JP6780225B2 - Composition for active energy ray-curable three-dimensional modeling, active energy ray-curable ink, composition storage container, image forming method and forming device, and molded product - Google Patents

Description

The present invention describes an active energy ray-curable composition, an active energy ray-curable ink, a container containing them, a method and an apparatus for forming a two-dimensional or three-dimensional image using them, and the image. Regarding molded products that are processed.

Conventionally, active energy ray-curable inks have been supplied and used for offsets, silk screens, topcoating agents, etc., but in recent years, cost reduction by simplifying the drying process and reduction of solvent volatilization as an environmental measure have been achieved. The amount used is increasing because of the advantages of.

The active energy ray-curable ink is required to have high hardness from the viewpoint of improving productivity and curability characteristics and handling printed matter, and after being ejected and cured on a substrate, it is molded as a post-treatment. Is often given. It is generally known to blend an active energy ray-curable polyfunctional monomer in order to improve the molding process and the characteristics of curability and hardness. It is known that when the polyfunctional monomer is blended, jetting suitability such as discharge stability is lowered, and curing shrinkage of the molded product occurs due to an increase in internal stress, and the dimensional stability of the molded product is significantly lowered. ing.

Therefore, a three-dimensional modeling material including a bonding material containing the polyfunctional monomer has been proposed (see, for example, Patent Document 1).

However, this proposal is a method in which only the bonding material containing the polyfunctional monomer is applied by an inkjet method, and since the non-polymerizable resin particles themselves have a large volume-based median diameter, they are applied using a blade. It cannot be applied by ting, and there is a problem that the ejection stability and productivity in the inkjet method are inferior.
An object of the present invention is to provide an active energy ray-curable composition capable of obtaining a cured product having excellent discharge stability and good dimensional stability.

The active energy ray-curable composition of the present invention as a means for solving the above-mentioned problems contains a polymerizable compound and non-polymerizable resin particles, and the volume-based median diameter of the non-polymerizable resin particles is 100 nm. It is 600 nm or less.

According to the present invention, it is possible to provide an active energy ray-curable composition capable of obtaining a cured product having excellent discharge stability and good dimensional stability.

FIG. 1 is a schematic view showing an example of an ink cartridge. FIG. 2 is a schematic view showing an example of an image forming apparatus provided with an inkjet ejection means. FIG. 3 is a schematic view showing another example (three-dimensional stereoscopic image manufacturing apparatus) of an image forming apparatus provided with an inkjet ejection means. FIG. 4 is a schematic view showing another example (three-dimensional stereoscopic image manufacturing apparatus) of an image forming apparatus provided with an inkjet ejection means.

(Active energy ray-curable composition)
The active energy ray-curable composition of the present invention contains a polymerizable compound and non-polymerizable resin particles, and further contains a polymerization initiator and other components, if necessary.

<Polymerizable compound>
The polymerizable compound is not particularly limited as long as it is polymerizable by irradiation with active energy rays, and can be appropriately selected depending on the intended purpose.

The polymerizable compound preferably contains a polyfunctional polymerizable compound, and may contain a monofunctional polymerizable compound, an oligomer, or other components, if necessary.

<< Polyfunctional polymerizable compound >>
The polyfunctional polymerizable compound is not particularly limited as long as it has two or more ethylenic double bonds in one molecule, and can be appropriately selected depending on the intended purpose.

Examples of the polyfunctional polymerizable compound include hexadiol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tricyclodecanedimethanol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, and tripropylene glycol tri. Aacrylate, neopentyl glycol diacrylate, bispentaerythritol hexaacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, ethoxylated 1,6-hexanediol diacrylate, polypropylene glycol diacrylate, 1, 4-Butandiol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl 1,3-propanediol diacrylate, neopentyl glycol diacrylate hydroxypivalate, 1 , 3-butylene glycol di (meth) acrylate, trimethylolpropane triacrylate hydroxypivalate, triacrylate ethoxylated phosphate, tripropylene glycol diacrylate ethoxylated, neopentyl glycol-modified trimethylolpropane diacrylate, stearic acid-modified pentaerythritol Diacrylate, tetramethylolpropane triacrylate, tetramethylolmethanetriacrylate, pentaerythritol tetraacrylate, caprolactone-modified trimethylolpropanetriacrylate, propoxylate glyceryltriacrylate, tetramethylolmethanetetraacrylate, dimethylolpropanetetraacrylate, pentaerythritol ethoxylated. Tetraacrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, neopentyl glycol oligoacrylate, 1,4-butanediol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylol Propane oligoacrylate, pentaerythritol oligo acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, tripropylene glyco Examples thereof include rudi (meth) acrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane triacrylate. These may be used alone or in combination of two or more. Among these, a polyfunctional polymerizable compound having an acrylic equivalent of more than 150 g / eq is preferable.

Examples of the polyfunctional polymerizable compound having an acrylic equivalent of more than 150 g / eq include dipropylene glycol diacrylate, tricyclodecanedimethanol diacrylate, pentaerythritol triacrylate and the like.
As the polyfunctional polymerizable compound having an acrylic equivalent of more than 150 g / eq, a commercially available product can be used. As the commercially available product, for example, trade name: DPGDA (dipropylene glycol diacrylate, Osaka Organic Chemical Industry Co., Ltd.) (Company), trade name: SR833 (tricyclodecanedimethanol diacrylate, manufactured by Sartmer), trade name: SR444 (pentaerythritol triacrylate, manufactured by Sartmer) and the like.

The content of the polyfunctional polymerizable compound is preferably 10% by mass or more based on the total amount of the active energy ray-curable composition. When the content is 10% by mass or more, cross-linking of the obtained cured product is likely to be formed, and the hardness of the cured product can be improved.

<< Monofunctional polymerizable compound >>
The monofunctional polymerizable compound is not particularly limited as long as it has one ethylenic double bond in one molecule, and can be appropriately selected depending on the intended purpose.

Examples of the monofunctional polymerizable compound include phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobolonyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, and isooctyl acrylate, 2. -Methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydixyl ethyl acrylate, ethyldiglycol acrylate, cyclic trimethylolpropane Formal monoacrylate, imide acrylate, isoamyl acrylate, ethoxylated succinate acrylate, trifluoroethyl acrylate, ω-carboxypolycaprolactone monoacrylate, N-vinylformamide, cyclohexyl acrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-t-butyl Cyclohexyl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, 2-phenoxyethyl acrylate, acryloyl morpholine, phenoxydiethylene glycol acrylate, vinyl caprolactam, vinyl pyrrolidone, 2-hydroxy-3-phenoxypropyl acrylate , 1,4-Cyclohexanedimethanol monoacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, stearyl acrylate, diethylene glycol monobutyl ether acrylate, lauryl acrylate, isodecyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, isooctyl Examples include acrylate, octyl / decyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated (4) nonylphenol acrylate, methoxypolyethylene glycol (350) monoacrylate, methoxypolyethylene glycol (550) monoacrylate, cyclic trimethylolpropaneformal acrylate, etc. Be done. These may be used alone or in combination of two or more.

Among these, from the viewpoint of hardness, it is preferable to contain a monofunctional polymerizable compound having an alicyclic structure, a cyclic ether structure, a pyrrolidone structure, and a caprolactam structure.
Examples of the monofunctional polymerizable compound having an alicyclic structure include cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-t-butylcyclohexyl acrylate, and caprolactone-modified tetrahydro. Flufuryl acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, 2-phenoxyethyl acrylate (or ethylene oxide and / or propylene oxide-added monomer thereof), acryloylmorpholine, isobornyl acrylate, phenoxydiethylene glycol acrylate, vinyl caprolactam , Vinylpyrrolidone, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol monoacrylate and the like. These may be used alone or in combination of two or more.

The monofunctional polymerizable compound having a cyclic ether structure is not particularly limited as long as it contains a cyclic ether as a partial structure, and can be appropriately selected depending on the intended purpose, and may be a monocyclic compound. However, it may be polycyclic.
The number of ring members in the cyclic ether structure is preferably 3 or more, and more preferably 3 or more and 4 or less, from the viewpoint of reactivity.
The number of carbon atoms contained in the cyclic ether structure is preferably 2 or more and 9 or less, and more preferably 2 or more and 6 or less.
Examples of the monofunctional polymerizable compound having a cyclic ether structure include phenylglycidyl ether, p-tert-butylphenylglycidyl ether, butylglycidyl ether, 2-ethylhexylglycidyl ether, allylglycidyl ether, 1,2-butylene oxide, and the like. 1,3-butadiene monooxide, 1,2-epoxidodecan, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3 -Vinylcyclohexene oxide, 4-vinylcyclohexene oxide and the like can be mentioned. These may be used alone or in combination of two or more.

Examples of the monofunctional polymerizable compound having a pyrrolidone structure include N-vinylpyrrolidone.

Examples of the monofunctional polymerizable compound having a caprolactam structure include N-vinylcaprolactam.

The content of the monofunctional polymerizable compound is preferably 0% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 90% by mass or less, and 20% by mass, based on the total amount of the active energy ray-curable composition. More than 80% by mass is particularly preferable. When the content is 0% by mass or more and 90% by mass or less, the effect of the polyfunctional polymerizable compound is likely to appear, and the hardness can be improved.

<< Oligomer >>
The oligomer is not particularly limited as long as it has two or more ethylenic double bonds in one molecule, and can be appropriately selected depending on the intended purpose. The oligomer means a polymer in which the number of repetitions of the monomer structural unit of the monofunctional polymerizable compound is 2 or more and 20 or less. Further, the "polyfunctional polymerizable compound" does not include an oligomer.

The weight average molecular weight of the oligomer is not particularly limited and may be appropriately selected depending on the intended purpose. In terms of polystyrene, it is preferably 1,000 or more and 30,000 or less, and 5,000 or more and 20,000 or less. preferable. The weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC).

Examples of the oligomer include aromatic urethane oligomers, aliphatic urethane oligomers, epoxy acrylate oligomers, polyester acrylate oligomers, and other special oligomers. These may be used alone or in combination of two or more.

As the oligomer, a commercially available product can be used, and as the commercially available product, for example, UV-2000B, UV-2750B, UV-3000B, UV-3010B, UV-3200B, UV manufactured by Nippon Synthetic Chemical Industry Co., Ltd. -3300B, UV-3700B, UV-6640B, UV-8630B, UV-7000B, UV-7610B, UV-1700B, UV-7630B, UV-6300B, UV-6640B, UV-7550B, UV-7600B, UV-7605B , UV-7610B, UV-7630B, UV-7640B, UV-7650B, UT-5449, UT-5454; CN902, CN902J75, CN929, CN940, CN944, CN944B85, CN959, CN961E75, CN961H81, CN962, CN963, manufactured by Sartmer. , CN963A80, CN963B80, CN963E75, CN963E80, CN963J85, CN964, CN965, CN965A80, CN966, CN966A80, CN966B85, CN966H90, CN966J75, CN966, CN9669, CN970, CN970A60, CN970, CN970, CN970A60, CN970. , CN973J75, CN975, CN977, CN977C70, CN978, CN980, CN981, CN981A75, CN981B88, CN982, CN982A75, CN982B88, CN982E75, CN983, CN984, CN985, CN985B88, CN986, CN9989, CN999, CN998, CN998 , CN9001, CN9002, CN9004, CN9005, CN9006, CN9007, CN9008, CN9009, CN9010, CN9011 , CN9783, CN9788, CN9893; EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, KRM8200, EBECRYL5129 manufactured by Daicel Cytec Co., Ltd. , EBECRYL8210, EBECRYL8301, EBECRYL8804, EBECRYL8807, EBECRYL9260, KRM7735, KRM8296, KRM8452, EBECRYL4858, EBECRYL8402, EBECRYL9270, EBECRYL9270, EBECRYL9270, These may be used alone or in combination of two or more.

The content of the oligomer is preferably 10% by mass or less, more preferably 9% by mass or less, further preferably 8% by mass or less, and particularly preferably 5% by mass or less, based on the total amount of the active energy ray-curable composition. .. When the content is 10% by mass or less, the hardness of the obtained cured product can be increased.

<Non-polymerizable resin particles>
The non-polymerizable resin particles are resin particles that do not undergo a polymerization reaction due to irradiation with active energy rays or heating, and even when added to an active energy ray-curable composition, the non-polymerizable resin particles are relative to the polymerizable compound. Since it is insoluble, it does not cause a significant increase in viscosity as in the case of adding a soluble polymer compound. Therefore, it is possible to suppress a decrease in the inkjet ejection characteristics (ejection stability, etc.) due to an increase in viscosity due to the addition of the non-polymerizable resin particles.
Further, in the non-polymerizable resin particles, the non-polymerizable resin particles act as hard segments in a cured product after the active energy ray-curable composition is irradiated with active energy rays and cured. Therefore, it is considered that the hardness can be improved.
Furthermore, by containing the non-polymerizable resin particles, the number of functional groups per unit volume can be reduced, so that curing shrinkage during curing can be suppressed.

The non-polymerizable resin particles are not particularly limited, and for example, polystyrene resin particles, acrylic resin particles, polyester resin particles, silicone resin particles, polyolefin resin particles, polyurethane resin particles, vinyl chloride resin particles, epoxy resin particles, acetic acid. Examples include vinyl resin particles. Among these, acrylic resin particles are preferable. The acrylic resin particles mean resin particles made of at least one polymer of an acrylic acid ester and a methacrylic acid ester.

Examples of the non-polymerizable resin particles include non-aqueous resin particles.
The non-aqueous resin particles are made of a resin having a core / shell structure. As the dispersion medium, aliphatic hydrocarbons are mainly used, and for example, hexane, heptane, octane, cyclohexane, mineral spirit, other paraffin-based and naphthenic petroleum fractions can be used. In order to stably disperse the non-polymerizable resin particles in the dispersion medium, the surface of the particles must be wrapped with a three-dimensional repulsion layer.
As the non-aqueous resin particles that have reached practical use at present, the dispersion-stabilizing agent is a copolymer in which a soluble polymer part and an insoluble polymer part are blocked or graft-polymerized in the dispersion. The monomer is polymerized in the presence of the agent, and the produced insoluble polymer is combined with the insoluble polymer portion of the dispersion stabilizer to form dispersed particle nuclei. The monomer in the dispersion medium gradually migrates to the formed dispersed particle nuclei, and the polymerization proceeds in the particles. By this process, polymer particles (core polymer) wrapped in a shell structure (corresponding to the above-mentioned three-dimensional repulsion layer) dispersible in the dispersion medium are finally formed.

The non-aqueous resin particles can be produced by the following method.
When producing non-aqueous resin particles formed of a core / shell structure, first, a shell polymer that is soluble in a solvent is prepared, and the shell polymer is used as a protective colloid to continuously process a core polymer that is insoluble in a solvent. To make a non-aqueous emulsion with a core / shell structure.

The non-aqueous resin particles are dispersed using a dispersion medium other than the polymerizable compound. However, as described above, it is preferable that the non-aqueous resin particles do not contain a solvent other than the polymerizable compound. Therefore, in this case, the dispersion-based solvent is polymerized. It is preferable to replace the solvent with a sex compound.

Examples of the solvent substitution include a method using a rotary evaporator, a method using a difference in boiling points such as steam distillation and vacuum distillation, and the like. By substituting the solvent with the above method or the like, even if the non-polymerizable resin particles are contained in the active energy ray-curable composition, the active energy ray-curable composition does not contain a compound (solvent) unnecessary for the curing reaction. Obtainable.

The volume-based median diameter of the non-polymerizable resin particles is not particularly limited, and is preferably 100 nm or more and 600 nm or less, and more preferably 100 nm or more and 300 nm or less. When the volume-based median diameter is 100 nm or more, the non-polymerizable resin particles can be easily dispersed in the dispersion medium, and when it is 600 nm or less, the discharge stability can be improved. Further, when it is 100 nm or more and 300 nm or less, the non-polymerizable resin particles have a sufficient size, so that they can sufficiently play a role as a hard segment and the hardness can be improved. Here, the volume-based median diameter can be measured by a dynamic light scattering method using, for example, a particle size analyzer (Microtrack MODEL UPA9340, manufactured by Nikkiso Co., Ltd.).

The glass transition temperature of the non-polymerizable resin particles is not particularly limited, and is preferably 10 ° C. or higher and 200 ° C. or lower, and more preferably 25 ° C. or higher and 200 ° C. or lower. When the glass transition temperature is 10 ° C. or higher and 200 ° C. or lower, even if the non-polymerizable resin particles are dispersed in the composition in a very unstable state, the non-polymerizable resin particles are in a normal temperature environment. It is possible to prevent agglomeration, improve discharge stability, and easily work as a hard segment in a cured product to improve hardness. Here, the glass transition temperature of the non-polymerizable resin particles can be measured by, for example, a differential scanning calorimetry (DSC) method. As the DSC device, for example, the device name: Seiko Instruments DSC120U (manufactured by Seiko Instruments Inc.) is used, the measurement temperature is 30 ° C. or higher and 200 ° C. or lower, and the temperature rise rate is 2.5 ° C. per minute. Can be done.

The content of the non-polymerizable resin particles is preferably 3% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 7% by mass or less, based on the total amount of the active energy ray-curable composition. When the content is 3% by mass or more, the hardness of the obtained cured product can be improved, the curing shrinkage can be reduced, and when it is 20% by mass or less, an increase in viscosity can be suppressed. It is possible to improve jetting suitability such as discharge stability.

<Method for quantifying each component contained in the active energy ray-curable composition>
As a method for quantifying the polyfunctional polymerizable compound, the non-polymerizable resin particles, the monofunctional polymerizable compound, and the oligomer contained in the active energy ray-curable composition of the present invention, for example, it can be obtained by GC-MS measurement. A method of quantifying from the peak intensity; a method of quantifying from the peak intensity obtained by measuring the molecular weight distribution by GPC; and a method of quantifying from the integrated value obtained by ¹ H NMR measurement. As one of the specific quantification methods, there is a method of creating a calibration curve. In addition, simply, by preparing a standard sample for each component (for example, a sample containing 15% by mass of the corresponding polyfunctional polymerizable compound) and measuring under the same conditions, the magnitude relationship of the content is relative. It is also possible to evaluate the target. If the blending amount of each component at the time of producing the active energy ray-curable composition is known, the value can be used as the content of each component.
When each component species is unknown, qualitative research can be performed in advance using GC-MS, ¹ H NMR, or the like. Further, the glass transition temperature of the homopolymer can be measured by using, for example, the differential scanning calorimetry (DSC) method. As the glass transition temperature by the differential scanning calorimetry (DSC) method, only the polymer component can be taken out and measured by extracting the sample with a poor solvent of the polymer.

<Polymerization initiator>
The polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose, but a photoradical polymerization initiator is preferable.
As the photoradical polymerization initiator, those having a negative skin sensitization property are more preferable.
When a high-energy light source such as an electron beam, α-ray, β-ray, γ-ray, or X-ray is used, the polymerization reaction can proceed without using a photopolymerization initiator.

Examples of the photoradical polymerization initiator include a molecular cleavage type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator.

Examples of the molecular cleavage type photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenylketone, and 2-hydroxy-2-methyl-1-phenylpropane-. 1-on, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1- {4- [4- (2-) Hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methyl-1-propan-1-one, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, phenyl Glyoxyc acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone- 1,2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butane-1-one, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide , Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoylphosphine oxide, 1,2-octanedione- [4- (phenylthio)- 2- (o-benzoyl oxime)], Etanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime), [4- ( Methylphenylthio) Phenyl] Phenylmethanone, 2,4-diethylthioxanthen-9-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, oligo [2-hydroxy-2-methyl-1- [ 4- (1-Methylvinyl) phenyl] propanone and the like can be mentioned. These may be used alone or in combination of two or more.

Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone compounds such as benzophenone, methylbenzophenone, methyl-2-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylsulfide, and phenylbenzophenone; 2,4-diethyl. Examples thereof include thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, and 1-chloro-4-propylthioxanthone. These may be used alone or in combination of two or more.

The content of the polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass or more and 20% by mass or less, preferably 5% by mass or more, based on the total amount of the polymerizable compound. It is preferably 15% by mass or less. When the content of the polymerization initiator is in the range of 1% by mass or more and 20% by mass or less, there is an advantage that the hardness of the obtained cured product can be maintained above a certain level.

<Other ingredients>
Examples of the other components include a polymerization accelerator, a colorant, a polymerization inhibitor, a surfactant, a polar group-containing polymer pigment dispersant, and the like. These may be used alone or in combination of two or more.

<< Polymerization Accelerator >>
In the active energy ray-curable composition of the present invention, an amine compound as a polymerization accelerator can also be used in combination with the photopolymerization initiator.
Examples of the amine compound include ethyl p-dimethylaminobenzoate, -2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, -2-dimethylaminoethyl benzoate, and p-dimethylaminobenzoic acid. Examples include butoxyethyl. These may be used alone or in combination of two or more.

The active energy ray-curable composition of the present invention may be a clear liquid containing no colorant, or may be a colorant containing a colorant. When the clear liquid is used or when it is desired to maintain the color tone of the colorant itself as much as possible, it is preferable to use a material other than the colorant described later, which is less colored.

<< Colorant >>
Inorganic pigments or organic pigments can be used as the colorant. In addition, various inorganic pigments and organic pigments can be used as needed in consideration of the physical properties of the ink.

Examples of the black pigment include carbon black produced by the furnace method or the channel method.

Examples of the yellow pigment include Pig. Examples include Yellow pigments. The Pig. Examples of Yellow pigments include Pigment Yellow 1, Pigment Yellow 2, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 16, Pigment Yellow 17, Pigment Yellow 73, Pigment Yellow 74, and Pigment. Yellow 75, Pigment Yellow 83, Pigment Yellow 93, Pigment Yellow 95, Pigment Yellow 97, Pigment Yellow 98, Pigment Yellow 114, Pigment Yellow 120, Pigment Yellow 128, Pigment Yellow 129, Pigment Yellow 138, Pigment Yellow 150, Pigment Yellow 151 , Pigment Yellow 154, Pigment Yellow 155, Pigment Yellow 180 and the like. In addition to these, Naftor Yellow S, Hansa Yellow (10G, 5G, G), Cadmium Yellow, Yellow Iron Oxide, Yellow Clay, Yellow Lead, Titanium Yellow, Polyazo Yellow, Oil Yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Balkan Fast Yellow (5G, R), Tartragin Lake, Kinolin Yellow Lake, Anthracan Yellow BGL, Isoindolinon Yellow, etc. Can be mentioned. These may be used alone or in combination of two or more.

Examples of magenta, red, and orange pigments include Pig. Red pigments and the like can be mentioned. The Pig. Examples of Red pigments include Pigment Red 5, Pigment Red 7, Pigment Red 12, Pigment Red 48 (Ca), Pigment Red 48 (Mn), Pigment Red 57 (Ca), Pigment Red 57: 1, Pigment Red. 112, Pigment Red 122, Pigment Red 123, Pigment Red 168, Pigment Red 184, Pigment Red 202, Pigment Violet 19, etc., as well as Bengala, Lead Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu , Permanent Red 4R, Para Red, Faise Red, Parachloro Orthonitroaniline Red, Resole Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Khanmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resole Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Truizin Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium , Eosin Lake, Rhodamin Lake B, Rhodamin Lake Y, Alizarin Lake, Thioinjigo Red B, Thioinjigo Maroon, Oil Red, Kinakridon Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinon Orange, Oil Orange, etc. Can be mentioned. These may be used alone or in combination of two or more.

Examples of cyan, blue, and green pigments include Pig. Blue pigments and the like can be mentioned. The Pig. Examples of Blue pigments include Pigment Blue 1, Pigment Blue 2, Pigment Blue 3, Pigment Blue 15, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 16, Pigment Blue 22, Pigment Blue 60, and Vat. Examples include Blue 4 and Bat Blue 60. Besides this, cobalt blue, cerulean blue, alkaline blue lake, peacock blue lake, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanslen blue (RS, BC), indigo, ultramarine blue, dark blue , Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zink Green, Chromium Oxide, Pyridian, Emerald Green, Pigment Green B, Naftor Green B, Green Gold, Acid Green rake, malakite green rake, phthalocyanine green, anthraquinone green, titanium oxide, zinc flower, lithobon and mixtures thereof can be used. These may be used alone or in combination of two or more.

Examples of the white pigment include sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, fine powder silicic acid, silicas such as synthetic silicates, calcium silicate, and alumina. Alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like can be mentioned. These may be used alone or in combination of two or more.

Examples of the silver pigment include aluminum, talc, clay and the like. These may be used alone or in combination of two or more.

As the golden pigment, a yellow pigment can be mixed with the silver pigment described above to obtain a golden ink, or an image can be formed by superimposing a silver color and a yellow color or forming dots in the vicinity. These may be used alone or in combination of two or more.
In addition, various inorganic pigments and organic pigments can be used as needed in consideration of physical properties and the like.

The content of the colorant is preferably 1% by mass or more and 30% by mass or less, and more preferably 1% by mass or more and 20% by mass or less, based on the total amount of the active energy ray-curable composition.

<< Polymerization inhibitor >>
Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, methylhydroquinone, hydroquinone, tert-butylhydroquinone, di-tert-butylhydroquinone, methquinone, 2,2'-dihydroxy-3,3'-di ( α-Methylcyclohexyl) -5,5'-dimethyldiphenylmethane, p-benzoquinone, di-tert-butyldiphenylamine, 9,10-di-n-butoxycyantrasen, 4,4'-[1,10-dioxo-1 , 10-decandylbis (oxy)] bis [2,2,6,6-tetramethyl] -1-piperidinyloxy and the like. These may be used alone or in combination of two or more.

If the viscosity of the active energy ray-curable composition of the present invention is too high and it becomes difficult to eject the ink when used in an active energy ray-curable ink, it may be diluted with a general solvent, but from the viewpoint of odor and the like Therefore, it is preferable to use a diluting monomer without using such a diluting solvent.
The solvent generally means a volatile organic compound (VOC), for example, ether, ketone, aromatic, xylene, ethyl ethoxypropionate, ethyl acetate, cyclohexanone, toluene and the like. It should be distinguished from the reactive monomer used for dilution.

<Viscosity>
The viscosity of the active energy ray-curable composition at 40 ° C. is preferably 8 mPa · s or more and 25 mPa · s or less. When the viscosity is 8 mPa · s or more and 25 mPa · s or less, the jetting suitability such as discharge stability can be improved. The viscosity can be measured by using a cone plate type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.) at a constant temperature circulating water temperature of 40 ° C.

The active energy ray-curable composition is preferably solvent-free. The solvent-free means, for example, ether, ketone, aromatic, xylene, ethyl ethoxypropionate, ethyl acetate, cyclohexanone, diethylene glycol monomethyl ether, diethylene glycol, monoethyl ether, γ-butyl lactone, ethyl lactate, cyclohexanemethyl ethyl ketone, toluene, etc. It means that it does not contain various known solvents such as ethyl ethoxypropionate, polymethacrylate or propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, diethylene glycol and triethylene glycol monobutyl ether.
When the active energy ray-curable composition is solvent-free, there is no residual volatile organic solvent in the ink film, safety at the printing site can be obtained, there is no environmental pollution, and the ink on the head. It is preferable because the printer does not dry out and the maintenance of the printer is easy.

<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.

<Use>
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, a molding resin, etc. It can be applied to paints, adhesives, insulating materials, mold release agents, coating materials, sealing materials, various resists, various optical materials, and the like.
Further, the active energy ray-curable composition of the present invention can be used not only as an ink to form a two-dimensional image but also as a three-dimensional modeling material for forming a three-dimensional stereoscopic image (three-dimensional model). It can be used, for example, as a binder between powder particles used in the powder laminating method, which is one of the three-dimensional modeling methods, and as shown in FIG. 3, an active energy ray-curable composition is placed in a predetermined region. Storage of the active energy ray-curable composition 5 as shown in the material jet method (stereolithography method) in which three-dimensional modeling is performed by sequentially laminating those that have been discharged and cured by irradiating them with active energy rays. As a three-dimensional object constituent material in a stereolithography method in which a pool (accommodation portion) 1 is irradiated with active energy rays 4 to form a cured layer 6 having a predetermined shape on a movable stage 3 and the layers are sequentially laminated to perform three-dimensional modeling. It can be utilized. A known three-dimensional modeling device for modeling a three-dimensional model using such an active energy ray-curable composition can be used, and is not particularly limited, but for example, a means for accommodating the composition. Those provided with a supply means, a discharge means, an active energy ray irradiation means, and the like can be used.
Further, the present invention processes a cured product (coating film or its laminate) obtained by curing an active energy ray-curable composition or a structure in which the cured product is formed on a base material such as a recording medium. Also includes molded products made from 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.

(Active energy ray-curable ink)
The active energy ray-curable ink of the present invention (hereinafter, may be referred to as "ink") comprises the active energy ray-curable composition of the present invention, and is preferably for an inkjet.
The viscosity of the active energy ray-curable ink at 40 ° C. is preferably 8 mPa · s or more and 25 mPa · s or less. When the viscosity is 8 mPa · s or more and 25 mPa · s or less, the inkjet characteristics such as ejection stability can be improved. The viscosity can be measured by using a cone plate type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.) at a constant temperature circulating water temperature of 40 ° C.

The static surface tension of the active energy ray-curable ink at 25 ° C. is preferably 20 mN / m or more and 40 mN / m or less, and more preferably 28 mN / m or more and 35 mN / m or less.
The static surface tension was measured at 25 ° C. using a static surface tension meter (CBVP-Z type manufactured by Kyowa Interface Science Co., Ltd.). The static surface tension is based on the specifications of a commercially available inkjet ejection head such as GEN4 manufactured by Ricoh Printing Systems Co., Ltd.

(Composition container)
The composition container of the present invention means a container in which the active energy ray-curable composition is stored, and is preferably used for 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, whereby the ink can be used in operations such as ink replacement. There is no need to touch it directly, 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. Further, the shape, size, material, etc. of the container itself may be suitable for the intended use and usage, and is not particularly limited, but it is desirable that the material has a light-shielding property.
FIG. 1 shows an example of an ink cartridge. The ink bag 11 has an ink injection port 12 and an ink discharge port 13. The ink bag 11 is filled with ink from the ink injection port 12, the air remaining in the ink bag 11 is exhausted, and then the ink injection port 12 is fused and sealed. When the ink bag 11 is used, the ink discharge port 13 is pierced with a needle formed in the main body of an ink ejection device such as an inkjet recording device to supply ink to the device. The ink discharge port 13 is formed of a rubber member or the like. The ink bag 11 is housed in a plastic cartridge case 14, and is detachably attached to an inkjet recording device as an ink cartridge 10. By making the structure removable, it is possible to improve the efficiency of work such as ink replenishment and replacement.

(Image forming method and image forming device)
The image forming method in the present invention includes, at least, an irradiation step of irradiating an active energy ray in order to cure the active energy ray-curable composition, and the image forming apparatus in the present invention irradiates the active energy ray. It is provided with an irradiation means for accommodating the active energy ray-curable composition and an accommodating portion for accommodating the active energy ray-curable composition. Further, it may have a discharge step and a discharge means for discharging the active energy ray-curable composition, and may have the discharge step and a heating step and a heating means for heating the ink before the discharge means. Good. 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. 2 is a schematic view showing 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.
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. 3 is a schematic view showing another example (three-dimensional stereoscopic image manufacturing apparatus) of an image forming apparatus provided with an inkjet ejection means. The image forming apparatus 39 of FIG. 3 uses a head unit (movable in the AB direction) in which the inkjet heads are arranged to inject the first active energy ray-curable composition from the injection head unit 30 for a modeled object for a support. A second active energy ray-curable composition having a composition different from that of the first composition is ejected from the head units 31 and 32, and these compositions are laminated while being cured by adjacent ultraviolet irradiation means 33 and 34. Although only one injection head unit 30 for a modeled object is provided in FIG. 3, two or more injection head units 30 can be provided. As a method of forming a three-dimensional stereoscopic image using such a device, for example, the second composition is discharged from the support injection head units 31 and 32 onto the modeled object support substrate 37 and activated. After irradiating an energy ray and solidifying it to form a first support layer having a reservoir, the first composition is discharged from the injection head unit 30 for a modeled object into the reservoir to form an active energy ray. The process of irradiating and solidifying to form the first modeled object layer is repeated a plurality of times while lowering the vertically movable stage 38 according to the number of times of stacking, thereby forming the support layer and the modeled object layer. The three-dimensional model 35 is manufactured by laminating. After that, the support laminated portion 36 is removed as needed.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

The volume-based median diameter, glass transition temperature, and viscosity were determined as follows.
<Volume-based median diameter>
The volume-based median diameter was measured by a dynamic light scattering method using a particle size analyzer (Microtrack MODEL UPA9340, manufactured by Nikkiso Co., Ltd.).

<Glass transition temperature>
The glass transition temperature is measured using a differential scanning calorimetry device (device name: Seiko Instruments DSC120U, manufactured by Seiko Instruments Inc.), the measurement temperature is 30 ° C. or higher and 200 ° C. or lower, and the temperature rise rate is 2.5 ° C. per minute. Measured at.

<Viscosity>
The viscosity of the active energy ray-curable composition was measured by using a cone plate type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.) at a constant temperature circulating water temperature of 40 ° C.

<Synthesis Example 1 of Non- Polymeric Resin Particles>
<< Synthesis of non- polymerizable resin particles A >>
150 parts by mass of petroleum hydrocarbon (trade name: A-solvent, manufactured by JX Nikko Nisseki Energy Co., Ltd., hereinafter sometimes referred to as "A-solvent") in a reaction vessel in which the air inside the vessel is replaced with nitrogen. After charging the temperature to 90 ° C., 100 parts by mass of styrene, 100 parts by mass of isobutyl methacrylate, and 50 parts by mass of 2-ethylhexyl acrylate, and benzoyl peroxide (hereinafter, also referred to as "BPO") 2 A mixture consisting of .5 parts by mass and 100 parts by mass of A-solvent was added dropwise over 3 hours, and after the addition was completed, the mixture was kept at the same temperature for 5 hours, and the non-volatile content was 49.8% by mass (that is,). A transparent resin solution having a monomer conversion rate of 99.6%) was obtained. The obtained resin solution comprises 100 parts by mass of vinyl acetate, 100 parts by mass of ethyl acrylate, 49 parts by mass of methyl methacrylate, 1 part by mass of methacrylic acid, 2.5 parts by mass of BPO, and 250 parts by mass of A-solvent. The mixture was added dropwise over 3 hours, and after the addition was completed, the mixture was kept at the same temperature for 1 hour, and milky white resin particles having a non-volatile content of 47.5% by mass (that is, a dispersoid monomer conversion rate of 90%). The dispersion liquid of was obtained. The obtained dispersion of resin particles was stirred with a stirrer for 30 minutes to obtain a dispersion of non- polymerizable resin particles A. The volume-based median diameter of the non- polymerizable resin particles A was 80 nm, and the glass transition temperature was 10 ° C.

<Synthesis Examples 2 to 4 of Non- Polymeric Resin Particles>
<< Synthesis of non- polymerizable resin particles B, C, and D >>
Non - polymerizable resin particles B, C, and D are the same as in Synthesis Example 1 of non- polymerizable resin particles, except that the dropping amount and time of the raw material mixture are changed in Synthesis Example 1 of non- polymerizable resin particles. (Non-volatile content: 47.5% by mass) was obtained. The volume-based median diameters of the non- polymerizable resin particles B, C, and D were 100 nm, 600 nm, and 1,000 nm, respectively, and the glass transition temperature was 10 ° C.

<Synthesis Example 5 of Non- Polymeric Resin Particles>
<< Synthesis of non- polymerizable resin particles E >>
150 parts by mass of A-solvent was charged into a reaction vessel in which the air in the vessel was replaced with nitrogen, and the temperature was raised to 90 ° C., then 100 parts by mass of styrene, 100 parts by mass of n-butyl methacrylate, and 2-ethylhexyl. A mixture consisting of 50 parts by mass of acrylate, 2.5 parts by mass of BPO, and 100 parts by mass of A-solvent was added dropwise over 3 hours, and even after the addition was completed, the mixture was kept at the same temperature for 5 hours, and the non-volatile content was 49. A transparent resin solution having a monomer conversion rate of 99.6% by mass was obtained. The obtained resin solution comprises 100 parts by mass of vinyl acetate, 100 parts by mass of ethyl acrylate, 49 parts by mass of butyl methacrylate, 1 part by mass of methacrylic acid, 2.5 parts by mass of BPO, and 250 parts by mass of A-solvent. The mixture was added dropwise over 5 hours, and after the addition was completed, the mixture was kept at the same temperature for 5 hours, and the non - polymerized white emulsion having a non- volatile content of 47.5% by mass (that is, the dissimilar monomer conversion rate was 90%). A dispersion liquid of the sex resin particles E was obtained. The volume-based median diameter of the obtained non- polymerizable resin particles E was 80 nm, and the glass transition temperature was 5 ° C.

<Synthesis Example 6 of Non- Polymeric Resin Particles>
<< Synthesis of non- polymerizable resin particles F >>
Synthesis Example 5 of the non-polymerizable resin particles, except that the raw material of butyl methacrylate octyl methacrylate, non-polymerizable in the same manner as in Synthesis Example 5 of the resin particles, non-polymerizable resin particles F dispersion of (non-volatile content : 47.5% by mass) was obtained. The volume-based median diameter of the obtained non- polymerizable resin particles F was 600 nm, and the glass transition temperature was −5 ° C.

<Synthesis Example 7 of Non- Polymeric Resin Particles>
<< Synthesis of non- polymerizable resin particles G >>
Synthesis Example 5 of the non-polymerizable resin particles, except that the raw material of butyl methacrylate and trimethylolpropane trimethacrylate, the same procedure as Synthesis Example 5 of the non-polymerizable resin particles, dispersion of non-polymerized resin particles G (Non-volatile content: 47.5% by mass) was obtained. The volume-based median diameter of the obtained non- polymerizable resin particles G was 600 nm, and the glass transition temperature was 54 ° C.

<Production example of colorant dispersion>
<< Preparation of cyan pigment dispersion >>
8 parts by mass of polymer dispersant (trade name: Sol Spurs 32000, manufactured by Abyssia Co., Ltd.) and 72 parts by mass of isobolonyl acrylate are placed in a stainless beaker and dissolved by stirring for 1 hour while heating on a hot plate at 65 ° C. did. Then, cool to room temperature, add 20 parts by mass of Pigment Blue 15: 4 (trade name: Cyanine Blue 4044, manufactured by Sanyo Dye Co., Ltd.), put in a glass bottle together with 200 parts by mass of zirconia beads having a diameter of 0.3 mm, and seal tightly. After 8 hours of dispersion treatment with a paint shaker, the zirconia beads were removed to prepare a cyan pigment dispersion.

(Example 1)
66 parts by mass of dipropylene glycol diacrylate (DPGDA), 7 parts by mass of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (TPO), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (810) 5 parts by mass and 2 parts by mass of 2,4-diethylthioxanthene-9-one (DETX) were added in this order and stirred for 1 hour. Next, 20 parts by mass of the dispersion liquid of the non-polymerizable resin particles B was added, and the mixture was stirred for 30 minutes. Then, it was filtered with a membrane filter to remove coarse particles causing head clogging, and an active energy ray-curable composition 1 was prepared. As the dispersion of the non-polymerizable resin particles B, a solution in which the difference in boiling points was utilized using a rotary evaporator and the solvent was substituted with tripropylene glycol diacrylate, which is a polyfunctional polymerizable compound, was used. ..

(Examples 2 to 12 and Comparative Examples 1 to 4)
In Example 1, active energy ray-curable compositions 2 to 16 were prepared in the same manner as in Example 1 except that the compositions and contents (parts by mass) shown in Tables 1 to 4 were changed. The dispersions of the resin particles A to G used were subjected to solvent substitution using phenoxyethyl acrylate using the difference in boiling points using a rotary evaporator.

The "discharge stability" and "dimensional stability" of the prepared active energy ray-curable compositions 1 to 16 of Examples 1 to 12 and Comparative Examples 1 to 4 were evaluated as follows. The results are shown in Tables 1 to 4.

<Discharge stability>
Using an inkjet ejection device equipped with a GEN4 head (manufactured by Ricoh Printing Systems Co., Ltd.), the prepared active energy ray-curable compositions 1 to 16 (inks 1 to 16) of Examples 1 to 12 and Comparative Examples 1 to 4 were used. , Each ink was ejected continuously for 60 minutes, the number of nozzles in which nozzle omission occurred was determined, and "ejection stability" was evaluated based on the following evaluation criteria. The inkjet ejection device had a drive frequency of 18 kHz, a heating temperature of 35 ° C., and an ink ejection amount of 2 pL per time.
-Evaluation criteria-
⊚: 1 or less ○: 2 or more and 5 or less △: 6 or more and 8 or less ×: 9 or more

<Dimensional stability>
Active energy ray-curable compositions 1 to 16 (inks 1 to 16) are ejected into the same section on a recording medium using an inkjet ejection device equipped with a GEN4 head (manufactured by Ricoh Co., Ltd.), and a UV irradiator (device name). : LH6, manufactured by Fusion Systems Japan Co., Ltd.) was irradiated with ultraviolet rays at a light intensity of 1,500 mJ / cm ² and cured. By repeating the discharge and curing operations, a cured product having a size of 3 mm (vertical) x 3 mm (horizontal) x 0.5 mm (thickness) was obtained. The cured product was formed using a PET film mirror (registered trademark) E20 (manufactured by Toray Industries, Inc.), and the evaluation was carried out by peeling it from the recording medium. After curing, it was allowed to stand at room temperature and normal pressure for 1 day, and then "dimensional stability" was evaluated based on the following evaluation criteria.
-Evaluation criteria-
⊚: Warpage of the molded product is not observed, and the measured dimension value for each dimension is 85% or more. ○: Warpage of the molded product is observed and 3 mm or less, and the measured dimension value for each dimension is 85% or more. Δ: Warpage of the molded product is observed and is 3 mm or less, and the value of the measured dimension for each dimension is less than 85%. ×: Warpage of the molded product is observed over 3 mm.

In Tables 1 to 4, the trade names and manufacturing company names of the compounds used are as follows.
-Isobolonyl acrylate: IBXA (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
・ Phenoxyethyl acrylate: PEA (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
-N-Vinylpyrrolidone: NVP (manufactured by ISP Japan)
・ N-Vinyl caprolactam: NVC (manufactured by ISP Japan)
-Cyclic trimethylolpropane formal acrylate: SR531 (manufactured by Sartmer)
-Dipropylene glycol diacrylate: DPGDA (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
-Tricyclodecanedimethanol diacrylate: SR833 (manufactured by Sartmer)
-Pentaerythritol triacrylate: SR444 (manufactured by Sartmer)
-2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide: TPO (manufactured by LAMBERTI)
Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide: Irg. 819 (manufactured by BASF)
-2,4-Diethylthioxanthene-9-on: DETX (manufactured by Daido Kasei Kogyo Co., Ltd.)
-Resin: Polyester resin (Byron 220, manufactured by Toyobo Co., Ltd.)
In the table, the resin is dissolved in the ink and is distinguished from the non-polymerizable resin particles (the one in which the resin fine particles are dispersed).

Examples of aspects of the present invention are as follows.
<1> Containing a polymerizable compound and non-polymerizable resin particles,
The active energy ray-curable composition is characterized in that the volume-based median diameter of the non-polymerizable resin particles is 100 nm or more and 600 nm or less.
<2> The active energy ray-curable composition according to <1>, wherein the resin particles are acrylic resin particles.
<3> The active energy ray-curable composition according to any one of <1> to <2>, wherein the viscosity at 40 ° C. is 8 mPa · s or more and 25 mPa · s or less.
<4> The active energy ray-curable composition according to any one of <1> to <3>, wherein the glass transition temperature of the non-polymerizable resin particles is 10 ° C. or higher and 200 ° C. or lower.
<5> The active energy ray-curable composition according to any one of <1> to <4>, wherein the polymerizable compound contains a polyfunctional polymerizable compound having an acrylic equivalent of more than 150 g / eq.
<6> The active energy ray-curable composition according to any one of <1> to <5>, wherein the polymerizable compound contains a monofunctional polymerizable compound having one ethylenic double bond in one molecule. It is a thing.
<7> The above-mentioned <6>, wherein the monofunctional polymerizable compound having one ethylenic double bond in one molecule has any one of an alicyclic structure, a cyclic ether structure, a pyrrolidone structure, and a caprolactam structure. It is an active energy ray-curable composition of.
<8> The active energy ray-curable composition according to any one of <1> to <7>, which further contains an oligomer.
<9> The active energy ray-curable composition according to <8>, wherein the oligomer is at least one selected from an aromatic urethane oligomer, an aliphatic urethane oligomer, an epoxy acrylate oligomer, and a polyester acrylate oligomer.
<10> The above-mentioned <6> to <9>, wherein the content of the monofunctional polymerizable compound having one ethylenic double bond in the one molecule is 0% by mass or more and 90% by mass or less. It is an active energy ray-curable composition of.
<11> The active energy ray-curable composition according to any one of <1> to <10>, which is a material for three-dimensional modeling.
<12> The active energy ray-curable ink, which comprises the active energy ray-curable composition according to any one of <1> to <11>.
<13> The active energy ray-curable ink according to <12>, which is used for an inkjet.
<14> A method for forming a two-dimensional or three-dimensional image, which comprises an irradiation step of irradiating the active energy ray-curable composition according to any one of <1> to <11> with active energy rays. Is.
<15> The method for forming a two-dimensional or three-dimensional image according to <14>, further comprising a ejection step of ejecting the active energy ray-curable composition by an inkjet recording method.
<16> The method for forming a two-dimensional or three-dimensional image according to <15>, which includes a heating step of heating the active energy ray-curable composition before the discharge step.
<17> The composition container is characterized in that the active energy ray-curable composition according to any one of <1> to <11> is contained in the container.
<18> An accommodating portion for accommodating the active energy ray-curable composition according to any one of <1> to <11>.
An irradiation means for irradiating the active energy ray-curable composition with active energy rays,
It is a two-dimensional or three-dimensional image forming apparatus characterized by having at least.
<19> The two-dimensional or three-dimensional image forming apparatus according to <18>, further comprising a ejection means for ejecting the active energy ray-curable composition by an inkjet recording method.
<20> A two-dimensional or three-dimensional image characterized in that the active energy ray-curable composition according to any one of <1> to <11> is irradiated with active energy rays and cured. is there.
<21> A molded product characterized in that the two-dimensional or three-dimensional image described in <20> is stretched.

The active energy ray-curable composition according to any one of <1> to <11>, the active energy ray-curable ink according to any one of <12> to <13>, and <14> to <16. > And the two-dimensional or three-dimensional image forming apparatus described in <18> to <19> have solved the conventional problems and described as follows. The task is to achieve the purpose. That is, the active energy ray-curable composition, the active energy ray-curable ink, the method for forming a two-dimensional or three-dimensional image, and the device for forming a two-dimensional or three-dimensional image are excellent in ejection stability and dimensional stability. It is an object of the present invention to provide an active energy ray-curable composition, an active energy ray-curable ink, a method for forming a two-dimensional or three-dimensional image, and a device for forming a two-dimensional or three-dimensional image. And.
The composition container according to <17> has an object of solving the above-mentioned problems in the past and achieving the following objectives. That is, an object of the composition container is to provide a composition container capable of accommodating an active energy ray-curable composition capable of obtaining a cured product having excellent discharge stability and good dimensional stability.
The two-dimensional or three-dimensional image described in <20> and the molded product described in <21> have problems of solving the above-mentioned problems in the past and achieving the following objectives. That is, the two-dimensional or three-dimensional image and the molded product are two-dimensional or three-dimensional obtained by curing an active energy ray-curable composition capable of obtaining a cured product having excellent discharge stability and good dimensional stability. It is an object of the present invention to provide an image of the above and a molded product.

JP-A-2009-275097

10 Composition storage container (ink cartridge)
39 Image forming device

Claims (17)

Contains polymerizable compounds and non-polymerizable resin particles,
The volume-based median diameter of the non-polymerizable resin particles is 100 nm or more and 600 nm or less.
A composition for active energy ray-curable three-dimensional modeling, wherein the glass transition temperature of the non-polymerizable resin particles is 10 ° C. or higher and 54 ° C. or lower. The active energy ray-curable three-dimensional modeling composition according to claim 1, wherein the viscosity at 40 ° C. is 8 mPa · s or more and 25 mPa · s or less. The active energy ray-curable three-dimensional modeling composition according to any one of claims 1 to 2, wherein the glass transition temperature of the non-polymerizable resin particles is 10 ° C. The activity according to any one of claims 1 to 3, wherein the polymerizable compound contains at least one polyfunctional polymerizable compound of dipropylene glycol diacrylate, tricyclodecanedimethanol diacrylate, and pentaerythritol triacrylate. Energy ray-curable three-dimensional modeling composition. The active energy ray-curable three-dimensional modeling composition according to any one of claims 1 to 4, wherein the polymerizable compound contains a monofunctional polymerizable compound having one ethylenic double bond in one molecule. The active energy ray according to claim 5, wherein the monofunctional polymerizable compound having one ethylenic double bond in one molecule has any one of an alicyclic structure, a cyclic ether structure, a pyrrolidone structure, and a caprolactam structure. Curable three-dimensional modeling composition. The active energy ray-curable three-dimensional modeling composition according to any one of claims 1 to 6, which is a material for discharge. An active energy ray-curable ink comprising the composition for active energy ray-curable three-dimensional modeling according to any one of claims 1 to 7. The active energy ray-curable ink according to claim 8, which is for an inkjet. A method of forming a three-dimensional image you comprising the irradiation step of irradiating an active energy ray in the active energy ray-curable stereolithographic composition according to any one of claims 1 to 7. The method for forming a three- dimensional image according to claim 10, further comprising a ejection step of ejecting the active energy ray-curable three-dimensional modeling composition by an inkjet recording method. The method for forming a three- dimensional image according to claim 11, further comprising a heating step of heating the active energy ray-curable three-dimensional modeling composition before the discharge step. A composition storage container according to any one of claims 1 to 7, wherein the composition for active energy ray-curable three-dimensional modeling is contained in the container. An accommodating portion for accommodating the active energy ray-curable three-dimensional modeling composition according to any one of claims 1 to 7.
An irradiation means for irradiating the active energy ray-curable three-dimensional modeling composition with active energy rays,
Forming apparatus of a three-dimensional image you wherein at least comprising a. The three- dimensional image forming apparatus according to claim 14, further comprising an ejection means for ejecting the active energy ray-curable three-dimensional modeling composition by an inkjet recording method. The active energy ray-curable stereolithographic composition according to any one of claims 1 to 7, the three-dimensional image you characterized by formed by curing by an active energy ray. A molded product according to claim 16, wherein the three- dimensional image is stretched.