JP2014210735A - (meth)acrylic acid ester compound, active energy ray-curable composition and ink for inkjet recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new (meth)acrylic acid ester compound as a polymerizable compound (monomer compound) in a liquid state at normal temperature which is excellent in photopolymerization reactivity and curability by an active energy ray and is improved in odor.SOLUTION: There is provided a (meth)acrylic acid ester compound having a urea structure represented by the following formula(1): [wherein, R, Rand Rrepresent any one of a hydrogen atom, a substituted or unsubstituted alkyl structure, a cycloalkyl structure and a hydrocarbon structure containing an aromatic ring; Rand Rmay be linked to form a ring structure; Rmay form a ring structure with Ror R; and Rmay form a ring structure with a bond of the nitrogen atom to which it is bonded.]

Description

  The present invention relates to a novel (meth) acrylic acid ester compound (polymerizable compound / monomer compound), an active energy ray-curable composition using the same, and an ink for ink jet recording.

  There are various methods for forming an image on a recording medium such as paper, such as an electrophotographic method, a sublimation recording method, a thermal transfer recording method, and an ink jet recording method. Among these, the ink jet recording method has high ink consumption efficiency and excellent resource saving, and can reduce the ink cost per unit recording. However, when water-based ink is used, there are various problems such as drying property and paper waving. There are inks that use an organic solvent instead of water, but there are other problems such as evaporation of a fixed solvent.

  Therefore, in recent years, an ink jet recording system using an active energy ray curable ink has attracted attention. The active energy ray curable ink is described in various books, literatures, etc. as an ultraviolet curable ink composition as an example, and usually contains a polymerization initiator and a monomer as essential components, and if necessary, a pigment, an oligomer and a polymer. In addition, components such as a sensitizer are blended (Non-Patent Documents 1 and 2, etc.).

  The monomer component uses a plurality of monomers from the viewpoints of curing speed (sensitivity), ink viscosity, film properties after curing, etc., a low molecular weight monomer with low viscosity and excellent reactivity, and a polyfunctional and molecular weight Often used in combination with large monomers. Since the monomer is a main component that occupies nearly 80% by mass of the ink for ink jet recording, in addition to material development, development relating to its blending (combination) is also being actively conducted.

  For example, an invention using a trifunctional or higher functional (meth) acrylic acid ester or amide compound having an alkylene oxide group in the molecule (Patent Document 1), a trifunctional or higher functional (meth) acrylic acid having an alkylene oxide group in the molecule Invention (patent document 2) which combines the ester or amide of a monofunctional (meth) acrylic acid which has a C6-C12 alkyl part (patent document 2), the aliphatic (meth) acrylate compound which has a secondary hydroxyl group, and intramolecular In combination with a nitrogen atom and a compound having a polymerizable unsaturated bond (Patent Document 3), an invention using a polymerizable compound having a polymerizable unsaturated bond and an amino group in the molecule (Patent Document 4), etc. Proposed.

  It has also been proposed to use a monomer compound having a urethane structure. For example, inventions containing urethane acrylate oligomers (Patent Documents 5 and 6) and inventions using low molecular weight (meth) acrylate monomers having a urethane structure ( Patent Document 7) has been proposed. Furthermore, an invention using a monomer having an aliphatic ring structure for the purpose of improving properties such as high curability and flexibility of a cured film, solvent resistance and adhesion to a substrate (Patent Document 8), dioxolane and dioxane An invention using a monomer having a heterocyclic structure such as (Patent Document 9), an invention using two or more types of monomers having an aliphatic ring structure, a heterocyclic structure, and an aromatic ring structure (Patent Document 10) is also proposed. ing.

  It has also been proposed to use a polymerizable compound (monomer) having two different polymerizable functional groups in the molecule of the polymerizable compound, and a compound having both a (meth) acrylate group and a vinyl ether group is used. It has been proposed. (Patent Documents 11 to 14)

When the conventional polymerizable compound (monomer compound) is used in ink, its odor (odor) is also an important issue. In general, various active energy ray curable inks contain a large amount of a low molecular weight reactive monomer called a diluent, which also serves as a solvent, and maintain ink physical properties such as viscosity in an appropriate state. However, such low molecular weight monomer compounds often have a specific odor and are uncomfortable.
In addition, since the low molecular weight monomer compound functions as a solvent in the ink, it is compatible with various materials included in the ink composition (monomer compound used together, polymerization initiator, various activators, and additives). However, for example, if the hydrophilicity of the monomer compound is made too high by introducing a strong polar structure or introducing a large number of polar structures, the solubility in other ink constituent materials may decrease, Crystallization (solidification) and an increase in viscosity are caused by an increase in the interaction between the molecules, and the suitability for ink use is deteriorated.

Since the odor of chemical substances is recognized by human detection of the compound molecules scattered in the air, the compound itself is not suitable for those having a specific odor such as the monomer compound. It is important that it is difficult to scatter in the air. Therefore, for example, by increasing the molecular weight of the monomer compound or introducing a polar functional group to strengthen the intermolecular interaction, suppressing the scattering of the monomer compound into the air improves the odor of the ink. It will be one of the ways to do this. However, when an ink is prepared only with a high molecular weight monomer compound, the viscosity becomes high, which is not suitable for an application requiring a low viscosity such as an ink for ink jet recording. In addition, introduction of a polar structure that forms a strong hydrogen bond into a molecule may cause the above-described problems.
Therefore, the present invention provides a novel (meth) acrylic acid ester compound as a polymerizable compound (monomer compound) that is excellent in photopolymerization reactivity and curability by active energy rays and has improved odor and is liquid at room temperature. With the goal.

〔上記式中、Ｒ₁、Ｒ₂は水素原子、又は置換もしくは無置換のアルキル構造、シクロアルキル構造、芳香環を含む炭化水素構造のいずれかを示し、Ｒ₁とＲ₂が連結して環構造を形成することもできる。Ｒ₃は、水素原子、又は置換もしくは無置換のアルキル構造、シクロアルキル構造、芳香環を含む炭化水素構造のいずれかを示し、Ｒ₁又はＲ₂との間で環構造を形成することもできる。また、Ｒ₃は、結合している窒素原子の結合手との間で環構造を形成することもできる。ただし、Ｒ₁、Ｒ₂は同時に水素原子であることはなく、上記ウレア構造においてカルボニル基に結合している２つの窒素原子の内、少なくとも１つは水素原子と結合していない。〕 As a result of intensive studies, the present inventors have reduced the unpleasant odor peculiar to the monomer by the (meth) acrylic acid ester compound having a specific urea structure in the molecular structure of the polymerizable compound, and are reactive to active energy rays. It was also found that a polymerizable compound that is liquid (has fluidity) at room temperature with excellent curability can be obtained.
That is, the above problem is solved by the following invention [1].
[1] A (meth) acrylic acid ester compound having a urea structure represented by the following formula (1).

[In the above formula, R ₁ and R ₂ are each a hydrogen atom or a substituted or unsubstituted alkyl structure, cycloalkyl structure, or hydrocarbon structure containing an aromatic ring, and R ₁ and R ₂ are linked to form a ring. A structure can also be formed. R ₃ represents a hydrogen atom or a substituted or unsubstituted alkyl structure, cycloalkyl structure, or hydrocarbon structure containing an aromatic ring, and can form a ring structure with R ₁ or R _2. . R ₃ can also form a ring structure with the bond of the nitrogen atom to which R ₃ is bonded. However, R ₁ and R ₂ are not simultaneously hydrogen atoms, and at least one of the two nitrogen atoms bonded to the carbonyl group in the urea structure is not bonded to a hydrogen atom. ]

  According to the present invention, it is possible to provide a (meth) acrylic acid ester compound (polymerizable compound / monomer compound) which is excellent in photopolymerization reactivity and curability by active energy rays and is liquid at room temperature with improved odor.

2 is a ¹ H-NMR spectrum of an acrylate compound represented by formula (3) prepared in Synthesis Example 1. FIG. 3 is an IR spectrum of an acrylate compound represented by formula (3) prepared in Synthesis Example 1. 2 is a ¹ H-NMR spectrum of an acrylate compound represented by formula (2) prepared in Synthesis Example 3. 4 is an IR spectrum of an acrylate compound represented by formula (2) prepared in Synthesis Example 3.

Hereinafter, the present invention will be described in detail.
The polymerizable compound of the present invention can be cured (dried) by irradiation with active energy rays. And an active energy ray hardening-type composition is produced using this and it can apply to printing ink, various adhesive agents, a coating agent, etc.
The printing ink can be applied to various printing applications such as offset printing and screen printing. Among them, ink for ink jet recording that requires low viscosity characteristics (hereinafter sometimes referred to as “ink”), and this Suitable for an ink jet recording method using

〔５〕前記〔１〕〜〔４〕のいずれかに記載の重合性化合物を含むことを特徴とする活性エネルギー線硬化型組成物。
〔６〕前記〔５〕に記載の活性エネルギー線硬化型組成物を含有することを特徴とするインクジェット記録用インク。 And as preferable embodiment of the polymeric compound of this invention, the following [2]-[6] are included.
[2] The (meth) acrylic acid ester compound according to [1], wherein R ₁ and R ₂ in the formula (1) are not hydrogen atoms.
[3] The (meth) acrylic acid ester compound according to [1] 1 or [2], wherein R ₃ in the formula (1) is an alkyl structure or a hydrogen atom.
[4] The (meth) acrylic ester compound according to any one of [1] to [3], wherein the (meth) acrylic acid ester compound is a compound represented by the following formula (2) or formula (3): Acrylic ester compound.

[5] An active energy ray-curable composition comprising the polymerizable compound according to any one of [1] to [4].
[6] An inkjet recording ink comprising the active energy ray-curable composition according to [5].

〔上記式中、Ｒ₁、Ｒ₂は水素原子、又は置換もしくは無置換のアルキル構造、シクロアルキル構造、芳香環を含む炭化水素構造のいずれかを示し、Ｒ₁とＲ₂が連結して環構造を形成することもできる。Ｒ₃は、水素原子、又は置換もしくは無置換のアルキル構造、シクロアルキル構造、芳香環を含む炭化水素構造のいずれかを示し、Ｒ₁又はＲ₂との間で環構造を形成することもできる。また、Ｒ₃は、結合している窒素原子の結合手との間で環構造を形成することもできる。ただし、Ｒ₁、Ｒ₂はともに水素原子であることはなく、上記ウレア構造においてカルボニル基に結合している２つの窒素原子の内、少なくとも１つは水素原子と結合していない。〕 <Polymerizable compound>
The (meth) acrylic acid ester compound of the present invention has a urea structure represented by the following formula (1) in the molecular structure.

[In the above formula, R ₁ and R ₂ are each a hydrogen atom or a substituted or unsubstituted alkyl structure, cycloalkyl structure, or hydrocarbon structure containing an aromatic ring, and R ₁ and R ₂ are linked to form a ring. A structure can also be formed. R ₃ represents a hydrogen atom or a substituted or unsubstituted alkyl structure, cycloalkyl structure, or hydrocarbon structure containing an aromatic ring, and can form a ring structure with R ₁ or R _2. . R ₃ can also form a ring structure with the bond of the nitrogen atom to which R ₃ is bonded. However, R ₁ and R ₂ are not hydrogen atoms, and at least one of the two nitrogen atoms bonded to the carbonyl group in the urea structure is not bonded to a hydrogen atom. ]

The alkyl structure in R ₁ , R ₂ and R ₃ is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group.
As said cycloalkyl structure, a cyclohexyl group, a cyclopentyl group, etc. are preferable.
The hydrocarbon structure containing an aromatic ring is preferably a monocyclic group such as a phenyl group or a benzyl group.
Examples of the substituent of the hydrocarbon structure including an alkyl structure, a cycloalkyl structure, and an aromatic ring include a halogen atom such as a chlorine atom and a bromine atom, a hydroxyl group, an amino group, an ether structure, and an ester structure.
When R ₁ and R ₂ are linked to form a ring structure, and when R ₃ and R ₁ or R ₂ form a ring structure, the ring structure is formed through a heteroatom other than carbon. The ring formed may have a substituent containing a hetero atom. For example, the ring structure when R ₁ and R ₂ are linked to form a ring structure is preferably a monocyclic group such as a piperidine ring, a pyrrolidine ring, or a morpholine ring.
Preferred embodiments include those in which R ₁ and R ₂ in Formula (1) are not both hydrogen atoms, and more preferred embodiments include those in which R ₃ is an alkyl structure and a hydrogen atom. be able to. Particularly preferred embodiments include those represented by the above formulas (2) and (3).

In general, many (meth) acrylic acid ester compounds have a (meth) acrylic acid ester structure with an alkyl, cycloalkyl, or a hydrocarbon structure containing an aromatic ring as a parent structure. These compounds not only have a simple hydrocarbon structure as a host nucleus, but also realize properties suitable for various applications by introducing structures containing various heteroatoms, introducing branched structures, and increasing the molecular weight.
For example, for applications that require a hardened film with excellent strength, use polyfunctional oligomer type (meth) acrylic acid ester compounds with various modifications, or applications that require water solubility, There are provided (meth) acrylic acid ester compounds into which strong hydrophilic functional groups such as phosphoric acid esters and sulfonic acid esters are introduced.
In general, low molecular weight (meth) acrylic acid ester compounds having no polar structure have a low viscosity and are convenient as diluent monomers for ink jet ink compositions, but on the other hand, they are highly volatile and have a specific odor. Therefore, there is a problem when using ink. On the other hand, oligomer-type polyfunctional (meth) acrylic acid ester compounds have a very high viscosity and are not suitable for use as curable compositions, especially ink-jet ink compositions, and use low-molecular-weight diluent monomers as solvents. Therefore, it was necessary to control the viscosity. In this case, the low-viscosity diluent monomer compound often uses the above-described low-volatility monomer compound having high volatility, which may cause a problem of odor and volatilization of the low-molecular monomer component.
In addition, phosphate compounds, sulfonic acid esters, and monomer compounds introduced with a strong polar structure such as a hydroxyl group (OH) are less volatile and odorous, but have a high viscosity and are sometimes solid. In addition, there are problems such as poor compatibility with other compounding components used in the curable composition.

On the other hand, the (meth) acrylic acid ester compound of the present invention has a urea structure represented by the formula (1) in the molecule, and in this urea structure, R ₁ and R ₂ are simultaneously hydrogen atoms. In other words, at least one of the two nitrogen (N) atoms bonded to the carbonyl (C═O) group is not bonded to a hydrogen atom.
This urea structure is a functional group having polarity, and has a function of suppressing the volatility of the low molecular weight (meth) acrylate compound and the generation of odor. In addition, when at least one of the two nitrogen atoms in the urea structure does not have a bond with a hydrogen atom, the strong intermolecular interaction caused by the NH bond can be reduced, resulting in extremely high viscosity. It is considered that the liquid is prevented from solidifying and a fluid liquid state is realized.
This also applies to the case where R ₁ and R ₂ are hydrogen atoms at the same time. At least one of them is not a hydrogen atom, so that it has excellent fluidity and low odor by suppressing volatility. In particular, when both R ₁ and R ₂ are not hydrogen atoms, the effect of reducing odor by suppressing fluidity and volatility is further improved.
Furthermore, when two nitrogen atoms do not have any bonds with hydrogen atoms, a lower viscosity state can be realized, fluidity can be improved, and low odor can be realized by suppressing volatility. .

Further, although the reason why the (meth) acrylic acid ester compound of the present invention has the above-mentioned characteristics is not clear, it is considered that it is related to the degree of polarity due to the urea structure represented by the formula (1). It is done.
The characteristics of polymerizable compounds such as low molecular weight (meth) acrylic acid ester compounds are easily affected by the strength (degree) of the polar structure introduced into the molecule, and not only the fluidity, volatility and odor mentioned above. It is important for compatibility with other constituent materials when constituting the curable composition. For example, if the polar structure of the (meth) acrylic acid ester compound is very strong, the compatibility with other compounds may be inferior when constituting the curable composition, or the flow due to an increase in viscosity. It will cause sex decline.
As described above, the compatibility and fluidity with the compound are complicatedly related to the types, number, and molecular size (molecular weight) of polar structures, but it is difficult to quantitatively indicate the degree. The (meth) acrylic acid ester compound of the present invention is considered to be in an excellent region in the balance. From this, it can be said that the (meth) acrylic acid ester compound of the present invention is suitable for various inks.

  The (meth) acrylic acid ester compound of the present invention can be synthesized by various methods. For example, by reaction of a carbamoyl chloride compound with an amino alcohol compound (a compound having an amino group and an alcoholic OH structure in the same molecule). It can be synthesized by a condensation reaction of the resulting urea compound (intermediate) having a hydroxyl group (OH) and a (meth) acrylic acid compound. Specific examples of the carbamoyl chloride compound and amino alcohol compound that can be used in this case are given below, but the (meth) acrylic acid ester compound of the present invention is not limited thereto.

Carbamoyl chloride compounds

Amino alcohol compound In the formula, n represents an integer of 2 to 4, and a represents an integer of 1 to 2.

Although the preferable specific example of the (meth) acrylic acid ester compound of this invention is given to the following, the monomer compound of this invention is not limited to these. In the formula, n represents an integer of 2 to 4, and X represents a hydrogen atom or a methyl group.

Further, as described above, the (meth) acrylic acid ester compound of the present invention can be obtained using a commercially available hydroxyl group-containing urea compound as a starting material without using a carbamoyl chloride compound and an amino alcohol as raw materials. Such compounds can be mentioned.

<Polymerization initiator>
The (meth) acrylic acid ester compound of the present invention can be made into an active energy ray curable composition by adding a polymerization initiator, and this active energy ray curable composition can be used for ink for ink jet recording.
Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators and the like, and radical polymerization initiators and anionic polymerization initiators are preferable, and radical polymerization initiators are particularly preferable.

The polymerization initiator can be appropriately selected according to the type of the polymerizable compound and the intended use of the ink.
In the case of ink, the polymerization initiator is a compound that absorbs external energy and generates a polymerization initiating species. External energy used for initiating polymerization is roughly divided into heat or active energy rays, and a thermal polymerization initiator or a photopolymerization initiator is used, respectively. Active energy rays include γ rays, β rays, electron beams, ultraviolet rays, visible rays, and infrared rays. Moreover, a well-known compound can be used as a thermal-polymerization initiator and a photoinitiator.

  Preferred radical polymerization initiators include (a) aromatic ketones, (b) acylphosphine oxide compounds, (c) aromatic onium salt compounds, (d) organic peroxides, (e) thio compounds, (f) hexa An arylbiimidazole compound, (g) a ketoxime ester compound, (h) a borate compound, (i) an azinium compound, (j) a metallocene compound, (k) an active ester compound, (l) a compound having a carbon halogen bond, (m ) Alkylamine compounds and the like. These radical polymerization initiators may be used alone or in combination of two or more.

  Specific examples of the radical polymerization initiator include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy- 2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2- Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-ben Ru-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (t -Hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3'-di (T-Butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3 ' Di (t-butylperoxycarbonyl) benzophenone, 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime), 2- (4′-methoxystyryl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl)- 4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s- Triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2 -(P-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonyl) Phenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl 1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6 -Bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (η5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro -3- (1H-pyrrol-1-yl) phenyl] titanium, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzene Nzoyldiphenylphosphine oxide and the like.

  Among them, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (IRGACURE 819 manufactured by BASF Japan) or 2,4,6-trimethylbenzoyldiphenylphosphine oxide (DAROCUR TPO manufactured by BASF Japan) : Trade name), 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184: trade name, manufactured by BASF Japan Ltd.), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (BASF IRGACURE 907 (trade name) manufactured by Japan, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-ylphenyl) butan-1-one (IRGACURE manufactured by BASF Japan) 379: Product name) And the like are preferable because they are highly compatible with other components contained in the ink composition and can cure the ink with a small amount of ultraviolet irradiation.

  The polymerization initiator is preferably in the range of 1 to 50% by mass, more preferably in the range of 2 to 40% by mass with respect to the total mass of the polymerizable compound and other polymerizable compounds and colorants described later used as optional components. The range of 5 to 30% by mass is more preferable. Moreover, when using together a polymerization initiator and the sensitizer mentioned later, 200: 1 to 1: 200 are preferable, and, as for mass ratio of a polymerization initiator: sensitizer, 50: 1 to 1:50 are more preferable. Range.

  The content of the reactive monomer including the (meth) acrylic acid ester compound of the present invention in the ink is preferably 20 to 98% by mass, more preferably 30 to 90% by mass, and particularly preferably in the range of 30 to 80% by mass. . Moreover, (meth) acrylic acid ester may be used individually by 1 type, and may be used in combination of 2 or more type.

  In addition to the above-described components, other components can be blended in the ink of the present invention for the purpose of improving physical properties, as long as the effects of the present invention are not impaired. Hereinafter, these optional components will be described.

<Colorant>
The ink of the present invention may contain a colorant, whereby a colored image can be formed. There is no restriction | limiting in particular about a coloring agent, It can select suitably from arbitrary well-known coloring agents, such as a pigment, an oil-soluble dye, a water-soluble dye, and a disperse dye.
As the colorant, a pigment or an oil-soluble dye having excellent weather resistance and high color reproducibility is preferable, and a pigment is more preferable. Further, the colorant that can be suitably used in the ink composition of the present invention is a compound that does not function as a polymerization inhibitor for the polymerization reaction that is a curing reaction, from the viewpoint of not reducing the sensitivity of the curing reaction by active energy rays. It is preferable to select.
Although it does not specifically limit as a pigment, For example, the organic or inorganic pigment of the following number described in a color index is mentioned, According to the objective, it can select suitably and can be used.

  Examples of the red or magenta pigment include Pigment Red 3, 5, 19, 22, 31, 38, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, 53. : 1, 57: 1, 57: 2, 58: 4, 63: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 88, 104, 108, 112, 122, 123, 144 , 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13, 16, 20, 36, and the like.

Examples of the blue or cyan pigment include Pigment Blue 1,15,15: 1,15: 2,15: 3, 15: 4,15: 6,16,17-1,22,27,28,29,36. , 60, and the like.
Examples of the green pigment include Pigment Green 7, 26, 36, 50, and the like.
Examples of the yellow pigment include Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, and 137. , 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193, and the like.
Examples of the black pigment include Pigment Black 7, 28, 26, and the like. Examples of the white pigment include Pigment White 6, 18, 21, and the like.

  The oil-soluble dye that can be used in the ink of the present invention will be described. The oil-soluble dye as used herein means a dye that is substantially insoluble in water. Specifically, the solubility in water at 25 ° C. (the mass of the dye that can be dissolved in 100 g of water) is 1 g or less, preferably 0.5 g or less, more preferably 0.1 g or less. Accordingly, the oil-soluble dye means a water-insoluble dye or an oil-soluble dye, and among these, an oil-soluble dye is preferable.

  Among oil-soluble dyes, yellow dyes include, for example, phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heteryl azo dyes having open-chain active methylene compounds as coupling components, and open chains as coupling components. Examples include azomethine dyes having a type active methylene compound, methine dyes such as benzylidene dyes and monomethine oxonol dyes, quinone dyes such as naphthoquinone dyes, anthraquinone dyes, and other dye species such as quinophthalone dyes, Examples thereof include nitro / nitroso dyes, acridine dyes, acridinone dyes, and the like.

  Among the oil-soluble dyes, magenta dyes include, for example, phenols, naphthols, aryl or heteryl azo dyes having coupling components, pyrazolones, azomethine dyes having pyrazolotriazoles, arylidene dyes as coupling components Methine dyes such as styryl dyes, merocyanine dyes, oxonol dyes, carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, and dioxazine dyes And condensed polycyclic dyes.

  Among oil-soluble dyes, examples of cyan dyes include indoaniline dyes, indophenol dyes, or azomethine dyes having pyrrolotriazoles as coupling components, cyanine dyes, oxonol dyes, polymethine dyes such as merocyanine dyes, diphenylmethane dyes, Examples thereof include carbonium dyes such as triphenylmethane dyes and xanthene dyes, phthalocyanine dyes, anthraquinone dyes, aryl or heteryl azo dyes having phenols, naphthols and anilines as coupling components, and indigo / thioindigo dyes.

  Preferable specific examples of the oil-soluble dye include C.I. I. Solvent Black 3, 7, 27, 29 and 34, C.I. I. Solvent Yellow 14, 16, 19, 29, 30, 56, 82, 93 and 162, C.I. I. Solvent Red 1, 3, 8, 18, 24, 27, 43, 49, 51, 72, 73, 109, 122, 132 and 218, C.I. I. Solvent Violet 3, C.I. I. Solvent Blue 2,11,25,35,38,67 and 70, C.I. I. Solvent Green 3 and 7, C.I. I. Solvent Orange 2 etc. are mentioned.

  In the ink of the present invention, a disperse dye can be used as long as it is soluble in a water-immiscible organic solvent. Preferred examples thereof include C.I. I. Disperse Yellow 5,42,54,64,79,82,83,93,99,100,119,122,124,126,160,184: 1,186,198,199,201,204,224,237 , C.I. I. Disperse Orange 13, 29, 31: 1, 33, 49, 54, 55, 66, 73, 118, 119, 163, C.I. I. Disperse Red 54, 60, 72, 73, 86, 88, 91, 92, 93, 111, 126, 127, 134, 135, 143, 145, 152, 153, 154, 159, 164, 167: 1,177 , 181, 204, 206, 207, 221, 239, 240, 258, 277, 278, 283, 311, 323, 343, 348, 356, 362, C.I. I. Dispers Violet 33, C.I. I. Disperse Blue 56, 60, 73, 87, 113, 128, 143, 148, 154, 158, 165, 165: 1, 165: 2, 176, 183, 185, 197, 198, 201, 214, 224, 225 , 257, 266, 267, 287, 354, 358, 365, 368, C.I. I. Disperse Green 6: 1, 9 etc. are mentioned.

The colorant is preferably appropriately dispersed in the ink. For dispersing the colorant, various dispersing devices such as a ball mill, a sand mill, a ring mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, and a paint shaker can be used.
Further, it is possible to add a dispersant when dispersing the colorant. The type of the dispersant is not particularly limited, but a polymer dispersant is preferable. These dispersants are preferably added in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the colorant.
One or more colorants may be appropriately selected and used depending on the intended use of the ink.

  When using a colorant such as a pigment that remains solid in the ink, the average particle diameter of the colorant particles is preferably 0.005 to 0.5 μm, more preferably 0.01 to 0.45 μm, More preferably, selection of a colorant, a dispersant, and a dispersion medium, a dispersion condition, and a filtration condition are set so as to be 0.015 to 0.4 μm. By controlling the particle size, clogging of the head nozzle can be suppressed, and the storage stability, transparency, and curing sensitivity of the ink can be maintained.

  The content of the colorant is appropriately selected according to the purpose of use of the ink. However, in consideration of ink physical properties and colorability, generally, the content of the ink is preferably 0.5 to 10% by mass, and 1 to 8% by mass. % Is more preferable. In the case of a white ink composition using a white pigment such as titanium oxide as a colorant, the content of the colorant is preferably 5 to 30% by mass with respect to the entire ink in order to ensure concealment. -25 mass% is more preferable.

<Other polymerizable compounds (monomer compounds)>
The ink of the present invention can also contain a polymerizable compound other than the (meth) acrylic acid ester compound. In this case, it can use in the range of 0.01-100 (mass ratio) with respect to the (meth) acrylic acid ester compound 1 of this invention, Preferably, it is 0.1-50 (mass ratio). Examples of the polymerizable compound that can be used in combination include a radical polymerizable compound, a cationic polymerizable compound, and an anion polymerizable compound.
The radical polymerizable compound is not particularly limited as long as it is a compound having at least one ethylenically unsaturated bond capable of radical polymerization in the molecule, and includes those having a chemical form such as a monomer, an oligomer, and a polymer. The radically polymerizable compounds used in combination may be used alone or in combination of two or more at any ratio in order to improve the desired properties.

  Examples of the radical polymerizable compound include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, salts thereof, compounds derived therefrom, and ethylenically unsaturated groups. And radically polymerizable compounds such as unsaturated acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes.

  Specifically, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) propane, neopentyl glycol diacrylate, ethoxylation 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 diac Rate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate Acrylic acid derivatives such as 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 Relate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, methacrylic acid derivatives such as 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, N-methylolacrylamide, Examples include acrylamide derivatives such as diacetone acrylamide, 2-hydroxyethyl acrylamide, and acryloylmorpholine, and derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate. Commercially available products or known reactive monomers, oligomers, and polymers described in the text of Non-Patent Document 1 and materials such as the photoreactive material data edition can be used.

  Furthermore, it is also preferable to use a vinyl ether compound as the radical polymerizable compound. Suitable vinyl ether compounds include, for example, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol. Di- or trivinyl ether compounds such as divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, trimethylolpropane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octade Monovinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether-o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether, etc. Examples include vinyl ether compounds. A vinyl ether compound may be used individually by 1 type, or may be used in combination of 2 or more type as appropriate.

Examples of other polymerizable compounds that can be used in combination with the ink of the present invention include (meth) acrylic esters such as (meth) acrylic monomers or prepolymers, epoxy monomers or prepolymers, urethane monomers or prepolymers. Can do.
Specifically, 2-ethylhexyl diglycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl acrylate, hydroxypivalate neopentyl glycol diacrylate, 2-acryloyloxyethylphthalic acid, methoxypolyethylene glycol acrylate , Tetramethylol methane triacrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic 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, Noxypolyethylene glycol acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, propylene oxide adduct diacrylate of bisphenol A, ethylene oxide adduct diacrylate of bisphenol A, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, tolylene diisocyanate Nate urethane prepolymer, lactone-modified flexible acrylate, butoxyethyl acrylate, propylene glycol diglycidyl ether acrylic acid adduct, pentaerythritol triacrylate, hexamethylene diisocyanate urethane prepolymer, 2-hydroxyethyl acrylate, methoxydipropylene glycol Acrylate, ditrimethylolpropane tetraacrylate, pen Triacrylate, hexamethylene diisocyanate urethane prepolymer, stearyl acrylate, isoamyl acrylate, isomyristyl acrylate, isostearyl acrylate, lactone-modified acrylate.

  In addition, regarding the selection of the polymerization initiator and the polymerizable compound, in addition to the combination of the radical polymerizable compound and the radical polymerization initiator according to various purposes, the cationic polymerizable compound and the cationic polymerization start as shown below. It is also possible to use a radical / cation hybrid curable ink in combination with an agent or a radical / anion hybrid curable ink in which an anion polymerizable compound and an anionic polymerization initiator are used in combination.

The cationically polymerizable compound is not particularly limited as long as it is a compound that initiates a polymerization reaction with an acid generated from a photoacid generator and cures, and various known cationically polymerizable monomers known as photocationically polymerizable monomers are used. can do. Examples thereof include various epoxy compounds, vinyl ether compounds, oxetane compounds described in Non-Patent Document 1 and the like. As the cationic polymerization initiator (photoacid generator) used in combination with the cationic polymerizable compound, various known materials can be used, for example, aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium, phosphonium, and the like. B (C ₆ F ₅ ) ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ salt, sulfonate that generates sulfonic acid, halide that generates hydrogen halide, iron allene A complex etc. are mentioned. The said cationic polymerization initiator may be used independently and may use 2 or more types together.

  Examples of the anionic polymerizable compound include various epoxy compounds, lactone compounds, acrylic compounds, and methacrylic compounds, among which the acrylic compounds and methacrylic compounds exemplified as the radical polymerizable compound are preferable. Examples of the anionic polymerization initiator include so-called photobase generators such as orthonitrobenzyl carbamate derivatives, orthoacyloxyl derivatives, orthocarbamoyloxime amidine derivatives, and the like.

<Sensitizer>
A sensitizer can be added to the ink of the present invention in order to promote decomposition of the polymerization initiator by irradiation with actinic rays. A sensitizer absorbs a specific active energy ray and becomes an electronically excited state. The sensitizer in an electronically excited state is brought into contact with the polymerization initiator to cause electron transfer, energy transfer, heat generation, etc., thereby causing a chemical change of the polymerization initiator (decomposition, generation of radical, acid or base). ). As the sensitizer, a compound corresponding to the wavelength of the active energy ray that generates an initiation species in the polymerization initiator may be used. A sensitizing dye is preferable as the sensitizer, and examples thereof include those having an absorption wavelength in the 350 to 450 nm region as follows.

  Polynuclear aromatics (eg pyrene, perylene, triphenylene), xanthenes (eg fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg , Merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squaryliums (eg, squarylium), coumarins (Eg 7-diethylamino-4-methylcoumarin)

<Co-sensitizer>
The ink of the present invention may contain a co-sensitizer. The co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye to the active energy ray and suppressing the inhibition of polymerization of the polymerizable compound by oxygen. Examples of cosensitizers include amine compounds such as triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole. Thiols and sulfides such as 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, and β-mercaptonaphthalene, but are not limited thereto.

<Other ingredients>
If necessary, other components such as a polymerization inhibitor and a solvent can be added to the ink of the present invention. The polymerization inhibitor is added from the viewpoint of improving the storage stability (storage stability) of the ink. In addition, the ink of the present invention can be heated and reduced in viscosity as needed to be ejected, and a polymerization inhibitor is preferably added in order to prevent head clogging due to thermal polymerization in that case.
Examples thereof include hydroquinone, benzoquinone, p-methoxyphenol, TEMPO, TEMPOL, and cuperon Al. The addition amount of the polymerization inhibitor is preferably 200 to 20,000 ppm with respect to the total amount of the ink.
The viscosity of the ink of the present invention is preferably 7 to 30 mPa · s, and more preferably 7 to 25 mPa · s in the environment at the time of discharge when the discharge property in the ink jet apparatus is taken into consideration.

The ink of the present invention is preferably an active energy ray curable ink, and preferably contains no solvent. However, in order to improve properties such as adhesion between the cured ink and the recording medium, the ink is cured at a high speed. Only when there is no influence, a solvent can be contained. An organic solvent or water can be used as the solvent. The content of the organic solvent is in the range of 0.1 to 5% by mass, preferably 0.1 to 3% by mass, based on the entire ink.
Furthermore, as necessary, surfactants, leveling additives, matting agents, polyester resins, polyurethane resins, vinyl resins, acrylic resins, rubber resins, which are used for adjusting film properties, are known additives. Waxes and the like can be appropriately selected and added. Moreover, in order to improve the adhesiveness with respect to polyolefin, PET, etc., it is also possible to contain a tackifier (tack fire) without polymerization inhibition.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples. In the following examples, “%” is “mass%”.
In order to clarify the effect of the polymerizable compound of the present invention, the sample used for the evaluation was a composition that did not contain various additive components including a colorant necessary for making an ink.
¹ H-NMR was measured using ¹ H-NMR (500 MHz) manufactured by JEOL, and IR was measured using FT-IR Spectrum GX manufactured by PERKIN ELMER.

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）：δ１．１５（ｔ，６Ｈ），３．２７（ｑ，４Ｈ），３．４１（ｑ，２Ｈ），３．７１（ｔ，２Ｈ），４．８４−４．９２（ｂｓ，１Ｈ）
ＩＲ（ＮａＣｌ）：３３５３，２９７４，２９３３，２８７５，１７１２，１６２６，１５３８，１４６０，１４０９，１３７９，１３６２，１２８３，１２２２，１１９８，１０７４，１０２９，９３４，８７３，８４０，７６９，５８３ｃｍ^-1 [Synthesis Example 1]
Diethylcarbamoyl chloride (24.4 g, 180 mmol) was dissolved in pyridine (250 ml). To this solution, 2-aminoethanol (14.3 g, 234 mmol) was slowly added while cooling in a water bath, followed by stirring at room temperature for 24 hours. The reaction mixture was concentrated under reduced pressure, and the resulting solution was extracted with ethyl acetate (350 ml). The extract was concentrated to obtain a brown liquid. The resulting liquid was purified by column chromatography (Wakogel C300 200 g) to obtain pale yellow needles (10.5 g). This pale yellow needle crystal was confirmed to be a compound (intermediate-1) represented by the following structural formula from ¹ H-NMR and IR. The yield after purification was about 36%.

¹ H-NMR (CDCl ₃ ): δ 1.15 (t, 6H), 3.27 (q, 4H), 3.41 (q, 2H), 3.71 (t, 2H), 4.84-4 .92 (bs, 1H)
IR (NaCl): 3353, 2974, 2933, 2875, 1712, 1626, 1538, 1460, 1409, 1379, 1362, 1283, 1222, 1198, 1074, 1029, 934, 873, 840, 769, 583 cm ⁻¹

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）：δ１．１３（ｔ，６Ｈ），３．２６（ｑ，４Ｈ），３．５５（ｑ，２Ｈ），４．２９（ｔ，２Ｈ），４．７７−４．８３（ｂｓ，１Ｈ），５．８４−５．８８（ｍ，１Ｈ），６．１１−６．１７（ｍ，１Ｈ），６．４１−６．４５（ｍ，１Ｈ）
ＩＲ（ＮａＣｌ）：３３５２，２９７４，２９３３，２８７５，１７２６，１６３０，１５３３，１４５５，１４０７，１３７９，１３６２，１２６９，１１９０，１０９９，１０６７，９８５，８１１，７６６，５５２ｃｍ^-1 The obtained intermediate-1 (4.7 g, 29 mmol) was added to dehydrated dichloromethane (70 mL), the inside of the flask was replaced with argon gas, and then triethylamine (4.6 g, 45 mmol) was added. After cooling the mixture to about −10 ° C., acrylic acid chloride (3.3 g, 36 mmol) was slowly added dropwise so that the system temperature was −10 to −5 ° C., and then stirred at room temperature for 2 hours. did. The precipitate was removed by filtration, and the filtrate was washed with water, a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution, dried over sodium sulfate, and then concentrated under reduced pressure to give a brown oil. The resulting oil was purified by column chromatography (Wakogel C300 300 g) to give a pale yellow oil (2.8 g). The pale yellow oil was confirmed to be a compound represented by the following structural formula from ¹ H-NMR and IR below. The yield after purification was about 45%. The ¹ H-NMR spectrum of this compound is shown in FIG. 1, and the IR spectrum is shown in FIG.

¹ H-NMR (CDCl ₃ ): δ 1.13 (t, 6H), 3.26 (q, 4H), 3.55 (q, 2H), 4.29 (t, 2H), 4.77-4 .83 (bs, 1H), 5.84-5.88 (m, 1H), 6.11-6.17 (m, 1H), 6.41-6.45 (m, 1H)
IR (NaCl): 3352, 2974, 2933, 2875, 1726, 1630, 1533, 1455, 1407, 1379, 1362, 1269, 1190, 1099, 1067, 985, 811, 766, 552 cm ⁻¹

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）：δ１．１３（ｔ，６Ｈ），１．９５（ｓ，３Ｈ），３．２５（ｑ，４Ｈ），３．５５（ｑ，２Ｈ），４．２８（ｔ，２Ｈ），４．７１−４．７６（ｂｓ，１Ｈ），５．５８−５．６０（ｍ，１Ｈ），６．１５−６．３０（ｍ，１Ｈ）
ＩＲ（ＮａＣｌ）：３３５４，２９７５，２９３２，１７２０，１６３０，１５３４，１４５４，１４０７，１３７９，１３６３，１３２１，１２８２，１２２３，１１６８，１０９９，１０８１，１０３２，９４１，８１６，７６６，６５４，５９２ｃｍ^-1 [Synthesis Example 2]
The obtained intermediate-1 (5.6 g, 35 mmol) was added to dehydrated dichloromethane (100 mL), the inside of the flask was replaced with argon gas, and then triethylamine (5.1 g, 50 mmol) was added. After the mixture was cooled to about −10 ° C., methacrylic acid chloride (4.4 g, 42 mmol) was slowly added dropwise so that the system temperature was −10 to −5 ° C., and then stirred at room temperature for 2 hours. did. The precipitate was removed by filtration, and the filtrate was washed with water, a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution, dried over sodium sulfate, and then concentrated under reduced pressure to give a brown oil. The resulting oil was purified by column chromatography (Wakogel C300 300 g) to give a pale yellow oil (5.2 g). The pale yellow oil was confirmed to be a compound represented by the following structural formula from ¹ H-NMR and IR below. The yield after purification was about 65%.

¹ H-NMR (CDCl ₃ ): δ 1.13 (t, 6H), 1.95 (s, 3H), 3.25 (q, 4H), 3.55 (q, 2H), 4.28 (t , 2H), 4.71-4.76 (bs, 1H), 5.58-5.60 (m, 1H), 6.15-6.30 (m, 1H)
IR (NaCl): 3354, 2975, 2932, 1720, 1630, 1534, 1454, 1407, 1379, 1363, 1321, 1282, 1223, 1168, 1099, 1081, 1032, 941, 816, 766, 654, 592 cm ^-1

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）：δ１．１４（ｔ，６Ｈ），２．８９（ｓ，３Ｈ），３．２１（ｑ，４Ｈ），３．３２−３．３６（ｍ，２Ｈ），３．７４−３．７９（ｍ，２Ｈ），４．９７（ｔ，１Ｈ）
ＩＲ（ＮａＣｌ）：３４０３，２９７１，２９３３，２８７４，１６１５，１４９４，１４６１，１４０３，１３８２，１３５５，１２８５，１２４８，１２０８，１１７９，１１３３，１０７９，１０４８，９９４，９３７，８６２，７９７，７７５，５９２ｃｍ^-1 [Synthesis Example 3]
Diethylcarbamoyl chloride (24.4 g, 180 mmol) was dissolved in pyridine (400 ml). N-methylethanolamine (13.5 g, 180 mmol) was slowly added to this solution while cooling in a water bath, and then stirred at room temperature for 24 hours. After adding ethyl acetate (200 ml), the precipitate was filtered off and the resulting solution was concentrated under reduced pressure to give a brown liquid. This liquid was purified by column chromatography (Wakogel C300 200 g) to obtain a pale yellow oil (12.4 g). This pale yellow oil was confirmed to be a compound (intermediate-2) represented by the following structural formula from ¹ H-NMR and IR. The yield after purification was about 40%.

¹ H-NMR (CDCl ₃ ): δ 1.14 (t, 6H), 2.89 (s, 3H), 3.21 (q, 4H), 3.32-3.36 (m, 2H), 3 .74-3.79 (m, 2H), 4.97 (t, 1H)
IR (NaCl): 3403, 2971, 2933, 2874, 1615, 1494, 1461, 1403, 1382, 1355, 1285, 1248, 1208, 1179, 1133, 1079, 1048, 994, 937, 862, 797, 775, 592 cm ^-1

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）：δ１．１１（ｔ，６Ｈ），２．８８（ｓ，３Ｈ），３．１６（ｑ，４Ｈ），３．５０（ｔ，２Ｈ），４．３３（ｔ，２Ｈ），５．８３−５．８６（ｍ，１Ｈ），６．０８−６．１５（ｍ，１Ｈ），６．３８−６．４３（ｍ，１Ｈ）
ＩＲ（ＮａＣｌ）：２９７１，２９３５，２８７５，１７２７，１６４５，１４８７，１４６１，１４０５，１３５４，１２９４，１２７０，１１８８，１１３４，１０６４，９８６，８１０，６６７，５６３ｃｍ^-1 The obtained intermediate-2 (5.0 g, 29 mmol) was added to dehydrated dichloromethane (70 mL), the inside of the flask was replaced with argon gas, and then triethylamine (4.6 g, 45 mmol) was added. After cooling the mixture to about −10 ° C., acrylic acid chloride (3.3 g, 36 mmol) was slowly added dropwise so that the system temperature was −10 to −5 ° C., and then stirred at room temperature for 2 hours. did. The precipitate was removed by filtration, and the filtrate was washed with water, a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution, dried over sodium sulfate, and then concentrated under reduced pressure to give a brown oil. The resulting oil was purified by column chromatography (Wakogel C300 300 g) to give a pale yellow oil (4.6 g). The pale yellow oil was confirmed to be a compound represented by the following structural formula from ¹ H-NMR and IR below. The yield after purification was about 70%. The ¹ H-NMR spectrum of this compound is shown in FIG. 3, and the IR spectrum is shown in FIG.

¹ H-NMR (CDCl ₃ ): δ 1.11 (t, 6H), 2.88 (s, 3H), 3.16 (q, 4H), 3.50 (t, 2H), 4.33 (t , 2H), 5.83-5.86 (m, 1H), 6.08-6.15 (m, 1H), 6.38-6.43 (m, 1H)
IR (NaCl): 2971, 935, 2875, 1727, 1645, 1487, 1461, 1405, 1354, 1294, 1270, 1188, 1134, 1064, 986, 810, 667, 563 cm ⁻¹

¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）：δ１．１１（ｔ，６Ｈ），１．９４（ｓ，３Ｈ），２．８９（ｓ，３Ｈ），３．１６（ｑ，４Ｈ），３．５０（ｔ，２Ｈ），４．３１（ｔ，２Ｈ），５．５６−５．５８（ｍ，１Ｈ），６．０９−６．１１（ｍ，１Ｈ）
ＩＲ（ＮａＣｌ）：２９７０，２９３３，２８７５，１７２０，１６４３，１４８７，１４５７，１４００，１３５３，１３１９，１２９６，１２３４，１１６４，１１３４，１０７３，１０３０，９４１，８１４，７９８，７７５，６５６，５９６ｃｍ^-1 [Synthesis Example 4]
The obtained intermediate-2 (7.0 g, 40 mmol) was added to dehydrated dichloromethane (100 mL), the inside of the flask was replaced with argon gas, and then triethylamine (5.9 g, 58 mmol) was added. After the mixture was cooled to about −10 ° C., methacrylic acid chloride (5.1 g, 48 mmol) was slowly added dropwise so that the system temperature was −10 to −5 ° C., and then stirred at room temperature for 2 hours. did. The precipitate was removed by filtration, and the filtrate was washed with water, a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution, dried over sodium sulfate, and then concentrated under reduced pressure to give a brown oil. The obtained oil was purified by column chromatography (Wakogel C300 300 g) to give a pale yellow oil (7.8 g). The pale yellow oil was confirmed to be a compound represented by the following structural formula from ¹ H-NMR and IR below. The yield after purification was about 80%.

¹ H-NMR (CDCl ₃ ): δ 1.11 (t, 6H), 1.94 (s, 3H), 2.89 (s, 3H), 3.16 (q, 4H), 3.50 (t , 2H), 4.31 (t, 2H), 5.56-5.58 (m, 1H), 6.09-6.11 (m, 1H)
IR (NaCl): 2970, 2933, 2875, 1720, 1643, 1487, 1457, 1400, 1353, 1319, 1296, 1334, 1164, 1134, 1073, 1030, 941, 814, 798, 775, 656, 596 cm ⁻¹

As reference examples, commercially available products (a) to (g) of the following monomer compounds were obtained.

[Examples 1 to 4, Comparative Examples 1 to 7]
950 mg of the monomer compound shown in the columns of Examples and Comparative Examples in Table 1 and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (BASF Japan) as a polymerization initiator IRGACURE 907) 50 mg was mixed with a magnetic stirrer to prepare each sample for evaluation.
Each of these samples was evaluated for photopolymerization reactivity, photocurability and sample odor as follows. The results are shown in Table 1.

<Evaluation of photopolymerization reactivity>
The photopolymerization reactivity of each sample was evaluated using a measuring apparatus (hereinafter referred to as “Photo-DSC”) that combines a DSC-7020 manufactured by SII and a spot light source (LA-410UV) manufactured by HAYASHI WATCH-WORKS. In addition, the light of wavelength 365nm was used for irradiation light, and the light quantity was 200 mW / cm < ² >.
The calorific value associated with the polymerization reaction that proceeds after the light irradiation was measured by Photo-DSC. However, the calorific value when the light was irradiated for a sufficient time to complete the polymerization reaction of the monomer compound was measured for one sample. Repeated twice. The calorific value obtained by the first measurement includes the calorific value associated with light irradiation in addition to the calorific value associated with the polymerization reaction of the monomer compound. Therefore, the sample for which the polymerization reaction was completed in the first measurement was again irradiated with light under the same conditions, and the heat generation amount other than the polymerization reaction heat of the monomer was measured. And the calorific value accompanying the polymerization reaction of the monomer compound was obtained from the difference in calorific value between the first time and the second time.
In this exothermic characteristic, the time from the start of light irradiation until reaching the maximum calorific value was defined as T1 (sec.), Which was used as an index for comparing the speed of the photopolymerization reaction.

<Photocurability evaluation>
Evaluation of curability of each sample by photopolymerization using a measuring device (hereinafter referred to as “Photo rheometer”) that combines a viscoelasticity measuring device VAR200AD manufactured by REOLOGICA and an LED light source (LIGHTNINGCURE LC-L1) manufactured by Hamamatsu Photonics. did.
The measurement is carried out by sandwiching a sample in a 10 μm gap using a φ20 mm cone plate, irradiating light (365 nm, 50 mW / cm ² ) using an LED as a light source, measuring a change in viscoelasticity due to curing, and measuring an elastic modulus ( Curing was terminated when Pa) was saturated. The reaching point of the elastic modulus was obtained from the measurement result and used as an index of the curing level. The light energy (curing energy) irradiated until the elastic modulus is saturated is calculated by the product of the irradiation light intensity (here, 50 mW / cm ² ) and the light irradiation time (sec.).

<Odor evaluation>
An odor evaluation test was performed according to the following procedure, and the discomfort when the odor of each sample was smelled was evaluated based on the following criteria.
〔procedure〕
(1) About 100 mg (0.1 g) is weighed into a 50 cc sample bottle (glass bottle) and the lid is capped.
(2) Leave at room temperature for about 30 minutes.
(3) Bring the nose close to the sample bottle (glass bottle), sniff the odor when the lid is opened, and evaluate the degree based on the evaluation criteria.
〔Evaluation criteria〕
◯: Level that does not feel odor or is uncomfortable even if smell is felt Δ: Discomfort occurs due to specific odor.
X: Strong discomfort occurs due to a specific odor.

As can be seen from Table 1, the samples using the (meth) acrylic acid ester compounds of Examples 1 to 4 are excellent in practicality because they have high photopolymerization reactivity and high photocurability and no odor problems. . These are T1 which is an index of photoreactivity and the progress of polymerization reaction by light is fast, the curing energy for curing evaluation is small, and the elastic modulus when cured is as large as 1.0 × 10 ⁵ level. Therefore, it has an excellent function as a component of the curable ink. Among these, Examples 1 to 3 have extremely high polymerization reactivity and curability, and have extremely excellent functions. In particular, Examples 1 and 3 are excellent.
On the other hand, in the comparative examples, when the polar group in the structure of the monomer compound has an ether structure (Comparative Examples 1 and 2), the odor of the monomer compound gives a strong discomfort. Moreover, also in the case of having a morpholine ring as a polar group (Comparative Example 3 and Comparative Example 4) and the case of having a urethane structure (Comparative Example 7), the odor is at a level that gives unpleasant feeling.
Furthermore, in the case of having a strong hydroxyl group (OH) as a polar group (Comparative Example 5 and Comparative Example 6), a good odor result was obtained. In Comparative Example 6, the polymerization reactivity is low and the energy required for curing is also a large value.
Moreover, when the whole comparative example is seen, when the reactive functional group is methacrylate (Comparative Example 2, Comparative Example 4, and Comparative Example 6), the polymerization reactivity is low and a large amount of energy is required for curing. As a result, the curing properties are inferior. On the other hand, when the reactive functional group is an acrylate (Comparative Example 1, Comparative Example 3, Comparative Example 5, Comparative Example 7), the polymerization reactivity is excellent, but the elastic modulus during curing is saturated at a low level. Therefore, it is considered that the strength as a cured product is inferior to that of the example.

  As described above, the (meth) acrylic acid ester compound of the present invention is excellent in practicality because it has high photopolymerization reactivity and photocurability and has no problem of odor. This is considered to be due to having a specific urea structure in the molecule. In other words, it is considered that high reactivity, curability, and low odor are compatible by having the balance of the intermolecular interaction by the polar structure of the (meth) acrylic ester compound in an appropriate region.

Further, 100 parts of the (meth) acrylic acid ester compound (polymerizable compound) of Example 3 and Example 4 of the present invention, 10 parts of the polymerization initiator (IRGACURE 907 manufactured by BASF Japan Ltd.) and 3 parts of the color pigment are used for inkjet. An ink was prepared. The blending cost (parts) at this time is based on mass. About the coloring pigment, BASF Japan KK and MICROLITH Black CK (carbon black pigment) were used as the black pigment, and BASF Japan KK and MICROLITH Blue 4G-K were used as the blue pigment. The ink-jet ink composition obtained here is ejected onto a commercially available slide glass by ink-jetting, and cured by irradiation with light of 200 mW / cm ^{2 with} a UV irradiation machine LH6 manufactured by Fusion Systems Japan. As a result, it was confirmed that the ink can be discharged without any problems and cured.

JP 2007-231231 A JP 2007-231233 A JP 2009-67926 A JP 2009-144057 A JP 2006-257155 A JP 2009-249561 A JP 2010-181677 A JP 2007-138118 A JP 2007-177174 A JP 2009-179681 A Japanese Patent No. 3461501 Japanese Patent No. 3544658 JP 2012-140551 A JP 2012-140583 A

Optical Application Technology / Material Encyclopedia (Edition Committee for Optical Application Technology / Material Encyclopedia, Industrial Technology Service Center Co., Ltd., 2006) The latest optimization of UV curable resin

Claims (6)

A (meth) acrylic acid ester compound having a urea structure represented by the following formula (1).

[In the above formula, R ₁ and R ₂ are each a hydrogen atom or a substituted or unsubstituted alkyl structure, cycloalkyl structure, or hydrocarbon structure containing an aromatic ring, and R ₁ and R ₂ are linked to form a ring. A structure can also be formed. R ₃ represents a hydrogen atom or a substituted or unsubstituted alkyl structure, cycloalkyl structure, or hydrocarbon structure containing an aromatic ring, and can form a ring structure with R ₁ or R _2. . R ₃ can also form a ring structure with the bond of the nitrogen atom to which R ₃ is bonded. However, R ₁ and R ₂ are not simultaneously hydrogen atoms, and at least one of the two nitrogen atoms bonded to the carbonyl group in the urea structure is not bonded to a hydrogen atom. ] The (meth) acrylic acid ester compound according to claim ₁ , wherein R ₁ and R ₂ in the formula (1) are not hydrogen atoms. The (meth) acrylic acid ester compound according to claim 1 or 2, wherein R ₃ in the formula (1) is an alkyl structure or a hydrogen atom. The (meth) acrylic acid ester compound according to any one of claims 1 to 3, wherein the (meth) acrylic acid ester compound is a compound represented by the following formula (2) or formula (3).

  An active energy ray-curable composition comprising the (meth) acrylic acid ester compound according to claim 1.   An ink for inkjet recording, comprising the active energy ray-curable composition according to claim 5.

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