JP2020152800A - Curable composition, printed matter, adhesive label, housing container, method and device for forming two-dimensional or three-dimensional image, cured article, structure, and molding processed article - Google Patents

Abstract

To provide a curable composition having excellent water discoloration resistance, water adhesion resistance, laminate adhesion property, and substrate adhesiveness.SOLUTION: There is provided a curable composition containing a polymerizable monomer consisting of a monofunctional monomer and a polyfunctional monomer, and a polymerization initiator, the polymerization initiator being an α-amino alkylphenone compound, the content of the polymerization initiator being 1 mass% or more and 3 mass% or less.SELECTED DRAWING: None

Description

The present invention relates to a curable composition, a printed matter, an adhesive label, a container, a method and an apparatus for forming a two-dimensional or three-dimensional image, a cured product, a structure, and a molded product.

In recent years, the applications of active energy ray-curable inks have expanded, and the obtained cured films have been used for various purposes, and those having a cured film whose characteristics do not easily change even in a harsh environment are desired. In particular, in applications such as those used in a high humidity environment or an environment exposed to moisture, it is difficult to suppress deterioration of the cured film because the cured film is impregnated with moisture.

Therefore, in order to improve the water resistance of the cured film, for example, an ultraviolet curable ink containing an amine-modified acrylate and caprolactone-modified tris- (2-acryloxyethyl) isocyanurate) has been proposed (for example, Patent Documents). 1).
Further, an ultraviolet curable ink containing a polycyclic epoxy compound has been proposed (see, for example, Patent Document 2).

Further, in order to reduce contact with water, for example, it has been proposed to laminate the surface of the cured film (see, for example, Patent Document 3). Further, it has been proposed to form a laminate protective layer on the surface of the cured film (see, for example, Patent Document 4).

Further, in order to improve the flexibility of the cured film, for example, a glass transition temperature (Tg) selected from (A) dipropylene glycol diacrylate, (B) N-vinylcaprolactam, (C) lauryl acrylate and ethoxyethoxyethyl acrylate. ) Has been proposed as an inkjet ink composed of a monofunctional acrylic monomer having a temperature of less than 20 ° C. (see, for example, Patent Document 5).

An object of the present invention is to provide a curable composition having excellent water discoloration resistance, water adhesion resistance, laminate adhesion, and substrate adhesion.

The curable composition of the present invention as a means for solving the above-mentioned problems is a curable composition containing a polymerizable monomer containing a monofunctional monomer and a polyfunctional monomer, and a polymerization initiator. The polymerization initiator is an α-aminoalkylphenone compound, and the content of the polymerization initiator is 1.0% by mass or more and 3% by mass or less.

According to the present invention, it is possible to provide a curable composition having excellent water discoloration resistance, water adhesion resistance, laminate adhesion, and substrate adhesion.

FIG. 1 is a schematic view showing an example (two-dimensional stereoscopic image manufacturing apparatus) of an image forming apparatus provided with an inkjet ejection means. FIG. 2 is a schematic view showing an example (three-dimensional stereoscopic image manufacturing apparatus) of an image forming apparatus provided with an inkjet ejection means. FIG. 3 is a schematic view showing another example of the image forming apparatus (three-dimensional stereoscopic image manufacturing apparatus). FIG. 4 is a sample adhesion rank of JIS-K5600. FIG. 5 is a model diagram when the cured film is laminated. FIG. 6 is a model diagram when the cured film is used as an adhesive label on a transparent substrate. FIG. 7 is a model diagram when the cured film is printed on a transparent base material and used as an adhesive label on an opaque base material. FIG. 8 is a model diagram in the case where the cured film is manufactured as an adhesive label, the back surface is coated with a water-repellent or oil-repellent material, and the film is wound up without the need for release paper.

(Curing composition)
The curable composition of the present invention is a curable composition containing a polymerizable monomer containing a monofunctional monomer and a polyfunctional monomer and a polymerization initiator, wherein the polymerization initiator is an α-aminoalkylphenone compound. The content of the polymerization initiator is 1.0% by mass or more and 3% by mass or less, and further contains other components as necessary.

In the prior art documents described in Patent Documents 1 and 2, the color of the printed layer is changed due to water content, and the adhesion between the base material and the cured film is lowered, so that sufficiently satisfactory characteristics are obtained. I haven't been able to.
Further, in the prior art documents described in Patent Documents 3 and 4, it is difficult to completely waterproof the cured film even if it is laminated, and discoloration of the cured film cannot be prevented unless the cured film itself retains water resistance to some extent or more. In addition, the adhesion strength between the cured film and the laminated layer could not be sufficiently increased.
Further, in the prior art document described in Patent Document 5, the flexibility of the cured film is improved by containing an acrylic monomer having a glass transition temperature (Tg) of less than 20 ° C., but water resistance and laminate adhesion are improved. It is not optimized for its properties, substrate adhesion, and use as an adhesive label, and it is not possible to obtain sufficiently satisfactory characteristics.
Therefore, in the prior art, it is difficult to obtain a curable composition having excellent water discoloration resistance, water adhesion resistance, laminate adhesion, and substrate adhesion.

<Polymerization initiator>
The present invention is characterized in that the polymerization initiator is an α-aminoalkylphenone compound and is contained in an amount of 1.0% by mass or more and 3% by mass or less with respect to the total amount of the curable composition.
When the α-aminoalkylphenon compound is used as the polymerization initiator and its content is 1.0% by mass or more and 3% by mass or less, the unreacted initiator that lowers the water resistance and its residue can be controlled and cured. Since the weight average molecular weight of the film can be increased, the water resistance can be improved.
When the content of the α-aminoalkylphenone compound is more than 3% by mass, a large amount of decomposition products of the polymerization initiator and unreacted polymerization initiator remain in the cured film, which lowers the water resistance. The cured film becomes a resin film with a high molecular weight integrated by the polymerization reaction of the monomer and the oligomer, but since the polymerization initiator and its decomposition products are not integrated with the cured film, the water resistance is lowered.
Further, when the content of the α-aminoalkylphenon compound is more than 3% by mass, the number of reaction sites of the monomer and the oligomer increases, the film becomes a cured film having a low molecular weight, and the water resistance is lowered. Further, when it is 1.0% by mass or less, the reactivity is lowered and the curability is lowered.

The polymerization initiator needs to have a function of generating active species such as radicals and cations by energy and initiating the polymerization of polymerizable compounds (polyfunctional monomer, monofunctional monomer, and polymerizable oligomer). The α-aminoalkylphenon compound is a polymerization initiator having extremely high reactivity and having high efficacy in a system containing a pigment. It is excellent in thin film curability and surface curability, and has an advantage that the curability does not decrease even if the content of the polymerization initiator is 1.0% by mass or more and 3% by mass or less as in the present invention.

Examples of the α-aminoalkylphenyl compound include 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name:). IRGACURE379, manufactured by BASF, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE369, manufactured by BASF), 2-methyl-1- [4-( Methylthio) phenyl] -2-morpholinopropane-1-one (trade name: IRGACURE907, manufactured by BASF) and the like can be mentioned.

Since the polymerization initiator has a great feature in the UV spectrum depending on the type, analysis by HPLC using a PDA (photodiode array) detector or LC / FT-MS (liquid chromatography /) using an LC UV detector By performing an electric field type Fourier transform mass spectrometer), these types and quantities can be specified.
When the cured film was immersed in warm water at 40 ° C. for 1 day and the color characteristics were evaluated immediately after taking out, the cured composition of the present invention has high water resistance, so that the color characteristics hardly change. The curable composition having poor water resistance greatly changes its color characteristics. Further, since the curable composition having poor water resistance contains water in the cured film or at the interface of the base material, the adhesion is lowered.

In addition to the polymerization initiator, a polymerization accelerator can also be used in combination.
The polymerization accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethyl p-dimethylaminobenzoate, -2-ethylhexyl p-dimethylaminobenzoate, p-dimethylaminobenzoic acid. Examples thereof include amine compounds such as methyl, -2-dimethylaminoethyl benzoate, and butoxyethyl p-dimethylaminobenzoate. These may be used alone or in combination of two or more.

<Polymerization inhibitor>
In the present invention, the content of the polymerization inhibitor is preferably 0.10% by mass or less. Since the polymerization inhibitor is contained in the polymerizable monomer at several hundred ppm, the polymerization inhibitor contained in the polymerizable monomer is used to maintain the storage stability without prescribing the polymerization inhibitor in the formulation of the curable composition. Is preferable.
When the content of the polymerization inhibitor is 0.10% by mass or less, curability is not impaired even if the content of the polymerization initiator is 1% by mass or more and 3% by mass or less. Further, the polymerization inhibitor itself causes a factor of lowering the water resistance, so it is preferable that the amount is small. Further, by controlling the content of the polymerization inhibitor within the above range, the weight average molecular weight of the cured film becomes high, so that the water resistance can be improved.

As described above, in the present invention, it is preferable that the polymerization inhibitor exerts the polymerization inhibitory effect in an amount previously contained in the polymerizable monomer and is not added as a formulation of the curable composition, but the curable composition When added to the formulation, the polymerization inhibitors include, for example, 4-methoxy-1-naphthol, methylhydroquinone, hydroquinone, t-butylhydroquinone, di-t-butylhydroquinone, methquinone, 2,2'-dihydroxy-3. , 3'-di (α-methylcyclohexyl) -5,5'-dimethyldiphenylmethane, p-benzoquinone, di-t-butyldiphenylamine, 9,10-di-n-butoxycyantrasen, 4,4'-[1 , 10-Dioxo-1,10-decandylbis (oxy)] bis [2,2,6,6-tetramethyl] -1-piperidinyloxy, p-methoxyphenol, 2,6-di-tert-butyl- Examples thereof include p-cresol.

The content of the polymerization inhibitor in the curable composition can be determined by, for example, a method using GPC (gel permeation chromatography), a polar graph method, an analysis by HPLC using a PDA (photodiode array) detector, or LC. It can be quantified by LC / FT-MS (liquid chromatography / electric field type Fourier transform mass spectrometer) using a UV detector or the like.

The curable composition of the present invention has few unreacted products and decomposition products of the polymerization initiator, and the content of the polymerization inhibitor is less than the specified amount. Therefore, there are few materials that impair the integration of the cured film and the water resistance is high. .. Therefore, the intrusion of water into the cured film is reduced and discoloration can be prevented. As a result, it is suitable for products such as automobile exterior paints, adhesive labels, home appliances, and adhesive tapes with patterns that require a high level of water resistance.

Examples of the curable composition of the present invention include a thermosetting composition and an active energy ray-curable composition, but an active energy ray-curable composition is more preferable.

<Polymerizable compound>
Examples of the polymerizable compound include a polymerizable monomer containing a monofunctional monomer and a polyfunctional monomer, and a polymerizable oligomer.

The SP value of the polymerizable monomer is preferably 7 (cal / cm ³ ) ^0.5 or more and 11 (cal / cm ³ ) ^0.5 or less, and 8.5 (cal / cm ³ ) ^0.5 or more and 10.5 ( cal / cm ³ ) ^0.5 or less is more preferable. The SP value is a value obtained by the Fedors method, and means that the SP value of each monomer contained in the polymerizable monomer is the SP value in the above numerical range.
When the SP value of the polymerizable monomer is 7 (cal / cm ³ ) ^0.5 or more and 11 (cal / cm ³ ) ^0.5 or less, the dispersion between the polymerizable monomer and the pigment becomes good, and the water resistance of the cured film is improved. Is improved. If the SP value of the polymerizable monomer is smaller than 7 (cal / cm ³ ) ^0.5 , dispersibility with the pigment may become difficult, or the solubility of the polymerization initiator and the polymerization inhibitor may decrease. Further, when the SP value is larger than 11 (cal / cm ³ ) ^0.5 , the hydrophilicity of the cured film is increased, and the water resistance of the cured film may be lowered.

− Monofunctional monomer −
Examples of the monofunctional monomer include benzyl acrylate (BzA, SP value: 10.1 (cal / cm ³ ) ^0.5 ), benzyl methacrylate, and phenoxyethyl acrylate (PEA, SP value: 10.1 (cal / cm ³ ) ³ ). ) ^0.5 ), Phenoxyethyl methacrylate, formalized trimethylolpropane (TMP) monoacrylate (SP value: 9.5 (cal / cm ³ ) ^0.5 ), formalized trimethylrolpropane (TMP) monomethacrylate, stearyl Acrylate (STA, SP value: 8.7 (cal / cm ³ ) ^0.5 ), stearyl methacrylate, cyclohexyl acrylate (CHA, SP value: 9.6 (cal / cm ³ ) ^0.5 ), cyclohexyl methacrylate, lauryl Acrylate (LA, SP value: 8.9 (cal / cm ³ ) ^0.5 ), lauryl methacrylate, tetrahydrofurfuryl acrylate (THFA, SP value: 9.4 (cal / cm ³ ) ^0.5 ), tetrahydroful Frill methacrylate, isobornyl acrylate (IBXA, SP value: 8.7 (cal / cm ³ ) ^0.5 ), isobornyl methacrylate, isoamyl acrylate (IAA, SP value: 9.0 (cal / cm ³ ) ⁰ ) ^.5 ) Isoamyl methacrylate, cyclic trimethylolpropaneformal acrylate (CTFA, SP value: 9.5 (cal / cm ³ ) ^0.5 ), cyclic trimethylolpropaneformal methacrylate, acryloylmorpholin (SP value: 11.2 (SP value: 11.2 cal / cm ³ ) ^0.5 ), metaacryloylmorpholine, 4-hydroxybutyl acrylate (SP value: 11.8 (cal / cm ³ ) ^0.5 ), 4-hydroxybutyl methacrylate, N-vinyl caprolactam (SP) Values: 10.8 (cal / cm ³ ) ^0.5 ) and the like.
These may be used alone or in combination of two or more.
Among these, benzyl acrylate, cyclohexyl acrylate, and cyclic trimethylolpropane formal acrylate are preferable because they have a ring structure and the strength of the cured film is increased.

-Polyfunctional monomer-
Examples of the polyfunctional monomer include 1,6-hexanediol diacrylate (1,6 HDDA, SP value: 10.0 (cal / cm ³ ) ^0.5 ), 1,6-hexanediol dimethacrylate, 1,9. -Nonandiol diacrylate (1,9NDDA, SP value: 9.8 (cal / cm ³ ) ^0.5 ), 1,9-Nonandiol dimethacrylate, diethylene glycol diallylate (SP value: 9.8 (cal / cm)) ³ ) ^0.5 ), Diethylene glycol dimetallicate, Dipropylene glycol diacrylate (PEDDA, SP value: 10.1 (cal / cm ³ ) ^0.5 ), Dipropylene glycol dimethacrylate, Trimethylol propanetriacrylate (TMPTA) , SP value: 10.4 (cal / cm ³ ) ^0.5 ), trimethylpropantrimethacrylate, pentaerythritol triacrylate (SP value: 10.5 (cal / cm ³ ) ^0.5 ), pentaerythritol trimethacrylate , Pentaerythritol tetraacrylate (PETA, SP value: 10.5 (cal / cm ³ ) ^0.5 ), pentaerythritol tetramethacrylate and the like. These may be used alone or in combination of two or more. Among these, 1,6-hexanediol dimethacrylate and 1,9-nonanediol dimethacrylate are preferable from the viewpoint of enhancing the stretchability of the cured film.

The saturated water content of the polymerizable monomer is preferably 0% by mass or more and 3% by mass or less, and more preferably 0% by mass or more and 1% by mass or less at 25 ° C. When the saturated water content of the polymerizable monomer is 0% by mass or more and 3% by mass or less, the water resistance of the cured film becomes good.
Examples of the polymerizable monomer having a saturated water content of 0% by mass or more and 3% by mass or less include the above-mentioned polymerizable monomer, and among these, a hydrophobic monomer containing no hydrophilic group is preferable.
The saturated water content of the polymerizable monomer can be obtained from, for example, the result measured by a Carl Fisher moisture meter.

The content of the polymerizable monomer is preferably 50% by mass or more and 90% by mass or less, and more preferably 65% by mass or more and 85% by mass or less, based on the total amount of the curable composition.
Assuming that the content of the monofunctional monomer is A and the content of the polyfunctional monomer is B, it is preferable to satisfy the following formula, A ≧ B, from the viewpoint of stretchability of the cured film.

The content of the polyfunctional monomer is preferably 1% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 5% by mass or less when high stretchability is required, based on the total amount of the curable composition. ..
When the content of the polyfunctional monomer is 1% by mass or more, a crosslinked structure can be formed, and water resistance and film strength are improved. Further, when the content of the polyfunctional monomer is 20% by mass or less, the stretchability and moldability are good.

The skin irritation (PI) of the polymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1.0 or less. When the skin irritation is 1.0 or less, the irritation to the skin can be reduced and the safety can be improved.

As the hue of the polymerizable monomer, the Gardner grayscale is preferably 2 or less, and colorless and transparent is more preferable. When the Gardner gray scale is 2 or less, it is possible to prevent the color of the image portion from changing. The Gardner grayscale can be measured according to the JIS-0071-2 color test method for chemical products-Gardner color number test method.

-Polymerizable oligomer-
The polymerizable oligomer preferably has one or more ethylenically unsaturated double bonds. The oligomer means a polymer in which the number of repetitions of the monomer structural unit is 2 or more and 20 or less.

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

Examples of the polymerizable oligomer include urethane acrylic oligomers (for example, aromatic urethane acrylic oligomers, aliphatic urethane acrylic oligomers, etc.), epoxy acrylate oligomers, polyester acrylate oligomers, and other special oligomers. These may be used alone or in combination of two or more. Among these, oligomers having 2 or more and 5 or less unsaturated carbon-carbon bonds are preferable, and oligomers having 2 unsaturated carbon-carbon bonds are more preferable. When the number of unsaturated carbon-carbon bonds is 2 or more and 5 or less, good curability can be obtained.

As the polymerizable oligomer, a commercially available product can be used, and as the commercially available product, for example, UV-2000B, UV-2750B, UV-3000B, UV-3010B, UV- manufactured by Nippon Synthetic Chemical Industry Co., Ltd. 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; Sartmer's CN902, CN902J75, CN929, CN940, CN944, CN944B85, CN959, CN961E75, CN961H81, CN962, CN963, CN963A80, CN963B80, CN963E75, CN963E80, CN963J85, CN964, CN965, CN965A80, CN966, CN966A80, CN966B85, CN966H90, CN966J75, CN9668, CN9669, CN970, CN970, CN970, CN970, CN970 CN973A80, CN973H85, CN973J75, CN975, CN977, CN977C70, CN978, CN980, CN981, CN981A75, CN981B88, CN982, CN982A75, CN982B88, CN982E75, CN983, CN984, CN985, CN9985B88, CN982, CN998 CN997, CN999, CN9001, CN9002, CN9004, CN9005, CN9006, CN9007, CN9008, CN9009, CN9010, CN9011 CN9290, CN9782, CN9783, CN9788, CN9893; EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, KRM8200, EBECRYL manufactured by Daicel Cytec Co., Ltd. 5129, EBECRYL8210, EBECRYL8301, EBECRYL8804, EBECRYL8807, EBECRYL9260, KRM7735, KRM8296, KRM8452, EBECRYL4858, EBECRYL8402, EBECRYL9270, EBECRYL9270, etc. These may be used alone or in combination of two or more.
Further, instead of a commercially available product, a synthetic product obtained by synthesis can be used, and the synthetic product and the commercially available product can be used in combination.

The skin irritation (PI) of the polymerizable oligomer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1.0 or less. When the skin irritation is 1.0 or less, the irritation to the skin can be reduced and the safety can be improved.

As the hue of the polymerizable oligomer, the Gardner grayscale is preferably 2 or less, and more preferably colorless and transparent. When the Gardner gray scale is 2 or less, it is possible to prevent the color of the image portion from changing. The Gardner grayscale can be measured according to the JIS-0071-2 color test method for chemical products-Gardner color number test method.

The content of the polymerizable oligomer is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 8% by mass or less, and particularly preferably 5% by mass or less, based on the total amount of the curable composition. When the content is 20% by mass or less, the hardness of the obtained cured product can be increased.

<Pigment>
The pigment used in the present invention is not particularly limited and may be appropriately selected depending on the intended purpose.
Examples of the yellow pigment include C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 180 and the like. It is preferable that the surface is acid-treated in order to obtain good dispersibility. The acidic treatment facilitates the adsorption of the basic polymer dispersant, and the steric repulsion effect improves the dispersibility.

As the magenta pigment, a quinacridone pigment is widely used. For example, the quinacridone pigment C.I. I. Pigment Red 122, C.I. I. Pigment Violet 19, C.I. I. Pigment Red 202 and the like. Among these, from the viewpoint of color characteristics and weather resistance, C.I. I. It is preferable to contain at least one Pigment Red 122. Further, two or more kinds may be mixed or a mixed crystal pigment may be used. It is preferable that the surface is acid-treated in order to obtain good dispersibility. The acidic treatment facilitates the adsorption of the basic polymer dispersant, and the steric repulsion effect improves the dispersibility.

Cyan pigments are C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4 and the like. Among these, from the viewpoint of color characteristics, dispersibility, and weather resistance, C.I. I. Pigment Blue 15: 4 is preferred. It is preferable that the surface is acid-treated in order to obtain good dispersibility. The acidic treatment facilitates the adsorption of the basic polymer dispersant and improves the dispersibility.

The black pigment is preferably carbon black. As the carbon black, it is preferable to use an oxidation-treated carbon black having a primary particle diameter of 35 nm or more and 60 nm or less, a DBP oil absorption amount of 35 g / 100 g or more and 55 g / 100 g or less, and a pH of 3.5 or less.

Titanium oxide is preferable as the white pigment. It is more preferable that the titanium oxide is surface-treated with alumina, silica, or the like. Further, a white inorganic pigment or the like may be mixed and used.
Examples of the white inorganic pigment include sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, fine powder silicic acid, silicas such as synthetic silicates, calcium silicate, and alumina. , Alumina hydrate, zinc oxide, talc, clay and the like.

The content of the pigment is 1% by mass or more and 5% by mass or less with respect to the total amount of the curable composition.
The pigment dispersant is adsorbed around the pigment, and voids are likely to be formed around the pigment. The polymerizable monomer and the polymerizable oligomer are integrated by the reaction, but the pigment and the pigment dispersant do not contain a reactive group that reacts with the polymerizable monomer, and when the cured film swells due to water content, the periphery of the pigment becomes a void. Prone. Therefore, it is important that the content of the pigment is 5% by mass or less with respect to the total amount of the curable composition, and it is preferable that the content is as small as possible if the print density can be secured. If the content of the pigment is less than 1% by mass, a sufficient print density required for image formation cannot be obtained, and if it exceeds 5% by mass, the water resistance of the cured film is lowered.

The pigment preferably exists as a pigment dispersion dispersed in the curable composition by a pigment dispersant.
The pigment dispersant is not particularly limited and may be appropriately selected depending on the intended purpose, but a polymer-based dispersant is preferable.
Examples of the polymer-based dispersant include polyoxyalkylene polyalkylene polyamines, vinyl-based polymers and copolymers, acrylic-based polymers and copolymers, polyesters, polyamides, polyimides, polyurethanes, and amino-based polymers.
Commercially available products can be used as the polymer dispersant. Examples of the commercially available products include the Ajinomoto Fine-Techno Co., Ltd. Azisper series and the Japan Louvre Resol Co., Ltd. (Avesia, Noveon) Solspers series. 32000 etc.), DISPERBYK series manufactured by Big Chemie, BYKJET series, Disparon series manufactured by Kusumoto Kasei Co., Ltd., etc.

The saturated water content of the pigment dispersant is preferably 0% by mass or more and 3% by mass or less, and more preferably 0% by mass or more and 1% by mass or less at 25 ° C. When the saturated water content of the pigment dispersant is 0% by mass or more and 3% by mass or less, the water resistance of the cured film is good.
The saturated water content of the pigment dispersant can be obtained from, for example, the result measured by a Carl Fisher moisture meter.
A commercially available product can be used as the pigment dispersant having a saturated water content of 0% by mass or more and 3% by mass or less at 25 ° C. Examples of the commercially available products include BYK-161, BYK-116, BYK-167, BYK-2163, BYK-2164, and BYK-174 (all manufactured by Big Chemie); , Solsperse 41000, Solsperse X300 (all manufactured by Big Chemie Japan Co., Ltd.) and the like. These may be used alone or in combination of two or more. Among these, a reactive dispersant such as Solsparse X300 is preferable from the viewpoint of improving water resistance because it is integrated with the cured film.
If the content of the pigment dispersant is too large, the water resistance is adversely affected, so the minimum dispersible content is preferable.

When the pigment dispersant is separately measured from the curable composition, it can be measured by, for example, the following method. Weigh 1.5 g of ink into a 1 mL sample holder for centrifugation. This is centrifuged at 100,000 rpm for 1 hour to remove the supernatant. Add approximately the same amount of acetone as the amount removed, stir with a spatula, and centrifuge in the same manner, for a total of 4 times. This is completely dried in a vacuum dryer. A separation extraction solvent such as methylene chloride is added to this, the pigment and the pigment dispersant are separated, the elution component contained in the pigment dispersant is dried, the pigment dispersant is separated, and the curl fisher is measured with a moisture meter.

<Saturated water content of polymerizable monomer and pigment dispersant>
Pure water was added to the polymerizable monomer and pigment dispersant in an amount of 0.25% by mass, and a Karl Fischer titer (MKA-610 type manufactured by Kyoto Denshi Kogyo Co., Ltd., measuring method: electric field method, heating temperature: 150 ° C.) , N ₂ purge flow rate: 200 mL / min) to measure the water content. The saturated water content was defined as the water content at which the water content did not change even when pure water was added above a certain level.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the intended purpose. For example, a surfactant, an organic solvent, a penetration accelerator, a wetting agent (moisturizing agent), a fixing agent, an antifungal agent, and an antiseptic. Examples include agents, antioxidants, UV absorbers, chelating agents, pH regulators, thickeners and the like.

-Surfactant-
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include higher fatty acid-based surfactants, silicone surfactants, and fluorine surfactants.

The silicone surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, side chain modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, one-ended modified polydimethylsiloxane, and both side chain ends. Examples thereof include modified polydimethylsiloxane. Among these, a polyether-modified silicone-based surfactant having a polyoxyethylene group and a polyoxyethylene polyoxypropylene group as modifying groups is particularly preferable because it exhibits good properties as an aqueous surfactant.
As such a surfactant, an appropriately synthesized one may be used, or a commercially available product may be used. Commercially available products can be obtained from, for example, Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., Kyoeisha Chemical Co., Ltd., and the like.

The polyether-modified silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the polyalkylene oxide structure represented by the following general formula (S-1) is dimethyl. Examples thereof include those introduced into the Si part side chain of polysiloxane.

[General formula (S-1)]
(However, in the general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R'represents an alkyl group.)

Commercially available products can be used as the above-mentioned polyether-modified silicone-based surfactant, for example, KF-618, KF-642, KF-643 (manufactured by Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, SS. -1906EX (manufactured by Nippon Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (manufactured by Toray Dow Corning Silicone Co., Ltd.), BYK -33, BYK-387, BYK-3510, BYK-3576 (manufactured by Big Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (manufactured by Toshiba Silicon Co., Ltd.) and the like.

The content of the surfactant is preferably 0.1% by mass or more and 3% by mass or less, more preferably 0.2% by mass or more and 1% by mass or less, based on the total amount of the curable composition.
When the content is 0.1% by mass or more, the wettability can be improved, and when the content is 3% by mass or less, the curability can be improved. When the content is within a more preferable range, the wettability and the leveling property can be improved.

-Organic solvent-
The curable composition of the present invention may contain an organic solvent, but it is preferable not to contain it if possible. By not containing an organic solvent (for example, VOC (Volatile Organic Compounds) free), there is no residual volatile organic solvent in the cured film, safety at the printing site can be obtained, and environmental pollution can be prevented. It becomes. The "organic solvent" means a solvent generally called a volatile organic compound (VOC), and examples thereof include ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and the reaction It should be distinguished from sex monomers. Further, "not containing" the organic solvent means that the organic solvent is substantially not contained, and the content thereof is preferably less than 0.1% by mass.

<Viscosity>
The viscosity of the curable composition of the present invention is not particularly limited and can be appropriately adjusted according to the application and application means. For example, when a discharge means for discharging the composition from a nozzle is applied. The viscosity in the range of 20 ° C. to 65 ° C., preferably the viscosity at 25 ° C. is 60 mPa · s or less, preferably 3 mPa · s or more and 40 mPa · s or less, more preferably 5 mPa · s or more and 30 mPa · s or less, and 5 mPa · s or less. -S or more and 15 mPa · s or less is more preferable, and 6 mPa · s or more and 12 mPa · s or less is particularly preferable.
Further, it is particularly preferable that the viscosity range is satisfied without containing the organic solvent. For the above viscosity, a cone rotor (1 ° 34'x R24) was used with a cone plate type rotational viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd., the rotation speed was 50 rpm, and the temperature of constant temperature circulating water was 20 ° C. It can be appropriately set and measured in the range of ~ 65 ° C. VISCOMATE VM-150III can be used to adjust the temperature of the circulating water.

<Curing means>
Examples of the curing means for curing the curable composition of the present invention include heat curing or curing with active energy rays, and among these, curing with active energy rays is preferable.
The active energy rays used to cure the curable composition include ultraviolet rays, electron beams, α rays, β rays, γ rays, X-rays, and other polymerizable components in the composition. It is not particularly limited as long as it can provide the necessary energy. In particular, when a high-energy light source is used, the polymerization reaction can proceed without using a polymerization initiator.

The light source of the active energy ray is not particularly limited and may be appropriately selected. Examples thereof include a mercury lamp, a metal halide lamp, and a UV-LED lamp.
The mercury lamp is a quartz glass arc tube filled with high-purity mercury (Hg) and a small amount of rare gas, and has a main wavelength of 365 nm and efficiently emits ultraviolet rays of 254 nm, 303 nm, and 313 nm. It emits light and has a high output of short-wavelength ultraviolet rays.
The metal halide lamp is a metal halide lamp in which a metal is encapsulated in the form of a halide in addition to mercury. It emits an active energy ray spectrum over a wide range from 200 nm to 450 nm, and is 300 nm or more and 450 nm or less as compared with a mercury lamp. It is characterized by high output of long-wavelength ultraviolet rays.
The UV-LED lamp has a feature that the environmental load can be reduced, ozone is not generated, and the apparatus can be made compact by the LED method having a long life and low power consumption, and when the curable composition of the present invention is cured. It is preferable as a lamp used for.

<Manufacturing method>
As a method for producing the curable composition, a pigment, a polymerizable compound, and a dispersant are put into a disperser using a medium such as a ball mill, a kitty mill, a disc mill, a pin mill, or a dyno mill, and the pigment is dispersed and kneaded to obtain a pigment. It can be obtained by preparing a dispersion and further mixing it with a polymerizable compound, a polymerization initiator, a polymerization inhibitor, a surfactant and the like. Further, a medialess disperser such as a dispar or a homogenizer may be used.

The water absorption rate of the cured film is preferably 0% or more and 5% or less.
When the water absorption rate of the cured film is 0% or more and 5% or less, the water discoloration resistance and the water adhesion resistance are good.
The water absorption rate of the cured film is obtained from the mass when immersed in warm water at 40 ° C. for 1 day by an evaluation method based on the method of the JIS-A5208 water absorption test (water absorption rate of 5.4 (3) of JIS-A5208). Calculation method).
Water absorption (%) = (increased mass of cured film / mass of initial cured film) x 100%

The glass transition temperature (Tg) of the cured film is preferably 0 ° C. or higher and 30 ° C. or lower. If the glass transition temperature is less than 0 ° C., the film strength may decrease, and if it is higher than 30 ° C., the adhesiveness decreases, and the laminate adhesion and the substrate adhesion on the adhesive label decrease.
The glass transition temperature (Tg) of the cured film can be measured by using, for example, differential scanning calorimetry (DSC), thermomechanical analysis (TMA), or the like.

(Use)
The curable composition of the present invention is not particularly limited as long as it is a field in which a curable material is generally used, and can be appropriately selected depending on the intended purpose. For example, a molding resin, a paint, an adhesive, and an insulating material. It can be applied to materials, mold release agents, coating materials, sealing materials, various resists, various optical materials, and the like. Among these, it is suitable for products such as automobile exterior paints, adhesive labels, home appliances, and adhesive tapes with patterns that require a high level of water resistance.
Further, the curable composition of the present invention is used not only as an ink to form two-dimensional characters and images, but also as a three-dimensional modeling material for forming a three-dimensional stereoscopic image (three-dimensional model). be able to.
As the material for three-dimensional modeling, for example, as a binder between powder particles used in the powder lamination method, which is one of the three-dimensional modeling methods, and as shown in FIG. 2, a curable composition is placed in a predetermined region. A storage pool (accommodation) of the curable composition 5 as shown in the material jet method (stereolithography method) in which three-dimensional modeling is performed by sequentially laminating those that have been discharged and cured by irradiating them with active energy rays. Part) 1 is irradiated with active energy rays 4 to form a cured layer 6 having a predetermined shape on a movable stage 3, and these are sequentially laminated and used as a three-dimensional object constituent material in a stereolithography method or the like. Can be done.
A known three-dimensional modeling device for modeling a three-dimensional model using such a curable composition can be used, and is not particularly limited, but for example, a means for accommodating the composition, a means for supplying the composition, and the like. Those provided with a discharge means, an active energy ray irradiation means, and the like can be used.

The present invention also includes a cured product obtained by curing a curable composition and a molded product obtained by processing a structure in which the cured product is formed on a base material such as a recording medium. The molded product is, for example, a cured product or structure formed in the form of a sheet or a film that has been subjected to molding processing such as heat stretching or punching. For example, automobiles, OA equipment, and electricity. -Suitably used for applications that require molding after decorating the surface, such as electronic devices, meters for cameras, and panels for operation units.
The base material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paper, plastic, metal, ceramic, glass, and composite materials thereof. From the viewpoint of processability, plastic is used. The base material is preferable.
The stretchability of the cured product in the present invention is 50% as the stretchability at 180 ° C. when expressed by the ratio of (length after tensile test-length before tensile test) / (length before tensile test). The above is preferable, and 100% or more is more preferable.

<Curing ink>
The curable ink used in the present invention comprises the curable composition of the present invention.

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

(Container)
The container of the present invention means a container in which a curable composition is contained, and is suitable for use in the above-mentioned applications. For example, when the curable composition of the present invention is used for ink, the container containing the ink can be used as an ink cartridge or an ink bottle, whereby in operations such as ink transfer and ink replacement. , It is not necessary to touch the ink directly, and it is possible to prevent the fingers and clothes from getting dirty. In addition, it is possible to prevent foreign substances such as dust from being mixed into the ink. The shape, size, material, etc. of the container itself may be suitable for the intended use and usage, and is not particularly limited, but the material is a light-shielding material that does not transmit light, or the container blocks light. It is preferable that it is covered with a sex sheet or the like.

(Image forming method and image forming device)
The image forming method of the present invention may use active energy rays, or may include heating. In order to cure the curable composition of the present invention with active energy rays, an irradiation step of irradiating the active energy rays is provided, and the image forming apparatus of the present invention is an irradiation means for irradiating the active energy rays. , The accommodating portion for accommodating the cured composition may be provided, and the container may be accommodated in the accommodating portion. Further, it may have a discharge step and a discharge means for discharging the curable composition. The method of discharging is not particularly limited, and examples thereof include a continuous injection type and an on-demand type. Examples of the on-demand type include a piezo method, a thermal method, and an electrostatic method.

Here, FIG. 1 is an example of an image forming apparatus provided with an inkjet ejection means. The ink is ejected to the recording medium 22 supplied from the supply roll 21 by the color printing units 23a, 23b, 23c, and 23d including the ink cartridges of the yellow, magenta, cyan, and black color-curable inks and the ejection head. Then, the light sources 24a, 24b, 24c, and 24d for curing the ink are irradiated with active energy rays to cure the ink, and a color image is formed. After that, the recording medium 22 is conveyed to the processing unit 25 and the printed matter winding roll 26. Each printing unit 23a, 23b, 23c, 23d may be provided with a heating mechanism so that the ink is liquefied at the ink ejection portion. Further, if necessary, a mechanism for cooling the recording medium to about room temperature by contact or non-contact may be provided. Further, with respect to a recording medium that moves intermittently according to the width of the ejection head, a serial method in which the head is moved to eject ink onto the recording medium or a recording medium is continuously moved and held at a fixed position. Any inkjet recording device of the line type that ejects ink from the head onto the recording medium can be applied.

The recording medium 22 is not particularly limited and may be appropriately selected depending on the intended purpose. Paper, film, metal, composite materials thereof and the like can be mentioned, and the recording medium 22 may be in the form of a sheet.
Further, the activation energy rays from the light sources 24a, 24b, and 24c may be weakened or omitted, and after printing a plurality of colors, the activation energy rays may be irradiated from the light source 24d. As a result, energy saving and cost reduction can be achieved.
The recorded material recorded by the curable ink used in the present invention includes not only those printed on a smooth surface such as ordinary paper or resin film, but also those printed on a surface to be printed having irregularities and metal. It also includes those printed on the surface to be printed made of various materials such as ceramics and ceramics. Further, by stacking two-dimensional images, it is possible to form a partially three-dimensional image (an image composed of two-dimensional and three-dimensional) or a three-dimensional object.

FIG. 2 is a schematic view showing an example of another image forming apparatus (three-dimensional stereoscopic image forming apparatus) used in the present invention. The image forming apparatus 39 of FIG. 2 uses a head unit (movable in the AB direction) in which the inkjet heads are arranged to transfer the first curable composition from the discharge head unit 30 for a modeled object to the discharge head unit for a support. The second curable composition having a composition different from that of the first curable composition is discharged from 31 and 32, and these compositions are laminated while being cured by the adjacent ultraviolet irradiation means 33 and 34.
More specifically, for example, the second curable composition is discharged from the support discharge head units 31 and 32 onto the modeled object support substrate 37, irradiated with active energy rays and solidified to form a reservoir. After forming the first support layer to have, the first curable composition is discharged from the discharge head unit 30 for a modeled object into the reservoir, and is irradiated with active energy rays to solidify the first modeled object. By repeating the step of forming the layer a plurality of times while lowering the stage 38 that is movable in the vertical direction according to the number of times of stacking, the support layer and the modeled object layer are laminated to produce the three-dimensional modeled object 35. After that, the support laminated portion 36 is removed as needed. In FIG. 2, only one discharge head unit 30 for a modeled object is provided, but two or more may be provided.

(2D or 3D image)
The two-dimensional or three-dimensional image of the present invention is obtained by applying the curable composition of the present invention on a substrate and curing it.
The two-dimensional or three-dimensional image recorded by the curable composition of the present invention is not only printed on a smooth surface such as ordinary paper or a resin film, but also recorded on a recording surface having irregularities. Also included are those recorded on a recording surface made of various materials such as metal and ceramics.

Examples of the two-dimensional image include characters, symbols, figures, combinations thereof, and solid images.
Examples of the three-dimensional image include a three-dimensional model.
The average thickness of the three-dimensional model is not particularly limited and can be appropriately selected depending on the intended purpose, and is preferably 10 μm or more.

Since the curable composition of the present invention is used for the two-dimensional or three-dimensional image, the two-dimensional or three-dimensional image formed on the impermeable substrate has good adhesion even after being immersed in water. It has excellent water resistance that can be maintained at.
The two-dimensional or three-dimensional image is preferably cured using light emitting diode light.

(Printed matter)
The printed matter of the present invention has a base material, a printing layer composed of the curable composition of the present invention on the base material, and a laminate layer or a film layer on the printing layer.
Water resistance can be further improved by laminating and using a cured film made of the curable composition of the present invention. Light resistance can also be improved by including an ultraviolet absorber in the laminated film.
The base material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paper, plastic, metal, ceramic, glass, and composite materials thereof. From the viewpoint of processability, plastic is used. The base material is preferable.
Here, FIG. 5 is a diagram showing a state when the cured film is laminated. In FIG. 5, 101 is a base material, 102 is a cured film, and 103 is a laminate layer or a film layer.

(Adhesive label)
The adhesive label of the present invention has a base material and a printed layer made of the curable composition of the present invention on the base material, and the printed layer has adhesiveness.
The adhesive label of the present invention has excellent adhesiveness and adhesiveness on the image printing surface, and can be strongly adhered to a transparent substrate such as glass. In addition, since it has high water resistance, it can be applied to, for example, a vehicle inspection label used by adhering to a car windshield, an advertising label attached to a train door, and the like.
FIG. 6 is a diagram showing a case where the cured film is used as an adhesive label on a transparent base material. In FIG. 6, 101 is a base material, 102 is a cured film, and 104 is a transparent base material.
It can also be applied to applications such as glass that are attached to a transparent substrate.

FIG. 7 is a diagram showing a case where a cured film is formed on a transparent base material and used as an adhesive label on an opaque base material. In FIG. 7, 105 is a transparent base material, 102 is a cured film, and 106 is an opaque base material.
When the curable composition of the present invention is formed on a transparent base material, the image surface can be attached to the base material and the image can be displayed from the transparent base material side.

FIG. 8 is a diagram showing a method of applying a water-repellent and oil-repellent material to the back surface of a cured film as an adhesive label and winding it up without the need for a release paper. In FIG. 8, 201 is a roller that feeds out a base material, 204 is a base material, 203 is an inkjet head, and 202 is a take-up roller.
Since the surface of the base material 201 that does not have the printing layer is water-repellent or oil-repellent, when the produced adhesive label is wound up by the winding roller 202, a release paper is not required and it is wound up. It can be manufactured.

(Structure)
The structure of the present invention has a base material and a two-dimensional or three-dimensional image of the present invention on the base material.
The base material is not particularly limited and may be appropriately selected depending on the intended purpose.

(Molded product)
The molded product of the present invention is formed by stretching either the two-dimensional or three-dimensional image of the present invention or the structure of the present invention.

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

(Production Example 1 of Pigment Dispersion)
-Preparation of pigment dispersion A-
Magenta pigment (trade name: RGT (PR122), manufactured by DIC Corporation) 15 parts by mass, polymerizable group-containing reactive dispersant (trade name: Solsparse X300, manufactured by Nippon Lusolbrizol Co., Ltd.) 10 parts by mass, and benzyl acrylate (Osaka) (Manufactured by Organic Chemical Industry Co., Ltd.) 75 parts by mass was placed in a 300 mL ball mill filled with 2 mm diameter zirconia beads (filling rate: 45% by volume) and dispersed at 70 rpm for 96 hours at a dispersion temperature of 25 ° C. A pigment dispersion A was prepared.

(Production Example 2 of Pigment Dispersion)
-Preparation of pigment dispersion B-
Cyan pigment (trade name: D7110F (PB15: 4), manufactured by BASF) 15 parts by mass, dispersant (trade name: BYK-9151, manufactured by Big Chemie) 5 parts by mass, and cyclic trimethylolpropane formal acrylate (Osaka Organic Chemistry) 80 parts by mass (manufactured by Kogyo Co., Ltd.) was dispersed in a homogenizer at 5,000 rpm for 20 minutes at a dispersion temperature of 35 ° C., and then filled with 0.3 mm diameter zirconia beads (filling ratio: 90% by mass) into a 1 L sand mill. The pigment dispersion B was prepared by dispersing the pigment at a peripheral speed of 10 m / sec and a dispersion temperature of 30 ° C. for 1 hour.

(Production Example 3 of Pigment Dispersion)
-Preparation of pigment dispersion C-
Black pigment (trade name: MOGUL-E (carbon black), manufactured by Orion Co., Ltd.) 15 parts by mass, dispersant (trade name: BYK167, manufactured by Big Chemie) 5 parts by mass, and phenoxyethyl acrylate (Osaka Organic Chemical Industry Co., Ltd.) (Manufactured) 80 parts by mass was placed in a 300 mL ball mill filled with 2 mm diameter zirconia beads (filling rate: 43% by mass) and dispersed at a dispersion temperature of 25 ° C. at 70 rpm for 180 hours to prepare a pigment dispersion C. did.

(Production Example 4 of Pigment Dispersion)
-Preparation of pigment dispersion D-
Yellow pigment (trade name: LIONOL YELLOW TT-1703 (PY17), manufactured by Toyo Ink Co., Ltd.) 15 parts by mass, polymerizable group-containing reactive dispersant (trade name: Solsparse X300, manufactured by Nippon Lusolbrizol Co., Ltd.), 2 parts by mass, And tetrahydrofurfuryl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.), 83 parts by mass was placed in a 300 mL ball mill filled with 2 mm diameter zirconia beads (filling ratio: 45% by volume), and allowed to rotate at a dispersion temperature of 25 ° C. for 200 hours at 70 rpm. To prepare a pigment dispersion D.

(Production Example 5 of Pigment Dispersion)
-Preparation of pigment dispersion E-
Yellow pigment (trade name: 4GC (PY155), manufactured by Clariant) 15 parts by mass, dispersant (trade name: BYK-9152, manufactured by Big Chemie) 10 parts by mass, and stearyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 75 The parts by mass were placed in a 300 mL ball mill filled with zirconia beads having a diameter of 2 mm (filling ratio: 45% by mass) and allowed to rotate at a dispersion temperature of 25 ° C. at 70 rpm for 200 hours to prepare a pigment dispersion E.

(Production Example 6 of Pigment Dispersion)
-Preparation of pigment dispersion F-
In Production Example 1 of the pigment dispersion, a polymerizable group-containing reactive dispersant (trade name: Solsparse X300, manufactured by Nippon Lusolbrizol Co., Ltd.) is used as a dispersant (trade name: BYK-9152, manufactured by Big Chemie) and is polymerizable. A pigment dispersion F was produced in the same manner as in Production Example 1 of the pigment dispersion except that the monomer was changed to acryloylmorpholin (manufactured by Kojin Co., Ltd.).

Next, the compositions of the obtained pigment dispersions A to F are shown in Table 1.

(Example 1)
10 parts by mass of the pigment dispersion A, 78 parts by mass of benzyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 3 parts by mass of 1,9-nonanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), urethane acrylate oligomer ( Product name: UV-3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., weight average molecular weight = 10,000) 7 parts by mass, and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1-[ 4- (4-Molphorinyl) phenyl] -1-butanone (trade name: IRGACURE379, manufactured by BASF) was mixed by 2 parts by mass to obtain a cured composition 1.

(Example 2)
20 parts by mass of the pigment dispersion B, 68.5 parts by mass of cyclic trimethylolpropanformal acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 5 parts by mass of 1,9-nonanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 5 parts by mass of urethane acrylate oligomer (trade name: UV-3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., weight average molecular weight = 10,000), and 2-benzyl-2-dimethylamino-1- (4-morpholino) Phenyl) -butanone-1 (trade name: IRGACURE369, manufactured by BASF) was mixed by 1.5 parts by mass to obtain a cured composition 2.

(Example 3)
20 parts by mass of the pigment dispersion A, 30 parts by mass of benzyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 30 parts by mass of cyclic trimethylolpropanformal acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), diethylene glycol diacrylate (Osaka) 11 parts by mass of Organic Chemical Industry Co., Ltd., 6 parts by mass of urethane acrylate oligomer (trade name: UV-3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., weight average molecular weight = 10,000), and 2- (dimethylamino)- 2-[(4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379, manufactured by BASF) 3 parts by mass are mixed to form a curable composition 3 Got

(Example 4)
20 parts by mass of the pigment dispersion C, 58.5 parts by mass of cyclohexyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 19 parts by mass of 1,6-hexanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE369, manufactured by BASF) was mixed by 2.5 parts by mass to obtain a cured composition 4.

(Example 5)
30 parts by mass of the pigment dispersion D, 30 parts by mass of isoamyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 38 parts by mass of cyclohexyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), trimethylpropan triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) Co., Ltd.) 1 part by mass and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379, 1 part by mass (manufactured by BASF) was mixed to obtain a curable composition 5.

(Example 6)
20 parts by mass of the pigment dispersion E, 30 parts by mass of stearyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 36 parts by mass of lauryl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), pentaerythritol triacrylate (Osaka Organic Chemical Industry Co., Ltd.) 1 part by mass of urethane acrylate oligomer (trade name: CN966, manufactured by Sartmer, weight average molecular weight = 9,000), 10 parts by mass, 2-methyl-1- [4- (methylthio) phenyl] -2-morpho 2.8 parts by mass of renopropane-1-one (trade name: IRGACURE907, manufactured by BASF) and 0.2 parts by mass of p-methoxyphenol (manufactured by Nippon Kayaku Co., Ltd.) are mixed to obtain a curable composition 6. Obtained.

(Example 7)
20 parts by mass of the pigment dispersion A, 30 parts by mass of benzyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 34.5 parts by mass of N-vinylcaprolactam (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 1,9-nonanediol Diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 8 parts by mass, urethane acrylate oligomer (trade name: UV-3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., weight average molecular weight = 10,000) 5 parts by mass, 2- (dimethyl) Amino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379, manufactured by BASF) 2.2 parts by mass, and acrylic functional 0.3 parts by mass of a group-containing modified polydimethylsiloxane (trade name: BYK-3576, manufactured by Big Chemie Japan Co., Ltd.) was mixed to obtain a cured composition 7.

(Comparative Example 1)
20 parts by mass of the pigment dispersion A, 8 parts by mass of benzyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 57 parts by mass of isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 1,9-nonanediol diacrylate (Manufactured by Osaka Organic Chemical Industry Co., Ltd.) 3 parts by mass, urethane acrylate oligomer (trade name: UV-3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., weight average molecular weight = 10,000) 7 parts by mass, 2- (dimethylamino) -2-[(4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379, manufactured by BASF) 4.5 parts by mass, p-methoxyphenol ( 0.2 parts by mass of Nippon Kayaku Co., Ltd.) and 0.3 parts by mass of polyether-modified polydimethylsiloxane (trade name: BYK3510, manufactured by Big Chemie Japan Co., Ltd.) were mixed to obtain a curable composition 8. ..

(Comparative Example 2)
20 parts by mass of the pigment dispersion F, 38 parts by mass of 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 25 parts by mass of acryloylmorpholin (manufactured by KJ Chemicals Co., Ltd.), 1,9-nonanediol diacrylate (Manufactured by Osaka Organic Chemical Industry Co., Ltd.) 5 parts by mass, urethane acrylate oligomer (trade name: UV-3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., weight average molecular weight = 10,000) 5 parts by mass, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE369, manufactured by BASF) 6.5 parts by mass, p-methoxyphenol (manufactured by Nippon Kayaku Co., Ltd.) 0.2 parts by mass, And 0.3 parts by mass of an acrylic functional group-containing modified polydimethylsiloxane (trade name: BYK-3576, manufactured by Big Chemie Japan Co., Ltd.) were mixed to obtain a cured composition 9.

(Comparative Example 3)
20 parts by mass of the pigment dispersion C, 20 parts by mass of stearyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 40 parts by mass of phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), diethylene glycol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (Manufactured by Co., Ltd.) 10 parts by mass, urethane acrylate oligomer (trade name: UV-3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., weight average molecular weight = 10,000) 6 parts by mass, 2- (dimethylamino) -2-[( 4-Methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379, manufactured by BASF) 3.5 parts by mass, p-methoxyphenol (Nippon Kayaku Co., Ltd.) (Manufactured) 0.2 parts by mass and 0.3 parts by mass of polyether-modified polydimethylsiloxane (trade name: BYK3510, manufactured by Big Chemie Japan Co., Ltd.) were mixed to obtain a cured composition 10.

(Comparative Example 4)
20 parts by mass of the pigment dispersion C, 38 parts by mass of stearyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 30 parts by mass of phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), bis (2,4,6-trimethyl) Benzoyl) -phenylphosphine oxide (trade name: IRGACURE819, manufactured by BASF) 5 parts by mass, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name: LUCIRIN TPO, manufactured by BASF) 3 parts by mass, 2,4-diethylthioxanthone (trade name: Speedcure DETX, manufactured by Rambson) 3.5 parts by mass, p-methoxyphenol (manufactured by Nippon Kayaku Co., Ltd.) 0.2 parts by mass, and polyether-modified polydimethylsiloxane (product) Name: BYK3510, manufactured by Big Chemie Japan Co., Ltd.) 0.3 parts by mass was mixed to obtain a curable composition 11.

(Comparative Example 5)
20 parts by mass of the pigment dispersion A, 30 parts by mass of benzyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 30 parts by mass of cyclic trimethylpropanformal acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 5 parts by mass of trifluoroethyl acrylate. , 5 parts by mass of diethylene glycol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 6 parts by mass of urethane acrylate oligomer (trade name: UV-3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., weight average molecular weight = 10,000), 2- (Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379, manufactured by BASF) 3.5 parts by mass , P-methoxyphenol (manufactured by Nippon Kayaku Co., Ltd.) 0.2 parts by mass, and polyether-modified polydimethylsiloxane (trade name: BYK3510, manufactured by Big Chemie Japan Co., Ltd.) 0.3 parts by mass are mixed and cured. Composition 12 was obtained.

(Comparative Example 6)
Benzyl acrylate of Example 1 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 79.2 parts by mass, and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone (trade name: IRGACURE379, manufactured by BASF) A curable composition 13 was obtained in the same manner as in Example 1 except that the amount was 0.8 parts by mass.

(Comparative Example 7)
Initiator of Example 1 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379, manufactured by BASF) ) Was changed to bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: IRGACURE819, manufactured by BASF), and a cured composition 14 was obtained in the same manner as in Example 1. ..

Various characteristics of the obtained curable compositions of Examples 1 to 7 and Comparative Examples 1 to 7 were evaluated as follows. The results are shown in Table 4.

<Preparation of cured film>
Each of the obtained curable compositions was applied to a base material (trade name: Cosmoshine A4300 coated PET film, manufactured by Toyobo Co., Ltd., average thickness: 100 μm, color: transparent) and a printer (device name: SG7100, manufactured by Ricoh Co., Ltd.). ) Was modified to obtain a solid image of 10 cm × 10 cm. The obtained solid image was cured by using a UV-LED device for an inkjet printer (device name: UV-LED module, single-pass water cooling, manufactured by Ushio Electric Co., Ltd.), and the average thickness was 10 μm and the width was 10 cm ×. An image (cured product) having a length of 10 cm was obtained.
The evaluation printer uses the transport and drive unit of the device name SG7100 (manufactured by Ricoh Co., Ltd.) and is changed to the MH2620 head (manufactured by Ricoh Co., Ltd.) that can heat and eject the head unit and can handle high-viscosity ink. Is.

<Water resistance test conditions>
Approximately 400 mL of pure water was placed in a 500 mL descup, covered with aluminum foil, placed in a constant temperature bath at 40 ° C., and when the liquid temperature reached 40 ° C., a printed sample of 10 cm × 10 cm was placed and stored for 24 hours. It was taken out after 24 hours, and the water resistance quality immediately after that was evaluated.

<Glass transition temperature (Tg)>
The glass transition temperature (Tg) of each of the obtained cured films was measured using a differential scanning calorimeter (DSC7000X, manufactured by Hitachi High-Tech Science Corporation).
The measurement conditions were a temperature rise rate of 5 ° C./min from room temperature (25 ° C.) to around 120 ° C., a sample amount of 10 mg, and a nitrogen atmosphere. The temperature of the peak top was defined as the glass transition temperature (Tg).

<Water absorption rate>
The water absorption rate of each cured film was calculated from the following formula by measuring the mass at the initial stage and when immersed in warm water at 40 ° C. for 1 day by an evaluation method according to JIS-A5208.
Water absorption rate (%) = (increased mass of cured film / initial mass of cured film) x 100%

<Water discoloration resistance>
A cured product of 10 cm × 10 cm and an average thickness of 20 μm was formed on a polyethylene terephthalate (PET) film which is a transparent base material. Before immersing the cured product on white paper (trade name: Type 6200 paper, manufactured by Ricoh Co., Ltd.) and immersing it in water using a reflection spectrophotometer (device name: X-Rite939, manufactured by X-Rite). L ^* value, a ^* value, and b ^* value were measured.
Next, 400 mL of pure water was placed in a 500 mL polypropylene beaker (trade name: Deathcup, manufactured by Terraoka Co., Ltd.), covered with aluminum foil, and placed in a constant temperature bath at 40 ° C. When the temperature of the pure water reached 40 ° C., the obtained cured product (length 10 cm × width 10 cm, average thickness 10 μm) was immersed in the water of the beaker and stored in a constant temperature bath for 24 hours. Then, the cured product was taken out, and the L ^* value, a ^* value, and b ^* value after being immersed in water were measured by the same method as before the immersion in water.
Then, the color difference ΔE was calculated from the following formula, and the “water discoloration resistance” was evaluated based on the following evaluation criteria. In addition, "○" or more is the feasible level.
ΔL ^* = (L ^* value before immersion in water)-(L ^* value after immersion in water)
Δa ^* = (a ^* value before immersion in water)-(a ^* value after immersion in water)
Δb ^* = (b ^* value before immersion in water)-(b ^* value after immersion in water)
ΔE = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2
[Evaluation criteria]
⊚: Color difference ΔE is 2.0 or less ◯: Color difference ΔE is more than 2.0 and 5.0 or less Δ: Color difference ΔE is more than 5.0 and 10.0 or less ×: Color difference ΔE Exceeds 10.0

<Water resistance>
The water resistance adhesion means the adhesion immediately after the water resistance after one day at 40 ° C., and the following adhesion test was performed on each cured film (length 10 cm × width 10 cm, average thickness 10 μm) taken out under the above water resistance test conditions. Was done.
Based on the JIS K5600 cross-cut test, the solid part of the obtained image (cured product) is cut with a cutter knife at 1 mm intervals according to JIS K5600, and cellophane adhesive tape (trade name: Scotch mending tape) 18mm), peeled off with 3M Japan Ltd.), and while looking at the loupe (trade name: PEAK No. 1961 (× 10), manufactured by Tokai Sangyo Co., Ltd.), based on the following evaluation criteria, "water resistance" evaluated. Note that FIG. 4 is a sample adhesion rank of JIS-K5600.
[Evaluation criteria]
⊚: JIS K5600 cross-cut evaluation rank classification 0 level ○: JIS K5600 cross-cut evaluation rank classification 1 level △: JIS K5600 cross-cut evaluation rank classification 2nd to 3rd level ×: JIS K5600 cross-cut evaluation rank classification 4th level or higher

<Laminate adhesion>
Lamination adhesion means the adhesion between the laminated surface and the cured film surface, and the obtained cured film is laminated at 100 ° C. using a hard vinyl chloride film with a thickness of 100 μm, and a cellophane adhesive tape (product). Name: Scotch mending tape (18 mm), manufactured by 3M Japan Ltd.) was applied to determine the number of peelings out of 10 times, and the laminate adhesion was evaluated based on the following evaluation criteria.
[Evaluation criteria]
⊚: Number of peeling is 0 times ○: Number of peeling is 1 or less △: Number of peeling is more than 1 and less than 3 ×: Number of peeling is 3 or more

<Base material adhesion>
Adhesion to the base material means the adhesion between the base material and the surface of the cured film, and the obtained cured film can be used as an OK top coat (manufactured by Oji Paper Co., Ltd., thickness: 101 μm), a glass plate (S9213, Matsunami Glass Co., Ltd.). (Made) and aluminum plate (model number: EA441WA-15, thickness 2 mm) were attached to three types of substrates, evaluated in the same manner as the above water resistance adhesion, and the substrate adhesion was evaluated based on the following evaluation criteria. ..
[Evaluation criteria]
⊚: JIS K5600 cross-cut evaluation rank classification 0 level ○: JIS K5600 cross-cut evaluation rank classification 1 level △: JIS K5600 cross-cut evaluation rank classification 2nd to 3rd level ×: JIS K5600 cross-cut evaluation rank classification 4th level or higher

From the results in Table 4, since the content of the polymerization initiator in Examples 1 to 7 is 1.0% by mass or more and 3% by mass or less, the water discoloration resistance and the water adhesion resistance are higher than those in Comparative Examples 1 to 7. It is good. In Example 6, since the content of the polymerization inhibitor exceeds 0.1% by mass, the water discoloration resistance and the water adhesion resistance are slightly inferior. Further, in Examples 1 to 7, the adhesion to the laminated film when the laminating process is performed and the adhesiveness when the printed surface of the cured film is bonded to the base material are also good, and these required characteristics can be compatible with each other. I understood.
In Comparative Example 6, since the content of the polymerization initiator was small, sufficient curability could not be obtained, and the adhesion property was deteriorated.
In Comparative Example 7, since the α-aminoalkylphenon compound was not used as the polymerization initiator, the water adhesion resistance was lowered.

Examples of aspects of the present invention are as follows.
<1> A curable composition containing a polymerizable monomer composed of a monofunctional monomer and a polyfunctional monomer and a polymerization initiator.
It is a curable composition characterized in that the polymerization initiator is an α-aminoalkylphenone compound and the content of the polymerization initiator is 1.0% by mass or more and 3% by mass or less.
<2> The α-aminoalkylphenyl compound is 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-. Selected from benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one. The curable composition according to <1>, which is at least one kind.
<3> The curable composition according to any one of <1> to <2>, which contains a polymerization inhibitor and has a content of the polymerization inhibitor of 0.10% by mass or less.
<4> The curing according to any one of <1> to <3>, wherein the SP value of the polymerizable monomer is 7 (cal / cm ³ ) ^0.5 or more and 11 (cal / cm ³ ) ^0.5 or less. It is a mold composition.
<5> The curable composition according to any one of <1> to <4>, wherein the saturated water content of the polymerizable monomer is 0% by mass or more and 3% by mass or less at 25 ° C.
<6> The curable composition according to any one of <1> to <5>, which further contains a polymerizable oligomer.
<7> The curable composition according to <6>, wherein the polymerizable oligomer has a weight average molecular weight of 5,000 or more and 20,000.
<8> The curable composition according to any one of <1> to <7>, which is an active energy ray-curable composition.
<9> The curable composition according to any one of <1> to <8>, which is a material for three-dimensional modeling.
<10> The curable composition according to any one of <1> to <9> for inkjet use.
<11> Having a base material, a printing layer composed of the curable composition according to any one of <1> to <10> on the base material, and a laminate layer or a film layer on the printing layer. It is a characteristic printed matter.
<12> It is characterized by having a base material and a printing layer made of the curable composition according to any one of <1> to <10> on the base material, and the printing layer has adhesiveness. It is an adhesive label.
<13> The adhesive label according to <12>, wherein the surface of the base material that does not have a print layer is water-repellent or oil-repellent.
<14> The storage container is characterized in that the curable composition according to any one of <1> to <10> is contained in the container.
<15> The accommodating portion for accommodating the curable composition according to any one of <1> to <10>, and the accommodating portion.
The imparting means for imparting the curable composition and
A curing means for curing the imparted curable composition and
It is a two-dimensional or three-dimensional image forming apparatus characterized by having.
<16> The application step of applying the curable composition according to any one of <1> to <10>, and the application step.
A curing step of curing the imparted curable composition and
It is a method for forming a two-dimensional or three-dimensional image, which comprises.
<17> A cured product, which is formed by using the curable composition according to any one of <1> to <10>.
<18> The cured product according to <17>, wherein the glass transition temperature (Tg) is 0 ° C. or higher and 30 ° C. or lower.
<19> The cured product according to any one of <17> to <18>, wherein the water absorption rate is 0% or more and 5% or less.
<20> A structure characterized by having a base material and a cured product according to any one of <17> to <19> on the base material.
<21> A molded product obtained by stretching any of the cured product according to any one of <18> to <19> and the structure according to <20>.

The curable composition according to any one of <1> to <10>, the printed matter according to <11>, the adhesive label according to any one of <12> to <13>, and the above <14>. The storage container, the two-dimensional or three-dimensional image forming apparatus according to <15>, the two-dimensional or three-dimensional image forming method according to <16>, or any of the above <17> to <19>. The cured product according to the above, the structure according to the above <20>, and the formed processed product according to the above <21>.

Japanese Unexamined Patent Publication No. 2016-69478 JP-A-2007-51244 JP-A-62-205174 Japanese Patent No. 4865484 Japanese Patent No. 5621251 Japanese Patent No. 6376505

Claims (20)

A curable composition containing a polymerizable monomer containing a monofunctional monomer and a polyfunctional monomer, and a polymerization initiator.
A curable composition, wherein the polymerization initiator is an α-aminoalkylphenone compound, and the content of the polymerization initiator is 1.0% by mass or more and 3% by mass or less. The α-aminoalkylphenone compound is 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-benzyl-2. At least one selected from −dimethylamino-1- (4-morpholinophenyl) -butanone-1, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one. The curable composition according to claim 1. The curable composition according to any one of claims 1 to 2, which contains a polymerization inhibitor and has a content of the polymerization inhibitor of 0.10% by mass or less. The curable composition according to any one of claims 1 to 3, wherein the SP value of the polymerizable monomer is 7 (cal / cm ³ ) ^0.5 or more and 11 (cal / cm ³ ) ^0.5 or less. The curable composition according to any one of claims 1 to 4, wherein the saturated water content of the polymerizable monomer is 0% by mass or more and 3% by mass or less at 25 ° C. The curable composition according to any one of claims 1 to 5, further containing a polymerizable oligomer. The curable composition according to claim 6, wherein the polymerizable oligomer has a weight average molecular weight of 5,000 or more and 20,000. The curable composition according to any one of claims 1 to 7, which is an active energy ray-curable composition. The curable composition according to any one of claims 1 to 8, which is a material for three-dimensional modeling. A printed matter comprising a base material, a printing layer composed of the curable composition according to any one of claims 1 to 9 on the base material, and a laminate layer or a film layer on the printing layer. An adhesive label having a base material and a printing layer made of the curable composition according to any one of claims 1 to 9 on the base material, and the printing layer has adhesiveness. The adhesive label according to claim 11, wherein the surface of the base material that does not have a printed layer is water-repellent or oil-repellent. A container for containing the curable composition according to any one of claims 1 to 9, wherein the curable composition is contained in the container. An accommodating portion for accommodating the curable composition according to any one of claims 1 to 9.
The imparting means for imparting the curable composition and
A curing means for curing the imparted curable composition and
A two-dimensional or three-dimensional image forming apparatus characterized by having. The applying step of applying the curable composition according to any one of claims 1 to 9,
A curing step of curing the imparted curable composition and
A method for forming a two-dimensional or three-dimensional image, which comprises. A cured product, which is formed by using the curable composition according to any one of claims 1 to 9. The cured product according to claim 16, wherein the glass transition temperature (Tg) is 0 ° C. or higher and 30 ° C. or lower. The cured product according to any one of claims 16 to 17, wherein the water absorption rate is 0% or more and 5% or less. A structure characterized by having a base material and a cured product according to any one of claims 16 to 18 on the base material. A molded product obtained by stretching any of the cured product according to any one of claims 16 to 18 and the structure according to claim 19.