Active energy ray curing composition, active energy ray curing ink composition, inkjet ink composition, composition container, apparatus for forming two-dimensional or three-dimensional image, method of forming two-dimensional or three-dimensional image, cured matter, decorative object, laminate, member for flexible device, and flexible device

Abstract

To provide an active energy ray curing composition which can form cured matter having strong adhesion, even after being placed under extremely severe conditions, such as in hot water or an alkali solution.SOLUTION: An active energy ray curing composition contains a polymerizable monomer having a phosphoric acid ester group, a polyester resin having an unsaturated bond, and a polyfunctional monomer having two or more polymerizable functional groups in its molecule. The content of the polyfunctional monomer having two or more polymerizable functional groups in its molecule is 10 mass% or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an active energy ray-curable composition, an active energy ray-curable ink composition, an inkjet ink composition, a composition storage container, a two-dimensional or three-dimensional image forming apparatus, a two-dimensional or three-dimensional image forming method, a cured product, a decorative body, a laminate, a member for a flexible device, and a flexible device. [Background technology]

[0002] Inkjet printers are increasingly being used for a wide variety of industrial applications, including printing large advertisements, printing on wallpaper, printing on packages, printing on beverage containers, etc. Examples of ink compositions used in inkjet printers include aqueous inkjet ink compositions, oil-based inkjet ink compositions, and actinic ray-curable inkjet ink compositions. Since the active energy ray-curable composition is cured by irradiation with active energy rays, it has excellent drying properties even on a non-permeable substrate. In addition, the cured product obtained by curing the active energy ray-curable composition after printing is also required to have durability against treatment under very severe conditions. For example, in applications related to food and drink, such as beverage containers, the containers may be treated with hot water, alkaline solutions, etc., from the viewpoint of sterilization of the containers, etc. Therefore, the cured product obtained by curing the active energy ray-curable composition after printing is required to have durability against treatment with hot water, alkaline solutions, etc.

[0003] As a curable composition having high adhesive strength and excellent heat resistance and moisture resistance, for example, a curable composition containing isosorbide di(meth)acrylate (A), a monovalent organic acid (B), a radical initiator (C) and an acid generator (D), or a radical polymerizable substance (E) other than (A), (B), (C), (D) and (A) has been proposed (see, for example, Patent Document 1). Furthermore, as an inkjet ink composition capable of obtaining a resin-coated metal sheet having a resin film with sufficient adhesion to metal and excellent strength, there has been proposed an inkjet ink composition comprising a polymerizable monomer polymerizable by active energy rays and a photopolymerization initiator, the polymerizable monomer containing, in total, 0.5 to 13 mass % of a polymerizable phosphate ester compound having a phosphate ester group and an ethylenic double bond group in the molecule and 10 to 75 mass % of a monofunctional monomer having one ethylenic double bond group in the molecule and no phosphate ester group, the photopolymerization initiator comprising an acylphosphine oxide initiator and an α-hydroxyketone initiator having one or less phenyl groups in the skeleton, and having a viscosity at 25°C of 3 to 50 mPa s (see, for example, Patent Document 2). Furthermore, as an energy curable ink or coating having improved adhesion to a flexible substrate such as a flexible film, for example, an energy curable printing ink or coating composition has been proposed that contains an acrylate group-containing monomer, an acrylate group-containing oligomer, or a combination thereof, wherein the composition has an acrylate group relative concentration of more than 4.0 (see, for example, Patent Document 3). 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 can form a cured product having excellent adhesion even after exposure to extremely harsh conditions such as hot water or an alkaline solution. [Means for solving the problem]

[0005] The active energy ray-curable composition of the present invention as a means for solving the above problems contains a polymerizable monomer having a phosphate ester group and a polyester resin. Effect of the Invention

[0006] According to the present invention, it is possible to provide an active energy ray-curable composition that can form a cured product having excellent adhesion even after exposure to extremely harsh conditions such as hot water or an alkaline solution. [Brief description 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 according to the present invention. [Diagram 2] FIG. 2 is a schematic diagram showing an 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 an example of another two-dimensional or three-dimensional image forming apparatus according to the present invention. [Figure 3B] FIG. 3B is a schematic diagram showing an example of another two-dimensional or three-dimensional image forming apparatus according to the present invention. [Figure 3C] FIG. 3C is a schematic diagram showing an example of another two-dimensional or three-dimensional image forming apparatus according to the present invention. [Figure 3D] FIG. 3D is a schematic diagram showing another example of a two-dimensional or three-dimensional imaging apparatus according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] (Active energy ray curable composition) The active energy ray-curable composition of the present invention contains a polymerizable monomer having a phosphate group and a polyester resin, and further contains other components as required.

[0009] Although the heat resistance and moisture resistance of the curable composition described in Patent Document 1 have been examined, the hot water resistance has not been examined. In other words, there has been no examination as to whether the cured product has adhesion even after being exposed to extremely harsh conditions such as hot water or an alkaline solution. Furthermore, although the adhesion of the inkjet ink composition described in Patent Document 2 has been investigated, there is a problem in that the adhesion may be poor after immersion in hot water, an alkaline solution, or the like. Furthermore, in the energy curable printing ink or coating composition described in Patent Document 3, only acidic acrylate oligomer, acrylic acid, β-carboxyethyl acrylate, and the like are described as exemplary acid-modified adhesion promoters, and although adhesiveness has been examined, there has been no examination as to whether the cured product exhibits adhesiveness even after being exposed to extremely harsh conditions such as hot water or an alkaline solution.

[0010] As a result of extensive research, the present inventors have found that by incorporating a polymerizable monomer having a phosphate ester group and a polyester resin in the composition, it is possible to obtain an active energy ray-curable composition that can form a cured product having excellent adhesion even after treatment under extremely harsh conditions, such as treatment with hot water or an alkaline solution. The reason for this is not clear, but is presumed to be as follows. For example, when an active energy ray-curable composition is applied to a non-permeable substrate such as glass, the composition does not penetrate into the substrate, and the adhesion between the cured product and the substrate tends to be low. However, it is believed that by using a polymerizable monomer having a phosphate ester group, the phosphate ester group portion dissolves the substrate and exerts an interaction between the substrate and the composition, thereby enabling the formation of extremely high adhesion between the cured product of the composition and the substrate. In addition, the use of polyester resin also exhibits high adhesion and is thought to have high affinity with polymerizable monomers having a phosphate ester group that has an ester structure similar to a polyester structure, making the cured product formed on the substrate stronger and suppressing cohesive failure of the cured product. It is believed that a decrease in adhesion between a substrate and a cured product can occur, for example, when a cured product formed on a substrate is immersed in hot water or an alkaline solution, resulting in a significant decrease in adhesion at the interface between the substrate and the cured product or inside the cured product due to the hot water or alkaline solution penetrating therein. However, by incorporating a polymerizable monomer having a phosphate ester group and a polyester resin in the composition, it is possible to achieve excellent interaction with the substrate and excellent strength of the cured product, and it is believed that penetration of hot water or alkaline solutions into the interface between the substrate and the cured product or into the interior of the cured product can be suppressed, and excellent adhesion can be achieved even after immersion in hot water or alkaline solutions. In this specification, "hot water" means water heated to 80°C or higher at normal pressure, that is, water having a temperature of 80°C or higher and 100°C or lower at normal pressure.

[0011] <Polymerizable monomer having a phosphoric acid ester group> The active energy ray-curable composition of the present invention contains a polymerizable monomer having a phosphate ester group. In the present invention, by containing a polymerizable monomer having a phosphate ester group, for example, when the substrate is glass, the phosphate ester group portion dissolves the substrate, thereby improving the interaction between the substrate and the composition, and very high adhesion can be exhibited between the cured product of the composition and the substrate.

[0012] The polymerizable functional group in the polymerizable monomer having a phosphate ester group is not particularly limited and may be appropriately selected depending on the purpose. Examples of the polymerizable functional group include a (meth)acryloyl group.

[0013] Furthermore, the polymerizable monomer having a phosphate ester group is preferably a polyfunctional monomer having two or more polymerizable functional groups in the molecule, and more preferably a polyfunctional monomer having three polymerizable functional groups in the molecule. When the polymerizable monomer having a phosphate ester group is a polyfunctional monomer having two or more polymerizable functional groups in the molecule, the adhesion between the cured product of the composition and the substrate after immersion in hot water or an alkaline solution can be improved.

[0014] Examples of the polymerizable monomer having a phosphate group include 2-acryloyloxyethyl acid phosphate (number of polymerizable functional groups: 1), 2-(meth)acryloyloxyethyl dihydrogen phosphate (number of polymerizable functional groups: 1), and dipentaerythritol penta(meth)acryloyloxydihydrogen phosphate (number of polymerizable functional groups: 5). These may be used alone or in combination of two or more. Commercially available products may be used as the polymerizable monomer having an acidic group. Examples of the commercially available products include SR9050NS (manufactured by Sartomer Corporation, number of polymerizable functional groups: 1), SR9051NS (manufactured by Sartomer Corporation, number of polymerizable functional groups: 3), and Light Acrylate P-1A(N) (manufactured by Kyoeisha Chemical Co., Ltd., number of polymerizable functional groups: 1).

[0015] The content of the polymerizable monomer having a phosphate group is preferably from 3% by mass to 10% by mass based on the total amount of the composition. When the content of the polymerizable monomer having a phosphate ester group is 3% by mass or more and 10% by mass or less based on the total amount of the composition, it is possible to obtain an active energy ray curable composition that is excellent in resistance to deterioration due to contact with liquid and in discharge stability even after immersion in hot water or an alkaline solution. The term "contact with liquid" refers to contact of a member such as a tool used for applying the active energy ray-curable composition, such as an inkjet head in the case of inkjet printing, with the active energy ray-curable composition. If the content of the polymerizable monomer having a phosphate ester group exceeds 10 mass %, the metal components may deteriorate, particularly when contacted with the metal components. Therefore, from the viewpoint of resistance to deterioration due to contact with liquids, it is preferable that the content of the polymerizable monomer having a phosphate ester group is 10 mass % or less.

[0016] <Polyester resin> The polyester resin is not particularly limited and can be appropriately selected depending on the purpose. The polyester resin has a similar chemical structure to the phosphate ester group in the phosphate ester group, and therefore the affinity between the molecules is high. Therefore, by using the polyester resin in combination with the monomer having the phosphate ester group, the hardness of the obtained cured product can be further increased, and the effect of suppressing cohesive failure of the cured product can be improved.

[0017] From the viewpoint of compatibility with monomers (e.g., monomers, organic solvents, etc.), the polyester resin is preferably a polyester resin that dissolves in monomers, organic solvents, etc. These may be used alone or in combination of two or more.

[0018] As the polyester resin, commercially available products can be used. Examples of commercially available products include UVAD-081 (manufactured by Osaka Soda Co., Ltd., number average molecular weight 1,400), UVAD-085 (manufactured by Osaka Soda Co., Ltd., number average molecular weight 2,000), Byron GK-810 (manufactured by Toyobo Co., Ltd., number average molecular weight 6,000), Byron 200 (manufactured by Toyobo Co., Ltd., number average molecular weight 17,000), Byron GK-360 (manufactured by Toyobo Co., Ltd., number average molecular weight 16,000), and Byron 600 (manufactured by Toyobo Co., Ltd., number average molecular weight 16,000). The polyester resin is preferably a polyester resin having an unsaturated bond. When the polyester resin has an unsaturated bond, the adhesion between the cured product and the substrate after immersion in hot water or an alkaline solution can be improved. Examples of the polyester resin having an unsaturated bond include UVAD-081 (manufactured by Osaka Soda Co., Ltd., number average molecular weight 1,400) and UVAD-085 (manufactured by Osaka Soda Co., Ltd., number average molecular weight 2,000).

[0019] The number average molecular weight of the polyester resin is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 500 to 2,000. When the number average molecular weight of the polyester resin is 3,000 or less, the adhesion between the cured product and the substrate can be improved. Furthermore, when the number average molecular weight of the polyester resin is 3,000 or less, the discharge stability of the composition can be improved.

[0020] The content of the polyester resin is preferably 3% by mass or more and 15% by mass or less, more preferably 3% by mass or more and 10% by mass or less, and even more preferably 5% by mass or more and 10% by mass or less, based on the total amount of the composition. When the content of the polyester resin is 3% by mass or more and 15% by mass or less, the adhesion between the cured product and the substrate can be made very excellent even after immersion in hot water or an alkaline solution. Furthermore, when the content of the polyester resin is 3% by mass or more and 15% by mass or less, the discharge stability of the composition can be improved.

[0021] <Other ingredients> Examples of the other components include polymerizable compounds other than the polymerizable monomer having a phosphate ester group, polymerization initiators, polymerization accelerators, coloring materials, organic solvents, and other components.

[0022] <<Polymerizable compounds other than polymerizable monomers having a phosphate ester group>> The polymerizable compound other than the polymerizable monomer having a phosphate ester group is not particularly limited, and any conventionally known polymerizable compound can be used. Examples of the polymerizable compound other than the polymerizable monomer having a phosphate group include polymerizable monomers and polymerizable oligomers.

[0023] Examples of the polymerizable compound other than the polymerizable monomer having a phosphate group include tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, ethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclic trimethylolpropane formal monoacrylate, imide acrylate, 2,2,2-trifluoroethyl acrylate, N-vinylformamide, cyclohexyl acrylate, and benzyl acrylate. Monofunctional polymerizable compounds such as tetrahydrofurfuryl acrylate, 4-t-butylcyclohexyl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, ethoxylated tribromophenyl acrylate, phenoxydiethylene glycol acrylate, vinylpyrrolidone, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, stearyl acrylate, lauryl acrylate, 3,3,5-trimethylcyclohexyl acrylate, ethoxylated nonylphenyl acrylate, alkoxylated 2-phenoxyethyl acrylate, phenoxypolyethylene glycol acrylate, dimethylacrylamide, hydroxyethylacrylamide, isopropylacrylamide, diethylacrylamide, and dimethylaminopropylacrylamide, pentaerythritol tri(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and the like. (meth)acrylate, dipentaerythritol (meth)hexaacrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,Examples of polyfunctional polymerizable compounds include 10-decanediol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, tetramethylolmethane tri(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, modified glycerin tri(meth)acrylate, bisphenol A diglycidyl ether (meth)acrylic acid adduct, modified bisphenol A di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hydroxypivalic acid neopentyl glycol (meth)acrylic acid adduct, 2-hydroxy-3-acryloyloxypropyl methacrylate, urethane acrylate oligomer, pentaerythritol tri(meth)acrylate hexamethylene diisocyanate urethane prepolymer, ditrimethylolpropane tetra(meth)acrylate, and pentaerythritol tri(meth)acrylate hexamethylene diisocyanate urethane prepolymer. These may be used alone or in combination of two or more. The (meth)acrylic acid adduct refers to an acrylic acid adduct or a methacrylic acid adduct, and the (meth)acrylate refers to an acrylate or a methacrylate.

[0024] The polymerizable compound other than the polymerizable monomer having a phosphate ester group is preferably a polyfunctional monomer having two or more polymerizable functional groups in the molecule. The content of the polyfunctional monomer having two or more polymerizable functional groups in the molecule is preferably 25% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total amount of the composition. When the content of the polyfunctional monomer having two or more polymerizable functional groups in the molecule is 25% by mass or less, the adhesion between the cured product and the substrate can be made very excellent even after immersion in hot water or an alkaline solution.

[0025] <<Polymerization initiator>> The active energy ray curable composition of the present invention may contain a polymerization initiator. The polymerization initiator may be any one that can generate active species such as radicals or cations by the energy of active energy rays and initiate polymerization of a polymerizable compound (monomer or oligomer). As such a polymerization initiator, known radical polymerization initiators, cationic polymerization initiators, base generators, etc., can be used alone or in combination of two or more kinds, and among them, it is preferable to use a radical polymerization initiator. In addition, in order to obtain a sufficient curing speed, the polymerization initiator is preferably contained in an amount of 5 to 20 mass% with respect to the total mass (100 mass%) of the composition. Examples of the radical polymerization initiator 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 carbon-halogen bonds, and alkylamine compounds. In addition to the above polymerization initiator, a polymerization promoter (sensitizer) can also be used in combination. The polymerization promoter is not particularly limited, but is preferably, for example, an amine compound such as trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, N,N-dimethylbenzylamine, and 4,4'-bis(diethylamino)benzophenone, and the content thereof may be appropriately set according to the polymerization initiator used and its amount.

[0026] <<Coloring materials>> The active energy ray curable composition of the present invention may contain a coloring material. As the coloring material, various pigments and dyes that impart glossy colors such as black, white, magenta, cyan, yellow, green, orange, gold, and silver can be used depending on the purpose and required properties of the composition of the present invention. The content of the coloring material may be appropriately determined in consideration of the desired color density and dispersibility in the composition, and is not particularly limited, but is preferably 0.1 to 20 mass% with respect to the total mass (100 mass%) of the composition. The active energy ray curable composition of the present invention may be colorless and transparent without containing a coloring material, and in that case, it is suitable as an overcoat layer for protecting an image, for example. As the pigment, an inorganic pigment or an organic pigment can be used, and one type may be used alone, or two or more types may be used in combination. Examples of inorganic pigments that can be used include carbon blacks (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide. Examples of organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelate azo pigments; polycyclic pigments such as phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments; dye chelates (e.g., basic dye chelates, acid dye chelates, etc.); dye lakes (basic dye lakes, acid dye lakes), nitro pigments, nitroso pigments, aniline black, and daylight fluorescent pigments. In order to improve the dispersibility of the pigment, a dispersant may be further included. The dispersant is not particularly limited, but examples thereof include dispersants commonly used in preparing pigment dispersions, such as polymer dispersants. As the dye, for example, acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and one type may be used alone, or two or more types may be used in combination.

[0027] <<Organic solvents>> The active energy ray curable composition of the present invention may contain an organic solvent, but preferably does not contain an organic solvent if possible. If the composition does not contain an organic solvent, particularly a volatile organic solvent (VOC (Volatile Organic Compounds)-free), the safety of the place where the composition is handled is improved and it is also possible to prevent environmental pollution. Note that the "organic solvent" means a general non-reactive organic solvent such as ether, ketone, xylene, ethyl acetate, cyclohexanone, toluene, etc., and should be distinguished from a reactive monomer. In addition, "not containing" an organic solvent means that it is substantially not contained, and it is preferable that the organic solvent is less than 0.1 mass%.

[0028] <<Other ingredients>> The active energy ray curable composition of the present invention may contain other known components as necessary. The other components are not particularly limited, but may include, for example, conventionally known surfactants, polymerization inhibitors, leveling agents, defoamers, fluorescent brighteners, penetration promoters, wetting agents (moisturizing agents), fixing agents, viscosity stabilizers, antifungal agents, preservatives, antioxidants, ultraviolet absorbers, chelating agents, pH adjusters, and thickeners.

[0029] <Preparation of active energy ray-curable composition> The active energy ray-curable composition of the present invention can be prepared using the various components described above. The preparation means and conditions are not particularly limited. For example, the active energy ray-curable composition can be prepared by putting a polymerizable monomer, a pigment, a dispersant, etc. into a dispersing machine such as a ball mill, a Kitty mill, a disk mill, a pin mill, or a Dyno mill, dispersing the polymerizable monomer, a pigment dispersion, and further mixing a polymerizable monomer, an initiator, a polymerization inhibitor, a surfactant, etc. into the pigment dispersion.

[0030] <Viscosity> The viscosity of the active energy ray-curable composition of the present invention may be appropriately adjusted depending on the application and means of application, and is not particularly limited. From the viewpoint of further enhancing the interaction between the substrate and the active energy ray-curable composition and achieving superior adhesion, the viscosity is preferably 40 mPa s or less, and more preferably 30 mPa s or less at 25° C. The viscosity can be measured, for example, by a cone-plate type rotational viscometer VISCOMETER TVE-25L manufactured by Toki Sangyo Co., Ltd., using a cone rotor (1°34'×R24), setting the rotation speed at 50 rpm and the temperature of the circulating water at a constant temperature of 25° C. A VISCOMATE VM-150III can be used to adjust the temperature of the circulating water.

[0031] <Active energy rays> The active energy rays used to cure the active energy ray curable composition of the present invention are not particularly limited, and may be any rays that can provide the energy required to promote the polymerization reaction of the polymerizable components in the composition, such as ultraviolet rays, electron beams, α rays, β rays, γ rays, and X-rays. In particular, when a high-energy light source is used, the polymerization reaction can be promoted without using a polymerization initiator. In addition, in the case of ultraviolet irradiation, mercury-free is strongly desired from the viewpoint of environmental protection, and replacement with GaN-based semiconductor ultraviolet light-emitting devices is very useful industrially and environmentally. 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.

[0032] <Application> The use of the active energy ray-curable composition of the present invention 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. Examples of the use include molding resins, paints, adhesives, insulating materials, release agents, coating materials, sealing materials, various resists, and various optical materials. Furthermore, the active energy ray curable composition of the present invention can be used not only as an ink to form two-dimensional characters and images, or decorative coatings on various substrates, but also as a material for three-dimensional modeling to form a three-dimensional image (three-dimensional object). This material for three-dimensional modeling can be used, for example, as a binder between powder particles used in a powder lamination method in which a three-dimensional object is modeled by repeatedly curing and laminating a powder layer, or as a three-dimensional construction material (model material) or a support member (support material) used in an additive manufacturing method (stereolithography) as shown in Figure 2 and Figures 3A to 3D.

[0033] FIG. 2 shows a method for discharging the active energy ray-curable composition of the present invention onto a predetermined area, irradiating it with active energy rays to cure it, and sequentially stacking the resulting pieces to form a three-dimensional object (described in detail later). FIGS. 3A to 3D show a method for irradiating a storage pool (container) 1 of the active energy ray-curable composition 5 of the present invention with active energy rays 4 to form a cured layer 6 of a predetermined shape on a movable stage 3, and sequentially stacking these layers to form a three-dimensional object.

[0034] In Fig. 3A, active energy rays 4 are irradiated to a storage pool (container) 1 of the active energy ray-curable composition 5 of the present invention. Then, in Fig. 3B, a cured layer 6 of a predetermined shape is formed on a movable stage 3 by irradiation with active energy rays 4. Then, in Fig. 3C, the movable stage 3 is lowered. Then, in Fig. 3D, a further cured layer 6 is formed on the obtained cured layer 6 by irradiation with active energy rays 4.

[0035] 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, there can be mentioned one equipped with a means for storing, supplying, and discharging the composition, and an active energy ray irradiation means, etc. The present invention also includes a molded article obtained by processing a cured product obtained by curing the active energy ray-curable composition or a structure formed on a substrate with the cured product. The molded article is, for example, a cured product or structure formed in a sheet or film shape, which is molded by heat stretching, punching, or the like, and is suitably used for applications requiring molding after surface decoration, such as meters and operation panels for automobiles, office automation equipment, electric and electronic equipment, and cameras. The substrate is not particularly limited and can be appropriately selected depending on the purpose. Examples of the substrate include paper, thread, fiber, cloth, leather, metal, plastic, glass, wood, ceramics, and composite materials thereof. The active energy ray-curable composition of the present invention can form a good cured product, particularly on non-permeable substrates such as metals, plastics, glass, and ceramics. The shape of the substrate may be, for example, a flat substrate or a non-flat substrate such as a bottle.

[0036] The active energy ray-curable composition of the present invention may be used alone or in combination with another composition. As an example of use in combination with another composition, for example, the active energy ray-curable composition of the present invention may be used as a primer by applying another composition (e.g., a pigment-containing composition) on the active energy ray-curable composition of the present invention applied onto a substrate.

[0037] (Active energy ray curable ink composition) The active energy ray-curable ink composition of the present invention contains the active energy ray-curable composition, and may further contain other components as necessary.

[0038] (Inkjet ink composition) The inkjet ink composition of the present invention contains the active energy ray-curable ink composition, and may further contain other components as required.

[0039] (Composition storage container) The composition storage container of the present invention means a container in which 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 inkjet ink composition of the present invention is stored, and is suitable for use in the above-mentioned applications. For example, when the active energy ray curable composition of the present invention is used for ink, the container in which the ink is stored 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, and can prevent the staining of hands, fingers, and clothing. In addition, it is possible to prevent the inclusion of foreign matter such as dust in the ink. In addition, the shape, size, material, and the like of the container itself may be suitable for the application and usage, and are not particularly limited, but it is preferable that the material is a light-shielding material that does not transmit light, or that the container is covered with a light-shielding sheet or the like.

[0040] (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 apparatus of the present invention has a composition-storing container of the present invention and an irradiation means for irradiating with active energy rays, and may have a discharge means for discharging the active energy ray-curable composition, and may further have other means as necessary. The two-dimensional or three-dimensional image forming method of the present invention includes an irradiation step of irradiating 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 inkjet ink composition of the present invention with active energy rays, and further includes other steps as necessary. The two-dimensional or three-dimensional image forming apparatus of the present invention may be referred to as an image forming apparatus. The two-dimensional or three-dimensional image forming method of the present invention may also be referred to as an image forming method. The image forming method of the present invention has at least an irradiation step of irradiating the active energy ray to cure the active energy ray curable composition of the present invention, and the image forming device of the present invention has an irradiation means for irradiating the active energy ray and a storage section for storing the active energy ray curable composition of the present invention, and the storage section may store the container. Furthermore, it may have a discharge step and a discharge means for discharging the active energy ray curable composition. The discharge method is not particularly limited, and examples thereof include a continuous spray type and an on-demand type. Examples of the on-demand type include a piezo type, a thermal type, and an electrostatic type. The active energy ray is preferably light, and particularly preferably ultraviolet rays having a wavelength of 220 nm to 400 nm. In addition to ultraviolet rays, electron beams, α rays, β rays, γ rays, X-rays, and the like may be used as long as they can provide the energy required to promote the polymerization reaction of the polymerizable components in the composition, and are not particularly limited. In particular, when a high-energy light source is used, the polymerization reaction can be promoted without using a polymerization initiator. In addition, in the case of ultraviolet irradiation, mercury-free devices are strongly desired from the viewpoint of environmental protection, and replacement with GaN-based semiconductor ultraviolet light-emitting devices is very useful industrially and environmentally. 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, and are therefore preferable as ultraviolet light sources.

[0041] FIG. 1 is an example of an image forming apparatus equipped with an inkjet ejection means. The ink is ejected onto a recording medium 22 supplied from a supply roll 21 by printing units 23a, 23b, 23c, and 23d, which are equipped with ink cartridges and ejection heads for active energy ray curable inks of each color of yellow, magenta, cyan, and black. Then, the ink is cured by irradiating the ink with active energy rays from light sources 24a, 24b, 24c, and 24d for curing the ink, forming a color image. Then, the recording medium 22 is conveyed to a processing unit 25 and a print winding roll 26. Each printing unit 23a, 23b, 23c, and 23d may be provided with a heating mechanism so that the ink is liquefied in the ink ejection section. If necessary, a mechanism for cooling the recording medium to about room temperature by contact or non-contact may be provided. In addition, the inkjet recording method can be either a serial method in which the head is moved to eject ink onto the recording medium, which moves intermittently according to the width of the ejection head, or a line method in which the recording medium is moved continuously and ink is ejected onto the recording medium from a head held at a fixed position. The recording medium 22 is not particularly limited, but may be paper, film, metal, a composite material thereof, or the like, and may be in the form of a sheet. Also, the recording medium 22 may be configured to allow only one-sided printing, or may be configured to allow both-sided printing. Furthermore, the irradiation of active energy rays from the light sources 24a, 24b, and 24c may be weakened or omitted, and after printing multiple colors, the active energy rays may be irradiated from the light source 24d, which can save energy and reduce costs. Recorded matters recorded with the ink of the present invention include not only those printed on smooth surfaces such as ordinary paper or resin film, but also those printed on uneven printing surfaces and those printed on printing surfaces made of various materials such as metals and ceramics. In addition, by laminating two-dimensional images, it is also possible to form an image with a partially three-dimensional effect (an image consisting of two and three dimensions) or a three-dimensional object. Fig. 2 is a schematic diagram showing an example of another image forming apparatus (a three-dimensional solid image forming apparatus) according to 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 from ejection head unit 30 for a model and ejects a second active energy ray-curable composition having a different composition from the first active energy ray-curable composition from ejection head units 31 and 32 for a support, and laminates these compositions while curing them with adjacent ultraviolet ray irradiation means 33 and 34. More specifically, for example, the second active energy ray curable composition is discharged from the support discharge head units 31 and 32 onto the object support substrate 37, and the first support layer having a reservoir is formed by irradiating the composition with active energy rays to solidify the composition, and then the first active energy ray curable composition is discharged from the object discharge head unit 30 into the reservoir, and the first object layer is formed by irradiating the composition with active energy rays to solidify the composition. This process is repeated several times while lowering the stage 38 movable in the vertical direction according to the number of layers to laminate the support layer and the object layer to produce a three-dimensional object 35. Thereafter, the support layer 36 is removed as necessary. Note that, although only one object discharge head unit 30 is provided in FIG. 2, two or more object discharge head units 30 may be provided.

[0042] (cured product) The cured product of the present invention is obtained 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 ink-jet ink composition of the present invention. As the active energy ray-curable composition, the same as the active energy ray-curable composition described above can be used, as the active energy ray-curable ink composition, the same as the active energy ray-curable ink composition described above can be used, and as the inkjet ink composition, the same as the inkjet ink composition described above can be used.

[0043] (Decorative body) The decorative body of the present invention comprises a substrate and the cured product of the present invention, and has a surface decoration made of the cured product on the substrate, and further comprises other members as necessary. The substrate is not particularly limited and can be appropriately selected depending on the purpose. Examples of the substrate include paper, thread, fiber, cloth, leather, metal, plastic, glass, wood, ceramics, and composite materials thereof. The shape of the substrate may be, for example, a planar shape or a non-planar shape such as a cylindrical shape.

[0044] (Laminate) The laminate of the present invention has a glass plate, a cured product of 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 inkjet ink composition of the present invention, and a resin film laminated in this order, and further has other members as necessary. The average thickness of the cured product layer is preferably 5 μm or more and 20 μm or less. When the average thickness of the cured product layer is 5 μm or more and 20 μm or less, the adhesion between the glass plate and the resin film and the flexibility of the formed laminate can be improved.

[0045] (Flexible device materials) The member for flexible devices of the present invention comprises the laminate of the present invention, and further comprises other members as necessary.

[0046] (Flexible Device) The member for flexible devices of the present invention comprises the laminate of the present invention, and further comprises other members as necessary. EXAMPLES

[0047] Examples of the present invention are shown below, but the scope of the present invention is not limited to these examples.

[0048] (Preparation Examples 1 to 27) -Preparation of active energy ray-curable compositions 1 to 27- The compositions shown in Tables 1 to 7 were mixed and stirred in a conventional manner to prepare active energy ray-curable compositions 1 to 27. Specifically, first, the monomers, the polyester resin, and the polymerization inhibitor were mixed and stirred to dissolve the polyester resin and the polymerization inhibitor, and then the polymerization initiator was added and mixed and stirred to dissolve the polymerization initiator, thereby obtaining an active energy ray curable composition. The stirring was carried out at room temperature using a stirrer, Three-One Motor (manufactured by Shinto Scientific Co., Ltd.).

[0049] [Table 1]

[0050] [Table 2]

[0051] [Table 3]

[0052] [Table 4]

[0053] [Table 5]

[0054] [Table 6]

[0055] [Table 7]

[0056] Details of the materials used are as follows: [Polymerizable monomers having phosphate ester groups] SR9050NS: Sartomer Corporation, polymerizable functional group number 1 SR9051NS: Sartomer Corporation, polymerizable functional group number 3 Light Acrylate P-1A(N): Kyoeisha Chemical Co., Ltd., polymerizable functional group number 1; compound name: 2-acryloyloxyethyl acid phosphate [Polyester resin] UVAD-081: Osaka Soda Co., Ltd., number average molecular weight 1,400, polyester resin with unsaturated bonds UVAD-085: Osaka Soda Co., Ltd., number average molecular weight 2,000, polyester resin with unsaturated bonds Vylon GK-810: Toyobo Co., Ltd., number average molecular weight 6,000 Vylon 802: Toyobo Co., Ltd., number average molecular weight 3,000 [Other polymerizable compounds] Cyclic trimethylolpropane formalmonoacrylate: Osaka Organic Chemical Industry Ltd. Tetrahydrofurfuryl acrylate: Osaka Organic Chemical Industry Ltd. Dipropylene glycol diacrylate: Tokyo Chemical Industry Co., Ltd. Trimethylolpropane triacrylate: Osaka Organic Chemical Industry Ltd. [Polymerization initiator] omnirad TPO: manufactured by IGM Omnirad 819: IGM [Polymerization inhibitor] BHT: Tokyo Chemical Industry Co., Ltd.

[0057] (Preparation of active energy ray-curable black pigment ink composition) 15 parts by mass of black pigment (trade name: MOGUL-E (carbon black), manufactured by Orion Co., Ltd.), 5 parts by mass of dispersant (trade name: BYK167, manufactured by BYK-Chemie Co., Ltd.), and 80 parts by mass of tetrahydrofurfuryl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) were placed in a 300 mL ball mill filled with zirconia beads with a diameter of 2 mm (filling rate: 43 volume%) and dispersed at a dispersion temperature of 25°C and 70 revolutions / minute for 180 hours to prepare a black pigment dispersion. The components shown in Table 8 were mixed and stirred in a conventional manner to prepare active energy ray-curable black pigment ink compositions 1 to 3. Specifically, first, the monomers and the polymerization inhibitor were mixed and stirred to dissolve the polymerization inhibitor, then the polymerization initiator was added and mixed and stirred to dissolve the polymerization initiator, and finally the black pigment dispersion was added and stirred to obtain an active energy ray curable black pigment ink composition. The stirring was carried out at room temperature using a stirrer, Three-One Motor (manufactured by Shinto Scientific Co., Ltd.).

[0058] [Table 8]

[0059] Example 1 The obtained active energy ray-curable composition of Preparation Example 1 was used in a 3000-kilometer-long inkjet printer using an inkjet head MH5420 (manufactured by Ricoh Co., Ltd.) and a metal halide lamp (3000 mJ / cm) manufactured by Ushio Inc. 2 ) was filled into an inkjet printing device with a head and substrate surface gap of 1 mm, 1.5 mg / cm 2 A solid image measuring 4 cm square was printed on a glass substrate (S9213, manufactured by Matsunami Glass Industry Co., Ltd.) so that the amount of adhesion was 100 μm, and a print 1 was obtained.

[0060] (Examples 2 to 20 and Comparative Examples 1 to 7) Printed matters 2 to 20 and 24 to 30 were obtained in the same manner as in Example 1, except that the active energy ray-curable composition of Preparation Example 1 was changed to the active energy ray-curable compositions of Preparation Examples 2 to 27.

[0061] Example 21 The obtained active energy ray-curable composition of Preparation Example 1 was used in a 3000-kilometer-long inkjet printer using an inkjet head MH5420 (manufactured by Ricoh Co., Ltd.) and a metal halide lamp (3000 mJ / cm) manufactured by Ushio Inc. 2 ) was filled into an inkjet printing device with a head and substrate surface gap of 1 mm, 1.5 mg / cm 2 A solid image measuring 4 cm square was printed on a glass substrate (S9213, Matsunami Glass Industry Co., Ltd.) so that the amount of adhesion was 100%. Subsequently, the active energy ray-curable black pigment ink composition 1 obtained in Preparation Example 24 was printed on the printed active energy ray-curable composition of Preparation Example 1 to obtain a printed matter 21. The active energy ray-curable black pigment ink composition 1 was printed by using an inkjet head MH5420 (manufactured by Ricoh Company, Ltd.) and a metal halide lamp (3000 mJ / cm) manufactured by Ushio Inc. 2 ) was filled into an inkjet printing device with a head and substrate surface gap of 1 mm, 1.5 mg / cm 2 The amount of ink applied was 4 cm x 4 cm solid image.

[0062] (Examples 22 to 23) Printed matters 22 to 23 were obtained in the same manner as in Example 21, except that the active energy ray-curable black pigment ink composition 1 in Example 21 was changed to active energy ray-curable black pigment ink compositions 2 and 3.

[0063] Next, for the printed matter 1 to 30 obtained in Examples 1 to 23 and Comparative Examples 1 to 7, "adhesion after immersion in hot water" and "adhesion after immersion in alkaline solution" and "ejection stability" using the active energy ray-curable compositions of Preparation Examples 1 to 27 were evaluated as follows. The results are shown in Table 9.

[0064] (Adhesion after immersion in hot water) The obtained print was immersed in hot water heated to 90° C. for 20 minutes so that the entire image portion and the substrate were immersed. After immersion, the print was taken out, water droplets adhering to the image surface were wiped off, and a tape peeling test was performed. In the tape peeling test, tape (CT-24, manufactured by Nichiban Co., Ltd.) was applied to the image area and strongly pressed, then quickly peeled off in a direction of 90° to the image surface, and the image surface after the tape was peeled off was visually observed and evaluated according to the following evaluation criteria. Note that "image peeling" in the evaluation criteria refers to the case where "cured product of active energy ray-curable composition" was peeled off. [Evaluation Criteria] ◎: No peeling of image observed after tape peeling ○: Slight peeling of image observed after tape peeling ×: The image peeled off entirely after the tape was peeled off, or the image peeled off during immersion in hot water.

[0065] (Adhesion after immersion in alkaline solution) The obtained print was immersed in a 3% by mass aqueous solution of sodium hydroxide heated to 80° C. for 20 minutes so that the image portion and the substrate were entirely immersed. After immersion, the print was taken out, water droplets adhering to the image surface were wiped off, and a tape peeling test was performed. In the tape peeling test, tape (CT-24, manufactured by Nichiban Co., Ltd.) was applied to the image area and strongly pressed, then quickly peeled off in a direction of 90° to the image surface, and the image surface after the tape was peeled off was visually observed and evaluated according to the following evaluation criteria. Note that "image peeling" in the evaluation criteria refers to the case where "cured product of active energy ray-curable composition" was peeled off. [Evaluation Criteria] ◎: No peeling of image observed after tape peeling ○: Slight peeling of image observed after tape peeling ×: Image peeling was observed over the entire surface after the tape was peeled off, or the image peeled off during immersion in a 3% by mass aqueous solution of sodium hydroxide.

[0066] (Discharge stability) In an extended type coating device EV2500 (manufactured by Ricoh Co., Ltd.) equipped with an inkjet head MH5420 (manufactured by Ricoh Co., Ltd.), the active energy ray curable compositions of Preparation Examples 1 to 27 were filled, and the head heater was turned on to warm the composition inside the head. Discharge was continued for 30 minutes, and the discharge state was observed with a camera and evaluated according to the following evaluation criteria. The discharge state was observed for one of the four rows of discharge ports. [Evaluation Criteria] ◎: Discharge from all nozzles ○: The number of nozzles where non-ejection was observed was 1 or more and less than 15 △: The number of nozzles where non-ejection was observed was 15 or more and less than 30. ×: The number of nozzles where non-ejection was observed was 30 or more.

[0067] [Table 9]

[0068] Next, the "adhesion of the laminate" was evaluated as follows for the active energy ray-curable compositions of Preparation Examples 1, 3, 8, 9, 13, 14, 18 and 21. The results are shown in Table 10.

[0069] (Adhesion of laminate) The prepared active energy ray curable composition was applied to the entire area of ​​the substrate in the width direction (direction perpendicular to the application direction) on a polyester film (A4360, thickness: 75 μm, manufactured by Toyobo Co., Ltd.) so that the average thickness after curing was 10 μm. Next, a glass plate (G-leaf, manufactured by Nippon Electric Glass Co., Ltd.) was placed on the applied active energy ray curable composition, and then the composition was exposed to an LED irradiation device (365 nm, 3000 mJ / cm 2 A laminate was produced by irradiating the substrate with LED light using a 300-nm thick film (manufactured by Heraeus). In the prepared laminate, a cut was made at an end of the polyester film, and the polyester film was peeled off by pulling it by hand from the cut, and the laminate was evaluated according to the following evaluation criteria. [Evaluation Criteria] ○: Cannot be easily peeled off ×: Easily peeled off

[0070] [Table 10]

[0071] For example, aspects of the present invention are as follows. <1> The active energy ray-curable composition is characterized by containing a polymerizable monomer having a phosphate ester group and a polyester resin. <2> The above-mentioned polymerizable composition further comprises a polyfunctional monomer having two or more polymerizable functional groups in the molecule. <1> The active energy ray-curable composition according to claim 1, <3> The content of the polyfunctional monomer having two or more polymerizable functional groups in the molecule is 25 mass % or less. <2> The active energy ray-curable composition according to claim 1, <4> The polyester resin is a polyester resin having an unsaturated bond. <1> from <3> 10. The active energy ray-curable composition according to claim 9, <5> The polyester resin content is 3% by mass or more and 15% by mass or less. <1> from <4> 10. The active energy ray-curable composition according to claim 9, <6> The number average molecular weight of the polyester resin is 2,000 or less. <1> from <5> 10. The active energy ray-curable composition according to claim 9, <7> The content of the polymerizable monomer having a phosphate ester group is 3% by mass or more and 10% by mass or less. <1> from <6> 10. The active energy ray-curable composition according to claim 9, <8> The polymerizable monomer having a phosphate ester group is a polyfunctional monomer having two or more polymerizable functional groups in the molecule. <1> from <7> 10. The active energy ray-curable composition according to claim 9, <9> The polymerizable monomer having a phosphate ester group is a polyfunctional monomer having three polymerizable functional groups in the molecule. <8> The active energy ray-curable composition according to claim 1, <10> The above <1> from <9> 2. An active energy ray-curable ink composition comprising the active energy ray-curable composition according to claim 1. <11> The above <10> 2. An ink-jet ink composition comprising the active energy ray-curable ink composition according to claim 1. <12> The above <1> from <9> The active energy ray-curable composition according to any one of the preceding claims. <10> and the active energy ray-curable ink composition according to the above. <11> The present invention relates to a composition storage container that stores at least one of the ink-jet ink compositions described above. <13> The above <12> and an irradiation means for irradiating with active energy rays. <14> The above <1> from <9> The active energy ray-curable composition according to any one of the preceding claims. <10> and the active energy ray-curable ink composition according to the above. <11> and a step of irradiating at least any one of the ink-jet ink compositions described in the above with active energy rays. <15> The above <1> from <9> The active energy ray-curable composition according to any one of the preceding claims. <10> and the active energy ray-curable ink composition according to the above. <11> The present invention relates to a cured product obtained by curing at least one of the ink-jet ink compositions described above. <16> A substrate and the <15> The cured product according to claim 1, The decorative body is characterized by having a surface decoration made of the cured product on the substrate. <17> The substrate has a cylindrical shape. <16> The decorative body according to the present invention is <18> A glass plate and The above <1> from <9> The active energy ray-curable composition according to any one of the preceding claims. <10> and the active energy ray-curable ink composition according to the above. <11> and a cured product of at least one of the ink-jet ink compositions described in and a resin film laminated in this order. <19> The above <18> 2. A member for a flexible device, comprising the laminate according to claim 1. <20> The above <18> A flexible device comprising the laminate according to claim 1.

[0072] The above <1> from <9> The active energy ray-curable composition according to any one of the preceding claims. <10> and the active energy ray-curable ink composition according to the above. <11> The ink composition for ink-jet recording according to the present invention <12> The composition container according to the <13> The two-dimensional or three-dimensional image forming apparatus according to <14> The method for forming a two-dimensional or three-dimensional image according to <15> The cured product according to <16> from <17> The decorative body according to <18> The laminate according to <19> The flexible device member according to claim 1, <20> According to the flexible device described in the above, the conventional problems can be solved and the object of the present invention can be achieved. [Explanation of symbols]

[0073] 1. Storage Pool 21 Supply roll 22 Recording media 23a, 23b, 23c, 23d Printing units 24a, 24b, 24c, 24d light source 25 Processing Unit 26 Printed matter winding roll 3 Movable stage 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 4. Active energy rays 5. Active energy ray curable composition 6 Hardened layer [Prior art documents] [Patent documents]

[0074] [Patent Document 1] JP 2015-034240 A [Patent Document 2] JP 2012-162615 A [Patent Document 3] JP 2015-513601 A

Claims

1. A polymerizable monomer having a phosphate ester group, A polyester resin having an unsaturated bond, and Contains a polyfunctional monomer having two or more polymerizable functional groups in the molecule, The active energy ray-curable composition, wherein the content of the polyfunctional monomer having two or more polymerizable functional groups in the molecule is 10 mass % or less.

2. The active energy ray-curable composition according to claim 1, wherein the polymerizable monomer having a phosphate ester group is a polyfunctional monomer having two or more polymerizable functional groups in the molecule.

3. 3. The active energy ray-curable composition according to claim 1, wherein the content of the polymerizable monomer having a phosphate ester group is from 3% by mass to 10% by mass.

4. 4. The active energy ray-curable composition according to claim 1, wherein the polymerizable monomer having a phosphate ester group is a polyfunctional monomer having three polymerizable functional groups in the molecule.

5. The active energy ray-curable composition according to claim 1 , which is for use on a glass substrate.

6. An active energy ray-curable ink composition comprising the active energy ray-curable composition according to claim 1 .

7. An ink-jet ink composition comprising the active energy ray-curable ink composition according to claim 6.

8. A composition storage container, comprising at least one of the active energy ray-curable composition according to claim 1, the active energy ray-curable ink composition according to claim 6, and the ink-jet ink composition according to claim 7.

9. A two-dimensional or three-dimensional image forming apparatus comprising: a composition container according to claim 8; and an irradiation means for irradiating with active energy rays.

10. 8. A method for forming a two-dimensional or three-dimensional image, comprising an irradiation step of irradiating at least one of the active energy ray-curable composition according to claim 1, the active energy ray-curable ink composition according to claim 6, or the ink-jet ink composition according to claim 7, with active energy rays.

11. A cured product obtained by curing at least one of the active energy ray-curable composition according to claim 1, the active energy ray-curable ink composition according to claim 6, and the ink-jet ink composition according to claim 7.

12. A substrate and the cured product according to claim 11, A decorated body having a surface decoration made of the cured product on the substrate.

13. The decorated body according to claim 12, wherein the base material has a cylindrical shape.

14. A glass plate and A cured product of at least one of the active energy ray-curable composition according to any one of claims 1 to 5, the active energy ray-curable ink composition according to claim 6, and the ink-jet ink composition according to claim 7; A laminate comprising: a resin film; and a laminated body having the above laminated body and the resin film laminated in this order.

15. A member for a flexible device, comprising the laminate according to claim 14.

16. A flexible device comprising the laminate according to claim 14.

Images