JP7336098B2 - Active energy ray-curable composition, active energy ray-curable ink composition, active energy ray-curable inkjet ink composition, composition container, two-dimensional or three-dimensional image forming apparatus, two-dimensional or three-dimensional image Forming method, cured product, and decorative body - Google Patents

Description

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

An inkjet recording method is known as a method for forming an image on a recording medium such as paper or plastic. This recording method has high ink consumption efficiency and is excellent in resource saving, and it is possible to keep the ink cost per unit recording low.
2. Description of the Related Art In recent years, attention has been paid to an inkjet recording method using an ultraviolet curable ink.

Patent Documents 1 and 2 disclose a monomer containing a vinyl ether group and a (meth)acrylate group, a monomer containing a five-membered cyclic anhydride curable by free radical polymerization, and an aliphatic tertiary amine, especially Radiation curable inks suitable for legend printing in printed circuit board manufacturing are disclosed.

Patent Document 3 discloses a) a polymerizable compound A having an acrylate group and a second ethylenically unsaturated polymerizable functional group selected from the group consisting of a vinyl ether group, an allyl ether group and an allyl ester group, and b) For reduced unpleasant odor food packaging applications comprising a polymerizable compound B consisting of a difunctional acrylate and c) a polymerizable compound C selected from the group consisting of triacrylates, tetraacrylates, pentaacrylates and hexaacrylates. Suitable free radical curable liquids are disclosed.

In Patent Document 4, an actinic radiation-curable ink composition containing a polyfunctional polymerizable compound and a sensitizer having a molecular weight of 1000 or more is applied from an inkjet head to an assembly of non-absorbent or low-absorbent fiber materials. An image is formed on the recording substrate by keeping a constant amount of ink droplets and a constant distance between the recording substrate and the inkjet head ^. It has a step of irradiating an actinic ray under conditions of ² MPa or less to cure the image, and has good film strength and excellent abrasion resistance, and the amount of residual monomer is small, and an image with high safety and low odor is formed. An ink jet recording method is disclosed.

Patent Document 5 discloses a compound or alcohol containing one or more epoxy groups in 2-(2′,4′-dihydroxyphenyl)-2H-benzotriazoles, which is an ultraviolet absorber to be blended in ink or the like. A non-bleeding reactive ultraviolet absorber containing a reactive group of an alcoholic hydroxyl group or an alcoholic hydroxyl group and an epoxy group obtained by reacting an alkyl halide having a reactive hydroxyl group is disclosed.

Since the active energy ray-curable composition is cured by irradiation with an active energy ray, it is superior in drying property and adhesion to a substrate as compared with a solvent-based ink composition. In recent years, there has been an increasing demand for the safety of compositions, and in particular, elution (migration) of components from cured products has sometimes become a problem in food packaging and printing on hard containers.
An object of the present invention is to provide an active energy ray-curable composition that suppresses migration from a cured product and increases hardness.

（式中Ｒは水素もしくはメチル基、Ａは下記構造式（II）～（VII）のいずれかで表される構造であり、それぞれアルキル基、アルコキシ等の置換基を有していても良く、ｊ及びｋは０以上の整数である。Ｘはヘテロ原子を含む置換基を示す。ｎは０以上の整数、ｍは１以上の整数、ｎ＋ｍは３以上、またはｎ＝０、ｍ＝２の整数を表す。なお、構造式（II）～（VII）中の波線はそれぞれ独立にＸまたは（メタ）アクリロイル基（Ｈ_２Ｃ＝ＣＲ－Ｃ（＝Ｏ）－）との結合手を示す。）

The active energy ray-curable composition of the present invention as a means for solving the above problems is an active energy ray-curable composition characterized by containing a compound represented by the following general formula (I).

(In the formula, R is hydrogen or a methyl group, A is a structure represented by any of the following structural formulas (II) to (VII), each of which may have a substituent such as an alkyl group or an alkoxy group, j and k are integers of 0 or more, X represents a substituent containing a hetero atom, n is an integer of 0 or more, m is an integer of 1 or more, n+m is 3 or more, or n=0, m=2 Each wavy line in structural formulas (II) to (VII) independently indicates a bond with X or a (meth)acryloyl group (H ₂ C═CR—C(═O)—). )

ADVANTAGE OF THE INVENTION According to this invention, the above-mentioned conventional problems can be solved and the active-energy-ray-curable composition which suppressed migration can be provided.

FIG. 1 is a schematic diagram showing an example of another image forming apparatus (three-dimensional stereoscopic image forming apparatus). FIG. 2 is a schematic explanatory diagram illustrating an example of a method for three-dimensional modeling using a composition.

（式中Ｒは水素もしくはメチル基、Ａは下記構造式（II）～（VII）のいずれかで表される構造であり、それぞれアルキル基、アルコキシ等の置換基を有していても良く、ｊ及びｋは０以上の整数である。Ｘはヘテロ原子を含む置換基を示す。ｎは０以上の整数、ｍは１以上の整数、ｎ＋ｍは３以上、またはｎ＝０、ｍ＝２の整数を表す。なお、構造式（II）～（VII）中の波線はそれぞれ独立にＸまたは（メタ）アクリロイル基（Ｈ_２Ｃ＝ＣＲ－Ｃ（＝Ｏ）－）との結合手を示す。）
なお、上記「（メタ）アクリロイル基」という用語は、「Ｈ_２Ｃ＝ＣＲ－Ｃ（＝Ｏ）－」で表されるアクリロイル基において、Ｒがメチル基である場合と、Ｒが水素である場合との両方を示す用語である。

An active energy ray-curable composition comprising a compound represented by the following general formula (I).

(In the formula, R is hydrogen or a methyl group, A is a structure represented by any of the following structural formulas (II) to (VII), each of which may have a substituent such as an alkyl group or an alkoxy group, j and k are integers of 0 or more, X represents a substituent containing a hetero atom, n is an integer of 0 or more, m is an integer of 1 or more, n+m is 3 or more, or n=0, m=2 Each wavy line in structural formulas (II) to (VII) independently indicates a bond with X or a (meth)acryloyl group (H ₂ C═CR—C(═O)—). )
The term "(meth)acryloyl group" refers to an acryloyl group represented by "H ₂ C=CR-C(=O)-" when R is a methyl group and when R is hydrogen. It is a term that indicates both when and when.

In order to improve reactivity and hardness, n and m are preferably integers of 1 or more, and n+m is preferably an integer of 3 or more.
X above is preferably a cyclic substituent containing a heteroatom.
The content of the compound of formula (I) is preferably 5 parts by mass to 20 parts by mass with respect to 100 parts by mass of the radically polymerizable compound described later.
The compounds represented by formula (I) may be used singly or in combination of two or more. Specific examples include compounds represented by the following structural formulas (A-1) to (A-20).

<Radical polymerizable compound>
The active energy ray-curable composition of the present invention contains a radically polymerizable compound in addition to the compound represented by the general formula (I). The radically polymerizable compound is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include compounds represented by the following structural formulas (B-1) to (B-24). These may be used individually by 1 type, and may use 2 or more types together.

<Polymerization initiator>
Any polymerization initiator may be used as long as it can generate active species such as radicals and cations by the energy of active energy rays to initiate polymerization of polymerizable compounds (monomers and oligomers). As such polymerization initiators, known radical polymerization initiators, cationic polymerization initiators, base generators and the like can be used singly or in combination of two or more. Among them, radical polymerization initiators are used. is preferred. Further, the polymerization initiator is preferably contained in an amount of 0.2 to 20 parts by mass with respect to the reactive compound (100 parts by mass) in order to obtain a sufficient curing speed.
Examples of radical polymerization initiators include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, Known compounds such as ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds, specific examples (C-1) to (C-6) below. things can be mentioned.

Moreover, in addition to the polymerization initiator, a polymerization accelerator (sensitizer) can be used in combination. Examples of the polymerization accelerator include, but are not limited to, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, N, Amine compounds such as N-dimethylbenzylamine and 4,4'-bis(diethylamino)benzophenone are preferred, and the content thereof may be appropriately set according to the polymerization initiator to be used and its amount.

<Curing means>
Examples of means for curing the curable composition of the present invention include heat curing and curing with active energy rays, and among these, curing with active energy rays is preferred.
Examples of the active energy ray used for curing the active energy ray-curable composition of the present invention 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 impart the energy necessary for proceeding with the polymerization reaction. Especially when using a high-energy light source, the polymerization reaction can proceed without using a polymerization initiator. Further, in the case of ultraviolet irradiation, there is a strong desire to eliminate mercury from the viewpoint of environmental protection, and replacement with GaN-based semiconductor ultraviolet light emitting devices is very useful both industrially and environmentally. Furthermore, ultraviolet light emitting diodes (UV-LEDs) and ultraviolet laser diodes (UV-LDs) are compact, have a long life, are highly efficient, and are low in cost, and are preferred as ultraviolet light sources.

The active energy ray-curable composition of the present invention may not contain a polymerization initiator in the active energy ray-curable composition. When it does not contain a polymerization initiator, it can be used as a composition set consisting of an active energy ray-curable composition containing no polymerization initiator and a polymerization initiator.

<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, lustrous colors such as gold and silver, etc., depending on the purpose and required properties 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 density, dispersibility in the composition, etc., and is not particularly limited. It is preferably 1 to 20% by mass. In addition, the active energy ray-curable composition of the present invention may be colorless and transparent without containing a coloring material, and in that case, it is suitable as an overcoat layer for protecting images, for example.
As the pigment, an inorganic pigment or an organic pigment can be used, and one kind may be used alone, or two or more kinds may be used in combination.
Examples of inorganic pigments that can be used include carbon black (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, and titanium oxide.
Examples of organic pigments include azo pigments such as insoluble azo pigments, condensed azo pigments, azo lakes, and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone. Polycyclic pigments such as pigments, dye chelates (for example, basic dye chelates, acid dye chelates, etc.), dyeing lakes (basic dye lakes, acid dye lakes), nitro pigments, nitroso pigments, aniline black, Daylight fluorescent pigments may be mentioned.
In addition, a dispersant may be further included in order to improve the dispersibility of the pigment. The dispersant is not particularly limited, but includes, for example, dispersants commonly used for preparing pigment dispersions such as polymeric dispersants.
As dyes, for example, acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and they may be used singly or in combination of two or more.

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

<Other ingredients>
The active energy ray-curable composition of the present invention may optionally contain other known components. Other components are not particularly limited, but include, for example, conventionally known surfactants, polymerization inhibitors, leveling agents, antifoaming agents, fluorescent whitening agents, penetration accelerators, humectants (moisturizing agents), and fixing agents. agents, viscosity stabilizers, antifungal agents, preservatives, antioxidants, ultraviolet absorbers, chelating agents, pH adjusters, and thickeners.

<Preparation of active energy ray-curable composition>
The active energy ray-curable composition of the present invention can be produced using the various components described above, and the preparation means and conditions are not particularly limited. Put into a dispersing machine such as kitty mill, disc mill, pin mill, dyno mill, etc., disperse to prepare pigment dispersion liquid, and further mix polymerizable monomer, initiator, polymerization inhibitor, surfactant, etc. into the pigment dispersion liquid. It can be prepared by

<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, when applying a discharge means for discharging the composition from a nozzle. is preferably 3 to 40 mPa·s, more preferably 5 to 15 mPa·s, particularly preferably 6 to 12 mPa·s, in the range of 20°C to 65°C, preferably 25°C. Moreover, it is particularly preferable that the viscosity range is satisfied without including the organic solvent. The above viscosity was measured using a cone-plate rotary viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd., using a cone rotor (1°34′×R24), rotating at 50 rpm, and constant temperature circulating water at 20°C. Measurement can be performed by appropriately setting the temperature in the range of ~65°C. VISCOMATE VM-150III can be used to adjust the temperature of the circulating water.

<Application>
The application of the active energy ray-curable composition of the present invention is not particularly limited as long as it is a field where active energy ray-curable materials are generally used, and can be appropriately selected according to the purpose. Examples include resins, paints, adhesives, insulating materials, release agents, coating materials, sealing materials, various resists, and various optical materials.
Furthermore, the active energy ray-curable composition of the present invention not only forms two-dimensional characters, images, and design coatings on various substrates, but also forms a three-dimensional three-dimensional image (three-dimensional object). It can also be used as a material for three-dimensional modeling. Moreover, it may be used as a three-dimensional structural material (model material) or a supporting member (supporting material) used in a layered manufacturing method (stereolithography method) as shown in FIGS. 1 and 2 . In addition, FIG. 1 shows a method of discharging the active energy ray-curable composition of the present invention to a predetermined region, irradiating the active energy ray to harden the composition, and stacking them one after another to form a three-dimensional model.

The image forming apparatus 39 in FIG. 1 uses a head unit (movable in the AB direction) in which inkjet heads are arranged to eject the first active energy ray-curable composition from the ejection head unit 30 for a modeled object. A second active energy ray-curable composition having a composition different from that of the first active energy ray-curable composition is ejected from the head units 31 and 32, and these compositions are cured by adjacent ultraviolet irradiation means 33 and 34. It is laminated while doing so. More specifically, for example, the second active energy ray-curable composition is ejected from the support ejection head units 31 and 32 onto the shaped object support substrate 37, and is irradiated with an active energy ray to be solidified. After forming the first support layer having a reservoir, the first active energy ray-curable composition is discharged from the discharge head unit 30 for a modeled object into the reservoir, and is irradiated with an active energy ray to be solidified. By repeating the step of forming the first model layer by pressing the support layer and the model layer a plurality of times while lowering the vertically movable stage 38 according to the number of layers, the support layer and the model layer are laminated to form the three-dimensional model 35 . to manufacture. Thereafter, the support laminate 36 is removed as required. Although only one ejection head unit 30 is provided in FIG. 1, two or more may be provided.

FIG. 2 shows that a storage pool (receiving portion) 1 for an active energy ray-curable composition 5 of the present invention is irradiated with an active energy ray 4 to form a cured layer 6 having a predetermined shape on a movable stage 3, which is sequentially formed. This is a method of layering and three-dimensional modeling.

As a stereolithography apparatus for molding a three-dimensional object using the active energy ray-curable composition of the present invention, a known apparatus can be used, and is not particularly limited. For example, means for containing the composition , supply means, discharge means, active energy ray irradiation means, and the like.

In addition, the present invention includes a molded product obtained by processing a cured product obtained by curing an active energy ray-curable composition or a structure in which the cured product is formed on a substrate, but particularly polymerized It is preferably used as a sexual dental material. The molded article is, for example, a sheet-shaped or film-shaped cured product or structure subjected to molding such as heat stretching or punching.・It is suitable for applications that require molding after surface decoration, such as electronic equipment, meters for cameras, and operation panels.
The base material is not particularly limited and can be appropriately selected depending on the purpose. Examples include paper, thread, fiber, fabric, leather, metal, plastic, glass, wood, ceramics, composite materials thereof, and the like. and a plastic substrate is preferable from the viewpoint of workability.

<Composition storage container>
The composition container of the present invention means a container containing an active energy ray-curable composition or a polymerizable dental material composition, and is suitable for the above uses. The shape, size, material, etc. of the container itself are not particularly limited as long as they are suitable for the application and usage. should be covered with a protective sheet or the like.

Examples of the present invention are shown below, but the scope of the present invention is not limited by these Synthesis Examples and Examples.

Among the compounds (A-1) to (A-20) shown as examples of the compound represented by the general formula (I), A-1, A-2, A-3, A-6, A- Synthesis examples of 7, A-8 and A-12 and NMR spectrum values of each compound are shown below.

(Synthesis example 1)
Synthesis example of (A-1) A 100 mL three-necked flask was charged with 5.93 g (20 mmol) of trimethylolpropane triacrylate (ARONIX M-309, manufactured by Toagosei), and 5.40 g (62 mmol) of morpholine was cooled with ice. was dripped. After completion of the dropwise addition, the mixture was returned to room temperature and stirred for 1 hour. This crude product was purified by silica gel column chromatography (filler: Wakogel C-300, developing solvent: ethyl acetate) to obtain 7.0 g of the desired product as a colorless liquid (yield 63%).
(NMR spectrum value)
¹ H-NMR (500 MHz, CDCl ₃ ): δ0.90(t, 3H), 1.49(q, 2H), 2.45(br, 12H), 2.51(t, 6H), 2.66(t, 6H), 3.68( t, 12H), 4.06(s, 6H)

(Synthesis example 2)
Synthesis example of (A-2) In a 100 mL three-necked flask, 8.89 g (30 mmol) of trimethylolpropane triacrylate (ARONIX M-309, manufactured by Toagosei Co., Ltd.) was charged, and 5.23 g (60 mmol) of morpholine was added while cooling with ice. was dripped. After completion of the dropwise addition, the mixture was returned to room temperature and stirred for 2 hours. This crude product was purified by silica gel column chromatography (filler: Wakogel C-300, developing solvent: ethyl acetate) to obtain 1.8 g of the desired product as a colorless liquid (yield 12%).
(NMR spectrum value)
¹ H-NMR (500 MHz, CDCl ₃ ): δ0.91(t, 3H), 1.51(q, 2H), 2.45(br, 8H), 2.51(t, 4H), 2.66(t, 4H), 3.68( t, 8H), 4.08(s, 4H), 4.12(s, 2H), 5.86-5.88(dd, 1H), 6.09-6.15(q, 1H), 6.39-6.43(dd, 1H)

(Synthesis Example 3)
Synthesis Example of (A-3) A 100 mL three-necked flask was charged with 11.85 g (40 mmol) of trimethylolpropane triacrylate (ARONIX M-309, manufactured by Toagosei Co., Ltd.) and 20 mL of ethyl acetate, and morpholine was added while cooling with ice. 48 g (40 mmol) was added dropwise. After dropping, the mixture was returned to room temperature and stirred for 1 hour, and then a polymerization inhibitor (MEHQ) was added. This crude product was purified by silica gel column chromatography (filler: Wakogel C-300, developing solvent: hexane/ethyl acetate = 1/1) to give 4.5 g of the desired product as a colorless liquid (yield 30%). got
(NMR spectrum value)
¹ H-NMR (500 MHz, CDCl ₃ ): δ0.92(t, 3H), 1.53(q, 2H), 2.44(br, 4H), 2.51(t, 2H), 2.66(t, 2H), 3.67( t, 4H), 4.11(s, 2H), 4.15(s, 4H), 5.85-5.88(dd, 2H), 6.09-6.15(q, 2H), 6.39-6.43(dd, 2H)

(Synthesis Example 4)
Synthesis Example of (A-6) A 100 mL three-necked flask was charged with 10.15 g (30 mmol) of trimethylolpropane trimethacrylate (SR-350, manufactured by Arkema), and 3.13 g (36 mmol) of morpholine was added dropwise. After that, the mixture was heated and reacted at 45° C. for 12 hours. This crude product was purified by silica gel column chromatography (filler: Wakogel C-300, developing solvent: hexane/ethyl acetate = 3/1) to give 4.9 g of the desired product as a colorless liquid (yield 38%). got
(NMR spectrum value)
¹ H-NMR (500 MHz, CDCl ₃ ): δ0.93(t, 3H), 1.13(d, 3H), 1.56(q, 2H), 1.95(t, 6H), 2.27(q, 1H), 2.36( br, 2H), ,2.47(br, 2H), 2.63(t, 1H), 2.70-2.73(m, 1H), 3.64(t, 4H), 4.11(d, 2H), 4.14(s, 4H), 5.58-5.59(m, 2H), 6.10-6.11(m, 2H)

(Synthesis Example 5)
Synthesis example of (A-7)
A 100-mL three-necked flask was charged with 3.62 g (30 mmol) of glycerin triacrylate (ARONIX MT-3547, manufactured by Toagosei) and 20 ml of ethyl acetate, and 8.10 g (93 mmol) of morpholine was added dropwise while cooling with ice. After completion of the dropwise addition, the mixture was returned to room temperature and stirred for 1 hour. This crude product was purified by silica gel column chromatography (filler: Wakogel C-300, developing solvent: ethyl acetate) to obtain 9.0 g of the desired product as a colorless liquid (yield 58%).
(NMR spectrum value)
¹ H-NMR (500 MHz, CDCl ₃ ): δ2.45(br, 12H), 2.52(m, 6H), 2.67(m, 6H), 3.69(t, 12H), 4.21(dd, 2H), 4.32( dd, 2H), 5.28(m, 1H)

(Synthesis Example 6)
Synthesis example of (A-8)
A 300 mL three-necked flask purged with nitrogen gas was charged with 1.69 g (14.5 mmol) of tetrahydrofuran-2-carboxylic acid (manufactured by Tokyo Kasei Kogyo), 50 mL of dehydrated dichloromethane, 5.45 mL of triethylamine (39.3 mmol), and 4-dimethylamino. 0.177 g (1.45 mmol) of pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5 g (14.5 mmol) of 2-methyl-6-nitrobenzoic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged and stirred at room temperature for 10 minutes. After that, 0.54 g (4.02 mmol) of trimethylolpropane was added little by little to this reaction solution, and the mixture was stirred at room temperature for 12 hours.
The reaction solution was transferred to a separatory funnel, washed with a saturated aqueous solution of sodium bicarbonate and then with a saturated saline solution in that order, sodium sulfate was added to the organic phase to dry it, and then the solvent was distilled off under reduced pressure. This crude product was purified by silica gel column chromatography (filler: Wakogel C-300, developing solvent: hexane/ethyl acetate = 1/1) to obtain 1.6 g of the target product as a colorless liquid (yield 94%). got
(NMR spectrum value)
¹ H-NMR (500 MHz, CDCl ₃ ): δ0.91(t, 3H), 1.49(q, 2H), 1.93(m, 6H), 1.96(m, 3H), 2.25(m, 3H), 3.93( m, 3H), 3.99(m, 3H), 4.09(m, 6H), 4.46(q, 3H)

(Synthesis Example 7)
Synthesis example of (A-12) A 50 mL three-necked flask was charged with 3.00 g (10 mmol) of tripropylene glycol diacrylate (ARONIX M-220, manufactured by Toagosei), and 1.92 g (22 mmol) of morpholine was added while cooling with ice. was dripped. After completion of the dropwise addition, the mixture was returned to room temperature and stirred for 1 hour. This crude product was purified by silica gel column chromatography (filler: Wakogel C-300, developing solvent: hexane/ethyl acetate = 1/2) to obtain 4.4 g of the desired product as a colorless liquid (yield 93%). got
(NMR spectrum value)
¹ H-NMR (500 MHz, CDCl ₃ ): δ 1.11-1.24(m, 9H), 2.46(br, 8H), 2.49(m, 4H), 2.68(m, 4H), 3.30-3.61(m, 6H) , 3.69(t, 8H), 5.01-5.11(m, 3H)

<Preparation of active energy ray-curable composition>
Based on the materials and contents (parts by mass) shown in Table 1, active energy ray-curable compositions of Examples and Comparative Examples were prepared by a conventional method. In addition, the code|symbol which represents each compound in Table 1 corresponds with the code|symbol of the compound illustrated above.
For the active energy ray-curable composition of each example and comparative example, a 10 μm film was prepared on a PET film (Toyobo E5100, thickness 100 μm) for evaluation of the amount of elution, and for evaluation of pencil hardness. , a 10 μm-thick film was formed on a PC (polycarbonate) substrate (NF-2000 manufactured by Mitsubishi Gas Chemical, thickness 500 μm), and each film was cured with a metal halide lamp (1000 mJ/cm ² ) manufactured by Ushio Electric.

The abbreviations in the table represent the following respectively.
B-1: Toagosei Co., Ltd. M-220
B-2: Toagosei Co., Ltd. M-309
B-10: Nippon Kayaku Co., Ltd. R-684
B-16: Osaka Organic Chemical Industry Co., Ltd. Viscoat #150
C-1: BASF Irgcure 907
C-4: BASF Lucirin TPO
CB: MICROLITH Black CK (carbon black pigment) manufactured by Ciba Japan Co., Ltd.
Blue: MICROLITH Blue 4G-K manufactured by Ciba Japan Co., Ltd.

<Elution amount>
The active energy ray-curable composition of each example and comparative example was evaluated as follows.
(1) A cured film on a PET film is cut into 1 cm squares.
(2) The film of (1) is immersed in 1.67 g of solvent (acetone, acetonitrile) and allowed to stand for 24 hours.
(3) Filter the solvent and analyze by GC-MS and LC-MS to evaluate the amount of elution.
Evaluation criteria are as follows.
◎: Elution amount less than 1 ppm ○: Elution amount 1 ppm or more and less than 5 ppm △: Elution amount 5 ppm or more and less than 10 ppm ×: Elution amount 10 ppm or more

<Pencil hardness>
The pencil hardness test was conducted according to JIS K5600-5-4 (scratch hardness: pencil method).
Table 1 shows the results.

From the results in Table 1, it can be seen that the active energy ray-curable composition of the present invention increases the pencil hardness and suppresses the elution amount of the polymerization initiator.

<Example of application as inkjet ink>
Three types of inkjet inks composed of the active energy ray-curable compositions of Examples 1 to 3 were evaluated for curability and ink jettability in the following manner.
[Evaluation method]
Each inkjet ink prepared based on the materials and contents (mass parts) shown in Table 1 was loaded into an inkjet ejection device (manufactured by Ricoh Co., Ltd., head: GEN4 manufactured by Ricoh Printing Systems), and commercially available polyethylene terephthalate (PET) ) A film (manufactured by Toyobo Co., Ltd., E5100, thickness 100 μm) is discharged with ink, and a solid coating film formed to an average thickness of 10 μm is irradiated with a UV irradiation machine (LH6, manufactured by Fusion Systems Japan) at 0.2 W. /cm2.
As a result, all of the inkjet inks had low viscosities (10 mPa·s to 15 mPa·s at 40° C.) and good ink ejection properties.

（式中Ｒは水素もしくはメチル基、Ａは下記構造式（II）～（VII）のいずれかで表される構造であり、それぞれアルキル基、アルコキシ等の置換基を有していても良く、ｊ及びｋは０以上の整数である。Ｘはヘテロ原子を含む置換基を示す。ｎは０以上の整数、ｍは１以上の整数、ｎ＋ｍは３以上、またはｎ＝０、ｍ＝２の整数を表す。なお、構造式（II）～（VII）中の波線はそれぞれ独立にＸまたは（メタ）アクリロイル基（Ｈ_２Ｃ＝ＣＲ－Ｃ（＝Ｏ）－）との結合手を示す。）

（２）前記活性エネルギー線硬化型組成物が、更にラジカル重合性化合物を含み、前記ラジカル重合性化合物１００質量部に対し、前記一般式（Ｉ）で表される化合物を４質量部～２０質量部含むことを特徴とする上記（１）に記載の活性エネルギー線硬化型組成物。
（３）前記一般式（Ｉ）で表される化合物が、ｎ、ｍは１以上の整数、ｎ＋ｍは３以上の整数であることを特徴とする上記（１）又は（２）に記載の活性エネルギー線硬化型組成物。
（４）前記一般式（Ｉ）中、Ｘがヘテロ原子を含む環状の置換基であることを特徴とする上記（１）乃至（３）のいずれか１項に記載の活性エネルギー線硬化型組成物。
（５）前記活性エネルギー線硬化型組成物が、重合開始剤を含むことを特徴とする上記（１）乃至（４）のいずれか１項に記載の活性エネルギー線硬化型組成物。
（６）前記一般式（Ｉ）で表される化合物が、下記の（Ａ－１）～（Ａ－２０）で表される構造を有する化合物である上記（１）乃至（５）のいずれか１項に記載の活性エネルギー線硬化型組成物。

（７）立体造形用材料であることを特徴とする上記（１）乃至（６）のいずれか１項に記載の活性エネルギー線硬化型組成物。
（８）上記（１）乃至（７）のいずれか１項に記載の活性エネルギー線硬化型組成物を用いたことを特徴とする活性エネルギー線硬化型インク組成物。
（９）上記（８）に記載の活性エネルギー線硬化型インク組成物を用いたことを特徴とする活性エネルギー線硬化型インクジェット用インク組成物。
（１０）上記（１）乃至（９）のいずれか１項に記載の組成物が収容された組成物収容容器。
（１１）上記（１）乃至（９）のいずれか１項に記載の組成物が収容された収容部と、活性エネルギー線を照射するための照射手段とを備えたことを特徴とする２次元または３次元の像形成装置。
（１２）上記（１）乃至（９）のいずれか１項に記載の組成物に活性エネルギー線を照射する照射工程を有する、２次元または３次元の像形成方法。
（１３）上記（１）乃至（９）のいずれか１項に記載の組成物の硬化物。
（１４）基材上に、上記（１３）に記載の硬化物からなる表面加飾を有することを特徴とする加飾体。
（１５）下記一般式（Ｉ）で表される化合物を含むことを特徴とする活性エネルギー線硬化型組成物。

（式中Ｒは水素もしくはメチル基、Ａは多価アルコール残基、Ｘはヘテロ原子を含む置換基を示す。ｎは０以上の整数、ｍは１以上の整数、ｎ＋ｍは３以上、またはｎ＝０、ｍ＝２の整数を表す。） The present invention relates to the active energy ray-curable composition of (1) below, and includes the following (2) to (15) as embodiments.
(1) An active energy ray-curable composition comprising a compound represented by the following general formula (I).

(In the formula, R is hydrogen or a methyl group, A is a structure represented by any of the following structural formulas (II) to (VII), each of which may have a substituent such as an alkyl group or an alkoxy group, j and k are integers of 0 or more, X represents a substituent containing a hetero atom, n is an integer of 0 or more, m is an integer of 1 or more, n+m is 3 or more, or n=0, m=2 Each wavy line in structural formulas (II) to (VII) independently indicates a bond with X or a (meth)acryloyl group (H ₂ C═CR—C(═O)—). )

(2) The active energy ray-curable composition further contains a radically polymerizable compound, and 4 parts by mass to 20 parts by mass of the compound represented by the general formula (I) with respect to 100 parts by mass of the radically polymerizable compound. The active energy ray-curable composition according to (1) above, characterized in that it contains
(3) The activity according to (1) or (2) above, wherein n and m are integers of 1 or more and n+m is an integer of 3 or more in the compound represented by the general formula (I). Energy ray-curable composition.
(4) The active energy ray-curable composition according to any one of (1) to (3) above, wherein X in general formula (I) is a heteroatom-containing cyclic substituent. thing.
(5) The active energy ray-curable composition according to any one of (1) to (4) above, which contains a polymerization initiator.
(6) Any one of the above (1) to (5), wherein the compound represented by the general formula (I) is a compound having a structure represented by the following (A-1) to (A-20) 1. The active energy ray-curable composition according to item 1.

(7) The active energy ray-curable composition according to any one of (1) to (6) above, which is a material for three-dimensional modeling.
(8) An active energy ray-curable ink composition using the active energy ray-curable composition according to any one of (1) to (7) above.
(9) An active-energy-ray-curable ink composition for inkjet, characterized by using the active-energy-ray-curable ink composition described in (8) above.
(10) A composition container containing the composition according to any one of (1) to (9) above.
(11) A two-dimensional composition comprising: a container containing the composition according to any one of (1) to (9) above; and irradiation means for irradiating an active energy ray. Or a three-dimensional imager.
(12) A two-dimensional or three-dimensional image forming method, comprising an irradiation step of irradiating the composition according to any one of (1) to (9) above with an active energy ray.
(13) A cured product of the composition according to any one of (1) to (9) above.
(14) A decorated body comprising a base material and a surface decorated with the cured product according to (13) above.
(15) An active energy ray-curable composition comprising a compound represented by the following general formula (I).

(In the formula, R is hydrogen or a methyl group, A is a polyhydric alcohol residue, and X is a substituent containing a heteroatom. n is an integer of 0 or more, m is an integer of 1 or more, n+m is 3 or more, or n = 0, m = represents an integer of 2.)

1 storage pool (accommodation part)
3 Movable stage 4 Active energy ray 5 Active energy ray-curable composition 6 Curing layer 30 Ejection head units 31 and 32 for molded object Ejection head units 33 and 34 for support Ultraviolet irradiation means 35 Three-dimensional object 36 Support laminate 37 Modeled object support substrate 38 Stage 39 Image forming device

Japanese Patent Publication No. 2015-531809 Japanese Patent Application Laid-Open No. 2017-110200 Japanese Patent No. 5959602 Japanese Patent No. 5788918 JP 2003-253248 A

Claims (13)

An active energy ray-curable composition comprising a compound represented by the following general formula (I) and a radically polymerizable compound.

(In the formula, R is hydrogen or a methyl group, A is a structure represented by any of the following structural formulas (II) to (V). X is the following structural formulas (X-1) to (X-4). n is an integer of 0 or more, m is an integer of 1 or more, and n+m is an integer of 3 or more, and each wavy line in structural formulas (II) to (V) is independent. indicates a bond with X or a (meth)acryloyl group (H ₂ C=CR-C(=O)-), and the * marks in structural formulas (X-1) to (X-4) indicate the binding sites. show.)

2. The method according to claim 1, wherein the active energy ray-curable composition contains 4 parts by mass to 20 parts by mass of the compound represented by the general formula (I) with respect to 100 parts by mass of the radically polymerizable compound. The active energy ray-curable composition as described. 3. The active energy ray-curable composition according to claim 1, wherein n and m are integers of 1 or more and n+m is an integer of 3 or more in the compound represented by the general formula (I). . 4. The active energy ray-curable composition according to claim 1, further comprising a polymerization initiator. Any one of claims 1 to 4, wherein the compound represented by the general formula (I) is a compound having a structure represented by the following (A-1) to (A-10), (A-16) 1. The active energy ray-curable composition according to item 1.

6. The active energy ray-curable composition according to any one of claims 1 to 5, which is a three-dimensional modeling material. An active energy ray-curable ink composition comprising the active energy ray-curable composition according to any one of claims 1 to 6. An active energy ray-curable inkjet ink composition, comprising the active energy ray-curable ink composition according to claim 7 . A composition container containing the composition according to any one of claims 1 to 8. 9. A two-dimensional or three-dimensional image formation comprising: a container containing the composition according to any one of claims 1 to 8; and irradiation means for irradiating an active energy ray. Device. 9. A two-dimensional or three-dimensional image forming method, comprising an irradiation step of irradiating the composition according to any one of claims 1 to 8 with an active energy ray. A cured product of the composition according to any one of claims 1 to 8. A decorative body comprising a base material and a surface decoration comprising the cured product according to claim 12 on the base material.

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