JP6844109B2 - Active energy ray-curable composition for three-dimensional modeling, composition storage container, two-dimensional or three-dimensional image forming device and forming method, and cured product - Google Patents

Description

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

Active energy ray-curable inkjet inks using (meth) acrylic acid esters are widely known (for example, Patent Document 1 and the like). Further, it has been proposed that various functions can be imparted to a coating film by blending a polymer component with a black ink composition containing a polymerizable compound (for example, Patent Document 2 and the like).

One of the advantages of blending the polymer component is that sufficient adhesion can be ensured even for substrates such as plastic materials, which are relatively smooth and difficult to secure the adhesion of the coating film because the liquid does not easily penetrate. is there.

An object of the present invention is to provide an active energy ray-curable composition having a viscosity low enough to be ejected by an inkjet device, having no problem in skin sensitivity, and having excellent adhesion to a polyethylene terephthalate substrate which has not been surface-treated. To do.

The active energy ray-curable composition of the present invention as a means for solving the above-mentioned problems includes a monofunctional (meth) acrylate, a polyfunctional (meth) acrylate, and a polymer having a polyester structure.

According to the present invention, it is possible to provide an active energy ray-curable composition having a viscosity low enough to be ejected by an inkjet device, having no problem in skin sensitivity, and having excellent adhesion to a surface-treated polyethylene terephthalate substrate. Can be done.

It is the schematic which shows an example of the image forming apparatus in this invention. It is the schematic which shows an example of another image forming apparatus in this invention. It is the schematic which shows an example of still another image forming apparatus in this invention. FIG. 4 is a schematic view showing an example of a composition bag of a composition container. FIG. 5 is a schematic view showing an example of a composition container containing a composition bag. FIG. 6 is a graph showing the relationship between the content F'of the polymerization inhibitor and the content C'of the polymerization initiator.

(Active energy ray-curable composition)
The active energy ray-curable composition of the present invention contains a polymer having a monofunctional (meth) acrylate, a polyfunctional (meth) acrylate, and a polyester structure, and further contains other components as necessary.
In the conventional active energy ray-curable ink, the active energy ray-curable composition of the present invention is a base photopolymerizable inkjet ink because the viscosity increases remarkably with the polymer component compounding when the polymer component is blended. This is based on the finding that it is difficult to reduce the viscosity of an active energy ray-curable ink containing a polymer component to a range that can be ejected unless a sufficiently low viscosity material is used as the monomer material. In addition, surface treatment such as corona treatment is generally performed on poorly adhesive substrates such as polyethylene terephthalate, but such treatment may be difficult due to restrictions on equipment and work sites, and the surface surface. It is also desired to ensure adhesion to a poorly adhesive substrate such as polyethylene terephthalate which has not been treated.

In addition, many of the monomer materials used in active energy ray-curable inkjet inks are toxic, and although they are sufficiently low in viscosity, especially in inexpensive and easily procurable (meth) acrylic acid esters, they are applied to the skin. It has a skin-sensing property that causes allergies when touched. At present, even such inks are sometimes used by wearing protective equipment, but it is desirable that there is no problem with skin sensitivity and even if a polymer component is blended, it can still be ejected at room temperature. It is required to obtain an active energy ray-curable inkjet ink having a sufficiently low viscosity.
Although the viscosity of the active energy ray-curable composition can be easily reduced by adding a diluting solvent, it is not preferable to volatilize the solvent and release it into the atmosphere, and it is not preferable for the ink. It should be avoided to mix solvents. It is also possible to use a water-soluble monomer and then add a diluent to reduce the viscosity, but the effect of permeation drying cannot be expected for a poorly adhesive substrate such as a plastic material. Therefore, in order to speed up the printing process, it is necessary to volatilize water for drying, and usually it is necessary to install a heat source or the like, which is not preferable from the viewpoint of energy saving.

<Monofunctional (meth) acrylate>
The monofunctional (meth) acrylate can maintain a sufficiently low viscosity of an ultraviolet (UV) polymerizable composition (including electron beam (EB) polymerizable which is higher energy irradiation) even when a polymer component is blended.
Examples of the monofunctional (meth) acrylate include t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, γ-butyrolactone (meth) acrylate, and isobornyl (meth) acrylate. Examples thereof include formalized trimethylolpropane mono (meth) acrylate, trimethylolpropane (meth) acrylic acid benzoic acid ester, and (meth) acryloyl morpholine. These may be used alone or in combination of two or more. Among these, t-butyl methacrylate, n-pentyl methacrylate, and n-hexyl methacrylate are preferable from the viewpoint of negative skin sensitivity.

The content of the monofunctional (meth) acrylate is preferably 50 parts by mass or more and 85 parts by mass or less with respect to 100 parts by mass in total of the monofunctional (meth) acrylate and the polyfunctional (meth) acrylate. When the content is 50 parts by mass or more and 85 parts by mass or less, the viscosity of the active energy ray-curable composition can be lowered.

<Polyfunctional (meth) acrylate>
The polyfunctional (meth) acrylate refers to a compound having two or more methacryloyl groups or acryloyl groups in the molecule, preferably 2 or more and 6 or less.
Examples of the polyfunctional (meth) acrylate include glycerol di (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, caprolactone-modified dimethylolpropane hexa (meth) acrylate, and triclodecanedimethanol di (meth). ) Acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate of hydroxypivalate, polytetramethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, tetra Ethylene glycol di (meth) acrylate, polyethylene glycol diacrylate [CH ₂ = CH-CO- (OC ₂ H ₄ ) _n- OCOCH = CH ₂ (n≈9), same (n≈14), same (n≈23) )], Dipropylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, Polypropylene glycol dimethacrate [CH ₂ = C (CH ₃ ) -CO- (OC ₃ H ₆ ) _n- OCOC (CH ₃₎ ) = CH ₂ (n≈7)], 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 − Nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane dimethanol diacrylate, propylene oxide-modified bisphenol A di (meth) acrylate, polyethylene glycol dimethacrylate represented by the following formula, dipenta. Ellisritol hexa (meth) acrylate, 2-hydroxypropyl (meth) acrylamide, propylene oxide-modified tetramethylolmethanetetra (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, caprolactone-modified dipentaerythritol hydroxypenta (meth) acrylate, Ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, caprolactone-modified tri. MethylolPro Pantri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propylene oxide-modified neopentyl glycol di (meth) Acrylate, propylene oxide modified glyceryl tri (meth) acrylate, polyester di (meth) acrylate, polyester tri (meth) acrylate, polyester tetra (meth) acrylate, polyester penta (meth) acrylate, polyester poly (meth) acrylate, polyurethane di (meth) Examples thereof include meta) acrylate, polyurethane tri (meth) acrylate, polyurethane tetra (meth) acrylate, polyurethane penta (meth) acrylate, and polyurethane poly (meth) acrylate. These may be used alone or in combination of two or more. Among these, glycerol dimethacrylate, ethylene oxide-modified trimethylolpropane trimethacrylate, caprolactone-modified dipentaerythrylolhexaacrylate, and triclodecanedimethanol dimethacrylate are represented by the following formulas because of their negative skin sensitivity. Polyethylene glycol dimethacrylate is preferred.
(However, in the above formula, n represents 2 to 23.)
In the above formula, n is preferably 2, 3, 4, 9, 14, 23, and more preferably 2, 9, 14.

The content of the polyfunctional (meth) acrylate is preferably 15 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass in total of the monofunctional (meth) acrylate and the polyfunctional (meth) acrylate. When the content is 15 parts by mass or more and 50 parts by mass or less, the curability can be improved.

The monofunctional (meth) acrylates such as the t-butyl methacrylate, the n-pentyl methacrylate, and the n-hexyl methacrylate have a low viscosity at 25 ° C. of 1 mPa · s or more and 2 mPa · s or less as a simple substance, and are activated energy ray-cured. The viscosity of the mold composition can be reduced to a range that allows inkjet ejection without any problem in skin sensitivity.
The vapor pressure of the monofunctional (meth) acrylate was 700 Pa (18.5 ° C.) for the t-butyl methacrylate, 69.1 Pa (25 ° C.) for the n-pentyl methacrylate, and 34 for the n-hexyl methacrylate. It is 7.7 Pa (20 ° C), which is higher than 9.7 Pa (25 ° C) of benzyl acrylate (positive for skin sensitivity), which is a general low-viscosity photopolymerizable monomer, and tends to be disadvantageous for dryness. is there. When low-viscosity monofunctional (meth) acrylate and polyfunctional (meth) acrylate are blended, they may volatilize in the vicinity of the nozzle.

In addition to the monofunctional (meth) acrylate, at least glycerol dimethacrylate, ethylene oxide-modified trimethylolpropane trimethacrylate, caprolactone-modified dipentaerythrylolhexaacrylate, triclodecanedimethanol dimethacrylate, and polyethylene glycol dimethacrylate represented by the above formula. When one kind of polyfunctional (meth) acrylate is used in combination, the curability can be further improved.

The active energy ray-curable composition of the present invention may contain other polymerizable compounds other than monofunctional (meth) acrylate and polyfunctional (meth) acrylate.
Examples of the other polymerizable compound include vinyl ether and the like.
Examples of the vinyl ether include N-vinyl caprolactam, N-vinylpyrrolidone, N-vinylformamide, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanedimethanol monovinyl ether, hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, and diethylene glycol di. Examples thereof include vinyl ether, dicyclopentadiene vinyl ether, tricyclodecane vinyl ether, benzyl vinyl ether, ethyloxetane methyl vinyl ether, triethylene glycol divinyl ether, hydroxybutyl vinyl ether and ethyl vinyl ether. These may be used alone or in combination of two or more.

[Skin sensitivity]
Examples of the polymerizable compound having a negative skin sensitivity include compounds corresponding to at least one of the following (1) to (3).
(1) In a skin sensitization test by a skin sensitization test (LLNA method: Local Lymph Node Asay), a compound having a Simulation Index (SI value) of less than 3 indicating the degree of sensitization (2) Chemical substance safety Compounds evaluated as "negative skin sensation" or "no skin sensation" in the Material Data Sheet (MSDS) (3) "Skin sensation" in the literature [for example, Contact Dermatitis 8 223-235 (1982)]. Compounds evaluated as "Negative" or "No skin sensation" Regarding (1) above, for example, "Functional Materials", September 2005, Vol. 25, No. As shown in 9 and P55, when the SI value is less than 3, it is judged that the skin sensitivities are negative. The lower the SI value, the lower the skin sensation.
In addition, in the above (2), when it is evaluated as "negative skin sensation" or "no skin sensation", it is synonymous with the SI value being less than 3.

The Stimulation Index (SI value) indicating the degree of sensitization of the monofunctional (meth) acrylate and the polyfunctional (meth) acrylate in the skin sensitization test (LLNA method) is preferably low, preferably less than 3. Preferably, 2 or less is more preferable, and 1.6 or less is particularly preferable.

<Polymer having a polyester structure>
The polymer having a polyester structure can improve good curability as an active energy ray-curable composition and good adhesion to a polyethylene terephthalate substrate which has not been surface-treated.

The polymer having the polyester structure is not particularly limited as long as it has good solubility in the monofunctional (meth) acrylate and the polyfunctional (meth) acrylate, and can be appropriately selected.
Examples of the polymer having a polyester structure include a (meth) acrylic-modified polyester resin having a polyester moiety on the main chain, a modified polyester resin having a polyester moiety on the side chain, and a polyester structure on the main chain (styrene-modified polyester resin). , A styrene-modified polyester resin having a polyester moiety on the side chain, a polyester-modified silicone resin, and the like. Specifically, the co-weight of the (meth) acrylic monomer and an unsaturated dicarboxylic acid such as maleic acid ester and fumaric acid ester. Combined, a copolymer of (meth) acrylic monomer in which the hydrogen atoms of the diols at both ends of bisphenol A are substituted with (meth) acryloyl groups and unsaturated dicarboxylic acid, and a polyester moiety consisting of a condensed moiety of oxocarboxylic acid on the side chain. Examples thereof include a modified polyester resin (or a polyester-modified acrylic resin) polymerized by blending a modified (meth) acrylic monomer having the same. Most of the polymers having a pure polyester structure are the monofunctional (meth) acrylates. And it is insoluble in the polyfunctional (meth) acrylate.
The polymer having a polyester structure preferably has a hydroxyl group.

As the polymer having a polyester structure, a commercially available product may be used. As the commercially available product, for example, the product name: Byron 802 (manufactured by Toyobo Co., Ltd., number average molecular weight: 3,000, hydroxyl value: 37 mgKOH) / G, acid value: less than 1 mgKOH / g), trade name: Byron GK810 (manufactured by Toyobo Co., Ltd., average molecular weight: 6,000, hydroxyl value: 19 mgKOH / g, acid value: 5 mgKOH / g), trade name: Byron 650 (Manufactured by Toyobo Co., Ltd., hydroxyl value: 5 mgKOH / g, acid value: less than 2 mgKOH / g, number average molecular weight: 23,000) and the like. These may be used alone or in combination of two or more.

The conditions under which the polymer having a polyester structure dissolves in the monofunctional (meth) acrylate and the polyfunctional (meth) acrylate are determined by the weight average molecular weight, conformation and configuration of the polymer having the polyester structure. However, the content of the polyester moiety in the polymer having the polyester structure is preferably 50% by mass or less, more preferably 30% by mass or less, based on the total amount of the polymer having the polyester structure. It is also known in the field of coating materials to form a so-called O / O type emulsion using a plurality of types of mixed solvents having different solubilities, but this technique is applied to reduce the viscosity of curability to achieve the object of the present invention. That is extremely difficult.

The polymer having the polyester structure preferably has good solubility in the monofunctional (meth) acrylate and the polyfunctional (meth) acrylate. Therefore, one having a crosslinked structure cannot be used, and a chain shape is preferable. Even if it is a chain, a polymer having an excessively large average molecular weight is not preferable because it significantly impairs workability when dissolved in ink, and the weight average molecular weight of the polymer having the polyester structure is preferably 100,000 or less. More preferably 50,000 or less, and more preferably 1,000 or more. The number average molecular weight is preferably 10,000 or less. Furthermore, regarding solubility, it is important that the polymer having a polyester structure is not very rigid and the crystallinity is not too high, and in addition, it is also important that it is practically inexpensive and easily procured. Further, depending on the solubility and other circumstances, those having an arbitrary acid value or hydroxyl value can also be used.

Here, the weight average molecular weight and the number average molecular weight are the weight average molecular weight and the number average molecular weight in terms of standard polystyrene molecular weight, and are high performance liquid chromatography (manufactured by Nippon Water Co., Ltd., "Waters 2695 (main body)" and "Waters 2414". (Detector) ”), column: Chromatography GPC KF-806L (exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical number of stages: 10,000 stages / piece, filler material: styrene It can be measured by using three series of −divinylbenzene copolymer and filler particle size: 10 μm).

The glass transition temperature of the polymer having a polyester structure is preferably 30 ° C. or higher, more preferably 50 ° C. or higher. When the glass transition temperature is 30 ° C. or higher, the polymer having the polyester structure can maintain a state of the glass transition temperature or higher in a general room temperature environment, which is suitable for keeping the coating strength high. is there.

Since the polymer having a polyester structure precipitates when the active energy ray-curable composition is added dropwise to a solvent such as methanol, it can be isolated by filtering the polymer, which can be isolated by infrared spectroscopy. It can be confirmed as an absorption peak derived from the ester bond near 1,700 cm ^-1. It can be confirmed whether the other components are the same as the polymer having the polyester structure by mass spectrometry gas chromatogram method or the like.

The content of the polymer having the polyester structure is preferably 10 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass in total of the monofunctional (meth) acrylate and the polyfunctional (meth) acrylate.

<Other polymers>
The other polymer is obtained by polymerizing at least one selected from styrene, a styrene derivative, an acrylic acid ester, and acrylic acid.
The other polymers include homopolymers and copolymers.
The other polymer can maintain better adhesion and improve water resistance even when an image or a cured product formed on a non-permeable substrate such as a brass material, metal, or glass is immersed in water. ..
The other polymer preferably has a hydroxyl group.

The glass transition temperature of the other polymer is preferably 30 ° C. or higher, more preferably 50 ° C. or higher. When the glass transition temperature is 30 ° C. or higher, the other polymer can maintain a state of the glass transition temperature or higher in a general room temperature environment, which is suitable for keeping the coating film strength high.
The weight average molecular weight of the other polymers is preferably 1,000 or more and 100,000 or less, and more preferably 1,000 or more and 50,000 or less.

As the other polymer, it may be synthesized as appropriate, or a commercially available product may be used.
Examples of the commercially available product include trade name: John Krill 611 (styrene-acrylic resin, manufactured by BASF, acid value: 53 mgKOH / g, glass transition temperature: 50 ° C.), trade name: John Krill 804 (acrylic resin, BASF). Manufactured by the company, acid value: 15 mgKOH / g, glass transition temperature: 70 ° C., trade name: Heimer ST-95 (low molecular weight polystyrene resin, manufactured by Sanyo Kasei Kogyo Co., Ltd., acid value: 0 mgKOH / g, glass transition temperature: 42 ℃), trade name: ARUFON (registered trademark) UC-3000 (solid) (acrylic resin, manufactured by Toa Synthetic Co., Ltd., acid value: 74 mgKOH / g, glass transition temperature: 65 ° C), trade name: VS-1063, polystyrene Resin, manufactured by Seikou PMC Co., Ltd., acid value: 0 mgKOH / g, glass transition temperature: 100 ° C.) and the like. These may be used alone or in combination of two or more.

<Polymerization initiator>
The active energy ray-curable composition of the present invention preferably further contains a polymerization initiator.
Examples of the polymerization initiator include a photoradical polymerization initiator. Among these, a photoradical polymerization initiator having a negative skin sensitivity is preferable.

Examples of the photoradical polymerization initiator include a molecular cleavage type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator.
Examples of the molecular cleavage type photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenylketone, and 2-hydroxy-2-methyl-1-phenylpropane-. 1-on, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1- {4- [4- (2-) Hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methyl-1-propan-1-one, phenylglycoxyacid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino Propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4) -Il-phenyl) butane-1-one, 2- (dimethylamino) -2- (4-methylbenzyl) -1- (4-morpholinophenyl) butane-1-one, bis (2,4,6-trimethyl) Phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoylphosphine oxide, 1,2-octanedione- [4 -(Phenylthio) -2- (o-benzoyloxime)], Etanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime) , [4- (Methylphenylthio) phenyl] phenylmethanone, 2- [4- (methylthio) benzoyl] -2- (4-morpholinyl) propane and the like. These may be used alone or in combination of two or more.
Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone compounds such as benzophenone, methylbenzophenone, methyl-2-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylsulfide, and phenylbenzophenone; 2,4-diethyl. Examples thereof include thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, and 1-chloro-4-propylthioxanthone. These may be used alone or in combination of two or more.
Among these, 1-hydroxycyclohexylphenyl ketone and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-) are low in skin sensitivity and can be easily procured at low cost. An equimolar mixture of morpholin-4-yl-phenyl) butane-1-one, 2,4-diethylthioxanthone and -2-ethylhexyl p-dimethylaminobenzoate is preferred.

As the polymerization initiator, a commercially available product can be used, and examples of the commercially available product include trade name: Irgacure 184, trade name: Irgacure 379, and trade name: Irgacure 907 (all manufactured by BASF). These may be used alone or in combination of two or more.

(Meta) acrylic acid esters, (meth) acrylamides and their derivatives, vinyl ethers, etc. are known to have ionic polymerization properties, but ionic polymerization initiators are generally expensive and are not exposed to light. In addition, since a strong acid and a strong alkali are slightly generated in the above, special consideration such as having acid resistance and alkali resistance in the ink supply path in the inkjet coating system is required. Therefore, there are restrictions on the selection of the members constituting the inkjet coating system. On the other hand, in the active energy ray-curable composition of the present invention, an inexpensive photoradical polymerization initiator that does not generate a strong acid or a strong alkali can be used, so that ink can be produced at low cost and an inkjet can be produced. It also facilitates the selection of materials for the coating system. Of course, when using a high-energy light source such as an electron beam, β-ray, X-ray, α-ray, or γ-ray, the polymerization reaction can proceed without using a polymerization initiator, but this is more common than before. This is well known, and will not be described in detail in the present invention.

The content of the polymerization initiator is preferably 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass in total of the monofunctional (meth) acrylate and the polyfunctional (meth) acrylate. When the content is 5 parts by mass or more and 15 parts by mass or less, the curability can be improved.

<Polymerization inhibitor>
In the vicinity of the nozzle of the inkjet ejection device, there is an environment in which the polymerization reaction easily proceeds due to the ejection temperature, the temperature rise in the UV lamp, the leaked light, and the like. Further, some of the low-viscosity monomers volatilize, and the volatilization may increase the concentration of the polymerization initiator to accelerate the polymerization reaction. In addition, when a polymer having a polyester structure is blended in the ink, adhesiveness is exhibited along with the polymerization reaction, so that the ink adheres to the nozzle and easily causes clogging or bending, and a predetermined recovery operation is performed. However, there were some things that could not be resolved. Therefore, by containing a polymerization inhibitor, the polymerization reaction can be suppressed even when the low-viscosity monomer volatilizes, and the discharge reliability can be improved.

The polymerization inhibitor preferably has two hydroxyl groups in the molecule. When the molecule has two hydroxyl groups, better ejection recovery can be obtained as compared with a polymerization inhibitor having one hydroxyl group in the molecule.

Examples of the polymerization inhibitor include 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 and the like. These may be used alone or in combination of two or more.

As the polymerization inhibitor, a commercially available product can be used, and as the commercially available product, trade name: methquinone (4-methoxyphenol, manufactured by Seiko Kagaku Co., Ltd.), trade name: MNT (4-methoxy-1- Naftor, manufactured by Kawasaki Kasei Kogyo Co., Ltd.), Product name: Hydroquinone (p-hydroxyphenol, manufactured by Seiko Chemical Co., Ltd.), Product name: MH (Methylhydroquinone, manufactured by Seiko Chemical Co., Ltd.), Product name :, Product name: Non Flex Alba (2,5-di-tert-butylhydroquinone, manufactured by Seiko Kagaku Co., Ltd.) and the like can be mentioned. These may be used alone or in combination of two or more.

The content of the polymerization inhibitor is preferably 0.01 × A mass% or more when the content of the polymerization initiator is A mass%.

<Polymerization accelerator>
The active energy ray-curable composition of the present invention can contain a polymerization accelerator.
Examples of the polymerization accelerator include amines and the like.
Examples of the amine include ethyl p-dimethylaminobenzoate, -2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, -2-dimethylaminoethyl benzoate, and butoxy p-dimethylaminobenzoate. Examples include ethyl.

<Color material>
The active energy ray-curable composition of the present invention may contain a coloring material. As the coloring material, various pigments and dyes that impart black, white, magenta, cyan, yellow, green, orange, glossy colors such as gold and silver, etc., depending on the purpose and required characteristics of the composition in the present invention. Can be used. The content of the coloring material may be appropriately determined in consideration of the desired color concentration, dispersibility in the composition, etc., and is not particularly limited, but is 0. It is preferably 1 to 20% by mass. The active energy ray-curable composition of the present invention may be colorless and transparent without containing a coloring material, and in that case, for example, it is suitable as an overcoat layer for protecting an image.
As the pigment, an inorganic pigment or an organic pigment can be used, and one type may be used alone or two or more types may be used in combination.
As the inorganic pigment, for example, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide can be used.
Examples of organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azolakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments and quinophthalones. Polycyclic pigments such as pigments, dye chelate (for example, basic dye type chelate, acidic dye type chelate, etc.), dyeing lake (basic dye type lake, acidic dye type lake), nitro pigment, nitroso pigment, aniline black, Daylight fluorescent pigments can be mentioned.
In addition, a dispersant may be further contained in order to improve the dispersibility of the pigment. The dispersant is not particularly limited, and examples thereof include dispersants commonly used for preparing pigment dispersions such as polymer dispersants.
As the dye, for example, an acid dye, a direct dye, a reactive dye, and a basic dye can be used, and one type may be used alone or two or more types may be used in combination.

<Organic solvent>
The active energy ray-curable composition of the present invention may contain an organic solvent, but it is preferable not to contain it if possible. If the composition does not contain an organic solvent, particularly a volatile organic solvent (VOC (Volatile Organic Compounds) free), the safety of the place where the composition is handled is further enhanced, and it is possible to prevent environmental pollution. .. The "organic solvent" means, for example, a general non-reactive organic solvent such as ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and should be distinguished from the reactive monomer. is there. Further, "not containing" the organic solvent means that it is substantially not contained, and it is preferably less than 0.1% by mass.

<Other ingredients>
Examples of the other components include a higher fatty acid ester having a polyether group, an amino group, a carboxyl group and a hydroxyl group; a polydimethylsiloxane compound having a polyether group, an amino group, a carboxyl group and a hydroxyl group at the side chain or the terminal; Surfactants such as fluoroalkyl compounds having ethers, amino groups, carboxyl groups and hydroxyl groups; polar group-containing polymer pigment dispersants and the like can be mentioned.

<Preparation of active energy ray-curable composition>
The active energy ray-curable composition of the present invention can be prepared by using the above-mentioned various components, and the preparation means and conditions thereof are not particularly limited. For example, a polymerizable monomer, a pigment, a dispersant and the like are used in a ball mill. It is put into a disperser such as a kitty mill, a disc mill, a pin mill, or a dyno mill, and dispersed to prepare a pigment dispersion, and the pigment dispersion is further mixed with a polymerizable monomer, an initiator, a polymerization inhibitor, a surfactant, and the like. It can be prepared by letting it.

<Active energy ray>
The active energy rays used for curing the active energy ray-curable composition of the present invention include, in addition to ultraviolet rays, polymerizable components in the composition such as electron beams, α rays, β rays, γ rays, and X rays. It is not particularly limited as long as it can impart the energy required for advancing the polymerization reaction of the above. In particular, when a high-energy light source is used, the polymerization reaction can proceed without using a polymerization initiator. Further, in the case of ultraviolet irradiation, mercury-free is strongly desired from the viewpoint of environmental protection, and replacement with a GaN-based semiconductor ultraviolet light emitting device is very useful industrially and environmentally. Further, the ultraviolet light emitting diode (UV-LED) and the ultraviolet laser diode (UV-LD) are compact, have a long life, have high efficiency, and are low in cost, and are preferable as an ultraviolet light source.

<Viscosity>
The viscosity of the active energy ray-curable composition of the present invention 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 the case, the viscosity in the range of 20 ° C. to 65 ° C., preferably the viscosity at 25 ° C., is preferably 5 mPa · s or more and 18 mPa · s or less. Further, it is more 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.

<Use>
The application of the active energy ray-curable composition of the present invention is not particularly limited as long as it is in a field in which an active energy ray-curable material is generally used, and can be appropriately selected depending on the intended purpose, for example, for molding. Examples thereof include resins, paints, adhesives, insulating materials, mold release agents, coating materials, sealing materials, various resists, and various optical materials.
Further, the active energy ray-curable composition of the present invention can be used as an ink to not only form two-dimensional characters and images and design coatings on various substrates, but also to form a three-dimensional three-dimensional image (three-dimensional model). It 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 repeatedly curing and laminating a powder layer, and is also shown in FIGS. 2 and 3. It may be used as a three-dimensional constituent material (model material) or a support member (support material) used in such a laminated modeling method (stereolithography). Note that FIG. 2 is a method in which the active energy ray-curable composition of the present invention is discharged into a predetermined region, and those cured by irradiating with active energy rays are sequentially laminated to perform three-dimensional modeling (details will be described later). FIG. 3 shows that the storage pool (accommodation portion) 1 of the active energy ray-curable composition 5 of the present invention is irradiated with the active energy ray 4 to form a cured layer 6 having a predetermined shape on the movable stage 3. This is a method of sequentially laminating and performing three-dimensional modeling.
As a three-dimensional modeling device for modeling a three-dimensional model using the active energy ray-curable composition of the present invention, a known one can be used, and the present invention is not particularly limited, but for example, a means for accommodating the composition. , A supply means, a discharge means, an active energy ray irradiation means, and the like.
The present invention also includes a cured product obtained by curing an active energy ray-curable composition and a molded product obtained by processing a structure in which the cured product is formed on a substrate. The molded product is, for example, a cured product or structure formed in a sheet shape or a film shape that has been subjected to molding processing such as heat stretching or punching, and is, for example, an automobile, an OA device, or electricity. -Suitably used for applications that require molding after decorating the surface, such as electronic devices, meters for cameras, panels for operation units, and the like.
The base material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, paper, thread, fiber, cloth, leather, metal, plastic, glass, wood, ceramics, or a composite material thereof and the like. From the viewpoint of processability, a plastic base material is preferable.

The active energy ray-curable composition of the present invention is preferably an ink for inkjet.

<Composition container>
The composition container of the present invention means a container in which an active energy ray-curable composition is contained, and is suitable for use in the above-mentioned applications. For example, when the active energy ray-curable composition of the present invention is used for ink, the container containing the ink can be used as an ink cartridge or an ink bottle, whereby ink transfer, ink replacement, etc. It is not necessary to directly touch the ink in the work, 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 desirable that it is covered with a sex sheet or the like.

The ink cartridge will be described with reference to FIGS. 4 and 5. FIG. 4 is a schematic view showing an example of the ink bag 241 of the composition container, and FIG. 5 is a schematic view showing the composition container 200 in which the ink bag 241 of FIG. 4 is housed in the cartridge case 244.
As shown in FIG. 4, ink is filled in the ink bag 241 from the ink injection port 242, the air remaining in the ink bag is exhausted, and then the ink injection port 242 is closed by fusion. At the time of use, the needle of the main body of the device is pierced into the ink discharge port 243 made of a rubber member to supply the ink to the device. The ink bag 241 is formed of a packaging member such as a non-permeable aluminum laminated film. Then, as shown in FIG. 5, it is usually housed in a plastic cartridge case 244, and is used as a composition storage container 200 by being detachably attached to various inkjet coating devices.
It is preferable that the composition container of the present invention is removable from the inkjet coating device. As a result, replenishment and replacement of ink can be simplified and workability can be improved.

<Image formation method, forming device>
The method for forming an image of the present invention includes, at least, an irradiation step of irradiating an active energy ray to cure the active energy ray-curable composition of the present invention, and the image forming apparatus of the present invention has an active energy. An irradiation means for irradiating the rays and an accommodating portion for accommodating the active energy ray-curable composition of the present invention 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 active energy ray-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.
FIG. 1 is an example of an image forming apparatus provided with an inkjet ejection means. Ink is ejected to the recording medium 22 supplied from the supply roll 21 by each color printing unit 23a, 23b, 23c, 23d provided with an ink cartridge for each color active energy ray-curable ink of yellow, magenta, cyan, and black and an ejection head. Will be done. Then, the light sources 24a, 24b, 24c, and 24d for curing the ink are irradiated with active energy rays to cure the ink, and a color image is formed. After that, the recording medium 22 is conveyed to the processing unit 25 and the printed matter take-up roll 26. Each printing unit 23a, 23b, 23c, 23d may be provided with a heating mechanism so that the ink is liquefied at the ink ejection portion. Further, if necessary, a mechanism for cooling the recording medium to about room temperature by contact or non-contact may be provided. Further, as an inkjet recording method, a serial method in which the head is moved to eject ink onto the recording medium or a recording medium is continuously moved with respect to a recording medium that moves intermittently according to the width of the ejection head. Any of the line methods of ejecting ink onto the recording medium from the head held at a fixed position can be applied.
The recording medium 22 is not particularly limited, and examples thereof include paper, film, metal, and composite materials thereof, and may be in the form of a sheet. Further, the configuration may be such that only single-sided printing is possible, or double-sided printing is also possible.
Further, the activation energy rays from the light sources 24a, 24b, and 24c may be weakened or omitted, and after printing a plurality of colors, the activation energy rays may be irradiated from the light source 24d. As a result, energy saving and cost reduction can be achieved.
The recorded matter recorded by the ink of the present invention includes not only those printed on a smooth surface such as ordinary paper or resin film, but also those printed on an uneven surface to be printed, metal, ceramic, and the like. It also includes those printed on the surface to be printed made of various materials. Further, by superimposing 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) according to the present invention. The image forming apparatus 39 of FIG. 2 uses a head unit (movable in the AB direction) in which inkjet heads are arranged to discharge the first active energy ray-curable composition from the discharge head unit 30 for a modeled object for a support. The second active energy ray-curable composition having a composition different from that of the first active energy ray-curable composition is discharged from the head units 31 and 32, and each of these compositions is cured by the adjacent ultraviolet irradiation means 33 and 34. While stacking. More specifically, for example, the second active energy ray-curable composition is discharged from the support discharge head units 31 and 32 onto the modeled object support substrate 37, and is irradiated with active energy rays to be solidified. After forming the first support layer having the reservoir portion, the first active energy ray-curable composition is discharged from the discharge head unit 30 for a modeled object to the reservoir portion, and is solidified by irradiating the reservoir portion with the active energy ray. By repeating the process of forming the first modeled object layer a plurality of times while lowering the vertically movable stage 38 according to the number of times of stacking, the support layer and the modeled object layer are laminated to form the three-dimensional modeled object 35. To make. 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.

<Base material>
Examples of the base material include paper, plastic, metal, ceramics, glass, and composite materials thereof. For a permeable base material such as woodfree paper, it is also practical to use a water-based ink or an oil-based ink that does not dry quickly because the effect of osmotic drying can be expected. On the other hand, for non-permeable substrates such as matte coated paper, gloss coated paper, plastic film, plastic moldings, ceramics, glass, and metal, it is more practical to use ink that can obtain quick drying, and it is more practical to use light irradiation. It can be suitably used for the active energy ray-curable composition of the present invention because it cures immediately. Examples of the non-permeable base material include a polyethylene terephthalate base material. In the polyethylene terephthalate base material, corona treatment may be performed for the purpose of activating the surface and improving the adhesion, but the treatment that generates such electric sparks is an activity corresponding to a dangerous substance under the Fire Service Act. Although it cannot normally be used at the coating site of the energy ray-curable composition, the active energy ray-curable composition of the present invention can obtain sufficient adhesion without surface treatment such as the corona treatment. Can be done.

(Cured product)
The cured product of the present invention has a base material and a cured film obtained by irradiating the active energy ray-curable composition of the present invention with active energy rays and curing the active energy ray-curable composition on the base material.
As the base material, a polyethylene terephthalate base material is preferable.
The coating film preferably contains a monofunctional (meth) acrylate, a polyfunctional (meth) acrylate, and a polymer having a polyester structure.
The cured product has an adhesion between the polyethylene terephthalate base material and the cured film of 1 kPa or more, preferably 10 kPa or more.

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

<SI value evaluation method>
The SI value was measured as follows according to a skin sensitivity test by the LLNA method (Local Lymph Node Asay).

[Test material]
<< Positive control substance >>
As a positive control substance, α-hexyl cinnamaldehyde (HCA, manufactured by Wako Pure Chemical Industries, Ltd.) was used.

<< Medium >>
As a medium, a mixed solution of acetone (manufactured by Wako Pure Chemical Industries, Ltd.) and olive oil (manufactured by Fujimi Pharmaceutical Industries, Ltd.) at a volume ratio (acetone: olive oil) = 4: 1 was used.

<< Animals used >>
Female mice were acclimated for 8 days, including 6 days of quarantine, for each of the test substance, positive control, and vehicle control. No abnormalities were found in any of the animals during the quarantine and acclimation period.
Using the body weight measured 2 days before the start of sensation, the animals were divided into 2 groups (4 animals / group) so that the average body weight of the individual was within ± 20% of the total body weight by the random sampling method by body weight group. .. The age of the animals at the onset of sensation was 8 to 9 weeks. Animals that were excluded from the grouping were excluded from the study.
Animals used were identified by applying oil-based ink to the tail throughout the test period, while cages were labeled and identified.

<< Breeding environment >>
The animals used had a temperature of 21 ° C or higher and 25 ° C or lower, a relative humidity of 40% or higher and 70% or lower, a ventilation rate of 10 times or more and 15 times or less / hour, and a light-dark cycle of 12 hours throughout the entire breeding period including the quarantine and acclimation period. It was bred in the breeding room of the barrier system set to 7 o'clock on and 19:00 off.
A polycarbonate cage was used as the breeding cage. The animals used were bred in 4 animals / cage.
As the feed, a solid feed MF for laboratory animals (manufactured by Oriental Yeast Co., Ltd.) was used, and the animals used were allowed to freely ingest. As drinking water, tap water to which sodium hypochlorite (Purax, manufactured by Oyalux Co., Ltd.) was added so that the chlorine concentration was approximately 5 ppm was freely ingested by the animals used by a water bottle. The floor was made of sunflake (fir wood, electric plane shavings, manufactured by Charles River Laboratories, Japan). As the feed and breeding equipment, those sterilized by autoclave (121 ° C., 30 minutes) were used.
The cage and bedding were replaced at the time of grouping and on the day of ingestion of the auricular lymph nodes (at the time of removal from the breeding room), and the water bottle and rack were replaced at the time of grouping.

[Test method]
<< Group composition >>
Table 1 shows the group composition used in the SI value measurement test.

[Preparation]
<< Test substance >>
Table 2 shows the weighing conditions of the test substance. The test substance was weighed in a volumetric flask, and the volume was adjusted to 1 mL while adding a medium. The preparation solution was placed in a light-shielded airtight container (made of glass).

<< Positive control substance >>
Approximately 0.25 g of HCA was accurately weighed and a 25.0 w / v% solution was prepared as 1 mL with the addition of medium. The preparation was placed in a light-tight airtight container (made of glass).

<< BrdU >>
200 mg of 5-bromo-2'-deoxyuridine (BrdU, manufactured by Nacalai Tesque, Inc.) was accurately weighed in a volumetric flask, physiological saline (manufactured by Otsuka Pharmaceutical Factory, Ltd.) was added, and ultrasonic irradiation was performed to dissolve it. .. Then, the volume was adjusted to 20 mL to prepare a 10 mg / mL solution (BrdU preparation solution). The prepared solution was sterilized by filtration using a sterilized filtration filter and placed in a sterilized container.

<< Preparation time and storage period >>
The positive control substance preparation solution was prepared the day before the start of sensation and stored in a cool place except when in use. The medium and the test substance preparation solution were prepared on each feeling day. BrdU solution was prepared 2 days before administration and stored in a cool place until the day of administration.

[Feeling and administration of BrdU]
<< Feeling >>
25 μL of each test substance and positive control substance preparation solution and medium were applied to both auricles of animals. A micropipettor was used for application. This operation was performed once a day for 3 consecutive days.
<< Administration of BrdU >>
Approximately 48 hours after the final sensation, 0.5 mL of BrdU preparation was intraperitoneally administered per animal.

[Observation and inspection]
<< General condition >>
All animals used in the test were observed at least once a day from the start date of sensation to the date of collection of auricular lymph nodes (the date of removal from the breeding room). In the calculation method of the observation date, the feeling start date was set to Day 1.

<< Weight measurement >>
Body weight was measured on the day when the feeling started and the day when the auricular lymph node was collected (the day when it was taken out of the breeding room). In addition, the average value and standard error of body weight for each group were calculated.

<< Collection and weight measurement of auricular lymph nodes >>
Animals were euthanized approximately 24 hours after BrdU administration and auricular lymph nodes were harvested. The surrounding tissue was removed and the bilateral auricular lymph nodes were weighed together. In addition, the mean value and standard error of the auricular lymph node weight for each group were calculated. After weighing, each individual was cryopreserved in a biomedical freezer set at −20 ° C.

<< Measurement of BrdU uptake >>
After returning the auricular lymph nodes to room temperature, they were ground and suspended while adding physiological saline. After filtering this suspension, 3 wells were dispensed into 96-well microplates for each individual, and the amount of BrdU uptake was measured by the ELISA method. The reagent was obtained from a multi-plate reader (FLUOstar OPTIMA, manufactured by BMG LABTECH) using a commercially available kit (Cell Proliferation ELISA, BrdU colorimetric, Cat. No. 1647229, manufactured by Roche Diagnostics Co., Ltd.). Regarding the absorbance (OD370 nm-OD492 nm, BrdU uptake amount) of each individual, the average value of 3 wells was taken as the BrdU measured value of each individual.

[Evaluation of results]
<< Calculation of Stimulation Index (SI) >>
As shown by the following formula, the SI value of each individual was calculated by dividing the BrdU measured value of each individual by the average value of the BrdU measured values of the medium control group. The SI value of each test group was the average value of SI of each individual. The SI value was rounded off to the first decimal place and displayed up to the first decimal place.

(Examples 1 to 15 and Comparative Examples 1 to 3)
The following materials (A) to (E) are used in the blending ratios (numerical values are parts by mass) shown in each column of Examples and Comparative Examples in Table 3 below, and each active energy ray-curable type is used according to a conventional method. The composition was obtained.
(A) Monofunctional (meth) acrylate (B) Polyfunctional (meth) acrylate (C) Photoradical polymerization initiator with negative skin sensitivity (D) Polymer with polyester structure (E) Other polymers

Using the obtained active energy ray-curable composition, the viscosity was measured as follows.

<Viscosity>
The viscosity of each prepared active energy ray-curable composition at 25 ° C. was rotated by using a cone rotor (1 ° 34'x R24) with a cone plate type rotational viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd. The measurement was performed by setting the temperature of the constant temperature circulating water to 25 ° C. at several 50 rpm. VISCOMATE VM-150III was used to adjust the temperature of the circulating water. The results are shown in Table 3. Each active energy ray-curable composition of the example had a viscosity range of 5 mPa · s or more and 18 mPa · s or less at 25 ° C.

First, as the handling of the active energy ray-curable composition, the ink was sealed in the aluminum pouch bag having the shape shown in FIG. 4 so as to prevent air bubbles from entering, and the ink was sealed in the plastic cartridge as shown in FIG. A propylene base material (trade name) in which the pouch bag is stored and the cartridge is placed in an ink flow path from the cartridge to the GEN4 head manufactured by Ricoh Printing Systems Co., Ltd. in a housing capable of storing the cartridge, and the surface is corona-treated. : Corona-treated surface of ester film E5100, manufactured by Toyo Boseki Co., Ltd.) or untreated polyethylene terephthalate substrate (trade name: untreated surface of ester film E5100, manufactured by Toyo Boseki Co., Ltd.) A solid coating film was prepared. The amount of ink droplets applied was adjusted so that the average thickness of the solid coating film was about 10 μm.
^{The produced solid printed coating film was cured at 0.2 (mW / cm 2} ) in a wavelength range corresponding to the UVA region under a light intensity condition of 3,000 (mJ / cm ² ) to obtain a cured product. Obtained. This was used for the adhesion evaluation.

Next, the adhesion of the cured coating film to the substrate was evaluated for each active energy ray-curable composition. The results are shown in Table 3.
<Adhesion>
For the adhesion of the cured coating film to the substrate, a commercially available PET film (manufactured by Toyo Boseki Co., Ltd., ester film E5100, average thickness: 100 μm) is used as a general-purpose film material widely used as a packaging material and an industrial material. In use, the active energy ray-curable composition is inkjet-discharged onto the corona-treated surface and the untreated surface of the PET film, and light is irradiated by a UV irradiator (LH6 (D valve), manufactured by Fusion Systems Japan Co., Ltd.). The cured solid coating film was measured by the cross-cut method shown in JIS-K-5600-5-6, and "adhesion" was evaluated based on the following evaluation criteria.
In addition, a tensile tester (device name: Autograph AG-10kNXplus, manufactured by Shimadzu Corporation) was used to measure the stress (adhesion) required to peel a coating film of a certain area from the substrate.
[Evaluation criteria]
⊚: No peeling or only small peeling at the intersection of cuts, and the adhesion was 10 kPa or more. ○: No peeling or only small peeling at the intersection of cuts. Adhesion was 1 kPa or more and less than 10 kPa Δ: No clear peeling was observed, but adhesion was less than 1 kPa ×: Clear peeling was observed.

* 2: Did not cure * 3: Cannot eject by inkjet due to high viscosity

Details of A1 to A4, B1 to B5, C1 to C2, D1 to D3, and E1 in Table 3 are as follows.
The numerical value in parentheses at the end is the SI value in the LLNA test of (1), and "negative" or "none" is the document of (2) or MSDS (chemical substance safety) of (3). In the data sheet), it was evaluated as "negative skin sensation" or "no skin sensation". In addition, "positive" is added with the warning phrase "R43" indicating that there is a problem with skin sensitization in the risk phrase notation rules in the European Directive, or "H317" indicating that there is a problem with skin sensitization in the CLP Regulation. Is to be done. Since the polymer component has a high molecular weight, it is difficult to pass through the skin and usually does not have skin sensation.

-(A) Monofunctional (meth) acrylate-
-A1: t-Butyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., "t-Butyl acrylate" (positive)
-A2: t-Butyl Methacrylate, manufactured by Mitsubishi Rayon Co., Ltd., "Acryester TB" (negative) Evaluation based on literature (test method: maximization method)
-A3: n-Pentyl Methacrylate, Zhangjiagang Render Chemical, "n-AmylMethacrylate" (negative) Evaluation based on literature (test method: maximization method)
-A4: n-hexyl methacrylate, manufactured by Tokyo Kasei Kogyo Co., Ltd., "n-HexylMesurate" (negative) Evaluation based on literature (test method: maximization method)

-(B) Polyfunctional (meth) acrylate-
-B1: Ethylene oxide-modified trimethylolpropane triacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd., "A-TMPT-3EO" (positive)
-B2: Glycerol dimethacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd., "701", (1.2)
-B3: Tricyclodecanedimethanol dimethacrylate, "DCP" manufactured by Shin Nakamura Chemical Industry Co., Ltd., (1.3)
-B4: Ethylene oxide-modified trimethylolpropane trimethacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd., "TMPT-3EO", (1.0)
-B5: Caprolactone-modified dipentaerythrylolhexaacrylate, evaluated by Nippon Kayaku Co., Ltd. (negative) MSDS (test method: OECD test guideline 406)

-(C) Photoradical polymerization initiator with negative skin sensitivity-
-C1: 1-Hydroxy-cyclohexylphenyl ketone, manufactured by BASF, "Irgacure 184" (none) Evaluation by MSDS (test method: OECD test guideline 406)
C2: 2-Dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butane-1-one, BASF, "Irgacure 379" (none) MSDS evaluation (Test method: OECD test guideline 406)

-(D) Polymer having a polyester structure-
D1: Polymer having a polyester structure, number average molecular weight: 3,000, hydroxyl value: 37 mgKOH / g, acid value: less than 1 mgKOH / g, manufactured by Toyobo Co., Ltd., "Byron 802"
-D2: Polymer having a polyester structure, number average molecular weight: 6,000, hydroxyl value: 19 mgKOH / g, acid value: 5 mgKOH / g, manufactured by Toyobo Co., Ltd., "Byron GK810"
-D3: Polymer having a polyester structure, number average molecular weight: 23,000, hydroxyl value: 5 mgKOH / g, acid value: less than 2 mgKOH / g, manufactured by Toyobo Co., Ltd., "Byron 650"

-Other polymers-
-E1: Styrene-acrylic resin, acid value: 53 mgKOH / g, weight average molecular weight: 8,100, manufactured by BASF, "John Krill 611"

-Carbon black-
The blending amount is shown as a state in which the polymer dispersant Solsperse 39000 manufactured by Japan Lubrizol Co., Ltd. is contained in a mass ratio of 3: 1 with respect to carbon black # 10 manufactured by Mitsubishi Chemical Corporation.

From Comparative Example 1 and Example 1, it was found that when a polymer having a polyester structure is contained as a polymer component of Group D, adhesion to a polyethylene terephthalate substrate which has not been surface-treated can be obtained.
As can be seen from Comparative Example 2, the curability was insufficient when the polyfunctional (meth) acrylate was not contained.
Further, as can be seen from Comparative Example 3, when the monofunctional (meth) acrylate was not contained, inkjet printing could not be performed due to the high viscosity.
From Examples 1 and 2, even when a monofunctional (meth) acrylate of Group A having no problem with skin sensitization is used, the adhesion to the polyethylene terephthalate substrate which has not been surface-treated is similarly maintained. Since it was found that the ink can be obtained, it is desirable to use an ink that does not have a problem with skin sensitization in consideration of safety in handling ink.
From Examples 2 and 3, even if different types of polymers having a polyester structure are used or a plurality of polymers are used in combination, adhesion to a polyethylene terephthalate substrate which has not been surface-treated can be obtained. all right.
From Examples 4 and 5, it was found that even if the compounding ratio of the polymer having a polyester structure was increased or decreased, adhesion to a polyethylene terephthalate substrate which had not been surface-treated could be obtained.
From Examples 1, 6 and 7, even when different monofunctional (meth) acrylates of Group A were used as those having no problem with skin sensitivities, none of them was subjected to surface treatment. It was found that adhesion was obtained.
From Example 8, it was found that adhesion to PET not subjected to surface treatment can be obtained even when a coloring material is contained or when the type of the polymerization initiator of Group C is different.
From Examples 9, 10, 11, 12, and 13, even when different types of polyfunctional (meth) acrylates of Group B are used, adhesion to PET without surface treatment can be obtained. Since it was found that, considering the safety in handling ink, it is desirable to use an ink that does not have a problem with skin sensitivity.
From Example 14, it was found that even if a plurality of materials of each group are used in combination, adhesion to a polyethylene terephthalate substrate which has not been surface-treated can be obtained. Therefore, the optimum material should be selected as necessary. Just do it.
Good adhesion was also obtained in Example 15, but as compared with other Examples, droplets were more likely to elongate during inkjet ejection and mist generation was slightly higher. Therefore, it is more preferable that the polymer component has a small molecular weight. I understood it.
In all the above-mentioned examples, the coating film after light irradiation was well cured without stickiness in the touch confirmation.
Since the polymer having a polyester structure precipitates when the active energy ray-curable composition is added dropwise to a solvent such as methanol, it can be isolated by filtering the polymer, which can be isolated by infrared spectroscopy. When analyzed by the method, it can be confirmed as an absorption peak derived from the ester bond near ^{1,700 cm -1.} It can be confirmed whether or not the other components are the same as the above components by mass spectrometry gas chromatogram method or the like.

(Examples 16 to 27 and Comparative Example 4)
The following materials (A) to (E) are used in the blending ratios (numerical values are parts by mass) shown in each column of Examples and Comparative Examples in Table 4 below, and each active energy ray-curable type is used according to a conventional method. The composition was obtained.
(A) Monofunctional (meth) acrylate (B) Polyfunctional (meth) acrylate (C) Photoradical polymerization initiator with negative skin sensitivity (D) Polymer with polyester structure (E) Other polymers

Using the obtained active energy ray-curable composition, the viscosity was measured as follows.

<Viscosity>
The viscosity was measured in the same manner as in Example 1. The results are shown in Table 4. Each active energy ray-curable composition of the example had a viscosity range of 8 mPa · s or more and 11 mPa · s or less at 25 ° C.

Using the obtained active energy ray-curable composition, a cured product was obtained in the same manner as in Example 1, and this was used for evaluation of "adhesion" to a polyethylene terephthalate substrate (untreated surface).
Further, in Example 1, a cured product was obtained in the same manner as in Example 1 except that the polyethylene terephthalate base material was changed to a color steel plate base material (trade name: Yodocolor GL (GS200), manufactured by Yodogawa Steel Co., Ltd.). , The water resistance of the coating film (change in appearance, water resistance and adhesion) on the color steel sheet substrate was evaluated.

<Adhesion>
Regarding the adhesion, "adhesion" was evaluated in the same manner as in Example 1. The numerical values in parentheses in the adhesion in Table 4 below represent the number of cells that did not peel off in 100 cells.

<Water resistance of coating film>
-Appearance change-
The obtained cured product was immersed in water at 40 ° C. together with a colored steel sheet base material, left to stand for 24 hours, and then the region in contact with water was visually observed to evaluate the "appearance change".
-Water resistance-
In the evaluation of adhesion in Example 1, the cured product formed on the polyethylene terephthalate base material was changed to the cured product formed on the colored steel plate base material, and the cross cut shown in JIS-K-5600-5-6 was changed. After cutting the cured product by the method, the cured product was further immersed in water at 40 ° C. and left for 24 hours, and the "water adhesion resistance" was evaluated in the same manner as in the evaluation of the adhesion in Example 1. The numerical value in parentheses in the water resistance adhesion in Table 4 below represents the number of cells that did not peel off in 100 cells.

Details of A2 to A4, B5 to B6, C2 to C3, D1 to D2, and E1 to E5 in Table 4 are as follows.
The numerical value in parentheses at the end is the SI value in the LLNA test of (1), and "negative" or "none" is the document of (2) or MSDS (chemical substance safety) of (3). In the data sheet), it was evaluated as "negative skin sensation" or "no skin sensation". In addition, "positive" is added with the warning phrase "R43" indicating that there is a problem with skin sensitization in the risk phrase notation rules in the European Directive, or "H317" indicating that there is a problem with skin sensitization in the CLP Regulation. Is to be done. Since the polymer component has a high molecular weight, it is difficult to pass through the skin and usually does not have skin sensation.

-(A) Monofunctional (meth) acrylate-
-A2: t-Butyl Methacrylate, manufactured by Mitsubishi Rayon Co., Ltd., "Acryester TB" (negative) Evaluation based on literature (test method: maximization method)
-A3: n-Pentyl Methacrylate, Zhangjiagang Render Chemical, "n-AmylMethacrylate" (negative) Evaluation based on literature (test method: maximization method)
-A4: n-hexyl methacrylate, manufactured by Tokyo Kasei Kogyo Co., Ltd., "n-HexylMesurate" (negative) Evaluation based on literature (test method: maximization method)

-(B) Polyfunctional (meth) acrylate-
-B5: Diethylene glycol dimethacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd., (1.1)
-B6: Trimethylolpropane trimethacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd., (1.9)

-(C) Photoradical polymerization initiator with negative skin sensitivity-
C2: 2- (dimethylamino) -2- (4-methylbenzyl) -1- (4-morpholinophenyl) butane-1-one, BASF, "Irgacure 379", (none) MSDS evaluation (test method) : OECD Test Guideline 406)
C3: 2- [4- (methylthio) benzoyl] -2- (4-morpholinyl) propane, manufactured by BASF, "Irgacure 907", (none) Evaluation by MSDS (test method: OECD test guideline 406)

-(D) Polymer having a polyester structure-
D1: Polymer having a polyester structure, number average molecular weight: 3,000, hydroxyl value: 37 mgKOH / g, acid value: less than 1 mgKOH / g, manufactured by Toyobo Co., Ltd., "Byron 802"
-D2: Polymer having a polyester structure, number average molecular weight: 6,000, hydroxyl value: 19 mgKOH / g, acid value: 5 mgKOH / g, manufactured by Toyobo Co., Ltd., "Byron GK810"

-(E) Other polymers-
-E1: Styrene-acrylic resin, manufactured by BASF, "John Krill 611", acid value: 53 mgKOH / g, glass transition temperature: 50 ° C.
-E2: Acrylic resin, manufactured by BASF, "John Krill 804", acid value: 15 mgKOH / g, glass transition temperature: 70 ° C.
-E3: Low molecular weight polystyrene resin, manufactured by Sanyo Chemical Industries, Ltd., "Hymer ST-95"
-E4: Acrylic resin, manufactured by Toagosei Co., Ltd., "ARUFON (registered trademark) UC-3000 (solid), acid value: 74 mgKOH / g, glass transition temperature: 65 ° C.
-E5: Polystyrene resin, manufactured by Seiko PMC Corporation, "VS-1063", acid value: 0 mgKOH / g, glass transition temperature: 100 ° C.

-Carbon black-
The blending amount is shown as a state in which the polymer dispersant Solsperse 39000 manufactured by Japan Lubrizol Co., Ltd. is contained in a mass ratio of 3: 1 with respect to carbon black # 10 manufactured by Mitsubishi Chemical Corporation.

From Examples 16 and 17, it was found that by using a polymer having a polyester structure and another polymer in combination, both adhesion to a polyethylene terephthalate substrate and water resistance to a colored steel sheet can be achieved at the same time. In addition, since it was found that there is no problem even if the ratios when used in combination are different, it was found that it can be appropriately selected according to other required physical characteristics.
From Examples 18 to 20, it was found that the adhesiveness and water resistance were excellent even when the monomers used were different, and therefore it was found that the monomer could be appropriately selected according to the required other physical characteristics.
From Examples 21 to 25, it was found that the polymer having the polyester structure to be used in combination and the other polymer are excellent in adhesion and water resistance even when the types of the polymer are different. I found that I could do it.
From Example 26, it was found that even when the polymerization initiator used was different, the adhesion and water resistance were excellent, and therefore it was found that the suitable selection could be made according to other required physical properties.
From Example 27, it was found that the adhesiveness and water resistance were excellent even when the coloring material was contained.
Since the polymer having a polyester structure precipitates when the active energy ray-curable composition is added dropwise to a solvent such as methanol, it can be isolated by filtering the polymer, which can be isolated by infrared spectroscopy. When analyzed by the method, it can be confirmed as an absorption peak derived from the ester bond near ^{1,700 cm -1.} It can be confirmed whether or not the other components are the same as the above components by mass spectrometry gas chromatogram method or the like.

(Examples 28 to 36 and Comparative Examples 5 to 13)
The following materials (A) to (F) were used in the blending ratios (numerical values are parts by weight) shown in each column of Examples and Comparative Examples in Table 5 to obtain an active energy ray-curable composition by a conventional method. ..
(A) Monofunctional (meth) acrylate (B) Polyfunctional (meth) acrylate (C) Photoradical polymerization initiator having a negative skin sensitivity (D) Polymer having a polyester structure (E) Other polymers (F) Polymerization inhibitor

Using the obtained active energy ray-curable composition, the viscosity was measured as follows.

<Viscosity>
The viscosity was measured in the same manner as in Example 1. The results are shown in Table 5. Each active energy ray-curable composition of the example had a viscosity range of 8 mPa · s or more and 15 mPa · s or less at 25 ° C.

Using the obtained active energy ray-curable composition, a cured product was obtained in the same manner as in Example 1, and in the same manner as in Example, for evaluation of "adhesion" to a polyethylene terephthalate substrate (untreated surface). Served.

<Adhesion>
Regarding the adhesion, "adhesion" was evaluated in the same manner as in Example 1.

<Discharge recovery>
Using the obtained active energy ray-curable composition, it was installed in the ink flow path until it reached the GEN4 head manufactured by Ricoh Printing Systems Co., Ltd. in the same manner as in Example 1, and the average thickness of the solid coating film with respect to the substrate was average. Was discharged so as to be 7 μm. Then, the head was left at 50 ° C. for 3 days with the cap removed, and pressure maintenance was performed with a predetermined pressing force. The number of nozzles that can be discharged was confirmed, and "discharge recovery" was evaluated based on the following evaluation criteria.
[Evaluation criteria]
⊚: The number of nozzles that can be ejected by 20 kPa pressurization maintenance is all nozzles (100%) ◯: The number of nozzles that can be ejected by 20 kPa pressurization maintenance is 90% or more, and the number of nozzles that can be ejected by 30 kPa pressurization maintenance is all nozzles. (100%) Δ: The number of nozzles that can be ejected by 30 kPa pressurization maintenance is 50% or more and less than 100% ×: The number of nozzles that can be ejected by 30 kPa pressurization maintenance is less than 50%.

* 2: Discharge was difficult

Details of A2 to A4, B2 to B3, B5, C1 to C2, D1 to D3, E1 and F1 to F5 in Table 5 are as follows. The numerical value in parentheses at the end is the SI value in the LLNA test of (1) above, and "negative" or "none" is the document of (2) above or the MSDS (Material Safety Data Sheet) of (3) above. ), It was evaluated as "negative skin sensation" or "no skin sensation". In addition, "positive" is added with the warning phrase "R43" indicating that there is a problem with skin sensitization in the risk phrase notation rules in the European Directive, or "H317" indicating that there is a problem with skin sensitization in the CLP Regulation. Is to be done. Since the polymer component has a high molecular weight, it is difficult to pass through the skin and usually does not have skin sensation.

-(A) Monofunctional (meth) acrylate-
-A2: t-Butyl Methacrylate, manufactured by Mitsubishi Rayon Co., Ltd., "Acryester TB" (negative) Evaluation based on literature (test method: maximization method)
-A3: n-Pentyl Methacrylate, Zhangjiagang Render Chemical, "n-AmylMethacrylate" (negative) Evaluation based on literature (test method: maximization method)
-A4: n-hexyl methacrylate, manufactured by Tokyo Kasei Kogyo Co., Ltd., "n-HexylMesurate" (negative) Evaluation based on literature (test method: maximization method)

-(B) Polyfunctional (meth) acrylate-
-B2: Glycerol dimethacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd., "701", (1.2)
-B3: Tricyclodecanedimethanol dimethacrylate, "DCP" manufactured by Shin Nakamura Chemical Industry Co., Ltd., (1.3)
B5: Polyethylene glycol dimethacrylate (n≈2) represented by the following formula 1, manufactured by Shin Nakamura Chemical Industry Co., Ltd., "2G", (1.1).

-(C) Photoradical polymerization initiator with negative skin sensitivity-
-C1: 1-Hydroxy-cyclohexylphenyl ketone, manufactured by BASF, "Irgacure 184" (none) Evaluation by MSDS (test method: OECD test guideline 406)
C2: 2-Dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butane-1-one, BASF, "Irgacure 379" (none) MSDS evaluation (Test method: OECD test guideline 406)

-(D) Polymer having a polyester structure-
D1: Polymer having a polyester structure, number average molecular weight: 3,000, hydroxyl value: 37 mgKOH / g, acid value: less than 1 mgKOH / g, manufactured by Toyobo Co., Ltd., "Byron 802"
-D2: Polymer having a polyester structure, number average molecular weight: 6,000, hydroxyl value: 19 mgKOH / g, acid value: 5 mgKOH / g, manufactured by Toyobo Co., Ltd., "Byron GK810"
-D3: Polymer having a polyester structure, number average molecular weight: 23,000, hydroxyl value: 5 mgKOH / g, acid value: less than 2 mgKOH / g, manufactured by Toyobo Co., Ltd., "Byron 650"

-(E) Other polymers-
-E1: Styrene-acrylic resin, acid value: 53 mgKOH / g, weight average molecular weight: 8,100, manufactured by BASF, "John Krill 611"

-(F) Polymerization inhibitor-
・ F1: 4-methoxyphenol, manufactured by Seiko Kagaku Co., Ltd., “methoquinone”, hydroxyl group: 1 ・ F2: 4-methoxy-1-naphthol, manufactured by Kawasaki Kasei Kogyo Co., Ltd., “MNT”, hydroxyl group: 1 ・ F3 : P-Hydroxyphenol, manufactured by Seiko Kagaku Co., Ltd., "hydroquinone", hydroxyl group: 2 ・ F4: methylhydroquinone, manufactured by Seiko Kagaku Co., Ltd., "MH", hydroxyl group: 2 ・ F5: tert-butylhydroquinone, Seiko Kagaku Made by Co., Ltd., "TBH", hydroxyl group: 2 ・ F6: 2,5-di-tert-butyl hydroquinone, manufactured by Seiko Kagaku Co., Ltd., "Non-flex Alba", hydroxyl group: 2

-Carbon black-
The blending amount is shown as a state in which the polymer dispersant Solsperse 39000 manufactured by Japan Lubrizol Co., Ltd. is contained in a mass ratio of 3: 1 with respect to carbon black # 10 manufactured by Mitsubishi Chemical Corporation.

From Examples 28 to 35 and Comparative Examples 5 to 13, it was found that good discharge recovery property can be obtained depending on the amount of the polymerization inhibitor of Group F. It was also found that there is a boundary line in the amount of the polymerization inhibitor that can obtain good ejection recovery, and the content F'of the polymerization inhibitor in group F is when the content of the polymerization initiator in group C is C'. It was found that F'= 0.01 × C'or more is preferable. FIG. 6 shows the relationship between F'and C'in Table 5.
In both Examples 28 to 35 and Comparative Examples 5 to 12, the polymerization inhibitor having two hydroxyl groups in the molecule has a better discharge recovery with a smaller amount than the polymerization inhibitor having one hydroxyl group in the molecule. It turned out that the sex was obtained. It is considered that this is because the polymerization inhibitor captures the radicals generated in the ink and efficiently forms stable radicals.
In Comparative Example 13, good adhesion was also obtained, but as compared with the other examples, droplets tended to elongate during ejection and a little more mist was generated, and it was difficult to follow high-frequency pulses. Therefore, it was found that a smaller molecular weight is more preferable as the polymer component.
Further, in all the examples, the coating film after light irradiation was well cured without stickiness in the touch confirmation.
Since the polymer having a polyester structure precipitates when the active energy ray-curable composition is added dropwise to a solvent such as methanol, it can be isolated by filtering the polymer, which can be isolated by infrared spectroscopy. When analyzed by the method, it can be confirmed as an absorption peak derived from the ester bond near ^{1,700 cm -1.} It can be confirmed whether or not the other components are the same as the above components by mass spectrometry gas chromatogram method or the like.

Examples of aspects of the present invention are as follows.
<1> An active energy ray-curable composition comprising a monofunctional (meth) acrylate, a polyfunctional (meth) acrylate, and a polymer having a polyester structure.
<2> The active energy ray-curable composition according to <1>, which further comprises a polymer obtained by polymerizing at least one selected from styrene, a styrene derivative, an acrylic acid ester, and acrylic acid.
<3> Further containing a polymerization initiator and a polymerization inhibitor,
The active energy according to any one of <1> to <2>, wherein the content of the polymerization inhibitor is 0.01 × A mass% or more when the content of the polymerization initiator is A mass%. It is a linear curable composition.
<4> The active energy ray-curable composition according to <3>, wherein the polymerization inhibitor has two hydroxyl groups in the molecule.
<5> The active energy ray-curable composition according to any one of <1> to <4>, wherein the Stimulation Index of the monofunctional (meth) acrylate is less than 3.
<6> The active energy ray-curable composition according to any one of <1> to <5>, wherein the Stimulation Index of the polyfunctional (meth) acrylate is less than 3.
<7> The active energy ray-curable composition according to any one of <1> to <6>, wherein the polymer having a polyester structure has a weight average molecular weight of 100,000 or less.
<8> The content of the polymer having the polyester structure is 10 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass in total of the monofunctional (meth) acrylate and the polyfunctional (meth) acrylate. The active energy ray-curable composition according to any one of 1> to <7>.
<9> The above-mentioned <1> to <8>, wherein the content of the polyester moiety in the polymer having the polyester structure is 50% by mass or less with respect to the total amount of the polymer having the polyester structure. It is an active energy ray-curable composition of.
<10> The content of the monofunctional (meth) acrylate is 50 parts by mass or more and 85 parts by mass or less with respect to 100 parts by mass in total of the monofunctional (meth) acrylate and the polyfunctional (meth) acrylate. The active energy ray-curable composition according to any one of 1> to <9>.
<11> The content of the polyfunctional (meth) acrylate is 15 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass in total of the monofunctional (meth) acrylate and the polyfunctional (meth) acrylate. The active energy ray-curable composition according to any one of 1> to <10>.
<12> The active energy ray-curable composition according to any one of <1> to <11>, wherein the viscosity at 25 ° C. is 5 mPa · s or more and 18 mPa · s or less.
<13> The active energy ray-curable composition according to any one of <1> to <12>, which is a material for three-dimensional modeling.
<14> The active energy ray-curable composition according to any one of <1> to <13>, which is an ink for an inkjet.
<15> A composition container containing the active energy ray-curable composition according to any one of <1> to <14>.
<16> A two-dimensional or three-dimensional image forming apparatus comprising the composition container according to the above <15>.
<17> A method for forming a two-dimensional or three-dimensional image, which comprises an irradiation step of irradiating the active energy ray-curable composition according to any one of <1> to <14> with active energy rays. Is.
<18> The method for forming a two-dimensional or three-dimensional image according to <17>, which comprises a discharge step of discharging the active energy ray-curable composition onto a polyethylene terephthalate substrate that has not been surface-treated. ..
<19> A base material and a cured film obtained by irradiating the base material with the active energy ray-curable composition according to any one of <1> to <14> and curing the active energy ray-curable composition. It is a cured product characterized by having.
<20> The base material is a polyethylene terephthalate base material.
The cured film contains a monofunctional (meth) acrylate, a polyfunctional (meth) acrylate, and a polymer having a polyester structure.
The cured product according to <19>, wherein the adhesion between the polyethylene terephthalate base material and the cured film is 1 kPa or more.

The active energy ray-curable composition according to any one of <1> to <14>, the composition storage container according to <15>, the composition discharge device according to <16>, and the above <17>. According to the method for forming a two-dimensional or three-dimensional image according to <18> and the cured product according to any one of <19> to <20>, the conventional problems are solved and the present invention is described. Can achieve the purpose of.

Japanese Unexamined Patent Publication No. 2009-57546 Japanese Unexamined Patent Publication No. 2012-207117

39 Image forming device 200 Composition storage container

Claims (14)

A monofunctional (meth) acrylate having a Stimulation Index of less than 3,
A polyfunctional (meth) acrylate having a Stimulation Index of less than 3,
Polymers with a polyester structure (except when containing polyester urethane (meth) acrylate) ,
Contains polymerization initiators and polymerization inhibitors
The content of the polymer having a polyester structure is 10 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass in total of the monofunctional (meth) acrylate and the polyfunctional (meth) acrylate.
When the content of the polymerization initiator is A mass% with respect to the total content of the monofunctional (meth) acrylate and the polyfunctional (meth) acrylate, the content of the polymerization inhibitor is 0.01 × A mass. der least% is,
The viscosity at 25 ° C. is 5 mPa · s or more and 18 mPa · s or less.
An active energy ray-curable composition for three-dimensional modeling. Styrene, A acrylic acid ester, and stereolithography for the active energy ray curable composition according to claim 1, further comprising a polymer obtained by polymerizing at least one member selected from acrylic acid. The active energy ray-curable composition for three-dimensional modeling according to any one of claims 1 to 2, wherein the polymerization inhibitor has two hydroxyl groups in the molecule. The active energy ray-curable composition for three-dimensional modeling according to any one of claims 1 to 3, wherein the polymer having a polyester structure has a weight average molecular weight of 100,000 or less. The active energy for three-dimensional modeling according to any one of claims 1 to 4, wherein the content of the polyester portion in the polymer having the polyester structure is 50% by mass or less with respect to the total amount of the polymer having the polyester structure. Linear curable composition. Claims 1 to 5 in which the content of the monofunctional (meth) acrylate is 50 parts by mass or more and 85 parts by mass or less with respect to 100 parts by mass in total of the monofunctional (meth) acrylate and the polyfunctional (meth) acrylate. The active energy ray-curable composition for three-dimensional modeling according to any one of. Claims 1 to 6 in which the content of the polyfunctional (meth) acrylate is 15 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass in total of the monofunctional (meth) acrylate and the polyfunctional (meth) acrylate. The active energy ray-curable composition for three-dimensional modeling according to any one of. The active energy ray-curable composition for three-dimensional modeling according to any one of claims 1 to 7, which is an ink for an inkjet. A composition container containing the active energy ray-curable composition for three-dimensional modeling according to any one of claims 1 to 8. A two-dimensional or three-dimensional image forming apparatus comprising the composition storage container according to claim 9. A method for forming a two-dimensional or three-dimensional image, which comprises an irradiation step of irradiating the active energy ray-curable composition for three-dimensional modeling with an active energy ray according to any one of claims 1 to 8. The method for forming a two-dimensional or three-dimensional image according to claim 11, further comprising a discharge step of discharging the active energy ray-curable composition for three-dimensional modeling onto a polyethylene terephthalate base material that has not been surface-treated. Having a base material and a cured film obtained by irradiating the base material with an active energy ray-curable composition for three-dimensional modeling according to any one of claims 1 to 8 and curing the active energy ray-curable composition. Characterized cured product. The base material is a polyethylene terephthalate base material.
The cured film contains a monofunctional (meth) acrylate, a polyfunctional (meth) acrylate, and a polymer having a polyester structure.
The cured product according to claim 13, wherein the adhesion between the polyethylene terephthalate base material and the cured film is 1 kPa or more.