JP6775758B2 - Active energy ray-curable ink, active energy ray-curable inkjet 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 an active energy ray-curable composition, an active energy ray-curable ink, an active energy ray-curable inkjet ink, a composition container, a two-dimensional or three-dimensional image forming apparatus, and a two-dimensional or three-dimensional image forming device. With respect to methods, cured products, decorators and photopolymerizable compounds.

An inkjet recording method is known as a method of forming an image on a recording medium such as paper. This 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, an inkjet recording method using an ultraviolet curable ink has attracted attention.
In Patent Document 1, a (meth) acrylate compound having an amide structure represented by [-C (= O) -NRR'] at the end can be used as a reactive diluent in an energy-curable resin used as a film for an optical fiber. It is shown. (R, R'are a hydrogen atom, an alkyl group, etc.) Further, Patent Document 2 discloses a (meth) acrylate compound having a similar terminal structure and a method for producing the same.

Further, in Patent Document 3, an ink composition having good curability and excellent flexibility of a cured product by using a monofunctional (meth) acrylate compound having an [-C (= O) NH-] structure in the molecule. It is shown. Among them, urethane structure [-OC (= O) -NH-], [-NH-C (= O) -O-] and urea structure [-NH-C (= O) -NH-] It has been shown that monofunctional (meth) acrylates having are preferred.

An object of the present invention is to provide an active energy ray-curable composition having less odor and excellent photopolymerizability and photocurability than the conventional active energy ray-curable composition.

（式中、Ｒ_１は水素原子又はメチル基を示し、Ｒ_２は側鎖を有していても良い炭素数１〜１２のアルキレン基を示し、Ｒ_３は不飽和結合を含まない炭素数１〜１０の炭化水素基を示す。） The above problem is solved by the invention of 1) below.
1) An active energy ray-curable ink containing a (meth) acrylic acid ester compound represented by the general formula (1).

(In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 1 to 12 carbon atoms which may have a side chain, and R ₃ represents an unsaturated bond-free carbon number 1. Shows 10 hydrocarbon groups.)

According to the present invention, it is possible to provide an active energy ray-curable composition having excellent photopolymerizability and photocurability, using a photopolymerizable compound having less odor.

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

（式中、Ｒ_１は水素原子又はメチル基を示す。）
３）前記一般式（２）で表される化合物が下記一般式（３）で表されることを特徴とする前記２）に記載の活性エネルギー線硬化型組成物。

４）前記１）から３）のいずれかに記載の化合物を含有することを特徴とした活性エネルギー線硬化型インク。
５）前記４）に記載された活性エネルギー線硬化型インクがインクジェット用であることを特徴とした活性エネルギー線硬化型インクジェットインク。
６）前記１）から５）のいずれかに記載の組成物又はインクが収容された組成物収容容器。
７）前記１）から５）のいずれかに記載の組成物又はインクが収容された収容部と、活性エネルギー線を照射するための照射手段と、を備える２次元または３次元の像形成装置。
８）前記１）から５）のいずれかに記載の組成物又はインクに活性エネルギー線を照射する照射工程を有する２次元または３次元の像形成方法。
９）前記１）から５）に記載の組成物又はインクに活性エネルギー線を照射して硬化させてなることを特徴とする硬化物。
１０）基材上に前記９）に記載の硬化物からなる表面加飾が施されてなることを特徴とする加飾体。
１１）下記一般式（１）で表されることを特徴とする化合物。

（式中、Ｒ_１は水素原子又はメチル基を示し、Ｒ_２は側鎖を有していても良い炭素数１〜１２のアルキレン基を示し、Ｒ_３は炭素数１〜１０の炭化水素基を示す。）
１２）下記一般式（２）で表されることを特徴とする前記１１）に記載の化合物。

（式中、Ｒ_１は水素原子又はメチル基を示す。）
１３）下記構造式（３）表されることを特徴とする前記１２）に記載の化合物。

Hereinafter, the present invention will be described in detail, but the following 2) to 13) are also included in the embodiments thereof, and these will also be described.
2) The active energy ray-curable composition according to 1) above, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(In the formula, R ₁ represents a hydrogen atom or a methyl group.)
3) The active energy ray-curable composition according to 2) above, wherein the compound represented by the general formula (2) is represented by the following general formula (3).

4) An active energy ray-curable ink characterized by containing the compound according to any one of 1) to 3) above.
5) An active energy ray-curable inkjet ink according to the above 4), wherein the active energy ray-curable ink is for an inkjet.
6) A composition container containing the composition or ink according to any one of 1) to 5) above.
7) A two-dimensional or three-dimensional image forming apparatus comprising an accommodating portion accommodating the composition or ink according to any one of 1) to 5) above and an irradiation means for irradiating active energy rays.
8) A two-dimensional or three-dimensional image forming method comprising an irradiation step of irradiating the composition or ink according to any one of 1) to 5) with active energy rays.
9) A cured product obtained by irradiating the composition or ink according to 1) to 5) with active energy rays and curing the composition or ink.
10) A decorative body characterized in that a surface decoration made of the cured product according to 9) is applied on a base material.
11) A compound characterized by being represented by the following general formula (1).

(In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 1 to 12 carbon atoms which may have a side chain, and R ₃ is a hydrocarbon group having 1 to 10 carbon atoms. Shows.)
12) The compound according to 11) above, which is represented by the following general formula (2).

(In the formula, R ₁ represents a hydrogen atom or a methyl group.)
13) The compound according to 12) above, which is represented by the following structural formula (3).

The compound represented by the general formula (1) contained in the ink of the present invention has an alkyl group-based (meth) acrylate compound terminal structure [-NH-C (= O) -R ₃ ]. It is characterized by having one.
In general, low-molecular-weight (meth) acrylate compounds have a strong odor peculiar to monomers because they are volatile, which makes them uncomfortable when handling curable compositions containing these compounds. .. It is possible to suppress the volatility of the compound and reduce the odor by introducing a functional group having a strong polarity to such a low molecular weight (meth) acrylate compound or increasing the molecular weight. In that case, This will result in an increase in viscosity, which will increase restrictions on the use of curable compositions, especially inkjet inks.

The compound represented by the general formula (1) contained in the curable composition of the present invention has a hydrogen-bonding amide structure [-NH (C = O) -R ₃ ] in the molecule. , It is a structure in which the increase in viscosity is suppressed because the intermolecular interaction is considered to be low with respect to a similar urea structure. Further, since the NH structure is located on the central side of the molecule, it is considered that the increase in viscosity is suppressed as compared with the case where the NH structure is located on the terminal side.
Further, the monofunctional (meth) acrylate having a urethane structure [-OC (= O) -NH-] and [-NH-C (= O) -O-] having similar structures is relatively relatively It is considered that the cured product tends to be in a soft state due to the presence of the CO bond having a large degree of freedom in the molecule, and it is difficult to form a hard and strong cured product.

As described above, the monofunctional (meth) acrylate compound represented by the general formula (1) contained in the curable composition of the present invention has one amide structure [-NH-C (= O) -R in the molecule. By having ₃ ], it is possible to achieve both curability and low odor due to intramolecular interaction while suppressing an increase in viscosity. Therefore, the compound of the present invention represented by the general formula (1) is suitable for a curable composition.

（式中、Ｒ_１は水素原子又はメチル基を示し、Ｒ_２は側鎖を有していても良い炭素数１〜１２のアルキレン基を示し、Ｒ_３は炭素数１〜１０の炭化水素基を示す。） There are various routes for the synthesis of the compound of the above general formula (1) of the present invention, and it can be appropriately selected depending on the available raw materials. As an example thereof, it can be easily synthesized by an esterification reaction between an alcohol having a secondary amide structure at the terminal and (meth) acrylic acid or (meth) acrylic acid chloride, but is not limited thereto.

(In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 1 to 12 carbon atoms which may have a side chain, and R ₃ is a hydrocarbon group having 1 to 10 carbon atoms. Shows.)

Next, specific examples of the photopolymerizable compound of the present invention will be shown, but the present invention is not limited thereto. R ₁ in these examples is as described above.

The photopolymerizable compound of the present invention can be used by mixing two or more different compounds with each other, and the different compounds in this case also include structural isomers. The mixing ratio is not particularly limited.
The content of the photopolymerizable compound in the curable 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 compound represented by the general formula (1). In that case, both can be used in an arbitrary ratio, but the mass ratio of the other photopolymerizable compounds to the compound 100 represented by the general formula (1) is usually 0.01 to 100, and 0. 1 to 50 are preferable.
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 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 acryliconitrile, styrene, unsaturated polyester, unsaturated polyether, unsaturated polyamide, and unsaturated urethane.

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 Acrylate derivatives such as methylolpropantriacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, 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, and acryloyl morpholine, derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triaryl 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, trimethylolpropan 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, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether, 2-ethylhexyl diglycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl acrylate, neopentyl hydroxypivalate Glycoldiacrylate, 2-acryloyloxyethyl phthalic acid, methoxypolyethylene glycol acrylate, tetramethylol methanetriacrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, dimethyloltricyclodecanediacrylate, ethoxylated phenylacrylate , 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 isocyanato urethane prepolymer, lactone-modified flexible acrylate, butoxyethyl Acrylic, propylene glycol diglycidyl ether acrylic acid adduct, pentaerythritol triacrylate , Hexamethylene diisocyanate urethane prepolymer, 2-hydroxyethyl acrylate, methoxydipropylene glycol acrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, hexamethylene diisocyanato urethane prepolymer, stearyl acrylate, isoamyl acrylate, isomyristyl Examples thereof include acrylate, isostearyl acrylate, and lactone-modified acrylate.

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 photoanion. Examples thereof include a combination of a polymerizable compound and a photoanion polymerization initiator.
Examples of the photocationically polymerizable compound include an epoxy compound, a vinyl ether compound, and an oxetane compound.

As the photo cationic polymerization initiator, diazonium, ammonium, iodonium, sulfonium, aromatic onium compounds of phosphonium such as ^{_{B (C 6 F 5) 4}} -, PF 6 -, AsF 6 -, SbF 6 -, CF 3 SO 3 ^- salts, sulfonated capable of generating a sulfonic acid, halide capable of generating a hydrogen halide, iron allene complexes.
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.

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 electron-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 formation of radicals) is promoted.
The mass ratio of the sensitizer to the photopolymerization initiator is usually 5 × 10 ^-3 to 200, preferably 0.02 to 50.

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, merocyanines, carbocyanines), thiadins (eg, thionin, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acryflabin), anthraquinones (eg, anthraquinone), squarylium. (Eg, squarylium), coumarins (eg, 7-diethylamino-4-methylcoumarin) and the like.

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

The curable composition may further contain a polymerization inhibitor. Thereby, the storage stability (storage stability) of the curable composition can be improved. 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 cuperon complex of aluminum. The content of the polymerization inhibitor in the ink is usually 200 to 20000 ppm.

<Active energy ray>
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 beams, α rays, β rays, γ rays, and X rays 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. 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.

<Polymerization initiator>
The active energy ray-curable composition of the present invention may contain a polymerization initiator. The polymerization initiator may be one that can generate active species such as radicals and cations by the energy of the active energy rays and initiate 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, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, -2-ethylhexyl p-dimethylaminobenzoate, 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.

<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 the 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 type may be used alone or two or more types 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 lake (basic dye type lake, acidic dye type lake), nitro pigment, nitroso pigment, aniline black, Daylight fluorescent pigments can be mentioned.
Moreover, in order to make the dispersibility of the pigment better, 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, for example, a general non-reactive organic solvent such as ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and should be distinguished from the reactive monomer. is there. Further, "not containing" the organic solvent means that it is substantially not contained, 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 ingredients, 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 (moisturizing agents), and fixing agents. Examples include agents, viscosity stabilizers, fungicides, preservatives, antioxidants, UV absorbers, chelating agents, pH regulators, thickeners and the like.

<Adjustment of active energy ray-curable composition>
The active energy ray-curable composition of the present invention can be prepared by using the above-mentioned various components, and the adjusting means and conditions thereof are not particularly limited. For example, a polymerizable monomer, a pigment, a dispersant and the like are used in a ball mill. It is put into a disperser such as a kitty mill, a disc mill, a pin mill, or 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 adjusted by making it.

<Viscosity>
The viscosity of the active energy ray-curable composition of the present invention may be appropriately adjusted according to the application and the 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 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. 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'x 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 ~ 65 ° C. VISCOMATE VM-150III can be used to adjust the temperature of the circulating water.

<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 in which 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 form not only two-dimensional characters and images and a design coating film on various substrates, but also 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 lamination 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 modeling method (stereolithography). In addition, 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 laminating 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 device can be used, and 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 the form of a sheet or a film, which has been subjected to molding processing such as heat stretching or punching. 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 contained, 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 directly touch the ink 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>
The method for forming an image of the present invention includes, at least, an irradiation step of irradiating an active energy ray to cure the active energy ray-curable composition of the present invention, and the image forming apparatus of the present invention has an active energy. An irradiation means for irradiating the rays 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 recording medium 22 supplied from the supply roll 21 by each color printing unit 23a, 23b, 23c, 23d including an ink cartridge of 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 an 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 a recording medium that moves intermittently according to the width of the ejection head. 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, 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 also possible.
Further, the activation 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. As a result, energy saving and cost reduction can be achieved.
The recorded matter recorded by the ink of the present invention includes not only those printed on a smooth surface such as ordinary paper or resin film, but also those printed on an uneven surface to be printed, metal, ceramic, and the like. It also includes those printed on the surface to be printed, which are 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 the 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. The 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 the 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, irradiated with active energy rays, and solidified. After forming the first support layer having a reservoir, the first active energy ray-curable composition is discharged from the discharge head unit 30 for a modeled object into the reservoir, and is irradiated with active energy rays to solidify. 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 times of stacking, 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.

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 addition, "part" and "%" in an example are "part by mass" and "mass%". The ¹ H-NMR spectrum was measured using ¹ H-NMR (500 MHz) (ECX500 manufactured by JEOL Ltd.), and the IR spectrum was measured using FT-IR Spectrum GX (Spectrem GX manufactured by PERKIN ELMER). ..

[Example 1a]
6.19 g (60 mmol) of 2-acetamidoethanol manufactured by Tokyo Chemical Industry Co., Ltd. was added to 100 m of dehydrated dichloromethane, the inside of the flask was replaced with argon gas, and then 9.11 g (90 mmol) of triethylamine was added. Next, after cooling to about -15 ° C, 6.52 g (72 mmol) of acrylic acid chloride manufactured by Wako Pure Chemical Industries, Ltd. was slowly added dropwise so that the temperature inside the system became -8 ° C to -9 ° C, and the room temperature was adjusted. It was stirred underneath for 3 hours. Further, after removing the precipitate by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution. Next, it was dried over sodium sulfate and then concentrated under reduced pressure to obtain an oil. Further, 300 g of silica gel (Wakogel C-300) manufactured by Wako Pure Chemical Industries, Ltd. was filled and purified by column chromatography using hexane and ethyl acetate as an eluate, and the single yellow color of Example Compound 1 represented by the following structural formula was obtained. 4.57 g of oil (yield about 48%) was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ2.00 (s, 3H), 3.56 (q, 2H), 4.26 (t, 2H), 5.88 (dd, 1H), 5.92-6 0.01 (br, 1H), 6.11-6.17 (m, 1H), 6.44 (dd, 1H)
IR (NaCl): 3290, 3081,295, 1727, 1655, 1554, 1409, 1373, 1295, 1271, 1191, 1129, 1067, 1041, 986, 907, 810, 723, 674,601 cm ^-1

[Example 2a]
9.28 g (90 mmol) of 2-acetamidoethanol manufactured by Tokyo Chemical Industry Co., Ltd. was added to 100 m of dehydrated dichloromethane, the inside of the flask was replaced with argon gas, and then 13.15 g (130 mmol) of triethylamine was added. Next, after cooling to about -15 ° C, 11.29 g (108 mmol) of methacrylic acid chloride manufactured by Wako Pure Chemical Industries, Ltd. was slowly added dropwise so that the temperature inside the system became -8 ° C to -9 ° C, and the room temperature was adjusted. It was stirred underneath for 3 hours. Further, after removing the precipitate by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution. Next, it was dried over sodium sulfate and then concentrated under reduced pressure to obtain an oil. Further, 300 g of silica gel (Wakogel C-300) manufactured by Wako Pure Chemical Industries, Ltd. was filled and purified by column chromatography using hexane and ethyl acetate as an eluate, and the single yellow color of Example Compound 2 represented by the following structural formula was obtained. 12.1 g of oil (yield about 79%) was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.95 (s, 3H), 2.00 (s, 3H), 3.56 (q, 2H), 4.25 (t, 2H), 5.60-5 .62 (m, 1H), 6.03-6.10 (br, 1H), 6.12-6.14 (m, 1H)
IR (NaCl): 3288, 3086, 2959, 1720, 1658, 1555, 1453, 1374, 1321, 1296, 1169, 1041, 945, 816, 654, 602 cm ^-1

[Example 3a]
7.03 g (60 mmol) of N- (2-hydroxyethyl) propionamide manufactured by Tokyo Chemical Industry Co., Ltd. was added to 100 m of dehydrated dichloromethane, the inside of the flask was replaced with argon gas, and then 9.11 g (90 mmol) of triethylamine was added. Next, after cooling to about -15 ° C, 6.52 g (72 mmol) of acrylic acid chloride manufactured by Wako Pure Chemical Industries, Ltd. was slowly added dropwise so that the temperature inside the system became -8 ° C to -9 ° C, and the room temperature was adjusted. It was stirred underneath for 3 hours. Further, after removing the precipitate by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution. Next, it was dried over sodium sulfate and then concentrated under reduced pressure to obtain an oil. Further, 300 g of silica gel (Wakogel C-300) manufactured by Wako Pure Chemical Industries, Ltd. was filled and purified by column chromatography using hexane and ethyl acetate as an eluate, and the single yellow color of Example Compound 3 represented by the following structural formula was obtained. 4.0 g of oil (yield about 39%) was obtained.
The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.16 (t, 3H), 2.23 (q, 2H), 3.56-3.59 (m, 2H), 4.27 (t, 2H), 5 .89 (dd, 1H), 5.80-5.90 (br, 1H), 6.11-6.17 (m, 1H), 6.44 (dd, 1H)
IR (NaCl): 3299,3083,2979,1726,1651,1549,1463,1410,1296,1192,1131,1068,985,810,666 cm ^-1

[Example 4a]
7.03 g (60 mmol) of N- (2-hydroxyethyl) propionamide manufactured by Tokyo Chemical Industry Co., Ltd. was added to 100 m of dehydrated dichloromethane, the inside of the flask was replaced with argon gas, and then 9.11 g (90 mmol) of triethylamine was added. Next, after cooling to about -15 ° C, 7.53 g (72 mmol) of methacrylic acid chloride manufactured by Wako Pure Chemical Industries, Ltd. was slowly added dropwise so that the temperature inside the system became -8 ° C to -9 ° C, and the room temperature was adjusted. It was stirred underneath for 2 hours. Further, after removing the precipitate by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution. Next, it was dried over sodium sulfate and then concentrated under reduced pressure to obtain an oil. Further, 300 g of silica gel (Wakogel C-300) manufactured by Wako Pure Chemical Industries, Ltd. was filled and purified by column chromatography using hexane and ethyl acetate as an eluate, and the single yellow color of Example Compound 4 represented by the following structural formula was obtained. 4.9 g of an oily substance (yield about 44%) was obtained.
The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.16 (t, 3H), 1.96 (s, 3H), 2.22 (q, 2H), 3.54-3.60 (m, 2H), 4 .26 (t, 2H), 5.60-5.62 (m, 1H), 5.78-5.88 (br, 1H), 6.12-6.13 (m, 1H)
IR (NaCl): 3299,3083,2980,2939,1720,1649,1550,1453,1376,1320,1296,1241,1159,1111,1038,948,815,696 cm ^-1

[Comparative Example 1a]
A commercially available hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following structural formula was used as the compound of Comparative Example 1a.

[Comparative Example 2a]
A commercially available hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following structural formula was used as the compound of Comparative Example 2a.

[Comparative Example 3a]
A commercially available compound of 2- (t-butylamino) ethyl methacrylate (manufactured by Polyscience) represented by the following structural formula was used as the compound of Comparative Example 3a.

[Comparative Example 4a]
A commercially available compound represented by the following structural formula (GEMONMER1122 manufactured by Rahn AG) was used as the compound of Comparative Example 4a.

[Comparative Example 5a]
The compound having the following structure synthesized by the following procedure was used as the compound of Comparative Example 5a.
Diethylcarbamoyl chloride (24.4 g, 180 mmol) was dissolved in pyridine (250 ml). 2-Aminoethanol (14.3 g, 234 mmol) was slowly added to this solution while cooling in a water bath, and then the mixture was stirred at room temperature for 24 hours. The reaction mixture was concentrated under reduced pressure and the resulting solution was extracted with ethyl acetate (350 ml). By concentrating this extract, a brown liquid was obtained. The obtained liquid was purified by column chromatography (Wakogel C300 200 g) to obtain pale yellow acicular crystals (10.5 g). From ^{1 1} H-NMR and IR, it was confirmed that this pale yellow needle-like crystal was a compound (intermediate-1) represented by the following structural formula. The yield after purification was about 36%.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.15 (t, 6H), 3.27 (q, 4H), 3.41 (q, 2H), 3.71 (t, 2H), 4.84-4 .92 (bs, 1H)
IR (NaCl): 3353, 2974, 2933, 2875, 1712, 1626, 1538, 1460, 1409, 1379, 1362, 1283, 122, 1198, 1074, 1029, 934, 873,840, 769, 583 cm ^-1

It was added to the obtained intermediate-1 (4.7 g, 29 mmol) dehydrated dichloromethane (70 mL), the inside of the flask was replaced with argon gas, and then triethylamine (4.6 g, 45 mmol) was added. After cooling the mixture to about -10 ° C, chloride chloride (3.3 g, 36 mmol) is slowly added dropwise to the system temperature at -10-5 ° C, followed by stirring at room temperature for 2 hours. did. The precipitate was removed by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogen carbonate solution, and saturated aqueous sodium chloride solution, dried over sodium sulfate, and then concentrated under reduced pressure to give a brown oil. The obtained oil was purified by column chromatography (Wakogel C300 300 g) to obtain a pale yellow oil (2.8 g). From the following ^{1 1} H-NMR and IR, it was confirmed that this pale yellow oily substance was a compound represented by the following structural formula. The yield after purification was about 45%.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.13 (t, 6H), 3.26 (q, 4H), 3.55 (q, 2H), 4.29 (t, 2H), 4.77-4 .83 (bs, 1H), 5.84-5.88 (m, 1H), 6.11-6.17 (m, 1H), 6.41-6.45 (m, 1H)
IR (NaCl): 3352, 2974, 2933, 2875, 1726, 1630, 1533, 1455, 1407, 1379, 1362, 1269, 1190, 1099, 1067, 985, 811, 766, 552 cm ^-1

[Comparative Example 6a]
The compound having the following structure synthesized by the following procedure was used as the compound of Comparative Example 6a.
It was added to Intermediate-1 (5.6 g, 35 mmol) dehydrated dichloromethane (100 mL) obtained above, the inside of the flask was replaced with argon gas, and then triethylamine (5.1 g, 50 mmol) was added. After cooling the mixture to about -10 ° C, chloride chloride (4.4 g, 42 mmol) is slowly added dropwise to the system temperature at -10-5 ° C, followed by stirring at room temperature for 2 hours. did. The precipitate was removed by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogen carbonate solution, and saturated aqueous sodium chloride solution, dried over sodium sulfate, and then concentrated under reduced pressure to give a brown oil. The obtained oil was purified by column chromatography (Wakogel C300 300 g) to obtain a pale yellow oil (5.2 g). From the following ^{1 1} H-NMR and IR, it was confirmed that this pale yellow oily substance was a compound represented by the following structural formula. The yield after purification was about 65%.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.13 (t, 6H), 1.95 (s, 3H), 3.25 (q, 4H), 3.55 (q, 2H), 4.28 (t) , 2H), 4.71-4.76 (bs, 1H), 5.58-5.60 (m, 1H), 6.15-6.30 (m, 1H)
IR (NaCl): 3354, 2975, 2932, 1720, 1630, 1534, 1454, 1407, 1379, 1363, 1321, 1282, 1223, 1168, 1099, 1081, 1032, 941, 816,766, 654,592 cm ^-1

<Measurement of viscosity>
The viscosities of the compounds of Examples 1a to 4a and Comparative Examples 1a to 6a were 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). , The rotation speed was 50 rpm, and the temperature of the constant temperature circulating water was measured at 25 ° C. The results are shown in Table 1.

<Evaluation of odor>
The odors of the compounds of Examples 1a to 4a and Comparative Examples 1a to 6a were evaluated by the following procedures (1) to (3). The evaluation criteria are as follows. The results are shown in Table 1.
(1) About 100 mg (0.1 g) of each compound was weighed into a 50 cc sample bottle (glass bottle) and covered.
(2) It was left for about 30 minutes under room temperature conditions.
(3) I brought my nose close to the sample bottle (glass bottle) and smelled the odor when the lid was opened.
〔Evaluation criteria〕
○: If you do not feel the odor, or if you feel it is not unpleasant △: If the peculiar odor causes discomfort ×: If the peculiar odor causes strong discomfort

[Examples 1b to 4b, Comparative Examples 1b to 6b]
[Preparation of active energy ray-curable composition]
950 mg of each of the compounds of Examples 1a to 4a and Comparative Examples 1a to 6a and the photopolymerization initiator IRGACURE 907 [2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one] (BASF). 50 mg (manufactured by Japan) was mixed using a magnetic stirrer to prepare active energy ray-curable compositions of Examples 1b to 2b and Comparative Examples 1b to 6b.

The photopolymerizability and photocurability of the active energy ray-curable compositions of Examples 1b to 4b and Comparative Examples 1b to 6b were evaluated as follows. The results are shown in Table 1.

<Photopolymerizable>
The photopolymerizability of each active energy ray-curable composition was evaluated using a measuring device combining DSC-7020 (manufactured by SII) and a spot light source LA-410UV (manufactured by HAYASHI WATCH-WORKS).
Specifically, the calorific value when the photopolymerizable compound was irradiated with ultraviolet rays having a wavelength of 365 nm at 200 mW / cm ² for a sufficient time to complete the polymerization was measured twice for one sample. The calorific value obtained in the first measurement includes not only the calorific value associated with the polymerization of the photopolymerizable compound but also the calorific value associated with ultraviolet irradiation. Therefore, the sample whose polymerization was completed in the first measurement was irradiated with ultraviolet rays again under the same conditions, and the calorific value other than the calorific value associated with the polymerization of the photopolymerizable compound was measured. Then, the calorific value associated with the polymerization of the photopolymerizable compound was calculated from the difference in calorific value between the first and second times. At this time, the time from the start of ultraviolet irradiation to the arrival at the maximum calorific value was defined as T1 [s], which was used as an index for comparing the speed of photopolymerization.

<Active energy ray curable>
The photocurability of each active energy ray-curable composition is measured using a measuring device that combines the viscoelasticity measuring device MCR-302 (manufactured by Anton Pearl) and the LED light source LIGHTNINGCURE LC-L1 (manufactured by Hamamatsu Photonics). did.
Specifically, after sandwiching the sample in a gap of 10 μm using a cone plate with a diameter of 20 mm, the sample is irradiated with ultraviolet rays having a wavelength of 365 nm at 50 mW / cm ² , and the change in viscoelasticity is changed until the storage elastic modulus G'is saturated. It was measured. The maximum elastic modulus was obtained from the measurement results and used as an index of the curing level.
Further, the energy of the ultraviolet rays irradiated until the elastic modulus is saturated, that is, the curing energy is calculated from the product of the intensity of the ultraviolet rays (50 mW / cm ² ) and the time [s] of the irradiation of the ultraviolet rays.

From Table 1, it can be seen that the photopolymerizable compounds of Examples 1a to 4a have a viscosity at 25 ° C. of 100 mPa · s or less and a small odor.
Further, the active energy ray-curable compositions of Examples 1b to 4b using the photopolymerizable compounds of Examples 1a to 4a are excellent in photopolymerizability and active energy ray-curable property, and particularly excellent in active energy ray-curable property. You can see that. Specifically, it can be seen that the storage elastic modulus at the time of curing is larger and the light energy required to reach saturation is smaller than that of the comparative example. This is due to the amide structure [-NH-C (= O) -R ₃ ] contained in the molecule, and in addition to the strength of the interaction between the amide groups, the degree of freedom of the CN bond. It is considered that a hard state after curing is created due to the low value. This can be seen from the fact that the storage elastic modulus is an order of magnitude higher than that of a system having a urethane structure having a similar structure. It can also be seen that the increase in viscosity is suppressed lower than that of a similar urea structure.

[Examples 1c to 4c]
[Making ink]
100 parts of each photopolymerizable compound of Examples 1a to 4a, 10 parts of the photopolymerization initiator IRGACURE 907 (manufactured by BASF Japan) and 3 parts of carbon black MICROLITH Black C-K (manufactured by BASF Japan) were mixed. Each ink of Examples 1c to 4c was obtained.

[Examples 1d to 4d]
100 parts of each photopolymerizable compound of Examples 1a to 4a, 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) were mixed, and Examples were used. Each ink of 1d to 4d was obtained.

[Ink evaluation 1]
After each of the inks of Examples 1c to 4c and Examples 1d to 4d is ejected by inkjet on a slide glass, ultraviolet rays having a wavelength of 365 nm are emitted at 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.
Further, each ink substantially corresponds to the one using each active energy ray-curable composition of Examples 1b to 4b, but just in case, light is applied in the same manner as in the case of each active energy ray-curable composition. When the polymerizable property and the photocurability were measured, it was confirmed that both of them were as excellent as the active energy ray-curable compositions.

[Ink evaluation 2]
Immerse the tip of the dip pen in the inks of Examples 1c to 2c and Examples 1d to 4d, 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 Curing type composition 6 Curing layer 21 Supply roll 22 Recording medium 23a, 23b, 23c, 23d Printing unit 24a, 24b, 24c, 24d Light source 25 Processing unit 26 Printed matter winding roll 30 Discharge head unit for modeled object 31, 32 Discharge head unit for support 33, 34 Ultraviolet irradiation means 35 Three-dimensional modeled object 36 Support laminated part 37 Modeled object support substrate 38 Stage 39 Image forming device

Japanese Unexamined Patent Publication No. 3-21910 Japanese Unexamined Patent Publication No. 2000-281634 JP-A-2007-77211

Claims (9)

An active energy ray-curable ink characterized by containing a (meth) acrylic acid ester compound represented by the following general formula (1).

(In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 1 to 12 carbon atoms which may have a side chain, and R ₃ represents an unsaturated bond-free carbon number 1. Shows 10 hydrocarbon groups.) The active energy ray-curable ink according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(In the formula, R ₁ represents a hydrogen atom or a methyl group.) The active energy ray-curable ink according to claim 2, wherein the compound represented by the general formula (2) is a compound represented by the following structural formula (3).

An active energy ray-curable inkjet ink according to any one of claims 1 to 3, wherein the active energy ray-curable ink is for an inkjet. Composition storage container Yi ink is accommodated according to any one of claims 1 to 4. A housing part b ink is accommodated according to any one of claims 1 to 4, 2-dimensional or 3-dimensional image forming apparatus and a radiation means for irradiating an active energy ray. 2-dimensional or 3-dimensional image forming method which has an irradiation step of irradiating an active energy ray to Lee ink according to any one of claims 1 to 4. Cured product, characterized in that formed by curing by an active energy ray to Lee ink according to any one of claims 1 to 4. A decorative body characterized in that a surface decoration made of the cured product according to claim 8 is applied on a base material.

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