JP7068643B2 - Active energy ray-curable ink, composition container, two-dimensional or three-dimensional image forming device, two-dimensional or three-dimensional image forming method, and method for producing a cured product. - Google Patents

Description

The present invention relates to an active energy ray-curable composition, an active energy ray-curable ink, a composition accommodating container, a two-dimensional or three-dimensional image forming apparatus, a two-dimensional or three-dimensional image forming method, and a method for producing a cured product. Regarding.

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 is excellent in resource saving, and it is possible to keep the ink cost per unit recording low.

In recent years, an inkjet recording method using an active energy ray-curable ink has attracted attention. For example, active energy ray-curable resin compositions containing urethane oligomers having (meth) acrylamide groups at the ends or side chains, N-substituted (meth) acrylamide and non-reactive diluents have been proposed (eg, patents). See Document 1).
Further, a compound having an organic group (including an aromatic ring) having 1 to 10 carbon atoms as a mother nucleus and a (meth) acrylic acid ester group and a vinyl group in one molecule and a composition for optical nanoimprint using the same have been proposed. (See, for example, Patent Document 2).

However, in the above-mentioned prior art, there is room for improvement in odor, photopolymerizability and photocurability associated with volatility.
Therefore, an object of the present invention is to provide an active energy ray-curable composition having less odor and excellent photopolymerizability and photocurability.

ただし、前記一般式（１）中、Ｒ¹は水素原子又はメチル基を表し、Ｘ¹～Ｘ⁵はそれぞれ独立に、水素原子、炭素数１～１０のアルキル基、炭素数１～９のアルコキシ基、炭素数２～８のアルケニルオキシ基、－ＯＣＯ－ＣＲ²＝ＣＨ₂（Ｒ²は水素原子又はメチル基を表す）のいずれかを表し、
Ｘ¹およびＸ⁵のいずれか一方が水素、残りが炭素数１～１０のアルキル基、炭素数１～９のアルコキシ基、炭素数２～８のアルケニルオキシ基、－ＯＣＯ－ＣＲ²＝ＣＨ₂のいずれかであるとき、および、Ｘ¹およびＸ⁵の両方が炭素数１～１０のアルキル基、炭素数１～９のアルコキシ基、炭素数２～８のアルケニルオキシ基、－ＯＣＯ－ＣＲ²＝ＣＨ₂のいずれかであるとき、Ｘ²～Ｘ⁴はそれぞれ独立に、水素原子、炭素数１～１０のアルキル基、炭素数１～９のアルコキシ基、炭素数２～８のアルケニルオキシ基、－ＯＣＯ－ＣＲ²＝ＣＨ₂のいずれかであり、
Ｘ¹およびＸ⁵が水素原子であるとき、Ｘ²～Ｘ⁴のいずれか１つは、炭素数１～１０のアルキル基、炭素数１～９のアルコキシ基、炭素数２～８のアルケニルオキシ基、－ＯＣＯ－ＣＲ²＝ＣＨ₂のいずれかであるが、
Ｘ¹およびＸ⁵が水素原子であり、かつＸ²～Ｘ⁴のいずれか１つが－ＯＣＯ－ＣＲ²＝ＣＨ₂であるとき、Ｘ²～Ｘ⁴の残りの少なくとも一方は炭素数１～１０のアルキル基、炭素数１～９のアルコキシ基、炭素数２～８のアルケニルオキシ基、－ＯＣＯ－ＣＲ²＝ＣＨ₂のいずれかであり、
Ｘ¹およびＸ⁵が水素原子であり、かつＸ³が炭素数１～９のアルコキシ基であるとき、Ｘ²およびＸ⁴のうち少なくとも一方は炭素数１～１０のアルキル基、炭素数２～８のアルケニルオキシ基、－ＯＣＯ－ＣＲ²＝ＣＨ₂のいずれかである。 The above problem is solved by the following configuration 1).
1) An active energy ray-curable composition containing a (meth) acrylate compound represented by the following general formula (1).

However, in the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and X ¹ to X ⁵ independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy having 1 to 9 carbon atoms. Represents one of a group, an alkenyloxy group having 2 to 8 carbon atoms, and -OCO-CR ² = CH ₂ (R ² represents a hydrogen atom or a methyl group).
One of X ¹ and X ⁵ is hydrogen, the rest is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and -OCO-CR ² = CH ₂ . And when both X ¹ and X ⁵ are an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, -OCO-CR ² . = When either CH ₂ is satisfied, X ² to X ⁴ are independently hydrogen atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and an alkenyloxy group having 2 to 8 carbon atoms. , -OCO-CR ² = CH ₂
When X ¹ and X ⁵ are hydrogen atoms, any one of X ² to X ⁴ has an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and an alkenyloxy having 2 to 8 carbon atoms. Group, -OCO-CR ² = CH ₂
When X ¹ and X ⁵ are hydrogen atoms and any one of X ² to X ⁴ is −OCO-CR ² = CH ₂ , at least one of the remaining X ² to X ⁴ has 1 to 10 carbon atoms. Alkyl group, alkoxy group having 1 to 9 carbon atoms, alkenyloxy group having 2 to 8 carbon atoms, and -OCO-CR ² = CH ₂ .
When X ¹ and X ⁵ are hydrogen atoms and X ³ is an alkoxy group having 1 to 9 carbon atoms, at least one of X ² and X ⁴ is an alkyl group having 1 to 10 carbon atoms and 2 to 9 carbon atoms. One of the alkenyloxy groups of 8 and -OCO-CR ² = CH ₂ .

According to the present invention, it is possible to provide an active energy ray-curable composition having less odor associated with volatility and having excellent photopolymerizability and photocurability.

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.

Hereinafter, the present invention will be described in more detail.
(Active energy ray-curable composition)
The active energy ray-curable composition of the present invention contains a (meth) acrylate compound represented by the following general formula (1), and other active energy ray-curable compounds, a polymerization initiator, an organic solvent, and further, if necessary. Depending on the situation, it may contain a coloring material and other components.

ただし、前記一般式（１）中、Ｒ¹は水素原子又はメチル基を表し、Ｘ¹～Ｘ⁵はそれぞれ独立に、水素原子、炭素数１～１０のアルキル基、炭素数１～９のアルコキシ基、炭素数２～８のアルケニルオキシ基、－ＯＣＯ－ＣＲ²＝ＣＨ₂（Ｒ²は水素原子又はメチル基を表す）のいずれかを表し、
Ｘ¹およびＸ⁵のいずれか一方が水素、残りが炭素数１～１０のアルキル基、炭素数１～９のアルコキシ基、炭素数２～８のアルケニルオキシ基、－ＯＣＯ－ＣＲ²＝ＣＨ₂のいずれかであるとき、および、Ｘ¹およびＸ⁵の両方が炭素数１～１０のアルキル基、炭素数１～９のアルコキシ基、炭素数２～８のアルケニルオキシ基、－ＯＣＯ－ＣＲ²＝ＣＨ₂のいずれかであるとき、Ｘ²～Ｘ⁴はそれぞれ独立に、水素原子、炭素数１～１０のアルキル基、炭素数１～９のアルコキシ基、炭素数２～８のアルケニルオキシ基、－ＯＣＯ－ＣＲ²＝ＣＨ₂のいずれかであり、
Ｘ¹およびＸ⁵が水素原子であるとき、Ｘ²～Ｘ⁴のいずれか１つは、炭素数１～１０のアルキル基、炭素数１～９のアルコキシ基、炭素数２～８のアルケニルオキシ基、－ＯＣＯ－ＣＲ²＝ＣＨ₂のいずれかであるが、
Ｘ¹およびＸ⁵が水素原子であり、かつＸ²～Ｘ⁴のいずれか１つが－ＯＣＯ－ＣＲ²＝ＣＨ₂であるとき、Ｘ²～Ｘ⁴の残りの少なくとも一方は炭素数１～１０のアルキル基、炭素数１～９のアルコキシ基、炭素数２～８のアルケニルオキシ基、－ＯＣＯ－ＣＲ²＝ＣＨ₂のいずれかであり、
Ｘ¹およびＸ⁵が水素原子であり、かつＸ³が炭素数１～９のアルコキシ基であるとき、Ｘ²およびＸ⁴のうち少なくとも一方は炭素数１～１０のアルキル基、炭素数２～８のアルケニルオキシ基、－ＯＣＯ－ＣＲ²＝ＣＨ₂のいずれかである。

However, in the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and X ¹ to X ⁵ independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy having 1 to 9 carbon atoms. Represents one of a group, an alkenyloxy group having 2 to 8 carbon atoms, and -OCO-CR ² = CH ₂ (R ² represents a hydrogen atom or a methyl group).
One of X ¹ and X ⁵ is hydrogen, the rest is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and -OCO-CR ² = CH ₂ . And when both X ¹ and X ⁵ are an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, -OCO-CR ² . = When either CH ₂ is satisfied, X ² to X ⁴ are independently hydrogen atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and an alkenyloxy group having 2 to 8 carbon atoms. , -OCO-CR ² = CH ₂
When X ¹ and X ⁵ are hydrogen atoms, any one of X ² to X ⁴ has an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and an alkenyloxy having 2 to 8 carbon atoms. Group, -OCO-CR ² = CH ₂
When X ¹ and X ⁵ are hydrogen atoms and any one of X ² to X ⁴ is −OCO-CR ² = CH ₂ , at least one of the remaining X ² to X ⁴ has 1 to 10 carbon atoms. Alkyl group, alkoxy group having 1 to 9 carbon atoms, alkenyloxy group having 2 to 8 carbon atoms, and -OCO-CR ² = CH ₂ .
When X ¹ and X ⁵ are hydrogen atoms and X ³ is an alkoxy group having 1 to 9 carbon atoms, at least one of X ² and X ⁴ is an alkyl group having 1 to 10 carbon atoms and 2 to 9 carbon atoms. One of the alkenyloxy groups of 8 and -OCO-CR ² = CH ₂ .

The (meth) acrylate compound represented by the general formula (1) may be referred to as an active energy ray-curable compound.

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

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

The (meth) acrylate compound represented by the general formula (1) has a phenyl (meth) acrylate compound as a mother nucleus. In general, low molecular weight (meth) acrylate compounds have a strong odor peculiar to monomers because they are volatile, which makes them uncomfortable when handling curable compositions containing these compounds. become. This also applies to compounds having an aromatic ring, and monofunctional monomer compounds such as phenyl acrylate, benzyl acrylate, and phenoxyethyl acrylate having one benzene ring emit a strong unpleasant odor by themselves. , The curable composition containing these compounds has a problem of odor.

It is possible to suppress the volatility of the (meth) acrylate compound and reduce the odor by introducing a highly polar functional group into such a low molecular weight (meth) acrylate compound or by increasing the molecular weight. Is. However, in that case, the viscosity increases, and in some cases, it may crystallize, which causes a problem that restrictions on the use of the curable composition, especially the ink for inkjet, become large. There is.
Therefore, the (meth) acrylate compound represented by the general formula (1) has a compact structure as a mother core, which does not have a linking structure such as an alkylene oxide between the aromatic ring and the (meth) acrylic acid ester structure. .. Therefore, the curability by polymerization is excellent, and the odor can be suppressed by lowering the volatility. Furthermore, since the mother nucleus structure is compact and has a large degree of freedom, and the substituents are asymmetric, the increase in viscosity is small, and it is considered that low viscosity can be maintained. In this case, the terminal structure of the ester is an alkyl group, and it is considered that the viscosity is less likely to increase as compared with a structure containing a carbon-carbon double bond. As a result, the (meth) acrylate compound represented by the general formula (1) can be suitably used as an active energy ray-curable composition.

The (meth) acrylate 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 (2) is preferable.

ただし、前記一般式（２）中、Ｒ¹およびＲ²は水素原子又はメチル基を表し、Ｘ²～Ｘ⁴はそれぞれ独立に、水素原子、炭素数１～１０のアルキル基、炭素数１～９のアルコキシ基、炭素数２～８のアルケニルオキシ基、－ＯＣＯ－ＣＲ²＝ＣＨ₂のいずれかを表す。

However, in the general formula (2), R ¹ and R ² represent a hydrogen atom or a methyl group, and X ² to X ⁴ independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms. It represents any of 9 alkoxy groups, alkenyloxy groups having 2 to 8 carbon atoms, and -OCO-CR ² = CH ₂ .

R ¹ and R ² in the general formula (2) represent a hydrogen atom or a methyl group.
Examples of X ² to X ⁴ in the general formula (2) include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and -OCO-CH. = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ .
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 an isopentyl group. Examples thereof include a neopentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group and a decyl group.
Examples of the alkoxy group having 1 to 9 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, and a nonyloxy group.
Examples of the alkenyloxy group having 2 to 8 carbon atoms include -OCH ₂ CH = CH ₂ , -OCH ₂ CH = CHCH ₃ , and -OCH ₂ CH = CHC ₂ H ₅ .

The 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 (3) is preferable.

ただし、前記一般式（３）中、Ｒ¹は水素原子又はメチル基を表し、Ｘ¹およびＸ²はそれぞれ独立に、水素原子、炭素数１～１０のアルキル基、炭素数１～９のアルコキシ基、炭素数２～８のアルケニルオキシ基のいずれかを表し、Ｘ³は水素原子、炭素数１～１０のアルキル基、炭素数２～８のアルケニルオキシ基のいずれかを表し、Ｘ¹およびＸ²が水素原子であるとき、Ｘ³は炭素数１～１０のアルキル基、炭素数２～８のアルケニルオキシ基のいずれかを表す。

However, in the general formula (3), R ¹ represents a hydrogen atom or a methyl group, and X ¹ and X ² are independently hydrogen atoms, an alkyl group having 1 to 10 carbon atoms, and an alkoxy having 1 to 9 carbon atoms. A group represents any of an alkenyloxy group having 2 to 8 carbon atoms, X ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, and X ¹ and When X ² is a hydrogen atom, X ³ represents either an alkyl group having 1 to 10 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms.

R ¹ in the general formula (3) represents a hydrogen atom or a methyl group.
The X ¹ and X ² in the general formula (3) represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, and an alkenyloxy group having 2 to 8 carbon atoms, and X ³ Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkenyloxy group having 2 to 8 carbon atoms. When X ¹ and X ² are hydrogen atoms, X ³ is an alkyl group having 1 to 10 carbon atoms and carbon. Represents an alkenyloxy group of number 2-8.
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 an isopentyl group. Examples thereof include a neopentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group and a decyl group.
Examples of the alkoxy group having 1 to 9 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, and a nonyloxy group.
Examples of the alkenyloxy group having 2 to 8 carbon atoms include -OCH ₂ CH = CH ₂ , -OCH ₂ CH = CHCH ₃ , and -OCH ₂ CH = CHC ₂ H ₅ .

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

ただし、前記一般式（２－１）中、Ｒ¹およびＲ²は水素原子又はメチル基を表す。

However, in the general formula (2-1), R ¹ and R ² represent a hydrogen atom or a methyl group.

ただし、前記一般式（３－１）および（３－２）中、Ｒ¹は水素原子又はメチル基を表し、Ｒ³は炭素数１～９のアルキル基を表す。
前記炭素数１～９のアルキル基としては、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、イソペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、２－エチルヘキシル基、ノニル基などが挙げられる。 The compound represented by the general formula (3) is not particularly limited and may be appropriately selected depending on the intended purpose. However, the compounds represented by the following general formulas (3-1) and (3-2) can be appropriately selected. Is preferable.

However, in the general formulas (3-1) and (3-2), R ¹ represents a hydrogen atom or a methyl group, and R ³ represents an alkyl group having 1 to 9 carbon atoms.
Examples of the alkyl group having 1 to 9 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 an isopentyl group. Examples thereof include a neopentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group and a nonyl group.

Next, as specific examples of the (meth) acrylate compound represented by the general formula (1), the exemplary compounds a to i are shown, but the present invention is not limited thereto. In addition, R ¹ and R ² in these examples are the same as R ¹ and R ² in the said general formula (1).

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

<< Exemplified compound a-1 >>

<< Exemplified compound a-2 >>

<< Exemplified compound a-3 >>

<< Exemplified compound a-4 >>

<< Exemplified compound a-5 >>

<< Exemplified compound a-6 >>

<< Exemplified compound a-7 >>

<< Exemplified compound a-8 >>

<< Exemplified compound a-9 >>

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

<< Exemplified compound b-1 >>

<< Exemplified compound b-2 >>

<< Exemplified compound b-3 >>

<< Exemplified compound b-4 >>

<< Exemplified compound b-5 >>

<< Exemplified compound b-6 >>

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

<< Exemplified compound c-1 >>

<< Exemplified compound c-2 >>

<< Exemplified compound c-3 >>

<< Exemplified compound c-4 >>

<< Exemplified compound c-5 >>

<< Exemplified compound c-6 >>

Examples of the exemplified compound d group include the compounds shown below. These may be used alone or in combination of two or more.

<< Exemplified compound d-1 >>

<< Exemplified compound d-2 >>

<< Exemplified compound d-3 >>

<< Exemplified compound d-4 >>

<< Exemplified compound d-5 >>

<< Exemplified compound d-6 >>

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

<< Exemplified compound e-1 >>

<< Exemplified compound e-2 >>

<< Exemplified compound e-3 >>

<< Exemplified compound e-5 >>

<< Exemplified compound e-6 >>

Examples of the exemplary compound f group include the compounds shown below. These may be used alone or in combination of two or more.

<< Exemplified compound f-1 >>

<< Exemplified compound f-2 >>

<< Exemplified compound f-3 >>

<< Exemplified compound f-4 >>

<< Exemplified compound f-5 >>

<< Exemplified compound f-6 >>

Examples of the exemplified compound g group include the compounds shown below. These may be used alone or in combination of two or more.

<< Exemplified compound g-1 >>

<< Exemplified compound g-2 >>

<< Exemplified compound g-3 >>

<< Exemplified compound g-4 >>

<< Exemplified compound g-5 >>

<< Exemplified compound g-6 >>

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

<< Exemplified compound h-1 >>

<< Exemplified compound h-2 >>

<< Exemplified compound h-3 >>

<< Exemplified compound h-4 >>

<< Exemplified compound h-5 >>

<< Exemplified compound h-6 >>

<< Exemplified compound h-7 >>

<< Exemplified compound h-8 >>

Examples of the exemplified compound i group include the compounds shown below. These may be used alone or in combination of two or more.

<< Exemplified compound i-1 >>

<< Exemplified compound i-2 >>

<< Exemplified compound i-3 >>

<< Exemplified compound i-4 >>

<< Exemplified Compound i-5 >>

<< Exemplified compound i-6 >>

Among the group a to the group i, the example compound a-1, the example compound b-1, the example compound c-1, the example compound d-1, the example compound e-1, and the example compound f-1 are preferable, and the following The compounds represented by the structural formulas (1-1) to (3-2) are more preferable, the compounds represented by the following structural formulas (1-1), the compounds represented by the following structural formulas (2-1), and the like. The compound represented by the following structural formula (3-1) is particularly preferable.

The (meth) acrylate 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.

Further, the compound represented by the following general formula (B) and the compound represented by the following structural formula (C) have a substituent having a carbon-carbon double bond in the terminal ester structure. It is considered that the viscosity is higher than that of the compound of the present invention having the same mother nucleus structure. This may make it difficult to use as a curable composition.

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

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

<Other active energy ray-curable compounds>
As the other active energy ray-curable compound, an active energy ray-curable compound other than the (meth) acrylate compound represented by the general formula (1) can be used.

The active energy ray-curable compound other than the (meth) acrylate compound represented by the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, active energy ray radical polymerizable. Examples thereof include compounds, active energy ray cationically polymerizable compounds, and active energy ray anion polymerizable compounds. These may be used alone or in combination of two or more.

The active energy ray radically polymerizable compound is not particularly limited as long as it is a compound having one or more ethylenically unsaturated groups capable of performing active energy ray radical polymerization, and can be appropriately selected depending on the intended purpose. For example, a compound containing a monomer, an oligomer, a polymer and the like can be mentioned. Among these, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, salts thereof, 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 active energy ray radically polymerizable compound include 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, and bis (4-acryloxypolyethoxyphenyl) propane. Neopentyl glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol di. Acrylate, 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 Propane Triacrylate, Tetramethylol Methan Tetraacrylate, Oligoester Acrylate, Acrylic Acid Derivatives such as Epoxy Acrylate, Methyl Methacrylate, n-butyl Methacrylate, Allyl Methacrylate, Glycidyl Methacrylate, benzyl Methacrylate, Dimethyl Amino Methyl 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-methacryloxypoly). Acrylate derivatives such as ethoxyphenyl) propane, acrylamide derivatives such as N-methylol acrylamide, diacetone acrylamide, 2-hydroxyethyl acrylamide, and acryloyl morpholine, and derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate. , Ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene Glycol monovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, trimethylol propane Monotrivinyl ether compounds such as trivinyl ether, divinyl ether compounds, or trivinyl ether compounds, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, Monovinyl ether compounds such as n-propyl 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 hydroxypivalate, 2-acryloyloxyethyl phthalic acid, methoxypolyethylene glycol acrylate, tetramethylol methanetriacrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, dimethylol tricyclo Decandy acrylate, ethoxylated phenyl acrylate, 2-acryloyloxyethyl succinic acid, nonylphenolethylene oxide adduct acrylate, modified glycerin triacrylate, bisphenol A diglycidyl ether acrylic acid adduct, modified bisphenol A diacrylate, phenoxypolyethylene glycol acrylate, 2 -Acryloyloxyethyl hexahydrophthalic acid, propylene oxide adduct diacrylate of bisphenol A, ethylene oxide adduct diacrylate of bisphenol A, dipentaerythritol hexaacrylate, tolylene isocyanato urethane prepolymer, lactone-modified flexible acrylate, butoxy Addition of ethyl acrylate and propylene glycol diglycidyl ether acrylic acid Examples thereof include hexamethylene disosocyanate 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 active energy ray cationically polymerizable compound include an epoxy compound, a vinyl ether compound, and an oxetane compound. These may be used alone or in combination of two or more.

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

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

<Polymer initiator>
The active energy ray-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 the energy of the active energy ray 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, p-dimethylaminobenzoate-2-ethylhexyl, 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.

<Color material>
The active energy ray-curable composition of the present invention may contain a coloring material. As the coloring material, various pigments and dyes that impart black, white, magenta, cyan, yellow, green, orange, glossy colors such as gold and silver, etc., depending on the purpose and required characteristics of the composition in the present invention. Can be used. The content of the coloring material may be appropriately determined in consideration of 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 active energy ray-curable composition of the present invention may be colorless and transparent without containing a coloring material, and in that case, for example, it is suitable as an overcoat layer for protecting an image.
As the pigment, an inorganic pigment or an organic pigment can be used, and one 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 active energy ray-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, defoaming agents, fluorescent whitening agents, penetration promoters, wetting agents (moisturizing agents), and fixing agents. Examples include agents, viscosity stabilizers, fungicides, preservatives, antioxidants, UV absorbers, chelating agents, pH regulators, thickeners and the like.

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

-Polymerization inhibitor-
The polymerization inhibitor can enhance the storage stability (storage stability) of the active energy ray-curable composition, and also heats the curable composition to reduce its viscosity and ejects the head by thermal polymerization. It is possible to prevent clogging.

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

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

The active energy ray-curable composition of the present invention may further contain a sensitizer in order to accelerate the decomposition of the photopolymerization initiator by irradiation with the active energy ray.
-Sensitizer-
The sensitizer can be contained to accelerate the decomposition of the photopolymerization initiator by irradiation with active energy rays.
The sensitizer absorbs active energy rays and becomes an electron-excited state, and in that state, it comes into contact with the polymerization initiator and undergoes a chemical change of the polymerization initiator by the action of, for example, electron transfer, energy transfer, heat generation, etc. Decomposition, radical, acid or base production) is promoted.

The mass ratio of the content (mass%) of the sensitizer to the content (mass%) of the photopolymerization initiator is preferably 5 × 10 ^-3 or more and 200 or less as the former / the latter, and 0. More preferably, it is 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), acridines (eg, acrydin orange, chloroflavin, acryflabin), anthraquinones (eg, erythrinone). , Anthraquinone), squaryliums (eg, squarylium), coumarins (eg, 7-diethylamino-4-methylcoumarin) and the like. These may be used alone or in combination of two or more.

-Co-sensitizer-
As the co-sensitizer, for example, the sensitivity of the sensitizing dye to active energy rays can be further improved, and the inhibition of polymerization of the photopolymerizable 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-mercaptobenzoimidazole, 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-
Since the active energy ray-curable composition is an active energy ray-curable composition, it is preferable that it does not contain a solvent. However, for example, in order to improve the adhesiveness between the cured ink and the recording medium, the ink A solvent may be contained as long as it does not affect the curing rate or the like.
The solvent is not particularly limited, and examples thereof include an organic solvent 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 active energy ray-curable composition.

<Organic solvent>
The active energy ray-curable composition of the present invention may contain an organic solvent, but it is preferable not to contain it if possible. If the composition does not contain an organic solvent, particularly a volatile organic solvent (VOC (Volatile Organic Compounds) free), the safety of the place where the composition is handled is further enhanced, and it is possible to prevent environmental pollution. .. The "organic solvent" means 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.

The active energy ray-curable composition of the present invention contains 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. Further may be included.
Further, the active energy ray-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.

<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 active energy ray-curable composition of the present invention include, in addition to ultraviolet rays, polymerizable components in the composition such as electron beams, α rays, β rays, γ rays, and X-rays. It is not particularly limited as long as it can impart the energy necessary for advancing the polymerization reaction of the above. 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 active energy ray-curable composition>
The active energy ray-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. For example, a polymerizable monomer, a pigment, a dispersant and the like can be used in a ball mill. It is put into a disperser such as a kitty mill, a disc mill, a pin mill, and a dyno mill, and dispersed to prepare a pigment dispersion, and the pigment dispersion is further mixed with a polymerizable monomer, an initiator, a polymerization inhibitor, a surfactant, and the like. It can be prepared by letting it.

<Viscosity>
The viscosity of the active energy ray-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 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 about 65 ° C. VISCOMATE VM-150III can be used to adjust the temperature of the circulating water.

<Use>
The application of the active energy ray-curable composition of the present invention is not particularly limited as long as it is in the field where the active energy ray-curable material is generally used, and can be appropriately selected depending on the intended purpose, for example, for molding. Examples thereof include resins, paints, adhesives, insulating materials, mold release agents, coating materials, sealing materials, various resists, and various optical materials.
Further, the active energy ray-curable composition of the present invention can be used as an ink to not only form a design coating film on two-dimensional characters and images and various substrates, but also to form a three-dimensional stereoscopic image (three-dimensional model). It can also be used as a three-dimensional modeling material for forming. This three-dimensional modeling material may be used, for example, as a binder between powder particles used in a powder 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 active energy ray-curable composition of the present invention is discharged into a predetermined region, and the ones cured by irradiating with active energy rays are sequentially laminated to perform three-dimensional modeling (details will be described later). FIG. 3 shows that the storage pool (accommodation portion) 1 of the active energy ray-curable composition 5 of the present invention is irradiated with the active energy ray 4 to form a cured layer 6 having a predetermined shape on the movable stage 3. This is a method of sequentially stacking and performing three-dimensional modeling.
As a three-dimensional modeling device for modeling a three-dimensional model using the active energy ray-curable composition of the present invention, a known one can be used, and the present invention is not particularly limited, but for example, a means for accommodating the composition. , A supply means, a discharge means, an active energy ray irradiation means, and the like.
The present invention also includes a cured product obtained by curing an active energy ray-curable composition and a molded product obtained by processing a structure in which the cured product is formed on a substrate. The molded product is, for example, a cured product or structure formed in 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, OA equipment, 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.

(Active energy ray-curable ink)
The active energy ray-curable ink contains an active energy ray-curable composition.
As the active energy ray-curable composition, the same as the active energy ray-curable composition of the present invention can be used.

The active energy ray-curable ink is preferably for inkjet.

<Composition container>
The composition container of the present invention means a container in which an active energy ray-curable composition is stored, and is suitable for use in the above-mentioned applications. For example, when the active energy ray-curable composition of the present invention is used for ink, the container containing the ink can be used as an ink cartridge or an ink bottle, whereby ink transfer, ink replacement, etc. It is not necessary to touch the ink directly in the work, and it is possible to prevent the fingers and clothes from getting dirty. In addition, it is possible to prevent foreign substances such as dust from being mixed into the ink. 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.

<Image formation 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, an irradiation step of irradiating the active energy rays is provided, and the image forming apparatus of the present invention comprises an irradiation means for irradiating the active energy rays. , The accommodating portion for accommodating the active energy ray-curable composition of the present invention may be provided, and the container may be accommodated in the accommodating portion. Further, it may have a discharge step and a discharge means for discharging the active energy ray-curable composition. The method of discharging is not particularly limited, and examples thereof include a continuous injection type and an on-demand type. Examples of the on-demand type include a piezo method, a thermal method, and an electrostatic method.
FIG. 1 is an example of an image forming apparatus provided with an inkjet ejection means. Ink is ejected to the recorded medium 22 supplied from the supply roll 21 by each color printing unit 23a, 23b, 23c, 23d provided with an ink cartridge for each color active energy ray-curable ink of yellow, magenta, cyan, and black and an ejection head. Will be done. Then, the light sources 24a, 24b, 24c, and 24d for curing the ink are irradiated with active energy rays to cure the ink, and a color image is formed. After that, the recording medium 22 is conveyed to the processing unit 25 and the printed matter take-up roll 26. Each printing unit 23a, 23b, 23c, 23d may be provided with a heating mechanism so that the ink is liquefied at the ink ejection portion. Further, if necessary, a mechanism for cooling the recording medium to about room temperature by contact or non-contact may be provided. Further, as an inkjet recording method, a serial method in which the head is moved to eject ink onto the recording medium or a recording medium is continuously moved with respect to a recording medium that moves intermittently according to the 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, building materials such as wallpaper and flooring, 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 discharge the first active energy ray-curable composition from the discharge head unit 30 for a modeled object for a support. The second active energy ray-curable composition having a composition different from that of the first active energy ray-curable composition is discharged from the head units 31 and 32, and each of these compositions is cured by the adjacent ultraviolet irradiation means 33 and 34. It is laminated while being laminated. More specifically, for example, the second active energy ray-curable composition is discharged from the support discharge head units 31 and 32 onto the modeled object support substrate 37, and is irradiated with the active energy rays to be solidified. After forming the first support layer having the reservoir, the first active energy ray-curable composition is discharged from the discharge head unit 30 for a modeled object to the reservoir, and the active energy ray is irradiated to solidify the reservoir. By repeating the process of forming the first modeled object layer a plurality of times while lowering the vertically movable stage 38 according to the number of times of stacking, the support layer and the modeled object layer are laminated to form the three-dimensional model 35. To make. After that, the support laminated portion 36 is removed as needed. In FIG. 2, only one discharge head unit 30 for a modeled object is provided, but two or more may be provided.

(Manufacturing method of cured product)
The cured product of the present invention can be produced by a method of irradiating at least one of an active energy ray-curable composition and an active energy ray-curable ink with active energy rays to cure the cured product.
As the active energy ray-curable composition, the same composition as the active energy ray-curable composition can be used.
As the active energy ray-curable ink, the same ink as the active energy ray-curable ink can be used.

(Decorative body)
The decorative body is formed by surface decoration made of a cured product on a base material.
As the cured product, the same cured product as that of the present invention 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 (300 MHz) (ECX300, manufactured by JEOL Ltd.).

<Active energy ray-curable compound 1>
(Synthesis of active energy ray-curable compound 1)
15.0 g (136 mmol) of catechol manufactured by Tokyo Chemical Industry Co., Ltd. was added to 200 mL of dehydrated dichloromethane, and 33.1 g (327 mmol) of triethylamine was added. Next, after cooling to about -15 ° C, 29.6 g (327 mmol) of acrylic acid chloride manufactured by Wako Pure Chemical Industries, Ltd. is slowly added dropwise so that the temperature inside the system becomes -8 ° C to -9 ° C. , Stirred at room temperature 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 magnesium sulfate and then concentrated under reduced pressure to obtain an oil. Further, silica gel is filled and purified by column chromatography using hexane and ethyl acetate as eluents to obtain a colorless oily substance of the active energy ray-curable compound 1 represented by the following structural formula (1-1). 1 g (yield: about 92.6%) was obtained.

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): 6.00 (d, 2H), 6.25 (dd, 2H), 6.58 (d, 2H), 7.20 (d, 2H), 7.31 (d). , 2H).

<Active energy ray-curable compounds 2 to 6 and active energy ray-curable comparative compounds 1 to 6>
In the synthesis of the active energy ray-curable compound 1, the reaction was carried out in the same manner as in the synthesis of the active energy ray-curable compound 1 except that the amine used in the reaction was replaced with the corresponding amine, and the respective active energy ray-curable compounds were cured. Active energy ray-curable compounds of sex compounds 2 to 6 and active energy ray-curable comparative compounds 3 to 6 were obtained.

(Active energy ray-curable compound 2)

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ2.07 (t, 6H), 5.73 (s, 2H), 6.37 (s, 2H), 6.95 (dd, 2H), 7.25 (dd) , 2H)

(Active energy ray-curable compound 3)

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ3.82 (s, 3H), 6.00 (d, 1H), 6.36 (dd, 1H), 6.62 (d, 1H), 6.95 (m). , 2H), 7.09 (d, 1H), 7.23 (dd, 1H).

(Active energy ray-curable compound 4)

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ2.08 (t, 3H), 3.81 (s, 3H), 5.74 (s, 1H), 6.35 (s, 1H), 6.95 (m). , 2H), 7.09 (d, 1H), 7.23 (dd, 1H).

(Active energy ray-curable compound 5)

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ3.82 (s, 3H), 6.00 (d, 1H), 6.36 (dd, 1H), 6.62 (d, 1H), 6.95-7 .09 (m, 3H), 7.23 (m, 1H).

(Active energy ray-curable compound 6)

The identification data are as shown below.
^{1 1} H-NMR (CDCl ₃ ): δ2.08 (t, 3H), 3.81 (s, 3H), 5.74 (s, 1H), 6.35 (s, 1H), 6.95-7 .09 (m, 3H), 7.23 (m, 1H).

(Active energy ray curable comparative compound 1)
A commercially available phenyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following structural formula (a-1) was used as the active energy ray-curable comparative compound 1.

(Active energy ray curable comparative compound 2)
A commercially available phenyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following structural formula (a-2) was used as the active energy ray-curable comparative compound 2.

(Active energy ray curable comparative compound 3)
The p-phenyldiacrylate represented by the following structural formula (b-1) was synthesized by the same method as the synthesis of the active energy ray-curable compound 1 to obtain an active energy ray-curable comparative compound 3. This compound crystallized after 1 day at room temperature.

(Active energy ray curable comparative compound 4)
P-Phenyl methacrylate represented by the following structural formula (b-2) was synthesized by the same method as in the synthesis of the active energy ray-curable compound 1 to obtain an active energy ray-curable comparative compound 4. This compound crystallized after 1 day at room temperature.

(Active energy ray curable comparative compound 5)
4-Methoxyphenyl acrylate represented by the following structural formula (c-1) was synthesized by the same method as the synthesis of the active energy ray-curable compound 1 to obtain a specific active energy ray-curable comparative compound 5. This compound crystallized after 1 day at room temperature.

(Active energy ray curable comparative compound 6)
4-Methoxyphenyl methacrylate represented by the following structural formula (c-2) was synthesized by the same method as in the synthesis of the active energy ray-curable compound 1 to obtain an active energy ray-curable comparative compound 6. This compound crystallized after 1 day at room temperature.

The viscosity and odorlessness of the obtained active energy ray-curable compound were evaluated as follows. The results are shown in Table 1 below.

<Measurement of viscosity>
The viscosity of the obtained active energy ray-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 rotation speed was 50 rpm, and the temperature of the constant temperature circulating water was measured at 25 ° C.

<Evaluation of volatility>
The volatility of the obtained active energy ray-curable compound was measured by TG-DTA (device name: TG / DTA7200, manufactured by Hitachi High-Tech) at a temperature when the mass was reduced by 10%. The TG-DTA is a device that continuously measures the mass change that occurs when a sample is heated and the thermal behavior of heat generation or endothermic. The measurement is performed according to JIS K0129. The measurement was performed in an atmosphere of an inert gas such as nitrogen, and the temperature rise rate was 10 ° C./min, and the temperature at 10% mass reduction was found to be 10% mass reduction with respect to the mass at room temperature in the TG curve. Let it be the temperature of the hour.

From the results in Table 1 above, it can be seen that the active energy ray-curable compounds 1 to 6 have low volatility and little odor. Further, it can be seen that the compound has a low viscosity without crystallization.

(Examples 1a to 6a and Comparative Examples 1a to 6a)
-Preparation of active energy ray-curable composition-
950 mg of each active energy ray-curable compound of the active energy ray-curable compounds 1 to 6 and the active energy ray-curable comparative compounds 1 to 6 and a photopolymerization initiator (trade name: IRGACURE 907, component name: 2-methyl-1). -[4- (Methylthio) phenyl] -2-morpholinopropane-1-one, manufactured by BASF Japan Co., Ltd.) 50 mg was mixed using a magnetic stirrer, and the active energies of Examples 1a to 6a and Comparative Examples 1a to 6a were mixed. A linear curable composition was prepared.

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

<Photocurability>
Each active energy ray curing 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 photocurability of the mold composition 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 is saturated, that is, the curing energy is calculated from the product of the intensity of the ultraviolet rays (50 mW / cm ² ) and the time [seconds] of the irradiation of the ultraviolet rays.

From the results in Table 2 above, it can be seen that the active energy ray-curable compositions of Examples 1a to 6a using the active energy ray-curable compounds 1 to 6 are excellent in photocurability. Specifically, the curing energy, which is an index of curability, is smaller than that of the comparative example, and the saturated storage elastic modulus, which indicates the level of curing, also shows a very large value. This is considered to indicate that the presence of the aromatic ring structure in the molecule promotes the polymerization, and the intramolecular interaction due to the polar structure acts in the cured product to form a harder state. ..

(Examples 1b to 6b)
-Making black ink-
100 parts by mass of active energy ray-curable compounds 1 to 6 of active energy ray-curable compounds, 10 parts by mass of photopolymerization initiator (trade name: IRGACURE 907, manufactured by BASF Japan Co., Ltd.), and carbon black (trade name: MICROLITH Black). CK, manufactured by BASF Japan Co., Ltd.) 3 parts by mass were mixed to obtain black inks of Examples 1b to 6b.

(Examples 1c to 6c)
-Making blue ink-
100 parts by mass of active energy ray-curable compounds 1 to 6 of active energy ray-curable compounds, 10 parts by mass of photopolymerization initiator (trade name: IRGACURE 907, manufactured by BASF Japan Co., Ltd.), and blue pigment (trade name: MICROLLITH Blue). 4G-K, manufactured by BASF Japan Co., Ltd.) 3 parts by mass were mixed to obtain blue inks of Examples 1c to 6c.

<Ink curability evaluation 1>
Each ink of Examples 1b to 6b and Examples 1c to 6c is inkjet-discharged onto a slide glass using an inkjet recording device (Head: GEN4 manufactured by Ricoh Printing System Co., Ltd.) and then UV-irradiated. Using a machine (trade name: LH6, manufactured by Fusion Systems Japan Co., Ltd.), ultraviolet rays having a wavelength of 365 nm were irradiated at 200 mW / cm ² and cured.
As a result, each 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 active energy ray-curable composition of Examples 1a to 6a, but just in case, light is applied in the same manner as in the case of each active energy ray-curable composition. When the polymerizable property and the photocurability were measured, it was confirmed that both were excellent as in the active energy ray-curable composition of Examples 1a to 6a.

<Ink curability evaluation 2>
After immersing the tip of the dip pen in the inks of Examples 1b to 6b and Examples 1c to 6c and writing characters on PET film and plain paper, a UV irradiator (trade name: LH6, Fusion System Japan Co., Ltd.) The product was cured by irradiating it with ultraviolet rays having a wavelength of 365 nm at 200 mW / cm ² .
As a result, the ink image was sufficiently cured.

1 Storage pool (accommodation)
3 Movable stage 4 Active energy ray 5 Active energy ray Curable composition 6 Cured layer 21 Supply roll 22 Recorded matter 23a, 23b, 23c, 23d Each color printing unit 24a, 24b, 24c, 24d Light source 25 Processing unit 26 Printed matter winding Roll 30 Discharge head unit for shaped object 31, 32 Discharge head unit for support 33, 34 Ultraviolet irradiation means 35 Three-dimensional model 36 Support laminated portion 37 Modeled object support substrate 38 Stage 39 Image forming device

Japanese Unexamined Patent Publication No. 2016-11518 Japanese Unexamined Patent Publication No. 2009-215179

Claims (9)

An active energy ray-curable ink containing a (meth) acrylate compound represented by the following general formula (2) as a polymerization initiator and a polymerizable compound that is cured by polymerization.

However, in the general formula (2), R ¹ and R ² represent a hydrogen atom or a methyl group, and X ² to X ⁴ independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms. It represents any of 9 alkoxy groups, alkenyloxy groups having 2 to 8 carbon atoms, and -OCO-CR ² = CH ₂ . An active energy ray-curable ink containing a (meth) acrylate compound represented by the following general formula (3) as a polymerization initiator and a polymerizable compound that is cured by polymerization.

However, in the general formula (3), R ¹ represents a hydrogen atom or a methyl group, and X ¹ and X ² are independently hydrogen atoms, an alkyl group having 1 to 10 carbon atoms, and an alkoxy having 1 to 9 carbon atoms. A group represents any of an alkenyloxy group having 2 to 8 carbon atoms, X ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, and X ¹ and When X ² is a hydrogen atom, X ³ represents either an alkyl group having 1 to 10 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms. The active energy ray-curable ink according to claim 1, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (2-1).

However, in the general formula (2-1), R ¹ and R ² represent a hydrogen atom or a methyl group. The active energy ray-curable ink according to claim 2, wherein the compound represented by the general formula (3) is a compound represented by the following general formula (3-1) or the general formula (3-2).

However, in the general formulas (3-1) and (3-2), R ¹ represents a hydrogen atom or a methyl group, and R ³ represents an alkyl group having 1 to 9 carbon atoms. The active energy ray-curable ink according to any one of claims 1 to 4, which is for inkjet. A composition container in which the active energy ray-curable ink according to any one of claims 1 to 4 is contained in the container. A two-dimensional or three-dimensional image forming apparatus having an accommodating portion for accommodating the active energy ray-curable ink according to any one of claims 1 to 4 in a container and an irradiation means for irradiating the active energy ray. .. A two-dimensional or three-dimensional image forming method for forming a two-dimensional or three-dimensional image by irradiating the active energy ray-curable ink according to any one of claims 1 to 4 with active energy rays. A method for producing a cured product, which comprises irradiating the active energy ray-curable ink according to any one of claims 1 to 4 with active energy rays to form a cured product.

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