JP7131116B2 - Active energy ray-curable composition, container, imaging apparatus, and imaging method - Google Patents

Description

TECHNICAL FIELD The present invention relates to an active energy ray-curable composition, a container, an imaging apparatus, and an imaging method.

An active energy ray-curable composition is ejected onto a recording medium such as a base material by an inkjet recording method or the like, and the ejected active energy ray-curable composition is polymerized by irradiating an active energy ray to obtain a cured product. It is known how to obtain

In such a method, curing in a short time is required in order to improve productivity. In addition, there is an increasing demand for post-processing such as deformation of the recording medium together with the cured product for the base material having the cured product produced by such a method. Abrasion resistance of the cured product is required. Furthermore, there is an increasing demand for imparting luster such as metallic luster to cured products. Know how to get.

Patent Document 1 discloses an image forming process in which an image is formed by ejecting an effect pigment ink containing a plate-shaped luster pigment that enhances luster onto a recording medium, and a transparent ink in which a transparent ink is applied onto the recording medium. An ink jet recording method is disclosed having an ink applying step and a curing step for curing the effect pigment ink and the clear ink on the recording medium.

However, in the case of using an active energy ray-curable composition containing a plate-like luster pigment that enhances brilliance, transparent ink or the like is applied onto the active energy ray-curable composition applied on the recording medium. When a cured product is produced without imparting a , there is a problem of abrasion resistance that the luster pigment tends to fall off when the surface of the cured product is rubbed. In addition, while solving this problem, it is difficult to simultaneously improve the adhesion of the cured product to the recording medium and improve the curing speed of the active energy ray-curable composition during the irradiation of the active energy ray. be.

The invention according to claim 1 is an active energy ray-curable composition that contains a coloring material and is cured by irradiation with an active energy ray, wherein the coloring material is a plate-shaped bright pigment and a resin chemically and wherein the resin is an actinic radiation curable composition that is a methyl methacrylate-butyl acrylate copolymer .

The active energy ray-curable composition of the present invention is excellent in scratch resistance, brilliance, and adhesion in a cured product of the active energy ray-curable composition. It has an effect of improving the curing speed.

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

Embodiments of the present invention will be described below.

[Active energy ray-curable composition]
The active energy ray-curable composition of the present embodiment is a liquid composition in which a polymerizable component in the active energy ray-curable composition is polymerized to form a cured product by irradiation with an active energy ray. , active energy ray-curable ink, and the like.
The active energy ray is not particularly limited as long as it can impart the energy necessary for promoting the polymerization reaction of the polymerizable component in the active energy ray-curable composition. Examples include ultraviolet rays, electron beams, and α. radiation, β-rays, γ-rays, X-rays and the like. Among these, ultraviolet rays are preferable. In particular, when using a high-energy light source, the polymerization reaction can proceed without using a polymerization initiator.
The active energy ray-curable composition contains a coloring material. In addition, if necessary, it contains a polymerizable monomer, a polymerizable oligomer, a polymerization initiator, an organic solvent, other components, and the like.

<<coloring material>>
The coloring material includes a composite pigment in which a plate-like luster pigment and a resin are chemically bonded. In addition, other coloring materials may be included as necessary.

<Composite pigment>
In the present embodiment, the composite pigment is a material in which a plate-like luster pigment and a resin are chemically bonded. Here, "chemically bonded" means that the bright pigment and the resin form a direct chemical bond, or indirectly through other atomic groups. Indicates that a bond is formed. In addition, "chemical bond" includes, for example, covalent bond. In addition, in the case of "indirectly forming a chemical bond through another atomic group", for example, the bright pigment and the resin form a chemical bond through a coupling agent and so on. In addition, in the case where "the bright pigment and the resin are chemically bonded", before and after the chemical bonding, part of the chemical structure of each component involved in the bonding changes. or detached. For example, some or all of the functional groups involved in chemical bonding between the bright pigment and the resin may be changed or eliminated.
Since the bright pigment and the resin are chemically bonded, the bright pigment and the resin may be separated even if a resin having a high compatibility with the polymerizable monomer is used as in the present embodiment. Suppressed. As a result, even if a plate-like bright pigment whose structure is apt to partially protrude from the surface of the cured product is used as in the present embodiment, part or all of the periphery of the bright pigment is coated with a resin. It is possible to form a cured product of the state. By partially or entirely coating the periphery of the bright pigment with a resin, the bright pigment is prevented from coming off even when the surface of the cured product is rubbed.
The term "chemically bonded" does not include the case where part or all of the luster pigment is physically coated with a resin and does not have a chemical bond. When a resin that is highly compatible with a polymerizable monomer is used without having a chemical bond between the glitter pigment and the resin, only physical coating of the glitter pigment with the resin will result in a glitter effect. The pigment and resin separate easily. Therefore, in general, when it can be observed that the bright pigment and the resin are stably present together for a long period of time in the active energy ray-curable composition, the bright pigment and the resin are chemically can be judged to have a strong bond. When the bright pigment and the resin are separated, a cured product is formed in which the bright pigment is not covered with the resin, making it difficult to prevent the bright pigment from coming off.
The composite pigment is a composite pigment in which a plate-like luster pigment and a resin are chemically bonded, but if necessary, other substances may be chemically bonded.

(Luminous pigment)
The luster pigment is not limited as long as it exhibits luster, and examples thereof include metal pigments and light interference pigments. Metal pigments include, for example, particles of aluminum, iron, copper, silver, gold, platinum, nickel, chromium, tin, zinc, indium, titanium, and the like. Light interference pigments include, for example, titanium dioxide-coated mica, iron oxide-coated mica, mixed oxide-coated mica (e.g., titanium dioxide and _{Fe2O3 -} coated mica, or particles such as mica coated with titanium dioxide and Cr ₂ O ₃ ), aluminum coated with metal oxides.
The bright pigment is preferably a metallic pigment, and more preferably particles using aluminum. Examples of the form of particles using aluminum include aluminum powder, aluminum paste, and aluminum flakes. Aluminum powder is powdered aluminum that does not contain a solvent. Aluminum paste is a material in which fine particles of aluminum are surface-treated and made into a paste with an organic solvent or the like. Aluminum flakes are materials produced by processing an aluminum deposition film or the like into thin scales. The surface of the aluminum particles may be coated with a resin material such as an acrylic resin, or an inorganic material such as silica or titanium oxide.

The shape of the luster pigment is tabular. The plate-like shape allows the bright pigment to have good light reflectivity. In the present embodiment, the term “plate shape” refers to a shape in which the area when observed from a predetermined angle (planar view) is larger than the area when observed from an angle perpendicular to the observation direction. In addition, the area S ₁ [μm ² ] when the bright pigment is observed in the direction in which the projected area is maximized (when viewed in plan) and the area when observed in the direction orthogonal to this observation direction are the maximum. The ratio (S ₁ /S ₀ ) of the area S ₀ [μm ² ] when observed from any direction is preferably 2 or more, preferably 5 or more, and preferably 8 or more. . As this value, for example, arbitrary 10 particles are observed, and an average value of values calculated for these particles can be adopted.

The average length of the longest portion of the particle diameter when the bright pigment is observed from the direction in which the projected area is maximized (when viewed from above) is preferably 0.5 μm or more and 20.0 μm or less.

The content of the bright pigment is preferably 0.1% by mass or more and 20.0% by mass or less, and 3.0% by mass or more and 9.0% by mass, based on the total amount of the active energy ray-curable composition. The following are more preferable.

(Resin chemically bonded to luster pigment)
The resin chemically bonded to the luster pigment is inert to active energy rays. In addition, the phrase "inert to active energy rays" means that the active energy ray-curable composition is not included in the above polymerizable components, and specifically, the active energy ray-curable composition is irradiated with active energy rays. It means that a polymerization reaction does not occur during the process. By making the active energy ray-curable composition contain a resin that is inactive to the active energy ray, the adhesion of the cured product to the recording medium is improved, and the active energy ray-curable composition is irradiated with the active energy ray. can improve the curing speed in In general, the inclusion of a resin that is inert to active energy rays in the active energy ray-curable composition increases the viscosity of the active energy ray-curable composition, leading to narrowing the range of applications. I don't like it because However, when the resin is chemically bonded to the bright pigment and used as a composite pigment as in the present embodiment, the increase in viscosity is suppressed. Therefore, it can be suitably used for applications requiring low viscosity, such as inkjet recording methods.

As the resin chemically bonded to the bright pigment, for example, a thermoplastic resin is preferable, and a (meth)acrylic resin can be mentioned. (Meth)acrylic resin indicates acrylic resin or methacrylic resin.
Since the resin to be chemically bonded to the bright pigment is inert to the active energy ray, the main chain should not substantially have a polymerizable functional group such as an ethylenically unsaturated double bond. preferable. Moreover, the resin preferably has an ester group in at least one side chain and has an ester group in half or more of the side chains. A resin having an ester group in its side chain has high compatibility with the polymerizable component in the active energy ray-curable composition, and high adsorptivity due to interaction with the cured product component obtained by polymerizing and curing the polymerizable component. . Therefore, the dispersion stability of the composite pigment in the active energy ray-curable composition can be improved, and the scratch resistance of the cured product can be improved. Furthermore, the resin preferably has an ester group in at least one side chain and the number of carbon atoms in the side chain is 5 or more and 10 or less, and more than half of the side chains have an ester group and More preferably, the number of carbon atoms is 5 or more and 10 or less. A resin having an ester group in a side chain and having 5 or more carbon atoms in the side chain has higher compatibility with the polymerizable component in the active energy ray-curable composition, and the polymerizable component is polymerized. Adsorptivity due to interaction with the cured product component cured by heating becomes higher. Moreover, the side chains of the resin may be linear or branched.

The weight average molecular weight of the resin is preferably 500 or more and 60000 or less.

The resin of this embodiment may be synthesized, or a commercially available resin may be used. Commercially available resins include, for example, Paraloid DM55 (manufactured by Dow Chemical Company), Paraloid DM66 (manufactured by Dow Chemical Company), Dianal BR115 (manufactured by Mitsubishi Chemical Corporation), Alfon UH-2000 (manufactured by Toagosei Co., Ltd.), and the like. mentioned.

The resin content is preferably 2.0% by mass or more and 15.0% by mass or less with respect to the total amount of the active energy ray-curable composition.

The mass ratio between the content of the bright pigment and the content of the resin (content of bright pigment/content of resin) is preferably from 1.0 to 3.0, and from 1.1 to 2.0. It is preferably 5 or less. When the ratio is within this range, even if a plate-like bright pigment whose structure is apt to partially protrude from the surface of the cured product as in the present embodiment is used, the resin sufficiently covers the periphery of the bright pigment. It is possible to form a cured product in a state where Since the periphery of the bright pigment is coated with a resin, the bright pigment is prevented from coming off even when the surface of the cured product is rubbed.

(Other resins)
Examples of resins other than the resin to be chemically bonded to the bright pigment include resins that are inert to active energy rays and do not have ester groups in side chains. Specific examples include polymers selected from polyester-based resins, polyurethane-based resins, PVC-based resins, ketone-based resins, epoxy-based resins, nitrocellulose-based resins, phenoxy-based resins, and mixtures thereof. Among these resins, commercially available resins include, for example, Elitel (manufactured by Unitika), Vylon (manufactured by Toyobo) and other polyester resins, Vylon UR (manufactured by Toyobo), NT-Hiramic (Dai Nissei Kagaku Co., Ltd.), Crisbon (Dainippon Ink and Chemicals Co., Ltd.), Nippolan (Nippon Polyurethane Co., Ltd.), and other polyurethane resins, SOLBIN (Nissin Chemical Co., Ltd.), Vinyblan (Nissin Chemical Co., Ltd.), Saran latex (manufactured by Asahi Kasei Chemicals), Sumierite (manufactured by Sumitomo Chemical Co., Ltd.), Sekisui PVC (manufactured by Sekisui Chemical Co., Ltd.), PVC resins such as UCAR (manufactured by Dow Chemical Co., Ltd.), Hilac (manufactured by Hitachi Chemical Co., Ltd.), SK Ketone resins such as (manufactured by Deguza), EPPN-201 (manufactured by Nippon Kayaku), epoxy resins such as HP-7200 (manufactured by DIC), HIG, LIG, SL, VX (manufactured by Asahi Kasei), industrial nitrocellulose resins such as nitrocellulose RS and SS (manufactured by Daicel Chemical Industries, Ltd.), and phenoxy resins such as YP-50 and YP-50S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.). Note that other resins may be synthesized.

In addition, the other resin may not be contained in the composite pigment, but when it is contained in the composite pigment, the total content of the resin and the other resin is, with respect to the total amount of the active energy ray-curable composition, It is preferably 2.0% by mass or more and 15.0% by mass or less.

(coupling agent)
A coupling agent is used as an example of means for chemically bonding the luster pigment and the resin. Even when a metal pigment or a light interference pigment is used as the luster pigment, the coupling agent can chemically bond the pigment and the resin to form a strong bond. Thereby, it is possible to suppress the separation of the metal pigment or the optical interference pigment from the resin in the active energy ray-curable composition. The type of coupling agent may be appropriately selected according to the type of metal pigment or optical interference pigment used. For example, when the surface of the luster pigment is aluminum, an aluminum coupling agent can be used. When the surface of the bright pigment is silica, a silane coupling agent can be used, and when the surface of the bright pigment is titanium oxide, a titanium coupling agent can be used.

<Other color materials>
The active energy ray-curable composition may contain other colorants in addition to the above composite pigments. Other coloring materials can be appropriately selected according to the purpose of use and required properties of the active energy ray-curable composition. Pigments and dyes are preferably used. The content of other colorants may be determined as appropriate in consideration of the desired color density and dispersibility in the composition, and is not particularly limited. ), it is preferably 0.1% by mass or more and 20% by mass or less.
As other pigments, inorganic pigments or organic pigments can be used, and they may be used singly or in combination of two or more.

Examples of inorganic pigments that can be used include carbon black (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide.

Examples of organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone. Polycyclic pigments such as pigments, dye chelates (for example, basic dye chelates, acid dye chelates, etc.), dyeing lakes (basic dye lakes, acid dye lakes), nitro pigments, nitroso pigments, aniline black, Daylight fluorescent pigments may be mentioned.

In addition, a dispersant may be further included in order to improve the dispersibility of the pigment. The dispersant is not particularly limited, but includes, for example, dispersants commonly used for preparing pigment dispersions such as polymeric dispersants.

As dyes, for example, acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and they may be used singly or in combination of two or more.

<<polymerizable monomer>>
The active energy ray-curable composition preferably contains a monofunctional monomer or a polyfunctional monomer as a polymerizable monomer, and more preferably contains a monofunctional monomer.

<Monofunctional monomer>
Monofunctional monomers having one polymerizable ethylenically unsaturated double bond that can be used in the present embodiment include, for example, 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 acrylates, ethoxydiethylene glycol acrylate, methoxydixyl ethyl acrylate, ethyl diglycol acrylate, cyclic trimethylolpropane formal monoacrylate, imide acrylate, isoamyl acrylate, 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, acryloyl Morpholine, phenoxydiethylene glycol acrylate, vinylcaprolactam, vinylpyrrolidone, 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 acrylate, octyl/decyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated (4) nylphenol acrylate, methoxypolyethylene glycol (350 ) monoacrylate, methoxy polyethylene glycol (550) monoacrylate, and the like. You may use these monofunctional monomers in combination of 2 or more types as needed. A more preferable cured film can be formed by setting the amount of the monofunctional monomer having one polymerizable ethylenically unsaturated double bond to be 80% by mass based on the total polymerizable compound.

<Polyfunctional monomer>
Polyfunctional monomers having two or more polymerizable ethylenically unsaturated double bonds that can be used in the present embodiment include, for example, hexadiol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylate, Dipropylene glycol diacrylate, tripropylene glycol triacrylate, 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-butanediol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl 1,3-propanediol diacrylate, Hydroxypivalic acid neopentyl glycol diacrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolpropane triacrylate, hydroxypivalic acid trimethylolpropane triacrylate, ethoxylated phosphoric acid triacrylate, ethoxylated tripropylene glycol diacrylate , neopentyl glycol-modified trimethylolpropane diacrylate, stearic acid-modified pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylolpropane triacrylate, tetramethylolmethane triacrylate, pentaerythritol tetraacrylate, caprolactone-modified trimethylolpropane triacrylate, propoxy late glyceryl triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, Neopentyl glycol oligoacrylate, 1,4-butanediol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate , ethoxylated neopentyl glycol di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, etc. can be, but are not limited to. These polyfunctional monomers may be used in combination of two or more as needed.

<<polymerizable oligomer>>
The active energy ray-curable composition may contain a polymerizable oligomer. Examples of polymerizable oligomers having a polymerizable ethylenically unsaturated double bond that can be used in the present embodiment include aromatic urethane oligomers, aliphatic urethane oligomers, epoxy acrylate oligomers, polyester acrylate oligomers, and other special oligomers. . Commercially available polymerizable oligomers include, for example, UV-2000B, UV-2750B, UV-3000B, UV-3010B, UV-3200B, UV-3300B, UV-3700B, UV-6640B manufactured by Nippon Chemical Synthesis Co., Ltd. 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、サートマー社製のＣＮ９０２、ＣＮ９０２Ｊ７５、ＣＮ９２９、ＣＮ９４０、ＣＮ９４４、ＣＮ９４４Ｂ８５、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、ＣＮ９８１Ｂ８８、ＣＮ９８２、ＣＮ９８２Ａ７５、ＣＮ９８２Ｂ８８、ＣＮ９８２Ｅ７５、ＣＮ９８３、ＣＮ９８４、ＣＮ９８５、ＣＮ９８５Ｂ８８、ＣＮ９８６、ＣＮ９８９、ＣＮ９９１、ＣＮ９９２、ＣＮ９９４、ＣＮ９９６、ＣＮ９９７、ＣＮ９９９、ＣＮ９００１、ＣＮ９００２、ＣＮ９００４、ＣＮ９００５、ＣＮ９００６、 ＣＮ９００７、ＣＮ９００８、ＣＮ９００９、ＣＮ９０１０、ＣＮ９０１１、ＣＮ９０１３、ＣＮ９０１８、ＣＮ９０１９、ＣＮ９０２４、ＣＮ９０２５、ＣＮ９０２６、ＣＮ９０２８、ＣＮ９０２９、ＣＮ９０３０、ＣＮ９０６０、ＣＮ９１６５、ＣＮ９１６７、ＣＮ９１７８、ＣＮ９２９０、ＣＮ９７８２、ＣＮ９７８３、ＣＮ９７８８、ＣＮ９８９３、ダイセル・サイテック社EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, KRM8200, EBECRYL5129, EBECRYL8210, EBECRYL830 1, EBECRYL8804, EBECRYL8807, EBECRYL9260, KRM7735, KRM8296, KRM8452, EBECRYL4858, EBECRYL8402, EBECRYL9270, EBECRYL8311, EBECRYL8701, etc., and these can be used in combination. Polymerizable oligomers obtained by synthesis can also be used instead of commercial products. Among polymerizable oligomers, polymerizable oligomers having 2 to 5 unsaturated carbon-carbon bonds are preferred, and polymerizable oligomers having 2 unsaturated carbon-carbon bonds are more preferred. When the number of unsaturated carbon-carbon bonds is 2 or more and 5 or less, the cured product has good stretchability.

<<polymerization initiator>>
The active energy ray-curable composition of the present embodiment may contain a polymerization initiator. Any polymerization initiator may be used as long as it can generate active species such as radicals and cations by the energy of active energy rays to initiate polymerization of polymerizable compounds (monomers and oligomers). As such polymerization initiators, known radical polymerization initiators, cationic polymerization initiators, base generators and the like can be used singly or in combination of two or more. Among them, radical polymerization initiators are used. is preferred. Also, in order to obtain a sufficient curing speed, the polymerization initiator is preferably contained in an amount of 5 to 20% by mass with respect to the total mass (100% by mass) of the composition.
Examples of radical polymerization initiators include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, Examples include ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds.
Moreover, in addition to the polymerization initiator, a polymerization accelerator (sensitizer) can be used in combination. Examples of the polymerization accelerator include, but are not limited to, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, N, Amine compounds such as N-dimethylbenzylamine and 4,4'-bis(diethylamino)benzophenone are preferred, and the content thereof may be appropriately set according to the polymerization initiator to be used and its amount.

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

<<Other Ingredients>>
The active energy ray-curable composition of the present embodiment may contain other known components as necessary. Other components include, but are not particularly limited to, conventionally known surfactants, polymerization inhibitors, leveling agents, antifoaming agents, fluorescent whitening agents, penetration accelerators, humectants (humectants), fixing agents, Viscosity stabilizers, antifungal agents, preservatives, antioxidants, ultraviolet absorbers, chelating agents, pH adjusters, thickeners, and the like.

<<Preparation of active energy ray-curable composition>>
The active energy ray-curable composition of the present embodiment can be produced using the various components described above, and the preparation means and conditions are not particularly limited. , kitty mill, disk mill, pin mill, dyno mill, etc., and disperse to prepare a pigment dispersion, and further add a polymerizable monomer, an initiator, a polymerization inhibitor, a surfactant, etc. to the pigment dispersion. It can be prepared by mixing.

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

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

[Container]
The storage container of the present embodiment means a container in which the active energy ray-curable composition is stored, and is suitable for the above uses. For example, when the active energy ray-curable composition of the present embodiment is used for ink, the container containing the ink can be used as an ink cartridge or an ink bottle. In such operations, there is no need to directly touch the ink, and fingers and clothes can be prevented from getting dirty. In addition, it is possible to prevent foreign matter such as dust from entering the ink. The shape, size, material, etc. of the container itself are not particularly limited as long as they are suitable for the application and usage. should be covered with a protective sheet or the like.

[Image Forming Method, Image Forming Apparatus]
The image forming method of the present embodiment has an irradiation step of irradiating an active energy ray in order to cure the active energy ray-curable composition with the active energy ray. and a container for containing the active energy ray-curable composition of the present embodiment, and the container may be contained in the container. Furthermore, it may have a discharge step and discharge means for discharging the active energy ray-curable composition. The method of discharging is not particularly limited, but examples include a continuous injection type, an on-demand type, and the like. The on-demand type includes a piezo system, a thermal system, an electrostatic system, and the like.
FIG. 1 shows an example of an image forming apparatus equipped with an inkjet ejection means. Ink is ejected onto the recording medium 22 supplied from the supply roll 21 by the respective color printing units 23a, 23b, 23c, and 23d, which are provided with ink cartridges and ejection heads for active energy ray-curable inks of yellow, magenta, cyan, and black. be done. After that, the light sources 24a, 24b, 24c, and 24d for curing the ink are irradiated with active energy rays to cure the ink, thereby forming a color image. After that, the recording medium 22 is conveyed to the processing unit 25 and the print take-up roll 26 . A heating mechanism may be provided in each of the printing units 23a, 23b, 23c, and 23d so that the ink is liquefied at the ink discharge section. Further, if necessary, a mechanism may be provided for cooling the recording medium to about room temperature by contact or non-contact. Inkjet recording methods include a serial method in which a head is moved to eject ink onto a recording medium that moves intermittently according to the width of an ejection head, and a serial method in which ink is ejected onto a recording medium by moving the recording medium continuously. Any line system in which ink is ejected onto a recording medium from a head held at a fixed position can be applied.
It should be noted that the image forming method of the present embodiment does not need to have means for applying transparent ink or the like onto the active energy ray-curable composition applied onto the recording medium. Composite pigments in which plate-shaped bright pigments and resins are chemically bonded are used as the coloring material, so even when the surface of a cured product that does not have a transparent ink layer is rubbed, the bright pigments are prevented from falling off. This is because
The recording medium 22 is not particularly limited, but includes paper, film, ceramics, glass, metal, composite materials thereof, and the like, and may be in the form of a sheet. Further, the configuration may be such that only single-sided printing is possible, or that double-sided printing is also possible. Not limited to those used as general recording media, corrugated cardboard, building materials such as wallpaper and flooring, concrete, cloth for clothing such as T-shirts, textiles, leather, and the like can be used as appropriate.
Furthermore, the active energy ray irradiation from the light sources 24a, 24b, and 24c may be weakened or omitted, and after printing a plurality of colors, the active energy ray may be irradiated from the light source 24d. Thereby, energy saving and cost reduction can be achieved.
The recorded matter to be recorded with the ink of the present embodiment is not limited to ordinary paper or resin film printed on a smooth surface. It also includes those printed on a printing surface made of various materials. In addition, by layering two-dimensional images, it is possible to form an image (an image consisting of two-dimensional and three-dimensional images) or a three-dimensional object with a partial three-dimensional effect.

FIG. 2 is a schematic diagram showing an example of another image forming apparatus (three-dimensional stereoscopic image forming apparatus). The image forming apparatus 39 in FIG. 2 uses a head unit (movable in the AB direction) in which inkjet heads are arranged, and ejects the first active energy ray-curable composition from the ejection head unit 30 for a modeled object. A second active energy ray-curable composition having a composition different from that of the first active energy ray-curable composition is ejected from the head units 31 and 32, and these compositions are cured by adjacent ultraviolet irradiation means 33 and 34. It is laminated while doing so. More specifically, for example, the second active energy ray-curable composition is ejected from the support ejection head units 31 and 32 onto the shaped object support substrate 37, and is irradiated with an active energy ray to be solidified. After forming the first support layer having a reservoir, the first active energy ray-curable composition is discharged from the discharge head unit 30 for a modeled object into the reservoir, and is irradiated with an active energy ray to be solidified. By repeating the step of forming the first model layer by pressing the support layer and the model layer a plurality of times while lowering the vertically movable stage 38 according to the number of layers, the support layer and the model layer are laminated to form the three-dimensional model 35 . to manufacture. After that, the support laminate 36 is removed as needed. In FIG. 2, only one ejection head unit 30 for a modeled object is provided, but two or more may be provided.

Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Preparation of composite pigment dispersion>
(Preparation of Composite Pigment Dispersion 1)
After mixing each of the following materials, they were stirred for 3 minutes (1,000 to 1,500 rpm) with a mixer manufactured by SILVERSON to obtain a uniform pre-dispersion liquid 1. The resulting pre-dispersion liquid was subjected to dispersion treatment using an ultrasonic dispersing machine (manufactured by AS ONE Co., Ltd., ultrasonic washing machine VS-150) for a dispersion time of 8 hours to prepare a glitter pigment dispersion liquid 1. Next, the volume average particle size and particle size distribution of the bright pigment were measured using Nanotrac WAVE II manufactured by Microtrack. The 50% average particle size of this bright pigment was 15 μm.
・ Isopropyl alcohol dispersion of flat aluminum particles (solid content: 20% by mass, trade name: METALURE W-52012 IL, manufactured by ECKART) 50.0 parts ・ Acidic dispersant (trade name: Solsperse 36000, manufactured by Luburizol) 10.0 parts by mass Isopropyl alcohol 40.0 parts by mass

Next, after mixing each of the following materials, they were stirred for 3 minutes (1,000 to 1,500 rpm) with a mixer manufactured by SILVERSON, and subjected to evaporator treatment until the mass reached 20% by mass of the initial mass to remove isopropanol. A composite pigment dispersion liquid 1 was obtained in which a composite pigment in which the luster pigment and the resin were chemically bonded was dispersed.
・Effective pigment dispersion liquid 1 65.0 parts by mass ・Aluminum coupling agent (trade name: PLENACT AL-M, manufactured by Ajinomoto Fine-Techno Co., Ltd.) 0.1 parts by mass ・Methyl methacrylate-butyl acrylate copolymer (side chain : straight chain, side chain carbon number: 2 or 5, weight average molecular weight (Mw): 6000, trade name: Paraloid DM55, Dow Chemical Company) 4.0 parts by mass

(Preparation of Composite Pigment Dispersion Liquid 2)
In the preparation of composite pigment dispersion liquid 1, "methyl methacrylate-butyl acrylate copolymer" was replaced with "polyisobutyl methacrylate (side chain: branched, number of carbon atoms in side chain: 5, weight average molecular weight (Mw): 55000, product A composite pigment dispersion 2 was obtained in the same manner, except that the name was changed to DIANAL BR115, manufactured by Mitsubishi Chemical Corporation).

(Preparation of Composite Pigment Dispersion 3)
In the preparation of composite pigment dispersion liquid 1, "methyl methacrylate-butyl acrylate copolymer" was replaced with "acrylic polymer (side chain: straight chain, number of carbon atoms in side chain: 2, weight average molecular weight (Mw): 11000, trade name: Alfon UH-2000, manufactured by Toa Gosei Co., Ltd.)” was used to obtain Composite Pigment Dispersion 3 in the same manner.

(Preparation of Composite Pigment Dispersion 4)
In the preparation of composite pigment dispersion 1, "methyl methacrylate-butyl acrylate copolymer" was replaced with "methyl methacrylate-butyl methacrylate copolymer (side chain: straight chain, number of carbon atoms in side chain: 2 or 5, weight average molecular weight ( Mw): 70000, trade name: Paraloid DM66, manufactured by The Dow Chemical Company)”, and a composite pigment dispersion 4 was obtained in the same manner.

(Preparation of Composite Pigment Dispersion Liquid 5)
In the preparation of Composite Pigment Dispersion 1, the "isopropyl alcohol dispersion of tabular aluminum particles" was changed to the "isopropyl alcohol dispersion of tabular aluminum particles coated with silica" prepared by the following method, and further " Composite Pigment Dispersion Liquid 5 was obtained in the same manner except that "aluminum coupling agent" was changed to "silane coupling agent (trade name: KBM 503, manufactured by Shin-Etsu Silicone Co., Ltd.)". The 50% average particle size of the bright pigment when the bright pigment dispersion 5 was prepared in the same manner as the bright pigment dispersion 1 was 12 μm.

-Isopropyl Alcohol Dispersion of Silica-Coated Tabular Aluminum Particles-
Silica-coated tabular aluminum particles (volume average particle size: 20 μm, trade name: CHROMASHINE CRS-GD20, manufactured by Toyo Aluminum Co., Ltd.) were diluted with isopropyl alcohol so that the solid content concentration was 20% by mass, and Dispersion treatment was performed for 3 hours using a sonic disperser (manufactured by AS ONE Co., Ltd., ultrasonic cleaner VS-150) to obtain an isopropyl alcohol dispersion of flat aluminum particles coated with silica.

(Preparation of Composite Pigment Dispersion 6)
In the preparation of Composite Pigment Dispersion 1, the "isopropyl alcohol dispersion of flat aluminum particles" was changed to "isopropyl alcohol dispersion of flat mica particles coated with titanium oxide" prepared by the following method, and A composite pigment dispersion 6 was obtained in the same manner except that the “aluminum coupling agent” was changed to “titanium coupling agent (trade name: ORGATICS TC-510, manufactured by Matsumoto Fine Chemicals Co., Ltd.)”. The 50% average particle size of the bright pigment when the bright pigment dispersion 6 was prepared in the same manner as the bright pigment dispersion 1 was 13 μm.

-Isopropyl alcohol dispersion of flat mica particles coated with titanium oxide-
Titanium oxide-coated flat mica particles (trade name: Pearl Graze MM-100, manufactured by Merck Performance Materials) were diluted with isopropyl alcohol to a solid content concentration of 20% by mass, and dispersed in an ultrasonic disperser ( Dispersion treatment was performed for 3 hours using an ultrasonic cleaner VS-150 manufactured by AS ONE Co., Ltd. to obtain an isopropyl alcohol dispersion of flat mica particles coated with titanium oxide.

(Preparation of Composite Pigment Dispersion 7)
After mixing each of the following materials, they were stirred for 3 minutes in a SILVERSON mixer (1,000 to 1,500 rpm), and subjected to evaporator treatment until the mass reached 20% by mass of the initial mass to remove isopropanol, and composite. A pigment dispersion 7 was obtained.
・Effective pigment dispersion 1 30.0 parts by weight ・Effective pigment dispersion 5 35.0 parts by weight ・Aluminum-based coupling agent (trade name: PLENACT AL-M, manufactured by Ajinomoto Fine-Techno Co., Ltd.) 0.05 parts by weight・ Silane coupling agent (trade name: KBM 503, manufactured by Shin-Etsu Silicone Co., Ltd.) 0.05 parts by mass ・ Methyl methacrylate - butyl acrylate copolymer (side chain: straight chain, number of carbon atoms in side chain: 2 or 5, weight average Molecular weight (Mw): 6000, trade name: Paraloid DM55, Dow Chemical Company) 4.0 parts by mass

(Preparation of Composite Pigment Dispersion 8)
In the preparation of composite pigment dispersion liquid 1, "methyl methacrylate-butyl acrylate copolymer" was replaced with "polyester resin (side chain: none, weight average molecular weight (Mw): 20000, trade name: GA-1310, manufactured by Mitsubishi Chemical Corporation )”, a composite pigment dispersion 8 was obtained in the same manner.

(Preparation of Composite Pigment Dispersion Liquid 9)
Composite pigment dispersion 9 was obtained in the same manner as in preparation of composite pigment dispersion 1, except that the “aluminum-based coupling agent” was not used.

(Preparation of composite pigment dispersions 10 to 13)
Composite Pigment Dispersions 10 to 13 were obtained in the same manner as in the preparation of Composite Pigment Dispersion 1, except that the amount of each material used was changed to the amount shown in Table 1 below.

Table 1 below shows the combination and amount of each material used in the preparation of the composite pigment dispersion. The unit of each number in Table 1 below is "parts by mass".

<Preparation of active energy ray-curable composition>
(Example 1)
Next, the following materials were sequentially added and stirred. After stirring for 1 hour, it was confirmed that there was no undissolved residue, and coarse particles were removed by filtering with a membrane filter to prepare an active energy ray-curable composition of Example 1.
・Tetrahydrofurfuryl acrylate (trade name: Viscoat #150, manufactured by Osaka Organic Industry Co., Ltd.) 70.0 parts by mass ・1,3-butylene glycol diacrylate (trade name: SR212, manufactured by Sartomer) 4.0 parts by mass ・Polyester -based urethane acrylate oligomer (trade name: Shikou UV-3010B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 4.0 parts by mass Composite pigment dispersion liquid 1 10.6 parts by mass 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184, manufactured by BASF) 6.0 parts by mass 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1- On (trade name: LUCIRIN TPO, manufactured by BASF) 4.0 parts by mass 2,4-diethylthioxanthone (KAYACURE DETX-S: manufactured by Nippon Kayaku Co., Ltd.) 1.4 parts by mass

(Examples 2-12, Comparative Examples 1-3)
The combination and addition amount of each material used in the preparation of the active energy ray-curable composition of Example 1 were changed to the combinations and addition amounts shown in Table 2 below, and Examples 2 to 12 and Comparative Examples 1 to 3 were obtained. An active energy ray-curable composition was produced. The unit of each number in Table 2 is "parts by mass".

In addition, in the above Table 2, the product names of materials and the names of manufacturers are as follows.
・Phenoxyethyl acrylate (trade name: SR339, manufactured by Sartomer)
・Dipropylene glycol diacrylate (trade name: SR508, manufactured by Arkema)
・Methyl methacrylate-butyl acrylate copolymer (trade name: Paraloid DM55, manufactured by Dow Chemical Company)

Next, using the active energy ray-curable composition of each example and each comparative example, according to the methods and evaluation criteria shown below, the scratch resistance, glitter, Also, the adhesiveness and the curing speed of the active energy ray-curable composition during the irradiation of the active energy ray were evaluated. The evaluation results are shown in Table 3 below.

[Scratch resistance]
A printer (apparatus: SG7100 modified A solid image of 10 cm×10 cm was formed using a printer for evaluation (manufactured by Ricoh Co., Ltd.). A UV-LED device for an inkjet printer (device name: UV-LED module (single-pass water-cooled, manufactured by Ushio Inc.)) was used for the obtained solid image with an illuminance of 1 W/cm ² and an irradiation amount of 500 mJ. A curing treatment was performed by irradiating ultraviolet rays so as to obtain an image (cured product) of ¹⁰ cm×10 cm with an average thickness of 10 μm.
The irradiation dose was measured using an ultraviolet intensity meter (apparatus name: UM-10, manufactured by Konica Minolta, Inc.) and a light receiving unit (apparatus name: UM-400, manufactured by Konica Minolta, Inc.). The average thickness was measured using an electronic micrometer (manufactured by Anritsu Co., Ltd.), and the average thickness at 10 points was obtained. In addition, the printer for evaluation used an SG7100 (manufactured by Ricoh Co., Ltd.) conveying and driving section, and the head section was changed to an MH2620 head (manufactured by Ricoh Co., Ltd.) capable of thermal ejection and capable of handling high-viscosity ink.

The resulting image (cured product) was rubbed back and forth 10 times with a white cotton cloth attached to a crockmeter (apparatus name: NO416, manufactured by Yasuda Seiki Seisakusho Co., Ltd.) under a load of 50 g/cm ² . After that, using a reflection spectral densitometer (device name: X-Rite 939, manufactured by X-Rite), the density of the white cotton cloth before and after reciprocating friction is measured, and the density before reciprocating friction is subtracted from the density after reciprocating friction. The value was calculated, and the "scratch resistance" was evaluated based on the following evaluation criteria. When the evaluation was B or higher, it was judged to be practicable.
-Evaluation criteria-
A: The value obtained by subtracting the density before reciprocating friction from the density after reciprocating friction is 0.001 or less. B: The value obtained by subtracting the density before reciprocating friction from the density after reciprocating friction is greater than 0.001 and 0.005. C: The value obtained by subtracting the density before reciprocating friction from the density after reciprocating friction is greater than 0.005 and 0.009 or less D: The value obtained by subtracting the density before reciprocating friction from the density after reciprocating friction greater than 0.009

[Brightness]
First, a cured product was obtained in the same procedure as in the evaluation of scratch resistance. Next, the glossiness of the cured product at 20° was measured using a micro-trigloss gloss meter manufactured by BYK Gardner, and the glossiness (specular gloss) was evaluated according to the following evaluation criteria. When the evaluation was B or higher, it was judged to be practicable.
-Evaluation criteria-
A: The glossiness is 600 or more B: The glossiness is 400 or more and less than 600 C: The glossiness is 200 or more and less than 400 D: The glossiness is less than 200

[Adhesion]
First, a cured product was obtained in the same procedure as in the evaluation of scratch resistance. Next, the adhesiveness of the resulting cured product was evaluated according to the following evaluation criteria in accordance with the JIS K5400 cross-cut test (old standard). When the evaluation was B or higher, it was judged to be practicable. In addition, when the adhesion is 100, it means that none of the 100 pieces of the grid portion are peeled off. When the adhesion is 80, it means that the area of the unpeeled portion is 80%.
-Evaluation criteria-
A: Adhesion is 95 or more and 100 or less B: Adhesion is 90 or more and less than 95 C: Adhesion is 80 or more and less than 90 D: Adhesion is less than 80

[Curing speed]
First, a solid image before curing was obtained in the same procedure as in the evaluation of scratch resistance. Next, a UV-LED device for inkjet printers (device name: UV-LED module (single-pass water-cooled, manufactured by Ushio Inc.)) is used to irradiate the solid image with ultraviolet rays to make the solid image into a non-tacky cured product. The amount of irradiation (mJ/cm ² ) required for this was measured, and the "curing speed" was evaluated based on the following evaluation criteria. When the evaluation was B or higher, it was judged to be practicable.
-Evaluation criteria-
A: The irradiation dose is 0 mJ/cm ² or more and less than 200 mJ/cm ² B: The irradiation dose is 200 mJ/cm ² or more and less than 300 mJ/cm ² C: The irradiation dose is 300 mJ/cm ² or more and less than 400 mJ/cm ² Yes D: The irradiation dose is 400 mJ/cm ² or more

39 image forming apparatus

JP 2012-210764 A

Claims (9)

An active energy ray-curable composition containing a coloring material and cured by irradiation with an active energy ray,
The coloring material includes a composite pigment in which a plate-like luster pigment and a resin are chemically bonded,
The active energy ray-curable composition, wherein the resin is a methyl methacrylate-butyl acrylate copolymer . 2. The active energy ray-curable composition according to claim 1, wherein in the composite pigment, the photoluminescent pigment and the resin are chemically bonded via a coupling agent. 3. The active energy ray-curable composition according to claim 2, wherein the coupling agent is at least one selected from silane coupling agents, titanium coupling agents, and aluminum coupling agents. The active energy ray-curable composition according to any one of claims 1 to 3 , wherein the resin has a weight average molecular weight of 500 or more and 60000 or less. The active energy ray-curable composition according to any one of claims 1 to 4 , wherein the resin is contained in an amount of 2.0% by mass or more and 15.0% by mass or less with respect to the total amount of the active energy ray-curable composition. Composition. 6. The method according to any one of claims 1 to 5 , wherein a mass ratio of the content of the bright pigment and the content of the resin (content of the bright pigment/content of the resin) is 1.0 or more and 3.0 or less. The active energy ray-curable composition according to any one of the items. A container containing the active energy ray-curable composition according to any one of claims 1 to 6 . 8. The storage container according to claim 7 , a discharging means for discharging the active energy ray-curable composition contained in the storage container, and the active energy ray-curable composition for the discharged active energy ray-curable composition. illuminating means for illuminating a line. A discharge step of discharging the active energy ray-curable composition according to any one of claims 1 to 6 , and irradiation of irradiating the discharged active energy ray-curable composition with the active energy ray and an imaging method comprising the steps of:

Images