JP2011184484A - Ink composition for inkjet recording, inkjet recording method, printed matter, method for producing molded printed matter, and molded printed matter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition for inkjet recording that is excellent in processing suitability of a cured film and does not cause contamination by a volatile component even under a high temperature, to provide an inkjet recording method using the ink composition for inkjet recording, to provide printed matter, to provide a method for producing molded printed matter and to provide molded printed matter. <P>SOLUTION: The ink composition for inkjet recording includes (component a) a heterocyclic polymerizable compound having one (meth)acryloyl group in the molecule and having one 5- or 6-membered heterocyclic ring containing an oxygen atom as a heteroatom, (component b) a polymerizable compound having one N-vinyl group in the molecule, (component c) a polymerizable compound having two vinyl ether groups in the molecule, (component d) a radical photopolymerization initiator having a molecular weight of not less than 250 and (component e) a polymerization inhibitor having a molecular weight of not less than 250. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an ink composition for ink jet recording, an ink jet recording method, a printed matter, a method for producing a shaped printed matter, and a shaped printed matter.

As an image recording method for forming an image on a support based on an image data signal, there are an electrophotographic method, a sublimation type and melt type thermal transfer method, an ink jet method and the like. The ink jet method is an inexpensive apparatus and ejects ink only to a required image portion to form an image directly on a support. Therefore, the ink composition can be used efficiently, and the running cost is low. Furthermore, there is little noise and it is excellent as an image recording method.
Specific examples of conventional ink compositions include the ink compositions described in Patent Documents 1 to 4.

JP 2008-075062 A JP 2008-105393 A JP 2009-197194 A JP 2007-056232 A

Conventionally, as a polymerizable compound contained in the radiation curable ink composition, by using a monofunctional polymerizable monomer, the cured image has been made flexible and stretchable, but the curability is low, When the image surface is sticky, and the molded printed matter (molded product) is stacked, the image surface and the back side of the molded printed matter adhere to each other, and so-called blocking resistance is insufficient. .
Conversely, there are also radiation curable ink compositions that use polyfunctional polymerizable monomers to increase polymerization cross-linking points, increase curability, and improve blocking resistance. There was a drawback that the drilling suitability was not sufficient.
In the present situation, an ink composition having such a high level of curability and low stickiness, stretchability, and perforating processability has not yet been developed.
In addition, if there are many non-curable low molecular components in the ink composition, the low molecular components will volatilize and diffuse from the cured image when heated and softened, contaminating the vicinity of the image and the heating device, or molding processed products at high temperatures. There was a problem that low-molecular components volatilized from the incorporated products.

  An object of the present invention is to provide an ink composition for ink jet recording which is excellent in processability of a cured film and does not generate contamination by volatile components even at high temperatures, an ink jet recording method using the ink composition for ink jet recording, a printed material, and a molded printed material. It is to provide a manufacturing method and a molded printed matter.

The above problems have been solved by the means described below.
<1> (Component a) A heterocyclic polymerizable compound having one (meth) acryloyl group in the molecule and one 5- or 6-membered heterocyclic ring containing an oxygen atom as a hetero atom (Component b) ) A polymerizable compound having one N-vinyl group in the molecule, (component c) a polymerizable compound having two vinyl ether groups in the molecule, (component d) a radical photopolymerization initiator having a molecular weight of 250 or more, and ( An ink composition for ink-jet recording, comprising component e) a polymerization inhibitor having a molecular weight of 250 or more,
<2> The content of the component a is 20 to 70% by weight, the content of the component b is 10 to 50% by weight, and the content of the component c is 0.1% with respect to the total weight of the ink composition. <3>, the ink composition according to <1>,
<3> The ratio of the total weight of the polymerizable compound including the component a, the component b, and the component c to the total weight of the component d and the component e is 1: 0.01 to 1: 0.2. The ink composition according to <1> or <2>,
<4> The ink composition according to any one of <1> to <3>, wherein the component a is a compound represented by the formula (a-1).

（式（ａ−１）中、Ｒ¹及びＲ²は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表し、Ｒ¹とＲ²とが結合して環を形成してもよく、Ｒ³は水素原子又は炭素数１〜３のアルキル基を表し、Ｘ¹及びＸ²は、それぞれ独立に、メチレン基又はエーテル性酸素原子を表し、少なくともＸ¹又はＸ²がエーテル酸素原子であり、Ｗ¹及びＷ²は、それぞれ独立に、単結合、メチレン基又はカルボニル基を表し、Ｚは、単結合、又は、炭素数１〜５のアルキレン基、炭素数１〜５のアルキレンオキシ基、エステル結合（−ＣＯＯ−又は−ＯＣＯ−）、もしくは、これらを組み合わせた２価の連結基を表し、Ａは水素原子又はメチル基を表す。）

(In Formula (a-1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹ and R ² may be bonded to form a ring. Well, R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X ¹ and X ² each independently represents a methylene group or an etheric oxygen atom, and at least X ¹ or X ² is an ether oxygen atom W ¹ and W ² each independently represent a single bond, a methylene group or a carbonyl group, Z represents a single bond, an alkylene group having 1 to 5 carbon atoms, or an alkyleneoxy group having 1 to 5 carbon atoms. Represents a group, an ester bond (—COO— or —OCO—), or a divalent linking group in combination of these, and A represents a hydrogen atom or a methyl group.)

<5> The ink composition according to any one of <1> to <4>, wherein the component a is tetrahydrofurfuryl (meth) acrylate,
<6> The ink composition according to any one of <1> to <5>, wherein the component b is N-vinylcaprolactam;
<7> An image forming step of forming an image on a support by discharging the ink composition according to any one of <1> to <6> by an inkjet method, and irradiating the obtained image with active radiation A curing step of curing the ink composition to obtain a printed material having a cured image on the support,
<8> Printed matter manufactured by the inkjet recording method according to <7>,
<9><1> to <6> An image forming step of forming an image on a support by ejecting the ink composition according to any one of the methods by an inkjet method, and irradiating the obtained image with actinic radiation A curing process for curing the ink composition to obtain a printed material having a cured image on the support; and a molding process for molding the printed material.
<10> The method for producing a molded printed material according to <9>, wherein the forming process is embossing, vacuum forming, pressure forming, or vacuum / pressure forming.
<11> The method for producing a molded printed matter according to <9> or <10>, including a punching step of punching the printed matter before or after the molding step.
<12> A molded printed material obtained by the method for producing a molded printed material according to any one of <9> to <11>.

  According to the present invention, an ink composition for ink jet recording which is excellent in processability of a cured film and does not cause contamination by volatile components even at high temperatures, an ink jet recording method using the ink composition for ink jet recording, a printed material, and a molded printed material. A production method and a molded printed material could be provided.

I. Ink composition for ink-jet recording The ink composition for ink-jet recording of the present invention (hereinafter also referred to as “ink composition”) has (component a) one (meth) acryloyl group in the molecule, as a hetero atom. A heterocyclic polymerizable compound having one 5- or 6-membered heterocyclic ring containing an oxygen atom, (component b) a polymerizable compound having one N-vinyl group in the molecule, and (component c) a vinyl ether group as a molecule And (component d) a radical photopolymerization initiator having a molecular weight of 250 or more, and (component e) a polymerization inhibitor having a molecular weight of 250 or more. In the specification, the description of “A to B” representing a numerical range is synonymous with “A or more and B or less” unless otherwise specified.

  The ink composition of the present invention is an oil-based ink composition that can be cured by actinic radiation. “Actinic radiation” is radiation that can give energy to generate polymerization initiation species in the ink composition by irradiation, and includes α rays, γ rays, X rays, ultraviolet rays, visible rays, electron rays, and the like. Of these, ultraviolet rays and electron beams are preferable from the viewpoint of curing sensitivity and device availability, and ultraviolet rays are more preferable.

The ink composition of the present invention is an ink composition having excellent processability. Specifically, the ink composition having excellent processability is excellent in curability, the blocking property of the cured ink composition film is high, the punching processability is excellent, the pencil hardness is high, and the stretchability is high. It means an ink composition excellent in.
The ink composition of the present invention is an ink composition that does not cause contamination around peripheral devices and image areas due to volatilization of volatile components such as low molecular components even at high temperatures after curing.

  From the viewpoints of blocking resistance, drilling suitability, pencil hardness, and stretchability, the content of the component a is 20 to 70% by weight and the content of the component b is 10 to 50% with respect to the total weight of the ink composition. It is preferable that the content of the component c is 0.1 to 3% by weight.

From the viewpoint of curability, blocking resistance, and contamination by volatile components, the ratio of the total weight of the polymerizable compound containing the component a, the component b, and the component c to the total weight of the component d and the component e is 1: 0.01-1: 0.2.
Hereinafter, each component will be described.

(Component a)
The ink composition of the present invention has (component a) (meth) acryloyl group in the molecule and a heterocyclic polymerizable property having one 5- or 6-membered heterocyclic ring containing an oxygen atom as a hetero atom. Contains compounds. Here, description such as “(meth) acryloyl group” means “acryloyl group and / or methacryloyl group”, and the same shall apply hereinafter. When component a is not included, the drilling suitability may be lowered, and the stretchability may be lowered.
Examples of the (meth) acryloyl group contained in the component a include a (meth) acrylamide group or a (meth) acryloyloxy group, and among them, a (meth) acryloyloxy group is preferable. Component a is preferably a compound having one (meth) acryloyloxy group in the molecule, and more preferably a compound having no addition polymerizable ethylenically unsaturated bond. Although the mechanism is unknown, excellent drilling suitability and stretchability can be imparted only when the hetero atom in the heterocycle is only an oxygen atom. Moreover, it is preferable that a heterocyclic ring does not contain an unsaturated bond in cyclic structure.
The (meth) acryloyloxy group and the heterocyclic ring are preferably bonded by a single bond or a divalent linking group.
In the present invention, component a is preferably a compound represented by formula (a-1).

（式（ａ−１）中、Ｒ¹及びＲ²は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表し、Ｒ¹とＲ²とが結合して環を形成してもよく、Ｒ³は水素原子又は炭素数１〜３のアルキル基を表し、Ｘ¹及びＸ²は、それぞれ独立に、メチレン基又はエーテル性酸素原子を表し、少なくともＸ¹又はＸ²がエーテル酸素原子であり、Ｗ¹及びＷ²は、それぞれ独立に、単結合、メチレン基又はカルボニル基を表し、Ｚは、単結合、又は、炭素数１〜５のアルキレン基、炭素数１〜５のアルキレンオキシ基、エステル結合（−ＣＯＯ−又は−ＯＣＯ−）、もしくは、これらを組み合わせた２価の連結基を表し、Ａは水素原子又はメチル基を表す。）

(In Formula (a-1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹ and R ² may be bonded to form a ring. Well, R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X ¹ and X ² each independently represents a methylene group or an etheric oxygen atom, and at least X ¹ or X ² is an ether oxygen atom W ¹ and W ² each independently represent a single bond, a methylene group or a carbonyl group, Z represents a single bond, an alkylene group having 1 to 5 carbon atoms, or an alkyleneoxy group having 1 to 5 carbon atoms. Represents a group, an ester bond (—COO— or —OCO—), or a divalent linking group in combination of these, and A represents a hydrogen atom or a methyl group.)

In formula (a-1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹ and R ² may be bonded to form a ring. . The alkyl group having 1 to 4 carbon atoms is preferably a methyl group, an ethyl group, or an isobutyl group. Moreover, as a ring which R < ¹ > and R < ² > couple | bonded, a C5-C6 cycloalkyl group is preferable.
R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ³ is preferably a hydrogen atom or an ethyl group.
X ¹ and X ² each independently represent a methylene group or an etheric oxygen atom, and at least X ¹ or X ² is an ether oxygen atom.
W ¹ and W ² each independently represent a single bond, a methylene group or a carbonyl group, preferably a single bond or a methylene group.
Z is a single bond, an alkylene group having 1 to 5 carbon atoms, an alkyleneoxy group having 1 to 5 carbon atoms, an ester bond (—COO— or —OCO—), or a divalent linking group obtained by combining these. Represents.
Examples of the combination of the linking group which bonds to acryloyloxy groups at ^* is attached _{portion, -CH 2 - (O-R} 4) n - *, _{or, -CH 2 - (OCO-R} 4) n - * Is preferred. R ⁴ represents a linear or branched alkylene group having 1 to 5 carbon atoms, and n represents an integer of 1 to 3.

  A represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom. That is, the component a is preferably an acrylate compound because the acrylate is more excellent in polymerizability than the methacrylate, and better curability can be obtained.

  Preferred specific examples of component a are shown below. In some of the following exemplified compounds, the hydrocarbon chain is described by a simplified structural formula in which symbols of carbon (C) and hydrogen (H) are omitted. A represents a hydrogen atom or a methyl group.

  Especially, it is preferable that the said component a is tetrahydrofurfuryl (meth) acrylate, and tetrahydrofurfuryl acrylate is more preferable.

  Since the balance of blocking resistance, drilling suitability, pencil hardness and stretchability is excellent, the content of component a relative to the total weight of the ink composition is preferably 20 to 70% by weight, and 30 to 60% by weight. Is more preferable, and 43 to 55 weight% is further more preferable.

(Component b)
The ink composition of the present invention comprises (Component b) a polymerizable compound having one N-vinyl group in the molecule. When component b is not contained, curability, blocking resistance, drilling suitability, pencil hardness, and stretching ratio may be reduced.
Component b is preferably an N-vinyl lactam. As the N-vinyl lactams, N-vinyl lactams represented by the formula (b-1) are preferable.

In the formula (b-1), n represents an integer of 1 to 5, and n is 2 to 2 from the viewpoint of flexibility after the ink composition is cured, adhesion to the support, and availability of raw materials. It is preferably an integer of 4, more preferably n is 2 or 4, and particularly preferably n is 4, that is, N-vinylcaprolactam. N-vinylcaprolactam is preferable because it is excellent in safety, is generally available and can be obtained at a relatively low price, and provides particularly good ink curability and adhesion of a cured film to a support.
The N-vinyl lactams may have a substituent such as an alkyl group or an aryl group on the lactam ring, and may be linked with a saturated or unsaturated ring structure.
Component b may be used alone or in combination of two or more.

  The content of component b is preferably 10 to 50% by weight, more preferably 20 to 40% by weight, and still more preferably 30 to 38% by weight, based on the total weight of the ink composition. It is excellent in the balance of blocking resistance, drilling suitability, pencil hardness, and stretchability within the above range.

(Component c)
The ink composition of the present invention includes (Component c) a polymerizable compound having two vinyl ether groups in the molecule. Hereinafter, the “polymerizable compound having two vinyl ether groups in the molecule” is also referred to as “divinyl ether compound”.

  Divinyl ether compounds include diethylene ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, and cyclohexanedimethanol divinyl ether. A vinyl ether compound is mentioned, and among them, triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, and 1,4-butanediol divinyl ether are preferable because they can impart appropriate crosslinkability to the film. A divinyl ether compound may be used individually by 1 type, and may be used in combination of 2 or more type as appropriate.

  The content of the component c is preferably 0.1 to 3.0% by weight, more preferably 0.2 to 2.0% by weight, and more preferably 0.5 to 1.5% by weight with respect to the total weight of the ink composition. Is more preferable. If it is within the above range, it is excellent in the balance of blocking resistance, drilling suitability and pencil hardness, and the divergence of the low-molecular compound is suppressed, so that no contamination occurs.

(Other polymerizable compounds)
The ink composition of the present invention may contain other polymerizable compounds in addition to the components a to c as long as the effects of the present invention are not impaired. The component b and the component c are preferably contained in an amount of 80% by weight or more, more preferably 90% by weight or more of the total polymerizable compound.
The other polymerizable compound is preferably a monofunctional ethylenically unsaturated compound that does not correspond to Component a and Component b.
When a polyfunctional polymerizable compound other than component c is added, the pencil hardness of the cured film is improved, but the holeability and stretchability may be reduced.
Preferable other polymerizable compounds include, for example, aromatic monofunctional radical polymerizable monomers described in JP-A-2009-096985, and monofunctional radical polymerizable monomers having an aliphatic cyclic structure, among which phenoxyethyl ( (Meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate are preferred.

(Component d)
The ink composition of the present invention contains (Component d) a radical photopolymerization initiator having a molecular weight of 250 or more (hereinafter also referred to as “polymerization initiator”). The polymerization initiator is a compound that absorbs external energy such as the actinic radiation to generate a polymerization initiating species.
If the molecular weight of the polymerization initiator is less than 250, contamination may occur. From the viewpoint of suppressing the occurrence of contamination, the molecular weight of component d is more preferably 300 to 500.

  Examples of the polymerization initiator that can be used in the present invention include aromatic ketones, acylphosphine compounds, aromatic onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, Examples thereof include azinium compounds, metallocene compounds, active ester compounds, and compounds having a carbon halogen bond. Specific examples of these polymerization initiators include polymerization initiators described in JP 2008-208190 A and JP 2009-096985 A. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

  Of these, acylphosphine compounds and aromatic ketones are preferred as the polymerization initiator. Examples of aromatic ketones include α-aminoacetophenone compounds, α-hydroxyacetophenone compounds, thioxanthone compounds, and benzyldimethyl ketal compounds.

<Acylphosphine compound>
Preferred examples of the acylphosphine compound include the acylphosphine oxide compounds described in paragraphs 0080 to 0098 of JP-A-2009-096985, and among them, the formula (d-1) or the formula (d-2) is included in the structure of the compound. Those having the following structural formula are preferred.

  In particular, as the acylphosphine oxide compound, those having a chemical structure of the formula (d-3) or the formula (d-4) are preferable.

（式（ｄ−３）中、Ｒ⁶、Ｒ⁷、Ｒ⁸はメチル基又はエチル基を置換基として有していてもよい芳香族炭化水素基を表す。）

(In the formula (d-3), R ⁶ , R ⁷ and R ⁸ represent an aromatic hydrocarbon group which may have a methyl group or an ethyl group as a substituent.)

As a monoacylphosphine oxide compound represented by the formula (d-3), R ^{6 to} R ⁸ are preferably phenyl groups optionally having a methyl group as a substituent, and R ⁷ and R ⁸ Is more preferably a phenyl group, and R ⁸ is more preferably a phenyl group having 1 to 3 methyl groups.
Among them, as the monoacylphosphine oxide compound represented by the formula (d-3), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Darocur TPO: manufactured by Ciba Specialty Chemicals, Lucirin TPO: manufactured by BASF) Is preferred.

（式（ｄ−４）中、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹はメチル基又はエチル基を置換基として有していてもよい芳香族炭化水素基を表す。）

(In the formula (d-4), R ⁹ , R ¹⁰ and R ¹¹ represent an aromatic hydrocarbon group which may have a methyl group or an ethyl group as a substituent.)

In the bisacylphosphine oxide compound represented by the formula (d-4), R ^{9 to} R ¹¹ are preferably a phenyl group which may have a methyl group as a substituent, and R ¹¹ is a phenyl group. And R ⁹ and R ¹¹ are more preferably a phenyl group having 1 to 3 methyl groups.
Among these, as the bisacylphosphine oxide compound represented by the formula (d-4), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (IRGACURE819, manufactured by Ciba Specialty Chemicals) is preferable.

  In the present invention, the combined use of a monoacylphosphine oxide compound and a bisacylphosphine oxide compound is more preferable.

<Α-Aminoacetophenone compound>
Examples of the α-aminoacetophenone compound include those having a molecular weight of 250 or more among the α-aminoacetophenone compounds described in paragraphs 0100 to 0118 of JP2009-096985A. As the α-aminoacetophenone compound, a compound represented by the formula (d-5) is preferable.

（式（ｄ−５）中、Ｘ¹及びＸ²はそれぞれ独立に、メチル基、エチル基、又は、ベンジル基を表し、−ＮＸ³Ｘ⁴はジメチルアミノ基、ジエチルアミノ基又は、モルフォリノ基を表し、Ｘ⁵は、水素原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数１〜８のアルキルチオ基、ジメチルアミノ基、又は、モルフォリノ基を表し、前記ベンジル基は、炭素数１〜４のアルキル基で置換されていてもよい。）

(In formula (d-5), X ¹ and X ² each independently represent a methyl group, an ethyl group, or a benzyl group, and —NX ³ X ⁴ represents a dimethylamino group, a diethylamino group, or a morpholino group. X ⁵ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, a dimethylamino group, or a morpholino group, and the benzyl group is And may be substituted with an alkyl group having 1 to 4 carbon atoms.)

In formula (d-5), —NX ³ X ⁴ is preferably a dimethylamino group or a morpholino group.
X ⁵ is preferably an alkylthio group having 1 to 4 carbon atoms or a morpholino group.

  As the α-aminoacetophenone compound represented by the formula (d-5), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals, IRGACURE) 907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (manufactured by Ciba Specialty Chemicals, IRGACURE 369), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (manufactured by Ciba Specialty Chemicals, IRGACURE 379) can be mentioned, and these can be preferably used. .

<Α-Hydroxyacetophenone compound>
As the α-hydroxyacetophenone compound, a compound represented by the formula (b-6) is preferable.

（式（ｄ−６）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に、水素原子、又は、炭素数１〜１０のアルキル基を表し、Ｒ¹とＲ²とが、又は、Ｒ³とＲ⁴とが結合して炭素数４〜８の環を形成していてもよく、Ｌは炭素数１〜１０のアルキレン基を表す。）

(In formula (d-6), R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ¹ and R ² , or R ³ and R 4, respectively. ⁴ may combine with each other to form a ring having 4 to 8 carbon atoms, and L represents an alkylene group having 1 to 10 carbon atoms.)

In Formula (d-6), R ^{1 to} R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. preferable.
L represents an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a methylene group.

  Examples of the α-hydroxyacetophenone compound represented by the formula (d-5) include 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one (IRGACURE 127). , Manufactured by Ciba Specialty Chemicals).

<Thioxanthone compound>
The thioxanthone compound is preferably a compound represented by the formula (d-7).

（式（ｄ−７）中、Ｒ¹〜Ｒ⁸はそれぞれ独立に、水素原子、アルキル基、ハロゲン原子、ヒドロキシ基、シアノ基、ニトロ基、アミノ基、アルキルチオ基、アルキルアミノ基（一置換及び二置換の場合を含む。）、アルコキシ基、アルコキシカルボニル基、アシルオキシ基、アシル基、カルボキシ基又はスルホ基を表す。）

(In formula (d-7), R ^{1 to} R ⁸ are each independently a hydrogen atom, an alkyl group, a halogen atom, a hydroxy group, a cyano group, a nitro group, an amino group, an alkylthio group, an alkylamino group (monosubstituted and Including a case of disubstitution.), An alkoxy group, an alkoxycarbonyl group, an acyloxy group, an acyl group, a carboxy group or a sulfo group.

The alkyl group, alkylthio group, alkylamino group, alkoxy group, alkoxycarbonyl group, acyloxy group, and the alkyl moiety in the acyl group preferably have 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms. Preferably, it is 1-4.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ^7, and R ⁸ may be linked to each other to form a ring. Examples of the ring structure in the case where these form a ring include a 5- or 6-membered aliphatic ring, an aromatic ring, etc., and may be a heterocyclic ring containing an element other than a carbon atom. The rings may be further combined to form a binuclear ring, for example, a condensed ring. These ring structures may further have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, a cyano group, a nitro group, an amino group, an alkylthio group, an alkylamino group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an acyl group, a carboxy group, and a sulfo group. N, O, and S can be mentioned as an example of a hetero atom in case the formed ring structure is a heterocyclic ring.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 1-methoxycarbonylthioxanthone, 2-ethoxycarbonylthioxanthone, 3- (2-methoxyethoxycarbonyl) thioxanthone, 4-butoxycarbonylthioxanthone. 3-butoxycarbonyl-7-methylthioxanthone, 1-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl-3-chlorothioxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone, 1-ethoxycarbonyl-3-aminothioxanthone, 1-ethoxycarbonyl-3-phenylsulfylthioxanthone, 3,4-di [2- (2-methoxyethoxy) ethoxycarbonyl] thioxanthone 1-ethoxycarbonyl-3- (1-methyl-1-morpholinoethyl) thioxanthone, 2-methyl-6-dimethoxymethylthioxanthone, 2-methyl-6- (1,1-dimethoxybenzyl) thioxanthone, 2-morpholinomethylthioxanthone 2-methyl-6-morpholinomethylthioxanthone, n-allylthioxanthone-3,4-dicarboximide, n-octylthioxanthone-3,4-dicarboximide, N- (1,1,3,3-tetramethyl Butyl) thioxanthone-3,4-dicarboximide, 1-phenoxythioxanthone, 6-ethoxycarbonyl-2-methoxythioxanthone, 6-ethoxycarbonyl-2-methylthioxanthone, thioxanthone-2-polyethylene glycol ester, 2-hydroxy 3- (3,4-dimethyl-9-oxo -9H- thioxanthone-2-yloxy) -N, N, N- trimethyl-1-propanaminium chloride can be exemplified. Among these, from the viewpoint of availability and curability, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,3-diethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4 -Propoxythioxanthone, 2-cyclohexylthioxanthone, and 4-cyclohexylthioxanthone are preferable, and 2-isopropylthioxanthone and 4-isopropylthioxanthone are more preferable. Preferred examples of the thioxanthone compound include isopropylthioxanthone (manufactured by ALBEMARLE, FIRSTCURE ITX).

<Benzyldimethyl ketal compound>
Preferable examples of the benzyldimethyl ketal compound include 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE 651, manufactured by Ciba Specialty Chemicals).

In the present invention, the polymerization initiator is preferably an acylphosphine compound or an aromatic ketone.
Preferred combinations of polymerization initiators include a combination of a bisacylphosphine oxide compound and a monoacylphosphine oxide compound, a combination of an acylphosphine oxide compound and an α-hydroxyacetophenone compound, and a combination of an acylphosphine oxide compound and a thioxanthone compound. Among them, a combination of a bisacylphosphine oxide compound and a monoacylphosphine oxide compound is more preferable.

In the present invention, the total amount of the polymerization initiator used is preferably 0.1 to 20% by weight with respect to the total amount of the polymerizable compound used from the viewpoint of curability and prevention of contamination at high temperatures, 15 weight% is more preferable and 1.0-12 weight% is further more preferable.
Of the total amount of the polymerization initiator, 70% by weight or more is preferably an acylphosphine oxide compound or an α-aminoacetophenone compound, and more preferably an acylphosphine oxide compound.
Moreover, when using a sensitizer, the total usage-amount of a polymerization initiator is a weight ratio of a polymerization initiator: sensitizer with respect to a sensitizer, Preferably it is 200: 1-1: 200, More preferably It is in the range of 50: 1 to 1:50, more preferably 20: 1 to 1: 5.

(Component e)
The ink composition of the present invention contains (Component e) a polymerization inhibitor having a molecular weight of 250 or more. If the ink composition does not contain a polymerization inhibitor, the storability of the ink composition may be reduced and head clogging may occur. Further, if the molecular weight of the polymerization inhibitor is less than 250, contamination with low molecular weight compounds may occur. The molecular weight of the polymerization inhibitor is preferably 300 or more, more preferably 350 or more.

  The polymerization inhibitor is not limited as long as the molecular weight is 250 or more, but examples include hindered phenol polymerization inhibitors, nitroso polymerization inhibitors, hindered amine polymerization inhibitors, and hindered phenol polymerizations. Inhibitors and nitroso polymerization inhibitors are preferred, and the use of nitroso polymerization inhibitors alone or the combined use of hindered phenol polymerization inhibitors and nitroso polymerization inhibitors is more preferred.

<Hindered phenol polymerization inhibitor>
The hindered phenol polymerization inhibitor that can be used in the present invention is not limited as long as the molecular weight is 250 or more. For example, among the phenolic antioxidants described in JP2009-120628A, the molecular weight is low. More than 250 can be used.
Among these, the hindered phenol polymerization inhibitor is preferably a compound represented by the formula (e-1).

（式（ｅ−１）中、Ｒ¹及びＲ²は、それぞれ独立に、直鎖又は分岐を有する炭素数１〜１０のアルキル基を表し、Ｌ¹は単結合又は炭素数１〜５のアルキレン基を表し、Ｒ³は、直鎖若しくは分岐を有する炭素数１〜３０のアルキル基、直鎖若しくは分岐を有する炭素数１〜３０のアルコキシカルボニル基、又は、カルボニル基を介してＬ¹に結合する直鎖若しくは分岐を有する炭素数１〜３０のＮ−アルキルアミド基を表す。）

(In formula (e-1), R ¹ and R ² each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, and L ¹ is a single bond or an alkylene having 1 to 5 carbon atoms. R ³ represents a linear or branched alkyl group having 1 to 30 carbon atoms, a linear or branched alkoxy group having 1 to 30 carbon atoms, or bonded to L ¹ via a carbonyl group. Represents a linear or branched N-alkylamide group having 1 to 30 carbon atoms.)

In formula (e-1), R ¹ and R ² each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, a methyl group or A tert-butyl group is more preferred.
R ³ is a linear or branched alkyl group having 1 to 30 carbon atoms, a linear or branched alkoxycarbonyl group having 1 to 30 carbon atoms, or a straight chain bonded to L ¹ via a carbonyl group or A branched C1-C30 N-alkylamide group is represented, and a linear or branched C5-C25 alkoxycarbonyl group is especially preferable.
The compound represented by the formula (e-1) may have a substituent on an introduceable carbon atom. Examples of the substituent include a hydroxy group, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), amino group, alkylamino group, dialkylamino group, alkoxy group, alkylthio group and the like.

  In the present invention, a compound represented by the formula (e-2) can also be preferably used.

（式（ｅ−２）中、Ｒ¹及びＲ²は、それぞれ独立に、水素原子、炭素数１〜１０の分岐を有していてもよいアルキル基を表し、Ｌ¹は単結合又は炭素数１〜５のアルキレン基を表し、Ｌ²は、炭素数１〜３０の直鎖又は分岐を有するアルキレン基、炭素数１〜３０の直鎖又は分岐を有するアルキレンオキシカルボニル基、又は、カルボニル基を介してＬ¹に結合する炭素数１〜３０の直鎖又は分岐を有するＮ−アルキレンアミド基を表し、ｍは２〜５の整数を表し、Ｘ¹はｍ価の連結基を表す。）

(In formula (e-2), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group which may have 1 to 10 carbon atoms, and L ¹ represents a single bond or a carbon number. 1 to 5 alkylene group, L ² represents a linear or branched alkylene group having 1 to 30 carbon atoms, a linear or branched alkyleneoxycarbonyl group having 1 to 30 carbon atoms, or a carbonyl group. Represents a linear or branched N-alkyleneamide group having 1 to 30 carbon atoms bonded to L ¹ through m, m represents an integer of 2 to 5, and X ¹ represents an m-valent linking group.

In the formula (e-2), R ¹ and R ² are the same as R ¹ and R ² in the formula (e-1), and preferred ranges are also the same.
L ¹ represents a single bond or an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms.
L ² is a C 1-30 straight-chain or branched alkylene group, a C 1-30 straight-chain or branched alkyleneoxycarbonyl group, or a carbon number bonded to L ¹ via a carbonyl group. An N-alkyleneamide group having 1 to 30 straight or branched chains is preferable, and an alkyleneoxycarbonyl group having 5 to 25 carbon atoms and having a straight chain or branched chain is particularly preferable.

X ¹ is a single bond, a carbonyl group, an ester bond (—COO—, —OCO—), a thio group, a sulfonyl group, a sulfinyl group, an oxy group, a phosphonic acid ester group, an alkylene group having 1 to 6 carbon atoms, or a carbon number 6-12 arylene group, amino group, m-valent C1-C6 aliphatic hydrocarbon group from which m hydrogen atoms have been removed, m-valent C6-C12 aromatic group from which m hydrogen atoms have been removed Examples thereof include m-valent 6- to 12-membered heterocyclic groups obtained by removing m hydrogen atoms from a heterocyclic ring such as a hydrocarbon group, triazine, and dioxane, and combinations of these linking groups.

When m is 3 or 4, X ¹ is an m-valent aliphatic hydrocarbon group having 1 to 6 carbon atoms from which m hydrogen atoms have been removed, or an m-valent carbon number from which m hydrogen atoms have been removed. Examples include 6-12 aromatic hydrocarbon groups and m-valent 6-12-membered heterocyclic groups excluding m hydrogen atoms. Specifically, the following linking groups are preferable. In the following linking groups, a plurality of Rs represent groups in parentheses in the formula (e-2). These Rs may be the same or different within one compound.

The compound represented by the formula (e-2) may have a substituent on an introduceable carbon atom, and examples of the substituent include the substituents in the formula (e-1).
Specific examples of hindered phenol polymerization inhibitors that can be preferably used in the present invention are shown below, but are not limited thereto. In the present invention, in the chemical formula, the hydrocarbon chain may be described by a simplified structural formula in which symbols of carbon (C) and hydrogen (H) are omitted.

  As the hindered phenol polymerization inhibitor, the compound (IR1NOX 1010, manufactured by Ciba Specialty Chemicals) and the compound (e6) (IRGANOX 1135, manufactured by Ciba Specialty Chemicals) are preferable.

<Nitroso polymerization inhibitor>
As the nitroso polymerization inhibitor, a known nitroso polymerization inhibitor can be used as long as the molecular weight is 250 or more. For example, the nitroso polymerization polymerization described in paragraphs 0082 to 0087 of JP2009-120628A is not limited. Among the inhibitors, those having a molecular weight of 250 or more can be used.
Examples of the nitroso polymerization inhibitor include tris (N-nitroso-N-phenylhydroxylamine) ammonium salt (manufactured by ALBEMARLE, FIRSTCURE ST-1).

  In the present invention, the total amount of the polymerization inhibitor having a molecular weight of 250 or more is preferably 0.01 to 2.0% by weight with respect to the total weight of the ink composition from the viewpoint of curability and prevention of contamination at high temperature. 0.1 to 1.5% by weight is more preferable, and 0.4 to 1.0% by weight is more preferable.

  In the present invention, in addition to the above components a to e, (component f) a colorant, (component g) a dispersant, and (component h) a surfactant may be contained. Sensitizers, co-sensitizers, ultraviolet absorbers, antioxidants, anti-fading agents, conductive salts, solvents, polymer compounds, basic compounds and the like may be included. These are described in Japanese Patent Application Laid-Open No. 2009-221416, and can also be used in the present invention.

(Component f) Colorant The ink composition of the present invention may contain a colorant in order to improve the visibility of the formed image area. A clear ink containing no colorant is also included in the ink composition of the present invention.
Although there is no restriction | limiting in particular as a coloring agent, The pigment and oil-soluble dye which were excellent in weather resistance and were rich in color reproducibility are preferable, and it can select and use arbitrarily from well-known coloring agents, such as a soluble dye. As the colorant, it is preferable to select a compound that does not function as a polymerization inhibitor from the viewpoint of not reducing the sensitivity of the curing reaction by actinic radiation.
Although it does not necessarily limit as a pigment which can be used for this invention, For example, the organic or inorganic pigment of the following number described in a color index can be used. Examples of red or magenta pigments include Pigment Red 3, 5, 19, 22, 31, 38, 42, 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, blue or cyan pigments include Pigment Blue 1,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,1 -1, 22, 27, 28, 29, 36, 60, Pigment Green 7, 26, 36, 50 as a green pigment, and Pigment Yellow 1, 3, 12, 13, 14, 17, 34 as a yellow pigment , 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 120, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 180 185, 193, Pigment Black 7, 28, 26 as the black pigment, and Pigment White 6, 18, 21, etc. as the white pigment according to the purpose.
In the present invention, a disperse dye can be used as long as it is soluble in a water-immiscible organic solvent. The disperse dye generally includes a water-soluble dye, but in the present invention, the disperse dye is preferably used as long as it is soluble in a water-immiscible organic solvent.
Preferable specific examples of the disperse dye 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 and 237 C. I. Disperse Orange 13, 29, 31: 1, 33, 49, 54, 55, 66, 73, 118, 119 and 163; 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 and 362; I. Disperse 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 and 368; I. Disperse Green 6: 1 and 9;

  It is preferable that the colorant is appropriately dispersed in the ink composition after being added to the ink composition. For dispersing the colorant, for example, a dispersion device such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, or a paint shaker can be used.

The colorant may be directly added together with each component when preparing the ink composition. Further, in order to improve dispersibility, it may be added to a dispersion medium such as a solvent or a polymerizable compound used in the present invention in advance and uniformly dispersed or dissolved, and then blended.
In the present invention, in order to avoid the deterioration of solvent resistance when the solvent remains in the cured image and the problem of VOC (Volatile Organic Compound) of the remaining solvent, the colorant is polymerizable. It is preferable to add and mix in advance in a dispersion medium such as a compound. In consideration of only dispersibility, it is preferable to select a monomer having the lowest viscosity as the polymerizable compound used for the addition of the colorant. One or more colorants may be appropriately selected and used according to the purpose of use of the ink composition.

When using a colorant such as a pigment that remains in the ink composition as a solid, the weight average particle diameter of the colorant particles is preferably 0.005 to 0.5 μm, more preferably 0.01. It is preferable to set the colorant, the dispersant, the dispersion medium, the dispersion conditions, and the filtration conditions so that the thickness becomes ˜0.45 μm, more preferably 0.015 to 0.4 μm. This particle size control is preferable because clogging of the head nozzle can be suppressed and the storage stability, transparency, and curing sensitivity of the ink composition can be maintained.
The content of the colorant in the ink composition is appropriately selected depending on the color and purpose of use, but is preferably 0.01 to 30% by weight with respect to the weight of the whole ink composition.

(Component g) Dispersant The ink composition of the present invention preferably contains a dispersant. In particular, when a pigment is used, a dispersant is preferably contained in order to stably disperse the pigment in the ink composition. As the dispersant, a polymer dispersant is preferable. The “polymer dispersing agent” in the present invention means a dispersing agent having a weight average molecular weight of 1,000 or more.

As the polymer dispersant, DISPERBYK-101, 102, 103, 106, 111, 161, 162, 163, 164, 166, 167, 168, 170, 171, 174, 182 (manufactured by BYK Chemie); EFKA 4010, 4046 4080, 5010, 5207, 5244, 6745, 6750, 7414, 745, 7462, 7500, 7570, 7575, 7580 (manufactured by Fuka Additive); Disperse Aid 6, 8, 15, 9100 (manufactured by San Nopco) ); SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, 22000, 24000, 26000, 28000, 32000, 36000, 39000, 41000, 71000, etc. Sparse dispersant (Noveon); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (( ADEKA Co., Ltd.), Ionette S-20 (manufactured by Sanyo Chemical Industries, Ltd.); Disparon KS-860, 873SN, 874 (polymer dispersing agent), # 2150 (aliphatic polycarboxylic acid), # 7004 (poly) Ether ester type) (manufactured by Enomoto Kasei Co., Ltd.).
The content of the dispersant in the ink composition is appropriately selected depending on the purpose of use, but is preferably 0.05 to 15% by weight with respect to the total weight of the ink composition.

(Component h) Surfactant A surfactant may be added to the ink composition of the present invention in order to impart stable discharge properties for a long time. Examples of the surfactant include those described in JP-A Nos. 62-173463 and 62-183457. For example, anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene blocks Nonionic surfactants such as copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts.

(Ink properties)
In the present invention, it is preferable that the viscosity of the ink composition at 25 ° C. is 40 mPa · s or less in consideration of dischargeability. More preferably, it is 5-40 mPa * s, More preferably, it is 7-30 mPa * s. Moreover, it is preferable that the viscosity in discharge temperature (Preferably 25-80 degreeC, More preferably, 25-50 degreeC) is 3-15 mPa * s, and it is more preferable that it is 3-13 mPa * s. It is preferable that the composition ratio of the ink composition of the present invention is appropriately adjusted so that the viscosity is in the above range. By setting the viscosity at room temperature high, even when a porous support is used, penetration of the ink composition into the support can be avoided, and uncured monomers can be reduced. Further, ink bleeding at the time of landing of the ink composition droplets can be suppressed, and as a result, the image quality is improved.

  The surface tension of the ink composition of the present invention at 25 ° C. is preferably 20 to 35 mN / m, and more preferably 23 to 33 mN / m. When recording on various supports such as polyolefin, PET, coated paper, and uncoated paper, 20 mN / m or more is preferable from the viewpoint of bleeding and penetration, and 35 mN / m or less is preferable in terms of wettability.

II. Inkjet recording method and printed matter The inkjet recording method of the present invention is an image forming step of forming an image on a support by ejecting the ink composition of the present invention by an inkjet method (hereinafter also referred to as (a) step). Further, the obtained image is irradiated with actinic radiation to cure the ink-jet ink composition, thereby obtaining a printed material having a cured image on the support (hereinafter also referred to as (b) step). ).
The printed matter of the present invention is manufactured by the ink jet recording method of the present invention.

First, step (a) will be described.
In the present invention, the support is not particularly limited, and a known support can be used. For example, paper, paper laminated with plastic (for example, polyethylene, polypropylene, polystyrene, etc.), metal plate (for example, , Aluminum, zinc, copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. ), Paper or plastic film on which the above-mentioned metal is laminated or vapor-deposited. Moreover, a nonabsorbable support body can be used suitably as a support body in this invention.

There is no restriction | limiting in particular as an inkjet recording device used for the inkjet recording method of this invention, The well-known inkjet recording device which can achieve the target resolution can be selected arbitrarily and can be used. That is, any known ink jet recording apparatus including a commercially available product can discharge the ink composition onto the support in the step (a) of the ink jet recording method of the present invention.
Examples of the ink jet recording apparatus that can be used in the present invention include an apparatus including an ink supply system, a temperature sensor, and an actinic radiation source.
The ink supply system includes, for example, an original tank containing the ink composition of the present invention, a supply pipe, an ink composition supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head. The piezo-type inkjet head is preferably 1 to 100 pL, more preferably 3 to 42 pL, still more preferably 8 to 30 pL, preferably 320 × 320 to 4,000 × 4,000 dpi, more preferably 400. It can be driven so that it can discharge at a resolution of × 400 to 1,600 × 1,600 dpi, more preferably 720 × 720 dpi. In the present invention, dpi represents the number of dots per 2.54 cm.

  In the present invention, since it is preferable to set the discharged ink composition to a constant temperature, heat insulation and heating can be performed from the ink composition supply tank to the inkjet head portion. The temperature control method is not particularly limited, but for example, it is preferable to provide a plurality of temperature sensors in each piping portion and perform heating control according to the flow rate of the ink composition and the environmental temperature. The temperature sensor can be provided near the ink composition supply tank and the nozzle of the inkjet head. Moreover, it is preferable that the head unit to be heated is thermally shielded or insulated so that the apparatus main body is not affected by the temperature from the outside air. In order to shorten the printer start-up time required for heating or to reduce the loss of heat energy, it is preferable to insulate from other parts and reduce the heat capacity of the entire heating unit.

  A radiation curable ink composition such as the ink composition of the present invention generally has a higher viscosity than a water-based ink composition usually used in an ink composition for ink jet recording, and therefore has a large viscosity fluctuation due to temperature fluctuations during ejection. Viscosity fluctuation of the ink composition has a great influence on the change of the droplet size and the change of the droplet discharge speed, and thus causes the image quality deterioration. Therefore, it is necessary to keep the temperature of the ink composition during ejection as constant as possible. Therefore, in the present invention, the control range of the temperature of the ink composition is preferably ± 5 ° C. of the set temperature, more preferably ± 2 ° C. of the set temperature, and ± 1 ° C. of the set temperature. Further preferred.

Next, step (b) will be described.
The ink composition ejected on the support is cured by irradiation with actinic radiation. This is because the polymerization initiator contained in the ink composition of the present invention is decomposed by irradiation with actinic radiation to generate a polymerization initiating species such as a radical, and the polymerization reaction of the polymerizable compound is a function of the polymerization initiating species. This is because it is created and promoted. At this time, if a sensitizer is present together with the polymerization initiator in the ink composition, the sensitizer in the system absorbs actinic radiation to be in an excited state, and promotes decomposition of the polymerization initiator by contacting with the polymerization initiator. And a more sensitive curing reaction can be achieved.

  Here, α rays, γ rays, electron beams, X rays, ultraviolet rays, visible light, infrared rays, or the like can be used as the active radiation used. Although the peak wavelength of actinic radiation is based also on the absorption characteristic of a sensitizer, it is preferable that it is 200-600 nm, for example, it is more preferable that it is 300-450 nm, and it is further more preferable that it is 350-420 nm.

Further, the ink composition of the present invention has sufficient sensitivity even with a low output actinic radiation. Therefore, it is appropriate to cure the exposed surface with an illuminance of 10 to 4,000 mW / cm ² , more preferably 20 to 2,500 mW / cm ² .

Mercury lamps and gas / solid lasers are mainly used as actinic radiation sources, and mercury lamps and metal halide lamps are widely known as light sources used for curing UV photocurable ink jet recording ink compositions. It has been. However, from the viewpoint of environmental protection, mercury-free is strongly desired, and replacement with a GaN-based semiconductor ultraviolet light-emitting device is very useful industrially and environmentally. Furthermore, LED (UV-LED) and LD (UV-LD) are small, have a long lifetime, high efficiency, and low cost, and are expected as light sources for photo-curable ink jets.
Further, a light emitting diode (LED) and a laser diode (LD) can be used as the active radiation source. In particular, when an ultraviolet light source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, Nichia Corporation has introduced a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm. If even shorter wavelengths are required, the LED disclosed in US Pat. No. 6,084,250 is capable of emitting actinic radiation centered between 300 nm and 370 nm. Can be illustrated. Other ultraviolet LEDs are also available and can emit radiation in different ultraviolet bands. The actinic radiation source preferred in the present invention is a UV-LED, particularly preferably a UV-LED having a peak wavelength at 350 to 420 nm.
Note that maximum illuminance of LED support on is preferably from 10 to 2,000 mW / cm ^2, more preferably 20 to 1,000 mW / cm ^2, is 50 to 800 mW / cm ² Is particularly preferred.

The ink composition of the present invention is suitably irradiated with such actinic radiation for 0.01 to 120 seconds, more preferably 0.01 to 90 seconds, and still more preferably 0.01 to 10 seconds. is there.
In the inkjet recording method of the present invention, the ink composition is irradiated with actinic radiation at an exposure surface illuminance of 2,000 mW / cm ² or less within 0.01 to 10 seconds after the ink composition is discharged. Is preferably cured.
Actinic radiation irradiation conditions and a basic irradiation method are disclosed in JP-A-60-132767. Specifically, the light source is provided on both sides of the head unit including the ink composition discharge device, and the head unit and the light source are scanned by a so-called shuttle method. Irradiation with actinic radiation is performed for a certain time (preferably 0.01 to 0.5 seconds, more preferably 0.01 to 0.3 seconds, still more preferably 0.01 to 0.15 seconds) after landing of the ink composition. ). In this way, by controlling the time from landing to irradiation of the ink composition to an extremely short time, it is possible to prevent the ink composition that has landed on the support from bleeding before curing. In addition, since the ink composition can be exposed to a porous support before reaching the deep part where the light source does not reach, it is preferable because residual unreacted monomer can be suppressed.
Further, the curing may be completed by another light source that is not driven. International Publication No. 99/54415 pamphlet discloses a method using an optical fiber or a method of irradiating a recording unit with UV light by applying a collimated light source to a mirror surface provided on the side of the head unit as an irradiation method. Such a curing method can also be applied to the ink jet recording method of the present invention.

  By adopting the ink jet recording method as described above, the dot diameter of the landed ink composition can be kept constant even on various supports having different surface wettability, and the image quality is improved. In addition, in order to obtain a color image, it is preferable to superimpose in order from the color with the lowest brightness. By superimposing the ink compositions in order of low lightness, it becomes easy for the irradiation rays to reach the lower ink composition, and good curing sensitivity, reduction of residual monomers, and improvement in adhesion can be expected. In addition, irradiation can be performed by discharging all colors and collectively exposing, but exposure for each color is preferable from the viewpoint of promoting curing.

In the ink jet recording method of the present invention, an ink set containing one or more ink compositions of the present invention can be suitably used. The order of the colored ink compositions to be ejected is not particularly limited, but it is preferable that the colored ink composition having a low lightness is applied to the support. When using an ink composition of yellow, cyan, magenta, and black as the ink composition of the present invention, it is preferably applied on the support in the order of yellow → cyan → magenta → black. Further, when white is added to this, it is preferably applied on the support in the order of white → yellow → cyan → magenta → black. Furthermore, the present invention is not limited to this, and the present invention is also used as an ink set including at least seven colors in total, that is, a light cyan and light magenta ink composition and a cyan, magenta, black, white and yellow dark ink composition. In this case, it is preferable to apply on the support in the order of white → light cyan → light magenta → yellow → cyan → magenta → black.
Thus, the ink composition of the present invention can form an image on the surface of the support by being cured with high sensitivity by irradiation with actinic radiation.

When the ink composition of the present invention is prepared in a plurality of colors and used as an ink set, at least one ink composition of the present invention is included, and two or more combinations of the ink composition of the present invention or an ink composition other than the present invention are combined The ink composition of the present invention having a color selected from the group consisting of cyan, magenta, yellow, black, white, light magenta, and light cyan is not particularly limited. It is preferable to include at least one.
The ink set of the present invention can be suitably used for the ink jet recording method of the present invention.
In order to obtain a full color image using the ink composition of the present invention, the ink set of the present invention is an ink set in which at least four dark ink compositions comprising yellow, cyan, magenta, and black are combined. It is more preferable that the ink set is a combination of five color ink compositions consisting of yellow, cyan, magenta, black, and white, and it is composed of yellow, cyan, magenta, black, and white. More preferably, the ink set is a combination of a five-color dark ink composition and a two-color ink composition comprising light cyan and light magenta.
The “dark ink composition” in the present invention means an ink composition in which the content of the colorant exceeds 1% by weight of the entire ink composition. There is no restriction | limiting in particular as said coloring agent, A well-known coloring agent can be used, A pigment and a disperse dye can be illustrated.
The ink set of the present invention includes at least one dark color ink composition and at least one light color ink composition, and the dark color ink composition and the light color ink composition use a colorant having a similar color. The ratio of the colorant concentration between the dark color ink composition and the light color ink composition is preferably dark color ink composition: light color ink composition = 15: 1 to 4: 1, and 12: 1 to The ratio is more preferably 4: 1, and more preferably 10: 1 to 4.5: 1. Within the above range, a vivid full-color image with little graininess can be obtained.

III. A method for producing a molded printed matter and a method for producing a molded printed matter according to the present invention include an image forming step of forming an image on a support by discharging the ink composition of the present invention by an ink jet method (hereinafter referred to as (a). Also referred to as a process.), A curing process (hereinafter referred to as (b) process) in which the obtained image is irradiated with actinic radiation to cure the inkjet ink composition and obtain a printed material having a cured image on the support. And a molding process for molding the printed matter (hereinafter also referred to as (c) process).
Moreover, the molded printed matter of the present invention is obtained by the method for producing a molded printed matter.

  The step (a) and step (b) in the method for producing a molded printed matter of the present invention are the same as the step (a) and step (b) in the inkjet recording method of the present invention. The support suitably used in the method for producing a molded printed matter of the invention will be described.

There is no particular limitation on the support that can be used in the method for producing a molded printed matter of the present invention, and a known support suitable for molding can be used. Specifically, polyolefin resins such as polyethylene, polypropylene, polymethylpentene, polybutene, olefin thermal plastic elastomer, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, terephthalic acid-isophthalic acid-ethylene glycol copolymer, Terephthalic acid-ethylene glycol-1,4 cyclohexane dimethanol copolymer, polyester resin such as polyester thermal plastic elastomer, polyamide resin such as nylon 6, nylon 9, nylon 6, 6, etc., polyvinyl fluoride, polyvinylidene fluoride, Fluorine resin such as poly (vinylidene trifluoride), ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene, acrylic resin, polyvinyl chloride, polystyrene, polycarbonate resin, etc. It can be exemplified.
Examples of the acrylic resin include polymethyl (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, ethyl (meth) acrylate-butyl (meth) ) Resins such as acrylate copolymers and methyl (meth) acrylate-styrene copolymers can be used alone or in a mixture of two or more.
Of these, polyethylene terephthalate, polycarbonate resin, and a resin resin blended with polycarbonate resin are preferably used in terms of ease of decorative printing and excellent durability of the finished molded product. A resin sheet blended with other resins is preferred. Moreover, the laminated body which laminated | stacked the 1 type (s) or 2 or more types of resin sheet may be sufficient as a support body.

  In the present invention, the thickness of the support (total thickness in the case of a laminated body) is a resin sheet having a thickness that allows vacuum / pressure forming using the principles of embossing, vacuum forming, pressure forming, and vacuum / pressure forming. Although it does not specifically limit, The thing of 50-2,000 micrometers is preferable, The thing of 100-1,500 micrometers is more preferable, The thing of 150-1,000 micrometers is further more preferable.

  Additives can be appropriately added to the thermoplastic resin sheet as necessary. Appropriate amounts of various additives can be added as long as they do not hinder the thermal behavior such as surface gloss and melting point. For example, UV stabilizers such as benzotriazole and benzophenone, light stabilizers such as hindered amine radical scavengers, lubricants such as silicone resins and waxes, colorants, plasticizers, heat stabilizers, antibacterial agents, antifungal agents And antistatic agents.

The formed printed matter of the present invention is produced by subjecting a thermoplastic resin sheet to a forming process such as vacuum forming, and an image is formed on the support by an ink jet method prior to forming.
The image is generally applied to the back side (the side in contact with the mold in vacuum forming) of the transparent sheet, but the image may be formed on the opposite side. In some cases, it is also possible to form an image only on the opposite surface. In this case, the thermoplastic resin sheet serving as the substrate does not need to be transparent.

  In the present invention, embossing, vacuum forming, pressure forming, or vacuum / pressure forming can be used for forming. A known apparatus can be used as an apparatus for forming a printed material, and may be an apparatus integrated with the ink jet recording apparatus or another apparatus.

  The embossing is a process of producing a three-dimensional effect by indenting a printed material or the like into an arbitrary shape such as a pattern or characters, and is performed using, for example, a roller or a press machine. An example of embossing is a hot and cold press method, and the method described in JP-A-10-199360 can be referred to. An example of an embossing apparatus by the hot and cold press method is shown below. In the embossing apparatus, a lower surface plate (lower surface plate) and an upper surface plate (upper surface plate) are disposed so as to be able to approach and separate from each other. A plate heater is fixed on the lower surface plate, and a plate heater is also fixed on the lower surface of the upper surface plate. Thereby, hot pressing can be performed while heating the support. In this hot press machine, a mold having a convex portion that follows a predetermined emboss shape is attached to the plate-type heater on the lower surface plate, and the convex portion is brought into contact with the heater fixed to the lower surface of the upper surface plate. A mold having a concave portion that matches the shape is attached. Then, an image-formed support is disposed, a cushion sheet is disposed between the support and the concave mold, and the upper surface plate is lowered to support it between the upper surface plate and the lower surface plate. Press the body and cushion sheet. The applied pressure in this hot pressing step is, for example, 30 tons, and the heating temperature by the plate type heater is, for example, 170 ° C. And an upper surface plate is pressed on a lower surface plate, a support body and a cushion sheet are pinched between metal mold | dies, and this hot press is hold | maintained for about 3 minutes. The support is heated by a heater through a mold, and a plurality of convex portions are formed by thermal deformation. Next, the support and the cushion sheet are sandwiched between the molds and placed between the internal water-cooled surface plates without a heater. For example, the internal water-cooled surface plate with a pressure of 30 tons and a holding time of about 3 minutes. Press and cold press. Thereby, the convex shape which carried out the heat deformation by the hot press is hold | maintained, and the molded printed matter which gave the embossing process is obtained. The applied pressure and heating temperature can be appropriately adjusted according to conditions such as the material of the printed matter used and the processed shape.

  Vacuum forming is a method in which a support on which an image has been formed is preheated to a temperature at which it can be thermally deformed in advance, and this is sucked into a mold by decompression and stretched while being compressed and cooled to the mold. In this method, the support on which the image is formed is preheated to a temperature at which it can be thermally deformed in advance, pressed from the opposite side of the mold, and then pressed and cooled on the mold. Vacuum / pressure forming is a method in which the pressure reduction and pressurization are performed simultaneously. For details, refer to Polymer Dictionary (Maruzen Co., Ltd.) p. Reference can be made to the item “thermoforming” described in 766 to 768 and the literature cited in the item.

(Drilling process)
Furthermore, it is preferable that the manufacturing method of the shaped printed matter of the present invention is a method including a punching step (step (d)) for punching the printed matter before or after the forming step. The drilling process is preferably provided after the molding process.
When the ink composition of the present invention is used, cracks do not occur in the cured film around the hole even if the hole is processed at room temperature (5 to 40 ° C.). As to whether or not cracking occurs, for example, punch No. without a large hole for manual OA. It is possible to evaluate by drilling using 200N (manufactured by Lion Office Co., Ltd.) and visually observing whether there are cracks or light transmission in the drilled portion of the image.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these examples. In the following description, “parts” means “parts by weight” unless otherwise specified.

(Preparation of cyan mill base A)
300 parts of IRGALITE BLUE GLVO (cyan pigment, manufactured by Ciba Specialty Chemicals), 620 parts of phenoxyethyl acrylate, and 80 parts of SOLPERSE 32000 were mixed with stirring to obtain cyan mill base A. Cyan mill base A was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed using a zirconia bead having a diameter of 0.65 mm for 4 hours at a peripheral speed of 9 m / s.

  Magenta mill base B, yellow mill base C, black mill base D and white mill base E were prepared in the same manner as cyan mill base A with the composition and dispersion conditions shown in Table 1.

(Coloring agent)
・ IRGALITE BLUE GLVO (Cyan Pigment, Ciba Specialty Chemicals)
・ CINQUASIA MAGENTA RT-335-D (magenta pigment, manufactured by Ciba Specialty Chemicals)
・ NOVOPERM YELLOW H2G (yellow pigment, manufactured by Clariant)
・ SPECIAL BLACK 250 (Black pigment, manufactured by Ciba Specialty Chemicals)
・ Taipeku CR60-2 (white pigment, manufactured by Ishihara Sangyo Co., Ltd.)
(Dispersant)
・ SOLSPERSE32000 (dispersant, manufactured by Noveon)

(Examples 1-33 and Comparative Examples 1-10)
<Method for producing ink composition>
Ink compositions of Examples 1 to 33 and Comparative Examples 1 to 10 were obtained by mixing and stirring the materials described in Tables 2 and 3.

<Inkjet image recording method>
An image was formed on the support using an inkjet recording experimental apparatus having a piezo-type inkjet nozzle. The ink supply system was composed of an original tank, supply piping, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head, and heat insulation and heating were performed from the ink supply tank to the inkjet head portion.
Temperature sensors were provided near the ink supply tank and the nozzle of the ink jet head, respectively, and temperature control was performed so that the nozzle portion was always 45 ° C. ± 2 ° C. The piezo-type inkjet head was driven so that 8 to 30 pl multi-size dots could be ejected at a resolution of 720 × 720 dpi. After landing, UV light was condensed to an exposure surface illuminance of 2,100 mW / cm ² , and the exposure system, main scanning speed and ejection frequency were adjusted so that irradiation started 0.1 seconds after the ink landed on the support. Further, the integrated light amount irradiated to the image was set to 3,000 mJ / cm ² . A HAN250NL high-cure mercury lamp (manufactured by GS Yuasa Corporation) was used as the ultraviolet lamp. In the present invention, dpi represents the number of dots per 2.54 cm. An ester film E5000 (film thickness 125 μm, manufactured by Toyobo Co., Ltd.) was used as a support. Each sample was drawn so that the average film thickness of the cured film of the ink composition was 12 μm.

<Evaluation method of curability>
In accordance with the inkjet recording method, a solid image having an average film thickness of 12 μm was drawn, and the degree of stickiness of the image was evaluated by palpation on the image surface after ultraviolet irradiation. The curing sensitivity was evaluated according to the following criteria.
○: No stickiness on the image.
Δ: The image is slightly sticky.
X: The uncured ink is not hardened so as to be transferred to the hand.

<Evaluation method of blocking resistance>
After drawing a solid image having an average film thickness of 12 μm in accordance with the ink jet recording method, an unprinted ester film E5000 is overlaid on the cured film so that the entire cured film of the printed material is covered. A load of / cm ² was applied and left for 1 day in an atmosphere at 30 ° C. Moreover, blocking resistance was evaluated according to the following criteria.
○: Transfer to the upper film, no sticking.
Δ: Transfer to the upper film is less than 5% of the total film area.
X: Transfer to the upper film is 5% or more of the total film area.

(Evaluation method for drilling suitability)
A printed material was produced in the same manner as the ink jet recording method described above except that Panlite PC-1151 (film thickness 500 μm, polycarbonate sheet, manufactured by Teijin Chemicals Ltd.) was used as the support.
Under the condition of 25 ° C., the printed material produced was punched with a large punch for manual OA No. Drilling was performed using 200N (manufactured by Lion Corporation). The image was visually observed for cracks and light transmission in the perforated portion of the image.
○: Cracks around the punch hole and no light was transmitted.
(Triangle | delta): Although there was a crack and permeation | transmission of light around a punch hole, it was a level which is satisfactory.
X: Cracks occurred around the punch holes, light was transmitted, and the product was unsuitable.

(Evaluation method of pencil hardness)
In accordance with JIS K 5600-5-4, evaluation was performed using a 2B to 3H pencil.

(Clouding evaluation method)
According to the above-mentioned ink jet recording method, a solid image having an average film thickness of 12 μm is drawn, and after ultraviolet irradiation, it is placed in a glass petri dish and heated on a hot plate at 95 ° C. ± 15 ° C. for 1 hour to evaluate the fog inside the petri dish did. When cloudiness occurs, it is determined that contamination with volatile components occurs.
○: No cloudiness
Δ: Cloudy but no problem.
X: Cloudy is very much, which causes a problem.

(Measurement method of stretch ratio)
A solid image having an average film thickness of 12 μm is drawn according to the above ink jet recording method except that Panlite PC-1151 (film thickness 500 μm, polycarbonate sheet, manufactured by Teijin Chemicals Ltd.) is used as the support, and the width is 2 .5cm, length 5.0cm cut out, using a precision universal testing machine (Autograph AGS-J) manufactured by Shimadzu Corporation and a thermostatic chamber TCR2W-200P to perform a tensile test in a 180 ° C. environment, The elongation ratio with respect to the length (5 cm) of the test piece before the test was measured.

The abbreviations described in Table 2 and Table 3 are as follows.
(Component a)

(Component d)
IRGACURE 819: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Ciba Specialty Chemicals)
DAROCUR TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Ciba Specialty Chemicals)
IRGACURE 907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals)
IRGACURE 651: 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by Ciba Specialty Chemicals)
IRGACURE 127: 2-Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (manufactured by Ciba Specialty Chemicals) )
FIRSTCURE ITX: Mixture of 2-isopropylthioxanthone and 4-isopropylthioxanthone (manufactured by ALBEMARLE)
(Comparative component d)
DAROCUR 1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by Ciba Specialty Chemicals)
IRGACURE 184: 1-hydroxy-cyclohexyl-phenyl-ketone (Ciba Specialty Chemicals)
(Component e)
FIRSTCURE ST-1: Mixture of tris (N-nitroso-N-phenylhydroxyamine) aluminum salt and 2-phenoxyethoxy acrylate IRGANOX 1135: Compound of (e6) (manufactured by Ciba Specialty Chemicals)
IRGANOX 1010: Compound of the above (e1) (manufactured by Ciba Specialty Chemicals)
(Comparative component e)
・ MEHQ: Hydroquinone monomethyl ether (Wako Pure Chemical Industries, Ltd.)
Q-1300: ammonium N-nitrosophenylhydroxylamine (manufactured by Wako Pure Chemical Industries, Ltd.)

  For the produced magenta mill base, yellow mill base, black mill base, and white mill base, an ink composition was prepared in the same manner as in Example 4, and evaluated in the same manner. As a result, the cured film was excellent in workability and no contamination occurred even at high temperatures. I understood it.

Claims (12)

(Component a) a heterocyclic polymerizable compound having one (meth) acryloyl group in the molecule and one 5- or 6-membered heterocyclic ring containing an oxygen atom as a hetero atom,
(Component b) a polymerizable compound having one N-vinyl group in the molecule,
(Component c) A polymerizable compound having two vinyl ether groups in the molecule,
(Component d) a radical photopolymerization initiator having a molecular weight of 250 or more, and
An ink composition for ink jet recording comprising (Component e) a polymerization inhibitor having a molecular weight of 250 or more.   The content of the component a is 20 to 70% by weight, the content of the component b is 10 to 50% by weight, and the content of the component c is 0.1 to 3% by weight with respect to the total weight of the ink composition. The ink composition according to claim 1, which is%.   The ratio of the total weight of the polymerizable compound containing the component a, the component b and the component c to the total weight of the component d and the component e is 1: 0.01 to 1: 0.2. The ink composition according to claim 1 or 2. The ink composition according to any one of claims 1 to 3, wherein the component a is a compound represented by the formula (a-1).

(In Formula (a-1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹ and R ² may be bonded to form a ring. Well, R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X ¹ and X ² each independently represents a methylene group or an etheric oxygen atom, and at least X ¹ or X ² is an ether oxygen atom W ¹ and W ² each independently represent a single bond, a methylene group or a carbonyl group, Z represents a single bond, an alkylene group having 1 to 5 carbon atoms, or an alkyleneoxy group having 1 to 5 carbon atoms. Represents a group, an ester bond (—COO— or —OCO—), or a divalent linking group in combination of these, and A represents a hydrogen atom or a methyl group.)   The ink composition according to claim 1, wherein the component a is tetrahydrofurfuryl (meth) acrylate.   The ink composition according to any one of claims 1 to 5, wherein the component b is N-vinylcaprolactam. An image forming step of forming an image on a support by discharging the ink composition according to any one of claims 1 to 6 by an inkjet method; and
An inkjet recording method comprising: a curing step of irradiating the obtained image with actinic radiation to cure the ink composition to obtain a printed material having a cured image on the support.   A printed matter produced by the ink jet recording method according to claim 7. An image forming step of forming an image on a support by discharging the ink composition according to any one of claims 1 to 6 by an inkjet method;
A curing step of irradiating the obtained image with actinic radiation to cure the ink composition to obtain a printed material having a cured image on the support; and
The manufacturing method of the molded printed matter characterized by including the shaping | molding process which shape | molds the said printed matter.   The method for producing a molded printed matter according to claim 9, wherein the forming process is embossing, vacuum forming, pressure forming, or vacuum / pressure forming.   The manufacturing method of the molded printed matter of Claim 9 or 10 including the punching process which punches the said printed matter before or after the said shaping | molding process process.   A shaped printed matter obtained by the method for producing a shaped printed matter according to any one of claims 9 to 11.