Active energy ray curable inkjet ink, storage container, image forming apparatus, image forming method and cured product

Abstract

To provide an active energy ray-curable composition whose cured product has high hardness.SOLUTION: A curable composition contains a (meth)acrylamide compound expressed by a general formula (I) below. In the (meth)acrylamide compound expressed by the general formula (I) below, a proton composing a methylene neighboring a nitrogen atom from among hydrogen atoms composing a pyrrolidine ring has a signal in a lower magnetic field than that of a proton bonded to another secondary carbon atom, in 1H-NMR measurement. In the formula, R1 denotes a hydrogen atom or a methyl group, and R2 denotes a straight-chain or branched alkyl group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a curable composition, an ink-jet ink, a storage container, an image-forming apparatus, an image-forming method, and a cured product thereof. [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 cost and storage stability of the ink. 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. In recent years, safety is one of the functions required for polymerizable monomers in ink raw materials, and (meth)acrylamide compounds have been considered as monomers (Patent Document 1). In addition, Patent Document 2 discloses a photocurable ink containing a (meth)acrylamide compound with excellent photopolymerization properties. Summary of the Invention [Problem to be solved by the invention]

[0003] However, the hardness of the cured product obtained from the photocurable ink of Patent Document 2 was not sufficient and the durability was poor. Therefore, an object of the present invention is to provide a curable composition which produces a cured product having high hardness. [Means for solving the problem]

[0004] The curable composition of the present invention which solves the above problems is as described below. A curable composition comprising a (meth)acrylamide compound represented by the following general formula (I): The (meth)acrylamide compound represented by the following general formula (I) is 1A curable composition, characterized in that the (meth)acrylamide compound is one in which, in H-NMR measurement, among the hydrogen atoms constituting a pyrrolidine ring, a proton constituting a methylene adjacent to a nitrogen atom exhibits a signal in a lower magnetic field than protons bonded to other secondary carbons. [ka] (In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents a linear or branched alkyl group.) Effect of the Invention

[0005] According to the present invention, it is possible to provide a curable composition which produces a cured product having high hardness. [Brief description of the drawings]

[0006] [Figure 1] FIG. 1 is a 1H-NMR spectrum diagram of an acrylamide compound in which R1 is a hydrogen atom and R2 is a methyl group in the general formula (I). [Diagram 2] FIG. 2 is an enlarged view of a portion of the 1H-NMR spectrum of FIG. [Diagram 3] FIG. 3 is a schematic diagram showing an example of an image forming apparatus equipped with an inkjet ejection means. [Figure 4] FIG. 4 is a schematic diagram showing an example of another image forming apparatus (a three-dimensional image forming apparatus). [Diagram 5] FIG. 5 is a schematic explanatory diagram illustrating an example of a method for forming a three-dimensional object using an active energy ray-curable composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] The present invention relates to the curable composition described in (1) below, but also includes the following (2) to (18) as embodiments of the invention, and these embodiments will also be described. (1) A curable composition comprising a (meth)acrylamide compound represented by the following general formula (I): The (meth)acrylamide compound represented by the following general formula (I) is1 A curable composition, characterized in that the (meth)acrylamide compound is one in which, in H-NMR measurement, among the hydrogen atoms constituting a pyrrolidine ring, a proton constituting a methylene adjacent to a nitrogen atom exhibits a signal in a lower magnetic field than protons bonded to other secondary carbons. [ka] (In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents a linear or branched alkyl group.) (2) The curable composition according to the above (1), wherein in the general formula (I), R2 has 1 or more and 6 or less carbon atoms. (3) The curable composition according to (1) or (2) above, which is an active energy ray-curable composition. (4) An active energy ray-curable inkjet ink comprising the curable composition according to (3) above. (5) A composition-containing container, characterized in that it contains the actinic radiation-curable ink-jet ink described in (4) above. (6) A two-dimensional or three-dimensional image forming apparatus comprising the composition container according to (5) above and an irradiation means for irradiating with active energy rays. (7) The two-dimensional or three-dimensional image forming apparatus according to the above (6), 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 step of irradiating the active energy ray-curable ink according to (4) above with active energy rays. (9) The method for forming a two-dimensional or three-dimensional image according to the above (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 curable composition described in any one of (1) to (3) above. (11) A decorated body, comprising a substrate and a surface decoration made of the cured product according to (10) above. (12) A nail cosmetic comprising the curable composition according to any one of (1) to (3) above. (13) A hydrogel comprising the cured product according to (10) above. (14) A cell culture medium comprising the hardened material according to (10) above and a nutrient source necessary for cell culture. (15) A sustained drug release gel comprising the cured product according to (10) above and a drug. (16) A transdermal absorption gel comprising the cured product according to (10) above and a drug. (17) A contact lens comprising the cured product according to (10) above. (18) A medical adhesive comprising the curable composition according to any one of (1) to (3) above.

[0008] Hereinafter, an embodiment of the present invention will be described. ((Meth)acrylamide compound represented by general formula (I)) The curable composition of the present invention contains a (meth)acrylamide compound represented by the following general formula (I) as a polymerizable monomer. However, the (meth)acrylamide compound represented by the following general formula (I) is 1 In H-NMR measurements, among the hydrogen atoms that make up the pyrrolidine ring, the proton that constitutes the methylene adjacent to the nitrogen atom has a signal in a lower magnetic field than the protons that are bonded to other secondary carbons. [ka] (In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents a linear or branched alkyl group.)

[0009] Examples of the linear or branched alkyl group represented by R2 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, a pentyl group, a neopentyl group, and a hexyl group.

[0010] In the structure of the compound represented by the general formula (I), the number of carbon atoms in the alkyl or alkylene group represented by R2 is preferably 3 or less. This is because as the number of carbon atoms in the alkyl or alkylene group increases, the viscosity of the compound decreases, increasing the degree of freedom of the molecule and facilitating the polymerization reaction, but on the other hand, if the alkyl or alkylene group is too long, there is a tendency that the strength of the cured product cannot be obtained.

[0011] The compound represented by the general formula (I) will be described with reference to Figs. 1 and 2, taking as an example the case where R2 in the general formula (I) is a methyl group. The synthesis method is described in the Examples below. Figure 1 shows the structure of acrylamide compounds. 1 The H-NMR spectrum and signal assignments are shown. When one of the protons constituting the alkene of acrylamide is designated as 1, the alkene can be assigned to a shown in Figure 1. Figure 2 is an enlarged view of a portion of Figure 1, in which the methylene proton adjacent to the N atom of the pyrrolidine ring overlaps with the methyl group at 3.74 ppm, resulting in multiple spectra at 3.70-3.80 ppm and multiple spectra at 3.60-3.65 ppm, with signals in a lower magnetic field than the other methylene protons (1.90-2.33 ppm) constituting the pyrrolidine ring.

[0012] (Curable composition, active energy ray curable ink) The curable composition of the present invention (hereinafter sometimes referred to as "active energy ray curable composition") can be used by mixing two or more different (meth)acrylamide compounds, 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. The content of the (meth)acrylamide compound 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.

[0013] The curable composition may contain other photopolymerizable compounds other than the (meth)acrylamide compound represented by general formula (I). The mass ratio of the other photopolymerizable compounds to the (meth)acrylamide compound represented by general formula (I) is usually 0.01 to 100 mass%, preferably 0.1 to 50 mass%, of the (meth)acrylamide compound represented by general formula (I) in the total polymerizable compounds.

[0014] 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.

[0015] 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.

[0016] 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.

[0017] <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.

[0018] 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. Examples of the photocationically polymerizable compound include an epoxy compound, a vinyl ether compound, and an oxetane compound.

[0019] 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.

[0020] 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.

[0021] (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 ratio of the sensitizer to the photopolymerization initiator is usually 5 × 10 to 100 parts by mass of the photopolymerization initiator. -3 The amount is from 0.02 to 50 parts by mass, preferably from 0.02 to 50 parts by mass.

[0022] 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).

[0023] (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.

[0024] (Polymerization inhibitor) The curable composition may further contain a polymerization inhibitor. This can improve the storage stability (storage stability) of the curable composition. 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.

[0025] <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.

[0026] <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%.

[0027] <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.

[0028] <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.

[0029] <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.

[0030] <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.

[0031] <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. 4 or FIG. 5. FIG. 4 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, and sequentially laminating the cured layers to perform three-dimensional modeling (described in detail later), and FIG. 5 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 the layers to perform 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.

[0032] <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 hands, fingers, and clothing from getting dirty. In addition, it is possible to prevent foreign matter such as dust from getting mixed into 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.

[0033] <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 active energy ray curable composition of the present invention with active energy rays, at least 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.

[0034] FIG. 3 is an example of an image forming apparatus equipped with an inkjet ejection means. The ink is ejected onto the recording medium 22 supplied from the supply roll 21 by the printing units 23a, 23b, 23c, and 23d, which are equipped with ink cartridges and ejection heads for the active energy ray curable inks of the respective colors 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 the processing unit 25 and the print winding roll 26. Each of the printing units 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.

[0035] 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. 4 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. 4 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. After that, the support layer 36 is removed as necessary. Although only one object discharge head unit 30 is provided in FIG. 4, 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. The cured product of the present invention can be obtained by irradiating the curable composition of the present invention or the active energy ray-curable inkjet ink of the present invention with active energy rays.

[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.

[0038] (Nail cosmetics) The nail cosmetic of the present invention contains the curable composition of the present invention. The nail cosmetic of the present invention can be produced, for example, by blending the curable composition of the present invention with appropriate amounts of additives such as colorants such as pigments and dyes for decorating or reinforcing nails, inorganic fillers such as metal powder, calcium carbonate, talc, silica, alumina, and aluminum hydroxide, flame retardants, organic fillers, antioxidants, polymerization inhibitors, defoamers, coupling agents, leveling agents, and rheology control agents for the purpose of nail decoration or reinforcement. The nail cosmetic of the present invention can be used by applying it to the nails of humans or animals or to artificial nails and curing it.

[0039] (Hydrogel) The hydrogel of the present invention contains a cured product of the curable composition of the present invention. The hydrogel of the present invention can be produced, for example, by polymerizing the setting type composition of the present invention in the presence of a water-swellable layered mineral uniformly dispersed in water.

[0040] (Cell culture medium) The cell culture medium of the present invention comprises a hardened product of the hardening type composition of the present invention and a nutrient source necessary for cell culture. The cell culture medium of the present invention can be produced, for example, by polymerizing and drying the hardening composition of the present invention in the presence of a water-swellable layered mineral uniformly dispersed in water, and then immersing the composition in a liquid cell culture medium to absorb the liquid medium. When the object to be cultured is a cell, glucose and glutamine can be used as the nutrient source. Any substance that can be turned into a gas by volatilization, evaporation, or sublimation at the culture temperature is suitable for culturing microorganisms, and volatile and sublimable substances can be used. For example, ethanol and dry ice as carbon sources, and ammonia as nitrogen sources can be used. Ethanol corresponds to a nutrient source substance consisting of a liquid or solution solute at room temperature or culture temperature, ammonia corresponds to a nutrient source substance consisting of a solution solute at room temperature or culture temperature, and dry ice corresponds to a nutrient source substance consisting of a solid at room temperature or culture temperature. The amount of the nutrient source substance to be supplied can be adjusted by the concentration and amount of the nutrient source substance, but can also be adjusted by increasing or decreasing the pressure of the gas phase. Here, "volatilization" refers to becoming a gas at room temperature, "evaporation" refers to the phenomenon in which a liquid evaporates from its surface, and "sublimation" refers to a solid directly becoming a gas without first becoming a liquid. In addition, "volatile" refers to the property of easily volatilizing or vaporizing in the air at room temperature and pressure, and "non-volatile" refers to the property of not easily volatilizing or vaporizing in the air at room temperature and pressure. Also, multiple nutrient sources may be added simultaneously.

[0041] (Drug release gel) The drug sustained-release gel of the present invention comprises a drug and a cured product of the curable composition of the present invention. The drug-releasing gel of the present invention can be produced, for example, by polymerizing and drying the setting type composition of the present invention in the presence of a water-swellable layered mineral uniformly dispersed in water, and then immersing the composition in a liquid containing the desired drug to absorb the drug. It may be combined with hyaluronic acid.

[0042] (Transdermal absorption gel) The transdermal absorption gel of the present invention comprises a drug and a cured product of the curable composition of the present invention. The transdermal absorption gel of the present invention can be produced, for example, by polymerizing the curable composition of the present invention on a substrate in the presence of the curable composition of the present invention and a water-swellable layered compound uniformly dispersed in water, drying the composition, and then immersing the composition in a liquid of a desired transdermal absorption agent. The production method can be changed depending on the intended use, and other production methods include a method in which the transdermal absorption gel is produced and then bonded to a substrate, or a transdermal absorption gel can be produced without using a substrate. The transdermal gel may also contain one or more suitable gelling or thickening agents, such as silicone, tragacanth, starch or starch derivatives, cellulose or cellulose derivatives, or polyacrylic acid or its derivatives, and may also contain substances that enhance transdermal absorption, such as bile salts or their derivatives and / or phospholipids.

[0043] (Contact Lenses) The contact lens of the present invention comprises a cured product of the curable composition of the present invention. The contact lens of the present invention can be produced, for example, by synthesizing a polymer of the curable composition of the present invention, forming a rod-shaped or other molded product as a cured product, cutting out a molded product of a desired size from the molded product, and then subjecting the molded product to finishing processing such as polishing. Another method is a molding method using a mold. In the molding method using a mold, the curable composition of the present invention can be injected into the gap between a concave mold and a convex mold, and then polymerized to produce the contact lens.

[0044] (Medical adhesive) The medical adhesive of the present invention comprises the curable composition of the present invention. The medical adhesive of the present invention has a substrate and a layer containing the curable composition of the present invention or a cured product of the curable composition on the substrate, and can be produced by further laminating other components as necessary. Medical adhesives are suitable for use in protecting wounds and surgical sites, bonding and covering, biorepair materials, artificial membranes, and the like. The content of the (meth)acrylamide compound represented by the general formula (I) contained in these curable compositions and cured products can be freely adjusted depending on the application, and the content ratio of the curable composition or cured product is preferably 5% by mass to 95% by mass. EXAMPLES

[0045] 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.

[0046] First, a synthesis example of the (meth)acrylamide compound represented by the general formula (I) used in the present invention will be described.

[0047] (Synthesis Example 1 of Acrylamide Compound) L-proline methyl ester acrylamide was synthesized by the reactions and procedures shown below. [ka] In a 300mL four-neck flask, 15.3g (92.4mmol) of L-proline-methyl ester hydrochloride (Tokyo Chemical Industry Co., Ltd.) and 60mL of tetrahydrofuran were charged and cooled with a cryogen. An aqueous solution of 25.5g (185mmol) of potassium carbonate dissolved in 35mL of pure water was gradually added with a pipette to perform dehydrochlorination treatment. After stirring at room temperature for 1 hour, the mixture was cooled again with a cryogen, and 8.78g (97mmol) of acryloyl chloride was added dropwise over 1 hour (liquid temperature: 0 to +1°C). After the dropwise addition, the mixture was returned to room temperature and stirred for 1 hour, then transferred to a separatory funnel, and the aqueous layer was extracted three times with ethyl acetate. The entire organic layer was washed in this order with a saturated aqueous sodium bicarbonate solution and a saturated sodium chloride solution, dried with sodium sulfate, and concentrated under reduced pressure to obtain a crude product. This crude product was purified and isolated by silica gel column chromatography (packing material: Wakogel C-300, developing solvent: n-hexane / ethyl acetate=1 / 2) to obtain 14.6 g (yield 86%) of the target product as a colorless liquid. To confirm the structure, 1Using H-NMR (500MHz) (JEOL) 1 The H-NMR spectrum was measured. The identification data are as follows. The measured spectrum is shown in Figures 1 and 2. 1 H-NMR(CDCl3): δ 1.93-2.32(m,4H), 3.60-3.66(m,1H), 3.70-3.79(m,1H), 3.75(m,3H), 4.51-4.58(m,1H), 5.65-5.73(m,1H), 6.22-6.51(m,2H)

[0048] (Synthesis Example 2 of an Acrylamide Compound) According to the procedure shown below, L-proline ethyl ester acrylamide represented by the following structural formula was synthesized. [ka] L-proline (Tokyo Chemical Industry Co., Ltd.) was dissolved in ethanol, and thionyl chloride was added dropwise to the solution in an ice bath, followed by stirring at room temperature for 10 hours. The liquid phase of the reaction solution was distilled off under reduced pressure to obtain L-proline ethyl ester hydrochloride as a white solid. Next, the L-proline ethyl ester hydrochloride was used to carry out the same procedure as described in Synthesis Example 1 to obtain L-proline ethyl ester acrylamide.

[0049] (Synthesis Example 3 of an Acrylamide Compound) According to the procedure shown below, L-proline propyl ester acrylamide represented by the following structural formula was synthesized. [ka] L-proline propyl ester acrylamide was obtained by carrying out the same procedure as in Synthesis Example 2, except that 1-propanol was used instead of ethanol.

[0050] (Comparative Example Compound) The compound having the structure shown below, which is described in Japanese Patent No. 6277806, was used as a comparative compound. [ka]

[0051] (Examples 1 to 3, Comparative Example 1) [Preparation of active energy ray-curable composition] The acrylamide compounds obtained in Synthesis Examples 1 to 3 and each of the compounds in the Comparative Examples (950 mg) were mixed with 50 mg of a photopolymerization initiator Irgacure TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF Japan Ltd.) and stirred to obtain active energy ray-curable compositions.

[0052] <Evaluation of curability> Each active energy ray curable composition was filled into a plastic composition storage container. The composition storage container was then placed in a container equipped with 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 for supplying ink from a composition storage container to the inkjet head were incorporated into an image forming apparatus. 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 discharged by inkjet 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 printed images were produced by irradiating ultraviolet rays using a UV-LED. 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. The evaluation results are shown in Table 1. The active energy ray curable composition using the (meth)acrylamide compound of the present invention cures with lower energy than the cured product obtained from the acrylamide compound of the comparative example.

[0053] <Evaluation of pencil hardness> The active energy ray curable compositions of Examples 1 to 3 and Comparative Example 1 were applied to a PET film to a thickness of 10 μm, and curing was performed using a UV-LED (Integration Technology Japan's "LED ZERO", wavelength 395 nm) as active energy ray irradiation means under conditions of a total irradiation energy of 2000 mJ / cm2. The cured samples were subjected to a pencil hardness test in accordance with the JIS K5600-5-4 standard. Here, a pencil scratch hardness tester (Cotec Co., Ltd., model KT-VF2391, load 750 g) and a pencil for pencil hardness test (Mitsubishi Pencil Co., Ltd.) were used. The evaluation results are shown in Table 1. The active energy ray-curable composition using the (meth)acrylamide compound of this example has a higher hardness than the cured product obtained in the comparative example using the comparative acrylamide compound.

[0054] [Table 1] [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 Document 2

Claims

1. An active energy ray-curable inkjet ink comprising a curable composition containing a (meth)acrylamide compound represented by the following general formula (I): The (meth)acrylamide compound represented by the following general formula (I) is １ a (meth)acrylamide compound in which, in H-NMR measurement, among hydrogen atoms constituting a pyrrolidine ring, a proton constituting a methylene adjacent to a nitrogen atom exhibits a signal in a lower magnetic field than protons bonded to other secondary carbons; The content of the (meth)acrylamide compound in the curable composition is 20% by mass or more and 98% by mass or less.

1. An actinic ray-curable ink-jet ink comprising: 【Chemistry 1】 (In the formula, R １ represents a hydrogen atom or a methyl group, R ２ represents a linear or branched alkyl group having 1 to 6 carbon atoms.

2. The active energy ray-curable inkjet ink according to claim 1, wherein the content of the (meth)acrylamide compound in the curable composition is 30% by mass or more and 90% by mass or less.

3. The active energy ray-curable inkjet ink according to claim 1, wherein the content of the (meth)acrylamide compound in the curable composition is 30% by mass or more and 80% by mass or less.

4. A composition-containing container, comprising the actinic ray-curable ink-jet ink according to claim 1 .

5. A two-dimensional or three-dimensional image forming apparatus comprising: a composition container according to claim 4; and an irradiation means for irradiating with active energy rays.

6. 6. The two-dimensional or three-dimensional image forming apparatus according to claim 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.

7. A method for forming a two-dimensional or three-dimensional image, comprising the step of irradiating the active energy ray-curable ink according to claim 1 with active energy rays.

8. 8. The method for forming a two-dimensional or three-dimensional image according to claim 7, wherein in the step of irradiating with active energy rays, ultraviolet rays having a peak wavelength of 365 to 405 nm are irradiated by a UV-LED.

9. A cured product of the actinic ray-curable ink-jet ink according to claim 1 .

10. A decorated body having a surface decorated with a cured product of an active energy ray-curable composition containing a (meth)acrylamide compound represented by the following general formula (I): The (meth)acrylamide compound represented by the following general formula (I) is a (meth)acrylamide compound in which, in 1 H-NMR measurement, among hydrogen atoms constituting a pyrrolidine ring, a proton constituting a methylene adjacent to a nitrogen atom exhibits a signal in a lower magnetic field than protons bonded to other secondary carbons: The content of the (meth)acrylamide compound in the curable composition is 20% by mass or more and 98% by mass or less. A decorative body characterized by the above. 【Chemistry 1】 (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a linear or branched alkyl group having 1 to 6 carbon atoms.)

11. A nail cosmetic comprising an active energy ray-curable composition containing a (meth)acrylamide compound represented by the following general formula (I), The (meth)acrylamide compound represented by the following general formula (I) is a (meth)acrylamide compound in which, in 1 H-NMR measurement, among hydrogen atoms constituting a pyrrolidine ring, a proton constituting a methylene adjacent to a nitrogen atom exhibits a signal in a lower magnetic field than protons bonded to other secondary carbons: The content of the (meth)acrylamide compound in the curable composition is 20% by mass or more and 98% by mass or less. A nail cosmetic characterized by the above. 【Chemistry 1】 (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a linear or branched alkyl group having 1 to 6 carbon atoms.)

12. A cell culture medium comprising a cured product of an active energy ray-curable composition containing a (meth)acrylamide compound represented by the following general formula (I) and a nutrient source necessary for cell culture, The (meth)acrylamide compound represented by the following general formula (I) is a (meth)acrylamide compound in which, in 1 H-NMR measurement, among hydrogen atoms constituting a pyrrolidine ring, a proton constituting a methylene adjacent to a nitrogen atom exhibits a signal in a lower magnetic field than protons bonded to other secondary carbons: The content of the (meth)acrylamide compound in the curable composition is 20% by mass or more and 98% by mass or less. A cell culture medium comprising: 【Chemistry 1】 (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a linear or branched alkyl group having 1 to 6 carbon atoms.)

13. A medical adhesive comprising an active energy ray-curable composition containing a (meth)acrylamide compound represented by the following general formula (I): The (meth)acrylamide compound represented by the following general formula (I) is a (meth)acrylamide compound in which, in 1 H-NMR measurement, among hydrogen atoms constituting a pyrrolidine ring, a proton constituting a methylene adjacent to a nitrogen atom exhibits a signal in a lower magnetic field than protons bonded to other secondary carbons: The content of the (meth)acrylamide compound in the curable composition is 20% by mass or more and 98% by mass or less. A medical adhesive characterized by: 【Chemistry 1】 (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a linear or branched alkyl group having 1 to 6 carbon atoms.)

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