Active energy ray-curable inkjet ink, image recording method, and method for producing molded article

Abstract

Provided is an active energy ray-curable inkjet ink or the like with which it is possible to obtain an image recording material having excellent impact resistance and blocking resistance. An active energy ray-curable inkjet ink containing a bifunctional (meth) acrylate having a C5-9 linear or branched alkylene group, a benzyl (meth) acrylate, and a colorant, the amount of the bifunctional (meth) acrylate being less than the total amount of the active energy ray-curable inkjet ink, and the amount of the benzyl (meth) acrylate being less than the total amount of the active energy ray-curable inkjet ink. The total content of the bifunctional (meth) acrylate and the benzyl (meth) acrylate is 60 mass% or more. And applications thereof.

Description

Technical Field

[0001] The present invention relates to an active energy ray-curable inkjet ink, an image recording method, and a method for producing a molded body. Background Art

[0002] Conventionally, there is known a method of using active energy rays to cure an image recorded on a substrate using ink.

[0003] For example, Patent Document 1 describes an image forming ink containing a photopolymerizable monomer and a photopolymerization initiator. Patent Document 2 describes an active energy ray-curable inkjet ink containing a polymerizable compound.

[0004] Patent Document 1: Japanese Patent Application Publication No. 2018-1676

[0005] Patent Document 2: Japanese Patent Application Publication No. 2017-25124

[0006] An image recorded material obtained by applying ink to a substrate may be required to have excellent impact resistance and blocking resistance. Summary of the invention

[0007] The present invention has been made in view of such circumstances, and an object of one embodiment of the present invention is to provide an active energy ray-curable inkjet ink capable of obtaining an image recorded material having excellent impact resistance and blocking resistance.

[0008] Furthermore, another embodiment of the present invention is to provide an image recording method and a method for producing a molded body using the active energy ray-curable inkjet ink.

[0009] The present invention includes the following aspects.

[0010] <1>

[0011] An active energy ray-curable inkjet ink comprising a bifunctional (meth)acrylate having a linear or branched alkylene group having 5 to 9 carbon atoms, benzyl (meth)acrylate, and a colorant.

[0012] The total content of the bifunctional (meth)acrylate and benzyl (meth)acrylate is 60% by mass or more based on the total amount of the active energy ray-curable inkjet ink.

[0013] <2>

[0014] The active energy ray-curable inkjet ink according to <1>, wherein

[0015] The total content of the bifunctional (meth)acrylate and benzyl (meth)acrylate is 95% by mass or more based on the total amount of the polymerizable compound.

[0016] <3>

[0017] The active energy ray-curable inkjet ink according to <1> or <2>, wherein

[0018] The mass ratio of the content of benzyl (meth)acrylate to the content of the bifunctional (meth)acrylate is 2.0 to 5.0.

[0019] <4>

[0020] The active energy ray-curable inkjet ink according to any one of <1> to <3>, wherein a content of benzyl (meth)acrylate is 50% by mass or more based on a total amount of the active energy ray-curable inkjet ink.

[0021] <5>

[0022] The active energy ray-curable inkjet ink according to any one of <1> to <4>, wherein

[0023] The surface tension is 23mN / m~26mN / m.

[0024] <6>

[0025] The active energy ray-curable inkjet ink according to any one of <1> to <5>, further comprising a silicone-based surfactant.

[0026] <7>

[0027] The active energy ray-curable inkjet ink according to <6>, wherein

[0028] Silicone surfactants contain polyether structures and polysiloxane structures.

[0029] The mass ratio of the content of the polysiloxane structure to the content of the polyether structure is 0.6 or less.

[0030] <8>

[0031] An image recording method comprises the following steps:

[0032] applying the active energy ray-curable inkjet ink described in any one of <1> to <7> to a substrate by an inkjet recording method; and

[0033] The applied active energy ray-curable inkjet ink is irradiated with active energy rays to record an image.

[0034] <9>

[0035] A method for manufacturing a molded body, comprising the following steps:

[0036] applying the active energy ray-curable inkjet ink described in any one of <1> to <7> to a substrate by an inkjet recording method;

[0037] irradiating the applied active energy ray-curable inkjet ink with active energy rays to record an image; and

[0038] The substrate on which the image is recorded is molded to produce a molded body.

[0039] Effects of the Invention

[0040] According to one embodiment of the present invention, there is provided an active energy ray-curable inkjet ink capable of obtaining an image recorded material having excellent impact resistance and blocking resistance.

[0041] According to another embodiment of the present invention, there are provided an image recording method and a method for producing a molded body using the above-mentioned active energy ray-curable inkjet ink. DETAILED DESCRIPTION

[0042] Hereinafter, the active energy ray-curable inkjet ink and the method for producing a molded body of the present invention will be described in detail.

[0043] In the present specification, a numerical range expressed using "to" indicates a range including the numerical values ​​described before and after "to" as the minimum value and the maximum value, respectively.

[0044] In the numerical ranges recorded in stages in this specification, the upper limit or lower limit recorded in a certain numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical ranges recorded in this specification, the upper limit or lower limit recorded in a certain numerical range can also be replaced by the value shown in the embodiment.

[0045] In the present specification, when a plurality of substances corresponding to each component are present in a composition, unless otherwise specified, the amount of each component in the composition means the total amount of the plurality of substances present in the composition.

[0046] In the present specification, a combination of two or more preferred aspects is a more preferred aspect.

[0047] In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process can be achieved.

[0048] In this specification, "image" means the entire film formed by applying ink, and "image recording" means the formation of an image (ie, film).

[0049] Furthermore, the concept of "image" in this specification also includes a solid image.

[0050] In this specification, "(meth)acrylate" is a concept including both acrylate and methacrylate. Also, "(meth)acrylic acid" is a concept including both acrylic acid and methacrylic acid.

[0051] An active energy ray-curable inkjet ink (hereinafter also referred to simply as "ink") as one embodiment of the present invention contains a bifunctional (meth)acrylate having a linear or branched alkylene group having 5 to 9 carbon atoms, benzyl (meth)acrylate, and a colorant, wherein the total content of the bifunctional (meth)acrylate and benzyl (meth)acrylate is 60% by mass or more relative to the total amount of the ink.

[0052] For example, an image recorded as an image in which an ink film is formed on a substrate can be obtained by applying the ink as one embodiment of the present invention to a substrate and then irradiating the substrate with active energy rays. Since the ink as one embodiment of the present invention contains a bifunctional (meth)acrylate and benzyl (meth)acrylate having a linear or branched alkylene group with 5 to 9 carbon atoms, a polymerization reaction is carried out by irradiating the substrate with active energy rays. It is believed that benzyl (meth)acrylate and the above-mentioned bifunctional (meth)acrylate contribute to achieving both impact resistance and blocking resistance. In particular, the total content of the above-mentioned bifunctional (meth)acrylate and benzyl (meth)acrylate is 60% by mass or more relative to the total amount of the ink, so the impact resistance and blocking resistance are excellent.

[0053] On the other hand, Patent Documents 1 and 2 do not assume that the bifunctional (meth)acrylate and benzyl (meth)acrylate described above are contained and the total content thereof is 60% by mass or more relative to the total amount of the ink.

[0054] Hereinafter, each component contained in the ink which is one embodiment of the present invention will be described.

[0055] [Active energy ray curable inkjet ink]

[0056] The ink as one embodiment of the present invention is an active energy ray curable ink. That is, the ink as one embodiment of the present invention is cured by irradiating active energy rays. As active energy rays, for example, gamma rays, beta rays, electron beams, ultraviolet rays and visible rays can be cited. Among them, the active energy rays are preferably ultraviolet rays. The ink as one embodiment of the present invention is preferably an ultraviolet curable ink.

[0057] <Bifunctional (meth)acrylate having a linear or branched alkylene group having 5 to 9 carbon atoms>

[0058] The ink according to one embodiment of the present invention contains a bifunctional (meth)acrylate having a linear or branched alkylene group having 5 to 9 carbon atoms (hereinafter also referred to as a “specific bifunctional (meth)acrylate”).

[0059] The bifunctional (meth)acrylate is a compound having two (meth)acryloyloxy groups.

[0060] The specific bifunctional (meth)acrylate has a linear or branched alkylene group and has 5 to 9 carbon atoms, and the image obtained thereby has excellent blocking resistance.

[0061] From the same viewpoint, the linear or branched alkylene group preferably has 6 to 8 carbon atoms, more preferably 6 carbon atoms.

[0062] The specific bifunctional (meth)acrylate contained in the ink may be only one kind or two or more kinds.

[0063] Examples of the specific bifunctional (meth)acrylate include 3-methyl-1,5-pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol diacrylate, 1,7-heptanediol diacrylate, 1,8-octanediol diacrylate, and 1,9-nonanediol di(meth)acrylate.

[0064] Among them, from the viewpoint of ejectability, the specific bifunctional (meth)acrylate is preferably at least one selected from the group consisting of 3-methyl-1,5-pentanediol di(meth)acrylate and 1,6-hexanediol diacrylate, and more preferably 3-methyl-1,5-pentanediol di(meth)acrylate.

[0065] From the viewpoint of blocking resistance, the content of the specific bifunctional (meth)acrylate is preferably 15% by mass to 40% by mass, and more preferably 17% by mass to 25% by mass, based on the total amount of the ink.

[0066] <Benzyl (meth)acrylate>

[0067] The ink which is one embodiment of the present invention contains benzyl (meth)acrylate.

[0068] From the viewpoint of impact resistance, the content of benzyl (meth)acrylate is preferably 50% by mass or more, more preferably 50% by mass to 70% by mass, and even more preferably 55% by mass to 65% by mass, based on the total amount of the ink.

[0069] From the viewpoint of further improving impact resistance and blocking resistance, the mass ratio of the content of benzyl (meth)acrylate to the content of the specific bifunctional (meth)acrylate is preferably 2.0 to 5.0, more preferably 2.0 to 4.0.

[0070] <Other polymerizable compounds>

[0071] The ink as one embodiment of the present invention may contain other polymerizable compounds in addition to the specific bifunctional (meth)acrylate and benzyl (meth)acrylate within a range that does not significantly impair the effects of the present invention.

[0072] However, from the viewpoint of impact resistance and blocking resistance, the content of other polymerizable compounds is preferably small.

[0073] Specifically, the total content of the specific bifunctional (meth)acrylate and benzyl (meth)acrylate is preferably 95% by mass or more, more preferably 98% by mass or more, relative to the total amount of the polymerizable compound. The polymerizable compound referred to herein refers to all polymerizable compounds contained in the ink. From the above viewpoint, the total content of the specific bifunctional (meth)acrylate and benzyl (meth)acrylate can be 100% by mass relative to the total amount of the polymerizable compound.

[0074] When the ink contains other polymerizable compounds, the other polymerizable compounds are not particularly limited as long as they are compounds having a polymerizable group other than the specific bifunctional (meth)acrylate and benzyl (meth)acrylate.

[0075] From the viewpoint of reactivity with specific bifunctional (meth)acrylate and benzyl (meth)acrylate, the polymerizable group in the other polymerizable compound is preferably a radical polymerizable group, more preferably an ethylenically unsaturated group, and further preferably a (meth)acryloyloxy group. That is, the other polymerizable compound is preferably a radical polymerizable compound, more preferably an ethylenically unsaturated compound, and further preferably a (meth)acrylate compound.

[0076] The other polymerizable compound may be a monofunctional polymerizable compound having one polymerizable group, or may be a polyfunctional polymerizable compound having two or more polymerizable groups.

[0077] (Monofunctional polymerizable compound)

[0078] Examples of the monofunctional polymerizable compound include monofunctional (meth)acrylates, monofunctional (meth)acrylamides, monofunctional aromatic vinyl compounds, monofunctional vinyl ethers, and monofunctional N-vinyl compounds.

[0079] Examples of the monofunctional (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, tert-octyl (meth)acrylate, isoamyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-n-butylcyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, bornyl (meth)acrylate, and butyl (meth)acrylate. Isobornyl (meth)acrylate, 2-ethylhexyl diglycol (meth)acrylate, butoxyethyl (meth)acrylate, 2-chloroethyl (meth)acrylate, 4-bromobutyl (meth)acrylate, cyanoethyl (meth)acrylate, butoxymethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 2-(2-butoxyethoxy)ethyl (meth)acrylate, 2,2,2-tetrafluoroethyl (meth)acrylate, 1H,1H,2H,2H-perfluorodecyl (meth)acrylate, 4-butylphenyl (meth)acrylate, phenyl (meth)acrylate, 2,4,5-tetramethylphenyl ester, 4-chlorophenyl (meth)acrylate, 2-phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, glycidyloxybutyl (meth)acrylate, glycidyloxyethyl (meth)acrylate, glycidyloxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, phenyl glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminopropyl (meth)acrylate, trimethoxysilylpropyl (meth)acrylate, trimethylsilylpropyl (meth)acrylate, polyethylene oxide monomethyl ether (meth)acrylate, polyethylene oxide monoalkyl (meth)acrylate Ether esters, dipropylene glycol (meth)acrylate, polypropylene oxide monoalkyl ether (meth)acrylate, 2-methacryloyloxyethyl succinate, 2-methacryloyloxyhexahydrophthalate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, ethoxydiethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, trifluoroethyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, ethylene oxide (EO) modified phenol (meth)acrylate , EO modified cresol (meth) acrylate, EO modified nonylphenol (meth) acrylate, propylene oxide (PO) modified nonylphenol (meth) acrylate, EO modified 2-ethylhexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (3-ethyl-3-oxetanylmethyl) (meth) acrylate, phenoxyethylene glycol (meth) acrylate, 2-carboxyethyl (meth) acrylate and 2-(meth) acryloyloxyethyl succinate. ,

[0080] Examples of the monofunctional (meth)acrylamide include (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-n-butyl (meth)acrylamide, N-tert-butyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-methylol (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide and (meth)acryloyl morpholine.

[0081] Examples of the monofunctional aromatic vinyl compound include styrene, dimethylstyrene, trimethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinyl benzoate, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3-(2-ethylhexyl)styrene, 4-(2-ethylhexyl)styrene, allylstyrene, isopropenylstyrene, butenylstyrene, octenylstyrene, 4-tert-butoxycarbonylstyrene and 4-tert-butoxystyrene.

[0082] Examples of the monofunctional vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenyloxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxyethyl vinyl ether, phenethyl vinyl ether, and phenoxypolyethylene glycol vinyl ether.

[0083] Examples of the monofunctional N-vinyl compound include N-vinyl-ε-caprolactam and N-vinyl pyrrolidone.

[0084] -Multifunctional polymerizable compound-

[0085] Examples of the polyfunctional polymerizable compound include polyfunctional (meth)acrylate compounds and polyfunctional vinyl ethers.

[0086] Examples of the polyfunctional (meth)acrylate include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, EO-modified neopentyl glycol di(meth)acrylate, PO-modified neopentyl glycol di(meth)acrylate, EO-modified hexanediol di(meth)acrylate, PO-modified hexanediol di(meth)acrylate, decanediol di(meth)acrylate, dodecanediol di(meth)acrylate, glycerol di(meth)acrylate, and polyfunctional (meth)acrylates. meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane EO addition tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxy trimethylolpropane, glycerol polyglycidyl ether poly(meth)acrylate, and tris(2-acryloyloxyethyl)isocyanurate.

[0087] Examples of the polyfunctional vinyl ethers include 1,4-butanediol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, bisphenol A epoxy alkyl divinyl ether, bisphenol F epoxy alkyl divinyl ether, trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane trivinyl ether, and the like. tetravinyl ether, glycerol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, EO addition trimethylolpropane trivinyl ether, PO addition trimethylolpropane trivinyl ether, EO addition ditrimethylolpropane tetravinyl ether, PO addition ditrimethylolpropane tetravinyl ether, EO addition pentaerythritol tetravinyl ether, PO addition pentaerythritol tetravinyl ether, EO addition dipentaerythritol hexavinyl ether and PO addition dipentaerythritol hexavinyl ether.

[0088] <Coloring agent>

[0089] The ink which is one embodiment of the present invention contains at least one colorant.

[0090] In the present invention, the colorant refers to a substance that, when contained in ink, can make the ink a color ink or a non-color ink.

[0091] The colorant may be a colorant (eg, cyan, magenta, yellow, etc.) or a non-colorant (eg, white and black).

[0092] Examples of the colorant include dyes and pigments. From the viewpoint of durability such as heat resistance, light resistance, and water resistance, the colorant is preferably a pigment.

[0093] When a pigment is used as a colorant, the ink can contain the pigment as a pigment dispersion. The pigment dispersion is a liquid obtained by dispersing the pigment in a liquid medium using a dispersant, and contains at least a pigment, a dispersant, and a liquid medium. The details of the dispersant will be described later. In addition, the liquid medium can be an organic solvent or a polymerizable compound.

[0094] As pigment, any of commercially available organic pigments and inorganic pigments can be used. As pigment, for example, the pigments described in "Dictionary of Pigments" (2000 edition) edited by Seijiro Ito, W.Herbst, K.Hunger "Industrial Organic Pigments", Japanese Patent Publication No. 2002-12607, Japanese Patent Publication No. 2002-188025, Japanese Patent Publication No. 2003-26978 and Japanese Patent Publication No. 2003-342503 can be cited.

[0095] The content of the colorant is preferably 0.5% by mass to 15% by mass, more preferably 1% by mass to 10% by mass, and even more preferably 2% by mass to 5% by mass, relative to the total amount of the ink.

[0096] <Dispersant>

[0097] When a pigment is used as a colorant, the ink can contain the pigment as a pigment dispersion. The pigment can be dispersed in a liquid medium using a dispersant. As the dispersant, a generally known dispersant can be used. From the viewpoint of dispersion stability, the dispersant is preferably a compound having both a hydrophilic structure and a hydrophobic structure.

[0098] As the dispersant, for example, there can be mentioned low molecular weight dispersants having a molecular weight of less than 1000, such as higher fatty acid salts, alkyl sulfates, alkyl ester sulfates, alkyl sulfonates, sulfosuccinates, alkyl naphthalene sulfonates, alkyl phosphates, polyoxyalkylene alkyl ether phosphates, polyoxyalkylene alkylphenyl ethers, polyoxyethylene polyoxypropylene glycols, glycerol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene fatty acid amides and amine oxides.

[0099] In addition, as a dispersant, a high molecular weight dispersant having a molecular weight of 1000 or more obtained by copolymerizing a hydrophilic monomer with a hydrophobic monomer can be exemplified. From the viewpoint of dispersion stability, the hydrophilic monomer is preferably a monomer containing a dissociative group, and more preferably a monomer containing a dissociative group having a dissociative group and an ethylenically unsaturated bond. As a monomer containing a dissociative group, for example, a carboxyl-containing monomer, a sulfonic acid-containing monomer, and a phosphoric acid-containing monomer can be exemplified. From the viewpoint of dispersion stability, the hydrophobic monomer is preferably a monomer containing an aromatic group having an aromatic group and an ethylenically unsaturated bond, or a monomer containing an aliphatic hydrocarbon group having an aliphatic hydrocarbon group and an ethylenically unsaturated bond. The polymer can be any of a random copolymer and a block copolymer.

[0100] The dispersant may be a commercially available product. Examples of commercially available products include DISPERBYK-101, DISPE RBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-110, DISPERBYK-111, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPE RBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, and DISPERBYK-182 (all manufactured by BYK-Chemie); and SOLSPERS E3000, SOLSPERSE5000, SOLSPERSE9000, SOLSPERSE12000, SOLSPERSE13240, SOLSPERSE13940, SOLSPERSE17000, SOLSPERSE22000, SOLSPERSE24000, SOLSPERSE26000, SOLSPERSE28000, SOLSPERSE32000, SOLSPERSE36000, SOLSP ERSE39000, SOLSPERSE41000, SOLSPERSE71000 (above, manufactured by Lubrizol Corporation).

[0101] As a dispersing device for dispersing the pigment, a known dispersing device can be used, for example, a ball mill, a sand mill, a bead mill, a roll mill, a jet mill, a paint shaker, an attritor, an ultrasonic disperser and a disperser can be mentioned.

[0102] From the viewpoint of dispersion stability, the content of the dispersant in the ink is preferably 0.05 to 1.0, more preferably 0.1 to 0.5, based on mass, relative to the content of the pigment.

[0103] <Surfactant>

[0104] The inks of the present invention preferably contain at least one surfactant.

[0105] Examples of the surfactant include silicone-based surfactants, acetylene glycol-based surfactants and polyoxyethylene alkyl ether-based surfactants.

[0106] The ink of the present invention preferably contains at least one silicone surfactant.

[0107] When a silicone-based surfactant is included, the surface tension of the ink is reduced, and the wettability with respect to the substrate or the base layer formed on the substrate is improved. As a result, the quality of the obtained image is improved.

[0108] Among them, the silicone-based surfactant is preferably a silicone-based surfactant having a (meth)acryloyl group.

[0109] When the ink contains a silicone surfactant having a (meth)acryloyl group, a polymerization reaction with the specific bifunctional (meth)acrylate and benzyl (meth)acrylate proceeds, and impact resistance and blocking resistance are improved.

[0110] The number of the (meth)acryloyl group contained in the silicone surfactant having a (meth)acryloyl group may be only one, or may be two or more.

[0111] From the viewpoint of separability, the number of (meth)acryloyl groups is preferably 2 or more, and more preferably 3 or more. The upper limit of the number of (meth)acryloyl groups is not particularly limited, but is, for example, 5 from the viewpoint of ejectability.

[0112] The silicone surfactant having a (meth)acryloyl group is preferably a polyether-modified polydimethylsiloxane having a (meth)acryloyl group. In the polyether-modified polydimethylsiloxane having a (meth)acryloyl group, the position of the polyether chain is not particularly limited, and may be one end of the main chain, both ends of the main chain, or a side chain. The polyether chain is preferably a polyoxyalkylene chain.

[0113] As commercially available products of the silicone surfactant having a (meth)acryloyl group, for example, BYK-UV3500, 3505, 3530, 3570, 3575, 3576 (manufactured by BYK), Tegorad 2100, 2200, 2250, 2300, 2500, 2600, 2700, 2800, 2010, 2011 (manufactured by Evonik Industries AG), EBECRYL 350, 1360 (manufactured by DAICEL-ALLNEX LTD.), and KP-410, 411, 412, 413, 414, 415, 416, 418, 420, 422, 423 (manufactured by Shin-Etsu Silicone Co., Ltd.) can be mentioned.

[0114] The silicone surfactant contains a polyether structure and a polysiloxane structure, and the mass ratio of the content of the polysiloxane structure to the content of the polyether structure is preferably 0.6 or less, and more preferably 0.4 or less. The lower limit of the mass ratio is, for example, 0.2.

[0115] When the mass ratio is 0.6 or less, when an overcoat layer is provided on an image, uneven application of an overcoat liquid used for forming the overcoat layer to the image surface can be suppressed.

[0116] The mass ratio of the content of the polysiloxane structure to the content of the polyether structure was determined by nuclear magnetic resonance spectroscopy. 1 H-NMR) to calculate.

[0117] The content of the surfactant is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 2% by mass, relative to the total amount of the ink.

[0118] <Polymerization initiator>

[0119] The ink according to one embodiment of the present invention may contain at least one polymerization initiator. The polymerization initiator is preferably a radical polymerization initiator that generates free radicals.

[0120] Examples of the radical polymerization initiator include alkylphenone compounds, acylphosphine compounds, aromatic onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds.

[0121] Among them, the polymerization initiator is preferably at least one selected from the group consisting of acylphosphine compounds and thio compounds, more preferably at least one selected from the group consisting of acylphosphine oxide compounds and thioxanthone compounds, and further preferably, using both acylphosphine oxide compounds and thioxanthone compounds.

[0122] Examples of the acylphosphine oxide compound include monoacylphosphine oxide compounds and bisacylphosphine oxide compounds.

[0123] Examples of the monoacylphosphine oxide compound include isobutyryldiphenylphosphine oxide, 2-ethylhexanoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide, o-toluoyldiphenylphosphine oxide, p-tert-butylbenzoyldiphenylphosphine oxide, 3-pyridylcarbonyldiphenylphosphine oxide, acryloyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide, and pivaloylphenylphosphine oxide. 4-(tert-butyl)benzoyldiphenylphosphine oxide, terephthaloylbisdiphenylphosphine oxide, 2-methylbenzoyldiphenylphosphine oxide, neodecanoyldiphenylphosphine oxide, 2-methyl-2-ethylhexanoyldiphenylphosphine oxide, 1-methyl-cyclohexanoyldiphenylphosphine oxide, methyl pivaloylphenylphosphinate and isopropyl pivaloylphenylphosphinate.

[0124] Examples of the bisacylphosphine oxide compound include bis(2,6-dichlorobenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-ethoxyphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2-naphthylphosphine oxide, bis(2,6-dichlorobenzoyl)-2-naphthylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-ethoxyphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2-naphthylphosphine oxide, bis(2,6-dichlorobenzoyl)- )-1-naphthylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-chlorophenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,4-dimethoxyphenylphosphine oxide, bis(2,6-dichlorobenzoyl)decylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-octylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-dimethoxyphenylphosphine oxide Methylphenylphosphine oxide, bis(2,6-dichloro-3,4,5-trimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichloro-3,4,5-trimethoxybenzoyl)-4-ethoxyphenylphosphine oxide, bis(2-methyl-1-naphthoyl)-2,5-dimethylphenylphosphine oxide, bis(2-methyl-1-naphthoyl)-4-ethoxyphenylphosphine oxide, bis(2-methyl-1-naphthoyl)- bis(2-methyl-1-naphthoyl)-4-propylphenylphosphine oxide, bis(2-methyl-1-naphthoyl)-2,5-dimethylphenylphosphine oxide, bis(2-methoxy-1-naphthoyl)-4-ethoxyphenylphosphine oxide, bis(2-chloro-1-naphthoyl)-2,5-dimethylphenylphosphine oxide and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

[0125] Examples of the thioxanthone compound include thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanthone, 2-ethoxycarbonylthioxanthone, 3-(2-methoxyethoxycarbonyl)thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl-7-methylthioxanthone, 1-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl-3-chlorothioxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone, 1-ethoxycarbonyl-3-aminothioxanthone, 1-ethoxycarbonyl-3-phenylsulfonylthioxanthone, 3,4-bis[2-(2-methoxyethoxy)ethoxycarbonyl]thioxanthone, 1-ethoxycarbonyl -3-(1-methyl-1-morpholinoethyl)thioxanthone, 2-methyl-6-dimethoxymethylthioxanthone, 2-methyl-6-(1,1-dimethoxybenzyl)thioxanthone, 2-morpholinomethylthioxanthone, 2-methyl-6-morpholinomethylthioxanthone, n-allylthioxanthone-3,4-dicarboxylic imide, n-octylthioxanthone-3,4-dicarboxylic imide, N-(1,1,3,3-tetramethylbutyl)thioxanthone-3,4-dicarboxylic imide, 1-phenoxythioxanthone, 6-ethoxycarbonyl-2-methoxythioxanthone, 6-ethoxycarbonyl-2-methylthioxanthone, thioxanthone-2-polyethylene glycol ester and 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy)-N,N,N-trimethyl-1-propaneammonium chloride.

[0126] The thioxanthone compound may be a commercially available product. Examples of the commercially available product include the SPEEDCURE series manufactured by Lambson (for example, SPEEDCURE 7010, SPEEDCURE CPTX, and SPEEDCURE ITX).

[0127] From the viewpoint of further reducing odor, the ink as one embodiment of the present invention preferably contains at least one selected from the group consisting of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide as a polymerization initiator, and more preferably contains bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide.

[0128] Furthermore, from the viewpoint of further reducing odor, the total content of at least one selected from the group consisting of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide (preferably the total content of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide) relative to the total amount of ink is preferably 3.5% by mass or more, more preferably 5% by mass or more. The upper limit of the above-mentioned total content is not particularly limited, and is, for example, 10% by mass.

[0129] Furthermore, from the viewpoint of further reducing odor, the ink as one embodiment of the present invention preferably contains a compound having two or more thioxanthone skeletons in the molecule as a polymerization initiator.

[0130] The content of the compound having two or more thioxanthone skeletons in the molecule is preferably 1% by mass to 10% by mass, more preferably 2% by mass to 8% by mass, based on the total amount of the ink.

[0131] <Polymerization inhibitor>

[0132] The ink as one embodiment of the present invention preferably contains at least one polymerization inhibitor.

[0133] Examples of the polymerization inhibitor include hydroquinone compounds, phenothiazines, catechols, alkylphenols, alkylbisphenols, zinc dimethyldithiocarbamate, copper dimethyldithiocarbamate, copper dibutyldithiocarbamate, copper salicylate, thiodipropionate, mercaptobenzimidazole, phosphites, nitrosamine compounds, hindered amine compounds and nitrosyl radicals.

[0134] Among them, the polymerization inhibitor is more preferably a nitrosamine compound.

[0135] Examples of the nitrosamine compound include N-nitroso-N-phenylhydroxylamine aluminum salt and N-nitroso-N-phenylhydroxylamine. Among them, the nitrosamine compound is preferably N-nitroso-N-phenylhydroxylamine aluminum salt.

[0136] From the viewpoint of improving the temporal stability of the ink, the content of the polymerization inhibitor is preferably 0.05% by mass to 1% by mass based on the total amount of the ink.

[0137] <Additives>

[0138] The ink as one embodiment of the present invention may contain additives such as a co-sensitizer, an ultraviolet absorber, an antioxidant, an anti-fading agent, a conductive salt, a solvent, and a basic compound as needed.

[0139] <Physical Properties>

[0140] The viscosity of the ink is preferably 0.5 to 50 mPa·s, more preferably 5 to 40 mPa·s, further preferably 7 to 35 mPa·s, and further preferably 8 to 30 mPa·s. The viscosity is measured at 25° C. using a viscometer, such as a TV-22 viscometer manufactured by TOKI SANGYO CO., LTD.

[0141] The surface tension of the ink is preferably 60 mN / m or less, more preferably 23 mN / m to 26 mN / m.

[0142] When the surface tension is 23 mN / m to 26 mN / m, when an overcoat layer is provided on an image, uneven application of an overcoat liquid used for forming the overcoat layer to the image surface can be suppressed.

[0143] The surface tension is measured at 25° C. using a surface tensiometer, for example, an automatic surface tensiometer manufactured by Kyowa Interface Science Co., Ltd. (product name “CBVP-Z”) and a plate method.

[0144] [Image recording method]

[0145] As one embodiment of the present invention, the image recording method includes the following steps: imparting the above-mentioned ink to a substrate using an inkjet recording method (hereinafter also referred to as the "ink imparting step"); and irradiating the imparted ink with active energy rays to record an image (hereinafter also referred to as the "active energy ray irradiation step").

[0146] (Step of applying ink using inkjet recording method)

[0147] -Base Material-

[0148] The type of substrate is not particularly limited, and a commonly known substrate can be used as the substrate. As the substrate, for example, metal, glass, quartz and plastic can be exemplified. As the resin constituting the plastic, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, acrylic resin, chlorinated polyolefin resin, polyether sulfone resin, polyethylene terephthalate (PET), polyethylene naphthalate, nylon, polyethylene, polystyrene, polypropylene, polycycloolefin resin, polyimide resin, polycarbonate resin and polyvinyl acetal can be exemplified. The plastic may be a film containing only one of these resins, or a film mixed with two or more of them.

[0149] The thickness of the substrate is not particularly limited, and is, for example, 1 μm to 10 mm.

[0150] Among them, the ink of the present invention has excellent impact resistance and blocking resistance, so as a substrate, metal or plastic is preferably used, and metal is more preferably used. After recording an image on a flat metal substrate, a molding process described later is implemented to obtain a metal molded body (for example, a food can, a beverage can, an aerosol can, etc.). In addition, in the image recording method of the present invention, an image can be recorded on the molded substrate.

[0151] - Basal layer -

[0152] When a metal is used as the substrate, it is preferred to provide an undercoat layer on the substrate and then apply ink on the undercoat layer.

[0153] Examples of the base layer include an anchor coating layer, a primer layer, and a white coating layer. When the base layer is a white coating layer, it is preferred that the base layer contain titanium oxide as a pigment.

[0154] The method for forming the base layer is not particularly limited, and for example, a method of coating a base layer-forming ink containing a crosslinkable resin or a method of laminating a film containing a crosslinkable resin may be used. In addition, the thickness of the base layer is not particularly limited and can be appropriately adjusted.

[0155] The base layer preferably contains a cross-linkable resin.

[0156] The crosslinkable resin may be a heat-crosslinkable resin that crosslinks by heat, or an active energy ray-crosslinkable resin that crosslinks by active energy rays.

[0157] As the crosslinkable resin, for example, there can be mentioned (meth) acrylic resins such as polyacrylonitrile, polymethacrylate, and polymethyl methacrylate; polyester resins such as polyethylene terephthalate, isophthalic acid-modified polyethylene terephthalate, and polyethylene naphthalate; epoxy resins such as bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and cresol novolac type epoxy resin; vinyl resins such as polyvinyl acetate and polyvinyl chloride; urethane resins such as diphenylmethane diisocyanate-polyethylene glycol copolymer; amino resins such as melamine resin, urea resin, and benzoguanamine resin. The crosslinkable resin may contain only one kind or two or more kinds.

[0158] The base layer may contain resins other than the cross-linkable resin, a cross-linking agent, a cross-linking accelerator, various additives, and the like.

[0159] The method for forming the base layer can be appropriately selected according to the cross-linkable resin.

[0160] When the crosslinkable resin is a thermally crosslinkable resin, it is preferred that the base layer forming ink be applied onto the substrate and then sintered.

[0161] The sintering temperature is, for example, 140°C to 230°C.

[0162] The sintering time is, for example, 1 minute to 60 minutes.

[0163] Furthermore, when the crosslinkable resin is an active energy ray crosslinkable resin, it is preferred that the base layer forming ink is applied onto the base material and then irradiated with active energy rays.

[0164] -Inkjet recording method-

[0165] The inkjet recording method is not particularly limited as long as it can record an image, and a known method can be used. Examples of the inkjet recording method include a charge control method that uses electrostatic induction force to eject ink, a drop-on-demand method (pressure pulse method) that uses vibration pressure of a piezoelectric element, an acoustic inkjet method that converts an electrical signal into an acoustic beam and irradiates the ink to eject the ink using radiation pressure, and a thermal inkjet (Bubble Jet (registered trademark)) method that heats the ink to form bubbles and uses the generated pressure.

[0166] As inkjet heads used in the inkjet recording method, there can be cited a shuttling method in which a short-sized serial head is used to record while scanning the head in the width direction of the substrate, and a line method in which a line head is used in which recording elements are arranged in the entire area corresponding to one side of the substrate.

[0167] In the inline method, the pattern can be formed on the entire surface of the substrate by scanning the substrate in a direction intersecting the arrangement direction of the recording elements, and a transport system such as a carriage for scanning a short-sized nozzle is not required. In addition, in the inline method, there is no need for complex scanning control of the substrate and only the substrate moves, so the recording speed can be increased compared to the reciprocating method.

[0168] The ejection amount of the ink ejected from the inkjet head is preferably 1 pL (picoliter) to 100 pL, more preferably 3 pL to 80 pL, and even more preferably 3 pL to 50 pL.

[0169] (Active Energy Ray Irradiation Step)

[0170] Examples of the active energy ray include gamma rays, beta rays, electron beams, ultraviolet rays, and visible rays. Among them, the active energy ray is preferably ultraviolet rays.

[0171] The peak wavelength of ultraviolet rays is, for example, preferably 200 nm to 405 nm, more preferably 250 nm to 400 nm, and further preferably 300 nm to 400 nm.

[0172] As the light source for ultraviolet irradiation, various lasers such as mercury lamps, gas lasers and solid lasers are mainly used, and discharge lamps such as mercury lamps, metal halide lamps and ultraviolet fluorescent lamps are widely known. In addition, semiconductor light sources such as UV-LED (ultraviolet light emitting diode) and UV-LD (ultraviolet laser diode) are small, long-life, high-efficiency and low-cost, and are expected to be used as light sources for ultraviolet irradiation. Among them, the light source for ultraviolet irradiation is preferably a metal halide lamp, a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp or UV-LED.

[0173] In the present invention, polymerizing only a part of the polymerizable monomers in the ink is also referred to as "temporary curing", and irradiation with active energy rays for the temporary curing is also referred to as "pinning exposure".

[0174] In the present invention, the process of polymerizing substantially all of the polymerizable compounds in the ink is also referred to as “main curing”, and the irradiation with active energy rays for the main curing is also referred to as “main exposure”.

[0175] In the active energy ray irradiation step, it is preferred to perform main curing after temporarily curing the ink. Specifically, it is preferred to perform pinning exposure on the ink after applying the ink, and finally perform main exposure.

[0176] The reaction rate of the ink after pinning exposure is preferably 10% to 80%.

[0177] Here, the reaction rate of the ink refers to the polymerization rate of the polymerizable compound contained in the ink determined by high performance liquid chromatography.

[0178] When the reaction rate of the ink is 10% or more, insufficient dot diffusion is suppressed, and as a result, the graininess of the image finally obtained is improved.

[0179] Furthermore, since the reaction rate of the ink is 80% or less, the ejection interference between the ink dots is suppressed, and as a result, the quality of the image finally obtained is improved.

[0180] From the viewpoint of further improving the graininess of the image finally obtained, the reaction rate of the ink is preferably 15% or more.

[0181] From the viewpoint of further improving the quality of the finally obtained image, the reaction rate of the ink is preferably 75% or less, more preferably 50% or less, further preferably 40% or less, further preferably 30% or less, and further preferably 25% or less.

[0182] The reaction rate of the ink after the main exposure is preferably more than 80% and 100% or less, more preferably 85% to 100%, and even more preferably 90% to 100%.

[0183] When the reaction rate exceeds 80%, the adhesion is further improved.

[0184] The reaction rate of the ink was obtained by the following method.

[0185] Prepare a substrate that has been subjected to the operation until the end of the irradiation of the active energy ray to the ink. Cut out a sample piece of 20 mm × 50 mm in size from the area of ​​the substrate where the ink film exists (hereinafter referred to as the irradiated sample piece). Immerse the cut irradiated sample piece in 10 mL of THF (tetrahydrofuran) for 24 hours to obtain an elution in which the ink is dissolved. The amount of the polymerizable compound (hereinafter referred to as "the amount of monomer after irradiation X1") is determined by high performance liquid chromatography for the obtained elution.

[0186] The same operation as above was carried out except that the ink on the substrate was not irradiated with active energy rays, and the amount of the polymerizable compound (hereinafter referred to as "monomer amount X1 before irradiation") was determined.

[0187] The reaction rate (%) of the ink is calculated from the following formula based on the monomer amount X1 after irradiation and the monomer amount X1 before irradiation.

[0188] Reaction rate of ink (%) = ((monomer amount before irradiation X1 - monomer amount after irradiation X1) / monomer amount before irradiation X1) × 100

[0189] From the viewpoint of making it easier to achieve the reaction rate of the ink, the exposure amount of the active energy ray used for pinning exposure is preferably 10 mJ / cm 2 ~100mJ / cm 2 , more preferably 20 mJ / cm 2 ~60mJ / cm 2 .

[0190] From the viewpoint of completely curing the ink, the exposure dose of the active energy ray used for the main exposure is preferably 50 mJ / cm 2 ~1000mJ / cm 2 , more preferably 200 mJ / cm 2 ~800mJ / cm 2 .

[0191] In the main exposure, from the viewpoint of improving adhesion to the substrate, active energy rays are preferably irradiated in an atmosphere with an oxygen concentration of less than 1 vol %. The oxygen concentration is more preferably 0.5 vol % or less, and even more preferably 0.3 vol % or less.

[0192] In the active energy ray irradiation process, from the viewpoint of image quality, it is preferred to irradiate the active energy ray within 0.1 to 5 seconds from the time when the ink lands. In the case of performing pinning exposure and main exposure, it is preferred to irradiate the active energy ray for pinning exposure within 0.1 to 5 seconds from the time when the ink lands. The time from the time when the ink lands to the time when the active energy ray is irradiated (in the case of performing pinning exposure and main exposure, the active energy ray for pinning exposure) is more preferably within 0.2 to 1 second.

[0193] (Overcoat layer forming step)

[0194] The image recording method of the present invention preferably further comprises a step of forming an overcoat layer on the recorded image.

[0195] By providing the overcoat layer, scratches on the image can be suppressed during the molding described later.

[0196] As the outer coating liquid for forming the outer coating, a generally known transparent coating can be used. As the known transparent coating, for example, there can be cited transparent coatings containing: thermosetting resins such as polyester resins, acrylic resins, and epoxy resins; curing agents such as amino resins, phenolic resins, and isocyanate resins; lubricants such as paraffin wax, polyethylene wax, and silicone wax; and the like.

[0197] The overcoat layer is formed by, for example, applying an overcoat liquid on an image and then sintering the liquid.

[0198] The sintering temperature is, for example, 140°C to 230°C.

[0199] The sintering time is, for example, 1 minute to 60 minutes.

[0200] [Method for producing molded article]

[0201] As one embodiment of the present invention, a method for manufacturing a molded body includes the following steps: imparting the above-mentioned ink to a substrate using an inkjet recording method (hereinafter also referred to as the "ink imparting step"); irradiating the imparted ink with active energy rays to record an image (hereinafter also referred to as the "active energy ray irradiation step"); and molding the substrate with the image recorded thereon to manufacture a molded body (hereinafter also referred to as the "molding step").

[0202] The ink applying step and the active energy ray irradiation step in the method for producing a molded body as one embodiment of the present invention are the same as those in the image recording method as one embodiment of the present invention except for the following points.

[0203] In the ink application step, the substrate is not particularly limited as long as it is a moldable substrate. The substrate is preferably metal or plastic, and more preferably metal.

[0204] (Molding process)

[0205] The molding method is not particularly limited, and examples thereof include bending molding, vacuum molding, extrusion molding, injection molding, compression molding, and blow molding.

[0206] The shape of the molded product is not particularly limited and can be appropriately set depending on the intended use.

[0207] The ink of the present invention has excellent anti-blocking property. For example, after recording an image on a flat metal substrate, even if the metal substrate with the image recorded thereon is laminated before the molding process, the image is not easily peeled off. Therefore, the metal substrate with the image recorded thereon can be stored before the molding process, and the molding process can be performed at a desired timing.

[0208] The ink of the present invention has excellent impact resistance. Therefore, even if the molding process is performed, cracks in the image are unlikely to occur. Therefore, a molded body with excellent decorative properties can be obtained.

[0209] Example

[0210] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it departs from the gist of the present invention.

[0211] <Example 1 to Example 14, Comparative Example 1 to Comparative Example 6>

[0212] [Preparation of cyan ink]

[0213] When preparing the cyan ink, a cyan pigment dispersion is first prepared.

[0214] (Cyan Pigment Dispersion A)

[0215] Cyan pigment (30 parts by mass), SOLSPERSE 32000 (9 parts by mass) as a dispersant, 3MPDDA (60 parts by mass) as a dispersion medium, and UV22 (1 part by mass) as an inhibitor were put into a disperser Motor Mill M50 (manufactured by EIGER), and a dispersion treatment was carried out for 4 hours at a peripheral speed of 9 m / s using zirconia beads with a diameter of 0.65 mm to obtain a cyan pigment dispersion A.

[0216] (Cyan Pigment Dispersion Liquid B)

[0217] Cyan pigment dispersion B was obtained by the same method as that of cyan pigment dispersion A except that DDDA was used instead of 3MPDDA as the dispersion medium.

[0218] (Cyan Pigment Dispersion Liquid C)

[0219] Cyan pigment dispersion C was obtained by the same method as that of cyan pigment dispersion A except that BDDA was used as the dispersion medium instead of 3MPDDA.

[0220] The details of the components contained in the cyan pigment dispersions A to C are as follows.

[0221] Cyan pigment: CI Pigment Blue 15:4 (product name: "Heliogen (registered trademark) Blue D7110F", manufactured by Sun Chemical (DIC) Co., Ltd.)

[0222] SOLSPERSE 32000: Polyethyleneimine dispersant (product name "SOLSPERSE 32000", manufactured by Lubrizol Corporation)

[0223] 3MPDDA: 3-methyl-1,5-pentanediol diacrylate (product name "SR341", manufactured by Sartomer)

[0224] DDDA: 1,10-decanediol diacrylate (product name "SR595", manufactured by Sartomer)

[0225] BDDA: 1,4-Butanediol diacrylate (product name "VISCOAT#195", manufactured by Osaka Organic Chemical Industry Co., Ltd.)

[0226] UV22: A mixture of 2,6-bis(1,1-dimethylethyl)-4-(phenylmethylene)-2,5-cyclohexadien-1-one and propoxylated glyceryl triacrylate (product name "IRGASTAB UV-22", manufactured by BASF)

[0227] In addition, UV22 contains propoxylated glyceryl triacrylate as another polymerizable compound. However, since the content of propoxylated glyceryl triacrylate is very small, the content of UV22 is entirely described in the column of “polymerization inhibitor” in the table.

[0228] Next, the prepared cyan pigment dispersion was mixed with the components listed in Tables 1 to 3 below so that the content of each component became the content (mass %) listed in Tables 1 to 3. In Examples 1 to 14 and Comparative Examples 3 to 6, cyan pigment dispersion A was used. In Comparative Example 1, cyan pigment dispersion B was used. In Comparative Example 2, cyan pigment dispersion C was used.

[0229] The mixture was stirred using a stirrer (product name "L4R", manufactured by Silverson) at 25° C. and 5,000 revolutions per minute for 20 minutes to obtain a cyan ink.

[0230] The details of the components described in Tables 1 to 3 are as follows.

[0231] In addition, Speedcure 7010L (manufactured by Lambson) was used in the preparation of the ink. Speedcure 7010L is a mixture of Speedcure 7010 and EOTMPTA, and the mixing ratio is 1:1 based on mass. Speedcure 7010 is a polymerization initiator, and EOTMPTA is another polymerizable compound, so they are described separately in the columns of polymerization initiator and other polymerizable compounds.

[0232] <Specific bifunctional (meth)acrylate>

[0233] The specific bifunctional (meth)acrylate is a bifunctional (meth)acrylate having a linear or branched alkylene group having 5 to 9 carbon atoms.

[0234] · 3MPDDA: As described above.

[0235] HDDA: 1,6-Hexanediol diacrylate (product name "VISCOAT#230", manufactured by Osaka Organic Chemical Industry Co., Ltd.)

[0236] NDDA: 1,9-hexanediol diacrylate (product name "VISCOAT#260", manufactured by Osaka Organic Chemical Industry Co., Ltd.)

[0237] PDDA: 1,5-pentanediol diacrylate (product name "QH-0602", manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0238] <Benzyl (meth)acrylate>

[0239] BzA: Benzyl acrylate (product name "VISCOAT#160", manufactured by Osaka Organic Chemical Industry Co., Ltd.)

[0240] <Other polymerizable compounds>

[0241] Other polymerizable compounds are polymerizable compounds other than the specific bifunctional (meth)acrylate and benzyl (meth)acrylate.

[0242] DDDA: As above.

[0243] BDDA: As above.

[0244] LA: Lauryl acrylate (product name "LA", manufactured by Osaka Organic Chemical Industries Co., Ltd.)

[0245] IBOA: Isobornyl acrylate (product name "IBXA", manufactured by Osaka Organic Chemical Industry Co., Ltd.)

[0246] · EOTMPTA: trimethylolpropane EO addition triacrylate (50% by mass contained in "product name 'Speedcure 7010L', manufactured by Lambson Corporation")

[0247] <Polymerization initiator>

[0248] BAPO: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name "Omnirad 819", manufactured by IGM Resins BV)

[0249] TPO-L: (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide (product name "Omnirad TPO-L", manufactured by IGM Resins BV)

[0250] Speedcure 7010: 1,3-bis({α-[1-chloro-9-oxo-9H-thioxanthen-4-yl)oxy]acetylpoly[oxy(1-methylethylene)]}oxy)-2,2-bis({α-[1-methylethylene)]}oxymethyl)propane (50% by mass of the product name "Speedcure 7010L", manufactured by Lambson)

[0251] <Polymerization inhibitor>

[0252] UV22: As described above.

[0253] <Silicone-based surfactant>

[0254] The mass ratio M of the content of the polysiloxane structure to the content of the polyether structure is as follows.

[0255] ·TEGORAD2500: a (meth)acryloyl group-containing silicone surfactant (product name "TEGORAD2500", manufactured by Evonik Industries AG, mass ratio M: 0.937369)

[0256] ·TEGORAD2200N: a (meth)acryloyl group-containing silicone surfactant (product name "TEGORAD2200N", manufactured by Evonik Industries AG, mass ratio M: 0.36319)

[0257] ·TEGORAD2250: a (meth)acryloyl group-containing silicone surfactant (product name: "TEGORAD2250", manufactured by Evonik Industries AG, mass ratio M: 0.451587)

[0258] ·TEGORAD2300: a (meth)acryloyl group-containing silicone surfactant (product name: "TEGORAD2300", manufactured by Evonik Industries AG, mass ratio M: 0.612617)

[0259] <Coloring agent>

[0260] Cyan pigment: as described above.

[0261] <Dispersant>

[0262] SOLSPERSE 32000: As described above.

[0263] [Image Record]

[0264] -Base layer forming step-

[0265] On a substrate (a tin-free steel plate (product name: "CANSUPER SR tin-free steel plate", manufactured by NIPPON STEEL CORPORATION)), the concentration of 70 mg / 100 cm 2 The base layer forming ink (product name "WA38", acrylic epoxy white undercoat, manufactured by DIC Graphics Corporation) was applied in an amount of 1000 Å. Then, the base layer was formed on the substrate by sintering at 190° C. for 5 minutes.

[0266] -Ink application step, active energy ray irradiation step-

[0267] Cyan ink was applied twice using an inkjet recording device equipped with an inkjet head (product name "Samba G3L", manufactured by FUJIFILM Dimatix). Specifically, as the first layer, cyan ink was applied to a rectangular area of ​​5 cm × 5 cm on the base layer at a resolution of 1200 × 1200 dpi (dots per inch) and the ink volume was 6.8 g / m 2 Then, the LED light source attached to the inkjet recording device was used to record the image at 20 mJ / cm 2 UV rays were irradiated with an exposure amount of 1000 nm. As the LED light source, a UV-LED irradiator with a peak wavelength of 385 nm (product name "G4B", manufactured by KYOCERA Corporation) was used. On the cyan image of the first layer, which was a rectangular shape of 5 cm × 5 cm, cyan ink was applied as the second layer at a resolution of 1200 × 1200 dpi (dot per inch), and the ink amount was recorded as 6.8 g / m 2 Then, the LED light source attached to the inkjet recording device was used to record the image at 800 mJ / cm 2 The ultraviolet rays were irradiated at an exposure amount of , and an image record was obtained.

[0268] -Outer coating formation process-

[0269] For the image recording surface of the image recording material, 10 g / m 2 An outer coating liquid (product name "GP505W-1 clear coating", manufactured by T&K TOKA CO., LTD., containing polyester resin) was applied in an amount of 1000 Å and sintered at 190° C. for 5 minutes.

[0270] [evaluate]

[0271] The obtained image recorded materials were used for evaluation of impact resistance, blocking resistance, adhesion, overcoatability, and image quality in each of the Examples and Comparative Examples.

[0272] The evaluation method is as follows.

[0273] <Impact resistance>

[0274] For an image recording formed with an outer coating, a DuPont impact tester (Toyo Seiki Sei saku-sho, Ltd.) was used to drop a ball weighing 500 g and having a ball radius of 12.7 mm at the impact tip. The drop height of the ball was set to 10 cm, and the image (ink film) on the image recording surface of the image recording was confirmed to be cracked. If the image had cracks, the test was terminated. If the image had no cracks, the drop height of the ball was set to 20 cm, and the same test was performed. The test was performed in the order of the drop height of the ball being 10 cm, 20 cm, 25 cm, and 30 cm. The evaluation criteria are as follows.

[0275] 5: No cracks occurred even at a height of 30 cm.

[0276] 4: Cracks occurred at a height of 30 cm.

[0277] 3: Cracks occurred at a height of 25 cm.

[0278] 2: Cracks occurred at a height of 20 cm.

[0279] 1: Cracks occurred at a height of 10 cm.

[0280] <Blocking resistance>

[0281] The image recording surface of the image recorded material before the overcoat layer was placed in contact with a tin-free steel plate, and a load of 0.5 ton / m was applied. 2 After being stored in a test environment at 10°C for 24 hours, the image recording surface was peeled off from the Wuxi steel plate in an environment at 25°C. At this time, the presence or absence of image (ink film) peeling was confirmed with the naked eye. In the case of image peeling, the test was terminated. In the case of no image peeling, the test environment was set to 25°C and the same test was performed. The test was performed in the order of test environments of 10°C, 25°C, 30°C, and 45°C. The evaluation criteria are as follows.

[0282] 5: No peeling occurred even at 45°C.

[0283] 4: Peeling occurred at 45°C.

[0284] 3: Peeling occurred at 30°C.

[0285] 2: Peeling occurred at 25°C.

[0286] 1: Peeling occurred at 10°C.

[0287] <Adhesion>

[0288] The image recorded material having the outer coating layer formed thereon was subjected to a cross-cut test. The test results were classified according to JIS K5600-5-6 (ISO 2409). Classification 0 indicated the best adhesion. The evaluation criteria were as follows.

[0289] 5: Classification is 0.

[0290] 4: Classification is 1.

[0291] 3: Classified as 2.

[0292] 2: Classified as 3.

[0293] 1: The classification is 4 or higher.

[0294] <Suitability for external coating>

[0295] For the image recording surface of the image recorded material before forming the overcoat layer, the 2 The coating amount of the outer coating liquid (product name "GP505W-1 clear coating", manufactured by T&K TOKA CO., LTD., containing polyester resin) was applied to confirm whether uneven coating occurred. If uneven coating occurred, the test was terminated. If uneven coating did not occur, the coating amount of the outer coating liquid was set to 15 g / m 2 The same test was carried out. The coating amount of the outer coating liquid was 20g / m 2 , 15g / m 2 , 10g / m 2 , 5g / m 2 The test was conducted in the following order. The evaluation criteria are as follows.

[0296] 5: Even if the coating amount is 5g / m 2 There is no uneven coating.

[0297] 4: coating amount is 5g / m 2 Uneven coating occurs.

[0298] 3: coating amount is 10g / m 2 Uneven coating occurs.

[0299] 2: coating amount is 15g / m 2 Uneven coating occurs.

[0300] 1: coating amount is 20g / m 2 Uneven coating occurs.

[0301] <Image quality>

[0302] After forming the base layer on the substrate, cyan ink was applied at a resolution of 1200×1200 dpi (dot per inch), and the ink volume was recorded as 7.4 g / m 2 Then, the LED light source attached to the inkjet recording device was used to record the image at 50 mJ / cm 2 The ultraviolet light was irradiated with an exposure amount of 1000 nm. The image recording surface was observed with a magnifying glass (50 times) to check whether there was a gap. If there was a gap, the test was terminated. If there was no gap, the ink volume was set to 7.1 g / m 2 , and the same test was carried out. The ink volume is 7.4g / m 2 , 7.1g / m 2 , 6.8g / m 2 , 6.5g / m 2 The test was conducted in the following order. The evaluation criteria are as follows.

[0303] 5: Even if the ink volume is 6.5g / m 2 There is no gap in time.

[0304] 4: The ink volume is 6.5g / m 2 There are gaps from time to time.

[0305] 3: The ink volume is 6.8g / m 2 There are gaps from time to time.

[0306] 2: The ink volume is 7.1g / m 2 There are gaps from time to time.

[0307] 1: The ink volume is 7.4g / m 2 There are gaps from time to time.

[0308] Tables 1 to 3 show the evaluation results.

[0309] In Tables 1 to 3, "BzA+M2" represents the total content (mass %) of benzyl acrylate and the specific bifunctional (meth)acrylate.

[0310] “BzA / M2” represents the mass ratio of the content of benzyl acrylate to the content of the specific bifunctional (meth)acrylate.

[0311] “(BzA+M2) / polymerizable compound” represents the total content of benzyl acrylate and specific bifunctional (meth)acrylate relative to the total content of all polymerizable compounds (excluding silicone surfactants) contained in the ink.

[0312] [Table 1]

[0313]

[0314] [Table 2]

[0315]

[0316] [Table 3]

[0317]

[0318] As shown in Tables 1 and 2, in Examples 1 to 14, it can be seen that the ink contains a specific bifunctional (meth)acrylate, benzyl (meth)acrylate and a colorant, and the total content of the specific bifunctional (meth)acrylate and benzyl (meth)acrylate is 60% by mass or more relative to the total amount of the ink, so the obtained image has excellent impact resistance and blocking resistance.

[0319] On the other hand, in Comparative Example 1, it was found that the ink did not contain the specific bifunctional (meth)acrylate and had poor blocking resistance.

[0320] In Comparative Example 2, it was found that the ink did not contain the specific bifunctional (meth)acrylate and had poor impact resistance.

[0321] In Comparative Example 3, it is found that the ink does not contain benzyl (meth)acrylate and has poor impact resistance.

[0322] In Comparative Example 4, it was found that the total content of the specific bifunctional (meth)acrylate and benzyl (meth)acrylate was less than 60% by mass, and the impact resistance was poor.

[0323] In Comparative Example 5, it is found that the ink does not contain benzyl (meth)acrylate and has poor blocking resistance.

[0324] In Comparative Example 6, it was found that the total content of the specific bifunctional (meth)acrylate and benzyl (meth)acrylate was less than 60% by mass, and the blocking resistance was poor.

[0325] In Example 1, since the total content of the specific bifunctional (meth)acrylate and benzyl acrylate is 95 mass % or more based on the total amount of the polymerizable compound, the impact resistance, blocking resistance and adhesion are excellent compared with Examples 5 and 6 and Comparative Examples.

[0326] In Example 1, it is found that the mass ratio of the content of benzyl acrylate to the content of the specific bifunctional (meth)acrylate is 2 or more, and therefore, compared with Example 9, the impact resistance and adhesion are excellent.

[0327] In Example 1, it is found that the mass ratio of the content of benzyl acrylate to the content of the specific bifunctional (meth)acrylate is 5 or less, and therefore, compared with Example 7, the blocking resistance is excellent.

[0328] In Example 9, since the content of benzyl acrylate is 50 mass % or more, it is found that the impact resistance and the adhesion are excellent compared with those of Example 10.

[0329] In Example 11, it is found that the surface tension of the ink is 23 mN / m or more, and the outer coating suitability is excellent compared with Examples 12 and 13.

[0330] In Example 1, it is found that the surface tension of the ink is 26 mN / m or less, and the image quality is excellent compared with that of Example 14.

[0331] In Example 11, it is found that the silicone surfactant contains a polyether structure and a polysiloxane structure, and the mass ratio of the content of the polysiloxane structure to the content of the polyether structure is 0.6 or less. Therefore, compared with Example 12, the external coating suitability is excellent.

[0332] <Example 101>

[0333] Ink C1 (cyan ink), ink M1 (magenta ink), ink Y1 (yellow ink), ink K1 (black ink), and ink W1 (white ink) were prepared.

[0334] As ink C1, the cyan ink in Example 1 was used.

[0335] [Preparation of inks M1, Y1, K1, and W1]

[0336] First, a magenta pigment dispersion, a yellow pigment dispersion, a black pigment dispersion, and a white pigment dispersion were prepared.

[0337] In the preparation of the cyan pigment dispersion, a magenta pigment dispersion, a yellow pigment dispersion, a black pigment dispersion, and a white pigment dispersion were prepared by replacing the cyan pigment with a magenta pigment, a yellow pigment, a black pigment, and a white pigment, respectively.

[0338] Details of the magenta pigment, the yellow pigment, the black pigment, and the white pigment are as follows.

[0339] Magenta pigment: CI Pigment RED 122, product name "TRM-33", manufactured by Dainichis eika Color & Chemicals Mfg. Co., Ltd.

[0340] Yellow pigment: CI Pigment Yellow 185, product name "Paliotol Yellow D1155", manufactured by Sun Chemical (DIC)

[0341] Black pigment: Carbon black, product name "MOGUL E", manufactured by CABOT

[0342] White pigment: Titanium oxide, product name "KRONOS 2300", manufactured by KRONOS

[0343] Next, the prepared magenta pigment dispersion, yellow pigment dispersion, black pigment dispersion, and white pigment dispersion were mixed with the components listed in Table 4, respectively, so that the content of each component became the content (mass %) listed in Table 4. The mixture was stirred for 20 minutes at 25° C. and 5000 rpm using a stirrer (product name “L4R”, manufactured by Silverson), to obtain inks M1, Y1, K1, and W1.

[0344] [Table 4]

[0345]

[0346] [Image Record]

[0347] The base layer was formed on the substrate by the same method as in the above-mentioned base layer forming step.

[0348] -2 color multi-layer printing-

[0349] Using an inkjet recording device equipped with an inkjet head (product name "Samba G3L", manufactured by FUJIFILM Dimatix), yellow ink (ink Y1) and magenta ink (ink M1) were applied once. Specifically, as the first layer, yellow ink was applied to a rectangular area of ​​5 cm × 5 cm on the base layer at a resolution of 1200 × 1200 dpi, and the ink volume was recorded at 6.8 g / m 2 A 100% solid image.

[0350] Then, the LED light source attached to the inkjet recording device was used to emit light at 20 mJ / cm 2 Ultraviolet rays were irradiated with an exposure amount of 1000 dpi. As the LED light source, a UV-LED irradiator with a peak wavelength of 385 nm (product name "G4B", manufactured by KYOCERA Corporation) was used. On the first layer, a 5 cm × 5 cm rectangular yellow image was applied with magenta ink as the second layer at a resolution of 1200 × 1200 dpi, and the ink amount was recorded as 6.8 g / m 2 Then, the LED light source attached to the inkjet recording device was used to record the image at 800 mJ / cm 2 The ultraviolet rays were irradiated at an exposure amount of , and an image record was obtained.

[0351] -3-color multi-layer printing-

[0352] An inkjet recording device equipped with an inkjet head (product name "Samba G3L", manufactured by FUJIFILM Dimatix) was used to apply yellow ink (ink Y1), magenta ink (ink M1), and cyan ink (ink C1) once. In the above two-color multi-layer printing, cyan ink was applied as the third layer on the 5 cm × 5 cm rectangular magenta image of the second layer at a resolution of 1200 × 1200 dpi, and the amount of each ink was changed to 4.8 g / m 2 , except for this, an image recorded material was obtained by the same method as the above-mentioned two-color multilayer printing.

[0353] -4-color multi-layer printing-

[0354] An inkjet recording device equipped with an inkjet head (product name "Samba G3L", manufactured by FUJIFILM Dimatix) was used to apply yellow ink (ink Y1), magenta ink (ink M1), cyan ink (ink C1), and black ink (ink K1) once. In the above three-color multi-layer printing, black ink was applied as the fourth layer on the cyan image of the third layer, which was a rectangular image of 5 cm × 5 cm, at a resolution of 1200 × 1200 dpi, and the amount of each ink was changed to 3.8 g / m 2 , except for this, an image recorded material was obtained by the same method as the above-mentioned three-color multilayer printing.

[0355] -5-color multi-layer printing-

[0356] Using an inkjet recording device equipped with an inkjet head (product name "Samba G3L", manufactured by FUJIFILM Dimatix), white ink (W1), yellow ink (ink Y1), magenta ink (ink M1), and cyan ink (ink C1) were applied once. Specifically, as the first layer, white ink was applied to a rectangular area of ​​5 cm × 5 cm in the base layer at a resolution of 1200 × 1200 dpi, and the ink volume was recorded at 6.8 g / m 2 Then, the LED light source attached to the inkjet recording device was used to record the image at 20 mJ / cm 2 The ultraviolet rays were irradiated with an exposure amount of 1.50%. As the LED light source, a UV-LED irradiator with a peak wavelength of 385 nm (product name "G4B", manufactured by KYOCERA Corporation) was used. Yellow ink was applied to the rectangular white image of 5 cm × 5 cm on the first layer, and an image record was obtained by the same method as the above-mentioned 4-color multilayer printing.

[0357] The image records thus obtained were evaluated for impact resistance, blocking resistance, adhesion, overcoatability, and image quality by the same evaluation methods as in Example 1. The evaluation results were all "5".

[0358] Each of the obtained image records was processed into a square can (depth 15 mm, corner diameter 6 mm) using an extruder. Each corner of the obtained square can was visually observed to confirm that there was no crack.

Claims

1. An active energy ray-curable inkjet ink comprising a bifunctional (meth)acrylate having a linear or branched alkylene group having 5 to 9 carbon atoms, benzyl (meth)acrylate, and a colorant, The total content of the bifunctional (meth)acrylate and the benzyl (meth)acrylate is 60% by mass to 100% by mass based on the total amount of the active energy ray-curable inkjet ink.

2. The active energy ray-curable inkjet ink according to claim 1, wherein The total content of the bifunctional (meth)acrylate and the benzyl (meth)acrylate is 95% by mass to 100% by mass based on the total amount of the polymerizable compound.

3. The active energy ray-curable inkjet ink according to claim 1 or 2, wherein: The mass ratio of the content of the benzyl (meth)acrylate to the content of the bifunctional (meth)acrylate is 2.0 to 5.

0.

4. The active energy ray-curable inkjet ink according to claim 1 or 2, wherein: The content of the benzyl (meth)acrylate is 50% by mass to 70% by mass based on the total amount of the active energy ray-curable inkjet ink.

5. The active energy ray-curable inkjet ink according to claim 1 or 2, wherein: The surface tension is 23mN / m~26mN / m.

6. The active energy ray-curable inkjet ink according to claim 1 or 2, wherein: The active energy ray-curable inkjet ink further includes a silicone-based surfactant.

7. The active energy ray-curable inkjet ink according to claim 6, wherein: The silicone-based surfactant comprises a polyether structure and a polysiloxane structure. The mass ratio of the content of the polysiloxane structure to the content of the polyether structure is 0.2 to 0.

6.

8. An image recording method comprising the following steps: A step of applying the active energy ray-curable inkjet ink according to claim 1 or 2 to a substrate by an inkjet recording method; and A step of irradiating the applied active energy ray-curable inkjet ink with active energy rays to record an image.

9. A method for producing a molded body, comprising the following steps: A step of applying the active energy ray-curable inkjet ink according to claim 1 or 2 to a substrate by an inkjet recording method; a step of irradiating the applied active energy ray-curable inkjet ink with active energy rays to record an image; and A step of molding a substrate having an image recorded thereon to produce a molded body.

Images