JP7283294B2 - Active energy ray-curable composition, active energy ray-curable ink, active energy ray-curable inkjet ink, container, two-dimensional or three-dimensional image forming apparatus, two-dimensional or three-dimensional image forming method, and cured product manufacturing method - Google Patents

Description

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

An inkjet recording method is known as a method for forming an image on a recording medium such as paper. This ink jet recording method has high ink consumption efficiency and excellent resource saving properties, and can keep the ink cost per unit recording low. Active energy ray-curable ink, which is cured by being irradiated with an active energy ray, is used as the ink used in this inkjet recording method.

Patent Document 1 discloses a tooth adhesive in which a phenyl (meth)acrylate derivative having a carboxyl group and a hydroxyl group as substituents on an aromatic ring is used in combination with another (meth)acrylate compound.

Patent Documents 2 and 3 disclose a compound having an organic group having 1 to 10 carbon atoms (including an aromatic ring) as a mother nucleus and a (meth)acrylic acid ester group and a vinyl group in one molecule, and this compound. A photo-nanoimprinting composition used is disclosed.

However, it is difficult to provide an active energy ray-curable composition with little odor and excellent photopolymerizability and photocurability.

（前記一般式（１）中、Ｒ１は水素原子を表し、Ｒ２は炭素数１のアルキル基を表し、Ｘは炭素数１～８のアルキル基を表し、Ｙは炭素数１のアルコキシ基を表し、ｍは０または１の整数を表し、ｎは１を表す。）
The invention according to claim 1 is an active energy ray-curable composition containing a (meth)acrylamide compound represented by the following general formula (1).

(In general formula (1) above, R1 represents a hydrogen atom , R2 represents an alkyl group having 1 carbon number , X represents an alkyl group having 1 to 8 carbon atoms, and Y represents an alkoxy group having 1 carbon number. ) , m represents an integer of 0 or 1 , and n represents 1. )

ADVANTAGE OF THE INVENTION The active-energy-ray-curable composition of this invention has little odor, and is excellent in photopolymerizability and photocurability.

1 is a schematic diagram showing an example of an image forming apparatus; FIG. FIG. 3 is a schematic diagram showing an example of another image forming apparatus; FIG. 11 is a schematic diagram showing an example of still another image forming apparatus;

An example of an embodiment of the present invention will be described below.
<<Active energy ray-curable composition>>
The active energy ray-curable composition of the present embodiment contains an active energy ray-polymerizable compound and, if necessary, a polymerization initiator, an organic solvent, a coloring material, other components, and the like. The active energy ray-polymerizable compound includes a (meth)acrylamide compound represented by the following general formula (1), and if necessary, an active energy ray polymerizable compound other than the (meth)acrylamide compound represented by the following general formula (1). Contains energy ray polymerizable compounds.

<(Meth)acrylamide compound represented by general formula (1)>
The (meth)acrylamide compound contained in the active energy ray-curable composition is represented by the following general formula (1). In addition, the (meth)acrylamide compound represents at least one selected from an acrylamide compound and a methacrylamide compound. Moreover, the (meth)acrylamide compound represented by the general formula (1) may be used alone or in combination of two or more.

R ¹ in general formula (1) represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

R ² in general formula (1) represents an alkyl group or alkenyloxy group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms.

Examples of alkyl groups having 1 to 5 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group and neopentyl. and the like.

Examples of alkenyloxy groups having 1 to 5 carbon atoms include -OCH ₂ CH=CH ₂ , -OCH ₂ CH=CHCH ₃ and -OCH ₂ CH=CHC ₂ H ₅ .

X in general formula (1) represents an alkyl group having 1 to 12 carbon atoms.

Examples of alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group and neopentyl. group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like.

Y in general formula (1) represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or an alkoxyalkyl group.

Examples of alkyl groups having 1 to 5 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group and neopentyl. and the like.

Examples of alkoxy groups having 1 to 5 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy, phenoxy, allyloxy, cyclohexyloxy and benzyloxy groups.

Examples of the alkoxyalkyl group having 1 to 5 carbon atoms include methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group, ethoxypropyl group, propoxymethyl group, propoxyethyl group and butoxymethyl group.

m in the general formula (1) represents an integer of 0 to 3, preferably 0.

n in the general formula (1) represents 1 or 2, preferably 1.

The (meth)acrylamide compound represented by the general formula (1) has a phenyl(meth)acrylamide as a mother nucleus and an ester structure as a substituent on the aromatic ring. In general, low-molecular-weight (meth)acrylate compounds are volatile, so they have a strong odor peculiar to monomers, and when handling a curable composition containing these compounds, it is unpleasant. become. This is the same for compounds having an aromatic ring, and monofunctional monomer compounds having one benzene ring such as phenyl acrylate, benzyl acrylate, and phenoxyethyl acrylate themselves emit a strong unpleasant odor. However, there is an odor problem with curable compositions containing these compounds.

By introducing a highly polar functional group or increasing the molecular weight of such low-molecular-weight (meth)acrylate compounds, it is possible to suppress the volatility of (meth)acrylate compounds and reduce their odor. is. However, in that case, the viscosity is increased, and there is a problem that restrictions on the use of the curable composition (for example, restrictions on use as an inkjet ink) become large.
Therefore, the (meth)acrylamide compound represented by the general formula (1) is a monofunctional (meth)acrylamide compound having an aromatic ring having an ester structure as a mother nucleus, and between the aromatic ring and the (meth)acrylamide structure The base nucleus is a compact structure that does not have a linked structure such as alkylene oxide. Therefore, by having an ester structure having an appropriate polarity on the aromatic ring, it is excellent in curability by polymerization, and odor can be suppressed by reducing volatility. Furthermore, the scaffold structure is compact and has a large degree of freedom, and the ester structure introduced onto the aromatic ring is not a strong polar group. In this case, the terminal structure of the ester is an alkyl group, and it is considered that the viscosity is less likely to increase than a structure containing a carbon-carbon double bond. As a result, the (meth)acrylamide compound represented by general formula (1) can be suitably used as an active energy ray-curable composition.

-(Meth)acrylamide compound represented by general formula (2)-
The (meth)acrylamide compound represented by the general formula (1) is not particularly limited and can be appropriately selected depending on the purpose, but the compound represented by the following general formula (2) is preferable.

R ¹ in general formula (2) is the same as R ¹ in general formula (1) and represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

R ² in general formula (2) is the same as R ² in general formula (1), represents an alkyl group or alkenyloxy group having 1 to 5 carbon atoms, and is preferably an alkyl group having 1 to 5 carbon atoms. preferable.
As the alkyl group and alkenyloxy group having 1 to 5 carbon atoms, the same groups as those for R ² in general formula (1) can be used.

X ¹ in general formula (2) represents an alkyl group having 1 to 4 carbon atoms.

Examples of alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and tert-butyl group.

Y in general formula (2) is the same as Y in general formula (1) and represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or an alkoxyalkyl group.
As the alkyl group, alkoxy group, and alkoxyalkyl group having 1 to 5 carbon atoms, those similar to Y in the general formula (1) can be used.

m in general formula (2) is the same as m in general formula (1) and represents an integer of 0 to 3, preferably 0.

-(Meth)acrylamide compounds represented by general formulas (3) to (5)-
The compound represented by the general formula (2) is not particularly limited and can be appropriately selected depending on the purpose. and at least one selected from compounds represented by the general formula (5).

R ¹ in general formula (3) is the same as R ¹ in general formula (2) and represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

R ² in general formula (3) represents an alkyl group having 1 to 5 carbon atoms.
Examples of alkyl groups having 1 to 5 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group and neopentyl. and the like.

X ¹ in general formula (3) is the same as X ¹ in general formula (2) and represents an alkyl group having 1 to 4 carbon atoms.
As the alkyl group having 1 to 4 carbon atoms, the same groups as X ¹ in formula (2) can be used.

R ¹ in general formula (4) is the same as R ¹ in general formula (2) and represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

R ² in general formula (4) represents an alkyl group having 1 to 5 carbon atoms.
Examples of alkyl groups having 1 to 5 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group and neopentyl. and the like.

X ¹ in general formula (4) is the same as X ¹ in general formula (2) and represents an alkyl group having 1 to 4 carbon atoms.
As the alkyl group having 1 to 4 carbon atoms, the same groups as X ¹ in formula (2) can be used.

R ¹ in general formula (5) is the same as R ¹ in general formula (2) and represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

R ² in general formula (5) represents an alkyl group having 1 to 5 carbon atoms.
Examples of alkyl groups having 1 to 5 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group and neopentyl. and the like.

X ¹ in general formula (5) is the same as X ¹ in general formula (2) and represents an alkyl group having 1 to 4 carbon atoms.
As the alkyl group having 1 to 4 carbon atoms, the same groups as X ¹ in formula (2) can be used.

-Specific examples of (meth)acrylamide compounds represented by general formula (1)-
Next, as specific examples of the (meth)acrylamide compound represented by the general formula (1), exemplary compound groups a to g are shown, but are not limited to these. R ¹ and R ² in these examples are the same as R ¹ and R ² in the general formula (1).

Exemplified compound a group includes, for example, the compounds shown below. These may be used individually by 1 type, and may use 2 or more types together.

(Exemplary compound a-1)

(Illustrative compound a-2)

(Exemplary compound a-3)

(Illustrative compound a-4)

(Exemplary compound a-5)

(Exemplary compound a-6)

(Illustrative compound a-7)

(Exemplary compound a-8)

(Illustrative compound a-9)

Exemplified compound group b includes, for example, compounds shown below. These may be used individually by 1 type, and may use 2 or more types together.

(Exemplary compound b-1)

(Exemplary compound b-2)

(Exemplary compound b-3)

(Exemplary compound b-4)

(Exemplary compound b-5)

(Illustrative compound b-6)

(Exemplary compound b-7)

(Exemplary compound b-8)

(Exemplary compound b-9)

Exemplary compound group c includes, for example, compounds shown below. These may be used individually by 1 type, and may use 2 or more types together.

(Exemplary compound c-1)

(Exemplary compound c-2)

(Exemplary compound c-3)

(Exemplary compound c-4)

(Exemplary compound c-5)

(Exemplary compound c-6)

(Exemplary compound c-7)

(Exemplary compound c-8)

(Exemplary compound c-9)

Exemplary compound group d includes, for example, compounds shown below. These may be used individually by 1 type, and may use 2 or more types together.

(exemplary compound d-1)

(Illustrative compound d-2)

(Illustrative compound d-3)

(Exemplary compound d-4)

(Illustrative compound d-5)

(Illustrative compound d-6)

Exemplary compound group e includes, for example, compounds shown below. These may be used individually by 1 type, and may use 2 or more types together.

(Exemplary compound e-1)

(Illustrative compound e-2)

(Illustrative compound e-3)

(Illustrative compound e-4)

(Illustrative compound e-5)

(Illustrative compound e-6)

Exemplary compound group f includes, for example, compounds shown below. These may be used individually by 1 type, and may use 2 or more types together.

(Illustrative compound f-1)

(Illustrative compound f-2)

(Illustrative compound f-3)

(Illustrative compound f-4)

(Illustrative compound f-5)

(Illustrative compound f-6)

Exemplary compound group g includes, for example, compounds shown below. These may be used individually by 1 type, and may use 2 or more types together.

(Illustrative compound g-1)

(Illustrative compound g-2)

(Illustrative compound g-3)

(Illustrative compound g-4)

(Illustrative compound g-5)

(Illustrative compound g-6)

(Illustrative compound g-7)

(Illustrative compound g-8)

(Illustrative compound g-9)

(Illustrative compound g-10)

Among Exemplified Compounds a to g groups, Exemplified Compound a-2, Exemplified Compound b-1, Exemplified Compound c-1, Exemplified Compound d-4, and Exemplified Compound g-7 are preferable, and the following structural formulas (1) to ( The compound represented by 5) is more preferable, and the compound represented by the following structural formula (1), the compound represented by the following structural formula (3), and the compound represented by the following structural formula (4) are particularly preferable.

As the (meth)acrylamide compound represented by the general formula (1), a mixture of two or more different compounds can be used, and the different compounds in this case also include structural isomers. Also, the mixing ratio of these is not particularly limited.

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

-others-
The compound represented by the following general formula (A), which is not included in the (meth)acrylamide compound represented by the general formula (1), has a highly polar carboxyl group and a hydroxyl group on the benzene ring. Therefore, it is considered that the compound has a very high viscosity and may be solid at room temperature (25° C.). In addition, it is a compound that has very high polarity and poor compatibility with polymerization initiators and other monomer compounds, making it difficult to use as a curable composition.

ただし、一般式（Ａ）中、Ｒは水素原子又はメチル基を示す。

However, in general formula (A), R represents a hydrogen atom or a methyl group.

Further, the compound represented by the following general formula (B) and the compound represented by the following structural formula (C), which are not included in the (meth)acrylamide compound represented by the general formula (1), have a terminal ester structure of carbon -Since it has a substituent having a carbon double bond, it is considered that the compound has a higher viscosity than the compound of the present embodiment having the same scaffold structure. For this reason, it may be difficult to use it as a curable composition.

ただし、一般式（Ｂ）中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２は炭素－炭素２重結合を有する置換基を表し、Ｘは炭素数１～１０の有機基を表し、ｍ及びｎはそれぞれ独立に、１～３の整数を表す。

However, in general formula (B), R ¹ represents a hydrogen atom or a methyl group, R ² represents a substituent having a carbon-carbon double bond, X represents an organic group having 1 to 10 carbon atoms, m and n each independently represents an integer of 1 to 3.

<Other Active Energy Ray Polymerizable Compounds>
The active energy ray-curable composition may contain an active energy ray-polymerizable compound other than the (meth)acrylamide compound represented by general formula (1).

The active energy ray-polymerizable compound other than the (meth)acrylamide compound represented by the general formula (1) is not particularly limited and can be appropriately selected depending on the purpose. , active energy ray cationic polymerizable compounds, active energy ray anionic polymerizable compounds, and the like. These may be used individually by 1 type, and may use 2 or more types together.

The active energy ray radically polymerizable compound is not particularly limited as long as it is a compound having one or more ethylenically unsaturated groups capable of undergoing active energy ray radical polymerization, and can be appropriately selected according to the purpose. Examples include compounds including monomers, oligomers, polymers, and the like. Among these, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid, salts thereof, or compounds derived from these, anhydrides having an ethylenically unsaturated group, Acrylonitrile, styrene, unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated urethanes and the like are preferred.

Active energy ray radically polymerizable compounds include, for example, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis(4-acryloxypolyethoxyphenyl)propane, neo Pentyl 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 tetraacrylate, Acrylic acid derivatives such as trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, 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, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis(4-methacryloxy polyethoxy phenyl)propane and other methacrylic acid derivatives, N-methylolacrylamide, diacetoneacrylamide, 2-hydroxyethylacrylamide, acryloylmorpholine and other acrylamide derivatives, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate and other derivatives of allyl compounds, Ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol Monotrivinyl ether compounds such as divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, trimethylolpropane trivinyl ether, divinyl ether compounds, or trivinyl ether compounds, 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, isopropenyl ether-o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, monovinyl ether compounds such as octadecyl vinyl ether, 2- ethylhexyl diglycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl acrylate, neopentyl glycol hydroxypivalate diacrylate, 2-acryloyloxyethyl phthalate, methoxypolyethylene glycol acrylate, tetramethylolmethane triacrylate, 2 -acryloyloxyethyl-2-hydroxyethyl phthalate, dimethyloltricyclodecane diacrylate, ethoxylated phenyl acrylate, 2-acryloyloxyethyl succinic acid, nonylphenol ethylene oxide adduct acrylate, modified glycerin triacrylate, bisphenol A diglycidyl ether acrylic acid adducts, modified bisphenol A diacrylate, phenoxypolyethylene glycol acrylate, 2-acryloyloxyethylhexahydrophthalic acid, propylene oxide adduct diacrylate of bisphenol A, ethylene oxide adduct diacrylate of bisphenol A, dipentaerythritol hexaacrylate, tolylene diisocyanate urethane prepolymer, lactone-modified flexible acrylate, butoxyethyl acrylate, propylene glycol diglycidyl ether acrylic acid adduct, hexamethylene diisocyanate urethane prepolymer, methoxydipropylene glycol acrylate, ditrimethylolpropane tetraacrylate, Examples include stearyl acrylate, isoamyl acrylate, isomyristyl acrylate, isostearyl acrylate, and lactone-modified acrylate. These may be used individually by 1 type, and may use 2 or more types together.

Examples of active energy ray cationic polymerizable compounds include epoxy compounds, vinyl ether compounds, and oxetane compounds. These may be used individually by 1 type, and may use 2 or more types together.

Examples of active energy ray anionically polymerizable compounds include epoxy compounds, lactone compounds, acrylic compounds, and methacrylic compounds. These may be used individually by 1 type, and may use 2 or more types together.

Among these other active energy ray-polymerizable compounds, acrylic acid derivatives, methacrylic acid derivatives, and the like exemplified as active energy ray radically polymerizable compounds are preferred.

The content of other active energy ray-polymerizable compounds is preferably 0.01 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the (meth)acrylamide compound represented by the general formula (1). 1 part by mass or more and 50 parts by mass or less is more preferable.

<Polymerization initiator>
The active energy ray-curable composition may contain a polymerization initiator. Any polymerization initiator may be used as long as it can generate active species such as radicals and cations by the energy of active energy rays to initiate polymerization of polymerizable compounds (monomers and oligomers). As such polymerization initiators, known radical polymerization initiators, cationic polymerization initiators, base generators and the like can be used singly or in combination of two or more. Among them, radical polymerization initiators are used. is preferred. Also, in order to obtain a sufficient curing speed, the polymerization initiator is preferably contained in an amount of 5 to 20% by mass with respect to the total mass (100% by mass) of the composition.

Examples of radical polymerization initiators include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, Examples include ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds.

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

<Organic solvent>
Although the active energy ray-curable composition may contain an organic solvent, it is preferable not to contain it. A composition that does not contain an organic solvent, especially a volatile organic solvent (VOC (volatile organic compound)-free) increases the safety of the place where the composition is handled and can also 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.

<Color material>
The active energy ray-curable composition may contain a coloring material. As the coloring material, various pigments imparting black, white, magenta, cyan, yellow, green, orange, glossy colors such as gold and silver, etc., depending on the purpose and required properties of the composition in the present embodiment, and Dyes 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 embodiment 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.

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

-Polymerization inhibitor-
The polymerization inhibitor can improve the storage stability (storage stability) of the active energy ray-curable composition, and also prevents head clogging due to thermal polymerization when the curable composition is heated to reduce its viscosity and discharged. can be prevented.

The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone, benzoquinone, p-methoxyphenol, TEMPO, TEMPOL, cupferron complex of aluminum, and the like. These may be used individually by 1 type, or may use 2 or more types together.

The content of the polymerization inhibitor is preferably 200 ppm or more and 20,000 ppm or less.

- Sensitizer -
A sensitizer can be contained in order to promote the decomposition of the photopolymerization initiator by irradiation with active energy rays. The sensitizer absorbs the active energy ray and becomes an electronically excited state, and in that state comes into contact with the polymerization initiator. For example, the polymerization initiator undergoes chemical changes (decomposition, radical , acid or base formation).

The mass ratio of the content (% by mass) of the sensitizer and the content (% by mass) of the photopolymerization initiator is preferably 5×10 ⁻³ or more and 200 or less, more preferably 0.02 or more and 50 or less. .

The sensitizer is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of sensitizing dyes include polynuclear aromatics (e.g., pyrene, perylene, triphenylene), xanthenes (e.g., fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (e.g., thiacarbocyanine). , oxacarbocyanine), merocyanines (e.g., merocyanine, carbomerocyanine), thiazines (e.g., thionine, methylene blue, toluidine blue), acridines (e.g., acridine orange, chloroflavin, acriflavin), anthraquinones (e.g., anthraquinone), squarylium (eg, squarylium), coumarins (eg, 7-diethylamino-4-methylcoumarin), and the like. These may be used individually by 1 type, and may use 2 or more types together.

-Co-sensitizer-
The co-sensitizer, for example, further improves the sensitivity of the sensitizing dye to actinic energy rays, and suppresses inhibition of polymerization of the photopolymerizable compound by oxygen.

The co-sensitizer is not particularly limited and can be appropriately selected depending on the intended purpose. amine compounds, thiols and sulfides such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4(3H)-quinazoline and β-mercaptonaphthalene. These may be used individually by 1 type, and may use 2 or more types together.

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

<Active energy ray>
Examples of active energy rays used for curing the active energy ray-curable composition include ultraviolet rays, electron beams, α rays, β rays, γ rays, X rays, and the like, which are used for the polymerization reaction of the polymerizable components in the composition. It is not particularly limited as long as it can provide the energy necessary to advance the process. 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.

<Preparation of active energy ray-curable composition>
The active energy ray-curable composition can be produced using the various components described above, and the preparation means and conditions are not particularly limited. It is put into a dispersing machine such as 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, etc. can be prepared.

<Viscosity>
The viscosity of the active energy ray-curable composition may be appropriately adjusted according to the application and application means, and is not particularly limited. The viscosity in the range of 20 to 65°C, desirably at 25°C, is preferably 3 to 40 mPa·s, more preferably 5 to 15 mPa·s, particularly preferably 6 to 12 mPa·s. Moreover, it is particularly preferable that the viscosity range is satisfied without including the above 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 setting the temperature of constant-temperature circulating water to 20 to 20. Measurement can be performed by appropriately setting the temperature within 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 is not particularly limited as long as it is a field in which active energy ray-curable materials are generally used, and can be appropriately selected according to the purpose. , adhesives, insulating materials, release agents, coating materials, sealing materials, various resists, various optical materials, and the like.
Furthermore, the active energy ray-curable composition is used as an active energy ray-curable ink, more preferably as an active energy ray-curable inkjet ink, to form two-dimensional characters, images, and design coatings on various substrates. In addition, it can also be used as a three-dimensional modeling material for forming a three-dimensional three-dimensional image (three-dimensional object). This three-dimensional modeling material may be used, for example, as a binder between powder particles used in a powder lamination method in which three-dimensional modeling is performed by repeating curing and lamination of powder layers. It may be used as a three-dimensional configuration material (model material) or a support member (support material) used in such a layered manufacturing method (stereolithography method). In addition, FIG. 2 shows a method of discharging an active energy ray-curable composition to a predetermined area, irradiating an active energy ray and curing the composition, and then sequentially laminating the material to form a three-dimensional model (details will be described later). irradiates a storage pool (accommodating portion) 1 of an active energy ray-curable composition 5 with an active energy ray 4 to form a cured layer 6 having a predetermined shape on a movable stage 3, which are sequentially stacked to perform three-dimensional modeling. is a method of doing
As a three-dimensional modeling apparatus for modeling a three-dimensional object using an active energy ray-curable composition, a known one can be used, and is not particularly limited. containing means (container), supply means for supplying the active energy ray-curable composition from the containing means, applying means for applying the active energy ray-curable composition supplied from the containing means, applied active energy ray Examples thereof include those equipped with an irradiation means for irradiating the curable composition with an active energy ray.
Further, the cured product obtained by curing the active energy ray-curable composition (in other words, the cured product derived from the active energy ray-curable composition) is obtained by processing the cured product formed on the substrate. Also includes molded products. Molded processed products are, for example, those obtained by subjecting cured products or structures formed in the form of sheets or films to molding processes such as heat stretching and punching. It is suitably used for applications that require surface molding after decoration, such as electronic devices, meters of cameras, and operation panel panels. In addition, in this application, the hardened|cured material formed on the base material is called a decorating part.
The base material is not particularly limited and can be appropriately selected depending on the intended purpose. A plastic substrate is preferable from the viewpoint of workability.

<<Active energy ray-curable ink, active energy ray-curable inkjet ink>>
The active energy ray-curable ink is an ink containing the above active energy ray-curable composition, and is used, for example, for forming two-dimensional characters and images, and for forming a design coating film on various substrates. , and for forming a three-dimensional stereoscopic image (three-dimensional object).
The active energy ray-curable inkjet ink is an active energy ray-curable ink that is ejected and used by an inkjet method.

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

<<Image Forming Method, Image Forming Apparatus>>
The image forming method includes applying an active energy ray-curable composition, an active energy ray-curable ink, or an active energy ray-curable inkjet ink (hereinafter referred to as "active energy ray-curable composition, etc."). and an irradiation step of irradiating the applied active energy ray-curable composition or the like with an active energy ray, and if necessary, other steps may be included.
The image forming apparatus includes storage means for storing the active energy ray-curable composition, etc., application means for applying the stored active energy ray-curable composition, etc., and applied active energy ray-curable composition, etc. irradiating means for irradiating the active energy ray to the surface, and if necessary, other means may be provided.
Examples of the application process and application means include a discharge process and a discharge means. The discharge method is not particularly limited, and may be a continuous injection type, an on-demand type, or the like. The on-demand type includes a piezo system, a thermal system, an electrostatic system, and the like.

FIG. 1 shows an example of an image forming apparatus equipped with an inkjet ejection means. Ink is ejected onto the recording medium 22 supplied from the supply roll 21 by the respective color printing units 23a, 23b, 23c, and 23d, which are provided with ink cartridges and ejection heads for active energy ray-curable inks of yellow, magenta, cyan, and black. be done. After that, the light sources 24a, 24b, 24c, and 24d for curing the ink are irradiated with active energy rays to cure the ink, thereby forming a color image. After that, the recording medium 22 is conveyed to the processing unit 25 and the print take-up roll 26 . A heating mechanism may be provided in each of the printing units 23a, 23b, 23c, and 23d so that the ink is liquefied at the ink discharge section. Further, if necessary, a mechanism may be provided for cooling the recording medium to about room temperature by contact or non-contact. Inkjet recording methods include a serial method in which a head is moved to eject ink onto a recording medium that moves intermittently according to the width of an ejection head, and a serial method in which ink is ejected onto a recording medium by moving the recording medium continuously. Any line system in which ink is ejected onto a recording medium from a head held at a fixed position can be applied.
The recording medium 22 is not particularly limited, but includes paper, film, metal, composite materials thereof, and the like, and may be in the form of a sheet. Further, the configuration may be such that only single-sided printing is possible, or that double-sided printing is also possible.
Furthermore, the active energy ray irradiation from the light sources 24a, 24b, and 24c may be weakened or omitted, and after printing a plurality of colors, the active energy ray may be irradiated from the light source 24d. Thereby, energy saving and cost reduction can be achieved.
Recordings recorded with ink include not only those printed on smooth surfaces such as ordinary paper and resin films, but also those printed on uneven surfaces to be printed, and various materials such as metals and ceramics. Also includes those printed on the printing surface consisting of. In addition, by layering two-dimensional images, it is possible to form an image (an image consisting of two-dimensional and three-dimensional images) or a three-dimensional object with a partial three-dimensional effect.

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

<< Cured product >>
The cured product is a structure derived from the active energy ray-curable composition or the like, in other words, a structure formed by curing the active energy ray-curable composition or the like by irradiating it with an active energy ray. .

<<Decoration body>>
The decorating body has a base material and a decorating part made of the cured product formed on the base material. The base material is not particularly limited and can be appropriately selected depending on the intended purpose. and plastic is preferable from the viewpoint of workability.

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

¹ H-NMR spectra in the following examples were measured using ¹ H-NMR (500 MHz) (manufactured by JEOL Ltd., ECX500).

<Synthesis Example of Active Energy Ray Polymerizable Compound>
(Synthesis Example 1a)
16.51 g (100 mmol) of methyl 4-(N-methylamino)benzoate from ABC Labtory Scientific was added in 200 mL of dehydrated dichloromethane and 15 mL of dehydrated tetrahydrofuran, and 17.2 g (170 mmol) of triethylamine was added. Next, after cooling to about -15°C, 12.67 g (140 mmol) of acrylic acid chloride manufactured by Wako Pure Chemical Industries, Ltd. was slowly added dropwise so that the temperature in the system became -8°C to -9°C. , and stirred at room temperature for 4 hours. Further, after the precipitate was removed by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogencarbonate solution and saturated aqueous sodium chloride solution. It was then dried over magnesium sulfate and then concentrated under reduced pressure to give an oil. Further, 340 g of silica gel 60N manufactured by Merck Co., Ltd. was packed, and purified by column chromatography using ethyl acetate as an eluent to obtain a colorless oil of active energy ray polymerizable compound 1 represented by the following structural formula (1). 18.72 g (yield: about 80.3%) was obtained.

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 1.40 (t, 3H), 3.31 (s, 3H), 4.38 (q, 2H), 6.04 (dd, 1H), 6.25-6 .37 (m, 1H), 6.62 (dd, 1H), 7.23 (d, 2H), 8.10 (d, 2H)

(Synthesis Example 2a)
11.85 g (45 mmol) of 2-ethylhexyl 4-(N-methylamino)benzoate from ABC Labtory Scientific was added to 75 mL of dry dichloromethane and 6.83 g (67.5 mmol) of triethylamine was added. Next, after cooling to about −15° C., 4.84 g (54 mmol) of acrylic acid chloride manufactured by Wako Pure Chemical Industries, Ltd. was diluted with 3.5 mL of dehydrated dichloromethane and slowly added dropwise, followed by stirring at room temperature for 3 hours. bottom. Further, after the precipitate was removed by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogencarbonate solution and saturated aqueous sodium chloride solution. Next, after drying with sodium sulfate, it was concentrated under reduced pressure to obtain an oil. Furthermore, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. was packed, purified by column chromatography using ethyl acetate as an eluent, and active energy ray polymerizable represented by the following structural formula (2). 8.99 g (yield: about 63%) of compound 2 as a colorless oil was obtained.

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 0.89-0.96 (m, 6H), 1.30-1.50 (m, 8H), 1.68-1.73 (m, 1H), 3. 30 (s, 3H), 4.24 (d, 2H), 6.04-6.07 (dd, 1H), 6.30-6.36 (m, 1H), 6.62-6.66 ( dd, 1H), 7.22 (d, 2H), 8.09 (d, 2H)

(Synthesis Example 3a)
9.91 g (60 mmol) of methyl 3-(N-methylamino)benzoate from ABC Labtory Scientific was added to 100 mL of dry dichloromethane and 7.89 g (78 mmol) of triethylamine was added. Next, after cooling to about −15° C., 6.52 g (72 mmol) of acrylic acid chloride manufactured by Wako Pure Chemical Industries, Ltd. was diluted with 4.5 mL of dehydrated dichloromethane and slowly added dropwise, followed by stirring at room temperature for 3 hours. bottom. Further, after the precipitate was removed by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogencarbonate solution and saturated aqueous sodium chloride solution. Next, after drying with sodium sulfate, it was concentrated under reduced pressure to obtain an oil. Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. was packed, purified by column chromatography using ethyl acetate as an eluent, and active energy ray polymerizable represented by the following structural formula (3). 10.48 g (yield: about 79%) of compound 3 as a colorless oil was obtained.

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 3.30 (s, 3H), 3.92 (s, 3H), 6.04-6.06 (dd, 1H), 6.31-6.36 (m, 1H), 6.61-6.65 (dd, 1H), 7.33-7.36 (dd, 1H), 7.48 (t, 1H), 7.80-7.82 (m, 1H) , 7.92-7.95 (m, 1H)

(Synthesis Example 4a)
9.91 g (60 mmol) of methyl N-methylanthranilate manufactured by Tokyo Kasei Kogyo Co., Ltd. was added to 95 mL of dehydrated dichloromethane, and 7.89 g (78 mmol) of triethylamine was added. Next, after cooling to about −15° C., 6.52 g (72 mmol) of acrylic acid chloride manufactured by Wako Pure Chemical Industries, Ltd. was diluted with 4.5 ml of dehydrated dichloromethane and slowly added dropwise, followed by stirring at room temperature for 3 hours. bottom. Further, after the precipitate was removed by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogencarbonate solution and saturated aqueous sodium chloride solution. Next, after drying with sodium sulfate, it was concentrated under reduced pressure to obtain an oil. Furthermore, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. was packed, purified by column chromatography using ethyl acetate as an eluent, and active energy ray polymerizable represented by the following structural formula (4). 8.0 g (yield: about 61%) of compound 4 as a colorless oil was obtained.

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 3.30 (s, 3H), 3.84 (s, 3H), 6.05-6.07 (dd, 1H), 6.36-6.42 (m, 1H), 6.63-6.66 (dd, 1H), 7.14-7.16 (dd, 1H), 7.34 (t, 1H), 7.58 (t, 1H), 8.03 -8.05 (dd, 1H)

(Synthesis Example 5a)
11.13 g (57 mmol) of methyl 3-methoxy-4-(methylamino)benzoate from ABC Labtory Scientific was added to 100 mL of dry dichloromethane and 7.55 g (74.6 mmol) of triethylamine was added. Next, after cooling to about −15° C., 6.23 g (68.9 mmol) of acrylic acid chloride manufactured by Wako Pure Chemical Industries, Ltd. was diluted with 5 mL of dehydrated dichloromethane and slowly added dropwise, followed by stirring at room temperature for 3 hours. bottom. Further, after the precipitate was removed by filtration, the filtrate was washed with water, saturated aqueous sodium hydrogencarbonate solution and saturated aqueous sodium chloride solution. Next, after drying with sodium sulfate, it was concentrated under reduced pressure to obtain an oil. Furthermore, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. was packed, purified by column chromatography using hexane and ethyl acetate as an eluent, and an active energy ray represented by the following structural formula (5). 11.26 g of polymerizable compound 5 as a colorless oil was obtained (yield: about 75%).

Identification data are as follows.
¹ H-NMR (CDCl ₃ ): δ 3.31 (s, 3H), 3.89 (s, 3H), 3.92 (s, 3H), 6.03-6.06 (dd, 1H), 6 .33-6.38 (m, 1H), 6.61-6.65 (dd, 1H), 7.14 (d, 1H), 7.67-7.69 (m, 2H)

(Comparative Synthesis Example 1a)
A commercially available phenoxyethyl acrylate represented by the following structural formula (6) (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the active energy ray-polymerizable compound 6.

(Comparative Synthesis Example 2a)
A commercially available phenyl acrylate represented by the following structural formula (7) (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the active energy ray-polymerizable compound 7.

Next, the obtained active energy ray-polymerizable compound was subjected to viscosity measurement and odor evaluation. The results are shown in Table 1 below.

<Measurement of viscosity>
The viscosity of the obtained active energy ray-polymerizable compound was measured using a cone rotor (1°34′×R24) with a cone and plate type rotational viscometer (device name: VISCOMETER TVE-22L, manufactured by Toki Sangyo Co., Ltd.). , and the number of revolutions was 50 rpm, and the temperature of constant temperature circulating water was measured at 25°C.

<Evaluation of Odor>
The odor of the obtained active energy ray-polymerizable compound was confirmed by the following procedures (1) to (3), and the “absence of odor” was evaluated based on the following evaluation criteria.
(1) About 100 mg (0.1 g) of each compound was placed in a 50 mL sample bottle (glass bottle) and the bottle was capped.
(2) Leave for about 30 minutes under room temperature conditions.
(3) The nose was brought close to the sample bottle (glass bottle) and the odor was smelled when the lid was opened.
〔Evaluation criteria〕
A: No smell or no discomfort if felt B: Unique odor causes discomfort C: Unique odor causes strong discomfort D: Unique odor causes strong discomfort for a long time

The results in Table 1 show that the active energy ray-polymerizable compounds of Synthesis Examples 1a to 5a have little odor.

<Preparation example of active energy ray-curable composition>
(Examples 1b-5b and Comparative Examples 1b-2b)
950 mg of each of the active energy ray-polymerizable compounds of Synthesis Examples 1a to 5a and Comparative Synthesis Examples 1a to 2a, and a photopolymerization initiator (trade name: IRGACURE 907, component name: 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholinopropan-1-one, manufactured by BASF Japan Ltd.) was mixed using a magnetic stirrer to prepare active energy ray-curable compositions of Examples 1b to 5b and Comparative Examples 1b to 2b. bottom.

Photocurability and photopolymerizability of each of the active energy ray-curable compositions of Examples 1b to 5b and Comparative Examples 1b to 2b were evaluated as follows. The results are shown in Table 2 below.

<Photocurability, photopolymerization>
Using a viscoelasticity measuring device (device name: MCR302, manufactured by Anton-Parr), an optional UV curing measurement cell, and an LED light source (trade name: LIGHTNINGCURE LC-L1, manufactured by Hamamatsu Photonics Co., Ltd.), each active energy ray curing Photocurability and photopolymerizability of the mold composition were evaluated.
Specifically, after sandwiching the sample in a gap of 10 μm using a cone plate with a diameter of 20 mm, it was irradiated with ultraviolet rays having a wavelength of 365 nm at 50 mW/cm ² , and changes in viscoelasticity were measured until the elastic modulus was saturated. The maximum value of the saturated storage elastic modulus was determined from the measurement results and used as an index of photocurability.
Also, the energy of the ultraviolet rays irradiated until the storage 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 irradiation time of the ultraviolet rays (seconds). This was used as an index of photopolymerizability.

From the results in Table 2, the active energy ray-curable compositions of Examples 1b to 5b using the active energy ray-polymerizable compounds of Synthesis Examples 1a to 5a have excellent photopolymerizability and photocurability, particularly photocurability. It can be seen that it is superior to Specifically, the curing energy, which is an index of photopolymerizability, is lower than that of the comparative examples, and the saturated storage elastic modulus, which indicates the level of photocurability, shows a very large value. This indicates that the polymerization is promoted by having a polar ester structure on the aromatic ring in the molecule, and that a harder state is formed by the intramolecular interaction due to the polar structure in the cured product. It is thought that Viscosity and curability differ depending on the size and substitution position of the ester structure, and the smaller the terminal structure of the ester is alkyl, the lower the viscosity and the smaller the curing energy, so that both low viscosity and curability are achieved.

<Preparation example of black ink>
(Examples 1c to 4c)
100 parts by mass of the active energy ray-polymerizable compound of Synthesis Examples 1a to 4a, 10 parts by mass of a photopolymerization initiator (trade name: IRGACURE 907, manufactured by BASF Japan Ltd.), and carbon black (trade name: MICROLITH Black CK, (manufactured by BASF Japan Ltd.) was mixed to obtain black inks of Examples 1c to 4c.

<Example of making blue ink>
(Examples 1d to 4d)
100 parts by mass of the active energy ray-polymerizable compound of Synthesis Examples 1a to 4a, 10 parts by mass of a photopolymerization initiator (trade name: IRGACURE 907, manufactured by BASF Japan Ltd.), and a blue pigment (trade name: MICROLITH Blue 4G-K, BASF Japan Ltd.) was mixed to obtain blue inks of Examples 1d to 4d.

<Curability Evaluation 1 of Inkjet Ink>
Each of the inks of Examples 1c to 4c and Examples 1d to 4d was ejected onto a slide glass using an inkjet recording apparatus (manufactured by Ricoh Co., Ltd., head: GEN4 manufactured by Ricoh Printing Systems Co., Ltd.), followed by UV irradiation. A machine (trade name: LH6, manufactured by Fusion Systems Japan Co., Ltd.) was used to irradiate ultraviolet rays having a wavelength of 365 nm at 200 mW/cm ² for curing.
As a result, each ink could be ejected by inkjet without any problem, and the ink image was sufficiently cured.
Each ink substantially corresponds to that using each active energy ray-curable composition of Examples 1b to 4b. When the polymerizability and photocurability were measured, it was confirmed that both of them were as excellent as the active energy ray-curable compositions of Examples 1b to 4b.

<Ink curability evaluation 2>
Dip the tip of the dip pen in each of the inks of Examples 1c to 4c and Examples 1d to 4d, write letters on PET film and plain paper, and then use a UV irradiation machine (trade name: LH6, Fusion System Japan Co., Ltd. (manufacturer), and cured by irradiating ultraviolet rays with a wavelength of 365 nm at 200 mW/cm ² . As a result, the ink image was sufficiently cured.

39 image forming apparatus

Japanese Patent No. 2688710 JP 2009-215179 A JP 2010-067621 A

Claims (8)

An active energy ray-curable composition containing a (meth)acrylamide compound represented by the following general formula (1).

(In the general formula (1), R1 represents a hydrogen atom, R2 represents an alkyl group having 1 carbon number, X represents an alkyl group having 1 to 8 carbon atoms, and Y represents an alkoxy group having 1 carbon number. , m represents an integer of 0 or 1, and n represents 1.) The active energy ray-curable composition according to claim 1, wherein the (meth)acrylamide compound represented by the general formula (1) is any one of the following structural formulas (1) to (5): .

An active energy ray-curable ink containing the active energy ray-curable composition according to claim 1 . An active energy ray-curable inkjet ink containing the active energy ray-curable composition according to claim 1 . The active energy ray-curable composition according to any one of claims 1 or 2, the active energy ray-curable ink according to claim 3, or the active energy ray-curable inkjet ink according to claim 4, Contained container. The active energy ray-curable composition according to any one of claims 1 or 2, the active energy ray-curable ink according to claim 3, or the active energy ray-curable inkjet ink according to claim 4, a contained containment means;
applying means for applying the stored active energy ray-curable composition, the active energy ray-curable ink, or the active energy ray-curable inkjet ink;
and irradiation means for irradiating the applied active energy ray-curable composition, active energy ray-curable ink, or active energy ray-curable inkjet ink with an active energy ray. forming device. The active energy ray-curable composition according to any one of claims 1 or 2, the active energy ray-curable ink according to claim 3, or the active energy ray-curable inkjet ink according to claim 4. a granting step of granting;
and an irradiation step of irradiating the applied active energy ray-curable composition, the active energy ray-curable ink, or the active energy ray-curable inkjet ink with an active energy ray. Forming method. The active energy ray-curable composition according to any one of claims 1 or 2, the active energy ray-curable ink according to claim 3, or the active energy ray-curable inkjet ink according to claim 4. a granting step of granting;
and an irradiation step of irradiating the applied active energy ray-curable composition, active energy ray-curable ink, or active energy ray-curable inkjet ink with an active energy ray.

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