JP7027971B2 - (Meta) acrylamide compound, curable composition, active energy ray curable ink, composition container, 2D or 3D image forming device, 2D or 3D image forming method, cured product and decoration - Google Patents

Description

The present invention relates to a (meth) acrylamide compound, a curable composition, an active energy ray curable ink, a composition accommodating container, a two-dimensional or three-dimensional image forming apparatus, a two-dimensional or three-dimensional image forming method, a cured product, and a cured product. Regarding decorative bodies.

An inkjet recording method is known as a method of forming an image on a recording medium such as paper. This inkjet recording method has high ink consumption efficiency and is excellent in resource saving, and it is possible to keep the ink cost per unit recording low.

In recent years, among them, an inkjet recording method using a curable ink has attracted attention. For example, an ink using a tertiary acrylamide compound having an ester structure has been proposed (see, for example, Patent Document 1).

However, conventional inks are not always satisfactory in terms of curability, and compounds having particularly excellent photopolymerizability have been required.
An object of the present invention is to provide a (meth) acrylamide compound having better curability than conventional ones.

In order to solve the above problems, the present invention is a (meth) acrylamide compound represented by the following general formula (1).

(In the equation, R ₁ indicates a hydrogen atom or a methyl group, R ₂ , R ₄ , R ₅ indicates a linear or branched alkyl group, and R ₂ , R ₄ and R ₅ may be the same or different, respectively. , R ₃ indicates a linear or branched alkylene group.)

According to the present invention, it is possible to provide a (meth) acrylamide compound having excellent curability.

It is a schematic diagram which shows an example of the image forming apparatus in this invention. It is a schematic diagram which shows an example of another image forming apparatus in this invention. It is a schematic diagram which shows an example of still another image forming apparatus in this invention.

((Meta) acrylamide compound)
The (meth) acrylamide compound of the present invention is represented by the following general formula (1).

(In the equation, R ₁ indicates a hydrogen atom or a methyl group, R ₂ , R ₄ , R ₅ indicates a linear or branched alkyl group, and R ₂ , R ₄ and R ₅ may be the same or different, respectively. , R ₃ indicates a linear or branched alkylene group.)

The (meth) acrylamide compound represented by the general formula (1) of the present invention is characterized by having a tertiary acrylamide and a carbamoyl group. Since it is a tertiary acrylamide compound, its viscosity is relatively low as compared with a secondary acrylamide compound, and it has almost no unpleasant odor like (meth) acrylate. Therefore, active energy ray-curable inks, especially inks, It is suitable for active energy ray-curable inkjet ink that ejects ink as minute droplets.

Examples of the linear or branched alkyl group in R ₂ , R ₄ , and R ₅ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, and a t-butyl group. , Pentyl group, neopentyl group, hexyl group and the like.
Examples of the linear or branched alkylene group in R ₃ include a methylene group, an ethylene group, a propylene group, a butylene group and the like.

Further, in the structure of the compound represented by the general formula (1), the carbon number of the alkyl group or the alkylene group represented by R ₂ , R _3, R ₄ and R ₅ is preferably 4 or less. This is because the viscosity of the compound decreases as the number of carbon atoms in the alkyl group or alkylene group increases, which increases the degree of freedom of the molecule and facilitates the polymerization reaction. On the other hand, if the alkyl group or alkylene group is too long. Since there is a tendency that the strength of the cured product cannot be obtained, the number of carbon atoms is preferably 4 or less.

The method for synthesizing the (meth) acrylamide compound of the present invention will be described.
Acrylamide alcohol, which is an intermediate, is obtained by reacting a secondary amino alcohol as a raw material with an acid chloride compound of acrylic acid chloride or methacrylic acid chloride. Then, the desired product can be obtained by reacting with N, N'-dialkylcarbamoyl chloride.

The solvent used for the reaction is not particularly determined as long as it is inert to the acid chloride, and for example, ethyl acetate, tetrahydrofuran, dioxane, dichloromethane, chloroform and the like are used.
In addition, it is preferable to use a base to capture hydrogen chloride, which is a by-product generated during the reaction, and examples thereof include triethylamine, potassium carbonate, and pyridine. Potassium carbonate can also be used as a powder or an aqueous solution. As the amount of the base used, it is preferable to use at least an equimolar amount of the acid chloride to be used.
As the reaction temperature, the reaction proceeds even at room temperature, but if the reactivity is high, it is preferable to cool it with a cryogen or the like, and if the reactivity is slow, it may be heated.
The purification operation can be carried out by a known method, and the (meth) acrylamide compound of the present invention can be obtained by column chromatography or distillation.
The above synthesis method is shown in the following equation.

Next, exemplary compounds (1-1 to 9-5) as specific examples of the (meth) acrylamide compound of the present invention are shown, but the present invention is not limited thereto. In the following specific examples, R ₁ represents a hydrogen atom or a methyl group.

(Curing composition, active energy ray curable ink)
In the curable composition of the present invention, two or more different (meth) acrylamide compounds can be mixed and used, and the different compounds in this case also include structural isomers. The mixing ratio is not particularly limited. The curable composition of the present invention is preferably used as an active energy ray-curable ink.
The content of the (meth) acrylamide compound in the cured composition is usually 20 to 98% by mass, preferably 30 to 90% by mass, and even more preferably 30 to 80% by mass.

The curable composition can also contain other photopolymerizable compounds other than the (meth) acrylamide compound represented by the general formula (1). The mass ratio of the other photopolymerizable compounds to the (meth) acrylamide compound represented by the general formula (1) is usually 0 for the (meth) acrylamide compound represented by the general formula (1) among all the polymerizable compounds. It is 0.01 to 100% by mass, preferably 0.1 to 50% by mass. Hereinafter, the curing type composition may be referred to as an active energy ray curing type composition.

The other photopolymerizable compound is not particularly limited, and examples thereof include a photoradical polymerizable compound, a photocationic polymerizable compound, a photoanionic polymerizable compound, and two or more thereof may be used in combination.

The photoradical polymerizable compound is not particularly limited as long as it is a compound having one or more ethylenically unsaturated groups capable of photoradical polymerization, and includes monomers, oligomers, polymers and the like. 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 from them, and anhydrides having ethylenically unsaturated groups. Examples thereof include acrylic nitrile, styrene, unsaturated polyester, unsaturated polyether, unsaturated polyamide, unsaturated urethane and the like.

Specific examples of the photoradical polymerizable compound include 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) propane, and 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, tri Acrylic acid derivatives such as methylol propanetriacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and epoxy acrylate, methyl methacrylate, n-butyl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexane. Didiol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylol ethanetrimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) ) Methacrylic acid derivatives such as propane, acrylamide derivatives such as N-methylol acrylamide, diacetone acrylamide, 2-hydroxyethyl acrylamide, acryloyl morpholine, allyl compound derivatives such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate, ethylene. Glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monobini Luether, 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, trimethylolpropane trivinyl ether. Di or trivinyl 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. Monovinyl ether compounds such as ether-o-propylene carbonate, dodecylvinyl ether, diethylene glycol monovinyl ether, octadecylvinyl ether, 2-ethylhexyl diglycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl acrylate, neopentyl hydroxypivalate Glycol diacrylate, 2-acryloyloxyethyl phthalic acid, methoxypolyethylene glycol acrylate, tetramethylol methanetriacrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, dimethylol tricyclodecandiacrylate, ethoxylated phenyl acrylate , 2-Acryloyloxyethyl succinic acid, nonylphenolethylene oxide adduct acrylate, modified glycerin triacrylate, bisphenol A diglycidyl ether acrylic acid adduct, modified bisphenol A diacrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl hexahydro Phthalic acid, propylene oxide adduct diacrylate of bisphenol A, ethylene oxide adduct diacrylate of bisphenol A, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, tolylene isosocyanato urethane prepolymer, lactone-modified flexible acrylate, butoxyethyl Acrylate, propylene glycol diglycidyl ether acrylic acid adduct, pentaerythritol triacrylate , Hexamethylene disosocyanate urethane prepolymer, 2-hydroxyethyl acrylate, methoxydipropylene glycol acrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, hexamethylene disosocyanato urethane prepolymer, stearyl acrylate, isoamyl acrylate, isomyristyl Examples thereof include acrylates, isostearyl acrylates and lactone-modified acrylates.

(Polymer initiator)
The active energy ray-curable composition of the present invention may contain a polymerization initiator. The polymerization initiator may be any one capable of generating active species such as radicals and cations by the energy of the active energy ray and initiating the polymerization of the polymerizable compound (monomer or oligomer). As such a polymerization initiator, known radical polymerization initiators, cationic polymerization initiators, base generators and the like can be used alone or in combination of two or more, and among them, a radical polymerization initiator is used. Is preferable. Further, the polymerization initiator is preferably contained in an amount of 5 to 20% by mass with respect to the total mass (100% by mass) of the composition in order to obtain a sufficient curing rate.
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, and the like. Examples thereof include ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.
Further, in addition to the above-mentioned polymerization initiator, a polymerization accelerator (sensitizer) can also be used in combination. The polymerization accelerator is not particularly limited, but for example, trimethylamine, methyldimethylamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, p-dimethylaminobenzoic acid-2-ethylhexyl, N, Amine compounds such as N-dimethylbenzylamine and 4,4'-bis (diethylamino) benzophenone are preferable, and the content thereof may be appropriately set according to the polymerization initiator used and the amount thereof.

The combination of the photopolymerizable compound and the photopolymerization initiator includes a combination of a photoradical polymerizable compound and a photoradical polymerization initiator, a combination of a photocationic polymerizable compound and a photocationic polymerization initiator, and a photoanionic anion. Examples thereof include a combination of a polymerizable compound and a photoanionic polymerization initiator.
Examples of the photocationically polymerizable compound include an epoxy compound, a vinyl ether compound, an oxetane compound and the like.
Examples of the photocationic polymerization initiator include B (C ₆ F ₅ ) _4- ^, PF _6- ^, AsF _6- ^, SbF _6- ^, and CF ₃ SO ₃ of aromatic onium compounds such as diazonium, ammonium, iodinenium, sulfonium, and phosphonium. ^-Salts , sulfonates capable of generating sulfonic acid, halides capable of generating hydrogen halides, iron allen complexes and the like can be mentioned.
Examples of the photoanionic polymerizable compound include epoxy compounds, lactone compounds, acrylic compounds, and methacrylic compounds. Of these, acrylic compounds and methacrylic compounds exemplified as photoradical polymerizable compounds are preferable.
Examples of the photoanionic polymerization initiator include an o-nitrobenzyl carbamate derivative, an o-acyloxyl derivative, an o-carbamoyloxime amidine derivative and the like.

(Sensitizer)
The curable composition may further contain a sensitizer in order to accelerate the decomposition of the photopolymerization initiator by irradiation with active energy rays.
The sensitizer absorbs active energy rays and becomes an electronically excited state, and in that state, it comes into contact with the polymerization initiator and undergoes chemical changes (decomposition, radicals, acids) of the polymerization initiator due to actions such as electron transfer, energy transfer, and heat generation. Or the generation of radicals) is promoted.
The mass ratio of the sensitizer to the photopolymerization initiator is usually 5 × 10 ^-3 to 200% by mass, preferably 0.02 to 50% by mass, based on the photopolymerization initiator.

The sensitizer is not particularly limited, but a sensitizing dye having an absorption wavelength in the wavelength region of 350 to 450 nm can be used. Examples include polynuclear aromatics (eg pyrene, perylene, triphenylene), xanthenes (eg fluoressein, eosin, erythrosin, rhodamine B, rosebengal), cyanines (eg thiacarbocyanine, oxacarbocyanine). ), Merocyanines (eg, merocyanine, carbocyanine), thiadins (eg, thionin, methylene blue, toluidin blue), acridins (eg, acridin orange, chloroflavin, acryflavin), anthraquinones (eg, anthraquinone), squarylium. Species (eg, squarylium), coumarins (eg, 7-diethylamino-4-methylcoumarin) and the like.

(Co-sensitizer)
The curable composition may further contain 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 by oxygen.
The co-sensitizer is not particularly limited, but is an amine compound such as triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline, 2-mercaptobenzothiazole, 2-mercapto. Examples thereof include thiols and sulfides such as benzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline and β-mercaptonaphthalene.

(Polymerization inhibitor)
The curable composition may further contain a polymerization inhibitor. This makes it possible to improve the storage stability (storage stability) of the curable composition. In addition, it is possible to prevent head clogging due to thermal polymerization when the curable composition is heated to reduce its viscosity and discharged.
The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone, benzoquinone, p-methoxyphenol, TEMPO, TEMPOL, and a cuperon complex of aluminum. The content of the polymerization inhibitor in the ink is usually 200 to 20000 ppm.

(Color 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 black, white, magenta, cyan, yellow, green, orange, glossy colors such as gold and silver, etc., depending on the purpose and required characteristics of the composition in the present invention. Can be used. The content of the coloring material may be appropriately determined in consideration of a desired color concentration, dispersibility in the composition, etc., and is not particularly limited, but is 0. It is preferably 1 to 20% by mass. The active energy ray-curable composition of the present invention may be colorless and transparent without containing a coloring material, and in that case, for example, it is suitable as an overcoat layer for protecting an image.
As the pigment, an inorganic pigment or an organic pigment can be used, and one kind may be used alone or two or more kinds may be used in combination.
As the inorganic pigment, for example, carbon black (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide can be used.
Examples of organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azolakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments and quinophthalones. Polycyclic pigments such as pigments, dye chelate (for example, basic dye type chelate, acidic dye type chelate, etc.), dyeing rake (basic dye type rake, acidic dye type rake), nitro pigment, nitroso pigment, aniline black, Daylight fluorescent pigments can be mentioned.
Further, in order to improve the dispersibility of the pigment, a dispersant may be further contained. The dispersant is not particularly limited, and examples thereof include dispersants commonly used for preparing pigment dispersions such as polymer dispersants.
As the dye, for example, an acid dye, a direct dye, a reactive dye, and a basic dye can be used, and one type may be used alone or two or more types may be used in combination.

(Organic solvent)
The active energy ray-curable composition of the present invention may contain an organic solvent, but it is preferable not to contain it 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 further enhanced, and it is possible to prevent environmental pollution. .. The "organic solvent" means a general non-reactive organic solvent such as ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and should be distinguished from the reactive monomer. be. Further, "not containing" the organic solvent means that it is substantially free of the organic solvent, and it is preferably less than 0.1% by mass.

(Other ingredients)
The active energy ray-curable composition of the present invention may contain other known components, if necessary. The other components are not particularly limited, but are, for example, conventionally known surfactants, polymerization inhibitors, leveling agents, antifoaming agents, fluorescent whitening agents, penetration promoters, wetting agents (moisturizers), and fixing agents. Agents, viscosity stabilizers, fungicides, preservatives, antioxidants, UV absorbers, chelating agents, pH regulators, thickeners and the like can be mentioned.

(Preparation of active energy ray-curable composition)
The active energy ray-curable composition of the present invention can be produced by using the above-mentioned various components, and the preparation means and conditions thereof are not particularly limited. For example, a polymerizable monomer, a pigment, a dispersant and the like can be used in a ball mill. It is put into a disperser such as a kitty mill, a disc mill, a pin mill, and a dyno mill, and dispersed to prepare a pigment dispersion, and the pigment dispersion is further mixed with a polymerizable monomer, an initiator, a polymerization inhibitor, a surfactant, and the like. It can be prepared by letting it.

(viscosity)
The viscosity of the active energy ray-curable composition of the present invention may be appropriately adjusted according to the intended use and application means, and is not particularly limited. For example, when a discharge means for discharging the composition from a nozzle is applied. The viscosity in the range of 20 ° C. to 65 ° C., preferably 3 to 40 mPa · s, more preferably 5 to 15 mPa · s, and particularly preferably 6 to 12 mPa · s at 25 ° C. Further, it is particularly preferable that the viscosity range is satisfied without containing the organic solvent. For the above viscosity, a cone rotor (1 ° 34'× R24) was used with a cone plate type rotational viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd., the rotation speed was 50 rpm, and the temperature of constant temperature circulating water was 20 ° C. It can be appropriately set and measured in the range of about 65 ° C. VISCOMATE VM-150III can be used to adjust the temperature of the circulating water.

(Curing means)
Examples of the means for curing the curable composition of the present invention include heat curing or curing with an active energy ray, and among these, curing with an active energy ray is preferable.
The active energy rays used for curing the active energy ray-curable composition of the present invention include polymerizable components in the composition such as electron beam, α ray, β ray, γ ray, and X ray in addition to ultraviolet rays. It is not particularly limited as long as it can impart the energy required for advancing the polymerization reaction of the above. In particular, when a high-energy light source is used, the polymerization reaction can proceed without using a polymerization initiator. Further, in the case of ultraviolet irradiation, mercury-free is strongly desired from the viewpoint of environmental protection, and replacement with a GaN-based semiconductor ultraviolet light emitting device is very useful industrially and environmentally. Further, the ultraviolet light emitting diode (UV-LED) and the ultraviolet laser diode (UV-LD) are compact, have a long life, have high efficiency, and are low in cost, and are preferable as an ultraviolet light source.

(Use)
The application of the active energy ray-curable composition of the present invention is not particularly limited as long as it is in a field where an active energy ray-curable material is generally used, and can be appropriately selected depending on the intended purpose, for example, for molding. Examples thereof include resins, paints, adhesives, insulating materials, mold release agents, coating materials, sealing materials, various resists, and various optical materials.
Further, the active energy ray-curable composition of the present invention can be used as an ink to not only form a design coating film on two-dimensional characters and images and various substrates, but also to form a three-dimensional stereoscopic image (three-dimensional model). It can also be used as a three-dimensional modeling material for forming. This three-dimensional modeling material may be used, for example, as a binder between powder particles used in a powder laminating method in which three-dimensional modeling is performed by repeatedly curing and laminating a powder layer, and is also shown in FIGS. 2 and 3. It may be used as a three-dimensional constituent material (model material) or a support member (support material) used in such a laminated molding method (stereolithography). Note that FIG. 2 is a method in which the active energy ray-curable composition of the present invention is discharged into a predetermined region, and the ones cured by irradiating with active energy rays are sequentially laminated to perform three-dimensional modeling (details will be described later). FIG. 3 shows that the storage pool (accommodation portion) 1 of the active energy ray-curable composition 5 of the present invention is irradiated with the active energy ray 4 to form a cured layer 6 having a predetermined shape on the movable stage 3. This is a method of sequentially stacking and performing three-dimensional modeling.
As a three-dimensional modeling device for modeling a three-dimensional model using the active energy ray-curable composition of the present invention, a known one can be used, and the present invention is not particularly limited, but for example, a means for accommodating the composition. , A supply means, a discharge means, an active energy ray irradiation means, and the like.
The present invention also includes a cured product obtained by curing an active energy ray-curable composition and a molded product obtained by processing a structure in which the cured product is formed on a substrate. The molded product is, for example, a cured product or structure formed in a sheet shape or a film shape, which has been subjected to molding processing such as heat stretching or punching, and is, for example, an automobile, an OA device, or electricity. -Suitably used for applications that require molding after decorating the surface, such as electronic devices, meters for cameras, and panels for operation units.
The base material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paper, thread, fiber, cloth, leather, metal, plastic, glass, wood, ceramics, or a composite material thereof and the like. From the viewpoint of processability, a plastic base material is preferable.

(Composition container)
The composition 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 containing the ink can be used as an ink cartridge or an ink bottle, whereby ink transfer, ink replacement, etc. It is not necessary to touch the ink directly in the work, and it is possible to prevent the fingers and clothes from getting dirty. In addition, it is possible to prevent foreign substances such as dust from being mixed into the ink. The shape, size, material, etc. of the container itself may be suitable for the intended use and usage, and is not particularly limited, but the material is a light-shielding material that does not transmit light, or the container blocks light. It is desirable that it is covered with a sex sheet or the like.

(Image formation method, forming device)
As the method for forming an image of the present invention, active energy rays may be used, or heating or the like may be mentioned.
At least, in order to cure the active energy ray-curable composition of the present invention with active energy rays, there is an irradiation step of irradiating the active energy rays, and the image forming apparatus of the present invention irradiates the active energy rays. An irradiation means for the purpose and an accommodating portion for accommodating the active energy ray-curable composition of the present invention may be provided, and the container may be accommodated in the accommodating portion. Further, it may have a discharge step and a discharge means for discharging the active energy ray-curable composition. The method of discharging is not particularly limited, and examples thereof include a continuous injection type and an on-demand type. Examples of the on-demand type include a piezo method, a thermal method, and an electrostatic method.
FIG. 1 is an example of an image forming apparatus provided with an inkjet ejection means. Ink is ejected to the recorded medium 22 supplied from the supply roll 21 by each color printing unit 23a, 23b, 23c, 23d provided with an ink cartridge for each color active energy ray-curable ink of yellow, magenta, cyan, and black and an ejection head. Will be done. Then, the light sources 24a, 24b, 24c, and 24d for curing the ink are irradiated with active energy rays to cure the ink, and a color image is formed. After that, the recording medium 22 is conveyed to the processing unit 25 and the printed matter take-up roll 26. Each printing unit 23a, 23b, 23c, 23d may be provided with a heating mechanism so that the ink is liquefied at the ink ejection portion. Further, if necessary, a mechanism for cooling the recording medium to about room temperature by contact or non-contact may be provided. Further, as the inkjet recording method, a serial method in which the head is moved to eject ink onto the recording medium or a recording medium is continuously moved with respect to the recording medium which moves intermittently according to the ejection head width. Any of the line methods of ejecting ink onto the recording medium from the head held at a fixed position can be applied.
The recording medium 22 is not particularly limited, and examples thereof include paper, film, ceramics, glass, metal, and composite materials thereof, and may be in the form of a sheet. Further, the configuration may be such that only single-sided printing is possible or double-sided printing is possible. Not limited to those used as general recording media, cardboard, building materials such as wallpaper and flooring, cloth for clothing such as concrete and T-shirts, textiles, leather and the like can be appropriately used.
Further, the activation of the active energy rays from the light sources 24a, 24b, and 24c may be weakened or omitted, and after printing a plurality of colors, the activation energy rays may be irradiated from the light source 24d. This makes it possible to save energy and reduce costs.
The recorded materials recorded by the ink of the present invention include not only those printed on a smooth surface such as ordinary paper or resin film, but also those printed on a surface to be printed having irregularities, metal, ceramics, and the like. It also includes those printed on the printed surface made of various materials. Further, by stacking two-dimensional images, it is possible to form a partially three-dimensional image (an image composed of two-dimensional and three-dimensional) or a three-dimensional object.
FIG. 2 is a schematic view showing an example of another image forming apparatus (three-dimensional stereoscopic image forming apparatus) according to the present invention. The image forming apparatus 39 of FIG. 2 uses a head unit (movable in the AB direction) in which inkjet heads are arranged to discharge the first active energy ray-curable composition from the discharge head unit 30 for a modeled object for a support. A second active energy ray-curable composition having a composition different from that of the first active energy ray-curable composition is discharged from the head units 31 and 32, and each of these compositions is cured by adjacent ultraviolet irradiation means 33 and 34. It is laminated while being laminated. More specifically, for example, the second active energy ray-curable composition is discharged from the support discharge head units 31 and 32 onto the modeled object support substrate 37, and is irradiated with the active energy rays to be solidified. After forming the first support layer having the reservoir portion, the first active energy ray-curable composition is discharged from the discharge head unit 30 for a modeled object to the reservoir portion, and is irradiated with the active energy ray to be solidified. By repeating the process of forming the first modeled object layer a plurality of times while lowering the vertically movable stage 38 according to the number of layers, the support layer and the modeled object layer are laminated to form the three-dimensional model 35. To make. After that, the support laminated portion 36 is removed as needed. In FIG. 2, only one discharge head unit 30 for a modeled object is provided, but two or more may be provided.

(Cursed product)
The cured product is formed by 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 the above-mentioned curable composition can be used.
As the active energy ray-curable ink, the same ink as the active energy ray-curable ink can be used.

(Decorative body)
As the decorative body, a surface decoration made of a cured product is applied on the base material, and the same one as the cured product can be used.

The base material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paper, thread, fiber, cloth, leather, metal, plastic, glass, wood, ceramics, or a composite material thereof and the like. From the viewpoint of workability, plastic is preferable.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the example, "parts" and "%" are "parts by mass" and "% by mass". The ¹ H-NMR spectrum was measured using ¹ H-NMR (500 MHz) (manufactured by JEOL Ltd.).

[Example 1]
(R ₁ is a hydrogen atom in Exemplified Compound 1-2)
2- (Methylamino) ethanol (6.01 g, 80 mmol) was dissolved in tetrahydrofuran (100 ml) and potassium carbonate (22.6 g, 164 mmol) was added. The mixture was cooled to −10 ° C. in an ice bath, acrylic acid chloride (6.88 g, 76 mmol) was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours. Then, the mixture was cooled to 5 ° C. again in an ice bath, diethylcarbamoyl chloride (10.84 g, 80 mmol) was slowly added dropwise, and the mixture was stirred at room temperature for 10 hours.
After filtering the precipitated salt with Celite, the aqueous layer is extracted with ethyl acetate, combined with the organic layer, washed in the order of saturated sodium hydrogen carbonate solution and saturated sodium chloride solution, dried with sodium sulfate, and then concentrated under reduced pressure. The crude product was obtained. This crude product was isolated by silica gel column chromatography (filler: Wakogel C-300, developing solvent: hexane / ethyl acetate = 1/2), and 3.3 g of a colorless oily substance of the following compound 1-2A (yield 18). %) Was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ 1.05-1.12 (m, 6H), 3.05 / 3.14 (d, 3H), 3.19-3.30 (m, 4H), 3 .66-3.73 (m, 2H), 4.19-4.26 (m, 2H), 5.67-5.71 (m, 1H), 6.30-6.38 (m, 1H) , 6.56-6.66 (m, 1H)

[Example 2]
(R ₁ is a hydrogen atom in Exemplified Compound 1-3)
An aqueous solution in which 2- (methylamino) ethanol (5.25 g, 70 mmol) was dissolved in tetrahydrofuran (80 ml) and potassium carbonate (23.2 g, 168 mmol) was dissolved in 50 ml of water was added. The mixture was cooled to 5 ° C. in an ice bath, acrylic acid chloride (6.0 g, 67 mmol) was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours. Then, the mixture was cooled to 5 ° C. again in an ice bath, N-ethyl-N-methylcarbamoyl chloride (7.5 g, 70 mmol) was slowly added dropwise, and then the mixture was stirred at 40 ° C. for 15 hours.
After filtering the precipitated salt with Celite, the aqueous layer is extracted with ethyl acetate, combined with the organic layer, washed in the order of saturated sodium hydrogen carbonate solution and saturated sodium chloride solution, dried with sodium sulfate, and then concentrated under reduced pressure. The crude product was obtained. This crude product was isolated by silica gel column chromatography (filler: Wakogel C-300, developing solvent: ethyl acetate) to obtain 2.3 g (yield 15%) of a colorless oil of compound 1-3A.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.05-1.15 (m, 3H), 2.86-2.89 (m, 2H), 3.05 / 3.14 (d, 3H), 3. 18-3.33 (m, 2H), 3.65-3.72 (m, 2H), 4.19-4.26 (m, 2H), 5.67-5.71 (m, 1H), 6.31-6.38 (m, 1H), 6.56-6.66 (m, 1H)

[Example 3]
(R ₁ is a hydrogen atom in Exemplified Compound 3-1)
2- (Isopropylamino) ethanol (7.22 g, 70 mmol) was dissolved in tetrahydrofuran (90 ml), and an aqueous solution of potassium carbonate (23.2 g, 168 mmol) in 40 ml of water was added. The mixture was cooled to 5 ° C. in an ice bath, acrylic acid chloride (6.0 g, 67 mmol) was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours. Then, the mixture was cooled to 5 ° C. again in an ice bath, dimethylcarbamoyl chloride (7.5 g, 70 mmol) was slowly added dropwise, and the mixture was stirred at 40 ° C. for 15 hours.
After filtering the precipitated salt with Celite, the aqueous layer is extracted with ethyl acetate, combined with the organic layer, washed in the order of saturated sodium hydrogen carbonate solution and saturated sodium chloride solution, dried with sodium sulfate, and then concentrated under reduced pressure. The crude product was obtained. This crude product was isolated by silica gel column chromatography (filler: Wakogel C-300, developing solvent: ethyl acetate) to obtain 3.8 g (yield 24%) of a colorless oil of compound 3-1A.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.21 (m, 6H), 2.86-2.93 (d, 6H), 3.51-3.54 (m, 2H), 3.76-3. 79 / 4.74-4.77 (m, 1H), 4.13-4.24 (m, 2H), 5.64-5.74 (m, 1H), 6.24-6.41 (m) , 1H), 6.57-6.73 (m, 1H)

[Example 4]
(R ₁ is a hydrogen atom in Exemplified Compound 6-2)
An aqueous solution prepared by dissolving 2- (isopropylamino) propanol (10.0 g, 85 mmol) in tetrahydrofuran (85 ml) and dissolving potassium carbonate (25.9 g, 187 mmol) in 45 ml of water was added. The mixture was cooled to 5 ° C. in an ice bath, acrylic acid chloride (7.3 g, 81 mmol) was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours. Then, the mixture was cooled to 5 ° C. again in an ice bath, diethylcarbamoyl chloride (11.6 g, 85 mmol) was slowly added dropwise, and the mixture was stirred at 40 ° C. for 20 hours.
After filtering the precipitated salt with Celite, the aqueous layer is extracted with ethyl acetate, combined with the organic layer, washed in the order of saturated sodium hydrogen carbonate solution and saturated sodium chloride solution, dried with sodium sulfate, and then concentrated under reduced pressure. The crude product was obtained. This crude product was isolated by silica gel column chromatography (filler: Wakogel C-300, developing solvent: ethyl acetate) to obtain 3.9 g (yield 17%) of a colorless oil of compound 6-2A.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.10-1.22 (m, 12H), 1.96 (m, 2H), 3.29-3.35 (m, 6H), 4.12 (t, 2H), 4.20 / 4.80 (m, 1H), 5.62-5.68 (m, 1H), 6.23-6.40 (m, 1H), 6.51-6.62 ( m, 1H)

[Comparative Example 1]
The acrylamide compound represented by the following structural formula was used as the compound of the comparative example.

<Measurement of viscosity>
The viscosity of each compound of Examples 1 to 4 was measured by using a cone rotor (1 ° 34'× R24) with a cone plate type rotational viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd., at a rotation speed of 50 rpm and a constant temperature. The temperature of the circulating water was measured at 40 ° C. As a result, the viscosities of the compounds of Examples 1 to 4 were 20 mPa · s or less.

Examples 1a to 4a, Comparative Example 1a [Preparation of photocurable composition]
900 mg of each of the compounds of Examples 1 to 4 and Comparative Example 1 and the photopolymerization initiator IRGACURE 907 [2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one] (BASF Japan, Inc.). (Manufactured) 100 mg was mixed using a magnetic stirrer to prepare each photocurable composition of Examples 1a to 4a and Comparative Example 1a.

[Evaluation of photochemical curability]
The photoreactivity of Examples 1a to 4a and Comparative Example 1a was evaluated as follows. The results are shown in Table 1.
(Evaluation methods)
With a leometer MCR-302 manufactured by Antonio-Paar, the plate diameter was set to 20 mm and the temperature was set to 25 ° C., and the energy (mJ / cm ² ) at which G'saturated was measured. The light source used was LC-L1 (365 nm) manufactured by Hamamatsu Photonics.

The curing energy of Examples 1a to 4a is less than half that of Comparative Example 1a, and the cured product can be obtained with less energy.

Examples 1b-4b [Preparation of ink]
Examples include 100 parts of each acrylamide compound of Examples 1 to 4, 10 parts of the photopolymerization initiator IRGACURE 907 (manufactured by BASF Japan) and 3 parts of carbon black MICROLITH Black CK (manufactured by BASF Japan). Each ink of 1b to 4b was obtained.

Examples 1c-4c [Preparation of ink]
100 parts of each acrylamide compound of Examples 1 to 4, 10 parts of the photopolymerization initiator IRGACURE 907 (manufactured by BASF Japan) and 3 parts of the blue pigment MICROLITH Blue 4G-K (manufactured by BASF Japan) are mixed, and Examples 1c to Each ink of 4c was obtained.

[Ink evaluation 1]
After inkjet ejection of the inks of Examples 1b to 4b and Examples 1c to 4c onto a slide glass, an ultraviolet ray having a wavelength of 365 nm is 200 mW / cm ² using a UV irradiator LH6 (manufactured by Fusion Systems Japan). It was irradiated with and cured. As a result, each ink could be ejected by inkjet without any problem, and each ink image was sufficiently cured.

[Ink evaluation 2]
Immerse the tip of the dip pen in the inks of Examples 1b to 4b and Examples 1c to 4c, write characters on PET film and plain paper, and then use a UV irradiator LH6 (manufactured by Fusion System Japan). It was cured by irradiating it with ultraviolet rays having a wavelength of 365 nm at 200 mW / cm ² . As a result, each ink image was sufficiently cured.

1 Storage pool (accommodation)
3 Movable stage 4 Active energy ray 5 Active energy ray Curable composition 6 Cured layer 21 Supply roll 22 Recorded matter 23a, 23b, 23c, 23d Each color printing unit 24a, 24b, 24c, 24d Light source 25 Processing unit 26 Printed matter winding Roll 30 Discharge head unit for shaped object 31, 32 Discharge head unit for support 33, 34 Ultraviolet irradiation means 35 Three-dimensional model 36 Support laminated portion 37 Modeled object support substrate 38 Stage 39 Image forming device

Japanese Unexamined Patent Publication No. 2015-013980

Claims (10)

A (meth) acrylamide compound represented by the following general formula (1).

(In the equation, R ₁ indicates a hydrogen atom or a methyl group, R ₂ , R ₄ , R ₅ indicates a linear or branched alkyl group, and R ₂ , R ₄ and R ₅ may be the same or different, respectively. , R ₃ indicates a linear or branched alkylene group.) The (meth) acrylamide compound according to claim 1, wherein in the general formula (1), the carbon atoms of R ₂ , R _3, R ₄ and R ₅ are all 4 or less. A curable composition comprising the compound according to claim 1 or 2. An active energy ray-curable ink comprising the compound according to claim 1 or 2. The active energy ray-curable ink according to claim 4, which is for inkjet use. A composition storage container comprising the curable composition according to claim 3 or the active energy ray-curable ink according to claim 4 or 5. A two-dimensional or three-dimensional image forming apparatus comprising the accommodating portion accommodating the active energy ray-curable ink according to claim 4 or 5, and an irradiation means for irradiating the active energy ray. .. A two-dimensional or three-dimensional image forming method comprising an irradiation step of irradiating the active energy ray-curable ink according to claim 4 or 5 with an active energy ray. A cured product according to claim 4 or 5, wherein the active energy ray-curable ink is irradiated with active energy rays and cured. A decorative body characterized in that a surface decoration made of the cured product according to claim 9 is applied on a base material.

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