JP7116921B2 - CURABLE COMPOSITION, CURABLE INK, COMPOSITION CONTAINER, IMAGE FORMING APPARATUS, IMAGE FORMING METHOD, CURED PRODUCT, AND DECORATION - Google Patents

Description

The present invention relates to a curable composition, a curable ink, a composition container, an image forming apparatus, an image forming method, a cured product, and a decorative body.

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

2. Description of the Related Art In recent years, an inkjet recording method using an active energy ray-curable ink has attracted attention. For example, an active energy ray-curable resin composition containing a urethane oligomer having a (meth)acrylamide group at the terminal or side chain, an N-substituted (meth)acrylamide, and a non-reactive diluent has been proposed (for example, patent Reference 1).
In addition, a compound having a (meth)acrylic acid ester group and a vinyl group in one molecule with an organic group (including an aromatic ring) having 1 to 10 carbon atoms as a core and a composition for photo-nanoimprinting using the compound are proposed. (See Patent Document 2, for example).

An object of the present invention is to provide a curable composition that is superior in photopolymerization reactivity and in cured film hardness to conventional compositions.

前記一般式（１）中、Ｘは炭素数２～５の分枝アルキレン基を表し、Ｙは下記一般式（２）を表す。

前記一般式（２）中、Ｒは炭素数１～４のアルキル基を表し、＊は前記Ｘとの結合部位を表す。 The above problem is solved by the following invention 1).
1) A curable composition containing an acrylamide compound represented by the following general formula (1).

In the general formula (1), X represents a branched alkylene group having 2 to 5 carbon atoms, and Y represents the following general formula (2).

In general formula (2) above, R represents an alkyl group having 1 to 4 carbon atoms, and * represents a bonding site with X above.

ADVANTAGE OF THE INVENTION According to this invention, the curable composition excellent in photopolymerization reactivity and the hardness of a cured film can be provided.

1 is a schematic diagram showing an example of an image forming apparatus according to the present invention; FIG. FIG. 3 is a schematic diagram showing an example of another image forming apparatus according to the present invention; FIG. 3 is a schematic diagram showing an example of still another image forming apparatus according to the present invention;

前記一般式（１）中、Ｘは炭素数２～５の分枝アルキレン基を表し、Ｙは下記一般式（２）を表す。

前記一般式（２）中、Ｒは炭素数１～４のアルキル基を表し、＊は前記Ｘとの結合部位を表す。
２）前記一般式（１）におけるＸが、炭素数４～５の分枝アルキレン基である前記１）に記載の硬化型組成物。
３）前記一般式（１）で表されるアクリルアミド化合物が、下記一般式（３）で表されるアクリルアミド化合物である前記１）に記載の硬化型組成物。

前記一般式（３）中、Ｚは炭素数１～４のアルキル基を表し、Ｙは下記一般式（２）を表す。

前記一般式（２）中、Ｒは炭素数１～４のアルキル基を表し、＊は前記炭素との結合部位を表す。
４）前記１）から３）のいずれかに記載の硬化型組成物を含有する硬化型インク。
５）前記硬化型インクがインクジェット用である前記４）に記載の硬化型インク。
６）前記１）から５）のいずれかに記載の硬化型組成物又は硬化型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硬化型組成物又は硬化型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硬化型組成物又は硬化型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）のいずれかに記載の硬化型組成物又は硬化型インクに活性エネルギー線を照射して硬化させてなる硬化物。
１０）基材上に前記９）の硬化物からなる表面加飾が施されてなる加飾体。 The present invention relates to the following 1), but also includes the following 2) to 10) as embodiments.
1) A curable composition containing an acrylamide compound represented by the following general formula (1).

In the general formula (1), X represents a branched alkylene group having 2 to 5 carbon atoms, and Y represents the following general formula (2).

In general formula (2) above, R represents an alkyl group having 1 to 4 carbon atoms, and * represents a bonding site with X above.
2) The curable composition according to 1) above, wherein X in the general formula (1) is a branched alkylene group having 4 to 5 carbon atoms.
3) The curable composition according to 1) above, wherein the acrylamide compound represented by the general formula (1) is an acrylamide compound represented by the following general formula (3).

In the general formula (3), Z represents an alkyl group having 1 to 4 carbon atoms, and Y represents the following general formula (2).

In the general formula (2), R represents an alkyl group having 1 to 4 carbon atoms, and * represents a bonding site with the carbon.
4) A curable ink containing the curable composition according to any one of 1) to 3) above.
5) The curable ink described in 4), which is for inkjet.
6) A composition container containing the curable composition or curable ink according to any one of 1) to 5) above.
7) A two-dimensional or three-dimensional device comprising a container containing the curable composition or curable ink according to any one of 1) to 5) above, and irradiation means for irradiating active energy rays. image forming device.
8) A two-dimensional or three-dimensional image forming method comprising an irradiation step of irradiating the curable composition or curable ink according to any one of 1) to 5) with an active energy ray.
9) A cured product obtained by irradiating the curable composition or curable ink according to any one of 1) to 5) above with an active energy ray to cure it.
10) A decorated body obtained by applying a surface decoration made of the cured product of 9) on a base material.

前記一般式（１）中、Ｘは炭素数２～５の分枝アルキレン基を表し、Ｙは下記一般式（２）を表す。

前記一般式（２）中、Ｒは炭素数１～４のアルキル基を表し、＊は前記Ｘとの結合部位を表す。
前記Ｘは、炭素数４～５の分枝アルキレン基であることが好ましい。 The present invention will now be described in more detail.
(Curable composition)
The curable composition of the present invention contains an acrylamide compound represented by the following general formula (1), other curable compounds, a polymerization initiator, an organic solvent, and, if necessary, a coloring material and other components. can contain

In the general formula (1), X represents a branched alkylene group having 2 to 5 carbon atoms, and Y represents the following general formula (2).

In general formula (2) above, R represents an alkyl group having 1 to 4 carbon atoms, and * represents a bonding site with X above.
X is preferably a branched alkylene group having 4 to 5 carbon atoms.

<Acrylamide compound represented by general formula (1)>
The compound represented by the general formula (1) contained in the curable composition and ink of the present invention is characterized by having a secondary acrylamide and an ester with respect to the core structure of an alkylene group containing a tertiary carbon. there is A compound having a large intermolecular interaction due to a polar functional group may be crystallized, and there is a problem that the use of the curable composition, especially the inkjet ink, is greatly restricted. Moreover, there is a problem that the strength of the cured product is lowered when the steric hindrance due to the alkyl chain is increased.
Therefore, the compound represented by the general formula (1) has a suitable degree of steric hindrance due to polarity due to secondary acrylamide and ester and tertiary carbon-containing alkylene group, so that the cured product has high hardness, Excellent photopolymerization reactivity. As a result, the acrylamide compound represented by the general formula (1) can be suitably used as a curable composition, especially as an inkjet ink.

前記一般式（３）中、Ｚは炭素数１～４のアルキル基を表し、Ｙは下記一般式（２）を表す。

前記一般式（２）中、Ｒは炭素数１～４のアルキル基を表し、＊は前記炭素との結合部位を表す。
前記Ｚは、炭素数が３～４の場合は、分岐のアルキル基であっても良い。 As the acrylamide compound represented by the general formula (1), a compound represented by the following general formula (3) is preferable because of its suitable polarity and steric hindrance.

In the general formula (3), Z represents an alkyl group having 1 to 4 carbon atoms, and Y represents the following general formula (2).

In the general formula (2), R represents an alkyl group having 1 to 4 carbon atoms, and * represents a bonding site with the carbon.
When Z has 3 to 4 carbon atoms, it may be a branched alkyl group.

Specific examples of the acrylamide compound represented by formula (1) are shown below, but the present invention is not limited thereto.

As the acrylamide compound represented by the general formula (1), a mixture of two or more different compounds can be used, and the different compounds in this case also include structural isomers. The mixing ratio is not particularly limited.
The content of the acrylamide compound in the curable composition or curable ink is generally 20 to 98% by mass, preferably 30 to 90% by mass.

<Other photopolymerizable compounds>
The curable composition can also contain photopolymerizable compounds other than the acrylamide compound represented by general formula (1). The mass ratio of the other photopolymerizable compound to the acrylamide compound represented by the general formula (1) is usually 0.01 to 100 when the mass of the acrylamide compound is 1, and the other photopolymerizable compound is 0.01 to 100. 0.1 to 50 are preferred.

The other photopolymerizable compounds are not particularly limited, but include radical photopolymerizable compounds, cationic photopolymerizable compounds, anionic photopolymerizable compounds, and the like, and two or more of them 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 undergoing 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, maleic acid, salts thereof and compounds derived from them, anhydrides having an ethylenically unsaturated group, Acrylonitrile, styrene, unsaturated polyester, unsaturated polyether, unsaturated polyamide, unsaturated urethane and the like.

Specific examples of photoradical polymerizable compounds 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 methylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, epoxy acrylate, methyl methacrylate, n-butyl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexane Diol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolethane trimethacrylate, 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, derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc., ethylene Glycol Divinyl Ether, Ethylene Glycol Monovinyl Ether, Diethylene Glycol Divinyl Ether, Triethylene Glycol Monovinyl Ether divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, 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, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether, 2-ethylhexyl diglycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl acrylate, neopentyl hydroxypivalate Glycol diacrylate, 2-acryloyloxyethyl phthalate, methoxypolyethylene glycol acrylate, tetramethylolmethane triacrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, dimethyloltricyclodecane diacrylate, ethoxylated phenyl acrylate , 2-acryloyloxyethyl succinic acid, nonylphenol ethylene 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 diisocyanate urethane prepolymer, lactone-modified flexible acrylate, butoxyethyl Acrylate, propylene glycol diglycidyl ether acrylic acid adduct, pentaerythritol triacrylate , hexamethylene diisocyanate urethane prepolymer, 2-hydroxyethyl acrylate, methoxydipropylene glycol acrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, hexamethylene diisocyanate urethane prepolymer, stearyl acrylate, isoamyl acrylate, isomyristyl Acrylate, isostearyl acrylate, lactone-modified acrylate, and the like.

Examples of photo-cationically polymerizable compounds include epoxy compounds, vinyl ether compounds, and oxetane compounds.
Examples of photo-anionically polymerizable compounds include epoxy compounds, lactone compounds, acrylic compounds, and methacrylic compounds. Among them, acrylic compounds and methacrylic compounds exemplified as photoradical polymerizable compounds are preferable.

<Polymerization initiator>
The active energy ray-curable composition of the present invention may contain a polymerization initiator. Any polymerization initiator may be used as long as it can generate active species such as radicals and cations by the energy of active energy rays to initiate polymerization of polymerizable compounds (monomers and oligomers). As such polymerization initiators, known radical polymerization initiators, cationic polymerization initiators, base generators and the like can be used singly or in combination of two or more. Among them, radical polymerization initiators are used. is preferred. Also, in order to obtain a sufficient curing speed, 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.
Examples of radical polymerization initiators include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, Examples include ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds. Aromatic ketones such as IRGACURE 907 are preferred as radical polymerization initiators.
Moreover, in addition to the polymerization initiator, a polymerization accelerator (sensitizer) can be used in combination. Examples of the polymerization accelerator include, but are not limited to, 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 preferred, and the content thereof may be appropriately set according to the polymerization initiator to be used and its amount.

As the combination of the photopolymerizable compound and the photopolymerization initiator, in addition to the combination of the photoradical polymerizable compound and the photoradical polymerization initiator, the combination of the photocationically polymerizable compound and the photocationic polymerization initiator, and the photoanion A combination of a polymerizable compound and a photoanionic polymerization initiator may be mentioned.

Examples of photocationic polymerization initiators include aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium and phosphonium B(C ₆ F ₅ ) ₄ ^- , PF ₆ ^- , AsF ₆ ^- , SbF ₆ ^- and CF ₃ SO ₃ . ^-salts , sulfonates capable of generating sulfonic acid, halides capable of generating hydrogen halide, iron allene complexes, and the like.

Examples of photoanionic polymerization initiators include o-nitrobenzyl carbamate derivatives, o-acyloxyl derivatives, o-carbamoyl oxime amidine derivatives and the like.

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

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

The curable composition of the present invention is cured by heating or active energy rays. Hereinafter, the curable composition of the present invention may be referred to as an active energy ray-curable composition, but it is not limited to the active energy ray-curable composition.

<Organic solvent>
Although the active energy ray-curable composition of the present invention may contain an organic solvent, it is preferable not to contain it if possible. If the composition does not contain organic solvents, especially volatile organic solvents (VOC (Volatile Organic Compounds) free), the safety of the place where the composition is handled is further increased, and it is possible to prevent environmental pollution. . The term "organic solvent" means general non-reactive organic solvents such as ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and should be distinguished from reactive monomers. be. In addition, "not including" an organic solvent means not including substantially an organic solvent, and it is preferably less than 0.1% by mass.

<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, lustrous colors such as gold and silver, etc., depending on the purpose and required properties 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 density, dispersibility in the composition, etc., and is not particularly limited. It is preferably 1 to 20% by mass. In addition, the active energy ray-curable composition of the present invention may be colorless and transparent without containing a coloring material, and in that case, it is suitable as an overcoat layer for protecting images, for example.
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.
Examples of inorganic pigments that can be used include carbon black (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide.
Examples of organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone. Polycyclic pigments such as pigments, dye chelates (for example, basic dye chelates, acid dye chelates, etc.), dyeing lakes (basic dye lakes, acid dye lakes), nitro pigments, nitroso pigments, aniline black, Daylight fluorescent pigments may be mentioned.
In addition, a dispersant may be further included in order to improve the dispersibility of the pigment. The dispersant is not particularly limited, but includes, for example, dispersants commonly used for preparing pigment dispersions such as polymeric dispersants.
As dyes, for example, acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and they may be used singly or in combination of two or more.

<Other ingredients>
The active energy ray-curable composition of the present invention may optionally contain other known components. Other components are not particularly limited, but include, for example, conventionally known surfactants, polymerization inhibitors, leveling agents, antifoaming agents, fluorescent whitening agents, penetration accelerators, humectants (moisturizing agents), and fixing agents. agents, viscosity stabilizers, antifungal agents, preservatives, antioxidants, ultraviolet absorbers, chelating agents, pH adjusters, and thickeners.

<Preparation of active energy ray-curable composition>
The active energy ray-curable composition of the present invention can be produced using the various components described above, and the preparation means and conditions are not particularly limited. Put into a dispersing machine such as kitty mill, disc mill, pin mill, dyno mill, etc., disperse to prepare pigment dispersion liquid, and further mix polymerizable monomer, initiator, polymerization inhibitor, surfactant, etc. into the pigment dispersion liquid. It can be prepared by

<Viscosity>
The viscosity of the active energy ray-curable composition of the present invention may be appropriately adjusted according to the application and application means, and is not particularly limited. For example, when applying a discharge means for discharging the composition from a nozzle. is preferably 3 to 40 mPa·s, more preferably 5 to 15 mPa·s, particularly preferably 6 to 12 mPa·s, in the range of 20°C to 65°C, preferably 25°C. Moreover, it is particularly preferable that the viscosity range is satisfied without including the organic solvent. The above viscosity was measured using a cone-plate rotary viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd., using a cone rotor (1°34′×R24), rotating at 50 rpm, and constant-temperature circulating water at a temperature of 20°C. Measurement can be performed by appropriately setting the temperature in the range of ~65°C. VISCOMATE VM-150III can be used to adjust the temperature of the circulating water.

<Curing means>
Examples of means for curing the curable composition of the present invention include heat curing and curing with active energy rays, and among these, curing with active energy rays is preferable.
Examples of the active energy ray used for curing the active energy ray-curable composition of the present invention include ultraviolet rays, electron beams, α rays, β rays, γ rays, X rays, and other polymerizable components in the composition. It is not particularly limited as long as it can impart the energy necessary for proceeding with the polymerization reaction. Especially when using a high-energy light source, the polymerization reaction can proceed without using a polymerization initiator. Further, in the case of ultraviolet irradiation, there is a strong desire to eliminate mercury from the viewpoint of environmental protection, and replacement with GaN-based semiconductor ultraviolet light emitting devices is very useful both industrially and environmentally. Furthermore, ultraviolet light emitting diodes (UV-LEDs) and ultraviolet laser diodes (UV-LDs) are compact, have a long life, are highly efficient, and are low in cost, and are preferred as ultraviolet light sources.

<Application>
The application of the active energy ray-curable composition of the present invention is not particularly limited as long as it is a field where active energy ray-curable materials are generally used, and can be appropriately selected according to the purpose. Examples include resins, paints, adhesives, insulating materials, release agents, coating materials, sealing materials, various resists, and various optical materials.
Furthermore, the active energy ray-curable composition of the present invention can be used not only as an ink to form two-dimensional characters and images, and to form a design coating film on various substrates, but also to form three-dimensional images (three-dimensional objects). 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 repeating curing and lamination of powder layers. It may be used as a three-dimensional configuration material (model material) or a support member (support material) used in such a layered manufacturing method (stereolithography method). In addition, FIG. 2 shows a method of discharging the active energy ray-curable composition of the present invention to a predetermined region, irradiating the active energy ray and curing it, and sequentially laminating the solidified product to form a three-dimensional shape (details will be described later). 3, a storage pool (receiving portion) 1 of the active energy ray-curable composition 5 of the present invention is irradiated with an active energy ray 4 to form a cured layer 6 having a predetermined shape on a movable stage 3, and this is This is a method for three-dimensional modeling by successively layering layers.
As a stereolithography apparatus for molding a three-dimensional object using the active energy ray-curable composition of the present invention, a known apparatus can be used, and is not particularly limited. For example, means for containing the composition , a supply means, a discharge means, an active energy ray irradiation means, and the like.
The present invention also includes a molded article obtained by processing a cured product obtained by curing an active energy ray-curable composition and a structure in which the cured product is formed on a substrate. The molded article is, for example, a sheet-shaped or film-shaped cured product or structure subjected to molding such as heat stretching or punching.・It is suitable for applications that require molding after surface decoration, such as electronic equipment, meters for cameras, and operation panels.
The base material is not particularly limited and can be appropriately selected according to the purpose. Examples include paper, thread, fiber, fabric, leather, metal, plastic, glass, wood, ceramics, composite materials thereof, and the like. and a plastic substrate is preferable from the viewpoint of workability.

<Composition storage container>
The composition storage container of the present invention means a container in which the active energy ray-curable composition is stored, and is suitable for the above uses. For example, when the active energy ray-curable composition of the present invention is used as an ink, the container containing the ink can be used as an ink cartridge or an ink bottle. In the work, it is no longer necessary to touch the ink directly, and it is possible to prevent stains on fingers and clothes. In addition, it is possible to prevent foreign matter such as dust from entering the ink. The shape, size, material, etc. of the container itself are not particularly limited as long as they are suitable for the application and usage. should be covered with a protective sheet or the like.

<Image Forming Method and Forming Apparatus>
In the image forming method of the present invention, an active energy ray may be used, or heating may be used.
In order to cure the curable composition of the present invention with an active energy ray, there is an irradiation step of irradiating the active energy ray, and the image forming apparatus of the present invention includes irradiation means for irradiating the active energy ray. and a container for containing the active energy ray-curable composition of the present invention, and the container may be contained in the container. Furthermore, it may have a discharge step and discharge means for discharging the active energy ray-curable composition. The method of discharging is not particularly limited, but examples include a continuous injection type, an on-demand type, and the like. The on-demand type includes a piezo system, a thermal system, an electrostatic system, and the like.
FIG. 1 shows an example of an image forming apparatus equipped with an inkjet ejection means. Ink is ejected onto the recording medium 22 supplied from the supply roll 21 by the respective color printing units 23a, 23b, 23c, and 23d provided with the ink cartridges and the ejection heads of the active energy radiation curable inks of yellow, magenta, cyan, and black. be done. After that, the light sources 24a, 24b, 24c, and 24d for curing the ink are irradiated with active energy rays to cure the ink, thereby forming a color image. After that, the recording medium 22 is conveyed to the processing unit 25 and the print take-up roll 26 . A heating mechanism may be provided in each of the printing units 23a, 23b, 23c, and 23d so that the ink is liquefied at the ink discharge section. Further, if necessary, a mechanism may be provided for cooling the recording medium to about room temperature by contact or non-contact. Inkjet recording methods include a serial method in which a head is moved to eject ink onto a recording medium that moves intermittently according to the width of an ejection head, and a serial method in which ink is ejected onto a recording medium by moving the recording medium continuously. Any line system in which ink is ejected onto a recording medium from a head held at a fixed position can be applied.
The recording medium 22 is not particularly limited, but includes paper, film, ceramics, glass, metal, composite materials thereof, and the like, and may be in the form of a sheet. Further, the configuration may be such that only single-sided printing is possible, or that double-sided printing is also possible. Not limited to those used as general recording media, corrugated cardboard, building materials such as wallpaper and flooring, concrete, cloth for clothing such as T-shirts, textiles, leather, and the like can be used as appropriate.
Furthermore, the active energy ray irradiation from the light sources 24a, 24b, and 24c may be weakened or omitted, and after printing a plurality of colors, the active energy ray may be irradiated from the light source 24d. As a result, energy saving and cost reduction can be achieved.
The recorded matter to be recorded with the ink of the present invention includes not only those printed on smooth surfaces such as ordinary paper and resin films, but also those printed on uneven surfaces to be printed, and those printed on metals, ceramics, and the like. It also includes those printed on a printing surface made of various materials. In addition, by layering two-dimensional images, it is possible to form an image (an image consisting of two-dimensional and three-dimensional images) or a three-dimensional object with a partial three-dimensional effect.
FIG. 2 is a schematic diagram showing an example of another image forming apparatus (three-dimensional stereoscopic image forming apparatus) according to the present invention. The image forming apparatus 39 in FIG. 2 uses a head unit (movable in the AB direction) in which inkjet heads are arranged, and ejects the first active energy ray-curable composition from the ejection head unit 30 for a modeled object. A second active energy ray-curable composition having a composition different from that of the first active energy ray-curable composition is ejected from the head units 31 and 32, and these compositions are cured by adjacent ultraviolet irradiation means 33 and 34. It is laminated while doing so. More specifically, for example, the second active energy ray-curable composition is ejected from the support ejection head units 31 and 32 onto the shaped object support substrate 37, and is irradiated with an active energy ray to be 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 an active energy ray to be solidified. By repeating the step of forming the first model layer by pressing the support layer and the model layer a plurality of times while lowering the vertically movable stage 38 according to the number of layers, the support layer and the model layer are laminated to form the three-dimensional model 35 . to manufacture. After that, the support laminate 36 is removed as needed. In FIG. 2, only one ejection head unit 30 for a modeled object is provided, but two or more may be provided.

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

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ１．４０－１．４５（ｍ，１２Ｈ），４．７２－４．７８（ｍ，１Ｈ），５．６８－５．７０（ｍ，１Ｈ），６．２３－６．２７（ｍ，２Ｈ），６．３１－６．３４（ｍ，１Ｈ） [Production Example 1]
5.00 g of L-alanine tert-butyl hydrochloride manufactured by Tokyo Chemical Industry Co., Ltd. was dissolved in 40 mL of water, and 40 mL of ethyl acetate and 39.51 g (286 mmol) of potassium carbonate were added. After cooling in an ice bath, 18.1 g (200 mmol) of acrylic acid chloride was added dropwise, and the mixture was stirred overnight at room temperature. The reaction liquid was extracted and separated, and the ethyl acetate layer was separated. The obtained ethyl acetate layer was concentrated to obtain 34.16 g of compound a-4 as a colorless oil (yield: about 97%).

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 1.40-1.45 (m, 12H), 4.72-4.78 (m, 1H), 5.68-5.70 (m, 1H), 6. 23-6.27 (m, 2H), 6.31-6.34 (m, 1H)

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ０．９２－０．９７（ｍ，６Ｈ），２．１６－２．２５（ｍ，１Ｈ），３．７６（ｓ，３Ｈ），４．６６－４．６９（ｍ，１Ｈ），５．６８－５．７１（ｍ，１Ｈ），６．１１（ｓｌ，１Ｈ），６．１４－６．２０（ｑ，１Ｈ），６．３１－６．３４（ｍ，１Ｈ） [Production Example 2]
After cooling the slurry obtained by mixing 22.33 g (191 mmol) of DL-valine manufactured by Tokyo Chemical Industry Co., Ltd. with 125 mL of methanol in an ice bath, 45.35 g (381 mmol) of thionyl chloride was added dropwise to react, A reaction liquid was obtained. After stirring the reaction solution overnight at room temperature, the obtained reaction solution was concentrated to obtain 32.35 g of DL-valine methyl ester hydrochloride as a white solid. The resulting DL-valine methyl ester hydrochloride was directly used in the next reaction.
32.35 g of methyl ester hydrochloride of DL-valine was dissolved in 250 mL of water, and 39.51 g (286 mmol) of potassium carbonate was added. After cooling in an ice bath, 18.1 g (200 mmol) of acrylic acid chloride was added dropwise, and the mixture was stirred overnight at room temperature. The reaction solution was extracted and separated with ethyl acetate, and the ethyl acetate layer was separated. The obtained ethyl acetate layer was concentrated to obtain 34.16 g of compound c-1 as a colorless oil (yield: about 97%).

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 0.92-0.97 (m, 6H), 2.16-2.25 (m, 1H), 3.76 (s, 3H), 4.66-4. 69 (m, 1H), 5.68-5.71 (m, 1H), 6.11 (sl, 1H), 6.14-6.20 (q, 1H), 6.31-6.34 ( m, 1H)

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ０．９２－０．９５（ｍ，６Ｈ），１．１６－１．２８（ｍ，１Ｈ），１．４３－１．５１（ｍ，１Ｈ），１．８９－１．９７（ｍ，１Ｈ），３．７６（ｓ，３Ｈ），４．６９－４．７２（ｍ，１Ｈ），５．６８－５．７０（ｍ，１Ｈ），６．１３－６．１９（ｍ，２Ｈ），６．３０－６．３４（ｍ，１Ｈ） [Production Example 3]
After cooling the slurry obtained by mixing 25.00 g (191 mmol) of DL-isoleucine manufactured by Tokyo Chemical Industry Co., Ltd. with 125 mL of methanol in an ice bath, 45.35 g (381 mmol) of thionyl chloride is added dropwise to react, A reaction liquid was obtained. After the reaction solution was stirred overnight at room temperature, the obtained reaction solution was concentrated to obtain 34.79 g of DL-isoleucine methyl ester hydrochloride as a white solid. The resulting DL-isoleucine methyl ester hydrochloride was directly used in the next reaction.
34.79 g of methyl ester hydrochloride of DL-isoleucine was dissolved in 250 mL of water, and 39.51 g (286 mmol) of potassium carbonate was added. After cooling in an ice bath, 18.1 g (200 mmol) of acrylic acid chloride was added dropwise, and the mixture was stirred overnight at room temperature. The reaction solution was extracted and separated with ethyl acetate, and the ethyl acetate layer was separated. The obtained ethyl acetate layer was concentrated to obtain 34.16 g of a colorless oil (yield: about 97%).
Furthermore, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. was packed and purified by column chromatography using hexane and ethyl acetate as eluents to obtain 32.7 g of compound d-1 as a colorless liquid (yield : about 86%).

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 0.92-0.95 (m, 6H), 1.16-1.28 (m, 1H), 1.43-1.51 (m, 1H), 1. 89-1.97 (m, 1H), 3.76 (s, 3H), 4.69-4.72 (m, 1H), 5.68-5.70 (m, 1H), 6.13- 6.19 (m, 2H), 6.30-6.34 (m, 1H)

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ０．９４－０．９７（ｍ，６Ｈ），１．５４－１．６１（ｍ，１Ｈ），１．６４－１．６８（ｍ，２Ｈ），３．７５（ｓ，３Ｈ），４．７２－４．７７（ｍ，１Ｈ），５．６６－５．６９（ｍ，１Ｈ），６．１２－６．１８（ｑ，１Ｈ），６．２２（ｓｌ，１Ｈ），６．３０－６．３３（ｍ，１Ｈ） [Production Example 4]
After cooling the slurry obtained by mixing 10.00 g (76 mmol) of DL-leucine manufactured by Tokyo Chemical Industry Co., Ltd. with 50 mL of methanol in an ice bath, 18.14 g (153 mmol) of thionyl chloride is added dropwise to react, A reaction liquid was obtained. After stirring the reaction solution overnight at room temperature, the obtained reaction solution was concentrated to obtain 13.50 g of DL-leucine methyl ester hydrochloride as a white solid. The obtained DL-leucine methyl ester hydrochloride was directly used in the next reaction.
13.50 g of methyl ester hydrochloride of DL-leucine was dissolved in 108 mL of water, and 15.80 g (114 mmol) of potassium carbonate was added. After cooling in an ice bath, 15.8 g (80 mmol) of acrylic acid chloride was added dropwise, and the mixture was stirred overnight at room temperature. The reaction solution was extracted and separated with ethyl acetate, and the ethyl acetate layer was separated. The obtained ethyl acetate layer was concentrated to obtain 13.40 g of compound e-1 as a colorless oil (yield: about 88%).

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 0.94-0.97 (m, 6H), 1.54-1.61 (m, 1H), 1.64-1.68 (m, 2H), 3. 75 (s, 3H), 4.72-4.77 (m, 1H), 5.66-5.69 (m, 1H), 6.12-6.18 (q, 1H), 6.22 ( sl, 1H), 6.30-6.33 (m, 1H)

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ１．２６－１．２７（ｄ，３Ｈ），２．５７－２．５８（ｄ，２Ｈ），３．７０（ｓ，３Ｈ），４．４０－４．４８（ｍ，１Ｈ），５．６３－５．６５（ｍ，１Ｈ），６．０６－６．１１（ｍ，１Ｈ），６．２５－６．２９（ｍ，１Ｈ），６．３６（ｓｌ，１Ｈ） [Production Example 5]
After cooling a slurry obtained by mixing 5.00 g (49 mmol) of DL-3-aminobutyric acid manufactured by Tokyo Chemical Industry Co., Ltd. with 25 mL of methanol in an ice bath, 11.54 g (97 mmol) of thionyl chloride was added dropwise. It was made to react and the reaction liquid was obtained. After stirring the reaction solution overnight at room temperature, the obtained reaction solution was concentrated to obtain 7.40 g of DL-3-aminobutyric acid methyl ester hydrochloride as a pale yellow oil. The resulting DL-3-aminobutyric acid methyl ester hydrochloride was directly used in the next reaction.
7.40 g of methyl ester hydrochloride of DL-3-aminobutyric acid was dissolved in 60 mL of water, and 60 ml of ethyl acetate and 10.06 g (73 mmol) of potassium carbonate were added. After cooling in an ice bath, 4.6 g (80 mmol) of acrylic acid chloride was added dropwise, and the mixture was stirred overnight at room temperature. The reaction liquid was extracted and separated, and the ethyl acetate layer was separated. The resulting ethyl acetate layer was concentrated to obtain 6.97 g of compound f-1 as a colorless oil (yield: about 84%).

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 1.26-1.27 (d, 3H), 2.57-2.58 (d, 2H), 3.70 (s, 3H), 4.40-4. 48 (m, 1H), 5.63-5.65 (m, 1H), 6.06-6.11 (m, 1H), 6.25-6.29 (m, 1H), 6.36 ( sl, 1H)

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ１．３４－１．４１（ｍ，２Ｈ），１．５４－１．６１（ｑｕｉｎ，２Ｈ），１．６３－１．６９（ｑｕｉｎ，２Ｈ），２．３１－２．３４（ｔ，２Ｈ），３．３３－３．３７（ｑ，２Ｈ），３．６７（ｓ，３Ｈ），５．６２－５．６５（ｍ，２Ｈ），６．０６－６．１１（ｑ，１Ｈ），６．２６－６．３０（ｍ，１Ｈ） [Comparative Production Example 1]
After cooling the slurry obtained by mixing 25.0 g (191 mmol) of 6-aminohexanoic acid manufactured by Tokyo Chemical Industry Co., Ltd. with 125 mL of methanol in an ice bath, 45.35 g (381 mmol) of thionyl chloride was added dropwise to react. to obtain a reaction solution. After stirring the reaction solution overnight at room temperature, the obtained reaction solution was concentrated to obtain 36.52 g of 6-aminohexanoic acid methyl ester hydrochloride as a white solid. The resulting 6-aminohexanoic acid methyl ester hydrochloride was directly used in the next reaction.
36.52 g of methyl ester hydrochloride of 6-aminohexanoic acid was dissolved in 250 mL of water, and 39.51 g (286 mmol) of potassium carbonate was added. After cooling in an ice bath, 18.1 g (200 mmol) of acrylic acid chloride was added dropwise, and the mixture was stirred overnight at room temperature. The reaction solution was extracted and separated with ethyl acetate, and the ethyl acetate layer was separated. The resulting ethyl acetate layer was concentrated to obtain 29.0 g (yield: about 76%) of a pale brown solid represented by the following structural formula (1), which was used as the compound of Comparative Production Example 1.

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 1.34-1.41 (m, 2H), 1.54-1.61 (quin, 2H), 1.63-1.69 (quin, 2H), 2. 31-2.34 (t, 2H), 3.33-3.37 (q, 2H), 3.67 (s, 3H), 5.62-5.65 (m, 2H), 6.06- 6.11 (q, 1H), 6.26-6.30 (m, 1H)

同定データは次に示すとおりである。
^１Ｈ－ＮＭＲ（ＣＤＣｌ_３）：δ１．４３－１．４４（ｄ,３Ｈ）,３．０３（ｓ,３Ｈ）,３．７２（ｓ，３Ｈ），５．２７－５．３１（ｍ，１Ｈ），５．６８－５．７６（ｍ，１Ｈ），６．３５－６．３９（ｍ，１Ｈ），６．５８－６．６３（ｍ，１Ｈ） [Comparative Production Example 2]
After cooling a slurry obtained by mixing 6.19 g (60 mmol) of N-methyl-DL-alanine manufactured by Combi-Blocks with 40 mL of methanol in an ice bath, 14.28 g (120 mmol) of thionyl chloride was added dropwise. to obtain a reaction solution. After stirring the reaction solution overnight at room temperature, the obtained reaction solution was concentrated to obtain 8.4 g of N-methyl-DL-alanine methyl ester as a colorless liquid. The obtained methyl ester of N-methyl-DL-alanine was directly used in the next reaction.
8.4 g of methyl ester of N-methyl-DL-alanine was dissolved in 40 mL of water, and 11.94 g (87 mmol) of potassium carbonate was added. After cooling in an ice bath, 5.38 g (59 mmol) of acrylic acid chloride was added dropwise, and the mixture was stirred overnight at room temperature. The reaction solution was extracted and separated with ethyl acetate, and the ethyl acetate layer was separated. The obtained ethyl acetate layer was concentrated to obtain a yellow oil.
Furthermore, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. was packed and purified by column chromatography using hexane and ethyl acetate as eluents to obtain 4.1 g of a colorless liquid of the following structural formula (2) ( Yield of about 44%) was obtained and used as the compound of Comparative Production Example 2.

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 1.43-1.44 (d, 3H), 3.03 (s, 3H), 3.72 (s, 3H), 5.27-5.31 (m, 1H), 5.68-5.76 (m, 1H), 6.35-6.39 (m, 1H), 6.58-6.63 (m, 1H)

[Active energy ray-curable comparative compound 3]
A commercially available hydroxyethyl acrylamide (manufactured by KJ Chemicals Co., Ltd.) represented by the following structural formula (3) was used as active energy ray-curable comparative compound 3.

Examples 1a-8a, Comparative Examples 1a-3a
[Preparation of photocurable composition]
Production Examples 1-5 and Comparative Production Examples 1-2, Comparative Compound 3, and a photopolymerization initiator IRGACURE 907 [2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one] ( BASF Japan) were mixed using a magnetic stirrer to prepare photocurable compositions of Examples 1a to 8a and Comparative Examples 1a to 3a.

The photopolymerization reactivity and pencil hardness of the photocurable compositions of Examples 1a to 8a and Comparative Examples 1a to 3a were evaluated as follows. Table 1 shows the results.
<Photopolymerizable>
The photopolymerization reactivity of each photocurable composition was evaluated using a measuring device combining a DSC-7020 (manufactured by SII) and a spot light source LA-410UV (manufactured by HAYASHI WATCH-WORKS).
Specifically, the calorific value (mJ/mg) per unit weight when irradiated with ultraviolet rays having a wavelength of 365 nm at 100 mW/cm ² for 0.02 minutes in the atmosphere was measured. The obtained calorific value per unit weight was multiplied by the molecular weight to calculate the calorific value per mol, which was used as an index for comparing the reactivity of the photopolymerization reaction.

<Pencil hardness>
The photocurable composition prepared above was coated on a PET film to a thickness of 10 μm, and irradiated 17 times under the condition that the irradiation energy per pass of a metahalal lamp was 600 mJ/cm ² in the atmosphere. Curing was performed with an integrated irradiation energy of 10600 mJ/cm ² . After allowing the sample to stand overnight, a pencil hardness test was performed according to JISK5600-5-4 standards. Here, a pencil scratch hardness tester (Cortec model KT-VF2391, load 750 g) and a pencil for pencil hardness test (manufactured by Mitsubishi Pencil Co., Ltd.) were used.

From Table 1, it can be seen that the photocurable compositions of Examples 1a to 8a using the photopolymerizable compounds of Production Examples 1 to 5 are excellent in photopolymerization reactivity and hardness (pencil hardness) of the cured film. . The polarity of the secondary acrylamide and the ester and the size of the steric hindrance by the alkylene group containing the tertiary carbon are appropriate, so the liquid state is realized, and the photopolymerization and hardness of the cured film are enhanced by the intermolecular interaction. It is considered that both properties can be achieved at a high level, and it can be said that they are suitable for active energy ray-curable compositions and inks, especially for inkjet inks.

Examples 1b-8b
[Preparation of ink]
100 parts of each photopolymerizable compound of Production Examples 1 to 5, 10 parts of photopolymerization initiator IRGACURE 907 (manufactured by BASF Japan) and 3 parts of carbon black MICROLITH Black CK (manufactured by BASF Japan) are mixed, Each of the inks of Examples 1b-8b was obtained.

Examples 1c-8c
100 parts of each photopolymerizable compound of Production Examples 1 to 5, a photopolymerization initiator IRGACURE 907 (manufactured by BASF Japan) 10 parts and a blue pigment MICROLITH Blue 4G-K (manufactured by BASF Japan) 3 parts were mixed, and Examples Inks 1c to 8c were obtained.

[Ink Evaluation 1]
After each of the inks of Examples 1b to 8b and Examples 1c to 8c was inkjet-discharged onto a slide glass, a UV irradiation machine LH6 (manufactured by Fusion Systems Japan) was used to apply ultraviolet rays having a wavelength of 365 nm at 200 mW/cm ² . 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]
After dipping the tip of the dip pen in each of the inks of Examples 1b to 8b and Examples 1c to 8c and writing letters on PET film and plain paper, using a UV irradiation machine LH6 (manufactured by Fusion System Japan), It was cured by irradiating ultraviolet rays with a wavelength of 365 nm at 200 mW/cm ² . As a result, each ink image was sufficiently cured.

1 Storage pool (accommodation part)
3 Movable stage 4 Active energy ray 5 Active energy ray-curable composition 6 Curing layer 21 Supply roll 22 Recording medium 23a, 23b, 23c, 23d Printing units 24a, 24b, 24c, 24d Light source 25 Processing unit 26 Print winding roll 30 modeled object ejection head units 31, 32 support member ejection head units 33, 34 ultraviolet ray irradiation means 35 three-dimensional modeled object 36 support laminate 37 modeled object support substrate 38 stage 39 image forming apparatus

JP 2016-113518 A JP 2009-215179 A

Claims (8)

The following general formula (3) A curable composition containing an acrylamide compound represented by

In the general formula (3), Z represents an alkyl group having 1 to 4 carbon atoms, and Y represents the following general formula (2).

In the general formula (2), R represents an alkyl group having 1 to 4 carbon atoms, and * represents a bonding site with the carbon. A curable ink containing the curable composition according to claim 1 . 3. The curable ink according to claim 2 , wherein the curable ink is for inkjet. A composition container containing the curable composition or curable ink according to any one of claims 1 to 3 . A two-dimensional or three-dimensional image forming apparatus comprising: a storage unit storing the curable composition or curable ink according to any one of claims 1 to 3 ; and irradiation means for irradiating active energy rays. . 4. A two-dimensional or three-dimensional image forming method, comprising an irradiation step of irradiating the curable composition or curable ink according to any one of claims 1 to 3 with an active energy ray. A cured product obtained by irradiating the curable composition or curable ink according to any one of claims 1 to 3 with an active energy ray to cure the composition. A decorated body obtained by applying a surface decoration comprising the cured product according to claim 7 on a base material.

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