JP2017002187A - Active energy ray curable composition, active energy ray curable ink, composition accommodating container, forming method of image and forming device of image and molded processed method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray curable composition capable of providing a cured article excellent in discharge stability, having high hardness and less in curing shrinkage.SOLUTION: There is provided an active energy ray curable composition containing a polymerizable compound, a resin particle and the polymerizable compound have acryl equivalence of 150 g/eq or less and containing a polyfunctional polymerizable compounds having 2 or more ethylenic double bonds in a molecule.SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray curable composition, an active energy ray curable ink, a container containing them, a two-dimensional or three-dimensional image forming method and an image forming apparatus using them, And a molded product obtained by processing the image.

  Conventionally, active energy ray-curable compositions have been supplied and used for offsets, silk screens, topcoats, etc., but recently, the cost of the solvent has been reduced by simplifying the drying process and reducing the amount of solvent volatilized as an environmental measure. The amount of use is increasing due to the advantages such as.

  The active energy ray-curable composition is required to obtain a cured product having a high hardness from the viewpoints of productivity and improved curability and handling of the cured product. In addition, after being discharged and cured on a base material, a molding process is often performed as a post-treatment. Then, in order to improve the said shaping | molding process, sclerosis | hardenability, and hardness, for example, the active energy ray hardening-type composition which mix | blended the active energy ray hardening-type polyfunctional monomer is proposed (for example, patent documents 1-1). 3).

However, in these inventions, since there are many polyfunctional monomers, the discharge stability is poor and it is difficult to obtain high hardness, and the internal stress increases, resulting in an increase in the cured product (coating film or laminate thereof). There is a problem that curing shrinkage occurs.
An object of the present invention is to provide an active energy ray-curable composition that is excellent in ejection stability, has high hardness, and provides a cured product with little curing shrinkage.

  The active energy ray-curable composition of the present invention as a means for solving the above problems contains a polymerizable compound, resin particles, and a polymerization initiator, and the polymerizable compound has an acrylic equivalent of 150 g / eq or less. And a polyfunctional polymerizable compound having two or more ethylenic double bonds in one molecule.

  ADVANTAGE OF THE INVENTION According to this invention, the active energy ray hardening-type composition which is excellent in discharge stability, is high hardness, and can obtain hardened | cured material with little hardening shrinkage can be provided.

FIG. 1 is a schematic diagram illustrating an example of an image forming apparatus (two-dimensional stereoscopic image manufacturing apparatus) provided with an inkjet discharge unit. FIG. 2 is a schematic diagram illustrating an example of an image forming apparatus (three-dimensional stereoscopic image manufacturing apparatus) provided with an inkjet discharge unit. FIG. 3 is a schematic diagram illustrating another example of an image forming apparatus (a three-dimensional stereoscopic image manufacturing apparatus).

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

<Polymerizable compound>
The polymerizable compound contains a polyfunctional polymerizable compound, and if necessary, another polyfunctional polymerizable compound, a monofunctional polymerizable compound, and an oligomer having two or more ethylenic double bonds in one molecule. It contains other components.

<< Polyfunctional polymerizable compound >>
The polyfunctional polymerizable compound has an acrylic equivalent of 150 g / eq or less and two or more ethylenic double bonds in one molecule. When the acrylic equivalent is 150 g / eq or less, the curability of the obtained cured product (coating film or laminate thereof) can be improved, and the network structure in the cured product can be firmly configured to improve the hardness. . Moreover, in addition to the polyfunctional polymerizable compound, a polyfunctional polymerizable compound having an acrylic equivalent of more than 150 g / eq can be used in combination. You may use together. In addition, the said acrylic equivalent means the value represented by the weight average molecular weight / functional group number of a compound. The weight average molecular weight / functional group number of the compound was obtained by identifying the compound using a gas chromatography mass spectrometer (GC / MS, apparatus name: GCMS-QP2010 Plus, manufactured by Shimadzu Corporation), and obtaining the weight average molecular weight. And the number of functional groups.

  The acrylic equivalent of the polyfunctional polymerizable compound is 150 g / eq or less, preferably 90 g / eq or more and 150 g / eq or less.

  There is no restriction | limiting in particular as a weight average molecular weight of the said polyfunctional polymerizable compound, 100 or more and 1,000 or less are preferable, and 200 or more and 800 or less are more preferable.

  Examples of the polyfunctional polymerizable compound include 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol oligoacrylate, diethylene glycol diacrylate, 1,6-hexanediol oligoacrylate, and neopentyl glycol diacrylate. , Triethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, cyclohexane dimethanol diacrylate, tricyclodecane dimethanol diacrylate, propoxylated (2) neopentyl glycol diacrylate, trimethylolpropane triacrylate, Tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylation (3) Trimethylolpropane triacrylate, propoxylated (3) glyceryl triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated (4) pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and the like. These may be used alone or in combination of two or more. Among these, neopentyl glycol diacrylate, tripropylene glycol diacrylate, and trimethylolpropane triacrylate are preferable.

  As content of the said polyfunctional polymerizable compound, 10 mass% or more is preferable with respect to the active energy ray hardening-type composition whole quantity. When the content is 10% by mass or more, crosslinking of the obtained cured product is easily formed, and the hardness of the cured product can be improved.

<< Other polyfunctional polymerizable compounds >>
The other polyfunctional polymerizable compound is not particularly limited as long as it is other than the polyfunctional polymerizable compound having an acrylic equivalent of 150 g / eq or less and having two or more ethylenic double bonds in one molecule. The polyfunctional polymerizable compound having an acrylic equivalent exceeding 150 g / eq and having two or more ethylenic double bonds in one molecule is preferable.

  Examples of the polyfunctional polymerizable compound having an acrylic equivalent exceeding 150 g / eq and having two or more ethylenic double bonds in one molecule include hexadiol diacrylate, polyethylene glycol diacrylate, and tripropylene glycol. Triacrylate, bispentaerythritol hexaacrylate, ethylene glycol diacrylate, 1,6-hexanediol diacrylate, ethoxylated 1,6-hexanediol diacrylate, polypropylene glycol diacrylate, 1,4-butanediol diacrylate, 1, 9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, hydroxypivalate neopentyl Coal diacrylate, 1,3-butylene glycol di (meth) acrylate, hydroxypivalic acid trimethylolpropane triacrylate, ethoxylated phosphoric acid triacrylate, ethoxylated tripropylene glycol diacrylate, neopentyl glycol modified trimethylolpropane diacrylate, Stearic acid-modified pentaerythritol diacrylate, tetramethylolpropane triacrylate, tetramethylolmethane triacrylate, caprolactone-modified trimethylolpropane triacrylate, propoxylate glyceryl triacrylate, tetramethylolmethane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol Hexaacrylate, caprolactone Dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, neopentyl glycol oligoacrylate, 1,4-butanediol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, ethoxy Neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, and the like. These may be used alone or in combination of two or more. Among these, polypropylene glycol diacrylate is preferable.

  As content of the said other polyfunctional polymerizable compound, 0 mass% or more and 60 mass% or less are preferable with respect to the active energy ray hardening-type composition whole quantity. When the content is 0% by mass or more and 60% by mass or less, crosslinking of the obtained cured product is easily 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 according to the purpose.
Examples of the monofunctional polymerizable compound include phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, 2 -Methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydixylethyl acrylate, ethyl diglycol acrylate, cyclic trimethylolpropane Formal monoacrylate, imide acrylate, isoamyl ar Relate, ethoxylated succinic acid acrylate, trifluoroethyl acrylate, ω-carboxypolycaprolactone monoacrylate, N-vinylformamide, cyclohexyl acrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-t-butylcyclohexyl acrylate, caprolactone modified tetrahydrofurfuryl Acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, 2-phenoxyethyl acrylate, acryloylmorpholine, phenoxydiethylene glycol acrylate, vinyl caprolactam, vinyl pyrrolidone, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol Monoacrylate, 2- (2-Ethoxy Ciethoxy) ethyl acrylate, stearyl acrylate, diethylene glycol monobutyl ether acrylate, lauryl acrylate, isodecyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, isooctyl acrylate, octyl / decyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylation ( 4) Nylphenol acrylate, methoxypolyethylene glycol (350) monoacrylate, methoxypolyethylene glycol (550) monoacrylate, and the like. These may be used alone or in combination of two or more.

Among these, from the point of hardness, it is preferable to include 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 phenoxyethyl acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl acrylate, methylphenoxyethyl acrylate, and 4-t-butylcyclohexyl acrylate. , Caprolactone-modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, 2-phenoxyethyl acrylate (or its ethylene oxide and / or propylene oxide addition monomer), acryloylmorpholine, isobornyl acrylate, phenoxydiethylene glycol Acrylate, vinyl caprolactam, vinyl pyrrolidone, 2-hydroxy-3-phenoxy Propyl 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 according to the purpose, and may be monocyclic And 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 phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3 -Vinylcyclohexene oxide, 4-vinylcyclohexene oxide, etc. are 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 to 90% by mass, more preferably 20% by mass to 90% by mass, and more preferably 20% by mass with respect to the total amount of the active energy ray-curable composition. The content is particularly preferably 80% by mass or less. When the content is 0% by mass or more and 90% by mass or less, the effect of the polyfunctional polymerizable compound tends to appear and the hardness can be improved.

<< Oligomer having two or more ethylenic double bonds in one molecule >>
The oligomer having two or more ethylenic double bonds in one molecule is not particularly limited as long as it has two or more ethylenic double bonds in one molecule, and should be appropriately selected according to the purpose. Can do. In addition, an oligomer means the polymer whose repeating number of the monomer structural unit of the said monofunctional polymerizable compound is 2-20. The “polyfunctional polymerizable compound” does not include an oligomer.

  The weight average molecular weight of the oligomer having two or more ethylenic double bonds in one molecule is not particularly limited and may be appropriately selected depending on the intended purpose. It is 1,000 or more and 30,000 in terms of polystyrene. The following is preferable, and 5,000 or more and 20,000 or less are more preferable. The weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC).

  Examples of the oligomer having two or more ethylenic double bonds in one molecule 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.

  A commercially available product can be used as the oligomer having two or more ethylenic double bonds in one molecule, and examples of the commercially available product include UV-2000B and UV-2750B manufactured by Nippon Synthetic Chemical Industry Co., Ltd. , UV-3000B, UV-3010B, UV-3200B, UV-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 manufactured by Sartomer , CN944, CN9 4B85, CN959, CN961E75, CN961H81, CN962, CN963, CN963A80, CN963B80, CN963E75, CN963E80, CN963J85, CN964, CN965, CN965A80, CN966, CN966A80, CN966B85, CN966H90, CN966J75, CN968, CN969, CN970, CN970A60, CN970E60, CN971, CN971A80, CN971J75, CN972, CN973, CN973A80, CN973H85, CN973J75, CN975, CN977, CN977C70, CN978, CN980, CN981, CN981A75, CN982B, N98288, C982 2E75, CN983, CN984, CN985, CN985B88, CN986, CN989, CN991, CN992, CN994, CN996, CN997, CN999, CN9001, CN9002, CN9004, CN9005, C9009, C9009, C9009, C9009, C9009 CN9019, CN9024, CN9025, CN9026, CN9028, CN9029, CN9030, CN9060, CN9165, CN9167, CN9178, CN9290, CN9782, CN9783, CN9788, CN9873E 70, KRM8200, EBECRYL5129, EBECRYL8210, EBECRYL8301, EBECRYL8804, EBECRYL8807, EBECRYL9260, KRM7735, KRM8296, KRM8451, EBECRYL8858, EBECRYL8858, EBECRYL8858, EBECRYL8858 These may be used alone or in combination of two or more.

  The content of the oligomer having two or more ethylenic double bonds in one molecule is preferably 10% by mass or less, more preferably 9% by mass or less, based on the total amount of the active energy ray-curable composition. It is more preferably at most 5% by mass, particularly preferably at most 5% by mass. When the content is 10% by mass or less, the hardness of the obtained cured product can be increased.

<Resin particles>
There is no restriction | limiting in particular as said resin particle, According to the objective, it can select suitably, For example, the resin particle etc. which the polymerization reaction by irradiation of an active energy ray or a heating does not occur are mentioned.
The resin particles (in which the non-aqueous polymer resin particles are dispersed) are added to the active energy ray-curable composition, and the resin particles are insoluble in the polymerizable compound. Does not cause a significant increase in viscosity as in the case of For this reason, the fall of the inkjet discharge characteristics (discharge stability etc.) by the viscosity raise by the addition of the said resin particle can be suppressed.
In addition, although the reason is not clear, the resin particles act as hard segments in the cured product after being cured by irradiating the active energy ray-curable composition with active energy rays. It is thought that the hardness can be improved.
Furthermore, by containing the resin particles, the number of functional groups per unit volume can be lowered, so that curing shrinkage during curing can be suppressed.

  The resin particles are not particularly limited. 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, vinyl acetate resin particles. Etc. Among these, acrylic resin particles are preferable. The acrylic resin particles mean resin particles made of a polymer of at least one of acrylic acid ester and methacrylic acid ester.

Examples of the resin particles include non-aqueous resin particles.
The non-aqueous resin particles are made of a core / shell structure resin. As the dispersion medium, aliphatic hydrocarbons are mainly used. For example, hexane, heptane, octane, cyclohexane, mineral spirit, and other paraffinic and naphthenic petroleum fractions can be used. In order to stably disperse the resin particles in the dispersion medium, the particle surface must be wrapped with a solid repulsive layer.
Non-aqueous resin particles that are currently in practical use include the above-mentioned dispersion stabilizers using a copolymer in which a soluble polymer part and an insoluble polymer part are blocked or graft-polymerized in the dispersion as a dispersion stabilizer. 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 moves to the formed dispersed particle nucleus, and polymerization proceeds in the particle. By this process, finally, polymer particles (core polymer) wrapped in a shell structure (corresponding to the above-mentioned steric repulsion layer) dispersible in a dispersion medium are 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 can be dissolved in a solvent is produced, and this shell polymer is used as a protective colloid and a core polymer insoluble in the solvent is continuously processed. To produce a non-aqueous emulsion having a core / shell structure.

  The non-aqueous resin particles are dispersed using a dispersion medium other than the polymerizable compound, but preferably contain no solvent other than the polymerizable compound as described above, and in this case, the dispersion solvent is polymerized. It is preferable to substitute a solvent for the active compound.

  Examples of the solvent replacement include a method using a rotary evaporator, a method using a difference in boiling points such as steam distillation and vacuum distillation. By replacing the solvent with the above method or the like, an active energy ray-curable composition that does not contain a compound (solvent) unnecessary for the curing reaction can be obtained even if the resin particles are contained in the active energy ray-curable composition. it can.

  There is no restriction | limiting in particular as a volume average particle diameter of the said resin particle, 30 nm or more and 600 nm or less are preferable, and 100 nm or more and 300 nm or less are more preferable. When the volume average particle size is 30 nm or more, the resin particles can be easily dispersed in the dispersion medium, and when the volume average particle size is 600 nm or less, ejection stability can be improved. Moreover, when it is 100 nm or more and 300 nm or less, since the resin particles have a sufficient size, the role as a hard segment can be sufficiently achieved, and the hardness can be improved. Here, the volume average particle diameter can be measured using, for example, a particle size analyzer (Microtrac Model UPA 9340, manufactured by Nikkiso Co., Ltd.).

  There is no restriction | limiting in particular as glass transition temperature of the said resin particle, 0 to 100 degreeC is preferable and 25 to 60 degreeC is more preferable. When the glass transition temperature is 0 ° C. or higher and 100 ° C. or lower, the resin particles can be prevented from agglomerating in a room temperature environment even if the resin particles are dispersed in the composition in a very unstable state. In addition, it is possible to improve the discharge stability, and it becomes easy to work as a hard segment in the cured product, thereby improving the hardness. Here, the glass transition temperature of the resin particles can be measured, for example, by a differential scanning calorimetry (DSC) method. As the DSC device, for example, Seiko Instruments DSC120U (manufactured by Seiko Instruments Inc.) can be used, and the measurement temperature can be 30 ° C. or more and 300 ° C. or less, and the temperature rise rate can be measured at 2.5 ° C. per minute.

  As content of the said resin particle, 3 mass% or more and 20 mass% or less are preferable with respect to an active energy ray hardening-type composition, and 5 mass% or more and 7 mass% or less are more preferable. When the content is 3% by mass or more, the hardness of the obtained cured product can be improved, and curing shrinkage can be reduced. When the content is 20% by mass or less, an increase in viscosity can be suppressed. Ink jet characteristics such as ejection stability can be improved.

<Method for quantifying each component contained in the active energy ray-curable composition>
As a method for quantifying the polyfunctional polymerizable compound, resin particles, monofunctional polymerizable compound, and oligomer contained in the active energy ray-curable composition of the present invention, for example, from peak intensity obtained by GC-MS measurement Examples include a method of quantifying; a method of quantifying from peak intensity obtained by molecular weight distribution measurement by GPC; and a method of quantifying from an integrated value obtained by ¹ H NMR measurement. One specific quantification method is a method of creating a calibration curve. Further, simply, a standard sample for each component (for example, a sample containing 15% by mass of the corresponding polyfunctional polymerizable compound) is prepared and measured under the same conditions, so that the relative relationship of the contents is relatively It is also possible to evaluate automatically. When the compounding 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.
Moreover, when each component type is unknown, qualitative can be performed in advance using GC-MS, ¹ H NMR, or the like. The glass transition temperature of the homopolymer can be measured using, for example, a differential scanning calorimetry (DSC) method. The glass transition temperature by the differential scanning calorimetry (DSC) method can be measured by extracting only the polymer component by extracting the sample with a poor polymer solvent.

<Other ingredients>
Other components are not particularly limited. For example, conventionally known polymerization initiators, polymerization accelerators, coloring materials, organic solvents, polymerization inhibitors, slip agents (surfactants), penetration enhancers, wetting agents ( Humectants), fixing agents, antifungal agents, preservatives, antioxidants, ultraviolet absorbers, chelating agents, pH adjusting agents, thickeners and the like.

<< Polymerization initiator >>
The polymerization initiator is not particularly limited 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 and cationic polymerization initiators may be used singly or in combination of two or more, and among them, it is preferable to use a radical polymerization initiator. Moreover, as content of the said polymerization initiator, in order to obtain sufficient hardening rate, 5 mass% or more and 20 mass% or less are preferable with respect to the active energy ray hardening-type composition whole quantity.

  Examples of the radical polymerization initiator include aromatic ketones, acyl phosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, and the like. Ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds. These may be used alone or in combination of two or more.

In addition to the polymerization initiator, a polymerization accelerator can be used in combination.
The polymerization accelerator is not particularly limited. For example, ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and amine compounds such as butoxyethyl p-dimethylaminobenzoate. 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 that does not contain a colorant, or may be a color liquid containing a colorant. When the clear liquid is used or when it is desired to keep the color tone of the color material itself as much as possible, it is preferable to use a material other than the color material to be described later that is less colored.

<< Color material >>
As the coloring material, a glossy color such as black, white, magenta, cyan, yellow, green, orange, gold or silver is given according to the purpose and required characteristics of the active energy ray-curable composition in the present invention. Various pigments and dyes can be used, and the content thereof is preferably 0.1% by mass or more and 20% by mass or less, and preferably 1% by mass or more and 10% by mass or less based on the total amount of the active energy ray-curable composition. More preferred.

Examples of the pigment include inorganic pigments and organic pigments. These may be used alone or in combination of two or more.
Examples of the inorganic pigment that can be used include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, titanium oxide, and the like.
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, Polycyclic pigments such as quinophthalone pigments, dye chelates (eg, basic dye chelates, acid dye chelates), dyeing lakes (basic dye rakes, acid dye rakes), nitro pigments, nitroso pigments, aniline black And daylight fluorescent pigments.
In order to further improve the dispersibility of the pigment, a dispersant may be further included.

  The dispersant is not particularly limited, and examples thereof include dispersants commonly used for preparing pigment dispersions such as polymer dispersants.

  There is no restriction | limiting in particular as said dye, For example, an acidic dye, a direct dye, a reactive dye, a basic dye etc. are mentioned. These may be used alone or in combination of two or more.

<< 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. By not containing organic solvents (for example, VOC (Volatile Organic Compounds) free), there is no residue of volatile organic solvents in the cured film, so that safety in the printing field can be obtained and environmental pollution can be prevented. It becomes. The “organic solvent” means what is generally called a volatile organic compound (VOC), and examples thereof include ether, ketone, xylene, ethyl acetate, cyclohexanone, toluene, and the like. It should be distinguished from the functional monomer. Further, “not containing” an organic solvent means substantially not containing, and the content is preferably less than 0.1% by mass.

<< Polymerization inhibitor >>
Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, methylhydroquinone, hydroquinone, t-butylhydroquinone, di-t-butylhydroquinone, methoquinone, 2,2′-dihydroxy-3,3′-di ( α-methylcyclohexyl) -5,5′-dimethyldiphenylmethane, p-benzoquinone, di-t-butyldiphenylamine, 9,10-di-n-butoxycyantracene, 4,4 ′-[1,10-dioxo-1 , 10-decandiylbis (oxy)] bis [2,2,6,6-tetramethyl] -1-piperidinyloxy and the like.

<< Slip agent (surfactant) >>
There is no restriction | limiting in particular as said slip agent (surfactant), According to the objective, it can select suitably, For example, higher fatty acid type surfactant, silicone type surfactant, fluorine type surfactant etc. are mentioned. It is done.

<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, the active energy ray-curable composition is discharged from a nozzle. When applying the discharging means, the viscosity in the range of 20 ° C. to 65 ° C., desirably the viscosity at 25 ° C. is preferably 3 mPa · s to 40 mPa · s, more preferably 5 mPa · s to 15 mPa · s, 6 mPa · s or more and 12 mPa · s or less is particularly preferable. Moreover, it is particularly preferable that the viscosity range is satisfied without including the organic solvent. In addition, the said viscosity uses a cone rotor (1 degree 34'xR24) by Toki Sangyo Co., Ltd. cone plate type rotational viscometer VISCOMETER TVE-22L, rotation speed is 50 rpm, and the temperature of constant temperature circulating water is 20 degreeC. It can be set and measured as appropriate within the range of 65 ° C. or lower. VISCOMATE VM-150III can be used for temperature adjustment of circulating water.

<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.

(Use)
The active energy ray-curable composition of the present invention is not particularly limited as long as the active energy ray-curable material is generally used in the field, and can be appropriately selected according to the purpose. For example, a molding resin, It can be applied to 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, but also as a three-dimensional modeling material for forming a three-dimensional three-dimensional image (three-dimensional model). Can also be used.
As the three-dimensional modeling material, for example, as a binder of powder particles used in a powder lamination method which is one of three-dimensional modeling methods, and as shown in FIG. 2, an active energy ray curable composition is used. As shown in FIG. 3, a material jet method (stereolithography method) in which three-dimensional modeling is performed by sequentially stacking materials that have been ejected to a predetermined area and irradiated with active energy rays and cured, and an active energy ray-curable composition. A solid object in an optical modeling method or the like in which a storage pool (container) 1 of 5 is irradiated with active energy rays 4 to form a hardened layer 6 having a predetermined shape on the movable stage 3, and this is sequentially laminated to perform three-dimensional modeling. It can be used as a constituent material.
A three-dimensional modeling apparatus for modeling a three-dimensional modeled object using such an active energy ray-curable composition can use a known one, and is not particularly limited. A thing provided with a supply means, a discharge means, an active energy ray irradiation means, etc. can be used.
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 such as a recording medium. . 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 may be appropriately selected depending on the purpose. Examples thereof include paper, plastic, metal, ceramic, glass, and composite materials thereof. From the viewpoint of workability, plastic is preferable. A substrate is preferred. In addition, the stretchability of the cured product in the present invention is expressed as a stretchability at 180 ° C. as a ratio of (length after tensile test−length before tensile test) / (length before tensile test). It is preferably 50% or more, and more preferably 100% or more.

(Active energy ray curable ink)
The active energy ray curable ink of the present invention (hereinafter sometimes referred to as “ink”) is made of the active energy ray curable composition of the present invention and is preferably used for inkjet.

The static surface tension at 25 ° C. of the active energy ray-curable ink 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 (manufactured by Kyowa Interface Science Co., Ltd., CBVP-Z type). The static surface tension assumes specifications of a commercially available inkjet discharge head such as GEN4 manufactured by Ricoh Printing Systems Co., Ltd., for example.

(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 the use and usage, and are not particularly limited. It is desirable to be covered with an adhesive sheet.

(Image Forming Method and Image 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, and the image forming apparatus of the present invention irradiates active energy rays. An irradiating means for carrying out, and an accommodating part for accommodating the active energy ray-curable composition, and the container may be accommodated in the accommodating part. Further, it may have a discharge step and discharge means for discharging the active energy ray-curable composition, or may have a heating step and heating means for heating ink before the discharge step and the discharge means. Good. 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.

It is preferable that the heating temperature (° C.) in the heating step and the glass transition temperature (° C.) of the resin particles satisfy the following formula (1).
Heating temperature (° C.) − Glass transition temperature of resin particles (° C.) ≦ 10 ° C. Formula (1)
The resin particles are dispersed in a very unstable state in the composition. When the formula (1) is satisfied, the resin particles can be prevented from aggregating due to heat or pressure during discharge. , Discharge stability can be improved.

  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, for a recording medium that moves intermittently according to the ejection head width, a serial method in which ink is ejected onto the recording medium by moving the head, or the recording medium is moved continuously and held at a fixed position. Any ink jet recording apparatus of a line system in which ink is ejected from a head onto a recording medium 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) used in the present invention. The image forming apparatus 39 in FIG. 2 uses a head unit (movable in the AB direction) in which inkjet heads are arranged to transfer the first active energy ray-curable composition from the molded article ejection head unit 30 to the support. 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 discharge head units 31 and 32, and these respective compositions are discharged by the adjacent ultraviolet irradiation means 33 and 34. It is laminated while curing. 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, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

<Volume average particle diameter>
The volume average particle size was measured using a particle size analyzer (Microtrac Model UPA9340, manufactured by Nikkiso Co., Ltd.).

<Glass transition temperature>
The glass transition temperature was measured using a differential scanning calorimeter (Seiko Instruments DSC120U, manufactured by Seiko Instruments Inc.) at a measurement temperature of 30 ° C. or more and 300 ° C. or less and a temperature increase rate of 2.5 ° C. per minute.

<Gardner viscosity>
The Gardner viscosity was measured at 25 ° C. at a solid content concentration of 35% by mass according to JIS K7233 4.3 as described in JP-A No. 2003-55890.

<Synthesis of resin particles>
-Synthesis of resin particles A-
150 mass of petroleum-based hydrocarbon (trade name: A-solvent, manufactured by JX Nippon Oil & Energy Corporation, hereinafter referred to as “A-solvent”) in a reaction vessel in which the air in the vessel is replaced with nitrogen Parts, and after raising the temperature to 90 ° C., 100 parts by mass of styrene, 100 parts by mass of isobutyl methacrylate, 50 parts by mass of 2-ethylhexyl acrylate, and benzoyl peroxide (hereinafter sometimes referred to as “BPO”) A mixture consisting of 10 parts by mass and 100 parts by mass of A-solvent was added dropwise over 3 hours. After completion of the addition, the mixture was maintained at the same temperature for 5 hours, and the non-volatile content was 49.8% by mass (that is, monomer) A transparent resin solution having a conversion of 99.6%) and a Gardner viscosity at 25 ° C. of XY was obtained. The obtained resin solution consists of 100 parts by weight of vinyl acetate, 100 parts by weight of ethyl acrylate, 49 parts by weight of methyl methacrylate, 1 part by weight of methacrylic acid, 2.5 parts by weight of BPO, and 250 parts by weight of A-solvent. The mixture is added dropwise over 3 hours, and after completion of the addition, milky white resin particles are maintained at the same temperature for 5 hours, and the nonvolatile content is 47.5% by mass (that is, the monomer conversion rate of the dispersoid is 90%). A dispersion was obtained. The obtained dispersion of resin particles was stirred with a stirrer for 30 minutes to obtain a dispersion of resin particles A (acrylic resin particles) having a volume average particle size of 80 nm (solid content concentration: 55% by mass). In addition, the glass transition temperature of the resin particle A was 25 degreeC.

-Synthesis of resin particles B-
In the synthesis of the resin particle A, the resin particle B (acrylic resin) having a volume average particle diameter of 120 nm is the same as the synthesis of the resin particle A, except that the amount of BPO at the time of synthesizing the core is changed to 8 parts by mass. Resin particles) (solid content concentration: 55% by mass) was obtained. In addition, the glass transition temperature of the resin particle B was 25 degreeC.

-Synthesis of resin particles C-
In the synthesis of the resin particle A, the resin particle C (acrylic resin) having a volume average particle size of 200 nm is the same as the synthesis of the resin particle A except that the amount of BPO at the time of synthesizing the core is changed to 6 parts by mass. Resin particles) (solid content concentration: 55% by mass) was obtained. In addition, the glass transition temperature of the resin particle C was 25 degreeC.

-Synthesis of resin particles D-
In the synthesis of the resin particle A, the resin particle D (acrylic resin) having a volume average particle size of 250 nm is the same as the synthesis of the resin particle A, except that the amount of BPO at the time of synthesizing the core is changed to 4 parts by mass. Resin particles) (solid content concentration: 55% by mass) was obtained. In addition, the glass transition temperature of the resin particle D was 25 degreeC.

-Synthesis of resin particles E-
In the synthesis of the resin particle A, the resin particle E (acrylic resin) having a volume average particle size of 20 nm is the same as the synthesis of the resin particle A, except that the amount of BPO at the time of synthesizing the core is changed to 2 parts by mass. Resin particles) (solid content concentration: 55% by mass) was obtained. In addition, the glass transition temperature of the resin particle E was 25 degreeC.

-Synthesis of resin particles F-
A reaction vessel in which the air in the vessel was replaced with nitrogen was charged with 150 parts by mass of A-solvent and heated to 90 ° C., and then 100 parts by mass of styrene, 100 parts by mass of n-butyl methacrylate, and 2-ethylhexyl. A mixture of 50 parts by mass of acrylate, 2.5 parts by mass of BPO, and 100 parts by mass of A-solvent was dropped over 3 hours, and after completion of the dropwise addition, the mixture was maintained at the same temperature for 5 hours, and the nonvolatile content was 49 A transparent resin solution having a mass conversion of 8% by mass (that is, a monomer conversion of 99.6%) and a Gardner viscosity at 25 ° C. of XY was obtained. The obtained resin solution consists of 100 parts by weight of vinyl acetate, 100 parts by weight of ethyl acrylate, 49 parts by weight of methyl methacrylate, 1 part by weight of methacrylic acid, 2.5 parts by weight of BPO, and 250 parts by weight of A-solvent. The mixture is added dropwise over 3 hours, and after completion of the addition, milky white resin particles are maintained at the same temperature for 5 hours, and the nonvolatile content is 47.5% by mass (that is, the monomer conversion rate of the dispersoid is 90%). A dispersion liquid (solid content concentration: 57% by mass) of F (acrylic resin particles) was obtained. The obtained resin particles F had a volume average particle size of 100 nm and a glass transition temperature of 15 ° C.

-Synthesis of resin particles G-
A reaction vessel in which the air in the vessel was replaced with nitrogen was charged with 150 parts by mass of A-solvent, heated to 90 ° C., 100 parts by mass of styrene, 100 parts by mass of iso-butyl methacrylate, and 2-ethylhexyl. A mixture of 50 parts by mass of acrylate, 2.5 parts by mass of BPO, and 100 parts by mass of A-solvent was dropped over 3 hours, and after completion of the dropwise addition, the mixture was maintained at the same temperature for 5 hours, and the nonvolatile content was 49 A transparent resin solution having a mass conversion of 8% by mass (that is, a monomer conversion of 99.6%) and a Gardner viscosity at 25 ° C. of XY was obtained. The obtained resin solution consists of 100 parts by weight of vinyl acetate, 100 parts by weight of ethyl acrylate, 49 parts by weight of methyl methacrylate, 1 part by weight of methacrylic acid, 2.5 parts by weight of BPO, and 250 parts by weight of A-solvent. The mixture is added dropwise over 3 hours, and after completion of the addition, milky white resin particles are maintained at the same temperature for 5 hours, and the nonvolatile content is 47.5% by mass (that is, the monomer conversion rate of the dispersoid is 90%). A dispersion liquid (solid content concentration: 57% by mass) of G (acrylic resin particles) was obtained. The obtained resin particles G had a volume average particle size of 95 nm and a glass transition temperature of −5 ° C.

-Synthesis of resin particles H-
A reaction vessel in which the air in the vessel was replaced with nitrogen was charged with 150 parts by mass of A-solvent and heated to 90 ° C., and then 100 parts by mass of tert-butylstyrene, 100 parts by mass of iso-butyl methacrylate, and A mixture composed of 50 parts by mass of 2-ethylhexyl acrylate, 2.5 parts by mass of BPO, and 100 parts by mass of A-solvent was dropped over 3 hours. A transparent resin solution having a content of 49.8% by mass (that is, a monomer conversion of 99.6%) and a Gardner viscosity at 25 ° C. of XY was obtained. The obtained resin solution consists of 100 parts by weight of vinyl acetate, 100 parts by weight of ethyl acrylate, 49 parts by weight of methyl methacrylate, 1 part by weight of methacrylic acid, 2.5 parts by weight of BPO, and 250 parts by weight of A-solvent. The mixture is added dropwise over 3 hours, and after completion of the addition, milky white resin particles are maintained at the same temperature for 5 hours, and the nonvolatile content is 47.5% by mass (that is, the monomer conversion rate of the dispersoid is 90%). A dispersion liquid (solid content concentration: 57 mass%) of H (acrylic resin particles) was obtained. The obtained resin particles H had a volume average particle size of 90 nm and a glass transition temperature of 52 ° C.

<Preparation of colorant dispersion>
-Preparation of cyan pigment dispersion-
8 parts by mass of a polymer dispersant (trade name: Solspers 32000, manufactured by Avicia Co., Ltd., acid value: 24.8 mgKOH / g, base number: 27.1 mgKOH / g) and 72 parts by mass of isobornyl acrylate in a stainless steel beaker The mixture was stirred and dissolved for 1 hour while heating on a hot plate at 65 ° C. Thereafter, it was cooled to room temperature, and Pigment Blue 15: 4 (trade name: Cyanine Blue 4044, manufactured by Sanyo Dye Co., Ltd., acid value: 0.0 mgKOH / g, base number 8.0 mgKOH / g) was added, 200 g of zirconia beads having a diameter of 0.3 mm were placed in a glass bottle and sealed, and dispersed for 8 hours with a paint shaker. Then, the zirconia beads were removed to prepare a cyan pigment dispersion.

<Example 1>
50% by mass of tripropylene glycol diacrylate (manufactured by Osaka Organic Chemical Co., Ltd.), 38% by mass of neopentyl glycol diacrylate (manufactured by Sartomer), 12% by mass of trimethylolpropane triacrylate (manufactured by Sartomer), 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by LAMBERTI) 5% by mass, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by BASF) 5% by mass, and 2,4-diethylthioxanthene -9-one (manufactured by Daido Kasei Kogyo Co., Ltd.) 2 mass% was added in order and stirred for 1 hour, and it was confirmed that there was no undissolved residue visually. Subsequently, the dispersion liquid of the resin particle A was added so that solid content concentration might be 7 mass%, and it stirred for 30 minutes. Then, it filtered with the membrane filter, the coarse particle which causes a head clogging was removed, and the active energy ray hardening-type composition 1 was produced. In addition, the dispersion of the resin particles A utilizes a difference in boiling points using a rotary evaporator, and uses tripropylene glycol diacrylate of a polyfunctional polymerizable compound which is a polymerizable compound having the largest content in the composition. Then, the solvent-substituted one was used.

<Examples 2 to 17 and Comparative Examples 1 to 4>
The active energy ray-curable compositions 2 to 21 of Examples 2 to 17 and Comparative Examples 1 to 4 were the same as Example 1 except that the compositions and contents described in Tables 1 to 5 were changed. Was made. In addition, the used dispersion liquid of the resin particles A to H uses a difference in boiling point using a rotary evaporator, and uses a solvent substituted with a polymerizable compound having the largest content in each composition. did.

  About the produced active energy ray hardening-type compositions 1-21 of Examples 1-17 produced and Comparative Examples 1-4, "discharge stability", "hardness", and "curing shrinkage" were evaluated as follows. did. The results are shown in Tables 1-5.

<Discharge stability>
The produced active energy ray-curable compositions 1 to 21 (inks 1 to 21) of Examples 1 to 17 and Comparative Examples 1 to 4 were used by using an inkjet discharge device equipped with a GEN4 head (manufactured by Ricoh Printing Systems Co., Ltd.). 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 discharge device was set to a driving frequency of 18 kHz, a heating temperature of 35 ° C., and an ink discharge amount per time of 2 pL. The term “nozzle missing” means that ink droplets are not ejected from the nozzle where clogging has occurred.
-Evaluation criteria-
◎: 1 or less ○: 2 or more and 5 or less △: 6 or more and 8 or less ×: 9 or more

[Production of cured product]
The produced active energy ray-curable compositions 1 to 21 (inks 1 to 21) of Examples 1 to 17 and Comparative Examples 1 to 4 were used by using an inkjet discharge device equipped with a GEN4 head (manufactured by Ricoh Printing Systems Co., Ltd.). The film was discharged on a polycarbonate film (Mitsubishi Engineering Plastics Co., Ltd., Iupilon 100FE2000 masking, average thickness: 100 μm) so that the average thickness was 10 μm. Regarding the inks 1 to 21, the maximum heating temperature of the head was set to 45 ° C., and the heating temperature was appropriately adjusted so that the viscosity of all the inks 1 to 21 was 11 mPa · s. Immediately after the ejection, a UV irradiation machine (device name: LH6, manufactured by Fusion Systems Japan Co., Ltd.) was used to irradiate ultraviolet rays with a light amount of 1,500 mJ / cm ² to obtain a cured product. As a measuring method of the average thickness, it was measured using an electronic micrometer (manufactured by Anritsu Co., Ltd.) and obtained from an average value of 10 thicknesses.

<Hardness>
About the obtained hardened | cured material, pencil hardness was measured based on JISK5600-5-4 scratch hardness (pencil method), and "hardness" was evaluated based on the following evaluation criteria.

-Equipment and instruments-
・ Apparatus: Scratched pencil hardness manufactured by COTEC Co., Ltd. TQC WW Tester (Load 750g only)
・ Pencil: Wooden drawing pencil set of the following hardness (Mitsubishi Pencil Co., Ltd.)
6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H
-Pencil scribing device: A special scribing device that leaves only the cylindrical core of the pencil and scrapes only the xylem.
-Evaluation criteria-
◎: Pencil hardness is H or higher ○: Pencil hardness is HB
Δ: Pencil hardness is B or 2B
X: Pencil hardness is 3B or less In addition, about the ink with low sclerosis | hardenability, when it hardens with the said light quantity, since it does not harden sufficiently, hardness also becomes low.

<Curing shrinkage>
In the production of the cured product, a width of 43 mm × a length of 190 mm was obtained in the same manner as the production of the hard material except that the polycarbonate film was changed to a PET film (trade name: E5100, manufactured by Toyobo Co., Ltd., average thickness: 100 μm). A cured product was obtained. After curing, it was allowed to stand at room temperature and normal pressure for 3 days, the degree of warping of the cured product on the PET film after standing was observed, and “hardness shrinkage” was evaluated based on the following evaluation criteria.
-Evaluation criteria-
○: Curing of cured product due to curing shrinkage is not observed Δ: Curing of cured product due to curing shrinkage is observed and less than 3 cm ×: Curing of cured product due to curing shrinkage is 3 cm or more

In Tables 1 to 5, trade names and manufacturing company names of the compounds used have the following contents.
・ Isobornyl acrylate: IBXA (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
・ Phenoxyethyl acrylate: PEA (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
・ Benzyl acrylate: BzA (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
・ Tripropylene glycol diacrylate: TPGDA (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
・ Neopentyl glycol diacrylate: SR247 (Sartomer)
Trimethylolpropane triacrylate: SR351S (Sartomer)
Polypropylene glycol (400) diacrylate: SR344 (manufactured by Sartomer)
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide: TPO (manufactured by LAMBERTI)
Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide: Irg. 819 (BASF)
・ 2,4-Diethylthioxanthen-9-one: DETX (manufactured by Daido Kasei Kogyo Co., Ltd.)
・ Polyester resin: Byron 220 (Toyobo Co., Ltd.)
In the table, the resin is not dissolved in the active energy ray-curable composition and is distinguished from the dispersed resin particles.

  From the results of Tables 1 to 5, the active energy ray curable compositions (active energy ray curable inks) of Examples 1 to 17 using the present invention are the active energy ray curable inks of Comparative Examples 1 to 4. It was found that a cured product having good ejection stability in inkjet, excellent hardness and curability, and reduced cure shrinkage can be obtained.

<Test on the effect of ink heating temperature on ejection stability>
The ink heating temperature of the active energy ray-curable composition 1 (ink 1) obtained in Example 1 was set to 25 ° C. (test 1) using an ink jet discharge device equipped with a GEN4 head (manufactured by Ricoh Printing Systems Co., Ltd.). “Discharge stability” was evaluated in the same manner as in Examples 1 to 17 and Comparative Examples 1 to 4 by adjusting to 35 ° C. (Test 2) or 45 ° C. (Test 3). In addition, the said inkjet discharge device set the drive frequency to 18 kHz, and set the ink discharge amount per time to 2 pL.

From the results shown in Table 6, when the relationship between the heating temperature at the ink head and the glass transition temperature of the resin particles satisfies the following formula (1), aggregation due to heat and pressure is eliminated, so that ejection stability can be improved. all right.
Heating temperature (° C.) − Glass transition temperature of resin particles (° C.) ≦ 10 ° C. Formula (1)

As an aspect of this invention, it is as follows, for example.
<1> Contains a polymerizable compound, resin particles, and a polymerization initiator,
An active energy ray curable type, wherein the polymerizable compound contains a polyfunctional polymerizable compound having an acrylic equivalent of 150 g / eq or less and having two or more ethylenic double bonds in one molecule. It is a composition.
<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 resin particles have a volume average particle size of 30 nm to 600 nm.
<4> The active energy ray-curable composition according to any one of <1> to <3>, wherein a glass transition temperature of the resin particles is 0 ° C. or higher and 100 ° C. or lower.
<5> The active energy ray curing according to any one of <1> to <4>, wherein the polymerizable compound further contains a monofunctional polymerizable compound having one ethylenic double bond in one molecule. Mold composition.
<6> The active energy ray-curable type according to any one of <1> to <5>, wherein the monofunctional polymerizable compound has any one of an alicyclic structure, a cyclic ether structure, a pyrrolidone structure, and a caprolactam structure. It is a composition.
<7> The number of functional groups in the polyfunctional polymerizable compound is two,
The active energy ray curing according to any one of <1> to <6>, wherein the resin particles have a glass transition temperature of 25 ° C. or more and 60 ° C. or less and a volume average particle size of 100 nm or more and 300 nm or less. Mold composition.
<8> The active energy ray-curable composition according to any one of <1> to <7>, which is a three-dimensional modeling material.
<9> The active energy ray-curable composition according to any one of <1> to <8>, further including an oligomer having two or more ethylenic double bonds in one molecule.
<10> An active energy ray-curable ink comprising the active energy ray-curable composition according to any one of <1> to <9>.
<11> The active energy ray-curable ink according to <10>, which is for inkjet.
<12> A method for forming a two-dimensional or three-dimensional image, comprising an irradiation step of irradiating the active energy ray-curable composition according to any one of <1> to <9> with an active energy ray. It is.
<13> The method for forming a two-dimensional or three-dimensional image according to <12>, further including a discharge step of discharging the active energy ray-curable composition by an inkjet recording method.
<14> The method for forming a two-dimensional or three-dimensional image according to <13>, including a heating step of heating the ink before the ejection step.
<15> The method for forming a two-dimensional or three-dimensional image according to <14>, wherein the heating temperature (° C.) in the heating step and the glass transition temperature (° C.) of the resin particles satisfy the following formula (1): It is.
Heating temperature (° C.) − Glass transition temperature of resin particles (° C.) ≦ 10 ° C. Formula (1)
<16> A composition storage container, wherein the active energy ray-curable composition according to any one of <1> to <9> is stored in a container.
<17> A housing part that houses the active energy ray-curable composition according to any one of <1> to <9>,
An irradiation means for irradiating the active energy ray-curable composition with active energy rays;
Is a two-dimensional or three-dimensional image forming apparatus.
<18> The two-dimensional or three-dimensional image forming apparatus according to <17>, further including discharge means for discharging the active energy ray-curable composition by an inkjet recording method.
<19> A two-dimensional or three-dimensional image obtained by irradiating and curing the active energy ray-curable composition according to any one of <1> to <9>, with active energy rays. is there.
<20> A molded product obtained by stretching the two-dimensional or three-dimensional image according to <19>.

The active energy ray-curable composition according to any one of <1> to <9>, the active energy ray-curable ink according to any one of <10> to <11>, and the <12> to <15. The method for forming a two-dimensional or three-dimensional image according to <1>, and the apparatus for forming a two-dimensional or three-dimensional image according to <17> to <18> described above solve the above-mentioned problems and The goal is to achieve this. That is, the active energy ray curable composition, the active energy ray curable ink, the two-dimensional or three-dimensional image forming method, and the two-dimensional or three-dimensional image forming apparatus have excellent ejection stability and high hardness. Active energy ray curable composition, active energy ray curable ink, two-dimensional or three-dimensional image forming method, and two-dimensional or three-dimensional image forming device The purpose is to provide.
The composition storage container described in <16> has an object to solve the conventional problems and achieve the following object. That is, the composition storage container provides a composition storage container that contains an active energy ray-curable composition that is excellent in ejection stability, has high hardness, and has a cured shrinkage that is small. Objective.
The two-dimensional or three-dimensional image described in <19> and the molded product described in <20> solve the above-described problems and achieve the following object. That is, a two-dimensional or three-dimensional image and a molded product are obtained by curing an active energy ray-curable composition that provides a cured product that is excellent in ejection stability, has high hardness, and has little curing shrinkage. An object is to provide a three-dimensional or three-dimensional image and a molded product.

Japanese Patent No. 5606817 Japanese Patent No. 2938808 JP 2014-205839 A

  39 Image forming apparatus

Claims (19)

Containing a polymerizable compound, resin particles, and a polymerization initiator;
An active energy ray curable type, wherein the polymerizable compound contains a polyfunctional polymerizable compound having an acrylic equivalent of 150 g / eq or less and having two or more ethylenic double bonds in one molecule. Composition.   The active energy ray-curable composition according to claim 1, wherein the resin particles are acrylic resin particles.   3. The active energy ray-curable composition according to claim 1, wherein the resin particles have a volume average particle size of 30 nm to 600 nm.   4. The active energy ray-curable composition according to claim 1, wherein the resin particles have a glass transition temperature of 0 ° C. or higher and 100 ° C. or lower.   The active energy ray-curable composition according to any one of claims 1 to 4, wherein the polymerizable compound further contains a monofunctional polymerizable compound having one ethylenic double bond in one molecule.   The active energy ray-curable composition according to claim 5, wherein the monofunctional polymerizable compound has any one of an alicyclic structure, a cyclic ether structure, a pyrrolidone structure, and a caprolactam structure. The number of functional groups in the polyfunctional polymerizable compound is two;
7. The active energy ray-curable composition according to claim 1, wherein the resin particles have a glass transition temperature of 25 ° C. or more and 60 ° C. or less and a volume average particle diameter of 100 nm or more and 300 nm or less. .   The active energy ray-curable composition according to any one of claims 1 to 7, which is a three-dimensional modeling material.   An active energy ray-curable ink comprising the active energy ray-curable composition according to any one of claims 1 to 8.   The active energy ray-curable ink according to claim 9, which is used for inkjet.   A method for forming a two-dimensional or three-dimensional image, comprising an irradiation step of irradiating the active energy ray-curable composition according to claim 1 with active energy rays.   The method for forming a two-dimensional or three-dimensional image according to claim 11, further comprising a discharge step of discharging the active energy ray-curable composition by an ink jet recording method.   The two-dimensional or three-dimensional image forming method according to claim 12, further comprising a heating step of heating the ink before the ejection step. The two-dimensional or three-dimensional image forming method according to claim 13, wherein a heating temperature (° C.) in the heating step and a glass transition temperature (° C.) of the resin particles satisfy the following formula (1).
Heating temperature (° C.) − Glass transition temperature of resin particles (° C.) ≦ 10 ° C. Formula (1)   A composition storage container comprising the active energy ray-curable composition according to claim 1 in a container. An accommodating portion accommodating the active energy ray-curable composition according to any one of claims 1 to 8;
An irradiation means for irradiating the active energy ray-curable composition with active energy rays;
An apparatus for forming a two-dimensional or three-dimensional image, comprising:   The two-dimensional or three-dimensional image forming apparatus according to claim 16, further comprising ejection means for ejecting the active energy ray curable composition by an ink jet recording method.   A two-dimensional or three-dimensional image obtained by irradiating and curing the active energy ray-curable composition according to any one of claims 1 to 8 with an active energy ray.   A molded product obtained by stretching the two-dimensional or three-dimensional image according to claim 18.