Compound, active energy ray curable composition, active energy ray curable ink, storage container, image forming apparatus, image forming method, and cured product

Abstract

To provide a compound that is used as a component of an active energy ray-curable composition to give a cured product that has improved adhesion to a substrate, particularly steel.SOLUTION: The present invention discloses a compound represented by general formula (1). (In the general formula (1), A is a (m+n)-valent polyhydric alcohol residue or a residue of a polyhydric alcohol condensate, p is an integer of 0 or more and 5 or less, q is 0 or 1, m is an integer of 0 or greater, n is an integer of 1 or greater, R1 is a hydrogen atom or a methyl group, R2 is a linear or branched alkyl group).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a compound, an active energy ray-curable composition, an active energy ray-curable ink, a storage container, an image forming apparatus, an image forming method, and a cured product. [Background technology]

[0002] As inks used in active energy ray-curable inkjet recording methods, radically polymerizable inks and cationic polymerizable inks are known. Among these, radically polymerizable inks are widely used from the viewpoints of production costs and storage stability of the ink.

[0003] Known active energy ray-curable radical polymerizable inks include inks that contain a polymerizable monomer such as an acrylic acid ester and a polymerization initiator that generates radicals when irradiated with active energy rays. One of the functions required for these inks is the adhesion of the cured product to the substrate. In order to improve the adhesion of the image formed with the ink to the substrate, a primer ink has been proposed for use together with the ink (see, for example, Patent Document 1). Summary of the Invention [Problem to be solved by the invention]

[0004] Cured products obtained from conventional active energy ray-curable compositions often lack sufficient adhesion to substrates and are poor in durability.

[0005] Accordingly, an object of the present invention is to provide a compound which, when used as a component of an active energy ray-curable composition, enhances the adhesion of the cured product to a substrate, particularly to steel. [Means for solving the problem]

[0006] The compound of the present invention which solves the above problems is a compound represented by the following general formula (1). [ka] (In the general formula (1), A represents a polyhydric alcohol residue having a valence of (m+n) or a residue of a polyhydric alcohol condensate, p represents an integer of 0 or more and 5 or less, q represents 0 or 1, m represents an integer of 0 or more, n represents an integer of 1 or more, R1 represents a hydrogen atom or a methyl group, and R2 represents a linear or branched alkyl group.) Effect of the Invention

[0007] According to the present invention, it is possible to provide a compound that, when used as a component of an active energy ray-curable composition, enhances the adhesion of the cured product to a substrate. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic diagram illustrating an example of an image forming apparatus according to the present invention. [Diagram 2] FIG. 2 is a schematic diagram showing an example of another image forming apparatus according to the present invention. [Diagram 3] FIG. 11 is a schematic diagram showing yet another example of an image forming apparatus according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The following description is for illustrating examples of the embodiments of the present invention, and is not intended to limit the scope of the claims.

[0010] (compound) The compound of the present invention is represented by the following general formula (1).

[0011] [ka] (In the general formula (1), A represents a polyhydric alcohol residue having a valence of (m+n) or a residue of a polyhydric alcohol condensate, p represents an integer of 0 or more and 5 or less, q represents 0 or 1, m represents an integer of 0 or more, n represents an integer of 1 or more, R1 represents a hydrogen atom or a methyl group, and R2 represents a linear or branched alkyl group.)

[0012] The compound of the present invention can be obtained in high yield by a Michael addition reaction between a (meth)acrylate or (meth)acrylamide compound and a proline alkyl ester. Specific examples of the compound of the present invention are shown below, but the present invention is not limited to these. In the following specific examples, R1 represents a hydrogen atom or a methyl group, and R2 represents a linear or branched alkyl group.

[0013] [ka]

[0014] [ka]

[0015] [ka]

[0016] (Active energy ray curable composition, active energy ray curable ink) The active energy ray curable composition of the present invention (hereinafter, sometimes referred to as "curable composition") can be used by mixing with a (meth)acrylate compound, a (meth)acrylamide compound, etc., and in this case, the different compounds also include structural isomers. The mixing ratio is not particularly limited. The curable composition of the present invention is suitably used as an active energy ray-curable ink, particularly an active energy ray-curable inkjet ink. The content of the compound of the present invention in the curable composition is usually from 20% by mass to 98% by mass, preferably from 30% by mass to 90% by mass, and more preferably from 30% by mass to 80% by mass.

[0017] The curable composition may contain other photopolymerizable compounds other than the compound represented by formula (1). The mass ratio of the other photopolymerizable compounds to the compound represented by formula (1) is usually 0.01 to 100 mass%, preferably 0.1 to 50 mass%, of the compound represented by formula (1) in all polymerizable compounds. The other photopolymerizable compounds are not particularly limited, and examples thereof include photoradical polymerizable compounds, photocationic polymerizable compounds, and photoanionic polymerizable compounds, and two or more of these may be used in combination.

[0018] The photoradical polymerizable compound is not particularly limited as long as it has one or more ethylenically unsaturated groups capable of photoradical polymerization, and includes monomers, oligomers, polymers, etc. Examples thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid, salts thereof, and compounds derived therefrom, anhydrides having an ethylenically unsaturated group, acrylonitrile, styrene, unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes.

[0019] Specific examples of photoradical polymerizable compounds include 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis(4-acryloxypolyethoxyphenyl)propane, neopentyl glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, and trimethylolpropane triacrylate. , acrylic acid derivatives such as tetramethylolmethane tetraacrylate, oligoester acrylate, and epoxy acrylate; methacrylic acid derivatives such as methyl methacrylate, n-butyl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, and 2,2-bis(4-methacryloxypolyethoxyphenyl)propane; acrylamide derivatives such as N-methylol acrylamide, diacetone acrylamide, 2-hydroxyethyl acrylamide, and acryloyl morpholine; derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate; ethylene glycol divinyl ether, ethylene glycol monovinyl ether, and diethylene glycol divinyl ether;Di- or trivinyl ether compounds such as triethylene glycol monovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, and trimethylolpropane trivinyl ether; monovinyl ether compounds such as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether-o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether; 2-ethylhexyl diglycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy ... xyloxybutyl acrylate, hydroxypivalic acid neopentyl glycol diacrylate, 2-acryloyloxyethyl phthalate, methoxypolyethylene glycol acrylate, tetramethylolmethane triacrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, dimethyloltricyclodecane diacrylate, ethoxylated phenyl acrylate, 2-acryloyloxyethyl succinate, nonylphenol ethylene oxide adduct acrylate, modified glycerin triacrylate, bisphenol A diglycidyl ether acrylate acid adduct, modified bisphenol A diacrylate, phenoxy polyethylene glycol acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, propylene oxide adduct of bisphenol A diacrylate, ethylene oxide adduct of bisphenol A diacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, tolylene diisocyanate urethane prepolymer, lactone modified flexible acrylate, butoxyethyl acrylate, propylene glycol diglycidyl ether acrylic acid adduct,Examples of the acrylates include pentaerythritol triacrylate, hexamethylene diisocyanate urethane prepolymer, 2-hydroxyethyl acrylate, methoxydipropylene glycol acrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, hexamethylene diisocyanate urethane prepolymer, stearyl acrylate, isoamyl acrylate, isomyristyl acrylate, isostearyl acrylate, and lactone-modified acrylates.

[0020] <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 a carbon-halogen bond, and alkylamine compounds. In addition to the polymerization initiator, a polymerization accelerator (sensitizer) can also be used in combination. The polymerization accelerator is not particularly limited, but for example, 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 are preferred, and the content thereof may be appropriately set according to the polymerization initiator used and its amount.

[0021] In addition, examples of combinations of photopolymerizable compounds and photopolymerization initiators include a combination of a photoradical polymerizable compound and a photoradical polymerization initiator, as well as a combination of a photocationic polymerizable compound and a photocationic polymerization initiator, and a combination of a photoanionic polymerizable compound and a photoanionic polymerization initiator.

[0022] Examples of the photocationically polymerizable compound include an epoxy compound, a vinyl ether compound, and an oxetane compound. Photo-cationic polymerization initiators include aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium, and phosphonium, such as B(C6F5)4. - , PF6 - , AsF6 - , SbF6 - , CF3SO3 - Examples of the metal complex include salts, sulfonates capable of generating sulfonic acid, halides capable of generating hydrogen halide, and iron-allene complexes. Examples of the photoanionically polymerizable compound include epoxy compounds, lactone compounds, acrylic compounds, methacrylic compounds, etc. Among these, the acrylic and methacrylic compounds exemplified as the photoradical polymerizable compound are preferred. Examples of the photoanionic polymerization initiator include o-nitrobenzyl carbamate derivatives, o-acyloxyl derivatives, and o-carbamoyloxime amidine derivatives.

[0023] (sensitizer) The curable composition may further contain a sensitizer in order to promote decomposition of the photopolymerization initiator by irradiation with active energy rays. The sensitizer absorbs active energy rays and becomes electronically excited, and in that state comes into contact with the polymerization initiator, promoting chemical changes in the polymerization initiator (decomposition, generation of radicals, acids or bases) through actions such as electron transfer, energy transfer and heat generation. The mass ratio of the sensitizer to the photopolymerization initiator is usually 5 × 10 -3 The content is from 0.02% by mass to 50% by mass, preferably from 0.02% by mass to 50% by mass.

[0024] The sensitizer is not particularly limited, and a sensitizing dye having an absorption wavelength in the wavelength region of 350 to 450 nm can be used. Examples thereof include polynuclear aromatics (e.g., pyrene, perylene, triphenylene), xanthenes (e.g., fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (e.g., thiacarbocyanine, oxacarbocyanine), merocyanines (e.g., merocyanine, carbomerocyanine), thiazines (e.g., thionine, methylene blue, toluidine blue), acridines (e.g., acridine orange, chloroflavine, acriflavine), anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), and coumarins (e.g., 7-diethylamino-4-methylcoumarin).

[0025] (Cosensitizer) The curable composition may further comprise a co-sensitizer. The co-sensitizer further improves the sensitivity of the sensitizing dye to active energy rays and suppresses the polymerization inhibition of the photopolymerizable compound caused by oxygen. The co-sensitizer is not particularly limited, but examples thereof include amine compounds such as triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, and p-methylthiodimethylaniline; thiols and sulfides such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4(3H)-quinazoline, and β-mercaptonaphthalene; and the like.

[0026] (Polymerization inhibitor) The curable composition may further contain a polymerization inhibitor. By containing a polymerization inhibitor, the preservability (storage stability) of the curable composition can be improved. In addition, when the curable composition is heated to reduce its viscosity and discharged, clogging of the head due to thermal polymerization can be prevented. The polymerization inhibitor is not particularly limited, but examples thereof include hydroquinone, benzoquinone, p-methoxyphenol, TEMPO, TEMPOL, aluminum cupferron complex, etc. The content of the polymerization inhibitor in the ink is usually 200 ppm or more and 20,000 ppm or less.

[0027] <Coloring material> 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.

[0028] <Organic solvent> 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%.

[0029] <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.

[0030] <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 ingredients to prepare a pigment dispersion, and further mixing a polymerizable monomer, an initiator, a polymerization inhibitor, a surfactant, etc. into the pigment dispersion.

[0031] <Viscosity> The viscosity of the active energy ray curable composition of the present invention may be adjusted appropriately depending on the application and application means, and is not particularly limited. For example, when applying an ejection means that ejects the composition from a nozzle, the viscosity in the range of 20°C to 65°C, desirably the viscosity at 25°C is preferably 3 to 40 mPa·s, more preferably 5 to 15 mPa·s, and particularly preferably 6 to 12 mPa·s. It is particularly preferable that the viscosity range is satisfied without containing the organic solvent. The viscosity can be measured by using a cone-plate type rotational viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd., using a cone rotor (1°34'×R24), with a rotation speed of 50 rpm and a temperature of the constant temperature circulating water appropriately set in the range of 20°C to 65°C. A VISCOMATE VM-150III can be used to adjust the temperature of the circulating water.

[0032] <Curing means> The curable composition of the present invention can be cured by heat curing or by curing with active energy rays, and among these, curing with active energy rays is preferred. 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.

[0033] <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 as an ink to form two-dimensional characters and images, and decorative coatings on various substrates, and can also be used 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 modeling is performed by repeatedly curing and laminating powder layers, 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 FIG. 2 or FIG. 3. FIG. 2 shows a method of discharging the active energy ray curable composition of the present invention into a predetermined area, irradiating it with active energy rays, curing it, and sequentially laminating it to perform a three-dimensional modeling (described in detail later), and FIG. 3 shows a method of 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 laminating it to perform a three-dimensional modeling. 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, and is not particularly limited. For example, the three-dimensional modeling apparatus may be one equipped with a means for storing, supplying, and discharging the composition, and an active energy ray irradiation means. 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. From the viewpoint of processability, a plastic substrate is preferred.

[0034] <Composition storage container> The composition-storing container of the present invention means a container in which an active energy ray-curable composition 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. 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.

[0035] <Image forming method and apparatus> The image forming method of the present invention may use active energy rays or heating. In order to cure the curable composition of the present invention with active energy rays, an irradiation step of irradiating active energy rays is provided, and the image forming apparatus of the present invention includes an irradiation means for irradiating active energy rays 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, the apparatus may include 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. 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, ceramics, glass, metal, a composite material thereof, or the like, and may be in the form of a sheet. The recording medium may be configured to allow only one-sided printing, or may be configured to allow both-sided printing. The recording medium is not limited to those generally used as recording media, and cardboard, building materials such as wallpaper and flooring, concrete, cloth for clothing such as T-shirts, textiles, leather, and the like may be used as appropriate. 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.

[0036] (cured product) The cured product is formed using at least one of the curable composition of the present invention and the active energy ray-curable ink of the present invention. As the curable composition, the same curable composition as described above can be used. As the active energy ray curable ink, the same active energy ray curable ink as described above can be used.

[0037] (Decorative body) The decorated body is formed by applying a surface decoration made of a cured product onto a substrate, and the same cured products as those mentioned above can be used. 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. From the viewpoint of processability, plastic is preferred. EXAMPLES

[0038] The present invention will be described in more detail below based on examples, but the technical scope of the present invention is not limited to the following examples in any way. First, a synthesis example of the compound represented by the general formula (1) used in the present invention will be described.

[0039] (Example 1-1) Synthesis of Example Compound No. 1 [ka]

[0040] In a 50mL three-neck flask, 179g (10.8mmol) of L-proline-methyl ester hydrochloride (Tokyo Chemical Industry Co., Ltd.), 8mL of tetrahydrofuran, and 2mL of pure water were charged, and 1.20g (11.9mmol) of triethylamine was gradually added with a pipette to perform dehydrochlorination treatment. After stirring at room temperature for 1 hour, ethyl acetate was added and transferred to a separatory funnel to separate the organic layer and the aqueous layer. This organic layer was dropped into another 50mL three-neck flask containing 0.89g (3mmol) of trimethylolpropane triacrylate, and stirred at room temperature for 1 hour. After extracting this reaction solution with pure water as a dichloromethane solution, the organic layer was concentrated under reduced pressure to obtain 1.82g of the target product (yield 89%) as a light yellow liquid. The identification data is as follows: 1 H-NMR (500MHz, CDCl 3):δ 0.84-0.92(m,3H),1.40-1.51(m,2H),1.70-2.15(m,12H),2.39-2.46(m,6H),2.51 -2.57(m,6H),2.71-2.76(m,6H),3.70-3.73(m,6H),3.77(m,9H),4.54-4.58(m,3H)

[0041] (Example 1-2) Synthesis of Example Compound No. 22 [ka] In a 50 mL three-neck flask, 179 g (10.8 mmol) of L-proline methyl ester hydrochloride (Tokyo Chemical Industry Co., Ltd.), 10 mL of tetrahydrofuran, and 2 mL of pure water were charged, and 1.32 g (13.0 mmol) of triethylamine was gradually added thereto using a pipette to carry out dehydrochlorination treatment. After stirring at room temperature for 1 hour, ethyl acetate was added and the mixture was transferred to a separatory funnel to separate the organic layer and the aqueous layer. This organic layer was Dipentaerythritol Hexaacrylate The reaction solution was then dissolved in dichloromethane and extracted with pure water. The organic layer was concentrated under reduced pressure to obtain 2.20 g (81% yield) of the target compound as a pale yellow liquid. The identification data is as follows: 1 H-NMR(500MHz, CDCl3):δ 1.73-2.17(m,24H),2.99-3.04(m,12H),3.09-3.15(m,12H),3.21-3.25(m,12H ),3.44-3.48(m,12H),3.71-3.74(m,18H),4.15-4.27(m,4H),4.31-4.34(m,6H)

[0042] (Examples 1-3) Synthesis of Example Compound No. 4 [ka] In a 50mL three-neck flask, 159g (9.6mmol) of L-proline-methyl ester hydrochloride (Tokyo Chemical Industry Co., Ltd.), 8mL of tetrahydrofuran, and 2mL of pure water were charged, and 1.07g (10.6mmol) of triethylamine was gradually added with a pipette to perform dehydrochlorination treatment. After stirring at room temperature for 1 hour, ethyl acetate was added and transferred to a separatory funnel to separate the organic layer and the aqueous layer. This organic layer was dropped into another 50mL three-neck flask containing 1.20g (4mmol) of tripropylene glycol diacrylate, and stirred at room temperature for 1 hour. After extracting this reaction solution with pure water as a dichloromethane solution, the organic layer was concentrated under reduced pressure to obtain 1.96g of the target product (yield 88%) as a light yellow liquid. The identification data is as follows: 1 H-NMR(500MHz,CDCl3): δ 1.12-1.28(m,9H),1.71-2.16(m,8H),2.40(m,4H),2.51-2,58(m,4H),2.71-2. 78(m,4H),3.00-3.06(m,4H),3.21-3.24(m,4H),3.72(m,6H),5.00-5.18(m,3H)

[0043] (Examples 1 to 4) Synthesis of Example Compound No. 5 [ka] In a 100mL three-neck flask, 3.31g (20.0mmol) of L-proline-methyl ester hydrochloride (Tokyo Chemical Industry Co., Ltd.), 15mL of tetrahydrofuran, and 5mL of pure water were charged, and 2.40g (24.0mmol) of triethylamine was gradually added with a pipette to perform dehydrochlorination treatment. After stirring at room temperature for 1 hour, ethyl acetate was added and transferred to a separatory funnel to separate the organic layer and the aqueous layer. This organic layer was dropped into another 100mL three-neck flask containing 6.0g (20mmol) of propylene glycol diacrylate, and stirred at room temperature for 1 hour. After extracting this reaction solution with pure water as a dichloromethane solution, the organic layer was concentrated under reduced pressure and purified and isolated by silica gel column chromatography (filler: Wakogel C-300, developing solvent: n-hexane / ethyl acetate = 1 / 1), and 1.72g of the target product was obtained as a light yellow liquid (yield 20%). The identification data is as follows: 1 H-NMR (500MHz, CDCl3): δ1.11-1.28(m,9H),1.71-2.16(m,4H),2.40(m,2H),2.71-2.78(m,2H),4.02-4.05(m,1H),3. 32-3.65(m,8H),3.75(m,2H),3.73(m,3H),5.00-5.18(m,1H),5.80-5.85(m,1H),6.09-6.17(m,1H),6.38-6.44(m,1H)

[0044] [Preparation of active energy ray-curable composition] (Example 2-1) An active energy ray-curable composition was obtained by mixing and stirring 60 parts by mass of tetrahydrofurfuryl acrylate (Viscoat #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 30 parts by mass of isobornyl acrylate (IBXA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 7 parts by mass of a photopolymerization initiator Irgacure TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF Japan Ltd.), and 10 parts by mass of the exemplary compound No. 1 obtained in Example 1.

[0045] (Example 2-2) An active energy ray-curable composition of Example 2-2 was obtained in the same manner as in Example 2-1, except that Exemplified Compound No. 1 in Example 2-1 was replaced with Exemplified Compound No. 22.

[0046] (Example 2-3) An active energy ray-curable composition of Example 2-3 was obtained in the same manner as in Example 2-1, except that Exemplified Compound No. 1 in Example 2-1 was replaced with Exemplified Compound No. 4.

[0047] (Examples 2-4) An active energy ray-curable composition of Example 2-4 was obtained in the same manner as in Example 2-1, except that Exemplified Compound No. 1 in Example 2-1 was replaced with Exemplified Compound No. 5.

[0048] (Comparative Example 2-1) An active energy ray-curable composition of Comparative Example 1 was obtained by mixing and stirring 70 parts by mass of tetrahydrofurfuryl acrylate (Viscoat #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 30 parts by mass of isobornyl acrylate (IBXA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and 7 parts by mass of a photopolymerization initiator IRGACURE TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF Japan Ltd.).

[0049] (Comparative Example 2-2) An active energy ray-curable composition of Comparative Example 2 was obtained by mixing and stirring 60 parts by mass of tetrahydrofurfuryl acrylate (Viscoat #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 30 parts by mass of isobornyl acrylate (IBXA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 7 parts by mass of photopolymerization initiator Irgacure TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF Japan Ltd.), and 10 parts by mass of trimethylolpropane trimethacrylate (SR350, manufactured by Sartomer Co., Ltd.).

[0050] <Evaluation of curability> The active energy ray-curable compositions were filled into plastic composition containers, and the compositions were then ejected using an inkjet head ("MH5440" manufactured by Ricoh Co., Ltd.) as a discharge means and a UV-LED ("LED ZERO" manufactured by Integration Technology Japan, Inc., wavelength 395 nm, illuminance on the irradiation surface 1.0 W / cm) as an active energy ray irradiation means. 2 ), a controller for controlling the discharge, and a supply path from a composition storage container to the inkjet head. The temperature of the inkjet head was appropriately adjusted so that the viscosity of the active energy ray curable composition was 10 to 12 mPa·s, and the active energy ray curable compositions of Examples 1 to 3 and Comparative Example 1 were each ink-jet discharged to a film thickness of 10 μm onto a commercially available PET film ("Cosmoshine A4100" manufactured by Toyobo Co., Ltd., thickness 188 μm), which is a general-purpose film material, and ultraviolet rays were irradiated using a UV-LED to produce a printed image. The coating film was judged to have cured when it reached a state where it was not sticky when touched with a finger, and the cumulative amount of irradiation light required for curing was used as an index of curability.

[0051] <Evaluation of adhesion to substrate> The active energy ray curable compositions of the Examples and Comparative Examples were applied to a steel substrate (tinplate) to a thickness of 10 μm, and the active energy ray was irradiated with a UV-LED ("LED ZERO" manufactured by Integration Technology Japan, Inc., wavelength 395 nm) at a total irradiation energy of 2000 mJ / cm. 2 The curing was carried out under the following conditions. The cured samples were subjected to an adhesion test by a cross-cut method in accordance with JIS K5600-5-6 standard, and the evaluation criteria are shown below. (Evaluation Criteria) 5: No peeling is observed except around the edges of the cut. 4: Thin strips of peeling have occurred along the cut lines, and the paint has peeled off at the intersections of the cuts. 3: Thick peeling is observed along the cut line. 2: Fewer than 50% of the cross-cut squares are completely peeled off. 1: More than 50% of the cross-cut squares are completely peeled off.

[0052] The evaluation results of the curability of the active energy ray-curable composition and the adhesion of the cured product to a substrate are shown in Table 1. By using the compound of the present invention, the curability is improved and the adhesion to a steel substrate is also improved.

[0053] [Table 1]

[0054] The present invention relates to the following compound (1), and also includes the following embodiments (2) to (10). (1) A compound represented by the following general formula (1): [ka] (In the general formula (1), A represents a polyhydric alcohol residue having a valence of (m+n) or a residue of a polyhydric alcohol condensate, p represents an integer of 0 or more and 5 or less, q represents 0 or 1, m represents an integer of 0 or more, n represents an integer of 1 or more, R1 represents a hydrogen atom or a methyl group, and R2 represents a linear or branched alkyl group.) (2) The compound according to (1) above, wherein in the general formula (1), R2 has 1 or more and 6 or less carbon atoms. (3) An active energy ray-curable composition comprising at least a compound represented by the following general formula (1) and a polymerizable compound that is polymerizable by active energy rays: [ka] (In the general formula (1), A represents a polyhydric alcohol residue having a valence of (m+n) or a residue of a polyhydric alcohol condensate, p represents an integer of 0 or more and 5 or less, q represents 0 or 1, m represents an integer of 0 or more, n represents an integer of 1 or more, R1 represents a hydrogen atom or a methyl group, and R2 represents a linear or branched alkyl group.) (4) An active energy ray-curable ink comprising the active energy ray-curable composition according to (3) above. (5) A storage container containing the ultraviolet ray-curable composition described in (3) above or the active energy ray-curable ink described in (4) above. (6) A two-dimensional or three-dimensional image forming apparatus comprising: a means for applying the ultraviolet ray curable composition described in (3) above or the active energy ray curable ink described in (4) above to a substrate; and a means for irradiating the substrate with active energy rays. (7) The image forming apparatus according to the above (5), wherein the irradiation means for irradiating the active energy rays is a UV-LED for irradiating ultraviolet rays having a peak wavelength of 365 to 405 nm. (8) A method for forming a two-dimensional or three-dimensional image, comprising the steps of: applying the ultraviolet ray curable composition described in (3) above or the active energy ray curable ink jet ink described in (4) above to a substrate; and irradiating the active energy ray curable ink on the substrate with active energy rays. (9) The image forming method according to the above (7), wherein in the irradiation step of irradiating with active energy rays, ultraviolet rays having a peak wavelength of 365 to 405 nm are irradiated by a UV-LED. (10) A cured product of the active energy ray-curable composition described in (3) above or the active energy ray-curable ink described in (4) above. [Explanation of symbols]

[0055] 1. Storage pool (containment area) 3 Movable stage 4. Active energy rays 5. Active energy ray curable composition 6 Hardened layer 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 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 Stages 39 Image forming device [Prior art documents] [Patent documents]

[0056] [Patent Document 1] Patent No. 5789183

Claims

1. A compound represented by the following general formula (1): 【Chemistry 1】 In the general formula (1), A represents a residue of tripropylene glycol, dipentaerythritol, or trimethylolpropane, m represents an integer of 0 or more, n represents an integer of 1 or more, R １ represents a hydrogen atom or a methyl group, R ２ represents a straight-chain or branched alkyl group.

2. In the general formula (1), the R ２ The compound according to claim 1 , wherein the carbon number of

3. An active energy ray-curable composition comprising at least a compound represented by the following general formula (1) and a polymerizable compound that is polymerizable by active energy rays: 【Chemistry 1】 In the general formula (1), A represents a residue of tripropylene glycol, dipentaerythritol, or trimethylolpropane, m represents an integer of 0 or more, n represents an integer of 1 or more, R １ represents a hydrogen atom or a methyl group, R ２ represents a straight-chain or branched alkyl group.

4. An active energy ray-curable ink comprising the active energy ray-curable composition according to claim 3 .

5. A container containing the ultraviolet ray curable composition according to claim 3 or the active energy ray curable ink according to claim 4.

6. A two-dimensional or three-dimensional image forming apparatus comprising: a means for applying the ultraviolet ray curable composition according to claim 3 or the active energy ray curable ink according to claim 4 to a substrate; and a means for irradiating the substrate with active energy rays.

7. 7. The image forming apparatus according to claim 6, wherein the irradiation means for irradiating the active energy rays is a UV-LED for irradiating ultraviolet rays having a peak wavelength in the range of 365 to 405 nm.

8. 13. A method for forming a two-dimensional or three-dimensional image, comprising the steps of: applying the ultraviolet ray-curable composition according to claim 3 or the active energy ray-curable ink according to claim 4 to a substrate; and irradiating the active energy ray-curable ink on the substrate with active energy rays.

9. 9. The image forming method according to claim 8, wherein in the irradiation step of irradiating with active energy rays, ultraviolet rays having a peak wavelength of 365 to 405 nm are irradiated by a UV-LED.

10. A cured product of the active energy ray-curable composition according to claim 3.

11. A cured product of the active energy ray-curable ink described in claim 4.

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