JP6972813B2 - Curable composition, curable ink, containment vessel, 2D or 3D image forming device, 2D or 3D image forming method, cured product, and curable compound. - Google Patents

Description

The present invention relates to a curable composition, a curable ink, a containment vessel, a two-dimensional or three-dimensional image forming apparatus, a two-dimensional or three-dimensional image forming method, a cured product, and a curable compound.

An inkjet recording method is known as a method of forming an image on a recording medium such as paper. This inkjet recording method has high ink consumption efficiency and excellent resource saving, and it is possible to keep the ink cost per unit recording low.

In recent years, an inkjet recording method using a curable ink has attracted attention. For example, an ink using a tertiary acrylamide compound having an ester structure has been proposed (see, for example, Patent Document 1).

An object of the present invention is to provide a curable composition having less odor, excellent polymerizable and curable properties, and highly safe.

ただし、前記一般式（１）中、Ｒ_１は炭素数１〜６のアルキル基を表し、Ｘは炭素数１〜６のアルキレン基を表し、Ｙは下記一般式（２）又は下記一般式（３）を表す。

ただし、前記一般式（２）中、Ｒ_２は炭素数１〜１０のアルキル基を表し、＊は前記Ｘとの結合部位を表す。

ただし、前記一般式（３）中、Ｒ_２は炭素数１〜１０のアルキル基を表し、＊は前記Ｘとの結合部位を表す。 The curable composition of the present invention as a means for solving the above-mentioned problems contains an acrylamide compound represented by the following general formula (1).

However, in the general formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 6 carbon atoms, and Y represents the following general formula (2) or the following general formula ( Represents 3).

However, in the general formula (2), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a binding site with X.

However, in the general formula (3), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a binding site with X.

According to the present invention, it is possible to provide a curable composition having less odor, excellent polymerizable and curable properties, and highly safe.

It is a schematic diagram which shows an example of the image forming apparatus in this invention. It is a schematic diagram which shows an example of another image forming apparatus in this invention. It is a schematic diagram which shows an example of still another image forming apparatus in this invention.

ただし、前記一般式（１）中、Ｒ_１は炭素数１〜６のアルキル基を表し、Ｘは炭素数１〜６のアルキレン基を表し、Ｙは下記一般式（２）又は下記一般式（３）を表す。

ただし、前記一般式（２）中、Ｒ_２は炭素数１〜１０のアルキル基を表し、＊は前記Ｘとの結合部位を表す。

ただし、前記一般式（３）中、Ｒ_２は炭素数１〜１０のアルキル基を表し、＊は前記Ｘとの結合部位を表す。 (Curing composition and curable compound)
The curable composition of the present invention contains an acrylamide compound represented by the following general formula (1), preferably contains other curable compounds, a polymerization initiator, and an organic solvent, and further, if necessary, Contains colorants and other ingredients.

However, in the general formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 6 carbon atoms, and Y represents the following general formula (2) or the following general formula ( Represents 3).

However, in the general formula (2), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a binding site with X.

However, in the general formula (3), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a binding site with X.

The curable compound of the present invention is an acrylamide compound represented by the general formula (1).

<Acrylamide compound>
The acrylamide compound is represented by the general formula (1).

_{R 1} in the general formula (1) represents an alkyl group having 1 to 6 carbon atoms, which may be a straight chain or a branched chain.
Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, a pentyl group and a neopentyl group. A hexyl group and the like can be mentioned.
X in the general formula (1) represents an alkylene group having 1 to 6 carbon atoms, which may be a straight chain or a branched chain.
Examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group, and a butylene group.
Y in the general formula (1) represents the general formula (2) or the general formula (3).

_{R 2} in the general formula (2) represents an alkyl group having 1 to 10 carbon atoms, which may be a straight chain or a branched chain.
Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, a pentyl group and a neopentyl group. Examples thereof include a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group.
* In the general formula (2) represents a binding site with X.

_{R 2} in the general formula (3) represents an alkyl group having 1 to 10 carbon atoms, which may be a straight chain or a branched chain.
Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, a pentyl group and a neopentyl group. Examples thereof include a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group.
* In the general formula (3) represents a binding site with X.

The acrylamide compound represented by the general formula (1) has an ester structure at the terminal of tertiary acrylamide which is monofunctional and does not have a ring structure. In general, since a low molecular weight tertiary acrylamide compound has volatility, it strongly feels an odor peculiar to a monomer, which causes discomfort in handling a cured composition containing these compounds.

It is possible to suppress the volatility of the acrylamide compound and reduce the odor by introducing a highly polar functional group into such a low molecular weight tertiary acrylamide compound or by increasing the molecular weight. However, in that case, there is a problem that the viscosity is increased, and the restrictions on the use of the curable composition, particularly the ink for inkjet, are increased.
Therefore, the tertiary acrylamide compound represented by the general formula (1) has an ester structure at the terminal portion. Therefore, the odor can be suppressed due to the decrease in volatility due to the ester structure. It is also considered that the curability is improved by the interaction between molecules due to the presence of the ester structure. Further, since the tertiary acrylamide compound having an ester structure does not form a strong hydrogen bond, it is considered that the increase in viscosity is small and the low viscosity can be maintained. As a result, the acrylamide compound represented by the general formula (1) can be suitably used as a curable composition, and among them, an ink jet ink.

In general, since acrylamide compounds have high acute oral toxicity, there are concerns about the safety of curable compositions containing these compounds, and care must be taken in handling.
On the other hand, the acrylamide compound having the ester structure of the present invention tends to have low acute oral toxicity. Among them, when Y in the general formula (1) is the case of the general formula (3), the acute oral toxicity tends to be very low. Therefore, the curable composition containing the acrylamide compound of the present invention is expected to have low acute oral toxicity and can enhance safety.

ただし、前記一般式（４）中、Ｒ_１は炭素数１〜６のアルキル基を表し、Ｘは炭素数１〜３のアルキレン基を表し、Ｒ_２は炭素数１〜４のアルキル基を表す。
前記Ｒ_１で表される炭素数１〜６のアルキル基としては、直鎖構造であってもよく、分岐構造であってもよく、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｓ−ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、ネオペンチル基、ヘキシル基などが挙げられる。これらの中でも、Ｒ_１が炭素数１〜３のアルキル基が好ましく、メチル基、エチル基がより好ましい。
前記Ｘで表される炭素数１〜３のアルキレン基としては、直鎖構造であってもよく、分岐構造であってもよく、例えば、メチレン基、エチレン基、プロピレン基、メチルメチレン基、ジメチルメチレン基などが挙げられる。これらの中でも、メチレン基、メチルメチレン基、ジメチルメチレン基が好ましく、メチレン基、メチルメチレン基がより好ましい。
前記Ｒ_２で表される炭素数１〜４のアルキル基としては、直鎖構造であってもよく、分岐構造であってもよく、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｓ−ブチル基、イソブチル基、ｔ−ブチル基などが挙げられる。これらの中でも、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基が好ましく、Ｒ_２が炭素数１〜３のアルキル基がより好ましい。 The acrylamide compound represented by the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose, but the compound represented by the following general formula (4) is preferable.

However, in the general formula (4), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 3 carbon atoms, and R ₂ represents an alkyl group having 1 to 4 carbon atoms. ..
The alkyl group having 1 to 6 carbon atoms represented by R _1, may be straight chain structure, it may be a branched structure, for example, a methyl group, an ethyl group, a propyl group, an isopropyl radical, n -Butyl group, s-butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group and the like can be mentioned. Among these, _{an alkyl group having R 1} having 1 to 3 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable.
The alkylene group having 1 to 3 carbon atoms represented by X may have a linear structure or a branched structure, for example, a methylene group, an ethylene group, a propylene group, a methylmethylene group, or a dimethyl group. Examples include a methylene group. Among these, a methylene group, a methylmethylene group and a dimethylmethylene group are preferable, and a methylene group and a methylmethylene group are more preferable.
The alkyl group having 1 to 4 carbon atoms represented by R _2, may be straight chain structure, it may be a branched structure, for example, a methyl group, an ethyl group, a propyl group, an isopropyl radical, n -Butyl group, s-butyl group, isobutyl group, t-butyl group and the like can be mentioned. Among these, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group are preferable, and _{an alkyl group having R 2} having 1 to 3 carbon atoms is more preferable.

Next, as specific examples of the acrylamide compound represented by the general formula (1), the exemplary compounds a to h are shown, but the present invention is not limited thereto.

Examples of the exemplified compound a group include the compounds of the a1 to a6 groups shown below. These may be used alone or in combination of two or more.

<< Example compound a1 group >>

<< Example compound a2 group >>

<< Example compound a3 group >>

<< Example compound a4 group >>

<< Example compound a5 group >>

<< Example compound a6 group >>

Examples of the example compound b group include the compounds of the groups b1 to b6 shown below. These may be used alone or in combination of two or more.

<< Example compound b1 group >>

<< Example compound b2 group >>

<< Example compound b3 group >>

<< Example compound b4 group >>

<< Example compound b5 group >>

<< Example compound b6 group >>

Examples of the exemplified compound c group include the compounds of the c1 to c6 groups shown below. These may be used alone or in combination of two or more.

<< Example compound c1 group >>

<< Example compound c2 group >>

<< Example compound c3 group >>

<< Example compound c4 group >>

<< Example compound c5 group >>

<< Example compound c6 group >>

Examples of the example compound d group include the compounds of the d1 to d6 groups shown below. These may be used alone or in combination of two or more.

<< Example compound d1 group >>

<< Example compound d2 group >>

<< Example compound d3 group >>

<< Example compound d4 group >>

<< Example compound d5 group >>

<< Example compound d6 group >>

Examples of the exemplified compound e group include the compounds of the e1 to e6 groups shown below. These may be used alone or in combination of two or more.

<< Example compound e1 group >>

<< Example compound e2 group >>

<< Example compound e3 group >>

<< Example compound e4 group >>

<< Example compound e5 group >>

<< Example compound e6 group >>

Examples of the example compound f group include the following compounds of the f1 group. These may be used alone or in combination of two or more.

<< Example compound f1 group >>

Examples of the example compound g group include compounds of the g1 to g6 groups shown below. These may be used alone or in combination of two or more.

<< Example compound g1 group >>

<< Example compound g2 group >>

<< Example compound g3 group >>

<< Example compound g4 group >>

<< Example compound g5 group >>

<< Example compound g6 group >>

Examples of the exemplified compound h group include the following compounds of the h1 group. These may be used alone or in combination of two or more.

<< Example compound h1 group >>

Among the above-mentioned exemplified compounds a to h groups, Exemplified Compound a1-1, Exemplified Compound a1-4, Exemplified Compound a6-1, Exemplified Compound d1-1, Exemplified Compound d1-2, Exemplified Compound d1-4, Exemplified Compound d1 -5, Exemplified compound d3-2, Exemplified compound d4-1, Exemplified compound d4-5, Exemplified compound d6-1, Exemplified compound d6-4, Exemplified compound g1-1, Exemplified compound g1-2, and Exemplified compound g1- 5 is preferable, and exemplary compound d1-1, exemplary compound d1-2, exemplary compound g1-1, exemplary compound g1-2, and exemplary compound g1-5 are more preferred.

The acrylamide compound represented by the general formula (1) can be used by mixing two or more different compounds with each other, and the different compounds in this case also include structural isomers. The mixing ratio is not particularly limited.

The content of the acrylamide compound represented by the general formula (1) is preferably 20% by mass or more and 98% by mass or less, more preferably 30% by mass or more and 90% by mass or less, based on the total amount of the cured composition. It is particularly preferable that it is 30% by mass or more and 80% by mass or less.

The acrylamide compound represented by the general formula (1) ^{can be structurally analyzed by using 1 1} H-NMR spectrum and IR spectrum.

<Other curable compounds>
As the other curable compound, a curable compound other than the acrylamide compound represented by the general formula (1) can be used.

The curable compound other than the acrylamide compound represented by the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a radical polymerizable compound, a cationically polymerizable compound, or anionic polymerization can be selected. Examples include sex compounds. These may be used alone or in combination of two or more.

The radically polymerizable compound is not particularly limited as long as it is a compound having one or more ethylenically unsaturated groups capable of radical polymerization, and can be appropriately selected depending on the intended purpose. For example, monomers and oligomers. , Compounds including 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, and anhydrides having ethylenically unsaturated groups. Acrylonitrile, styrene, unsaturated polyester, unsaturated polyether, unsaturated polyamide, and unsaturated urethane are preferable.

Examples of the radically polymerizable compound include 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) propane, and 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 tetraacrylate, trimethylol Acrylic acid derivatives such as propanetriacrylate, 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-methacryloxypolyethoxyphenyl) Methacrylic acid derivatives such as propane, acrylamide derivatives such as N-methylol acrylamide, diacetone acrylamide, 2-hydroxyethyl acrylamide, acryloyl morpholine, allyl compound derivatives such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate, ethylene glycol. Divinyl Ether, Ethylene Glycol Monovinyl Ether, Diethylene Glycol Divinyl Ether, Triethylene Glycol Monobi Nyl 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, trimethylolpropane trivinyl ether. Monovinyl ether compound such as, divinyl ether compound, or trivinyl ether compound, 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. Monovinyl ether compounds such as vinyl ether, isopropyl vinyl ether, 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, Neopentyl glycol diacrylate of hydroxypivalate, 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-acryloyloxy Ethylhexahydrophthalic acid, propylene oxide adduct diacrylate of bisphenol A, ethylene oxide adduct diacrylate of bisphenol A, dipentaerythritol hexaacrylate, tolylene diisocyanato urethane prepolymer, lactone-modified flexible acrylate, butoxyethyl acrylate, Propylene glycol diglycidyl ether acrylic acid adduct, hexamethylene di Examples thereof include isocyanato urethane prepolymer, methoxydipropylene glycol acrylate, ditrimethylolpropane tetraacrylate, stearyl acrylate, isoamyl acrylate, isomyristyl acrylate, isostearyl acrylate, and lactone-modified acrylate. These may be used alone or in combination of two or more.

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

Examples of the anionic polymerizable compound include epoxy compounds, lactone compounds, acrylic compounds, and methacrylic compounds. These may be used alone or in combination of two or more. Among these, acrylic acid derivatives and methacrylic acid derivatives exemplified as the radically polymerizable compound are preferable.

The content of the other curable compound is preferably 0.01 parts by mass or more and 100 parts by mass or less, preferably 0.1 parts by mass or more, with respect to 100 parts by mass of the acrylamide compound represented by the general formula (1). More preferably, it is 50 parts by mass or less.

<Polymerization initiator>
The curable composition of the present invention may contain a polymerization initiator. The polymerization initiator may be any one capable of generating active species such as radicals and cations by energy and initiating 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, and is, for example, trimethylamine, methyldimethylamine, 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.

The cationic As the polymerization initiator, for example, diazonium, ammonium, iodonium, sulfonium, aromatic onium compounds of phosphonium such as ^{_{B (C 6 F 5) 4}} -, PF 6 -, AsF 6 -, SbF 6 -, CF 3 Examples thereof include SO ₃ ^- salts, sulfonates capable of generating sulfonic acid, halides capable of generating hydrogen halides, and iron allen complexes.

Examples of the anionic polymerization initiator include an o-nitrobenzyl carbamate derivative, an o-acyloxyl derivative, an o-carbamoyloxime amidine derivative and the like.

Examples of the combination of the curable compound and the polymerization initiator include a combination of the radical polymerizable compound and the radical polymerization initiator, a combination of the cationically polymerizable compound and the cationic polymerization initiator, and the anionic polymerization. Examples thereof include a combination of the sex compound and the anionic polymerization initiator.

<Organic solvent>
The 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 a general non-reactive organic solvent such as ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and should be distinguished from the reactive monomer. be. Further, "not containing" the organic solvent means that it is substantially free of the organic solvent, and it is preferably less than 0.1% by mass.

<Color material>
The 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 a desired color concentration, dispersibility in the composition, etc., and is not particularly limited, but is 0. It is preferably 1 to 20% by mass. The curable composition of the present invention may be colorless and transparent without containing a coloring material, and in that case, it is suitable as, for example, an overcoat layer for protecting an image.
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.
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 rake (basic dye type rake, acidic dye type rake), nitro pigment, nitroso pigment, aniline black, Daylight fluorescent pigments can be mentioned.
Further, in order to improve the dispersibility of the pigment, a dispersant may be further contained. 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.

<Other ingredients>
The curable composition of the present invention may contain other known components, if necessary. The other components are not particularly limited, but are, for example, conventionally known surfactants, polymerization inhibitors, leveling agents, antifoaming agents, fluorescent whitening agents, penetration promoters, wetting agents (moisturizers), and fixing agents. Agents, viscosity stabilizers, fungicides, preservatives, antioxidants, UV absorbers, chelating agents, pH regulators, thickeners and the like can be mentioned.

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

The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone, benzoquinone, p-methoxyphenol, TEMPO, TEMPOL, and cuperon complexes 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.

-Sensitizer-
The curable composition of the present invention may further contain a sensitizer in order to accelerate the decomposition of the polymerization initiator by applying energy.
The sensitizer absorbs active energy rays and heat and becomes an excited state, and in that state, it comes into contact with the polymerization initiator, and for example, chemical changes in the polymerization initiator due to actions such as electron transfer, energy transfer, and heat generation. Promotes (degradation or formation of radicals, acids, or bases).

The mass ratio (A / B) of the content A (mass%) of the sensitizer and the content B (mass%) of the polymerization initiator ^{is preferably 5 × 10 -3} or more and 200 or less, preferably 0. More preferably, it is 0.02 or more and 50 or less.

The sensitizer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a sensitizing dye having an absorption wavelength in a region having a wavelength of 350 nm or more and 450 nm or less.
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, carbomerocyanine), thiadins (eg, thionin, methyl blue, toluidin blue), acridins (eg, acrydin orange, chloroflavin, acryflavin), 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.

-Co-sensitizer-
The curable composition of the present invention may further contain a co-sensitizer.
As the co-sensitizer, for example, the sensitivity of the sensitizing dye to active energy rays and heat can be further improved, and the polymerization inhibition of the curable compound by oxygen can be suppressed.

The co-sensitizer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline. Examples thereof include amine compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, and thiols and sulfides such as β-mercaptonaphthalene. These may be used alone or in combination of two or more.

-Solvent-
The curable composition preferably does not contain a solvent, but for example, in order to improve the adhesiveness between the cured ink and the recording medium, the curable composition contains a solvent only when it does not affect the curing speed of the ink. You may.
The solvent is not particularly limited, and examples thereof include organic solvents and water. These may be used alone or in combination of two or more.
The content of the solvent is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 3% by mass or less, based on the total amount of the cured composition.

The curable composition of the present invention further contains a surfactant, a leveling additive, a matting agent, a polyester resin for adjusting film properties, a polyurethane resin, a vinyl resin, an acrylic resin, a rubber resin, waxes and the like. May be good.
Further, the curable composition of the present invention may further contain a tackifier (tacky fire) that does not inhibit polymerization in order to improve the adhesiveness to the polyolefin film, PET film and the like.

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

<Curing method>
Examples of the method for curing the curable composition of the present invention include a method of applying energy to cure the composition.
Examples of the energy include heat, active energy rays, and the like. These may be used alone or in combination of two or more. Among these, active energy rays are preferable.

<Curing means>
Examples of the means for curing the curable composition of the present invention include heat curing or curing with an active energy ray, and among these, curing with an active energy ray is preferable.
The active energy rays used for curing the curable composition of the present invention include ultraviolet rays, as well as polymerization reactions of 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 provide the energy necessary for advancing. 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.

<Preparation of curable composition>
The curable composition of the present invention can be produced by using the above-mentioned various components, and the preparation means and conditions thereof are not particularly limited. By putting it in a disperser such as a disc mill, a pin mill, or a dyno mill, and dispersing it to prepare a pigment dispersion, a polymerizable monomer, an initiator, a polymerization inhibitor, a surfactant, etc. are further mixed with the pigment dispersion. Can be prepared.

<Viscosity>
The viscosity of the curable composition of the present invention may be appropriately adjusted according to the intended use 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 is not particularly limited. The viscosity in the range of 20 ° C. to 65 ° C., preferably 3 to 40 mPa · s, more preferably 5 to 15 mPa · s, and particularly preferably 6 to 12 mPa · s at 25 ° C. 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'× R24) was used with a cone plate type rotational viscometer VISCOMETER TVE-22L manufactured by Toki Sangyo Co., Ltd., the rotation speed was 50 rpm, and the temperature of constant temperature circulating water was 20 ° C. It can be appropriately set and measured in the range of ~ 65 ° C. VISCOMATE VM-150III can be used to adjust the temperature of the circulating water.

<Use>
The application of the curable composition of the present invention is not particularly limited as long as it is in a field where a curable material is generally used, and can be appropriately selected depending on the intended purpose. For example, a molding resin, a paint, or an adhesive. , Insulation material, mold release agent, coating material, sealing material, various resists, various optical materials and the like.
Further, the curable composition of the present invention is used as an ink to not only form a design coating film on two-dimensional characters and images and various substrates, but also form a three-dimensional stereoscopic image (three-dimensional model). It can also be used as a material for three-dimensional modeling. This three-dimensional modeling material may be used, for example, as a binder between powder particles used in a powder laminating 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 molding method (stereolithography). Note that FIG. 2 is a method in which the cured composition of the present invention is discharged into a predetermined region, and the cured composition is sequentially laminated by irradiating it with active energy rays to perform three-dimensional modeling (details will be described later). Is to irradiate the storage pool (accommodation portion) 1 of the cured composition 5 of the present invention with active energy rays 4 to form a cured layer 6 having a predetermined shape on a movable stage 3, and sequentially stack these to form a three-dimensional shape. Is a way to do.
As a three-dimensional modeling apparatus for modeling a three-dimensional model using the curable composition of the present invention, a known one can be used, and the present invention is not particularly limited, but for example, a means for accommodating the composition and a means for supplying the composition. , Those equipped with a discharge means, an irradiation means, and the like.
The present invention also includes a cured product obtained by curing a cured composition and a molded product obtained by processing a structure in which the cured product is formed on a substrate. The molded product is, for example, a cured product or structure formed in a sheet shape or a film shape that has been subjected to molding processing such as heat stretching or punching, and is, for example, an automobile, an OA device, or electricity. -Suitably used for applications that require molding after decorating the surface, such as electronic devices, meters for cameras, 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.

(Curing ink)
The curable ink of the present invention contains the curable composition of the present invention.
As the curable composition, the same curable composition as that of the present invention can be used.

The curable ink is preferably for inkjet.

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

The two-dimensional or three-dimensional image forming apparatus of the present invention has an accommodating portion for accommodating at least one of the curable composition and the curable ink, and an imparting means for imparting energy.
The two-dimensional or three-dimensional image forming method of the present invention applies energy to at least one of the curable composition and the curable ink to form a two-dimensional or three-dimensional image.

<Image forming method, forming device>
As the method for forming an image of the present invention, active energy rays may be used, or heating or the like may be mentioned. In order to cure the curable composition of the present invention with active energy rays, there is an irradiation step of irradiating the active energy rays, and the image forming apparatus of the present invention is an irradiation means for irradiating the active energy rays. , The accommodating portion for accommodating the 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 cured 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. The ink is ejected to the recording medium 22 supplied from the supply roll 21 by the color printing units 23a, 23b, 23c, 23d including the ink cartridges of the yellow, magenta, cyan, and black color curable inks and the ejection head. Then, the light sources 24a, 24b, 24c, and 24d for curing the ink are irradiated with active energy rays to cure the ink, and a color image is formed. After that, the recording medium 22 is conveyed to the processing unit 25 and the printed matter 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 the 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 ejection head width. 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, ceramics, glass, 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 possible. Not limited to those used as general recording media, cardboard, building materials such as wallpaper and floor materials, cloth for clothing such as concrete and T-shirts, textiles, leather and the like can be appropriately used.
Further, the activation of the active 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. This makes it possible to save energy and reduce costs.
The recorded materials recorded by the ink of the present invention include 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, ceramics, and the like. It also includes those printed on the printed surface 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 transfer the first cured composition from the discharge head unit 30 for a modeled object to the discharge head unit 31 for a support. , 32 is a second curable composition having a composition different from that of the first curable composition, and these compositions are laminated while being cured by the adjacent ultraviolet irradiation means 33 and 34. More specifically, for example, the second curable composition is discharged from the support discharge head units 31 and 32 onto the modeled object support substrate 37, and is irradiated with active energy rays to be solidified to form a reservoir. After forming the first support layer to be held, the first cured composition is discharged from the discharge head unit 30 for a modeled object into the reservoir, and is irradiated with active energy rays to be solidified to form the first modeled object. By repeating the step of forming the layer a plurality of times while lowering the stage 38 that is movable in the vertical direction according to the number of times of stacking, the support layer and the modeled object layer are laminated to produce the three-dimensional modeled object 35. After that, the support laminated portion 36 is removed as needed. In FIG. 2, only one discharge head unit 30 for a modeled object is provided, but two or more may be provided.

(Cursed product)
The cured product is formed by using at least one of the curable composition of the present invention and the curable ink of the present invention.
As the curable composition, the same curable composition as the curable composition can be used.
As the curable ink, the same ink as the curable ink can be used.

(Decorative body)
As the decorative body, a surface decoration made of a cured product is applied on a base material, and the same one as the cured product can be used.

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.

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.
The ¹ H-NMR spectrum was ^{measured using 1} H-NMR (500 MHz) (device name: ECX500, manufactured by JEOL Ltd.). The IR spectrum was measured using FT-IR (device name: Spectrum GX, manufactured by PERKIN ELMER).

(Example 1a)
15.02 g (200 mmol) of 2- (methylamino) ethanol manufactured by Tokyo Chemical Industry Co., Ltd. was added to 200 mL of dehydrated dichloromethane, and 46.8 g (462 mmol) of triethylamine was added. Next, after cooling to about -60 ° C. in a dry ice-acetone mixture, 15.39 g (170 mmol) of acrylic acid chloride manufactured by Wako Pure Chemical Industries, Ltd. was diluted with 8 mL of dehydrated dichloromethane and slowly added dropwise to room temperature. It was stirred underneath for 2 hours. Again, the mixture was cooled to about −60 ° C. in a dry ice-acetone mixture, 15.7 g (200 mmol) of acetyl chloride was diluted with 8 mL of dehydrated dichloromethane and slowly added dropwise, followed by stirring at room temperature for about 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. Next, it was dried over sodium sulfate and then concentrated under reduced pressure to obtain an oil. Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. is filled, purified by column chromatography using hexane and ethyl acetate as an eluent, and cured by the following structural formula (a1-1). 6.1 g (yield: about 21%) of a light brown oily substance of the sex compound was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ2.04-2.08 (m, 3H), 3.04-3.15 (m, 3H), 3.63-3.71 (m, 2H), 4. 20-4.27 (m, 2H), 5.69-5.72 (m, 1H), 6.32-6.37 (m, 1H), 6.56-6.63 (m, 1H)
IR (NaCl): 3474, 2957, 1740, 1649, 1612, 1450, 1418, 1407, 1378, 1235, 1137, 1047, 981, 795, 605 cm ^-1

(Example 2a)
6.01 g (80 mmol) of 2- (methylamino) ethanol manufactured by Tokyo Chemical Industry Co., Ltd. was added to 120 mL of dehydrated dichloromethane, and 18.7 g (185 mmol) of triethylamine was added. Next, after cooling to about -15 ° C. in an ice-NaCl mixture, 6.15 g (68 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. The mixture was stirred at room temperature for 2.5 hours. Again, the mixture was cooled to about -15 ° C. in an ice-NaCl mixture, 8.52 g (80 mmol) of isobutyl chloride was diluted with 4.5 mL of dehydrated dichloromethane and slowly added dropwise, followed by stirring at room temperature for about 3.5 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. Next, it was dried over sodium sulfate and then concentrated under reduced pressure to obtain an oil. Further, 360 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. is filled, purified by column chromatography using hexane and ethyl acetate as an eluent, and cured by the following structural formula (a1-4). 2.2 g (yield: about 16%) of a pale yellow oily substance of the sex compound was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.15-1.20 (m, 6H), 2.52-2.57 (m, 1H), 3.05-3.15 (m, 3H), 3. 65-3.71 (m, 2H), 4.20-4.27 (m, 2H), 5.69-5.72 (m, 1H), 6.31-6.38 (m, 1H), 6.55-6.65 (m, 1H)
IR (NaCl): 3474, 2975, 1734, 1649, 1613, 1471, 1417, 1343, 1260, 1191, 115, 1082, 981, 795, 753 cm ^-1

(Example 3a)
11.72 g (100 mmol) of 2- (t-butylamino) ethanol manufactured by Tokyo Chemical Industry Co., Ltd. was added to 110 mL of dehydrated dichloromethane, and 23.07 g (228 mmol) of triethylamine was added. Next, after cooling to about -15 ° C. in an ice-NaCl mixture, 8.14 g (90 mmol) of acrylic acid chloride manufactured by Wako Pure Chemical Industries, Ltd. was diluted with 4 mL of dehydrated dichloromethane and slowly added dropwise at room temperature. Was stirred for 3 hours. Again, the mixture was cooled to about −15 ° C. in an ice-NaCl mixture, 7.85 g (100 mmol) of acetyl chloride was diluted with 4 mL of dehydrated dichloromethane and slowly added dropwise, followed by stirring at room temperature for about 1.5 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. Next, it was dried over sodium sulfate and then concentrated under reduced pressure to obtain an oil. Further, 320 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. is filled, purified by column chromatography using hexane and ethyl acetate as an eluent, and cured by the following structural formula (a6-1). 0.94 g (yield: about 4.9%) of a pale yellow oily substance of the sex compound was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.48 (s, 9H), 2.06 (s, 3H), 3.63 (t, 2H), 4.14 (t, 2H), 5.62 (dd) , 1H), 6.26 (dd, 1H), 6.63-6.69 (m, 1H)
IR (NaCl): 2966,1743,1650,1612,1415,1368,1234,1105,1051,981,798cm ^-1

(Example 4a)
8.37 g (60 mmol) of sarcosine methyl ester hydrochloride manufactured by Tokyo Chemical Industry Co., Ltd. was added to 100 mL of dehydrated dichloromethane, and 17.49 g (172 mmol) of triethylamine was added. Next, after cooling to about -15 ° C. in an ice-NaCl mixture, 6.52 g (72 mmol) of acrylic acid chloride manufactured by Wako Pure Chemical Industries, Ltd. was diluted with 4 mL of dehydrated dichloromethane and slowly added dropwise at room temperature. Was stirred for 3 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. Next, it was dried over sodium sulfate and then concentrated under reduced pressure to obtain an oil. Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. is filled, purified by column chromatography using hexane and ethyl acetate as an eluent, and cured by the following structural formula (d1-1). 4.69 g (yield: about 50%) of a pale yellow oily substance of the sex compound was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ3.05 / 3.16 (s, 3H), 3.75 / 3.78 (s, 3H), 4.13 / 4.20 (s, 2H), 5. 68-5.76 (m, 1H), 6.28-6.44 / 6.61-6.66 (m, 2H)
IR (NaCl): 3484, 2955, 1748, 1650, 1614, 1482, 1459, 1437, 1420, 1367, 1280, 1212, 1125, 1060, 1010, 981, 940, 890, 847, 797, 709, 555 cm ^-1

(Example 5a)
12.29 g (80 mmol) of sarcosine ethyl ester hydrochloride manufactured by Tokyo Kasei Kogyo Co., Ltd. was added to 110 mL of dehydrated dichloromethane, and 22.34 g (220 mmol) of triethylamine was added. Next, after cooling to about -15 ° C. in an ice-NaCl mixture, 8.69 g (96 mmol) of acrylic acid chloride manufactured by Wako Pure Chemical Industries, Ltd. was diluted with 5 mL of dehydrated dichloromethane and slowly added dropwise at room temperature. Was stirred for 3 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. Next, it was dried over sodium sulfate and then concentrated under reduced pressure to obtain an oil. Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. is filled, purified by column chromatography using hexane and ethyl acetate as an eluent, and cured by the following structural formula (d1-2). 7.58 g (yield: about 55%) of a pale yellow oily substance of the sex compound was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.26-1.31 (m, 3H), 3.06 / 3.16 (s, 3H), 4.11-4.25 (m, 4H), 5. 68-5.76 (m, 1H), 6.28-6.44 / 6.61-6.66 (m, 2H)
IR (NaCl): 3484, 2984, 1745, 1653, 1614, 1477, 1419, 1375, 1280, 1201, 1123, 1032, 980, 797 cm ^-1

(Example 6a)
Add 9.68 g (70 mmol) of potassium carbonate to 31.05 g (70 mmol) of a methylamine 7% tetrahydrofuran (hereinafter, also referred to as "THF") solution manufactured by Tokyo Chemical Industry Co., Ltd. and 15 mL of THF, and stir at room temperature. , 11.60 g (77 mmol) of n-butyl chloroacetate manufactured by Tokyo Chemical Industry Co., Ltd. was added dropwise to a solution dissolved in 5 mL of THF and reacted to obtain a reaction solution. Next, the obtained reaction solution was filtered, and a solution of 9.68 g (70 mmol) of potassium carbonate dissolved in 50 mL of water was added to the obtained filtrate and cooled in an ice bath. After slowly dropping 6.96 g (77 mmol) of acrylic acid chloride, the mixture was stirred at room temperature for 2 hours. Then, using ethyl acetate, each layer was separated by extraction, and the ethyl acetate layer was separated. The obtained ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous sodium sulfate, and concentrated to obtain 13.3 g of a colorless solution.
Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. is filled, purified by column chromatography using hexane and ethyl acetate as an eluent, and cured by the following structural formula (d1-4). 5.5 g (yield: about 39%) of a colorless liquid of the sex compound was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ0.93 (t, 3H), 1.34-1.42 (m, 2H), 1.59-1.66 (m, 2H), 3.06 / 3. 16 (s, 3H), 4.11-4.19 (m, 4H), 5.68-5.76 (m, 1H), 6.28-6.44 / 6.60-6.66 (m) , 2H)
IR (NaCl): 2961,2936, 2874, 1747, 1655, 1617, 1466, 1418, 1378, 1362, 1308, 1279, 1198, 1122, 1061, 1031, 979, 797 cm ^-1

(Example 7a)
Methylamine 7% THF solution manufactured by Tokyo Chemical Industry Co., Ltd. 31.05 g (70 mmol), potassium carbonate 9.68 g (70 mmol) added to 15 mL of THF, stirred at room temperature, and isopropyl chloroacetate 10 manufactured by Tokyo Chemical Industry Co., Ltd. A solution prepared by dissolving .52 g (77 mmol) in 5 mL of THF was added dropwise and reacted to obtain a reaction solution. Next, the obtained reaction solution was filtered, and a solution of 9.68 g (70 mmol) of potassium carbonate dissolved in 50 mL of water was added to the obtained filtrate and cooled in an ice bath. After slowly dropping 6.96 g (77 mmol) of acrylic acid chloride, the mixture was stirred at room temperature for 2 hours. Then, using ethyl acetate, each layer was separated by extraction, and the ethyl acetate layer was separated. The obtained ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous sodium sulfate, and concentrated to obtain 8.4 g of a colorless solution.
Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. is filled, purified by column chromatography using hexane and ethyl acetate as an eluent, and cured by the following structural formula (d1-5). 3.9 g (yield: about 30%) of a colorless liquid of the sex compound was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.26 (d, 6H), 3.05 / 3.15 (s, 3H), 4.07 / 4.16 (s, 2H), 5.04-5. 10 (m, 1H), 5.67-5.75 (m, 1H), 6.28-6.44 / 6.61-6.66 (m, 2H)
IR (NaCl): 2938, 2982, 1741, 1655, 1617, 1467, 1418, 1374, 1279, 1211, 1107, 1060, 980, 957, 900, 837, 797, 726 cm ^-1

(Example 8a)
5.25 g (88.8 mmol) of n-propylamine manufactured by Tokyo Chemical Industry Co., Ltd. was dissolved in 60 mL of ethyl acetate, and 12.27 g (88.8 mmol) of potassium carbonate was added. Next, a solution prepared by dissolving 10.88 g (88.8 mmol) of ethyl chloroacetate manufactured by Tokyo Chemical Industry Co., Ltd. in 10 mL of ethyl acetate was added dropwise at room temperature, and the mixture was stirred for 4 hours to react to obtain a reaction solution. Next, the obtained reaction solution was filtered to remove the precipitated salt, and then concentrated to obtain 12.3 g of a colorless solution. The solution was left at room temperature, and the precipitated colorless crystals were washed with ethyl acetate and dried to obtain 5.8 g of N-propylsarcosine ethyl ester. This compound was used as it was in the following reaction.
10 mL of water was added to 5.8 g (40 mmol) of N-propylsarcosine ethyl ester, and then a solution of 6.08 g (44 mmol) of potassium carbonate in 20 mL of water was added and cooled in an ice bath. 3.98 g (44 mmol) of acrylic acid chloride was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours. Then, using ethyl acetate, each layer was separated by extraction, and the ethyl acetate layer was separated. The obtained ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous sodium sulfate, and concentrated to obtain 7.0 g of a colorless solution.
Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. is filled, purified by column chromatography using hexane and ethyl acetate as an eluent, and cured by the following structural formula (d3-2). A colorless liquid of 4.9 g (yield: about 62%) of the sex compound was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ0.90-0.95 (m, 3H), 1.26-1.30 (m, 3H), 1.56-1.71 (m, 2H), 3. 37-3.44 (m, 2H), 4.08 / 4.12 (s, 2H) 4.18-4.25 (m, 2H), 5.67-5.74 (m, 1H), 6 .28-6.42 / 6.58-6.63 (m, 2H)
IR (NaCl): 2966, 2937, 2877, 1749, 1653, 1616, 1442, 1406, 1374, 1233, 1198, 1185, 1025, 979, 796 cm ^-1

(Example 9a)
2.95 g (50 mmol) of isopropylamine manufactured by Tokyo Chemical Industry Co., Ltd. was dissolved in 50 mL of ethyl acetate, 6.91 (50 mmol) of potassium carbonate was added, and the mixture was stirred at room temperature. Next, a solution prepared by dissolving 5.43 g (50 mmol) of methyl chloroacetate manufactured by Tokyo Chemical Industry Co., Ltd. in 5 mL of ethyl acetate was added dropwise at room temperature and stirred for 2 hours to react to obtain a reaction solution. Next, the obtained reaction solution was filtered to remove the precipitated salt, and then an aqueous solution prepared by dissolving 6.91 g (50 mmol) of potassium carbonate in 50 mL of water was added. After cooling in an ice bath, 4.98 g (55 mmol) of acrylic acid chloride was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours. Then, using ethyl acetate, each layer was separated by extraction, and the ethyl acetate layer was separated. The obtained ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous sodium sulfate, and concentrated to obtain 9.8 g of a colorless solution.
Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. is filled, purified by column chromatography using hexane and ethyl acetate as an eluent, and cured by the following structural formula (d4-1). 3.7 g (yield: about 40%) of a colorless liquid of the sex compound was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.11 / 1.22 (d, 6H), 3.74 / 3.77 (s, 3H), 3.99 (s, 2H), 4.26-4. 32 (m, 1H), 5.66-5.73 (m, 1H), 6.31-6.35 / 6.62-6.67 (m, 2H)
IR (NaCl): 2974, 1755, 1645, 1612, 1542, 1446, 1368, 1341, 1205, 1129, 1884, 1062, 985, 797 cm ^-1

(Example 10a)
A mixture of 2.95 g (50 mmol) of isopropylamine manufactured by Tokyo Kasei Kogyo Co., Ltd., 50 mL of ethyl acetate and 6.91 g (50 mmol) of potassium carbonate is mixed with 6.83 (50 mmol) of isopropylchloroacetate manufactured by Tokyo Kasei Kogyo Co., Ltd. A solution diluted with 5 mL of ethyl was added dropwise and reacted to obtain a reaction solution. Next, the obtained reaction solution was filtered to remove the precipitated salt, and then an aqueous solution prepared by dissolving 6.91 g (50 mmol) of potassium carbonate in 50 mL of water was added. After cooling in an ice bath, 4.98 g (55 mmol) of acrylic acid chloride was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours. Then, using ethyl acetate, each layer was separated by extraction, and the ethyl acetate layer was separated. The obtained ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous sodium sulfate, and concentrated to obtain 8.5 g of a colorless solution.
Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. is filled, purified by column chromatography using hexane and ethyl acetate as an eluent, and cured by the following structural formula (d4-5). 1.3 g (yield: about 12%) of a colorless liquid of the sex compound was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.11 / 1.21 (d, 6H), 1.25 (d, 6H), 3.95 (s, 2H), 4.28 / 4.93 (m, 1H), 5.05 (m, 1H), 5.65-5.71 (m, 1H), 6.29-6.34 / 6.61-6.67 (m, 2H)
IR (NaCl): 2981,239, 2879, 1746, 1650, 1614, 1465, 1443, 1373, 1340, 1286, 1256, 1202, 1146, 1108, 1084, 1060, 1010, 977, 958, 900, 836, 796 , 757,718cm ^-1

(Example 11a)
A mixture of 8.10 g (80 mmol) of n-hexylamine manufactured by Tokyo Chemical Industry Co., Ltd., 55 mL of ethyl acetate and 11.3 g (81.8 mmol) of potassium carbonate and 9.55 g of methyl chloroacetate manufactured by Tokyo Chemical Industry Co., Ltd. ( 88 mmol) was added dropwise and reacted to obtain a reaction solution. Next, the obtained reaction solution was filtered to remove the precipitated salt, and then an aqueous solution prepared by dissolving 11.05 g (80 mmol) of potassium carbonate in 80 mL of water was added. After cooling in an ice bath, 8.0 g (88 mmol) of acrylic acid chloride was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours. Then, using ethyl acetate, each layer was separated by extraction, and the ethyl acetate layer was separated. The obtained ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous sodium sulfate, and concentrated to obtain 16.1 g of a colorless solution.
Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. is filled, purified by column chromatography using hexane and ethyl acetate as an eluent, and cured by the following structural formula (d6-1). 3.5 g (yield: about 19%) of a colorless liquid of the sex compound was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ0.89 (t, 3H), 1.26-1.33 (m, 6H), 1.58-1.61 (m, 2H), 3.40 / 3. 44 (t, 2H), 3.74 / 3.77 (s, 3H), 4.10 / 4.13 (s, 2H), 5.67-5.75 (m, 1H), 6.29- 6.42 / 6.57-6.62 (m, 2H)
IR (NaCl): 2955,2931,2858,1753,1653,1616,1439,1406,1373,1250,1206,1178,1138,1063,979,796cm ^-1

(Example 12a)
A mixture of 5.06 g (50 mmol) of n-hexylamine manufactured by Tokyo Kasei Kogyo Co., Ltd., 50 mL of ethyl acetate and 6.91 g (50 mmol) of potassium carbonate and 7.53 g of n-butylchloroacetate manufactured by Tokyo Kasei Kogyo Co., Ltd. ( A solution diluted with 5 mL of ethyl acetate (50 mmol) was added dropwise and reacted to obtain a reaction solution. Next, the obtained reaction solution was filtered to remove the precipitated salt, and then an aqueous solution prepared by dissolving 6.91 g (50 mmol) of potassium carbonate in 50 mL of water was added. After cooling in an ice bath, 4.98 g (55 mmol) of acrylic acid chloride was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours. Then, using ethyl acetate, each layer was separated by extraction, and the ethyl acetate layer was separated. The obtained ethyl acetate layer was washed with saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous sodium sulfate, and concentrated to obtain 13.4 g of a colorless solution.
Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. is filled, purified by column chromatography using hexane and ethyl acetate as an eluent, and cured by the following structural formula (d6-4). A colorless liquid of 5.8 g (yield: about 43%) of the sex compound was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ0.88-1.62 (m, 18H), 3.40 / 3.44 (t, 2H), 4.05 / 4.08 (s, 2H), 4. 14 (t, 2H), 5.66-5.74 (m, 1H), 6.29-6.41 / 6.56-6.62 (m, 2H)
IR (NaCl): 2958,2931,288,2860,1748,1652,1614,1539,1456,1377,1196,1137,1064,1022,977,795,725cm ^-1

(Example 13a)
The slurry obtained by mixing 6.19 g (60 mmol) of N-methyl-DL-alanine manufactured by Combi-Blocks with 40 mL of methanol is cooled in an ice bath, and then 14.28 g (120 mmol) of thionyl chloride is slowly added dropwise. The reaction was carried out to obtain a reaction solution. During the dropping, the reaction solution became a transparent solution, and the mixture was stirred as it was at room temperature overnight. Next, the obtained reaction solution was concentrated to obtain 8.3 g of a colorless viscous liquid of methyl ester hydrochloride of N-methyl-DL-alanine. The obtained methyl ester hydrochloride of N-methyl-DL-alanine was used as it was in the next reaction.
8.3 g (54 mmol) of methyl ester hydrochloride of N-methyl-DL-alanine was dissolved in 20 mL of water, an aqueous solution of 11.94 g (86.5 mmol) of potassium carbonate dissolved in 20 mL of water was added, and the mixture was added at room temperature for 1 hour. Stirred. After cooling in an ice bath, 5.38 g (59.4 mmol) of acrylic acid chloride was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours. Then, using ethyl acetate, each layer was separated by extraction, and the ethyl acetate layer was separated. The obtained ethyl acetate layer was washed with saturated brine and concentrated to obtain 6.0 g of a pale yellow liquid.
Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. is filled, purified by column chromatography using hexane and ethyl acetate as an eluent, and cured by the following structural formula (g1-1). 4.1 g (yield: about 44%) of a colorless liquid of the sex compound was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.43 / 1.49 (d, 3H), 2.91 / 3.03 (s, 3H), 3.72 / 3.75 (s, 3H), 4. 68 / 5.29 (q, 1H), 5.68-5.76 (m, 1H), 6.22-6.39 (m, 1H), 6.49-6.63 (m, 1H)
IR (NaCl): 2989,2952,1742,1651,1614,1446,1416,1332,1281,1211,1096,981,845,796cm ^-1

(Example 14a)
The slurry obtained by mixing 6.19 g (60 mmol) of N-methyl-DL-alanine manufactured by Combi-Blocks with 40 mL of ethanol is cooled in an ice bath, and then 14.28 g (120 mmol) of thionyl chloride is slowly added dropwise. The reaction was carried out to obtain a reaction solution. During the dropping, the reaction solution became a transparent solution, and then a white solid was precipitated to form a slurry. When it was stirred at room temperature overnight, the white solid dissolved and became transparent. The obtained reaction solution was concentrated to obtain 10.3 g of a colorless solid of ethyl ester hydrochloride of N-methyl-DL-alanine. The obtained ethyl ester hydrochloride of N-methyl-DL-alanine was used as it was in the next reaction.
Next, 10.3 g (61.4 mmol) of ethyl ester hydrochloride of N-methyl-DL-alanine was dissolved in 12 mL of water, and an aqueous solution of 15.28 g (110.6 mmol) of potassium carbonate in 25 mL of water was added. The mixture was stirred at room temperature for 1 hour. After cooling in an ice bath, 6.11 g (67.5 mmol) of acrylate chloride was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours. Then, using ethyl acetate, each layer was separated by extraction, and the ethyl acetate layer was separated. The obtained ethyl acetate layer was washed with saturated brine and concentrated to obtain 11.5 g of a pale yellow liquid.
Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. is filled, purified by column chromatography using hexane and ethyl acetate as an eluent, and cured by the following structural formula (g1-2). 8.1 g (yield: about 71%) of a colorless liquid of the sex compound was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.27 (t, 3H), 1.43 / 1.48 (d, 3H), 2.91 / 3.03 (s, 3H), 4.14-4. 22 (m, 2H), 4.66 / 5.29 (q, 1H), 5.67-5.75 (m, 1H), 6.22-6.38 (m, 1H), 6.50- 6.63 (m, 1H)
IR (NaCl): 2984,2941,1738,1651,1613,1447,1416,1378,1329,1281,1203,1094,1023,981,859,796cm ^-1

(Example 15a)
The slurry obtained by mixing 6.19 g (60 mmol) of N-methyl-DL-alanine manufactured by Combi-Blocks with 40 mL of isopropyl alcohol was cooled in an ice bath, and then 14.28 g (120 mmol) of thionyl chloride was slowly added. The reaction solution was obtained by dropping and reacting. During the dropping, the reaction solution became a transparent solution, and then a white solid was precipitated to form a slurry. The mixture was stirred at room temperature overnight, but the white solid did not dissolve and remained in a slurry state. The obtained reaction solution was concentrated to obtain 10.0 g of a colorless solid of isopropyl ester hydrochloride of N-methyl-DL-alanine. The obtained N-methyl-DL-alanine isopropyl ester hydrochloride was used as it was in the next reaction.
Next, 10.0 g (55 mmol) of isopropyl ester hydrochloride of N-methyl-DL-alanine was dissolved in 12 mL of water, an aqueous solution of 13.69 g (99.1 mmol) of potassium carbonate dissolved in 25 mL of water was added, and the temperature was lowered to room temperature. Was stirred for 1 hour. After cooling in an ice bath, 5.48 g (60.6 mmol) of acrylic acid chloride was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours. Then, using ethyl acetate, each layer was separated by extraction, and the ethyl acetate layer was separated. The obtained ethyl acetate layer was washed with saturated brine and concentrated to obtain 5.5 g of a light brown liquid.
Further, 300 g of silica gel C-300 manufactured by Wako Pure Chemical Industries, Ltd. is filled, purified by column chromatography using hexane and ethyl acetate as an eluent, and cured by the following structural formula (g1-5). A light brown liquid of the sex compound (1.9 g) (yield: about 17%) was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ1.25 (d, 6H), 1.41 / 1.46 (d, 3H), 2.90 / 3.02 (s, 3H), 4.99-5. 07 (m, 1H), 4.62 / 5.27 (q, 1H), 5.67-5.75 (m, 1H), 6.22-6.38 (m, 1H), 6.50- 6.63 (m, 1H)
IR (NaCl): 2892, 2940, 1735, 1652, 1614, 1466, 1453, 1415, 1375, 1235, 1281, 1207, 1109, 1018, 981, 910, 856, 828, 796 cm ^-1

(Comparative Example 1a)
Commercially available N, N-diethylacrylamide (manufactured by KJ Chemicals Co., Ltd.) represented by the following structural formula (1) was used as the compound of Comparative Example 1a.

(Comparative Example 2a)
Acrylamide represented by the following structural formula (2) was synthesized by the same method as in Example 1 described in JP-A-2015-13980 to obtain a compound of Comparative Example 2a.

(Comparative Example 3a)
Acrylamide represented by the following structural formula (3) was synthesized by the same method as in Example 5 described in JP-A-2015-13980 to obtain a compound of Comparative Example 3a.

The obtained curable compound was evaluated for viscosity, odorlessness, and safety as follows. The results are shown in Table 1 below.

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

<Evaluation of odor>
The odor of the obtained curable compound was confirmed by the following procedures (1) to (3), and "no odor" was evaluated based on the following evaluation criteria.
(1) About 100 mg (0.1 g) of each compound was weighed in a 50 mL 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 is felt or it is not unpleasant to feel it △: Discomfort is caused by the peculiar odor ×: Strong discomfort is caused by the peculiar odor

<Safety evaluation>
The curable compounds of Example 1a, Example 4a, Comparative Example 1a, and Comparative Example 2a were subjected to a limit test based on the acute oral toxicity test (OECD TG423) by the toxicity grading method as follows to determine the safety. evaluated.

[Limited test based on acute oral toxicity test]
<< Animals used >>
Regarding the curable compound of the present invention as a test substance, 24 females of 5-week-old Slc: Wistar / ST system rats were ordered from Nippon SLC Co., Ltd. as animals to be used. The animals used were acclimatized for one week. No abnormalities were observed in any of the animals during the acclimatization period.
Using the body weight measured 2 days before the start of administration, the animals were divided into 4 groups (6 animals / group) so that the body weight of the individual was within ± 20% of the average body weight of the whole by a random sampling method by body weight group. Animals that were excluded from the grouping were excluded from the study.
Animals used were identified by applying oil-based ink to the tail throughout the test period, while cages were labeled and identified.

<< Breeding environment >>
The animals used were quarantined and acclimated throughout the entire breeding period, with a temperature of 19 ° C to 25 ° C, a relative humidity of 40% to 70%, a ventilation rate of 10 to 15 times / hour, and a light-dark cycle at 12-hour intervals (lights up at 7 o'clock). It was bred in the breeding room of the barrier system set to (19:00 off).
A polycarbonate cage was used as the breeding cage. The animals used were bred at 6 animals / cage.
As the feed, solid samples for mice and rats (trade name: Lab MR Stock, manufactured by Nosan Corporation) were used, and the animals used were allowed to freely ingest.
Cages and bedding were replaced at the time of grouping and at the time of removal from the breeding room, and water bottles and racks were replaced at the time of grouping.

[Test method]
<< Group composition >>
The group composition used in the limited test is shown below.
-Group 1 Example 1a: Curable compound represented by the test substance structural formula (a1-1), dose: 2,000 mg / kg body weight, number of animals used: 6-Group 2 Example 4a: test Curable compound represented by the material structural formula (d1-1), dose: 2,000 mg / kg body weight, number of animals used: 6 ・ Group 3 Comparative Example 1a: Test substance represented by the structural formula (1) N, N-diethylacrylamide, dose: 2,000 mg / kg body weight, number of animals used: 6-Group 4 Comparative Example 2a: acrylamide represented by the test substance structural formula (2), dose: 2, 000mg / kg body weight, number of animals used: 6

<< Preparation of test substance >>
100 mg of the test substance was weighed in a measuring flask, water was added as a solvent, and the mixture was quantified to 1 mL to prepare a preparation solution having an adjusted concentration of 100 mg / mL. The test substance preparation solution was prepared on the day of administration.

<< Administration >>
The animals used were fed only with water and fasted for about 17 hours before administration. After fasting, the body weight was measured, and the test substance was orally administered once by force using a gastric sonde. No feed was given for another 3-4 hours after administration.
Administration was performed at a dose of 2,000 mg / kg body weight, and 6 animals used were used per test substance.

<< Observation >>
All animals used in the test were observed at least once a day for 14 days from the start date of administration. In the calculation method of the observation date, the administration start date was set as the first day.
The number of animals that died during the test period was calculated.

From the results in Table 1, it can be seen that the curable compounds of Examples 1a to 15a have a low viscosity, a low odor, are easy to handle, and are highly safe.

(Examples 1b to 15b and Comparative Examples 1b to 3b)
-Preparation of curable composition-
950 mg of each curable compound of Examples 1a to 15a and Comparative Examples 1a to 3a and a polymerization initiator (trade name: IRGACURE 907, component name: 2-methyl-1- [4- (methylthio) phenyl] -2- 50 mg of morpholinopropane-1-one (manufactured by BASF Japan Ltd.) was mixed using a magnetic stirrer to prepare cured compositions of Examples 1b to 15b and Comparative Examples 1b to 3b.

The curability and curability of each of the curable compositions of Examples 1b to 15b and Comparative Examples 1b to 3b were evaluated as follows. The results are shown in Table 2 below.

<Evaluation of polymerizable property>
Each curing type using a measuring device that combines a differential scanning calorimeter (device name: DSC-7020, manufactured by Seiko Instruments Inc.) and a spot light source (device name: LA-410UV, manufactured by Hayashi Clock Industry Co., Ltd.). The "polymerizability" of the composition was evaluated.
Specifically, the calorific value when the curable 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 the calorific value associated with the polymerization of the curable compound as well as the calorific value associated with the irradiation with ultraviolet rays. Therefore, the sample for which the 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 curable compound was measured. Then, the calorific value associated with the polymerization of the curable 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 of the maximum calorific value was defined as T ₁ [sec], which was used as an index for comparing the speed of polymerization.

<Evaluation of curability>
Each curable composition using a viscoelasticity measuring device (device 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 curability of was evaluated.
Specifically, after sandwiching the sample in a gap of 10 μm using a cone plate having a diameter of 20 mm, ultraviolet rays having a wavelength of 365 nm were irradiated 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 obtained from the measurement results and used as an index of the curing level.
Further, the energy of the ultraviolet rays irradiated until the storage elastic modulus was saturated, that is, the curing energy, was ^{calculated from the product of the intensity of the ultraviolet rays (50 mW / cm 2} ) and the time [seconds] of the irradiation of the ultraviolet rays.

From the results in Table 2 above, it can be seen that the curable compositions of Examples 1b to 15b using the curable compounds of Examples 1a to 15a are excellent in the balance between the polymerizable property and the curable property. This is because the tertiary acrylamide structure, which does not have a ring structure, realizes low viscosity, and the ester structure introduced into the molecule suppresses volatility, achieving both reduction of odor and low viscosity. Conceivable. Further, this ester structure provides a curable composition having excellent reactivity and curability, and having a very well-balanced combination of odor reduction, safety and low viscosity.

(Examples 1c to 15c)
-Making black ink-
100 parts by mass of the curable compound of Examples 1a to 15a, 10 parts by mass of a polymerization initiator (trade name: IRGACURE 907, manufactured by BASF Japan Ltd.), and carbon black (trade name: MICROLITH Black CK, BASF Japan Ltd.) (Manufactured) 3 parts by mass were mixed to obtain black inks of Examples 1c to 15c.

(Examples 1d to 15d)
-Making blue ink-
100 parts by mass of the curable compound of Examples 1a to 15a, 10 parts by mass of a polymerization initiator (trade name: IRGACURE 907, manufactured by BASF Japan Ltd.), and a blue pigment (trade name: MICROLITH Blue 4G-K, BASF Japan Ltd.) (Manufactured) 3 parts by mass were mixed to obtain blue inks of Examples 1d to 15d.

<Ink curability evaluation 1>
The inks of Examples 1c to 15c and Examples 1d to 15d are inkjet-ejected onto the slide glass using an inkjet recording device (Head: GEN4 manufactured by Ricoh Printing Systems Co., Ltd.), and then UV. Using an irradiator (device 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 ink could be ejected by inkjet without any problem, and the ink image was sufficiently cured.
Further, each ink substantially corresponds to the one using each of the curable compositions of Examples 1b to 15b, but just in case, the polymerizable and curable properties are measured in the same manner as in the case of each of the curable compositions. As a result, it was confirmed that all of them were as excellent as the curable compositions of Examples 1b to 15b.

<Ink curability evaluation 2>
After immersing the tip of the dip pen in the inks of Examples 1c to 15c and Examples 1d to 15d and writing characters on PET film and plain paper, a UV irradiator (device name: LH6, Fusion Systems Japan). It was cured by irradiating it with ultraviolet rays having a wavelength of 365 nm at 200 mW / cm ^{2 using (manufactured by Co., Ltd.).}
As a result, the ink image was sufficiently cured.

ただし、前記一般式（１）中、Ｒ_１は炭素数１〜６のアルキル基を表し、Ｘは炭素数１〜６のアルキレン基を表し、Ｙは下記一般式（２）又は下記一般式（３）を表す。

ただし、前記一般式（２）中、Ｒ_２は炭素数１〜１０のアルキル基を表し、＊は前記Ｘとの結合部位を表す。

ただし、前記一般式（３）中、Ｒ_２は炭素数１〜１０のアルキル基を表し、＊は前記Ｘとの結合部位を表す。
＜２＞ 前記一般式（１）で表されるアクリルアミド化合物が、下記一般式（４）で表される化合物である前記＜１＞に記載の硬化型組成物である。

ただし、前記一般式（４）中、Ｒ_１は炭素数１〜６のアルキル基を表し、Ｘは炭素数１〜３のアルキレン基を表し、Ｒ_２は炭素数１〜４のアルキル基を表す。
＜３＞ 前記一般式（４）中のＲ_１が炭素数１〜３のアルキル基、及びＲ_２が炭素数１〜３のアルキル基である前記＜２＞に記載の硬化型組成物である。
＜４＞ 前記一般式（４）中のＸがメチレン基、及びメチルメチレン基のいずれかである前記＜２＞から＜３＞のいずれかに記載の硬化型組成物である。
＜５＞ 前記一般式（４）で表されるアクリルアミド化合物が、下記構造式（ｄ１−１）、下記構造式（ｄ１−２）、下記構造式（ｇ１−１）、下記構造式（ｇ１−２）、及び下記構造式（ｇ１−５）で表される化合物の少なくともいずれかである前記＜２＞から＜４＞のいずれかに記載の硬化型組成物である。

＜６＞ 前記一般式（１）で表されるアクリルアミド化合物が、下記構造式（ａ１−１）で表される化合物である前記＜１＞に記載の硬化型組成物である。

＜７＞ 前記一般式（１）で表されるアクリルアミド化合物が、下記構造式（ａ１−４）で表される化合物である前記＜１＞に記載の硬化型組成物である。

＜８＞ 前記一般式（１）で表されるアクリルアミド化合物が、下記構造式（ａ６−１）で表される化合物である前記＜１＞に記載の硬化型組成物である。

＜９＞ 前記＜１＞から＜８＞のいずれかに記載の硬化型組成物を含有することを特徴とする硬化型インクである。
＜１０＞ インクジェット用である前記＜９＞に記載に記載の硬化型インクである。
＜１１＞ 前記＜１＞から＜８＞のいずれかに記載の硬化型組成物、及び前記＜９＞から＜１０＞のいずれかに記載の硬化型インクの少なくともいずれかを収容してなることを特徴とする収容容器である。
＜１２＞ 前記＜１＞から＜８＞のいずれかに記載の硬化型組成物、及び前記＜９＞から＜１０＞のいずれかに記載の硬化型インクの少なくともいずれかを収容する収容部と、エネルギーを付与するための付与手段と、を有することを特徴とする２次元又は３次元の像形成装置である。
＜１３＞ 前記＜１＞から＜８＞のいずれかに記載の硬化型組成物、及び前記＜９＞から＜１０＞のいずれかに記載の硬化型インクの少なくともいずれかにエネルギーを付与して２次元又は３次元の像を形成することを特徴とする２次元又は３次元の像形成方法である。
＜１４＞ 前記＜１＞から＜８＞のいずれかに記載の硬化型組成物、及び前記＜９＞から＜１０＞のいずれかに記載の硬化型インクの少なくともいずれかを用いて形成されることを特徴とする硬化物である。
＜１５＞ 基材上に前記＜１４＞に記載の硬化物からなる表面加飾が施されてなることを特徴とする加飾体である。
＜１６＞ 下記一般式（１）で表されるアクリルアミド化合物であることを特徴とする硬化性化合物である。

ただし、前記一般式（１）中、Ｒ_１は炭素数１〜６のアルキル基を表し、Ｘは炭素数１〜６のアルキレン基を表し、Ｙは下記一般式（２）又は下記一般式（３）を表す。

ただし、前記一般式（２）中、Ｒ_２は炭素数１〜１０のアルキル基を表し、＊は前記Ｘとの結合部位を表す。

ただし、前記一般式（３）中、Ｒ_２は炭素数１〜１０のアルキル基を表し、＊は前記Ｘとの結合部位を表す。
＜１７＞ 前記一般式（１）で表されるアクリルアミド化合物が、下記一般式（４）で表される化合物である前記＜１６＞に記載の硬化性化合物である。

ただし、前記一般式（４）中、Ｒ_１は炭素数１〜６のアルキル基を表し、Ｘは炭素数１〜３のアルキレン基を表し、Ｒ_２は炭素数１〜４のアルキル基を表す。
＜１８＞ 前記一般式（４）中のＲ_１が炭素数１〜３のアルキル基、及びＲ_２が炭素数１〜３のアルキル基である前記＜１７＞に記載の硬化性化合物である。
＜１９＞ 前記一般式（４）中のＸがメチレン基、及びメチルメチレン基のいずれかである前記＜１７＞から＜１８＞のいずれかに記載の硬化性化合物である。
＜２０＞ 前記一般式（４）で表されるアクリルアミド化合物が、下記構造式（ｄ１−１）、下記構造式（ｄ１−２）、下記構造式（ｇ１−１）、下記構造式（ｇ１−２）、及び下記構造式（ｇ１−５）で表される化合物の少なくともいずれかである前記＜１９＞に記載の硬化性化合物である。

＜２１＞ 前記一般式（１）で表されるアクリルアミド化合物が、下記構造式（ａ１−１）で表される化合物である前記＜１６＞に記載の硬化性化合物である。

＜２２＞ 前記一般式（１）で表されるアクリルアミド化合物が、下記構造式（ａ１−４）で表される化合物である前記＜１６＞に記載の硬化性化合物である。

＜２３＞ 前記一般式（１）で表されるアクリルアミド化合物が、下記構造式（ａ６−１）で表される化合物である前記＜１６＞に記載の硬化性化合物である。

Aspects of the present invention are, for example, as follows.
<1> A curable composition comprising an acrylamide compound represented by the following general formula (1).

However, in the general formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 6 carbon atoms, and Y represents the following general formula (2) or the following general formula ( Represents 3).

However, in the general formula (2), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a binding site with X.

However, in the general formula (3), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a binding site with X.
<2> The curable composition according to <1>, wherein the acrylamide compound represented by the general formula (1) is a compound represented by the following general formula (4).

However, in the general formula (4), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 3 carbon atoms, and R ₂ represents an alkyl group having 1 to 4 carbon atoms. ..
_{<3> The curable composition according to <2>, wherein R 1} in the general formula (4) is an alkyl group _{having 1 to 3 carbon atoms and R 2} is an alkyl group having 1 to 3 carbon atoms. ..
<4> The cured composition according to any one of <2> to <3>, wherein X in the general formula (4) is either a methylene group or a methylmethylene group.
<5> The acrylamide compound represented by the general formula (4) has the following structural formula (d1-1), the following structural formula (d1-2), the following structural formula (g1-1), and the following structural formula (g1-). 2), and the curable composition according to any one of <2> to <4>, which is at least one of the compounds represented by the following structural formula (g1-5).

<6> The curable composition according to <1>, wherein the acrylamide compound represented by the general formula (1) is a compound represented by the following structural formula (a1-1).

<7> The curable composition according to <1>, wherein the acrylamide compound represented by the general formula (1) is a compound represented by the following structural formula (a1-4).

<8> The curable composition according to <1>, wherein the acrylamide compound represented by the general formula (1) is a compound represented by the following structural formula (a6-1).

<9> A curable ink comprising the curable composition according to any one of <1> to <8>.
<10> The curable ink according to the above <9>, which is for inkjet.
<11> Containing at least one of the curable composition according to any one of <1> to <8> and the curable ink according to any one of <9> to <10>. It is a storage container characterized by.
<12> With the accommodating portion for accommodating at least one of the curable composition according to any one of <1> to <8> and the curable ink according to any one of <9> to <10>. , A two-dimensional or three-dimensional image forming apparatus, characterized by having an applying means for applying energy.
<13> Energy is applied to at least one of the curable composition according to any one of <1> to <8> and the curable ink according to any one of <9> to <10>. It is a two-dimensional or three-dimensional image forming method characterized by forming a two-dimensional or three-dimensional image.
<14> Formed using at least one of the curable composition according to any one of <1> to <8> and the curable ink according to any one of <9> to <10>. It is a cured product characterized by this.
<15> A decorative body characterized in that a surface decoration made of the cured product according to <14> is applied on a base material.
<16> A curable compound characterized by being an acrylamide compound represented by the following general formula (1).

However, in the general formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 6 carbon atoms, and Y represents the following general formula (2) or the following general formula ( Represents 3).

However, in the general formula (2), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a binding site with X.

However, in the general formula (3), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a binding site with X.
<17> The acrylamide compound represented by the general formula (1) is the curable compound according to the above <16>, which is a compound represented by the following general formula (4).

However, in the general formula (4), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents an alkylene group having 1 to 3 carbon atoms, and R ₂ represents an alkyl group having 1 to 4 carbon atoms. ..
_{<18> The curable compound according to <17>, wherein R 1} in the general formula (4) is an alkyl group _{having 1 to 3 carbon atoms and R 2} is an alkyl group having 1 to 3 carbon atoms.
<19> The curable compound according to any one of <17> to <18>, wherein X in the general formula (4) is either a methylene group or a methylmethylene group.
<20> The acrylamide compound represented by the general formula (4) has the following structural formula (d1-1), the following structural formula (d1-2), the following structural formula (g1-1), and the following structural formula (g1-). 2) and the curable compound according to <19>, which is at least one of the compounds represented by the following structural formula (g1-5).

<21> The acrylamide compound represented by the general formula (1) is the curable compound according to the above <16>, which is a compound represented by the following structural formula (a1-1).

<22> The acrylamide compound represented by the general formula (1) is the curable compound according to <16>, which is a compound represented by the following structural formula (a1-4).

<23> The acrylamide compound represented by the general formula (1) is the curable compound according to the above <16>, which is a compound represented by the following structural formula (a6-1).

The curable composition according to any one of <1> to <8>, the curable ink according to any one of <9> to <10>, the storage container according to <11>, and the above <12>. > The two-dimensional or three-dimensional image forming apparatus, the two-dimensional or three-dimensional image forming method according to <13>, the cured product according to <14>, and the decoration according to <15>. According to the body and the curable compound according to any one of <16> to <23>, the conventional problems can be solved and the object of the present invention can be achieved.

Japanese Unexamined Patent Publication No. 2015-013980

Claims (12)

A curable composition comprising an acrylamide compound represented by the following general formula (1).

However, in the general formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms , and Y represents the following general formula (2) or the following general formula (3). When Y represents the following general formula (2), X represents an alkylene group having 1 to 6 carbon atoms, and when Y represents the following general formula (3), X represents a methylmethylene group, a butylene group, and a hexylene group. Represents one selected from.

However, in the general formula (2), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a binding site with X.

However, in the general formula (3), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a binding site with X. The curable composition according to claim 1, wherein the acrylamide compound represented by the general formula (1) is a compound represented by the following general formula (4).

However, in the general formula (4), R ₁ represents an alkyl group having 1 to 6 carbon atoms, X represents a methylmethylene group , and R ₂ represents an alkyl group having 1 to 4 carbon atoms. _{The cured composition according to claim 2, wherein R 1} in the general formula (4) is an alkyl group _{having 1 to 3 carbon atoms and R 2} is an alkyl group having 1 to 3 carbon atoms. The curable composition according to any one of claims 1 to 3, wherein the acrylamide compound represented by the general formula (1) is at least one of the compounds represented by the following structural formula.

Acrylamide compound represented by the general formula (4) is, under Symbol structural formula (g1-1), the following structural formula (g1-2), and at least one of the compounds represented by the following structural formula (G1-5) The curable composition according to any one of claims 2 to 3.

A curable ink comprising the curable composition according to any one of claims 1 to 5. The curable ink according to claim 6, which is for inkjet. A storage container comprising at least one of the curable composition according to any one of claims 1 to 5 and the curable ink according to any one of claims 6 to 7. An accommodating portion for accommodating at least one of the curable composition according to any one of claims 1 to 5 and the curable ink according to any one of claims 6 to 7, and an imparting means for imparting energy. And, a two-dimensional or three-dimensional image forming apparatus characterized by having. Energy is applied to at least one of the curable composition according to any one of claims 1 to 5 and the curable ink according to any one of claims 6 to 7 to form a two-dimensional or three-dimensional image. A two-dimensional or three-dimensional image forming method, characterized in that. A cured product, which is formed by using at least one of the curable composition according to any one of claims 1 to 5 and the curable ink according to any one of claims 6 to 7. A curable compound characterized by being an acrylamide compound represented by the following general formula (1).

However, in the general formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms , and Y represents the following general formula (2) or the following general formula (3). When Y represents the following general formula (2), X represents an alkylene group having 1 to 6 carbon atoms, and when Y represents the following general formula (3), X represents a methylmethylene group, a butylene group, and a hexylene group. Represents one selected from.

However, in the general formula (2), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a binding site with X.

However, in the general formula (3), R ₂ represents an alkyl group having 1 to 10 carbon atoms, and * represents a binding site with X.

Images