JP2017095676A - Active energy ray curable composition, active energy ray curable ink, composition accommodating container, two-dimensional or three-dimensional image formation device, image formation method, cured article and structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray curable composition capable of providing a cured article having excellent stretchability and solvent resistance.SOLUTION: There is provided an active energy ray curable composition containing at least an active energy ray polymerizable compound, containing a monofunctional monomer, a bifunctional monomer, a trifunctional monomer satisfying following conditions (1) and (2) as the active energy ray polymerizable compound and stretchability of the cured article is 100% or more. (1) [the number of functional groups derived from the monofunctional monomer]>[the number of functional groups derived from the bifunctional monomer]>[the number of functional groups derived from the trifunctional monomer]. (2) standard deviation of functional group ratio represented by [the number of functional groups derived from N functional monomer]/([the number of functional groups derived from the monofunctional monomer]+[the number of functional groups derived from the bifunctional monomer]+[the number of functional groups derived from the trifunctional monomer] is 0.003 to 0.030, where N=mono, bi, tri.SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray-curable composition, an active energy ray-curable ink, a composition container, a two-dimensional or three-dimensional image forming apparatus, an image forming method, a cured product, and a structure.

  In recent years, it has been studied to replace water-based and solvent-based ink-jet inks with ink-jet inks using an active energy ray-curable composition having relatively low volatility.

  Recently, there is an increasing demand for an active energy ray-curable ink-jet ink that can be printed on an ink-jet system on a substrate that is later subjected to stretching or punching.

Patent Document 1 proposes an active energy ray-curable ink that forms a cured product having adhesion to a substrate, hardness, and stretchability. This active energy ray-curable ink contains a monofunctional polymerizable monomer having a glass transition temperature of 90 ° C. or higher of a homopolymer, and forms a coating film having an average thickness of 10 μm on a polycarbonate substrate. When the film is cured by irradiation with an active energy ray with a light amount of 1,500 mJ / cm ² 1) Stretchability of the cured product when stretched at a tensile speed of 20 mm / min and a temperature of 180 ° C. using a tensile tester. = (Length after tensile test) / (Length before tensile test) is 2 or more 2) Adhesion between the polycarbonate substrate and the cured product measured according to the cross-cut test of JIS K5400 This gives a cured product of 70 or more.

  In Patent Document 2, it is easy to make an ink, low viscosity, high safety, excellent curability and adhesion to a substrate, and the cured product has an excellent balance between film strength and dimensional stability. An active energy ray-curable inkjet ink composition has been proposed. This active energy ray-curable inkjet ink composition contains a liquid polymerizable monomer that can be cured by active energy rays, has a viscosity at 25 ° C. of 3 to 70 mPa · s, and the polymerizable monomer is (a) Two or more hexafunctional polyfunctional monomers having six or more ethylenic double bond groups in the molecule and (b) 100 parts by mass of the polyfunctional monomer (a), 60 to 500 parts by mass of a bifunctional monomer having an ethylenic double bond group and (c) one ethylenic double bond in the molecule with respect to 100 parts by mass of the polyfunctional monomer of (a). It contains 0 to 15 parts by mass of a monofunctional monomer having a group.

A cured film made of an active energy ray-curable composition using a conventional monofunctional active energy ray polymerizable compound and a polyfunctional active energy ray polymerizable compound has high coating film hardness. For this reason, when a drawing process is performed after printing, there is a problem that the cured film cannot follow the deformation of the substrate, and the drawing processability of the printed matter is lowered. In addition, the conventional active energy ray-curable composition is greatly inferior in stretch processability compared to conventional solvent-based inks. The current situation is that switching does not proceed.
An object of this invention is to provide the active energy ray hardening-type composition which can obtain the hardened | cured material which has the outstanding extending | stretching property and solvent resistance.

The active energy ray-curable inkjet ink as a means for solving the above-described problems comprises at least an active energy ray polymerizable compound, and the active energy ray polymerizable compound includes a monofunctional monomer, a bifunctional monomer, a trifunctional monomer, and a trifunctional monomer. A functional monomer is contained so as to satisfy the following conditions (1) and (2), and the stretchability of the cured product is 100% or more.
(1) [Number of functional groups derived from monofunctional monomer]> [Number of functional groups derived from bifunctional monomer]> [Number of functional groups derived from trifunctional monomer]
(2) Standard deviation of functional group ratio represented by [number of functional groups derived from N functional monomer] / ([number of functional groups derived from monofunctional monomer] + [number of functional groups derived from bifunctional monomer] + [number of functional groups derived from trifunctional monomer]) Is 0.003 to 0.030.
However, N = single, a few, or three.

  ADVANTAGE OF THE INVENTION According to this invention, the active energy ray hardening-type composition which can obtain the hardened | cured material which has the outstanding extending | stretching property and solvent resistance can be provided.

FIG. 1 is a schematic view showing an example of an image forming apparatus according to the present invention. FIG. 2 is a schematic view showing an example of another image forming apparatus according to the present invention. FIG. 3 is a schematic view showing an example of still another image forming apparatus according to the present invention.

Hereinafter, the monomer which comprises the active energy ray hardening-type composition of this invention is demonstrated.
<Monofunctional monomer>
As a monofunctional monomer, it can select suitably according to the objective, for example, hydroxyethyl (meth) acrylamide, isobornyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, (Meth) acryloylmorpholine, dimethylaminopropylacrylamide, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl methacrylate, etc. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.

<Bifunctional monomer>
Examples of the bifunctional monomer include neopentyl glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meta). ) Acrylate, polypropylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (meth) acrylate, propylene oxide (PO) adduct di (meth) acrylate of bisphenol A, ethoxylated neopentyl glycol di (meth) acrylate, Propoxylated neopentylglycol di (meth) acrylate, ethylene oxide (EO) adduct di (meth) acrylate of bisphenol A, 1,6-hexanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.

<Trifunctional monomer>
Examples of trifunctional monomers include EO-modified pentaerythritol tri (meth) acrylate, PO-modified pentaerythritol tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and allyl trimellitate. Etc. These may be used individually by 1 type and may use 2 or more types together.

<Hexafunctional monomer>
The solvent resistance of the cured product can be improved by adding a hexafunctional monomer to the ink.
The content of hexafunctional monomers in all monomers is preferably 1 to 5% by mass.
Examples of the hexafunctional monomer include dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, and sorbitol hexaacrylate. These may be used individually by 1 type and may use 2 or more types together. Sorbitol hexaacrylate is most desirable because of good crosslinking.

<Functional group ratio>
The “functional group ratio” in the present invention is defined by the following formula.
[Number of functional groups derived from N functional monomer] / ([number of functional groups derived from monofunctional monomer] + [number of functional groups derived from bifunctional monomer] + [number of functional groups derived from trifunctional monomer])
However, N = single, a few, and three.
The sum of the monofunctional monomer-derived functional group ratio, the bifunctional monomer-derived functional group ratio, and the trifunctional monomer-derived functional group ratio is always 1, and their standard deviation is 0.003 to 0.030, and 0.009 to 0.014 is preferred. The value of this standard deviation is in a range where both stretchability and solvent resistance can be achieved.

<Monomer analysis method>
Examples of the monomer composition analysis method include a gas chromatograph analysis method. Quantitative analysis can be performed by performing qualitative analysis, specifying monomers from the contents, and drawing a calibration curve.

<Active energy rays>
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 rays, α rays, β rays, γ rays, and X rays in addition to ultraviolet rays. There is no particular limitation as long as it can provide the energy necessary for proceeding the polymerization reaction. In particular, when a high energy light source is used, the polymerization reaction can proceed without using a polymerization initiator. 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. Furthermore, an ultraviolet light emitting diode (UV-LED) and an ultraviolet laser diode (UV-LD) are small, have a long lifetime, high efficiency, and low 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. 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 and initiate polymerization of a 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 singly or in combination of two or more, and among them, radical polymerization initiators are used. It is preferable. Moreover, in order to obtain a sufficient curing rate, 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 thereof include ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.
In addition to the polymerization initiator, a polymerization accelerator (sensitizer) can be used in combination. The polymerization accelerator is not particularly limited. For example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, p-dimethylaminobenzoic acid-2-ethylhexyl, N, Amine compounds such as N-dimethylbenzylamine and 4,4′-bis (diethylamino) benzophenone are preferable, and the content thereof may be appropriately set according to the polymerization initiator used and the amount thereof.

<Color material>
The active energy ray-curable composition of the present invention may contain a coloring material. As the color 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 of the present invention Can be used. The content of the color material may be appropriately determined in consideration of a desired color density, dispersibility in the composition, and the like, and is not particularly limited. It is preferable that it is 1-20 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, is suitable as an overcoat layer for protecting an image.
As the pigment, an inorganic pigment or an organic pigment can be used, and one kind may be used alone, or two or more kinds may be used in combination.
As the inorganic pigment, for example, carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, iron oxide, and titanium oxide can be used.
Examples of the organic pigment 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 type chelates, acidic dye type chelates), dyeing lakes (basic dye type lakes, acid dye type lakes), nitro pigments, nitroso pigments, aniline black, A daylight fluorescent pigment is mentioned.
Moreover, in order to make the dispersibility of a pigment more favorable, you may further contain a dispersing agent. Although it does not specifically limit as a dispersing agent, For example, the dispersing agent conventionally used for preparing pigment dispersions, such as a polymer dispersing agent, is mentioned.
As the dye, for example, an acid dye, a direct dye, a reactive dye, and a basic dye can be used. One kind may be used alone, or two or more kinds may be used in combination.

<Polyrotaxane resin>
Polyrotaxane-based resins, also called slide ring materials, have a structure in which rod-like molecules of linear polymers penetrate through holes in macrocyclic compounds such as cyclodextrins, and bulky like an adamant group at both ends of the linear polymers. A high part is bonded, and this bulky part serves as a stopper to prevent the macrocyclic compound from escaping. As a product, there is Advanced Polymer Materials Co., Ltd. Super Polymer Series. Compared to conventional polymers, macrocyclic compounds can slide freely, so that they have spreadability and are difficult to break. Examples of the central polymer include polyethylene glycol, polyalkane, polyester, and linear silicone, and examples of the macrocyclic compound include cyclodextrin, crown ether, and cyclosiloxane. A polyrotaxane comprising a combination of polyethylene glycol and cyclodextrin is desirable from the intermolecular force and durability of the resins.

<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, especially a volatile organic solvent (VOC (Volatile Organic Compounds) free), the safety of the place where the composition is handled is further improved, and it is possible to prevent environmental pollution. . The “organic solvent” means a general non-reactive organic solvent such as ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and should be distinguished from a reactive monomer. is there. Further, “not including” an organic solvent means that it does not substantially include, and 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 as necessary. Other components are not particularly limited. For example, conventionally known surfactants, polymerization inhibitors, leveling agents, antifoaming agents, fluorescent whitening agents, penetration accelerators, wetting agents (humectants), fixing Agents, viscosity stabilizers, antifungal agents, antiseptics, 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 prepared using the various components described above, and the adjusting means and conditions thereof are not particularly limited. For example, a polymerizable monomer, a pigment, a dispersant, and the like are ball milled, Put into a disperser such as a kitty mill, disc mill, pin mill, dyno mill and disperse to prepare a pigment dispersion, which is further mixed with a polymerizable monomer, initiator, polymerization inhibitor, surfactant, etc. Can be adjusted.

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

<Application>
The use of the active energy ray-curable composition of the present invention is not particularly limited as long as it is a field where an active energy ray-curable material is generally used, and can be appropriately selected according to the purpose. Examples thereof 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 is not only used as an ink to form two-dimensional characters and images, and design coatings on various substrates, but also as a three-dimensional solid image (three-dimensional model). It can also be used as a material for three-dimensional modeling for forming the shape. 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, as shown in FIGS. 2 and 3. You may use as a three-dimensional constituent material (model material) and support member (support material) which are used in such a layered modeling method (optical modeling method). FIG. 2 shows a method for three-dimensional modeling by sequentially laminating the active energy ray-curable composition of the present invention onto a predetermined region and sequentially irradiating and curing the active energy rays (details will be described later). 3, the active energy ray curable composition 5 of the present invention is irradiated with the active energy ray 4 on the storage pool (container) 1 to form a cured layer 6 having a predetermined shape on the movable stage 3. This is a method of performing three-dimensional modeling by sequentially stacking.
As a three-dimensional modeling apparatus for modeling a three-dimensional modeled object using the active energy ray-curable composition of the present invention, a known one can be used, and is not particularly limited. For example, means for containing the composition , Supply means, discharge means, active energy ray irradiation means, and the like.
The present invention also includes a cured product obtained by curing the 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 obtained by subjecting a cured product or structure formed in a sheet shape or a film shape to a molding process such as heat stretching or punching, for example, an automobile, an OA device, an electric -It is suitably used for applications that require the surface to be molded after decorating, such as meters for electronic devices and cameras, and panels for operation units.
The substrate is not particularly limited and can be appropriately selected depending on the purpose. For example, paper, yarn, fiber, fabric, leather, metal, plastic, glass, wood, ceramics, or a composite material thereof. From the viewpoint of processability, a plastic substrate is preferable.

<Composition 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 use in the above applications. For example, when the active energy ray-curable composition of the present invention is used for ink, the container in which the ink is stored can be used as an ink cartridge or an ink bottle. In this operation, it is not necessary to directly touch the ink, and the fingers and clothes can be prevented from being stained. In addition, foreign matters such as dust can be prevented from entering the ink. Further, the shape, size, material, etc. of the container itself may be suitable for use and usage, and are not particularly limited. However, the material is a light-shielding material that does not transmit light, or the container is shielded from light. It is desirable to be covered with an adhesive sheet.

<Image Forming Method and Forming Apparatus>
The image forming method of the present invention includes an irradiation step of irradiating active energy rays in order to cure at least the active energy ray-curable composition of the present invention. An irradiation means for irradiating a line and an accommodating part for accommodating the active energy ray-curable composition of the present invention may be provided, and the container may be accommodated in the accommodating part. Furthermore, you may have the discharge process and discharge means which discharge an active energy ray hardening-type composition. A method for 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 ink jet ejection unit. Ink is ejected to the recording medium 22 supplied from the supply roll 21 by each color printing unit 23a, 23b, 23c, 23d including ink cartridges and discharge heads of active energy ray curable inks of yellow, magenta, cyan, and black. Is done. Thereafter, the light is cured by irradiating active energy rays from the light sources 24a, 24b, 24c, and 24d for curing the ink, thereby forming a color image. Thereafter, the recording medium 22 is conveyed to the processing unit 25 and the printed matter winding roll 26. Each of the printing units 23a, 23b, 23c, and 23d may be provided with a heating mechanism so that the ink is liquefied by the ink discharge unit. If necessary, a mechanism for cooling the recording medium to about room temperature by contact or non-contact may be provided. In addition, as an ink jet recording system, a serial system in which ink is ejected onto a recording medium by moving the head relative to a recording medium that moves intermittently according to the ejection head width, or the recording medium is moved continuously, Any of the line systems 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, and examples thereof include paper, a film, a metal, a composite material thereof, and the like, and may be a sheet shape. Moreover, even if it is the structure which enables only single-sided printing, the structure which also enables double-sided printing may be sufficient.
Further, the active energy ray irradiation from the light sources 24a, 24b, and 24c may be weakened or omitted, and the active energy ray may be irradiated from the light source 24d after printing a plurality of colors. Thereby, energy saving and cost reduction can be achieved.
The recorded matter recorded by the ink of the present invention is not only printed on a smooth surface such as ordinary paper or resin film, but also printed on a surface to be printed having irregularities, such as metal or ceramic. It includes those printed on a printing surface made of various materials. Further, by stacking two-dimensional images, it is possible to form an image having a stereoscopic effect (an image composed of two and three dimensions) 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 in FIG. 2 discharges the first active energy ray-curable composition from the modeling object discharge head unit 30 by using a head unit (movable in the AB direction) in which inkjet heads are arranged. A second active energy ray-curable composition having a composition different from that of the first active energy ray-curable composition is discharged from the head units 31 and 32, and these respective compositions are cured by the adjacent ultraviolet irradiation means 33 and 34. While laminating. More specifically, for example, the second active energy ray-curable composition is ejected from the support ejection head units 31 and 32 on the model support substrate 37 and solidified by irradiation with active energy rays. After forming the first support layer having the reservoir, the first active energy ray-curable composition is discharged from the ejection head unit 30 for a molded article into the reservoir and is solidified by irradiation with active energy rays. Then, the step of forming the first modeled object layer is repeated a plurality of times while lowering the stage 38 movable in the vertical direction in accordance with the number of stacking, thereby stacking the support layer and the modeled object layer to form the three-dimensional modeled object 35. Is produced. Thereafter, the support laminate 36 is removed as necessary. In FIG. 2, only one shaped article discharge head unit 30 is provided, but two or more shaped article discharge head units 30 may be provided.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples.
Below, the case where an active energy ray curable composition is used as an active energy ray curable ink is described.

(Examples 1-14 and Comparative Examples 1-5)
-Production of active energy ray-curable inkjet ink-
The raw materials listed in Table 1 below were added with sequential stirring. After stirring for 1 hour, it was confirmed that there was no dissolution residue, filtered with a membrane filter to remove coarse particles causing head clogging, and active energy rays of Examples 1 to 14 and Comparative Examples 1 to 5 A curable inkjet ink was prepared.
In Table 1, the “input amount” of the active energy ray polymerizable compound indicates “part by mass”.
As a photopolymerization initiator, 2,4,6-trimethylbenzoyldiphenyl-5-phosphine oxide and 1-phenyl-2-hydroxy-2-methylpropane were added in an amount of 5 parts per 100 parts of the total monomer amount. . The polyrotaxane is Super Polymer SH1310P manufactured by Advanced Soft Material Co., Ltd.

Next, each cured product was produced as follows using each produced active energy ray-curable inkjet ink.
A polycarbonate substrate (Mitsubishi Engineering Plastics Co., Ltd., Iupilon 100FE2000 masking) is used so that each active energy ray-curable inkjet ink has an average thickness of 10 μm by an inkjet discharge device equipped with GEN4 head (manufactured by Ricoh Printing Systems Co., Ltd.) It was discharged on a thickness of 100 μm). Immediately after the discharge, each cured product was obtained by irradiating ultraviolet rays with a light amount of 1,500 mJ / cm ² by a UV irradiator LH6 manufactured by Fusion Systems Japan.
About each obtained hardened | cured material, extending property and solvent resistance were evaluated as follows. The results are shown in Table 2.

<Extendability evaluation>
The stretchability in the present invention is evaluated by 180 ° C. elongation at break (tensile test).
About the dumbbell-shaped cured product, using a tensile tester (Autograph AGS-5kNX, manufactured by Shimadzu Corporation), pulling speed: 20 mm / min, temperature 180 ° C., sample: JIS K6251 dumbbell-shaped (No. 6) Measured and evaluated stretchability based on the following formula.
[(Length after tensile test−Length before tensile test) / Length before tensile test] × 100

<Solvent resistance>
A slide glass (26 × 76 mm, thickness 0.9 to 1.2 mm) is heat-washed at 450 ° C./3 minutes, and the mass of the slide glass is measured.
A solid coating film is produced by ink-jet printing ink on the slide glass, and is photocured with an integrated light amount of 0.3 J / cm ² (a minimum light amount when a large amount of light is required for curing).
The mass of the slide glass on which the cured product is formed is measured, and the mass (W1) of the cured product before the test is calculated based on the calculation formula [(slide glass + cured product) mass−slide glass mass].
Next, the entire slide glass on which the cured product has been formed is immersed in about 200 mL of solvent and left at 5 ° C. for 18 hours. Take out the slide glass on which the cured product has been formed, thoroughly wash it with the agent, dry it, measure its mass, and measure the cured product based on the formula [(slide glass + cured product) mass−slide glass mass]. The mass (W2) of is calculated.
Next, the mass change rate of the cured product is calculated based on the following calculation formula. The smaller the mass change rate, the better the solvent resistance.
Mass change rate (%) = [(W1-W2) / W1] × 100
Acetone and toluene were used as the solvent, and each solvent was tested.

1 Reservation pool (container)
DESCRIPTION OF SYMBOLS 3 Movable stage 4 Active energy ray 5 Active energy ray hardening-type composition 6 Hardened layer 21 Supply roll 22 Recording medium 23a, 23b, 23c, 23d Printing unit 24a, 24b, 24c, 24d Light source 25 Processing unit 26 Print winding roll DESCRIPTION OF SYMBOLS 30 Modeled object discharge head units 31 and 32 Support body discharge head units 33 and 34 Ultraviolet irradiation means 35 Three-dimensional modeled object 36 Support body laminated part 37 Modeled object support substrate 38 Stage 39 Image forming apparatus

Japanese Patent Laying-Open No. 2015-83656 JP 2011-252053 A

Claims (11)

An active energy ray-curable composition comprising an active energy ray polymerizable compound,
The active energy ray includes a monofunctional monomer, a bifunctional monomer, and a trifunctional monomer so as to satisfy the following conditions (1) and (2), and the stretchability of the cured product is 100% or more: An active energy ray-curable composition.
(1) [Number of functional groups derived from monofunctional monomer]> [Number of functional groups derived from bifunctional monomer]> [Number of functional groups derived from trifunctional monomer]
(2) Standard deviation of functional group ratio represented by [number of functional groups derived from N functional monomer] / ([number of functional groups derived from monofunctional monomer] + [number of functional groups derived from bifunctional monomer] + [number of functional groups derived from trifunctional monomer]) Is 0.003 to 0.030.
However, N = single, a few, or three.   The active energy ray-curable composition according to claim 1, wherein the standard deviation is 0.009 to 0.014.   The active energy ray-curable composition according to claim 1, comprising a hexafunctional monomer.   The active energy ray-curable composition according to claim 3, wherein the hexafunctional monomer is sorbitol hexaacrylate.   An active energy ray-curable ink comprising the composition according to claim 1.   A composition storage container in which the composition according to claim 1 is stored.   5. A two-dimensional or three-dimensional image forming apparatus comprising: a storage unit in which the composition according to claim 1 is stored; and irradiation means for irradiating active energy rays.   A two-dimensional or three-dimensional image forming method comprising an irradiation step of irradiating an active energy ray to the composition according to claim 1.   Hardened | cured material formed by hardening | curing the composition in any one of Claims 1 thru | or 4.   The structure which has a base material and the hardened | cured material formed by hardening | curing the composition in any one of Claims 1 thru | or 4.   The active energy ray-curable composition according to claim 1, comprising a polyrotaxane in an amount of 1% by mass to 10% by mass.

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