Active energy ray-curable composition, active energy ray-curable ink composition, active energy ray-curable inkjet ink composition, composition container, and two-dimensional or three-dimensional image-forming device

Abstract

To provide an active energy-ray curable composition that achieves both of excellent adhesion to a recording medium and excellent blocking resistance, in a balanced manner.SOLUTION: An active energy-ray curable composition contains a trifunctional adduct urethane methacrylate oligomer, a monomer with a glass transition temperature of 90°C or higher, and a monomer with a glass transition temperature of 30°C or lower. The content of the monomer with a glass transition temperature of 90°C or higher is 10 mass% or more and 30 mass% or less, and the content of the monomer with a glass transition temperature of 30°C or lower is 20 mass% or more and 50 mass% or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an actinic energy ray-curable composition, an actinic energy ray-curable ink composition, an actinic energy ray-curable inkjet ink composition, a composition container, and a two-dimensional or three-dimensional image-forming device. [Background technology]

[0002] Since active energy ray-curable compositions are cured by irradiation with active energy rays, they are required to have excellent drying properties compared to solvent-based ink compositions and to have good adhesion to plastic substrates such as acrylic and metal substrates such as aluminum.

[0003] For example, an inkjet recording method has been proposed in which a first undercoat layer containing a thermosetting resin, an acrylic resin, and a cellulose resin is formed on an aluminum foil substrate, a second undercoat layer containing a compound having an isocyanate group, a radically polymerizable monomer, and a radical polymerization initiator is formed on the first undercoat layer, and the second undercoat layer is cured by irradiating with ultraviolet light, thereby improving the heat-resistant adhesion of printed matter (see, for example, Patent Document 1). Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide an active energy ray-curable composition that has excellent adhesion to a recording medium and excellent blocking resistance, and that satisfies both of these requirements. [Means for solving the problem]

[0005] The active energy ray-curable composition of the present invention, which is a means for solving the above problems, contains a trifunctional adduct urethane (meth)acrylate oligomer, a monomer having a glass transition temperature of 90°C or higher, and a monomer having a glass transition temperature of 30°C or lower, wherein the content of the monomer having a glass transition temperature of 90°C or higher is 10% by mass or more and 30% by mass or less, and the content of the monomer having a glass transition temperature of 30°C or lower is 20% by mass or more and 50% by mass or less. [Effects of the Invention]

[0006] According to the present invention, it is possible to provide an active energy ray-curable composition that has excellent adhesion to a recording medium and excellent blocking resistance, and that satisfies both of these properties. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic diagram showing an example of a two-dimensional or three-dimensional image forming apparatus of the present invention. [Figure 2] FIG. 2 is a schematic diagram showing another example of another two-dimensional or three-dimensional image forming apparatus according to the present invention. [Figure 3A] FIG. 3A is a schematic diagram showing another example of another two-dimensional or three-dimensional imaging device of the present invention. [Figure 3B] FIG. 3B is a schematic diagram showing another example of another two-dimensional or three-dimensional imaging device of the present invention. [Figure 3C] FIG. 3C is a schematic diagram showing another example of another two-dimensional or three-dimensional imaging device of the present invention. [Figure 3D] FIG. 3D is a schematic diagram showing another example of another two-dimensional or three-dimensional imaging device of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0008] The active energy ray-curable composition, active energy ray-curable ink composition, active energy ray-curable inkjet ink composition, inkjet recording method, composition container, and two-dimensional or three-dimensional image forming apparatus according to the present invention will be described below. The present invention is not limited to the embodiments shown below, and can be modified within the scope of what a person skilled in the art can conceive, such as adding, modifying, and deleting other embodiments, and as long as the functions and effects of the present invention are achieved in any aspect, it is included in the scope of the present invention.

[0009] (Active energy ray curable composition) The active energy ray-curable composition of the present invention contains a trifunctional adduct urethane (meth)acrylate oligomer, a monomer having a glass transition temperature (Tg) of 90°C or higher, and a monomer having a glass transition temperature (Tg) of 30°C or lower, and may further contain other components as necessary.

[0010] In conventional active energy ray-curable compositions, when the coating film is softened in order to improve adhesion to the recording medium, blocking resistance may decrease. Furthermore, when a crosslinking component such as a polyfunctional monomer is added as a means to improve blocking resistance, there is a problem in that adhesion to the substrate decreases.

[0011] For example, an inkjet ink composition containing a colorant, a monofunctional acrylate monomer, a tri- or higher functional urethane acrylate oligomer, and a photopolymerization initiator has been proposed as an inkjet ink composition capable of improving the adhesion of an image formed on a recording medium (substrate) made of an ink-non-absorbent material (see, for example, JP 2006-257155 A). However, when attempting to achieve adhesion to the substrate, problems have arisen in that the coating film strength is reduced and the blocking resistance of the coating film is reduced. On the other hand, adding a crosslinking component to improve blocking resistance increases the internal stress of the coating film, resulting in a trade-off problem of reduced adhesion to the substrate. Since there is a trade-off between adhesion to the recording medium and blocking resistance, it is difficult to achieve both qualities.

[0012] Furthermore, a primer composition has been proposed that contains a compound having an isocyanate group, a specific radically polymerizable monomer, and a radical polymerization initiator, thereby providing excellent application properties and excellent adhesion and blocking prevention for the resulting printed matter (see, for example, JP 2016-069654 A). However, the blocking property referred to here is only effective in the primer layer, and does not have anti-blocking effect on the upper layer, so there is a problem in that it is not possible to impart blocking resistance to the entire coating film.

[0013] In response to this, the present inventors have conducted extensive research and found that an active energy ray-curable composition capable of forming a cured product that combines flexibility, which affects adhesion to a recording medium, with blocking resistance can be obtained by containing a trifunctional adduct urethane (meth)acrylate oligomer, a predetermined content of a monomer having a glass transition temperature (Tg) of 90°C or higher, and a predetermined content of a monomer having a glass transition temperature (Tg) of 30°C or lower.

[0014] Furthermore, it has also been found that the active energy ray-curable composition has excellent ejection stability in an inkjet system, and that the cured product obtained by curing the active energy ray-curable composition has excellent crack resistance of the coating film (cured product) on a plastic substrate.

[0015] <Trifunctional adduct urethane (meth)acrylate oligomer> The trifunctional adduct urethane (meth)acrylate oligomer must be an adduct. The adduct has crosslinking points that are composed of C-C bonds with little steric hindrance, and therefore is highly effective as a chemical crosslinking point. Therefore, by including the trifunctional adduct urethane acrylate oligomer in the active energy ray-curable composition, it is possible to obtain a cured ink product that has both flexibility, which affects adhesion to a recording medium, and blocking resistance.

[0016] In this specification, the term "oligomer" refers to a polymer having 2 or more and 20 or less repeating monomer structural units.

[0017] In addition, in this specification, "(meth)acrylate" means "acrylate" or "methacrylate".

[0018] The weight-average molecular weight of the trifunctional adduct urethane (meth)acrylate oligomer is not particularly limited and can be appropriately selected depending on the purpose. The weight-average molecular weight can be measured, for example, by gel permeation chromatography (GPC).

[0019] The trifunctional urethane (meth)acrylate oligomer may be a synthetic product appropriately synthesized by a known method, a commercially available product, or a combination of a synthetic product and a commercially available product.

[0020] The method for synthesizing the trifunctional urethane (meth)acrylate oligomer is not particularly limited and can be appropriately selected from known methods. For example, the oligomer can be synthesized by the method described in JP-A-2002-256053.

[0021] A specific example of a method for synthesizing the trifunctional urethane (meth)acrylate oligomer is a method of reacting an organic isocyanate (A) having three isocyanate groups in one molecule, a long-chain alkyl alcohol (B), and a polycaprolactone-modified hydroxyethyl (meth)acrylate (C).

[0022] <<Organic isocyanate (A)>> The organic isocyanate (A) is obtained by modifying a diisocyanate monomer (a) having two isocyanate groups, and has three isocyanate groups per molecule. The method for modifying the diisocyanate monomer (b) is adduct modification.

[0023] The diisocyanate monomer (a) is not particularly limited and can be appropriately selected from known diisocyanate monomers, such as tolylene diisocyanate (TDI) represented by the following structural formula (1), naphthalene diisocyanate (NDI) represented by the following structural formula (2), diphenylmethane diisocyanate (MDI) represented by the following structural formula (3), isophorone diisocyanate (IPDI) represented by the following structural formula (4), xylylene diisocyanate (XDI) represented by the following structural formula (5), hexamethylene diisocyanate (HDI) represented by the following structural formula (6), dicyclohexylmethane diisocyanate (H-MDI) represented by the following structural formula (7), 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, or norbornane diisocyanate methyl. These may be used alone or in combination of two or more.

[0024] [ka]

[0025] [ka]

[0026] [ka]

[0027] [ka]

[0028] [ka]

[0029] [ka]

[0030] [ka]

[0031] Examples of the organic isocyanate (A) obtained by adduct-modifying the diisocyanate monomer (a) include compounds represented by the following general formula (1).

[0032] [ka]

[0033] In the general formula (1), R1, R2, and R3 each independently represent any one of the following general formulae (1-i) to (1-vii): R1, R2, and R3 may be the same or different.

[0034] [ka] In the general formulae (1-i) to (1-vii), "*" represents a bond.

[0035] <<Long-chain alkyl alcohol (B)>> The long-chain alkyl alcohol (B) is not particularly limited and can be appropriately selected depending on the purpose, but is preferably one having a long-chain alkyl group with 13 to 25 carbon atoms.

[0036] Specific examples of the long-chain alkyl alcohol (B) include tridecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, polyoxyethylene monostearate, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and glycerol monostearate.

[0037] <<Polycaprolactone-modified hydroxyethyl (meth)acrylate (C)>> The polycaprolactone-modified hydroxyethyl (meth)acrylate (C) is not particularly limited and can be appropriately selected depending on the purpose, but a compound represented by the following general formula (2) is preferred because it is reactive with an isocyanate group and has an active energy ray-curable functional group (CH2=).

[0038] [ka]

[0039] In the general formula (2), R4 represents H or CH3.

[0040] In the general formula (2), n represents an integer of 1 to 25, and is preferably an integer of 2 to 5, since this can suppress poor curing due to an increase in the molecular weight between crosslinks of the active energy ray-curable composition.

[0041] The method for synthesizing the trifunctional adduct urethane (meth)acrylate oligomer is not particularly limited and can be appropriately selected from known methods. For example, there can be mentioned a method in which an organic isocyanate (A) having three isocyanate groups in one molecule and the long-chain alkyl alcohol (B) are mixed and reacted (hereinafter, sometimes referred to as "reaction I"), and then the polycaprolactone-modified hydroxyethyl (meth)acrylate (C) is further added and reacted (hereinafter, sometimes referred to as "reaction II").

[0042] The reaction I and the reaction II may be carried out in a solution or in a solvent-free system, but are usually carried out in a solution.

[0043] The solution used in Reaction I and Reaction II is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as ethyl acetate, propyl acetate, isobutyl acetate and butyl acetate, etc. These may be used alone or in combination of two or more.

[0044] Furthermore, the reactions I and II can also be carried out in a compound having an active energy ray-curable functional group (CH2=), such as styrene, diethylene glycol diacrylate, or triethylene glycol diacrylate.

[0045] The reaction temperature in the reaction I and the reaction II is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 23°C to 100°C, more preferably 60°C to 80°C.

[0046] The reaction time in the reaction I and the reaction II is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 hour to 10 hours, more preferably 1 hour to 5 hours.

[0047] The mixing ratio of the organic isocyanate (A), the polycaprolactone-modified hydroxyethyl (meth)acrylate (C), and the long-chain alkyl alcohol (B) is not particularly limited and can be appropriately selected depending on the purpose. However, it is preferable that the molar ratio of the isocyanate groups of the organic isocyanate (A), the hydroxyl groups of the polycaprolactone-modified hydroxyethyl (meth)acrylate (C), and the hydroxyl groups of the long-chain alkyl alcohol (B) [(A):(C):(B)] is 1:0.8-1.50:0.02-0.33.

[0048] In the synthesis of the trifunctional adduct urethane (meth)acrylate oligomer, a catalyst may be further used, if necessary. The catalyst is not particularly limited and can be appropriately selected from known catalysts, and examples thereof include dibutyltin dilaurate, dibutyltin diethylhexoate, dibutyltin sulfite, etc. These may be used alone or in combination of two or more.

[0049] The amount of the catalyst to be added is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.01 to 1 part by mass, more preferably 0.01 to 0.1 parts by mass, per 100 parts by mass of the organic isocyanate (A).

[0050] When the reaction II is terminated, a polymerization inhibitor such as hydroquinone monomethyl ether may be used. The amount of the polymerization inhibitor to be added is not particularly limited as long as it can stop the reaction II, but is preferably 0.01 to 1 part by mass, more preferably 0.01 to 0.1 part by mass, relative to 100 parts by mass of the polycaprolactone-modified hydroxyethyl (meth)acrylate (C).

[0051] The content of the trifunctional adduct urethane (meth)acrylate oligomer in the active energy ray-curable composition is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1.0% by mass or more and 5.0% by mass or less, based on the total mass of the active energy ray-curable composition. When the content of the trifunctional adduct urethane (meth)acrylate oligomer is 1.0% by mass or more, excellent blocking resistance is achieved, and when it is 5.0% by mass or less, excellent continuous discharge stability and adhesion to the recording medium are achieved.

[0052] <Monomers with a glass transition temperature (Tg) of 90°C or higher> The monomer having a glass transition temperature (Tg) of 90°C or higher is not particularly limited and can be appropriately selected from known monomers, such as trimethylolethane tri(meth)acrylate (Tg 250°C or higher), acryloylmorpholine (ACMO (registered trademark)) (Tg 145°C), dipropylene glycol di(meth)acrylate (Tg 110°C), isobornyl (meth)acrylate (Tg 97°C), and hydroxyethyl acrylamide (HEAA (registered trademark)) (Tg 90°C). These may be used alone or in combination of two or more.

[0053] The monomer having a glass transition temperature (Tg) of 90° C. or higher may be a synthetic product appropriately synthesized by a known method, a commercially available product, or a combination of a synthetic product and a commercially available product.

[0054] In this specification, "(meth)acryloxy" means "acryloxy" or "methacryloxy".

[0055] The content of the monomer having a glass transition temperature (Tg) of 90° C. or higher in the active energy ray-curable composition is 10% by mass to 30% by mass, and preferably 10% by mass to 20% by mass, based on the total mass of the active energy ray-curable composition. If the content of the monomer having a glass transition temperature (Tg) of 90° C. or higher is less than 10% by mass, blocking resistance decreases, and if it exceeds 30% by mass, adhesion to a recording medium decreases.

[0056] <Monomers with glass transition temperature (Tg) of 30°C or less> The monomer having a glass transition temperature (Tg) of 30° C. or less is not particularly limited and can be appropriately selected from known monomers, such as cyclic trimethylolpropane formal (meth)acrylate (Tg 27° C.), phenoxyethyl (meth)acrylate (Tg 2° C.), etc. These may be used alone or in combination of two or more.

[0057] The monomer having a glass transition temperature (Tg) of 30° C. or less may be a synthetic product appropriately synthesized by a known method, a commercially available product, or a combination of a synthetic product and a commercially available product.

[0058] The content of the monomer having a glass transition temperature (Tg) of 30° C. or less in the active energy ray-curable composition is 20% by mass to 50% by mass, and preferably 30% by mass to 40% by mass, based on the total mass of the active energy ray-curable composition. If the content of the monomer having a glass transition temperature (Tg) of 30° C. or less is less than 20% by mass, adhesion to the recording medium decreases, and if it exceeds 50% by mass, blocking resistance decreases.

[0059] The glass transition temperatures of the monomers having a glass transition temperature (Tg) of 90° C. or higher and the monomers having a glass transition temperature (Tg) of 30° C. or lower can be measured by a differential scanning calorimeter (DSC).

[0060] <Other ingredients> The other components are not particularly limited as long as they do not impair the effects of the present invention and can be appropriately selected depending on the purpose, and examples thereof include polymerization initiators, polymerization accelerators (sensitizers), colorants, organic solvents, surfactants, polymerization inhibitors, leveling agents, antifoaming agents, fluorescent brighteners, penetration accelerators, wetting agents (moisturizing agents), fixing agents, viscosity stabilizers, antifungal agents, preservatives, antioxidants, ultraviolet absorbers, chelating agents, pH adjusters, thickeners, etc. These may be used alone or in combination of two or more.

[0061] <<Polymerization initiator>> The polymerization initiator is not particularly limited as long as it is capable of generating active species such as radicals or cations by the energy of active energy rays and initiating polymerization of a polymerizable compound (monomer or oligomer), and known radical polymerization initiators, known cationic polymerization initiators, known base generators, etc. can be used. These may be used alone or in combination of two or more. Among these, radical polymerization initiators are preferred as the polymerization initiator from the viewpoint of high material selectivity.

[0062] The radical polymerization initiator is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds.

[0063] Specific examples of the radical polymerization initiator include benzophenone, acetophenone, 2-hydroxy-2-phenylacetophenone, 2-ethoxy-2-phenylacetophenone, 2-methoxy-2-phenylacetophenone, 2-isopropoxy-2-phenylacetophenone, 2-isobutoxy-2-phenylacetophenone, 4-methoxyacetophenone, 4-benzyloxyacetophenone, 4-phenylacetophenone, 4-benzoyl 4'-methyldiphenyl sulfide, methyl benzoylformate, and ethyl benzoylformate, 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-1-one oligomer [benzene, (1-methylethynyl)-, homopolymer, ar-(2-hydroxy-2-methyl-1-oxopropyl) derivative] (trade names: Esacure ONE, IGM Resins BV), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (trade name: Irgacure 369, IGM Resins BV), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Irgacure 819, IGM Resins BV), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name: Irgacure TPO, IGM Resins BV), polyethylene glycol 200-di(β-4(4-(2-dimethylamino-2-benzyl)butanonylphenyl)piperazine) (trade name: Omnipol 910, IGM Resins BV), BV), 1,3-di({α-[1-chloro-9-oxo-9H-thioxanthen-4-yl)oxy]acetylpoly[oxy(1-methylethylene)]}oxy)-2,2-bis({α-[1-chloro-9-oxo-9H-thioxanthen-4-yl)oxy]acetylpoly[oxy(1-methylethylene)]}oxymethyl)propane (trade name: SpeedCure7010, Lambson), polybutylene glycol bis(9-oxo-9H-thioxanthinyloxy)acetate (trade name: Omnipol TX, IGM Resins BV), polymeric thioxanthene compound (trade name: Genepol *TX-2, manufactured by Lahn AG) and the like. These may be used alone or in combination of two or more. The radical polymerization initiator may be an appropriately synthesized one or a commercially available product.

[0064] The content of the polymerization initiator in the active energy ray-curable composition is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of obtaining a sufficient curing rate, the content is preferably 5% by mass to 20% by mass relative to the total mass of the active energy ray-curable composition.

[0065] <<Polymerization accelerator (sensitizer)>> The active energy ray-curable composition may contain a polymerization accelerator (sensitizer) in addition to the polymerization initiator. The polymerization accelerator (sensitizer) is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include amine compounds such as trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, N,N-dimethylbenzylamine, and 4,4'-bis(diethylamino)benzophenone. These may be used alone or in combination of two or more.

[0066] The content of the polymerization initiator in the active energy ray-curable composition is not particularly limited and can be appropriately selected depending on the polymerization initiator to be used and the amount used.

[0067] <<Colorants>> As the coloring material, various pigments and dyes that impart black, white, magenta, cyan, yellow, green, orange, glossy colors (for example, gold or silver), etc. can be used depending on the purpose and required properties of the active energy ray-curable composition.

[0068] The pigment is not particularly limited and can be appropriately selected depending on the purpose, and for example, inorganic pigments, organic pigments, etc. The pigments may be used alone or in combination of two or more.

[0069] The inorganic pigment is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include carbon blacks (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide.

[0070] Examples of the organic pigment include azo pigments (for example, insoluble azo pigments, condensed azo pigments, azo lakes, and chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments), dye chelates (for example, basic dye chelates and acid dye chelates), dye lakes (for example, basic dye lakes and acid dye lakes), nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments.

[0071] Furthermore, in order to improve the dispersibility of the pigment, a dispersant may be further contained. The dispersant is not particularly limited, but examples thereof include dispersants commonly used in preparing pigment dispersions, such as polymer dispersants.

[0072] The dye is not particularly limited and can be appropriately selected depending on the purpose, and for example, acid dyes, direct dyes, reactive dyes, or basic dyes can be used. These can be used alone or in combination of two or more.

[0073] The content of the colorant in the active energy ray-curable composition is not particularly limited and can be appropriately selected in consideration of the desired color density, dispersibility in the active energy ray-curable composition, and the like; however, the content is preferably 0.1% by mass or more and 20% by mass or less with respect to the total mass of the active energy ray-curable composition.

[0074] The active energy ray-curable composition may be colorless and transparent without containing a coloring material, which is suitable for use as an overcoat layer for protecting an image, for example.

[0075] <<Organic solvents>> The active energy ray-curable composition may contain the organic solvent, but preferably does not contain the organic solvent if possible. If the active energy ray-curable composition is a composition that does not contain an organic solvent, particularly a volatile organic solvent (VOC (Volatile Organic Compounds)-free composition), the safety of the place where the active energy ray-curable composition is handled can be further improved, and it is also possible to prevent environmental pollution.

[0076] In this specification, the term "organic solvent" refers to a general non-reactive organic solvent such as ether, ketone, xylene, ethyl acetate, cyclohexanone, or toluene, and should be distinguished from the monomer having a glass transition temperature (Tg) of 90°C or higher or the monomer having a glass transition temperature (Tg) of 30°C or lower.

[0077] In this specification, "not containing" an organic solvent means that the organic solvent is substantially not contained, and preferably less than 0.1% by mass.

[0078] <<Surfactants>> The surfactant is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include silicone surfactants, fluorine surfactants, etc. These surfactants may be used alone or in combination of two or more.

[0079] <<Polymerization inhibitor>> The polymerization inhibitor is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include 4-methoxyphenol, dibutylhydroxytoluene, phenothiazine, etc. These may be used alone or in combination of two or more.

[0080] -Viscosity of active energy ray curable composition- When a discharge means is used that discharges the active energy ray-curable composition from a nozzle, the viscosity in the range of 20° C. to 65° C., desirably the viscosity at 25° C., is preferably 3 mPa·s to 40 mPa·s, more preferably 5 mPa·s to 15 mPa·s, and particularly preferably 6 mPa·s to 12 mPa·s. It is particularly preferred that the viscosity range be satisfied without containing the organic solvent.

[0081] The viscosity of the active energy ray-curable composition can be measured using a cone-plate type rotational viscometer (VISCOMETER TVE-22L, manufactured by Toki Sangyo Co., Ltd.) with a cone rotor (1°34' x R24) at a rotation speed of 50 rpm, with the temperature of the constant temperature circulating water appropriately set in the range of 20° C. to 65° C. A circulating constant temperature bath (VISCOMATE VM-150III, manufactured by Toki Sangyo Co., Ltd.) can be used to adjust the temperature of the circulating water.

[0082] -Method of manufacturing an active energy ray-curable composition- The active energy ray-curable composition can be produced using the various components described above. The production method and conditions are not particularly limited, but the composition can be produced, for example, by adding the trifunctional adduct urethane (meth)acrylate oligomer, the monomer having a glass transition temperature of 90°C or higher, the monomer having a glass transition temperature of 30°C or lower, the pigment, the dispersant, and the like to a media-based disperser such as a ball mill, Kitty mill, disk mill, pin mill, or Dyno mill, dispersing the mixture to prepare a pigment dispersion, and then further mixing the trifunctional adduct urethane (meth)acrylate oligomer, the monomer having a glass transition temperature of 90°C or higher, the monomer having a glass transition temperature of 30°C or lower, and, if necessary, other components such as the polymerization initiator, the polymerization inhibitor, and the surfactant with the pigment dispersion. Alternatively, a media-less dispersing device such as a disperser or homogenizer may be used.

[0083] -Applications- The use of the active energy ray-curable composition is not particularly limited as long as it is in a field in which active energy ray-curable materials are generally used, and can be appropriately selected depending on the purpose. For example, the composition can be used as a molding resin, a paint, an adhesive, an insulating material, a mold release agent, a coating material, a sealing material, various resists, various optical materials, etc.

[0084] Furthermore, the active energy ray-curable composition has both good adhesion to a recording medium and good blocking resistance, and further has excellent ejection stability when ejected by inkjet. Therefore, the active energy ray-curable composition is suitably used for the active energy ray-curable ink composition of the present invention described below, and is particularly suitably used for the active energy ray-curable inkjet ink composition described below.

[0085] (Actinic Energy Ray-Curable Ink Composition and Actinic Energy Ray-Curable Inkjet Ink Composition) The actinic energy ray-curable ink composition of the present invention contains the actinic energy ray-curable composition of the present invention, and further contains other components as necessary. The actinic ray-curable ink jet ink composition of the present invention contains the actinic ray-curable ink composition, and further contains other components as necessary. The actinic ray-curable ink composition of the present invention and the actinic ray ink jet ink composition of the present invention will be described below.

[0086] <Active energy ray-curable composition> The content of the actinic energy ray-curable composition in the actinic energy ray-curable ink composition is not particularly limited and can be appropriately selected depending on the purpose. The actinic energy ray-curable ink composition may be the actinic energy ray-curable composition itself.

[0087] <Actinic energy ray-curable ink composition> The content of the actinic ray-curable ink composition in the actinic ray-inkjet ink composition is not particularly limited and can be appropriately selected depending on the purpose. The actinic ray-curable ink composition may be the actinic ray-curable ink composition itself.

[0088] <Other ingredients> The other components in the actinic ray-curable ink composition or the actinic ray-inkjet ink composition are not particularly limited and can be appropriately selected from known components typically contained in ink compositions, such as coloring materials, organic solvents, water, resins, surfactants, additives, etc. These may be used alone or in combination of two or more.

[0089] -Coloring materials- The coloring material is not particularly limited and can be appropriately selected depending on the purpose. For example, the same coloring material as those described in the "Coloring material" section of the (Active energy ray-curable composition) above can be used.

[0090] The content of the colorant in the actinic ray-curable ink composition or the actinic ray-inkjet ink composition is not particularly limited and can be appropriately selected depending on the purpose. However, the content is preferably 0.1% by mass or more and 20% by mass or less, relative to the total mass of the actinic ray-curable ink composition or the actinic ray-inkjet ink composition.

[0091] -Additives- Examples of the additives include foam inhibitors (antifoaming agents), pH adjusters, antiseptics and antifungals, chelating agents, rust inhibitors, antioxidants, ultraviolet absorbers, oxygen absorbers, light stabilizers, resins, etc. These may be used alone or in combination of two or more.

[0092] The content of the other components in the actinic ray-curable ink composition or the actinic ray-inkjet ink composition is not particularly limited as long as it does not impair the effects of the present invention, and can be appropriately selected depending on the purpose.

[0093] <Application> The active energy ray-curable ink composition and the active energy ray-curable inkjet ink composition can be used not only to form two-dimensional characters and images, and decorative coating films on various recording media, but also as a three-dimensional modeling material for forming three-dimensional solid images (three-dimensional models).

[0094] (Composition container) The composition-storage container of the present invention stores any one of the active energy ray-curable composition of the present invention, the active energy ray-curable ink composition of the present invention, and the active energy ray-curable inkjet ink composition of the present invention. That is, the composition-storage container of the present invention means a container in which any one of the active energy ray-curable composition, the active energy ray-curable ink composition, and the active energy ray-curable inkjet ink composition is stored.

[0095] In this specification, the terms "active energy ray-curable composition," "active energy ray-curable ink composition," and "active energy ray-curable inkjet ink composition" may be collectively abbreviated as "active energy ray-curable composition, etc."

[0096] The shape, size, material, etc. of the composition container are not particularly limited as long as they are suitable for the intended use and usage, but it is desirable that the material be a light-blocking material that does not transmit light, or that the container be covered with a light-blocking sheet or the like.

[0097] The composition container is suitable for use in the applications described above in the section (Active energy ray-curable composition). For example, when the active energy ray-curable composition of the present invention is used for ink applications, the container containing the ink can be used as an ink cartridge or ink bottle, which eliminates the need to directly touch the ink during ink transport, ink replacement, and other operations, thereby preventing staining of hands and clothing. Furthermore, it is possible to prevent foreign matter such as dust from getting into the ink.

[0098] (Inkjet recording method) The inkjet recording method of the present invention comprises a step of applying an actinic ray-curable inkjet ink composition containing a colorant (hereinafter sometimes referred to as a "first ink") to a recording medium (hereinafter sometimes referred to as a "first ink applying step"), and a step of applying an actinic ray-curable inkjet ink composition of the present invention to an area of ​​the recording medium to which the actinic ray-curable ink (first ink) has been applied (hereinafter sometimes referred to as a "second ink applying step"), and may further comprise other steps as necessary.

[0099] <First ink application step> The first ink application step is a step of applying an actinic ray-curable inkjet ink composition (first ink) containing a coloring material to a recording medium. The first ink application method is an inkjet ejection method.

[0100] The inkjet ejection method is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a continuous ejection type and an on-demand type. Examples of the on-demand type include a piezoelectric type, a thermal type, and an electrostatic type.

[0101] <<First Ink>> The first ink contains a coloring material, and may further contain other components as required.

[0102] -Coloring materials- The coloring material is not particularly limited and can be appropriately selected depending on the purpose. For example, the same coloring material as those described in the "Coloring material" section of the (Active energy ray-curable composition) above can be used.

[0103] The content of the coloring material in the first ink is not particularly limited and can be selected appropriately depending on the purpose, but it is preferably 0.1% by mass or more and 20% by mass or less with respect to the total mass of the first ink.

[0104] -Other ingredients- The other components are not particularly limited and can be appropriately selected depending on the purpose. Examples include the same components as those other than the colorant in <Other components> in (Activin energy ray-curable ink composition and activation energy ray-curable inkjet ink composition) above.

[0105] The content of the other components in the first ink is not particularly limited and can be appropriately selected depending on the purpose.

[0106] <<Recording Media>> The recording medium is not particularly limited and can be appropriately selected depending on the purpose. Examples include paper, thread, fiber, fabric, leather, metal, film, plastic, glass, wood, ceramics, and composite materials thereof. In this specification, the terms "recording medium", "substrate" and "substrate" are synonymous.

[0107] The shape of the recording medium is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a sheet shape, etc. The recording medium may be configured to allow only single-sided printing or double-sided printing.

[0108] The recording medium is not limited to those commonly used as recording media as described above, but may also be appropriately used such as cardboard; building materials such as wallpaper and flooring; concrete; cloth for clothing such as T-shirts; textiles; leather; etc.

[0109] <Second ink application step> The second ink application step is a step of applying the actinic energy ray-curable inkjet ink composition (second ink) of the present invention to the area of ​​the recording medium to which the actinic energy ray-curable inkjet ink composition (first ink) has been applied in the first ink application step. The method for applying the second ink is an inkjet ejection method, and the mode thereof is the same as the mode described in the <First ink application step>.

[0110] <Other processes> The other steps are not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a first curing step and a second curing step.

[0111] <<First curing process>> The first curing step is a step that is carried out between the first ink application step and the second ink application step, and is a step of curing the first ink in the area where the first ink has been applied before the second ink is applied.

[0112] The method for curing the first ink is not particularly limited and can be appropriately selected depending on the purpose. Examples include a method of curing by heating, and a method of curing by using active energy rays.

[0113] The active energy rays are not particularly limited, and the same ones as those described in the section "Active energy rays" below (Two-dimensional or three-dimensional image forming apparatus and two-dimensional or three-dimensional image forming method) can be used.

[0114] <<Second curing process>> The second curing step is a step that is carried out after the second ink applying step, and is a step of curing the second ink in the region where the second ink has been applied.

[0115] The method for curing the second ink is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a method of curing by heating, a method of curing by using active energy rays, etc. Among these, curing by using active energy rays is preferred.

[0116] The inkjet recording method can be used not only as a method for forming two-dimensional characters and images, and decorative coating films on various recording media, but also as a method for forming three-dimensional solid images (three-dimensional shaped objects).

[0117] (Two-dimensional or three-dimensional image forming device and two-dimensional or three-dimensional image forming method) The two-dimensional or three-dimensional image forming device of the present invention comprises a containing means and an irradiating means, and preferably further comprises a discharging means, and further comprises other means as necessary. The two-dimensional or three-dimensional image forming method of the present invention includes an irradiation step, and preferably further includes a discharge step, and further includes other steps as necessary. In this specification, a "two-dimensional or three-dimensional image forming apparatus" may be abbreviated as an "image forming apparatus," and a "two-dimensional or three-dimensional image forming method" may be abbreviated as an "image forming method."

[0118] In the two-dimensional or three-dimensional image forming method of the present invention, an image may be formed by applying active energy rays to the active energy ray-curable composition or the like, or by heating the active energy ray-curable composition or the like.

[0119] <Means of Containment> The storage means is a means for storing any one of the active energy ray-curable composition of the present invention, the active energy ray-curable ink composition of the present invention, and the active energy ray-curable inkjet ink composition of the present invention (the active energy ray-curable composition, etc.). The storage means may be a container for storing the composition of the present invention.

[0120] The number of the storage means in the image forming apparatus is not particularly limited and can be appropriately selected depending on the purpose. For example, when the image forming apparatus has the active energy ray-curable compositions or the like of multiple colors such as yellow, magenta, cyan, and black, it is preferable that the storage means independently store each of the multiple active energy ray-curable compositions or the like.

[0121] Furthermore, when the image forming apparatus has the plurality of active energy ray-curable compositions, the containing means may be an ink cartridge, and such an ink cartridge is also within the scope of the present invention.

[0122] The ink cartridge includes the plurality of active energy ray-curable compositions and a container, and may further include other components as required. The ink cartridge is advantageous in that there is no need to directly touch the ink when replacing the ink, so there is no need to worry about staining your fingers or clothes, and it is possible to prevent foreign matter such as dust from getting into the ink.

[0123] The ink cartridge may contain the plurality of active energy ray-curable compositions and the like integrally, or may contain the plurality of active energy ray-curable compositions and the like independently.

[0124] The container is not particularly limited, and its shape, structure, size, material, etc. can be appropriately selected depending on the purpose. For example, a container having an ink bag formed from an aluminum laminate film, a resin film, etc. is preferred.

[0125] The method for producing the ink cartridge is not particularly limited, and the ink cartridge can be produced by any known method.

[0126] The ink cartridge is preferably configured to be used by further accommodating the plurality of active energy ray-curable compositions housed in a container such as an ink bag in a cartridge case (e.g., a plastic case) and being detachably mounted on the image forming apparatus, thereby simplifying ink refilling and replacement and improving operability.

[0127] <Discharge means and discharge process> The discharge means is a means for discharging the active energy ray-curable composition or the like contained in the container means. The discharging step is a step of discharging the active energy ray-curable composition and the like contained in the container. The ejection step is preferably carried out before the irradiation step. The discharging step is preferably carried out by the discharging means.

[0128] The method for applying the active energy ray-curable composition and the like is not particularly limited and can be appropriately selected depending on the purpose, but is preferably a discharge method, and more preferably an inkjet discharge method.

[0129] The inkjet ejection method is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a continuous ejection type and an on-demand type. Examples of the on-demand type include a piezoelectric type, a thermal type, and an electrostatic type.

[0130] <Irradiation means and irradiation process> The irradiation means is a means for irradiating any one of the active energy ray-curable composition, active energy ray-curable ink composition, and active energy ray-curable inkjet ink composition of the present invention (the active energy ray-curable composition, etc.) with active energy rays. The irradiation step is a step of irradiating any one of the active energy ray-curable composition, active energy ray-curable ink composition, and active energy ray-curable inkjet ink composition of the present invention (the active energy ray-curable composition, etc.) with active energy rays. The irradiation step is preferably carried out by the irradiation means. The active energy ray-curable composition is cured by the irradiation means and the irradiation step.

[0131] Examples of the curing method for curing the active energy ray-curable composition of the present invention include heat curing, active energy ray curing, etc. Among these, active energy ray curing is preferred.

[0132] <<Active energy rays>> The active energy rays are not particularly limited as long as they can impart the energy necessary to promote a polymerization reaction between the trifunctional adduct urethane (meth)acrylate oligomer in the active energy ray-curable composition, the monomer having a glass transition temperature of 90°C or higher, and the monomer having a glass transition temperature of 30°C or lower, and can be appropriately selected depending on the purpose. Examples of the active energy rays include ultraviolet rays, electron beams, α-rays, β-rays, γ-rays, and X-rays. These rays may be used alone or in combination of two or more. In particular, when a high-energy light source is used, the polymerization reaction can be promoted without using the polymerization initiator.

[0133] When the active energy rays are ultraviolet rays, mercury-free devices are strongly desired from the viewpoint of environmental protection, and replacement with GaN-based semiconductor ultraviolet light-emitting devices is extremely useful from both an industrial and environmental perspective. Furthermore, ultraviolet light-emitting diodes (UV-LEDs) and ultraviolet laser diodes (UV-LDs) are small, have a long life, are highly efficient, and are low cost, making them preferable as ultraviolet light sources. Among these, from the viewpoint of energy saving and device miniaturization, ultraviolet light irradiated from ultraviolet light-emitting diodes (hereinafter also referred to as UV-LEDs) preferably has a peak wavelength of 285 nm to 405 nm, and more preferably has a peak wavelength of 365 nm to 405 nm.

[0134] In addition, the light absorption spectrum of a polymerization initiator is generally broad, and the use of a UV-LED that irradiates a narrow specific wavelength range makes it difficult to improve the curability of the active energy ray-curable composition. Therefore, it is preferable to use the active energy ray-curable composition of the present invention, which has curability that allows sufficient curing even when a UV-LED is used.

[0135] <Other means and other steps> The other means and steps are not particularly limited and can be appropriately selected depending on the purpose.

[0136] The two-dimensional or three-dimensional image forming apparatus and the two-dimensional or three-dimensional image forming method will be described below with reference to the drawings, but the present invention is not limited thereto.

[0137] FIG. 1 shows an example of an image forming apparatus equipped with an inkjet ejection unit. Each color printing unit 23a, 23b, 23c, and 23d includes an ink cartridge as a storage unit containing a yellow, magenta, cyan, or black active energy ray-curable ink composition and an ejection head. The ink is then ejected onto a recording medium 22 supplied from a supply roll 21. The ink is then cured by irradiating it with active energy rays from light sources 24a, 24b, 24c, and 24d as an irradiation unit for curing the ink, forming a color image. The recording medium 22 is then transported to a processing unit 25 and a print take-up roll 26. Each printing unit 23a, 23b, 23c, and 23d may be equipped with a heating mechanism to liquefy the ink at the ink ejection section. If necessary, a mechanism for cooling the recording medium to approximately room temperature, either by contact or non-contact, may also be provided. In addition, as an inkjet recording method, either a serial method in which the recording medium moves intermittently according to the width of the ejection head and the head moves to eject ink onto the recording medium, or a line method in which the recording medium moves continuously and ink is ejected onto the recording medium from a head held at a fixed position can be applied.

[0138] Furthermore, the active energy ray irradiation from the light sources 24a, 24b, and 24c may be weakened or omitted, and after printing multiple colors, the active energy ray may be irradiated from the light source 24d, which can save energy and reduce costs.

[0139] Recorded materials recorded using the active energy ray-curable composition of the present invention include not only those printed on smooth surfaces such as ordinary paper or resin films, but also those printed on uneven printing surfaces and those printed on printing surfaces made of various materials such as metals and ceramics. Furthermore, by laminating two-dimensional images, it is also possible to form images (two-dimensional or three-dimensional images) or three-dimensional objects with a partial three-dimensional effect.

[0140] Fig. 2 is a schematic diagram showing another example of an image forming apparatus (a device for forming a three-dimensional solid image) of the present invention. The image forming apparatus 39 in Fig. 2 uses a head unit (movable in the AB direction) in which inkjet heads are arranged, and ejects a first active energy ray-curable composition or the like from ejection head unit 30 for a model, and ejects a second active energy ray-curable composition or the like having a different composition from the first active energy ray-curable composition or the like from ejection head units 31 and 32 for a support, and laminates these active energy ray-curable compositions or the like while curing them with adjacent ultraviolet irradiation means 33 and 34. More specifically, for example, a second active energy ray-curable composition or the like is ejected from the ejection head units 31 and 32 onto a support substrate 37, and the composition is irradiated with active energy rays to solidify the composition, forming a first support layer having a reservoir. Then, a first active energy ray-curable composition or the like is ejected from the ejection head unit 30 into the reservoir, and the composition is irradiated with active energy rays to solidify the composition, forming a first object layer. This process is repeated multiple times while lowering the vertically movable stage 38 in accordance with the number of layers to be stacked, thereby stacking the support layer and the object layer to produce a three-dimensional object 35. Thereafter, the support layer stacking unit 36 ​​is removed as necessary. Although only one ejection head unit 30 for the object is shown in FIG. 2, two or more may be provided.

[0141] This three-dimensional modeling material may be used, for example, as a binder between powder particles in a powder additive manufacturing process, in which three-dimensional modeling is performed by repeatedly curing and stacking powder layers. It may also be used as a three-dimensional component (model material) or support member (support material) in an additive manufacturing process (stereolithography) such as that shown in FIG. 2 and FIGS. 3A-3D. FIG. 2 illustrates a method for three-dimensional modeling in which an active energy ray-curable composition of the present invention is dispensed into a predetermined area, cured by irradiation with active energy rays, and sequentially stacked. FIGS. 3A-3D illustrate a method for three-dimensional modeling in which a storage pool (storage unit) 1 for the active energy ray-curable composition of the present invention 5 is irradiated with active energy rays 4 to form a cured layer 6 of a predetermined shape on a movable stage 3, and these layers are sequentially stacked. First, in FIG. 3A, the storage pool (storage unit) 1 for the active energy ray-curable composition of the present invention 5 is irradiated with active energy rays 4. Next, in Fig. 3B, a cured layer 6 having a predetermined shape is formed on the movable stage 3 by irradiation with active energy rays 4. Next, in Fig. 3C, the movable stage 3 is lowered. Next, in Fig. 3D, another cured layer 6 is formed on the obtained cured layer 6 by irradiation with active energy rays 4.

[0142] As a three-dimensional modeling apparatus for forming a three-dimensional object using the active energy ray-curable composition of the present invention, a known one can be used without any particular limitation and can be appropriately selected depending on the purpose. For example, it may be one equipped with a means for storing, supplying, and discharging the composition, and an active energy ray irradiation means.

[0143] In this way, by applying the active energy ray-curable composition or the like to a recording medium and curing it using the image forming apparatus and the image forming method, a two-dimensional or three-dimensional image is formed. The two-dimensional or three-dimensional image thus formed is also included in the scope of the present invention.

[0144] Examples of the two-dimensional image include characters, symbols, figures, or combinations thereof, and solid images.

[0145] The three-dimensional image may be, for example, a three-dimensional object.

[0146] The average thickness of the three-dimensional object is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 μm or more.

[0147] The two-dimensional or three-dimensional image is formed using the active energy ray-curable composition or the like, and therefore has excellent water resistance, meaning that the two-dimensional or three-dimensional image formed on the non-permeable recording medium can maintain good adhesion even after immersion in water.

[0148] (cured product) The cured product of the present invention is formed by curing at least one of the active energy ray-curable composition of the present invention, the active energy ray-curable ink composition of the present invention, and the active energy ray-curable inkjet ink composition of the present invention with active energy rays.

[0149] (decorative body) The decorated body of the present invention is a substrate on which a surface decoration made of the cured product of the present invention is applied. That is, it is a molded article obtained by processing a structure in which the cured product is formed on the substrate.

[0150] The substrate is not particularly limited and may be the same as the recording medium described in the section (Inkjet recording method). Among these, plastic substrates are preferred from the viewpoint of processability.

[0151] The shape of the decorative body is not particularly limited and can be appropriately selected depending on the purpose. For example, the cured product formed into a sheet or film shape may be subjected to molding processing such as heat stretching or punching.

[0152] <Application> The decorated article of the present invention is suitable for use in applications where the surface needs to be shaped after decoration, such as meters and operation panels for automobiles, office automation equipment, electrical equipment, electronic equipment, cameras, etc. [Example]

[0153] The present invention will be specifically explained below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to these synthesis examples and examples.

[0154] (Synthesis Example 1: Synthesis of Urethane Acrylate Oligomer A) A 500 mL flask equipped with a stirrer, thermometer, and condenser was charged with 33 parts by mass of toluene and 4.8 parts by mass of stearyl alcohol (NAA-46, manufactured by NOF Corporation) and heated to 40°C. After confirming that the stearyl alcohol was completely dissolved, 50 parts by mass of hexamylene diisocyanate modified with trimethylolpropane adduct (Burnoc DN-950; manufactured by DIC Corporation, NV: 75, NCO%: 12) was charged and heated to 70°C. After reacting at 70°C for 30 minutes, 0.02 parts by mass of dibutyltin laurate was charged and the temperature was maintained at 70°C for 3 hours. Subsequently, 63.9 parts by mass of polycaprolactone-modified hydroxyethyl acrylate (Placcel FA3, manufactured by Daicel Corporation, hydroxyl value: 122), 0.02 parts by mass of dibutyltin laurate, and 0.02 parts by mass of hydroquinone monomethyl ether were added, and the mixture was maintained at 70°C for 3 hours to terminate the reaction. 60.7 parts by mass of toluene were then added to obtain urethane acrylate oligomer A (trifunctional adduct) with a solids content of 50% by mass.

[0155] (Synthesis Example 2: Synthesis of Urethane Acrylate Oligomer B) A 500 mL flask equipped with a stirrer, thermometer, and condenser was charged with 60.8 parts by mass of toluene and 8.4 parts by mass of stearyl alcohol (NAA-46), and the temperature was raised to 40°C. After confirming that the stearyl alcohol was completely dissolved, 50 parts by mass of isocyanurate-modified hexamethylene diisocyanate (Takenate (registered trademark) D-170N, manufactured by Mitsui Chemicals, Inc., NCO%: 20.9) was charged, and the temperature was raised to 70°C. After reacting at 70°C for 30 minutes, 0.02 parts by mass of dibutyltin laurate was charged, and the temperature was maintained at 70°C for 3 hours. Subsequently, 83.5 parts by mass of polycaprolactone-modified hydroxyethyl acrylate (Placcel FA2D, manufactured by Daicel Corporation), 0.02 parts by mass of dibutyltin laurate, and 0.02 parts by mass of hydroquinone monomethyl ether were added, and the mixture was maintained at 70°C for 3 hours to terminate the reaction. 81.1 parts by mass of toluene were then added to obtain urethane acrylate oligomer B (trifunctional isocyanurate) with a solids content of 50% by mass.

[0156] (Synthesis Example 3: Synthesis of urethane acrylate oligomer C) A 500 mL flask equipped with a stirrer, thermometer, and condenser was charged with 78.3 parts by mass of toluene and 8.5 parts by mass of stearyl alcohol (NAA-46), and the temperature was raised to 40°C. After confirming that the stearyl alcohol was completely dissolved, 50 parts by mass of biuret-modified hexamethylene diisocyanate (Duranate 24A-90CX, manufactured by Asahi Kasei Corporation, NV: 90, NCO%: 21.2) was charged, and the temperature was raised to 70°C. After reacting at 70°C for 30 minutes, 0.02 parts by mass of dibutyltin laurate was charged, and the temperature was maintained at 70°C for 3 hours. Subsequently, 140.8 parts by mass of polycaprolactone-modified hydroxyethyl acrylate (Placcel FA4, manufactured by Daicel Corporation, hydroxyl value: 98), 0.02 parts by mass of dibutyltin laurate, and 0.02 parts by mass of hydroquinone monomethyl ether were added, and the mixture was maintained at 70°C for 3 hours to terminate the reaction. 111 parts by mass of toluene were then added to obtain urethane acrylate oligomer C (trifunctional biuret compound) with a solids content of 50% by mass.

[0157] Example 1 <Preparation of active energy ray-curable composition> An oligomer (urethane acrylate oligomer A obtained in Synthesis Example 1), a monomer having a Tg of 90°C or higher, a monomer having a Tg of 30°C or lower, other monomers, a polymerization initiator (TPO), and a polymerization inhibitor (MEHQ) were mixed in a Three-One Motor (manufactured by Shinto Scientific Co., Ltd.) based on the composition (mass%) shown in Table 1 below to obtain an active energy ray-curable composition.

[0158] <Preparation of cured product> A 10 μm thick film was formed on an acrylic substrate using an active energy ray-curable composition, and the coating film was illuminated with an LED lamp (peak wavelength 395 nm, 3,000 mJ / cm) manufactured by Ushio Inc. 2 ) to cure the composition, yielding a cured product.

[0159] (Examples 2 to 5 and Comparative Examples 1 to 15) In Example 1, the active energy ray-curable composition and its cured product were obtained in the same manner as in Example 1, except that the composition and content (mass%) of the active energy ray-curable composition were changed to the composition and content (mass%) shown in Tables 1 to 3.

[0160] Next, the active energy ray-curable compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 15 were evaluated for "continuous discharge stability" as described below, and the cured products obtained in Examples 1 to 5 and Comparative Examples 1 to 15 were evaluated for "blocking resistance" and "substrate adhesion" as described below. The results are shown in Tables 1 to 3.

[0161] <Blocking resistance> Blocking resistance was evaluated based on the presence or absence of sticking between the coating film and the substrate and the degree of change in the coating film after placing the cured coating surface of each cured product on an acrylic substrate and applying a load of 5 kg per A4 size. The coating was then left at room temperature for 24 hours and evaluated according to the following criteria. [Evaluation criteria] ◎: No sticking and no change in the coating 〇: Sticking occurs, but there is no change in the coating △: Sticking occurs, and the change in the coating is less than 10% ×: Sticking occurs and the change in coating is 10% or more.

[0162] <Adhesion to substrate> The adhesion of each cured product to the substrate was evaluated according to the cross-cut method of adhesion test JIS K5600-5-6, based on the following criteria. [Evaluation criteria] 〇: No peeling at all △: Peeling only along the cutter notch ×: The mass peels off

[0163] <Continuous discharge stability> Using an inkjet ejection device having an inkjet head MH5420 (manufactured by Ricoh Company, Ltd.), the number of nozzles that failed to eject when each active energy ray-curable composition was continuously ejected for 1 minute at a frequency of 28 kHz under conditions where the flying speed of the composition was 7±1 m / s was measured, and the ejection stability was evaluated based on the following criteria. [Evaluation criteria] ◎: The number of non-ejecting nozzles is 0 ○: The number of non-ejecting nozzles is 1 or more but less than 4 △: The number of non-ejecting nozzles is 4 or more but less than 10 ×: 10 or more non-ejecting nozzles

[0164] <Overall Judgment> In the three evaluation results of the "blocking resistance", the "adhesion to substrate", and the "continuous discharge stability", if there was no "x" then the overall judgment was "good", and if there was even one "x" then the overall judgment was "x".

[0165] [Table 1]

[0166] [Table 2]

[0167] [Table 3]

[0168] (Examples 6 to 14 and Comparative Examples 16 to 22) <Preparation of active energy ray-curable ink composition> Based on the compositions and contents (mass %) shown in Tables 4 and 5, the first inks and second inks of Examples 6 to 14 and Comparative Examples 16 to 22 were prepared by a conventional method.

[0169] <Preparation of cured product> Using each of the first inks and second inks obtained in Examples 6 to 14 and Comparative Examples 16 to 22, a 10 μm film was formed on an acrylic substrate, and the coating film was then applied to an LED lamp (peak wavelength 395 nm, 3,000 mJ / cm) manufactured by Ushio Inc. 2 ) to cure the composition, yielding a cured product.

[0170] Next, the cured products of the first ink and the cured products of the second ink obtained in Examples 6 to 14 and Comparative Examples 16 to 22 were evaluated for "blocking resistance" and "substrate adhesion" using the same methods as in Examples 1 to 5 and Comparative Examples 1 to 15. Furthermore, the cured products of the first ink and the cured products of the second ink obtained in Examples 6 to 14 and Comparative Examples 16 to 22 were evaluated for "stretchability" as follows. The results are shown in Tables 4 and 5.

[0171] <Stretchability> The condition of the coating film immediately after curing, printed to 3 cm x 10 cm, was visually observed when it was stretched 5 cm in the longitudinal direction (the coating film itself was stretched to 15 cm), and evaluated based on the following evaluation criteria. The evaluation results of "◎", "◯", and "△" indicated that the coating was usable. [Evaluation criteria] ◎: No cracks ○: Minor cracks △: Cracks present ×: Breaks when stretched

[0172] <Overall Judgment> In the three evaluation results of the "blocking resistance", the "adhesion to substrate", and the "stretchability", if there was no "x" then the overall judgment was "good", and if there was even one "x", then the overall judgment was "x".

[0173] [Table 4]

[0174] [Table 5]

[0175] The present invention includes, for example, the following aspects. <1> a trifunctional adduct urethane (meth)acrylate oligomer; A monomer with a glass transition temperature of 90°C or higher, a monomer having a glass transition temperature of 30°C or less; Contains The active energy ray-curable composition is characterized in that the content of the monomer having a glass transition temperature of 90°C or higher is 10% by mass or more and 30% by mass or less, and the content of the monomer having a glass transition temperature of 30°C or lower is 20% by mass or more and 50% by mass or less. <2> The content of the monomer having a glass transition temperature of 90° C. or higher is 10% by mass or more and 20% by mass or less, and the content of the monomer having a glass transition temperature of 30° C. or lower is 30% by mass or more and 40% by mass or less. <1> 1. The active energy ray-curable composition according to claim 1. <3> The content of the trifunctional adduct urethane (meth)acrylate oligomer is 1.0 mass % or more and 5.0 mass % or less. <1> from <2> The active energy ray-curable composition according to any one of the above items. <4> The aforementioned <1> from <3> 1. An actinic ray-curable ink composition comprising the actinic ray-curable composition according to any one of claims 1 to 9. <5> The aforementioned <4> 1. An actinic ray-curable ink jet ink composition comprising the actinic ray-curable ink composition according to claim 1. <6> applying an actinic ray-curable inkjet ink composition containing a colorant to a recording medium; The active energy ray curable ink composition is applied to the area of ​​the recording medium. <5> applying the actinic ray-curable inkjet ink composition according to the above; and a method for ink jet recording, the method comprising: <7> The aforementioned <1> from <3> The active energy ray-curable composition according to any one of the preceding claims. <4> and the active energy ray-curable ink composition according to the above item. <5> 1. A composition container characterized by containing any one of the actinic ray-curable inkjet ink compositions described in 1. <8> The aforementioned <1> from <3> The active energy ray-curable composition according to any one of the preceding claims. <4> and the active energy ray-curable ink composition according to the above item. <5> a storage means for storing any one of the actinic ray-curable inkjet ink compositions described in an irradiation means for irradiating with active energy rays; The present invention relates to a two-dimensional or three-dimensional image forming device.

[0176] The aforementioned <1> from <3> The active energy ray-curable composition according to any one of the preceding claims. <4> The actinic ray curable ink composition according to any one of claims 1 to 5, <5> The actinic energy ray-curable inkjet ink composition according to the present invention <6> The ink jet recording method according to the <7> A container for storing the composition according to the above item, <8> The two-dimensional or three-dimensional image forming apparatus described above can solve the above-mentioned problems in the prior art and achieve the object of the present invention. [Explanation of symbols]

[0177] 21 Supply Roll 22 Recording media 23a, 23b, 23c, 23d Printing units 24a, 24b, 24c, 24d light source 25 Processing Unit 26 Printed material winding roll 30. Discharge head unit for modeling 31, 32 Support ejection head unit 33, 34 Ultraviolet irradiation means 35 Three-dimensional sculpture 36 Support layer section 37 Object support substrate 38 Movable Stage 39 Image forming device 1. Storage pool 3 Movable stage 4. Active energy rays 5. Active energy ray curable compositions, etc. 6 Hardened layer [Prior art documents] [Patent documents]

[0178] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-256053

Claims

1. a trifunctional adduct urethane (meth)acrylate oligomer; a monomer having a glass transition temperature of 90°C or higher; a monomer having a glass transition temperature of 30°C or less; Contains the functional group of the trifunctional adduct urethane (meth)acrylate oligomer is an active energy ray-curable functional group having CH 2 =; the content of the trifunctional adduct urethane (meth)acrylate oligomer is 1.0% by mass or more and 5.0% by mass or less, an active energy ray-curable composition, wherein the content of the monomer having a glass transition temperature of 90°C or higher is 10% by mass or more and 30% by mass or less, and the content of the monomer having a glass transition temperature of 30°C or lower is 20% by mass or more and 50% by mass or less.

2. 2. The active energy ray-curable composition according to claim 1, wherein the content of the monomer having a glass transition temperature of 90°C or higher is 10% by mass or more and 20% by mass or less, and the content of the monomer having a glass transition temperature of 30°C or lower is 30% by mass or more and 40% by mass or less.

3. 3. The active energy ray-curable composition according to claim 1, wherein the trifunctional adduct urethane (meth)acrylate oligomer is a polymer of an organic isocyanate (A) having three isocyanate groups in one molecule, a long-chain alkyl alcohol (B), and a polycaprolactone-modified hydroxyethyl (meth)acrylate (C).

4. An actinic ray-curable ink composition comprising the actinic ray-curable composition according to claim 1 .

5. An actinic ray-curable ink jet ink composition comprising the actinic ray-curable ink composition according to claim 4.

6. applying an actinic ray-curable inkjet ink composition containing a colorant to a recording medium; applying the actinic ray-curable inkjet ink composition according to claim 5 to the area of ​​the recording medium to which the actinic ray-curable ink composition has been applied; An inkjet recording method comprising:

7. A composition container containing the active energy ray-curable composition according to any one of claims 1 to 3, the active energy ray-curable ink composition according to claim 4, and the active energy ray-curable inkjet ink composition according to claim 5.

8. a container for containing the actinic ray-curable composition according to any one of claims 1 to 3, the actinic ray-curable ink composition according to claim 4, or the actinic ray-curable inkjet ink composition according to claim 5; an irradiation means for irradiating with active energy rays; A two-dimensional or three-dimensional image forming device comprising:

Images