JP6776627B2 - Active energy ray-curable composition, active energy ray-curable ink, composition container, image forming apparatus, image forming method, cured product, molded product and compound. - Google Patents

Description

The present invention relates to an active energy ray-curable composition, an active energy ray-curable ink, a composition container, an image forming apparatus, an image forming method, a cured product, a molded product, and a compound.

As an inkjet ink, an active energy ray-curable inkjet ink that is cured and fixed by an active energy ray is known. Ink for inkjet is usually required to have a viscosity low enough to be ejected, but if a large amount of polyfunctional monomer is used in order to increase the curability of the ink and the hardness of the cured product, the viscosity becomes high. Discharge from the inkjet head may be difficult.

On the other hand, for inkjet inks, it is an important issue to reduce the odor (odor). In general, conventional active energy ray-curable inkjet inks contain a large amount of low molecular weight reactive monomer called a diluent, which also serves as a solvent, and keeps ink physical properties such as viscosity in an appropriate state. ing. However, such low molecular weight monomer compounds have a peculiar odor and often cause discomfort.

For the purpose of improving the viscosity, curing rate, odor, adhesion and the like of the active energy ray-curable composition, for example, Patent Documents 1 to 4 disclose acrylate compounds having an amide structure. However, in the prior art, the viscosity, odor and curability of the active energy ray-curable composition have not been simultaneously satisfied to the desired levels.

Therefore, an object of the present invention is to provide an active energy ray-curable composition having a sufficiently low viscosity, suppressing odor, and having excellent curability.

The above problem is solved by the configuration of 1) below.
1) An active energy ray-curable composition comprising at least a compound represented by the general formula (I).

(In the formula, R ₁ represents a hydrogen or methyl group. R ₂ and R ₃ each independently represent a linear or branched alkyl group . However, at least one of R ₂ and R ₃ has 2 or more carbon atoms. A represents an alkylene group.)

According to the present invention, there is provided an active energy ray-curable composition having a sufficiently low viscosity, suppressing odor, and having excellent curability.

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.

Hereinafter, the present invention will be described in more detail.
The active energy ray-curable composition in the present invention contains at least a compound represented by the following general formula (I) as a polymerizable compound, and if necessary, a polymerization initiator, a coloring material, an organic solvent, and the like. Including the components of.

(In the formula, R ₁ represents a hydrogen or a methyl group. R ₂ and R ₃ each independently represent an alkyl group which may have a substituent. However, at least one carbon of R ₂ and R ₃ is carbon. The number is 2 or more. A represents an alkylene group.)

Since the compound represented by the general formula (I) has a sufficiently low viscosity, suppresses odor, and has excellent curability, it is an active energy ray-curable ink, especially an active energy ray-curable ink for inkjet. It is useful as a mold ink.

The alkyl group R _2, for example, an alkyl group having 1 to 6 carbon atoms, among them preferably an alkyl group having 2 to 6 carbon atoms.

Examples of the alkyl group of R ₃ include an alkyl group having 1 to 7 carbon atoms, and an alkyl group having 2 to 7 carbon atoms is preferable.
When R ₂ and R ₃ are linear or branched alkyl groups, the viscosity of the active energy ray-curable composition can be further reduced, which is preferable.

Further, if both R ₂ and R ₃ are methyl groups, they tend to volatilize, which is not preferable from the viewpoint of odor. Therefore, at least one of R ₂ and R ₃ needs to have 2 or more carbon atoms. When R ₂ is a methyl group, R ₃ is preferably an alkyl group having 2 to 7 carbon atoms. On the contrary, when R ₃ is a methyl group, R ₂ is preferably an alkyl group having 2 to 6 carbon atoms.

Examples of the alkylene group of A include an alkylene group having 2 to 4 carbon atoms.

There are various routes for the synthesis of the compound represented by the general formula (I), which can be appropriately selected depending on the available raw materials. For example, the corresponding amino alcohol is amidated and then acrylicized. The compound of the general formula (I) can be obtained.

Specific examples (A-1) to (A-10) of the compound represented by the general formula (I) are shown below, but the present invention is not limited to the following specific examples. Further, the compound represented by the general formula (I) may be used alone or in combination of two or more.

<Other polymerizable compounds>
The active energy ray-curable composition of the present invention can also contain other polymerizable compounds other than the compound represented by the general formula (I).

The other polymerizable compound is not particularly limited as long as it is a compound having one or more polymerizable ethylenically unsaturated groups, 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 (B-1) to (B-14) of other polymerizable compounds are shown below, but the present invention is not limited to the following specific examples. Further, these may be used alone or in combination of two or more.

The proportion of the compound represented by the general formula (I) in the polymerizable compound is, for example, 40 to 100% by mass, preferably 50 to 100% by mass.

<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 components, if necessary. The other components are not particularly limited, but are, for example, conventionally known surfactants, polymerization inhibitors, leveling agents, antifoaming agents, fluorescent whitening agents, penetration promoters, wetting agents (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.

The present invention will be further described below with reference to Examples and Comparative Examples, but the present invention is not limited to the following examples.

<Synthesis example 1>
Synthesis of the compound A-1 The compound A-1 was synthesized by the following procedure.
12.97 g of 2- (t-Buthylamino) ethylmethacrylate manufactured by Wako Pure Chemical Industries, Ltd. was added to 100 mL of dehydrated dichloromethane, then 10.12 g of triethylamine was added and cooled to -10 ° C., and then acetyl chloride manufactured by Tokyo Chemical Industry Co., Ltd. 6.59 g was added dropwise over 1 hour, and the mixture was further stirred at room temperature for 1.5 hours. Further, the precipitate was removed by filtration and then concentrated under reduced pressure to obtain 15 g of brown oil. Further, 350 g of Wakogel C-300 (manufactured by Wako Pure Chemical Industries, Ltd.) was filled, and 11.2 g of a transparent oil-like target product was obtained by column chromatography.

The obtained compound was subjected to NMR analysis using ECX500 manufactured by JEOL Ltd. and FT-IR analysis using Spectrem GX manufactured by Perkin Elmer, and the following results were obtained.
^{1 1} H-NMR (CDCl ₃ ): δ1.46 (s, 9H), 1.95 (s, 3H), 2.19 (s, 3H), 3.63 (t, 2H), 4.22 (t) , 2H), 5.62 (s, 1H), 6.12 (s, 1H)
FT-IR: 2964, 2929, 1720, 1651, 1397, 1295, 1162, 1012, 943,814 (cm ^-1 )

<Synthesis example 2>
Synthesis of Compound A-3 Compound A-3 was synthesized in the same procedure except that the acetyl chloride of Synthesis Example 1 was replaced with octanoyl chloride.

The obtained compound was subjected to NMR analysis using ECX500 manufactured by JEOL Ltd. and FT-IR analysis using Spectrem GX manufactured by Perkin Elmer, and the following results were obtained.
^{1 1} H-NMR (CDCl ₃ ): δ0.88 (t, 3H), 1.3 (m, 10H), 1.45 (s, 9H), 1.95 (s, 3H), 2.38 (t) , 2H), 3.63 (t, 2H), 4.20 (t, 2H), 5.61 (s, 1H), 6.12 (s, 1H)
FT-IR: 2959, 2928, 2856, 1722, 1654, 1397, 1295, 1158, 941, 813 (cm ^-1 )

<Synthesis example 3>
Synthesis of the compound A-4 The compound A-4 was synthesized by the following procedure.
After adding 7.03 g of 4-ethylamino-1-butanol manufactured by Tokyo Chemical Industry Co., Ltd. to 110 mL of dehydrated dichloromethane and then adding 13.66 g of triethylamine and cooling to −70 ° C., acetyl chloride manufactured by Tokyo Chemical Industry Co., Ltd. 3. 77 g and 3 ml of dehydrated dichloromethane were added dropwise and stirred for 20 minutes, and further stirred at room temperature for 1.5 hours. Next, the solution was cooled to −55 ° C., 5.43 g of acryloyl chloride manufactured by Wako Pure Chemical Industries, Ltd. and 4 ml of dehydrated dichloromethane were added dropwise thereto, and the mixture was stirred for 30 minutes. Further, the precipitate was removed by filtration and then concentrated under reduced pressure to obtain 9.8 g of yellow oil. Further, 300 g of Wakogel C-300 (manufactured by Wako Pure Chemical Industries, Ltd.) was filled, and 5.86 g of a light yellow oil-like target product was obtained by column chromatography.

The obtained compound was subjected to NMR analysis using ECX500 manufactured by JEOL Ltd. and FT-IR analysis using Spectrem GX manufactured by Perkin Elmer, and the following results were obtained.
^{1 1} H-NMR (CDCl ₃ ): δ1.2 (m, 3H), 1.7 (m, 4H), 2.08 (s, 3H), 3.4 (m, 4H), 4.2 (m) , 2H), 5.8 (m, 1H), 6.1 (m, 1H), 6.4 (m, 1H)
FT-IR: 2937,1721, 1636,1409,1275,1192,812 (cm ^-1 )

<Synthesis example 4>
Synthesis of compound A-5
Compound (A-5) was synthesized by the same procedure except that the acetyl chloride of Synthesis Example 1 was replaced with cyclohexanecarbonyl chloride.

The obtained compound was subjected to NMR analysis using ECX500 manufactured by JEOL Ltd. and FT-IR analysis using Spectrem GX manufactured by Perkin Elmer, and the following results were obtained.
^{1 1} H-NMR (CDCl ₃ ): δ1.44 (s, 9H), 1.5 (m, 10H), 1.96 (s, 3H), 2.5 (m, 1H), 3.61 (t) , 2H), 4.20 (t, 2H), 5.62 (s, 1H), 6.13 (s, 1H)
FT-IR: 2929, 2855, 1721, 1650, 1452, 1401, 1295, 1200, 1159, 942, 814 (cm ^-1 )

<Synthesis example 5>
Synthesis of Compound A-6 Compound A-6 was synthesized by the same procedure except that 4-ethylamino-1-butanol of Synthesis Example 3 was replaced with 2- (isopropylamino) ethanol and acetyl chloride was replaced with propionyl chloride. did.
^{1 1} H-NMR (CDCl ₃ ): δ1.2 (m, 9H), 2.4 (m, 2H), 3.5 (m, 3H), 4.3 (m, 2H), 5.8 (m) , 1H), 6.1 (m, 1H), 6.4 (m, 1H)
FT-IR: 2976, 2939, 1726, 1643, 1408, 1294, 1189, 1065, 985, 811 (cm ^-1 )

<Preparation of active energy ray-curable composition>
Based on the materials and contents (parts by mass) shown in Table 1 below, active energy ray-curable compositions of Examples and Comparative Examples were prepared by a conventional method. The reference numerals representing each compound in Table 1 correspond to the reference numerals of the compounds exemplified above.

<Curing energy>
For the active energy ray-curable compositions of each Example and Comparative Example, the plate diameter was set to 20 mm and the temperature was set to 25 ° C by the Anton-Paar rheometer MCR-302, and the energy at which G'saturated (mJ / cm ² ). Was measured. The light source used was LC-L1 (365 nm) manufactured by Hamamatsu Photonics. The results are shown in Table 1.

<Viscosity>
The active energy ray-curable compositions of each Example and Comparative Example were measured with a cone plate type rotational viscometer manufactured by Toki Sangyo Co., Ltd., VISCOMETER TVE-22L, with the temperature of constant temperature circulating water set to 25 ° C. The unit was mPa · s, and the temperature was adjusted by VISCOMATER VM-150III (manufactured by Toki Sangyo Co., Ltd.). The results are shown in Table 1.

<Odor>
The odor was evaluated by the following procedures (1) to (3). The evaluation criteria are as follows.
(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

In Table 1, the polymerization initiators C-1, C-2 and the comparative components D-1 and D-2 are as follows.

The color materials CB and Blue are as follows.
CB: MICROLITH Black CK (carbon black pigment) manufactured by BASF Japan Ltd.
Blue: MICROLITH Blue 4G-K manufactured by BASF Japan Limited

From the results in Table 1, it can be seen that the active energy ray-curable composition of the present invention has a low viscosity and is excellent in curability. From Comparative Example 1, it was found that having a secondary amide structure increases the viscosity. It was also found from Comparative Example 2 that if R ₂ and R ₃ in the general formula (I) were as small as a methyl group, a problem of odor would occur.

<Application example as an inkjet ink>
The curability and ink ejection property of three types of inkjet inks composed of the active energy ray-curable compositions of Examples 1, 7 and 8 were evaluated as follows.
[Evaluation methods]
Each inkjet ink prepared based on the materials and contents (parts by mass) shown in Table 1 is loaded into an inkjet ejection device (manufactured by Ricoh Co., Ltd., head: GEN4 manufactured by Ricoh Printing Systems), and is commercially available polyethylene terephthalate (PET). ) 0.2W by a UV irradiator (LH6, manufactured by Fusion Systems Japan) for a solid coating film formed by ejecting ink on a film (manufactured by Toyo Spinning Co., Ltd., E5100, thickness 100 μm) to an average thickness of 10 μm. It was cured with an illumination of / cm ² .
As a result, all of the inkjet inks had a low viscosity (15 mPa · s to 30 mPa · s at 25 ° C.), had good ink ejection properties, and had good curability.

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

Japanese Unexamined Patent Publication No. 2000-281634 Japanese Unexamined Patent Publication No. 3-21910 Japanese Unexamined Patent Publication No. 8-41133 Japanese Unexamined Patent Publication No. 2011-178863

Claims (9)

An active energy ray-curable composition comprising at least a compound represented by the general formula (I).
(In the formula, R ₁ represents a hydrogen or methyl group. R ₂ and R ₃ each independently represent a linear or branched alkyl group . However, at least one of R ₂ and R ₃ has 2 or more carbon atoms. A represents an alkylene group.) The active energy ray-curable composition according to claim 1 , which is a material for three-dimensional modeling. An active energy ray-curable ink using the composition according to claim 1 or 2 . The active energy ray-curable ink according to claim 3 , which is for an inkjet. A composition container containing the composition according to claim 1 or 2 . A two-dimensional or three-dimensional image forming apparatus including an accommodating portion accommodating the composition according to claim 1 and an irradiation means for irradiating active energy rays. A two-dimensional or three-dimensional image forming method comprising an irradiation step of irradiating the composition according to claim 1 with active energy rays. A cured product according to claim 1 or 2 , wherein the composition is cured by irradiating it with active energy rays. A molded product, which is obtained by molding the cured product according to claim 8 .