surface tension of the second actinic energy ray-curable inkjet ink composition before curing) - (surface tension of the first actinic energy ray-curable inkjet ink composition before curing) is 4.0 mN / m or more

2. Condition 3: (surface tension of the first actinic energy ray-curable inkjet ink composition before curing) - (surface tension of the substrate surface) is -15.0 mN / m or more.

3. 3. The method for creating a digital embossment according to claim 1 or 2, wherein the surface tension of the substrate surface is 22.0 to 40.0 mN / m, the surface tension of the first actinic energy ray-curable inkjet ink composition before curing is 22.0 to 29.0 mN / m, and the surface tension of the second actinic energy ray-curable inkjet ink composition before curing is 26.0 to 34.0 mN / m.

4. The method for creating a digital embossment according to any one of claims 1 to 3, wherein, after the first actinic energy ray-curable inkjet ink composition and the second actinic energy ray-curable inkjet ink composition have been deposited, the time required for pinning curing by irradiating each coating film with actinic energy rays is 0.5 seconds or less.

5. The method for creating a digital embossment according to any one of claims 1 to 4, wherein the first actinic energy ray-curable inkjet ink composition and the second actinic energy ray-curable inkjet ink composition each independently contain a monofunctional photopolymerizable compound, a polyfunctional photopolymerizable compound, and a surfactant.

6. The method for creating a digital embossment according to any one of claims 1 to 5, wherein the sum of the film thickness of the cured layer of the first active energy ray-curable inkjet ink composition and the film thickness of the cured layer of the second active energy ray-curable inkjet ink composition is 80.0 µm or more.

7. 7. The method for creating a digital embossment according to claim 1, wherein the first and second actinic ray-curable inkjet ink compositions contain at least one monomer selected from the group consisting of an alicyclic alkyl group-containing (meth)acrylate, acryloylmorpholine, and an amine-modified acrylate monomer.

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