JP6759577B2 - Active energy ray-curable composition, active energy ray-curable ink, composition container, two-dimensional or three-dimensional image forming device, two-dimensional or three-dimensional image forming method, cured product, decorative body, and active energy. Linearly polymerizable compound - Google Patents

Description

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

The inkjet recording method has high ink consumption efficiency and excellent resource saving, and can keep the ink cost per unit recording low.

However, in the above-mentioned inkjet recording method, when formed on an absorbent recording medium such as plain paper using ink, bleeding of print dots is likely to occur, and the dryness is poor, so that the paper cannot be stacked immediately after printing. Problems may occur.

Therefore, by curing the ink with active energy rays such as ultraviolet rays, it is possible to prevent bleeding of print dots, and an active energy ray-curable inkjet recording method having excellent drying properties is drawing attention.

The ink composition used in the active energy ray-curable inkjet recording method includes, for example, a polyfunctional (meth) acrylic acid containing a secondary or tertiary hydroxyl group in the molecule and a hetero atom capable of forming a hydrogen bond with the hydroxyl group. Ink composition for inkjet containing an ester or amide compound (see, for example, Patent Document 1); Ink composition for ink jet using a polyfunctional (meth) acrylic acid ester compound having a secondary hydroxyl group (see, for example, Patent Document 2). An ink composition for inkjet (see, for example, Patent Document 3) in which an aliphatic (meth) acrylic acid ester compound having a secondary hydroxyl group in the molecule and another nitrogen-containing polymerizable monomer compound are combined has been proposed. ..

An object of the present invention is to provide an active energy ray-curable composition having less odor and excellent in active energy ray-polymerizable and active energy ray-curable properties.

The active energy ray-curable composition of the present invention as a means for solving the above-mentioned problems contains a (meth) acrylic acid ester compound represented by the following general formula (1) having a tertiary hydroxyl group in the molecule. ..
(However, in the general formula (1), OH represents a tertiary hydroxyl group, m and n represent integers of 1 or more and 2 or less, R ¹ represents either a hydrogen atom or a methyl group, and X is carbon. It represents either a group consisting of an aliphatic hydrocarbon having a number of 4 or more and 10 or less and a group consisting of an aliphatic cyclic hydrocarbon having 4 or more and 10 or less carbon atoms.

According to the present invention, it is possible to provide an active energy ray-curable composition having less odor and excellent in active energy ray-polymerizable and active energy ray-curable properties.

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.

The active energy ray-curable composition of the present invention contains a (meth) acrylic acid ester compound represented by the following general formula (1) having a tertiary hydroxyl group in the molecule, and further contains other components as necessary. It contains.
(However, in the general formula (1), OH represents a tertiary hydroxyl group, m and n represent integers of 1 or more and 2 or less, R ¹ represents either a hydrogen atom or a methyl group, and X is carbon. It represents either a group consisting of an aliphatic hydrocarbon having a number of 4 or more and 10 or less and a group consisting of an aliphatic cyclic hydrocarbon having 4 or more and 10 or less carbon atoms.
In the present invention, since the ink composition used in the conventional active energy ray-curable inkjet recording method has an odor peculiar to the (meth) acrylic acid ester compound, the working environment such as giving discomfort due to the odor. It is based on the finding that there is the above problem and it is desired to further improve the active energy ray polymerizable property and the active energy ray curable property.

The active energy ray-polymerizable compound of the present invention is a (meth) acrylic acid ester compound represented by the general formula (1) having a tertiary hydroxyl group in the molecule.

(Active energy ray-polymerizable compound)
The active energy ray-polymerizable compound of the present invention is a (meth) acrylic acid ester compound represented by the following general formula (1) having a tertiary hydroxyl group in the molecule.
(However, in the general formula (1), OH represents a tertiary hydroxyl group, m and n represent integers of 1 or more and 2 or less, R ¹ represents either a hydrogen atom or a methyl group, and X is carbon. It represents either a group consisting of an aliphatic hydrocarbon having a number of 4 or more and 10 or less and a group consisting of an aliphatic cyclic hydrocarbon having 4 or more and 10 or less carbon atoms.

<(Meta) acrylic acid ester compound>
The (meth) acrylic acid ester compound is represented by the general formula (1).

OH in the general formula (1) represents a tertiary hydroxyl group.
M and n in the general formula (1) represent integers of 1 or more and 2 or less, and 1 is preferable.
R ¹ in the general formula (1) represents either a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

X in the general formula (1) represents either a group composed of an aliphatic hydrocarbon having 4 or more and 10 or less carbon atoms and a group composed of an aliphatic cyclic hydrocarbon having 4 or more and 10 or less carbon atoms. When the number of carbon atoms is 10 or less, when the (meth) acrylic acid ester compound represented by the general formula (1) is synthesized, it is possible to prevent the viscosity from increasing or to prevent the compound from becoming a solid. Can be done.
Further, the above-mentioned aliphatic hydrocarbon and aliphatic cyclic hydrocarbon may be saturated or unsaturated, and oxygen atom, nitrogen atom, sulfur atom chlorine atom and the like are bonded to the carbon chain. May be.
The (meth) acrylic acid ester compound represented by the general formula (1) has one or more (meth) acrylic acid ester structures as a polymerizable functional group, and has one or more and two or less tertiary hydroxyl groups. Have. In general, a polyfunctional monomer having a plurality of (meth) acrylic acid ester structures which are polymerizable functional groups in a molecule can improve curability as compared with a monofunctional monomer by forming a crosslinked structure between molecules accompanying a polymerization reaction. There is a tendency. On the other hand, a monofunctional monomer compound having only one (meth) acrylic acid ester as a polymerizable functional group tends to be inferior in curing function to a polyfunctional monomer because it cannot form a crosslinked structure in the polymerization process. It is in.
In the (meth) acrylic acid ester compound represented by the general formula (1), the distance between the monomers becomes closer due to the intermolecular interaction by introducing a polar structure having a strong hydrogen bond property into the molecule of the monomer. The polymerization reaction by the active energy ray becomes easy to proceed, and the active energy ray curability can be improved. Curability can also be improved by introducing a cyclic structure or a branched structure into the monomer molecule, which is polymerized due to the presence of the branched structure or ring structure in the polymer produced by the polymerization reaction with active energy rays. It is considered that this is due to the decrease in molecular motility and flexibility of the later cured product. The "(meth) acrylic acid" of the (meth) acrylic acid ester compound means acrylic acid or methacrylic acid.

The (meth) acrylic acid ester compound represented by the general formula (1), which is the active energy ray-polymerizable compound of the present invention, has a (meth) acrylic acid ester structure of 1 or more and 2 or less, and 1 or more and 2 or less. It is a polyfunctional monomer having a secondary hydroxyl group, and by having the tertiary hydroxyl group, excellent active energy ray polymerizable property, active energy ray curable property, and low odor property can be realized. That is, having a tertiary hydroxyl group reduces the distance between the monomers due to the interaction between the monomer molecules, and facilitates the polymerization reaction by the active energy ray. Furthermore, the presence of a tertiary hydroxyl group means that a branched structure is present at the same time, and the branched structure containing the tertiary hydroxyl group introduced into the polymer tends to harden the polymer, resulting in active energy ray curability. Excellent for. This is superior to a monomer compound having a primary hydroxyl group or a secondary hydroxyl group having the same branched structure. In addition, since the tertiary hydroxyl group has a highly polar hydroxyl group even though it has a large steric disorder, volatility is suppressed by intermolecular interaction, and generation of odor is suppressed to achieve low odor. Excellent.

Examples of the group composed of the aliphatic hydrocarbon having 4 or more and 10 or less carbon atoms include a 2-methylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, and 2 -Methylhexyl group, 3-methylhexyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 2,2-dimethyloctyl group, 2,3-dimethyloctyl group, 2,4-dimethyl Examples thereof include an octyl group, a 3,6-dimethyloctyl group and a 3,7-dimethyloctyl group.

Examples of the group composed of an aliphatic cyclic hydrocarbon having 4 or more and 10 or less carbon atoms include a 2-methylcyclohexyl group, a 3-methylcyclohexyl group, and a 1,4-dimethylcyclohexyl group.

Next, specific examples of the (meth) acrylic acid ester compound represented by the general formula (1) will be shown separately for the case where n is 2 and the case where n is 1 in the general formula (1). , Not limited to these.

As the (meth) acrylic acid ester compound represented by the general formula (1) when n in the general formula (1) is 2, for example, a compound represented by the following general formula (6) is preferable. Listed in.
(However, in the general formula (6), Y ¹ and Y ² each independently represent a substituted or unsubstituted alkylene group having 1 or more and 6 or less carbon atoms, and Z represents an alkyl group having 1 or more and 3 or less carbon atoms. Representing, R ¹ and R ² independently represent either a hydrogen atom or a methyl group.)

In the general formula (6), Y ¹ and Y ² each independently represent a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, and Y ¹ and Y ² are different even if they are the same. May be good.
Examples of the substituent include a chlorine atom and the like.
In the general formula (6), Z represents an alkyl group having 1 or more carbon atoms and 3 or less carbon atoms.
In the general formula (6), R ¹ and R ² independently represent either a hydrogen atom or a methyl group, and R ¹ and R ² may be the same or different.

Examples of the alkylene group having 1 or more and 6 or less carbon atoms include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group and an n-hexylene group.
Examples of the alkyl group having 1 or more and 3 or less carbon atoms include a methyl group, an ethyl group, and a propyl group.

As the compound represented by the general formula (6), for example, a compound represented by the following general formula (7) is preferably mentioned.
(However, in the general formula (7), R ¹ and R ² independently represent either a hydrogen atom or a methyl group, respectively.)

In the general formula (7), R ¹ and R ² independently represent either a hydrogen atom or a methyl group, and R ¹ and R ² may be the same or different, and the hydrogen atom may be different. preferable.

An exemplary compound in the case where n in the general formula (1) is 2 is shown below.

<Exemplary compound A1>

<Example compound A2>

<Example compound B1>

<Example compound B2>

<Example compound C1>

<Example compound C2>

<Example compound D1>

<Exemplary compound D2>

<Exemplary compound E1>

<Example compound E2>

<Exemplary compound F1>

<Example compound F2>

<Exemplary compound G1>

<Example compound G2>

As the (meth) acrylic acid ester compound represented by the general formula (1) when n in the general formula (1) is 1, for example, a compound represented by the following general formula (2) is preferable. Listed in.
(However, in the general formula (2), OH represents a tertiary hydroxyl group, R ¹ represents either a hydrogen atom or a methyl group, and X ¹ is a substituted or unsubstituted carbon number of 4 or more and 10 or less. Represents a branched alkylene group.)

OH in the general formula (2) represents a tertiary hydroxyl group.
In the general formula (2), X ¹ represents a branched alkylene group having 4 or more and 10 or less carbon atoms, which is substituted or unsubstituted.
Examples of the substituent include a chlorine atom and the like.
In the general formula (2), R ¹ represents either a hydrogen atom or a methyl group.
Examples of the branched alkylene group having 4 or more and 10 or less carbon atoms include a t-butylene group, a t-pentylene group, a t-hexylene group, a t-heptylene group, a t-octylene group, a t-nonylene group, and a t-decylene group. And so on.

As the compound represented by the general formula (2), for example, a compound represented by the following general formula (3), a compound represented by the following general formula (8), and the like are preferably mentioned.
(However, in the general formula (3), OH represents a tertiary hydroxyl group, R ¹ represents either a hydrogen atom or a methyl group, and Y is a substituted or unsubstituted branch having 3 or more and 9 or less carbon atoms. Represents an alkylene group.)
OH in the general formula (3) represents a tertiary hydroxyl group.
In the general formula (3), X ¹ represents a branched alkylene group having 3 or more and 9 or less carbon atoms, which is substituted or unsubstituted.
Examples of the substituent include a chlorine atom and the like.
Examples of the branched alkylene group having 3 or more carbon atoms and 9 or less carbon atoms include a t-propylene group, a t-butylene group, a t-pentylene group, a t-hexylene group, a t-heptylene group, a t-octylene group and a t-nonylene group. And so on.

(However, in the general formula (8), R ¹ represents either a hydrogen atom or a methyl group.)

In the general formula (8), R ¹ represents either a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

As the compound represented by the general formula (3), for example, a compound represented by the following general formula (4), a compound represented by the following general formula (5), and the like are preferably mentioned. Among these, the compound represented by the general formula (5) is more preferable from the viewpoint of active energy ray polymerization and active energy ray curability.

(However, in the general formula (4), R ¹ represents either a hydrogen atom or a methyl group.)

In the general formula (4), R ¹ represents either a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

(However, in the general formula (5), R ¹ represents either a hydrogen atom or a methyl group.)

In the general formula (5), R ¹ represents either a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

An exemplary compound in the case where n in the general formula (1) is 1 is shown below.

<Example compound H1>

<Exemplary compound H2>

<Example compound I1>

<Example compound I2>

<Example compound J1>

<Example compound J2>

<Example compound K1>

<Example compound K2>

<Example compound L1>

<Example compound L2>

<Example compound M1>

<Example compound M2>

<Exemplary compound N1>

<Exemplary compound N2>

<Example compound O1>

<Exemplary compound O2>

<Example compound P1>

<Example compound P2>

<Example compound Q1>

<Example compound Q2>

<Example compound R1>

<Example compound R2>

<Example compound S1>

<Example compound S2>

Examples are represented by the general formula (1) (meth) acrylic acid ester compound, m in the general formula (1), n, and becomes a different compound of structure according to the type of R ^1, these, 1 The species may be used alone, or two or more different compounds may be mixed and used. In this case, the different compounds also include structural isomers, and the mixing ratio of the two or more kinds is not particularly limited, and the purpose is It can be appropriately selected accordingly.

-Manufacturing method-
As a method for producing the (meth) acrylic acid ester compound represented by the general formula (1), for example, triol or diol is added to dehydrated dichloromethane, the inside of the flask is replaced with argon gas, and then triethylamine is added. Next, after cooling to about −10 ° C., methacrylic acid chloride is slowly added dropwise so that the temperature inside the system becomes −10 ° C. or higher and −5 ° C. or lower, and the mixture is stirred at room temperature for 2 hours. Further, after removing the precipitate by filtration, the filtrate is washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution. It can then be dried over sodium sulphate and then concentrated under reduced pressure to give a brown oil. Further, the product name: Wakogel (registered trademark) C300 (manufactured by Wako Pure Chemical Industries, Ltd.) was filled, and the oily substance was purified by column chromatography using hexane and ethyl acetate as the eluate, and the above general formula ( The (meth) acrylic acid ester compound represented by 1) can be obtained. In addition to the above method, for example, triol or diol and methacrylic acid can be obtained by dehydration condensation in a hydrophobic solvent such as toluene in the presence of an acid catalyst.

-Identification method-
As a method for identifying the (meth) acrylic acid ester compound represented by the general formula (1), for example, ¹ H-NMR spectrum and IR spectrum can be used for identification.
The ¹ H-NMR spectrum can be measured using ¹ H-NMR (500 MHz) (manufactured by JEOL Ltd.). In the measured spectrum, it can be confirmed that the (meth) acrylic acid ester structure is introduced by the presence of the peak generated on the low magnetic field side of about 5.5 ppm to 6.5 ppm.
The IR spectrum can be measured using FT-IR Spectrem GX (manufactured by PERKIN ELMER). In the measured spectrum, the presence of a peak near about 1,700 cm ^-1 to 1,750 cm ^{-1 and} a peak near about 810 cm ^-1 confirms that the (meth) acrylic acid ester structure is introduced. it can. Furthermore, the presence of a broad peak near 3,500 cm ^-1 indicates that the hydroxyl group is introduced.

(Active energy ray-curable composition)
The active energy ray-curable composition of the present invention contains a (meth) acrylic acid ester compound represented by the following general formula (1) having a tertiary hydroxyl group in the molecule, and further contains other components as necessary. It contains.
(However, in the general formula (1), OH represents a tertiary hydroxyl group, m and n represent integers of 1 or more and 2 or less, R ¹ represents either a hydrogen atom or a methyl group, and X is carbon. It represents either a group consisting of an aliphatic hydrocarbon having a number of 4 or more and 10 or less and a group consisting of an aliphatic cyclic hydrocarbon having 4 or more and 10 or less carbon atoms.

As the (meth) acrylic acid ester compound represented by the general formula (1), the same compound as the active energy ray-polymerizable compound of the present invention can be used.

The content of the (meth) acrylic acid ester compound represented by the general formula (1) is preferably 20% by mass or more and 98% by mass or less, preferably 30% by mass or more, based on the total amount of the active energy ray-curable composition. 90% by mass or less is more preferable, and 30% by mass or more and 80% by mass or less is particularly preferable.

<Other ingredients>
Examples of the other components include a polymerization initiator, a colorant, an active energy ray-polymerizable compound other than the (meth) acrylic acid ester compound represented by the general formula (1), a sensitizer, and a co-sensitizer. , Polymerization initiator, solvent, surfactant, leveling additive, matting agent, polyester resin for adjusting film physical properties, polyurethane resin, vinyl resin, acrylic resin, rubber resin, waxes, adhesive Examples include agents (tack fire). These may be used alone or in combination of two or more.

<Polymerization initiator>
The active energy ray-curable composition of the present invention may contain a polymerization initiator. The polymerization initiator may be one that can generate active species such as radicals and cations by the energy of the active energy ray and initiate the polymerization of the polymerizable compound (monomer or oligomer). As such a polymerization initiator, known radical polymerization initiators, cationic polymerization initiators, base generators and the like can be used alone or in combination of two or more, and among them, a radical polymerization initiator is used. Is preferable. Further, the polymerization initiator is preferably contained in an amount of 5 to 20% by mass with respect to the total mass (100% by mass) of the composition in order to obtain a sufficient curing rate.
Examples of the radical polymerization initiator include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, and the like. Examples thereof include ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.
Further, in addition to the above-mentioned polymerization initiator, a polymerization accelerator (sensitizer) can also be used in combination. The polymerization accelerator is not particularly limited, but for example, 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 preferable, and the content thereof may be appropriately set according to the polymerization initiator used and the amount thereof.

<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. 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.

<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 density, 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.
Further, 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.

The coloring material is preferably dispersed appropriately in the active energy ray-curable composition, and examples of the dispersion include a method using a disperser and a method of adding a dispersant.
The disperser is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a ball mill, a sand mill, a ring mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, or a wet type. Examples include jet mills and paint shakers.
The dispersant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polymer dispersants.

The volume average particle diameter of the coloring material is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.005 μm or more and 0.5 μm or less, and more preferably 0.01 μm or more and 0.45 μm or less. , 0.015 μm or more and 0.4 μm or less is particularly preferable. When the volume average particle diameter is 0.005 μm or more and 0.5 μm or less, clogging of the head nozzle is suppressed, and storage stability, transparency and active energy ray curability of the active energy ray-curable composition are maintained. be able to.

The mass ratio (dispersant / color material) of the content of the coloring material (mass%) and the content of the dispersant (mass%) is preferably 0.01 or more and 0.50 or less.

The content of the coloring material is preferably 0.5% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 8% by mass or less, based on the total amount of the active energy ray-curable composition.
The content of the coloring material in the white active energy ray-curable composition using a white pigment such as titanium oxide as a coloring material is preferably 5% by mass or more and 30% by mass or less from the viewpoint of ensuring concealment. More preferably, it is 10% by mass or more and 25% by mass or less.

-Active energy ray-polymerizable compounds other than the (meth) acrylic acid ester compound represented by the general formula (1)-
The active energy ray-polymerizable compound other than the (meth) acrylic acid ester compound represented by the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, photoradical polymerization. Examples thereof include sex compounds, photocationic polymerizable compounds, and photoanionic polymerizable compounds. These may be used alone or in combination of two or more.

The photoradical polymerizable compound is not particularly limited as long as it is a compound having one or more ethylenically unsaturated groups capable of photoradical polymerization, and examples thereof include monomers, oligomers, and polymers. These may be used alone or in combination of two or more.
Examples of the photoradical polymerizable compound include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid, salts thereof, compounds derived from these, and ethylenically unsaturated compounds. Examples thereof include anhydrides having a group, acrylonitrile, styrene, unsaturated polyester, unsaturated polyether, unsaturated polyamide, and unsaturated urethane. These may be used alone or in combination of two or more.

Specific examples of the photoradical polymerizable compound include 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, and bis (4-acryloxypolyethoxyphenyl) propane. , Neopentyl glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol Diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetra Acrylate derivatives such as acrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, epoxy acrylate, methyl methacrylate, n-butyl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1, 6-Hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylol ethanetrimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxy) Polyethoxyphenyl) Methacrylic acid derivatives such as propane, acrylamide derivatives such as N-methylolacrylamide, diacetoneacrylamide, 2-hydroxyethylacrylamide, acryloylmorpholin, and allyl compounds such as allylglycidyl ether, diallyl phthalate, and triallyl trimellitate. Derivatives: ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glyco Lumonovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, trimethylol propane Di or trivinyl ether compounds such as trivinyl ether; ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, Monovinyl ether compounds such as isopropenyl ether-o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether; 2-ethylhexyl diglycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl acrylate, hydroxypivalic acid Neopentyl glycol diacrylate, 2-acryloyloxyethyl phthalic acid, methoxypolyethylene glycol acrylate, tetramethylol methanetriacrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, dimethylol tricyclodecane diacrylate, ethoxylated Phenyl acrylate, 2-acryloyloxyethyl succinic acid, nonylphenol ethylene oxide adduct acrylate, modified glycerin triacrylate, bisphenol A diglycidyl ether acrylic acid adduct, modified bisphenol A diacrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethyl Hexahydrophthalic acid, propylene oxide adduct diacrylate of bisphenol A, ethylene oxide adduct diacrylate of bisphenol A, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, tolylene isocyanato urethane prepolymer, lactone-modified flexible acrylate, Butoxyethyl acrylate, propylene glycol diglycidyl ether acrylic acid adduct, pentaerythritol tri Acrylate, Hexamethylene Diisocyanato Urethane Prepolymer, 2-Hydroxyethyl Acrylate, methoxydipropylene Glycol Acrylate, Ditrimethylol Propane Tetraacrylate, Pentaerythritol Triacrylate, Hexamethylene Diisocyanato Urethane Prepolymer, Stearyl Acrylate, Isoamyl Acrylate, Iso Examples thereof include myristyl acrylate, isostearyl acrylate, and lactone-modified acrylate. These may be used alone or in combination of two or more.

Examples of the photocationically polymerizable compound include an epoxy compound, a vinyl ether compound, and an oxetane compound. These may be used alone or in combination of two or more.

Examples of the photoanionic polymerizable compound include epoxy compounds, lactone compounds, acrylic compounds, and methacrylic compounds. Among these, acrylic compounds and methacrylic compounds exemplified as photoradical polymerizable compounds are preferable.

Examples of the combination of the active energy ray-polymerizable compound and the polymerization initiator include a combination of a photoradical polymerizable compound and a photoradical polymerization initiator, a combination of a photocationic polymerizable compound and a photocationic polymerization initiator, and the like. Examples thereof include a combination of a photoanionic polymerizable compound and a photoanionic polymerization initiator.

Mass ratio of the content (mass%) of the (meth) acrylic acid ester compound represented by the general formula (1) to the content (mass%) of the other active energy ray-polymerizable compound (other active energy rays). The polymerizable compound / (meth) acrylic acid ester compound represented by the general formula (1) is preferably 0.01 or more and 100 or less, and more preferably 0.1 or more and 50 or less.

Mass ratio of the content (mass%) of the active energy ray-polymerizable compound and the coloring material to the content (mass%) of the polymerization initiator [(polymerization initiator / (active energy ray-polymerizable compound + said) The color material)) is preferably 0.01 or more and 0.50 or less, more preferably 0.02 or more and 0.40 or less, and particularly preferably 0.05 or more and 0.30 or less.

<Sensitizer>
The sensitizer can be contained to accelerate the decomposition of the polymerization initiator by irradiation with active energy rays.
The sensitizer absorbs active energy rays to be in an electron-excited state, and in that state, comes into contact with the polymerization initiator, and chemically changes the polymerization initiator by the action of, for example, electron transfer, energy transfer, heat generation, etc. Decomposition, radical, acid or base production) is promoted.

The mass ratio (sensitizer / polymerization initiator) between the content of the sensitizer (mass%) and the content of the polymerization initiator (mass%) is preferably 5 × 10 ^-3 or more and 200 or less. , 0.02 or more and 50 or less is more preferable.

The sensitizer is not particularly limited, and a sensitizing dye having an absorption wavelength in a wavelength region of 350 nm or more and 450 nm or less can be used.
Examples of the sensitizing dye include polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluoressein, eosin, erythrosin, rhodamine B, rosebengal), cyanines (eg, thiacarbo). Cyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbocyanine), thiadins (eg, thionin, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acryflabin), anthraquinones (eg, erythrinone) , Anthraquinone), squaryliums (eg, squarylium), coumarins (eg, 7-diethylamino-4-methylcoumarin) and the like. These may be used alone or in combination of two or more.

-Cosensitizer-
As the co-sensitizer, for example, the sensitivity of the sensitizing dye to active energy rays can be further improved, and the inhibition of polymerization of the active energy ray-polymerizable compound by oxygen can be suppressed.

The co-sensitizer is not particularly limited, and is, for example, an amine compound such as triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline, 2-mercaptobenzothiazole. , 2-Mercaptobenzoxazole, 2-Mercaptobenzoimidazole, 2-Mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene and other thiols and sulfides. These may be used alone or in combination of two or more.

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

-Polymerization inhibitor-
The polymerization inhibitor is used for improving the storage stability (storage stability) of the active energy ray-curable composition, and for the head by thermal polymerization when the active energy ray-curable composition is heated to reduce its viscosity and discharged. It can be contained to prevent clogging.

The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone, benzoquinone, p-methoxyphenol, TEMPO, TEMPOL, and a cuperon complex of aluminum. These may be used alone or in combination of two or more.

The content of the polymerization inhibitor is preferably 200 ppm or more and 20,000 ppm or less.
The content of the polymerization inhibitor is preferably 0.05% by mass or more and 1.0% by mass or less with respect to the total amount of the active energy ray-curable composition.

<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.

-Adhesive agent-
The tackifier (tack fire) can be contained in order to improve the adhesiveness to polyolefin, PET and the like.

The active energy ray-curable composition can be contained in a container and used as an ink cartridge. As a result, it is not necessary to directly touch the active energy ray-curable composition in work such as replacement of the active energy ray-curable composition, and it is possible to prevent the fingers and clothes from becoming dirty. In addition, it is possible to prevent foreign substances such as dust from being mixed into the active energy ray-curable composition.

<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 a discharge means for discharging the composition from a nozzle is applied. The viscosity in the range of 20 ° C. to 65 ° C., preferably the viscosity at 25 ° C. is preferably 3 mPa · s or more and 70 mPa · s or less, more preferably 5 mPa · s or more and 15 mPa · s or less, and 6 mPa · s or more and 12 mPa · s. The following are particularly preferred. Further, it is particularly preferable that the viscosity range is satisfied without containing the organic solvent. For the above viscosity, a cone rotor (1 ° 34'x R24) was used with a cone plate type rotational viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd., the rotation speed was 50 rpm, and the temperature of constant temperature circulating water was 20 ° C. It can be appropriately set and measured in the range of ~ 65 ° C. VISCOMATE VM-150III can be used to adjust the temperature of the circulating water.

<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.

<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. 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). In addition, FIG. 2 is a method of discharging the active energy ray-curable composition of the present invention into a predetermined region, irradiating the active energy ray and curing the composition, and sequentially laminating them 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 device can be used, and 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 the form of a sheet or a film that has been subjected to molding processing such as heat stretching or punching. For example, automobiles, OA equipment, and electricity. -Suitably used for applications that require molding after decorating the surface, such as electronic devices, meters for cameras, and panels for operation units.
The base material is not particularly limited and may be appropriately selected depending on the intended purpose. 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.

(Active energy ray-curable ink)
The active energy ray-curable ink of the present invention contains the active energy ray-curable composition of the present invention, and further contains other components as necessary.

<Other ingredients>
As the other component, the same component as the other component in the active energy ray-curable composition of the present invention can be used.

The active energy ray-curable ink of the present invention is preferably 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.

<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 a surface to be printed having irregularities, metal, ceramic, and the like. It also includes those printed on the surface to be printed, which are made of various materials. Further, by stacking two-dimensional images, it is possible to form a partially three-dimensional image (an image composed of two-dimensional and three-dimensional) or a three-dimensional object.
FIG. 2 is a schematic view showing an example of another image forming apparatus (three-dimensional stereoscopic image forming apparatus) 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, irradiated with active energy rays, and 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 active energy rays to solidify. 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 model 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.

(Printed matter)
The printed matter is not only a printed matter printed on a smooth surface such as ordinary paper or a resin film using the active energy ray-curable composition of the present invention or an active energy ray-curable ink, but also a subject having irregularities. It also includes those printed on the printed surface and those printed on the printed surface made of various materials such as metal and ceramic.
Further, the active energy ray-polymerizable compound and the active energy ray-curable composition of the present invention are suitable as materials for ink, but they are molding resins, paints, adhesives, insulating materials, mold release agents, coating materials, and sealing materials. It can also be applied to materials, various resists, various optical materials, and the like.

(Hardened product)
The cured product of the present invention is obtained by irradiating the active energy ray-curable composition of the present invention and the active energy ray-curable ink of the present invention with active energy rays to cure the cured product.
As the active energy ray, the same as the active energy ray of the active energy ray-curable composition can be used.

(Decorative body)
As the decorative body of the present invention, a surface decoration made of the cured product of the present invention is applied on a base material.
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 workability, plastic is preferable.

(Photocurable composition)
The photocurable composition contains the active energy ray-polymerizable compound of the present invention, and if necessary, contains other components.
As the other component, the same component as the other component in the active energy ray-curable composition can be used.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, "part" and "%" in an example are "part by mass" and "mass%". In addition, each compound was identified using ^{1 1} H-NMR spectrum and IR spectrum. The ¹ H-NMR spectrum was measured using ¹ H-NMR (500 MHz) (manufactured by JEOL), and the IR spectrum was measured using FT-IR Spectrum GX (manufactured by PERKIN ELMER). Furthermore, the viscosity was adjusted 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., at a rotation speed of 50 rpm and a constant temperature circulating water temperature of 25 ° C. Was measured. VISCOMATE VM-150III was used to adjust the temperature of the circulating water.

<Example 1A>
-Synthesis example of active energy ray-polymerizable compound 1-
12.98 g (180 mmol) of isobutylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 140 mL of dehydrated acetonitrile, and 1.3 g (4 mmol) of tetrabutylammonium bromide was added. After slowly adding 10.8 g (150 mmol) of acrylic acid at room temperature, the mixture was heated and refluxed for 4.5 hours. The filtrate (colorless solution) obtained by filtering the reaction mixture was concentrated under reduced pressure. 80 mL of a 5 mass% sodium carbonate aqueous solution was added to the obtained concentrate, and then extraction was performed using dichloromethane. The dichloromethane solution was dried over sodium sulfate and then concentrated under reduced pressure to give a colorless oil. Further, 350 g of Wakogel C300 (manufactured by Wako Pure Chemical Industries, Ltd.) is filled, purified by column chromatography using hexane and ethyl acetate as an eluent, and activated energy ray polymerization represented by the following structural formula (1). 2.3 g (yield of about 11%) of a colorless oily substance of the sex compound 1 was obtained.
[Active energy ray-polymerizable compound 1]

The identification data of the active energy ray-polymerizable compound 1 is as follows.
^{1 1} H-NMR (CDCl ₃ ): δ1.28 (s, 6H), 1.61 (bs, 1H), 4.06 (s, 2H), 5.89 (dd, 1H), 6.16-6 .21 (m, 1H), 6.46 (dd, 1H)
IR (NaCl): 3442, 2979, 1727, 1634, 1618, 1471, 1409, 1383, 1637, 1298, 1201, 1066, 1010, 985, 924, 814, 774, 667 cm ^-1

<Example 2A>
-Example of synthesis of active energy ray-polymerizable compound 2-
12.5 g (120 mmol) of 3-methyl-1,3-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 130 mL of dehydrated dichloromethane, the inside of the flask was replaced with argon gas, and then 14.6 g (144 mmol) of triethylamine was added. added. Next, after cooling to about −10 ° C., 13.0 g (144 mmol) of acrylic acid chloride was slowly added dropwise so that the temperature inside the system became −10 ° C. to −5 ° C., and the mixture was stirred at room temperature for 2 hours. .. Further, after removing the precipitate by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution. It was then dried over sodium sulfate and then concentrated under reduced pressure to give a brown oil. Further, 350 g of Wakogel C300 (manufactured by Wako Pure Chemical Industries, Ltd.) is filled, and the brown oily substance is purified by column chromatography using hexane and ethyl acetate as the eluate, and is represented by the following structural formula (2). 7.7 g (yield of about 41%) of a colorless oily substance of the active energy ray-polymerizable compound 2 was obtained.
[Active energy ray-polymerizable compound 2]

The identification data of the active energy ray-polymerizable compound 2 is as follows.
^{1 1} H-NMR (CDCl ₃ ): δ1.28 (s, 6H), 1.67 (bs, 1H), 1.89 (t, 2H), 4.34 (t, 2H), 5.84 (dd) , 1H), 6.09-6.15 (m, 1H), 6.40 (dd, 1H)
IR (NaCl): 3441,297,2936,1725,1636,1619,1470,1410,1380,1298,1198,1056,984,940,877,812,667cm ^-1

<Example 3A>
-Example of synthesis of active energy ray-polymerizable compound 3-
After adding 14.2 g (120 mmol) of 2-methylpentane-2,4-diol (manufactured by Tokyo Chemical Industry Co., Ltd.) to 130 mL of dehydrated dichloromethane and replacing the inside of the flask with argon gas, 14.6 g (144 mmol) of triethylamine was added. added. Next, after cooling to about −10 ° C., 13.0 g (144 mmol) of acrylic acid chloride was slowly added dropwise so that the temperature inside the system became −10 ° C. to −5 ° C., and the mixture was stirred at room temperature for 2 hours. .. Further, after removing the precipitate by filtration, the obtained solution was concentrated under reduced pressure. Ethyl acetate (150 mL) was added to this concentrate and stirred, and the precipitated solid was removed by filtration, and the obtained filtrate was concentrated under reduced pressure to obtain a yellow solution. Further, 350 g of Wakogel C300 (manufactured by Wako Pure Chemical Industries, Ltd.) is filled, and the yellow oil is purified by column chromatography using hexane and ethyl acetate as the eluate, and is represented by the following structural formula (3). 8.0 g (yield of about 39%) of a colorless oily substance of the active energy ray-polymerizable compound 3 was obtained.
[Active energy ray-polymerizable compound 3]

The identification data of the active energy ray-polymerizable compound 3 is as follows. In addition, spectrum analysis is required.
^{1 1} H-NMR (CDCl ₃ ): δ1.23 (s, 3H), 1.24 (s, 3H), 1.31 (d, 3H), 1.69 (dd, 1H), 1.94 (dd) , 1H), 2.05 (bs, 1H), 5.21-5.28 (b, 1H), 5.83 (dd, 1H), 6.07-6.14 (m, 1H), 6. 40 (dd, 1H)
IR (NaCl): 3444, 2975, 2936, 1721, 1638, 1619, 1461, 1407, 1378, 1299, 1204, 1128, 1089, 1049, 984, 946, 897, 812, 767, 675 cm ^-1

<Example 4A>
-Example of synthesis of active energy ray-polymerizable compound 4-
8.3 g (70 mmol) of 2-methylpentane-2,4-diol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 100 mL of dehydrated dichloromethane, the inside of the flask was replaced with argon gas, and then 8.5 g (84 mmol) of triethylamine was added. added. Next, after cooling to about −10 ° C., 8.8 g (84 mmol) of methacrylic acid chloride was slowly added dropwise so that the temperature inside the system became −10 ° C. to −5 ° C., and the mixture was stirred at room temperature for 2 hours. .. Further, after removing the precipitate by filtration, the obtained solution was concentrated under reduced pressure. Ethyl acetate (150 mL) was added to this concentrate and stirred, and the precipitated solid was removed by filtration, and the obtained filtrate was concentrated under reduced pressure to obtain a brown solution. Further, 350 g of Wakogel C300 (manufactured by Wako Pure Chemical Industries, Ltd.) is filled, and the brown oily substance is purified by column chromatography using hexane and ethyl acetate as the eluate, and is represented by the following structural formula (4). 8.1 g (yield of about 62%) of a colorless oily substance of the active energy ray-polymerizable compound 4 was obtained.
[Active energy ray-polymerizable compound 4]

The identification data of the active energy ray-polymerizable compound 4 is as shown below. In addition, spectrum analysis is required.
^{1 1} H-NMR (CDCl ₃ ): δ1.23 (s, 3H), 1.24 (s, 3H), 1.30 (d, 3H), 1.69 (dd, 1H), 1.93 (dd) , 3H), 1.94 (dd, 1H), 2.06 (bs, 1H), 5.18-5.26 (m, 1H), 5.55-5.58 (m, 1H), 6. 08-6.10 (m, 1H)
IR (NaCl): 3424, 2976, 2933, 1715, 1635, 1453, 1402, 1378, 1321, 1300, 1174, 1127, 1089, 1043, 1009, 942, 900, 858, 816, 767, 653 cm ^-1

<Example 5A>
-Example of synthesis of active energy ray-polymerizable compound 5-
6.7 g (50 mmol) of 3-methylpentane-1,3,5-triol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 100 mL of dehydrated dichloromethane, the inside of the flask was replaced with argon gas, and then 12.1 g (120 mmol) of triethylamine. ) Was added. Next, after cooling to about −10 ° C., 10.5 g (100 mmol) of methacrylic acid chloride was slowly added dropwise so that the temperature inside the system became −10 ° C. to −5 ° C., and the mixture was stirred at room temperature for 2 hours. .. Further, after removing the precipitate by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution. It was then dried over sodium sulfate and then concentrated under reduced pressure to give a brown oil. Further, 350 g of Wakogel C300 (manufactured by Wako Pure Chemical Industries, Ltd.) is filled, and the brown oily substance is purified by column chromatography using hexane and ethyl acetate as the eluate, and is represented by the following structural formula (5). 8.9 g (yield of about 66%) of a pale yellow oily substance of the active energy ray-polymerizable compound 5 was obtained.
[Active energy ray-polymerizable compound 5]

The identification data of the active energy ray-polymerizable compound 5 is as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.30 (s, 3H), 1.91-1.95 (s + t, 6H + 4H), 2.15 (br, 1H), 4.34 (t, 4H), 5 .55-5.59 (m, 2H), 6.07-6.10 (m, 2H)
IR (NaCl): 3504,2972,1717,1637,1453,1376,1235,1298,1163,1013,943,815cm ^-1

<Example 6A>
-Synthesis example of active energy ray-polymerizable compound 6-
3-Methylpentane-1,3,5-triol (manufactured by Tokyo Chemical Industry Co., Ltd.) 13.4 g (100 mmol) was added to 100 mL of dehydrated dichloromethane, the inside of the flask was replaced with argon gas, and then 24.3 g (240 mmol) of triethylamine was added. ) Was added. Next, after cooling to about −10 ° C., 21.7 g (240 mmol) of acrylic acid chloride was slowly added dropwise so that the temperature inside the system became −10 ° C. to −5 ° C., and the mixture was stirred at room temperature for 2 hours. .. Further, after removing the precipitate by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution. It was then dried over sodium sulfate and then concentrated under reduced pressure to give a brown oil. Further, 350 g of Wakogel C300 (manufactured by Wako Pure Chemical Industries, Ltd.) was filled, and the brown oil was purified by column chromatography using hexane and ethyl acetate as the eluate, and represented by the following structural formula (6). 4.1 g (yield of about 17%) of a colorless oily substance of the active energy ray-polymerizable compound 6 was obtained.
[Active energy ray-polymerizable compound 6]

The identification data of the active energy ray-polymerizable compound 6 is as follows.
^{1 1} H-NMR (CDCl ₃ ): δ1.30 (s, 3H), 1.88-1.98 (m, 5H), 4.36 (t, 4H), 5.84 (dd, 2H), 6 .08-6.15 (m, 2H), 6.40 (dd, 2H)
IR (NaCl): 3491,297,172, 1636, 1619, 1463, 1410, 1298, 1277, 1199, 1057, 984,812 cm ^-1

<Comparative Example 1A>
A commercially available compound of 1,6-hexanediol dimethacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following structural formula (7) was used as the compound of Comparative Example 1A.

<Comparative Example 2A>
A commercially available compound of 1,3-butanediol dimethacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following structural formula (8) was used as the compound of Comparative Example 2A.

<Comparative Example 3A>
A commercially available neopentyl glycol dimethacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following structural formula (9) was used as the compound of Comparative Example 3A.

<Comparative Example 4A>
A commercially available glycerol dimethacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following structural formula (10) was used as the compound of Comparative Example 4A.

<Comparative Example 5A>
A commercially available hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following structural formula (11) was used as the compound of Comparative Example 5A.

<Comparative Example 6A>
A commercially available hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following structural formula (12) was used as the compound of Comparative Example 6A.

The viscosity and lack of odor of each of the compounds of Examples 1A to 6A and Comparative Examples 1A to 6A were evaluated as follows. The results are shown in Table 1 below.

<Measurement of viscosity>
The viscosities of the compounds of Examples 1A to 6A and Comparative Examples 1A to 6A were measured by using a cone plate type rotational viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd. using a cone rotor (1 ° 34'x R24). The measurement was carried out at a rotation speed of 50 rpm and a constant temperature circulating water temperature of 25 ° C. VISCOMATE VM-150III was used to adjust the temperature of the circulating water.

<No odor>
Regarding the odors of the compounds of Examples 1A to 5A and Comparative Examples 1A to 6A, the "no odor" was evaluated by the following procedures (1) to (3). The evaluation criteria are as follows.
(1) About 100 mg (0.1 g) of each compound was weighed into a 50 cc sample bottle (glass bottle) and covered.
(2) It was left for about 30 minutes under room temperature conditions.
(3) I brought my nose close to the sample bottle (glass bottle) and smelled the odor when the lid was opened.
-Evaluation criteria-
◯: No odor or discomfort even if it is felt Δ: Discomfort is caused by a peculiar odor ×: Strong discomfort is caused by a peculiar odor

From the results in Table 1 above, it can be seen that the active energy ray-polymerizable compounds of Examples 1A to 6A have less odor.

<Example 1B>
-Example of producing an active energy ray-curable composition-
950 mg of the active energy ray-polymerizable compound of Example 1A and a polymerization initiator (trade name: IRGACURE 907, component name: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one , BASF Japan Co., Ltd.) 50 mg was mixed using a magnetic stirrer to prepare an active energy ray-curable composition 1 of Example 1B.

<Example 2B to Example 6B and Comparative Example 1B to Comparative Example 6B>
In Example 1B, the active energy ray sclerotherapy of Examples 2B to 6B and Comparative Examples 1B to 6B was carried out in the same manner as in Example 1B except that the compounds were changed to the active energy ray-polymerizable compounds shown in Table 2 below. Mold compositions 2-12 were made.

The active energy ray-curable and active energy ray-curable compositions of Examples 1B to 6B and Comparative Examples 1B to 6B were evaluated as follows. The results are shown in Table 2 below.

<Active energy ray polymerizable>
The active energy ray polymerizable composition of each active energy ray-curable composition was evaluated using a differential scanning calorimeter (trade name: DSC-7020, manufactured by Seiko Instruments Co., Ltd.) and an ultraviolet irradiation device (PDC-7). ..
Specifically, the calorific value when the active energy ray-polymerizable compound was irradiated with ultraviolet rays having a wavelength of 365 nm at 200 mW / cm ² for a sufficient time to complete the polymerization was measured twice for one sample. .. The calorific value obtained in the first measurement includes not only the calorific value associated with the polymerization of the active energy ray-polymerizable compound but also the calorific value associated with ultraviolet irradiation. Therefore, the sample whose polymerization was completed in the first measurement was irradiated with ultraviolet rays again under the same conditions, and the calorific value other than the calorific value associated with the polymerization of the active energy ray-polymerizable compound was measured. Then, the calorific value associated with the polymerization of the active energy ray-polymerizable compound was calculated from the difference between the calorific value of the first time and the calorific value of the second time. At this time, the time from the start of ultraviolet irradiation to the arrival at the maximum calorific value was defined as T ₁ [s], which was used as an index for comparing the speed of active energy ray polymerization.

<Active energy ray curable>
Each active energy ray curing is performed using a viscoelasticity measuring device (trade name: MCR302, manufactured by Antonio-Parr), an optional UV curing measuring cell, and an LED light source (trade name: LIGHTNINGCURE LC-L1, manufactured by Hamamatsu Photonics Co., Ltd.). The active energy ray curability of the mold composition was measured.
Specifically, a sample (thickness 10 μm) is sandwiched in a gap of 10 μm using a cone plate having a diameter of 20 mm, and then ultraviolet rays having a wavelength of 365 nm are irradiated at 50 mW / cm ² , and the viscoelasticity changes until the elastic modulus is saturated. Was measured. The maximum elastic modulus was obtained from the measurement results and used as an index of the curing level.
Normally, if the elastic modulus is 1 × 10 ⁴ Pa, it can be said that it is at a sufficiently cured level, but most of the active energy ray-curable compositions of Examples and Comparative Examples are 1 × 10 ⁵ Pa. It was. This is because the conditions of the active energy ray-curable measurement, because the elastic modulus will almost saturated at 1 × 10 5 ^Pa, can not be measured for more resilient modulus. This indicates that any sample saturated at 1 × 10 ⁵ Pa can form a hard state by irradiating with sufficient active energy rays (giving a large amount of active energy ray energy), but for a short time. by light irradiation as a sample of the elastic modulus reaches a saturation of 1 × 10 5 ^Pa, it can be cured at low energy, so that the excellent active energy ray-curable.
Further, the energy of the ultraviolet rays irradiated until the elastic modulus is saturated, that is, the curing energy, is calculated from the product of the intensity of the ultraviolet rays (50 mW / cm ² ) and the time [s] of the irradiation of the ultraviolet rays.

From the results in Table 2, the active energy ray-curable compositions of Examples 1B to 6B using the active energy ray-polymerizable compounds of Examples 1A to 6A are excellent in active energy ray-polymerizable property and active energy ray-curable property. You can see that. Specifically, Examples 5B to 6B having a plurality (two) of (meth) acrylic groups in the molecule have T ₁ which is an index of active energy ray polymerization and curability as compared with Comparative Examples 1B to 4B. The curing energy, which is an index of, is both small. It is considered that this is due to the tertiary hydroxyl group in the active energy ray-polymerizable compounds of Examples 5A and 6A.
Further, it can be seen that Examples 1B to 4B having only one (meth) acrylic group in the molecule are also excellent in active energy ray polymerization and active energy ray curability as compared with Comparative Examples 5B to 6B. Specifically, when the acrylate-based Examples 1B to 3B and 6B are compared with Comparative Example 5B, Examples 1B to 3B and 6B are more excellent in active energy ray polymerization. I understand. Further, regarding the active energy ray curability, Examples 1B to 2B have small curing energies and are excellent, and Example 3B is not so inferior to Comparative Example 5B. Further, from the comparison between Examples 1B to 2B and Example 3B, when the hydrocarbon structure adjacent to the (meth) acrylic acid ester is a methylene structure (−CH ₂₋ ), the activation energy ray curability is improved. It turns out to be excellent.
On the other hand, when the methacrylate-based Example 4B and Comparative Example 6B are compared, it can be seen that Example 4B is superior in both active energy ray polymerization property and active energy ray curability. From this, it can be seen that the active energy ray-polymerizable compound having a tertiary hydroxyl group in the molecule is superior to the active energy ray-polymerizable compound having a primary hydroxyl group.

<Example 1C>
-Example of manufacturing active energy ray-curable ink-
100 parts of the active energy ray-polymerizable compound 1 obtained in Example 1A, 10 parts of a polymerization initiator (trade name: IRGACURE 907, manufactured by BASF Japan Ltd.) and carbon black (trade name: MICROLITH Black CK, BASF Japan Ltd.) 3 parts (manufactured by the company) were mixed to obtain the ink of Example 1C.

<Examples 2C to 6C>
Examples 2C to 2C to the same as in Example 1C, except that the active energy ray-polymerizable compound 1 obtained in Example 1A was changed to the active energy ray-polymerizable compounds 2 to 6 obtained in Examples 2C to 6C. A 6C active energy ray-curable ink was obtained.

<Examples 1D to 6D>
Examples 1C to 6C except that carbon black (trade name: MICROLITH Black C-K, manufactured by BASF Japan Ltd.) was changed to blue pigment (trade name: MICROLLITH Blue 4G-K, manufactured by BASF Japan Ltd.). In the same manner, active energy ray-curable inks of Examples 1D to 6D were obtained.

-Ink curability evaluation 1-
The active energy ray-curable inks of Examples 1C to 6C and Examples 1D to 6D were inkjet-discharged onto a slide glass using an inkjet recording device (manufactured by Ricoh Co., Ltd., head: GEN4 manufactured by Ricoh Printing System Co., Ltd.). After that, using a UV irradiator (trade name: LH6, manufactured by Fusion Systems Japan Co., Ltd.), ultraviolet rays having a wavelength of 365 nm were irradiated at 200 mW / cm ² and cured.

As a result, each active energy ray-curable ink could be ejected by inkjet without any problem, and each ink image was sufficiently cured.
Further, each active energy ray-curable ink substantially corresponds to the one using each active energy ray-curable composition of Examples 1B to 6B, but in the case of each active energy ray-curable composition just in case. When the active energy ray-curable and the active energy ray-curable were measured in the same manner as in the above, it was confirmed that both were excellent as in the active energy ray-curable compositions of Examples 1B to 6B.

− Evaluation of curability of active energy ray-curable ink 2-
Immerse the tip of the dip pen in the inks of Examples 1C to 6C and 1D to 6D, write characters on PET film and plain paper, and then use a UV irradiator (trade name: LH6, manufactured by Fusion System Japan Co., Ltd.). ) Was irradiated with ultraviolet rays having a wavelength of 365 nm at 200 mW / cm ² , and the mixture was cured. As a result, each active energy ray-curable ink image was sufficiently cured.

Examples of aspects of the present invention are as follows.
<1> An active energy ray-curable composition comprising a (meth) acrylic acid ester compound represented by the following general formula (1) having a tertiary hydroxyl group in the molecule.
(However, in the general formula (1), OH represents a tertiary hydroxyl group, m and n represent integers of 1 or more and 2 or less, R ¹ represents either a hydrogen atom or a methyl group, and X is carbon. It represents either a group consisting of an aliphatic hydrocarbon having a number of 4 or more and 10 or less and a group consisting of an aliphatic cyclic hydrocarbon having 4 or more and 10 or less carbon atoms.
<2> The active energy ray-curable composition according to <1>, wherein the (meth) acrylic acid ester compound represented by the general formula (1) is a compound represented by the following general formula (2). is there.
(However, in the general formula (2), OH represents a tertiary hydroxyl group, R ¹ represents either a hydrogen atom or a methyl group, and X ¹ is a substituted or unsubstituted carbon number of 4 or more and 10 or less. Represents a branched alkylene group.)
<3> The active energy ray-curable composition according to <2>, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).
(However, in the general formula (3), OH represents a tertiary hydroxyl group, R ¹ represents either a hydrogen atom or a methyl group, and Y is a substituted or unsubstituted branch having 3 or more and 9 or less carbon atoms. Represents an alkylene group.)
<4> In the above <3>, the compound represented by the general formula (3) is at least one of the compound represented by the following general formula (4) and the compound represented by the following general formula (5). The active energy ray-curable composition according to the above.
(However, in the general formula (4), R ¹ represents either a hydrogen atom or a methyl group.)
(However, in the general formula (5), R ¹ represents either a hydrogen atom or a methyl group.)
<5> The active energy ray-curable composition according to any one of <2> to <4>, wherein R ¹ in the general formula (2) is a hydrogen atom.
<6> The active energy ray-curable composition according to <1>, wherein the (meth) acrylic acid ester compound represented by the general formula (1) is a compound represented by the following general formula (6). is there.
(However, in the general formula (6), Y ¹ and Y ² each independently represent a substituted or unsubstituted alkylene group having 1 or more and 6 or less carbon atoms, and Z represents an alkyl group having 1 or more and 3 or less carbon atoms. Representing, R ¹ and R ² independently represent either a hydrogen atom or a methyl group.)
<7> The active energy ray-curable composition according to <6>, wherein the compound represented by the general formula (6) is a compound represented by the following general formula (7).
(However, in the general formula (7), R ¹ and R ² independently represent either a hydrogen atom or a methyl group, respectively.)
<8> The active energy ray-curable composition according to <1>, wherein n in the general formula (1) is 1.
<9> The active energy ray-curable composition according to any one of <1> to <8>, which further contains a polymerization initiator.
<10> The activity according to any one of <1> to <9>, wherein the content of the (meth) acrylic acid ester compound represented by the general formula (1) is 20% by mass or more and 98% by mass or less. It is an energy ray-curable composition.
<11> An active energy ray-curable ink comprising the active energy ray-curable composition according to any one of <1> to <10>.
<12> The active energy ray-curable ink according to <11>, which is used for an inkjet.
<13> The active energy ray-curable ink according to any one of <11> to <12>, which further contains a coloring material.
<14> At least one of the active energy ray-curable composition according to any one of <1> to <10> and the active energy ray-curable ink according to any one of <11> to <13>. It is a composition storage container characterized by containing the above in a container.
<15> At least one of the active energy ray-curable composition according to any one of <1> to <10> and the active energy ray-curable ink according to any one of <11> to <13>. It is a two-dimensional or three-dimensional image forming apparatus characterized by having an accommodating portion for accommodating the above in a container and an irradiation means for irradiating active energy rays.
<16> At least one of the active energy ray-curable composition according to any one of <1> to <10> and the active energy ray-curable ink according to any one of <11> to <13>. This is a two-dimensional or three-dimensional image forming method, which comprises an irradiation step of irradiating an active energy ray.
<17> At least one of the active energy ray-curable composition according to any one of <1> to <10> and the active energy ray-curable ink according to any one of <11> to <13>. It is a cured product characterized in that it is cured by irradiating it with active energy rays.
<18> A decorative body characterized in that a surface decoration made of the cured product according to <17> is applied on a base material.
<19> An active energy ray-polymerizable compound characterized by containing a (meth) acrylic acid ester compound represented by the following general formula (1).
(However, in the general formula (1), OH represents a tertiary hydroxyl group, m and n represent integers of 1 or more and 2 or less, R ¹ represents either a hydrogen atom or a methyl group, and X is carbon. It represents either a group consisting of an aliphatic hydrocarbon having a number of 4 or more and 10 or less and a group consisting of an aliphatic cyclic hydrocarbon having 4 or more and 10 or less carbon atoms.
<20> A photocurable composition characterized by being the active energy ray-polymerizable compound according to <19>.

The active energy ray-curable composition according to any one of <1> to <10>, the active energy ray-curable composition ink according to any one of <11> to <13>, the above <14>. The composition storage container, the two-dimensional or three-dimensional image forming apparatus according to <15>, the two-dimensional or three-dimensional image forming method according to <16>, and the cured product according to <17>. According to the above-mentioned decorative body according to <18>, the active energy ray-polymerizable compound according to the above <19>, and the photocurable composition according to the above <20>, the above-mentioned problems in the prior art are solved. , The object of the present invention can be achieved.

Japanese Unexamined Patent Publication No. 2012-193292 Japanese Unexamined Patent Publication No. 2011-195724 Japanese Unexamined Patent Publication No. 2009-67726

4: Active energy ray 6: Active energy ray curable composition, active energy ray curable ink 22: Recording medium (base material)
39: Image forming apparatus

Claims (9)

An active energy ray-curable composition comprising a (meth) acrylic acid ester compound represented by the following general formula (6) having a tertiary hydroxyl group in the molecule.
(However, in the general formula (6), Y ¹ and Y ² each independently represent a substituted or unsubstituted alkylene group having 1 or more and 6 or less carbon atoms, and Z represents an alkyl group having 1 or more and 3 or less carbon atoms. Representing , R ¹ and R ² independently represent either a hydrogen atom or a methyl group .) The active energy ray-curable composition according to claim 1 , wherein the compound represented by the general formula (6) is a compound represented by the following general formula (7).
(However, in the general formula (7), R ¹ and R ² independently represent either a hydrogen atom or a methyl group, respectively.) An active energy ray-curable ink comprising the active energy ray-curable composition according to any one of claims 1 to 2 . The active energy ray-curable ink according to claim 3 , which is for an inkjet. At least one of the active energy ray-curable composition according to any one of claims 1 to 2 and the active energy ray-curable ink according to any one of claims 3 to 4 is contained in a container. A composition storage container characterized by. An accommodating portion for accommodating at least one of the active energy ray-curable composition according to any one of claims 1 to 2 and the active energy ray-curable ink according to any one of claims 3 to 4 in a container. , A two-dimensional or three-dimensional image forming apparatus comprising an irradiation means for irradiating an active energy ray. An irradiation step of irradiating at least one of the active energy ray-curable composition according to any one of claims 1 to 2 and the active energy ray-curable ink according to any one of claims 3 to 4 with active energy rays. A method for forming a two-dimensional or three-dimensional image, which comprises. Irradiate at least one of the active energy ray-curable composition according to any one of claims 1 to 2 and the active energy ray-curable ink according to any one of claims 3 to 4 with active energy rays to cure. A cured product characterized by being made to grow. A decorative body characterized in that a surface decoration made of the cured product according to claim 8 is applied on a base material.