JP5842459B2 - Actinic ray curable composition and actinic ray curable ink jet ink - Google Patents

Description

  The present invention relates to an actinic ray curable composition and an actinic ray curable inkjet ink using the composition.

As an actinic ray curable composition, a composition comprising a radical reactive (polymerizable) compound and a radical photopolymerization initiator is widely known. Although this radical polymerizable curable composition is cured at high speed, the radical generated by light irradiation is immediately deactivated by oxygen in the air and the reaction is stopped. In this case, a low molecular weight radical monomer that is VOC (volatile organic compound) remains, which causes a problem in safety and the like.
A composition comprising a cation reactive (polymerizable) compound and a photoacid generator is also known. In this combination, the strong acid, which is a reactive species, is not inhibited by oxygen (although it is inhibited by moisture or base), the reaction proceeds (post-curing) even after light irradiation, and the residual monomer can be reduced. . However, due to the presence of a strong acid, problems such as corrosion and modification around the cured product may occur.
A composition comprising an anion reactive (polymerizable) compound and a photobase generator is also known. In this combination, as in the case of the cationic system, in addition to the progress of the reaction after the light irradiation, a weak base can be used, so that problems such as corrosion and denaturation hardly occur. However, this system has a problem that the reaction rate is very slow and it is difficult to use in applications where high-speed curing is required.
In addition, although the technique using the same or similar compound used by this invention is well-known (patent document 1, nonpatent literature 1, etc.), the use form of a monomer, an application, etc. differ from this invention.

  The present invention has been made to solve the above-described problems of the prior art, and an object thereof is to provide an actinic ray curable composition that can be cured at high speed and that does not easily stop the curing reaction.

上記式中、Ａは脂環式構造又は環構成原子として酸素原子を含む複素環式構造を表し、置換基を有していても良く、環の中に二重結合を二つ有していても良い。
２） 更に光ラジカル重合開始剤を含むことを特徴とする１）に記載の活性光線硬化組成物。
３） 更に、ラジカル重合性化合物を含むことを特徴とする１）又は２）に記載の活性光線硬化組成物。
４） 前記ラジカル重合性化合物が多官能モノマーであることを特徴とする３）に記載の活性光線硬化組成物。
５） １）〜４）のいずれかに記載の活性光線硬化組成物を含むことを特徴とする活性光線硬化型インクジェット用インク。 The above problems are solved by the following inventions 1) to 5).
1) An actinic ray curable composition comprising a base-reactive compound represented by the following general formula (1) and a photobase generator.

In the above formula, A represents an alicyclic structure or a heterocyclic structure containing an oxygen atom as a ring constituent atom, may have a substituent, and has two double bonds in the ring. Also good.
2) The actinic ray curable composition according to 1), further comprising a photoradical polymerization initiator.
3) The active ray curable composition according to 1) or 2), further comprising a radical polymerizable compound.
4) The actinic ray curable composition according to 3), wherein the radical polymerizable compound is a polyfunctional monomer.
5) An actinic radiation curable inkjet ink comprising the actinic radiation curable composition according to any one of 1) to 4).

  According to the present invention, it is possible to provide an actinic ray curable composition that can be cured at high speed and does not easily stop the curing reaction.

Hereinafter, the present invention will be described in detail.
As described above, the radical-reactive compound cures at high speed, but it is difficult to complete the reaction and causes problems such as VOC. On the other hand, since an anion reactive compound can be expected to be postcured, problems such as VOC are less likely to occur but the reaction is slow.
Thus, combining a radical reaction with a very fast curing speed and an anionic reaction with a slow reaction speed but post-curing and less likely to cause problems such as VOC can compensate for each other's drawbacks.
The present invention realizes a combination of the above two types of reactions by using a compound having an anion reactivity and at the same time a radical reactivity.

上記式中、Ａは脂環式構造又は環構成原子として酸素原子を含む複素環式構造を表し、アルキル基等の置換基を有していても良く、環の中に二重結合を二つ有していても良い。
具体的には、Ａは５〜７員環であり、環はアルキル基、アルコキシ基、エステル基等を有していても良く、これらの基の炭素数は１〜６が好ましい。
具体例としては以下のようなものが挙げられるが、これらに限定されるものではない。 The actinic ray curable composition of the present invention includes a base-reactive compound represented by the following general formula (1).

In the above formula, A represents an alicyclic structure or a heterocyclic structure containing an oxygen atom as a ring-constituting atom, may have a substituent such as an alkyl group, and has two double bonds in the ring. You may have.
Specifically, A is a 5- to 7-membered ring, and the ring may have an alkyl group, an alkoxy group, an ester group, or the like, and these groups preferably have 1 to 6 carbon atoms.
Specific examples include, but are not limited to, the following.

When these base-reactive compounds and photobase generators are combined, a base generated by actinic ray irradiation becomes a trigger, and the base-reactive compound reacts and cures. Further, the base is not a very strong base such as alkali metal or alkyl lithium, but may be an organic base such as amine, amidine, guanidine, or phosphazene. Therefore, it can be combined with a photobase generator that generates a so-called organic base. As a result, problems such as corrosion and modification around the cured composition can be avoided.
Various known compounds can be used as the photobase generator, but preferably oxime esters, quaternary ammonium salts, acyl compounds, carbamates, aminoacetophenones, and the like are used.

Among the basic reactive compounds, those having an oxygen atom as a ring-constituting atom and also having radical reactivity can achieve a high curing rate by adding a photo radical polymerization initiator. As the radical photopolymerization initiator, various known compounds can be used. Preferably, benzophenones, alkylphenones, acylphosphine oxides, oxyphenyl acetates, benzoin ethers, oxime esters, thioxanthones, Etc. can be used.
Further, when other radical polymerizable compounds, particularly polyfunctional monomers are used, curing can be performed at a higher speed.

Specific examples of the radical polymerizable compound include vinyl compounds, (meth) acrylate compounds, crotonic acid compounds, and acrylamide compounds. From the viewpoint of curing speed, (meth) acrylate compounds and (meth) acrylamide compounds are exemplified. preferable.
Furthermore, various known colorants, sensitizers, viscosity modifiers, surfactants, and the like can be added to the actinic ray curable composition of the present invention as necessary.
The use of the above-mentioned actinic ray curable composition is not particularly limited as long as it is a field in which a photocurable material is generally used, but it is preferably used as an actinic ray curable inkjet ink.

As a colorant when used as an inkjet ink, various known dyes and pigments can be used. When a pigment is used, a dispersant or the like may be used as necessary.
As the colorant, those excellent in light resistance and rich in color reproducibility are preferable, and those which do not affect the curing reaction and do not inhibit the polymerization are preferable.
Examples of the ink receptor to which the ink jet ink of the present invention can be applied include papers such as plain paper and coated paper, and various known materials such as non-permeable plastic, metal, and glass.
Various light sources such as a mercury lamp, a metal halide lamp, a xenon lamp, and an LED can be used as the light source for irradiating the active light curable composition of the present invention with active light.

  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.

Examples 1-8, Comparative Examples 1-2
Actinic ray curable compositions were prepared by mixing and stirring materials having the composition ratios shown in the columns of Examples and Comparative Examples in Table 1. In Examples 5 and 6 and Comparative Example 2, a pigment was further added and mixed and stirred to prepare an actinic ray curable inkjet ink. The numbers in parentheses in the table are parts by weight.
The following pigments were used.
CB: carbon black pigment, manufactured by Ciba Japan Co., Ltd .: MICROLITH Black CK)
・ Blue: Ciba Japan Co., Ltd .: MICROLITH Blue 4G-K

Moreover, as a monomer, (A-2)-(A-4), (A-10), (A-12), the following (B-1)-(B-6), and (D-1) mentioned above are mentioned. ), The following (C-1) and (C-2) compounds are used as photobase generators, and the following (C-3) and (C-4) are used as photoradical polymerization initiators. The following compounds were used.

After each ink of Examples and Comparative Examples was applied to a slide glass, light irradiation was performed with a mercury lamp (manufactured by HOYA-SCHOTT: EX-250, 25 mW / cm ² ) to evaluate curability. The comparative evaluation was performed based on the surface tackiness. The surface tack (stickiness) was performed by touching the sample after measurement with a finger. The results are shown in Table 1.

上記比較例１、２は、一般式（１）と異なる構造のモノマーのため、粘つきが残り十分に硬化していないことが分かった。

Since the comparative examples 1 and 2 are monomers having a structure different from that of the general formula (1 ), it has been found that the adhesive remains and is not sufficiently cured.

JP 2002-328475 A

Polymer Preprints, Japan Vol. 58, no. 2 (2009), p. 2429

Claims (5)

An actinic ray curable composition comprising a base-reactive compound represented by the following general formula (1) and a photobase generator.

In the above formula, A represents an alicyclic structure or a heterocyclic structure containing an oxygen atom as a ring constituent atom, may have a substituent, and has two double bonds in the ring. Also good.   The actinic ray curable composition according to claim 1, further comprising a photo radical polymerization initiator.   The actinic ray curable composition according to claim 1, further comprising a radical polymerizable compound.   The actinic ray curable composition according to claim 3, wherein the radical polymerizable compound is a polyfunctional monomer.   An actinic ray curable inkjet ink comprising the actinic ray curable composition according to claim 1.