WO2015137506A1 - Active light curing-type inkjet ink, filling method, and image forming method - Google Patents

Abstract

The purpose of the present invention is to provide an active light curing-type inkjet ink by which can be obtained favorable image quality such that uneven density does not occur in images by preventing the separation of a gelling agent and a liquid component. This active light curing-type inkjet ink is subject to reversible sol-gel phase transition according to temperature, and is characterized by the following: at least including at least one kind of gelling agent and at least one kind of monomer; the at least one kind of monomer including a monomer A which has a viscosity of at least 50cp at 25˚C; the content of the monomer A being at least 40 mass% with respect to the total mass% of the inkjet ink; the viscosity of the inkjet ink prior to shearing being 50Pa·s-2000Pa·s; and the viscosity of the inkjet ink when sheared and filled into an ink pack being no more than 20Pa·s.

Description

Actinic ray curable inkjet ink, filling method and image forming method

The present invention relates to an actinic ray curable inkjet ink. The present invention also relates to a method for filling an ink pack with an actinic ray curable inkjet ink. Furthermore, the present invention relates to an image forming method using an actinic ray curable inkjet ink.

The ink jet recording method is used in various printing fields because it can form an image easily and inexpensively. As one of the ink jet recording methods, there is an ultraviolet curable ink jet method in which droplets of ultraviolet curable ink jet ink are landed on a recording medium and then cured by irradiation with ultraviolet rays to form an image. The ultraviolet curable ink jet method has been attracting attention in recent years because it can form an image having high scratch resistance and adhesion even on a recording medium having no ink absorbability.

For example, Patent Document 1 includes a carrier composition containing one or more radiation curable compounds and a drug capable of reversibly gelling the carrier composition, and the drug is transferred to the carrier composition at an ink discharge temperature. A radiation curable hot melt ink jet ink that is soluble and that produces a gelled carrier when the drug is below the discharge temperature. The gelled carrier composition is a gel that is mechanically broken into gels. The radiation curable hot melt ink jet ink is disclosed, characterized in that it is a thixotropic composition having a recovery time longer than 60 seconds after the viscosity is stepped down.

Also, for example, in Patent Document 2, at least one curable wax that can be cured by free radical polymerization; and a liquid at a temperature of about 20 to about 25 ° C., the total weight of the curable paste ink composition At least one curable liquid component present in an amount of less than about 20% by weight; optionally a non-curable wax; at least one free radical photoinitiator or photoinitiating moiety; at least one curable A gelling agent; and optionally a colorant, and this component forms a curable ink composition that is a paste at a first temperature, wherein the first temperature is from about 20 to about 25 ° C .; This component forms a liquid composition at a second temperature, the second temperature being greater than about 40 ° C .; the at least one curable wax is an acrylate, methacrylate, alkene, Radiation curable paste ink composition comprising a functional group of nyl, allyl ether, wherein at least one liquid component is selected from the group consisting of monofunctional monomers, difunctional monomers, trifunctional monomers, pentafunctional monomers and combinations thereof Things are disclosed.

Special table 2009-510184 JP 2012-236998 A

Conventionally, as in Patent Document 1 and Patent Document 2, droplets that have undergone an instantaneous phase change when landed on a recording medium, such as plain paper, with an ink obtained by adding a gelling agent to an actinic ray curable compound. There is a technology for preventing the mixing of images and forming a high-definition image even at high-speed printing.

However, the inkjet ink to which the gelling agent is added, the gel collapses before transportation or before being put into a printing machine such as an inkjet recording apparatus, and the gelling agent and the liquid component (from the actinic radiation curable inkjet ink to the gelling agent). There is a problem in that separation from the removed component) occurs and density unevenness occurs in the image. In addition, since the gel collapses and separation of the gelling agent and the liquid component (the component obtained by removing the gelling agent from the actinic radiation curable inkjet ink) occurs, the work efficiency when filling the ink pack with the inkjet ink is reduced. There is a problem of doing.

In view of the above circumstances, the present invention prevents the separation of the gelling agent and the liquid component (the component obtained by removing the gelling agent from the actinic ray curable ink-jet ink), and provides good image quality that does not cause density unevenness in the image. It is an object of the present invention to provide an actinic ray curable inkjet ink from which In addition, the present invention prevents the separation of the gelling agent and the liquid component (the component obtained by removing the gelling agent from the actinic radiation curable inkjet ink), and increases the working efficiency when filling the ink pack. An object of the present invention is to provide a type inkjet ink. Furthermore, the present invention prevents the separation of the gelling agent and the liquid component (the component obtained by removing the gelling agent from the actinic radiation curable ink-jet ink), thereby increasing the working efficiency. An object is to provide a filling method for filling. Furthermore, the present invention prevents the separation of the gelling agent and the liquid component (the component obtained by removing the gelling agent from the actinic ray curable ink-jet ink), and provides an activity capable of obtaining a good image quality without causing density unevenness in the image. It is an object of the present invention to provide an image forming method using a light curable inkjet ink.

As a result of intensive studies to achieve the above object, the present inventors have conducted the present invention, that is, separation of the gelling agent from the liquid component (the component obtained by removing the gelling agent from the actinic radiation curable inkjet ink). The present inventors have completed an invention relating to an actinic ray curable inkjet ink capable of preventing the above, a filling method for filling the ink pack with the inkjet ink, and an image forming method using the inkjet ink.

Specific means for achieving the above object are the following items (1) to (7).
(1) An actinic ray curable inkjet ink that reversibly undergoes a sol-gel phase change depending on temperature, comprising at least one gelling agent and at least one monomer, wherein the at least one monomer is 25 A monomer A having a viscosity at 50 ° C. of 50 cp or more, and the content of the monomer A is 40% by mass or more based on the total mass of the inkjet ink;
The viscosity before shearing and / or stirring the inkjet ink is 50 Pa · s or more and 2000 Pa · s or less, and the viscosity when the inkjet ink is sheared and filled in an ink pack is 20 Pa · s or less. An actinic ray curable ink jet ink characterized by the above.
(2) The at least one monomer includes a monomer B having a viscosity at 25 ° C. of 50 cp or more, a ClogP value of 4.5 or more and less than 7, and a molecular weight of 300 or more, The actinic ray curable inkjet ink according to item (1), wherein the content of the monomer B is 20% by mass or more based on the total mass of the inkjet ink.
(3) Item (1) or wherein the at least one gelling agent comprises a compound represented by the following general formula (G1) or a compound represented by the general formula (G2) The actinic ray curable inkjet ink according to item (2).
General formula (G1): R ₁ —CO—R ₂
General formula (G2): R ₃ —COO—R ₄
(In the general formulas (G1) and (G2), R ₁ to R ₄ each independently represents a hydrocarbon group containing a straight chain portion having 12 or more carbon atoms.)
(4) The at least one gelling agent contains two kinds of compounds represented by the following general formula (G1) and a compound represented by the general formula (G2) in combination. The actinic ray curable inkjet ink according to item (1) or item (2).
General formula (G1): R ₁ —CO—R ₂
General formula (G2): R ₃ —COO—R ₄
(In the general formulas (G1) and (G2), R ₁ to R ₄ each independently represents a hydrocarbon group containing a straight chain portion having 12 or more carbon atoms.)
(5) Any one of items (1) to (4), wherein the content of the at least one gelling agent is less than 5% by mass with respect to the total mass of the inkjet ink. 2. The actinic ray curable inkjet ink according to item 1.
(6) A filling method of filling an ink pack with the actinic ray curable inkjet ink according to any one of items (1) to (5), wherein the inkjet ink is sheared while being cooled. And / or filling the ink pack with stirring.
(7) A step of ejecting the actinic radiation curable inkjet ink according to any one of items (1) to (5) onto a recording medium, and irradiating the ink ejected onto the recording medium with actinic rays And a step of curing the ink.

According to the present invention, active light that prevents separation of the gelling agent and the liquid component (component obtained by removing the gelling agent from the actinic radiation curable ink-jet ink) and provides a good image quality with no density unevenness in the image is obtained. A curable inkjet ink is provided. In addition, according to the present invention, the separation of the gelling agent and the liquid component (the component obtained by removing the gelling agent from the actinic ray curable inkjet ink) is prevented, and the working efficiency when filling the ink pack is increased. A light curable inkjet ink is provided. Furthermore, the present invention prevents the separation of the gelling agent and the liquid component (the component obtained by removing the gelling agent from the actinic radiation curable ink-jet ink), thereby increasing the working efficiency. A filling method for filling is provided. Furthermore, the present invention prevents the separation of the gelling agent and the liquid component (the component obtained by removing the gelling agent from the actinic ray curable ink-jet ink), and provides an activity capable of obtaining a good image quality without causing density unevenness in the image. An image forming method using a photocurable ink-jet ink is provided.

FIG. 1A is a side view showing an example of a configuration of a main part of an ink jet recording apparatus 10 of a line recording type, which is one aspect of an ink jet recording apparatus in which an actinic ray curable ink jet ink according to the present invention is used. is there. FIG. 1B is a top view showing an example of a configuration of a main part of a line recording type inkjet recording apparatus 10 which is one aspect of an inkjet recording apparatus in which the actinic ray curable inkjet ink according to the present invention is used. is there. FIG. 2 is a top view showing an example of a configuration of a main part of a serial recording type inkjet recording apparatus 20 in which the actinic ray curable inkjet ink according to the present invention is used.

The present invention will be described in detail below.

1. Actinic ray curable inkjet ink The actinic ray curable inkjet ink according to the present invention (hereinafter sometimes simply referred to as inkjet ink) is an inkjet ink that reversibly undergoes sol-gel phase transition depending on temperature, and is at least one kind of ink A gelling agent and at least one monomer are included, and at least one monomer includes monomer A having a viscosity at 25 ° C. of 50 cp or more, and the content of monomer A is the total mass of the inkjet ink. The viscosity before shearing the inkjet ink is 50 Pa · s or more and 2000 Pa · s or less, and the inkjet ink is sheared and / or stirred to be filled in the ink pack. An ink jet having a viscosity of 20 Pa · s or less. Ink.

The inkjet ink according to the present invention can prevent separation of the gelling agent and the liquid component (the liquid component is a component obtained by removing the gelling agent from the inkjet ink; the same shall apply hereinafter). When an image is formed using the image, it is possible to obtain a good image quality that does not cause density unevenness in the image. In the actinic ray curable inkjet ink according to the present invention, at least when the inkjet ink is filled in the ink pack, the gelling agent and the liquid component are not separated. Moreover, since the gelling agent and the liquid component are not separated in the ink jet ink according to the present invention, the working efficiency when filling the ink pack with the ink jet ink is increased. That is, the actinic radiation curable inkjet ink according to the present invention is not separated into at least a gelling agent and a liquid component when filled in the ink pack, and therefore the actinic radiation curable inkjet ink according to the present invention has uniform fluidity. The operator can smoothly and efficiently fill the ink pack with the inkjet ink.

[Gelling agent]
The actinic ray curable inkjet ink according to the present invention contains at least one gelling agent. At least one gelling agent has a function of reversibly sol-gel phase transition of the actinic ray curable inkjet ink according to the present invention depending on temperature. The gelling agent may be soluble in at least one monomer at a temperature higher than the gelling temperature, and may be crystallized in the actinic radiation curable inkjet ink according to the present invention at a temperature equal to or lower than the gelling temperature.

When at least one kind of gelling agent crystallizes in the ink jet ink, a plate-like crystal which is a crystallized product of the gelling agent forms a space three-dimensionally and includes at least one monomer in the space. It is preferable. Thus, a structure in which at least one monomer is encapsulated in a space three-dimensionally surrounded by a plate-like crystal is sometimes referred to as a “card house structure”. When the card house structure is formed, at least one monomer of the liquid can be retained, and a droplet of the actinic ray curable inkjet ink can be pinned. Thereby, coalescence of droplets can be suppressed. In order to form a card house structure, it is preferable that at least one monomer dissolved in the ink and at least one gelling agent are compatible. On the other hand, when at least one monomer dissolved in the ink and at least one gelling agent are phase-separated, it may be difficult to form a card house structure.

The actinic ray curable ink-jet ink according to the present invention contains one kind, preferably two or more kinds of gelling agents in combination, and particularly in the case of a crystalline gelling agent, the crystals remain in the monomer even after the gel collapses. Can be mixed uniformly, and separation of the gelling agent and the liquid component can be effectively prevented.

In order to stably discharge the droplets of the actinic ray curable inkjet ink according to the present invention from the inkjet recording apparatus, the compatibility between the photopolymerizable compound and the gelling agent is good in the sol-like ink (at high temperature). It is necessary to be. Furthermore, in order to stably suppress coalescence of droplets even during high-speed printing, after the inkjet ink droplets have landed on the recording medium, the gelling agent quickly crystallizes to form a strong card house structure. It is preferable.

Examples of such gelling agents include
An aliphatic ketone compound;
Aliphatic ester compounds;
Petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam;
Plant waxes such as candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil, jojoba solid wax, and jojoba ester;
Animal waxes such as beeswax, lanolin and whale wax;
Mineral waxes such as montan wax and hydrogenated wax;
Hydrogenated castor oil or hydrogenated castor oil derivative;
Modified waxes such as montan wax derivatives, paraffin wax derivatives, microcrystalline wax derivatives or polyethylene wax derivatives;
Higher fatty acids such as behenic acid, arachidic acid, stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, and erucic acid;
Higher alcohols such as stearyl alcohol and behenyl alcohol;
Hydroxystearic acid such as 12-hydroxystearic acid;
12-hydroxystearic acid derivatives; fatty acid amides such as lauric acid amide, stearic acid amide, behenic acid amide, oleic acid amide, erucic acid amide, ricinoleic acid amide, 12-hydroxystearic acid amide (for example, Nikka Amide series manufactured by Nippon Kasei Co., Ltd.) ITOWAX series manufactured by Ito Oil Co., Ltd., FATTYAMID series manufactured by Kao Corporation, etc.);
N-substituted fatty acid amides such as N-stearyl stearic acid amide, N-oleyl palmitic acid amide;
Special fatty acid amides such as N, N′-ethylenebisstearylamide, N, N′-ethylenebis-12-hydroxystearylamide, and N, N′-xylylenebisstearylamide;
Higher amines such as dodecylamine, tetradecylamine or octadecylamine;
Stearyl stearic acid, oleyl palmitic acid, glycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, ethylene glycol fatty acid ester, polyoxyethylene fatty acid ester, etc. Marl series, RIKEN VITAMIN POM series, etc.);
Esters of sucrose fatty acids such as sucrose stearic acid and sucrose palmitic acid (eg Ryoto Sugar Ester series manufactured by Mitsubishi Chemical Foods);
Synthetic waxes such as polyethylene wax and α-olefin maleic anhydride copolymer wax (UNILIN series manufactured by Baker-Petrolite);
Dimer acid;
Dimer diol (such as PRIDA series manufactured by CRODA);
Fatty acid inulins such as inulin stearate;
Fatty acid dextrins such as dextrin palmitate and dextrin myristate (such as Leopard series manufactured by Chiba Flour Mills);
Glyceryl behenate eicosane diacid;
Eicosane polyglyceryl behenate (Nomshin Eulio Co., Ltd. Nomucoat series, etc.);
Amide compounds such as N-lauroyl-L-glutamic acid dibutylamide and N- (2-ethylhexanoyl) -L-glutamic acid dibutylamide (available from Ajinomoto Fine Techno);
Dibenzylidene sorbitols such as 1,3: 2,4-bis-O-benzylidene-D-glucitol (available from Gelol D Shin Nippon Rika);
Low molecular oil gelling agents described in JP-A-2005-126507, JP-A-2005-255821 and JP-A-2010-111170;
Etc. are included.

The actinic ray curable inkjet ink according to the present invention preferably contains a compound containing a linear alkyl group having 12 or more carbon atoms as a gelling agent. When the gelling agent contains a linear alkyl group having 12 or more carbon atoms, the aforementioned “card house structure” is easily formed. The structure of the gelling agent may have a branched chain.

Specific examples of the gelling agent containing a linear alkyl group having 12 or more carbon atoms include aliphatic ketone compounds, aliphatic ester compounds, higher fatty acids, higher alcohols having a linear alkyl group having 12 or more carbon atoms, Fatty acid amides and the like are included. However, a gelling agent having a polar group such as —OH or —COOH at the end of the alkyl chain has poor stability in a sol-like ink, and may precipitate or phase-separate. In addition, the gelling agent may gradually bleed out with time from the cured film of the ink. Therefore, the gelling agent is preferably an aliphatic ketone compound or an aliphatic ester compound.

The at least one gelling agent contained in the actinic radiation curable inkjet ink according to the present invention preferably contains a compound represented by the following general formula (G1) or a compound represented by the following general formula (G2). In addition, at least one gelling agent contained in the actinic radiation curable inkjet ink according to the present invention includes two kinds of compounds represented by the following general formula (G1) and the following general formula (G2). It is preferable to include it in combination. These two preferred embodiments more effectively prevent separation of at least one gelling agent and a liquid component contained in the actinic ray curable inkjet ink according to the present invention at least when filling the ink pack. Can do.

The compound represented by the general formula (G1) and the compound represented by the following general formula (G2) are as follows.
General formula (G1): R ₁ —CO—R ₂
General formula (G2): R ₃ —COO—R ₄
(In the general formulas (G1) and (G2), R ₁ to R ₄ each independently represents a hydrocarbon group containing a straight chain portion having 12 or more carbon atoms.)

In General Formula (G1), the hydrocarbon groups represented by R ₁ and R ₂ are each independently preferably an aliphatic hydrocarbon group including a linear portion having 12 to 25 carbon atoms. If the straight chain portion contained in the aliphatic hydrocarbon group represented by R ₁ and R ₂ has less than 12 carbon atoms, it does not function as a gelling agent because it does not have sufficient crystallinity. In this card house structure, there is a possibility that a sufficient space for encapsulating the photopolymerizable compound cannot be formed. On the other hand, if the number of carbon atoms in the straight chain portion contained in the aliphatic hydrocarbon group exceeds 25, the melting point becomes too high, so that the ink may not be dissolved in the ink unless the ink discharge temperature is increased.

Examples of the aliphatic ketone compound represented by the general formula (G1) include dilignoceryl ketone (C24-C24), dibehenyl ketone (C22-C22, melting point 88 ° C.), distearyl ketone (C18-C18, 84 ° C.), dieicosyl ketone (C20-C20), dipalmityl ketone (C16-C16, melting point 80 ° C.), dimyristyl ketone (C14-C14), dilauryl ketone (C12-C12, melting point 68 ° C.) , Lauryl myristyl ketone (C12-C14), lauryl palmityl ketone (C12-C16), myristyl palmityl ketone (C14-C16), myristyl stearyl ketone (C14-C18), myristyl behenyl ketone (C14-C22), palmityl Stearyl ketone (C16-C18), Valmityl behenyl ketone ( 16-C22), include stearyl and behenyl ketone (C18-C22) and the like.

Examples of commercial products of the compound represented by the general formula (G1) include 18-Pentriacontanon (made by Alfa Aeser), Hentriacontan-16-on (made by Alfa Aeser), Kao wax T1 (made by Kao Corporation) and the like. Is included.
The aliphatic ketone compound contained in the ink may be only one type or a mixture of two or more types.

In the general formula (G2), the hydrocarbon group represented by R ₃ and R ₄ is not particularly limited, but is preferably an aliphatic hydrocarbon group including a straight chain portion having 12 to 26 carbon atoms. . When the number of carbon atoms in the straight chain portion contained in the aliphatic hydrocarbon group represented by R ₃ and R ₄ is 12 or more and 26 or less, the gelling agent is formed in the same manner as the compound represented by the general formula (G1). The above-mentioned card house structure can be formed while having the necessary crystallinity, and the melting point does not become too high.
Examples of the aliphatic ester compound represented by the formula (G2) include behenyl behenate (C21-C22, melting point 70 ° C.), icosyl icosanoate (C19-C20), stearyl stearate (C17-C18, melting point 60 ° C.). ), Palmitic acid stearate (C17-C16), lauryl stearate (C17-C12), cetyl palmitate (C15-C16, melting point 54 ° C.), stearyl palmitate (C15-C18), myristyl myristate (C13-C14), Melting point 43 ° C), cetyl myristate (C13-C16, melting point 50 ° C), octyldodecyl myristate (C13-C20), stearyl oleate (C17-C18), stearyl erucate (C21-C18), stearyl linoleate ( C17-C18), behenyl oleate (C18-C 2), myricyl cellotate (C25-C16), stearyl montanate (C27-C18), behenyl montanate (C27-C22), arachidyl linoleate (C17-C20), palmityl triacontanoate (C29-C16), etc. included.

Examples of commercially available aliphatic ester compounds represented by the formula (G2) include Unistar M-2222SL (manufactured by NOF Corporation), EXCEPARL SS (manufactured by Kao Corporation, melting point 60 ° C.), EMALEX CC-18 ( Nippon Emulsion Co., Ltd.), Amreps PC (manufactured by Higher Alcohol Industry Co., Ltd.), Exepar MY-M (Kao Co., Ltd.), Spalm Acechi (Nissho Co., Ltd.), EMALEX CC-10 (Nihon Emulsion Co., Ltd.) Is included. Since these commercial products are often a mixture of two or more types, they may be separated and purified as necessary.

The aliphatic ester compound contained in at least one gelling agent in the present invention may be only one kind or a mixture of two or more kinds.

The content of at least one gelling agent contained in the actinic radiation curable inkjet ink according to the present invention is preferably less than 5% by mass relative to the total mass of the inkjet ink, and is “less than 3.5% by mass”. Is more preferable. When the content of at least one gelling agent is less than 5% by mass with respect to the total mass of the ink-jet ink, it is included in the actinic ray curable ink-jet ink according to the present invention at least when filling the ink pack, Separation of at least one gelling agent and the liquid component can be more effectively prevented.

[At least one monomer]
The actinic ray curable inkjet ink according to the present invention includes at least one monomer, and the at least one monomer includes monomer A. The ink-jet ink according to the present invention preferably contains at least one monomer, and at least one monomer contains monomer B.

(Monomer A and Monomer B)
The monomer A is a monomer having a viscosity of 50 cp or more at 25 ° C. When the viscosity of the monomer A at 25 ° C. is 50 cp or more, at least when the ink is filled in the ink pack, the actinic ray curable inkjet ink according to the present invention is used. Separation between the contained at least one gelling agent and the liquid component can be effectively prevented.

The content of the monomer A is 40% by mass or more, preferably 45% by mass or more, and more preferably 50% by mass or more with respect to the total mass of the inkjet ink. When the content of the monomer A is preferably 45% by mass or more, at least when the ink pack is filled, at least one gelling agent and a liquid component contained in the actinic radiation curable inkjet ink according to the present invention. Separation can be prevented more effectively.

Monomer B has a viscosity at 25 ° C. of 50 cp or more, a ClogP value of 4.5 or more and less than 7, and a molecular weight of 300 or more. The viscosity of the monomer B at 25 ° C. is preferably 60 cp or more, and more preferably 70 cp or more at 25 ° C. When the viscosity of the monomer B at 25 ° C. is preferably 60 cp or more, at least when the ink pack is filled, at least one gelling agent contained in the actinic radiation curable inkjet ink according to the present invention and the liquid component are separated. Can be prevented more effectively.

The ClogP value of monomer B is preferably 4.5 or more and less than 5.5. When the ClogP value of the monomer B is preferably 4.5 or more and less than 5.5, at least one gelling agent contained in the actinic ray curable ink-jet ink according to the present invention is used when the ink pack is filled. Separation from the liquid component can be more effectively prevented.

Here, the “Log P value” is a coefficient indicating the affinity of an organic compound for water and 1-octanol. The 1-octanol / water partition coefficient P is a distribution equilibrium when a trace amount of compound is dissolved as a solute in a two-liquid solvent of 1-octanol and water, and is a ratio of the equilibrium concentration of the compound in each solvent. Their logarithm LogP for the base 10 is shown. That is, the “log P value” is a logarithmic value of the 1-octanol / water partition coefficient and is known as an important parameter representing the hydrophilicity / hydrophobicity of a molecule.

“ClogP value” is a LogP value calculated by calculation. The CLogP value can be calculated by a fragment method, an atomic approach method, or the like. More specifically, ClogP values are calculated in the literature (C. Hansch and A. Leo, “Substitutants Constants for Correlation Analysis in Chemistry and Biology” (John Wiley & Sons 69, described in John Wiley & Sons 69). Or the following commercially available software package 1 or 2 may be used.

Software Package 1: MedChem Software (Release 3.54, Aug. 1991, Medicinal Chemistry Project, Pomona College, Clarmont, CA)
Software package 2: Chem Draw Ultra ver. 8.0. (April 2003, CambridgeSoft Corporation, USA)

The numerical value of the ClogP value described in the present specification and the like is a “ClogP value” calculated using the software package 2.

The molecular weight of the monomer B is preferably 400 or more, and more preferably 450 or more. When the molecular weight of the monomer B is preferably 400 or more, at least when the ink pack is filled, at least one gelling agent and the liquid component contained in the actinic radiation curable inkjet ink according to the present invention are more separated. It can be effectively prevented.

The content of the monomer B is 20% by mass or more, preferably 25% by mass or more, and more preferably 30% by mass or more with respect to the total mass of the inkjet ink. When the content of the monomer B is preferably 25% by mass or more, at least when the ink pack is filled, at least one gelling agent and a liquid component contained in the actinic radiation curable inkjet ink according to the present invention. Separation can be prevented more effectively.

The viscosity of the monomer A and the monomer B is measured in a rotation mode using, for example, an apparatus MCR-300 (manufactured by Physica) (a cone plate uses 75Φ). Ten points are measured every 10 seconds at 25 ° C. and a shear rate of 1000 1 / s, and the viscosity when the seven points are averaged from the last measurement point is taken as the viscosity of monomers A and B.

Monomer A and monomer B are photopolymerizable compounds that are crosslinked or polymerized by actinic rays. The actinic rays are, for example, electron beams, ultraviolet rays, α rays, γ rays, and X-rays, and preferably ultraviolet rays and electron beams. Monomer A and monomer B are radically polymerizable compounds or cationically polymerizable compounds, preferably radically polymerizable compounds.

The radical polymerizable compound is a compound (monomer) having an ethylenically unsaturated bond capable of radical polymerization. A radically polymerizable compound may be used independently and may be used in combination of 2 or more type.

Examples of the compound having an ethylenically unsaturated bond capable of radical polymerization include an unsaturated carboxylic acid and a salt thereof, an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid urethane compound, an unsaturated carboxylic acid amide compound and an anhydride thereof, Examples include acrylonitrile, styrene, unsaturated polyester, unsaturated polyether, unsaturated polyamide, and unsaturated urethane. Examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and the like.

Among these, the radical polymerizable compound is preferably an unsaturated carboxylic acid ester compound, and more preferably a (meth) acrylate compound. The (meth) acrylate compound may be not only a monomer described later, but also an oligomer, a mixture of a monomer and an oligomer, a modified product, an oligomer having a polymerizable functional group, and the like. Here, “(meth) acrylate” refers to both and / or “acrylate” and “methacrylate”, and “(meth) acryl” refers to both and / or “acryl” and “methacryl”.

The relationship between monomer A and monomer B will be described. If one specific monomeric compound corresponds to monomer B, it also corresponds to monomer A. Further, one specific monomer compound does not correspond to the monomer B, but may correspond to the monomer A. That is, monomer B is included in monomer A.

In the following, preferred exemplary compounds of monomer A and monomer B are shown, but not limited thereto. In addition, the viscosity of the following preferable all exemplary compounds of the monomer A and the monomer B is 50 cp or more at 25 degreeC.

Examples of monomer A and monomer B include alkoxylated neopentyl glycol diacrylate (viscosity 131), polyethylene glycol # 600 dimethacrylate (viscosity 77.2, molecular weight 770), polyethylene glycol # 400 diacrylate (viscosity 59.4). , Molecular weight 508, Clog P0.47), polyethylene glycol # 600 diacrylate (viscosity 97.1, molecular weight 742), dioxane glycol diacrylate (viscosity 260, molecular weight 326, Clog P3.03), 3EO-modified trimethylolpropane triacrylate (viscosity) 61.2, molecular weight 429, ClogP 3.97), 9EO modified trimethylolpropane triacrylate (viscosity 108, molecular weight 693, ClogP3.21), tetramethylol methanetri Chryrate (viscosity 490, molecular weight 298), 4EO modified pentaerythritol tetraacrylate (viscosity 131, molecular weight 528, Clog P2.28), 5EO modified pentaerythritol tetraacrylate (viscosity 176), dipentaerythritol polyacrylate (viscosity 6500, molecular weight 525, ClogP1.53 or 2.94), glycerin propoxyacrylate (viscosity 94.4, molecular weight 428, ClogP2.66), caprolactone-modified dipentaerythritol hexaacrylate (viscosity 80), caprolactone acrylate (viscosity 80, molecular weight 344, ClogP2.09) In addition, tricyclodecane dimethanol diacrylate (viscosity 131, molecular weight 304, Clog P4.69), 6EO-modified trimethylo Lepropane triacrylate (viscosity 92, molecular weight 560, ClogP 3.57), 3PO-modified trimethylolpropane triacrylate (viscosity 82.2, molecular weight 471, ClogP4.9), ditrimethylolpropane tetraacrylate (viscosity 617, molecular weight 467, ClogP4) .85), nonylphenol 8EO modified acrylate (viscosity 180, molecular weight 626, ClogP6.42), tricyclodecane dimethanol dimethacrylate (viscosity 100, molecular weight 332, ClogP5.12) and the like.

[Viscosity of actinic ray curable inkjet ink]
The viscosity of the actinic radiation curable inkjet ink according to the present invention is 50 Pa · s or more and 2000 Pa · s or less before the inkjet ink is sheared and / or stirred, and the inkjet ink is sheared and filled into an ink pack. The viscosity when it is used is 20 Pa · s or less. Here, the viscosity before shearing and / or stirring the ink-jet ink is the viscosity at room temperature when the dissolved ink-jet ink (80 ° C. to 90 ° C.) is cooled to room temperature without shearing and / or stirring. means. The viscosity when ink jet ink is sheared and / or stirred and filled into the ink pack is when shearing and / or stirring is performed and the gelling agent and the monomer in the ink jet ink are in a uniform state. The viscosity of

Even if the ink is once sheared and / or stirred, the ink that has been heated and dissolved at 80 ° C. to 90 ° C. and then cooled to near room temperature resets the sheared state, so before the shearing and / or stirring. It can be regarded as an inkjet ink. That is, the viscosity of the actinic radiation curable inkjet ink according to the present invention may be 50 Pa · s or more and 2000 Pa · s or less in any given state, and the viscosity after shearing may be 20 Pa · s or less.

The viscosity before shearing and / or stirring the ink-jet ink is 50 Pa · s or more and 2000 Pa · s or less, at least when it is filled in the ink pack, at least contained in the actinic radiation curable ink-jet ink according to the present invention, Separation of one kind of gelling agent and liquid component can be effectively prevented.

When the ink is sheared and / or stirred and filled into the ink pack with a viscosity of 20 Pa · s or less, at least when the ink is filled into the ink pack, it is contained in the actinic radiation curable inkjet ink according to the present invention. Separation of at least one gelling agent and the liquid component can be effectively prevented.

The shearing and stirring may be performed by any method as long as the effects of the present invention are achieved. As a preferable method of shearing and stirring, while the inkjet ink in a dissolved state (80 ° C. to 90 ° C.) is cooled to 50 ° C. or lower, Examples of the method include shearing and / or stirring. By this preferable method, before forming a strong card house structure, the crystal can be made into a single form, and the storage stability and work efficiency can be further improved. When shearing and / or stirring is performed after cooling, the crystals may be difficult to become single, and the storage stability may not be further improved. In addition, since it takes some time to become uniform, there is a possibility that workability and the like may be reduced. In addition, although it is preserving, it means that the gelling agent and the liquid component (the component obtained by removing the gelling agent from the actinic ray curable ink-jet ink) are not easily separated.

The viscosity before shearing the inkjet ink is measured in an oscillation mode using, for example, an apparatus MCR-300 (manufactured by Physica) (a cone plate uses 75Φ). Cooling from 90 ° C. to 30 ° C. at a speed of 0.1 ° C./second, while cooling, the complex viscosity at a strain of 5% and an angular frequency of 10 rad / s is measured every 2 seconds, and the complex viscosity at 30 ° C. is measured. The viscosity before shearing the inkjet ink.

The viscosity when ink-jet ink is sheared and filled into the ink pack is measured in the oscillation mode using, for example, the apparatus MCR-300 (manufactured by Physica) (the cone plate uses 75Φ). At 30 ° C., the complex viscosity is measured at a strain of 5% and an angular frequency of 10 rad / s. 30 points are measured every 2 seconds, and the value obtained by averaging 5 points from the last point is taken as the viscosity when ink-jet ink is sheared and filled into the ink pack.

[Photopolymerization initiator]
The actinic radiation curable inkjet ink according to the present invention may further contain a photopolymerization initiator. Specifically, when the actinic ray is an electron beam, a photopolymerization initiator may ordinarily not be included. However, when the actinic ray is an ultraviolet ray, a photopolymerization initiator is preferably contained.

The photopolymerization initiator includes an intramolecular bond cleavage type and an intramolecular hydrogen abstraction type. Examples of intramolecular bond cleavage type photopolymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2 -Hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4 Acetophenones such as -thiomethylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 2 , 4,6-Trimethylbenzoindiphenylphosphine Acylphosphine oxide, such as Sid; as benzyl and methyl phenylglyoxylate esters include.

Examples of intramolecular hydrogen abstraction type photopolymerization initiators include benzophenone, methyl 4-phenylbenzophenone, o-benzoylbenzoate, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl Benzophenones such as sulfide, acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4 -Thioxanthone series such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; Aminobenzophenone series such as Michler's ketone, 4,4'-diethylaminobenzophenone; 10-Butyl-2-chloroaclide , 2-ethyl anthraquinone, 9,10-phenanthrenequinone, include camphorquinone, and the like.

The content of the photopolymerization initiator in the actinic ray curable inkjet ink according to the present invention is preferably 0.01% by mass to 10% by mass, although it depends on the actinic ray and the type of the actinic ray curable compound. It is more preferably 2 to 8% by mass.

The actinic ray curable inkjet ink according to the present invention may contain a photoacid generator as a photopolymerization initiator. Examples of photoacid generators include chemically amplified photoresists and compounds used for photocationic polymerization (Organic Electronics Materials Study Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), 187. See page 192).

The actinic ray curable inkjet ink according to the present invention may further contain a photopolymerization initiator auxiliary agent, a polymerization inhibitor, and the like, if necessary. The photopolymerization initiator assistant may be a tertiary amine compound, preferably an aromatic tertiary amine compound. Examples of aromatic tertiary amine compounds include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethylamino-p-benzoic acid ethyl ester, N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester, N, N-dihydroxyethylaniline, triethylamine, N, N-dimethylhexylamine and the like are included. Of these, N, N-dimethylamino-p-benzoic acid ethyl ester and N, N-dimethylamino-p-benzoic acid isoamyl ethyl ester are preferred. These compounds may be used alone or in combination of two or more.

Examples of polymerization inhibitors include (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone , Nitrosobenzene, 2,5-di-t-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3-oxyanilino- 1,3-Dimethylbutylidene) aniline oxide, dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraloxime, methyl ethyl ketoxime, cyclohexanone oxime It is included.

[Color material]
The actinic ray curable ink-jet ink may further contain a coloring material as necessary. The coloring material can be a dye or a pigment, but is preferably a pigment because it has good dispersibility with respect to the components of the ink and is excellent in weather resistance. The pigment is not particularly limited, and may be, for example, an organic pigment or an inorganic pigment having the following numbers described in the color index.

Examples of red or magenta pigments include Pigment Red 3, 5, 19, 22, 31, 38, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, 53. : 1, 57: 1, 57: 2, 58: 4, 63: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 88, 104, 108, 112, 122, 123, 144 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13, 16, 20, 36, etc. are included. Examples of blue or cyan pigments include Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17-1, 22, 27, 28, 29, 36. , 60 and the like. Examples of green pigments include Pigment Green 7, 26, 36, and 50. Examples of yellow pigments include Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 137. 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193 and the like. Examples of the black pigment include Pigment Black 7, 28, 26 and the like.

Examples of commercially available pigments include chromofine yellow 2080, 5900, 5930, AF-1300, 2700L, chromofine orange 3700L, 6730, chromofine scarlet 6750, chromofine magenta 6880, 6886, 6891N, 6790, 6887, chromo Fine Violet RE, Chromo Fine Red 6820, 6830, Chromo Fine Blue HS-3, 5187, 5108, 5197, 5085N, SR-5020, 5026, 5050, 4920, 4927, 4937, 4824, 4933GN-EP, 4940, 4973, 5205, 5208, 5214, 5221, 5000P, Chromofine Green 2GN, 2GO, 2G-550D, 5310, 5370, 6830, Chromofine Black A-1103, Seika Fast Yellow 10GH, A-3, 2035, 2054, 2200, 2270, 2300, 2400 (B), 2500, 2600, ZAY-260, 2700 (B), 2770, Seica Fast Red 8040, C405 (F), CA120, LR-116, 1531B, 8060R, 1547, ZAW-262, 1537B, GY, 4R-4016, 3820, 3891, ZA-215, Seika Fast Carmine 6B1476T-7, 1483LT, 3840, 3870, Seika Fast Bordeaux 10B-430, Seikalite Rose R40, Seikalite Violet B800, 7805, Seika Fast Maroon 460N, Seika Fast Orange 900, 2900, Seika Light Blue C718, A 12, Cyanine Blue 4933M, 4933GN-EP, 4940,4973 (manufactured by Dainichiseika Color & Chemicals Mfg.);
KET Yellow 401, 402, 403, 404, 405, 406, 416, 424, KET Orange 501, KET Red 301, 302, 303, 304, 305, 306, 307, 308, 309, 310, 336, 337, 338, 346, KET Blue 101, 102, 103, 104, 105, 106, 111, 118, 124, KET Green 201 (Dainippon Ink Chemical Co., Ltd.);
Colortex Yellow 301, 314, 315, 316, P-624, 314, U10GN, U3GN, UNN, UA-414, U263, Finecol Yellow T-13, T-05, Pigment Yellow 1705, Colortex Orange 202, Color103 101, Color103 101 115, 116, D3B, P-625, 102, H-1024, 105C, UFN, UCN, UBN, U3BN, URN, UGN, UG276, U456, U457, 105C, USN, Colortex Maroon601, Colortex Brownex600 Red 122, Colortex Blue 516, 517, 518, 519, A8 8, P-908,510, Colortex Green402,403, Colortex Black 702, U905 (manufactured by Sanyo Color Works);
Lionol Yellow 1405G, Lionol Blue FG7330, FG7350, FG7400G, FG7405G, ES, ESP-S (manufactured by Toyo Ink),
Toner Magenta E02, Permanent RubinF6B, Toner Yellow HG, Permanent Yellow GG-02, Hostapeam Blue B2G (manufactured by Hoechst Industry);
Novoperm P-HG, Hostaperm Pink E, Hostaperm Blue B2G (manufactured by Clariant);
Carbon black # 2600, # 2400, # 2350, # 2200, # 1000, # 990, # 980, # 970, # 960, # 950, # 850, MCF88, # 750, # 650, MA600, MA7, MA8, MA11 , MA100, MA100R, MA77, # 52, # 50, # 47, # 45, # 45L, # 40, # 33, # 32, # 30, # 25, # 20, # 10, # 5, # 44, CF9 (Mitsubishi Chemical).

The pigment can be dispersed by, for example, a ball mill, sand mill, attritor, roll mill, agitator, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, wet jet mill, paint shaker, or the like. The pigment is dispersed such that the volume average particle diameter of the pigment particles is preferably 0.08 to 0.5 μm, and the maximum particle diameter is preferably 0.3 to 10 μm, more preferably 0.3 to 3 μm. It is preferable. The dispersion of the pigment is adjusted by the selection of the pigment, the dispersant, and the dispersion medium, the dispersion conditions, the filtration conditions, and the like.

The actinic ray curable inkjet ink according to the present invention may further contain a dispersant in order to enhance the dispersibility of the pigment. Examples of the dispersant include a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, a high molecular weight unsaturated acid ester , Polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, polyoxyethylene Nonylphenyl ether, stearylamine acetate and the like are included. Examples of commercially available dispersants include Avecia's Solsperse series and Ajinomoto Fine-Techno's PB series.

The actinic ray curable inkjet ink according to the present invention may further contain a dispersion aid as necessary. The dispersion aid may be selected according to the pigment.

The total amount of the dispersing agent and the dispersing aid is preferably 1 to 50% by mass with respect to the pigment.

The actinic ray curable inkjet ink according to the present invention may further include a dispersion medium for dispersing the pigment, if necessary. A solvent may be included in the ink as a dispersion medium. However, in order to suppress the residual solvent in the formed image, the actinic ray curable compound (particularly a monomer having a low viscosity) is used as the dispersion medium. It is preferable.

The dye can be an oil-soluble dye or the like. Examples of oil-soluble dyes include the following various dyes. Examples of magenta dyes include MS Magenta VP, MS Magenta HM-1450, MS Magenta HSo-147 (above, manufactured by Mitsui Toatsu), AIZENSOT Red-1, AIZEN SOT Red-2, AIZEN SOTRed-3, AIZEN SOT Pink-1, SPIRON Red GEH SPECIAL (above, manufactured by Hodogaya Chemical Co., Ltd.), RESOLIN Red FB 200%, MACROLEX Red Violet R, MACROLEX ROT5B (above, manufactured by Bayer Japan Co., Ltd.), KAYASET Red K, RED A 802 (above, Nippon Kayaku Co., Ltd.), PHLOXIN, ROSE Bengal, ACID Red (above, Manufactured by Iva Kasei), HSR-31, DIARESIN Red K (manufactured by Mitsubishi Kasei Corp.), include Oil Red (manufactured by BASF Japan Ltd.).

Examples of cyan dyes include MS Cyan HM-1238, MS Cyan HSo-16, Cyan HSo-144, MS Cyan VPG (manufactured by Mitsui Toatsu), AIZEN SOT Blue-4 (manufactured by Hodogaya Chemical Co., Ltd.), RESOLIN BR. Blue BGLN 200%, MACROLEX Blue RR, CERES Blue GN, SIRIUS SUPRATURQ. Blue Z-BGL, SIRIUS SUTRA TURQ. Blue FB-LL 330% (from Bayer Japan), KAYASET Blue FR, KAYASET Blue N, KAYASET Blue 814, Turq. Blue GL-5 200, Light Blue BGL-5 200 (Nippon Kayaku Co., Ltd.), DAIWA Blue 7000, Olesol Fast Blue GL (Daiwa Kasei Co., Ltd.), DIARESIN Blue P (Mitsubishi Chemical Co., Ltd.) Blue 670, NEOPEN Blue 808, ZAPON Blue 806 (above, manufactured by BASF Japan Ltd.) and the like are included.

Examples of yellow dyes include MS Yellow HSm-41, Yellow KX-7, Yellow EX-27 (Mitsui Toatsu), AIZEN SOT Yellow-1, AIZEN SOT Yellow W-3, AIZEN SOT Yellow-6 (above, Hodogaya (Manufactured by Kagakusha), MACROLEX Yellow 6G, MACROLEX FLUOR. Yellow 10GN (above, Bayer Japan), KAYASET Yellow SF-G, KAYASET Yellow 2G, KAYASET Yellow A-G, KAYASET Yellow EG (above, Nippon Kayaku), DAIWA Yellow 330B HSY-68 (manufactured by Mitsubishi Kasei Co., Ltd.), SUDAN Yellow 146, NEOPEN Yellow 075 (manufactured by BASF Japan Ltd.) and the like.

Examples of black dyes include MS Black VPC (Mitsui Toatsu Co., Ltd.), AIZEN SOT Black-1, AIZEN SOT Black-5 (above, manufactured by Hodogaya Chemical Co., Ltd.), RESORIN Black GSN 200%, RESOLIN BlackBS (above, Bayer Japan), KAYASET Black AN (Nippon Kayaku), DAIWA Black MSC (Daiwa Kasei), HSB-202 (Mitsubishi Kasei), NEPTUNE Black X60, NEOPEN Black X58 (above, BASF) Japan product).

The content of the pigment or dye is preferably 0.1 to 20% by mass, more preferably 0.4 to 10% by mass with respect to the actinic ray curable inkjet ink. This is because if the content of the pigment or dye is too small, the color of the resulting image is not sufficient, and if it is too large, the viscosity of the ink increases and the jetting property decreases.

[Other ingredients]
The actinic ray curable inkjet ink according to the present invention may further contain other components as necessary. Other components may be various additives, other resins, and the like. Examples of the additive include a surfactant, a leveling additive, a matting agent, an ultraviolet absorber, an infrared absorber, an antibacterial agent, and a basic compound for enhancing the storage stability of the ink. Examples of basic compounds include basic alkali metal compounds, basic alkaline earth metal compounds, basic organic compounds such as amines, and the like. Examples of other resins include resins for adjusting the physical properties of the cured film, such as polyester resins, polyurethane resins, vinyl resins, acrylic resins, rubber resins, and waxes. It is.

(Method for preparing actinic ray curable inkjet ink)
The actinic ray curable inkjet ink according to the present invention is obtained by mixing at least one gelling agent and at least one monomer, and a colorant and a photopolymerization initiator suitably contained under heating. For example, a pigment dispersion in which a color material (particularly a pigment) is dispersed in a part of the photopolymerizable compound is prepared and mixed with the pigment dispersion and other ink components. The obtained ink is preferably filtered through a predetermined filter. In order to improve the discharge property of the actinic ray curable inkjet ink according to the present invention, the viscosity of the ink at a high temperature is preferably not more than a certain level. Specifically, the viscosity of the actinic ray curable inkjet ink at 80 ° C. is preferably 3 to 20 mPa · s.

2. Filling Method The filling method according to the present invention is a filling method in which the actinic ray curable inkjet ink of the present invention is filled in an ink pack, and the ink pack is sheared and / or stirred while cooling the inkjet ink of the present invention. It is characterized by filling. It is preferable to shear and / or stir the inkjet ink in a dissolved state (80 ° C. to 90 ° C.) while cooling to 50 ° C. or less, but the gelling agent and the liquid component do not separate before filling the ink pack. In order to obtain a uniform state, it is preferable to cool to at least 70 ° C. to 50 ° C. and to shear and / or stir. In order to further enhance the effect of the present invention, it is preferable that the inkjet ink of the present invention is sheared and / or stirred while being cooled to 40 ° C. or lower, preferably 30 ° C. or lower.

3. Image Forming Method An image forming method according to the present invention includes a step of ejecting the actinic ray curable inkjet ink of the present invention onto a recording medium, a step of irradiating the ink ejected onto the recording medium with an actinic ray to cure the ink, , Including.

1) In the ejection process, the inkjet ink stored in the ejection recording head may be ejected as droplets toward the recording medium through the nozzles.

2) In the curing process, the ink that has landed on the recording medium is irradiated with light. What is necessary is just to select suitably the light irradiated according to the kind of actinic-light curable compound, and may be an ultraviolet-ray, an electron beam, etc.

The recording medium may be paper or a resin film. Examples of paper include coated paper for printing, coated paper B for printing, and the like. Examples of the resin film include a polyethylene terephthalate film and a vinyl chloride film.

4). Inkjet recording apparatus An actinic ray curable inkjet recording apparatus using the actinic radiation curable inkjet of the present invention will be described. Actinic ray curable ink jet recording apparatuses include a line recording method (single pass recording method) and a serial recording method. The line recording method (single-pass recording method) is preferable from the viewpoint of high-speed recording, although it may be selected according to the required image resolution and recording speed.

FIG. 1 is a diagram illustrating an example of a configuration of a main part of a line recording type inkjet recording apparatus. Among these, Fig.1 (a) is a side view, FIG.1 (b) is a top view. As shown in FIG. 1, the inkjet recording apparatus 10 covers a head carriage 16 that accommodates a plurality of ejection recording heads 14 and the entire width of the recording medium 12, and is downstream of the head carriage 16 (the conveyance direction of the recording medium). The actinic ray irradiation unit 18 disposed on the side and the temperature control unit 19 disposed on the lower surface of the recording medium 12 are provided.

The head carriage 16 is fixedly disposed so as to cover the entire width of the recording medium 12, and accommodates a plurality of ejection recording heads 14 provided for each color. Ink is supplied to the ejection recording head 14. For example, the ink may be supplied directly or by an ink supply unit (not shown) from an ink cartridge (not shown) that is detachably attached to the inkjet recording apparatus 10.

A plurality of ejection recording heads 14 are arranged in the transport direction of the recording medium 12 for each color. The number of ejection recording heads 14 arranged in the conveyance direction of the recording medium 12 is set according to the nozzle density of the ejection recording head 14 and the resolution of the print image. For example, when an image having a resolution of 1440 dpi is formed using the ejection recording head 14 having a droplet amount of 2 pl and a nozzle density of 360 dpi, the four ejection recording heads 14 are shifted with respect to the conveyance direction of the recording medium 12. What is necessary is just to arrange. Further, when an image having a resolution of 720 × 720 dpi is formed using the ejection recording head 14 having a droplet amount of 6 pl and a nozzle density of 360 dpi, the two ejection recording heads 14 may be arranged in a shifted manner. dpi represents the number of ink droplets (dots) per 2.54 cm.

The actinic ray irradiation unit 18 covers the entire width of the recording medium 12 and is arranged on the downstream side of the head carriage 16 in the conveyance direction of the recording medium. The actinic ray irradiation unit 18 irradiates the droplets ejected by the ejection recording head 14 and landed on the recording medium with actinic rays to cure the droplets.

When the active light is ultraviolet light, examples of the active light irradiation unit 18 (ultraviolet irradiation means) include a fluorescent tube (low pressure mercury lamp, germicidal lamp), a cold cathode tube, an ultraviolet laser, and an operating pressure of several hundred Pa to 1 MPa. These include low pressure, medium pressure, high pressure mercury lamps, metal halide lamps and LEDs. From the viewpoint of curability, ultraviolet irradiation means for irradiating ultraviolet rays having an illuminance of 100 mW / cm ² or more; specifically, high-pressure mercury lamps, metal halide lamps, and LEDs are preferable, and LEDs are more preferable from the viewpoint of low power consumption. Specifically, a 395 nm, water-cooled LED manufactured by Phoseon Technology can be used.

When the actinic ray is an electron beam, examples of the actinic ray irradiating unit 18 (electron beam irradiating unit) include electron beam irradiating means such as a scanning method, a curtain beam method, and a broad beam method. Therefore, a curtain beam type electron beam irradiation means is preferable. Examples of electron beam irradiation means include “Curetron EBC-200-20-30” manufactured by Nissin High Voltage Co., Ltd., “Min-EB” manufactured by AIT Co., Ltd., and the like.

The temperature control unit 19 is disposed on the lower surface of the recording medium 12 and maintains the recording medium 12 at a predetermined temperature. The temperature control unit 19 can be, for example, various heaters.

Hereinafter, an image forming method using the line recording type inkjet recording apparatus 10 will be described. The recording medium 12 is conveyed between the head carriage 16 and the temperature control unit 19 of the inkjet recording apparatus 10. On the other hand, the recording medium 12 is adjusted to a predetermined temperature by the temperature control unit 19. Next, high-temperature ink is ejected from the ejection recording head 14 of the head carriage 16 and adhered (landed) on the recording medium 12. Then, the actinic ray irradiating unit 18 irradiates the ink droplets attached on the recording medium 12 with an actinic ray to cure.

When the ink is ejected from the ejection recording head 14, the temperature of the ink in the ejection recording head 14 is 10 to 30 ° C. higher than the gelation temperature of the ink in order to improve the ink ejection property. It is preferably set. When the ink temperature in the ejection recording head 14 is less than (gelation temperature + 10) ° C., the ink gels in the ejection recording head 14 or on the nozzle surface, and the ink ejection property is likely to deteriorate. On the other hand, when the temperature of the ink in the ejection recording head 14 exceeds (gelation temperature + 30) ° C., the ink becomes too high, and the ink component may deteriorate.

Although the amount of droplets ejected from each nozzle of the ejection recording head 14 depends on the resolution of the image, it is preferably 1 pl to 10 pl in order to form a high resolution image. More preferably, it is from 5 to 4.0 pl.

Irradiation with actinic rays is performed within 10 seconds, preferably within 0.001 seconds to 5 seconds, more preferably after the ink droplets are deposited on the recording medium, in order to prevent adjacent ink droplets from coalescing. It is preferable to carry out within 0.01 second to 2 seconds. Irradiation with actinic rays is preferably performed after ink is ejected from all ejection recording heads 14 accommodated in the head carriage 16.

When the actinic ray is an electron beam, the acceleration voltage for electron beam irradiation is preferably 30 to 250 kV and more preferably 30 to 100 kV in order to perform sufficient curing. When the acceleration voltage is 100 to 250 kV, the electron beam irradiation amount is preferably 30 to 100 kGy, and more preferably 30 to 60 kGy.

The total ink film thickness after curing is preferably 2 to 25 μm. The “total ink film thickness” is the maximum value of the ink film thickness drawn on the recording medium.

FIG. 2 is a diagram illustrating an example of a configuration of a main part of the serial recording type inkjet recording apparatus 20. As shown in FIG. 2, the inkjet recording apparatus 20 has a width narrower than the entire width of the recording medium instead of the head carriage 16 fixedly arranged so as to cover the entire width of the recording medium, and a plurality of ejection recordings. Except for having a head carriage 26 that houses the head 24 and a guide portion 27 for moving the head carriage 26 in the width direction of the recording medium 12, the configuration can be the same as in FIG.

In the serial recording type inkjet recording apparatus 20, the head carriage 26 is ejected from the ejection recording head 24 accommodated in the head carriage 26 while moving in the width direction of the recording medium 12 along the guide portion 27. After the head carriage 26 has completely moved in the width direction of the recording medium 12 (for each pass), the recording medium 12 is fed in the transport direction. Except for these operations, an image is recorded in substantially the same manner as the line recording type inkjet recording apparatus 10 described above.

Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not construed as being limited by these descriptions.

[Production of actinic ray curable inkjet ink]
An actinic ray curable inkjet ink was prepared using the following components (gelator (wax), polymerizable compound, polymerization inhibitor, polymerization initiator, pigment dispersion).

[Gelling agent (wax)]
Distearyl ketone (Kao wax T1, manufactured by Kao Corporation)
Dipalmityl ketone (Hentriacontan-16-on, reagent (Arfa Aser))
Dilauryl ketone (12-tricosanone, reagent (Arfa Aser))
Behenyl behenate (Unistar M-2222SL, NOF Corporation)
Stearyl stearate (Exepal SS, manufactured by Kao Corporation)
Cetyl palmitate (Amreps PC, high alcohol industry)
Behenic acid (Lunac BA, manufactured by Kao Corporation)
Erucamide (Neutron S, manufactured by Nippon Seika Co., Ltd.)

[Polymerizable compound]
Polyethylene glycol # 400 diacrylate / A-400 Viscosity 56.8 ClogP 0.47
Nonylphenol 8EO modified acrylate / Miramer M166 Viscosity 180 ClogP 6.42
Tricyclodecane dimethanol diacrylate / SR833S Viscosity 130 ClogP 4.69
Others Tripropylene glycol diacrylate / EM223 Viscosity 12 ClogP 2.21

[Polymerization inhibitor]
Irgastab UV10 (Ciba Specialty Chemical)

[Polymerization initiator]
DAROCURE TPO (Ciba Specialty Chemical)

[Pigment dispersion]
Preparation of Pigment Dispersion Liquid 1 (M: Magenta) The following dispersant, actinic ray curable compound and polymerization inhibitor were placed in a stainless beaker and dissolved by heating and stirring for 1 hour while heating on a 65 ° C hot plate. It was. The resulting solution was cooled to room temperature, then the following magenta pigment 1 was added, put into a glass bottle together with 200 g of zirconia beads having a diameter of 0.5 mm, and sealed with a paint shaker for 8 hours. Thereafter, the zirconia beads were removed to prepare a pigment dispersion 1 having the following composition.

[Composition of Pigment Dispersion Liquid 1]
Dispersant: Azisper PB824 (manufactured by Ajinomoto Fine Techno Co., Ltd.) 9 parts by mass Actinic ray curable compound: EM-223 (tripropylene glycol diacrylate, manufactured by Choko Chemical Co., Ltd.) 70 parts by mass Polymerization inhibitor: Irgastab UV10 (Ciba Japan) 0.02 parts by mass Magenta pigment 1: Pigment Red 122 (manufactured by Dainichi Seika, Chromofine Red 6112JC) 21 parts by mass

[Preparation of ink]
According to the composition shown in the following Table 1, the mixture obtained by mixing each component was heated to 80 ° C. and stirred. The obtained solution was filtered through a # 3000 metal mesh filter under heating, and then cooled to prepare an ink. In Table 1, the unit of the amount of each component is part by mass.

[Pack filling method]
After filtering through a filter, cool to room temperature in a stationary state, shear and stir at room temperature, and fill the pack into method A. After filtering, cool from 80 ° C. to 50 ° C. with cooling and stirring Then, the method of stirring in a room temperature and filling the pack in a uniform state was designated as Method B.

[Image Forming Method]
A single color image was formed using the line type ink jet recording apparatus with the actinic ray curable ink jet ink obtained in each of the examples (Examples 1 to 12) and Comparative Examples 1 to 5. The temperature of the inkjet head of the inkjet recording apparatus was set to 80 ° C. A blank character, a solid image of 5 cm × 5 cm, or a density gradation patch was printed on the recording medium. After the image was formed, the ink was cured by irradiating the image with ultraviolet light using an LED lamp (395 nm manufactured by Phoseon Technology, water-cooled LED) disposed in the downstream portion of the recording apparatus. As the ejection recording head, a piezo head having a nozzle diameter of 20 μm and 512 nozzles (256 nozzles × 2 rows, staggered arrangement, 1 row nozzle pitch 360 dpi) was used. The ejection conditions were such that the amount of one droplet was 2.5 pl, and ejection was performed at a droplet velocity of about 6 m / s, and recording was performed at a resolution of 1440 dpi × 1440 dpi. The recording speed was 500 mm / s. Image formation was performed in an environment of 23 ° C. and 55% RH. dpi represents the number of dots per 2.54 cm.

[Evaluation of workability during filling]
The time taken from ink adjustment (after filter filtration) to filling the pack and the ease of work were ranked.
Rank 0: Gel fluidity is low and pack filling is difficult Rank 1: It takes time to disintegrate the gel, although fluidity is observed but variation is possible Rank 2: Time required to disintegrate the gel Uniform solution shorter than 1, high fluidity and easy filling

[Separation evaluation by transportation]
Whether or not there is a bias in the gelling agent after making clear ink prepared from the above ink manufacturing method using components excluding pigment dispersion, filling a transparent container 5kg each, loading it on a truck and transporting it Evaluation was made visually.
Rank 0: Less than 1000km, Separation rank 1: Up to 1000km No separation Rank 2: No separation up to 1500km Rank 3: No separation up to 2000km Rank 4: No separation up to 2500km Rank 5: No separation up to 3000km Is done.

[Evaluation of injection stability]
Ink jet recording apparatus equipped with each of the inks prepared above ejected ink from the ink jet head, visually observed for the absence of nozzles and ejection bends, and evaluated ejection stability according to the following criteria.
◎: No nozzle missing was observed. ○: Nozzle missing was observed in 1 to 4 nozzles in all nozzles 512. ×: Nozzle missing was observed in 5 or more nozzles in all nozzles 512. The

[Image quality evaluation: density unevenness / surface roughness]
By the above method, a solid image of 5 cm × 5 cm was printed on a recording medium for printing coated paper A (manufactured by OK TOPCOAT rice basis weight 128 g / m ² Oji Paper Co., Ltd.) was visually evaluated, density unevenness in accordance with the following evaluation criteria Was evaluated.
0: Clear density unevenness is observed 1: Density unevenness is observed 2: There is surface unevenness, but it can be used as image quality Level 3: Improved surface unevenness than 2: 4: Improved surface unevenness than 3: 5: almost no surface unevenness 6: no surface unevenness at all

(Results and discussion)
Compared with Comparative Examples 1 and 2, when no wax is included, the ejection stability is good, but the density is uneven and cannot be used. In contrast, in Examples 1 to 12, the density is not uneven and can be used as the image quality. Met.
According to the results, the surface roughness is good in the order of the wax amount of 5% by mass or more and less than 10% by mass (Examples 1 to 5), 3.5% by mass or more and less than 5% by mass, and less than 3.5% by mass. became.
According to Comparative Example 5, the ink cannot be filled without fluidity unless it is sheared and stirred before ink filling, and Comparative Examples 3 to 5 and when working from the Examples, the workability becomes Rank 1 level, and further cooling while shearing. It was found that the workability rank was 2 when shearing was performed by the B method (Examples 6 to 12).
In separation evaluation by transportation, separation occurs when the monomer of 50 cP or more is not contained or less than 40% from Comparative Examples 4 and 5, and in Examples 1 to 12, the monomer of 50 cP or more is 40% by mass. Since these are included, all of them can be used without being separated for transportation of 1000 km or more.
Furthermore, nonylphenol 8EO-modified acrylate Miramer M166 and / or tricyclodecane dimethanol diacrylate SR833S (viscosity at 25 ° C. is 50 cp or more, ClogP value is 4.5 or more and less than 7, and molecular weight is 300 20% by mass or more (Examples 2 to 12), the use of a ketone and an ester as a gelling agent (wax) (Examples 3 and 4), and the gelling agent (wax) as a ketone and an ester In combination with the above two types (Examples 5 to 12), the content of the gelling agent (wax) is reduced to 3.5% by mass or less (Examples 7 to 12) in order of transport test rank. It became.

The actinic ray curable inkjet ink of the present invention has good work efficiency and does not cause density unevenness, so that the image quality is good and is suitable for forming an image on a recording medium.

This application claims priority based on Japanese Patent Application No. 2014-052554 filed on March 14, 2014, and the contents described in the specification and drawings of the application are incorporated in this application. .

DESCRIPTION OF SYMBOLS 10, 20 Inkjet recording apparatus 12 Recording medium 14, 24 Ejection recording head 16, 26 Head carriage 18, 28 Actinic ray irradiation part 19 Temperature control part 27 Guide part

Claims (7)

1. An actinic ray curable inkjet ink that reversibly undergoes a sol-gel phase transition with temperature,
   At least one gelling agent;
   At least one monomer and at least
   The at least one monomer includes monomer A having a viscosity at 25 ° C. of 50 cp or more;
   The content of the monomer A is 40% by mass or more based on the total mass of the inkjet ink,
   The viscosity before shearing and / or stirring the inkjet ink is 50 Pa · s or more and 2000 Pa · s or less, and the viscosity when the inkjet ink is sheared and / or stirred and filled into an ink pack is 20 Pa. An actinic ray curable ink-jet ink, characterized by being s or less.
2. The at least one monomer includes a monomer B having a viscosity at 25 ° C. of 50 cp or more, a ClogP value of 4.5 or more and less than 7, and a molecular weight of 300 or more;
   The actinic ray curable inkjet ink according to claim 1, wherein the content of the monomer B is 20% by mass or more based on the total mass of the inkjet ink.
3. The activity according to claim 1 or 2, wherein the at least one gelling agent comprises a compound represented by the following general formula (G1) or a compound represented by the general formula (G2). Light curable inkjet ink.
   General formula (G1): R ₁ —CO—R ₂
   General formula (G2): R ₃ —COO—R ₄
   (In the general formulas (G1) and (G2), R ₁ to R ₄ each independently represents a hydrocarbon group containing a straight chain portion having 12 or more carbon atoms.)
4. The at least one gelling agent contains a compound represented by the following general formula (G1) and a compound represented by the general formula (G2) in combination. Or the actinic-light curable inkjet ink of 2.
   General formula (G1): R ₁ —CO—R ₂
   General formula (G2): R ₃ —COO—R ₄
   (In the general formulas (G1) and (G2), R ₁ to R ₄ each independently represents a hydrocarbon group containing a straight chain portion having 12 or more carbon atoms.)
5. The actinic ray curing according to any one of claims 1 to 4, wherein the content of the at least one gelling agent is less than 5% by mass with respect to the total mass of the inkjet ink. Type inkjet ink.
6. A filling method of filling an ink pack with the actinic ray curable inkjet ink according to any one of claims 1 to 5,
   A filling method comprising filling the ink pack by shearing and / or stirring while cooling the inkjet ink.
7. A step of ejecting the actinic radiation curable inkjet ink according to any one of claims 1 to 5 onto a recording medium, and a step of irradiating the ink ejected onto the recording medium with an actinic ray to cure the ink And an image forming method.

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